Chlorido{μ-2,6-bis-[(2-amino-eth-yl)imino-meth-yl]-4-chloro-phenolato}-μ-oxido-dicopper(II) trihydrate.

In the title dinuclear complex, [Cu(2)(C(14)H(20)ClN(4)O)ClO]·3H(2)O, one Cu(II) cation assumes a distorted square-planar coordination geometry and the other a distorted square-pyramidal coordination geometry. Both Cu(II) cations are N,N',O-chelated by one arm of the 2,6-bis-[(2-amino-eth-yl)imino-meth-yl]-4-chloro-phenolate anion, and one oxide anion bridges the two Cu(II) cations, forming a dinuclear complex. One of the Cu(II) cations is further coordinated by an Cl(-) anion in the apical direction. In the crystal, lattice water mol-ecules are linked with the complex mol-ecule via O-H⋯Cl hydrogen bonds while O-H⋯O hydrogen bonding occurs between lattice water mol-ecules , forming three-dimensional network structure.

Related literature

For the synthesis, see: Gagne et al. (1981 ▶). For a related oxygen anion-bridging complex, see: Olmstead et al. (2011 ▶). For the biological activity of Schiff bases, see: Raman et al. (2007 ▶); Hao et al. (2006 ▶). For the biological properties of binuclear complexes, see: Tian et al. (2007 ▶); Anbu et al. (2009 ▶). Several proteins in vivo contain transition metal atoms, especially, CuII, see: Dede et al. (2009 ▶); Veysel et al. (2003 ▶); Asokan et al. (1995 ▶).

Experimental

Crystal data

[Cu2(C14H20ClN4O)ClO]·3H2O

M = 528.37

Monoclinic,

a = 11.201 (5) Å

b = 12.387 (7) Å

c = 16.718 (7) Å

β = 93.18 (4)°

V = 2316.0 (19) Å3

Z = 4

Mo Kα radiation

μ = 2.10 mm−1

T = 291 K

0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.572, T max = 0.633

12029 measured reflections

4087 independent reflections

3286 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.175

S = 1.02

4087 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.94 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008) ▶; program(s) used to refine structure: SHELXTL ▶; molecular graphics: SHELXTL ▶; software used to prepare material for publication: SHELXTL ▶.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202301X/xu5529sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202301X/xu5529Isup2.hkl

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

[Cu2(C14H20ClN4O)ClO]·3H2O	F(000) = 1080
Mr = 528.37	Dx = 1.515 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4001 reflections
a = 11.201 (5) Å	θ = 2.4–26.6°
b = 12.387 (7) Å	µ = 2.10 mm−1
c = 16.718 (7) Å	T = 291 K
β = 93.18 (4)°	Block, green
V = 2316.0 (19) Å3	0.30 × 0.26 × 0.24 mm
Z = 4

Bruker SMART APEX CCD diffractometer	4087 independent reflections
Radiation source: sealed tube	3286 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.572, Tmax = 0.633	k = −14→11
12029 measured reflections	l = −19→19

