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

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 Cu^II atom is coordinated by two carboxylate O atoms and two N atoms from two different fusaric acid ligands, and displays a square-planar geometry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.107
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.103
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.10

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.14

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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 Cu^II 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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5 U_eq(C_methyl) and 1.2 U_eq(C) for all other carbon atoms.

Computing details

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

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)

Crystal data

[Cu(C10H12O2N)2]	Z = 1
Mr = 419.95	F(000) = 219
Triclinic, P1	Dx = 1.507 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5052 (1) Å	Cell parameters from 3400 reflections
b = 8.0683 (3) Å	θ = 1.6–28.0°
c = 11.3008 (5) Å	µ = 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) Å^3

Data collection

Bruker APEX II area-detector diffractometer	1788 independent reflections
Radiation source: fine-focus sealed tube	1592 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.103
φ and ω scan	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.889, Tmax = 0.935	k = −8→9
3391 measured reflections	l = −13→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0515P)^2] where P = (Fo^2 + 2Fc^2)/3
1788 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.57 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3420 (5)	0.7152 (3)	−0.0530 (3)	0.0335 (6)
C2	0.2087 (5)	0.7509 (3)	0.0571 (2)	0.0283 (5)
C3	0.2515 (5)	0.8740 (4)	0.1089 (3)	0.0347 (6)
H3	0.3761	0.9382	0.0804	0.042*
C4	0.1075 (5)	0.9019 (4)	0.2042 (3)	0.0369 (6)
H4	0.1342	0.9861	0.2395	0.044*
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	−0.2280	0.6144	0.2191	0.041*
C7	−0.2327 (5)	0.8267 (4)	0.3538 (3)	0.0423 (7)
H7A	−0.3602	0.7561	0.3640	0.051*
H7B	−0.3147	0.9518	0.3320	0.051*
C8	−0.0814 (5)	0.7686 (4)	0.4779 (3)	0.0419 (7)
H8A	0.0079	0.6457	0.4962	0.050*
H8B	0.0409	0.8434	0.4677	0.050*
C9	−0.2294 (6)	0.7787 (4)	0.5904 (3)	0.0513 (8)
H9A	−0.1149	0.7486	0.6627	0.062*
H9B	−0.3188	0.9015	0.5727	0.062*
C10	−0.4130 (7)	0.6552 (5)	0.6239 (3)	0.0606 (9)
H10A	−0.5392	0.6931	0.5569	0.091*
H10B	−0.4880	0.6598	0.7001	0.091*
H10C	−0.3282	0.5343	0.6359	0.091*
Cu1	0.0000	0.5000	0.0000	0.0349 (2)
N1	0.0302 (4)	0.6562 (3)	0.0972 (2)	0.0306 (5)
O1	0.2520 (4)	0.6114 (3)	−0.09783 (18)	0.0393 (5)
O2	0.5192 (4)	0.7848 (3)	−0.0923 (2)	0.0468 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0425 (15)	0.0329 (13)	0.0321 (14)	−0.0187 (11)	0.0102 (11)	−0.0141 (12)
C2	0.0325 (12)	0.0285 (12)	0.0269 (13)	−0.0120 (10)	0.0052 (10)	−0.0101 (11)
C3	0.0441 (14)	0.0345 (13)	0.0355 (15)	−0.0229 (11)	0.0094 (11)	−0.0167 (12)
C4	0.0445 (15)	0.0375 (14)	0.0387 (15)	−0.0140 (12)	0.0043 (12)	−0.0226 (13)
C5	0.0341 (13)	0.0410 (14)	0.0335 (14)	−0.0077 (11)	0.0035 (11)	−0.0188 (12)
C6	0.0343 (13)	0.0436 (15)	0.0332 (14)	−0.0174 (11)	0.0090 (11)	−0.0195 (12)
C7	0.0403 (15)	0.0574 (17)	0.0386 (16)	−0.0098 (13)	0.0089 (12)	−0.0287 (14)
C8	0.0450 (15)	0.0478 (16)	0.0412 (16)	−0.0133 (13)	0.0053 (12)	−0.0237 (14)
C9	0.064 (2)	0.0558 (18)	0.0372 (17)	−0.0060 (16)	0.0062 (14)	−0.0233 (15)
C10	0.057 (2)	0.083 (2)	0.0418 (19)	−0.0143 (18)	0.0130 (15)	−0.0211 (18)
Cu1	0.0485 (3)	0.0414 (3)	0.0307 (3)	−0.0303 (2)	0.0160 (2)	−0.0215 (2)
N1	0.0344 (11)	0.0344 (11)	0.0302 (11)	−0.0170 (9)	0.0086 (9)	−0.0151 (10)
O1	0.0533 (11)	0.0479 (11)	0.0355 (10)	−0.0325 (9)	0.0198 (8)	−0.0265 (9)
O2	0.0561 (12)	0.0531 (12)	0.0519 (13)	−0.0392 (10)	0.0278 (10)	−0.0298 (10)

