Bromido{N-methyl-N′-[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ3N,N′,N′′}­(thio­cyanato-κN)­copper(II)

Liu, L.-J.

doi:10.1107/S1600536810027534

metal-organic compounds

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Volume 66| Part 8| August 2010| Page m939

https://doi.org/10.1107/S1600536810027534

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Bromido{N-methyl-N′-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ³N,N′,N′′}(thiocyanato-κN)copper(II)

Li-Jun Liu ^a ^*

^aExperimental Center, Linyi Normal University, Linyi Shandong 276005, People's Republic of China
^*Correspondence e-mail: xiaoerduoaa@hotmail.com

(Received 12 July 2010; accepted 12 July 2010; online 17 July 2010)

In the title mononuclear copper(II) compound, [CuBr(NCS)(C₁₀H₁₅N₃)], the Cu^II atom is five-coordinated by three N atoms of the Schiff base ligand, the N atom of a thiocyanate ligand and by one bromide ion forming a distorted square-pyramidal geometry. In the crystal structure, molecules are linked through intermolecular N—H⋯Br hydrogen bonds into chains propagating along [101].

Related literature

For general background to Schiff base–copper(II) complexes, see: Adhikary et al. (2009 ); Al-Karawi (2009 ); Xiao & Zhang (2009 ); Rajasekar et al. (2010 ); Sang & Lin (2010 ); Qin et al. (2010 ). For related copper complexes with square-pyramidal coordination, see: Wang et al. (2010 ); Zhang et al. (2009 ); Wei et al. (2007 ).

Experimental

Crystal data

[CuBr(NCS)(C₁₀H₁₅N₃)]
M_r = 378.78
Monoclinic, P 2₁ /n
a = 10.979 (2) Å
b = 11.407 (2) Å
c = 12.001 (3) Å
β = 109.033 (2)°
V = 1420.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.48 mm⁻¹
T = 298 K
0.30 × 0.27 × 0.27 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.347, T_max = 0.377
8078 measured reflections
3022 independent reflections
1892 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.137
S = 0.97
3022 reflections
168 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N4	1.949 (5)
Cu1—N2	1.965 (5)
Cu1—N1	2.019 (5)
Cu1—N3	2.044 (5)
Cu1—Br1	2.7228 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Br1ⁱ	0.90 (1)	2.69 (4)	3.494 (5)	150 (6)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027534/ci5132sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027534/ci5132Isup2.hkl

checkCIF report

Comment top

Copper(II) complexes with Schiff bases have been widely investigated in coordination chemistry and biological chemistry (Adhikary et al., 2009; Al-Karawi, 2009; Xiao & Zhang, 2009; Rajasekar et al., 2010; Sang & Lin, 2010; Qin et al., 2010). In the present paper, the title new copper complex with the Schiff base ligand Nmethyl-N'-(1-pyridin-2-ylethylidene)ethane-1,2-diamine, is reported.

The Cu^II atom in the title complex (Fig. 1) is five-coordinated by one pyridine N, one imine N, and one amine N atoms of a Schiff base ligand, by one bromide atom, and by one N atom of a thiocyanate ligand, forming a square-pyramidal geometry. The bond lengths (Table 1) related to the Cu atom are comparable with those observed in similar copper complexes with square-pyramidal geometry (Wang et al., 2010; Zhang et al., 2009; Wei et al., 2007).

In the crystal structure, molecules are linked through intermolecular N—H···Br hydrogen bonds (Table 2) to form chains running along the a axis (Fig. 2).

Related literature top

For general background to Schiff base–copper(II) complexes, see: Adhikary et al. (2009); Al-Karawi (2009); Xiao & Zhang (2009); Rajasekar et al. (2010); Sang & Lin (2010); Qin et al. (2010). For related copper complexes with square-pyramidal coordination, see: Wang et al. (2010); Zhang et al. (2009); Wei et al. (2007).

Experimental top

2-Acetylpyridine (0.1 mmol, 12.1 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg), and copper bromide (0.1 mmol, 22.3 mg) were mixed and stirred in methanol (20 ml) at reflux for 2 h, to give a blue solution. The solution was cooled to room temperature, and blue block-shaped single crystals were formed by slow evaporation of the solution in air.

