metal-organic compounds
Poly[[(μ2-4,4′-bipyridyl-κ2N:N′)bis{μ2-N-[2-(2-hydroxybenzoyl)carbamothioyl]acetamidato-κ4O,N,O′:S}bis(nitrato-κ2O,O′)dicadmium] dimethylformamide tetrasolvate]
aZhicheng College, Fuzhou University, Fuzhou, Fujian 350108, People's Republic of China
*Correspondence e-mail: yyomh@163.com
The 2(C10H10N3O3S)2(C10H8N2)(NO3)2]·4C3H7NO}n, consists of one CdII cation, one N-[2-(2-hydroxybenzoyl)carbamothioyl]acetamidate ligand, half a 4,4′-bipyridyl ligand, one coordinating nitrate anion and two dimethylformamide solvent molecules of crystallization. The bipyridine ligand is completed by inversion symmetry. The metal cation exhibits a distorted pentagonal–bipyramidal coordination geometry provided by two O and one N atoms of the thiosemicarbazide ligand, two O atoms of the nitrate anion, one S atom of a neighbouring thiosemicarbazide ligand and one 4,4′-bipyridine N atom. The bridging role of the thiosemicarbazide ligand through the S atom leads to centrosymmetric binuclear units, which are further linked by 4,4′-bipyridine units, forming polymeric chains extending along the b-axis direction. An intramolecular N—H⋯O hydrogen bond occurs. The also features N—H⋯O and O—H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.
of the title complex, {[CdCCDC reference: 969916
Related literature
For background to the properties and applications of thiosemicarbazone complexes, see: Quiroga & Ranninger (2004); Kasuga et al. (2003); Floquet et al. (2009); Hassanien et al. (2008); Latheef et al. (2006); Babb et al. (2003). For related structures, see: Ke et al. (2007); Wang et al. (2010); Liu et al. (2013). For the synthesis of the N-(2-(2-hydroxybenzoyl)carbamothioyl)acetamide ligand, see: Wang et al. (2000).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; 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: SHELXL97.
Supporting information
CCDC reference: 969916
10.1107/S1600536813030055/rz5087sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813030055/rz5087Isup2.hkl
N-(2-(2-Hydroxybenzoyl)hydrazinecarbonothioyl)acetamide (H3L) was prepared according to the literature method (Wang et al., 2000). H3L (0.0251 g, 0.10 mmol) and cadmium nitrate tetrahydrate (0.0472 g, 0.20 mmol) were dissolved in a mixed solvent of methanol and dimethylformamide (12 ml, 5:1 v/v). 4,4'-Bipyridine (0.0102 g 0.05 mmol) was added and the solution was stirred for 4 h at room temperature. The resulting white suspension was filltered and the filtrate allowed to evaporate in air at room temperature. Colourless crystals of the title compound were separated from the filtrate after 10 days.
