(Nitrato-κO)oxido(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)molybdenum(V) benzene solvate

Carter, S.M.; Xu, N.; Khan, M.A.; Powell, D.R.; Richter-Addo, G.B.

doi:10.1107/S1600536808030705

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1337

doi:10.1107/S1600536808030705

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(Nitrato-κO)oxido(5,10,15,20-tetraphenylporphyrinato-κ⁴N)molybdenum(V) benzene solvate

Shawn M. Carter,^a Nan Xu,^a Masood A. Khan,^a Douglas R. Powell ^a and George B. Richter-Addo ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, OK 73019, USA
^*Correspondence e-mail: grichteraddo@ou.edu

(Received 19 September 2008; accepted 23 September 2008; online 27 September 2008)

In the title compound, [Mo(C₄₄H₂₈N₄)(NO₃)O]·C₆H₆, the porphyrin ring is centrosymmetric. The Mo atom, oxide ion and nitrate ion are equally disordered over two sites, such that the Mo atom is displaced by 0.366 (1) Å towards the oxide ion from the 24-atom mean plane of the porphyrin, and also makes a long Mo—O bond to a nitrate O atom. A centrosymmetric benzene solvent molecule is situated between adjacent porphyrin molecules.

Related literature

For the structure of (TPP)Mo(O)(ONO₂) (TPP is the tetraphenylporphyrinate dianion) with CH₂Cl₂ as the solvate, see: Okubo et al. (1999 ). For the crystal structures of related molybdenum(V)-oxo porphyrin complexes, see: Harada et al. (2004 ); Kim et al. (1987 ); Hamstra et al. (1999 ); Fujihara et al. (2002 ); Ledon & Mentzen (1978 ); Liu et al. (2001 ); Imamura & Furusaki (1990 ); Cheng & Scheidt (1996 ).

Experimental

Crystal data

[Mo(C₄₄H₂₈N₄)(NO₃)O]·C₆H₆
M_r = 864.76
Triclinic, $[P \overline 1]$
a = 8.6846 (14) Å
b = 11.2895 (18) Å
c = 11.7180 (18) Å
α = 61.617 (5)°
β = 79.283 (6)°
γ = 76.354 (6)°
V = 978.6 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 120 (2) K
0.16 × 0.08 × 0.02 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.938, T_max = 0.994
10263 measured reflections
3836 independent reflections
3395 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.108
S = 1.16
3836 reflections
298 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—O1	1.678 (9)
Mo1—N1ⁱ	2.039 (2)
Mo1—N2ⁱ	2.044 (2)
Mo1—N2	2.139 (2)
Mo1—N1	2.159 (2)
Mo1—O2	2.227 (9)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030705/hb2799sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030705/hb2799Isup2.hkl

checkCIF report

Comment top

In this paper, we report the structure of the title compound, (I), a six-coordinate nitrate molybdenum(V)-oxo tetraphenylporphyrin with benzene as solvate, and the new approach to synthesize the compound using oxochloromolybdenum tetraphenylporphyrin as the precursor. The structure of the related compound with CH₂Cl₂ as solvate has been reported previously (Okubo et al. 1999).

The molecular structure of (I) is shown in Fig. 1. Both the metal complex and the benzene molecule were found to sit on a crystallographic center of symmetry. The porphyrin core of the compound has a slight wave shape. The Mo atom is displaced by 0.366 (1) Å from the 24-atom mean porphyrin plane toward the oxo ion. The nitrate ligand binds to the molybdenum atom through one of its oxygen atoms. Selected bond lengths are given in Table 1. The Mo(V)═O distance of 1.678 (9) Å in (I) is in the range of those [1.658 (2)–1.722 (6) Å] reported previously for other molybdenum(V)-oxo porphyrin complexes (Harada et al., 2004; Kim et al., 1987; Hamstra et al., 1999; Fujihara et al., 2002; Ledon & Mentzen, 1978; Liu et al., 2001; Imamura & Furusaki, 1990; Cheng & Scheidt, 1996). The O═Mo—O linkage in (I) is essentially linear with a bond angle of 174.4 (16)°. A benzene molecule is situated between two adjacent porphyrin molecules with 1:1 benzene/porphyrin stoichiometry.

