Di-μ-thio-cyanato-κN:N-bis-({5-meth-oxy-2-[3-(methyl-amino)propyl-imino-meth-yl]phenolato-κO,N,N'}copper(II)).

The title thio-cyanate-bridged dinuclear copper(II) complex, [Cu(2)(C(12)H(17)N(2)O(2))(2)(NCS)(2)], possesses crystallographic inversion symmetry. Each Cu(II) atom is five-coordinated by one imine N, one amine N and one phenolate O atom of the Schiff base ligand, and by two N atoms from two bridging thio-cyanate ligands, forming a square-pyramidal geometry. Beside the two thio-cyanate bridges, there are two intra-molecular N-H⋯O hydrogen bonds, which further link the two Cu(C(12)H(17)N(2)O(2))(NCS) units. The Cu⋯Cu separation is 3.261 (2) Å. Parts of the methylaminopropylimino segment are disordered over two sites with occupancies of 0.669(9) and 0.331(9).

Related literature

For general background to copper complexes, see: Reddy et al. (2000 ▶); Ray et al. (2003 ▶); Arnold et al. (2003 ▶); Raptopoulou et al. (1998 ▶). For our previous reports of copper(II) complexes, see: Wang & Li (2005 ▶); Wang et al. (2006 ▶). For related structures, see: Elmali et al. (2000 ▶); You & Zhu (2005 ▶); Liu et al. (2004 ▶); Datta et al. (2008 ▶); Habibi et al. (2007 ▶).

Experimental

Crystal data

[Cu2(C12H17N2O2)2(NCS)2]

M = 685.79

Monoclinic,

a = 11.8003 (18) Å

b = 15.373 (2) Å

c = 8.6740 (13) Å

β = 108.972 (7)°

V = 1488.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.61 mm−1

T = 298 K

0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.739, T max = 0.760

9297 measured reflections

3544 independent reflections

2496 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.108

S = 1.05

3544 reflections

211 parameters

50 restraints

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; 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: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015564/ci5079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015564/ci5079Isup2.hkl

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

[Cu2(C12H17N2O2)2(NCS)2]	F(000) = 708
Mr = 685.79	Dx = 1.531 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2304 reflections
a = 11.8003 (18) Å	θ = 2.5–25.1°
b = 15.373 (2) Å	µ = 1.61 mm−1
c = 8.6740 (13) Å	T = 298 K
β = 108.972 (7)°	Block, blue
V = 1488.0 (4) Å3	0.20 × 0.20 × 0.18 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	3544 independent reflections
Radiation source: fine-focus sealed tube	2496 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω scans	θmax = 28.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.739, Tmax = 0.760	k = −20→19
9297 measured reflections	l = −11→10

