Coordination Chemistry of Polynitriles, Part XI. Influence of 4,4′-Bipyridine and Solvent on the Crystal and Molecular Structures of Alkaline Earth Pentacyanocyclopentadienides
Round 1
Reviewer 1 Report
This manuscript reported the systematic investigations on the influence of 4,4’-bipyridyl and solvent on the crystal and molecular structures of the alkaline earth (Mg2+, Ca2+, Sr2+ and Ba2+) pentacryanocyclopentadienides. It is an interesting work, I think it could be published after minor revisions.
- How the composition of [Mg(MeOH)6][C5(CN)5]2*2.5 Bipy*2 MeOH and [Mg(MeOH)6][C5(CN)5]2*2.5 Bipy*2 MeOH was determined ?
- The authors wrote:Anyway, it was clear that in both crystals neither the pentacyanocyclopentadienide nor the bipyridyl coordinate to Magnesium. I am wondering how the authors know the coordination situation of the compound since they did not get the crystal structures.
- The central metal ion in compound 3 and 4 is Sr2+, why the coordination pattern for 3 and 4 is so different?
Author Response
- How the composition of [Mg(MeOH)6][C5(CN)5]2*2.5 Bipy*2 MeOH and [Mg(MeOH)6][C5(CN)5]2*2.5 Bipy*2 MeOH was determined ?
- The authors wrote:Anyway, it was clear that in both crystals neither the pentacyanocyclopentadienide nor the bipyridyl coordinate to Magnesium. I am wondering how the authors know the coordination situation of the compound since they did not get the crystal structures.
- The central metal ion in compound 3 and 4 is Sr2+, why the coordination pattern for 3 and 4 is so different?
RESPONSE #1
- The suggested formulae were derived from the structure solution of the obtained crystals, which showed clearly the coordination sphere of the metals. However it was not possible to refine the structures properly. I had now a look at the old “solutions” and tried to refine them again. In case of the MeOH crystals, the metal coordination sphere remained stable; however, one of the lattice bipyridines appeared to be severely disordered at least over three positions, including the position of one lattice MeOH molecule. In my hands, it was not possible to resolve this disorder properly and a high wR2 value > 30% remained. As the found solution did not contain neither coordinated anion nor coordinated bipyridine, it did not seem appropriate to put further effort into this refinement.
- On the other hand, further refinement of the ethanol crystals produced more and more spurious peaks around the metal like isolated 5- or6 membered rings. It was therefore decided, not to continue postulating the original formulation and any sentences relating to the ethanol product were eliminated from the manuscript.
- We have no explanation, why the two strontium crystals are so different, particular for the fact that in methanol only the solvent acts as a ligand, especially as both crystals came from the same crude product. One possibility might be, that the original product from methanol had a similar composition as the butanol crystals, but upon prolonged standing some kind of “disproportionation” occurred with the observed compound 3 as one product and a methanol-free compound as the other product, which unfortunately did not crystallize. This interpretation is however highly speculative.
Reviewer 2 Report
The manuscript contains description of six crystal structures. These structures are based on acceptable experimental data, however four of them contain some errors which require additional work and subsequent refinement. This needs to be done before any additional reviewing.
Bond parameters - and appropriate Tables - will change after this process. They'll need to be replaced,
Following structures require some work: they (1,4,5,6) must be re-refined and appropriate CIF files re-submitted to CSD with the same numbers. Two sample RES files are included.
Compound 1 2213249.
All hydrogen atoms of bipyridyl and water molecules are refined isotropically. It is unnecessary at resolution of 0.84 A. Please re-refine aromatic hydrogens with AFIX 43 and -1.2 for isotropic displacement;
Please use -1.5 for water hydrogen atoms; AFIX 147 and -1.5 for H3 atom of butanol.
Compound 2 2213250
ADDSYM Detects Noncrystallographic Inversion: indeed, this structure can be solved in P21/n with very high R-factor. This feature would be interesting to discuss.
It seems that one of bipyridyl molecules is disordered. However, I do not see any reason to resolve this disorder: it would change almost nothing. The structure can be left as is: just please add some discussion of additional symmetry.
Compound 4 2213251:
A SQUEEZEd molecule is butanol, with occupancy of 0.3, disordered in two positions.
It is possible to refine it. Please do.
Compound 5:2213253
A number of disordered ethanol are not correctly refined.
All carbon atoms must be made anisotropic with appropriate restraints.
Carbon atom C39E is in fact splitted in two, belonging to appropriate ethanol molecules.
Occupancies of disordered fragments should not be fixed but refined. Please attach correct number of methylene and methyl hydrogen atoms to each of ethanol carbons.
Hydrogen of water molecule O5 (H5WB) is misplaced – it makes a hydrogen bond with another water O1W.
Compound 6:2213254
Both disordered butanol molecules need to be corrected.
Butanol with O5 oxygen: the occupancy of carbon atoms is fixed to 0.75, they’re left isotropic.
The actual occupancy when refined is at least 0.91 and should be fixed as 1; carbon atoms should be refined as anisotropic with appropriate restraints.
Butanol with O6 atoms: for some reasons, most of carbon atoms are left with various occupancies. A water molecule is assumed (for what reason) with occupancy of 0.2 only (undetectable with this quality of the structure experiment). All carbons are left isotropic.
This fragment must be re-refined with two butanol chains; this chains must be isotropic with appropriate restraints.
In my hands, such changes result in a visible improvement of the structure R-factor.
A RES file is included: please don’t consider it as a final version, it still may need some work.
2213251_sx.res
TITL file DDJOB.res = = DIRDIF output for SHELX
2213251_sx.res
created by SHELXL-2018/3 at 00:24:16 on 24-Oct-2022
CELL 0.71073 13.7982 14.7801 16.518 64.558 66.682 65.115
ZERR 2 0.0006 0.0006 0.0007 0.001 0.001 0.001
LATT 1
SFAC C H N Sr O
UNIT 106 88 30 2 8
EQIV $1 -X,-Y,1-Z
EQIV $2 1+X,1+Y,+Z
EQIV $3 -X,1-Y,1-Z
EQIV $4 1-X,-Y,1-Z
EQIV $5 -1+X,+Y,+Z
EQIV $6 +X,+Y,-1+Z
SADI O1W H1Wa O1W H1Wb O2W H2Wa O2W H2Wb
SADI H1Wa H1Wb H2Wa H2Wb
ISOR C8 C7 O3
L.S. 12 0 7
PLAN 6
SIZE 0.08 0.09 0.1
TEMP -173