Related literature top

For the structure of (TPP)Mo(O)(ONO₂) (TPP = tetraphenylporphyrin) with CH₂Cl₂ as the solvate, see: Okubo et al. (1999). For the crystal structures of related molybdenum(V)-oxo porphyrin complexes, see: Harada et al. (2004); Kim et al. (1987); Hamstra et al. (1999); Fujihara et al. (2002); Ledon & Mentzen (1978); Liu et al. (2001); Imamura & Furusaki (1990); Cheng & Scheidt (1996).

Experimental top

To a toluene solution (20 ml) of (TPP)Mo(O)Cl (0.015 g, 0.020 mmol) (Ledon & Mentzen, 1978) under nitrogen was added LiAlH₄ (0.0016 g, 0.42 mmol) (Aldrich Chemical Company, used as received). Then, nitric oxide (98%; Matheson Gas, purified by passing through KOH pellets and a cold trap (dry ice/acetone) to remove higher nitrogen oxides) was bubbled through the mixture for 15 min. The mixture was stirred for an additional 30 min and filtered. A dark green solid was obtained after removal of solvent under vacuum. A suitable dark green prism-shaped crystal of (I) was grown by slow evaporation of a benzene solution of the product at room temperature under nitrogen.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level (H atoms omitted for clarity). The unlabelled atoms of the complex and the benzene molecule are generated by the symmetry operations (1-x, 1-y, 1-z) and (-x, -y, 1-z), respectively.

(Nitrato-κO)oxido(tetraphenylporphyrinato-κ⁴N)molybdenum(V) benzene solvate top

Crystal data top

[Mo(C₄₄H₂₈N₄)(NO₃)O]·C₆H₆	Z = 1
M_r = 864.76	F(000) = 443
Triclinic, P1	D_x = 1.467 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6846 (14) Å	Cell parameters from 7414 reflections
b = 11.2895 (18) Å	θ = 3.2–26.3°
c = 11.7180 (18) Å	µ = 0.39 mm⁻¹
α = 61.617 (5)°	T = 120 K
β = 79.283 (6)°	Prism, green
γ = 76.354 (6)°	0.16 × 0.08 × 0.02 mm
V = 978.6 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3836 independent reflections
Radiation source: fine-focus sealed tube	3395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −10→10
T_min = 0.938, T_max = 0.994	k = −13→13
10263 measured reflections	l = −14→14

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.032P)² + P] where P = (F_o² + 2F_c²)/3
3836 reflections	(Δ/σ)_max < 0.001
298 parameters	Δρ_max = 0.43 e Å⁻³
3 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Mo(C₄₄H₂₈N₄)(NO₃)O]·C₆H₆	γ = 76.354 (6)°
M_r = 864.76	V = 978.6 (3) Å³
Triclinic, P1	Z = 1
a = 8.6846 (14) Å	Mo Kα radiation
b = 11.2895 (18) Å	µ = 0.39 mm⁻¹
c = 11.7180 (18) Å	T = 120 K
α = 61.617 (5)°	0.16 × 0.08 × 0.02 mm
β = 79.283 (6)°

