Di-μ-azido-κ(4)N(1):N(1')-bis-({1-[(E)-phen-yl(pyridin-2-yl-κN)methyl-idene]thio-semi-carbazidato-κ(2)N(1),S}copper(II)).

In the title compound, [Cu(2)(C(13)H(11)N(4)S)(2)(N(3))(2)], the Cu(II) cation is N,N',S-chelated by the deprotonated Schiff base ligand and is coordinated by the azide anion, while an N atom from an adjacent azide anion bridges the Cu(II) cation at the apical position with a longer Cu-N distance of 2.533 (3) Å, completing the distorted N(4)S square-pyramidal coordination geometry. A pair of azide anions bridge the two Cu(II) cations, forming a centrosymmetric binuclear mol-ecule. In the crystal, the binuclear mol-ecules are linked by an N-H⋯N hydrogen bond into a ribbon running along the a axis.

Related literature

For the structure of the parent Schiff base, see: Casas et al. (2003 ▶).

Experimental

Crystal data

[Cu2(C13H11N4S)2(N3)2]

M = 721.78

Monoclinic,

a = 11.2462 (12) Å

b = 7.2344 (10) Å

c = 18.519 (2) Å

β = 96.653 (5)°

V = 1496.5 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.61 mm−1

T = 295 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.604, T max = 0.690

13614 measured reflections

3747 independent reflections

2973 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.134

S = 1.04

3747 reflections

205 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.66 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035751/xu5611sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035751/xu5611Isup2.hkl

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

[Cu2(C13H11N4S)2(N3)2]	F(000) = 732
Mr = 721.78	Dx = 1.602 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4663 reflections
a = 11.2462 (12) Å	θ = 3.0–28.3°
b = 7.2344 (10) Å	µ = 1.61 mm−1
c = 18.519 (2) Å	T = 295 K
β = 96.653 (5)°	Prism, dark green
V = 1496.5 (3) Å3	0.35 × 0.30 × 0.25 mm
Z = 2

Bruker Kappa APEXII diffractometer	3747 independent reflections
Radiation source: fine-focus sealed tube	2973 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
ω scans	θmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→15
Tmin = 0.604, Tmax = 0.690	k = −9→9
13614 measured reflections	l = −24→24

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0694P)2 + 0.1161P] where P = (Fo2 + 2Fc2)/3
3747 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.54 e Å−3
2 restraints	Δρmin = −0.66 e Å−3

	x	y	z	Uiso*/Ueq
Cu1	0.40816 (2)	0.66511 (5)	0.521018 (15)	0.03737 (14)
S1	0.31362 (6)	0.55753 (11)	0.61376 (3)	0.0469 (2)
N1	0.24572 (17)	0.7151 (3)	0.47503 (10)	0.0345 (4)
N2	0.14750 (19)	0.6402 (3)	0.50005 (12)	0.0408 (5)
N3	0.0841 (2)	0.4802 (5)	0.59265 (14)	0.0617 (8)
H1	0.023 (2)	0.456 (6)	0.5610 (15)	0.074*
H2	0.101 (3)	0.422 (5)	0.6343 (12)	0.074*
N4	0.44641 (18)	0.8236 (3)	0.43679 (11)	0.0377 (5)
N5	0.5749 (2)	0.6199 (4)	0.55657 (12)	0.0468 (6)
N6	0.6113 (2)	0.5803 (4)	0.61823 (13)	0.0487 (6)
N7	0.6497 (3)	0.5408 (5)	0.67545 (14)	0.0721 (9)
C1	0.1174 (2)	0.8573 (3)	0.37564 (12)	0.0340 (5)
C2	0.0861 (3)	0.7823 (4)	0.30754 (14)	0.0454 (6)
H2A	0.1412	0.7109	0.2861	0.054*
C3	−0.0264 (3)	0.8127 (5)	0.27110 (15)	0.0506 (7)
H3	−0.0470	0.7627	0.2251	0.061*
C4	−0.1078 (2)	0.9171 (5)	0.30306 (16)	0.0506 (7)
H4	−0.1848	0.9339	0.2796	0.061*
C5	−0.0752 (3)	0.9963 (5)	0.36967 (17)	0.0556 (8)
H5	−0.1294	1.0707	0.3906	0.067*
C6	0.0364 (2)	0.9669 (4)	0.40563 (14)	0.0456 (6)
H6	0.0576	1.0216	0.4507	0.055*
C7	0.2345 (2)	0.8130 (3)	0.41657 (12)	0.0335 (5)
C8	0.1738 (2)	0.5609 (4)	0.56389 (13)	0.0414 (6)
C9	0.3482 (2)	0.8757 (4)	0.39278 (13)	0.0349 (5)
C10	0.3555 (2)	0.9761 (4)	0.33033 (14)	0.0438 (6)
H10	0.2866	1.0115	0.3010	0.053*
C11	0.4675 (3)	1.0232 (5)	0.31207 (16)	0.0510 (7)
H11	0.4750	1.0910	0.2702	0.061*
C12	0.5668 (3)	0.9688 (5)	0.35637 (17)	0.0546 (7)
H12	0.6428	0.9978	0.3446	0.065*
C13	0.5534 (2)	0.8708 (4)	0.41863 (16)	0.0460 (6)
H13	0.6214	0.8364	0.4490	0.055*

