Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003440/cv6006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003440/cv6006Isup2.hkl |
CCDC reference: 159834
The compound (DMDPP)Re(CO)3(CH3CN)(PF6) was prepared by modifying the literature method of Caspar & Meyer (1983). To a 250 ml flask containing (DMDPP)Re(CO)3Br (500 mg, 0.7 mmol) and AgPF6 (215 mg, 0.85 mmol) was added 100 ml anhydrous CH3CN. The resulting mixture was refluxed under argon for 8 h. The solvent was filtered under argon to remove AgBr precipitate and the filtrate was evaporated to dryness under reduced pressure. The crude product was recrystallized from CH3CN/ether to afford a bright-yellow solid in 92% yield. IR [ν(C═O), CH3CN, cm-1]: 2038, 1937. 1H NMR (DMSO-d6): 8.23 (s, 2 H, H5,6-phen), 8.05 (s, 2 H, H3,8-phen), 7.70–7.63 (m, 10 H, ph), 3.33 (s, 6 H, CH3), 2.28 (s, 3 H, CH3CN). 13C NMR (DMSO-d6): 196.0, 191.4, 163.4, 151.2, 147.6, 135.2, 129.8, 129.6, 129.1, 128.9, 127.0, 124.6, 118.0, 30.4, 1.06. Single crystals were grown by layering an acetonitrile solution of the complex with ether.
It is well known (Sun & Lees, 2000) that rhenium(I) readily forms tricarbonyl molecular complexes of the general formula (L)Re(CO)3X, where L is chelating bipyridyl ligand, and X is Cl or Br. Substitution of the halogen with neutral molecule such as CH3CN leads to formation of a complex cation and an additional anion is needed for charge compensation.
A new molecular ionic compound has been prepared by reacting BrRe(CO)3(DMDPP) and AgPF6 in refluxing CH3CN (DMDPP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, C26H20N2). The crystal structure of this molecular ionic compound, acetonitriletricarbonyl(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)- rhenium(I) hexafluorophosphate, (I), has been determined. The Re atom is octahedrally coordinated and the base of the octahedron is formed by two N atoms (N2 and N3) of the chelating DMDPP ligand and C atoms (C1 and C2) of two carbonyl groups, whereas the third carbonyl ligand (C3) and acetonitrile (N1) form apexes (Fig. 1). This octahedron is slightly distorted (see N—Re—C angles in Table 1) due to the chelating DMDPP ligand. However, the C3 and N1 forming apexes are practically on one line with Re [N1—Re—C3 is 179.1 (2)°].
All aromatic rings in the DMDPP ligand lie in a plane with deviations of less than 0.01 Å. This deviation is tripled when three rings of phenanthroline are taken together, but even then this does not exeed 0.03 Å. The two phenyl groups, C10–C15 and C26–C31, are tilted from the phenanthroline plane by 64.7 (2) and 56.1 (2)°, respectively. The ligand has only a twofold axis as the local symmetry element because of this tilt.
