A 4-ethyl­pyridine complex of tetra­chloro­molybdenum(III) and its oxidation product

The Mo atoms in the title compounds, i.e. triethyl­ammonium cis-tetra­chloro­bis(4-ethyl­pyridine-N)­molybdate(III), cis-(C₆H₁₆N)­[MoCl₄(C₇H₉N)₂], and trans-tetra­chloro­bis(4-ethyl­pyridine-N)molybdenum(IV), trans-[MoCl₄(C₇H₉N)₂], are six-coordinate with octahedral geometry. The Mo atom in the latter complex lies on a site with crystallographic 2/m symmetry.

S1. Comment

[MoX₆]³⁻ (X = Cl⁻ or Br⁻) reacts with pyridine to give various halopyridine complexes, e.g. [MoX₅(py)]²⁻ (py = pyridine, C₅H₅N; Modec et al., 1998), trans- and cis-[MoX₄py₂]⁻ (Brenčič et al., 1993, 1994), mer-[MoX₃py₃] (Brenčič, 1974) and trans-[MoX₂py₄]⁺ (Brenčič et al., 1996). On partial substitution of the chloro ligands in [MoCl₆]³⁻ with 4-ethylpyridine (4-Etpy), both trans and cis geometric isomers of [MoCl₄(4-EtPy)₂]⁻ were obtained. Bromine oxidation of both resulted in a molybdenum(IV) complex with a trans configuration of 4-ethylpyridine ligands suggesting a rearrangement of ligands during the electron transfer. We report here the structures of triethylammonium cis-tetrachlorobis(4-ethylpyridine-N)molybdate(III), (I), and trans-tetrachlorobis(4-ethylpyridine-N)molybdenum(IV), (II).

While many tetrahalodipyridinemetalates(III) with the trans configuration of ligands are known, there are only a few structurally characterized cis isomers, namely cis-NH₄[MoCl₄(py)₂].py·H₂O (Leban et al., 1994), cis-NH₄[MoBr₄(py)₂].1/3H₂O (Brenčič et al., 1994) and cis-(Et₄N)[OsCl₄(py)₂] (Kolf & Preetz, 1999). Also (PPh₄)[MoCl₄(bipy)] (Richards et al., 1987), with the bidentate N-donor ligand 2,2'-bipyridine (bipy), displays a similar geometry, with the two N atoms in a cis arrangement. Selected bond lengths and angles for (I) are given in Table 1. Four Cl atoms at distances in the range 2.423 (1)–2.438 (1) Å and two N atoms at distances of 2.196 (2) and 2.206 (4) Å make up the octahedral coordination of the Mo atom. These distances are comparable to those found in related compounds, for example, in cis-NH₄[MoCl₄(py)₂].py·H₂O [Mo—Cl 2.423 (2)–2.446 (2) Å and Mo—N 2.202 (5)–2.206 (4) Å; Leban et al., 1994]. Because of the orientation of the aromatic rings, the cis-[MoCl₄(4-Etpy)₂]⁻ complex anion possesses no symmetry element. The dihedral angle between the planes of the two pyridine ligands is 49.8 (2)°. Compound (I) crystallizes in an acentric space group, Pca2₁, while other cis compounds crystallize as racemic mixtures in centrosymmetric space groups. The N3 atom of the triethylammonium cation is linked via two hydrogen bonds with chlorines from the coordination anion [N3···Cl3 3.482 (4) Å and N3···Cl4 3.449 (4) Å]. High thermal motion was observed for the ethyl C atoms of the 4-ethylpyridine ligand and in the case of C27, a possible disorder over two positions was suggested.

Among the compounds [ZrCl₄(py)₂] (CSD refcode FUFSOO), [TiCl₄(py)₂] (GAMGAC), [TaCl₄(py)₂] (LATVUX), [PtCl₄(py)₂] (TULFIP) and [WCl₄(py)₂] (CPYRDW10) [Cambridge Structural Database (CSD), October 1999 release; Allen & Kennard, 1993], not only are they all trans isomers but their structures are isotypic, as shown by a comparison of the unit-cell dimensions. [M^IVCl₄(py)₂] has a C_{2 h} site-group symmetry. The ethyl groups on pyridine in (II) affect the unit-cell dimensions, leaving the overall symmetry of the complex intact. The Mo atom occupies a 2/m special position. The 4-ethylpyridine rings, which lie on a mirror plane, are in an eclipsed configuration. Four Cl atoms are bonded to molybdenum at distances of 2.340 (1) Å and two N atoms at distances of 2.195 (3) Å (Table 3).

