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Ceratospong­amide, cyclo(-Ile-Oxz-Phe-Pro-Thz-Phe-Pro-) (Oxz = oxazoline and Thz = thia­zole), C41H49N7O6S, is a thia­zole-containing cyclic peptide isolated from marine sources. Two stable isomers are known and the structure of the cis,cis-isomer has been determined. The peptide ring is folded in a new manner for thia­zole-containing peptides. The thia­zole ring faces the amide bond plane between the Oxz and Phe residues, with π–π interactions. This interaction stabilizes the peptide conformation with no hydrogen bonding.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801021079/bt6093sup1.cif
Contains datablocks cerato, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801021079/bt6093Isup2.hkl
Contains datablock I

CCDC reference: 180548

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.020 Å
  • R factor = 0.098
  • wR factor = 0.155
  • Data-to-parameter ratio = 8.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5376
Author response: In the shell over 2q\=112 \%, the completeness was very low. Therefore, reflections of this shell were omitted at the final refinement stage.
PLAT_601  Alert A Structure Contains Solvent Accessible VOIDS of     227.00 A   3
Author response: I think the structures of peptides often give bigger VOIDS because the amino acids have relatively many branches.

Amber Alert Alert Level B:
RINTA_01 Alert B The value of Rint is greater than 0.15 Rint given 0.193
Author response: Reflections are quite weak, and date collection could not cover enough region.

Yellow Alert Alert Level C:
PLAT_213 Alert C Atom C21 has ADP max/min Ratio ........... 3.50 prolate PLAT_360 Alert C Short C(sp3)-C(sp3) Bond C(51) - C(52) = 1.43 Ang. PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C(33) - C(36) = 1.53 Ang. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 55.98 From the CIF: _reflns_number_total 4062 From the CIF: _diffrn_reflns_limit_ max hkl 13. 9. 58. From the CIF: _diffrn_reflns_limit_ min hkl 0. 0. -16. TEST1: Expected hkl limits for theta max Calculated maximum hkl 13. 13. 58. Calculated minimum hkl -13. -13. -58. ALERT: Expected hkl max differ from CIF values REFLT_03 From the CIF: _diffrn_reflns_theta_max 55.98 From the CIF: _reflns_number_total 4062 Count of symmetry unique reflns 3433 Completeness (_total/calc) 118.32% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 629 Fraction of Friedel pairs measured 0.183 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
2 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
3 Alert Level C = Please check

Comment top

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 ππ electron interaction between the Thz ring and amide bond. This interaction stabilizes the folded structure with no hydrogen bond.

Experimental top

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).

