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BY-NC-ND 3.0 license Open Access Published by De Gruyter September 11, 2017

The crystal structures of two 2-methoxycarbonylethyltin trichloride adducts

  • Minghui Guo , Yichao Lin , Yanze Yao and Laijin Tian EMAIL logo

Abstract

The crystal structures of two adducts of 2-methoxycarbonylethyltin trichloride with hexamethylphosphoryltriamide (HMPA) and 1,10-phenanthroline (phen), CH3OCOCH2CH2SnCl3·L (L=HMPA, 1; L=phen, 2), have been determined. The tin atom in 1 is six-coordinated and adopts a distorted [CSnCl3O2] octahedral geometry involving an oxygen atom of HMPA and an oxygen atom of intramolecularly coordinating carbonyl group (Sn-O 2.462(2) Å). The tin atom in 2 is also six-coordinated and possesses a distorted [CSnCl3N2] octahedral geometry with two nitrogen atoms of a chelating phenanthrolin. The carbonyl oxygen atom does not coordinate to the tin center (Sn···O 4.985(2) Å).

Introduction

2-Alkoxycarbonylethyltin trichloride, ROCOCH2CH2SnCl3, a class of monoorganotin compounds containing a functional group, has received considerable attention owing to the variety of coordination geometries of the tin atom (Hutton et al., 1978; Harrison et al., 1979; Howie et al., 1986; Tian et al., 2005; de Lima et al., 2009; Liu et al., 2015). In the solid state and solution, the ROCOCH2CH2 unit is a C,O-chelating ligand by the intramolecular coordination of the carbonyl oxygen atom to the tin center. However, the coordination can be broken and replaced by other N and O donors such as dialkylsulfoxide, hexamethylphosphoryltriamide (HMPA), 2,2-bipyridine, 1,10-phenanthrolin (phen), etc. (Maughan et al., 1981; Fu et al., 1990; Tian et al., 1998, 2016a). The crystal structures of the adducts of 2-alkoxycarbonylethyltin trichloride with monodentate Lewis base ligands, such as CH2=CHCH2OCOCH2CH2SnCl3·OPPh3 (Gielen et al., 1993), CH3CH2OCOCH2CH2SnCl3·OS(C4H9-n)2 (Tian et al., 1998), and CH3CH2CH2OCOCH2CH2SnCl3·OS(CH2Ph)2 (Tian et al., 2001), have been determined, but the adducts with bidentate Lewis base ligands have not been reported in the literature. In order to expand the structural chemistry of 2-alkoxycarbonylethyltin trichloride and compare the coordination strength of the chelating ligands ROCOCH2CH2 and phen to the tin atom, we determined the crystal structures of 1:1 adducts of 2-methoxycarbonylethyltin trichloride with HMPA and phen, CH3OCOCH2CH2SnCl3·L (L=HMPA, 1; L=phen, 2).

