Next Article in Journal
Biologically Active 1-Arylpiperazines. Synthesis of New N-(4-Aryl-1-piperazinyl)alkyl Derivatives of Quinazolidin-4(3H)-one, 2,3-Dihydrophthalazine-1,4-dione and 1,2-Dihydropyridazine-3,6-dione as Potential Serotonin Receptor Ligands
Previous Article in Journal
Niobium Pentachloride Catalysed Ring Opening of Epoxides
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Crystal and molecular structure of cis-Dichlorobis(triphenylphosphite) Platinum(II)

Chemistry. Dept., Science Faculty, Bu-Ali-Sina University Hamadan, Iran
*
Author to whom correspondence should be addressed.
Molecules 2001, 6(9), 777-783; https://doi.org/10.3390/60900777
Submission received: 5 December 2000 / Revised: 26 August 2001 / Accepted: 27 August 2001 / Published: 31 August 2001

Abstract

:
The single crystal structure of cis-dichlorobis(triphenyphosphite) platinum(II), [PtCl2(P(OPh)3)2] has been determined. This complex crystallises in the orthorhombic space group, P212121 with cell constant, a=10.4135(13), b=14.0635(16), c=23.505(3) Ǻ and v=3448.3(7) Ǻ 3. The Pt-Cl1 and Pt-Cl2 distances are 2.3390(10) Ǻ and 2.3256 Ǻ, which are longer than Pt-P1 and Pt-P2 with 2.1985(12) Ǻ and 2.1998(10) Ǻ respectively. These data together with bond angles suggest a distorted square planar geometry for this complex with two chlorine ligands in a cis configuration.

Introduction

In spite of the extensive structural studies on platinum and palladium complexes containing a variety of P-donor ligands [1,2], X-ray structure analyses of platinum derivatives containing triphenylphosphite derivatives are scarce. To the best of our knowledge no such determinations of the title compound have been reported so far. We have recently reported a new procedure for the synthesis of a palladium complex [3] and herein we describe the synthesis and structure determination of an analogous platinum complex.

