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Acta Cryst. (2009). E65, m1238    [ doi:10.1107/S1600536809037672 ]

Bis(imidazole-[kappa]N3)bis(nitrato-[kappa]O)zinc(II)

A. Sy, A. H. Barry, F. Ben Amor, A. Driss, M. Gaye and A. S. Sall

Abstract top

The title complex, [Zn(NO3)2(C3H4N2)2], contains a ZnII centre with a slightly distorted tetrahedral coordination environment, involving two N atoms from imidazole ligands and two O atoms from nitrate anions. The imino NH groups participate in intermolecular N-H...O hydrogen bonds.

Comment top

The asymmetric unit of the title compound, contains a ZnII cation, two imidazole ligands and two nitrate anions acting as monodentate ligands (Fig. 1). In the molecule the ZnII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two imidazole molecules and two O atoms from monodentate two nitrate groups (Table 1). The angles O4—Zn—N5 and O1—Zn—O4 are reduced while all the others angles are increased in comparison with the ideal tetrahedral angle of 109.5° (Li et al., 2007) The values of Zn–N distances, 2.011 (3) and 2.015 (3) Å, are little far to that found for tris(2-ethyl-1H-imidazole-κN3)(terephthalato-κO)zinc(II) (Xie et al. 2009) and bis(1H-imidazole-κN3)[(2-oxidobenzylideneamino)methanesulfonato-κ2N,O]zinc(II) (He et al. 2007). The Zn—O coordinating distances of 1.966 (4) and 1.999 (3) Å are comparable of those found in diphenyldipyrazolylmethane complexes with zinc(II) (Shaw et al. 2009). The mononuclear complex is joined into a two-dimensional layer by N—H···O type hydrogen-bonds; details have been provided in Table 2.

Related literature top

For related structures, see: Li et al. (2007); Xie et al. (2009); He et al. (2007); Shaw et al. (2009).

Experimental top

Zinc(II) acetate dihydrate (0.1320 g; 0.6 mmol) and lanthanum nitrate hexahydrate (0.0433 g; 0.01 mmol) were dissolved in 10 ml of a mixture of water and methanol (1/2). To this solution was added imidazole (0.0408 g; 0.6 mmol) and tartaric acid (0.0900 g; 0.6 mmol) dissolved in 12 ml of an aqueous NaOH 0.1 M solution. After 120 m of stirring, a solution of tartaric acid (0.0900 g; 0.6 mmlol) in 5 ml of methanol was added again. The reaction mixture give white solid which was filtered and dried in air. The filtrate was left to crystallize. The crystals of (I) which formed were filtered off and dried [yield 82%]. Analysis calculated for [Zn(C3H4N2)2(NO3)2]: C 22.14, H 2.48, N 25.81%; found: C 22.09, H 2.46, N 25.78%. Spectroscopic analysis, IR (ν, cm-1): 3111, 3058, 1621, 1603, 1571, 1543, 1449, 1332 and 1072. The IR spectra were recorded with a Nicolet Magna 760 IR spectrophotometer in KBr pellets.