Data collection top

Bruker SMART APEX CCD diffractometer	3836 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3395 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.994	R_int = 0.023
10263 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.16	Δρ_max = 0.43 e Å⁻³
3836 reflections	Δρ_min = −0.47 e Å⁻³
298 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	Occ. (<1)
Mo1	0.47549 (6)	0.53402 (4)	0.48115 (5)	0.02365 (15)	0.50
O1	0.354 (3)	0.668 (2)	0.380 (2)	0.031 (3)	0.50
O2	0.652 (3)	0.356 (2)	0.598 (2)	0.035 (3)	0.50
N3	0.6402 (5)	0.2554 (5)	0.7138 (5)	0.0285 (10)	0.50
O4	0.5111 (4)	0.2409 (4)	0.7791 (4)	0.0340 (9)	0.50
O3	0.7618 (5)	0.1698 (4)	0.7537 (4)	0.0369 (9)	0.50
N1	0.3480 (3)	0.3743 (2)	0.5196 (2)	0.0283 (5)
N2	0.6227 (2)	0.4736 (2)	0.3433 (2)	0.0275 (5)
C1	0.2198 (3)	0.3414 (3)	0.6109 (3)	0.0289 (6)
C2	0.1423 (3)	0.2553 (3)	0.5895 (3)	0.0335 (6)
H2	0.0503	0.2181	0.6382	0.040*
C3	0.2241 (3)	0.2368 (3)	0.4875 (3)	0.0323 (6)
H3	0.1994	0.1845	0.4516	0.039*
C4	0.3545 (3)	0.3100 (3)	0.4433 (2)	0.0272 (6)
C5	0.4674 (3)	0.3184 (3)	0.3386 (2)	0.0275 (6)
C6	0.5898 (3)	0.3952 (3)	0.2919 (2)	0.0275 (6)
C7	0.7039 (3)	0.4052 (3)	0.1842 (3)	0.0310 (6)
H7	0.7085	0.3621	0.1307	0.037*
C8	0.8043 (3)	0.4869 (3)	0.1715 (3)	0.0314 (6)
H8	0.8924	0.5105	0.1083	0.038*
C9	0.7534 (3)	0.5311 (3)	0.2710 (3)	0.0294 (6)
C10	0.8261 (3)	0.6181 (3)	0.2904 (3)	0.0288 (6)
C11	0.4563 (3)	0.2361 (3)	0.2711 (3)	0.0287 (6)
C12	0.3794 (4)	0.2953 (3)	0.1587 (3)	0.0498 (9)
H12	0.3345	0.3897	0.1219	0.060*
C13	0.3678 (5)	0.2168 (3)	0.0993 (3)	0.0553 (10)
H13	0.3158	0.2583	0.0214	0.066*
C14	0.4304 (4)	0.0806 (3)	0.1518 (3)	0.0380 (7)
H14	0.4194	0.0271	0.1121	0.046*
C15	0.5086 (3)	0.0221 (3)	0.2614 (3)	0.0354 (6)
H15	0.5536	−0.0722	0.2976	0.042*
C16	0.5226 (3)	0.1001 (3)	0.3206 (3)	0.0326 (6)
H16	0.5789	0.0588	0.3962	0.039*
C17	0.9593 (3)	0.6766 (3)	0.1930 (3)	0.0300 (6)
C18	1.1139 (4)	0.6125 (3)	0.2087 (3)	0.0480 (8)
H18	1.1393	0.5289	0.2842	0.058*
C19	1.2343 (4)	0.6692 (4)	0.1146 (4)	0.0599 (10)
H19	1.3417	0.6248	0.1263	0.072*
C20	1.1979 (4)	0.7891 (4)	0.0050 (3)	0.0495 (9)
H20	1.2803	0.8280	−0.0590	0.059*
C21	1.0445 (4)	0.8521 (3)	−0.0122 (3)	0.0480 (8)
H21	1.0194	0.9340	−0.0892	0.058*
C22	0.9241 (4)	0.7975 (3)	0.0823 (3)	0.0412 (7)
H22	0.8172	0.8433	0.0707	0.049*
C26	0.0430 (5)	−0.0977 (4)	0.6200 (4)	0.0581 (10)
H26	0.0726	−0.1658	0.7037	0.070*
C27	−0.0779 (4)	0.0081 (4)	0.6088 (4)	0.0515 (9)
H27	−0.1319	0.0135	0.6850	0.062*
C28	−0.1220 (4)	0.1060 (4)	0.4897 (4)	0.0566 (9)
