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The title compound, (C2H10N2)2[Ni(C2HN2O4)2]·2H2O, has an ionic structure containing a centrosymmetric complex 4- anion, charge-balancing ethyl­ene­diaminium dications and solvent water mol­ecules. The oxalohydroxamate unit is triply deprotonated and forms five-membered chelate rings with the central Ni ion; the Ni ion lies on an inversion centre. The two hydroxamate O atoms in the complex anion are linked by short intra­molecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106036201/ga3019sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106036201/ga3019Isup2.hkl
Contains datablock I

CCDC reference: 625683

Comment top

Many mononuclear complexes of transition metals containing additional vacant donor sets and chelate centers are taken as ligands for building of homo- and heteropolynuclear systems which are widely used in bioinorganic modeling, electron transfer and molecular magnetism (Kokozay & Vassilyeva, 2002; Powell et al., 1995; Goodwin et al., 2000; Kahn, 1993). Polydentate ligands containing hydroxamic groups attract particular attention owing to their potential for the bridging mode of coordination and mediation of very strong magnetic exchange interactions between metal ions analogously to bridging oxime-containing complexes (Colacio et al., 1994). Oxalodihydroxamic acid (oxha) is an efficient chelating ligand for CuII and NiII ions (Świątek-Kozłowska et al., 2000). Several possible coordination modes of oxha have been realised in metal complexes, as summarized by Świątek-Kozłowska et al. (2000) and Huang et al. (1991). To date, only complexes containing the doubly deprotonated ligand have been isolated, and one of them, K2[Ni(oxha-2H)2]·2H2O, (II), has been structurally characterized (Świątek-Kozłowska et al., 2000).

The title compound, (I), has an ionic structure containing 4- charged NiII-centered complex anions, 2+ charged ethylenediaminium cations and solvent water molecules (Fig. 1). The NiII complex anion is centrosymmetric with a distorted square-planar coordination geometry formed by four N atoms belonging to the deprotonated hydroxamic groups. Thus the coordinated residues of oxha are triply deprotonated (two N and one O hydroxamic atoms), resulting in non-equivalence of two hydroxamic functions.

The Ni—N bond lengths (Table 1) are typical for square-planar NiII complexes with deprotonated amide ligands (Leininger et al., 2000; Hlavica & Lewis, 2001). The bite angles around the central atom deviate from an ideal square-planar configuration [e.g. N1—Ni1—N2 = 82.17 (8)°], which is a consequence of the formation of five-membered chelate rings. The latter ring is puckered, with a deviation of the Ni atom from the plane defined by the other four atoms of 0.0376 (1) Å. The C—O, N—O and C—N bond lengths in the coordinated hydroxamate group suggest its existence in the hydroxamic form rather than in the oximic form (Brown et al., 1982).

The structure of the complex anion of (I) is similar in its geometrical parameters to that of complex (II) (Świątek-Kozłowska et al., 2000). The principal differences between these compounds are in the charge of the complex anions (4- and 2-, respectively) and in the parameters of the short intramolecular hydrogen bonds between the hydroxamate O atoms. The O3···O4 separations (Table 2) in (I) are significantly shorter than those in (II) [2.64 (3) Å] and close to those observed in typical cis-bis(oximate) complexes (Dobosz et al., 1998, 1999).

In the crystal packing the ethylenediaminium cations are connected with the complex anions through ordinary and bifurcated hydrogen bonds, where NH3+ groups act as donors, and the amide O, hydroxamic O, water O and hydroxamic N atoms act as acceptors. In addition, the complex anions are connected to each other by hydrogen bonds to the water molecules (Table 2). An extensive three-dimensional system of hydrogen bonds results, as shown in Fig. 2.

Experimental top

Ni(NO3)2·6H2O (0.291 g, 1 mmol) was dissolved in water (15 ml) and added to an aqueous solution (15 ml) of oxha (0.240 g, 2 mmol); ethylenediamine (0.342 ml) in water (15 ml) was added to the resulting blue suspension. The mixture was stirred for 30 min at ambient temperature. The resulting clear solution was left at room temperature for crystallization in air. Bright-red crystals were separated by filtration after 72 h, washed with cold water (10 ml) and dried.

