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Acta Cryst. (2007). E63, m2177    [ doi:10.1107/S1600536807033983 ]

catena-Poly[[bis(2-aminothiazole-[kappa]N)cadmium(II)]-di-[mu]-thiocyanato-[kappa]2N:S;[kappa]2S:N\]

S. W. Suh, C.-H. Kim and I. H. Kim

Abstract top

There are two independent Cd atoms in the title compound, [Cd(NCS)2(C3H4N2S)2]n; one lies on a twofold rotation axis and another is situated on an inversion center, but they are each in a distorted octahedral environment within N4S2 donor sets. One NH2 group is disordered equally over two positions. Each Cd atom is doubly bridged by thiocyanate ligands to neighboring Cd atoms. The 2-aminothiazole ligands are alternately coordinated to one Cd atom in a cis conformation and to the other Cd atom in a trans conformation. Overall, the structure is a one-dimensional zigzag chain.

Comment top

Crystal engineering of coordination complexes is motivated by the development of materials with useful properties such as catalytic, magnetic, electronic and optical (Braga et al., 1998). The pseudo-halide ions, e.g. CN-, SCN-, N3-, are known to build up 1-, 2- and 3-D structures by bridging metal centers (Vrieze & Koten, 1987). Using complementary organic ligands, such as aliphatic and aromatic amines, is known to play an important role in stabilizing multi-dimensional structures. Especially, aromatic heterocycles such as imidazole and thiazole derivatives represent an important class of ligands in coordination chemistry. A number of metal complexes of various imidazole derivatives have been synthesized and characterized (Balch et al., 1993; Costes et al., 1991). However, the frameworks of metal complexes containing thiazole derivatives have been considerably less investigated. Our research is focused on the development of novel supramolecular framework structures (Kim et al., 2004; Suh et al., 2005) utilizing the terminal and bridging properties of pseudo-halide ions, and the coordination behaviour of imidazole or thiazole derivatives as complementary organic ligands. Herein, we present the synthesis and structure determination of a cadmium(II) thiocyanato complex, (I), with 2-aminothiazole, Fig. 1. Each Cd atom has an octahedral geometry being hexa-coordinated by two amino-N atoms of 2-aminothiazole, and two N and two S atoms derived from four thiocyanate ligands. The 2-aminothiazole ligands are coordinated to the Cd(1) atom, which lies on a center of inversion, in a cis-conformation and to the Cd(2) atom, which lies on a 2-fold axis, in a trans manner. With the aforementioned bridging, an infinite 1-D zigzag chain results. Bond lengths and angles, Table 1, of the 2-aminothiazole ligand are similar to the related compound, tetrakis(2-aminothiazole)bis(isothiocyanate)cobalt(II) (Raper et al., 1984).

Related literature top

For related literature, see: Balch et al. (1993); Braga et al. (1998); Costes et al. (1991); Kim et al. (2004); Raper et al. (1984); Suh et al. (2005); Vrieze & Koten (1987).

Experimental top

A water-methanolic (2:1) solution (30 ml) of potassium thiocyanate (9 mmol, 0.88 g) was added to a water-methanolic (2:1) solution (30 ml) of Cd(NO3).4H2O (3 mmol, 0.93 g). To this mixture solution, a water-methanolic (2:1) solution (30 ml) of 2-aminothiazole (10 mmol, 1.00 g) was introduced, with stirring. The small amount of precipitates formed from the resulting solution were filtered off. The filtered solution was allowed to stand at room temperature. After a few days dark-yellow block crystals suitable for X-ray analysis were obtained. Analysis found: C 22.45, H 1.82, Cd 26.20, N 19.63, S 30.48%; C8H8CdN6S4 requires: C 22.40, H 1.88, Cd 26.21, N 19.60, S 29.90%.

