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

Bustos, C.; Alvarez-Thon, L.; Ibañez, A.; Sánchez, C.

doi:10.1107/S1600536811015881

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m675-m676

doi:10.1107/S1600536811015881

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(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 and Christian Sánchez ^a

^aInstituto de Ciencias Químicas, Universidad Austral de Chile, Avda. Los Robles s/n, Campus Isla Teja, Casilla 567, Valdivia, Chile, ^bDepartamento de Ciencias Físicas, Universidad Andres Bello, Avda. República 220, Santiago de Chile, Chile, and ^cLaboratorio de Cristalografía, Difracción de Rayos-X, Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago, Chile
^*Correspondence e-mail: lalvarez@unab.cl

(Received 20 April 2011; accepted 26 April 2011; online 7 May 2011)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.024
wR(F²) = 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

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)

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
Symmetry code: (i) -x+1, -y, -z.

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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure, showing the formation of dimer connected via two weak contacts (dashed lines) and one π–π stacking interaction. It is also shown intramolecular π–π stacking interactions (dotted lines) [symmetry code: (i) 1 - x, -y, -z]. H atoms not involved in the interactions have been omitted for clarity.

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

Crystal data top

[MoBr₂(C₁₂H₁₁N₂)(C₁₂H₁₀N₂)(C₅H₇O₂)]	F(000) = 1432
M_r = 720.29	D_x = 1.702 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 999 reflections
a = 9.5828 (11) Å	θ = 2.1–26.3°
b = 32.187 (4) Å	µ = 3.34 mm⁻¹
c = 9.1455 (10) Å	T = 150 K
β = 94.601 (2)°	Block, red
V = 2811.8 (6) Å³	0.36 × 0.31 × 0.29 mm
Z = 4

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	5678 independent reflections
Radiation source: fine-focus sealed tube	5133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.324, T_max = 0.379	k = −39→40
22331 measured 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.034P)² + 1.394P] where P = (F_o² + 2F_c²)/3
5678 reflections	(Δ/σ)_max = 0.001
349 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[MoBr₂(C₁₂H₁₁N₂)(C₁₂H₁₀N₂)(C₅H₇O₂)]	V = 2811.8 (6) Å³
M_r = 720.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5828 (11) Å	µ = 3.34 mm⁻¹
b = 32.187 (4) Å	T = 150 K
c = 9.1455 (10) Å	0.36 × 0.31 × 0.29 mm
β = 94.601 (2)°

