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The polycyclic title compound {systematic name: (1S,16S,17S,31S)-3,20-diaza­tetra­cyclo­[15.15.01,17.13,31.116,20]tetra­tria­conta-6,8,23,25-tetra­ene}, C32H52N2, has recently been isolated and characterized structurally, in solution by NMR spectroscopy and in the solid state by X-ray crystallography. At 130 K the structure is monoclinic (P21, Z = 4) and comprises two mol­ecules in the asymmetric unit with distinctly different conformations in the twelve-C-atom bridging chains. We report that, at 250 K, a phase change from monoclinic to ortho­rhom­bic (P22121, Z = 4) occurs. The higher-temperature phase is structurally characterized herein at 293 K. The two different conformers resolved in the monoclinic low-temperature form merge to give a single disordered mol­ecule in the asymmetric unit of the high-temperature phase.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110004634/sk3354sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110004634/sk3354Isup2.hkl
Contains datablock I

CCDC reference: 774898

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. (a) The structure of (I), with the atom-numbering scheme, showing the methylene group disorder between atoms C17 and C20; the C—C and C—H bonds of the minor contributor are shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Parts (b) and (c) show the crystallographically independent molecules of (I) in the 130 K structure (Mudianta et al., 2010). [NB Part (b) has not been received - please supply the required plot]
[Figure 2] Fig. 2. PLUTON plot (Spek, 2009) of the 293 K orthorhombic unit cell of (I), viewed in the [010] direction, and the variations in unit-cell dimensions as a function of temperature. [Axes are very faint - please provide revised plot]
(1S,16S,17S,31S)-3,20- Diazatetracyclo[15,15,01,17,13,31,116,20]tetratriaconta-6,8,23,25- tetraene top
Crystal data top
C32H52N2F(000) = 1032
Mr = 464.76Dx = 1.046 Mg m3
Orthorhombic, P22121Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2bc 2Cell parameters from 1581 reflections
a = 9.8895 (3) Åθ = 2.7–62.5°
b = 16.1689 (5) ŵ = 0.44 mm1
c = 18.4642 (7) ÅT = 293 K
V = 2952.47 (17) Å3Prism, colourless
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Oxford Diffraction Gemini S Ultra
diffractometer
2628 independent reflections
Radiation source: Ultra (Cu) X-ray Source1427 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.036
Detector resolution: 16.0696 pixels mm-1θmax = 62.5°, θmin = 3.6°
ω scansh = 711
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 = 1815
Tmin = 0.820, Tmax = 1.000l = 2117
8051 measured reflections
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)] = 0.049H-atom parameters constrained