The Re cations and PF6 anions are held together by weak C—H···F hydrogen bonds, as listed in Table 2.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Re(C26H20N2)(C2H3N)(CO)3](PF6) | F(000) = 1592 |
Mr = 816.7 | Dx = 1.757 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2648 (5) Å | Cell parameters from 7718 reflections |
b = 23.4667 (11) Å | θ = 4.4–54.7° |
c = 13.2040 (6) Å | µ = 4.06 mm−1 |
β = 103.847 (1)° | T = 293 K |
V = 3088.2 (3) Å3 | Prizm, yellow |
Z = 4 | 0.20 × 0.18 × 0.13 mm |
CCD Smart Apex diffractometer | 9420 independent reflections |
Radiation source: fine-focus sealed tube | 6049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 30.6°, θmin = 1.7° |
Absorption correction: ψ scan (SADABS; Sheldrick, 1996) | h = −13→14 |
Tmin = 0.46, Tmax = 0.59 | k = −25→33 |
26336 measured reflections | l = −11→18 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0464P)2] where P = (Fo2 + 2Fc2)/3 |
9420 reflections | (Δ/σ)max < 0.001 |
409 parameters | Δρmax = 1.03 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[Re(C26H20N2)(C2H3N)(CO)3](PF6) | V = 3088.2 (3) Å3 |
Mr = 816.7 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.2648 (5) Å | µ = 4.06 mm−1 |
b = 23.4667 (11) Å | T = 293 K |
c = 13.2040 (6) Å | 0.20 × 0.18 × 0.13 mm |
β = 103.847 (1)° |
CCD Smart Apex diffractometer | 9420 independent reflections |
Absorption correction: ψ scan (SADABS; Sheldrick, 1996) | 6049 reflections with I > 2σ(I) |
Tmin = 0.46, Tmax = 0.59 | Rint = 0.047 |
26336 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 1.03 e Å−3 |
9420 reflections | Δρmin = −0.50 e Å−3 |
409 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 | ||
Re1 | 0.15826 (2) | 0.10161 (1) | 0.61269 (1) | 0.04285 (7) | |
P1 | 0.39210 (15) | 0.06783 (7) | 0.24644 (10) | 0.0628 (4) | |
F1 | 0.3868 (6) | 0.0785 (2) | 0.3612 (3) | 0.156 (2) | |
F2 | 0.3990 (6) | 0.0556 (2) | 0.1335 (3) | 0.163 (2) | |
F3 | 0.5145 (7) | 0.1030 (3) | 0.2608 (7) | 0.233 (4) | |
F4 | 0.2646 (5) | 0.0327 (3) | 0.2325 (5) | 0.209 (3) | |
F5 | 0.4679 (5) | 0.0110 (2) | 0.2817 (3) | 0.1388 (18) | |
F6 | 0.3117 (7) | 0.1231 (3) | 0.2162 (4) | 0.180 (3) | |
C1 | 0.0113 (5) | 0.1011 (2) | 0.4918 (4) | 0.0605 (13) | |
O1 | −0.0826 (4) | 0.09915 (18) | 0.4241 (3) | 0.0863 (14) | |
C2 | 0.0435 (5) | 0.0503 (3) | 0.6618 (4) | 0.0679 (16) | |
O2 | −0.0330 (4) | 0.0203 (3) | 0.6862 (3) | 0.118 (2) | |
