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Acta Cryst. (2008). E64, m1177    [ doi:10.1107/S1600536808025890 ]

([mu]-Piperazine-1,4-dicarbodithioato-[kappa]4S,S':S'',S''')bis[triphenyltin(IV)] dichloromethane solvate

P. Poplaukhin and E. R. T. Tiekink

Abstract top

The dinuclear centrosymmetric title compound, [Sn2(C6H5)6(C6H8N2S4)]·CH2Cl2, features a distorted cis-trigonal-bipyramidal coordination geometry for Sn based on a C3S2 donor set. The dinuclear molecule lies across a centre of inversion. The solvent dichloromethane molecule is disordered about a centre of inversion.

Comment top

Tin dithiocarbamates continue to attract interest owing to their variety of applications (Tiekink, 2008). The title compound, Ph3SnS2CN(CH2CH2)2NCS2SnPh3, has been reported previously as a methanol solvate (Yin et al., 2002). The present structure (I) has been isolated as a dichloromethane solvate, Fig. 1. The molecule is centrosymmetric so that the Ph3Sn entities lie to either side of the pyrrolidine ring which adopts a chair conformation. The dithiocarbamate ligand coordinates in an asymmetric mode, forming Sn—S1 and Sn—S2 distances of 2.4699 (13) and 3.0715 (13) Å, respectively. The coordination geometry is based on a distorted trigonal bipyramid as indicated by the value of τ = 0.64 (Addison et al., 1984).

Related literature top

For a review of tin dithiocarbamates, see: Tiekink (2008). For a related structure, see: Yin et al. (2002). For analysis of trigonal–bipyramidal geometries, see: Addison et al. (1984).

Experimental top

The title compound was prepared by following a literature procedure (Yin et al., 2002). Colourless crystals were isolated by the slow evaporation of a dichloromethane solution of (I); m.p. 487–489 K (crystal turned opaque at 363–368 K). TGA: two steps, First mass loss 7.2% (onset 388.3 K, midpoint 392.6 K, endset 396.9 K) corresponds to loss CH2Cl2 (8.2% theoretical). Second mass loss 69.3% (onset 558.5 K, midpoint 620 K, endset 680 K), corresponds to decomposition to SnS (total experimental mass loss 76.5% cf. theoretical value 70.5%). IR (cm-1): 1427, 1416 (strong, C═N), 1214 (strong, C—S).

