4-Nitro-9,10-di­hydro­phenanthrene and a polymorphic form of 4-nitro­phenanthrene

The crystal structures of 4-nitro-9,10-di­hydro­phenanthrene, C₁₄H₁₁NO₂, (I), and 4-nitro­phenanthrene, C₁₄H₉NO₂, (II), the latter having two crystallographically independent mol­ecules, show that the mol­ecules are not planar. The dihedral angles between the phenyl rings of the bi­phenyl skeletons are 28.64 (8)° for (I), and 10.34 (15) and 11.75 (13)° for the two mol­ecules of (II). The differences in the dihedral angles have an effect on the photochemical reactivity of the mol­ecules.

S1. Comment

New triplet species for 2-nitrobiphenyl and 2,2'-dinitrobiphenyl were detected by electron paramagnetic resonance (EPR) after UV irradiation in ethanol glass with an He–Xe lamp at 77 K (Tanigaki et al., 1988). The structures of the two molecules are twisted around the central C—C bonds; the dihedral angles of the two rings being 63.1 (3) and 62.6 (3)° for 2-nitro- and 2,2'-dinitrobiphenyl, respectively (Sekine et al., 1994). The relationship between the nature of the triplet species and the molecular conformation has been discussed (Higuchi et al., 1995, 1999). In order to examine the relationship more precisely, the title compounds, 4-nitro-9,10-dihydrophenanthrene, (I), and 4-nitrophenanthrene, (II), in which the two rings are connected by a –CH₂—CH₂– group (I) and by a –CH═ CH– group in (II), were analyzed by X-ray diffraction. The molecular structures of (I) and (II) are shown in Fig. 1 and 2, respectively.

There are two independent molecules of (II) in the crystal; however, their structural differences are minor. The dihedral angles between the phenyl rings of the biphenyl skeleton are 28.64 (8)° in (I), and 10.34 (15) and 11.75 (13)° in the two molecules of (II). These values are much smaller than that found in 2-nitrobiphenyl, (III) (Sekine et al., 1994), of 63.1 (3)° because (III) has no intramolecular restriction between the two phenyl rings. The dihedral angles between the NO₂ groups and the phenyl ring to which they are bonded are 56.5 (1)° in (I), 70.3 (2) and 67.4 (2)° in (II), and 44.7 (4)° in (III).

The biphenyl skeleton of (II) is nearly coplanar due to the strongly conjugated system, while that of (I) is not coplanar because of the bulky ο-ο'-linkage. Assuming the molecular structure at the lowest excited triplet state is not different from its ground-state structure, the difference in the EPR signals of these compounds would be due to the molecular structure differences, i.e. the angles between the two phenyl rings.

The crystal structure of 4-nitrophenanthrene, (II), has also been reported by Taylor & Thompson (2001) in a different (polymorphic) form [TT form, P2₁/c, Z = 4, a = 8.061 (2), b = 12.449 (3), c = 11.32 (3) Å, β = 109.73 (1)°]. As the TT form was measured at the lower temperature of 168 (2) K, there is a possibility of a phase change from the room temperature form of this study. It is interesting that the two forms have the same space group and unit-cell dimensions, except for a halving of the a cell length for the TT form, and very similar molecular packing. In both structures, dimeric pairs of molecules are related by an inversion center, show a herring-bone motif and make a sheet structure parallel to the (011) face. In our new form, the two independent molecules have slightly different orientations, however, they make similar sheet structures, stacking alternately.

In both forms, the molecular dimensions show no significant differences when the difference in temperature of the structure determinations is considered. The dihedral angles are also comparable; for NO₂–phenyl and in the biphenyl skeleton, they are 72.7 (7) and 10.40 (8)° in TT form, respectively.

Related literature

For related literature, see: Boekelheide & Hylton (1970); Higuchi et al. (1995, 1999); Krueger & Mosettig (1939); Sekine et al. (1994); Tanigaki et al. (1988).

S2. Experimental

Compound (I) was synthesized according to the method of Krueger & Mosettig (1939). Light-yellow crystals were obtained by recrystallization from a hexane solution (yield 10.5%). Compound (II) was obtained by modifying the dehydrogenation reported by Boekelheide & Hylton (1970). A solution of compound (I) and 2,3-dichloro-5,6-dicyanoquinone in o-dichlorobenzene was stirred in the dark at 473 K for 24 h. Yellow crystals were obtained by recrystallization from a hexane solution (yield 81.6%).

