Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100002535/qb0178sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100002535/qb0178Isup2.hkl |
CCDC reference: 143326
The synthesis of (I) was carried out by the reaction of 3-cyano-6-ferrocenyl-4-methylthio-2H-pyran-2-one with 5-(4-bromophenyl)-3-cyanomethyl-1H-pyrazole in a 1:1 molar ratio in dry DMF in the presence of KOH (Nath et al., 1998). Diffraction quality crystals were grown by slow evaporation from a mixture of dichloromethane and hexane at room temperature.
All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, to which each was bonded for the final cycles of refinement. Nine reflections [most disagreeable, Δ(F2)/σ > 5.0] were suppressed during the last cycles of refinement.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: NRCVAX (Gabe et al., 1989); software used to prepare material for publication: SHELXL93.
[Fe(C5H5)(C21H12BrN4)] | F(000) = 524 |
Mr = 521.20 | Dx = 1.628 Mg m−3 |
Triclinic, P1 | Melting point: 230 K |
a = 7.9608 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6844 (1) Å | Cell parameters from 509 reflections |
c = 12.8215 (3) Å | θ = 3.0–25.6° |
α = 93.577 (1)° | µ = 2.61 mm−1 |
β = 97.737 (1)° | T = 150 K |
γ = 99.046 (1)° | Plate, red |
V = 1063.28 (3) Å3 | 0.25 × 0.15 × 0.06 mm |
Z = 2 |
Bruker SMARTCCD diffractometer | 4823 independent reflections |
Radiation source: fine-focus sealed tube | 3953 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: ψ scan (XPREP; Sheldrick, 1994) | h = −10→9 |
Tmin = 0.606, Tmax = 0.855 | k = −13→10 |
7790 measured reflections | l = −16→16 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.03 | Calculated w = 1/[σ2(Fo2) + (0.0381P)2 + 4.8638P] where P = (Fo2 + 2Fc2)/3 |
4783 reflections | (Δ/σ)max = −0.001 |
289 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Fe(C5H5)(C21H12BrN4)] | γ = 99.046 (1)° |
Mr = 521.20 | V = 1063.28 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9608 (1) Å | Mo Kα radiation |
b = 10.6844 (1) Å | µ = 2.61 mm−1 |
c = 12.8215 (3) Å | T = 150 K |
α = 93.577 (1)° | 0.25 × 0.15 × 0.06 mm |
β = 97.737 (1)° |
Bruker SMARTCCD diffractometer | 4823 independent reflections |
Absorption correction: ψ scan (XPREP; Sheldrick, 1994) | 3953 reflections with I > 2σ(I) |
Tmin = 0.606, Tmax = 0.855 | Rint = 0.040 |
7790 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.46 e Å−3 |
4783 reflections | Δρmin = −0.36 e Å−3 |
289 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 on F2 for ALL reflections except for 40 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
Br | 0.44869 (6) | 0.74199 (5) | 0.35615 (3) | 0.03315 (14) | |
Fe | 1.00953 (8) | 1.43332 (6) | 1.27215 (5) | 0.0236 (2) | |
N1 | 1.0036 (4) | 1.0849 (3) | 0.7807 (3) | 0.0212 (7) | |
C2 | 0.8354 (5) | 1.0328 (4) | 0.7704 (3) | 0.0227 (8) | |
C1' | 0.7432 (5) | 0.9683 (4) | 0.6690 (3) | 0.0225 (8) | |
C2' | 0.5900 (5) | 0.8835 (4) | 0.6689 (3) | 0.0265 (9) | |