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.080P)2 + 12.660P] where P = (Fo2 + 2Fc2)/3
4087 reflections	(Δ/σ)max = 0.076
244 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.94 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 > 2sigma(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
Cl1	0.29197 (15)	0.09726 (13)	0.30847 (10)	0.0409 (4)
Cl2	0.31005 (15)	0.62287 (14)	0.44102 (10)	0.0435 (4)
Cu1	0.43928 (7)	0.66390 (6)	0.32886 (5)	0.0360 (2)
Cu2	0.22384 (7)	0.67193 (6)	0.21370 (5)	0.0360 (2)
C1	0.6375 (6)	0.7673 (6)	0.4411 (4)	0.0388 (15)
H1A	0.6233	0.8117	0.4874	0.047*
H1B	0.7089	0.7953	0.4180	0.047*
C2	0.6665 (7)	0.6538 (6)	0.4715 (4)	0.0451 (17)
H2A	0.6055	0.6302	0.5066	0.054*
H2B	0.7427	0.6541	0.5020	0.054*
C3	0.6721 (6)	0.5750 (5)	0.4003 (4)	0.0376 (15)
H3A	0.7219	0.6064	0.3607	0.045*
H3B	0.7101	0.5086	0.4191	0.045*
C4	0.5264 (6)	0.4435 (6)	0.3522 (4)	0.0395 (15)
H4	0.5824	0.3950	0.3744	0.047*
C5	0.3361 (6)	0.4596 (5)	0.2694 (4)	0.0360 (15)
C6	0.4249 (6)	0.3996 (6)	0.3141 (4)	0.0412 (16)
C7	0.4106 (6)	0.2905 (6)	0.3267 (4)	0.0358 (14)
H7	0.4677	0.2524	0.3577	0.043*
C8	0.3091 (7)	0.2369 (6)	0.2923 (4)	0.0460 (17)
C9	0.2214 (6)	0.2954 (5)	0.2455 (4)	0.0369 (14)
H9	0.1554	0.2602	0.2215	0.044*
C10	0.2354 (6)	0.4051 (5)	0.2363 (4)	0.0396 (15)
C11	0.1424 (6)	0.4496 (5)	0.1867 (4)	0.0409 (16)
H11	0.0913	0.3989	0.1621	0.049*
C12	0.0115 (6)	0.5819 (6)	0.1123 (5)	0.0472 (18)
H12A	−0.0533	0.6059	0.1440	0.057*
H12B	−0.0157	0.5176	0.0837	0.057*
C13	0.0339 (7)	0.6702 (6)	0.0498 (4)	0.0428 (16)
H13A	−0.0303	0.6710	0.0084	0.051*
H13B	0.1087	0.6570	0.0249	0.051*
C14	0.0392 (6)	0.7802 (5)	0.0960 (4)	0.0376 (15)
H14A	0.0569	0.8361	0.0578	0.045*
H14B	−0.0403	0.7947	0.1136	0.045*
N1	0.5352 (5)	0.7852 (5)	0.3811 (3)	0.0398 (13)
H1C	0.5640	0.8243	0.3411	0.048*
H1D	0.4827	0.8279	0.4050	0.048*
N2	0.5521 (5)	0.5481 (5)	0.3605 (3)	0.0417 (13)
N3	0.1152 (5)	0.5507 (5)	0.1690 (3)	0.0405 (13)
N4	0.1253 (5)	0.7929 (5)	0.1670 (3)	0.0437 (14)
H4A	0.0830	0.8191	0.2069	0.052*
H4B	0.1768	0.8452	0.1545	0.052*
O1	0.3458 (4)	0.5674 (4)	0.2586 (2)	0.0373 (10)
O2	0.3320 (4)	0.7525 (3)	0.2702 (3)	0.0360 (10)
O1W	0.2820 (9)	−0.0067 (9)	0.4419 (7)	0.144 (4)
H1WD	0.2653	0.0494	0.4142	0.173*
H1WC	0.2692	0.0055	0.4907	0.216*
O2W	0.1297 (9)	0.4729 (8)	0.3981 (7)	0.150 (4)
H2WD	0.1802	0.4946	0.3656	0.180*
H2WB	0.1094	0.5253	0.4272	0.224*
O3W	0.0267 (9)	0.7040 (8)	0.3693 (5)	0.120 (3)
H3WD	0.0988	0.6829	0.3681	0.144*
H3WA	−0.0136	0.6575	0.3937	0.181*

