Diaqua-bis(5-bromo-2-hydroxy-benzoato)bis-(N-methyl-nicotinamide)zinc(II).

The title mononuclear complex mol-ecule, [Zn(C(7)H(4)BrO(3))(2)(C(7)H(8)N(2)O)(2)(H(2)O)(2)], has a crystallographically imposed centre of symmetry. The zinc(II) atom is coordinated by two N atoms from two N-methyl-nicotinamide ligands, two O atoms from two 5-bromo-salicylate anions and two aqua O atoms in a slightly distorted octa-hedral geometry. Intra-molecular O-H⋯O hydrogen-bonding inter-actions are present. In the crystal structure, mol-ecules are linked by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds, forming a two-dimensional network perpendicular to [100].

Related literature

For general background to the properties of carboxylic acid–metal complexes, see: Nagar (1990 ▶); Cavagiolio et al. (2000 ▶). For the synthesis and properties of zinc(II) carboxyl­ates reported by our group, see: Györyová et al. (2005 ▶, 2006 ▶); Bujdošová et al. (2009 ▶); Gebicki et al. (2003 ▶). For related structures, see: Necefoglu et al. (2001a ▶,b ▶); Hökelek et al. (2007 ▶, 2009a ▶,b ▶); Öztürk et al. (2008 ▶); Sarı et al. (2007 ▶); Liu et al. (2004 ▶).

Experimental

Crystal data

[Zn(C7H4BrO3)2(C7H8N2O)2(H2O)2]

M = 805.73

Triclinic,

a = 8.1600 (2) Å

b = 10.1122 (3) Å

c = 10.4291 (3) Å

α = 66.800 (3)°

β = 74.334 (2)°

γ = 80.743 (2)°

V = 760.15 (4) Å3

Z = 1

Mo Kα radiation

μ = 3.50 mm−1

T = 290 K

0.57 × 0.30 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer

Absorption correction: numerical [Clark & Reid (1995 ▶) in CrysAlis PRO (Oxford Diffraction, 2009 ▶)] T min = 0.289, T max = 0.484

32240 measured reflections

3153 independent reflections

2686 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.064

S = 1.15

3153 reflections

195 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Crystal Impact, 2007 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008834/rz2423sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008834/rz2423Isup2.hkl

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

[Zn(C7H4BrO3)2(C7H8N2O)2(H2O)2]	Z = 1
Mr = 805.73	F(000) = 404
Triclinic, P1	Dx = 1.760 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1600 (2) Å	Cell parameters from 19248 reflections
b = 10.1122 (3) Å	θ = 3.0–29.6°
c = 10.4291 (3) Å	µ = 3.50 mm−1
α = 66.800 (3)°	T = 290 K
β = 74.334 (2)°	Prism, colourless
γ = 80.743 (2)°	0.56 × 0.30 × 0.26 mm
V = 760.15 (4) Å3

Oxford Diffraction Xcalibur Sapphire2 diffractometer	3153 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2686 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 8.3438 pixels mm-1	θmax = 26.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: numerical [Clark & Reid (1995) in CrysAlis PRO (Oxford Diffraction, 2009)]	k = −12→12
Tmin = 0.289, Tmax = 0.484	l = −13→13
32240 measured reflections

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H-atom parameters constrained
S = 1.15	w = 1/[σ2(Fo2) + (0.0404P)2] where P = (Fo2 + 2Fc2)/3
3153 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