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Stereoview of ceratospongamide with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Conformation of peptide ring. (a) Projection on Thz ring, and (b) orthogonal projection. Side chains and H atoms have been omitted for clarity. Colored balls of black, red, blue and green represent C, O, N and S atoms, respectively. cis-Amide bonds are represented by green rods.
[cis,cis]-Ceratospongamide cyclo(–Ile-Oxz-Phe-Pro-Thz-Phe-Pro-) Oxz=oxazoline, Thz=thiazole top
Crystal data top
C41H49N7O6SDx = 1.152 Mg m3
Mr = 767.93Cu Kα radiation, λ = 1.54180 Å
Tetragonal, P41212Cell parameters from 24 reflections
a = 12.805 (2) Åθ = 9.8–21.2°
c = 54.013 (11) ŵ = 1.06 mm1
V = 8857 (3) Å3T = 293 K
Z = 8Plate, colorless
F(000) = 32640.26 × 0.17 × 0.06 mm
Data collection top
Rigaku AFC-5R
diffractometer
2203 reflections with I > 2σ(I)
Radiation source: Rigaku RU200Rint = 0.194
Graphite monochromatorθmax = 56.0°, θmin = 3.6°
\2q–ω scansh = 013
Absorption correction: ψ scan
(North et al., 1968)
k = 09
Tmin = 0.78, Tmax = 0.97l = 1658
4364 measured reflections3 standard reflections every 150 reflections
4062 independent reflections intensity decay: 98.2%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.098H-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 reflectionsΔρmax = 0.30 e Å3
496 parametersΔρmin = 0.22 e Å3
0 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (6)
Crystal data top
C41H49N7O6SZ = 8
Mr = 767.93Cu Kα radiation
Tetragonal, P41212µ = 1.06 mm1
a = 12.805 (2) ÅT = 293 K
c = 54.013 (11) Å0.26 × 0.17 × 0.06 mm
V = 8857 (3) Å3
Data collection top
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 = 0.97θmax = 56.0°
4364 measured reflections3 standard reflections every 150 reflections
4062 independent reflections intensity decay: 98.2%
Refinement top
R[F2 > 2σ(F2)] = 0.098H-atom parameters constrained
wR(F2) = 0.155Δρmax = 0.30 e Å3
S = 1.69Δρmin = 0.22 e Å3
4062 reflectionsAbsolute structure: Flack (1983)
496 parametersAbsolute structure parameter: 0.04 (6)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.9625 (6)0.8438 (6)0.20055 (14)0.068 (2)
H10.95500.79060.21010.082*
C21.0515 (8)0.8480 (8)0.1830 (2)0.069 (3)
H21.06040.92120.17810.083*
C31.1559 (8)0.8122 (9)0.1955 (2)0.080 (3)
H31.21040.81440.18280.096*
C41.1871 (11)0.8854 (10)0.2153 (2)0.118 (4)
H4A1.19290.95460.20860.177*
H4B1.25320.86440.22200.177*
H4C1.13530.88490.22820.177*
C51.1512 (9)0.7035 (10)0.2049 (3)0.112 (4)
H5A1.11370.66140.19290.135*
H5B1.11070.70340.22010.135*
C61.2555 (11)0.6508 (12)0.2101 (3)0.166 (7)
H6A1.24350.58150.21630.248*
H6B1.29330.69050.22220.248*
H6C1.29550.64710.19510.248*
C71.0285 (8)0.7893 (8)0.1606 (2)0.060 (3)
N80.9578 (6)0.7187 (7)0.15750 (15)0.074 (2)
C90.9691 (7)0.6790 (8)0.1332 (2)0.072 (3)
H90.90600.69590.12370.086*
C101.0639 (9)0.7417 (9)0.1219 (2)0.080 (3)
H101.12140.69400.11800.096*
O111.0925 (5)0.8081 (5)0.14172 (13)0.0754 (19)
C121.0353 (9)0.8044 (10)0.0996 (2)0.106 (4)
H12A1.09600.83990.09350.158*
H12B0.98290.85470.10400.158*
H12C1.00840.75890.08700.158*
C130.9864 (9)0.5617 (10)0.1322 (3)0.084 (3)