	U11	U22	U33	U12	U13	U23
Cl1	0.0444 (9)	0.0364 (9)	0.0429 (9)	−0.0072 (7)	0.0111 (7)	0.0118 (7)
Cl2	0.0412 (9)	0.0478 (10)	0.0426 (9)	−0.0115 (7)	0.0131 (7)	0.0021 (7)
Cu1	0.0350 (4)	0.0388 (5)	0.0352 (4)	−0.0085 (3)	0.0097 (3)	0.0019 (3)
Cu2	0.0359 (4)	0.0376 (5)	0.0352 (4)	0.0013 (3)	0.0082 (3)	0.0003 (3)
C1	0.038 (3)	0.045 (4)	0.034 (3)	0.009 (3)	0.007 (3)	0.010 (3)
C2	0.047 (4)	0.039 (4)	0.050 (4)	−0.003 (3)	0.014 (3)	0.014 (3)
C3	0.046 (4)	0.036 (3)	0.033 (3)	−0.005 (3)	0.015 (3)	0.016 (3)
C4	0.034 (3)	0.040 (4)	0.044 (4)	0.003 (3)	0.003 (3)	0.005 (3)
C5	0.040 (3)	0.039 (4)	0.030 (3)	0.017 (3)	0.009 (3)	−0.010 (3)
C6	0.038 (4)	0.042 (4)	0.044 (4)	0.012 (3)	0.012 (3)	−0.006 (3)
C7	0.038 (3)	0.043 (4)	0.026 (3)	0.002 (3)	0.006 (3)	0.003 (3)
C8	0.054 (4)	0.032 (4)	0.051 (4)	0.007 (3)	0.000 (3)	−0.008 (3)
C9	0.039 (4)	0.038 (3)	0.035 (3)	−0.007 (3)	0.006 (3)	−0.001 (3)
C10	0.047 (4)	0.028 (3)	0.044 (4)	0.016 (3)	0.000 (3)	0.007 (3)
C11	0.047 (4)	0.035 (4)	0.041 (4)	0.011 (3)	−0.002 (3)	−0.016 (3)
C12	0.038 (4)	0.031 (4)	0.073 (5)	0.002 (3)	−0.003 (3)	−0.008 (3)
C13	0.043 (4)	0.047 (4)	0.038 (4)	0.005 (3)	0.001 (3)	−0.005 (3)
C14	0.038 (3)	0.032 (3)	0.040 (4)	−0.011 (3)	−0.020 (3)	0.017 (3)
N1	0.036 (3)	0.040 (3)	0.044 (3)	0.009 (2)	0.008 (2)	−0.015 (3)
N2	0.047 (3)	0.042 (3)	0.037 (3)	0.007 (3)	0.016 (3)	−0.002 (2)
N3	0.046 (3)	0.039 (3)	0.038 (3)	0.002 (3)	0.014 (2)	−0.007 (2)
N4	0.044 (3)	0.045 (3)	0.040 (3)	−0.020 (3)	−0.014 (3)	0.010 (3)
O1	0.036 (2)	0.043 (3)	0.034 (2)	0.001 (2)	0.0127 (19)	−0.0118 (19)
O2	0.036 (2)	0.032 (2)	0.041 (2)	−0.0120 (19)	0.0114 (19)	0.0163 (19)
O1W	0.139 (9)	0.154 (9)	0.141 (9)	−0.022 (7)	0.014 (7)	−0.009 (7)
O2W	0.133 (8)	0.115 (8)	0.208 (12)	0.016 (6)	0.076 (8)	0.047 (8)
O3W	0.123 (7)	0.119 (7)	0.118 (7)	−0.016 (6)	0.000 (6)	0.015 (6)

