organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 11| November 2012| Pages o3095-o3096

(±)-(4bS,8aR,10aS)-10a-Ethynyl-4b,8,8-tri­methyl-3,7-dioxo-3,4b,7,8,8a,9,10,10a-octa­hydro­phenanthrene-2,6-dicarbo­nitrile

aInstitute of Chemical Biology and Drug Discovery, Stony Brook University, Stony Brook, NY 11794, USA, bDepartment of Chemistry, Stony Brook University, Stony Brook, NY 11794, USA, and cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*Correspondence e-mail: jjasinski@keene.edu

(Received 17 August 2012; accepted 1 October 2012; online 10 October 2012)

The anti-inflammatory and cytoprotective tricyclic title compound, C21H18N2O2, also known as TBE-31, crystallizes with two nearly superimposable mol­ecules in the asymmetric unit. In both mol­ecules, the three ring systems conform to an envelope–chair–planar arrangement. The central ring, in a cyclohexane chair conformation, contains an axial ethynyl group that bends slightly off from a nearby axial methyl group because of the 1,3-diaxial repulsion between the two groups. In the crystal, weak C—H⋯N and C—H⋯O inter­actions form chains along [001].

Related literature

For anti-inflammatory, growth suppressive, and proapoptotic properties of TBE-31 and the structural assignment of racemic TBE-31 by NMR spectroscopy, see: Honda et al. (2007[Honda, T., Sundararajan, C., Yoshizawa, H., Su, X., Honda, Y., Liby, K. T., Sporn, M. B. & Gribble, G. W. (2007). J. Med. Chem. 50, 1731-1734.], 2011[Honda, T., Yoshizawa, H., Sundararajan, C., David, E., Lajoie, M. J., Favaloro, F. G. Jr, Janosik, T., Su, X., Honda, Y., Roebuck, B. D. & Gribble, G. W. (2011). J. Med. Chem. 54, 1762-1778.]). For inducing NQO1 and GST in the liver, skin, and stomach in mice, see: Dinkova-Kostova et al. (2010[Dinkova-Kostova, A. T., Talalay, P., Sharkey, J., Zhang, Y., Holtzclaw, W. D., Xiu Jun Wang, X. J., David, E., Schiavoni, K. H., Finlayson, S., Dale, F., Mierke, D. F. & Honda, T. (2010). J. Biol. Chem. 285, 33747-33755.]). For TBE-31 activity against aflatoxin-induced liver cancer in rats, see: Liby et al. (2008[Liby, K., Yore, M. M., Roebuck, B. D., Baumgartner, K. J., Honda, T., Sundararajan, C., Yoshizawa, H., Gribble, G. W., Williams, C. R., Risingsong, R., Royce, D. B., Dinkova-Kostova, A. T., Stephenson, K. K., Egner, P. A., Yates, M. S., Groopman, J. D., Kensler, T. W. & Sporn, M. B. (2008). Cancer Res. 68, 6727-6732.]). For reactivity of the non-enolizable cyano­enone in ring C of TBE-31 compared to that of MCE-1, see: Dinkova-Kostova et al. (2010[Dinkova-Kostova, A. T., Talalay, P., Sharkey, J., Zhang, Y., Holtzclaw, W. D., Xiu Jun Wang, X. J., David, E., Schiavoni, K. H., Finlayson, S., Dale, F., Mierke, D. F. & Honda, T. (2010). J. Biol. Chem. 285, 33747-33755.]). For the biological potency in bioassays for inhibition of inflammation and carcinogenesis and related biological potency, see: Zheng et al. (2012[Zheng, S., Laximi, Y. R. S., David, E., Dinkova-Kostova, A. T., Shiavoni, K. H., Ren, Y., Zheng, Y., Trevino, I., Bumeister, R., Ojima, I., Wigley, W. C., Bliska, J. B., Mierke, D. F. & Honda, T. (2012). J. Med. Chem. 55, 4837-4846.]). For the synthesis of TBE-31, see: Honda et al. (2011[Honda, T., Yoshizawa, H., Sundararajan, C., David, E., Lajoie, M. J., Favaloro, F. G. Jr, Janosik, T., Su, X., Honda, Y., Roebuck, B. D. & Gribble, G. W. (2011). J. Med. Chem. 54, 1762-1778.]). For literature on the number of chemical formula units per asymmetric unit, Z′, see: Steiner (2000[Steiner, T. (2000). Acta Cryst. B56, 673-676.]); Steed (2003[Steed, J. W. (2003). CrystEngComm, 5, 169-179.]); Gavezzotti (2008[Gavezzotti, A. (2008). CrystEngComm, 10, 389-398.]). For ring-puckering parameters, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]). For all-trans-perhydro­phenanthrene comparisons, see: Marcos et al. (2005[Marcos, I. S., Cubillo, M. A., Moro, R. F., Carballares, S., Díez, D., Basabe, P., Llamazares, C. F., Benéitez, A., Sanz, F., Broughton, H. B. & Urones, J. G. (2005). Tetrahedron, 61, 977-1003.]). For a related structure, see: Bore et al. (2002[Bore, L., Honda, T., Gribble, G. W., Lork, E. & Jasinski, J. P. (2002). Acta Cryst. C58, o199-o200.]).

[Scheme 1]

Experimental

Crystal data
  • C21H18N2O2

  • Mr = 330.37

  • Triclinic, [P \overline 1]

  • a = 7.3012 (2) Å

  • b = 12.9843 (3) Å

  • c = 18.4254 (4) Å

  • α = 95.051 (2)°

  • β = 96.284 (2)°

  • γ = 92.338 (2)°

  • V = 1727.26 (7) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 0.66 mm−1

  • T = 299 K

  • 0.71 × 0.46 × 0.29 mm

Data collection
  • Oxford Diffraction Xcalibur Atlas Gemini diffractometer

  • Absorption correction: Gaussian (CrysAlis RED; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]) Tmin = 0.745, Tmax = 0.897