wR(F2) = 0.148 w = 1/[s2(Fo2) + (0.091P)2]
S = 0.88(Δ/σ)max < 0.001
2628 reflectionsΔρmax = 0.16 e Å3
307 parametersΔρmin = 0.12 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0028 (5)
Crystal data top
C32H52N2V = 2952.47 (17) Å3
Mr = 464.76Z = 4
Orthorhombic, P22121Cu Kα radiation
a = 9.8895 (3) ŵ = 0.44 mm1
b = 16.1689 (5) ÅT = 293 K
c = 18.4642 (7) Å0.3 × 0.2 × 0.2 mm
Data collection top
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 = 1.000Rint = 0.036
8051 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0492 restraints
wR(F2) = 0.148H-atom parameters constrained
S = 0.88Δρmax = 0.16 e Å3
2628 reflectionsΔρmin = 0.12 e Å3
307 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C11.1498 (4)0.8609 (2)0.9062 (2)0.0855 (12)
H1A1.07720.88080.87550.103*
H1B1.17180.90430.94050.103*
C21.1018 (4)0.7836 (2)0.9477 (2)0.0804 (11)
H21.17960.76560.97650.096*
C31.0714 (4)0.7105 (2)0.8941 (2)0.0796 (11)
H31.07520.66080.92440.096*
C41.1925 (4)0.7017 (3)0.8418 (2)0.0887 (13)
H4A1.26780.67740.86790.106*
H4B1.16780.66380.80330.106*
C51.2381 (4)0.7821 (3)0.8086 (2)0.0877 (12)
H5A1.31840.77230.77970.105*
H5B1.16780.80260.77670.105*
C60.6495 (5)0.7221 (3)0.8212 (3)0.1003 (14)
H6A0.62290.76320.85670.120*
H6B0.56990.70680.79350.120*
C70.7538 (5)0.7581 (3)0.7715 (3)0.0970 (14)
H70.77780.71480.73660.116*
C80.8816 (4)0.7789 (2)0.8136 (2)0.0827 (12)
H8A0.95080.79810.78040.099*
H8B0.86260.82310.84750.099*
C90.9334 (4)0.7044 (2)0.8544 (2)0.0745 (10)
H90.94720.66200.81720.089*
C100.8205 (4)0.6711 (3)0.9010 (2)0.0872 (12)
H10A0.85150.62210.92640.105*
H10B0.79570.71210.93690.105*
C111.3378 (4)0.9172 (3)0.8373 (3)0.1020 (15)
H11A1.41490.89960.80880.122*
H11B1.37280.94560.87960.122*
C121.2579 (5)0.9797 (3)0.7926 (3)0.1173 (17)
H12A1.17680.99420.81930.141*
H12B1.31191.02960.78810.141*
C131.2163 (6)0.9523 (3)0.7169 (3)0.1128 (17)
H131.28200.92610.68910.135*
C141.0963 (6)0.9619 (3)0.6869 (3)0.1009 (15)
H141.02960.98770.71430.121*
C151.0618 (7)0.9362 (3)0.6169 (3)0.1248 (19)
H151.12990.90990.59090.150*
C160.9460 (8)0.9445 (3)0.5833 (3)0.1238 (19)
H160.94360.92690.53540.149*
C170.8190 (6)0.9784 (3)0.6128 (3)0.1109 (16)
H17A0.78391.01430.57510.133*0.654 (13)
H17B0.84661.01440.65210.133*0.654 (13)
H17C0.83080.99500.66290.133*0.346 (13)
H17D0.79071.02600.58470.133*0.346 (13)
C18A0.7182 (9)0.9141 (5)0.6061 (6)0.111 (3)*0.654 (13)
H18A0.71080.90050.55510.133*0.654 (13)
H18B0.63140.93650.62080.133*0.654 (13)
C19A0.7387 (9)0.8319 (5)0.6471 (5)0.110 (3)*0.654 (13)
H19A0.83350.81670.64480.131*0.654 (13)
H19B0.68820.78940.62170.131*0.654 (13)
C18B0.6958 (19)0.9298 (10)0.6440 (13)0.123 (6)*0.346 (13)
H18C0.64830.90110.60550.148*0.346 (13)