H28	−0.2066	0.1794	0.4823	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0272 (3)	0.0225 (3)	0.0250 (3)	−0.0065 (2)	0.0001 (2)	−0.0135 (3)
O1	0.043 (4)	0.030 (6)	0.011 (5)	−0.001 (4)	0.002 (3)	−0.006 (5)
O2	0.035 (4)	0.038 (6)	0.026 (8)	−0.004 (4)	−0.008 (5)	−0.008 (5)
N3	0.024 (2)	0.033 (3)	0.039 (3)	−0.005 (2)	0.002 (2)	−0.026 (3)
O4	0.035 (2)	0.028 (2)	0.037 (2)	−0.0094 (16)	0.0041 (17)	−0.0134 (18)
O3	0.036 (2)	0.029 (2)	0.044 (2)	−0.0025 (17)	−0.0056 (18)	−0.0156 (19)
N1	0.0291 (12)	0.0361 (13)	0.0240 (11)	−0.0124 (10)	0.0033 (9)	−0.0160 (10)
N2	0.0271 (12)	0.0343 (13)	0.0255 (11)	−0.0119 (9)	0.0022 (9)	−0.0156 (10)
C1	0.0284 (14)	0.0314 (14)	0.0267 (14)	−0.0088 (11)	0.0002 (11)	−0.0123 (12)
C2	0.0318 (15)	0.0360 (16)	0.0354 (16)	−0.0125 (12)	0.0014 (12)	−0.0167 (13)
C3	0.0351 (15)	0.0309 (15)	0.0348 (15)	−0.0095 (12)	−0.0004 (12)	−0.0172 (13)
C4	0.0297 (14)	0.0276 (14)	0.0252 (13)	−0.0069 (11)	−0.0018 (11)	−0.0120 (11)
C5	0.0311 (14)	0.0268 (14)	0.0251 (13)	−0.0055 (11)	−0.0026 (11)	−0.0117 (11)
C6	0.0306 (14)	0.0264 (14)	0.0237 (13)	−0.0040 (11)	−0.0020 (11)	−0.0102 (11)
C7	0.0389 (16)	0.0281 (14)	0.0264 (14)	−0.0062 (12)	0.0014 (12)	−0.0140 (12)
C8	0.0344 (15)	0.0308 (15)	0.0267 (14)	−0.0086 (12)	0.0042 (11)	−0.0122 (12)
C9	0.0301 (14)	0.0334 (15)	0.0252 (14)	−0.0080 (11)	0.0008 (11)	−0.0135 (12)
C10	0.0268 (14)	0.0320 (14)	0.0267 (14)	−0.0079 (11)	0.0017 (11)	−0.0125 (12)
C11	0.0310 (14)	0.0313 (14)	0.0266 (14)	−0.0109 (11)	0.0038 (11)	−0.0149 (12)
C12	0.075 (2)	0.0312 (16)	0.0470 (19)	0.0034 (16)	−0.0252 (17)	−0.0198 (15)
C13	0.083 (3)	0.0436 (19)	0.047 (2)	0.0021 (18)	−0.0304 (19)	−0.0239 (17)
C14	0.0465 (18)	0.0402 (17)	0.0360 (16)	−0.0147 (14)	0.0011 (13)	−0.0224 (14)
C15	0.0397 (16)	0.0299 (15)	0.0363 (16)	−0.0106 (12)	0.0029 (13)	−0.0148 (13)
C16	0.0373 (16)	0.0329 (15)	0.0275 (14)	−0.0085 (12)	−0.0033 (12)	−0.0123 (12)
C17	0.0328 (15)	0.0342 (15)	0.0290 (14)	−0.0126 (12)	0.0038 (11)	−0.0183 (12)
C18	0.0372 (18)	0.0411 (18)	0.049 (2)	−0.0083 (14)	0.0055 (14)	−0.0095 (15)
C19	0.0358 (19)	0.058 (2)	0.072 (3)	−0.0119 (16)	0.0178 (17)	−0.025 (2)
C20	0.061 (2)	0.048 (2)	0.048 (2)	−0.0306 (17)	0.0262 (17)	−0.0293 (17)
C21	0.069 (2)	0.0421 (18)	0.0316 (17)	−0.0245 (17)	0.0027 (15)	−0.0112 (14)
C22	0.0448 (18)	0.0402 (17)	0.0358 (17)	−0.0139 (14)	−0.0026 (14)	−0.0122 (14)
C26	0.064 (2)	0.046 (2)	0.056 (2)	−0.0140 (18)	−0.0220 (19)	−0.0079 (17)
C27	0.0438 (19)	0.062 (2)	0.057 (2)	−0.0220 (17)	−0.0022 (16)	−0.0294 (19)
C28	0.047 (2)	0.046 (2)	0.082 (3)	0.0000 (16)	−0.0212 (19)	−0.031 (2)