S2. Experimental

To the solution of cis-LH[MoCl₄L₂] (L= 4-ethylpyridine; 150 mg, 0.268 mmol) in acetonitrile (15 ml), triethylamine (5 ml) and ether (50 ml) were added. The solution was left to stand overnight in the ice bath. Crystals of (I) were obtained in 35% yield (52 mg). Analysis calculated (found) in %: C 43.34 (43.38), H 6.18 (6.31), N 7.58 (7.40). IR data (nujol, cm⁻¹): 3091 (m), 1617 (vvs), 1550 (w), 1315 (w), 1285 (w), 1224 (m), 1207 (w), 1180 (w), 1172 (w), 1153 (w), 1083 (w), 1065 (m), 1054 (w), 1028 (versus), 1009 (w), 976 (w), 845 (vvs), 789 (m), 722 (m), 667 (w), 578 (m), 512 (m), 304 (vvs), 284 (s), 272 (sh). A solution of trans-LH[MoCl₄L₂] (L = 4-ethylpyridine; 30 mg, 0.0535 mmol) in nitromethane (5 ml) and acetonitrile (5 ml) was placed in a chamber containing bromine fumes. Within a few hours, red crystals of (II) had grown from the solution. Analysis calculated (found) in %: C 37.20 (36.92), H 4.01 (3.90), N 6.20 (6.29). IR data (nujol, cm⁻¹): 1618 (versus), 1549 (w), 1500(m), 1308(m), 1222 (m), 1193 (w), 1063 (versus), 1054 (m), 1030 (versus), 979 (w), 957 (w), 833 (vvs), 792 (m), 780 (w), 767 (w), 721 (m), 702 (w), 669 (w), 561 (w), 497 (s), 430 (w)

Computing details

Data collection: D*TREK (Molecular Structure Corporation, 1997) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: D*TREK for (I); CAD-4 Software for (II). Data reduction: D*TREK for (I); Xtal3.4 DIFDAT, SORTRF and ADDREF (Hall et al., 1995) for (II). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); Xtal3.4 for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); Xtal3.4 CRYLSQ for (II). For both compounds, molecular graphics: ORTEPIII (Burnett & Johnson, 1996). Software used to prepare material for publication: Xtal3.4 BONDLA and CIFIO for (II).

Figures

	Fig. 1. The structure of (I) with displacement ellipsoids drawn at the 30% probability level. H atoms are of arbitrary size.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms are of arbitrary size.

(I) triethylammonium cis-tetrachlorodi(4-ethylpyridine)molybdenum(III)

Crystal data

(C6H16N)[MoCl4(C7H9N)2]	F(000) = 1140
Mr = 554.24	Dx = 1.433 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 12687 reflections
a = 19.7025 (9) Å	θ = 3.8–25.0°
b = 7.766 (2) Å	µ = 0.94 mm^−1
c = 16.7929 (6) Å	T = 293 K
V = 2569.6 (6) Å^3	Prism, yellow
Z = 4	0.50 × 0.30 × 0.15 mm

Data collection

Quantum CCD Rigaku AFC7 diffractometer	5860 independent reflections
Radiation source: fine-focus sealed tube	3267 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 14.14 pixels mm^-1	θmax = 26.4°, θmin = 2.6°
ϕ and ω scans	h = 0→23
Absorption correction: empirical (using intensity measurements) (REQABA; Jacobson, 1997)	k = −8→8
Tmin = 0.739, Tmax = 0.869	l = −19→19
18043 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.059	Calculated w = 1/[σ^2(Fo^2) + (0.0285P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4069 reflections	Δρmax = 0.81 e Å^−3
253 parameters	Δρmin = −0.49 e Å^−3
1 restraint	Absolute structure: Flack, 1983
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (4)

