Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801020451/wn6071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801020451/wn6071Isup2.hkl |
CCDC reference: 180515
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.002 Å
- R factor = 0.022
- wR factor = 0.057
- Data-to-parameter ratio = 15.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
ABSTM_02 Alert B The ratio of Tmax/Tmin expected RT(exp) is > 1.20 Absorption corrections should be applied. Tmin and Tmax expected: 0.610 0.775 RT(exp) = 1.272
Alert Level C:
PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ C(AV.) FE C(AV.) PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ C(CP) C(CP) C(CP)(A PLAT_711 Alert C BOND Unknown or Inconsistent Label ........ C(CP) C(CP) C(CP)(A
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
3 Alert Level C = Please check
Methyl 1'-acetamidoferrocene-1-carboxylate was prepared by heating a solution of methyl 1'-azidocarbonylferrocene-1-carboxylate in acetic anhydride at 353 K for 8 h. Work-up of the reaction mixture in the usual manner gave orange crystals (m.p. 381.5–382.0 K), in 42% yield. The structure of the resulting compound was confirmed by elemental analysis, IR, 1H and 13C NMR spectra. (Barišić et al., 2002.). The single crystals were obtained from dichloromethane and n-pentane as precipitant.
Diffraction data were collected on a Nonius KappaCCD diffractometer (capillary optics) at 200 K. 385 frames were collected at a crystal-detector distance of 35 mm, 10 s/°, 8 sets of ω scans, 1° per frame. Program DENZO-SMN was used for data reduction (Otwinowski & Minor, 1997). No absorption correction has been applied, only scaling. All H atoms were included in calculated positions as riding atoms, with SHELXL97 (Sheldrick, 1997) default parameters, except for atom H1N. It was found in an electron-density Fourier map at a distance from N of 0.82 (2) Å and refined freely.
Cell refinement: DENZO and COLLECT (Otwinowski & Minor, 1997); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.
[Fe(C7H8NO)(C7H7O2)] | Z = 2 |
Mr = 301.12 | F(000) = 312 |
Triclinic, P1 | Dx = 1.604 Mg m−3 |
a = 7.6200 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.5052 (1) Å | Cell parameters from 2145 reflections |
c = 10.3956 (2) Å | θ = 1–27.5° |
α = 107.553 (1)° | µ = 1.21 mm−1 |
β = 99.684 (1)° | T = 200 K |
γ = 113.209 (1)° | Irregular prism, orange |
V = 623.39 (2) Å3 | 0.42 × 0.38 × 0.21 mm |
Nonius KappaCCD area-detector diffractometer | 2639 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 27.4°, θmin = 4.4° |
ω scans | h = −9→9 |
4713 measured reflections | k = −12→12 |
2772 independent reflections | l = −13→13 |
