Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009349/bk1610sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009349/bk1610Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009349/bk1610IIsup3.hkl |
CCDC references: 174792; 174793
The synthesis of (I) was carried out by refluxing Re(CO)5Br and tris(pyrazol-1-yl)methane (1:1) in ethanol for 4 h. Crystals were obtained after allowing the solution to cool overnight to 295 K. Stirring (I) with sodium methoxide (1:1) in methanol for 30 min effected its deprotonation; the neutral product was isolated by evaporation of solvent followed by extraction into CH2Cl2. Addition of excess CH3I to this extract, followed by stirring for 4 h, converted the neutral compound to (II). The crude product, (II), was isolated as a colorless solid by evaporating the methylene chloride. Crystals of (II) were obtained by dissolving the product in ethanol and allowing the solution to stand for several days at 253 K.
H-atom positions were all calculated and their refinement was constrained with C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C) for the pyrazole, methylene and methine H atoms. For the methyl groups, the torsion angle which defined the orientation was not allowed to refine, and these atoms were assigned Uiso(H) = 1.5Ueq(C). The occupancy factor of the ethanol solvate was varied during the initial stages of the refinement; since the value converged to about 0.5 it was set at 0.5 for the final cycles. The highest peak in (I) is located 0.93 Å from Re, 1.39 Å from C1 and 1.93 Å from N3, and the deepest trough is 0.98 Å from Re and 1.35 Å from N5. In (II), the highest peak and deepest trough are 1.24 Å from Re and 1.02 Å from C2, respectively.
For both compounds, data collection: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Diffractometer Control Software; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Re(C10H10N6)(CO)3]Br | F(000) = 2112 |
Mr = 564.38 | Dx = 2.183 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.565 (4) Å | Cell parameters from 25 reflections |
b = 9.002 (2) Å | θ = 15.0–18.0° |
c = 18.396 (4) Å | µ = 9.43 mm−1 |
β = 105.93 (3)° | T = 293 K |
V = 3434 (1) Å3 | Block, colorless |
Z = 8 | 0.33 × 0.26 × 0.17 mm |
Enraf-Nonius CAD-4 diffractometer | 3172 reflections with I > 2σ(I) |
Radiation source: normal focus Philips sealed tube | Rint = 0.036 |
Equatorial mounted graphite monochromator | θmax = 27.5°, θmin = 2.3° |
ω/2θ scans | h = 0→27 |
Absorption correction: ψ scan (North et al., 1968) | k = −11→0 |
Tmin = 0.07, Tmax = 0.21 | l = −23→23 |
4033 measured reflections | 3 standard reflections every 60 min |
3929 independent reflections | intensity decay: <2% |
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 not refined |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0412P)2 + 1.98P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.01 |
3929 reflections | Δρmax = 0.55 e Å−3 |
