Bis(μ-2,2'-{[4-(carb-oxy-meth-oxy)phen-yl]aza-nedi-yl}diacetato)-bis-[(1,10-phenanthroline)copper(II)].

The crystal structure of the binuclear title compound, [Cu(2)(C(12)H(11)NO(7))(2)(C(12)H(8)N(2))(2)], consists of a complex mol-ecule, which lies about a crystallographic inversion centre with one half-mol-ecule in the asymmetric unit. The Cu(II) cation is bonded to three N atoms and three O atoms, in a Jahn-Teller-distorted octa-hedral geometry. The basal plane is defined by the two N atoms from the 1,10-phenathroline and two deprotonated O atoms of the polycarboxyl-ate ligand. The axial positions are occupied by the azane N atom and a bridging carboxyl-ate O atom from the second polycarboxyl-ate ligand. The complex mol-ecules are linked through O-H⋯O hydrogen bonds into extended chains running parallel to [010].

Related literature

For general background to the applications of polycarboxyl­ate ligands, see: Ghermani et al. (1994 ▶); Ruiz-Perez et al. (2000 ▶); Ye et al. (2005 ▶); Kido et al. (2003 ▶). For the features of flexible multidentate aromatic polycarboxyl­ate ligands, see: Wang et al. (2009 ▶); Pan et al. (2008 ▶); Dong et al. (2006 ▶).

Experimental

Crystal data

[Cu2(C12H11NO7)2(C12H8N2)2]

M = 1049.92

Monoclinic,

a = 8.7410 (17) Å

b = 10.886 (2) Å

c = 22.239 (4) Å

β = 90.85 (3)°

V = 2115.8 (7) Å3

Z = 2

Mo Kα radiation

μ = 1.09 mm−1

T = 293 K

0.26 × 0.18 × 0.12 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer

Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 1998 ▶) T min = 0.85, T max = 1.00

14139 measured reflections

3604 independent reflections

3408 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.103

S = 1.25

3604 reflections

317 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.35 e Å−3

Data collection: CrystalClear (Rigaku, 2002 ▶); 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/S1600536810048488/sj5063sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048488/sj5063Isup2.hkl

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

[Cu2(C12H11NO7)2(C12H8N2)2]	F(000) = 1076
Mr = 1049.92	Dx = 1.648 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.7410 (17) Å	θ = 12–18°
b = 10.886 (2) Å	µ = 1.09 mm−1
c = 22.239 (4) Å	T = 293 K
β = 90.85 (3)°	Block, blue
V = 2115.8 (7) Å3	0.26 × 0.18 × 0.12 mm
Z = 2

Rigaku Mercury CCD area-detector diffractometer	3604 independent reflections
Radiation source: fine-focus sealed tube	3408 reflections with I > 2σ(I)
graphite	Rint = 0.052
ω scans	θmax = 24.7°, θmin = 3.1°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 1998)	h = −10→10
Tmin = 0.85, Tmax = 1.00	k = −12→12
14139 measured reflections	l = −26→26

