Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110004634/sk3354sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110004634/sk3354Isup2.hkl |
CCDC reference: 774898
Compound (I) was obtained from a CH2Cl2:MeOH (Ratio?) extract from a sponge sample (500 g wet weight) of Halichondria sp. (order Halichondrida) collected at Tulamben Bay, Bali (Indonesia), as described by Mudianta et al. (2010). The same crystal structurally characterised at 130 K (Mudianta et al., 2010) was used here for studying both the phase transition temperature and the higher-temperature structure.
A conclusive absolute structure determination was not possible with the 293 K data set and the chirality of (I) was assigned on the previously reported 130 K structure using the analysis of Hooft et al. (2008). The Flack parameter (Flack, 1983) was also indeterminate in the absence of any atoms heavier than N, so all Friedel equivalent reflections were merged prior to refinement. The three most intense reflections (202, 122 and 004) were omitted from the data set.
Alkyl and olefinic H atoms were included at estimated positions using a riding model, with C—H = 0.93–0.98 Å [Please check added text] and with Uiso(H) = 1.2Ueq(C).
Disorder in the methylene groups from C17 to C20 was identified. Alternate positions for atoms C18 and C19 were resolved and their complementary occupancies were refined to a ratio of 0.65:0.35, with isotropic displacement parameters. The disorder led to alternate positions for all H atoms attached to atoms C17–C20 inclusive on the basis of their different dihedral angles. Restraints were applied to keep the C18A—C19A and C18B—C19B bond lengths the same (and corresponding angles involving attached H atoms) to aid refinement.
Data collection: CrysAlis PRO (Oxford Diffraction, 2008); cell refinement: CrysAlis PRO (Oxford Diffraction, 2008); data reduction: CrysAlis PRO (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C32H52N2 | F(000) = 1032 |
Mr = 464.76 | Dx = 1.046 Mg m−3 |
Orthorhombic, P22121 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2bc 2 | Cell parameters from 1581 reflections |
a = 9.8895 (3) Å | θ = 2.7–62.5° |
b = 16.1689 (5) Å | µ = 0.44 mm−1 |
c = 18.4642 (7) Å | T = 293 K |
V = 2952.47 (17) Å3 | Prism, colourless |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
Oxford Diffraction Gemini S Ultra diffractometer | 2628 independent reflections |
Radiation source: Ultra (Cu) X-ray Source | 1427 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.036 |
Detector resolution: 16.0696 pixels mm-1 | θmax = 62.5°, θmin = 3.6° |
ω scans | h = −7→11 |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | k = −18→15 |
Tmin = 0.820, Tmax = 1.000 | l = −21→17 |
8051 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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.148 | w = 1/[s2(Fo2) + (0.091P)2] |
S = 0.88 | (Δ/σ)max < 0.001 |
2628 reflections | Δρmax = 0.16 e Å−3 |
307 parameters | Δρmin = −0.12 e Å−3 |
2 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (5) |
C32H52N2 | V = 2952.47 (17) Å3 |
