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The coordination geometry of the CdII atom in the title complex, [Cd(NCS)2(C12H12N6)2]n or [Cd(NCS)2(mbtz)2]n, where mbtz is 1,3-bis­(1,2,4-triazol-1-ylmeth­yl)benzene, is a distorted compressed octa­hedron in which the CdII atom lies on an inversion centre, coordinated by four N atoms from the triazole rings of four mbtz ligands and two N atoms from two monodentate NCS ligands. The structure is polymeric, with 24-membered spiro-fused rings extending along [100] and with the 24-membered ring containing two inversion-related mbtz mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010603294X/gd3044sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010603294X/gd3044Isup2.hkl
Contains datablock I

CCDC reference: 625684

Comment top

Recently, considerable attention has been paid to the metal coordination polymers for their intriguing structures and potential application as functional materials (Batten & Robson, 1998; Blake et al., 1999; Kitagawa et al., 2004). The design of coordination polymers is greatly influenced by several factors, such as the metal coordination preference, the structural characteristics of the polydentate organic ligand, the metal–ligand ratio, the solvent system and the counter-ion. The ligand is no doubt the key factor in constructing topological motifs.

1,2,4-Triazole and its derivatives are very interesting ligands because they combine the coordination geometry of pyrazole and imidazole with regard to the arrangement of the three heteroatoms. Some novel coordination polymers containing flexible bis(triazole) ligands have been reported recently (Haasnoot, 2000; Albada et al., 2000; Zhao et al., 2002; Meng et al., 2004). Our interest is the study of the coordination chemistry of 1,2,4-triazole and its derivatives with potential applications in materials science. We have already reported the crystal structures of coordination polymers containing the flexible ligands 1,2-bis(1,2,4-triazol-1-yl)ethane (bte) (Li et al., 2004; Wang et al., 2005) and 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (bbtz) (Li et al., 2005; Peng et al., 2006). We report here the crystal structure of a novel one-dimensional double-stranded chain polymer, [Cd(NCS)2(mbtz)2]n (I), which has been synthesized using the ligand 1,3-bis(1,2,4-triazol-1-ylmethyl)benzene (mbtz).

In the complex, the Cd atom lies on an inversion centre (Fig. 1). The coordination geometry of the CdII atom is a distorted compressed octahedron, coordinated by four N atoms from the triazole rings of mbtz ligands forming the equatorial plane, and two N atoms from two monodentate NCS ligands occupying the axial sites. The Cd—N bond lengths (Table 1) are in the range 2.302 (2) to 2.371 (2) Å, similar to those in Cd–triazole complexes reported previously (Li et al., 2004, 2005; Meng et al., 2004). The r.m.s. deviations of the atoms from the mean planes of the triazole rings N1–N3/C9/C10 and N4–N6/C11/C12 and the benzene ring C1–C6 are 0.0024 (14), 0.0043 (16) and 0.0023 (18) Å, respectively. The dihedral angles between the benzene ring and the N1–N3/C9/C10 and N4–N6/C11/C12 triazole rings are 84.24 (9) and 79.32 (8)°, respectively. The dihedral angle between two triazole rings is 70.01 (10)°. The mbtz ligands exhibit the gauchegauche conformation in complex (I). The centroid-to-centroid distance between adjacent triazole rings is 6.921 Å.

Compound (I) has a one-dimensional double-chain structure, with two strands of mbtz ligands held together by CdII atoms (Li et al., 2004, 2005; Zhao et al., 1999). The chain runs along [100] and consists of 24-membered spiro-fused rings, in which two CdII atoms are joined via two mbtz molecules. The Cd···Cd separation across the bridging mbtz ligand is equal to the a-axis translation. The shortest inter-chain Cd···Cd distances are 8.7717 (13) and 8.988 (2) Å, along [010] and [001], respectively (Fig. 2).

