Bis(imidazole-κN3)bis­(nitrato-κO)zinc(II)

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

doi:10.1107/S1600536809037672

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1238

doi:10.1107/S1600536809037672

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Bis(imidazole-κN³)bis(nitrato-κO)zinc(II)

Adama Sy,^a Aliou Hamady Barry,^b Fatma Ben Amor,^c Ahmed Driss,^c Mohamed Gaye ^a ^* and Abdou Salam Sall ^a

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bDépartement de Chimie, Faculté des Sciences, Université de Nouakchott, Nouakchott, Mauritania, and ^cCampus Universitaire, Département de Chimie, Faculté des Sciences, Université de Tunis, 1060 Tunis, Tunisia
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 10 September 2009; accepted 17 September 2009; online 26 September 2009)

The title complex, [Zn(NO₃)₂(C₃H₄N₂)₂], contains a Zn^II 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.

Related literature

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

Experimental

Crystal data

[Zn(NO₃)₂(C₃H₄N₂)₂]
M_r = 325.55
Triclinic, $[P \overline 1]$
a = 7.785 (6) Å
b = 8.126 (2) Å
c = 11.394 (2) Å
α = 92.36 (2)°
β = 99.67 (4)°
γ = 96.32 (7)°
V = 704.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.77 mm⁻¹
T = 293 K
0.1 × 0.1 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
3798 measured reflections
3068 independent reflections
2733 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.07
3068 reflections
173 parameters
H-atom parameters not refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O4	1.966 (3)
Zn1—O1	1.999 (3)
Zn1—N3	2.011 (3)
Zn1—N5	2.015 (3)

O4—Zn1—O1	104.93 (12)
O4—Zn1—N3	113.61 (12)
O1—Zn1—N3	113.00 (11)
O4—Zn1—N5	95.75 (11)
O1—Zn1—N5	118.25 (12)
N3—Zn1—N5	110.03 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯O1ⁱ	0.86	1.96	2.808 (4)	170
N6—H6N⋯O6ⁱⁱ	0.86	1.91	2.741 (4)	161
Symmetry codes: (i) x-1, y, z; (ii) x, y+1, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 EXPRESS; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809037672/fj2244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037672/fj2244Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound, contains a Zn^II cation, two imidazole ligands and two nitrate anions acting as monodentate ligands (Fig. 1). In the molecule the Zn^II 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.

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

	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.
	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
M_r = 325.55	F(000) = 328
Triclinic, P1	D_x = 1.534 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.785 (6) Å	Cell parameters from 25 reflections
b = 8.126 (2) Å	θ = 11–15°
c = 11.394 (2) Å	µ = 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 tube	R_int = 0.014
Graphite monochromator	θ_max = 27.0°, θ_min = 2.5°
ω scans	h = −9→2
3798 measured reflections	k = −10→10
3068 independent reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters not refined
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0746P)² + 0.6727P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.003
3068 reflections	Δρ_max = 0.53 e Å⁻³
173 parameters	Δρ_min = −0.64 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (3)

Crystal data top

[Zn(NO₃)₂(C₃H₄N₂)₂]	γ = 96.32 (7)°
M_r = 325.55	V = 704.9 (6) Å³
Triclinic, P1	Z = 2
a = 7.785 (6) Å	Mo Kα radiation
b = 8.126 (2) Å	µ = 1.77 mm⁻¹
c = 11.394 (2) Å	T = 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	2733 reflections with I > 2σ(I)
3798 measured reflections	R_int = 0.014
3068 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.127	H-atom parameters not refined
S = 1.07	Δρ_max = 0.53 e Å⁻³
3068 reflections	Δρ_min = −0.64 e Å⁻³
173 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

