Bis(μ-4-chloro-2-oxidobenzoato)bis-[(1,10-phenanthroline)copper(II)] dihydrate.

The structure of the the title compound, [Cu(2)(C(7)H(3)ClO(3))(2)(C(12)H(8)N(2))(2)]·2H(2)O, consists of a dimeric unit involving a planar Cu(2)O(2) group arranged around an inversion center. The coordination sphere of the Cu(II) atom can be described as an elongated distorted square pyramid where the basal plane is formed by the two N atoms of the 1,10-phenanthroline mol-ecule and the two O atoms of the hydroxy-chloro-benzoate (hcbe) anion. The long apical Cu-O distance of 2.569 (2) Å involves the O atom of a symmetry-related hcbe anion, building up the dinuclear unit. Each dinuclear unit is connected through O-H⋯O hydrogen bonds involving two water mol-ecules, resulting in an R(4) (2)(8) graph-set motif and building up an infinite chain parallel to (10). C-H⋯O inter-actions further stabilize the chain.

Related literature

For our ongoing investigation of the nature of π–π stacking, see: Su & Xu (2004 ▶); Xu et al. (2007 ▶). For related structures, see: Yang et al. (2006 ▶); Garland et al. (1987 ▶); Li et al. (1995 ▶); Fan & Zhu (2005 ▶); Song et al. (2007 ▶). For a structural discussion on hydrogen bonding, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Cu2(C7H3ClO3)2(C12H8N2)2]·2H2O

M = 864.60

Monoclinic,

a = 8.1941 (17) Å

b = 18.851 (4) Å

c = 11.873 (3) Å

β = 105.993 (8)°

V = 1763.0 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.42 mm−1

T = 294 K

0.33 × 0.30 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.656, T max = 0.730

18894 measured reflections

3163 independent reflections

2162 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.103

S = 1.03

3163 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.36 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008354/dn2542sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008354/dn2542Isup2.hkl

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

[Cu2(C7H3ClO3)2(C12H8N2)2]·2H2O	F(000) = 876
Mr = 864.60	Dx = 1.629 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5352 reflections
a = 8.1941 (17) Å	θ = 2.2–24.2°
b = 18.851 (4) Å	µ = 1.42 mm−1
c = 11.873 (3) Å	T = 294 K
β = 105.993 (8)°	Prism, blue
V = 1763.0 (6) Å3	0.33 × 0.30 × 0.22 mm
Z = 2

Rigaku R-AXIS RAPID IP diffractometer	3163 independent reflections
Radiation source: fine-focus sealed tube	2162 reflections with I > 2σ(I)
graphite	Rint = 0.047
Detector resolution: 10.0 pixels mm-1	θmax = 25.2°, θmin = 2.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
Tmin = 0.656, Tmax = 0.730	l = −13→14
18894 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0509P)2 + 0.5996P] where P = (Fo2 + 2Fc2)/3
3163 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cu	0.28977 (4)	0.501289 (19)	0.46012 (3)	0.04370 (15)
Cl	0.68680 (17)	0.80306 (6)	0.36270 (13)	0.1107 (5)
N1	0.2931 (3)	0.50654 (13)	0.6296 (2)	0.0456 (6)
N2	0.1240 (3)	0.42264 (13)	0.4601 (2)	0.0480 (6)
O1	0.2426 (3)	0.49404 (12)	0.2962 (2)	0.0596 (6)
O2	0.2234 (3)	0.52593 (16)	0.1153 (2)	0.0750 (7)
O3	0.4451 (3)	0.57734 (11)	0.47282 (18)	0.0507 (5)
C1	0.2743 (4)	0.5384 (2)	0.2219 (3)	0.0555 (9)
C2	0.3717 (4)	0.60392 (18)	0.2646 (3)	0.0512 (8)
C3	0.4487 (4)	0.61966 (16)	0.3838 (3)	0.0472 (7)
C4	0.5430 (4)	0.68293 (17)	0.4110 (3)	0.0577 (9)
H4	0.5950	0.6941	0.4889	0.069*
C5	0.5593 (5)	0.72807 (19)	0.3250 (4)	0.0718 (11)
C6	0.4837 (5)	0.7141 (2)	0.2088 (4)	0.0851 (14)
H6	0.4947	0.7455	0.1509	0.102*
C7	0.3919 (5)	0.6528 (2)	0.1802 (3)	0.0711 (11)
H7	0.3408	0.6431	0.1015	0.085*
C8	0.3797 (4)	0.55026 (19)	0.7127 (3)	0.0569 (9)
H8	0.4424	0.5868	0.6923	0.068*
C9	0.3792 (5)	0.5429 (2)	0.8297 (3)	0.0728 (11)
H9	0.4401	0.5745	0.8857	0.087*
C10	0.2897 (5)	0.4896 (2)	0.8616 (4)	0.0765 (13)
H10	0.2892	0.4847	0.9394	0.092*
C11	0.1979 (5)	0.4418 (2)	0.7767 (3)	0.0635 (10)
C12	0.1001 (6)	0.3835 (3)	0.7997 (4)	0.0854 (14)
H12	0.0971	0.3746	0.8761	0.102*
C13	0.0125 (6)	0.3412 (3)	0.7126 (5)	0.0876 (14)
H13	−0.0510	0.3041	0.7306	0.105*
C14	0.0135 (5)	0.3514 (2)	0.5930 (4)	0.0675 (11)
C15	−0.0751 (6)	0.3107 (2)	0.4968 (5)	0.0882 (14)
H15	−0.1426	0.2731	0.5076	0.106*
C16	−0.0626 (5)	0.3259 (2)	0.3884 (5)	0.0849 (13)
H16	−0.1223	0.2990	0.3247	0.102*
C17	0.0394 (5)	0.38181 (19)	0.3716 (3)	0.0639 (10)
H17	0.0486	0.3909	0.2966	0.077*
C18	0.1106 (4)	0.40810 (17)	0.5688 (3)	0.0505 (8)
C19	0.2019 (4)	0.45334 (17)	0.6605 (3)	0.0499 (8)
O1W	0.0002 (4)	0.59767 (16)	−0.0734 (2)	0.0934 (9)
H1A	0.0653	0.5735	−0.0124	0.140*
H1B	−0.0941	0.5733	−0.0960	0.140*

