Redetermination of the twinned structure of triacetone amine ­monohydrate

The structure of triacetone amine monohydrate (systematic name: 2,2,6,6-tetra­methyl­piperidin-4-one monohydrate), C₉H₁₇NO·H₂O, has been redetermined at 180 K. The compound crystallizes in space group P2₁/c with a monoclinic angle of 90.084 (3)°. All crystals examined exhibited twinning and appeared orthorhombic, with a unit-cell volume half that of the true volume.

S1. Comment

Triacetone amine monohydrate, (I), has been reported previously to crystallize in the orthorhombic space group Pna2₁ with four molecules in the unit cell (De Camp et al., 1974). The single independent molecule of C₉H₁₇NO in this structure displays rather curious disorder of the O atom over two sites displaced either side of the position expected for the carbonyl group (Fig. 1). The structure of (I) has been redetermined and is shown in fact to be ordered in the monoclinic space group P2₁/c, with a monoclinic angle very close to 90° and two independent C₉H₁₇NO molecules. Several crystals have been examined, and in each case they exhibit twinning and appear orthorhombic, with a unit cell volume half that of the true volume. \sch

The orthorhombic structure of (I) reported previously by De Camp et al. has unit-cell parameters a = 9.219 (1), b = 8.956 (1) and c = 13.113 (2) Å in the space group Pna2₁. Initial examination of the crystal of (I) suggested an orthorhombic lattice with unit-cell parameters (refined against all 11277 data) a = 9.0870 (4), b = 17.7379 (6) and c = 13.0508 (5) Å, i.e. the true b repeat distance may be twice that reported by De Camp. Merging of the data in the Laue group mmm, however, gave an R_int of 0.120, and examination of the data revealed that the systematic absence conditions are not consistent with any orthorhombic space group. Several crystals were examined, and the same result was obtained in each case. Processing the data in Laue group 1, with the unit-cell parameters refined without constraint, showed that while α and β did not deviate significantly from 90°, the angle γ refined to be 89.916 (3)°. Transformation into the standard setting gives a monoclinic lattice with unit-cell parameters (refined against all 11277 data) a = 9.0860 (4), b = 13.0550 (6) and c = 17.7367 (6) Å, and β = 90.084 (3)°. The value of R_int for this lattice in Laue group 2/m is 0.050, significantly smaller than that obtained for the orthorhombic lattice. The systematic absence conditions are consistent with the space group P2₁/c and the structure was solved by direct methods using SIR92 (Altomare et al., 1994) to reveal two symmetry-independent molecules.

Refinement of this structure did not proceed satisfactorily, however, stalling with R1 = 0.257 for isotropic atoms prior to the addition of H atoms. This observation, together with the fact that β is so close to 90° (i.e. the metric symmetry appears higher than the Laue symmetry) suggests that the crystal may be twinned. Introduction of the twin law (100/010/001) immediately reduced R1 to 0.160 and the refinement proceeded satisfactorily, converging with R1 = 0.0532. The scale factor for the two twin components refined to be 0.328 (2). The structure is ordered, with the carbonyl groups in each independent C₉H₁₇NO molecule adopting a chemically reasonable geometry (Fig. 2). An extensive network of hydrogen bonds (see Table 1) exists within the structure, as illustrated in Fig. 3.

Comparison of the monoclinic structure of (I) with that reported previously in Pna2₁ by De Camp et al. may be made by bringing the 2₁ screw axes into coincidence [by transforming the orthorhombic lattice by the matrix (100/001/010), followed by an origin shift of (0,1/2,0), such that the space group becomes Pn2₁a]. The significant difference between the structures arises along the c direction: in the true monoclinic structure, molecules are related by a c glide perpendicular to b at y = 1/4, while in the Pn2₁a structure, the corresponding molecules are related by the c lattice translation. In the orthorhombic model, therefore, two glide-related molecules are superimposed, giving rise to the observed disorder of the carbonyl group.

S2. Experimental

The crystal of (I) was prepared by sublimation in air at room temperature, from a sample supplied by John Foulkes (Alpherantz Research, Cambridge).

S3. Refinement

H atoms attached to C were placed geometrically and refined using a riding model with U_eq(H) = xU_eq(C), where x = 1.5 for methyl H atoms and 1.2 for all others. C—H distances were fixed at 0.98 Å for methyl groups and 0.99 Å for methylene groups. H atoms bound to N and O were located in difference Fourier maps and their coordinates were refined with U_eq(H) = 1.2U_eq(N or O). To ensure a reasonable geometry for the water molecules, the O—H bond distances were restrained to be equivalent, with an s.u. of 0.01 Å, and the H···H distances within each molecule were restrained to be 1.633 times this value, with an s.u. of 0.01 Å.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view (XP; Sheldrick, 1993) of the disorder in the single independent molecule in De Camp's Pna21 structure of (I) (De Camp et al., 1974).
	Fig. 2. The molecular structure and atom-labelling scheme for the two independent molecules in (I), showing displacement ellipsoids at the 30% probability level. H atoms bound to C have been omitted for clarity.
	Fig. 3. A projection along the a direction showing the hydrogen-bond network in (I) (CAMERON; Watkin et al., 1996). O atoms are shown as white circles, H as small white circles, C as light-grey circles and N as dark-grey circles. H atoms bound to C have been omitted for clarity.