	x	y	z	U_iso*/U_eq
Zn1	0.15424 (5)	0.41605 (4)	0.23967 (3)	0.03654 (17)
O1	0.3369 (3)	0.3103 (3)	0.3456 (2)	0.0430 (5)
O2	0.3189 (6)	0.3208 (6)	−0.0920 (4)	0.0971 (13)
O3	0.1851 (4)	0.4038 (4)	0.4754 (2)	0.0547 (6)
O4	0.2364 (4)	0.4269 (3)	0.0859 (2)	0.0558 (7)
O5	0.4232 (7)	0.2470 (7)	0.5506 (5)	0.1252 (18)
O6	0.2253 (4)	0.1542 (3)	0.0596 (2)	0.0574 (7)
N1	0.3052 (4)	0.3279 (4)	0.4537 (3)	0.0510 (7)
N2	0.2542 (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	−0.4528	0.2558	0.2868	0.057*
N5	0.1481 (4)	0.6622 (3)	0.2647 (2)	0.0385 (6)
N6	0.1656 (4)	0.9234 (3)	0.2214 (3)	0.0509 (7)
H6N	0.1862	1.0114	0.1842	0.061*
C1	−0.1781 (5)	0.1749 (4)	0.1439 (3)	0.0440 (7)
H1	−0.1308	0.1226	0.0847	0.053*
C2	−0.3456 (5)	0.1454 (5)	0.1615 (4)	0.0535 (9)
H2	−0.4340	0.0700	0.1178	0.064*
C3	−0.2038 (4)	0.3359 (4)	0.2941 (3)	0.0417 (7)
H3	−0.1791	0.4147	0.3581	0.050*
C4	0.0906 (5)	0.7536 (4)	0.3524 (3)	0.0429 (7)
H4	0.0509	0.7110	0.4189	0.051*
C5	0.1012 (5)	0.9154 (4)	0.3262 (4)	0.0507 (8)
H5	0.0708	1.0031	0.3704	0.061*
C6	0.1905 (5)	0.7699 (4)	0.1878 (3)	0.0445 (7)
H6	0.2325	0.7422	0.1187	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0395 (2)	0.0308 (2)	0.0420 (2)	0.00520 (14)	0.01374 (15)	0.00335 (14)
O1	0.0397 (12)	0.0507 (13)	0.0420 (12)	0.0110 (10)	0.0144 (10)	0.0003 (10)
O2	0.124 (3)	0.106 (3)	0.069 (2)	0.009 (3)	0.041 (2)	0.013 (2)
O3	0.0595 (16)	0.0674 (17)	0.0446 (13)	0.0221 (13)	0.0207 (12)	0.0009 (12)
O4	0.0794 (19)	0.0442 (13)	0.0528 (15)	0.0118 (13)	0.0342 (14)	0.0027 (11)
O5	0.130 (4)	0.144 (5)	0.095 (3)	0.039 (3)	−0.018 (3)	0.028 (3)
O6	0.082 (2)	0.0396 (13)	0.0546 (15)	−0.0006 (13)	0.0282 (14)	0.0086 (11)
N1	0.0515 (17)	0.0519 (17)	0.0489 (16)	0.0010 (14)	0.0108 (13)	0.0008 (13)
N2	0.0495 (17)	0.0553 (18)	0.0472 (16)	0.0039 (14)	0.0126 (13)	0.0046 (13)
N3	0.0364 (13)	0.0365 (13)	0.0361 (13)	0.0051 (10)	0.0094 (10)	0.0005 (10)
N4	0.0363 (14)	0.0550 (17)	0.0559 (17)	0.0096 (12)	0.0167 (13)	0.0031 (14)
N5	0.0459 (14)	0.0319 (12)	0.0396 (13)	0.0048 (11)	0.0118 (11)	0.0051 (10)
N6	0.063 (2)	0.0332 (14)	0.0614 (19)	0.0060 (13)	0.0214 (16)	0.0147 (13)
C1	0.0432 (17)	0.0485 (18)	0.0397 (16)	0.0090 (14)	0.0062 (13)	−0.0084 (14)
C2	0.0428 (19)	0.052 (2)	0.061 (2)	0.0028 (15)	0.0023 (16)	−0.0091 (17)
C3	0.0446 (17)	0.0444 (17)	0.0385 (16)	0.0070 (14)	0.0141 (13)	−0.0018 (13)
C4	0.0528 (19)	0.0368 (16)	0.0407 (16)	0.0038 (14)	0.0138 (14)	0.0030 (13)
C5	0.063 (2)	0.0346 (16)	0.058 (2)	0.0075 (15)	0.0181 (18)	0.0001 (15)
C6	0.0516 (19)	0.0407 (17)	0.0453 (17)	0.0067 (14)	0.0178 (15)	0.0090 (13)