  • 33944 measured reflections

  • 6478 independent reflections

  • 5160 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.140

  • S = 1.03

  • 6478 reflections

  • 458 parameters

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C4A—H4A⋯N2Bi 0.93 2.66 3.572 (3) 166
C4B—H4B⋯N2Ai 0.93 2.69 3.580 (2) 161
C7B—H7B⋯O1Bii 0.93 2.43 3.246 (2) 146
C13B—H13D⋯O1Biii 0.97 2.38 3.324 (2) 163
C13B—H13C⋯O2Aiv 0.97 2.57 3.435 (2) 148
C13A—H13A⋯O1Ai 0.97 2.37 3.295 (2) 159
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z; (iii) -x+1, -y+1, -z; (iv) x, y, z-1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]); software used to prepare material for publication: Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]), PLATON (Spek, 2009)[Spek, A. L. (2009). Acta Cryst. D65, 148-155.] and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The tricyclic compound (±)-(4bS,8aR,10aS)-10a-ethynyl-4b,8,8-trimethyl-3,7-dioxo-3,4b,7,8,8a,9,10,10a-octahydrophenanthrene-2,6-dicarbonitrile (TBE-31) with nonenolizable cyanoenones in rings A and C is a potential anti-inflammatory, growth suppressive, and proapoptotic compound. TBE-31 inhibits nitric oxide (NO) production at low nanomolar concentrations in RAW 264.1 cells and mouse primary macrophages stimulated with IFN-γ (Honda et al., 2007; 2011). TBE-31 induces cytoprotective enzymes HO-1 in RAW cells and in mice (Honda et al., 2007) and NQO1 in Hepa1c1c murine hepatoma cells (Honda et al., 2011). Incorporation of small quantities of TBE-31 in the diet robustly induces NQO1 and GST in the liver, skin, and stomach in mice (Dinkova-Kostova et al., 2010). TBE-31 is orally highly active against aflatoxin–induced liver cancer in rats (Liby et al., 2008). The nonenolizable cyanoenone in ring C of TBE-31 is a highly reactive Michael acceptor and the reactivity is higher than that of MCE-1 (Fig. 3a), which has the same structure as that of ring C (Dinkova-Kostova et al., 2010). Moreover, in this series of Michael acceptors, the reactivity is closely related to the biological potency in the bioassays for inhibition of inflammation and carcinogenesis (Zheng et al., 2012). It has been speculated that the reactivity of the cyanoenone in ring C of TBE-31 would be enhanced because the same structure as that of MCE-1 exists in an unusually unsaturated tricyclic ring system containing eight sp2 carbons. Thus, we have synthesized TBE-31 from cyclohexanone in 14 steps (Honda et al., 2011) and determined the crystal structure of TBE-31. We herein report the crystal structure determination of the title compound, C21H18N2O2, TBE-31, and subsequently discuss its reactivity.

This reported crystal structure confirms previous assignments made by NMR spectroscopy (Honda et al., 2007; 2011). Aside from structural confirmation, the X-ray crystal structure of TBE-31 is interesting due to the presence of two independent molecules in the asymmetric unit (Z' = 2) (Fig. 1). Steiner (2000) reported finding 73% of the organic crystal structures in the Cambridge Structural Database (CSD) with a Z' = 1 while only 9% have Z' = 2. Strong intermolecular interactions have been suspect in the phenomenon of Z' > 1, but Steed concluded that it is not possible to use this information to predict the contents of the asymmetric unit (Steed, 2003). Further analysis of the organic crystal structures in the CSD by Gavezzotti showed that certain space groups show higher frequency of Z' = 2 (Gavezzotti, 2008). In the space group P1, 25% of all the organic crystal structures analyzed by Gavezzotti have Z' = 2 (Gavezzotti, 2008). He also found that 64% of all the organic crystal structures with Z' = 2 contain the ketone functional group. In addition, hydrogen bond accepting nitrogen groups were found in 58% of the Z' = 2 crystal structures (Gavezzotti, 2008). TBE-31 solves in the P1 space group, possesses the ketone functional group, and displays weak C—H···N and C—H···O intermolecular interactions (Table 1) forming chains along (001) (Fig. 2). No H-bond donors are present in TBE-31, but it is crystallized from H-bond donating methanol. The structural attributes of TBE-31 imply it is reasonable to have Z' = 2. The two molecules in the asymmetric unit (A and B molecule; Fig. 1) are also superimposable (r.m.s.d. = 0.091 (1)Å) by local symmetry.

The crystal structure of the title compound, TBE-31, is the latest addition to an important class of cyanoenone-based drugs. The only previously reported crystal structure of a cyanoenone-based drug, to our knowledge, is methyl 2-cyano-3,12-dioxooleana-1,9(11)-dien-28-oate (bardoxolone methyl, CDDO-Me, (Fig. 3(b)) (Bore et al., 2002), which is in phase 3 clinical trials for the treatment of chronic kidney disease in type 2 diabetic patients. It is essential to further study the role of ring strain in these drugs to understand their chemical reactivity as Michael acceptors because it is closely related to their biological potency (Zheng et al., 2012). Ring A (C6A–C11A or C6B–C11B) assumes a slightly distorted envelope conformation (Q = 0.4295 (2) or 0.433 (2), θ = 124.8 (3)° or 57.7 (3)°, ϕ = 120.7 (3)° or 304.7 (3)° for the 1st and 2nd molecule, respectively) (Cremer & Pople, 1975). A typical envelope conformation in this case would maintain a θ value of 54.7° (or 180° - 54.7° = 125.3°) so the distortion is minor. Ring A maintains this conformation due to the rigid Csp2 hybridization at C7A, C8A, and C9A or C7B, C8B and C9B, respectively. Atoms C6A and C10A or C6B and C10B deviate from the Cremer-Pople plane by 0.204 (2) Å and 0.200 (2) Å or 0.215 (2) Å and 0.185 (2) Å, for the 1st or 2nd molecule, respectively. This deviation is most likely influenced by ring B. Ring B (C5A/C6A/C11A—C14A or C5B/C6B/C11B—C14B) is found to be in a slightly distorted cyclohexane chair conformation: Q = 0.5901 (2) or 0.5914 (2), θ = 6.93 (2)° or 173.74 (2)°. A typical θ value for a chair conformtion is 0.00° or 180°. The rigid dienone functionality in ring C (C1A—C5A/C14A or C1B—C5B/C14B) leads to a fully planar geometry (r.m.s.d. = 0.0111 (9) Å or 0.0167 (2) Å for the 1st and 2nd molecule). Therefore, in summary, while both rings A and B are distorted from ideal conformations, Ring C, has a very slight deviation from planarity.