Results and discussion

The molecular structures of adducts 1 and 2 are shown in Figures 1 and 2, respectively, and selected bond lengths and angles are given in Table 1. Adduct 1 crystallizes in the space group Pbcn. The Sn center is six-coordinated with coordinating atoms C(1), Cl(1), Cl(2), Cl(3), O(1), and O(2) and possesses a distorted octahedral geometry with one octahedral face defined by three chlorine atoms. The O(2)-Sn(1)-Cl(1), C(1)-Sn(1)-Cl(2), and O(1)-Sn(1)-Cl(3) bond angles are 174.70(7), 157.5(8), and 171.18(7)°, respectively. A five-membered chelate ring with a narrow bite angle C(1)-Sn(1)-O(2) (74.8(8)°) was formed by the intramolecular coordination of the carbonyl O(2) atom to the Sn(1) atom. The Sn(1)-O(2) separation of 2.462(2) Å is obviously longer than the 2.347(5) Å reported for CH3OCOCH2CH2SnCl3 (Harrison et al., 1979; de Lima et al., 2009) and Sn(1)-O(1) (2.142(2) Å), which indicates that the additional intermolecular P=O→Sn coordination weakens the intramolecular C=O→Sn coordination and confirms the weak nature of the Sn(1)-O(2) interaction. Thus, when HMPA/CH3OCOCH2CH2SnCl3 is beyond a 1:1 molar ratio, the intramolecular coordination Sn(1)-O(2) is replaced by the oxygen atom of HMPA and the 1:2 addition complex is formed (Fu et al., 1990). The three Sn-Cl distances are significantly different, ranging between 2.3422(11) (Sn(1)-Cl(2)) and 2.4529(14) Å (Sn(1)-Cl(3)). Adduct 1 exists as a discrete molecule, and there are only very weak intermolecular interactions C(2)-H(2A)···Cl(3)#1 (symmetry code #1: x, 1−y, 1/2+z) (C(2)···Cl(3)#1 3.659(15) Å, C(2)-H(2A)···Cl(3)#1 146.3(9)°) and C(10)-H(10B)···Cl(2)#2 (symmetry code #2: x, −y, 1/2+z) (C(10)···Cl(2)#2 3.527(8) Å, C(10)-H(10B)···Cl(2)#2 131.7(5)°). These structural features of 1 are similar to those reported for CH2=CHCH2OCOCH2CH2SnCl3·OPPh3 (Gielen et al., 1993) and CH3CH2CH2OCOCH2CH2SnCl3·OS(CH2Ph)2 (Tian et al., 2001).

Figure 1: The molecular structure of 1.Anisotropic ellipsoids are represented at a 30% probability level.
Figure 1:

The molecular structure of 1.

Anisotropic ellipsoids are represented at a 30% probability level.

Figure 2: The molecular structure of 2·0.5C6H6.Anisotropic ellipsoids are represented at a 30% probability level. The benzene solvate molecule has been omitted for clarity.
Figure 2:

The molecular structure of 2·0.5C6H6.

Anisotropic ellipsoids are represented at a 30% probability level. The benzene solvate molecule has been omitted for clarity.

Table 1:

Selected bond lengths (Å) and angles (°) for 1 and 2·0.5C6H6.

1
Sn(1)-O(1)2.142(2)Sn(1)-Cl(1)2.3709(10)C(3)-O(2)1.194(4)
Sn(1)-O(2)2.462(2)Sn(1)-Cl(2)2.3422(12)C(3)-O(3)1.310(4)
Sn(1)-C(1)2.123(9)Sn(1)-Cl(3)2.4529(14)P(1)-O(1)1.496(3)
C(1)-Sn(1)-O(1)92.3(4)Cl(2)-Sn(1)-Cl(1)99.76(5)C(1)-Sn(1)-O(2)74.8(8)
C(1)-Sn(1)-Cl(2)157.5(8)C(1)-Sn(1)-Cl(3)90.6(4)O(1)-Sn(1)-O(2)84.49(9)
O(1)-Sn(1)-Cl(2)84.98(7)O(1)-Sn(1)-Cl(3)171.18(7)Cl(2)-Sn(1)-O(2)82.66(7)
C(1)-Sn(1)-Cl(1)102.6(8)Cl(2)-Sn(1)-Cl(3)89.22(6)Cl(1)-Sn(1)-O(2)174.70(7)
O(1)-Sn(1)-Cl(1)91.00(7)Cl(1)-Sn(1)-Cl(3)96.53(5)Cl(3)-Sn(1)-O(2)88.19(7)
2
Sn(1)-C(13)2.145(3)Sn(1)-Cl(1)2.4204(8)C(15)-O(1)1.223(19)
Sn(1)-N(1)2.259(2)Sn(1)-Cl(2)2.4397(9)C(15)-O(2)1.300(4)
Sn(1)-N(2)2.270(2)Sn(1)-Cl(3)2.4413(9)
C(13)-Sn(1)-N(1)95.92(12)N(2)-Sn(1)-Cl(1)89.10(6)C(13)-Sn(1)-Cl(3)97.03(11)
C(13)-Sn(1)-N(2)168.23(11)C(13)-Sn(1)-Cl(2)94.20(11)N(1)-Sn(1)-Cl(3)87.15(6)
N(1)-Sn(1)-N(2)72.76(9)N(1)-Sn(1)-Cl(2)86.70(6)N(2)-Sn(1)-Cl(3)85.86(7)
C(13)-Sn(1)-Cl(1)102.19(9)N(2)-Sn(1)-Cl(2)82.14(7)Cl(1)-Sn(1)-Cl(3)91.55(3)
N(1)-Sn(1)-Cl(1)161.87(6)Cl(1)-Sn(1)-Cl(2)90.99(3)Cl(2)-Sn(1)-Cl(3)167.69(4)

