Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105015258/dn1081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015258/dn1081Isup2.hkl |
CCDC reference: 278557
The synthesis of Boc-Gly ΔZPhe has been described by Makowski et al. (1985). Boc-Gly ΔEPhe-L-Phe-p-NA was obtained in the same manner as its Z isomer (Makowski et al., 2001); instead of TBTU [2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate], isobutyl chloroformate (0.26 ml, 2 mmol) in tetrahydrofuran (3.5 ml) was used. Isomers E and Z of Boc-Gly ΔPhe-L-Phe-p-NA were separated on a silica gel H-60 (Merck) column eluted with EtOAc (1–40%) in benzene. Yields of isomers E and Z were 18% and 53%, respectively. Gly ΔEPhe-L-Phe-p-NA was obtained according to the method described by Makowski et al. (2001) and used for further synthesis without characterization. The only modification was that, instead of dissolution in ethyl ether and evaporation, the oily deblocked peptide was dissolved in propan-2-ol (20 ml) and precipitated with hexane. TFA (trifluoroacetic acid) (0.139 ml, 1 mmol) was added to a solution of Boc-Gly–ΔZPhe (0.16 g, 0.5 mmol) in tetrahydrofuran (2 ml) and the solution was cooled to 263 K. Isobutyl chloroformate (0.066 ml, 0.5 mmol) was then added and the mixture was left for 1.5 min at this temperature. Finally, Gly ΔEPhe-L-Phe-p-NA (0.3 g, 0.5 mmol) was added and the reaction was carried out for 22 h at room temperature. The precipitate which formed was filtered off and the solvent was removed under reduced pressure. The resulting oil was dissolved in EtOAc (50 ml) and washed successively with 2 M HCl (2 × 3 ml), saturated potassium bicarbonate (3 × 3 ml) and brine (3 ml). The organic layer was dried over MgSO4, the drying agent was removed by filtration and the solvent was evaporated. The product was crystallized from EtOAc–benzene (1:1)/hexane. The purity of the peptide (100%) was checked by high-perfomance liquid chromatography, using an Alltech Alltima column (C-18, 5 µm, 150 × 4.6 mm). Solvent system: A 0.1% TFA, B ACN (acetonitrile?), A:B 35:65, flow rate 1 ml min−1. Yield 0.305 g (77%), m.p. 476–478 K. Elemental analysis, calculated for C42H43N7O9 (789.844): C 63.87, H 5.49%; found: C 64.04, H 5.28%. Long thin needle crystals of Boc0—Gly1-ΔZPhe2—Gly3-ΔEPhe4—L-Phe5-p-NA·C2H5OH, (I), suitable for X-ray structure analysis were grown at room temperature from a solution in ethanol. The crystals are sensitive and decompose in air.
All H atoms were placed in calculated positions, with C—H distances in the range 0.95–1.00 Å and N—H distances of 0.88 Å, and were allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N). Please check added text. The absolute structure was chosen on the basis of the known absolute configuration of the L-phenylalanine residue. The Friedel pairs were merged. Owing to the large anisotropic displacement parameter, the ethanol molecule is certainly slightly disordered but the type of disorder could not be resolved.
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXD (Sheldrick, 2002); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.
C42H43N7O9·C2H6O | F(000) = 884 |
Mr = 835.90 | Dx = 1.299 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2yb | Cell parameters from 7064 reflections |
a = 13.080 (4) Å | θ = 3–73° |
b = 8.998 (3) Å | µ = 0.77 mm−1 |
c = 18.406 (5) Å | T = 100 K |
β = 99.37 (3)° | Long thin needle, yellow |
V = 2137.4 (11) Å3 | 0.45 × 0.04 × 0.02 mm |
Z = 2 |
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 4423 independent reflections |
Radiation source: fine-focus sealed tube | 2794 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
ω and ϕ scans | θmax = 73.5°, θmin = 3.9° |
Absorption correction: analytical CrysAlis RED (Oxford Diffraction, 2003) | h = −16→13 |
Tmin = 0.828, Tmax = 0.988 | k = −9→11 |