H2' | 0.5473 | 0.8709 | 0.7321 | 0.032* | |
C3' | 0.5009 (5) | 0.8177 (4) | 0.5759 (3) | 0.0274 (9) | |
H3' | 0.3985 | 0.7621 | 0.5761 | 0.033* | |
C4' | 0.5687 (5) | 0.8370 (4) | 0.4824 (3) | 0.0253 (9) | |
C5' | 0.7189 (5) | 0.9210 (4) | 0.4792 (3) | 0.0268 (9) | |
H5' | 0.7607 | 0.9333 | 0.4156 | 0.032* | |
C6' | 0.8064 (5) | 0.9868 (4) | 0.5733 (3) | 0.0259 (9) | |
H6' | 0.9075 | 1.0435 | 0.5724 | 0.031* | |
C3 | 0.7656 (5) | 1.0495 (4) | 0.8640 (3) | 0.0211 (8) | |
H3 | 0.6531 | 1.0217 | 0.8749 | 0.025* | |
C4 | 0.9184 (5) | 1.1670 (4) | 1.0441 (3) | 0.0208 (8) | |
C5 | 1.0748 (5) | 1.2339 (4) | 1.0944 (3) | 0.0223 (8) | |
C1A | 1.1057 (5) | 1.2849 (4) | 1.2055 (3) | 0.0221 (8) | |
C2A | 1.0095 (6) | 1.2438 (4) | 1.2890 (3) | 0.0279 (9) | |
H2A | 0.9129 | 1.1806 | 1.2816 | 0.034* | |
C3A | 1.0890 (6) | 1.3172 (4) | 1.3849 (3) | 0.0317 (10) | |
H3A | 1.0536 | 1.3095 | 1.4507 | 0.038* | |
C4A | 1.2314 (6) | 1.4041 (4) | 1.3624 (3) | 0.0288 (9) | |
H4A | 1.3044 | 1.4635 | 1.4109 | 0.035* | |
C5A | 1.2430 (5) | 1.3848 (4) | 1.2530 (3) | 0.0245 (8) | |
H5A | 1.3254 | 1.4291 | 1.2179 | 0.029* | |
C1B | 0.8700 (7) | 1.5064 (5) | 1.1520 (4) | 0.0410 (12) | |
H1B | 0.8555 | 1.4791 | 1.0806 | 0.049* | |
C2B | 0.7626 (6) | 1.4611 (5) | 1.2255 (5) | 0.0456 (14) | |
H2B | 0.6657 | 1.3982 | 1.2109 | 0.055* | |
C3B | 0.8282 (7) | 1.5283 (5) | 1.3255 (5) | 0.0420 (12) | |
H3B | 0.7822 | 1.5173 | 1.3878 | 0.050* | |
C4B | 0.9764 (6) | 1.6150 (4) | 1.3129 (4) | 0.0333 (10) | |
H4B | 1.0443 | 1.6716 | 1.3657 | 0.040* | |
C5B | 1.0040 (6) | 1.6009 (5) | 1.2063 (4) | 0.0344 (10) | |
H5B | 1.0937 | 1.6455 | 1.1770 | 0.041* | |
C6 | 1.2138 (5) | 1.2519 (4) | 1.0331 (3) | 0.0219 (8) | |
H6 | 1.3193 | 1.2980 | 1.0646 | 0.026* | |
C7 | 1.1965 (5) | 1.2038 (4) | 0.9302 (3) | 0.0218 (8) | |
N8 | 1.0405 (4) | 1.1352 (3) | 0.8837 (3) | 0.0198 (7) | |
C9 | 0.8985 (5) | 1.1159 (4) | 0.9364 (3) | 0.0204 (8) | |
C10 | 0.7638 (6) | 1.1435 (4) | 1.0915 (3) | 0.0270 (9) | |
N11 | 0.6341 (5) | 1.1199 (5) | 1.1207 (3) | 0.0423 (11) | |
C12 | 1.3299 (5) | 1.2185 (4) | 0.8572 (3) | 0.0255 (9) | |
H12A | 1.3596 | 1.1358 | 0.8401 | 0.031* | |
H12B | 1.2809 | 1.2487 | 0.7920 | 0.031* | |
C13 | 1.4873 (6) | 1.3068 (5) | 0.9018 (3) | 0.0299 (9) | |
N14 | 1.6111 (5) | 1.3756 (5) | 0.9303 (3) | 0.0460 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0301 (2) | 0.0418 (3) | 0.0227 (2) | −0.0025 (2) | 0.0016 (2) | −0.0084 (2) |
Fe | 0.0249 (3) | 0.0244 (3) | 0.0202 (3) | 0.0031 (2) | 0.0017 (2) | −0.0025 (2) |
N1 | 0.024 (2) | 0.021 (2) | 0.016 (2) | −0.0013 (13) | 0.0026 (13) | −0.0029 (13) |
C2 | 0.022 (2) | 0.024 (2) | 0.021 (2) | 0.001 (2) | 0.0004 (15) | −0.002 (2) |
C1' | 0.020 (2) | 0.025 (2) | 0.022 (2) | 0.007 (2) | 0.0010 (15) | 0.000 (2) |
C2' | 0.025 (2) | 0.033 (2) | 0.020 (2) | 0.001 (2) | 0.004 (2) | −0.001 (2) |
C3' | 0.020 (2) | 0.035 (2) | 0.025 (2) | 0.000 (2) | 0.004 (2) | −0.001 (2) |
