Bis{μ-2-meth-oxy-6-[(methyl-imino)-meth-yl]phenolato}bis-({2-meth-oxy-6-[(methyl-imino)-meth-yl]phenolato}copper(II)).

The title compound, [Cu2(C9H10NO2)4], is built of discrete centrosymmetric dimers. The Cu(II) atoms are each five coordinated by two deprotonated Schiff base ligands that are bonded differently to the metal atoms. Of the two phenolate O atoms, one is coordinated to one Cu(II) atom, whereas another bridges the two metal atoms. The basal plane of the square pyramid around Cu(II) atoms is formed by the imino N and phenolate O atoms of the bidentate and the monodentate/bidentate Schiff base ligands. The bridging phenolate oxygen occupies the apical position of the coordination sphere with a considerably longer Cu-O bond length. In the crystal, the dimeric mol-ecules pack relative to each other in such a way that the Cu2O2 planes of adjacent dimers are orthogonal.

Related literature

For direct synthesis using metal powders and Schiff base ligands, see: Chygorin et al. (2012a ▶,b ▶) and references therein. For the structure of the Schiff base ligand 2-meth­oxy-6-imino­methyl­phenol, see: Chatziefthimiou et al. (2006 ▶). For structures of metal complexes of this Schiff base ligand, see: Meally et al. (2010 ▶, 2012 ▶); Zhang & Feng (2010 ▶).

Experimental

Crystal data

[Cu2(C9H10NO2)4]

M = 783.8

Orthorhombic,

a = 10.1889 (12) Å

b = 15.2033 (5) Å

c = 21.6254 (9) Å

V = 3349.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.33 mm−1

T = 100 K

0.59 × 0.47 × 0.10 mm

Data collection

Oxford Diffraction Gemini diffractometer

Absorption correction: analytical [CrysAlis PRO (Agilent, 2011 ▶) based on Clark & Reid (1995 ▶)] T min = 0.597, T max = 0.88

110425 measured reflections

8673 independent reflections

7021 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.084

S = 1.05

8673 reflections

231 parameters

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813025105/hg5344sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813025105/hg5344Isup2.hkl

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

[Cu2(C9H10NO2)4]	F(000) = 1624
Mr = 783.8	Dx = 1.554 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2ab	Cell parameters from 25414 reflections
a = 10.1889 (12) Å	θ = 3.7–37.4°
b = 15.2033 (5) Å	µ = 1.33 mm−1
c = 21.6254 (9) Å	T = 100 K
V = 3349.9 (4) Å3	Plate, dark green
Z = 4	0.59 × 0.47 × 0.10 mm

Oxford Diffraction Gemini diffractometer	8673 independent reflections
Graphite monochromator	7021 reflections with I > 2σ(I)
Detector resolution: 10.4738 pixels mm-1	Rint = 0.045
ω scans	θmax = 37.5°, θmin = 3.7°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011) based on Clark & Reid (1995)]	h = −17→17
Tmin = 0.597, Tmax = 0.88	k = −25→25
110425 measured reflections	l = −36→36