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
Mo1	0.130288 (12)	0.08905 (4)	−0.00133 (3)	0.02836 (8)
Cl1	0.16937 (7)	0.29341 (17)	−0.10021 (6)	0.0462 (3)
Cl2	0.07785 (7)	−0.11467 (17)	0.09026 (6)	0.0453 (3)
Cl3	0.17528 (7)	0.25470 (18)	0.10958 (7)	0.0498 (4)
Cl4	0.23359 (4)	−0.08283 (13)	−0.00960 (9)	0.0442 (3)
N1	0.03516 (12)	0.2361 (4)	0.0038 (3)	0.0307 (6)
N2	0.0874 (2)	−0.0640 (5)	−0.0998 (2)	0.0311 (10)
C11	0.03533 (18)	0.4079 (5)	0.0131 (2)	0.0335 (11)
H11	0.0767	0.4635	0.0204	0.040*
C12	−0.02234 (18)	0.5039 (5)	0.0123 (3)	0.0424 (11)
H12	−0.0196	0.6220	0.0207	0.051*
C13	−0.08537 (15)	0.4285 (5)	−0.0007 (4)	0.0446 (9)
C14	−0.08561 (16)	0.2503 (6)	−0.0067 (4)	0.0454 (10)
H14	−0.1266	0.1920	−0.0120	0.055*
C15	−0.02594 (16)	0.1593 (5)	−0.0048 (3)	0.0377 (8)
H15	−0.0276	0.0400	−0.0095	0.045*
C16	−0.1502 (2)	0.5326 (6)	−0.0029 (6)	0.0778 (14)
H16A	−0.1868	0.4595	−0.0217	0.093*
H16B	−0.1614	0.5685	0.0509	0.093*
C17	−0.1466 (3)	0.6824 (10)	−0.0528 (5)	0.148 (4)
H17A	−0.1047	0.7419	−0.0430	0.178*
H17B	−0.1840	0.7574	−0.0410	0.178*
H17C	−0.1486	0.6482	−0.1076	0.178*
C21	0.05061 (19)	0.0091 (6)	−0.1583 (2)	0.0375 (10)
H21	0.0458	0.1283	−0.1590	0.045*
C22	0.01970 (19)	−0.0868 (6)	−0.2175 (2)	0.0389 (10)
H22	−0.0058	−0.0318	−0.2566	0.047*
C23	0.0264 (2)	−0.2627 (6)	−0.2189 (2)	0.0413 (11)
C24	0.0662 (2)	−0.3356 (6)	−0.1595 (2)	0.0396 (10)
H24	0.0732	−0.4540	−0.1588	0.048*
C25	0.0950 (2)	−0.2347 (5)	−0.1022 (2)	0.0382 (10)
H25	0.1211	−0.2873	−0.0630	0.046*
C26	−0.0054 (3)	−0.3696 (7)	−0.2836 (3)	0.0707 (17)
H26A	−0.0444	−0.3076	−0.3041	0.085*
H26B	0.0270	−0.3799	−0.3269	0.085*
C27	−0.0269 (5)	−0.5386 (12)	−0.2618 (5)	0.184 (5)
H27A	−0.0580	−0.5314	−0.2180	0.221*
H27B	0.0119	−0.6058	−0.2464	0.221*
H27C	−0.0489	−0.5923	−0.3063	0.221*
N3	0.24771 (19)	−0.1105 (5)	0.1947 (2)	0.0506 (11)
H3	0.2245	−0.0485	0.1576	0.061*
C1	0.3230 (3)	−0.0911 (8)	0.1752 (3)	0.0706 (18)
H1A	0.3492	−0.1404	0.2184	0.085*
H1B	0.3328	−0.1575	0.1276	0.085*
C2	0.3455 (3)	0.0845 (9)	0.1625 (4)	0.096 (2)
H2A	0.3195	0.1356	0.1204	0.144*
H2B	0.3927	0.0846	0.1483	0.144*
H2C	0.3392	0.1496	0.2106	0.144*
C3	0.2262 (3)	−0.2928 (7)	0.1855 (3)	0.0664 (15)
H3A	0.2368	−0.3302	0.1318	0.080*
H3B	0.1774	−0.2993	0.1920	0.080*
C4	0.2597 (6)	−0.4172 (6)	0.2446 (5)	0.099 (3)
H4A	0.3061	−0.4360	0.2294	0.149*
