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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): m721.
Published online 2008 April 26. doi:  10.1107/S1600536808011070
PMCID: PMC2961118

Aqua­chloridodimethyl­phenyltin(IV)–15-crown-5 (2/1)

Abstract

The SnIV atom in the title compound, 2[Sn(CH3)2(C6H5)Cl(H2O)]·C10H20O5, exists in a trans-C3SnClO trigonal bipyramidal geometry in which the organo substituents occupy the equatorial sites. The coordinated water mol­ecule forms two hydrogen bonds to the 15-crown-5 mol­ecule, which is disordered about a center of inversion.

Related literature

For ‘outer-sphere coordination’ organotin complexes with 15-crown-5, see: Amini et al. (1994 [triangle]); Chee et al. (2003 [triangle]); Yap et al. (1996 [triangle]). For the refinement of 15-crown-5 type crystal structures that are disordered about a center of inversion, see: Ng (2005 [triangle]). For the analogous adduct of SnCl(CH3)2(C6H5)(H2O) with 18-crown-6, see: Amini et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m721-scheme1.jpg

Experimental

Crystal data

  • 2[Sn(CH3)2(C6H5)Cl(H2O)]·C10H20O5
  • M r = 778.91
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m721-efi1.jpg
  • a = 9.8700 (3) Å
  • b = 18.9814 (5) Å
  • c = 9.8770 (3) Å
  • β = 113.636 (1)°
  • V = 1695.2 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.67 mm−1
  • T = 295 (2) K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.534, T max = 0.732
  • 16379 measured reflections
  • 3869 independent reflections
  • 3433 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.128
  • S = 1.06
  • 3869 reflections
  • 159 parameters
  • 30 restraints
  • H-atom parameters constrained
  • Δρmax = 1.29 e Å−3
  • Δρmin = −1.14 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011070/tk2247sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011070/tk2247Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Shahid Beheshti University, Heilongjiang University and the University of Malaya for supporting this work.

supplementary crystallographic information

Comment

Water-coordinated triorganotin salts form "outer-sphere coordination" complexes with crown ethers. In these, the water molecules interact with the crown ether through hydrogen bonds (Amini et al., 1994; Chee et al., 2003; Yap et al., 1996). The refinement of such crystal structures present special difficulties when the odd-numbered crown ether is disordered about a center of inversion. The refinement of such crystal structures has been described in detail (Ng, 2005). The mixed-organo SnIV title compound, (I), has the tin atom in a trans-C3SnClO trigonal bipyramidal geometry, Fig. 1 & Table 1, in which the electronegative substituents occupy the axial sites. The coordinated water molecule forms two hydrogen bonds to the 15-crown-5, which is disordered about a center-of-inversion; Table 2.

Experimental

ChlorodimethylphenylSnIV was synthesized by the cleavage of dimethyldiphenyltin with hydrogen chloride in a methanol/carbon tetrachloride mixture at 283 K and was purified by distillation at 363 K/1 Torr. ChlorodimethylphenylSnIV (0.26 g, 1 mmol) and 15-crown-5 (0.22 g, 1 mmol) were dissolved in ethanol (20 ml). The co-crystal (I), m.p. 347–349 K, separated when the solvent was allowed to evaporate. 1H-NMR in CDCl3: 0.90 (CH3), 1.60 (H2O), 3.72 (CH2), 7.27–7.70 (C6H5) p.p.m. 119Sn NMR 115.7 p.p.m. 2J(119Sn–1H) = 60 Hz.

Refinement

The 15-crown-5 lies about a center of inversion and the molecule was refined as a 15-atom species of half site-occupancy. All 1,2-related atoms were restrained to 1.45±0.01 Å and 1,3-related atoms to 2.35±0.01 Å. The displacement factors of the O atoms were restrained to be equal, as were those of the C atoms.

The carbon-bound H atoms were placed in calculated positions with C–H 0.93 to 0.97 Å, and with Uiso(H) 1.2–1.5Ueq(C), and were included in the refinement in the riding-model approximation. The water H-atoms were placed in chemically sensible positions on the basis of hydrogen bonds but were not refined [O–H 0.82 Å and Uiso(H) 1.5Ueq(O)].

The final difference Fourier map had a relatively large peak/deep hole in the vicinity of the crown ether.

Figures

Fig. 1.
Molecular structure of (I); ellipsoids are drawn at the 30% probability level, and H atoms as spheres of arbitrary radius. The 15-crown-5 is disordered about a center of inversion, only one orientation is shown for reasons of clarity. Dashed lines denote ...