C3 | 0.0735 (5) | 0.1628 (3) | 0.6659 (4) | 0.0712 (16) | |
O3 | 0.0143 (4) | 0.1977 (2) | 0.6969 (4) | 0.1159 (18) | |
N1 | 0.2529 (4) | 0.03391 (17) | 0.5509 (3) | 0.0493 (9) | |
C4 | 0.2920 (5) | −0.0038 (2) | 0.5138 (4) | 0.0534 (12) | |
C5 | 0.3409 (6) | −0.0520 (2) | 0.4648 (4) | 0.0711 (15) | |
H5A | 0.2903 | −0.0854 | 0.4728 | 0.107* | |
H5B | 0.4340 | −0.0582 | 0.4972 | 0.107* | |
H5C | 0.3307 | −0.0442 | 0.3919 | 0.107* | |
C6 | 0.1546 (5) | 0.1865 (3) | 0.3953 (4) | 0.085 (2) | |
H6A | 0.1563 | 0.2136 | 0.3410 | 0.128* | |
H6B | 0.0887 | 0.1979 | 0.4320 | 0.128* | |
H6C | 0.1323 | 0.1495 | 0.3651 | 0.128* | |
C7 | 0.2885 (4) | 0.1843 (2) | 0.4689 (3) | 0.0518 (12) | |
C8 | 0.3957 (5) | 0.2117 (2) | 0.4416 (3) | 0.0551 (12) | |
H8 | 0.3800 | 0.2305 | 0.3779 | 0.066* | |
C9 | 0.5223 (4) | 0.2120 (2) | 0.5037 (3) | 0.0461 (10) | |
C10 | 0.6350 (4) | 0.2394 (2) | 0.4704 (3) | 0.0488 (11) | |
C11 | 0.6770 (5) | 0.2171 (2) | 0.3872 (4) | 0.0604 (13) | |
H11 | 0.6309 | 0.1867 | 0.3495 | 0.073* | |
C12 | 0.7890 (6) | 0.2401 (3) | 0.3596 (5) | 0.0727 (15) | |
H12 | 0.8188 | 0.2245 | 0.3044 | 0.087* | |
C13 | 0.8546 (5) | 0.2850 (3) | 0.4129 (5) | 0.0697 (15) | |
H13 | 0.9282 | 0.3006 | 0.3933 | 0.084* | |
C14 | 0.8130 (6) | 0.3076 (3) | 0.4954 (4) | 0.0764 (16) | |
H14 | 0.8582 | 0.3385 | 0.5318 | 0.092* | |
C15 | 0.7057 (5) | 0.2848 (2) | 0.5241 (4) | 0.0662 (14) | |
H15 | 0.6791 | 0.3000 | 0.5810 | 0.079* | |
N2 | 0.3056 (3) | 0.15518 (16) | 0.5589 (3) | 0.0419 (8) | |
C16 | 0.4328 (4) | 0.15575 (17) | 0.6251 (3) | 0.0372 (9) | |
C17 | 0.5410 (4) | 0.18393 (18) | 0.6013 (3) | 0.0412 (9) | |
C18 | 0.6688 (4) | 0.1818 (2) | 0.6741 (3) | 0.0474 (11) | |
H18 | 0.7419 | 0.1999 | 0.6580 | 0.057* | |
C19 | 0.6850 (4) | 0.1541 (2) | 0.7653 (3) | 0.0466 (10) | |
H19 | 0.7690 | 0.1540 | 0.8117 | 0.056* | |
C20 | 0.5770 (4) | 0.12494 (19) | 0.7926 (3) | 0.0377 (9) | |
C21 | 0.4498 (4) | 0.12524 (18) | 0.7222 (3) | 0.0360 (8) | |
N3 | 0.3395 (3) | 0.09939 (14) | 0.7434 (3) | 0.0388 (8) | |
C22 | 0.2369 (5) | 0.0478 (3) | 0.8665 (4) | 0.0731 (17) | |
H22A | 0.1625 | 0.0738 | 0.8510 | 0.110* | |
H22B | 0.2594 | 0.0394 | 0.9398 | 0.110* | |
H22C | 0.2128 | 0.0132 | 0.8278 | 0.110* | |
C23 | 0.3544 (4) | 0.0741 (2) | 0.8372 (3) | 0.0438 (10) | |
C24 | 0.4770 (4) | 0.0734 (2) | 0.9088 (3) | 0.0451 (10) | |
H24 | 0.4830 | 0.0558 | 0.9728 | 0.054* | |
