Aqua­chloro­di­methyl­phenyl­tin–18-crown-6 (2/1)

In the crystal structure of the title compound, [SnCl(CH₃)₂(C₆H₅)(H₂O)]₂·C₁₂H₂₄O₈, the crown ether, which lies on a center of inversion, interacts with the five-coordinate trans-C₃SnClO trigonal-bipyramidal aqua­chloro­di­methyl­phenyl­tin moieties; the coordinated water mol­ecule, at a distance of 2.445 (4) Å from Sn, forms two hydrogen bonds with the O atoms of the crown ether [O_water...O_crown = 2.851 (6) and 2.884 (5) Å].

Key indicators

• Single-crystal X-ray study
• T = 168 K
• Mean [sigma](C-C) = 0.010 Å
• Disorder in main residue
• R factor = 0.060
• wR factor = 0.107
• Data-to-parameter ratio = 19.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.50
         From the CIF: _reflns_number_total               3392
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3676
         Completeness (_total/calc)             92.27%
          Alert C: < 95% complete

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.104

PLAT_731  Alert C Bond    Calc     0.84(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O1W  -H1W2    1.555   1.555

PLAT_732  Alert C Angle   Calc      110(5), Rep      110(2) ....       2.50 s.u-Ratio
                     H1W1 -O1W  -H1W2    1.555   1.555   1.555

PLAT_735  Alert C D-H     Calc     0.86(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O1W  -H1W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.84(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O1W  -H1W2    1.555   1.555

PLAT_736  Alert C H...A   Calc     2.01(4), Rep   2.010(10) ....       4.00 s.u-Ratio
                     H1W2 -O3      1.555   1.555

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.939
          Tmax scaled      0.553 Tmin scaled      0.471


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 7 Alert Level C = Please check

---

S1. Comment

The coordination status of the Sn atom in mixed triorganotin compounds featuring one methyl group can be investigated from the magnitude of the tin–methyl coupling constants in the NMR. Unfortunately, the synthesis of the mixed triorganotin entity presents difficulties, and only a few such compounds have been synthesized. Earlier, we reported the 2:1 methyldiphenyltin trifluoroacetate complex of 18-crown-6; this exists as a dihydrate in which the coordinated water molecules interact with the centrosymmetric cyclic polyether through hydrogen bonds [Sn—O_water = 2.483 (5) Å; O_water···O_18-crown-6 = 2.901 (8) and 2.983 (7) Å; Amini et al., 2002]. In this compound, the trifluoroacetate anion serves to increase the Lewis acidity of the Sn atom through its electron-withdrawing ability.

In the title compound, (I), the dimethylphenyltin chloride moiety is also coordinated by a water molecule [Sn—O = 2.445 (4) Å], and the water molecule similarly interacts with the cyclic polyether [O_water···O_18-crown-6 = 2.851 (6) and 2.884 (5) Å]. The two-bond coupling constant of the adduct in solution (83 Hz) is significantly larger than that of the parent Lewis acid (59 Hz), so that the water molecule probably remains attached to the Sn atom even in solution.

S2. Experimental

The title adduct was synthesized from the reaction of equimolar quantities of dimethylphenyltin chloride (0.20 g, 0.75 mmol) and 18-crown-6 (0.20 g, 0.75 mmol) in chloroform. The reagents were dissolved in the solvent and crystals of the 2:1 complex (m.p. 344–349 K) separated when the solvent was allowed to evaporate. IR: 3440 (H₂O), 2880 (C—H), 1099 (C—O—C), 550 (Sn—C, asymmetric), 520 (Sn—C, symmetric) cm^{−1. 1}H NMR in CDCl₃: 0.90 (CH₃, 12H), 2.45 (H₂O, 4H), 3.65 (CH₂, 24H), 7.46–7.60 (C₆H₅, 10H) p.p.m. ²J|¹¹⁹–¹H| = 83 Hz. Dimethylphenyltin chloride was synthesizd 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 (Simmones, 1977).