C4' | 0.028 (2) | 0.026 (2) | 0.019 (2) | 0.003 (2) | 0.000 (2) | −0.004 (2) |
C5' | 0.025 (2) | 0.034 (2) | 0.020 (2) | 0.000 (2) | 0.005 (2) | −0.001 (2) |
C6' | 0.026 (2) | 0.029 (2) | 0.022 (2) | 0.000 (2) | 0.003 (2) | 0.000 (2) |
C3 | 0.020 (2) | 0.025 (2) | 0.018 (2) | 0.002 (2) | 0.0031 (14) | −0.0007 (15) |
C4 | 0.022 (2) | 0.021 (2) | 0.021 (2) | 0.003 (2) | 0.0072 (15) | 0.0019 (15) |
C5 | 0.027 (2) | 0.020 (2) | 0.020 (2) | 0.005 (2) | 0.002 (2) | 0.004 (2) |
C1A | 0.025 (2) | 0.025 (2) | 0.017 (2) | 0.004 (2) | 0.0018 (15) | 0.0014 (15) |
C2A | 0.038 (2) | 0.024 (2) | 0.021 (2) | 0.001 (2) | 0.005 (2) | 0.001 (2) |
C3A | 0.044 (3) | 0.032 (2) | 0.019 (2) | 0.006 (2) | 0.003 (2) | 0.001 (2) |
C4A | 0.030 (2) | 0.032 (2) | 0.022 (2) | 0.006 (2) | −0.004 (2) | −0.002 (2) |
C5A | 0.023 (2) | 0.026 (2) | 0.023 (2) | 0.004 (2) | 0.000 (2) | 0.000 (2) |
C1B | 0.049 (3) | 0.040 (3) | 0.032 (3) | 0.023 (2) | −0.011 (2) | −0.007 (2) |
C2B | 0.023 (2) | 0.044 (3) | 0.065 (4) | 0.007 (2) | −0.004 (2) | −0.017 (3) |
C3B | 0.037 (3) | 0.040 (3) | 0.050 (3) | 0.008 (2) | 0.014 (2) | −0.010 (2) |
C4B | 0.036 (2) | 0.026 (2) | 0.036 (2) | 0.005 (2) | 0.003 (2) | −0.010 (2) |
C5B | 0.039 (3) | 0.032 (2) | 0.036 (3) | 0.016 (2) | 0.007 (2) | 0.006 (2) |
C6 | 0.019 (2) | 0.025 (2) | 0.020 (2) | −0.0014 (15) | 0.0011 (14) | 0.001 (2) |
C7 | 0.021 (2) | 0.022 (2) | 0.022 (2) | 0.0016 (15) | 0.0029 (15) | −0.001 (2) |
N8 | 0.019 (2) | 0.022 (2) | 0.017 (2) | 0.0016 (13) | 0.0032 (12) | 0.0006 (13) |
C9 | 0.021 (2) | 0.023 (2) | 0.018 (2) | 0.0036 (15) | 0.0041 (15) | 0.0044 (15) |
C10 | 0.027 (2) | 0.030 (2) | 0.021 (2) | −0.002 (2) | 0.005 (2) | −0.004 (2) |
N11 | 0.032 (2) | 0.059 (3) | 0.031 (2) | −0.010 (2) | 0.012 (2) | −0.009 (2) |
C12 | 0.022 (2) | 0.031 (2) | 0.023 (2) | 0.000 (2) | 0.007 (2) | −0.002 (2) |
C13 | 0.030 (2) | 0.037 (3) | 0.022 (2) | 0.001 (2) | 0.007 (2) | 0.002 (2) |
N14 | 0.032 (2) | 0.066 (3) | 0.032 (2) | −0.015 (2) | 0.006 (2) | −0.006 (2) |
Br—C4' | 1.907 (4) | C5—C1A | 1.468 (5) |
Fe—C5B | 2.031 (5) | C1A—C5A | 1.441 (6) |
Fe—C4B | 2.045 (4) | C1A—C2A | 1.449 (6) |
Fe—C2B | 2.049 (5) | C2A—C3A | 1.428 (6) |
Fe—C1A | 2.054 (4) | C2A—H2A | 0.93 |
Fe—C5A | 2.048 (4) | C3A—C4A | 1.422 (7) |
Fe—C2A | 2.050 (4) | C3A—H3A | 0.93 |
Fe—C1B | 2.044 (5) | C4A—C5A | 1.423 (6) |
Fe—C4A | 2.055 (4) | C4A—H4A | 0.93 |
Fe—C3B | 2.054 (5) | C5A—H5A | 0.93 |
Fe—C3A | 2.062 (5) | C1B—C2B | 1.413 (8) |
N1—C2 | 1.353 (5) | C1B—C5B | 1.419 (7) |
N1—N8 | 1.370 (4) | C1B—H1B | 0.93 |
C2—C3 | 1.401 (5) | C2B—C3B | 1.420 (7) |
C2—C1' | 1.475 (5) | C2B—H2B | 0.93 |
C1'—C2' | 1.400 (6) | C3B—C4B | 1.415 (7) |
C1'—C6' | 1.402 (6) | C3B—H3B | 0.93 |
C2'—C3' | 1.389 (6) | C4B—C5B | 1.416 (7) |
C2'—H2' | 0.93 | C4B—H4B | 0.93 |
C3'—C4' | 1.394 (6) | C5B—H5B | 0.93 |
C3'—H3' | 0.93 | C6—C7 | 1.367 (5) |
C4'—C5' | 1.385 (6) | C6—H6 | 0.93 |
C5'—C6' | 1.396 (6) | C7—N8 | 1.377 (5) |
