Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110025746/em3033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110025746/em3033Isup2.hkl |
CCDC reference: 796057
Boc-NH-Fc-COOMe (2.19 g, 6.1 mmol) was dissolved in dichloromethane (20 ml) and trifluoroacetic acid (20 ml) was added at 273 K. The resulting red solution was warmed to room temperature and stirred for 2 h. The solvent was removed in vacuo and the residue was dissolved in water (200 ml) and washed with diethyl ether (3 × 50 ml). The water layer was made alkaline (pH 8) by the addition of 5% aqueous NaOH solution and extracted with ethyl acetate (3 × 100 ml) until the water layer was nearly colourless. The organic layer was dried over MgSO4 and the solvent removed in vacuo (yield 89%, 1.40 g, 5.4 mmol). The product, (I), H2N-Fc-COOMe (20 mg), was dissolved in ethyl acetate (3 ml) and hexane (1 ml) was added. Crystallization at 277 K yielded the title compound, (I), as orange plates.
The positions of all H atoms, except those of the amine group (H1 and H2), were generated with appropriate geometric constraints and allowed to ride on their respective parent C atoms, with C—H = 1.00 Å (0.98 Å for methyl C—H) and Uiso(H) = 1.2Ueq(C) [1.5Ueq(C) for methyl H atoms]. The H atoms of the amine group were found in a difference Fourier map and refined with bond lengths restrained to 0.87 (2) Å [N1—H1 = 0.831 (16) Å and Uiso(H) = 0.069 (8) Å2; N1—H2 = 0.869 (16) Å and Uiso(H) = 0.058 (8) Å2].
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Version 2.3; Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Fe(C5H6N)(C7H7O2)] | F(000) = 536 |
Mr = 259.08 | Dx = 1.609 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9950 reflections |
a = 13.72031 (18) Å | θ = 3.1–28.4° |
b = 7.34436 (10) Å | µ = 1.39 mm−1 |
c = 11.04962 (14) Å | T = 173 K |
β = 106.1201 (7)° | Plate, orange |
V = 1069.66 (3) Å3 | 0.30 × 0.20 × 0.08 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2763 independent reflections |
Radiation source: fine-focus sealed tube | 2425 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
ω and ϕ scans | θmax = 28.9°, θmin = 3.1° |
Absorption correction: multi-scan (MULABS; Spek, 2003) | h = −18→18 |
Tmin = 0.680, Tmax = 0.897 | k = −9→9 |
25686 measured reflections | l = −14→14 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0392P)2 + 0.0934P] where P = (Fo2 + 2Fc2)/3 |
2763 reflections | (Δ/σ)max < 0.001 |
153 parameters | Δρmax = 0.33 e Å−3 |
