Bis(4-hy­droxy­benzoato-κ2O,O′)bis­(pyridine-κN)copper(II)

Ozair, L.N.; Abdullah, N.; Lo, K.M.

doi:10.1107/S1600536811023038

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m952

doi:10.1107/S1600536811023038

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Bis(4-hydroxybenzoato-κ²O,O′)bis(pyridine-κN)copper(II)

Lailatun Nazirah Ozair,^a Norbani Abdullah ^a and Kong Mun Lo ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: kmlo@um.edu.my

(Received 21 May 2011; accepted 14 June 2011; online 18 June 2011)

In the title compound, [Cu(C₇H₅O₃)₂(C₅H₅N)₂], the Cu atom is located on an inversion center and is coordinated by the N atoms of the two pyridine ligands, trans to each other, and to the carboxylate O atoms of two bidentate 4-hydroxybenzoate ligands [Cu—O = 1.9706 (10) and 2.5204 (11) Å]. Hydrogen bonding between hydroxy H and carboxylate O atoms results in a layer structure parallel to the ab plane.

Related literature

For the structure of bis(p-hydroxybenzoate)dipicoline–copper(II), see: Sharma et al. (2009 ).

Experimental

Crystal data

[Cu(C₇H₅O₃)₂(C₅H₅N)₂]
M_r = 495.96
Monoclinic, P 2₁ /c
a = 10.6715 (2) Å
b = 8.5385 (1) Å
c = 12.3988 (2) Å
β = 109.124 (1)°
V = 1067.41 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 100 K
0.30 × 0.26 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.663, T_max = 0.746
9756 measured reflections
2448 independent reflections
2202 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.066
S = 1.06
2448 reflections
152 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.84	1.87	2.7028 (16)	171
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023038/om2435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023038/om2435Isup2.hkl

checkCIF report

Comment top

The copper atom in the title complex is located on an inversion center and adopts a distorted octahedral geometry, with the oxygen atoms of the carboxylic groups occupying the equatorial positions (Fig. 1). The axial Cu—N bond distance of 2.0076 (13) Å is comparable with that of bis(p-hydroxybenzoate)dipicoline-copper(II) which is 1.987 (2) Å (Sharma et al., 2009). The 4-hydroxybenzoate group acts as a bidentate ligand with Cu—O bond distances of 1.9706 (10) and 2.5204 (11) Å. The dipicoline-copper(II) complex differs from the title complex in that the two picoline ligands are cis to each other (N—Cu—N 91.50 (10)^o) whereas the two pyridine ligands in the title complex are trans to each other. The distortion from ideal octahedral geometry for the title compound is mainly due to the small bite angle (57.60 (4)°) formed by the bidentate carboxylate moiety. In the crystal structure, intermolecular O—H···O hydrogen bonds link the molecules into layers parallel to the ab plane (Fig. 2). The π-π contacts between the pyridine rings, Cg1-Cg1' [symmetry code: 2 - x, 1 - y, 2 - z, where Cg1 is the centroid of the ring (N1, C8—C12)] may further stabilize the overall structure, with centroid-centroid distance of 3.7878 (10) Å.

Related literature top

For the X-ray structure of bis(p-hydroxybenzoate)dipicoline-copper(II), see: Sharma et al. (2009).

Experimental top

p-Hydroxybenzoic acid (0.35 g, 2.5 mmol) was dissolved in 100 ml of ethanol. While stirring and gently heating the solution, copper(II) acetate monohydrate (0.26 g, 1.3 mmol) was added portionwise. This was followed by 0.5 ml of pyridine and the mixture was heated for 30 minutes. The solution mixture was then filtered and upon cooling of the filtrate gave the title compound as a dark green crystalline solid.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of bis(4-hydroxybenzoato-O, O')dipyridylcopper(II), showing 50% probability displacement ellipsoids and the atom numbering. Hydrogen atoms are drawn as spheres of arbitrary radius. (Symmetry code (i): -x + 2, -y, -z + 2).
	Fig. 2. A view down the c-axis of the crystal packing of the title compound. Hydrogen atoms have been omitted for clarity and the O—H···O hydrogen bonds are shown as red dotted lines.

