Two novel tri­methyl­sulfonium salts with polymeric {[SbCl₄]⁻}_n or {[CdCl₃]⁻}_n anions

The title organic–inorganic hybrid salts poly[tri­methyl­sul­fon­ium [[di­chlorido­anti­mony(III)]-di-μ-chlorido]], {(C₃H₉S)[SbCl₄]}_n, (I), and catena-poly[tri­methyl­sulfonium [cadmium(II)-tri-μ-chlorido]], {(C₃H₉S)[CdCl₃]}_n, (II), consist of tri­methyl­sul­fon­ium cations and polymeric {[SbCl₄]⁻}_n or {[CdCl₃]⁻}_n anions. The central metal atoms are coordinated by six Cl atoms, forming an anionic {[SbCl₄]⁻}_n three-dimensional framework (two of the four bridging chloride anions are located on two different centres of inversion) or anionic {[CdCl₃]⁻}_n one-dimensional chains. The tri­methyl­sulfonium cation of (II) is disordered over two sets of sites in a 0.791 (4):0.209 (4) ratio. All the anions are linked by tri­methyl­sulfonium cations through weak C—H...Cl hydrogen bonds to form three-dimensional structures.

S1. Introduction

Recently, much attention has been concentrated on studies of new dielectric and ferroelectric materials, due to the discovery of dielectric–ferroelectric systems and their wide range of applications, for instance as filters, capacitors, resonators or solid-state transducer components in microwave communication systems (Fu et al., 2008; Vanderah, 2002; Ye et al., 2009; Zhang et al., 2010; Zhang & Xiong, 2012). In the search for potential ferroelectric materials, molecular-based chlorido­anti­monate(III) or chloridocadmate(II) organic–inorganic compounds have been of inter­est, as they often display solid–solid phase transitions induced by a variation in temperature (Walther et al., 1978; Piecha et al., 2012; Chaabouni et al., 2003; Zaleski, 1997; Bujak & Zaleski, 2004; Ma et al., 2006; Peral et al., 2000; Kind et al., 1979). In previously reported ferroelectric metal–organic frameworks, compounds having the formulae A[SbX₄] or A[CdX₃] (A = organic cation and X = halide) often exhibit phase transitions, such as the structures of (4-NH₂PyH)[SbCl₄] and [(CH₃)₄N][CdBr₃] (4-NH₂PyH is 4-amino­pyridinium; Zhang & Xiong, 2012). In addition, chlorido­anti­monates and chloridocadmates show a wide variety of stereochemical complexity because of both the variability of the metal-ion coordination geometry and the bridging capability of the halide anions. Knowing that the structures of [CH₃C₆H₄NH(CH₃)₂(SbCl₄)]_n and [(C₃H₁₀N)(CdCl₃)]_n, which contain polymeric anions, undergo solid–solid phase transitions (Walther et al., 1978; Chaabouni et al., 2003), we expected to obtain their tri­methyl­sulfonium analogues which would possibly have solid–solid phase transitions. With these in mind, two new organic–inorganic hybrid complexes {(C₃H₉S)[SbCl₄]}_n, (I), and {(C₃H₉S)[CdCl₃]}_n, (II), were prepared and characterized.

S2. Experimental

S2.1. Synthesis and crystallization

Mixtures of tri­methyl­sulfonium iodide (1.02 g, 5 mmol) and silver carbonate (0.69 g, 2.5 mmol) were added to water (30 ml) and stirred for 30 min at room temperature. The mixtures were then filtered and hydro­chloric acid (0.97 g, 5 mmol, 37% solution in water) was added to the filtrate with stirring over a period of 2 min. SbCl₃ (1.14 g, 5 mmol) or CdCl₂.2.5H₂O (1.14 g, 5 mmol) was added to the above solutions to afford a colourless solution in each case. These solutions were left to evaporate at room temperature in air for two weeks and yielded colourless crystals of (I) and (II) suitable for single-crystal X-ray diffraction.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For both compounds, C-bound H atoms were included in calculated positions and refined using a riding model, with C—H = 0.97 Å and U_iso(H) = 1.5U_eq(C). The tri­methyl­sulfonium cation in (II) was modelled as disordered over two sites, with a site-occupancy ratio of 0.791 (4):0.209 (4). Rigid-bond and similarity restraints were applied to all atoms of the cations to ensure reasonable displacement parameters and constraints were added to give equivalent displacement parameters for the corresponding atoms of the minor and major disorder components.