Crystal data

2[Sn(CH3)2(C6H5)Cl(H2O)]·C10H20O5F000 = 784
Mr = 778.91Dx = 1.526 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 13887 reflections
a = 9.8700 (3) Åθ = 3.1–27.4º
b = 18.9814 (5) ŵ = 1.67 mm1
c = 9.8770 (3) ÅT = 295 (2) K
β = 113.636 (1)ºBlock, colorless
V = 1695.2 (1) Å30.30 × 0.25 × 0.20 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer3869 independent reflections
Radiation source: fine-focus sealed tube3433 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
Detector resolution: 10.0 pixels mm-1θmax = 27.4º
T = 295(2) Kθmin = 3.1º
ω scansh = −10→12
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)k = −24→24
Tmin = 0.534, Tmax = 0.732l = −12→12
16379 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.128  w = 1/[σ2(Fo2) + (0.0816P)2 + 1.7228P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3869 reflectionsΔρmax = 1.29 e Å3
159 parametersΔρmin = −1.14 e Å3
30 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Sn10.55993 (3)0.385283 (13)0.73184 (3)0.04272 (13)
Cl10.31360 (13)0.32890 (8)0.60646 (14)0.0700 (3)
O1w0.7986 (3)0.44517 (17)0.8682 (4)0.0634 (8)
H1w0.79200.48660.84310.095*
H2w0.86360.42600.84950.095*
C10.6070 (6)0.3380 (3)0.9397 (6)0.0719 (14)
H1A0.64380.37301.01590.108*
H1B0.68020.30190.95710.108*
H1C0.51840.31750.94060.108*
C20.4774 (6)0.4899 (3)0.6902 (7)0.0696 (13)
H2A0.55120.52020.68130.104*
H2B0.45370.50560.77040.104*
H2C0.39010.49100.60000.104*
C30.6535 (4)0.34520 (18)0.5860 (4)0.0448 (8)
C40.5616 (6)0.3317 (2)0.4393 (5)0.0584 (10)
H40.45990.33740.40720.070*
C50.6219 (7)0.3095 (3)0.3396 (6)0.0741 (14)
H50.55920.29990.24220.089*
C60.7687 (7)0.3019 (3)0.3827 (6)0.0749 (14)
H60.80730.28810.31500.090*
C70.8608 (6)0.3144 (3)0.5261 (7)0.0719 (13)
H70.96230.30870.55630.086*
C80.8038 (5)0.3356 (3)0.6281 (5)0.0602 (11)
H80.86780.34350.72590.072*
O10.8394 (11)0.5945 (5)0.8704 (10)0.0982 (12)0.50
O21.0758 (10)0.5345 (4)0.8227 (10)0.0982 (12)0.50
O31.0975 (10)0.4055 (5)0.9549 (9)0.0982 (12)0.50
O41.1086 (10)0.4378 (5)1.2332 (10)0.0982 (12)0.50
O50.9190 (10)0.5479 (5)1.1592 (10)0.0982 (12)0.50
C90.9218 (17)0.6312 (6)0.8003 (17)0.0922 (11)0.50
H9A0.85970.66610.73170.111*0.50
H9B1.00620.65500.87390.111*0.50
C100.9708 (14)0.5796 (6)0.7224 (12)0.0922 (11)0.50
H10A0.88690.55230.65740.111*0.50
H10B1.01400.60340.66220.111*0.50
C111.1043 (16)0.4717 (5)0.7580 (12)0.0922 (11)0.50
H11A1.15980.48290.69900.111*0.50
H11B1.01180.44980.69430.111*0.50
C121.1889 (15)0.4240 (7)0.8775 (15)0.0922 (11)0.50
H12A1.21590.38210.83790.111*0.50
H12B1.27880.44690.94430.111*0.50
C131.1716 (15)0.3633 (6)1.0805 (11)0.0922 (11)0.50
H13A1.27270.37971.13040.111*0.50
H13B1.17440.31501.04970.111*0.50
C141.1003 (19)0.3657 (6)1.1805 (15)0.0922 (11)0.50
H14A1.14920.33401.26290.111*0.50
H14B0.99780.35121.13080.111*0.50
C151.0198 (14)0.4487 (6)1.3105 (12)0.0922 (11)0.50
H15A0.97830.40361.32000.111*0.50
H15B1.08310.46411.40940.111*0.50
C160.9041 (13)0.4965 (6)1.2534 (15)0.0922 (11)0.50
H16A0.89250.51991.33530.111*0.50
H16B0.81380.47041.19990.111*0.50
C170.7917 (15)0.5900 (8)1.0850 (13)0.0922 (11)0.50
H17A0.77200.61891.15610.111*0.50
H17B0.70660.55991.03570.111*0.50
C180.8149 (16)0.6343 (6)0.9783 (12)0.0922 (11)0.50
H18A0.72890.66410.93080.111*0.50
H18B0.89950.66451.02830.111*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.04543 (19)0.04251 (18)0.03998 (18)−0.00211 (9)0.01686 (13)0.00193 (8)
Cl10.0538 (6)0.0880 (8)0.0622 (7)−0.0244 (6)0.0171 (5)−0.0039 (6)
O1w0.0542 (16)0.0637 (18)0.068 (2)−0.0146 (14)0.0198 (14)−0.0190 (15)
C10.072 (3)0.082 (3)0.052 (3)−0.010 (3)0.015 (2)0.019 (2)
C20.067 (3)0.053 (2)0.087 (4)0.007 (2)0.029 (3)0.007 (2)
C30.0526 (19)0.0369 (16)0.0439 (19)−0.0036 (15)0.0183 (16)0.0006 (14)
C40.066 (3)0.062 (2)0.041 (2)0.004 (2)0.0158 (18)−0.0013 (17)
C50.097 (4)0.076 (3)0.049 (3)0.005 (3)0.028 (3)−0.006 (2)
C60.110 (4)0.061 (3)0.074 (3)0.003 (3)0.058 (3)−0.008 (2)
C70.071 (3)0.071 (3)0.086 (4)0.006 (2)0.044 (3)−0.006 (3)
C80.058 (2)0.069 (3)0.055 (2)−0.006 (2)0.024 (2)−0.013 (2)
O10.094 (3)0.106 (3)0.088 (3)0.004 (3)0.031 (2)0.003 (2)
O20.094 (3)0.106 (3)0.088 (3)0.004 (3)0.031 (2)0.003 (2)
O30.094 (3)0.106 (3)0.088 (3)0.004 (3)0.031 (2)0.003 (2)
O40.094 (3)0.106 (3)0.088 (3)0.004 (3)0.031 (2)0.003 (2)
O50.094 (3)0.106 (3)0.088 (3)0.004 (3)0.031 (2)0.003 (2)
C90.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C100.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C110.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C120.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C130.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C140.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C150.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C160.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C170.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)
C180.092 (2)0.104 (3)0.090 (3)0.007 (2)0.046 (2)−0.005 (2)

