catena-Poly[[bis­[2-chloro-6-(1H-1,2,4-triazol-1-yl-κN4)pyridine]cadmium(II)]-di-μ-thio­cyanato-κ2N:S;κ2S:N]: a one-dimensional coordination polymer

Yang, Z.N.; Sun, T.T.

doi:10.1107/S1600536808030547

metal-organic compounds

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Volume 64| Part 10| October 2008| Page m1327

doi:10.1107/S1600536808030547

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catena-Poly[[bis[2-chloro-6-(1H-1,2,4-triazol-1-yl-κN⁴)pyridine]cadmium(II)]-di-μ-thiocyanato-κ²N:S;κ²S:N]: a one-dimensional coordination polymer

Zhong Nian Yang ^a ^* and Ting Ting Sun ^b

^aDepartment of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: yangzhongnian1978@yahoo.com.cn

(Received 20 September 2008; accepted 22 September 2008; online 27 September 2008)

In the crystal structure of the title complex, [Cd(NCS)₂(C₇H₅ClN₄)₂]_n, the Cd^II 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 μ_1,3-bridging units connecting adjacent Cd^II atoms with a separation of 5.7525 (11) Å, forming a one-dimensional chain along the a axis.

Related literature

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

Experimental

Crystal data

[Cd(NCS)₂(C₇H₅ClN₄)₂]
M_r = 589.76
Triclinic, $[P \overline 1]$
a = 5.7525 (11) Å
b = 8.0180 (15) Å
c = 12.212 (2) Å
α = 107.609 (3)°
β = 90.095 (2)°
γ = 91.950 (3)°
V = 536.53 (18) Å³
Z = 1
Mo Kα radiation
μ = 1.49 mm⁻¹
T = 298 (2) K
0.23 × 0.21 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.726, T_max = 0.865
2892 measured reflections
2005 independent reflections
1903 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.03
2005 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—N5	2.319 (2)
Cd1—N1	2.328 (2)
Cd1—S1ⁱ	2.7696 (9)

N5ⁱⁱ—Cd1—N1	89.51 (9)
N5—Cd1—N1	90.49 (9)
N5—Cd1—S1ⁱ	88.71 (7)
N1—Cd1—S1ⁱ	90.02 (6)
N5—Cd1—S1ⁱⁱⁱ	91.29 (7)
N1—Cd1—S1ⁱⁱⁱ	89.98 (6)
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+2, -z+2; (iii) -x+1, -y+2, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030547/is2339sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030547/is2339Isup2.hkl

checkCIF report

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 Cd^II 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···Cg2ⁱ_perp = 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···Cg2ⁱ_perp 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.

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

	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].
	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
M_r = 589.76	F(000) = 290
Triclinic, P1	D_x = 1.825 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7525 (11) Å	Cell parameters from 1921 reflections
b = 8.0180 (15) Å	θ = 2.7–28.1°
c = 12.212 (2) Å	µ = 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 tube	1903 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.8°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.726, T_max = 0.865	k = −9→8
2892 measured reflections	l = −11→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.0366P)² + 0.1572P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
2005 reflections	Δρ_max = 0.34 e Å⁻³
143 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (2)

Crystal data top

[Cd(NCS)₂(C₇H₅ClN₄)₂]	γ = 91.950 (3)°
M_r = 589.76	V = 536.53 (18) Å³
Triclinic, P1	Z = 1
a = 5.7525 (11) Å	Mo Kα radiation
b = 8.0180 (15) Å	µ = 1.49 mm⁻¹
c = 12.212 (2) Å	T = 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)
T_min = 0.726, T_max = 0.865	R_int = 0.016
2892 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.03	Δρ_max = 0.34 e Å⁻³
2005 reflections	Δρ_min = −0.36 e Å⁻³
143 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

