(Methanol-κO){1-[2-(piperazin-4-ium-1-yl-κN(1))ethyl-imino-methyl-κN]naphthalen-2-olato-κO}bis-(thio-cyanato-κN)nickel(II) methanol monosolvate.

In the title solvated complex, [Ni(C(17)H(21)N(3)O)(NCS)(2)(CH(3)OH)]·CH(3)OH, the Ni(2+) ion is coordinated by one phenolate O, one imine N, and one amine N atom of the tridentate Schiff base ligand, two thio-cyanate N atoms and one methanol O atom, resulting in a distorted cis-NiO(2)N(4) octa-hedral geometry. The chelate ring formed by the phenolate O and imine N atoms approximates to an envelope with the Ni atom as the flap, whereas the chelate ring formed by the two N atoms is twisted about the C-C bond. In the crystal, the components are linked by O-H⋯O, N-H⋯O, N-H⋯S, and O-H⋯S hydrogen bonds.

Related literature

For background to the biological properties of nickel complexes of Schiff bases, see: Chohan & Kausar (1993 ▶); Osowole et al. (2008 ▶); Arif et al. (2011 ▶). For related structures, see: Ji & Lu (2010 ▶); Wang (2010 ▶); Xue et al. (2010 ▶).

Experimental

Crystal data

[Ni(C17H21N3O)(NCS)2(CH4O)]·CH4O

M = 522.32

Monoclinic,

a = 9.7420 (19) Å

b = 15.304 (3) Å

c = 18.302 (5) Å

β = 116.01 (2)°

V = 2452.3 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.99 mm−1

T = 298 K

0.17 × 0.15 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.849, T max = 0.865

16581 measured reflections

4196 independent reflections

2354 reflections with I > 2σ(I)

R int = 0.153

Refinement

R[F 2 > 2σ(F 2)] = 0.092

wR(F 2) = 0.209

S = 1.00

4196 reflections

295 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.05 e Å−3

Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812013773/hb6710sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013773/hb6710Isup2.hkl

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

[Ni(C17H21N3O)(NCS)2(CH4O)]·CH4O	F(000) = 1096
Mr = 522.32	Dx = 1.415 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.7420 (19) Å	Cell parameters from 888 reflections
b = 15.304 (3) Å	θ = 2.3–24.5°
c = 18.302 (5) Å	µ = 0.99 mm−1
β = 116.01 (2)°	T = 298 K
V = 2452.3 (10) Å3	Block, green
Z = 4	0.17 × 0.15 × 0.15 mm

Bruker SMART 1000 CCD diffractometer	4196 independent reflections
Radiation source: fine-focus sealed tube	2354 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.153
ω scan	θmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −11→11
Tmin = 0.849, Tmax = 0.865	k = −18→18
16581 measured reflections	l = −21→21

