μ-Adipato-bis-[chlorido(2,2':6',2''-terpyridine)-copper(II)] tetra-hydrate.

In the title compound, [Cu(2)(C(6)H(8)O(4))Cl(2)(C(15)H(11)N(3))(2)]·4H(2)O, the dinuclear copper complex is located on a crystallographic inversion centre. Each Cu atom is in a distorted square-pyramidal coordination environment, with one O atom of an adipate dianion and three N atoms from the 2,2':6',2''-terpyridine ligand occupying the basal plane, and one chlorine in the apical site. In addition, there is weak Cu-O inter-action opposite of the chlorine with a distance of 2.768 (1) Å. The adipate ligand adopts a gauche-anti-gauche conformation. The inter-stitial water mol-ecules form hydrogen-bonded tertramers that are connected to the complexes via O-H⋯O and O-H⋯Cl hydrogen bonds, thus leading to the formation of tightly hydrogen-bonded layers extending perpendicular to the b-axis direction.

Related literature

For general background to the use of saturated aliphatic dicarboxyl­ate ligands as flexible spacer ligands, see: Forster & Cheetham (2002 ▶); Vaidhyanathan et al. (2002 ▶); Zheng, Lin et al. (2008 ▶). For related structures, see: Zheng, Cheng et al. (2008 ▶).

Experimental

Crystal data

[Cu2(C6H8O4)Cl2(C15H11N3)2]·4H2O

M = 880.70

Triclinic,

a = 8.2334 (16) Å

b = 9.5678 (19) Å

c = 11.548 (2) Å

α = 83.42 (3)°

β = 81.69 (3)°

γ = 84.38 (3)°

V = 891.2 (3) Å3

Z = 1

Mo Kα radiation

μ = 1.41 mm−1

T = 298 K

0.25 × 0.22 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.680, T max = 0.892

8834 measured reflections

4046 independent reflections

3751 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.080

S = 1.25

4046 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.51 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810027005/zl2287sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027005/zl2287Isup2.hkl

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

[Cu2(C6H8O4)Cl2(C15H11N3)2]·4H2O	Z = 1
Mr = 880.70	F(000) = 452
Triclinic, P1	Dx = 1.641 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2334 (16) Å	Cell parameters from 7883 reflections
b = 9.5678 (19) Å	θ = 3.0–27.4°
c = 11.548 (2) Å	µ = 1.41 mm−1
α = 83.42 (3)°	T = 298 K
β = 81.69 (3)°	Plate, green
γ = 84.38 (3)°	0.25 × 0.22 × 0.07 mm
V = 891.2 (3) Å3

