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Acta Cryst. (2012). E68, m354    [ doi:10.1107/S1600536812008781 ]

Di-[mu]-chlorido-bis[aquachloridodimethyltin(IV)]-1,4,7,10,13-pentaoxacyclopentadecane (1/1)

M. M. Amini and S. W. Ng

Abstract top

The Sn, Cl and water O atoms of the title compound, [Sn2(CH3)4Cl4(H2O)2]·C10H20O5, lie on a special position of 2 site symmetry. The SnIV atom shows cis-C2SnCl2O trigonal-bipyramidal coordination [C-Sn-C = 157.0 (1)°]; however, two [Me2SnCl2(H2O)] units are linked by a tin-chlorine bridge [Sn[leftwards arrow]Cl = 3.247 (1) Å] across a center of inversion, generating a dinuclear species, so that the geometry is better regarded as a mer-C2SnCl3O octahedron. The crown ether interacts through O-H...O hydrogen with the metal atom through the coordinated water molecules in an outer-sphere manner, generating a hydrogen-bonded chain running along [101]. The 15-crown-5 molecule is disordered over the 2/m site.

Comment top

Dimethyltin dichloride in the form of its dihydrate forms a 1:1 co-crystal with 15-crown-5; the adduct belongs to the C2/c space group at room temperature [a 9.313 (2), b 17.266 (3), c 13.525 (3) Å; β 107.37 (2) %]. The SnIV atom lies on a twofold rotation axis, and the O atoms of the crown ether all point away from the middle of the ring so that all Owater···Ocrown ether interactions exceed 3.5 Å (Amini et al., 1994). A later, low-temperature (233 K) study corrected the space group of the room-temperature study to P21/n because dynamic disorder gave rise to ambiguities in identifying atoms (Yap et al., 1996). In fact, the water molecule does interact with the crown ether. We repeated the synthesis and used chloform as solvent for crystallization in a 100 K study to confirm the hydrogen bonding interactions (Amini & Ng, Unpublished results).

We then used the chloroform-crystallized compound, [Me2SnCl2(H2O)2].15-crown-5, in a further recrystalliation from methanol, and we obtained the monoaqua 2:1 adduct (Scheme I). The isolation of the 2:1 adduct is reproducible as a second recrystallization from solvent gave an identical compound, so that attempt represents an example of the influence of solvent in the formation of co-crystals.

In [Me2SnCl2(H2O)]2.15-crown-5, the SnIV atom shows cis-C2SnCl2O trigonal bipyramidal coordination [C–Sn–C 157.0 (1) °]; however, two [Me2SnCl2(H2O)] units are linked by a tin–chlorine bridge [Sn←Cl 3.247 (1) Å] across a center-of-inversion to generate a dinuclear species, so that the geometry is better regarded as a mer-C2SnCl3O octahedron (Fig. 1). The crown ether interacts indirectly with the metal atom through the coordinated water molecules in an outer-sphere manner to generate a hydrogen-bonded chain running along [1 0 1] (Table 1).

Related literature top

For [Me2SnCl2(H2O)2].15-crown-5, see: Amini et al. (1994); Yap et al. (1996).

Experimental top

Dimethyltin dichloride (0.22 g, 1 mmol) and 15-crown-5 (0.24 g, 1 mol) were dissolved in chloroform (20 ml) to give clear solution. Colorless crystals of Me2SnCl2(H2O)2.15-crown-5 were formed within a day (Amini et al., 1994); the identity was confirmed by a low-temperature diffraction study.

The 1:1 adduct was recrystallized from methanol to yield the [Me2SnCl2(H2O)]2.15-crown-5 adduct.

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 0.99 Å, Uiso(H) 1.2 to 1.5Ueq(C)] and were included in the refinement in the riding model approximation.

The water H-atom, whose O atom lies on a twofold rotation axis, was similar treated [O–H 0.84 Å] and its temperature factor s were tied by a factor of 1.5 times.

The 15-crown-5 molecule is disordered over the 2/m site. The ring was refined as a 15-atom species subject to 1,2 related distances being restrained to 1.50±0.01 Å. The temperature factors of the five O atoms were made identical, as were those of the ten C atoms. The anisotropic temperature factors of the sole C and O atoms were restrained to be nearly isotropic.