H18D0.63320.96480.67040.148*0.346 (13)
C19B0.7806 (17)0.8700 (10)0.6907 (9)0.106 (6)*0.346 (13)
H19C0.83170.83230.66040.127*0.346 (13)
H19D0.84290.90030.72140.127*0.346 (13)
C200.6977 (6)0.8327 (4)0.7270 (3)0.1318 (19)
H20A0.72640.88380.74980.158*0.654 (13)
H20B0.59990.83020.72950.158*0.654 (13)
H20C0.62800.81260.69450.158*0.346 (13)
H20D0.65570.87060.76090.158*0.346 (13)
C210.6009 (5)0.6022 (3)0.8941 (3)0.1185 (17)
H21A0.64510.55380.91400.142*
H21B0.53760.58280.85770.142*
C220.5168 (5)0.6426 (4)0.9560 (3)0.1223 (17)
H22A0.48100.69480.93870.147*
H22B0.44050.60700.96690.147*
C230.5904 (5)0.6574 (4)1.0220 (3)0.1110 (16)
H230.64110.61321.03930.133*
C240.5952 (5)0.7264 (3)1.0615 (3)0.1054 (15)
H240.64560.72471.10390.126*
C250.5297 (6)0.8025 (4)1.0443 (3)0.1275 (19)
H250.47870.80451.00200.153*
C260.5363 (6)0.8723 (4)1.0851 (4)0.144 (2)
H260.48830.91741.06710.173*
C270.6096 (7)0.8872 (4)1.1546 (3)0.132 (2)
H27A0.65550.83671.16900.158*
H27B0.54460.90081.19200.158*
C280.7128 (8)0.9568 (4)1.1486 (3)0.146 (2)
H28A0.66691.00681.13320.175*
H28B0.75120.96711.19610.175*
C290.8270 (7)0.9382 (3)1.0956 (3)0.1227 (18)
H29A0.78790.92001.05020.147*
H29B0.87610.98911.08620.147*
C300.9266 (5)0.8732 (3)1.1214 (2)0.1101 (15)
H30A0.87810.82221.13120.132*
H30B0.96750.89151.16630.132*
C311.0393 (5)0.8558 (3)1.0654 (2)0.1045 (15)
H31A1.07330.90811.04710.125*
H31B1.11340.82771.08940.125*
C320.9917 (4)0.8033 (3)1.0018 (2)0.0826 (12)
H32A0.95500.75181.02030.099*
H32B0.91920.83220.97710.099*
N11.2672 (3)0.8432 (2)0.86212 (19)0.0869 (10)
N20.7026 (3)0.6504 (2)0.8575 (2)0.0925 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.081 (3)0.080 (3)0.095 (3)0.005 (2)0.000 (3)0.003 (2)
C20.079 (3)0.079 (3)0.083 (2)0.005 (2)0.003 (2)0.011 (2)
C30.082 (3)0.064 (2)0.093 (3)0.009 (2)0.001 (3)0.020 (2)
C40.082 (3)0.083 (3)0.101 (3)0.016 (2)0.012 (3)0.006 (3)
C50.068 (3)0.100 (3)0.095 (3)0.010 (3)0.012 (2)0.007 (3)
C60.090 (3)0.112 (4)0.099 (3)0.006 (3)0.012 (3)0.008 (3)
C70.099 (3)0.093 (3)0.100 (3)0.021 (3)0.009 (3)0.000 (3)
C80.076 (3)0.077 (3)0.096 (3)0.002 (2)0.006 (2)0.007 (2)
C90.079 (3)0.062 (2)0.082 (2)0.008 (2)0.001 (2)0.000 (2)
C100.081 (3)0.076 (3)0.104 (3)0.007 (2)0.000 (3)0.005 (2)
C110.074 (3)0.117 (4)0.115 (3)0.022 (3)0.003 (3)0.011 (3)
C120.106 (4)0.095 (3)0.151 (4)0.032 (3)0.006 (4)0.024 (4)
C130.104 (4)0.113 (4)0.121 (4)0.007 (3)0.023 (4)0.030 (3)
C140.116 (4)0.079 (3)0.108 (4)0.014 (3)0.020 (4)0.009 (3)
C150.159 (6)0.116 (4)0.100 (4)0.025 (4)0.021 (4)0.021 (4)
C160.170 (6)0.103 (4)0.098 (4)0.028 (4)0.001 (5)0.005 (3)
C170.146 (4)0.083 (3)0.103 (3)0.001 (3)0.036 (4)0.012 (3)
C200.120 (4)0.145 (5)0.131 (4)0.048 (4)0.010 (4)0.008 (4)
C210.103 (4)0.107 (3)0.145 (4)0.033 (3)0.014 (4)0.015 (4)