S3. Refinement

H atoms were refined as riding with C—H distances of 0.93 and 0.97 Å for (I) and 0.93 Å for (II).

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1993b)'; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: PLATON (Spek, 1990).

Figures

	Fig. 1. The molecular structure of (I) showing the atom labelling. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. The molecular structures of the two independent molecules of (II), showing the atom labelling. Displacement ellipsoids are shown at the 50% probability level.

(I)

Crystal data

C14H11NO2	F(000) = 472
Mr = 225.24	Dx = 1.343 Mg m^−3
Monoclinic, P21/a	Cu Kα radiation, λ = 1.54178 Å
a = 8.6710 (5) Å	Cell parameters from 3 reflections
b = 16.4284 (8) Å	θ = 55.0–60.0°
c = 7.8287 (7) Å	µ = 0.74 mm^−1
β = 92.542 (6)°	T = 296 K
V = 1114.11 (13) Å^3	Prismatic, light yellow
Z = 4	0.5 × 0.3 × 0.3 mm

Data collection

Rigaku AFC-5R diffractometer	1476 reflections with I > 2σ(I)
Radiation source: Rigaku U-200 rotating anode	Rint = 0.014
Graphite monochromator	θmax = 62.5°, θmin = 5.0°
θ–2θ scans	h = −9→9
Absorption correction: y scan (North et al., 1968).	k = 0→18
Tmin = 0.643, Tmax = 0.802	l = 0→8
1966 measured reflections	3 standard reflections every 150 reflections
1763 independent reflections	intensity decay: 2.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.09	w = 1/[s^2(Fo^2) + ( 0.0417P)^2 + 0.1823P] where P = (Fo^2 + 2Fc^2)/3
1762 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.11 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1686 (2)	0.03296 (8)	0.69547 (15)	0.0612 (4)
O2	0.2442 (2)	−0.07687 (8)	0.8237 (2)	0.0734 (4)
N1	0.2224 (2)	−0.00368 (8)	0.8199 (2)	0.0458 (4)
C1	0.2809 (2)	0.13308 (11)	1.2687 (2)	0.0531 (5)
H1	0.2882	0.16406	1.3681	0.064*
C2	0.1915 (2)	0.06386 (12)	1.2654 (2)	0.0546 (5)
H2	0.1399	0.04810	1.3617	0.066*
C3	0.1791 (2)	0.01819 (10)	1.1179 (2)	0.0473 (4)
H3	0.1194	−0.02887	1.1132	0.057*
C4	0.2566 (2)	0.04342 (9)	0.9773 (2)	0.0385 (4)
C4a	0.3524 (2)	0.11179 (9)	0.9763 (2)	0.0381 (4)