Adduct 2, as its benzene solvate 2·0.5C6H6, crystallizes in the monoclinic space group C2/c. The central Sn atom exists in a distorted octahedral geometry defined by a C atom of the methoxycarbonylethyl group, three Cl atoms, and the two N atoms from a chelating phen ligand with the C(13)-Sn(1)-N(2), N(1)-Sn(1)-Cl(1), and Cl(2)-Sn(1)-Cl(3) angles of 168.23(11), 161.87(6), and 167.69(4)°, respectively. The distortions from the ideal geometry may be rationalized by the restricted bite angle N(1)-Sn(1)-N(2) (72.76(9)°) of the chelate ligand (Tian et al., 2016b). The five-membered chelate ring formed by the intramolecular C=O→Sn coordination in CH3OCOCH2CH2SnCl3 (Harrison et al., 1979) has been broken, and the carbonyl oxygen atom does not coordinate to the tin center (Sn(1)···O(1) 4.985(2) Å). The new five-membered chelate ring consisting of N(1), Sn(1), N(2), C(5), and C(6) is essentially planar with a maximum deviation from the mean plane of 0.043(3) Å for the Sn(1) atom. The Sn(1)-N(1) distance (2.259(2) Å) involving the N(l) atom trans to the Cl(1) atom is slightly shorter than the Sn(1)-N(2) distance (2.270(2) Å) involving the N(2) atom trans to the methoxycarbonylethyl group. The dimensions of six bonds surrounding the Sn(1) atom are similar to those found in a closely related adduct, C6H5CH2SnCl3·phen (Hall and Tiekink, 1996). However, an arrangement of the Cl3N2C donor atoms is not different, and in the structure of C6H5CH2SnCl3·phen, the tin-bound organic substituent is trans to a chlorine atom. In the lattice, there is a benzene solvent molecule of crystallization which does not interact significantly with the adduct molecule. In 2·0.5C6H6, there is no major intermolecular contacts and only two weak interactions, C(1)-H(1)···Cl(2)#1 (symmetry code #1: x, −y, 1/2+z) (C(1)···Cl(2)#1 3.528(5) Å, C(1)-H(1)···Cl(2)#1 138.9(2)°) and C(2)-H(2)···O(1)#2 (symmetry code #2: −x, −y, 1−z) (C(2)···O(1)#2 3.185(10) Å, C(2)-H(2)···O(1)#2 142.6(2)°).

In summary, the tin centers in adducts 1 and 2·0.5C6H6 both have distorted octahedral geometry. The intramolecular C=O→Sn coordination still exists in 1 (Sn-O 2.462(2) Å), but in 2·0.5C6H6 it has been replaced by the chelating phenanthrolin ligand, resulting in an Sn···O distance of 4.985(2) Å.

