Poly[[(μ2-4,4'-bipyridyl-κ(2) N:N')bis-{μ2-N-[2-(2-hy-droxy-benzo-yl)carbamo-thio-yl]acetamidato-κ(4) O,N,O':S}bis-(nitrato-κ(2) O,O')dicadmium] di-methyl-formamide tetra-solvate].

The asymmetric unit of the title complex, {[Cd2(C10H10N3O3S)2(C10H8N2)(NO3)2]·4C3H7NO} n , consists of one Cd(II) cation, one N-[2-(2-hy-droxy-benzo-yl)carbamo-thio-yl]acetamidate ligand, half a 4,4'-bipyridyl ligand, one coordinating nitrate anion and two di-methyl-formamide solvent mol-ecules of crystallization. The bipyridine ligand is completed by inversion symmetry. The metal cation exhibits a distorted penta-gonal-bipyramidal coordination geometry provided by two O and one N atoms of the thio-semicarbazide ligand, two O atoms of the nitrate anion, one S atom of a neighbouring thio-semicarbazide ligand and one 4,4'-bi-pyridine N atom. The bridging role of the thio-semicarbazide ligand through the S atom leads to centrosymmetric binuclear units, which are further linked by 4,4'-bi-pyridine units, forming polymeric chains extending along the b-axis direction. An intra-molecular N-H⋯O hydrogen bond occurs. The crystal structure also features N-H⋯O and O-H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.

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

[Cd2(C10n class="Species">H10N3O3S)2(C10H8N2)(NO3)2]·4C3H7NO

M = 1301.93

Monoclinic,

a = 13.831 (3) Å

b = 15.280 (3) Å

c = 14.363 (3) Å

β = 110.55 (3)°

V = 2842.4 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.90 mm−1

T = 293 K

0.30 × 0.18 × 0.08 mm

Data collection

Rigaku Saturn 724+ CCD diffractometer

Absorption correction: numerical (CrystalClear; Rigaku, 2007 ▶) T min = 0.813, T max = 0.946

18197 measured reflections

4980 independent reflections

4753 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.141

S = 1.28

4980 reflections

349 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.63 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: 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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813030055/rz5087sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813030055/rz5087Isup2.hkl

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

[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

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

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

Table 1

Hydrogen-bond geometry (Å, °)

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
O6—H6⋯O8ii	0.82	1.70	2.502 (9)	164

Symmetry codes: (i) ; (ii) .