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In the title compound, catena-poly­[[bis­(aniline-N)cadmium(II)]-di-μ-thio­cyanato-S:N;N:S], [Cd­(SCN)2­(C6H7N)2], the CdII atom lies on an inversion centre and is in a distorted octahedral geometry. The coordination sphere contains two thio­cyanate (SCN) S atoms, two iso­thio­cyanate (NCS) N atoms and two aniline N atoms. The six-coordinated Cd atoms run parallel to the b axis and are doubly bridged with neighbouring Cd atoms by SCN and NCS ligands. Thus, this complex has a one-dimensional coordination polymeric chain structure in which the aniline ligand is in the trans conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100000160/ja1012sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000160/ja1012Isup2.hkl
Contains datablock I

CCDC reference: 144614

Comment top

The supramolecular architecture of multi-dimensional networks has become of great interest recently. It has been reported that these networks may have electronic, magnetic, optical, or catalytic applications (Batten & Robson, 1998; Dunbar & Heintz, 1997). For designing infinite inorganic-organic frameworks, we and others (Kim et al., 1999; Cortes et al., 1997; Demunno et al., 1997) have used various pseudohalide ions, such as CN-, OCN-, SCN-, SeCN-, CNO- and N3-, and complementary organic ligands. Due to the terminal and bridging bonding properties, multi-dimensional framework structures linking one metal atom M to another metal atom M' alternately could be built by using pseudohalide ions (Wells, 1984). As an extension of the study, we have introduced the thiocyanate and aniline as complementary ligands. We here report the one-dimensional inorganic-organic composite coordination polymeric structure of the compound [Cd(SCN)2(C6H5NH2)2], (I). \sch

As shown in Figs. 1 and 2, each cadmium(II) atom lies on an inversion centre and is hexacoordinated by the two thiocyanate sulfur atoms, two isothiocyanate nitrogen atoms, and two aniline nitrogen atoms. The pairs of the same kinds of ligands are all in trans-configurations. The coordination environment of the central cadmium(II) atom adopts a distorted octahedral geometry. The bond length of Cd—SSCN is longer than that of Cd—NNCS in the corresponding cation [2.7485 (6) versus 2.283 (2) Å]. The bond length of Cd—NNCS is shorter than that of Cd—Naniline [2.283 (2) versus 2.358 (2) Å]. The variations in the Cd—S—CSCN and Cd—N—CNCS bond angles are all within the reported range (Wells, 1984). The bond lengths and angles of the SCN and aniline ligands of (I) are unexceptional and similar to those reported in the literature (Zukerman-Schpector et al., 1988).

As shown in Fig. 2, the octahedral Cd centres run in parallel to the b axis and are doubly bridged with neighbouring Cd centres by the SCN and NCS ligands to form an eight-membered ring with a repeating unit of Cd—S—C—N—Cd—S—C—N– and a centre of inversion in the centre of the ring. Thus, (I) forms a one-dimensional infinite polymeric linear chain structure. In comparison with other similar systems, the coordination geometry and crystal structure of (I) is very different. In the crystal structure of cadmium dithiocyanate itself, the cadmium atom is six-coordinated by four sulfur and two trans-nitrogen atoms (Cannas et al., 1976a). Treatment with an amine such as tetramethylethylenediamine furnishes an adduct in which adjacent cadmium atoms are bridged by a pair of NCS/SCN bridges (Zukerman-Schpector et al., 1988). 1,2,4-Triazole can be used for the purpose of forming the [Cd(NCS)2]n chains (Haasnoot et al., 1983; Biagini Cingi et al., 1986). On the other hand, with 2,2'-bipyridine, the resulting complex exists as a monomer and the bridges are absent (Rodesiler et al., 1984). When a triamine is used, the resulting complex has the cadmium atom bonded by five nitrogen atoms (Cannas et al., 1976b). These observations indicate that the crystal structure of the thiocyanate complexes is significantly affected by the bonding properties of the thiocyanate group and the skeleton of the organic ligand.

