catena-Poly[[bis­(2-amino­thia­zole-κN)cadmium(II)]-di-μ-thio­cyanato-κ²N:S;κ²S:N]

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.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.028
• wR factor = 0.078
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         S1

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.94
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cd1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT322_ALERT_2_C Check Hybridisation of  S11    in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S21    in Main Residue .          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N26    -   H26A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N26    -   H26B   ...          ?

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.944
            Tmax scaled      0.565 Tmin scaled      0.447

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C, N).

Computing details

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

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]

Crystal data

[Cd(NCS)2(C3H4N2S)2]	F(000) = 1680
Mr = 428.84	Dx = 1.929 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 42 reflections
a = 18.7079 (18) Å	θ = 4.7–12.5°
b = 9.0553 (13) Å	µ = 2.04 mm^−1
c = 18.661 (2) Å	T = 295 K
β = 110.918 (8)°	Block, dark-yellow
V = 2953.0 (6) Å^3	0.43 × 0.31 × 0.28 mm
Z = 8

Data collection

Bruker P4 diffractometer	2860 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 26.5°, θmin = 2.3°
2θ/ω scans	h = −1→23
Absorption correction: empirical (using intensity measurements) (XSCANS; Bruker, 1996)	k = −11→1
Tmin = 0.474, Tmax = 0.599	l = −23→22
3784 measured reflections	3 standard reflections every 97 reflections
3046 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0328P)^2 + 7.3517P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
3046 reflections	Δρmax = 0.60 e Å^−3
178 parameters	Δρmin = −0.76 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00205 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.0000	0.49223 (3)	0.2500	0.03120 (11)
Cd2	−0.2500	0.7500	0.0000	0.03061 (11)
S1	0.02580 (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)
S11	0.01787 (7)	0.13108 (14)	0.06482 (7)	0.0750 (4)
C12	0.0430 (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	−0.0958	0.2019	0.1669	0.058*
C15	−0.0577 (2)	0.1020 (4)	0.0934 (2)	0.0541 (9)
H15	−0.0933	0.0264	0.0756	0.065*
N16	0.1189 (7)	0.3314 (14)	0.1494 (7)	0.079 (4)	0.50
H16A	0.1377	0.3820	0.1909	0.095*	0.50
H16B	0.1466	0.3116	0.1224	0.095*	0.50
N17	0.0918 (7)	0.3884 (15)	0.1145 (6)	0.079 (4)	0.50
H17A	0.0927	0.4756	0.1330	0.095*	0.50
H17B	0.1208	0.3671	0.0891	0.095*	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	−0.1557	0.8118	0.1847	0.053*
C25	−0.1850 (2)	0.9956 (4)	0.2256 (2)	0.0537 (9)
H25	−0.1559	0.9878	0.2775	0.064*
N26	−0.3175 (2)	1.1158 (4)	0.0324 (2)	0.0675 (10)
H26A	−0.3287	1.0712	−0.0109	0.081*
H26B	−0.3383	1.1995	0.0349	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02668 (17)	0.03422 (18)	0.02801 (17)	0.000	0.00404 (12)	0.000
Cd2	0.02562 (17)	0.03635 (19)	0.02680 (17)	0.00368 (11)	0.00563 (12)	0.00005 (11)
S1	0.0393 (5)	0.0744 (7)	0.0720 (7)	−0.0191 (5)	−0.0118 (5)	0.0359 (6)
C2	0.0349 (16)	0.0333 (15)	0.0392 (16)	0.0035 (12)	0.0117 (13)	0.0099 (13)
N3	0.0300 (14)	0.0555 (17)	0.0416 (15)	0.0058 (12)	0.0085 (12)	0.0088 (13)
S4	0.0267 (4)	0.0563 (5)	0.0364 (4)	−0.0026 (3)	0.0039 (3)	0.0128 (4)
C5	0.0323 (15)	0.0317 (14)	0.0305 (14)	−0.0001 (11)	0.0125 (12)	0.0027 (11)
N6	0.0305 (14)	0.0439 (15)	0.0417 (15)	0.0016 (11)	0.0046 (12)	0.0052 (12)
S11	0.0784 (7)	0.0805 (8)	0.0858 (8)	−0.0401 (6)	0.0535 (7)	−0.0548 (7)
C12	0.068 (3)	0.075 (3)	0.071 (3)	−0.043 (2)	0.047 (2)	−0.045 (2)
N13	0.0401 (14)	0.0470 (16)	0.0429 (14)	−0.0187 (12)	0.0224 (12)	−0.0175 (13)
C14	0.0460 (19)	0.0444 (18)	0.063 (2)	−0.0173 (16)	0.0285 (17)	−0.0110 (17)
C15	0.048 (2)	0.0454 (19)	0.070 (2)	−0.0200 (16)	0.0222 (18)	−0.0173 (18)
N16	0.078 (8)	0.092 (9)	0.095 (8)	−0.052 (6)	0.066 (7)	−0.054 (6)
N17	0.078 (8)	0.092 (9)	0.095 (8)	−0.052 (6)	0.066 (7)	−0.054 (6)
S21	0.0670 (6)	0.0438 (5)	0.0630 (6)	−0.0083 (4)	0.0380 (5)	−0.0182 (4)
C22	0.0494 (19)	0.0349 (16)	0.0509 (19)	−0.0010 (14)	0.0275 (16)	−0.0030 (15)
N23	0.0415 (14)	0.0350 (13)	0.0347 (13)	0.0013 (11)	0.0157 (11)	−0.0018 (11)
C24	0.0522 (19)	0.0434 (18)	0.0362 (16)	−0.0038 (15)	0.0152 (15)	−0.0027 (14)
C25	0.066 (2)	0.057 (2)	0.0404 (19)	−0.0098 (18)	0.0227 (18)	−0.0064 (16)
N26	0.079 (2)	0.0529 (19)	0.062 (2)	0.0277 (18)	0.0156 (19)	0.0011 (17)