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0508P)2 + 0.2175P] where P = (Fo2 + 2Fc2)/3
3544 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.48 e Å−3
50 restraints	Δρmin = −0.41 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	Occ. (<1)
Cu1	0.44981 (3)	0.09693 (2)	0.01842 (4)	0.04380 (14)
S1	0.77288 (9)	0.09042 (7)	−0.17937 (13)	0.0751 (3)
O1	0.33324 (18)	0.07895 (14)	−0.1912 (2)	0.0557 (6)
O2	−0.03088 (19)	0.11364 (15)	−0.6308 (3)	0.0612 (6)
N1	0.3347 (2)	0.14948 (17)	0.1093 (3)	0.0578 (7)
N2	0.5877 (3)	0.1033 (2)	0.2257 (4)	0.0775 (10)
H2A	0.6321	0.0548	0.2262	0.093*	0.669 (9)
H2B	0.6324	0.0572	0.2174	0.093*	0.331 (9)
N3	0.5707 (2)	0.06534 (19)	−0.0884 (3)	0.0608 (7)
C1	0.1697 (2)	0.15468 (16)	−0.1467 (3)	0.0412 (6)
C2	0.2230 (2)	0.10933 (17)	−0.2462 (4)	0.0433 (7)
C3	0.1564 (3)	0.09443 (17)	−0.4110 (4)	0.0447 (7)
H3	0.1906	0.0638	−0.4774	0.054*
C4	0.0408 (2)	0.12515 (19)	−0.4741 (4)	0.0458 (7)
C5	−0.0121 (3)	0.1713 (2)	−0.3762 (4)	0.0558 (8)
H5	−0.0897	0.1925	−0.4201	0.067*
C6	0.0507 (3)	0.18466 (18)	−0.2176 (4)	0.0516 (7)
H6	0.0145	0.2146	−0.1528	0.062*
C7	0.0149 (3)	0.0685 (2)	−0.7408 (4)	0.0664 (9)
H7A	0.0827	0.0993	−0.7513	0.080*
H7B	−0.0461	0.0646	−0.8454	0.080*
H7C	0.0391	0.0110	−0.6998	0.080*
C8	0.2262 (3)	0.16936 (18)	0.0221 (4)	0.0516 (7)
H8	0.1799	0.1965	0.0768	0.062*
C9	0.3506 (5)	0.1469 (5)	0.2885 (6)	0.0633 (17)	0.669 (9)
H9A	0.3322	0.0889	0.3178	0.076*	0.669 (9)
H9B	0.2951	0.1872	0.3117	0.076*	0.669 (9)
C10	0.4770 (5)	0.1705 (5)	0.3900 (8)	0.068 (2)	0.669 (9)
H10A	0.4972	0.2259	0.3522	0.082*	0.669 (9)
H10B	0.4798	0.1780	0.5022	0.082*	0.669 (9)
C11	0.5706 (8)	0.1048 (6)	0.3857 (7)	0.080 (3)	0.669 (9)
H11A	0.6459	0.1191	0.4689	0.096*	0.669 (9)
H11B	0.5462	0.0475	0.4098	0.096*	0.669 (9)
C9A	0.3884 (12)	0.1980 (8)	0.2722 (11)	0.068 (4)	0.331 (9)
H9AA	0.4489	0.2391	0.2655	0.082*	0.331 (9)
H9AB	0.3265	0.2293	0.3004	0.082*	0.331 (9)
C10A	0.4432 (15)	0.1287 (10)	0.397 (2)	0.086 (5)	0.331 (9)
H10C	0.3808	0.0888	0.4019	0.103*	0.331 (9)
H10D	0.4758	0.1559	0.5033	0.103*	0.331 (9)
C11A	0.5414 (14)	0.0777 (10)	0.3617 (15)	0.085 (6)	0.331 (9)
H11C	0.6096	0.0773	0.4613	0.102*	0.331 (9)
H11D	0.5137	0.0181	0.3414	0.102*	0.331 (9)
C12	0.6695 (4)	0.1786 (3)	0.2263 (7)	0.1234 (19)
H12A	0.6282	0.2323	0.2276	0.148*
H12B	0.6930	0.1762	0.1303	0.148*
H12C	0.7394	0.1753	0.3214	0.148*
C13	0.6548 (3)	0.07722 (19)	−0.1263 (4)	0.0500 (7)

