Diaqua-bis(2-bromo-benzoato-κO)bis-(nicotinamide-κN)zinc(II).

The title Zn(II) complex, [Zn(C(7)H(4)BrO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], is centrosymmetric with the Zn atom on an inversion center. The mol-ecule contains two 2-bromo-benzoate (BB) and two nicotinamide (NA) ligands and two coordinated water mol-ecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Zn atom form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 31.14 (12)°, while the pyridine and benzene rings are oriented at a dihedral angle of 83.54 (5)°. In the crystal structure, O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into infinite chains. A weak C-H⋯π inter-action is also present.

Related literature

For general backgroud to the properties of transition metal complexes with biochemically active ligands, see: Antolini et al. (1982 ▶); Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶); Nad­zhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek et al. (1995 ▶, 1997 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶).

Experimental

Crystal data

[Zn(C7H4BrO2)2(C6H6N2O)2(H2O)2]

M = 745.68

Monoclinic,

a = 7.9111 (2) Å

b = 18.1604 (4) Å

c = 9.8345 (3) Å

β = 106.346 (1)°

V = 1355.80 (6) Å3

Z = 2

Mo Kα radiation

μ = 3.91 mm−1

T = 100 K

0.43 × 0.33 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffctometer diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.230, T max = 0.393

12839 measured reflections

3416 independent reflections

2948 reflections with I > 2σ(I)

R int = 0.081

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.065

S = 1.06

3416 reflections

203 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.77 e Å−3

Δρmin = −0.51 e Å−3

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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015645/xu2517sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015645/xu2517Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(C7H4BrO2)2(C6H6N2O)2(H2O)2]	F(000) = 744
Mr = 745.68	Dx = 1.827 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7038 reflections
a = 7.9111 (2) Å	θ = 2.4–28.4°
b = 18.1604 (4) Å	µ = 3.91 mm−1
c = 9.8345 (3) Å	T = 100 K
β = 106.346 (1)°	Block, colorless
V = 1355.80 (6) Å3	0.43 × 0.33 × 0.24 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffctometer diffractometer	3416 independent reflections
Radiation source: fine-focus sealed tube	2948 reflections with I > 2σ(I)
graphite	Rint = 0.081
φ and ω scans	θmax = 28.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→10
Tmin = 0.230, Tmax = 0.393	k = −24→23
12839 measured reflections	l = −13→13

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) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0306P)2] where P = (Fo2 + 2Fc2)/3
3416 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 0.77 e Å−3
1 restraint	Δρmin = −0.51 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.90022 (2)	0.210886 (11)	0.671443 (19)	0.02134 (7)
Zn1	1.0000	0.5000	1.0000	0.01096 (8)
O1	1.11803 (16)	0.40204 (7)	0.95347 (12)	0.0142 (3)
O2	0.89388 (16)	0.36730 (8)	0.77083 (12)	0.0163 (3)
O3	1.45377 (17)	0.51058 (8)	0.67688 (12)	0.0186 (3)
O4	1.26223 (16)	0.54361 (8)	1.09090 (12)	0.0145 (3)
H41	1.238 (4)	0.5757 (17)	1.143 (3)	0.048 (9)*
H42	1.343 (3)	0.5165 (13)	1.146 (2)	0.030 (6)*
N1	1.00804 (19)	0.54424 (9)	0.80326 (14)	0.0126 (3)
N2	1.3585 (2)	0.58056 (11)	0.48109 (16)	0.0193 (4)
H21	1.272 (3)	0.6009 (14)	0.427 (2)	0.031 (7)*
H22	1.447 (4)	0.5666 (15)	0.452 (3)	0.031 (7)*
C1	1.0529 (2)	0.36488 (10)	0.84198 (16)	0.0125 (3)
C2	1.1764 (2)	0.31803 (10)	0.78680 (16)	0.0127 (3)
C3	1.3510 (2)	0.34108 (11)	0.81090 (17)	0.0149 (4)
H3	1.3907	0.3815	0.8692	0.018*
C4	1.4661 (2)	0.30548 (11)	0.75047 (18)	0.0177 (4)
H4	1.5816	0.3219	0.7683	0.021*
C5	1.4089 (2)	0.24503 (12)	0.66281 (17)	0.0171 (4)
H5	1.4850	0.2220	0.6193	0.021*
C6	1.2392 (2)	0.21919 (11)	0.64049 (17)	0.0157 (4)
H6	1.2014	0.1780	0.5838	0.019*
C7	1.1250 (2)	0.25506 (11)	0.70332 (16)	0.0133 (4)
C8	1.1546 (2)	0.53766 (10)	0.76238 (16)	0.0133 (4)
H8	1.2498	0.5127	0.8216	0.016*
C9	1.1722 (2)	0.56605 (10)	0.63648 (16)	0.0126 (3)
C10	1.0301 (2)	0.60450 (11)	0.54960 (17)	0.0162 (4)
H10	1.0381	0.6251	0.4650	0.019*
C11	0.8777 (2)	0.61176 (11)	0.58996 (17)	0.0171 (4)
H11	0.7815	0.6372	0.5333	0.020*
C12	0.8705 (2)	0.58033 (11)	0.71677 (17)	0.0147 (4)
H12	0.7669	0.5843	0.7431	0.018*
C13	1.3397 (2)	0.55091 (11)	0.59974 (17)	0.0147 (4)