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 > 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
Zn1	0.5000	0.0000	0.0000	0.02312 (9)
O1	0.67676 (14)	−0.02707 (13)	−0.17587 (12)	0.0305 (3)
O2	0.5864 (2)	0.14251 (15)	−0.36177 (15)	0.0493 (4)
O3	0.6562 (2)	0.11216 (16)	−0.60156 (15)	0.0550 (4)
H1O3	0.6075	0.1466	−0.5409	0.083*
C1	0.6699 (2)	0.02704 (19)	−0.30545 (19)	0.0299 (4)
C2	0.7659 (2)	−0.05359 (18)	−0.40050 (18)	0.0270 (4)
C3	0.7497 (2)	−0.00760 (19)	−0.54230 (19)	0.0348 (4)
C4	0.8343 (3)	−0.0873 (2)	−0.6265 (2)	0.0425 (5)
H4	0.8233	−0.0574	−0.7204	0.051*
C5	0.9340 (3)	−0.2099 (2)	−0.5713 (2)	0.0403 (5)
H5	0.9899	−0.2629	−0.6276	0.048*
C6	0.9505 (2)	−0.25379 (19)	−0.43114 (19)	0.0319 (4)
C7	0.8667 (2)	−0.17721 (18)	−0.34631 (18)	0.0295 (4)
H7	0.8777	−0.2085	−0.2522	0.035*
Br1	1.08861 (3)	−0.42202 (2)	−0.35493 (2)	0.05222 (9)
N1	0.66055 (11)	0.14385 (9)	0.01039 (9)	0.0245 (3)
N2	0.48397 (11)	0.41145 (9)	0.24800 (9)	0.0384 (4)
H1N2	0.4560	0.3237	0.2876	0.046*
C8	0.82847 (11)	0.13682 (9)	−0.04349 (9)	0.0302 (4)
H8	0.8741	0.0682	−0.0843	0.036*
C9	0.9368 (2)	0.2262 (2)	−0.0414 (2)	0.0373 (4)
H9	1.0533	0.2178	−0.0794	0.045*
C10	0.8694 (2)	0.32926 (19)	0.0186 (2)	0.0352 (4)
H10	0.9399	0.3919	0.0205	0.042*
C11	0.6960 (2)	0.33753 (16)	0.07550 (17)	0.0250 (3)
C12	0.5966 (2)	0.24263 (16)	0.06900 (17)	0.0241 (3)
H12	0.4799	0.2479	0.1072	0.029*
C13	0.6211 (2)	0.44766 (17)	0.14122 (19)	0.0282 (4)
C14	0.39754 (10)	0.50534 (8)	0.32554 (9)	0.0531 (6)
H14C	0.2890	0.4692	0.3828	0.080*
H14A	0.3809	0.6011	0.2583	0.080*
H14B	0.4660	0.5074	0.3864	0.080*
O4	0.68500 (13)	0.56491 (9)	0.09551 (11)	0.0373 (3)
O5	0.63493 (12)	−0.17592 (8)	0.13428 (10)	0.0300 (3)
H2O5	0.5760	−0.1834	0.2138	0.045*
H1O5	0.6509	−0.2531	0.1229	0.045*

	U11	U22	U33	U12	U13	U23
Zn1	0.02369 (15)	0.02253 (14)	0.02842 (16)	−0.00151 (10)	−0.00284 (11)	−0.01690 (11)
O1	0.0301 (6)	0.0377 (7)	0.0285 (7)	−0.0004 (5)	−0.0009 (5)	−0.0214 (6)
O2	0.0659 (10)	0.0349 (7)	0.0386 (8)	0.0174 (7)	−0.0051 (7)	−0.0168 (6)
O3	0.0737 (11)	0.0479 (9)	0.0376 (9)	0.0209 (8)	−0.0187 (8)	−0.0152 (7)
C1	0.0294 (9)	0.0296 (9)	0.0322 (10)	−0.0047 (7)	0.0013 (7)	−0.0175 (8)
C2	0.0290 (9)	0.0285 (9)	0.0242 (9)	−0.0033 (7)	0.0008 (7)	−0.0143 (7)
C3	0.0416 (11)	0.0330 (10)	0.0272 (9)	−0.0004 (8)	−0.0060 (8)	−0.0102 (8)
C4	0.0580 (13)	0.0465 (12)	0.0239 (10)	0.0003 (10)	−0.0069 (9)	−0.0170 (9)
C5	0.0489 (12)	0.0433 (11)	0.0322 (10)	−0.0008 (9)	0.0002 (9)	−0.0246 (9)
C6	0.0315 (10)	0.0310 (9)	0.0344 (10)	0.0009 (7)	−0.0031 (8)	−0.0172 (8)
C7	0.0321 (9)	0.0342 (9)	0.0247 (9)	−0.0028 (7)	−0.0033 (7)	−0.0152 (7)
Br1	0.05614 (16)	0.04580 (14)	0.05557 (16)	0.01938 (10)	−0.01506 (11)	−0.02663 (11)
N1	0.0260 (7)	0.0214 (7)	0.0303 (8)	−0.0008 (5)	−0.0066 (6)	−0.0140 (6)
N2	0.0486 (10)	0.0283 (8)	0.0416 (10)	−0.0049 (7)	−0.0014 (8)	−0.0213 (7)
C8	0.0287 (9)	0.0277 (9)	0.0376 (10)	0.0011 (7)	−0.0036 (7)	−0.0192 (8)
C9	0.0248 (9)	0.0371 (10)	0.0539 (12)	−0.0040 (8)	−0.0013 (8)	−0.0249 (9)
C10	0.0346 (10)	0.0300 (9)	0.0462 (11)	−0.0087 (7)	−0.0085 (8)	−0.0173 (8)
C11	0.0327 (9)	0.0181 (8)	0.0272 (9)	−0.0012 (6)	−0.0100 (7)	−0.0097 (7)
C12	0.0262 (8)	0.0215 (8)	0.0273 (9)	0.0006 (6)	−0.0069 (7)	−0.0122 (7)
C13	0.0331 (9)	0.0229 (8)	0.0359 (10)	0.0034 (7)	−0.0163 (7)	−0.0151 (7)
C14	0.0612 (15)	0.0488 (13)	0.0547 (14)	−0.0050 (11)	0.0057 (11)	−0.0365 (11)
O4	0.0450 (8)	0.0217 (6)	0.0504 (8)	−0.0032 (5)	−0.0097 (6)	−0.0191 (6)
O5	0.0316 (7)	0.0239 (6)	0.0381 (7)	0.0014 (5)	−0.0059 (5)	−0.0175 (5)