Mr = 464.76 | Z = 4 |
Orthorhombic, P22121 | Cu Kα radiation |
a = 9.8895 (3) Å | µ = 0.44 mm−1 |
b = 16.1689 (5) Å | T = 293 K |
c = 18.4642 (7) Å | 0.3 × 0.2 × 0.2 mm |
Oxford Diffraction Gemini S Ultra diffractometer | 2628 independent reflections |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | 1427 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 1.000 | Rint = 0.036 |
8051 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 2 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.16 e Å−3 |
2628 reflections | Δρmin = −0.12 e Å−3 |
307 parameters |
Experimental. none |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 1.1498 (4) | 0.8609 (2) | 0.9062 (2) | 0.0855 (12) | |
H1A | 1.0772 | 0.8808 | 0.8755 | 0.103* | |
H1B | 1.1718 | 0.9043 | 0.9405 | 0.103* | |
C2 | 1.1018 (4) | 0.7836 (2) | 0.9477 (2) | 0.0804 (11) | |
H2 | 1.1796 | 0.7656 | 0.9765 | 0.096* | |
C3 | 1.0714 (4) | 0.7105 (2) | 0.8941 (2) | 0.0796 (11) | |
H3 | 1.0752 | 0.6608 | 0.9244 | 0.096* | |
C4 | 1.1925 (4) | 0.7017 (3) | 0.8418 (2) | 0.0887 (13) | |
H4A | 1.2678 | 0.6774 | 0.8679 | 0.106* | |
H4B | 1.1678 | 0.6638 | 0.8033 | 0.106* | |
C5 | 1.2381 (4) | 0.7821 (3) | 0.8086 (2) | 0.0877 (12) | |
H5A | 1.3184 | 0.7723 | 0.7797 | 0.105* | |
H5B | 1.1678 | 0.8026 | 0.7767 | 0.105* | |
C6 | 0.6495 (5) | 0.7221 (3) | 0.8212 (3) | 0.1003 (14) | |
H6A | 0.6229 | 0.7632 | 0.8567 | 0.120* | |
H6B | 0.5699 | 0.7068 | 0.7935 | 0.120* | |
C7 | 0.7538 (5) | 0.7581 (3) | 0.7715 (3) | 0.0970 (14) | |
H7 | 0.7778 | 0.7148 | 0.7366 | 0.116* | |
C8 | 0.8816 (4) | 0.7789 (2) | 0.8136 (2) | 0.0827 (12) | |
H8A | 0.9508 | 0.7981 | 0.7804 | 0.099* | |
H8B | 0.8626 | 0.8231 | 0.8475 | 0.099* | |
C9 | 0.9334 (4) | 0.7044 (2) | 0.8544 (2) | 0.0745 (10) | |
H9 | 0.9472 | 0.6620 | 0.8172 | 0.089* | |
C10 | 0.8205 (4) | 0.6711 (3) | 0.9010 (2) | 0.0872 (12) | |
H10A | 0.8515 | 0.6221 | 0.9264 | 0.105* | |
H10B | 0.7957 | 0.7121 | 0.9369 | 0.105* | |
C11 | 1.3378 (4) | 0.9172 (3) | 0.8373 (3) | 0.1020 (15) | |
H11A | 1.4149 | 0.8996 | 0.8088 | 0.122* | |
H11B | 1.3728 | 0.9456 | 0.8796 | 0.122* | |
C12 | 1.2579 (5) | 0.9797 (3) | 0.7926 (3) | 0.1173 (17) | |
H12A | 1.1768 | 0.9942 | 0.8193 | 0.141* | |
H12B | 1.3119 | 1.0296 | 0.7881 | 0.141* | |
C13 | 1.2163 (6) | 0.9523 (3) | 0.7169 (3) | 0.1128 (17) | |
H13 | 1.2820 | 0.9261 | 0.6891 | 0.135* | |
C14 | 1.0963 (6) | 0.9619 (3) | 0.6869 (3) | 0.1009 (15) | |
H14 | 1.0296 | 0.9877 | 0.7143 | 0.121* | |
C15 | 1.0618 (7) | 0.9362 (3) | 0.6169 (3) | 0.1248 (19) | |
H15 | 1.1299 | 0.9099 | 0.5909 | 0.150* | |
C16 | 0.9460 (8) | 0.9445 (3) | 0.5833 (3) | 0.1238 (19) | |
H16 | 0.9436 | 0.9269 | 0.5354 | 0.149* | |
C17 | 0.8190 (6) | 0.9784 (3) | 0.6128 (3) | 0.1109 (16) | |
H17A | 0.7839 | 1.0143 | 0.5751 | 0.133* | 0.654 (13) |
H17B | 0.8466 | 1.0144 | 0.6521 | 0.133* | 0.654 (13) |
H17C | 0.8308 | 0.9950 | 0.6629 | 0.133* | 0.346 (13) |
H17D | 0.7907 | 1.0260 | 0.5847 | 0.133* | 0.346 (13) |
C18A | 0.7182 (9) | 0.9141 (5) | 0.6061 (6) | 0.111 (3)* | 0.654 (13) |
H18A | 0.7108 | 0.9005 | 0.5551 | 0.133* | 0.654 (13) |