S3. Comment

The asymmetric unit of (I) consists of a tri­methyl­sulfonium cation and an [SbCl₄]^- anion, with three terminal Cl atoms and two halves of the bridging Cl atom, located on two different centres of inversion. As shown in Fig. 1, there are SbCl₃ pyramids (Sb1, Cl1, Cl2 and Cl3) in the structure, with Sb—Cl(terminal) bond lengths ranging from 2.3754 (9) to 2.4931 (9) Å. The average Cl—Sb—Cl angle for these atoms is 90.82 (3)°. The C1^- anions (Cl4 and Cl5) form bridges with considerably longer Sb—Cl distances [2.9024 (7) and 3.0325 (6) Å] between the SbC1₃ subunits (symmetry codes as in Fig. 1). Additionally, Cl3 is in a short, probably bonding, contact with another Sb centre [3.4542 (13) Å]. Each Sb atom therefore accepts three long Sb—C1 contacts, although these are still much shorter than the sum of the van der Waals radii of Sb and Cl (4.0 Å; Pauling, 1960). The six Cl atoms bonded to each Sb atom form a distorted o­cta­hedron, with the short and long contacts in trans positions. As a consequence, the SbCl₃ subunit is considerably deformed compared with gaseous SbC1₃ (Konaka & Kimura, 1973), which has an Sb—Cl bond length of 2.333 (3) Å and a bond angle of 97.2 (9)°.

A coordination very similar to that in (I) is found in the crystal structure of [NH(CH₃)₃]₃[Sb₂Cl₉] (Kallel & Bats, 1985). In the crystal structure of SbCl₃, on the other hand, no coordinative Sb—Cl bonds are longer than 3.457 (1) Å; thus, an almost undistorted SbCl₃ molecule is observed, with bond lengths between 2.340 (2) and 2.368 (1) Å (Lipka, 1979). Almost undistorted SbCl₃ subunits are also observed in many other SbCl₃ adducts (Demaldé et al., 1972; Lipka & Mootz, 1978).

The Sb—Cl distances of (I) are very different, unlike those in Cd complexes such as the structure reported by Corradi et al. (1997), and this may be induced by the difference in valence electron count. The Cl—Sb—Cl angles are in the ranges 82.05 (2)–103.653 (10) and 166.24 (2)–169.06 (2)°, deviating slightly from ideal o­cta­hedral angle values (90 and 180°). The Sb atoms are bridged by Cl atoms (Cl4 and Cl5), giving rise to infinite polymeric chains extending in the [110] and [110] directions, with an Sb1ⁱⁱ···Sb1···Sb1ⁱⁱⁱ angle of 103.653 (4)° (symmetry codes as in Fig. 1), indicating that the polymer chain is a zigzag chain (Fig. 1). The Sb···Sb distances are 6.0648 (13) and 5.8046 (15) Å, which are much longer than those found in the previously reported structures (C₅H₁₄n₃)(SbCl₄) and (C₂H₅N)₄(Sb₄Cl₁₆) (Bujak et al., 1999; Zaleski, 1997), but comparable with those found in (C₃n₅n₂)₄(Sb₂Cl₁₀) and [BeCl(12-crown-4)][SbCl₄] (Neumuller & Dehnicke, 2006; Piecha et al., 2012). The nearest two perpendicularly oriented chains are linked to each other by long Sb—Cl3^v contacts in the [001] direction, forming Sb₂Cl₂ loops with an Sb···Sb distance of 4.5725 (12) Å, which results in the three-dimensional framework (symmetry codes as in Fig. 1). The tri­methyl­sulfonium cations are located in the inter-framework space and the charges of the cations are balanced by the anionic {[SbCl₄]^-}_∞ polymer framework.