C4b	0.4483 (2)	0.13688 (9)	0.8333 (2)	0.0389 (4)
C5	0.5071 (2)	0.08126 (10)	0.7185 (2)	0.0442 (4)
H5	0.4851	0.02617	0.7298	0.053*
C6	0.5977 (2)	0.10705 (12)	0.5884 (2)	0.0549 (5)
H6	0.6364	0.06943	0.5125	0.066*
C7	0.6307 (2)	0.18820 (13)	0.5712 (3)	0.0635 (5)
H7	0.6893	0.20573	0.4815	0.076*
C8	0.5774 (2)	0.24389 (12)	0.6865 (3)	0.0608 (5)
H8	0.6015	0.29869	0.6744	0.073*
C8a	0.4881 (2)	0.21937 (9)	0.8202 (2)	0.0468 (4)
C9	0.4404 (2)	0.27667 (10)	0.9572 (2)	0.0588 (5)
H9A	0.3343	0.29364	0.9343	0.071*
H9B	0.5053	0.32476	0.9580	0.071*
C10	0.4553 (2)	0.23471 (11)	1.1298 (2)	0.0573 (5)
H10A	0.5628	0.22161	1.1565	0.069*
H10B	0.4204	0.27108	1.2178	0.069*
C10a	0.3606 (2)	0.15803 (10)	1.1280 (2)	0.0454 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0700 (8)	0.0697 (8)	0.0430 (7)	−0.0090 (7)	−0.0075 (6)	0.0005 (6)
O2	0.1094 (12)	0.0380 (7)	0.0739 (9)	−0.0083 (7)	0.0166 (8)	−0.0073 (6)
N1	0.0488 (8)	0.0430 (8)	0.0462 (8)	−0.0093 (6)	0.0100 (6)	−0.0020 (6)
C1	0.0553 (10)	0.0628 (11)	0.0411 (9)	0.0158 (9)	0.0003 (8)	−0.0111 (8)
C2	0.0544 (10)	0.0691 (12)	0.0410 (9)	0.0084 (9)	0.0087 (8)	0.0062 (8)
C3	0.0462 (9)	0.0502 (10)	0.0456 (9)	0.0004 (7)	0.0053 (7)	0.0075 (8)
C4	0.0394 (8)	0.0386 (8)	0.0375 (8)	0.0039 (6)	0.0019 (6)	−0.0011 (6)
C4a	0.0359 (8)	0.0359 (8)	0.0424 (8)	0.0058 (6)	−0.0005 (6)	−0.0009 (6)
C4b	0.0347 (8)	0.0390 (8)	0.0426 (9)	0.0005 (6)	−0.0026 (6)	0.0016 (7)
C5	0.0428 (9)	0.0442 (9)	0.0457 (9)	−0.0011 (7)	0.0035 (7)	−0.0009 (7)
C6	0.0522 (10)	0.0676 (12)	0.0455 (10)	−0.0024 (9)	0.0086 (8)	0.0013 (8)
C7	0.0585 (11)	0.0779 (14)	0.0543 (11)	−0.0154 (10)	0.0062 (9)	0.0151 (10)
C8	0.0596 (11)	0.0514 (10)	0.0704 (12)	−0.0155 (9)	−0.0063 (9)	0.0167 (10)
C8a	0.0408 (9)	0.0397 (9)	0.0591 (10)	−0.0032 (7)	−0.0086 (7)	0.0036 (7)
C9	0.0555 (11)	0.0364 (9)	0.0834 (13)	−0.0029 (8)	−0.0081 (9)	−0.0066 (9)
C10	0.0570 (11)	0.0500 (10)	0.0643 (12)	−0.0002 (8)	−0.0045 (9)	−0.0182 (9)
C10a	0.0416 (9)	0.0459 (9)	0.0484 (9)	0.0087 (7)	−0.0035 (7)	−0.0088 (7)

