Bis(benzohydrazide-κ² O,N′)bis­(nitrato-κO)copper(II)

Abstract

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,

• a = 10.259 (5) Å

• b = 10.078 (5) Å

• c = 9.762 (4) Å

• β = 106.85 (1)°

• V = 966.0 (8) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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-Gilet 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).

Experimental

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).

Refinement

The H atoms of the NH and NH₂ groups were located in the Fourier difference maps and refined with N—H = 0.96 (2) Å. The remaining H atoms were placed geometrically and refined in the riding model approximation with C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C)].

Figures

Fig. 1.

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

Crystal data

[Cu(NO3)2(C7H8N2O)2]	F(000) = 470
Mr = 459.86	Dx = 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

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

Refinement

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(Fo2) + (0.0419P)2 + 0.3254P] where P = (Fo2 + 2Fc2)/3
1768 reflections	(Δ/σ)max = 0.003
145 parameters	Δρmax = 0.24 e Å−3
3 restraints	Δρmin = −0.26 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, °)

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