HTAB C2 N40
HTAB C6 N30
HTAB C11 N43_$2
HTAB C26 N42_$1
HTAB O1W N11_$3
HTAB O1W N44_$1
HTAB O2W N20_$4
HTAB O2W O1W_$1
HTAB O3B N10_$5
HTAB O4B N21_$6
CONF
HTAB 2.0
BOND $H
fmap 2
acta
MORE -1
MERG 2
OMIT -1 1 0
OMIT 1 1 2
OMIT 0 -1 1
OMIT 0 2 2
OMIT 0 0 2
OMIT 0 1 2
REM <olex2.extras>
REM <HklSrc "%.\\2213251_sx.hkl">
REM </olex2.extras>
WGHT 0.045400 2.850300
FVAR 0.36712 0.29600
C2 1 0.249859 0.057482 0.090820 11.00000 0.01806 0.03006 =
0.01915 -0.00718 -0.00597 -0.00527
AFIX 43
H2 2 0.182465 0.061532 0.084591 11.00000 -1.20000
AFIX 0
C3 1 0.346747 0.024309 0.027722 11.00000 0.02020 0.03029 =
0.01525 -0.00936 -0.00446 -0.00424
AFIX 43
H3 2 0.344666 0.005904 -0.019920 11.00000 -1.20000
AFIX 0
C4 1 0.446868 0.017677 0.033370 11.00000 0.01896 0.02878 =
0.01612 -0.00803 -0.00303 -0.00372
C5 1 0.442301 0.045913 0.105262 11.00000 0.01866 0.08379 =
0.03739 -0.03939 -0.00314 -0.00888
AFIX 43
H5 2 0.508449 0.043060 0.112741 11.00000 -1.20000
AFIX 0
C6 1 0.342099 0.077982 0.165591 11.00000 0.02316 0.07313 =
0.03238 -0.03511 -0.00266 -0.00874
AFIX 43
H6 2 0.341712 0.096794 0.213979 11.00000 -1.20000
AFIX 0
C10 1 0.742812 0.488607 0.264283 11.00000 0.02235 0.04495 =
0.03293 -0.01312 -0.00697 -0.00458
AFIX 43
H10 2 0.810262 0.503293 0.247216 11.00000 -1.20000
AFIX 0
C11 1 0.649956 0.543800 0.316687 11.00000 0.02504 0.03538 =
0.02963 -0.01506 -0.00464 -0.00763
AFIX 43
H11 2 0.654615 0.594816 0.334351 11.00000 -1.20000
AFIX 0
C12 1 0.550506 0.524691 0.343300 11.00000 0.02384 0.01638 =
0.01804 -0.00225 -0.00772 -0.00314
C13 1 0.551266 0.450434 0.312988 11.00000 0.03250 0.04762 =
0.06399 -0.03727 0.00567 -0.01555
AFIX 43
H13 2 0.484971 0.434666 0.328038 11.00000 -1.20000
AFIX 0
C14 1 0.648736 0.399195 0.260728 11.00000 0.04395 0.04117 =
0.06711 -0.03787 0.00160 -0.00902
AFIX 43
H14 2 0.646865 0.348248 0.241240 11.00000 -1.20000
AFIX 0
C15 1 0.255701 0.617439 0.478077 11.00000 0.02132 0.03529 =
0.03824 -0.01601 0.00108 -0.01181
AFIX 43
H15 2 0.187993 0.603788 0.493806 11.00000 -1.20000
AFIX 0
C16 1 0.348642 0.562122 0.426360 11.00000 0.02655 0.02799 =
0.03593 -0.01542 -0.00504 -0.01041
AFIX 43
H16 2 0.344254 0.511500 0.408027 11.00000 -1.20000
AFIX 0
C17 1 0.448497 0.580664 0.401227 11.00000 0.02236 0.01572 =
0.01576 0.00000 -0.00801 -0.00357
C18 1 0.448180 0.653118 0.433358 11.00000 0.02309 0.03184 =
0.04061 -0.01825 -0.00674 -0.00690
AFIX 43
H18 2 0.514975 0.667315 0.419787 11.00000 -1.20000
AFIX 0
C19 1 0.350919 0.704918 0.485166 11.00000 0.02787 0.02945 =
0.03301 -0.01650 -0.00820 -0.00504
AFIX 43
H19 2 0.353051 0.754679 0.505936 11.00000 -1.20000
AFIX 0
C20 1 0.783547 0.221631 0.770128 11.00000 0.02175 0.04664 =
0.04016 -0.00281 -0.00646 -0.00119
AFIX 43
H20 2 0.854713 0.226630 0.758006 11.00000 -1.20000
AFIX 0
C21 1 0.698811 0.260000 0.838807 11.00000 0.02528 0.05127 =
0.03347 -0.01122 -0.00717 -0.00457
AFIX 43
H21 2 0.712435 0.289600 0.872677 11.00000 -1.20000
AFIX 0
C22 1 0.593997 0.254580 0.857365 11.00000 0.02485 0.03867 =
0.02106 -0.00013 -0.01014 -0.00231
C23 1 0.580438 0.211689 0.803141 11.00000 0.03152 0.03382 =
0.02326 0.00156 -0.01251 -0.00170
AFIX 43
H23 2 0.509667 0.208328 0.811588 11.00000 -1.20000
AFIX 0
C24 1 0.670905 0.174266 0.737200 11.00000 0.04016 0.02807 =
0.02351 0.00051 -0.01152 0.00128
AFIX 43
H24 2 0.660416 0.143937 0.702096 11.00000 -1.20000
AFIX 0
C25 1 0.307038 0.345065 1.003998 11.00000 0.02214 0.05565 =
0.03778 -0.01617 -0.00597 -0.01335
AFIX 43
H25 2 0.233314 0.370259 0.998914 11.00000 -1.20000
AFIX 0
C26 1 0.392007 0.325308 0.928491 11.00000 0.02538 0.04331 =
0.02771 -0.01123 -0.00835 -0.01018
AFIX 43
H26 2 0.376533 0.338069 0.872715 11.00000 -1.20000
AFIX 0
C27 1 0.500688 0.286578 0.934046 11.00000 0.02310 0.05136 =
0.02386 -0.00809 -0.00624 -0.00942
C28 1 0.517355 0.274843 1.016199 11.00000 0.02732 0.10775 =
0.02925 -0.02113 -0.00904 -0.01779
AFIX 43
H28 2 0.590288 0.251266 1.022575 11.00000 -1.20000
AFIX 0
C29 1 0.427037 0.297746 1.088308 11.00000 0.03995 0.12750 =
0.02815 -0.02749 -0.00418 -0.03198
AFIX 43
H29 2 0.440030 0.289561 1.143767 11.00000 -1.20000
AFIX 0
C30 1 0.300991 0.053953 0.505166 11.00000 0.01509 0.02727 =
0.02054 -0.01024 -0.00498 -0.00317
C31 1 0.289595 -0.027717 0.589998 11.00000 0.01519 0.02501 =
0.02072 -0.01100 -0.00539 -0.00249
C32 1 0.346846 -0.025712 0.643022 11.00000 0.01803 0.02848 =
0.02275 -0.01022 -0.00935 -0.00198
C33 1 0.392350 0.057457 0.591072 11.00000 0.01947 0.03036 =
0.03169 -0.01390 -0.01046 -0.00368
C34 1 0.364037 0.107172 0.505538 11.00000 0.01786 0.02763 =
0.02727 -0.00979 -0.00675 -0.00449
C35 1 0.251341 0.078221 0.434147 11.00000 0.01694 0.02447 =
0.01979 -0.00870 -0.00269 -0.00440
C36 1 0.224502 -0.095130 0.619161 11.00000 0.01617 0.02808 =
0.01594 -0.01069 -0.00485 -0.00095
C37 1 0.353637 -0.094270 0.734354 11.00000 0.02403 0.03920 =
0.02970 -0.01472 -0.01268 -0.00204
C38 1 0.455280 0.086831 0.621286 11.00000 0.02759 0.03527 =
0.03960 -0.01335 -0.01554 -0.00620
C39 1 0.394197 0.195580 0.432641 11.00000 0.02575 0.03551 =
0.03753 -0.01174 -0.00937 -0.01096
C40 1 -0.086135 -0.088967 0.225482 11.00000 0.01895 0.02278 =
0.01967 -0.00818 -0.00575 -0.00639
C41 1 -0.133190 -0.088077 0.163505 11.00000 0.02902 0.02573 =
0.02197 -0.00597 -0.01202 -0.00965
C42 1 -0.180282 -0.170480 0.207966 11.00000 0.03827 0.02929 =
0.03005 -0.00401 -0.02028 -0.01542
C43 1 -0.163003 -0.222147 0.297075 11.00000 0.02886 0.02519 =
0.02713 -0.00370 -0.01389 -0.01082
C44 1 -0.104154 -0.172675 0.307914 11.00000 0.01792 0.02331 =
0.02210 -0.00853 -0.00741 -0.00536
C45 1 -0.034250 -0.016597 0.212033 11.00000 0.01868 0.02105 =
0.01531 -0.00742 -0.00569 -0.00281
C46 1 -0.135494 -0.016013 0.072113 11.00000 0.03684 0.02945 =
0.02730 -0.00842 -0.01608 -0.01303
C47 1 -0.235098 -0.200996 0.171155 11.00000 0.08429 0.04102 =
0.04286 0.01360 -0.04332 -0.04060
C48 1 -0.205246 -0.305141 0.365946 11.00000 0.03898 0.03281 =
0.03403 -0.00325 -0.02181 -0.01620
C49 1 -0.069780 -0.203259 0.389117 11.00000 0.01859 0.02157 =
0.02159 -0.00821 -0.00382 -0.00739
C50 1 -0.004306 0.341952 0.077890 11.00000 0.05891 0.04394 =
0.02574 0.00043 -0.00558 -0.02431
AFIX 23
H50A 2 0.074672 0.300842 0.061644 11.00000 -1.20000
H50B 2 -0.006942 0.411250 0.074955 11.00000 -1.20000
AFIX 0
C51 1 -0.052994 0.358366 0.009008 11.00000 0.09628 0.10194 =
0.04321 -0.00874 -0.01924 -0.05429
AFIX 23
H51A 2 -0.127640 0.409790 0.018991 11.00000 -1.20000
H51B 2 -0.008303 0.391199 -0.052493 11.00000 -1.20000
AFIX 0
C52 1 -0.063772 0.270431 0.005048 11.00000 0.11241 0.03922 =
0.05071 -0.00282 -0.03695 -0.00929
AFIX 23
H52A 2 -0.110050 0.237906 0.065670 11.00000 -1.20000
