Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106041345/gd3052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041345/gd3052Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106041345/gd3052IIsup3.hkl |
CCDC references: 628511; 628512
A mixture of oxalyl chloride (3 ml, 34.4 mmol), 1,1'-ferrocenedicarboxylic acid (1.37 g, 5 mmol) and DMF (0.5 ml) in 20 ml of dichloromethane was stirred under nitrogen to give a clear solution. After removal of excess oxalyl chloride, the residue was dissolved in 10 ml of tetrahydrofuran (THF); to the solution was dropwise added a mixture of NEt3 (3.036 g, 30 mmol) and 2-pyridylmethylamine or 3-pyridylmethylamine (0.757 g, 7 mmol) in 25 ml of THF. The mixture was stirred overnight. The resulting crude solid was collected, washed with water, air-dried and recrystallized from 95% ethanol to afford the orange title compounds [(I): m.p. 499.55–500.25 K, yield 57%; (II): m.p. 474.95–475.05 K, yield 51%]. For (I), analysis calculated for C24H22FeN4O2: C 63.45, H 4.88, N 12.33%; found: C 63.50, H 4.72, N 12.51%. IR (KBr): 3273 (m, NH), 1648 (vs, O═C) cm−1. UV [λmax, (ε× 104), in DMF]: 263.00 (2.78, B-band), 345.00 (0.17, R-band), 431.00 (0.09, d-d band) nm. 1H NMR (600 MHz, CDCl3, p.p.m.): δ 10.032 (2H, s, 2NH), 8.602, 7.764, 7.469, 7.292 (2H, s, 2H, s, 2H, s, 2H, s, 2C5H4N), 4.748, 4.350 (4H, s, 4H, s, C5H4), 4.551 (2H, s, CH2). For (II), analysis calculated for C24H22FeN4O2: C 63.45, H 4.88, N 12.33%; found: C 63.49, H 4.76, N 12.31%. IR (KBr): 3217 (m, NH), 1642 (vs, O═ C) cm−1. UV [λmax, (ε× 104), in DMF]: 264.00 (2.93, B-band), 310.50 (1.02, R-band), 503.50 (0.13, d-d band) nm. 1H NMR (600 MHz, CDCl3, p.p.m.): δ 8.578 (2H, s, 2NH), 8.495–8.514, 8.467–8.474, 7.750–7.763, 7.372–7.393 (2H, t, 2H, d, 2H, d, 2H, q, 2C5H4N), 4.759, 4.231 (4H, s, 4H, s, C5H4), 4.403–4.413 (2H, d, CH2).
All H atoms in (I) and (II) were placed at geometrically idealized positions and subsequently treated as riding atoms, with C—H distances of 0.93 (pyridyl group), 0.97 (CH2) and 0.98 (cyclopentadienyl group), and N—H distances of 0.86 Å at 295 K for (I), and C—H distances of 0.95 (pyridyl group), 0.99 (CH2) and 1.00 (cyclopentadienyl group), and an N—H distance of 0.88 Å at 193 K for (II); Uiso(H) values were set at 1.2Ueq(C,N).
Data collection: CAD-4 Software (Enraf–Nonius, 1989) for (I); CrystalClear (Rigaku Corporation & Molecular Structure Corporation, 2001) for (II). Cell refinement: CAD-4 Software for (I); CrystalClear for (II). Data reduction: XCAD4 (Harms & Wocadlo, 1995) for (I); CrystalStructure (Rigaku Corporation & Molecular Structure Corporation, 2004) for (II). For both compounds, program(s) used to solve structure: OSCAIL-X (McArdle, 2005) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL-X and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
[Fe(C12H11N2O)2] | Z = 2 |
Mr = 454.31 | F(000) = 472 |
Triclinic, P1 | Dx = 1.447 Mg m−3 |
a = 8.9859 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.8987 (2) Å | Cell parameters from 25 reflections |
c = 13.7459 (3) Å | θ = 9–15° |
α = 100.297 (2)° | µ = 0.75 mm−1 |
β = 102.114 (2)° | T = 295 K |
γ = 114.051 (1)° | Prism, orange |
V = 1042.75 (4) Å3 | 0.23 × 0.15 × 0.12 mm |
Enraf–Nonius CAD-4 diffractometer | 3611 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 27.5°, θmin = 3.4° |
ω/2θ scans | h = −11→11 |
Absorption correction: empirical ψ scan (North et al., 1968) | k = −12→12 |
Tmin = 0.858, Tmax = 0.914 | l = −17→17 |
14739 measured reflections | 3 standard reflections every 200 reflections |
4769 independent reflections | intensity decay: none |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0348P)2 + 0.4231P] where P = (Fo2 + 2Fc2)/3 |
4769 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Fe(C12H11N2O)2] | γ = 114.051 (1)° |
Mr = 454.31 | V = 1042.75 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9859 (2) Å | Mo Kα radiation |
b = 9.8987 (2) Å | µ = 0.75 mm−1 |