S3. Refinement

The minor disorder in the 18-crown-6 ring was treated by constraining the C—O distances to be approximated equal by a SADI 0.01 instruction in SHELXL97; the C—C distances were also constrained by another SADI 0.01 instruction. The phenyl ring was refined as a rigid hexagon. The carbon-bound H atoms were positioned geometrically, and were allowed to ride on the parent C atoms, with U(H) = 1.2U_eq(C). The water H atoms were located and their positions refined, subject to O—H = 0.85±0.01, H···H = 1.39±0.01 Å, and U_iso(H) = 1.2U_eq(O). The final difference map had a large peak/hole at about 1 Å from atom Sn1.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of the title dinuclear complex, with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Bis(aquachlorodimethylphenyltin)^.18-crown-6

Crystal data

[SnCl(CH3)2(C6H5)(H2O)]2·C12H24O8	F(000) = 832
Mr = 822.96	Dx = 1.541 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6395 (6) Å	Cell parameters from 4938 reflections
b = 19.472 (1) Å	θ = 2.4–26.5°
c = 10.5110 (7) Å	µ = 1.60 mm^−1
β = 116.015 (1)°	T = 168 K
V = 1773.0 (2) Å^3	Block, colorless
Z = 2	0.50 × 0.48 × 0.37 mm

Data collection

Siemens CCD area-detector diffractometer	3392 independent reflections
Radiation source: fine-focus sealed tube	2495 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
ω scans	θmax = 26.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.502, Tmax = 0.589	k = −24→24
9926 measured reflections	l = −10→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0348P)^2] where P = (Fo^2 + 2Fc^2)/3
3392 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 2.62 e Å^−3
21 restraints	Δρmin = −1.76 e Å^−3

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

	x	y	z	Uiso*/Ueq
Sn1	0.36801 (5)	0.11313 (2)	0.25316 (5)	0.0261 (2)
Cl1	0.6100 (2)	0.18146 (8)	0.3566 (2)	0.0379 (4)
O1	0.1800 (5)	−0.1056 (2)	0.1746 (4)	0.035 (1)
O2	−0.0522 (5)	−0.0498 (2)	0.2397 (4)	0.038 (1)
O3	−0.1683 (5)	0.0761 (2)	0.0958 (5)	0.036 (1)
O1w	0.1378 (5)	0.0411 (2)	0.1432 (5)	0.036 (1)
C1	0.2951 (8)	0.1546 (3)	0.0483 (7)	0.045 (2)
C2	0.4793 (7)	0.0165 (3)	0.3101 (7)	0.034 (2)
C3	0.2772 (5)	0.1511 (2)	0.3949 (4)	0.028 (2)
C4	0.1233 (4)	0.1702 (2)	0.3452 (4)	0.032 (2)
C5	0.0676 (4)	0.1933 (2)	0.4392 (5)	0.043 (2)
C6	0.1659 (6)	0.1973 (2)	0.5830 (5)	0.048 (2)
C7	0.3198 (6)	0.1783 (2)	0.6327 (3)	0.050 (2)
C8	0.3755 (4)	0.1552 (2)	0.5387 (4)	0.041 (2)
C9	0.1272 (8)	−0.1370 (3)	0.2686 (7)	0.044 (2)
