Bis(2-hy-droxy-imino-methyl-6-meth-oxy-phenolato-κ(2)N,O(1))copper(II).

In the title compound, [Cu(C(8)H(8)NO(3))(2)], the nearly planar mol-ecule (r.m.s. deviation = 0.037 Å) is centrosymmetric with the Cu(II) atom lying on an inversion center. The Cu(II) atom is tetra-coordinated, displaying a slightly distorted square-planar geometry. The main deviation from the ideal geometry is seen in the differences in the Cu-O [1.8833 (10) Å] and Cu-N [1.9405 (13) Å] bond lengths, while angular deviations are less than 3°. Intra-molecular O-H⋯O and inter-molecular Csp(2)-H⋯O hydrogen bonds form S(5) and R(2) (2)(8) ring motifs, respectively. The latter inter-action results in chains of mol-ecules along [100].

Related literature

For related structures, see: Zhang et al. (2008 ▶); Li et al. (2004 ▶), 2009 ▶). For bond-valence-sum calculations, see: Brown & Altermatt (1985 ▶). For in situ formation of polydentate ligands, see: Coxall et al. (2000 ▶). For background to direct synthesis, see: Makhankova (2011 ▶).

Experimental

Crystal data

[Cu(C8H8NO3)2]

M = 395.85

Monoclinic,

a = 8.4906 (4) Å

b = 4.8997 (2) Å

c = 18.9309 (9) Å

β = 94.906 (4)°

V = 784.67 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.43 mm−1

T = 293 K

0.50 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur/Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.535, T max = 0.763

8497 measured reflections

2245 independent reflections

1816 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.077

S = 1.01

2245 reflections

132 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812032187/lr2071sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032187/lr2071Isup2.hkl

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

[Cu(C8H8NO3)2]	F(000) = 406
Mr = 395.85	Dx = 1.675 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2721 reflections
a = 8.4906 (4) Å	θ = 3.1–32.2°
b = 4.8997 (2) Å	µ = 1.43 mm−1
c = 18.9309 (9) Å	T = 293 K
β = 94.906 (4)°	Needle, gold–green
V = 784.67 (6) Å3	0.50 × 0.20 × 0.10 mm
Z = 2

Oxford Diffraction Xcalibur/Sapphire3 diffractometer	2245 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1816 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 16.1827 pixels mm-1	θmax = 30.0°, θmin = 3.9°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −6→6
Tmin = 0.535, Tmax = 0.763	l = −26→26
8497 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)] = 0.028	Hydrogen site location: difference Fourier map
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0486P)2] where P = (Fo2 + 2Fc2)/3
2245 reflections	(Δ/σ)max = 0.001
132 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.19 e Å−3
11 constraints

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2010. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.5000	0.5000	0.03633 (10)
N1	0.27576 (15)	0.5566 (3)	0.50728 (7)	0.0398 (3)
C1	0.60680 (18)	0.0698 (3)	0.59715 (8)	0.0378 (3)
O1	0.49066 (12)	0.2223 (2)	0.56829 (5)	0.0446 (2)
O2	0.41409 (14)	−0.1275 (2)	0.66227 (6)	0.0541 (3)
C2	0.56941 (19)	−0.1252 (3)	0.64921 (7)	0.0416 (3)
O3	0.20159 (13)	0.3924 (3)	0.55453 (6)	0.0518 (3)
H3O	0.2665	0.2879	0.5745	0.078*
C3	0.6860 (2)	−0.2899 (3)	0.68168 (8)	0.0488 (4)
H3	0.6603	−0.4164	0.7155	0.059*
C4	0.8415 (2)	−0.2687 (3)	0.66435 (8)	0.0512 (4)
H4	0.9189	−0.3814	0.6865	0.061*
C5	0.8809 (2)	−0.0838 (4)	0.61520 (9)	0.0467 (3)
H5	0.9853	−0.0700	0.6043	0.056*
C6	0.76430 (18)	0.0881 (3)	0.58031 (8)	0.0393 (3)
C7	0.81554 (18)	0.2753 (3)	0.52815 (8)	0.0420 (3)
H7	0.920 (2)	0.279 (4)	0.5214 (9)	0.054 (5)*
C8	0.3647 (3)	−0.3339 (4)	0.70831 (10)	0.0572 (4)
H8A	0.392 (3)	−0.514 (4)	0.6925 (12)	0.050 (6)*
H8B	0.418 (3)	−0.314 (4)	0.7595 (12)	0.072 (6)*
H8C	0.255 (3)	−0.322 (4)	0.7053 (10)	0.064 (6)*