H18B | 0.6314 | 0.9365 | 0.6208 | 0.133* | 0.654 (13) |
C19A | 0.7387 (9) | 0.8319 (5) | 0.6471 (5) | 0.110 (3)* | 0.654 (13) |
H19A | 0.8335 | 0.8167 | 0.6448 | 0.131* | 0.654 (13) |
H19B | 0.6882 | 0.7894 | 0.6217 | 0.131* | 0.654 (13) |
C18B | 0.6958 (19) | 0.9298 (10) | 0.6440 (13) | 0.123 (6)* | 0.346 (13) |
H18C | 0.6483 | 0.9011 | 0.6055 | 0.148* | 0.346 (13) |
H18D | 0.6332 | 0.9648 | 0.6704 | 0.148* | 0.346 (13) |
C19B | 0.7806 (17) | 0.8700 (10) | 0.6907 (9) | 0.106 (6)* | 0.346 (13) |
H19C | 0.8317 | 0.8323 | 0.6604 | 0.127* | 0.346 (13) |
H19D | 0.8429 | 0.9003 | 0.7214 | 0.127* | 0.346 (13) |
C20 | 0.6977 (6) | 0.8327 (4) | 0.7270 (3) | 0.1318 (19) | |
H20A | 0.7264 | 0.8838 | 0.7498 | 0.158* | 0.654 (13) |
H20B | 0.5999 | 0.8302 | 0.7295 | 0.158* | 0.654 (13) |
H20C | 0.6280 | 0.8126 | 0.6945 | 0.158* | 0.346 (13) |
H20D | 0.6557 | 0.8706 | 0.7609 | 0.158* | 0.346 (13) |
C21 | 0.6009 (5) | 0.6022 (3) | 0.8941 (3) | 0.1185 (17) | |
H21A | 0.6451 | 0.5538 | 0.9140 | 0.142* | |
H21B | 0.5376 | 0.5828 | 0.8577 | 0.142* | |
C22 | 0.5168 (5) | 0.6426 (4) | 0.9560 (3) | 0.1223 (17) | |
H22A | 0.4810 | 0.6948 | 0.9387 | 0.147* | |
H22B | 0.4405 | 0.6070 | 0.9669 | 0.147* | |
C23 | 0.5904 (5) | 0.6574 (4) | 1.0220 (3) | 0.1110 (16) | |
H23 | 0.6411 | 0.6132 | 1.0393 | 0.133* | |
C24 | 0.5952 (5) | 0.7264 (3) | 1.0615 (3) | 0.1054 (15) | |
H24 | 0.6456 | 0.7247 | 1.1039 | 0.126* | |
C25 | 0.5297 (6) | 0.8025 (4) | 1.0443 (3) | 0.1275 (19) | |
H25 | 0.4787 | 0.8045 | 1.0020 | 0.153* | |
C26 | 0.5363 (6) | 0.8723 (4) | 1.0851 (4) | 0.144 (2) | |
H26 | 0.4883 | 0.9174 | 1.0671 | 0.173* | |
C27 | 0.6096 (7) | 0.8872 (4) | 1.1546 (3) | 0.132 (2) | |
H27A | 0.6555 | 0.8367 | 1.1690 | 0.158* | |
H27B | 0.5446 | 0.9008 | 1.1920 | 0.158* | |
C28 | 0.7128 (8) | 0.9568 (4) | 1.1486 (3) | 0.146 (2) | |
H28A | 0.6669 | 1.0068 | 1.1332 | 0.175* | |
H28B | 0.7512 | 0.9671 | 1.1961 | 0.175* | |
C29 | 0.8270 (7) | 0.9382 (3) | 1.0956 (3) | 0.1227 (18) | |
H29A | 0.7879 | 0.9200 | 1.0502 | 0.147* | |
H29B | 0.8761 | 0.9891 | 1.0862 | 0.147* | |
C30 | 0.9266 (5) | 0.8732 (3) | 1.1214 (2) | 0.1101 (15) | |
H30A | 0.8781 | 0.8222 | 1.1312 | 0.132* | |
H30B | 0.9675 | 0.8915 | 1.1663 | 0.132* | |
C31 | 1.0393 (5) | 0.8558 (3) | 1.0654 (2) | 0.1045 (15) | |
H31A | 1.0733 | 0.9081 | 1.0471 | 0.125* | |
H31B | 1.1134 | 0.8277 | 1.0894 | 0.125* | |
C32 | 0.9917 (4) | 0.8033 (3) | 1.0018 (2) | 0.0826 (12) | |
H32A | 0.9550 | 0.7518 | 1.0203 | 0.099* | |
H32B | 0.9192 | 0.8322 | 0.9771 | 0.099* | |
N1 | 1.2672 (3) | 0.8432 (2) | 0.86212 (19) | 0.0869 (10) | |
N2 | 0.7026 (3) | 0.6504 (2) | 0.8575 (2) | 0.0925 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.081 (3) | 0.080 (3) | 0.095 (3) | −0.005 (2) | 0.000 (3) | −0.003 (2) |
C2 | 0.079 (3) | 0.079 (3) | 0.083 (2) | 0.005 (2) | −0.003 (2) | 0.011 (2) |
C3 | 0.082 (3) | 0.064 (2) | 0.093 (3) | 0.009 (2) | 0.001 (3) | 0.020 (2) |
C4 | 0.082 (3) | 0.083 (3) | 0.101 (3) | 0.016 (2) | 0.012 (3) | 0.006 (3) |
C5 | 0.068 (3) | 0.100 (3) | 0.095 (3) | 0.010 (3) | 0.012 (2) | 0.007 (3) |