2,2,6,6-tetramethylpiperidin-4-one monohydrate

Crystal data

C9H17NO·H2O	Dx = 1.094 Mg m^−3
Mr = 173.25	Melting point = 311–313 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
a = 9.0860 (4) Å	Cell parameters from 11277 reflections
b = 13.0550 (6) Å	θ = 1.0–25.0°
c = 17.7367 (6) Å	µ = 0.08 mm^−1
β = 90.084 (3)°	T = 180 K
V = 2103.89 (15) Å^3	Block, colourless
Z = 8	0.37 × 0.30 × 0.30 mm
F(000) = 768

Data collection

Nonius KappaCCD diffractometer	3679 independent reflections
Radiation source: fine-focus sealed tube	2795 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Thin slice ω and ϕ scans	θmax = 25.0°, θmin = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −10→10
Tmin = 0.934, Tmax = 0.979	k = −15→15
15306 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.073P)^2 + 0.408P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3679 reflections	Δρmax = 0.51 e Å^−3
246 parameters	Δρmin = −0.30 e Å^−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (3)

Special details

Experimental. Crystal twinned to appear orthorhombic.

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 (Ų)

	x	y	z	Uiso*/Ueq
O100	0.8645 (2)	0.2267 (2)	0.31352 (12)	0.0829 (8)
H100	0.805 (3)	0.238 (3)	0.3522 (11)	0.099*
H101	0.818 (3)	0.240 (3)	0.2707 (12)	0.099*
O101	0.3567 (2)	0.20849 (17)	−0.05934 (11)	0.0596 (6)
H102	0.306 (3)	0.234 (2)	−0.0211 (10)	0.071*
H103	0.301 (3)	0.209 (2)	−0.1005 (10)	0.071*
O1A	0.7511 (3)	0.2686 (2)	0.16842 (11)	0.0918 (9)
N1A	0.6968 (2)	0.24812 (14)	−0.05136 (11)	0.0334 (5)
H1NA	0.606 (3)	0.2402 (19)	−0.0638 (15)	0.040*
C1A	0.6874 (3)	0.2594 (2)	0.10801 (14)	0.0529 (7)
C2A	0.6355 (3)	0.3487 (2)	0.06436 (13)	0.0458 (6)
H2AA	0.6613	0.4125	0.0915	0.055*
H2AB	0.5271	0.3458	0.0593	0.055*
C3A	0.6598 (3)	0.1583 (2)	0.07113 (14)	0.0538 (7)
H3AA	0.5525	0.1475	0.0651	0.065*
H3AB	0.6992	0.1025	0.1032	0.065*
C4A	0.7070 (3)	0.34985 (18)	−0.01537 (12)	0.0381 (6)
C5A	0.7358 (3)	0.15571 (19)	−0.00754 (13)	0.0434 (6)
C6A	0.8652 (3)	0.3890 (2)	−0.00916 (15)	0.0574 (8)
H6AA	0.9149	0.3807	−0.0578	0.086*
H6AB	0.9178	0.3497	0.0295	0.086*
H6AC	0.8644	0.4616	0.0048	0.086*
C7A	0.6209 (3)	0.42269 (18)	−0.06626 (15)	0.0521 (7)
H7AA	0.6614	0.4201	−0.1174	0.078*
H7AB	0.6289	0.4927	−0.0467	0.078*
H7AC	0.5172	0.4021	−0.0674	0.078*
C8A	0.6794 (4)	0.0646 (2)	−0.05218 (18)	0.0691 (9)
H8AA	0.5736	0.0725	−0.0612	0.104*
H8AB	0.6972	0.0016	−0.0236	0.104*
H8AC	0.7311	0.0610	−0.1006	0.104*
C9A	0.9034 (3)	0.1463 (3)	0.00321 (16)	0.0646 (9)
H9AA	0.9367	0.1970	0.0403	0.097*
H9AB	0.9528	0.1586	−0.0450	0.097*
H9AC	0.9274	0.0773	0.0212	0.097*
O1B	0.2392 (2)	0.29864 (16)	0.07831 (9)	0.0620 (6)
