Download citation
Download citation
link to html
The asymmetric unit of the title complex, [CdCl2(C14H12N4O2S)2]n, consists of one CdII ion located on the crystallographic inversion centre, one 4-benzoyl-1-­iso­nicotinoyl­thio­semi­carbazide ligand and one chloride ligand. The central CdII ion adopts a distorted octa­hedral coordination geometry formed by two pyridyl N atoms of two ligands, two S atoms of two other ligands and two chloride ligands. The thio­semi­carbazide ligands act as bridges, linking the metal ions into a two-dimensional layered structure parallel to the bc plane. Inter­molecular N—H...O hydrogen bonds and C—H...π inter­actions exist between adjacent layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110011455/fn3054sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110011455/fn3054Isup2.hkl
Contains datablock I

CCDC reference: 767690

Comment top

Thiosemicarbazides and their derivatives have attracted considerable interest, not only because of their potentially beneficial biological properties, such as antibacterial, antitumour and antiviral activities (Angelusiu et al., 2009; Belicchi-Ferrari et al., 2007; Palaska et al., 2002), but also because of their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Many metal complexes derived from thiosemicarbazone, particularly the 1,4-substituted derivatives, have been prepared and characterized, and have been found to possess a wide variety of biological activities (Floquet et al., 2009; Leovac et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al., 2002; Belicchi-Ferrari et al., 2000). However, only a few 1,4-bisacylthiosemicarbazone ligands have been reported so far (Xue et al., 2006; Ali et al., 2004; Yamin & Yusof, 2003; Yusof et al., 2003). Acylthiosemicarbazide ligands contain O, S and N as potential donor atoms and can support mononuclear, multinuclear or even extended structure complexes. They can also form hydrogen bonds in the crystal structure, which is very important in the design and synthesis of novel supramolecular structures.

Recently, much attention has been paid to coordination polymers with a framework structure, because of their potential applications and theoretical significance (Uemura et al., 2009; Tranchemontagne et al., 2009; Kurmoo, 2009; Lee et al., 2009). However, there is no previous report of coordination polymers with a 1,4-bisacylthiosemicarbazone ligand. Our group reported the first transition metal complex with a 1,4-bisacylthiosemicarbazone ligand (Ke et al., 2007). That cobalt complex is mononuclear. In order to connect the metal centres to form a framework, we increased the possible donor atoms by replacing one of the phenyl groups with a pyridine ring. Here, we report the title two-dimensional coordination polymer, (I), which is the first transition metal complex with such ligands with an extended structure.

The asymmetric unit of complex (I) contains one CdII ion located on an inversion centre, one independent ligand and one chloride ion. The local coordination geometry around the CdII centre can be described as distorted octahedral (Fig. 1 and Table 1). The equatorial plane is formed by two N atoms [N4i and N4ii; symmetry codes: (i) -x + 1, y - 1, -z + 3/2; (ii) x, -y + 2, z - 1/2] of two pyridine rings with a Cd—N bond of 2.373 (3) Å, and two Cl- ions [Cl1 and Cl1iii; symmetry code: (iii) -x + 1, -y + 1, -z + 1] with a Cd—Cl bond length of 2.583 (3) Å. The axial positions are occupied by two S atoms (S1 and S1iii) from two other ligands with a Cd—S bond of 2.736 (4) Å.

Each thiosemicarbazide ligand acts as a linear linker to coordinate two metal centers, while each metal ion is linked by four ligands and two chloride ligands in a trans configuration. Thus, twodimensional undulating layers are formed parallel to the bc plane (Fig. 2). The benzoyl groups are located on both sides of the layers. There are three types of intralayer hydrogen bonds, namely N1—H1···Cl1, N3—H3···Cl1 and N2—H10···O1 while there is one type of interlayer hydrogen bond. Neighboring layers are further connected to each other via N2—H10···O1 hydrogen bonds [N2···O1 = 3.010 (3) Å and N2—H10···O1 = 141°] and C6—H6···π interactions [C6···pyridyl = 3.327 (4) Å and C6—H6···Cg = 122°] (Fig. 3 and Table 2).

Compared with the previously reported cobalt complex (Ke et al., 2007), in this cadmium polymer the ligands coordinate to the CdII ions with atoms N4 and S1 in a bridging motif, and the structure is characterized by a two-dimensional architecture. The dihedral angle between the phenyl and pyridyl groups is 39.46 (9)°. However, in the previously reported complex, the tridentate ligands coordinate to the CoII centre through one N atom and two carbonyl O atoms in a chelating mode and the complex presents a mononuclear structure. The dihedral angles between the two phenyl groups are 28.03 (1) and 10.38 (2)°. The discrepancy indicates that 1,4-bisacylthiosemicarbazone ligands have varied coordination motifs.

