Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024105/im2012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024105/im2012Isup2.hkl |
CCDC reference: 657599
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.096
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (3) 3.79
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Solid 1-hydroxybenzotriazole (HOBt) (4.40 mmol, 0.67 g) and 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl) (4.40 mmol, 0.84 g) were added to a solution of 1'-(methoxycarbonyl)-ferrocene-1-carboxylic acid (3.93 mmol, 0.80 g) in CH2Cl2 (50 ml). The reaction mixture was stirred for 2 h at room temperature, and then washed with aqueous solutions of saturated sodium bicarbonate (NaHCO3), citric acid, and water. The organic phase was separated and dried with anhydrous Na2SO4, then filtered and the solvent CH2Cl2 evaporated under reduced pressure. The crude product was purified by flash chromatography (SiO2, Rf = 0.55, EtOAc/hexane, 1:2) to give dark orange crystals of (Benzotriazole-1-yl)-1'-(methoxycarbonyl)-ferrocene-1- carboxylate (1) (2.38 mmol, 0.9678 g, yield: 61%).
Suitable crystals of (1) for X-ray diffraction were obtained by slow diffusion (layering technique) of n-hexane into a solution of (1) in CH2Cl2. Dark orange crystals were obtained after 24 h. An orange squared-like crystal of (1) was coated with oil (Paratone 8277, Exxon), was collected onto the nylon fiber of a mounted CryoLoopTM (Hampton Research, USA) under a microscope. The crystal was then mounted onto the goniometer head, which was quickly transferred to the cold stream of the X-ray diffractometer.
The structure was solved using direct methods (SIR97) and refined by full-matrix least-squares method on F2 with SHELXL97–2. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included at geometrically idealized positions (C—H bond distances 0.95/0.98/1.00) and were not refined. The isotropic thermal parameters of the hydrogen atoms were fixed at 1.2 times that of the preceding carbon atom.
The ferrocene ester of 1-hydroxybenzotriazole (HOBt) is useful in the preparation of ferrocene peptide conjugates (Kraatz et al., 1997; Mahmoud et al., 2005). The reactivity of Fc-OBt ester towards external nucleophiles is attributed to the increasing electrophilicity of the carbonyl carbon upon esterfication, driven by the lack of interaction between the Cp and OBt π-systems (Mahmoud et al., 2005). Compound (1) crystalizes in the monoclinic space group P21/c. The two cyclopentadienyl groups of the ferrocence moiety are in the eclipsed conformation with a Cp—Fe—Cp angle 177.8 (6)°. The two ester groups are in the 1,2' conformation around the ferrocene center, they are almost coplanar to the Cp rings with torsion angles for C(14)—C10)—C(15)—O(12) and C(24)—C(20)—C(25)—O(22) of 1.1 (3)° and -0.3 (3)°, respectively, unlike to those found in Fc—C(O)-OBt (10.06 (10)°; Kraatz et al., 1997) and Boc-N(H)—Fc—C(O)-OBt (5.0 (7)°; Mahmoud et al., 2005). The benzotriazole moiety is perpendicular with respect to the Cp it is attached to [C(15)—O(12)—N(11)—C(16)] = 87.0 (0)°). This type of arrangement is also found in the related compounds with cis-configuration relative to ferrocene moiety in Fc—C(O)-OBt (96.56 (6)°; Kraatz et al., 1997), Boc-N(H)—Fc—C(O)-OBt (80.8 (2)°); Mahmoud et al., 2005) and trans-configuration in Ac—N(H)—Fc—C(O)-OBt (88.6°) (Heinze et al., 2004). Presumably the weak hydrogen bond interaction between O(21) and C(17)(H) is responsible for the observed conformation in 1, (C=O(21)—C(17)(H) 3.233 Å; sum of the van der waals radii 3.25 Å; Taylor et al.,1982).
For related literature, see: Heinze & Schlenker (2004); Kraatz et al. (1997); Mahmoud et al. (2005).
For related literature, see: Taylor & Kennard (1982).
Data collection: COLLECT (Nonius, 1998); cell refinement: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP in SHELXTL-NT (Bruker, 2003); software used to prepare material for publication: WinGX (Version 1.70.01; Farrugia, 1999).