C6 | 0.090 (3) | 0.112 (4) | 0.099 (3) | 0.006 (3) | −0.012 (3) | −0.008 (3) |
C7 | 0.099 (3) | 0.093 (3) | 0.100 (3) | 0.021 (3) | −0.009 (3) | 0.000 (3) |
C8 | 0.076 (3) | 0.077 (3) | 0.096 (3) | 0.002 (2) | −0.006 (2) | 0.007 (2) |
C9 | 0.079 (3) | 0.062 (2) | 0.082 (2) | 0.008 (2) | 0.001 (2) | 0.000 (2) |
C10 | 0.081 (3) | 0.076 (3) | 0.104 (3) | −0.007 (2) | 0.000 (3) | 0.005 (2) |
C11 | 0.074 (3) | 0.117 (4) | 0.115 (3) | −0.022 (3) | 0.003 (3) | 0.011 (3) |
C12 | 0.106 (4) | 0.095 (3) | 0.151 (4) | −0.032 (3) | 0.006 (4) | 0.024 (4) |
C13 | 0.104 (4) | 0.113 (4) | 0.121 (4) | −0.007 (3) | 0.023 (4) | 0.030 (3) |
C14 | 0.116 (4) | 0.079 (3) | 0.108 (4) | −0.014 (3) | 0.020 (4) | 0.009 (3) |
C15 | 0.159 (6) | 0.116 (4) | 0.100 (4) | 0.025 (4) | 0.021 (4) | 0.021 (4) |
C16 | 0.170 (6) | 0.103 (4) | 0.098 (4) | 0.028 (4) | 0.001 (5) | 0.005 (3) |
C17 | 0.146 (4) | 0.083 (3) | 0.103 (3) | 0.001 (3) | −0.036 (4) | 0.012 (3) |
C20 | 0.120 (4) | 0.145 (5) | 0.131 (4) | 0.048 (4) | −0.010 (4) | 0.008 (4) |
C21 | 0.103 (4) | 0.107 (3) | 0.145 (4) | −0.033 (3) | −0.014 (4) | −0.015 (4) |
C22 | 0.087 (3) | 0.152 (5) | 0.128 (4) | −0.024 (3) | 0.004 (3) | −0.010 (4) |
C23 | 0.098 (3) | 0.118 (4) | 0.117 (4) | −0.009 (4) | 0.004 (3) | −0.001 (4) |
C24 | 0.081 (3) | 0.120 (4) | 0.115 (4) | −0.001 (3) | 0.003 (3) | 0.018 (4) |
C25 | 0.109 (4) | 0.136 (5) | 0.137 (4) | 0.021 (4) | 0.001 (4) | 0.002 (4) |
C26 | 0.133 (5) | 0.129 (5) | 0.171 (6) | 0.038 (4) | 0.008 (5) | −0.010 (5) |
C27 | 0.142 (5) | 0.141 (5) | 0.112 (4) | 0.022 (4) | 0.032 (4) | −0.022 (4) |
C28 | 0.198 (7) | 0.120 (4) | 0.119 (4) | 0.033 (5) | 0.017 (5) | −0.031 (4) |
C29 | 0.155 (5) | 0.088 (3) | 0.125 (4) | −0.004 (3) | 0.014 (4) | −0.003 (3) |
C30 | 0.123 (4) | 0.123 (4) | 0.085 (3) | −0.005 (4) | −0.005 (3) | −0.017 (3) |
C31 | 0.101 (3) | 0.130 (4) | 0.083 (3) | −0.010 (3) | −0.003 (3) | −0.008 (3) |
C32 | 0.091 (3) | 0.085 (3) | 0.072 (2) | −0.006 (2) | −0.002 (2) | 0.002 (2) |
N1 | 0.069 (2) | 0.096 (2) | 0.095 (2) | −0.008 (2) | 0.004 (2) | 0.001 (2) |
N2 | 0.086 (2) | 0.080 (2) | 0.111 (3) | −0.015 (2) | −0.005 (2) | −0.010 (2) |
C1—N1 | 1.447 (5) | C17—H17C | 0.9700 |
C1—C2 | 1.541 (5) | C17—H17D | 0.9700 |
C1—H1A | 0.9700 | C18A—C19A | 1.542 (8) |
C1—H1B | 0.9700 | C18A—H18A | 0.9700 |
C2—C32 | 1.512 (5) | C18A—H18B | 0.9700 |
C2—C3 | 1.570 (6) | C19A—C20 | 1.530 (10) |
C2—H2 | 0.9800 | C19A—H19A | 0.9700 |
C3—C4 | 1.545 (5) | C19A—H19B | 0.9701 |
C3—C9 | 1.552 (5) | C18B—C19B | 1.543 (8) |
C3—H3 | 0.9800 | C18B—H18C | 0.9700 |
C4—C5 | 1.506 (6) | C18B—H18D | 0.9700 |
C4—H4A | 0.9700 | C19B—C20 | 1.219 (14) |
C4—H4B | 0.9700 | C19B—H19C | 0.9700 |
C5—N1 | 1.427 (5) | C19B—H19D | 0.9700 |
C5—H5A | 0.9700 | C20—H20A | 0.9699 |
C5—H5B | 0.9700 | C20—H20B | 0.9700 |
C6—N2 | 1.438 (5) | C20—H20C | 0.9700 |
C6—C7 | 1.499 (6) | C20—H20D | 0.9699 |
C6—H6A | 0.9700 | C21—N2 | 1.441 (6) |
C6—H6B | 0.9700 | C21—C22 | 1.558 (7) |
C7—C8 | 1.522 (6) | C21—H21A | 0.9700 |
C7—C20 | 1.561 (6) | C21—H21B | 0.9700 |
C7—H7 | 0.9800 | C22—C23 | 1.439 (6) |
C8—C9 | 1.510 (5) | C22—H22A | 0.9700 |