H52B 2 0.010378 0.218256 -0.004848 11.00000 -1.20000
AFIX 0
C53 1 -0.116243 0.295568 -0.073024 11.00000 0.16594 0.08731 =
0.10762 -0.01372 -0.08348 -0.04823
AFIX 137
H53A 2 -0.190025 0.346742 -0.063609 11.00000 -1.50000
H53B 2 -0.122441 0.230889 -0.070928 11.00000 -1.50000
H53C 2 -0.069274 0.324887 -0.133653 11.00000 -1.50000
AFIX 0
C60 1 0.071262 0.391219 0.249835 11.00000 0.03022 0.03014 =
0.03864 -0.01285 -0.00569 -0.00912
AFIX 23
H60A 2 -0.002000 0.384877 0.291769 11.00000 -1.20000
H60B 2 0.058859 0.453262 0.194353 11.00000 -1.20000
AFIX 0
C61 1 0.131767 0.407826 0.299383 11.00000 0.03543 0.03448 =
0.03991 -0.01240 -0.01195 -0.00893
AFIX 23
H61A 2 0.152123 0.342534 0.350357 11.00000 -1.20000
H61B 2 0.200974 0.422631 0.255110 11.00000 -1.20000
AFIX 0
C62 1 0.062360 0.497065 0.338676 11.00000 0.05647 0.04220 =
0.05020 -0.01884 -0.01584 -0.00837
AFIX 23
H62A 2 -0.003007 0.478938 0.387730 11.00000 -1.20000
H62B 2 0.035437 0.560618 0.288944 11.00000 -1.20000
AFIX 0
C63 1 0.126022 0.520856 0.378987 11.00000 0.09006 0.04927 =
0.07180 -0.02961 -0.03696 -0.01105
AFIX 137
H63A 2 0.154565 0.457582 0.427092 11.00000 -1.50000
H63B 2 0.076992 0.577056 0.406401 11.00000 -1.50000
H63C 2 0.187983 0.543431 0.329731 11.00000 -1.50000
AFIX 0
N1 3 0.245085 0.084239 0.160113 11.00000 0.01956 0.03225 =
0.01873 -0.01077 -0.00369 -0.00424
N10 3 0.743962 0.416724 0.236341 11.00000 0.03004 0.03059 =
0.03022 -0.01118 -0.00815 0.00480
N11 3 0.254622 0.688754 0.507428 11.00000 0.02316 0.02396 =
0.01901 -0.00556 -0.00529 -0.00310
N20 3 0.771886 0.178390 0.720189 11.00000 0.03975 0.03237 =
0.02697 -0.00190 -0.00796 0.00368
N21 3 0.321952 0.330918 1.084376 11.00000 0.03082 0.08978 =
0.03449 -0.02636 0.00072 -0.02428
N30 3 0.209035 0.095165 0.379885 11.00000 0.02237 0.03460 =
0.02228 -0.01053 -0.00696 -0.00515
N31 3 0.168516 -0.145751 0.642709 11.00000 0.02133 0.03535 =
0.02099 -0.01088 -0.00391 -0.00934
N32 3 0.358996 -0.149392 0.807747 11.00000 0.04693 0.05637 =
0.03057 -0.00979 -0.02021 -0.00192
N33 3 0.505287 0.109012 0.647377 11.00000 0.04503 0.05019 =
0.06119 -0.01767 -0.02839 -0.01634
N34 3 0.418162 0.266196 0.373908 11.00000 0.04622 0.04349 =
0.05395 -0.00462 -0.01061 -0.02332
N40 3 0.005657 0.040114 0.207423 11.00000 0.02280 0.02501 =
0.01895 -0.00842 -0.00565 -0.00727
N41 3 -0.139238 0.040247 -0.001003 11.00000 0.05854 0.03948 =
0.02884 -0.00515 -0.02219 -0.01942
N42 3 -0.279074 -0.228784 0.144789 11.00000 0.16739 0.07252 =
0.07050 0.03078 -0.08682 -0.08668
N43 3 -0.241745 -0.370965 0.421093 11.00000 0.06243 0.04793 =
0.04394 0.00441 -0.02639 -0.03559
N44 3 -0.042141 -0.230723 0.454823 11.00000 0.02983 0.02950 =
0.02227 -0.00839 -0.00950 -0.01000
SR1 4 0.053772 0.145303 0.284779 11.00000 0.01413 0.02038 =
0.01283 -0.00633 -0.00286 -0.00464
O1W 5 -0.041913 0.199996 0.428142 11.00000 0.01666 0.03437 =
0.02048 -0.01494 -0.00359 -0.00600
H1WA 2 -0.108746 0.229479 0.444629 11.00000 0.04200
H1WB 2 -0.012291 0.216901 0.451047 11.00000 0.04059
O2W 5 0.082517 -0.044595 0.383551 11.00000 0.03680 0.02498 =
0.02057 -0.00318 -0.00885 -0.00746
H2WA 2 0.119322 -0.091095 0.359730 11.00000 0.04498
H2WB 2 0.070067 -0.073634 0.439529 11.00000 0.05675
O3B 5 -0.053326 0.289702 0.170753 11.00000 0.01908 0.02492 =
0.02056 -0.00460 -0.00457 -0.00394
H3B 2 -0.112841 0.325771 0.188442 11.00000 0.04556
O4B 5 0.131623 0.299779 0.222085 11.00000 0.02589 0.03430 =
0.02730 -0.01257 -0.00287 -0.01385
H4B 2 0.192475 0.309384 0.185201 11.00000 0.04713
PART 1
C7 1 0.471839 0.463387 1.132433 21.00000 0.09465 0.07303 =
0.07839 -0.00937 -0.02489 -0.05847
AFIX 43
H7 2 0.544897 0.430035 1.139910 21.00000 -1.20000
AFIX 0
C8 1 0.449534 0.509018 1.039244 21.00000 0.08793 0.03295 =
0.08979 -0.00622 -0.02698 -0.03749
AFIX 23
H8A 2 0.413187 0.585670 1.026598 21.00000 -1.20000
H8B 2 0.396952 0.478412 1.041003 21.00000 -1.20000
AFIX 0
O3 5 0.384932 0.472001 1.203192 20.50000 0.06702 0.03553 =
0.09731 0.00083 -0.02631 -0.02431
AFIX 147
H3A 2 0.380039 0.411885 1.238033 21.00000 -1.50000
AFIX 0
HKLF 4
REM file DDJOB.res = = DIRDIF output for SHELX
REM wR2 = 0.0985, GooF = S = 1.064, Restrained GooF = 1.063 for all data
REM R1 = 0.0377 for 8562 Fo > 4sig(Fo) and 0.0471 for all 9809 data
REM 713 parameters refined using 25 restraints
END
WGHT 0.0454 2.8503
REM Instructions for potential hydrogen bonds
HTAB C2 N40
HTAB C6 N30
HTAB C11 N43_$2
HTAB C26 N42_$1
HTAB C61 O3_$6
HTAB O1W N11_$3
HTAB O1W N44_$1
HTAB O2W N20_$4
HTAB O2W O1W_$1
HTAB O3B N10_$5
HTAB O4B N21_$6
HTAB C8 N21
EQIV $9 x, y, z+1
HTAB O3 N34_$9
REM Highest difference peak 1.024, deepest hole -0.581, 1-sigma level 0.068
Q1 1 -0.2195 0.3775 0.0040 11.00000 0.05 1.02
Q2 1 -0.1631 0.2756 0.0454 11.00000 0.05 0.88
Q3 1 -0.1644 0.3618 0.0133 11.00000 0.05 0.68
Q4 1 -0.0007 0.2871 0.0121 11.00000 0.05 0.67
Q5 1 0.0999 0.4289 0.3459 11.00000 0.05 0.49
Q6 1 0.0837 0.4758 0.2553 11.00000 0.05 0.48
REM The information below was added by Olex2.
REM
REM R1 = 0.0377 for 8562 Fo > 4sig(Fo) and 0.0471 for all 52743 data
REM 713 parameters refined using n/a restraints
REM Highest difference peak 1.02, deepest hole -0.58
REM Mean Shift 0, Max Shift 0.000.
REM +++ Tabular Listing of Refinement Information +++
REM R1_all = 0.0471
REM R1_gt = 0.0377
REM wR_ref = 0.0985
REM GOOF = 1.064
REM Shift_max = 0.000
REM Shift_mean = 0
REM Reflections_all = 52743
REM Reflections_gt = 8562
REM Parameters = 713
REM Hole = -0.58
REM Peak = 1.02
REM Flack = n/a
2213254
TITL SIR2014 run in space group P 21/n
2213254_sx.res
created by SHELXL-2018/3 at 22:28:56 on 23-Oct-2022
CELL 0.71073 14.6646 26.4428 24.9814 90 91.201 90
ZERR 2 0.0006 0.0009 0.0009 0 0.001 0
LATT 1
SYMM 0.5-X,0.5+Y,0.5-Z
SFAC C H N O Ba
UNIT 388 296 116 28 8
EQIV $1 1-X,-Y,2-Z
EQIV $2 0.5-X,-0.5+Y,1.5-Z
EQIV $3 1.5-X,-0.5+Y,1.5-Z
EQIV $4 1+X,+Y,+Z
EQIV $5 -1+X,+Y,+Z
EQIV $6 0.5+X,0.5-Y,-0.5+Z
EQIV $7 -0.5+X,0.5-Y,0.5+Z
EQIV $8 -0.5+X,0.5-Y,-0.5+Z
SADI O1BU C11B O5 C51B O6 C61B O6 C65B
SADI C11B C12B C12B C13B C13B C14B C51B C52B C52B C53B C53B C54B C61B C62B
SADI C11B C12B C62B C63B C63B C64B C65B C66B C66B C67B C67B C68B
SADI C11B C13B C12B C14B C51B C53B C52B C54B C61B C63B C62B C64B C65B C67B
DFIX 0.85 O1BU H1BU O6 H6a O5 H5
DFIX 0.85 O1W H1Wa O1W H1Wb O2W H2Wa O2W H2Wb O3W H3Wa O3W H3Wb O4W H4Wa
SADI H1Wa H1Wb H2Wa H2Wb H3Wa H3Wb H4Wa H4Wb
DELU 0.002 0.002 O6 C61B C62B C63B C64B C65B C66B C67B C68B
ISOR 0.02 0.05 C61B C62B C63B C64B C65B C66B C67B C68B
EXYZ H6a H6b
L.S. 11
PLAN 8
SIZE 0.08 0.1 0.11
TEMP -173
CONF
HTAB O1BU N94_$2
HTAB O6 N70
HTAB O6 N4_$3
HTAB C65B N94_$2
HTAB O1W N73_$1
HTAB O1W N8_$4
HTAB O2W N91
HTAB O2W N2_$5
HTAB C10 N60
HTAB C11 N83_$6
HTAB C14 N74_$1