	U11	U22	U33	U12	U13	U23
Cu1	0.0406 (2)	0.0484 (2)	0.0408 (2)	0.00958 (15)	0.01100 (16)	−0.00055 (14)
S1	0.0543 (5)	0.1109 (8)	0.0669 (6)	−0.0065 (5)	0.0290 (5)	0.0033 (5)
O1	0.0440 (12)	0.0789 (15)	0.0409 (11)	0.0279 (10)	0.0095 (9)	−0.0046 (10)
O2	0.0424 (12)	0.0714 (15)	0.0598 (15)	0.0034 (10)	0.0026 (11)	−0.0030 (11)
N1	0.0597 (16)	0.0727 (18)	0.0399 (14)	0.0239 (14)	0.0149 (13)	−0.0057 (12)
N2	0.0566 (18)	0.093 (2)	0.063 (2)	0.0254 (16)	−0.0074 (15)	−0.0285 (16)
N3	0.0474 (15)	0.0776 (18)	0.0592 (17)	0.0080 (14)	0.0195 (14)	0.0049 (14)
C1	0.0389 (14)	0.0394 (14)	0.0484 (16)	0.0053 (12)	0.0185 (13)	0.0028 (12)
C2	0.0404 (15)	0.0425 (16)	0.0472 (17)	0.0080 (12)	0.0146 (13)	0.0073 (12)
C3	0.0411 (15)	0.0495 (16)	0.0435 (16)	0.0043 (12)	0.0140 (13)	0.0037 (12)
C4	0.0387 (16)	0.0446 (15)	0.0500 (17)	0.0000 (12)	0.0088 (14)	0.0074 (13)
C5	0.0328 (15)	0.0577 (19)	0.073 (2)	0.0075 (13)	0.0113 (16)	0.0021 (16)
C6	0.0410 (16)	0.0481 (17)	0.070 (2)	0.0043 (13)	0.0239 (16)	−0.0047 (14)
C7	0.061 (2)	0.079 (2)	0.0491 (19)	−0.0022 (18)	0.0044 (17)	0.0007 (17)
C8	0.0577 (19)	0.0498 (17)	0.0539 (18)	0.0126 (14)	0.0271 (16)	0.0011 (14)
C9	0.072 (4)	0.075 (4)	0.044 (3)	0.013 (3)	0.021 (3)	−0.004 (3)
C10	0.080 (4)	0.073 (4)	0.042 (3)	0.010 (3)	0.007 (3)	−0.021 (3)
C11	0.104 (5)	0.086 (5)	0.030 (3)	0.029 (4)	−0.007 (3)	−0.017 (3)
C9A	0.070 (7)	0.080 (7)	0.053 (6)	0.028 (6)	0.018 (5)	−0.008 (5)
C10A	0.089 (9)	0.106 (9)	0.062 (7)	0.005 (7)	0.024 (7)	0.018 (7)
C11A	0.100 (9)	0.085 (8)	0.038 (7)	0.041 (7)	−0.022 (6)	−0.032 (6)
C12	0.066 (3)	0.138 (4)	0.148 (4)	−0.020 (3)	0.010 (3)	−0.070 (3)
C13	0.0459 (17)	0.0568 (18)	0.0452 (17)	0.0038 (14)	0.0118 (15)	0.0024 (13)