C8—H8A | 0.9700 | C22—H22B | 0.9700 |
C8—H8B | 0.9700 | C23—C24 | 1.333 (6) |
C9—C10 | 1.509 (5) | C23—H23 | 0.9300 |
C9—H9 | 0.9800 | C24—C25 | 1.426 (7) |
C10—N2 | 1.455 (5) | C24—H24 | 0.9300 |
C10—H10A | 0.9700 | C25—C26 | 1.359 (8) |
C10—H10B | 0.9700 | C25—H25 | 0.9300 |
C11—N1 | 1.459 (5) | C26—C27 | 1.493 (8) |
C11—C12 | 1.526 (6) | C26—H26 | 0.9300 |
C11—H11A | 0.9700 | C27—C28 | 1.524 (8) |
C11—H11B | 0.9700 | C27—H27A | 0.9700 |
C12—C13 | 1.522 (8) | C27—H27B | 0.9700 |
C12—H12A | 0.9700 | C28—C29 | 1.523 (7) |
C12—H12B | 0.9700 | C28—H28A | 0.9700 |
C13—C14 | 1.319 (7) | C28—H28B | 0.9700 |
C13—H13 | 0.9300 | C29—C30 | 1.517 (7) |
C14—C15 | 1.400 (7) | C29—H29A | 0.9700 |
C14—H14 | 0.9300 | C29—H29B | 0.9700 |
C15—C16 | 1.309 (8) | C30—C31 | 1.546 (6) |
C15—H15 | 0.9300 | C30—H30A | 0.9700 |
C16—C17 | 1.475 (7) | C30—H30B | 0.9700 |
C16—H16 | 0.9300 | C31—C32 | 1.523 (6) |
C17—C18A | 1.446 (9) | C31—H31A | 0.9700 |
C17—C18B | 1.56 (2) | C31—H31B | 0.9700 |
C17—H17A | 0.9699 | C32—H32A | 0.9700 |
C17—H17B | 0.9699 | C32—H32B | 0.9700 |
N1—C1—C2 | 111.5 (3) | C17—C18A—C19A | 119.2 (7) |
N1—C1—H1A | 109.3 | C17—C18A—H18A | 107.3 |
C2—C1—H1A | 109.3 | C19A—C18A—H18A | 106.9 |
N1—C1—H1B | 109.3 | C17—C18A—H18B | 108.5 |
C2—C1—H1B | 109.3 | C19A—C18A—H18B | 107.6 |
H1A—C1—H1B | 108.0 | H18A—C18A—H18B | 106.7 |
C32—C2—C1 | 112.3 (3) | C20—C19A—C18A | 115.5 (6) |
C32—C2—C3 | 115.9 (3) | C20—C19A—H19A | 107.4 |
C1—C2—C3 | 110.9 (3) | C18A—C19A—H19A | 108.9 |
C32—C2—H2 | 105.6 | C20—C19A—H19B | 109.6 |
C1—C2—H2 | 105.6 | C18A—C19A—H19B | 107.8 |
C3—C2—H2 | 105.6 | H19A—C19A—H19B | 107.3 |
C4—C3—C9 | 112.4 (3) | C19B—C18B—C17 | 95.6 (11) |
C4—C3—C2 | 108.3 (3) | C19B—C18B—H18C | 111.8 |
C9—C3—C2 | 121.0 (3) | C17—C18B—H18C | 110.5 |
C4—C3—H3 | 104.5 | C19B—C18B—H18D | 115.5 |
C9—C3—H3 | 104.5 | C17—C18B—H18D | 113.0 |
C2—C3—H3 | 104.5 | H18C—C18B—H18D | 109.7 |
C5—C4—C3 | 114.0 (3) | C20—C19B—C18B | 104.6 (14) |
C5—C4—H4A | 108.8 | C20—C19B—H19C | 110.8 |
C3—C4—H4A | 108.8 | C18B—C19B—H19C | 110.8 |
C5—C4—H4B | 108.8 | C20—C19B—H19D | 110.8 |
C3—C4—H4B | 108.8 | C18B—C19B—H19D | 110.8 |
H4A—C4—H4B | 107.7 | H19C—C19B—H19D | 108.9 |
N1—C5—C4 | 112.1 (4) | C19B—C20—C7 | 115.7 (7) |
N1—C5—H5A | 109.2 | C19A—C20—C7 | 114.0 (5) |
C4—C5—H5A | 109.2 | C19A—C20—H20A | 110.4 |
N1—C5—H5B | 109.2 | C7—C20—H20A | 109.0 |
C4—C5—H5B | 109.2 | C19A—C20—H20B | 108.0 |
H5A—C5—H5B | 107.9 | C7—C20—H20B | 107.3 |
N2—C6—C7 | 110.3 (4) | H20A—C20—H20B | 107.8 |
N2—C6—H6A | 109.6 | C19B—C20—H20C | 107.7 |
C7—C6—H6A | 109.6 | C7—C20—H20C | 108.6 |
N2—C6—H6B | 109.6 | C19B—C20—H20D | 109.3 |
C7—C6—H6B | 109.6 | C7—C20—H20D | 107.5 |
H6A—C6—H6B | 108.1 | H20C—C20—H20D | 107.8 |
C6—C7—C8 | 110.1 (4) | N2—C21—C22 | 119.4 (4) |
C6—C7—C20 | 112.2 (4) | N2—C21—H21A | 107.5 |
C8—C7—C20 | 113.2 (4) | C22—C21—H21A | 107.5 |
C6—C7—H7 | 107.0 | N2—C21—H21B | 107.5 |
C8—C7—H7 | 107.0 | C22—C21—H21B | 107.5 |
C20—C7—H7 | 107.0 | H21A—C21—H21B | 107.0 |
C9—C8—C7 | 111.1 (3) | C23—C22—C21 | 114.9 (4) |
C9—C8—H8A | 109.4 | C23—C22—H22A | 108.5 |