C25 | 0.5901 (4) | 0.09747 (19) | 0.8897 (3) | 0.0420 (10) | |
C26 | 0.7172 (4) | 0.0964 (2) | 0.9719 (3) | 0.0488 (11) | |
C27 | 0.7171 (6) | 0.1155 (3) | 1.0708 (4) | 0.0695 (16) | |
H27 | 0.6383 | 0.1296 | 1.0843 | 0.083* | |
C28 | 0.8330 (7) | 0.1139 (3) | 1.1499 (5) | 0.093 (2) | |
H28 | 0.8312 | 0.1265 | 1.2164 | 0.112* | |
C29 | 0.9501 (6) | 0.0940 (3) | 1.1311 (5) | 0.084 (2) | |
H29 | 1.0285 | 0.0941 | 1.1839 | 0.101* | |
C30 | 0.9512 (5) | 0.0740 (3) | 1.0337 (5) | 0.0729 (16) | |
H30 | 1.0305 | 0.0599 | 1.0211 | 0.088* | |
C31 | 0.8354 (4) | 0.0744 (3) | 0.9539 (4) | 0.0576 (13) | |
H31 | 0.8368 | 0.0601 | 0.8886 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.03226 (9) | 0.05381 (12) | 0.04068 (10) | −0.00301 (8) | 0.00519 (6) | 0.00153 (8) |
P1 | 0.0658 (9) | 0.0751 (11) | 0.0457 (7) | 0.0005 (8) | 0.0099 (6) | 0.0000 (7) |
F1 | 0.270 (6) | 0.138 (4) | 0.071 (3) | 0.074 (4) | 0.060 (3) | 0.001 (3) |
F2 | 0.295 (7) | 0.146 (5) | 0.059 (2) | 0.019 (4) | 0.065 (3) | 0.000 (3) |
F3 | 0.166 (6) | 0.255 (9) | 0.305 (9) | −0.146 (6) | 0.106 (6) | −0.105 (6) |
F4 | 0.102 (4) | 0.265 (8) | 0.243 (7) | −0.070 (4) | 0.011 (4) | 0.029 (6) |
F5 | 0.194 (5) | 0.122 (4) | 0.098 (3) | 0.074 (4) | 0.030 (3) | 0.001 (3) |
F6 | 0.266 (7) | 0.163 (5) | 0.122 (4) | 0.111 (5) | 0.066 (4) | 0.068 (4) |
C1 | 0.048 (3) | 0.065 (4) | 0.063 (3) | −0.011 (2) | 0.003 (2) | 0.011 (3) |
O1 | 0.059 (2) | 0.110 (4) | 0.071 (3) | −0.019 (2) | −0.0224 (19) | 0.021 (2) |
C2 | 0.045 (3) | 0.095 (5) | 0.056 (3) | −0.022 (3) | −0.004 (2) | 0.014 (3) |
O2 | 0.070 (3) | 0.181 (6) | 0.091 (3) | −0.069 (3) | −0.002 (2) | 0.044 (3) |
C3 | 0.041 (3) | 0.094 (5) | 0.075 (4) | 0.010 (3) | 0.009 (2) | −0.015 (3) |
O3 | 0.074 (3) | 0.137 (5) | 0.133 (4) | 0.035 (3) | 0.018 (3) | −0.043 (3) |
N1 | 0.053 (2) | 0.047 (2) | 0.046 (2) | 0.0042 (19) | 0.0080 (17) | −0.0009 (18) |
C4 | 0.051 (3) | 0.058 (3) | 0.045 (3) | 0.001 (2) | 0.001 (2) | 0.007 (2) |
C5 | 0.081 (4) | 0.067 (4) | 0.063 (3) | 0.010 (3) | 0.013 (3) | −0.012 (3) |
C6 | 0.048 (3) | 0.117 (6) | 0.078 (4) | −0.005 (3) | −0.009 (3) | 0.045 (4) |
C7 | 0.043 (2) | 0.061 (3) | 0.048 (3) | −0.001 (2) | 0.0039 (19) | 0.010 (2) |
C8 | 0.055 (3) | 0.065 (3) | 0.044 (3) | −0.001 (2) | 0.009 (2) | 0.020 (2) |
C9 | 0.047 (2) | 0.047 (3) | 0.046 (2) | −0.003 (2) | 0.0143 (19) | 0.005 (2) |
C10 | 0.050 (3) | 0.046 (3) | 0.051 (3) | −0.003 (2) | 0.013 (2) | 0.007 (2) |
