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Acta Cryst. (2008). E64, m1327    [ doi:10.1107/S1600536808030547 ]

catena-Poly[[bis[2-chloro-6-(1H-1,2,4-triazol-1-yl-[kappa]N4)pyridine]cadmium(II)]-di-[mu]-thiocyanato-[kappa]2N:S;[kappa]2S:N]: a one-dimensional coordination polymer

Z. N. Yang and T. T. Sun

Abstract top

In the crystal structure of the title complex, [Cd(NCS)2(C7H5ClN4)2]n, the CdII atom lies on a crystallographic inversion center and assumes a distorted octahedral geometry. The 2-chloro-6-(1H-1,2,4-triazol-1-yl)pyridine molecule acts as a terminal ligand. The thiocyanate ligands function as [mu]1,3-bridging units connecting adjacent CdII atoms with a separation of 5.7525 (11) Å, forming a one-dimensional chain along the a axis.

Comment top

For a long time, thiocyanate anion has been used as a bridge ligand and a number of complexes with it have been published (Shi et al., 2006). But complex dealing with 2-chloro-6-(1H-1,2,4-triazol-1-yl)pyridine as a ligand has not been reported as yet as our knowledge. The interest in complexes with mixed bridge ligands resulted in us synthesizing the title complex and here we report its crystal structure, (I).

The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1. Atom Cd1 is located on an inversion center and is in a distorted octahedral CdN4S2 coordination geometry (Table 1). In the crystal 2-chloro-6-(1H-1,2,4-triazol-1-yl)pyridine molecule only acts as a unidentate terminal ligand, and thiocyanate anion functions as a µ-1,3 bridge ligand and joins a pair of CdII ions with separation of 5.7525 (11) Å. In this way a one-dimensional chain along a axis was fabricated as shown in Fig. 2. In addition, there is a weak π-π stacking interaction involving symmetry related 2-chloro-6-(1H-1,2,4-triazol-1-yl)pyridine molecules, with relevant distances being Cg1···Cg2i = 3.7095 (19) Å, Cg1···Cg2iperp = 3.427 Å, α = 4.24° [symmetry code: (i) -x, 2-y,1-z; Cg1 and Cg2 are the centroids of the pyrazole ring and pyridyl ring, respectively; Cg1···Cg2iperp is the perpendicular distance from ring Cg1 to ring Cg2i; α is the dihedral angle between plane Cg1 and plane Cg2i.

Related literature top

For arelated structure, see: Shi et al. (2006).

Experimental top

15 ml H2O solution containing Cd(ClO4)2.6H2O (0.1507 g, 0.359 mmol) and NaSCN (0.0591 g, 0.729 mmol) was added into 15 ml methanol solution of 2-chloro-6-(1H-1,2,4-triazol-1-yl)pyridine (0.1203 g, 0.666 mmol), and the mixed solution was stirred for a few minutes. The colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for about three weeks.

