Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014305/gd1168sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014305/gd1168Isup2.hkl |
CCDC reference: 175073
For related literature, see: Chen et al. (1999); Ram et al. (1981); Taniguchi & Ouchi (1987); Taniguchi, Sugita & Ouchi (1987); Yang et al. (2001).
A hot ethanol-water (1:1 v/v) solution (5 ml) of 4,4'-oxydianiline (0.50 g, 2.5 mmol) was added to an aqueous solution (5 ml) of Cd(SCN)2 (0.57 g, 2.5 mmol). After vigorous stirring, the solution was adjusted to pH 5 by addition of dilute HNO3 and the resulting solution was allowed to evaporate at room temperature for 6 d, resulting in the formation of colourless crystals of (I) (yield 56%). IR data (ν, cm-1): 3329 (m), 3237 (s), 3149 (m), 3017 (w), 2869 (w), 2115 (versus), 1876 (w), 1590 (m), 1499 (s), 1211 (s), 1094 (w), 991 (s), 925 (w), 828 (w), 785 (m), 573 (m), 523 (m), 439 (w). Elemental analysis, found: C 39.5, H 2.9, N 12.9, S 14.9%; calculated for C14H12CdN4OS2: C 39.2, H 2.8, N 13.1, S 15.0%.
Data collection: SHELXTL-Plus (Siemens, 1990); cell refinement: SHELXTL-Plus; data reduction: SHELXTL-Plus; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.
[Cd(C12H12N2O)(CNS)2] | F(000) = 848 |
Mr = 428.80 | Dx = 1.809 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.441 (4) Å | Cell parameters from 25 reflections |
b = 8.085 (3) Å | θ = 7–14° |
c = 20.666 (11) Å | µ = 1.66 mm−1 |
β = 93.490 (1)° | T = 293 K |
V = 1574.5 (12) Å3 | Block, colourless |
Z = 4 | 0.38 × 0.35 × 0.29 mm |
Siemens R3m diffractometer | 1433 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.0°, θmin = 3.3° |
ω scans | h = 0→12 |
Absorption correction: semi-empirical (using intensity measurements) based on ψ-scan (Kopfman & Huber, 1968) | k = 0→10 |
Tmin = 0.555, Tmax = 0.618 | l = −27→26 |
1833 measured reflections | 2 standard reflections every 200 reflections |
1717 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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0504P)2 + 0.4572P] where P = (Fo2 + 2Fc2)/3 |
1717 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Cd(C12H12N2O)(CNS)2] | V = 1574.5 (12) Å3 |
Mr = 428.80 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.441 (4) Å | µ = 1.66 mm−1 |
b = 8.085 (3) Å | T = 293 K |
c = 20.666 (11) Å | 0.38 × 0.35 × 0.29 mm |
β = 93.490 (1)° |
Siemens R3m diffractometer | 1433 reflections with I > 2σ(I) |
Absorption correction: semi-empirical (using intensity measurements) based on ψ-scan (Kopfman & Huber, 1968) | Rint = 0.021 |
Tmin = 0.555, Tmax = 0.618 | 2 standard reflections every 200 reflections |
1833 measured reflections | intensity decay: none |
1717 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.49 e Å−3 |
1717 reflections | Δρmin = −0.36 e Å−3 |
103 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 | 0.0000 | 0.0000 | 0.5000 | 0.02878 (15) | |
C1 | 0.1479 (3) | −0.3798 (4) | 0.53864 (15) | 0.0270 (6) | |
C2 | 0.1891 (4) | 0.0104 (4) | 0.64003 (15) | 0.0279 (6) | |
C3 | 0.1521 (4) | −0.1143 (5) | 0.68226 (17) | 0.0384 (8) | |
H3A | 0.0538 | −0.1407 | 0.6861 | 0.080* | |
C4 | 0.2560 (4) | −0.2005 (4) | 0.71909 (17) | 0.0389 (8) | |
H4A | 0.2301 | −0.2878 | 0.7476 | 0.080* | |
C5 | 0.3977 (3) | −0.1604 (4) | 0.71383 (15) | 0.0296 (7) | |
C6 | 0.4359 (4) | −0.0382 (4) | 0.67143 (17) | 0.0331 (7) | |
H6A | 0.5343 | −0.0118 | 0.6678 | 0.080* | |
C7 | 0.3311 (4) | 0.0463 (4) | 0.63408 (17) | 0.0317 (7) | |
H7A | 0.3576 | 0.1297 | 0.6040 | 0.080* | |