HTAB C15 N94_$3
HTAB O5 N9
HTAB C52B N84
HTAB O3W O1W
HTAB O3W N7
HTAB O4W N73_$1
HTAB O4W N6_$4
HTAB C20 O5
HTAB C34 N84
HTAB C35 N92_$7
HTAB C36 N92_$7
HTAB C39 N82_$8
HTAB C53 N64_$7
HTAB 2.0
BOND $H
LIST 4
fmap 2
acta
MORE -1
MERG 2
OMIT 0 1 2
OMIT 0 3 2
OMIT 1 3 1
OMIT 0 2 3
OMIT 1 2 1
OMIT 0 3 1
OMIT -1 1 2
OMIT 1 1 3
OMIT 0 1 3
OMIT -2 1 0
REM <olex2.extras>
REM <HklSrc "%.\\2213254_sx.hkl">
REM </olex2.extras>
WGHT 0.024900 22.266701
FVAR 0.11924 0.41689
BA1 5 0.430041 0.103837 0.866937 11.00000 0.02113 0.02331 =
0.02135 0.00174 0.00540 0.00183
O1BU 4 0.294353 0.048350 0.913775 11.00000 0.03787 0.03196 =
0.04198 -0.00287 0.00995 -0.01142
H1BU 2 0.271447 0.028723 0.890150 11.00000 -1.50000
C11B 1 0.280061 0.027802 0.965851 11.00000 0.04303 0.04202 =
0.04212 0.00110 0.00694 -0.00678
AFIX 23
H11A 2 0.312542 0.048954 0.992817 11.00000 -1.20000
H11B 2 0.306451 -0.006631 0.967677 11.00000 -1.20000
AFIX 0
C12B 1 0.179398 0.025157 0.979608 11.00000 0.05342 0.03827 =
0.04068 0.00032 0.01522 -0.00704
AFIX 23
H12A 2 0.148299 0.001892 0.954107 11.00000 -1.20000
H12B 2 0.174141 0.010483 1.015872 11.00000 -1.20000
AFIX 0
C13B 1 0.130421 0.075200 0.978262 11.00000 0.04638 0.03994 =
0.04282 0.00336 0.00978 -0.00615
AFIX 23
H13A 2 0.134481 0.089734 0.941868 11.00000 -1.20000
H13B 2 0.161609 0.098709 1.003470 11.00000 -1.20000
AFIX 0
C14B 1 0.030834 0.071331 0.992860 11.00000 0.05336 0.04779 =
0.05274 -0.00501 0.00563 -0.00031
AFIX 137
H14A 2 -0.000425 0.047752 0.968405 11.00000 -1.50000
H14B 2 0.002279 0.104750 0.989913 11.00000 -1.50000
H14C 2 0.026277 0.058991 1.029698 11.00000 -1.50000
AFIX 0
O6 4 0.441153 0.046470 0.775890 11.00000 0.04359 0.05348 =
0.03128 -0.00691 -0.00058 0.00319
PART 1
H6A 2 0.494573 0.039389 0.765854 21.00000 -1.50000
C61B 1 0.369978 0.030991 0.738691 21.00000 0.07907 0.05661 =
0.06918 -0.01191 -0.03773 0.01160
AFIX 23
H61A 2 0.310394 0.029994 0.756573 21.00000 -1.20000
H61B 2 0.383053 -0.003030 0.724196 21.00000 -1.20000
AFIX 0
C62B 1 0.368634 0.069586 0.694743 21.00000 0.06698 0.09359 =
0.07281 0.00751 -0.03094 0.03562
AFIX 23
H62A 2 0.342259 0.101279 0.708752 21.00000 -1.20000
H62B 2 0.432339 0.076882 0.684896 21.00000 -1.20000
AFIX 0
C63B 1 0.316661 0.054879 0.645612 21.00000 0.08796 0.06843 =
0.06111 0.00712 -0.01452 -0.00033
AFIX 23
H63A 2 0.356092 0.033333 0.623407 21.00000 -1.20000
H63B 2 0.302274 0.085818 0.624778 21.00000 -1.20000
AFIX 0
C64B 1 0.229889 0.027152 0.655352 21.00000 0.09373 0.12261 =
0.14043 0.02542 -0.02380 -0.02357
AFIX 33
H64A 2 0.200017 0.018910 0.620992 21.00000 -1.50000
H64B 2 0.243307 -0.004120 0.675042 21.00000 -1.50000
H64C 2 0.189386 0.048465 0.676415 21.00000 -1.50000
AFIX 0
PART 2
H6B 2 0.494573 0.039389 0.765854 -21.00000 -1.50000
C65B 1 0.385511 0.007434 0.749999 -21.00000 0.05773 0.06688 =
0.05771 -0.01406 0.00266 -0.01311
AFIX 23
H65A 2 0.424190 -0.013000 0.726239 -21.00000 -1.20000
H65B 2 0.360908 -0.015342 0.777640 -21.00000 -1.20000
AFIX 0
C66B 1 0.310602 0.028940 0.718867 -21.00000 0.09565 0.08676 =
0.13852 -0.02326 -0.06531 -0.01772
AFIX 23
H66A 2 0.266536 0.043423 0.744145 -21.00000 -1.20000
H66B 2 0.279213 0.000986 0.699624 -21.00000 -1.20000
AFIX 0
C67B 1 0.332351 0.068313 0.679358 -21.00000 0.20390 0.13091 =
0.13288 0.01830 -0.13342 -0.04104
AFIX 23
H67A 2 0.356953 0.096981 0.700666 -21.00000 -1.20000
H67B 2 0.384417 0.054698 0.659284 -21.00000 -1.20000
AFIX 0
C68B 1 0.272889 0.090964 0.639423 -21.00000 0.34690 0.13442 =
0.20526 -0.01846 -0.18687 0.08310
AFIX 33
H68A 2 0.306965 0.116078 0.619051 -21.00000 -1.50000
H68B 2 0.249542 0.064702 0.615085 -21.00000 -1.50000
H68C 2 0.221736 0.107511 0.656983 -21.00000 -1.50000
AFIX 0
PART 0
O1W 4 0.477781 0.203776 0.891293 11.00000 0.02719 0.03396 =
0.03500 -0.00387 0.00410 -0.00053
H1WA 2 0.479232 0.212627 0.923803 11.00000 -1.50000
H1WB 2 0.527570 0.212433 0.877601 11.00000 -1.50000
O2W 4 0.274343 0.130758 0.819356 11.00000 0.02604 0.05457 =
0.05301 0.02284 -0.00188 -0.00124
H2WA 2 0.270647 0.155312 0.797516 11.00000 -1.50000
H2WB 2 0.227452 0.112491 0.814426 11.00000 -1.50000
N1 3 0.622850 0.095802 0.845759 11.00000 0.02079 0.02700 =
0.03472 0.00155 0.00495 0.00018
N2 3 1.100261 0.091325 0.806075 11.00000 0.02344 0.04897 =
0.06126 0.00487 0.00100 0.00060
C10 1 0.659091 0.113920 0.800955 11.00000 0.02579 0.02913 =
0.03207 0.00473 -0.00115 0.00550
AFIX 43
H10 2 0.619118 0.128787 0.775005 11.00000 -1.20000
AFIX 0
C11 1 0.750858 0.112359 0.790092 11.00000 0.02746 0.02380 =
0.03074 0.00516 0.00384 0.00122
AFIX 43
H11 2 0.772553 0.125566 0.757365 11.00000 -1.20000
AFIX 0
C12 1 0.811058 0.091402 0.827246 11.00000 0.02230 0.01942 =
0.02728 -0.00306 0.00029 -0.00228
C13 1 0.773913 0.071895 0.873689 11.00000 0.02354 0.03716 =
0.02698 0.00373 -0.00292 0.00276
AFIX 43
H13 2 0.812384 0.056703 0.900197 11.00000 -1.20000
AFIX 0
C14 1 0.681530 0.074642 0.881146 11.00000 0.03019 0.03624 =
0.02956 0.00566 0.00401 -0.00272
AFIX 43
H14 2 0.657843 0.060817 0.913084 11.00000 -1.20000
AFIX 0
C15 1 1.059113 0.055201 0.834119 11.00000 0.02561 0.04484 =
0.05669 0.00742 0.00134 0.00588
AFIX 43
H15 2 1.095927 0.029570 0.850170 11.00000 -1.20000
AFIX 0
C16 1 0.966218 0.053074 0.841042 11.00000 0.02545 0.03038 =
0.04022 0.00189 0.00081 -0.00042
AFIX 43
H16 2 0.940317 0.026486 0.861291 11.00000 -1.20000
AFIX 0
C17 1 0.910508 0.090327 0.818045 11.00000 0.02132 0.02512 =
0.02979 -0.00434 -0.00237 0.00012
C18 1 0.953099 0.126860 0.787202 11.00000 0.02679 0.02669 =
0.04080 0.00369 0.00142 0.00101
AFIX 43
H18 2 0.917993 0.152173 0.769343 11.00000 -1.20000
AFIX 0
C19 1 1.046145 0.126025 0.782797 11.00000 0.02795 0.03790 =
0.05627 0.00395 0.00974 -0.00261
AFIX 43
H19 2 1.073842 0.151617 0.761969 11.00000 -1.20000
AFIX 0
N60 3 0.462591 0.172846 0.775619 11.00000 0.03173 0.03516 =
0.03107 0.00804 0.00308 0.00336
N61 3 0.467797 0.335930 0.805135 11.00000 0.05199 0.03898 =
0.02903 -0.00123 0.01438 0.00394
N62 3 0.517090 0.414459 0.652251 11.00000 0.08172 0.03032 =
0.04339 0.00620 -0.00249 -0.00359
N63 3 0.549877 0.293963 0.525944 11.00000 0.12875 0.06382 =
0.02872 0.00420 0.01239 -0.01015
N64 3 0.507525 0.147839 0.600035 11.00000 0.11584 0.04108 =
0.04578 -0.01034 0.01150 0.00506
C60 1 0.488062 0.241119 0.704168 11.00000 0.02175 0.02765 =
0.02478 0.00403 0.00349 0.00392
C61 1 0.490623 0.293407 0.713811 11.00000 0.01847 0.02978 =
0.02630 0.00048 0.00365 0.00212
C62 1 0.505892 0.318052 0.664863 11.00000 0.02747 0.02583 =
0.02394 0.00406 0.00135 -0.00029
C63 1 0.513673 0.280759 0.625058 11.00000 0.03299 0.03532 =
0.02209 0.00322 0.00085 0.00240
C64 1 0.501736 0.233260 0.649334 11.00000 0.03068 0.03022 =