Geometric parameters (Å, º)

O1—N1	1.220 (2)	C7—C6	1.371 (3)
O2—N1	1.217 (2)	C6—C5	1.380 (2)
N1—C4	1.474 (2)	C5—C4b	1.394 (2)
C4—C3	1.379 (2)	C4a—C4b	1.482 (2)
C4—C4a	1.397 (2)	H3—C3	0.93
C3—C2	1.377 (2)	H2—C2	0.93
C2—C1	1.376 (3)	H1—C1	0.93
C1—C10a	1.387 (2)	H10A—C10	0.97
C10a—C4a	1.409 (2)	H10B—C10	0.97
C10a—C10	1.504 (2)	H9A—C9	0.97
C10—C9	1.517 (3)	H9B—C9	0.97
C9—C8a	1.499 (2)	H8—C8	0.93
C8a—C8	1.390 (2)	H7—C7	0.93
C8a—C4b	1.403 (2)	H6—C6	0.93
C8—C7	1.379 (3)	H5—C5	0.93
O1—N1—O2	124.09 (15)	C10a—C4a—C4b	118.56 (14)
O1—N1—C4	117.66 (13)	C4—C3—H3	120.56
O2—N1—C4	118.20 (14)	C2—C3—H3	120.57
C3—C4—C4a	123.88 (14)	C3—C2—H2	120.35
C3—C4—N1	114.97 (14)	C1—C2—H2	120.37
C4a—C4—N1	121.00 (13)	C2—C1—H1	119.05
C2—C3—C4	118.9 (2)	C10a—C1—H1	119.00
C1—C2—C3	119.3 (2)	C10a—C10—H10A	109.59
C2—C1—C10a	121.9 (2)	C10a—C10—H10B	109.58
C1—C10a—C4a	120.1 (2)	C9—C10—H10A	109.61
C1—C10a—C10	122.07 (15)	C9—C10—H10B	109.61
C4a—C10a—C10	117.80 (15)	H10A—C10—H10B	108.09
C10a—C10—C9	110.33 (14)	C10—C9—H9A	109.73
C8a—C9—C10	109.67 (14)	C10—C9—H9B	109.75
C8—C8a—C4b	118.8 (2)	C8a—C9—H9A	109.73
C8—C8a—C9	122.5 (2)	C8a—C9—H9B	109.74
C4b—C8a—C9	118.57 (15)	H9A—C9—H9B	108.20
C7—C8—C8a	121.0 (2)	C8a—C8—H8	119.52
C6—C7—C8	120.2 (2)	C7—C8—H8	119.48
C7—C6—C5	119.9 (2)	C8—C7—H7	119.91
C6—C5—C4b	120.7 (2)	C6—C7—H7	119.88
C5—C4b—C8a	119.23 (15)	C7—C6—H6	120.03
C5—C4b—C4a	122.55 (14)	C5—C6—H6	120.04
C8a—C4b—C4a	118.11 (14)	C6—C5—H5	119.66
C4—C4a—C10a	115.84 (14)	C4b—C5—H5	119.61
C4—C4a—C4b	125.55 (13)

