Poly[bis-{μ-N'-[(pyridin-4-yl)methyl-idene]benzohydrazidato}copper(II)].

In the title complex, [Cu(C13H10N3O)2] n , the copper(II) cation is located on a crystallographic inversion centre and adopts an elongated octa-hedral coordination geometry with the equatorial plane provided by trans-arranged bis-N,O-chelating acyl-hydrazine groups from two ligands and the apices by the N atoms of two pyridine rings belonging to symmetry-related ligands. The ligand adopts a Z conformation about the C=N double bond. The dihedral angle between the pyridine and phenyl rings is 2.99 (13)°. An intra-ligand C-H⋯N hydrogen bond is observed. In the crystal, each ligand bridges two adjacent metal ions, forming a (4,4) grid layered structure. π-π stacking inter-actions [centroid-centroid distances in the range 3.569 (4)-3.584 (9) Å] involving rings of adjacent layers result in the formation of a three-dimensional supra-molecular network.

Related literature

For background to properties and applications of Schiff base–metal complexes, see: Schurig et al. (1980 ▶); Siddall et al. (1983 ▶); Maurya et al. (2005 ▶); Cozzi (2004 ▶); Liu et al. (2010 ▶). For the structures of related compounds, see: Yin (2008 ▶); Uçar et al. (2004 ▶); Sommerer et al. (1998 ▶); Moya-Hernández et al. (2003 ▶).

Experimental

Crystal data

[Cu(C13H10N3O)2]

M = 512.02

Monoclinic,

a = 12.288 (3) Å

b = 13.349 (3) Å

c = 14.244 (3) Å

β = 113.39 (3)°

V = 2144.5 (10) Å3

Z = 4

Mo Kα radiation

μ = 1.06 mm−1

T = 173 K

0.40 × 0.20 × 0.12 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T min = 0.843, T max = 1.000

10356 measured reflections

2460 independent reflections

2033 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.080

S = 1.05

2460 reflections

160 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CrystalClear; 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, global. DOI: 10.1107/S1600536813015882/rz5068sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015882/rz5068Isup2.hkl

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

[Cu(C13H10N3O)2]	Z = 4
Mr = 512.02	F(000) = 1052
Monoclinic, C2/c	Dx = 1.586 Mg m−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.288 (3) Å	µ = 1.06 mm−1
b = 13.349 (3) Å	T = 173 K
c = 14.244 (3) Å	Block, brown
β = 113.39 (3)°	0.40 × 0.20 × 0.12 mm
V = 2144.5 (10) Å3

Rigaku Mercury CCD area-detector diffractometer	2460 independent reflections
Radiation source: fine-focus sealed tube	2033 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scan	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −15→15
Tmin = 0.843, Tmax = 1.000	k = −17→17
10356 measured reflections	l = −18→18

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.038P)2 + 1.4497P] where P = (Fo2 + 2Fc2)/3
2460 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.19 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	0.2500	0.2500	0.0000	0.03006 (12)
O1	0.07807 (11)	0.24346 (9)	−0.06638 (10)	0.0309 (3)
N3	0.27033 (14)	−0.10391 (12)	0.38950 (12)	0.0319 (4)
N2	0.21900 (13)	0.15245 (10)	0.09372 (11)	0.0246 (3)
N1	0.09996 (13)	0.13652 (11)	0.06875 (12)	0.0278 (3)
C13	0.38186 (16)	−0.00109 (14)	0.32256 (15)	0.0323 (4)
H13	0.4576	0.0211	0.3281	0.039*
C10	0.17175 (16)	0.00125 (14)	0.24281 (15)	0.0321 (4)
H10	0.0988	0.0242	0.1923	0.038*
C11	0.17304 (17)	−0.06719 (15)	0.31632 (15)	0.0346 (4)
H11	0.0988	−0.0896	0.3143	0.042*
C9	0.27962 (16)	0.03584 (13)	0.24435 (14)	0.0265 (4)
C7	0.03622 (16)	0.18736 (13)	−0.01562 (14)	0.0258 (4)
C12	0.37330 (17)	−0.06991 (15)	0.39198 (15)	0.0329 (4)
H12	0.4444	−0.0941	0.4440	0.039*
C1	−0.16555 (18)	0.23105 (14)	−0.13975 (16)	0.0339 (4)
H1	−0.1296	0.2705	−0.1751	0.041*
C6	−0.09470 (16)	0.17841 (13)	−0.05313 (14)	0.0278 (4)
C8	0.29530 (15)	0.10671 (13)	0.17138 (14)	0.0265 (4)
H8	0.3756	0.1211	0.1839	0.032*
C3	−0.34020 (18)	0.16951 (16)	−0.12463 (17)	0.0405 (5)
H3	−0.4241	0.1675	−0.1482	0.049*
C4	−0.27127 (19)	0.11491 (17)	−0.03975 (18)	0.0418 (5)
H4	−0.3079	0.0743	−0.0058	0.050*
C2	−0.28764 (18)	0.22705 (15)	−0.17542 (17)	0.0389 (5)
H2	−0.3352	0.2638	−0.2347	0.047*
C5	−0.14871 (17)	0.11890 (15)	−0.00365 (16)	0.0362 (4)
H5	−0.1015	0.0810	0.0549	0.043*

