Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101279X/wn6037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101279X/wn6037Isup2.hkl |
CCDC reference: 172205
Key indicators
- Single-crystal synchrotron study
- T = 100 K
- Mean (C-C) = 0.015 Å
- Disorder in main residue
- R factor = 0.097
- wR factor = 0.259
- Data-to-parameter ratio = 8.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
PLAT_420 Alert B D-H Without Acceptor O(124) - H(134) ?
Alert Level C:
DIFMN_02 Alert C The minimum difference density is < -0.1*ZMAX*0.75 _refine_diff_density_min given = -1.214 Test value = -1.200 DIFMN_03 Alert C The minimum difference density is < -0.1*ZMAX*0.75 The relevant atom site should be identified. DIFMX_01 Alert C The maximum difference density is > 0.1*ZMAX*0.75 _refine_diff_density_max given = 1.515 Test value = 1.200 DIFMX_02 Alert C The minimum difference density is > 0.1*ZMAX*0.75 The relevant atom site should be identified. REFLT_03 From the CIF: _diffrn_reflns_theta_max 30.25 From the CIF: _reflns_number_total 8977 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 9641 Completeness (_total/calc) 93.11% Alert C: < 95% complete RFACR_01 Alert C The value of the weighted R factor is > 0.25 Weighted R factor given 0.259 PLAT_202 Alert C Isotropic non-H Atoms in Anion/Solvent = 2 PLAT_213 Alert C Atom O39 has ADP max/min Ratio ........... 3.10 PLAT_213 Alert C Atom C5 has ADP max/min Ratio ........... 3.50 PLAT_213 Alert C Atom C31 has ADP max/min Ratio ........... 3.60 PLAT_213 Alert C Atom C45 has ADP max/min Ratio ........... 3.20 PLAT_213 Alert C Atom C57 has ADP max/min Ratio ........... 3.30 PLAT_213 Alert C Atom C58 has ADP max/min Ratio ........... 3.10 PLAT_213 Alert C Atom C67 has ADP max/min Ratio ........... 3.20 PLAT_214 Alert C Atom N121 (Anion/Solvent) ADP max/min Ratio 4.30 PLAT_301 Alert C Main Residue Disorder ........................ 1.00 Perc. PLAT_320 Alert C Check Hybridisation of S(25) in main residue ? PLAT_320 Alert C Check Hybridisation of S(52) in main residue ? PLAT_320 Alert C Check Hybridisation of S(79) in main residue ? PLAT_320 Alert C Check Hybridisation of S(106) in main residue ? PLAT_367 Alert C Long? C(sp?)-C(sp?) Bond C(45) - C(46) = 1.70 Ang. General Notes
ABSMU_01 Radiation type not identified. Calculation of _exptl_absorpt_correction_mu not performed. REFLT_03 From the CIF: _diffrn_reflns_theta_max 30.25 From the CIF: _reflns_number_total 8977 Count of symmetry unique reflns 9641 Completeness (_total/calc) 93.11% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
21 Alert Level C = Please check
dASC and dASC2 analogues were synthesized by a previously reported method (Hamada et al., 1987). Dimerization of dASC was controlled by the concentration of starting linear peptides. The cyclization reaction was performed in 10mM of the linear peptide, but dimerization mainly occurred above this concentration. dASC2 analogues (ca 20 mg) were dissolved in DMF (0.2 ml), and water was added to the solution just before the solution became unclear. The aqueous DMF solution was sealed in vials at room temperature. A crystal was mounted on a nylon loop in the mother liquor, and frozen under a nitrogen stream (100 K).
A total of 90 images with oscillation-angle of 2° were measured on a synchrotron using RAXIS-IV, and the first 87 frames were processed by MOSFLM (Leslie, 1999). The 37199 observed reflections were successively processed by the CCP4 program suite (1994), and the reflections were merged to 17325 reflections with an Rmerg value of 0.060. The structure was solved using all reflections. H atoms of the peptide were positioned at calculated positions and constrained during the refinement. H atoms of the water molecules were positioned by considering the hydrogen-bonding networks and fixed during the refinement. The resolution of the diffraction data was 0.80 Å, but reflections of 0.83–0.80 Å resolution were omitted in the final refinement stage because of the higher R value of that shell. Disorder was observed in the D-Val7 side chain, relating to the rotation of the Cα-Cβ bond. The occupancies of the two disordered sites were 0.59 and 0.41.
Data collection: PROCESS (Higashi, 1996); cell refinement: MOSFLM (Leslie, 1999); data reduction: MOSFLM; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: PARST (Nardelli, 1995).
C72H112N16O16S4·3C3H7NO·H2O | Z = 2 |
Mr = 1823.32 | F(000) = 1956 |
Monoclinic, P21 | Dx = 1.222 Mg m−3 |
a = 11.5563 (1) Å | Synchrotron radiation, λ = 0.83600 Å |
b = 9.9957 (2) Å | µ = 0.17 mm−1 |
c = 42.9208 (10) Å | T = 100 K |
β = 91.3492 (15)° | Cubic, colorless |
V = 4956.55 (16) Å3 | 0.01 × 0.01 × 0.01 mm |
Rigaku RAXIS-IV diffractometer | 8977 independent reflections |
Radiation source: double monochromated beam | 8890 reflections with I > 2σ(I) |
Diamond monochromator | Rint = 0.038 |
Detector resolution: 10 pixels mm-1 | θmax = 30.3°, θmin = 2.6° |
oscillation scans | h = −13→13 |
Absorption correction: for a cylinder mounted on the ϕ axis (CYLABS; Nardelli, 1998) | k = −11→12 |
Tmin = 0.657, Tmax = 0.661 | l = 0→51 |
15629 measured reflections |
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)] = 0.097 | H-atom parameters constrained |
wR(F2) = 0.259 | w = 1/[σ2(Fo2) + (0.1312P)2 + 5.0564P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max = 0.017 |
8977 reflections | Δρmax = 1.52 e Å−3 |
1119 parameters | Δρmin = −1.21 e Å−3 |
4 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.17 (14) |
C72H112N16O16S4·3C3H7NO·H2O | V = 4956.55 (16) Å3 |
Mr = 1823.32 | Z = 2 |
Monoclinic, P21 | Synchrotron radiation, λ = 0.83600 Å |
a = 11.5563 (1) Å | µ = 0.17 mm−1 |
b = 9.9957 (2) Å | T = 100 K |
c = 42.9208 (10) Å | 0.01 × 0.01 × 0.01 mm |
β = 91.3492 (15)° |
Rigaku RAXIS-IV diffractometer | 8977 independent reflections |
Absorption correction: for a cylinder mounted on the ϕ axis (CYLABS; Nardelli, 1998) | 8890 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.661 | Rint = 0.038 |
15629 measured reflections |
R[F2 > 2σ(F2)] = 0.097 | H-atom parameters constrained |
wR(F2) = 0.259 | Δρmax = 1.52 e Å−3 |
S = 1.25 | Δρmin = −1.21 e Å−3 |
8977 reflections | Absolute structure: Flack (1983) |
1119 parameters | Absolute structure parameter: −0.17 (14) |
