Tripyridinium cis-tetra­chlorido­dioxido­molybdate(VI) chloride

Fernandes, J.A.; Gomes, A.C.; Figueiredo, S.; Gago, S.; Ribeiro-Claro, P.J.A.; Gonçalves, I.S.; Almeida Paz, F.A.

doi:10.1107/S1600536810023950

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m862-m863

doi:10.1107/S1600536810023950

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Tripyridinium cis-tetrachloridodioxidomolybdate(VI) chloride

José A. Fernandes,^a Ana C. Gomes,^a Sónia Figueiredo,^a,^b Sandra Gago,^a Paulo J. A. Ribeiro-Claro,^a Isabel S. Gonçalves ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bDepartment of Chemistry, University of Algarve, Campus de Gambelas, 8005-139 Faro, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 6 June 2010; accepted 20 June 2010; online 26 June 2010)

In the title compound, (C₅H₆N)₃[MoCl₄O₂]Cl, the pyridinium cations are N—H⋯Cl hydrogen bonded to the anionic [MoCl₄O₂]²⁻ complexes and to the two crystallographically independent chloride anions (located on C2 axes). The Mo⁶⁺ centre adopts a highly distorted octahedral geometry, being surrounded by four chloride and two terminal oxide groups. The oxide ligands are mutually cis.

Related literature

For a related structure, see: Luan et al. (2008 ). For previous studies by our group on dioxidomolybdenum complexes, see: Monteiro et al. (2010 ); Gago et al. (2009 ); Pereira et al. (2007 ); Cunha-Silva et al. (2007 ); Bruno et al. (2007 ). For graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

(C₅H₆N)₃[MoCl₄O₂]Cl
M_r = 545.51
Trigonal, P 3₁ 21
a = 11.3972 (2) Å
c = 29.4265 (9) Å
V = 3310.28 (13) Å³
Z = 6
Mo Kα radiation
μ = 1.21 mm⁻¹
T = 150 K
0.18 × 0.12 × 0.10 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.811, T_max = 0.888
33230 measured reflections
10395 independent reflections
8105 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.074
S = 1.05
10395 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.68 e Å⁻³
Absolute structure: Flack (1983 ), 4490 Friedel pairs
Flack parameter: 0.03 (4)

Table 1
Selected geometric parameters (Å, °)

Mo1—O2	1.6988 (13)
Mo1—O1	1.7004 (13)
Mo1—Cl2	2.3750 (6)
Mo1—Cl1	2.3995 (6)
Mo1—Cl3	2.5746 (5)
Mo1—Cl4	2.5953 (5)

O2—Mo1—O1	102.11 (7)
O2—Mo1—Cl2	94.45 (6)
O1—Mo1—Cl2	95.78 (6)
O2—Mo1—Cl1	94.06 (6)
O1—Mo1—Cl1	93.64 (6)
Cl2—Mo1—Cl1	165.71 (2)
O2—Mo1—Cl3	169.07 (5)
O1—Mo1—Cl3	88.75 (5)
Cl2—Mo1—Cl3	85.57 (2)
Cl1—Mo1—Cl3	83.91 (2)
O2—Mo1—Cl4	87.40 (5)
O1—Mo1—Cl4	170.36 (5)
Cl2—Mo1—Cl4	84.99 (2)
Cl1—Mo1—Cl4	83.94 (2)
Cl3—Mo1—Cl4	81.717 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl6ⁱ	0.88	2.16	3.0424 (19)	175
N2—H2A⋯Cl5ⁱⁱ	0.88	2.17	3.0304 (19)	166
N3—H3A⋯Cl4	0.88	2.45	3.243 (2)	150
N3—H3A⋯Cl3	0.88	2.69	3.277 (2)	126
Symmetry codes: (i) x, y, z+1; (ii) x-1, y+1, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810023950/sj5018sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023950/sj5018Isup2.hkl

checkCIF report

Comment top

Our research group has been interested in the development of novel catalysts based on dioxomolybdenum complexes (Monteiro et al., 2010; Gago et al., 2009; Pereira et al., 2007; Cunha-Silva et al., 2007; Bruno et al., 2007). During our recent efforts to coordinate pyridine to the molybdenum centre, we have isolated the title compound: [C₅H₆N]₃[MoCl₄O₂]Cl. Remarkably, a search in the literature and in the Cambridge Structural Database (Allen, 2002) reveals the existence of only one other structure with the [MoCl₄O₂]^2- anion (Luan et al., 2008).