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0415P)2 + 0.9858P] where P = (Fo2 + 2Fc2)/3
8673 reflections	(Δ/σ)max = 0.004
231 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.402856 (11)	0.587478 (7)	0.514407 (5)	0.01235 (3)
C11	0.32361 (9)	0.46134 (6)	0.42192 (4)	0.01446 (14)
O11	0.42030 (7)	0.50521 (5)	0.44728 (3)	0.01630 (12)
C12	0.33769 (10)	0.43410 (6)	0.35910 (4)	0.01654 (15)
O12	0.45029 (8)	0.46267 (6)	0.33152 (3)	0.02223 (15)
C121	0.47672 (13)	0.43092 (8)	0.27121 (5)	0.0262 (2)
H12A	0.4814	0.3665	0.272	0.039*
H12B	0.5606	0.4548	0.2567	0.039*
H12C	0.4064	0.4494	0.2431	0.039*
C13	0.24123 (11)	0.38471 (7)	0.33053 (5)	0.02007 (17)
H13	0.2522	0.3668	0.2888	0.024*
C14	0.12726 (12)	0.36098 (7)	0.36284 (5)	0.02237 (19)
H14	0.0614	0.3269	0.343	0.027*
C15	0.11093 (10)	0.38700 (7)	0.42308 (5)	0.01978 (17)
H15	0.0337	0.3705	0.4448	0.024*
C16	0.20753 (9)	0.43801 (6)	0.45312 (4)	0.01527 (15)
C17	0.18368 (9)	0.46319 (6)	0.51653 (4)	0.01637 (15)
H17	0.1114	0.4362	0.5367	0.02*
N17	0.25120 (8)	0.51886 (5)	0.54829 (4)	0.01518 (13)
C18	0.21142 (10)	0.53316 (7)	0.61269 (4)	0.01945 (17)
H18A	0.1379	0.4942	0.6228	0.029*
H18B	0.1843	0.5945	0.6181	0.029*
H18C	0.2855	0.5204	0.6402	0.029*
C21	0.44917 (9)	0.73470 (6)	0.59567 (4)	0.01441 (14)
O21	0.37172 (7)	0.67187 (5)	0.57781 (4)	0.01810 (13)
C22	0.41886 (9)	0.78000 (6)	0.65201 (4)	0.01576 (15)
O22	0.30820 (7)	0.75006 (5)	0.68125 (3)	0.01921 (13)
C221	0.25933 (13)	0.80269 (8)	0.73029 (5)	0.0256 (2)
H22A	0.3214	0.8015	0.7649	0.038*
H22B	0.1743	0.7796	0.744	0.038*
H22C	0.2485	0.8634	0.7159	0.038*
C23	0.49660 (11)	0.84784 (6)	0.67335 (5)	0.01998 (17)
H23	0.4745	0.8767	0.7109	0.024*
C24	0.60788 (11)	0.87448 (7)	0.64016 (5)	0.0236 (2)
H24	0.6615	0.9209	0.6552	0.028*
C25	0.63872 (11)	0.83310 (7)	0.58585 (5)	0.02131 (18)
H25	0.7141	0.8513	0.5634	0.026*
C26	0.56052 (9)	0.76367 (6)	0.56242 (4)	0.01585 (15)
C27	0.58954 (9)	0.73111 (7)	0.50142 (5)	0.01682 (16)
H27	0.6603	0.7582	0.4801	0.02*
N27	0.52864 (8)	0.66860 (5)	0.47287 (4)	0.01607 (14)
C28	0.56176 (12)	0.65605 (7)	0.40743 (5)	0.02199 (19)
H28A	0.6356	0.6943	0.3964	0.033*
H28B	0.4856	0.671	0.3818	0.033*
H28C	0.5862	0.5945	0.4003	0.033*