C220.087 (3)0.152 (5)0.128 (4)0.024 (3)0.004 (3)0.010 (4)
C230.098 (3)0.118 (4)0.117 (4)0.009 (4)0.004 (3)0.001 (4)
C240.081 (3)0.120 (4)0.115 (4)0.001 (3)0.003 (3)0.018 (4)
C250.109 (4)0.136 (5)0.137 (4)0.021 (4)0.001 (4)0.002 (4)
C260.133 (5)0.129 (5)0.171 (6)0.038 (4)0.008 (5)0.010 (5)
C270.142 (5)0.141 (5)0.112 (4)0.022 (4)0.032 (4)0.022 (4)
C280.198 (7)0.120 (4)0.119 (4)0.033 (5)0.017 (5)0.031 (4)
C290.155 (5)0.088 (3)0.125 (4)0.004 (3)0.014 (4)0.003 (3)
C300.123 (4)0.123 (4)0.085 (3)0.005 (4)0.005 (3)0.017 (3)
C310.101 (3)0.130 (4)0.083 (3)0.010 (3)0.003 (3)0.008 (3)
C320.091 (3)0.085 (3)0.072 (2)0.006 (2)0.002 (2)0.002 (2)
N10.069 (2)0.096 (2)0.095 (2)0.008 (2)0.004 (2)0.001 (2)
N20.086 (2)0.080 (2)0.111 (3)0.015 (2)0.005 (2)0.010 (2)
Geometric parameters (Å, º) top
C1—N11.447 (5)C17—H17C0.9700
C1—C21.541 (5)C17—H17D0.9700
C1—H1A0.9700C18A—C19A1.542 (8)
C1—H1B0.9700C18A—H18A0.9700
C2—C321.512 (5)C18A—H18B0.9700
C2—C31.570 (6)C19A—C201.530 (10)
C2—H20.9800C19A—H19A0.9700
C3—C41.545 (5)C19A—H19B0.9701
C3—C91.552 (5)C18B—C19B1.543 (8)
C3—H30.9800C18B—H18C0.9700
C4—C51.506 (6)C18B—H18D0.9700
C4—H4A0.9700C19B—C201.219 (14)
C4—H4B0.9700C19B—H19C0.9700
C5—N11.427 (5)C19B—H19D0.9700
C5—H5A0.9700C20—H20A0.9699
C5—H5B0.9700C20—H20B0.9700
C6—N21.438 (5)C20—H20C0.9700
C6—C71.499 (6)C20—H20D0.9699
C6—H6A0.9700C21—N21.441 (6)
C6—H6B0.9700C21—C221.558 (7)
C7—C81.522 (6)C21—H21A0.9700
C7—C201.561 (6)C21—H21B0.9700
C7—H70.9800C22—C231.439 (6)
C8—C91.510 (5)C22—H22A0.9700
C8—H8A0.9700C22—H22B0.9700
C8—H8B0.9700C23—C241.333 (6)
C9—C101.509 (5)C23—H230.9300
C9—H90.9800C24—C251.426 (7)
C10—N21.455 (5)C24—H240.9300
C10—H10A0.9700C25—C261.359 (8)
C10—H10B0.9700C25—H250.9300
C11—N11.459 (5)C26—C271.493 (8)
C11—C121.526 (6)C26—H260.9300
C11—H11A0.9700C27—C281.524 (8)
C11—H11B0.9700C27—H27A0.9700
C12—C131.522 (8)C27—H27B0.9700
C12—H12A0.9700C28—C291.523 (7)
C12—H12B0.9700C28—H28A0.9700
C13—C141.319 (7)C28—H28B0.9700
C13—H130.9300C29—C301.517 (7)
C14—C151.400 (7)C29—H29A0.9700
C14—H140.9300C29—H29B0.9700
C15—C161.309 (8)C30—C311.546 (6)
C15—H150.9300C30—H30A0.9700
C16—C171.475 (7)C30—H30B0.9700
C16—H160.9300C31—C321.523 (6)
C17—C18A1.446 (9)C31—H31A0.9700
C17—C18B1.56 (2)C31—H31B0.9700
C17—H17A0.9699C32—H32A0.9700
C17—H17B0.9699C32—H32B0.9700
N1—C1—C2111.5 (3)C17—C18A—C19A119.2 (7)
N1—C1—H1A109.3C17—C18A—H18A107.3
C2—C1—H1A109.3C19A—C18A—H18A106.9
N1—C1—H1B109.3C17—C18A—H18B108.5
C2—C1—H1B109.3C19A—C18A—H18B107.6
H1A—C1—H1B108.0H18A—C18A—H18B106.7
C32—C2—C1112.3 (3)C20—C19A—C18A115.5 (6)
C32—C2—C3115.9 (3)C20—C19A—H19A107.4
C1—C2—C3110.9 (3)C18A—C19A—H19A108.9
C32—C2—H2105.6C20—C19A—H19B109.6
C1—C2—H2105.6C18A—C19A—H19B107.8
C3—C2—H2105.6H19A—C19A—H19B107.3
C4—C3—C9112.4 (3)C19B—C18B—C1795.6 (11)
