Tetra-μ-acetato-κ8O:O′-bis­[(2-amino-3,5-dichloro­pyridine-κN1)copper(II)](Cu—Cu)

Chang, H.-C.; Cole, J.M.; Lin, T.-C.; Waddell, P.G.

doi:10.1107/S1600536811015662

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m691

doi:10.1107/S1600536811015662

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Tetra-μ-acetato-κ⁸O:O′-bis[(2-amino-3,5-dichloropyridine-κN¹)copper(II)](Cu—Cu)

Hui-Chang Chang,^a Jacqueline M. Cole,^a ^*‡ Tze-Chia Lin ^a and Paul G. Waddell ^a §

^aCavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, England
^*Correspondence e-mail: jmc61@cam.ac.uk

(Received 22 February 2011; accepted 26 April 2011; online 7 May 2011)

The title binuclear Cu(II) complex, [Cu₂(CH₃CO₂)₄(C₅H₄Cl₂N₂)₂], is disposed about a crystallographic inversion center, located at the mid-point of the Cu—Cu connecting line. The Cu⋯Cu distance is 2.6600 (6) Å and each metal atom exhibits a Jahn–Teller-distorted octahedral geometry.

Related literature

For the structures of polymorphic tetrakis(μ-acetato-O:O′)bis[(pyridine-N)copper(II)], see: Barclay & Kennard (1961 ); Hanic et al. (1964 ); Uekusa et al. (1989 ).

Experimental

Crystal data

[Cu₂(C₂H₃O₂)₄(C₅H₄Cl₂N₂)₂]
M_r = 689.26
Monoclinic, P 2₁ /c
a = 8.2857 (17) Å
b = 17.010 (3) Å
c = 9.3159 (19) Å
β = 103.07 (3)°
V = 1279.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 150 K
0.44 × 0.37 × 0.17 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.407, T_max = 0.696
18645 measured reflections
3028 independent reflections
2996 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.077
S = 1.10
3028 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015662/bh2343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015662/bh2343Isup2.hkl

checkCIF report

Comment top

The title compound is binuclear and disposed about a crystallographic centre of symmetry with a Cu—Cu distance of 2.6600 (8) Å. It has a similar geometry to that observed in the two known polymorphs of monopyridinecopper(II) acetate (Barclay & Kennard, 1961; Hanic et al., 1964; Uekusa et al., 1989). However, the Cu—N bond distance in the title compound is ca. 0.05 Å longer than that observed in the orthorhombic polymorph and ca. 0.08 Å longer than that in the monoclinic polymorph.

Related literature top

For the structures of polymorphic tetrakis(µ-acetato-O:O')bis[(pyridine-N)copper(II)], see: Barclay & Kennard (1961); Hanic et al. (1964); Uekusa et al. (1989).

Experimental top

A suspension of (3,5-dichloro-2-pyridylimino)-o-cresol copper (II) (1 mg, 0.0016 mmol) in ethanol (ca. 3 ml) was heated to ca. 323 K until fully dissolved. The solution was then allowed to cool to room temperature. Crystals suitable for single-crystal X-ray crystallography were grown via slow evaporation of methanol over seven days.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); 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: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level; hydrogen atoms omitted for clarity. Atoms labeled with flag A are generated by symmetry 1-x, 1-y, 1-z.

Tetra-µ-acetato-κ⁸O:O'-bis[(2-amino-3,5-dichloropyridine- κN¹)copper(II)](Cu—Cu) top

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₅H₄Cl₂N₂)₂]	F(000) = 692
M_r = 689.26	D_x = 1.79 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6896 reflections
a = 8.2857 (17) Å	θ = 4.8–36.7°
b = 17.010 (3) Å	µ = 2.13 mm⁻¹
c = 9.3159 (19) Å	T = 150 K
β = 103.07 (3)°	Prism, blue
V = 1279.0 (4) Å³	0.44 × 0.37 × 0.17 mm
Z = 2

Data collection top

Rigaku Saturn724+ diffractometer	3028 independent reflections
Radiation source: fine-focus sealed tube	2996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 28.5714 pixels mm^-1	θ_max = 28.3°, θ_min = 4.8°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→20
T_min = 0.407, T_max = 0.696	l = −12→12
18645 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0389P)² + 0.9376P] where P = (F_o² + 2F_c²)/3
3028 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³
0 constraints