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)] = 0.022 | Hydrogen site location: geom and difmap |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0236P)2 + 0.2165P] where P = (Fo2 + 2Fc2)/3 |
2772 reflections | (Δ/σ)max = 0.001 |
178 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Fe(C7H8NO)(C7H7O2)] | γ = 113.209 (1)° |
Mr = 301.12 | V = 623.39 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6200 (1) Å | Mo Kα radiation |
b = 9.5052 (1) Å | µ = 1.21 mm−1 |
c = 10.3956 (2) Å | T = 200 K |
α = 107.553 (1)° | 0.42 × 0.38 × 0.21 mm |
β = 99.684 (1)° |
Nonius KappaCCD area-detector diffractometer | 2639 reflections with I > 2σ(I) |
4713 measured reflections | Rint = 0.018 |
2772 independent reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2772 reflections | Δρmin = −0.37 e Å−3 |
178 parameters |
Experimental. IR spectrum (KBr) νmax/cm-1: 3280 m (N—H), 1713 s (C=O, COCH3), 1660 s (C=O, COCH3); 1H NMR spectrum (CDCl3) δ/p.p.m.: 2.09 (s, 3H, COCH3), 3.80 (s, 3H, COCH3), 4.03 (s, 2 H, H-3' H-4', Fn), 4.40 (s, 2H, H-3' H-4', Fn), 4.63 (s, 2 H, H-2' H-5', Fn), 4.80 (s, 2 H, H-2 H-5, Fn), 7.40 (bs, 1H, NH); 13C NMR, APT spectrum (CDCl3) δ/p.p.m.: 23.60 (COCH3), 51.42 (COCH3), 62.98 (C-3' C-4', Fn), 66.04 (C-3 C-4, Fn), 70.86 (C-2' C-5', Fn), 72.15 (C-2 C-5, Fn), 71.85 (C-1, Fn), 95.05 (C-1', Fn), 168.83 (COCH3), 171.69 (COCH3). |
x | y | z | Uiso*/Ueq | ||
Fe | 0.22187 (2) | 0.31394 (2) | 0.724869 (17) | 0.01462 (7) | |
O1 | −0.14595 (15) | 0.46605 (13) | 0.59145 (10) | 0.0269 (2) | |
O2 | 0.02910 (15) | 0.61561 (12) | 0.82581 (10) | 0.0245 (2) | |
O3 | 0.61946 (19) | 0.85023 (13) | 0.92423 (12) | 0.0383 (3) | |
N | 0.41977 (17) | 0.66127 (14) | 0.69876 (12) | 0.0190 (2) | |
H1N | 0.356 (3) | 0.646 (2) | 0.620 (2) | 0.031 (5)* | |
C1 | −0.03082 (18) | 0.33983 (16) | 0.72714 (13) | 0.0184 (2) | |
C2 | 0.05831 (19) | 0.33790 (17) | 0.85957 (14) | 0.0199 (3) | |
H2 | 0.1058 | 0.4231 | 0.9499 | 0.024* | |
C3 | 0.0609 (2) | 0.18237 (17) | 0.82783 (15) | 0.0226 (3) | |
H3 | 0.1099 | 0.1480 | 0.8940 | 0.027* | |
C4 | −0.0245 (2) | 0.08831 (17) | 0.67690 (15) | 0.0234 (3) | |
H4 | −0.0406 | −0.0179 | 0.6279 | 0.028* | |
C5 | −0.08086 (19) | 0.18458 (16) | 0.61424 (14) | 0.0208 (3) | |
H5 | −0.1397 | 0.1527 | 0.5173 | 0.025* | |
C6 | 0.43403 (18) | 0.52163 (15) | 0.70782 (13) | 0.0168 (2) | |
C7 | 0.51375 (18) | 0.50441 (16) | 0.83319 (14) | 0.0188 (2) | |
H7 | 0.5608 | 0.5828 | 0.9268 | 0.023* | |
C8 | 0.50796 (19) | 0.34470 (16) | 0.78862 (15) | 0.0222 (3) | |
H8 | 0.5528 | 0.3014 | 0.8483 | 0.027* | |
C9 | 0.4216 (2) | 0.26301 (17) | 0.63690 (15) | 0.0227 (3) | |
H9 | 0.4005 | 0.1573 | 0.5806 | 0.027* | |
