{5,5'-Dihydr-oxy-2,2'-[o-phenyl-enebis-(nitrilo-methyl-idyne)]diphenolato}nickel(II) dihydrate.

In the title complex, [Ni(C(20)H(14)N(2)O(4))]·2H(2)O, the Ni(II) ion is in an essentially square-planar geometry involving an N(2)O(2) atom set of the tetra-dentate Schiff base ligand. The Ni atom lies on a crystallographic twofold rotation axis. The asymmetric unit contains one half-mol-ecule of the complex and a water mol-ecule. An inter-molecular O-H⋯O hydrogen bond forms a four-membered ring, producing an R(1) (2)(4) ring motif involving a bifurcated hydrogen bond to the phenolate O atoms of the complex mol-ecule. In the crystal structure, mol-ecules are linked by π-π stacking inter-actions, with centroid-centroid distances in the range 3.5750 (11)-3.7750 (11) Å. As a result of the twofold symmetry, the central benzene ring makes the same dihedral angle of 15.75 (9)° with the two outer benzene rings. The dihedral angle between the two hydroxy-phenyl rings is 13.16 (5)°. In the crystal structure, mol-ecules are linked into infinite one-dimensional chains by directed four-membered O-H⋯O-H inter-actions along the c axis and are further connected by C-H⋯O and π-π stacking into a three-dimensional network. An inter-esting feature of the crystal structure is the short Ni⋯O, O⋯O and N⋯N inter-actions which are shorter than the sum of the van der Waals radii of the relevant atoms. The crystal structure is stabilized by inter-molecular O-H⋯O and C-H⋯O hydrogen bonds and by π-π stacking inter-actions.

Related literature

For bond-length data, see Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see, for example: Clark et al. (1968 ▶, 1969 ▶, 1970 ▶); Hodgson 1975 ▶. For applications and bioactivities, see, for example: Elmali et al. (2000 ▶); Blower (1998 ▶); Granovski et al. (1993 ▶); Li & Chang (1991 ▶); Shahrokhian et al. (2000 ▶); Fun & Kia (2008 ▶).

Experimental

Crystal data

[Ni(C20H14N2O4)]·2H2O

M = 441.07

Monoclinic,

a = 10.9049 (2) Å

b = 17.6602 (3) Å

c = 9.0375 (3) Å

β = 101.150 (1)°

V = 1707.61 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.18 mm−1

T = 100.0 (1) K

0.35 × 0.12 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.683, T max = 0.881

14574 measured reflections

3566 independent reflections

2388 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.120

S = 1.12

3566 reflections

136 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.61 e Å−3

Δρmin = −0.73 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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 and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026093/pk2114sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026093/pk2114Isup2.hkl

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

[Ni(C20H14N2O4)]·2H2O	F000 = 912
Mr = 441.07	Dx = 1.716 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3113 reflections
a = 10.9049 (2) Å	θ = 2.3–29.1º
b = 17.6602 (3) Å	µ = 1.18 mm−1
c = 9.0375 (3) Å	T = 100.0 (1) K
β = 101.150 (1)º	Block, red
V = 1707.61 (7) Å3	0.35 × 0.12 × 0.11 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3566 independent reflections
Radiation source: fine-focus sealed tube	2388 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.046
T = 100.0(1) K	θmax = 34.3º
φ and ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2005)	h = −17→17
Tmin = 0.683, Tmax = 0.881	k = −23→27
14574 measured reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0492P)2] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
3566 reflections	Δρmax = 0.61 e Å−3
136 parameters	Δρmin = −0.73 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cryosystem Cobra low-temperature attachment

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 > 2sigma(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	0.0000	0.246535 (17)	0.7500	0.01493 (11)
O1	0.04391 (12)	0.32501 (7)	0.88434 (14)	0.0174 (3)
O2	0.18665 (13)	0.44913 (8)	1.35074 (15)	0.0215 (3)
N1	0.06039 (14)	0.17016 (8)	0.88409 (17)	0.0152 (3)
C1	0.09715 (16)	0.32009 (10)	1.0287 (2)	0.0159 (4)
C2	0.11546 (17)	0.38691 (10)	1.1132 (2)	0.0175 (4)
H2A	0.0908	0.4329	1.0668	0.021*
C3	0.16965 (17)	0.38546 (10)	1.2647 (2)	0.0161 (4)
C4	0.21006 (17)	0.31684 (11)	1.3364 (2)	0.0200 (4)
H4A	0.2474	0.3160	1.4380	0.024*
C5	0.1937 (2)	0.25113 (10)	1.2545 (2)	0.0192 (4)
H5A	0.2218	0.2058	1.3015	0.023*
C6	0.13518 (18)	0.25029 (10)	1.1002 (2)	0.0160 (3)
C7	0.11768 (17)	0.17979 (10)	1.0251 (2)	0.0172 (4)
H7A	0.1490	0.1369	1.0793	0.021*
C8	0.03852 (17)	0.09645 (10)	0.8211 (2)	0.0181 (4)
C9	0.08370 (18)	0.02822 (10)	0.8878 (2)	0.0206 (4)
H9A	0.1404	0.0281	0.9790	0.025*
C10	0.04344 (18)	−0.03919 (11)	0.8171 (2)	0.0232 (4)
H10A	0.0748	−0.0849	0.8598	0.028*
O1W	0.15531 (13)	0.42836 (7)	0.67062 (15)	0.0240 (3)
H1W1	0.0971	0.3950	0.6774	0.036*
H2W1	0.1630	0.4380	0.5829	0.036*
H1O2	0.170 (2)	0.4836 (15)	1.304 (3)	0.047 (9)*