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)] = 0.092	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0864P)2] where P = (Fo2 + 2Fc2)/3
4196 reflections	(Δ/σ)max < 0.001
295 parameters	Δρmax = 1.05 e Å−3
1 restraint	Δρmin = −0.47 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	0.08725 (12)	0.32345 (6)	0.35614 (6)	0.0356 (3)
S1	−0.3385 (3)	0.40557 (18)	0.11040 (14)	0.0662 (8)
S2	−0.1939 (3)	0.23841 (17)	0.50772 (14)	0.0641 (8)
O1	0.1635 (7)	0.4331 (3)	0.4268 (3)	0.0465 (15)
O2	0.2267 (8)	0.3634 (4)	0.2996 (4)	0.0612 (17)
O3	0.0875 (10)	0.4095 (6)	0.1353 (4)	0.097 (3)
H3	0.0055	0.3840	0.1128	0.145*
N1	0.2670 (7)	0.2604 (4)	0.4397 (4)	0.0437 (18)
N2	0.0484 (7)	0.1938 (4)	0.2933 (4)	0.0348 (15)
N3	−0.0853 (8)	0.3835 (4)	0.2599 (4)	0.0488 (19)
N4	−0.0474 (8)	0.2903 (4)	0.4131 (4)	0.0412 (17)
N5	−0.1175 (7)	0.0886 (4)	0.1435 (4)	0.0450 (18)
H5A	−0.1729	0.1302	0.1080	0.054*
H5B	−0.1389	0.0370	0.1173	0.054*
C1	0.3224 (8)	0.3598 (5)	0.5527 (4)	0.0374 (19)
C2	0.2355 (9)	0.4313 (5)	0.5085 (5)	0.041 (2)
C3	0.2202 (10)	0.5057 (6)	0.5479 (5)	0.053 (2)
H3A	0.1582	0.5512	0.5174	0.063*
C4	0.2957 (11)	0.5132 (6)	0.6318 (5)	0.054 (2)
H4	0.2873	0.5643	0.6569	0.065*
C5	0.3847 (9)	0.4438 (5)	0.6788 (5)	0.043 (2)
C6	0.4632 (11)	0.4468 (7)	0.7668 (5)	0.058 (3)
H6	0.4564	0.4978	0.7926	0.070*
C7	0.5449 (10)	0.3806 (7)	0.8133 (5)	0.054 (3)
H7	0.5940	0.3861	0.8696	0.065*
C8	0.5545 (10)	0.3047 (7)	0.7763 (5)	0.060 (3)
H8	0.6101	0.2581	0.8082	0.072*
C9	0.4832 (9)	0.2953 (6)	0.6919 (5)	0.046 (2)
H9	0.4903	0.2426	0.6685	0.055*
C10	0.3988 (9)	0.3667 (6)	0.6409 (4)	0.042 (2)
C11	0.3444 (11)	0.2811 (5)	0.5145 (5)	0.052 (2)
H11	0.4209	0.2428	0.5471	0.062*
C12	0.2999 (10)	0.1768 (6)	0.4112 (5)	0.055 (3)
H12A	0.3612	0.1398	0.4570	0.066*
H12B	0.3554	0.1865	0.3790	0.066*
C13	0.1465 (10)	0.1340 (5)	0.3598 (5)	0.049 (2)
H13A	0.1623	0.0800	0.3367	0.059*
H13B	0.0960	0.1199	0.3937	0.059*
C14	0.0892 (9)	0.1941 (5)	0.2235 (4)	0.040 (2)
H14A	0.1981	0.2043	0.2441	0.048*
H14B	0.0366	0.2421	0.1875	0.048*
C15	0.0481 (10)	0.1082 (5)	0.1741 (5)	0.043 (2)
H15A	0.0732	0.1135	0.1285	0.052*
H15B	0.1076	0.0606	0.2082	0.052*
C16	−0.1588 (10)	0.0854 (5)	0.2119 (5)	0.048 (2)
H16A	−0.1049	0.0375	0.2478	0.058*
H16B	−0.2675	0.0745	0.1912	0.058*
C17	−0.1185 (10)	0.1709 (5)	0.2595 (5)	0.048 (2)
H17A	−0.1780	0.2177	0.2242	0.057*
H17B	−0.1467	0.1665	0.3040	0.057*
C18	−0.1908 (10)	0.3914 (5)	0.1988 (5)	0.0382 (19)
C19	−0.1038 (10)	0.2711 (5)	0.4529 (5)	0.041 (2)
C20	0.3836 (12)	0.3845 (8)	0.3386 (7)	0.087 (4)
H20A	0.3976	0.4441	0.3269	0.130*
H20B	0.4389	0.3466	0.3192	0.130*
H20C	0.4208	0.3773	0.3962	0.130*
C22	0.1608 (19)	0.4057 (12)	0.0882 (9)	0.148 (7)
H22A	0.1522	0.4610	0.0618	0.222*
H22B	0.1160	0.3609	0.0480	0.222*
H22C	0.2666	0.3925	0.1212	0.222*
H2	0.189 (11)	0.361 (7)	0.2499 (8)	0.080*