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.25	w = 1/[σ2(Fo2) + (0.0128P)2 + 3.5126P] where P = (Fo2 + 2Fc2)/3
3604 reflections	(Δ/σ)max = 0.001
317 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.35 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	0.05701 (5)	0.10839 (4)	0.04897 (2)	0.03031 (15)
O5	−0.0341 (3)	0.0219 (2)	0.11910 (12)	0.0356 (7)
O7	0.1363 (3)	−0.0478 (2)	0.01526 (12)	0.0326 (6)
N1	0.2819 (4)	0.0561 (3)	0.11173 (14)	0.0304 (7)
N2	0.0092 (4)	0.2758 (3)	0.08106 (15)	0.0319 (8)
N3	0.1739 (4)	0.2109 (3)	−0.01248 (15)	0.0330 (8)
O6	0.3412 (3)	−0.1600 (3)	−0.00516 (14)	0.0459 (8)
O2	0.1572 (4)	0.7030 (3)	0.24279 (14)	0.0528 (9)
H2	0.1176	0.7503	0.2184	0.063*
O3	0.4623 (4)	0.4841 (3)	0.23479 (15)	0.0550 (9)
O1	0.3190 (4)	0.6653 (3)	0.16736 (15)	0.0605 (9)
O4	−0.0057 (3)	−0.1359 (3)	0.18195 (14)	0.0500 (8)
C1	0.2762 (5)	0.6474 (4)	0.2177 (2)	0.0434 (11)
C2	0.3508 (6)	0.5602 (4)	0.2620 (2)	0.0546 (13)
H2A	0.3991	0.6073	0.2941	0.066*
H2B	0.2728	0.5089	0.2798	0.066*
C3	0.4095 (5)	0.3800 (4)	0.2047 (2)	0.0401 (10)
C4	0.2869 (5)	0.3104 (4)	0.2226 (2)	0.0482 (12)
H4	0.2304	0.3347	0.2557	0.058*
C5	0.2476 (5)	0.2047 (4)	0.19176 (19)	0.0432 (11)
H5	0.1638	0.1593	0.2043	0.052*
C6	0.3299 (4)	0.1642 (4)	0.14239 (17)	0.0291 (9)
C7	0.4531 (4)	0.2351 (4)	0.12463 (18)	0.0335 (9)
H7	0.5100	0.2110	0.0917	0.040*
C8	0.4928 (5)	0.3423 (4)	0.15567 (19)	0.0377 (10)
H8	0.5759	0.3888	0.1432	0.045*
C9	0.2205 (4)	−0.0419 (4)	0.14958 (18)	0.0349 (10)
H9A	0.2570	−0.0290	0.1905	0.042*
H9B	0.2618	−0.1197	0.1360	0.042*
C10	0.0478 (5)	−0.0518 (4)	0.15017 (18)	0.0342 (10)
C11	0.3746 (4)	0.0071 (4)	0.06312 (18)	0.0325 (9)
H11A	0.4592	−0.0398	0.0801	0.039*
H11B	0.4168	0.0745	0.0402	0.039*
C12	0.2791 (5)	−0.0758 (4)	0.02112 (18)	0.0327 (9)
C13	0.2498 (4)	0.1765 (4)	−0.06094 (19)	0.0378 (10)
H13	0.2383	0.0963	−0.0746	0.045*
C14	0.3463 (5)	0.2557 (4)	−0.0924 (2)	0.0452 (11)
H14	0.3974	0.2285	−0.1262	0.054*
C15	0.3644 (5)	0.3735 (4)	−0.0725 (2)	0.0466 (12)
H15	0.4320	0.4259	−0.0918	0.056*
C16	0.2812 (5)	0.4161 (4)	−0.02308 (19)	0.0381 (10)
C17	0.1868 (4)	0.3301 (4)	0.00554 (18)	0.0317 (9)
C18	0.0961 (4)	0.3654 (4)	0.05541 (18)	0.0336 (10)
C19	0.0966 (5)	0.4885 (4)	0.0753 (2)	0.0378 (10)
C20	0.1934 (5)	0.5738 (4)	0.0444 (2)	0.0487 (12)
H20	0.1951	0.6554	0.0568	0.058*
C21	0.2807 (5)	0.5397 (4)	−0.0012 (2)	0.0465 (12)
H21	0.3430	0.5978	−0.0193	0.056*
C22	0.0007 (5)	0.5157 (4)	0.1236 (2)	0.0452 (11)
H22	−0.0044	0.5955	0.1383	0.054*
C23	−0.0846 (5)	0.4261 (4)	0.1489 (2)	0.0475 (12)
H23	−0.1471	0.4445	0.1812	0.057*
C24	−0.0788 (5)	0.3064 (4)	0.12670 (19)	0.0407 (10)
H24	−0.1386	0.2462	0.1445	0.049*