2 restraints | Δρmin = −0.34 e Å−3 |
[Fe(C5H6N)(C7H7O2)] | V = 1069.66 (3) Å3 |
Mr = 259.08 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.72031 (18) Å | µ = 1.39 mm−1 |
b = 7.34436 (10) Å | T = 173 K |
c = 11.04962 (14) Å | 0.30 × 0.20 × 0.08 mm |
β = 106.1201 (7)° |
Bruker SMART CCD area-detector diffractometer | 2763 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003) | 2425 reflections with I > 2σ(I) |
Tmin = 0.680, Tmax = 0.897 | Rint = 0.077 |
25686 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 2 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.33 e Å−3 |
2763 reflections | Δρmin = −0.34 e Å−3 |
153 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 | 0.318458 (14) | 0.01441 (2) | 0.576038 (17) | 0.01770 (8) | |
C1 | 0.25803 (11) | 0.1302 (2) | 0.71354 (14) | 0.0259 (3) | |
C2 | 0.26476 (12) | 0.2588 (2) | 0.62054 (15) | 0.0293 (3) | |
H2A | 0.2069 | 0.3295 | 0.5656 | 0.035* | |
C3 | 0.36877 (12) | 0.2724 (2) | 0.62021 (16) | 0.0309 (3) | |
H3A | 0.3968 | 0.3559 | 0.5667 | 0.037* | |
C4 | 0.42497 (12) | 0.1483 (2) | 0.71119 (15) | 0.0299 (3) | |
H4A | 0.4999 | 0.1281 | 0.7327 | 0.036* | |
C5 | 0.35674 (12) | 0.0584 (2) | 0.76753 (14) | 0.0270 (3) | |
H5A | 0.3752 | −0.0375 | 0.8342 | 0.032* | |
C6 | 0.21889 (11) | −0.17557 (19) | 0.47933 (13) | 0.0219 (3) | |
C7 | 0.24208 (12) | −0.0472 (2) | 0.39320 (13) | 0.0244 (3) | |
H7A | 0.1924 | 0.0331 | 0.3332 | 0.029* | |
C8 | 0.34813 (12) | −0.0548 (2) | 0.40876 (14) | 0.0275 (3) | |
H8A | 0.3865 | 0.0211 | 0.3624 | 0.033* | |
C9 | 0.39128 (11) | −0.1850 (2) | 0.50437 (14) | 0.0269 (3) | |
H9A | 0.4649 | −0.2166 | 0.5358 | 0.032* | |
C10 | 0.31205 (11) | −0.25978 (19) | 0.54913 (14) | 0.0238 (3) | |
H10A | 0.3197 | −0.3549 | 0.6159 | 0.029* | |
C11 | 0.11676 (11) | −0.20298 (19) | 0.49409 (13) | 0.0228 (3) | |
O1 | 0.11666 (8) | −0.30407 (15) | 0.59491 (10) | 0.0294 (2) | |
O2 | 0.03996 (8) | −0.14231 (18) | 0.42246 (10) | 0.0368 (3) | |
C12 | 0.01896 (12) | −0.3250 (2) | 0.61994 (16) | 0.0350 (4) | |
H12A | 0.0266 | −0.4010 | 0.6949 | 0.053* | |
H12B | −0.0287 | −0.3831 | 0.5475 | 0.053* | |
H12C | −0.0070 | −0.2051 | 0.6344 | 0.053* | |
N1 | 0.17156 (11) | 0.0860 (2) | 0.75051 (16) | 0.0377 (4) | |
H1 | 0.1183 (14) | 0.108 (3) | 0.694 (2) | 0.069 (8)* | |
H2 | 0.1724 (18) | −0.021 (2) | 0.784 (2) | 0.058 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01891 (12) | 0.01568 (11) | 0.01822 (12) | −0.00004 (7) | 0.00467 (8) | −0.00151 (7) |
