Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801021079/bt6093sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801021079/bt6093Isup2.hkl |
CCDC reference: 180548
Ceratospongamide was synthesized by a reported method (Yokokawa et al., 2001) considering the synthetic methods of thiazole-containing peptides (Hamamoto et al., 1983; Hamada et al., 1987).
H atoms of the peptide were positioned at calculated positions and constrained during the refinement. The absolute structure agreed with the L-configurations of material amino acids and with the Flack X parameter of 0.04 (6).
Data collection: MSC/AFC Diffractmeter Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractmeter Control Software; data reduction: MSC/AFC Diffractmeter Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PARST (Nardelli, 1983).
C41H49N7O6S | Dx = 1.152 Mg m−3 |
Mr = 767.93 | Cu Kα radiation, λ = 1.54180 Å |
Tetragonal, P41212 | Cell parameters from 24 reflections |
a = 12.805 (2) Å | θ = 9.8–21.2° |
c = 54.013 (11) Å | µ = 1.06 mm−1 |
V = 8857 (3) Å3 | T = 293 K |
Z = 8 | Plate, colorless |
F(000) = 3264 | 0.26 × 0.17 × 0.06 mm |
Rigaku AFC-5R diffractometer | 2203 reflections with I > 2σ(I) |
Radiation source: Rigaku RU200 | Rint = 0.194 |
Graphite monochromator | θmax = 56.0°, θmin = 3.6° |
\2q–ω scans | h = 0→13 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.78, Tmax = 0.97 | l = −16→58 |
4364 measured reflections | 3 standard reflections every 150 reflections |
4062 independent reflections | intensity decay: 98.2% |
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)] = 0.098 | H-atom parameters constrained |
wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.002P)2 + 5.20P] where P = (Fo2 + 2Fc2)/3 |
S = 1.69 | (Δ/σ)max = 0.007 |
4062 reflections | Δρmax = 0.30 e Å−3 |
496 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (6) |
C41H49N7O6S | Z = 8 |
Mr = 767.93 | Cu Kα radiation |
Tetragonal, P41212 | µ = 1.06 mm−1 |
a = 12.805 (2) Å | T = 293 K |
c = 54.013 (11) Å | 0.26 × 0.17 × 0.06 mm |
V = 8857 (3) Å3 |
Rigaku AFC-5R diffractometer | 2203 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.194 |
Tmin = 0.78, Tmax = 0.97 | θmax = 56.0° |
4364 measured reflections | 3 standard reflections every 150 reflections |
4062 independent reflections | intensity decay: 98.2% |
R[F2 > 2σ(F2)] = 0.098 | H-atom parameters constrained |
wR(F2) = 0.155 | Δρmax = 0.30 e Å−3 |
S = 1.69 | Δρmin = −0.22 e Å−3 |
4062 reflections | Absolute structure: Flack (1983) |
496 parameters | Absolute structure parameter: 0.04 (6) |
0 restraints |