Experimental section

2-Methoxycarbonylethyltin trichloride and its adducts with HMPA and phen were prepared according to the reported methods, respectively (Hutton et al., 1978; Maughan et al., 1981; Fu et al., 1990). The colorless single crystals were obtained from benzene by slow evaporation at room temperature. The intensity data for crystals of the adducts were measured at 295(2) K on a Bruker Smart Apex area detector (Bruker AXS Inc., Madison, WI, USA) fitted with graphite monochromatized Mo- radiation (0.71073 Å) using the φ and ω scan technique. Empirical corrections for absorption effects were made using the SADABS program (Sheldrick, 2002). The structures were solved by the direct method and refined by a full-matrix least squares procedure based on F2 using the SHELXL-97 (Sheldrick, 2008). The non-hydrogen atoms were refined anisotropically, and hydrogen atoms were placed at calculated positions (C-H=0.93 Å for aromatic H atoms, C-H=0.96 Å for methyl H atoms, and C-H=0.97 Å for methylene H atoms) and were included in the refinement in the riding model approximation. In 1, the C(1) and C(2) atoms were disordered over two conformations. The site occupancies were refined to 0.616(19):0.384(19). In 2·0.5C6H6, the occupancies of O(1) and O(1)′ were refined to 0.53(2):0.47(2). Six carbon atoms of the solvent benzene were restricted in the same plane, and the C-C bond and 1,3 distance were restricted to 1.39(1) and 2.40(2) Å, respectively. The crystallographic parameters and refinements are summarized in Table 2. Crystallographic data have been deposited in the Cambridge Crystallographic Data Centre (supplementary publication numbers CCDC 1549827 and 1549828).

Table 2:

Crystallographic data and structure refinements of 1 and 2·0.5C6H6.

12·0.5C6H6
Empirical formulaC10H25Cl3N3O3PSnC19H18Cl3N2O2Sn
Formula weight491.34531.39
Crystal systemOrthorhombicMonoclinic
Temperature/K295(2)295(2)
Space groupPbcnC2/c
a/(Å)26.0386(8)20.0417(14)
b/(Å)10.6996(10)18.6369(13)
c/(Å)14.4302(19)13.3203(9)
β/(°)90124.170(1)
Volume/Å34020.3(7)4116.5(5)
Z88
Dc/(g·cm−3)1.6241.715
μ/mm−11.7591.648
F(000)19682104
θ range (°)1.6–26.01.9−26.0
Crystal size (mm)0.45×0.26×0.200.35×0.17×0.17
Tot. reflections29 52315 779
Uniq. reflections, Rint3948, 0.0354037, 0.020
Reflections with I>2σ(I)31373413
GOF on F21.031.03
R1, wR2 [I>2σ(I)]0.034, 0.0770.029, 0.074
R1, wR2 (all data)0.047, 0.0850.036, 0.081
Δρmin, Δρmax/(e·Å−3)−0.75, 0.52−0.69, 0.59

Acknowledgments

This work was supported by the Experimental Teaching Reform Project of Qufu Normal University (sj2016) and Shandong Provincial Natural Science Foundation, China (ZR2013BM007).

References

de Lima, G. M.; Milne, B. F.; Pereira, R. P.; Rocco, A. M.; Skakle, J. M. S.; Travis, A. J.; Wardell, J. L.; Wardell, S. M. S. V. Experimental and ab initio structural study of estertin compounds, X3SnCH2CH2CO2Me: crystal structures of Cl3SnCH2CH2CO2Me at 120 K and Br3SnCH2CH2CO2Me at 120 and 291 K. J. Mol. Struct.2009, 921, 244–250.10.1016/j.molstruc.2008.12.064Search in Google Scholar

Fu, F.; Tian, L.; Pan, H.; Willem, R.; Gielen, M. Synthesis and characterization of DMSO and HMPA adducts of R′OCOCHRCH2SnCl3. Bull. Soc. Chim. Belg.1990, 99, 789–796.10.1002/bscb.19900991005Search in Google Scholar

Gielen, M.; Pan, H.; Tiekink, E. R. T. Crystal structures of CH2=CHCH2OCOCH2– CH2SnCl3·O=PPh3 and BuOCOCH(CH3)CH2SnCl3·O=PPh3. Bull. Soc. Chim. Belg.1993, 102, 447–453.10.1002/bscb.19931020703Search in Google Scholar