C5'—H5' | 0.93 | C7—C12 | 1.503 (5) |
C6'—H6' | 0.93 | N8—C9 | 1.388 (5) |
C3—C9 | 1.379 (5) | C10—N11 | 1.142 (6) |
C3—H3 | 0.93 | C12—C13 | 1.468 (6) |
C4—C5 | 1.387 (6) | C12—H12A | 0.97 |
C4—C9 | 1.432 (5) | C12—H12B | 0.97 |
C4—C10 | 1.439 (6) | C13—N14 | 1.134 (6) |
C5—C6 | 1.436 (6) | ||
C5B—Fe—C4B | 40.7 (2) | C2A—C1A—C5 | 127.5 (4) |
C5B—Fe—C2B | 68.4 (2) | C5A—C1A—Fe | 69.2 (2) |
C4B—Fe—C2B | 67.9 (2) | C2A—C1A—Fe | 69.2 (2) |
C5B—Fe—C1A | 123.2 (2) | C5—C1A—Fe | 127.8 (3) |
C4B—Fe—C1A | 160.3 (2) | C3A—C2A—C1A | 108.1 (4) |
C2B—Fe—C1A | 121.5 (2) | C3A—C2A—Fe | 70.1 (3) |
C5B—Fe—C5A | 105.6 (2) | C1A—C2A—Fe | 69.5 (2) |
C4B—Fe—C5A | 123.4 (2) | C3A—C2A—H2A | 126.0 (3) |
C2B—Fe—C5A | 156.1 (2) | C1A—C2A—H2A | 126.0 (2) |
C1A—Fe—C5A | 41.1 (2) | Fe—C2A—H2A | 126.01 (13) |
C5B—Fe—C2A | 161.7 (2) | C4A—C3A—C2A | 108.4 (4) |
C4B—Fe—C2A | 156.8 (2) | C4A—C3A—Fe | 69.5 (3) |
C2B—Fe—C2A | 109.2 (2) | C2A—C3A—Fe | 69.2 (2) |
C1A—Fe—C2A | 41.4 (2) | C4A—C3A—H3A | 125.8 (2) |
C5A—Fe—C2A | 68.9 (2) | C2A—C3A—H3A | 125.8 (3) |
C5B—Fe—C1B | 40.8 (2) | Fe—C3A—H3A | 127.00 (13) |
C4B—Fe—C1B | 68.1 (2) | C5A—C4A—C3A | 108.3 (4) |
C2B—Fe—C1B | 40.4 (2) | C5A—C4A—Fe | 69.5 (2) |
C1A—Fe—C1B | 106.9 (2) | C3A—C4A—Fe | 70.1 (3) |
C5A—Fe—C1B | 120.1 (2) | C5A—C4A—H4A | 125.8 (2) |
C2A—Fe—C1B | 125.6 (2) | C3A—C4A—H4A | 125.8 (2) |
C5B—Fe—C4A | 119.4 (2) | Fe—C4A—H4A | 126.21 (13) |
C4B—Fe—C4A | 107.0 (2) | C4A—C5A—C1A | 108.6 (4) |
C2B—Fe—C4A | 162.7 (2) | C4A—C5A—Fe | 70.0 (2) |
C1A—Fe—C4A | 68.9 (2) | C1A—C5A—Fe | 69.7 (2) |
C5A—Fe—C4A | 40.6 (2) | C4A—C5A—H5A | 125.7 (2) |
C2A—Fe—C4A | 68.5 (2) | C1A—C5A—H5A | 125.7 (2) |
C1B—Fe—C4A | 154.9 (2) | Fe—C5A—H5A | 126.25 (12) |
C5B—Fe—C3B | 68.4 (2) | C2B—C1B—C5B | 108.1 (4) |
C4B—Fe—C3B | 40.4 (2) | C2B—C1B—Fe | 70.0 (3) |
C2B—Fe—C3B | 40.5 (2) | C5B—C1B—Fe | 69.1 (3) |
C1A—Fe—C3B | 157.4 (2) | C2B—C1B—H1B | 126.0 (3) |
C5A—Fe—C3B | 160.8 (2) | C5B—C1B—H1B | 126.0 (3) |
C2A—Fe—C3B | 122.3 (2) | Fe—C1B—H1B | 126.47 (14) |
C1B—Fe—C3B | 68.1 (2) | C3B—C2B—C1B | 108.2 (5) |
C4A—Fe—C3B | 125.1 (2) | C3B—C2B—Fe | 69.9 (3) |
C5B—Fe—C3A | 155.2 (2) | C1B—C2B—Fe | 69.6 (3) |
C4B—Fe—C3A | 121.3 (2) | C3B—C2B—H2B | 125.9 (3) |
C2B—Fe—C3A | 126.8 (2) | C1B—C2B—H2B | 125.9 (3) |
C1A—Fe—C3A | 68.9 (2) | Fe—C2B—H2B | 126.1 (2) |
C5A—Fe—C3A | 68.3 (2) | C4B—C3B—C2B | 107.5 (5) |
C2A—Fe—C3A | 40.6 (2) | C4B—C3B—Fe | 69.4 (3) |
C1B—Fe—C3A | 163.2 (2) | C2B—C3B—Fe | 69.5 (3) |
C4A—Fe—C3A | 40.4 (2) | C4B—C3B—H3B | 126.2 (3) |
C3B—Fe—C3A | 109.0 (2) | C2B—C3B—H3B | 126.2 (3) |
C2—N1—N8 | 103.5 (3) | Fe—C3B—H3B | 126.3 (2) |
N1—C2—C3 | 112.5 (3) | C3B—C4B—C5B | 108.5 (4) |
N1—C2—C1' | 121.1 (4) | C3B—C4B—Fe | 70.2 (3) |
C3—C2—C1' | 126.4 (4) | C5B—C4B—Fe | 69.2 (3) |
C2'—C1'—C6' | 119.0 (4) | C3B—C4B—H4B | 125.7 (3) |
C2'—C1'—C2 | 118.9 (4) | C5B—C4B—H4B | 125.7 (3) |
C6'—C1'—C2 | 122.0 (4) | Fe—C4B—H4B | 126.50 (13) |
C3'—C2'—C1' | 121.2 (4) | C4B—C5B—C1B | 107.6 (5) |