Refinement top

All H atoms were placed in calculated positions (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of complex (I), showing the atom numbering scheme with displacement ellipsoids drawn at the 30% probability level [symmetry codes: (i) -x, -y + 2, -z + 2; (ii) x - 1, y, -z + 1; (iii) x + 1, y, z; (iv) -x + 1, -y + 2, -z + 2].
[Figure 2] Fig. 2. Packing diagram of (I), showing one-dimensional chains.
catena-Poly[[bis[2-chloro-6-(1H-1,2,4-triazol-1-yl- κN4)pyridine]cadmium(II)]-di-µ-thiocyanato-κ2N:S;κ2S:N] top
Crystal data top
[Cd(NCS)2(C7H5ClN4)2]Z = 1
Mr = 589.76F(000) = 290
Triclinic, P1Dx = 1.825 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.7525 (11) ÅCell parameters from 1921 reflections
b = 8.0180 (15) Åθ = 2.7–28.1°
c = 12.212 (2) ŵ = 1.49 mm−1
α = 107.609 (3)°T = 298 K
β = 90.095 (2)°Block, colorless
γ = 91.950 (3)°0.23 × 0.21 × 0.10 mm
V = 536.53 (18) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		2005 independent reflections
Radiation source: fine-focus sealed tube1903 reflections with I > 2σ(I)
graphiteRint = 0.016
φ and ω scansθmax = 25.8°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→7
Tmin = 0.726, Tmax = 0.865k = −9→8
2892 measured reflectionsl = −11→14
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) = 0.071 w = 1/[σ2(Fo2) + (0.0366P)2 + 0.1572P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
2005 reflectionsΔρmax = 0.34 e Å−3
143 parametersΔρmin = −0.36 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.021 (2)
Crystal data top
[Cd(NCS)2(C7H5ClN4)2]γ = 91.950 (3)°
Mr = 589.76V = 536.53 (18) Å3
Triclinic, P1Z = 1
a = 5.7525 (11) ÅMo Kα radiation
b = 8.0180 (15) ŵ = 1.49 mm−1
c = 12.212 (2) ÅT = 298 K
α = 107.609 (3)°0.23 × 0.21 × 0.10 mm
β = 90.095 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2005 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1903 reflections with I > 2σ(I)
Tmin = 0.726, Tmax = 0.865Rint = 0.016
2892 measured reflectionsθmax = 25.8°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.071Δρmax = 0.34 e Å−3
S = 1.03Δρmin = −0.36 e Å−3
2005 reflectionsAbsolute structure: ?
143 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*/Ueq
C1−0.0042 (5)0.8697 (4)0.7162 (2)0.0411 (6)
H1−0.14360.80650.71390.049*
C20.1609 (7)0.7193 (5)0.3111 (3)0.0639 (9)
H20.25490.73100.25180.077*
C30.2948 (5)1.0298 (4)0.7697 (2)0.0534 (8)
H30.40581.10350.81780.064*
C40.5043 (5)1.2276 (4)1.0409 (2)0.0421 (6)
C50.2157 (6)0.8143 (4)0.4239 (2)0.0543 (8)
H50.34440.89130.44260.065*
C60.0695 (5)0.7883 (3)0.5063 (2)0.0406 (6)
C7−0.1629 (6)0.5969 (4)0.3779 (2)0.0484 (7)
C8−0.0303 (7)0.6092 (4)0.2872 (2)0.0597 (8)
H8−0.06960.54460.21210.072*
Cd10.00001.00001.00000.04300 (14)
Cl1−0.40595 (17)0.45711 (12)0.35184 (8)0.0709 (3)
N10.1037 (4)0.9656 (3)0.81047 (18)0.0446 (5)
N20.1161 (4)0.8768 (3)0.62460 (17)0.0401 (5)
N30.3112 (4)0.9806 (3)0.65819 (19)0.0530 (6)
N4−0.1181 (4)0.6839 (3)0.48723 (18)0.0420 (5)
N50.3274 (4)1.1798 (4)1.0652 (2)0.0538 (6)
S10.75769 (13)1.29435 (10)1.00393 (6)0.0488 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0387 (14)0.0535 (15)0.0288 (12)−0.0045 (11)0.0033 (10)0.0098 (11)
C20.081 (2)0.078 (2)0.0301 (15)−0.0033 (18)0.0091 (14)0.0133 (14)
C30.0507 (17)0.073 (2)0.0300 (13)−0.0198 (15)0.0021 (12)0.0083 (13)
C40.0382 (15)0.0524 (16)0.0289 (12)−0.0036 (12)−0.0049 (10)0.0026 (11)
C50.065 (2)0.0628 (19)0.0318 (14)−0.0065 (15)0.0078 (13)0.0112 (13)
