(Acetyl­acetonato)dibromido[2,2-diphenyl­hydrazin-1-ido(1−)][2,2-diphenyl­hydrazin-1-ido(2−)]molybdenum(VI)

Carlos Bustos; Luis Alvarez-Thon; Andrés Ibañez; Christian Sánchez

doi:10.1107/S1600536811015881

. 2011 May 7;67(Pt 6):m675–m676. doi: 10.1107/S1600536811015881

(Acetylacetonato)dibromido[2,2-diphenylhydrazin-1-ido(1−)][2,2-diphenylhydrazin-1-ido(2−)]molybdenum(VI)

Carlos Bustos ^a, Luis Alvarez-Thon ^b,^*, Andrés Ibañez ^c, Christian Sánchez ^a

PMCID: PMC3120344 PMID: 21754584

Abstract

In the title compound, [MoBr₂(C₁₂H₁₁N₂)(C₁₂H₁₀N₂)(C₅H₇O₂)], the Mo^VI atom is six-coordinated in a distorted octahedral geometry by two N atoms from the diphenylhydrazide(1−) and diphenylhydrazide(2−) ligands, two O atoms from a bidentate acetylacetonate ligand and two Br⁻ ions. The molecules form an inversion dimer via a pair of weak C—H⋯O hydrogen bonds and a π–π stacking interaction with a centroid–centroid distance of 3.7401 (12) Å. Weak intramolecular C—H⋯Br interactions and an intramolecular π–π stacking interaction with a centroid–centroid distance of 3.8118 (15) Å are also observed.

Related literature

For related structures, see: Bustos et al. (1994 ▶, 2006 ▶). For the importance of these compounds as potential models of intermediates in the conversion of coordinated dinitrogen into ammonia, see: Henderson et al. (1983 ▶); McCleverty (1987 ▶).

Experimental

Crystal data

[MoBr₂(C₁₂H₁₁N₂)(C₁₂H₁₀N₂)(C₅H₇O₂)]
M _r = 720.29
Monoclinic,
a = 9.5828 (11) Å
b = 32.187 (4) Å
c = 9.1455 (10) Å
β = 94.601 (2)°
V = 2811.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 3.34 mm⁻¹
T = 150 K
0.36 × 0.31 × 0.29 mm

Data collection

Bruker D8 Discover with SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.324, T _max = 0.379
22331 measured reflections
5678 independent reflections
5133 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.063
S = 1.05
5678 reflections
349 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015881/is2705sup1.cif

e-67-0m675-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015881/is2705Isup2.hkl

e-67-0m675-Isup2.hkl^{(278KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mo1—Br1	2.6023 (5)
Mo1—Br2	2.5646 (4)
Mo1—O1	2.1074 (16)
Mo1—O2	2.0530 (13)
Mo1—N1	1.9638 (16)
Mo1—N3	1.7559 (18)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Br2	0.95	2.92	3.712 (3)	142
C20—H20⋯Br2	0.95	2.85	3.788 (2)	168
C23—H23⋯O2ⁱ	0.95	2.49	3.392 (2)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the FONDECYT (grant Nos. 11100446 and 1080269) and the Universidad Andrés Bello (grant No. DI-06-10-R).

supplementary crystallographic information

Comment

In a previous paper, it was published a series of molybdenum complexes containing both end-on organohydrazide(1-) and organohydrazide(2-) ligands (Bustos et al., 1994), formulated as [Mo(NHNRPh)(NNRPh)(acac)X₂] (R= Me, Ph; X = Cl, Br, I). These compounds are of remarkable importance as potential models of intermediates in the conversion of coordinated dinitrogen into ammonia (McCleverty, 1987; Henderson et al., 1983). Here, the crystalline and molecular structure of [Mo(NHNPh₂)(NNPh₂)(acac)Br₂] is reported.

The molecular structure of the title compound, (I), is shown in Fig. 1. This compound which crystallizes in space group P2₁/c, is equivalent in topology to [Mo(NHNPh₂)(NNPh₂)(acac)Cl₂] (Bustos et al., 1994), (code HEDCIC), where the bromine atoms are replaced by chlorine atoms.

The coordination geometry about the Mo^VI atom can be described as a distorted octahedron (Table 1). The bromine ligands occupy two trans-axial sites while the equatorial positions are occupied by two cis-hydrazide ligands and the oxygen atoms of the acetylacetonate ligand. The two hydrazide ligands are different due to the location of the hydrogen atom attached to the N1 atom. In effect the Mo1, N3 and N4 atoms are almost linear [171.87 (14)°] while the Mo1—N1—N2 angle is 140.98 (15)°. In (I), there are two weak intramolecular C—H···Br hydrogen bonds (Table 2) and one intramolecular π–π stacking interaction involving the C1—C6 and C13—C18 rings, with a distance of 3.8118 (15) Å between ring centroids (Fig. 2).

In the crystal structure, two weak hydrogen bonds C23—H23···O2ⁱ and C23ⁱ—H23ⁱ..O2 (Table 2) link the molecules into dimers. In addition these dimers are further stabilized by a π–π stacking interaction with distance Cg···Cgⁱ of 3.7401 (12) Å, where Cg is the centroids of the C19–C24 ring (Fig. 2). [symmetry code: (i) 1 - x, -y, -z]. The entire three-dimensional network is constructed mainly by weak C—H···Br interactions (Bustos et al., 2006).

Experimental

This compound was synthesized as was described in the literature (Bustos et al., 1994), and single crystals suitable for X-ray diffraction were obtained by diffusion of diethylether on a concentrated solution of the compound in chloroform.