Bis[μ-2-(2-pyridylmethyl-amino-meth-yl)phenolato]-κN,N',O:O;κO:N,N',O-bis-[(thio-cyanato-κN)copper(II)].

The centrosymmetric binuclear complex, [Cu(2)(C(13)H(13)N(2)O)(2)(NCS)(2)], formed via phenolate oxygen bridges, involves the Cu(II) atoms in a distorted square-pyramidal coordination [τ = 0.197 (1)]. A Cu⋯Cu separation of 3.2281 (3) Å is observed. The in-plane Cu-O(phenolate) distance [1.9342 (8) Å] is shorter than the axial distance [2.252 (8) Å]. The Cu-N(amine) and Cu-N(py) distances are similar [2.0095 (10) and 2.0192 (10) Å, respectively]. The Cu-N(thio-cyanate) distance [1.9678 (11) Å] is in the range found for Cu-N distances in previously determined structures containing coordinated thio-cyanate anions. There is an inter-molecular hydrogen bond between the amine H atom and the S atom of a coordinated thio-cyanate anion.

Related literature

For the chemical properties, ligand binding properties and the synthesis of related copper complexes: Kuzmic et al. (1992 ▶); Lim et al. (2006 ▶); Rogers & Wolf (2002 ▶); Sharma et al. (2008 ▶); Yisgedu (2001 ▶). For related structures, see: Assey et al. (2009 ▶); Biswas et al. (2005 ▶); Sarkar et al. (2006 ▶); Shakya et al. (2006 ▶); Wang & Li (2005 ▶); You & Zhu (2004 ▶, 2005 ▶); You (2005 ▶). For the τ parameter, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu2(C13H13N2O)2(NCS)2]

M = 669.75

Monoclinic,

a = 7.4747 (1) Å

b = 16.9237 (3) Å

c = 11.0714 (2) Å

β = 91.1317 (18)°

V = 1400.25 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.71 mm−1

T = 200 K

0.44 × 0.37 × 0.28 mm

Data collection

Oxford Diffraction Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.944, T max = 1.000 (expected range = 0.586–0.620)

18586 measured reflections

7024 independent reflections

4611 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.071

S = 0.89

7024 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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 I, global. DOI: 10.1107/S1600536809031742/kp2227sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031742/kp2227Isup2.hkl

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

[Cu2(C13H13N2O)2(NCS)2]	F(000) = 684
Mr = 669.75	Dx = 1.588 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4747 (1) Å	Cell parameters from 7409 reflections
b = 16.9237 (3) Å	θ = 4.5–37.4°
c = 11.0714 (2) Å	µ = 1.71 mm−1
β = 91.1317 (18)°	T = 200 K
V = 1400.25 (4) Å3	Chunk, dark green
Z = 2	0.44 × 0.37 × 0.28 mm