Experimental. Data collection was attempted to measure reflections until approximately 2θ = 120°, but the completeness of observed reflections (the fraction of unique reflections measured out) decreased at the shell of 2θ > 110°. In early stage of refinements, all reflections were used, but reflections of 2θ > 112° were omitted in the final refinement because of low completeness and high R-value in this shell. The completeness was finally 0.935 until 2θ = 112°. |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 11.1837 x + 5.5301 y - 12.1652 z = 8.8514 * 0.0104 C31 * -0.0220 N32 * 0.0260 C33 * -0.0170 C34 * 0.0026 S35 Rms deviation of fitted atoms = 0.0177 12.6273 x + 2.1012 y - 1.4040 z = 13.4656 Angle to previous plane = 20.29 * -0.0082 N15 * -0.0160 C13 * 0.0027 O14 * 0.0114 C9 * 0.0101 C16 Rms deviation of fitted atoms = 0.0106 |
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 | ||
N1 | 0.9625 (6) | 0.8438 (6) | 0.20055 (14) | 0.068 (2) | |
H1 | 0.9550 | 0.7906 | 0.2101 | 0.082* | |
C2 | 1.0515 (8) | 0.8480 (8) | 0.1830 (2) | 0.069 (3) | |
H2 | 1.0604 | 0.9212 | 0.1781 | 0.083* | |
C3 | 1.1559 (8) | 0.8122 (9) | 0.1955 (2) | 0.080 (3) | |
H3 | 1.2104 | 0.8144 | 0.1828 | 0.096* | |
C4 | 1.1871 (11) | 0.8854 (10) | 0.2153 (2) | 0.118 (4) | |
H4A | 1.1929 | 0.9546 | 0.2086 | 0.177* | |
H4B | 1.2532 | 0.8644 | 0.2220 | 0.177* | |
H4C | 1.1353 | 0.8849 | 0.2282 | 0.177* | |
C5 | 1.1512 (9) | 0.7035 (10) | 0.2049 (3) | 0.112 (4) | |
H5A | 1.1137 | 0.6614 | 0.1929 | 0.135* | |
H5B | 1.1107 | 0.7034 | 0.2201 | 0.135* | |
C6 | 1.2555 (11) | 0.6508 (12) | 0.2101 (3) | 0.166 (7) | |
H6A | 1.2435 | 0.5815 | 0.2163 | 0.248* | |
H6B | 1.2933 | 0.6905 | 0.2222 | 0.248* | |
H6C | 1.2955 | 0.6471 | 0.1951 | 0.248* | |
C7 | 1.0285 (8) | 0.7893 (8) | 0.1606 (2) | 0.060 (3) | |
N8 | 0.9578 (6) | 0.7187 (7) | 0.15750 (15) | 0.074 (2) | |
C9 | 0.9691 (7) | 0.6790 (8) | 0.1332 (2) | 0.072 (3) | |
H9 | 0.9060 | 0.6959 | 0.1237 | 0.086* | |
C10 | 1.0639 (9) | 0.7417 (9) | 0.1219 (2) | 0.080 (3) | |
H10 | 1.1214 | 0.6940 | 0.1180 | 0.096* | |
O11 | 1.0925 (5) | 0.8081 (5) | 0.14172 (13) | 0.0754 (19) | |
C12 | 1.0353 (9) | 0.8044 (10) | 0.0996 (2) | 0.106 (4) | |
H12A | 1.0960 | 0.8399 | 0.0935 | 0.158* | |
H12B | 0.9829 | 0.8547 | 0.1040 | 0.158* | |
H12C | 1.0084 | 0.7589 | 0.0870 | 0.158* | |
C13 | 0.9864 (9) | 0.5617 (10) | 0.1322 (3) | 0.084 (3) | |
O14 | 0.9925 (7) | 0.5193 (6) | 0.11106 (13) | 0.104 (3) | |
N15 | 0.9971 (7) | 0.5146 (7) | 0.15265 (18) | 0.076 (3) | |
H15 | 0.9924 | 0.5490 | 0.1663 | 0.091* | |
C16 | 1.0171 (8) | 0.4034 (8) | 0.1533 (2) | 0.075 (3) | |