H4B	0.2358	−0.5249	0.2443	0.149*
H4C	0.2582	−0.3685	0.2971	0.149*
C5	0.2317 (3)	−0.0321 (8)	0.2742 (3)	0.0729 (19)
H5A	0.2576	−0.0916	0.3149	0.087*
H5B	0.2461	0.0873	0.2740	0.087*
C6	0.1595 (3)	−0.0395 (11)	0.2952 (4)	0.099 (3)
H6A	0.1330	0.0105	0.2532	0.149*
H6B	0.1520	0.0235	0.3436	0.149*
H6C	0.1462	−0.1573	0.3027	0.149*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.02555 (14)	0.03087 (16)	0.02867 (13)	−0.00095 (14)	−0.0027 (2)	0.0027 (2)
Cl1	0.0407 (7)	0.0448 (8)	0.0530 (7)	−0.0041 (6)	0.0085 (6)	0.0168 (6)
Cl2	0.0548 (8)	0.0461 (8)	0.0350 (6)	−0.0082 (7)	0.0019 (6)	0.0113 (6)
Cl3	0.0487 (8)	0.0491 (8)	0.0517 (7)	−0.0010 (6)	−0.0161 (6)	−0.0127 (6)
Cl4	0.0324 (4)	0.0494 (6)	0.0510 (7)	0.0105 (5)	−0.0054 (6)	0.0023 (7)
N1	0.0256 (14)	0.0300 (17)	0.0365 (15)	−0.0013 (13)	0.005 (2)	0.004 (2)
N2	0.024 (2)	0.040 (3)	0.0291 (19)	0.0062 (18)	−0.0013 (16)	0.0018 (17)
C11	0.0299 (18)	0.036 (2)	0.034 (3)	−0.0079 (19)	−0.0019 (16)	0.004 (2)
C12	0.037 (2)	0.034 (2)	0.056 (3)	0.0054 (19)	0.002 (2)	−0.001 (2)
C13	0.0289 (18)	0.051 (3)	0.0541 (19)	0.0081 (18)	−0.007 (4)	0.003 (3)
C14	0.0255 (18)	0.054 (3)	0.056 (3)	−0.0062 (18)	0.006 (3)	−0.003 (4)
C15	0.0363 (19)	0.037 (2)	0.0402 (19)	−0.0078 (17)	0.003 (3)	−0.005 (3)
C16	0.041 (2)	0.065 (3)	0.128 (4)	0.014 (2)	0.012 (6)	0.014 (6)
C17	0.077 (5)	0.155 (8)	0.213 (9)	0.051 (5)	0.005 (5)	0.079 (7)
C21	0.035 (2)	0.039 (3)	0.038 (2)	0.005 (2)	0.0029 (18)	0.006 (2)
C22	0.033 (2)	0.056 (3)	0.028 (2)	0.001 (2)	−0.0069 (16)	0.003 (2)
C23	0.040 (2)	0.052 (3)	0.032 (2)	−0.010 (2)	−0.0019 (18)	−0.005 (2)
C24	0.048 (3)	0.035 (3)	0.036 (2)	−0.001 (2)	−0.0010 (19)	−0.004 (2)
C25	0.044 (3)	0.033 (3)	0.037 (2)	0.008 (2)	−0.0010 (19)	0.007 (2)
C26	0.088 (4)	0.073 (5)	0.051 (3)	−0.020 (3)	−0.024 (3)	−0.015 (3)
C27	0.309 (14)	0.143 (9)	0.102 (6)	−0.136 (9)	−0.056 (7)	−0.015 (6)
N3	0.052 (2)	0.061 (3)	0.039 (2)	0.008 (2)	−0.0134 (18)	0.0065 (19)
C1	0.048 (3)	0.099 (5)	0.065 (3)	0.011 (4)	−0.016 (3)	0.006 (3)
C2	0.059 (4)	0.125 (7)	0.104 (5)	−0.015 (4)	−0.010 (3)	0.053 (5)
C3	0.084 (4)	0.056 (4)	0.060 (3)	−0.012 (3)	−0.028 (3)	−0.003 (3)
C4	0.126 (7)	0.055 (3)	0.117 (4)	0.005 (5)	−0.065 (4)	0.010 (5)
C5	0.100 (6)	0.072 (4)	0.047 (3)	−0.005 (4)	−0.005 (3)	−0.006 (3)
C6	0.058 (4)	0.176 (8)	0.064 (4)	0.005 (5)	0.012 (3)	0.012 (4)

