Download citation
Download citation
link to html
The title polymeric complex, [Cd(SCN)2(C12H12N2O)], exhibits a three-dimensional framework in which each CdII atom is bridged by two η-1,3-(SCN) groups, forming a double-stranded chain. The unique CdII atom lies on an inversion centre and the coordination sphere is completed by two terminal N atoms from two different 4,4′-oxy­dianiline (4,4′-Oda) ligands, furnishing a CdS2N4 octahedral geometry. Adjacent polymeric double-stranded chains are linked via the 4,4′-Oda ligands, which lie across twofold rotation axes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014305/gd1168sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014305/gd1168Isup2.hkl
Contains datablock I

CCDC reference: 175073

Comment top

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.

Related literature top

For related literature, see: Chen et al. (1999); Ram et al. (1981); Taniguchi & Ouchi (1987); Taniguchi, Sugita & Ouchi (1987); Yang et al. (2001).

Experimental top

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%.

Refinement top

All H atoms were treated as riding, with C—H = 0.96 Å.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the coordination environment in (I), with 30% probability displacement ellipsoids [symmetry codes: (i) -x, -y, 1 - z; (ii) 1/2 - x, -1/2 - y, 1 - z; (iii) x - 1/2, 1/2 + y, z].
[Figure 2] Fig. 2. A view of the three-dimensional framework of (I); the 4,4'-oxydianiline ligand is simplified to a stick for clarity.
poly[Cadmium(II)-µ-4,4'-oxydianiline-N:N'-di-µ-thiocyanato-N:S] top
Crystal data top
[Cd(C12H12N2O)(CNS)2]F(000) = 848
Mr = 428.80Dx = 1.809 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 9.441 (4) ÅCell parameters from 25 reflections
b = 8.085 (3) Åθ = 7–14°
c = 20.666 (11) ŵ = 1.66 mm1
β = 93.490 (1)°T = 293 K
V = 1574.5 (12) Å3Block, colourless
Z = 40.38 × 0.35 × 0.29 mm
Data collection top
Siemens R3m
diffractometer
1433 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
Graphite monochromatorθmax = 27.0°, θmin = 3.3°
ω scansh = 012
Absorption correction: semi-empirical (using intensity measurements)
based on ψ-scan (Kopfman & Huber, 1968)
k = 010
Tmin = 0.555, Tmax = 0.618l = 2726
1833 measured reflections2 standard reflections every 200 reflections
1717 independent reflections intensity decay: none
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-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 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Cd(C12H12N2O)(CNS)2]V = 1574.5 (12) Å3
Mr = 428.80Z = 4
Monoclinic, C2/cMo Kα radiation
a = 9.441 (4) ŵ = 1.66 mm1
b = 8.085 (3) ÅT = 293 K
c = 20.666 (11) Å0.38 × 0.35 × 0.29 mm
β = 93.490 (1)°
Data collection top
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 = 0.6182 standard reflections every 200 reflections
1833 measured reflections intensity decay: none
1717 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.07Δρmax = 0.49 e Å3
1717 reflectionsΔρmin = 0.36 e Å3
103 parameters
Special details top