N1 | 0.0760 (3) | −0.2677 (3) | 0.52703 (15) | 0.0364 (7) | |
N2 | 0.0815 (3) | 0.0997 (3) | 0.60249 (13) | 0.0309 (6) | |
O1 | 0.5000 | −0.2531 (4) | 0.7500 | 0.0379 (8) | |
S1 | 0.24723 (10) | −0.54422 (12) | 0.55763 (6) | 0.0440 (3) | |
H2B | −0.0009 | 0.1039 | 0.6219 | 0.080* | |
H2A | 0.1173 | 0.2011 | 0.5959 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0293 (2) | 0.0264 (2) | 0.0298 (2) | 0.00725 (13) | −0.00561 (12) | 0.00048 (13) |
C1 | 0.0246 (15) | 0.0250 (15) | 0.0316 (16) | 0.0005 (12) | 0.0042 (12) | 0.0020 (13) |
C2 | 0.0320 (16) | 0.0274 (15) | 0.0237 (14) | −0.0002 (13) | −0.0025 (12) | −0.0027 (12) |
C3 | 0.0298 (17) | 0.048 (2) | 0.0368 (19) | −0.0087 (15) | −0.0030 (14) | 0.0064 (16) |
C4 | 0.0396 (19) | 0.042 (2) | 0.0339 (19) | −0.0101 (16) | −0.0036 (15) | 0.0126 (16) |
C5 | 0.0323 (16) | 0.0273 (16) | 0.0277 (16) | 0.0014 (13) | −0.0093 (13) | −0.0023 (13) |
C6 | 0.0263 (16) | 0.0380 (18) | 0.0349 (17) | −0.0002 (13) | 0.0013 (13) | −0.0004 (14) |
C7 | 0.0321 (17) | 0.0292 (15) | 0.0340 (17) | −0.0001 (13) | 0.0035 (13) | 0.0033 (13) |
N1 | 0.0350 (15) | 0.0282 (15) | 0.0463 (17) | 0.0064 (12) | 0.0044 (13) | 0.0053 (13) |
N2 | 0.0297 (14) | 0.0314 (14) | 0.0313 (14) | 0.0023 (11) | −0.0011 (11) | −0.0015 (11) |
O1 | 0.0417 (19) | 0.0290 (17) | 0.0406 (19) | 0.000 | −0.0181 (16) | 0.000 |
S1 | 0.0277 (4) | 0.0306 (4) | 0.0747 (7) | 0.0084 (3) | 0.0113 (4) | 0.0211 (4) |
Cd1—N1 | 2.338 (3) | C3—H3A | 0.9600 |
Cd1—N1i | 2.338 (3) | C4—C5 | 1.387 (5) |
Cd1—N2i | 2.352 (3) | C4—H4A | 0.9599 |
Cd1—N2 | 2.352 (3) | C5—C6 | 1.383 (5) |
Cd1—S1ii | 2.7544 (13) | C5—O1 | 1.402 (3) |
Cd1—S1iii | 2.7544 (13) | C6—C7 | 1.396 (5) |
C1—N1 | 1.149 (4) | C6—H6A | 0.9600 |
C1—S1 | 1.660 (3) | C7—H7A | 0.9600 |
C2—C7 | 1.384 (5) | N2—H2B | 0.8978 |
C2—C3 | 1.392 (5) | N2—H2A | 0.9002 |
C2—N2 | 1.435 (4) | O1—C5iv | 1.402 (3) |
C3—C4 | 1.391 (5) | S1—Cd1v | 2.7544 (13) |
N1—Cd1—N1i | 180.0 | C5—C4—C3 | 119.4 (3) |
N1—Cd1—N2i | 88.66 (10) | C5—C4—H4A | 120.2 |
N1i—Cd1—N2i | 91.34 (10) | C3—C4—H4A | 120.4 |
N1—Cd1—N2 | 91.34 (10) | C6—C5—C4 | 120.4 (3) |
N1i—Cd1—N2 | 88.66 (10) | C6—C5—O1 | 121.5 (3) |
N2i—Cd1—N2 | 180.0 | C4—C5—O1 | 118.0 (3) |
N1—Cd1—S1ii | 87.83 (8) | C5—C6—C7 | 119.8 (3) |
N1i—Cd1—S1ii | 92.17 (8) | C5—C6—H6A | 119.9 |
N2i—Cd1—S1ii | 84.24 (7) | C7—C6—H6A | 120.3 |
N2—Cd1—S1ii | 95.76 (7) | C2—C7—C6 | 120.4 (3) |
N1—Cd1—S1iii | 92.17 (8) | C2—C7—H7A | 119.8 |
N1i—Cd1—S1iii | 87.83 (8) | C6—C7—H7A | 119.8 |
N2i—Cd1—S1iii | 95.76 (7) | C1—N1—Cd1 | 161.7 (3) |
N2—Cd1—S1iii | 84.24 (7) | C2—N2—Cd1 | 119.76 (19) |
S1ii—Cd1—S1iii | 180.0 | C2—N2—H2B | 112.4 |
N1—C1—S1 | 177.6 (3) | Cd1—N2—H2B | 99.9 |
C7—C2—C3 | 119.3 (3) | C2—N2—H2A | 106.3 |
C7—C2—N2 | 120.2 (3) | Cd1—N2—H2A | 106.3 |
C3—C2—N2 | 120.5 (3) | H2B—N2—H2A | 112.2 |
C4—C3—C2 | 120.7 (3) | C5iv—O1—C5 | 115.4 (3) |
C4—C3—H3A | 119.7 | C1—S1—Cd1v | 106.59 (11) |
C2—C3—H3A | 119.6 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1/2, −y−1/2, −z+1; (iii) x−1/2, y+1/2, z; (iv) −x+1, y, −z+3/2; (v) x+1/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···S1iii | 0.90 | 2.91 | 3.438 (3) | 119 |
N2—H2A···S1vi | 0.90 | 2.55 | 3.431 (3) | 167 |
Symmetry codes: (iii) x−1/2, y+1/2, z; (vi) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C12H12N2O)(CNS)2] |
Mr | 428.80 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.441 (4), 8.085 (3), 20.666 (11) |
β (°) | 93.490 (1) |
V (Å3) | 1574.5 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.66 |