Geometric parameters (Å, º)

Mo1—N1	2.196 (2)	C24—C25	1.365 (6)
Mo1—N2	2.206 (4)	C24—H24	0.9300
Mo1—Cl1	2.4226 (12)	C25—H25	0.9300
Mo1—Cl3	2.4309 (13)	C26—C27	1.427 (9)
Mo1—Cl2	2.4364 (12)	C26—H26A	0.9700
Mo1—Cl4	2.4379 (9)	C26—H26B	0.9700
N1—C11	1.343 (4)	C27—H27A	0.9600
N1—C15	1.351 (4)	C27—H27B	0.9600
N2—C25	1.334 (5)	C27—H27C	0.9600
N2—C21	1.346 (5)	N3—C3	1.486 (6)
C11—C12	1.359 (5)	N3—C5	1.501 (6)
C11—H11	0.9300	N3—C1	1.527 (6)
C12—C13	1.390 (5)	N3—H3	0.9100
C12—H12	0.9300	C1—C2	1.450 (7)
C13—C14	1.388 (5)	C1—H1A	0.9700
C13—C16	1.513 (5)	C1—H1B	0.9700
C14—C15	1.372 (5)	C2—H2A	0.9600
C14—H14	0.9300	C2—H2B	0.9600
C15—H15	0.9300	C2—H2C	0.9600
C16—C17	1.435 (9)	C3—C4	1.534 (8)
C16—H16A	0.9700	C3—H3A	0.9700
C16—H16B	0.9700	C3—H3B	0.9700
C17—H17A	0.9600	C4—H4A	0.9600
C17—H17B	0.9600	C4—H4B	0.9600
C17—H17C	0.9600	C4—H4C	0.9600
C21—C22	1.384 (6)	C5—C6	1.466 (7)
C21—H21	0.9300	C5—H5A	0.9700
C22—C23	1.373 (6)	C5—H5B	0.9700
C22—H22	0.9300	C6—H6A	0.9600
C23—C24	1.389 (5)	C6—H6B	0.9600
C23—C26	1.505 (6)	C6—H6C	0.9600
N1—Mo1—N2	88.97 (14)	C23—C24—H24	119.8
N1—Mo1—Cl1	87.55 (9)	N2—C25—C24	123.0 (4)
N2—Mo1—Cl1	87.76 (11)	N2—C25—H25	118.5
N1—Mo1—Cl3	90.36 (11)	C24—C25—H25	118.5
N2—Mo1—Cl3	178.47 (11)	C27—C26—C23	116.4 (5)
Cl1—Mo1—Cl3	93.59 (4)	C27—C26—H26A	108.2
N1—Mo1—Cl2	87.20 (9)	C23—C26—H26A	108.2
N2—Mo1—Cl2	87.75 (10)	C27—C26—H26B	108.2
Cl1—Mo1—Cl2	173.16 (5)	C23—C26—H26B	108.2
Cl3—Mo1—Cl2	90.84 (5)	H26A—C26—H26B	107.3
N1—Mo1—Cl4	177.83 (9)	C26—C27—H27A	109.5
N2—Mo1—Cl4	88.99 (11)	C26—C27—H27B	109.5
Cl1—Mo1—Cl4	93.11 (5)	H27A—C27—H27B	109.5
Cl3—Mo1—Cl4	91.66 (5)	C26—C27—H27C	109.5
Cl2—Mo1—Cl4	91.98 (5)	H27A—C27—H27C	109.5
C11—N1—C15	116.9 (3)	H27B—C27—H27C	109.5
C11—N1—Mo1	121.2 (2)	C3—N3—C5	114.8 (4)
C15—N1—Mo1	121.8 (2)	C3—N3—C1	110.4 (4)
C25—N2—C21	117.3 (4)	C5—N3—C1	110.9 (4)
C25—N2—Mo1	120.9 (3)	C3—N3—H3	106.8
C21—N2—Mo1	121.7 (3)	C5—N3—H3	106.8
N1—C11—C12	122.8 (3)	C1—N3—H3	106.8
N1—C11—H11	118.6	C2—C1—N3	114.9 (5)
C12—C11—H11	118.6	C2—C1—H1A	108.5
C11—C12—C13	121.2 (4)	N3—C1—H1A	108.5
C11—C12—H12	119.4	C2—C1—H1B	108.5
C13—C12—H12	119.4	N3—C1—H1B	108.5
C14—C13—C12	115.7 (3)	H1A—C1—H1B	107.5
C14—C13—C16	121.9 (3)	C1—C2—H2A	109.5
C12—C13—C16	122.2 (4)	C1—C2—H2B	109.5
C15—C14—C13	120.6 (3)	H2A—C2—H2B	109.5
C15—C14—H14	119.7	C1—C2—H2C	109.5
C13—C14—H14	119.7	H2A—C2—H2C	109.5
N1—C15—C14	122.6 (3)	H2B—C2—H2C	109.5
N1—C15—H15	118.7	N3—C3—C4	114.2 (4)
C14—C15—H15	118.7	N3—C3—H3A	108.7
C17—C16—C13	113.9 (5)	C4—C3—H3A	108.7
C17—C16—H16A	108.8	N3—C3—H3B	108.7
C13—C16—H16A	108.8	C4—C3—H3B	108.7
C17—C16—H16B	108.8	H3A—C3—H3B	107.6
C13—C16—H16B	108.8	C3—C4—H4A	109.5
H16A—C16—H16B	107.7	C3—C4—H4B	109.5
C16—C17—H17A	109.5	H4A—C4—H4B	109.5
C16—C17—H17B	109.5	C3—C4—H4C	109.5
H17A—C17—H17B	109.5	H4A—C4—H4C	109.5
C16—C17—H17C	109.5	H4B—C4—H4C	109.5
H17A—C17—H17C	109.5	C6—C5—N3	113.7 (5)
H17B—C17—H17C	109.5	C6—C5—H5A	108.8
N2—C21—C22	122.3 (4)	N3—C5—H5A	108.8
N2—C21—H21	118.9	C6—C5—H5B	108.8
C22—C21—H21	118.9	N3—C5—H5B	108.8
C23—C22—C21	120.4 (4)	H5A—C5—H5B	107.7
C23—C22—H22	119.8	C5—C6—H6A	109.5
C21—C22—H22	119.8	C5—C6—H6B	109.5
C22—C23—C24	116.6 (4)	H6A—C6—H6B	109.5
C22—C23—C26	121.4 (4)	C5—C6—H6C	109.5
C24—C23—C26	121.9 (5)	H6A—C6—H6C	109.5
C25—C24—C23	120.5 (4)	H6B—C6—H6C	109.5
C25—C24—H24	119.8