218 parameters | Δρmin = −0.59 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00343 (9) |
[Re(C10H10N6)(CO)3]Br | V = 3434 (1) Å3 |
Mr = 564.38 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.565 (4) Å | µ = 9.43 mm−1 |
b = 9.002 (2) Å | T = 293 K |
c = 18.396 (4) Å | 0.33 × 0.26 × 0.17 mm |
β = 105.93 (3)° |
Enraf-Nonius CAD-4 diffractometer | 3172 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.036 |
Tmin = 0.07, Tmax = 0.21 | 3 standard reflections every 60 min |
4033 measured reflections | intensity decay: <2% |
3929 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters not refined |
S = 1.06 | Δρmax = 0.55 e Å−3 |
3929 reflections | Δρmin = −0.59 e Å−3 |
218 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. The coordinates for the highest peak are (0.3734, 0.8890, 0.2270) locating it 0.93 Å from Re, 1.39 Å from C1 and 1.93 Å from N3. The deepest trough is found at (0.3133, 0.8349, 0.1508) which is 0.98 Å from Re and 1.35 Å from N5. |
x | y | z | Uiso*/Ueq | ||
Re | 0.330173 (9) | 0.88021 (2) | 0.200909 (10) | 0.03940 (9) | |
Br | 0.41970 (3) | 0.30361 (6) | 0.03315 (3) | 0.05823 (16) | |
N1 | 0.37570 (19) | 0.6766 (4) | 0.2542 (2) | 0.0392 (8) | |
O1 | 0.4131 (3) | 1.0946 (6) | 0.3166 (3) | 0.0975 (19) | |
C1 | 0.3828 (3) | 1.0137 (6) | 0.2729 (3) | 0.0608 (15) | |
C2 | 0.2659 (3) | 0.8897 (6) | 0.2546 (3) | 0.0513 (13) | |
O2 | 0.2253 (2) | 0.8932 (6) | 0.2839 (3) | 0.0786 (15) | |
N2 | 0.39157 (18) | 0.5692 (4) | 0.2103 (2) | 0.0385 (8) | |
N3 | 0.4001 (2) | 0.8491 (4) | 0.1368 (2) | 0.0419 (9) | |
O3 | 0.2657 (3) | 1.1480 (5) | 0.1075 (3) | 0.0898 (17) | |
C3 | 0.2899 (3) | 1.0497 (7) | 0.1431 (3) | 0.0567 (14) | |
N4 | 0.40772 (19) | 0.7119 (4) | 0.1092 (2) | 0.0426 (9) | |
C4 | 0.3749 (2) | 0.5861 (5) | 0.1292 (3) | 0.0410 (10) | |
H4A | 0.3885 | 0.4966 | 0.1074 | 0.049* | |
N5 | 0.27532 (18) | 0.7188 (5) | 0.1207 (2) | 0.0417 (9) | |
C5 | 0.3949 (3) | 0.6235 (6) | 0.3244 (3) | 0.0488 (12) | |
H5A | 0.3906 | 0.6731 | 0.3671 | 0.059* | |
N6 | 0.30618 (19) | 0.6022 (4) | 0.0992 (2) | 0.0396 (9) | |
C6 | 0.4224 (3) | 0.4825 (6) | 0.3249 (3) | 0.0579 (14) | |
H6A | 0.4393 | 0.4228 | 0.3670 | 0.070* | |
C7 | 0.4197 (2) | 0.4504 (6) | 0.2525 (3) | 0.0478 (12) | |
H7A | 0.4342 | 0.3640 | 0.2348 | 0.057* | |
C8 | 0.4393 (3) | 0.9367 (7) | 0.1121 (3) | 0.0551 (13) | |
H8A | 0.4444 | 1.0380 | 0.1219 | 0.066* | |
C9 | 0.4718 (3) | 0.8564 (6) | 0.0695 (4) | 0.0585 (15) | |
H9A | 0.5016 | 0.8930 | 0.0459 | 0.070* | |
C10 | 0.4518 (2) | 0.7169 (6) | 0.0691 (3) | 0.0507 (13) | |
H10A | 0.4655 | 0.6369 | 0.0455 | 0.061* | |
C11 | 0.2646 (3) | 0.5066 (6) | 0.0549 (3) | 0.0511 (13) | |
H11A | 0.2747 | 0.4186 | 0.0343 | 0.061* | |
C12 | 0.2043 (3) | 0.5642 (8) | 0.0463 (3) | 0.0636 (15) | |
H12A | 0.1654 | 0.5242 | 0.0179 | 0.076* | |
C13 | 0.2128 (3) | 0.6945 (7) | 0.0884 (3) | 0.0546 (13) | |
H13A | 0.1795 | 0.7561 | 0.0933 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re | 0.04381 (13) | 0.03421 (12) | 0.04082 (12) | 0.00841 (8) | 0.01270 (8) | −0.00313 (8) |