O140.9925 (7)0.5193 (6)0.11106 (13)0.104 (3)
N150.9971 (7)0.5146 (7)0.15265 (18)0.076 (3)
H150.99240.54900.16630.091*
C161.0171 (8)0.4034 (8)0.1533 (2)0.075 (3)
H160.97690.36850.14030.090*
C171.1349 (8)0.3792 (8)0.1501 (2)0.093 (4)
H17A1.17370.41310.16320.112*
H17B1.15840.40810.13440.112*
C181.1592 (9)0.2605 (9)0.1505 (3)0.084 (3)
C191.1319 (10)0.2052 (13)0.1310 (3)0.120 (4)
H191.09340.24310.11950.144*
C201.148 (2)0.105 (2)0.1243 (9)0.28 (2)
H201.13050.07390.10930.335*
C211.199 (2)0.0540 (19)0.1457 (8)0.224 (19)
H211.21060.01760.14480.269*
C221.2310 (12)0.1028 (18)0.1664 (4)0.152 (8)
H221.26640.06600.17860.182*
C231.2098 (10)0.2130 (14)0.1696 (3)0.109 (5)
H231.22960.24920.18370.131*
C240.9773 (10)0.3649 (9)0.1801 (2)0.076 (3)
O251.0284 (6)0.3925 (7)0.19786 (17)0.122 (3)
N260.8920 (7)0.3075 (6)0.18148 (16)0.071 (2)
C270.8260 (8)0.2758 (7)0.1602 (2)0.074 (3)
H270.86710.23860.14770.089*
C280.7523 (9)0.2033 (8)0.1733 (2)0.088 (3)
H28A0.68590.20030.16470.106*
H28B0.78140.13340.17400.106*
C290.7385 (8)0.2453 (10)0.1981 (2)0.093 (3)
H29A0.71400.19200.20940.111*
H29B0.68950.30310.19810.111*
C300.8459 (9)0.2809 (8)0.20469 (18)0.083 (3)
H30A0.84330.34110.21560.099*
H30B0.88470.22550.21280.099*
C310.7705 (7)0.3716 (7)0.14883 (17)0.063 (3)
N320.7438 (6)0.4505 (6)0.16275 (13)0.057 (2)
C330.6961 (8)0.5222 (7)0.1475 (2)0.062 (3)
C340.6795 (8)0.4974 (7)0.1246 (2)0.080 (3)
H340.64360.53850.11320.096*
S350.7339 (2)0.37708 (18)0.11833 (5)0.0703 (8)
C360.6630 (9)0.6287 (9)0.1579 (2)0.080 (3)
O370.6245 (6)0.6958 (5)0.14532 (13)0.079 (2)
N380.6865 (6)0.6370 (5)0.18204 (14)0.067 (2)
H380.70910.58330.19000.080*
C390.6736 (7)0.7387 (7)0.19520 (17)0.065 (3)
H390.70210.79760.18580.077*
C400.5551 (8)0.7515 (9)0.2009 (2)0.095 (4)
H40A0.51570.74360.18570.114*
H40B0.53320.69690.21220.114*
C410.5316 (7)0.8559 (9)0.21206 (18)0.063 (3)
C420.5184 (9)0.9398 (12)0.1960 (2)0.091 (4)
H420.52460.92950.17910.109*
C430.4967 (12)1.0360 (15)0.2048 (4)0.128 (5)
H430.48691.09040.19360.154*
C440.4891 (11)1.0545 (13)0.2280 (5)0.128 (5)
H440.47291.12190.23310.154*
C450.5042 (9)0.9782 (18)0.2457 (3)0.119 (5)
H450.50220.99330.26250.143*
C460.5236 (8)0.8725 (11)0.2366 (2)0.086 (3)
H460.53030.81720.24770.103*
C470.7323 (8)0.7203 (9)0.2199 (2)0.074 (3)
O480.7307 (7)0.6391 (5)0.23082 (13)0.105 (3)
N490.7859 (6)0.8062 (6)0.22807 (14)0.067 (2)
C500.7940 (8)0.9103 (6)0.21684 (16)0.062 (3)
H500.73110.92840.20740.074*
C510.8063 (9)0.9805 (8)0.2407 (2)0.083 (3)
H51A0.84431.04380.23680.100*
H51B0.73820.99960.24720.100*
C520.8627 (11)0.9204 (9)0.2587 (2)0.104 (4)
H52A0.84520.94270.27540.125*
H52B0.93740.92770.25630.125*
C530.8264 (9)0.8011 (8)0.25414 (17)0.088 (3)
H53A0.88480.75310.25550.105*
H53B0.77210.78040.26570.105*
C540.8920 (8)0.9247 (9)0.20162 (18)0.062 (3)
O550.9054 (6)1.0044 (6)0.18901 (17)0.117 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.082 (6)0.057 (5)0.066 (5)0.007 (5)0.013 (5)0.013 (4)
C20.075 (8)0.059 (7)0.075 (7)0.001 (6)0.006 (7)0.001 (6)
C30.090 (9)0.080 (8)0.071 (7)0.005 (7)0.008 (7)0.014 (7)
C40.154 (12)0.121 (10)0.079 (8)0.014 (10)0.006 (8)0.022 (9)
C50.097 (9)0.112 (10)0.128 (11)0.006 (8)0.026 (8)0.014 (9)