Structure description top

In the crystal structure, molecules are linked through intermolecular N—H···Br hydrogen bonds (Table 2) to form chains running along the a axis (Fig. 2).

For general background to Schiff base–copper(II) complexes, see: Adhikary et al. (2009); Al-Karawi (2009); Xiao & Zhang (2009); Rajasekar et al. (2010); Sang & Lin (2010); Qin et al. (2010). For related copper complexes with square-pyramidal coordination, see: Wang et al. (2010); Zhang et al. (2009); Wei et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex with 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title complex, viewed along the c axis. Hydrogen bonds are shown as dashed lines.

Bromido{N-methyl-N'-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine- κ³N,N',N''}(thiocyanato-κN)copper(II) top

Crystal data top

[CuBr(NCS)(C₁₀H₁₅N₃)]	F(000) = 756
M_r = 378.78	D_x = 1.771 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2570 reflections
a = 10.979 (2) Å	θ = 2.5–26.5°
b = 11.407 (2) Å	µ = 4.48 mm⁻¹
c = 12.001 (3) Å	T = 298 K
β = 109.033 (2)°	Block, blue
V = 1420.8 (5) Å³	0.30 × 0.27 × 0.27 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3022 independent reflections
Radiation source: fine-focus sealed tube	1892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→14
T_min = 0.347, T_max = 0.377	k = −14→12
8078 measured reflections	l = −15→8

Refinement top

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
3022 reflections	(Δ/σ)_max = 0.001
168 parameters	Δρ_max = 0.86 e Å⁻³
1 restraint	Δρ_min = −1.01 e Å⁻³