C7—C8—H8A | 109.4 | C21—C22—H22A | 108.5 |
C9—C8—H8B | 109.4 | C23—C22—H22B | 108.5 |
C7—C8—H8B | 109.4 | C21—C22—H22B | 108.5 |
H8A—C8—H8B | 108.0 | H22A—C22—H22B | 107.5 |
C10—C9—C8 | 108.5 (3) | C24—C23—C22 | 128.3 (6) |
C10—C9—C3 | 113.9 (3) | C24—C23—H23 | 115.8 |
C8—C9—C3 | 118.8 (3) | C22—C23—H23 | 115.8 |
C10—C9—H9 | 104.7 | C23—C24—C25 | 125.8 (6) |
C8—C9—H9 | 104.7 | C23—C24—H24 | 117.1 |
C3—C9—H9 | 104.7 | C25—C24—H24 | 117.1 |
N2—C10—C9 | 111.1 (3) | C26—C25—C24 | 124.9 (6) |
N2—C10—H10A | 109.4 | C26—C25—H25 | 117.5 |
C9—C10—H10A | 109.4 | C24—C25—H25 | 117.5 |
N2—C10—H10B | 109.4 | C25—C26—C27 | 129.3 (6) |
C9—C10—H10B | 109.4 | C25—C26—H26 | 115.4 |
H10A—C10—H10B | 108.0 | C27—C26—H26 | 115.4 |
N1—C11—C12 | 117.8 (4) | C26—C27—C28 | 112.4 (6) |
N1—C11—H11A | 107.9 | C26—C27—H27A | 109.1 |
C12—C11—H11A | 107.9 | C28—C27—H27A | 109.1 |
N1—C11—H11B | 107.9 | C26—C27—H27B | 109.1 |
C12—C11—H11B | 107.9 | C28—C27—H27B | 109.1 |
H11A—C11—H11B | 107.2 | H27A—C27—H27B | 107.9 |
C13—C12—C11 | 116.3 (5) | C29—C28—C27 | 113.4 (5) |
C13—C12—H12A | 108.2 | C29—C28—H28A | 108.9 |
C11—C12—H12A | 108.2 | C27—C28—H28A | 108.9 |
C13—C12—H12B | 108.2 | C29—C28—H28B | 108.9 |
C11—C12—H12B | 108.2 | C27—C28—H28B | 108.9 |
H12A—C12—H12B | 107.4 | H28A—C28—H28B | 107.7 |
C14—C13—C12 | 126.5 (6) | C30—C29—C28 | 114.6 (4) |
C14—C13—H13 | 116.8 | C30—C29—H29A | 108.6 |
C12—C13—H13 | 116.8 | C28—C29—H29A | 108.6 |
C13—C14—C15 | 124.9 (6) | C30—C29—H29B | 108.6 |
C13—C14—H14 | 117.6 | C28—C29—H29B | 108.6 |
C15—C14—H14 | 117.6 | H29A—C29—H29B | 107.6 |
C16—C15—C14 | 128.3 (6) | C29—C30—C31 | 112.6 (4) |
C16—C15—H15 | 115.8 | C29—C30—H30A | 109.1 |
C14—C15—H15 | 115.8 | C31—C30—H30A | 109.1 |
C15—C16—C17 | 127.5 (5) | C29—C30—H30B | 109.1 |
C15—C16—H16 | 116.3 | C31—C30—H30B | 109.1 |
C17—C16—H16 | 116.3 | H30A—C30—H30B | 107.8 |
C18A—C17—C16 | 106.7 (6) | C32—C31—C30 | 113.2 (4) |
C16—C17—C18B | 127.9 (8) | C32—C31—H31A | 108.9 |
C18A—C17—H17A | 97.1 | C30—C31—H31A | 108.9 |
C16—C17—H17A | 105.2 | C32—C31—H31B | 108.9 |
C18B—C17—H17A | 106.7 | C30—C31—H31B | 108.9 |
C18A—C17—H17B | 133.6 | H31A—C31—H31B | 107.8 |
C16—C17—H17B | 105.0 | C2—C32—C31 | 113.9 (3) |
C18B—C17—H17B | 104.2 | C2—C32—H32A | 108.8 |
H17A—C17—H17B | 106.2 | C31—C32—H32A | 108.8 |
C18A—C17—H17C | 111.3 | C2—C32—H32B | 108.8 |
C16—C17—H17C | 110.6 | C31—C32—H32B | 108.8 |
C18B—C17—H17C | 83.2 | H32A—C32—H32B | 107.7 |
H17A—C17—H17C | 124.1 | C5—N1—C1 | 111.4 (3) |
C18A—C17—H17D | 109.1 | C5—N1—C11 | 116.6 (3) |
C16—C17—H17D | 110.1 | C1—N1—C11 | 113.5 (4) |
C18B—C17—H17D | 111.9 | C6—N2—C21 | 113.5 (4) |
H17B—C17—H17D | 90.3 | C6—N2—C10 | 111.5 (3) |
H17C—C17—H17D | 109.0 | C21—N2—C10 | 115.1 (4) |
N1—C1—C2—C32 | 172.1 (3) | C17—C18B—C19B—C20 | 171.8 (16) |
N1—C1—C2—C3 | −56.5 (4) | C18B—C19B—C20—C7 | 171.1 (9) |
C32—C2—C3—C4 | 178.2 (3) | C18A—C19A—C20—C7 | −164.7 (6) |
C1—C2—C3—C4 | 48.6 (4) | C6—C7—C20—C19B | 173.1 (12) |
C32—C2—C3—C9 | 46.4 (5) | C8—C7—C20—C19B | 47.8 (13) |
C1—C2—C3—C9 | −83.2 (4) | C6—C7—C20—C19A | −136.8 (6) |
C9—C3—C4—C5 | 88.1 (5) | C8—C7—C20—C19A | 97.9 (7) |
