Tetra-kis(di-4-pyridylsulfane)dinitratocopper(II).

In the title complex, [Cu(NO(3))(2)(C(10)H(8)N(2)S)(4)], the Cu(II) atom (site symmetry ) is coordinated by two monodentate nitrate ions and two monodentate di-4-pyridylsulfane ligands, resulting in a slightly distorted trans-arranged CuO(2)N(4) octa-hedral geometry. Intra-molecular C-H⋯O hydrogen bonds are present. In the crystal, adjacent mol-ecules are linked via C-H⋯N hydrogen bonds into chains parallel to the a axis. Inter-molecular C-H⋯O inter-actions also occur.

Related literature

For transition-metal complexes of di-4-pyridylsulfane, see: Wen et al. (2004 ▶); Muthu et al. (2005 ▶); Xu et al. (2007 ▶); Zhang et al. (2008 ▶).

Experimental

Crystal data

[Cu(NO3)2(C10H8N2S)4]

M = 940.59

Triclinic,

a = 9.299 (4) Å

b = 10.765 (5) Å

c = 10.978 (5) Å

α = 84.408 (6)°

β = 73.759 (6)°

γ = 79.180 (6)°

V = 1035.1 (8) Å3

Z = 1

Mo Kα radiation

μ = 0.79 mm−1

T = 296 K

0.21 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.847, T max = 0.874

7479 measured reflections

3728 independent reflections

2392 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.100

S = 0.90

3679 reflections

277 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.33 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810011414/rz2428sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011414/rz2428Isup2.hkl

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

[Cu(NO3)2(C10H8N2S)4]	Z = 1
Mr = 940.59	F(000) = 483
Triclinic, P1	Dx = 1.509 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.299 (4) Å	Cell parameters from 4796 reflections
b = 10.765 (5) Å	θ = 2.3–28.2°
c = 10.978 (5) Å	µ = 0.79 mm−1
α = 84.408 (6)°	T = 296 K
β = 73.759 (6)°	Block, blue
γ = 79.180 (6)°	0.21 × 0.19 × 0.17 mm
V = 1035.1 (8) Å3

Bruker SMART APEXII diffractometer	3728 independent reflections
Radiation source: fine-focus sealed tube	2392 reflections with I > 2σ(I)
graphite	Rint = 0.061
ω scans	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.847, Tmax = 0.874	k = −12→12
7479 measured reflections	l = −13→12