The benzene ring plane C1–C6 is parallel to the adjacent benzene ring plane C1–C6 at (−x, −y, 1 − z), with an interplanar spacing of 3.409 (2) Å and a ring-centroid separation of 3.973 (2) Å, indicating ππ stacking along [010].

Experimental top

A water–methanol solution (20 ml, 1:1 v/v) of Cd(NO3)2·4H2O (0.156 g, 0.50 mmol) was added to one leg of an H-shaped tube, and a water–methanol solution (20 ml, 1:1 v/v) of KNCS (0.097 g, 1.00 mmol) and mbtz (0.240 g, 1.00 mmol) was added to the other leg of the tube. After several weeks, well shaped colourless single crystals were obtained. Analysis found: C 43.95, H 3.3, N 27.6%; C26H24CdN14S2 requires: C 44.0, H 3.4, N 27.7%.

Refinement top

H atom were placed in idealized positions and treated as riding atoms, with C—H distances of 0.95 (triazole and benzene) and 0.99 Å (CH2), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The coordination environment of the Cd atom of (I) at the 30% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x, −y + 1, −z + 1; (iii) x + 1, y, z; (iv) x − 1, y, z.] For the sake of clarity the H atoms have been omitted.
[Figure 2] Fig. 2. The packing of (I) viewed along [010]. For the sake of clarity the H atoms have been omitted.
catena-Poly[[diisothiocyanatocadmium(II)]-bis[µ-1,3-bis(1,2,4-triazol- 1-ylmethyl)benzene-κ2N4:N4']] top
Crystal data top
[Cd(NCS)2(C12H12N6)2]F(000) = 716
Mr = 709.11Dx = 1.600 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 5078 reflections
a = 10.9140 (16) Åθ = 3.0–25.4°
b = 8.7717 (13) ŵ = 0.93 mm1
c = 15.692 (2) ÅT = 153 K
β = 101.488 (3)°Block, colorless
V = 1472.1 (4) Å30.30 × 0.30 × 0.17 mm
Z = 2
Data collection top
Rigaku Mercury CCD
diffractometer
2691 independent reflections
Radiation source: fine-focus sealed tube2502 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 25.4°, θmin = 3.0°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 1313
Tmin = 0.768, Tmax = 0.858k = 1010
13865 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0282P)2 + 1.434P]
where P = (Fo2 + 2Fc2)/3
2691 reflections(Δ/σ)max < 0.001
197 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
[Cd(NCS)2(C12H12N6)2]V = 1472.1 (4) Å3
Mr = 709.11Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.9140 (16) ŵ = 0.93 mm1
b = 8.7717 (13) ÅT = 153 K
c = 15.692 (2) Å0.30 × 0.30 × 0.17 mm
β = 101.488 (3)°
Data collection top
Rigaku Mercury CCD
diffractometer