	U11	U22	U33	U12	U13	U23
Cu1	0.01144 (5)	0.01349 (5)	0.01214 (5)	−0.00031 (3)	0.00112 (3)	−0.00053 (3)
C11	0.0148 (3)	0.0148 (3)	0.0138 (3)	0.0015 (3)	−0.0024 (3)	−0.0005 (3)
O11	0.0141 (3)	0.0204 (3)	0.0145 (3)	−0.0013 (2)	−0.0003 (2)	−0.0039 (2)
C12	0.0177 (4)	0.0175 (4)	0.0145 (4)	0.0035 (3)	−0.0022 (3)	−0.0015 (3)
O12	0.0198 (3)	0.0319 (4)	0.0149 (3)	0.0009 (3)	0.0021 (3)	−0.0060 (3)
C121	0.0323 (6)	0.0315 (5)	0.0147 (4)	0.0057 (4)	0.0027 (4)	−0.0042 (4)
C13	0.0247 (4)	0.0186 (4)	0.0169 (4)	0.0022 (3)	−0.0059 (3)	−0.0037 (3)
C14	0.0264 (5)	0.0189 (4)	0.0218 (4)	−0.0045 (4)	−0.0071 (4)	−0.0014 (3)
C15	0.0209 (4)	0.0183 (4)	0.0201 (4)	−0.0050 (3)	−0.0040 (3)	0.0008 (3)
C16	0.0156 (4)	0.0148 (3)	0.0153 (4)	−0.0013 (3)	−0.0022 (3)	0.0011 (3)
C17	0.0159 (4)	0.0165 (4)	0.0167 (4)	−0.0024 (3)	−0.0003 (3)	0.0023 (3)
N17	0.0148 (3)	0.0170 (3)	0.0137 (3)	−0.0011 (3)	0.0009 (2)	0.0004 (3)
C18	0.0201 (4)	0.0232 (4)	0.0151 (4)	−0.0040 (3)	0.0041 (3)	−0.0008 (3)
C21	0.0138 (3)	0.0128 (3)	0.0166 (4)	0.0005 (3)	−0.0003 (3)	0.0008 (3)
O21	0.0164 (3)	0.0173 (3)	0.0206 (3)	−0.0037 (2)	0.0050 (2)	−0.0050 (2)
C22	0.0177 (4)	0.0136 (3)	0.0160 (4)	0.0016 (3)	−0.0013 (3)	0.0010 (3)
O22	0.0204 (3)	0.0189 (3)	0.0183 (3)	0.0008 (3)	0.0036 (2)	−0.0030 (2)
C221	0.0350 (6)	0.0231 (5)	0.0187 (4)	0.0054 (4)	0.0062 (4)	−0.0026 (4)
C23	0.0256 (5)	0.0150 (4)	0.0193 (4)	−0.0008 (3)	−0.0057 (3)	−0.0003 (3)
C24	0.0269 (5)	0.0191 (4)	0.0248 (5)	−0.0074 (4)	−0.0070 (4)	0.0022 (4)
C25	0.0197 (4)	0.0198 (4)	0.0244 (5)	−0.0064 (3)	−0.0025 (3)	0.0046 (3)
C26	0.0145 (3)	0.0147 (3)	0.0184 (4)	−0.0011 (3)	−0.0010 (3)	0.0028 (3)
C27	0.0145 (4)	0.0166 (4)	0.0194 (4)	0.0007 (3)	0.0023 (3)	0.0042 (3)
N27	0.0162 (3)	0.0158 (3)	0.0162 (3)	0.0018 (3)	0.0034 (3)	0.0028 (3)
C28	0.0268 (5)	0.0220 (4)	0.0172 (4)	0.0019 (4)	0.0078 (4)	0.0030 (3)