Refinement top

All H atoms were observed in a difference Fourier map, but the methylene and NH H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.97 Å (C—H) and 0.89 Å (N—H), and Uiso(H) values at 1.2Ueq(C) and 1.5Ueq (N). The H atoms of the water molecule were located in the difference Fourier map and their coordinates were allowed to ride on the coordinates of the parent atom with Uiso(H) = 1.5Ueq(O) Please check this. For the H atom on O3 (H1), both the coordinates and the isotropic displacement parameter were refined without constraints.

Computing details top

Data collection: KM-4-CCD Software (Kuma, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of compound (1), with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are indicated by dashed lines. Atoms labelled with the suffix A are related to their counterparts by symmetry operation (2 − x, 1 − y, 1 − z).
[Figure 2] Fig. 2. A packing diagram for complex (1) (projection along z direction). Hydrogen bonds are indicated by dashed lines. Representative atom labels are shown (see Table 2).
Bis(ethylenediaminium) bis[N,N-dihydroxyoxamidato(3-)]nickelate(II) dihydrate top
Crystal data top
(C2H10N2)2[Ni(C2HN2O4)2]·2H2OF(000) = 476
Mr = 453.06Dx = 1.694 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6046 reflections
a = 5.961 (1) Åθ = 3.3–28.4°
b = 17.604 (4) ŵ = 1.16 mm1
c = 8.917 (2) ÅT = 100 K
β = 108.38 (3)°Needle, red
V = 888.0 (4) Å30.25 × 0.15 × 0.1 mm
Z = 2
Data collection top
Kuma KM-4 CCD area-detector
diffractometer
2052 independent reflections
Radiation source: fine-focus sealed tube1936 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ω scansθmax = 28.4°, θmin = 3.3°
Absorption correction: ψ scan
(North et al., 1968)
h = 77
Tmin = 0.74, Tmax = 0.89k = 2323
6046 measured reflectionsl = 611
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0393P)2 + 1.6718P]
where P = (Fo2 + 2Fc2)/3
2052 reflections(Δ/σ)max = 0.001
130 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.85 e Å3
Crystal data top
(C2H10N2)2[Ni(C2HN2O4)2]·2H2OV = 888.0 (4) Å3
Mr = 453.06Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.961 (1) ŵ = 1.16 mm1
b = 17.604 (4) ÅT = 100 K
c = 8.917 (2) Å0.25 × 0.15 × 0.1 mm
β = 108.38 (3)°
Data collection top
Kuma KM-4 CCD area-detector
diffractometer
2052 independent reflections
Absorption correction: ψ scan
(North et al., 1968)
1936 reflections with I > 2σ(I)
Tmin = 0.74, Tmax = 0.89Rint = 0.045
6046 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.50 e Å3
2052 reflectionsΔρmin = 0.85 e Å3
130 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni11.00000.50000.50000.00909 (13)
O10.5743 (3)0.66992 (9)0.52158 (18)0.0150 (3)
O20.5363 (3)0.63697 (8)0.20336 (17)0.0104 (3)