4 restraints |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 0.3629 x + 9.7478 y + 9.4330 z = 10.7033 * -0.0033 C21 * 0.0057 N22 * -0.0058 C23 * 0.0033 C24 * 0.0000 S25 Rms deviation of fitted atoms = 0.0042 - 10.6859 x - 0.3847 y + 17.1882 z = 10.9015 Angle to previous plane = 85.73 Thz4-Thz8 * -0.0022 C48 * 0.0093 N49 * -0.0136 C50 * 0.0107 C51 * -0.0043 S52 Rms deviation of fitted atoms = 0.0091 - 3.4107 x + 9.5134 y - 3.3086 z = 6.5795 Angle to previous plane = 78.20 Thz8-Thz12 * -0.0075 C75 * -0.0055 N76 * 0.0202 C77 * -0.0216 C78 * 0.0144 S79 Rms deviation of fitted atoms = 0.0153 - 0.3629 x + 9.7478 y + 9.4330 z = 10.7033 Angle to previous plane = 23.22 Thz12-Thz4 * -0.0033 C21 * 0.0057 N22 * -0.0058 C23 * 0.0033 C24 * 0.0000 S25 Rms deviation of fitted atoms = 0.0042 10.6609 x + 0.1294 y - 17.4834 z = 2.4178 Angle to previous plane = 84.21 Thz4-Thz16 * -0.0053 C102 * 0.0054 N103 * -0.0024 C104 * -0.0007 C105 * 0.0029 S106 Rms deviation of fitted atoms = 0.0038 - 3.4107 x + 9.5134 y - 3.3086 z = 6.5795 Angle to previous plane = 76.85 Thz16-Thz12 * -0.0075 C75 * -0.0055 N76 * 0.0202 C77 * -0.0216 C78 * 0.0144 S79 Rms deviation of fitted atoms = 0.0153 - 10.6859 x - 0.3847 y + 17.1882 z = 10.9015 Angle to previous plane = 78.20 Thz12-Thz8 * -0.0022 C48 * 0.0093 N49 * -0.0136 C50 * 0.0107 C51 * -0.0043 S52 Rms deviation of fitted atoms = 0.0091 10.6609 x + 0.1294 y - 17.4834 z = 2.4178 Angle to previous plane = 1.52 Thz8-Thz16 * -0.0053 C102 * 0.0054 N103 * -0.0024 C104 * -0.0007 C105 * 0.0029 S106 Rms deviation of fitted atoms = 0.0038 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.3244 (4) | 1.1096 (5) | 0.06135 (14) | 0.0349 (12) | |
H1 | 0.3440 | 1.0266 | 0.0607 | 0.042* | |
C2 | 0.2624 (5) | 1.1671 (6) | 0.03467 (19) | 0.0385 (16) | |
H2 | 0.2326 | 1.2546 | 0.0409 | 0.046* | |
C3 | 0.3359 (7) | 1.1875 (11) | 0.0059 (2) | 0.064 (3) | |
H3 | 0.2868 | 1.2321 | −0.0098 | 0.077* | |
C4 | 0.3744 (9) | 1.0584 (15) | −0.0079 (2) | 0.083 (4) | |
H4 | 0.3095 | 0.9969 | −0.0086 | 0.099* | |
H5 | 0.4340 | 1.0197 | 0.0056 | 0.099* | |
C5 | 0.4368 (7) | 1.2776 (13) | 0.0126 (4) | 0.098 (5) | |
H6 | 0.4100 | 1.3596 | 0.0216 | 0.098* | |
H7 | 0.4754 | 1.2968 | −0.0065 | 0.098* | |
H8 | 0.4898 | 1.2344 | 0.0269 | 0.098* | |
C6 | 0.4221 (12) | 1.073 (2) | −0.0410 (3) | 0.131 (8) | |
H9 | 0.4452 | 0.9865 | −0.0485 | 0.131* | |
H10 | 0.4878 | 1.1316 | −0.0404 | 0.131* | |
H11 | 0.3631 | 1.1089 | −0.0547 | 0.131* | |
C7 | 0.1594 (5) | 1.0770 (6) | 0.02725 (13) | 0.0269 (12) | |
O8 | 0.1611 (4) | 0.9568 (4) | 0.03542 (9) | 0.0294 (9) | |
N9 | 0.0721 (4) | 1.1309 (5) | 0.01103 (11) | 0.0255 (10) | |
H12 | 0.0750 | 1.2142 | 0.0061 | 0.031* | |
C10 | −0.0278 (5) | 1.0527 (6) | 0.00139 (13) | 0.0249 (11) | |
H13 | −0.0019 | 0.9845 | −0.0133 | 0.030* | |
C11 | −0.1147 (5) | 1.1446 (6) | −0.01612 (13) | 0.0293 (12) | |
H14 | −0.0757 | 1.1848 | −0.0339 | 0.035* | |
O12 | −0.1452 (4) | 1.2483 (4) | 0.00487 (10) | 0.0307 (9) | |
H15 | −0.1543 | 1.3181 | −0.0050 | 0.031* | |
C13 | −0.2232 (6) | 1.0727 (8) | −0.02822 (16) | 0.0407 (15) | |
H16 | −0.2734 | 1.1356 | −0.0386 | 0.041* | |
H17 | −0.2626 | 1.0333 | −0.0110 | 0.041* | |
H18 | −0.2017 | 1.0038 | −0.0426 | 0.041* | |
C14 | −0.0847 (4) | 0.9809 (5) | 0.02840 (11) | 0.0191 (10) | |
O15 | −0.1202 (3) | 0.8648 (4) | 0.02536 (9) | 0.0260 (8) | |
N16 | −0.0972 (4) | 1.0524 (5) | 0.05514 (10) | 0.0213 (9) | |
H19 | −0.0683 | 1.1315 | 0.0566 | 0.026* | |
C17 | −0.1592 (4) | 0.9960 (6) | 0.08137 (12) | 0.0246 (11) | |
H20 | −0.1771 | 0.9033 | 0.0756 | 0.030* | |
C18 | −0.2759 (6) | 1.0641 (8) | 0.08651 (16) | 0.0419 (17) | |
H21 | −0.3079 | 1.0281 | 0.1057 | 0.050* | |
C19 | −0.3589 (7) | 1.0274 (16) | 0.05931 (18) | 0.076 (4) | |
H22 | −0.3638 | 0.9318 | 0.0575 | 0.076* | |
H23 | −0.3303 | 1.0641 | 0.0403 | 0.076* | |
H24 | −0.4342 | 1.0634 | 0.0631 | 0.076* | |
C20 | −0.2637 (11) | 1.2135 (11) | 0.0902 (3) | 0.082 (4) | |
H25 | −0.3386 | 1.2523 | 0.0933 | 0.082* | |
H26 | −0.2306 | 1.2506 | 0.0718 | 0.082* | |
H27 | −0.2143 | 1.2326 | 0.1080 | 0.082* | |
C21 | −0.0809 (5) | 0.9882 (6) | 0.11003 (12) | 0.0258 (11) | |
N22 | −0.1183 (5) | 0.9611 (6) | 0.13760 (11) | 0.0347 (12) | |
C23 | −0.0259 (6) | 0.9436 (10) | 0.15802 (14) | 0.0458 (19) | |
C24 | 0.0797 (6) | 0.9600 (10) | 0.14601 (14) | 0.049 (2) | |
H28 | 0.1491 | 0.9524 | 0.1573 | 0.059* | |
S25 | 0.06873 (13) | 0.9967 (2) | 0.10733 (3) | 0.0381 (4) | |
C26 | −0.0474 (7) | 0.9103 (12) | 0.19168 (16) | 0.058 (3) | |
O27 | 0.0363 (5) | 0.8948 (10) | 0.20993 (11) | 0.078 (3) | |
N28 | −0.1567 (6) | 0.9076 (10) | 0.20027 (13) | 0.060 (2) | |
H29 | −0.2103 | 0.9148 | 0.1861 | 0.072* | |
C29 | −0.1899 (8) | 0.8931 (14) | 0.23256 (16) | 0.068 (3) | |
H30 | −0.1242 | 0.8550 | 0.2444 | 0.081* | |
C30 | −0.2200 (12) | 1.0276 (17) | 0.2470 (2) | 0.090 (4) | |
H31 | −0.2769 | 1.0735 | 0.2335 | 0.107* | |
C31 | −0.268 (3) | 1.014 (3) | 0.2795 (3) | 0.190 (12) | |
H32 | −0.3336 | 0.9554 | 0.2789 | 0.190* | |
H33 | −0.2911 | 1.1006 | 0.2868 | 0.190* | |
H34 | −0.2092 | 0.9782 | 0.2933 | 0.190* | |
C32 | −0.113 (2) | 1.120 (3) | 0.2523 (5) | 0.154 (9) | |
H35 | −0.0467 | 1.0688 | 0.2600 | 0.184* | |
H36 | −0.0926 | 1.1648 | 0.2332 | 0.184* | |
C33 | −0.152 (2) | 1.220 (3) | 0.2767 (5) | 0.164 (10) | |
H37 | −0.0993 | 1.2938 | 0.2775 | 0.164* | |
H38 | −0.1534 | 1.1770 | 0.2967 | 0.164* | |
H39 | −0.2283 | 1.2514 | 0.2712 | 0.164* | |
C34 | −0.2928 (6) | 0.7976 (14) | 0.23504 (14) | 0.063 (3) | |
O35 | −0.3766 (6) | 0.7999 (12) | 0.21688 (12) | 0.086 (3) | |
N36 | −0.2840 (6) | 0.7119 (10) | 0.25932 (14) | 0.057 (2) | |
H40 | −0.2183 | 0.7044 | 0.2690 | 0.069* | |
C37 | −0.3803 (7) | 0.6318 (12) | 0.26982 (19) | 0.060 (2) | |
H41 | −0.4528 | 0.6735 | 0.2626 | 0.072* | |
C38 | −0.3758 (11) | 0.4933 (18) | 0.2577 (3) | 0.104 (5) | |
H42 | −0.2986 | 0.4561 | 0.2619 | 0.125* | |
O39 | −0.3963 (12) | 0.502 (2) | 0.2235 (3) | 0.178 (8) | |
H43 | −0.3677 | 0.4321 | 0.2158 | 0.178* | |
C40 | −0.4656 (13) | 0.4025 (16) | 0.2717 (4) | 0.103 (5) | |
H44 | −0.4573 | 0.3137 | 0.2636 | 0.103* | |
H45 | −0.5417 | 0.4355 | 0.2666 | 0.103* | |
H46 | −0.4549 | 0.4006 | 0.2940 | 0.103* | |
C41 | −0.3747 (6) | 0.6354 (9) | 0.30591 (17) | 0.0479 (18) | |