Refinement top

All H atoms were placed geometrically and refined with a riding model. Uiso(H) for H was assigned as 1.2Ueq of the attached C atoms.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: CAD-4 EXPRESS (Enraf–Nonius, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. An ORTEP view of the asymmetric unit of the title compound, showing the atom-numbering scheme (for all no H-atoms). Displacement ellipsoids are plotted at the 50% probability level.
[Figure 2] Fig. 2. Molecular representation of the compound showing hydrogen bonds. The broken lines indicate hydrogen bonds.
Bis(imidazole-κN3)bis(nitrato-κO)zinc(II) top
Crystal data top
[Zn(NO3)2(C3H4N2)2]Z = 2
Mr = 325.55F(000) = 328
Triclinic, P1Dx = 1.534 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.785 (6) ÅCell parameters from 25 reflections
b = 8.126 (2) Åθ = 11–15°
c = 11.394 (2) ŵ = 1.77 mm−1
α = 92.36 (2)°T = 293 K
β = 99.67 (4)°Prism, colourless
γ = 96.32 (7)°0.1 × 0.1 × 0.1 mm
V = 704.9 (6) Å3
Data collection top
Enraf–Nonius CAD-4
diffractometer		2733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
graphiteθmax = 27.0°, θmin = 2.5°
ω scansh = −9→2
3798 measured reflectionsk = −10→10
3068 independent reflectionsl = −14→14
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)] = 0.044H-atom parameters not refined
wR(F2) = 0.127 w = 1/[σ2(Fo2) + (0.0746P)2 + 0.6727P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.003
3068 reflectionsΔρmax = 0.53 e Å−3
173 parametersΔρmin = −0.64 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (3)
Crystal data top
[Zn(NO3)2(C3H4N2)2]γ = 96.32 (7)°
Mr = 325.55V = 704.9 (6) Å3
Triclinic, P1Z = 2
a = 7.785 (6) ÅMo Kα radiation
b = 8.126 (2) ŵ = 1.77 mm−1
c = 11.394 (2) ÅT = 293 K
α = 92.36 (2)°0.1 × 0.1 × 0.1 mm
β = 99.67 (4)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.014
3798 measured reflectionsθmax = 27.0°
3068 independent reflectionsStandard reflections: none
2733 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters not refined
wR(F2) = 0.127Δρmax = 0.53 e Å−3
S = 1.07Δρmin = −0.64 e Å−3
3068 reflectionsAbsolute structure: ?
173 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Zn10.15424 (5)0.41605 (4)0.23967 (3)0.03654 (17)
O10.3369 (3)0.3103 (3)0.3456 (2)0.0430 (5)
O20.3189 (6)0.3208 (6)−0.0920 (4)0.0971 (13)
O30.1851 (4)0.4038 (4)0.4754 (2)0.0547 (6)
O40.2364 (4)0.4269 (3)0.0859 (2)0.0558 (7)
O50.4232 (7)0.2470 (7)0.5506 (5)0.1252 (18)
O60.2253 (4)0.1542 (3)0.0596 (2)0.0574 (7)
N10.3052 (4)0.3279 (4)0.4537 (3)0.0510 (7)
N20.2542 (4)0.2947 (4)0.0259 (3)0.0503 (7)
N3−0.0884 (3)0.2952 (3)0.2279 (2)0.0360 (5)
N4−0.3596 (4)0.2487 (4)0.2566 (3)0.0477 (7)
H4N−0.45280.25580.28680.057*
N50.1481 (4)0.6622 (3)0.2647 (2)0.0385 (6)
N60.1656 (4)0.9234 (3)0.2214 (3)0.0509 (7)
H6N0.18621.01140.18420.061*
C1−0.1781 (5)0.1749 (4)0.1439 (3)0.0440 (7)
H1−0.13080.12260.08470.053*
C2−0.3456 (5)0.1454 (5)0.1615 (4)0.0535 (9)
H2−0.43400.07000.11780.064*
C3−0.2038 (4)0.3359 (4)0.2941 (3)0.0417 (7)
H3−0.17910.41470.35810.050*
C40.0906 (5)0.7536 (4)0.3524 (3)0.0429 (7)
H40.05090.71100.41890.051*
C50.1012 (5)0.9154 (4)0.3262 (4)0.0507 (8)
H50.07081.00310.37040.061*
C60.1905 (5)0.7699 (4)0.1878 (3)0.0445 (7)
H60.23250.74220.11870.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0395 (2)0.0308 (2)0.0420 (2)0.00520 (14)0.01374 (15)0.00335 (14)
O10.0397 (12)0.0507 (13)0.0420 (12)0.0110 (10)0.0144 (10)0.0003 (10)