14511 measured reflections | l = −22→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
wR(F2) = 0.192 | w = 1/[σ2(Fo2) + (0.085P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
4423 reflections | Δρmax = 0.57 e Å−3 |
552 parameters | Δρmin = −0.32 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0051 (7) |
C42H43N7O9·C2H6O | V = 2137.4 (11) Å3 |
Mr = 835.90 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 13.080 (4) Å | µ = 0.77 mm−1 |
b = 8.998 (3) Å | T = 100 K |
c = 18.406 (5) Å | 0.45 × 0.04 × 0.02 mm |
β = 99.37 (3)° |
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 4423 independent reflections |
Absorption correction: analytical CrysAlis RED (Oxford Diffraction, 2003) | 2794 reflections with I > 2σ(I) |
Tmin = 0.828, Tmax = 0.988 | Rint = 0.085 |
14511 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 1 restraint |
wR(F2) = 0.192 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.57 e Å−3 |
4423 reflections | Δρmin = −0.32 e Å−3 |
552 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 | 0.0130 (5) | 0.3239 (9) | 0.9257 (5) | 0.049 (2) | |
C2 | −0.0488 (6) | 0.4123 (11) | 0.8636 (5) | 0.057 (2) | |
H2A | −0.0724 | 0.5053 | 0.8831 | 0.068* | |
H2B | −0.1089 | 0.3540 | 0.8409 | 0.068* | |
H2C | −0.0050 | 0.4348 | 0.8265 | 0.068* | |
C3 | −0.0471 (6) | 0.2995 (12) | 0.9868 (6) | 0.066 (3) | |
H3A | −0.0653 | 0.3957 | 1.0062 | 0.079* | |
H3B | −0.0050 | 0.2425 | 1.0262 | 0.079* | |
H3C | −0.1105 | 0.2441 | 0.9683 | 0.079* | |
C4 | 0.0535 (7) | 0.1804 (10) | 0.8964 (6) | 0.068 (3) | |
H4A | 0.0911 | 0.1229 | 0.9375 | 0.081* | |
H4B | 0.1002 | 0.2045 | 0.8615 | 0.081* | |
H4C | −0.0049 | 0.1217 | 0.8714 | 0.081* | |
O1 | 0.1017 (3) | 0.4236 (5) | 0.9486 (3) | 0.0401 (12) | |
C5 | 0.1721 (5) | 0.3895 (7) | 1.0076 (4) | 0.0343 (15) | |
O2 | 0.1736 (4) | 0.2795 (6) | 1.0468 (3) | 0.0461 (13) | |
N1 | 0.2432 (4) | 0.5021 (7) | 1.0207 (4) | 0.0420 (15) | |
H1D | 0.2345 | 0.5819 | 0.9927 | 0.050* | |
C6 | 0.3318 (5) | 0.4949 (9) | 1.0784 (4) | 0.0387 (16) | |
H6A | 0.3127 | 0.4393 | 1.1207 | 0.046* | |
H6B | 0.3514 | 0.5970 | 1.0954 | 0.046* | |
C7 | 0.4232 (5) | 0.4213 (7) | 1.0541 (3) | 0.0276 (13) | |
O3 | 0.4193 (3) | 0.3411 (5) | 0.9989 (3) | 0.0334 (10) | |
N2 | 0.5136 (4) | 0.4473 (6) | 1.1016 (3) | 0.0295 (12) | |
H2D | 0.5142 | 0.5120 | 1.1375 | 0.035* | |
C8 | 0.6062 (5) | 0.3713 (7) | 1.0937 (3) | 0.0259 (13) | |
C9 | 0.6604 (5) | 0.2886 (8) | 1.1474 (4) | 0.0304 (14) | |
H9A | 0.7246 | 0.2525 | 1.1368 | 0.037* | |
C10 | 0.6370 (5) | 0.2449 (7) | 1.2194 (4) | 0.0315 (14) | |
C11 | 0.5348 (5) | 0.2412 (8) | 1.2368 (4) | 0.0370 (16) | |
H11A | 0.4778 | 0.2728 | 1.2014 | 0.044* | |
C12 | 0.5184 (6) | 0.1917 (9) | 1.3051 (4) | 0.0422 (17) | |
H12A | 0.4500 | 0.1864 | 1.3161 | 0.051* | |
C13 | 0.6018 (6) | 0.1497 (9) | 1.3575 (4) | 0.0465 (18) | |
H13A | 0.5901 | 0.1173 | 1.4045 | 0.056* | |
C14 | 0.7019 (6) | 0.1543 (8) | 1.3422 (4) | 0.0446 (18) | |
H14A | 0.7585 | 0.1272 | 1.3790 | 0.053* | |
C15 | 0.7197 (5) | 0.1987 (8) | 1.2728 (4) | 0.0358 (15) | |
H15A | 0.7881 | 0.1977 | 1.2617 | 0.043* | |
C16 | 0.6463 (5) | 0.3885 (7) | 1.0232 (4) | 0.0299 (14) | |
O4 | 0.7000 (4) | 0.2891 (6) | 1.0008 (3) | 0.0469 (13) | |
N3 | 0.6195 (4) | 0.5096 (6) | 0.9815 (3) | 0.0291 (12) | |
H3D | 0.5812 | 0.5793 | 0.9971 | 0.035* | |
C17 | 0.6542 (5) | 0.5249 (8) | 0.9105 (4) | 0.0333 (15) | |
H17A | 0.7264 | 0.4884 | 0.9154 | 0.040* | |
H17B | 0.6545 | 0.6317 | 0.8977 | 0.040* | |
C18 | 0.5882 (5) | 0.4418 (7) | 0.8476 (4) | 0.0309 (14) | |
O5 | 0.6208 (3) | 0.4256 (6) | 0.7890 (2) | 0.0343 (10) | |
N4 | 0.4946 (4) | 0.3907 (6) | 0.8597 (3) | 0.0295 (12) | |
H4D | 0.4777 | 0.4004 | 0.9038 | 0.035* | |
C19 | 0.4231 (5) | 0.3222 (7) | 0.8030 (4) | 0.0279 (13) | |
C20 | 0.3204 (5) | 0.3393 (8) | 0.8024 (4) | 0.0328 (15) | |