	U11	U22	U33	U12	U13	U23
Cu1	0.0304 (3)	0.0260 (3)	0.0346 (3)	−0.0016 (2)	0.0050 (2)	0.0013 (2)
O5	0.0316 (15)	0.0351 (16)	0.0403 (17)	0.0001 (13)	0.0064 (13)	0.0070 (13)
O7	0.0301 (16)	0.0294 (15)	0.0383 (16)	−0.0020 (12)	0.0024 (12)	−0.0052 (12)
N1	0.0304 (18)	0.0289 (18)	0.0320 (18)	−0.0030 (15)	0.0074 (14)	0.0003 (15)
N2	0.0305 (18)	0.0294 (18)	0.0358 (19)	0.0004 (15)	−0.0009 (15)	0.0044 (15)
N3	0.0286 (18)	0.0318 (19)	0.039 (2)	−0.0017 (15)	0.0023 (15)	0.0029 (15)
O6	0.0423 (18)	0.0338 (17)	0.062 (2)	−0.0010 (14)	0.0179 (15)	−0.0130 (15)
O2	0.064 (2)	0.053 (2)	0.0415 (19)	0.0204 (17)	0.0086 (16)	0.0072 (16)
O3	0.048 (2)	0.0419 (18)	0.075 (2)	0.0052 (16)	−0.0136 (17)	−0.0256 (17)
O1	0.072 (2)	0.060 (2)	0.050 (2)	0.0073 (19)	0.0139 (18)	0.0041 (18)
O4	0.0411 (18)	0.0484 (19)	0.061 (2)	−0.0050 (15)	0.0101 (15)	0.0244 (16)
C1	0.053 (3)	0.033 (2)	0.044 (3)	−0.003 (2)	−0.002 (2)	−0.007 (2)
C2	0.064 (3)	0.044 (3)	0.056 (3)	0.013 (2)	−0.016 (3)	−0.018 (2)
C3	0.038 (2)	0.034 (2)	0.048 (3)	0.002 (2)	−0.011 (2)	−0.008 (2)
C4	0.037 (2)	0.059 (3)	0.049 (3)	−0.001 (2)	0.004 (2)	−0.022 (2)
C5	0.034 (2)	0.053 (3)	0.044 (3)	−0.013 (2)	0.0040 (19)	−0.011 (2)
C6	0.024 (2)	0.031 (2)	0.032 (2)	−0.0003 (17)	−0.0007 (16)	0.0014 (18)
C7	0.032 (2)	0.032 (2)	0.037 (2)	0.0009 (18)	0.0025 (18)	0.0010 (18)
C8	0.039 (2)	0.029 (2)	0.045 (3)	−0.0052 (19)	−0.003 (2)	0.004 (2)
C9	0.033 (2)	0.037 (2)	0.035 (2)	−0.0031 (18)	0.0012 (18)	0.0068 (19)
C10	0.035 (2)	0.035 (2)	0.033 (2)	−0.005 (2)	0.0054 (18)	0.0002 (19)
C11	0.025 (2)	0.031 (2)	0.042 (2)	0.0012 (17)	0.0034 (17)	0.0002 (18)
C12	0.033 (2)	0.025 (2)	0.040 (2)	−0.0044 (18)	0.0132 (18)	0.0025 (18)
C13	0.033 (2)	0.039 (2)	0.042 (2)	−0.0031 (19)	0.0045 (19)	0.004 (2)
C14	0.041 (3)	0.050 (3)	0.045 (3)	0.003 (2)	0.008 (2)	0.011 (2)
C15	0.033 (2)	0.050 (3)	0.056 (3)	−0.006 (2)	0.005 (2)	0.016 (2)
C16	0.035 (2)	0.032 (2)	0.047 (3)	−0.0062 (19)	−0.009 (2)	0.014 (2)
C17	0.027 (2)	0.030 (2)	0.038 (2)	−0.0023 (17)	−0.0051 (17)	0.0051 (19)
C18	0.031 (2)	0.032 (2)	0.037 (2)	−0.0028 (18)	−0.0089 (18)	0.0046 (18)
C19	0.036 (2)	0.031 (2)	0.046 (3)	−0.0014 (19)	−0.0115 (19)	0.001 (2)
C20	0.057 (3)	0.030 (2)	0.059 (3)	−0.010 (2)	−0.017 (3)	0.002 (2)
C21	0.044 (3)	0.038 (3)	0.058 (3)	−0.013 (2)	−0.006 (2)	0.009 (2)
C22	0.045 (3)	0.035 (3)	0.056 (3)	0.002 (2)	−0.011 (2)	−0.009 (2)
C23	0.050 (3)	0.049 (3)	0.044 (3)	0.010 (2)	−0.002 (2)	−0.009 (2)
C24	0.038 (2)	0.042 (3)	0.042 (3)	0.002 (2)	0.003 (2)	0.002 (2)

