Diaqua­bis­(4-bromo­benzoato-κO)bis­(nicotinamide-κN1)copper(II)

Necefoğlu, H.; Özbek, F.E.; Öztürk, V.; Tercan, B.; Hökelek, T.

doi:10.1107/S1600536811021696

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m900-m901

doi:10.1107/S1600536811021696

Open

access

Diaquabis(4-bromobenzoato-κO)bis(nicotinamide-κN¹)copper(II)

Hacali Necefoğlu,^a Füreya Elif Özbek,^a Vijdan Öztürk,^a Barış Tercan ^b and Tuncer Hökelek ^c ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Karabük University, 78050, Karabük, Turkey, and ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 25 May 2011; accepted 6 June 2011; online 11 June 2011)

The asymmetric unit of the title mononuclear Cu^II complex, [Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂], contains one half-molecule, the Cu^II atom being located on an inversion center. The unit cell contains two nicotinamide (NA), two 4-bromobenzoate (PBB) ligands and two coordinated water molecules. The four O atoms in the equatorial plane around the Cu^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 22.17 (16)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.80 (6)°. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. A weak C—H⋯π interaction is also observed.

Related literature

For literature on niacin, see: Krishnamachari (1974 ). For infomation on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1996 , 2009a ,b ); Hökelek & Necefoğlu (1998 , 2007 ); Necefoğlu et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r = 743.84
Triclinic, $[P \overline 1]$
a = 7.7072 (3) Å
b = 9.7536 (5) Å
c = 9.8471 (4) Å
α = 76.273 (2)°
β = 74.240 (2)°
γ = 85.024 (3)°
V = 691.86 (5) Å³
Z = 1
Mo Kα radiation
μ = 3.73 mm⁻¹
T = 100 K
0.41 × 0.38 × 0.35 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.236, T_max = 0.271
11758 measured reflections
3515 independent reflections
3172 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.13
3515 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −1.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C8–C12 pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2ⁱ	0.85 (3)	2.06 (3)	2.831 (2)	151 (3)
N2—H22⋯O3ⁱⁱ	0.88 (3)	2.03 (3)	2.893 (3)	166 (3)
O4—H41⋯O2ⁱⁱⁱ	0.87 (4)	1.86 (4)	2.718 (2)	167 (4)
O4—H42⋯O3^iv	0.78 (4)	2.17 (4)	2.911 (2)	159 (4)
C6—H6⋯O2^v	0.95	2.43	3.377 (3)	172
C4—H4⋯Cg^vi	0.95	2.63	3.581 (3)	176
Symmetry codes: (i) -x, -y, -z+2; (ii) -x+1, -y, -z+2; (iii) -x, -y, -z+1; (iv) -x+1, -y, -z+1; (v) x+1, y, z; (vi) x, y+1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811021696/su2279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021696/su2279Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

The asymmetric unit of the title mononuclear Cu^IIcomplex, (Fig. 1), contains one-half molecule. It consists of two nicotinamide (NA), two 4-bromobenzoate (PBB) ligands and two coordinated water molecules, all ligands coordinating in a monodentate manner. Atom Cu1 is located on an inversion center. The crystal structures of similar complexes of Cu^II, Co^II, Ni^II, Mn^II and Zn^II ions, [Cu(C₇H₅O₂)₂(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1996), [Co(C₆H₆N₂O)₂(C₇H₄NO₄)₂(H₂O)₂] (Hökelek & Necefoğlu, 1998), [Co(C₉H₉O₂)₂(C₁₀H₁₄N₂O)₂(H₂O)₂] (Necefoğlu et al., 2011), [Ni(C₇H₄ClO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009a), [Mn(C₉H₁₀NO₂)₂(H₂O)₄].2H₂O (Hökelek & Necefoğlu, 2007) and [Zn(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂] (Hökelek et al., 2009b) have also been reported. In the copper(II) complex mentioned above the two benzoate ions coordinate to the Cu^II atom as bidentate ligands, while in the other structures all the ligands coordinate in a monodentate manner.