Geometric parameters (Å, º) top

Mo1—O1	1.678 (9)	C10—C17	1.493 (4)
Mo1—N1ⁱ	2.039 (2)	C11—C16	1.373 (4)
Mo1—N2ⁱ	2.044 (2)	C11—C12	1.380 (4)
Mo1—N2	2.139 (2)	C12—C13	1.391 (4)
Mo1—N1	2.159 (2)	C12—H12	0.9500
Mo1—O2	2.227 (9)	C13—C14	1.367 (4)
O2—N3	1.30 (2)	C13—H13	0.9500
N3—O4	1.232 (6)	C14—C15	1.361 (4)
N3—O3	1.241 (6)	C14—H14	0.9500
N1—C1	1.377 (3)	C15—C16	1.391 (4)
N1—C4	1.382 (3)	C15—H15	0.9500
N1—Mo1ⁱ	2.039 (2)	C16—H16	0.9500
N2—C9	1.377 (3)	C17—C18	1.366 (4)
N2—C6	1.385 (3)	C17—C22	1.381 (4)
N2—Mo1ⁱ	2.044 (2)	C18—C19	1.391 (4)
C1—C10ⁱ	1.398 (4)	C18—H18	0.9500
C1—C2	1.436 (4)	C19—C20	1.370 (5)
C2—C3	1.352 (4)	C19—H19	0.9500
C2—H2	0.9500	C20—C21	1.356 (5)
C3—C4	1.432 (4)	C20—H20	0.9500
C3—H3	0.9500	C21—C22	1.387 (4)
C4—C5	1.400 (4)	C21—H21	0.9500
C5—C6	1.395 (4)	C22—H22	0.9500
C5—C11	1.507 (3)	C26—C27	1.363 (5)
C6—C7	1.428 (4)	C26—C28ⁱⁱ	1.374 (5)
C7—C8	1.354 (4)	C26—H26	0.9500
C7—H7	0.9500	C27—C28	1.360 (5)
C8—C9	1.436 (4)	C27—H27	0.9500
C8—H8	0.9500	C28—C26ⁱⁱ	1.374 (5)
C9—C10	1.404 (4)	C28—H28	0.9500
C10—C1ⁱ	1.398 (4)

O1—Mo1—N1ⁱ	101.6 (11)	C9—C8—H8	126.2
O1—Mo1—N2ⁱ	100.8 (9)	N2—C9—C10	126.3 (2)
N1ⁱ—Mo1—N2ⁱ	90.76 (8)	N2—C9—C8	108.4 (2)
O1—Mo1—N2	99.3 (8)	C10—C9—C8	125.3 (2)
N1ⁱ—Mo1—N2	88.93 (8)	C1ⁱ—C10—C9	125.7 (2)
N2ⁱ—Mo1—N2	159.56 (3)	C1ⁱ—C10—C17	117.6 (2)
O1—Mo1—N1	98.5 (11)	C9—C10—C17	116.7 (2)
N1ⁱ—Mo1—N1	159.74 (3)	C16—C11—C12	118.7 (3)
N2ⁱ—Mo1—N1	88.23 (8)	C16—C11—C5	120.4 (2)
N2—Mo1—N1	85.07 (8)	C12—C11—C5	120.9 (2)
O1—Mo1—O2	174.4 (16)	C11—C12—C13	120.0 (3)
N1ⁱ—Mo1—O2	77.5 (8)	C11—C12—H12	120.0
N2ⁱ—Mo1—O2	84.8 (7)	C13—C12—H12	120.0
N2—Mo1—O2	75.2 (7)	C14—C13—C12	120.6 (3)
N1—Mo1—O2	82.2 (8)	C14—C13—H13	119.7
N3—O2—Mo1	132.5 (17)	C12—C13—H13	119.7
O4—N3—O3	121.0 (5)	C15—C14—C13	119.6 (3)
O4—N3—O2	121.1 (11)	C15—C14—H14	120.2
O3—N3—O2	117.8 (10)	C13—C14—H14	120.2
C1—N1—C4	107.7 (2)	C14—C15—C16	120.1 (3)
C1—N1—Mo1ⁱ	126.60 (17)	C14—C15—H15	119.9
C4—N1—Mo1ⁱ	124.54 (17)	C16—C15—H15	119.9
C1—N1—Mo1	123.63 (17)	C11—C16—C15	120.8 (3)
C4—N1—Mo1	127.31 (17)	C11—C16—H16	119.6
C9—N2—C6	107.7 (2)	C15—C16—H16	119.6
C9—N2—Mo1ⁱ	126.73 (17)	C18—C17—C22	119.2 (3)
C6—N2—Mo1ⁱ	124.14 (17)	C18—C17—C10	122.1 (3)
C9—N2—Mo1	123.49 (17)	C22—C17—C10	118.7 (3)
C6—N2—Mo1	127.58 (17)	C17—C18—C19	120.3 (3)
N1—C1—C10ⁱ	126.1 (2)	C17—C18—H18	119.9
N1—C1—C2	108.4 (2)	C19—C18—H18	119.9
C10ⁱ—C1—C2	125.4 (2)	C20—C19—C18	120.0 (3)
C3—C2—C1	107.7 (2)	C20—C19—H19	120.0
C3—C2—H2	126.2	C18—C19—H19	120.0
C1—C2—H2	126.2	C21—C20—C19	120.0 (3)
C2—C3—C4	107.9 (2)	C21—C20—H20	120.0
C2—C3—H3	126.0	C19—C20—H20	120.0
C4—C3—H3	126.0	C20—C21—C22	120.3 (3)
N1—C4—C5	125.5 (2)	C20—C21—H21	119.9
N1—C4—C3	108.3 (2)	C22—C21—H21	119.9
C5—C4—C3	126.2 (2)	C17—C22—C21	120.2 (3)
C6—C5—C4	126.0 (2)	C17—C22—H22	119.9
C6—C5—C11	117.1 (2)	C21—C22—H22	119.9
C4—C5—C11	116.9 (2)	C27—C26—C28ⁱⁱ	120.0 (3)
N2—C6—C5	125.8 (2)	C27—C26—H26	120.0
N2—C6—C7	108.2 (2)	C28ⁱⁱ—C26—H26	120.0
C5—C6—C7	126.0 (2)	C28—C27—C26	120.6 (4)
C8—C7—C6	108.1 (2)	C28—C27—H27	119.7
C8—C7—H7	125.9	C26—C27—H27	119.7
C6—C7—H7	125.9	C27—C28—C26ⁱⁱ	119.3 (3)
C7—C8—C9	107.5 (2)	C27—C28—H28	120.3
C7—C8—H8	126.2	C26ⁱⁱ—C28—H28	120.3

