[1-(5-Bromo-2-oxidobenzyl-idene)thio-semicarbazidato-κ(3)O,N(1),S](pyridine-κN)nickel(II).

The reaction of 5-bromo-salicyl-aldehyde thio-semicarbazone with nickel acetate tetra-hydrate and pyridine yielded the title compound, [Ni(C(8)H(6)BrN(3)OS)(C(5)H(5)N)]. The Ni(II) atom is four-coordinated in a square-planar environment by one deprotonated dianionic thio-semicarbazone ligand, acting in a tridentate chelating mode through N, O and S atoms forming two metalla-rings, and by one pyridine mol-ecule. The complex mol-ecules are linked into dimers by pairs of centrosym-metrical N-H⋯N inter-actions. In addition, mol-ecules are connected through inter-molecular Br⋯Br inter-actions [3.545 (1) Å], forming chains along the b-axis direction.

Related literature

For the synthesis of 5-bromo­salicyl­aldehyde thio­semi­carba­zones and for the anti­bacterial activity of their complexes, see: Joseph et al. (2010 ▶). For the crystal structure of 5-bromo­salicyl­aldehyde thio­semicarbazone, see: Kargar et al. (2010 ▶). For the crystal structure of an NiII complex with a similar coordination environment, see: Güveli et al. (2009 ▶). For the coordination chemistry of thio­semicarbazone derivatives, see: Lobana et al. (2009 ▶).

Experimental

Crystal data

[Ni(C8H6BrN3OS)(C5H5N)]

M = 409.94

Monoclinic,

a = 12.2447 (4) Å

b = 4.1135 (1) Å

c = 31.1380 (11) Å

β = 112.646 (1)°

V = 1447.46 (8) Å3

Z = 4

Mo Kα radiation

μ = 4.25 mm−1

T = 293 K

0.93 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.443, T max = 0.830

13946 measured reflections

3224 independent reflections

2697 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.083

S = 1.05

3224 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.66 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028917/zl2486sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028917/zl2486Isup2.hkl

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

[Ni(C8H6BrN3OS)(C5H5N)]	F(000) = 816
Mr = 409.94	Dx = 1.881 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17227 reflections
a = 12.2447 (4) Å	θ = 2.9–27.5°
b = 4.1135 (1) Å	µ = 4.25 mm−1
c = 31.1380 (11) Å	T = 293 K
β = 112.646 (1)°	Needle, red
V = 1447.46 (8) Å3	0.93 × 0.10 × 0.05 mm
Z = 4

Nonius KappaCCD diffractometer	3224 independent reflections
Radiation source: fine-focus sealed tube, Bruker Kappa CCD	2697 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9 pixels mm-1	θmax = 27.6°, θmin = 3.3°
CCD rotation images, thick slices scans	h = −15→15
Absorption correction: multi-scan (Blessing, 1995)	k = −5→5
Tmin = 0.443, Tmax = 0.830	l = −40→40
13946 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0442P)2 + 0.6555P] where P = (Fo2 + 2Fc2)/3
3224 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.66 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	1.37247 (2)	0.72025 (7)	0.228104 (10)	0.04622 (11)
Ni1	0.80812 (3)	−0.06339 (9)	0.089703 (11)	0.03527 (11)
S1	0.71884 (6)	−0.35252 (19)	0.02859 (2)	0.04380 (17)
O1	0.87955 (16)	0.1736 (5)	0.14418 (7)	0.0419 (4)
N1	0.93997 (18)	−0.0757 (5)	0.07408 (7)	0.0339 (4)
N2	0.9399 (2)	−0.2507 (6)	0.03540 (8)	0.0403 (5)
N3	0.8245 (2)	−0.5541 (7)	−0.02746 (9)	0.0519 (6)
H1	0.8831	−0.6069	−0.03	0.062*
H2	0.7769	−0.6986	−0.0334	0.062*
N4	0.67067 (19)	−0.0743 (6)	0.10494 (8)	0.0383 (5)
C1	1.0684 (2)	0.2490 (6)	0.13889 (9)	0.0350 (5)
C2	0.9877 (2)	0.2887 (6)	0.16117 (9)	0.0357 (5)
C3	1.0269 (2)	0.4575 (7)	0.20359 (10)	0.0423 (6)
H3	0.9751	0.4858	0.2187	0.051*
C4	1.1399 (2)	0.5829 (7)	0.22359 (10)	0.0428 (6)
H4	1.1642	0.6923	0.2519	0.051*
C5	1.2167 (2)	0.5430 (6)	0.20077 (9)	0.0377 (5)
C6	1.1830 (2)	0.3830 (7)	0.15955 (10)	0.0377 (5)
H6	1.2358	0.3616	0.1448	0.045*
C7	1.0394 (2)	0.0704 (7)	0.09658 (9)	0.0380 (6)
H7	1.0971	0.0579	0.0841	0.046*
C8	0.8393 (2)	−0.3869 (7)	0.01258 (9)	0.0390 (6)
C9	0.5660 (2)	0.0532 (7)	0.07772 (10)	0.0439 (6)
H9	0.558	0.1437	0.0493	0.053*
C10	0.4699 (3)	0.0547 (9)	0.09040 (12)	0.0553 (8)
H10	0.3986	0.1475	0.0711	0.066*
C11	0.4810 (3)	−0.0826 (9)	0.13187 (12)	0.0586 (8)
H11	0.4172	−0.0845	0.1411	0.07*
C12	0.5869 (3)	−0.2171 (8)	0.15973 (11)	0.0569 (8)
H12	0.5955	−0.3131	0.1879	0.068*
C13	0.6808 (3)	−0.2087 (8)	0.14557 (10)	0.0476 (7)
H13	0.7528	−0.2985	0.1647	0.057*