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₅H₄Cl₂N₂)₂]	V = 1279.0 (4) Å³
M_r = 689.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2857 (17) Å	µ = 2.13 mm⁻¹
b = 17.010 (3) Å	T = 150 K
c = 9.3159 (19) Å	0.44 × 0.37 × 0.17 mm
β = 103.07 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	3028 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2996 reflections with I > 2σ(I)
T_min = 0.407, T_max = 0.696	R_int = 0.032
18645 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.10	Δρ_max = 0.51 e Å⁻³
3028 reflections	Δρ_min = −0.35 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.42778 (2)	0.430189 (12)	0.47068 (2)	0.01965 (8)
Cl1	0.39574 (7)	0.08106 (3)	0.48552 (6)	0.03401 (12)
Cl2	−0.03256 (6)	0.24404 (3)	0.07032 (6)	0.03440 (12)
N2	0.5053 (2)	0.24052 (10)	0.5958 (2)	0.0307 (4)
H10	0.5454	0.2843	0.6342	0.037*
H8	0.5429	0.1967	0.6361	0.037*
O1	0.26762 (16)	0.47238 (8)	0.57766 (15)	0.0273 (3)
N1	0.32520 (17)	0.30954 (9)	0.40958 (17)	0.0219 (3)
O3	0.60795 (16)	0.41098 (8)	0.36793 (17)	0.0288 (3)
C7	0.1925 (2)	0.16842 (10)	0.2815 (2)	0.0247 (3)
H7	0.1496	0.1214	0.2379	0.03*
C3	0.3140 (2)	0.55353 (11)	0.26647 (19)	0.0232 (3)
C1	0.2771 (2)	0.54062 (11)	0.63179 (19)	0.0225 (3)
C8	0.1324 (2)	0.24062 (11)	0.2229 (2)	0.0235 (3)
C9	0.2019 (2)	0.30880 (10)	0.2871 (2)	0.0234 (3)
H9	0.1624	0.3565	0.2445	0.028*
C5	0.3835 (2)	0.24049 (10)	0.4722 (2)	0.0226 (3)
O4	0.57808 (18)	0.40136 (8)	0.65883 (16)	0.0313 (3)
C6	0.3169 (2)	0.16920 (10)	0.4057 (2)	0.0234 (3)
C4	0.1985 (3)	0.58896 (14)	0.1340 (2)	0.0343 (4)
H5	0.2616	0.6087	0.0672	0.052*
H6	0.1377	0.6313	0.165	0.052*
H4	0.1226	0.5495	0.0855	0.052*
O2	0.29538 (16)	0.48257 (8)	0.29448 (14)	0.0268 (3)
C2	0.1372 (2)	0.56626 (12)	0.7009 (2)	0.0311 (4)
H2	0.1617	0.6172	0.7448	0.047*
H1	0.1249	0.5291	0.7752	0.047*
H3	0.0361	0.5688	0.6264	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02168 (12)	0.01600 (12)	0.02151 (13)	0.00133 (6)	0.00540 (8)	0.00034 (7)
Cl1	0.0456 (3)	0.0184 (2)	0.0364 (3)	0.00489 (17)	0.0057 (2)	0.00646 (17)
Cl2	0.0360 (2)	0.0319 (3)	0.0301 (2)	0.00245 (18)	−0.00326 (19)	−0.00169 (18)
N2	0.0313 (8)	0.0209 (8)	0.0354 (9)	0.0017 (6)	−0.0016 (7)	0.0037 (6)
O1	0.0303 (6)	0.0243 (6)	0.0310 (7)	−0.0009 (5)	0.0144 (5)	−0.0015 (5)
N1	0.0219 (6)	0.0182 (7)	0.0267 (7)	0.0017 (5)	0.0077 (5)	0.0000 (6)
O3	0.0269 (6)	0.0249 (6)	0.0377 (7)	0.0009 (5)	0.0139 (5)	−0.0034 (6)
C7	0.0291 (8)	0.0191 (8)	0.0276 (9)	−0.0010 (6)	0.0101 (7)	−0.0033 (7)
C3	0.0244 (8)	0.0254 (8)	0.0203 (8)	0.0064 (6)	0.0059 (6)	0.0020 (6)
C1	0.0238 (8)	0.0237 (8)	0.0206 (7)	0.0049 (6)	0.0063 (6)	0.0043 (6)
C8	0.0236 (8)	0.0238 (8)	0.0234 (8)	0.0025 (6)	0.0060 (6)	0.0001 (6)
C9	0.0233 (7)	0.0203 (8)	0.0277 (8)	0.0034 (6)	0.0084 (6)	0.0016 (7)
C5	0.0226 (7)	0.0202 (8)	0.0267 (9)	0.0023 (6)	0.0091 (6)	0.0012 (6)
O4	0.0382 (7)	0.0223 (7)	0.0289 (7)	0.0014 (5)	−0.0019 (5)	0.0038 (5)
C6	0.0285 (8)	0.0156 (7)	0.0283 (9)	0.0039 (6)	0.0112 (7)	0.0037 (6)
C4	0.0334 (10)	0.0389 (11)	0.0278 (9)	0.0106 (8)	0.0009 (7)	0.0072 (8)
O2	0.0295 (6)	0.0239 (6)	0.0250 (6)	0.0007 (5)	0.0023 (5)	0.0022 (5)
C2	0.0301 (9)	0.0328 (10)	0.0346 (10)	0.0050 (7)	0.0159 (8)	−0.0004 (8)