O42 | −0.2819 (5) | 0.6183 (10) | 0.31941 (14) | 0.072 (2) | |
N43 | −0.4729 (5) | 0.6618 (7) | 0.31967 (13) | 0.0444 (15) | |
H47 | −0.5352 | 0.6729 | 0.3086 | 0.053* | |
C44 | −0.4762 (8) | 0.6724 (9) | 0.35366 (17) | 0.0501 (19) | |
H48 | −0.4072 | 0.6265 | 0.3620 | 0.060* | |
C45 | −0.5805 (19) | 0.604 (2) | 0.3679 (4) | 0.146 (10) | |
H49 | −0.6458 | 0.6165 | 0.3532 | 0.175* | |
C46 | −0.5503 (18) | 0.4379 (15) | 0.3683 (4) | 0.112 (5) | |
H50 | −0.6153 | 0.3896 | 0.3761 | 0.112* | |
H51 | −0.4835 | 0.4217 | 0.3815 | 0.112* | |
H52 | −0.5348 | 0.4085 | 0.3475 | 0.112* | |
C47 | −0.620 (2) | 0.624 (2) | 0.3957 (4) | 0.091 (7) | 0.59 (3) |
H53 | −0.6914 | 0.5748 | 0.3979 | 0.091* | 0.59 (3) |
H54 | −0.6347 | 0.7173 | 0.3987 | 0.091* | 0.59 (3) |
H55 | −0.5647 | 0.5931 | 0.4110 | 0.091* | 0.59 (3) |
C47' | −0.6833 (18) | 0.625 (2) | 0.3582 (4) | 0.043 (6) | 0.41 (3) |
H53' | −0.7359 | 0.5736 | 0.3703 | 0.043* | 0.41 (3) |
H54' | −0.6907 | 0.6001 | 0.3367 | 0.043* | 0.41 (3) |
H55' | −0.7010 | 0.7187 | 0.3604 | 0.043* | 0.41 (3) |
C48 | −0.4651 (6) | 0.8186 (8) | 0.36330 (15) | 0.0402 (15) | |
N49 | −0.4245 (5) | 0.8579 (6) | 0.39010 (13) | 0.0365 (12) | |
C50 | −0.4246 (6) | 0.9966 (8) | 0.39179 (17) | 0.0430 (16) | |
C51 | −0.4699 (10) | 1.0608 (10) | 0.3665 (2) | 0.065 (3) | |
H56 | −0.4782 | 1.1530 | 0.3646 | 0.079* | |
S52 | −0.5092 (3) | 0.9470 (3) | 0.33864 (5) | 0.0663 (7) | |
C53 | −0.3778 (7) | 1.0676 (8) | 0.42048 (17) | 0.0424 (16) | |
O54 | −0.3719 (7) | 1.1901 (6) | 0.42159 (16) | 0.0681 (18) | |
N55 | −0.3467 (4) | 0.9860 (6) | 0.44366 (12) | 0.0350 (12) | |
H57 | −0.3637 | 0.9026 | 0.4418 | 0.042* | |
C56 | −0.2853 (6) | 1.0293 (8) | 0.47217 (16) | 0.0399 (16) | |
H58 | −0.2562 | 1.1203 | 0.4690 | 0.048* | |
C57 | −0.3617 (9) | 1.0291 (18) | 0.5011 (2) | 0.108 (7) | |
H59 | −0.3089 | 1.0560 | 0.5182 | 0.130* | |
C58 | −0.4495 (9) | 1.1380 (18) | 0.4996 (3) | 0.113 (7) | |
H60 | −0.4152 | 1.2174 | 0.4913 | 0.113* | |
H61 | −0.4766 | 1.1561 | 0.5202 | 0.113* | |
H62 | −0.5134 | 1.1108 | 0.4864 | 0.113* | |
C59 | −0.4137 (13) | 0.900 (2) | 0.5122 (3) | 0.117 (6) | |
H63 | −0.4921 | 0.9130 | 0.5193 | 0.140* | |
H64 | −0.4132 | 0.8319 | 0.4962 | 0.140* | |
C60 | −0.3349 (16) | 0.869 (2) | 0.5378 (3) | 0.133 (7) | |
H65 | −0.3572 | 0.7858 | 0.5471 | 0.133* | |
H66 | −0.3372 | 0.9388 | 0.5531 | 0.133* | |
H67 | −0.2578 | 0.8612 | 0.5301 | 0.133* | |
C61 | −0.1829 (5) | 0.9363 (7) | 0.47664 (13) | 0.0286 (12) | |
O62 | −0.1861 (4) | 0.8190 (5) | 0.46723 (10) | 0.0353 (10) | |
N63 | −0.0903 (4) | 0.9887 (5) | 0.49189 (11) | 0.0283 (10) | |
H68 | −0.0894 | 1.0731 | 0.4959 | 0.034* | |
C64 | 0.0086 (5) | 0.9068 (7) | 0.50188 (13) | 0.0295 (12) | |
H69 | −0.0188 | 0.8345 | 0.5152 | 0.035* | |
C65 | 0.0916 (7) | 0.9958 (7) | 0.52100 (15) | 0.0425 (16) | |
H70 | 0.0481 | 1.0382 | 0.5377 | 0.051* | |
O66 | 0.1297 (4) | 1.0984 (5) | 0.50017 (11) | 0.0390 (11) | |
H71 | 0.1467 | 1.1656 | 0.5104 | 0.039* | |
C67 | 0.1921 (10) | 0.9200 (11) | 0.5357 (3) | 0.078 (4) | |
H72 | 0.2409 | 0.9809 | 0.5472 | 0.078* | |
H73 | 0.2360 | 0.8782 | 0.5196 | 0.078* | |
H74 | 0.1633 | 0.8527 | 0.5494 | 0.078* | |
C68 | 0.0716 (5) | 0.8459 (6) | 0.47454 (12) | 0.0259 (12) | |
O69 | 0.1223 (4) | 0.7369 (5) | 0.47813 (11) | 0.0394 (11) | |
N70 | 0.0740 (4) | 0.9157 (5) | 0.44821 (10) | 0.0265 (10) | |
H75 | 0.0340 | 0.9880 | 0.4466 | 0.032* | |
C71 | 0.1431 (5) | 0.8725 (8) | 0.42167 (12) | 0.0344 (14) | |
H76 | 0.1747 | 0.7845 | 0.4272 | 0.041* | |
C72 | 0.2471 (7) | 0.9631 (12) | 0.41591 (17) | 0.058 (2) | |
H77 | 0.2873 | 0.9261 | 0.3980 | 0.070* | |
C73 | 0.3317 (8) | 0.9574 (19) | 0.4438 (2) | 0.091 (5) | |
H78 | 0.3504 | 0.8658 | 0.4484 | 0.091* | |
H79 | 0.2967 | 0.9976 | 0.4616 | 0.091* | |
H80 | 0.4010 | 1.0052 | 0.4389 | 0.091* | |
C74 | 0.2152 (12) | 1.1039 (15) | 0.4079 (3) | 0.089 (4) | |
H81 | 0.2842 | 1.1549 | 0.4045 | 0.089* | |
H82 | 0.1732 | 1.1427 | 0.4247 | 0.089* | |
H83 | 0.1676 | 1.1047 | 0.3892 | 0.089* | |
C75 | 0.0653 (6) | 0.8511 (8) | 0.39358 (14) | 0.0383 (15) | |
N76 | 0.1034 (5) | 0.8551 (8) | 0.36525 (12) | 0.0436 (15) | |
C77 | 0.0140 (7) | 0.8185 (12) | 0.34446 (16) | 0.058 (2) | |
C78 | −0.0874 (7) | 0.7822 (14) | 0.35704 (16) | 0.065 (3) | |
H84 | −0.1518 | 0.7508 | 0.3459 | 0.078* | |
S79 | −0.07962 (16) | 0.8025 (3) | 0.39670 (4) | 0.0538 (6) | |
C80 | 0.0395 (7) | 0.8194 (13) | 0.31066 (15) | 0.059 (3) | |
O81 | −0.0342 (5) | 0.7849 (12) | 0.29068 (12) | 0.085 (3) | |
N82 | 0.1460 (5) | 0.8616 (10) | 0.30400 (13) | 0.0545 (19) | |
H85 | 0.1942 | 0.8718 | 0.3194 | 0.065* | |
C83 | 0.1875 (7) | 0.8919 (11) | 0.27283 (15) | 0.055 (2) | |
H86 | 0.1206 | 0.9028 | 0.2586 | 0.066* | |
C84 | 0.2555 (9) | 1.0218 (13) | 0.2737 (2) | 0.068 (3) | |
H87 | 0.3190 | 1.0099 | 0.2890 | 0.081* | |
C85 | 0.3103 (12) | 1.0470 (15) | 0.2422 (2) | 0.085 (4) | |
H88 | 0.3560 | 0.9709 | 0.2366 | 0.085* | |
H89 | 0.3590 | 1.1248 | 0.2436 | 0.085* | |
H90 | 0.2506 | 1.0613 | 0.2267 | 0.085* | |
C86 | 0.1853 (14) | 1.1412 (14) | 0.2844 (3) | 0.090 (4) | |
H91 | 0.1501 | 1.1839 | 0.2662 | 0.108* | |
H92 | 0.1232 | 1.1092 | 0.2973 | 0.108* | |
C87 | 0.252 (2) | 1.242 (2) | 0.3020 (5) | 0.148 (8) | |
H93 | 0.2015 | 1.3123 | 0.3083 | 0.148* | |
H94 | 0.3113 | 1.2776 | 0.2891 | 0.148* | |
H95 | 0.2872 | 1.2006 | 0.3201 | 0.148* | |
C88 | 0.2607 (6) | 0.7785 (11) | 0.26133 (16) | 0.051 (2) | |
O89 | 0.3421 (5) | 0.7322 (9) | 0.27728 (12) | 0.068 (2) | |
N90 | 0.2366 (6) | 0.7350 (9) | 0.23214 (14) | 0.0521 (17) | |
H96 | 0.1754 | 0.7650 | 0.2228 | 0.062* | |
C91 | 0.3088 (9) | 0.6393 (10) | 0.21548 (18) | 0.055 (2) | |
H97 | 0.3847 | 0.6309 | 0.2259 | 0.066* | |
C92 | 0.2474 (17) | 0.5002 (15) | 0.2137 (4) | 0.114 (5) | |
H98 | 0.1715 | 0.5146 | 0.2036 | 0.136* | |
O93 | 0.2280 (13) | 0.4456 (14) | 0.2422 (3) | 0.138 (5) | |
H99 | 0.1639 | 0.4762 | 0.2481 | 0.138* | |
C94 | 0.3128 (19) | 0.4040 (14) | 0.1932 (4) | 0.122 (6) | |
H100 | 0.2722 | 0.3202 | 0.1921 | 0.122* | |
H101 | 0.3891 | 0.3897 | 0.2019 | 0.122* | |
H102 | 0.3184 | 0.4410 | 0.1727 | 0.122* | |
C95 | 0.3219 (7) | 0.6934 (8) | 0.18265 (16) | 0.0446 (17) | |
O96 | 0.2364 (5) | 0.7152 (8) | 0.16664 (12) | 0.0610 (17) | |