(II) trans-tetrachlorodi(4-ethylpyridine)molybdenum(IV)

Crystal data

[MoCl4(C7H9N)2]	F(000) = 452
Mr = 452.06	Dx = 1.715 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 50 reflections
a = 16.1077 (8) Å	θ = 10.0–20.1°
b = 7.6691 (4) Å	µ = 1.35 mm^−1
c = 7.1566 (4) Å	T = 293 K
β = 98.012 (4)°	Prism, red
V = 875.44 (8) Å^3	0.19 × 0.11 × 0.10 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 2.6°
Graphite monochromator	h = −22→22
ω/2θ scans	k = −10→10
5116 measured reflections	l = −10→10
1358 independent reflections	3 standard reflections every 300 reflections
1114 reflections with > 3σ(I)	intensity decay: 0.6%

Refinement

Refinement on F	Primary atom site location: real-space vector search
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.028	H-atom parameters not refined
S = 1.32	w = WF^.WS, where WF(Fo < 20) = (Fo/20)^1.5, WF(Fo > 22) = (22/Fo)^1, WF(20 < Fo<22) = 1, and WS(sinΘ < 0.48) = (0.48/sinΘ)^2.0 WS(sinΘ > 0.56) = (sinΘ/0.56)^2.0 WS(0.48 < sinΘ < 0.56) = 1
1114 reflections	(Δ/σ)max = 0.001
62 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mo	0.50000	0.50000	0.50000	0.0265 (3)
Cl	0.55020 (5)	0.28486 (12)	0.31276 (13)	0.0422 (6)
N	0.6201 (2)	0.50000	0.6875 (5)	0.0306 (19)
C1	0.6944 (3)	0.50000	0.6173 (7)	0.038 (3)
C2	0.7701 (3)	0.50000	0.7319 (7)	0.036 (2)
C3	0.7738 (3)	0.50000	0.9287 (7)	0.033 (2)
C4	0.6972 (3)	0.50000	0.9985 (7)	0.043 (3)
C5	0.6223 (3)	0.50000	0.8759 (7)	0.040 (3)
C6	0.8580 (3)	0.50000	1.0530 (7)	0.043 (3)
C7	0.8538 (3)	0.50000	1.2652 (8)	0.049 (3)
H1	0.69150	0.50000	0.46570	0.03600*
H2	0.82350	0.50000	0.66820	0.03600*
H4	0.69370	0.50000	1.14440	0.04300*
H5	0.56420	0.50000	0.92540	0.04100*
H6	0.89020	0.39770	1.00000	0.04400*
H71	0.82290	0.39680	1.30180	0.05200*
H72	0.91190	0.50000	1.32900	0.05200*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo	0.0219 (3)	0.0341 (3)	0.0243 (3)	0.00000	0.0059 (2)	0.00000
Cl	0.0397 (5)	0.0469 (6)	0.0412 (6)	0.0073 (4)	0.0097 (4)	−0.0103 (4)
N	0.0249 (18)	0.039 (2)	0.028 (2)	0.00000	0.0040 (15)	0.00000
C1	0.028 (2)	0.053 (3)	0.032 (3)	0.00000	0.008 (2)	0.00000
C2	0.027 (2)	0.053 (3)	0.030 (3)	0.00000	0.0059 (19)	0.00000
C3	0.027 (2)	0.037 (3)	0.034 (3)	0.00000	0.0023 (19)	0.00000
C4	0.031 (3)	0.066 (4)	0.031 (3)	0.00000	0.005 (2)	0.00000
C5	0.033 (2)	0.061 (4)	0.028 (3)	0.00000	0.005 (2)	0.00000
C6	0.029 (2)	0.066 (4)	0.031 (3)	0.00000	−0.003 (2)	0.00000
C7	0.041 (3)	0.070 (4)	0.032 (3)	0.00000	−0.007 (2)	0.00000

