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

Amini, M.M.; Ng, S.W.

doi:10.1107/S1600536812008781

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

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 Sn^IV 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, 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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812008781/xu5444sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812008781/xu5444Isup2.hkl Contains datablock I

CCDC reference: 877024

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (Sn-O) = 0.003 Å
Disorder in main residue
R factor = 0.017
wR factor = 0.042
Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT415_ALERT_2_B Short Inter D-H..H-X       H1     ..  H4B     ..       1.93 Ang.
PLAT415_ALERT_2_B Short Inter D-H..H-X       H1     ..  H7A     ..       2.08 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O1W    -   H1     ...          ?

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         17
PLAT976_ALERT_2_C Negative Residual Density at 1.02A from O1W    .      -0.52 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ....          2
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          1
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................        100 Perc.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         43

   0 ALERT level A = Most likely a serious problem - resolve or explain
   3 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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 Sn^IV 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 O_water···O_{crown 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 Sn^IV 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.

Structure description top

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

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

	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.
	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]·C₁₀H₂₀O₅	F(000) = 688
M_r = 695.61	D_x = 1.820 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 5314 reflections
a = 14.2351 (13) Å	θ = 2.5–27.5°
b = 11.4115 (5) Å	µ = 2.42 mm⁻¹
c = 9.8100 (9) Å	T = 100 K
β = 127.183 (14)°	Block, colorless
V = 1269.6 (3) Å³	0.30 × 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 Source	1495 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.016
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.5°
ω scan	h = −16→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→14
T_min = 0.531, T_max = 0.644	l = −12→12
5824 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.042	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.023P)² + 2.1038P] where P = (F_o² + 2F_c²)/3
1524 reflections	(Δ/σ)_max = 0.001
93 parameters	Δρ_max = 0.48 e Å⁻³
43 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[Sn₂(CH₃)₄Cl₄(H₂O)₂]·C₁₀H₂₀O₅	V = 1269.6 (3) Å³
M_r = 695.61	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 14.2351 (13) Å	µ = 2.42 mm⁻¹
b = 11.4115 (5) Å	T = 100 K
c = 9.8100 (9) Å	0.30 × 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)
T_min = 0.531, T_max = 0.644	R_int = 0.016
5824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	43 restraints
wR(F²) = 0.042	H-atom parameters constrained
S = 0.99	Δρ_max = 0.48 e Å⁻³
1524 reflections	Δρ_min = −0.72 e Å⁻³
93 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.655960 (17)	0.5000	0.51206 (2)	0.01800 (8)
Cl1	0.43822 (7)	0.5000	0.25799 (9)	0.02629 (17)
Cl2	0.73232 (8)	0.5000	0.35183 (10)	0.02918 (17)
O1W	0.8420 (2)	0.5000	0.7676 (3)	0.0329 (5)
H1	0.8512	0.5605	0.8232	0.049*
O1	0.8868 (4)	0.5018 (14)	1.0827 (5)	0.0187 (5)	0.25
O2	1.0086 (8)	0.6816 (7)	1.0770 (10)	0.0187 (5)	0.25
O3	1.0110 (5)	0.6179 (5)	0.7954 (7)	0.0187 (5)	0.25
O4	1.0459 (5)	0.3741 (5)	0.8555 (7)	0.0187 (5)	0.25
O5	1.0106 (8)	0.3021 (7)	1.1028 (10)	0.0187 (5)	0.25
C1	0.8963 (15)	0.6095 (12)	1.164 (2)	0.0199 (5)	0.25
H1A	0.9664	0.6078	1.2858	0.024*	0.25
H1B	0.8255	0.6215	1.1595	0.024*	0.25
C2	0.9075 (17)	0.7073 (16)	1.072 (3)	0.0199 (5)	0.25
H2A	0.8355	0.7121	0.9520	0.024*	0.25
H2B	0.9183	0.7831	1.1288	0.024*	0.25
C3	1.0255 (10)	0.7633 (8)	0.9801 (15)	0.0199 (5)	0.25
H3A	1.0707	0.8324	1.0511	0.024*	0.25
H3B	0.9482	0.7904	0.8774	0.024*	0.25
C4	1.0921 (13)	0.7001 (12)	0.928 (2)	0.0199 (5)	0.25
H4A	1.1211	0.7565	0.8846	0.024*	0.25
H4B	1.1606	0.6582	1.0273	0.024*	0.25
C5	1.0639 (7)	0.5468 (6)	0.7385 (10)	0.0199 (5)	0.25
H5A	1.1192	0.5954	0.7333	0.024*	0.25
H5B	1.0017	0.5182	0.6215	0.024*	0.25
C6	1.1287 (7)	0.4445 (6)	0.8525 (11)	0.0199 (5)	0.25
H6A	1.1640	0.3978	0.8088	0.024*	0.25
H6B	1.1929	0.4717	0.9695	0.024*	0.25
C7	1.0979 (8)	0.2730 (8)	0.9620 (13)	0.0199 (5)	0.25
H7A	1.1728	0.2947	1.0729	0.024*	0.25
H7B	1.1153	0.2138	0.9063	0.024*	0.25
C8	1.0136 (11)	0.2234 (7)	0.9908 (17)	0.0199 (5)	0.25
H8A	0.9339	0.2159	0.8806	0.024*	0.25
H8B	1.0402	0.1447	1.0436	0.024*	0.25
C9	0.9022 (14)	0.2965 (13)	1.084 (3)	0.0199 (5)	0.25
H9A	0.8978	0.2221	1.1316	0.024*	0.25
H9B	0.8338	0.3004	0.9611	0.024*	0.25
C10	0.9009 (15)	0.3995 (12)	1.179 (2)	0.0199 (5)	0.25
H10A	0.8346	0.3926	1.1861	0.024*	0.25
H10B	0.9756	0.4036	1.2963	0.024*	0.25
C11	0.6536 (2)	0.68104 (19)	0.5528 (3)	0.0271 (5)
H11	0.6202	0.6940	0.6144	0.041*
H12	0.6053	0.7215	0.4423	0.041*
H13	0.7343	0.7118	0.6206	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.02135 (12)	0.01588 (12)	0.01478 (11)	0.000	0.00988 (9)	0.000
Cl1	0.0286 (4)	0.0210 (3)	0.0177 (3)	0.000	0.0079 (3)	0.000
Cl2	0.0375 (4)	0.0312 (4)	0.0283 (4)	0.000	0.0249 (4)	0.000
O1W	0.0301 (12)	0.0391 (14)	0.0182 (11)	0.000	0.0088 (10)	0.000
O1	0.0216 (11)	0.0195 (12)	0.0150 (15)	−0.0018 (15)	0.0111 (11)	0.0016 (13)
O2	0.0216 (11)	0.0195 (12)	0.0150 (15)	−0.0018 (15)	0.0111 (11)	0.0016 (13)
O3	0.0216 (11)	0.0195 (12)	0.0150 (15)	−0.0018 (15)	0.0111 (11)	0.0016 (13)
O4	0.0216 (11)	0.0195 (12)	0.0150 (15)	−0.0018 (15)	0.0111 (11)	0.0016 (13)
O5	0.0216 (11)	0.0195 (12)	0.0150 (15)	−0.0018 (15)	0.0111 (11)	0.0016 (13)
C1	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C2	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C3	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C4	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C5	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C6	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C7	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C8	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C9	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C10	0.0250 (10)	0.0192 (13)	0.0199 (13)	−0.0014 (16)	0.0159 (9)	0.0018 (15)
C11	0.0345 (12)	0.0181 (10)	0.0345 (12)	−0.0066 (9)	0.0239 (11)	−0.0058 (9)