Rigaku R-AXIS RAPID diffractometer	4046 independent reflections
Radiation source: fine-focus sealed tube	3751 reflections with I > 2σ(I)
graphite	Rint = 0.016
Detector resolution: 0 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.680, Tmax = 0.892	l = −14→14
8834 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.25	w = 1/[σ2(Fo2) + (0.0414P)2 + 0.4176P] where P = (Fo2 + 2Fc2)/3
4046 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.51 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
Cu	0.13815 (3)	0.79530 (2)	0.258347 (18)	0.00798 (8)
Cl	0.00080 (5)	0.61527 (4)	0.17386 (4)	0.01293 (10)
O1	0.31683 (16)	0.65682 (13)	0.29993 (11)	0.0110 (3)
O2	0.41422 (18)	0.84454 (14)	0.35396 (12)	0.0158 (3)
O3	0.40877 (18)	0.42538 (14)	0.16550 (12)	0.0173 (3)
H3C	0.5094	0.4458	0.1431	0.021*
H3D	0.3784	0.4760	0.2132	0.021*
O4	−0.30631 (19)	0.54262 (18)	0.05804 (13)	0.0244 (3)
H4C	−0.2000	0.5478	0.0749	0.029*
H4D	−0.2994	0.5637	−0.0183	0.029*
N1	−0.00477 (19)	0.78588 (16)	0.41703 (13)	0.0093 (3)
N2	0.01050 (18)	0.97845 (15)	0.24509 (13)	0.0089 (3)
N3	0.24603 (19)	0.88021 (16)	0.10055 (13)	0.0097 (3)
C1	−0.0037 (2)	0.67745 (19)	0.50071 (16)	0.0121 (3)
H1A	0.0753	0.6020	0.4902	0.014*
C2	−0.1158 (2)	0.6730 (2)	0.60277 (16)	0.0139 (4)
H2A	−0.1120	0.5962	0.6598	0.017*
C3	−0.2338 (2)	0.7858 (2)	0.61759 (16)	0.0151 (4)
H3A	−0.3115	0.7851	0.6846	0.018*
C4	−0.2350 (2)	0.90009 (19)	0.53138 (16)	0.0131 (4)
H4A	−0.3123	0.9771	0.5404	0.016*
C5	−0.1188 (2)	0.89694 (18)	0.43166 (16)	0.0098 (3)
C6	−0.1046 (2)	1.01126 (19)	0.33414 (16)	0.0104 (3)
C7	−0.1938 (2)	1.14257 (19)	0.33008 (16)	0.0128 (4)
H7A	−0.2752	1.1655	0.3912	0.015*
C8	−0.1577 (2)	1.23842 (19)	0.23184 (17)	0.0138 (4)
H8A	−0.2157	1.3269	0.2272	0.017*
C9	−0.0360 (2)	1.20397 (19)	0.14023 (16)	0.0126 (4)
H9A	−0.0112	1.2683	0.0748	0.015*
C10	0.0474 (2)	1.06991 (18)	0.14981 (16)	0.0100 (3)
C11	0.1807 (2)	1.01092 (18)	0.06390 (15)	0.0093 (3)
C12	0.2341 (2)	1.07967 (19)	−0.04513 (16)	0.0122 (3)
H12A	0.1876	1.1691	−0.0687	0.015*
C13	0.3592 (2)	1.0118 (2)	−0.11900 (16)	0.0134 (4)
H13A	0.3983	1.0557	−0.1924	0.016*
C14	0.4240 (2)	0.8782 (2)	−0.08133 (16)	0.0137 (4)
H14A	0.5065	0.8308	−0.1296	0.016*
C15	0.3649 (2)	0.81548 (19)	0.02906 (16)	0.0117 (3)
H15A	0.4092	0.7258	0.0541	0.014*
C16	0.4287 (2)	0.71750 (18)	0.33897 (15)	0.0095 (3)
C17	0.5825 (2)	0.62512 (19)	0.36324 (16)	0.0121 (3)
H17A	0.6498	0.6774	0.4025	0.015*
H17B	0.6456	0.6031	0.2890	0.015*
C18	0.5460 (2)	0.48718 (19)	0.43937 (15)	0.0117 (4)
H18A	0.4804	0.4338	0.3997	0.014*
H18C	0.6489	0.4311	0.4487	0.014*

