Diaquabis-[3-(hydroxy-imino)-butanoato]nickel(II).

In the neutral, mononuclear title complex, [Ni(C(4)H(6)NO(3))(2)(H(2)O)(2)], the Ni atom lies on a crystallographic inversion centre within a distorted octa-hedral N(2)O(4) environment. Two trans-disposed anions of 3-hydroxy-imino-butanoic acid occupy four equatorial sites, coordinated by the deprotonated carboxyl-ate and protonated oxime groups and forming six-membered chelate rings, while the two axial positions are occupied by the water O atoms. The O atom of the oxime group forms an intra-molecular hydrogen bond with the coordinated carboxyl-ate O atom. The complex mol-ecules are linked into chains along b by hydrogen bonds between the water O atom and the carboxyl-ate O of a neighbouring mol-ecule. The chains are linked by further hydrogen bonds into a layer structure.

Related literature

For the coordination chemistry of 2-hydroxy­imino­propanoic acid and its amide derivatives, see: Onindo et al. (1995 ▶); Duda et al. (1997 ▶); Moroz et al. (2008 ▶). For 2-hydroxy­imino­carboxylic acids as efficient metal chelators, see: Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶); Gumienna-Kontecka et al. (2000 ▶). For the use of 2-hydroxy­imino­carboxylic acid derivatives as efficient ligands for the stabilization of high oxidation states of transitional metals, see: Fritsky et al. (1998 ▶, 2006 ▶). For the structures of hydroxy­imino­carboxylic acid derivatives, see: Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶); Mokhir et al. (2002 ▶). For structures with monodentately coordinated carboxylic groups, see: Wörl et al. (2005a ▶,b ▶). For the synthesis, see: Khromov (1950 ▶).

Experimental

Crystal data

[Ni(C4H6NO3)2(H2O)2]

M = 326.94

Monoclinic,

a = 9.6071 (9) Å

b = 7.1721 (7) Å

c = 9.6805 (9) Å

β = 107.557 (5)°

V = 635.94 (10) Å3

Z = 2

Mo Kα radiation

μ = 1.56 mm−1

T = 120 K

0.23 × 0.15 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS, Sheldrick, 2001 ▶) T min = 0.622, T max = 0.796

4576 measured reflections

1626 independent reflections

1286 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.060

S = 1.05

1626 reflections

101 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.32 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004605/jh2130sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004605/jh2130Isup2.hkl

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

[Ni(C4H6NO3)2(H2O)2]	F(000) = 340
Mr = 326.94	Dx = 1.707 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3254 reflections
a = 9.6071 (9) Å	θ = 3.6–27.5°
b = 7.1721 (7) Å	µ = 1.56 mm−1
c = 9.6805 (9) Å	T = 120 K
β = 107.557 (5)°	Block, lilac
V = 635.94 (10) Å3	0.23 × 0.15 × 0.11 mm
Z = 2

Nonius KappaCCD diffractometer	1626 independent reflections
Radiation source: fine-focus sealed tube	1286 reflections with I > 2σ(I)
horizontally mounted graphite crystal	Rint = 0.032
Detector resolution: 9 pixels mm-1	θmax = 36.4°, θmin = 3.6°
φ scans and ω scans with κ offset	h = −16→16
Absorption correction: multi-scan (SADABS, Sheldrick, 2001)	k = −11→11
Tmin = 0.622, Tmax = 0.796	l = −16→16
4576 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0307P)2] where P = (Fo2 + 2Fc2)/3
1626 reflections	(Δ/σ)max < 0.001
101 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.32 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 > 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	0.0000	0.0000	0.00914 (9)
O1	−0.07925 (12)	0.23226 (15)	−0.10969 (11)	0.0129 (2)
O2	−0.16372 (12)	0.51946 (16)	−0.14813 (12)	0.0144 (3)
O3	0.00013 (14)	−0.01018 (19)	0.30386 (13)	0.0163 (3)
O4	−0.20766 (13)	−0.12137 (18)	−0.07790 (13)	0.0129 (3)
N1	−0.05011 (15)	0.09879 (19)	0.17719 (13)	0.0114 (3)
C1	−0.13309 (17)	0.3773 (2)	−0.07010 (16)	0.0110 (3)
C2	−0.1685 (2)	0.3862 (2)	0.07312 (17)	0.0150 (3)
H2A	−0.1448	0.5116	0.1102	0.018*
H2B	−0.2736	0.3737	0.0495	0.018*
C3	−0.10320 (18)	0.2559 (2)	0.19819 (17)	0.0122 (3)
C4	−0.1086 (2)	0.3230 (3)	0.34280 (18)	0.0226 (4)
H4A	−0.0824	0.2229	0.4116	0.034*
H4B	−0.2056	0.3649	0.3350	0.034*
H4C	−0.0412	0.4243	0.3746	0.034*
H1O3	0.038 (3)	−0.085 (3)	0.281 (2)	0.026 (7)*
H1O4	−0.253 (3)	−0.063 (3)	−0.158 (3)	0.036 (6)*
H2O4	−0.201 (2)	−0.227 (3)	−0.099 (2)	0.028 (6)*