H16 | 0.9769 | 0.3685 | 0.1403 | 0.090* | |
C17 | 1.1349 (8) | 0.3792 (8) | 0.1501 (2) | 0.093 (4) | |
H17A | 1.1737 | 0.4131 | 0.1632 | 0.112* | |
H17B | 1.1584 | 0.4081 | 0.1344 | 0.112* | |
C18 | 1.1592 (9) | 0.2605 (9) | 0.1505 (3) | 0.084 (3) | |
C19 | 1.1319 (10) | 0.2052 (13) | 0.1310 (3) | 0.120 (4) | |
H19 | 1.0934 | 0.2431 | 0.1195 | 0.144* | |
C20 | 1.148 (2) | 0.105 (2) | 0.1243 (9) | 0.28 (2) | |
H20 | 1.1305 | 0.0739 | 0.1093 | 0.335* | |
C21 | 1.199 (2) | 0.0540 (19) | 0.1457 (8) | 0.224 (19) | |
H21 | 1.2106 | −0.0176 | 0.1448 | 0.269* | |
C22 | 1.2310 (12) | 0.1028 (18) | 0.1664 (4) | 0.152 (8) | |
H22 | 1.2664 | 0.0660 | 0.1786 | 0.182* | |
C23 | 1.2098 (10) | 0.2130 (14) | 0.1696 (3) | 0.109 (5) | |
H23 | 1.2296 | 0.2492 | 0.1837 | 0.131* | |
C24 | 0.9773 (10) | 0.3649 (9) | 0.1801 (2) | 0.076 (3) | |
O25 | 1.0284 (6) | 0.3925 (7) | 0.19786 (17) | 0.122 (3) | |
N26 | 0.8920 (7) | 0.3075 (6) | 0.18148 (16) | 0.071 (2) | |
C27 | 0.8260 (8) | 0.2758 (7) | 0.1602 (2) | 0.074 (3) | |
H27 | 0.8671 | 0.2386 | 0.1477 | 0.089* | |
C28 | 0.7523 (9) | 0.2033 (8) | 0.1733 (2) | 0.088 (3) | |
H28A | 0.6859 | 0.2003 | 0.1647 | 0.106* | |
H28B | 0.7814 | 0.1334 | 0.1740 | 0.106* | |
C29 | 0.7385 (8) | 0.2453 (10) | 0.1981 (2) | 0.093 (3) | |
H29A | 0.7140 | 0.1920 | 0.2094 | 0.111* | |
H29B | 0.6895 | 0.3031 | 0.1981 | 0.111* | |
C30 | 0.8459 (9) | 0.2809 (8) | 0.20469 (18) | 0.083 (3) | |
H30A | 0.8433 | 0.3411 | 0.2156 | 0.099* | |
H30B | 0.8847 | 0.2255 | 0.2128 | 0.099* | |
C31 | 0.7705 (7) | 0.3716 (7) | 0.14883 (17) | 0.063 (3) | |
N32 | 0.7438 (6) | 0.4505 (6) | 0.16275 (13) | 0.057 (2) | |
C33 | 0.6961 (8) | 0.5222 (7) | 0.1475 (2) | 0.062 (3) | |
C34 | 0.6795 (8) | 0.4974 (7) | 0.1246 (2) | 0.080 (3) | |
H34 | 0.6436 | 0.5385 | 0.1132 | 0.096* | |
S35 | 0.7339 (2) | 0.37708 (18) | 0.11833 (5) | 0.0703 (8) | |
C36 | 0.6630 (9) | 0.6287 (9) | 0.1579 (2) | 0.080 (3) | |
O37 | 0.6245 (6) | 0.6958 (5) | 0.14532 (13) | 0.079 (2) | |
N38 | 0.6865 (6) | 0.6370 (5) | 0.18204 (14) | 0.067 (2) | |
H38 | 0.7091 | 0.5833 | 0.1900 | 0.080* | |
C39 | 0.6736 (7) | 0.7387 (7) | 0.19520 (17) | 0.065 (3) | |
H39 | 0.7021 | 0.7976 | 0.1858 | 0.077* | |
C40 | 0.5551 (8) | 0.7515 (9) | 0.2009 (2) | 0.095 (4) | |
H40A | 0.5157 | 0.7436 | 0.1857 | 0.114* | |
H40B | 0.5332 | 0.6969 | 0.2122 | 0.114* | |
C41 | 0.5316 (7) | 0.8559 (9) | 0.21206 (18) | 0.063 (3) | |
C42 | 0.5184 (9) | 0.9398 (12) | 0.1960 (2) | 0.091 (4) | |
H42 | 0.5246 | 0.9295 | 0.1791 | 0.109* | |
C43 | 0.4967 (12) | 1.0360 (15) | 0.2048 (4) | 0.128 (5) | |
