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Acta Cryst. (2007). E63, m2575    [ doi:10.1107/S1600536807044893 ]

[[mu]-4,7-Dioxa-1,10-diazaoctane-1,1,10,10-tetraacetat0-1[kappa]4O1,O1',N1,O4:2[kappa]4O7,N10,O10,O10']bis[aquanickel(II)] dihydrate

H.-Q. Liu

Abstract top

The Ni atom in the title complex, [Ni2(C14H20N2O10)(H2O)2]·2H2O or {[Ni2(egta)·2H2O]·2H2O}] [egtaH4 is 3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedioic acid], has a square-pyramidal coordination geometry. Both NiII centres are pentacoordinated by one N atom and three O atoms of egta, forming the basal plane, and one O donor water molecule in the apical position. The dinuclear complex is arranged around an inversion centre. The solvent water molecules and coordinated water molecules are involved in hydrogen bonds with uncoordinated O atoms of carboxylate groups, which link the complex molecules to form a three-dimensional supramolecular network structure.

Comment top

The coordination of multipyridine and multi-carboxylate ligands to metal centers has proved to be an excellent tool in the assembly process and has been highly influenced by the structural characterizations of tectonic spacers. Polydentate amino-polycarboxylate acid [H4egta=3,12-bis (carboxymethyl)-6, 9-dioxa-3, 12-diazatetradecanedioic acid], being extensively used as a calcium buffer in biological research, possesses symmetrical four potential coordinating sites and renders it an appropriate candidate to improve the extension of the ferrimagnetic lattice from one dimensional (one-dimensional) systems to two-dimensional and three-dimensional networks (Bomas-Almenar et al., 1993). In this paper, we report the synthesis and crystal structure of the title complex,(I).

As illustrated in Fig. 1, the neutral dinuclear molecule, lies on a centre of symmetry. Both nickel(II) centers are pentacoordinated to one N atom and three O atoms of egta, forming the basal plane, and one O donors of water molecule being in axial position, then leading to a distorted square-pyramid environment. The structural components are connected through O—H···O hydrogen bonding involving the lattice water molecules as donors and the uncoordinated O atoms as acceptors thus forming a three dimensionnal supramolecular network structure (Table 1).

Related literature top

For related literature, see: Bomas-Almenar et al. (1993).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of nickel chloride (1 mmol) to a hot methanol solution (10 ml) of egtaH4 (1 mmol). The resulting solution was filtered, and pale green blocky crystals were obtained on slow evaporation of the solvent over several days at room temperature.