c = 13.7459 (3) Å | T = 295 K |
α = 100.297 (2)° | 0.23 × 0.15 × 0.12 mm |
β = 102.114 (2)° |
Enraf–Nonius CAD-4 diffractometer | 3611 reflections with I > 2σ(I) |
Absorption correction: empirical ψ scan (North et al., 1968) | Rint = 0.050 |
Tmin = 0.858, Tmax = 0.914 | 3 standard reflections every 200 reflections |
14739 measured reflections | intensity decay: none |
4769 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.24 e Å−3 |
4769 reflections | Δρmin = −0.40 e Å−3 |
280 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 | ||
C1 | 0.4562 (3) | 0.2882 (3) | 0.05827 (18) | 0.0443 (6) | |
H1 | 0.5169 | 0.3719 | 0.0306 | 0.053* | |
C2 | 0.5007 (4) | 0.1708 (3) | 0.0753 (2) | 0.0502 (7) | |
H2 | 0.5992 | 0.1603 | 0.0624 | 0.060* | |
C3 | 0.3808 (4) | 0.0723 (3) | 0.1160 (2) | 0.0502 (7) | |
H3 | 0.3821 | −0.0177 | 0.1357 | 0.060* | |
C4 | 0.2607 (3) | 0.1278 (3) | 0.12431 (19) | 0.0432 (6) | |
H4 | 0.1637 | 0.0827 | 0.1505 | 0.052* | |
C5 | 0.3059 (3) | 0.2622 (3) | 0.08875 (17) | 0.0378 (6) | |
C6 | 0.2204 (3) | 0.3619 (3) | 0.08464 (18) | 0.0396 (6) | |
C7 | −0.0035 (4) | 0.4176 (3) | 0.1251 (2) | 0.0468 (6) | |
H7A | −0.1109 | 0.3594 | 0.1374 | 0.056* | |
H7B | −0.0313 | 0.4333 | 0.0573 | 0.056* | |
C8 | 0.0944 (3) | 0.5741 (3) | 0.2071 (2) | 0.0402 (6) | |
C9 | 0.0614 (4) | 0.6965 (4) | 0.1943 (2) | 0.0565 (8) | |
H9 | −0.0168 | 0.6858 | 0.1335 | 0.068* | |
C10 | 0.1473 (5) | 0.8340 (4) | 0.2738 (3) | 0.0672 (9) | |
H10 | 0.1255 | 0.9168 | 0.2678 | 0.081* | |
C11 | 0.2642 (4) | 0.8484 (3) | 0.3614 (3) | 0.0582 (8) | |
H11 | 0.3253 | 0.9412 | 0.4150 | 0.070* | |
C12 | 0.2892 (4) | 0.7227 (3) | 0.3683 (2) | 0.0544 (7) | |
H12 | 0.3676 | 0.7319 | 0.4285 | 0.065* | |
C13 | 0.5550 (3) | 0.4906 (3) | 0.32137 (18) | 0.0392 (6) | |
H13 | 0.4965 | 0.5548 | 0.3150 | 0.047* | |
C14 | 0.7029 (3) | 0.5103 (3) | 0.2920 (2) | 0.0497 (7) | |
H14 | 0.7639 | 0.5899 | 0.2615 | 0.060* | |
C15 | 0.7462 (4) | 0.3939 (4) | 0.3138 (2) | 0.0544 (8) | |
H15 | 0.8420 | 0.3786 | 0.3004 | 0.065* | |
C16 | 0.6257 (4) | 0.3022 (3) | 0.35723 (19) | 0.0467 (6) | |
H16 | 0.6238 | 0.2128 | 0.3792 | 0.056* | |
C17 | 0.5068 (3) | 0.3626 (3) | 0.36235 (17) | 0.0363 (5) | |
C18 | 0.3619 (3) | 0.2982 (3) | 0.40347 (17) | 0.0341 (5) | |
C19 | 0.1032 (3) | 0.2981 (3) | 0.42747 (19) | 0.0412 (6) | |
H19A | 0.0614 | 0.3743 | 0.4351 | 0.049* | |
H19B | 0.1392 | 0.2864 | 0.4957 | 0.049* | |
C20 | −0.0426 (3) | 0.1449 (3) | 0.35616 (19) | 0.0368 (5) | |
C21 | −0.1457 (4) | 0.0388 (3) | 0.3968 (2) | 0.0494 (7) | |
H21 | −0.1226 | 0.0591 | 0.4685 | 0.059* | |
C22 | −0.2819 (4) | −0.0963 (3) | 0.3312 (3) | 0.0642 (9) | |
H22 | −0.3531 | −0.1678 | 0.3577 | 0.077* | |
C23 | −0.3121 (4) | −0.1249 (3) | 0.2257 (3) | 0.0643 (9) | |
H23 | −0.4035 | −0.2157 | 0.1791 | 0.077* | |
C24 | −0.2030 (4) | −0.0151 (3) | 0.1912 (2) | 0.0561 (8) | |
H24 | −0.2227 | −0.0347 | 0.1198 | 0.067* | |
Fe1 | 0.50233 (5) | 0.29617 (4) | 0.21164 (3) | 0.03613 (12) | |
N1 | 0.0872 (3) | 0.3262 (2) | 0.12258 (16) | 0.0412 (5) | |
H1N | 0.0555 | 0.2472 | 0.1458 | 0.049* | |
N2 | 0.2067 (3) | 0.5870 (2) | 0.29298 (17) | 0.0448 (5) | |
N3 | 0.2504 (3) | 0.3557 (2) | 0.39139 (15) | 0.0367 (5) | |
H3N | 0.2665 | 0.4278 | 0.3618 | 0.044* | |
N4 | −0.0694 (3) | 0.1189 (2) | 0.25385 (16) | 0.0449 (5) | |
O1 | 0.2657 (3) | 0.4695 (2) | 0.04623 (16) | 0.0601 (6) | |
O2 | 0.3471 (3) | 0.1989 (2) | 0.44891 (14) | 0.0481 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0446 (15) | 0.0515 (15) | 0.0278 (12) | 0.0165 (13) | 0.0115 (11) | 0.0050 (11) |
C2 | 0.0479 (17) | 0.0579 (17) | 0.0368 (14) | 0.0249 (14) | 0.0115 (12) | −0.0029 (12) |
C3 | 0.0546 (18) | 0.0414 (14) | 0.0466 (16) | 0.0205 (13) | 0.0125 (13) | 0.0030 (12) |
C4 | 0.0425 (15) | 0.0419 (14) | 0.0355 (13) | 0.0138 (12) | 0.0095 (11) | 0.0066 (11) |
C5 | 0.0381 (14) | 0.0426 (13) | 0.0254 (11) | 0.0144 (11) | 0.0076 (10) | 0.0066 (10) |
C6 | 0.0386 (14) | 0.0492 (14) | 0.0268 (12) | 0.0167 (12) | 0.0070 (10) | 0.0144 (11) |