C10 | 0.37316 (19) | 0.37141 (16) | 0.58648 (14) | 0.0200 (3) | |
H10 | 0.3130 | 0.3485 | 0.4919 | 0.024* | |
C11 | −0.05735 (18) | 0.47597 (16) | 0.70480 (13) | 0.0185 (2) | |
C12 | 0.0089 (2) | 0.75673 (18) | 0.81521 (17) | 0.0300 (3) | |
H12A | 0.0378 | 0.7703 | 0.7320 | 0.045* | |
H12B | 0.1021 | 0.8563 | 0.8988 | 0.045* | |
H12C | −0.1266 | 0.7375 | 0.8077 | 0.045* | |
C13 | 0.5172 (2) | 0.81806 (17) | 0.80547 (15) | 0.0222 (3) | |
C14 | 0.4944 (2) | 0.95123 (18) | 0.76663 (18) | 0.0298 (3) | |
H14A | 0.4373 | 1.0025 | 0.8292 | 0.045* | |
H14B | 0.4069 | 0.9018 | 0.6697 | 0.045* | |
H14C | 0.6245 | 1.0346 | 0.7761 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.01333 (10) | 0.01424 (10) | 0.01305 (10) | 0.00500 (8) | 0.00243 (7) | 0.00455 (7) |
O1 | 0.0268 (5) | 0.0345 (6) | 0.0196 (5) | 0.0154 (5) | 0.0028 (4) | 0.0126 (4) |
O2 | 0.0283 (5) | 0.0236 (5) | 0.0202 (5) | 0.0143 (4) | 0.0052 (4) | 0.0060 (4) |
O3 | 0.0487 (7) | 0.0231 (5) | 0.0262 (5) | 0.0175 (5) | −0.0104 (5) | 0.0004 (4) |
N | 0.0204 (5) | 0.0177 (5) | 0.0151 (5) | 0.0069 (4) | 0.0010 (4) | 0.0071 (4) |
C1 | 0.0133 (5) | 0.0226 (6) | 0.0166 (6) | 0.0073 (5) | 0.0042 (5) | 0.0067 (5) |
C2 | 0.0188 (6) | 0.0249 (7) | 0.0160 (6) | 0.0095 (5) | 0.0069 (5) | 0.0088 (5) |
C3 | 0.0209 (6) | 0.0241 (7) | 0.0240 (7) | 0.0082 (5) | 0.0080 (5) | 0.0143 (6) |
C4 | 0.0185 (6) | 0.0164 (6) | 0.0272 (7) | 0.0030 (5) | 0.0058 (5) | 0.0070 (5) |
C5 | 0.0143 (6) | 0.0212 (6) | 0.0178 (6) | 0.0045 (5) | 0.0009 (5) | 0.0040 (5) |
C6 | 0.0142 (5) | 0.0162 (6) | 0.0170 (6) | 0.0051 (5) | 0.0042 (5) | 0.0064 (5) |
C7 | 0.0145 (6) | 0.0168 (6) | 0.0187 (6) | 0.0042 (5) | 0.0006 (5) | 0.0063 (5) |
C8 | 0.0151 (6) | 0.0196 (6) | 0.0301 (7) | 0.0075 (5) | 0.0029 (5) | 0.0111 (5) |
C9 | 0.0191 (6) | 0.0186 (6) | 0.0286 (7) | 0.0090 (5) | 0.0098 (5) | 0.0062 (5) |
C10 | 0.0189 (6) | 0.0206 (6) | 0.0169 (6) | 0.0067 (5) | 0.0075 (5) | 0.0058 (5) |
C11 | 0.0130 (5) | 0.0238 (6) | 0.0172 (6) | 0.0077 (5) | 0.0055 (5) | 0.0074 (5) |
C12 | 0.0293 (7) | 0.0236 (7) | 0.0380 (8) | 0.0141 (6) | 0.0113 (6) | 0.0113 (6) |
C13 | 0.0195 (6) | 0.0186 (6) | 0.0256 (7) | 0.0084 (5) | 0.0040 (5) | 0.0077 (5) |
C14 | 0.0273 (7) | 0.0213 (7) | 0.0388 (8) | 0.0109 (6) | 0.0054 (6) | 0.0137 (6) |
Fe—C1 | 2.0381 (12) | C3—H3 | 0.9300 |
Fe—C9 | 2.0417 (13) | C4—C5 | 1.4217 (19) |
Fe—C8 | 2.0425 (13) | C4—H4 | 0.9300 |
Fe—C5 | 2.0433 (13) | C5—H5 | 0.9300 |
Fe—C2 | 2.0456 (13) | C6—C7 | 1.4266 (17) |
Fe—C10 | 2.0573 (13) | C6—C10 | 1.4282 (17) |
Fe—C4 | 2.0591 (13) | C7—C8 | 1.4274 (18) |
Fe—C7 | 2.0607 (12) | C7—H7 | 0.9300 |
Fe—C3 | 2.0625 (13) | C8—C9 | 1.426 (2) |
Fe—C6 | 2.0819 (12) | C8—H8 | 0.9300 |