	U11	U22	U33	U12	U13	U23
Br1	0.01423 (10)	0.02129 (13)	0.02759 (11)	−0.00591 (7)	0.00440 (7)	−0.00471 (7)
Zn1	0.00902 (14)	0.01609 (17)	0.00751 (12)	0.00017 (10)	0.00189 (10)	0.00020 (10)
O1	0.0127 (6)	0.0182 (7)	0.0104 (5)	0.0032 (5)	0.0010 (4)	−0.0004 (5)
O2	0.0098 (6)	0.0249 (8)	0.0128 (5)	0.0021 (5)	0.0010 (5)	−0.0018 (5)
O3	0.0129 (6)	0.0297 (9)	0.0133 (6)	0.0062 (6)	0.0040 (5)	0.0051 (5)
O4	0.0102 (6)	0.0197 (8)	0.0127 (6)	0.0009 (5)	0.0019 (5)	−0.0007 (5)
N1	0.0102 (7)	0.0158 (8)	0.0112 (6)	0.0000 (6)	0.0020 (5)	−0.0002 (5)
N2	0.0131 (8)	0.0325 (10)	0.0139 (7)	0.0068 (7)	0.0064 (6)	0.0069 (7)
C1	0.0120 (8)	0.0154 (9)	0.0099 (7)	−0.0004 (7)	0.0029 (6)	0.0031 (6)
C2	0.0135 (8)	0.0145 (9)	0.0091 (7)	0.0019 (7)	0.0018 (6)	0.0018 (6)
C3	0.0128 (8)	0.0163 (10)	0.0139 (7)	0.0002 (7)	0.0011 (6)	−0.0006 (7)
C4	0.0114 (8)	0.0231 (11)	0.0185 (8)	−0.0010 (7)	0.0038 (7)	0.0016 (7)
C5	0.0169 (9)	0.0211 (11)	0.0149 (8)	0.0056 (7)	0.0069 (7)	0.0030 (7)
C6	0.0176 (9)	0.0162 (10)	0.0122 (7)	0.0016 (7)	0.0023 (7)	−0.0007 (6)
C7	0.0111 (8)	0.0168 (10)	0.0107 (7)	−0.0008 (7)	0.0007 (6)	0.0016 (6)
C8	0.0119 (8)	0.0154 (10)	0.0115 (7)	0.0013 (7)	0.0013 (6)	0.0004 (6)
C9	0.0115 (8)	0.0155 (10)	0.0109 (7)	0.0003 (6)	0.0033 (6)	−0.0008 (6)
C10	0.0146 (8)	0.0238 (11)	0.0103 (7)	0.0025 (7)	0.0038 (6)	0.0042 (7)
C11	0.0132 (8)	0.0216 (11)	0.0142 (7)	0.0048 (7)	0.0003 (7)	0.0042 (7)
C12	0.0122 (8)	0.0180 (10)	0.0141 (7)	0.0018 (7)	0.0038 (6)	0.0001 (7)
C13	0.0120 (8)	0.0199 (10)	0.0119 (7)	0.0002 (7)	0.0031 (6)	−0.0016 (6)