C1 | 0.0234 (7) | 0.0276 (7) | 0.0276 (7) | −0.0006 (6) | 0.0085 (6) | −0.0113 (6) |
C2 | 0.0310 (8) | 0.0196 (7) | 0.0356 (8) | 0.0060 (6) | 0.0064 (7) | −0.0049 (6) |
C3 | 0.0346 (9) | 0.0206 (7) | 0.0397 (9) | −0.0073 (6) | 0.0140 (7) | −0.0087 (6) |
C4 | 0.0217 (7) | 0.0335 (8) | 0.0333 (8) | −0.0035 (6) | 0.0059 (6) | −0.0149 (6) |
C5 | 0.0281 (8) | 0.0306 (7) | 0.0200 (7) | 0.0015 (6) | 0.0026 (6) | −0.0066 (6) |
C6 | 0.0246 (7) | 0.0200 (6) | 0.0205 (6) | −0.0030 (5) | 0.0053 (5) | −0.0031 (5) |
C7 | 0.0273 (7) | 0.0283 (7) | 0.0166 (6) | −0.0052 (6) | 0.0042 (6) | −0.0016 (6) |
C8 | 0.0310 (8) | 0.0312 (7) | 0.0232 (7) | −0.0069 (6) | 0.0123 (6) | −0.0067 (6) |
C9 | 0.0247 (7) | 0.0246 (7) | 0.0326 (8) | 0.0000 (6) | 0.0099 (6) | −0.0102 (6) |
C10 | 0.0273 (7) | 0.0159 (6) | 0.0278 (7) | 0.0002 (5) | 0.0068 (6) | −0.0034 (5) |
C11 | 0.0251 (7) | 0.0227 (7) | 0.0205 (6) | −0.0034 (5) | 0.0063 (6) | −0.0028 (5) |
O1 | 0.0243 (5) | 0.0365 (6) | 0.0279 (5) | −0.0044 (5) | 0.0081 (4) | 0.0084 (5) |
O2 | 0.0249 (6) | 0.0528 (8) | 0.0310 (6) | 0.0027 (5) | 0.0047 (5) | 0.0106 (5) |
C12 | 0.0295 (8) | 0.0440 (9) | 0.0350 (8) | −0.0062 (7) | 0.0148 (7) | 0.0057 (7) |
N1 | 0.0276 (8) | 0.0502 (10) | 0.0389 (8) | −0.0051 (7) | 0.0153 (7) | −0.0138 (7) |
Fe1—C1 | 2.1021 (14) | C5—H5 | 1.0000 |
Fe1—C2 | 2.0513 (14) | C6—C10 | 1.437 (2) |
Fe1—C3 | 2.0293 (15) | C6—C7 | 1.437 (2) |
Fe1—C4 | 2.0300 (15) | C6—C11 | 1.469 (2) |
Fe1—C5 | 2.0591 (14) | C7—C8 | 1.418 (2) |
Fe1—C6 | 2.0358 (14) | C7—H7 | 1.0000 |
Fe1—C7 | 2.0515 (14) | C8—C9 | 1.426 (2) |
Fe1—C8 | 2.0637 (14) | C8—H8 | 1.0000 |
Fe1—C9 | 2.0517 (14) | C9—C10 | 1.424 (2) |
Fe1—C10 | 2.0340 (14) | C9—H9 | 1.0000 |
C1—N1 | 1.396 (2) | C10—H10 | 1.0000 |
C1—C2 | 1.418 (2) | C11—O2 | 1.2133 (17) |
C1—C5 | 1.421 (2) | C11—O1 | 1.3390 (17) |
C2—C3 | 1.432 (2) | O1—C12 | 1.4501 (18) |
C2—H2A | 1.0000 | C12—H12A | 0.9800 |
C3—C4 | 1.416 (2) | C12—H12B | 0.9800 |
C3—H3 | 1.0000 | C12—H12C | 0.9800 |
C4—C5 | 1.423 (2) | N1—H1 | 0.831 (16) |
C4—H4 | 1.0000 | N1—H2 | 0.869 (16) |
C3—Fe1—C4 | 40.84 (7) | C2—C3—Fe1 | 70.29 (8) |
C3—Fe1—C10 | 163.27 (6) | C4—C3—H3 | 126.3 |
C4—Fe1—C10 | 125.46 (6) | C2—C3—H3 | 126.3 |
C3—Fe1—C6 | 154.17 (6) | Fe1—C3—H3 | 126.3 |
C4—Fe1—C6 | 163.59 (6) | C3—C4—C5 | 108.35 (14) |
C10—Fe1—C6 | 41.34 (6) | C3—C4—Fe1 | 69.56 (9) |
C3—Fe1—C2 | 41.07 (6) | C5—C4—Fe1 | 70.75 (8) |
C4—Fe1—C2 | 68.46 (6) | C3—C4—H4 | 125.8 |
