Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004911/na1469sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004911/na1469Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004911/na1469IIsup3.hkl |
CCDC references: 147619; 147620
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)
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).
(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) Å3 | Prism, yellow |
Z = 4 | 0.50 × 0.30 × 0.15 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.059 | Calculated w = 1/[σ2(Fo2) + (0.0285P)2] where P = (Fo2 + 2Fc2)/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) |
(C6H16N)[MoCl4(C7H9N)2] | V = 2569.6 (6) Å3 |
Mr = 554.24 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 19.7025 (9) Å | µ = 0.94 mm−1 |
b = 7.766 (2) Å | T = 293 K |
c = 16.7929 (6) Å | 0.50 × 0.30 × 0.15 mm |
Quantum CCD Rigaku AFC7 diffractometer | 5860 independent reflections |
Absorption correction: empirical (using intensity measurements) (REQABA; Jacobson, 1997) | 3267 reflections with I > 2σ(I) |
Tmin = 0.739, Tmax = 0.869 | Rint = 0.041 |
18043 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.059 | Δρmax = 0.81 e Å−3 |
S = 1.03 | Δρmin = −0.49 e Å−3 |
4069 reflections | Absolute structure: Flack, 1983 |
253 parameters | Absolute structure parameter: −0.03 (4) |
1 restraint |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
[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) Å3 | 0.19 × 0.11 × 0.10 mm |
Z = 2 |
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 on F | Primary atom site location: real-space vector search |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 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 |
[MoCl4(C7H9N)2] | V = 875.44 (8) Å3 |
Mr = 452.06 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 16.1077 (8) Å | µ = 1.35 mm−1 |
b = 7.6691 (4) Å | T = 293 K |
c = 7.1566 (4) Å | 0.19 × 0.11 × 0.10 mm |
β = 98.012 (4)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.015 |
5116 measured reflections | 3 standard reflections every 300 reflections |
1358 independent reflections | intensity decay: 0.6% |
1114 reflections with > 3σ(I) |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.028 | H-atom parameters not refined |
S = 1.32 | Δρmax = 0.54 e Å−3 |
1114 reflections | Δρmin = −0.53 e Å−3 |
62 parameters |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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 |
Mo—Cl | 2.3396 (9) | C3—C4 | 1.394 (7) |
Mo—N | 2.195 (3) | C3—C6 | 1.515 (6) |
Mo—Cli | 2.3396 (9) | C4—C5 | 1.389 (6) |
Mo—Ni | 2.195 (3) | C4—H4 | 1.054 (5) |
Mo—Clii | 2.3396 (9) | C5—H5 | 1.046 (5) |
Mo—Cliii | 2.3396 (9) | C6—C7 | 1.529 (8) |
N—C1 | 1.361 (6) | C6—H6 | 1.041 (4) |
N—C5 | 1.344 (6) | C6—H6iii | 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—H71iii | 0.990 (3) |
C2—H2 | 1.028 (5) | ||
Cl—Mo—N | 90.27 (8) | C3—C2—H2 | 121.7 (4) |
Cl—Mo—Cli | 90.31 (3) | C2—C3—C4 | 116.4 (4) |
Cl—Mo—Ni | 89.73 (8) | C2—C3—C6 | 120.0 (4) |
Cl—Mo—Clii | 180.0000 | C4—C3—C6 | 123.6 (4) |
Cl—Mo—Cliii | 89.69 (3) | C3—C4—C5 | 120.5 (5) |
N—Mo—Cli | 89.73 (8) | C3—C4—H4 | 121.8 (4) |