H43 | 0.4869 | 1.0904 | 0.1936 | 0.154* | |
C44 | 0.4891 (11) | 1.0545 (13) | 0.2280 (5) | 0.128 (5) | |
H44 | 0.4729 | 1.1219 | 0.2331 | 0.154* | |
C45 | 0.5042 (9) | 0.9782 (18) | 0.2457 (3) | 0.119 (5) | |
H45 | 0.5022 | 0.9933 | 0.2625 | 0.143* | |
C46 | 0.5236 (8) | 0.8725 (11) | 0.2366 (2) | 0.086 (3) | |
H46 | 0.5303 | 0.8172 | 0.2477 | 0.103* | |
C47 | 0.7323 (8) | 0.7203 (9) | 0.2199 (2) | 0.074 (3) | |
O48 | 0.7307 (7) | 0.6391 (5) | 0.23082 (13) | 0.105 (3) | |
N49 | 0.7859 (6) | 0.8062 (6) | 0.22807 (14) | 0.067 (2) | |
C50 | 0.7940 (8) | 0.9103 (6) | 0.21684 (16) | 0.062 (3) | |
H50 | 0.7311 | 0.9284 | 0.2074 | 0.074* | |
C51 | 0.8063 (9) | 0.9805 (8) | 0.2407 (2) | 0.083 (3) | |
H51A | 0.8443 | 1.0438 | 0.2368 | 0.100* | |
H51B | 0.7382 | 0.9996 | 0.2472 | 0.100* | |
C52 | 0.8627 (11) | 0.9204 (9) | 0.2587 (2) | 0.104 (4) | |
H52A | 0.8452 | 0.9427 | 0.2754 | 0.125* | |
H52B | 0.9374 | 0.9277 | 0.2563 | 0.125* | |
C53 | 0.8264 (9) | 0.8011 (8) | 0.25414 (17) | 0.088 (3) | |
H53A | 0.8848 | 0.7531 | 0.2555 | 0.105* | |
H53B | 0.7721 | 0.7804 | 0.2657 | 0.105* | |
C54 | 0.8920 (8) | 0.9247 (9) | 0.20162 (18) | 0.062 (3) | |
O55 | 0.9054 (6) | 1.0044 (6) | 0.18901 (17) | 0.117 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.082 (6) | 0.057 (5) | 0.066 (5) | 0.007 (5) | 0.013 (5) | 0.013 (4) |
C2 | 0.075 (8) | 0.059 (7) | 0.075 (7) | 0.001 (6) | 0.006 (7) | −0.001 (6) |
C3 | 0.090 (9) | 0.080 (8) | 0.071 (7) | 0.005 (7) | 0.008 (7) | −0.014 (7) |
C4 | 0.154 (12) | 0.121 (10) | 0.079 (8) | −0.014 (10) | −0.006 (8) | 0.022 (9) |
C5 | 0.097 (9) | 0.112 (10) | 0.128 (11) | −0.006 (8) | −0.026 (8) | 0.014 (9) |
C6 | 0.136 (12) | 0.156 (13) | 0.205 (17) | 0.056 (11) | −0.039 (13) | 0.047 (12) |
C7 | 0.056 (6) | 0.054 (7) | 0.069 (8) | 0.014 (6) | −0.004 (7) | 0.019 (6) |
N8 | 0.071 (6) | 0.081 (6) | 0.070 (6) | 0.001 (5) | 0.004 (5) | −0.021 (5) |
C9 | 0.056 (7) | 0.074 (8) | 0.086 (8) | 0.000 (6) | −0.010 (6) | 0.008 (7) |
C10 | 0.099 (9) | 0.078 (7) | 0.064 (7) | 0.037 (7) | 0.019 (7) | −0.009 (7) |
O11 | 0.089 (5) | 0.084 (5) | 0.053 (4) | 0.003 (4) | 0.020 (4) | −0.004 (4) |
C12 | 0.094 (9) | 0.124 (10) | 0.100 (9) | 0.008 (8) | 0.023 (8) | 0.009 (9) |
C13 | 0.086 (9) | 0.086 (9) | 0.080 (10) | −0.004 (7) | −0.017 (8) | −0.016 (9) |
O14 | 0.166 (8) | 0.090 (6) | 0.055 (5) | −0.002 (5) | 0.002 (5) | −0.010 (4) |
N15 | 0.107 (7) | 0.063 (6) | 0.058 (6) | −0.001 (5) | −0.005 (6) | −0.014 (5) |
C16 | 0.069 (8) | 0.063 (8) | 0.094 (9) | 0.003 (6) | 0.000 (7) | −0.025 (7) |
C17 | 0.079 (8) | 0.081 (8) | 0.119 (10) | −0.005 (7) | 0.012 (8) | −0.033 (8) |
