- Email: [email protected]
Main group metal halide complexes with sterically hindered thioureas part XVIII: The synthesis, characterization, and X-ray crystallographic study of a BiCl3 complex with 1-methyl-2(3H)-imidazolethione
Inorganica Chimica Acta 359 (2006) 2252–2255 www.elsevier.com/locate/ica
Main group metal halide complexes with sterically hindered thioureas part XVIII: The synthesis, characterization, and X-ray crystallographic study of a BiCl3 complex with 1-methyl-2(3H)-imidazolethione Daniel J. Williams a,*, Anna M. Hutchings a, Natalia E. McConnell a, Roland A. Faucher a, Benjamin E. Huck a, Carol A.S. Brevett b, Donald VanDerveer c a
Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, GA 30144, USA b SAIC, P.O. Box 68, Gunpowder Branch, Aberdeen Proving Ground, MD 21010, USA c Department of Chemistry, Clemson University, Clemson, SC 29634, USA Received 23 November 2005; accepted 31 December 2005 Available online 28 February 2006
Abstract A new bismuth(III) chloride complex with 1-methyl-2(3H)-imidazolethione (meimtH) has been synthesized and characterized via standard methods including solid state 13C nuclear magnetic resonance (NMR) and single crystal X-ray diffractometry. The complex, BiCl3[meimtH]2.5 Æ H2O, crystallizes in a triclinic space group. The complex has two different coordination spheres for bismuth, which are linked together in the solid state via hydrogen bonding. One coordination sphere is distorted octahedral with the ligands in meridional positions, while the other is a dimer consisting of two octahedra sharing a common edge through bridging chlorine atoms. The ligands are cis to each other and trans to the chlorine bridges, while the remaining four chlorine atoms are trans to each other and perpendicular to the chlorine–sulfur plane. There is no strong evidence for a stereoactive lone pair in either coordination sphere. 2006 Elsevier B.V. All rights reserved. Keywords: Bismuth(III) chloride complex; Thione complex; mer-Isomer; X-ray crystal structure; Thiourea ligands
1. Introduction Several years ago, we noted very interesting structural differences between two different bis-thiourea adducts of BiCl3, and this study launched a series of articles dealing with the effects of sterically hindered thioureas complexed with main group metal halides. The two inaugural complexes compared were BiCl3(etu)2 [1] and BiCl3(dmit)2 [2], where etu = ethylenethiourea and dmit = 1,3-dimethyl2(3H)-imidazolethione. Both thioureas are five-membered ring heterocycles with etu having hydrogens bonded to the ring nitrogens and dmit having N-methyl groups, thus making the thione group more sterically hindered. Additionally, the imidazole ring in dmit is quasi-aromatic [3,4], whereas
*
Corresponding author. E-mail address: [email protected] (D.J. Williams).
0020-1693/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2005.12.074
the etu ring is saturated. Thus, both ligands are very similar. The structural difference between BiCl3(etu)2 and BiCl3(dmit)2 is dramatic, however. BiCl3(dmit)2 in the solid state has a dimeric structure of two distorted octahedra sharing a common edge through cis-bonded chlorines. The thione ligands are bonded trans to each other and perpendicular to the plane made by the two bismuth atoms and six chlorine atoms [2]. The etu complex, however, is made up of a polymeric zig-zag chain of octahedra connected by common chlorine vertices cis to each other in the coordination sphere of the bismuth atom. Additionally, the two thiourea ligands are cis to each other and trans to the bridging chlorine atoms [1]. There is also an evidence of hydrogen bonding between the N-hydrogens and the neighboring chlorine atoms. Clearly, the presence of the N-bonded methyl groups forces a trans configuration for the ligands, thus keeping the structure dimeric as opposed to polymeric because of ligand placement.