Geometric parameters (Å, º) top

Sn1—C11	2.108 (2)	C3—H3A	0.9900
Sn1—C11ⁱ	2.108 (2)	C3—H3B	0.9900
Sn1—O1W	2.296 (2)	C4—H4A	0.9900
Sn1—Cl2	2.3912 (8)	C4—H4B	0.9900
Sn1—Cl1	2.5459 (10)	C5—C6	1.489 (8)
Sn1—Cl1ⁱⁱ	3.2467 (9)	C5—H5A	0.9900
O1W—H1	0.8400	C5—H5B	0.9900
O1—C1	1.427 (9)	C6—H6A	0.9900
O1—C10	1.438 (9)	C6—H6B	0.9900
O2—C2	1.440 (10)	C7—C8	1.501 (8)
O2—C3	1.452 (8)	C7—H7A	0.9900
O3—C5	1.430 (7)	C7—H7B	0.9900
O3—C4	1.447 (10)	C8—H8A	0.9900
O4—C7	1.427 (8)	C8—H8B	0.9900
O4—C6	1.442 (7)	C9—C10	1.508 (9)
O5—C8	1.439 (8)	C9—H9A	0.9900
O5—C9	1.439 (9)	C9—H9B	0.9900
C1—C2	1.505 (9)	C10—H10A	0.9900
C1—H1A	0.9900	C10—H10B	0.9900
C1—H1B	0.9900	C11—H11	0.9800
C2—H2A	0.9900	C11—H12	0.9800
C2—H2B	0.9900	C11—H13	0.9800
C3—C4	1.504 (9)