All C- and N-bound H atoms were placed in idealized positions using the riding-model approximation, with C—H = 0.93-0.96 Å, N—H = 0.86 Å, O—H = 0.86 Å, and with Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C, N, O) otherwise. In the last cycles of
three outliers (-4 6 8, -3 5 6, 1 2 0) were omitted.Data collection: CrystalClear (Rigaku, 2007); cell
CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); 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: SHELXL97 (Sheldrick, 2008).[Cd2(C10H10N3O3S)2(C10H8N2)(NO3)2]·4C3H7NO | F(000) = 1324 |
Mr = 1301.93 | Dx = 1.521 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 10007 reflections |
a = 13.831 (3) Å | θ = 3.0–27.5° |
b = 15.280 (3) Å | µ = 0.90 mm−1 |
c = 14.363 (3) Å | T = 293 K |
β = 110.55 (3)° | Block, colourless |
V = 2842.4 (12) Å3 | 0.30 × 0.18 × 0.08 mm |
Z = 2 |
Rigaku Saturn 724+ CCD diffractometer | 4980 independent reflections |
Radiation source: fine-focus sealed tube | 4753 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans at fixed χ = 45° | θmax = 25.0°, θmin = 3.0° |
Absorption correction: numerical (CrystalClear; Rigaku, 2007) | h = −16→16 |
Tmin = 0.813, Tmax = 0.946 | k = −18→18 |
18197 measured reflections | l = −16→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.28 | w = 1/[σ2(Fo2) + (0.0474P)2 + 4.0842P] where P = (Fo2 + 2Fc2)/3 |
4980 reflections | (Δ/σ)max < 0.001 |
349 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[Cd2(C10H10N3O3S)2(C10H8N2)(NO3)2]·4C3H7NO | V = 2842.4 (12) Å3 |
Mr = 1301.93 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.831 (3) Å | µ = 0.90 mm−1 |
b = 15.280 (3) Å | T = 293 K |
c = 14.363 (3) Å | 0.30 × 0.18 × 0.08 mm |
β = 110.55 (3)° |
Rigaku Saturn 724+ CCD diffractometer | 4980 independent reflections |
Absorption correction: numerical (CrystalClear; Rigaku, 2007) | 4753 reflections with I > 2σ(I) |
Tmin = 0.813, Tmax = 0.946 | Rint = 0.043 |
18197 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.28 | Δρmax = 0.70 e Å−3 |
4980 reflections | Δρmin = −0.63 e Å−3 |
349 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.93079 (3) | 0.13619 (3) | 0.35688 (3) | 0.05085 (16) | |
N4 | 0.9607 (3) | 0.2863 (3) | 0.3953 (4) | 0.0603 (11) | |
O2 | 0.8129 (3) | 0.1541 (3) | 0.4400 (3) | 0.0618 (10) | |
C4 | 0.8420 (4) | 0.1339 (3) | 0.5294 (4) | 0.0520 (12) | |
N2 | 1.0120 (3) | 0.1051 (3) | 0.5329 (3) | 0.0482 (10) | |
C6 | 0.7984 (5) | 0.1324 (4) | 0.6899 (5) | 0.0704 (17) | |
O4 | 0.7810 (3) | 0.1911 (3) | 0.2065 (3) | 0.0824 (13) | |
C5 | 0.7705 (4) | 0.1409 (4) | 0.5870 (5) | 0.0631 (15) | |
O6 | 0.8984 (3) | 0.1126 (4) | 0.7441 (3) | 0.0897 (15) | |
H6 | 0.9043 | 0.1049 | 0.8024 | 0.108* | |
O5 | 0.8031 (4) | 0.2180 (5) | 0.0673 (4) | 0.118 (2) | |