Cu1—O1	1.910 (2)	C5—H5	0.93
Cu1—N1	1.953 (2)	C6—H6	0.93
Cu1—N2	1.997 (3)	C7—H7A	0.96
Cu1—N3	1.998 (3)	C7—H7B	0.96
Cu1—N3i	2.598 (4)	C7—H7C	0.96
S1—C13	1.616 (3)	C8—H8	0.93
O1—C2	1.317 (3)	C9—C10	1.509 (6)
O2—C4	1.359 (3)	C9—H9A	0.97
O2—C7	1.421 (4)	C9—H9B	0.97
N1—C8	1.294 (4)	C10—C11	1.506 (6)
N1—C9	1.504 (5)	C10—H10A	0.97
N1—C9A	1.540 (8)	C10—H10B	0.97
N2—C11	1.467 (6)	C11—H11A	0.97
N2—C12	1.505 (5)	C11—H11B	0.97
N2—C11A	1.506 (9)	C9A—C10A	1.507 (8)
N2—H2A	0.91	C9A—H9AA	0.97
N2—H2B	0.90	C9A—H9AB	0.97
N3—C13	1.157 (4)	C10A—C11A	1.510 (8)
C1—C2	1.407 (4)	C10A—H10C	0.97
C1—C6	1.415 (4)	C10A—H10D	0.97
C1—C8	1.416 (4)	C11A—H11C	0.97
C2—C3	1.408 (4)	C11A—H11D	0.97
C3—C4	1.378 (4)	C12—H12A	0.96
C3—H3	0.93	C12—H12B	0.96
C4—C5	1.399 (4)	C12—H12C	0.96
C5—C6	1.350 (4)
O1—Cu1—N1	93.67 (10)	H7A—C7—H7B	109.5
O1—Cu1—N2	171.12 (10)	O2—C7—H7C	109.5
N1—Cu1—N2	94.96 (12)	H7A—C7—H7C	109.5
O1—Cu1—N3	85.70 (10)	H7B—C7—H7C	109.5
N1—Cu1—N3	169.45 (12)	N1—C8—C1	127.6 (3)
N2—Cu1—N3	86.20 (12)	N1—C8—H8	116.2
N3i—Cu1—N1	99.91 (15)	C1—C8—H8	116.2
N3i—Cu1—N2	87.06 (15)	N1—C9—C10	111.3 (5)
N3i—Cu1—N3	90.57 (15)	N1—C9—H9A	109.4
N3i—Cu1—O1	89.50 (15)	C10—C9—H9A	109.4
C2—O1—Cu1	127.91 (18)	N1—C9—H9B	109.4
C4—O2—C7	119.1 (2)	C10—C9—H9B	109.4
C8—N1—C9	112.2 (3)	H9A—C9—H9B	108.0
C8—N1—C9A	117.1 (5)	C11—C10—C9	114.7 (6)
C8—N1—Cu1	123.2 (2)	C11—C10—H10A	108.6
C9—N1—Cu1	122.4 (3)	C9—C10—H10A	108.6
C9A—N1—Cu1	116.0 (5)	C11—C10—H10B	108.6
C11—N2—C12	105.7 (5)	C9—C10—H10B	108.6
C12—N2—C11A	126.4 (7)	H10A—C10—H10B	107.6
C11—N2—Cu1	122.0 (4)	N2—C11—C10	111.2 (5)
C12—N2—Cu1	112.0 (3)	N2—C11—H11A	109.4
C11A—N2—Cu1	107.2 (7)	C10—C11—H11A	109.4
C11—N2—H2A	105.3	N2—C11—H11B	109.4
C12—N2—H2A	105.3	C10—C11—H11B	109.4
C11A—N2—H2A	97.8	H11A—C11—H11B	108.0
Cu1—N2—H2A	105.3	C10A—C9A—N1	105.7 (11)
C11—N2—H2B	110.6	C10A—C9A—H9AA	110.6
C12—N2—H2B	102.4	N1—C9A—H9AA	110.6
C11A—N2—H2B	103.1	C10A—C9A—H9AB	110.6
Cu1—N2—H2B	102.5	N1—C9A—H9AB	110.6
C13—N3—Cu1	154.3 (3)	H9AA—C9A—H9AB	108.7
C2—C1—C6	118.3 (3)	C9A—C10A—C11A	113.5 (12)
C2—C1—C8	124.0 (3)	C9A—C10A—H10C	108.9
C6—C1—C8	117.7 (3)	C11A—C10A—H10C	108.9
O1—C2—C1	122.6 (3)	C9A—C10A—H10D	108.9
O1—C2—C3	118.0 (3)	C11A—C10A—H10D	108.9