N1ⁱ—Mo1—O2—N3	126 (3)	C3—C4—C5—C6	176.7 (3)
N2ⁱ—Mo1—O2—N3	34 (2)	N1—C4—C5—C11	178.0 (2)
N2—Mo1—O2—N3	−142 (3)	C3—C4—C5—C11	−3.8 (4)
N1—Mo1—O2—N3	−55 (2)	C9—N2—C6—C5	179.1 (2)
Mo1—O2—N3—O4	4 (3)	Mo1ⁱ—N2—C6—C5	11.8 (4)
Mo1—O2—N3—O3	179.8 (15)	Mo1—N2—C6—C5	−13.2 (4)
O1—Mo1—N1—C1	−82.6 (9)	C9—N2—C6—C7	−0.2 (3)
N1ⁱ—Mo1—N1—C1	105.4 (2)	Mo1ⁱ—N2—C6—C7	−167.48 (17)
N2ⁱ—Mo1—N1—C1	18.0 (2)	Mo1—N2—C6—C7	167.58 (17)
N2—Mo1—N1—C1	178.7 (2)	C4—C5—C6—N2	1.7 (4)
O2—Mo1—N1—C1	103.0 (7)	C11—C5—C6—N2	−177.8 (2)
O1—Mo1—N1—C4	82.4 (9)	C4—C5—C6—C7	−179.2 (3)
N1ⁱ—Mo1—N1—C4	−89.6 (2)	C11—C5—C6—C7	1.3 (4)
N2ⁱ—Mo1—N1—C4	−177.0 (2)	N2—C6—C7—C8	0.5 (3)
N2—Mo1—N1—C4	−16.4 (2)	C5—C6—C7—C8	−178.7 (3)
O2—Mo1—N1—C4	−92.0 (7)	C6—C7—C8—C9	−0.7 (3)
O1—Mo1—N1—Mo1ⁱ	172.0 (9)	C6—N2—C9—C10	179.9 (3)
N1ⁱ—Mo1—N1—Mo1ⁱ	0.0	Mo1ⁱ—N2—C9—C10	−13.2 (4)
N2ⁱ—Mo1—N1—Mo1ⁱ	−87.39 (11)	Mo1—N2—C9—C10	11.6 (4)
N2—Mo1—N1—Mo1ⁱ	73.28 (10)	C6—N2—C9—C8	−0.2 (3)
O2—Mo1—N1—Mo1ⁱ	−2.4 (7)	Mo1ⁱ—N2—C9—C8	166.65 (18)
O1—Mo1—N2—C9	84.7 (11)	Mo1—N2—C9—C8	−168.61 (17)
N1ⁱ—Mo1—N2—C9	−16.9 (2)	C7—C8—C9—N2	0.6 (3)
N2ⁱ—Mo1—N2—C9	−106.2 (2)	C7—C8—C9—C10	−179.6 (3)
N1—Mo1—N2—C9	−177.5 (2)	N2—C9—C10—C1ⁱ	1.8 (4)
O2—Mo1—N2—C9	−94.2 (8)	C8—C9—C10—C1ⁱ	−178.0 (3)
O1—Mo1—N2—C6	−81.3 (11)	N2—C9—C10—C17	−175.5 (2)
N1ⁱ—Mo1—N2—C6	177.2 (2)	C8—C9—C10—C17	4.8 (4)
N2ⁱ—Mo1—N2—C6	87.9 (2)	C6—C5—C11—C16	96.5 (3)
N1—Mo1—N2—C6	16.6 (2)	C4—C5—C11—C16	−83.0 (3)
O2—Mo1—N2—C6	99.8 (8)	C6—C5—C11—C12	−83.6 (3)
O1—Mo1—N2—Mo1ⁱ	−169.1 (11)	C4—C5—C11—C12	96.9 (3)
N1ⁱ—Mo1—N2—Mo1ⁱ	89.31 (11)	C16—C11—C12—C13	1.2 (5)
N2ⁱ—Mo1—N2—Mo1ⁱ	−0.003 (2)	C5—C11—C12—C13	−178.7 (3)
N1—Mo1—N2—Mo1ⁱ	−71.32 (10)	C11—C12—C13—C14	0.7 (6)
O2—Mo1—N2—Mo1ⁱ	11.9 (8)	C12—C13—C14—C15	−1.8 (5)
C4—N1—C1—C10ⁱ	177.8 (3)	C13—C14—C15—C16	0.9 (5)
Mo1ⁱ—N1—C1—C10ⁱ	9.8 (4)	C12—C11—C16—C15	−2.1 (4)
Mo1—N1—C1—C10ⁱ	−14.7 (4)	C5—C11—C16—C15	177.9 (3)
