{5,5'-Bis(methoxy-carbonyl-meth-oxy)-2,2'-[ethane-1,2-diylbis(nitrilo-methyl-idyne)]-diphenolato}copper(II).

The title compound, [Cu(C(22)H(22)N(2)O(8))], is a tetra-dentate Schiff base complex. The Cu(II) ion has a nearly square-planar geometry, being coordinated by two N atoms and two O atoms. The two chemically equivalent halves of the mol-ecule are crystallographically independent. One of the carboxylic acid methyl ester units is located in the main plane of the mol-ecule and the other is rotated by 65.3 (5)° with respect to this unit. In the crystal structure, there are π-π stacking inter-actions between adjacent six-membered chelate rings, with centroid-to-centroid distances of 3.602 (2) Å.

Related literature

For general background, see: Paschke et al. (2002 ▶); Blake et al. (1995 ▶). For related structures, see: Bbadbhade & Srinivas (1993 ▶). Shamim et al. (1988 ▶) report the synthesis of the precursor of the organic ligand.

Experimental

Crystal data

[Cu(C22H22N2O8)]

M = 505.96

Triclinic,

a = 9.668 (1) Å

b = 10.012 (1) Å

c = 11.763 (2) Å

α = 85.251 (2)°

β = 80.381 (2)°

γ = 75.383 (2)°

V = 1085.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.06 mm−1

T = 293 (2) K

0.40 × 0.30 × 0.25 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.677, T max = 0.778

6326 measured reflections

4482 independent reflections

3096 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.124

S = 1.03

4482 reflections

298 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033084/zl2141sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033084/zl2141Isup2.hkl

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

[Cu(C22H22N2O8)]	Z = 2
Mr = 505.96	F(000) = 522
Triclinic, P1	Dx = 1.548 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.668 (1) Å	Cell parameters from 4482 reflections
b = 10.012 (1) Å	θ = 1.8–26.7°
c = 11.763 (2) Å	µ = 1.06 mm−1
α = 85.251 (2)°	T = 293 K
β = 80.381 (2)°	Block, brown
γ = 75.383 (2)°	0.40 × 0.30 × 0.25 mm
V = 1085.3 (2) Å3

Bruker APEX CCD area-detector diffractometer	4482 independent reflections
Radiation source: fine-focus sealed tube	3096 reflections with I > 2σ(I)
graphite	Rint = 0.018
ω scans	θmax = 26.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→12
Tmin = 0.677, Tmax = 0.778	k = −9→12
6326 measured reflections	l = −13→14

