Cocrystals of 2-Aminopyrimidine with Boric Acid—Crystal Engineering of a Novel Nonlinear Optically (NLO) Active Crystal
Abstract
:1. Introduction
2. Experimental Setup
2.1. Materials and Methods
2.2. Syntheses
2.3. Crystal Structure Determination
2.4. Crystal Growth
2.5. Quantum Chemical Computations
2.6. Optical Properties
3. Results and Discussion
3.1. Crystal Structure Description
3.2. Vibrational and UV-Vis Spectra
3.3. Optical Properties of (2-AMP)3(H3BO3)2
3.4. Second Harmonic Generation (SHG) Measurements of (2-AMP)3(H3BO3)2
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Identification code | (2-AMP)3(H3BO3)2 | 2-AMP(H3BO3)2 |
---|---|---|
Empirical formula | C12H21B2N9O6 | C4H11B2N3O6 |
Formula weight | 409.00 | 218.78 |
Temperature (K) | 150(2) | 150(2) |
a (Å) | 13.1632(4) | 3.7634(2) |
b (Å) | 13.1632(4) | 13.8978(7) |
c (Å) | 9.9288(3) | 18.2041(8) |
α (°) | 90 | 90 |
β (°) | 90 | 91.757(2) |
γ (°) | 120 | 90 |
Volume (Å3) | 1489.88(10) | 951.68(8) |
Z | 3 | 4 |
Calculated density (Mg/m3) | 1.368 | 1.527 |
Crystal system | Trigonal | Monoclinic |
Space group | P3221 | C2/c |
Absoption coefficient (mm-1) | 0.108 mm−1 | 0.134 mm−1 |
F(000) | 642 | 456 |
Crystal size (mm) | 0.60 × 0.57 × 0.31 | 0.58 × 0.17 × 0.16 |
Diffractometer and radiation | Nonius Kappa CCD, Mo λ = 0.71073 Å | |
Scan technique | ω and ψ scans to fill the Ewald sphere | |
Completeness to θ | 99.9% | 99.9% |
Range of h, k and l | −17→17, −17→17, −12→12 | −4→3, −18→18, −20→23 |
θ Range for data collection (°) | 1.79–27.47° | 2.24–27.48° |
Refl. collected/unique (Rint) | 26047/2287 (0.022) | 7829/1097 (0.019) |
No. of observed reflections | 2216 | 997 |
Criterion for observed reflections | I > 2σ(I) | |
Absorption correction | multi-scan | multi-scan |
Function minimized | Σ w(Fo2 - Fc2)2 | |
Parameters refined | 134 | 70 |
R; wR(F2) (I>2σ(I)) | 0.0267; 0.0752 | 0.0293; 0.0769 |
R; wR(F2) (all data) | 0.0280; 0.0764 | 0.0326; 0.0791 |
Value of S | 1.074 | 1.080 |
Absolut struct. param. (Flack) | -0.1(2) | |
Δρmax and Δρmin (eÅ−3) | 0.17 and −0.16 | 0.18 and –0.19 |
Weighting scheme | W = [σ2(Fo2) + aP2 + bP]−1 | |
P = (Fo2 + 2Fc2)/3 | ||
a = 0.0491 | a = 0.0418 | |
b = 0.1274 | b = 0.4767 |
Compound | (2-AMP)3(H3BO3)2 | 2-AMP(H3BO3)2 | ||||||
---|---|---|---|---|---|---|---|---|
Representations | A1 | A2 | E | Ag | Au | Bg | Bu | |
Acoustic | 1 | 1 | 1 | 2 | ||||
External modes | Translational | 7 | 7 | 14 | 4 | 3 | 5 | 3 |
Librational | 7 | 8 | 15 | 4 | 4 | 5 | 5 | |
Internal modes | 59 | 61 | 120 | 29 | 29 | 31 | 31 | |
Total | 73 | 77 | 150 | 37 | 37 | 41 | 41 | |
Activity | IR | z | x, y | x | y, z | |||
Raman | αxx+αyy, αzz | (αxxx-αyyx,αxyy), (αxzy,αyzx) | αxx,αyy,αzz, αxy | αxz,αyz |
IR | Raman | Assignment | IR | Raman | Assignment |
---|---|---|---|---|---|
174w | γrg, γC-NH2 | 1416m | νBO, δBOH | ||