Cu1—O21	1.9044 (7)	C18—H18A	0.98
Cu1—O11	1.9243 (7)	C18—H18B	0.98
Cu1—N27	1.9925 (8)	C18—H18C	0.98
Cu1—N17	2.0032 (8)	C21—O21	1.2979 (11)
Cu1—O11i	2.4329 (8)	C21—C26	1.4135 (13)
C11—O11	1.3101 (11)	C21—C22	1.4333 (13)
C11—C16	1.4071 (13)	C22—O22	1.3705 (12)
C11—C12	1.4274 (13)	C22—C23	1.3799 (14)
O11—Cu1i	2.4329 (8)	O22—C221	1.4187 (13)
C12—O12	1.3640 (13)	C221—H22A	0.98
C12—C13	1.3825 (14)	C221—H22B	0.98
O12—C121	1.4165 (13)	C221—H22C	0.98
C121—H12A	0.98	C23—C24	1.4017 (16)
C121—H12B	0.98	C23—H23	0.95
C121—H12C	0.98	C24—C25	1.3689 (17)
C13—C14	1.4026 (16)	C24—H24	0.95
C13—H13	0.95	C25—C26	1.4163 (14)
C14—C15	1.3716 (15)	C25—H25	0.95
C14—H14	0.95	C26—C27	1.4396 (14)
C15—C16	1.4115 (14)	C27—N27	1.2922 (14)
C15—H15	0.95	C27—H27	0.95
C16—C17	1.4444 (14)	N27—C28	1.4673 (13)
C17—N17	1.2890 (12)	C28—H28A	0.98
C17—H17	0.95	C28—H28B	0.98
N17—C18	1.4667 (13)	C28—H28C	0.98
O21—Cu1—O11	175.12 (3)	N17—C18—H18A	109.5
O21—Cu1—N27	90.84 (3)	N17—C18—H18B	109.5
O11—Cu1—N27	90.16 (3)	H18A—C18—H18B	109.5
O21—Cu1—N17	87.65 (3)	N17—C18—H18C	109.5
O11—Cu1—N17	90.50 (3)	H18A—C18—H18C	109.5
N27—Cu1—N17	169.53 (3)	H18B—C18—H18C	109.5
O21—Cu1—O11i	105.57 (3)	O21—C21—C26	124.47 (9)
O11—Cu1—O11i	79.17 (3)	O21—C21—C22	118.40 (8)
N27—Cu1—O11i	92.04 (3)	C26—C21—C22	117.11 (8)
N17—Cu1—O11i	98.34 (3)	C21—O21—Cu1	127.51 (6)
O11—C11—C16	124.03 (8)	O22—C22—C23	124.49 (9)
O11—C11—C12	118.08 (9)	O22—C22—C21	114.20 (8)
C16—C11—C12	117.89 (8)	C23—C22—C21	121.32 (9)
C11—O11—Cu1	125.26 (6)	C22—O22—C221	116.50 (8)
C11—O11—Cu1i	113.86 (6)	O22—C221—H22A	109.5
Cu1—O11—Cu1i	100.84 (3)	O22—C221—H22B	109.5
O12—C12—C13	125.13 (9)	H22A—C221—H22B	109.5
O12—C12—C11	114.10 (8)	O22—C221—H22C	109.5
C13—C12—C11	120.76 (9)	H22A—C221—H22C	109.5
C12—O12—C121	117.00 (9)	H22B—C221—H22C	109.5
O12—C121—H12A	109.5	C22—C23—C24	120.60 (10)
O12—C121—H12B	109.5	C22—C23—H23	119.7
H12A—C121—H12B	109.5	C24—C23—H23	119.7
O12—C121—H12C	109.5	C25—C24—C23	119.49 (10)
H12A—C121—H12C	109.5	C25—C24—H24	120.3
H12B—C121—H12C	109.5	C23—C24—H24	120.3
C12—C13—C14	120.37 (9)	C24—C25—C26	121.35 (10)
C12—C13—H13	119.8	C24—C25—H25	119.3
C14—C13—H13	119.8	C26—C25—H25	119.3
C15—C14—C13	119.97 (10)	C21—C26—C25	120.12 (9)
C15—C14—H14	120	C21—C26—C27	121.59 (9)
C13—C14—H14	120	C25—C26—C27	117.94 (9)
C14—C15—C16	120.73 (10)	N27—C27—C26	126.30 (9)
C14—C15—H15	119.6	N27—C27—H27	116.8
C16—C15—H15	119.6	C26—C27—H27	116.8
C11—C16—C15	120.26 (9)	C27—N27—C28	116.49 (9)
C11—C16—C17	122.00 (8)	C27—N27—Cu1	123.28 (7)
C15—C16—C17	117.72 (9)	C28—N27—Cu1	120.15 (7)
N17—C17—C16	126.16 (9)	N27—C28—H28A	109.5
N17—C17—H17	116.9	N27—C28—H28B	109.5
C16—C17—H17	116.9	H28A—C28—H28B	109.5
C17—N17—C18	117.11 (8)	N27—C28—H28C	109.5
C17—N17—Cu1	123.97 (7)	H28A—C28—H28C	109.5
C18—N17—Cu1	118.90 (6)	H28B—C28—H28C	109.5

Table 1

Selected bond lengths (Å)

Cu1—O21	1.9044 (7)
Cu1—O11	1.9243 (7)
Cu1—N27	1.9925 (8)
Cu1—N17	2.0032 (8)
Cu1—O11i	2.4329 (8)

Symmetry code: (i) .