C18 | 0.074 (8) | 0.077 (9) | 0.103 (10) | −0.024 (7) | 0.029 (8) | −0.020 (9) |
C19 | 0.101 (10) | 0.087 (11) | 0.172 (14) | 0.002 (8) | 0.018 (11) | −0.025 (11) |
C20 | 0.17 (2) | 0.12 (2) | 0.55 (7) | −0.054 (17) | 0.05 (3) | −0.04 (3) |
C21 | 0.15 (2) | 0.115 (19) | 0.41 (5) | −0.057 (16) | 0.19 (3) | −0.13 (3) |
C22 | 0.119 (14) | 0.118 (15) | 0.22 (2) | 0.033 (12) | 0.097 (15) | 0.097 (15) |
C23 | 0.084 (9) | 0.148 (16) | 0.095 (9) | −0.013 (9) | 0.032 (8) | 0.036 (10) |
C24 | 0.067 (8) | 0.068 (8) | 0.094 (10) | 0.015 (7) | −0.007 (8) | 0.002 (7) |
O25 | 0.103 (6) | 0.155 (8) | 0.108 (7) | −0.045 (6) | −0.043 (6) | −0.013 (6) |
N26 | 0.071 (6) | 0.071 (6) | 0.070 (6) | −0.002 (5) | −0.011 (5) | −0.005 (5) |
C27 | 0.072 (7) | 0.058 (7) | 0.093 (7) | 0.005 (6) | −0.029 (7) | 0.002 (7) |
C28 | 0.092 (9) | 0.070 (7) | 0.104 (9) | 0.004 (7) | −0.040 (8) | 0.022 (8) |
C29 | 0.060 (7) | 0.119 (10) | 0.098 (9) | −0.014 (7) | −0.023 (7) | 0.006 (8) |
C30 | 0.100 (9) | 0.091 (8) | 0.057 (6) | −0.005 (7) | 0.005 (7) | 0.024 (6) |
C31 | 0.077 (7) | 0.049 (6) | 0.061 (6) | 0.000 (6) | −0.020 (6) | 0.007 (6) |
N32 | 0.076 (5) | 0.048 (5) | 0.048 (4) | 0.015 (4) | −0.007 (4) | 0.003 (4) |
C33 | 0.081 (7) | 0.046 (6) | 0.059 (7) | −0.016 (6) | −0.013 (6) | −0.017 (6) |
C34 | 0.100 (8) | 0.043 (6) | 0.097 (9) | 0.010 (5) | −0.016 (8) | 0.016 (6) |
S35 | 0.085 (2) | 0.0591 (15) | 0.0668 (15) | −0.0033 (14) | −0.0115 (15) | −0.0027 (15) |
C36 | 0.086 (8) | 0.059 (8) | 0.094 (10) | −0.023 (7) | −0.008 (8) | −0.009 (8) |
O37 | 0.118 (6) | 0.053 (4) | 0.067 (4) | 0.007 (4) | −0.024 (4) | 0.002 (4) |
N38 | 0.090 (6) | 0.049 (5) | 0.061 (5) | −0.001 (5) | −0.021 (5) | −0.002 (5) |
C39 | 0.063 (6) | 0.052 (6) | 0.079 (7) | −0.003 (5) | −0.006 (6) | −0.015 (6) |
C40 | 0.086 (8) | 0.094 (9) | 0.106 (8) | −0.015 (7) | 0.022 (7) | −0.034 (8) |
C41 | 0.068 (7) | 0.079 (8) | 0.041 (6) | −0.007 (6) | −0.002 (5) | 0.002 (6) |
C42 | 0.093 (9) | 0.096 (9) | 0.084 (9) | −0.006 (8) | 0.003 (7) | −0.002 (9) |
C43 | 0.140 (13) | 0.129 (16) | 0.115 (14) | 0.028 (11) | 0.034 (11) | 0.003 (12) |
C44 | 0.109 (12) | 0.103 (12) | 0.172 (17) | 0.030 (9) | 0.023 (13) | −0.016 (14) |
C45 | 0.069 (9) | 0.199 (17) | 0.090 (10) | 0.017 (11) | 0.012 (8) | −0.024 (13) |
C46 | 0.080 (8) | 0.113 (10) | 0.066 (8) | 0.024 (7) | −0.007 (7) | 0.013 (7) |
C47 | 0.068 (7) | 0.078 (8) | 0.077 (8) | −0.013 (7) | −0.029 (6) | −0.026 (7) |
O48 | 0.176 (8) | 0.050 (4) | 0.088 (5) | −0.027 (5) | −0.003 (5) | 0.027 (4) |
N49 | 0.067 (5) | 0.070 (6) | 0.064 (5) | −0.002 (5) | 0.002 (5) | −0.002 (5) |