Cu1—O7	1.987 (3)	C5—H5	0.9300
Cu1—O5	1.997 (3)	C6—C7	1.387 (5)
Cu1—N2	2.003 (3)	C7—C8	1.397 (6)
Cu1—N3	2.049 (3)	C7—H7	0.9300
Cu1—O7i	2.293 (3)	C8—H8	0.9300
Cu1—N1	2.460 (3)	C9—C10	1.514 (5)
O5—C10	1.272 (5)	C9—H9A	0.9700
O7—C12	1.290 (5)	C9—H9B	0.9700
O7—Cu1i	2.293 (3)	C11—C12	1.536 (5)
N1—C6	1.420 (5)	C11—H11A	0.9700
N1—C11	1.462 (5)	C11—H11B	0.9700
N1—C9	1.465 (5)	C13—C14	1.401 (6)
N2—C24	1.325 (5)	C13—H13	0.9300
N2—C18	1.366 (5)	C14—C15	1.364 (6)
N3—C13	1.327 (5)	C14—H14	0.9300
N3—C17	1.363 (5)	C15—C16	1.406 (6)
O6—C12	1.219 (4)	C15—H15	0.9300
O2—C1	1.333 (5)	C16—C17	1.406 (5)
O2—H2	0.8200	C16—C21	1.431 (6)
O3—C3	1.392 (5)	C17—C18	1.426 (5)
O3—C2	1.422 (5)	C18—C19	1.411 (6)
O1—C1	1.201 (5)	C19—C22	1.405 (6)
O4—C10	1.252 (5)	C19—C20	1.437 (6)
C1—C2	1.510 (6)	C20—C21	1.331 (6)
C2—H2A	0.9700	C20—H20	0.9300
C2—H2B	0.9700	C21—H21	0.9300
C3—C4	1.376 (6)	C22—C23	1.354 (6)
C3—C8	1.382 (6)	C22—H22	0.9300
C4—C5	1.381 (6)	C23—C24	1.395 (6)
C4—H4	0.9300	C23—H23	0.9300
C5—C6	1.393 (5)	C24—H24	0.9300
O7—Cu1—O5	92.08 (11)	C3—C8—C7	120.5 (4)
O7—Cu1—N2	171.29 (12)	C3—C8—H8	119.8
O5—Cu1—N2	93.61 (12)	C7—C8—H8	119.8
O7—Cu1—N3	91.96 (12)	N1—C9—C10	115.5 (3)
O5—Cu1—N3	170.40 (12)	N1—C9—H9A	108.4
N2—Cu1—N3	81.44 (13)	C10—C9—H9A	108.4
O7—Cu1—O7i	77.11 (11)	N1—C9—H9B	108.4
O5—Cu1—O7i	93.01 (10)	C10—C9—H9B	108.4
N2—Cu1—O7i	109.13 (11)	H9A—C9—H9B	107.5
N3—Cu1—O7i	96.38 (11)	O4—C10—O5	123.8 (4)
O7—Cu1—N1	74.69 (11)	O4—C10—C9	116.0 (4)
O5—Cu1—N1	76.84 (11)	O5—C10—C9	120.2 (3)
N2—Cu1—N1	100.21 (12)	N1—C11—C12	111.2 (3)
N3—Cu1—N1	95.87 (12)	N1—C11—H11A	109.4
O7i—Cu1—N1	149.54 (10)	C12—C11—H11A	109.4
C10—O5—Cu1	119.6 (2)	N1—C11—H11B	109.4
C12—O7—Cu1	120.4 (2)	C12—C11—H11B	109.4
C12—O7—Cu1i	134.3 (2)	H11A—C11—H11B	108.0
Cu1—O7—Cu1i	102.89 (11)	O6—C12—O7	124.5 (4)
C6—N1—C11	119.6 (3)	O6—C12—C11	119.4 (4)
C6—N1—C9	115.8 (3)	O7—C12—C11	116.1 (3)
C11—N1—C9	111.7 (3)	N3—C13—C14	122.9 (4)
C6—N1—Cu1	108.0 (2)	N3—C13—H13	118.5
