Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800021139/ob6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800021139/ob6009Isup2.hkl |
CCDC reference: 159703
The substituted formamidines and the Mo2(form)4 systems were prepared according to published syntheses (Cotton et al., 1989). Crystals were grown by the diffusion of hexanes into dichloromethane solution.
H atoms were added at idealized positions, constrained to ride on the atom to which they are bonded and given displacement parameters equal to 1.2 or 1.5Uiso of that bonded atom.
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Mo2(C13H9Cl2N2)4] | Z = 1 |
Mr = 1248.37 | F(000) = 624 |
Triclinic, P1 | Dx = 1.616 Mg m−3 |
a = 10.347 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.496 (2) Å | Cell parameters from 25 reflections |
c = 12.569 (3) Å | θ = 20–23° |
α = 106.61 (3)° | µ = 0.95 mm−1 |
β = 92.04 (3)° | T = 296 K |
γ = 114.55 (3)° | Block, yellow |
V = 1282.7 (4) Å3 | 0.33 × 0.33 × 0.20 mm |
Enraf-Nonius CAD-4 diffractometer | 4196 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
ω–2θ scans | h = 0→12 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→12 |
Tmin = 0.744, Tmax = 0.833 | l = −14→14 |
4498 measured reflections | 3 standard reflections every 60 min |
4498 independent reflections | intensity decay: 0.1% |
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) = 0.064 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.5743P] where P = (Fo2 + 2Fc2)/3 |
4498 reflections | (Δ/σ)max = 0.001 |
316 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
0 constraints |
[Mo2(C13H9Cl2N2)4] | γ = 114.55 (3)° |
Mr = 1248.37 | V = 1282.7 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.347 (2) Å | Mo Kα radiation |
b = 11.496 (2) Å | µ = 0.95 mm−1 |
c = 12.569 (3) Å | T = 296 K |
α = 106.61 (3)° | 0.33 × 0.33 × 0.20 mm |
β = 92.04 (3)° |
Enraf-Nonius CAD-4 diffractometer | 4196 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.744, Tmax = 0.833 | 3 standard reflections every 60 min |
4498 measured reflections | intensity decay: 0.1% |
4498 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.44 e Å−3 |
4498 reflections | Δρmin = −0.50 e Å−3 |
316 parameters |
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 | −0.090740 (17) | 0.440239 (17) | −0.063783 (13) | 0.03207 (7) | |
Cl1 | −0.30161 (11) | −0.18371 (9) | −0.54433 (7) | 0.0947 (3) | |
Cl3 | −0.24097 (15) | 0.16068 (11) | −0.66765 (7) | 0.1148 (4) | |
N3 | 0.02354 (19) | 0.49800 (18) | −0.19250 (14) | 0.0392 (4) | |
N1 | −0.04335 (19) | 0.26818 (18) | −0.10847 (15) | 0.0398 (4) | |
