Di-μ-chlorido-bis­{[2-(2-pyridylmethyl­amino)ethanesulfonato-κ3N,N′,O]copper(II)}

Du, Z.-X.; Qin, J.-H.; Wang, J.-G.

doi:10.1107/S1600536808000779

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m341

doi:10.1107/S1600536808000779

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Di-μ-chlorido-bis{[2-(2-pyridylmethylamino)ethanesulfonato-κ³N,N′,O]copper(II)}

Zhong-Xiang Du,^a ^* Jian-Hua Qin ^a and Jian-Ge Wang ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
^*Correspondence e-mail: dzx101012@126.com

(Received 30 November 2007; accepted 21 December 2007; online 11 January 2008)

In the title compound, [Cu₂(C₈H₁₁N₂O₃S)₂Cl₂], the Cu atoms are five-coordinated in a distorted square-pyramidal geometry by three donor atoms of the deprotonated anionic 2-(2-pyridylmethylamino)ethanesulfonate (pmt) ligand and two Cl atoms. The Cl atoms bridge two Cu atoms, giving a binuclear structure; the centroid of the Cu₂Cl₂ ring lies on a crystallographic center of inversion. The complex is stabilized by hydrogen bonds and π–π stacking interactions [average interplanar distance = 3.4969 (1) Å and ring-centroid separation distance = 4.1068 (4) Å].

Related literature

For related literature, see: Li et al. (2006 , 2007a ,b ).

Experimental

Crystal data

[Cu₂(C₈H₁₁N₂O₃S)₂Cl₂]
M_r = 628.48
Triclinic, $[P \overline 1]$
a = 8.294 (1) Å
b = 8.362 (1) Å
c = 9.110 (1) Å
α = 103.773 (2)°
β = 98.118 (2)°
γ = 113.043 (2)°
V = 544.9 (1) Å³
Z = 1
Mo Kα radiation
μ = 2.43 mm⁻¹
T = 291 (2) K
0.33 × 0.20 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.504, T_max = 0.811
3270 measured reflections
2385 independent reflections
2224 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.067
S = 1.10
2385 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O3ⁱ	0.95 (3)	2.20 (3)	2.966 (2)	137 (2)
Symmetry code: (i) -x, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000779/im2051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000779/im2051Isup2.hkl

checkCIF report

Comment top

Previously, one Co (Li et al., 2006) and two Cu complexes (Li et al., 2007a,b) containing the reduced schiff base ligand 2-pyridine-2-ylmethylamino-ethanesulfonic acid (Hpmt) have been reported. Herein we describe the structure of another dinuclear Cu compound, Figure 1.

The title compound is a binuclear Cu complex and each Cu center has square-pyramidal geometry formed by two N and one O atoms of an anionic pmt ligand and two chlorine atoms. The plane N1/N2/O1/Cl1A defines the base of the pyramid while Cl1 occupies the apical position. Cu1 is situated 0.168 (1) Å above the N1/N2/O1/Cl1A plane. The chlorine atoms bridge the Cu atoms to form this binuclear structure, with a Cu1···Cu1(-x, -y + 2, -z + 1) distance of 3.461 (2) Å.

The N—H donor and S?O acceptor (Table 1) groups of the pmt ligand participate in hydrogen bonding and they join the dinuclear complex units into a one-dimensional chain structure along b axis (Figure 2 and Table 1). These chains are further expanded into a two-dimensional network via π-π stacking between the pyridine rings of adjacent parallel chains. The interplanar average distance and ring-centroid separation disstance are 3.4969 (1) Å and 4.1068 (4) Å, respectively.

Related literature top

For related literature, see: Li et al. (2006, 2007a,b).

Experimental top

The ligand 2-pyridin-2-ylmethylamino-ethanesulfonic acid (Hpmt) was prepared according to the method of Li et al. (2006). 10 ml of an aqueous solution of CuCl₂ × 2 H₂O (0.171 g, 1 mmol) was dropped into 10 ml of an methanolic solution of Hpmt (0.216 g, 1 mmol). Then the mixture was stirred for 6 h at 343 K.The filtrate was left to stand under air for about one week to obtain blue block-shaped crystals. Analysis, found (%): C, 30.51; H, 3.50; N, 8.91; S, 10.18. [C₁₆H₂₂N₄O₆S₂Cl₂Cu₂] requires (%): C,30.55; H,5.55; N,12.96; S,14.81.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (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 (I) with atom-numbering scheme. Atoms with the suffix A are at the symmetry position (-x, -y + 2, -z + 1).
	Fig. 2. Packing diagram, projected on the bc plane, showing the hydrogen bonding and π-π stacking interactions. H atoms have partially been omitted for the sake of clarity.