	U11	U22	U33	U12	U13	U23
Br1	0.03290 (15)	0.0510 (2)	0.05011 (18)	−0.00359 (11)	0.01082 (12)	−0.00312 (13)
Ni1	0.03052 (17)	0.0412 (2)	0.03447 (17)	0.00019 (13)	0.01296 (13)	0.00106 (13)
S1	0.0378 (3)	0.0507 (4)	0.0424 (4)	−0.0046 (3)	0.0148 (3)	−0.0052 (3)
O1	0.0321 (9)	0.0540 (12)	0.0406 (10)	−0.0025 (8)	0.0151 (8)	−0.0049 (9)
N1	0.0352 (10)	0.0337 (11)	0.0336 (10)	0.0034 (8)	0.0141 (9)	0.0010 (9)
N2	0.0419 (12)	0.0419 (13)	0.0399 (12)	0.0010 (10)	0.0189 (10)	−0.0039 (10)
N3	0.0488 (14)	0.0583 (17)	0.0502 (14)	−0.0046 (12)	0.0210 (12)	−0.0152 (12)
N4	0.0346 (11)	0.0443 (13)	0.0356 (11)	−0.0030 (9)	0.0130 (9)	−0.0002 (9)
C1	0.0327 (12)	0.0355 (13)	0.0367 (13)	0.0030 (10)	0.0132 (10)	0.0025 (10)
C2	0.0297 (11)	0.0387 (14)	0.0389 (13)	0.0030 (10)	0.0134 (10)	0.0046 (11)
C3	0.0359 (13)	0.0526 (17)	0.0410 (13)	0.0018 (12)	0.0179 (11)	−0.0023 (12)
C4	0.0387 (13)	0.0475 (16)	0.0393 (13)	0.0025 (12)	0.0118 (11)	−0.0041 (12)
C5	0.0289 (11)	0.0358 (14)	0.0438 (14)	0.0008 (10)	0.0089 (10)	0.0030 (11)
C6	0.0311 (12)	0.0391 (14)	0.0443 (14)	0.0020 (10)	0.0159 (11)	0.0018 (11)
C7	0.0348 (12)	0.0405 (15)	0.0426 (14)	0.0023 (11)	0.0191 (11)	0.0007 (11)
C8	0.0431 (14)	0.0363 (14)	0.0376 (13)	0.0049 (11)	0.0157 (11)	0.0021 (11)
C9	0.0365 (13)	0.0535 (18)	0.0393 (14)	0.0004 (12)	0.0120 (11)	0.0060 (12)
C10	0.0349 (14)	0.072 (2)	0.0588 (18)	0.0048 (14)	0.0179 (13)	0.0068 (16)
C11	0.0478 (17)	0.076 (2)	0.064 (2)	−0.0003 (16)	0.0339 (16)	0.0031 (17)
C12	0.062 (2)	0.071 (2)	0.0460 (17)	−0.0009 (17)	0.0303 (16)	0.0069 (16)
C13	0.0418 (14)	0.0607 (19)	0.0390 (14)	0.0018 (13)	0.0141 (12)	0.0074 (13)

Br1—C5	1.909 (3)	C2—C3	1.403 (4)
Ni1—N1	1.858 (2)	C3—C4	1.380 (4)
Ni1—O1	1.8576 (19)	C3—H3	0.93
Ni1—N4	1.917 (2)	C4—C5	1.390 (4)
Ni1—S1	2.1516 (8)	C4—H4	0.93
S1—C8	1.735 (3)	C5—C6	1.358 (4)
O1—C2	1.311 (3)	C6—H6	0.93
N1—C7	1.295 (3)	C7—H7	0.93
N1—N2	1.403 (3)	C9—C10	1.378 (4)
N2—C8	1.289 (4)	C9—H9	0.93
N3—C8	1.373 (4)	C10—C11	1.367 (5)
N3—H1	0.7822	C10—H10	0.93
N3—H2	0.8025	C11—C12	1.369 (5)
N4—C9	1.341 (4)	C11—H11	0.93
N4—C13	1.342 (4)	C12—C13	1.381 (4)
C1—C6	1.411 (4)	C12—H12	0.93
C1—C2	1.419 (3)	C13—H13	0.93
C1—C7	1.429 (4)
N1—Ni1—O1	95.87 (9)	C5—C4—H4	120.5
N1—Ni1—N4	177.00 (10)	C6—C5—C4	121.4 (2)
O1—Ni1—N4	86.32 (9)	C6—C5—Br1	119.63 (19)
N1—Ni1—S1	87.15 (7)	C4—C5—Br1	118.9 (2)
O1—Ni1—S1	176.46 (6)	C5—C6—C1	120.5 (2)
N4—Ni1—S1	90.60 (7)	C5—C6—H6	119.8
C8—S1—Ni1	95.77 (10)	C1—C6—H6	119.8
C2—O1—Ni1	127.26 (17)	N1—C7—C1	125.8 (2)
C7—N1—N2	113.1 (2)	N1—C7—H7	117.1
C7—N1—Ni1	125.23 (18)	C1—C7—H7	117.1
N2—N1—Ni1	121.70 (16)	N2—C8—N3	118.8 (2)
C8—N2—N1	112.4 (2)	N2—C8—S1	122.9 (2)
C8—N3—H1	115.1	N3—C8—S1	118.2 (2)
C8—N3—H2	114.2	N4—C9—C10	122.3 (3)
H1—N3—H2	112.6	N4—C9—H9	118.8
C9—N4—C13	118.4 (2)	C10—C9—H9	118.8
C9—N4—Ni1	123.42 (18)	C11—C10—C9	118.9 (3)
C13—N4—Ni1	118.17 (19)	C11—C10—H10	120.5
C6—C1—C2	119.3 (2)	C9—C10—H10	120.5
C6—C1—C7	118.2 (2)	C10—C11—C12	119.4 (3)
C2—C1—C7	122.5 (2)	C10—C11—H11	120.3
O1—C2—C3	119.0 (2)	C12—C11—H11	120.3
O1—C2—C1	123.2 (2)	C11—C12—C13	119.3 (3)
C3—C2—C1	117.8 (2)	C11—C12—H12	120.4
C4—C3—C2	122.0 (2)	C13—C12—H12	120.4
C4—C3—H3	119	N4—C13—C12	121.7 (3)
C2—C3—H3	119	N4—C13—H13	119.2
C3—C4—C5	118.9 (3)	C12—C13—H13	119.2
C3—C4—H4	120.5
N1—Ni1—S1—C8	1.82 (11)	C3—C4—C5—C6	−0.3 (4)
N4—Ni1—S1—C8	−176.20 (12)	C3—C4—C5—Br1	179.4 (2)
N1—Ni1—O1—C2	1.9 (2)	C4—C5—C6—C1	−0.7 (4)
N4—Ni1—O1—C2	179.8 (2)	Br1—C5—C6—C1	179.7 (2)
O1—Ni1—N1—C7	−4.3 (2)	C2—C1—C6—C5	1.3 (4)
S1—Ni1—N1—C7	177.6 (2)	C7—C1—C6—C5	−177.2 (2)
O1—Ni1—N1—N2	175.74 (19)	N2—N1—C7—C1	−175.7 (2)
S1—Ni1—N1—N2	−2.40 (18)	Ni1—N1—C7—C1	4.3 (4)
C7—N1—N2—C8	−178.1 (2)	C6—C1—C7—N1	177.7 (3)
Ni1—N1—N2—C8	1.9 (3)	C2—C1—C7—N1	−0.7 (4)
O1—Ni1—N4—C9	119.2 (2)	N1—N2—C8—N3	177.0 (2)
S1—Ni1—N4—C9	−62.5 (2)	N1—N2—C8—S1	0.2 (3)
O1—Ni1—N4—C13	−58.9 (2)	Ni1—S1—C8—N2	−1.6 (3)
S1—Ni1—N4—C13	119.3 (2)	Ni1—S1—C8—N3	−178.4 (2)
Ni1—O1—C2—C3	−178.72 (19)	C13—N4—C9—C10	1.0 (4)
Ni1—O1—C2—C1	0.8 (4)	Ni1—N4—C9—C10	−177.1 (2)
C6—C1—C2—O1	179.6 (2)	N4—C9—C10—C11	−0.9 (5)
C7—C1—C2—O1	−2.0 (4)	C9—C10—C11—C12	0.1 (5)
C6—C1—C2—C3	−0.9 (4)	C10—C11—C12—C13	0.6 (5)
C7—C1—C2—C3	177.5 (2)	C9—N4—C13—C12	−0.2 (4)
O1—C2—C3—C4	179.5 (3)	Ni1—N4—C13—C12	178.0 (2)
C1—C2—C3—C4	0.0 (4)	C11—C12—C13—N4	−0.6 (5)
C2—C3—C4—C5	0.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N2i	0.78	2.31	3.095 (3)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯N2i	0.78	2.31	3.095 (3)	178

Symmetry code: (i) .