O30.8540 (3)0.57552 (9)0.74518 (16)0.0125 (3)
O40.8194 (3)0.52092 (9)0.15972 (16)0.0100 (3)
O1W0.5477 (3)0.85948 (9)0.58242 (19)0.0143 (3)
N10.8244 (3)0.56559 (10)0.58313 (19)0.0109 (3)
N20.8128 (3)0.54253 (10)0.30957 (19)0.0089 (3)
N30.0115 (3)0.90182 (10)0.3903 (2)0.0100 (3)
H130.11820.93900.36740.015*
H140.10460.91310.35130.015*
H150.04730.89660.49470.015*
N40.2588 (3)0.77022 (10)0.3308 (2)0.0097 (3)
H230.34410.80860.38470.015*
H240.22160.77940.22770.015*
H250.34240.72750.35410.015*
C10.6844 (4)0.61442 (12)0.4874 (2)0.0101 (4)
C20.6702 (4)0.59797 (11)0.3170 (2)0.0089 (4)
C30.0384 (4)0.76213 (12)0.3742 (3)0.0132 (4)
H3A0.07930.75730.48810.016*
H3B0.04330.71620.32690.016*
C40.1255 (4)0.82964 (12)0.3195 (3)0.0125 (4)
H4A0.17150.83330.20530.015*
H4B0.26750.82180.34850.015*
H10.953 (5)0.5378 (14)0.782 (3)0.042 (10)*
H1W0.67520.86330.61300.021*
H2W0.48690.89700.60940.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0102 (2)0.0109 (2)0.00642 (19)0.00218 (13)0.00295 (14)0.00013 (12)
O10.0187 (8)0.0156 (8)0.0101 (7)0.0091 (6)0.0037 (6)0.0002 (6)
O20.0092 (7)0.0120 (7)0.0090 (7)0.0027 (5)0.0012 (5)0.0016 (5)
O30.0157 (8)0.0177 (8)0.0043 (6)0.0070 (6)0.0037 (6)0.0001 (5)
O40.0125 (7)0.0129 (7)0.0055 (6)0.0008 (5)0.0043 (5)0.0024 (5)
O1W0.0096 (7)0.0172 (8)0.0153 (7)0.0003 (6)0.0027 (6)0.0051 (6)
N10.0149 (9)0.0138 (8)0.0045 (7)0.0034 (7)0.0034 (6)0.0015 (6)
N20.0110 (8)0.0114 (8)0.0045 (7)0.0010 (6)0.0026 (6)0.0016 (6)
N30.0098 (8)0.0123 (8)0.0080 (7)0.0013 (6)0.0029 (6)0.0005 (6)
N40.0091 (8)0.0097 (8)0.0102 (8)0.0003 (6)0.0028 (6)0.0004 (6)
C10.0113 (10)0.0103 (9)0.0086 (9)0.0011 (7)0.0030 (7)0.0008 (7)
C20.0090 (9)0.0096 (9)0.0079 (9)0.0014 (7)0.0022 (7)0.0001 (7)
C30.0146 (10)0.0125 (10)0.0156 (10)0.0026 (8)0.0090 (8)0.0001 (8)
C40.0081 (10)0.0158 (10)0.0135 (9)0.0018 (7)0.0034 (8)0.0042 (8)
Geometric parameters (Å, º) top
Ni1—N1i1.8621 (17)N3—C41.485 (3)
Ni1—N11.8621 (17)N3—H130.8900
Ni1—N2i1.8694 (18)N3—H140.8900
Ni1—N21.8694 (18)N3—H150.8900
O1—C11.267 (3)N4—C31.489 (3)
O2—C21.275 (2)N4—H230.8900
O3—N11.410 (2)N4—H240.8900
O3—O4i2.520 (2)N4—H250.8900
O3—H10.88 (3)C1—C21.523 (3)
O4—N21.402 (2)C3—C41.518 (3)
O1W—H1W0.7252C3—H3A0.9700
O1W—H2W0.8249C3—H3B0.9700
N1—C11.309 (3)C4—H4A0.9700
N2—C21.309 (3)C4—H4B0.9700
N1i—Ni1—N1180.00 (9)H23—N4—H24109.5
N1i—Ni1—N2i82.17 (8)C3—N4—H25109.5
N1—Ni1—N2i97.83 (8)H23—N4—H25109.5
N1i—Ni1—N297.83 (8)H24—N4—H25109.5
N1—Ni1—N282.17 (8)O1—C1—N1128.43 (19)
N2i—Ni1—N2180.0O1—C1—C2121.11 (18)
N1—O3—O4i95.45 (11)N1—C1—C2110.44 (17)
N1—O3—H198.3 (16)O2—C2—N2127.96 (18)
H1W—O1W—H2W108.7O2—C2—C1120.97 (18)
C1—N1—O3115.76 (16)N2—C2—C1111.05 (17)
C1—N1—Ni1118.05 (14)N4—C3—C4111.89 (17)
O3—N1—Ni1125.48 (13)N4—C3—H3A109.2
C2—N2—O4117.66 (16)C4—C3—H3A109.2