The asymmetric unit of the title compound I is composed of three pyridinium (PyH) cations whose charge is balanced by the metallic dianion, [MoCl₄O₂]^2-, and by two chloride anions located at special positions (Cl5 and Cl6 on C₂ axes) The Mo⁶⁺ centre is coordinated by four chloro and two oxo terminal ligands in a distorted octahedral geometry (Figure 1), {MoCl₄O₂}. The Mo—Cl distances range from 2.3750 (6) to 2.5953 (5) Å and the Mo═O distance is either 1.6988 (13) or 1.7004 (13) Å (Table 1). The cis and trans octahedral angles fall within a short range of the ideal values [81.717 (16)—103.11 (7)° and 165.71 (2)—170.36 (5)°, respectively - see Table 1].

The PyH cations are engaged in strong and relatively directional N⁺—H···Cl^- hydrogen bonds with the chloride anions (not shown; Table 2). We note that N3 is interacting with two spatially close chloro ligands (Cl3 and Cl4), forming a R₁²(4) graph set motif (Grell et al.,1999) typical of bifurcated interactions. The crystal packing is, thus, mediated by the need to effectively fill the available space (Figure 2) since no significant supramolecular contacts are present in the crystal structure (e.g., C—H···O or C—H···Cl contacts are all greater than 3.18 Å).

Related literature top

For a related structure, see: Luan et al. (2008). For previous studies by our group on dioxomolybdenum complexes, see: Monteiro et al. (2010); Gago et al. (2009); Pereira et al. (2007); Cunha-Silva et al. (2007); Bruno et al. (2007). For graph-set notation for hydrogen-bonded aggregates, see: Grell et al. (1999). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Chemicals were purchased from commercial sources and were used as received without purification.

To an aqueous solution (30 ml) of HCl (3.3 mol dm^-3) containing 2.0 g (8.3 mmol) of Na₂MoO₄^.2H₂O, a solution of pyridine (1.34 ml, 16.6 mmol) in CH₂Cl₂ (60 ml) was slowly added dropwise. The biphasic mixture was vigorously stirred for 3 h at ambient temperature. The aqueous phase was separated and washed three times with CH₂Cl₂, and then allowed to evaporate yielding a solid. Crystals of the title compound were ultimately isolated by slow diffusion of diethyl ether into a concentrated solution in acetonitrile.

Crystals of the title compound were ultimately isolated by slow diffusion of diethyl ether into a concentrated solution in acetonitrile. Yield: 65%.

¹H NMR (300.13 MHz, 298 K, CD₃CN): δ = 8.75 (d, 2H), 8.56 (t, 1H), 8.03 (t, 2H) p.p.m..

Selected FT—IR (ATR, cm^-1): 923 [vs, ν_sym(Mo═O)], 884 [vs, ν_asym(Mo═O)], 320 [vs, ν(Mo—Cl)].

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 and SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Schematic representation of the asymmetric unit. The [MoCl₄O₂]^2- anion has a highly distorted {MoCl₄O₂} octahedral coordination environment, and the anions Cl5 and Cl6 are located on C2 axes. Thermal ellipsoids are drawn at the 50% probability level. For selected bond lengths (in Å) and angles (in degrees) see Table 1.
	Fig. 2. Crystal packing of the title compound viewed in perspective along the (a) [001] and (b) [110] directions of the unit cell.

Tripyridinium cis-tetrachloridodioxidomolybdate(VI) chloride top

Crystal data top

(C₅H₆N)₃[MoCl₄O₂]Cl	D_x = 1.642 Mg m⁻³
M_r = 545.51	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 6207 reflections
Hall symbol: P 31 2"	θ = 5.5–33.1°
a = 11.3972 (2) Å	µ = 1.21 mm⁻¹
c = 29.4265 (9) Å	T = 150 K
V = 3310.28 (13) Å³	Block, yellow
Z = 6	0.18 × 0.12 × 0.10 mm
F(000) = 1632

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	10395 independent reflections
Radiation source: fine-focus sealed tube	8105 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω & ϕ scans	θ_max = 36.3°, θ_min = 5.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −18→16
T_min = 0.811, T_max = 0.888	k = −17→8
33230 measured reflections	l = −48→49