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
Recently, we prepared a complex which could be considered an example of intermediate ligand steric bulk, and the results are once again dramatic. Reported below is the synthesis, characterization, and results of X-ray crystallographic structural determination of a new complex of BiCl3 with 1-methyl-2(3H)-imidazolethione (meimtH). 2. Experimental 2.1. General All chemicals were commercially obtained and used without further purification. Elemental analysis was performed by Atlanta Microlabs Inc. Fourier transform infrared spectroscopy (FT-IR) was performed on powdered solids using a Perkin–Elmer Spectrum One spectrophotometer fitted with a diamond attenuated reflectance stage (ATR). Results are reported in cm 1 (±2.0). Key: vs – very strong, s – strong, m – medium, w – weak, vw – very weak, br – broad. Melting point was determined in an open capillary tube on a MelTemp II melting point apparatus. A Carbon-13 solid state magic angle spinning nuclear magnet resonance spectrum (13C SSMAS NMR) was collected at 9.4 T using a Varian Inova 400 MHz NMR spectrometer equipped with a Doty Scientific 7 mm standard series VT-MAS (variable temperature magic angle spinning) probe. The spectrum was obtained using direct polarization with the ‘‘TOSS’’ sideband suppression pulse sequence at spinning rates of 3000 Hz. Delay times between transients were 600 s, 128 transients were collected, and spectra were referenced to external tetramethylsilane. Values are reported in ppm (d) relative to external tetramethylsilane. Assignments and integration values are given in parentheses. 2.2. Synthesis In a 250 mL beaker, 3.30 g (10.0 mmol) of BiCl3 Æ H2O (Aldrich) was dissolved in approximately 40 mL acetonitrile. To this solution, 2.28 g of meimtH (20.0 mmol) dissolved in 40 mL acetonitrile was added, and a bright orange precipitate formed. Filtration and washing with small portions of the solvent yielded 5.00 g of crude BiCl3(meimtH)2.5 (92% yield). Orange crystals suitable for X-ray study recrystallized as the monohydrate out of 10% (v/v) HCl. Melting point 145–147 C. Anal. Calc. for C10H17N5OS2.5BiCl3: C, 19.41; H, 2.76; N, 11.32; Cl, 17.18. Found: C, 19.63; H, 2.69; N, 11.35; Cl, 17.11%. FT-IR: 3118m, 1698m, 1571s, 1469m, 1439m, 1352m, 1285s, 1226m, 1158s, 1102m, 1080w, 1033m, 917m, 855w, 743vs, 671vs. 13C SSMAS NMR (ppm): 37.0 (methyl, 1); 120.1; 123.9 (ring olefinic, 2); 149.7 (thiocarbonyl, 1).
Table 1 Crystal data and structure for refinement for BiCl3(meimtH)2.5 Empirical formula Formula weight Temperature (K) ˚) Wavelength (A Crystal system, space group Unit cell dimensions ˚) a (A ˚) b (A ˚) c (A a () b () c () ˚ 3) Volume (A Z, calculated density (Mg/m3) Absorption coefficient (mm 1) F(0 0 0) Crystal size (mm) h Range for data collection range () Reflections collected/unique (Rint) Completeness to h = 25.1 (%) Absorption correction Maximum and minimum transmission Refinement method Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2r(I)] R indices (all data) Extinction coefficient ˚ 3) Largest difference in peak and hole (e A
C20H34Bi2Cl6N10S5O2 1237.53 198(2) 0.71073 triclinic, P 1 9.9522(8) 10.3940(8) 19.6112(15) 98.792(1) 94.884(1) 99.673(1) 1963.5(3) 2, 2.093 9.660 1176 0.41 · 0.31 · 0.10 1.06–28.76 18 121/9185 (0.0552) 90.1 none 0.4390 and 0.1104 full-matrix least-squares on F2 9185/0/433 1.248 R1 = 0.0444, wR2 = 0.1151 xR1 = 0.0560, wR2 = 0.1228 0.00165(19) 5.489 and 2.545
Table 2 ˚ ) and angles () Selected coordination sphere bond distances (A Distances Bi(1)–Cl(1) Bi(1)–Cl(2) Bi(1)–S(2) Bi(1)–S(1) Bi(1)–Cl(3) Bi(1)–S(3) Bi(2)–Cl(6) Bi(2)–Cl(4) Bi(2)–S(5) Bi(2)–S(4) Bi(2)–Cl(5A) Bi(2)–Cl(5)
2.584(2) 2.700(2) 2.762(2) 2.777(2) 2.876(2) 2.948(2) 2.651(2) 2.673(2) 2.679(2) 2.736(2) 2.876(2) 3.000(2)
3. Crystallographic studies Intensity data for BiCl3[meimtH]2.5 Æ H2O were measured at 198 ± 2 K with graphite monochromated Mo
2253
Estimated SDs given in parentheses.