Hall, V. J.; Tiekink, E. R. T. Benzyltriehloro(1,10-phenanthroline-N,N′)tin(IV) benzene solvate. Acta Crystallogr. C1996, 52, 2141–2143.10.1107/S0108270195009334Search in Google Scholar

Harrison, P. G.; King, T. J.; Healy, M. A. Structural studies in main group chemistry: XXIII. Estertin derivatives, structural and spectroscopic studies. J. Organometal. Chem.1979, 182, 17–36.10.1016/S0022-328X(00)85873-8Search in Google Scholar

Howie, R. A.; Paterson, E. S.; Wardell, J. L.; Burley, J. W. Further study of estertin trichlorides, Cl3SnCH2CH2CO2R, Lewis acidity towards acetonitrile. Crystal structure of Cl3SnCH2CH2CO2Pr-i.J. Organomet. Chem.1986, 304, 301–308.10.1016/0022-328X(86)80148-6Search in Google Scholar

Hutton, R. E.; Burley, J. W.; Oakes, V. β-Substituted alkyltin halides: I. Monoalkyltin trihalides: synthetic, mechanistic and spectroscopic aspects. J. Organometal. Chem.1978, 156, 369–382.10.1016/S0022-328X(00)93543-5Search in Google Scholar

Liu, Q.; Shi, X.; Zhang, C.; Tian, L. Synthesis and structure of [2-((L)-menthoxycarbonyl)ethyl]diphenyltin halides. Main Group Met. Chem.2015, 38, 93–97.10.1515/mgmc-2015-0020Search in Google Scholar

Maughan, D.; Wardell, J. L.; Burley, J. W. Lewis acidity of carboxyethyltin chlorides, Cl3SnCH2CH2CO2R and Cl2Sn(CH2CH2CO2R)2. J. Organomet. Chem.1981, 212, 59–70.10.1016/S0022-328X(00)85526-6Search in Google Scholar

Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction of Area Detector Data, Bruker AXS Inc., Madison, Wisconsin, USA, 2002.Search in Google Scholar

Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A2008, 64, 112–122.10.1107/S0108767307043930Search in Google Scholar PubMed

Tian, L.; Zhou, Z.; Zhao, B.; Yu W. Synthesis and characterization of β-alkoxycarbonylethyltin trichloride complexes with dibutylsulfoxide. Crystal structure of CH3CH2OCOCH2CH2SnCl3·(n-C4H9)2SO. Polyhedron1998, 17, 1275–1279.10.1016/S0277-5387(97)00378-1Search in Google Scholar

Tian, L.; Zhao, B.; Li, F. Synthesis, crystal structure and transesterification reaction of the β-propoxycarbonylethyltin trichloride complexes with dibenzylsulfoxide. Synth. React. Inorg. Met.-Org. Chem.2001, 31, 139–148.10.1081/SIM-100001939Search in Google Scholar

Tian, L.-J.; Sun, Y.-X.; Liu, X.-J.; Yang, G.-M.; Shang, Z.-C. Synthesis and structural characterization of 2-(-)-menthoxycarbonylethyltin compounds. Polyhredron2005, 24, 2027–2034.10.1016/j.poly.2005.05.025Search in Google Scholar

Tian, L.; Zhang, S.; Yao, Y.; Shi X. Synthesis and crystal structure of [2-(menthoxycarbonyl)ethyl]tris(8-quinolinato)tin. Main Group Met. Chem.2016a, 39, 209–212.10.1515/mgmc-2016-0030Search in Google Scholar

Tian, L.-J.; Yao, Y.-Z.; Liu, Q.-T.; Zheng, X.-F. Synthesis, characterization and antibacterial activity of cyclohexyltin complexes of N-(3,5-dibromosalicylidene)valine. Chin. J. Struct. Chem.2016b, 35, 849–856.Search in Google Scholar

Received: 2017-6-7
Accepted: 2017-8-14
Published Online: 2017-9-11
Published in Print: 2017-8-28

©2017 Walter de Gruyter GmbH, Berlin/Boston

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