Experimental top

The ligand was prepared following the procedure described by Xue et al. (2006). The ligand (0.0189 g, 0.10 mmol) and cadmium chloride hydrate (0.0115 g, 0.05 mmol) were dissolved in a mixed solvent of methanol and N,N-dimethylformamide (11 ml, 10:1 v/v). After 5 min, dichloromethane (2 ml) was added and the solution was then stirred for 3 h at room temperature. Colourless cube-shaped crystals of (I) crystallized from the solvent mixture after about 10 d.

Refinement top

All H atoms bonded to C and N atoms were allowed for in idealized positions using the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-labelling scheme and 30% probability displacement ellipsoids. H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1, y - 1, -z + 3/2; (ii) x, -y + 2, z - 1/2; (iii) -x + 1, -y + 1, -z + 1.] [Symops have been swapped to match order in text and table - please check]
[Figure 2] Fig. 2. A view of the two-dimensional layer in (I).
[Figure 3] Fig. 3. A packing diagram for (I), with hydrogen bonds shown as dashed lines.
Poly[bis(µ-4-benzoyl-1-isonicotinoylthiosemicarbazide- κ2N:S)dichloridocadmium(II)] top
Crystal data top
[CdCl2(C14H12N4O2S)2]F(000) = 1576
Mr = 783.97Dx = 1.711 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 26.272 (5) Åθ = 12–18°
b = 8.8773 (18) ŵ = 1.08 mm1
c = 14.453 (3) ÅT = 293 K
β = 115.46 (3)°Cube, colourless
V = 3043.5 (11) Å30.24 × 0.21 × 0.17 mm
Z = 4
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
3349 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 27.5°, θmin = 3.1°
ω scansh = 3433
12400 measured reflectionsk = 1111
3494 independent reflectionsl = 1318
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.23 w = 1/[σ2(Fo2) + (0.0113P)2 + 5.5854P]
where P = (Fo2 + 2Fc2)/3
3494 reflections(Δ/σ)max < 0.001
205 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[CdCl2(C14H12N4O2S)2]V = 3043.5 (11) Å3
Mr = 783.97Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.272 (5) ŵ = 1.08 mm1
b = 8.8773 (18) ÅT = 293 K
c = 14.453 (3) Å0.24 × 0.21 × 0.17 mm
β = 115.46 (3)°
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
3349 reflections with I > 2σ(I)
12400 measured reflectionsRint = 0.035
3494 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 1.23Δρmax = 0.39 e Å3
3494 reflectionsΔρmin = 0.26 e Å3
205 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cd10.50000.50000.50000.02616 (8)
Cl10.41333 (3)0.34130 (8)0.38539 (5)0.03487 (15)
S10.45032 (3)0.63726 (8)0.60981 (5)0.02923 (14)
O10.25935 (8)0.6262 (2)0.44396 (17)0.0468 (6)
N10.34748 (9)0.5318 (2)0.48917 (16)0.0287 (5)
H10.36560.46420.47260.034*
N20.35198 (9)0.7333 (2)0.59269 (16)0.0304 (5)
H100.31580.73140.56600.037*
N30.38086 (9)0.8371 (2)0.66833 (16)0.0297 (5)
H30.38840.81830.73120.036*
N40.46686 (9)1.3021 (2)0.87810 (16)0.0293 (5)
O20.38809 (11)0.9997 (2)0.55513 (15)0.0547 (6)
C10.21305 (15)0.1154 (4)0.2926 (3)0.0593 (10)