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0224P)² + 0.183P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
10395 reflections	Δρ_max = 0.46 e Å⁻³
237 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 4490 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (4)

Crystal data top

(C₅H₆N)₃[MoCl₄O₂]Cl	Z = 6
M_r = 545.51	Mo Kα radiation
Trigonal, P3₁21	µ = 1.21 mm⁻¹
a = 11.3972 (2) Å	T = 150 K
c = 29.4265 (9) Å	0.18 × 0.12 × 0.10 mm
V = 3310.28 (13) Å³

Data collection top

Bruker X8 Kappa CCD APEXII diffractometer	10395 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	8105 reflections with I > 2σ(I)
T_min = 0.811, T_max = 0.888	R_int = 0.047
33230 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.074	Δρ_max = 0.46 e Å⁻³
S = 1.05	Δρ_min = −0.68 e Å⁻³
10395 reflections	Absolute structure: Flack (1983), 4490 Friedel pairs
237 parameters	Absolute structure parameter: 0.03 (4)
0 restraints

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
Mo1	0.663054 (16)	0.338004 (17)	0.915715 (4)	0.01643 (3)
O1	0.77729 (15)	0.39544 (18)	0.87246 (4)	0.0238 (3)
O2	0.76505 (15)	0.38526 (17)	0.96219 (4)	0.0233 (3)
Cl1	0.64140 (7)	0.53687 (6)	0.916423 (17)	0.02869 (12)
Cl2	0.62465 (7)	0.11310 (6)	0.914936 (17)	0.02893 (12)
Cl3	0.47182 (5)	0.25297 (6)	0.856354 (14)	0.02601 (11)
Cl4	0.45883 (5)	0.24295 (6)	0.971200 (14)	0.02623 (11)
Cl5	1.00836 (8)	0.0000	0.8333	0.0421 (2)
Cl6	0.94835 (8)	0.94835 (8)	0.0000	0.0352 (2)
N1	0.6973 (2)	0.8428 (2)	0.94054 (6)	0.0266 (4)
H1A	0.7726	0.8765	0.9564	0.032*
N2	0.1156 (2)	0.8720 (2)	0.89938 (5)	0.0306 (4)
H2A	0.0989	0.9161	0.8782	0.037*
N3	0.2586 (2)	0.3111 (2)	0.91300 (7)	0.0333 (5)
H3A	0.3299	0.3029	0.9186	0.040*
C1	0.5793 (3)	0.7649 (3)	0.96154 (7)	0.0289 (5)
H1	0.5782	0.7449	0.9929	0.035*
C2	0.4601 (3)	0.7139 (3)	0.93800 (7)	0.0304 (5)
H2	0.3759	0.6572	0.9526	0.037*
C3	0.4649 (3)	0.7467 (3)	0.89223 (7)	0.0321 (5)
H3	0.3832	0.7154	0.8756	0.039*
C4	0.5876 (3)	0.8244 (3)	0.87119 (7)	0.0313 (6)
H4	0.5916	0.8454	0.8398	0.038*
C5	0.7049 (3)	0.8714 (3)	0.89623 (7)	0.0295 (5)
H5	0.7907	0.9239	0.8821	0.035*
C6	0.2380 (3)	0.9313 (3)	0.91843 (8)	0.0335 (6)
H6	0.3064	1.0183	0.9085	0.040*
C7	0.2645 (3)	0.8657 (3)	0.95249 (8)	0.0327 (6)
H7	0.3501	0.9082	0.9673	0.039*
C8	0.1656 (3)	0.7374 (3)	0.96502 (8)	0.0345 (6)
H8	0.1833	0.6902	0.9882	0.041*
C9	0.0411 (3)	0.6777 (3)	0.94404 (8)	0.0367 (6)
H9	−0.0272	0.5887	0.9522	0.044*
C10	0.0168 (3)	0.7481 (3)	0.91116 (8)	0.0345 (6)
H10	−0.0693	0.7094	0.8969	0.041*