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 0.90	w = 1/[σ2(Fo2) + (0.0391P)2] where P = (Fo2 + 2Fc2)/3
3679 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.43 e Å−3
6 restraints	Δρmin = −0.33 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
Cu1	0.5000	1.0000	0.5000	0.03494 (19)
S1	0.46635 (10)	0.45645 (8)	0.29541 (10)	0.0526 (3)
S2	0.38860 (11)	1.20522 (11)	−0.05513 (9)	0.0609 (3)
O1	0.7889 (3)	0.9473 (2)	0.4138 (2)	0.0586 (7)
O2	0.9388 (3)	1.0613 (3)	0.2949 (3)	0.0869 (10)
O3	1.0298 (3)	0.8845 (3)	0.3704 (3)	0.1064 (12)
N1	0.4896 (3)	0.8203 (2)	0.4611 (2)	0.0337 (6)
N2	−0.0360 (3)	0.4563 (3)	0.3369 (3)	0.0556 (9)
N3	0.4666 (3)	1.0575 (2)	0.3276 (2)	0.0327 (6)
N4	−0.1253 (4)	1.2525 (3)	0.0096 (3)	0.0642 (9)
N5	0.9202 (4)	0.9628 (3)	0.3612 (3)	0.0538 (7)
C1	0.6125 (4)	0.7481 (3)	0.3889 (3)	0.0381 (8)
H1	0.7061	0.7748	0.3711	0.046*
C2	0.6058 (4)	0.6377 (3)	0.3409 (3)	0.0381 (8)
H2	0.6937	0.5908	0.2917	0.046*
C3	0.4684 (4)	0.5955 (3)	0.3654 (3)	0.0359 (8)
C4	0.3437 (4)	0.6656 (3)	0.4452 (3)	0.0433 (9)
H4	0.2500	0.6385	0.4682	0.052*
C5	0.3596 (4)	0.7753 (3)	0.4899 (3)	0.0413 (9)
H5	0.2746	0.8210	0.5436	0.050*
C6	0.2705 (3)	0.4599 (3)	0.3124 (3)	0.0385 (8)
C7	0.1802 (4)	0.5620 (3)	0.2676 (4)	0.0510 (10)
H7	0.2205	0.6326	0.2270	0.061*
C8	0.0298 (4)	0.5550 (4)	0.2851 (4)	0.0560 (10)
H8	−0.0309	0.6253	0.2586	0.067*
C9	0.0547 (4)	0.3585 (3)	0.3756 (4)	0.0556 (10)
H9	0.0133	0.2866	0.4105	0.067*
C10	0.2053 (4)	0.3570 (3)	0.3674 (3)	0.0453 (9)
H10	0.2621	0.2871	0.3987	0.054*
C11	0.3401 (4)	1.0425 (3)	0.2976 (3)	0.0365 (8)
H11	0.2705	1.0005	0.3569	0.044*
C12	0.3082 (4)	1.0855 (3)	0.1852 (3)	0.0386 (8)
H12	0.2191	1.0726	0.1693	0.046*
C13	0.4103 (4)	1.1485 (3)	0.0953 (3)	0.0389 (8)
C14	0.5424 (4)	1.1637 (3)	0.1250 (3)	0.0404 (9)
H14	0.6140	1.2051	0.0671	0.049*
C15	0.5658 (4)	1.1175 (3)	0.2396 (3)	0.0369 (8)
H15	0.6547	1.1281	0.2575	0.044*
C16	0.1889 (4)	1.2224 (3)	−0.0291 (3)	0.0415 (9)
C17	0.1259 (4)	1.1460 (3)	−0.0847 (3)	0.0504 (10)
H17	0.1873	1.0824	−0.1364	0.061*
C18	−0.0290 (5)	1.1645 (4)	−0.0632 (4)	0.0592 (11)
H18	−0.0694	1.1118	−0.1022	0.071*
C19	0.0927 (4)	1.3150 (4)	0.0459 (4)	0.0603 (11)
H19	0.1307	1.3701	0.0843	0.072*
C20	−0.0611 (5)	1.3244 (4)	0.0630 (4)	0.0725 (13)
H20	−0.1250	1.3859	0.1161	0.087*