Experimental top

To a 30 ml aqueous solution containing CdCl2·2.5H2O (1.45 g, 5 mmol) and KSCN (2.91 g, 10 mmol), aniline (1.9 ml, 20 mmol) was added; the pH of the solution was adjusted to 9 by adding 2-aminoethanol and citric acid. After a small amount of the precipitate was filtered off, the aqueous solution was allowed to stand in a refrigerator at 278 K. After a few weeks, pale yellow crystals were obtained.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); 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. Coordination environment around the cadmium(II) atom in (I) with 30% probability ellipsoids. H atoms are shown as small circles of arbitrary radii.
[Figure 2] Fig. 2. Perspective view of the unit cell of (I) along the c axis. H atoms are omitted for clarity.
Bis(aniline)dithiocyanatocadmium(II) top
Crystal data top
[Cd(CNS)2(C6H7N)2]F(000) = 412
Mr = 414.81Dx = 1.635 Mg m3
Dm = 1.64 Mg m3
Dm measured by flotation in mesitylene-bromoform
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.1132 (13) ÅCell parameters from 39 reflections
b = 5.8547 (6) Åθ = 4.7–12.5°
c = 13.1706 (13) ŵ = 1.54 mm1
β = 100.466 (9)°T = 293 K
V = 842.68 (16) Å3Block, pale yellow
Z = 20.40 × 0.31 × 0.22 mm
Data collection top
Siemens P4
diffractometer
1616 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
Graphite monochromatorθmax = 27.5°, θmin = 1.9°
2θ/ω scansh = 114
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
k = 17
Tmin = 0.510, Tmax = 0.712l = 1717
2664 measured reflections3 standard reflections every 97 reflections
1943 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)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068 w = 1/[σ2(Fo2) + (0.0289P)2 + 0.222P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1943 reflectionsΔρmax = 0.25 e Å3
98 parametersΔρmin = 0.47 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0317 (14)
Crystal data top
[Cd(CNS)2(C6H7N)2]V = 842.68 (16) Å3
Mr = 414.81Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.1132 (13) ŵ = 1.54 mm1
b = 5.8547 (6) ÅT = 293 K
c = 13.1706 (13) Å0.40 × 0.31 × 0.22 mm
β = 100.466 (9)°
Data collection top
Siemens P4
diffractometer
1616 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
(North et al., 1968)
Rint = 0.021
Tmin = 0.510, Tmax = 0.7123 standard reflections every 97 reflections
2664 measured reflections intensity decay: none
1943 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.25 e Å3
1943 reflectionsΔρmin = 0.47 e Å3
98 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.