Bis(4-hydroxybenzoato-κ²O,O')bis(pyridine-κN)copper(II) top

Crystal data top

[Cu(C₇H₅O₃)₂(C₅H₅N)₂]	F(000) = 510
M_r = 495.96	D_x = 1.543 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4633 reflections
a = 10.6715 (2) Å	θ = 3.0–28.2°
b = 8.5385 (1) Å	µ = 1.07 mm⁻¹
c = 12.3988 (2) Å	T = 100 K
β = 109.124 (1)°	Block, dark green
V = 1067.41 (3) Å³	0.30 × 0.26 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	2448 independent reflections
Radiation source: fine-focus sealed tube	2202 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.663, T_max = 0.746	k = −11→11
9756 measured reflections	l = −16→16

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0301P)² + 0.7197P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu(C₇H₅O₃)₂(C₅H₅N)₂]	V = 1067.41 (3) Å³
M_r = 495.96	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.6715 (2) Å	µ = 1.07 mm⁻¹
b = 8.5385 (1) Å	T = 100 K
c = 12.3988 (2) Å	0.30 × 0.26 × 0.20 mm
β = 109.124 (1)°

Data collection top

Bruker SMART APEXII diffractometer	2448 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2202 reflections with I > 2σ(I)
T_min = 0.663, T_max = 0.746	R_int = 0.023
9756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.06	Δρ_max = 0.38 e Å⁻³
2448 reflections	Δρ_min = −0.32 e Å⁻³
152 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

	x	y	z	U_iso*/U_eq
Cu1	1.0000	0.0000	1.0000	0.01147 (8)
O1	0.82299 (10)	0.04277 (13)	1.01071 (9)	0.0143 (2)
O2	0.81152 (11)	0.10333 (13)	0.83387 (9)	0.0162 (2)
O3	0.28650 (12)	0.42997 (16)	0.85782 (10)	0.0258 (3)
H3A	0.2618	0.4788	0.7956	0.039*
N1	1.05579 (12)	0.21481 (15)	1.06344 (11)	0.0139 (3)
C1	0.76211 (15)	0.10384 (17)	0.91341 (13)	0.0138 (3)
C2	0.63226 (15)	0.18074 (17)	0.89663 (13)	0.0152 (3)
C3	0.56256 (16)	0.24646 (19)	0.79114 (14)	0.0181 (3)
H3	0.5956	0.2350	0.7291	0.022*
C4	0.44571 (16)	0.32832 (19)	0.77537 (14)	0.0191 (3)
H4	0.3985	0.3717	0.7028	0.023*