Cremer-Pople analysis, therefore, supports the assignments of the ring systems in TBE-31 as envelope-chair-planar. The distortions from the ideal parameters can be attributed to the result of the rigidity of ring C. The X-ray structure reveals that the methyl group at C6 and hydrogen at C11 is trans and that the methyl group at C6 and alkyne group at C14 is cis. Consequently, two 1,3-diaxial interactions between the methyl group on C6 and ethynyl group on C14 and between the methyl groups on C6 and C10 are observed. In addition, the ethynyl group at C14 bends slightly off from the axial methyl group at C6 because of the 1,3-diaxial repulsion between both groups. These observations contribute to the higher strain seen in TBE-31 as compared to the all-trans perhydrophenanthrene with all chairs, (Marcos et al., 2005). Overall, the X-ray structure of TBE-31 indicates that the unusually unsaturated tricyclic ring systems containing eight sp2 carbons and two 1,3-diaxial interactions, which are closely affected with each other, impose rigid constraints on the conformation of TBE-31. This high strain would increase the reactivity of the nonenolizable cyanoenone in ring C in comparison with that of MCE-1, because MCE-1, which is monocyclic, does not have such strain.

Related literature top

For anti-inflammatory, growth suppressive, and proapoptotic properties of TBE-31 and the structural assignment of racemic TBE-31 by NMR spectroscopy, see: Honda et al. (2007, 2011). For inducing NQO1 and GST in the liver, skin, and stomach in mice, see: Dinkova-Kostova et al. (2010). For TBE-31 activity against aflatoxin-induced liver cancer in rats, see: Liby et al. (2008). For reactivity of the non-enolizable cyanoenone in ring C of TBE-31 compared to that of MCE-1, see: Dinkova-Kostova et al. (2010). For the biological potency in bioassays for inhibition of inflammation and carcinogenesis and related biological potency, see: Zheng et al. (2012). For the synthesis of TBE-31, see: Honda et al. (2011). For literature on the number of chemical formula units per asymmetric crystal unit, Z', see: Steiner (2000); Steed (2003); Gavezzotti (2008). For ring-puckering parameters, see: Cremer & Pople (1975). For all-trans-perhydrophenanthrene comparisons, see: Marcos et al. (2005). For a related structure, see: Bore et al. (2002).

Experimental top

The title compound, C21H18N2O2, was synthesized in 14 steps from cyclohexanone, as described by Honda et al. (2007 and 2011). Recrystallization from methanol gave colorless rectangular crystals (m.p. 502–504 K).