Refinement top

The 2-aminothiazole-N16 atom was found to be disordered over two positions and from refinement, the final occupancy factors were 0.50. Positional parameters for the H atoms were calculated geometrically and constrained to ride on their attached atoms with C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Portion of the 1-D polymer in (I) showing the coordination geometries for the Cd(II) atoms and the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The disordered N17 atom of one 2-aminothiazole is omitted for clarity.
catena-Poly[[bis(2-aminothiazole-κN)cadmium(II)]-di-µ-thiocyanato- κ2N:S;κ2S:N] top
Crystal data top
[Cd(NCS)2(C3H4N2S)2]F(000) = 1680
Mr = 428.84Dx = 1.929 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 42 reflections
a = 18.7079 (18) Åθ = 4.7–12.5°
b = 9.0553 (13) ŵ = 2.04 mm−1
c = 18.661 (2) ÅT = 295 K
β = 110.918 (8)°Block, dark-yellow
V = 2953.0 (6) Å30.43 × 0.31 × 0.28 mm
Z = 8
Data collection top
Bruker P4
diffractometer		2860 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 26.5°, θmin = 2.3°
2θ/ω scansh = −1→23
Absorption correction: empirical (using intensity measurements)
(XSCANS; Bruker, 1996)		k = −11→1
Tmin = 0.474, Tmax = 0.599l = −23→22
3784 measured reflections3 standard reflections every 97 reflections
3046 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0328P)2 + 7.3517P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
3046 reflectionsΔρmax = 0.60 e Å−3
178 parametersΔρmin = −0.76 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00205 (11)
Crystal data top
[Cd(NCS)2(C3H4N2S)2]V = 2953.0 (6) Å3
Mr = 428.84Z = 8
Monoclinic, C2/cMo Kα radiation
a = 18.7079 (18) ŵ = 2.04 mm−1
b = 9.0553 (13) ÅT = 295 K
c = 18.661 (2) Å0.43 × 0.31 × 0.28 mm
β = 110.918 (8)°
Data collection top
Bruker P4
diffractometer		2860 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
(XSCANS; Bruker, 1996)		Rint = 0.025
Tmin = 0.474, Tmax = 0.599θmax = 26.5°
3784 measured reflections3 standard reflections every 97 reflections
3046 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.078Δρmax = 0.60 e Å−3
S = 1.11Δρmin = −0.76 e Å−3
3046 reflectionsAbsolute structure: ?
178 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
Cd10.00000.49223 (3)0.25000.03120 (11)
Cd2−0.25000.75000.00000.03061 (11)
S10.02580 (6)0.70476 (14)0.15739 (7)0.0705 (4)
C2−0.05999 (18)0.7030 (3)0.09211 (18)0.0362 (6)
N3−0.12043 (15)0.7042 (4)0.04573 (16)0.0436 (6)
S4−0.28158 (4)0.53426 (11)0.08902 (5)0.0418 (2)
C5−0.19410 (17)0.5119 (3)0.15148 (17)0.0312 (6)
N6−0.13341 (15)0.4965 (3)0.19488 (17)0.0410 (6)
S110.01787 (7)0.13108 (14)0.06482 (7)0.0750 (4)
C120.0430 (3)0.2810 (5)0.1256 (3)0.0649 (13)
N13−0.00175 (16)0.3065 (3)0.16315 (16)0.0413 (6)
C14−0.0586 (2)0.2022 (4)0.1446 (2)0.0486 (8)
H14A−0.09580.20190.16690.058*
C15−0.0577 (2)0.1020 (4)0.0934 (2)0.0541 (9)
H15−0.09330.02640.07560.065*
N160.1189 (7)0.3314 (14)0.1494 (7)0.079 (4)0.50
H16A0.13770.38200.19090.095*0.50
H16B0.14660.31160.12240.095*0.50
N170.0918 (7)0.3884 (15)0.1145 (6)0.079 (4)0.50