C2 | 0.1618 (2) | 0.5846 (2) | −0.16174 (18) | 0.0415 (5) | |
H2 | 0.2160 | 0.6096 | −0.2159 | 0.050* | |
C1 | 0.0668 (2) | 0.2794 (2) | −0.04261 (18) | 0.0430 (5) | |
H1 | 0.0875 | 0.2058 | −0.0540 | 0.052* | |
C11 | −0.1042 (2) | 0.1557 (2) | −0.20989 (18) | 0.0407 (5) | |
C31 | −0.0335 (2) | 0.4263 (2) | −0.30878 (17) | 0.0411 (5) | |
C12 | −0.0216 (3) | 0.1010 (3) | −0.2711 (2) | 0.0577 (6) | |
H12A | 0.0763 | 0.1358 | −0.2436 | 0.069* | |
C35 | −0.2438 (3) | 0.2988 (3) | −0.4557 (2) | 0.0635 (7) | |
H35A | −0.3423 | 0.2664 | −0.4791 | 0.076* | |
C15 | −0.3099 (3) | −0.0021 (3) | −0.3560 (2) | 0.0613 (7) | |
H15A | −0.4074 | −0.0367 | −0.3848 | 0.074* | |
C16 | −0.2492 (3) | 0.1013 (2) | −0.2538 (2) | 0.0521 (6) | |
H16A | −0.3070 | 0.1350 | −0.2137 | 0.063* | |
C13 | −0.0831 (3) | −0.0044 (3) | −0.3722 (2) | 0.0647 (7) | |
H13A | −0.0272 | −0.0417 | −0.4112 | 0.078* | |
C32 | 0.0471 (3) | 0.3923 (3) | −0.3859 (2) | 0.0638 (7) | |
H32A | 0.1451 | 0.4217 | −0.3630 | 0.077* | |
C34 | −0.1614 (4) | 0.2674 (3) | −0.5297 (2) | 0.0642 (8) | |
C33 | −0.0164 (4) | 0.3150 (3) | −0.4971 (2) | 0.0761 (9) | |
H33A | 0.0394 | 0.2955 | −0.5493 | 0.091* | |
C36 | −0.1803 (3) | 0.3790 (3) | −0.3459 (2) | 0.0523 (6) | |
H36A | −0.2364 | 0.4020 | −0.2955 | 0.063* | |
C14 | −0.2258 (3) | −0.0536 (3) | −0.4147 (2) | 0.0599 (7) | |
Cl4 | 0.84649 (7) | 1.02265 (7) | 0.06607 (7) | 0.0712 (2) | |
Cl2 | 0.56040 (8) | 0.40108 (10) | 0.38273 (7) | 0.0755 (2) | |
N4 | 0.22380 (18) | 0.63630 (18) | −0.05369 (14) | 0.0377 (4) | |
N2 | 0.14781 (19) | 0.39444 (18) | 0.03926 (15) | 0.0408 (4) | |
C41 | 0.3708 (2) | 0.7349 (2) | −0.02570 (18) | 0.0377 (4) | |
C21 | 0.2465 (2) | 0.3908 (2) | 0.11889 (18) | 0.0388 (5) | |
C43 | 0.5978 (2) | 0.8462 (2) | 0.1048 (2) | 0.0475 (5) | |
H43A | 0.6511 | 0.8597 | 0.1721 | 0.057* | |
C26 | 0.3940 (3) | 0.4623 (3) | 0.1259 (2) | 0.0482 (5) | |
H26A | 0.4286 | 0.5078 | 0.0749 | 0.058* | |
C25 | 0.4901 (3) | 0.4667 (3) | 0.2075 (2) | 0.0526 (6) | |
H25A | 0.5890 | 0.5156 | 0.2120 | 0.063* | |
C22 | 0.1980 (3) | 0.3224 (3) | 0.1944 (2) | 0.0541 (6) | |
H22A | 0.0993 | 0.2736 | 0.1905 | 0.065* | |
C42 | 0.4518 (2) | 0.7577 (2) | 0.07538 (19) | 0.0419 (5) | |
H42A | 0.4071 | 0.7125 | 0.1243 | 0.050* | |
C46 | 0.4384 (3) | 0.8104 (2) | −0.0931 (2) | 0.0478 (5) | |
H46A | 0.3851 | 0.8023 | −0.1582 | 0.057* | |
C23 | 0.2935 (3) | 0.3252 (3) | 0.2754 (2) | 0.0598 (7) | |
H23A | 0.2597 | 0.2778 | 0.3253 | 0.072* | |
C44 | 0.6622 (2) | 0.9136 (2) | 0.0326 (2) | 0.0468 (5) | |
C24 | 0.4388 (3) | 0.3986 (3) | 0.2818 (2) | 0.0488 (5) | |
C45 | 0.5837 (3) | 0.8974 (2) | −0.0648 (2) | 0.0532 (6) | |