	U11	U22	U33	U12	U13	U23
Cu	0.00828 (12)	0.00753 (11)	0.00710 (12)	0.00144 (7)	−0.00039 (8)	0.00098 (8)
Cl	0.0137 (2)	0.0122 (2)	0.0137 (2)	−0.00219 (15)	−0.00496 (16)	0.00018 (16)
O1	0.0104 (6)	0.0105 (6)	0.0121 (6)	0.0011 (5)	−0.0030 (5)	−0.0010 (5)
O2	0.0188 (7)	0.0106 (6)	0.0179 (7)	0.0001 (5)	−0.0016 (5)	−0.0031 (5)
O3	0.0191 (7)	0.0159 (6)	0.0161 (7)	−0.0004 (5)	0.0020 (5)	−0.0052 (5)
O4	0.0184 (8)	0.0409 (9)	0.0157 (7)	−0.0097 (7)	−0.0021 (6)	−0.0040 (7)
N1	0.0105 (7)	0.0089 (7)	0.0086 (7)	−0.0010 (5)	−0.0017 (5)	−0.0008 (6)
N2	0.0092 (7)	0.0083 (7)	0.0092 (7)	−0.0006 (5)	−0.0026 (6)	0.0001 (6)
N3	0.0098 (7)	0.0105 (7)	0.0090 (7)	−0.0011 (5)	−0.0020 (5)	−0.0001 (6)
C1	0.0117 (8)	0.0115 (8)	0.0133 (8)	−0.0008 (6)	−0.0034 (7)	−0.0004 (7)
C2	0.0171 (9)	0.0145 (8)	0.0108 (8)	−0.0047 (7)	−0.0037 (7)	0.0015 (7)
C3	0.0174 (9)	0.0176 (9)	0.0100 (8)	−0.0050 (7)	0.0025 (7)	−0.0024 (7)
C4	0.0139 (9)	0.0123 (8)	0.0129 (8)	−0.0017 (7)	0.0008 (7)	−0.0028 (7)
C5	0.0109 (8)	0.0086 (8)	0.0106 (8)	−0.0011 (6)	−0.0027 (6)	−0.0019 (7)
C6	0.0099 (8)	0.0116 (8)	0.0105 (8)	−0.0010 (6)	−0.0026 (6)	−0.0031 (7)
C7	0.0117 (9)	0.0128 (8)	0.0142 (9)	0.0018 (7)	−0.0026 (7)	−0.0045 (7)
C8	0.0147 (9)	0.0093 (8)	0.0177 (9)	0.0020 (6)	−0.0055 (7)	−0.0016 (7)
C9	0.0152 (9)	0.0102 (8)	0.0130 (8)	−0.0022 (7)	−0.0048 (7)	0.0017 (7)
C10	0.0102 (8)	0.0104 (8)	0.0100 (8)	−0.0017 (6)	−0.0035 (6)	0.0003 (7)
C11	0.0093 (8)	0.0089 (8)	0.0102 (8)	−0.0020 (6)	−0.0038 (6)	0.0011 (7)
C12	0.0133 (9)	0.0125 (8)	0.0116 (8)	−0.0034 (7)	−0.0035 (7)	−0.0002 (7)
C13	0.0140 (9)	0.0177 (9)	0.0092 (8)	−0.0068 (7)	−0.0013 (7)	−0.0003 (7)
C14	0.0117 (9)	0.0182 (9)	0.0114 (8)	−0.0030 (7)	0.0013 (7)	−0.0049 (7)
C15	0.0121 (9)	0.0109 (8)	0.0117 (8)	−0.0004 (6)	−0.0021 (7)	−0.0002 (7)
C16	0.0120 (8)	0.0100 (8)	0.0053 (7)	−0.0016 (6)	0.0016 (6)	0.0018 (6)
C17	0.0100 (8)	0.0144 (8)	0.0116 (8)	−0.0003 (6)	−0.0020 (6)	−0.0002 (7)
C18	0.0119 (8)	0.0122 (8)	0.0109 (8)	0.0036 (6)	−0.0044 (7)	−0.0012 (7)

