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

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ISSN: 2056-9890
Volume 64| Part 3| March 2008| Pages m448-m449

Poly[μ4-succinato-μ2-succinato-bis­[diamminecopper(II)]]

aFaculty of Science, ZheJiang Forestry University, Lin'An 311300, People's Republic of China, and bDepartment of Chemistry, Liaocheng University, Liaocheng, Shandong 252059, People's Republic of China
*Correspondence e-mail: jinsw@zjfc.edu.cn

(Received 28 October 2007; accepted 23 January 2008; online 6 February 2008)

In the title compound, [Cu(C4H4O4)(NH3)2]n, the Cu atom is coordinated by the N atoms of two ammonia mol­ecules and four O atoms from three different succinate ligands in a highly distorted octa­hedral geometry. The Cu atom and the C and O atoms of the succinate ligands lie on a mirror plane. Two adjacent CuO4N2 octa­hedra share one common O–O edge, forming a Cu2O6N4 biocta­hedron with a Cu⋯Cu separation of 3.524 (2) Å. Neighboring biocta­hedra are connected by bis-unidentate succinate anions in the a-axis direction, while in the c-axis direction biocta­hedra are connected by bis-bidentate succinate anions, leading to an infinite two-dimensional network structure. These networks are further connected along the a-axis direction by hydrogen bonds between ammonia ligands and carboxyl­ate O atoms of neighboring network layers, forming a three-dimensional lamellar structure.

Related literature

For related literature, see: Halcrow (2001[Halcrow, M. A. (2001). Angew. Chem. Int. Ed. 40, 1433-1436.]); Holm et al. (1996[Holm, R. H., Kennepohl, P. & Solomon, E. I. (1996). Chem. Rev. 96, 2239-2341.]); Jin & Chen (2007a[Jin, S. W. & Chen, W. Z. (2007a). Polyhedron, 26, 3074-3084.],b[Jin, S. W. & Chen, W. Z. (2007b). Inorg. Chim. Acta, 12, 3756-3764.]); Jin et al. (2007[Jin, S. W., Wang, D. Q. & Chen, W. Z. (2007). Inorg. Chem. Commun. 10, 685-689.]); Kato & Muto (1988[Kato, M. & Muto, Y. (1988). Coord. Chem. Rev. 92, 45-83.]); Lassahn et al. (2004[Lassahn, P. G., Lozan, V., Timco, G. A., Christian, P., Janiak, C. & Winpenny, R. E. P. (2004). J. Catal. 222, 260-267.]); Mehrotra & Bohra (1983[Mehrotra, R. C. & Bohra, R. (1983). Metal Carboxylates. New York: Academic Press.]); Park et al. (2001[Park, E. D., Hwang, Y. S. & Lee, J. S. (2001). Catal. Commun. 2, 187-190.]); Rao et al. (2004[Rao, C. N. R., Natarajan, S. & Vaidhyanathan, R. (2004). Angew. Chem. Int. Ed. 43, 1466-1296.]); Zheng et al. (2000[Zheng, Y. Q., Sun, J. & Lin, J. L. (2000). Z. Anorg. Allg. Chem. 626, 1271-1273.], 2001[Zheng, Y. Q., Lin, J. L. & Sun, J. (2001). Z. Anorg. Allg. Chem. 627, 1993-1996.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C4H4O4)(NH3)2]

  • Mr = 213.68

  • Monoclinic, C 2/m

  • a = 13.761 (6) Å

  • b = 7.374 (3) Å

  • c = 8.709 (4) Å

  • β = 124.515 (4)°

  • V = 728.2 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.97 mm−1

  • T = 293 (2) K

  • 0.27 × 0.15 × 0.09 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.501, Tmax = 0.776

  • 1874 measured reflections

  • 694 independent reflections

  • 641 reflections with I > 2σ(I)

  • Rint = 0.036

Refinement
  • R[F2 > 2σ(F2)] = 0.026

  • wR(F2) = 0.072

  • S = 1.14

  • 694 reflections

  • 64 parameters

  • H-atom parameters constrained

  • Δρmax = 0.37 e Å−3

  • Δρmin = −0.58 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H3⋯O4i 0.86 2.44 3.272 (3) 164
N1—H2⋯O2ii 0.86 2.32 3.133 (3) 159
N1—H1⋯O3iii 0.86 2.48 3.331 (3) 169
N1—H1⋯O4iii 0.86 2.41 3.085 (3) 136
Symmetry codes: (i) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (ii) [-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]; (iii) [-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+2].