C60.136 (12)0.156 (13)0.205 (17)0.056 (11)0.039 (13)0.047 (12)
C70.056 (6)0.054 (7)0.069 (8)0.014 (6)0.004 (7)0.019 (6)
N80.071 (6)0.081 (6)0.070 (6)0.001 (5)0.004 (5)0.021 (5)
C90.056 (7)0.074 (8)0.086 (8)0.000 (6)0.010 (6)0.008 (7)
C100.099 (9)0.078 (7)0.064 (7)0.037 (7)0.019 (7)0.009 (7)
O110.089 (5)0.084 (5)0.053 (4)0.003 (4)0.020 (4)0.004 (4)
C120.094 (9)0.124 (10)0.100 (9)0.008 (8)0.023 (8)0.009 (9)
C130.086 (9)0.086 (9)0.080 (10)0.004 (7)0.017 (8)0.016 (9)
O140.166 (8)0.090 (6)0.055 (5)0.002 (5)0.002 (5)0.010 (4)
N150.107 (7)0.063 (6)0.058 (6)0.001 (5)0.005 (6)0.014 (5)
C160.069 (8)0.063 (8)0.094 (9)0.003 (6)0.000 (7)0.025 (7)
C170.079 (8)0.081 (8)0.119 (10)0.005 (7)0.012 (8)0.033 (8)
C180.074 (8)0.077 (9)0.103 (10)0.024 (7)0.029 (8)0.020 (9)
C190.101 (10)0.087 (11)0.172 (14)0.002 (8)0.018 (11)0.025 (11)
C200.17 (2)0.12 (2)0.55 (7)0.054 (17)0.05 (3)0.04 (3)
C210.15 (2)0.115 (19)0.41 (5)0.057 (16)0.19 (3)0.13 (3)
C220.119 (14)0.118 (15)0.22 (2)0.033 (12)0.097 (15)0.097 (15)
C230.084 (9)0.148 (16)0.095 (9)0.013 (9)0.032 (8)0.036 (10)
C240.067 (8)0.068 (8)0.094 (10)0.015 (7)0.007 (8)0.002 (7)
O250.103 (6)0.155 (8)0.108 (7)0.045 (6)0.043 (6)0.013 (6)
N260.071 (6)0.071 (6)0.070 (6)0.002 (5)0.011 (5)0.005 (5)
C270.072 (7)0.058 (7)0.093 (7)0.005 (6)0.029 (7)0.002 (7)
C280.092 (9)0.070 (7)0.104 (9)0.004 (7)0.040 (8)0.022 (8)
C290.060 (7)0.119 (10)0.098 (9)0.014 (7)0.023 (7)0.006 (8)
C300.100 (9)0.091 (8)0.057 (6)0.005 (7)0.005 (7)0.024 (6)
C310.077 (7)0.049 (6)0.061 (6)0.000 (6)0.020 (6)0.007 (6)
N320.076 (5)0.048 (5)0.048 (4)0.015 (4)0.007 (4)0.003 (4)
C330.081 (7)0.046 (6)0.059 (7)0.016 (6)0.013 (6)0.017 (6)
C340.100 (8)0.043 (6)0.097 (9)0.010 (5)0.016 (8)0.016 (6)
S350.085 (2)0.0591 (15)0.0668 (15)0.0033 (14)0.0115 (15)0.0027 (15)
C360.086 (8)0.059 (8)0.094 (10)0.023 (7)0.008 (8)0.009 (8)
O370.118 (6)0.053 (4)0.067 (4)0.007 (4)0.024 (4)0.002 (4)
N380.090 (6)0.049 (5)0.061 (5)0.001 (5)0.021 (5)0.002 (5)
C390.063 (6)0.052 (6)0.079 (7)0.003 (5)0.006 (6)0.015 (6)
C400.086 (8)0.094 (9)0.106 (8)0.015 (7)0.022 (7)0.034 (8)
C410.068 (7)0.079 (8)0.041 (6)0.007 (6)0.002 (5)0.002 (6)
C420.093 (9)0.096 (9)0.084 (9)0.006 (8)0.003 (7)0.002 (9)
C430.140 (13)0.129 (16)0.115 (14)0.028 (11)0.034 (11)0.003 (12)
C440.109 (12)0.103 (12)0.172 (17)0.030 (9)0.023 (13)0.016 (14)
C450.069 (9)0.199 (17)0.090 (10)0.017 (11)0.012 (8)0.024 (13)
C460.080 (8)0.113 (10)0.066 (8)0.024 (7)0.007 (7)0.013 (7)
C470.068 (7)0.078 (8)0.077 (8)0.013 (7)0.029 (6)0.026 (7)
O480.176 (8)0.050 (4)0.088 (5)0.027 (5)0.003 (5)0.027 (4)
N490.067 (5)0.070 (6)0.064 (5)0.002 (5)0.002 (5)0.002 (5)
C500.095 (8)0.041 (5)0.049 (5)0.001 (5)0.022 (6)0.004 (5)
C510.089 (8)0.072 (7)0.089 (8)0.002 (6)0.002 (7)0.025 (7)
C520.138 (11)0.096 (9)0.079 (8)0.007 (8)0.038 (8)0.034 (7)
C530.108 (8)0.096 (8)0.060 (7)0.014 (7)0.034 (6)0.007 (6)
C540.069 (7)0.071 (8)0.047 (6)0.012 (6)0.003 (6)0.012 (6)
O550.108 (6)0.100 (6)0.143 (8)0.021 (4)0.032 (5)0.067 (6)
Geometric parameters (Å, º) top
N1—C541.375 (11)C27—C311.545 (12)
N1—C21.484 (12)C28—C291.455 (14)
C2—C71.453 (13)C29—C301.492 (13)
C2—C31.566 (13)C31—N321.304 (10)
C3—C41.479 (13)C31—S351.714 (9)
