Redetermination of catena-poly­[bis­[chloro(μ-pyridine N-oxide-κ²O:O)copper(II)]-di-μ-chloro]

The title compound, [Cu₂Cl₄(C₅H₅NO)₂]_n, is a one-dimensional polymer in which the Cu^II atoms are alternately bridged by two O atoms [Cu...Cu = 3.2131 (10) Å] and two Cl atoms [Cu...Cu = 3.7061 (11) Å]. The metal centers display a very distorted coordination geometry, with the four stronger bonds defining a CuCl₂O₂ polyhedron midway between square planar and tetrahedral, which serves as the base of a pyramid, while the loosely bound Cl atom in the bridge occupies the apex. The simultaneous presence of a good hydrogen-bond acceptor and an adequate C—H donor leads to a network of C—H...Cl interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.087
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

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Computing details

Data collection: SMART-NT (Bruker, 2001); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

catena-poly[bis[chloro(µ_{-pyridine N-oxide-κ²O:O)copper(II)]-di-µ-chloro]}

Crystal data

[Cu2Cl4(C5H5NO)2]	F(000) = 452
Mr = 459.08	Dx = 2.022 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.7929 (18) Å	Cell parameters from 123 reflections
b = 13.509 (4) Å	θ = 3.1–24.7°
c = 9.980 (3) Å	µ = 3.53 mm^−1
β = 105.049 (5)°	T = 293 K
V = 754.2 (4) Å^3	Parallelepiped, dark_green
Z = 2	0.60 × 0.20 × 0.18 mm

Data collection

Bruker Smart APEX CCD area-detector diffractometer	1664 independent reflections
Radiation source: fine-focus sealed tube	1478 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 27.6°, θmin = 2.6°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −7→7
Tmin = 0.27, Tmax = 0.53	k = −17→17
5290 measured reflections	l = −12→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.1682P] where P = (Fo^2 + 2Fc^2)/3
1664 reflections	(Δ/σ)max = 0.012
92 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.62 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.26717 (5)	0.51602 (3)	0.59519 (4)	0.03047 (15)
Cl1	0.36018 (13)	0.61306 (6)	0.77684 (8)	0.0411 (2)
Cl2	0.58762 (12)	0.42200 (6)	0.63963 (8)	0.0357 (2)
O1	0.0344 (3)	0.41617 (13)	0.4887 (2)	0.0328 (5)
N1	0.0775 (4)	0.32101 (16)	0.4612 (2)	0.0263 (5)
C1	−0.0270 (5)	0.2504 (2)	0.5159 (3)	0.0365 (7)
H1A	−0.1288	0.2661	0.5710	0.044*
C2	0.0169 (7)	0.1543 (3)	0.4901 (4)	0.0518 (9)
H2A	−0.0569	0.1035	0.5262	0.062*
C3	0.1709 (7)	0.1330 (3)	0.4105 (4)	0.0520 (9)
H3A	0.2054	0.0676	0.3940	0.062*
C4	0.2729 (6)	0.2084 (3)	0.3557 (3)	0.0438 (8)
H4A	0.3771	0.1947	0.3012	0.053*
C5	0.2217 (5)	0.3034 (2)	0.3810 (3)	0.0351 (7)
H5A	0.2873	0.3555	0.3423	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0189 (2)	0.0273 (2)	0.0451 (3)	0.00219 (13)	0.00808 (15)	−0.00682 (14)
Cl1	0.0371 (4)	0.0471 (5)	0.0416 (4)	−0.0053 (3)	0.0150 (3)	−0.0120 (3)
Cl2	0.0243 (4)	0.0368 (4)	0.0481 (4)	0.0088 (3)	0.0132 (3)	0.0101 (3)
O1	0.0204 (9)	0.0182 (10)	0.0589 (13)	0.0026 (7)	0.0089 (9)	−0.0099 (9)
N1	0.0205 (11)	0.0196 (11)	0.0405 (13)	0.0008 (8)	0.0107 (10)	−0.0061 (10)
C1	0.0401 (17)	0.0325 (17)	0.0440 (16)	−0.0010 (13)	0.0236 (14)	−0.0003 (13)
C2	0.073 (3)	0.0260 (18)	0.064 (2)	−0.0018 (16)	0.032 (2)	0.0038 (15)
C3	0.067 (2)	0.0271 (18)	0.063 (2)	0.0105 (16)	0.0186 (19)	−0.0093 (15)
C4	0.0389 (18)	0.044 (2)	0.0538 (19)	0.0058 (14)	0.0207 (15)	−0.0157 (15)
C5	0.0283 (15)	0.0350 (17)	0.0478 (17)	−0.0029 (12)	0.0203 (13)	−0.0049 (13)

Geometric parameters (Å, º)

Cu1—O1^i	1.9579 (18)	C1—H1A	0.9300
Cu1—O1	2.0055 (19)	C2—C3	1.370 (5)
Cu1—Cl1	2.1881 (9)	C2—H2A	0.9300
Cu1—Cl2	2.1973 (9)	C3—C4	1.360 (5)
Cu1—Cl2^ii	2.8150 (10)	C3—H3A	0.9300
O1—N1	1.351 (3)	C4—C5	1.356 (4)
N1—C5	1.320 (3)	C4—H4A	0.9300
N1—C1	1.321 (4)	C5—H5A	0.9300
C1—C2	1.360 (5)
O1^i—Cu1—O1	71.67 (9)	N1—C1—C2	118.8 (3)
O1^i—Cu1—Cl1	94.28 (6)	N1—C1—H1A	120.6
O1—Cu1—Cl1	145.98 (6)	C2—C1—H1A	120.6
O1^i—Cu1—Cl2	165.94 (6)	C1—C2—C3	119.5 (3)
O1—Cu1—Cl2	97.74 (6)	C1—C2—H2A	120.3
Cl1—Cu1—Cl2	99.54 (3)	C3—C2—H2A	120.3
O1^i—Cu1—Cl2^ii	86.04 (7)	C4—C3—C2	119.5 (3)
O1—Cu1—Cl2^ii	93.68 (7)	C4—C3—H3A	120.3
Cl1—Cu1—Cl2^ii	116.68 (4)	C2—C3—H3A	120.3
Cl2—Cu1—Cl2^ii	85.44 (3)	C5—C4—C3	119.7 (3)
N1—O1—Cu1^i	123.34 (15)	C5—C4—H4A	120.2
N1—O1—Cu1	127.82 (15)	C3—C4—H4A	120.2
Cu1^i—O1—Cu1	108.33 (9)	N1—C5—C4	119.1 (3)
C5—N1—C1	123.4 (3)	N1—C5—H5A	120.4
C5—N1—O1	118.3 (2)	C4—C5—H5A	120.4
C1—N1—O1	118.3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl2^iii	0.93	2.86	3.649 (3)	143
C2—H2A···Cl1^iv	0.93	2.96	3.624 (4)	130
C3—H3A···Cl1^v	0.93	2.94	3.846 (3)	164
C4—H4A···Cl2^v	0.93	2.76	3.622 (3)	155
C5—H5A···Cl1^ii	0.93	2.65	3.406 (3)	139

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x, y−1/2, −z+3/2; (v) x, −y+1/2, z−1/2.