C1—C2—C3	119.3 (3)	H10C—C10A—H10D	107.7
C4—C3—C2	120.1 (3)	N2—C11A—C10A	121.4 (11)
C4—C3—H3	120.0	N2—C11A—H11C	107.0
C2—C3—H3	120.0	C10A—C11A—H11C	107.0
O2—C4—C3	124.5 (3)	N2—C11A—H11D	107.0
O2—C4—C5	114.7 (2)	C10A—C11A—H11D	107.0
C3—C4—C5	120.8 (3)	H11C—C11A—H11D	106.7
C6—C5—C4	119.4 (3)	N2—C12—H12A	109.5
C6—C5—H5	120.3	N2—C12—H12B	109.5
C4—C5—H5	120.3	H12A—C12—H12B	109.5
C5—C6—C1	122.1 (3)	N2—C12—H12C	109.5
C5—C6—H6	118.9	H12A—C12—H12C	109.5
C1—C6—H6	118.9	H12B—C12—H12C	109.5
O2—C7—H7A	109.5	N3—C13—S1	178.1 (3)
O2—C7—H7B	109.5
N1—Cu1—O1—C2	10.5 (3)	C7—O2—C4—C5	179.3 (3)
N3—Cu1—O1—C2	−159.0 (3)	C2—C3—C4—O2	−179.5 (3)
O1—Cu1—N1—C8	−8.2 (3)	C2—C3—C4—C5	0.0 (4)
N2—Cu1—N1—C8	173.9 (3)	O2—C4—C5—C6	178.6 (3)
N3—Cu1—N1—C8	78.0 (7)	C3—C4—C5—C6	−0.9 (4)
O1—Cu1—N1—C9	153.7 (4)	C4—C5—C6—C1	1.0 (5)
N2—Cu1—N1—C9	−24.2 (4)	C2—C1—C6—C5	−0.2 (4)
N3—Cu1—N1—C9	−120.1 (6)	C8—C1—C6—C5	−177.8 (3)
O1—Cu1—N1—C9A	−165.8 (6)	C9—N1—C8—C1	−160.8 (4)
N2—Cu1—N1—C9A	16.3 (6)	C9A—N1—C8—C1	160.1 (7)
N3—Cu1—N1—C9A	−79.5 (8)	Cu1—N1—C8—C1	2.8 (5)
N1—Cu1—N2—C11	25.6 (5)	C2—C1—C8—N1	4.5 (5)
N3—Cu1—N2—C11	−164.9 (5)	C6—C1—C8—N1	−178.0 (3)
N1—Cu1—N2—C12	−101.1 (3)	C8—N1—C9—C10	−150.3 (5)
N3—Cu1—N2—C12	68.4 (3)	C9A—N1—C9—C10	−44.3 (8)
N1—Cu1—N2—C11A	41.7 (6)	Cu1—N1—C9—C10	46.0 (7)
N3—Cu1—N2—C11A	−148.9 (6)	N1—C9—C10—C11	−68.3 (9)
O1—Cu1—N3—C13	123.7 (6)	C12—N2—C11—C10	81.1 (7)
N1—Cu1—N3—C13	36.7 (10)	C11A—N2—C11—C10	−97 (2)
N2—Cu1—N3—C13	−60.0 (6)	Cu1—N2—C11—C10	−48.3 (8)
Cu1—O1—C2—C1	−6.7 (4)	C9—C10—C11—N2	69.8 (9)
Cu1—O1—C2—C3	174.05 (19)	C8—N1—C9A—C10A	132.2 (9)
C6—C1—C2—O1	−180.0 (2)	C9—N1—C9A—C10A	41.3 (8)
C8—C1—C2—O1	−2.5 (4)	Cu1—N1—C9A—C10A	−68.8 (12)
C6—C1—C2—C3	−0.8 (4)	N1—C9A—C10A—C11A	60.8 (18)
C8—C1—C2—C3	176.7 (3)	C11—N2—C11A—C10A	78 (2)
O1—C2—C3—C4	−179.9 (2)	C12—N2—C11A—C10A	75.1 (16)
C1—C2—C3—C4	0.9 (4)	Cu1—N2—C11A—C10A	−60.6 (15)
C7—O2—C4—C3	−1.2 (4)	C9A—C10A—C11A—N2	7(2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1i	0.91	2.14	2.999 (3)	157

Table 1

Selected bond lengths (Å)

Cu1—O1	1.910 (2)
Cu1—N1	1.953 (2)
Cu1—N2	1.997 (3)
Cu1—N3	1.998 (3)
Cu1—N3i	2.598 (4)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1i	0.91	2.14	2.999 (3)	157

Symmetry code: (i) .