H20A | 0.3004 | 0.4075 | 0.8369 | 0.039* | |
C21 | 0.2354 (5) | 0.2618 (7) | 0.7531 (4) | 0.0312 (14) | |
C22 | 0.2420 (5) | 0.1139 (7) | 0.7331 (4) | 0.0322 (15) | |
H22A | 0.3038 | 0.0599 | 0.7499 | 0.039* | |
C23 | 0.1603 (5) | 0.0435 (8) | 0.6893 (4) | 0.0392 (17) | |
H23A | 0.1658 | −0.0580 | 0.6762 | 0.047* | |
C24 | 0.0710 (5) | 0.1222 (8) | 0.6648 (4) | 0.0394 (17) | |
H24A | 0.0149 | 0.0744 | 0.6344 | 0.047* | |
C25 | 0.0617 (5) | 0.2686 (8) | 0.6835 (4) | 0.0401 (17) | |
H25A | −0.0003 | 0.3217 | 0.6663 | 0.048* | |
C26 | 0.1435 (5) | 0.3383 (8) | 0.7278 (4) | 0.0357 (16) | |
H26A | 0.1371 | 0.4394 | 0.7412 | 0.043* | |
C27 | 0.4695 (5) | 0.2233 (7) | 0.7526 (4) | 0.0277 (13) | |
O6 | 0.5207 (3) | 0.1116 (5) | 0.7765 (3) | 0.0301 (10) | |
N5 | 0.4520 (4) | 0.2578 (5) | 0.6804 (3) | 0.0283 (11) | |
H5A | 0.4175 | 0.3397 | 0.6666 | 0.034* | |
C28 | 0.4876 (5) | 0.1657 (7) | 0.6239 (3) | 0.0269 (13) | |
H28A | 0.5180 | 0.0745 | 0.6499 | 0.032* | |
C29 | 0.3986 (5) | 0.1114 (7) | 0.5656 (4) | 0.0301 (14) | |
H29A | 0.4276 | 0.0471 | 0.5303 | 0.036* | |
H29B | 0.3517 | 0.0494 | 0.5901 | 0.036* | |
C30 | 0.3360 (5) | 0.2317 (7) | 0.5233 (4) | 0.0305 (14) | |
C31 | 0.3610 (5) | 0.2834 (9) | 0.4570 (4) | 0.0417 (17) | |
H31A | 0.4201 | 0.2437 | 0.4399 | 0.050* | |
C32 | 0.3033 (6) | 0.3893 (10) | 0.4157 (5) | 0.054 (2) | |
H32A | 0.3211 | 0.4193 | 0.3698 | 0.064* | |
C33 | 0.2190 (6) | 0.4529 (9) | 0.4406 (5) | 0.053 (2) | |
H33A | 0.1800 | 0.5289 | 0.4129 | 0.064* | |
C34 | 0.1924 (6) | 0.4046 (9) | 0.5061 (4) | 0.0450 (19) | |
H34A | 0.1347 | 0.4474 | 0.5239 | 0.054* | |
C35 | 0.2498 (5) | 0.2937 (8) | 0.5461 (4) | 0.0386 (16) | |
H35A | 0.2293 | 0.2593 | 0.5904 | 0.046* | |
C36 | 0.5741 (5) | 0.2364 (7) | 0.5911 (4) | 0.0295 (13) | |
O7 | 0.5864 (3) | 0.2075 (6) | 0.5281 (3) | 0.0391 (12) | |
N6 | 0.6379 (4) | 0.3314 (6) | 0.6366 (3) | 0.0278 (11) | |
H6C | 0.6208 | 0.3481 | 0.6802 | 0.033* | |
C37 | 0.7281 (5) | 0.4057 (7) | 0.6213 (4) | 0.0287 (13) | |
C38 | 0.7667 (5) | 0.3841 (7) | 0.5549 (4) | 0.0302 (14) | |
H38A | 0.7362 | 0.3137 | 0.5194 | 0.036* | |
C39 | 0.8513 (5) | 0.4699 (7) | 0.5433 (4) | 0.0335 (15) | |
H39A | 0.8780 | 0.4597 | 0.4986 | 0.040* | |
C40 | 0.8962 (5) | 0.5682 (8) | 0.5953 (4) | 0.0320 (14) | |
C41 | 0.8597 (5) | 0.5863 (8) | 0.6616 (4) | 0.0356 (15) | |
H41A | 0.8924 | 0.6538 | 0.6978 | 0.043* | |
C42 | 0.7747 (5) | 0.5037 (8) | 0.6736 (4) | 0.0329 (15) | |
H42A | 0.7484 | 0.5151 | 0.7184 | 0.039* | |
N7 | 0.9832 (4) | 0.6591 (6) | 0.5827 (4) | 0.0367 (14) | |
O8 | 1.0103 (4) | 0.6543 (6) | 0.5212 (3) | 0.0459 (14) | |
O9 | 1.0280 (4) | 0.7377 (7) | 0.6329 (4) | 0.0580 (16) | |
O10 | 0.1999 (6) | 0.2949 (8) | 1.2030 (4) | 0.085 (2) | |
H10A | 0.1910 | 0.2909 | 1.1568 | 0.127* | |
C43 | 0.1370 (10) | 0.4094 (13) | 1.2255 (8) | 0.101 (5) | |
H43A | 0.1192 | 0.3845 | 1.2743 | 0.121* | |
H43C | 0.0716 | 0.4163 | 1.1899 | 0.121* | |
C44 | 0.1953 (9) | 0.5664 (13) | 1.2301 (7) | 0.086 (4) | |
H44A | 0.2012 | 0.6001 | 1.1803 | 0.129* | |
H44B | 0.2647 | 0.5556 | 1.2591 | 0.129* | |
H44D | 0.1558 | 0.6394 | 1.2536 | 0.129* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.026 (3) | 0.044 (4) | 0.073 (6) | −0.008 (3) | 0.000 (4) | −0.004 (4) |
C2 | 0.043 (4) | 0.055 (5) | 0.066 (6) | −0.002 (4) | −0.012 (4) | 0.011 (5) |
C3 | 0.037 (4) | 0.067 (6) | 0.095 (8) | −0.004 (4) | 0.016 (5) | 0.021 (6) |
C4 | 0.062 (5) | 0.037 (5) | 0.097 (8) | 0.005 (4) | −0.009 (5) | −0.012 (5) |
O1 | 0.031 (2) | 0.032 (3) | 0.055 (3) | −0.004 (2) | −0.002 (2) | 0.009 (3) |
C5 | 0.028 (3) | 0.028 (3) | 0.043 (4) | −0.004 (3) | −0.003 (3) | −0.001 (3) |
O2 | 0.047 (3) | 0.032 (3) | 0.058 (4) | 0.002 (2) | 0.005 (3) | 0.015 (3) |
N1 | 0.038 (3) | 0.031 (3) | 0.053 (4) | 0.002 (3) | −0.003 (3) | 0.007 (3) |