C3'—C2'—H2' | 119.4 (2) | C4B—C5B—Fe | 70.2 (3) |
C1'—C2'—H2' | 119.4 (2) | C1B—C5B—Fe | 70.1 (3) |
C2'—C3'—C4' | 118.3 (4) | C4B—C5B—H5B | 126.2 (3) |
C2'—C3'—H3' | 120.8 (2) | C1B—C5B—H5B | 126.2 (3) |
C4'—C3'—H3' | 120.8 (2) | Fe—C5B—H5B | 125.14 (14) |
C5'—C4'—C3' | 122.2 (4) | C7—C6—C5 | 122.4 (4) |
C5'—C4'—Br | 119.9 (3) | C7—C6—H6 | 118.8 (2) |
C3'—C4'—Br | 117.8 (3) | C5—C6—H6 | 118.8 (2) |
C4'—C5'—C6' | 118.7 (4) | C6—C7—N8 | 118.8 (4) |
C4'—C5'—H5' | 120.7 (2) | C6—C7—C12 | 127.5 (4) |
C6'—C5'—H5' | 120.7 (2) | N8—C7—C12 | 113.7 (3) |
C5'—C6'—C1' | 120.6 (4) | N1—N8—C7 | 125.0 (3) |
C5'—C6'—H6' | 119.7 (2) | N1—N8—C9 | 112.4 (3) |
C1'—C6'—H6' | 119.7 (2) | C7—N8—C9 | 122.5 (3) |
C9—C3—C2 | 105.6 (3) | C3—C9—N8 | 106.0 (3) |
C9—C3—H3 | 127.2 (2) | C3—C9—C4 | 135.9 (4) |
C2—C3—H3 | 127.2 (2) | N8—C9—C4 | 118.0 (3) |
C5—C4—C9 | 121.0 (4) | N11—C10—C4 | 174.0 (5) |
C5—C4—C10 | 125.0 (4) | C13—C12—C7 | 113.5 (3) |
C9—C4—C10 | 114.0 (3) | C13—C12—H12A | 108.9 (3) |
C4—C5—C6 | 117.2 (4) | C7—C12—H12A | 108.9 (2) |
C4—C5—C1A | 123.8 (4) | C13—C12—H12B | 108.9 (2) |
C6—C5—C1A | 119.0 (4) | C7—C12—H12B | 108.9 (2) |
C5A—C1A—C2A | 106.7 (3) | H12A—C12—H12B | 107.7 |
C5A—C1A—C5 | 125.8 (4) | N14—C13—C12 | 175.9 (5) |
N8—N1—C2—C3 | 0.3 (5) | C5B—Fe—C5A—C1A | −122.9 (3) |
N8—N1—C2—C1' | 179.5 (4) | C4B—Fe—C5A—C1A | −163.5 (2) |
N1—C2—C1'—C2' | 160.5 (4) | C2B—Fe—C5A—C1A | −51.3 (6) |
C3—C2—C1'—C2' | −20.4 (6) | C2A—Fe—C5A—C1A | 38.6 (2) |
N1—C2—C1'—C6' | −17.8 (6) | C1B—Fe—C5A—C1A | −81.3 (3) |
C3—C2—C1'—C6' | 161.3 (4) | C4A—Fe—C5A—C1A | 119.8 (4) |
C6'—C1'—C2'—C3' | 0.2 (6) | C3B—Fe—C5A—C1A | 168.0 (6) |
C2—C1'—C2'—C3' | −178.2 (4) | C3A—Fe—C5A—C1A | 82.4 (3) |
C1'—C2'—C3'—C4' | 0.7 (7) | C5B—Fe—C1B—C2B | −119.5 (4) |
C2'—C3'—C4'—C5' | −1.3 (7) | C4B—Fe—C1B—C2B | −81.3 (3) |
C2'—C3'—C4'—Br | 178.0 (3) | C1A—Fe—C1B—C2B | 119.0 (3) |
C3'—C4'—C5'—C6' | 1.0 (7) | C5A—Fe—C1B—C2B | 161.8 (3) |
Br—C4'—C5'—C6' | −178.4 (3) | C2A—Fe—C1B—C2B | 77.3 (4) |
C4'—C5'—C6'—C1' | 0.0 (7) | C4A—Fe—C1B—C2B | −164.6 (4) |
C2'—C1'—C6'—C5' | −0.5 (6) | C3B—Fe—C1B—C2B | −37.6 (3) |
C2—C1'—C6'—C5' | 177.8 (4) | C3A—Fe—C1B—C2B | 46.0 (8) |
N1—C2—C3—C9 | 0.0 (5) | C4B—Fe—C1B—C5B | 38.2 (3) |
C1'—C2—C3—C9 | −179.2 (4) | C2B—Fe—C1B—C5B | 119.5 (4) |
C9—C4—C5—C6 | 1.4 (6) | C1A—Fe—C1B—C5B | −121.5 (3) |
C10—C4—C5—C6 | −177.7 (4) | C5A—Fe—C1B—C5B | −78.7 (3) |
C9—C4—C5—C1A | −177.8 (4) | C2A—Fe—C1B—C5B | −163.2 (3) |
C10—C4—C5—C1A | 3.1 (7) | C4A—Fe—C1B—C5B | −45.2 (6) |
C4—C5—C1A—C5A | −160.1 (4) | C3B—Fe—C1B—C5B | 81.9 (3) |
C6—C5—C1A—C5A | 20.6 (6) | C3A—Fe—C1B—C5B | 165.5 (6) |
C4—C5—C1A—C2A | 21.8 (7) | C5B—C1B—C2B—C3B | 0.7 (6) |
C6—C5—C1A—C2A | −157.4 (4) | Fe—C1B—C2B—C3B | 59.5 (4) |
C4—C5—C1A—Fe | −69.8 (5) | C5B—C1B—C2B—Fe | −58.8 (3) |
C6—C5—C1A—Fe | 110.9 (4) | C5B—Fe—C2B—C3B | −81.7 (3) |
C5B—Fe—C1A—C5A | 74.9 (3) | C4B—Fe—C2B—C3B | −37.7 (3) |
