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Acta Cryst. (2007). E63, m1649    [ doi:10.1107/S1600536807024580 ]

Bis(5-n-butylpyridine-2-carboxylato)copper(II)

L. He, J.-B. Yan, X.-X. Guo and W.-D. Song

Abstract top

The title complex, [Cu(C10H12NO2)2], was obtained by the reaction of 5-butylpyridyl-2-carboxylic acid (fusaric acid), extracted from blasted leaves of Rhizophora stylosa, with copper(II) chloride in aqueous solution. The metal atom lies on a center of symmetry. The CuII atom is coordinated by two carboxylate O atoms and two N atoms from two different fusaric acid ligands, and displays a square-planar geometry.

Comment top

Some structures of transition metal complexes containing the 5-butyl-pyridyl-2-carboxylic acid (fusaric acid) ligand have been reported. In the structural investigation of these complexes, it has been found that the fusaric acid functions as a multidentate ligand (Okabe, Muranishi & Wada (2002); Okabe, Wada & Muranishi (2002), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Cu complex obtained by the reaction of fusaric acid extracted from blasted leaves of Rhizophora Stylosa with copper chloride in aqueous solution.

As illustrated in Fig. 1, the CuII atom lies on a centre of symmetry and has a square planar geometry with the four coordinating atoms being two carboxyl O and two N atoms from two different fusaric acid ligands (Table 1).

Related literature top

For related literature, see: Okabe, Muranishi & Wada (2002); Okabe, Wada & Muranishi (2002).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of copper chloride (20 mmol) to a hot aqueous solution (25 ml) of 5-butyl-pyridyl-2-carboxylic acid (fusaric acid, 30 mmol) which was extracted from blasted leaves of Rhizophora Stylosa. The pH was then adjusted to 7.0–8.0 with NaOH (30 mmol). The resulting solution was filtered, and blue crystals were obtained at room temperature over several days.