Geometric parameters (Å, º)

Cd1—S1^i	2.7422 (11)	C12—N17	1.399 (13)
Cd1—S1	2.7422 (11)	N13—C14	1.371 (4)
Cd1—N6	2.336 (3)	C14—C15	1.321 (5)
Cd1—N6^i	2.336 (3)	C14—H14A	0.9300
Cd1—N13	2.328 (3)	C15—H15	0.9300
Cd1—N13^i	2.328 (3)	N16—H16A	0.8600
Cd2—S4	2.7616 (9)	N16—H16B	0.8600
Cd2—N3^ii	2.302 (3)	N17—H17A	0.8600
Cd2—N3	2.302 (3)	N17—H17B	0.8600
Cd2—S4^ii	2.7616 (9)	S21—C22	1.733 (4)
Cd2—N23	2.373 (3)	S21—C25	1.717 (4)
Cd2—N23^ii	2.373 (3)	C22—N23	1.317 (4)
S1—C2	1.632 (3)	C22—N26	1.332 (5)
C2—N3	1.153 (4)	N23—C24	1.386 (4)
S4—C5	1.648 (3)	C24—C25	1.332 (5)
C5—N6	1.144 (4)	C24—H24A	0.9300
S11—C12	1.723 (4)	C25—H25	0.9300
S11—C15	1.701 (4)	N26—H26A	0.8600
C12—N13	1.289 (4)	N26—H26B	0.8600
C12—N16	1.404 (13)
S1^i—Cd1—S1	90.85 (7)	C24—N23—Cd2	119.7 (2)
N6—Cd1—S1	96.40 (7)	N3—C2—S1	178.8 (3)
N6^i—Cd1—S1	82.24 (8)	N6—C5—S4	179.9 (4)
N6—Cd1—S1^i	82.24 (8)	C12—N13—C14	109.6 (3)
N6^i—Cd1—S1^i	96.40 (7)	N13—C12—S11	114.9 (3)
N6—Cd1—N6^i	178.08 (14)	N13—C12—N16	123.4 (6)
N13^i—Cd1—S1^i	91.73 (8)	N13—C12—N17	122.7 (7)
N13—Cd1—S1	91.73 (8)	C14—C15—S11	110.3 (3)
N13—Cd1—S1^i	169.74 (7)	C15—S11—C12	88.67 (18)
N13^i—Cd1—S1	169.74 (7)	C15—C14—N13	116.5 (3)
N13—Cd1—N6	87.61 (10)	N16—C12—S11	118.1 (6)
N13^i—Cd1—N6	93.78 (10)	N17—C12—S11	119.2 (6)
N13—Cd1—N6^i	93.78 (10)	S11—C15—H15	124.8
N13^i—Cd1—N6^i	87.61 (10)	C12—N16—H16A	120.0
N13—Cd1—N13^i	87.47 (15)	C12—N16—H16B	120.0
N3^ii—Cd2—N3	180.00 (16)	C12—N17—H17A	120.0
N3^ii—Cd2—S4	85.83 (8)	C12—N17—H17B	120.0
N3—Cd2—S4	94.17 (8)	N13—C14—H14A	121.7
N3^ii—Cd2—S4^ii	94.17 (8)	C14—C15—H15	124.8
N3—Cd2—S4^ii	85.83 (8)	C15—C14—H14A	121.7
N3^ii—Cd2—N23	89.73 (10)	H16A—N16—H16B	120.0
N3—Cd2—N23	90.27 (10)	H17A—N17—H17B	120.0
N3^ii—Cd2—N23^ii	90.27 (10)	C22—N23—C24	110.1 (3)
N3—Cd2—N23^ii	89.73 (10)	N23—C22—N26	124.6 (3)
S4—Cd2—S4^ii	180.00 (3)	N23—C22—S21	114.0 (3)
N23—Cd2—S4	90.82 (7)	C24—C25—S21	110.5 (3)
N23^ii—Cd2—S4	89.18 (7)	C25—S21—C22	89.30 (17)