| Figure 1 ORTEP diagram of the molecular structure of (1). Displacement ellipsoids are drawn at the 30% probability level. |
[Fe(C7H7O2)(C12H8N3O2)] | F(000) = 832 |
Mr = 405.19 | Dx = 1.590 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3308 reflections |
a = 8.2720 (3) Å | θ = 1.0–27.9° |
b = 10.9180 (3) Å | µ = 0.92 mm−1 |
c = 18.7460 (5) Å | T = 173 K |
β = 91.383 (2)° | Square, orange |
V = 1692.53 (9) Å3 | 0.20 × 0.20 × 0.13 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 3460 independent reflections |
Radiation source: Nonius FR590D, fine-focus sealed tube | 2801 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.060 |
CCD rotation images, thick slices scans | θmax = 26.4°, θmin = 2.9° |
Absorption correction: multi-scan (HKL SCALEPACK; (Otwinowski & Minor, 1997) | h = −10→10 |
Tmin = 0.837, Tmax = 0.889 | k = −13→13 |
12048 measured reflections | l = −23→22 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0414P)2 + 1.2132P] where P = (Fo2 + 2Fc2)/3 |
3460 reflections | (Δ/σ)max = 0.001 |
245 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[Fe(C7H7O2)(C12H8N3O2)] | V = 1692.53 (9) Å3 |
Mr = 405.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2720 (3) Å | µ = 0.92 mm−1 |
b = 10.9180 (3) Å | T = 173 K |
c = 18.7460 (5) Å | 0.20 × 0.20 × 0.13 mm |
β = 91.383 (2)° |
Bruker–Nonius KappaCCD diffractometer | 3460 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; (Otwinowski & Minor, 1997) | 2801 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.889 | Rint = 0.060 |
12048 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.31 e Å−3 |
3460 reflections | Δρmin = −0.47 e Å−3 |
245 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 | 0.48612 (4) | 0.32889 (3) | 0.651633 (18) | 0.01915 (11) | |
O11 | 0.3274 (2) | 0.24087 (16) | 0.46478 (10) | 0.0306 (4) | |
O12 | 0.1545 (2) | 0.37941 (16) | 0.51327 (9) | 0.0269 (4) | |
O21 | 0.0387 (2) | 0.30425 (16) | 0.68935 (10) | 0.0301 (4) | |
O22 | 0.1579 (2) | 0.43584 (16) | 0.76631 (9) | 0.0288 (4) | |
N11 | 0.0386 (3) | 0.32276 (19) | 0.47099 (11) | 0.0268 (5) | |
N12 | 0.0142 (3) | 0.3614 (2) | 0.40315 (12) | 0.0331 (5) | |
N13 | −0.0968 (3) | 0.2906 (2) | 0.37430 (12) | 0.0313 (5) | |
C10 | 0.4275 (3) | 0.3847 (2) | 0.55082 (13) | 0.0215 (5) | |
C11 | 0.5928 (3) | 0.3463 (2) | 0.55495 (14) | 0.0243 (5) | |
H11 | 0.6395 | 0.2819 | 0.5283 | 0.029* | |
C12 | 0.6745 (3) | 0.4212 (2) | 0.60574 (14) | 0.0278 (6) | |
H12 | 0.7858 | 0.4160 | 0.6191 | 0.033* | |
C13 | 0.5608 (3) | 0.5061 (2) | 0.63342 (14) | 0.0276 (6) | |
H13 | 0.5838 | 0.5673 | 0.6683 | 0.033* | |
C14 | 0.4077 (3) | 0.4839 (2) | 0.60019 (13) | 0.0241 (5) | |
H14 | 0.3102 | 0.5267 | 0.6090 | 0.029* | |
C15 | 0.3077 (3) | 0.3240 (2) | 0.50473 (13) | 0.0222 (5) | |
C16 | −0.0509 (3) | 0.2232 (2) | 0.48724 (13) | 0.0207 (5) | |
C17 | −0.0671 (3) | 0.1509 (2) | 0.54821 (13) | 0.0234 (5) | |
H17 | −0.0060 | 0.1659 | 0.5909 | 0.028* | |
C18 | −0.1770 (3) | 0.0568 (2) | 0.54249 (13) | 0.0256 (5) | |
H18 | −0.1903 | 0.0033 | 0.5819 | 0.031* | |
C19 | −0.2711 (3) | 0.0377 (2) | 0.47938 (14) | 0.0269 (5) | |