C6 | 0.031 (3) | 0.044 (4) | 0.040 (4) | 0.007 (3) | 0.003 (3) | −0.005 (3) |
C7 | 0.033 (3) | 0.024 (3) | 0.025 (3) | −0.005 (3) | 0.002 (2) | −0.002 (3) |
O3 | 0.042 (2) | 0.031 (2) | 0.027 (2) | −0.006 (2) | 0.004 (2) | −0.003 (2) |
N2 | 0.031 (3) | 0.031 (3) | 0.025 (3) | 0.004 (2) | 0.002 (2) | −0.007 (2) |
C8 | 0.031 (3) | 0.026 (3) | 0.021 (3) | 0.003 (2) | 0.004 (2) | −0.003 (3) |
C9 | 0.032 (3) | 0.033 (3) | 0.027 (3) | 0.002 (3) | 0.007 (3) | 0.002 (3) |
C10 | 0.044 (3) | 0.026 (3) | 0.026 (3) | 0.002 (3) | 0.009 (3) | −0.003 (3) |
C11 | 0.045 (4) | 0.036 (4) | 0.032 (4) | 0.000 (3) | 0.010 (3) | 0.000 (3) |
C12 | 0.054 (4) | 0.041 (4) | 0.035 (4) | −0.006 (3) | 0.018 (3) | −0.004 (3) |
C13 | 0.065 (5) | 0.038 (4) | 0.034 (4) | −0.009 (4) | 0.001 (4) | −0.003 (3) |
C14 | 0.057 (5) | 0.030 (4) | 0.044 (4) | −0.001 (3) | 0.000 (4) | 0.002 (3) |
C15 | 0.042 (4) | 0.028 (3) | 0.035 (4) | 0.008 (3) | −0.001 (3) | 0.011 (3) |
C16 | 0.034 (3) | 0.031 (3) | 0.026 (3) | 0.001 (3) | 0.007 (3) | −0.003 (3) |
O4 | 0.060 (3) | 0.039 (3) | 0.048 (3) | 0.018 (2) | 0.027 (3) | 0.007 (3) |
N3 | 0.039 (3) | 0.023 (3) | 0.028 (3) | −0.002 (2) | 0.013 (2) | −0.001 (2) |
C17 | 0.036 (3) | 0.038 (4) | 0.027 (3) | −0.007 (3) | 0.008 (3) | −0.006 (3) |
C18 | 0.037 (3) | 0.024 (3) | 0.033 (4) | −0.004 (3) | 0.008 (3) | 0.000 (3) |
O5 | 0.038 (2) | 0.039 (3) | 0.028 (2) | −0.007 (2) | 0.012 (2) | −0.002 (2) |
N4 | 0.025 (2) | 0.032 (3) | 0.031 (3) | −0.010 (2) | 0.006 (2) | −0.004 (2) |
C19 | 0.031 (3) | 0.031 (3) | 0.024 (3) | −0.002 (3) | 0.009 (3) | −0.001 (3) |
C20 | 0.031 (3) | 0.032 (3) | 0.035 (4) | 0.001 (3) | 0.004 (3) | 0.000 (3) |
C21 | 0.028 (3) | 0.025 (3) | 0.040 (4) | −0.002 (2) | 0.004 (3) | −0.002 (3) |
C22 | 0.032 (3) | 0.025 (3) | 0.040 (4) | −0.001 (3) | 0.005 (3) | 0.003 (3) |
C23 | 0.038 (4) | 0.030 (4) | 0.049 (5) | −0.001 (3) | 0.005 (3) | −0.005 (3) |
C24 | 0.032 (3) | 0.036 (4) | 0.048 (4) | −0.003 (3) | −0.001 (3) | 0.000 (3) |
C25 | 0.029 (3) | 0.039 (4) | 0.052 (5) | −0.003 (3) | 0.005 (3) | 0.000 (4) |
C26 | 0.032 (3) | 0.026 (3) | 0.047 (4) | 0.007 (3) | 0.000 (3) | −0.001 (3) |
C27 | 0.031 (3) | 0.018 (3) | 0.035 (4) | −0.002 (2) | 0.010 (3) | 0.004 (3) |
O6 | 0.031 (2) | 0.025 (2) | 0.033 (2) | 0.0011 (18) | 0.0034 (19) | 0.006 (2) |
N5 | 0.039 (3) | 0.018 (2) | 0.028 (3) | 0.002 (2) | 0.006 (2) | 0.001 (2) |
C28 | 0.030 (3) | 0.025 (3) | 0.027 (3) | −0.005 (2) | 0.008 (3) | −0.011 (3) |
C29 | 0.031 (3) | 0.029 (3) | 0.028 (3) | −0.001 (3) | −0.004 (3) | −0.006 (3) |
C30 | 0.032 (3) | 0.023 (3) | 0.036 (3) | 0.003 (2) | 0.003 (3) | −0.002 (3) |
C31 | 0.029 (3) | 0.056 (5) | 0.038 (4) | 0.000 (3) | 0.000 (3) | 0.004 (4) |
C32 | 0.039 (4) | 0.061 (5) | 0.056 (5) | −0.004 (4) | −0.007 (4) | 0.022 (5) |
C33 | 0.047 (4) | 0.036 (4) | 0.069 (6) | −0.005 (3) | −0.015 (4) | 0.006 (4) |
C34 | 0.043 (4) | 0.034 (4) | 0.051 (5) | 0.009 (3) | −0.010 (3) | −0.015 (4) |
C35 | 0.037 (3) | 0.038 (4) | 0.038 (4) | −0.002 (3) | 0.000 (3) | −0.013 (3) |
C36 | 0.030 (3) | 0.029 (3) | 0.029 (3) | −0.001 (3) | 0.005 (3) | −0.001 (3) |
O7 | 0.039 (2) | 0.053 (3) | 0.027 (3) | −0.001 (2) | 0.010 (2) | −0.013 (2) |
N6 | 0.029 (2) | 0.027 (3) | 0.028 (3) | −0.008 (2) | 0.007 (2) | −0.003 (2) |
C37 | 0.030 (3) | 0.031 (3) | 0.027 (3) | 0.002 (3) | 0.011 (3) | 0.008 (3) |
C38 | 0.035 (3) | 0.028 (3) | 0.028 (3) | −0.003 (3) | 0.006 (3) | −0.001 (3) |
C39 | 0.032 (3) | 0.034 (4) | 0.036 (4) | 0.003 (3) | 0.009 (3) | 0.009 (3) |
C40 | 0.026 (3) | 0.029 (3) | 0.042 (4) | 0.003 (3) | 0.010 (3) | 0.005 (3) |
C41 | 0.032 (3) | 0.032 (3) | 0.042 (4) | 0.001 (3) | 0.005 (3) | −0.001 (3) |
C42 | 0.034 (3) | 0.036 (4) | 0.029 (3) | −0.010 (3) | 0.007 (3) | −0.005 (3) |
N7 | 0.031 (3) | 0.031 (3) | 0.050 (4) | −0.004 (2) | 0.012 (3) | 0.005 (3) |