	U11	U22	U33	U12	U13	U23
Ni1	0.0411 (6)	0.0276 (5)	0.0256 (5)	0.0056 (5)	0.0031 (4)	0.0015 (4)
S1	0.0644 (17)	0.0600 (17)	0.0413 (14)	0.0051 (13)	−0.0072 (12)	−0.0074 (12)
S2	0.084 (2)	0.0604 (17)	0.0447 (14)	−0.0249 (14)	0.0252 (14)	−0.0107 (12)
O1	0.077 (4)	0.017 (3)	0.028 (3)	0.012 (3)	0.006 (3)	0.002 (2)
O2	0.062 (5)	0.062 (4)	0.051 (4)	−0.018 (3)	0.017 (4)	−0.021 (4)
O3	0.100 (7)	0.124 (8)	0.056 (5)	−0.019 (6)	0.025 (5)	−0.004 (5)
N1	0.047 (4)	0.042 (4)	0.025 (4)	0.013 (3)	0.000 (3)	−0.008 (3)
N2	0.045 (4)	0.026 (4)	0.027 (3)	0.006 (3)	0.010 (3)	0.002 (3)
N3	0.052 (5)	0.040 (4)	0.038 (4)	0.006 (3)	0.005 (4)	0.004 (3)
N4	0.058 (5)	0.034 (4)	0.031 (4)	0.011 (3)	0.019 (4)	−0.004 (3)
N5	0.053 (5)	0.034 (4)	0.035 (4)	0.009 (3)	0.007 (4)	−0.002 (3)
C1	0.033 (5)	0.030 (4)	0.029 (4)	0.002 (4)	−0.005 (4)	−0.001 (3)
C2	0.045 (5)	0.032 (5)	0.033 (5)	−0.003 (4)	0.005 (4)	0.001 (4)
C3	0.068 (7)	0.034 (5)	0.054 (6)	0.007 (4)	0.025 (5)	−0.001 (4)
C4	0.072 (7)	0.039 (5)	0.038 (5)	0.020 (5)	0.012 (5)	−0.001 (4)
C5	0.043 (5)	0.043 (5)	0.040 (5)	−0.009 (4)	0.014 (4)	−0.015 (4)
C6	0.059 (6)	0.072 (7)	0.040 (5)	−0.005 (5)	0.018 (5)	−0.006 (5)
C7	0.059 (6)	0.074 (8)	0.029 (5)	−0.019 (5)	0.018 (5)	−0.010 (5)
C8	0.043 (6)	0.082 (8)	0.043 (6)	0.004 (5)	0.008 (5)	0.019 (5)
C9	0.051 (6)	0.052 (6)	0.026 (4)	−0.008 (4)	0.009 (4)	0.007 (4)
C10	0.037 (5)	0.049 (5)	0.027 (4)	0.001 (4)	0.001 (4)	−0.004 (4)
C11	0.062 (6)	0.035 (5)	0.048 (6)	0.019 (4)	0.013 (5)	0.007 (4)
C12	0.056 (6)	0.049 (5)	0.030 (5)	0.031 (5)	−0.009 (4)	−0.009 (4)
C13	0.080 (7)	0.030 (5)	0.037 (5)	0.005 (4)	0.024 (5)	−0.005 (4)
C14	0.044 (5)	0.021 (4)	0.034 (4)	0.000 (3)	−0.001 (4)	−0.004 (3)
C15	0.052 (6)	0.037 (5)	0.040 (5)	−0.004 (4)	0.019 (4)	−0.007 (4)
C16	0.042 (5)	0.036 (5)	0.054 (6)	−0.011 (4)	0.010 (4)	−0.010 (4)
C17	0.062 (6)	0.024 (4)	0.057 (6)	−0.005 (4)	0.026 (5)	−0.006 (4)
C18	0.050 (5)	0.023 (4)	0.038 (5)	0.006 (4)	0.015 (4)	0.002 (4)
C19	0.048 (6)	0.044 (5)	0.028 (5)	0.006 (4)	0.012 (4)	−0.008 (4)
C20	0.056 (7)	0.104 (10)	0.104 (9)	−0.015 (7)	0.040 (7)	−0.002 (8)
C22	0.141 (14)	0.199 (19)	0.132 (13)	−0.042 (13)	0.085 (13)	−0.032 (13)