0.02366 0.00228 0.00035 0.00556
C65 1 0.473423 0.203007 0.743354 11.00000 0.01932 0.03146 =
0.02809 -0.00051 0.00068 0.00276
C66 1 0.478950 0.317158 0.764534 11.00000 0.02311 0.02994 =
0.02974 0.00497 0.00628 0.00231
C67 1 0.512253 0.371554 0.657637 11.00000 0.04022 0.03631 =
0.02437 0.00205 -0.00041 -0.00185
C68 1 0.533336 0.288599 0.570246 11.00000 0.07544 0.03644 =
0.02699 0.00298 0.00505 -0.00072
C69 1 0.505256 0.185671 0.622397 11.00000 0.05803 0.03596 =
0.03041 -0.00125 0.00391 0.00333
N70 3 0.488635 -0.001150 0.884761 11.00000 0.03896 0.02807 =
0.03467 0.00055 0.00159 0.00545
N71 3 0.513442 -0.108151 0.741564 11.00000 0.09920 0.03999 =
0.02498 -0.00289 0.00510 -0.00449
N72 3 0.506220 -0.260691 0.801436 11.00000 0.07974 0.03652 =
0.04595 -0.01175 -0.00314 -0.00221
N73 3 0.467067 -0.251525 0.982638 11.00000 0.05631 0.05024 =
0.05481 0.02284 0.00793 0.00013
N74 3 0.473475 -0.096557 1.027738 11.00000 0.04709 0.05014 =
0.02422 0.00027 0.00428 0.00716
C70 1 0.485244 -0.098326 0.884193 11.00000 0.02002 0.02563 =
0.02304 -0.00006 -0.00133 -0.00023
C71 1 0.492353 -0.131317 0.840338 11.00000 0.01947 0.03738 =
0.02093 0.00189 -0.00306 -0.00492
C72 1 0.488437 -0.181259 0.859511 11.00000 0.01955 0.02767 =
0.02868 -0.00425 -0.00431 -0.00196
C73 1 0.477608 -0.178968 0.915138 11.00000 0.02198 0.03053 =
0.02519 0.00669 -0.00202 -0.00191
C74 1 0.475939 -0.127722 0.930591 11.00000 0.01653 0.03300 =
0.02275 -0.00057 0.00042 0.00024
C75 1 0.487092 -0.044423 0.883578 11.00000 0.02311 0.03588 =
0.01828 0.00134 -0.00063 0.00222
C76 1 0.503531 -0.117708 0.785593 11.00000 0.04831 0.02824 =
0.02900 -0.00466 -0.00117 -0.00517
C77 1 0.497447 -0.225632 0.827757 11.00000 0.03624 0.03420 =
0.03634 0.00430 -0.00400 -0.00484
C78 1 0.471588 -0.219847 0.951593 11.00000 0.02930 0.03914 =
0.03390 0.00589 0.00121 -0.00438
C79 1 0.472550 -0.109441 0.984148 11.00000 0.02219 0.03735 =
0.02886 0.00735 0.00328 0.00399
N80 3 0.335874 0.154982 0.957923 11.00000 0.04325 0.03040 =
0.03371 -0.00316 0.01650 -0.00589
N81 3 0.276255 0.060615 1.105520 11.00000 0.05238 0.03221 =
0.04272 0.00591 -0.00059 -0.00328
N82 3 0.219364 0.162856 1.234437 11.00000 0.06864 0.04973 =
0.02437 -0.00044 0.00589 -0.00927
N83 3 0.240262 0.322789 1.172280 11.00000 0.10412 0.04775 =
0.04213 -0.01806 0.00099 0.00101
N84 3 0.317727 0.308948 0.997867 11.00000 0.04092 0.03279 =
0.03017 0.00406 0.00028 -0.00360
C80 1 0.293689 0.186245 1.051377 11.00000 0.01651 0.02939 =
0.02212 -0.00015 0.00310 -0.00166
C81 1 0.275615 0.157594 1.097045 11.00000 0.01871 0.02887 =
0.02549 0.00187 0.00122 -0.00382
C82 1 0.258605 0.190981 1.139238 11.00000 0.02681 0.03363 =
0.01967 -0.00049 -0.00244 -0.00470
C83 1 0.266338 0.240795 1.119762 11.00000 0.02652 0.03195 =
0.02231 -0.00203 -0.00018 -0.00126
C84 1 0.288728 0.237667 1.065339 11.00000 0.02351 0.02451 =
0.02267 0.00008 0.00161 -0.00320
C85 1 0.316089 0.168135 0.999700 11.00000 0.02337 0.02244 =
0.03117 0.00172 0.00649 -0.00567
C86 1 0.276028 0.103695 1.101432 11.00000 0.02492 0.03762 =
0.02492 0.00258 0.00240 -0.00352
C87 1 0.236761 0.176353 1.192361 11.00000 0.03980 0.03521 =
0.02313 -0.00443 -0.00069 -0.00533
C88 1 0.252823 0.286332 1.149165 11.00000 0.05634 0.03503 =
0.02593 -0.00365 -0.00212 -0.00377
C89 1 0.303987 0.278200 1.028815 11.00000 0.02569 0.02938 =
0.02290 -0.00526 -0.00026 -0.00080
BA2 5 0.354877 0.365044 0.898327 11.00000 0.02271 0.02308 =
0.02310 -0.00105 0.00407 -0.00284
O5 4 0.395480 0.427095 0.985290 11.00000 0.05821 0.04082 =
0.03508 -0.00825 0.00195 -0.00537
H5 2 0.349368 0.444928 0.993346 11.00000 -1.50000
PART 1
C51B 1 0.465426 0.422169 1.026931 11.00000 0.09402 0.05168 =
0.06394 -0.02189 -0.01195 -0.00153
AFIX 23
H51A 2 0.492607 0.455834 1.034064 11.00000 -1.20000
H51B 2 0.514341 0.399799 1.013907 11.00000 -1.20000
AFIX 0
C52B 1 0.430350 0.401199 1.078104 11.00000 0.18231 0.06476 =
0.05090 -0.00063 -0.03821 -0.03494
AFIX 23
H52A 2 0.404588 0.367262 1.070610 11.00000 -1.20000
H52B 2 0.379647 0.422994 1.089839 11.00000 -1.20000
AFIX 0
C53B 1 0.498801 0.396400 1.124384 11.00000 0.17601 0.06182 =
0.10591 -0.01974 -0.02373 0.00069
AFIX 23
H53A 2 0.523899 0.430281 1.132902 11.00000 -1.20000
H53B 2 0.466805 0.384075 1.156358 11.00000 -1.20000
AFIX 0
C54B 1 0.574738 0.361794 1.112973 11.00000 0.20367 0.12742 =
0.17282 -0.02501 -0.04643 0.06729
AFIX 33
H54A 2 0.616410 0.360258 1.144115 11.00000 -1.50000
H54B 2 0.550584 0.327939 1.105345 11.00000 -1.50000
H54C 2 0.607715 0.374174 1.081873 11.00000 -1.50000
AFIX 0
PART 0
O3W 4 0.320412 0.270089 0.868719 11.00000 0.02412 0.02611 =
0.05246 -0.00328 -0.00339 -0.00061
H3WA 2 0.360027 0.247178 0.868520 11.00000 -1.50000
H3WB 2 0.268034 0.257646 0.863562 11.00000 -1.50000
O4W 4 0.508977 0.327739 0.935361 11.00000 0.02500 0.05728 =
0.04007 0.01552 0.00680 0.00471
H4WA 2 0.517754 0.304609 0.957548 11.00000 -1.50000
H4WB 2 0.565492 0.332746 0.921351 11.00000 -1.50000
N3 3 0.451895 0.450230 0.851778 11.00000 0.05204 0.04119 =
0.04864 -0.00661 0.01343 -0.01808
N4 3 0.891918 0.515087 0.761123 11.00000 0.05008 0.04744 =
0.03929 0.01477 0.01232 0.00126
C20 1 0.523158 0.458457 0.884763 11.00000 0.06649 0.03601 =
0.04010 -0.00945 0.01938 -0.01822
AFIX 43
H20 2 0.514639 0.453774 0.922029 11.00000 -1.20000
AFIX 0
C21 1 0.608566 0.473342 0.868334 11.00000 0.05403 0.03816 =
0.03496 -0.00593 0.01312 -0.01255
AFIX 43
H21 2 0.656601 0.478687 0.893813 11.00000 -1.20000
AFIX 0
C22 1 0.623166 0.480380 0.813970 11.00000 0.04994 0.02141 =
0.03548 -0.00184 0.00903 -0.00428
C23 1 0.548932 0.472816 0.779165 11.00000 0.06095 0.03022 =
0.03792 0.00253 0.01039 -0.01093
AFIX 43
H23 2 0.554933 0.477555 0.741708 11.00000 -1.20000
AFIX 0
C24 1 0.466544 0.458322 0.800021 11.00000 0.05635 0.04408 =
0.05025 -0.00015 0.00384 -0.01912
AFIX 43
H24 2 0.416579 0.453778 0.775676 11.00000 -1.20000
AFIX 0
C25 1 0.862046 0.531891 0.808033 11.00000 0.05462 0.06282 =
0.03381 0.00368 0.00601 -0.01951
AFIX 43
H25 2 0.902005 0.551716 0.829874 11.00000 -1.20000
AFIX 0
C26 1 0.775796 0.521744 0.826164 11.00000 0.05628 0.05953 =
0.02899 -0.00210 0.01174 -0.01702
AFIX 43
H26 2 0.757866 0.534106 0.860063 11.00000 -1.20000
AFIX 0
C27 1 0.714854 0.493392 0.794875 11.00000 0.05121 0.02538 =
0.03023 0.00477 0.01207 -0.00255
C28 1 0.745890 0.476495 0.745853 11.00000 0.05641 0.02209 =
0.03545 0.00070 0.01206 -0.00087
AFIX 43
H28 2 0.707213 0.456920 0.722982 11.00000 -1.20000
AFIX 0
C29 1 0.833104 0.488296 0.730595 11.00000 0.05579 0.03030 =
0.03616 0.00621 0.01490 0.00444
AFIX 43
H29 2 0.852620 0.476852 0.696656 11.00000 -1.20000
AFIX 0
N5 3 0.162655 0.376866 0.918804 11.00000 0.02045 0.04942 =
0.03151 -0.00396 0.00378 -0.00099