The bond lengths and angles of the tri­methyl­sulfonium cations of (I) are in agreement with those reported in the literature (Hess et al., 2007). The elongated displacement ellipsoids of atoms Cl5 and C3 show traces of disorder, which means that atoms C3 and Cl5 are quite mobile at room temperature, but examination of a difference map of the two atoms does show they exist as distinct atoms, so this kind of disorder could be dynamic disorder. All the tri­methyl­sulfonium cations are linked by the anionic {[SbCl₄]^-}_n polymer framework, with weak C1—H1A···Cl3(-x, y, -z + 3/2), C1—H1B···Cl1(x, -y, z - 1/2), C2—H2C···Cl1 and C3—H3B···Cl2(x + 1/2, -y + 1/2, z - 1/2) hydrogen bonds, forming a three-dimensional structure (Fig. 2 and Table 2).

Salt (II) has an asymmetric unit that consists of a disordered tri­methyl­sulfonium cation and a [CdCl₃]^- anion. The other three chloride ligands (Cl1ⁱⁱ, Cl2ⁱⁱ and Clⁱⁱ) are generated by the (x - 1/2, -y + 3/2, -z + 1) twofold screw-axis operation (Fig. 3). The tri­methyl­sulfonium cation is more mobile than that of (I), so is disordered over two sets of sites in a ratio of 0.791 (4):0.209 (4), but the bond lengths and angles of the cations are similar to those of (I), which is consistent with structures reported in the literature (Hess et al., 2007). The Cd atoms are hexacoordinated in a slightly distorted o­cta­hedral Cd(µ-Cl)₆ arrangement. The Cd—Cl bond lengths are in the range 2.618 (2)–2.664 (2) Å, which are comparable with those found in a previously reported structure (Corradi et al., 1997). The Cl—Cd—Cl angles are in the ranges 82.86 (7)–97.99 (7) and 178.91 (8)–179.17 (4)°, deviating slightly from ideal o­cta­hedral angle values (90 and 180°). The o­cta­hedra are linked by two opposite shared faces, giving rise to infinite {[Cd(µ-Cl)₃]^-}_n chains parallel to the [100] direction, with a Cd1···Cd1ⁱⁱ distance of 3.3724 (6) Å, which is much shorter than those reported in other one-dimensional cadmium polymers bridged by Cl atoms (Huang et al., 1998; Hu et al., 2003; Laskar et al., 2002), and a Cd1ⁱ···Cd1···Cd1ⁱⁱ angle of 178.75 (4)° [symmetry codes: (i) x + 1/2, -y + 3/2, -z + 1; (ii) x - 1/2, -y + 3/2, -z + 1], indicating that the polymer chain is nearly linear. Thus, all the chloride ligands act as bridges between two consecutive Cd atoms, and each pair of consecutive Cd atoms is linked by three corner-shared bridging chloride ligands (Fig. 4). The tri­methyl­sulfonium cations are located in the inter-chain space and the charges of the cations are balanced by the anionic {[Cd(µ-Cl)₃]^-}_n polymer chains.

There are numerous nonclassical C—H···Cl hydrogen bonds in the structure of (II). The crystal structure is stabilized by C3—H3B···Cl1(x + 1, y, z) and C3—H3C···Cl1(x + 1/2, -y + 1/2, -z + 1) hydrogen-bond inter­actions, linking the cations and anionic chains (Fig. 4 and Table 3).

Our original inter­est in (I) and (II) lay mainly in their potential as molecular ferroelectric materials. The variable-temperature dielectric constants of (I) and (II) were initially measured on powder samples in the form of pressed pellets with a sandwich architecture, Ag/sample/Ag, in the temperature range 275–345 K. However, measurement of their dielectric properties with varying temperature did not show any dielectric anomaly but only a smooth increase in the measured temperature range. The steady dielectric constants of the two compounds are the result of the contribution of electronic and ionic displacements. A contribution from dipolar reorientation does not occur under the measuring conditions used here, although it is what we are searching for. This implies that there is no structural phase transition within this temperature range and so (I) and (II) are not ferroelectric materials, unlike those reported earlier (Ye et al., 2009; Fu et al., 2008). Other related materials are currently being investigated for ferroelectric activity.