C7 | 0.0426 (15) | 0.0646 (17) | 0.0379 (14) | 0.0268 (14) | 0.0141 (12) | 0.0194 (13) |
C8 | 0.0381 (14) | 0.0533 (15) | 0.0412 (14) | 0.0257 (12) | 0.0183 (11) | 0.0235 (12) |
C9 | 0.067 (2) | 0.074 (2) | 0.0561 (18) | 0.0484 (18) | 0.0241 (16) | 0.0387 (16) |
C10 | 0.092 (3) | 0.062 (2) | 0.081 (2) | 0.052 (2) | 0.041 (2) | 0.0385 (19) |
C11 | 0.068 (2) | 0.0469 (16) | 0.065 (2) | 0.0282 (15) | 0.0275 (17) | 0.0169 (15) |
C12 | 0.0570 (19) | 0.0548 (17) | 0.0516 (17) | 0.0296 (15) | 0.0117 (14) | 0.0138 (14) |
C13 | 0.0399 (14) | 0.0340 (12) | 0.0340 (13) | 0.0127 (11) | 0.0081 (11) | 0.0035 (10) |
C14 | 0.0395 (16) | 0.0534 (16) | 0.0398 (15) | 0.0105 (13) | 0.0122 (12) | 0.0034 (12) |
C15 | 0.0417 (16) | 0.081 (2) | 0.0382 (15) | 0.0331 (16) | 0.0089 (12) | 0.0067 (14) |
C16 | 0.0485 (16) | 0.0646 (17) | 0.0345 (13) | 0.0358 (14) | 0.0093 (12) | 0.0123 (12) |
C17 | 0.0373 (14) | 0.0423 (13) | 0.0269 (12) | 0.0206 (11) | 0.0052 (10) | 0.0053 (10) |
C18 | 0.0391 (14) | 0.0341 (12) | 0.0245 (11) | 0.0175 (11) | 0.0042 (10) | 0.0037 (9) |
C19 | 0.0401 (14) | 0.0492 (14) | 0.0318 (13) | 0.0213 (12) | 0.0102 (11) | 0.0063 (11) |
C20 | 0.0374 (14) | 0.0420 (13) | 0.0358 (13) | 0.0210 (11) | 0.0139 (11) | 0.0131 (11) |
C21 | 0.0559 (18) | 0.0552 (16) | 0.0435 (15) | 0.0254 (14) | 0.0228 (13) | 0.0211 (13) |
C22 | 0.066 (2) | 0.0477 (17) | 0.074 (2) | 0.0131 (15) | 0.0327 (18) | 0.0263 (16) |
C23 | 0.059 (2) | 0.0428 (16) | 0.065 (2) | 0.0051 (14) | 0.0124 (16) | 0.0085 (15) |
C24 | 0.0593 (19) | 0.0518 (16) | 0.0372 (15) | 0.0146 (14) | 0.0048 (13) | 0.0074 (13) |
Fe1 | 0.0382 (2) | 0.0407 (2) | 0.02800 (19) | 0.01942 (16) | 0.00887 (14) | 0.00591 (14) |
N1 | 0.0438 (13) | 0.0437 (12) | 0.0389 (12) | 0.0189 (10) | 0.0171 (10) | 0.0170 (9) |
N2 | 0.0492 (14) | 0.0481 (12) | 0.0405 (12) | 0.0271 (11) | 0.0087 (10) | 0.0158 (10) |
N3 | 0.0369 (12) | 0.0381 (11) | 0.0364 (11) | 0.0178 (9) | 0.0110 (9) | 0.0136 (9) |
N4 | 0.0476 (13) | 0.0438 (12) | 0.0313 (11) | 0.0117 (10) | 0.0091 (10) | 0.0105 (9) |
O1 | 0.0600 (13) | 0.0780 (14) | 0.0671 (14) | 0.0372 (11) | 0.0317 (11) | 0.0513 (12) |
O2 | 0.0626 (13) | 0.0493 (10) | 0.0475 (11) | 0.0330 (10) | 0.0210 (9) | 0.0263 (9) |
C1—C2 | 1.414 (4) | C13—C17 | 1.422 (3) |
C1—C5 | 1.434 (3) | C13—Fe1 | 2.031 (2) |
C1—Fe1 | 2.042 (2) | C13—H13 | 0.9800 |
C1—H1 | 0.9800 | C14—C15 | 1.417 (4) |
C2—C3 | 1.420 (4) | C14—Fe1 | 2.044 (3) |
C2—Fe1 | 2.048 (2) | C14—H14 | 0.9800 |
C2—H2 | 0.9800 | C15—C16 | 1.420 (4) |
C3—C4 | 1.412 (4) | C15—Fe1 | 2.050 (3) |
C3—Fe1 | 2.053 (3) | C15—H15 | 0.9800 |
C3—H3 | 0.9800 | C16—C17 | 1.428 (3) |
C4—C5 | 1.431 (3) | C16—Fe1 | 2.052 (3) |
C4—Fe1 | 2.043 (3) | C16—H16 | 0.9800 |
C4—H4 | 0.9800 | C17—C18 | 1.477 (3) |
C5—C6 | 1.480 (4) | C17—Fe1 | 2.045 (2) |
C5—Fe1 | 2.035 (2) | C18—O2 | 1.233 (3) |
C6—O1 | 1.231 (3) | C18—N3 | 1.337 (3) |
C6—N1 | 1.346 (3) | C19—N3 | 1.442 (3) |
C7—N1 | 1.444 (3) | C19—C20 | 1.512 (3) |
C7—C8 | 1.514 (4) | C19—H19A | 0.9700 |
C7—H7A | 0.9700 | C19—H19B | 0.9700 |
C7—H7B | 0.9700 | C20—N4 | 1.334 (3) |
C8—N2 | 1.331 (3) | C20—C21 | 1.381 (3) |
C8—C9 | 1.390 (4) | C21—C22 | 1.368 (4) |
C9—C10 | 1.379 (4) | C21—H21 | 0.9300 |
C9—H9 | 0.9300 | C22—C23 | 1.372 (4) |
C10—C11 | 1.363 (5) | C22—H22 | 0.9300 |
C10—H10 | 0.9300 | C23—C24 | 1.370 (4) |
C11—C12 | 1.367 (4) | C23—H23 | 0.9300 |
C11—H11 | 0.9300 | C24—N4 | 1.342 (3) |
C12—N2 | 1.340 (3) | C24—H24 | 0.9300 |
C12—H12 | 0.9300 | N1—H1N | 0.8600 |
C13—C14 | 1.417 (4) | N3—H3N | 0.8600 |
C2—C1—C5 | 107.5 (2) | C13—C17—Fe1 | 69.04 (13) |
C2—C1—Fe1 | 70.01 (15) | C16—C17—Fe1 | 69.84 (14) |
C5—C1—Fe1 | 69.15 (14) | C18—C17—Fe1 | 126.33 (16) |
C2—C1—H1 | 126.2 | O2—C18—N3 | 121.7 (2) |
C5—C1—H1 | 126.2 | O2—C18—C17 | 121.5 (2) |
Fe1—C1—H1 | 126.2 | N3—C18—C17 | 116.7 (2) |
C1—C2—C3 | 108.7 (2) | N3—C19—C20 | 114.03 (19) |
C1—C2—Fe1 | 69.53 (14) | N3—C19—H19A | 108.7 |