N6 3 -0.317709 0.351838 0.910139 11.00000 0.02819 0.03957 =
0.03354 -0.00257 0.00089 -0.00149
C30 1 0.111062 0.409152 0.890375 11.00000 0.03244 0.03864 =
0.03000 -0.00170 0.00772 -0.00436
AFIX 43
H30 2 0.141103 0.434226 0.869986 11.00000 -1.20000
AFIX 0
C31 1 0.017384 0.408473 0.888690 11.00000 0.03017 0.03486 =
0.02568 -0.00171 0.00363 0.00212
AFIX 43
H31 2 -0.015770 0.432369 0.867599 11.00000 -1.20000
AFIX 0
C32 1 -0.028280 0.372114 0.918462 11.00000 0.02555 0.03065 =
0.02129 -0.00629 0.00486 0.00223
C33 1 0.024650 0.339250 0.949291 11.00000 0.03245 0.03555 =
0.02516 -0.00052 0.00351 -0.00045
AFIX 43
H33 2 -0.003594 0.314540 0.971018 11.00000 -1.20000
AFIX 0
C34 1 0.117910 0.342606 0.948250 11.00000 0.02691 0.04675 =
0.02842 0.00093 0.00137 0.00223
AFIX 43
H34 2 0.152795 0.319533 0.969428 11.00000 -1.20000
AFIX 0
C35 1 -0.269754 0.344193 0.955723 11.00000 0.02995 0.03520 =
0.03175 0.00482 0.00243 -0.00331
AFIX 43
H35 2 -0.301675 0.333554 0.986449 11.00000 -1.20000
AFIX 0
C36 1 -0.176845 0.350905 0.960465 11.00000 0.02872 0.03195 =
0.02975 0.00289 -0.00172 -0.00290
AFIX 43
H36 2 -0.145929 0.344690 0.993612 11.00000 -1.20000
AFIX 0
C37 1 -0.128674 0.366935 0.916030 11.00000 0.02828 0.02473 =
0.02456 -0.00478 0.00449 0.00071
C38 1 -0.178644 0.375456 0.868784 11.00000 0.03046 0.03603 =
0.02350 -0.00426 0.00324 0.00260
AFIX 43
H38 2 -0.149130 0.387158 0.837640 11.00000 -1.20000
AFIX 0
C39 1 -0.270722 0.366771 0.867769 11.00000 0.03291 0.04180 =
0.02523 -0.00430 -0.00214 0.00740
AFIX 43
H39 2 -0.303172 0.371679 0.834867 11.00000 -1.20000
AFIX 0
N90 3 0.254923 0.375848 0.796143 11.00000 0.03841 0.03748 =
0.02360 0.00346 0.00341 0.00501
N91 3 0.244732 0.211249 0.742301 11.00000 0.04463 0.03239 =
0.05341 0.00640 -0.00161 0.00656
N92 3 0.274167 0.209886 0.569660 11.00000 0.07358 0.06877 =
0.06159 -0.03591 -0.00350 0.00215
N93 3 0.276752 0.371208 0.512088 11.00000 0.09037 0.08903 =
0.03024 0.00267 0.00317 -0.00648
N94 3 0.265442 0.468642 0.653923 11.00000 0.05603 0.03702 =
0.05307 0.01584 -0.00341 -0.00332
C90 1 0.255242 0.341276 0.700031 11.00000 0.01881 0.03095 =
0.02172 0.00153 0.00006 0.00112
C91 1 0.255848 0.290541 0.683636 11.00000 0.02037 0.02837 =
0.03085 0.00030 -0.00390 0.00418
C92 1 0.263266 0.290064 0.627354 11.00000 0.02163 0.04087 =
0.03172 -0.00614 -0.00198 0.00244
C93 1 0.266390 0.340124 0.609271 11.00000 0.02879 0.04710 =
0.02362 0.00255 -0.00179 -0.00086
C94 1 0.262054 0.371550 0.654261 11.00000 0.02527 0.03243 =
0.02494 0.00470 -0.00439 0.00024
C95 1 0.253997 0.359876 0.753565 11.00000 0.02309 0.02458 =
0.02867 0.00697 -0.00171 0.00030
C96 1 0.249279 0.246682 0.716470 11.00000 0.02273 0.03097 =
0.03858 -0.00243 -0.00508 0.00476
C97 1 0.268567 0.245615 0.594947 11.00000 0.03581 0.05999 =
0.03859 -0.01418 -0.00540 -0.00102
C98 1 0.272728 0.357233 0.555141 11.00000 0.05350 0.06177 =
0.02709 -0.00312 -0.00095 -0.00383
C99 1 0.264156 0.425240 0.653930 11.00000 0.03197 0.03976 =
0.02777 0.00999 -0.00349 -0.00258
N7 3 0.138932 0.243879 0.860659 11.00000 0.02666 0.03718 =
0.03895 -0.00506 0.00197 -0.00558
N8 3 -0.343588 0.224194 0.867879 11.00000 0.02898 0.02519 =
0.07166 0.00404 0.00218 -0.00436
C49 1 -0.301592 0.241809 0.825288 11.00000 0.03380 0.03438 =
0.07043 0.01691 -0.01682 -0.00700
AFIX 43
H49 2 -0.337986 0.252184 0.795355 11.00000 -1.20000
AFIX 0
C40 1 0.097447 0.210102 0.891732 11.00000 0.03320 0.03598 =
0.03696 0.00566 -0.00903 0.00126
AFIX 43
H40 2 0.134637 0.188509 0.913341 11.00000 -1.20000
AFIX 0
C41 1 0.004765 0.204680 0.894362 11.00000 0.03212 0.02989 =
0.03536 0.00625 -0.00234 -0.00575
AFIX 43
H41 2 -0.020539 0.179816 0.917136 11.00000 -1.20000
AFIX 0
C42 1 -0.052260 0.235739 0.863541 11.00000 0.03068 0.02379 =
0.02790 -0.00333 -0.00196 -0.00578
C43 1 -0.009744 0.270797 0.830922 11.00000 0.02987 0.02576 =
0.02993 0.00311 0.00033 -0.00089
AFIX 43
H43 2 -0.045178 0.292705 0.808671 11.00000 -1.20000
AFIX 0
C44 1 0.083362 0.273549 0.831062 11.00000 0.02863 0.03197 =
0.03271 0.00107 0.00189 -0.00502
AFIX 43
H44 2 0.110550 0.298119 0.808700 11.00000 -1.20000
AFIX 0
C45 1 -0.290591 0.209491 0.908547 11.00000 0.04125 0.04509 =
0.05481 0.00663 0.00981 -0.01211
AFIX 43
H45 2 -0.319120 0.195830 0.939127 11.00000 -1.20000
AFIX 0
C46 1 -0.197133 0.212698 0.909406 11.00000 0.03327 0.04227 =
0.04045 0.00620 0.00299 -0.00447
AFIX 43
H46 2 -0.163026 0.202205 0.940191 11.00000 -1.20000
AFIX 0
C47 1 -0.152732 0.231391 0.864961 11.00000 0.02958 0.01915 =
0.03866 0.00055 -0.00294 -0.00389
C48 1 -0.208080 0.245970 0.821859 11.00000 0.03303 0.03232 =
0.05157 0.01504 -0.00525 -0.00892
AFIX 43
H48 2 -0.181696 0.258738 0.790188 11.00000 -1.20000
AFIX 0
N9 3 0.237534 0.475692 1.015643 11.00000 0.06656 0.05189 =
0.05790 -0.02387 0.01065 -0.01211
C50 1 0.205405 0.517643 0.992002 11.00000 0.06747 0.04189 =
0.10796 -0.00649 0.03426 -0.01506
AFIX 43
H50 2 0.248245 0.541388 0.979028 11.00000 -1.20000
AFIX 0
C51 1 0.114778 0.528429 0.985375 11.00000 0.06777 0.03152 =
0.09991 -0.00075 0.02958 -0.01168
AFIX 43
H51 2 0.096381 0.558881 0.968102 11.00000 -1.20000
AFIX 0
C52 1 0.049686 0.495149 1.003736 11.00000 0.06541 0.03336 =
0.03886 -0.01901 0.01827 -0.01694
C53 1 0.082711 0.452130 1.029214 11.00000 0.06453 0.05075 =
0.03539 -0.00808 0.00445 -0.02534
AFIX 43
H53 2 0.041481 0.428322 1.043726 11.00000 -1.20000
AFIX 0
C54 1 0.174278 0.443995 1.033444 11.00000 0.07593 0.04846 =
0.04019 -0.00993 0.00099 -0.01228
AFIX 43
H54 2 0.194480 0.413646 1.050234 11.00000 -1.20000
AFIX 0
HKLF 4
REM SIR2014 run in space group P 21/n
REM wR2 = 0.0977, GooF = S = 1.195, Restrained GooF = 1.204 for all data
REM R1 = 0.0463 for 14305 Fo > 4sig(Fo) and 0.0677 for all 17832 data
REM 1287 parameters refined using 171 restraints
END
WGHT 0.0244 22.8491
REM Instructions for potential hydrogen bonds
HTAB O1BU N94_$2
HTAB O6 N4_$3
HTAB C65B N94_$2
HTAB O1W N73_$1
HTAB O1W N8_$4
HTAB O2W N91
HTAB O2W N2_$5
HTAB C10 N60
HTAB C11 N83_$6
HTAB C14 N74_$1
HTAB C15 N94_$3
HTAB O5 N9
HTAB C52B N84
HTAB O3W O1W
HTAB O3W N7
HTAB O4W N73_$1
HTAB O4W N6_$4
HTAB C20 O5
HTAB C34 N84
HTAB C35 N92_$7
HTAB C36 N92_$7
HTAB C39 N82_$8
HTAB C53 N64_$7
REM Highest difference peak 0.971, deepest hole -0.782, 1-sigma level 0.086
Q1 1 0.4238 0.3627 0.9006 11.00000 0.05 0.97
Q2 1 0.2914 0.3639 0.8997 11.00000 0.05 0.97
Q3 1 0.4979 0.1041 0.8675 11.00000 0.05 0.91
Q4 1 0.5680 0.4039 1.0971 11.00000 0.05 0.90
Q5 1 0.3608 0.1036 0.8638 11.00000 0.05 0.89
Q6 1 0.3145 0.4266 0.8973 11.00000 0.05 0.75
Q7 1 0.3596 0.3643 0.8593 11.00000 0.05 0.68
Q8 1 0.5419 0.3898 1.1631 11.00000 0.05 0.64
REM The information below was added by Olex2.