N97 | 0.4278 (5) | 0.7105 (7) | 0.17234 (12) | 0.0400 (13) | |
H103 | 0.4864 | 0.6982 | 0.1847 | 0.048* | |
C98 | 0.4463 (7) | 0.7504 (8) | 0.13985 (17) | 0.0422 (16) | |
H104 | 0.3809 | 0.7134 | 0.1277 | 0.051* | |
C99 | 0.5548 (9) | 0.6884 (10) | 0.1263 (3) | 0.066 (3) | |
H105 | 0.5566 | 0.7173 | 0.1045 | 0.079* | |
C100 | 0.5456 (13) | 0.5367 (11) | 0.1257 (4) | 0.087 (4) | |
H106 | 0.4735 | 0.5111 | 0.1158 | 0.087* | |
H107 | 0.5488 | 0.5030 | 0.1466 | 0.087* | |
H108 | 0.6086 | 0.5002 | 0.1142 | 0.087* | |
C101 | 0.6621 (11) | 0.7322 (12) | 0.1405 (3) | 0.078 (3) | |
H109 | 0.7256 | 0.6894 | 0.1305 | 0.078* | |
H110 | 0.6635 | 0.7089 | 0.1622 | 0.078* | |
H111 | 0.6690 | 0.8275 | 0.1384 | 0.078* | |
C102 | 0.4384 (6) | 0.9012 (7) | 0.13602 (16) | 0.0389 (15) | |
N103 | 0.3975 (5) | 0.9565 (6) | 0.11087 (12) | 0.0332 (11) | |
C104 | 0.3992 (6) | 1.0958 (8) | 0.11336 (18) | 0.0416 (15) | |
C105 | 0.4437 (9) | 1.1431 (9) | 0.1407 (2) | 0.056 (2) | |
H112 | 0.4508 | 1.2332 | 0.1458 | 0.067* | |
S106 | 0.4849 (3) | 1.0140 (3) | 0.16474 (4) | 0.0682 (7) | |
C107 | 0.3523 (5) | 1.1810 (7) | 0.08709 (19) | 0.0393 (15) | |
O108 | 0.3435 (5) | 1.3010 (6) | 0.08957 (17) | 0.0605 (16) | |
O109 | 0.0104 (7) | 0.3136 (7) | 0.07110 (17) | 0.0718 (19) | |
C110 | 0.0581 (7) | 0.4000 (9) | 0.0848 (2) | 0.0537 (19) | |
H113 | 0.1323 | 0.3809 | 0.0924 | 0.064* | |
N111 | 0.0179 (8) | 0.5228 (8) | 0.0908 (2) | 0.070 (2) | |
C112 | −0.0943 (15) | 0.5616 (18) | 0.0788 (4) | 0.148 (10) | |
H114 | −0.1109 | 0.6514 | 0.0852 | 0.148* | |
H115 | −0.1519 | 0.5021 | 0.0866 | 0.148* | |
H116 | −0.0951 | 0.5573 | 0.0564 | 0.148* | |
C113 | 0.077 (3) | 0.626 (2) | 0.1065 (4) | 0.183 (13) | |
H117 | 0.0268 | 0.7024 | 0.1079 | 0.183* | |
H118 | 0.1444 | 0.6498 | 0.0952 | 0.183* | |
H119 | 0.0991 | 0.5965 | 0.1270 | 0.183* | |
O114 | −0.0518 (10) | 1.1520 (12) | 0.4231 (3) | 0.118 (4) | |
C115 | −0.107 (2) | 1.189 (2) | 0.4000 (5) | 0.153 (10) | |
H120 | −0.1727 | 1.1460 | 0.3921 | 0.184* | |
N116 | −0.058 (2) | 1.311 (3) | 0.3859 (6) | 0.179 (8)* | |
C117 | 0.055 (2) | 1.407 (3) | 0.3973 (5) | 0.171 (11) | |
H121 | 0.0620 | 1.4810 | 0.3832 | 0.171* | |
H122 | 0.1243 | 1.3550 | 0.3974 | 0.171* | |
H123 | 0.0419 | 1.4407 | 0.4179 | 0.171* | |
C118 | −0.130 (2) | 1.371 (4) | 0.3615 (6) | 0.180 (10)* | |
H124 | −0.0951 | 1.4532 | 0.3547 | 0.180* | |
H125 | −0.2053 | 1.3899 | 0.3694 | 0.180* | |
H126 | −0.1371 | 1.3107 | 0.3442 | 0.180* | |
O119 | −0.3309 (14) | 0.317 (2) | 0.1859 (3) | 0.163 (6) | |
C120 | −0.2342 (16) | 0.287 (2) | 0.1764 (4) | 0.120 (6) | |
H127 | −0.2267 | 0.2025 | 0.1674 | 0.145* | |
N121 | −0.1332 (15) | 0.3678 (15) | 0.1779 (3) | 0.146 (7) | |
C122 | −0.140 (2) | 0.509 (3) | 0.1937 (6) | 0.160 (9) | |
H128 | −0.0671 | 0.5550 | 0.1915 | 0.160* | |
H129 | −0.1551 | 0.4988 | 0.2155 | 0.160* | |
H130 | −0.2004 | 0.5609 | 0.1840 | 0.160* | |
C123 | −0.0247 (19) | 0.313 (2) | 0.1639 (4) | 0.152 (9) | |
H131 | 0.0331 | 0.3820 | 0.1635 | 0.152* | |
H132 | −0.0414 | 0.2829 | 0.1431 | 0.152* | |
H133 | 0.0035 | 0.2395 | 0.1763 | 0.152* | |
O124 | 0.0280 (14) | 0.5350 (18) | 0.2669 (4) | 0.178 (7) | |
H134 | 0.0030 | 0.4891 | 0.2830 | 0.214* | |
H135 | 0.0125 | 0.6103 | 0.2752 | 0.214* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.018 (3) | 0.024 (3) | 0.063 (3) | 0.0003 (19) | −0.010 (2) | 0.002 (2) |
C2 | 0.012 (3) | 0.025 (3) | 0.078 (5) | 0.001 (2) | −0.005 (3) | 0.016 (3) |
C3 | 0.024 (4) | 0.084 (7) | 0.086 (6) | 0.009 (4) | 0.004 (4) | 0.052 (5) |
C4 | 0.050 (5) | 0.144 (12) | 0.055 (5) | 0.033 (6) | 0.018 (4) | 0.054 (6) |
C5 | 0.020 (4) | 0.099 (9) | 0.176 (12) | 0.001 (4) | 0.005 (5) | 0.094 (9) |
C6 | 0.079 (8) | 0.26 (2) | 0.059 (6) | 0.049 (11) | 0.024 (5) | 0.067 (10) |
C7 | 0.023 (3) | 0.025 (3) | 0.033 (3) | 0.002 (2) | 0.002 (2) | 0.002 (2) |
O8 | 0.033 (2) | 0.023 (2) | 0.0318 (19) | 0.0022 (17) | −0.0059 (16) | 0.0022 (16) |
N9 | 0.020 (2) | 0.019 (2) | 0.037 (2) | 0.0024 (18) | −0.0004 (18) | 0.0047 (19) |
C10 | 0.026 (3) | 0.021 (3) | 0.027 (2) | −0.002 (2) | −0.003 (2) | 0.004 (2) |
C11 | 0.031 (3) | 0.027 (3) | 0.030 (3) | 0.002 (2) | −0.007 (2) | 0.006 (2) |
O12 | 0.030 (2) | 0.025 (2) | 0.036 (2) | 0.0048 (17) | −0.0040 (16) | 0.0064 (17) |
C13 | 0.037 (4) | 0.043 (4) | 0.041 (3) | −0.004 (3) | −0.019 (3) | 0.005 (3) |
C14 | 0.012 (2) | 0.020 (3) | 0.026 (2) | −0.0016 (19) | −0.0057 (17) | 0.0003 (19) |
O15 | 0.025 (2) | 0.0220 (19) | 0.0310 (19) | −0.0024 (15) | −0.0034 (15) | −0.0010 (15) |
N16 | 0.020 (2) | 0.020 (2) | 0.024 (2) | −0.0040 (17) | 0.0002 (16) | 0.0005 (17) |
C17 | 0.018 (3) | 0.030 (3) | 0.026 (2) | −0.002 (2) | −0.0015 (19) | 0.000 (2) |
C18 | 0.029 (3) | 0.061 (5) | 0.036 (3) | 0.015 (3) | 0.006 (2) | 0.011 (3) |
C19 | 0.033 (4) | 0.155 (12) | 0.040 (4) | 0.025 (6) | −0.001 (3) | 0.003 (6) |
C20 | 0.088 (8) | 0.063 (6) | 0.097 (7) | 0.042 (6) | 0.042 (6) | 0.012 (6) |
C21 | 0.021 (3) | 0.032 (3) | 0.024 (2) | 0.006 (2) | −0.0037 (19) | −0.006 (2) |
N22 | 0.028 (3) | 0.050 (3) | 0.025 (2) | 0.007 (2) | −0.0045 (18) | −0.004 (2) |
C23 | 0.033 (4) | 0.080 (6) | 0.024 (3) | 0.014 (3) | −0.013 (2) | −0.009 (3) |
C24 | 0.031 (4) | 0.092 (6) | 0.024 (3) | 0.013 (4) | −0.015 (2) | −0.003 (3) |
S25 | 0.0204 (7) | 0.0655 (11) | 0.0281 (7) | 0.0063 (7) | −0.0055 (5) | −0.0034 (7) |
C26 | 0.038 (4) | 0.110 (8) | 0.026 (3) | 0.019 (5) | −0.008 (3) | −0.003 (4) |
O27 | 0.043 (3) | 0.169 (8) | 0.023 (2) | 0.028 (4) | −0.0080 (19) | 0.001 (3) |
N28 | 0.043 (4) | 0.116 (7) | 0.022 (3) | 0.009 (4) | −0.004 (2) | 0.002 (3) |
C29 | 0.048 (5) | 0.132 (10) | 0.023 (3) | 0.000 (5) | −0.004 (3) | −0.001 (4) |
C30 | 0.095 (8) | 0.127 (11) | 0.047 (5) | 0.007 (8) | 0.005 (5) | −0.011 (6) |
C31 | 0.37 (4) | 0.146 (17) | 0.055 (7) | −0.01 (2) | 0.083 (14) | −0.026 (10) |
C32 | 0.155 (19) | 0.20 (3) | 0.106 (12) | 0.005 (19) | −0.016 (12) | −0.024 (16) |
C33 | 0.17 (2) | 0.21 (3) | 0.115 (14) | 0.00 (2) | −0.002 (13) | −0.023 (17) |
C34 | 0.032 (4) | 0.139 (9) | 0.018 (3) | 0.000 (5) | −0.001 (2) | −0.013 (4) |
O35 | 0.047 (4) | 0.180 (9) | 0.031 (2) | −0.011 (5) | −0.009 (2) | −0.010 (4) |
N36 | 0.030 (3) | 0.104 (6) | 0.038 (3) | 0.006 (3) | 0.000 (2) | −0.007 (4) |
C37 | 0.038 (4) | 0.097 (7) | 0.044 (4) | −0.002 (4) | −0.002 (3) | −0.023 (5) |
