Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807016984/hk2227sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807016984/hk2227Isup2.hkl |
CCDC reference: 646646
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.020
- wR factor = 0.056
- Data-to-parameter ratio = 20.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) . 500 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 500 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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)].
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).
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.
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).
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).
[Cd(SCN)2(C4H8O2S)2] | Z = 1 |
Mr = 468.89 | F(000) = 234 |
Triclinic, P1 | Dx = 1.830 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 5.9138 (1) Å | Cell parameters from 3568 reflections |
b = 8.5561 (2) Å | θ = 2.4–27.6° |
c = 9.4413 (2) Å | µ = 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 |
Bruker APEXII CCD area-detector diffractometer | 1937 independent reflections |
Radiation source: fine-focus sealed tube | 1881 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 27.6°, θmin = 2.4° |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | h = −7→6 |
Tmin = 0.585, Tmax = 0.710 | k = −10→11 |
3857 measured reflections | l = −12→12 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-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 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.62 e Å−3 |
[Cd(SCN)2(C4H8O2S)2] | γ = 94.512 (1)° |
Mr = 468.89 | V = 425.48 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.9138 (1) Å | Mo Kα radiation |
b = 8.5561 (2) Å | µ = 1.79 mm−1 |
c = 9.4413 (2) Å | T = 294 K |
α = 115.246 (1)° | 0.31 × 0.23 × 0.19 mm |
β = 96.147 (1)° |
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 = 0.710 | Rint = 0.014 |
3857 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.42 e Å−3 |
1937 reflections | Δρmin = −0.62 e Å−3 |
97 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.5000 | 0.0000 | 0.5000 | 0.03334 (8) | |
S1 | 0.31205 (8) | 0.13344 (6) | 0.20978 (6) | 0.03717 (11) | |
S2 | 1.32208 (8) | 0.25374 (7) | 0.72442 (6) | 0.04356 (13) | |
O1 | 0.2601 (3) | −0.0393 (2) | 0.0826 (2) | 0.0583 (4) | |
O2 | 0.4885 (3) | 0.1593 (2) | 0.3410 (2) | 0.0489 (4) | |
N1 | 0.8515 (3) | 0.1461 (2) | 0.6227 (2) | 0.0418 (4) | |
C1 | 0.0585 (4) | 0.2137 (3) | 0.2838 (3) | 0.0474 (5) | |
H1A | −0.0782 | 0.1404 | 0.2130 | 0.057* | |
H1B | 0.0545 | 0.2189 | 0.3882 | 0.057* | |
C2 | 0.0768 (5) | 0.3954 (3) | 0.2911 (3) | 0.0604 (6) | |
H2A | 0.1752 | 0.4783 | 0.3875 | 0.072* | |
H2B | −0.0737 | 0.4329 | 0.2900 | 0.072* | |
C3 | 0.1777 (5) | 0.3854 (3) | 0.1473 (3) | 0.0559 (6) | |
H3A | 0.0662 | 0.3217 | 0.0518 | 0.067* | |
H3B | 0.2221 | 0.5016 | 0.1571 | 0.067* | |
C4 | 0.3848 (4) | 0.2918 (3) | 0.1400 (3) | 0.0507 (5) | |
H4A | 0.5189 | 0.3727 | 0.2069 | 0.061* | |
H4B | 0.4167 | 0.2357 | 0.0322 | 0.061* | |
C5 | 1.0453 (3) | 0.1882 (2) | 0.6641 (2) | 0.0313 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01888 (11) | 0.03835 (12) | 0.04516 (12) | 0.00468 (7) | 0.00290 (7) | 0.02091 (9) |
S1 | 0.0352 (2) | 0.0394 (2) | 0.0443 (2) | 0.01258 (19) | 0.00901 (19) | 0.0234 (2) |
S2 | 0.0227 (2) | 0.0446 (3) | 0.0495 (3) | 0.00226 (19) | 0.00154 (19) | 0.0089 (2) |
O1 | 0.0628 (11) | 0.0463 (8) | 0.0592 (9) | 0.0139 (8) | 0.0077 (8) | 0.0165 (7) |
O2 | 0.0399 (8) | 0.0564 (9) | 0.0595 (9) | 0.0059 (7) | 0.0001 (7) | 0.0359 (8) |
N1 | 0.0239 (8) | 0.0412 (8) | 0.0523 (9) | 0.0050 (6) | 0.0061 (7) | 0.0129 (7) |
C1 | 0.0368 (11) | 0.0630 (13) | 0.0554 (12) | 0.0179 (10) | 0.0174 (9) | 0.0338 (11) |
C2 | 0.0557 (15) | 0.0549 (13) | 0.0758 (16) | 0.0272 (12) | 0.0236 (13) | 0.0273 (12) |