C4—C3—C2108.3 (3)C19B—C18B—H18C111.8
C9—C3—C2121.0 (3)C17—C18B—H18C110.5
C4—C3—H3104.5C19B—C18B—H18D115.5
C9—C3—H3104.5C17—C18B—H18D113.0
C2—C3—H3104.5H18C—C18B—H18D109.7
C5—C4—C3114.0 (3)C20—C19B—C18B104.6 (14)
C5—C4—H4A108.8C20—C19B—H19C110.8
C3—C4—H4A108.8C18B—C19B—H19C110.8
C5—C4—H4B108.8C20—C19B—H19D110.8
C3—C4—H4B108.8C18B—C19B—H19D110.8
H4A—C4—H4B107.7H19C—C19B—H19D108.9
N1—C5—C4112.1 (4)C19B—C20—C7115.7 (7)
N1—C5—H5A109.2C19A—C20—C7114.0 (5)
C4—C5—H5A109.2C19A—C20—H20A110.4
N1—C5—H5B109.2C7—C20—H20A109.0
C4—C5—H5B109.2C19A—C20—H20B108.0
H5A—C5—H5B107.9C7—C20—H20B107.3
N2—C6—C7110.3 (4)H20A—C20—H20B107.8
N2—C6—H6A109.6C19B—C20—H20C107.7
C7—C6—H6A109.6C7—C20—H20C108.6
N2—C6—H6B109.6C19B—C20—H20D109.3
C7—C6—H6B109.6C7—C20—H20D107.5
H6A—C6—H6B108.1H20C—C20—H20D107.8
C6—C7—C8110.1 (4)N2—C21—C22119.4 (4)
C6—C7—C20112.2 (4)N2—C21—H21A107.5
C8—C7—C20113.2 (4)C22—C21—H21A107.5
C6—C7—H7107.0N2—C21—H21B107.5
C8—C7—H7107.0C22—C21—H21B107.5
C20—C7—H7107.0H21A—C21—H21B107.0
C9—C8—C7111.1 (3)C23—C22—C21114.9 (4)
C9—C8—H8A109.4C23—C22—H22A108.5
C7—C8—H8A109.4C21—C22—H22A108.5
C9—C8—H8B109.4C23—C22—H22B108.5
C7—C8—H8B109.4C21—C22—H22B108.5
H8A—C8—H8B108.0H22A—C22—H22B107.5
C10—C9—C8108.5 (3)C24—C23—C22128.3 (6)
C10—C9—C3113.9 (3)C24—C23—H23115.8
C8—C9—C3118.8 (3)C22—C23—H23115.8
C10—C9—H9104.7C23—C24—C25125.8 (6)
C8—C9—H9104.7C23—C24—H24117.1
C3—C9—H9104.7C25—C24—H24117.1
N2—C10—C9111.1 (3)C26—C25—C24124.9 (6)
N2—C10—H10A109.4C26—C25—H25117.5
C9—C10—H10A109.4C24—C25—H25117.5
N2—C10—H10B109.4C25—C26—C27129.3 (6)
C9—C10—H10B109.4C25—C26—H26115.4
H10A—C10—H10B108.0C27—C26—H26115.4
N1—C11—C12117.8 (4)C26—C27—C28112.4 (6)
N1—C11—H11A107.9C26—C27—H27A109.1
C12—C11—H11A107.9C28—C27—H27A109.1
N1—C11—H11B107.9C26—C27—H27B109.1
C12—C11—H11B107.9C28—C27—H27B109.1
H11A—C11—H11B107.2H27A—C27—H27B107.9
C13—C12—C11116.3 (5)C29—C28—C27113.4 (5)
C13—C12—H12A108.2C29—C28—H28A108.9
C11—C12—H12A108.2C27—C28—H28A108.9
C13—C12—H12B108.2C29—C28—H28B108.9
C11—C12—H12B108.2C27—C28—H28B108.9
H12A—C12—H12B107.4H28A—C28—H28B107.7
C14—C13—C12126.5 (6)C30—C29—C28114.6 (4)
C14—C13—H13116.8C30—C29—H29A108.6
C12—C13—H13116.8C28—C29—H29A108.6
C13—C14—C15124.9 (6)C30—C29—H29B108.6
C13—C14—H14117.6C28—C29—H29B108.6
C15—C14—H14117.6H29A—C29—H29B107.6
C16—C15—C14128.3 (6)C29—C30—C31112.6 (4)
C16—C15—H15115.8C29—C30—H30A109.1
C14—C15—H15115.8C31—C30—H30A109.1
C15—C16—C17127.5 (5)C29—C30—H30B109.1
C15—C16—H16116.3C31—C30—H30B109.1
C17—C16—H16116.3H30A—C30—H30B107.8
C18A—C17—C16106.7 (6)C32—C31—C30113.2 (4)
C16—C17—C18B127.9 (8)C32—C31—H31A108.9
C18A—C17—H17A97.1C30—C31—H31A108.9
C16—C17—H17A105.2C32—C31—H31B108.9
C18B—C17—H17A106.7C30—C31—H31B108.9
C18A—C17—H17B133.6H31A—C31—H31B107.8