C3—C2—Fe1 | 69.94 (15) | C20—C19—H19A | 108.7 |
C1—C2—H2 | 125.6 | N3—C19—H19B | 108.7 |
C3—C2—H2 | 125.6 | C20—C19—H19B | 108.7 |
Fe1—C2—H2 | 125.6 | H19A—C19—H19B | 107.6 |
C4—C3—C2 | 108.0 (3) | N4—C20—C21 | 122.0 (2) |
C4—C3—Fe1 | 69.44 (14) | N4—C20—C19 | 117.6 (2) |
C2—C3—Fe1 | 69.56 (15) | C21—C20—C19 | 120.4 (2) |
C4—C3—H3 | 126.0 | C22—C21—C20 | 119.8 (3) |
C2—C3—H3 | 126.0 | C22—C21—H21 | 120.1 |
Fe1—C3—H3 | 126.0 | C20—C21—H21 | 120.1 |
C3—C4—C5 | 108.2 (2) | C21—C22—C23 | 119.1 (3) |
C3—C4—Fe1 | 70.23 (15) | C21—C22—H22 | 120.4 |
C5—C4—Fe1 | 69.17 (14) | C23—C22—H22 | 120.4 |
C3—C4—H4 | 125.9 | C24—C23—C22 | 117.8 (3) |
C5—C4—H4 | 125.9 | C24—C23—H23 | 121.1 |
Fe1—C4—H4 | 125.9 | C22—C23—H23 | 121.1 |
C4—C5—C1 | 107.5 (2) | N4—C24—C23 | 124.3 (3) |
C4—C5—C6 | 128.1 (2) | N4—C24—H24 | 117.8 |
C1—C5—C6 | 124.4 (2) | C23—C24—H24 | 117.8 |
C4—C5—Fe1 | 69.75 (14) | C13—Fe1—C5 | 106.64 (10) |
C1—C5—Fe1 | 69.65 (14) | C13—Fe1—C1 | 120.44 (11) |
C6—C5—Fe1 | 124.96 (16) | C5—Fe1—C1 | 41.20 (10) |
O1—C6—N1 | 121.7 (2) | C13—Fe1—C4 | 124.54 (10) |
O1—C6—C5 | 121.9 (2) | C5—Fe1—C4 | 41.08 (10) |
N1—C6—C5 | 116.4 (2) | C1—Fe1—C4 | 68.91 (10) |
N1—C7—C8 | 114.6 (2) | C13—Fe1—C14 | 40.71 (10) |
N1—C7—H7A | 108.6 | C5—Fe1—C14 | 122.50 (11) |
C8—C7—H7A | 108.6 | C1—Fe1—C14 | 105.58 (11) |
N1—C7—H7B | 108.6 | C4—Fe1—C14 | 160.32 (12) |
C8—C7—H7B | 108.6 | C13—Fe1—C17 | 40.84 (10) |
H7A—C7—H7B | 107.6 | C5—Fe1—C17 | 122.05 (10) |
N2—C8—C9 | 121.8 (3) | C1—Fe1—C17 | 157.18 (10) |
N2—C8—C7 | 117.3 (2) | C4—Fe1—C17 | 108.83 (10) |
C9—C8—C7 | 120.8 (3) | C14—Fe1—C17 | 68.53 (10) |
C10—C9—C8 | 118.5 (3) | C13—Fe1—C2 | 156.06 (11) |
C10—C9—H9 | 120.8 | C5—Fe1—C2 | 68.49 (11) |
C8—C9—H9 | 120.8 | C1—Fe1—C2 | 40.46 (11) |
C11—C10—C9 | 119.9 (3) | C4—Fe1—C2 | 68.11 (11) |
C11—C10—H10 | 120.1 | C14—Fe1—C2 | 120.70 (11) |
C9—C10—H10 | 120.1 | C17—Fe1—C2 | 161.53 (11) |
C10—C11—C12 | 118.2 (3) | C13—Fe1—C15 | 68.38 (11) |
C10—C11—H11 | 120.9 | C5—Fe1—C15 | 158.94 (12) |
C12—C11—H11 | 120.9 | C1—Fe1—C15 | 122.25 (11) |
N2—C12—C11 | 123.4 (3) | C4—Fe1—C15 | 158.36 (12) |
N2—C12—H12 | 118.3 | C14—Fe1—C15 | 40.50 (12) |
C11—C12—H12 | 118.3 | C17—Fe1—C15 | 68.43 (10) |
C14—C13—C17 | 108.3 (2) | C2—Fe1—C15 | 107.29 (11) |
C14—C13—Fe1 | 70.13 (15) | C13—Fe1—C16 | 68.56 (11) |
C17—C13—Fe1 | 70.12 (13) | C5—Fe1—C16 | 158.65 (11) |
C14—C13—H13 | 125.8 | C1—Fe1—C16 | 159.42 (11) |
C17—C13—H13 | 125.8 | C4—Fe1—C16 | 123.33 (11) |
Fe1—C13—H13 | 125.8 | C14—Fe1—C16 | 68.29 (12) |
C15—C14—C13 | 108.0 (3) | C17—Fe1—C16 | 40.81 (10) |
C15—C14—Fe1 | 70.00 (16) | C2—Fe1—C16 | 124.40 (11) |
C13—C14—Fe1 | 69.16 (14) | C15—Fe1—C16 | 40.52 (11) |
C15—C14—H14 | 126.0 | C13—Fe1—C3 | 161.57 (11) |
C13—C14—H14 | 126.0 | C5—Fe1—C3 | 68.56 (11) |
Fe1—C14—H14 | 126.0 | C1—Fe1—C3 | 68.47 (11) |
C14—C15—C16 | 108.2 (2) | C4—Fe1—C3 | 40.33 (11) |
C14—C15—Fe1 | 69.50 (15) | C14—Fe1—C3 | 156.96 (11) |
C16—C15—Fe1 | 69.79 (16) | C17—Fe1—C3 | 125.43 (11) |
C14—C15—H15 | 125.9 | C2—Fe1—C3 | 40.51 (11) |
C16—C15—H15 | 125.9 | C15—Fe1—C3 | 122.51 (12) |
Fe1—C15—H15 | 125.9 | C16—Fe1—C3 | 109.05 (12) |
C15—C16—C17 | 107.9 (2) | C6—N1—C7 | 121.4 (2) |
C15—C16—Fe1 | 69.69 (16) | C6—N1—H1N | 119.3 |
C17—C16—Fe1 | 69.35 (14) | C7—N1—H1N | 119.3 |
C15—C16—H16 | 126.1 | C8—N2—C12 | 118.2 (2) |
C17—C16—H16 | 126.1 | C18—N3—C19 | 120.6 (2) |
Fe1—C16—H16 | 126.1 | C18—N3—H3N | 119.7 |
C13—C17—C16 | 107.6 (2) | C19—N3—H3N | 119.7 |
C13—C17—C18 | 128.3 (2) | C20—N4—C24 | 117.0 (2) |
C16—C17—C18 | 124.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N4 | 0.86 | 2.30 | 3.079 (3) | 151 |
N3—H3N···N2 | 0.86 | 2.16 | 2.974 (3) | 157 |
C1—H1···O1i | 0.98 | 2.52 | 3.452 (4) | 159 |
C11—H11···O2ii | 0.93 | 2.43 | 3.173 (4) | 137 |
C12—H12···O2iii | 0.93 | 2.49 | 3.374 (4) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1. |
[Fe(C12H11N2O)2] | Z = 1 |
Mr = 454.31 | F(000) = 236 |
Triclinic, P1 | Dx = 1.512 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 6.386 (3) Å | Cell parameters from 1980 reflections |