N5 | 0.8361 (4) | 0.1955 (4) | 0.1550 (4) | 0.0747 (14) | |
O3 | 0.9307 (3) | 0.1752 (4) | 0.1959 (3) | 0.0837 (13) | |
C7 | 0.7240 (6) | 0.1425 (6) | 0.7354 (6) | 0.097 (2) | |
H7 | 0.7435 | 0.1375 | 0.8041 | 0.116* | |
C10 | 0.6671 (5) | 0.1583 (6) | 0.5319 (6) | 0.094 (2) | |
H10 | 0.6465 | 0.1641 | 0.4632 | 0.113* | |
C8 | 0.6238 (7) | 0.1596 (8) | 0.6796 (8) | 0.129 (4) | |
H8 | 0.5750 | 0.1662 | 0.7101 | 0.154* | |
C9 | 0.5949 (6) | 0.1669 (8) | 0.5777 (8) | 0.131 (4) | |
H9 | 0.5262 | 0.1778 | 0.5395 | 0.157* | |
O1 | 1.1075 (3) | 0.1222 (3) | 0.3888 (3) | 0.0616 (10) | |
N1 | 1.1819 (3) | 0.0725 (3) | 0.5489 (3) | 0.0519 (10) | |
H1 | 1.2402 | 0.0541 | 0.5895 | 0.062* | |
N3 | 0.9386 (3) | 0.1056 (3) | 0.5792 (3) | 0.0510 (10) | |
H3 | 0.9551 | 0.0879 | 0.6396 | 0.061* | |
C3 | 1.1007 (4) | 0.0711 (3) | 0.5871 (4) | 0.0470 (11) | |
C13 | 0.9920 (4) | 0.4559 (3) | 0.4777 (4) | 0.0540 (12) | |
C2 | 1.1834 (4) | 0.0978 (4) | 0.4592 (4) | 0.0542 (13) | |
N6 | 0.5321 (4) | 0.1122 (4) | 0.2567 (5) | 0.0908 (18) | |
C15 | 0.8837 (5) | 0.3441 (4) | 0.3760 (5) | 0.0714 (17) | |
H15 | 0.8182 | 0.3272 | 0.3343 | 0.086* | |
C14 | 0.8962 (4) | 0.4273 (4) | 0.4146 (5) | 0.0675 (16) | |
H14 | 0.8398 | 0.4649 | 0.3983 | 0.081* | |
C16 | 0.6130 (4) | 0.0601 (5) | 0.2860 (5) | 0.0717 (17) | |
H16 | 0.6719 | 0.0790 | 0.2747 | 0.086* | |
C11 | 1.0539 (5) | 0.3136 (4) | 0.4533 (6) | 0.089 (2) | |
H11 | 1.1093 | 0.2752 | 0.4667 | 0.107* | |
C12 | 1.0716 (5) | 0.3966 (4) | 0.4944 (6) | 0.093 (2) | |
H12 | 1.1383 | 0.4126 | 0.5340 | 0.111* | |
C17 | 0.5353 (8) | 0.1979 (6) | 0.2137 (8) | 0.126 (3) | |
H17A | 0.6029 | 0.2080 | 0.2114 | 0.189* | |
H17B | 0.5198 | 0.2422 | 0.2538 | 0.189* | |
H17C | 0.4852 | 0.2002 | 0.1476 | 0.189* | |
C18 | 0.4398 (7) | 0.0860 (10) | 0.2729 (12) | 0.218 (8) | |
H18A | 0.4575 | 0.0504 | 0.3316 | 0.327* | |
H18B | 0.3970 | 0.0529 | 0.2167 | 0.327* | |
H18C | 0.4030 | 0.1369 | 0.2811 | 0.327* | |
O7 | 0.6180 (3) | −0.0114 (4) | 0.3271 (4) | 0.0868 (14) | |
C1 | 1.2880 (4) | 0.0956 (5) | 0.4484 (5) | 0.0683 (16) | |
H1A | 1.2857 | 0.0572 | 0.3948 | 0.103* | |
H1B | 1.3385 | 0.0748 | 0.5091 | 0.103* | |
H1C | 1.3062 | 0.1535 | 0.4344 | 0.103* | |
S1 | 1.12907 (10) | 0.02354 (9) | 0.70412 (10) | 0.0547 (3) | |
N7 | 0.5920 (7) | 0.3996 (9) | 0.5419 (6) | 0.167 (4) | |
C20 | 0.6425 (12) | 0.4109 (13) | 0.4690 (11) | 0.249 (9) | |
H20A | 0.5981 | 0.3896 | 0.4055 | 0.374* | |
H20B | 0.7062 | 0.3788 | 0.4899 | 0.374* | |
H20C | 0.6565 | 0.4719 | 0.4637 | 0.374* | |
C21 | 0.6531 (8) | 0.3997 (10) | 0.6491 (8) | 0.169 (5) | |
H21A | 0.6078 | 0.3928 | 0.6862 | 0.253* | |
H21B | 0.6897 | 0.4541 | 0.6668 | 0.253* | |
H21C | 0.7016 | 0.3522 | 0.6641 | 0.253* | |