Angles Cl(1)–Bi(1)–Cl(2) Cl(1)–Bi(1)–S(2) Cl(2)–Bi(1)–S(2) Cl(1)–Bi(1)–S(1) S(2)–Bi(1)–S(1) Cl(2)–Bi(1)–Cl(3) S(2)–Bi(1)–Cl(3) S(1)–Bi(1)–Cl(3) Cl(1)–Bi(1)–S(3) Cl(2)–Bi(1)–S(3) S(1)–Bi(1)–S(3) Cl(3)–Bi(1)–S(3) Cl(6)–Bi(2)–S(5) Cl(4)–Bi(2)–S(5) Cl(6)–Bi(2)–S(4) Cl(4)–Bi(2)–S(4) S(5)–Bi(2)–S(4) Cl(6)–Bi(2)–Cl(5A) Cl(4)–Bi(2)–Cl(5A) S(5)–Bi(2)–Cl(5A) Cl(6)–Bi(2)–Cl(5) Cl(4)–Bi(2)–Cl(5) S(4)–Bi(2)–Cl(5) Cl(5A)–Bi(2)–Cl(5) Bi(2A)–Cl(5)–Bi(2)
93.75(8) 93.26(7) 90.68(6) 89.12(6) 81.50(6) 102.01(7) 93.35(6) 76.22(6) 88.74(6) 90.24(6) 97.49(6) 84.44(6) 85.67(8) 89.59(6) 77.76(6) 86.76(6) 94.90(7) 100.21(7) 95.26(6) 84.88(6) 97.39(7) 91.54(6) 101.04(6) 79.18(6) 100.82(6)
2254
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
˚ ) on a Bruker 1 K CCD difKa radiation (k = 0.71073 A fractometer. Data were collected to a maximum 2h value of 57.5 (1.06 < h < 28.76) in 0.3 oscillations (in x) with two 15.0 s exposures (to identify detector anomalies) for a total of 18 121/9185 (Rint = 0.0552) reflections collected. Data were corrected for Lorentz and polarization effects, and no absorption correction was applied [5]. The structure was solved by full-matrix least-squares on F2. All nonhydrogen atoms were refined anisotropically; hydrogen atoms were calculated in the riding mode, and their isotropic temperature factors were refined. Data processing was performed with SAINT [6], and structure solution, refinement and calculation of the derived results were performed with SHELXTL [7]. Neutral atom scattering factors were those of Cromer and Waber [8], and the real and imaginary anomalous dispersion corrections were those of Cromer [9]. Relevant crystallographic data are given in Table 1 and selected bond lengths and angles for the bismuth coordination sphere are given in Table 2. 4. Results and discussion The new complex of bismuth(III) chloride and meimtH shown in Fig. 1 fits, in part, the same general structural pattern observed for BiCl3(dmit)2 [2] with two BiCl4L2 (L = ligand) octahedra sharing a common edge through bridging chlorine atoms. Two major differences appear in the new structure reported here, however. The ligands are cis to each other and occupy the same plane as the bridging chlorine atoms as opposed to being trans and perpendicular to the six atom chlorine plane as observed in the structure of BiCl3(dmit)2. Additionally, there is a separate octahedral BiCl3(meimtH)3 unit tethered to the dimer via ˚ (H8– hydrogen bonding (Fig. 1) at distances of 2.39 A ˚ (H10–Cl3). The octahedral unit shows a Cl3) and 2.33 A meridional (OC-6-21) configuration of ligands similar to that observed for Bi(SCN)3(dmit)3 [10]. Bismuth chlorine bond distances in both the octahedral unit (Fig. 2) and ˚ the dimer (Fig. 3) are similar and range from 2.584(2) A [Bi(1)–Cl(1)] observed in the octahedral unit to the longest ˚ [Bi(2)–Cl(5) and Bi(2A)–Cl(5A)] as bonds of 3.000(2) A expected, since they are involved in bridging within the ˚ dimeric unit. The next longest bond Bi–Cl at 2.876(2) A is the bridging complement [Bi(2)–Cl(5A) or Bi(2A)–
Fig. 1. Structure of BiCl3[meimtH]2.5 Æ H2O showing dimeric unit and octahedral portion with hydrogen bonding signified by dashed lines.
Fig. 2. ORTEP drawing at 50% probability level showing octahedral portion of BiCl3[meimtH]2.5 Æ H2O with one-half occupancy for C(8).
Cl(5)] and happens to be the same length as Bi(1)–Cl(3), the bond involved in hydrogen bonding in the octahedral ˚ [Bi(2)– unit. Bismuth–sulfur bonds range from 2.679(2) A ˚ [Bi(1)–S(3)]. Overall, both Bi–Cl and S(5)] to 2.948(2) A Bi–S bond distances do not deviate significantly from those noted in the literature for similar bismuth(III) chloride thione complexes [1,2,10]. Bond angles in the bismuth coordination sphere show deviation from ideal angles of 90 in both the dimer and the octahedron. The narrowest angle is 76.22(6) [S(1)– Bi(1)–Cl(3)] which also contains one of the chlorine atoms involved in hydrogen bonding to the dimer. The largest angle of 102.01(7) also involves Cl(3) and it is likely that these distortions are due to hydrogen bonding with the dimer. There is no firm evidence for a stereoactive lone pair of electrons in either the octahedron or the dimer. We have
Fig. 3. ORTEP drawing at 50% probability level of dimeric portion of BiCl3[meimtH]2.5 Æ H2O.