C3—C51.483 (14)N32—C331.375 (11)
C5—C61.523 (14)C33—C341.297 (13)
C7—N81.289 (11)C33—C361.533 (14)
C7—O111.332 (10)C34—S351.725 (10)
N8—C91.417 (11)C36—O371.200 (12)
C9—C131.519 (14)C36—N381.345 (12)
C9—C101.576 (13)N38—C391.493 (10)
C10—O111.415 (12)C39—C471.550 (13)
C10—C121.492 (14)C39—C401.557 (13)
C13—N151.264 (13)C40—C411.498 (14)
C13—O141.269 (12)C41—C461.347 (13)
N15—C161.447 (11)C41—C421.390 (13)
C16—C171.550 (13)C42—C431.348 (17)
C16—C241.610 (15)C43—C441.28 (2)
C17—C181.552 (15)C44—C451.381 (19)
C18—C191.314 (16)C45—C461.460 (18)
C18—C231.361 (15)C47—O481.195 (11)
C19—C201.35 (3)C47—N491.369 (11)
C20—C211.48 (5)N49—C501.468 (10)
C21—C221.34 (3)N49—C531.502 (11)
C22—C231.45 (2)C50—C541.512 (13)
C24—O251.214 (13)C50—C511.581 (12)
C24—N261.318 (12)C51—C521.434 (13)
N26—C301.427 (12)C52—C531.616 (13)
N26—C271.484 (11)C54—O551.239 (10)
C27—C281.500 (13)
C54—N1—C2120.3 (8)C29—C28—C27106.3 (9)
C7—C2—N1110.9 (8)C28—C29—C30102.8 (9)
C7—C2—C3112.3 (8)N26—C30—C29104.1 (9)
N1—C2—C3111.6 (8)N32—C31—C27120.4 (8)
C4—C3—C5111.0 (10)N32—C31—S35116.8 (6)
C4—C3—C2110.9 (9)C27—C31—S35122.7 (8)
C5—C3—C2112.9 (9)C31—N32—C33106.8 (7)
C3—C5—C6116.4 (11)C34—C33—N32118.7 (9)
N8—C7—O11117.3 (10)C34—C33—C36121.3 (11)
N8—C7—C2127.9 (10)N32—C33—C36120.0 (9)
O11—C7—C2114.7 (10)C33—C34—S35109.8 (8)
C7—N8—C9107.5 (9)C31—S35—C3487.6 (5)
N8—C9—C13113.6 (10)O37—C36—N38125.7 (10)
N8—C9—C10104.6 (8)O37—C36—C33123.1 (10)
C13—C9—C10112.3 (9)N38—C36—C33111.2 (11)
O11—C10—C12110.5 (9)C36—N38—C39120.4 (8)
O11—C10—C9102.4 (7)N38—C39—C47102.9 (7)
C12—C10—C9113.3 (9)N38—C39—C40107.0 (7)
C7—O11—C10108.1 (8)C47—C39—C40108.6 (8)
N15—C13—O14125.1 (11)C41—C40—C39111.6 (8)
N15—C13—C9117.4 (11)C46—C41—C42118.8 (11)
O14—C13—C9117.5 (12)C46—C41—C40123.6 (11)
C13—N15—C16120.7 (10)C42—C41—C40117.6 (10)
N15—C16—C17111.5 (9)C43—C42—C41120.9 (13)
N15—C16—C24105.6 (8)C44—C43—C42122.0 (17)
C17—C16—C24110.4 (9)C43—C44—C45122.4 (16)
C16—C17—C18113.0 (9)C44—C45—C46116.7 (13)
C19—C18—C23119.5 (13)C41—C46—C45119.3 (12)
C19—C18—C17117.5 (15)O48—C47—N49123.3 (9)
C23—C18—C17123.0 (14)O48—C47—C39123.3 (9)
C18—C19—C20133 (2)N49—C47—C39113.4 (10)
C19—C20—C21106 (4)C47—N49—C50129.2 (8)
C22—C21—C20125 (3)C47—N49—C53116.1 (8)
C21—C22—C23120 (2)C50—N49—C53113.7 (7)
C18—C23—C22115.8 (15)N49—C50—C54113.2 (8)
O25—C24—N26124.2 (12)N49—C50—C51100.7 (7)
O25—C24—C16116.8 (11)C54—C50—C51106.9 (8)
N26—C24—C16119.0 (11)C52—C51—C50107.4 (8)
C24—N26—C30121.8 (10)C51—C52—C53105.0 (9)
C24—N26—C27125.5 (10)N49—C53—C52101.7 (8)
C30—N26—C27112.3 (8)O55—C54—N1120.4 (9)
N26—C27—C2899.4 (8)O55—C54—C50120.9 (9)
N26—C27—C31110.7 (8)N1—C54—C50118.4 (9)
C28—C27—C31112.9 (8)
C54—N1—C2—C797.9 (10)C27—C31—N32—C33179.7 (8)
N1—C2—C7—N818.5 (15)C31—N32—C33—C36175.1 (9)
C2—C7—N8—C9176.3 (10)N32—C33—C36—N380.3 (13)
C7—N8—C9—C100.1 (11)C33—C36—N38—C39172.3 (8)
N8—C9—C13—N155.5 (15)C36—N38—C39—C47167.3 (9)
C9—C13—N15—C16178.1 (10)N38—C39—C47—N49142.5 (8)
C13—N15—C16—C24156.2 (11)C39—C47—N49—C500.4 (14)
N15—C16—C24—N26109.0 (11)C47—N49—C50—C5497.2 (11)
C16—C24—N26—C271.4 (15)N49—C50—C54—N12.2 (12)
C24—N26—C27—C3167.7 (13)C2—N1—C54—C50170.9 (8)
N26—C27—C31—N3231.5 (12)