Refinement top

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H= 97Å and with Uiso(H) = 1.2Ueq(C). H atoms attached to water molecules were found in a difference map and their positions were refined using restraints (O—H= 0.84 (2)Å and H···H= 1.38 Å) with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Ref??).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Free water molecule has been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 1 − z].
[µ-4,7-dioxa-1,10-diazaoctane-1,1,10,10-tetraacetato- 1κ4O1,O1',N1,O4:2κ4O7,N10,O10,O10'] bis[aquanickel(II)] dihydrate top
Crystal data top
[Ni2(C14H20N2O10)(H2O)2]·2H2OF000 = 1176
Mr = 565.80Dx = 1.748 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2007 reflections
a = 21.031 (2) Åθ = 2.9–25.5º
b = 7.5299 (9) ŵ = 1.83 mm−1
c = 13.5789 (16) ÅT = 298 (2) K
β = 90.4640 (10)ºBlock, green
V = 2150.3 (4) Å30.34 × 0.12 × 0.04 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2007 independent reflections
Radiation source: fine-focus sealed tube1756 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 298(2) Kθmax = 25.5º
φ and ω scansθmin = 2.9º
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		h = −25→25
Tmin = 0.580, Tmax = 0.931k = −9→9
7928 measured reflectionsl = −16→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.060  w = 1/[σ2(Fo2) + (0.0294P)2 + 0.9421P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.002
2007 reflectionsΔρmax = 0.34 e Å−3
157 parametersΔρmin = −0.19 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni2(C14H20N2O10)(H2O)2]·2H2OV = 2150.3 (4) Å3
Mr = 565.80Z = 4
Monoclinic, C2/cMo Kα
a = 21.031 (2) ŵ = 1.83 mm−1
b = 7.5299 (9) ÅT = 298 (2) K
c = 13.5789 (16) Å0.34 × 0.12 × 0.04 mm
β = 90.4640 (10)º
Data collection top
Bruker APEXII area-detector
diffractometer		2007 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		1756 reflections with I > 2σ(I)
Tmin = 0.580, Tmax = 0.931Rint = 0.027
7928 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0246 restraints
wR(F2) = 0.060H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.34 e Å−3
2007 reflectionsΔρmin = −0.19 e Å−3
157 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
Ni10.628725 (12)0.21993 (3)0.564464 (18)0.02584 (10)
O10.67589 (7)0.37797 (18)0.47843 (11)0.0328 (3)
O20.74168 (7)0.3724 (2)0.35187 (12)0.0412 (4)
O30.60468 (7)0.02307 (18)0.64666 (10)0.0352 (4)
O40.62324 (9)−0.2649 (2)0.66266 (12)0.0497 (5)
O50.53305 (7)0.28393 (19)0.47083 (11)0.0336 (4)
O60.61807 (8)0.3871 (2)0.67071 (12)0.0383 (4)
H1W0.6396 (12)0.354 (3)0.7181 (16)0.057*
H2W0.6247 (12)0.492 (2)0.6580 (18)0.057*
O70.70120 (9)0.2874 (2)0.80982 (13)0.0453 (4)
H3W0.7178 (12)0.385 (3)0.828 (2)0.068*
H4W0.7255 (12)0.239 (3)0.7706 (19)0.068*
N10.63903 (8)0.0375 (2)0.45889 (11)0.0250 (4)
C10.70315 (10)0.2990 (3)0.40776 (16)0.0290 (5)
C20.68935 (9)0.1023 (3)0.39122 (15)0.0282 (5)
H2A0.67570.08400.32360.034*
H2B0.72800.03440.40200.034*
C30.65593 (10)−0.1272 (3)0.51335 (15)0.0306 (5)
H3A0.7018−0.13530.52060.037*
H3B0.6414−0.23000.47650.037*
C40.62514 (10)−0.1259 (3)0.61503 (15)0.0318 (5)
C50.57655 (10)0.0158 (3)0.40651 (15)0.0315 (5)
H5A0.5477−0.05020.44820.038*
H5B0.5829−0.05220.34670.038*
C60.54713 (10)0.1921 (3)0.38073 (16)0.0346 (5)
H6A0.57640.26170.34160.042*
H6B0.50840.17420.34260.042*
C70.51520 (11)0.4654 (3)0.45390 (16)0.0399 (6)
H7A0.48550.47290.39910.048*
H7B0.55240.53570.43820.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.03413 (17)0.01904 (16)0.02442 (16)−0.00075 (11)0.00398 (11)−0.00223 (11)
O10.0396 (8)0.0230 (8)0.0360 (8)−0.0019 (6)0.0064 (7)−0.0023 (6)