Data collection: SMART (Bruker, 1997[Bruker (1997). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: SHELXTL.

Supporting information


Comment top

Carboxylate complexes have been intensively investigated in recent years due to their interesting coordination chemistry allowing for unusual structural features and leading to various physical and chemical properties and practical applications in fields such as dyes, extractants, drugs, pesticides and catalysts (Mehrotra & Bohra, 1983; Rao et al., 2004; Lassahn et al., 2004; Park et al., 2001). Among them copper(II) carboxylates are of special interest as they are easily obtained as polynuclear units having relevance to magnetic materials (Kato & Muto, 1988) and biology (Holm et al., 1996; Halcrow, 2001) As an extension of our research on carboxylate coordination compounds (Jin & Chen, 2007a; Jin & Chen, 2007b; Jin et al., 2007), we herein report the synthesis and crystal structure of copper succinate diammonia.

The compound of the formula (C4H10CuN2O4)n was obtained by reacting copper(II) chloride dihydrate with succinic acid in basic solution in the presence of bis(N-benzimidazolyl)methane. However, bis(N-benzimidazolyl)methane does not appear in the title compound. Single crystals of the title compound suitable for X-ray diffraction analysis cannot be obtained by evaporating an appropriate solution of the title compound in water or organic solvents. We found that it can be dissolved in a concentrated solution of ammonia obviously substituting bis(N-benzimidazolyl)methane ligands bound to Cu(II) cations against ammonia. The title compound is stable in air, insoluble in water and common organic solvents. The basic building blocks in the title compound are the edge-shared Cu2O6N4 bioctahedra. The Cu atoms are each coordinated by four oxygen atoms of three different succinato ligands and two ammonia nitrogen atoms to complete CuO4N2 octahedral geometry (Fig. 1). Two of the coordinated succinate ions act as bis-tridentate bridging ligands. The other succinate ions function as bis-monodentate bridging ligands. Four succinate ions and four copper atoms form 28-membered rings. One oxygen atom of the succinate ions acts as bidentate ligand bridging two copper atoms. The Cu—O bond distances (varying in the range of 1.978 (3)–2.001 (3) Å), and Cu(1)—N(1) bond distances (1.993 (3) Å), are comparable with some known Cu dicarboxylates (Zheng et al., 2000). The O—Cu—O (O(3)—Cu(1)—O(1),176.92 (9) degree) bond angles exhibit significant close to 180 degree, and O—Cu—N bond angles are close to 90 degree also, which implies the CuO4N2 octahedra to be slightly distorted. Two adjacent octahedra are condensed via two carboxylate O atoms to form Cu2O6N4 bioctahedra. The Cu—Cu separation within the bioctahedra is of 3.035 Å, much shorter than those reported earlier (Zheng et al., 2001). Obviously such large Cu—Cu distance along the acute O—Cu—O (75.7 degree), and obtuse Cu—O—Cu angles (104.3 degree) subtended at the Cu and the bridging O atoms implies that there is no or just a very weak interaction between the paired Cu atoms.

Neighboring bioctahedras are additionally connected by bis-unidentate succinate ions in a axis direction, while in c axis direction bioctahedra are connected by bis-tridentate succinate ions, leading to a two-dimensional network structure. Within the network, the closest intra-bioctahedra Cu—Cu distance of 3.035 (1) Å is substantially smaller than the nearest inter-bioctahedra Cu—Cu distance of 8.350 (1) Å. The resulting infinite layers are further connected through hydrogen bonds between ammonia molecules and carboxylate O atoms of neighboring network layers to form three-dimensional lamellar structure, as demonstrated in Fig. 2.

Related literature top

For related literature, see: Halcrow (2001); Holm et al. (1996); Jin & Chen (2007a,b); Jin et al. (2007); Kato & Muto (1988); Lassahn et al. (2004); Mehrotra & Bohra (1983); Park et al. (2001); Rao et al. (2004); Zheng et al. (2000, 2001).

Experimental top

All reagents and solvents were used as obtained without further purification. The CHN elemental analyses were performed on a Perkin-Elmer model 2400 elemental analyzer.