	U11	U22	U33	U12	U13	U23
Cu1	0.03127 (19)	0.0431 (2)	0.0358 (2)	0.00031 (11)	−0.00433 (13)	0.00303 (12)
S1	0.0438 (4)	0.0589 (5)	0.0356 (3)	−0.0033 (3)	−0.0049 (3)	0.0100 (3)
N1	0.0312 (9)	0.0386 (12)	0.0328 (9)	−0.0013 (8)	−0.0002 (7)	0.0049 (8)
N2	0.0332 (10)	0.0478 (14)	0.0404 (11)	−0.0046 (9)	−0.0003 (8)	0.0132 (9)
N3	0.0541 (15)	0.079 (2)	0.0504 (14)	−0.0192 (14)	−0.0032 (11)	0.0287 (14)
N4	0.0325 (10)	0.0390 (13)	0.0410 (11)	−0.0018 (8)	0.0018 (8)	−0.0002 (8)
N5	0.0366 (11)	0.0595 (16)	0.0412 (12)	0.0036 (11)	−0.0092 (9)	0.0006 (11)
N6	0.0408 (11)	0.0518 (16)	0.0499 (13)	0.0046 (10)	−0.0099 (10)	−0.0094 (11)
N7	0.081 (2)	0.083 (2)	0.0462 (14)	0.0153 (16)	−0.0196 (13)	−0.0044 (14)
C1	0.0341 (11)	0.0368 (14)	0.0308 (11)	−0.0008 (9)	0.0026 (9)	0.0077 (9)
C2	0.0456 (14)	0.0489 (17)	0.0402 (13)	0.0035 (12)	−0.0013 (10)	−0.0058 (12)
C3	0.0508 (16)	0.061 (2)	0.0370 (13)	−0.0032 (13)	−0.0064 (11)	0.0039 (12)
C4	0.0367 (13)	0.060 (2)	0.0527 (15)	0.0040 (12)	−0.0052 (11)	0.0219 (14)
C5	0.0421 (14)	0.065 (2)	0.0608 (17)	0.0200 (14)	0.0120 (12)	0.0086 (15)
C6	0.0455 (14)	0.0547 (18)	0.0368 (12)	0.0050 (12)	0.0057 (10)	0.0012 (11)
C7	0.0319 (11)	0.0343 (14)	0.0337 (11)	0.0022 (9)	0.0012 (9)	0.0002 (9)
C8	0.0409 (13)	0.0449 (17)	0.0370 (12)	−0.0025 (11)	−0.0006 (10)	0.0075 (10)
C9	0.0348 (11)	0.0332 (13)	0.0369 (11)	−0.0001 (10)	0.0050 (9)	−0.0004 (9)
C10	0.0446 (14)	0.0453 (17)	0.0418 (13)	−0.0020 (11)	0.0062 (11)	0.0050 (11)
C11	0.0551 (17)	0.0497 (18)	0.0508 (15)	−0.0051 (13)	0.0171 (13)	0.0057 (13)
C12	0.0425 (14)	0.055 (2)	0.0695 (19)	−0.0090 (13)	0.0208 (13)	−0.0018 (15)
C13	0.0336 (12)	0.0482 (17)	0.0557 (16)	−0.0032 (11)	0.0034 (11)	−0.0029 (12)

