Bis[2-(amino­meth­yl)pyridine-κ2N,N′]bis­(thio­cyanato-κN)copper(II)

Karan, N.K.; Chan, K.-T.; Lee, H.M.

doi:10.1107/S1600536809013427

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m525

doi:10.1107/S1600536809013427

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Bis[2-(aminomethyl)pyridine-κ²N,N′]bis(thiocyanato-κN)copper(II)

Nirmal Kumar Karan,^a Kai-Ting Chan ^a and Hon Man Lee ^a ^*

^aNational Changhua University of Education, Department of Chemistry, Changhua, Taiwan 50058
^*Correspondence e-mail: leehm@cc.ncue.edu.tw

(Received 2 April 2009; accepted 9 April 2009; online 18 April 2009)

In the title complex, [Cu(NCS)₂(C₆H₈N₂)₂], the Cu^II atom, lying on an inversion center, adopts a Jahn–Teller distorted octahedral CuN₆ coordination geometry. The two bidentate 2-aminomethylpyridine ligands are coordinated in a trans fashion, while the two thiocyanate ligands are at the axial positions and coordinate to the Cu atom in a bent mode with a C—N—Cu angle of 127.49 (10)°. Intermolecular N—H⋯N and N—H⋯S hydrogen bonds link the copper complex molecules into an infinite two-dimensional network.

Related literature

For six-coordinate trans-dithiocyanato Cu(II) complexes similar to the title complex, see: Gary et al. (2004 ); Ferrer et al. (1992 ); Gorji et al. (2001 ); Kozlowski & Hodgson (1975 ); Li & Zhang (2004 ).

Experimental

Crystal data

[Cu(NCS)₂(C₆H₈N₂)₂]
M_r = 395.99
Monoclinic, P 2₁ /c
a = 9.1023 (4) Å
b = 9.1740 (4) Å
c = 9.6895 (4) Å
β = 91.872 (3)°
V = 808.69 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 150 K
0.46 × 0.38 × 0.31 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.497, T_max = 0.603
11419 measured reflections
2086 independent reflections
1776 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.063
S = 1.13
2086 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N3ⁱ	0.92	2.27	3.0717 (19)	145
N2—H2B⋯S1ⁱⁱ	0.92	2.60	3.4628 (13)	156
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 I, global. DOI: 10.1107/S1600536809013427/pv2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013427/pv2151Isup2.hkl

checkCIF report

Comment top

The tilte complex was readily obtained from the reaction between copper(II) acetate, 2-aminomethylpyridine, and sodium thiocyanate. The complex consists of two trans bidentate ligands and two trans thiocyanate ligands (Fig. 1). It exhibits an octahedron coordination geometry at the Cu atom which is located on the inversion center. The bent coordination of thiocyanate results in the C5—N1—Cu1 bond angle of 127.49 (10)°. The pyridine ring is twisted from the equatorial plane defined by the Cu and the four N atoms; the interplanar angle is 17.86 (8)°. Intermolecular H-bonds of the type N—H···N and N—H···S exist, linking the complex into a into a two-dimensional hydrogen bonded network (Table 1).

Six-coordinate trans-dithiocyanato Cu(II) complexes similar to the title complex have been reported in the literature (Gary et al., 2004; Ferrer et al., 1992; Gorji et al., 2001; Kozlowski & Hodgson, 1975; Li & Zhang, 2004).

Related literature top

For six-coordinate trans-dithiocyanato Cu(II) complexes similar to the title complex, see: Gary et al. (2004); Ferrer et al. (1992); Gorji et al. (2001); Kozlowski & Hodgson (1975); Li & Zhang (2004).

Experimental top

To a methanolic solution (10 ml) of Cu(O₂CCH₃)₂.H₂O (1.0 mmol, 0.199 g), a methanolic solution (10.0 ml) of 2-aminomethylpyridine (2.0 mmol, 0.207 ml) was added dropwise with stirring. Then to this mixture of solution, NaSCN (2.0 mmol, 0.162 g) in methanol (5.0 ml) was added and the mixture was stirred for 5 min. The solution was kept undisturbed. Blue crystals suitable for X-ray crystallography were obtained after one week by slow evaporation of the solvent.

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 structure of the title complex, showing 50% displacement ellipsoids for non-H atoms. The H atoms are dipicted by circles of an arbitrary radius. The unlabelled atoms are related to the labelled ones by -x, 1 - y, 1 - z.
	Fig. 2. A packing diagram of the title compound along the a axis. Hyrogen bonds are shown as dashed lines.