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	5678 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	5133 reflections with I > 2σ(I)
T_min = 0.324, T_max = 0.379	R_int = 0.021
22331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.063	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.68 e Å⁻³
5678 reflections	Δρ_min = −0.29 e Å⁻³
349 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Mo1	0.81628 (2)	0.10424 (1)	0.25802 (2)	0.0187 (1)
Br1	0.92515 (2)	0.10449 (1)	0.00633 (3)	0.0275 (1)
Br2	0.75285 (3)	0.09355 (1)	0.52256 (2)	0.0295 (1)
O1	1.02455 (16)	0.10749 (5)	0.35070 (18)	0.0265 (5)
O2	0.85400 (15)	0.04148 (4)	0.25378 (16)	0.0246 (4)
N1	0.8420 (2)	0.16473 (5)	0.26814 (19)	0.0209 (5)
N2	0.77411 (19)	0.20059 (5)	0.2310 (2)	0.0244 (5)
N3	0.64377 (18)	0.10063 (5)	0.17844 (19)	0.0190 (5)
N4	0.51707 (18)	0.09218 (5)	0.11958 (19)	0.0213 (5)
C1	0.6275 (2)	0.20319 (6)	0.2423 (2)	0.0225 (6)
C2	0.5436 (2)	0.22312 (7)	0.1319 (3)	0.0271 (7)
C3	0.4013 (3)	0.22633 (7)	0.1446 (3)	0.0317 (7)
C4	0.3422 (3)	0.20957 (8)	0.2650 (3)	0.0343 (8)
C5	0.4264 (3)	0.19004 (8)	0.3739 (3)	0.0326 (8)
C6	0.5696 (3)	0.18676 (7)	0.3642 (3)	0.0278 (7)
C7	0.8529 (2)	0.23412 (7)	0.1783 (3)	0.0259 (7)
C8	0.8250 (3)	0.27458 (7)	0.2205 (3)	0.0359 (8)
C9	0.9034 (3)	0.30687 (8)	0.1696 (4)	0.0496 (10)
C10	1.0081 (3)	0.29879 (9)	0.0774 (4)	0.0544 (10)
C11	1.0352 (3)	0.25879 (10)	0.0369 (3)	0.0467 (10)
C12	0.9578 (2)	0.22561 (8)	0.0865 (3)	0.0324 (8)
C13	0.4572 (2)	0.11994 (6)	0.0079 (2)	0.0208 (6)
C14	0.3143 (2)	0.12864 (7)	0.0017 (2)	0.0248 (6)
C15	0.2557 (2)	0.15429 (7)	−0.1079 (3)	0.0272 (7)
C16	0.3388 (2)	0.17196 (7)	−0.2082 (3)	0.0296 (7)
C17	0.4815 (2)	0.16334 (8)	−0.2006 (3)	0.0299 (7)
C18	0.5410 (2)	0.13723 (7)	−0.0931 (2)	0.0252 (7)
C19	0.4587 (2)	0.05174 (6)	0.1439 (2)	0.0204 (6)
C20	0.5015 (2)	0.03015 (7)	0.2715 (2)	0.0238 (6)
C21	0.4490 (2)	−0.00941 (7)	0.2924 (2)	0.0274 (7)
C22	0.3528 (2)	−0.02705 (7)	0.1882 (2)	0.0262 (7)
C23	0.3110 (2)	−0.00517 (7)	0.0626 (2)	0.0261 (7)
C24	0.3641 (2)	0.03414 (7)	0.0386 (2)	0.0241 (6)
C25	1.2505 (3)	0.09211 (8)	0.4574 (3)	0.0380 (8)
C26	1.1132 (2)	0.07829 (7)	0.3829 (2)	0.0259 (7)
C27	1.0882 (2)	0.03647 (7)	0.3542 (3)	0.0315 (7)
C28	0.9644 (2)	0.01997 (7)	0.2893 (2)	0.0257 (7)
C29	0.9515 (3)	−0.02542 (7)	0.2557 (3)	0.0345 (8)
H1	0.928 (3)	0.1690 (9)	0.292 (3)	0.039 (8)*
H2	0.58380	0.23430	0.04890	0.0320*
H3	0.34360	0.24010	0.07040	0.0380*
H4	0.24410	0.21150	0.27250	0.0410*
H5	0.38560	0.17870	0.45640	0.0390*
H6	0.62720	0.17350	0.43980	0.0330*
H8	0.75300	0.28000	0.28360	0.0430*
H9	0.88540	0.33460	0.19790	0.0590*
H10	1.06120	0.32110	0.04210	0.0650*
H11	1.10770	0.25360	−0.02570	0.0560*
H12	0.97640	0.19790	0.05800	0.0390*
H14	0.25780	0.11710	0.07210	0.0300*
H15	0.15800	0.15980	−0.11440	0.0330*
H16	0.29840	0.19000	−0.28230	0.0360*
H17	0.53830	0.17550	−0.26960	0.0360*
H18	0.63830	0.13120	−0.08840	0.0300*
H20	0.56590	0.04230	0.34340	0.0290*
H21	0.47890	−0.02460	0.37830	0.0330*
H22	0.31610	−0.05400	0.20360	0.0310*
H23	0.24510	−0.01710	−0.00840	0.0310*
H24	0.33610	0.04890	−0.04890	0.0290*
H25A	1.29850	0.11010	0.39110	0.0570*