Cu1—N5	1.942 (2)	C2—C3	1.381 (4)
Cu1—N1	1.9578 (19)	C2—H2A	0.9300
Cu1—N4	2.022 (2)	C3—C4	1.373 (4)
Cu1—S1	2.2603 (8)	C3—H3	0.9300
Cu1—N5i	2.533 (3)	C4—C5	1.371 (5)
S1—C8	1.729 (3)	C4—H4	0.9300
N1—C7	1.287 (3)	C5—C6	1.368 (4)
N1—N2	1.359 (3)	C5—H5	0.9300
N2—C8	1.316 (3)	C6—H6	0.9300
N3—C8	1.329 (4)	C7—C9	1.472 (3)
N3—H1	0.872 (10)	C9—C10	1.376 (3)
N3—H2	0.879 (10)	C10—C11	1.384 (4)
N4—C13	1.331 (3)	C10—H10	0.9300
N4—C9	1.348 (3)	C11—C12	1.364 (4)
N5—N6	1.202 (3)	C11—H11	0.9300
N6—N7	1.134 (3)	C12—C13	1.377 (4)
C1—C6	1.372 (4)	C12—H12	0.9300
C1—C2	1.380 (4)	C13—H13	0.9300
C1—C7	1.477 (3)
N5—Cu1—N1	173.91 (9)	C2—C3—H3	120.1
N5—Cu1—N4	94.22 (9)	C5—C4—C3	119.7 (2)
N1—Cu1—N4	80.26 (8)	C5—C4—H4	120.1
N5—Cu1—S1	101.84 (7)	C3—C4—H4	120.1
N1—Cu1—S1	84.08 (6)	C6—C5—C4	120.5 (3)
N4—Cu1—S1	160.44 (7)	C6—C5—H5	119.7
N5—Cu1—N5i	85.54 (9)	C4—C5—H5	119.7
N1—Cu1—N5i	91.79 (8)	C5—C6—C1	120.5 (3)
N4—Cu1—N5i	89.28 (8)	C5—C6—H6	119.8
S1—Cu1—N5i	102.92 (6)	C1—C6—H6	119.8
C8—S1—Cu1	93.90 (9)	N1—C7—C9	114.7 (2)
C7—N1—N2	120.1 (2)	N1—C7—C1	123.1 (2)
C7—N1—Cu1	117.58 (17)	C9—C7—C1	122.3 (2)
N2—N1—Cu1	122.15 (15)	N2—C8—N3	116.7 (2)
C8—N2—N1	111.9 (2)	N2—C8—S1	125.6 (2)
C8—N3—H1	114 (2)	N3—C8—S1	117.71 (19)
C8—N3—H2	118 (3)	N4—C9—C10	122.1 (2)
H1—N3—H2	124 (4)	N4—C9—C7	114.3 (2)
C13—N4—C9	118.5 (2)	C10—C9—C7	123.6 (2)
C13—N4—Cu1	128.30 (19)	C9—C10—C11	118.7 (3)
C9—N4—Cu1	113.11 (16)	C9—C10—H10	120.7
N6—N5—Cu1	124.8 (2)	C11—C10—H10	120.7
N7—N6—N5	177.3 (3)	C12—C11—C10	119.1 (3)
C6—C1—C2	119.1 (2)	C12—C11—H11	120.4
C6—C1—C7	120.8 (2)	C10—C11—H11	120.4
C2—C1—C7	120.1 (2)	C11—C12—C13	119.4 (3)
C1—C2—C3	120.4 (3)	C11—C12—H12	120.3
C1—C2—H2A	119.8	C13—C12—H12	120.3