b = 7.882 (3) Å | θ = 3.2–25.3° |
c = 9.987 (4) Å | µ = 0.79 mm−1 |
α = 85.305 (17)° | T = 193 K |
β = 89.53 (2)° | Block, orange |
γ = 84.831 (19)° | 0.30 × 0.25 × 0.10 mm |
V = 499.0 (4) Å3 |
Rigaku Mercury diffractometer | 1810 independent reflections |
Radiation source: fine-focus sealed tube | 1602 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.3°, θmin = 3.2° |
ω scans | h = −7→7 |
Absorption correction: multi-scan Jacobson, 1998) | k = −9→8 |
Tmin = 0.811, Tmax = 0.917 | l = −11→12 |
4908 measured reflections |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0253P)2 + 0.3145P] where P = (Fo2 + 2Fc2)/3 |
1810 reflections | (Δ/σ)max < 0.001 |
143 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[Fe(C12H11N2O)2] | γ = 84.831 (19)° |
Mr = 454.31 | V = 499.0 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.386 (3) Å | Mo Kα radiation |
b = 7.882 (3) Å | µ = 0.79 mm−1 |
c = 9.987 (4) Å | T = 193 K |
α = 85.305 (17)° | 0.30 × 0.25 × 0.10 mm |
β = 89.53 (2)° |
Rigaku Mercury diffractometer | 1810 independent reflections |
Absorption correction: multi-scan Jacobson, 1998) | 1602 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.917 | Rint = 0.035 |
4908 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.36 e Å−3 |
1810 reflections | Δρmin = −0.45 e Å−3 |
143 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 | ||
Fe1 | 0.5000 | 0.5000 | 0.5000 | 0.02325 (17) | |
O1 | 0.2129 (3) | 0.4104 (2) | 0.17427 (18) | 0.0344 (5) | |
N1 | 0.4427 (3) | 0.6125 (3) | 0.13850 (19) | 0.0231 (5) | |
H1N | 0.5681 | 0.6431 | 0.1560 | 0.028* | |
N2 | −0.2239 (3) | 0.8381 (3) | 0.1824 (2) | 0.0298 (5) | |
C5 | 0.5048 (4) | 0.3941 (3) | 0.3208 (2) | 0.0234 (6) | |
C4 | 0.4270 (4) | 0.2788 (3) | 0.4235 (2) | 0.0268 (6) | |
H4 | 0.2857 | 0.2333 | 0.4254 | 0.032* | |
C3 | 0.5854 (4) | 0.2419 (3) | 0.5222 (3) | 0.0313 (6) | |
H3 | 0.5746 | 0.1663 | 0.6069 | 0.038* | |
C2 | 0.7611 (4) | 0.3321 (3) | 0.4820 (3) | 0.0313 (6) | |
H2 | 0.8955 | 0.3303 | 0.5330 | 0.038* | |
C1 | 0.7121 (4) | 0.4261 (3) | 0.3569 (2) | 0.0262 (6) | |
H1 | 0.8060 | 0.5015 | 0.3039 | 0.031* | |
C6 | 0.3751 (4) | 0.4719 (3) | 0.2054 (2) | 0.0226 (5) | |
C7 | 0.3117 (4) | 0.7142 (3) | 0.0379 (2) | 0.0245 (6) | |
H7A | 0.2519 | 0.6379 | −0.0229 | 0.029* | |
H7B | 0.3984 | 0.7918 | −0.0166 | 0.029* | |
C8 | 0.1349 (4) | 0.8182 (3) | 0.1044 (2) | 0.0216 (5) | |
C12 | −0.0630 (4) | 0.7612 (3) | 0.1156 (2) | 0.0265 (6) | |
H12 | −0.0874 | 0.6611 | 0.0733 | 0.032* | |
C11 | −0.1864 (4) | 0.9809 (3) | 0.2381 (3) | 0.0298 (6) | |
H11 | −0.2968 | 1.0366 | 0.2869 | 0.036* | |
C10 | 0.0026 (4) | 1.0518 (3) | 0.2287 (3) | 0.0289 (6) | |
H10 | 0.0206 | 1.1556 | 0.2676 | 0.035* | |
C9 | 0.1661 (4) | 0.9684 (3) | 0.1612 (2) | 0.0261 (6) | |
H9 | 0.2988 | 1.0139 | 0.1539 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0273 (3) | 0.0200 (3) | 0.0221 (3) | 0.0022 (2) | 0.0001 (2) | −0.0039 (2) |
O1 | 0.0363 (11) | 0.0331 (11) | 0.0354 (11) | −0.0135 (9) | −0.0083 (9) | 0.0010 (9) |
N1 | 0.0187 (11) | 0.0243 (11) | 0.0258 (11) | −0.0010 (9) | 0.0002 (9) | 0.0007 (9) |
N2 | 0.0236 (12) | 0.0310 (13) | 0.0355 (12) | −0.0056 (10) | 0.0020 (10) | −0.0035 (10) |
C5 | 0.0263 (14) | 0.0198 (13) | 0.0242 (13) | 0.0018 (11) | 0.0019 (11) | −0.0072 (11) |
C4 | 0.0358 (16) | 0.0186 (13) | 0.0265 (13) | −0.0023 (11) | 0.0045 (12) | −0.0060 (11) |
C3 | 0.0491 (18) | 0.0175 (13) | 0.0253 (14) | 0.0075 (12) | 0.0022 (13) | −0.0014 (11) |
C2 | 0.0300 (15) | 0.0320 (15) | 0.0299 (14) | 0.0124 (12) | −0.0037 (12) | −0.0075 (12) |
C1 | 0.0244 (14) | 0.0263 (14) | 0.0272 (13) | 0.0042 (11) | 0.0023 (11) | −0.0061 (11) |
C6 | 0.0245 (14) | 0.0210 (13) | 0.0231 (12) | −0.0001 (11) | 0.0017 (11) | −0.0078 (10) |
C7 | 0.0262 (14) | 0.0260 (14) | 0.0203 (12) | 0.0014 (11) | 0.0016 (10) | 0.0008 (11) |
C8 | 0.0244 (14) | 0.0217 (13) | 0.0174 (12) | −0.0007 (10) | −0.0017 (10) | 0.0042 (10) |