Crystal size (mm) | 0.38 × 0.35 × 0.29 |
Data collection | |
Diffractometer | Siemens R3m diffractometer |
Absorption correction | Semi-empirical (using intensity measurements) based on ψ-scan (Kopfman & Huber, 1968) |
Tmin, Tmax | 0.555, 0.618 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1833, 1717, 1433 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.07 |
No. of reflections | 1717 |
No. of parameters | 103 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.36 |
Computer programs: SHELXTL-Plus (Siemens, 1990), SHELXTL-Plus, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cd1—N1 | 2.338 (3) | C1—S1 | 1.660 (3) |
Cd1—N2 | 2.352 (3) | C2—N2 | 1.435 (4) |
Cd1—S1i | 2.7544 (13) | C5—O1 | 1.402 (3) |
C1—N1 | 1.149 (4) | ||
N1—Cd1—N2ii | 88.66 (10) | N1—C1—S1 | 177.6 (3) |
N1—Cd1—N2 | 91.34 (10) | C1—N1—Cd1 | 161.7 (3) |
N1—Cd1—S1i | 87.83 (8) | C2—N2—Cd1 | 119.76 (19) |
N2—Cd1—S1i | 95.76 (7) | H2B—N2—H2A | 112.2 |
N1—Cd1—S1iii | 92.17 (8) | C5iv—O1—C5 | 115.4 (3) |
N2—Cd1—S1iii | 84.24 (7) | C1—S1—Cd1v | 106.59 (11) |
Symmetry codes: (i) −x+1/2, −y−1/2, −z+1; (ii) −x, −y, −z+1; (iii) x−1/2, y+1/2, z; (iv) −x+1, y, −z+3/2; (v) x+1/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···S1iii | 0.90 | 2.91 | 3.438 (3) | 119 |
N2—H2A···S1vi | 0.90 | 2.55 | 3.431 (3) | 167 |
Symmetry codes: (iii) x−1/2, y+1/2, z; (vi) x, y+1, z. |
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In the past two decades, polymeric Lewis base adducts of cadmium(II) thiocyanate, [Cd(SCN)2(L)2]n (where L is 2-, 3- or 4-methylpyridine, benzylamine, dibenzylamine, tri-m-tolyphosphine or 1H-1,2,4-triazole), exhibiting one-dimensional double-stranded chain structures comprising (–N—C—S—Cd)2 eight-membered rings in a chair conformation, have been documented (Ram et al., 1981; Taniguchi et al., 1987; Taniguchi & Ouchi, 1987). Recently, these one-dimensional chains have been linked into a two-dimensional hydrogen-bonded network by means of the bifunctional ligands imidazole and nicotinic acid (Chen et al., 1999; Yang et al., 2001). We report here the title covalent polymeric complex, [Cd(SCN)2(4,4'-Oda)]n, (I), where the organic ligand 4,4'-Oda (4,4'-Oda is 4,4'-oxydianiline) links the one-dimensional chains into a three-dimensional framework. \sch
In compound (I), the CdII ion is located at an inversion centre, and is octahedrally coordinated by a pair of S atoms from two (SCN)- groups, a pair of N atoms from another two (SCN)- groups and a pair of N atoms from two 4,4'-Oda organic ligands. Each pair of adjacent metal atoms is bridged by a pair of (SCN)- groups through opposite ends, resulting in a double-stranded chain comprising eight-membered (–N—C—S—Cd)2 rings in a chair conformation, with a Cd—Cd atom separation of 6.215 Å (Fig. 1). Within each unit cell, two such chains, related by the C-centring operation, run parallel to [110] at z = 1/2, and a further pair of chains, generated from the first pair by the twofold rotation axes, run parallel to [100] at z = 0.
As expected, adjacent double-stranded chains are linked by the 4,4'-Oda ligands, which lie across twofold rotation axes with a dihedral angle between the two aryl rings of 85.3 (3)°. This results in a three-dimensional framework, in which each double-stranded chain between adjacent layers runs towards the intercross direction, respectively *please explain*, with a Cd—Cd atom separation of 13.566 Å, as shown in Fig. 2. Each 4,4'-Oda ligand links one [110] chain to one [110] chain.