C38 | 0.075 (7) | 0.132 (12) | 0.105 (9) | 0.000 (8) | 0.026 (6) | −0.072 (10) |
O39 | 0.151 (10) | 0.27 (2) | 0.115 (8) | −0.080 (12) | 0.054 (7) | −0.131 (12) |
C40 | 0.093 (9) | 0.102 (10) | 0.116 (10) | −0.001 (8) | 0.006 (7) | −0.062 (9) |
C41 | 0.034 (4) | 0.067 (5) | 0.043 (4) | −0.007 (3) | −0.002 (3) | −0.011 (4) |
O42 | 0.032 (3) | 0.123 (6) | 0.060 (3) | −0.004 (3) | −0.007 (2) | −0.004 (4) |
N43 | 0.031 (3) | 0.065 (4) | 0.038 (3) | −0.001 (3) | −0.003 (2) | −0.019 (3) |
C44 | 0.058 (5) | 0.059 (5) | 0.033 (3) | −0.011 (4) | 0.003 (3) | −0.011 (3) |
C45 | 0.178 (18) | 0.144 (14) | 0.121 (11) | −0.114 (14) | 0.107 (13) | −0.097 (11) |
C46 | 0.172 (16) | 0.066 (8) | 0.098 (9) | −0.011 (9) | −0.037 (10) | 0.003 (7) |
C47 | 0.14 (2) | 0.073 (13) | 0.063 (11) | −0.022 (13) | 0.009 (11) | 0.001 (9) |
C47' | 0.043 (12) | 0.044 (10) | 0.045 (9) | −0.001 (8) | 0.014 (7) | −0.001 (7) |
C48 | 0.034 (4) | 0.052 (4) | 0.034 (3) | 0.003 (3) | −0.005 (2) | −0.004 (3) |
N49 | 0.030 (3) | 0.042 (3) | 0.037 (3) | 0.000 (2) | −0.005 (2) | −0.006 (2) |
C50 | 0.044 (4) | 0.041 (4) | 0.044 (3) | 0.005 (3) | −0.006 (3) | −0.004 (3) |
C51 | 0.098 (8) | 0.046 (5) | 0.051 (5) | 0.014 (5) | −0.015 (5) | 0.000 (4) |
S52 | 0.0941 (18) | 0.0644 (14) | 0.0392 (9) | 0.0167 (13) | −0.0223 (10) | −0.0008 (9) |
C53 | 0.046 (4) | 0.036 (4) | 0.045 (4) | 0.001 (3) | −0.004 (3) | −0.004 (3) |
O54 | 0.102 (5) | 0.030 (3) | 0.071 (4) | 0.000 (3) | −0.015 (4) | −0.004 (3) |
N55 | 0.029 (3) | 0.035 (3) | 0.041 (3) | −0.003 (2) | −0.008 (2) | −0.009 (2) |
C56 | 0.024 (3) | 0.047 (4) | 0.048 (4) | 0.003 (3) | −0.011 (3) | −0.020 (3) |
C57 | 0.042 (5) | 0.23 (2) | 0.050 (5) | 0.060 (9) | −0.003 (4) | −0.032 (8) |
C58 | 0.034 (5) | 0.170 (15) | 0.136 (11) | 0.018 (6) | −0.004 (5) | −0.112 (11) |
C59 | 0.099 (11) | 0.163 (17) | 0.090 (9) | −0.026 (12) | 0.024 (8) | −0.025 (11) |
C60 | 0.155 (15) | 0.172 (19) | 0.073 (8) | 0.009 (15) | 0.035 (9) | 0.024 (11) |
C61 | 0.019 (3) | 0.040 (3) | 0.027 (3) | −0.005 (2) | −0.002 (2) | −0.007 (2) |
O62 | 0.032 (2) | 0.037 (3) | 0.036 (2) | −0.0063 (19) | −0.0061 (17) | −0.0078 (19) |
N63 | 0.023 (2) | 0.032 (3) | 0.030 (2) | −0.003 (2) | −0.0024 (18) | −0.004 (2) |
C64 | 0.028 (3) | 0.036 (3) | 0.024 (2) | −0.005 (2) | −0.005 (2) | 0.003 (2) |
C65 | 0.058 (4) | 0.034 (3) | 0.034 (3) | −0.006 (3) | −0.025 (3) | 0.008 (3) |
O66 | 0.034 (3) | 0.035 (2) | 0.048 (3) | −0.0077 (19) | −0.0114 (19) | 0.002 (2) |
C67 | 0.089 (8) | 0.057 (6) | 0.085 (6) | 0.012 (5) | −0.070 (6) | −0.002 (5) |
C68 | 0.014 (3) | 0.038 (3) | 0.025 (2) | −0.002 (2) | −0.0071 (18) | 0.004 (2) |
O69 | 0.028 (2) | 0.044 (3) | 0.046 (2) | 0.007 (2) | 0.0051 (18) | 0.019 (2) |
N70 | 0.022 (2) | 0.034 (3) | 0.023 (2) | 0.005 (2) | −0.0022 (17) | 0.0052 (19) |
C71 | 0.022 (3) | 0.059 (4) | 0.022 (2) | 0.008 (3) | −0.002 (2) | 0.002 (3) |
C72 | 0.037 (4) | 0.105 (8) | 0.034 (3) | −0.023 (4) | 0.004 (3) | −0.003 (4) |
C73 | 0.042 (5) | 0.189 (15) | 0.043 (4) | −0.032 (7) | −0.004 (3) | −0.017 (7) |
C74 | 0.101 (9) | 0.095 (9) | 0.072 (6) | −0.055 (8) | 0.015 (6) | 0.003 (6) |
C75 | 0.026 (3) | 0.066 (5) | 0.023 (3) | 0.005 (3) | −0.001 (2) | 0.000 (3) |
N76 | 0.028 (3) | 0.080 (5) | 0.023 (2) | 0.004 (3) | −0.0039 (19) | 0.001 (3) |
C77 | 0.034 (4) | 0.109 (8) | 0.029 (3) | −0.003 (4) | −0.009 (3) | −0.003 (4) |
C78 | 0.033 (4) | 0.134 (9) | 0.028 (3) | −0.005 (5) | −0.006 (3) | −0.012 (5) |
S79 | 0.0296 (9) | 0.1023 (17) | 0.0296 (7) | −0.0099 (10) | 0.0006 (6) | −0.0059 (9) |
C80 | 0.032 (4) | 0.119 (8) | 0.026 (3) | 0.004 (4) | −0.006 (2) | −0.009 (4) |
O81 | 0.047 (3) | 0.180 (9) | 0.029 (2) | −0.021 (5) | −0.008 (2) | −0.014 (4) |
N82 | 0.032 (3) | 0.107 (6) | 0.024 (2) | 0.002 (3) | −0.005 (2) | 0.003 (3) |
C83 | 0.037 (4) | 0.103 (7) | 0.025 (3) | 0.009 (4) | −0.003 (3) | 0.001 (4) |
C84 | 0.061 (6) | 0.101 (8) | 0.041 (4) | 0.003 (5) | −0.007 (4) | 0.003 (5) |
C85 | 0.092 (8) | 0.106 (10) | 0.056 (5) | −0.023 (7) | 0.001 (5) | 0.014 (6) |
C86 | 0.118 (11) | 0.077 (8) | 0.074 (7) | 0.014 (7) | −0.016 (7) | 0.006 (6) |
C87 | 0.20 (2) | 0.091 (12) | 0.147 (16) | −0.010 (14) | −0.001 (15) | −0.018 (12) |
C88 | 0.033 (4) | 0.091 (7) | 0.029 (3) | −0.004 (4) | 0.000 (3) | 0.010 (4) |
O89 | 0.042 (3) | 0.127 (6) | 0.034 (2) | 0.019 (4) | −0.006 (2) | 0.013 (3) |
N90 | 0.037 (3) | 0.090 (5) | 0.029 (3) | −0.003 (3) | 0.000 (2) | 0.002 (3) |
C91 | 0.069 (6) | 0.059 (5) | 0.038 (4) | 0.002 (4) | 0.000 (3) | 0.003 (4) |
C92 | 0.163 (15) | 0.068 (8) | 0.112 (10) | −0.016 (9) | 0.051 (10) | 0.016 (8) |
O93 | 0.164 (11) | 0.103 (8) | 0.151 (10) | 0.026 (8) | 0.068 (9) | 0.022 (8) |
C94 | 0.183 (17) | 0.052 (7) | 0.133 (12) | 0.012 (9) | 0.054 (12) | 0.002 (8) |
C95 | 0.051 (4) | 0.049 (4) | 0.034 (3) | 0.004 (3) | −0.002 (3) | −0.008 (3) |
O96 | 0.043 (3) | 0.103 (5) | 0.037 (2) | 0.003 (3) | −0.005 (2) | −0.015 (3) |
N97 | 0.034 (3) | 0.053 (4) | 0.032 (3) | −0.001 (3) | −0.007 (2) | −0.002 (3) |
C98 | 0.047 (4) | 0.040 (4) | 0.039 (3) | 0.003 (3) | 0.000 (3) | 0.002 (3) |
C99 | 0.069 (6) | 0.050 (5) | 0.079 (6) | 0.009 (4) | 0.035 (5) | 0.003 (4) |
C100 | 0.101 (9) | 0.046 (6) | 0.117 (9) | 0.019 (5) | 0.043 (7) | 0.004 (6) |
C101 | 0.093 (8) | 0.064 (6) | 0.078 (6) | 0.000 (6) | 0.025 (6) | −0.007 (5) |
C102 | 0.041 (4) | 0.036 (4) | 0.040 (3) | −0.004 (3) | 0.013 (3) | −0.009 (3) |
N103 | 0.027 (3) | 0.032 (3) | 0.040 (3) | 0.004 (2) | 0.000 (2) | −0.005 (2) |
C104 | 0.038 (4) | 0.034 (4) | 0.054 (4) | −0.001 (3) | 0.008 (3) | −0.010 (3) |
C105 | 0.077 (6) | 0.043 (4) | 0.049 (4) | 0.003 (4) | 0.002 (4) | −0.017 (4) |
S106 | 0.119 (2) | 0.0530 (12) | 0.0329 (9) | −0.0009 (13) | 0.0008 (10) | −0.0157 (9) |
C107 | 0.019 (3) | 0.030 (3) | 0.069 (4) | 0.000 (2) | 0.001 (3) | −0.008 (3) |
O108 | 0.050 (3) | 0.029 (3) | 0.102 (5) | 0.003 (2) | −0.012 (3) | −0.009 (3) |
O109 | 0.088 (5) | 0.044 (3) | 0.084 (4) | −0.016 (3) | 0.005 (4) | −0.030 (3) |
C110 | 0.045 (5) | 0.046 (5) | 0.070 (5) | 0.002 (4) | −0.005 (4) | −0.004 (4) |
N111 | 0.088 (6) | 0.043 (4) | 0.080 (5) | −0.005 (4) | 0.014 (4) | −0.027 (4) |
C112 | 0.143 (14) | 0.131 (14) | 0.176 (16) | 0.102 (12) | 0.108 (13) | 0.089 (13) |
C113 | 0.36 (4) | 0.095 (13) | 0.099 (11) | −0.097 (18) | 0.010 (16) | −0.043 (10) |