H19 | −0.3470 | −0.0276 | 0.4778 | 0.032* | |
C20 | 0.3148 (3) | 0.2773 (2) | 0.72174 (12) | 0.0220 (5) | |
C21 | 0.3525 (3) | 0.1773 (2) | 0.67550 (13) | 0.0233 (5) | |
H21 | 0.2788 | 0.1359 | 0.6442 | 0.028* | |
C22 | 0.5201 (3) | 0.1511 (2) | 0.68493 (14) | 0.0284 (6) | |
H22 | 0.5779 | 0.0890 | 0.6609 | 0.034* | |
C23 | 0.5864 (3) | 0.2336 (3) | 0.73637 (14) | 0.0317 (6) | |
H23 | 0.6960 | 0.2359 | 0.7527 | 0.038* | |
C24 | 0.4609 (3) | 0.3119 (2) | 0.75923 (13) | 0.0272 (6) | |
H24 | 0.4717 | 0.3759 | 0.7933 | 0.033* | |
C25 | 0.1567 (3) | 0.3375 (2) | 0.72331 (12) | 0.0211 (5) | |
C26 | 0.0080 (4) | 0.5040 (3) | 0.76726 (15) | 0.0345 (6) | |
H26A | −0.0236 | 0.5276 | 0.7185 | 0.041* | |
H26B | 0.0229 | 0.5778 | 0.7965 | 0.041* | |
H26C | −0.0768 | 0.4529 | 0.7875 | 0.041* | |
C110 | −0.2558 (3) | 0.1102 (2) | 0.42076 (14) | 0.0270 (6) | |
H110 | −0.3208 | 0.0974 | 0.3790 | 0.032* | |
C111 | −0.1408 (3) | 0.2044 (2) | 0.42423 (13) | 0.0233 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01780 (19) | 0.01764 (18) | 0.02191 (19) | 0.00037 (13) | −0.00146 (13) | 0.00061 (13) |
O11 | 0.0315 (11) | 0.0281 (10) | 0.0320 (10) | −0.0011 (8) | −0.0020 (8) | −0.0040 (8) |
O12 | 0.0203 (9) | 0.0268 (9) | 0.0333 (10) | −0.0017 (7) | −0.0065 (7) | −0.0018 (8) |
O21 | 0.0234 (10) | 0.0329 (10) | 0.0339 (10) | −0.0006 (8) | −0.0027 (8) | −0.0069 (8) |
O22 | 0.0311 (10) | 0.0283 (9) | 0.0270 (9) | 0.0061 (8) | −0.0019 (7) | −0.0103 (8) |
N11 | 0.0212 (11) | 0.0313 (11) | 0.0274 (11) | −0.0044 (9) | −0.0084 (9) | 0.0039 (9) |
N12 | 0.0286 (13) | 0.0399 (13) | 0.0306 (12) | −0.0005 (10) | −0.0040 (10) | 0.0100 (10) |
N13 | 0.0284 (12) | 0.0359 (12) | 0.0294 (12) | −0.0022 (10) | −0.0074 (10) | 0.0063 (10) |
C10 | 0.0206 (13) | 0.0194 (11) | 0.0245 (12) | −0.0008 (9) | 0.0011 (10) | 0.0044 (9) |
C11 | 0.0197 (12) | 0.0255 (12) | 0.0276 (13) | 0.0006 (10) | 0.0018 (10) | 0.0020 (10) |
C12 | 0.0173 (12) | 0.0329 (14) | 0.0331 (14) | −0.0062 (10) | −0.0015 (10) | 0.0045 (11) |
C13 | 0.0304 (14) | 0.0191 (12) | 0.0333 (14) | −0.0063 (10) | −0.0022 (11) | −0.0007 (10) |
C14 | 0.0232 (13) | 0.0184 (11) | 0.0309 (13) | 0.0008 (10) | 0.0030 (10) | 0.0052 (10) |
C15 | 0.0214 (13) | 0.0216 (12) | 0.0237 (12) | 0.0007 (10) | 0.0016 (10) | 0.0068 (10) |
C16 | 0.0159 (11) | 0.0226 (12) | 0.0234 (12) | 0.0017 (9) | −0.0007 (9) | −0.0012 (10) |
C17 | 0.0195 (12) | 0.0296 (13) | 0.0210 (12) | 0.0038 (10) | −0.0019 (10) | 0.0007 (10) |
C18 | 0.0235 (13) | 0.0256 (12) | 0.0279 (13) | 0.0052 (10) | 0.0047 (10) | 0.0024 (10) |
C19 | 0.0217 (13) | 0.0238 (12) | 0.0352 (14) | −0.0014 (10) | 0.0002 (10) | −0.0049 (11) |
C20 | 0.0295 (14) | 0.0190 (11) | 0.0174 (11) | −0.0014 (10) | −0.0013 (10) | 0.0007 (9) |
C21 | 0.0272 (13) | 0.0177 (11) | 0.0251 (12) | −0.0021 (10) | 0.0025 (10) | 0.0005 (10) |
C22 | 0.0319 (15) | 0.0213 (12) | 0.0322 (14) | 0.0075 (10) | 0.0045 (11) | 0.0058 (10) |
C23 | 0.0270 (14) | 0.0379 (15) | 0.0299 (14) | 0.0044 (11) | −0.0054 (11) | 0.0089 (12) |
C24 | 0.0291 (14) | 0.0307 (14) | 0.0215 (12) | 0.0015 (11) | −0.0067 (10) | −0.0012 (10) |