C11—N1—Cu1	96.4 (2)	C14—C13—H13	118.5
C9—N1—Cu1	101.4 (2)	C15—C14—C13	119.0 (4)
C24—N2—C18	118.2 (4)	C15—C14—H14	120.5
C24—N2—Cu1	128.9 (3)	C13—C14—H14	120.5
C18—N2—Cu1	112.4 (3)	C14—C15—C16	120.3 (4)
C13—N3—C17	117.8 (3)	C14—C15—H15	119.9
C13—N3—Cu1	130.4 (3)	C16—C15—H15	119.9
C17—N3—Cu1	111.3 (3)	C17—C16—C15	116.6 (4)
C1—O2—H2	109.5	C17—C16—C21	117.8 (4)
C3—O3—C2	117.1 (4)	C15—C16—C21	125.5 (4)
O1—C1—O2	124.9 (4)	N3—C17—C16	123.2 (4)
O1—C1—C2	125.0 (4)	N3—C17—C18	116.1 (3)
O2—C1—C2	110.1 (4)	C16—C17—C18	120.7 (4)
O3—C2—C1	112.3 (4)	N2—C18—C19	123.1 (4)
O3—C2—H2A	109.1	N2—C18—C17	116.9 (4)
C1—C2—H2A	109.1	C19—C18—C17	120.0 (4)
O3—C2—H2B	109.1	C22—C19—C18	116.2 (4)
C1—C2—H2B	109.1	C22—C19—C20	126.3 (4)
H2A—C2—H2B	107.9	C18—C19—C20	117.6 (4)
C4—C3—C8	119.2 (4)	C21—C20—C19	122.1 (4)
C4—C3—O3	124.2 (4)	C21—C20—H20	118.9
C8—C3—O3	116.5 (4)	C19—C20—H20	118.9
C3—C4—C5	120.2 (4)	C20—C21—C16	121.7 (4)
C3—C4—H4	119.9	C20—C21—H21	119.1
C5—C4—H4	119.9	C16—C21—H21	119.1
C4—C5—C6	121.9 (4)	C23—C22—C19	120.3 (4)
C4—C5—H5	119.1	C23—C22—H22	119.8
C6—C5—H5	119.1	C19—C22—H22	119.8
C7—C6—C5	117.4 (4)	C22—C23—C24	120.1 (4)
C7—C6—N1	123.3 (3)	C22—C23—H23	119.9
C5—C6—N1	119.2 (3)	C24—C23—H23	119.9
C6—C7—C8	120.8 (4)	N2—C24—C23	122.1 (4)
C6—C7—H7	119.6	N2—C24—H24	119.0
C8—C7—H7	119.6	C23—C24—H24	119.0

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ii	0.82	1.82	2.622 (4)	164

Cu1—O7	1.987 (3)
Cu1—O5	1.997 (3)
Cu1—N2	2.003 (3)
Cu1—N3	2.049 (3)
Cu1—O7i	2.293 (3)
Cu1—N1	2.460 (3)

O7—Cu1—O5	92.08 (11)
O7—Cu1—N2	171.29 (12)
O5—Cu1—N2	93.61 (12)
O7—Cu1—N3	91.96 (12)
O5—Cu1—N3	170.40 (12)
N2—Cu1—N3	81.44 (13)
O7—Cu1—O7i	77.11 (11)
O5—Cu1—O7i	93.01 (10)
N2—Cu1—O7i	109.13 (11)
N3—Cu1—O7i	96.38 (11)
O7—Cu1—N1	74.69 (11)
O5—Cu1—N1	76.84 (11)
N2—Cu1—N1	100.21 (12)
N3—Cu1—N1	95.87 (12)
O7i—Cu1—N1	149.54 (10)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4ii	0.82	1.82	2.622 (4)	164

Symmetry code: (ii) .