The crystal when measured with Cu radiation in place of Mo radiation in the expectation of resolving the disorder gave a marginally worse outcome, probably because of absorption difficulties.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [Me2SnCl2(H2O)2]2.15-crown-5 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. Thermal ellipsoid plot (Barbour, 2001) of [Me2SnCl2(H2O)2].15-crown-5 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius (Amini & Ng, Unpublished results).
Di-µ-chlorido-bis[aquachloridodimethyltin(IV)]–1,4,7,10,13- pentaoxacyclopentadecane (1/1) top
Crystal data top
[Sn2(CH3)4Cl4(H2O)2]·C10H20O5F(000) = 688
Mr = 695.61Dx = 1.820 Mg m−3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 5314 reflections
a = 14.2351 (13) Åθ = 2.5–27.5°
b = 11.4115 (5) ŵ = 2.42 mm−1
c = 9.8100 (9) ÅT = 100 K
β = 127.183 (14)°Block, colorless
V = 1269.6 (3) Å30.30 × 0.25 × 0.20 mm
Z = 2
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		1524 independent reflections
Radiation source: SuperNova (Mo) X-ray Source1495 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.016
Detector resolution: 10.4041 pixels mm-1θmax = 27.6°, θmin = 2.5°
ω scanh = −16→18
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)		k = −13→14
Tmin = 0.531, Tmax = 0.644l = −12→12
5824 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.042H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.023P)2 + 2.1038P]
where P = (Fo2 + 2Fc2)/3
1524 reflections(Δ/σ)max = 0.001
93 parametersΔρmax = 0.48 e Å−3
43 restraintsΔρmin = −0.72 e Å−3
Crystal data top
[Sn2(CH3)4Cl4(H2O)2]·C10H20O5V = 1269.6 (3) Å3
Mr = 695.61Z = 2
Monoclinic, C2/mMo Kα radiation
a = 14.2351 (13) ŵ = 2.42 mm−1
b = 11.4115 (5) ÅT = 100 K
c = 9.8100 (9) Å0.30 × 0.25 × 0.20 mm
β = 127.183 (14)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector		1524 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)		1495 reflections with I > 2σ(I)
Tmin = 0.531, Tmax = 0.644Rint = 0.016
5824 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.042Δρmax = 0.48 e Å−3
S = 0.99Δρmin = −0.72 e Å−3
1524 reflectionsAbsolute structure: ?
93 parametersFlack parameter: ?
43 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.655960 (17)0.50000.51206 (2)0.01800 (8)
Cl10.43822 (7)0.50000.25799 (9)0.02629 (17)
Cl20.73232 (8)0.50000.35183 (10)0.02918 (17)
O1W0.8420 (2)0.50000.7676 (3)0.0329 (5)
H10.85120.56050.82320.049*
O10.8868 (4)0.5018 (14)1.0827 (5)0.0187 (5)0.25
O21.0086 (8)0.6816 (7)1.0770 (10)0.0187 (5)0.25
O31.0110 (5)0.6179 (5)0.7954 (7)0.0187 (5)0.25
O41.0459 (5)0.3741 (5)0.8555 (7)0.0187 (5)0.25
O51.0106 (8)0.3021 (7)1.1028 (10)0.0187 (5)0.25
C10.8963 (15)0.6095 (12)1.164 (2)0.0199 (5)0.25
