Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023901/wq3048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023901/wq3048Isup2.hkl |
CCDC reference: 969454
The design and construction of novel organically templated halometallates have attracted much attention due to their intriguing architectures and topologies (Wu et al., 2009; Arnby et al., 2004; Corradi et al., 1998; Subramanian & Hoffmann, 1992; Costin-Hogan et al., 2008) and their potential applications in many fields, including ferroelectricity, optics, magnetism, electrical conductivity and catalysis (Zhang & Xiong, 2012; Corradi et al., 1993, 2001; Martin & Greenwood, 1997; Willett et al., 2004; Yu et al., 2003). Based on the strategy of employing various organic N-heterocyclic/amine molecules as the templating agents, a large number of halometallates with interesting structures and useful properties have been obtained in acidic solutions under ambient/hydro(solvo)thermal conditions in the past two decades. It is known that the size, charge and form of the organic N-heterocyclic/amine molecules has a significant impact on the halometallate frameworks. Although some significant conclusions about the structures have been drawn (Thorn et al., 2005, 2006), it is still difficult to predict the structure of the obtained halometallate when a new organic N-heterocyclic/amine molecule is used, because the anionic halometallate framework may be modified. To introduce another kind of potential bridging inorganic anionic group into the halometallate framework is a useful strategy. In consideration of the potential diversity of coordination modes for the thiocyanate (SCN-) group, we focused on the structural characterization of organically templated halocadmates containing the SCN- group. Recently, several examples of organically templated halocadmates modified with SCN- groups have been obtained, including the chains [H2bp][CdCl2(SCN)2], [H2bp][Cd(SCN)4] (H2bp is ????), [H2bpp][Cd3Br(SCN)7] (H2bpp is ????), [H2bpy][CdBr2(SCN)2] (H2bpy is ?,?'-bipyridinediium), [H2bpe][Cd(SCN)4] (H2bpe is ????) and [H2dach][CdCl4] (H2dach is ????) (Jia et al., 2012) and tubes [H2pip]4[Cd3Br8(SCN)2(SO4)2(H2O)].4H2O (H2pip is piperidinediium) (Jin, Jia, Peng et al., 2011). Compared with the above-mentioned cases, two-dimensional organically templated halocadmates modified with SCN- groups are rare. We report here the synthesis and crystal structure of a two-dimensional trimethylsulfonium-templated chlorocadmate, (I), containing the SCN- group.
A mixture 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 temperture. After filtering the mixtures, CdCl2 (0.92 g, 5 mmol) and NH4SCN (0.38 g, 5 mmol) were added to the filtrate and stirring continued for 2 min. Hydrochloric acid (0.97 g, 5 mmol, 37% solution in water) was added to the above solution until all the precipitates dissolved. The solution was left to evaporate at room temperature in air for 4 d and afforded colourless crystals suitable for single-crystal X-ray diffraction. IR spectra (4000–400 cm-1) were recorded on a Shimadzu IR Prestige-21 spectrophotometer with KBr pellets. IR (KBr pellet, ν, cm-1): 3015 (m), 2927 (m), 2852 (w), 2106 (s), 1625 (s), 1414 (m), 1340 (w), 1039 (m), 938 (w), 755 (w), 462 (m).
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C atoms were included in calculated positions and were refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C).