In summary, two novel organic–inorganic complexes which contain the same cation and different kinds of polymeric anions were prepared, and the possibility of undergoing a phase transition was investigated. They form two distinct types of polymer anions linked by tri­methyl­sulfonium cations with different C—H···Cl nonclassical hydrogen-bonding inter­actions, forming the three dimensional structures with different packing modes.

Related literature

For related literature, see: Bujak & Zaleski (2004); Bujak et al. (1999); Chaabouni et al. (2003); Corradi et al. (1997); Demaldé et al. (1972); Fu et al. (2008); Hess et al. (2007); Hu et al. (2003); Huang et al. (1998); Kallel & Bats (1985); Kind et al. (1979); Konaka & Kimura (1973); Laskar et al. (2002); Lipka (1979); Lipka & Mootz (1978); Ma et al. (2006); Neumuller & Dehnicke (2006); Pauling (1960); Peral et al. (2000); Piecha et al. (2012); Vanderah (2002); Walther et al. (1978); Ye et al. (2009); Zaleski (1997); Zhang & Xiong (2012); Zhang et al. (2010).

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The one-dimensional polymeric zigzag chain of (I) with the SbCl₃ pyramids (shaded), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x - 1/2, y + 1/2, z; (ii) -x , -y + 1, -z + 2; (iii) -x + 1/2, -y + 1/2, -z + 2; (iv) x + 1/2, y - 1/2, z; (v) -x, y, -z + 3/2; (vi) x, -y + 1, z + 1/2; (vii) ?, ?, ? [Please provide missing details]]

Fig. 2. A packing diagram for (I), viewed along the b axis, with weak C—H···Cl hydrogen-bond interactions shown as dashed lines.

Fig. 3. The one-dimensional {[Cd(µ-Cl)₃]^-}_n chain in (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x + 1/2, -y + 3/2, -z + 1; (ii) x - 1/2, -y + 3/2, -z + 1.]

Fig. 4. A packing diagram for (II), with weak C—H···Cl hydrogen-bond interactions shown as dashed lines.

(Sb) Poly[trimethylsulfonium [[dichloridoantimony(III)]-di-µ-chlorido]]

Crystal data

(C3H9S)[SbCl4]	Z = 8
Mr = 340.71	F(000) = 1296
Monoclinic, C2/c	Dx = 2.101 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 13.182 (3) Å	Cell parameters from 2461 reflections
b = 13.214 (3) Å	µ = 3.68 mm^−1
c = 12.374 (3) Å	T = 293 K
β = 91.58 (3)°	Block, colourless
V = 2154.7 (7) Å^3	0.36 × 0.32 × 0.28 mm

Data collection

Rigaku Mercury2 diffractometer	2335 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
CCD profile fitting scans	h = −17→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
Tmin = 0.275, Tmax = 0.355	l = −16→16
10903 measured reflections	3 standard reflections every 180 reflections
2461 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.0117P)^2 + 2.4036P] where P = (Fo^2 + 2Fc^2)/3
S = 1.22	(Δ/σ)max = 0.001
2461 reflections	Δρmax = 0.49 e Å^−3
89 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00423 (10)