	U11	U22	U33	U12	U13	U23
Cu1	0.0427 (4)	0.0243 (3)	0.0432 (4)	−0.0055 (2)	−0.0207 (3)	0.0000 (3)
S1	0.0416 (6)	0.0364 (5)	0.0856 (8)	−0.0001 (4)	−0.0239 (5)	−0.0226 (5)
S2	0.0406 (6)	0.0945 (8)	0.0442 (6)	−0.0093 (5)	−0.0137 (5)	0.0163 (6)
O1	0.0421 (14)	0.0601 (14)	0.0723 (17)	−0.0193 (12)	−0.0018 (13)	−0.0171 (13)
O2	0.073 (2)	0.064 (2)	0.107 (3)	−0.0221 (16)	0.0062 (18)	0.0106 (18)
O3	0.069 (2)	0.089 (2)	0.148 (3)	0.0266 (18)	−0.036 (2)	0.000 (2)
N1	0.0358 (16)	0.0265 (14)	0.0415 (17)	−0.0050 (12)	−0.0151 (14)	−0.0005 (12)
N2	0.0396 (18)	0.052 (2)	0.076 (2)	−0.0107 (16)	−0.0115 (17)	−0.0103 (18)
N3	0.0353 (16)	0.0287 (14)	0.0370 (17)	−0.0077 (12)	−0.0128 (14)	−0.0015 (12)
N4	0.045 (2)	0.073 (2)	0.072 (3)	−0.0104 (19)	−0.0154 (19)	0.006 (2)
N5	0.0412 (16)	0.0535 (16)	0.0649 (18)	−0.0102 (15)	−0.0065 (15)	−0.0127 (14)
C1	0.0317 (19)	0.0398 (19)	0.046 (2)	−0.0101 (16)	−0.0133 (17)	−0.0003 (17)
C2	0.035 (2)	0.0339 (19)	0.047 (2)	−0.0037 (15)	−0.0122 (17)	−0.0078 (16)
C3	0.040 (2)	0.0269 (17)	0.044 (2)	−0.0049 (15)	−0.0170 (17)	−0.0005 (15)
C4	0.0293 (19)	0.0364 (19)	0.065 (3)	−0.0094 (15)	−0.0092 (18)	−0.0096 (18)
C5	0.037 (2)	0.0347 (19)	0.051 (2)	−0.0030 (16)	−0.0087 (18)	−0.0083 (17)
C6	0.038 (2)	0.0345 (18)	0.048 (2)	−0.0056 (15)	−0.0179 (17)	−0.0093 (16)
C7	0.049 (2)	0.040 (2)	0.069 (3)	−0.0125 (17)	−0.023 (2)	0.0068 (19)
C8	0.050 (2)	0.046 (2)	0.077 (3)	−0.0013 (19)	−0.030 (2)	−0.001 (2)
C9	0.054 (3)	0.044 (2)	0.065 (3)	−0.0131 (19)	−0.006 (2)	−0.004 (2)
C10	0.047 (2)	0.0341 (19)	0.054 (2)	−0.0027 (17)	−0.0130 (19)	−0.0068 (17)
C11	0.0350 (19)	0.0340 (18)	0.042 (2)	−0.0104 (15)	−0.0114 (17)	0.0008 (16)
C12	0.0321 (19)	0.0406 (19)	0.045 (2)	−0.0078 (15)	−0.0133 (17)	0.0028 (17)
C13	0.0323 (19)	0.044 (2)	0.037 (2)	−0.0021 (16)	−0.0084 (17)	−0.0008 (16)
C14	0.034 (2)	0.043 (2)	0.042 (2)	−0.0099 (16)	−0.0081 (17)	0.0042 (17)
C15	0.0321 (19)	0.0322 (18)	0.049 (2)	−0.0054 (15)	−0.0136 (18)	−0.0035 (17)
C16	0.037 (2)	0.050 (2)	0.036 (2)	−0.0015 (17)	−0.0137 (17)	0.0079 (17)
C17	0.053 (2)	0.045 (2)	0.051 (3)	−0.0016 (18)	−0.015 (2)	−0.0030 (19)
C18	0.062 (3)	0.061 (3)	0.068 (3)	−0.024 (2)	−0.032 (2)	0.006 (2)
C19	0.053 (3)	0.068 (3)	0.065 (3)	−0.006 (2)	−0.021 (2)	−0.018 (2)
C20	0.053 (3)	0.079 (3)	0.080 (3)	0.008 (2)	−0.015 (3)	−0.024 (3)