Zn1—O1i	2.0879 (11)	N1—C8	1.3352 (13)
Zn1—O1	2.0879 (11)	N1—C12	1.3359 (17)
Zn1—O5	2.1396 (9)	N2—C13	1.328 (2)
Zn1—O5i	2.1396 (9)	N2—C14	1.4609 (13)
Zn1—N1i	2.1583 (9)	N2—H1N2	0.8578
Zn1—N1	2.1583 (9)	C8—C9	1.372 (2)
O1—C1	1.256 (2)	C8—H8	0.9300
O2—C1	1.262 (2)	C9—C10	1.387 (2)
O3—C3	1.341 (2)	C9—H9	0.9300
O3—H1O3	0.8200	C10—C11	1.382 (2)
C1—C2	1.508 (2)	C10—H10	0.9300
C2—C7	1.386 (2)	C11—C12	1.384 (2)
C2—C3	1.402 (3)	C11—C13	1.497 (2)
C3—C4	1.396 (2)	C12—H12	0.9300
C4—C5	1.377 (3)	C13—O4	1.235 (2)
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.389 (3)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.376 (2)	O5—H2O5	0.8196
C6—Br1	1.8968 (18)	O5—H1O5	0.8197
C7—H7	0.9300
O1i—Zn1—O1	180.00 (8)	C6—C7—H7	119.9
O1i—Zn1—O5	92.30 (4)	C2—C7—H7	119.9
O1—Zn1—O5	87.70 (4)	C8—N1—C12	117.96 (11)
O1i—Zn1—O5i	87.70 (4)	C8—N1—Zn1	120.28 (7)
O1—Zn1—O5i	92.30 (4)	C12—N1—Zn1	121.77 (9)
O5—Zn1—O5i	180.00 (10)	C13—N2—C14	122.98 (11)
O1i—Zn1—N1i	91.23 (4)	C13—N2—H1N2	120.1
O1—Zn1—N1i	88.77 (4)	C14—N2—H1N2	115.5
O5—Zn1—N1i	91.78 (3)	N1—C8—C9	122.98 (11)
O5i—Zn1—N1i	88.22 (3)	N1—C8—H8	118.5
O1i—Zn1—N1	88.77 (4)	C9—C8—H8	118.5
O1—Zn1—N1	91.23 (4)	C8—C9—C10	118.76 (15)
O5—Zn1—N1	88.22 (4)	C8—C9—H9	120.6
O5i—Zn1—N1	91.78 (3)	C10—C9—H9	120.6
N1i—Zn1—N1	180.00 (4)	C11—C10—C9	118.99 (16)
C1—O1—Zn1	128.42 (11)	C11—C10—H10	120.5
C3—O3—H1O3	109.5	C9—C10—H10	120.5
O1—C1—O2	125.03 (16)	C10—C11—C12	118.22 (15)
O1—C1—C2	117.54 (15)	C10—C11—C13	119.77 (15)
O2—C1—C2	117.42 (16)	C12—C11—C13	122.01 (15)
C7—C2—C3	119.42 (15)	N1—C12—C11	123.07 (14)
C7—C2—C1	119.96 (15)	N1—C12—H12	118.5
C3—C2—C1	120.57 (16)	C11—C12—H12	118.5
O3—C3—C4	118.17 (17)	O4—C13—N2	123.41 (16)
O3—C3—C2	122.26 (16)	O4—C13—C11	120.51 (15)
C4—C3—C2	119.57 (17)	N2—C13—C11	116.08 (15)
C5—C4—C3	120.41 (18)	N2—C14—H14C	109.5
C5—C4—H4	119.8	N2—C14—H14A	109.5
