(Cyanato-κN){1-[(E)-phen-yl(pyridin-2-yl-κN)methyl-idene]semicarbazidato-κ(2)N(1),O}copper(II).

The Cu(II) atom in the title compound, [Cu(C(13)H(11)N(4)O)(NCO)], is N,N',O-chelated by the mono-deprotonated Schiff base ligand and it is also covalently bonded to the nitro-gen end of the cyanate ion. The Cu(II) atom shows a square-planar coordination that is distorted towards square-pyramidal owing to an inter-molecular Cu⋯N(cyanate) inter-action [2.623 (2) Å], which gives a centrosymmetric dimer. In the square-planar description, the Cu(II) atom is displaced out of the square plane [r.m.s. deviation = 0.048 Å] by 0.084 (1) Å in the direction of the apical occupant. In the crystal, adjacent complex dimers are linked by an amine N-H⋯N hydrogen-bond pair, also giving a centrosymmetric cyclic association [graph set R(2) (2)(8)], generating a linear chain parallel to [110].

Related literature

For the synthesis of the Schiff base, see: de Lima et al. (2008 ▶). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006 ▶). For graph-set notation, see: Etter et al. (1990 ▶).

Experimental

Crystal data

[Cu(C13H11N4O)(NCO)]

M = 344.82

Monoclinic,

a = 8.7601 (1) Å

b = 7.6732 (1) Å

c = 20.0819 (3) Å

β = 96.7467 (7)°

V = 1340.52 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.64 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.638, T max = 0.735

11886 measured reflections

3069 independent reflections

2728 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.093

S = 1.03

3069 reflections

208 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.47 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/S1600536812035386/zs2226sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035386/zs2226Isup2.hkl

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

[Cu(C13H11N4O)(NCO)]	F(000) = 700
Mr = 344.82	Dx = 1.709 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 838 reflections
a = 8.7601 (1) Å	θ = 2.4–28.3°
b = 7.6732 (1) Å	µ = 1.64 mm−1
c = 20.0819 (3) Å	T = 293 K
β = 96.7467 (7)°	Prism, dark green
V = 1340.52 (3) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker Kappa APEXII diffractometer	3069 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.638, Tmax = 0.735	k = −9→9
11886 measured reflections	l = −26→26

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0579P)2 + 0.5121P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3069 reflections	Δρmax = 0.37 e Å−3
208 parameters	Δρmin = −0.47 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0221 (17)

	x	y	z	Uiso*/Ueq
Cu1	0.31070 (2)	0.50325 (3)	0.506177 (10)	0.03203 (12)
O1	0.28257 (17)	0.3049 (2)	0.56285 (6)	0.0473 (4)
O2	0.5831 (2)	0.6387 (3)	0.67349 (8)	0.0696 (6)
N1	0.26412 (17)	0.6848 (2)	0.43675 (7)	0.0323 (3)
N2	0.13987 (16)	0.38948 (19)	0.45304 (7)	0.0287 (3)
N3	0.09476 (17)	0.2331 (2)	0.47511 (7)	0.0332 (3)
N4	0.1503 (3)	0.0571 (3)	0.56674 (9)	0.0526 (5)
H41	0.078 (2)	−0.018 (3)	0.5525 (15)	0.057 (8)*
H42	0.196 (3)	0.034 (4)	0.6065 (8)	0.059 (8)*
N5	0.47729 (18)	0.6213 (2)	0.56268 (8)	0.0391 (4)
C1	0.3226 (2)	0.8437 (3)	0.43590 (10)	0.0425 (4)
H1	0.3972	0.8773	0.4703	0.051*
C2	0.2763 (3)	0.9611 (3)	0.38550 (13)	0.0480 (5)
H2	0.3178	1.0727	0.3862	0.058*
C3	0.1682 (2)	0.9104 (3)	0.33440 (11)	0.0448 (5)
H3	0.1354	0.9875	0.2999	0.054*
C4	0.1084 (2)	0.7441 (3)	0.33435 (9)	0.0383 (4)
H4	0.0364	0.7071	0.2995	0.046*
C5	0.15699 (19)	0.6327 (2)	0.38691 (8)	0.0299 (3)
C6	0.09472 (19)	0.4563 (3)	0.39498 (8)	0.0289 (3)
C7	−0.00451 (19)	0.3697 (2)	0.34034 (8)	0.0295 (3)
C8	0.0435 (2)	0.3596 (3)	0.27703 (9)	0.0373 (4)
H8	0.1360	0.4106	0.2691	0.045*
C9	−0.0453 (2)	0.2744 (3)	0.22558 (9)	0.0438 (5)
H9	−0.0119	0.2674	0.1834	0.053*
C10	−0.1826 (2)	0.2003 (3)	0.23667 (10)	0.0453 (5)
H10	−0.2419	0.1424	0.2021	0.054*
C11	−0.2324 (2)	0.2114 (3)	0.29881 (11)	0.0438 (5)
H11	−0.3263	0.1626	0.3060	0.053*
C12	−0.1440 (2)	0.2947 (3)	0.35081 (9)	0.0351 (4)
H12	−0.1779	0.3006	0.3929	0.042*
C13	0.1784 (2)	0.2042 (3)	0.53522 (8)	0.0369 (4)
C14	0.5253 (2)	0.6252 (3)	0.61718 (10)	0.0396 (4)