	x	y	z	U_iso*/U_eq
C1	−0.0042 (5)	0.8697 (4)	0.7162 (2)	0.0411 (6)
H1	−0.1436	0.8065	0.7139	0.049*
C2	0.1609 (7)	0.7193 (5)	0.3111 (3)	0.0639 (9)
H2	0.2549	0.7310	0.2518	0.077*
C3	0.2948 (5)	1.0298 (4)	0.7697 (2)	0.0534 (8)
H3	0.4058	1.1035	0.8178	0.064*
C4	0.5043 (5)	1.2276 (4)	1.0409 (2)	0.0421 (6)
C5	0.2157 (6)	0.8143 (4)	0.4239 (2)	0.0543 (8)
H5	0.3444	0.8913	0.4426	0.065*
C6	0.0695 (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	−0.0696	0.5446	0.2121	0.072*
Cd1	0.0000	1.0000	1.0000	0.04300 (14)
Cl1	−0.40595 (17)	0.45711 (12)	0.35184 (8)	0.0709 (3)
N1	0.1037 (4)	0.9656 (3)	0.81047 (18)	0.0446 (5)
N2	0.1161 (4)	0.8768 (3)	0.62460 (17)	0.0401 (5)
N3	0.3112 (4)	0.9806 (3)	0.65819 (19)	0.0530 (6)
N4	−0.1181 (4)	0.6839 (3)	0.48723 (18)	0.0420 (5)
N5	0.3274 (4)	1.1798 (4)	1.0652 (2)	0.0538 (6)
S1	0.75769 (13)	1.29435 (10)	1.00393 (6)	0.0488 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0387 (14)	0.0535 (15)	0.0288 (12)	−0.0045 (11)	0.0033 (10)	0.0098 (11)
C2	0.081 (2)	0.078 (2)	0.0301 (15)	−0.0033 (18)	0.0091 (14)	0.0133 (14)
C3	0.0507 (17)	0.073 (2)	0.0300 (13)	−0.0198 (15)	0.0021 (12)	0.0083 (13)
C4	0.0382 (15)	0.0524 (16)	0.0289 (12)	−0.0036 (12)	−0.0049 (10)	0.0026 (11)
C5	0.065 (2)	0.0628 (19)	0.0318 (14)	−0.0065 (15)	0.0078 (13)	0.0112 (13)
C6	0.0517 (16)	0.0411 (14)	0.0278 (12)	0.0034 (12)	0.0011 (11)	0.0084 (10)
C7	0.0575 (18)	0.0419 (15)	0.0413 (15)	0.0064 (12)	−0.0075 (13)	0.0052 (11)
C8	0.083 (2)	0.0602 (19)	0.0292 (14)	0.0067 (17)	−0.0040 (14)	0.0025 (13)
Cd1	0.02956 (18)	0.0703 (2)	0.02358 (16)	−0.01005 (12)	0.00224 (10)	0.00706 (12)
Cl1	0.0652 (6)	0.0672 (5)	0.0659 (5)	−0.0086 (4)	−0.0153 (4)	0.0000 (4)
N1	0.0437 (13)	0.0585 (14)	0.0279 (11)	−0.0047 (10)	0.0042 (9)	0.0085 (10)
N2	0.0434 (13)	0.0482 (12)	0.0263 (10)	−0.0039 (10)	0.0034 (9)	0.0082 (9)
N3	0.0533 (15)	0.0698 (16)	0.0312 (12)	−0.0195 (12)	0.0052 (10)	0.0105 (11)
N4	0.0487 (14)	0.0434 (12)	0.0321 (11)	0.0048 (10)	−0.0018 (9)	0.0084 (9)
N5	0.0360 (14)	0.0676 (16)	0.0479 (14)	−0.0086 (11)	0.0004 (10)	0.0035 (12)
S1	0.0407 (4)	0.0620 (5)	0.0401 (4)	−0.0104 (3)	0.0037 (3)	0.0113 (3)

Geometric parameters (Å, º) top

C1—N1	1.316 (3)	C6—N2	1.425 (3)
C1—N2	1.331 (3)	C7—N4	1.326 (3)
C1—H1	0.9300	C7—C8	1.372 (5)
C2—C8	1.361 (5)	C7—Cl1	1.729 (3)
C2—C5	1.387 (4)	C8—H8	0.9300
C2—H2	0.9300	Cd1—N5ⁱ	2.319 (2)
C3—N3	1.303 (3)	Cd1—N5	2.319 (2)
C3—N1	1.356 (3)	Cd1—N1	2.328 (2)
C3—H3	0.9300	Cd1—N1ⁱ	2.328 (2)
C4—N5	1.146 (4)	Cd1—S1ⁱⁱ	2.7696 (9)
C4—S1	1.646 (3)	Cd1—S1ⁱⁱⁱ	2.7696 (9)
C5—C6	1.371 (4)	N2—N3	1.360 (3)
C5—H5	0.9300	S1—Cd1^iv	2.7696 (9)
C6—N4	1.319 (4)

