Bis(benzohydrazide-κ2O,N′)bis­(nitrato-κO)copper(II)

Thiam, E.I.; Barry, A.H.; Navaza, A.; Retailleau, P.; Gaye, M.; Sall, A.S.

doi:10.1107/S1600536809029936

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m1014

doi:10.1107/S1600536809029936

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Bis(benzohydrazide-κ²O,N′)bis(nitrato-κO)copper(II)

Elhadj Ibrahima Thiam,^a Aliou Hamady Barry,^a Alda Navaza,^b Pascal Retailleau,^c Mohamed Gaye ^a ^* and Abdou Salam Sall ^a

^aDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Sénégal, ^bANBioPhi FRE 3207 CNRS, Université de Paris 13, 74 Rue Marcel Cachin, 93017, Bobigny, France, and ^cICSN-CNRS, Laboratoire de Cristallochimie, 1 Avenue la Terasse, 91198 Gift sur Yvette, France
^*Correspondence e-mail: mlgayeastou@yahoo.fr

(Received 23 July 2009; accepted 28 July 2009; online 31 July 2009)

In the title compound, [Cu(NO₃)₂(C₇H₈N₂O)₂], the Cu^II atom is located on a centre of inversion, and is coordinated by two bidentate benzohydrazide ligands and two monodentate nitrate anions in an axially distorted octahedral geometry within an N₂O₄ donor set. The crystal structure is stabilized by N—H⋯O and weak N—H⋯N hydrogen bonds.

Related literature

For related structures, see: Sousa-Pedrares et al. (2008 ); Despaigne et al. (2009 ); Hernández-Gil et al. (2009 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₇H₈N₂O)₂]
M_r = 459.86
Monoclinic, P 2₁ /c
a = 10.259 (5) Å
b = 10.078 (5) Å
c = 9.762 (4) Å
β = 106.85 (1)°
V = 966.0 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
3237 measured reflections
1768 independent reflections
1278 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.05
1768 reflections
145 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.911 (17)	1.94 (2)	2.794 (4)	156 (3)
N1—H1⋯N3ⁱ	0.911 (17)	2.64 (2)	3.371 (4)	138 (2)
N2—H2A⋯O2ⁱⁱ	0.929 (18)	2.03 (2)	2.813 (3)	141 (3)
N2—H2A⋯O3ⁱ	0.929 (18)	2.60 (3)	3.186 (3)	122 (2)
N2—H2B⋯O2ⁱⁱⁱ	0.912 (18)	1.97 (2)	2.834 (3)	159 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z; (iii) $[-x, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809029936/tk2516sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029936/tk2516Isup2.hkl

checkCIF report

Comment top

The Cu^II cation in (I), Fig. 1, is located on a centre of inversion. The Cu^II ion is coordinated to two neutral hydrazone molecules functioning as chelating ligands through the amine-N and carbonyl-O atoms. The equatorial bond Cu–O and Cu-N lengths [1.940 (2) and 1.970 (3) Å, respectively] are similar to those observed in related compounds (Sousa-Pedrares et al.<i\>, 2008; Despaigne et al.<i\>, 2009). The remaining coordination positions are occupied by two nitrate-O atoms which are located in apical positions [O1–Cu–O3 = 82.49 (8) °; and Cu–O3 = 2.589 (2) Å]. The axially distorted N₂O₄ coordination geometry is consistent with a Jahn–Teller effect (Hernández-Gil et al.<i\>, 2009). In the crystal structure, intermolecular N—H···O and (weak) N—H···N hydrogen bonds interactions link the molecules into a 2-D array (Table 1).

Related literature top

For related structures, see: Sousa-Pedrares et al. (2008); Despaigne et al. (2009); Hernández-Gil et al. (2009).