Br | 0.0784 (4) | 0.0437 (3) | 0.0612 (3) | 0.0076 (3) | 0.0336 (3) | −0.0052 (2) |
N1 | 0.040 (2) | 0.036 (2) | 0.041 (2) | 0.0048 (17) | 0.0114 (17) | −0.0002 (17) |
O1 | 0.100 (4) | 0.062 (3) | 0.103 (4) | −0.005 (3) | −0.017 (3) | −0.029 (3) |
C1 | 0.064 (4) | 0.043 (3) | 0.069 (4) | 0.009 (3) | 0.007 (3) | −0.007 (3) |
C2 | 0.054 (3) | 0.057 (3) | 0.042 (2) | 0.019 (3) | 0.011 (2) | −0.002 (2) |
O2 | 0.073 (3) | 0.113 (4) | 0.061 (3) | 0.034 (3) | 0.037 (2) | 0.006 (2) |
N2 | 0.039 (2) | 0.0323 (19) | 0.046 (2) | 0.0009 (16) | 0.0143 (17) | 0.0026 (16) |
N3 | 0.042 (2) | 0.030 (2) | 0.058 (2) | 0.0004 (16) | 0.0207 (18) | 0.0045 (17) |
O3 | 0.137 (5) | 0.056 (3) | 0.064 (3) | 0.040 (3) | 0.007 (3) | 0.007 (2) |
C3 | 0.073 (4) | 0.047 (3) | 0.048 (3) | 0.019 (3) | 0.013 (3) | −0.007 (2) |
N4 | 0.046 (2) | 0.033 (2) | 0.056 (2) | 0.0020 (17) | 0.0268 (19) | 0.0012 (17) |
C4 | 0.046 (3) | 0.035 (2) | 0.048 (3) | 0.004 (2) | 0.023 (2) | −0.0002 (19) |
N5 | 0.040 (2) | 0.046 (2) | 0.0386 (19) | 0.0029 (18) | 0.0108 (16) | −0.0032 (17) |
C5 | 0.046 (3) | 0.055 (3) | 0.039 (2) | −0.002 (2) | 0.002 (2) | 0.001 (2) |
N6 | 0.047 (2) | 0.037 (2) | 0.0385 (19) | 0.0011 (17) | 0.0177 (17) | −0.0009 (16) |
C6 | 0.058 (3) | 0.054 (3) | 0.053 (3) | 0.001 (3) | 0.000 (3) | 0.017 (3) |
C7 | 0.040 (3) | 0.036 (3) | 0.066 (3) | 0.006 (2) | 0.012 (2) | 0.009 (2) |
C8 | 0.052 (3) | 0.040 (3) | 0.075 (4) | 0.000 (2) | 0.020 (3) | 0.012 (3) |
C9 | 0.053 (3) | 0.059 (4) | 0.073 (4) | 0.005 (3) | 0.034 (3) | 0.019 (3) |
C10 | 0.049 (3) | 0.051 (3) | 0.061 (3) | 0.012 (3) | 0.030 (2) | 0.012 (3) |
C11 | 0.063 (3) | 0.051 (3) | 0.036 (2) | −0.009 (3) | 0.009 (2) | −0.005 (2) |
C12 | 0.058 (3) | 0.075 (4) | 0.050 (3) | −0.013 (3) | 0.001 (3) | −0.002 (3) |
C13 | 0.040 (3) | 0.072 (4) | 0.049 (3) | 0.002 (3) | 0.008 (2) | −0.003 (3) |
Re—C1 | 1.913 (6) | N5—C13 | 1.335 (6) |
Re—C2 | 1.911 (5) | N5—N6 | 1.359 (5) |
Re—C3 | 1.925 (6) | C5—C6 | 1.400 (8) |
Re—N1 | 2.181 (4) | C5—H5A | 0.93 |
Re—N3 | 2.172 (4) | N6—C11 | 1.345 (6) |
Re—N5 | 2.175 (4) | C6—C7 | 1.349 (8) |
N1—C5 | 1.333 (6) | C6—H6A | 0.93 |
N1—N2 | 1.361 (5) | C7—H7A | 0.93 |
O1—C1 | 1.146 (7) | C8—C9 | 1.388 (8) |
C2—O2 | 1.150 (7) | C8—H8A | 0.93 |
N2—C7 | 1.362 (6) | C9—C10 | 1.327 (8) |
N2—C4 | 1.444 (6) | C9—H9A | 0.93 |
N3—C8 | 1.326 (7) | C10—H10A | 0.93 |
N3—N4 | 1.362 (5) | C11—C12 | 1.367 (8) |
O3—C3 | 1.139 (7) | C11—H11A | 0.93 |
N4—C10 | 1.354 (6) | C12—C13 | 1.389 (9) |
N4—C4 | 1.436 (6) | C12—H12A | 0.93 |
C4—N6 | 1.439 (6) | C13—H13A | 0.93 |
C4—H4A | 0.98 | ||
C1—Re—C2 | 89.5 (3) | N2—C4—H4A | 108.6 |
C1—Re—C3 | 88.6 (3) | C13—N5—N6 | 105.0 (4) |
C2—Re—C3 | 88.2 (2) | C13—N5—Re | 135.0 (4) |
C1—Re—N1 | 96.2 (2) | N6—N5—Re | 119.7 (3) |
C1—Re—N3 | 95.1 (2) | N1—C5—C6 | 110.5 (5) |
C1—Re—N5 | 176.4 (2) | N1—C5—H5A | 124.8 |
C2—Re—N1 | 96.1 (2) | C6—C5—H5A | 124.8 |