O20.124 (3)0.106 (3)0.069 (2)0.009 (3)0.041 (2)0.013 (2)
O30.0595 (16)0.0674 (17)0.0446 (13)0.0221 (13)0.0207 (12)0.0009 (12)
O40.0794 (19)0.0442 (13)0.0528 (15)0.0118 (13)0.0342 (14)0.0027 (11)
O50.130 (4)0.144 (5)0.095 (3)0.039 (3)−0.018 (3)0.028 (3)
O60.082 (2)0.0396 (13)0.0546 (15)−0.0006 (13)0.0282 (14)0.0086 (11)
N10.0515 (17)0.0519 (17)0.0489 (16)0.0010 (14)0.0108 (13)0.0008 (13)
N20.0495 (17)0.0553 (18)0.0472 (16)0.0039 (14)0.0126 (13)0.0046 (13)
N30.0364 (13)0.0365 (13)0.0361 (13)0.0051 (10)0.0094 (10)0.0005 (10)
N40.0363 (14)0.0550 (17)0.0559 (17)0.0096 (12)0.0167 (13)0.0031 (14)
N50.0459 (14)0.0319 (12)0.0396 (13)0.0048 (11)0.0118 (11)0.0051 (10)
N60.063 (2)0.0332 (14)0.0614 (19)0.0060 (13)0.0214 (16)0.0147 (13)
C10.0432 (17)0.0485 (18)0.0397 (16)0.0090 (14)0.0062 (13)−0.0084 (14)
C20.0428 (19)0.052 (2)0.061 (2)0.0028 (15)0.0023 (16)−0.0091 (17)
C30.0446 (17)0.0444 (17)0.0385 (16)0.0070 (14)0.0141 (13)−0.0018 (13)
C40.0528 (19)0.0368 (16)0.0407 (16)0.0038 (14)0.0138 (14)0.0030 (13)
C50.063 (2)0.0346 (16)0.058 (2)0.0075 (15)0.0181 (18)0.0001 (15)
C60.0516 (19)0.0407 (17)0.0453 (17)0.0067 (14)0.0178 (15)0.0090 (13)
Geometric parameters (Å, °) top
Zn1—O41.966 (3)N4—H4N0.8600
Zn1—O11.999 (3)N5—C61.320 (4)
Zn1—N32.011 (3)N5—C41.383 (4)
Zn1—N52.015 (3)N6—C61.334 (5)
O1—N11.301 (4)N6—C51.372 (5)
O2—N21.526 (5)N6—H6N0.8600
O3—N11.228 (4)C1—C21.350 (5)
O4—N21.282 (4)C1—H10.9300
O5—N11.532 (5)C2—H20.9300
O6—N21.229 (4)C3—H30.9300
N3—C31.327 (4)C4—C51.356 (5)
N3—C11.381 (4)C4—H40.9300
N4—C31.330 (5)C5—H50.9300
N4—C21.369 (5)C6—H60.9300
O4—Zn1—O1104.93 (12)C4—N5—Zn1131.1 (2)
O4—Zn1—N3113.61 (12)C6—N6—C5107.5 (3)
O1—Zn1—N3113.00 (11)C6—N6—H6N126.2
O4—Zn1—N595.75 (11)C5—N6—H6N126.2
O1—Zn1—N5118.25 (12)C2—C1—N3109.0 (3)
N3—Zn1—N5110.03 (13)C2—C1—H1125.5
N1—O1—Zn1107.0 (2)N3—C1—H1125.5
N2—O4—Zn1121.2 (2)C1—C2—N4106.4 (3)
O3—N1—O1121.1 (3)C1—C2—H2126.8
O3—N1—O5122.4 (4)N4—C2—H2126.8
O1—N1—O5116.5 (3)N3—C3—N4110.7 (3)
O6—N2—O4123.7 (3)N3—C3—H3124.6
O6—N2—O2120.5 (3)N4—C3—H3124.6
O4—N2—O2115.8 (3)C5—C4—N5109.2 (3)
C3—N3—C1105.9 (3)C5—C4—H4125.4
C3—N3—Zn1124.1 (2)N5—C4—H4125.4
C1—N3—Zn1129.5 (2)C4—C5—N6106.2 (3)
C3—N4—C2108.0 (3)C4—C5—H5126.9
C3—N4—H4N126.0N6—C5—H5126.9
C2—N4—H4N126.0N5—C6—N6111.5 (3)
C6—N5—C4105.5 (3)N5—C6—H6124.2
C6—N5—Zn1123.2 (2)N6—C6—H6124.2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4N···O1i0.861.962.808 (4)170
N6—H6N···O6ii0.861.912.741 (4)161
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O41.966 (3)Zn1—N32.011 (3)
Zn1—O11.999 (3)Zn1—N52.015 (3)
O4—Zn1—O1104.93 (12)O4—Zn1—N595.75 (11)
O4—Zn1—N3113.61 (12)O1—Zn1—N5118.25 (12)
O1—Zn1—N3113.00 (11)N3—Zn1—N5110.03 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4N···O1i0.861.962.808 (4)170
N6—H6N···O6ii0.861.912.741 (4)161
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z.
Acknowledgements top

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No. 6301PS48)

references
References top

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.

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

He, K.-H., Li, J.-M. & Jiang, Y.-M. (2007). Acta Cryst. E63, m2992–m2993.

Li, J., Noll, B. C. & Scheidt, W. R. (2007). Acta Cryst. E63, m1048–m1049.

Shaw, J. L., Gwaltney, K. P. & Keer, N. (2009). Inorg. Chim. Acta, 362, 2396-2401.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Xie, Q.-A., Dong, G.-Y., Yu, Y.-M. & Wang, Y.-G. (2009). Acta Cryst. E65, m576.