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0435P)2 + 0.7616P] where P = (Fo2 + 2Fc2)/3
4482 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.32 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	−0.02639 (5)	0.15738 (5)	0.40718 (4)	0.04568 (17)
C1	0.8714 (5)	0.5674 (5)	0.3845 (4)	0.0811 (15)
H1A	0.8657	0.6225	0.4488	0.122*
H1B	0.8845	0.6213	0.3139	0.122*
H1C	0.9518	0.4882	0.3850	0.122*
C2	0.7312 (5)	0.4448 (4)	0.3101 (4)	0.0581 (11)
C3	0.5930 (4)	0.3988 (4)	0.3310 (3)	0.0519 (10)
H3A	0.5849	0.3465	0.4039	0.062*
H3B	0.5108	0.4782	0.3334	0.062*
C4	0.4834 (4)	0.2571 (4)	0.2380 (3)	0.0528 (10)
C5	0.4966 (4)	0.1810 (5)	0.1410 (3)	0.0578 (11)
H5	0.5777	0.1718	0.0845	0.069*
C6	0.3889 (4)	0.1208 (4)	0.1310 (3)	0.0558 (10)
H6	0.3973	0.0705	0.0661	0.067*
C7	0.2642 (4)	0.1313 (4)	0.2149 (3)	0.0466 (9)
C8	0.2522 (4)	0.2083 (4)	0.3138 (3)	0.0447 (9)
C9	0.3649 (4)	0.2707 (4)	0.3234 (3)	0.0499 (9)
H9	0.3593	0.3212	0.3877	0.060*
C10	0.1556 (4)	0.0667 (4)	0.1949 (3)	0.0546 (10)
H10	0.1739	0.0167	0.1286	0.066*
C11	−0.0766 (5)	0.0142 (6)	0.2262 (4)	0.0791 (15)
H11A	−0.1344	0.0822	0.1785	0.095*
H11B	−0.0307	−0.0662	0.1809	0.095*
C12	−0.1694 (5)	−0.0249 (5)	0.3272 (4)	0.0785 (15)
H12A	−0.1265	−0.1178	0.3546	0.094*
H12B	−0.2629	−0.0241	0.3069	0.094*
C13	−0.2968 (4)	0.0871 (4)	0.4993 (4)	0.0567 (11)
H13	−0.3664	0.0395	0.4938	0.068*
C14	−0.3203 (4)	0.1694 (4)	0.5965 (3)	0.0484 (9)
C15	−0.2202 (4)	0.2436 (4)	0.6176 (3)	0.0461 (9)
C16	−0.2502 (4)	0.3153 (4)	0.7201 (3)	0.0501 (10)
H16	−0.1866	0.3655	0.7347	0.060*
C17	−0.4452 (4)	0.1743 (5)	0.6791 (4)	0.0609 (11)
H17	−0.5127	0.1285	0.6649	0.073*
C18	−0.4712 (4)	0.2421 (5)	0.7772 (4)	0.0628 (12)
H18	−0.5545	0.2420	0.8297	0.075*
C19	−0.3721 (4)	0.3127 (4)	0.7997 (3)	0.0548 (10)
C20	−0.3016 (4)	0.4378 (5)	0.9347 (4)	0.0638 (12)
H20A	−0.3435	0.4885	1.0040	0.077*
H20B	−0.2760	0.5030	0.8741	0.077*
C21	−0.1672 (5)	0.3315 (5)	0.9570 (3)	0.0571 (11)
C22	0.0779 (5)	0.3088 (6)	0.9761 (5)	0.1005 (19)
H22A	0.1489	0.3625	0.9632	0.151*
H22B	0.1110	0.2290	0.9299	0.151*
H22C	0.0634	0.2799	1.0562	0.151*
N1	−0.1881 (3)	0.0725 (3)	0.4185 (3)	0.0542 (8)
N2	0.0342 (3)	0.0715 (3)	0.2610 (3)	0.0540 (8)
O1	−0.1002 (3)	0.2473 (3)	0.5482 (2)	0.0537 (7)
O2	0.1423 (3)	0.2237 (3)	0.3977 (2)	0.0534 (7)
O3	−0.4053 (3)	0.3772 (3)	0.9017 (2)	0.0682 (8)
O4	0.5962 (3)	0.3158 (3)	0.2393 (2)	0.0674 (8)
O5	−0.1593 (3)	0.2113 (3)	0.9815 (3)	0.0723 (9)
O6	−0.0568 (3)	0.3915 (3)	0.9447 (3)	0.0736 (9)
O7	0.7385 (3)	0.5219 (3)	0.3929 (2)	0.0650 (8)
O8	0.8223 (4)	0.4170 (5)	0.2289 (4)	0.1257 (18)