C25 | 0.0257 (13) | 0.0204 (11) | 0.0171 (11) | −0.0029 (10) | 0.0017 (10) | 0.0006 (9) |
C26 | 0.0395 (16) | 0.0336 (14) | 0.0307 (14) | 0.0123 (12) | 0.0055 (12) | −0.0017 (12) |
C110 | 0.0219 (13) | 0.0274 (13) | 0.0312 (13) | 0.0024 (10) | −0.0088 (11) | −0.0076 (11) |
C111 | 0.0207 (12) | 0.0269 (12) | 0.0221 (12) | 0.0038 (10) | −0.0034 (10) | −0.0017 (10) |
Fe1—C10 | 2.033 (2) | C13—C14 | 1.419 (4) |
Fe1—C20 | 2.035 (2) | C13—H13 | 0.9500 |
Fe1—C24 | 2.041 (3) | C14—H14 | 0.9500 |
Fe1—C11 | 2.044 (3) | C16—C111 | 1.396 (3) |
Fe1—C14 | 2.046 (2) | C16—C17 | 1.398 (3) |
Fe1—C21 | 2.046 (2) | C17—C18 | 1.375 (4) |
Fe1—C22 | 2.056 (2) | C17—H17 | 0.9500 |
Fe1—C23 | 2.057 (3) | C18—C19 | 1.415 (4) |
Fe1—C12 | 2.062 (3) | C18—H18 | 0.9500 |
Fe1—C13 | 2.062 (2) | C19—C110 | 1.363 (4) |
O11—C15 | 1.191 (3) | C19—H19 | 0.9500 |
O12—N11 | 1.376 (3) | C20—C21 | 1.433 (3) |
O12—C15 | 1.416 (3) | C20—C24 | 1.433 (4) |
O21—C25 | 1.208 (3) | C20—C25 | 1.465 (3) |
O22—C25 | 1.342 (3) | C21—C22 | 1.423 (4) |
O22—C26 | 1.447 (3) | C21—H21 | 0.9500 |
N11—N12 | 1.350 (3) | C22—C23 | 1.420 (4) |
N11—C16 | 1.354 (3) | C22—H22 | 0.9500 |
N12—N13 | 1.308 (3) | C23—C24 | 1.420 (4) |
N13—C111 | 1.382 (3) | C23—H23 | 0.9500 |
C10—C11 | 1.431 (3) | C24—H24 | 0.9500 |
C10—C14 | 1.437 (3) | C26—H26A | 0.9800 |
C10—C15 | 1.458 (3) | C26—H26B | 0.9800 |
C11—C12 | 1.415 (4) | C26—H26C | 0.9800 |
C11—H11 | 0.9500 | C110—C111 | 1.401 (4) |
C12—C13 | 1.427 (4) | C110—H110 | 0.9500 |
C12—H12 | 0.9500 | ||
C10—Fe1—C20 | 121.94 (10) | C14—C13—Fe1 | 69.16 (13) |
C10—Fe1—C24 | 156.62 (10) | C12—C13—Fe1 | 69.74 (14) |
C20—Fe1—C24 | 41.17 (10) | C14—C13—H13 | 125.7 |
C10—Fe1—C11 | 41.09 (9) | C12—C13—H13 | 125.7 |
C20—Fe1—C11 | 157.02 (10) | Fe1—C13—H13 | 127.0 |
C24—Fe1—C11 | 160.29 (11) | C13—C14—C10 | 107.3 (2) |
C10—Fe1—C14 | 41.25 (10) | C13—C14—Fe1 | 70.43 (14) |
C20—Fe1—C14 | 108.41 (10) | C10—C14—Fe1 | 68.91 (13) |
C24—Fe1—C14 | 120.14 (10) | C13—C14—H14 | 126.3 |
C11—Fe1—C14 | 69.14 (10) | C10—C14—H14 | 126.3 |
C10—Fe1—C21 | 109.12 (10) | Fe1—C14—H14 | 125.9 |
C20—Fe1—C21 | 41.10 (9) | O11—C15—O12 | 122.2 (2) |
C24—Fe1—C21 | 69.00 (10) | O11—C15—C10 | 128.1 (2) |
C11—Fe1—C21 | 121.08 (10) | O12—C15—C10 | 109.7 (2) |
C14—Fe1—C21 | 127.26 (10) | N11—C16—C111 | 102.1 (2) |
C10—Fe1—C22 | 126.35 (10) | N11—C16—C17 | 134.5 (2) |
C20—Fe1—C22 | 68.58 (10) | C111—C16—C17 | 123.3 (2) |
C24—Fe1—C22 | 68.34 (10) | C18—C17—C16 | 115.7 (2) |
C11—Fe1—C22 | 107.34 (10) | C18—C17—H17 | 122.1 |
C14—Fe1—C22 | 164.48 (11) | C16—C17—H17 | 122.1 |
C21—Fe1—C22 | 40.59 (10) | C17—C18—C19 | 121.6 (2) |
C10—Fe1—C23 | 162.20 (10) | C17—C18—H18 | 119.2 |
C20—Fe1—C23 | 68.61 (10) | C19—C18—H18 | 119.2 |
C24—Fe1—C23 | 40.54 (11) | C110—C19—C18 | 121.9 (2) |
C11—Fe1—C23 | 123.85 (11) | C110—C19—H19 | 119.0 |
C14—Fe1—C23 | 154.17 (11) | C18—C19—H19 | 119.0 |
C21—Fe1—C23 | 68.40 (11) | C21—C20—C24 | 107.8 (2) |
C22—Fe1—C23 | 40.38 (11) | C21—C20—C25 | 124.1 (2) |
C10—Fe1—C12 | 68.37 (10) | C24—C20—C25 | 127.9 (2) |
C20—Fe1—C12 | 161.79 (10) | C21—C20—Fe1 | 69.86 (14) |