Geometric parameters (Å, °)

Sn1—C12.115 (5)O4—C151.389 (8)
Sn1—C22.122 (5)O4—C141.454 (9)
Sn1—C32.139 (4)O5—C161.397 (8)
Sn1—O1w2.472 (3)O5—C171.420 (9)
Sn1—Cl12.485 (1)C9—C101.442 (9)
O1w—H1w0.8200C9—H9A0.9700
O1w—H2w0.8200C9—H9B0.9700
C1—H1A0.9600C10—H10A0.9700
C1—H1B0.9600C10—H10B0.9700
C1—H1C0.9600C11—C121.455 (9)
C2—H2A0.9600C11—H11A0.9700
C2—H2B0.9600C11—H11B0.9700
C2—H2C0.9600C12—H12A0.9700
C3—C81.383 (6)C12—H12B0.9700
C3—C41.390 (6)C13—C141.425 (8)
C4—C51.404 (7)C13—H13A0.9700
C4—H40.9300C13—H13B0.9700
C5—C61.345 (8)C14—H14A0.9700
C5—H50.9300C14—H14B0.9700
C6—C71.362 (8)C15—C161.388 (8)
C6—H60.9300C15—H15A0.9700
C7—C81.396 (7)C15—H15B0.9700
C7—H70.9300C16—H16A0.9700
C8—H80.9300C16—H16B0.9700
O1—C181.404 (9)C17—C181.437 (8)
O1—C91.442 (9)C17—H17A0.9700
O2—C101.402 (8)C17—H17B0.9700
O2—C111.433 (9)C18—H18A0.9700
O3—C131.410 (9)C18—H18B0.9700
O3—C121.441 (9)
C1—Sn1—C2120.2 (2)O2—C10—C9110.4 (8)
C1—Sn1—C3121.1 (2)O2—C10—H10A109.6
C2—Sn1—C3116.0 (2)C9—C10—H10A109.6
C1—Sn1—O1w82.9 (2)O2—C10—H10B109.6
C2—Sn1—O1w83.3 (2)C9—C10—H10B109.6
C3—Sn1—O1w87.5 (1)H10A—C10—H10B108.1
C1—Sn1—Cl195.2 (2)O2—C11—C12107.9 (8)
C2—Sn1—Cl194.8 (2)O2—C11—H11A110.1
C3—Sn1—Cl196.4 (1)C12—C11—H11A110.1
O1w—Sn1—Cl1176.1 (1)O2—C11—H11B110.1
Sn1—O1w—H1w109.5C12—C11—H11B110.1
Sn1—O1w—H2w109.5H11A—C11—H11B108.4
H1w—O1w—H2w109.5O3—C12—C11107.7 (8)
Sn1—C1—H1A109.5O3—C12—H12A110.2
Sn1—C1—H1B109.5C11—C12—H12A110.2
H1A—C1—H1B109.5O3—C12—H12B110.2
Sn1—C1—H1C109.5C11—C12—H12B110.2
H1A—C1—H1C109.5H12A—C12—H12B108.5
H1B—C1—H1C109.5O3—C13—C14111.5 (8)
Sn1—C2—H2A109.5O3—C13—H13A109.3
Sn1—C2—H2B109.5C14—C13—H13A109.3
H2A—C2—H2B109.5O3—C13—H13B109.3
Sn1—C2—H2C109.5C14—C13—H13B109.3
H2A—C2—H2C109.5H13A—C13—H13B108.0
H2B—C2—H2C109.5C13—C14—O4107.7 (8)
C8—C3—C4117.5 (4)C13—C14—H14A110.2
C8—C3—Sn1123.0 (3)O4—C14—H14A110.2
C4—C3—Sn1119.3 (3)C13—C14—H14B110.2
C3—C4—C5120.2 (5)O4—C14—H14B110.2