C2—Re—N3 | 174.8 (2) | C11—N6—N5 | 111.8 (4) |
C2—Re—N5 | 92.5 (2) | C11—N6—C4 | 127.8 (4) |
C3—Re—N1 | 173.5 (2) | N5—N6—C4 | 120.1 (4) |
C3—Re—N3 | 94.4 (2) | C7—C6—C5 | 106.5 (5) |
C3—Re—N5 | 94.4 (2) | C7—C6—H6A | 126.8 |
N1—Re—N3 | 80.9 (1) | C5—C6—H6A | 126.8 |
N1—Re—N5 | 80.6 (1) | C6—C7—N2 | 106.6 (5) |
N3—Re—N5 | 82.8 (1) | C6—C7—H7A | 126.7 |
C5—N1—N2 | 104.9 (4) | N2—C7—H7A | 126.7 |
C5—N1—Re | 135.9 (4) | N3—C8—C9 | 110.6 (5) |
N2—N1—Re | 119.1 (3) | N3—C8—H8A | 124.7 |
O1—C1—Re | 178.4 (6) | C9—C8—H8A | 124.7 |
O2—C2—Re | 176.9 (5) | C10—C9—C8 | 106.4 (5) |
N1—N2—C7 | 111.4 (4) | C10—C9—H9A | 126.8 |
N1—N2—C4 | 120.3 (4) | C8—C9—H9A | 126.8 |
C7—N2—C4 | 128.1 (4) | C9—C10—N4 | 107.7 (5) |
C8—N3—N4 | 104.9 (4) | C9—C10—H10A | 126.1 |
C8—N3—Re | 135.5 (4) | N4—C10—H10A | 126.1 |
N4—N3—Re | 119.5 (3) | N6—C11—C12 | 106.4 (5) |
O3—C3—Re | 178.4 (5) | N6—C11—H11A | 126.8 |
C10—N4—N3 | 110.3 (4) | C12—C11—H11A | 126.8 |
C10—N4—C4 | 129.4 (4) | C11—C12—C13 | 106.3 (5) |
N3—N4—C4 | 120.0 (4) | C11—C12—H12A | 126.8 |
N6—C4—N4 | 110.5 (4) | C13—C12—H12A | 126.8 |
N6—C4—N2 | 110.3 (4) | N5—C13—C12 | 110.4 (5) |
N4—C4—N2 | 110.3 (4) | N5—C13—H13A | 124.8 |
N6—C4—H4A | 108.6 | C12—C13—H13A | 124.8 |
N4—C4—H4A | 108.6 |
[Re(C11H12N6)(CO)3]I·0.5C2H6O | F(000) = 1233 |
Mr = 648.44 | Dx = 2.022 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.361 (3) Å | Cell parameters from 25 reflections |
b = 11.803 (2) Å | θ = 15.0–18.0° |
c = 15.543 (3) Å | µ = 7.13 mm−1 |
β = 108.83 (3)° | T = 293 K |
V = 2146.3 (7) Å3 | Block, colorless |
Z = 4 | 0.41 × 0.23 × 0.23 mm |
Enraf-Nonius CAD-4 diffractometer | 4128 reflections with I > 2σ(I) |
Radiation source: normal focus Philips sealed tube | Rint = 0.068 |
Equatorial mounted graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ω/2θ scans | h = −16→16 |
Absorption correction: ψ scan North et al. (1968) | k = 0→15 |
Tmin = 0.08, Tmax = 0.20 | l = 0→20 |
5073 measured reflections | 3 standard reflections every 60 min |
4896 independent reflections | intensity decay: <2% |
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)] = 0.045 | H-atom parameters not refined |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0778P)2 + 1.9504P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.014 |
4896 reflections | Δρmax = 1.37 e Å−3 |
254 parameters | Δρmin = −1.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0094 (5) |
[Re(C11H12N6)(CO)3]I·0.5C2H6O | V = 2146.3 (7) Å3 |
Mr = 648.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.361 (3) Å | µ = 7.13 mm−1 |
b = 11.803 (2) Å | T = 293 K |
c = 15.543 (3) Å | 0.41 × 0.23 × 0.23 mm |
β = 108.83 (3)° |
Enraf-Nonius CAD-4 diffractometer | 4128 reflections with I > 2σ(I) |
Absorption correction: ψ scan North et al. (1968) | Rint = 0.068 |
Tmin = 0.08, Tmax = 0.20 | 3 standard reflections every 60 min |
5073 measured reflections | intensity decay: <2% |
4896 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters not refined |