C10	0.0834 (8)	−0.0817 (3)	0.3427 (7)	0.044 (2)
C11	−0.1049 (8)	0.0044 (3)	0.2975 (7)	0.044 (2)
C12	−0.2286 (8)	0.0426 (3)	0.1818 (7)	0.050 (2)
C13	−0.2773 (8)	0.1215 (3)	−0.0037 (7)	0.048 (2)
C14	−0.2066 (9)	0.1554 (3)	−0.0883 (7)	0.047 (2)
H1w1	0.148 (6)	−0.001 (1)	0.125 (7)	0.043*
H1w2	0.047 (3)	0.048 (2)	0.133 (7)	0.043*
H1a	0.3803	0.1525	0.0213	0.067*
H1b	0.2639	0.2025	0.0479	0.067*
H1c	0.2075	0.1280	−0.0193	0.067*
H2a	0.4103	−0.0166	0.3235	0.051*
H2b	0.5741	0.0210	0.3985	0.051*
H2c	0.5051	0.0003	0.2348	0.051*
H4	0.0561	0.1674	0.2469	0.039*
H5	−0.0376	0.2063	0.4052	0.052*
H6	0.1279	0.2131	0.6472	0.058*
H7	0.3870	0.1811	0.7310	0.060*
H8	0.4807	0.1421	0.5727	0.049*
H9a	0.2101	−0.1658	0.3387	0.052*
H9b	0.0370	−0.1666	0.2145	0.052*
H10a	0.0631	−0.1016	0.4196	0.053*
H10b	0.1678	−0.0477	0.3844	0.053*
H11a	−0.0183	0.0358	0.3522	0.052*
H11b	−0.1448	−0.0145	0.3625	0.052*
H12a	−0.3117	0.0105	0.1230	0.060*
H12b	−0.2734	0.0772	0.2221	0.060*
H13a	−0.3088	0.1567	0.0465	0.057*
H13b	−0.3704	0.0956	−0.0673	0.057*
H14a	−0.2765	0.1916	−0.1488	0.057*
H14b	−0.1077	0.1772	−0.0240	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0353 (3)	0.0215 (2)	0.0182 (2)	−0.0007 (2)	0.0086 (2)	−0.0004 (2)
Cl1	0.041 (1)	0.0354 (9)	0.0283 (10)	−0.0104 (7)	0.0071 (9)	−0.0027 (7)
O1	0.047 (3)	0.020 (2)	0.032 (3)	−0.001 (2)	0.011 (3)	0.002 (2)
O2	0.048 (3)	0.041 (3)	0.018 (3)	−0.005 (2)	0.010 (3)	−0.003 (2)
O3	0.032 (3)	0.040 (3)	0.031 (3)	−0.002 (2)	0.010 (3)	−0.008 (2)
O1w	0.042 (3)	0.026 (2)	0.043 (3)	−0.003 (2)	0.020 (3)	−0.006 (2)
C1	0.049 (5)	0.042 (4)	0.020 (4)	−0.011 (3)	−0.007 (4)	0.006 (3)
C2	0.032 (4)	0.028 (3)	0.029 (4)	0.002 (3)	0.003 (4)	0.004 (3)
C3	0.037 (4)	0.019 (3)	0.026 (4)	−0.002 (3)	0.011 (4)	−0.002 (3)
C4	0.037 (4)	0.025 (3)	0.024 (4)	−0.008 (3)	0.005 (4)	−0.003 (3)
C5	0.049 (5)	0.023 (3)	0.071 (6)	−0.005 (3)	0.039 (5)	−0.006 (3)
C6	0.080 (6)	0.031 (4)	0.047 (5)	−0.007 (4)	0.040 (5)	−0.007 (3)
C7	0.068 (6)	0.047 (4)	0.032 (4)	−0.004 (4)	0.019 (5)	−0.006 (4)
C8	0.049 (5)	0.039 (4)	0.030 (4)	0.001 (3)	0.013 (4)	−0.005 (3)
C9	0.050 (5)	0.034 (3)	0.027 (4)	−0.009 (3)	−0.001 (4)	0.011 (3)
C10	0.058 (5)	0.046 (4)	0.021 (4)	−0.017 (4)	0.010 (4)	0.001 (3)
C11	0.057 (5)	0.057 (5)	0.019 (4)	−0.008 (4)	0.019 (4)	−0.004 (3)
C12	0.058 (5)	0.053 (5)	0.061 (6)	−0.010 (4)	0.045 (5)	−0.019 (4)
C13	0.048 (5)	0.039 (4)	0.056 (5)	0.007 (4)	0.023 (5)	−0.015 (4)
C14	0.058 (5)	0.025 (4)	0.043 (5)	0.010 (3)	0.007 (4)	−0.002 (3)

