Bis{μ-2-[1-(2-Pyridylmethyl-imino)eth-yl]phenolato}bis-[azido-copper(II)].

The title compound, [Cu(2)(C(14)H(13)N(2)O)(2)(N(3))(2)], was synthesized by the reaction of Cu(NO(3))(2)·3H(2)O with the Schiff base 2-[1-(2-pyridylmethyl-imino)eth-yl]phenol (HL) in methanol-water solution, adding NaN(3) as the bridging ligand. The asymmetric unit contains one half-mol-ecule, the other half being generated by the inversion center. Each Cu(II) atom shows a slightly distorted trigonal-pyramidal geometry formed by two N atoms and one O atom from one Schiff base ligand, by another O atom of a second Schiff base ligand and by an azide N atom. The crystal structure is stabilized by intermolecular C-H⋯N hydrogen bonds.

Related literature

For the potential applications in catalysis and enzymatic reactions, magnetism and mol­ecular architecture of transition metal compounds containing Schiff base ligands, see: Li & Zhang (2004 ▶); You & Zhu (2004 ▶). For the synthesis, see: Pointeau et al. (1986 ▶).

Experimental

Crystal data

[Cu2(C14H13N2O)2(N3)2]

M = 661.67

Monoclinic,

a = 10.1066 (12) Å

b = 8.0545 (10) Å

c = 16.7027 (18) Å

β = 96.251 (1)°

V = 1351.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.62 mm−1

T = 298 K

0.20 × 0.12 × 0.09 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.737, T max = 0.868

6641 measured reflections

2379 independent reflections

1720 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.062

S = 1.02

2379 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536809030475/at2842sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030475/at2842Isup2.hkl

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

[Cu2(C14H13N2O)2(N3)2]	F(000) = 676
Mr = 661.67	Dx = 1.626 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13380 reflections
a = 10.1066 (12) Å	θ = 3.0–27.6°
b = 8.0545 (10) Å	µ = 1.62 mm−1
c = 16.7027 (18) Å	T = 298 K
β = 96.251 (1)°	Prism, dark green
V = 1351.6 (3) Å3	0.20 × 0.12 × 0.09 mm
Z = 2

Rigaku SCXmini diffractometer	2379 independent reflections
Radiation source: fine-focus sealed tube	1720 reflections with I > 2σ(I)
graphite	Rint = 0.042
Detector resolution: 8.192 pixels mm-1	θmax = 25.0°, θmin = 2.3°
Thin–slice ω scans	h = −12→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.737, Tmax = 0.868	l = −19→19
6641 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0192P)2] where P = (Fo2 + 2Fc2)/3
2379 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.35 e Å−3
0 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	0.00744 (4)	0.69734 (4)	0.00638 (2)	0.03343 (13)
N1	−0.0002 (2)	0.6887 (3)	0.12413 (13)	0.0349 (6)
N2	−0.1427 (2)	0.8584 (3)	0.01237 (14)	0.0324 (6)
N3	0.0263 (3)	0.7564 (3)	−0.10588 (15)	0.0448 (7)
N4	0.1145 (3)	0.7080 (3)	−0.14292 (14)	0.0391 (7)
N5	0.1975 (3)	0.6669 (4)	−0.18111 (16)	0.0579 (9)
O1	0.14375 (17)	0.5289 (2)	0.01510 (10)	0.0333 (5)
C1	0.0637 (3)	0.6042 (5)	0.26461 (17)	0.0594 (10)
H1A	0.1024	0.6932	0.2975	0.089*
H1B	0.1029	0.5008	0.2834	0.089*
H1C	−0.0305	0.6009	0.2678	0.089*
C2	0.0898 (3)	0.6322 (4)	0.17764 (17)	0.0374 (8)
C3	0.2216 (3)	0.5861 (4)	0.15511 (17)	0.0359 (8)
C4	0.2396 (3)	0.5298 (4)	0.07618 (17)	0.0347 (8)
C5	0.3666 (3)	0.4732 (4)	0.06349 (19)	0.0417 (8)
H5	0.3788	0.4258	0.0141	0.050*
C6	0.4741 (3)	0.4850 (4)	0.1214 (2)	0.0530 (9)
H6	0.5573	0.4477	0.1104	0.064*
C7	0.4584 (4)	0.5521 (4)	0.1957 (2)	0.0583 (11)
H7	0.5314	0.5661	0.2340	0.070*
C8	0.3338 (4)	0.5977 (4)	0.21236 (19)	0.0482 (9)
H8	0.3230	0.6379	0.2634	0.058*
C9	−0.1311 (3)	0.7385 (4)	0.14550 (18)	0.0443 (9)
H9A	−0.1217	0.7914	0.1980	0.053*
H9B	−0.1871	0.6413	0.1483	0.053*
C10	−0.1947 (3)	0.8571 (4)	0.08326 (18)	0.0366 (8)
C11	−0.2990 (3)	0.9584 (4)	0.0981 (2)	0.0496 (10)
H11	−0.3332	0.9548	0.1475	0.060*
C12	−0.3517 (3)	1.0650 (4)	0.0388 (2)	0.0528 (10)
H12	−0.4217	1.1350	0.0478	0.063*
C13	−0.3000 (3)	1.0671 (4)	−0.0340 (2)	0.0473 (9)
H13	−0.3352	1.1373	−0.0752	0.057*
C14	−0.1951 (3)	0.9631 (4)	−0.04483 (19)	0.0421 (8)
H14	−0.1593	0.9658	−0.0938	0.050*