O8 | 0.038 (3) | 0.046 (3) | 0.058 (4) | 0.003 (2) | 0.021 (3) | 0.012 (3) |
O9 | 0.046 (3) | 0.059 (4) | 0.073 (4) | −0.019 (3) | 0.020 (3) | −0.013 (3) |
O10 | 0.114 (6) | 0.070 (5) | 0.075 (5) | 0.030 (5) | 0.026 (5) | 0.026 (4) |
C43 | 0.117 (9) | 0.073 (8) | 0.127 (11) | 0.045 (7) | 0.062 (9) | 0.061 (8) |
C44 | 0.093 (8) | 0.070 (7) | 0.097 (9) | 0.001 (6) | 0.023 (7) | 0.016 (7) |
C1—O1 | 1.472 (8) | C20—H20A | 0.9500 |
C1—C3 | 1.489 (12) | C21—C22 | 1.387 (9) |
C1—C2 | 1.514 (11) | C21—C26 | 1.397 (9) |
C1—C4 | 1.528 (12) | C22—C23 | 1.383 (9) |
C2—H2A | 0.9800 | C22—H22A | 0.9500 |
C2—H2B | 0.9800 | C23—C24 | 1.379 (10) |
C2—H2C | 0.9800 | C23—H23A | 0.9500 |
C3—H3A | 0.9800 | C24—C25 | 1.372 (10) |
C3—H3B | 0.9800 | C24—H24A | 0.9500 |
C3—H3C | 0.9800 | C25—C26 | 1.385 (10) |
C4—H4A | 0.9800 | C25—H25A | 0.9500 |
C4—H4B | 0.9800 | C26—H26A | 0.9500 |
C4—H4C | 0.9800 | C27—O6 | 1.247 (7) |
O1—C5 | 1.340 (8) | C27—N5 | 1.348 (8) |
C5—O2 | 1.223 (8) | N5—H5A | 0.8800 |
C5—N1 | 1.370 (9) | C28—C36 | 1.507 (8) |
N1—C6 | 1.441 (9) | C28—H28A | 1.0000 |
N1—H1D | 0.8800 | C29—C30 | 1.497 (9) |
C6—C7 | 1.497 (9) | C29—H29A | 0.9900 |
C6—H6A | 0.9900 | C29—H29B | 0.9900 |
C6—H6B | 0.9900 | C30—C35 | 1.383 (9) |
C7—O3 | 1.241 (7) | C30—C31 | 1.394 (10) |
C7—N2 | 1.371 (7) | C31—C32 | 1.367 (11) |
N2—C8 | 1.419 (7) | C31—H31A | 0.9500 |
N4—C19 | 1.423 (8) | C32—C33 | 1.386 (12) |
N5—C28 | 1.464 (7) | C32—H32A | 0.9500 |
N2—H2D | 0.8800 | C33—C34 | 1.379 (12) |
C8—C9 | 1.344 (9) | C33—H33A | 0.9500 |
C19—C20 | 1.351 (8) | C34—C35 | 1.387 (10) |
C28—C29 | 1.529 (8) | C34—H34A | 0.9500 |
C8—C16 | 1.484 (9) | C35—H35A | 0.9500 |
C9—C10 | 1.462 (9) | C36—O7 | 1.225 (8) |
C9—H9A | 0.9500 | C36—N6 | 1.378 (8) |
C10—C15 | 1.400 (9) | N6—C37 | 1.424 (8) |
C10—C11 | 1.425 (9) | N6—H6C | 0.8800 |
C11—C12 | 1.383 (10) | C37—C42 | 1.373 (9) |
C11—H11A | 0.9500 | C37—C38 | 1.410 (9) |
C12—C13 | 1.386 (11) | C38—C39 | 1.393 (9) |
C12—H12A | 0.9500 | C38—H38A | 0.9500 |
C13—C14 | 1.384 (11) | C39—C40 | 1.363 (10) |
C13—H13A | 0.9500 | C39—H39A | 0.9500 |
C14—C15 | 1.394 (10) | C40—C41 | 1.391 (10) |
C14—H14A | 0.9500 | C40—N7 | 1.450 (8) |
C15—H15A | 0.9500 | C41—C42 | 1.385 (9) |
C16—O4 | 1.248 (8) | C41—H41A | 0.9500 |
C16—N3 | 1.345 (8) | C42—H42A | 0.9500 |
N3—C17 | 1.457 (8) | N7—O9 | 1.234 (8) |
N3—H3D | 0.8800 | N7—O8 | 1.242 (8) |
C17—C18 | 1.523 (9) | O10—C43 | 1.422 (13) |
C17—H17A | 0.9900 | O10—H10A | 0.8400 |
C17—H17B | 0.9900 | C43—C44 | 1.601 (17) |
C18—O5 | 1.230 (8) | C43—H43A | 0.9900 |
C18—N4 | 1.360 (8) | C43—H43C | 0.9900 |
N4—H4D | 0.8800 | C44—H44A | 0.9800 |
C19—C27 | 1.485 (8) | C44—H44B | 0.9800 |
C20—C21 | 1.490 (9) | C44—H44D | 0.9800 |
O1—C1—C3 | 111.2 (7) | C26—C21—C20 | 119.2 (6) |
O1—C1—C2 | 101.3 (6) | C23—C22—C21 | 121.2 (6) |
C3—C1—C2 | 111.4 (7) | C23—C22—H22A | 119.4 |
O1—C1—C4 | 108.3 (6) | C21—C22—H22A | 119.4 |
C3—C1—C4 | 113.4 (8) | C24—C23—C22 | 119.3 (7) |
C2—C1—C4 | 110.5 (8) | C24—C23—H23A | 120.4 |
C1—C2—H2A | 109.5 | C22—C23—H23A | 120.4 |
C1—C2—H2B | 109.5 | C25—C24—C23 | 121.0 (7) |
H2A—C2—H2B | 109.5 | C25—C24—H24A | 119.5 |
C1—C2—H2C | 109.5 | C23—C24—H24A | 119.5 |
H2A—C2—H2C | 109.5 | C24—C25—C26 | 119.4 (7) |
H2B—C2—H2C | 109.5 | C24—C25—H25A | 120.3 |
C1—C3—H3A | 109.5 | C26—C25—H25A | 120.3 |
C1—C3—H3B | 109.5 | C25—C26—C21 | 120.8 (7) |
H3A—C3—H3B | 109.5 | C25—C26—H26A | 119.6 |
C1—C3—H3C | 109.5 | C21—C26—H26A | 119.6 |
H3A—C3—H3C | 109.5 | O6—C27—N5 | 121.9 (6) |
H3B—C3—H3C | 109.5 | O6—C27—C19 | 120.9 (6) |
C1—C4—H4A | 109.5 | N5—C27—C19 | 117.2 (5) |
C1—C4—H4B | 109.5 | C27—N5—C28 | 123.2 (5) |
H4A—C4—H4B | 109.5 | C27—N5—H5A | 118.4 |
C1—C4—H4C | 109.5 | C28—N5—H5A | 118.4 |
H4A—C4—H4C | 109.5 | N5—C28—C36 | 113.1 (5) |
H4B—C4—H4C | 109.5 | N5—C28—C29 | 112.7 (5) |
C5—O1—C1 | 119.9 (6) | C36—C28—C29 | 112.9 (5) |