O1—C11 | 1.2118 (16) | C9—C10 | 1.4258 (19) |
O2—C11 | 1.3428 (16) | C9—H9 | 0.9300 |
O2—C12 | 1.4427 (17) | C10—H10 | 0.9300 |
O3—C13 | 1.2189 (17) | C12—H12A | 0.9600 |
N—C13 | 1.3626 (17) | C12—H12B | 0.9600 |
N—C6 | 1.4029 (16) | C12—H12C | 0.9600 |
N—H1N | 0.812 (19) | C13—C14 | 1.5011 (19) |
C1—C5 | 1.4359 (18) | C14—H14A | 0.9600 |
C1—C2 | 1.4378 (18) | C14—H14B | 0.9600 |
C1—C11 | 1.4632 (18) | C14—H14C | 0.9600 |
C2—C3 | 1.4234 (19) | Fe—C(av.) | 2.053 (5) |
C2—H2 | 0.9300 | C(Cp)—C(Cp)(av.)unsubst. | 1.425 (1) |
C3—C4 | 1.427 (2) | C(Cp)—C(Cp)(av.)subst. | 1.432 (4) |
C1—Fe—C9 | 156.53 (6) | C2—C3—H3 | 125.9 |
C1—Fe—C8 | 161.37 (6) | C4—C3—H3 | 125.9 |
C9—Fe—C8 | 40.87 (6) | Fe—C3—H3 | 127.0 |
C1—Fe—C5 | 41.20 (5) | C5—C4—C3 | 108.38 (12) |
C9—Fe—C5 | 120.76 (5) | C5—C4—Fe | 69.13 (7) |
C8—Fe—C5 | 155.66 (6) | C3—C4—Fe | 69.87 (7) |
C1—Fe—C2 | 41.23 (5) | C5—C4—H4 | 125.8 |
C9—Fe—C2 | 160.83 (6) | C3—C4—H4 | 125.8 |
C8—Fe—C2 | 123.70 (5) | Fe—C4—H4 | 126.8 |
C5—Fe—C2 | 69.14 (5) | C4—C5—C1 | 107.88 (11) |
C1—Fe—C10 | 121.39 (5) | C4—C5—Fe | 70.32 (7) |
C9—Fe—C10 | 40.71 (5) | C1—C5—Fe | 69.21 (7) |
C8—Fe—C10 | 68.59 (5) | C4—C5—H5 | 126.1 |
C5—Fe—C10 | 108.02 (5) | C1—C5—H5 | 126.1 |
C2—Fe—C10 | 156.76 (6) | Fe—C5—H5 | 126.0 |
C1—Fe—C4 | 68.64 (5) | N—C6—C7 | 127.69 (11) |
C9—Fe—C4 | 107.45 (6) | N—C6—C10 | 123.66 (11) |
C8—Fe—C4 | 120.38 (5) | C7—C6—C10 | 108.62 (11) |
C5—Fe—C4 | 40.55 (5) | N—C6—Fe | 129.30 (9) |
C2—Fe—C4 | 68.47 (5) | C7—C6—Fe | 69.06 (7) |
C10—Fe—C4 | 125.27 (5) | C10—C6—Fe | 68.89 (7) |
C1—Fe—C7 | 124.73 (5) | C6—C7—C8 | 107.41 (11) |
C9—Fe—C7 | 68.61 (5) | C6—C7—Fe | 70.66 (7) |
C8—Fe—C7 | 40.71 (5) | C8—C7—Fe | 68.96 (7) |
C5—Fe—C7 | 162.49 (5) | C6—C7—H7 | 126.3 |
C2—Fe—C7 | 106.87 (5) | C8—C7—H7 | 126.3 |
C10—Fe—C7 | 68.53 (5) | Fe—C7—H7 | 125.7 |
C4—Fe—C7 | 155.40 (6) | C9—C8—C7 | 108.26 (12) |
C1—Fe—C3 | 68.66 (5) | C9—C8—Fe | 69.54 (7) |
C9—Fe—C3 | 124.33 (6) | C7—C8—Fe | 70.33 (7) |
C8—Fe—C3 | 106.75 (6) | C9—C8—H8 | 125.9 |
C5—Fe—C3 | 68.48 (5) | C7—C8—H8 | 125.9 |
C2—Fe—C3 | 40.54 (5) | Fe—C8—H8 | 125.8 |
C10—Fe—C3 | 161.67 (6) | C10—C9—C8 | 108.21 (11) |
C4—Fe—C3 | 40.52 (5) | C10—C9—Fe | 70.24 (7) |
C7—Fe—C3 | 120.28 (5) | C8—C9—Fe | 69.60 (7) |
C1—Fe—C6 | 108.62 (5) | C10—C9—H9 | 125.9 |
C9—Fe—C6 | 67.83 (5) | C8—C9—H9 | 125.9 |
C8—Fe—C6 | 67.79 (5) | Fe—C9—H9 | 125.8 |
C5—Fe—C6 | 126.19 (5) | C9—C10—C6 | 107.47 (11) |
C2—Fe—C6 | 121.55 (5) | C9—C10—Fe | 69.05 (7) |
C10—Fe—C6 | 40.36 (5) | C6—C10—Fe | 70.74 (7) |
C4—Fe—C6 | 162.66 (5) | C9—C10—H10 | 126.3 |
C7—Fe—C6 | 40.28 (5) | C6—C10—H10 | 126.3 |
C3—Fe—C6 | 155.98 (6) | Fe—C10—H10 | 125.5 |
C11—O2—C12 | 116.11 (11) | O1—C11—O2 | 123.31 (12) |
