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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1361.
Published online 2009 October 17. doi:  10.1107/S1600536809041221
PMCID: PMC2970992

Tetra­aqua­(4,5-diaza­fluoren-9-one-κ2 N,N′)nickel(II) dinitrate

Abstract

The title compound, [Ni(C11H6N2O)(H2O)4](NO3)2, was prepared by the reaction of Ni(NO3)2 and 4,5-diaza­fluoren-9-one (dafo). The crystal packing consists of a three-dimensional network via O—H(...)O hydrogen bonds between the coordin­ated water mol­ecules and the nitrate anions. The Ni atom lies on a special position (Wyckoff position 4e, site symmetry 2), as does the carbonyl O atom.

Related literature

For properties of 4,5-diaza­fluoren-9-one compounds, see: Prasad et al. (2001 [triangle], 2002 [triangle]). For coordination compounds with dafo, see: Prasad et al. (2001 [triangle], 2002 [triangle]); Li et al. (2003 [triangle]); Wu et al. (2003 [triangle]); Zhang et al. (2003 [triangle]). For Ni—N and Ni—O bond lengths in related structures, see: Swamy et al. (2001 [triangle]); Kramer et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1361-scheme1.jpg

Experimental

Crystal data

  • [Ni(C11H6N2O)(H2O)4](NO3)2
  • M r = 436.97
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1361-efi1.jpg
  • a = 12.904 (3) Å
  • b = 10.207 (2) Å
  • c = 13.084 (3) Å
  • β = 105.85 (3)°
  • V = 1657.8 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.24 mm−1
  • T = 293 K
  • 0.26 × 0.25 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.739, T max = 0.790
  • 4262 measured reflections
  • 1465 independent reflections
  • 1303 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.107
  • S = 1.14
  • 1465 reflections
  • 124 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809041221/fi2084sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041221/fi2084Isup2.hkl

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

supplementary crystallographic information

Comment

4,5-diazafluoren-9-one (dafo), as well as the modified 1,10-phenanthroline (phen) neutral ligand, have allured interest in electrochemical, DNA intercalation and biological properties (Prasad et al., 2002 & Prasad et al., 2001). Because of the larger bite distance (2.99 Å) between two coordination nitrogen atoms, dafo provides an uncommon coordination environment, yielding a number of coordination compounds, such as two-dimensional sheets of [(dafone)2Cu(NCS)]n (Prasad et al., 2002), the zigzag chain structure of [Cu(Hnta)(afo)] (nta=nitrilotriacetate) (Li et al., 2003), the helical chains of cations formed by π-π stacking interaction in [Cd(dafo)2(tphpo)(CH3COO)]ClO4 (tphpo=triphenylphosphine oxide) (Wu et al., 2003), [Cu(dafone)2Cl2(dafoneH+H2O)2(ClO4)2] (Prasad et al., 2001) and [Zn(C11H6N2O)2(H2O)2](NO3)2 (Zhang et al., 2003). Compared to phen and 2,2'-bipyridine, the number of characterised metal compounds with dafo ligand is still small. Here we report the synthesis and structure of the title compound, which formes a three-dimensional network by O–H···O bonding.

The title structure (Fig. 1) features one Ni atom on a special position (Wyckoff position 4e, site symmetry 2), one 4,5-diazafluoren-9-one (dafo) ligand, four coordination water molecules and two nitrate anion. Even the dafo ligand lies on a special position (Wyckoff position 4e, site symmetry 2 with the C=O bond containing the twofold axis). Ni is coordinated by the two N atoms from dafo ligand, and four water molecules, yielding an overall tetragonally distorted octahedral geometry. The nitrogen donor atoms and two coordinated water molecules are found in the equatorial plane while the remaining two water molecules occupy the axial positions. The mean Ni—N and Ni—O bond lengths are similar to the reported (Swamy et al., 2001, Kramer et al., 2002). The torsion angles of O1W—Ni1—N2—C1, O2W—Ni1—N2—C1 are -91.30 (2) and -3.40 (2)°, respectively.

Hydrogen bonds are formed between the water molecules and O atoms from nitrate anions and the carbonyl group of the dafo ligand. O2w···O4 hydrogen-bond interactions link neighboring cations and form the one-dimensional chains. The anion NO3- link these chains together by O1w···O and O2w···O hydrogen bonds, resulting in the three-dimensional network (Fig.2).

Experimental

All commercially obtained reagent-grade chemicals were used without further purification. To a solution of dafo (0.452 g, 2.5 mmol) in methanol solution (30 ml) was added Ni(NO3)2 6(H2O) (0.581 g, 2.0 mmol) in water (20 ml). The solution was stirred for 1.5 h. The resultant dark green precipitate was filtered and dried thoroughly in air. The green crystals (yield 0.79 g) were grown by slow evaporation from the water and methanol (2:3 v/v) mixed solution.

Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H and O—H distances of 0.93 and 0.85 Å, respectively, and with Uiso(H) = 1.2Ueq of the parent atoms.

Figures

Fig. 1.
The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The chains formed by direct O(water)–H···O(carbonyl). H bonds as dashed lines
Fig. 3.
The network formed by O–H···ONO2 hydrogen bonds. H bonds as dashed lines. Only the C=O groups from the dafo ligand in the upper right and lower left corner are shown.

Crystal data

[Ni(C11H6N2O)(H2O)4](NO3)2F(000) = 896
Mr = 436.97Dx = 1.751 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1023 reflections
a = 12.904 (3) Åθ = 2.6–25.0°
b = 10.207 (2) ŵ = 1.24 mm1
c = 13.084 (3) ÅT = 293 K
β = 105.85 (3)°Prism, green
V = 1657.8 (6) Å30.26 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1465 independent reflections
Radiation source: fine-focus sealed tube1303 reflections with I > 2σ(I)
graphiteRint = 0.018
[var phi] and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −15→14
Tmin = 0.739, Tmax = 0.790k = −12→6
4262 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0607P)2 + 2.0108P] where P = (Fo2 + 2Fc2)/3
1465 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.60 e Å3

Special details

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)

xyzUiso*/Ueq
Ni10.00000.25222 (4)0.25000.0324 (2)
O40.00000.8551 (3)0.25000.0626 (9)
N20.06304 (18)0.4111 (2)0.35714 (17)0.0364 (5)
C10.1215 (2)0.4279 (3)0.4587 (2)0.0457 (7)
H1A0.14660.35440.50000.055*
C20.1455 (3)0.5512 (3)0.5037 (2)0.0532 (8)
H2A0.18560.55810.57420.064*
C30.1109 (2)0.6640 (3)0.4459 (2)0.0509 (7)
H3A0.12650.74670.47590.061*
C40.0525 (2)0.6478 (3)0.3418 (2)0.0398 (6)
C50.0318 (2)0.5207 (2)0.3050 (2)0.0338 (6)
C60.00000.7384 (4)0.25000.0452 (10)
O1W0.13445 (18)0.24757 (16)0.19659 (18)0.0457 (5)
H1W10.18480.27890.17350.055*
H2W10.15430.17230.22230.055*
O2W0.07053 (17)0.11039 (19)0.35806 (16)0.0494 (5)
H1W20.10310.09880.42330.059*
H2W20.03980.03870.33410.059*
N10.1702 (2)0.9279 (3)0.1387 (2)0.0557 (7)
O10.2159 (2)0.9812 (3)0.2222 (2)0.0748 (8)
O20.1842 (2)0.8094 (3)0.1304 (3)0.0966 (11)
O30.1130 (3)0.9928 (4)0.0676 (2)0.1121 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0441 (3)0.0220 (3)0.0305 (3)0.0000.0092 (2)0.000
O40.093 (2)0.0298 (16)0.073 (2)0.0000.0366 (19)0.000
N20.0461 (12)0.0296 (11)0.0330 (11)0.0009 (9)0.0098 (9)0.0010 (9)
C10.0495 (15)0.0509 (17)0.0345 (14)0.0049 (13)0.0078 (11)0.0055 (12)
C20.0532 (17)0.067 (2)0.0363 (15)−0.0054 (15)0.0063 (13)−0.0120 (15)
C30.0580 (17)0.0455 (17)0.0504 (17)−0.0118 (14)0.0172 (14)−0.0173 (14)
C40.0476 (14)0.0297 (13)0.0458 (15)−0.0041 (11)0.0190 (12)−0.0067 (11)
C50.0395 (13)0.0297 (13)0.0336 (13)−0.0008 (10)0.0123 (11)−0.0028 (10)
C60.055 (2)0.029 (2)0.060 (3)0.0000.030 (2)0.000
O1W0.0526 (12)0.0386 (12)0.0502 (13)−0.0020 (8)0.0214 (10)0.0063 (8)
O2W0.0717 (14)0.0324 (10)0.0403 (11)0.0043 (9)0.0089 (9)0.0060 (9)
N10.0442 (13)0.0670 (18)0.0534 (16)0.0116 (13)0.0092 (12)−0.0186 (14)
O10.0706 (15)0.0778 (18)0.0633 (15)0.0083 (13)−0.0032 (12)−0.0237 (13)
O20.090 (2)0.070 (2)0.134 (3)−0.0015 (16)0.0374 (19)−0.052 (2)
O30.103 (2)0.172 (3)0.0543 (16)0.077 (2)0.0078 (15)0.0039 (19)