In the title complex, the four symmetry related O atoms (O1, O1', O4 and O4') in the equatorial plane around the Cu^II ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two symmetry related N atoms of the NA ligands (N1 and N1') in the axial positions. The near equalities of the C1—O1 [1.272 (3) Å] and C1—O2 [1.246 (3) Å] bonds in the carboxylate group indicate delocalized bonding arrangement, rather than localized single and double bonds. The Cu—O bond lengths are 1.9756 (16) Å (for benzoate oxygens) and 2.4199 (16) Å (for water oxygens), and the Cu—N bond length is 2.0116 (16) Å, close to standard values (Allen et al., 1987). The Cu atom is displaced out of the mean-plane of the carboxylate group (O1/C1/O2) by -0.5279 (1) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring A (C2—C7) is 22.17 (16)°. The benzene A (C2—C7) and the pyridine B (N1/C8—C12) rings are oriented at a dihedral angle of A/B = 82.80 (6)°.

In the crystal, intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds link the molecules into a three-dimensional network (Table 1). There also exists a weak C-H···π interaction (Table 1).

Related literature top

For literature on niacin, see: Krishnamachari (1974). For infomation on the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1996, 2009a,b); Hökelek & Necefoğlu (1998, 2007); Necefoğlu et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of CuSO₄.5H₂O (1.23 g, 5 mmol) in H₂O (20 ml) and NA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-bromobenzoate (2.23 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving blue single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (') -x, -y, -z+1].

Diaquabis(4-bromobenzoato-κO)bis(nicotinamide-κN¹)copper(II) top

Crystal data top

[Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	Z = 1
M_r = 743.84	F(000) = 371
Triclinic, P1	D_x = 1.785 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7072 (3) Å	Cell parameters from 7694 reflections
b = 9.7536 (5) Å	θ = 2.2–28.7°
c = 9.8471 (4) Å	µ = 3.73 mm⁻¹
α = 76.273 (2)°	T = 100 K
β = 74.240 (2)°	Block, blue
γ = 85.024 (3)°	0.41 × 0.38 × 0.35 mm
V = 691.86 (5) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3515 independent reflections
Radiation source: fine-focus sealed tube	3172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 28.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
T_min = 0.236, T_max = 0.271	k = −12→13
11758 measured reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0563P)² + 0.169P] where P = (F_o² + 2F_c²)/3
3515 reflections	(Δ/σ)_max = 0.001
203 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −1.29 e Å⁻³