Cu1—N3i	2.023 (3)	C4—H4	0.9300
Cu1—N3	2.023 (3)	C5—H5	0.9300
Cu1—N1i	2.047 (3)	C6—C10	1.370 (4)
Cu1—N1	2.047 (3)	C6—C7	1.390 (4)
Cu1—O1	2.558 (3)	C7—C8	1.373 (5)
Cu1—O1i	2.558 (3)	C7—H7	0.9300
S1—C3	1.754 (3)	C8—H8	0.9300
S1—C6	1.772 (3)	C9—C10	1.375 (5)
S2—C13	1.757 (3)	C9—H9	0.9300
S2—C16	1.775 (3)	C10—H10	0.9300
O1—N5	1.231 (3)	C11—C12	1.366 (4)
O2—N5	1.238 (4)	C11—H11	0.9300
O3—N5	1.216 (4)	C12—C13	1.387 (4)
N1—C5	1.331 (4)	C12—H12	0.9300
N1—C1	1.348 (4)	C13—C14	1.397 (4)
N2—C8	1.326 (4)	C14—C15	1.367 (4)
N2—C9	1.334 (4)	C14—H14	0.9300
N3—C15	1.344 (4)	C15—H15	0.9300
N3—C11	1.347 (4)	C16—C17	1.367 (4)
N4—C20	1.326 (5)	C16—C19	1.374 (5)
N4—C18	1.329 (5)	C17—C18	1.372 (5)
C1—C2	1.365 (4)	C17—H17	0.9300
C1—H1	0.9300	C18—H18	0.9300
C2—C3	1.383 (4)	C19—C20	1.375 (5)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.383 (4)	C20—H20	0.9300
C4—C5	1.370 (4)
N3i—Cu1—N3	180.000 (1)	C10—C6—S1	119.4 (3)
N3i—Cu1—N1i	87.75 (10)	C7—C6—S1	122.4 (3)
N3—Cu1—N1i	92.25 (10)	C8—C7—C6	117.8 (3)
N3i—Cu1—N1	92.25 (10)	C8—C7—H7	121.1
N3—Cu1—N1	87.75 (10)	C6—C7—H7	121.1
N1i—Cu1—N1	180.00 (14)	N2—C8—C7	125.3 (3)
N3i—Cu1—O1	86.21 (9)	N2—C8—H8	117.3
N3—Cu1—O1	93.79 (9)	C7—C8—H8	117.3
N1i—Cu1—O1	91.99 (9)	N2—C9—C10	124.3 (3)
N1—Cu1—O1	88.01 (9)	N2—C9—H9	117.9
N3i—Cu1—O1i	93.79 (9)	C10—C9—H9	117.9
N3—Cu1—O1i	86.21 (9)	C6—C10—C9	119.0 (3)
N1i—Cu1—O1i	88.01 (9)	C6—C10—H10	120.5
N1—Cu1—O1i	91.99 (9)	C9—C10—H10	120.5
O1—Cu1—O1i	180.000 (1)	N3—C11—C12	123.8 (3)
C3—S1—C6	103.18 (15)	N3—C11—H11	118.1
C13—S2—C16	101.57 (15)	C12—C11—H11	118.1
N5—O1—Cu1	159.3 (2)	C11—C12—C13	119.2 (3)
C5—N1—C1	116.5 (3)	C11—C12—H12	120.4
C5—N1—Cu1	122.5 (2)	C13—C12—H12	120.4
C1—N1—Cu1	120.4 (2)	C12—C13—C14	117.5 (3)
C8—N2—C9	115.3 (3)	C12—C13—S2	124.7 (3)
C15—N3—C11	116.8 (3)	C14—C13—S2	117.8 (3)
C15—N3—Cu1	121.7 (2)	C15—C14—C13	119.6 (3)
C11—N3—Cu1	121.4 (2)	C15—C14—H14	120.2
C20—N4—C18	115.0 (3)	C13—C14—H14	120.2
O3—N5—O1	122.4 (4)	N3—C15—C14	123.1 (3)
O3—N5—O2	119.9 (4)	N3—C15—H15	118.4
O1—N5—O2	117.7 (3)	C14—C15—H15	118.4
N1—C1—C2	122.9 (3)	C17—C16—C19	117.9 (3)
N1—C1—H1	118.5	C17—C16—S2	121.4 (3)
C2—C1—H1	118.5	C19—C16—S2	120.7 (3)
C1—C2—C3	120.0 (3)	C16—C17—C18	119.1 (4)
C1—C2—H2	120.0	C16—C17—H17	120.4
C3—C2—H2	120.0	C18—C17—H17	120.4
C4—C3—C2	117.2 (3)	N4—C18—C17	124.5 (4)