Experimental details

Crystal data
Chemical formulaC41H49N7O6S
Mr767.93
Crystal system, space groupTetragonal, P41212
Temperature (K)293
a, c (Å)12.805 (2), 54.013 (11)
V3)8857 (3)
Z8
Radiation typeCu Kα
µ (mm1)1.06
Crystal size (mm)0.26 × 0.17 × 0.06
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.78, 0.97
No. of measured, independent and
observed [I > 2σ(I)] reflections
4364, 4062, 2203
Rint0.194
θmax (°)56.0
(sin θ/λ)max1)0.538
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.098, 0.155, 1.69
No. of reflections4062
No. of parameters496
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.22
Absolute structureFlack (1983)
Absolute structure parameter0.04 (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).

Selected torsion angles (º) top
C54—N1—C2—C797.9 (10)C27—C31—N32—C33179.7 (8)
N1—C2—C7—N818.5 (15)C31—N32—C33—C36175.1 (9)
C2—C7—N8—C9176.3 (10)N32—C33—C36—N380.3 (13)
C7—N8—C9—C100.1 (11)C33—C36—N38—C39172.3 (8)
N8—C9—C13—N155.5 (15)C36—N38—C39—C47167.3 (9)
C9—C13—N15—C16178.1 (10)N38—C39—C47—N49142.5 (8)
C13—N15—C16—C24156.2 (11)C39—C47—N49—C500.4 (14)
N15—C16—C24—N26109.0 (11)C47—N49—C50—C5497.2 (11)
C16—C24—N26—C271.4 (15)N49—C50—C54—N12.2 (12)
C24—N26—C27—C3167.7 (13)C2—N1—C54—C50170.9 (8)
N26—C27—C31—N3231.5 (12)
 

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