C50 | 0.095 (8) | 0.041 (5) | 0.049 (5) | 0.001 (5) | 0.022 (6) | −0.004 (5) |
C51 | 0.089 (8) | 0.072 (7) | 0.089 (8) | 0.002 (6) | 0.002 (7) | −0.025 (7) |
C52 | 0.138 (11) | 0.096 (9) | 0.079 (8) | 0.007 (8) | −0.038 (8) | −0.034 (7) |
C53 | 0.108 (8) | 0.096 (8) | 0.060 (7) | −0.014 (7) | −0.034 (6) | −0.007 (6) |
C54 | 0.069 (7) | 0.071 (8) | 0.047 (6) | 0.012 (6) | −0.003 (6) | 0.012 (6) |
O55 | 0.108 (6) | 0.100 (6) | 0.143 (8) | 0.021 (4) | 0.032 (5) | 0.067 (6) |
N1—C54 | 1.375 (11) | C27—C31 | 1.545 (12) |
N1—C2 | 1.484 (12) | C28—C29 | 1.455 (14) |
C2—C7 | 1.453 (13) | C29—C30 | 1.492 (13) |
C2—C3 | 1.566 (13) | C31—N32 | 1.304 (10) |
C3—C4 | 1.479 (13) | C31—S35 | 1.714 (9) |
C3—C5 | 1.483 (14) | N32—C33 | 1.375 (11) |
C5—C6 | 1.523 (14) | C33—C34 | 1.297 (13) |
C7—N8 | 1.289 (11) | C33—C36 | 1.533 (14) |
C7—O11 | 1.332 (10) | C34—S35 | 1.725 (10) |
N8—C9 | 1.417 (11) | C36—O37 | 1.200 (12) |
C9—C13 | 1.519 (14) | C36—N38 | 1.345 (12) |
C9—C10 | 1.576 (13) | N38—C39 | 1.493 (10) |
C10—O11 | 1.415 (12) | C39—C47 | 1.550 (13) |
C10—C12 | 1.492 (14) | C39—C40 | 1.557 (13) |
C13—N15 | 1.264 (13) | C40—C41 | 1.498 (14) |
C13—O14 | 1.269 (12) | C41—C46 | 1.347 (13) |
N15—C16 | 1.447 (11) | C41—C42 | 1.390 (13) |
C16—C17 | 1.550 (13) | C42—C43 | 1.348 (17) |
C16—C24 | 1.610 (15) | C43—C44 | 1.28 (2) |
C17—C18 | 1.552 (15) | C44—C45 | 1.381 (19) |
C18—C19 | 1.314 (16) | C45—C46 | 1.460 (18) |
C18—C23 | 1.361 (15) | C47—O48 | 1.195 (11) |
C19—C20 | 1.35 (3) | C47—N49 | 1.369 (11) |
C20—C21 | 1.48 (5) | N49—C50 | 1.468 (10) |
C21—C22 | 1.34 (3) | N49—C53 | 1.502 (11) |
C22—C23 | 1.45 (2) | C50—C54 | 1.512 (13) |
C24—O25 | 1.214 (13) | C50—C51 | 1.581 (12) |
C24—N26 | 1.318 (12) | C51—C52 | 1.434 (13) |
N26—C30 | 1.427 (12) | C52—C53 | 1.616 (13) |
N26—C27 | 1.484 (11) | C54—O55 | 1.239 (10) |
C27—C28 | 1.500 (13) | ||
C54—N1—C2 | 120.3 (8) | C29—C28—C27 | 106.3 (9) |
C7—C2—N1 | 110.9 (8) | C28—C29—C30 | 102.8 (9) |
C7—C2—C3 | 112.3 (8) | N26—C30—C29 | 104.1 (9) |
N1—C2—C3 | 111.6 (8) | N32—C31—C27 | 120.4 (8) |
C4—C3—C5 | 111.0 (10) | N32—C31—S35 | 116.8 (6) |
C4—C3—C2 | 110.9 (9) | C27—C31—S35 | 122.7 (8) |
C5—C3—C2 | 112.9 (9) | C31—N32—C33 | 106.8 (7) |
C3—C5—C6 | 116.4 (11) | C34—C33—N32 | 118.7 (9) |
N8—C7—O11 | 117.3 (10) | C34—C33—C36 | 121.3 (11) |
N8—C7—C2 | 127.9 (10) | N32—C33—C36 | 120.0 (9) |
O11—C7—C2 | 114.7 (10) | C33—C34—S35 | 109.8 (8) |
C7—N8—C9 | 107.5 (9) | C31—S35—C34 | 87.6 (5) |
N8—C9—C13 | 113.6 (10) | O37—C36—N38 | 125.7 (10) |
N8—C9—C10 | 104.6 (8) | O37—C36—C33 | 123.1 (10) |
