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Acta Cryst. (2007). E63, m1461-m1462    [ doi:10.1107/S1600536807016984 ]

Poly[bis(sulfolane-[kappa]O)di-[mu]2-thiocyanato-cadmium(II)]

X.-Q. Wang, J.-D. Fan, W.-T. Yu, D. Xu and W.-L. Liu

Abstract top

In the title complex, [Cd(SCN)2(C4H8O2S)2]n, the CdII atom, on an inversion centre, is within a distorted N2S2O2 octahedron and the five-membered ring has a distorted envelope conformation. In the crystal structure, neighbouring Cd atoms are connected by -SCN- bridges, leading to the formation of an infinite three-dimensional -Cd-NCS-Cd- network.

Comment top

A variety of polymeric structures of the monometallic thiocyanates of the IIB metals and of their Lewis base adducts are interesting themes of structural chemistry and nonlinear optics (Lipkowski, 1990; Wang, et al., 2000; Chenskaya et al., 2000; Zhu et al., 2006). According to the hard and soft acids and bases (HSAB) theory (Pearson, 1966), cadmium is a rather soft metal, although its softness is less than that of mercury or lead. Therefore, it is expected that the N and S atoms of the thiocyanate ion are able to bond easily with Cd, and that SCN-bridged polymeric complexes are stable (Yamaguchi et al., 1985; Taniguchi et al., 1986, 1987; Taniguchi & Ouchi, 1987a,b; Ouchi & Taniguchi, 1988; Ozutsmi et al., 1989). In the present work, the title sulfolane adduct of Cd(SCN)2, (I), has been characterized.

In (I), the CdII atom is within a distorted N2S2O2 octahedron (Fig. 1). The Cd—N, Cd—O and Cd—S bonds are shorter, longer and shorter, respectively, than the sums of the ionic radii, i.e. 2.41, 2.30 and 2.79 Å, respectively (Shannon, 1976). The bond angles (Table 1) deviate significantly from ideal octahedral geometry. The C—N—Cd and C—S—Cd bond angles (close to 180° and 90°, respectively) show that the these groups are quasi-linear and significantly bent, respectively.

The five-membered S1/C1–C4 ring is not planar, having a distorted envelope conformation, with C2 as the flap atom displaced by 0.589 (3) Å from the mean plane of the other four atoms. It has also a pseudo twofold axis passing through atom S1 and the mid-point of the C2—C3 bond, as evidenced by the torsion angles (Table 1).

In the crystal structure, neighbouring Cd atoms are connected by –SCN– bridges, which leads to the formation of an infinite three-dimensional –Cd—NCS—Cd–network.

Related literature top

For related literature, see: Chenskaya et al. (2000); Lipkowski (1990); Ouchi & Taniguchi (1988); Ozutsmi et al. (1989); Pearson (1966); Shannon (1976); Taniguchi et al. (1986, 1987); Taniguchi & Ouchi (1987a,b); Wang et al. (2000); Yamaguchi et al. (1985); Zhu et al. (2006).

Experimental top

Cd(SCN)2 was prepared by the reaction of Cd(NO3)2.4H2O (6.170 g, 20 mmol) and NH4SCN (3.045 g, 40 mmol) in water (6 ml). The crystalline powder of Cd(SCN)2 (3.438 g, 15 mmol) was dissolved in water (50 ml) at about 313 K, and then sulfolane (2.5 ml) was added. The mixture was left standing at room temperature, yielding colourless crystals of (I) suitable for X-ray vrystal structure analysis. IR (Nicolet 20 SX FTIR spectrometer; cm-1): 2945.88 and 2878.38 [ν(CH)], 2107.92 and 2078.99 [ν(CN)], 1447.39, 1409.78, 1384.71, 1290.21 and 1254.53 [δ(HCH)], 1204.39, 1145.57, 1108.92, 1086.75, 1031.78, 991.28, 672.10, 570.85 and 516.85 [ν(SO)], 967.17 and 907.39 [2δ(SCN)], 735.75[ν(CS)], 465.75, 418.50 and 407.89 [δ(SCN)]. Raman (NXR FT-Raman spectrometer using InGaAs laser at 1064 nm, cm-1): 3008.5, 2977.6 and 2947.9 [ν(CH)], 2107.0 [ν(CN)], 1450.5, 1253.0 [δ(HCH)], 1132.8, 1095.2, 1073.9, 1026.2, 666.5 and 561.5 [ν(SO)], 967.0 and 877.3 [2δ(SCN)], 777.9 and 734.0 [ν(CS)], 476.9 and 444.9 [δ(SCN)], 385.5 [ν(CdN)], 260.9 [ν(CdO)], 193.7, 161.7 and 129.0 [ν(CdS)].