H25B	1.30890	0.06780	0.48280	0.0570*
H25C	1.23390	0.10750	0.54690	0.0570*
H27	1.16190	0.01760	0.38120	0.0380*
H29A	0.85890	−0.03530	0.27850	0.0520*
H29B	1.02400	−0.04070	0.31510	0.0520*
H29C	0.96300	−0.03000	0.15140	0.0520*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0180 (1)	0.0146 (1)	0.0227 (1)	−0.0005 (1)	−0.0028 (1)	0.0006 (1)
Br1	0.0241 (1)	0.0284 (1)	0.0307 (1)	−0.0020 (1)	0.0060 (1)	−0.0039 (1)
Br2	0.0391 (1)	0.0259 (1)	0.0226 (1)	−0.0065 (1)	−0.0034 (1)	0.0040 (1)
O1	0.0217 (8)	0.0211 (8)	0.0353 (9)	0.0005 (6)	−0.0063 (7)	−0.0004 (6)
O2	0.0245 (8)	0.0169 (7)	0.0311 (8)	0.0017 (6)	−0.0049 (6)	0.0005 (6)
N1	0.0207 (10)	0.0171 (9)	0.0244 (9)	0.0010 (7)	−0.0014 (8)	0.0006 (7)
N2	0.0248 (9)	0.0147 (9)	0.0333 (10)	0.0015 (7)	0.0008 (8)	0.0041 (8)
N3	0.0206 (9)	0.0154 (8)	0.0208 (9)	−0.0014 (7)	0.0010 (7)	0.0008 (7)
N4	0.0172 (9)	0.0213 (9)	0.0246 (9)	−0.0019 (7)	−0.0029 (7)	0.0043 (7)
C1	0.0234 (11)	0.0165 (10)	0.0274 (11)	0.0024 (8)	0.0018 (9)	−0.0032 (8)
C2	0.0297 (12)	0.0218 (11)	0.0294 (12)	0.0020 (9)	0.0009 (10)	0.0001 (9)
C3	0.0312 (13)	0.0257 (12)	0.0372 (13)	0.0056 (10)	−0.0034 (10)	−0.0043 (10)
C4	0.0260 (12)	0.0316 (13)	0.0457 (15)	0.0021 (10)	0.0058 (11)	−0.0102 (11)
C5	0.0375 (14)	0.0292 (13)	0.0327 (13)	−0.0021 (10)	0.0125 (11)	−0.0045 (10)
C6	0.0347 (13)	0.0228 (11)	0.0260 (11)	0.0035 (9)	0.0035 (10)	−0.0023 (9)
C7	0.0244 (11)	0.0207 (11)	0.0307 (12)	−0.0045 (8)	−0.0088 (9)	0.0070 (9)
C8	0.0364 (14)	0.0221 (12)	0.0466 (15)	0.0010 (10)	−0.0128 (11)	0.0052 (11)
C9	0.0506 (18)	0.0220 (13)	0.070 (2)	−0.0098 (12)	−0.0329 (16)	0.0139 (13)
C10	0.0444 (17)	0.0439 (17)	0.069 (2)	−0.0262 (14)	−0.0325 (16)	0.0357 (15)
C11	0.0277 (13)	0.062 (2)	0.0485 (16)	−0.0142 (13)	−0.0088 (12)	0.0283 (15)
C12	0.0289 (13)	0.0319 (13)	0.0351 (13)	−0.0045 (10)	−0.0045 (10)	0.0088 (10)
C13	0.0206 (10)	0.0181 (10)	0.0229 (10)	−0.0017 (8)	−0.0034 (8)	0.0012 (8)
C14	0.0219 (11)	0.0251 (11)	0.0275 (11)	−0.0014 (9)	0.0023 (9)	0.0023 (9)
C15	0.0211 (11)	0.0280 (12)	0.0316 (12)	0.0022 (9)	−0.0039 (9)	0.0009 (10)
C16	0.0324 (13)	0.0286 (12)	0.0265 (12)	0.0010 (10)	−0.0062 (10)	0.0067 (10)
C17	0.0289 (12)	0.0340 (13)	0.0266 (11)	−0.0079 (10)	0.0013 (10)	0.0069 (10)
C18	0.0204 (11)	0.0282 (12)	0.0266 (11)	−0.0024 (9)	−0.0014 (9)	0.0014 (9)
C19	0.0177 (10)	0.0183 (10)	0.0255 (11)	−0.0009 (8)	0.0031 (8)	−0.0001 (8)
C20	0.0236 (11)	0.0249 (11)	0.0225 (11)	−0.0035 (9)	−0.0003 (9)	0.0009 (9)
C21	0.0320 (12)	0.0248 (12)	0.0255 (11)	−0.0033 (9)	0.0024 (9)	0.0054 (9)
C22	0.0307 (12)	0.0194 (11)	0.0291 (12)	−0.0052 (9)	0.0070 (10)	−0.0011 (9)
C23	0.0257 (11)	0.0257 (12)	0.0264 (11)	−0.0064 (9)	−0.0005 (9)	−0.0048 (9)
C24	0.0251 (11)	0.0252 (11)	0.0216 (11)	−0.0016 (9)	−0.0006 (9)	0.0015 (9)
C25	0.0255 (13)	0.0363 (14)	0.0501 (16)	0.0037 (10)	−0.0107 (11)	−0.0099 (12)
C26	0.0206 (11)	0.0294 (12)	0.0273 (11)	0.0038 (9)	−0.0001 (9)	−0.0007 (9)
C27	0.0263 (12)	0.0274 (12)	0.0392 (14)	0.0106 (10)	−0.0075 (10)	−0.0061 (10)
C28	0.0311 (12)	0.0209 (11)	0.0246 (11)	0.0038 (9)	−0.0005 (9)	−0.0001 (9)
C29	0.0399 (14)	0.0213 (12)	0.0405 (14)	0.0071 (10)	−0.0082 (11)	−0.0053 (10)