O2—C5—O1 | 127.3 (6) | N5—C28—H28A | 105.8 |
O2—C5—N1 | 123.4 (6) | C36—C28—H28A | 105.8 |
O1—C5—N1 | 109.3 (6) | C29—C28—H28A | 105.8 |
C5—N1—C6 | 122.5 (6) | C30—C29—C28 | 115.1 (5) |
C5—N1—H1D | 118.7 | C30—C29—H29A | 108.5 |
C6—N1—H1D | 118.7 | C28—C29—H29A | 108.5 |
N1—C6—C7 | 112.6 (6) | C30—C29—H29B | 108.5 |
N1—C6—H6A | 109.1 | C28—C29—H29B | 108.5 |
C7—C6—H6A | 109.1 | H29A—C29—H29B | 107.5 |
N1—C6—H6B | 109.1 | C35—C30—C31 | 116.8 (6) |
C7—C6—H6B | 109.1 | C35—C30—C29 | 122.5 (7) |
H6A—C6—H6B | 107.8 | C31—C30—C29 | 120.7 (6) |
O3—C7—N2 | 122.4 (6) | C32—C31—C30 | 122.2 (7) |
O3—C7—C6 | 125.0 (6) | C32—C31—H31A | 118.9 |
N2—C7—C6 | 112.5 (5) | C30—C31—H31A | 118.9 |
C7—N2—C8 | 121.0 (5) | C31—C32—C33 | 120.1 (8) |
C7—N2—H2D | 119.5 | C31—C32—H32A | 120.0 |
C8—N2—H2D | 119.5 | C33—C32—H32A | 120.0 |
C9—C8—N2 | 123.2 (6) | C34—C33—C32 | 119.2 (8) |
C9—C8—C16 | 118.8 (6) | C34—C33—H33A | 120.4 |
N2—C8—C16 | 117.9 (5) | C32—C33—H33A | 120.4 |
C8—C9—C10 | 130.8 (6) | C33—C34—C35 | 120.0 (7) |
C8—C9—H9A | 114.6 | C33—C34—H34A | 120.0 |
C10—C9—H9A | 114.6 | C35—C34—H34A | 120.0 |
C15—C10—C11 | 118.8 (6) | C30—C35—C34 | 121.8 (7) |
C15—C10—C9 | 117.7 (6) | C30—C35—H35A | 119.1 |
C11—C10—C9 | 123.5 (6) | C34—C35—H35A | 119.1 |
C12—C11—C10 | 120.1 (7) | O7—C36—N6 | 123.1 (6) |
C12—C11—H11A | 120.0 | O7—C36—C28 | 120.8 (6) |
C10—C11—H11A | 120.0 | N6—C36—C28 | 116.0 (5) |
C11—C12—C13 | 120.0 (7) | C36—N6—C37 | 127.6 (5) |
C11—C12—H12A | 120.0 | C36—N6—H6C | 116.2 |
C13—C12—H12A | 120.0 | C37—N6—H6C | 116.2 |
C14—C13—C12 | 121.0 (8) | C42—C37—C38 | 121.0 (6) |
C14—C13—H13A | 119.5 | C42—C37—N6 | 116.8 (5) |
C12—C13—H13A | 119.5 | C38—C37—N6 | 122.1 (6) |
C13—C14—C15 | 119.9 (7) | C39—C38—C37 | 117.5 (6) |
C13—C14—H14A | 120.0 | C39—C38—H38A | 121.3 |
C15—C14—H14A | 120.0 | C37—C38—H38A | 121.3 |
C14—C15—C10 | 120.2 (7) | C40—C39—C38 | 121.0 (6) |
C14—C15—H15A | 119.9 | C40—C39—H39A | 119.5 |
C10—C15—H15A | 119.9 | C38—C39—H39A | 119.5 |
O4—C16—N3 | 120.0 (6) | C39—C40—C41 | 121.4 (6) |
O4—C16—C8 | 120.8 (6) | C39—C40—N7 | 121.0 (6) |
N3—C16—C8 | 119.1 (5) | C41—C40—N7 | 117.6 (6) |
C16—N3—C17 | 119.8 (5) | C42—C41—C40 | 118.5 (7) |
C16—N3—H3D | 120.1 | C42—C41—H41A | 120.8 |
C17—N3—H3D | 120.1 | C40—C41—H41A | 120.8 |
N3—C17—C18 | 114.5 (5) | C37—C42—C41 | 120.6 (6) |
N3—C17—H17A | 108.6 | C37—C42—H42A | 119.7 |
C18—C17—H17A | 108.6 | C41—C42—H42A | 119.7 |
N3—C17—H17B | 108.6 | O9—N7—O8 | 122.1 (6) |
C18—C17—H17B | 108.6 | O9—N7—C40 | 119.6 (6) |
H17A—C17—H17B | 107.6 | O8—N7—C40 | 118.3 (6) |
O5—C18—N4 | 123.6 (6) | C43—O10—H10A | 109.5 |
O5—C18—C17 | 119.4 (6) | O10—C43—C44 | 111.1 (9) |
N4—C18—C17 | 117.1 (6) | O10—C43—H43A | 109.4 |
C18—N4—C19 | 121.9 (6) | C44—C43—H43A | 109.4 |
C18—N4—H4D | 119.0 | O10—C43—H43C | 109.4 |
C19—N4—H4D | 119.0 | C44—C43—H43C | 109.4 |
C20—C19—N4 | 119.4 (6) | H43A—C43—H43C | 108.0 |
C20—C19—C27 | 124.8 (6) | C43—C44—H44A | 109.5 |
N4—C19—C27 | 115.5 (5) | C43—C44—H44B | 109.5 |
C19—C20—C21 | 126.5 (6) | H44A—C44—H44B | 109.5 |
C19—C20—H20A | 116.8 | C43—C44—H44D | 109.5 |
C21—C20—H20A | 116.8 | H44A—C44—H44D | 109.5 |
C22—C21—C26 | 118.2 (6) | H44B—C44—H44D | 109.5 |
C22—C21—C20 | 122.6 (6) | ||
C3—C1—O1—C5 | 56.3 (9) | C23—C24—C25—C26 | 0.0 (12) |
C2—C1—O1—C5 | 174.8 (7) | C24—C25—C26—C21 | 0.5 (11) |
C4—C1—O1—C5 | −69.0 (9) | C22—C21—C26—C25 | −0.6 (11) |
C1—O1—C5—O2 | 1.1 (11) | C20—C21—C26—C25 | −178.2 (7) |
O1—C5—N1—C6 | −176.9 (6) | C20—C19—C27—O6 | −113.2 (8) |
C1—O1—C5—N1 | −176.4 (6) | N4—C19—C27—O6 | 60.5 (8) |
O2—C5—N1—C6 | 5.5 (11) | C20—C19—C27—N5 | 65.4 (9) |
C5—N1—C6—C7 | 87.5 (8) | N4—C19—C27—N5 | −120.8 (6) |
N1—C6—C7—O3 | −17.8 (10) | O6—C27—N5—C28 | 2.4 (9) |
N1—C6—C7—N2 | 164.5 (6) | C19—C27—N5—C28 | −176.3 (5) |
O3—C7—N2—C8 | −6.3 (9) | C27—N5—C28—C36 | −109.7 (7) |