Refinement top

All of the H atoms were positioned geometrically and then refined using the riding model with C—H lengths of 0.96 Å (CH), 0.97 Å (CH2) or 0.93 Å (CH3). The isotropic displacement parameters for these atoms were set to 1.20 (CH, CH2) or 1.50 (CH3) times Ueq of the parent atom. Weak high angle reflections (2θ > 140°) with intensity less than 2 σ(I) were omitted in the final refinement.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis RED (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: Mercury (Macrae et al., 2006), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 2] Fig. 2. The packing arrangement of the title compound, C21H18N2O2, containing both entaniomers viewed along the a axis. Dashed lines indicate C—H···N hydrogen bonds and weak C—H···O intermolecular interactions forming chains along [001].
[Figure 3] Fig. 3. Molecular structure diagram of MCE-1 (a) and bardoxolone methyl (b).
(±)-(4bS,8aR,10aS)-10a-Ethynyl-4b,8,8-trimethyl-3,7- dioxo-3,4b,7,8,8a,9,10,10a-octahydrophenanthrene-2,6-dicarbonitrile top
Crystal data top
C21H18N2O2Z = 4
Mr = 330.37F(000) = 696
Triclinic, P1Dx = 1.270 Mg m3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54178 Å
a = 7.3012 (2) ÅCell parameters from 16712 reflections
b = 12.9843 (3) Åθ = 4.0–73.2°
c = 18.4254 (4) ŵ = 0.66 mm1
α = 95.051 (2)°T = 299 K
β = 96.284 (2)°Prism, colourless
γ = 92.338 (2)°0.71 × 0.46 × 0.29 mm
V = 1727.26 (7) Å3
Data collection top
Oxford Diffraction Xcalibur Atlas Gemini
diffractometer
6478 independent reflections
Radiation source: fine-focus sealed tube5160 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scansθmax = 69.5°, θmin = 4.0°
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2010)
h = 87
Tmin = 0.745, Tmax = 0.897k = 1515
33944 measured reflectionsl = 2222
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.140 w = 1/[σ2(Fo2) + (0.0731P)2 + 0.4667P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
6478 reflectionsΔρmax = 0.22 e Å3
458 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0024 (4)
Crystal data top
C21H18N2O2γ = 92.338 (2)°
Mr = 330.37V = 1727.26 (7) Å3
Triclinic, P1Z = 4
a = 7.3012 (2) ÅCu Kα radiation
b = 12.9843 (3) ŵ = 0.66 mm1
c = 18.4254 (4) ÅT = 299 K
α = 95.051 (2)°0.71 × 0.46 × 0.29 mm
β = 96.284 (2)°
Data collection top
Oxford Diffraction Xcalibur Atlas Gemini
diffractometer
6478 independent reflections
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2010)
5160 reflections with I > 2σ(I)
Tmin = 0.745, Tmax = 0.897Rint = 0.035
33944 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å3
6478 reflectionsΔρmin = 0.18 e Å3
458 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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*/Ueq
O1A0.7242 (2)0.61192 (10)0.49832 (8)0.0625 (4)
O2A0.6374 (2)0.18345 (11)0.77597 (7)0.0649 (4)
N1A0.6155 (3)0.61182 (13)0.31626 (10)0.0667 (5)
N2A0.8755 (3)0.41471 (15)0.84087 (9)0.0693 (5)
C1A0.6816 (3)0.37153 (14)0.38940 (10)0.0486 (5)
H1A0.64630.34610.34090.058*
C2A0.6841 (3)0.47338 (13)0.40640 (9)0.0441 (4)
C3A0.7309 (3)0.51902 (13)0.48269 (10)0.0423 (4)
C4A0.7798 (3)0.44778 (13)0.53745 (9)0.0414 (4)
H4A0.80820.47500.58600.050*
C5A0.7864 (2)0.34548 (12)0.52233 (9)0.0370 (4)
C6A0.8231 (2)0.27223 (12)0.58271 (9)0.0387 (4)
C7A0.8644 (3)0.33248 (13)0.65657 (9)0.0419 (4)
H7A0.93940.39280.66050.050*
C8A0.7985 (3)0.30344 (13)0.71694 (9)0.0407 (4)
C9A0.6819 (3)0.20774 (13)0.71829 (9)0.0429 (4)
C10A0.6279 (3)0.13976 (13)0.64671 (9)0.0413 (4)
C11A0.6413 (2)0.20507 (12)0.58059 (9)0.0373 (4)
H11A0.54450.25490.58400.045*
C12A0.5947 (3)0.14469 (13)0.50516 (9)0.0458 (4)
H12A0.69480.10060.49510.055*
H12B0.48410.10070.50520.055*
C13A0.5641 (3)0.21787 (14)0.44515 (9)0.0472 (4)
H13A0.45600.25670.45260.057*
H13B0.54060.17750.39790.057*
C14A0.7328 (3)0.29491 (13)0.44422 (9)0.0430 (4)
C15A0.6422 (3)0.54746 (14)0.35364 (10)0.0505 (5)
C16A0.8435 (3)0.36536 (14)0.78652 (10)0.0493 (5)
C17A0.8861 (3)0.24025 (14)0.41381 (10)0.0516 (5)
C18A1.0007 (4)0.20171 (19)0.38268 (13)0.0751 (7)
H18A1.09180.17110.35790.090*
C19A0.9995 (3)0.21202 (15)0.57255 (11)0.0500 (5)
H19A1.04120.18350.61740.075*
H19B1.09430.25830.55990.075*
H19C0.97180.15700.53400.075*
C20A0.4273 (3)0.10060 (18)0.64789 (12)0.0628 (6)
H20A0.34910.15830.64850.094*
H20B0.41750.06500.69090.094*
H20C0.38960.05400.60500.094*
C21A0.7504 (3)0.04632 (14)0.64789 (11)0.0549 (5)
H21A0.71890.00410.68540.082*
H21B0.87760.07020.65790.082*
H21C0.73110.00630.60110.082*
O1B0.2331 (2)0.59090 (9)0.04320 (7)0.0543 (4)