(II)

Crystal data

C14H9NO2	F(000) = 928
Mr = 223.22	Dx = 1.393 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.934 (7) Å	Cell parameters from 25 reflections
b = 12.471 (5) Å	θ = 55.0–60.0°
c = 11.436 (5) Å	µ = 0.09 mm^−1
β = 110.48 (5)°	T = 296 K
V = 2129.0 (16) Å^3	Prismatic, yellow
Z = 8	0.4 × 0.3 × 0.3 mm

Data collection

Riguak AFC-7S diffractometer	2240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 24.1°, θmin = 1.4°
θ–2θ scans	h = −18→17
Absorption correction: ψ scan (North et al., 1968).	k = 0→14
Tmin = 0.797, Tmax = 0.972	l = 0→13
3583 measured reflections	3 standard reflections every 150 reflections
3398 independent reflections	intensity decay: 0.2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.163	H-atom parameters constrained
S = 1.04	w = 1/[s^2(Fo^2) + (0.0868P)^2 + 0.2279P] where P = (Fo^2 + 2Fc^2)/3
3398 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6026 (2)	0.3115 (2)	1.0396 (2)	0.0552 (6)
O1	0.65477 (15)	0.2549 (2)	1.1180 (2)	0.0719 (7)
O2	0.6251 (2)	0.3922 (2)	0.9962 (2)	0.0805 (7)
C1	0.3289 (2)	0.2457 (3)	0.9488 (3)	0.0589 (8)
H1	0.2685	0.2322	0.9328	0.071*
C2	0.3664 (2)	0.3368 (3)	1.0105 (3)	0.0652 (9)
H2	0.3316	0.3854	1.0352	0.078*
C3	0.4567 (2)	0.3571 (3)	1.0365 (3)	0.0596 (8)
H3	0.4830	0.4184	1.0804	0.072*
C4	0.5067 (2)	0.2858 (2)	0.9970 (2)	0.0467 (6)
C4a	0.4712 (2)	0.1907 (2)	0.9282 (2)	0.0417 (6)
C4b	0.5204 (2)	0.1149 (2)	0.8791 (2)	0.0422 (6)
C5	0.6061 (2)	0.1335 (2)	0.8722 (2)	0.0494 (7)
H5	0.6341	0.1990	0.8989	0.059*
C6	0.6487 (2)	0.0574 (3)	0.8270 (3)	0.0592 (8)
H6	0.7048	0.0721	0.8227	0.071*
C7	0.6090 (2)	−0.0417 (3)	0.7875 (3)	0.0619 (8)
H7	0.6394	−0.0942	0.7604	0.074*
C8	0.5256 (2)	−0.0614 (2)	0.7887 (3)	0.0583 (8)
H8	0.4991	−0.1277	0.7614	0.070*
C8a	0.4779 (2)	0.0159 (2)	0.8303 (2)	0.0464 (6)
C9	0.3874 (2)	−0.0020 (2)	0.8184 (3)	0.0562 (7)
H9	0.3604	−0.0669	0.7863	0.067*
C10	0.3398 (2)	0.0726 (2)	0.8523 (3)	0.0557 (7)
H10	0.2797	0.0601	0.8391	0.067*
C10a	0.3801 (2)	0.1710 (2)	0.9086 (2)	0.0477 (7)
N11	0.8639 (2)	0.3028 (2)	0.9130 (3)	0.0639 (7)
O11	0.8352 (2)	0.3760 (2)	0.8385 (3)	0.1024 (10)
O12	0.8162 (2)	0.2440 (2)	0.9473 (3)	0.0859 (8)
C11	1.1404 (2)	0.2669 (3)	1.0986 (3)	0.0620 (8)
H11	1.2011	0.2598	1.1446	0.074*
C12	1.0952 (2)	0.3554 (3)	1.1156 (3)	0.0694 (9)
H12	1.1254	0.4091	1.1708	0.083*
C13	1.0047 (2)	0.3643 (2)	1.0506 (3)	0.0630 (8)
H13	0.9731	0.4230	1.0637	0.076*
C14	0.9615 (2)	0.2871 (2)	0.9669 (3)	0.0493 (7)
C14a	1.0042 (2)	0.1953 (2)	0.9402 (2)	0.0433 (6)
C14b	0.9618 (2)	0.1122 (2)	0.8481 (2)	0.0423 (6)
C15	0.8750 (2)	0.1185 (2)	0.7578 (3)	0.0529 (7)
H15	0.8420	0.1811	0.7516	0.064*
C16	0.8379 (2)	0.0348 (3)	0.6789 (3)	0.0617 (8)
H16	0.7804	0.0413	0.6203	0.074*
C17	0.8856 (2)	−0.0598 (3)	0.6857 (3)	0.0637 (8)
H17	0.8592	−0.1178	0.6351	0.076*