H17A0.09270.47560.13300.095*0.50
H17B0.12080.36710.08910.095*0.50
S21−0.24556 (6)1.13954 (10)0.18452 (6)0.0539 (2)
C22−0.2680 (2)1.0552 (4)0.0958 (2)0.0425 (7)
N23−0.23323 (15)0.9279 (3)0.09804 (15)0.0364 (6)
C24−0.1856 (2)0.8968 (4)0.17249 (18)0.0441 (7)
H24A−0.15570.81180.18470.053*
C25−0.1850 (2)0.9956 (4)0.2256 (2)0.0537 (9)
H25−0.15590.98780.27750.064*
N26−0.3175 (2)1.1158 (4)0.0324 (2)0.0675 (10)
H26A−0.32871.0712−0.01090.081*
H26B−0.33831.19950.03490.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02668 (17)0.03422 (18)0.02801 (17)0.0000.00404 (12)0.000
Cd20.02562 (17)0.03635 (19)0.02680 (17)0.00368 (11)0.00563 (12)0.00005 (11)
S10.0393 (5)0.0744 (7)0.0720 (7)−0.0191 (5)−0.0118 (5)0.0359 (6)
C20.0349 (16)0.0333 (15)0.0392 (16)0.0035 (12)0.0117 (13)0.0099 (13)
N30.0300 (14)0.0555 (17)0.0416 (15)0.0058 (12)0.0085 (12)0.0088 (13)
S40.0267 (4)0.0563 (5)0.0364 (4)−0.0026 (3)0.0039 (3)0.0128 (4)
C50.0323 (15)0.0317 (14)0.0305 (14)−0.0001 (11)0.0125 (12)0.0027 (11)
N60.0305 (14)0.0439 (15)0.0417 (15)0.0016 (11)0.0046 (12)0.0052 (12)
S110.0784 (7)0.0805 (8)0.0858 (8)−0.0401 (6)0.0535 (7)−0.0548 (7)
C120.068 (3)0.075 (3)0.071 (3)−0.043 (2)0.047 (2)−0.045 (2)
N130.0401 (14)0.0470 (16)0.0429 (14)−0.0187 (12)0.0224 (12)−0.0175 (13)
C140.0460 (19)0.0444 (18)0.063 (2)−0.0173 (16)0.0285 (17)−0.0110 (17)
C150.048 (2)0.0454 (19)0.070 (2)−0.0200 (16)0.0222 (18)−0.0173 (18)
N160.078 (8)0.092 (9)0.095 (8)−0.052 (6)0.066 (7)−0.054 (6)
N170.078 (8)0.092 (9)0.095 (8)−0.052 (6)0.066 (7)−0.054 (6)
S210.0670 (6)0.0438 (5)0.0630 (6)−0.0083 (4)0.0380 (5)−0.0182 (4)
C220.0494 (19)0.0349 (16)0.0509 (19)−0.0010 (14)0.0275 (16)−0.0030 (15)
N230.0415 (14)0.0350 (13)0.0347 (13)0.0013 (11)0.0157 (11)−0.0018 (11)
C240.0522 (19)0.0434 (18)0.0362 (16)−0.0038 (15)0.0152 (15)−0.0027 (14)
C250.066 (2)0.057 (2)0.0404 (19)−0.0098 (18)0.0227 (18)−0.0064 (16)
N260.079 (2)0.0529 (19)0.062 (2)0.0277 (18)0.0156 (19)0.0011 (17)
Geometric parameters (Å, °) top
Cd1—S1i2.7422 (11)C12—N171.399 (13)
Cd1—S12.7422 (11)N13—C141.371 (4)
Cd1—N62.336 (3)C14—C151.321 (5)
Cd1—N6i2.336 (3)C14—H14A0.9300
Cd1—N132.328 (3)C15—H150.9300
Cd1—N13i2.328 (3)N16—H16A0.8600
Cd2—S42.7616 (9)N16—H16B0.8600
Cd2—N3ii2.302 (3)N17—H17A0.8600
Cd2—N32.302 (3)N17—H17B0.8600
Cd2—S4ii2.7616 (9)S21—C221.733 (4)
Cd2—N232.373 (3)S21—C251.717 (4)
Cd2—N23ii2.373 (3)C22—N231.317 (4)
S1—C21.632 (3)C22—N261.332 (5)
C2—N31.153 (4)N23—C241.386 (4)
S4—C51.648 (3)C24—C251.332 (5)
C5—N61.144 (4)C24—H24A0.9300
S11—C121.723 (4)C25—H250.9300
S11—C151.701 (4)N26—H26A0.8600
C12—N131.289 (4)N26—H26B0.8600
C12—N161.404 (13)
S1i—Cd1—S190.85 (7)C24—N23—Cd2119.7 (2)
N6—Cd1—S196.40 (7)N3—C2—S1178.8 (3)
N6i—Cd1—S182.24 (8)N6—C5—S4179.9 (4)
N6—Cd1—S1i82.24 (8)C12—N13—C14109.6 (3)
N6i—Cd1—S1i96.40 (7)N13—C12—S11114.9 (3)
N6—Cd1—N6i178.08 (14)N13—C12—N16123.4 (6)
N13i—Cd1—S1i91.73 (8)N13—C12—N17122.7 (7)
N13—Cd1—S191.73 (8)C14—C15—S11110.3 (3)
N13—Cd1—S1i169.74 (7)C15—S11—C1288.67 (18)
N13i—Cd1—S1169.74 (7)C15—C14—N13116.5 (3)
N13—Cd1—N687.61 (10)N16—C12—S11118.1 (6)