Di-µ-chlorido-bis{[2-(2-pyridylmethylamino)ethanesulfonato- κ³N,N',O]copper(II)} top

Crystal data top

[Cu₂(C₈H₁₁N₂O₃S)₂Cl₂]	Z = 1
M_r = 628.28	F(000) = 318
Triclinic, P1	D_x = 1.915 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.294 (1) Å	Cell parameters from 2667 reflections
b = 8.362 (1) Å	θ = 2.4–28.3°
c = 9.110 (1) Å	µ = 2.43 mm⁻¹
α = 103.773 (2)°	T = 291 K
β = 98.118 (2)°	Block, blue
γ = 113.043 (2)°	0.33 × 0.20 × 0.09 mm
V = 544.9 (1) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	2385 independent reflections
Radiation source: fine-focus sealed tube	2224 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.009
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.505, T_max = 0.811	k = −10→10
3270 measured reflections	l = −9→11

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) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.037P)² + 0.2091P] where P = (F_o² + 2F_c²)/3
2385 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu₂(C₈H₁₁N₂O₃S)₂Cl₂]	γ = 113.043 (2)°
M_r = 628.28	V = 544.9 (1) Å³
Triclinic, P1	Z = 1
a = 8.294 (1) Å	Mo Kα radiation
b = 8.362 (1) Å	µ = 2.43 mm⁻¹
c = 9.110 (1) Å	T = 291 K
α = 103.773 (2)°	0.33 × 0.20 × 0.09 mm
β = 98.118 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2385 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2224 reflections with I > 2σ(I)
T_min = 0.505, T_max = 0.811	R_int = 0.009
3270 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.48 e Å⁻³
2385 reflections	Δρ_min = −0.34 e Å⁻³
149 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
Cu1	−0.00815 (3)	0.79189 (3)	0.40050 (2)	0.02480 (9)
Cl1	0.21525 (6)	1.15056 (7)	0.48221 (5)	0.02695 (12)
S1	0.25729 (6)	0.72960 (7)	0.64825 (6)	0.02540 (12)
O1	0.09412 (19)	0.7556 (2)	0.59265 (16)	0.0311 (3)
O2	0.4160 (2)	0.9013 (2)	0.72554 (19)	0.0385 (4)
O3	0.2140 (2)	0.6050 (2)	0.74013 (19)	0.0381 (4)
N1	−0.1223 (2)	0.7825 (2)	0.18742 (18)	0.0257 (3)
N2	0.1380 (2)	0.6952 (2)	0.2771 (2)	0.0276 (3)
C1	−0.2789 (3)	0.7931 (4)	0.1445 (3)	0.0382 (5)
H1	−0.3426	0.8078	0.2188	0.046*
C2	−0.3480 (3)	0.7828 (4)	−0.0065 (3)	0.0443 (6)
H2	−0.4578	0.7878	−0.0340	0.053*
C3	−0.2519 (3)	0.7652 (3)	−0.1151 (2)	0.0391 (5)
H3	−0.2961	0.7581	−0.2174	0.047*
C4	−0.0881 (3)	0.7580 (3)	−0.0712 (2)	0.0332 (5)
H4	−0.0203	0.7481	−0.1430	0.040*
C5	−0.0275 (3)	0.7659 (3)	0.0813 (2)	0.0264 (4)
C6	0.1491 (3)	0.7631 (3)	0.1417 (2)	0.0314 (4)
H6A	0.1726	0.6835	0.0600	0.038*
H6B	0.2478	0.8857	0.1731	0.038*
C7	0.3187 (3)	0.7178 (3)	0.3579 (2)	0.0287 (4)
H7A	0.3988	0.8472	0.4099	0.034*
H7B	0.3725	0.6699	0.2812	0.034*
C8	0.2998 (3)	0.6170 (3)	0.4776 (2)	0.0296 (4)
H8A	0.4104	0.6049	0.5074	0.035*
H8B	0.2011	0.4944	0.4297	0.035*
H1N	0.051 (4)	0.570 (4)	0.233 (3)	0.045 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02148 (14)	0.03819 (16)	0.02055 (13)	0.01626 (11)	0.00702 (9)	0.01323 (10)
Cl1	0.0222 (2)	0.0363 (3)	0.0269 (2)	0.01426 (19)	0.01029 (18)	0.01360 (18)
S1	0.0178 (2)	0.0297 (3)	0.0285 (2)	0.00845 (19)	0.00306 (18)	0.01438 (19)
O1	0.0270 (7)	0.0504 (9)	0.0255 (7)	0.0230 (7)	0.0082 (6)	0.0174 (6)
O2	0.0268 (8)	0.0346 (8)	0.0401 (8)	0.0044 (6)	0.0010 (6)	0.0087 (6)
O3	0.0324 (8)	0.0455 (9)	0.0432 (9)	0.0154 (7)	0.0091 (7)	0.0296 (7)
N1	0.0243 (8)	0.0332 (9)	0.0211 (7)	0.0132 (7)	0.0053 (6)	0.0109 (6)
N2	0.0229 (8)	0.0328 (9)	0.0281 (8)	0.0125 (7)	0.0071 (7)	0.0112 (7)
C1	0.0324 (11)	0.0617 (15)	0.0289 (10)	0.0259 (11)	0.0085 (9)	0.0196 (10)
C2	0.0384 (13)	0.0680 (17)	0.0339 (11)	0.0295 (12)	0.0035 (10)	0.0217 (11)
C3	0.0485 (14)	0.0455 (13)	0.0227 (10)	0.0210 (11)	0.0021 (9)	0.0139 (9)
C4	0.0422 (12)	0.0353 (11)	0.0224 (9)	0.0166 (10)	0.0103 (9)	0.0096 (8)
C5	0.0294 (10)	0.0245 (9)	0.0236 (9)	0.0101 (8)	0.0073 (8)	0.0080 (7)
C6	0.0297 (10)	0.0429 (12)	0.0262 (9)	0.0174 (9)	0.0123 (8)	0.0139 (8)
C7	0.0204 (9)	0.0343 (11)	0.0319 (10)	0.0118 (8)	0.0072 (8)	0.0115 (8)
C8	0.0246 (10)	0.0280 (10)	0.0388 (11)	0.0132 (8)	0.0078 (8)	0.0130 (8)