All non-H atoms were refined anisotropically. All hydrogen atoms were fixed at their calculated positions with the isotropic displacement parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.00000.50000.50000.04603 (11)
S10.10627 (8)0.74326 (10)0.63889 (5)0.0663 (2)
C10.0890 (2)1.0014 (3)0.59413 (18)0.0442 (5)
N10.0779 (2)1.1809 (3)0.56386 (16)0.0564 (5)
N100.1773 (2)0.5709 (4)0.37581 (16)0.0563 (5)
H10A0.21290.69900.39390.068*
H10B0.15450.59780.31470.068*
C110.2668 (2)0.3916 (5)0.36198 (18)0.0528 (6)
C120.2635 (2)0.2250 (5)0.2885 (2)0.0607 (6)
H12A0.20480.23140.24640.073*
C130.3465 (3)0.0503 (6)0.2777 (3)0.0742 (8)
H13A0.34430.06110.22770.089*
C140.4337 (3)0.0375 (6)0.3403 (4)0.0826 (10)
H14A0.48970.08210.33310.099*
C150.4362 (3)0.2026 (7)0.4122 (3)0.0835 (10)
H15A0.49490.19580.45430.100*
C160.3526 (3)0.3819 (6)0.4243 (2)0.0680 (7)
H16A0.35500.49350.47420.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.06856 (18)0.02665 (14)0.04478 (15)0.00455 (10)0.01534 (10)0.00278 (8)
S10.1231 (6)0.0290 (3)0.0606 (3)0.0041 (3)0.0535 (4)0.0022 (3)
C10.0662 (13)0.0304 (11)0.0400 (10)0.0033 (10)0.0203 (9)0.0043 (8)
N10.0834 (14)0.0314 (10)0.0610 (12)0.0019 (10)0.0301 (11)0.0038 (9)
N100.0726 (14)0.0475 (11)0.0507 (11)0.0015 (11)0.0160 (10)0.0094 (10)
C110.0567 (14)0.0506 (15)0.0516 (12)0.0068 (12)0.0113 (10)0.0105 (11)
C120.0597 (14)0.0618 (17)0.0613 (14)0.0038 (13)0.0130 (11)0.0025 (13)
C130.0692 (18)0.0599 (17)0.089 (2)0.0040 (15)0.0015 (16)0.0072 (16)
C140.0660 (18)0.065 (2)0.114 (3)0.0063 (15)0.0080 (19)0.0123 (19)
C150.0694 (18)0.086 (2)0.103 (2)0.0017 (17)0.0379 (18)0.022 (2)
C160.0792 (18)0.0639 (19)0.0667 (16)0.0106 (16)0.0289 (14)0.0056 (14)
Geometric parameters (Å, º) top
Cd1—N1i2.283 (2)C11—C161.368 (3)
Cd1—N1ii2.283 (2)C11—C121.379 (4)
Cd1—N102.358 (2)C12—C131.368 (4)
Cd1—N10iii2.358 (2)C12—H12A0.9300
Cd1—S1iii2.7485 (6)C13—C141.384 (6)
Cd1—S12.7485 (6)C13—H13A0.9300
S1—C11.646 (2)C14—C151.358 (5)
C1—N11.139 (3)C14—H14A0.9300
N1—Cd1iv2.2830 (19)C15—C161.391 (4)
N10—C111.434 (4)C15—H15A0.9300
N10—H10A0.9000C16—H16A0.9300
N10—H10B0.9000
N1i—Cd1—N1ii180.0C11—N10—H10B108.4
N1i—Cd1—N1094.27 (8)Cd1—N10—H10B108.4
N1ii—Cd1—N1085.73 (8)H10A—N10—H10B107.4
N1i—Cd1—N10iii85.73 (8)C16—C11—C12120.1 (3)
N1ii—Cd1—N10iii94.27 (8)C16—C11—N10119.8 (3)
N10—Cd1—N10iii180.0C12—C11—N10120.0 (2)
N1i—Cd1—S1iii93.37 (5)C13—C12—C11119.9 (3)
N1ii—Cd1—S1iii86.63 (5)C13—C12—H12A120.0
N10—Cd1—S1iii92.04 (6)C11—C12—H12A120.0
N10iii—Cd1—S1iii87.96 (6)C12—C13—C14120.7 (3)
N1i—Cd1—S186.63 (5)C12—C13—H13A119.7
N1ii—Cd1—S193.37 (5)C14—C13—H13A119.7
N10—Cd1—S187.96 (6)C15—C14—C13118.8 (3)
N10iii—Cd1—S192.04 (6)C15—C14—H14A120.6
S1iii—Cd1—S1180.000 (18)C13—C14—H14A120.6
C1—S1—Cd198.36 (8)C14—C15—C16121.3 (3)
N1—C1—S1179.2 (2)C14—C15—H15A119.3
C1—N1—Cd1iv163.1 (2)C16—C15—H15A119.3
C11—N10—Cd1115.59 (16)C11—C16—C15119.1 (3)
C11—N10—H10A108.4C11—C16—H16A120.4
Cd1—N10—H10A108.4C15—C16—H16A120.4
N1i—Cd1—S1—C1168.68 (11)S1—Cd1—N10—C1196.85 (17)
N1ii—Cd1—S1—C111.32 (11)Cd1—N10—C11—C1686.1 (3)
N10—Cd1—S1—C174.28 (12)Cd1—N10—C11—C1291.5 (2)
N10iii—Cd1—S1—C1105.72 (12)C16—C11—C12—C130.3 (4)
S1iii—Cd1—S1—C150 (100)N10—C11—C12—C13178.0 (3)
Cd1—S1—C1—N1169 (100)C11—C12—C13—C140.5 (5)
S1—C1—N1—Cd1iv148 (24)C12—C13—C14—C150.5 (5)
N1i—Cd1—N10—C1110.38 (18)C13—C14—C15—C160.4 (5)
N1ii—Cd1—N10—C11169.62 (18)C12—C11—C16—C150.2 (4)
N10iii—Cd1—N10—C11156 (100)N10—C11—C16—C15177.9 (3)
S1iii—Cd1—N10—C1183.15 (17)C14—C15—C16—C110.3 (5)
Symmetry codes: (i) x, y1, z; (ii) x, y+2, z+1; (iii) x, y+1, z+1; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cd(CNS)2(C6H7N)2]
Mr414.81
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)11.1132 (13), 5.8547 (6), 13.1706 (13)
β (°) 100.466 (9)
V3)842.68 (16)
Z2
Radiation typeMo Kα
µ (mm1)1.54
Crystal size (mm)0.40 × 0.31 × 0.22
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(North et al., 1968)
Tmin, Tmax0.510, 0.712
No. of measured, independent and
observed [I > 2σ(I)] reflections
2664, 1943, 1616
Rint0.021
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.068, 1.05
No. of reflections1943
No. of parameters98
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.47

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Siemens, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Cd1—N1i2.283 (2)C11—C161.368 (3)
Cd1—N102.358 (2)C11—C121.379 (4)
Cd1—S12.7485 (6)C12—C131.368 (4)
S1—C11.646 (2)C13—C141.384 (6)
C1—N11.139 (3)C14—C151.358 (5)
N10—C111.434 (4)C15—C161.391 (4)
N1i—Cd1—N1094.27 (8)C16—C11—N10119.8 (3)
N1i—Cd1—S186.63 (5)C12—C11—N10120.0 (2)
N10—Cd1—S187.96 (6)C13—C12—C11119.9 (3)
C1—S1—Cd198.36 (8)C12—C13—C14120.7 (3)
N1—C1—S1179.2 (2)C15—C14—C13118.8 (3)
C1—N1—Cd1ii163.1 (2)C14—C15—C16121.3 (3)
C11—N10—Cd1115.59 (16)C11—C16—C15119.1 (3)
C16—C11—C12120.1 (3)
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.
 

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