O8 | 0.4333 (8) | 0.3831 (12) | 0.4272 (6) | 0.334 (11) | |
C19 | 0.4931 (10) | 0.3835 (13) | 0.5125 (8) | 0.235 (10) | |
H19 | 0.4658 | 0.3713 | 0.5617 | 0.282* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0399 (2) | 0.0541 (3) | 0.0550 (3) | 0.00047 (16) | 0.01226 (17) | −0.00090 (17) |
N4 | 0.050 (3) | 0.049 (3) | 0.074 (3) | −0.001 (2) | 0.012 (2) | −0.001 (2) |
O2 | 0.044 (2) | 0.076 (3) | 0.063 (2) | 0.0082 (18) | 0.0158 (18) | 0.003 (2) |
C4 | 0.038 (3) | 0.051 (3) | 0.065 (3) | −0.001 (2) | 0.014 (2) | −0.011 (3) |
N2 | 0.036 (2) | 0.048 (2) | 0.062 (3) | −0.0030 (18) | 0.0188 (19) | −0.003 (2) |
C6 | 0.054 (3) | 0.086 (4) | 0.080 (4) | 0.000 (3) | 0.034 (3) | −0.010 (3) |
O4 | 0.057 (2) | 0.107 (4) | 0.083 (3) | −0.004 (2) | 0.024 (2) | 0.004 (3) |
C5 | 0.049 (3) | 0.068 (4) | 0.076 (4) | −0.003 (3) | 0.026 (3) | −0.012 (3) |
O6 | 0.057 (3) | 0.145 (5) | 0.070 (3) | 0.013 (3) | 0.027 (2) | 0.010 (3) |
O5 | 0.082 (3) | 0.181 (6) | 0.073 (3) | 0.012 (4) | 0.007 (3) | 0.047 (4) |
N5 | 0.064 (3) | 0.086 (4) | 0.064 (3) | 0.000 (3) | 0.011 (3) | 0.010 (3) |
O3 | 0.054 (3) | 0.126 (4) | 0.068 (3) | 0.013 (3) | 0.016 (2) | 0.016 (3) |
C7 | 0.082 (5) | 0.138 (7) | 0.089 (5) | 0.008 (5) | 0.052 (4) | −0.006 (5) |
C10 | 0.047 (4) | 0.147 (7) | 0.091 (5) | 0.008 (4) | 0.026 (3) | −0.016 (5) |
C8 | 0.074 (6) | 0.217 (12) | 0.118 (7) | 0.014 (6) | 0.062 (5) | −0.008 (7) |
C9 | 0.049 (4) | 0.228 (12) | 0.120 (7) | 0.025 (6) | 0.034 (4) | −0.019 (8) |
O1 | 0.043 (2) | 0.081 (3) | 0.059 (2) | 0.0057 (18) | 0.0148 (18) | 0.0052 (19) |
N1 | 0.033 (2) | 0.056 (3) | 0.064 (3) | 0.0051 (18) | 0.0145 (19) | 0.001 (2) |
N3 | 0.042 (2) | 0.058 (3) | 0.054 (2) | 0.0056 (19) | 0.0178 (19) | −0.002 (2) |
C3 | 0.038 (2) | 0.041 (3) | 0.058 (3) | −0.001 (2) | 0.013 (2) | −0.009 (2) |
C13 | 0.042 (3) | 0.051 (3) | 0.063 (3) | −0.001 (2) | 0.011 (2) | 0.002 (2) |
C2 | 0.041 (3) | 0.052 (3) | 0.068 (3) | −0.005 (2) | 0.017 (3) | −0.007 (3) |
N6 | 0.056 (3) | 0.108 (5) | 0.110 (5) | 0.027 (3) | 0.032 (3) | 0.027 (4) |
C15 | 0.049 (3) | 0.061 (4) | 0.086 (4) | 0.003 (3) | 0.002 (3) | −0.010 (3) |
C14 | 0.048 (3) | 0.055 (3) | 0.086 (4) | 0.006 (3) | 0.007 (3) | −0.004 (3) |
C16 | 0.039 (3) | 0.102 (5) | 0.069 (4) | 0.004 (3) | 0.012 (3) | −0.005 (4) |
C11 | 0.051 (4) | 0.060 (4) | 0.133 (6) | 0.007 (3) | 0.003 (4) | −0.024 (4) |
C12 | 0.042 (3) | 0.064 (4) | 0.144 (7) | −0.002 (3) | −0.002 (4) | −0.031 (4) |
C17 | 0.126 (8) | 0.112 (7) | 0.150 (9) | 0.042 (6) | 0.061 (7) | 0.028 (7) |
C18 | 0.066 (6) | 0.262 (16) | 0.35 (2) | 0.055 (8) | 0.103 (9) | 0.148 (15) |
O7 | 0.056 (3) | 0.102 (4) | 0.096 (3) | 0.014 (2) | 0.019 (2) | 0.022 (3) |
C1 | 0.042 (3) | 0.087 (4) | 0.081 (4) | 0.000 (3) | 0.028 (3) | 0.000 (3) |