	U11	U22	U33	U12	U13	U23
Ni1	0.01179 (16)	0.00714 (14)	0.00827 (13)	0.00080 (13)	0.00266 (10)	−0.00010 (12)
O1	0.0177 (7)	0.0086 (6)	0.0119 (5)	0.0016 (5)	0.0037 (5)	0.0000 (4)
O2	0.0171 (6)	0.0095 (6)	0.0139 (5)	0.0014 (5)	0.0004 (5)	0.0008 (4)
O3	0.0226 (7)	0.0163 (6)	0.0109 (5)	0.0079 (6)	0.0066 (5)	0.0046 (5)
O4	0.0156 (7)	0.0096 (6)	0.0126 (6)	0.0009 (5)	0.0029 (5)	−0.0003 (5)
N1	0.0119 (7)	0.0131 (7)	0.0085 (6)	0.0000 (6)	0.0021 (5)	0.0022 (5)
C1	0.0082 (8)	0.0095 (8)	0.0120 (7)	−0.0021 (6)	−0.0021 (6)	−0.0014 (6)
C2	0.0173 (9)	0.0119 (8)	0.0167 (8)	0.0029 (7)	0.0064 (7)	−0.0011 (6)
C3	0.0104 (8)	0.0138 (8)	0.0130 (7)	−0.0012 (7)	0.0042 (6)	−0.0016 (6)
C4	0.0324 (12)	0.0199 (10)	0.0177 (9)	0.0072 (8)	0.0110 (8)	−0.0031 (7)

Ni1—O1i	1.9986 (10)	O4—H2O4	0.79 (2)
Ni1—O1	1.9986 (10)	N1—C3	1.278 (2)
Ni1—N1	2.0431 (13)	C1—C2	1.525 (2)
Ni1—N1i	2.0431 (13)	C2—C3	1.508 (2)
Ni1—O4i	2.0973 (12)	C2—H2A	0.9700
Ni1—O4	2.0973 (12)	C2—H2B	0.9700
O1—C1	1.2714 (18)	C3—C4	1.496 (2)
O2—C1	1.2499 (19)	C4—H4A	0.9600
O3—N1	1.4108 (17)	C4—H4B	0.9600
O3—H1O3	0.72 (2)	C4—H4C	0.9600
O4—H1O4	0.87 (3)
O1i—Ni1—O1	180.00 (7)	C3—N1—Ni1	130.22 (11)
O1i—Ni1—N1	89.51 (5)	O3—N1—Ni1	115.60 (10)
O1—Ni1—N1	90.49 (5)	O2—C1—O1	121.88 (14)
O1i—Ni1—N1i	90.49 (5)	O2—C1—C2	116.05 (14)
O1—Ni1—N1i	89.51 (5)	O1—C1—C2	122.04 (14)
N1—Ni1—N1i	180.00 (7)	C3—C2—C1	123.47 (14)
O1i—Ni1—O4i	89.21 (5)	C3—C2—H2A	106.5
O1—Ni1—O4i	90.79 (5)	C1—C2—H2A	106.5
N1—Ni1—O4i	89.63 (5)	C3—C2—H2B	106.5
N1i—Ni1—O4i	90.37 (5)	C1—C2—H2B	106.5
O1i—Ni1—O4	90.79 (5)	H2A—C2—H2B	106.5
O1—Ni1—O4	89.21 (5)	N1—C3—C4	124.10 (15)
N1—Ni1—O4	90.37 (5)	N1—C3—C2	120.51 (14)
N1i—Ni1—O4	89.63 (5)	C4—C3—C2	115.38 (14)
O4i—Ni1—O4	180.00 (4)	C3—C4—H4A	109.5
C1—O1—Ni1	130.26 (10)	C3—C4—H4B	109.5
N1—O3—H1O3	102.5 (18)	H4A—C4—H4B	109.5
Ni1—O4—H1O4	106.8 (16)	C3—C4—H4C	109.5
Ni1—O4—H2O4	110.0 (15)	H4A—C4—H4C	109.5
H1O4—O4—H2O4	107 (2)	H4B—C4—H4C	109.5
C3—N1—O3	113.48 (13)
N1i—Ni1—O1—C1	−178.29 (14)	Ni1—O1—C1—O2	172.23 (11)
O4i—Ni1—O1—C1	−87.93 (13)	Ni1—O1—C1—C2	−9.7 (2)
O4—Ni1—O1—C1	92.07 (13)	O2—C1—C2—C3	−162.17 (15)
O1i—Ni1—N1—C3	176.44 (15)	O1—C1—C2—C3	19.6 (2)
O1—Ni1—N1—C3	−3.56 (15)	O3—N1—C3—C4	1.8 (2)
O4i—Ni1—N1—C3	87.23 (15)	Ni1—N1—C3—C4	−168.07 (13)
O4—Ni1—N1—C3	−92.77 (15)	O3—N1—C3—C2	−177.11 (14)
O1i—Ni1—N1—O3	6.79 (10)	Ni1—N1—C3—C2	13.1 (2)
O1—Ni1—N1—O3	−173.21 (10)	C1—C2—C3—N1	−21.1 (2)
O4i—Ni1—N1—O3	−82.43 (10)	C1—C2—C3—C4	159.90 (16)
O4—Ni1—N1—O3	97.57 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2O4···O2ii	0.79 (2)	1.94 (2)	2.7293 (17)	175 (2)
O3—H1O3···O1i	0.72 (2)	2.10 (2)	2.7404 (17)	148 (2)
O4—H1O4···O2iii	0.87 (3)	1.90 (3)	2.7576 (16)	167 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H2O4⋯O2i	0.79 (2)	1.94 (2)	2.7293 (17)	175 (2)
O3—H1O3⋯O1ii	0.72 (2)	2.10 (2)	2.7404 (17)	148 (2)
O4—H1O4⋯O2iii	0.87 (3)	1.90 (3)	2.7576 (16)	167 (2)

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