Refinement top

H atoms were positioned geometrically, with C—H = 0.97 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A fragment of the polymeric structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Atoms N1A, O2A, S2A and S2B are at the symmetry positions (1 - x, -y, 1 - z), (1 - x, -y, 1 - z), (x - 1, y, z) and (2 - x, -y, 1 - z), respectively.
Poly[Bis(sulfolane-κO)di-µ2-thiocyanato-cadmium(II)] top
Crystal data top
[Cd(SCN)2(C4H8O2S)2]Z = 1
Mr = 468.89F(000) = 234
Triclinic, P1Dx = 1.830 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 5.9138 (1) ÅCell parameters from 3568 reflections
b = 8.5561 (2) Åθ = 2.4–27.6°
c = 9.4413 (2) ŵ = 1.79 mm−1
α = 115.246 (1)°T = 294 K
β = 96.147 (1)°Prism, colourless
γ = 94.512 (1)°0.31 × 0.23 × 0.19 mm
V = 425.48 (2) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1937 independent reflections
Radiation source: fine-focus sealed tube1881 reflections with I > 2σ(I)
graphiteRint = 0.014
φ and ω scansθmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan
(APEX2; Bruker, 2005)		h = −7→6
Tmin = 0.585, Tmax = 0.710k = −10→11
3857 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0333P)2 + 0.1407P]
where P = (Fo2 + 2Fc2)/3
1937 reflections(Δ/σ)max = 0.017
97 parametersΔρmax = 0.42 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
[Cd(SCN)2(C4H8O2S)2]γ = 94.512 (1)°
Mr = 468.89V = 425.48 (2) Å3
Triclinic, P1Z = 1
a = 5.9138 (1) ÅMo Kα radiation
b = 8.5561 (2) ŵ = 1.79 mm−1
c = 9.4413 (2) ÅT = 294 K
α = 115.246 (1)°0.31 × 0.23 × 0.19 mm
β = 96.147 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1937 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2005)		1881 reflections with I > 2σ(I)
Tmin = 0.585, Tmax = 0.710Rint = 0.014
3857 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.020H-atom parameters constrained
wR(F2) = 0.056Δρmax = 0.42 e Å−3
S = 1.08Δρmin = −0.62 e Å−3
1937 reflectionsAbsolute structure: ?
97 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. IR (Nicolet 20 SX FTIR spectrometer; cm-1): 2945.88 and 2878.38 [ν(CH)], 2107.92 and 2078.99 [ν(CN)], 1447.39, 1409.78, 1384.71, 1290.21 and 1254.53 [δ(HCH)], 1204.39, 1145.57, 1108.92, 1086.75, 1031.78, 991.28, 672.10, 570.85 and 516.85 [ν(SO)], 967.17 and 907.39 [2δ(SCN)], 735.75[ν(CS)], 465.75, 418.50 and 407.89 [δ(SCN)]. Raman (NXR FT-Raman spectrometer using InGaAs laser at 1064 nm, cm-1): 3008.5, 2977.6 and 2947.9 [ν(CH)], 2107.0 [ν(CN)], 1450.5, 1253.0 [δ(HCH)], 1132.8, 1095.2, 1073.9, 1026.2, 666.5 and 561.5 [ν(SO)], 967.0 and 877.3 [2δ(SCN)], 777.9 and 734.0 [ν(CS)], 476.9 and 444.9 [δ(SCN)], 385.5 [ν(CdN)], 260.9 [ν(CdO)], 193.7, 161.7 and 129.0 [ν(CdS)].