C11—Sn1—C11ⁱ	157.00 (13)	H4A—C4—H4B	108.6
C11—Sn1—O1W	86.16 (7)	O3—C5—C6	112.7 (5)
C11ⁱ—Sn1—O1W	86.16 (7)	O3—C5—H5A	109.1
C11—Sn1—Cl2	100.96 (6)	C6—C5—H5A	109.1
C11ⁱ—Sn1—Cl2	100.96 (6)	O3—C5—H5B	109.1
O1W—Sn1—Cl2	92.01 (7)	C6—C5—H5B	109.1
C11—Sn1—Cl1	92.07 (7)	H5A—C5—H5B	107.8
C11ⁱ—Sn1—Cl1	92.07 (7)	O4—C6—C5	108.0 (6)
O1W—Sn1—Cl1	170.83 (7)	O4—C6—H6A	110.1
Cl2—Sn1—Cl1	97.16 (3)	C5—C6—H6A	110.1
C11—Sn1—Cl1ⁱⁱ	78.93 (6)	O4—C6—H6B	110.1
C11ⁱ—Sn1—Cl1ⁱⁱ	78.93 (6)	C5—C6—H6B	110.1
O1W—Sn1—Cl1ⁱⁱ	85.96 (7)	H6A—C6—H6B	108.4
Cl2—Sn1—Cl1ⁱⁱ	177.97 (3)	O4—C7—C8	108.9 (7)
Cl1—Sn1—Cl1ⁱⁱ	84.87 (3)	O4—C7—H7A	109.9
Sn1—O1W—H1	109.5	C8—C7—H7A	109.9
C1—O1—C10	113.8 (4)	O4—C7—H7B	109.9
C2—O2—C3	113.8 (7)	C8—C7—H7B	109.9
C5—O3—C4	113.4 (6)	H7A—C7—H7B	108.3
C7—O4—C6	113.4 (6)	O5—C8—C7	107.7 (7)
C8—O5—C9	113.4 (8)	O5—C8—H8A	110.2
O1—C1—C2	108.1 (8)	C7—C8—H8A	110.2
O1—C1—H1A	110.1	O5—C8—H8B	110.2
C2—C1—H1A	110.1	C7—C8—H8B	110.2
O1—C1—H1B	110.1	H8A—C8—H8B	108.5
C2—C1—H1B	110.1	O5—C9—C10	107.4 (8)
H1A—C1—H1B	108.4	O5—C9—H9A	110.2
O2—C2—C1	107.1 (8)	C10—C9—H9A	110.2
O2—C2—H2A	110.3	O5—C9—H9B	110.2
C1—C2—H2A	110.3	C10—C9—H9B	110.2
O2—C2—H2B	110.3	H9A—C9—H9B	108.5
C1—C2—H2B	110.3	O1—C10—C9	106.0 (8)
H2A—C2—H2B	108.5	O1—C10—H10A	110.5
O2—C3—C4	107.6 (8)	C9—C10—H10A	110.5
O2—C3—H3A	110.2	O1—C10—H10B	110.5
C4—C3—H3A	110.2	C9—C10—H10B	110.5
O2—C3—H3B	110.2	H10A—C10—H10B	108.7
C4—C3—H3B	110.2	Sn1—C11—H11	109.5
H3A—C3—H3B	108.5	Sn1—C11—H12	109.5
O3—C4—C3	107.0 (9)	H11—C11—H12	109.5
O3—C4—H4A	110.3	Sn1—C11—H13	109.5
C3—C4—H4A	110.3	H11—C11—H13	109.5
O3—C4—H4B	110.3	H12—C11—H13	109.5
C3—C4—H4B	110.3

Symmetry codes: (i) x, −y+1, z; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1···O1	0.84	2.37	2.753 (4)	108
O1w—H1···O1ⁱ	0.84	2.38	2.753 (4)	107
O1w—H1···O2ⁱⁱⁱ	0.84	2.12	2.687 (9)	125
O1w—H1···O5^iv	0.84	2.26	2.810 (9)	123

Symmetry codes: (i) x, −y+1, z; (iii) −x+2, y, −z+2; (iv) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Sn₂(CH₃)₄Cl₄(H₂O)₂]·C₁₀H₂₀O₅
M_r	695.61
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	100
a, b, c (Å)	14.2351 (13), 11.4115 (5), 9.8100 (9)
β (°)	127.183 (14)
V (Å³)	1269.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.42
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.531, 0.644
No. of measured, independent and observed [I > 2σ(I)] reflections	5824, 1524, 1495
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.042, 0.99
No. of reflections	1524
No. of parameters	93
No. of restraints	43
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.72

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).