C3 | 0.0543 (14) | 0.0506 (12) | 0.0758 (16) | 0.0154 (11) | 0.0105 (12) | 0.0386 (12) |
C4 | 0.0526 (13) | 0.0558 (12) | 0.0649 (13) | 0.0190 (10) | 0.0239 (11) | 0.0410 (11) |
C5 | 0.0281 (9) | 0.0300 (8) | 0.0364 (8) | 0.0073 (6) | 0.0075 (7) | 0.0139 (6) |
Cd1—N1i | 2.251 (2) | C1—H1B | 0.9700 |
Cd1—N1 | 2.251 (2) | C2—C3 | 1.513 (4) |
Cd1—O2 | 2.4192 (17) | C2—H2A | 0.9700 |
Cd1—O2i | 2.4192 (17) | C2—H2B | 0.9700 |
Cd1—S2ii | 2.6875 (11) | C3—C4 | 1.507 (3) |
Cd1—S2iii | 2.6875 (11) | C3—H3A | 0.9700 |
S2—Cd1iv | 2.6875 (11) | C3—H3B | 0.9700 |
O1—S1 | 1.4341 (19) | C4—S1 | 1.785 (2) |
O2—S1 | 1.4580 (17) | C4—H4A | 0.9700 |
C1—C2 | 1.521 (3) | C4—H4B | 0.9700 |
C1—S1 | 1.785 (2) | C5—N1 | 1.147 (3) |
C1—H1A | 0.9700 | C5—S2 | 1.644 (2) |
C2—C1—S1 | 103.85 (16) | N1i—Cd1—N1 | 180.00 (10) |
C2—C1—H1A | 111.0 | N1i—Cd1—O2 | 90.81 (7) |
S1—C1—H1A | 111.0 | N1—Cd1—O2 | 89.19 (7) |
C2—C1—H1B | 111.0 | N1i—Cd1—O2i | 89.19 (7) |
S1—C1—H1B | 111.0 | N1—Cd1—O2i | 90.81 (7) |
H1A—C1—H1B | 109.0 | O2—Cd1—O2i | 180.0 |
C1—C2—C3 | 107.17 (19) | N1i—Cd1—S2ii | 88.25 (6) |
C1—C2—H2A | 110.3 | N1—Cd1—S2ii | 91.75 (6) |
C3—C2—H2A | 110.3 | O2—Cd1—S2ii | 89.81 (6) |
C1—C2—H2B | 110.3 | O2i—Cd1—S2ii | 90.19 (6) |
C3—C2—H2B | 110.3 | N1i—Cd1—S2iii | 91.75 (6) |
H2A—C2—H2B | 108.5 | N1—Cd1—S2iii | 88.25 (6) |
C4—C3—C2 | 106.69 (19) | O2—Cd1—S2iii | 90.19 (6) |
C4—C3—H3A | 110.4 | O2i—Cd1—S2iii | 89.81 (6) |
C2—C3—H3A | 110.4 | S2ii—Cd1—S2iii | 180.00 (2) |
C4—C3—H3B | 110.4 | C5—N1—Cd1 | 165.48 (15) |
C2—C3—H3B | 110.4 | S1—O2—Cd1 | 127.40 (10) |
H3A—C3—H3B | 108.6 | O1—S1—O2 | 116.68 (11) |
C3—C4—S1 | 105.34 (16) | O1—S1—C4 | 111.75 (13) |
C3—C4—H4A | 110.7 | O2—S1—C4 | 108.46 (12) |
S1—C4—H4A | 110.7 | O1—S1—C1 | 111.28 (13) |
C3—C4—H4B | 110.7 | O2—S1—C1 | 109.89 (12) |
S1—C4—H4B | 110.7 | C4—S1—C1 | 96.99 (11) |
H4A—C4—H4B | 108.8 | C5—S2—Cd1iv | 101.40 (7) |
N1—C5—S2 | 178.52 (17) | ||
O2—Cd1—N1—C5 | −101.9 (7) | C2—C1—S1—C4 | −15.3 (2) |
O2i—Cd1—N1—C5 | 78.1 (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—C5 | 167.9 (7) | C2—C3—C4—S1 | 35.0 (3) |
N1i—Cd1—O2—S1 | −5.53 (13) | C3—C4—S1—C1 | −11.2 (2) |
N1—Cd1—O2—S1 | 174.47 (13) | C3—C4—S1—O1 | 105.05 (19) |
S2ii—Cd1—O2—S1 | 82.72 (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—C3 | 37.9 (2) | Cd1—O2—S1—C4 | 177.92 (11) |
C2—C1—S1—O2 | 97.29 (18) | Cd1—O2—S1—C1 | 73.02 (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. |
Experimental details
Crystal data | |
Chemical formula | [Cd(SCN)2(C4H8O2S)2] |
Mr | 468.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 5.9138 (1), 8.5561 (2), 9.4413 (2) |
α, β, γ (°) | 115.246 (1), 96.147 (1), 94.512 (1) |
V (Å3) | 425.48 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.79 |
Crystal size (mm) | 0.31 × 0.23 × 0.19 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (APEX2; Bruker, 2005) |
Tmin, Tmax | 0.585, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3857, 1937, 1881 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.056, 1.08 |
No. of reflections | 1937 |
No. of parameters | 97 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.62 |
Computer programs: APEX2 (Bruker, 2005), APEX2, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), WinGX (Farrugia, 1999).
Cd1—N1 | 2.251 (2) | C5—N1 | 1.147 (3) |
Cd1—O2 | 2.4192 (17) | C5—S2 | 1.644 (2) |
Cd1—S2i | 2.6875 (11) | ||
N1—C5—S2 | 178.52 (17) | O2—Cd1—S2i | 89.81 (6) |
N1ii—Cd1—N1 | 180.00 (10) | N1—Cd1—S2iii | 88.25 (6) |
N1ii—Cd1—O2 | 90.81 (7) | O2—Cd1—S2iii | 90.19 (6) |
N1—Cd1—O2 | 89.19 (7) | S2i—Cd1—S2iii | 180.00 (2) |
O2—Cd1—O2ii | 180.0 | C5—N1—Cd1 | 165.48 (15) |
N1—Cd1—S2i | 91.75 (6) | C5—S2—Cd1iv | 101.40 (7) |
S1—C1—C2—C3 | 37.9 (2) | C2—C3—C4—S1 | 35.0 (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. |
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.