Ni1—N1	1.997 (6)	C5—C10	1.406 (11)
Ni1—N3	2.044 (7)	C5—C6	1.450 (11)
Ni1—O1	2.049 (5)	C6—C7	1.337 (12)
Ni1—N4	2.064 (7)	C6—H6	0.9300
Ni1—O2	2.128 (7)	C7—C8	1.369 (12)
Ni1—N2	2.241 (6)	C7—H7	0.9300
S1—C18	1.641 (9)	C8—C9	1.396 (11)
S2—C19	1.673 (10)	C8—H8	0.9300
O1—C2	1.344 (9)	C9—C10	1.438 (11)
O2—C20	1.411 (11)	C9—H9	0.9300
O2—H2	0.818 (10)	C11—H11	0.9300
O3—C22	1.339 (13)	C12—C13	1.521 (12)
O3—H3	0.8200	C12—H12A	0.9700
N1—C11	1.281 (10)	C12—H12B	0.9700
N1—C12	1.468 (9)	C13—H13A	0.9700
N2—C13	1.487 (9)	C13—H13B	0.9700
N2—C14	1.495 (9)	C14—C15	1.546 (10)
N2—C17	1.505 (10)	C14—H14A	0.9700
N3—C18	1.146 (9)	C14—H14B	0.9700
N4—C19	1.128 (9)	C15—H15A	0.9700
N5—C16	1.473 (9)	C15—H15B	0.9700
N5—C15	1.488 (10)	C16—C17	1.525 (10)
N5—H5A	0.9000	C16—H16A	0.9700
N5—H5B	0.9000	C16—H16B	0.9700
C1—C2	1.403 (10)	C17—H17A	0.9700
C1—C10	1.454 (10)	C17—H17B	0.9700
C1—C11	1.455 (11)	C20—H20A	0.9600
C2—C3	1.390 (11)	C20—H20B	0.9600
C3—C4	1.386 (12)	C20—H20C	0.9600
C3—H3A	0.9300	C22—H22A	0.9600
C4—C5	1.402 (11)	C22—H22B	0.9600
C4—H4	0.9300	C22—H22C	0.9600
N1—Ni1—N3	172.3 (3)	C9—C8—H8	119.1
N1—Ni1—O1	87.7 (2)	C8—C9—C10	120.4 (8)
N3—Ni1—O1	96.3 (2)	C8—C9—H9	119.8
N1—Ni1—N4	91.9 (3)	C10—C9—H9	119.8
N3—Ni1—N4	94.6 (3)	C5—C10—C9	118.0 (7)
O1—Ni1—N4	91.0 (2)	C5—C10—C1	119.7 (7)
N1—Ni1—O2	88.8 (3)	C9—C10—C1	122.3 (7)
N3—Ni1—O2	84.9 (3)	N1—C11—C1	125.3 (8)
O1—Ni1—O2	86.6 (2)	N1—C11—H11	117.4
N4—Ni1—O2	177.4 (2)	C1—C11—H11	117.4
N1—Ni1—N2	81.9 (2)	N1—C12—C13	106.7 (7)
N3—Ni1—N2	93.8 (2)	N1—C12—H12A	110.4
O1—Ni1—N2	169.1 (2)	C13—C12—H12A	110.4
N4—Ni1—N2	92.3 (2)	N1—C12—H12B	110.4
O2—Ni1—N2	90.3 (2)	C13—C12—H12B	110.4
C2—O1—Ni1	123.5 (4)	H12A—C12—H12B	108.6
C20—O2—Ni1	126.9 (6)	N2—C13—C12	110.2 (7)
C20—O2—H2	116 (8)	N2—C13—H13A	109.6
Ni1—O2—H2	117 (7)	C12—C13—H13A	109.6
C22—O3—H3	109.5	N2—C13—H13B	109.6
C11—N1—C12	118.5 (7)	C12—C13—H13B	109.6
C11—N1—Ni1	127.3 (6)	H13A—C13—H13B	108.1
C12—N1—Ni1	113.8 (5)	N2—C14—C15	113.6 (6)