C11 | 0.069 (3) | 0.053 (3) | 0.063 (3) | −0.008 (3) | 0.023 (3) | 0.002 (2) |
C12 | 0.081 (4) | 0.065 (4) | 0.084 (4) | −0.002 (3) | 0.044 (3) | 0.005 (3) |
C13 | 0.062 (3) | 0.063 (4) | 0.090 (4) | −0.014 (3) | 0.031 (3) | 0.013 (3) |
C14 | 0.091 (4) | 0.066 (4) | 0.075 (4) | −0.032 (3) | 0.027 (3) | −0.002 (3) |
C15 | 0.076 (4) | 0.059 (4) | 0.071 (3) | −0.016 (3) | 0.031 (3) | −0.003 (3) |
N2 | 0.0352 (17) | 0.045 (2) | 0.0429 (19) | 0.0007 (15) | 0.0050 (14) | 0.0039 (16) |
C16 | 0.036 (2) | 0.036 (2) | 0.038 (2) | 0.0002 (17) | 0.0073 (16) | −0.0023 (17) |
C17 | 0.037 (2) | 0.043 (3) | 0.045 (2) | 0.0000 (18) | 0.0121 (17) | 0.0025 (18) |
C18 | 0.038 (2) | 0.054 (3) | 0.051 (3) | −0.006 (2) | 0.0129 (18) | 0.000 (2) |
C19 | 0.036 (2) | 0.055 (3) | 0.046 (2) | −0.0055 (19) | 0.0023 (17) | −0.002 (2) |
C20 | 0.034 (2) | 0.044 (2) | 0.035 (2) | 0.0004 (17) | 0.0065 (16) | −0.0041 (17) |
C21 | 0.0341 (19) | 0.040 (2) | 0.034 (2) | 0.0000 (17) | 0.0084 (15) | −0.0029 (17) |
N3 | 0.0348 (17) | 0.046 (2) | 0.0360 (18) | −0.0047 (15) | 0.0092 (13) | 0.0001 (15) |
C22 | 0.053 (3) | 0.115 (5) | 0.050 (3) | −0.026 (3) | 0.009 (2) | 0.024 (3) |
C23 | 0.041 (2) | 0.054 (3) | 0.037 (2) | −0.004 (2) | 0.0107 (17) | 0.001 (2) |
C24 | 0.047 (2) | 0.055 (3) | 0.032 (2) | 0.003 (2) | 0.0069 (17) | 0.0074 (19) |
C25 | 0.037 (2) | 0.052 (3) | 0.036 (2) | 0.0039 (19) | 0.0078 (16) | 0.0001 (19) |
C26 | 0.039 (2) | 0.060 (3) | 0.042 (2) | 0.004 (2) | 0.0010 (18) | 0.005 (2) |
C27 | 0.067 (3) | 0.090 (5) | 0.048 (3) | 0.013 (3) | 0.006 (2) | −0.009 (3) |
C28 | 0.087 (5) | 0.129 (6) | 0.049 (3) | 0.016 (4) | −0.013 (3) | −0.021 (3) |
C29 | 0.057 (4) | 0.105 (6) | 0.075 (4) | −0.003 (3) | −0.013 (3) | 0.002 (4) |
C30 | 0.036 (3) | 0.096 (5) | 0.081 (4) | 0.004 (3) | 0.003 (2) | 0.015 (3) |
C31 | 0.042 (3) | 0.080 (4) | 0.050 (3) | 0.008 (2) | 0.008 (2) | 0.004 (3) |
Re1—C3 | 1.899 (6) | C11—C12 | 1.395 (7) |
Re1—C2 | 1.904 (5) | C12—C13 | 1.355 (8) |
Re1—C1 | 1.916 (5) | C13—C14 | 1.368 (7) |
Re1—N1 | 2.125 (4) | C14—C15 | 1.358 (7) |
Re1—N2 | 2.211 (3) | N2—C16 | 1.387 (5) |
Re1—N3 | 2.215 (3) | C16—C17 | 1.392 (5) |
P1—F1 | 1.549 (4) | C16—C21 | 1.442 (5) |
P1—F2 | 1.536 (4) | C17—C18 | 1.429 (6) |
P1—F3 | 1.477 (5) | C18—C19 | 1.343 (6) |
P1—F4 | 1.521 (5) | C19—C20 | 1.420 (6) |
P1—F5 | 1.558 (4) | C20—C21 | 1.410 (5) |
P1—F6 | 1.537 (5) | C20—C25 | 1.412 (6) |