Geometric parameters (Å, º) top

Cu1—O1	1.9665 (14)	C7—H7	0.93
Cu1—O4	1.9688 (15)	C3—O2	1.252 (2)
Cu1—O2	1.9691 (14)	C3—O4ⁱ	1.262 (2)
Cu1—O3	1.9743 (14)	C3—C4	1.505 (2)
Cu1—N1	2.2449 (15)	C1—O3ⁱ	1.259 (2)
Cu1—Cu1ⁱ	2.6600 (6)	C1—C2	1.511 (2)
Cl1—C6	1.7342 (18)	C8—C9	1.371 (3)
Cl2—C8	1.735 (2)	C9—H9	0.93
N2—C5	1.349 (2)	C5—C6	1.416 (3)
N2—H10	0.86	O4—C3ⁱ	1.262 (2)
N2—H8	0.86	C4—H5	0.96
O1—C1	1.261 (2)	C4—H6	0.96
N1—C9	1.348 (2)	C4—H4	0.96
N1—C5	1.351 (2)	C2—H2	0.96
O3—C1ⁱ	1.259 (2)	C2—H1	0.96
C7—C6	1.365 (3)	C2—H3	0.96
C7—C8	1.390 (2)

O1—Cu1—O4	90.18 (6)	O3ⁱ—C1—O1	125.55 (16)
O1—Cu1—O2	86.83 (6)	O3ⁱ—C1—C2	117.59 (17)
O4—Cu1—O2	167.37 (6)	O1—C1—C2	116.85 (16)
O1—Cu1—O3	167.68 (6)	C9—C8—C7	119.85 (17)
O4—Cu1—O3	89.71 (7)	C9—C8—Cl2	120.30 (14)
O2—Cu1—O3	90.60 (6)	C7—C8—Cl2	119.83 (14)
O1—Cu1—N1	101.65 (6)	N1—C9—C8	122.72 (16)
O4—Cu1—N1	97.18 (6)	N1—C9—H9	118.6
O2—Cu1—N1	95.43 (6)	C8—C9—H9	118.6
O3—Cu1—N1	90.58 (6)	N2—C5—N1	119.58 (16)
O1—Cu1—Cu1ⁱ	83.91 (4)	N2—C5—C6	121.08 (16)
O4—Cu1—Cu1ⁱ	82.81 (5)	N1—C5—C6	119.34 (16)
O2—Cu1—Cu1ⁱ	84.67 (4)	C3ⁱ—O4—Cu1	124.50 (12)
O3—Cu1—Cu1ⁱ	83.85 (4)	C7—C6—C5	121.61 (16)
N1—Cu1—Cu1ⁱ	174.44 (4)	C7—C6—Cl1	119.62 (14)
C5—N2—H10	120	C5—C6—Cl1	118.77 (14)
C5—N2—H8	120	C3—C4—H5	109.5
H10—N2—H8	120	C3—C4—H6	109.5
C1—O1—Cu1	123.41 (12)	H5—C4—H6	109.5
C9—N1—C5	119.05 (15)	C3—C4—H4	109.5
C9—N1—Cu1	113.20 (11)	H5—C4—H4	109.5
C5—N1—Cu1	127.40 (12)	H6—C4—H4	109.5
C1ⁱ—O3—Cu1	123.07 (12)	C3—O2—Cu1	122.58 (12)
C6—C7—C8	117.37 (16)	C1—C2—H2	109.5
C6—C7—H7	121.3	C1—C2—H1	109.5
C8—C7—H7	121.3	H2—C2—H1	109.5
O2—C3—O4ⁱ	125.23 (16)	C1—C2—H3	109.5
O2—C3—C4	118.13 (17)	H2—C2—H3	109.5
O4ⁱ—C3—C4	116.64 (17)	H1—C2—H3	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂H₃O₂)₄(C₅H₄Cl₂N₂)₂]
M_r	689.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.2857 (17), 17.010 (3), 9.3159 (19)
β (°)	103.07 (3)
V (Å³)	1279.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.44 × 0.37 × 0.17

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.407, 0.696
No. of measured, independent and observed [I > 2σ(I)] reflections	18645, 3028, 2996
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.077, 1.10
No. of reflections	3028
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.35

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Footnotes

‡Other affiliation: Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada E3B 5A3.

§Other affiliation: Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada E3B 5A3

Acknowledgements

JMC thanks the Royal Society for a University Research Fellowship, the Taiwanese Ministry of Education for a partially funded PhD studentship (for TCL), the University of New Brunswick for the UNB Vice-Chancellor's Research Chair (JMC), and NSERC Discovery Grant 355708 (for PGW).

References

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