	U11	U22	U33	U12	U13	U23
Cu1	0.0420 (3)	0.0513 (3)	0.0476 (3)	−0.0201 (2)	−0.0019 (2)	−0.0069 (2)
C1	0.071 (3)	0.092 (4)	0.095 (4)	−0.043 (3)	−0.011 (3)	−0.020 (3)
C2	0.058 (3)	0.058 (3)	0.062 (3)	−0.023 (2)	0.001 (2)	−0.009 (2)
C3	0.051 (2)	0.059 (3)	0.049 (2)	−0.0212 (19)	−0.0031 (18)	−0.003 (2)
C4	0.052 (2)	0.061 (3)	0.048 (2)	−0.024 (2)	−0.0011 (19)	−0.001 (2)
C5	0.050 (2)	0.075 (3)	0.048 (2)	−0.023 (2)	0.0092 (19)	−0.008 (2)
C6	0.056 (2)	0.066 (3)	0.044 (2)	−0.018 (2)	0.0061 (19)	−0.016 (2)
C7	0.049 (2)	0.044 (2)	0.046 (2)	−0.0125 (17)	−0.0030 (18)	−0.0057 (18)
C8	0.042 (2)	0.048 (2)	0.045 (2)	−0.0152 (17)	0.0003 (17)	−0.0038 (17)
C9	0.051 (2)	0.057 (2)	0.047 (2)	−0.0233 (19)	0.0004 (18)	−0.0109 (19)
C10	0.059 (2)	0.060 (3)	0.049 (2)	−0.022 (2)	−0.001 (2)	−0.016 (2)
C11	0.073 (3)	0.113 (4)	0.069 (3)	−0.053 (3)	0.000 (2)	−0.033 (3)
C12	0.073 (3)	0.093 (4)	0.086 (3)	−0.050 (3)	−0.005 (3)	−0.025 (3)
C13	0.046 (2)	0.065 (3)	0.066 (3)	−0.029 (2)	−0.007 (2)	0.002 (2)
C14	0.039 (2)	0.055 (2)	0.053 (2)	−0.0189 (18)	−0.0059 (18)	0.0068 (19)
C15	0.0350 (19)	0.055 (2)	0.047 (2)	−0.0136 (17)	−0.0037 (17)	0.0067 (19)
C16	0.040 (2)	0.062 (3)	0.049 (2)	−0.0179 (18)	−0.0001 (17)	−0.0035 (19)
C17	0.044 (2)	0.073 (3)	0.071 (3)	−0.029 (2)	−0.004 (2)	0.002 (2)
C18	0.041 (2)	0.077 (3)	0.066 (3)	−0.018 (2)	0.011 (2)	0.003 (2)
C19	0.041 (2)	0.064 (3)	0.052 (2)	−0.0060 (19)	0.0019 (19)	0.000 (2)
C20	0.053 (2)	0.072 (3)	0.061 (3)	−0.011 (2)	0.009 (2)	−0.018 (2)
C21	0.065 (3)	0.065 (3)	0.038 (2)	−0.014 (2)	0.0038 (19)	−0.010 (2)
C22	0.075 (4)	0.095 (4)	0.136 (5)	−0.007 (3)	−0.044 (3)	−0.012 (4)
N1	0.0485 (19)	0.060 (2)	0.061 (2)	−0.0244 (16)	−0.0032 (17)	−0.0137 (17)
N2	0.054 (2)	0.063 (2)	0.053 (2)	−0.0263 (17)	−0.0062 (16)	−0.0137 (17)
O1	0.0457 (14)	0.0697 (19)	0.0502 (15)	−0.0286 (13)	0.0075 (12)	−0.0129 (14)
O2	0.0483 (15)	0.0673 (18)	0.0489 (15)	−0.0277 (13)	0.0086 (12)	−0.0172 (13)
O3	0.0498 (17)	0.088 (2)	0.0567 (18)	−0.0110 (16)	0.0147 (14)	−0.0127 (16)
O4	0.0584 (17)	0.093 (2)	0.0611 (18)	−0.0453 (17)	0.0108 (14)	−0.0208 (16)
O5	0.087 (2)	0.063 (2)	0.065 (2)	−0.0197 (17)	−0.0041 (16)	−0.0023 (16)
O6	0.066 (2)	0.070 (2)	0.086 (2)	−0.0150 (17)	−0.0160 (17)	−0.0054 (18)
O7	0.0600 (18)	0.078 (2)	0.0647 (19)	−0.0299 (16)	−0.0067 (15)	−0.0144 (16)
O8	0.093 (3)	0.181 (4)	0.126 (3)	−0.091 (3)	0.052 (3)	−0.097 (3)