The title salt, catena-poly[trimethylsulfonium [µ2-chlorido-di-µ2-thiocyanato-cadmate(II)]], (I), has an asymmetric unit consisting of a trimethylsulphonium cation with an anion consisting of a CdII cation, two coordinated isothiocyanates and a chloride ligand. Both thiocyanate ligands and the chloride ligand bridge to inversion-related CdII centres resulting in a cadmium complex which has a distorted octahedral geometry, with two N-coordinated NCS- ligands, two S-coordinated NCS- ligands and two chloride ligands (Fig. 1). IR spectroscopic analysis of (I) revealed a strong peak at 2106 cm-1 that is consistent with the presence of SCN- groups. As is shown in Fig. 1, the local coordination environment around the crystallographically unique Cd1 cation can be best described as a distorted octahedron with coordination from two thiocyanate N atoms (N1 and N2), two thiocyanate S atoms (S2 and S3iii; symmetry codes as in Fig. 1) and two bridging Cl atoms (Cl1 and Cl1ii). The equatorial plane for the Cd octahedron is occupied by one µ2-Cl1 ion, one SCN- S atom (Siii) and two SCN- N atoms (N1 and N2), whereas the axis is occupied by the µ2-Cl1ii ion and the SCN- S atom (S2) (symmetry codes as in Fig. 1). Note that the same atoms adopt the trans arrangement. The Cd1—N distances of 2.311 (5) and 2.286 (5) Å the Cd1—S distances of 2.7334 (18) and 2.765 (2) Å are comparable with those observed in previously reported compounds (Yu et al., 2008; Jin, Jia, Wang et al., 2011), however, the bridged Cd1—Cl distances of 2.6204 (16) and 2.6440 (16) Å are shorter than distances observed in other reported compounds (Jin, Jia, Wang et al., 2011) which are 2.7636 (9) and 2.7347 (9) Å. The µ2-SCN- groups bridge the CdII centres into a one-dimensional zigzag chain extended along the [110] direction consisting of eight-membered Cd2(SCN)2 loops (Fig. 2). The atoms of the resulting eight-membered Cd2(SCN)2 ring are nearly coplanar (mean deviation = 0.0060 Å); this is similar to the Cd2(SCN)2 ring in [Cd(SCN)2(dach)] (Jin, Jia, Wang et al., 2011), but is different to the chair-like conformation exhibited by many other Cd2(SCN)2 rings whose mean deviations from the least-squares plane are generally larger (ca 0.7 Å) (Yu et al., 2008; Vujovic et al., 2004; Bose et al., 2004; Jia et al., 2012). Between the zigzag chains, the Cl/Clii and Clv/Clvi atoms bridge the Cd1/Cd1ii and Cdv/Cdvi atoms (symmetry codes as in Fig. 3), respectively, forming a two-dimensional layer structure extending along the ab plane. Thus, two Cl atoms, six CdII atoms and four SCN- groups form a 20-membered ring, as shown in Fig. 3. The two-dimensional structure is also stabilized by weak Cl···S interactions with distances of 3.517 (3) Å. The Cd···Cd distance bridged by Cl atoms is 3.9110 (12) Å, while the Cd···Cd distances in the Cd2(SCN)2 rings are 5.9848 (19) and 6.1697 (17) Å. The C3H9S+ cations are located in the inter-layer space and the charges of the cations are balanced by the anionic layers. The bond lengths and angles of the C3H9S+ cations are in agreement with those reported in the literature (Hess et al., 2007). The anionic layers are linked by trimethylsulfonium cations by weak intermolecular C1—H1C···Cl1(x-1, y, z-1) hydrogen bonds, forming a three-dimensional structure (Table 2 and Fig. 4).
In the Cambridge Structural Database (CSD; Version 5.33; Allen 2002), the reported two-dimensional organically templated halocadmates with an introduced SCN-group, can be divided as two types: (a) salt complexes containing organic cations and polymeric anions, with the polymeric anions constructed from Cd atoms and SCN- groups only without halogen atoms, for example, [BMIM]2[Cd2(SCN)6] (BMIM = 1-butyl-3-methylimidazolium; Gao et al., 2008); (b) two-dimensional layered cadmium–thiocyanate coordination polymers, where the organic templating agents are coordinated to the Cd atoms, for example, [Cd(SCN)2(dach)] (Jin, Jia, Peng et al., 2011; OR Jin, Jia, Wang et al., 2011). But the title salt does not fit into either of these types and contains organic cations and novel polymeric anions constructed by Cd atoms, µ2-SCN- groups and bridging Cl atoms, which means that halogen atoms have been incorporated successfully into the anionic layers of the two-dimensional organically templated halocadmates.