	U11	U22	U33	U12	U13	U23
Cu	0.0459 (2)	0.0543 (2)	0.0309 (2)	−0.00153 (17)	0.01078 (16)	0.00139 (17)
Cl	0.1106 (10)	0.0650 (6)	0.1553 (13)	−0.0153 (6)	0.0347 (9)	0.0283 (7)
N1	0.0459 (14)	0.0589 (15)	0.0335 (14)	0.0089 (13)	0.0134 (11)	−0.0016 (13)
N2	0.0424 (15)	0.0544 (15)	0.0472 (17)	0.0028 (12)	0.0124 (12)	−0.0025 (13)
O1	0.0688 (16)	0.0716 (15)	0.0349 (13)	−0.0104 (12)	0.0085 (11)	−0.0014 (11)
O2	0.0772 (18)	0.117 (2)	0.0277 (14)	0.0076 (16)	0.0085 (12)	0.0011 (13)
O3	0.0577 (13)	0.0586 (13)	0.0357 (12)	−0.0060 (10)	0.0125 (10)	0.0031 (10)
C1	0.0470 (19)	0.081 (2)	0.038 (2)	0.0107 (18)	0.0103 (15)	0.0060 (18)
C2	0.0443 (18)	0.069 (2)	0.0419 (19)	0.0106 (16)	0.0144 (15)	0.0163 (16)
C3	0.0443 (18)	0.0539 (18)	0.046 (2)	0.0079 (15)	0.0176 (15)	0.0062 (16)
C4	0.057 (2)	0.0537 (19)	0.064 (2)	0.0052 (16)	0.0197 (18)	0.0051 (17)
C5	0.060 (2)	0.058 (2)	0.099 (3)	0.0067 (18)	0.025 (2)	0.025 (2)
C6	0.075 (3)	0.095 (3)	0.089 (3)	0.008 (2)	0.028 (3)	0.053 (3)
C7	0.063 (2)	0.099 (3)	0.052 (2)	0.010 (2)	0.0164 (19)	0.028 (2)
C8	0.056 (2)	0.071 (2)	0.042 (2)	0.0117 (17)	0.0109 (16)	−0.0050 (17)
C9	0.074 (3)	0.102 (3)	0.038 (2)	0.021 (2)	0.0075 (19)	−0.011 (2)
C10	0.078 (3)	0.119 (4)	0.040 (2)	0.034 (3)	0.028 (2)	0.013 (2)
C11	0.058 (2)	0.089 (3)	0.052 (2)	0.024 (2)	0.0296 (18)	0.018 (2)
C12	0.076 (3)	0.118 (4)	0.078 (3)	0.031 (3)	0.050 (3)	0.045 (3)
C13	0.074 (3)	0.089 (3)	0.117 (4)	0.009 (2)	0.055 (3)	0.040 (3)
C14	0.054 (2)	0.064 (2)	0.094 (3)	0.0047 (18)	0.035 (2)	0.016 (2)
C15	0.077 (3)	0.062 (2)	0.129 (5)	−0.013 (2)	0.034 (3)	0.004 (3)
C16	0.069 (3)	0.069 (3)	0.113 (4)	−0.014 (2)	0.019 (3)	−0.024 (3)
C17	0.057 (2)	0.062 (2)	0.069 (3)	0.0008 (18)	0.0128 (19)	−0.0129 (19)
C18	0.0417 (18)	0.0575 (19)	0.055 (2)	0.0093 (15)	0.0183 (16)	0.0081 (17)
C19	0.0462 (19)	0.062 (2)	0.047 (2)	0.0175 (16)	0.0226 (15)	0.0131 (16)
O1W	0.097 (2)	0.111 (2)	0.0617 (18)	0.0296 (18)	0.0041 (15)	0.0005 (16)