S = 1.12 | Δρmax = 1.37 e Å−3 |
4896 reflections | Δρmin = −1.29 e Å−3 |
254 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. The coordinates for the highest peak are (0.2837, 1.0333, 0.0653) and for the deepest trough are (0.1779, 0.9883, 0.1437) which is 1.24 Å from Re and 1.02 Å from C2. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Re | 0.26460 (2) | 0.99066 (2) | 0.120017 (16) | 0.04659 (13) | |
I | 0.32805 (5) | 0.93586 (4) | −0.33990 (4) | 0.07274 (19) | |
N1 | 0.1725 (4) | 0.8358 (4) | 0.0678 (3) | 0.0474 (11) | |
O1 | 0.3584 (6) | 0.9032 (7) | 0.3157 (4) | 0.102 (2) | |
C1 | 0.3234 (7) | 0.9381 (7) | 0.2419 (5) | 0.0660 (18) | |
N2 | 0.1740 (4) | 0.7893 (4) | −0.0111 (3) | 0.0461 (10) | |
C2 | 0.1396 (6) | 1.0643 (6) | 0.1452 (5) | 0.0595 (16) | |
O2 | 0.0643 (5) | 1.1101 (5) | 0.1566 (5) | 0.0850 (17) | |
C3 | 0.3506 (6) | 1.1280 (6) | 0.1567 (5) | 0.0612 (16) | |
N3 | 0.3912 (4) | 0.9044 (5) | 0.0744 (4) | 0.0504 (11) | |
O3 | 0.4005 (6) | 1.2099 (5) | 0.1777 (5) | 0.0906 (18) | |
C4 | 0.2417 (5) | 0.8414 (5) | −0.0634 (4) | 0.0463 (12) | |
N4 | 0.3612 (4) | 0.8459 (4) | −0.0059 (4) | 0.0499 (11) | |
N5 | 0.2010 (4) | 1.0334 (4) | −0.0221 (4) | 0.0473 (11) | |
C5 | 0.1075 (6) | 0.7677 (6) | 0.0984 (5) | 0.0593 (16) | |
H5 | 0.0915 | 0.7791 | 0.1523 | 0.071* | |
N6 | 0.2013 (5) | 0.9564 (4) | −0.0880 (4) | 0.0489 (11) | |
C6 | 0.0674 (6) | 0.6790 (6) | 0.0408 (6) | 0.0678 (19) | |
H6 | 0.0203 | 0.6204 | 0.0472 | 0.081* | |
C7 | 0.1109 (5) | 0.6950 (5) | −0.0281 (5) | 0.0557 (15) | |
H7 | 0.0989 | 0.6483 | −0.0785 | 0.067* | |
C8 | 0.5045 (6) | 0.8925 (7) | 0.1097 (6) | 0.0649 (18) | |
H8 | 0.5492 | 0.9250 | 0.1641 | 0.078* | |
C9 | 0.5454 (7) | 0.8271 (8) | 0.0558 (7) | 0.085 (3) | |
H9 | 0.6211 | 0.8059 | 0.0668 | 0.102* | |
C10 | 0.4538 (7) | 0.7982 (7) | −0.0181 (6) | 0.070 (2) | |
H10 | 0.4555 | 0.7540 | −0.0672 | 0.084* | |
C11 | 0.1638 (7) | 1.0057 (6) | −0.1708 (5) | 0.0572 (16) | |
H11 | 0.1576 | 0.9711 | −0.2260 | 0.069* | |
C12 | 0.1370 (6) | 1.1148 (6) | −0.1592 (5) | 0.0595 (16) | |
H12 | 0.1079 | 1.1690 | −0.2042 | 0.071* | |
C13 | 0.1621 (5) | 1.1284 (6) | −0.0667 (5) | 0.0537 (14) | |
H13 | 0.1528 | 1.1959 | −0.0391 | 0.064* | |
C14 | 0.2297 (7) | 0.7714 (6) | −0.1479 (5) | 0.0644 (18) | |
H14A | 0.2742 | 0.8051 | −0.1816 | 0.097* | |
H14B | 0.1508 | 0.7690 | −0.1851 | 0.097* | |
H14C | 0.2564 | 0.6957 | −0.1305 | 0.097* | |
O20 | 0.112 (2) | 1.065 (3) | 0.3861 (15) | 0.188 (12) | 0.50 |
C20 | 0.099 (3) | 0.968 (2) | 0.3882 (19) | 0.140 (14) | 0.50 |
C21 | −0.0366 (14) | 0.9400 (13) | 0.3796 (9) | 0.066 (4) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re | 0.04932 (18) | 0.04296 (17) | 0.04910 (18) | 0.00482 (9) | 0.01813 (12) | −0.00250 (9) |
I | 0.1069 (4) | 0.0458 (3) | 0.0779 (4) | −0.0022 (2) | 0.0470 (3) | 0.0021 (2) |
N1 | 0.049 (3) | 0.045 (3) | 0.054 (3) | 0.002 (2) | 0.024 (2) | 0.005 (2) |