2691 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
2502 reflections with I > 2σ(I)
Tmin = 0.768, Tmax = 0.858Rint = 0.030
13865 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.070H-atom parameters constrained
S = 1.08Δρmax = 0.26 e Å3
2691 reflectionsΔρmin = 0.32 e Å3
197 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
xyzUiso*/Ueq
Cd10.50000.50000.50000.02308 (10)
S10.29960 (7)0.51548 (9)0.74310 (5)0.03710 (19)
N10.37597 (19)0.0519 (2)0.58345 (14)0.0220 (5)
N20.3507 (2)0.0267 (3)0.49581 (15)0.0274 (5)
N30.43983 (19)0.2561 (2)0.52712 (14)0.0242 (5)
N40.11685 (19)0.3462 (2)0.63188 (14)0.0253 (5)
N50.0765 (2)0.4344 (3)0.57120 (16)0.0354 (6)
N60.2863 (2)0.4396 (3)0.55171 (15)0.0276 (5)
N70.4790 (2)0.5645 (3)0.64135 (15)0.0338 (6)
C10.1936 (2)0.0362 (3)0.63697 (17)0.0230 (5)
C20.1476 (2)0.0953 (3)0.66964 (16)0.0241 (6)
H2A0.20440.16920.69890.029*
C30.0201 (2)0.1194 (3)0.65995 (16)0.0237 (6)
C40.0625 (2)0.0097 (3)0.61718 (16)0.0255 (6)
H4A0.15010.02470.61020.031*
C50.0174 (3)0.1201 (3)0.58510 (17)0.0287 (6)
H5A0.07420.19410.55580.034*
C60.1104 (2)0.1440 (3)0.59521 (16)0.0264 (6)
H6A0.14070.23460.57340.032*
C70.3326 (2)0.0546 (3)0.64292 (19)0.0284 (6)
H7A0.37720.03460.70320.034*
H7B0.35120.16040.62770.034*
C80.0286 (3)0.2609 (3)0.69710 (17)0.0315 (6)
H8A0.07050.23110.74500.038*
H8B0.04270.32780.72170.038*
C90.3916 (2)0.1526 (3)0.46503 (17)0.0249 (6)
H9A0.38770.16940.40470.030*
C100.4281 (2)0.1885 (3)0.60029 (17)0.0235 (6)
H10A0.45330.23110.65670.028*
C110.1811 (3)0.4887 (3)0.52541 (19)0.0313 (6)
H11A0.18350.55650.47790.038*
C120.2404 (2)0.3502 (3)0.61845 (18)0.0307 (6)
H12A0.28940.29620.65210.037*
C130.4035 (3)0.5444 (3)0.68332 (17)0.0255 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02345 (16)0.02030 (16)0.02658 (16)0.00320 (11)0.00757 (11)0.00309 (11)
S10.0377 (4)0.0443 (4)0.0322 (4)0.0012 (3)0.0140 (3)0.0018 (3)
N10.0174 (10)0.0202 (11)0.0286 (12)0.0019 (9)0.0051 (9)0.0006 (9)
N20.0197 (11)0.0321 (13)0.0302 (13)0.0014 (9)0.0044 (9)0.0033 (10)
N30.0214 (11)0.0223 (11)0.0287 (12)0.0023 (9)0.0044 (9)0.0009 (9)
N40.0206 (11)0.0301 (12)0.0253 (12)0.0023 (9)0.0051 (9)0.0031 (9)
N50.0302 (13)0.0350 (13)0.0411 (14)0.0053 (11)0.0073 (11)0.0032 (12)
N60.0231 (11)0.0266 (12)0.0330 (13)0.0044 (10)0.0058 (10)0.0025 (10)
N70.0389 (14)0.0324 (13)0.0317 (13)0.0038 (11)0.0109 (12)0.0010 (11)
C10.0215 (13)0.0231 (13)0.0246 (13)0.0005 (10)0.0052 (10)0.0063 (10)
