Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229613034207/ku3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034207/ku3119Sbsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229613034207/ku3119Cdsup3.hkl |
CCDC references: 978080; 978081
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.
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.
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 Uiso(H) = 1.5Ueq(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.
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—Cl3v 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.
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).
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. |
(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) Å3 | 0.36 × 0.32 × 0.28 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.045 | w = 1/[σ2(Fo2) + (0.0117P)2 + 2.4036P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00423 (10) |
(C3H9S)[SbCl4] | V = 2154.7 (7) Å3 |
Mr = 340.71 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.182 (3) Å | µ = 3.68 mm−1 |
b = 13.214 (3) Å | T = 293 K |
c = 12.374 (3) Å | 0.36 × 0.32 × 0.28 mm |
β = 91.58 (3)° |
Rigaku Mercury2 diffractometer | 2335 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.031 |
Tmin = 0.275, Tmax = 0.355 | 3 standard reflections every 180 reflections |
10903 measured reflections | intensity decay: none |
2461 independent reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.22 | Δρmax = 0.49 e Å−3 |
2461 reflections | Δρmin = −0.39 e Å−3 |
89 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Sb1—Cl3i | 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 |
Cl3i—Sb1—Cl1 | 81.87 (2) | S1—C2—H2C | 109.5 |
Cl3i—Sb1—Cl2 | 169.30 (3) | H2A—C2—H2C | 109.5 |
Cl3i—Sb1—Cl3 | 80.54 (2) | H2B—C2—H2C | 109.5 |
Cl3i—Sb1—Cl4 | 106.987 (15) | S1—C3—H3A | 109.5 |
Cl3i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cl3i | 0.96 | 2.83 | 3.765 (3) | 165 |
C1—H1B···Cl1ii | 0.96 | 2.83 | 3.771 (3) | 166 |
C2—H2C···Cl1 | 0.96 | 2.81 | 3.610 (3) | 142 |
C3—H3B···Cl2iii | 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. |
(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) Å3 | 0.2 × 0.2 × 0.2 mm |
Z = 4 |
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 on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.041P)2 + 0.750P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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+0.001xFc2λ3/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) |
(C3H9S)[CdCl3] | V = 924.6 (3) Å3 |
Mr = 295.91 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7443 (13) Å | µ = 3.37 mm−1 |
b = 9.0050 (18) Å | T = 293 K |
c = 15.224 (3) Å | 0.2 × 0.2 × 0.2 mm |
Rigaku Mercury2 diffractometer | 1990 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.038 |
Tmin = 0.500, Tmax = 0.513 | 3 standard reflections every 180 reflections |
8566 measured reflections | intensity decay: none |
2108 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 1.25 e Å−3 |
S = 1.01 | Δρmin = −0.79 e Å−3 |
2108 reflections | Absolute structure: Flack (1983), with 868 Friedel pairs |
117 parameters | Absolute structure parameter: −0.01 (7) |
198 restraints |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—Cl1i | 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—Cl2i | 2.6559 (11) |
S1B—C1B | 1.766 (9) | Cd1—Cl3 | 2.6596 (12) |
S1B—C2B | 1.769 (9) | Cd1—Cl3i | 2.6647 (11) |
S1B—C3B | 1.776 (9) | Cd1—Cd1i | 3.3723 (6) |
C1B—H1BA | 0.9600 | Cd1—Cd1ii | 3.3723 (7) |
C2—S1—C1 | 101.0 (4) | Cl1—Cd1—Cl2i | 95.58 (4) |
C2—S1—C3 | 101.1 (4) | Cl2—Cd1—Cl2i | 179.06 (3) |