Results and discussion

Cis-dichlorobis(triphenylphophite)platinum, [PtCl2(P(OPh)3)2], (1) has been studied in solution This complex was synthesised using a new method but the IR and NMR data are in excellent agreement with an earlier conclusion [1]. However, relatively little work has been done on structural determinations of this type of complex and this lack of information is probably due to difficulty experienced in crystallising the compound from the ethanol reaction solution [4,5]. This work describes the new method of the preparation and characterisation of (1). The structure of (1) is shown in Figure 1.
Figure 1. Molecular structure of [PtCl2(P(OPh)3)2] showing the atom numbering scheme used.
Figure 1. Molecular structure of [PtCl2(P(OPh)3)2] showing the atom numbering scheme used.
Molecules 06 00777 g001
Crystal data, structural refinement are summarised in Table 1.
Table 1. Crystal data and structure refinement
Table 1. Crystal data and structure refinement
Identification codejsa1
Empirical formulaC36H30Cl2O6P2Pt
Formula weight886.59
Temperature213(2) K
Wavelength0.71073 A
Crystal system, space grouporthorhombic, P 21 21 21
Unit cell dimensionsa = 10.4315 (13 ) Ǻ alpha = 90 deg.
b = 14.0635 (16) Ǻ beta = 90 deg
c = 23.505 ( 3 ) Ǻ gamma = 90 deg.
Volume3448.3 ( 7 ) Ǻ 3
Z, calculated density4, 1.708 Mg/m3
Absorption coefficient4.164 mm-1
F (000)1744
Crystal size0.68 × 0.20 × 0.16 mm
Theta range for data collection1.73 to 24.26 deg.
Index ranges-11<=h<11, -16<=k<=16, -26<=1<=26
Reflections collected / unique22003/5449 [R(int)=0.0534]
Completeness to 2theta = 24.2698.0%
Max. and min. transmission0.5554 and 0.1640
Refinement methodfull-matrix least-squares on F2
Data / restraints / parameters5449 / 0 /424
Goodness-of-fit on F20.943
Final r indices [I>2sigma(I)]R1 = 0.0203, WR2 = 0.0410
R indices (all data)R1 = 0.0280, WR2 = 0.0425
Absolute structure parameter-0.018(5)
Largest diff. peak and hole0.559 and -0.783 e.A−3
Absorption correctionnumerical (X-SHAPE : Stoe, 1997)
Tmin =0.1640, Tmax =0.5554
22003 measured reflections
5449 independent reflections
4677 reflections with> 2sigma(I
Rint = 0.0534
The more important bond lengths and angles together with references are presented in Table 2.
Table 2. Selected distances and angles for [PtCl2(P(OPh)3)2].
Table 2. Selected distances and angles for [PtCl2(P(OPh)3)2].
Distances (Ǻ)
O1-P11.579(3)O6-P21.577(3)
O2-P21.589(3)P1-Pt12.1985(2)
O3-P11.484(3)P2-Pt12.1998(10)
O4-P21.570(3)Cl1-Pt12.3390(10)
O5-P21.589(3)Cl2-Pt12.3256(11)
Angles (°)
O1-P1-O2104.69(17)O4-P2-Pt1117.27(14)
O1-P1-O398.42(19)O5-P2-Pt1111.30(13)
O2-P1-O3 103.42(17)O6-P2-Pt1119.44(13)
O1-P1-Pt1118.46(12)P1-Pt1-P293.56(4)
O2-P1-Pt1113.57(12)P1-Pt1-Cl2177.20(4)
O3-P1-Pt1116.12(14)P1-Pt1Cl189.38(4)
O4-P2-O5104.7(2)P2-Pt1-Cl288.58(4)
O4-P2-O696.90(18)P2-Pt1-Cl1176.93(4)
O5-P2-O6105.27(18)P1 -Pt1 -Cl288.51(4)
Data collection: EXPOSE [5]. Cell refinement: CELL [6]. Data reduction: INTEGRATE [7]. Program(s) used to solve structure: [8]. Program(s) used to refine structure: SHELXL97 [9]. Molecular graphic: ORTEP3 (Farrugia, 1997).
Atomic coordinates are given in Table 3.
Table 3. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2 x 103) U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
Table 3. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2 x 103) U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
XYZU(eq)
C(1)-2590(4)790(3)676(2)23(1)
C(2)-3845(4)792(3)527(2)27(1)
C(3)-4399(5)1648(4)360(2)38(1)
C(4)-3686(5)2466(4)354(2)33(1)
C(5)-2407(5)2449(3)506(2)29(1)
C(6)-1838(4)1607(3)666(2)29(1)
C(7)-1961(4)353(3)2097(2)29(1)
C(8)-2141 (4)-373(3)2478(2)33(1)
C(9)-3208(6)-338(4)2833(2)43(2)
C(10)-4054(6)411(4)2806(3)50(2)
C(11)-3837(6)1135(4)2425(3)45(2)
C(12)-2744(5)1116(4)2075(2)37(1)
C(13)-363(4)-2130(3)1175(2)27(1)
C(14)-472(6)-2386(4)629(3)43(2)
C(15)169(7)-3192(4)440(3)59(2)
C(16)863(8)-3722(4)806(3)59(2)
C(17)940(9)-3467(4)1371(3)51(2)
C(18)327(6)-2650(4)1571(3)37(2)
C(19)1955(5)1924(3)1511(2)29(1)
C(20)2633(7)2444(4)1139(3)60(2)
C(21)2063(9)3343(5)949(3)68(2)
C(22)900(10)3581(5)1160(4)59(2)
C(23)272(8)3078(5)1545(4)60(2)
C(24)793(6)2243(4)1729(3)45(2)
C(25)2115(5)-548(3)2526(2)26(1)
C(26)1685(4)120(5)2905(2)36(1)
C(27)2154(5)107(5)3455(2)41(1)
C(28)3020(5)-574(4)3614(2)39(1)
C(29)3433(5)-1243(4)3231(2)37(1)
C(30)2986(5)-1238(3)2681(2)30(1)
C(31)4158(4)-1167(3)1316(2)24(1)
C(32)5391(5)-1294(4)1486(3)38(1)
C(33)5971(6)-2158(4)1380(3)51(2)
C(34)5323(5)-2877(4)1112(3)43(2)
C(35)4070(6)-2743(3)951(2)38(1)
C(36)3466(5)-1882(4)1050(2)32(1)
O(1)-2095(3)-105(3)865(1)26(1)
O(2)-868(3)348(2)1741(1)26(1)
O(3)-1010(3)-1320(2)1391(1)30(1)
O(4)2427(3)1063(2)1730(2)36(1)
O(5)1607(3)-558(2)1966(1)28(1)
O(6)3653(3)-252(2)1432(1)24(1)
P(1)-772(1)-267(1)1176(1)22(1)
P(2)2200(1)53(1)1446(1)22(1)
Cl(1)-175(1)-72(1)-151(1)30(1)
Cl(2)2851(1)175(1)153(1)32(1)
Pt(1)1005(1)-26(1)694(1)18(1)
The structural analysis proved a cis-distorted square planar arrangement for 1, and different interatomic distances and bond angles in comparison with [PtCl4]2-(2) was observed. The Pt-P and Pt-Cl bonds are approximately within the same range of other phosphine complexes [1,2], but the Pt-Cl distances are significantly shorter than Pt-P (see Table 3). This causes a big distortion which leads to asymmetric structure and is much bigger than what we observed in cis-[PdCl2(P(OPh)3)2] (3) structure [3]. Evidently the small difference between Cl2-Pt1-P1 [177.20° (4)] and Cl1-Pt1-P2 [176.93°(4)] angles also confirms the distorted square planar geometry of 1. This is in contrast with what has been observed in solution [5]. Discussion of bond-length in 1 [in comparison with 2 containing a C2 axis] in relation to the above configuration is quite interesting. We noticed that 1 with the different P1-Pt1-P2 [93.56° (4)], P1-Pt1-Cl1 [89.38° (4)], P2-Pt1-Cl2 [88.58° (4)] and Cl1Pt1-Cl2 [88.51° (4)] angles is completely asymmetrical. Not only it changes from D4h and C2v symmetry from 2 and 3 respectively but it is also consistent with C1 symmetry structure. These can be taken probably as a structural confirmation of the effect of different metal atoms in 1 and 3 or a larger proportion of σ -donor character in the Pt-P bonds for 1 in comparison with the Pd-P bonds of 3, which results in a greater strict effect of the phosphite ligands. All the bond lengths (Table 2) are approximately within the normal range compared with other phosphine complexes [1,2]. Finally as one can see the P1-Pt1-Cl2 angle [88.51°(4)] is narrower than the P1-Pt1-P2 [93.56°(4)] angle and this is apparently due to the steric effect of phosphite ligands.