O1 | 0.105 (5) | 0.129 (6) | 0.063 (4) | 0.015 (4) | 0.012 (3) | 0.021 (4) |
C1 | 0.079 (5) | 0.062 (4) | 0.054 (4) | 0.008 (4) | 0.017 (4) | −0.002 (3) |
N2 | 0.048 (2) | 0.037 (2) | 0.056 (3) | −0.0013 (19) | 0.020 (2) | 0.004 (2) |
C2 | 0.065 (4) | 0.056 (4) | 0.064 (4) | 0.006 (3) | 0.031 (3) | 0.005 (3) |
O2 | 0.080 (4) | 0.079 (4) | 0.113 (5) | 0.023 (3) | 0.054 (4) | 0.010 (3) |
C3 | 0.070 (4) | 0.055 (4) | 0.063 (4) | 0.005 (3) | 0.027 (3) | −0.006 (3) |
N3 | 0.048 (3) | 0.048 (3) | 0.054 (3) | 0.000 (2) | 0.014 (2) | −0.008 (2) |
O3 | 0.107 (5) | 0.057 (3) | 0.104 (5) | −0.020 (3) | 0.030 (4) | −0.023 (3) |
C4 | 0.053 (3) | 0.038 (3) | 0.053 (3) | −0.003 (2) | 0.023 (3) | −0.001 (2) |
N4 | 0.046 (3) | 0.044 (3) | 0.065 (3) | 0.000 (2) | 0.026 (2) | −0.002 (2) |
N5 | 0.053 (3) | 0.032 (2) | 0.060 (3) | 0.001 (2) | 0.022 (2) | −0.002 (2) |
C5 | 0.061 (4) | 0.052 (4) | 0.076 (4) | 0.008 (3) | 0.038 (3) | 0.015 (3) |
N6 | 0.059 (3) | 0.033 (2) | 0.057 (3) | −0.003 (2) | 0.022 (2) | −0.001 (2) |
C6 | 0.066 (4) | 0.045 (4) | 0.102 (6) | −0.008 (3) | 0.041 (4) | 0.007 (4) |
C7 | 0.052 (3) | 0.039 (3) | 0.077 (4) | −0.006 (2) | 0.021 (3) | −0.001 (3) |
C8 | 0.042 (3) | 0.066 (4) | 0.085 (5) | 0.001 (3) | 0.018 (3) | −0.008 (4) |
C9 | 0.055 (4) | 0.079 (6) | 0.132 (8) | 0.007 (4) | 0.044 (5) | −0.016 (5) |
C10 | 0.057 (4) | 0.061 (4) | 0.107 (6) | −0.002 (3) | 0.046 (4) | −0.019 (4) |
C11 | 0.071 (4) | 0.052 (4) | 0.049 (3) | −0.008 (3) | 0.019 (3) | 0.005 (3) |
C12 | 0.061 (4) | 0.054 (4) | 0.061 (4) | 0.004 (3) | 0.017 (3) | 0.016 (3) |
C13 | 0.050 (3) | 0.043 (3) | 0.066 (4) | 0.005 (2) | 0.016 (3) | 0.006 (3) |
C14 | 0.093 (5) | 0.043 (3) | 0.067 (4) | −0.003 (3) | 0.039 (4) | −0.011 (3) |
O20 | 0.18 (2) | 0.27 (3) | 0.108 (15) | −0.08 (2) | 0.034 (15) | −0.06 (2) |
C20 | 0.19 (3) | 0.055 (11) | 0.12 (2) | −0.015 (15) | −0.03 (2) | −0.025 (13) |
C21 | 0.088 (10) | 0.056 (8) | 0.046 (7) | −0.006 (7) | 0.011 (7) | 0.016 (6) |
Re—C1 | 1.901 (8) | C5—C6 | 1.363 (11) |
Re—C2 | 1.920 (7) | C5—H5 | 0.9300 |
Re—C3 | 1.922 (8) | N6—C11 | 1.351 (9) |
Re—N5 | 2.152 (6) | C6—C7 | 1.358 (10) |
Re—N1 | 2.168 (5) | C6—H6 | 0.9300 |
Re—N3 | 2.169 (5) | C7—H7 | 0.9300 |
Re—N5 | 2.152 (6) | C8—C9 | 1.351 (11) |
N1—C5 | 1.328 (8) | C8—H8 | 0.9300 |
N1—N2 | 1.349 (7) | C9—C10 | 1.371 (13) |
O1—C1 | 1.163 (9) | C9—H9 | 0.9300 |
N2—C7 | 1.336 (8) | C10—H10 | 0.9300 |
N2—C4 | 1.474 (7) | C11—C12 | 1.356 (10) |
C2—O2 | 1.139 (8) | C11—H11 | 0.9300 |
C3—O3 | 1.135 (9) | C12—C13 | 1.379 (9) |
N3—C8 | 1.336 (8) | C12—H12 | 0.9300 |
N3—N4 | 1.369 (7) | C13—H13 | 0.9300 |
C4—N6 | 1.455 (8) | C14—H14A | 0.9600 |
C4—N4 | 1.460 (8) | C14—H14B | 0.9600 |
C4—C14 | 1.518 (9) | C14—H14C | 0.9600 |
N4—C10 | 1.344 (8) | O20—C20 | 1.16 (4) |
N5—C13 | 1.324 (8) | C20—C21 | 1.67 (4) |
N5—N6 | 1.371 (7) | ||
C1—Re—C2 | 91.1 (3) | N6—N5—Re | 121.6 (4) |
C1—Re—C3 | 89.0 (3) | N1—C5—C6 | 111.3 (6) |
C2—Re—C3 | 87.8 (3) | N1—C5—H5 | 124.4 |
C1—Re—N1 | 94.8 (3) | C6—C5—H5 | 124.4 |