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
recent by performed density functional theory (DFT) calculations on similar compounds and have discovered a large amount of s character associated with the highest occupied molecular orbitals (HOMO) of bismuth [11]. This is in keeping with many similar findings involving lead(II) complexes [12], and in part can be correlated to the hard– soft acid–base nature of the ligand [12,13]. In soft–soft interactions, the lone pair tends to be stereoinactive [13] or what is termed ‘‘holodirected’’, whereas in hard–hard interactions, the lone pairs were stereoactive or ‘‘hemidirected’’ [12]. Ligand bond distances and angles agree well with literature values [14]. In the case of one of the ligands, there is disorder in the solid state where C8 has 50% occupancy on either one of two ring nitrogens (N3, N4). Solid state 13 C NMR shows good agreement with other chemical shifts published for these types of thione ligands [15,16], but it cannot differentiate between the dimer and the octahedral environment. Particularly sensitive to coordination is the thionyl carbon which is observed at 147.9 ppm for this complex, but is normally seen at 164.2 ppm when not coordinated [16]. 5. Conclusions The title compound provides yet another example of ligand steric bulk influencing the overall structure of a heavy main group halide complex. Whereas smaller compact ligands (L) such as etu allowed for the polymerization of BiCl4L2 octahedra, the dimethyl analog blocked such polymerization to give a dimer only. The intermediate monomethyl ligand gave both the dimer with an altered ligand arrangement and a mer-BiCl3L3 octahedron. Other Bi(III) complexes are currently under investigation with ligands of varying bulk to determine if a structural pattern is present, and to further investigate DFT calculations in relationship to the structure.
2255
Appendix A. Supplementary data CCDC 279926 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.ica.2005.12.074. References [1] L.P. Battaglia, A. Bonamartini Corradi, M. Nardelli, M.E. Vidoni Tani, J. Chem. Soc., Dalton Trans. (1978) 583. [2] D.J. Williams, B. Rubin, J. Epstein, W.K. Dean, A. Viehbeck, Cryst. Struct. Commun. 11 (1982) 1. [3] D.J. Williams, D. VanDerveer, B.R. Crouse, R.R. Raye, T. Carter, K.S. Hagen, M. Brewer, Main Group Chem. 2 (1997) 61. [4] P.D Boyle, S.M. Godfrey, J. Chem. Soc., Dalton Trans. (2000) 1959. [5] SADABS R.H. Blessing, Acta Crystallogr. A51 (1995) 33. [6] SMART 5.054, SAINT 6.01, SHELXTL 5.1, Bruker AXS, Madison, WI, USA, 1998–1999. [7] G.M. Sheldrick, SHELXTL: Crystallographic Computing System, Version 5.1, Bruker Analytical X-ray Systems, Madison, WI, 1997. [8] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, vol. C, Kluwer Academic Publishers, Dordrecht, 1992, pp. 500–502, Table 6.1.1.4. [9] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, vol. C, Kluwer Academic Publishers, Dordrecht, 1992, pp. 219–222, Table 4.2.6.8. [10] D.J Williams, T. Carter, K.L. Fahn, D. VanDerveer, Inorg. Chim. Acta 228 (1995) 69. [11] J.J. Concepcion, D.J. Williams, Unpublished results. [12] L. Shimoni-Livny, J.P. Glusker, C.W. Bock, Inorg. Chem. 37 (1998) 1853. [13] K.J. Wynne, J. Chem. Ed. 50 (1973) 328. [14] J.S. Casas, E. Garcia Martinez, A. Sanchez Gonzales, J. Sordo, U. Casellato, R. Graziani, U. Russo, J. Organomet. Chem. 493 (1995) 107. [15] D.J. Williams, V.L.H. Bevilacqua, P.A. Morson, W.T. Pennington, G.L. Schimek, N.T. Kawai, Inorg. Chim. Acta 308 (2000) 129. [16] D.J. Williams, V.L.H. Bevilacqua, P.A. Morson, K.J. Dennison, W.T. Pennington, G.L. Schimek, D. VanDerveer, J.S. Kruger, N.T. Kawai, Inorg. Chim. Acta 285 (1999) 217.