C13—N—C6 | 125.09 (11) | O1—C11—C1 | 124.79 (12) |
C13—N—H1N | 119.6 (13) | O2—C11—C1 | 111.89 (11) |
C6—N—H1N | 115.0 (13) | O2—C12—H12A | 109.5 |
C5—C1—C2 | 107.68 (11) | O2—C12—H12B | 109.5 |
C5—C1—C11 | 124.27 (12) | H12A—C12—H12B | 109.5 |
C2—C1—C11 | 127.95 (12) | O2—C12—H12C | 109.5 |
C5—C1—Fe | 69.59 (7) | H12A—C12—H12C | 109.5 |
C2—C1—Fe | 69.67 (7) | H12B—C12—H12C | 109.5 |
C11—C1—Fe | 123.30 (9) | O3—C13—N | 122.80 (12) |
C3—C2—C1 | 107.85 (11) | O3—C13—C14 | 121.64 (13) |
C3—C2—Fe | 70.37 (7) | N—C13—C14 | 115.55 (12) |
C1—C2—Fe | 69.11 (7) | C13—C14—H14A | 109.5 |
C3—C2—H2 | 126.1 | C13—C14—H14B | 109.5 |
C1—C2—H2 | 126.1 | H14A—C14—H14B | 109.5 |
Fe—C2—H2 | 126.0 | C13—C14—H14C | 109.5 |
C2—C3—C4 | 108.21 (12) | H14A—C14—H14C | 109.5 |
C2—C3—Fe | 69.09 (7) | H14B—C14—H14C | 109.5 |
C4—C3—Fe | 69.61 (8) | ||
C9—Fe—C1—C5 | 47.06 (17) | C2—Fe—C6—N | −43.61 (13) |
C8—Fe—C1—C5 | −160.31 (15) | C10—Fe—C6—N | 116.86 (15) |
C2—Fe—C1—C5 | −118.91 (11) | C4—Fe—C6—N | 77.8 (2) |
C10—Fe—C1—C5 | 81.55 (9) | C7—Fe—C6—N | −122.20 (15) |
C4—Fe—C1—C5 | −37.64 (8) | C3—Fe—C6—N | −79.22 (17) |
C7—Fe—C1—C5 | 165.89 (8) | C1—Fe—C6—C7 | 122.17 (8) |
C3—Fe—C1—C5 | −81.29 (8) | C9—Fe—C6—C7 | −82.62 (8) |
C6—Fe—C1—C5 | 124.13 (8) | C8—Fe—C6—C7 | −38.32 (8) |
C9—Fe—C1—C2 | 165.97 (12) | C5—Fe—C6—C7 | 164.66 (8) |
C8—Fe—C1—C2 | −41.4 (2) | C2—Fe—C6—C7 | 78.59 (9) |
C5—Fe—C1—C2 | 118.91 (11) | C10—Fe—C6—C7 | −120.94 (11) |
C10—Fe—C1—C2 | −159.54 (8) | C4—Fe—C6—C7 | −159.99 (16) |
C4—Fe—C1—C2 | 81.27 (8) | C3—Fe—C6—C7 | 42.97 (15) |
C7—Fe—C1—C2 | −75.20 (9) | C1—Fe—C6—C10 | −116.90 (8) |
C3—Fe—C1—C2 | 37.63 (8) | C9—Fe—C6—C10 | 38.32 (8) |
C6—Fe—C1—C2 | −116.96 (8) | C8—Fe—C6—C10 | 82.62 (8) |
C9—Fe—C1—C11 | −71.26 (18) | C5—Fe—C6—C10 | −74.40 (9) |
C8—Fe—C1—C11 | 81.4 (2) | C2—Fe—C6—C10 | −160.47 (8) |
C5—Fe—C1—C11 | −118.32 (14) | C4—Fe—C6—C10 | −39.0 (2) |
C2—Fe—C1—C11 | 122.77 (14) | C7—Fe—C6—C10 | 120.94 (11) |
C10—Fe—C1—C11 | −36.77 (12) | C3—Fe—C6—C10 | 163.91 (12) |
C4—Fe—C1—C11 | −155.96 (12) | N—C6—C7—C8 | −176.44 (12) |
C7—Fe—C1—C11 | 47.57 (13) | C10—C6—C7—C8 | 1.81 (14) |
C3—Fe—C1—C11 | 160.39 (12) | Fe—C6—C7—C8 | 59.41 (9) |
C6—Fe—C1—C11 | 5.81 (12) | N—C6—C7—Fe | 124.15 (13) |
C5—C1—C2—C3 | −0.51 (14) | C10—C6—C7—Fe | −57.60 (9) |
C11—C1—C2—C3 | −176.92 (12) | C1—Fe—C7—C6 | −77.46 (9) |
Fe—C1—C2—C3 | −59.95 (9) | C9—Fe—C7—C6 | 80.53 (8) |
C5—C1—C2—Fe | 59.44 (9) | C8—Fe—C7—C6 | 118.35 (11) |
C11—C1—C2—Fe | −116.97 (13) | C5—Fe—C7—C6 | −45.2 (2) |
C1—Fe—C2—C3 | 118.98 (11) | C2—Fe—C7—C6 | −119.21 (8) |
C9—Fe—C2—C3 | −43.92 (19) | C10—Fe—C7—C6 | 36.65 (7) |
C8—Fe—C2—C3 | −75.72 (9) | C4—Fe—C7—C6 | 165.82 (12) |