O114 | 0.115 (8) | 0.108 (8) | 0.133 (8) | 0.051 (7) | 0.024 (6) | 0.053 (7) |
C115 | 0.18 (2) | 0.133 (16) | 0.151 (16) | 0.075 (15) | 0.072 (15) | 0.067 (14) |
C117 | 0.19 (2) | 0.20 (3) | 0.129 (14) | −0.10 (2) | 0.009 (14) | −0.043 (17) |
O119 | 0.156 (12) | 0.219 (18) | 0.114 (8) | 0.023 (13) | −0.011 (8) | −0.006 (11) |
C120 | 0.110 (12) | 0.122 (13) | 0.131 (13) | 0.017 (11) | 0.048 (10) | −0.028 (11) |
N121 | 0.190 (14) | 0.115 (10) | 0.140 (11) | −0.015 (10) | 0.139 (12) | −0.047 (9) |
C122 | 0.18 (2) | 0.138 (18) | 0.158 (18) | −0.051 (17) | −0.021 (16) | 0.047 (17) |
C123 | 0.196 (19) | 0.126 (14) | 0.133 (14) | 0.049 (14) | −0.038 (13) | −0.100 (13) |
O124 | 0.192 (13) | 0.159 (13) | 0.190 (13) | −0.032 (11) | 0.132 (11) | −0.038 (11) |
N1—C107 | 1.348 (10) | C59—C60 | 1.443 (16) |
N1—C2 | 1.455 (9) | C61—O62 | 1.240 (8) |
C2—C7 | 1.520 (8) | C61—N63 | 1.347 (7) |
C2—C3 | 1.528 (11) | N63—C64 | 1.463 (8) |
C3—C4 | 1.491 (19) | C64—C68 | 1.522 (8) |
C3—C5 | 1.496 (15) | C64—C65 | 1.532 (9) |
C4—C6 | 1.544 (12) | C65—O66 | 1.437 (9) |
C7—O8 | 1.251 (8) | C65—C67 | 1.511 (10) |
C7—N9 | 1.327 (8) | C68—O69 | 1.245 (8) |
N9—C10 | 1.446 (7) | C68—N70 | 1.329 (7) |
C10—C14 | 1.525 (7) | N70—C71 | 1.471 (7) |
C10—C11 | 1.543 (8) | C71—C75 | 1.502 (8) |
C11—O12 | 1.424 (8) | C71—C72 | 1.530 (11) |
C11—C13 | 1.526 (9) | C72—C74 | 1.49 (2) |
C14—O15 | 1.237 (7) | C72—C73 | 1.529 (11) |
C14—N16 | 1.363 (7) | C75—N76 | 1.304 (8) |
N16—C17 | 1.462 (7) | C75—S79 | 1.752 (7) |
C17—C21 | 1.511 (7) | N76—C77 | 1.398 (9) |
C17—C18 | 1.531 (8) | C77—C78 | 1.351 (12) |
C18—C20 | 1.508 (15) | C77—C80 | 1.487 (9) |
C18—C19 | 1.538 (11) | C78—S79 | 1.715 (7) |
C21—N22 | 1.297 (8) | C80—O81 | 1.243 (9) |
C21—S25 | 1.738 (6) | C80—N82 | 1.338 (11) |
N22—C23 | 1.376 (8) | N82—C83 | 1.463 (9) |
C23—C24 | 1.346 (11) | C83—C88 | 1.504 (14) |
C23—C26 | 1.509 (10) | C83—C84 | 1.518 (16) |
C24—S25 | 1.702 (6) | C84—C86 | 1.520 (18) |
C26—O27 | 1.240 (9) | C84—C85 | 1.526 (13) |
C26—N28 | 1.325 (11) | C86—C87 | 1.47 (2) |
N28—C29 | 1.454 (9) | C88—O89 | 1.240 (10) |
C29—C30 | 1.52 (2) | C88—N90 | 1.349 (10) |
C29—C34 | 1.531 (15) | N90—C91 | 1.466 (12) |
C30—C31 | 1.520 (16) | C91—C95 | 1.520 (10) |
C30—C32 | 1.55 (3) | C91—C92 | 1.562 (18) |
C32—C33 | 1.52 (3) | C92—O93 | 1.363 (18) |
C34—O35 | 1.229 (9) | C92—C94 | 1.52 (2) |
C34—N36 | 1.351 (13) | C95—O96 | 1.210 (10) |
N36—C37 | 1.451 (13) | C95—N97 | 1.322 (10) |
C37—C38 | 1.480 (19) | N97—C98 | 1.471 (9) |
C37—C41 | 1.549 (10) | C98—C102 | 1.519 (11) |
C38—O39 | 1.48 (2) | C98—C99 | 1.527 (11) |
C38—C40 | 1.51 (2) | C99—C101 | 1.438 (17) |
C41—O42 | 1.219 (10) | C99—C100 | 1.520 (15) |
C41—N43 | 1.318 (10) | C102—N103 | 1.292 (10) |
N43—C44 | 1.464 (9) | C102—S106 | 1.746 (7) |
C44—C48 | 1.523 (12) | N103—C104 | 1.397 (10) |
C44—C45 | 1.526 (14) | C104—C105 | 1.357 (11) |
C45—C47' | 1.27 (3) | C104—C107 | 1.503 (11) |
C45—C47 | 1.30 (2) | C105—S106 | 1.711 (10) |
C45—C46 | 1.70 (3) | C107—O108 | 1.208 (9) |
C48—N49 | 1.293 (9) | O109—C110 | 1.175 (11) |
C48—S52 | 1.733 (8) | C110—N111 | 1.339 (12) |
N49—C50 | 1.388 (11) | N111—C113 | 1.398 (18) |
C50—C51 | 1.356 (12) | N111—C112 | 1.438 (19) |
C50—C53 | 1.511 (10) | O114—C115 | 1.23 (2) |
C51—S52 | 1.704 (10) | C115—N116 | 1.48 (4) |
C53—O54 | 1.227 (10) | N116—C118 | 1.45 (3) |
C53—N55 | 1.329 (10) | N116—C117 | 1.68 (3) |
N55—C56 | 1.466 (8) | O119—C120 | 1.24 (2) |
C56—C61 | 1.514 (9) | C120—N121 | 1.42 (2) |
C56—C57 | 1.542 (12) | N121—C123 | 1.51 (2) |
C57—C58 | 1.489 (19) | N121—C122 | 1.57 (3) |
C57—C59 | 1.503 (17) | ||
C107—N1—C2 | 122.6 (6) | C58—C57—C56 | 111.5 (12) |
N1—C2—C7 | 107.4 (5) | C59—C57—C56 | 119.9 (11) |
N1—C2—C3 | 114.6 (5) | C60—C59—C57 | 100.2 (13) |
C7—C2—C3 | 110.9 (7) | O62—C61—N63 | 122.9 (6) |
C4—C3—C5 | 111.0 (9) | O62—C61—C56 | 121.5 (5) |
C4—C3—C2 | 112.4 (7) | N63—C61—C56 | 115.6 (6) |
C5—C3—C2 | 111.8 (10) | C61—N63—C64 | 122.1 (5) |
C3—C4—C6 | 113.6 (12) | N63—C64—C68 | 112.5 (5) |
O8—C7—N9 | 122.9 (6) | N63—C64—C65 | 107.9 (5) |
O8—C7—C2 | 120.2 (5) | C68—C64—C65 | 109.9 (5) |
N9—C7—C2 | 116.9 (5) | O66—C65—C67 | 111.9 (8) |
C7—N9—C10 | 121.6 (5) | O66—C65—C64 | 106.1 (5) |
N9—C10—C14 | 113.1 (4) | C67—C65—C64 | 113.4 (7) |
N9—C10—C11 | 108.9 (5) | O69—C68—N70 | 123.1 (5) |
C14—C10—C11 | 111.3 (5) | O69—C68—C64 | 119.1 (5) |
O12—C11—C13 | 110.2 (5) | N70—C68—C64 | 117.7 (5) |
O12—C11—C10 | 107.0 (4) | C68—N70—C71 | 121.8 (5) |
C13—C11—C10 | 113.9 (5) | N70—C71—C75 | 109.7 (5) |
O15—C14—N16 | 122.7 (5) | N70—C71—C72 | 113.2 (6) |
O15—C14—C10 | 120.6 (5) | C75—C71—C72 | 114.3 (6) |
N16—C14—C10 | 116.7 (5) | C74—C72—C73 | 111.5 (11) |
C14—N16—C17 | 120.6 (4) | C74—C72—C71 | 113.9 (8) |
N16—C17—C21 | 110.6 (4) | C73—C72—C71 | 110.0 (8) |
N16—C17—C18 | 112.9 (5) | N76—C75—C71 | 122.4 (6) |
C21—C17—C18 | 114.7 (5) | N76—C75—S79 | 115.1 (5) |
C20—C18—C17 | 112.1 (7) | C71—C75—S79 | 122.2 (4) |
C20—C18—C19 | 111.8 (9) | C75—N76—C77 | 109.1 (6) |
C17—C18—C19 | 108.7 (6) | C78—C77—N76 | 116.8 (6) |
N22—C21—C17 | 123.2 (5) | C78—C77—C80 | 125.8 (7) |
N22—C21—S25 | 115.1 (4) | N76—C77—C80 | 117.4 (7) |
C17—C21—S25 | 121.3 (4) | C77—C78—S79 | 109.8 (6) |
C21—N22—C23 | 109.7 (5) | C78—S79—C75 | 89.1 (3) |
C24—C23—N22 | 115.9 (6) | O81—C80—N82 | 124.0 (7) |
C24—C23—C26 | 124.4 (6) | O81—C80—C77 | 121.5 (7) |
N22—C23—C26 | 119.7 (6) | N82—C80—C77 | 114.5 (6) |
C23—C24—S25 | 110.7 (5) | C80—N82—C83 | 125.7 (6) |
C24—S25—C21 | 88.6 (3) | N82—C83—C88 | 110.1 (8) |
O27—C26—N28 | 123.8 (7) | N82—C83—C84 | 109.6 (7) |
O27—C26—C23 | 119.3 (7) | C88—C83—C84 | 111.0 (7) |
N28—C26—C23 | 116.8 (6) | C83—C84—C86 | 113.6 (9) |
C26—N28—C29 | 122.8 (6) | C83—C84—C85 | 110.2 (9) |
N28—C29—C30 | 111.5 (10) | C86—C84—C85 | 111.9 (11) |
N28—C29—C34 | 110.6 (7) | C87—C86—C84 | 114.5 (15) |
C30—C29—C34 | 109.7 (9) | O89—C88—N90 | 121.9 (9) |
C31—C30—C29 | 112.8 (14) | O89—C88—C83 | 121.7 (7) |
C31—C30—C32 | 102.8 (15) | N90—C88—C83 | 116.3 (7) |
C29—C30—C32 | 113.2 (13) | C88—N90—C91 | 123.8 (7) |
C33—C32—C30 | 104.0 (19) | N90—C91—C95 | 106.9 (7) |
O35—C34—N36 | 123.0 (10) | N90—C91—C92 | 110.0 (9) |
O35—C34—C29 | 123.1 (10) | C95—C91—C92 | 109.1 (9) |
N36—C34—C29 | 113.9 (6) | O93—C92—C94 | 111.2 (14) |