C3—C4—H4119.9H14A—C14—H14B108.5
C5—C4—H4119.9C16—C15—O4118.2 (8)
C6—C5—C4121.1 (5)C16—C15—H15A107.8
C6—C5—H5119.5O4—C15—H15A107.8
C4—C5—H5119.5C16—C15—H15B107.8
C5—C6—C7119.7 (5)O4—C15—H15B107.8
C5—C6—H6120.1H15A—C15—H15B107.1
C7—C6—H6120.1C15—C16—O5116.0 (8)
C6—C7—C8120.4 (5)C15—C16—H16A108.3
C6—C7—H7119.8O5—C16—H16A108.3
C8—C7—H7119.8C15—C16—H16B108.3
C3—C8—C7121.0 (5)O5—C16—H16B108.3
C3—C8—H8119.5H16A—C16—H16B107.4
C7—C8—H8119.5O5—C17—C18109.8 (8)
C18—O1—C9114.0 (8)O5—C17—H17A109.7
C10—O2—C11114.5 (8)C18—C17—H17A109.7
C13—O3—C12113.0 (7)O5—C17—H17B109.7
C15—O4—C14112.3 (8)C18—C17—H17B109.7
C16—O5—C17115.4 (8)H17A—C17—H17B108.2
C10—C9—O1107.7 (8)O1—C18—C17111.6 (8)
C10—C9—H9A110.2O1—C18—H18A109.3
O1—C9—H9A110.2C17—C18—H18A109.3
C10—C9—H9B110.2O1—C18—H18B109.3
O1—C9—H9B110.2C17—C18—H18B109.3
H9A—C9—H9B108.5H18A—C18—H18B108.0
C1—Sn1—C3—C8−54.1 (4)C18—O1—C9—C10165.5 (11)
C2—Sn1—C3—C8107.3 (4)C11—O2—C10—C9165.4 (11)
O1w—Sn1—C3—C826.0 (4)O1—C9—C10—O2−67.6 (15)
Cl1—Sn1—C3—C8−154.1 (3)C10—O2—C11—C12−167.9 (11)
C1—Sn1—C3—C4129.8 (3)C13—O3—C12—C11−175.6 (11)
C2—Sn1—C3—C4−68.8 (4)O2—C11—C12—O363.6 (15)
O1w—Sn1—C3—C4−150.1 (3)C12—O3—C13—C14160.1 (12)
Cl1—Sn1—C3—C429.7 (3)O3—C13—C14—O4−63.5 (16)
C8—C3—C4—C5−0.2 (7)C15—O4—C14—C13169.2 (11)
Sn1—C3—C4—C5176.1 (4)C14—O4—C15—C16−117.0 (15)
C3—C4—C5—C6−1.1 (8)O4—C15—C16—O5−24 (2)
C4—C5—C6—C71.4 (9)C17—O5—C16—C15171.3 (13)
C5—C6—C7—C8−0.6 (9)C16—O5—C17—C18−172.7 (12)
C4—C3—C8—C71.1 (7)C9—O1—C18—C17−155.4 (12)
Sn1—C3—C8—C7−175.1 (4)O5—C17—C18—O161.1 (16)
C6—C7—C8—C3−0.7 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H1w···O10.822.092.86 (1)156
O1w—H1w···O4i0.822.052.74 (1)143
O1w—H2w···O30.822.152.82 (1)139
O1w—H2w···O5i0.822.242.91 (1)139

Symmetry codes: (i) −x+2, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2247).

References

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