	U11	U22	U33	U12	U13	U23
Ni1	0.01935 (18)	0.01096 (18)	0.01281 (16)	0.000	−0.00102 (12)	0.000
O1	0.0240 (7)	0.0128 (6)	0.0126 (6)	0.0004 (5)	−0.0033 (5)	−0.0004 (5)
O2	0.0320 (8)	0.0146 (7)	0.0156 (6)	−0.0001 (6)	−0.0007 (6)	−0.0040 (6)
N1	0.0177 (7)	0.0109 (7)	0.0161 (7)	−0.0006 (6)	0.0012 (6)	−0.0003 (6)
C1	0.0189 (8)	0.0149 (9)	0.0129 (8)	0.0002 (7)	0.0002 (7)	0.0020 (7)
C2	0.0201 (9)	0.0156 (9)	0.0148 (8)	−0.0007 (7)	−0.0012 (7)	0.0009 (7)
C3	0.0192 (9)	0.0142 (9)	0.0145 (8)	−0.0009 (7)	0.0020 (7)	−0.0020 (7)
C4	0.0260 (10)	0.0209 (10)	0.0111 (8)	0.0015 (8)	−0.0011 (7)	0.0013 (7)
C5	0.0256 (10)	0.0168 (9)	0.0139 (8)	0.0010 (7)	0.0006 (7)	0.0047 (7)
C6	0.0189 (8)	0.0154 (9)	0.0126 (7)	−0.0004 (7)	0.0004 (6)	0.0010 (7)
C7	0.0215 (9)	0.0132 (9)	0.0158 (8)	0.0007 (7)	0.0009 (7)	0.0040 (7)
C8	0.0192 (9)	0.0151 (9)	0.0188 (9)	0.0006 (7)	0.0011 (7)	0.0016 (7)
C9	0.0224 (9)	0.0173 (9)	0.0207 (9)	0.0005 (8)	0.0007 (7)	0.0022 (8)
C10	0.0293 (11)	0.0153 (9)	0.0252 (10)	0.0014 (8)	0.0055 (8)	0.0039 (8)
O1W	0.0312 (8)	0.0175 (7)	0.0232 (7)	−0.0055 (6)	0.0050 (6)	0.0009 (6)