C3—C4—H4	119.8	H14C—C14—H14A	109.5
C4—C5—C6	119.57 (17)	N2—C14—H14B	109.5
C4—C5—H5	120.2	H14C—C14—H14B	109.5
C6—C5—H5	120.2	H14A—C14—H14B	109.5
C7—C6—C5	120.74 (17)	Zn1—O5—H2O5	100.9
C7—C6—Br1	119.51 (14)	Zn1—O5—H1O5	119.2
C5—C6—Br1	119.74 (14)	H2O5—O5—H1O5	111.8
C6—C7—C2	120.28 (16)
O5—Zn1—O1—C1	167.76 (16)	O1—Zn1—N1—C8	−24.26 (8)
O5i—Zn1—O1—C1	−12.24 (16)	O5—Zn1—N1—C8	63.39 (8)
N1i—Zn1—O1—C1	75.93 (14)	O5i—Zn1—N1—C8	−116.61 (8)
N1—Zn1—O1—C1	−104.07 (14)	O1i—Zn1—N1—C12	−24.81 (11)
Zn1—O1—C1—O2	24.7 (3)	O1—Zn1—N1—C12	155.19 (11)
Zn1—O1—C1—C2	−153.98 (11)	O5—Zn1—N1—C12	−117.16 (10)
O1—C1—C2—C7	−4.4 (2)	O5i—Zn1—N1—C12	62.84 (10)
O2—C1—C2—C7	176.77 (16)	C12—N1—C8—C9	−0.15 (17)
O1—C1—C2—C3	173.34 (16)	Zn1—N1—C8—C9	179.32 (11)
O2—C1—C2—C3	−5.5 (3)	N1—C8—C9—C10	−0.4 (2)
C7—C2—C3—O3	−178.98 (17)	C8—C9—C10—C11	0.7 (3)
C1—C2—C3—O3	3.3 (3)	C9—C10—C11—C12	−0.5 (3)
C7—C2—C3—C4	0.4 (3)	C9—C10—C11—C13	179.74 (17)
C1—C2—C3—C4	−177.40 (16)	C8—N1—C12—C11	0.3 (2)
O3—C3—C4—C5	179.01 (19)	Zn1—N1—C12—C11	−179.13 (12)
C2—C3—C4—C5	−0.4 (3)	C10—C11—C12—N1	0.0 (2)
C3—C4—C5—C6	−0.2 (3)	C13—C11—C12—N1	179.73 (14)
C4—C5—C6—C7	0.8 (3)	C14—N2—C13—O4	−2.0 (2)
C4—C5—C6—Br1	−179.66 (15)	C14—N2—C13—C11	178.73 (11)
C5—C6—C7—C2	−0.8 (3)	C10—C11—C13—O4	31.6 (2)
Br1—C6—C7—C2	179.66 (13)	C12—C11—C13—O4	−148.18 (17)
C3—C2—C7—C6	0.2 (3)	C10—C11—C13—N2	−149.10 (16)
C1—C2—C7—C6	178.00 (16)	C12—C11—C13—N2	31.1 (2)
O1i—Zn1—N1—C8	155.74 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O2	0.82	1.81	2.540 (2)	147
N2—H1N2···O3ii	0.86	2.55	3.1109 (19)	123
O5—H2O5···O2i	0.82	1.88	2.6694 (18)	162
O5—H1O5···O4iii	0.82	1.94	2.7568 (13)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O2	0.82	1.81	2.540 (2)	147
N2—H1N2⋯O3i	0.86	2.55	3.1109 (19)	123
O5—H2O5⋯O2ii	0.82	1.88	2.6694 (18)	162
O5—H1O5⋯O4iii	0.82	1.94	2.7568 (13)	179

Symmetry codes: (i) ; (ii) ; (iii) .