H40.19500.02640.26200.071*
C20.26365 (16)0.1101 (4)0.3779 (3)0.0557 (9)
H20.28000.01760.40450.067*
C30.29043 (13)0.2425 (3)0.4247 (2)0.0434 (7)
H90.32530.23910.48130.052*
C40.26513 (11)0.3792 (3)0.3869 (2)0.0340 (6)
C50.21404 (12)0.3845 (4)0.3002 (2)0.0452 (8)
H50.19680.47650.27460.054*
C60.18907 (13)0.2514 (4)0.2525 (3)0.0578 (10)
H60.15570.25420.19260.069*
C70.28880 (11)0.5233 (3)0.4406 (2)0.0321 (6)
C80.37951 (10)0.6364 (3)0.56055 (18)0.0248 (5)
C90.39726 (11)0.9688 (3)0.6423 (2)0.0318 (6)
C100.42468 (11)1.0792 (3)0.72875 (19)0.0291 (5)
C110.44504 (14)1.0437 (3)0.8315 (2)0.0458 (8)
H110.44480.94460.85230.055*
C120.46586 (14)1.1585 (3)0.9029 (2)0.0441 (8)
H120.47991.13360.97200.053*
C130.42716 (12)1.2273 (3)0.7029 (2)0.0324 (6)
H130.41511.25480.63460.039*
C140.44756 (12)1.3344 (3)0.7789 (2)0.0326 (6)
H140.44791.43440.76010.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02771 (13)0.02192 (13)0.02609 (13)0.00408 (11)0.00894 (10)0.00354 (10)
Cl10.0310 (3)0.0327 (3)0.0398 (4)0.0015 (3)0.0142 (3)0.0098 (3)
S10.0229 (3)0.0317 (3)0.0297 (3)0.0009 (3)0.0081 (3)0.0057 (3)
O10.0265 (10)0.0482 (13)0.0578 (13)0.0032 (9)0.0106 (10)0.0231 (11)
N10.0242 (10)0.0261 (11)0.0347 (11)0.0002 (9)0.0116 (9)0.0113 (9)
N20.0247 (10)0.0291 (11)0.0342 (12)0.0027 (9)0.0095 (9)0.0137 (9)
N30.0334 (12)0.0262 (11)0.0268 (11)0.0029 (9)0.0102 (9)0.0093 (9)
N40.0326 (12)0.0246 (11)0.0260 (10)0.0043 (9)0.0081 (9)0.0031 (9)
O20.0878 (18)0.0362 (11)0.0285 (10)0.0085 (12)0.0141 (11)0.0026 (9)
C10.052 (2)0.054 (2)0.078 (3)0.0258 (18)0.034 (2)0.039 (2)
C20.065 (2)0.0378 (18)0.067 (2)0.0123 (17)0.031 (2)0.0146 (16)
C30.0446 (17)0.0367 (16)0.0457 (17)0.0073 (14)0.0163 (14)0.0087 (13)
C40.0280 (13)0.0381 (15)0.0378 (15)0.0075 (12)0.0160 (12)0.0143 (12)
C50.0296 (15)0.0530 (19)0.0510 (18)0.0025 (14)0.0154 (14)0.0195 (15)
C60.0314 (16)0.076 (3)0.062 (2)0.0154 (17)0.0158 (16)0.037 (2)
C70.0260 (12)0.0359 (15)0.0334 (13)0.0031 (11)0.0119 (11)0.0105 (11)
C80.0267 (12)0.0214 (12)0.0246 (12)0.0002 (10)0.0096 (10)0.0002 (10)
C90.0346 (14)0.0266 (14)0.0279 (13)0.0012 (11)0.0075 (11)0.0051 (10)
C100.0287 (13)0.0249 (13)0.0285 (13)0.0016 (11)0.0074 (11)0.0037 (10)
C110.066 (2)0.0206 (13)0.0322 (15)0.0040 (13)0.0032 (14)0.0002 (11)
C120.065 (2)0.0239 (14)0.0274 (14)0.0070 (14)0.0049 (14)0.0012 (11)
C130.0403 (15)0.0294 (14)0.0264 (13)0.0058 (12)0.0132 (12)0.0008 (11)
C140.0413 (15)0.0235 (13)0.0317 (13)0.0059 (11)0.0143 (12)0.0006 (11)
Geometric parameters (Å, º) top
Cd1—N4i2.373 (2)C1—C21.371 (5)
Cd1—N4ii2.373 (2)C1—H40.9300
Cd1—Cl12.5828 (10)C2—C31.387 (4)
Cd1—Cl1iii2.5828 (10)C2—H20.9300
Cd1—S12.7364 (8)C3—C41.378 (4)
Cd1—S1iii2.7364 (8)C3—H90.9300
S1—C81.682 (3)C4—C51.388 (4)
O1—C71.211 (3)C4—C71.487 (4)
N1—C81.374 (3)C5—C61.384 (4)
N1—C71.395 (3)C5—H50.9300
N1—H10.8600C6—H60.9300
N2—C81.330 (3)C9—C101.505 (3)
N2—N31.381 (3)C10—C131.376 (4)
N2—H100.8600C10—C111.381 (4)
N3—C91.354 (3)C11—C121.385 (4)