Oxford Diffraction Gemini R diffractometer	7024 independent reflections
Radiation source: fine-focus sealed tube	4611 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 10.5081 pixels mm-1	θmax = 37.5°, θmin = 4.5°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −28→25
Tmin = 0.944, Tmax = 1.000	l = −18→12
18586 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H-atom parameters constrained
S = 0.89	w = 1/[σ2(Fo2) + (0.037P)2] where P = (Fo2 + 2Fc2)/3
7024 reflections	(Δ/σ)max = 0.004
181 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.15 (release 10-01-2008 CrysAlis171 .NET) (compiled Jan 10 2008,16:37:18) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	0.200074 (18)	0.530744 (8)	0.531057 (12)	0.01989 (4)
S	0.40414 (4)	0.472939 (18)	0.13944 (3)	0.02856 (7)
O	0.07568 (10)	0.43052 (4)	0.52958 (7)	0.02117 (15)
N	0.31981 (15)	0.51404 (7)	0.37642 (10)	0.0315 (2)
N1	0.19612 (12)	0.53813 (5)	0.71214 (9)	0.02082 (18)
H1A	0.3146	0.5407	0.7390	0.025*
N2	0.27182 (13)	0.64484 (6)	0.55436 (9)	0.02351 (19)
C	0.35464 (15)	0.49643 (7)	0.27835 (11)	0.0232 (2)
C1	0.13193 (14)	0.37486 (6)	0.60789 (10)	0.0201 (2)
C2	0.15668 (15)	0.29704 (7)	0.56836 (11)	0.0243 (2)
H2A	0.1256	0.2832	0.4875	0.029*
C3	0.22630 (16)	0.23993 (7)	0.64630 (12)	0.0286 (3)
H3A	0.2415	0.1873	0.6185	0.034*
C4	0.27368 (17)	0.25921 (8)	0.76442 (12)	0.0314 (3)
H4A	0.3271	0.2208	0.8163	0.038*
C5	0.24208 (16)	0.33520 (7)	0.80592 (11)	0.0271 (2)
H5A	0.2722	0.3483	0.8873	0.033*
C6	0.16704 (15)	0.39265 (7)	0.73042 (10)	0.0216 (2)
C7	0.11123 (16)	0.47201 (6)	0.77868 (11)	0.0238 (2)
H7A	−0.0205	0.4770	0.7716	0.029*
H7B	0.1453	0.4756	0.8654	0.029*
C8	0.11526 (16)	0.61569 (7)	0.73720 (11)	0.0253 (2)
H8A	0.1373	0.6305	0.8227	0.030*
H8B	−0.0156	0.6136	0.7220	0.030*
C9	0.19939 (15)	0.67555 (6)	0.65499 (11)	0.0232 (2)
C10	0.20102 (17)	0.75594 (7)	0.67794 (12)	0.0293 (3)
H10A	0.1478	0.7766	0.7485	0.035*
C11	0.28194 (18)	0.80584 (7)	0.59583 (14)	0.0351 (3)
H11A	0.2836	0.8613	0.6091	0.042*
C12	0.35985 (17)	0.77426 (7)	0.49476 (13)	0.0330 (3)
H12A	0.4180	0.8075	0.4386	0.040*
C13	0.35215 (17)	0.69330 (7)	0.47618 (12)	0.0287 (2)
H13A	0.4051	0.6715	0.4063	0.034*

	U11	U22	U33	U12	U13	U23
Cu	0.02292 (7)	0.01935 (6)	0.01741 (7)	−0.00059 (5)	0.00062 (5)	−0.00060 (5)
S	0.03068 (15)	0.03244 (15)	0.02262 (15)	0.00118 (12)	0.00194 (11)	−0.00631 (12)
O	0.0239 (4)	0.0196 (3)	0.0198 (4)	0.0005 (3)	−0.0051 (3)	0.0021 (3)
N	0.0326 (6)	0.0367 (6)	0.0256 (5)	−0.0008 (4)	0.0074 (4)	−0.0037 (4)
N1	0.0204 (4)	0.0215 (4)	0.0205 (5)	0.0007 (3)	−0.0009 (3)	−0.0009 (3)
N2	0.0214 (4)	0.0230 (4)	0.0260 (5)	−0.0020 (3)	−0.0025 (4)	0.0003 (4)
C	0.0199 (5)	0.0226 (5)	0.0271 (6)	0.0003 (4)	0.0010 (4)	0.0003 (4)
C1	0.0180 (4)	0.0210 (5)	0.0215 (5)	0.0000 (4)	0.0004 (4)	0.0033 (4)
C2	0.0268 (5)	0.0218 (5)	0.0243 (6)	0.0014 (4)	0.0018 (4)	0.0008 (4)
C3	0.0298 (6)	0.0207 (5)	0.0356 (7)	0.0043 (4)	0.0055 (5)	0.0048 (5)
C4	0.0310 (6)	0.0296 (6)	0.0336 (7)	0.0067 (5)	0.0014 (5)	0.0138 (5)
C5	0.0282 (6)	0.0311 (6)	0.0219 (6)	0.0002 (5)	−0.0026 (4)	0.0068 (5)
C6	0.0216 (5)	0.0229 (5)	0.0204 (5)	−0.0007 (4)	−0.0002 (4)	0.0041 (4)
C7	0.0284 (5)	0.0253 (5)	0.0176 (5)	−0.0001 (4)	0.0024 (4)	0.0015 (4)
C8	0.0280 (6)	0.0230 (5)	0.0249 (6)	0.0006 (4)	0.0024 (4)	−0.0056 (4)
C9	0.0223 (5)	0.0223 (5)	0.0249 (6)	0.0002 (4)	−0.0045 (4)	−0.0026 (4)
C10	0.0313 (6)	0.0236 (5)	0.0329 (7)	0.0002 (5)	−0.0042 (5)	−0.0055 (5)
C11	0.0353 (7)	0.0211 (5)	0.0484 (9)	−0.0039 (5)	−0.0095 (6)	−0.0004 (5)
C12	0.0302 (6)	0.0279 (6)	0.0405 (8)	−0.0065 (5)	−0.0043 (5)	0.0071 (5)
C13	0.0270 (5)	0.0294 (6)	0.0297 (7)	−0.0040 (5)	0.0000 (5)	0.0036 (5)