N23—Cd2—S4^ii	89.18 (7)	C25—C24—N23	116.1 (3)
N23^ii—Cd2—S4^ii	90.82 (7)	N26—C22—S21	121.4 (3)
N23—Cd2—N23^ii	180.00 (9)	S21—C25—H25	124.8
C2—S1—Cd1	96.66 (11)	C22—N26—H26A	120.0
C5—N6—Cd1	161.5 (3)	C22—N26—H26B	120.0
C12—N13—Cd1	131.1 (2)	N23—C24—H24A	121.9
C14—N13—Cd1	119.3 (2)	C24—C25—H25	124.8
C2—N3—Cd2	154.3 (3)	C25—C24—H24A	121.9
C5—S4—Cd2	98.09 (10)	H26A—N26—H26B	120.0
C22—N23—Cd2	130.0 (2)
Cd1—N13—C14—C15	178.2 (3)	N13—Cd1—N6—C5	−65.9 (8)
Cd2—N23—C24—C25	−173.5 (3)	N13^i—Cd1—N6—C5	−153.2 (8)
S1^i—Cd1—S1—C2	−97.42 (14)	N13^i—Cd1—N13—C12	−124.6 (5)
S1^i—Cd1—N6—C5	115.6 (8)	N13^i—Cd1—N13—C14	56.3 (3)
S1—Cd1—N6—C5	25.6 (8)	N23—Cd2—N3—C2	22.6 (6)
S1^i—Cd1—N13—C12	149.7 (4)	N23^ii—Cd2—N3—C2	−157.4 (6)
S1—Cd1—N13—C12	45.2 (4)	N23—Cd2—S4—C5	−73.06 (13)
S1^i—Cd1—N13—C14	−29.5 (7)	N23^ii—Cd2—S4—C5	106.94 (13)
S1—Cd1—N13—C14	−134.0 (3)	S11—C12—N13—Cd1	−178.3 (2)
N3^ii—Cd2—S4—C5	−162.73 (14)	S11—C12—N13—C14	0.9 (5)
N3—Cd2—S4—C5	17.27 (14)	C12—S11—C15—C14	−0.2 (4)
N3^ii—Cd2—N23—C22	−37.4 (3)	C12—N13—C14—C15	−1.1 (6)
N3—Cd2—N23—C22	142.6 (3)	N13—C14—C15—S11	0.8 (5)
N3^ii—Cd2—N23—C24	136.1 (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—N16	158.8 (6)
S4^ii—Cd2—N3—C2	111.8 (6)	N16—C12—N13—Cd1	23.7 (9)
S4—Cd2—N23—C22	−123.2 (3)	N16—C12—N13—C14	−157.1 (7)
S4^ii—Cd2—N23—C22	56.8 (3)	N17—C12—N13—Cd1	−18.4 (9)
S4—Cd2—N23—C24	50.3 (2)	N17—C12—N13—C14	160.8 (7)
S4^ii—Cd2—N23—C24	−129.7 (2)	S21—C22—N23—Cd2	172.61 (15)
N6—Cd1—S1—C2	−15.13 (15)	S21—C22—N23—C24	−1.4 (4)
N6^i—Cd1—S1—C2	166.23 (15)	C22—S21—C25—C24	−0.3 (3)
N6—Cd1—N13—C12	141.5 (4)	C22—N23—C24—C25	1.2 (4)
N6^i—Cd1—N13—C12	−37.1 (4)	N23—C24—C25—S21	−0.4 (4)
N6—Cd1—N13—C14	−37.6 (3)	C25—S21—C22—N23	1.0 (3)
N6^i—Cd1—N13—C14	143.7 (3)	C25—S21—C22—N26	179.7 (3)
N13—Cd1—S1—C2	72.66 (15)	N26—C22—N23—Cd2	−6.1 (5)
N13^i—Cd1—S1—C2	158.0 (5)	N26—C22—N23—C24	180.0 (4)

Symmetry codes: (i) −x, y, −z+1/2; (ii) −x−1/2, −y+3/2, −z.