Refinement top

The H atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The solvent dichloromethane molecule was disordered about a centre of inversion and was modelled with anisotropic displacement parameters.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing the crystallographic numbering scheme. Displacement ellipsoids are shown at the 70% probability level. Unlabelled atoms are related by the symmetry operation i: -x, 1-y, 1-z. The disordered dichloromethane molecule is omitted.
(µ-Piperazine-1,4-dicarbodithioto- κ4S,S':S'',S''')bis[triphenyltin(IV)] dichloromethane solvate top
Crystal data top
[Sn2(C6H5)6(C6H8N2S4)]·CH2Cl2F000 = 1020
Mr = 1021.37Dx = 1.594 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 13756 reflections
a = 14.681 (5) Åθ = 2.4–40.7º
b = 10.758 (3) ŵ = 1.53 mm−1
c = 13.470 (4) ÅT = 98 (2) K
β = 90.379 (6)ºPlate, colourless
V = 2127.3 (11) Å30.35 × 0.15 × 0.02 mm
Z = 2
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer		4389 independent reflections
Radiation source: fine-focus sealed tube4021 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 98(2) Kθmax = 26.5º
ω scansθmin = 2.4º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −17→18
Tmin = 0.354, Tmax = 1k = −13→13
14400 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.113  w = 1/[σ2(Fo2) + (0.04P)2 + 8.4194P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
4389 reflectionsΔρmax = 0.77 e Å−3
244 parametersΔρmin = −1.12 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Sn2(C6H5)6(C6H8N2S4)]·CH2Cl2V = 2127.3 (11) Å3
Mr = 1021.37Z = 2
Monoclinic, P21/cMo Kα
a = 14.681 (5) ŵ = 1.53 mm−1
b = 10.758 (3) ÅT = 98 (2) K
c = 13.470 (4) Å0.35 × 0.15 × 0.02 mm
β = 90.379 (6)º
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer		4389 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		4021 reflections with I > 2σ(I)
Tmin = 0.354, Tmax = 1Rint = 0.048
14400 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048244 parameters
wR(F2) = 0.113H-atom parameters constrained
S = 1.10Δρmax = 0.77 e Å−3
4389 reflectionsΔρmin = −1.12 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn0.23132 (2)0.37950 (3)0.17164 (2)0.02056 (11)
S10.10733 (8)0.32408 (10)0.28651 (9)0.0237 (3)
S20.12861 (8)0.59723 (11)0.26696 (9)0.0244 (3)
N10.0190 (3)0.4872 (4)0.3970 (3)0.0250 (9)
C10.0795 (3)0.4757 (4)0.3239 (3)0.0228 (9)
C2−0.0077 (3)0.6087 (4)0.4381 (4)0.0264 (11)
H2A−0.07450.61930.43200.032*
H2B0.02200.67610.40020.032*
C30.0208 (3)0.6161 (4)0.5471 (4)0.0260 (10)
H3A0.08800.61280.55250.031*
H3B0.00010.69610.57560.031*
C40.2559 (3)0.1881 (4)0.1326 (3)0.0212 (9)
C50.2678 (3)0.1546 (5)0.0335 (4)0.0238 (10)
H50.26900.2174−0.01600.029*
C60.2780 (3)0.0316 (5)0.0060 (4)0.0284 (11)
H60.28460.0103−0.06200.034*
C70.2785 (3)−0.0610 (4)0.0782 (4)0.0284 (11)
H70.2869−0.14530.05960.034*
C80.2666 (4)−0.0303 (5)0.1768 (4)0.0320 (12)
H80.2664−0.09360.22590.038*
C90.2549 (3)0.0934 (4)0.2042 (4)0.0270 (10)
H90.24620.11390.27210.032*
C100.1869 (3)0.4710 (4)0.0402 (3)0.0231 (10)
C110.2262 (4)0.5821 (5)0.0088 (4)0.0413 (14)
H110.27670.61570.04420.050*
C120.1920 (4)0.6440 (5)−0.0742 (5)0.0424 (15)
H120.21840.7205−0.09440.051*
C130.1199 (4)0.5948 (4)−0.1273 (4)0.0272 (10)
H130.09660.6377−0.18360.033*