H45A | 0.6285 | 0.9452 | −0.1121 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.02872 (10) | 0.03397 (11) | 0.02740 (10) | 0.01083 (7) | 0.00068 (6) | 0.00676 (7) |
Cl1 | 0.1102 (7) | 0.0721 (5) | 0.0520 (4) | 0.0181 (5) | 0.0033 (4) | −0.0141 (4) |
Cl3 | 0.1781 (11) | 0.1075 (7) | 0.0414 (4) | 0.0783 (8) | −0.0351 (5) | −0.0163 (4) |
N3 | 0.0369 (9) | 0.0430 (10) | 0.0302 (9) | 0.0127 (8) | 0.0012 (7) | 0.0099 (8) |
N1 | 0.0418 (10) | 0.0363 (9) | 0.0358 (9) | 0.0156 (8) | 0.0032 (8) | 0.0073 (7) |
C2 | 0.0399 (12) | 0.0431 (12) | 0.0344 (11) | 0.0128 (10) | 0.0071 (9) | 0.0116 (9) |
C1 | 0.0480 (13) | 0.0413 (12) | 0.0406 (12) | 0.0221 (10) | 0.0068 (10) | 0.0114 (10) |
C11 | 0.0479 (12) | 0.0336 (11) | 0.0355 (11) | 0.0151 (10) | 0.0052 (9) | 0.0091 (9) |
C31 | 0.0468 (12) | 0.0406 (11) | 0.0306 (10) | 0.0147 (10) | 0.0024 (9) | 0.0118 (9) |
C12 | 0.0559 (15) | 0.0579 (15) | 0.0504 (14) | 0.0256 (13) | 0.0066 (12) | 0.0056 (12) |
C35 | 0.0676 (17) | 0.0636 (17) | 0.0465 (15) | 0.0255 (14) | −0.0163 (13) | 0.0086 (13) |
C15 | 0.0542 (15) | 0.0538 (15) | 0.0530 (15) | 0.0119 (12) | −0.0024 (12) | 0.0052 (12) |
C16 | 0.0498 (14) | 0.0478 (13) | 0.0472 (13) | 0.0186 (11) | 0.0064 (11) | 0.0042 (11) |
C13 | 0.078 (2) | 0.0611 (16) | 0.0506 (15) | 0.0344 (15) | 0.0167 (14) | 0.0054 (13) |
C32 | 0.0559 (16) | 0.0771 (19) | 0.0451 (14) | 0.0268 (14) | 0.0078 (12) | 0.0054 (13) |
C34 | 0.096 (2) | 0.0546 (15) | 0.0320 (12) | 0.0341 (15) | −0.0129 (13) | 0.0024 (11) |
C33 | 0.096 (2) | 0.087 (2) | 0.0397 (14) | 0.0454 (19) | 0.0168 (15) | 0.0046 (14) |
C36 | 0.0509 (14) | 0.0570 (15) | 0.0392 (12) | 0.0202 (12) | −0.0011 (10) | 0.0090 (11) |
C14 | 0.0798 (19) | 0.0408 (13) | 0.0385 (13) | 0.0142 (13) | 0.0062 (13) | 0.0036 (10) |
Cl4 | 0.0366 (3) | 0.0564 (4) | 0.0962 (5) | 0.0032 (3) | 0.0119 (3) | 0.0173 (4) |
Cl2 | 0.0620 (4) | 0.1122 (6) | 0.0685 (4) | 0.0472 (4) | 0.0014 (3) | 0.0409 (4) |
N4 | 0.0312 (9) | 0.0401 (9) | 0.0337 (9) | 0.0107 (7) | 0.0028 (7) | 0.0092 (7) |
N2 | 0.0406 (10) | 0.0420 (10) | 0.0384 (10) | 0.0195 (8) | 0.0017 (8) | 0.0101 (8) |
C41 | 0.0337 (10) | 0.0358 (11) | 0.0382 (11) | 0.0133 (9) | 0.0071 (9) | 0.0079 (9) |
C21 | 0.0402 (11) | 0.0390 (11) | 0.0383 (11) | 0.0210 (9) | 0.0045 (9) | 0.0095 (9) |
C43 | 0.0366 (12) | 0.0473 (13) | 0.0497 (13) | 0.0143 (10) | 0.0009 (10) | 0.0107 (11) |
C26 | 0.0453 (13) | 0.0601 (15) | 0.0512 (13) | 0.0277 (11) | 0.0170 (11) | 0.0278 (12) |
C25 | 0.0342 (11) | 0.0623 (15) | 0.0649 (16) | 0.0214 (11) | 0.0083 (11) | 0.0264 (13) |