Experimental

Refluxing PtCl2 and POPh3 at 60 ºC in a molar ratio of 1:2 in toluene for 6 h. gave a yellowish precipitate, which was extracted from the obtained suspension. Colourless crystals suitable for X-ray diffraction analysis were obtained by slow addition of methanol to a chloroform solution containing the compound. Crystallographic data was recorded on a Stoe IPDS diffractometer using graphite monochromated Mokα-radiation (λ = 0.71073 Å), T = 200 K. Structures were solved by direct methods and refined by full-matrix least squares against F2 using all data. Supplementary material, comprising crystallographic experimental details, positional parameters for all atoms, bond distances and angles, anisotropic thermal parameters and hydrogen atoms coordinates has been deposited with the Cambridge Crystallographic Database. The deposition code is CCDC144750.

Acknowledgements

We thank the University of Bu-Ali-Sina for grant support to A.N and Dr. Jamie F. Bickley, University of Liverpool, UK, for the crystal structure analysis.

References

  1. Kitano, Y.; Ashida, T. Acta Crystallogr. 1983, C39, 1015.
  2. Davies, J.A.; Pinkerton, A.A.; Staples, R.J. Acta Crystallogr. 1990, C48, 48.
  3. Sabounchei, S.J.; Naghipour, A; Bickley, J.F. Acta Crystallgr. 2000, C56, 280.
  4. Allen, F.A.; Pidcok, A.; Waterhouse, C.R. J. Chem. Soc. (A) 1970, 2087.
  5. Ahmed, N.; Ainscough, E.W.; James, T.A.; Robinson, S.D. J. Chem. Soc. Dalton Trans. 1973, 1148.
  6. EXPOS, Stoe IPDS Software for Publication, version 2.79. Stoe IPDS: Darmstadt, Germany, Stoe 1997a.
  7. Cell Program for Cell Refinement; Version 2.79. Stoe IPDS: Darmstadt, Germany, Stoe 1997b.
  8. INTEGRATE Program for Reduction of IPDS Data, Version 2.79. Stoe IPDS: Darmstadt, Germany, Stoe 1997c.
  9. Sheldrick, G.M. Acta Crytallogr. 1990, A46, 467.
  10. Sheldrick, G.M. SHELXL 97 release 97-1; Program for Refinement of [3d] Crystal Structure; University of Göttingen: Germany, 1997.
  • Sample Availability: The product reported in this paper is available from MDPI

Share and Cite

MDPI and ACS Style

Sabounchei, S.J.; Naghipour, A. Crystal and molecular structure of cis-Dichlorobis(triphenylphosphite) Platinum(II). Molecules 2001, 6, 777-783. https://doi.org/10.3390/60900777

AMA Style

Sabounchei SJ, Naghipour A. Crystal and molecular structure of cis-Dichlorobis(triphenylphosphite) Platinum(II). Molecules. 2001; 6(9):777-783. https://doi.org/10.3390/60900777

Chicago/Turabian Style

Sabounchei, Seyyed Javad, and Ali Naghipour. 2001. "Crystal and molecular structure of cis-Dichlorobis(triphenylphosphite) Platinum(II)" Molecules 6, no. 9: 777-783. https://doi.org/10.3390/60900777

Article Metrics

Back to TopTop