C11	0.1483 (3)	0.2387 (3)	0.93686 (7)	0.0339 (6)
H11	0.1464	0.1775	0.9592	0.041*
C12	0.0362 (3)	0.2502 (3)	0.92996 (8)	0.0361 (6)
H12	−0.0434	0.1989	0.9475	0.043*
C13	0.0413 (3)	0.3393 (3)	0.89645 (9)	0.0395 (6)
H13	−0.0356	0.3487	0.8908	0.047*
C14	0.1574 (3)	0.4132 (3)	0.87173 (9)	0.0389 (7)
H14	0.1618	0.4743	0.8490	0.047*
C15	0.2673 (3)	0.3979 (3)	0.88024 (8)	0.0351 (6)
H15	0.3485	0.4478	0.8633	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01527 (8)	0.01530 (8)	0.01882 (5)	0.00773 (7)	0.00036 (5)	0.00003 (5)
O1	0.0216 (7)	0.0270 (9)	0.0249 (5)	0.0137 (7)	0.0046 (5)	0.0054 (6)
O2	0.0215 (7)	0.0220 (9)	0.0248 (5)	0.0096 (7)	−0.0042 (5)	−0.0012 (6)
Cl1	0.0361 (3)	0.0210 (3)	0.0348 (2)	0.0187 (3)	−0.0008 (2)	−0.0004 (2)
Cl2	0.0381 (4)	0.0186 (3)	0.0334 (2)	0.0167 (3)	0.0018 (2)	−0.0006 (2)
Cl3	0.0213 (2)	0.0335 (3)	0.02208 (16)	0.0128 (2)	−0.00321 (16)	−0.00294 (19)
Cl4	0.0216 (2)	0.0311 (3)	0.02295 (17)	0.0109 (2)	0.00463 (16)	0.00273 (19)
Cl5	0.0355 (3)	0.0628 (7)	0.0371 (3)	0.0314 (3)	0.01181 (18)	0.0236 (4)
Cl6	0.0300 (3)	0.0300 (3)	0.0359 (3)	0.0077 (4)	−0.00797 (16)	0.00797 (16)
N1	0.0273 (10)	0.0259 (11)	0.0312 (7)	0.0169 (10)	−0.0071 (7)	−0.0074 (8)
N2	0.0337 (13)	0.0350 (13)	0.0280 (7)	0.0208 (10)	−0.0009 (8)	0.0038 (8)
N3	0.0245 (12)	0.0311 (13)	0.0480 (11)	0.0166 (10)	0.0007 (9)	0.0044 (9)
C1	0.0393 (14)	0.0348 (14)	0.0213 (7)	0.0250 (12)	0.0004 (8)	−0.0004 (8)
C2	0.0297 (12)	0.0334 (14)	0.0304 (9)	0.0174 (11)	0.0053 (8)	−0.0008 (9)
C3	0.0338 (13)	0.0349 (15)	0.0303 (9)	0.0192 (12)	−0.0104 (8)	−0.0087 (9)
C4	0.0473 (16)	0.0272 (13)	0.0220 (8)	0.0206 (12)	−0.0018 (9)	−0.0011 (8)
C5	0.0323 (13)	0.0228 (13)	0.0340 (9)	0.0141 (11)	0.0068 (9)	0.0018 (9)
C6	0.0337 (15)	0.0233 (13)	0.0389 (11)	0.0108 (12)	0.0003 (10)	0.0010 (10)
C7	0.0234 (13)	0.0319 (14)	0.0363 (10)	0.0091 (11)	−0.0074 (9)	−0.0007 (10)
C8	0.0315 (14)	0.0366 (16)	0.0336 (10)	0.0157 (13)	0.0005 (10)	0.0110 (10)
C9	0.0247 (13)	0.0299 (14)	0.0458 (12)	0.0064 (11)	0.0035 (10)	0.0090 (11)
C10	0.0224 (13)	0.0401 (16)	0.0370 (11)	0.0126 (12)	−0.0048 (10)	−0.0032 (10)
C11	0.0409 (16)	0.0288 (13)	0.0285 (9)	0.0148 (12)	0.0000 (9)	0.0074 (9)
C12	0.0300 (14)	0.0321 (15)	0.0416 (11)	0.0122 (12)	0.0131 (11)	0.0031 (10)
C13	0.0250 (14)	0.0436 (18)	0.0508 (13)	0.0178 (14)	−0.0058 (11)	−0.0029 (12)
C14	0.0353 (15)	0.0410 (18)	0.0414 (12)	0.0200 (14)	−0.0006 (11)	0.0158 (12)
C15	0.0325 (15)	0.0338 (16)	0.0395 (11)	0.0169 (13)	0.0130 (10)	0.0128 (10)