C1—O1 | 1.148 (6) | C21—N3 | 1.371 (5) |
C2—O2 | 1.156 (6) | N3—C23 | 1.348 (5) |
C3—O3 | 1.152 (6) | C22—C23 | 1.486 (6) |
N1—C4 | 1.132 (6) | C23—C24 | 1.382 (5) |
C4—C5 | 1.450 (7) | C24—C25 | 1.367 (6) |
C6—C7 | 1.482 (6) | C25—C26 | 1.484 (6) |
C7—N2 | 1.345 (5) | C26—C27 | 1.381 (7) |
C7—C8 | 1.394 (6) | C26—C31 | 1.390 (6) |
C8—C9 | 1.360 (6) | C27—C28 | 1.384 (7) |
C9—C17 | 1.419 (6) | C28—C29 | 1.366 (9) |
C9—C10 | 1.480 (6) | C29—C30 | 1.371 (8) |
C10—C11 | 1.377 (6) | C30—C31 | 1.387 (6) |
C10—C15 | 1.384 (7) | ||
C3—Re1—C2 | 88.7 (3) | C11—C10—C9 | 119.2 (4) |
C3—Re1—C1 | 88.5 (2) | C15—C10—C9 | 122.2 (4) |
C2—Re1—C1 | 81.5 (2) | C10—C11—C12 | 119.7 (5) |
C3—Re1—N1 | 179.1 (2) | C13—C12—C11 | 120.3 (5) |
C2—Re1—N1 | 92.0 (2) | C12—C13—C14 | 120.2 (5) |
C1—Re1—N1 | 91.0 (2) | C15—C14—C13 | 119.9 (5) |
C3—Re1—N2 | 95.6 (2) | C14—C15—C10 | 121.4 (5) |
C2—Re1—N2 | 174.82 (19) | C7—N2—C16 | 117.2 (4) |
C1—Re1—N2 | 101.47 (17) | C7—N2—Re1 | 128.2 (3) |
N1—Re1—N2 | 83.73 (15) | C16—N2—Re1 | 114.6 (3) |
C3—Re1—N3 | 95.91 (18) | N2—C16—C17 | 122.9 (4) |
C2—Re1—N3 | 101.09 (16) | N2—C16—C21 | 116.8 (3) |
C1—Re1—N3 | 174.91 (18) | C17—C16—C21 | 120.3 (3) |
N1—Re1—N3 | 84.58 (13) | C16—C17—C9 | 118.9 (4) |
N2—Re1—N3 | 75.66 (12) | C16—C17—C18 | 119.0 (4) |
F3—P1—F4 | 178.8 (5) | C9—C17—C18 | 122.0 (4) |
F3—P1—F2 | 89.6 (4) | C19—C18—C17 | 121.1 (4) |
F4—P1—F2 | 91.1 (4) | C18—C19—C20 | 121.6 (4) |
F3—P1—F6 | 87.1 (5) | C21—C20—C25 | 118.1 (4) |
F4—P1—F6 | 91.9 (4) | C21—C20—C19 | 119.1 (4) |
F2—P1—F6 | 93.0 (3) | C25—C20—C19 | 122.7 (4) |
F3—P1—F1 | 90.7 (4) | N3—C21—C20 | 122.9 (4) |
F4—P1—F1 | 88.6 (4) | N3—C21—C16 | 118.1 (3) |
F2—P1—F1 | 178.4 (3) | C20—C21—C16 | 118.9 (4) |
F6—P1—F1 | 88.6 (3) | C23—N3—C21 | 117.7 (3) |
F3—P1—F5 | 95.3 (4) | C23—N3—Re1 | 128.0 (3) |
F4—P1—F5 | 85.7 (4) | C21—N3—Re1 | 114.3 (2) |
F2—P1—F5 | 89.7 (3) | N3—C23—C24 | 121.2 (4) |
F6—P1—F5 | 176.5 (3) | N3—C23—C22 | 120.1 (4) |
F1—P1—F5 | 88.7 (2) | C24—C23—C22 | 118.7 (4) |
O1—C1—Re1 | 174.8 (5) | C25—C24—C23 | 122.9 (4) |
O2—C2—Re1 | 175.5 (5) | C24—C25—C20 | 117.1 (4) |
O3—C3—Re1 | 175.3 (5) | C24—C25—C26 | 119.6 (4) |
C4—N1—Re1 | 173.8 (4) | C20—C25—C26 | 123.2 (4) |
N1—C4—C5 | 179.2 (5) | C27—C26—C31 | 118.7 (4) |
N2—C7—C8 | 121.2 (4) | C27—C26—C25 | 119.1 (4) |
N2—C7—C6 | 120.1 (4) | C31—C26—C25 | 122.1 (4) |
C8—C7—C6 | 118.7 (4) | C26—C27—C28 | 120.7 (5) |