	U11	U22	U33	U12	U13	U23
Cu1	0.02433 (17)	0.0392 (2)	0.02625 (18)	−0.00444 (14)	0.00965 (13)	0.01200 (14)
O1	0.0302 (6)	0.0357 (7)	0.0279 (7)	−0.0040 (6)	0.0128 (6)	0.0066 (5)
N3	0.0378 (9)	0.0309 (8)	0.0280 (9)	0.0025 (7)	0.0141 (7)	0.0053 (6)
N2	0.0270 (7)	0.0247 (7)	0.0247 (8)	−0.0015 (6)	0.0130 (6)	−0.0002 (6)
N1	0.0257 (7)	0.0301 (8)	0.0282 (8)	−0.0026 (6)	0.0113 (6)	0.0050 (6)
C13	0.0284 (9)	0.0358 (10)	0.0337 (11)	0.0008 (8)	0.0136 (8)	0.0044 (8)
C10	0.0285 (9)	0.0346 (9)	0.0307 (10)	0.0012 (8)	0.0090 (8)	0.0077 (8)
C11	0.0315 (10)	0.0369 (10)	0.0363 (11)	−0.0004 (8)	0.0144 (9)	0.0088 (8)
C9	0.0309 (9)	0.0235 (8)	0.0262 (9)	0.0025 (7)	0.0125 (8)	0.0013 (7)
C7	0.0314 (9)	0.0238 (8)	0.0247 (9)	−0.0023 (7)	0.0139 (8)	−0.0017 (7)
C12	0.0320 (9)	0.0353 (10)	0.0289 (10)	0.0065 (8)	0.0094 (8)	0.0072 (8)
C1	0.0352 (10)	0.0333 (10)	0.0337 (11)	−0.0001 (8)	0.0143 (9)	0.0064 (8)
C6	0.0308 (9)	0.0272 (9)	0.0276 (10)	−0.0028 (7)	0.0139 (8)	−0.0006 (7)
C8	0.0279 (9)	0.0265 (8)	0.0272 (9)	0.0003 (7)	0.0133 (8)	0.0017 (7)
C3	0.0301 (10)	0.0448 (12)	0.0471 (13)	−0.0040 (9)	0.0159 (9)	−0.0033 (9)
C4	0.0391 (11)	0.0462 (12)	0.0455 (12)	−0.0106 (10)	0.0227 (10)	0.0031 (10)
C2	0.0340 (10)	0.0396 (11)	0.0382 (12)	0.0031 (9)	0.0092 (9)	0.0068 (8)
C5	0.0350 (10)	0.0402 (11)	0.0339 (11)	−0.0026 (9)	0.0141 (9)	0.0080 (8)