C4B—Fe—C1A—C5A | 44.5 (6) | C1A—Fe—C2B—C3B | 161.7 (3) |
C2B—Fe—C1A—C5A | 158.3 (3) | C5A—Fe—C2B—C3B | −161.3 (4) |
C2A—Fe—C1A—C5A | −118.2 (3) | C2A—Fe—C2B—C3B | 117.7 (3) |
C1B—Fe—C1A—C5A | 116.6 (3) | C1B—Fe—C2B—C3B | −119.4 (5) |
C4A—Fe—C1A—C5A | −37.2 (2) | C4A—Fe—C2B—C3B | 38.5 (8) |
C3B—Fe—C1A—C5A | −169.7 (5) | C3A—Fe—C2B—C3B | 75.7 (4) |
C3A—Fe—C1A—C5A | −80.7 (3) | C5B—Fe—C2B—C1B | 37.7 (3) |
C5B—Fe—C1A—C2A | −166.8 (3) | C4B—Fe—C2B—C1B | 81.6 (3) |
C4B—Fe—C1A—C2A | 162.7 (5) | C1A—Fe—C2B—C1B | −78.9 (3) |
C2B—Fe—C1A—C2A | −83.5 (3) | C5A—Fe—C2B—C1B | −41.9 (6) |
C5A—Fe—C1A—C2A | 118.2 (3) | C2A—Fe—C2B—C1B | −122.9 (3) |
C1B—Fe—C1A—C2A | −125.2 (3) | C4A—Fe—C2B—C1B | 157.9 (6) |
C4A—Fe—C1A—C2A | 81.0 (3) | C3B—Fe—C2B—C1B | 119.4 (5) |
C3B—Fe—C1A—C2A | −51.5 (6) | C3A—Fe—C2B—C1B | −164.9 (3) |
C3A—Fe—C1A—C2A | 37.6 (3) | C1B—C2B—C3B—C4B | 0.0 (6) |
C5B—Fe—C1A—C5 | −44.9 (4) | Fe—C2B—C3B—C4B | 59.3 (4) |
C4B—Fe—C1A—C5 | −75.3 (7) | C1B—C2B—C3B—Fe | −59.3 (4) |
C2B—Fe—C1A—C5 | 38.5 (5) | C5B—Fe—C3B—C4B | −37.4 (3) |
C5A—Fe—C1A—C5 | −119.8 (5) | C2B—Fe—C3B—C4B | −118.9 (5) |
C2A—Fe—C1A—C5 | 122.0 (5) | C1A—Fe—C3B—C4B | −163.0 (4) |
C1B—Fe—C1A—C5 | −3.2 (4) | C5A—Fe—C3B—C4B | 37.9 (8) |
C4A—Fe—C1A—C5 | −157.0 (4) | C2A—Fe—C3B—C4B | 159.3 (3) |
C3B—Fe—C1A—C5 | 70.4 (7) | C1B—Fe—C3B—C4B | −81.4 (3) |
C3A—Fe—C1A—C5 | 159.5 (4) | C4A—Fe—C3B—C4B | 74.2 (4) |
C5A—C1A—C2A—C3A | −0.4 (5) | C3A—Fe—C3B—C4B | 116.3 (3) |
C5—C1A—C2A—C3A | 177.9 (4) | C5B—Fe—C3B—C2B | 81.5 (4) |
Fe—C1A—C2A—C3A | −59.7 (3) | C4B—Fe—C3B—C2B | 118.9 (5) |
C5A—C1A—C2A—Fe | 59.3 (3) | C1A—Fe—C3B—C2B | −44.1 (7) |
C5—C1A—C2A—Fe | −122.3 (4) | C5A—Fe—C3B—C2B | 156.8 (6) |
C5B—Fe—C2A—C3A | 156.5 (6) | C2A—Fe—C3B—C2B | −81.8 (4) |
C4B—Fe—C2A—C3A | −46.1 (6) | C1B—Fe—C3B—C2B | 37.5 (4) |
C2B—Fe—C2A—C3A | −124.6 (3) | C4A—Fe—C3B—C2B | −166.9 (3) |
C1A—Fe—C2A—C3A | 119.2 (4) | C3A—Fe—C3B—C2B | −124.8 (4) |
C5A—Fe—C2A—C3A | 80.8 (3) | C2B—C3B—C4B—C5B | −0.6 (6) |
C1B—Fe—C2A—C3A | −166.6 (3) | Fe—C3B—C4B—C5B | 58.7 (3) |
C4A—Fe—C2A—C3A | 37.1 (3) | C2B—C3B—C4B—Fe | −59.3 (4) |
C3B—Fe—C2A—C3A | −81.7 (3) | C5B—Fe—C4B—C3B | 119.9 (4) |
C5B—Fe—C2A—C1A | 37.3 (7) | C2B—Fe—C4B—C3B | 37.9 (3) |
C4B—Fe—C2A—C1A | −165.2 (4) | C1A—Fe—C4B—C3B | 160.5 (5) |
C2B—Fe—C2A—C1A | 116.2 (3) | C5A—Fe—C4B—C3B | −166.0 (3) |
C5A—Fe—C2A—C1A | −38.4 (2) | C2A—Fe—C4B—C3B | −49.4 (6) |
C1B—Fe—C2A—C1A | 74.2 (3) | C1B—Fe—C4B—C3B | 81.6 (4) |
C4A—Fe—C2A—C1A | −82.1 (3) | C4A—Fe—C4B—C3B | −124.5 (3) |
C3B—Fe—C2A—C1A | 159.1 (3) | C3A—Fe—C4B—C3B | −82.8 (4) |
C3A—Fe—C2A—C1A | −119.2 (4) | C2B—Fe—C4B—C5B | −82.0 (3) |
C1A—C2A—C3A—C4A | 0.7 (5) | C1A—Fe—C4B—C5B | 40.6 (6) |
Fe—C2A—C3A—C4A | −58.7 (3) | C5A—Fe—C4B—C5B | 74.1 (3) |
C1A—C2A—C3A—Fe | 59.3 (3) | C2A—Fe—C4B—C5B | −169.3 (4) |
C5B—Fe—C3A—C4A | −42.5 (6) | C1B—Fe—C4B—C5B | −38.3 (3) |
C4B—Fe—C3A—C4A | −79.3 (3) | C4A—Fe—C4B—C5B | 115.6 (3) |
C2B—Fe—C3A—C4A | −163.9 (3) | C3B—Fe—C4B—C5B | −119.9 (4) |