	U11	U22	U33	U12	U13	U23
Cu1	0.0379 (2)	0.0380 (2)	0.0248 (2)	0.0016 (2)	0.00541 (15)	−0.00083 (19)
N1	0.0380 (16)	0.0401 (16)	0.0275 (14)	−0.0004 (13)	0.0078 (11)	−0.0019 (13)
N2	0.0352 (16)	0.0305 (15)	0.0317 (15)	−0.0032 (11)	0.0049 (12)	−0.0038 (11)
N3	0.0442 (18)	0.061 (2)	0.0314 (15)	0.0104 (14)	0.0125 (13)	0.0084 (13)
N4	0.0471 (19)	0.0414 (17)	0.0282 (15)	−0.0024 (15)	0.0017 (13)	0.0035 (13)
N5	0.063 (2)	0.066 (2)	0.0480 (18)	0.0109 (17)	0.0234 (16)	−0.0012 (16)
O1	0.0343 (12)	0.0404 (14)	0.0245 (11)	0.0027 (10)	0.0009 (9)	−0.0022 (9)
C1	0.075 (3)	0.076 (3)	0.029 (2)	0.009 (2)	0.0094 (17)	0.0074 (18)
C2	0.053 (2)	0.0332 (19)	0.0261 (18)	−0.0024 (16)	0.0044 (16)	−0.0019 (14)
C3	0.042 (2)	0.0366 (19)	0.0282 (18)	−0.0008 (16)	−0.0008 (15)	0.0049 (14)
C4	0.0376 (19)	0.032 (2)	0.0349 (19)	−0.0034 (14)	0.0051 (15)	0.0039 (14)
C5	0.039 (2)	0.047 (2)	0.0389 (19)	0.0029 (17)	0.0041 (15)	0.0007 (16)
C6	0.039 (2)	0.060 (2)	0.058 (2)	0.0060 (19)	−0.0008 (17)	0.006 (2)
C7	0.047 (2)	0.069 (3)	0.053 (3)	−0.0019 (19)	−0.0188 (18)	0.004 (2)
C8	0.061 (3)	0.049 (2)	0.033 (2)	−0.0034 (19)	−0.0043 (17)	0.0018 (16)
C9	0.049 (2)	0.053 (2)	0.0342 (19)	0.0045 (17)	0.0166 (16)	0.0016 (16)
C10	0.038 (2)	0.035 (2)	0.037 (2)	−0.0054 (15)	0.0083 (15)	−0.0065 (15)
C11	0.048 (2)	0.051 (3)	0.051 (2)	0.0052 (18)	0.0162 (18)	−0.0071 (18)
C12	0.042 (2)	0.052 (2)	0.065 (3)	0.0054 (18)	0.0059 (19)	−0.016 (2)
C13	0.044 (2)	0.039 (2)	0.056 (2)	−0.0018 (17)	−0.0072 (17)	0.0015 (17)
C14	0.046 (2)	0.042 (2)	0.038 (2)	−0.0022 (16)	0.0022 (15)	−0.0026 (16)