Main group metal halide complexes with sterically hindered thioureas part XVIII: The synthesis, characterization, and X-ray crystallographic study of a BiCl3 complex with 1-methyl-2(3H)-imidazolethione Daniel J. Williams a,*, Anna M. Hutchings a, Natalia E. McConnell a, Roland A. Faucher a, Benjamin E. Huck a, Carol A.S. Brevett b, Donald VanDerveer c a
Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, GA 30144, USA b SAIC, P.O. Box 68, Gunpowder Branch, Aberdeen Proving Ground, MD 21010, USA c Department of Chemistry, Clemson University, Clemson, SC 29634, USA Received 23 November 2005; accepted 31 December 2005 Available online 28 February 2006
Abstract A new bismuth(III) chloride complex with 1-methyl-2(3H)-imidazolethione (meimtH) has been synthesized and characterized via standard methods including solid state 13C nuclear magnetic resonance (NMR) and single crystal X-ray diffractometry. The complex, BiCl3[meimtH]2.5 Æ H2O, crystallizes in a triclinic space group. The complex has two different coordination spheres for bismuth, which are linked together in the solid state via hydrogen bonding. One coordination sphere is distorted octahedral with the ligands in meridional positions, while the other is a dimer consisting of two octahedra sharing a common edge through bridging chlorine atoms. The ligands are cis to each other and trans to the chlorine bridges, while the remaining four chlorine atoms are trans to each other and perpendicular to the chlorine–sulfur plane. There is no strong evidence for a stereoactive lone pair in either coordination sphere. 2006 Elsevier B.V. All rights reserved. Keywords: Bismuth(III) chloride complex; Thione complex; mer-Isomer; X-ray crystal structure; Thiourea ligands
1. Introduction Several years ago, we noted very interesting structural differences between two different bis-thiourea adducts of BiCl3, and this study launched a series of articles dealing with the effects of sterically hindered thioureas complexed with main group metal halides. The two inaugural complexes compared were BiCl3(etu)2 [1] and BiCl3(dmit)2 [2], where etu = ethylenethiourea and dmit = 1,3-dimethyl2(3H)-imidazolethione. Both thioureas are five-membered ring heterocycles with etu having hydrogens bonded to the ring nitrogens and dmit having N-methyl groups, thus making the thione group more sterically hindered. Additionally, the imidazole ring in dmit is quasi-aromatic [3,4], whereas
*
Corresponding author. E-mail address: [email protected] (D.J. Williams).
0020-1693/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2005.12.074
the etu ring is saturated. Thus, both ligands are very similar. The structural difference between BiCl3(etu)2 and BiCl3(dmit)2 is dramatic, however. BiCl3(dmit)2 in the solid state has a dimeric structure of two distorted octahedra sharing a common edge through cis-bonded chlorines. The thione ligands are bonded trans to each other and perpendicular to the plane made by the two bismuth atoms and six chlorine atoms [2]. The etu complex, however, is made up of a polymeric zig-zag chain of octahedra connected by common chlorine vertices cis to each other in the coordination sphere of the bismuth atom. Additionally, the two thiourea ligands are cis to each other and trans to the bridging chlorine atoms [1]. There is also an evidence of hydrogen bonding between the N-hydrogens and the neighboring chlorine atoms. Clearly, the presence of the N-bonded methyl groups forces a trans configuration for the ligands, thus keeping the structure dimeric as opposed to polymeric because of ligand placement.