C34—N36—C37 | 123.0 (7) | O93—C92—C91 | 113.4 (14) |
N36—C37—C38 | 111.9 (8) | C94—C92—C91 | 111.2 (12) |
N36—C37—C41 | 106.5 (6) | O96—C95—N97 | 122.5 (7) |
C38—C37—C41 | 111.8 (10) | O96—C95—C91 | 119.5 (7) |
C37—C38—O39 | 106.5 (15) | N97—C95—C91 | 118.0 (7) |
C37—C38—C40 | 113.0 (9) | C95—N97—C98 | 120.5 (6) |
O39—C38—C40 | 109.6 (12) | N97—C98—C102 | 111.2 (6) |
O42—C41—N43 | 124.9 (7) | N97—C98—C99 | 113.0 (7) |
O42—C41—C37 | 119.2 (7) | C102—C98—C99 | 114.1 (7) |
N43—C41—C37 | 115.9 (7) | C101—C99—C100 | 111.7 (11) |
C41—N43—C44 | 120.3 (6) | C101—C99—C98 | 115.0 (9) |
N43—C44—C48 | 109.6 (7) | C100—C99—C98 | 110.7 (9) |
N43—C44—C45 | 114.0 (9) | N103—C102—C98 | 122.3 (7) |
C48—C44—C45 | 112.6 (8) | N103—C102—S106 | 114.5 (5) |
C47'—C45—C47 | 85.7 (17) | C98—C102—S106 | 123.2 (6) |
C47'—C45—C44 | 122 (2) | C102—N103—C104 | 111.0 (6) |
C47—C45—C44 | 126.8 (15) | C105—C104—N103 | 114.7 (8) |
C47'—C45—C46 | 111.1 (14) | C105—C104—C107 | 125.1 (7) |
C47—C45—C46 | 102.4 (19) | N103—C104—C107 | 120.2 (6) |
C44—C45—C46 | 106.2 (15) | C104—C105—S106 | 110.7 (7) |
N49—C48—C44 | 124.0 (7) | C105—S106—C102 | 89.2 (4) |
N49—C48—S52 | 114.4 (6) | O108—C107—N1 | 125.4 (8) |
C44—C48—S52 | 121.5 (5) | O108—C107—C104 | 121.7 (8) |
C48—N49—C50 | 110.4 (7) | N1—C107—C104 | 112.9 (6) |
C51—C50—N49 | 115.6 (7) | O109—C110—N111 | 127.5 (9) |
C51—C50—C53 | 123.6 (8) | C110—N111—C113 | 127.0 (16) |
N49—C50—C53 | 120.7 (7) | C110—N111—C112 | 119.5 (11) |
C50—C51—S52 | 109.7 (7) | C113—N111—C112 | 113.4 (17) |
C51—S52—C48 | 89.8 (4) | O114—C115—N116 | 113 (3) |
O54—C53—N55 | 124.7 (7) | C118—N116—C115 | 115 (2) |
O54—C53—C50 | 121.3 (8) | C118—N116—C117 | 114 (3) |
N55—C53—C50 | 114.0 (6) | C115—N116—C117 | 131 (2) |
C53—N55—C56 | 124.1 (6) | O119—C120—N121 | 126.5 (19) |
N55—C56—C61 | 106.7 (5) | C120—N121—C123 | 117.8 (14) |
N55—C56—C57 | 113.4 (7) | C120—N121—C122 | 119.1 (14) |
C61—C56—C57 | 111.0 (7) | C123—N121—C122 | 123.1 (17) |
C58—C57—C59 | 111.3 (12) | ||
C107—N1—C2—C7 | −128.0 (6) | C53—N55—C56—C61 | −129.8 (7) |
N1—C2—C7—N9 | 158.6 (5) | N55—C56—C61—N63 | 151.6 (5) |
C2—C7—N9—C10 | 177.0 (5) | C56—C61—N63—C64 | 171.2 (5) |
C7—N9—C10—C14 | 54.2 (7) | C61—N63—C64—C68 | 63.9 (7) |
N9—C10—C14—N16 | 43.0 (6) | N63—C64—C68—N70 | 32.5 (7) |
C10—C14—N16—C17 | 174.9 (5) | C64—C68—N70—C71 | 173.2 (5) |
C14—N16—C17—C21 | 120.2 (5) | C68—N70—C71—C75 | 120.5 (6) |
N16—C17—C21—N22 | 169.3 (5) | N70—C71—C75—N76 | 157.4 (6) |
C17—C21—N22—C23 | 172.1 (6) | C71—C75—N76—C77 | 174.1 (7) |
C21—N22—C23—C26 | −179.7 (7) | C75—N76—C77—C80 | 178.8 (8) |
N22—C23—C26—N28 | −4.0 (12) | N76—C77—C80—N82 | −2.8 (12) |
C23—C26—N28—C29 | −172.4 (8) | C77—C80—N82—C83 | −170.0 (8) |
C26—N28—C29—C34 | −138.5 (9) | C80—N82—C83—C88 | −102.1 (10) |
N28—C29—C34—N36 | 138.3 (9) | N82—C83—C88—N90 | 132.2 (8) |
C29—C34—N36—C37 | 167.3 (8) | C83—C88—N90—C91 | 170.9 (8) |
C34—N36—C37—C41 | −138.6 (9) | C88—N90—C91—C95 | −134.9 (8) |
N36—C37—C41—N43 | 132.2 (8) | N90—C91—C95—N97 | 125.0 (8) |
C37—C41—N43—C44 | −177.8 (7) | C91—C95—N97—C98 | 174.2 (7) |
C41—N43—C44—C48 | 95.4 (8) | C95—N97—C98—C102 | 84.8 (8) |
N43—C44—C48—N49 | −154.2 (7) | N97—C98—C102—N103 | −146.4 (7) |
C44—C48—N49—C50 | 179.6 (7) | C98—C102—N103—C104 | 179.7 (6) |
C48—N49—C50—C53 | −178.1 (7) | C102—N103—C104—C107 | −178.2 (6) |
N49—C50—C53—N55 | −4.8 (10) | N103—C104—C107—N1 | −7.4 (10) |
C50—C53—N55—C56 | 171.7 (6) | C2—N1—C107—C104 | 171.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H12···O12 | 0.86 | 2.57 | 2.779 (7) | 95 |
N16—H19···O12 | 0.86 | 2.64 | 2.957 (6) | 103 |
C24—H28···O96 | 0.93 | 2.60 | 3.158 (11) | 119 |
N36—H40···O81 | 0.86 | 2.44 | 3.240 (9) | 155 |
O39—H43···O119 | 0.844 | 1.782 | 2.58 (2) | 156.8 |
N63—H68···O66 | 0.86 | 2.55 | 2.784 (7) | 97 |
N70—H75···O66 | 0.86 | 2.76 | 2.942 (7) | 94 |
N70—H75···O114 | 0.86 | 2.15 | 2.963 (13) | 157 |
C78—H84···O42 | 0.93 | 2.29 | 3.190 (12) | 164 |
N90—H96···O27 | 0.86 | 2.13 | 2.952 (10) | 161 |
O93—H99···O124 | 0.846 | 1.877 | 2.72 (2) | 171.8 |
O124—H135···O81 | 0.854 | 1.948 | 2.80 (2) | 174.2 |
N16—H19···O109i | 0.86 | 2.12 | 2.965 (9) | 167 |
O12—H15···O8ii | 0.822 | 1.905 | 2.712 (6) | 166.9 |
N9—H12···O15ii | 0.86 | 2.10 | 2.873 (6) | 150 |
N43—H47···O89iii | 0.86 | 2.02 | 2.862 (8) | 166 |
O66—H71···O62iv | 0.824 | 1.860 | 2.684 (7) | 178.8 |
N63—H68···O69iv | 0.86 | 2.02 | 2.823 (7) | 154 |
N97—H103···O35v | 0.86 | 2.31 | 3.059 (9) | 146 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z; (iii) x−1, y, z; (iv) −x, y+1/2, −z+1; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C72H112N16O16S4·3C3H7NO·H2O |
Mr | 1823.32 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 11.5563 (1), 9.9957 (2), 42.9208 (10) |
β (°) | 91.3492 (15) |
V (Å3) | 4956.55 (16) |
Z | 2 |
Radiation type | Synchrotron, λ = 0.83600 Å |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.01 × 0.01 × 0.01 |
Data collection | |
Diffractometer | Rigaku RAXIS-IV diffractometer |
Absorption correction | For a cylinder mounted on the ϕ axis (CYLABS; Nardelli, 1998) |
Tmin, Tmax | 0.657, 0.661 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15629, 8977, 8890 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.097, 0.259, 1.25 |
No. of reflections | 8977 |
No. of parameters | 1119 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.52, −1.21 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.17 (14) |
Computer programs: PROCESS (Higashi, 1996), MOSFLM (Leslie, 1999), MOSFLM, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1998), PARST (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H12···O12 | 0.860 | 2.567 | 2.779 (7) | 95.1 |
N16—H19···O12 | 0.860 | 2.644 | 2.957 (6) | 102.9 |
C24—H28···O96 | 0.930 | 2.604 | 3.158 (11) | 118.7 |
N36—H40···O81 | 0.860 | 2.439 | 3.240 (9) | 155.2 |
O39—H43···O119 | 0.844 | 1.782 | 2.579 (24) | 156.8 |
N63—H68···O66 | 0.861 | 2.547 | 2.784 (7) | 96.8 |
N70—H75···O66 | 0.860 | 2.758 | 2.942 (7) | 93.7 |
N70—H75···O114 | 0.860 | 2.154 | 2.963 (13) | 156.6 |
C78—H84···O42 | 0.930 | 2.286 | 3.190 (12) | 163.8 |
N90—H96···O27 | 0.859 | 2.129 | 2.952 (10) | 160.5 |
O93—H99···O124 | 0.846 | 1.877 | 2.717 (22) | 171.8 |
O124—H135···O81 | 0.854 | 1.948 | 2.799 (21) | 174.2 |
N16—H19···O109i | 0.860 | 2.122 | 2.965 (9) | 166.7 |