C5	0.39815 (16)	0.3465 (2)	0.86627 (14)	0.0193 (3)
C6	0.46532 (18)	0.2783 (2)	0.97123 (15)	0.0270 (4)
H6	0.4314	0.2881	1.0328	0.032*
C7	0.58159 (17)	0.1960 (2)	0.98591 (14)	0.0232 (4)
H7	0.6271	0.1496	1.0577	0.028*
C8	1.01481 (17)	0.27077 (19)	1.14781 (14)	0.0188 (3)
H8	0.9540	0.2105	1.1719	0.023*
C9	1.05787 (19)	0.4126 (2)	1.20074 (15)	0.0242 (4)
H9	1.0285	0.4478	1.2611	0.029*
C10	1.14449 (18)	0.50256 (19)	1.16446 (15)	0.0226 (3)
H10	1.1758	0.6003	1.1996	0.027*
C11	1.18455 (16)	0.4474 (2)	1.07611 (15)	0.0205 (3)
H11	1.2425	0.5076	1.0485	0.025*
C12	1.13899 (15)	0.30311 (18)	1.02847 (14)	0.0170 (3)
H12	1.1678	0.2651	0.9685	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01118 (13)	0.00913 (13)	0.01483 (14)	−0.00004 (9)	0.00523 (9)	−0.00102 (10)
O1	0.0129 (5)	0.0132 (5)	0.0172 (5)	0.0019 (4)	0.0054 (4)	0.0005 (4)
O2	0.0161 (5)	0.0159 (5)	0.0175 (5)	−0.0010 (4)	0.0066 (4)	−0.0009 (4)
O3	0.0220 (6)	0.0344 (7)	0.0245 (6)	0.0126 (5)	0.0124 (5)	0.0100 (5)
N1	0.0142 (6)	0.0115 (6)	0.0158 (6)	0.0012 (5)	0.0045 (5)	0.0001 (5)
C1	0.0132 (7)	0.0085 (6)	0.0193 (7)	−0.0027 (5)	0.0047 (6)	−0.0019 (6)
C2	0.0128 (7)	0.0117 (7)	0.0200 (8)	−0.0013 (6)	0.0039 (6)	−0.0020 (6)
C3	0.0199 (8)	0.0170 (7)	0.0186 (8)	0.0011 (6)	0.0080 (6)	−0.0001 (6)
C4	0.0204 (8)	0.0188 (8)	0.0173 (7)	0.0026 (6)	0.0050 (6)	0.0027 (6)
C5	0.0140 (7)	0.0208 (8)	0.0237 (8)	0.0024 (6)	0.0070 (6)	0.0037 (7)
C6	0.0255 (9)	0.0378 (11)	0.0227 (9)	0.0111 (8)	0.0148 (7)	0.0085 (8)
C7	0.0207 (8)	0.0299 (9)	0.0197 (8)	0.0066 (7)	0.0076 (6)	0.0075 (7)
C8	0.0265 (8)	0.0140 (7)	0.0199 (8)	−0.0026 (6)	0.0130 (7)	−0.0004 (6)
C9	0.0374 (10)	0.0175 (8)	0.0222 (8)	−0.0034 (7)	0.0160 (7)	−0.0052 (7)
C10	0.0292 (9)	0.0139 (7)	0.0251 (8)	−0.0052 (7)	0.0094 (7)	−0.0049 (7)
C11	0.0202 (8)	0.0151 (7)	0.0281 (9)	−0.0039 (6)	0.0107 (7)	−0.0009 (7)
C12	0.0169 (7)	0.0151 (7)	0.0210 (8)	−0.0003 (6)	0.0089 (6)	−0.0016 (6)