C5—Fe—C2—C3 | 80.88 (8) | C3—Fe—C7—C6 | −161.26 (7) |
C10—Fe—C2—C3 | 168.12 (12) | C1—Fe—C7—C8 | 164.19 (8) |
C4—Fe—C2—C3 | 37.25 (8) | C9—Fe—C7—C8 | −37.82 (8) |
C7—Fe—C2—C3 | −117.14 (8) | C5—Fe—C7—C8 | −163.56 (16) |
C6—Fe—C2—C3 | −158.62 (8) | C2—Fe—C7—C8 | 122.45 (8) |
C9—Fe—C2—C1 | −162.90 (15) | C10—Fe—C7—C8 | −81.70 (9) |
C8—Fe—C2—C1 | 165.29 (7) | C4—Fe—C7—C8 | 47.47 (16) |
C5—Fe—C2—C1 | −38.10 (8) | C3—Fe—C7—C8 | 80.39 (9) |
C10—Fe—C2—C1 | 49.14 (16) | C6—Fe—C7—C8 | −118.35 (11) |
C4—Fe—C2—C1 | −81.73 (8) | C6—C7—C8—C9 | −1.08 (15) |
C7—Fe—C2—C1 | 123.87 (8) | Fe—C7—C8—C9 | 59.41 (9) |
C3—Fe—C2—C1 | −118.98 (11) | C6—C7—C8—Fe | −60.49 (9) |
C6—Fe—C2—C1 | 82.40 (9) | C1—Fe—C8—C9 | −163.75 (15) |
C1—C2—C3—C4 | 0.38 (14) | C5—Fe—C8—C9 | 48.83 (16) |
Fe—C2—C3—C4 | −58.78 (9) | C2—Fe—C8—C9 | 164.66 (8) |
C1—C2—C3—Fe | 59.16 (9) | C10—Fe—C8—C9 | −37.70 (8) |
C1—Fe—C3—C2 | −38.24 (7) | C4—Fe—C8—C9 | 81.58 (9) |
C9—Fe—C3—C2 | 163.99 (8) | C7—Fe—C8—C9 | −119.25 (11) |
C8—Fe—C3—C2 | 122.65 (8) | C3—Fe—C8—C9 | 123.52 (8) |
C5—Fe—C3—C2 | −82.65 (8) | C6—Fe—C8—C9 | −81.32 (8) |
C10—Fe—C3—C2 | −165.03 (15) | C1—Fe—C8—C7 | −44.5 (2) |
C4—Fe—C3—C2 | −119.93 (11) | C9—Fe—C8—C7 | 119.25 (11) |
C7—Fe—C3—C2 | 80.46 (9) | C5—Fe—C8—C7 | 168.08 (12) |
C6—Fe—C3—C2 | 49.77 (15) | C2—Fe—C8—C7 | −76.09 (9) |
C1—Fe—C3—C4 | 81.68 (8) | C10—Fe—C8—C7 | 81.55 (8) |
C9—Fe—C3—C4 | −76.09 (10) | C4—Fe—C8—C7 | −159.17 (8) |
C8—Fe—C3—C4 | −117.43 (8) | C3—Fe—C8—C7 | −117.23 (8) |
C5—Fe—C3—C4 | 37.27 (8) | C6—Fe—C8—C7 | 37.93 (8) |
C2—Fe—C3—C4 | 119.93 (11) | C7—C8—C9—C10 | −0.05 (15) |
C10—Fe—C3—C4 | −45.1 (2) | Fe—C8—C9—C10 | 59.86 (9) |
C7—Fe—C3—C4 | −159.62 (8) | C7—C8—C9—Fe | −59.90 (9) |
C6—Fe—C3—C4 | 169.69 (11) | C1—Fe—C9—C10 | 47.83 (17) |
C2—C3—C4—C5 | −0.10 (15) | C8—Fe—C9—C10 | −119.20 (11) |
Fe—C3—C4—C5 | −58.56 (9) | C5—Fe—C9—C10 | 81.96 (9) |
C2—C3—C4—Fe | 58.46 (9) | C2—Fe—C9—C10 | −161.28 (14) |
C1—Fe—C4—C5 | 38.22 (8) | C4—Fe—C9—C10 | 124.25 (8) |
C9—Fe—C4—C5 | −117.22 (8) | C7—Fe—C9—C10 | −81.53 (8) |
C8—Fe—C4—C5 | −159.94 (8) | C3—Fe—C9—C10 | 165.63 (8) |
C2—Fe—C4—C5 | 82.67 (8) | C6—Fe—C9—C10 | −38.00 (7) |
C10—Fe—C4—C5 | −75.89 (9) | C1—Fe—C9—C8 | 167.03 (12) |
C7—Fe—C4—C5 | 166.20 (11) | C5—Fe—C9—C8 | −158.83 (8) |
C3—Fe—C4—C5 | 119.94 (11) | C2—Fe—C9—C8 | −42.08 (19) |
C6—Fe—C4—C5 | −45.9 (2) | C10—Fe—C9—C8 | 119.20 (11) |
C1—Fe—C4—C3 | −81.73 (8) | C4—Fe—C9—C8 | −116.55 (8) |
C9—Fe—C4—C3 | 122.84 (8) | C7—Fe—C9—C8 | 37.68 (8) |
C8—Fe—C4—C3 | 80.12 (9) | C3—Fe—C9—C8 | −75.17 (9) |
C5—Fe—C4—C3 | −119.94 (11) | C6—Fe—C9—C8 | 81.20 (8) |
C2—Fe—C4—C3 | −37.27 (8) | C8—C9—C10—C6 | 1.16 (14) |
C10—Fe—C4—C3 | 164.16 (8) | Fe—C9—C10—C6 | 60.62 (9) |