C10—Fe1—C2 | 153.85 (6) | C5—C4—H4 | 125.8 |
C6—Fe1—C2 | 119.49 (6) | Fe1—C4—H4 | 125.8 |
C3—Fe1—C7 | 119.30 (7) | C1—C5—C4 | 108.07 (14) |
C4—Fe1—C7 | 153.87 (6) | C1—C5—Fe1 | 71.67 (8) |
C10—Fe1—C7 | 69.40 (6) | C4—C5—Fe1 | 68.54 (8) |
C6—Fe1—C7 | 41.16 (6) | C1—C5—H5 | 126.0 |
C2—Fe1—C7 | 108.05 (6) | C4—C5—H5 | 126.0 |
C3—Fe1—C9 | 126.14 (6) | Fe1—C5—H5 | 126.0 |
C4—Fe1—C9 | 107.55 (6) | C10—C6—C7 | 108.09 (13) |
C10—Fe1—C9 | 40.78 (6) | C10—C6—C11 | 127.98 (13) |
C6—Fe1—C9 | 68.65 (6) | C7—C6—C11 | 123.85 (13) |
C2—Fe1—C9 | 164.35 (7) | C10—C6—Fe1 | 69.26 (8) |
C7—Fe1—C9 | 68.46 (6) | C7—C6—Fe1 | 70.01 (8) |
C3—Fe1—C5 | 68.52 (7) | C11—C6—Fe1 | 123.88 (10) |
C4—Fe1—C5 | 40.71 (6) | C8—C7—C6 | 107.60 (13) |
C10—Fe1—C5 | 107.08 (6) | C8—C7—Fe1 | 70.31 (8) |
C6—Fe1—C5 | 126.11 (6) | C6—C7—Fe1 | 68.84 (8) |
C2—Fe1—C5 | 67.83 (6) | C8—C7—H7 | 126.2 |
C7—Fe1—C5 | 164.01 (6) | C6—C7—H7 | 126.2 |
C9—Fe1—C5 | 119.73 (6) | Fe1—C7—H7 | 126.2 |
C3—Fe1—C8 | 107.87 (7) | C7—C8—C9 | 108.49 (13) |
C4—Fe1—C8 | 119.83 (6) | C7—C8—Fe1 | 69.38 (8) |
C10—Fe1—C8 | 68.68 (6) | C9—C8—Fe1 | 69.28 (8) |
C6—Fe1—C8 | 68.38 (6) | C7—C8—H8 | 125.7 |
C2—Fe1—C8 | 127.13 (7) | C9—C8—H8 | 125.7 |
C7—Fe1—C8 | 40.31 (6) | Fe1—C8—H8 | 125.7 |
C9—Fe1—C8 | 40.55 (6) | C10—C9—C8 | 108.43 (13) |
C5—Fe1—C8 | 154.36 (7) | C10—C9—Fe1 | 68.94 (8) |
C3—Fe1—C1 | 67.94 (6) | C8—C9—Fe1 | 70.18 (8) |
C4—Fe1—C1 | 67.67 (6) | C10—C9—H9 | 125.8 |
C10—Fe1—C1 | 119.77 (6) | C8—C9—H9 | 125.8 |
C6—Fe1—C1 | 108.35 (6) | Fe1—C9—H9 | 125.8 |
C2—Fe1—C1 | 39.89 (6) | C9—C10—C6 | 107.38 (13) |
C7—Fe1—C1 | 127.22 (6) | C9—C10—Fe1 | 70.28 (8) |
C9—Fe1—C1 | 154.14 (6) | C6—C10—Fe1 | 69.40 (8) |
C5—Fe1—C1 | 39.93 (6) | C9—C10—H10 | 126.3 |
C8—Fe1—C1 | 164.27 (6) | C6—C10—H10 | 126.3 |
N1—C1—C2 | 126.78 (15) | Fe1—C10—H10 | 126.3 |
N1—C1—C5 | 125.39 (16) | O2—C11—O1 | 123.03 (13) |
C2—C1—C5 | 107.78 (14) | O2—C11—C6 | 124.03 (13) |
N1—C1—Fe1 | 130.94 (11) | O1—C11—C6 | 112.94 (12) |
C2—C1—Fe1 | 68.12 (8) | C11—O1—C12 | 115.59 (12) |
C5—C1—Fe1 | 68.41 (8) | O1—C12—H12A | 109.5 |
C1—C2—C3 | 108.30 (14) | O1—C12—H12B | 109.5 |
C1—C2—Fe1 | 71.99 (8) | H12A—C12—H12B | 109.5 |
C3—C2—Fe1 | 68.64 (8) | O1—C12—H12C | 109.5 |
C1—C2—H2A | 125.8 | H12A—C12—H12C | 109.5 |
C3—C2—H2A | 125.8 | H12B—C12—H12C | 109.5 |
Fe1—C2—H2A | 125.8 | C1—N1—H1 | 112.4 (17) |
C4—C3—C2 | 107.45 (14) | C1—N1—H2 | 115.1 (16) |
C4—C3—Fe1 | 69.61 (9) | H1—N1—H2 | 113 (2) |