O2B0.3443 (3)0.18811 (12)0.26554 (7)0.0739 (5)
N1B0.4173 (3)0.59329 (14)0.20451 (10)0.0731 (6)
N2B0.0835 (4)0.40614 (15)0.29028 (11)0.0835 (7)
C1B0.3689 (3)0.35541 (13)0.12918 (9)0.0441 (4)
H1B0.42210.33210.17080.053*
C2B0.3422 (3)0.45595 (13)0.11789 (9)0.0429 (4)
C3B0.2610 (2)0.49869 (13)0.05254 (9)0.0406 (4)
C4B0.2208 (2)0.42658 (13)0.00024 (9)0.0407 (4)
H4B0.18040.45310.04390.049*
C5B0.2381 (2)0.32459 (12)0.01003 (8)0.0365 (4)
C6B0.2005 (2)0.25142 (13)0.04851 (9)0.0391 (4)
C7B0.1386 (3)0.31054 (14)0.11468 (10)0.0457 (4)
H7B0.05660.36250.10720.055*
C8B0.1951 (3)0.29232 (13)0.18311 (9)0.0457 (4)
C9B0.3180 (3)0.20864 (14)0.20232 (10)0.0495 (5)
C10B0.3991 (3)0.14548 (14)0.14088 (10)0.0488 (5)
C11B0.3891 (3)0.20508 (12)0.07121 (9)0.0385 (4)
H11B0.47520.26540.08460.046*
C12B0.4612 (3)0.14779 (13)0.00498 (9)0.0439 (4)
H12C0.57530.11630.02070.053*
H12D0.37200.09310.01640.053*
C13B0.4954 (3)0.22156 (13)0.05243 (9)0.0427 (4)
H13C0.53810.18310.09440.051*
H13D0.59160.27300.03210.051*
C14B0.3177 (3)0.27718 (12)0.07820 (9)0.0394 (4)
C15B0.3863 (3)0.53055 (14)0.16767 (10)0.0518 (5)
C16B0.1314 (3)0.35449 (15)0.24348 (11)0.0575 (5)
C17B0.1887 (3)0.20143 (14)0.12493 (10)0.0484 (5)
C18B0.1001 (4)0.14161 (19)0.16700 (12)0.0741 (7)
H18B0.02960.09400.20050.089*
C19B0.0366 (3)0.17316 (16)0.01889 (11)0.0563 (5)
H19D0.00960.14220.05910.085*
H19E0.07820.12020.01430.085*
H19F0.05990.20880.00650.085*
C20B0.6023 (4)0.1310 (2)0.16788 (13)0.0761 (7)
H20D0.67110.19600.17050.114*
H20E0.65200.08160.13440.114*
H20F0.61070.10620.21570.114*
C21B0.2943 (4)0.03946 (15)0.13001 (12)0.0746 (7)
H21D0.32500.00230.17210.112*
H21E0.32830.00090.08710.112*
H21F0.16400.04890.12410.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0943 (12)0.0354 (7)0.0570 (8)0.0079 (7)0.0032 (8)0.0036 (6)
O2A0.0980 (12)0.0608 (9)0.0384 (7)0.0080 (8)0.0199 (7)0.0098 (6)
N1A0.0991 (15)0.0513 (10)0.0524 (10)0.0162 (10)0.0058 (10)0.0175 (8)
N2A0.0989 (16)0.0633 (11)0.0424 (9)0.0044 (10)0.0005 (9)0.0046 (8)
C1A0.0721 (14)0.0424 (10)0.0319 (8)0.0071 (9)0.0039 (8)0.0069 (7)
C2A0.0551 (12)0.0403 (9)0.0391 (9)0.0071 (8)0.0071 (8)0.0116 (7)
C3A0.0467 (11)0.0369 (9)0.0446 (9)0.0035 (7)0.0086 (8)0.0052 (7)
C4A0.0505 (11)0.0387 (9)0.0348 (8)0.0022 (8)0.0056 (7)0.0025 (7)
C5A0.0411 (10)0.0381 (8)0.0327 (8)0.0025 (7)0.0054 (7)0.0058 (7)
C6A0.0462 (10)0.0366 (8)0.0338 (8)0.0025 (7)0.0040 (7)0.0062 (7)
C7A0.0477 (11)0.0390 (9)0.0379 (9)0.0004 (7)0.0008 (7)0.0062 (7)
C8A0.0487 (11)0.0400 (9)0.0331 (8)0.0047 (7)0.0016 (7)0.0035 (7)
C9A0.0516 (11)0.0417 (9)0.0374 (9)0.0079 (8)0.0072 (8)0.0094 (7)
C10A0.0498 (11)0.0360 (8)0.0387 (9)0.0003 (7)0.0057 (7)0.0073 (7)
C11A0.0453 (10)0.0319 (8)0.0347 (8)0.0039 (7)0.0019 (7)0.0052 (6)
C12A0.0596 (12)0.0370 (9)0.0392 (9)0.0023 (8)0.0005 (8)0.0023 (7)
C13A0.0631 (12)0.0409 (9)0.0352 (9)0.0010 (8)0.0023 (8)0.0013 (7)
C14A0.0623 (12)0.0346 (8)0.0326 (8)0.0073 (8)0.0048 (8)0.0043 (7)
C15A0.0669 (13)0.0424 (10)0.0436 (10)0.0095 (9)0.0064 (9)0.0086 (8)
C16A0.0647 (13)0.0444 (10)0.0390 (10)0.0049 (9)0.0043 (9)0.0070 (8)
C17A0.0762 (15)0.0426 (10)0.0383 (9)0.0085 (9)0.0123 (9)0.0061 (8)
C18A0.102 (2)0.0725 (15)0.0586 (13)0.0294 (14)0.0306 (13)0.0106 (11)
C19A0.0501 (12)0.0538 (11)0.0492 (10)0.0108 (9)0.0073 (9)0.0163 (9)
C20A0.0626 (14)0.0693 (14)0.0571 (12)0.0130 (11)0.0059 (10)0.0174 (10)
C21A0.0788 (15)0.0401 (10)0.0486 (11)0.0117 (9)0.0098 (10)0.0128 (8)
O1B0.0689 (9)0.0358 (7)0.0592 (8)0.0092 (6)0.0076 (7)0.0065 (6)
O2B0.1148 (14)0.0751 (10)0.0388 (8)0.0313 (9)0.0169 (8)0.0212 (7)
N1B0.1133 (17)0.0531 (10)0.0526 (10)0.0171 (10)0.0080 (10)0.0151 (8)
N2B0.143 (2)0.0590 (11)0.0570 (11)0.0193 (12)0.0420 (12)0.0056 (9)
C1B0.0576 (12)0.0432 (9)0.0328 (8)0.0024 (8)0.0093 (8)0.0053 (7)
C2B0.0532 (11)0.0392 (9)0.0362 (9)0.0013 (8)0.0029 (8)0.0080 (7)
C3B0.0422 (10)0.0377 (9)0.0406 (9)0.0037 (7)0.0014 (7)0.0037 (7)
C4B0.0471 (11)0.0405 (9)0.0351 (8)0.0075 (8)0.0064 (7)0.0028 (7)
C5B0.0388 (9)0.0399 (9)0.0309 (8)0.0031 (7)0.0022 (7)0.0056 (6)
C6B0.0462 (10)0.0375 (9)0.0349 (8)0.0040 (7)0.0071 (7)0.0062 (7)
C7B0.0553 (12)0.0436 (9)0.0428 (10)0.0114 (8)0.0161 (8)0.0127 (8)
C8B0.0644 (13)0.0384 (9)0.0374 (9)0.0053 (8)0.0168 (8)0.0066 (7)
C9B0.0699 (13)0.0432 (10)0.0377 (9)0.0058 (9)0.0099 (9)0.0105 (8)
C10B0.0707 (13)0.0396 (9)0.0397 (9)0.0147 (9)0.0116 (9)0.0120 (7)
C11B0.0490 (11)0.0337 (8)0.0345 (8)0.0056 (7)0.0075 (7)0.0068 (6)
C12B0.0538 (11)0.0386 (9)0.0411 (9)0.0116 (8)0.0088 (8)0.0056 (7)
C13B0.0517 (11)0.0411 (9)0.0367 (9)0.0064 (8)0.0108 (8)0.0028 (7)