C1A—Fe—C3A—C4A | 81.9 (3) | C3A—Fe—C4B—C5B | 157.3 (3) |
C5A—Fe—C3A—C4A | 37.5 (3) | C3B—C4B—C5B—C1B | 1.0 (5) |
C2A—Fe—C3A—C4A | 120.1 (4) | Fe—C4B—C5B—C1B | 60.4 (3) |
C1B—Fe—C3A—C4A | 160.6 (6) | C3B—C4B—C5B—Fe | −59.3 (4) |
C3B—Fe—C3A—C4A | −122.1 (3) | C2B—C1B—C5B—C4B | −1.0 (5) |
C5B—Fe—C3A—C2A | −162.6 (4) | Fe—C1B—C5B—C4B | −60.4 (3) |
C4B—Fe—C3A—C2A | 160.6 (3) | C2B—C1B—C5B—Fe | 59.4 (4) |
C2B—Fe—C3A—C2A | 76.0 (3) | C2B—Fe—C5B—C4B | 80.9 (3) |
C1A—Fe—C3A—C2A | −38.2 (3) | C1A—Fe—C5B—C4B | −164.8 (3) |
C5A—Fe—C3A—C2A | −82.5 (3) | C5A—Fe—C5B—C4B | −123.5 (3) |
C1B—Fe—C3A—C2A | 40.5 (8) | C2A—Fe—C5B—C4B | 166.6 (5) |
C4A—Fe—C3A—C2A | −120.1 (4) | C1B—Fe—C5B—C4B | 118.2 (4) |
C3B—Fe—C3A—C2A | 117.8 (3) | C4A—Fe—C5B—C4B | −81.9 (3) |
C2A—C3A—C4A—C5A | −0.6 (5) | C3B—Fe—C5B—C4B | 37.2 (3) |
Fe—C3A—C4A—C5A | −59.1 (3) | C3A—Fe—C5B—C4B | −51.8 (6) |
C2A—C3A—C4A—Fe | 58.5 (3) | C4B—Fe—C5B—C1B | −118.2 (4) |
C5B—Fe—C4A—C5A | −79.4 (3) | C2B—Fe—C5B—C1B | −37.4 (3) |
C4B—Fe—C4A—C5A | −121.8 (3) | C1A—Fe—C5B—C1B | 77.0 (3) |
C2B—Fe—C4A—C5A | 167.9 (6) | C5A—Fe—C5B—C1B | 118.2 (3) |
C1A—Fe—C4A—C5A | 37.7 (2) | C2A—Fe—C5B—C1B | 48.4 (7) |
C2A—Fe—C4A—C5A | 82.3 (3) | C4A—Fe—C5B—C1B | 159.8 (3) |
C1B—Fe—C4A—C5A | −47.3 (5) | C3B—Fe—C5B—C1B | −81.1 (3) |
C3B—Fe—C4A—C5A | −162.5 (3) | C3A—Fe—C5B—C1B | −170.0 (4) |
C3A—Fe—C4A—C5A | 119.5 (4) | C4—C5—C6—C7 | −1.3 (6) |
C5B—Fe—C4A—C3A | 161.1 (3) | C1A—C5—C6—C7 | 177.9 (4) |
C4B—Fe—C4A—C3A | 118.6 (3) | C5—C6—C7—N8 | −0.2 (6) |
C2B—Fe—C4A—C3A | 48.3 (8) | C5—C6—C7—C12 | 178.5 (4) |
C1A—Fe—C4A—C3A | −81.8 (3) | C2—N1—N8—C7 | −176.9 (4) |
C5A—Fe—C4A—C3A | −119.5 (4) | C2—N1—N8—C9 | −0.4 (4) |
C2A—Fe—C4A—C3A | −37.3 (3) | C6—C7—N8—N1 | 178.0 (4) |
C1B—Fe—C4A—C3A | −166.8 (4) | C12—C7—N8—N1 | −0.9 (6) |
C3B—Fe—C4A—C3A | 77.9 (3) | C6—C7—N8—C9 | 1.8 (6) |
C3A—C4A—C5A—C1A | 0.4 (5) | C12—C7—N8—C9 | −177.1 (4) |
Fe—C4A—C5A—C1A | −59.1 (3) | C2—C3—C9—N8 | −0.3 (4) |
C3A—C4A—C5A—Fe | 59.5 (3) | C2—C3—C9—C4 | 178.2 (5) |
C2A—C1A—C5A—C4A | 0.0 (5) | N1—N8—C9—C3 | 0.5 (4) |
C5—C1A—C5A—C4A | −178.4 (4) | C7—N8—C9—C3 | 177.1 (4) |
Fe—C1A—C5A—C4A | 59.3 (3) | N1—N8—C9—C4 | −178.3 (3) |
C2A—C1A—C5A—Fe | −59.3 (3) | C7—N8—C9—C4 | −1.7 (6) |
C5—C1A—C5A—Fe | 122.3 (4) | C5—C4—C9—C3 | −178.3 (5) |
C5B—Fe—C5A—C4A | 117.3 (3) | C10—C4—C9—C3 | 0.9 (7) |
C4B—Fe—C5A—C4A | 76.7 (3) | C5—C4—C9—N8 | 0.1 (6) |
C2B—Fe—C5A—C4A | −171.1 (5) | C10—C4—C9—N8 | 179.2 (4) |
C1A—Fe—C5A—C4A | −119.8 (4) | C5—C4—C10—N11 | 177 (5) |
C2A—Fe—C5A—C4A | −81.2 (3) | C9—C4—C10—N11 | −2 (5) |
C1B—Fe—C5A—C4A | 158.9 (3) | C6—C7—C12—C13 | −7.2 (6) |
C3B—Fe—C5A—C4A | 48.2 (7) | N8—C7—C12—C13 | 171.6 (4) |
C3A—Fe—C5A—C4A | −37.4 (3) | C7—C12—C13—N14 | −161 (8) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C21H12BrN4)] |
Mr | 521.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 7.9608 (1), 10.6844 (1), 12.8215 (3) |
α, β, γ (°) | 93.577 (1), 97.737 (1), 99.046 (1) |