C2—C3—C4—C5 | −48.2 (5) | N2—C21—C22—C23 | −71.3 (7) |
C3—C4—C5—N1 | 54.4 (5) | C21—C22—C23—C24 | 131.5 (6) |
N2—C6—C7—C8 | −56.7 (5) | C22—C23—C24—C25 | −2.3 (9) |
N2—C6—C7—C20 | 176.3 (4) | C23—C24—C25—C26 | −179.7 (6) |
C6—C7—C8—C9 | 54.7 (5) | C24—C25—C26—C27 | 0.1 (11) |
C20—C7—C8—C9 | −178.8 (4) | C25—C26—C27—C28 | 120.6 (8) |
C7—C8—C9—C10 | −54.3 (4) | C26—C27—C28—C29 | −63.8 (7) |
C7—C8—C9—C3 | 173.5 (3) | C27—C28—C29—C30 | −71.4 (6) |
C4—C3—C9—C10 | 151.5 (3) | C28—C29—C30—C31 | 179.3 (5) |
C2—C3—C9—C10 | −78.4 (4) | C29—C30—C31—C32 | −75.9 (6) |
C4—C3—C9—C8 | −78.7 (4) | C1—C2—C32—C31 | −67.9 (4) |
C2—C3—C9—C8 | 51.4 (5) | C3—C2—C32—C31 | 163.2 (3) |
C8—C9—C10—N2 | 57.2 (4) | C30—C31—C32—C2 | −178.3 (4) |
C3—C9—C10—N2 | −168.0 (3) | C4—C5—N1—C1 | −59.7 (5) |
N1—C11—C12—C13 | −68.8 (6) | C4—C5—N1—C11 | 168.0 (3) |
C11—C12—C13—C14 | 134.8 (5) | C2—C1—N1—C5 | 61.5 (4) |
C12—C13—C14—C15 | 179.6 (5) | C2—C1—N1—C11 | −164.6 (3) |
C13—C14—C15—C16 | −179.1 (6) | C12—C11—N1—C5 | 73.2 (5) |
C14—C15—C16—C17 | −4.4 (10) | C12—C11—N1—C1 | −58.2 (5) |
C15—C16—C17—C18A | −121.3 (7) | C7—C6—N2—C21 | −167.5 (4) |
C15—C16—C17—C18B | −97.6 (12) | C7—C6—N2—C10 | 60.6 (5) |
C16—C17—C18A—C19A | 62.0 (10) | C22—C21—N2—C6 | −61.1 (5) |
C18B—C17—C18A—C19A | −78.2 (13) | C22—C21—N2—C10 | 69.0 (5) |
C17—C18A—C19A—C20 | 81.6 (12) | C9—C10—N2—C6 | −61.5 (5) |
C16—C17—C18B—C19B | 45.6 (16) | C9—C10—N2—C21 | 167.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C32H52N2 |
Mr | 464.76 |
Crystal system, space group | Orthorhombic, P22121 |
Temperature (K) | 293 |
a, b, c (Å) | 9.8895 (3), 16.1689 (5), 18.4642 (7) |
V (Å3) | 2952.47 (17) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini S Ultra diffractometer |
Absorption correction | Multi-scan [CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] |
Tmin, Tmax | 0.820, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8051, 2628, 1427 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.575 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.148, 0.88 |
No. of reflections | 2628 |
No. of parameters | 307 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.12 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2008), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
From both a structural and a biosynthetic perspective, 3-alkylpiperidines are among the most intriguing of metabolites isolated from marine sponge extracts. Over 30 different carbon skeletons have been documented, with the haliclonacyclamine/arenosclerin skeleton providing more than ten examples from Indo-Pacific, Brazilian and Red Sea sponges (Berlinck, 2007). Our recent isolation of a crystalline sample of tetradehydrohaliclonacyclamine A, (I), from a sponge specimen provisionally identified as Halichondria sp. (Mudianta et al., 2010) afforded an opportunity to determine the absolute configuration of this sponge metabolite crystallographically, and to compare it with our earlier structural data for the haliclonacyclamines A, (II), and B, (III) (Charan et al., 1996; Clark et al., 1998; Mudianta et al., 2009).