C12 | 0.0294 (15) | 0.0215 (13) | 0.0287 (14) | −0.0018 (11) | −0.0001 (11) | −0.0039 (11) |
C11 | 0.0295 (15) | 0.0284 (14) | 0.0309 (14) | 0.0021 (12) | 0.0034 (12) | −0.0044 (12) |
C10 | 0.0317 (15) | 0.0220 (14) | 0.0336 (15) | −0.0026 (11) | −0.0045 (12) | −0.0059 (12) |
C9 | 0.0234 (14) | 0.0261 (14) | 0.0291 (14) | −0.0071 (11) | −0.0026 (11) | 0.0008 (11) |
Fe1—C5i | 2.035 (2) | C4—C3 | 1.413 (4) |
Fe1—C5 | 2.035 (2) | C4—H4 | 1.0000 |
Fe1—C1i | 2.044 (2) | C3—C2 | 1.420 (4) |
Fe1—C1 | 2.044 (2) | C3—H3 | 1.0000 |
Fe1—C2i | 2.050 (3) | C2—C1 | 1.422 (4) |
Fe1—C2 | 2.050 (3) | C2—H2 | 1.0000 |
Fe1—C4i | 2.052 (2) | C1—H1 | 1.0000 |
Fe1—C4 | 2.052 (2) | C7—C8 | 1.516 (3) |
Fe1—C3i | 2.053 (3) | C7—H7A | 0.9900 |
Fe1—C3 | 2.053 (3) | C7—H7B | 0.9900 |
O1—C6 | 1.235 (3) | C8—C12 | 1.380 (4) |
N1—C6 | 1.349 (3) | C8—C9 | 1.385 (3) |
N1—C7 | 1.454 (3) | C12—H12 | 0.9500 |
N1—H1N | 0.8800 | C11—C10 | 1.375 (4) |
N2—C11 | 1.336 (3) | C11—H11 | 0.9500 |
N2—C12 | 1.346 (3) | C10—C9 | 1.383 (4) |
C5—C1 | 1.425 (4) | C10—H10 | 0.9500 |
C5—C4 | 1.430 (3) | C9—H9 | 0.9500 |
C5—C6 | 1.483 (3) | ||
C5i—Fe1—C5 | 180.000 (1) | C1—C5—Fe1 | 69.92 (14) |
C5i—Fe1—C1i | 40.89 (10) | C4—C5—Fe1 | 70.19 (13) |
C5—Fe1—C1i | 139.11 (10) | C6—C5—Fe1 | 121.80 (16) |
C5i—Fe1—C1 | 139.11 (10) | C3—C4—C5 | 107.6 (2) |
C5—Fe1—C1 | 40.89 (10) | C3—C4—Fe1 | 69.89 (15) |
C1i—Fe1—C1 | 180.0 | C5—C4—Fe1 | 68.86 (13) |
C5i—Fe1—C2i | 68.49 (10) | C3—C4—H4 | 126.2 |
C5—Fe1—C2i | 111.51 (10) | C5—C4—H4 | 126.2 |
C1i—Fe1—C2i | 40.65 (10) | Fe1—C4—H4 | 126.2 |
C1—Fe1—C2i | 139.35 (10) | C4—C3—C2 | 108.6 (2) |
C5i—Fe1—C2 | 111.51 (10) | C4—C3—Fe1 | 69.86 (14) |
C5—Fe1—C2 | 68.49 (10) | C2—C3—Fe1 | 69.63 (14) |
C1i—Fe1—C2 | 139.35 (10) | C4—C3—H3 | 125.7 |
C1—Fe1—C2 | 40.65 (10) | C2—C3—H3 | 125.7 |
C2i—Fe1—C2 | 180.000 (1) | Fe1—C3—H3 | 125.7 |
C5i—Fe1—C4i | 40.95 (10) | C3—C2—C1 | 108.0 (2) |
C5—Fe1—C4i | 139.05 (10) | C3—C2—Fe1 | 69.87 (14) |
C1i—Fe1—C4i | 68.68 (10) | C1—C2—Fe1 | 69.47 (14) |
C1—Fe1—C4i | 111.32 (10) | C3—C2—H2 | 126.0 |
C2i—Fe1—C4i | 68.23 (11) | C1—C2—H2 | 126.0 |
C2—Fe1—C4i | 111.77 (11) | Fe1—C2—H2 | 126.0 |
C5i—Fe1—C4 | 139.05 (10) | C2—C1—C5 | 107.7 (2) |
C5—Fe1—C4 | 40.95 (10) | C2—C1—Fe1 | 69.88 (14) |
C1i—Fe1—C4 | 111.32 (10) | C5—C1—Fe1 | 69.19 (14) |
C1—Fe1—C4 | 68.68 (10) | C2—C1—H1 | 126.2 |
C2i—Fe1—C4 | 111.77 (11) | C5—C1—H1 | 126.2 |
C2—Fe1—C4 | 68.23 (11) | Fe1—C1—H1 | 126.2 |
C4i—Fe1—C4 | 180.0 | O1—C6—N1 | 122.5 (2) |
C5i—Fe1—C3i | 68.27 (10) | O1—C6—C5 | 120.9 (2) |
C5—Fe1—C3i | 111.73 (10) | N1—C6—C5 | 116.6 (2) |
C1i—Fe1—C3i | 68.28 (10) | N1—C7—C8 | 110.49 (19) |
C1—Fe1—C3i | 111.72 (11) | N1—C7—H7A | 109.6 |
C2i—Fe1—C3i | 40.50 (11) | C8—C7—H7A | 109.6 |
C2—Fe1—C3i | 139.50 (11) | N1—C7—H7B | 109.6 |
C4i—Fe1—C3i | 40.25 (10) | C8—C7—H7B | 109.6 |
C4—Fe1—C3i | 139.75 (10) | H7A—C7—H7B | 108.1 |
C5i—Fe1—C3 | 111.73 (10) | C12—C8—C9 | 117.4 (2) |
C5—Fe1—C3 | 68.27 (10) | C12—C8—C7 | 120.5 (2) |
C1i—Fe1—C3 | 111.72 (11) | C9—C8—C7 | 122.1 (2) |
C1—Fe1—C3 | 68.28 (10) | N2—C12—C8 | 124.3 (2) |
C2i—Fe1—C3 | 139.50 (11) | N2—C12—H12 | 117.8 |
C2—Fe1—C3 | 40.50 (11) | C8—C12—H12 | 117.8 |
C4i—Fe1—C3 | 139.75 (10) | N2—C11—C10 | 123.9 (2) |
C4—Fe1—C3 | 40.25 (10) | N2—C11—H11 | 118.1 |
C3i—Fe1—C3 | 180.000 (1) | C10—C11—H11 | 118.1 |
C6—N1—C7 | 121.1 (2) | C11—C10—C9 | 118.3 (2) |
C6—N1—H1N | 119.5 | C11—C10—H10 | 120.8 |
C7—N1—H1N | 119.5 | C9—C10—H10 | 120.8 |
C11—N2—C12 | 116.4 (2) | C10—C9—C8 | 119.6 (2) |
C1—C5—C4 | 108.1 (2) | C10—C9—H9 | 120.2 |
C1—C5—C6 | 128.8 (2) | C8—C9—H9 | 120.2 |
C4—C5—C6 | 122.9 (2) | ||
C2—Fe1—C5—C1 | −37.76 (15) | C5—Fe1—C2—C1 | 37.97 (15) |
C4—Fe1—C5—C1 | −118.9 (2) | C4—Fe1—C2—C1 | 82.18 (17) |
C3—Fe1—C5—C1 | −81.47 (16) | C3—Fe1—C2—C1 | 119.3 (2) |
C1—Fe1—C5—C4 | 118.9 (2) | C3—C2—C1—C5 | 0.4 (3) |
C2—Fe1—C5—C4 | 81.14 (17) | Fe1—C2—C1—C5 | −59.08 (16) |
C3—Fe1—C5—C4 | 37.42 (15) | C3—C2—C1—Fe1 | 59.46 (16) |
C1—Fe1—C5—C6 | −123.9 (3) | C4—C5—C1—C2 | −0.5 (3) |