409w | δNCN | 1446w | δCH, νrg, δNCN | ||
460m | 460w | γrg | 1467m | νC-NH2, δNH2, δNCN, νBO, | |
513w | 518w | τNH2, δOBO, δBOH | 1493s | δBOH | |
546w | γCH, γrg, δOBO, δBOH | 1510sh | |||
597w | δrg, δNCN | 1568s | νrg, δrg, δNCN, ρNH2, δCH | ||
657w | 657w | 1592m | 1589w | δNH2, νC-NH2, νrg | |
670w | γBO3 | 1652m | |||
693w | ? | 1664m | 1660w | ||
760w | γBO3, γXH(…X) | 2364w | ? | ||
779w | γCH, γBO3, γXH(…X) | 2418w | |||
817w | 818w | γrg, γCN3, γBO3 | 2641w | ||
874w | 877vs | δBO3, γBO3, νsrg, δsrg | 2700w | ||
981w | γCH | 3012s | 3012w | νOH(…N), νCH | |
1008w | νrg, δrg | 3030s | 3033w | ||
1050w | 1050w | ρNH2, δCH | 3060sb | νOH(…N) | |
1080w | 1081s | δCH, νrg | 3100sh | 3102w | νOH(…N), νCH |
1131w | 1131w | δCH, ρNH2 | 3140w | ||
1185sh | ? | 3205s | 3200wb | νNH(…O) | |
1196m | νBO, δBOH | 3345s | |||
1233m | νrg, δrg, ρNH2 | 3378m | |||
1362m | 1365w | δCH, νC-NH2 |
IR | Raman | Assignment | IR | Raman | Assignment |
---|---|---|---|---|---|
195w | external mode | 1212m | νrg, δrg, ρNH2 | ||
406w | 408w | δNCN | 1244m | νrg, δrg, ρNH2, νBO, δBOH | |
446m | 451w | γrg | 1319m | 1319w | δCH, ρNH2 |
482w | δOBO, δBOH | 1359m | 1360w | δCH, νC-NH2 | |
515w | τNH2, δOBO, δBOH | 1421s | νBO, δBOH | ||
524w | 520w | 1468s | νC-NH2, δNH2, δNCN, νBO, | ||
537w | γCH, γrg, δOBO, δBOH | 1501s | 1496w | δBOH | |
601w | δrg, δNCN | 1582s | νrg, δrg, δNCN, ρNH2, δCH | ||
623w | 1599m | 1600m | δNH2, νC-NH2, νrg | ||
658m | 661w | δrg, δNCN, γBO3 | 1629s | 1626m | |
726m | γBO3, γXH(…X) | 2263m | ? | ||
777m | γCH, γBO3 | 2313m | |||
794m | 2410m | ||||
821m | 816w | γrg, γCN3, γBO3 | 3000sb | 3020w | νOH(…N), νCH |
870m | 879vs | δBO3, γBO3, νsrg, δsrg | 3047w | νCH | |
990w | γCH | 3124sh | 3124m | ||
1022m | νrg, δrg | 3159w | νOH(…O) | ||
1087m | 1089m | δCH, νrg | 3230sb | 3220w | |
1135m | 1128w | δCH, ρNH2 | 3350s | νOH(…N), νNH(…O) | |
1174s | 1180w | δCH, ρNH2, νBO, δBOH | 3480m |
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Kloda, M.; Matulková, I.; Císařová, I.; Becker, P.; Bohatý, L.; Němec, P.; Gyepes, R.; Němec, I. Cocrystals of 2-Aminopyrimidine with Boric Acid—Crystal Engineering of a Novel Nonlinear Optically (NLO) Active Crystal. Crystals 2019, 9, 403. https://doi.org/10.3390/cryst9080403
Kloda M, Matulková I, Císařová I, Becker P, Bohatý L, Němec P, Gyepes R, Němec I. Cocrystals of 2-Aminopyrimidine with Boric Acid—Crystal Engineering of a Novel Nonlinear Optically (NLO) Active Crystal. Crystals. 2019; 9(8):403. https://doi.org/10.3390/cryst9080403
Chicago/Turabian StyleKloda, Matouš, Irena Matulková, Ivana Císařová, Petra Becker, Ladislav Bohatý, Petr Němec, Róbert Gyepes, and Ivan Němec. 2019. "Cocrystals of 2-Aminopyrimidine with Boric Acid—Crystal Engineering of a Novel Nonlinear Optically (NLO) Active Crystal" Crystals 9, no. 8: 403. https://doi.org/10.3390/cryst9080403