Cu—N2	1.9552 (16)	C5—C6	1.478 (3)
Cu—O1	1.9562 (14)	C6—C7	1.391 (2)
Cu—N3	2.0257 (17)	C7—C8	1.391 (3)
Cu—N1	2.0274 (16)	C7—H7A	0.9300
Cu—Cl	2.5067 (8)	C8—C9	1.393 (3)
O1—C16	1.294 (2)	C8—H8A	0.9300
O2—C16	1.239 (2)	C9—C10	1.395 (2)
O3—H3C	0.8658	C9—H9A	0.9300
O3—H3D	0.7734	C10—C11	1.483 (2)
O4—H4C	0.9308	C11—C12	1.385 (3)
O4—H4D	0.8764	C12—C13	1.397 (3)
N1—C1	1.335 (2)	C12—H12A	0.9300
N1—C5	1.356 (2)	C13—C14	1.383 (3)
N2—C6	1.337 (2)	C13—H13A	0.9300
N2—C10	1.343 (2)	C14—C15	1.387 (3)
N3—C15	1.337 (2)	C14—H14A	0.9300
N3—C11	1.358 (2)	C15—H15A	0.9300
C1—C2	1.387 (3)	C16—C17	1.513 (3)
C1—H1A	0.9300	C17—C18	1.530 (3)
C2—C3	1.389 (3)	C17—H17A	0.9700
C2—H2A	0.9300	C17—H17B	0.9700
C3—C4	1.392 (3)	C18—C18i	1.527 (3)
C3—H3A	0.9300	C18—H18A	0.9700
C4—C5	1.388 (3)	C18—H18C	0.9700
C4—H4A	0.9300
N2—Cu—O1	157.68 (6)	C8—C7—H7A	121.0
N2—Cu—N3	79.61 (7)	C6—C7—H7A	121.0
O1—Cu—N3	99.40 (6)	C7—C8—C9	121.01 (17)
N2—Cu—N1	79.49 (7)	C7—C8—H8A	119.5
O1—Cu—N1	98.23 (6)	C9—C8—H8A	119.5
N3—Cu—N1	158.62 (6)	C8—C9—C10	117.87 (17)
N2—Cu—Cl	110.17 (5)	C8—C9—H9A	121.1
O1—Cu—Cl	92.15 (4)	C10—C9—H9A	121.1
N3—Cu—Cl	94.79 (5)	N2—C10—C9	120.32 (17)
N1—Cu—Cl	96.54 (5)	N2—C10—C11	112.50 (15)
C16—O1—Cu	110.59 (11)	C9—C10—C11	127.18 (17)
H3C—O3—H3D	102.7	N3—C11—C12	122.00 (16)
H4C—O4—H4D	104.5	N3—C11—C10	113.92 (15)
C1—N1—C5	119.25 (16)	C12—C11—C10	124.06 (16)
C1—N1—Cu	125.82 (13)	C11—C12—C13	118.57 (17)
C5—N1—Cu	114.70 (12)	C11—C12—H12A	120.7
C6—N2—C10	122.21 (15)	C13—C12—H12A	120.7
C6—N2—Cu	118.81 (12)	C14—C13—C12	119.01 (17)
C10—N2—Cu	118.88 (12)	C14—C13—H13A	120.5
C15—N3—C11	119.08 (16)	C12—C13—H13A	120.5
C15—N3—Cu	125.77 (12)	C13—C14—C15	119.40 (17)
C11—N3—Cu	114.98 (12)	C13—C14—H14A	120.3
N1—C1—C2	122.57 (17)	C15—C14—H14A	120.3
N1—C1—H1A	118.7	N3—C15—C14	121.92 (17)
C2—C1—H1A	118.7	N3—C15—H15A	119.0
C1—C2—C3	118.37 (18)	C14—C15—H15A	119.0
C1—C2—H2A	120.8	O2—C16—O1	122.70 (17)
C3—C2—H2A	120.8	O2—C16—C17	121.07 (17)
C2—C3—C4	119.53 (18)	O1—C16—C17	116.22 (15)
C2—C3—H3A	120.2	C16—C17—C18	113.19 (15)
C4—C3—H3A	120.2	C16—C17—H17A	108.9
C5—C4—C3	118.75 (17)	C18—C17—H17A	108.9
C5—C4—H4A	120.6	C16—C17—H17B	108.9
C3—C4—H4A	120.6	C18—C17—H17B	108.9
N1—C5—C4	121.52 (17)	H17A—C17—H17B	107.8
N1—C5—C6	113.96 (16)	C18i—C18—C17	112.17 (18)
C4—C5—C6	124.51 (16)	C18i—C18—H18A	109.2
N2—C6—C7	120.59 (17)	C17—C18—H18A	109.2
N2—C6—C5	112.72 (15)	C18i—C18—H18C	109.2
C7—C6—C5	126.68 (17)	C17—C18—H18C	109.2
C8—C7—C6	117.98 (17)	H18A—C18—H18C	107.9

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3C···O4ii	0.87	1.94	2.767 (2)	160
O3—H3D···O1	0.77	2.08	2.829 (2)	163
O4—H4C···Cl	0.93	2.32	3.194 (2)	156
O4—H4D···O3iii	0.88	2.02	2.805 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3C⋯O4i	0.87	1.94	2.767 (2)	160
O3—H3D⋯O1	0.77	2.08	2.829 (2)	163
O4—H4C⋯Cl	0.93	2.32	3.194 (2)	156
O4—H4D⋯O3ii	0.88	2.02	2.805 (2)	148

Symmetry codes: (i) ; (ii) .