Cu—O	1.9342 (8)	C3—H3A	0.9500
Cu—N	1.9678 (11)	C4—C5	1.3874 (18)
Cu—N1	2.0095 (10)	C4—H4A	0.9500
Cu—N2	2.0192 (10)	C5—C6	1.3929 (16)
Cu—Oi	2.2526 (8)	C5—H5A	0.9500
S—C	1.6378 (12)	C6—C7	1.5073 (16)
O—C1	1.3421 (13)	C7—H7A	0.9900
O—Cui	2.2526 (8)	C7—H7B	0.9900
N—C	1.1605 (16)	C8—C9	1.5076 (16)
N1—C8	1.4737 (14)	C8—H8A	0.9900
N1—C7	1.4886 (14)	C8—H8B	0.9900
N1—H1A	0.9300	C9—C10	1.3840 (16)
N2—C13	1.3427 (15)	C10—C11	1.3882 (19)
N2—C9	1.3521 (15)	C10—H10A	0.9500
C1—C2	1.4012 (15)	C11—C12	1.379 (2)
C1—C6	1.4092 (16)	C11—H11A	0.9500
C2—C3	1.3900 (17)	C12—C13	1.3865 (18)
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.387 (2)	C13—H13A	0.9500
O—Cu—N	95.37 (4)	C5—C4—H4A	120.4
O—Cu—N1	92.66 (3)	C4—C5—C6	121.16 (12)
N—Cu—N1	153.23 (5)	C4—C5—H5A	119.4
O—Cu—N2	165.03 (4)	C6—C5—H5A	119.4
N—Cu—N2	97.14 (4)	C5—C6—C1	119.59 (11)
N1—Cu—N2	79.76 (4)	C5—C6—C7	121.35 (11)
O—Cu—Oi	79.39 (3)	C1—C6—C7	118.94 (10)
N—Cu—Oi	102.22 (4)	N1—C7—C6	111.76 (9)
N1—Cu—Oi	104.35 (3)	N1—C7—H7A	109.3
N2—Cu—Oi	89.94 (3)	C6—C7—H7A	109.3
C1—O—Cu	117.75 (7)	N1—C7—H7B	109.3
C1—O—Cui	132.06 (7)	C6—C7—H7B	109.3
Cu—O—Cui	100.61 (3)	H7A—C7—H7B	107.9
C—N—Cu	164.84 (11)	N1—C8—C9	107.90 (9)
C8—N1—C7	113.33 (9)	N1—C8—H8A	110.1
C8—N1—Cu	104.92 (7)	C9—C8—H8A	110.1
C7—N1—Cu	117.50 (7)	N1—C8—H8B	110.1
C8—N1—H1A	106.8	C9—C8—H8B	110.1
C7—N1—H1A	106.8	H8A—C8—H8B	108.4
Cu—N1—H1A	106.8	N2—C9—C10	121.79 (11)
C13—N2—C9	119.20 (10)	N2—C9—C8	114.69 (9)
C13—N2—Cu	128.51 (9)	C10—C9—C8	123.50 (11)
C9—N2—Cu	111.30 (7)	C9—C10—C11	118.70 (12)
N—C—S	179.16 (12)	C9—C10—H10A	120.7
O—C1—C2	119.97 (10)	C11—C10—H10A	120.7
O—C1—C6	121.46 (10)	C12—C11—C10	119.47 (12)
C2—C1—C6	118.57 (10)	C12—C11—H11A	120.3
C3—C2—C1	120.65 (12)	C10—C11—H11A	120.3
C3—C2—H2A	119.7	C11—C12—C13	119.10 (12)
C1—C2—H2A	119.7	C11—C12—H12A	120.5
C4—C3—C2	120.48 (12)	C13—C12—H12A	120.5
C4—C3—H3A	119.8	N2—C13—C12	121.71 (12)
C2—C3—H3A	119.8	N2—C13—H13A	119.1
C3—C4—C5	119.23 (11)	C12—C13—H13A	119.1
