Di-μ-thio­cyanato-κ⁴N:N-bis­({2-[2-(methyl­amino)ethyl­imino­meth­yl]­phenolato}copper(II))

The asymmetric unit of the title compound, [Cu₂(NCS)₂(C₁₀H₁₃N₂O)₂], contains one-half of the centrosymmetric dinuclear complex, which exhibits a Cu...Cu separation of 3.255 (2) Å. In the complex, each Cu^II ion is penta­coordinated in a square-pyramidal geometry. The basal plane is formed by one phenol O [Cu—O = 1.910 (4) Å], one imine N [Cu—N = 1.922 (5) Å] and one amine N [Cu—N = 2.041 (5) Å] atoms from the Schiff base ligand, and by the N atom [Cu—N = 1.940 (6) Å] from a thio­cyanate ligand. The apical position is occupied by the N atom [Cu—N = 2.768 (6) Å] of another thio­cyanate ligand. There are intramolecular N—H...O hydrogen bonds linking the two ligands.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.064
• wR factor = 0.160
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

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Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          S
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.22
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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   0 ALERT level B = Potentially serious problem
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   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
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S1. Comment

In continuation of our study of copper complexes with Shiff base ligands (Wei, 2005a,b; Wei & Wang, 2006), we report here the crystal structure of the title compound- a new dinuclear copper(II) complex (Fig. 1).

Each Cu atom in the complex is pentacoordinate in a square pyramidal geometry, with one phenolic O, one imine N, and one amine N atoms of one Schiff base ligand, and with one N atom of a thiocyanate ligand defining the basal plane, and with one N atom of another thiocyanate ligand occupying the apical position. The thiocyanate ligands adopt end-on coordination mode, with the Cu···Cu distance of 3.255 (2) Å. The coordinate bond lengths and angles are comparable with those observed in other Schiff base copper(II) complexes (Diao, Shu et al., 2007; Diao & Li, 2007).

Related literature

For related structures, see: Diao et al. (2007); Diao & Li (2007); Wei (2005a,b); Wei & Wang (2006).

S2. Experimental

Salicyaldehyde (1.0 mmol, 122.1 mg), N-methylethane-1,2-diamine (1.0 mmol, 74.0 mg), NH₄NCS (1.0 mmol, 7.6 mg) and Cu(CH₃COO)₂.H₂O (1.0 mmol, 199.1 mg) were dissolved in a methanol solution (150 ml). The mixture was refluxed at 340 K for about 1 h to give a clear blue solution. After keeping the cooled resulting solution in dark for five days, blue needle-shaped crystals were formed.

S3. Refinement

Atom H2 attached to N2 was located from a difference Fourier map and refined isotropically, with N–H distance restrained to 0.90 (3) Å. Other H atoms were placed geometrically, with C–H distances in the range 0.93–0.97 Å, and with U_iso(H) set to 1.2U_eq(C) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Unlabelled atoms are related with labelled ones by symmetry code (-x + 2, -y, -z + 1).

Di-µ-thiocyanato-κ⁴N:N-bis({2-[2- (methylamino)ethyliminomethyl]phenolato}copper(II))