	U11	U22	U33	U12	U13	U23
Cu1	0.03601 (17)	0.03610 (18)	0.02273 (15)	−0.00921 (8)	−0.00184 (10)	−0.00184 (7)
O1	0.0603 (9)	0.0532 (9)	0.0253 (6)	−0.0211 (7)	−0.0086 (6)	0.0083 (6)
O2	0.0639 (10)	0.1105 (17)	0.0313 (7)	−0.0030 (10)	−0.0079 (7)	−0.0060 (9)
N1	0.0361 (7)	0.0323 (8)	0.0282 (7)	−0.0055 (6)	0.0017 (6)	−0.0025 (6)
N2	0.0310 (7)	0.0321 (7)	0.0227 (6)	−0.0053 (6)	0.0020 (5)	−0.0012 (5)
N3	0.0399 (7)	0.0341 (8)	0.0250 (6)	−0.0089 (6)	0.0013 (6)	0.0017 (6)
N4	0.0713 (13)	0.0508 (11)	0.0329 (9)	−0.0212 (10)	−0.0060 (8)	0.0121 (8)
N5	0.0370 (8)	0.0480 (10)	0.0316 (8)	−0.0072 (7)	0.0011 (6)	−0.0007 (7)
C1	0.0503 (11)	0.0374 (10)	0.0396 (10)	−0.0124 (8)	0.0041 (8)	−0.0064 (8)
C2	0.0609 (13)	0.0314 (9)	0.0536 (13)	−0.0093 (10)	0.0149 (10)	0.0014 (9)
C3	0.0528 (11)	0.0375 (11)	0.0452 (11)	0.0039 (9)	0.0104 (9)	0.0092 (9)
C4	0.0400 (9)	0.0381 (10)	0.0358 (9)	0.0018 (8)	−0.0002 (7)	0.0037 (8)
C5	0.0295 (7)	0.0314 (9)	0.0288 (7)	−0.0007 (6)	0.0034 (6)	−0.0017 (6)
C6	0.0270 (7)	0.0332 (8)	0.0261 (8)	−0.0013 (7)	0.0014 (6)	−0.0013 (7)
C7	0.0296 (7)	0.0297 (8)	0.0273 (7)	−0.0003 (6)	−0.0041 (6)	0.0010 (6)
C8	0.0344 (9)	0.0473 (11)	0.0295 (8)	−0.0053 (8)	0.0008 (7)	−0.0012 (8)
C9	0.0500 (11)	0.0512 (12)	0.0285 (8)	0.0002 (9)	−0.0031 (8)	−0.0051 (8)
C10	0.0465 (11)	0.0454 (12)	0.0396 (10)	−0.0040 (9)	−0.0142 (8)	−0.0070 (8)
C11	0.0317 (9)	0.0455 (11)	0.0515 (11)	−0.0083 (8)	−0.0062 (8)	0.0002 (9)
C12	0.0309 (8)	0.0368 (10)	0.0368 (9)	−0.0022 (7)	0.0013 (7)	0.0002 (7)
C13	0.0456 (10)	0.0403 (10)	0.0247 (8)	−0.0078 (8)	0.0039 (7)	0.0023 (7)
C14	0.0350 (9)	0.0442 (11)	0.0398 (10)	−0.0061 (8)	0.0060 (7)	−0.0032 (8)