Geometric parameters (Å, º) top

Mo1—O2	1.6988 (13)	C4—C5	1.379 (4)
Mo1—O1	1.7004 (13)	C4—H4	0.9500
Mo1—Cl2	2.3750 (6)	C5—H5	0.9500
Mo1—Cl1	2.3995 (6)	C6—C7	1.372 (4)
Mo1—Cl3	2.5746 (5)	C6—H6	0.9500
Mo1—Cl4	2.5953 (5)	C7—C8	1.377 (4)
N1—C1	1.335 (3)	C7—H7	0.9500
N1—C5	1.336 (3)	C8—C9	1.375 (4)
N1—H1A	0.8800	C8—H8	0.9500
N2—C6	1.332 (4)	C9—C10	1.371 (4)
N2—C10	1.338 (4)	C9—H9	0.9500
N2—H2A	0.8800	C10—H10	0.9500
N3—C11	1.310 (3)	C11—C12	1.363 (4)
N3—C15	1.349 (3)	C11—H11	0.9500
N3—H3A	0.8800	C12—C13	1.395 (4)
C1—C2	1.369 (3)	C12—H12	0.9500
C1—H1	0.9500	C13—C14	1.369 (4)
C2—C3	1.392 (3)	C13—H13	0.9500
C2—H2	0.9500	C14—C15	1.370 (4)
C3—C4	1.373 (4)	C14—H14	0.9500
C3—H3	0.9500	C15—H15	0.9500

O2—Mo1—O1	102.11 (7)	C5—C4—H4	120.4
O2—Mo1—Cl2	94.45 (6)	N1—C5—C4	119.6 (2)
O1—Mo1—Cl2	95.78 (6)	N1—C5—H5	120.2
O2—Mo1—Cl1	94.06 (6)	C4—C5—H5	120.2
O1—Mo1—Cl1	93.64 (6)	N2—C6—C7	119.4 (3)
Cl2—Mo1—Cl1	165.71 (2)	N2—C6—H6	120.3
O2—Mo1—Cl3	169.07 (5)	C7—C6—H6	120.3
O1—Mo1—Cl3	88.75 (5)	C6—C7—C8	119.2 (3)
Cl2—Mo1—Cl3	85.57 (2)	C6—C7—H7	120.4
Cl1—Mo1—Cl3	83.91 (2)	C8—C7—H7	120.4
O2—Mo1—Cl4	87.40 (5)	C9—C8—C7	120.0 (2)
O1—Mo1—Cl4	170.36 (5)	C9—C8—H8	120.0
Cl2—Mo1—Cl4	84.99 (2)	C7—C8—H8	120.0
Cl1—Mo1—Cl4	83.94 (2)	C10—C9—C8	119.2 (3)
Cl3—Mo1—Cl4	81.717 (16)	C10—C9—H9	120.4
C1—N1—C5	122.4 (2)	C8—C9—H9	120.4
C1—N1—H1A	118.8	N2—C10—C9	119.4 (2)
C5—N1—H1A	118.8	N2—C10—H10	120.3
C6—N2—C10	122.8 (2)	C9—C10—H10	120.3
C6—N2—H2A	118.6	N3—C11—C12	120.6 (2)
C10—N2—H2A	118.6	N3—C11—H11	119.7
C11—N3—C15	122.7 (2)	C12—C11—H11	119.7
C11—N3—H3A	118.6	C11—C12—C13	118.4 (3)
C15—N3—H3A	118.6	C11—C12—H12	120.8
N1—C1—C2	120.24 (19)	C13—C12—H12	120.8
N1—C1—H1	119.9	C14—C13—C12	119.9 (3)
C2—C1—H1	119.9	C14—C13—H13	120.0
C1—C2—C3	118.6 (2)	C12—C13—H13	120.0
C1—C2—H2	120.7	C13—C14—C15	119.2 (3)
C3—C2—H2	120.7	C13—C14—H14	120.4
C4—C3—C2	120.0 (2)	C15—C14—H14	120.4
C4—C3—H3	120.0	N3—C15—C14	119.1 (3)
C2—C3—H3	120.0	N3—C15—H15	120.4
C3—C4—C5	119.14 (19)	C14—C15—H15	120.4
C3—C4—H4	120.4