Experimental top

All purchased chemicals and solvents were reagent grade and used without further purification. To a mixture of benzohydrazide (0.2721 g, 2 mmol) and methanol (10 ml) was added dropwise a solution of copper nitrate trihydrate (0.2416 g, 1 mmol) in methanol (10 ml). The resulting green solution was stirred and refluxed for 2 h. The compound was filtered, and slow evaporation of the filtrate gave 0.2930 g (63.7 %) of (I). Analysis: calculated for C₁₄H₁₆CuN₄O₈: C 36.57, H 3.51, N 18.28 %; found: C 36.55, H 3.48, N 18.13. Crystals were obtained from slow evaporation of an ethanol solution of (I).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. Symmetry code: (i) -x, -y, -z

Bis(benzohydrazide-κ²O,N')bis(nitrato-κO)copper(II) top

Crystal data top

[Cu(NO₃)₂(C₇H₈N₂O)₂]	F(000) = 470
M_r = 459.86	D_x = 1.581 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1847 reflections
a = 10.259 (5) Å	θ = 0.4–25.4°
b = 10.078 (5) Å	µ = 1.19 mm⁻¹
c = 9.762 (4) Å	T = 293 K
β = 106.85 (1)°	Prism, blue
V = 966.0 (8) Å³	0.10 × 0.10 × 0.10 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	1278 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 25.4°, θ_min = 2.9°
π scans	h = −12→12
3237 measured reflections	k = −12→11
1768 independent reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0419P)² + 0.3254P] where P = (F_o² + 2F_c²)/3
1768 reflections	(Δ/σ)_max = 0.003
145 parameters	Δρ_max = 0.24 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₇H₈N₂O)₂]	V = 966.0 (8) Å³
M_r = 459.86	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.259 (5) Å	µ = 1.19 mm⁻¹
b = 10.078 (5) Å	T = 293 K
c = 9.762 (4) Å	0.10 × 0.10 × 0.10 mm
β = 106.85 (1)°