REM
REM R1 = 0.0463 for 14305 Fo > 4sig(Fo) and 0.0677 for all 160829 data
REM 1287 parameters refined using n/a restraints
REM Highest difference peak 0.97, deepest hole -0.78
REM Mean Shift 0, Max Shift -0.002.
REM +++ Tabular Listing of Refinement Information +++
REM R1_all = 0.0677
REM R1_gt = 0.0463
REM wR_ref = 0.0977
REM GOOF = 1.195
REM Shift_max = -0.002
REM Shift_mean = 0
REM Reflections_all = 160829
REM Reflections_gt = 14305
REM Parameters = 1287
REM Hole = -0.78
REM Peak = 0.97
REM Flack = n/a
Author Response
The manuscript contains description of six crystal structures. These structures are based on acceptable experimental data, however four of them contain some errors which require additional work and subsequent refinement. This needs to be done before any additional reviewing.
Bond parameters - and appropriate Tables - will change after this process. They'll need to be replaced,
Following structures require some work: they (1,4,5,6) must be re-refined and appropriate CIF files re-submitted to CSD with the same numbers. Two sample RES files are included.
Compound 1 2213249.
All hydrogen atoms of bipyridyl and water molecules are refined isotropically. It is unnecessary at resolution of 0.84 A. Please re-refine aromatic hydrogens with AFIX 43 and -1.2 for isotropic displacement;
Please use -1.5 for water hydrogen atoms; AFIX 147 and -1.5 for H3 atom of butanol.
Compound 2 2213250
ADDSYM Detects Noncrystallographic Inversion: indeed, this structure can be solved in P21/n with very high R-factor. This feature would be interesting to discuss.
It seems that one of bipyridyl molecules is disordered. However, I do not see any reason to resolve this disorder: it would change almost nothing. The structure can be left as is: just please add some discussion of additional symmetry.
Compound 4 2213251:
A SQUEEZEd molecule is butanol, with occupancy of 0.3, disordered in two positions.
It is possible to refine it. Please do.
Compound 5:2213253
A number of disordered ethanol are not correctly refined.
All carbon atoms must be made anisotropic with appropriate restraints.
Carbon atom C39E is in fact splitted in two, belonging to appropriate ethanol molecules.
Occupancies of disordered fragments should not be fixed but refined. Please attach correct number of methylene and methyl hydrogen atoms to each of ethanol carbons.
Hydrogen of water molecule O5 (H5WB) is misplaced – it makes a hydrogen bond with another water O1W.
Compound 6:2213254
Both disordered butanol molecules need to be corrected.
Butanol with O5 oxygen: the occupancy of carbon atoms is fixed to 0.75, they’re left isotropic.
The actual occupancy when refined is at least 0.91 and should be fixed as 1; carbon atoms should be refined as anisotropic with appropriate restraints.
Butanol with O6 atoms: for some reasons, most of carbon atoms are left with various occupancies. A water molecule is assumed (for what reason) with occupancy of 0.2 only (undetectable with this quality of the structure experiment). All carbons are left isotropic.
This fragment must be re-refined with two butanol chains; this chains must be isotropic with appropriate restraints.
In my hands, such changes result in a visible improvement of the structure R-factor.
A RES file is included: please don’t consider it as a final version, it still may need some work.
Response:
First, I want to thank this reviewer for putting so much effort in performing his own refinements on these structures, and to share his/her results with me.
Second, I also want to state that I did perform my original refinements deliberately the way I described. Particularly, I had my reasons to use these “strange” looking stoichiometries. My general idea is, that molecules with identical composition and more or less identical environment should have approximately have the same thermal parameters when on the isotropic stage. First assuming full occupancy for combined positions, an average isotropic U value was chosen for all chemically identical positions (e.g. in the case of a butanol ligand, same U for Carbons 1, same U for carbons 2, and so on). Then the s.o.f was refined with a free variable with occupancy sum 1.0. When this refinement was stable, the obtained s.o.f.’s were fixed and the U values were freed. When this refinement gave for analogous atoms more or less identical values, they were allowed to refine anisotropically. If not, the s.o.f. were adjusted until the corresponding U values were near identical. Then the s.o.f.’s were fixed again, the U values were refined, and if they kept on being close to identical, an anisotropic refinement was tried. If this was not successful, the atoms were kept isotropic.. If it was not possible to obtain identical isotropic U values with this approach, it was tried to introduce either a third position, or, another ligand like water instead of alcohol or vice versa. This approach of mine lead to the results described in the original manuscript.
Anyway, I followed most of this reviewer’s suggestions and thus produced new cif-files, with corresponding new tables, and where necessary, also new figures.
I must say, that I am still not convinced that “my” approach could not also have been kept. The R-values did not really change significantly: they got slightly worse for structures 1 and 4 and slightly better for structures 5 and 6. And the number of checkcif complaints did also not really improve…
P.S. In structure 5, I did not change the hydrogen on water molecule O5. The positions of all water hydrogens had been determined with the program “CALC-OH” of wingx, and were then either refined with appropriate restraints, or were fixed, when refinements were not stable. The latter had been done for the water hydrogens at O5. Thus, these coordinates are those from the output of “CALC_OH”, which is a program that evaluates residual electron density maps for local maxima that “make sense” in the context of hydrogen bonding. Actually I think, considering the relative close distance of several hydrogen bond acceptors and donors, there are many possible orientations of this particular water molecule. But in a barium structure, any attempts of refinement of H atoms are senseless.
Reviewer 3 Report
The work entitled “Coordination Chemistry of Polynitriles, Part XI. Influence of 4,4’-Bipyridyl and Solvent on the Crystal and Molecular Structures of Alkaline Earth Pentacyanocyclopentadienides” by P. Nimax and K. Sünkel, described the synthesis and structural characterization of a series of Alkaline Earth Pentacyanocyclopentadienides having as additional ligand or guest molecule 4,4’-Bipyridyl.
Please use for 4,4’-bipyridyl the abbreviation 4,4’-bipy, in order not to make confusion with 2,2’-bipy used more often and known in literature as bipy. Please replace “*” in the formulas in all the manuscript with “·”. So, instead of
[Mg(H2O)4(η1-Bipy)2][C5(CN)5]2*2BuOH to have
[Mg(H2O)4(η-4,4’bipy)2][C5(CN)5]2·2BuOH.
4, 4’-bipy can act as monodentate ligand and in this case can be used without “η1” or as bidendate bridging ligand and in this case “µ” can be used, but not “µ2”
Please decide what you use for 4,4’-Bipyridyl, 4,4’-bipy or C10H8N2 , like in [Ag{C5(CN)5}(C10H8N2)(H2O)1.25] from experimental section? On the same description of the procedure A, the autors wrote “A suspension of [Ag{C5(CN)5}(C10H8N2)(H2O)1.25] in MeOH (20 mL) was treated with a solution of the dichloride in MeOH”. Please mention what means a solution of the dichloride? MCl2, alkaline earth dichloride?
The authors mention “When the mother liquors were evaporated and dried, the obtained elemental analyses did not agree with the composition of the crystalline material.” This is happening in most of the case. In the mother liquors you could have unreacted reagent, secondary products, aside the main compound. Procedure A and B give similar products? The analysed single-crystals were obtained by different recrystallization of the brute dried materials obtained in both procedures? It is confusing!!