Geometric parameters (Å, º) top

Cu1—O1	1.9706 (10)	C4—H4	0.9500
Cu1—N1	2.0076 (13)	C5—C6	1.391 (2)
Cu1—O2	2.5204 (11)	C6—C7	1.385 (2)
O1—C1	1.2790 (19)	C6—H6	0.9500
O2—C1	1.2614 (18)	C7—H7	0.9500
O3—C5	1.3624 (19)	C8—C9	1.382 (2)
O3—H3A	0.8400	C8—H8	0.9500
N1—C12	1.340 (2)	C9—C10	1.386 (2)
N1—C8	1.347 (2)	C9—H9	0.9500
C1—C2	1.485 (2)	C10—C11	1.383 (2)
C2—C7	1.388 (2)	C10—H10	0.9500
C2—C3	1.393 (2)	C11—C12	1.384 (2)
C3—C4	1.386 (2)	C11—H11	0.9500
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.388 (2)

O1—Cu1—O1ⁱ	180.0	C5—C4—H4	120.2
O1—Cu1—N1ⁱ	91.60 (5)	O3—C5—C4	122.64 (15)
O1—Cu1—N1	88.40 (5)	O3—C5—C6	117.43 (15)
O1ⁱ—Cu1—N1	91.60 (5)	C4—C5—C6	119.94 (15)
N1ⁱ—Cu1—N1	180.0	C7—C6—C5	120.02 (15)
O1—Cu1—O2	57.60 (4)	C7—C6—H6	120.0
O1ⁱ—Cu1—O2	122.40 (4)	C5—C6—H6	120.0
N1ⁱ—Cu1—O2	86.83 (4)	C6—C7—C2	120.61 (15)
N1—Cu1—O2	93.17 (4)	C6—C7—H7	119.7
C1—O1—Cu1	102.35 (9)	C2—C7—H7	119.7
C1—O2—Cu1	77.78 (8)	N1—C8—C9	122.52 (15)
C5—O3—H3A	109.5	N1—C8—H8	118.7
C12—N1—C8	118.01 (13)	C9—C8—H8	118.7
C12—N1—Cu1	122.01 (10)	C8—C9—C10	119.02 (15)
C8—N1—Cu1	119.89 (10)	C8—C9—H9	120.5
O2—C1—O1	121.52 (14)	C10—C9—H9	120.5
O2—C1—C2	120.11 (14)	C11—C10—C9	118.72 (15)
O1—C1—C2	118.34 (13)	C11—C10—H10	120.6
C7—C2—C3	118.88 (14)	C9—C10—H10	120.6
C7—C2—C1	121.28 (14)	C10—C11—C12	119.01 (15)
C3—C2—C1	119.75 (14)	C10—C11—H11	120.5
C4—C3—C2	120.95 (15)	C12—C11—H11	120.5
C4—C3—H3	119.5	N1—C12—C11	122.69 (15)
C2—C3—H3	119.5	N1—C12—H12	118.7
C3—C4—C5	119.55 (15)	C11—C12—H12	118.7
C3—C4—H4	120.2

O1ⁱ—Cu1—O1—C1	−98 (46)	O1—C1—C2—C7	4.3 (2)
N1ⁱ—Cu1—O1—C1	−90.19 (9)	O2—C1—C2—C3	2.7 (2)
N1—Cu1—O1—C1	89.81 (9)	O1—C1—C2—C3	−179.10 (14)
O2—Cu1—O1—C1	−4.95 (8)	C7—C2—C3—C4	1.1 (2)
O1—Cu1—O2—C1	5.02 (8)	C1—C2—C3—C4	−175.51 (14)
O1ⁱ—Cu1—O2—C1	−174.98 (8)	C2—C3—C4—C5	0.7 (2)
N1ⁱ—Cu1—O2—C1	98.93 (9)	C3—C4—C5—O3	177.74 (15)
N1—Cu1—O2—C1	−81.07 (9)	C3—C4—C5—C6	−2.2 (3)
O1—Cu1—N1—C12	−143.73 (12)	O3—C5—C6—C7	−178.07 (17)
O1ⁱ—Cu1—N1—C12	36.27 (12)	C4—C5—C6—C7	1.9 (3)
N1ⁱ—Cu1—N1—C12	0 (100)	C5—C6—C7—C2	0.0 (3)
O2—Cu1—N1—C12	−86.30 (12)	C3—C2—C7—C6	−1.5 (3)
O1—Cu1—N1—C8	39.72 (12)	C1—C2—C7—C6	175.12 (17)
O1ⁱ—Cu1—N1—C8	−140.28 (12)	C12—N1—C8—C9	−1.7 (2)
N1ⁱ—Cu1—N1—C8	0 (95)	Cu1—N1—C8—C9	175.01 (13)
O2—Cu1—N1—C8	97.15 (12)	N1—C8—C9—C10	1.3 (3)
Cu1—O2—C1—O1	−7.68 (13)	C8—C9—C10—C11	0.2 (3)
Cu1—O2—C1—C2	170.43 (13)	C9—C10—C11—C12	−1.2 (3)
Cu1—O1—C1—O2	9.84 (16)	C8—N1—C12—C11	0.6 (2)
Cu1—O1—C1—C2	−168.30 (11)	Cu1—N1—C12—C11	−176.06 (12)
O2—C1—C2—C7	−173.84 (15)	C10—C11—C12—N1	0.9 (3)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱⁱ	0.84	1.87	2.7028 (16)	171

Symmetry code: (ii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₅O₃)₂(C₅H₅N)₂]
M_r	495.96
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.6715 (2), 8.5385 (1), 12.3988 (2)
β (°)	109.124 (1)
V (Å³)	1067.41 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.30 × 0.26 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.663, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9756, 2448, 2202
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.066, 1.06
No. of reflections	2448
No. of parameters	152
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.32

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.84	1.87	2.7028 (16)	171

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

We thank the University of Malaya (grant Nos. PS345/2010 A and TA010/2010) for supporting this study.

References

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