Br1—C7	1.8950 (18)	C4—C3	1.380 (3)
Zn1—O1i	2.1182 (13)	C4—H4	0.9300
Zn1—O1	2.1182 (13)	C5—C4	1.390 (3)
Zn1—O4i	2.1647 (12)	C5—C6	1.380 (3)
Zn1—O4	2.1647 (12)	C5—H5	0.9300
Zn1—N1	2.1124 (14)	C6—H6	0.9300
Zn1—N1i	2.1124 (14)	C7—C2	1.400 (3)
O1—C1	1.267 (2)	C7—C6	1.392 (3)
O2—C1	1.256 (2)	C8—C9	1.384 (2)
O3—C13	1.242 (2)	C8—H8	0.9300
O4—H41	0.83 (3)	C10—C9	1.393 (2)
O4—H42	0.869 (16)	C10—C11	1.378 (3)
N1—C8	1.335 (2)	C10—H10	0.9300
N1—C12	1.347 (2)	C11—C12	1.387 (3)
N2—H21	0.83 (2)	C11—H11	0.9300
N2—H22	0.86 (3)	C12—H12	0.9300
C1—C2	1.507 (3)	C13—N2	1.331 (2)
C2—C3	1.399 (2)	C13—C9	1.494 (2)
C3—H3	0.9300
O1i—Zn1—O1	180.0	C4—C3—C2	121.78 (17)
O1—Zn1—O4	88.11 (5)	C4—C3—H3	119.1
O1i—Zn1—O4	91.89 (5)	C3—C4—C5	119.88 (17)
O1—Zn1—O4i	91.89 (5)	C3—C4—H4	120.1
O1i—Zn1—O4i	88.11 (5)	C5—C4—H4	120.1
O4i—Zn1—O4	180.0	C4—C5—H5	120.0
N1—Zn1—O1	89.59 (5)	C6—C5—C4	119.94 (17)
N1i—Zn1—O1	90.41 (5)	C6—C5—H5	120.0
N1—Zn1—O1i	90.41 (5)	C5—C6—C7	119.62 (17)
N1i—Zn1—O1i	89.59 (5)	C5—C6—H6	120.2
N1—Zn1—O4	88.09 (5)	C7—C6—H6	120.2
N1i—Zn1—O4	91.91 (5)	C2—C7—Br1	123.15 (14)
N1—Zn1—O4i	91.91 (5)	C6—C7—Br1	115.13 (14)
N1i—Zn1—O4i	88.09 (5)	C6—C7—C2	121.70 (16)
N1—Zn1—N1i	180.000 (1)	N1—C8—C9	123.40 (15)
Zn1—O4—H42	120.3 (18)	N1—C8—H8	118.3
Zn1—O4—H41	99 (2)	C9—C8—H8	118.3
H42—O4—H41	106 (2)	C8—C9—C10	117.95 (17)
C1—O1—Zn1	122.52 (11)	C8—C9—C13	117.85 (15)
C8—N1—Zn1	119.62 (11)	C10—C9—C13	124.15 (15)
C8—N1—C12	117.94 (15)	C9—C10—H10	120.3
C12—N1—Zn1	122.42 (12)	C11—C10—C9	119.46 (16)
C13—N2—H21	117.7 (18)	C11—C10—H10	120.3
C13—N2—H22	118.2 (17)	C10—C11—C12	118.67 (16)
H21—N2—H22	121 (2)	C10—C11—H11	120.7
O1—C1—C2	117.73 (15)	C12—C11—H11	120.7
O2—C1—O1	124.27 (17)	N1—C12—C11	122.55 (17)
O2—C1—C2	117.91 (15)	N1—C12—H12	118.7