C9—C8—C7 | 123.1 (4) | C29—C28—C27 | 120.5 (6) |
C8—C9—C17 | 116.6 (4) | C28—C29—C30 | 119.5 (5) |
C8—C9—C10 | 121.7 (4) | C29—C30—C31 | 120.8 (5) |
C17—C9—C10 | 121.7 (4) | C30—C31—C26 | 119.9 (5) |
C11—C10—C15 | 118.4 (4) | ||
C24—C25—C26—C27 | −51.4 (7) | H6C—C6—C7—N2 | −69 |
C8—C9—C10—C11 | −65.9 (6) | H22A—C22—C23—N3 | −47 |
H6A—C6—C7—N2 | 171 | H22B—C22—C23—N3 | −167 |
H6B—C6—C7—N2 | 51 | H22C—C22—C23—N3 | 72 |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···F1i | 0.96 (1) | 2.34 (1) | 3.226 (8) | 154 (1) |
C11—H11···F3 | 0.93 (1) | 2.45 (1) | 3.377 (9) | 176 (1) |
C24—H24···F2ii | 0.93 (1) | 2.47 (1) | 3.280 (6) | 145 (1) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Re(C26H20N2)(C2H3N)(CO)3](PF6) |
Mr | 816.7 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.2648 (5), 23.4667 (11), 13.2040 (6) |
β (°) | 103.847 (1) |
V (Å3) | 3088.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.06 |
Crystal size (mm) | 0.20 × 0.18 × 0.13 |
Data collection | |
Diffractometer | CCD Smart Apex |
Absorption correction | ψ scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.46, 0.59 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26336, 9420, 6049 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.100, 0.93 |
No. of reflections | 9420 |
No. of parameters | 409 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.03, −0.50 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Re1—C3 | 1.899 (6) | C11—C12 | 1.395 (7) |
Re1—C2 | 1.904 (5) | C12—C13 | 1.355 (8) |
Re1—C1 | 1.916 (5) | C13—C14 | 1.368 (7) |
Re1—N1 | 2.125 (4) | C14—C15 | 1.358 (7) |
Re1—N2 | 2.211 (3) | N2—C16 | 1.387 (5) |
Re1—N3 | 2.215 (3) | C16—C17 | 1.392 (5) |
P1—F1 | 1.549 (4) | C16—C21 | 1.442 (5) |
P1—F2 | 1.536 (4) | C17—C18 | 1.429 (6) |
P1—F3 | 1.477 (5) | C18—C19 | 1.343 (6) |
P1—F4 | 1.521 (5) | C19—C20 | 1.420 (6) |
P1—F5 | 1.558 (4) | C20—C21 | 1.410 (5) |
P1—F6 | 1.537 (5) | C20—C25 | 1.412 (6) |
C1—O1 | 1.148 (6) | C21—N3 | 1.371 (5) |
C2—O2 | 1.156 (6) | N3—C23 | 1.348 (5) |
C3—O3 | 1.152 (6) | C22—C23 | 1.486 (6) |
N1—C4 | 1.132 (6) | C23—C24 | 1.382 (5) |
C4—C5 | 1.450 (7) | C24—C25 | 1.367 (6) |
C6—C7 | 1.482 (6) | C25—C26 | 1.484 (6) |
C7—N2 | 1.345 (5) | C26—C27 | 1.381 (7) |
C7—C8 | 1.394 (6) | C26—C31 | 1.390 (6) |
C8—C9 | 1.360 (6) | C27—C28 | 1.384 (7) |
C9—C17 | 1.419 (6) | C28—C29 | 1.366 (9) |
C9—C10 | 1.480 (6) | C29—C30 | 1.371 (8) |
C10—C11 | 1.377 (6) | C30—C31 | 1.387 (6) |