C22 | 0.0360 (12) | 0.0592 (15) | 0.0687 (16) | 0.0144 (11) | 0.0077 (11) | 0.0340 (13) |
C42 | 0.0360 (11) | 0.0423 (12) | 0.0405 (12) | 0.0119 (9) | 0.0065 (9) | 0.0125 (10) |
C46 | 0.0492 (13) | 0.0433 (12) | 0.0432 (12) | 0.0130 (10) | 0.0037 (10) | 0.0156 (10) |
C23 | 0.0520 (15) | 0.0763 (18) | 0.0669 (17) | 0.0286 (14) | 0.0146 (12) | 0.0456 (15) |
C44 | 0.0337 (11) | 0.0352 (11) | 0.0601 (15) | 0.0097 (9) | 0.0117 (10) | 0.0080 (10) |
C24 | 0.0451 (13) | 0.0604 (15) | 0.0473 (13) | 0.0290 (11) | 0.0035 (10) | 0.0191 (11) |
C45 | 0.0535 (14) | 0.0412 (12) | 0.0555 (15) | 0.0098 (11) | 0.0173 (12) | 0.0192 (11) |
Mo1—Mo1i | 2.0899 (12) | C13—C14 | 1.366 (4) |
Mo1—N3 | 2.1342 (19) | C32—C33 | 1.383 (4) |
Mo1—N1 | 2.1585 (18) | C34—C33 | 1.365 (5) |
Mo1—N2i | 2.1602 (18) | Cl4—C44 | 1.744 (2) |
Mo1—N4i | 2.1751 (18) | Cl2—C24 | 1.741 (2) |
Cl1—C14 | 1.746 (3) | N4—C41 | 1.422 (3) |
Cl3—C34 | 1.741 (3) | N4—Mo1i | 2.1751 (18) |
N3—C2 | 1.320 (3) | N2—C21 | 1.426 (3) |
N3—C31 | 1.418 (3) | N2—Mo1i | 2.1602 (18) |
N1—C1 | 1.323 (3) | C41—C46 | 1.385 (3) |
N1—C11 | 1.420 (3) | C41—C42 | 1.392 (3) |
C2—N4 | 1.330 (3) | C21—C22 | 1.380 (3) |
C1—N2 | 1.323 (3) | C21—C26 | 1.386 (3) |
C11—C16 | 1.382 (3) | C43—C44 | 1.372 (3) |
C11—C12 | 1.391 (3) | C43—C42 | 1.387 (3) |
C31—C32 | 1.378 (3) | C26—C25 | 1.377 (3) |
C31—C36 | 1.393 (3) | C25—C24 | 1.370 (3) |
C12—C13 | 1.381 (4) | C22—C23 | 1.377 (3) |
C35—C34 | 1.358 (4) | C46—C45 | 1.377 (3) |
C35—C36 | 1.376 (3) | C23—C24 | 1.370 (4) |
C15—C14 | 1.369 (4) | C44—C45 | 1.367 (4) |
C15—C16 | 1.381 (4) | ||
Mo1i—Mo1—N3 | 93.63 (5) | C33—C34—Cl3 | 118.9 (2) |
Mo1i—Mo1—N1 | 93.78 (6) | C34—C33—C32 | 119.7 (3) |
N3—Mo1—N1 | 86.82 (7) | C35—C36—C31 | 121.1 (3) |
Mo1i—Mo1—N2i | 91.62 (6) | C13—C14—C15 | 120.4 (2) |
N3—Mo1—N2i | 89.16 (7) | C13—C14—Cl1 | 119.7 (2) |
N1—Mo1—N2i | 173.45 (6) | C15—C14—Cl1 | 119.9 (2) |
Mo1i—Mo1—N4i | 91.91 (5) | C2—N4—C41 | 117.33 (18) |
N3—Mo1—N4i | 174.15 (6) | C2—N4—Mo1i | 116.63 (14) |
N1—Mo1—N4i | 90.92 (7) | C41—N4—Mo1i | 126.04 (14) |
N2i—Mo1—N4i | 92.58 (7) | C1—N2—C21 | 116.80 (19) |
C2—N3—C31 | 118.96 (19) | C1—N2—Mo1i | 117.87 (15) |
C2—N3—Mo1 | 117.38 (14) | C21—N2—Mo1i | 123.95 (14) |
C31—N3—Mo1 | 122.17 (14) | C46—C41—C42 | 117.8 (2) |
C1—N1—C11 | 117.59 (19) | C46—C41—N4 | 123.8 (2) |
C1—N1—Mo1 | 115.89 (15) | C42—C41—N4 | 118.39 (19) |
C11—N1—Mo1 | 125.77 (14) | C22—C21—C26 | 118.5 (2) |
N3—C2—N4 | 120.3 (2) | C22—C21—N2 | 121.1 (2) |
N2—C1—N1 | 120.5 (2) | C26—C21—N2 | 120.4 (2) |
C16—C11—C12 | 117.8 (2) | C44—C43—C42 | 118.7 (2) |
C16—C11—N1 | 119.8 (2) | C25—C26—C21 | 120.8 (2) |