Ni1—O1	1.8436 (12)	C4—C5	1.369 (3)
Ni1—O1i	1.8436 (12)	C4—H4A	0.9300
Ni1—N1i	1.8474 (15)	C5—C6	1.417 (3)
Ni1—N1	1.8474 (15)	C5—H5A	0.9300
O1—C1	1.324 (2)	C6—C7	1.414 (2)
O2—C3	1.359 (2)	C7—H7A	0.9300
O2—H1O2	0.74 (3)	C8—C8i	1.392 (4)
N1—C7	1.317 (2)	C8—C9	1.394 (2)
N1—C8	1.422 (2)	C9—C10	1.382 (3)
C1—C2	1.399 (2)	C9—H9A	0.9300
C1—C6	1.416 (2)	C10—C10i	1.387 (4)
C2—C3	1.383 (2)	C10—H10A	0.9300
C2—H2A	0.9300	O1W—H1W1	0.8771
C3—C4	1.404 (3)	O1W—H2W1	0.8309
Cg1···Cg4ii	3.7364 (11)	Cg4···Cg4v	3.7750 (11)
Cg2···Cg2ii	3.7380 (9)	Ni1···O1Wi	3.7635 (13)
Cg2···Cg3iii	3.7381 (9)	O1···O1i	2.4319 (18)
Cg3···Cg4iv	3.5766 (10)	N1···N1i	2.525 (2)
O1—Ni1—O1i	82.53 (8)	C5—C4—H4A	120.5
O1—Ni1—N1i	174.29 (5)	C3—C4—H4A	120.5
O1i—Ni1—N1i	95.89 (7)	C4—C5—C6	121.82 (17)
O1—Ni1—N1	95.89 (7)	C4—C5—H5A	119.1
O1i—Ni1—N1	174.29 (6)	C6—C5—H5A	119.1
N1i—Ni1—N1	86.21 (9)	C7—C6—C1	123.15 (17)
C1—O1—Ni1	127.44 (11)	C7—C6—C5	118.38 (16)
C3—O2—H1O2	111 (2)	C1—C6—C5	118.47 (16)
C7—N1—C8	121.12 (15)	N1—C7—C6	124.97 (17)
C7—N1—Ni1	125.63 (13)	N1—C7—H7A	117.5
C8—N1—Ni1	113.24 (12)	C6—C7—H7A	117.5
O1—C1—C2	118.13 (16)	C8i—C8—C9	119.92 (11)
O1—C1—C6	122.74 (16)	C8i—C8—N1	113.20 (9)
C2—C1—C6	119.12 (17)	C9—C8—N1	126.87 (17)
C3—C2—C1	120.89 (17)	C10—C9—C8	119.37 (18)
C3—C2—H2A	119.6	C10—C9—H9A	120.3
C1—C2—H2A	119.6	C8—C9—H9A	120.3
O2—C3—C2	122.42 (17)	C9—C10—C10i	120.43 (11)
O2—C3—C4	117.00 (16)	C9—C10—H10A	119.8
C2—C3—C4	120.59 (17)	C10i—C10—H10A	119.8
C5—C4—C3	119.06 (17)	H1W1—O1W—H2W1	114.3
O1i—Ni1—O1—C1	−176.47 (18)	O1—C1—C6—C5	178.70 (17)
N1i—Ni1—N1—C7	−176.59 (19)	C2—C1—C6—C5	−1.7 (3)
O1—Ni1—N1—C8	177.60 (12)	C4—C5—C6—C7	−177.71 (18)
N1i—Ni1—N1—C8	2.93 (9)	C4—C5—C6—C1	2.4 (3)
Ni1—O1—C1—C2	−176.01 (12)	C8—N1—C7—C6	−175.09 (17)
Ni1—O1—C1—C6	3.6 (3)	Ni1—N1—C7—C6	4.4 (3)
O1—C1—C2—C3	179.49 (17)	C1—C6—C7—N1	−3.0 (3)
C6—C1—C2—C3	−0.1 (3)	C5—C6—C7—N1	177.10 (18)
C1—C2—C3—O2	−178.73 (16)	C7—N1—C8—C8i	171.2 (2)
C1—C2—C3—C4	1.4 (3)	Ni1—N1—C8—C8i	−8.3 (3)
O2—C3—C4—C5	179.35 (17)	C7—N1—C8—C9	−7.6 (3)
C2—C3—C4—C5	−0.8 (3)	Ni1—N1—C8—C9	172.86 (16)
C3—C4—C5—C6	−1.1 (3)	C8i—C8—C9—C10	−5.1 (3)
O1—C1—C6—C7	−1.2 (3)	N1—C8—C9—C10	173.65 (18)
C2—C1—C6—C7	178.37 (17)	C8—C9—C10—C10i	−1.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1	0.88	2.40	3.0733 (18)	133
O1W—H1W1···O1i	0.88	1.97	2.8072 (19)	160
O1W—H2W1···O2vi	0.83	2.17	2.9985 (19)	173
C9—H9A···O2vii	0.93	2.60	3.394 (2)	144

Table 1

Selected interatomic distances (Å)

Cg1, Cg2, Cg3, and Cg4 are the centroids of the Ni1/N1/C8/C8A/N1A, Ni1/O1/C1/C6/C7/N1, Ni1/O1A/C1A/C6A/C7A/N1A and C1–C6 rings, respectively.

Cg1⋯Cg4i	3.7364 (11)
Cg2⋯Cg2i	3.7380 (9)
Cg2⋯Cg3ii	3.7381 (9)
Cg3⋯Cg4iii	3.5766 (10)
Cg4⋯Cg4iv	3.7750 (11)
Ni1⋯O1Wv	3.7635 (13)
O1⋯O1v	2.4319 (18)
N1⋯N1v	2.525 (2)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1	0.88	2.40	3.0733 (18)	133
O1W—H1W1⋯O1v	0.88	1.97	2.8072 (19)	160
O1W—H2W1⋯O2vi	0.83	2.17	2.9985 (19)	173
C9—H9A⋯O2vii	0.93	2.60	3.394 (2)	144

Symmetry codes: (v) ; (vi) ; (vii) .