C14B0.0518 (11)0.0340 (8)0.0330 (8)0.0033 (7)0.0076 (7)0.0032 (6)
C15B0.0717 (14)0.0416 (10)0.0416 (10)0.0046 (9)0.0055 (9)0.0061 (8)
C16B0.0911 (17)0.0443 (10)0.0419 (10)0.0093 (10)0.0219 (10)0.0101 (8)
C17B0.0637 (13)0.0441 (10)0.0374 (9)0.0017 (9)0.0035 (9)0.0066 (8)
C18B0.099 (2)0.0655 (14)0.0514 (12)0.0145 (13)0.0106 (12)0.0025 (11)
C19B0.0561 (13)0.0623 (12)0.0515 (11)0.0109 (10)0.0088 (9)0.0132 (9)
C20B0.0853 (18)0.0932 (18)0.0565 (13)0.0401 (14)0.0086 (12)0.0275 (12)
C21B0.133 (2)0.0385 (11)0.0569 (13)0.0057 (12)0.0219 (14)0.0154 (9)
Geometric parameters (Å, º) top
O1A—C3A1.219 (2)O1B—C3B1.223 (2)
O2A—C9A1.208 (2)O2B—C9B1.214 (2)
N1A—C15A1.138 (2)N1B—C15B1.136 (2)
N2A—C16A1.137 (2)N2B—C16B1.139 (3)
C1A—C2A1.331 (2)C1B—C2B1.329 (2)
C1A—C14A1.508 (2)C1B—C14B1.506 (2)
C1A—H1A0.9300C1B—H1B0.9300
C2A—C15A1.445 (2)C2B—C15B1.442 (2)
C2A—C3A1.475 (2)C2B—C3B1.475 (2)
C3A—C4A1.454 (2)C3B—C4B1.452 (2)
C4A—C5A1.337 (2)C4B—C5B1.334 (2)
C4A—H4A0.9300C4B—H4B0.9300
C5A—C14A1.531 (2)C5B—C14B1.532 (2)
C5A—C6A1.535 (2)C5B—C6B1.538 (2)
C6A—C7A1.503 (2)C6B—C7B1.505 (2)
C6A—C11A1.553 (2)C6B—C11B1.555 (2)
C6A—C19A1.553 (3)C6B—C19B1.556 (3)
C7A—C8A1.337 (2)C7B—C8B1.327 (3)
C7A—H7A0.9300C7B—H7B0.9300
C8A—C16A1.450 (2)C8B—C16B1.446 (3)
C8A—C9A1.481 (3)C8B—C9B1.480 (3)
C9A—C10A1.525 (2)C9B—C10B1.526 (3)
C10A—C20A1.534 (3)C10B—C21B1.534 (3)
C10A—C21A1.536 (3)C10B—C20B1.537 (3)
C10A—C11A1.554 (2)C10B—C11B1.553 (2)
C11A—C12A1.531 (2)C11B—C12B1.527 (2)
C11A—H11A0.9800C11B—H11B0.9800
C12A—C13A1.524 (2)C12B—C13B1.522 (2)
C12A—H12A0.9700C12B—H12C0.9700
C12A—H12B0.9700C12B—H12D0.9700
C13A—C14A1.557 (3)C13B—C14B1.559 (3)
C13A—H13A0.9700C13B—H13C0.9700
C13A—H13B0.9700C13B—H13D0.9700
C14A—C17A1.484 (3)C14B—C17B1.481 (3)
C17A—C18A1.170 (3)C17B—C18B1.169 (3)
C18A—H18A0.9300C18B—H18B0.9300
C19A—H19A0.9600C19B—H19D0.9600
C19A—H19B0.9600C19B—H19E0.9600
C19A—H19C0.9600C19B—H19F0.9600
C20A—H20A0.9600C20B—H20D0.9600
C20A—H20B0.9600C20B—H20E0.9600
C20A—H20C0.9600C20B—H20F0.9600
C21A—H21A0.9600C21B—H21D0.9600
C21A—H21B0.9600C21B—H21E0.9600
C21A—H21C0.9600C21B—H21F0.9600
C2A—C1A—C14A123.82 (16)C2B—C1B—C14B123.56 (16)
C2A—C1A—H1A118.1C2B—C1B—H1B118.2
C14A—C1A—H1A118.1C14B—C1B—H1B118.2
C1A—C2A—C15A124.07 (17)C1B—C2B—C15B123.65 (17)
C1A—C2A—C3A121.19 (16)C1B—C2B—C3B121.25 (16)
C15A—C2A—C3A114.74 (15)C15B—C2B—C3B115.09 (15)
O1A—C3A—C4A122.47 (16)O1B—C3B—C4B122.28 (16)
O1A—C3A—C2A120.75 (16)O1B—C3B—C2B120.98 (16)
C4A—C3A—C2A116.76 (15)C4B—C3B—C2B116.73 (14)
C5A—C4A—C3A124.00 (16)C5B—C4B—C3B124.08 (15)
C5A—C4A—H4A118.0C5B—C4B—H4B118.0
C3A—C4A—H4A118.0C3B—C4B—H4B118.0
C4A—C5A—C14A120.71 (15)C4B—C5B—C14B120.39 (15)
C4A—C5A—C6A122.14 (15)C4B—C5B—C6B122.36 (14)
C14A—C5A—C6A116.69 (13)C14B—C5B—C6B116.92 (13)
C7A—C6A—C5A110.68 (13)C7B—C6B—C5B110.75 (13)
C7A—C6A—C11A109.43 (14)C7B—C6B—C11B108.83 (14)
C5A—C6A—C11A105.41 (13)C5B—C6B—C11B105.36 (13)
C7A—C6A—C19A104.61 (14)C7B—C6B—C19B105.03 (15)
C5A—C6A—C19A110.83 (14)C5B—C6B—C19B110.11 (14)
C11A—C6A—C19A115.95 (14)C11B—C6B—C19B116.80 (15)
C8A—C7A—C6A123.10 (16)C8B—C7B—C6B123.41 (16)
C8A—C7A—H7A118.5C8B—C7B—H7B118.3
C6A—C7A—H7A118.5C6B—C7B—H7B118.3
C7A—C8A—C16A120.27 (17)C7B—C8B—C16B119.65 (18)
C7A—C8A—C9A123.61 (16)C7B—C8B—C9B123.64 (16)
C16A—C8A—C9A116.11 (15)C16B—C8B—C9B116.69 (16)
O2A—C9A—C8A119.60 (16)O2B—C9B—C8B119.72 (17)
O2A—C9A—C10A121.65 (16)O2B—C9B—C10B121.47 (17)
C8A—C9A—C10A118.69 (14)C8B—C9B—C10B118.69 (15)
C9A—C10A—C20A106.60 (15)C9B—C10B—C21B106.79 (17)
C9A—C10A—C21A107.22 (15)C9B—C10B—C20B107.19 (17)
C20A—C10A—C21A108.35 (16)C21B—C10B—C20B109.00 (19)
C9A—C10A—C11A109.79 (13)C9B—C10B—C11B110.05 (14)
C20A—C10A—C11A109.59 (15)C21B—C10B—C11B114.39 (16)
C21A—C10A—C11A114.95 (15)C20B—C10B—C11B109.17 (17)
C12A—C11A—C6A110.22 (14)C12B—C11B—C10B114.85 (13)
C12A—C11A—C10A114.83 (13)C12B—C11B—C6B110.69 (14)
C6A—C11A—C10A115.50 (14)C10B—C11B—C6B115.74 (14)
C12A—C11A—H11A105.0C12B—C11B—H11B104.7
C6A—C11A—H11A105.0C10B—C11B—H11B104.7
C10A—C11A—H11A105.0C6B—C11B—H11B104.7
C13A—C12A—C11A111.05 (14)C13B—C12B—C11B110.78 (13)
C13A—C12A—H12A109.4C13B—C12B—H12C109.5
C11A—C12A—H12A109.4C11B—C12B—H12C109.5
C13A—C12A—H12B109.4C13B—C12B—H12D109.5
C11A—C12A—H12B109.4C11B—C12B—H12D109.5
H12A—C12A—H12B108.0H12C—C12B—H12D108.1
C12A—C13A—C14A112.38 (15)C12B—C13B—C14B111.87 (15)
C12A—C13A—H13A109.1C12B—C13B—H13C109.2
C14A—C13A—H13A109.1C14B—C13B—H13C109.2
C12A—C13A—H13B109.1C12B—C13B—H13D109.2
C14A—C13A—H13B109.1C14B—C13B—H13D109.2
H13A—C13A—H13B107.9H13C—C13B—H13D107.9
C17A—C14A—C1A103.64 (15)C17B—C14B—C1B104.38 (14)
C17A—C14A—C5A112.85 (16)C17B—C14B—C5B113.64 (15)