O12—H15···O8ii | 0.822 | 1.905 | 2.712 (6) | 166.9 |
N9—H12···O15ii | 0.860 | 2.097 | 2.873 (6) | 149.9 |
N43—H47···O89iii | 0.860 | 2.020 | 2.862 (8) | 166.1 |
O66—H71···O62iv | 0.824 | 1.860 | 2.684 (7) | 178.8 |
N63—H68···O69iv | 0.861 | 2.022 | 2.823 (7) | 154.4 |
N97—H103···O35v | 0.859 | 2.312 | 3.059 (9) | 145.6 |
Symmetry codes: (i) x, y+1, z; (ii) −x, y+1/2, −z; (iii) x−1, y, z; (iv) −x, y+1/2, −z+1; (v) x+1, y, z. |
C107—N1—C2—C7 | ϕ1 | -128.0 (6) |
N1—C2—C7—N9 | ψ1 | 158.6 (5) |
C2—C7—N9—C10 | ω1 | 177.0 (5) |
C7—N9—C10—C14 | ϕ2 | 54.2 (7) |
N9—C10—C14—N16 | ψ2 | 43.0 (6) |
C10—C14—N16—C17 | ω2 | 174.9 (5) |
C14—N16—C17—C21 | ϕ3 | 120.2 (5) |
N16—C17—C21—N22 | ψ3 | 169.3 (5) |
C17—C21—N22—C23 | ω3 | 172.1 (6) |
C21—N22—C23—C26 | ϕ4 | -179.7 (7) |
N22—C23—C26—N28 | ψ4 | -4.0 (12) |
C23—C26—N28—C29 | ω4 | -172.4 (8) |
C26—N28—C29—C34 | ϕ5 | -138.5 (9) |
N28—C29—C34—N36 | ψ5 | 138.3 (9) |
C29—C34—N36—C37 | ω5 | 167.3 (8) |
C34—N36—C37—C41 | ϕ6 | -138.6 (9) |
N36—C37—C41—N43 | ψ6 | 132.2 (8) |
C37—C41—N43—C44 | ω6 | -177.8 (7) |
C41—N43—C44—C48 | ϕ7 | 95.4 (8) |
N43—C44—C48—N49 | ψ7 | -154.2 (7) |
C44—C48—N49—C50 | ω7 | 179.6 (7) |
C48—N49—C50—C53 | ϕ8 | -178.1 (7) |
N49—C50—C53—N55 | ψ8 | -4.8 (10) |
C50—C53—N55—C56 | ω8 | 171.7 (6) |
C53—N55—C56—C61 | ϕ9 | -129.8 (7) |
N55—C56—C61—N63 | ψ9 | 151.6 (5) |
C56—C61—N63—C64 | ω9 | 171.2 (5) |
C61—N63—C64—C68 | ϕ10 | 63.9 (7) |
N63—C64—C68—N70 | ψ10 | 32.5 (7) |
C64—C68—N70—C71 | ω10 | 173.2 (5) |
C68—N70—C71—C75 | ϕ11 | 120.5 (6) |
N70—C71—C75—N76 | ψ11 | 157.4 (6) |
C71—C75—N76—C77 | ω11 | 174.1 (7) |
C75—N76—C77—C80 | ϕ12 | 178.8 (8) |
N76—C77—C80—N82 | ψ12 | -2.8 (12) |
C77—C80—N82—C83 | ω12 | -170.0 (8) |
C80—N82—C83—C88 | ϕ13 | -102.1 (10) |
N82—C83—C88—N90 | ψ13 | 132.2 (8) |
C83—C88—N90—C91 | ω13 | 170.9 (8) |
C88—N90—C91—C95 | ϕ14 | -134.9 (8) |
N90—C91—C95—N97 | ψ14 | 125.0 (8) |
C91—C95—N97—C98 | ω14 | 174.2 (7) |
C95—N97—C98—C102 | ϕ15 | 84.8 (8) |
N97—C98—C102—N103 | ψ15 | -146.4 (7) |
C98—C102—N103—C104 | ω15 | 179.7 (6) |
C102—N103—C104—C107 | ϕ16 | -178.2 (6) |
N103—C104—C107—N1 | ψ16 | -7.4 (10) |
C2—N1—C107—C104 | ω16 | 171.0 (6) |
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Ascidiacyclamide (ASC) is a cytotoxic peptide isolated from marine organisms (Ireland et al., 1982; Hamamoto et al., 1983), and includes unusualamino acids (Fig. 1), thiazole (Thz) and oxazoline (Oxz). Two major structures are known for this peptide (Ishida et al., 1989). We have attempted to control its structure by chemical modification, e.g. substitution of amino acids or changing the chirality (Doi et al., 1999). The conformations of ASC analogues seem to be restricted by the rigid blocks composed of Thz and Oxz, since these blocks limit the rotations of peptide backbones (N—Cα and Cα-C bonds). Therefore, we tried to break the Oxz blocks to increase backbone flexibility. The Oxz block is synthesized from threonine and modification would result in threonine residues in place of the Oxz blocks. Threonine has two chiral C atoms at the α and β positions, and both C atoms could be targets of the chiral modifications (a diastereomer of threonine at the Cβ position is named allo-threonine, aThr). Such desoxazoline-ASC analogues (dASC) prefer a single conformation, viz. a folded form (Asano et al., 2001). It was postulated that the molecular size of these cyclic peptides (24-membered ring) could limit the conformational variations.
Thus, we attempted a dimerization of these dASC diastereomers to give more conformational freedom to the peptide backbone (Fig. 1). The dimeric desoxazoline-ASC (dASC2) analogues have a 48-membered ring in place of the 24-membered ring of ASC in dASC analogues. Crystals of [Thr,D-aThr]-dASC2 were obtained from the dASC2 diastereomers. The structure of this analogue is completely different from the folded or squared structure of ASC and a related peptide, patellamide (Schmitz et al., 1989). We report here the crystal structure of [D-aThr,Thr]-dASC2.
Crystals of [D-aThr,Thr]-dASC2 were grown in aqueous dimethylformamide (DMF) solution and the X-ray diffraction data were measured on s synchrotron source. The structure is shown in Fig. 2. The peptide is slightly twisted, but no large folding is observed. In dASC analogues, the peptide molecules are folded such that the Thz rings face each other (Asano et al., 2001), and the Thz-Thz stacking is a notable feature of a folded dASC. In this structure, the four Thz rings are separated from each other and no stacking is observed. The Thz4 and Thz12 rings are both roughly perpendicular to the Thz8 and Thz16 rings; the angles between the least-squares planes are Thz4···Thz8 = 85.7°, Thz4···Thz16 = 84.2°, Thz12···Thz8 = 78.2° and Thz12···Thz16 = 76.9°. The conformation of the peptide backbone is shown in Figs. 3 and 4. The peptide backbone forms a unique β-sheet structure (Fig. 3). In this β-sheet, C—H···O hydrogen bonds are formed between the Thz and carbonyl O atoms (Table 2): C24(Thz4)···O96(Thr14) = 3.158 (11) Å and C78(Thz12)···O42(Thr6) = 3.190 (12) Å. Such hydrogen bonds lead to a parallel arrangement of Thz4 and Thz12; the angle between the least-squares planes of Thz4 and Thz12 is 23.2°. Consequently, the 48-membered ring is relatively flat (Fig. 4). Furthermore, the peptide has a repeated sequence, and structural symmetry is found in the torsion angles of the backbone (Table 1). Although this implies the existence of a pseudo-twofold axis in the molecule, the crystallographic symmetry is distorted by local conformations and interactions with the solvent molecules (Fig. 1); O39(Thr6)···O119(DMF) = 2.579 (24) Å, N70(D-Val11)···O114(DMF) = 2.963 (13) Å, N16(D-Val3)···O109(DMF) = 2.965 (9) Å and O93(Thr14)···O124(W) = 2.717 (22) Å.
The conformational properties which were found in the folded and squared structures of ASC and dASC analogues are not found in the structure of [D-aThr,Thr]-dASC2. The molecule is relatively flat, with accompanying slight twisting, and a unique β-sheet is formed, involving C—H···O hydrogen bonds. Dimerization gives conformational flexibility to the peptide molecule, and the resulting novel flat structure is the first such example in ASC analogues.