Cu1—O1	1.9278 (18)	C4—C5	1.399 (4)
Cu1—N3	1.964 (2)	C5—C6	1.377 (4)
Cu1—N1	1.978 (2)	C5—H5	0.9300
Cu1—N2	2.007 (2)	C6—C7	1.379 (4)
Cu1—O1i	2.3799 (19)	C6—H6	0.9300
N1—C2	1.287 (4)	C7—C8	1.369 (4)
N1—C9	1.463 (3)	C7—H7	0.9300
N2—C14	1.340 (4)	C8—H8	0.9300
N2—C10	1.347 (3)	C9—C10	1.503 (4)
N3—N4	1.204 (3)	C9—H9A	0.9700
N4—N5	1.156 (3)	C9—H9B	0.9700
O1—C4	1.328 (3)	C10—C11	1.377 (4)
O1—Cu1i	2.3799 (19)	C11—C12	1.373 (4)
C1—C2	1.521 (4)	C11—H11	0.9300
C1—H1A	0.9600	C12—C13	1.375 (4)
C1—H1B	0.9600	C12—H12	0.9300
C1—H1C	0.9600	C13—C14	1.378 (4)
C2—C3	1.471 (4)	C13—H13	0.9300
C3—C8	1.404 (4)	C14—H14	0.9300
C3—C4	1.424 (4)
O1—Cu1—N3	95.73 (9)	C5—C4—C3	117.1 (3)
O1—Cu1—N1	90.30 (9)	C6—C5—C4	122.5 (3)
N3—Cu1—N1	167.49 (11)	C6—C5—H5	118.7
O1—Cu1—N2	171.51 (8)	C4—C5—H5	118.7
N3—Cu1—N2	92.50 (10)	C5—C6—C7	120.0 (3)
N1—Cu1—N2	82.03 (10)	C5—C6—H6	120.0
O1—Cu1—O1i	85.08 (7)	C7—C6—H6	120.0
N3—Cu1—O1i	99.74 (9)	C8—C7—C6	119.1 (3)
N1—Cu1—O1i	91.66 (8)	C8—C7—H7	120.4
N2—Cu1—O1i	91.47 (8)	C6—C7—H7	120.4
C2—N1—C9	121.1 (2)	C7—C8—C3	122.4 (3)
C2—N1—Cu1	127.0 (2)	C7—C8—H8	118.8
C9—N1—Cu1	111.55 (18)	C3—C8—H8	118.8
C14—N2—C10	118.1 (3)	N1—C9—C10	109.6 (2)
C14—N2—Cu1	127.9 (2)	N1—C9—H9A	109.8
C10—N2—Cu1	114.1 (2)	C10—C9—H9A	109.8
N4—N3—Cu1	124.5 (2)	N1—C9—H9B	109.8
N5—N4—N3	176.9 (3)	C10—C9—H9B	109.8
C4—O1—Cu1	120.63 (17)	H9A—C9—H9B	108.2
C4—O1—Cu1i	121.52 (17)	N2—C10—C11	122.2 (3)
Cu1—O1—Cu1i	94.91 (7)	N2—C10—C9	115.8 (3)
C2—C1—H1A	109.5	C11—C10—C9	122.0 (3)
C2—C1—H1B	109.5	C12—C11—C10	119.1 (3)
H1A—C1—H1B	109.5	C12—C11—H11	120.5
C2—C1—H1C	109.5	C10—C11—H11	120.5
H1A—C1—H1C	109.5	C11—C12—C13	119.4 (3)
H1B—C1—H1C	109.5	C11—C12—H12	120.3
N1—C2—C3	120.2 (3)	C13—C12—H12	120.3
N1—C2—C1	122.2 (3)	C12—C13—C14	118.7 (3)
C3—C2—C1	117.6 (3)	C12—C13—H13	120.7
C8—C3—C4	118.5 (3)	C14—C13—H13	120.7