Crystal data top

[Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]	γ = 85.024 (3)°
M_r = 743.84	V = 691.86 (5) Å³
Triclinic, P1	Z = 1
a = 7.7072 (3) Å	Mo Kα radiation
b = 9.7536 (5) Å	µ = 3.73 mm⁻¹
c = 9.8471 (4) Å	T = 100 K
α = 76.273 (2)°	0.41 × 0.38 × 0.35 mm
β = 74.240 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3515 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3172 reflections with I > 2σ(I)
T_min = 0.236, T_max = 0.271	R_int = 0.057
11758 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.86 e Å⁻³
3515 reflections	Δρ_min = −1.29 e Å⁻³
203 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	0.50803 (3)	0.60173 (3)	0.78887 (3)	0.02585 (11)
Cu1	0.0000	0.0000	0.5000	0.00979 (12)
O1	0.1042 (2)	0.17464 (16)	0.50913 (16)	0.0123 (3)
O2	−0.1351 (2)	0.26522 (18)	0.64918 (17)	0.0160 (3)
O3	0.4297 (2)	−0.00851 (18)	0.84131 (16)	0.0182 (4)
O4	0.3099 (2)	−0.0838 (2)	0.43625 (18)	0.0172 (4)
H41	0.271 (5)	−0.146 (4)	0.402 (4)	0.036 (9)*
H42	0.383 (5)	−0.042 (4)	0.371 (4)	0.043 (11)*
N1	−0.0003 (2)	−0.08494 (19)	0.70725 (18)	0.0111 (4)
N2	0.3330 (3)	−0.1428 (2)	1.0661 (2)	0.0176 (4)
H21	0.251 (4)	−0.189 (3)	1.134 (3)	0.028 (10)*
H22	0.417 (4)	−0.110 (3)	1.094 (3)	0.016 (7)*
C1	0.0294 (3)	0.2585 (2)	0.5904 (2)	0.0103 (4)
C2	0.1508 (3)	0.3509 (2)	0.6240 (2)	0.0116 (4)
C3	0.0789 (3)	0.4675 (2)	0.6809 (2)	0.0149 (4)
H3	−0.0442	0.4943	0.6883	0.018*
C4	0.1860 (3)	0.5448 (3)	0.7267 (3)	0.0174 (5)
H4	0.1375	0.6251	0.7644	0.021*
C5	0.3644 (3)	0.5032 (2)	0.7167 (2)	0.0145 (4)
C6	0.4403 (3)	0.3898 (2)	0.6570 (2)	0.0158 (5)
H6	0.5638	0.3638	0.6490	0.019*
C7	0.3328 (3)	0.3151 (2)	0.6094 (2)	0.0144 (4)
H7	0.3837	0.2384	0.5663	0.017*
C8	−0.1393 (3)	−0.1592 (2)	0.8002 (2)	0.0132 (4)
H8	−0.2407	−0.1721	0.7675	0.016*
C9	−0.1386 (3)	−0.2178 (3)	0.9430 (2)	0.0170 (5)
H9	−0.2382	−0.2703	1.0072	0.020*
C10	0.0077 (3)	−0.1992 (2)	0.9903 (2)	0.0150 (4)
H10	0.0101	−0.2388	1.0877	0.018*
C11	0.1524 (3)	−0.1221 (2)	0.8948 (2)	0.0109 (4)
C12	0.1421 (3)	−0.0671 (2)	0.7527 (2)	0.0122 (4)
H12	0.2405	−0.0151	0.6859	0.015*
C13	0.3162 (3)	−0.0880 (2)	0.9325 (2)	0.0137 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02453 (18)	0.03006 (18)	0.03230 (18)	−0.00115 (12)	−0.01163 (13)	−0.01980 (13)
Cu1	0.0109 (2)	0.0129 (2)	0.00714 (19)	0.00162 (14)	−0.00356 (14)	−0.00453 (14)
O1	0.0122 (7)	0.0149 (8)	0.0112 (7)	−0.0005 (6)	−0.0023 (6)	−0.0064 (6)
O2	0.0104 (8)	0.0214 (9)	0.0164 (8)	0.0013 (6)	−0.0016 (6)	−0.0073 (6)
O3	0.0165 (8)	0.0292 (9)	0.0101 (7)	−0.0054 (7)	−0.0030 (6)	−0.0053 (7)
O4	0.0150 (8)	0.0222 (9)	0.0147 (8)	0.0026 (7)	−0.0015 (7)	−0.0085 (7)
N1	0.0115 (9)	0.0131 (9)	0.0100 (8)	0.0037 (7)	−0.0032 (7)	−0.0062 (7)
N2	0.0172 (10)	0.0277 (11)	0.0090 (9)	−0.0027 (9)	−0.0044 (8)	−0.0043 (8)
C1	0.0091 (9)	0.0127 (10)	0.0087 (9)	−0.0004 (7)	−0.0024 (8)	−0.0014 (8)
C2	0.0141 (10)	0.0129 (10)	0.0083 (9)	0.0016 (8)	−0.0027 (8)	−0.0038 (8)
C3	0.0132 (10)	0.0162 (11)	0.0152 (10)	0.0034 (8)	−0.0025 (8)	−0.0057 (9)
C4	0.0200 (12)	0.0152 (11)	0.0189 (11)	0.0042 (9)	−0.0040 (9)	−0.0102 (9)
C5	0.0151 (11)	0.0175 (11)	0.0139 (10)	−0.0030 (8)	−0.0044 (8)	−0.0075 (8)
C6	0.0117 (10)	0.0192 (11)	0.0179 (10)	0.0029 (8)	−0.0045 (9)	−0.0070 (9)
C7	0.0157 (11)	0.0150 (11)	0.0131 (10)	0.0030 (8)	−0.0024 (8)	−0.0072 (8)
C8	0.0112 (10)	0.0169 (11)	0.0129 (10)	0.0037 (8)	−0.0030 (8)	−0.0073 (8)
C9	0.0175 (12)	0.0190 (11)	0.0129 (10)	0.0011 (9)	0.0000 (9)	−0.0055 (9)
C10	0.0153 (11)	0.0189 (11)	0.0097 (9)	0.0008 (9)	−0.0009 (8)	−0.0045 (8)
C11	0.0107 (10)	0.0140 (10)	0.0094 (9)	0.0019 (8)	−0.0025 (8)	−0.0061 (8)
C12	0.0136 (10)	0.0143 (10)	0.0100 (9)	0.0037 (8)	−0.0030 (8)	−0.0065 (8)
C13	0.0153 (11)	0.0187 (11)	0.0090 (10)	0.0043 (9)	−0.0035 (8)	−0.0082 (8)