C1—S1—C3 | 101.1 (4) | Cl1i—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) | Cl2i—Cd1—Cl3 | 98.07 (4) |
S1B—C1B—H1BA | 109.5 | Cl1i—Cd1—Cl3i | 83.77 (4) |
S1B—C1B—H1BB | 109.5 | Cl1—Cd1—Cl3i | 95.51 (4) |
H1BA—C1B—H1BB | 109.5 | Cl2—Cd1—Cl3i | 96.32 (4) |
S1B—C1B—H1BC | 109.5 | Cl2i—Cd1—Cl3i | 82.74 (4) |
H1BA—C1B—H1BC | 109.5 | Cl3—Cd1—Cl3i | 178.93 (4) |
H1BB—C1B—H1BC | 109.5 | Cl1i—Cd1—Cd1i | 50.03 (3) |
S1B—C2B—H2BA | 109.5 | Cl1—Cd1—Cd1i | 129.64 (3) |
S1B—C2B—H2BB | 109.5 | Cl2—Cd1—Cd1i | 128.76 (3) |
H2BA—C2B—H2BB | 109.5 | Cl2i—Cd1—Cd1i | 50.55 (2) |
S1B—C2B—H2BC | 109.5 | Cl3—Cd1—Cd1i | 130.43 (3) |
H2BA—C2B—H2BC | 109.5 | Cl3i—Cd1—Cd1i | 50.63 (3) |
H2BB—C2B—H2BC | 109.5 | Cl1i—Cd1—Cd1ii | 130.48 (3) |
S1B—C3B—H3BA | 109.5 | Cl1—Cd1—Cd1ii | 49.84 (3) |
S1B—C3B—H3BB | 109.5 | Cl2—Cd1—Cd1ii | 50.60 (2) |
H3BA—C3B—H3BB | 109.5 | Cl2i—Cd1—Cd1ii | 130.08 (3) |
S1B—C3B—H3BC | 109.5 | Cl3—Cd1—Cd1ii | 50.77 (3) |
H3BA—C3B—H3BC | 109.5 | Cl3i—Cd1—Cd1ii | 128.17 (3) |
H3BB—C3B—H3BC | 109.5 | Cd1i—Cd1—Cd1ii | 178.80 (2) |
Cl1i—Cd1—Cl1 | 179.23 (2) | Cd1ii—Cl1—Cd1 | 80.13 (3) |
Cl1i—Cd1—Cl2 | 95.27 (4) | Cd1—Cl2—Cd1ii | 78.85 (3) |
Cl1—Cd1—Cl2 | 84.51 (4) | Cd1—Cl3—Cd1ii | 78.60 (3) |
Cl1i—Cd1—Cl2i | 84.62 (4) | ||
Cl1i—Cd1—Cl1—Cd1ii | −115 (3) | Cl3—Cd1—Cl2—Cd1ii | −43.77 (3) |
Cl2—Cd1—Cl1—Cd1ii | −41.12 (3) | Cl3i—Cd1—Cl2—Cd1ii | 135.53 (4) |
Cl2i—Cd1—Cl1—Cd1ii | 139.82 (3) | Cd1i—Cd1—Cl2—Cd1ii | 178.70 (3) |
Cl3—Cd1—Cl1—Cd1ii | 42.28 (4) | Cl1i—Cd1—Cl3—Cd1ii | 138.11 (4) |
Cl3i—Cd1—Cl1—Cd1ii | −136.97 (4) | Cl1—Cd1—Cl3—Cd1ii | −41.58 (3) |
Cd1i—Cd1—Cl1—Cd1ii | −178.60 (3) | Cl2—Cd1—Cl3—Cd1ii | 43.64 (3) |
Cl1i—Cd1—Cl2—Cd1ii | −140.17 (3) | Cl2i—Cd1—Cl3—Cd1ii | −136.36 (3) |
Cl1—Cd1—Cl2—Cd1ii | 40.57 (3) | Cl3i—Cd1—Cl3—Cd1ii | 3.3 (8) |
Cl2i—Cd1—Cl2—Cd1ii | 136.2 (18) | Cd1i—Cd1—Cl3—Cd1ii | 179.87 (3) |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3C···Cl1iii | 0.96 | 2.72 | 3.596 (10) | 152 |
C3—H3B···Cl1iv | 0.96 | 3.06 | 3.592 (9) | 116 |
Symmetry codes: (iii) x+1/2, −y+1/2, −z+1; (iv) x+1, y, z. |
Experimental details
(Sb) | (Cd) | |
Crystal data | ||
Chemical formula | (C3H9S)[SbCl4] | (C3H9S)[CdCl3] |
Mr | 340.71 | 295.91 |
Crystal system, space group | Monoclinic, C2/c | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 13.182 (3), 13.214 (3), 12.374 (3) | 6.7443 (13), 9.0050 (18), 15.224 (3) |
α, β, γ (°) | 90, 91.58 (3), 90 | 90, 90, 90 |
V (Å3) | 2154.7 (7) | 924.6 (3) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.68 | 3.37 |
Crystal size (mm) | 0.36 × 0.32 × 0.28 | 0.2 × 0.2 × 0.2 |
Data collection | ||
Diffractometer | Rigaku Mercury2 diffractometer | Rigaku Mercury2 diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.275, 0.355 | 0.500, 0.513 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10903, 2461, 2335 | 8566, 2108, 1990 |
Rint | 0.031 | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.045, 1.22 | 0.029, 0.077, 1.01 |
No. of reflections | 2461 | 2108 |
No. of parameters | 89 | 117 |
No. of restraints | 0 | 198 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.39 | 1.25, −0.79 |
Absolute structure | ? | Flack (1983), with 868 Friedel pairs |
Absolute structure parameter | ? | −0.01 (7) |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2005), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cl3i | 0.96 | 2.83 | 3.765 (3) | 165 |
C1—H1B···Cl1ii | 0.96 | 2.83 | 3.771 (3) | 166 |
C2—H2C···Cl1 | 0.96 | 2.81 | 3.610 (3) | 142 |
C3—H3B···Cl2iii | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3C···Cl1i | 0.96 | 2.72 | 3.596 (10) | 152.3 |
C3—H3B···Cl1ii | 0.96 | 3.06 | 3.592 (9) | 116.1 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1, y, z. |