N13i—Cd1—N693.78 (10)N17—C12—S11119.2 (6)
N13—Cd1—N6i93.78 (10)S11—C15—H15124.8
N13i—Cd1—N6i87.61 (10)C12—N16—H16A120.0
N13—Cd1—N13i87.47 (15)C12—N16—H16B120.0
N3ii—Cd2—N3180.00 (16)C12—N17—H17A120.0
N3ii—Cd2—S485.83 (8)C12—N17—H17B120.0
N3—Cd2—S494.17 (8)N13—C14—H14A121.7
N3ii—Cd2—S4ii94.17 (8)C14—C15—H15124.8
N3—Cd2—S4ii85.83 (8)C15—C14—H14A121.7
N3ii—Cd2—N2389.73 (10)H16A—N16—H16B120.0
N3—Cd2—N2390.27 (10)H17A—N17—H17B120.0
N3ii—Cd2—N23ii90.27 (10)C22—N23—C24110.1 (3)
N3—Cd2—N23ii89.73 (10)N23—C22—N26124.6 (3)
S4—Cd2—S4ii180.00 (3)N23—C22—S21114.0 (3)
N23—Cd2—S490.82 (7)C24—C25—S21110.5 (3)
N23ii—Cd2—S489.18 (7)C25—S21—C2289.30 (17)
N23—Cd2—S4ii89.18 (7)C25—C24—N23116.1 (3)
N23ii—Cd2—S4ii90.82 (7)N26—C22—S21121.4 (3)
N23—Cd2—N23ii180.00 (9)S21—C25—H25124.8
C2—S1—Cd196.66 (11)C22—N26—H26A120.0
C5—N6—Cd1161.5 (3)C22—N26—H26B120.0
C12—N13—Cd1131.1 (2)N23—C24—H24A121.9
C14—N13—Cd1119.3 (2)C24—C25—H25124.8
C2—N3—Cd2154.3 (3)C25—C24—H24A121.9
C5—S4—Cd298.09 (10)H26A—N26—H26B120.0
C22—N23—Cd2130.0 (2)
Cd1—N13—C14—C15178.2 (3)N13—Cd1—N6—C5−65.9 (8)
Cd2—N23—C24—C25−173.5 (3)N13i—Cd1—N6—C5−153.2 (8)
S1i—Cd1—S1—C2−97.42 (14)N13i—Cd1—N13—C12−124.6 (5)
S1i—Cd1—N6—C5115.6 (8)N13i—Cd1—N13—C1456.3 (3)
S1—Cd1—N6—C525.6 (8)N23—Cd2—N3—C222.6 (6)
S1i—Cd1—N13—C12149.7 (4)N23ii—Cd2—N3—C2−157.4 (6)
S1—Cd1—N13—C1245.2 (4)N23—Cd2—S4—C5−73.06 (13)
S1i—Cd1—N13—C14−29.5 (7)N23ii—Cd2—S4—C5106.94 (13)
S1—Cd1—N13—C14−134.0 (3)S11—C12—N13—Cd1−178.3 (2)
N3ii—Cd2—S4—C5−162.73 (14)S11—C12—N13—C140.9 (5)
N3—Cd2—S4—C517.27 (14)C12—S11—C15—C14−0.2 (4)
N3ii—Cd2—N23—C22−37.4 (3)C12—N13—C14—C15−1.1 (6)
N3—Cd2—N23—C22142.6 (3)N13—C14—C15—S110.8 (5)
N3ii—Cd2—N23—C24136.1 (2)C15—S11—C12—N13−0.4 (4)
N3—Cd2—N23—C24−43.9 (2)C15—S11—C12—N17−161.1 (7)
S4—Cd2—N3—C2−68.2 (6)C15—S11—C12—N16158.8 (6)
S4ii—Cd2—N3—C2111.8 (6)N16—C12—N13—Cd123.7 (9)
S4—Cd2—N23—C22−123.2 (3)N16—C12—N13—C14−157.1 (7)
S4ii—Cd2—N23—C2256.8 (3)N17—C12—N13—Cd1−18.4 (9)
S4—Cd2—N23—C2450.3 (2)N17—C12—N13—C14160.8 (7)
S4ii—Cd2—N23—C24−129.7 (2)S21—C22—N23—Cd2172.61 (15)
N6—Cd1—S1—C2−15.13 (15)S21—C22—N23—C24−1.4 (4)
N6i—Cd1—S1—C2166.23 (15)C22—S21—C25—C24−0.3 (3)
N6—Cd1—N13—C12141.5 (4)C22—N23—C24—C251.2 (4)
N6i—Cd1—N13—C12−37.1 (4)N23—C24—C25—S21−0.4 (4)
N6—Cd1—N13—C14−37.6 (3)C25—S21—C22—N231.0 (3)
N6i—Cd1—N13—C14143.7 (3)C25—S21—C22—N26179.7 (3)
N13—Cd1—S1—C272.66 (15)N26—C22—N23—Cd2−6.1 (5)
N13i—Cd1—S1—C2158.0 (5)N26—C22—N23—C24180.0 (4)
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x−1/2, −y+3/2, −z.
Table 1
Selected geometric parameters (Å, °) top
Cd1—S12.7422 (11)Cd2—S42.7616 (9)
Cd1—N62.336 (3)Cd2—N32.302 (3)
Cd1—N132.328 (3)Cd2—N232.373 (3)
S1i—Cd1—S190.85 (7)N3ii—Cd2—N3180.00 (16)
N6—Cd1—S196.40 (7)N3—Cd2—S494.17 (8)
N6—Cd1—N6i178.08 (14)N3—Cd2—N2390.27 (10)
N13—Cd1—S191.73 (8)S4—Cd2—S4ii180.00 (3)
N13—Cd1—S1i169.74 (7)N23—Cd2—S490.82 (7)
N13—Cd1—N687.61 (10)N23—Cd2—N23ii180.00 (9)
N13—Cd1—N13i87.47 (15)
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x−1/2, −y+3/2, −z.
references
References top

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