Geometric parameters (Å, º) top

Zn1—O4	1.966 (3)	N4—H4N	0.8600
Zn1—O1	1.999 (3)	N5—C6	1.320 (4)
Zn1—N3	2.011 (3)	N5—C4	1.383 (4)
Zn1—N5	2.015 (3)	N6—C6	1.334 (5)
O1—N1	1.301 (4)	N6—C5	1.372 (5)
O2—N2	1.526 (5)	N6—H6N	0.8600
O3—N1	1.228 (4)	C1—C2	1.350 (5)
O4—N2	1.282 (4)	C1—H1	0.9300
O5—N1	1.532 (5)	C2—H2	0.9300
O6—N2	1.229 (4)	C3—H3	0.9300
N3—C3	1.327 (4)	C4—C5	1.356 (5)
N3—C1	1.381 (4)	C4—H4	0.9300
N4—C3	1.330 (5)	C5—H5	0.9300
N4—C2	1.369 (5)	C6—H6	0.9300

O4—Zn1—O1	104.93 (12)	C4—N5—Zn1	131.1 (2)
O4—Zn1—N3	113.61 (12)	C6—N6—C5	107.5 (3)
O1—Zn1—N3	113.00 (11)	C6—N6—H6N	126.2
O4—Zn1—N5	95.75 (11)	C5—N6—H6N	126.2
O1—Zn1—N5	118.25 (12)	C2—C1—N3	109.0 (3)
N3—Zn1—N5	110.03 (13)	C2—C1—H1	125.5
N1—O1—Zn1	107.0 (2)	N3—C1—H1	125.5
N2—O4—Zn1	121.2 (2)	C1—C2—N4	106.4 (3)
O3—N1—O1	121.1 (3)	C1—C2—H2	126.8
O3—N1—O5	122.4 (4)	N4—C2—H2	126.8
O1—N1—O5	116.5 (3)	N3—C3—N4	110.7 (3)
O6—N2—O4	123.7 (3)	N3—C3—H3	124.6
O6—N2—O2	120.5 (3)	N4—C3—H3	124.6
O4—N2—O2	115.8 (3)	C5—C4—N5	109.2 (3)
C3—N3—C1	105.9 (3)	C5—C4—H4	125.4
C3—N3—Zn1	124.1 (2)	N5—C4—H4	125.4
C1—N3—Zn1	129.5 (2)	C4—C5—N6	106.2 (3)
C3—N4—C2	108.0 (3)	C4—C5—H5	126.9
C3—N4—H4N	126.0	N6—C5—H5	126.9
C2—N4—H4N	126.0	N5—C6—N6	111.5 (3)
C6—N5—C4	105.5 (3)	N5—C6—H6	124.2
C6—N5—Zn1	123.2 (2)	N6—C6—H6	124.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O1ⁱ	0.86	1.96	2.808 (4)	170
N6—H6N···O6ⁱⁱ	0.86	1.91	2.741 (4)	161

Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Zn(NO₃)₂(C₃H₄N₂)₂]
M_r	325.55
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.785 (6), 8.126 (2), 11.394 (2)
α, β, γ (°)	92.36 (2), 99.67 (4), 96.32 (7)
V (Å³)	704.9 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.77
Crystal size (mm)	0.1 × 0.1 × 0.1

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3798, 3068, 2733
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.07
No. of reflections	3068
No. of parameters	173
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.64

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Zn1—O4	1.966 (3)	Zn1—N3	2.011 (3)
Zn1—O1	1.999 (3)	Zn1—N5	2.015 (3)

O4—Zn1—O1	104.93 (12)	O4—Zn1—N5	95.75 (11)
O4—Zn1—N3	113.61 (12)	O1—Zn1—N5	118.25 (12)
O1—Zn1—N3	113.00 (11)	N3—Zn1—N5	110.03 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O1ⁱ	0.86	1.96	2.808 (4)	170
N6—H6N···O6ⁱⁱ	0.86	1.91	2.741 (4)	161

Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z.

Acknowledgements

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

References

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