H1A0.96640.60781.28580.024*0.25
H1B0.82550.62151.15950.024*0.25
C20.9075 (17)0.7073 (16)1.072 (3)0.0199 (5)0.25
H2A0.83550.71210.95200.024*0.25
H2B0.91830.78311.12880.024*0.25
C31.0255 (10)0.7633 (8)0.9801 (15)0.0199 (5)0.25
H3A1.07070.83241.05110.024*0.25
H3B0.94820.79040.87740.024*0.25
C41.0921 (13)0.7001 (12)0.928 (2)0.0199 (5)0.25
H4A1.12110.75650.88460.024*0.25
H4B1.16060.65821.02730.024*0.25
C51.0639 (7)0.5468 (6)0.7385 (10)0.0199 (5)0.25
H5A1.11920.59540.73330.024*0.25
H5B1.00170.51820.62150.024*0.25
C61.1287 (7)0.4445 (6)0.8525 (11)0.0199 (5)0.25
H6A1.16400.39780.80880.024*0.25
H6B1.19290.47170.96950.024*0.25
C71.0979 (8)0.2730 (8)0.9620 (13)0.0199 (5)0.25
H7A1.17280.29471.07290.024*0.25
H7B1.11530.21380.90630.024*0.25
C81.0136 (11)0.2234 (7)0.9908 (17)0.0199 (5)0.25
H8A0.93390.21590.88060.024*0.25
H8B1.04020.14471.04360.024*0.25
C90.9022 (14)0.2965 (13)1.084 (3)0.0199 (5)0.25
H9A0.89780.22211.13160.024*0.25
H9B0.83380.30040.96110.024*0.25
C100.9009 (15)0.3995 (12)1.179 (2)0.0199 (5)0.25
H10A0.83460.39261.18610.024*0.25
H10B0.97560.40361.29630.024*0.25
C110.6536 (2)0.68104 (19)0.5528 (3)0.0271 (5)
H110.62020.69400.61440.041*
H120.60530.72150.44230.041*
H130.73430.71180.62060.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.02135 (12)0.01588 (12)0.01478 (11)0.0000.00988 (9)0.000
Cl10.0286 (4)0.0210 (3)0.0177 (3)0.0000.0079 (3)0.000
Cl20.0375 (4)0.0312 (4)0.0283 (4)0.0000.0249 (4)0.000
O1W0.0301 (12)0.0391 (14)0.0182 (11)0.0000.0088 (10)0.000
O10.0216 (11)0.0195 (12)0.0150 (15)−0.0018 (15)0.0111 (11)0.0016 (13)
O20.0216 (11)0.0195 (12)0.0150 (15)−0.0018 (15)0.0111 (11)0.0016 (13)
O30.0216 (11)0.0195 (12)0.0150 (15)−0.0018 (15)0.0111 (11)0.0016 (13)
O40.0216 (11)0.0195 (12)0.0150 (15)−0.0018 (15)0.0111 (11)0.0016 (13)
O50.0216 (11)0.0195 (12)0.0150 (15)−0.0018 (15)0.0111 (11)0.0016 (13)
C10.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C20.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C30.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C40.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C50.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C60.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C70.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C80.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C90.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C100.0250 (10)0.0192 (13)0.0199 (13)−0.0014 (16)0.0159 (9)0.0018 (15)
C110.0345 (12)0.0181 (10)0.0345 (12)−0.0066 (9)0.0239 (11)−0.0058 (9)
Geometric parameters (Å, º) top
Sn1—C112.108 (2)C3—H3A0.9900
Sn1—C11i2.108 (2)C3—H3B0.9900
Sn1—O1W2.296 (2)C4—H4A0.9900
Sn1—Cl22.3912 (8)C4—H4B0.9900
Sn1—Cl12.5459 (10)C5—C61.489 (8)