C140.0818 (4)0.4841 (5)−0.0989 (4)0.0344 (12)
H140.03240.4497−0.13560.041*
C150.1166 (4)0.4223 (5)−0.0151 (4)0.0307 (11)
H150.09080.34490.00380.037*
C160.3474 (3)0.4550 (4)0.2475 (4)0.0238 (10)
C170.4094 (3)0.3737 (5)0.2921 (4)0.0297 (11)
H170.40110.28650.28600.036*
C180.4830 (4)0.4199 (5)0.3453 (4)0.0369 (12)
H180.52470.36400.37590.044*
C190.4966 (4)0.5477 (5)0.3543 (4)0.0378 (13)
H190.54750.57910.39040.045*
C200.4352 (3)0.6280 (5)0.3103 (4)0.0308 (11)
H200.44390.71510.31650.037*
C210.3608 (3)0.5833 (4)0.2570 (4)0.0247 (10)
H210.31910.63970.22700.030*
C220.5409 (12)0.0134 (14)0.5721 (11)0.066 (4)0.50
H22A0.60460.04340.57640.080*0.50
H22B0.51720.00060.64000.080*0.50
Cl10.4667 (2)0.1259 (2)0.4994 (2)0.0958 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.02652 (19)0.01628 (17)0.01887 (18)−0.00089 (12)−0.00114 (13)0.00000 (11)
S10.0281 (6)0.0167 (5)0.0263 (6)−0.0002 (4)0.0029 (5)−0.0026 (4)
S20.0294 (6)0.0191 (5)0.0247 (6)0.0000 (5)0.0020 (5)−0.0025 (4)
N10.027 (2)0.0180 (19)0.030 (2)0.0038 (16)0.0035 (17)0.0006 (16)
C10.024 (2)0.023 (2)0.021 (2)0.0046 (18)−0.0024 (18)−0.0055 (18)
C20.025 (2)0.019 (2)0.035 (3)0.0045 (18)0.010 (2)−0.0009 (19)
C30.024 (2)0.018 (2)0.036 (3)0.0017 (18)0.007 (2)−0.001 (2)
C40.026 (2)0.015 (2)0.023 (2)0.0014 (17)0.0030 (18)−0.0032 (17)
C50.024 (2)0.027 (2)0.021 (2)0.0037 (19)0.0010 (18)−0.0005 (19)
C60.032 (3)0.030 (3)0.023 (3)0.001 (2)−0.001 (2)−0.008 (2)
C70.029 (3)0.018 (2)0.038 (3)−0.0012 (19)−0.002 (2)−0.007 (2)
C80.043 (3)0.021 (2)0.032 (3)0.001 (2)0.007 (2)0.006 (2)
C90.035 (3)0.024 (2)0.022 (2)0.001 (2)0.003 (2)0.0007 (19)
C100.032 (2)0.018 (2)0.019 (2)0.0025 (18)0.0003 (19)−0.0009 (17)
C110.057 (4)0.033 (3)0.034 (3)−0.019 (3)−0.024 (3)0.012 (2)
C120.060 (4)0.029 (3)0.039 (3)−0.014 (3)−0.013 (3)0.013 (2)
C130.041 (3)0.022 (2)0.019 (2)0.006 (2)−0.001 (2)−0.0006 (19)
C140.039 (3)0.029 (3)0.035 (3)−0.004 (2)−0.016 (2)0.002 (2)
C150.038 (3)0.024 (2)0.030 (3)−0.007 (2)−0.009 (2)0.003 (2)
C160.018 (2)0.027 (2)0.026 (3)−0.0031 (18)−0.0007 (18)−0.0023 (19)
C170.028 (3)0.031 (3)0.030 (3)0.001 (2)−0.004 (2)0.001 (2)
C180.029 (3)0.036 (3)0.045 (3)0.002 (2)−0.006 (2)0.004 (3)
C190.032 (3)0.040 (3)0.041 (3)−0.011 (2)−0.005 (2)−0.005 (3)
C200.026 (3)0.032 (3)0.034 (3)−0.009 (2)−0.002 (2)−0.003 (2)
C210.023 (2)0.023 (2)0.027 (3)−0.0027 (19)0.0017 (19)0.0021 (19)
C220.102 (12)0.050 (8)0.048 (9)0.001 (8)0.023 (8)0.001 (7)
Cl10.155 (3)0.0477 (11)0.0854 (17)0.0173 (13)0.0274 (17)0.0024 (11)
Geometric parameters (Å, °) top
Sn—C102.125 (5)C10—C151.373 (7)
Sn—C162.141 (5)C10—C111.394 (7)
Sn—C42.157 (4)C11—C121.392 (8)
Sn—S12.4699 (13)C11—H110.9500
Sn—S23.0715 (13)C12—C131.378 (8)
S1—C11.756 (5)C12—H120.9500
S2—C11.680 (5)C13—C141.370 (7)
N1—C11.337 (6)C13—H130.9500
N1—C3i1.466 (6)C14—C151.403 (7)
N1—C21.473 (6)C14—H140.9500
C2—C31.527 (7)C15—H150.9500
C2—H2A0.9900C16—C171.396 (7)
C2—H2B0.9900C16—C211.400 (7)
C3—N1i1.466 (6)C17—C181.385 (7)
C3—H3A0.9900C17—H170.9500
C3—H3B0.9900C18—C191.395 (8)
C4—C51.394 (6)C18—H180.9500
C4—C91.403 (7)C19—C201.380 (8)
C5—C61.382 (7)C19—H190.9500
C5—H50.9500C20—C211.389 (7)
C6—C71.392 (7)C20—H200.9500
C6—H60.9500C21—H210.9500
C7—C81.380 (7)C22—Cl1ii1.784 (15)
C7—H70.9500C22—Cl11.896 (16)
C8—C91.392 (7)C22—H22A0.9900
C8—H80.9500C22—H22B0.9900