V (Å3) | 1063.28 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.61 |
Crystal size (mm) | 0.25 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Bruker SMARTCCD diffractometer |
Absorption correction | ψ scan (XPREP; Sheldrick, 1994) |
Tmin, Tmax | 0.606, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7790, 4823, 3953 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.140, 1.03 |
No. of reflections | 4783 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.36 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), NRCVAX (Gabe et al., 1989), SHELXL93.
Fe—C5B | 2.031 (5) | Fe—C2A | 2.050 (4) |
Fe—C4B | 2.045 (4) | Fe—C1B | 2.044 (5) |
Fe—C2B | 2.049 (5) | Fe—C4A | 2.055 (4) |
Fe—C1A | 2.054 (4) | Fe—C3B | 2.054 (5) |
Fe—C5A | 2.048 (4) | Fe—C3A | 2.062 (5) |
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In view of the recent growing interest in the field of asymmetric synthesis, ferrocene and its derivatives occupy an important place in synthetic and materials chemistry due to their unique non-linear optical, liquid and crystalline and ferromagnetic properties (Hayashi, 1995). The 1,2- and 1,3-disubstituted ferrocene derivatives, having planar chirality, are suitable chiral reference systems for asymmetric induced synthesis (Marquarding et al., 1970). The unique properties of these compounds encouraged the synthesis of ferrocene derivatives with highly functionalized ring systems directly linked to one of the cyclopentadiene moieties. These compounds do not exhibit optical activity due to lack of restricted rotation. The title compound was synthesized following a procedure reported earlier (Nath et al., 1998). The structure of the title compound, (I), was assigned by IR, NMR and mass spectra, but the conformation of the ferrocene moiety with respect to the heterocyclic ring was of particular interest and prompted us to undertake the present X-ray diffraction study.
The title molecule contains one pyrazolo[2,3-a]pyridine fused-ring system (PP), one bromo-phenyl ring (BP) and one ferrocenyl moiety. The two individual rings [inclined to each other by an angle 1.9 (2)°] in the PP system and the BP ring are planar [the deviations of the atoms from the least-squares planes are within the range -0.012 (3)–0.006 (3) Å]. The –CN group at C12 lies slightly out of the PP ring system [torsion angle C6—C7—C12—C13 - 7.2 (6)°]. The cyclopentadiene rings of the ferrocene moiety are essentually elipsed [the mean value of the five torsion angles CnA—CgA—CgB—CnB (where n = 1–5, and CgA and CgB are the Cp ring centroids) is 4.9 (6)°]. The Cp rings are parallel [dihedral angle 2.4 (3)°] and each lies equidistant [1.65 (1) Å] from the Fe atom. Both the BP and Cp rings adopt a twist conformation with respect to the PP ring system [torsion angle N1—C2—C1'—C6' -17.8 (6)° and C6—C5—C1A—C5A 20.6 (6)°]. There are no short contacts or intermolecular stacking interactions in the lattice.