N—Mo—Ni | 180.0000 | C5—C4—H4 | 117.7 (5) |
N—Mo—Clii | 89.73 (8) | N—C5—C4 | 122.2 (5) |
N—Mo—Cliii | 90.27 (8) | N—C5—H5 | 116.1 (4) |
Cli—Mo—Ni | 90.27 (8) | C4—C5—H5 | 121.7 (5) |
Cli—Mo—Clii | 89.69 (3) | C3—C6—C7 | 115.1 (4) |
Cli—Mo—Cliii | 180.0000 | C3—C6—H6 | 103.7 (3) |
Ni—Mo—Clii | 90.27 (8) | C3—C6—H6iii | 103.7 (3) |
Ni—Mo—Cliii | 89.73 (8) | C7—C6—H6 | 117.1 (3) |
Clii—Mo—Cliii | 90.31 (3) | C7—C6—H6iii | 117.1 (3) |
Mo—N—C1 | 121.3 (3) | H6—C6—H6iii | 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—H71iii | 110.9 (3) |
N—C1—H1 | 117.0 (4) | H71—C7—H72 | 111.0 (3) |
C2—C1—H1 | 120.7 (5) | H71—C7—H71iii | 106.2 (5) |
C1—C2—C3 | 120.7 (4) | H72—C7—H71iii | 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. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C6H16N)[MoCl4(C7H9N)2] | [MoCl4(C7H9N)2] |
Mr | 554.24 | 452.06 |
Crystal system, space group | Orthorhombic, Pca21 | Monoclinic, C2/m |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 19.7025 (9), 7.766 (2), 16.7929 (6) | 16.1077 (8), 7.6691 (4), 7.1566 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 98.012 (4), 90 |
V (Å3) | 2569.6 (6) | 875.44 (8) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.94 | 1.35 |
Crystal size (mm) | 0.50 × 0.30 × 0.15 | 0.19 × 0.11 × 0.10 |
Data collection | ||
Diffractometer | Quantum CCD Rigaku AFC7 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (REQABA; Jacobson, 1997) | – |
Tmin, Tmax | 0.739, 0.869 | – |
No. of measured, independent and observed reflections | 18043, 5860, 3267 [I > 2σ(I)] | 5116, 1358, 1114 [ > 3σ(I)] |
Rint | 0.041 | 0.015 |
(sin θ/λ)max (Å−1) | 0.625 | 0.702 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.059, 1.03 | 0.017, 0.028, 1.32 |
No. of reflections | 4069 | 1114 |
No. of parameters | 253 | 62 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.81, −0.49 | 0.54, −0.53 |
Absolute structure | Flack, 1983 | ? |
Absolute structure parameter | −0.03 (4) | ? |
Computer programs: D*TREK (Molecular Structure Corporation, 1997), CAD-4 Software (Enraf-Nonius, 1989), D*TREK, CAD-4 Software, Xtal3.4 DIFDAT, SORTRF and ADDREF (Hall et al., 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Xtal3.4 CRYLSQ, ORTEPIII (Burnett & Johnson, 1996), Xtal3.4 BONDLA and CIFIO.
Mo1—N1 | 2.196 (2) | Mo1—Cl3 | 2.4309 (13) |
Mo1—N2 | 2.206 (4) | Mo1—Cl2 | 2.4364 (12) |
Mo1—Cl1 | 2.4226 (12) | Mo1—Cl4 | 2.4379 (9) |
N1—Mo1—N2 | 88.97 (14) | Cl1—Mo1—Cl2 | 173.16 (5) |
N1—Mo1—Cl1 | 87.55 (9) | Cl3—Mo1—Cl2 | 90.84 (5) |
N2—Mo1—Cl1 | 87.76 (11) | N1—Mo1—Cl4 | 177.83 (9) |
N1—Mo1—Cl3 | 90.36 (11) | N2—Mo1—Cl4 | 88.99 (11) |
N2—Mo1—Cl3 | 178.47 (11) | Cl1—Mo1—Cl4 | 93.11 (5) |
Cl1—Mo1—Cl3 | 93.59 (4) | Cl3—Mo1—Cl4 | 91.66 (5) |
N1—Mo1—Cl2 | 87.20 (9) | Cl2—Mo1—Cl4 | 91.98 (5) |
N2—Mo1—Cl2 | 87.75 (10) |
Mo—Cl | 2.3396 (9) | Mo—N | 2.195 (3) |
Cl—Mo—N | 90.27 (8) | Cl—Mo—Ni | 89.73 (8) |
Cl—Mo—Cli | 90.31 (3) | Cl—Mo—Clii | 89.69 (3) |
Symmetry codes: (i) −x+1, y, −z+1; (ii) x, −y+1, z. |
[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. [MIVCl4(py)2] has a C2 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).