Data collection top

Nonius KappaCCD diffractometer	1278 reflections with I > 2σ(I)
3237 measured reflections	R_int = 0.029
1768 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	3 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.24 e Å⁻³
1768 reflections	Δρ_min = −0.26 e Å⁻³
145 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
Cu1	0.0000	0.0000	0.0000	0.04486 (19)
O1	−0.19749 (19)	0.00452 (19)	−0.0567 (2)	0.0488 (5)
O2	−0.0400 (3)	−0.1377 (2)	−0.3265 (2)	0.0779 (8)
O3	−0.0372 (2)	0.0668 (2)	−0.2647 (2)	0.0604 (6)
O4	−0.1549 (3)	0.0048 (2)	−0.4748 (2)	0.0777 (8)
N1	−0.1582 (2)	0.2195 (3)	−0.0063 (3)	0.0490 (6)
H1	−0.183 (3)	0.3054 (19)	0.001 (3)	0.058 (9)*
N2	−0.0173 (2)	0.1913 (2)	0.0322 (2)	0.0431 (6)
H2A	0.020 (3)	0.212 (3)	0.128 (2)	0.065 (10)*
H2B	0.023 (3)	0.243 (3)	−0.020 (3)	0.061 (10)*
N3	−0.0780 (3)	−0.0207 (2)	−0.3550 (3)	0.0492 (6)
C1	−0.2427 (3)	0.1197 (3)	−0.0488 (3)	0.0466 (7)
C2	−0.3914 (3)	0.1439 (3)	−0.0875 (3)	0.0544 (8)
C3	−0.4773 (3)	0.0501 (4)	−0.1710 (4)	0.0732 (10)
H3	−0.4410	−0.0246	−0.2024	0.088*
C4	−0.6155 (4)	0.0674 (6)	−0.2074 (4)	0.0973 (14)
H4	−0.6723	0.0049	−0.2653	0.117*
C5	−0.6709 (4)	0.1739 (6)	−0.1605 (5)	0.1008 (16)
H5	−0.7649	0.1841	−0.1857	0.121*
C6	−0.5871 (5)	0.2671 (5)	−0.0752 (6)	0.1043 (16)
H6	−0.6248	0.3400	−0.0423	0.125*
C7	−0.4457 (4)	0.2523 (4)	−0.0379 (5)	0.0804 (11)
H7	−0.3890	0.3150	0.0198	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0462 (3)	0.0307 (3)	0.0588 (3)	−0.0001 (2)	0.0170 (2)	−0.0012 (2)
O1	0.0476 (11)	0.0350 (11)	0.0640 (12)	−0.0019 (10)	0.0166 (10)	−0.0027 (10)
O2	0.146 (2)	0.0381 (13)	0.0555 (13)	0.0204 (14)	0.0385 (14)	0.0072 (10)
O3	0.0891 (17)	0.0414 (12)	0.0477 (12)	−0.0098 (12)	0.0154 (12)	−0.0092 (10)
O4	0.104 (2)	0.0504 (15)	0.0546 (14)	−0.0168 (13)	−0.0155 (14)	0.0068 (11)
N1	0.0501 (15)	0.0358 (14)	0.0573 (15)	0.0064 (12)	0.0097 (12)	−0.0033 (12)
N2	0.0495 (15)	0.0348 (13)	0.0426 (14)	−0.0011 (11)	0.0095 (12)	−0.0008 (11)
N3	0.0673 (16)	0.0380 (16)	0.0437 (14)	−0.0045 (12)	0.0182 (13)	0.0015 (11)
C1	0.0523 (17)	0.0462 (19)	0.0420 (16)	0.0038 (14)	0.0147 (14)	0.0047 (13)
C2	0.0501 (17)	0.060 (2)	0.0540 (18)	0.0083 (16)	0.0171 (15)	0.0102 (16)
C3	0.054 (2)	0.099 (3)	0.062 (2)	0.000 (2)	0.0083 (17)	−0.004 (2)
C4	0.057 (2)	0.150 (5)	0.075 (3)	−0.007 (3)	0.003 (2)	0.005 (3)
C5	0.051 (2)	0.136 (5)	0.111 (4)	0.017 (3)	0.016 (2)	0.051 (3)
C6	0.079 (3)	0.097 (4)	0.153 (4)	0.040 (3)	0.059 (3)	0.039 (3)
C7	0.065 (2)	0.068 (3)	0.114 (3)	0.014 (2)	0.035 (2)	0.011 (2)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.940 (2)	N2—H2B	0.912 (18)
Cu1—O1	1.940 (2)	C1—C2	1.482 (4)
Cu1—N2ⁱ	1.970 (3)	C2—C7	1.377 (5)
Cu1—N2	1.970 (3)	C2—C3	1.385 (5)
Cu1—O3	2.589 (2)	C3—C4	1.369 (5)
O1—C1	1.261 (3)	C3—H3	0.9300
O2—N3	1.249 (3)	C4—C5	1.355 (7)
O3—N3	1.231 (3)	C4—H4	0.9300
O4—N3	1.233 (3)	C5—C6	1.378 (7)
N1—C1	1.314 (4)	C5—H5	0.9300
N1—N2	1.413 (3)	C6—C7	1.397 (5)
N1—H1	0.911 (17)	C6—H6	0.9300
N2—H2A	0.929 (18)	C7—H7	0.9300

O1ⁱ—Cu1—O1	180.00 (3)	O4—N3—O2	118.7 (3)
O1ⁱ—Cu1—N2ⁱ	83.53 (9)	O1—C1—N1	120.2 (3)
O1—Cu1—N2ⁱ	96.47 (9)	O1—C1—C2	120.4 (3)
O1ⁱ—Cu1—N2	96.47 (9)	N1—C1—C2	119.4 (3)
O1—Cu1—N2	83.53 (9)	C7—C2—C3	119.7 (3)
N2ⁱ—Cu1—N2	180.00 (14)	C7—C2—C1	122.2 (3)
O1ⁱ—Cu1—O3	97.51 (8)	C3—C2—C1	118.0 (3)
O1—Cu1—O3	82.49 (8)	C4—C3—C2	120.0 (4)
N2ⁱ—Cu1—O3	95.12 (8)	C4—C3—H3	120.0
N2—Cu1—O3	84.88 (8)	C2—C3—H3	120.0
C1—O1—Cu1	112.10 (18)	C5—C4—C3	121.2 (5)
N3—O3—Cu1	116.74 (17)	C5—C4—H4	119.4
C1—N1—N2	117.4 (2)	C3—C4—H4	119.4
C1—N1—H1	125.2 (19)	C4—C5—C6	119.7 (4)
N2—N1—H1	117.4 (19)	C4—C5—H5	120.2
N1—N2—Cu1	106.71 (17)	C6—C5—H5	120.2
N1—N2—H2A	108.4 (19)	C5—C6—C7	120.2 (4)
Cu1—N2—H2A	111 (2)	C5—C6—H6	119.9
N1—N2—H2B	109.6 (19)	C7—C6—H6	119.9
Cu1—N2—H2B	113 (2)	C2—C7—C6	119.2 (4)
H2A—N2—H2B	108 (3)	C2—C7—H7	120.4
O3—N3—O4	121.4 (3)	C6—C7—H7	120.4
O3—N3—O2	119.8 (3)