N1—C1—N2	109.8 (2)	N5—Cd1—N1	90.49 (9)
N1—C1—H1	125.1	N5ⁱ—Cd1—N1ⁱ	90.49 (9)
N2—C1—H1	125.1	N5—Cd1—N1ⁱ	89.51 (9)
C8—C2—C5	120.1 (3)	N1—Cd1—N1ⁱ	180.000 (1)
C8—C2—H2	120.0	N5ⁱ—Cd1—S1ⁱⁱ	91.29 (7)
C5—C2—H2	120.0	N5—Cd1—S1ⁱⁱ	88.71 (7)
N3—C3—N1	115.0 (3)	N1—Cd1—S1ⁱⁱ	90.02 (6)
N3—C3—H3	122.5	N1ⁱ—Cd1—S1ⁱⁱ	89.98 (6)
N1—C3—H3	122.5	N5ⁱ—Cd1—S1ⁱⁱⁱ	88.71 (7)
N5—C4—S1	179.1 (3)	N5—Cd1—S1ⁱⁱⁱ	91.29 (7)
C6—C5—C2	116.3 (3)	N1—Cd1—S1ⁱⁱⁱ	89.98 (6)
C6—C5—H5	121.9	N1ⁱ—Cd1—S1ⁱⁱⁱ	90.02 (6)
C2—C5—H5	121.9	S1ⁱⁱ—Cd1—S1ⁱⁱⁱ	180.0
N4—C6—C5	125.8 (3)	C1—N1—C3	103.0 (2)
N4—C6—N2	114.1 (2)	C1—N1—Cd1	127.88 (18)
C5—C6—N2	120.1 (3)	C3—N1—Cd1	129.05 (18)
N4—C7—C8	124.9 (3)	C1—N2—N3	110.0 (2)
N4—C7—Cl1	115.9 (2)	C1—N2—C6	129.0 (2)
C8—C7—Cl1	119.2 (2)	N3—N2—C6	120.9 (2)
C2—C8—C7	117.6 (3)	C3—N3—N2	102.2 (2)
C2—C8—H8	121.2	C6—N4—C7	115.4 (2)
C7—C8—H8	121.2	C4—N5—Cd1	145.7 (2)
N5ⁱ—Cd1—N5	180.0	C4—S1—Cd1^iv	97.18 (11)
N5ⁱ—Cd1—N1	89.51 (9)

C8—C2—C5—C6	0.6 (5)	N1—C1—N2—N3	0.1 (3)
C2—C5—C6—N4	−1.0 (5)	N1—C1—N2—C6	177.3 (3)
C2—C5—C6—N2	178.3 (3)	N4—C6—N2—C1	−1.0 (4)
C5—C2—C8—C7	0.0 (5)	C5—C6—N2—C1	179.6 (3)
N4—C7—C8—C2	−0.3 (5)	N4—C6—N2—N3	175.9 (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—C3	0.0 (3)
N3—C3—N1—C1	0.1 (4)	C6—N2—N3—C3	−177.5 (3)
N3—C3—N1—Cd1	176.6 (2)	C5—C6—N4—C7	0.8 (4)
N5ⁱ—Cd1—N1—C1	−1.9 (3)	N2—C6—N4—C7	−178.6 (2)
N5—Cd1—N1—C1	178.1 (3)	C8—C7—N4—C6	−0.1 (4)
S1ⁱⁱ—Cd1—N1—C1	−93.2 (2)	Cl1—C7—N4—C6	179.1 (2)
S1ⁱⁱⁱ—Cd1—N1—C1	86.8 (2)	N1—Cd1—N5—C4	−14.4 (5)
N5ⁱ—Cd1—N1—C3	−177.6 (3)	N1ⁱ—Cd1—N5—C4	165.6 (5)
N5—Cd1—N1—C3	2.4 (3)	S1ⁱⁱ—Cd1—N5—C4	−104.4 (4)
S1ⁱⁱ—Cd1—N1—C3	91.1 (3)	S1ⁱⁱⁱ—Cd1—N5—C4	75.6 (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.

Experimental details

Crystal data
Chemical formula	[Cd(NCS)₂(C₇H₅ClN₄)₂]
M_r	589.76
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.7525 (11), 8.0180 (15), 12.212 (2)
α, β, γ (°)	107.609 (3), 90.095 (2), 91.950 (3)
V (Å³)	536.53 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.49
Crystal size (mm)	0.23 × 0.21 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.726, 0.865
No. of measured, independent and observed [I > 2σ(I)] reflections	2892, 2005, 1903
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.03
No. of reflections	2005
No. of parameters	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cd1—N5	2.319 (2)	Cd1—S1ⁱ	2.7696 (9)
Cd1—N1	2.328 (2)

N5ⁱⁱ—Cd1—N1	89.51 (9)	N1—Cd1—S1ⁱ	90.02 (6)
N5—Cd1—N1	90.49 (9)	N5—Cd1—S1ⁱⁱⁱ	91.29 (7)
N5—Cd1—S1ⁱ	88.71 (7)	N1—Cd1—S1ⁱⁱⁱ	89.98 (6)

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

Acknowledgements

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

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, J. M., Sun, Y. M., Liu, Z., Liu, L. D., Shi, W. & Cheng, P. (2006). Dalton Trans. pp. 376–380. CSD CrossRef PubMed Google Scholar

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