Geometric parameters (Å, º) top

Cu1—O1	1.9775 (14)	C1—H1	0.9300
Cu1—N1	2.0051 (16)	C2—C3	1.371 (4)
Cu1—N2	2.0268 (17)	C2—H2	0.9300
Cu1—Cl1ⁱ	2.2901 (5)	C3—C4	1.390 (3)
Cu1—Cl1	2.6796 (7)	C3—H3	0.9300
Cl1—Cu1ⁱ	2.2901 (5)	C4—C5	1.386 (3)
S1—O2	1.4380 (16)	C4—H4	0.9300
S1—O3	1.4568 (15)	C5—C6	1.501 (3)
S1—O1	1.4916 (14)	C6—H6A	0.9700
S1—C8	1.774 (2)	C6—H6B	0.9700
N1—C5	1.345 (3)	C7—C8	1.519 (3)
N1—C1	1.346 (3)	C7—H7A	0.9700
N2—C6	1.475 (3)	C7—H7B	0.9700
N2—C7	1.492 (2)	C8—H8A	0.9700
N2—H1N	0.95 (3)	C8—H8B	0.9700
C1—C2	1.382 (3)

O1—Cu1—N1	169.95 (7)	C3—C2—C1	118.9 (2)
O1—Cu1—N2	92.73 (6)	C3—C2—H2	120.5
N1—Cu1—N2	81.18 (7)	C1—C2—H2	120.5
O1—Cu1—Cl1ⁱ	89.03 (4)	C2—C3—C4	119.45 (19)
N1—Cu1—Cl1ⁱ	95.57 (5)	C2—C3—H3	120.3
N2—Cu1—Cl1ⁱ	169.68 (5)	C4—C3—H3	120.3
O1—Cu1—Cl1	96.00 (5)	C5—C4—C3	118.9 (2)
N1—Cu1—Cl1	92.76 (5)	C5—C4—H4	120.5
N2—Cu1—Cl1	97.82 (5)	C3—C4—H4	120.5
Cl1ⁱ—Cu1—Cl1	92.091 (19)	N1—C5—C4	121.49 (19)
Cu1ⁱ—Cl1—Cu1	87.910 (19)	N1—C5—C6	115.27 (16)
O2—S1—O3	114.61 (10)	C4—C5—C6	123.21 (18)
O2—S1—O1	112.23 (10)	N2—C6—C5	108.83 (16)
O3—S1—O1	109.38 (9)	N2—C6—H6A	109.9
O2—S1—C8	107.16 (10)	C5—C6—H6A	109.9
O3—S1—C8	106.96 (10)	N2—C6—H6B	109.9
O1—S1—C8	105.98 (9)	C5—C6—H6B	109.9
S1—O1—Cu1	134.45 (9)	H6A—C6—H6B	108.3
C5—N1—C1	119.10 (17)	N2—C7—C8	110.64 (16)
C5—N1—Cu1	114.53 (13)	N2—C7—H7A	109.5
C1—N1—Cu1	126.36 (14)	C8—C7—H7A	109.5
C6—N2—C7	111.18 (16)	N2—C7—H7B	109.5
C6—N2—Cu1	108.32 (13)	C8—C7—H7B	109.5
C7—N2—Cu1	120.32 (13)	H7A—C7—H7B	108.1
C6—N2—H1N	104.2 (16)	C7—C8—S1	113.05 (14)
C7—N2—H1N	112.8 (16)	C7—C8—H8A	109.0
Cu1—N2—H1N	98.3 (16)	S1—C8—H8A	109.0
N1—C1—C2	122.1 (2)	C7—C8—H8B	109.0
N1—C1—H1	119.0	S1—C8—H8B	109.0
C2—C1—H1	119.0	H8A—C8—H8B	107.8