N2ⁱ—Cu1—O1—C1	−179.41 (19)	N2—N1—C1—O1	−1.4 (4)
N2—Cu1—O1—C1	0.59 (19)	N2—N1—C1—C2	178.8 (2)
O3—Cu1—O1—C1	−85.07 (19)	O1—C1—C2—C7	157.9 (3)
O1ⁱ—Cu1—O3—N3	105.7 (2)	N1—C1—C2—C7	−22.2 (4)
O1—Cu1—O3—N3	−74.3 (2)	O1—C1—C2—C3	−19.0 (4)
N2ⁱ—Cu1—O3—N3	21.6 (2)	N1—C1—C2—C3	160.8 (3)
N2—Cu1—O3—N3	−158.4 (2)	C7—C2—C3—C4	1.9 (5)
C1—N1—N2—Cu1	1.7 (3)	C1—C2—C3—C4	179.0 (3)
O1ⁱ—Cu1—N2—N1	178.82 (16)	C2—C3—C4—C5	−1.5 (6)
O1—Cu1—N2—N1	−1.18 (16)	C3—C4—C5—C6	0.3 (7)
O3—Cu1—N2—N1	81.82 (16)	C4—C5—C6—C7	0.4 (7)
Cu1—O3—N3—O4	146.4 (2)	C3—C2—C7—C6	−1.2 (5)
Cu1—O3—N3—O2	−34.6 (3)	C1—C2—C7—C6	−178.2 (3)
Cu1—O1—C1—N1	0.2 (3)	C5—C6—C7—C2	0.1 (6)
Cu1—O1—C1—C2	−179.91 (19)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱⁱ	0.91 (2)	1.94 (2)	2.794 (4)	156 (3)
N1—H1···N3ⁱⁱ	0.91 (2)	2.64 (2)	3.371 (4)	138 (2)
N2—H2A···O2ⁱ	0.93 (2)	2.03 (2)	2.813 (3)	141 (3)
N2—H2A···O3ⁱⁱ	0.93 (2)	2.60 (3)	3.186 (3)	122 (2)
N2—H2B···O2ⁱⁱⁱ	0.91 (2)	1.97 (2)	2.834 (3)	159 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₇H₈N₂O)₂]
M_r	459.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.259 (5), 10.078 (5), 9.762 (4)
β (°)	106.85 (1)
V (Å³)	966.0 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3237, 1768, 1278
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.05
No. of reflections	1768
No. of parameters	145
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26

Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.911 (17)	1.94 (2)	2.794 (4)	156 (3)
N1—H1···N3ⁱ	0.911 (17)	2.64 (2)	3.371 (4)	138 (2)
N2—H2A···O2ⁱⁱ	0.929 (18)	2.03 (2)	2.813 (3)	141 (3)
N2—H2A···O3ⁱ	0.929 (18)	2.60 (3)	3.186 (3)	122 (2)
N2—H2B···O2ⁱⁱⁱ	0.912 (18)	1.97 (2)	2.834 (3)	159 (3)

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

Acknowledgements

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No. 6314PS804).

References

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