Special details

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

	x	y	z	Uiso*/Ueq
Cl4	0.0000	0.5000	1.0000	0.0525 (2)
Sb1	0.040593 (11)	0.283935 (11)	0.930824 (12)	0.02777 (7)
Cl3	−0.12572 (5)	0.29406 (5)	0.83051 (6)	0.04424 (16)
Cl1	0.04484 (5)	0.10404 (5)	0.89532 (6)	0.04289 (16)
Cl2	−0.03173 (6)	0.24786 (6)	1.10026 (6)	0.05281 (19)
Cl5	0.2500	0.2500	1.0000	0.0772 (4)
S1	0.27952 (5)	−0.02123 (5)	0.65738 (5)	0.03736 (15)
C1	0.2351 (2)	0.0576 (2)	0.5493 (2)	0.0501 (7)
H1A	0.1947	0.1114	0.5775	0.075*
H1B	0.1947	0.0182	0.4991	0.075*
H1C	0.2920	0.0856	0.5128	0.075*
C2	0.1642 (2)	−0.0672 (2)	0.7104 (2)	0.0480 (7)
H2A	0.1785	−0.1036	0.7762	0.072*
H2B	0.1317	−0.1116	0.6587	0.072*
H2C	0.1201	−0.0113	0.7249	0.072*
C3	0.3196 (3)	0.0687 (2)	0.7563 (3)	0.0602 (9)
H3A	0.2651	0.1148	0.7696	0.090*
H3B	0.3768	0.1057	0.7305	0.090*
H3C	0.3386	0.0343	0.8221	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0417 (5)	0.0513 (6)	0.0647 (7)	−0.0002 (4)	0.0040 (5)	−0.0022 (5)
Sb1	0.02639 (9)	0.02787 (10)	0.02887 (10)	−0.00162 (6)	−0.00261 (6)	0.00209 (6)
Cl3	0.0326 (3)	0.0458 (4)	0.0538 (4)	0.0047 (3)	−0.0091 (3)	0.0047 (3)
Cl1	0.0447 (3)	0.0294 (3)	0.0542 (4)	0.0036 (3)	−0.0055 (3)	−0.0061 (3)
Cl2	0.0675 (5)	0.0541 (4)	0.0378 (4)	0.0132 (4)	0.0181 (3)	0.0094 (3)
Cl5	0.0754 (8)	0.0749 (8)	0.0792 (9)	−0.0256 (7)	−0.0383 (7)	0.0287 (7)
S1	0.0323 (3)	0.0373 (3)	0.0427 (4)	0.0049 (3)	0.0045 (3)	−0.0002 (3)
C1	0.0496 (16)	0.0600 (18)	0.0406 (15)	0.0053 (14)	−0.0021 (12)	0.0071 (13)
C2	0.0387 (14)	0.0503 (16)	0.0555 (17)	−0.0063 (13)	0.0102 (13)	−0.0035 (14)
C3	0.072 (2)	0.0560 (19)	0.0515 (18)	−0.0225 (17)	−0.0186 (16)	0.0033 (15)

Geometric parameters (Å, º)

Sb1—Cl3^i	3.4542 (13)	C1—H1A	0.9600
Cl4—Sb1	3.0325 (6)	C1—H1B	0.9600
Sb1—Cl2	2.3754 (9)	C1—H1C	0.9600
Sb1—Cl1	2.4183 (8)	C2—H2A	0.9600
Sb1—Cl3	2.4931 (9)	C2—H2B	0.9600
Sb1—Cl5	2.9024 (7)	C2—H2C	0.9600
S1—C3	1.776 (3)	C3—H3A	0.9600
S1—C2	1.779 (3)	C3—H3B	0.9600
S1—C1	1.782 (3)	C3—H3C	0.9600
Cl1—Sb1—Cl4	169.082 (18)	S1—C1—H1A	109.5
Cl1—Sb1—Cl3	89.24 (2)	S1—C1—H1B	109.5
Cl1—Sb1—Cl5	82.827 (17)	H1A—C1—H1B	109.5
Cl2—Sb1—Cl1	88.56 (3)	S1—C1—H1C	109.5
Cl2—Sb1—Cl3	94.67 (3)	H1A—C1—H1C	109.5
Cl2—Sb1—Cl5	96.33 (3)	H1B—C1—H1C	109.5
Cl2—Sb1—Cl4	82.04 (2)	S1—C2—H2A	109.5
Cl3—Sb1—Cl5	166.250 (19)	S1—C2—H2B	109.5
Cl3—Sb1—Cl4	86.010 (18)	H2A—C2—H2B	109.5
Cl3^i—Sb1—Cl1	81.87 (2)	S1—C2—H2C	109.5
Cl3^i—Sb1—Cl2	169.30 (3)	H2A—C2—H2C	109.5
Cl3^i—Sb1—Cl3	80.54 (2)	H2B—C2—H2C	109.5
Cl3^i—Sb1—Cl4	106.987 (15)	S1—C3—H3A	109.5
Cl3^i—Sb1—Cl5	87.204 (13)	S1—C3—H3B	109.5
Cl5—Sb1—Cl4	103.651 (3)	H3A—C3—H3B	109.5
C3—S1—C2	102.44 (16)	S1—C3—H3C	109.5
C3—S1—C1	102.21 (16)	H3A—C3—H3C	109.5
C2—S1—C1	102.13 (15)	H3B—C3—H3C	109.5