C18	0.9710 (2)	−0.0669 (2)	0.7668 (3)	0.0565 (8)
H18	1.0034	−0.1293	0.7691	0.068*
C18a	1.0118 (2)	0.0184 (2)	0.8480 (2)	0.0466 (6)
C19	1.1037 (2)	0.0108 (2)	0.9271 (3)	0.0531 (7)
H19	1.1357	−0.0514	0.9265	0.064*
C20	1.1441 (2)	0.0922 (2)	1.0019 (3)	0.0543 (7)
H20	1.2049	0.0872	1.0484	0.065*
C20a	1.0963 (2)	0.1861 (2)	1.0122 (2)	0.0475 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0584 (15)	0.0468 (14)	0.0546 (14)	−0.0048 (12)	0.0124 (12)	−0.0069 (12)
O1	0.0659 (14)	0.0654 (14)	0.0665 (14)	0.0039 (12)	0.0007 (11)	0.0058 (12)
O2	0.074 (2)	0.0576 (15)	0.100 (2)	−0.0172 (12)	0.0173 (13)	0.0143 (13)
C1	0.052 (2)	0.065 (2)	0.066 (2)	0.0067 (15)	0.0286 (15)	0.010 (2)
C2	0.076 (2)	0.062 (2)	0.068 (2)	0.016 (2)	0.038 (2)	0.002 (2)
C3	0.074 (2)	0.049 (2)	0.054 (2)	0.0055 (15)	0.0216 (15)	−0.0040 (13)
C4	0.054 (2)	0.0433 (15)	0.0440 (14)	0.0008 (12)	0.0183 (12)	0.0017 (12)
C4a	0.0440 (14)	0.0396 (14)	0.0413 (13)	−0.0016 (11)	0.0147 (11)	0.0040 (11)
C4b	0.0476 (15)	0.0399 (14)	0.0377 (13)	0.0002 (11)	0.0131 (11)	0.0035 (11)
C5	0.047 (2)	0.049 (2)	0.052 (2)	−0.0009 (13)	0.0175 (13)	0.0006 (13)
C6	0.051 (2)	0.071 (2)	0.058 (2)	0.0119 (15)	0.0210 (14)	0.005 (2)
C7	0.069 (2)	0.064 (2)	0.053 (2)	0.022 (2)	0.0207 (15)	0.0009 (15)
C8	0.079 (2)	0.044 (2)	0.047 (2)	0.0067 (15)	0.0167 (14)	−0.0028 (13)
C8a	0.057 (2)	0.0426 (15)	0.0365 (13)	−0.0007 (13)	0.0122 (12)	0.0038 (11)
C9	0.061 (2)	0.050 (2)	0.053 (2)	−0.0164 (15)	0.0144 (14)	−0.0005 (13)
C10	0.044 (2)	0.063 (2)	0.058 (2)	−0.0081 (14)	0.0159 (13)	0.0047 (15)
C10a	0.0469 (15)	0.052 (2)	0.0451 (14)	0.0013 (13)	0.0172 (12)	0.0093 (13)
N11	0.061 (2)	0.0495 (15)	0.089 (2)	0.0058 (14)	0.0363 (15)	−0.0079 (14)
O11	0.081 (2)	0.067 (2)	0.143 (3)	0.0188 (14)	0.018 (2)	0.029 (2)
O12	0.070 (2)	0.082 (2)	0.126 (2)	−0.0068 (13)	0.060 (2)	−0.009 (2)
C11	0.061 (2)	0.074 (2)	0.050 (2)	−0.010 (2)	0.0180 (15)	0.003 (2)
C12	0.083 (2)	0.069 (2)	0.061 (2)	−0.020 (2)	0.032 (2)	−0.017 (2)
C13	0.080 (2)	0.050 (2)	0.070 (2)	−0.006 (2)	0.040 (2)	−0.010 (2)
C14	0.055 (2)	0.045 (2)	0.055 (2)	−0.0003 (13)	0.0291 (13)	0.0023 (13)
C14a	0.0487 (15)	0.0406 (14)	0.0477 (14)	−0.0005 (12)	0.0257 (12)	0.0062 (12)
C15	0.049 (2)	0.056 (2)	0.057 (2)	0.0036 (13)	0.0227 (13)	0.0009 (14)
C16	0.052 (2)	0.076 (2)	0.057 (2)	−0.010 (2)	0.0206 (14)	−0.010 (2)
C17	0.075 (2)	0.063 (2)	0.060 (2)	−0.018 (2)	0.032 (2)	−0.013 (2)
C18	0.077 (2)	0.042 (2)	0.063 (2)	−0.0006 (14)	0.040 (2)	0.0003 (14)
C18a	0.056 (2)	0.0423 (15)	0.052 (2)	0.0015 (12)	0.0314 (13)	0.0036 (12)
C14b	0.0416 (14)	0.0443 (15)	0.0464 (14)	0.0019 (11)	0.0222 (11)	0.0063 (12)
C19	0.053 (2)	0.051 (2)	0.064 (2)	0.0134 (14)	0.0313 (14)	0.0138 (14)
C20	0.043 (2)	0.061 (2)	0.059 (2)	0.0070 (14)	0.0184 (13)	0.0161 (15)
C20a	0.048 (2)	0.051 (2)	0.0471 (15)	−0.0034 (13)	0.0213 (12)	0.0069 (13)