Crystal data top

[CuBr(NCS)(C₁₀H₁₅N₃)]	V = 1420.8 (5) Å³
M_r = 378.78	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.979 (2) Å	µ = 4.48 mm⁻¹
b = 11.407 (2) Å	T = 298 K
c = 12.001 (3) Å	0.30 × 0.27 × 0.27 mm
β = 109.033 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3022 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1892 reflections with I > 2σ(I)
T_min = 0.347, T_max = 0.377	R_int = 0.070
8078 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	1 restraint
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.86 e Å⁻³
3022 reflections	Δρ_min = −1.01 e Å⁻³
168 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.18062 (6)	0.60367 (6)	0.05737 (6)	0.0319 (2)
Br1	0.38736 (6)	0.64845 (6)	0.25208 (5)	0.0412 (2)
N1	0.2487 (4)	0.4486 (4)	0.0218 (4)	0.0292 (11)
N2	0.2631 (5)	0.6533 (5)	−0.0577 (4)	0.0356 (12)
N3	0.1033 (5)	0.7682 (4)	0.0253 (4)	0.0405 (13)
N4	0.0715 (5)	0.5412 (5)	0.1429 (5)	0.0451 (14)
S1	−0.03147 (18)	0.50606 (17)	0.32203 (16)	0.0522 (5)
C1	0.2396 (6)	0.3440 (5)	0.0690 (5)	0.0390 (15)
H1	0.1917	0.3382	0.1200	0.047*
C2	0.2974 (7)	0.2460 (6)	0.0456 (7)	0.0527 (19)
H2	0.2893	0.1748	0.0803	0.063*
C3	0.3683 (7)	0.2534 (6)	−0.0307 (6)	0.0528 (19)
H3	0.4090	0.1874	−0.0474	0.063*
C4	0.3778 (6)	0.3601 (6)	−0.0815 (6)	0.0454 (17)
H4	0.4249	0.3672	−0.1330	0.054*
C5	0.3152 (5)	0.4572 (5)	−0.0541 (5)	0.0314 (13)
C6	0.3174 (5)	0.5760 (5)	−0.1021 (5)	0.0331 (14)
C7	0.3743 (7)	0.5979 (6)	−0.1975 (6)	0.0519 (18)
H7A	0.3179	0.5672	−0.2706	0.078*
H7B	0.4566	0.5597	−0.1780	0.078*
H7C	0.3851	0.6806	−0.2052	0.078*
C8	0.2442 (7)	0.7750 (6)	−0.0943 (6)	0.0518 (18)
H8A	0.1787	0.7814	−0.1712	0.062*
H8B	0.3238	0.8082	−0.0987	0.062*
C9	0.2019 (7)	0.8386 (6)	−0.0024 (6)	0.0535 (19)
H9A	0.2752	0.8504	0.0683	0.064*
H9B	0.1669	0.9148	−0.0322	0.064*
C10	0.0578 (8)	0.8231 (6)	0.1167 (6)	0.064 (2)
H10A	0.1306	0.8425	0.1842	0.096*
H10B	0.0030	0.7692	0.1395	0.096*
H10C	0.0104	0.8931	0.0855	0.096*
C11	0.0286 (5)	0.5262 (5)	0.2159 (5)	0.0312 (14)
H3A	0.038 (5)	0.760 (6)	−0.043 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0334 (4)	0.0328 (4)	0.0350 (4)	0.0035 (3)	0.0184 (3)	0.0024 (3)
Br1	0.0369 (4)	0.0467 (4)	0.0389 (4)	0.0031 (3)	0.0108 (3)	−0.0090 (3)
N1	0.028 (3)	0.034 (3)	0.029 (3)	−0.001 (2)	0.014 (2)	0.000 (2)
N2	0.030 (3)	0.042 (3)	0.036 (3)	0.004 (2)	0.013 (2)	0.011 (2)
N3	0.049 (3)	0.030 (3)	0.043 (3)	0.007 (2)	0.014 (3)	−0.003 (2)
N4	0.039 (3)	0.056 (4)	0.050 (3)	0.000 (3)	0.028 (3)	0.000 (3)
S1	0.0599 (12)	0.0548 (11)	0.0570 (11)	−0.0083 (9)	0.0397 (10)	−0.0003 (9)
C1	0.041 (4)	0.036 (4)	0.040 (4)	−0.001 (3)	0.015 (3)	0.003 (3)
C2	0.052 (5)	0.029 (4)	0.071 (5)	0.001 (3)	0.012 (4)	−0.003 (3)
C3	0.055 (5)	0.040 (5)	0.057 (5)	0.006 (3)	0.009 (4)	−0.016 (4)
C4	0.039 (4)	0.058 (5)	0.042 (4)	0.006 (3)	0.017 (3)	−0.016 (3)
C5	0.026 (3)	0.039 (4)	0.028 (3)	0.001 (3)	0.008 (3)	−0.002 (3)
C6	0.023 (3)	0.050 (4)	0.029 (3)	0.002 (3)	0.013 (2)	0.007 (3)
C7	0.046 (4)	0.077 (5)	0.041 (4)	0.002 (4)	0.026 (3)	0.013 (4)
C8	0.056 (5)	0.046 (5)	0.066 (5)	0.006 (3)	0.036 (4)	0.020 (4)
C9	0.055 (5)	0.033 (4)	0.065 (5)	0.002 (3)	0.008 (4)	0.008 (3)
C10	0.079 (6)	0.060 (5)	0.054 (5)	0.026 (4)	0.022 (4)	−0.008 (4)
C11	0.022 (3)	0.029 (3)	0.044 (4)	0.000 (2)	0.012 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Cu1—N4	1.949 (5)	C3—C4	1.380 (9)
Cu1—N2	1.965 (5)	C3—H3	0.93
Cu1—N1	2.019 (5)	C4—C5	1.398 (8)
Cu1—N3	2.044 (5)	C4—H4	0.93
Cu1—Br1	2.7228 (10)	C5—C6	1.476 (8)
N1—C1	1.338 (7)	C6—C7	1.494 (8)
N1—C5	1.343 (7)	C7—H7A	0.96
N2—C6	1.274 (7)	C7—H7B	0.96
N2—C8	1.451 (8)	C7—H7C	0.96
N3—C9	1.470 (9)	C8—C9	1.514 (9)
N3—C10	1.484 (8)	C8—H8A	0.97
N3—H3A	0.899 (10)	C8—H8B	0.97
N4—C11	1.135 (7)	C9—H9A	0.97
S1—C11	1.630 (7)	C9—H9B	0.97
C1—C2	1.359 (9)	C10—H10A	0.96
C1—H1	0.93	C10—H10B	0.96
C2—C3	1.384 (10)	C10—H10C	0.96
C2—H2	0.93