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl3^i	0.96	2.83	3.765 (3)	165
C1—H1B···Cl1^ii	0.96	2.83	3.771 (3)	166
C2—H2C···Cl1	0.96	2.81	3.610 (3)	142
C3—H3B···Cl2^iii	0.96	2.81	3.695 (3)	153

Symmetry codes: (i) −x, y, −z+3/2; (ii) x, −y, z−1/2; (iii) x+1/2, −y+1/2, z−1/2.

(Cd) catena-Poly[trimethylsulfonium [cadmium(II)-tri-µ-chlorido]]

Crystal data

(C3H9S)[CdCl3]	F(000) = 568
Mr = 295.91	Dx = 2.126 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2108 reflections
a = 6.7443 (13) Å	µ = 3.37 mm^−1
b = 9.0050 (18) Å	T = 293 K
c = 15.224 (3) Å	Block, colourless
V = 924.6 (3) Å^3	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer	1990 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
CCD profile fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
Tmin = 0.500, Tmax = 0.513	l = −19→19
8566 measured reflections	3 standard reflections every 180 reflections
2108 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.029	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 0.750P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max = 0.001
S = 1.01	Δρmax = 1.25 e Å^−3
2108 reflections	Δρmin = −0.79 e Å^−3
117 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
198 restraints	Extinction coefficient: 0.0519 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 868 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (7)

Special details

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.8203 (2)	0.27333 (17)	0.30541 (10)	0.0517 (5)	0.791 (4)
C1	0.8469 (12)	0.0804 (7)	0.2875 (6)	0.076 (2)	0.791 (4)
H1A	0.7867	0.0542	0.2325	0.114*	0.791 (4)
H1B	0.7832	0.0269	0.3341	0.114*	0.791 (4)
H1C	0.9852	0.0553	0.2860	0.114*	0.791 (4)
C2	0.5610 (9)	0.2890 (11)	0.3144 (8)	0.095 (3)	0.791 (4)
H2A	0.4991	0.2359	0.2671	0.142*	0.791 (4)
H2B	0.5238	0.3918	0.3116	0.142*	0.791 (4)
H2C	0.5186	0.2479	0.3695	0.142*	0.791 (4)
C3	0.8924 (15)	0.2878 (10)	0.4168 (5)	0.102 (3)	0.791 (4)
H3A	0.8638	0.3859	0.4379	0.153*	0.791 (4)
H3B	1.0320	0.2689	0.4218	0.153*	0.791 (4)
H3C	0.8205	0.2163	0.4511	0.153*	0.791 (4)
S1B	0.7112 (10)	0.2074 (7)	0.3669 (3)	0.0586 (18)	0.209 (4)
C1B	0.739 (4)	0.070 (3)	0.2850 (18)	0.080 (7)	0.209 (4)
H1BA	0.6190	0.0132	0.2806	0.121*	0.209 (4)
H1BB	0.8469	0.0054	0.3003	0.121*	0.209 (4)
H1BC	0.7664	0.1168	0.2297	0.121*	0.209 (4)
C2B	0.608 (5)	0.354 (3)	0.305 (2)	0.090 (7)	0.209 (4)
H2BA	0.6502	0.4476	0.3289	0.135*	0.209 (4)
H2BB	0.4663	0.3481	0.3064	0.135*	0.209 (4)
H2BC	0.6527	0.3468	0.2449	0.135*	0.209 (4)
C3B	0.960 (2)	0.270 (3)	0.377 (2)	0.088 (7)	0.209 (4)
H3BA	0.9950	0.2767	0.4376	0.132*	0.209 (4)
H3BB	0.9729	0.3655	0.3496	0.132*	0.209 (4)
H3BC	1.0469	0.2005	0.3479	0.132*	0.209 (4)
Cd1	0.04558 (4)	0.75139 (4)	0.499184 (19)	0.03614 (13)
Cl1	0.29509 (18)	0.54036 (11)	0.45567 (8)	0.0485 (3)
Cl2	0.29369 (17)	0.79899 (13)	0.63156 (6)	0.0461 (3)
Cl3	0.29817 (19)	0.92520 (12)	0.41299 (7)	0.0495 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0550 (9)	0.0452 (8)	0.0549 (8)	−0.0035 (7)	0.0038 (6)	0.0167 (6)
C1	0.075 (6)	0.062 (5)	0.091 (5)	0.020 (4)	0.001 (4)	−0.023 (4)
C2	0.072 (6)	0.093 (7)	0.120 (7)	0.025 (5)	0.000 (5)	−0.009 (6)
C3	0.131 (8)	0.081 (6)	0.093 (6)	−0.031 (6)	−0.052 (6)	−0.005 (5)
S1B	0.068 (4)	0.067 (4)	0.041 (3)	−0.006 (3)	0.000 (3)	0.000 (2)
C1B	0.093 (14)	0.056 (11)	0.092 (12)	−0.015 (12)	−0.018 (13)	−0.032 (10)
C2B	0.087 (13)	0.082 (14)	0.102 (13)	0.001 (13)	−0.006 (13)	−0.002 (13)
C3B	0.089 (14)	0.079 (13)	0.096 (14)	−0.013 (12)	−0.009 (12)	−0.016 (13)
Cd1	0.02240 (17)	0.04097 (19)	0.04506 (19)	0.00103 (8)	−0.00014 (8)	−0.00222 (14)
Cl1	0.0332 (5)	0.0379 (5)	0.0743 (7)	0.0032 (5)	−0.0062 (6)	−0.0155 (5)
Cl2	0.0351 (5)	0.0661 (6)	0.0370 (4)	−0.0072 (5)	0.0015 (4)	−0.0052 (4)
Cl3	0.0352 (5)	0.0546 (6)	0.0589 (6)	0.0047 (5)	0.0032 (5)	0.0200 (5)