C2—Fe1—C5—C6 | −161.7 (2) | C6—C5—C1—C2 | 174.7 (2) |
C4—Fe1—C5—C6 | 117.2 (3) | Fe1—C5—C1—C2 | 59.51 (17) |
C3—Fe1—C5—C6 | 154.6 (2) | C4—C5—C1—Fe1 | −60.06 (16) |
C1—C5—C4—C3 | 0.5 (3) | C6—C5—C1—Fe1 | 115.2 (2) |
C6—C5—C4—C3 | −175.1 (2) | C5—Fe1—C1—C2 | −119.0 (2) |
Fe1—C5—C4—C3 | −59.38 (17) | C4—Fe1—C1—C2 | −81.00 (17) |
C1—C5—C4—Fe1 | 59.89 (16) | C3—Fe1—C1—C2 | −37.58 (16) |
C6—C5—C4—Fe1 | −115.7 (2) | C2—Fe1—C1—C5 | 119.0 (2) |
C5—Fe1—C4—C3 | 119.1 (2) | C4—Fe1—C1—C5 | 38.03 (14) |
C1—Fe1—C4—C3 | 81.15 (16) | C3—Fe1—C1—C5 | 81.44 (16) |
C2—Fe1—C4—C3 | 37.29 (15) | C7—N1—C6—O1 | 9.1 (3) |
C1—Fe1—C4—C5 | −37.97 (14) | C7—N1—C6—C5 | −170.26 (19) |
C2—Fe1—C4—C5 | −81.83 (16) | C1—C5—C6—O1 | 167.4 (2) |
C3—Fe1—C4—C5 | −119.1 (2) | C4—C5—C6—O1 | −17.9 (4) |
C5—C4—C3—C2 | −0.3 (3) | Fe1—C5—C6—O1 | −103.7 (2) |
Fe1—C4—C3—C2 | −59.00 (17) | C1—C5—C6—N1 | −13.2 (4) |
C5—C4—C3—Fe1 | 58.74 (16) | C4—C5—C6—N1 | 161.5 (2) |
C5—Fe1—C3—C4 | −38.06 (14) | Fe1—C5—C6—N1 | 75.7 (3) |
C1—Fe1—C3—C4 | −82.23 (16) | C6—N1—C7—C8 | 74.1 (3) |
C2—Fe1—C3—C4 | −120.0 (2) | N1—C7—C8—C12 | −98.0 (3) |
C5—Fe1—C3—C2 | 81.90 (16) | N1—C7—C8—C9 | 79.1 (3) |
C1—Fe1—C3—C2 | 37.72 (15) | C11—N2—C12—C8 | 1.6 (4) |
C4—Fe1—C3—C2 | 120.0 (2) | C9—C8—C12—N2 | −2.9 (4) |
C4—C3—C2—C1 | −0.1 (3) | C7—C8—C12—N2 | 174.4 (2) |
Fe1—C3—C2—C1 | −59.21 (16) | C12—N2—C11—C10 | 0.9 (4) |
C4—C3—C2—Fe1 | 59.14 (17) | N2—C11—C10—C9 | −2.0 (4) |
C5—Fe1—C2—C3 | −81.29 (16) | C11—C10—C9—C8 | 0.6 (4) |
C1—Fe1—C2—C3 | −119.3 (2) | C12—C8—C9—C10 | 1.6 (4) |
C4—Fe1—C2—C3 | −37.07 (15) | C7—C8—C9—C10 | −175.6 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O1ii | 0.95 | 2.56 | 3.242 (3) | 129 |
N1—H1N···N2iii | 0.88 | 2.15 | 2.952 (3) | 151 |
Symmetry codes: (ii) x, y+1, z; (iii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Fe(C12H11N2O)2] | [Fe(C12H11N2O)2] |
Mr | 454.31 | 454.31 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 295 | 193 |
a, b, c (Å) | 8.9859 (2), 9.8987 (2), 13.7459 (3) | 6.386 (3), 7.882 (3), 9.987 (4) |
α, β, γ (°) | 100.297 (2), 102.114 (2), 114.051 (1) | 85.305 (17), 89.53 (2), 84.831 (19) |
V (Å3) | 1042.75 (4) | 499.0 (4) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.75 | 0.79 |
Crystal size (mm) | 0.23 × 0.15 × 0.12 | 0.30 × 0.25 × 0.10 |
Data collection | ||
Diffractometer | Enraf–Nonius CAD-4 diffractometer | Rigaku Mercury diffractometer |
Absorption correction | Empirical ψ scan (North et al., 1968) | Multi-scan Jacobson, 1998) |
Tmin, Tmax | 0.858, 0.914 | 0.811, 0.917 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14739, 4769, 3611 | 4908, 1810, 1602 |
Rint | 0.050 | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.105, 1.07 | 0.041, 0.082, 1.09 |
No. of reflections | 4769 | 1810 |
No. of parameters | 280 | 143 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.40 | 0.36, −0.45 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CrystalClear (Rigaku Corporation & Molecular Structure Corporation, 2001), CAD-4 Software, CrystalClear, XCAD4 (Harms & Wocadlo, 1995), CrystalStructure (Rigaku Corporation & Molecular Structure Corporation, 2004), OSCAIL-X (McArdle, 2005) and SHELXS97 (Sheldrick, 1997), OSCAIL-X and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
C5—C6 | 1.480 (4) | C17—C18 | 1.477 (3) |
C6—O1 | 1.231 (3) | C18—O2 | 1.233 (3) |
C6—N1 | 1.346 (3) | C18—N3 | 1.337 (3) |
C7—N1 | 1.444 (3) | C19—N3 | 1.442 (3) |
N1—C7—C8 | 114.6 (2) | N3—C19—C20 | 114.03 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N4 | 0.86 | 2.30 | 3.079 (3) | 151 |
N3—H3N···N2 | 0.86 | 2.16 | 2.974 (3) | 157 |
C1—H1···O1i | 0.98 | 2.52 | 3.452 (4) | 159 |
C11—H11···O2ii | 0.93 | 2.43 | 3.173 (4) | 137 |
C12—H12···O2iii | 0.93 | 2.49 | 3.374 (4) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1. |
O1—C6 | 1.235 (3) | N1—C7 | 1.454 (3) |
N1—C6 | 1.349 (3) | C5—C6 | 1.483 (3) |
N1—C7—C8 | 110.49 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2i | 0.88 | 2.15 | 2.952 (3) | 151 |