Geometric parameters (Å, º) top

Br1—C5	1.895 (2)	C3—H3	0.9500
Cu1—O1	1.9756 (16)	C4—C5	1.383 (3)
Cu1—O1ⁱ	1.9756 (16)	C4—H4	0.9500
Cu1—N1	2.0116 (16)	C6—C5	1.386 (3)
Cu1—N1ⁱ	2.0116 (16)	C6—C7	1.384 (3)
Cu1—O4	2.4199 (16)	C6—H6	0.9500
Cu1—O4ⁱ	2.4199 (16)	C7—H7	0.9500
O1—C1	1.272 (3)	C8—N1	1.340 (3)
O2—C1	1.246 (3)	C8—H8	0.9500
O3—C13	1.238 (3)	C9—C8	1.388 (3)
O4—H41	0.87 (4)	C9—H9	0.9500
O4—H42	0.79 (4)	C10—C9	1.371 (3)
N2—C13	1.334 (3)	C10—C11	1.391 (3)
N2—H21	0.85 (3)	C10—H10	0.9500
N2—H22	0.88 (3)	C11—C12	1.396 (3)
C1—C2	1.502 (3)	C11—C13	1.493 (3)
C2—C7	1.393 (3)	C12—N1	1.331 (3)
C3—C2	1.392 (3)	C12—H12	0.9500
C3—C4	1.387 (3)

O1—Cu1—O1ⁱ	180.0	C4—C3—C2	120.4 (2)
O1—Cu1—O4	85.01 (6)	C4—C3—H3	119.8
O1ⁱ—Cu1—O4	94.99 (6)	C3—C4—H4	120.5
O1—Cu1—O4ⁱ	94.99 (6)	C5—C4—C3	119.0 (2)
O1ⁱ—Cu1—O4ⁱ	85.01 (6)	C5—C4—H4	120.5
O1—Cu1—N1	90.51 (7)	C4—C5—Br1	119.31 (17)
O1ⁱ—Cu1—N1	89.49 (7)	C4—C5—C6	121.7 (2)
O1—Cu1—N1ⁱ	89.49 (7)	C6—C5—Br1	119.02 (17)
O1ⁱ—Cu1—N1ⁱ	90.51 (7)	C5—C6—H6	120.6
O4ⁱ—Cu1—O4	180.0	C7—C6—C5	118.7 (2)
N1ⁱ—Cu1—N1	180.0	C7—C6—H6	120.6
N1—Cu1—O4	86.82 (6)	C2—C7—H7	119.6
N1ⁱ—Cu1—O4	93.18 (6)	C6—C7—C2	120.8 (2)
N1—Cu1—O4ⁱ	93.18 (6)	C6—C7—H7	119.6
N1ⁱ—Cu1—O4ⁱ	86.82 (6)	N1—C8—C9	121.6 (2)
C1—O1—Cu1	125.94 (15)	N1—C8—H8	119.2
Cu1—O4—H41	87 (2)	C9—C8—H8	119.2
Cu1—O4—H42	122 (3)	C8—C9—H9	120.4
H41—O4—H42	105 (3)	C10—C9—C8	119.3 (2)
C8—N1—Cu1	121.83 (14)	C10—C9—H9	120.4
C12—N1—Cu1	118.84 (15)	C9—C10—C11	119.6 (2)
C12—N1—C8	119.33 (18)	C9—C10—H10	120.2
C13—N2—H21	124.3 (19)	C11—C10—H10	120.2
C13—N2—H22	118.4 (19)	C10—C11—C12	117.8 (2)
H22—N2—H21	115 (3)	C10—C11—C13	125.52 (19)
O1—C1—C2	117.12 (18)	C12—C11—C13	116.7 (2)
O2—C1—O1	125.2 (2)	N1—C12—C11	122.5 (2)
O2—C1—C2	117.63 (19)	N1—C12—H12	118.8
C3—C2—C1	119.91 (19)	C11—C12—H12	118.8
C3—C2—C7	119.4 (2)	O3—C13—N2	122.1 (2)
C7—C2—C1	120.53 (19)	O3—C13—C11	119.74 (18)
C2—C3—H3	119.8	N2—C13—C11	118.2 (2)