C7—Fe—C4—C3 | 46.26 (16) | C8—C9—C10—Fe | −59.46 (9) |
C6—Fe—C4—C3 | −165.86 (15) | N—C6—C10—C9 | 176.50 (11) |
C3—C4—C5—C1 | −0.22 (15) | C7—C6—C10—C9 | −1.84 (14) |
Fe—C4—C5—C1 | −59.24 (9) | Fe—C6—C10—C9 | −59.54 (9) |
C3—C4—C5—Fe | 59.02 (9) | N—C6—C10—Fe | −123.96 (12) |
C2—C1—C5—C4 | 0.45 (14) | C7—C6—C10—Fe | 57.71 (9) |
C11—C1—C5—C4 | 177.02 (11) | C1—Fe—C10—C9 | −159.77 (8) |
Fe—C1—C5—C4 | 59.93 (9) | C8—Fe—C10—C9 | 37.84 (8) |
C2—C1—C5—Fe | −59.49 (9) | C5—Fe—C10—C9 | −116.52 (8) |
C11—C1—C5—Fe | 117.09 (12) | C2—Fe—C10—C9 | 164.51 (12) |
C1—Fe—C5—C4 | −118.99 (11) | C4—Fe—C10—C9 | −74.99 (9) |
C9—Fe—C5—C4 | 80.85 (9) | C7—Fe—C10—C9 | 81.73 (8) |
C8—Fe—C5—C4 | 45.88 (16) | C3—Fe—C10—C9 | −40.7 (2) |
C2—Fe—C5—C4 | −80.86 (8) | C6—Fe—C10—C9 | 118.30 (11) |
C10—Fe—C5—C4 | 123.63 (8) | C1—Fe—C10—C6 | 81.93 (9) |
C7—Fe—C5—C4 | −160.73 (16) | C9—Fe—C10—C6 | −118.30 (11) |
C3—Fe—C5—C4 | −37.24 (8) | C8—Fe—C10—C6 | −80.46 (8) |
C6—Fe—C5—C4 | 164.62 (8) | C5—Fe—C10—C6 | 125.17 (8) |
C9—Fe—C5—C1 | −160.16 (8) | C2—Fe—C10—C6 | 46.20 (16) |
C8—Fe—C5—C1 | 164.86 (12) | C4—Fe—C10—C6 | 166.71 (7) |
C2—Fe—C5—C1 | 38.13 (8) | C7—Fe—C10—C6 | −36.58 (7) |
C10—Fe—C5—C1 | −117.39 (8) | C3—Fe—C10—C6 | −158.99 (15) |
C4—Fe—C5—C1 | 118.99 (11) | C12—O2—C11—O1 | 0.88 (18) |
C7—Fe—C5—C1 | −41.7 (2) | C12—O2—C11—C1 | −179.23 (11) |
C3—Fe—C5—C1 | 81.75 (8) | C5—C1—C11—O1 | 9.3 (2) |
C6—Fe—C5—C1 | −76.40 (9) | C2—C1—C11—O1 | −174.82 (13) |
C13—N—C6—C7 | 14.2 (2) | Fe—C1—C11—O1 | 96.04 (14) |
C13—N—C6—C10 | −163.80 (13) | C5—C1—C11—O2 | −170.58 (11) |
C13—N—C6—Fe | 107.01 (14) | C2—C1—C11—O2 | 5.28 (18) |
C1—Fe—C6—N | −0.03 (13) | Fe—C1—C11—O2 | −83.86 (12) |
C9—Fe—C6—N | 155.18 (13) | C6—N—C13—O3 | −4.3 (2) |
C8—Fe—C6—N | −160.52 (13) | C6—N—C13—C14 | 174.46 (12) |
C5—Fe—C6—N | 42.46 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1i | 0.82 (2) | 2.14 (2) | 2.934 (2) | 164 (1) |
C3—H3···O3ii | 0.93 | 2.54 | 3.411 (2) | 156 |
C12—H12B···O3iii | 0.96 | 2.57 | 3.506 (2) | 166 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C7H8NO)(C7H7O2)] |
Mr | 301.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 7.6200 (1), 9.5052 (1), 10.3956 (2) |
α, β, γ (°) | 107.553 (1), 99.684 (1), 113.209 (1) |
V (Å3) | 623.39 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.42 × 0.38 × 0.21 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4713, 2772, 2639 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.057, 1.04 |
No. of reflections | 2772 |
No. of parameters | 178 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.37 |
Computer programs: DENZO and COLLECT (Otwinowski & Minor, 1997), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990), SHELXL97.