O1—Cu1—Cl1—Cu1ⁱ	−89.25 (4)	N1—Cu1—N2—C7	158.15 (16)
N1—Cu1—Cl1—Cu1ⁱ	95.68 (5)	Cl1ⁱ—Cu1—N2—C7	−129.6 (2)
N2—Cu1—Cl1—Cu1ⁱ	177.15 (5)	Cl1—Cu1—N2—C7	66.55 (14)
Cl1ⁱ—Cu1—Cl1—Cu1ⁱ	0.0	C5—N1—C1—C2	1.6 (4)
O2—S1—O1—Cu1	86.40 (15)	Cu1—N1—C1—C2	−179.12 (19)
O3—S1—O1—Cu1	−145.24 (13)	N1—C1—C2—C3	−1.4 (4)
C8—S1—O1—Cu1	−30.26 (16)	C1—C2—C3—C4	0.0 (4)
N1—Cu1—O1—S1	70.6 (4)	C2—C3—C4—C5	1.1 (4)
N2—Cu1—O1—S1	18.24 (15)	C1—N1—C5—C4	−0.5 (3)
Cl1ⁱ—Cu1—O1—S1	−171.93 (14)	Cu1—N1—C5—C4	−179.82 (16)
Cl1—Cu1—O1—S1	−79.93 (14)	C1—N1—C5—C6	177.54 (19)
O1—Cu1—N1—C5	−68.7 (4)	Cu1—N1—C5—C6	−1.8 (2)
N2—Cu1—N1—C5	−15.48 (14)	C3—C4—C5—N1	−0.9 (3)
Cl1ⁱ—Cu1—N1—C5	174.39 (13)	C3—C4—C5—C6	−178.7 (2)
Cl1—Cu1—N1—C5	82.02 (14)	C7—N2—C6—C5	−170.83 (17)
O1—Cu1—N1—C1	112.1 (4)	Cu1—N2—C6—C5	−36.51 (19)
N2—Cu1—N1—C1	165.2 (2)	N1—C5—C6—N2	25.8 (2)
Cl1ⁱ—Cu1—N1—C1	−4.89 (19)	C4—C5—C6—N2	−156.21 (19)
Cl1—Cu1—N1—C1	−97.27 (19)	C6—N2—C7—C8	−169.70 (17)
O1—Cu1—N2—C6	−159.28 (14)	Cu1—N2—C7—C8	62.2 (2)
N1—Cu1—N2—C6	28.76 (14)	N2—C7—C8—S1	−74.07 (19)
Cl1ⁱ—Cu1—N2—C6	101.0 (3)	O2—S1—C8—C7	−65.44 (17)
Cl1—Cu1—N2—C6	−62.84 (13)	O3—S1—C8—C7	171.21 (14)
O1—Cu1—N2—C7	−29.89 (15)	O1—S1—C8—C7	54.58 (17)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O3ⁱⁱ	0.95 (3)	2.20 (3)	2.966 (2)	137 (2)

Symmetry code: (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₁₁N₂O₃S)₂Cl₂]
M_r	628.28
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.294 (1), 8.362 (1), 9.110 (1)
α, β, γ (°)	103.773 (2), 98.118 (2), 113.043 (2)
V (Å³)	544.9 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.43
Crystal size (mm)	0.33 × 0.20 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.505, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	3270, 2385, 2224
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.067, 1.10
No. of reflections	2385
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.34

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—H1N···O3ⁱ	0.95 (3)	2.20 (3)	2.966 (2)	137 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20471026) and the Natural Science Foundation of Henan Province (No. 0311021200).

References

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