Sn1—Cl1ii3.2467 (9)C5—H5A0.9900
O1W—H10.8400C5—H5B0.9900
O1—C11.427 (9)C6—H6A0.9900
O1—C101.438 (9)C6—H6B0.9900
O2—C21.440 (10)C7—C81.501 (8)
O2—C31.452 (8)C7—H7A0.9900
O3—C51.430 (7)C7—H7B0.9900
O3—C41.447 (10)C8—H8A0.9900
O4—C71.427 (8)C8—H8B0.9900
O4—C61.442 (7)C9—C101.508 (9)
O5—C81.439 (8)C9—H9A0.9900
O5—C91.439 (9)C9—H9B0.9900
C1—C21.505 (9)C10—H10A0.9900
C1—H1A0.9900C10—H10B0.9900
C1—H1B0.9900C11—H110.9800
C2—H2A0.9900C11—H120.9800
C2—H2B0.9900C11—H130.9800
C3—C41.504 (9)
C11—Sn1—C11i157.00 (13)H4A—C4—H4B108.6
C11—Sn1—O1W86.16 (7)O3—C5—C6112.7 (5)
C11i—Sn1—O1W86.16 (7)O3—C5—H5A109.1
C11—Sn1—Cl2100.96 (6)C6—C5—H5A109.1
C11i—Sn1—Cl2100.96 (6)O3—C5—H5B109.1
O1W—Sn1—Cl292.01 (7)C6—C5—H5B109.1
C11—Sn1—Cl192.07 (7)H5A—C5—H5B107.8
C11i—Sn1—Cl192.07 (7)O4—C6—C5108.0 (6)
O1W—Sn1—Cl1170.83 (7)O4—C6—H6A110.1
Cl2—Sn1—Cl197.16 (3)C5—C6—H6A110.1
C11—Sn1—Cl1ii78.93 (6)O4—C6—H6B110.1
C11i—Sn1—Cl1ii78.93 (6)C5—C6—H6B110.1
O1W—Sn1—Cl1ii85.96 (7)H6A—C6—H6B108.4
Cl2—Sn1—Cl1ii177.97 (3)O4—C7—C8108.9 (7)
Cl1—Sn1—Cl1ii84.87 (3)O4—C7—H7A109.9
Sn1—O1W—H1109.5C8—C7—H7A109.9
C1—O1—C10113.8 (4)O4—C7—H7B109.9
C2—O2—C3113.8 (7)C8—C7—H7B109.9
C5—O3—C4113.4 (6)H7A—C7—H7B108.3
C7—O4—C6113.4 (6)O5—C8—C7107.7 (7)
C8—O5—C9113.4 (8)O5—C8—H8A110.2
O1—C1—C2108.1 (8)C7—C8—H8A110.2
O1—C1—H1A110.1O5—C8—H8B110.2
C2—C1—H1A110.1C7—C8—H8B110.2
O1—C1—H1B110.1H8A—C8—H8B108.5
C2—C1—H1B110.1O5—C9—C10107.4 (8)
H1A—C1—H1B108.4O5—C9—H9A110.2
O2—C2—C1107.1 (8)C10—C9—H9A110.2
O2—C2—H2A110.3O5—C9—H9B110.2
C1—C2—H2A110.3C10—C9—H9B110.2
O2—C2—H2B110.3H9A—C9—H9B108.5
C1—C2—H2B110.3O1—C10—C9106.0 (8)
H2A—C2—H2B108.5O1—C10—H10A110.5
O2—C3—C4107.6 (8)C9—C10—H10A110.5
O2—C3—H3A110.2O1—C10—H10B110.5
C4—C3—H3A110.2C9—C10—H10B110.5
O2—C3—H3B110.2H10A—C10—H10B108.7
C4—C3—H3B110.2Sn1—C11—H11109.5
H3A—C3—H3B108.5Sn1—C11—H12109.5
O3—C4—C3107.0 (9)H11—C11—H12109.5
O3—C4—H4A110.3Sn1—C11—H13109.5
C3—C4—H4A110.3H11—C11—H13109.5
O3—C4—H4B110.3H12—C11—H13109.5
C3—C4—H4B110.3
Symmetry codes: (i) x, −y+1, z; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H1···O10.842.372.753 (4)108
O1w—H1···O1i0.842.382.753 (4)107
O1w—H1···O2iii0.842.122.687 (9)125
O1w—H1···O5iv0.842.262.810 (9)123
Symmetry codes: (i) x, −y+1, z; (iii) −x+2, y, −z+2; (iv) −x+2, −y+1, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H1···O10.842.372.753 (4)108
O1w—H1···O1i0.842.382.753 (4)107
O1w—H1···O2ii0.842.122.687 (9)125
O1w—H1···O5iii0.842.262.810 (9)123
Symmetry codes: (i) x, −y+1, z; (ii) −x+2, y, −z+2; (iii) −x+2, −y+1, −z+2.
Acknowledgements top

We thank Shahid Beheshti University and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

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