C13—N2—C14	112.6 (6)	N2—C14—H14A	108.9
C13—N2—C17	112.5 (6)	C15—C14—H14A	108.9
C14—N2—C17	107.1 (6)	N2—C14—H14B	108.9
C13—N2—Ni1	102.8 (4)	C15—C14—H14B	108.9
C14—N2—Ni1	112.8 (4)	H14A—C14—H14B	107.7
C17—N2—Ni1	109.0 (4)	N5—C15—C14	110.6 (6)
C18—N3—Ni1	159.3 (7)	N5—C15—H15A	109.5
C19—N4—Ni1	171.1 (7)	C14—C15—H15A	109.5
C16—N5—C15	110.0 (6)	N5—C15—H15B	109.5
C16—N5—H5A	109.7	C14—C15—H15B	109.5
C15—N5—H5A	109.7	H15A—C15—H15B	108.1
C16—N5—H5B	109.7	N5—C16—C17	111.0 (7)
C15—N5—H5B	109.7	N5—C16—H16A	109.4
H5A—N5—H5B	108.2	C17—C16—H16A	109.4
C2—C1—C10	118.0 (7)	N5—C16—H16B	109.4
C2—C1—C11	123.1 (7)	C17—C16—H16B	109.4
C10—C1—C11	118.8 (7)	H16A—C16—H16B	108.0
O1—C2—C3	115.9 (7)	N2—C17—C16	113.3 (6)
O1—C2—C1	123.2 (7)	N2—C17—H17A	108.9
C3—C2—C1	120.9 (7)	C16—C17—H17A	108.9
C4—C3—C2	121.1 (8)	N2—C17—H17B	108.9
C4—C3—H3A	119.4	C16—C17—H17B	108.9
C2—C3—H3A	119.4	H17A—C17—H17B	107.7
C3—C4—C5	120.2 (8)	N3—C18—S1	177.8 (8)
C3—C4—H4	119.9	N4—C19—S2	176.6 (8)
C5—C4—H4	119.9	O2—C20—H20A	109.5
C4—C5—C10	120.0 (7)	O2—C20—H20B	109.5
C4—C5—C6	122.8 (8)	H20A—C20—H20B	109.5
C10—C5—C6	117.2 (8)	O2—C20—H20C	109.5
C7—C6—C5	124.1 (9)	H20A—C20—H20C	109.5
C7—C6—H6	118.0	H20B—C20—H20C	109.5
C5—C6—H6	118.0	O3—C22—H22A	109.5
C6—C7—C8	118.6 (8)	O3—C22—H22B	109.5
C6—C7—H7	120.7	H22A—C22—H22B	109.5
C8—C7—H7	120.7	O3—C22—H22C	109.5
C7—C8—C9	121.8 (9)	H22A—C22—H22C	109.5
C7—C8—H8	119.1	H22B—C22—H22C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82 (1)	2.03 (4)	2.793 (10)	155 (10)
N5—H5B···O1i	0.90	1.75	2.649 (8)	175
N5—H5A···S2ii	0.90	2.67	3.480 (7)	150
O3—H3···S2ii	0.82	2.78	3.532 (9)	154

Table 1

Selected bond lengths (Å)

Ni1—N1	1.997 (6)
Ni1—N3	2.044 (7)
Ni1—O1	2.049 (5)
Ni1—N4	2.064 (7)
Ni1—O2	2.128 (7)
Ni1—N2	2.241 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82 (1)	2.03 (4)	2.793 (10)	155 (10)
N5—H5B⋯O1i	0.90	1.75	2.649 (8)	175
N5—H5A⋯S2ii	0.90	2.67	3.480 (7)	150
O3—H3⋯S2ii	0.82	2.78	3.532 (9)	154

Symmetry codes: (i) ; (ii) .