Geometric parameters (Å, º) top

Mo1—Br1	2.6023 (5)	C20—C21	1.388 (3)
Mo1—Br2	2.5646 (4)	C21—C22	1.393 (3)
Mo1—O1	2.1074 (16)	C22—C23	1.379 (3)
Mo1—O2	2.0530 (13)	C23—C24	1.388 (3)
Mo1—N1	1.9638 (16)	C25—C26	1.500 (3)
Mo1—N3	1.7559 (18)	C26—C27	1.389 (3)
O1—C26	1.285 (3)	C27—C28	1.389 (3)
O2—C28	1.284 (2)	C28—C29	1.496 (3)
N1—N2	1.355 (2)	C2—H2	0.9500
N2—C1	1.419 (3)	C3—H3	0.9500
N2—C7	1.423 (3)	C4—H4	0.9500
N3—N4	1.316 (2)	C5—H5	0.9500
N4—C13	1.441 (3)	C6—H6	0.9500
N4—C19	1.441 (3)	C8—H8	0.9500
N1—H1	0.85 (3)	C9—H9	0.9500
C1—C6	1.389 (3)	C10—H10	0.9500
C1—C2	1.395 (3)	C11—H11	0.9500
C2—C3	1.382 (3)	C12—H12	0.9500
C3—C4	1.387 (4)	C14—H14	0.9500
C4—C5	1.382 (4)	C15—H15	0.9500
C5—C6	1.386 (4)	C16—H16	0.9500
C7—C12	1.388 (3)	C17—H17	0.9500
C7—C8	1.390 (3)	C18—H18	0.9500
C8—C9	1.385 (4)	C20—H20	0.9500
C9—C10	1.386 (5)	C21—H21	0.9500
C10—C11	1.370 (4)	C22—H22	0.9500
C11—C12	1.397 (4)	C23—H23	0.9500
C13—C14	1.394 (3)	C24—H24	0.9500
C13—C18	1.388 (3)	C25—H25A	0.9800
C14—C15	1.383 (3)	C25—H25B	0.9800
C15—C16	1.384 (3)	C25—H25C	0.9800
C16—C17	1.392 (3)	C27—H27	0.9500
C17—C18	1.381 (3)	C29—H29A	0.9800
C19—C24	1.389 (3)	C29—H29B	0.9800
C19—C20	1.392 (3)	C29—H29C	0.9800

