catena-Poly[[bis­[2-chloro-6-(1H-1,2,4-triazol-1-yl-κN ⁴)pyridine]cadmium(II)]-di-μ-thio­cyanato-κ² N:S;κ² S:N]: a one-dimensional coordination polymer

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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

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

Figures

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.

Crystal data

[Cd(NCS)2(C7H5ClN4)2]	Z = 1
Mr = 589.76	F(000) = 290
Triclinic, P1	Dx = 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

Bruker SMART APEX CCD diffractometer	2005 independent reflections
Radiation source: fine-focus sealed tube	1903 reflections with I > 2σ(I)
graphite	Rint = 0.016
φ and ω scans	θmax = 25.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
Tmin = 0.726, Tmax = 0.865	k = −9→8
2892 measured reflections	l = −11→14

Refinement

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(Fo2) + (0.0366P)2 + 0.1572P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.002
2005 reflections	Δρmax = 0.34 e Å−3
143 parameters	Δρmin = −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)

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
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 (Ų)

	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, °)

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—Cd1iv	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—Cd1iv	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.