Geometric parameters (Å, º)

S1—C2	1.760 (6)	C1B—H1BB	0.9600
S1—C1	1.768 (6)	C1B—H1BC	0.9600
S1—C3	1.769 (6)	C2B—H2BA	0.9600
C1—H1A	0.9600	C2B—H2BB	0.9600
C1—H1B	0.9600	C2B—H2BC	0.9600
C1—H1C	0.9600	C3B—H3BA	0.9600
C2—H2A	0.9600	C3B—H3BB	0.9600
C2—H2B	0.9600	C3B—H3BC	0.9600
C2—H2C	0.9600	Cd1—Cl1^i	2.6159 (11)
C3—H3A	0.9600	Cd1—Cl1	2.6233 (12)
C3—H3B	0.9600	Cd1—Cl2	2.6543 (11)
C3—H3C	0.9600	Cd1—Cl2^i	2.6559 (11)
S1B—C1B	1.766 (9)	Cd1—Cl3	2.6596 (12)
S1B—C2B	1.769 (9)	Cd1—Cl3^i	2.6647 (11)
S1B—C3B	1.776 (9)	Cd1—Cd1^i	3.3723 (6)
C1B—H1BA	0.9600	Cd1—Cd1^ii	3.3723 (7)
C2—S1—C1	101.0 (4)	Cl1—Cd1—Cl2^i	95.58 (4)
C2—S1—C3	101.1 (4)	Cl2—Cd1—Cl2^i	179.06 (3)
C1—S1—C3	101.1 (4)	Cl1^i—Cd1—Cl3	96.98 (4)
C1B—S1B—C2B	100.8 (7)	Cl1—Cd1—Cl3	83.73 (4)
C1B—S1B—C3B	100.3 (6)	Cl2—Cd1—Cl3	82.86 (4)
C2B—S1B—C3B	100.3 (6)	Cl2^i—Cd1—Cl3	98.07 (4)
S1B—C1B—H1BA	109.5	Cl1^i—Cd1—Cl3^i	83.77 (4)
S1B—C1B—H1BB	109.5	Cl1—Cd1—Cl3^i	95.51 (4)
H1BA—C1B—H1BB	109.5	Cl2—Cd1—Cl3^i	96.32 (4)
S1B—C1B—H1BC	109.5	Cl2^i—Cd1—Cl3^i	82.74 (4)
H1BA—C1B—H1BC	109.5	Cl3—Cd1—Cl3^i	178.93 (4)
H1BB—C1B—H1BC	109.5	Cl1^i—Cd1—Cd1^i	50.03 (3)
S1B—C2B—H2BA	109.5	Cl1—Cd1—Cd1^i	129.64 (3)
S1B—C2B—H2BB	109.5	Cl2—Cd1—Cd1^i	128.76 (3)
H2BA—C2B—H2BB	109.5	Cl2^i—Cd1—Cd1^i	50.55 (2)
S1B—C2B—H2BC	109.5	Cl3—Cd1—Cd1^i	130.43 (3)