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 (Å2) top
xyzUiso*/Ueq
Cd10.50000.00000.50000.03334 (8)
S10.31205 (8)0.13344 (6)0.20978 (6)0.03717 (11)
S21.32208 (8)0.25374 (7)0.72442 (6)0.04356 (13)
O10.2601 (3)−0.0393 (2)0.0826 (2)0.0583 (4)
O20.4885 (3)0.1593 (2)0.3410 (2)0.0489 (4)
N10.8515 (3)0.1461 (2)0.6227 (2)0.0418 (4)
C10.0585 (4)0.2137 (3)0.2838 (3)0.0474 (5)
H1A−0.07820.14040.21300.057*
H1B0.05450.21890.38820.057*
C20.0768 (5)0.3954 (3)0.2911 (3)0.0604 (6)
H2A0.17520.47830.38750.072*
H2B−0.07370.43290.29000.072*
C30.1777 (5)0.3854 (3)0.1473 (3)0.0559 (6)
H3A0.06620.32170.05180.067*
H3B0.22210.50160.15710.067*
C40.3848 (4)0.2918 (3)0.1400 (3)0.0507 (5)
H4A0.51890.37270.20690.061*
H4B0.41670.23570.03220.061*
C51.0453 (3)0.1882 (2)0.6641 (2)0.0313 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.01888 (11)0.03835 (12)0.04516 (12)0.00468 (7)0.00290 (7)0.02091 (9)
S10.0352 (2)0.0394 (2)0.0443 (2)0.01258 (19)0.00901 (19)0.0234 (2)
S20.0227 (2)0.0446 (3)0.0495 (3)0.00226 (19)0.00154 (19)0.0089 (2)
O10.0628 (11)0.0463 (8)0.0592 (9)0.0139 (8)0.0077 (8)0.0165 (7)
O20.0399 (8)0.0564 (9)0.0595 (9)0.0059 (7)0.0001 (7)0.0359 (8)
N10.0239 (8)0.0412 (8)0.0523 (9)0.0050 (6)0.0061 (7)0.0129 (7)
C10.0368 (11)0.0630 (13)0.0554 (12)0.0179 (10)0.0174 (9)0.0338 (11)
C20.0557 (15)0.0549 (13)0.0758 (16)0.0272 (12)0.0236 (13)0.0273 (12)
C30.0543 (14)0.0506 (12)0.0758 (16)0.0154 (11)0.0105 (12)0.0386 (12)
C40.0526 (13)0.0558 (12)0.0649 (13)0.0190 (10)0.0239 (11)0.0410 (11)
C50.0281 (9)0.0300 (8)0.0364 (8)0.0073 (6)0.0075 (7)0.0139 (6)
Geometric parameters (Å, °) top
Cd1—N1i2.251 (2)C1—H1B0.9700
Cd1—N12.251 (2)C2—C31.513 (4)
Cd1—O22.4192 (17)C2—H2A0.9700
Cd1—O2i2.4192 (17)C2—H2B0.9700
Cd1—S2ii2.6875 (11)C3—C41.507 (3)
Cd1—S2iii2.6875 (11)C3—H3A0.9700
S2—Cd1iv2.6875 (11)C3—H3B0.9700
O1—S11.4341 (19)C4—S11.785 (2)
O2—S11.4580 (17)C4—H4A0.9700
C1—C21.521 (3)C4—H4B0.9700
C1—S11.785 (2)C5—N11.147 (3)
C1—H1A0.9700C5—S21.644 (2)
C2—C1—S1103.85 (16)N1i—Cd1—N1180.00 (10)
C2—C1—H1A111.0N1i—Cd1—O290.81 (7)
S1—C1—H1A111.0N1—Cd1—O289.19 (7)
C2—C1—H1B111.0N1i—Cd1—O2i89.19 (7)
S1—C1—H1B111.0N1—Cd1—O2i90.81 (7)