C2—N2—Ni1117.63 (13)N4—C3—H3B109.2
O4—N2—Ni1124.68 (13)C4—C3—H3B109.2
C4—N3—H13109.5H3A—C3—H3B107.9
C4—N3—H14109.5N3—C4—C3111.81 (17)
H13—N3—H14109.5N3—C4—H4A109.3
C4—N3—H15109.5C3—C4—H4A109.3
H13—N3—H15109.5N3—C4—H4B109.3
H14—N3—H15109.5C3—C4—H4B109.3
C3—N4—H23109.5H4A—C4—H4B107.9
C3—N4—H24109.5
O4i—O3—N1—C1171.30 (16)O3—N1—C1—C2179.35 (16)
O4i—O3—N1—Ni11.22 (17)Ni1—N1—C1—C28.5 (2)
N2i—Ni1—N1—C1172.19 (16)O4—N2—C2—O21.5 (3)
N2—Ni1—N1—C17.81 (16)Ni1—N2—C2—O2176.57 (17)
N2i—Ni1—N1—O32.32 (18)O4—N2—C2—C1179.92 (16)
N2—Ni1—N1—O3177.68 (18)Ni1—N2—C2—C11.8 (2)
N1i—Ni1—N2—C2174.95 (16)O1—C1—C2—O24.1 (3)
N1—Ni1—N2—C25.05 (16)N1—C1—C2—O2177.31 (19)
N1i—Ni1—N2—O42.97 (17)O1—C1—C2—N2174.44 (19)
N1—Ni1—N2—O4177.03 (17)N1—C1—C2—N24.1 (3)
O3—N1—C1—O10.9 (3)N4—C3—C4—N359.9 (2)
Ni1—N1—C1—O1169.95 (19)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H13···O4ii0.891.842.729 (2)174
N3—H14···O3iii0.892.012.891 (2)172
N3—H15···O2iv0.891.972.799 (2)154
N4—H24···O1iii0.891.982.831 (2)159
N4—H23···O1W0.892.012.834 (2)154
N4—H25···O10.891.972.744 (2)145
O1W—H1W···O2v0.732.052.769 (2)175
O1W—H2W···O4iv0.821.892.712 (2)175
O3—H1···O4i0.88 (3)1.65 (3)2.520 (2)167 (3)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x1/2, y+3/2, z+1/2; (v) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula(C2H10N2)2[Ni(C2HN2O4)2]·2H2O
Mr453.06
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)5.961 (1), 17.604 (4), 8.917 (2)
β (°) 108.38 (3)
V3)888.0 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.16
Crystal size (mm)0.25 × 0.15 × 0.1
Data collection
DiffractometerKuma KM-4 CCD area-detector
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.74, 0.89
No. of measured, independent and
observed [I > 2σ(I)] reflections
6046, 2052, 1936
Rint0.045
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.095, 1.08
No. of reflections2052
No. of parameters130
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.50, 0.85

Computer programs: KM-4-CCD Software (Kuma, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Ni1—N11.8621 (17)O3—N11.410 (2)
Ni1—N21.8694 (18)O3—O4i2.520 (2)
O1—C11.267 (3)O4—N21.402 (2)
O2—C21.275 (2)N1—C11.309 (3)
N1—Ni1—N2i97.83 (8)N1—Ni1—N282.17 (8)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H13···O4ii0.891.842.729 (2)174
N3—H14···O3iii0.892.012.891 (2)172
N3—H15···O2iv0.891.972.799 (2)154
N4—H24···O1iii0.891.982.831 (2)159
N4—H23···O1W0.892.012.834 (2)154
N4—H25···O10.891.972.744 (2)145
O1W—H1W···O2v0.732.052.769 (2)175
O1W—H2W···O4iv0.821.892.712 (2)175
O3—H1···O4i0.88 (3)1.65 (3)2.520 (2)167 (3)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2; (iii) x1/2, y+3/2, z1/2; (iv) x1/2, y+3/2, z+1/2; (v) x+1/2, y+3/2, z+1/2.
 

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