Bis[2-(aminomethyl)pyridine-κ²N,N']bis(thiocyanato- κN)copper(II) top

Crystal data top

[Cu(NCS)₂(C₆H₈N₂)₂]	F(000) = 406
M_r = 395.99	D_x = 1.626 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3360 reflections
a = 9.1023 (4) Å	θ = 3.1–28.0°
b = 9.1740 (4) Å	µ = 1.62 mm⁻¹
c = 9.6895 (4) Å	T = 150 K
β = 91.872 (3)°	Plate, blue
V = 808.69 (6) Å³	0.46 × 0.38 × 0.31 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	2086 independent reflections
Radiation source: fine-focus sealed tube	1776 reflections with I > 2σ
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 28.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
T_min = 0.497, T_max = 0.603	k = −12→12
11419 measured reflections	l = −13→12

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0308P)² + 0.2097P] where P = (F_o² + 2F_c²)/3
2086 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Cu(NCS)₂(C₆H₈N₂)₂]	V = 808.69 (6) Å³
M_r = 395.99	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1023 (4) Å	µ = 1.62 mm⁻¹
b = 9.1740 (4) Å	T = 150 K
c = 9.6895 (4) Å	0.46 × 0.38 × 0.31 mm
β = 91.872 (3)°

Data collection top

Bruker SMART APEXII diffractometer	2086 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1776 reflections with I > 2σ
T_min = 0.497, T_max = 0.603	R_int = 0.031
11419 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.13	Δρ_max = 0.35 e Å⁻³
2086 reflections	Δρ_min = −0.40 e Å⁻³
106 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.27555 (16)	0.35413 (16)	0.48964 (15)	0.0151 (3)
C2	0.41671 (16)	0.30420 (16)	0.52349 (17)	0.0187 (3)
H2	0.4607	0.2302	0.4701	0.022*
C3	0.49184 (16)	0.36421 (17)	0.63614 (17)	0.0199 (3)
H3	0.5878	0.3311	0.6618	0.024*
C4	0.42557 (17)	0.47314 (17)	0.71109 (17)	0.0190 (3)
H4	0.4759	0.5170	0.7878	0.023*
C5	0.28491 (17)	0.51688 (16)	0.67232 (16)	0.0170 (3)
H5	0.2395	0.5917	0.7236	0.020*
C6	0.18680 (17)	0.29582 (17)	0.36793 (16)	0.0188 (3)
H6A	0.2513	0.2813	0.2888	0.023*
H6B	0.1435	0.2005	0.3918	0.023*
C7	−0.15576 (16)	0.17946 (16)	0.52438 (16)	0.0175 (3)
Cu1	0.0000	0.5000	0.5000	0.01369 (8)
N1	0.20991 (13)	0.45719 (14)	0.56437 (13)	0.0142 (2)
N2	0.06857 (13)	0.39999 (14)	0.32960 (13)	0.0161 (3)
H2A	−0.0087	0.3513	0.2869	0.019*
H2B	0.1030	0.4680	0.2688	0.019*
N3	−0.08726 (15)	0.26276 (15)	0.58955 (15)	0.0244 (3)
S1	−0.25589 (5)	0.06047 (5)	0.43612 (4)	0.02601 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0159 (7)	0.0142 (6)	0.0154 (7)	0.0005 (5)	0.0020 (5)	0.0008 (5)
C2	0.0166 (7)	0.0171 (7)	0.0225 (8)	0.0036 (6)	0.0032 (6)	0.0011 (6)
C3	0.0140 (7)	0.0215 (7)	0.0243 (8)	0.0029 (6)	0.0003 (6)	0.0069 (6)
C4	0.0167 (7)	0.0224 (8)	0.0177 (8)	−0.0027 (6)	−0.0030 (6)	0.0016 (6)
C5	0.0164 (7)	0.0187 (7)	0.0159 (7)	−0.0008 (6)	0.0001 (6)	−0.0009 (5)
C6	0.0187 (7)	0.0201 (7)	0.0176 (8)	0.0052 (6)	−0.0015 (6)	−0.0049 (6)
C7	0.0168 (7)	0.0183 (7)	0.0175 (8)	0.0037 (6)	0.0027 (6)	0.0057 (6)
Cu1	0.01194 (13)	0.01631 (13)	0.01273 (14)	0.00240 (9)	−0.00107 (9)	−0.00347 (9)
N1	0.0130 (6)	0.0152 (5)	0.0143 (6)	0.0009 (5)	0.0004 (5)	0.0000 (5)
N2	0.0154 (6)	0.0190 (6)	0.0140 (6)	0.0017 (5)	−0.0006 (5)	−0.0019 (5)
N3	0.0261 (7)	0.0213 (7)	0.0255 (8)	−0.0016 (6)	−0.0033 (6)	0.0040 (6)
S1	0.0235 (2)	0.0293 (2)	0.0251 (2)	−0.00253 (17)	−0.00159 (16)	−0.00652 (17)