H1A—C1—H1B109.0O2—Cd1—O2i180.0
C1—C2—C3107.17 (19)N1i—Cd1—S2ii88.25 (6)
C1—C2—H2A110.3N1—Cd1—S2ii91.75 (6)
C3—C2—H2A110.3O2—Cd1—S2ii89.81 (6)
C1—C2—H2B110.3O2i—Cd1—S2ii90.19 (6)
C3—C2—H2B110.3N1i—Cd1—S2iii91.75 (6)
H2A—C2—H2B108.5N1—Cd1—S2iii88.25 (6)
C4—C3—C2106.69 (19)O2—Cd1—S2iii90.19 (6)
C4—C3—H3A110.4O2i—Cd1—S2iii89.81 (6)
C2—C3—H3A110.4S2ii—Cd1—S2iii180.00 (2)
C4—C3—H3B110.4C5—N1—Cd1165.48 (15)
C2—C3—H3B110.4S1—O2—Cd1127.40 (10)
H3A—C3—H3B108.6O1—S1—O2116.68 (11)
C3—C4—S1105.34 (16)O1—S1—C4111.75 (13)
C3—C4—H4A110.7O2—S1—C4108.46 (12)
S1—C4—H4A110.7O1—S1—C1111.28 (13)
C3—C4—H4B110.7O2—S1—C1109.89 (12)
S1—C4—H4B110.7C4—S1—C196.99 (11)
H4A—C4—H4B108.8C5—S2—Cd1iv101.40 (7)
N1—C5—S2178.52 (17)
O2—Cd1—N1—C5−101.9 (7)C2—C1—S1—C4−15.3 (2)
O2i—Cd1—N1—C578.1 (7)C2—C1—S1—O1−131.90 (18)
S2ii—Cd1—N1—C5−12.1 (7)C1—C2—C3—C4−48.4 (3)
S2iii—Cd1—N1—C5167.9 (7)C2—C3—C4—S135.0 (3)
N1i—Cd1—O2—S1−5.53 (13)C3—C4—S1—C1−11.2 (2)
N1—Cd1—O2—S1174.47 (13)C3—C4—S1—O1105.05 (19)
S2ii—Cd1—O2—S182.72 (13)C3—C4—S1—O2−124.95 (19)
S2iii—Cd1—O2—S1−97.28 (13)Cd1—O2—S1—O1−54.85 (16)
S1—C1—C2—C337.9 (2)Cd1—O2—S1—C4177.92 (11)
C2—C1—S1—O297.29 (18)Cd1—O2—S1—C173.02 (15)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1; (iii) x−1, y, z; (iv) x+1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N12.251 (2)C5—N11.147 (3)
Cd1—O22.4192 (17)C5—S21.644 (2)
Cd1—S2i2.6875 (11)
N1—C5—S2178.52 (17)O2—Cd1—S2i89.81 (6)
N1ii—Cd1—N1180.00 (10)N1—Cd1—S2iii88.25 (6)
N1ii—Cd1—O290.81 (7)O2—Cd1—S2iii90.19 (6)
N1—Cd1—O289.19 (7)S2i—Cd1—S2iii180.00 (2)
O2—Cd1—O2ii180.0C5—N1—Cd1165.48 (15)
N1—Cd1—S2i91.75 (6)C5—S2—Cd1iv101.40 (7)
S1—C1—C2—C337.9 (2)C2—C3—C4—S135.0 (3)
C2—C1—S1—C4−15.3 (2)C3—C4—S1—C1−11.2 (2)
C1—C2—C3—C4−48.4 (3)
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) x+1, y, z.
Acknowledgements top

This work was supported by the Foundation for the Authors of National Excellent Doctoral Dissertations of China (grant No. 200539) and the National Natural Science Foundation of China (grant Nos. 60476020, 60608010 and 50672049).

references
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