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
Recently, we prepared a complex which could be considered an example of intermediate ligand steric bulk, and the results are once again dramatic. Reported below is the synthesis, characterization, and results of X-ray crystallographic structural determination of a new complex of BiCl3 with 1-methyl-2(3H)-imidazolethione (meimtH). 2. Experimental 2.1. General All chemicals were commercially obtained and used without further purification. Elemental analysis was performed by Atlanta Microlabs Inc. Fourier transform infrared spectroscopy (FT-IR) was performed on powdered solids using a Perkin–Elmer Spectrum One spectrophotometer fitted with a diamond attenuated reflectance stage (ATR). Results are reported in cm 1 (±2.0). Key: vs – very strong, s – strong, m – medium, w – weak, vw – very weak, br – broad. Melting point was determined in an open capillary tube on a MelTemp II melting point apparatus. A Carbon-13 solid state magic angle spinning nuclear magnet resonance spectrum (13C SSMAS NMR) was collected at 9.4 T using a Varian Inova 400 MHz NMR spectrometer equipped with a Doty Scientific 7 mm standard series VT-MAS (variable temperature magic angle spinning) probe. The spectrum was obtained using direct polarization with the ‘‘TOSS’’ sideband suppression pulse sequence at spinning rates of 3000 Hz. Delay times between transients were 600 s, 128 transients were collected, and spectra were referenced to external tetramethylsilane. Values are reported in ppm (d) relative to external tetramethylsilane. Assignments and integration values are given in parentheses. 2.2. Synthesis In a 250 mL beaker, 3.30 g (10.0 mmol) of BiCl3 Æ H2O (Aldrich) was dissolved in approximately 40 mL acetonitrile. To this solution, 2.28 g of meimtH (20.0 mmol) dissolved in 40 mL acetonitrile was added, and a bright orange precipitate formed. Filtration and washing with small portions of the solvent yielded 5.00 g of crude BiCl3(meimtH)2.5 (92% yield). Orange crystals suitable for X-ray study recrystallized as the monohydrate out of 10% (v/v) HCl. Melting point 145–147 C. Anal. Calc. for C10H17N5OS2.5BiCl3: C, 19.41; H, 2.76; N, 11.32; Cl, 17.18. Found: C, 19.63; H, 2.69; N, 11.35; Cl, 17.11%. FT-IR: 3118m, 1698m, 1571s, 1469m, 1439m, 1352m, 1285s, 1226m, 1158s, 1102m, 1080w, 1033m, 917m, 855w, 743vs, 671vs. 13C SSMAS NMR (ppm): 37.0 (methyl, 1); 120.1; 123.9 (ring olefinic, 2); 149.7 (thiocarbonyl, 1).
Table 1 Crystal data and structure for refinement for BiCl3(meimtH)2.5 Empirical formula Formula weight Temperature (K) ˚) Wavelength (A Crystal system, space group Unit cell dimensions ˚) a (A ˚) b (A ˚) c (A a () b () c () ˚ 3) Volume (A Z, calculated density (Mg/m3) Absorption coefficient (mm 1) F(0 0 0) Crystal size (mm) h Range for data collection range () Reflections collected/unique (Rint) Completeness to h = 25.1 (%) Absorption correction Maximum and minimum transmission Refinement method Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2r(I)] R indices (all data) Extinction coefficient ˚ 3) Largest difference in peak and hole (e A
C20H34Bi2Cl6N10S5O2 1237.53 198(2) 0.71073 triclinic, P 1 9.9522(8) 10.3940(8) 19.6112(15) 98.792(1) 94.884(1) 99.673(1) 1963.5(3) 2, 2.093 9.660 1176 0.41 · 0.31 · 0.10 1.06–28.76 18 121/9185 (0.0552) 90.1 none 0.4390 and 0.1104 full-matrix least-squares on F2 9185/0/433 1.248 R1 = 0.0444, wR2 = 0.1151 xR1 = 0.0560, wR2 = 0.1228 0.00165(19) 5.489 and 2.545
Table 2 ˚ ) and angles () Selected coordination sphere bond distances (A Distances Bi(1)–Cl(1) Bi(1)–Cl(2) Bi(1)–S(2) Bi(1)–S(1) Bi(1)–Cl(3) Bi(1)–S(3) Bi(2)–Cl(6) Bi(2)–Cl(4) Bi(2)–S(5) Bi(2)–S(4) Bi(2)–Cl(5A) Bi(2)–Cl(5)
2.584(2) 2.700(2) 2.762(2) 2.777(2) 2.876(2) 2.948(2) 2.651(2) 2.673(2) 2.679(2) 2.736(2) 2.876(2) 3.000(2)
3. Crystallographic studies Intensity data for BiCl3[meimtH]2.5 Æ H2O were measured at 198 ± 2 K with graphite monochromated Mo
2253
Estimated SDs given in parentheses.