Geometric parameters (Å, º)

C1—O2	1.225 (3)	C7—H7B	0.9700
C1—O1	1.288 (3)	C8—C9	1.520 (4)
C1—C2	1.519 (4)	C8—H8A	0.9700
C2—N1	1.344 (3)	C8—H8B	0.9700
C2—C3	1.367 (4)	C9—C10	1.514 (5)
C3—C4	1.383 (4)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.389 (4)	C10—H10A	0.9600
C4—H4	0.9300	C10—H10B	0.9600
C5—C6	1.375 (4)	C10—H10C	0.9600
C5—C7	1.511 (4)	Cu1—O1^i	1.9344 (18)
C6—N1	1.345 (3)	Cu1—O1	1.9344 (18)
C6—H6	0.9300	Cu1—N1	1.960 (2)
C7—C8	1.520 (4)	Cu1—N1^i	1.960 (2)
C7—H7A	0.9700
O2—C1—O1	125.5 (3)	C7—C8—H8A	108.4
O2—C1—C2	119.8 (2)	C9—C8—H8B	108.4
O1—C1—C2	114.7 (2)	C7—C8—H8B	108.4
N1—C2—C3	121.3 (2)	H8A—C8—H8B	107.5
N1—C2—C1	113.9 (2)	C10—C9—C8	113.9 (3)
C3—C2—C1	124.7 (2)	C10—C9—H9A	108.8
C2—C3—C4	119.3 (2)	C8—C9—H9A	108.8
C2—C3—H3	120.4	C10—C9—H9B	108.8
C4—C3—H3	120.4	C8—C9—H9B	108.8
C3—C4—C5	120.1 (3)	H9A—C9—H9B	107.7
C3—C4—H4	119.9	C9—C10—H10A	109.5
C5—C4—H4	119.9	C9—C10—H10B	109.5
C6—C5—C4	117.1 (2)	H10A—C10—H10B	109.5
C6—C5—C7	121.1 (2)	C9—C10—H10C	109.5
C4—C5—C7	121.8 (3)	H10A—C10—H10C	109.5
N1—C6—C5	123.1 (2)	H10B—C10—H10C	109.5
N1—C6—H6	118.5	O1^i—Cu1—O1	180.00 (11)
C5—C6—H6	118.5	O1^i—Cu1—N1	96.03 (8)
C5—C7—C8	112.8 (2)	O1—Cu1—N1	83.97 (8)
C5—C7—H7A	109.0	O1^i—Cu1—N1^i	83.97 (8)
C8—C7—H7A	109.0	O1—Cu1—N1^i	96.03 (8)
C5—C7—H7B	109.0	N1—Cu1—N1^i	180.00 (8)
C8—C7—H7B	109.0	C2—N1—C6	119.1 (2)
H7A—C7—H7B	107.8	C2—N1—Cu1	112.24 (17)
C9—C8—C7	115.4 (2)	C6—N1—Cu1	128.59 (18)
C9—C8—H8A	108.4	C1—O1—Cu1	114.62 (17)

Symmetry code: (i) −x, −y+1, −z.