C24—Fe1—C12 | 123.59 (10) | C24—C20—Fe1 | 69.64 (14) |
C11—Fe1—C12 | 40.32 (10) | C25—C20—Fe1 | 121.63 (16) |
C14—Fe1—C12 | 68.47 (10) | C22—C21—C20 | 107.6 (2) |
C21—Fe1—C12 | 154.80 (10) | C22—C21—Fe1 | 70.09 (14) |
C22—Fe1—C12 | 119.28 (11) | C20—C21—Fe1 | 69.04 (13) |
C23—Fe1—C12 | 105.95 (11) | C22—C21—H21 | 126.2 |
C10—Fe1—C13 | 68.33 (10) | C20—C21—H21 | 126.2 |
C20—Fe1—C13 | 125.65 (10) | Fe1—C21—H21 | 126.3 |
C24—Fe1—C13 | 106.68 (11) | C23—C22—C21 | 108.4 (2) |
C11—Fe1—C13 | 68.19 (10) | C23—C22—Fe1 | 69.83 (15) |
C14—Fe1—C13 | 40.41 (10) | C21—C22—Fe1 | 69.32 (13) |
C21—Fe1—C13 | 163.93 (10) | C23—C22—H22 | 125.8 |
C22—Fe1—C13 | 153.73 (11) | C21—C22—H22 | 125.8 |
C23—Fe1—C13 | 119.06 (11) | Fe1—C22—H22 | 126.6 |
C12—Fe1—C13 | 40.49 (11) | C22—C23—C24 | 108.3 (2) |
N11—O12—C15 | 110.85 (18) | C22—C23—Fe1 | 69.78 (15) |
C25—O22—C26 | 115.1 (2) | C24—C23—Fe1 | 69.13 (14) |
N12—N11—C16 | 113.1 (2) | C22—C23—H23 | 125.9 |
N12—N11—O12 | 119.2 (2) | C24—C23—H23 | 125.9 |
C16—N11—O12 | 127.5 (2) | Fe1—C23—H23 | 126.8 |
N13—N12—N11 | 107.0 (2) | C23—C24—C20 | 107.9 (2) |
N12—N13—C111 | 108.4 (2) | C23—C24—Fe1 | 70.33 (14) |
C11—C10—C14 | 108.0 (2) | C20—C24—Fe1 | 69.19 (14) |
C11—C10—C15 | 122.3 (2) | C23—C24—H24 | 126.1 |
C14—C10—C15 | 129.6 (2) | C20—C24—H24 | 126.1 |
C11—C10—Fe1 | 69.86 (14) | Fe1—C24—H24 | 126.0 |
C14—C10—Fe1 | 69.84 (14) | O21—C25—O22 | 123.5 (2) |
C15—C10—Fe1 | 123.94 (16) | O21—C25—C20 | 124.4 (2) |
C12—C11—C10 | 107.9 (2) | O22—C25—C20 | 112.1 (2) |
C12—C11—Fe1 | 70.52 (15) | O22—C26—H26A | 109.5 |
C10—C11—Fe1 | 69.05 (14) | O22—C26—H26B | 109.5 |
C12—C11—H11 | 126.0 | H26A—C26—H26B | 109.5 |
C10—C11—H11 | 126.0 | O22—C26—H26C | 109.5 |
Fe1—C11—H11 | 126.0 | H26A—C26—H26C | 109.5 |
C11—C12—C13 | 108.2 (2) | H26B—C26—H26C | 109.5 |
C11—C12—Fe1 | 69.16 (14) | C19—C110—C111 | 117.7 (2) |
C13—C12—Fe1 | 69.77 (14) | C19—C110—H110 | 121.1 |
C11—C12—H12 | 125.9 | C111—C110—H110 | 121.1 |
C13—C12—H12 | 125.9 | N13—C111—C16 | 109.3 (2) |
Fe1—C12—H12 | 126.7 | N13—C111—C110 | 131.1 (2) |
C14—C13—C12 | 108.6 (2) | C16—C111—C110 | 119.6 (2) |
C15—O12—N11—N12 | −87.7 (3) | C16—C17—C18—C19 | −2.0 (4) |
C15—O12—N11—C16 | 87.0 (3) | C17—C18—C19—C110 | 1.0 (4) |
C16—N11—N12—N13 | 2.4 (3) | C10—Fe1—C20—C21 | 82.68 (17) |
O12—N11—N12—N13 | 177.9 (2) | C24—Fe1—C20—C21 | −118.9 (2) |
N11—N12—N13—C111 | −1.2 (3) | C11—Fe1—C20—C21 | 46.3 (3) |
C20—Fe1—C10—C11 | −159.35 (14) | C14—Fe1—C20—C21 | 126.10 (15) |
C24—Fe1—C10—C11 | 163.1 (2) | C22—Fe1—C20—C21 | −37.71 (15) |
C14—Fe1—C10—C11 | 119.1 (2) | C23—Fe1—C20—C21 | −81.23 (16) |
C21—Fe1—C10—C11 | −115.71 (15) | C12—Fe1—C20—C21 | −157.0 (3) |
C22—Fe1—C10—C11 | −73.68 (18) | C13—Fe1—C20—C21 | 167.61 (15) |
C23—Fe1—C10—C11 | −37.0 (4) | C10—Fe1—C20—C24 | −158.47 (14) |
C12—Fe1—C10—C11 | 37.51 (14) | C11—Fe1—C20—C24 | 165.1 (2) |
C13—Fe1—C10—C11 | 81.22 (15) | C14—Fe1—C20—C24 | −115.04 (15) |
C20—Fe1—C10—C14 | 81.57 (16) | C21—Fe1—C20—C24 | 118.9 (2) |
C24—Fe1—C10—C14 | 44.1 (3) | C22—Fe1—C20—C24 | 81.15 (16) |
C11—Fe1—C10—C14 | −119.1 (2) | C23—Fe1—C20—C24 | 37.63 (15) |