C9—H90.9500Cl1—C22ii1.784 (15)
C10—Sn—C16117.43 (18)C8—C9—H9119.7
C10—Sn—C4106.86 (18)C4—C9—H9119.7
C16—Sn—C4110.16 (18)C15—C10—C11118.3 (5)
C10—Sn—S1114.23 (13)C15—C10—Sn120.1 (4)
C16—Sn—S1112.36 (13)C11—C10—Sn121.7 (4)
C4—Sn—S192.74 (12)C12—C11—C10120.4 (5)
C10—Sn—S281.15 (12)C12—C11—H11119.8
C16—Sn—S284.41 (13)C10—C11—H11119.8
C4—Sn—S2156.03 (12)C13—C12—C11120.3 (5)
S1—Sn—S263.66 (4)C13—C12—H12119.9
C1—S1—Sn97.41 (16)C11—C12—H12119.9
C1—S2—Sn79.09 (16)C14—C13—C12120.2 (5)
C1—N1—C3i125.3 (4)C14—C13—H13119.9
C1—N1—C2122.6 (4)C12—C13—H13119.9
C3i—N1—C2111.8 (4)C13—C14—C15119.3 (5)
N1—C1—S2123.6 (4)C13—C14—H14120.4
N1—C1—S1117.0 (4)C15—C14—H14120.4
S2—C1—S1119.4 (3)C10—C15—C14121.6 (5)
N1—C2—C3109.6 (4)C10—C15—H15119.2
N1—C2—H2A109.7C14—C15—H15119.2
C3—C2—H2A109.7C17—C16—C21119.2 (5)
N1—C2—H2B109.7C17—C16—Sn118.9 (4)
C3—C2—H2B109.7C21—C16—Sn121.9 (4)
H2A—C2—H2B108.2C18—C17—C16120.2 (5)
N1i—C3—C2110.3 (4)C18—C17—H17119.9
N1i—C3—H3A109.6C16—C17—H17119.9
C2—C3—H3A109.6C17—C18—C19120.6 (5)
N1i—C3—H3B109.6C17—C18—H18119.7
C2—C3—H3B109.6C19—C18—H18119.7
H3A—C3—H3B108.1C20—C19—C18119.1 (5)
C5—C4—C9118.2 (4)C20—C19—H19120.4
C5—C4—Sn120.2 (3)C18—C19—H19120.4
C9—C4—Sn121.5 (3)C19—C20—C21121.0 (5)
C6—C5—C4121.2 (5)C19—C20—H20119.5
C6—C5—H5119.4C21—C20—H20119.5
C4—C5—H5119.4C20—C21—C16119.8 (5)
C5—C6—C7119.8 (5)C20—C21—H21120.1
C5—C6—H6120.1C16—C21—H21120.1
C7—C6—H6120.1Cl1ii—C22—Cl1102.9 (8)
C8—C7—C6120.1 (5)Cl1ii—C22—H22A111.2
C8—C7—H7120.0Cl1—C22—H22A111.2
C6—C7—H7120.0Cl1ii—C22—H22B111.2
C7—C8—C9120.0 (5)Cl1—C22—H22B111.2
C7—C8—H8120.0H22A—C22—H22B109.1
C9—C8—H8120.0C22ii—Cl1—C2277.1 (8)
C8—C9—C4120.6 (5)
C10—Sn—S1—C1−69.6 (2)Sn—C4—C9—C8176.9 (4)
C16—Sn—S1—C167.4 (2)C16—Sn—C10—C15175.8 (4)
C4—Sn—S1—C1−179.5 (2)C4—Sn—C10—C1551.5 (4)
S2—Sn—S1—C1−3.88 (16)S1—Sn—C10—C15−49.5 (4)
C10—Sn—S2—C1126.8 (2)S2—Sn—C10—C15−105.3 (4)
C16—Sn—S2—C1−114.3 (2)C16—Sn—C10—C11−5.6 (5)
C4—Sn—S2—C115.0 (4)C4—Sn—C10—C11−129.8 (5)
S1—Sn—S2—C14.10 (17)S1—Sn—C10—C11129.2 (4)
C3i—N1—C1—S2−175.8 (4)S2—Sn—C10—C1173.4 (4)
C2—N1—C1—S2−2.8 (7)C15—C10—C11—C122.7 (9)
C3i—N1—C1—S14.6 (7)Sn—C10—C11—C12−176.0 (5)
C2—N1—C1—S1177.6 (4)C10—C11—C12—C13−1.2 (10)
Sn—S2—C1—N1174.5 (4)C11—C12—C13—C14−0.4 (9)
Sn—S2—C1—S1−5.9 (2)C12—C13—C14—C150.5 (8)
Sn—S1—C1—N1−173.0 (3)C11—C10—C15—C14−2.6 (8)
Sn—S1—C1—S27.3 (3)Sn—C10—C15—C14176.1 (4)
C1—N1—C2—C3−116.5 (5)C13—C14—C15—C101.1 (8)
C3i—N1—C2—C357.4 (5)C10—Sn—C16—C17−143.2 (4)
N1—C2—C3—N1i−56.4 (5)C4—Sn—C16—C17−20.6 (4)
C10—Sn—C4—C518.7 (4)S1—Sn—C16—C1781.2 (4)
C16—Sn—C4—C5−110.0 (4)S2—Sn—C16—C17139.8 (4)
S1—Sn—C4—C5135.0 (4)C10—Sn—C16—C2139.4 (5)
S2—Sn—C4—C5125.3 (3)C4—Sn—C16—C21162.0 (4)
C10—Sn—C4—C9−157.4 (4)S1—Sn—C16—C21−96.1 (4)
C16—Sn—C4—C974.0 (4)S2—Sn—C16—C21−37.6 (4)
S1—Sn—C4—C9−41.1 (4)C21—C16—C17—C180.2 (8)
S2—Sn—C4—C9−50.8 (6)Sn—C16—C17—C18−177.2 (4)
C9—C4—C5—C60.3 (7)C16—C17—C18—C19−0.5 (9)
Sn—C4—C5—C6−175.9 (4)C17—C18—C19—C200.6 (9)
C4—C5—C6—C7−1.4 (7)C18—C19—C20—C21−0.4 (9)
C5—C6—C7—C81.6 (8)C19—C20—C21—C160.0 (8)
C6—C7—C8—C9−0.5 (8)C17—C16—C21—C200.0 (7)
C7—C8—C9—C4−0.6 (8)Sn—C16—C21—C20177.4 (4)
C5—C4—C9—C80.7 (7)Cl1ii—C22—Cl1—C22ii0.000 (2)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.
references
References top

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