Br1—Mo1—Br2	167.70 (1)	O1—C26—C25	115.3 (2)
Br1—Mo1—O1	85.51 (4)	O1—C26—C27	124.39 (18)
Br1—Mo1—O2	84.42 (4)	C26—C27—C28	125.5 (2)
Br1—Mo1—N1	88.90 (5)	C27—C28—C29	121.0 (2)
Br1—Mo1—N3	93.70 (6)	O2—C28—C27	124.1 (2)
Br2—Mo1—O1	85.17 (5)	O2—C28—C29	114.94 (19)
Br2—Mo1—O2	86.63 (4)	C1—C2—H2	120.00
Br2—Mo1—N1	97.29 (5)	C3—C2—H2	120.00
Br2—Mo1—N3	95.49 (6)	C2—C3—H3	120.00
O1—Mo1—O2	83.91 (6)	C4—C3—H3	120.00
O1—Mo1—N1	79.66 (7)	C3—C4—H4	120.00
O1—Mo1—N3	178.77 (7)	C5—C4—H4	120.00
O2—Mo1—N1	162.71 (7)	C4—C5—H5	120.00
O2—Mo1—N3	95.07 (7)	C6—C5—H5	120.00
N1—Mo1—N3	101.28 (8)	C1—C6—H6	121.00
Mo1—O1—C26	130.03 (14)	C5—C6—H6	121.00
Mo1—O2—C28	131.95 (13)	C7—C8—H8	120.00
Mo1—N1—N2	140.98 (15)	C9—C8—H8	120.00
Mo1—N3—N4	171.87 (14)	C8—C9—H9	120.00
N1—N2—C1	119.35 (16)	C10—C9—H9	120.00
N1—N2—C7	118.28 (17)	C9—C10—H10	120.00
C1—N2—C7	122.35 (16)	C11—C10—H10	120.00
N3—N4—C13	117.61 (16)	C10—C11—H11	119.00
N3—N4—C19	118.70 (16)	C12—C11—H11	120.00
C13—N4—C19	122.14 (16)	C7—C12—H12	121.00
Mo1—N1—H1	107 (2)	C11—C12—H12	121.00
N2—N1—H1	111 (2)	C13—C14—H14	120.00
N2—C1—C2	119.38 (17)	C15—C14—H14	120.00
C2—C1—C6	120.8 (2)	C14—C15—H15	120.00
N2—C1—C6	119.83 (19)	C16—C15—H15	120.00
C1—C2—C3	119.3 (2)	C15—C16—H16	120.00
C2—C3—C4	120.4 (3)	C17—C16—H16	120.00
C3—C4—C5	119.8 (3)	C16—C17—H17	120.00
C4—C5—C6	120.8 (3)	C18—C17—H17	120.00
C1—C6—C5	118.9 (2)	C13—C18—H18	120.00
C8—C7—C12	121.2 (2)	C17—C18—H18	120.00
N2—C7—C12	119.0 (2)	C19—C20—H20	120.00
N2—C7—C8	119.8 (2)	C21—C20—H20	120.00
C7—C8—C9	119.2 (3)	C20—C21—H21	120.00
C8—C9—C10	120.2 (3)	C22—C21—H21	120.00
C9—C10—C11	120.2 (3)	C21—C22—H22	120.00
C10—C11—C12	120.9 (3)	C23—C22—H22	120.00
C7—C12—C11	118.4 (2)	C22—C23—H23	120.00
N4—C13—C14	119.16 (17)	C24—C23—H23	120.00
C14—C13—C18	120.74 (18)	C19—C24—H24	120.00
N4—C13—C18	120.10 (17)	C23—C24—H24	120.00
C13—C14—C15	119.33 (18)	C26—C25—H25A	109.00
C14—C15—C16	120.26 (18)	C26—C25—H25B	110.00
C15—C16—C17	120.0 (2)	C26—C25—H25C	110.00
C16—C17—C18	120.3 (2)	H25A—C25—H25B	109.00
C13—C18—C17	119.32 (18)	H25A—C25—H25C	109.00
C20—C19—C24	120.65 (19)	H25B—C25—H25C	109.00
N4—C19—C24	120.07 (17)	C26—C27—H27	117.00
N4—C19—C20	119.25 (17)	C28—C27—H27	117.00
C19—C20—C21	119.21 (18)	C28—C29—H29A	110.00
C20—C21—C22	120.48 (18)	C28—C29—H29B	109.00
C21—C22—C23	119.6 (2)	C28—C29—H29C	109.00
C22—C23—C24	120.77 (18)	H29A—C29—H29B	109.00
C19—C24—C23	119.29 (18)	H29A—C29—H29C	109.00
C25—C26—C27	120.34 (19)	H29B—C29—H29C	110.00