Geometric parameters (Å, º)

N1—O1	1.213 (3)	C20a—C20	1.424 (4)
N1—O2	1.230 (3)	C20—C19	1.339 (4)
N1—C4	1.468 (4)	C19—C18a	1.429 (4)
C4—C3	1.371 (4)	C18a—C18	1.412 (4)
C4—C4a	1.427 (4)	C18a—C14b	1.416 (4)
C3—C2	1.386 (4)	C18—C17	1.355 (4)
C2—C1	1.360 (4)	C17—C16	1.391 (4)
C1—C10a	1.418 (4)	C16—C15	1.372 (4)
C10a—C4a	1.411 (4)	C15—C14b	1.409 (4)
C10a—C10	1.430 (4)	C14b—C14a	1.464 (4)
C10—C9	1.339 (4)	C13—H13	0.93
C9—C8a	1.419 (4)	C12—H12	0.93
C8a—C8	1.409 (4)	C11—H11	0.93
C8a—C4b	1.424 (4)	C20—H20	0.93
C8—C7	1.357 (4)	C19—H19	0.93
C7—C6	1.390 (4)	C18—H18	0.93
C6—C5	1.370 (4)	C17—H17	0.93
C5—C4b	1.414 (4)	C16—H16	0.93
C4a—C4b	1.460 (4)	C15—H15	0.93
N11—O11	1.223 (4)	C3—H3	0.93
N11—O12	1.217 (3)	C2—H2	0.93
N11—C14	1.471 (4)	C1—H1	0.93
C14—C13	1.363 (4)	C10—H10	0.93
C14—C14a	1.418 (4)	C9—H9	0.93
C13—C12	1.376 (5)	C8—H8	0.93
C12—C11	1.369 (5)	C7—H7	0.93
C11—C20a	1.413 (4)	C6—H6	0.93
C20a—C14a	1.414 (4)	C5—H5	0.93
O1—N1—O2	123.6 (3)	C18—C17—C16	119.5 (3)
O1—N1—C4	118.9 (2)	C15—C16—C17	120.5 (3)
O2—N1—C4	117.4 (2)	C16—C15—C14b	121.7 (3)
C3—C4—C4a	123.9 (3)	C15—C14b—C18a	117.0 (2)
C3—C4—N1	114.1 (3)	C15—C14b—C14a	125.1 (2)
C4a—C4—N1	121.9 (2)	C18a—C14b—C14a	117.8 (2)
C4—C3—C2	119.3 (3)	C20a—C14a—C14	114.7 (3)
C1—C2—C3	119.9 (3)	C20a—C14a—C14b	119.1 (2)
C2—C1—C10a	121.2 (3)	C14—C14a—C14b	126.2 (2)
C4a—C10a—C1	120.8 (3)	C14—C13—H13	120.04
C4a—C10a—C10	119.8 (3)	C11—C12—H12	120.26
C1—C10a—C10	119.4 (3)	C20a—C20—H20	119.22
C9—C10—C10a	121.1 (3)	C18a—C19—H19	119.58
C10—C9—C8a	121.5 (3)	C18—C17—H17	120.16
C8—C8a—C9	120.6 (3)	C15—C16—H16	119.80
C8—C8a—C4b	119.2 (3)	C4—C3—H3	120.45
C9—C8a—C4b	120.1 (3)	C1—C2—H2	120.11
C7—C8—C8a	121.6 (3)	C10a—C10—H10	119.49
C8—C7—C6	119.7 (3)	C8a—C9—H9	119.31
C5—C6—C7	120.6 (3)	C8—C7—H7	120.16
C6—C5—C4b	121.6 (3)	C5—C6—H6	119.72
C5—C4b—C8a	117.1 (2)	C12—C13—H13	120.04
C5—C4b—C4a	125.0 (2)	C12—C11—H11	119.44
C8a—C4b—C4a	117.8 (2)	C19—C20—H20	119.11
C10a—C4a—C4	114.8 (2)	C18a—C18—H18	119.27
C10a—C4a—C4b	119.1 (2)	C16—C17—H17	120.38
C4—C4a—C4b	126.1 (2)	C16—C15—H15	119.13
O12—N11—O11	123.4 (3)	C2—C3—H3	120.23
O12—N11—C14	118.2 (3)	C2—C1—H1	119.32
O11—N11—C14	118.3 (3)	C9—C10—H10	119.47
C13—C14—C14a	124.0 (3)	C8a—C8—H8	119.06
C13—C14—N11	113.6 (3)	C6—C7—H7	120.24
C14a—C14—N11	122.3 (2)	C6—C5—H5	119.26
C14—C13—C12	119.9 (3)	C13—C12—H12	120.25
C11—C12—C13	119.5 (3)	C20a—C11—H11	119.46
C12—C11—C20a	121.1 (3)	C20—C19—H19	119.68
C11—C20a—C14a	120.7 (3)	C17—C18—H18	119.28
C11—C20a—C20	119.7 (3)	C17—C16—H16	119.70
C14a—C20a—C20	119.6 (3)	C14b—C15—H15	119.11
C19—C20—C20a	121.7 (3)	C3—C2—H2	120.02
C20—C19—C18a	120.8 (3)	C10a—C1—H1	119.40
C18—C18a—C14b	119.5 (3)	C10—C9—H9	119.20
C18—C18a—C19	120.0 (3)	C7—C8—H8	119.24
C14b—C18a—C19	120.4 (3)	C7—C6—H6	119.63
C17—C18—C18a	121.5 (3)	C4b—C5—H5	119.18