Geometric parameters (Å, º) top

C1—N1	1.3430 (19)	C6—N2	1.4775 (18)
C1—C2	1.393 (2)	C6—H6A	0.9900
C1—C6	1.506 (2)	C6—H6B	0.9900
C2—C3	1.383 (2)	C7—N3	1.160 (2)
C2—H2	0.9500	C7—S1	1.6440 (16)
C3—C4	1.385 (2)	Cu1—N2	2.0062 (12)
C3—H3	0.9500	Cu1—N2ⁱ	2.0062 (12)
C4—C5	1.382 (2)	Cu1—N1	2.0288 (12)
C4—H4	0.9500	Cu1—N1ⁱ	2.0288 (12)
C5—N1	1.3466 (19)	N2—H2A	0.9200
C5—H5	0.9500	N2—H2B	0.9200

N1—C1—C2	121.85 (14)	C1—C6—H6B	109.8
N1—C1—C6	115.83 (12)	H6A—C6—H6B	108.2
C2—C1—C6	122.32 (13)	N3—C7—S1	178.26 (15)
C3—C2—C1	118.90 (14)	N2—Cu1—N2ⁱ	180.0
C3—C2—H2	120.5	N2—Cu1—N1	81.33 (5)
C1—C2—H2	120.5	N2ⁱ—Cu1—N1	98.67 (5)
C2—C3—C4	119.23 (14)	N2—Cu1—N1ⁱ	98.67 (5)
C2—C3—H3	120.4	N2ⁱ—Cu1—N1ⁱ	81.33 (5)
C4—C3—H3	120.4	N1—Cu1—N1ⁱ	180.0
C5—C4—C3	118.84 (14)	C1—N1—C5	118.81 (13)
C5—C4—H4	120.6	C1—N1—Cu1	113.68 (10)
C3—C4—H4	120.6	C5—N1—Cu1	127.49 (10)
N1—C5—C4	122.33 (14)	C6—N2—Cu1	109.43 (9)
N1—C5—H5	118.8	C6—N2—H2A	109.8
C4—C5—H5	118.8	Cu1—N2—H2A	109.8
N2—C6—C1	109.56 (12)	C6—N2—H2B	109.8
N2—C6—H6A	109.8	Cu1—N2—H2B	109.8
C1—C6—H6A	109.8	H2A—N2—H2B	108.2
N2—C6—H6B	109.8

N1—C1—C2—C3	−0.9 (2)	C6—C1—N1—Cu1	3.52 (16)
C6—C1—C2—C3	179.38 (14)	C4—C5—N1—C1	−1.7 (2)
C1—C2—C3—C4	−0.7 (2)	C4—C5—N1—Cu1	176.34 (11)
C2—C3—C4—C5	1.1 (2)	N2—Cu1—N1—C1	−17.99 (10)
C3—C4—C5—N1	0.1 (2)	N2ⁱ—Cu1—N1—C1	162.01 (10)
N1—C1—C6—N2	19.63 (18)	N2—Cu1—N1—C5	163.84 (13)
C2—C1—C6—N2	−160.67 (14)	N2ⁱ—Cu1—N1—C5	−16.16 (13)
C2—C1—N1—C5	2.2 (2)	C1—C6—N2—Cu1	−33.03 (14)
C6—C1—N1—C5	−178.14 (13)	N1—Cu1—N2—C6	27.99 (10)
C2—C1—N1—Cu1	−176.18 (11)	N1ⁱ—Cu1—N2—C6	−152.01 (10)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱⁱ	0.92	2.27	3.0717 (19)	145
N2—H2B···S1ⁱⁱⁱ	0.92	2.60	3.4628 (13)	156

Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(NCS)₂(C₆H₈N₂)₂]
M_r	395.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.1023 (4), 9.1740 (4), 9.6895 (4)
β (°)	91.872 (3)
V (Å³)	808.69 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.62
Crystal size (mm)	0.46 × 0.38 × 0.31

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.497, 0.603
No. of measured, independent and observed (I > 2σ) reflections	11419, 2086, 1776
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.063, 1.13
No. of reflections	2086
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.40

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.92	2.27	3.0717 (19)	145
N2—H2B···S1ⁱⁱ	0.92	2.60	3.4628 (13)	156

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+1/2.

Acknowledgements

We thank the National Science Council of Taiwan for financial support of this work.

References

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