The information concerning the poor quality of the recrystalised compounds from MeOH and EtOH is repeated in the experimental section and in the discussion. This include estimation of some materials formula, based on what? Elemental analysis and other investigation should sustain the claim and all other investigated compounds formula! And again, written the formula [Mg(C10N5)2(H2O)4(EtOH)2(C10H8N2)] with C10H8N2 instead of 4,4’-bipy.
The asymmetric units for 1 shows the compound [Mg(H2O)4(4,4’-bipy)2]·[C5(CN)5]·BuOH instead of [Mg(H2O)4(η1-Bipy)2][C5(CN)5]2*2BuOH; for 2 [Ca(H2O)4(4,4’-bipy)2] · [C5(CN)5]2·(4,4’bipy); for 3 [Sr(MeOH)8] · [C5(CN)5]2·3(4,4’bipy).
The formula for 4 is quite strange:
[Sr(H2O)2(BuOH)2(η1-{C5(CN)5})]2[µ2-Bipy][µ2-C5(CN)5]2*4 Bipy. Please reformulate by checking the repeating units in your polymeric structure and use only “µ” in the formula just for the bridging ligands.
All the formula needs to be corrected. Some of them need to be reformulated based on the crystal structures. Elemental analysis and any other investigation which could support the structures are missing. The description of the structures is poor or inadequate. Based on all that, I recommend a major revision of the manuscript.
Author Response
The work entitled “Coordination Chemistry of Polynitriles, Part XI. Influence of 4,4’-Bipyridyl and Solvent on the Crystal and Molecular Structures of Alkaline Earth Pentacyanocyclopentadienides” by P. Nimax and K. Sünkel, described the synthesis and structural characterization of a series of Alkaline Earth Pentacyanocyclopentadienides having as additional ligand or guest molecule 4,4’-Bipyridyl.
Please use for 4,4’-bipyridyl the abbreviation 4,4’-bipy, in order not to make confusion with 2,2’-bipy used more often and known in literature as bipy. Please replace “*” in the formulas in all the manuscript with “·”. So, instead of
[Mg(H2O)4(η1-Bipy)2][C5(CN)5]2*2BuOH to have
[Mg(H2O)4(η-4,4’bipy)2][C5(CN)5]2·2BuOH.
RESPONSE: The * has been replaced by a ∙ as demanded.
4, 4’-bipy can act as monodentate ligand and in this case can be used without “η1” or as bidendate bridging ligand and in this case “µ” can be used, but not “µ2”
RESPONSE: „µ“ without any number has now been used throughout in the manuscript. Although I think, it should be possible somehow to symbolize the number of actually bridged atoms (there is no ambiguity in bipy, but pentacyanocyclopentadienide could bridge 2 to 5 or even more metals)
Please decide what you use for 4,4’-Bipyridyl, 4,4’-bipy or C10H8N2 , like in [Ag{C5(CN)5}(C10H8N2)(H2O)1.25] from experimental section?
RESPONSE: “4,4’-bipy” was now used in all formulae. Within a running text, sometimes the term “bipyridine(s)” was used. I also decided to replace “Bipyridyl” by “Bipyridine”, which is apparently the nomenclature used in the vast majority of recent publications.
On the same description of the procedure A, the autors wrote “A suspension of [Ag{C5(CN)5}(C10H8N2)(H2O)1.25] in MeOH (20 mL) was treated with a solution of the dichloride in MeOH”. Please mention what means a solution of the dichloride? MCl2, alkaline earth dichloride?
RESPONSE: The term “alkaline earth dichloride” was used now.
The authors mention “When the mother liquors were evaporated and dried, the obtained elemental analyses did not agree with the composition of the crystalline material.” This is happening in most of the case. In the mother liquors you could have unreacted reagent, secondary products, aside the main compound. Procedure A and B give similar products? The analysed single-crystals were obtained by different recrystallization of the brute dried materials obtained in both procedures? It is confusing!!
RESPONSE: The sentence about EA of mother liquor was eliminated from the manuscript, because it does not really contain any useful information. A few sentences about the origin of the different structures described in this manuscript have now been added. This should take away the reviewer’s confusion.
The information concerning the poor quality of the recrystalised compounds from MeOH and EtOH is repeated in the experimental section and in the discussion. This include estimation of some materials formula, based on what? Elemental analysis and other investigation should sustain the claim and all other investigated compounds formula! And again, written the formula [Mg(C10N5)2(H2O)4(EtOH)2(C10H8N2)] with C10H8N2 instead of 4,4’-bipy.
RESPONSE: The origin of the presented formulae was the obtained first structure solutions. As mentioned in the original manuscript, refinement of these first solutions did not work sufficiently. I had a closer look at these refinements again, and decided to take the sentences about the EtOH product completely out of the manuscript, and added some explanatory remarks about the MeOH product.
The asymmetric units for 1 shows the compound [Mg(H2O)4(4,4’-bipy)2]·[C5(CN)5]·BuOH instead of [Mg(H2O)4(η1-Bipy)2][C5(CN)5]2*2BuOH; for 2 [Ca(H2O)4(4,4’-bipy)2] · [C5(CN)5]2·(4,4’bipy); for 3 [Sr(MeOH)8] · [C5(CN)5]2·3(4,4’bipy).
RESPONSE: I do not see the reason for these remarks. Nowhere in the manuscript formulae of the asymmetric units had been used. The reviewer is however wrong for compound 1: The asymmetric unit contains only half a molecule, ie [Mg0.5(H2O)2(4,4’-bipy)] with one anion and one butanol.
The formula for 4 is quite strange:
[Sr(H2O)2(BuOH)2(η1-{C5(CN)5})]2[µ2-Bipy][µ2-C5(CN)5]2*4 Bipy. Please reformulate by checking the repeating units in your polymeric structure and use only “µ” in the formula just for the bridging ligands.
RESPONSE: Indeed, it is very difficult to write a formula that describes the coordination situation correctly. I have decided to use a new „dimeric“ formula (see manuscript).
All the formula needs to be corrected. Some of them need to be reformulated based on the crystal structures. Elemental analysis and any other investigation which could support the structures are missing. The description of the structures is poor or inadequate. Based on all that, I recommend a major revision of the manuscript.
RESPONSE: What am I supposed to do with this? I have given some new formulae, hopefully being better “understandable”. The problems with the elemental analysis had been mentioned in the original manuscript, and one explanatory example has been added to the new version of the manuscript. But why do you think that the descriptions of the structures is “poor or inadequate”? Without a clear indication about the reasons for this statement I cannot change anything, particularly, since the other reviewers did not leave it with such “diffuse” comments.
I changed the nomenclatures according to your suggestions, but I want to emphasize, that none of the original formulae were wrong.
Round 2
Reviewer 2 Report
You are 100% correct that the hydrogen refinement in your structures is senseless. It's not because of any errors from your side, it's technically impossible at this level of data. It's okay!
However, I would like to ask you to check that water molecule once again: my suggestion would be to open your CIF in Mercury, remove the hydrogen of question, and check the possible H-bonds without the H atom position requirement. It must show a short contact with another oxygen atom.
Place H on that bond, and don't refine it if you don't want.
Author Response
Please see the attachment
Author Response File: 
Author Response.pdf
Reviewer 3 Report
The revised form of the work entitled “Coordination Chemistry of Polynitriles, Part XI. Influence of 4,4’-Bipyridyl and Solvent on the Crystal and Molecular Structures of Alkaline Earth Pentacyanocyclopentadienides” by P. Nimax and K. Sünkel, shows the nomenclatures and formula changes as suggested, but didn’t answer to all raised issues. In the paper are presented six new crystal structures for interesting compounds, but there is no other investigation which can support the structures. In any of the previous publication with the same title “Coordination Chemistry of Polynitriles, Part I to X” the authors presented elemental analysis and/or spectral measurements, IR, Mass spectra aside the crystallographic measurements, so I wonder why cannot do it this time?
Author Response
I agree, it is somewhat unsatisfying not to have all the other usual characterizations in the manuscript. Therefore, I put the available spectroscopic data (of the crude products) into the manuscript (NMR data for compounds obtained with procedure A, MS data for compounds obtained with procedure B). As you can see, they are all the same, although the products are quite different. Apparently, either in solution, the coordinated and uncoordinated bipyridines are in fast exchange or they are replaced by the solvent methanol (which is in large excess). From other studies, we knew already that methanol replaces the PCC ligand from the coordination sphere. In the mass spectra only the free ligands 4,4‘- bipy and PCC- can be observed. This is an observation that we made quite often with other PCC systems as well- we don’t have experience with MS of other 4,4‘-bipy coordination compounds, but we didn’t find any examples of reported mass spectra of alkaline earth-4,4‘-bipy complexes.
What is left as possible characterization method is IR and EA. I admit, we did not even try to get IR spectra. Already in the first revised version of the manuscript was an example for the general problems with elemental analysis. The EA values of the crude products did not correspond with the composition of the crystalline material, as calculated from the crystal structures. The reason, why we did not get EA from the single-crystalline material is rather profane. The crystals did not grow quickly. The solutions were standing for many weeks, and when finally the first crystals appeared, the coworker isolated them quickly and brought them to the X-ray diffraction operator. They were always only very few crystals, never enough to perform any kind of characterization (MS and UV might have been possible). If the coworker had been more patient and left the mother liquor for several more weeks or months, more crystals might have appeared. However, he was not. He evaporated the mother liquors completely, and performed characterization attempts on the residues. This was senseless, of course, because all the impurities of the crude products necessarily were present in them.