S1 | 0.0464 (7) | 0.0602 (8) | 0.0516 (7) | 0.0013 (6) | 0.0098 (6) | −0.0056 (6) |
N7 | 0.105 (6) | 0.306 (14) | 0.098 (6) | −0.052 (8) | 0.043 (5) | 0.008 (7) |
C20 | 0.192 (15) | 0.40 (3) | 0.210 (15) | −0.070 (17) | 0.140 (13) | 0.001 (17) |
C21 | 0.094 (7) | 0.279 (16) | 0.115 (8) | −0.040 (9) | 0.012 (6) | −0.018 (9) |
O8 | 0.182 (9) | 0.72 (3) | 0.071 (5) | −0.177 (13) | 0.015 (5) | 0.056 (9) |
C19 | 0.119 (9) | 0.51 (3) | 0.070 (6) | −0.087 (13) | 0.028 (6) | 0.031 (11) |
Cd1—O1 | 2.332 (4) | C13—C14 | 1.388 (7) |
Cd1—O2 | 2.350 (4) | C13—C13ii | 1.476 (10) |
Cd1—N4 | 2.362 (5) | C2—C1 | 1.509 (7) |
Cd1—O3 | 2.387 (4) | N6—C16 | 1.317 (8) |
Cd1—N2 | 2.426 (4) | N6—C18 | 1.433 (10) |
Cd1—O4 | 2.553 (5) | N6—C17 | 1.456 (10) |
Cd1—S1i | 2.6270 (15) | C15—C14 | 1.373 (8) |
N4—C11 | 1.332 (7) | C15—H15 | 0.9300 |
N4—C15 | 1.336 (7) | C14—H14 | 0.9300 |
O2—C4 | 1.242 (7) | C16—O7 | 1.232 (8) |
C4—N3 | 1.346 (6) | C16—H16 | 0.9300 |
C4—C5 | 1.499 (8) | C11—C12 | 1.384 (9) |
N2—C3 | 1.307 (6) | C11—H11 | 0.9300 |
N2—N3 | 1.396 (5) | C12—H12 | 0.9300 |
C6—O6 | 1.361 (8) | C17—H17A | 0.9600 |
C6—C5 | 1.397 (9) | C17—H17B | 0.9600 |
C6—C7 | 1.408 (9) | C17—H17C | 0.9600 |
O4—N5 | 1.237 (6) | C18—H18A | 0.9600 |
C5—C10 | 1.395 (9) | C18—H18B | 0.9600 |
O6—H6 | 0.8200 | C18—H18C | 0.9600 |
O5—N5 | 1.229 (7) | C1—H1A | 0.9600 |
N5—O3 | 1.270 (6) | C1—H1B | 0.9600 |
C7—C8 | 1.361 (12) | C1—H1C | 0.9600 |
C7—H7 | 0.9300 | S1—Cd1i | 2.6270 (15) |
C10—C9 | 1.382 (10) | N7—C19 | 1.305 (14) |
C10—H10 | 0.9300 | N7—C20 | 1.458 (13) |
C8—C9 | 1.380 (12) | N7—C21 | 1.474 (12) |
C8—H8 | 0.9300 | C20—H20A | 0.9600 |
C9—H9 | 0.9300 | C20—H20B | 0.9600 |
O1—C2 | 1.232 (6) | C20—H20C | 0.9600 |
N1—C2 | 1.352 (7) | C21—H21A | 0.9600 |
N1—C3 | 1.412 (6) | C21—H21B | 0.9600 |
N1—H1 | 0.8600 | C21—H21C | 0.9600 |
N3—H3 | 0.8600 | O8—C19 | 1.214 (13) |
C3—S1 | 1.745 (5) | C19—H19 | 0.9300 |
C13—C12 | 1.381 (8) | ||
O1—Cd1—O2 | 140.93 (13) | N2—C3—S1 | 125.9 (4) |
O1—Cd1—N4 | 87.55 (15) | N1—C3—S1 | 116.1 (3) |
O2—Cd1—N4 | 82.21 (15) | C12—C13—C14 | 115.3 (5) |
O1—Cd1—O3 | 81.83 (14) | C12—C13—C13ii | 122.4 (6) |
O2—Cd1—O3 | 134.28 (14) | C14—C13—C13ii | 122.3 (6) |
N4—Cd1—O3 | 85.65 (18) | O1—C2—N1 | 125.1 (5) |
O1—Cd1—N2 | 72.96 (13) | O1—C2—C1 | 119.6 (5) |
O2—Cd1—N2 | 69.13 (13) | N1—C2—C1 | 115.3 (5) |
N4—Cd1—N2 | 88.16 (15) | C16—N6—C18 | 119.0 (8) |
O3—Cd1—N2 | 154.27 (14) | C16—N6—C17 | 122.1 (7) |
O1—Cd1—O4 | 132.81 (14) | C18—N6—C17 | 118.8 (7) |
O2—Cd1—O4 | 83.67 (14) | N4—C15—C14 | 123.3 (5) |
N4—Cd1—O4 | 84.38 (16) | N4—C15—H15 | 118.3 |
O3—Cd1—O4 | 51.27 (14) | C14—C15—H15 | 118.3 |
N2—Cd1—O4 | 152.53 (14) | C15—C14—C13 | 120.8 (5) |