Angles Cl(1)–Bi(1)–Cl(2) Cl(1)–Bi(1)–S(2) Cl(2)–Bi(1)–S(2) Cl(1)–Bi(1)–S(1) S(2)–Bi(1)–S(1) Cl(2)–Bi(1)–Cl(3) S(2)–Bi(1)–Cl(3) S(1)–Bi(1)–Cl(3) Cl(1)–Bi(1)–S(3) Cl(2)–Bi(1)–S(3) S(1)–Bi(1)–S(3) Cl(3)–Bi(1)–S(3) Cl(6)–Bi(2)–S(5) Cl(4)–Bi(2)–S(5) Cl(6)–Bi(2)–S(4) Cl(4)–Bi(2)–S(4) S(5)–Bi(2)–S(4) Cl(6)–Bi(2)–Cl(5A) Cl(4)–Bi(2)–Cl(5A) S(5)–Bi(2)–Cl(5A) Cl(6)–Bi(2)–Cl(5) Cl(4)–Bi(2)–Cl(5) S(4)–Bi(2)–Cl(5) Cl(5A)–Bi(2)–Cl(5) Bi(2A)–Cl(5)–Bi(2)
93.75(8) 93.26(7) 90.68(6) 89.12(6) 81.50(6) 102.01(7) 93.35(6) 76.22(6) 88.74(6) 90.24(6) 97.49(6) 84.44(6) 85.67(8) 89.59(6) 77.76(6) 86.76(6) 94.90(7) 100.21(7) 95.26(6) 84.88(6) 97.39(7) 91.54(6) 101.04(6) 79.18(6) 100.82(6)
2254
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
˚ ) on a Bruker 1 K CCD difKa radiation (k = 0.71073 A fractometer. Data were collected to a maximum 2h value of 57.5 (1.06 < h < 28.76) in 0.3 oscillations (in x) with two 15.0 s exposures (to identify detector anomalies) for a total of 18 121/9185 (Rint = 0.0552) reflections collected. Data were corrected for Lorentz and polarization effects, and no absorption correction was applied [5]. The structure was solved by full-matrix least-squares on F2. All nonhydrogen atoms were refined anisotropically; hydrogen atoms were calculated in the riding mode, and their isotropic temperature factors were refined. Data processing was performed with SAINT [6], and structure solution, refinement and calculation of the derived results were performed with SHELXTL [7]. Neutral atom scattering factors were those of Cromer and Waber [8], and the real and imaginary anomalous dispersion corrections were those of Cromer [9]. Relevant crystallographic data are given in Table 1 and selected bond lengths and angles for the bismuth coordination sphere are given in Table 2. 4. Results and discussion The new complex of bismuth(III) chloride and meimtH shown in Fig. 1 fits, in part, the same general structural pattern observed for BiCl3(dmit)2 [2] with two BiCl4L2 (L = ligand) octahedra sharing a common edge through bridging chlorine atoms. Two major differences appear in the new structure reported here, however. The ligands are cis to each other and occupy the same plane as the bridging chlorine atoms as opposed to being trans and perpendicular to the six atom chlorine plane as observed in the structure of BiCl3(dmit)2. Additionally, there is a separate octahedral BiCl3(meimtH)3 unit tethered to the dimer via ˚ (H8– hydrogen bonding (Fig. 1) at distances of 2.39 A ˚ (H10–Cl3). The octahedral unit shows a Cl3) and 2.33 A meridional (OC-6-21) configuration of ligands similar to that observed for Bi(SCN)3(dmit)3 [10]. Bismuth chlorine bond distances in both the octahedral unit (Fig. 2) and ˚ the dimer (Fig. 3) are similar and range from 2.584(2) A [Bi(1)–Cl(1)] observed in the octahedral unit to the longest ˚ [Bi(2)–Cl(5) and Bi(2A)–Cl(5A)] as bonds of 3.000(2) A expected, since they are involved in bridging within the ˚ dimeric unit. The next longest bond Bi–Cl at 2.876(2) A is the bridging complement [Bi(2)–Cl(5A) or Bi(2A)–
Fig. 1. Structure of BiCl3[meimtH]2.5 Æ H2O showing dimeric unit and octahedral portion with hydrogen bonding signified by dashed lines.
Fig. 2. ORTEP drawing at 50% probability level showing octahedral portion of BiCl3[meimtH]2.5 Æ H2O with one-half occupancy for C(8).
Cl(5)] and happens to be the same length as Bi(1)–Cl(3), the bond involved in hydrogen bonding in the octahedral ˚ [Bi(2)– unit. Bismuth–sulfur bonds range from 2.679(2) A ˚ [Bi(1)–S(3)]. Overall, both Bi–Cl and S(5)] to 2.948(2) A Bi–S bond distances do not deviate significantly from those noted in the literature for similar bismuth(III) chloride thione complexes [1,2,10]. Bond angles in the bismuth coordination sphere show deviation from ideal angles of 90 in both the dimer and the octahedron. The narrowest angle is 76.22(6) [S(1)– Bi(1)–Cl(3)] which also contains one of the chlorine atoms involved in hydrogen bonding to the dimer. The largest angle of 102.01(7) also involves Cl(3) and it is likely that these distortions are due to hydrogen bonding with the dimer. There is no firm evidence for a stereoactive lone pair of electrons in either the octahedron or the dimer. We have
Fig. 3. ORTEP drawing at 50% probability level of dimeric portion of BiCl3[meimtH]2.5 Æ H2O.