In summary, a rare two-dimensional organically templated halocadmate with a novel polymeric anion has been synthetized and characterized. There are no complex with such an anion in the CSD.
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).
(C3H9S)[CdCl(NCS)2] | V = 586.1 (2) Å3 |
Mr = 341.17 | Z = 2 |
Triclinic, P1 | F(000) = 332 |
Hall symbol: -P 1 | Dx = 1.933 Mg m−3 |
a = 8.0676 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.8427 (18) Å | µ = 2.58 mm−1 |
c = 9.0977 (18) Å | T = 293 K |
α = 105.64 (3)° | Block, colourless |
β = 105.18 (3)° | 0.2 × 0.2 × 0.2 mm |
γ = 98.56 (3)° |
Rigaku Mercury2 diffractometer | 2251 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
CCD_Profile_fitting scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→11 |
Tmin = 0.599, Tmax = 0.602 | l = −11→11 |
6135 measured reflections | 3 standard reflections every 180 reflections |
2689 independent reflections | intensity decay: none |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0488P)2 + 1.3869P] where P = (Fo2 + 2Fc2)/3 |
2689 reflections | (Δ/σ)max = 0.001 |
112 parameters | Δρmax = 2.43 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
(C3H9S)[CdCl(NCS)2] | γ = 98.56 (3)° |
Mr = 341.17 | V = 586.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0676 (16) Å | Mo Kα radiation |
b = 8.8427 (18) Å | µ = 2.58 mm−1 |
c = 9.0977 (18) Å | T = 293 K |
α = 105.64 (3)° | 0.2 × 0.2 × 0.2 mm |
β = 105.18 (3)° |
Rigaku Mercury2 diffractometer | 2251 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | Rint = 0.037 |
Tmin = 0.599, Tmax = 0.602 | 3 standard reflections every 180 reflections |
6135 measured reflections | intensity decay: none |
2689 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.09 | Δρmax = 2.43 e Å−3 |
2689 reflections | Δρmin = −0.81 e Å−3 |
112 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 | ||
Cd1 | 0.86066 (5) | 0.16318 (5) | 0.51766 (5) | 0.03287 (15) | |
Cl1 | 0.9935 (2) | −0.01563 (17) | 0.68752 (17) | 0.0396 (3) | |
S3 | 0.8315 (2) | 0.6143 (2) | 0.2782 (2) | 0.0525 (5) | |
S2 | 0.6964 (2) | 0.27693 (18) | 0.7376 (2) | 0.0450 (4) | |
N2 | 0.8133 (7) | 0.3471 (6) | 0.3859 (7) | 0.0466 (13) | |
N1 | 0.5958 (7) | −0.0174 (6) | 0.3573 (7) | 0.0489 (14) | |
C5 | 0.8253 (7) | 0.4587 (7) | 0.3425 (7) | 0.0342 (12) | |
C4 | 0.5235 (8) | 0.1251 (7) | 0.6802 (6) | 0.0354 (12) | |
S1 | 0.2606 (2) | 0.1828 (2) | 0.14064 (19) | 0.0457 (4) | |
C1 | 0.0818 (9) | 0.2742 (8) | 0.0798 (8) | 0.0480 (15) | |
H1A | 0.1280 | 0.3858 | 0.0952 | 0.072* | |
H1B | 0.0049 | 0.2665 | 0.1434 | 0.072* | |
H1C | 0.0167 | 0.2191 | −0.0318 | 0.072* | |
C2 | 0.4073 (10) | 0.2480 (13) | 0.0441 (9) | 0.077 (3) | |
H2A | 0.4274 | 0.3631 | 0.0684 | 0.116* | |
H2B | 0.3568 | 0.1964 | −0.0702 | 0.116* | |
H2C | 0.5175 | 0.2198 | 0.0814 | 0.116* | |
C3 | 0.3675 (9) | 0.3103 (9) | 0.3439 (7) | 0.0518 (17) | |
H3A | 0.4792 | 0.2860 | 0.3847 | 0.078* | |
H3B | 0.2945 | 0.2921 | 0.4085 | 0.078* | |
H3C | 0.3862 | 0.4213 | 0.3480 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0327 (2) | 0.0279 (2) | 0.0392 (2) | 0.00456 (15) | 0.01092 (17) | 0.01454 (17) |
Cl1 | 0.0512 (8) | 0.0372 (7) | 0.0403 (7) | 0.0134 (6) | 0.0212 (6) | 0.0201 (6) |
S3 | 0.0507 (9) | 0.0420 (9) | 0.0542 (10) | −0.0053 (7) | −0.0063 (8) | 0.0295 (8) |