C21—Fe1—C10—C14 | 125.21 (14) | C12—Fe1—C20—C24 | −38.1 (4) |
C22—Fe1—C10—C14 | 167.24 (15) | C13—Fe1—C20—C24 | −73.54 (18) |
C23—Fe1—C10—C14 | −156.0 (3) | C10—Fe1—C20—C25 | −35.8 (2) |
C12—Fe1—C10—C14 | −81.57 (15) | C24—Fe1—C20—C25 | 122.7 (2) |
C13—Fe1—C10—C14 | −37.86 (14) | C11—Fe1—C20—C25 | −72.2 (3) |
C20—Fe1—C10—C15 | −43.3 (2) | C14—Fe1—C20—C25 | 7.7 (2) |
C24—Fe1—C10—C15 | −80.8 (3) | C21—Fe1—C20—C25 | −118.4 (3) |
C11—Fe1—C10—C15 | 116.0 (3) | C22—Fe1—C20—C25 | −156.1 (2) |
C14—Fe1—C10—C15 | −124.9 (3) | C23—Fe1—C20—C25 | 160.3 (2) |
C21—Fe1—C10—C15 | 0.3 (2) | C12—Fe1—C20—C25 | 84.6 (4) |
C22—Fe1—C10—C15 | 42.4 (3) | C13—Fe1—C20—C25 | 49.2 (2) |
C23—Fe1—C10—C15 | 79.1 (4) | C24—C20—C21—C22 | 0.1 (3) |
C12—Fe1—C10—C15 | 153.6 (2) | C25—C20—C21—C22 | 174.9 (2) |
C13—Fe1—C10—C15 | −162.7 (2) | Fe1—C20—C21—C22 | 59.70 (17) |
C14—C10—C11—C12 | −0.4 (3) | C24—C20—C21—Fe1 | −59.56 (17) |
C15—C10—C11—C12 | −178.2 (2) | C25—C20—C21—Fe1 | 115.2 (2) |
Fe1—C10—C11—C12 | −60.06 (17) | C10—Fe1—C21—C22 | 124.03 (15) |
C14—C10—C11—Fe1 | 59.64 (16) | C20—Fe1—C21—C22 | −118.9 (2) |
C15—C10—C11—Fe1 | −118.2 (2) | C24—Fe1—C21—C22 | −80.81 (16) |
C10—Fe1—C11—C12 | 119.0 (2) | C11—Fe1—C21—C22 | 80.28 (17) |
C20—Fe1—C11—C12 | 169.0 (2) | C14—Fe1—C21—C22 | 166.62 (15) |
C24—Fe1—C11—C12 | −41.1 (4) | C23—Fe1—C21—C22 | −37.16 (15) |
C14—Fe1—C11—C12 | 80.92 (16) | C12—Fe1—C21—C22 | 44.4 (3) |
C21—Fe1—C11—C12 | −157.29 (15) | C13—Fe1—C21—C22 | −158.0 (3) |
C22—Fe1—C11—C12 | −115.08 (16) | C10—Fe1—C21—C20 | −117.03 (15) |
C23—Fe1—C11—C12 | −73.80 (18) | C24—Fe1—C21—C20 | 38.14 (15) |
C13—Fe1—C11—C12 | 37.40 (15) | C11—Fe1—C21—C20 | −160.77 (14) |
C20—Fe1—C11—C10 | 50.0 (3) | C14—Fe1—C21—C20 | −74.43 (17) |
C24—Fe1—C11—C10 | −160.0 (3) | C22—Fe1—C21—C20 | 118.9 (2) |
C14—Fe1—C11—C10 | −38.07 (14) | C23—Fe1—C21—C20 | 81.79 (16) |
C21—Fe1—C11—C10 | 83.72 (16) | C12—Fe1—C21—C20 | 163.3 (2) |
C22—Fe1—C11—C10 | 125.93 (15) | C13—Fe1—C21—C20 | −39.1 (4) |
C23—Fe1—C11—C10 | 167.21 (14) | C20—C21—C22—C23 | 0.0 (3) |
C12—Fe1—C11—C10 | −119.0 (2) | Fe1—C21—C22—C23 | 59.05 (18) |
C13—Fe1—C11—C10 | −81.59 (15) | C20—C21—C22—Fe1 | −59.04 (16) |
C10—C11—C12—C13 | 0.1 (3) | C10—Fe1—C22—C23 | 163.61 (15) |
Fe1—C11—C12—C13 | −59.05 (18) | C20—Fe1—C22—C23 | −81.75 (16) |
C10—C11—C12—Fe1 | 59.14 (17) | C24—Fe1—C22—C23 | −37.33 (16) |
C10—Fe1—C12—C11 | −38.20 (14) | C11—Fe1—C22—C23 | 122.25 (16) |
C20—Fe1—C12—C11 | −166.2 (3) | C14—Fe1—C22—C23 | −163.4 (3) |
C24—Fe1—C12—C11 | 164.58 (14) | C21—Fe1—C22—C23 | −119.9 (2) |
C14—Fe1—C12—C11 | −82.72 (16) | C12—Fe1—C22—C23 | 80.04 (18) |
C21—Fe1—C12—C11 | 50.9 (3) | C13—Fe1—C22—C23 | 46.5 (3) |
C22—Fe1—C12—C11 | 82.38 (17) | C10—Fe1—C22—C21 | −76.47 (18) |
C23—Fe1—C12—C11 | 123.96 (15) | C20—Fe1—C22—C21 | 38.17 (14) |
C13—Fe1—C12—C11 | −119.7 (2) | C24—Fe1—C22—C21 | 82.59 (16) |
C10—Fe1—C12—C13 | 81.52 (16) | C11—Fe1—C22—C21 | −117.83 (15) |
C20—Fe1—C12—C13 | −46.5 (4) | C14—Fe1—C22—C21 | −43.5 (4) |
C24—Fe1—C12—C13 | −75.70 (18) | C23—Fe1—C22—C21 | 119.9 (2) |
C11—Fe1—C12—C13 | 119.7 (2) | C12—Fe1—C22—C21 | −160.04 (14) |
C14—Fe1—C12—C13 | 37.01 (15) | C13—Fe1—C22—C21 | 166.5 (2) |