C20.0191 (13)0.0260 (14)0.0252 (14)0.0021 (11)0.0005 (10)0.0005 (11)
C30.0227 (13)0.0306 (14)0.0172 (13)0.0030 (11)0.0026 (10)0.0038 (11)
C40.0193 (12)0.0378 (16)0.0187 (13)0.0027 (11)0.0019 (10)0.0034 (11)
C50.0285 (15)0.0324 (15)0.0235 (14)0.0100 (12)0.0007 (11)0.0012 (12)
C60.0340 (15)0.0217 (13)0.0242 (14)0.0015 (11)0.0075 (11)0.0018 (11)
C70.0253 (14)0.0209 (13)0.0390 (16)0.0024 (11)0.0064 (12)0.0075 (12)
C80.0257 (14)0.0425 (17)0.0251 (14)0.0061 (13)0.0020 (11)0.0062 (12)
C90.0184 (13)0.0301 (14)0.0254 (14)0.0021 (11)0.0025 (11)0.0002 (11)
C100.0199 (13)0.0211 (13)0.0288 (14)0.0024 (11)0.0028 (11)0.0022 (11)
C110.0289 (15)0.0275 (15)0.0375 (16)0.0035 (12)0.0069 (13)0.0054 (12)
C120.0204 (14)0.0398 (16)0.0329 (15)0.0049 (12)0.0080 (12)0.0062 (13)
C130.0326 (15)0.0194 (13)0.0213 (13)0.0042 (11)0.0022 (12)0.0020 (10)
Geometric parameters (Å, º) top
Cd1—N32.302 (2)C1—C61.383 (4)
Cd1—N3i2.302 (2)C1—C21.395 (4)
Cd1—N7i2.344 (2)C1—C71.509 (4)
Cd1—N72.344 (2)C2—C31.385 (4)
Cd1—N6ii2.371 (2)C2—H2A0.9500
Cd1—N6iii2.371 (2)C3—C41.396 (4)
S1—C131.629 (3)C3—C81.512 (4)
N1—C101.330 (3)C4—C51.375 (4)
N1—N21.366 (3)C4—H4A0.9500
N1—C71.464 (3)C5—C61.388 (4)
N2—C91.318 (3)C5—H5A0.9500
N3—C101.321 (3)C6—H6A0.9500
N3—C91.359 (3)C7—H7A0.9900
N4—C121.323 (3)C7—H7B0.9900
N4—N51.366 (3)C8—H8A0.9900
N4—C81.464 (3)C8—H8B0.9900
N5—C111.312 (4)C9—H9A0.9500
N6—C121.325 (3)C10—H10A0.9500
N6—C111.365 (4)C11—H11A0.9500
N6—Cd1iv2.371 (2)C12—H12A0.9500
N7—C131.166 (3)
N3—Cd1—N3i180.0C2—C3—C8120.4 (2)
N3—Cd1—N7i92.05 (8)C4—C3—C8120.5 (2)
N3i—Cd1—N7i87.95 (8)C5—C4—C3120.2 (2)
N3—Cd1—N787.95 (8)C5—C4—H4A119.9
N3i—Cd1—N792.05 (8)C3—C4—H4A119.9
N7i—Cd1—N7180.0C4—C5—C6120.5 (2)
N3—Cd1—N6ii88.48 (7)C4—C5—H5A119.7
N3i—Cd1—N6ii91.52 (7)C6—C5—H5A119.7
N7i—Cd1—N6ii90.29 (8)C1—C6—C5120.1 (2)
N7—Cd1—N6ii89.71 (8)C1—C6—H6A120.0
N3—Cd1—N6iii91.52 (7)C5—C6—H6A120.0
N3i—Cd1—N6iii88.48 (7)N1—C7—C1109.9 (2)
N7i—Cd1—N6iii89.71 (8)N1—C7—H7A109.7
N7—Cd1—N6iii90.29 (8)C1—C7—H7A109.7
N6ii—Cd1—N6iii180.0N1—C7—H7B109.7
C10—N1—N2109.8 (2)C1—C7—H7B109.7
C10—N1—C7128.9 (2)H7A—C7—H7B108.2
N2—N1—C7120.8 (2)N4—C8—C3112.5 (2)
C9—N2—N1102.6 (2)N4—C8—H8A109.1
C10—N3—C9103.4 (2)C3—C8—H8A109.1
C10—N3—Cd1131.19 (17)N4—C8—H8B109.1
C9—N3—Cd1124.93 (17)C3—C8—H8B109.1
C12—N4—N5109.5 (2)H8A—C8—H8B107.8
C12—N4—C8129.2 (2)N2—C9—N3114.1 (2)
N5—N4—C8121.2 (2)N2—C9—H9A122.9
C11—N5—N4102.8 (2)N3—C9—H9A122.9
C12—N6—C11102.5 (2)N3—C10—N1110.1 (2)