Cu1—O2	1.894 (2)	C11—H11A	0.9700
Cu1—O1	1.897 (3)	C11—H11B	0.9700
Cu1—N2	1.922 (3)	C12—N1	1.469 (5)
Cu1—N1	1.941 (3)	C12—H12A	0.9700
C1—O7	1.454 (5)	C12—H12B	0.9700
C1—H1A	0.9600	C13—N1	1.281 (5)
C1—H1B	0.9600	C13—C14	1.419 (6)
C1—H1C	0.9600	C13—H13	0.9300
C2—O8	1.186 (5)	C14—C17	1.411 (5)
C2—O7	1.313 (5)	C14—C15	1.422 (5)
C2—C3	1.497 (5)	C15—O1	1.309 (4)
C3—O4	1.407 (4)	C15—C16	1.405 (5)
C3—H3A	0.9700	C16—C19	1.381 (5)
C3—H3B	0.9700	C16—H16	0.9300
C4—O4	1.366 (4)	C17—C18	1.342 (6)
C4—C9	1.379 (5)	C17—H17	0.9300
C4—C5	1.394 (5)	C18—C19	1.395 (6)
C5—C6	1.353 (5)	C18—H18	0.9300
C5—H5	0.9300	C19—O3	1.362 (5)
C6—C7	1.412 (5)	C20—O3	1.415 (5)
C6—H6	0.9300	C20—C21	1.504 (6)
C7—C8	1.421 (5)	C20—H20A	0.9700
C7—C10	1.423 (5)	C20—H20B	0.9700
C8—O2	1.310 (4)	C21—O5	1.200 (5)
C8—C9	1.410 (5)	C21—O6	1.333 (5)
C9—H9	0.9300	C22—O6	1.444 (5)
C10—N2	1.287 (5)	C22—H22A	0.9600
C10—H10	0.9300	C22—H22B	0.9600
C11—C12	1.453 (6)	C22—H22C	0.9600
C11—N2	1.463 (5)
O2—Cu1—O1	89.23 (10)	C11—C12—H12B	109.7
O2—Cu1—N2	93.86 (12)	N1—C12—H12B	109.7
O1—Cu1—N2	175.69 (13)	H12A—C12—H12B	108.2
O2—Cu1—N1	174.74 (13)	N1—C13—C14	125.7 (4)
O1—Cu1—N1	92.91 (12)	N1—C13—H13	117.2
N2—Cu1—N1	84.26 (13)	C14—C13—H13	117.2
O7—C1—H1A	109.5	C17—C14—C13	119.1 (4)
O7—C1—H1B	109.5	C17—C14—C15	117.9 (4)
H1A—C1—H1B	109.5	C13—C14—C15	123.0 (3)
O7—C1—H1C	109.5	O1—C15—C16	117.8 (3)
H1A—C1—H1C	109.5	O1—C15—C14	124.0 (4)
H1B—C1—H1C	109.5	C16—C15—C14	118.2 (3)
O8—C2—O7	123.9 (4)	C19—C16—C15	121.4 (4)
O8—C2—C3	124.7 (4)	C19—C16—H16	119.3
O7—C2—C3	111.4 (4)	C15—C16—H16	119.3
O4—C3—C2	107.1 (3)	C18—C17—C14	123.0 (4)
O4—C3—H3A	110.3	C18—C17—H17	118.5
C2—C3—H3A	110.3	C14—C17—H17	118.5
O4—C3—H3B	110.3	C17—C18—C19	119.4 (4)
C2—C3—H3B	110.3	C17—C18—H18	120.3
H3A—C3—H3B	108.5	C19—C18—H18	120.3
O4—C4—C9	124.2 (4)	O3—C19—C16	124.2 (4)
O4—C4—C5	114.2 (3)	O3—C19—C18	115.8 (3)
C9—C4—C5	121.7 (4)	C16—C19—C18	120.0 (4)
C6—C5—C4	118.6 (4)	O3—C20—C21	112.0 (4)
C6—C5—H5	120.7	O3—C20—H20A	109.2
C4—C5—H5	120.7	C21—C20—H20A	109.2
C5—C6—C7	122.7 (4)	O3—C20—H20B	109.2
C5—C6—H6	118.6	C21—C20—H20B	109.2
C7—C6—H6	118.6	H20A—C20—H20B	107.9
C6—C7—C8	118.3 (3)	O5—C21—O6	125.0 (4)
C6—C7—C10	118.4 (4)	O5—C21—C20	125.8 (4)
C8—C7—C10	123.3 (3)	O6—C21—C20	109.2 (4)
O2—C8—C9	117.8 (3)	O6—C22—H22A	109.5