Geometric parameters (Å, º)

Sn1—C1	2.111 (6)	C1—H1b	0.9800
Sn1—C2	2.119 (5)	C1—H1c	0.9800
Sn1—C3	2.163 (3)	C2—H2a	0.9800
Sn1—O1w	2.445 (4)	C2—H2b	0.9800
Sn1—Cl1	2.484 (2)	C2—H2c	0.9800
O1—C14^i	1.426 (6)	C4—H4	0.9500
O1—C9	1.431 (6)	C5—H5	0.9500
O2—C11	1.419 (6)	C6—H6	0.9500
O2—C10	1.423 (6)	C7—H7	0.9500
O3—C13	1.419 (6)	C8—H8	0.9500
O3—C12	1.429 (6)	C9—H9a	0.9900
C3—C4	1.3900	C9—H9b	0.9900
C3—C8	1.3900	C10—H10a	0.9900
C4—C5	1.3900	C10—H10b	0.9900
C5—C6	1.3900	C11—H11a	0.9900
C6—C7	1.3900	C11—H11b	0.9900
C7—C8	1.3900	C12—H12a	0.9900
C9—C10	1.494 (7)	C12—H12b	0.9900
C11—C12	1.477 (7)	C13—H13a	0.9900
C13—C14	1.491 (7)	C13—H13b	0.9900
O1w—H1w1	0.85 (1)	C14—H14a	0.9900
O1w—H1w2	0.85 (1)	C14—H14b	0.9900
C1—H1a	0.9800
C1—Sn1—C2	121.9 (3)	H2b—C2—H2c	109.5
C1—Sn1—C3	121.2 (2)	C5—C4—H4	120.0
C1—Sn1—O1w	84.9 (2)	C3—C4—H4	120.0
C1—Sn1—Cl1	94.0 (2)	C4—C5—H5	120.0
C2—Sn1—C3	114.6 (2)	C6—C5—H5	120.0
C2—Sn1—O1w	82.3 (2)	C7—C6—H6	120.0
C2—Sn1—Cl1	95.2 (2)	C5—C6—H6	120.0
C3—Sn1—O1w	88.0 (2)	C6—C7—H7	120.0
C3—Sn1—Cl1	95.8 (1)	C8—C7—H7	120.0
O1w—Sn1—Cl1	176.1 (1)	C7—C8—H8	120.0
C14^i—O1—C9	111.5 (5)	C3—C8—H8	120.0
C11—O2—C10	112.4 (5)	O1—C9—H9a	110.0
C13—O3—C12	112.0 (5)	C10—C9—H9a	110.0
C4—C3—C8	120.0	O1—C9—H9b	110.0
C4—C3—Sn1	121.3 (2)	C10—C9—H9b	110.0
C8—C3—Sn1	118.7 (2)	H9a—C9—H9b	108.3
C5—C4—C3	120.0	O2—C10—H10a	110.3
C4—C5—C6	120.0	C9—C10—H10a	110.3
C7—C6—C5	120.0	O2—C10—H10b	110.3
C6—C7—C8	120.0	C9—C10—H10b	110.3
C7—C8—C3	120.0	H10a—C10—H10b	108.6
O1—C9—C10	108.6 (5)	O2—C11—H11a	109.8
O2—C10—C9	107.0 (5)	C12—C11—H11a	109.8
O2—C11—C12	109.5 (5)	O2—C11—H11b	109.8
O3—C12—C11	110.2 (5)	C12—C11—H11b	109.8
O3—C13—C14	109.3 (5)	H11a—C11—H11b	108.2
O1^i—C14—C13	109.6 (5)	O3—C12—H12a	109.6
Sn1—O1w—H1w1	119 (3)	C11—C12—H12a	109.6
Sn1—O1w—H1w2	130 (3)	O3—C12—H12b	109.6
H1w1—O1w—H1w2	110 (2)	C11—C12—H12b	109.6
Sn1—C1—H1a	109.5	H12a—C12—H12b	108.1
Sn1—C1—H1b	109.5	O3—C13—H13a	109.8
H1a—C1—H1b	109.5	C14—C13—H13a	109.8
Sn1—C1—H1c	109.5	O3—C13—H13b	109.8
H1a—C1—H1c	109.5	C14—C13—H13b	109.8
H1b—C1—H1c	109.5	H13a—C13—H13b	108.3
Sn1—C2—H2a	109.5	O1^i—C14—H14a	109.7
Sn1—C2—H2b	109.5	C13—C14—H14a	109.7
H2a—C2—H2b	109.5	O1^i—C14—H14b	109.7
Sn1—C2—H2c	109.5	C13—C14—H14b	109.7
H2a—C2—H2c	109.5	H14a—C14—H14b	108.2
C1—Sn1—C3—C4	37.7 (3)	C5—C6—C7—C8	0.0
C2—Sn1—C3—C4	−125.6 (3)	C6—C7—C8—C3	0.0
O1w—Sn1—C3—C4	−45.0 (2)	C4—C3—C8—C7	0.0
Cl1—Sn1—C3—C4	136.0 (2)	Sn1—C3—C8—C7	−178.9 (3)
C1—Sn1—C3—C8	−143.4 (3)	C14^i—O1—C9—C10	−173.2 (5)
C2—Sn1—C3—C8	53.3 (3)	C11—O2—C10—C9	−179.5 (5)
O1w—Sn1—C3—C8	133.9 (2)	O1—C9—C10—O2	69.4 (7)
Cl1—Sn1—C3—C8	−45.1 (2)	C10—O2—C11—C12	170.4 (5)
C8—C3—C4—C5	0.0	C13—O3—C12—C11	−171.3 (5)
Sn1—C3—C4—C5	178.9 (3)	O2—C11—C12—O3	−65.5 (7)
C3—C4—C5—C6	0.0	C12—O3—C13—C14	179.2 (5)
C4—C5—C6—C7	0.0	O3—C13—C14—O1^i	67.0 (7)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.85 (1)	2.10 (3)	2.884 (5)	153 (6)
O1w—H1w2···O3	0.85 (1)	2.01 (1)	2.851 (6)	172 (6)