Cl1—C8	1.763 (7)	C7—C8	1.411 (10)
Cl2—Cu1	2.484 (2)	C7—H7	0.9300
Cu1—O2	1.865 (4)	C8—C9	1.420 (10)
Cu1—O1	1.941 (4)	C9—C10	1.377 (9)
Cu1—N2	1.965 (6)	C9—H9	0.9300
Cu1—N1	2.017 (6)	C10—C11	1.408 (9)
Cu1—Cu2	3.0040 (18)	C11—N3	1.319 (9)
Cu2—O2	1.797 (4)	C11—H11	0.9300
Cu2—N4	1.994 (6)	C12—N3	1.508 (9)
Cu2—O1	1.997 (5)	C12—C13	1.542 (10)
Cu2—N3	2.048 (6)	C12—H12A	0.9700
C1—N1	1.498 (8)	C12—H12B	0.9700
C1—C2	1.524 (9)	C13—C14	1.565 (9)
C1—H1A	0.9700	C13—H13A	0.9700
C1—H1B	0.9700	C13—H13B	0.9700
C2—C3	1.543 (10)	C14—N4	1.496 (7)
C2—H2A	0.9700	C14—H14A	0.9700
C2—H2B	0.9700	C14—H14B	0.9700
C3—N2	1.503 (9)	N1—H1C	0.9000
C3—H3A	0.9700	N1—H1D	0.9000
C3—H3B	0.9700	N4—H4A	0.9000
C4—N2	1.333 (9)	N4—H4B	0.9000
C4—C6	1.384 (10)	O1W—H1WD	0.8501
C4—H4	0.9300	O1W—H1WC	0.8499
C5—O1	1.353 (8)	O2W—H2WD	0.8496
C5—C10	1.401 (10)	O2W—H2WB	0.8500
C5—C6	1.420 (9)	O3W—H3WD	0.8500
C6—C7	1.378 (10)	O3W—H3WA	0.8501
O2—Cu1—O1	74.6 (2)	C7—C8—C9	120.1 (6)
O2—Cu1—N2	163.2 (2)	C7—C8—Cl1	119.4 (5)
O1—Cu1—N2	91.8 (2)	C9—C8—Cl1	120.5 (5)
O2—Cu1—N1	95.8 (2)	C10—C9—C8	119.0 (6)
O1—Cu1—N1	167.6 (2)	C10—C9—H9	120.5
N2—Cu1—N1	96.2 (2)	C8—C9—H9	120.5
O2—Cu1—Cl2	97.57 (13)	C9—C10—C5	121.7 (6)
O1—Cu1—Cl2	90.79 (13)	C9—C10—C11	111.5 (6)
N2—Cu1—Cl2	92.30 (16)	C5—C10—C11	126.7 (6)
N1—Cu1—Cl2	98.30 (17)	N3—C11—C10	131.2 (7)
O2—Cu1—Cu2	34.16 (13)	N3—C11—H11	114.4
O1—Cu1—Cu2	41.00 (14)	C10—C11—H11	114.4
N2—Cu1—Cu2	132.74 (18)	N3—C12—C13	117.3 (6)
N1—Cu1—Cu2	129.95 (17)	N3—C12—H12A	108.0
Cl2—Cu1—Cu2	90.55 (6)	C13—C12—H12A	108.0
O2—Cu2—N4	97.5 (2)	N3—C12—H12B	108.0
O2—Cu2—O1	74.66 (19)	C13—C12—H12B	108.0
N4—Cu2—O1	170.4 (2)	H12A—C12—H12B	107.2
O2—Cu2—N3	165.6 (2)	C12—C13—C14	106.7 (5)
N4—Cu2—N3	95.9 (2)	C12—C13—H13A	110.4
O1—Cu2—N3	92.4 (2)	C14—C13—H13A	110.4
O2—Cu2—Cu1	35.64 (14)	C12—C13—H13B	110.4
N4—Cu2—Cu1	133.09 (16)	C14—C13—H13B	110.4
O1—Cu2—Cu1	39.61 (13)	H13A—C13—H13B	108.6
N3—Cu2—Cu1	130.51 (17)	N4—C14—C13	119.2 (5)
N1—C1—C2	120.0 (6)	N4—C14—H14A	107.5
N1—C1—H1A	107.3	C13—C14—H14A	107.5
C2—C1—H1A	107.3	N4—C14—H14B	107.5
N1—C1—H1B	107.3	C13—C14—H14B	107.5
C2—C1—H1B	107.3	H14A—C14—H14B	107.0
H1A—C1—H1B	106.9	C1—N1—Cu1	123.3 (4)
C1—C2—C3	110.1 (6)	C1—N1—H1C	106.5
C1—C2—H2A	109.6	Cu1—N1—H1C	106.5
C3—C2—H2A	109.6	C1—N1—H1D	106.5
C1—C2—H2B	109.6	Cu1—N1—H1D	106.5
C3—C2—H2B	109.6	H1C—N1—H1D	106.5
H2A—C2—H2B	108.2	C4—N2—C3	116.4 (6)
N2—C3—C2	114.1 (5)	C4—N2—Cu1	123.3 (5)
N2—C3—H3A	108.7	C3—N2—Cu1	120.2 (4)
C2—C3—H3A	108.7	C11—N3—C12	123.0 (6)
N2—C3—H3B	108.7	C11—N3—Cu2	119.3 (5)
C2—C3—H3B	108.7	C12—N3—Cu2	117.5 (4)
H3A—C3—H3B	107.6	C14—N4—Cu2	123.4 (4)
N2—C4—C6	126.7 (6)	C14—N4—H4A	106.5
N2—C4—H4	116.7	Cu2—N4—H4A	106.5
C6—C4—H4	116.7	C14—N4—H4B	106.5
O1—C5—C10	119.5 (6)	Cu2—N4—H4B	106.5
O1—C5—C6	121.8 (6)	H4A—N4—H4B	106.5
C10—C5—C6	118.7 (6)	C5—O1—Cu1	124.8 (4)
C7—C6—C4	114.4 (6)	C5—O1—Cu2	129.2 (4)
C7—C6—C5	120.6 (7)	Cu1—O1—Cu2	99.4 (2)
C4—C6—C5	124.8 (7)	Cu2—O2—Cu1	110.2 (2)
C6—C7—C8	119.8 (6)	H1WD—O1W—H1WC	109.5
C6—C7—H7	120.1	H2WD—O2W—H2WB	109.5
C8—C7—H7	120.1	H3WD—O3W—H3WA	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WD···Cl1	0.85	1.90	2.583 (12)	136
O2W—H2WB···O3W	0.85	2.57	3.114 (13)	123
O3W—H3WD···Cl2	0.85	2.70	3.478 (10)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WD⋯Cl1	0.85	1.90	2.583 (12)	136
O2W—H2WB⋯O3W	0.85	2.57	3.114 (13)	123
O3W—H3WD⋯Cl2	0.85	2.70	3.478 (10)	152