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
Cd10.00000.00000.50000.02878 (15)
C10.1479 (3)0.3798 (4)0.53864 (15)0.0270 (6)
C20.1891 (4)0.0104 (4)0.64003 (15)0.0279 (6)
C30.1521 (4)0.1143 (5)0.68226 (17)0.0384 (8)
H3A0.05380.14070.68610.080*
C40.2560 (4)0.2005 (4)0.71909 (17)0.0389 (8)
H4A0.23010.28780.74760.080*
C50.3977 (3)0.1604 (4)0.71383 (15)0.0296 (7)
C60.4359 (4)0.0382 (4)0.67143 (17)0.0331 (7)
H6A0.53430.01180.66780.080*
C70.3311 (4)0.0463 (4)0.63408 (17)0.0317 (7)
H7A0.35760.12970.60400.080*
N10.0760 (3)0.2677 (3)0.52703 (15)0.0364 (7)
N20.0815 (3)0.0997 (3)0.60249 (13)0.0309 (6)
O10.50000.2531 (4)0.75000.0379 (8)
S10.24723 (10)0.54422 (12)0.55763 (6)0.0440 (3)
H2B0.00090.10390.62190.080*
H2A0.11730.20110.59590.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0293 (2)0.0264 (2)0.0298 (2)0.00725 (13)0.00561 (12)0.00048 (13)
C10.0246 (15)0.0250 (15)0.0316 (16)0.0005 (12)0.0042 (12)0.0020 (13)
C20.0320 (16)0.0274 (15)0.0237 (14)0.0002 (13)0.0025 (12)0.0027 (12)
C30.0298 (17)0.048 (2)0.0368 (19)0.0087 (15)0.0030 (14)0.0064 (16)
C40.0396 (19)0.042 (2)0.0339 (19)0.0101 (16)0.0036 (15)0.0126 (16)
C50.0323 (16)0.0273 (16)0.0277 (16)0.0014 (13)0.0093 (13)0.0023 (13)
C60.0263 (16)0.0380 (18)0.0349 (17)0.0002 (13)0.0013 (13)0.0004 (14)
C70.0321 (17)0.0292 (15)0.0340 (17)0.0001 (13)0.0035 (13)0.0033 (13)
N10.0350 (15)0.0282 (15)0.0463 (17)0.0064 (12)0.0044 (13)0.0053 (13)
N20.0297 (14)0.0314 (14)0.0313 (14)0.0023 (11)0.0011 (11)0.0015 (11)
O10.0417 (19)0.0290 (17)0.0406 (19)0.0000.0181 (16)0.000
S10.0277 (4)0.0306 (4)0.0747 (7)0.0084 (3)0.0113 (4)0.0211 (4)
Geometric parameters (Å, º) top
Cd1—N12.338 (3)C3—H3A0.9600
Cd1—N1i2.338 (3)C4—C51.387 (5)
Cd1—N2i2.352 (3)C4—H4A0.9599
Cd1—N22.352 (3)C5—C61.383 (5)
Cd1—S1ii2.7544 (13)C5—O11.402 (3)
Cd1—S1iii2.7544 (13)C6—C71.396 (5)
C1—N11.149 (4)C6—H6A0.9600
C1—S11.660 (3)C7—H7A0.9600
C2—C71.384 (5)N2—H2B0.8978
C2—C31.392 (5)N2—H2A0.9002
C2—N21.435 (4)O1—C5iv1.402 (3)
C3—C41.391 (5)S1—Cd1v2.7544 (13)
N1—Cd1—N1i180.0C5—C4—C3119.4 (3)
N1—Cd1—N2i88.66 (10)C5—C4—H4A120.2
N1i—Cd1—N2i91.34 (10)C3—C4—H4A120.4
N1—Cd1—N291.34 (10)C6—C5—C4120.4 (3)
N1i—Cd1—N288.66 (10)C6—C5—O1121.5 (3)
N2i—Cd1—N2180.0C4—C5—O1118.0 (3)
N1—Cd1—S1ii87.83 (8)C5—C6—C7119.8 (3)
N1i—Cd1—S1ii92.17 (8)C5—C6—H6A119.9
N2i—Cd1—S1ii84.24 (7)C7—C6—H6A120.3
N2—Cd1—S1ii95.76 (7)C2—C7—C6120.4 (3)
N1—Cd1—S1iii92.17 (8)C2—C7—H7A119.8
N1i—Cd1—S1iii87.83 (8)C6—C7—H7A119.8
N2i—Cd1—S1iii95.76 (7)C1—N1—Cd1161.7 (3)
N2—Cd1—S1iii84.24 (7)C2—N2—Cd1119.76 (19)
S1ii—Cd1—S1iii180.0C2—N2—H2B112.4
N1—C1—S1177.6 (3)Cd1—N2—H2B99.9
C7—C2—C3119.3 (3)C2—N2—H2A106.3
C7—C2—N2120.2 (3)Cd1—N2—H2A106.3
C3—C2—N2120.5 (3)H2B—N2—H2A112.2
C4—C3—C2120.7 (3)C5iv—O1—C5115.4 (3)
C4—C3—H3A119.7C1—S1—Cd1v106.59 (11)
C2—C3—H3A119.6
Symmetry codes: (i) x, y, z+1; (ii) x+1/2, y1/2, z+1; (iii) x1/2, y+1/2, z; (iv) x+1, y, z+3/2; (v) x+1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···S1iii0.902.913.438 (3)119
N2—H2A···S1vi0.902.553.431 (3)167
Symmetry codes: (iii) x1/2, y+1/2, z; (vi) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cd(C12H12N2O)(CNS)2]
Mr428.80
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)9.441 (4), 8.085 (3), 20.666 (11)
β (°) 93.490 (1)
V3)1574.5 (12)
Z4
Radiation typeMo Kα
µ (mm1)1.66
Crystal size (mm)0.38 × 0.35 × 0.29
Data collection
DiffractometerSiemens R3m
diffractometer
Absorption correctionSemi-empirical (using intensity measurements)
based on ψ-scan (Kopfman & Huber, 1968)
Tmin, Tmax0.555, 0.618
No. of measured, independent and
observed [I > 2σ(I)] reflections
1833, 1717, 1433
Rint0.021
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.083, 1.07
No. of reflections1717
No. of parameters103
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.36

Computer programs: SHELXTL-Plus (Siemens, 1990), SHELXTL-Plus, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Cd1—N12.338 (3)C1—S11.660 (3)
Cd1—N22.352 (3)C2—N21.435 (4)
Cd1—S1i2.7544 (13)C5—O11.402 (3)
C1—N11.149 (4)
N1—Cd1—N2ii88.66 (10)N1—C1—S1177.6 (3)
N1—Cd1—N291.34 (10)C1—N1—Cd1161.7 (3)
N1—Cd1—S1i87.83 (8)C2—N2—Cd1119.76 (19)
N2—Cd1—S1i95.76 (7)H2B—N2—H2A112.2
N1—Cd1—S1iii92.17 (8)C5iv—O1—C5115.4 (3)
N2—Cd1—S1iii84.24 (7)C1—S1—Cd1v106.59 (11)
Symmetry codes: (i) x+1/2, y1/2, z+1; (ii) x, y, z+1; (iii) x1/2, y+1/2, z; (iv) x+1, y, z+3/2; (v) x+1/2, y1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···S1iii0.902.913.438 (3)119
N2—H2A···S1vi0.902.553.431 (3)167
Symmetry codes: (iii) x1/2, y+1/2, z; (vi) x, y+1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds