Bis(4-hy-droxy-3-meth-oxy-benzaldehyde 4-phenyl-thio-semicarbazonato-N (1),S)nickel(II).

In the title compound, [Ni(C15H14N3O2S)2], the Ni(II) atom lies on a center of symmetry. The deprotonated ligands act as N,S-donors, forming five-membered metalla-rings. The Ni(II) atom is four-coordinated in a slightly distorted square-planar environment. In the crystal, the discrete complex mol-ecules are linked by weak N-H⋯O hydrogen bonds, generating chains along [110]. The chains are further connected via weak O-H⋯N inter-actions into a layered network extending parallel to (001).

Related literature

For the crystal structure of the ligand, see: Oliveira et al. (2013 ▶). For the crystal structure of a similar complex, see: Akinchan & Abram (2000 ▶). For the coordination chemistry of thio­semicarbazone compounds, see: Lobana et al. (2009 ▶).

Experimental

Crystal data

[Ni(C15n class="Species">H14N3O2S)2]

M = 659.41

Triclinic,

a = 6.8080 (4) Å

b = 7.5569 (4) Å

c = 14.3902 (8) Å

α = 98.514 (4)°

β = 92.062 (5)°

γ = 102.698 (5)°

V = 712.47 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.88 mm−1

T = 200 K

0.12 × 0.08 × 0.04 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.800, T max = 0.936

3117 measured reflections

2539 independent reflections

2539 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.06

3117 reflections

206 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.19 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▶); 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. DOI: 10.1107/S1600536814009027/lr2126sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009027/lr2126Isup2.hkl

CCDC reference: 998671

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(C15H14N3O2S)2]	V = 712.47 (7) Å3
Mr = 659.41	Z = 1
Triclinic, P1	F(000) = 342
Hall symbol: -P 1	Dx = 1.537 Mg m−3
a = 6.8080 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5569 (4) Å	θ = 1.4–27.0°
c = 14.3902 (8) Å	µ = 0.88 mm−1
α = 98.514 (4)°	T = 200 K
β = 92.062 (5)°	Prism, red
γ = 102.698 (5)°	0.12 × 0.08 × 0.04 mm

Stoe IPDS-1 diffractometer	2539 independent reflections
Radiation source: fine-focus sealed tube, Stoe IPDS-1	2539 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ scans	θmax = 27.0°, θmin = 1.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −8→8
Tmin = 0.800, Tmax = 0.936	k = −9→9
3117 measured reflections	l = −18→16

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.0121P] where P = (Fo2 + 2Fc2)/3
3117 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.19 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
Ni1	0.5000	1.0000	0.0000	0.02742 (11)
C1	0.1523 (3)	0.8520 (2)	0.32101 (13)	0.0331 (4)
C2	0.3262 (3)	0.8457 (3)	0.37156 (15)	0.0435 (5)
H2	0.4537	0.8789	0.3463	0.052*
C3	0.3138 (4)	0.7905 (3)	0.45971 (16)	0.0516 (6)
H3	0.4338	0.7874	0.4946	0.062*
C4	0.1309 (5)	0.7404 (4)	0.49672 (18)	0.0651 (7)
H4	0.1233	0.7025	0.5568	0.078*
C5	−0.0420 (5)	0.7461 (5)	0.4453 (2)	0.0808 (10)
H5	−0.1697	0.7112	0.4701	0.097*
C6	−0.0314 (4)	0.8019 (4)	0.35813 (18)	0.0580 (6)
H6	−0.1516	0.8058	0.3236	0.070*
N1	0.1511 (3)	0.9162 (2)	0.23399 (12)	0.0329 (3)
H1N1	0.056 (4)	0.957 (3)	0.2191 (18)	0.051 (7)*
C7	0.2813 (3)	0.9123 (2)	0.16455 (13)	0.0281 (4)
S1	0.21900 (7)	1.00329 (7)	0.06685 (3)	0.03549 (13)
N2	0.4377 (2)	0.8401 (2)	0.17166 (11)	0.0312 (3)
N3	0.5427 (2)	0.8441 (2)	0.08926 (11)	0.0300 (3)
C8	0.6613 (3)	0.7309 (3)	0.07729 (14)	0.0337 (4)
H8	0.739 (3)	0.737 (3)	0.0244 (16)	0.035 (5)*
C9	0.6955 (3)	0.5875 (2)	0.12971 (13)	0.0317 (4)
C10	0.8662 (3)	0.5206 (3)	0.10650 (14)	0.0364 (4)
H10	0.9538	0.5760	0.0637	0.044*
C11	0.9096 (3)	0.3751 (3)	0.14491 (14)	0.0362 (4)
H11	1.0260	0.3307	0.1286	0.043*
C12	0.7829 (3)	0.2951 (2)	0.20690 (14)	0.0322 (4)
C13	0.6150 (3)	0.3636 (2)	0.23340 (13)	0.0302 (4)
C14	0.5702 (3)	0.5083 (2)	0.19495 (13)	0.0315 (4)
H14	0.4552	0.5539	0.2126	0.038*
O1	0.8234 (2)	0.14835 (19)	0.24410 (11)	0.0411 (3)
H1O1	0.7174	0.0896	0.2635	0.062*
O2	0.5064 (2)	0.27403 (18)	0.29749 (10)	0.0392 (3)
C15	0.3366 (4)	0.3391 (3)	0.33051 (18)	0.0478 (5)
H15A	0.3816	0.4655	0.3637	0.072*
H15B	0.2688	0.2604	0.3736	0.072*
H15C	0.2423	0.3362	0.2769	0.072*

	U11	U22	U33	U12	U13	U23
Ni1	0.03166 (19)	0.03038 (17)	0.02632 (18)	0.01380 (13)	0.00733 (13)	0.01269 (13)
C1	0.0424 (11)	0.0294 (8)	0.0300 (10)	0.0098 (8)	0.0091 (8)	0.0086 (7)
C2	0.0491 (12)	0.0518 (12)	0.0369 (11)	0.0196 (10)	0.0086 (9)	0.0170 (9)
C3	0.0757 (17)	0.0529 (12)	0.0328 (11)	0.0258 (12)	0.0006 (11)	0.0125 (10)
C4	0.094 (2)	0.0699 (16)	0.0338 (12)	0.0125 (15)	0.0135 (14)	0.0237 (12)
C5	0.073 (2)	0.120 (3)	0.0497 (16)	0.0017 (18)	0.0235 (15)	0.0408 (17)
C6	0.0508 (14)	0.0816 (17)	0.0419 (13)	0.0049 (12)	0.0113 (11)	0.0246 (12)
N1	0.0338 (8)	0.0393 (8)	0.0330 (8)	0.0168 (7)	0.0097 (7)	0.0155 (7)
C7	0.0309 (9)	0.0265 (8)	0.0288 (9)	0.0073 (7)	0.0057 (7)	0.0092 (7)
S1	0.0338 (3)	0.0491 (3)	0.0333 (3)	0.0198 (2)	0.0090 (2)	0.0209 (2)
N2	0.0375 (8)	0.0353 (8)	0.0285 (8)	0.0173 (7)	0.0103 (7)	0.0140 (6)
N3	0.0349 (8)	0.0322 (7)	0.0281 (8)	0.0136 (6)	0.0083 (6)	0.0114 (6)
C8	0.0405 (10)	0.0369 (9)	0.0320 (10)	0.0188 (8)	0.0123 (8)	0.0149 (8)
C9	0.0377 (10)	0.0332 (9)	0.0302 (9)	0.0166 (8)	0.0069 (8)	0.0106 (7)
C10	0.0432 (11)	0.0371 (9)	0.0360 (10)	0.0180 (8)	0.0142 (9)	0.0127 (8)
C11	0.0366 (10)	0.0402 (10)	0.0393 (11)	0.0204 (8)	0.0094 (8)	0.0118 (8)
C12	0.0360 (10)	0.0306 (8)	0.0347 (10)	0.0137 (7)	0.0011 (8)	0.0114 (7)
C13	0.0334 (9)	0.0293 (8)	0.0303 (9)	0.0091 (7)	0.0043 (8)	0.0096 (7)
C14	0.0343 (9)	0.0308 (8)	0.0351 (10)	0.0152 (7)	0.0067 (8)	0.0112 (7)
O1	0.0414 (8)	0.0405 (7)	0.0524 (9)	0.0213 (6)	0.0094 (7)	0.0239 (6)
O2	0.0418 (8)	0.0387 (7)	0.0475 (8)	0.0176 (6)	0.0163 (7)	0.0240 (6)
C15	0.0532 (13)	0.0436 (11)	0.0576 (14)	0.0213 (10)	0.0292 (11)	0.0226 (10)

Ni1—N3	1.9220 (15)	N2—N3	1.407 (2)
Ni1—N3i	1.9220 (15)	N3—C8	1.298 (2)
Ni1—S1i	2.1753 (5)	C8—C9	1.462 (2)
Ni1—S1	2.1753 (5)	C8—H8	0.94 (2)
C1—C6	1.376 (3)	C9—C10	1.398 (3)
C1—C2	1.380 (3)	C9—C14	1.402 (3)
C1—N1	1.409 (2)	C10—C11	1.383 (3)
C2—C3	1.392 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.375 (3)
C3—C4	1.370 (4)	C11—H11	0.9500
C3—H3	0.9500	C12—O1	1.375 (2)
C4—C5	1.380 (5)	C12—C13	1.398 (3)
C4—H4	0.9500	C13—O2	1.367 (2)
C5—C6	1.381 (4)	C13—C14	1.381 (2)
C5—H5	0.9500	C14—H14	0.9500
C6—H6	0.9500	O1—H1O1	0.8400
N1—C7	1.361 (2)	O2—C15	1.423 (2)
N1—H1N1	0.81 (3)	C15—H15A	0.9800
C7—N2	1.306 (2)	C15—H15B	0.9800
C7—S1	1.7322 (18)	C15—H15C	0.9800
N3—Ni1—N3i	180.00 (6)	C8—N3—N2	115.09 (15)
N3—Ni1—S1i	95.42 (5)	C8—N3—Ni1	123.66 (13)
N3i—Ni1—S1i	84.58 (5)	N2—N3—Ni1	121.20 (11)
N3—Ni1—S1	84.58 (5)	N3—C8—C9	131.97 (17)
N3i—Ni1—S1	95.42 (5)	N3—C8—H8	116.2 (13)
S1i—Ni1—S1	180.00 (3)	C9—C8—H8	111.8 (13)
C6—C1—C2	119.5 (2)	C10—C9—C14	119.10 (16)
C6—C1—N1	116.8 (2)	C10—C9—C8	114.36 (17)
C2—C1—N1	123.65 (18)	C14—C9—C8	126.46 (16)
C1—C2—C3	119.7 (2)	C11—C10—C9	120.99 (18)
C1—C2—H2	120.1	C11—C10—H10	119.5
C3—C2—H2	120.1	C9—C10—H10	119.5
C4—C3—C2	120.9 (2)	C12—C11—C10	119.49 (17)
C4—C3—H3	119.6	C12—C11—H11	120.3
C2—C3—H3	119.6	C10—C11—H11	120.3
C3—C4—C5	118.9 (2)	C11—C12—O1	119.75 (16)
C3—C4—H4	120.5	C11—C12—C13	120.43 (16)
C5—C4—H4	120.5	O1—C12—C13	119.81 (17)
C4—C5—C6	120.7 (3)	O2—C13—C14	125.69 (16)
C4—C5—H5	119.6	O2—C13—C12	113.95 (15)
C6—C5—H5	119.6	C14—C13—C12	120.35 (17)
C1—C6—C5	120.3 (3)	C13—C14—C9	119.58 (16)
C1—C6—H6	119.8	C13—C14—H14	120.2
C5—C6—H6	119.8	C9—C14—H14	120.2
C7—N1—C1	130.38 (17)	C12—O1—H1O1	109.5
C7—N1—H1N1	111.6 (19)	C13—O2—C15	117.54 (14)
C1—N1—H1N1	117.9 (19)	O2—C15—H15A	109.5
N2—C7—N1	121.37 (16)	O2—C15—H15B	109.5
N2—C7—S1	123.56 (14)	H15A—C15—H15B	109.5
N1—C7—S1	115.05 (13)	O2—C15—H15C	109.5
C7—S1—Ni1	96.21 (6)	H15A—C15—H15C	109.5
C7—N2—N3	110.66 (14)	H15B—C15—H15C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ii	0.81 (3)	2.37 (3)	3.122 (2)	154 (2)
O1—H1O1···N2iii	0.84	2.54	3.131 (2)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.81 (3)	2.37 (3)	3.122 (2)	154 (2)
O1—H1O1⋯N2ii	0.84	2.54	3.131 (2)	129

Symmetry codes: (i) ; (ii) .