N3—H30.8600C11—H110.9300
N4—C121.327 (3)C12—H120.9300
N4—C141.330 (3)C13—C141.376 (4)
N4—Cd1iv2.373 (2)C13—H130.9300
O2—C91.209 (3)C14—H140.9300
C1—C61.370 (5)
N4i—Cd1—N4ii180.00 (9)C4—C3—H9120.1
N4i—Cd1—Cl190.76 (6)C2—C3—H9120.1
N4ii—Cd1—Cl189.24 (6)C3—C4—C5120.1 (3)
N4i—Cd1—Cl1iii89.24 (6)C3—C4—C7121.9 (3)
N4ii—Cd1—Cl1iii90.76 (6)C5—C4—C7117.8 (3)
Cl1—Cd1—Cl1iii180.0C6—C5—C4119.2 (3)
N4i—Cd1—S190.77 (6)C6—C5—H5120.4
N4ii—Cd1—S189.23 (6)C4—C5—H5120.4
Cl1—Cd1—S196.09 (2)C1—C6—C5120.6 (3)
Cl1iii—Cd1—S183.91 (2)C1—C6—H6119.7
N4i—Cd1—S1iii89.23 (6)C5—C6—H6119.7
N4ii—Cd1—S1iii90.77 (6)O1—C7—N1121.8 (2)
Cl1—Cd1—S1iii83.91 (2)O1—C7—C4122.6 (2)
Cl1iii—Cd1—S1iii96.09 (3)N1—C7—C4115.6 (2)
S1—Cd1—S1iii180.000 (18)N2—C8—N1116.8 (2)
C8—S1—Cd1117.96 (9)N2—C8—S1121.17 (19)
C8—N1—C7127.0 (2)N1—C8—S1122.00 (19)
C8—N1—H1116.5O2—C9—N3122.7 (2)
C7—N1—H1116.5O2—C9—C10121.9 (2)
C8—N2—N3120.8 (2)N3—C9—C10115.3 (2)
C8—N2—H10119.6C13—C10—C11117.9 (2)
N3—N2—H10119.6C13—C10—C9117.3 (2)
C9—N3—N2119.3 (2)C11—C10—C9124.7 (2)
C9—N3—H3120.4C10—C11—C12118.7 (3)
N2—N3—H3120.4C10—C11—H11120.7
C12—N4—C14117.1 (2)C12—C11—H11120.7
C12—N4—Cd1iv123.66 (18)N4—C12—C11123.6 (3)
C14—N4—Cd1iv119.24 (17)N4—C12—H12118.2
C6—C1—C2120.2 (3)C11—C12—H12118.2
C6—C1—H4119.9C14—C13—C10119.4 (2)
C2—C1—H4119.9C14—C13—H13120.3
C1—C2—C3120.1 (3)C10—C13—H13120.3
C1—C2—H2119.9N4—C14—C13123.3 (2)
C3—C2—H2119.9N4—C14—H14118.4
C4—C3—C2119.7 (3)C13—C14—H14118.4
Symmetry codes: (i) x+1, y1, z+3/2; (ii) x, y+2, z1/2; (iii) x+1, y+1, z+1; (iv) x+1, y+1, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.862.393.214 (2)161
N3—H3···Cl1v0.862.483.283 (3)156
N2—H10···O10.861.982.637 (3)132
N2—H10···O1vi0.862.303.010 (3)141
C6—H6···Cg1vi0.932.743.327 (4)122
Symmetry codes: (v) x, y+1, z+1/2; (vi) x+1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[CdCl2(C14H12N4O2S)2]
Mr783.97
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)26.272 (5), 8.8773 (18), 14.453 (3)
β (°) 115.46 (3)
V3)3043.5 (11)
Z4
Radiation typeMo Kα
µ (mm1)1.08
Crystal size (mm)0.24 × 0.21 × 0.17
Data collection
DiffractometerRigaku Mercury CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
12400, 3494, 3349
Rint0.035
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.068, 1.23
No. of reflections3494
No. of parameters205
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.26

Computer programs: CrystalClear (Rigaku, 2002), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Cd1—N4i2.373 (2)Cd1—S12.7364 (8)
Cd1—Cl12.5828 (10)
N4i—Cd1—Cl190.76 (6)Cl1—Cd1—S196.09 (2)
N4i—Cd1—S190.77 (6)
Symmetry code: (i) x+1, y1, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.862.393.214 (2)161
N3—H3···Cl1ii0.862.483.283 (3)156
N2—H10···O10.861.982.637 (3)132
N2—H10···O1iii0.862.303.010 (3)141
C6—H6···Cg1iii0.932.743.327 (4)122
Symmetry codes: (ii) x, y+1, z+1/2; (iii) x+1/2, y+3/2, z+1.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds