Crystal structures of (E)-1-naphthaldehyde oxime and (E)-phenanthrene-9-carbaldehyde oxime.

The aldoximes C11H9NO (I) and C15H11NO (II), synthesized in ca 90% yield, by treatment of 1-naphthaldehyde or phenanthrene-9-carbaldehyde, respectively, with hydroxyl-amine hydro-chloride and sodium carbonate, have been characterized by IR, 1H, 13C and DEPT-135 NMR spectroscopies, and also by single-crystal X-ray diffraction analysis. The mol-ecules of (I) and (II) are conformationally similar, with the aldoxime substituent groups lying outside the planes of the naphthalene or phenanthrene rings, forming dihedral angles with them of 23.9 (4) and 27.9 (6)°, respectively. The crystal structures of both (I) and (II) are similar with a single inter-molecular O-H⋯N hydrogen-bonding inter-action, giving rise to the formation of one-dimensional polymeric chains extending along the 21 (b) screw axes in each.

Chemical context

Oxime compounds have found many applications; for example in the medical field, they are used as anti­dotes for nerve agents (Kassa, 2002 ▸). Oximes are also used as inter­mediates in the industrial production of caprolactam, a precursor to Nylon 6 (Ritz et al., 2012 ▸). Oximes, HO—N=CR 1 R 2, are also valuable and simple reagents containing the O—N=C moiety (Kukushkin & Pombeiro, 1999 ▸), which easily adds to nitrile ligands, to form a variety of nitro­gen-containing products e.g. imino­acyl­ated compounds (Kopylovich et al., 2009 ▸; Lasri et al., 2007 ▸, 2008 ▸), amidines (Kopylovich et al., 2001 ▸), carboxamides (Kopylovich et al., 2002 ▸), phthalocyanines (Kopylovich et al., 2004 ▸), or 1,3,5-tri­aza­penta­diene species (Kopylovich et al., 2007 ▸). In this work, we report the synthesis and crystal structures of two aldoximes, viz. (E)-1-naphthaldehyde oxime (I) and (E)-phenanthrene-9-carbaldehyde oxime (II), by treatment of 1-naphthaldehyde or phenanthrene-9-carbaldehyde, respectively, with hydroxyl­amine hydro­chloride and sodium carbonate.

Structural commentary

The title compounds (I) and (II) both crystallize in the non-centrosymmetric monoclinic space group P21 with Z = 2, with similar unit-cell parameters. The asymmetric unit contents for each are shown in Figs. 1 ▸ and 2 ▸. Compound (I) comprises a naphthalene unit functionalized with an aldoxime group at position 1. The naphthalene unit is, as expected, essentially planar but the plane containing the aldoxime atoms lies significantly out of the naphthalene plane [torsion angle N1—C11—C1—C2 = 23.6 (6)°] (Table 1 ▸). In the case of compound (II), the plane of the aldoxime group lies similarly out-of-plane with the phenanthrene ring system [comparative torsion angle N1—C11—C9—C10 = 27.6 (4)°], corresponding to dihedral angles between the two planes of 23.9 (4) and 27.9 (5)° for (I) and (II), respectively. The aldoxime group shows similar bond lengths for both structures: 1.395 (5) and 1.405 (3) Å for O1—N1, 1.273 (5) and 1.268 (3) Å for N1—C11, 1.461 (6) and 1.466 (4) Å for C1—C11 or C9—C11, for (I) and (II), respectively.

Figure 1

The mol­ecular conformation and atom-numbering scheme for (I), with non-H atoms represented as 30% probability ellipsoids.

Figure 2

The mol­ecular conformation and atom-numbering scheme for (II), with non-H atoms represented as 30% probability ellipsoids.

Table 1

Selected torsion angles (°) for the aldoxime groups in (I) and (II)

	Compound (I)	Compound (II)
C1/C9—C11—N1—O1	−175.5 (4)	−175.3 (2)
C2/C10—C1/C9—C11—N1	23.6 (6)	27.6 (4)
C8′—C1—C11—N1	−160.4 (4)	–
C8′—C9—C11—N1	–	−156.1 (2)

Supra­molecular features

Similar inter­molecular inter­actions are observed in the crystal structures of both (I) and (II). In each, mol­ecules are linked through a single inter­molecular O1—H⋯N1i hydrogen-bonding inter­action [Tables 2 ▸ and 3 ▸ for (I) and (II), respectively]. These basic inter­actions are shown in Fig. 3 ▸, defining an oxime C(3) type II motif. It is well known that oximes are able to form different types of hydrogen-bonding motifs (Bruton et al., 2003 ▸). In the structures of both (I) and (II), the formation of a one-dimensional polymeric chain arrangement of mol­ecules results, extending along the 21 (b) screw axes in each (Fig. 4 ▸).

Table 2

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1i	0.90 (6)	1.94 (6)	2.834 (5)	177 (6)

Symmetry code: (i) .

Table 3

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H⋯N1i	0.88 (3)	1.99 (3)	2.852 (3)	169 (3)

Symmetry code: (i) .

Figure 3

Inter­molecular hydrogen-bonding associations for (I) (left) and (II) (right), shown as dashed lines. Non-associative H atoms have been omitted for clarity.

Figure 4

A packing diagram viewed along the a axis for (I) (top) and (II) (bottom), showing polymeric chain extensions.

Database survey

Many naphthalene-carbaldehyde oxime derivatives are present in the Cambridge Structural Database (Version 5.38; Groom et al. 2016 ▸) but no one crystal structure containing only an aldoxime group in position 1 of the naphthalene ring system has been reported. The most similar structures that can be found are LIVROY/LIVROY01 (Guo et al., 2008 ▸; Tarai & Baruah, 2016 ▸) with an additional hydroxyl group in position 2 and TIJPOS (Asaad et al., 2005 ▸) with a di­methyl­amino group in position 9. The most important difference between (I) and LIVROY/LIVROY01 are the two hydrogen bonds: one intra­molecular O—H⋯N and another inter­molecular O—H⋯O. As a result of the intra­molecular hydrogen-bonding inter­action, the aldoxime group in the latter compound is coplanar with the central naphthalene ring with a dihedral angle of 1.21° and torsion angles C1—C11—N1—O2 = 179.27, C3—C1—C11—N1 = −179.91 and C4—C1—C11—N1 = −0.76°. However, TIJPOS (Asaad et al., 2005 ▸), with just one type of inter­molecular hydrogen bond, shows a rotation in the aldoxime group that is more dramatic than in (I) and (II) (Table 1 ▸), with a 40.35° deviation from the central naphthalene plane.

No examples of structures of phenanthrene-carbaldehyde oxime derivatives are present in the Cambridge Structural Database.

Synthesis and crystallization

The aldoximes (E)-1-naphthaldehyde oxime (I) and (E)-phen­an­threne-9-carbaldehyde oxime (II) were synthesized, in ca 90% yield, by treatment of 1-naphthaldehyde or phenanthrene-9-carbaldehyde, respectively, with hydroxyl­amine hydro­chloride and sodium carbonate in MeOH at room temperature. To a solution of hydroxyl­amine hydro­chloride (41.6 mg, 0.60 mmol) in MeOH (10 ml) was added sodium carbonate (31.7 mg, 0.30 mmol). The reaction mixture was stirred at room temperature for 5 min. 1-Naphthaldehyde (85.0 mg, 0.54 mmol) or phenanthrene-9-carbaldehyde (112.2 mg, 0.54 mmol) was added and the reaction mixture was stirred at room temperature for 12 h. The precipitate formed was then filtered off and the filtrate was evaporated in vacuo. The crude residue was purified by column chroma­tography on silica (CHCl3 as the eluent, 50 ml), followed by evaporation of the solvent in vacuo to give the pure aldoximes [(I), 84 mg, 90% yield and (II), 107 mg, 89% yield] (see reaction scheme).

Single crystals of the aldoximes (I) and (II) suitable for X-ray diffraction were obtained by slow evaporation of their 10 ml CHCl3 solutions at room temperature. Compounds (I) and (II) were characterized by IR, 1H, 13C and DEPT-135 NMR spectroscopies and also by single crystal X-ray diffraction analysis.

In the IR spectra of (I) and (II), the characteristic bands at wavenumbers 3389 and 3200 cm−1 (O—H), and 1614 and 1607 cm-1 (C=N), confirm the formation of the aldoximes (I) and (II), respectively. In the 1H NMR spectra, we observed the absence of the signal of the aldehyde at ca 10 ppm and a new signal at ca 8.8 ppm due to the imine proton CH=N was detected. Moreover, in the 13C and DEPT-135 NMR spectra, the signal of the aldehyde at ca 190 ppm was not observed, and a new signal at ca 150 ppm due to the oxime carbon CH=NOH was detected, confirming the formation of the aldoximes (I) and (II).

( )-1-naphthaldehyde oxime (I)

Yield: 90%. IR (cm−1): 3389 (OH), 1614 (C=N). 1H NMR (CDCl3), δ: 7.53 (t, J HH 7.5 Hz, 1H, CH aromatic), 7.56 (t, J HH 7.0 Hz, 1H, CH aromatic), 7.61 (t, J HH 7.0 Hz, 1H, CH aromatic), 7.82 (d, J HH 7.1 Hz, 1H, CH aromatic), 7.93 (t, J HH 8.1 Hz, 2H, CH aromatic), 8.48 (d, J HH 8.3 Hz, 1H, CH aromatic), 8.87 (s, 1H, CH=N). 13C NMR (CDCl3), δ: 124.2, 125.4, 126.2, 127.0, 127.1 (CHaromatic), 128.0 (Caromatic), 128.8, 130.6 (CHaromatic), 130.8, 133.8 (Caromatic), 150.0 (CH=N). DEPT-135 NMR (CDCl3), δ: 124.2, 125.4, 126.2, 127.0, 127.1, 128.8, 130.6 (CHaromatic), 150.0 (CH=N).

-phenanthrene-9-carbaldehyde oxime (II)

Yield: 89%. IR (cm−1): 3200 (OH), 1607 (C=N). 1H NMR (CDCl3), δ: 7.64 (t, J HH 7.9 Hz, 1H, CH aromatic), 7.68–7.75 (m, 3H, CH aromatic), 7.94 (d, J HH 7.9 Hz, 1H, CH aromatic), 8.04 (s, 1H, CH aromatic), 8.62 (d, J HH 7.9 Hz, 1H, CH aromatic), 8.70 (d, J HH 8.2 Hz, 1H, CH aromatic), 8.77 (d, J HH 8.2 Hz, 1H, CH aromatic), 8.85 (s, 1H, CH=N). 13C NMR (CDCl3), δ: 122.6, 123.1, 125.4 (CHaromatic), 126.8 (Caromatic), 126.9, 127.0, 127.2, 127.9, 129.3 (CHaromatic), 130.7, 131.0, 131.1 (Caromatic), 150.8 (CH=N). DEPT-135 NMR (CDCl3), δ: 122.6, 123.1, 125.4, 126.9, 127.0, 127.2, 127.9, 129.3 (CHaromatic), 150.8 (CH=N).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All C-bound H atoms were located in difference-Fourier maps but were subsequently treated as riding with C—H = 0.93 Å and with U iso(H) = 1.2U eq(C). The H atoms of the OH groups were positioned with idealized geometry and were refined freely in both structures.

Table 4

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C11H9NO	C15H11NO
M r	171.19	221.25
Crystal system, space group	Monoclinic, P21	Monoclinic, P21
Temperature (K)	295	295
a, b, c (Å)	7.928 (5), 4.843 (3), 11.444 (7)	8.2397 (8), 4.9728 (5), 13.9332 (14)
β (°)	94.03 (5)	106.680 (7)
V (Å3)	438.3 (5)	546.88 (10)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.08	0.09
Crystal size (mm)	0.10 × 0.06 × 0.02	0.16 × 0.09 × 0.05
Data collection
Diffractometer	Bruker D8 Quest	Bruker D8 Quest
Absorption correction	Multi-scan (SADABS; Bruker, 2016 ▸)	Multi-scan (SADABS; Bruker, 2016 ▸)
T min, T max	0.684, 0.745	0.698, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	5762, 1570, 957	7330, 1988, 1509
R int	0.100	0.053
(sin θ/λ)max (Å−1)	0.603	0.602
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.055, 0.098, 1.06	0.040, 0.093, 1.04
No. of reflections	1570	1988
No. of parameters	122	159
No. of restraints	1	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.15, −0.15	0.15, −0.15

Computer programs: APEX3 and SAINT (Bruker, 2016 ▸), SHELXT2014 (Sheldrick, 2015a ▸) and SHELXL2014 (Sheldrick, 2015b ▸).

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018002116/zs2397sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018002116/zs2397Isup4.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989018002116/zs2397IIsup5.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018002116/zs2397Isup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018002116/zs2397IIsup5.cml

CCDC references: 1821856, 1821855

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H9NO	F(000) = 180
Mr = 171.19	Dx = 1.297 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.928 (5) Å	Cell parameters from 1367 reflections
b = 4.843 (3) Å	θ = 2.6–22.6°
c = 11.444 (7) Å	µ = 0.08 mm−1
β = 94.03 (5)°	T = 295 K
V = 438.3 (5) Å3	Block, colourless
Z = 2	0.10 × 0.06 × 0.02 mm

Bruker D8 Quest diffractometer	957 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.100
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 25.4°, θmin = 2.6°
Tmin = 0.684, Tmax = 0.745	h = −9→9
5762 measured reflections	k = −5→5
1570 independent reflections	l = −13→13

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0164P)2 + 0.1408P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1570 reflections	Δρmax = 0.15 e Å−3
122 parameters	Δρmin = −0.15 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.8254 (4)	−0.0401 (7)	0.5056 (3)	0.0458 (9)
N1	0.8708 (5)	0.1715 (9)	0.4312 (3)	0.0418 (11)
C1	0.7559 (5)	0.4959 (10)	0.2895 (4)	0.0318 (12)
C2	0.8998 (6)	0.5156 (11)	0.2295 (4)	0.0452 (14)
H2	0.9903	0.3987	0.2494	0.054*
C3	0.9129 (7)	0.7072 (14)	0.1393 (5)	0.0569 (16)
H3	1.0128	0.7207	0.1017	0.068*
C4	0.7801 (7)	0.8737 (11)	0.1066 (4)	0.0499 (15)
H4	0.7888	0.9970	0.0450	0.060*
C4'	0.6296 (6)	0.8624 (10)	0.1645 (4)	0.0377 (12)
C5	0.4924 (6)	1.0383 (10)	0.1338 (4)	0.0468 (15)
H5	0.5009	1.1626	0.0726	0.056*
C6	0.3485 (7)	1.0323 (12)	0.1907 (5)	0.0570 (17)
H6	0.2585	1.1479	0.1677	0.068*
C7	0.3370 (6)	0.8491 (11)	0.2846 (4)	0.0478 (15)
H7	0.2393	0.8461	0.3250	0.057*
C8	0.4663 (5)	0.6760 (11)	0.3176 (4)	0.0387 (13)
H8	0.4557	0.5558	0.3800	0.046*
C8'	0.6172 (5)	0.6760 (10)	0.2582 (4)	0.0285 (11)
C11	0.7413 (6)	0.2826 (9)	0.3785 (4)	0.0350 (12)
H11	0.6343	0.2264	0.3972	0.042*
H1	0.922 (7)	−0.129 (13)	0.528 (5)	0.10 (2)*

	U11	U22	U33	U12	U13	U23
O1	0.041 (2)	0.044 (2)	0.051 (2)	0.008 (2)	−0.0047 (18)	0.008 (2)
N1	0.040 (2)	0.038 (3)	0.046 (3)	0.001 (2)	−0.005 (2)	−0.005 (2)
C1	0.033 (3)	0.029 (3)	0.033 (3)	−0.007 (3)	−0.002 (2)	−0.007 (3)
C2	0.035 (3)	0.054 (4)	0.048 (3)	−0.005 (3)	0.009 (2)	−0.014 (3)
C3	0.051 (3)	0.080 (5)	0.043 (3)	−0.018 (4)	0.021 (3)	−0.012 (4)
C4	0.064 (4)	0.051 (4)	0.036 (3)	−0.017 (3)	0.011 (3)	−0.005 (3)
C4'	0.046 (3)	0.037 (3)	0.029 (3)	−0.008 (3)	−0.003 (2)	−0.007 (3)
C5	0.060 (4)	0.037 (4)	0.041 (3)	−0.009 (3)	−0.011 (3)	0.008 (3)
C6	0.049 (3)	0.049 (4)	0.070 (4)	0.006 (3)	−0.013 (3)	0.008 (4)
C7	0.035 (3)	0.048 (4)	0.060 (4)	0.002 (3)	0.000 (3)	0.009 (3)
C8	0.036 (3)	0.039 (3)	0.040 (3)	0.002 (3)	−0.002 (2)	0.008 (3)
C8'	0.029 (2)	0.027 (3)	0.029 (3)	−0.004 (2)	−0.0016 (19)	−0.008 (3)
C11	0.032 (3)	0.029 (3)	0.044 (3)	0.002 (2)	0.003 (2)	−0.008 (3)

O1—N1	1.395 (5)	C4'—C5	1.407 (6)
O1—H1	0.90 (6)	C4'—C8'	1.410 (6)
N1—C11	1.273 (5)	C5—C6	1.353 (6)
C1—C2	1.375 (6)	C5—H5	0.9300
C1—C8'	1.429 (6)	C6—C7	1.402 (7)
C1—C11	1.461 (6)	C6—H6	0.9300
C2—C3	1.397 (7)	C7—C8	1.357 (6)
C2—H2	0.9300	C7—H7	0.9300
C3—C4	1.358 (7)	C8—C8'	1.417 (5)
C3—H3	0.9300	C8—H8	0.9300
C4—C4'	1.406 (6)	C11—H11	0.9300
C4—H4	0.9300
N1—O1—H1	106 (4)	C6—C5—H5	119.0
C11—N1—O1	111.5 (4)	C4'—C5—H5	119.0
C2—C1—C8'	118.9 (4)	C5—C6—C7	119.0 (5)
C2—C1—C11	120.4 (5)	C5—C6—H6	120.5
C8'—C1—C11	120.6 (4)	C7—C6—H6	120.5
C1—C2—C3	121.5 (5)	C8—C7—C6	121.0 (5)
C1—C2—H2	119.3	C8—C7—H7	119.5
C3—C2—H2	119.3	C6—C7—H7	119.5
C4—C3—C2	120.1 (5)	C7—C8—C8'	120.9 (5)
C4—C3—H3	119.9	C7—C8—H8	119.5
C2—C3—H3	119.9	C8'—C8—H8	119.5
C3—C4—C4'	120.9 (5)	C4'—C8'—C8	118.1 (4)
C3—C4—H4	119.5	C4'—C8'—C1	119.2 (4)
C4'—C4—H4	119.5	C8—C8'—C1	122.7 (4)
C4—C4'—C5	121.7 (5)	N1—C11—C1	121.9 (4)
C4—C4'—C8'	119.3 (5)	N1—C11—H11	119.0
C5—C4'—C8'	118.9 (4)	C1—C11—H11	119.0
C6—C5—C4'	122.0 (5)
C8'—C1—C2—C3	0.1 (7)	C5—C4'—C8'—C8	−0.3 (6)
C11—C1—C2—C3	176.2 (5)	C4—C4'—C8'—C1	−2.1 (6)
C1—C2—C3—C4	−2.0 (8)	C5—C4'—C8'—C1	179.7 (4)
C2—C3—C4—C4'	1.8 (8)	C7—C8—C8'—C4'	0.5 (7)
C3—C4—C4'—C5	178.3 (5)	C7—C8—C8'—C1	−179.6 (4)
C3—C4—C4'—C8'	0.3 (7)	C2—C1—C8'—C4'	1.9 (6)
C4—C4'—C5—C6	−178.7 (5)	C11—C1—C8'—C4'	−174.2 (4)
C8'—C4'—C5—C6	−0.6 (7)	C2—C1—C8'—C8	−178.0 (4)
C4'—C5—C6—C7	1.3 (8)	C11—C1—C8'—C8	5.9 (6)
C5—C6—C7—C8	−1.2 (8)	O1—N1—C11—C1	−175.5 (4)
C6—C7—C8—C8'	0.2 (7)	C2—C1—C11—N1	23.6 (6)
C4—C4'—C8'—C8	177.8 (4)	C8'—C1—C11—N1	−160.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1i	0.90 (6)	1.94 (6)	2.834 (5)	177 (6)

C15H11NO	F(000) = 232
Mr = 221.25	Dx = 1.344 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 8.2397 (8) Å	Cell parameters from 2141 reflections
b = 4.9728 (5) Å	θ = 2.6–24.9°
c = 13.9332 (14) Å	µ = 0.09 mm−1
β = 106.680 (7)°	T = 295 K
V = 546.88 (10) Å3	Block, colourless
Z = 2	0.16 × 0.09 × 0.05 mm

Bruker D8 Quest diffractometer	1509 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.053
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 25.3°, θmin = 2.6°
Tmin = 0.698, Tmax = 0.745	h = −9→9
7330 measured reflections	k = −5→5
1988 independent reflections	l = −16→16

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.093	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.15 e Å−3
1988 reflections	Δρmin = −0.15 e Å−3
159 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.058 (11)

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.

	x	y	z	Uiso*/Ueq
O1	0.3294 (3)	1.0407 (5)	0.49418 (15)	0.0446 (6)
N1	0.4084 (3)	0.8293 (5)	0.55737 (16)	0.0371 (6)
C11	0.3086 (4)	0.7264 (5)	0.6016 (2)	0.0340 (7)
H11	0.197024	0.785637	0.585614	0.041*
C9	0.3660 (3)	0.5157 (6)	0.67732 (18)	0.0322 (7)
C10	0.5314 (4)	0.5027 (7)	0.7316 (2)	0.0366 (7)
H10	0.607395	0.622514	0.716727	0.044*
C10'	0.5935 (3)	0.3140 (6)	0.81023 (19)	0.0349 (7)
C1	0.7655 (4)	0.3096 (7)	0.8651 (2)	0.0472 (8)
H1	0.840812	0.427685	0.848577	0.057*
C2	0.8232 (4)	0.1335 (8)	0.9426 (2)	0.0510 (9)
H2	0.937339	0.131717	0.978623	0.061*
C3	0.7116 (4)	−0.0423 (7)	0.9676 (2)	0.0481 (9)
H3	0.751583	−0.162219	1.020293	0.058*
C4	0.5438 (4)	−0.0424 (6)	0.9159 (2)	0.0445 (8)
H4	0.470941	−0.162230	0.933886	0.053*
C4'	0.4792 (4)	0.1366 (6)	0.83561 (19)	0.0333 (7)
C5'	0.3013 (4)	0.1442 (6)	0.77844 (19)	0.0334 (7)
C5	0.1811 (4)	−0.0332 (6)	0.7975 (2)	0.0431 (8)
H5	0.215809	−0.156417	0.849626	0.052*
C6	0.0153 (4)	−0.0300 (7)	0.7419 (3)	0.0499 (9)
H6	−0.061247	−0.149898	0.756119	0.060*
C7	−0.0389 (4)	0.1524 (7)	0.6641 (2)	0.0499 (9)
H7	−0.151904	0.154288	0.626056	0.060*
C8	0.0728 (4)	0.3292 (7)	0.6429 (2)	0.0424 (8)
H8	0.034520	0.451063	0.590667	0.051*
C8'	0.2453 (3)	0.3306 (6)	0.69893 (19)	0.0317 (7)
H	0.413 (4)	1.109 (7)	0.475 (2)	0.061 (12)*

	U11	U22	U33	U12	U13	U23
O1	0.0474 (13)	0.0426 (14)	0.0448 (12)	0.0035 (11)	0.0145 (10)	0.0153 (11)
N1	0.0446 (14)	0.0344 (14)	0.0343 (13)	0.0040 (13)	0.0142 (11)	0.0020 (12)
C11	0.0375 (16)	0.0301 (17)	0.0356 (15)	0.0031 (14)	0.0127 (13)	−0.0001 (13)
C9	0.0408 (16)	0.0295 (16)	0.0284 (14)	0.0016 (16)	0.0131 (12)	−0.0015 (14)
C10	0.0416 (16)	0.0334 (17)	0.0352 (14)	−0.0037 (15)	0.0116 (12)	0.0008 (15)
C10'	0.0427 (16)	0.0307 (16)	0.0313 (14)	0.0026 (15)	0.0106 (12)	−0.0056 (14)
C1	0.0453 (18)	0.046 (2)	0.0475 (18)	0.0005 (19)	0.0093 (14)	0.0020 (17)
C2	0.0461 (19)	0.053 (2)	0.0475 (19)	0.0078 (18)	0.0024 (15)	−0.0014 (17)
C3	0.060 (2)	0.044 (2)	0.0371 (17)	0.0147 (18)	0.0089 (15)	0.0060 (15)
C4	0.0555 (19)	0.041 (2)	0.0390 (17)	0.0035 (17)	0.0168 (14)	0.0040 (15)
C4'	0.0464 (17)	0.0265 (15)	0.0294 (14)	0.0033 (15)	0.0149 (13)	−0.0035 (13)
C5'	0.0432 (16)	0.0297 (15)	0.0306 (14)	0.0021 (15)	0.0157 (12)	−0.0040 (14)
C5	0.0552 (19)	0.036 (2)	0.0441 (18)	−0.0002 (17)	0.0247 (15)	0.0039 (15)
C6	0.0458 (19)	0.047 (2)	0.065 (2)	−0.0071 (18)	0.0282 (16)	0.0019 (18)
C7	0.0401 (18)	0.051 (2)	0.059 (2)	−0.0031 (18)	0.0148 (15)	0.0046 (19)
C8	0.0440 (18)	0.0402 (18)	0.0413 (17)	0.0011 (17)	0.0096 (14)	0.0018 (16)
C8'	0.0386 (15)	0.0285 (15)	0.0305 (14)	0.0027 (15)	0.0139 (12)	−0.0031 (14)

O1—N1	1.405 (3)	C3—C4	1.363 (4)
O1—H	0.88 (3)	C3—H3	0.9300
N1—C11	1.268 (3)	C4—C4'	1.409 (4)
C11—C9	1.466 (4)	C4—H4	0.9300
C11—H11	0.9300	C4'—C5'	1.454 (4)
C9—C10	1.357 (3)	C5'—C5	1.408 (4)
C9—C8'	1.448 (4)	C5'—C8'	1.416 (4)
C10—C10'	1.422 (4)	C5—C6	1.364 (4)
C10—H10	0.9300	C5—H5	0.9300
C10'—C1	1.405 (4)	C6—C7	1.385 (4)
C10'—C4'	1.408 (4)	C6—H6	0.9300
C1—C2	1.365 (4)	C7—C8	1.365 (4)
C1—H1	0.9300	C7—H7	0.9300
C2—C3	1.384 (5)	C8—C8'	1.412 (4)
C2—H2	0.9300	C8—H8	0.9300
N1—O1—H	102 (2)	C3—C4—H4	119.5
C11—N1—O1	110.9 (2)	C4'—C4—H4	119.5
N1—C11—C9	121.2 (3)	C10'—C4'—C4	117.9 (2)
N1—C11—H11	119.4	C10'—C4'—C5'	119.2 (2)
C9—C11—H11	119.4	C4—C4'—C5'	122.9 (3)
C10—C9—C8'	119.6 (2)	C5—C5'—C8'	118.0 (2)
C10—C9—C11	120.0 (3)	C5—C5'—C4'	122.2 (3)
C8'—C9—C11	120.4 (2)	C8'—C5'—C4'	119.8 (2)
C9—C10—C10'	122.9 (3)	C6—C5—C5'	122.0 (3)
C9—C10—H10	118.6	C6—C5—H5	119.0
C10'—C10—H10	118.6	C5'—C5—H5	119.0
C1—C10'—C4'	119.8 (3)	C5—C6—C7	119.9 (3)
C1—C10'—C10	120.9 (3)	C5—C6—H6	120.1
C4'—C10'—C10	119.2 (2)	C7—C6—H6	120.1
C2—C1—C10'	120.6 (3)	C8—C7—C6	120.3 (3)
C2—C1—H1	119.7	C8—C7—H7	119.8
C10'—C1—H1	119.7	C6—C7—H7	119.8
C1—C2—C3	119.9 (3)	C7—C8—C8'	121.2 (3)
C1—C2—H2	120.1	C7—C8—H8	119.4
C3—C2—H2	120.1	C8'—C8—H8	119.4
C4—C3—C2	120.9 (3)	C8—C8'—C5'	118.6 (3)
C4—C3—H3	119.5	C8—C8'—C9	122.0 (3)
C2—C3—H3	119.5	C5'—C8'—C9	119.3 (2)
C3—C4—C4'	120.9 (3)
O1—N1—C11—C9	−175.3 (2)	C4—C4'—C5'—C5	−1.9 (4)
N1—C11—C9—C10	27.6 (4)	C10'—C4'—C5'—C8'	−0.5 (4)
N1—C11—C9—C8'	−156.1 (2)	C4—C4'—C5'—C8'	179.7 (3)
C8'—C9—C10—C10'	−0.2 (4)	C8'—C5'—C5—C6	0.2 (4)
C11—C9—C10—C10'	176.1 (3)	C4'—C5'—C5—C6	−178.2 (3)
C9—C10—C10'—C1	−179.3 (3)	C5'—C5—C6—C7	−0.1 (5)
C9—C10—C10'—C4'	−1.9 (4)	C5—C6—C7—C8	−0.1 (5)
C4'—C10'—C1—C2	0.4 (5)	C6—C7—C8—C8'	0.3 (5)
C10—C10'—C1—C2	177.9 (3)	C7—C8—C8'—C5'	−0.2 (4)
C10'—C1—C2—C3	0.0 (5)	C7—C8—C8'—C9	179.7 (3)
C1—C2—C3—C4	−0.2 (5)	C5—C5'—C8'—C8	−0.1 (4)
C2—C3—C4—C4'	0.0 (5)	C4'—C5'—C8'—C8	178.4 (3)
C1—C10'—C4'—C4	−0.5 (4)	C5—C5'—C8'—C9	−179.9 (2)
C10—C10'—C4'—C4	−178.1 (3)	C4'—C5'—C8'—C9	−1.5 (4)
C1—C10'—C4'—C5'	179.7 (3)	C10—C9—C8'—C8	−178.0 (3)
C10—C10'—C4'—C5'	2.2 (4)	C11—C9—C8'—C8	5.7 (4)
C3—C4—C4'—C10'	0.3 (4)	C10—C9—C8'—C5'	1.9 (4)
C3—C4—C4'—C5'	−179.9 (3)	C11—C9—C8'—C5'	−174.4 (2)
C10'—C4'—C5'—C5	177.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H···N1i	0.88 (3)	1.99 (3)	2.852 (3)	169 (3)