O1—Cd1—S1i | 99.58 (10) | C15—C14—H14 | 119.6 |
O2—Cd1—S1i | 94.80 (10) | C13—C14—H14 | 119.6 |
N4—Cd1—S1i | 171.58 (11) | O7—C16—N6 | 126.0 (6) |
O3—Cd1—S1i | 90.91 (14) | O7—C16—H16 | 117.0 |
N2—Cd1—S1i | 98.16 (10) | N6—C16—H16 | 117.0 |
O4—Cd1—S1i | 87.47 (12) | N4—C11—C12 | 122.8 (6) |
C11—N4—C15 | 116.7 (5) | N4—C11—H11 | 118.6 |
C11—N4—Cd1 | 120.1 (4) | C12—C11—H11 | 118.6 |
C15—N4—Cd1 | 122.1 (4) | C13—C12—C11 | 121.1 (5) |
C4—O2—Cd1 | 117.7 (3) | C13—C12—H12 | 119.5 |
O2—C4—N3 | 122.0 (5) | C11—C12—H12 | 119.5 |
O2—C4—C5 | 121.0 (5) | N6—C17—H17A | 109.5 |
N3—C4—C5 | 117.0 (5) | N6—C17—H17B | 109.5 |
C3—N2—N3 | 114.0 (4) | H17A—C17—H17B | 109.5 |
C3—N2—Cd1 | 133.8 (3) | N6—C17—H17C | 109.5 |
N3—N2—Cd1 | 110.3 (3) | H17A—C17—H17C | 109.5 |
O6—C6—C5 | 118.2 (5) | H17B—C17—H17C | 109.5 |
O6—C6—C7 | 121.3 (7) | N6—C18—H18A | 109.5 |
C5—C6—C7 | 120.4 (6) | N6—C18—H18B | 109.5 |
N5—O4—Cd1 | 92.1 (3) | H18A—C18—H18B | 109.5 |
C10—C5—C6 | 117.7 (6) | N6—C18—H18C | 109.5 |
C10—C5—C4 | 116.4 (6) | H18A—C18—H18C | 109.5 |
C6—C5—C4 | 125.9 (5) | H18B—C18—H18C | 109.5 |
C6—O6—H6 | 109.5 | C2—C1—H1A | 109.5 |
O5—N5—O4 | 123.0 (6) | C2—C1—H1B | 109.5 |
O5—N5—O3 | 119.6 (6) | H1A—C1—H1B | 109.5 |
O4—N5—O3 | 117.4 (5) | C2—C1—H1C | 109.5 |
N5—O3—Cd1 | 99.2 (3) | H1A—C1—H1C | 109.5 |
C8—C7—C6 | 120.5 (8) | H1B—C1—H1C | 109.5 |
C8—C7—H7 | 119.8 | C3—S1—Cd1i | 97.32 (16) |
C6—C7—H7 | 119.8 | C19—N7—C20 | 120.1 (10) |
C9—C10—C5 | 121.1 (8) | C19—N7—C21 | 119.3 (9) |
C9—C10—H10 | 119.4 | C20—N7—C21 | 120.4 (10) |
C5—C10—H10 | 119.4 | N7—C20—H20A | 109.5 |
C7—C8—C9 | 119.8 (7) | N7—C20—H20B | 109.5 |
C7—C8—H8 | 120.1 | H20A—C20—H20B | 109.5 |
C9—C8—H8 | 120.1 | N7—C20—H20C | 109.5 |
C8—C9—C10 | 120.6 (8) | H20A—C20—H20C | 109.5 |
C8—C9—H9 | 119.7 | H20B—C20—H20C | 109.5 |
C10—C9—H9 | 119.7 | N7—C21—H21A | 109.5 |
C2—O1—Cd1 | 136.2 (4) | N7—C21—H21B | 109.5 |
C2—N1—C3 | 130.9 (4) | H21A—C21—H21B | 109.5 |
C2—N1—H1 | 114.6 | N7—C21—H21C | 109.5 |
C3—N1—H1 | 114.6 | H21A—C21—H21C | 109.5 |
C4—N3—N2 | 120.1 (4) | H21B—C21—H21C | 109.5 |
C4—N3—H3 | 119.9 | O8—C19—N7 | 126.4 (11) |
N2—N3—H3 | 119.9 | O8—C19—H19 | 116.8 |
N2—C3—N1 | 118.1 (5) | N7—C19—H19 | 116.8 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O7i | 0.86 | 2.01 | 2.871 (6) | 174 |
N3—H3···O6 | 0.86 | 1.96 | 2.619 (6) | 133 |
N3—H3···S1 | 0.86 | 2.46 | 2.901 (4) | 113 |
O6—H6···O8iii | 0.82 | 1.70 | 2.502 (9) | 164 |
Symmetry codes: (i) −x+2, −y, −z+1; (iii) x+1/2, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O7i | 0.86 | 2.01 | 2.871 (6) | 174.1 |
N3—H3···O6 | 0.86 | 1.96 | 2.619 (6) | 132.6 |
O6—H6···O8ii | 0.82 | 1.70 | 2.502 (9) | 163.8 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x+1/2, −y+1/2, z+1/2. |