S2 | 0.0393 (8) | 0.0330 (8) | 0.0515 (9) | −0.0021 (6) | 0.0151 (7) | 0.0010 (7) |
N2 | 0.035 (3) | 0.038 (3) | 0.061 (3) | −0.001 (2) | 0.001 (2) | 0.025 (3) |
N1 | 0.042 (3) | 0.042 (3) | 0.051 (3) | −0.012 (2) | 0.021 (2) | 0.001 (2) |
C5 | 0.028 (3) | 0.035 (3) | 0.033 (3) | 0.004 (2) | 0.001 (2) | 0.011 (2) |
C4 | 0.040 (3) | 0.037 (3) | 0.030 (3) | 0.011 (2) | 0.012 (2) | 0.009 (2) |
S1 | 0.0481 (9) | 0.0432 (9) | 0.0422 (9) | 0.0075 (7) | 0.0139 (7) | 0.0103 (7) |
C1 | 0.047 (4) | 0.053 (4) | 0.043 (3) | 0.015 (3) | 0.011 (3) | 0.015 (3) |
C2 | 0.051 (4) | 0.127 (8) | 0.055 (5) | 0.008 (5) | 0.023 (4) | 0.032 (5) |
C3 | 0.050 (4) | 0.068 (5) | 0.029 (3) | 0.011 (3) | 0.004 (3) | 0.013 (3) |
Cd1—N2 | 2.286 (5) | S1—C2 | 1.766 (7) |
Cd1—N1 | 2.311 (5) | S1—C3 | 1.785 (6) |
Cd1—Cl1i | 2.6204 (16) | S1—C1 | 1.791 (7) |
Cd1—Cl1 | 2.6440 (16) | C1—H1A | 0.9600 |
Cd1—S2 | 2.7334 (18) | C1—H1B | 0.9600 |
Cd1—S3ii | 2.765 (2) | C1—H1C | 0.9600 |
Cl1—Cd1i | 2.6204 (16) | C2—H2A | 0.9600 |
S3—C5 | 1.633 (6) | C2—H2B | 0.9600 |
S3—Cd1ii | 2.765 (2) | C2—H2C | 0.9600 |
S2—C4 | 1.644 (6) | C3—H3A | 0.9600 |
N2—C5 | 1.158 (7) | C3—H3B | 0.9600 |
N1—C4iii | 1.153 (7) | C3—H3C | 0.9600 |
C4—N1iii | 1.153 (7) | ||
N2—Cd1—N1 | 93.2 (2) | C2—S1—C3 | 101.4 (4) |
N2—Cd1—Cl1i | 91.08 (15) | C2—S1—C1 | 102.0 (4) |
N1—Cd1—Cl1i | 87.67 (14) | C3—S1—C1 | 101.3 (3) |
N2—Cd1—Cl1 | 166.65 (13) | S1—C1—H1A | 109.5 |
N1—Cd1—Cl1 | 98.94 (16) | S1—C1—H1B | 109.5 |
Cl1i—Cd1—Cl1 | 84.04 (5) | H1A—C1—H1B | 109.5 |
N2—Cd1—S2 | 95.95 (15) | S1—C1—H1C | 109.5 |
N1—Cd1—S2 | 88.36 (14) | H1A—C1—H1C | 109.5 |
Cl1i—Cd1—S2 | 172.11 (5) | H1B—C1—H1C | 109.5 |
Cl1—Cd1—S2 | 89.86 (5) | S1—C2—H2A | 109.5 |
N2—Cd1—S3ii | 87.08 (13) | S1—C2—H2B | 109.5 |
N1—Cd1—S3ii | 176.85 (14) | H2A—C2—H2B | 109.5 |
Cl1i—Cd1—S3ii | 95.46 (6) | S1—C2—H2C | 109.5 |
Cl1—Cd1—S3ii | 81.05 (5) | H2A—C2—H2C | 109.5 |
S2—Cd1—S3ii | 88.49 (6) | H2B—C2—H2C | 109.5 |
Cd1i—Cl1—Cd1 | 95.96 (5) | S1—C3—H3A | 109.5 |
C5—S3—Cd1ii | 105.4 (2) | S1—C3—H3B | 109.5 |
C4—S2—Cd1 | 100.4 (2) | H3A—C3—H3B | 109.5 |
C5—N2—Cd1 | 165.0 (5) | S1—C3—H3C | 109.5 |
C4iii—N1—Cd1 | 157.6 (5) | H3A—C3—H3C | 109.5 |
N2—C5—S3 | 177.2 (5) | H3B—C3—H3C | 109.5 |
N1iii—C4—S2 | 178.4 (6) | ||
N2—Cd1—Cl1—Cd1i | −69.0 (6) | N1—Cd1—N2—C5 | −178 (2) |
N1—Cd1—Cl1—Cd1i | 86.69 (14) | Cl1i—Cd1—N2—C5 | −91 (2) |
Cl1i—Cd1—Cl1—Cd1i | 0.0 | Cl1—Cd1—N2—C5 | −23 (3) |
S2—Cd1—Cl1—Cd1i | 175.00 (5) | S2—Cd1—N2—C5 | 93 (2) |
S3ii—Cd1—Cl1—Cd1i | −96.50 (7) | S3ii—Cd1—N2—C5 | 5 (2) |
N2—Cd1—S2—C4 | 112.2 (2) | N2—Cd1—N1—C4iii | −161.2 (13) |
N1—Cd1—S2—C4 | 19.1 (3) | Cl1i—Cd1—N1—C4iii | 107.8 (13) |
Cl1—Cd1—S2—C4 | −79.9 (2) | Cl1—Cd1—N1—C4iii | 24.2 (13) |
S3ii—Cd1—S2—C4 | −160.9 (2) | S2—Cd1—N1—C4iii | −65.4 (13) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1C···Cl1iv | 0.96 | 2.76 | 3.606 (7) | 147 |
Symmetry code: (iv) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | (C3H9S)[CdCl(NCS)2] |
Mr | 341.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.0676 (16), 8.8427 (18), 9.0977 (18) |
α, β, γ (°) | 105.64 (3), 105.18 (3), 98.56 (3) |
V (Å3) | 586.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.58 |
Crystal size (mm) | 0.2 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Rigaku Mercury2 diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.599, 0.602 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6135, 2689, 2251 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.115, 1.09 |
No. of reflections | 2689 |
No. of parameters | 112 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.43, −0.81 |
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—H1C···Cl1i | 0.96 | 2.76 | 3.606 (7) | 146.9 |
Symmetry code: (i) x−1, y, z−1. |