C5—N1—C1—C2	−1.7 (4)	C7—C8—C9—C10	−0.9 (4)
N1—C1—C2—C3	−1.0 (4)	C6—N2—C10—C9	−0.3 (4)
C1—C2—C3—C4	2.5 (4)	C8—C9—C10—N2	1.6 (4)
C2—C3—C4—C5	−1.5 (4)	C15—N3—C11—C12	−1.3 (4)
C1—N1—C5—C4	2.8 (4)	N3—C11—C12—C13	1.0 (4)
C3—C4—C5—N1	−1.1 (4)	C11—C12—C13—C14	−0.5 (4)
C10—N2—C6—C7	−1.9 (4)	C12—C13—C14—C15	0.2 (5)
N2—C6—C7—C8	2.6 (4)	C11—N3—C15—C14	1.0 (4)
C6—C7—C8—C9	−1.2 (4)	C13—C14—C15—N3	−0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl6ⁱ	0.88	2.16	3.0424 (19)	175
N2—H2A···Cl5ⁱⁱ	0.88	2.17	3.0304 (19)	166
N3—H3A···Cl4	0.88	2.45	3.243 (2)	150
N3—H3A···Cl3	0.88	2.69	3.277 (2)	126

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

Experimental details

Crystal data
Chemical formula	(C₅H₆N)₃[MoCl₄O₂]Cl
M_r	545.51
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	150
a, c (Å)	11.3972 (2), 29.4265 (9)
V (Å³)	3310.28 (13)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.21
Crystal size (mm)	0.18 × 0.12 × 0.10

Data collection
Diffractometer	Bruker X8 Kappa CCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.811, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	33230, 10395, 8105
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.833

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.074, 1.05
No. of reflections	10395
No. of parameters	237
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.68
Absolute structure	Flack (1983), 4490 Friedel pairs
Absolute structure parameter	0.03 (4)

Computer programs: APEX2 (Bruker, 2006), APEX2 and SAINT-Plus (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top

Mo1—O2	1.6988 (13)	Mo1—Cl1	2.3995 (6)
Mo1—O1	1.7004 (13)	Mo1—Cl3	2.5746 (5)
Mo1—Cl2	2.3750 (6)	Mo1—Cl4	2.5953 (5)

O2—Mo1—O1	102.11 (7)	Cl2—Mo1—Cl3	85.57 (2)
O2—Mo1—Cl2	94.45 (6)	Cl1—Mo1—Cl3	83.91 (2)
O1—Mo1—Cl2	95.78 (6)	O2—Mo1—Cl4	87.40 (5)
O2—Mo1—Cl1	94.06 (6)	O1—Mo1—Cl4	170.36 (5)
O1—Mo1—Cl1	93.64 (6)	Cl2—Mo1—Cl4	84.99 (2)
Cl2—Mo1—Cl1	165.71 (2)	Cl1—Mo1—Cl4	83.94 (2)
O2—Mo1—Cl3	169.07 (5)	Cl3—Mo1—Cl4	81.717 (16)
O1—Mo1—Cl3	88.75 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl6ⁱ	0.88	2.16	3.0424 (19)	175.4
N2—H2A···Cl5ⁱⁱ	0.88	2.17	3.0304 (19)	165.8
N3—H3A···Cl4	0.88	2.45	3.243 (2)	149.5
N3—H3A···Cl3	0.88	2.69	3.277 (2)	125.6

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

Acknowledgements

We wish to thank Dr Martyn Pillinger (CICECO, University of Aveiro) and Dr André D. Lopes (University of the Algarve) for their collaboration in the preparation of this communication. We are also grateful to Fundação para a Ciência e a Tecnologia (FCT, Portugal) for their general financial support, for the post-doctoral research grant SFRH/BPD/63736/2009 (to JAF), SFRH/BPD/25269/2005 (to SG), SFRH/BD/45116/2008 (to SF) and for specific funding toward the purchase of the single-crystal diffractometer. We also wish to thank the Associated Laboratory CICECO for a research grant to AG.

References

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Volume 66| Part 7| July 2010| Pages m862-m863

doi:10.1107/S1600536810023950

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