C60.0517 (16)0.0411 (14)0.0278 (12)0.0034 (12)0.0011 (11)0.0084 (10)
C70.0575 (18)0.0419 (15)0.0413 (15)0.0064 (12)−0.0075 (13)0.0052 (11)
C80.083 (2)0.0602 (19)0.0292 (14)0.0067 (17)−0.0040 (14)0.0025 (13)
Cd10.02956 (18)0.0703 (2)0.02358 (16)−0.01005 (12)0.00224 (10)0.00706 (12)
Cl10.0652 (6)0.0672 (5)0.0659 (5)−0.0086 (4)−0.0153 (4)0.0000 (4)
N10.0437 (13)0.0585 (14)0.0279 (11)−0.0047 (10)0.0042 (9)0.0085 (10)
N20.0434 (13)0.0482 (12)0.0263 (10)−0.0039 (10)0.0034 (9)0.0082 (9)
N30.0533 (15)0.0698 (16)0.0312 (12)−0.0195 (12)0.0052 (10)0.0105 (11)
N40.0487 (14)0.0434 (12)0.0321 (11)0.0048 (10)−0.0018 (9)0.0084 (9)
N50.0360 (14)0.0676 (16)0.0479 (14)−0.0086 (11)0.0004 (10)0.0035 (12)
S10.0407 (4)0.0620 (5)0.0401 (4)−0.0104 (3)0.0037 (3)0.0113 (3)
Geometric parameters (Å, °) top
C1—N11.316 (3)C6—N21.425 (3)
C1—N21.331 (3)C7—N41.326 (3)
C1—H10.9300C7—C81.372 (5)
C2—C81.361 (5)C7—Cl11.729 (3)
C2—C51.387 (4)C8—H80.9300
C2—H20.9300Cd1—N5i2.319 (2)
C3—N31.303 (3)Cd1—N52.319 (2)
C3—N11.356 (3)Cd1—N12.328 (2)
C3—H30.9300Cd1—N1i2.328 (2)
C4—N51.146 (4)Cd1—S1ii2.7696 (9)
C4—S11.646 (3)Cd1—S1iii2.7696 (9)
C5—C61.371 (4)N2—N31.360 (3)
C5—H50.9300S1—Cd1iv2.7696 (9)
C6—N41.319 (4)
N1—C1—N2109.8 (2)N5—Cd1—N190.49 (9)
N1—C1—H1125.1N5i—Cd1—N1i90.49 (9)
N2—C1—H1125.1N5—Cd1—N1i89.51 (9)
C8—C2—C5120.1 (3)N1—Cd1—N1i180.000 (1)
C8—C2—H2120.0N5i—Cd1—S1ii91.29 (7)
C5—C2—H2120.0N5—Cd1—S1ii88.71 (7)
N3—C3—N1115.0 (3)N1—Cd1—S1ii90.02 (6)
N3—C3—H3122.5N1i—Cd1—S1ii89.98 (6)
N1—C3—H3122.5N5i—Cd1—S1iii88.71 (7)
N5—C4—S1179.1 (3)N5—Cd1—S1iii91.29 (7)
C6—C5—C2116.3 (3)N1—Cd1—S1iii89.98 (6)
C6—C5—H5121.9N1i—Cd1—S1iii90.02 (6)
C2—C5—H5121.9S1ii—Cd1—S1iii180.0
N4—C6—C5125.8 (3)C1—N1—C3103.0 (2)
N4—C6—N2114.1 (2)C1—N1—Cd1127.88 (18)
C5—C6—N2120.1 (3)C3—N1—Cd1129.05 (18)
N4—C7—C8124.9 (3)C1—N2—N3110.0 (2)
N4—C7—Cl1115.9 (2)C1—N2—C6129.0 (2)
C8—C7—Cl1119.2 (2)N3—N2—C6120.9 (2)
C2—C8—C7117.6 (3)C3—N3—N2102.2 (2)
C2—C8—H8121.2C6—N4—C7115.4 (2)
C7—C8—H8121.2C4—N5—Cd1145.7 (2)
N5i—Cd1—N5180.0C4—S1—Cd1iv97.18 (11)
N5i—Cd1—N189.51 (9)
C8—C2—C5—C60.6 (5)N1—C1—N2—N30.1 (3)
C2—C5—C6—N4−1.0 (5)N1—C1—N2—C6177.3 (3)
C2—C5—C6—N2178.3 (3)N4—C6—N2—C1−1.0 (4)
C5—C2—C8—C70.0 (5)C5—C6—N2—C1179.6 (3)
N4—C7—C8—C2−0.3 (5)N4—C6—N2—N3175.9 (2)
Cl1—C7—C8—C2−179.4 (3)C5—C6—N2—N3−3.5 (4)
N2—C1—N1—C3−0.1 (3)N1—C3—N3—N2−0.1 (4)
N2—C1—N1—Cd1−176.61 (18)C1—N2—N3—C30.0 (3)
N3—C3—N1—C10.1 (4)C6—N2—N3—C3−177.5 (3)
N3—C3—N1—Cd1176.6 (2)C5—C6—N4—C70.8 (4)
N5i—Cd1—N1—C1−1.9 (3)N2—C6—N4—C7−178.6 (2)
N5—Cd1—N1—C1178.1 (3)C8—C7—N4—C6−0.1 (4)
S1ii—Cd1—N1—C1−93.2 (2)Cl1—C7—N4—C6179.1 (2)
S1iii—Cd1—N1—C186.8 (2)N1—Cd1—N5—C4−14.4 (5)
N5i—Cd1—N1—C3−177.6 (3)N1i—Cd1—N5—C4165.6 (5)
N5—Cd1—N1—C32.4 (3)S1ii—Cd1—N5—C4−104.4 (4)
S1ii—Cd1—N1—C391.1 (3)S1iii—Cd1—N5—C475.6 (4)
S1iii—Cd1—N1—C3−88.9 (3)
Symmetry codes: (i) −x, −y+2, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+2, −z+2; (iv) x+1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N52.319 (2)Cd1—S1i2.7696 (9)
Cd1—N12.328 (2)
N5ii—Cd1—N189.51 (9)N1—Cd1—S1i90.02 (6)
N5—Cd1—N190.49 (9)N5—Cd1—S1iii91.29 (7)
N5—Cd1—S1i88.71 (7)N1—Cd1—S1iii89.98 (6)
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+2; (iii) −x+1, −y+2, −z+2.
Acknowledgements top

This work is supported by the Doctors' Foundation of Binzhou University.

references
References top

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shi, J. M., Sun, Y. M., Liu, Z., Liu, L. D., Shi, W. & Cheng, P. (2006). Dalton Trans. pp. 376–380.