C13—C9—C10 | 112.3 (9) | N38—C36—C33 | 111.2 (11) |
O11—C10—C12 | 110.5 (9) | C36—N38—C39 | 120.4 (8) |
O11—C10—C9 | 102.4 (7) | N38—C39—C47 | 102.9 (7) |
C12—C10—C9 | 113.3 (9) | N38—C39—C40 | 107.0 (7) |
C7—O11—C10 | 108.1 (8) | C47—C39—C40 | 108.6 (8) |
N15—C13—O14 | 125.1 (11) | C41—C40—C39 | 111.6 (8) |
N15—C13—C9 | 117.4 (11) | C46—C41—C42 | 118.8 (11) |
O14—C13—C9 | 117.5 (12) | C46—C41—C40 | 123.6 (11) |
C13—N15—C16 | 120.7 (10) | C42—C41—C40 | 117.6 (10) |
N15—C16—C17 | 111.5 (9) | C43—C42—C41 | 120.9 (13) |
N15—C16—C24 | 105.6 (8) | C44—C43—C42 | 122.0 (17) |
C17—C16—C24 | 110.4 (9) | C43—C44—C45 | 122.4 (16) |
C16—C17—C18 | 113.0 (9) | C44—C45—C46 | 116.7 (13) |
C19—C18—C23 | 119.5 (13) | C41—C46—C45 | 119.3 (12) |
C19—C18—C17 | 117.5 (15) | O48—C47—N49 | 123.3 (9) |
C23—C18—C17 | 123.0 (14) | O48—C47—C39 | 123.3 (9) |
C18—C19—C20 | 133 (2) | N49—C47—C39 | 113.4 (10) |
C19—C20—C21 | 106 (4) | C47—N49—C50 | 129.2 (8) |
C22—C21—C20 | 125 (3) | C47—N49—C53 | 116.1 (8) |
C21—C22—C23 | 120 (2) | C50—N49—C53 | 113.7 (7) |
C18—C23—C22 | 115.8 (15) | N49—C50—C54 | 113.2 (8) |
O25—C24—N26 | 124.2 (12) | N49—C50—C51 | 100.7 (7) |
O25—C24—C16 | 116.8 (11) | C54—C50—C51 | 106.9 (8) |
N26—C24—C16 | 119.0 (11) | C52—C51—C50 | 107.4 (8) |
C24—N26—C30 | 121.8 (10) | C51—C52—C53 | 105.0 (9) |
C24—N26—C27 | 125.5 (10) | N49—C53—C52 | 101.7 (8) |
C30—N26—C27 | 112.3 (8) | O55—C54—N1 | 120.4 (9) |
N26—C27—C28 | 99.4 (8) | O55—C54—C50 | 120.9 (9) |
N26—C27—C31 | 110.7 (8) | N1—C54—C50 | 118.4 (9) |
C28—C27—C31 | 112.9 (8) | ||
C54—N1—C2—C7 | −97.9 (10) | C27—C31—N32—C33 | −179.7 (8) |
N1—C2—C7—N8 | −18.5 (15) | C31—N32—C33—C36 | −175.1 (9) |
C2—C7—N8—C9 | −176.3 (10) | N32—C33—C36—N38 | −0.3 (13) |
C7—N8—C9—C10 | 0.1 (11) | C33—C36—N38—C39 | 172.3 (8) |
N8—C9—C13—N15 | −5.5 (15) | C36—N38—C39—C47 | −167.3 (9) |
C9—C13—N15—C16 | −178.1 (10) | N38—C39—C47—N49 | 142.5 (8) |
C13—N15—C16—C24 | −156.2 (11) | C39—C47—N49—C50 | 0.4 (14) |
N15—C16—C24—N26 | 109.0 (11) | C47—N49—C50—C54 | −97.2 (11) |
C16—C24—N26—C27 | −1.4 (15) | N49—C50—C54—N1 | −2.2 (12) |
C24—N26—C27—C31 | −67.7 (13) | C2—N1—C54—C50 | 170.9 (8) |
N26—C27—C31—N32 | −31.5 (12) |
Experimental details
Crystal data | |
Chemical formula | C41H49N7O6S |
Mr | 767.93 |
Crystal system, space group | Tetragonal, P41212 |
Temperature (K) | 293 |
a, c (Å) | 12.805 (2), 54.013 (11) |
V (Å3) | 8857 (3) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.26 × 0.17 × 0.06 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.78, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4364, 4062, 2203 |