Geometric parameters (Å, °)

Ni1—O1Wi2.040 (2)C3—C41.374 (4)
Ni1—O1W2.040 (2)C3—H3A0.9300
Ni1—O2Wi2.054 (2)C4—C51.383 (3)
Ni1—O2W2.054 (2)C4—C61.521 (4)
Ni1—O2W2.054 (2)C5—C5i1.450 (5)
Ni1—N22.153 (2)C6—C4i1.521 (4)
Ni1—N2i2.153 (2)O1W—H1W10.8502
O4—C61.191 (4)O1W—H2W10.8501
N2—C51.315 (3)O2W—O2W0.000 (4)
N2—C11.347 (4)O2W—H1W20.8501
C1—C21.388 (4)O2W—H2W20.8500
C1—H1A0.9300N1—O31.214 (4)
C2—C31.382 (5)N1—O11.219 (4)
C2—H2A0.9300N1—O21.231 (4)
O1Wi—Ni1—O1W177.33 (10)C3—C2—C1121.5 (3)
O1Wi—Ni1—O2Wi87.77 (8)C3—C2—H2A119.3
O1W—Ni1—O2Wi90.35 (9)C1—C2—H2A119.3
O1Wi—Ni1—O2W90.35 (9)C4—C3—C2116.7 (3)
O1W—Ni1—O2W87.77 (8)C4—C3—H3A121.7
O2Wi—Ni1—O2W90.39 (12)C2—C3—H3A121.7
O1Wi—Ni1—O2W90.35 (9)C3—C4—C5117.3 (3)
O1W—Ni1—O2W87.77 (8)C3—C4—C6135.6 (3)
O2Wi—Ni1—O2W90.39 (12)C5—C4—C6107.1 (2)
O2W—Ni1—O2W0.00 (12)N2—C5—C4127.9 (2)
O1Wi—Ni1—N289.99 (8)N2—C5—C5i121.67 (14)
O1W—Ni1—N292.01 (8)C4—C5—C5i110.40 (16)
O2Wi—Ni1—N2175.31 (8)O4—C6—C4i127.46 (15)
O2W—Ni1—N293.74 (9)O4—C6—C4127.46 (15)
O2W—Ni1—N293.74 (9)C4i—C6—C4105.1 (3)
O1Wi—Ni1—N2i92.01 (8)Ni1—O1W—H1W1156.5
O1W—Ni1—N2i89.99 (8)Ni1—O1W—H2W194.5
O2Wi—Ni1—N2i93.74 (9)H1W1—O1W—H2W1107.7
O2W—Ni1—N2i175.31 (8)O2W—O2W—Ni10(10)
O2W—Ni1—N2i175.31 (8)O2W—O2W—H1W20.0
N2—Ni1—N2i82.22 (12)Ni1—O2W—H1W2142.5
C5—N2—C1114.4 (2)O2W—O2W—H2W20.0
C5—N2—Ni1107.21 (16)Ni1—O2W—H2W2106.1
C1—N2—Ni1138.41 (19)H1W2—O2W—H2W2107.7
N2—C1—C2122.2 (3)O3—N1—O1119.1 (3)
N2—C1—H1A118.9O3—N1—O2122.8 (3)
C2—C1—H1A118.9O1—N1—O2118.1 (3)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H2W1···O2W0.852.402.838 (3)113
O1W—H1W1···O1ii0.852.613.070 (3)115
O1W—H2W1···O1iii0.852.112.901 (3)156
O2W—H1W2···O3iv0.852.082.848 (4)150
O2W—H2W2···O4iii0.852.162.986 (3)163

Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) x, −y+1, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FI2084).

References

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  • Li, B. L., Li, B. Z., Zhu, X. & Zhang, Y. (2003). Inorg. Chem. Commun.6, 1304–1306.
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  • Prasad, K., Subhash, P., Ekkehard, S., Christopher, E. A. & Annie, K. P. (2002). Inorg. Chim. Acta, 332, 167–175.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Swamy, G. Y. S. K., Mohan, K. C. & Ravikumar, K. (2001). Cryst. Res. Technol.36, 615–622.
  • Wu, B.-L., Zhang, H.-Y., Wu, Q.-A., Hou, H.-W. & Zh, Y. (2003). J. Mol. Struct.655, 467–472.
  • Zhang, R. L., Zhao, J. S., Shi, Q. Z. & Ng, S. W. (2003). Acta Cryst. E59, m476–m477.

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