C1A—C14A—C5A113.42 (14)C1B—C14B—C5B113.76 (13)
C17A—C14A—C13A110.09 (15)C17B—C14B—C13B108.64 (14)
C1A—C14A—C13A108.47 (16)C1B—C14B—C13B108.01 (15)
C5A—C14A—C13A108.25 (14)C5B—C14B—C13B108.18 (13)
N1A—C15A—C2A174.5 (2)N1B—C15B—C2B176.3 (2)
N2A—C16A—C8A178.7 (2)N2B—C16B—C8B177.9 (2)
C18A—C17A—C14A172.5 (2)C18B—C17B—C14B173.0 (2)
C17A—C18A—H18A180.0C17B—C18B—H18B180.0
C6A—C19A—H19A109.5C6B—C19B—H19D109.5
C6A—C19A—H19B109.5C6B—C19B—H19E109.5
H19A—C19A—H19B109.5H19D—C19B—H19E109.5
C6A—C19A—H19C109.5C6B—C19B—H19F109.5
H19A—C19A—H19C109.5H19D—C19B—H19F109.5
H19B—C19A—H19C109.5H19E—C19B—H19F109.5
C10A—C20A—H20A109.5C10B—C20B—H20D109.5
C10A—C20A—H20B109.5C10B—C20B—H20E109.5
H20A—C20A—H20B109.5H20D—C20B—H20E109.5
C10A—C20A—H20C109.5C10B—C20B—H20F109.5
H20A—C20A—H20C109.5H20D—C20B—H20F109.5
H20B—C20A—H20C109.5H20E—C20B—H20F109.5
C10A—C21A—H21A109.5C10B—C21B—H21D109.5
C10A—C21A—H21B109.5C10B—C21B—H21E109.5
H21A—C21A—H21B109.5H21D—C21B—H21E109.5
C10A—C21A—H21C109.5C10B—C21B—H21F109.5
H21A—C21A—H21C109.5H21D—C21B—H21F109.5
H21B—C21A—H21C109.5H21E—C21B—H21F109.5
C14A—C1A—C2A—C15A177.48 (19)C14B—C1B—C2B—C15B178.20 (18)
C14A—C1A—C2A—C3A2.6 (3)C14B—C1B—C2B—C3B0.9 (3)
C1A—C2A—C3A—O1A176.5 (2)C1B—C2B—C3B—O1B178.44 (18)
C15A—C2A—C3A—O1A3.4 (3)C15B—C2B—C3B—O1B0.7 (3)
C1A—C2A—C3A—C4A2.0 (3)C1B—C2B—C3B—C4B3.0 (3)
C15A—C2A—C3A—C4A178.11 (17)C15B—C2B—C3B—C4B177.85 (16)
O1A—C3A—C4A—C5A179.23 (19)O1B—C3B—C4B—C5B175.56 (18)
C2A—C3A—C4A—C5A0.8 (3)C2B—C3B—C4B—C5B5.9 (3)
C3A—C4A—C5A—C14A2.8 (3)C3B—C4B—C5B—C14B4.6 (3)
C3A—C4A—C5A—C6A174.82 (16)C3B—C4B—C5B—C6B177.81 (16)
C4A—C5A—C6A—C7A4.8 (2)C4B—C5B—C6B—C7B1.7 (2)
C14A—C5A—C6A—C7A177.07 (15)C14B—C5B—C6B—C7B175.09 (15)
C4A—C5A—C6A—C11A113.46 (18)C4B—C5B—C6B—C11B115.85 (18)
C14A—C5A—C6A—C11A58.85 (19)C14B—C5B—C6B—C11B57.58 (18)
C4A—C5A—C6A—C19A120.35 (19)C4B—C5B—C6B—C19B117.39 (19)
C14A—C5A—C6A—C19A67.3 (2)C14B—C5B—C6B—C19B69.2 (2)
C5A—C6A—C7A—C8A138.96 (18)C5B—C6B—C7B—C8B139.05 (19)
C11A—C6A—C7A—C8A23.2 (2)C11B—C6B—C7B—C8B23.7 (2)
C19A—C6A—C7A—C8A101.6 (2)C19B—C6B—C7B—C8B102.1 (2)
C6A—C7A—C8A—C16A179.86 (16)C6B—C7B—C8B—C16B178.71 (18)
C6A—C7A—C8A—C9A1.6 (3)C6B—C7B—C8B—C9B3.1 (3)
C7A—C8A—C9A—O2A175.28 (18)C7B—C8B—C9B—O2B170.4 (2)
C16A—C8A—C9A—O2A3.3 (3)C16B—C8B—C9B—O2B7.8 (3)
C7A—C8A—C9A—C10A2.1 (3)C7B—C8B—C9B—C10B5.7 (3)
C16A—C8A—C9A—C10A179.36 (16)C16B—C8B—C9B—C10B176.02 (18)
O2A—C9A—C10A—C20A41.6 (2)O2B—C9B—C10B—C21B70.5 (3)
C8A—C9A—C10A—C20A141.06 (17)C8B—C9B—C10B—C21B105.6 (2)
O2A—C9A—C10A—C21A74.2 (2)O2B—C9B—C10B—C20B46.2 (3)
C8A—C9A—C10A—C21A103.07 (18)C8B—C9B—C10B—C20B137.69 (19)
O2A—C9A—C10A—C11A160.26 (18)O2B—C9B—C10B—C11B164.8 (2)
C8A—C9A—C10A—C11A22.4 (2)C8B—C9B—C10B—C11B19.1 (3)
C7A—C6A—C11A—C12A178.85 (13)C9B—C10B—C11B—C12B178.19 (17)
C5A—C6A—C11A—C12A59.80 (17)C21B—C10B—C11B—C12B58.0 (2)
C19A—C6A—C11A—C12A63.18 (18)C20B—C10B—C11B—C12B64.4 (2)
C7A—C6A—C11A—C10A48.96 (18)C9B—C10B—C11B—C6B47.2 (2)
C5A—C6A—C11A—C10A168.01 (13)C21B—C10B—C11B—C6B73.0 (2)
C19A—C6A—C11A—C10A69.01 (19)C20B—C10B—C11B—C6B164.62 (16)
C9A—C10A—C11A—C12A178.62 (15)C7B—C6B—C11B—C12B177.78 (14)
C20A—C10A—C11A—C12A64.6 (2)C5B—C6B—C11B—C12B58.97 (17)
C21A—C10A—C11A—C12A57.7 (2)C19B—C6B—C11B—C12B63.59 (19)
C9A—C10A—C11A—C6A48.63 (19)C7B—C6B—C11B—C10B49.32 (19)
C20A—C10A—C11A—C6A165.39 (15)C5B—C6B—C11B—C10B168.12 (14)
C21A—C10A—C11A—C6A72.33 (19)C19B—C6B—C11B—C10B69.31 (19)
C6A—C11A—C12A—C13A61.7 (2)C10B—C11B—C12B—C13B164.38 (16)
C10A—C11A—C12A—C13A165.77 (16)C6B—C11B—C12B—C13B62.27 (19)
C11A—C12A—C13A—C14A56.2 (2)C11B—C12B—C13B—C14B57.5 (2)
C2A—C1A—C14A—C17A122.1 (2)C2B—C1B—C14B—C17B122.2 (2)
C2A—C1A—C14A—C5A0.6 (3)C2B—C1B—C14B—C5B2.2 (3)
C2A—C1A—C14A—C13A120.9 (2)C2B—C1B—C14B—C13B122.32 (19)
C4A—C5A—C14A—C17A119.57 (18)C4B—C5B—C14B—C17B119.76 (18)
C6A—C5A—C14A—C17A68.0 (2)C6B—C5B—C14B—C17B66.67 (19)
C4A—C5A—C14A—C1A2.1 (3)C4B—C5B—C14B—C1B0.5 (2)
C6A—C5A—C14A—C1A174.52 (16)C6B—C5B—C14B—C1B174.06 (15)
C4A—C5A—C14A—C13A118.33 (18)C4B—C5B—C14B—C13B119.51 (17)
C6A—C5A—C14A—C13A54.1 (2)C6B—C5B—C14B—C13B54.06 (19)
C12A—C13A—C14A—C17A73.72 (18)C12B—C13B—C14B—C17B72.61 (17)
C12A—C13A—C14A—C1A173.52 (15)C12B—C13B—C14B—C1B174.72 (14)
C12A—C13A—C14A—C5A50.06 (19)C12B—C13B—C14B—C5B51.18 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4A—H4A···N2Bi0.932.663.572 (3)166
C4B—H4B···N2Ai0.932.693.580 (2)161
C7B—H7B···O1Bii0.932.433.246 (2)146
C13B—H13D···O1Biii0.972.383.324 (2)163
C13B—H13C···O2Aiv0.972.573.435 (2)148
C13A—H13A···O1Ai0.972.373.295 (2)159
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) x, y, z1.