D.J. Williams et al. / Inorganica Chimica Acta 359 (2006) 2252–2255
recent by performed density functional theory (DFT) calculations on similar compounds and have discovered a large amount of s character associated with the highest occupied molecular orbitals (HOMO) of bismuth [11]. This is in keeping with many similar findings involving lead(II) complexes [12], and in part can be correlated to the hard– soft acid–base nature of the ligand [12,13]. In soft–soft interactions, the lone pair tends to be stereoinactive [13] or what is termed ‘‘holodirected’’, whereas in hard–hard interactions, the lone pairs were stereoactive or ‘‘hemidirected’’ [12]. Ligand bond distances and angles agree well with literature values [14]. In the case of one of the ligands, there is disorder in the solid state where C8 has 50% occupancy on either one of two ring nitrogens (N3, N4). Solid state 13 C NMR shows good agreement with other chemical shifts published for these types of thione ligands [15,16], but it cannot differentiate between the dimer and the octahedral environment. Particularly sensitive to coordination is the thionyl carbon which is observed at 147.9 ppm for this complex, but is normally seen at 164.2 ppm when not coordinated [16]. 5. Conclusions The title compound provides yet another example of ligand steric bulk influencing the overall structure of a heavy main group halide complex. Whereas smaller compact ligands (L) such as etu allowed for the polymerization of BiCl4L2 octahedra, the dimethyl analog blocked such polymerization to give a dimer only. The intermediate monomethyl ligand gave both the dimer with an altered ligand arrangement and a mer-BiCl3L3 octahedron. Other Bi(III) complexes are currently under investigation with ligands of varying bulk to determine if a structural pattern is present, and to further investigate DFT calculations in relationship to the structure.
2255
Appendix A. Supplementary data CCDC 279926 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.ica.2005.12.074. References [1] L.P. Battaglia, A. Bonamartini Corradi, M. Nardelli, M.E. Vidoni Tani, J. Chem. Soc., Dalton Trans. (1978) 583. [2] D.J. Williams, B. Rubin, J. Epstein, W.K. Dean, A. Viehbeck, Cryst. Struct. Commun. 11 (1982) 1. [3] D.J. Williams, D. VanDerveer, B.R. Crouse, R.R. Raye, T. Carter, K.S. Hagen, M. Brewer, Main Group Chem. 2 (1997) 61. [4] P.D Boyle, S.M. Godfrey, J. Chem. Soc., Dalton Trans. (2000) 1959. [5] SADABS R.H. Blessing, Acta Crystallogr. A51 (1995) 33. [6] SMART 5.054, SAINT 6.01, SHELXTL 5.1, Bruker AXS, Madison, WI, USA, 1998–1999. [7] G.M. Sheldrick, SHELXTL: Crystallographic Computing System, Version 5.1, Bruker Analytical X-ray Systems, Madison, WI, 1997. [8] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, vol. C, Kluwer Academic Publishers, Dordrecht, 1992, pp. 500–502, Table 6.1.1.4. [9] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, vol. C, Kluwer Academic Publishers, Dordrecht, 1992, pp. 219–222, Table 4.2.6.8. [10] D.J Williams, T. Carter, K.L. Fahn, D. VanDerveer, Inorg. Chim. Acta 228 (1995) 69. [11] J.J. Concepcion, D.J. Williams, Unpublished results. [12] L. Shimoni-Livny, J.P. Glusker, C.W. Bock, Inorg. Chem. 37 (1998) 1853. [13] K.J. Wynne, J. Chem. Ed. 50 (1973) 328. [14] J.S. Casas, E. Garcia Martinez, A. Sanchez Gonzales, J. Sordo, U. Casellato, R. Graziani, U. Russo, J. Organomet. Chem. 493 (1995) 107. [15] D.J. Williams, V.L.H. Bevilacqua, P.A. Morson, W.T. Pennington, G.L. Schimek, N.T. Kawai, Inorg. Chim. Acta 308 (2000) 129. [16] D.J. Williams, V.L.H. Bevilacqua, P.A. Morson, K.J. Dennison, W.T. Pennington, G.L. Schimek, D. VanDerveer, J.S. Kruger, N.T. Kawai, Inorg. Chim. Acta 285 (1999) 217.