C8—C3—C2	119.7 (3)	N2—C14—C13	122.6 (3)
C4—C3—C2	121.9 (3)	N2—C14—H14	118.7
O1—C4—C5	119.1 (3)	C13—C14—H14	118.7
O1—C4—C3	123.8 (3)
O1—Cu1—N1—C2	20.2 (3)	C1—C2—C3—C4	149.0 (3)
N3—Cu1—N1—C2	−98.8 (6)	Cu1—O1—C4—C5	−146.9 (2)
N2—Cu1—N1—C2	−163.5 (3)	Cu1i—O1—C4—C5	94.4 (3)
O1i—Cu1—N1—C2	105.2 (3)	Cu1—O1—C4—C3	32.9 (4)
O1—Cu1—N1—C9	−153.2 (2)	Cu1i—O1—C4—C3	−85.7 (3)
N3—Cu1—N1—C9	87.8 (5)	C8—C3—C4—O1	−173.3 (3)
N2—Cu1—N1—C9	23.2 (2)	C2—C3—C4—O1	6.6 (5)
O1i—Cu1—N1—C9	−68.1 (2)	C8—C3—C4—C5	6.5 (4)
N3—Cu1—N2—C14	−2.0 (3)	C2—C3—C4—C5	−173.6 (3)
N1—Cu1—N2—C14	166.7 (3)	O1—C4—C5—C6	173.6 (3)
O1i—Cu1—N2—C14	−101.8 (2)	C3—C4—C5—C6	−6.2 (5)
N3—Cu1—N2—C10	177.8 (2)	C4—C5—C6—C7	1.1 (5)
N1—Cu1—N2—C10	−13.5 (2)	C5—C6—C7—C8	3.6 (5)
O1i—Cu1—N2—C10	78.0 (2)	C6—C7—C8—C3	−3.1 (5)
O1—Cu1—N3—N4	−9.5 (3)	C4—C3—C8—C7	−2.1 (5)
N1—Cu1—N3—N4	109.0 (5)	C2—C3—C8—C7	178.0 (3)
N2—Cu1—N3—N4	172.6 (3)	C2—N1—C9—C10	158.1 (3)
O1i—Cu1—N3—N4	−95.5 (3)	Cu1—N1—C9—C10	−28.1 (3)
N3—Cu1—O1—C4	129.3 (2)	C14—N2—C10—C11	0.3 (4)
N1—Cu1—O1—C4	−39.7 (2)	Cu1—N2—C10—C11	−179.6 (2)
O1i—Cu1—O1—C4	−131.4 (2)	C14—N2—C10—C9	−179.4 (3)
N3—Cu1—O1—Cu1i	−99.33 (9)	Cu1—N2—C10—C9	0.8 (3)
N1—Cu1—O1—Cu1i	91.64 (8)	N1—C9—C10—N2	17.9 (4)
O1i—Cu1—O1—Cu1i	0.0	N1—C9—C10—C11	−161.8 (3)
C9—N1—C2—C3	−178.8 (3)	N2—C10—C11—C12	−0.2 (5)
Cu1—N1—C2—C3	8.5 (4)	C9—C10—C11—C12	179.4 (3)
C9—N1—C2—C1	3.6 (5)	C10—C11—C12—C13	0.5 (5)
Cu1—N1—C2—C1	−169.1 (2)	C11—C12—C13—C14	−0.9 (5)
N1—C2—C3—C8	151.1 (3)	C10—N2—C14—C13	−0.7 (4)
C1—C2—C3—C8	−31.2 (4)	Cu1—N2—C14—C13	179.1 (2)
N1—C2—C3—C4	−28.7 (4)	C12—C13—C14—N2	1.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N5i	0.97	2.55	3.399 (5)	147
C14—H14···N3	0.93	2.55	3.052 (4)	114

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯N5i	0.97	2.55	3.399 (5)	147
C14—H14⋯N3	0.93	2.55	3.052 (4)	114

Symmetry code: (i) .