O20.0463 (10)0.0303 (9)0.0472 (10)−0.0061 (7)0.0184 (8)0.0033 (7)
O30.0509 (9)0.0244 (8)0.0305 (8)−0.0004 (7)0.0112 (7)−0.0017 (6)
O40.0880 (14)0.0262 (9)0.0349 (9)0.0034 (9)0.0107 (9)0.0057 (7)
O50.0361 (9)0.0321 (8)0.0326 (8)0.0080 (7)0.0034 (7)0.0013 (6)
O60.0560 (11)0.0231 (8)0.0358 (9)0.0043 (8)0.0001 (8)−0.0041 (7)
O70.0633 (12)0.0324 (9)0.0404 (10)−0.0015 (8)0.0109 (9)−0.0031 (8)
N10.0269 (9)0.0236 (9)0.0247 (9)−0.0006 (7)0.0034 (7)0.0001 (7)
C10.0274 (11)0.0259 (11)0.0336 (12)0.0016 (9)−0.0005 (9)0.0032 (9)
C20.0288 (11)0.0267 (11)0.0293 (11)−0.0013 (9)0.0066 (9)−0.0014 (9)
C30.0390 (12)0.0225 (11)0.0306 (11)0.0030 (9)0.0043 (9)−0.0015 (9)
C40.0390 (13)0.0285 (12)0.0279 (11)−0.0033 (9)0.0005 (9)0.0008 (10)
C50.0318 (12)0.0320 (12)0.0308 (11)−0.0044 (9)0.0027 (9)−0.0060 (9)
C60.0325 (12)0.0442 (14)0.0273 (12)0.0036 (10)0.0003 (9)−0.0013 (10)
C70.0415 (13)0.0351 (13)0.0433 (14)0.0119 (10)0.0036 (10)0.0064 (11)
Geometric parameters (Å, °) top
Ni1—O31.9255 (14)N1—C51.498 (3)
Ni1—O61.9293 (15)C1—C21.525 (3)
Ni1—O11.9451 (14)C2—H2A0.9700
Ni1—N11.9986 (16)C2—H2B0.9700
O1—C11.270 (2)C3—C41.530 (3)
O2—C11.244 (2)C3—H3A0.9700
O3—C41.277 (2)C3—H3B0.9700
O4—C41.231 (3)C5—C61.505 (3)
O5—C71.436 (3)C5—H5A0.9700
O5—C61.438 (2)C5—H5B0.9700
O6—H1W0.823 (16)C6—H6A0.9700
O6—H2W0.821 (16)C6—H6B0.9700
O7—H3W0.847 (16)C7—C7i1.503 (4)
O7—H4W0.826 (16)C7—H7A0.9700
N1—C31.486 (2)C7—H7B0.9700
N1—C21.489 (2)
O3—Ni1—O692.08 (7)N1—C3—C4110.04 (16)
O3—Ni1—O1163.08 (6)N1—C3—H3A109.7
O6—Ni1—O196.47 (7)C4—C3—H3A109.7
O3—Ni1—N185.25 (6)N1—C3—H3B109.7
O6—Ni1—N1177.32 (7)C4—C3—H3B109.7
O1—Ni1—N186.04 (6)H3A—C3—H3B108.2
C1—O1—Ni1113.76 (13)O4—C4—O3123.9 (2)
C4—O3—Ni1112.98 (13)O4—C4—C3118.98 (19)
C7—O5—C6112.13 (16)O3—C4—C3117.09 (18)
Ni1—O6—H1W108.7 (19)N1—C5—C6111.81 (17)
Ni1—O6—H2W116.7 (19)N1—C5—H5A109.3
H1W—O6—H2W111 (2)C6—C5—H5A109.3
H3W—O7—H4W108 (2)N1—C5—H5B109.3
C3—N1—C2114.36 (16)C6—C5—H5B109.3
C3—N1—C5110.52 (16)H5A—C5—H5B107.9
C2—N1—C5111.58 (15)O5—C6—C5108.25 (17)
C3—N1—Ni1104.10 (11)O5—C6—H6A110.0
C2—N1—Ni1107.40 (12)C5—C6—H6A110.0
C5—N1—Ni1108.41 (12)O5—C6—H6B110.0
O2—C1—O1123.58 (19)C5—C6—H6B110.0
O2—C1—C2117.76 (18)H6A—C6—H6B108.4
O1—C1—C2118.65 (18)O5—C7—C7i108.0 (2)
N1—C2—C1111.27 (16)O5—C7—H7A110.1
N1—C2—H2A109.4C7i—C7—H7A110.1
C1—C2—H2A109.4O5—C7—H7B110.1
N1—C2—H2B109.4C7i—C7—H7B110.1
C1—C2—H2B109.4H7A—C7—H7B108.4
H2A—C2—H2B108.0
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H1W···O70.823 (16)1.859 (17)2.671 (3)169 (3)
O6—H2W···O4ii0.821 (16)1.832 (18)2.625 (2)162 (3)
O7—H3W···O2iii0.847 (16)1.924 (17)2.758 (2)168 (3)
O7—H4W···O2iv0.826 (16)1.991 (17)2.785 (2)161 (3)
Symmetry codes: (ii) x, y+1, z; (iii) x, −y+1, z+1/2; (iv) −x+3/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H1W···O70.823 (16)1.859 (17)2.671 (3)169 (3)
O6—H2W···O4i0.821 (16)1.832 (18)2.625 (2)162 (3)
O7—H3W···O2ii0.847 (16)1.924 (17)2.758 (2)168 (3)
O7—H4W···O2iii0.826 (16)1.991 (17)2.785 (2)161 (3)
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z+1/2; (iii) −x+3/2, −y+1/2, −z+1.
Acknowledgements top

The authors are grateful to the Natural Science Foundation of Guangdong Province (grant No. M203066) for financial support.

references
References top

Bomas-Almenar, J. J., Coronado, E., Gomez-Gareia, C. J. & Ouahab, L. (1993). Angew. Chem. Int. Ed. Engl. 32, 561–563.

Bruker (1998). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Author APEXII instrument uses APEX2 software rather than SMART. Please check year of reference.

Bruker (1999). SAINT. Version 6.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.