C1—Re—N3 | 95.1 (3) | C11—N6—N5 | 110.1 (5) |
C1—Re—N5 | 174.3 (3) | C11—N6—C4 | 129.5 (6) |
C2—Re—N1 | 95.6 (3) | N5—N6—C4 | 120.3 (5) |
C2—Re—N3 | 172.8 (3) | C7—C6—C5 | 105.0 (6) |
C2—Re—N5 | 92.9 (3) | C7—C6—H6 | 127.5 |
C3—Re—N5 | 95.2 (3) | C5—C6—H6 | 127.5 |
C3—Re—N3 | 96.0 (2) | N2—C7—C6 | 108.3 (6) |
C3—Re—N1 | 174.8 (2) | N2—C7—H7 | 125.8 |
N1—Re—N3 | 80.17 (18) | C6—C7—H7 | 125.8 |
N1—Re—N5 | 80.77 (19) | N3—C8—C9 | 111.0 (7) |
N3—Re—N5 | 80.7 (2) | N3—C8—H8 | 124.5 |
C5—N1—N2 | 105.5 (5) | C9—C8—H8 | 124.5 |
C5—N1—Re | 132.9 (5) | C8—C9—C10 | 106.8 (7) |
N2—N1—Re | 121.5 (3) | C8—C9—H9 | 126.6 |
O1—C1—Re | 178.3 (8) | C10—C9—H9 | 126.6 |
C7—N2—N1 | 109.9 (5) | N4—C10—C9 | 106.7 (7) |
C7—N2—C4 | 129.6 (5) | N4—C10—H10 | 126.7 |
N1—N2—C4 | 120.5 (5) | C9—C10—H10 | 126.7 |
O2—C2—Re | 177.1 (7) | N6—C11—C12 | 107.8 (7) |
O3—C3—Re | 179.2 (8) | N6—C11—H11 | 126.1 |
C8—N3—N4 | 105.1 (5) | C12—C11—H11 | 126.1 |
C8—N3—Re | 133.4 (5) | C11—C12—C13 | 105.5 (6) |
N4—N3—Re | 121.5 (4) | C11—C12—H12 | 127.3 |
N6—C4—N4 | 108.7 (5) | C13—C12—H12 | 127.3 |
N6—C4—N2 | 109.1 (5) | N5—C13—C12 | 111.7 (6) |
N4—C4—N2 | 108.7 (5) | N5—C13—H13 | 124.2 |
N6—C4—C14 | 110.5 (5) | C12—C13—H13 | 124.2 |
N4—C4—C14 | 110.3 (5) | C4—C14—H14A | 109.5 |
N2—C4—C14 | 109.6 (5) | C4—C14—H14B | 109.5 |
C10—N4—N3 | 110.4 (6) | H14A—C14—H14B | 109.5 |
C10—N4—C4 | 129.6 (6) | C4—C14—H14C | 109.5 |
N3—N4—C4 | 119.9 (5) | H14A—C14—H14C | 109.5 |
C13—N5—N6 | 104.9 (5) | H14B—C14—H14C | 109.5 |
C13—N5—Re | 133.4 (4) | O20—C20—C21 | 110 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Re(C10H10N6)(CO)3]Br | [Re(C11H12N6)(CO)3]I·0.5C2H6O |
Mr | 564.38 | 648.44 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 21.565 (4), 9.002 (2), 18.396 (4) | 12.361 (3), 11.803 (2), 15.543 (3) |
β (°) | 105.93 (3) | 108.83 (3) |
V (Å3) | 3434 (1) | 2146.3 (7) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 9.43 | 7.13 |
Crystal size (mm) | 0.33 × 0.26 × 0.17 | 0.41 × 0.23 × 0.23 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan North et al. (1968) |
Tmin, Tmax | 0.07, 0.21 | 0.08, 0.20 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4033, 3929, 3172 | 5073, 4896, 4128 |
Rint | 0.036 | 0.068 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.071, 1.06 | 0.045, 0.123, 1.12 |
No. of reflections | 3929 | 4896 |
No. of parameters | 218 | 254 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.55, −0.59 | 1.37, −1.29 |
Computer programs: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1988), CAD-4 Diffractometer Control Software, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Re—C1 | 1.913 (6) | Re—N1 | 2.181 (4) |
Re—C2 | 1.911 (5) | Re—N3 | 2.172 (4) |
Re—C3 | 1.925 (6) | Re—N5 | 2.175 (4) |
C1—Re—C2 | 89.5 (3) | C2—Re—N5 | 92.5 (2) |
C1—Re—C3 | 88.6 (3) | C3—Re—N1 | 173.5 (2) |
C2—Re—C3 | 88.2 (2) | C3—Re—N3 | 94.4 (2) |
C1—Re—N1 | 96.2 (2) | C3—Re—N5 | 94.4 (2) |
C1—Re—N3 | 95.1 (2) | N1—Re—N3 | 80.9 (1) |