Br1—Mo1—O1—C26	−86.31 (17)	C6—C1—C2—C3	−0.2 (3)
Br2—Mo1—O1—C26	85.66 (17)	N2—C1—C2—C3	−178.7 (2)
O2—Mo1—O1—C26	−1.46 (17)	C2—C1—C6—C5	0.7 (3)
N1—Mo1—O1—C26	−176.01 (18)	C1—C2—C3—C4	−0.6 (4)
Br1—Mo1—O2—C28	83.01 (17)	C2—C3—C4—C5	0.9 (4)
Br2—Mo1—O2—C28	−88.54 (17)	C3—C4—C5—C6	−0.3 (4)
O1—Mo1—O2—C28	−3.05 (17)	C4—C5—C6—C1	−0.5 (4)
N3—Mo1—O2—C28	176.24 (17)	N2—C7—C12—C11	−179.3 (2)
Br1—Mo1—N1—N2	90.8 (2)	N2—C7—C8—C9	179.4 (3)
Br2—Mo1—N1—N2	−99.9 (2)	C8—C7—C12—C11	−0.1 (4)
O1—Mo1—N1—N2	176.5 (2)	C12—C7—C8—C9	0.1 (4)
N3—Mo1—N1—N2	−2.7 (2)	C7—C8—C9—C10	0.2 (5)
Mo1—O1—C26—C25	−176.12 (15)	C8—C9—C10—C11	−0.4 (5)
Mo1—O1—C26—C27	3.4 (3)	C9—C10—C11—C12	0.5 (5)
Mo1—O2—C28—C27	5.7 (3)	C10—C11—C12—C7	−0.2 (4)
Mo1—O2—C28—C29	−174.32 (15)	C18—C13—C14—C15	1.0 (3)
Mo1—N1—N2—C1	36.7 (3)	N4—C13—C14—C15	−178.12 (19)
Mo1—N1—N2—C7	−141.8 (2)	C14—C13—C18—C17	0.0 (3)
C7—N2—C1—C6	−138.8 (2)	N4—C13—C18—C17	179.2 (2)
N1—N2—C7—C8	−140.8 (2)	C13—C14—C15—C16	−1.6 (3)
N1—N2—C1—C2	−138.6 (2)	C14—C15—C16—C17	1.2 (4)
N1—N2—C7—C12	38.5 (3)	C15—C16—C17—C18	−0.1 (4)
C7—N2—C1—C2	39.8 (3)	C16—C17—C18—C13	−0.5 (4)
C1—N2—C7—C8	40.8 (3)	C20—C19—C24—C23	0.8 (3)
N1—N2—C1—C6	42.8 (3)	C24—C19—C20—C21	0.3 (3)
C1—N2—C7—C12	−139.9 (2)	N4—C19—C24—C23	178.77 (18)
N3—N4—C13—C18	37.7 (3)	N4—C19—C20—C21	−177.72 (18)
C13—N4—C19—C20	−166.35 (18)	C19—C20—C21—C22	−1.1 (3)
N3—N4—C19—C24	−149.82 (19)	C20—C21—C22—C23	0.8 (3)
N3—N4—C19—C20	28.2 (3)	C21—C22—C23—C24	0.3 (3)
C13—N4—C19—C24	15.6 (3)	C22—C23—C24—C19	−1.1 (3)
C19—N4—C13—C14	51.2 (3)	O1—C26—C27—C28	−1.1 (4)
N3—N4—C13—C14	−143.23 (19)	C25—C26—C27—C28	178.4 (2)
C19—N4—C13—C18	−128.0 (2)	C26—C27—C28—C29	176.5 (2)
N2—C1—C6—C5	179.3 (2)	C26—C27—C28—O2	−3.5 (4)

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[MoBr₂(C₁₂H₁₁N₂)(C₁₂H₁₀N₂)(C₅H₇O₂)]
M_r	720.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.5828 (11), 32.187 (4), 9.1455 (10)
β (°)	94.601 (2)
V (Å³)	2811.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.34
Crystal size (mm)	0.36 × 0.31 × 0.29

Data collection
Diffractometer	Bruker D8 Discover with SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.324, 0.379
No. of measured, independent and observed [I > 2σ(I)] reflections	22331, 5678, 5133
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.063, 1.05
No. of reflections	5678
No. of parameters	349
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

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

References

Bruker (2000). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bustos, C., Manzur, C., Carrillo, D., Robert, F. & Gouzerh, P. (1994). Inorg. Chem. 33, 1427–1433. CrossRef CAS Google Scholar
Bustos, C., Sánchez, C., Schott, E., Garland, M. T. & Alvarez-Thon, L. (2006). Acta Cryst. E62, m3104–m3106. Web of Science CSD CrossRef IUCr Journals Google Scholar
Henderson, R. A., Leigh, G. J. & Pickett, C. J. (1983). Adv. Inorg. Radiochem. 27, 197–292. CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
McCleverty, J. A. (1987). Transition Met. Chem. 12, 282–287. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 6| June 2011| Pages m675-m676

doi:10.1107/S1600536811015881

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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