Geometric parameters (Å, º)

Mo—Cl	2.3396 (9)	C3—C4	1.394 (7)
Mo—N	2.195 (3)	C3—C6	1.515 (6)
Mo—Cl^i	2.3396 (9)	C4—C5	1.389 (6)
Mo—N^i	2.195 (3)	C4—H4	1.054 (5)
Mo—Cl^ii	2.3396 (9)	C5—H5	1.046 (5)
Mo—Cl^iii	2.3396 (9)	C6—C7	1.529 (8)
N—C1	1.361 (6)	C6—H6	1.041 (4)
N—C5	1.344 (6)	C6—H6^iii	1.041 (4)
C1—C2	1.372 (6)	C7—H71	0.990 (3)
C1—H1	1.079 (5)	C7—H72	0.982 (5)
C2—C3	1.401 (7)	C7—H71^iii	0.990 (3)
C2—H2	1.028 (5)
Cl—Mo—N	90.27 (8)	C3—C2—H2	121.7 (4)
Cl—Mo—Cl^i	90.31 (3)	C2—C3—C4	116.4 (4)
Cl—Mo—N^i	89.73 (8)	C2—C3—C6	120.0 (4)
Cl—Mo—Cl^ii	180.0000	C4—C3—C6	123.6 (4)
Cl—Mo—Cl^iii	89.69 (3)	C3—C4—C5	120.5 (5)
N—Mo—Cl^i	89.73 (8)	C3—C4—H4	121.8 (4)
N—Mo—N^i	180.0000	C5—C4—H4	117.7 (5)
N—Mo—Cl^ii	89.73 (8)	N—C5—C4	122.2 (5)
N—Mo—Cl^iii	90.27 (8)	N—C5—H5	116.1 (4)
Cl^i—Mo—N^i	90.27 (8)	C4—C5—H5	121.7 (5)
Cl^i—Mo—Cl^ii	89.69 (3)	C3—C6—C7	115.1 (4)
Cl^i—Mo—Cl^iii	180.0000	C3—C6—H6	103.7 (3)
N^i—Mo—Cl^ii	90.27 (8)	C3—C6—H6^iii	103.7 (3)
N^i—Mo—Cl^iii	89.73 (8)	C7—C6—H6	117.1 (3)
Cl^ii—Mo—Cl^iii	90.31 (3)	C7—C6—H6^iii	117.1 (3)
Mo—N—C1	121.3 (3)	H6—C6—H6^iii	97.8 (4)
Mo—N—C5	120.8 (3)	C6—C7—H71	110.9 (3)
C1—N—C5	117.9 (4)	C6—C7—H72	106.9 (5)
N—C1—C2	122.3 (5)	C6—C7—H71^iii	110.9 (3)
N—C1—H1	117.0 (4)	H71—C7—H72	111.0 (3)
C2—C1—H1	120.7 (5)	H71—C7—H71^iii	106.2 (5)
C1—C2—C3	120.7 (4)	H72—C7—H71^iii	111.0 (3)
C1—C2—H2	117.7 (5)

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