metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Barclay, G. A. & Kennard, C. H. L. (1961). J. Chem. Soc. pp. 5244-5251.]); Hanic et al. (1964[Hanic, F., Štempelová, D. & Hanicová, K. (1964). Acta Cryst. 17, 633-639.]); Uekusa et al. (1989[Uekusa, H., Ohba, S., Saito, Y., Kato, M., Tokii, T. & Muto, Y. (1989). Acta Cryst. C45, 377-380.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu2(C2H3O2)4(C5H4Cl2N2)2]

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.407, Tmax = 0.696

  • 18645 measured reflections

  • 3028 independent reflections

  • 2996 reflections with I > 2σ(I)

  • Rint = 0.032

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.077

  • S = 1.10

  • 3028 reflections

  • 166 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −0.35 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2008[Rigaku/MSC (2008). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


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.

Refinement top

All H atoms were placed in idealized positions and refined as riding to their parent atoms, with bond lengths fixed to C—H = 0.93 (aromatic CH), 0.96 (methyl CH3) or 0.86 Å (amine NH2). Isotropic displacement parameters were calculated as Uiso(H) = 1.5 Ueq(carrier atom) for methyl groups and Uiso(H) = 1.2 Ueq(carrier atom) otherwise.

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
[Figure 1] 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)](CuCu) top
Crystal data top
[Cu2(C2H3O2)4(C5H4Cl2N2)2]F(000) = 692
Mr = 689.26Dx = 1.79 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6896 reflections
a = 8.2857 (17) Åθ = 4.8–36.7°
b = 17.010 (3) ŵ = 2.13 mm1
c = 9.3159 (19) ÅT = 150 K
β = 103.07 (3)°Prism, blue
V = 1279.0 (4) Å30.44 × 0.37 × 0.17 mm
Z = 2
Data collection top
Rigaku Saturn724+
diffractometer
3028 independent reflections
Radiation source: fine-focus sealed tube2996 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 28.5714 pixels mm-1θmax = 28.3°, θmin = 4.8°
ω scansh = 1111
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 2220
Tmin = 0.407, Tmax = 0.696l = 1212
18645 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0389P)2 + 0.9376P]
where P = (Fo2 + 2Fc2)/3
3028 reflections(Δ/σ)max = 0.001
166 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.35 e Å3
0 constraints
Crystal data top
[Cu2(C2H3O2)4(C5H4Cl2N2)2]V = 1279.0 (4) Å3
Mr = 689.26Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.2857 (17) ŵ = 2.13 mm1
b = 17.010 (3) ÅT = 150 K
c = 9.3159 (19) Å0.44 × 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)
Tmin = 0.407, Tmax = 0.696Rint = 0.032
18645 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.10Δρmax = 0.51 e Å3
3028 reflectionsΔρmin = 0.35 e Å3
166 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.42778 (2)0.430189 (12)0.47068 (2)0.01965 (8)
Cl10.39574 (7)0.08106 (3)0.48552 (6)0.03401 (12)
Cl20.03256 (6)0.24404 (3)0.07032 (6)0.03440 (12)
N20.5053 (2)0.24052 (10)0.5958 (2)0.0307 (4)
H100.54540.28430.63420.037*
H80.54290.19670.63610.037*
O10.26762 (16)0.47238 (8)0.57766 (15)0.0273 (3)
N10.32520 (17)0.30954 (9)0.40958 (17)0.0219 (3)
O30.60795 (16)0.41098 (8)0.36793 (17)0.0288 (3)
C70.1925 (2)0.16842 (10)0.2815 (2)0.0247 (3)
H70.14960.12140.23790.03*
C30.3140 (2)0.55353 (11)0.26647 (19)0.0232 (3)
C10.2771 (2)0.54062 (11)0.63179 (19)0.0225 (3)
C80.1324 (2)0.24062 (11)0.2229 (2)0.0235 (3)
C90.2019 (2)0.30880 (10)0.2871 (2)0.0234 (3)
H90.16240.35650.24450.028*
C50.3835 (2)0.24049 (10)0.4722 (2)0.0226 (3)
O40.57808 (18)0.40136 (8)0.65883 (16)0.0313 (3)
C60.3169 (2)0.16920 (10)0.4057 (2)0.0234 (3)
C40.1985 (3)0.58896 (14)0.1340 (2)0.0343 (4)
H50.26160.60870.06720.052*
H60.13770.63130.1650.052*
H40.12260.54950.08550.052*
O20.29538 (16)0.48257 (8)0.29448 (14)0.0268 (3)
C20.1372 (2)0.56626 (12)0.7009 (2)0.0311 (4)
H20.16170.61720.74480.047*
H10.12490.52910.77520.047*