Cu1—O1i	1.9440 (15)	C11—H11	0.9500
Cu1—O1	1.9440 (15)	C9—C8	1.474 (2)
Cu1—N2i	2.0066 (14)	C7—C6	1.485 (2)
Cu1—N2	2.0066 (14)	C12—H12	0.9500
O1—C7	1.282 (2)	C1—C2	1.381 (3)
N3—C11	1.329 (2)	C1—C6	1.386 (3)
N3—C12	1.331 (2)	C1—H1	0.9500
N2—C8	1.285 (2)	C6—C5	1.393 (3)
N2—N1	1.378 (2)	C8—H8	0.9500
N1—C7	1.331 (2)	C3—C4	1.377 (3)
C13—C12	1.384 (3)	C3—C2	1.379 (3)
C13—C9	1.397 (3)	C3—H3	0.9500
C13—H13	0.9500	C4—C5	1.386 (3)
C10—C11	1.385 (3)	C4—H4	0.9500
C10—C9	1.395 (3)	C2—H2	0.9500
C10—H10	0.9500	C5—H5	0.9500
O1i—Cu1—O1	180.0	N1—C7—C6	116.68 (15)
O1i—Cu1—N2i	80.66 (6)	N3—C12—C13	123.25 (18)
O1—Cu1—N2i	99.34 (6)	N3—C12—H12	118.4
O1i—Cu1—N2	99.34 (6)	C13—C12—H12	118.4
O1—Cu1—N2	80.66 (6)	C2—C1—C6	120.98 (18)
N2i—Cu1—N2	180.00 (8)	C2—C1—H1	119.5
C7—O1—Cu1	110.72 (12)	C6—C1—H1	119.5
C11—N3—C12	116.40 (16)	C1—C6—C5	118.85 (17)
C8—N2—N1	119.06 (15)	C1—C6—C7	119.16 (16)
C8—N2—Cu1	127.92 (12)	C5—C6—C7	121.98 (17)
N1—N2—Cu1	113.01 (11)	N2—C8—C9	131.08 (16)
C7—N1—N2	109.77 (14)	N2—C8—H8	114.5
C12—C13—C9	120.31 (18)	C9—C8—H8	114.5
C12—C13—H13	119.8	C4—C3—C2	120.16 (19)
C9—C13—H13	119.8	C4—C3—H3	119.9
C11—C10—C9	118.73 (18)	C2—C3—H3	119.9
C11—C10—H10	120.6	C3—C4—C5	120.28 (19)
C9—C10—H10	120.6	C3—C4—H4	119.9
N3—C11—C10	124.95 (18)	C5—C4—H4	119.9
N3—C11—H11	117.5	C3—C2—C1	119.68 (19)
C10—C11—H11	117.5	C3—C2—H2	120.2
C10—C9—C13	116.34 (17)	C1—C2—H2	120.2
C10—C9—C8	126.20 (17)	C4—C5—C6	120.01 (19)
C13—C9—C8	117.45 (16)	C4—C5—H5	120.0
O1—C7—N1	125.68 (16)	C6—C5—H5	120.0
O1—C7—C6	117.64 (16)
N2i—Cu1—O1—C7	−176.85 (12)	C11—N3—C12—C13	−0.8 (3)
N2—Cu1—O1—C7	3.15 (12)	C9—C13—C12—N3	−0.5 (3)
O1i—Cu1—N2—C8	−2.68 (16)	C2—C1—C6—C5	1.6 (3)
O1—Cu1—N2—C8	177.32 (16)	C2—C1—C6—C7	−178.12 (18)
O1i—Cu1—N2—N1	176.46 (11)	O1—C7—C6—C1	−0.6 (3)
O1—Cu1—N2—N1	−3.54 (11)	N1—C7—C6—C1	178.95 (17)
C8—N2—N1—C7	−177.64 (15)	O1—C7—C6—C5	179.64 (17)
Cu1—N2—N1—C7	3.13 (17)	N1—C7—C6—C5	−0.8 (3)
C12—N3—C11—C10	1.3 (3)	N1—N2—C8—C9	−0.2 (3)
C9—C10—C11—N3	−0.3 (3)	Cu1—N2—C8—C9	178.87 (14)
C11—C10—C9—C13	−1.0 (3)	C10—C9—C8—N2	0.8 (3)
C11—C10—C9—C8	178.68 (18)	C13—C9—C8—N2	−179.51 (18)
C12—C13—C9—C10	1.4 (3)	C2—C3—C4—C5	1.2 (3)
C12—C13—C9—C8	−178.30 (17)	C4—C3—C2—C1	−1.1 (3)
Cu1—O1—C7—N1	−2.6 (2)	C6—C1—C2—C3	−0.3 (3)
Cu1—O1—C7—C6	176.93 (12)	C3—C4—C5—C6	0.1 (3)
N2—N1—C7—O1	−0.4 (2)	C1—C6—C5—C4	−1.5 (3)
N2—N1—C7—C6	−179.92 (14)	C7—C6—C5—C4	178.24 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N1	0.95	2.32	2.907 (3)	120

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯N1	0.95	2.32	2.907 (3)	120