C1—Re—N5 | 176.4 (2) | N1—Re—N5 | 80.6 (1) |
C2—Re—N1 | 96.1 (2) | N3—Re—N5 | 82.8 (1) |
C2—Re—N3 | 174.8 (2) |
Re—C1 | 1.901 (8) | Re—N1 | 2.168 (5) |
Re—C2 | 1.920 (7) | Re—N3 | 2.169 (5) |
Re—C3 | 1.922 (8) | Re—N5 | 2.152 (6) |
Re—N5 | 2.152 (6) | ||
C1—Re—C2 | 91.1 (3) | C2—Re—N5 | 92.9 (3) |
C1—Re—C3 | 89.0 (3) | C3—Re—N5 | 95.2 (3) |
C2—Re—C3 | 87.8 (3) | C3—Re—N3 | 96.0 (2) |
C1—Re—N1 | 94.8 (3) | C3—Re—N1 | 174.8 (2) |
C1—Re—N3 | 95.1 (3) | N1—Re—N3 | 80.17 (18) |
C1—Re—N5 | 174.3 (3) | N1—Re—N5 | 80.77 (19) |
C2—Re—N1 | 95.6 (3) | N3—Re—N5 | 80.7 (2) |
C2—Re—N3 | 172.8 (3) |
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The title compounds, (I) and (II), respectively, have been prepared as part of a general study of ligand systems which are capable of variable denticity. The tris(pyrazol-1-yl)methane ligand [HC(pz)3] has previously demonstrated the capacity for either bidentate or tridentate coordination (Macchioni et al., 1998). Flexibility in changing between these two coordination modes may play an important role in catalytic processes, as demonstrated for some of the closely related tris(pyrazol-1-yl)borate complexes (Bromberg et al., 1996). Compounds (I) and (II) have been characterized in order to increase our knowledge of the structural charcterstics of metal complexes with this ligand.
Fig. 1 shows an ORTEP-3 diagram (Farrugia, 1997) illustrating the cation of (I). The constraints of the η3-coordinated HC(pz)3 ligand reduce the N—Re—N bond angles well below the preferred value of 90°. The N—Re—N bond angles in (I) are also smaller [average 81.4 (1)°] than those in [HC(3-iPrpz)3Mn(CO)3](SO3CF3) (Reger et al., 2000), which average 85.0 (3)°. The C—Re—C bond angles associated with the three facial carbonyl groups in (I) average 88.8 (3)°, whereas the corresponding angles in the Mn complex are slightly greater, with an average of 89.6 (5)°. The constraints of the HC(pz)3 ligand in (I) also ensure that trans arrangements such as C3—Re—N1 will be well below 180°; they range from 173.5 (2)° for C3—Re—N1 to 176.4 (2)° for C1—Re—N5, and all are bent toward the HC(pz)3 ligand. The corresponding angles in the manganese complex are slightly larger, ranging from 175.7 (4) to 177.7 (4)°, reflecting the influence of the isopropyl substituents at position 3 of the pyrazole ring.
An ORTEP-3 diagram (Farrugia, 1997) of the cation of (II) is shown in Fig. 2; similar distortions are seen in (II). The bond angles for trans groups, such as C3—Re—N1, are again well below 180°; they range from 172.4 (3)° for C2—Re—N3 to 174.9 (3)° for C3—Re—N1. The N—Re—N bond angles are even smaller in (II) than in (I) [average 80.5 (2)°], but the C—Re—C bond angles associated with the three facial carbonyl groups are slightly larger than the corresponding angles in (I) [average 89.4 (4)°]. Replacement of hydrogen by methyl in CH3C(pz)3 does not appear to cause any significant distortions in the complex.