C16—C17—H17B105.0C2—C32—C31113.9 (3)
C18B—C17—H17B104.2C2—C32—H32A108.8
H17A—C17—H17B106.2C31—C32—H32A108.8
C18A—C17—H17C111.3C2—C32—H32B108.8
C16—C17—H17C110.6C31—C32—H32B108.8
C18B—C17—H17C83.2H32A—C32—H32B107.7
H17A—C17—H17C124.1C5—N1—C1111.4 (3)
C18A—C17—H17D109.1C5—N1—C11116.6 (3)
C16—C17—H17D110.1C1—N1—C11113.5 (4)
C18B—C17—H17D111.9C6—N2—C21113.5 (4)
H17B—C17—H17D90.3C6—N2—C10111.5 (3)
H17C—C17—H17D109.0C21—N2—C10115.1 (4)
N1—C1—C2—C32172.1 (3)C17—C18B—C19B—C20171.8 (16)
N1—C1—C2—C356.5 (4)C18B—C19B—C20—C7171.1 (9)
C32—C2—C3—C4178.2 (3)C18A—C19A—C20—C7164.7 (6)
C1—C2—C3—C448.6 (4)C6—C7—C20—C19B173.1 (12)
C32—C2—C3—C946.4 (5)C8—C7—C20—C19B47.8 (13)
C1—C2—C3—C983.2 (4)C6—C7—C20—C19A136.8 (6)
C9—C3—C4—C588.1 (5)C8—C7—C20—C19A97.9 (7)
C2—C3—C4—C548.2 (5)N2—C21—C22—C2371.3 (7)
C3—C4—C5—N154.4 (5)C21—C22—C23—C24131.5 (6)
N2—C6—C7—C856.7 (5)C22—C23—C24—C252.3 (9)
N2—C6—C7—C20176.3 (4)C23—C24—C25—C26179.7 (6)
C6—C7—C8—C954.7 (5)C24—C25—C26—C270.1 (11)
C20—C7—C8—C9178.8 (4)C25—C26—C27—C28120.6 (8)
C7—C8—C9—C1054.3 (4)C26—C27—C28—C2963.8 (7)
C7—C8—C9—C3173.5 (3)C27—C28—C29—C3071.4 (6)
C4—C3—C9—C10151.5 (3)C28—C29—C30—C31179.3 (5)
C2—C3—C9—C1078.4 (4)C29—C30—C31—C3275.9 (6)
C4—C3—C9—C878.7 (4)C1—C2—C32—C3167.9 (4)
C2—C3—C9—C851.4 (5)C3—C2—C32—C31163.2 (3)
C8—C9—C10—N257.2 (4)C30—C31—C32—C2178.3 (4)
C3—C9—C10—N2168.0 (3)C4—C5—N1—C159.7 (5)
N1—C11—C12—C1368.8 (6)C4—C5—N1—C11168.0 (3)
C11—C12—C13—C14134.8 (5)C2—C1—N1—C561.5 (4)
C12—C13—C14—C15179.6 (5)C2—C1—N1—C11164.6 (3)
C13—C14—C15—C16179.1 (6)C12—C11—N1—C573.2 (5)
C14—C15—C16—C174.4 (10)C12—C11—N1—C158.2 (5)
C15—C16—C17—C18A121.3 (7)C7—C6—N2—C21167.5 (4)
C15—C16—C17—C18B97.6 (12)C7—C6—N2—C1060.6 (5)
C16—C17—C18A—C19A62.0 (10)C22—C21—N2—C661.1 (5)
C18B—C17—C18A—C19A78.2 (13)C22—C21—N2—C1069.0 (5)
C17—C18A—C19A—C2081.6 (12)C9—C10—N2—C661.5 (5)
C16—C17—C18B—C19B45.6 (16)C9—C10—N2—C21167.3 (3)

Experimental details

Crystal data
Chemical formulaC32H52N2
Mr464.76
Crystal system, space groupOrthorhombic, P22121
Temperature (K)293
a, b, c (Å)9.8895 (3), 16.1689 (5), 18.4642 (7)
V3)2952.47 (17)
Z4
Radiation typeCu Kα
µ (mm1)0.44
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerOxford Diffraction Gemini S Ultra
diffractometer
Absorption correctionMulti-scan
[CrysAlis RED (Oxford Diffraction, 2008); empirical (using intensity measurements) absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm]
Tmin, Tmax0.820, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8051, 2628, 1427
Rint0.036
(sin θ/λ)max1)0.575
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.148, 0.88
No. of reflections2628
No. of parameters307
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

 

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