Symmetry code: (i) x+1, y, z. |
Amide moieties, because of their unique stereoelectronic character, can interact with electron deficient centres through carbonyl groups and with electron rich centres through N—H units. This dual character has been successfully used for the design of amide-based receptors for recognizing a variety of guests including cations, anions and neutral molecules (Ranganathan et al., 1998; Kumar et al., 2003). Ferrocenyl compounds possess redox-responsive character and they can be used for electrochemical recognition of guests (Bernhardt & Creevey, 2004). In view of the above essential components for the molecular and electrochemical recognition of anionic guests, we have designed and synthesized the title compounds, (I) and (II) (Figs. 1 and 2), and we report their structures here.
The most striking difference between (I) and (II) lies in their conformations. In (I), the two substituents attached to the cyclopentadienyl groups are synclinal, whereas in (II),, they are antiperiplanar, as indicated by the torsion angles C5···Cg1···Cg2···C17 [69.3 (2)°] for (I) and C5···Cg1···Cg1*···C5* [−180.0 (2)°] for (II), where Cg1, Cg2, Cg1 and Cg1* are the centroids of the cyclopentadienyl rings. Moreover, the dihedral angles between the cyclopentadienyl groups and the amide planes (the O1/C6/N1 and O2/C18/N3 planes) are 4.3 (3) and 8.7 (3)° in (I); the corresponding values for (II) are 16.5 (3) and 16.5 (3)°. However, the bond dimensions in (I) and the centrosymmetric compound (II) are similar, except that the N1—C7 and N3—C19 bond lengths in (I) are shorter than the N1—C7 and N1* —C7* bond lengths in (II), and the N1—C7—C8 and N3—C19—C20 bond angles in (I) are larger than those in (II) (Tables 1 and 4). For each of (I) and (II), the bonds linking the cyclopentadienyl group and the carbonyl group are typical of a single bond (Csp2—Csp2); this fact suggests that the carbonyl group is not involved in the conjugation of the cyclopentadienyl group (Shi et al., 2006).
Although both compounds crystallize in the same space group, they show markedly different packing modes (Figs. 3 and 4). Compound (I) displays C—H···O═C intermolecular hydrogen bonds in addition to N—H···N intramolecular hydrogen bonds (Table 2). Atom C11 of the 2-pyridyl group in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H11, to carbonyl atom O2 in the molecule at (x, 1 + y, z), so generating a chain in the [010] direction. Two chains of this type passing through each unit cell are linked by C—H···O═C hydrogen bonds in which atom C12 of the 2-pyridyl group in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O2 in the molecule at (1 − x, 1 − y, 1 − z), thus leading to a [010] double chain along with the formation of an R22(24) (Bernstein et al., 1995) ring (Fig. 3). Two such double chains are further linked along the [001] direction via a C—H···O═C hydrogen bond involving atom C1 of the cyclopentadienyl group and carbonyl atom O1 in the molecule at (1 − x, 1 − y, −z), thus resulting in a chain parallel to [001] along with the formation of an R22(10) ring. The combination of the [001] chain and the [010] double chain leads to a two-dimensional network.
Unlike those of (I), the molecules of compound (II) lie across an inversion centre, and they are linked by intermolecular N—H···N hydrogen bonds (Table 4). Atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H1N, to pyridyl atom N2 in the molecule at (1 + x, y, z) to form a [100] chain. The chain passing through each unit cell is further linked along [010] by a π–π stacking interaction between the 3-pyridyl group in the molecule at (x, y, z) and the corresponding group in the molecule at (−x, 2 − y, −z) to give a [010] chain: the ring-centroid and interplanar distances are 3.668 (2) and 3.361 Å, respectively (Glidewell et al., 2005). The combination of the [100] and [010] chains generates a two-dimensional network.