C3—Fe1—C1—N1 | 158.79 (18) | C9—Fe1—C6—C10 | 38.14 (9) |
C4—Fe1—C1—N1 | −156.94 (18) | C5—Fe1—C6—C10 | −73.82 (10) |
C10—Fe1—C1—N1 | −37.75 (18) | C8—Fe1—C6—C10 | 81.86 (9) |
C6—Fe1—C1—N1 | 6.06 (18) | C1—Fe1—C6—C10 | −114.52 (9) |
C2—Fe1—C1—N1 | 120.4 (2) | C3—Fe1—C6—C7 | 48.95 (17) |
C7—Fe1—C1—N1 | 47.97 (19) | C4—Fe1—C6—C7 | −160.81 (19) |
C9—Fe1—C1—N1 | −72.7 (2) | C10—Fe1—C6—C7 | −119.41 (12) |
C5—Fe1—C1—N1 | −118.8 (2) | C2—Fe1—C6—C7 | 83.90 (10) |
C8—Fe1—C1—N1 | 81.3 (3) | C9—Fe1—C6—C7 | −81.27 (10) |
C3—Fe1—C1—C2 | 38.40 (9) | C5—Fe1—C6—C7 | 166.78 (9) |
C4—Fe1—C1—C2 | 82.67 (10) | C8—Fe1—C6—C7 | −37.54 (9) |
C10—Fe1—C1—C2 | −158.14 (9) | C1—Fe1—C6—C7 | 126.08 (9) |
C6—Fe1—C1—C2 | −114.32 (9) | C3—Fe1—C6—C11 | −69.06 (19) |
C7—Fe1—C1—C2 | −72.41 (11) | C4—Fe1—C6—C11 | 81.2 (2) |
C9—Fe1—C1—C2 | 166.94 (12) | C10—Fe1—C6—C11 | 122.57 (15) |
C5—Fe1—C1—C2 | 120.85 (13) | C2—Fe1—C6—C11 | −34.11 (14) |
C8—Fe1—C1—C2 | −39.1 (2) | C7—Fe1—C6—C11 | −118.02 (16) |
C3—Fe1—C1—C5 | −82.44 (10) | C9—Fe1—C6—C11 | 160.71 (14) |
C4—Fe1—C1—C5 | −38.17 (10) | C5—Fe1—C6—C11 | 48.76 (14) |
C10—Fe1—C1—C5 | 81.01 (10) | C8—Fe1—C6—C11 | −155.56 (14) |
C6—Fe1—C1—C5 | 124.83 (9) | C1—Fe1—C6—C11 | 8.06 (14) |
C2—Fe1—C1—C5 | −120.85 (13) | C10—C6—C7—C8 | 0.88 (16) |
C7—Fe1—C1—C5 | 166.74 (9) | C11—C6—C7—C8 | 177.92 (13) |
C9—Fe1—C1—C5 | 46.09 (17) | Fe1—C6—C7—C8 | 59.87 (10) |
C8—Fe1—C1—C5 | −159.9 (2) | C10—C6—C7—Fe1 | −58.99 (9) |
N1—C1—C2—C3 | 175.17 (14) | C11—C6—C7—Fe1 | 118.05 (13) |
C5—C1—C2—C3 | −2.31 (16) | C3—Fe1—C7—C8 | 83.25 (11) |
Fe1—C1—C2—C3 | −59.28 (10) | C4—Fe1—C7—C8 | 48.94 (18) |
N1—C1—C2—Fe1 | −125.56 (15) | C10—Fe1—C7—C8 | −80.95 (10) |
C5—C1—C2—Fe1 | 56.96 (10) | C6—Fe1—C7—C8 | −118.88 (13) |
C3—Fe1—C2—C1 | −118.79 (13) | C2—Fe1—C7—C8 | 126.67 (10) |
C4—Fe1—C2—C1 | −80.53 (10) | C9—Fe1—C7—C8 | −37.11 (9) |
C10—Fe1—C2—C1 | 47.16 (18) | C5—Fe1—C7—C8 | −161.0 (2) |
C6—Fe1—C2—C1 | 83.53 (10) | C1—Fe1—C7—C8 | 166.68 (9) |
C7—Fe1—C2—C1 | 127.03 (9) | C3—Fe1—C7—C6 | −157.87 (9) |
C9—Fe1—C2—C1 | −158.6 (2) | C4—Fe1—C7—C6 | 167.82 (12) |
C5—Fe1—C2—C1 | −36.51 (9) | C10—Fe1—C7—C6 | 37.93 (8) |
C8—Fe1—C2—C1 | 167.63 (9) | C2—Fe1—C7—C6 | −114.45 (9) |
C4—Fe1—C2—C3 | 38.27 (10) | C9—Fe1—C7—C6 | 81.77 (9) |
C10—Fe1—C2—C3 | 165.96 (13) | C5—Fe1—C7—C6 | −42.1 (3) |
C6—Fe1—C2—C3 | −157.67 (9) | C8—Fe1—C7—C6 | 118.88 (13) |
C7—Fe1—C2—C3 | −114.18 (10) | C1—Fe1—C7—C6 | −74.44 (11) |
C9—Fe1—C2—C3 | −39.8 (3) | C6—C7—C8—C9 | −0.58 (16) |