Cu1—O1	1.9335 (14)	C2—H2	0.9300
Cu1—N2	1.9404 (14)	C3—C4	1.379 (3)
Cu1—N5	1.9618 (16)	C3—H3	0.9300
Cu1—N1	1.9790 (15)	C4—C5	1.385 (2)
Cu1—N5i	2.6225 (17)	C4—H4	0.9300
O1—C13	1.272 (2)	C5—C6	1.475 (2)
O2—C14	1.188 (2)	C6—C7	1.475 (2)
N1—C1	1.324 (2)	C7—C8	1.388 (2)
N1—C5	1.349 (2)	C7—C12	1.388 (2)
N2—C6	1.293 (2)	C8—C9	1.382 (3)
N2—N3	1.354 (2)	C8—H8	0.9300
N3—C13	1.355 (2)	C9—C10	1.372 (3)
N4—C13	1.331 (3)	C9—H9	0.9300
N4—H41	0.876 (10)	C10—C11	1.372 (3)
N4—H42	0.869 (10)	C10—H10	0.9300
N5—C14	1.126 (2)	C11—C12	1.382 (3)
C1—C2	1.380 (3)	C11—H11	0.9300
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.368 (3)
O1—Cu1—N2	79.99 (6)	C3—C4—C5	119.16 (18)
O1—Cu1—N5	99.25 (6)	C3—C4—H4	120.4
N2—Cu1—N5	177.52 (6)	C5—C4—H4	120.4
O1—Cu1—N1	159.83 (6)	N1—C5—C4	120.48 (17)
N2—Cu1—N1	81.22 (6)	N1—C5—C6	115.08 (15)
N5—Cu1—N1	99.23 (7)	C4—C5—C6	124.40 (16)
O1—Cu1—N5i	99.82 (6)	N2—C6—C7	125.67 (17)
N2—Cu1—N5i	95.41 (6)	N2—C6—C5	112.66 (15)
N5—Cu1—N5i	87.05 (6)	C7—C6—C5	121.65 (15)
N1—Cu1—N5i	89.15 (6)	C8—C7—C12	118.85 (16)
C13—O1—Cu1	110.84 (11)	C8—C7—C6	119.40 (16)
C1—N1—C5	119.97 (16)	C12—C7—C6	121.74 (16)
C1—N1—Cu1	127.54 (13)	C9—C8—C7	120.43 (18)
C5—N1—Cu1	112.47 (12)	C9—C8—H8	119.8
C6—N2—N3	125.23 (14)	C7—C8—H8	119.8
C6—N2—Cu1	116.88 (12)	C10—C9—C8	120.13 (19)
N3—N2—Cu1	117.03 (10)	C10—C9—H9	119.9
N2—N3—C13	106.76 (14)	C8—C9—H9	119.9
C13—N4—H41	124 (2)	C9—C10—C11	120.02 (17)
C13—N4—H42	121 (2)	C9—C10—H10	120.0
H41—N4—H42	114 (3)	C11—C10—H10	120.0
C14—N5—Cu1	137.89 (16)	C10—C11—C12	120.38 (18)
N1—C1—C2	121.99 (19)	C10—C11—H11	119.8
N1—C1—H1	119.0	C12—C11—H11	119.8
C2—C1—H1	119.0	C11—C12—C7	120.18 (18)
C3—C2—C1	118.8 (2)	C11—C12—H12	119.9
C3—C2—H2	120.6	C7—C12—H12	119.9
C1—C2—H2	120.6	O1—C13—N4	118.09 (17)