	U11	U22	U33	U12	U13	U23
Cu1	0.03102 (14)	0.03680 (14)	0.04131 (15)	−0.00245 (9)	0.00388 (9)	0.00387 (9)
N1	0.0332 (6)	0.0452 (6)	0.0413 (6)	−0.0056 (5)	0.0060 (5)	0.0017 (5)
C1	0.0405 (7)	0.0349 (6)	0.0379 (7)	−0.0014 (6)	0.0017 (6)	−0.0020 (5)
O1	0.0358 (5)	0.0457 (5)	0.0525 (5)	0.0010 (4)	0.0052 (4)	0.0134 (5)
O2	0.0521 (7)	0.0494 (6)	0.0621 (7)	−0.0034 (5)	0.0118 (5)	0.0163 (6)
C2	0.0463 (8)	0.0360 (7)	0.0422 (7)	−0.0041 (6)	0.0021 (6)	−0.0008 (6)
O3	0.0370 (5)	0.0640 (7)	0.0550 (6)	−0.0058 (6)	0.0083 (5)	0.0176 (6)
C3	0.0611 (10)	0.0393 (7)	0.0451 (7)	−0.0020 (7)	−0.0013 (7)	0.0044 (6)
C4	0.0554 (9)	0.0464 (8)	0.0499 (8)	0.0099 (7)	−0.0072 (7)	−0.0004 (7)
C5	0.0402 (8)	0.0483 (7)	0.0505 (8)	0.0060 (7)	−0.0024 (7)	−0.0055 (7)
C6	0.0391 (7)	0.0369 (6)	0.0410 (7)	0.0000 (6)	−0.0009 (6)	−0.0049 (6)
C7	0.0320 (7)	0.0477 (8)	0.0463 (7)	−0.0020 (6)	0.0033 (6)	−0.0023 (6)
C8	0.0656 (12)	0.0517 (9)	0.0560 (10)	−0.0083 (9)	0.0151 (9)	0.0089 (8)

Cu1—O1i	1.8833 (10)	C3—C4	1.392 (3)
Cu1—O1	1.8833 (10)	C3—H3	0.9300
Cu1—N1	1.9405 (13)	C4—C5	1.361 (2)
Cu1—N1i	1.9405 (13)	C4—H4	0.9300
N1—C7i	1.281 (2)	C5—C6	1.419 (2)
N1—O3	1.3928 (17)	C5—H5	0.9300
C1—O1	1.3179 (17)	C6—C7	1.442 (2)
C1—C6	1.404 (2)	C7—N1i	1.281 (2)
C1—C2	1.428 (2)	C7—H7	0.903 (19)
O2—C2	1.362 (2)	C8—H8A	0.965 (18)
O2—C8	1.422 (2)	C8—H8B	1.04 (2)
C2—C3	1.380 (2)	C8—H8C	0.93 (2)
O3—H3O	0.8200
O1i—Cu1—O1	180.0	C4—C3—H3	119.7
O1i—Cu1—N1	92.56 (5)	C5—C4—C3	120.27 (15)
O1—Cu1—N1	87.44 (5)	C5—C4—H4	119.9
O1i—Cu1—N1i	87.44 (5)	C3—C4—H4	119.9
O1—Cu1—N1i	92.56 (5)	C4—C5—C6	120.76 (16)
N1—Cu1—N1i	180.00 (8)	C4—C5—H5	119.6
C7i—N1—O3	114.91 (13)	C6—C5—H5	119.6
C7i—N1—Cu1	127.46 (11)	C1—C6—C5	119.77 (15)
O3—N1—Cu1	117.60 (10)	C1—C6—C7	123.03 (14)
O1—C1—C6	124.28 (14)	C5—C6—C7	117.20 (15)
O1—C1—C2	117.57 (14)	N1i—C7—C6	124.28 (14)
C6—C1—C2	118.15 (14)	N1i—C7—H7	117.8 (12)
C1—O1—Cu1	128.33 (10)	C6—C7—H7	117.8 (12)
C2—O2—C8	117.25 (14)	O2—C8—H8A	111.8 (14)
O2—C2—C3	125.65 (14)	O2—C8—H8B	112.2 (12)
O2—C2—C1	113.99 (13)	H8A—C8—H8B	106.2 (18)
C3—C2—C1	120.35 (15)	O2—C8—H8C	105.2 (13)
N1—O3—H3O	109.5	H8A—C8—H8C	107.6 (19)
C2—C3—C4	120.69 (15)	H8B—C8—H8C	113.9 (17)
C2—C3—H3	119.7
O1i—Cu1—N1—C7i	2.42 (14)	C6—C1—C2—C3	0.0 (2)
O1—Cu1—N1—C7i	−177.58 (14)	O2—C2—C3—C4	−179.65 (14)
O1i—Cu1—N1—O3	−179.73 (11)	C1—C2—C3—C4	0.1 (2)
O1—Cu1—N1—O3	0.27 (11)	C2—C3—C4—C5	0.3 (2)
C6—C1—O1—Cu1	−0.8 (2)	C3—C4—C5—C6	−0.6 (2)
C2—C1—O1—Cu1	178.82 (10)	O1—C1—C6—C5	179.24 (14)
N1—Cu1—O1—C1	−177.96 (12)	C2—C1—C6—C5	−0.4 (2)
N1i—Cu1—O1—C1	2.04 (12)	O1—C1—C6—C7	−1.0 (2)
C8—O2—C2—C3	−6.2 (2)	C2—C1—C6—C7	179.38 (13)
C8—O2—C2—C1	174.03 (14)	C4—C5—C6—C1	0.7 (2)
O1—C1—C2—O2	0.10 (19)	C4—C5—C6—C7	−179.06 (14)
C6—C1—C2—O2	179.74 (13)	C1—C6—C7—N1i	0.6 (2)
O1—C1—C2—C3	−179.64 (13)	C5—C6—C7—N1i	−179.65 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.82	1.94	2.5840 (16)	134
C7—H7···O3ii	0.903 (19)	2.49 (2)	3.3231 (19)	154.3 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1	0.82	1.94	2.5840 (16)	134
C7—H7⋯O3i	0.903 (19)	2.49 (2)	3.3231 (19)	154.3 (15)

Symmetry code: (i) .