C5—Fe1—C2—C3 | 82.28 (10) | Fe1—C7—C8—C9 | 58.37 (10) |
C8—Fe1—C2—C3 | −73.57 (11) | C6—C7—C8—Fe1 | −58.94 (10) |
C1—Fe1—C2—C3 | 118.79 (13) | C3—Fe1—C8—C7 | −114.50 (10) |
C1—C2—C3—C4 | 1.42 (17) | C4—Fe1—C8—C7 | −157.50 (9) |
Fe1—C2—C3—C4 | −59.95 (10) | C10—Fe1—C8—C7 | 82.89 (10) |
C1—C2—C3—Fe1 | 61.38 (10) | C6—Fe1—C8—C7 | 38.31 (9) |
C10—Fe1—C3—C4 | −40.0 (3) | C2—Fe1—C8—C7 | −73.04 (11) |
C6—Fe1—C3—C4 | 167.62 (12) | C9—Fe1—C8—C7 | 120.31 (13) |
C2—Fe1—C3—C4 | 118.24 (13) | C5—Fe1—C8—C7 | 168.05 (13) |
C7—Fe1—C3—C4 | −157.69 (9) | C1—Fe1—C8—C7 | −42.6 (3) |
C9—Fe1—C3—C4 | −74.10 (11) | C3—Fe1—C8—C9 | 125.19 (9) |
C5—Fe1—C3—C4 | 37.77 (9) | C4—Fe1—C8—C9 | 82.20 (10) |
C8—Fe1—C3—C4 | −115.23 (10) | C10—Fe1—C8—C9 | −37.42 (8) |
C1—Fe1—C3—C4 | 80.91 (10) | C6—Fe1—C8—C9 | −82.00 (9) |
C4—Fe1—C3—C2 | −118.24 (13) | C2—Fe1—C8—C9 | 166.65 (9) |
C10—Fe1—C3—C2 | −158.2 (2) | C7—Fe1—C8—C9 | −120.31 (13) |
C6—Fe1—C3—C2 | 49.38 (18) | C5—Fe1—C8—C9 | 47.75 (18) |
C7—Fe1—C3—C2 | 84.07 (10) | C1—Fe1—C8—C9 | −162.90 (19) |
C9—Fe1—C3—C2 | 167.67 (9) | C7—C8—C9—C10 | 0.05 (16) |
C5—Fe1—C3—C2 | −80.46 (10) | Fe1—C8—C9—C10 | 58.48 (10) |
C8—Fe1—C3—C2 | 126.53 (10) | C7—C8—C9—Fe1 | −58.43 (10) |
C1—Fe1—C3—C2 | −37.33 (9) | C3—Fe1—C9—C10 | 165.68 (9) |
C2—C3—C4—C5 | 0.02 (16) | C4—Fe1—C9—C10 | 124.41 (9) |
Fe1—C3—C4—C5 | −60.37 (10) | C6—Fe1—C9—C10 | −38.65 (8) |
C2—C3—C4—Fe1 | 60.39 (10) | C2—Fe1—C9—C10 | −163.0 (2) |
C10—Fe1—C4—C3 | 166.88 (9) | C7—Fe1—C9—C10 | −83.03 (9) |
C6—Fe1—C4—C3 | −160.69 (18) | C5—Fe1—C9—C10 | 81.71 (10) |
C2—Fe1—C4—C3 | −38.48 (9) | C8—Fe1—C9—C10 | −119.93 (12) |
C7—Fe1—C4—C3 | 48.74 (18) | C1—Fe1—C9—C10 | 49.54 (17) |
C9—Fe1—C4—C3 | 125.46 (9) | C3—Fe1—C9—C8 | −74.39 (11) |
C5—Fe1—C4—C3 | −119.08 (13) | C4—Fe1—C9—C8 | −115.66 (9) |
C8—Fe1—C4—C3 | 82.96 (11) | C10—Fe1—C9—C8 | 119.93 (12) |
C1—Fe1—C4—C3 | −81.62 (10) | C6—Fe1—C9—C8 | 81.28 (9) |
C3—Fe1—C4—C5 | 119.08 (13) | C2—Fe1—C9—C8 | −43.0 (3) |
C10—Fe1—C4—C5 | −74.04 (11) | C7—Fe1—C9—C8 | 36.91 (9) |
C6—Fe1—C4—C5 | −41.6 (2) | C5—Fe1—C9—C8 | −158.36 (9) |
C2—Fe1—C4—C5 | 80.60 (10) | C1—Fe1—C9—C8 | 169.47 (12) |
C7—Fe1—C4—C5 | 167.82 (13) | C8—C9—C10—C6 | 0.50 (16) |
C9—Fe1—C4—C5 | −115.46 (9) | Fe1—C9—C10—C6 | 59.74 (9) |
C8—Fe1—C4—C5 | −157.96 (9) | C8—C9—C10—Fe1 | −59.24 (10) |
C1—Fe1—C4—C5 | 37.46 (9) | C7—C6—C10—C9 | −0.85 (15) |
N1—C1—C5—C4 | −175.20 (14) | C11—C6—C10—C9 | −177.73 (13) |
C2—C1—C5—C4 | 2.32 (16) | Fe1—C6—C10—C9 | −60.30 (9) |