C3—C2—C1	118.66 (17)	C11—C12—H12	118.7
C3—C2—C7	116.98 (16)	O3—C13—N2	122.19 (18)
C7—C2—C1	124.19 (16)	O3—C13—C9	120.18 (16)
C2—C3—H3	119.1	N2—C13—C9	117.61 (16)
O4i—Zn1—O1—C1	36.30 (14)	C1—C2—C3—C4	−172.78 (16)
O4—Zn1—O1—C1	−143.70 (14)	C7—C2—C3—C4	2.7 (3)
N1—Zn1—O1—C1	−55.59 (14)	C5—C4—C3—C2	0.1 (3)
N1i—Zn1—O1—C1	124.41 (14)	C6—C5—C4—C3	−2.3 (3)
O1i—Zn1—N1—C8	134.53 (14)	C4—C5—C6—C7	1.6 (3)
O1—Zn1—N1—C8	−45.47 (14)	Br1—C7—C2—C1	−10.0 (2)
O1i—Zn1—N1—C12	−44.44 (14)	Br1—C7—C2—C3	174.80 (12)
O1—Zn1—N1—C12	135.56 (14)	C6—C7—C2—C1	171.77 (16)
O4i—Zn1—N1—C8	−137.35 (14)	C6—C7—C2—C3	−3.4 (2)
O4—Zn1—N1—C8	42.65 (14)	Br1—C7—C6—C5	−177.00 (13)
O4i—Zn1—N1—C12	43.68 (14)	C2—C7—C6—C5	1.4 (3)
O4—Zn1—N1—C12	−136.32 (14)	N1—C8—C9—C10	1.1 (3)
Zn1—O1—C1—O2	−22.3 (2)	N1—C8—C9—C13	−176.47 (16)
Zn1—O1—C1—C2	154.15 (12)	C11—C10—C9—C8	−1.2 (3)
Zn1—N1—C8—C9	−178.88 (14)	C11—C10—C9—C13	176.27 (18)
C12—N1—C8—C9	0.1 (3)	C9—C10—C11—C12	0.0 (3)
Zn1—N1—C12—C11	177.59 (15)	C10—C11—C12—N1	1.3 (3)
C8—N1—C12—C11	−1.4 (3)	O3—C13—C9—C8	4.0 (3)
O1—C1—C2—C3	−30.2 (2)	O3—C13—C9—C10	−173.46 (18)
O1—C1—C2—C7	154.63 (17)	N2—C13—C9—C8	−177.63 (18)
O2—C1—C2—C3	146.41 (17)	N2—C13—C9—C10	4.9 (3)
O2—C1—C2—C7	−28.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.83 (2)	2.10 (2)	2.870 (2)	155 (2)
O4—H41···O2i	0.83 (3)	1.84 (3)	2.6339 (19)	159 (3)
C11—H11···Cg1iii	0.93	2.87	3.600 (3)	136

Table 1

Selected bond lengths (Å)

Zn1—O1	2.1182 (13)
Zn1—O4	2.1647 (12)
Zn1—N1	2.1124 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.83 (2)	2.10 (2)	2.870 (2)	155 (2)
O4—H41⋯O2ii	0.83 (3)	1.84 (3)	2.6339 (19)	159 (3)
C11—H11⋯Cg1iii	0.93	2.87	3.600 (3)	136

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C2–C7 ring.