O1—C11 | 1.2118 (16) | N—C6 | 1.4029 (16) |
O2—C11 | 1.3428 (16) | Fe—C(av.) | 2.053 (5) |
O2—C12 | 1.4427 (17) | C(Cp)—C(Cp)(av.)unsubst. | 1.425 (1) |
O3—C13 | 1.2189 (17) | C(Cp)—C(Cp)(av.)subst. | 1.432 (4) |
N—C13 | 1.3626 (17) | ||
C1—Fe—C9 | 156.53 (6) | C1—Fe—C10 | 121.39 (5) |
C1—Fe—C8 | 161.37 (6) | C2—Fe—C10 | 156.76 (6) |
C9—Fe—C5 | 120.76 (5) | C11—O2—C12 | 116.11 (11) |
C8—Fe—C5 | 155.66 (6) | C13—N—C6 | 125.09 (11) |
C9—Fe—C2 | 160.83 (6) | C13—N—H1N | 119.6 (13) |
C8—Fe—C2 | 123.70 (5) | C6—N—H1N | 115.0 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O1i | 0.82 (2) | 2.14 (2) | 2.934 (2) | 164 (1) |
C3—H3···O3ii | 0.93 | 2.54 | 3.411 (2) | 156 |
C12—H12B···O3iii | 0.96 | 2.57 | 3.506 (2) | 166 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+2, −z+2. |
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Metallocenes and their derivatives are hydrophobic, neutral compounds soluble in organic solvents. They can easily cross cellular membranes and, as a result of these properties, can provide therapeutic and investigation functions in biochemistry, microbiology and medicine (Dombrowski et al., 1986; Ferle-Vidović et al., 2000). The conformational flexibility and the redox properties of ferrocene complexes play important roles in their various applications. Metal-containing polymeric materials with cyclopentadienyl moieties are very attractive materials for electronic, magnetic and optical uses (Okamura et al., 1998). The electronic properties of ferrocene derivatives are considerably influenced by the presence of different functional groups on the cyclopentadienyl (Cp) rings (acyl-, carboxylic derived functional groups etc.) leading to potentially different applications of these complexes (Oberhoff et al., 1996).
The present study of the title ferrocene derivative, (I), is part of our continuous investigation of differently substituted ferrocene compounds (Lisac & Rapić, 1996; Kovač et al., 1997; Lisac et al., 1997, 1999; Lapić & Rapić, 2000; Pavlović et al., 2000). A survey of the Cambridge Structural Database (CSD; Allen & Kennard, 1993) lists only two examples of structurally characterized ferrocene compounds functionalized by the acetamido group, namely the monomer Fe(C5H4NHCOCH3)2 and dimer (CH3CONHC5H4)Fe(C5H4CONHC5H4)Fe(C5H4CONHCH3) (Okamura et al., 1998). The main stereochemical features of these two complexes is the coplanarity of the amido groups and Cp rings and very short intermolecular N···O hydrogen bonds in the range 2.74 (2)–2.90 (2) Å. The molecules are joined into polypeptide infinite chains by N—H···O═C hydrogen bonds. This is not the case with the title compound, since the previously mentioned ferrocene derivatives contain two N—H proton-donor and two C═O proton-acceptor groups per molecule in contrast to the one N—H and one C═O group per molecule in the title compound. To the best of our knowledge, this is the first example of 1,1'-difunctionalized ferrocenes containing NHCOCH3 and COOCH3 groups.
The orientation of the cyclopentadienyl rings (Cp) deviates slightly from the ferrocene eclipsed conformation (Fig. 1). The rotation defined by the torsion angle C(any Cp atom in ring 1)—Cg1—Cg2—C(any Cp atom in ring 2) is in the range 3.84 (1)–3.92 (1)°. The non-H atoms of the NHCOCH3 group lie in a plane with the largest displacement being -0.007 (2) Å for atom C13. Similarly, the non-H atoms of the COOCH3 group are coplanar, with O2 being displaced by 0.007 (1) Å from that plane. The dihedral angle between the plane defined by the non-H atoms of the NHCOCH3 group and the cyclopentadienyl ring to which it is attached is 14.55 (10)°. The dihedral angle between the plane of the COOCH3 group and the attached cyclopentadienyl ring is 7.64 (9)°.
The acetamido N—H1N and C13═O3 groups are E oriented with respect to the N—C13 single bond. The average ring bond distances are 1.4293 (9) and 1.4268 (9) Å for the C1–C5 and C6–C10 rings, respectively. The average C—C ring bond distances for unsubstituted and substituted C atoms are given in Table 1. The Fe—C bond distances are in the range 2.0381 (15)–2.0626 (16) Å for the C1–C5 ring and 2.0418 (16)–2.0819 (14) Å for the C6–C10 ring. The Fe—C1 bond distance of 2.0381 (15) Å and Fe—C6 bond of 2.0819 (14) Å are the shortest and longest Fe—C bond distances in the two Cp rings. The value of the average Fe—C bond distance is given in Table 1. The distances from the Fe atom to the ring centroids (Cg) are 1.6503 (2) and 1.6607 (2) Å, respectively, with a Cg1—Fe—Cg2 angle of 179.05 (1)°. The acetamide and methylcarboxylate groups are stacked in an ABBA fashion (Fig. 2), enabling centrosymmetrical dimerization by N—H···O═C intermolecular hydrogen bonds. The dimers are further interconnected by the C—H···O hydrogen bonds into a three-dimensional network (Table 2).