C4—N1—C1—C2	−0.9 (3)	C14—C15—C16—C11	1.0 (4)
Mo1ⁱ—N1—C1—C2	−168.85 (18)	C1ⁱ—C10—C17—C18	92.1 (3)
Mo1—N1—C1—C2	166.57 (17)	C9—C10—C17—C18	−90.4 (3)
N1—C1—C2—C3	0.4 (3)	C1ⁱ—C10—C17—C22	−89.6 (3)
C10ⁱ—C1—C2—C3	−178.3 (3)	C9—C10—C17—C22	87.8 (3)
C1—C2—C3—C4	0.3 (3)	C22—C17—C18—C19	0.6 (5)
C1—N1—C4—C5	179.5 (2)	C10—C17—C18—C19	178.8 (3)
Mo1ⁱ—N1—C4—C5	−12.2 (4)	C17—C18—C19—C20	−0.7 (6)
Mo1—N1—C4—C5	12.7 (4)	C18—C19—C20—C21	−0.4 (6)
C1—N1—C4—C3	1.1 (3)	C19—C20—C21—C22	1.5 (5)
Mo1ⁱ—N1—C4—C3	169.33 (17)	C18—C17—C22—C21	0.5 (4)
Mo1—N1—C4—C3	−165.80 (17)	C10—C17—C22—C21	−177.8 (3)
C2—C3—C4—N1	−0.8 (3)	C20—C21—C22—C17	−1.6 (5)
C2—C3—C4—C5	−179.3 (3)	C28ⁱⁱ—C26—C27—C28	0.3 (6)
N1—C4—C5—C6	−1.5 (4)	C26—C27—C28—C26ⁱⁱ	−0.3 (6)

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

Experimental details

Crystal data
Chemical formula	[Mo(C₄₄H₂₈N₄)(NO₃)O]·C₆H₆
M_r	864.76
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.6846 (14), 11.2895 (18), 11.7180 (18)
α, β, γ (°)	61.617 (5), 79.283 (6), 76.354 (6)
V (Å³)	978.6 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.16 × 0.08 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.938, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	10263, 3836, 3395
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.108, 1.16
No. of reflections	3836
No. of parameters	298
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.47

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mo1—O1	1.678 (9)	Mo1—N2	2.139 (2)
Mo1—N1ⁱ	2.039 (2)	Mo1—N1	2.159 (2)
Mo1—N2ⁱ	2.044 (2)	Mo1—O2	2.227 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank the National Science Foundation (grant Nos. CHE-0079282 and CHE-0076640) and the University of Oklahoma for funds to support this research and to acquire the diffractometer and computers used in this work.

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