A mixture of copper chloride dihydrate (34.2 mg, 0.2 mmol), NaOH (16 mg, 0.4 mmol), succinic acid (23.6 mg, 0.2 mmol), and bis(N-benzimidazolyl)methane (30 mg, 0.2 mmol), in methanol (10 ml) was refluxed for 1 h. The resulted blue precipitate was collected and dissolved in a minimum amount of concentrated ammonia. Blue single crystals of the title compound were obtained by slow evaporation of the ammonia solution at ambient temperature. Yield: 32 mg, 75%. Anal. Calcd for C4H10CuN2O4: C, 22.46; H, 4.68; N 13.10. Found: C, 22.41; H, 4.63; N 13.07.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.86 Å, C—H = 0.96 Å, and Uiso(H) = 1.2Ueq(C). Hydrogen atoms bound to water molecules were located in the Fourier difference map, and their distances were fixed.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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
[Figure 1] Fig. 1. The molecular structure of one repeating unit the title coordination polymer, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Three dimensional network structure connected via hydrogen bonds.
Poly[µ4-succinato-µ2-succinato-bis[diamminecopper(II)]] top
Crystal data top
[Cu(C4H4O4)(NH3)2]F(000) = 436
Mr = 213.68Dx = 1.949 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 1618 reflections
a = 13.761 (6) Åθ = 2.8–28.2°
b = 7.374 (3) ŵ = 2.97 mm1
c = 8.709 (4) ÅT = 293 K
β = 124.515 (4)°Block, blue
V = 728.2 (5) Å30.27 × 0.15 × 0.09 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
694 independent reflections
Radiation source: fine-focus sealed tube641 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1516
Tmin = 0.501, Tmax = 0.776k = 88
1874 measured reflectionsl = 910
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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0361P)2 + 0.9127P]
where P = (Fo2 + 2Fc2)/3
694 reflections(Δ/σ)max = 0.001
64 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.58 e Å3
Crystal data top
[Cu(C4H4O4)(NH3)2]V = 728.2 (5) Å3
Mr = 213.68Z = 4
Monoclinic, C2/mMo Kα radiation
a = 13.761 (6) ŵ = 2.97 mm1
b = 7.374 (3) ÅT = 293 K
c = 8.709 (4) Å0.27 × 0.15 × 0.09 mm
β = 124.515 (4)°
Data collection top
Bruker SMART APEX CCD
diffractometer
694 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
641 reflections with I > 2σ(I)
Tmin = 0.501, Tmax = 0.776Rint = 0.036
1874 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.14Δρmax = 0.37 e Å3
694 reflectionsΔρmin = 0.58 e Å3
64 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
xyzUiso*/Ueq
Cu10.84469 (3)0.50000.85475 (5)0.0211 (2)
O10.9788 (2)0.50000.8255 (3)0.0239 (6)
O20.8291 (2)0.50000.5275 (4)0.0387 (8)
O30.7184 (2)0.50000.8984 (4)0.0280 (6)
O40.5330 (2)0.50000.8099 (4)0.0381 (7)
N10.83799 (18)0.7693 (4)0.8316 (3)0.0280 (5)
H10.83350.82630.91340.042*
H20.77970.80730.72510.042*
H30.89900.81310.84070.042*
C10.9363 (3)0.50000.6510 (5)0.0223 (8)
C21.0265 (3)0.50000.6041 (5)0.0275 (9)
H2A1.07630.39390.65990.033*
C30.6069 (3)0.50000.7718 (5)0.0241 (8)
C40.5663 (3)0.50000.5694 (5)0.0261 (8)
H40.59870.39390.54800.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0203 (3)0.0245 (3)0.0180 (3)0.0000.0106 (2)0.000