Rint | 0.194 |
θmax (°) | 56.0 |
(sin θ/λ)max (Å−1) | 0.538 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.098, 0.155, 1.69 |
No. of reflections | 4062 |
No. of parameters | 496 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.04 (6) |
Computer programs: MSC/AFC Diffractmeter Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractmeter Control Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), PARST (Nardelli, 1983).
C54—N1—C2—C7 | −97.9 (10) | C27—C31—N32—C33 | −179.7 (8) |
N1—C2—C7—N8 | −18.5 (15) | C31—N32—C33—C36 | −175.1 (9) |
C2—C7—N8—C9 | −176.3 (10) | N32—C33—C36—N38 | −0.3 (13) |
C7—N8—C9—C10 | 0.1 (11) | C33—C36—N38—C39 | 172.3 (8) |
N8—C9—C13—N15 | −5.5 (15) | C36—N38—C39—C47 | −167.3 (9) |
C9—C13—N15—C16 | −178.1 (10) | N38—C39—C47—N49 | 142.5 (8) |
C13—N15—C16—C24 | −156.2 (11) | C39—C47—N49—C50 | 0.4 (14) |
N15—C16—C24—N26 | 109.0 (11) | C47—N49—C50—C54 | −97.2 (11) |
C16—C24—N26—C27 | −1.4 (15) | N49—C50—C54—N1 | −2.2 (12) |
C24—N26—C27—C31 | −67.7 (13) | C2—N1—C54—C50 | 170.9 (8) |
N26—C27—C31—N32 | −31.5 (12) |
Ceratospongamide (CS), cyclo(–Ile-Oxz-Phe-Pro-Thz-Phe-Pro-), was isolated from the marine red alga (Rhodophyta) Ceratodictyon spongiosum (Tan et al., 2000). This cyclic heptapeptide contains oxazoline (Oxz) and thiazole (Thz), and is a potent inhibitor of secreted phospholipase A2 (sPLA2). It is known that two stable isomers related with the two proline amide bonds exist in nature and show different activities for sPLA2: the ED50 of [trans,trans]-CS is 32 nM in inhibition for sPLA2, but [cis,cis]-CS is inactive. Such a conformation-depending activity is strikingly interesting to study the relationships between its activity and structure.
Synthesized CS, (I), was crystallized from methanol solution and its structure is shown in Fig. 1. The torsion angles C16—C24—N26—C27 and C39—C47—N49—C50 are -1.4 (15) and 0.4 (14)° (Table 1), respectively, and show a cis-form of both two proline residues. The peptide backbone is folded, but its manner is different from those of other Thz-containing peptides, ascidiacyclamides (Ishida et al., 1988). The backbone is turned at two Pro residues (Fig. 2), and their cis-forms is important in this folded ring. The Thz ring and amide bond plane (composed of atoms C13, O14, N15 and C16 atoms) are faced with a plane–plane angle of 13.5°. Furthermore, the short contact is observed between N15 and N32 atoms (3.39 Å). These indicate a π–π electron interaction between the Thz ring and amide bond. This interaction stabilizes the folded structure with no hydrogen bond.