H30.03610.56880.62640.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02168 (12)0.01600 (12)0.02151 (13)0.00133 (6)0.00540 (8)0.00034 (7)
Cl10.0456 (3)0.0184 (2)0.0364 (3)0.00489 (17)0.0057 (2)0.00646 (17)
Cl20.0360 (2)0.0319 (3)0.0301 (2)0.00245 (18)0.00326 (19)0.00169 (18)
N20.0313 (8)0.0209 (8)0.0354 (9)0.0017 (6)0.0016 (7)0.0037 (6)
O10.0303 (6)0.0243 (6)0.0310 (7)0.0009 (5)0.0144 (5)0.0015 (5)
N10.0219 (6)0.0182 (7)0.0267 (7)0.0017 (5)0.0077 (5)0.0000 (6)
O30.0269 (6)0.0249 (6)0.0377 (7)0.0009 (5)0.0139 (5)0.0034 (6)
C70.0291 (8)0.0191 (8)0.0276 (9)0.0010 (6)0.0101 (7)0.0033 (7)
C30.0244 (8)0.0254 (8)0.0203 (8)0.0064 (6)0.0059 (6)0.0020 (6)
C10.0238 (8)0.0237 (8)0.0206 (7)0.0049 (6)0.0063 (6)0.0043 (6)
C80.0236 (8)0.0238 (8)0.0234 (8)0.0025 (6)0.0060 (6)0.0001 (6)
C90.0233 (7)0.0203 (8)0.0277 (8)0.0034 (6)0.0084 (6)0.0016 (7)
C50.0226 (7)0.0202 (8)0.0267 (9)0.0023 (6)0.0091 (6)0.0012 (6)
O40.0382 (7)0.0223 (7)0.0289 (7)0.0014 (5)0.0019 (5)0.0038 (5)
C60.0285 (8)0.0156 (7)0.0283 (9)0.0039 (6)0.0112 (7)0.0037 (6)
C40.0334 (10)0.0389 (11)0.0278 (9)0.0106 (8)0.0009 (7)0.0072 (8)
O20.0295 (6)0.0239 (6)0.0250 (6)0.0007 (5)0.0023 (5)0.0022 (5)
C20.0301 (9)0.0328 (10)0.0346 (10)0.0050 (7)0.0159 (8)0.0004 (8)
Geometric parameters (Å, º) top
Cu1—O11.9665 (14)C7—H70.93
Cu1—O41.9688 (15)C3—O21.252 (2)
Cu1—O21.9691 (14)C3—O4i1.262 (2)
Cu1—O31.9743 (14)C3—C41.505 (2)
Cu1—N12.2449 (15)C1—O3i1.259 (2)
Cu1—Cu1i2.6600 (6)C1—C21.511 (2)
Cl1—C61.7342 (18)C8—C91.371 (3)
Cl2—C81.735 (2)C9—H90.93
N2—C51.349 (2)C5—C61.416 (3)
N2—H100.86O4—C3i1.262 (2)
N2—H80.86C4—H50.96
O1—C11.261 (2)C4—H60.96
N1—C91.348 (2)C4—H40.96
N1—C51.351 (2)C2—H20.96
O3—C1i1.259 (2)C2—H10.96
C7—C61.365 (3)C2—H30.96
C7—C81.390 (2)
O1—Cu1—O490.18 (6)O3i—C1—O1125.55 (16)
O1—Cu1—O286.83 (6)O3i—C1—C2117.59 (17)
O4—Cu1—O2167.37 (6)O1—C1—C2116.85 (16)
O1—Cu1—O3167.68 (6)C9—C8—C7119.85 (17)
O4—Cu1—O389.71 (7)C9—C8—Cl2120.30 (14)
O2—Cu1—O390.60 (6)C7—C8—Cl2119.83 (14)
O1—Cu1—N1101.65 (6)N1—C9—C8122.72 (16)
O4—Cu1—N197.18 (6)N1—C9—H9118.6
O2—Cu1—N195.43 (6)C8—C9—H9118.6
O3—Cu1—N190.58 (6)N2—C5—N1119.58 (16)
O1—Cu1—Cu1i83.91 (4)N2—C5—C6121.08 (16)
O4—Cu1—Cu1i82.81 (5)N1—C5—C6119.34 (16)
O2—Cu1—Cu1i84.67 (4)C3i—O4—Cu1124.50 (12)
O3—Cu1—Cu1i83.85 (4)C7—C6—C5121.61 (16)
N1—Cu1—Cu1i174.44 (4)C7—C6—Cl1119.62 (14)
C5—N2—H10120C5—C6—Cl1118.77 (14)
C5—N2—H8120C3—C4—H5109.5
H10—N2—H8120C3—C4—H6109.5
C1—O1—Cu1123.41 (12)H5—C4—H6109.5
C9—N1—C5119.05 (15)C3—C4—H4109.5
C9—N1—Cu1113.20 (11)H5—C4—H4109.5
C5—N1—Cu1127.40 (12)H6—C4—H4109.5
C1i—O3—Cu1123.07 (12)C3—O2—Cu1122.58 (12)
C6—C7—C8117.37 (16)C1—C2—H2109.5
C6—C7—H7121.3C1—C2—H1109.5
C8—C7—H7121.3H2—C2—H1109.5
O2—C3—O4i125.23 (16)C1—C2—H3109.5
O2—C3—C4118.13 (17)H2—C2—H3109.5
O4i—C3—C4116.64 (17)H1—C2—H3109.5
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu2(C2H3O2)4(C5H4Cl2N2)2]
Mr689.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)8.2857 (17), 17.010 (3), 9.3159 (19)
β (°) 103.07 (3)
V3)1279.0 (4)
Z2
Radiation typeMo Kα
µ (mm1)2.13
Crystal size (mm)0.44 × 0.37 × 0.17
Data collection
DiffractometerRigaku Saturn724+
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.407, 0.696
No. of measured, independent and
observed [I > 2σ(I)] reflections
18645, 3028, 2996
Rint0.032
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.077, 1.10
No. of reflections3028
No. of parameters166
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBarclay, G. A. & Kennard, C. H. L. (1961). J. Chem. Soc. pp. 5244–5251.  CrossRef Web of Science Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationHanic, F., Štempelová, D. & Hanicová, K. (1964). Acta Cryst. 17, 633–639.  CSD CrossRef IUCr Journals Web of Science Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2008). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationUekusa, H., Ohba, S., Saito, Y., Kato, M., Tokii, T. & Muto, Y. (1989). Acta Cryst. C45, 377–380.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar

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