O10.0217 (13)0.0359 (16)0.0144 (12)0.0000.0104 (11)0.000
O20.0267 (15)0.068 (2)0.0187 (13)0.0000.0111 (12)0.000
O30.0188 (13)0.0446 (17)0.0191 (12)0.0000.0097 (11)0.000
O40.0252 (15)0.066 (2)0.0255 (14)0.0000.0159 (12)0.000
N10.0283 (12)0.0266 (14)0.0233 (11)0.0018 (10)0.0111 (10)0.0004 (10)
C10.0249 (18)0.024 (2)0.0183 (16)0.0000.0127 (15)0.000
C20.0256 (19)0.039 (2)0.0200 (19)0.0000.0139 (16)0.000
C30.0256 (19)0.0239 (19)0.0215 (17)0.0000.0126 (16)0.000
C40.028 (2)0.031 (2)0.0179 (17)0.0000.0118 (17)0.000
Geometric parameters (Å, º) top
Cu1—O31.978 (3)N1—H20.8599
Cu1—N1i1.993 (3)N1—H30.8599
Cu1—N11.993 (3)C1—C21.510 (5)
Cu1—O12.001 (3)C2—C2ii1.524 (7)
O1—C11.282 (4)C2—H2A0.9698
O2—C11.240 (5)C3—C41.517 (5)
O3—C31.286 (5)C4—C4iii1.514 (7)
O4—C31.236 (5)C4—H40.9696
N1—H10.8599
O3—Cu1—N1i91.38 (6)H2—N1—H3104.0
O3—Cu1—N191.38 (6)O2—C1—O1123.2 (3)
N1i—Cu1—N1170.34 (12)O2—C1—C2121.5 (3)
O3—Cu1—O1176.92 (9)O1—C1—C2115.3 (3)
N1i—Cu1—O188.87 (6)C1—C2—C2ii114.1 (4)
N1—Cu1—O188.87 (6)C1—C2—H2A108.7
C1—O1—Cu1108.5 (2)C2ii—C2—H2A108.8
C3—O3—Cu1125.9 (2)O4—C3—O3122.2 (3)
Cu1—N1—H1115.1O4—C3—C4119.7 (3)
Cu1—N1—H2113.3O3—C3—C4118.1 (3)
H1—N1—H2105.8C4iii—C4—C3114.3 (4)
Cu1—N1—H3112.2C4iii—C4—H4108.9
H1—N1—H3105.4C3—C4—H4108.5
O3—Cu1—O1—C1180.000 (10)Cu1—O1—C1—C2180.000 (1)
N1i—Cu1—O1—C185.31 (6)O2—C1—C2—C2ii0.000 (1)
N1—Cu1—O1—C185.31 (6)O1—C1—C2—C2ii180.000 (2)
N1i—Cu1—O3—C385.37 (6)Cu1—O3—C3—O4180.000 (1)
N1—Cu1—O3—C385.37 (6)Cu1—O3—C3—C40.000 (2)
O1—Cu1—O3—C3180.000 (12)O4—C3—C4—C4iii0.0
Cu1—O1—C1—O20.0O3—C3—C4—C4iii180.000 (2)
Symmetry codes: (i) x, y+1, z; (ii) x+2, y+1, z+1; (iii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H3···O4iv0.862.443.272 (3)164
N1—H2···O2v0.862.323.133 (3)159
N1—H1···O3vi0.862.483.331 (3)169
N1—H1···O4vi0.862.413.085 (3)136
Symmetry codes: (iv) x+1/2, y+1/2, z; (v) x+3/2, y+3/2, z+1; (vi) x+3/2, y+3/2, z+2.

Experimental details

Crystal data
Chemical formula[Cu(C4H4O4)(NH3)2]
Mr213.68
Crystal system, space groupMonoclinic, C2/m
Temperature (K)293
a, b, c (Å)13.761 (6), 7.374 (3), 8.709 (4)
β (°) 124.515 (4)
V3)728.2 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.97
Crystal size (mm)0.27 × 0.15 × 0.09
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.501, 0.776
No. of measured, independent and
observed [I > 2σ(I)] reflections
1874, 694, 641
Rint0.036
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.072, 1.14
No. of reflections694
No. of parameters64
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.58

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H3···O4i0.862.443.272 (3)164.3
N1—H2···O2ii0.862.323.133 (3)158.5
N1—H1···O3iii0.862.483.331 (3)169.4
N1—H1···O4iii0.862.413.085 (3)135.8
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+3/2, y+3/2, z+1; (iii) x+3/2, y+3/2, z+2.
 

Acknowledgements

The authors thank the Zhejiang Forestry University Science Foundation for financial support.

References

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ISSN: 2056-9890
Volume 64| Part 3| March 2008| Pages m448-m449
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