C3—C4—H4A	120.4
N—Cu—O—C1	108.23 (8)	Cui—O—C1—C6	−92.44 (11)
N1—Cu—O—C1	−46.20 (8)	O—C1—C2—C3	175.63 (10)
N2—Cu—O—C1	−105.16 (15)	C6—C1—C2—C3	−4.46 (16)
Oi—Cu—O—C1	−150.31 (9)	C1—C2—C3—C4	−0.47 (18)
N—Cu—O—Cui	−101.46 (4)	C2—C3—C4—C5	3.37 (18)
N1—Cu—O—Cui	104.11 (4)	C3—C4—C5—C6	−1.27 (19)
N2—Cu—O—Cui	45.15 (15)	C4—C5—C6—C1	−3.70 (18)
Oi—Cu—O—Cui	0.0	C4—C5—C6—C7	172.27 (11)
O—Cu—N—C	37.5 (4)	O—C1—C6—C5	−173.61 (10)
N1—Cu—N—C	144.3 (4)	C2—C1—C6—C5	6.48 (16)
N2—Cu—N—C	−134.3 (4)	O—C1—C6—C7	10.32 (15)
Oi—Cu—N—C	−42.8 (4)	C2—C1—C6—C7	−169.59 (10)
O—Cu—N1—C8	−126.33 (7)	C8—N1—C7—C6	166.99 (10)
N—Cu—N1—C8	126.22 (10)	Cu—N1—C7—C6	44.27 (12)
N2—Cu—N1—C8	40.68 (7)	C5—C6—C7—N1	125.30 (11)
Oi—Cu—N1—C8	−46.61 (7)	C1—C6—C7—N1	−58.71 (14)
O—Cu—N1—C7	0.59 (8)	C7—N1—C8—C9	−174.09 (9)
N—Cu—N1—C7	−106.86 (11)	Cu—N1—C8—C9	−44.65 (10)
N2—Cu—N1—C7	167.59 (8)	C13—N2—C9—C10	1.96 (17)
Oi—Cu—N1—C7	80.31 (8)	Cu—N2—C9—C10	−167.62 (9)
O—Cu—N2—C13	−137.76 (14)	C13—N2—C9—C8	−179.11 (10)
N—Cu—N2—C13	8.72 (11)	Cu—N2—C9—C8	11.31 (12)
N1—Cu—N2—C13	161.81 (11)	N1—C8—C9—N2	22.59 (14)
Oi—Cu—N2—C13	−93.59 (10)	N1—C8—C9—C10	−158.50 (11)
O—Cu—N2—C9	30.60 (19)	N2—C9—C10—C11	−1.00 (19)
N—Cu—N2—C9	177.08 (8)	C8—C9—C10—C11	−179.83 (12)
N1—Cu—N2—C9	−29.83 (8)	C9—C10—C11—C12	−0.7 (2)
Oi—Cu—N2—C9	74.77 (8)	C10—C11—C12—C13	1.4 (2)
Cu—N—C—S	117 (8)	C9—N2—C13—C12	−1.24 (18)
Cu—O—C1—C2	−133.51 (9)	Cu—N2—C13—C12	166.32 (10)
Cui—O—C1—C2	87.46 (12)	C11—C12—C13—N2	−0.4 (2)
Cu—O—C1—C6	46.58 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Sii	0.93	2.48	3.3866 (10)	164

Cu—O	1.9342 (8)
Cu—N	1.9678 (11)
Cu—N1	2.0095 (10)
Cu—N2	2.0192 (10)
Cu—Oi	2.2526 (8)

O—Cu—N	95.37 (4)
O—Cu—N1	92.66 (3)
N—Cu—N1	153.23 (5)
O—Cu—N2	165.03 (4)
N—Cu—N2	97.14 (4)
N1—Cu—N2	79.76 (4)
O—Cu—Oi	79.39 (3)
N—Cu—Oi	102.22 (4)
N1—Cu—Oi	104.35 (3)
N2—Cu—Oi	89.94 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Sii	0.93	2.48	3.3866 (10)	164

Symmetry code: (ii) .