Fe1—C1—C5—C4 | 59.11 (10) | C7—C6—C10—Fe1 | 59.45 (10) |
N1—C1—C5—Fe1 | 125.69 (15) | C11—C6—C10—Fe1 | −117.43 (14) |
C2—C1—C5—Fe1 | −56.79 (10) | C3—Fe1—C10—C9 | −43.9 (3) |
C3—C4—C5—C1 | −1.45 (16) | C4—Fe1—C10—C9 | −74.98 (11) |
Fe1—C4—C5—C1 | −61.07 (10) | C6—Fe1—C10—C9 | 118.28 (12) |
C3—C4—C5—Fe1 | 59.63 (10) | C2—Fe1—C10—C9 | 169.68 (13) |
C3—Fe1—C5—C1 | 80.88 (10) | C7—Fe1—C10—C9 | 80.51 (9) |
C4—Fe1—C5—C1 | 118.77 (13) | C5—Fe1—C10—C9 | −115.98 (9) |
C10—Fe1—C5—C1 | −116.24 (9) | C8—Fe1—C10—C9 | 37.21 (9) |
C6—Fe1—C5—C1 | −74.66 (11) | C1—Fe1—C10—C9 | −157.52 (9) |
C2—Fe1—C5—C1 | 36.48 (9) | C3—Fe1—C10—C6 | −162.2 (2) |
C7—Fe1—C5—C1 | −41.5 (3) | C4—Fe1—C10—C6 | 166.74 (8) |
C9—Fe1—C5—C1 | −158.78 (9) | C2—Fe1—C10—C6 | 51.40 (17) |
C8—Fe1—C5—C1 | 167.57 (13) | C7—Fe1—C10—C6 | −37.77 (8) |
C3—Fe1—C5—C4 | −37.89 (9) | C9—Fe1—C10—C6 | −118.28 (12) |
C10—Fe1—C5—C4 | 124.99 (9) | C5—Fe1—C10—C6 | 125.74 (8) |
C6—Fe1—C5—C4 | 166.57 (9) | C8—Fe1—C10—C6 | −81.07 (9) |
C2—Fe1—C5—C4 | −82.29 (10) | C1—Fe1—C10—C6 | 84.20 (9) |
C7—Fe1—C5—C4 | −160.3 (2) | C10—C6—C11—O2 | −171.48 (14) |
C9—Fe1—C5—C4 | 82.45 (11) | C7—C6—C11—O2 | 12.1 (2) |
C8—Fe1—C5—C4 | 48.80 (19) | Fe1—C6—C11—O2 | 99.48 (16) |
C1—Fe1—C5—C4 | −118.77 (13) | C10—C6—C11—O1 | 7.9 (2) |
C3—Fe1—C6—C10 | 168.36 (13) | C7—C6—C11—O1 | −168.49 (13) |
C4—Fe1—C6—C10 | −41.4 (2) | Fe1—C6—C11—O1 | −81.09 (15) |
C2—Fe1—C6—C10 | −156.69 (9) | O2—C11—O1—C12 | −4.9 (2) |
C7—Fe1—C6—C10 | 119.41 (12) | C6—C11—O1—C12 | 175.68 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.83 (2) | 2.21 (2) | 3.028 (2) | 167 (2) |
C12—H12A···O2ii | 0.98 | 2.49 | 3.283 (2) | 138 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H6N)(C7H7O2)] |
Mr | 259.08 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 13.72031 (18), 7.34436 (10), 11.04962 (14) |
β (°) | 106.1201 (7) |
V (Å3) | 1069.66 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.39 |
Crystal size (mm) | 0.30 × 0.20 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2003) |
Tmin, Tmax | 0.680, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25686, 2763, 2425 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.679 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 1.07 |
No. of reflections | 2763 |
No. of parameters | 153 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.34 |
Computer programs: APEX2 (Bruker, 2006), SHELXTL (Sheldrick, 2008), Mercury (Version 2.3; Macrae et al., 2006).