O4—Cu1—O1—C1	−150.09 (16)	C4—C3—C2—C7	−1.9 (3)
O4ⁱ—Cu1—O1—C1	29.91 (16)	C2—C3—C4—C5	−0.8 (3)
N1—Cu1—O1—C1	−63.33 (16)	C3—C4—C5—Br1	−176.52 (17)
N1ⁱ—Cu1—O1—C1	116.67 (16)	C3—C4—C5—C6	2.5 (4)
O1—Cu1—N1—C12	−42.00 (15)	C7—C6—C5—Br1	177.63 (17)
O1ⁱ—Cu1—N1—C12	138.00 (15)	C7—C6—C5—C4	−1.4 (4)
O1—Cu1—N1—C8	138.32 (16)	C5—C6—C7—C2	−1.4 (3)
O1ⁱ—Cu1—N1—C8	−41.68 (16)	C9—C8—N1—Cu1	179.86 (16)
O4—Cu1—N1—C12	42.98 (15)	C9—C8—N1—C12	0.2 (3)
O4ⁱ—Cu1—N1—C12	−137.02 (15)	C10—C9—C8—N1	0.1 (3)
O4—Cu1—N1—C8	−136.71 (16)	C11—C10—C9—C8	0.0 (3)
O4ⁱ—Cu1—N1—C8	43.29 (16)	C9—C10—C11—C12	−0.4 (3)
Cu1—O1—C1—O2	−19.3 (3)	C9—C10—C11—C13	177.1 (2)
Cu1—O1—C1—C2	157.31 (13)	C10—C11—C12—N1	0.7 (3)
O1—C1—C2—C3	164.19 (19)	C13—C11—C12—N1	−177.08 (18)
O1—C1—C2—C7	−20.9 (3)	C10—C11—C13—O3	−174.0 (2)
O2—C1—C2—C3	−19.0 (3)	C10—C11—C13—N2	4.7 (3)
O2—C1—C2—C7	156.0 (2)	C12—C11—C13—O3	3.6 (3)
C1—C2—C7—C6	−171.9 (2)	C12—C11—C13—N2	−177.76 (19)
C3—C2—C7—C6	3.0 (3)	C11—C12—N1—Cu1	179.75 (15)
C4—C3—C2—C1	173.1 (2)	C11—C12—N1—C8	−0.6 (3)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C8–C12 pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱⁱ	0.85 (3)	2.06 (3)	2.831 (2)	151 (3)
N2—H22···O3ⁱⁱⁱ	0.88 (3)	2.03 (3)	2.893 (3)	166 (3)
O4—H41···O2ⁱ	0.87 (4)	1.86 (4)	2.718 (2)	167 (4)
O4—H42···O3^iv	0.78 (4)	2.17 (4)	2.911 (2)	159 (4)
C6—H6···O2^v	0.95	2.43	3.377 (3)	172
C4—H4···Cg^vi	0.95	2.63	3.581 (3)	176

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y, −z+2; (iii) −x+1, −y, −z+2; (iv) −x+1, −y, −z+1; (v) x+1, y, z; (vi) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄BrO₂)₂(C₆H₆N₂O)₂(H₂O)₂]
M_r	743.84
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.7072 (3), 9.7536 (5), 9.8471 (4)
α, β, γ (°)	76.273 (2), 74.240 (2), 85.024 (3)
V (Å³)	691.86 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.73
Crystal size (mm)	0.41 × 0.38 × 0.35

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.236, 0.271
No. of measured, independent and observed [I > 2σ(I)] reflections	11758, 3515, 3172
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.13
No. of reflections	3515
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −1.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C8–C12 pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ⁱ	0.85 (3)	2.06 (3)	2.831 (2)	151 (3)
N2—H22···O3ⁱⁱ	0.88 (3)	2.03 (3)	2.893 (3)	166 (3)
O4—H41···O2ⁱⁱⁱ	0.87 (4)	1.86 (4)	2.718 (2)	167 (4)
O4—H42···O3^iv	0.78 (4)	2.17 (4)	2.911 (2)	159 (4)
C6—H6···O2^v	0.95	2.43	3.377 (3)	172
C4—H4···Cg^vi	0.95	2.63	3.581 (3)	176

Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) x+1, y, z; (vi) x, y+1, z.

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 108 T657).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009a). Acta Cryst. E65, m466–m467. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Özbek, F. E. & Necefoğlu, H. (2009b). Acta Cryst. E65, m607–m608. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Gündüz, H. & Necefoğlu, H. (1996). Acta Cryst. C52, 2470–2473. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (1998). Acta Cryst. C54, 1242–1244. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (2007). Acta Cryst. E63, m821–m823. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Necefoğlu, H., Maracı, A., Özbek, F. E., Tercan, B. & Hökelek, T. (2011). Acta Cryst. E67, m619–m620. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m900-m901

doi:10.1107/S1600536811021696

Open

access