C21—Fe1—C12—C13 | 170.7 (2) | C21—C22—C23—C24 | −0.2 (3) |
C22—Fe1—C12—C13 | −157.90 (16) | Fe1—C22—C23—C24 | 58.57 (18) |
C23—Fe1—C12—C13 | −116.32 (16) | C21—C22—C23—Fe1 | −58.73 (17) |
C11—C12—C13—C14 | 0.3 (3) | C10—Fe1—C23—C22 | −48.0 (4) |
Fe1—C12—C13—C14 | −58.39 (17) | C20—Fe1—C23—C22 | 81.67 (16) |
C11—C12—C13—Fe1 | 58.68 (18) | C24—Fe1—C23—C22 | 119.9 (2) |
C10—Fe1—C13—C14 | 38.62 (15) | C11—Fe1—C23—C22 | −76.42 (19) |
C20—Fe1—C13—C14 | −75.94 (18) | C14—Fe1—C23—C22 | 169.9 (2) |
C24—Fe1—C13—C14 | −117.17 (16) | C21—Fe1—C23—C22 | 37.34 (15) |
C11—Fe1—C13—C14 | 83.02 (16) | C12—Fe1—C23—C22 | −116.68 (16) |
C21—Fe1—C13—C14 | −45.3 (4) | C13—Fe1—C23—C22 | −158.43 (16) |
C22—Fe1—C13—C14 | 168.1 (2) | C10—Fe1—C23—C24 | −167.9 (3) |
C23—Fe1—C13—C14 | −159.34 (15) | C20—Fe1—C23—C24 | −38.20 (15) |
C12—Fe1—C13—C14 | 120.3 (2) | C11—Fe1—C23—C24 | 163.70 (15) |
C10—Fe1—C13—C12 | −81.64 (16) | C14—Fe1—C23—C24 | 50.0 (3) |
C20—Fe1—C13—C12 | 163.80 (14) | C21—Fe1—C23—C24 | −82.54 (17) |
C24—Fe1—C13—C12 | 122.57 (16) | C22—Fe1—C23—C24 | −119.9 (2) |
C11—Fe1—C13—C12 | −37.25 (15) | C12—Fe1—C23—C24 | 123.44 (16) |
C14—Fe1—C13—C12 | −120.3 (2) | C13—Fe1—C23—C24 | 81.69 (18) |
C21—Fe1—C13—C12 | −165.5 (3) | C22—C23—C24—C20 | 0.2 (3) |
C22—Fe1—C13—C12 | 47.8 (3) | Fe1—C23—C24—C20 | 59.22 (17) |
C23—Fe1—C13—C12 | 80.39 (17) | C22—C23—C24—Fe1 | −58.97 (18) |
C12—C13—C14—C10 | −0.5 (3) | C21—C20—C24—C23 | −0.2 (3) |
Fe1—C13—C14—C10 | −59.28 (16) | C25—C20—C24—C23 | −174.8 (2) |
C12—C13—C14—Fe1 | 58.74 (18) | Fe1—C20—C24—C23 | −59.93 (18) |
C11—C10—C14—C13 | 0.6 (3) | C21—C20—C24—Fe1 | 59.70 (17) |
C15—C10—C14—C13 | 178.2 (2) | C25—C20—C24—Fe1 | −114.8 (2) |
Fe1—C10—C14—C13 | 60.25 (17) | C10—Fe1—C24—C23 | 170.7 (2) |
C11—C10—C14—Fe1 | −59.65 (16) | C20—Fe1—C24—C23 | 119.0 (2) |
C15—C10—C14—Fe1 | 117.9 (3) | C11—Fe1—C24—C23 | −43.7 (4) |
C10—Fe1—C14—C13 | −118.4 (2) | C14—Fe1—C24—C23 | −157.28 (16) |
C20—Fe1—C14—C13 | 123.83 (15) | C21—Fe1—C24—C23 | 80.91 (17) |
C24—Fe1—C14—C13 | 80.22 (18) | C22—Fe1—C24—C23 | 37.19 (17) |
C11—Fe1—C14—C13 | −80.46 (16) | C12—Fe1—C24—C23 | −74.39 (19) |
C21—Fe1—C14—C13 | 165.70 (15) | C13—Fe1—C24—C23 | −115.46 (17) |
C22—Fe1—C14—C13 | −160.1 (3) | C10—Fe1—C24—C20 | 51.7 (3) |
C23—Fe1—C14—C13 | 45.1 (3) | C11—Fe1—C24—C20 | −162.7 (3) |
C12—Fe1—C14—C13 | −37.08 (15) | C14—Fe1—C24—C20 | 83.73 (16) |
C20—Fe1—C14—C10 | −117.79 (14) | C21—Fe1—C24—C20 | −38.08 (14) |
C24—Fe1—C14—C10 | −161.39 (14) | C22—Fe1—C24—C20 | −81.80 (16) |
C11—Fe1—C14—C10 | 37.93 (14) | C23—Fe1—C24—C20 | −119.0 (2) |
C21—Fe1—C14—C10 | −75.92 (17) | C12—Fe1—C24—C20 | 166.62 (14) |
C22—Fe1—C14—C10 | −41.7 (4) | C13—Fe1—C24—C20 | 125.56 (15) |
C23—Fe1—C14—C10 | 163.4 (2) | C26—O22—C25—O21 | −2.5 (3) |
C12—Fe1—C14—C10 | 81.31 (15) | C26—O22—C25—C20 | 176.6 (2) |
C13—Fe1—C14—C10 | 118.4 (2) | C21—C20—C25—O21 | 5.1 (4) |
N11—O12—C15—O11 | 1.0 (3) | C24—C20—C25—O21 | 178.8 (2) |
N11—O12—C15—C10 | −179.20 (18) | Fe1—C20—C25—O21 | 91.0 (3) |
C11—C10—C15—O11 | −1.8 (4) | C21—C20—C25—O22 | −174.0 (2) |