C1—N1 | 1.396 (2) | O1—C12 | 1.4501 (18) |
C6—C11 | 1.469 (2) | N1—H1 | 0.831 (16) |
C11—O2 | 1.2133 (17) | N1—H2 | 0.869 (16) |
C11—O1 | 1.3390 (17) | ||
O2—C11—O1 | 123.03 (13) | C1—N1—H1 | 112.4 (17) |
O2—C11—C6 | 124.03 (13) | C1—N1—H2 | 115.1 (16) |
O1—C11—C6 | 112.94 (12) | H1—N1—H2 | 113 (2) |
C11—O1—C12 | 115.59 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.831 (16) | 2.212 (17) | 3.028 (2) | 167 (2) |
C12—H12A···O2ii | 0.98 | 2.49 | 3.283 (2) | 137.8 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y−1/2, z+1/2. |
The artificial amino acid 1-aminoferrocene-1'-carboxylic acid (Fca) (Heinze & Schlenker, 2004; Barišić et al., 2002; Butler & Quayle, 1998) plays an important role in the fields of organometallic oligomers (Khan et al., 2006; Heinze & Siebler, 2007) and bioorganometallic chemistry as a building block for artificial peptides, and therefore as an organometallic β-turn mimetic in ferrocene conjugates of amino acids and peptides (van Staveren & Metzler-Nolte, 2004; Kirin et al., 2006). The latter application is based on the favourable inter-ring distance of ferrocene of about 3.3 Å, close to the N···O distance in β-sheets of peptides. Thus, many Fca derivatives and related compounds have been investigated on the basis of their ability to form hydrogen bonds and in order to study the respective bonding patterns (Okamura et al., 1998; Pavlović et al., 2002, 2003; Heinze & Schlenker, 2004; Chowdhury et al., 2006; Barišić et al., 2006; Heinze & Siebler, 2007).
The synthetic procedure and spectroscopic data of the title compound, (I), were described previously by Butler & Quayle (1998) and Barišić et al. (2002), but any attempts at structural characterization were without success due to twinning problems. It was proposed that (I) crystallizes as a hydrogen-bonded dimer (Butler & Quayle, 1998), which is now confirmed by the crystal structure analysis in this work (Fig. 1). In contrast with previous attempts, no twinning problem was observed for the crystal analysed here.
The asymmetric unit of (I) consists of one independent molecule. The mean Fe—C bond distance is 2.0509 (15) Å. The mean C—C bond distance for the cyclopentadienyl ring Cp1 (C1–C5) is 1.4216 (9) Å and that for Cp2 (C6–C10) is 1.4284 (9) Å. The Cp rings are parallel to each other, as indicated by the angle between the centroids of the Cp rings, Cg1 (Cp1) and Cg2 (Cp2), and atom Fe1 of 0.33 (3)°. The orientation of the Cp rings deviates from the eclipsed 1,1'-conformation by a maximum of 9.32°, as defined by the torsion angles C(any C atom in Cp1)—Cg1—Cg2—C(any C atom in Cp2), where 0° describes the fully eclipsed and 36° the fully staggered conformation. The dihedral angle between the mean plane of C6—COOMe and the Cp2 mean plane is 11.33 (8)°, defined with non-H atoms. This is likely due to the intermolecular hydrogen bonds (see below). Atoms H1 and H2 of the amine group could be localized and refined with restrained N—H bond lengths (Table 1). The sum of the X—N—Y angles (340.5°) quantifies the pyramidal geometry of the amine group. The bond between atoms C6 and C11 shows some π character [1.469 (2) Å], due to extension of the Cp π system to the C═O group. The same characteristics can be found for the N1—C1 bond, where the distance of 1.396 (2) Å is between a single and a double bond (Standard reference?). Similar geometric parameters for partial double bonds were also found for related compounds: Fc-NH2 (Heinze & Schlenker, 2004), Fc-COOMe (Beck et al., 2001) and MeOOC-NH-Fc-COOMe (Pavlović et al., 2002).
As mentioned above and proposed by Butler & Quayle (1998), (I) forms a centrosymmetric dimer with a neighbouring molecule at (-x, -y, -z + 1), connected via a pair of N—H···O═C hydrogen bonds between the amine and carbonyl groups (Table 2). The O atom of the ester group of (I) acts as a double H-atom acceptor in the formation of another hydrogen bond of the type C12— H12A···O2═C11 with a second at neighbour (x, -y - 1/2, z - 1/2). Furthermore, the methyl group interacts with a third molecule (x, -y - 1/2, z + 1/2) in the latter described fashion. In conclusion, each dimer is connected to four other dimers, which leads to the formation of a two-dimensional network parallel to the bc plane along the 21 screw axis (b axis) and the c-glide plane (Table 2, Fig. 2).