C2—C3—C4	119.53 (19)	O1—C13—N3	125.08 (17)
C2—C3—H3	120.2	N4—C13—N3	116.82 (17)
C4—C3—H3	120.2	N5—C14—O2	175.1 (2)
N2—Cu1—O1—C13	3.55 (14)	Cu1—N1—C5—C4	179.09 (14)
N5—Cu1—O1—C13	−178.85 (14)	C1—N1—C5—C6	−177.08 (16)
N1—Cu1—O1—C13	25.1 (3)	Cu1—N1—C5—C6	1.45 (19)
N5i—Cu1—O1—C13	−90.27 (14)	C3—C4—C5—N1	−1.5 (3)
O1—Cu1—N1—C1	150.16 (19)	C3—C4—C5—C6	175.87 (18)
N2—Cu1—N1—C1	171.58 (18)	N3—N2—C6—C7	−4.9 (3)
N5—Cu1—N1—C1	−5.94 (18)	Cu1—N2—C6—C7	164.10 (13)
N5i—Cu1—N1—C1	−92.81 (17)	N3—N2—C6—C5	176.72 (15)
O1—Cu1—N1—C5	−28.2 (3)	Cu1—N2—C6—C5	−14.28 (19)
N2—Cu1—N1—C5	−6.80 (12)	N1—C5—C6—N2	8.2 (2)
N5—Cu1—N1—C5	175.67 (12)	C4—C5—C6—N2	−169.37 (17)
N5i—Cu1—N1—C5	88.80 (12)	N1—C5—C6—C7	−170.28 (15)
O1—Cu1—N2—C6	−175.17 (14)	C4—C5—C6—C7	12.2 (3)
N1—Cu1—N2—C6	12.18 (13)	N2—C6—C7—C8	−126.9 (2)
N5i—Cu1—N2—C6	−76.12 (14)	C5—C6—C7—C8	51.4 (2)
O1—Cu1—N2—N3	−5.25 (12)	N2—C6—C7—C12	51.9 (3)
N1—Cu1—N2—N3	−177.90 (13)	C5—C6—C7—C12	−129.86 (18)
N5i—Cu1—N2—N3	93.80 (12)	C12—C7—C8—C9	−0.8 (3)
C6—N2—N3—C13	174.42 (17)	C6—C7—C8—C9	178.00 (19)
Cu1—N2—N3—C13	5.43 (18)	C7—C8—C9—C10	0.5 (3)
O1—Cu1—N5—C14	−22.4 (3)	C8—C9—C10—C11	0.4 (3)
N1—Cu1—N5—C14	149.4 (2)	C9—C10—C11—C12	−1.0 (3)
N5i—Cu1—N5—C14	−121.9 (3)	C10—C11—C12—C7	0.8 (3)
C5—N1—C1—C2	0.7 (3)	C8—C7—C12—C11	0.2 (3)
Cu1—N1—C1—C2	−177.57 (16)	C6—C7—C12—C11	−178.62 (18)
N1—C1—C2—C3	−1.0 (3)	Cu1—O1—C13—N4	176.97 (17)
C1—C2—C3—C4	0.0 (3)	Cu1—O1—C13—N3	−1.7 (3)
C2—C3—C4—C5	1.3 (3)	N2—N3—C13—O1	−2.4 (3)
C1—N1—C5—C4	0.6 (3)	N2—N3—C13—N4	178.93 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···N3ii	0.88 (1)	2.27 (1)	3.139 (2)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯N3i	0.88 (1)	2.27 (1)	3.139 (2)	173 (3)

Symmetry code: (i) .