C6—C7—N2—C8 | 171.5 (6) | C27—N5—C28—C29 | 120.7 (6) |
C7—N2—C8—C9 | −122.8 (7) | N5—C28—C29—C30 | 60.4 (7) |
C7—N2—C8—C16 | 59.1 (8) | C36—C28—C29—C30 | −69.3 (7) |
N2—C8—C9—C10 | 6.3 (11) | C28—C29—C30—C35 | −89.6 (8) |
C16—C8—C9—C10 | −175.6 (7) | C28—C29—C30—C31 | 92.3 (8) |
C8—C9—C10—C15 | −160.4 (7) | C35—C30—C31—C32 | −0.5 (11) |
C8—C9—C10—C11 | 22.3 (11) | C29—C30—C31—C32 | 177.6 (7) |
C15—C10—C11—C12 | −0.5 (10) | C30—C31—C32—C33 | 2.4 (13) |
C9—C10—C11—C12 | 176.8 (7) | C31—C32—C33—C34 | −2.0 (12) |
C10—C11—C12—C13 | 1.9 (11) | C32—C33—C34—C35 | 0.0 (12) |
C11—C12—C13—C14 | −1.0 (12) | C31—C30—C35—C34 | −1.6 (10) |
C12—C13—C14—C15 | −1.3 (12) | C29—C30—C35—C34 | −179.8 (6) |
C13—C14—C15—C10 | 2.8 (11) | C33—C34—C35—C30 | 1.9 (11) |
C11—C10—C15—C14 | −1.9 (10) | N5—C28—C36—O7 | −152.2 (6) |
C9—C10—C15—C14 | −179.3 (7) | C29—C28—C36—O7 | −22.7 (9) |
C9—C8—C16—O4 | 29.1 (9) | N5—C28—C36—N6 | 28.9 (8) |
N2—C8—C16—O4 | −152.8 (6) | C29—C28—C36—N6 | 158.4 (5) |
C9—C8—C16—N3 | −154.5 (6) | O7—C36—N6—C37 | −2.7 (10) |
N2—C8—C16—N3 | 23.7 (9) | C28—C36—N6—C37 | 176.1 (6) |
O4—C16—N3—C17 | −0.6 (9) | C36—N6—C37—C42 | 175.4 (6) |
C8—C16—N3—C17 | −177.1 (6) | C36—N6—C37—C38 | −2.7 (10) |
C16—N3—C17—C18 | 82.2 (8) | C42—C37—C38—C39 | −2.3 (9) |
N3—C17—C18—O5 | −167.2 (6) | N6—C37—C38—C39 | 175.7 (6) |
N3—C17—C18—N4 | 13.6 (9) | C37—C38—C39—C40 | 1.6 (9) |
O5—C18—N4—C19 | −4.2 (10) | C38—C39—C40—C41 | 0.1 (10) |
C17—C18—N4—C19 | 174.9 (6) | C38—C39—C40—N7 | −179.0 (6) |
C18—N4—C19—C20 | −147.2 (7) | C39—C40—C41—C42 | −1.1 (10) |
C18—N4—C19—C27 | 38.6 (8) | N7—C40—C41—C42 | 178.0 (6) |
N4—C19—C20—C21 | −172.3 (6) | C38—C37—C42—C41 | 1.4 (10) |
C27—C19—C20—C21 | 1.2 (11) | N6—C37—C42—C41 | −176.7 (6) |
C19—C20—C21—C22 | 38.3 (11) | C40—C41—C42—C37 | 0.4 (10) |
C19—C20—C21—C26 | −144.2 (7) | C39—C40—N7—O9 | −173.8 (6) |
C26—C21—C22—C23 | 0.2 (11) | C41—C40—N7—O9 | 7.1 (9) |
C20—C21—C22—C23 | 177.7 (7) | C39—C40—N7—O8 | 5.8 (9) |
C21—C22—C23—C24 | 0.3 (11) | C41—C40—N7—O8 | −173.3 (6) |
C22—C23—C24—C25 | −0.4 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···O4i | 0.88 | 2.05 | 2.734 (8) | 134 |
N2—H2D···O6i | 0.88 | 1.94 | 2.784 (7) | 161 |
N3—H3D···O3i | 0.88 | 2.36 | 3.057 (7) | 137 |
C6—H6B···O4i | 0.99 | 2.49 | 3.018 (10) | 113 |
C13—H13A···O7ii | 0.95 | 2.42 | 3.222 (9) | 142 |
C3—H3B···O2 | 0.98 | 2.33 | 2.924 (10) | 118 |
C4—H4A···O2 | 0.98 | 2.55 | 3.085 (12) | 114 |
C31—H31A···O7 | 0.95 | 2.51 | 3.101 (8) | 120 |
C38—H38A···O7 | 0.95 | 2.21 | 2.820 (8) | 121 |
C11—H11A···N2 | 0.95 | 2.52 | 3.080 (9) | 118 |
N4—H4D···O3 | 0.88 | 2.09 | 2.925 (7) | 158 |
N6—H6C···O5 | 0.88 | 2.12 | 2.974 (7) | 163 |
N4—H4D···N3 | 0.88 | 2.36 | 2.766 (8) | 108 |
N6—H6C···N5 | 0.88 | 2.35 | 2.764 (7) | 109 |
O10—H10A···O2 | 0.84 | 2.00 | 2.843 (10) | 178 |
C4—H4B···Cg1 | 0.98 | 3.00 | 3.883 | 150 |
C35—H35A···Cg1 | 0.95 | 2.61 | 3.557 | 172 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C42H43N7O9·C2H6O |
Mr | 835.90 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 13.080 (4), 8.998 (3), 18.406 (5) |
β (°) | 99.37 (3) |
V (Å3) | 2137.4 (11) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.45 × 0.04 × 0.02 |
Data collection | |
Diffractometer | Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector |
Absorption correction | Analytical CrysAlis RED (Oxford Diffraction, 2003) |
Tmin, Tmax | 0.828, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14511, 4423, 2794 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.622 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.192, 1.10 |
No. of reflections | 4423 |
No. of parameters | 552 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.32 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXD (Sheldrick, 2002), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97.