Crystal data

[Cu2(NCS)2(C10H13N2O)2]	F(000) = 612
Mr = 597.69	Dx = 1.602 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3305 (19) Å	Cell parameters from 944 reflections
b = 16.982 (4) Å	θ = 2.3–24.9°
c = 9.137 (2) Å	µ = 1.92 mm^−1
β = 106.562 (3)°	T = 298 K
V = 1239.0 (5) Å^3	Needle, blue
Z = 2	0.20 × 0.07 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2431 independent reflections
Radiation source: fine-focus sealed tube	1510 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.700, Tmax = 0.894	k = −20→20
9340 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0643P)^2 + 0.4135P] where P = (Fo^2 + 2Fc^2)/3
2431 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.45 e Å^−3
1 restraint	Δρmin = −0.67 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.96892 (9)	0.04411 (4)	0.33613 (8)	0.0410 (3)
S1	1.4907 (3)	0.09746 (15)	0.6792 (3)	0.1066 (10)
O1	1.0498 (5)	−0.0513 (2)	0.2719 (4)	0.0443 (10)
N1	0.7859 (6)	0.0530 (3)	0.1529 (5)	0.0398 (12)
N2	0.8447 (7)	0.1282 (3)	0.4207 (5)	0.0463 (13)
N3	1.1753 (7)	0.0566 (3)	0.4992 (6)	0.0558 (15)
C1	0.8475 (8)	−0.0616 (3)	0.0253 (7)	0.0412 (14)
C2	0.9862 (7)	−0.0881 (3)	0.1430 (6)	0.0372 (14)
C3	1.0614 (9)	−0.1608 (4)	0.1219 (8)	0.0530 (17)
H3	1.1495	−0.1808	0.2000	0.064*
C4	1.0052 (10)	−0.2015 (4)	−0.0123 (9)	0.066 (2)
H4	1.0556	−0.2491	−0.0237	0.079*
C5	0.8739 (10)	−0.1731 (5)	−0.1324 (9)	0.070 (2)
H5	0.8393	−0.2008	−0.2238	0.084*
C6	0.7964 (9)	−0.1042 (4)	−0.1144 (7)	0.0562 (18)
H6	0.7093	−0.0851	−0.1944	0.067*
C7	0.7571 (7)	0.0073 (3)	0.0369 (6)	0.0406 (14)
H7	0.6687	0.0207	−0.0475	0.049*
C8	0.6778 (8)	0.1198 (4)	0.1574 (7)	0.0503 (16)
H8A	0.5665	0.1106	0.0896	0.060*
H8B	0.7224	0.1672	0.1243	0.060*
C9	0.6698 (8)	0.1295 (4)	0.3187 (7)	0.0554 (17)
H9A	0.6163	0.1791	0.3295	0.066*
H9B	0.6054	0.0871	0.3451	0.066*
C10	0.9218 (9)	0.2060 (4)	0.4491 (8)	0.072 (2)
H10A	0.9340	0.2272	0.3554	0.108*
H10B	1.0299	0.2018	0.5224	0.108*
H10C	0.8521	0.2403	0.4881	0.108*
C11	1.3052 (9)	0.0744 (4)	0.5740 (7)	0.0510 (17)
H2	0.841 (9)	0.110 (4)	0.512 (4)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0387 (4)	0.0473 (5)	0.0355 (4)	0.0051 (4)	0.0082 (3)	−0.0031 (4)
S1	0.0748 (16)	0.1044 (19)	0.1027 (17)	−0.0400 (14)	−0.0359 (13)	0.0478 (15)
O1	0.050 (3)	0.049 (3)	0.033 (2)	0.011 (2)	0.0107 (19)	−0.0028 (19)
N1	0.034 (3)	0.045 (3)	0.041 (3)	0.008 (2)	0.011 (2)	0.010 (2)
N2	0.054 (3)	0.044 (3)	0.042 (3)	0.003 (3)	0.017 (3)	−0.010 (2)
N3	0.047 (3)	0.072 (4)	0.047 (3)	0.007 (3)	0.011 (3)	−0.007 (3)
C1	0.040 (4)	0.044 (4)	0.046 (4)	−0.014 (3)	0.021 (3)	−0.006 (3)
C2	0.041 (4)	0.045 (4)	0.032 (3)	−0.004 (3)	0.020 (3)	0.006 (3)
C3	0.069 (5)	0.042 (4)	0.057 (4)	0.006 (3)	0.034 (4)	0.003 (3)
C4	0.085 (6)	0.049 (4)	0.078 (5)	−0.008 (4)	0.048 (5)	−0.013 (4)
C5	0.087 (6)	0.076 (5)	0.064 (5)	−0.036 (5)	0.050 (5)	−0.037 (4)
C6	0.059 (4)	0.077 (5)	0.039 (4)	−0.017 (4)	0.024 (3)	−0.009 (4)
C7	0.042 (4)	0.050 (4)	0.026 (3)	−0.003 (3)	0.004 (3)	0.002 (3)
C8	0.048 (4)	0.056 (4)	0.044 (4)	0.010 (3)	0.009 (3)	0.006 (3)
C9	0.042 (4)	0.059 (4)	0.067 (5)	0.011 (3)	0.018 (3)	−0.003 (4)
C10	0.078 (6)	0.058 (5)	0.084 (5)	0.001 (4)	0.032 (4)	−0.016 (4)
C11	0.050 (4)	0.056 (4)	0.041 (4)	−0.001 (3)	0.005 (3)	0.008 (3)