Experimental details

Crystal data
Chemical formulaC21H18N2O2
Mr330.37
Crystal system, space groupTriclinic, P1
Temperature (K)299
a, b, c (Å)7.3012 (2), 12.9843 (3), 18.4254 (4)
α, β, γ (°)95.051 (2), 96.284 (2), 92.338 (2)
V3)1727.26 (7)
Z4
Radiation typeCu Kα
µ (mm1)0.66
Crystal size (mm)0.71 × 0.46 × 0.29
Data collection
DiffractometerOxford Diffraction Xcalibur Atlas Gemini
diffractometer
Absorption correctionGaussian
(CrysAlis RED; Oxford Diffraction, 2010)
Tmin, Tmax0.745, 0.897
No. of measured, independent and
observed [I > 2σ(I)] reflections
33944, 6478, 5160
Rint0.035
(sin θ/λ)max1)0.607
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.140, 1.03
No. of reflections6478
No. of parameters458
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999), Mercury (Macrae et al., 2006), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4A—H4A···N2Bi0.932.663.572 (3)165.9
C4B—H4B···N2Ai0.932.693.580 (2)161.2
C7B—H7B···O1Bii0.932.433.246 (2)146.1
C13B—H13D···O1Biii0.972.383.324 (2)163.4
C13B—H13C···O2Aiv0.972.573.435 (2)148.3
C13A—H13A···O1Ai0.972.373.295 (2)158.6
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) x, y, z1.
 

Acknowledgements

We thank Drs Iwao Ojima and Nancy S. Goroff for their helpful suggestions and discussions. This investigation was supported by funds from NIH grant R03-CA105294 and Reata Pharmaceuticals. The Stony Brook University single-crystal diffractometer was obtained through the support of the National Science Foundation (NSF) grant CHE-0840483.

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Volume 68| Part 11| November 2012| Pages o3095-o3096
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