C10—C15 | 1.384 (7) | ||
C3—Re1—N1 | 179.1 (2) | F6—P1—F5 | 176.5 (3) |
C2—Re1—N2 | 174.82 (19) | O1—C1—Re1 | 174.8 (5) |
C1—Re1—N3 | 174.91 (18) | O2—C2—Re1 | 175.5 (5) |
N2—Re1—N3 | 75.66 (12) | O3—C3—Re1 | 175.3 (5) |
F3—P1—F4 | 178.8 (5) | C4—N1—Re1 | 173.8 (4) |
F2—P1—F1 | 178.4 (3) | N1—C4—C5 | 179.2 (5) |
C24—C25—C26—C27 | −51.4 (7) | C8—C9—C10—C11 | −65.9 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···F1i | 0.960 (6) | 2.337 (5) | 3.226 (8) | 153.7 (3) |
C11—H11···F3 | 0.932 (5) | 2.447 (8) | 3.377 (9) | 176.2 (4) |
C24—H24···F2ii | 0.929 (4) | 2.474 (5) | 3.280 (6) | 145.1 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z+1. |
It is well known (Sun & Lees, 2000) that rhenium(I) readily forms tricarbonyl molecular complexes of the general formula (L)Re(CO)3X, where L is chelating bipyridyl ligand, and X is Cl or Br. Substitution of the halogen with neutral molecule such as CH3CN leads to formation of a complex cation and an additional anion is needed for charge compensation.
A new molecular ionic compound has been prepared by reacting BrRe(CO)3(DMDPP) and AgPF6 in refluxing CH3CN (DMDPP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, C26H20N2). The crystal structure of this molecular ionic compound, acetonitriletricarbonyl(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)- rhenium(I) hexafluorophosphate, (I), has been determined. The Re atom is octahedrally coordinated and the base of the octahedron is formed by two N atoms (N2 and N3) of the chelating DMDPP ligand and C atoms (C1 and C2) of two carbonyl groups, whereas the third carbonyl ligand (C3) and acetonitrile (N1) form apexes (Fig. 1). This octahedron is slightly distorted (see N—Re—C angles in Table 1) due to the chelating DMDPP ligand. However, the C3 and N1 forming apexes are practically on one line with Re [N1—Re—C3 is 179.1 (2)°].
All aromatic rings in the DMDPP ligand lie in a plane with deviations of less than 0.01 Å. This deviation is tripled when three rings of phenanthroline are taken together, but even then this does not exeed 0.03 Å. The two phenyl groups, C10–C15 and C26–C31, are tilted from the phenanthroline plane by 64.7 (2) and 56.1 (2)°, respectively. The ligand has only a twofold axis as the local symmetry element because of this tilt.
The Re cations and PF6 anions are held together by weak C—H···F hydrogen bonds, as listed in Table 2.