C4—C3—S1	125.1 (3)	N4—C18—H18	117.7
C2—C3—S1	117.7 (2)	C17—C18—H18	117.7
C5—C4—C3	119.3 (3)	C16—C19—C20	118.4 (4)
C5—C4—H4	120.4	C16—C19—H19	120.8
C3—C4—H4	120.4	C20—C19—H19	120.8
N1—C5—C4	123.9 (3)	N4—C20—C19	125.0 (4)
N1—C5—H5	118.1	N4—C20—H20	117.5
C4—C5—H5	118.1	C19—C20—H20	117.5
C10—C6—C7	118.1 (3)
N3i—Cu1—O1—N5	−120.2 (7)	C3—S1—C6—C10	−127.2 (3)
N3—Cu1—O1—N5	59.8 (7)	C3—S1—C6—C7	55.2 (3)
N1i—Cu1—O1—N5	−32.6 (7)	C10—C6—C7—C8	2.2 (5)
N1—Cu1—O1—N5	147.4 (7)	S1—C6—C7—C8	179.8 (3)
N3—Cu1—N1—C5	−89.3 (3)	C9—N2—C8—C7	1.1 (6)
O1—Cu1—N1—C5	176.8 (3)	C6—C7—C8—N2	−3.0 (6)
O1i—Cu1—N1—C5	−3.2 (3)	C8—N2—C9—C10	1.6 (6)
N3i—Cu1—N1—C1	−98.5 (2)	C7—C6—C10—C9	0.2 (5)
N3—Cu1—N1—C1	81.5 (2)	S1—C6—C10—C9	−177.4 (3)
O1—Cu1—N1—C1	−12.3 (2)	N2—C9—C10—C6	−2.3 (6)
O1i—Cu1—N1—C1	167.7 (2)	C15—N3—C11—C12	−0.6 (4)
N1i—Cu1—N3—C15	57.4 (2)	Cu1—N3—C11—C12	176.5 (2)
N1—Cu1—N3—C15	−122.6 (2)	N3—C11—C12—C13	0.0 (5)
O1—Cu1—N3—C15	−34.7 (2)	C11—C12—C13—C14	0.5 (5)
O1i—Cu1—N3—C15	145.3 (2)	C11—C12—C13—S2	178.0 (2)
N1i—Cu1—N3—C11	−119.5 (2)	C16—S2—C13—C12	23.8 (3)
N1—Cu1—N3—C11	60.5 (2)	C16—S2—C13—C14	−158.6 (3)
O1—Cu1—N3—C11	148.3 (2)	C12—C13—C14—C15	−0.3 (5)
O1i—Cu1—N3—C11	−31.7 (2)	S2—C13—C14—C15	−178.0 (2)
Cu1—O1—N5—O3	166.9 (5)	C11—N3—C15—C14	0.8 (4)
Cu1—O1—N5—O2	−14.5 (9)	Cu1—N3—C15—C14	−176.3 (2)
C5—N1—C1—C2	3.5 (5)	C13—C14—C15—N3	−0.4 (5)
Cu1—N1—C1—C2	−167.9 (2)	C13—S2—C16—C17	−111.6 (3)
N1—C1—C2—C3	0.1 (5)	C13—S2—C16—C19	69.8 (3)
C1—C2—C3—C4	−3.6 (5)	C19—C16—C17—C18	−0.2 (5)
C1—C2—C3—S1	177.4 (2)	S2—C16—C17—C18	−179.0 (3)
C6—S1—C3—C4	16.6 (3)	C20—N4—C18—C17	−0.3 (6)
C6—S1—C3—C2	−164.5 (3)	C16—C17—C18—N4	−0.3 (6)
C2—C3—C4—C5	3.5 (5)	C17—C16—C19—C20	1.2 (5)
S1—C3—C4—C5	−177.6 (3)	S2—C16—C19—C20	179.9 (3)
C1—N1—C5—C4	−3.6 (5)	C18—N4—C20—C19	1.4 (6)
Cu1—N1—C5—C4	167.5 (2)	C16—C19—C20—N4	−1.9 (7)
C3—C4—C5—N1	0.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1i	0.93	2.52	3.063 (4)	118
C5—H5···O2i	0.93	2.49	3.419 (4)	174
C5—H5···O1i	0.93	2.51	3.193 (4)	130
C14—H14···N4ii	0.93	2.47	3.279 (5)	146
C1—H1···O1	0.93	2.27	3.008 (4)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1i	0.93	2.52	3.063 (4)	118
C5—H5⋯O2i	0.93	2.49	3.419 (4)	174
C5—H5⋯O1i	0.93	2.51	3.193 (4)	130
C14—H14⋯N4ii	0.93	2.47	3.279 (5)	146
C1—H1⋯O1	0.93	2.27	3.008 (4)	135

Symmetry codes: (i) ; (ii) .