Geometric parameters (Å, º)

Cu1—O1	1.910 (4)	C3—C4	1.369 (9)
Cu1—N1	1.922 (5)	C3—H3	0.9300
Cu1—N3	1.940 (6)	C4—C5	1.396 (10)
Cu1—N2	2.041 (5)	C4—H4	0.9300
S1—C11	1.617 (7)	C5—C6	1.368 (10)
O1—C2	1.305 (6)	C5—H5	0.9300
N1—C7	1.280 (7)	C6—H6	0.9300
N1—C8	1.457 (7)	C7—H7	0.9300
N2—C10	1.459 (8)	C8—C9	1.503 (8)
N2—C9	1.490 (8)	C8—H8A	0.9700
N2—H2	0.90 (4)	C8—H8B	0.9700
N3—C11	1.144 (8)	C9—H9A	0.9700
C1—C2	1.410 (8)	C9—H9B	0.9700
C1—C7	1.411 (8)	C10—H10A	0.9600
C1—C6	1.423 (8)	C10—H10B	0.9600
C2—C3	1.422 (8)	C10—H10C	0.9600
O1—Cu1—N1	93.47 (18)	C6—C5—C4	119.5 (6)
O1—Cu1—N3	90.91 (19)	C6—C5—H5	120.3
N1—Cu1—N3	165.9 (2)	C4—C5—H5	120.3
O1—Cu1—N2	166.3 (2)	C5—C6—C1	120.8 (7)
N1—Cu1—N2	85.0 (2)	C5—C6—H6	119.6
N3—Cu1—N2	93.8 (2)	C1—C6—H6	119.6
C2—O1—Cu1	126.6 (4)	N1—C7—C1	125.9 (5)
C7—N1—C8	121.6 (5)	N1—C7—H7	117.0
C7—N1—Cu1	126.0 (4)	C1—C7—H7	117.0
C8—N1—Cu1	112.3 (4)	N1—C8—C9	108.3 (5)
C10—N2—C9	113.6 (5)	N1—C8—H8A	110.0
C10—N2—Cu1	117.1 (4)	C9—C8—H8A	110.0
C9—N2—Cu1	106.5 (4)	N1—C8—H8B	110.0
C10—N2—H2	106 (5)	C9—C8—H8B	110.0
C9—N2—H2	107 (5)	H8A—C8—H8B	108.4
Cu1—N2—H2	105 (5)	N2—C9—C8	107.7 (5)
C11—N3—Cu1	165.6 (6)	N2—C9—H9A	110.2
C2—C1—C7	123.1 (5)	C8—C9—H9A	110.2
C2—C1—C6	119.5 (6)	N2—C9—H9B	110.2
C7—C1—C6	117.4 (6)	C8—C9—H9B	110.2
O1—C2—C1	124.7 (5)	H9A—C9—H9B	108.5
O1—C2—C3	117.2 (5)	N2—C10—H10A	109.5
C1—C2—C3	118.1 (5)	N2—C10—H10B	109.5
C4—C3—C2	120.6 (6)	H10A—C10—H10B	109.5
C4—C3—H3	119.7	N2—C10—H10C	109.5
C2—C3—H3	119.7	H10A—C10—H10C	109.5
C3—C4—C5	121.4 (7)	H10B—C10—H10C	109.5
C3—C4—H4	119.3	N3—C11—S1	178.6 (7)
C5—C4—H4	119.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.90 (4)	2.17 (3)	2.993 (6)	153 (6)

Symmetry code: (i) −x+2, −y, −z+1.