Cu—O1	1.882 (2)	C8—C9	1.397 (5)
Cu—O3	1.895 (2)	C8—H8	0.9300
Cu—O3i	2.569 (2)	C9—C10	1.358 (6)
Cu—N1	2.007 (3)	C9—H9	0.9300
Cu—N2	2.011 (3)	C10—C11	1.405 (6)
Cl—C5	1.741 (4)	C10—H10	0.9300
N1—C8	1.331 (4)	C11—C19	1.406 (4)
N1—C19	1.360 (4)	C11—C12	1.430 (6)
N2—C17	1.332 (4)	C12—C13	1.346 (6)
N2—C18	1.353 (4)	C12—H12	0.9300
O1—C1	1.292 (4)	C13—C14	1.435 (6)
O2—C1	1.241 (4)	C13—H13	0.9300
O3—C3	1.331 (4)	C14—C15	1.401 (6)
C1—C2	1.482 (5)	C14—C18	1.409 (5)
C2—C7	1.404 (4)	C15—C16	1.350 (6)
C2—C3	1.413 (4)	C15—H15	0.9300
C3—C4	1.409 (5)	C16—C17	1.393 (5)
C4—C5	1.363 (5)	C16—H16	0.9300
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.374 (6)	C18—C19	1.423 (5)
C6—C7	1.370 (6)	O1W—H1A	0.8969
C6—H6	0.9300	O1W—H1B	0.8747
C7—H7	0.9300
O1—Cu—O3	94.54 (9)	C2—C7—H7	118.6
O1—Cu—N1	169.27 (10)	N1—C8—C9	121.9 (4)
O3—Cu—N1	93.42 (10)	N1—C8—H8	119.1
O1—Cu—N2	90.01 (10)	C9—C8—H8	119.1
O3—Cu—N2	175.25 (9)	C10—C9—C8	120.1 (4)
N1—Cu—N2	81.90 (11)	C10—C9—H9	120.0
O1—Cu—O3i	101.17 (9)	C8—C9—H9	120.0
O3—Cu—O3i	85.40 (9)	C9—C10—C11	119.8 (4)
N1—Cu—O3i	86.62 (8)	C9—C10—H10	120.1
N2—Cu—O3i	95.07 (9)	C11—C10—H10	120.1
C8—N1—C19	118.5 (3)	C10—C11—C19	116.9 (4)
C8—N1—Cu	129.1 (2)	C10—C11—C12	125.0 (4)
C19—N1—Cu	112.2 (2)	C19—C11—C12	118.1 (4)
C17—N2—C18	118.3 (3)	C13—C12—C11	121.2 (4)
C17—N2—Cu	129.1 (3)	C13—C12—H12	119.4
C18—N2—Cu	112.4 (2)	C11—C12—H12	119.4
C1—O1—Cu	129.5 (2)	C12—C13—C14	122.2 (4)
C3—O3—Cu	123.5 (2)	C12—C13—H13	118.9
O2—C1—O1	119.9 (3)	C14—C13—H13	118.9
O2—C1—C2	120.3 (3)	C15—C14—C18	116.3 (4)
O1—C1—C2	119.8 (3)	C15—C14—C13	126.2 (4)
C7—C2—C3	118.0 (3)	C18—C14—C13	117.5 (4)
C7—C2—C1	117.4 (3)	C16—C15—C14	120.2 (4)
C3—C2—C1	124.6 (3)	C16—C15—H15	119.9
O3—C3—C4	117.2 (3)	C14—C15—H15	119.9
O3—C3—C2	124.6 (3)	C15—C16—C17	120.3 (4)
C4—C3—C2	118.2 (3)	C15—C16—H16	119.9
C5—C4—C3	121.2 (4)	C17—C16—H16	119.9
C5—C4—H4	119.4	N2—C17—C16	121.8 (4)
C3—C4—H4	119.4	N2—C17—H17	119.1
C6—C5—C4	121.5 (4)	C16—C17—H17	119.1
C6—C5—Cl	119.1 (3)	N2—C18—C14	123.2 (3)
C4—C5—Cl	119.4 (3)	N2—C18—C19	116.4 (3)
C5—C6—C7	118.5 (3)	C14—C18—C19	120.4 (3)
C5—C6—H6	120.8	N1—C19—C11	122.8 (3)
C7—C6—H6	120.8	N1—C19—C18	116.6 (3)
C6—C7—C2	122.7 (4)	C11—C19—C18	120.6 (3)
C6—C7—H7	118.6	H1A—O1W—H1B	105.1

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2	0.90	1.92	2.817 (4)	175
O1W—H1B···O2ii	0.88	2.13	2.921 (4)	150
C10—H10···O2iii	0.93	2.42	3.277 (5)	153
C17—H17···O1Wii	0.93	2.58	3.487 (4)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2	0.90	1.92	2.817 (4)	175
O1W—H1B⋯O2i	0.88	2.13	2.921 (4)	150
C10—H10⋯O2ii	0.93	2.42	3.277 (5)	153
C17—H17⋯O1Wi	0.93	2.58	3.487 (4)	166

Symmetry codes: (i) ; (ii) .