N4—Cu1—N2	168.1 (2)	C3—C4—H4	120.6
N4—Cu1—N1	97.2 (2)	C5—C4—H4	120.6
N2—Cu1—N1	79.4 (2)	N1—C5—C4	121.3 (6)
N4—Cu1—N3	98.4 (2)	N1—C5—C6	114.4 (5)
N2—Cu1—N3	82.0 (2)	C4—C5—C6	124.3 (6)
N1—Cu1—N3	157.5 (2)	N2—C6—C5	113.7 (5)
N4—Cu1—Br1	95.75 (16)	N2—C6—C7	125.1 (6)
N2—Cu1—Br1	95.90 (14)	C5—C6—C7	121.1 (6)
N1—Cu1—Br1	94.79 (12)	C6—C7—H7A	109.5
N3—Cu1—Br1	99.67 (15)	C6—C7—H7B	109.5
C1—N1—C5	118.9 (5)	H7A—C7—H7B	109.5
C1—N1—Cu1	127.4 (4)	C6—C7—H7C	109.5
C5—N1—Cu1	113.6 (4)	H7A—C7—H7C	109.5
C6—N2—C8	125.1 (5)	H7B—C7—H7C	109.5
C6—N2—Cu1	118.7 (4)	N2—C8—C9	106.6 (5)
C8—N2—Cu1	115.8 (4)	N2—C8—H8A	110.4
C9—N3—C10	112.8 (5)	C9—C8—H8A	110.4
C9—N3—Cu1	104.6 (4)	N2—C8—H8B	110.4
C10—N3—Cu1	117.9 (4)	C9—C8—H8B	110.4
C9—N3—H3A	106 (5)	H8A—C8—H8B	108.6
C10—N3—H3A	111 (5)	N3—C9—C8	109.1 (5)
Cu1—N3—H3A	104 (5)	N3—C9—H9A	109.9
C11—N4—Cu1	160.6 (5)	C8—C9—H9A	109.9
N1—C1—C2	122.8 (6)	N3—C9—H9B	109.9
N1—C1—H1	118.6	C8—C9—H9B	109.9
C2—C1—H1	118.6	H9A—C9—H9B	108.3
C1—C2—C3	119.2 (7)	N3—C10—H10A	109.5
C1—C2—H2	120.4	N3—C10—H10B	109.5
C3—C2—H2	120.4	H10A—C10—H10B	109.5
C4—C3—C2	119.1 (6)	N3—C10—H10C	109.5
C4—C3—H3	120.5	H10A—C10—H10C	109.5
C2—C3—H3	120.5	H10B—C10—H10C	109.5
C3—C4—C5	118.7 (6)	N4—C11—S1	179.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Br1ⁱ	0.90 (1)	2.69 (4)	3.494 (5)	150 (6)

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[CuBr(NCS)(C₁₀H₁₅N₃)]
M_r	378.78
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.979 (2), 11.407 (2), 12.001 (3)
β (°)	109.033 (2)
V (Å³)	1420.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.48
Crystal size (mm)	0.30 × 0.27 × 0.27

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.347, 0.377
No. of measured, independent and observed [I > 2σ(I)] reflections	8078, 3022, 1892
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.137, 0.97
No. of reflections	3022
No. of parameters	168
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −1.01

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N4	1.949 (5)	Cu1—N3	2.044 (5)
Cu1—N2	1.965 (5)	Cu1—Br1	2.7228 (10)
Cu1—N1	2.019 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Br1ⁱ	0.90 (1)	2.69 (4)	3.494 (5)	150 (6)

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.

Acknowledgements

The author acknowledges Linyi Normal University for supporting this work.

References

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