H2BA—C2B—H2BC	109.5	Cl3^i—Cd1—Cd1^i	50.63 (3)
H2BB—C2B—H2BC	109.5	Cl1^i—Cd1—Cd1^ii	130.48 (3)
S1B—C3B—H3BA	109.5	Cl1—Cd1—Cd1^ii	49.84 (3)
S1B—C3B—H3BB	109.5	Cl2—Cd1—Cd1^ii	50.60 (2)
H3BA—C3B—H3BB	109.5	Cl2^i—Cd1—Cd1^ii	130.08 (3)
S1B—C3B—H3BC	109.5	Cl3—Cd1—Cd1^ii	50.77 (3)
H3BA—C3B—H3BC	109.5	Cl3^i—Cd1—Cd1^ii	128.17 (3)
H3BB—C3B—H3BC	109.5	Cd1^i—Cd1—Cd1^ii	178.80 (2)
Cl1^i—Cd1—Cl1	179.23 (2)	Cd1^ii—Cl1—Cd1	80.13 (3)
Cl1^i—Cd1—Cl2	95.27 (4)	Cd1—Cl2—Cd1^ii	78.85 (3)
Cl1—Cd1—Cl2	84.51 (4)	Cd1—Cl3—Cd1^ii	78.60 (3)
Cl1^i—Cd1—Cl2^i	84.62 (4)
Cl1^i—Cd1—Cl1—Cd1^ii	−115 (3)	Cl3—Cd1—Cl2—Cd1^ii	−43.77 (3)
Cl2—Cd1—Cl1—Cd1^ii	−41.12 (3)	Cl3^i—Cd1—Cl2—Cd1^ii	135.53 (4)
Cl2^i—Cd1—Cl1—Cd1^ii	139.82 (3)	Cd1^i—Cd1—Cl2—Cd1^ii	178.70 (3)
Cl3—Cd1—Cl1—Cd1^ii	42.28 (4)	Cl1^i—Cd1—Cl3—Cd1^ii	138.11 (4)
Cl3^i—Cd1—Cl1—Cd1^ii	−136.97 (4)	Cl1—Cd1—Cl3—Cd1^ii	−41.58 (3)
Cd1^i—Cd1—Cl1—Cd1^ii	−178.60 (3)	Cl2—Cd1—Cl3—Cd1^ii	43.64 (3)
Cl1^i—Cd1—Cl2—Cd1^ii	−140.17 (3)	Cl2^i—Cd1—Cl3—Cd1^ii	−136.36 (3)
Cl1—Cd1—Cl2—Cd1^ii	40.57 (3)	Cl3^i—Cd1—Cl3—Cd1^ii	3.3 (8)
Cl2^i—Cd1—Cl2—Cd1^ii	136.2 (18)	Cd1^i—Cd1—Cl3—Cd1^ii	179.87 (3)

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3C···Cl1^iii	0.96	2.72	3.596 (10)	152
C3—H3B···Cl1^iv	0.96	3.06	3.592 (9)	116

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