C12—N6—Cd1iv126.48 (18)N3—C10—H10A125.0
C11—N6—Cd1iv130.95 (18)N1—C10—H10A125.0
C13—N7—Cd1135.3 (2)N5—C11—N6114.4 (2)
C6—C1—C2119.2 (2)N5—C11—H11A122.8
C6—C1—C7120.9 (2)N6—C11—H11A122.8
C2—C1—C7119.8 (2)N4—C12—N6110.8 (2)
C3—C2—C1120.9 (2)N4—C12—H12A124.6
C3—C2—H2A119.6N6—C12—H12A124.6
C1—C2—H2A119.6N7—C13—S1179.2 (3)
C2—C3—C4119.0 (2)
C10—N1—N2—C90.6 (3)C7—C1—C6—C5175.5 (2)
C7—N1—N2—C9173.3 (2)C4—C5—C6—C10.7 (4)
N7i—Cd1—N3—C10167.7 (2)C10—N1—C7—C196.8 (3)
N7—Cd1—N3—C1012.3 (2)N2—N1—C7—C174.3 (3)
N6ii—Cd1—N3—C10102.0 (2)C6—C1—C7—N1106.2 (3)
N6iii—Cd1—N3—C1078.0 (2)C2—C1—C7—N170.2 (3)
N7i—Cd1—N3—C921.3 (2)C12—N4—C8—C3101.6 (3)
N7—Cd1—N3—C9158.7 (2)N5—N4—C8—C376.1 (3)
N6ii—Cd1—N3—C968.9 (2)C2—C3—C8—N4125.9 (3)
N6iii—Cd1—N3—C9111.1 (2)C4—C3—C8—N455.5 (3)
C12—N4—N5—C111.1 (3)N1—N2—C9—N30.6 (3)
C8—N4—N5—C11179.2 (2)C10—N3—C9—N20.4 (3)
N3—Cd1—N7—C1347.0 (3)Cd1—N3—C9—N2172.61 (16)
N3i—Cd1—N7—C13133.0 (3)C9—N3—C10—N10.1 (3)
N6ii—Cd1—N7—C1341.5 (3)Cd1—N3—C10—N1172.40 (15)
N6iii—Cd1—N7—C13138.5 (3)N2—N1—C10—N30.4 (3)
C6—C1—C2—C30.7 (4)C7—N1—C10—N3172.3 (2)
C7—C1—C2—C3175.8 (2)N4—N5—C11—N60.9 (3)
C1—C2—C3—C40.3 (4)C12—N6—C11—N50.4 (3)
C1—C2—C3—C8178.9 (2)Cd1iv—N6—C11—N5177.96 (18)
C2—C3—C4—C50.2 (4)N5—N4—C12—N61.0 (3)
C8—C3—C4—C5178.7 (2)C8—N4—C12—N6178.9 (2)
C3—C4—C5—C60.4 (4)C11—N6—C12—N40.4 (3)
C2—C1—C6—C50.9 (4)Cd1iv—N6—C12—N4177.33 (17)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x+1, y, z; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formula[Cd(NCS)2(C12H12N6)2]
Mr709.11
Crystal system, space groupMonoclinic, P21/c
Temperature (K)153
a, b, c (Å)10.9140 (16), 8.7717 (13), 15.692 (2)
β (°) 101.488 (3)
V3)1472.1 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.93
Crystal size (mm)0.30 × 0.30 × 0.17
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.768, 0.858
No. of measured, independent and
observed [I > 2σ(I)] reflections
13865, 2691, 2502
Rint0.030
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.070, 1.08
No. of reflections2691
No. of parameters197
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.32

Computer programs: CrystalClear (Rigaku, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Cd1—N32.302 (2)S1—C131.629 (3)
Cd1—N72.344 (2)N7—C131.166 (3)
Cd1—N6i2.371 (2)
N3—Cd1—N787.95 (8)N7—Cd1—N6i89.71 (8)
N3—Cd1—N6i88.48 (7)N7—C13—S1179.2 (3)
Symmetry code: (i) x, y+1, z+1.
 

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