C14—C10—C15—O11 | −179.1 (2) | C24—C20—C25—O22 | −0.3 (3) |
Fe1—C10—C15—O11 | −88.1 (3) | Fe1—C20—C25—O22 | −88.0 (2) |
C11—C10—C15—O12 | 178.4 (2) | C18—C19—C110—C111 | 1.1 (4) |
C14—C10—C15—O12 | 1.1 (3) | N12—N13—C111—C16 | −0.3 (3) |
Fe1—C10—C15—O12 | 92.1 (2) | N12—N13—C111—C110 | 178.5 (3) |
N12—N11—C16—C111 | −2.5 (3) | N11—C16—C111—N13 | 1.6 (3) |
O12—N11—C16—C111 | −177.5 (2) | C17—C16—C111—N13 | 179.9 (2) |
N12—N11—C16—C17 | 179.5 (3) | N11—C16—C111—C110 | −177.3 (2) |
O12—N11—C16—C17 | 4.5 (5) | C17—C16—C111—C110 | 1.0 (4) |
N11—C16—C17—C18 | 178.7 (3) | C19—C110—C111—N13 | 179.3 (3) |
C111—C16—C17—C18 | 1.0 (4) | C19—C110—C111—C16 | −2.0 (4) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C7H7O2)(C12H8N3O2)] |
Mr | 405.19 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.2720 (3), 10.9180 (3), 18.7460 (5) |
β (°) | 91.383 (2) |
V (Å3) | 1692.53 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.20 × 0.20 × 0.13 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD |
Absorption correction | Multi-scan (HKL SCALEPACK; (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.837, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12048, 3460, 2801 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.096, 1.05 |
No. of reflections | 3460 |
No. of parameters | 245 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.47 |
Computer programs: COLLECT (Nonius, 1998), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP in SHELXTL-NT (Bruker, 2003), WinGX (Version 1.70.01; Farrugia, 1999).
The ferrocene ester of 1-hydroxybenzotriazole (HOBt) is useful in the preparation of ferrocene peptide conjugates (Kraatz et al., 1997; Mahmoud et al., 2005). The reactivity of Fc-OBt ester towards external nucleophiles is attributed to the increasing electrophilicity of the carbonyl carbon upon esterfication, driven by the lack of interaction between the Cp and OBt π-systems (Mahmoud et al., 2005). Compound (1) crystalizes in the monoclinic space group P21/c. The two cyclopentadienyl groups of the ferrocence moiety are in the eclipsed conformation with a Cp—Fe—Cp angle 177.8 (6)°. The two ester groups are in the 1,2' conformation around the ferrocene center, they are almost coplanar to the Cp rings with torsion angles for C(14)—C10)—C(15)—O(12) and C(24)—C(20)—C(25)—O(22) of 1.1 (3)° and -0.3 (3)°, respectively, unlike to those found in Fc—C(O)-OBt (10.06 (10)°; Kraatz et al., 1997) and Boc-N(H)—Fc—C(O)-OBt (5.0 (7)°; Mahmoud et al., 2005). The benzotriazole moiety is perpendicular with respect to the Cp it is attached to [C(15)—O(12)—N(11)—C(16)] = 87.0 (0)°). This type of arrangement is also found in the related compounds with cis-configuration relative to ferrocene moiety in Fc—C(O)-OBt (96.56 (6)°; Kraatz et al., 1997), Boc-N(H)—Fc—C(O)-OBt (80.8 (2)°); Mahmoud et al., 2005) and trans-configuration in Ac—N(H)—Fc—C(O)-OBt (88.6°) (Heinze et al., 2004). Presumably the weak hydrogen bond interaction between O(21) and C(17)(H) is responsible for the observed conformation in 1, (C=O(21)—C(17)(H) 3.233 Å; sum of the van der waals radii 3.25 Å; Taylor et al.,1982).