C12—C11—N1 | 122.4 (2) | C24—C25—C26 | 119.4 (2) |
C32—C31—C36 | 118.0 (2) | C23—C22—C21 | 121.1 (2) |
C32—C31—N3 | 123.2 (2) | C43—C42—C41 | 121.5 (2) |
C36—C31—N3 | 118.6 (2) | C45—C46—C41 | 120.8 (2) |
C13—C12—C11 | 120.9 (3) | C24—C23—C22 | 119.3 (2) |
C34—C35—C36 | 119.4 (3) | C45—C44—C43 | 121.0 (2) |
C14—C15—C16 | 119.7 (3) | C45—C44—Cl4 | 119.39 (19) |
C15—C16—C11 | 121.3 (2) | C43—C44—Cl4 | 119.6 (2) |
C14—C13—C12 | 119.9 (3) | C23—C24—C25 | 121.0 (2) |
C31—C32—C33 | 120.7 (3) | C23—C24—Cl2 | 119.7 (2) |
C35—C34—C33 | 121.0 (2) | C25—C24—Cl2 | 119.35 (19) |
C35—C34—Cl3 | 120.1 (2) | C44—C45—C46 | 120.1 (2) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mo2(C13H9Cl2N2)4] |
Mr | 1248.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.347 (2), 11.496 (2), 12.569 (3) |
α, β, γ (°) | 106.61 (3), 92.04 (3), 114.55 (3) |
V (Å3) | 1282.7 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.33 × 0.33 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.744, 0.833 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4498, 4498, 4196 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.064, 1.08 |
No. of reflections | 4498 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.50 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Mo1—Mo1i | 2.0899 (12) | Mo1—N2i | 2.1602 (18) |
Mo1—N3 | 2.1342 (19) | Mo1—N4i | 2.1751 (18) |
Mo1—N1 | 2.1585 (18) | ||
Mo1i—Mo1—N3 | 93.63 (5) | Mo1i—Mo1—N2i | 91.62 (6) |
Mo1i—Mo1—N1 | 93.78 (6) | Mo1i—Mo1—N4i | 91.91 (5) |
Symmetry code: (i) −x, −y+1, −z. |
Metal–metal interactions are central to the behavior of a wide variety of molecules, clusters, interfaces, and materials. Our interest in the bonding of metal atoms to each other has led us to examine the electronic structures of numerous such systems via gas-phase photoelectron spectroscopy (Lichtenberger et al., 1999, 2000). Part of this effort has been focused on understanding the effect of substitution of functional groups at the phenyl rings of the diphenylformamidinate ligand on the electronic structure of metal–metal bonded systems as a whole. As we intend to report shortly, the use of various substituents on the formamidine ligand set affects the relative ease of the gas-phase oxidation of the various components of the Mo—Mo quadruple bond of Mo2(form)4 [form = N,N'-bis(4-X-phenyl)formamidinate] and makes for an interesting comparison with the solution-phase oxidation potentials reported by Ren and coworkers (Lin et al., 1995, 1996). The crystal structure of the 3-Cl—Ph derivative related closely to the title 4-Cl—Ph complex, (I), was determined by Lin et al. (1996).