Refinement top

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.5 Ueq(Cmethyl) and 1.2 Ueq(C) for all other carbon atoms.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 50% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry operator (-x, 1 - y, -z).
Bis(5-n-butylpyridine-2-carboxylato)copper(II) top
Crystal data top
[Cu(C10H12O2N)2]Z = 1
Mr = 419.95F(000) = 219
Triclinic, P1Dx = 1.507 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.5052 (1) ÅCell parameters from 3400 reflections
b = 8.0683 (3) Åθ = 1.6–28.0°
c = 11.3008 (5) ŵ = 1.21 mm−1
α = 70.338 (2)°T = 293 K
β = 89.399 (2)°Lamellar, blue
γ = 78.706 (1)°0.10 × 0.08 × 0.06 mm
V = 462.70 (3) Å3
Data collection top
Bruker APEX II area-detector
diffractometer		1788 independent reflections
Radiation source: fine-focus sealed tube1592 reflections with I > 2σ(I)
graphiteRint = 0.103
φ and ω scanθmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.889, Tmax = 0.935k = −8→9
3391 measured reflectionsl = −13→13
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0515P)2]
where P = (Fo2 + 2Fc2)/3
1788 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.57 e Å−3
Crystal data top
[Cu(C10H12O2N)2]γ = 78.706 (1)°
Mr = 419.95V = 462.70 (3) Å3
Triclinic, P1Z = 1
a = 5.5052 (1) ÅMo Kα radiation
b = 8.0683 (3) ŵ = 1.21 mm−1
c = 11.3008 (5) ÅT = 293 K
α = 70.338 (2)°0.10 × 0.08 × 0.06 mm
β = 89.399 (2)°
Data collection top
Bruker APEX II area-detector
diffractometer		1788 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1592 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.935Rint = 0.103
3391 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.107Δρmax = 0.43 e Å−3
S = 1.03Δρmin = −0.57 e Å−3
1788 reflectionsAbsolute structure: ?
125 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.3420 (5)0.7152 (3)−0.0530 (3)0.0335 (6)
C20.2087 (5)0.7509 (3)0.0571 (2)0.0283 (5)
C30.2515 (5)0.8740 (4)0.1089 (3)0.0347 (6)
H30.37610.93820.08040.042*
C40.1075 (5)0.9019 (4)0.2042 (3)0.0369 (6)
H40.13420.98610.23950.044*
C5−0.0768 (5)0.8045 (4)0.2472 (3)0.0346 (6)
C6−0.1070 (5)0.6822 (4)0.1910 (3)0.0340 (6)
H6−0.22800.61440.21910.041*
C7−0.2327 (5)0.8267 (4)0.3538 (3)0.0423 (7)
H7A−0.36020.75610.36400.051*
H7B−0.31470.95180.33200.051*
C8−0.0814 (5)0.7686 (4)0.4779 (3)0.0419 (7)
H8A0.00790.64570.49620.050*
H8B0.04090.84340.46770.050*
C9−0.2294 (6)0.7787 (4)0.5904 (3)0.0513 (8)
H9A−0.11490.74860.66270.062*
H9B−0.31880.90150.57270.062*
C10−0.4130 (7)0.6552 (5)0.6239 (3)0.0606 (9)
H10A−0.53920.69310.55690.091*
H10B−0.48800.65980.70010.091*
H10C−0.32820.53430.63590.091*
Cu10.00000.50000.00000.0349 (2)
N10.0302 (4)0.6562 (3)0.0972 (2)0.0306 (5)
O10.2520 (4)0.6114 (3)−0.09783 (18)0.0393 (5)
O20.5192 (4)0.7848 (3)−0.0923 (2)0.0468 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0425 (15)0.0329 (13)0.0321 (14)−0.0187 (11)0.0102 (11)−0.0141 (12)
C20.0325 (12)0.0285 (12)0.0269 (13)−0.0120 (10)0.0052 (10)−0.0101 (11)
C30.0441 (14)0.0345 (13)0.0355 (15)−0.0229 (11)0.0094 (11)−0.0167 (12)
C40.0445 (15)0.0375 (14)0.0387 (15)−0.0140 (12)0.0043 (12)−0.0226 (13)
C50.0341 (13)0.0410 (14)0.0335 (14)−0.0077 (11)0.0035 (11)−0.0188 (12)
C60.0343 (13)0.0436 (15)0.0332 (14)−0.0174 (11)0.0090 (11)−0.0195 (12)
C70.0403 (15)0.0574 (17)0.0386 (16)−0.0098 (13)0.0089 (12)−0.0287 (14)
C80.0450 (15)0.0478 (16)0.0412 (16)−0.0133 (13)0.0053 (12)−0.0237 (14)
C90.064 (2)0.0558 (18)0.0372 (17)−0.0060 (16)0.0062 (14)−0.0233 (15)
C100.057 (2)0.083 (2)0.0418 (19)−0.0143 (18)0.0130 (15)−0.0211 (18)
Cu10.0485 (3)0.0414 (3)0.0307 (3)−0.0303 (2)0.0160 (2)−0.0215 (2)
N10.0344 (11)0.0344 (11)0.0302 (11)−0.0170 (9)0.0086 (9)−0.0151 (10)
O10.0533 (11)0.0479 (11)0.0355 (10)−0.0325 (9)0.0198 (8)−0.0265 (9)
O20.0561 (12)0.0531 (12)0.0519 (13)−0.0392 (10)0.0278 (10)−0.0298 (10)
Geometric parameters (Å, °) top
C1—O21.225 (3)C7—H7B0.9700
C1—O11.288 (3)C8—C91.520 (4)
C1—C21.519 (4)C8—H8A0.9700
C2—N11.344 (3)C8—H8B0.9700
C2—C31.367 (4)C9—C101.514 (5)
C3—C41.383 (4)C9—H9A0.9700
C3—H30.9300C9—H9B0.9700
C4—C51.389 (4)C10—H10A0.9600
C4—H40.9300C10—H10B0.9600
C5—C61.375 (4)C10—H10C0.9600
C5—C71.511 (4)Cu1—O1i1.9344 (18)
C6—N11.345 (3)Cu1—O11.9344 (18)
C6—H60.9300Cu1—N11.960 (2)
C7—C81.520 (4)Cu1—N1i1.960 (2)
C7—H7A0.9700
O2—C1—O1125.5 (3)C7—C8—H8A108.4
O2—C1—C2119.8 (2)C9—C8—H8B108.4
O1—C1—C2114.7 (2)C7—C8—H8B108.4
N1—C2—C3121.3 (2)H8A—C8—H8B107.5
N1—C2—C1113.9 (2)C10—C9—C8113.9 (3)
C3—C2—C1124.7 (2)C10—C9—H9A108.8
C2—C3—C4119.3 (2)C8—C9—H9A108.8
C2—C3—H3120.4C10—C9—H9B108.8
C4—C3—H3120.4C8—C9—H9B108.8
C3—C4—C5120.1 (3)H9A—C9—H9B107.7
C3—C4—H4119.9C9—C10—H10A109.5
C5—C4—H4119.9C9—C10—H10B109.5
C6—C5—C4117.1 (2)H10A—C10—H10B109.5
C6—C5—C7121.1 (2)C9—C10—H10C109.5
C4—C5—C7121.8 (3)H10A—C10—H10C109.5
N1—C6—C5123.1 (2)H10B—C10—H10C109.5
N1—C6—H6118.5O1i—Cu1—O1180.00 (11)
C5—C6—H6118.5O1i—Cu1—N196.03 (8)
C5—C7—C8112.8 (2)O1—Cu1—N183.97 (8)
C5—C7—H7A109.0O1i—Cu1—N1i83.97 (8)
C8—C7—H7A109.0O1—Cu1—N1i96.03 (8)
C5—C7—H7B109.0N1—Cu1—N1i180.00 (8)
C8—C7—H7B109.0C2—N1—C6119.1 (2)
H7A—C7—H7B107.8C2—N1—Cu1112.24 (17)
C9—C8—C7115.4 (2)C6—N1—Cu1128.59 (18)
C9—C8—H8A108.4C1—O1—Cu1114.62 (17)
Symmetry codes: (i) −x, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.9344 (18)Cu1—N11.960 (2)
O1i—Cu1—O1180.00 (11)O1—Cu1—N183.97 (8)
O1i—Cu1—N196.03 (8)N1—Cu1—N1i180.00 (8)
Symmetry codes: (i) −x, −y+1, −z.
Acknowledgements top

The authors thank the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) and Guangdong Ocean University for supporting this study.

references
References top

Bruker (2004). APEX2 (Version 7.23A) and SMART (Version 7.23A). Bruker AXS Inc, Madison, Wisconsin, USA. Should SMART be replace by SAINT here? [Please also check version.]

Okabe, N., Muranishi, Y. & Wada, Y. (2002). Acta Cryst. C58, m511–m513.

Okabe, N., Wada, Y. & Muranishi, Y. (2002). Acta Cryst. E58, m372–m374.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.