N2—C8 | 1.419 (7) | C8—C9 | 1.344 (9) |
N4—C19 | 1.423 (8) | C19—C20 | 1.351 (8) |
N5—C28 | 1.464 (7) | C28—C29 | 1.529 (8) |
C9—C8—N2 | 123.2 (6) | N4—C19—C27 | 115.5 (5) |
C9—C8—C16 | 118.8 (6) | N5—C28—C36 | 113.1 (5) |
N2—C8—C16 | 117.9 (5) | N5—C28—C29 | 112.7 (5) |
C20—C19—N4 | 119.4 (6) | C36—C28—C29 | 112.9 (5) |
C20—C19—C27 | 124.8 (6) | ||
O1—C5—N1—C6 | −176.9 (6) | N3—C17—C18—N4 | 13.6 (9) |
C1—O1—C5—N1 | −176.4 (6) | C17—C18—N4—C19 | 174.9 (6) |
C5—N1—C6—C7 | 87.5 (8) | C18—N4—C19—C27 | 38.6 (8) |
N1—C6—C7—N2 | 164.5 (6) | N4—C19—C20—C21 | −172.3 (6) |
C6—C7—N2—C8 | 171.5 (6) | C19—C20—C21—C22 | 38.3 (11) |
C7—N2—C8—C16 | 59.1 (8) | C19—C20—C21—C26 | −144.2 (7) |
N2—C8—C9—C10 | 6.3 (11) | N4—C19—C27—N5 | −120.8 (6) |
C8—C9—C10—C15 | −160.4 (7) | C19—C27—N5—C28 | −176.3 (5) |
C8—C9—C10—C11 | 22.3 (11) | C27—N5—C28—C36 | −109.7 (7) |
N2—C8—C16—N3 | 23.7 (9) | N5—C28—C36—N6 | 28.9 (8) |
C8—C16—N3—C17 | −177.1 (6) | C28—C36—N6—C37 | 176.1 (6) |
C16—N3—C17—C18 | 82.2 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···O4i | 0.88 | 2.05 | 2.734 (8) | 134 |
N2—H2D···O6i | 0.88 | 1.94 | 2.784 (7) | 161 |
N3—H3D···O3i | 0.88 | 2.36 | 3.057 (7) | 137 |
C6—H6B···O4i | 0.99 | 2.49 | 3.018 (10) | 113 |
C13—H13A···O7ii | 0.95 | 2.42 | 3.222 (9) | 142 |
C3—H3B···O2 | 0.98 | 2.33 | 2.924 (10) | 118 |
C4—H4A···O2 | 0.98 | 2.55 | 3.085 (12) | 114 |
C31—H31A···O7 | 0.95 | 2.51 | 3.101 (8) | 120 |
C38—H38A···O7 | 0.95 | 2.21 | 2.820 (8) | 121 |
C11—H11A···N2 | 0.95 | 2.52 | 3.080 (9) | 118 |
N4—H4D···O3 | 0.88 | 2.09 | 2.925 (7) | 158 |
N6—H6C···O5 | 0.88 | 2.12 | 2.974 (7) | 163 |
N4—H4D···N3 | 0.88 | 2.36 | 2.766 (8) | 108 |
N6—H6C···N5 | 0.88 | 2.35 | 2.764 (7) | 109 |
O10—H10A···O2 | 0.84 | 2.00 | 2.843 (10) | 178 |
C4—H4B···Cg1 | 0.98 | 3.00 | 3.883 | 150 |
C35—H35A···Cg1 | 0.95 | 2.61 | 3.557 | 172 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x, y, z+1. |
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α,β-Dehydroamino acid residues (amino acids with a double bond between the Cα and Cβ atoms) have been found in many biologically active peptides having antibiotic properties (Noda et al., 1983). Incorporation of a dehydroamino acid into a peptide decreases conformational flexibility (Aubry et al., 1984). The molecular structures of α,β-dehydrophenylalanine-containing (ΔPhe) peptides have shown that α,β-dehydrophenylalanine induces β turns (Venkatachalam, 1968) in short sequences with one ΔPhe residue (Główka et al., 1987; Główka, 1988) and a 310 helical conformation in longer sequences (Rajashankar et al., 1992; Rajashankar, Ramakumar, Jain et al., 1995; Rajashankar, Ramakumar, Mal et al., 1995; Padmanabhan & Singh, 1993; Jain et al., 1997). The number and position of ΔPhe residues and the type of neighbouring amino acids also play an important role in peptide chain conformation (Rajashankar et al., 1996).
The present paper reports the crystal structure of the title pentapeptide Boc0—Gly1–ΔZPhe2—Gly3–ΔEPhe4—L-Phe5–p-NA ethanol solvate, (I) (p-NA is para-nitroaniline), containing one ΔZPhe (isomer Z of an α,β-dehydrophenylalanine residue, i.e. with the aromatic ring cis to the N atom) between two flexible glycine residues and one ΔEPhe (isomer E of an α,β-dehydrophenylalanine residue, i.e. with the aromatic ring trans to the N atom) between glycine and phenylalanine residues. There is one molecule in the asymmetric part of the unit cell. The atom-numbering scheme and a general view of the molecule are shown in Fig. 1, while selected bond lengths and angles are given in Table 1.
The Cα═Cβ (C8═C9 and C19═C20) distances for the ΔPhe residues of (I) are in agreement with those found in other structures containing ΔPhe (Główka, 1988). A shortening of about 0.045 (7) Å for the N2—Cα8 bond in ΔZPhe2 and 0.041 (7) Å for the N4—Cα19 bond in ΔEPhe4 is observed with respect to the corresponding bonds in the saturated Phe5 residue (N5—Cα28). The torsion angles χ2 [6.3 (11)°], χ2,1 [22.3 (11)°] and χ2,2 [−160.4 (7)°] of the ΔZPhe2 residue suggest that its side chain is almost planar. The torsion angles χ4 [−172.3 (6)°], χ4,1 [38.3 (11)°] and χ4,2 [−144.2 (7)°] of the ΔEPhe4 residue suggest that, in this case, the side chain is antiperiplanar (Table 1). Are definitions needed for these χ angles? The steric contacts between the side-chain and main-chain atoms of ΔZPhe2 and ΔEPhe4 are partially relaxed by rearrangement of the bond angles at the Cα and Cβ atoms of these residues. As in other cases (Pieroni et al., 1975, 1976/77; Aubry et al., 1985), the cinnamic moieties of the ΔPhe residues in the title peptide are not planar. The torsion angles between the C═C and C═O bonds of ΔZPhe2 and ΔEPhe4 are 29.1 (9) and −113.2 (8)°, respectively.
All the amino acids in the title pentapeptide are linked trans to each other. The deviations of all ω angles are not larger than 9°. The values of torsion angles ϕ and ψ of the ΔZPhe2 and Gly3 residues suggest a type I β turn conformation, while the torsion angles of ΔEPhe4 and Phe5 indicate that these residues form a type II β turn. The torsion angles of the tert-butoxycarbonyl group (ϕ0 and ω0) correspond to a trans–trans conformation.
The conformation of (I) is stabilized by nine intramolecular and four intermolecular hydrogen bonds of different types, namely N—H···O, C—H···N, N—H···N and C—H···O (Table 2). The carbonyl O atoms of Gly1 (O3) and Gly3 (O5) take part in the N4—H4D···O3 and N6—H6C···O5 hydrogen bonds, respectively, as shown in Fig. 1. The π electrons of the aromatic ring of ΔEPhe4 take part in C—H···π interactions with atom H4B of Boc and atom H35A of L-Phe5. The distances and angles between C—H in alkyl group and the centre of the ΔEPhe4 ring (denoted Cg1) are 3.883 Å and 150° for the C4—H4B···Cg1 contact and 3.557 Å and 172° for the C35—H35A···Cg1 contact, respectively (Table 2).
These results show that the presence of two α,β-dehydrophenylalanyl residues induces β turns in the pentapeptide Boc0—Gly1–ΔZPhe2—Gly3–ΔEPhe4—L-Phe5–p-NA. This is consistent with the results for other short peptides, such as the tetrapeptide Boc0—Gly1–ΔZPhe2—Gly3—Phe4–p-NA (Ejsmont et al., 2001).
Table 2. Hydrogen-bonding geometry (Å, °). The C—H···π interaction is a hydrogen bond occurring between C—H in an alkyl group and the π system of ΔEPhe4. The centroid of the ΔEPhe4 ring is denoted Cg1.