C3—C2—H2A	119.8	N4—C13—C12	122.2 (3)
C4—C3—C2	119.8 (3)	N4—C13—H13	118.9
C4—C3—H3	120.1	C12—C13—H13	118.9
N5—Cu1—S1—C8	−167.21 (13)	C2—C1—C6—C5	2.2 (4)
N1—Cu1—S1—C8	11.35 (12)	C7—C1—C6—C5	−175.2 (3)
N4—Cu1—S1—C8	48.2 (2)	N2—N1—C7—C9	−176.1 (2)
N5i—Cu1—S1—C8	−79.13 (11)	Cu1—N1—C7—C9	−0.5 (3)
N4—Cu1—N1—C7	1.37 (19)	N2—N1—C7—C1	3.0 (4)
S1—Cu1—N1—C7	169.6 (2)	Cu1—N1—C7—C1	178.59 (18)
N5i—Cu1—N1—C7	−87.6 (2)	C6—C1—C7—N1	65.7 (4)
N4—Cu1—N1—N2	176.9 (2)	C2—C1—C7—N1	−111.7 (3)
S1—Cu1—N1—N2	−14.88 (19)	C6—C1—C7—C9	−115.3 (3)
N5i—Cu1—N1—N2	87.9 (2)	C2—C1—C7—C9	67.3 (3)
C7—N1—N2—C8	−173.5 (2)	N1—N2—C8—N3	−178.8 (3)
Cu1—N1—N2—C8	11.1 (3)	N1—N2—C8—S1	2.6 (4)
N5—Cu1—N4—C13	−0.4 (2)	Cu1—S1—C8—N2	−11.5 (3)
N1—Cu1—N4—C13	−177.8 (3)	Cu1—S1—C8—N3	170.0 (3)
S1—Cu1—N4—C13	144.9 (2)	C13—N4—C9—C10	−0.3 (4)
N5i—Cu1—N4—C13	−85.9 (2)	Cu1—N4—C9—C10	−176.6 (2)
N5—Cu1—N4—C9	175.44 (18)	C13—N4—C9—C7	178.6 (2)
N1—Cu1—N4—C9	−1.97 (17)	Cu1—N4—C9—C7	2.2 (3)
S1—Cu1—N4—C9	−39.2 (3)	N1—C7—C9—N4	−1.2 (3)
N5i—Cu1—N4—C9	89.97 (18)	C1—C7—C9—N4	179.7 (2)
N4—Cu1—N5—N6	155.8 (3)	N1—C7—C9—C10	177.6 (3)
S1—Cu1—N5—N6	−13.0 (3)	C1—C7—C9—C10	−1.5 (4)
N5i—Cu1—N5—N6	−115.3 (3)	N4—C9—C10—C11	0.6 (4)
C6—C1—C2—C3	−2.0 (4)	C7—C9—C10—C11	−178.1 (3)
C7—C1—C2—C3	175.5 (3)	C9—C10—C11—C12	0.0 (5)
C1—C2—C3—C4	−0.5 (5)	C10—C11—C12—C13	−0.9 (5)
C2—C3—C4—C5	2.6 (5)	C9—N4—C13—C12	−0.7 (4)
C3—C4—C5—C6	−2.3 (5)	Cu1—N4—C13—C12	175.0 (2)
C4—C5—C6—C1	−0.1 (5)	C11—C12—C13—N4	1.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N2ii	0.87 (1)	2.22 (1)	3.075 (3)	168 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯N2i	0.87 (1)	2.22 (1)	3.075 (3)	168 (4)

Symmetry code: (i) .