O2—C8—C7	123.6 (3)	O6—C22—H22B	109.5
C9—C8—C7	118.5 (3)	H22A—C22—H22B	109.5
C4—C9—C8	120.2 (4)	O6—C22—H22C	109.5
C4—C9—H9	119.9	H22A—C22—H22C	109.5
C8—C9—H9	119.9	H22B—C22—H22C	109.5
N2—C10—C7	125.5 (4)	C13—N1—C12	120.7 (3)
N2—C10—H10	117.2	C13—N1—Cu1	126.4 (3)
C7—C10—H10	117.2	C12—N1—Cu1	112.7 (2)
C12—C11—N2	110.4 (4)	C10—N2—C11	121.1 (3)
C12—C11—H11A	109.6	C10—N2—Cu1	125.9 (3)
N2—C11—H11A	109.6	C11—N2—Cu1	112.9 (3)
C12—C11—H11B	109.6	C15—O1—Cu1	128.0 (2)
N2—C11—H11B	109.6	C8—O2—Cu1	127.6 (2)
H11A—C11—H11B	108.1	C19—O3—C20	118.2 (3)
C11—C12—N1	109.6 (4)	C4—O4—C3	119.5 (3)
C11—C12—H12A	109.7	C21—O6—C22	117.1 (4)
N1—C12—H12A	109.7	C2—O7—C1	116.2 (3)
O8—C2—C3—O4	1.7 (7)	C14—C13—N1—C12	174.8 (4)
O7—C2—C3—O4	−179.1 (3)	C14—C13—N1—Cu1	0.4 (6)
O4—C4—C5—C6	−178.9 (4)	C11—C12—N1—C13	158.0 (4)
C9—C4—C5—C6	0.7 (7)	C11—C12—N1—Cu1	−26.8 (5)
C4—C5—C6—C7	−0.4 (7)	O1—Cu1—N1—C13	0.8 (4)
C5—C6—C7—C8	−0.1 (6)	N2—Cu1—N1—C13	−175.9 (4)
C5—C6—C7—C10	178.6 (4)	O1—Cu1—N1—C12	−174.0 (3)
C6—C7—C8—O2	−179.2 (4)	N2—Cu1—N1—C12	9.3 (3)
C10—C7—C8—O2	2.2 (6)	C7—C10—N2—C11	173.2 (4)
C6—C7—C8—C9	0.1 (6)	C7—C10—N2—Cu1	−4.0 (6)
C10—C7—C8—C9	−178.5 (4)	C12—C11—N2—C10	154.5 (4)
O4—C4—C9—C8	178.9 (4)	C12—C11—N2—Cu1	−28.0 (5)
C5—C4—C9—C8	−0.7 (6)	O2—Cu1—N2—C10	2.8 (4)
O2—C8—C9—C4	179.6 (4)	N1—Cu1—N2—C10	−172.3 (4)
C7—C8—C9—C4	0.3 (6)	O2—Cu1—N2—C11	−174.6 (3)
C6—C7—C10—N2	−177.2 (4)	N1—Cu1—N2—C11	10.3 (3)
C8—C7—C10—N2	1.4 (7)	C16—C15—O1—Cu1	177.8 (3)
N2—C11—C12—N1	34.7 (6)	C14—C15—O1—Cu1	−0.9 (5)
N1—C13—C14—C17	−179.5 (4)	O2—Cu1—O1—C15	−175.7 (3)
N1—C13—C14—C15	−2.2 (7)	N1—Cu1—O1—C15	−0.6 (3)
C17—C14—C15—O1	179.8 (3)	C9—C8—O2—Cu1	178.0 (3)
C13—C14—C15—O1	2.5 (6)	C7—C8—O2—Cu1	−2.7 (5)
C17—C14—C15—C16	1.1 (5)	O1—Cu1—O2—C8	−176.5 (3)
C13—C14—C15—C16	−176.2 (4)	N2—Cu1—O2—C8	0.4 (3)
O1—C15—C16—C19	−177.8 (3)	C16—C19—O3—C20	−7.3 (6)
C14—C15—C16—C19	1.0 (6)	C18—C19—O3—C20	173.4 (4)
C13—C14—C17—C18	175.5 (4)	C21—C20—O3—C19	−65.3 (5)
C15—C14—C17—C18	−1.9 (6)	C9—C4—O4—C3	−1.7 (6)
C14—C17—C18—C19	0.6 (7)	C5—C4—O4—C3	177.9 (4)
C15—C16—C19—O3	178.4 (4)	C2—C3—O4—C4	178.6 (3)
C15—C16—C19—C18	−2.4 (6)	O5—C21—O6—C22	−7.4 (6)
C17—C18—C19—O3	−179.1 (4)	C20—C21—O6—C22	172.9 (4)
C17—C18—C19—C16	1.5 (6)	O8—C2—O7—C1	−3.5 (7)
O3—C20—C21—O5	−22.9 (6)	C3—C2—O7—C1	177.3 (4)
O3—C20—C21—O6	156.8 (3)