Previously we have reported the absolute structure determinations of haliclonacyclamines A, (II), and B, (III) (Mudianta et al., 2009), isolated from a Haliclona species collected at Heron Island (Australia). Absolute structures of compounds from this family are few and these provide an important link with optical rotation data that cannot be relied upon for absolute structure assignment alone. This is evident from our report that (-)-haliclonacyclamine A, (II), and (+)-haliclonacyclamine B, (II) [(III)?] each share the same absolute configuration of 2R,3R,7R,9R (Mudianta et al., 2009). Interestingly, the closely related unsaturated analogue, (I), from the Indonesian sponge Halichondria sp., has an opposite absolute configuration (2S,3S,7S,9S), as shown by a recent low-temperature crystallographic structure determination (Mudianta et al., 2010). Full characterization of this compound was reported, including its NMR solution structure. During the course of our crystallographic study we observed a totally reversible phase change at ca 250 K from a monoclinic (P21, Z = 4) form to an orthorhombic (higher-temperature) lattice. We report here the details of this higher-temperature form and identify the molecular features that are altered upon conversion to the higher-symmetry lattice at room temperature.
The crystal structure of (I) was determined at 293 K. The compound crystallizes in the orthorhombic space group P22121 and all molecules occupy general sites. Discussion of the structure is aided by comparison with its low-temperature form. Note that we report the variant P22121 form (instead of the standard setting P21212) to aid comparison with the monoclinic structure where the axes are conserved. Inspection of the lattice dimensions of the high- and low-temperature forms illustrates the most significant changes between the two structures. The phase change from monoclinic to orthorhombic is subtle and the unit cells are very similar. In the monoclinic form at 130 K, the cell dimensions are a = 9.8074 (1) Å [cf. 9.8895 (3) Å at 293 K], b = 15.9505 (2) Å [cf. 16.1689 (5) Å at 293 K], c 18.3186 (2) Å [cf. 18.4642 (7) Å at 293 K] and β 92.449 (1)°, which is naturally 90° at 293 K. The unit-cell dimensions were measured at various temperatures between 130 K and 293 K and an approximate phase transition at 250 K was defined. When the phase change is complete, the new crystallographic twofold screw axis parallel with c and the twofold rotation axis parallel with a emerge, and the two independent molecules found in the monoclinic phase become symmetry related.
The gross features of the orthorhombic structure of (I) at 293 K are similar to those found in the low-temperature (130 K) monoclinic phase. In the low-temperature phase two independent molecules exhibiting different conformations in the region spanned by methylene atoms C17–C20 were identified. In the high-temperature phase, all molecules are disordered between two different conformations (Fig. 1a). The A conformer in the high-temperature phase closely resembles the A conformer seen in the monoclinic form shown in Fig. 1(b) (Mudianta et al., 2010). The relevant torsion angles are 81.6 (12) and 85.2 (2)°, respectively. Interestingly, the occupancies of the two conformers in the high-temperature form are significantly different (0.65 for molecule A and 0.35 for molecule B), while the ratio of the two conformers in the monoclinic low-temperature phase is necessarily 1:1.
The absolute structure of (I) was established previously at 130 K (Mudianta et al., 2010) by the Bijvoet pair analysis (Hooft et al., 2008) implemented within the PLATON program (Spek, 2009). The same crystal previously examined at 130 K (Mudianta et al., 2010) was used here for the 293 K structure.
The transformation between the low-temperature monoclinic form of (I) and the high-temperature orthorhombic phase is totally reversible. As the temperature is raised, β decreases gradually until at ca. 250 K the orthorhombic form is dominant. Concurrently, the three unit-cell lengths all increase with temperature, as shown in Fig. 2. As we have shown, this is coupled with the relative proportions of the two distinct molecular conformations of (I). At 250 K and above, one conformer (indicated by the suffix A in Fig. 1a) becomes dominant (65%) and disorder is found in all molecules. At low temperature, two crystallographically distinct molecules exist in equal proportions and are locked into their respective conformations with no disorder.
This work has identified an interesting phase transformation between two crystal systems linked to an actuation of conformational disorder in the higher-temperature phase and a redistribution of the proportions of these distinct conformers.