Acknowledgements
This work was supported by the National Training Programs of Innovation and Entrepreneurship for Undergraduates (grant No. 201313470010).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Thiosemicarbazones complexes have received considerable attentions in the past decades due to their interesting biological activities, including antibacterial, antimalarial, antiviral and antitumor activities (Quiroga & Ranninger, 2004; Kasuga et al., 2003;). In order to figure out their structure-property relationship, a great number of metal complexes based on thiosemicarbazone derivatives, particularly the 1,4-disubstituted ones have been prepared and their biological activities were investigated systematically (Floquet et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003). In this paper, we report the crystal structure of the title one-dimensional coordination polymer based on diacylthiosemicarbazone.
The asymmetric unit of the title complex consists of one cadmium(II) cation, one N-(2-(2-hydroxybenzoyl)carbamothioyl)acetamide ligand, one half of a 4,4'-bipyridine, one coordinated nitrate anion and two dimethylformamide molecules of crystallization (Fig. 1). In the structure, each Cd center adopts a distorted pentagonal bipyramidal coordination geometry with the equatorial plane formed two O atoms and one N atom from the thiosemicarbazide ligand and two O atoms from the bidentate nitrate anion. These five atoms (O1, N2, O2, O4, O3) and the metal center are almost coplanar (maximum deviation from the least-squares plane is 0.6560 (3) Å for the O3 atom). The Cd1—O3 and Cd1—O4 bond lengths involving the nitrate anion are remarkably different (2.387 (4) and 2.553 (5) Å, respectively). The axial positions are occupied by one N atom from 4,4'-bipyridine and one S atom from a neighbouring thiosemicarbazide ligand. The Cd1—N4 bond distance is 2.360 (5) Å, indicating the strong coordination between Cd and 4,4'-bipyridine, while the Cd1—S1i [symmetry code: (i) -x+2, -y, -z+1] bond length is 2.628 (5) Å, which is slightly shorter than that previously reported (2.7364 (8) Å) for a Cd complex with thiosemicarbazones (Wang et al., 2010). Due to the axial coordination of S atoms, two neighbouring cadmium(II) cations are interconnected to generate a centrosymmetric binuclear unit with a Cd···Cd separation of 5.6889 (12) Å (Fig. 2). Along the b axis, such binuclear units are further bridged by 4,4'-bipyridine linkers to form a one-dimensional zigzag coordination polymer. In the structure of the title complex, N—H···O and O—H···O hydrogen bonds (Table 1) play an important role in stabilizing the packing (Fig. 3).