N1B	0.1957 (2)	0.27460 (13)	0.30070 (10)	0.0319 (5)
H1NB	0.099 (3)	0.2670 (17)	0.3147 (15)	0.038*
C1B	0.1829 (3)	0.28667 (19)	0.13980 (13)	0.0400 (6)
C2B	0.1667 (3)	0.18482 (18)	0.17761 (14)	0.0475 (7)
H2BA	0.2112	0.1310	0.1456	0.057*
H2BB	0.0609	0.1688	0.1836	0.057*
C3B	0.1264 (3)	0.37406 (18)	0.18529 (12)	0.0393 (6)
H3BA	0.0183	0.3678	0.1906	0.047*
H3BB	0.1474	0.4390	0.1586	0.047*
C4B	0.2423 (3)	0.18454 (18)	0.25599 (13)	0.0410 (6)
C5B	0.1979 (3)	0.37719 (16)	0.26464 (12)	0.0355 (6)
C6B	0.1930 (4)	0.09084 (19)	0.30047 (16)	0.0620 (8)
H6BA	0.2427	0.0900	0.3495	0.093*
H6BB	0.2183	0.0286	0.2724	0.093*
H6BC	0.0862	0.0936	0.3081	0.093*
C7B	0.4101 (3)	0.1816 (2)	0.24650 (18)	0.0645 (8)
H7BA	0.4574	0.1928	0.2955	0.097*
H7BB	0.4406	0.2354	0.2113	0.097*
H7BC	0.4395	0.1146	0.2266	0.097*
C8B	0.3528 (3)	0.4215 (2)	0.25951 (14)	0.0555 (7)
H8BA	0.4029	0.4132	0.3081	0.083*
H8BB	0.3470	0.4944	0.2469	0.083*
H8BC	0.4080	0.3853	0.2203	0.083*
C9B	0.1065 (3)	0.44628 (19)	0.31553 (14)	0.0537 (7)
H9BA	0.1501	0.4477	0.3661	0.081*
H9BB	0.0058	0.4198	0.3185	0.081*
H9BC	0.1048	0.5158	0.2947	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O100	0.0399 (12)	0.172 (2)	0.0372 (11)	0.0005 (14)	0.0048 (10)	0.0081 (14)
O101	0.0459 (12)	0.0915 (15)	0.0413 (10)	0.0094 (10)	−0.0079 (9)	−0.0153 (11)
O1A	0.0620 (15)	0.184 (3)	0.0293 (11)	−0.0062 (17)	−0.0088 (11)	0.0108 (12)
N1A	0.0321 (11)	0.0404 (10)	0.0276 (10)	0.0019 (10)	0.0020 (9)	0.0006 (8)
C1A	0.0336 (14)	0.098 (2)	0.0272 (14)	−0.0013 (15)	0.0087 (12)	0.0053 (13)
C2A	0.0437 (16)	0.0570 (15)	0.0368 (13)	−0.0058 (12)	0.0038 (12)	−0.0125 (12)
C3A	0.0537 (17)	0.0610 (16)	0.0466 (15)	0.0153 (14)	0.0111 (14)	0.0243 (13)
C4A	0.0365 (14)	0.0428 (13)	0.0350 (12)	−0.0063 (11)	0.0020 (10)	−0.0046 (10)
C5A	0.0451 (15)	0.0444 (14)	0.0408 (13)	0.0127 (12)	0.0070 (12)	0.0092 (11)
C6A	0.0490 (17)	0.0695 (18)	0.0537 (16)	−0.0190 (16)	0.0049 (13)	−0.0077 (14)
C7A	0.0590 (17)	0.0363 (13)	0.0610 (16)	0.0007 (12)	0.0020 (14)	0.0055 (12)
C8A	0.086 (2)	0.0383 (14)	0.083 (2)	0.0100 (16)	0.0149 (18)	0.0019 (14)
C9A	0.0536 (18)	0.089 (2)	0.0510 (16)	0.0284 (17)	0.0075 (14)	0.0159 (16)
O1B	0.0662 (13)	0.0894 (14)	0.0306 (10)	−0.0084 (11)	0.0090 (10)	−0.0055 (9)
N1B	0.0293 (10)	0.0344 (10)	0.0320 (11)	−0.0018 (8)	0.0035 (9)	0.0036 (7)
C1B	0.0356 (14)	0.0562 (15)	0.0280 (13)	−0.0037 (12)	−0.0034 (11)	−0.0047 (11)
C2B	0.0597 (17)	0.0406 (14)	0.0422 (14)	0.0044 (13)	−0.0046 (13)	−0.0114 (11)
C3B	0.0426 (15)	0.0414 (13)	0.0337 (12)	−0.0039 (11)	−0.0035 (11)	0.0058 (10)
C4B	0.0475 (15)	0.0356 (12)	0.0400 (13)	0.0081 (11)	−0.0017 (12)	−0.0038 (10)
C5B	0.0448 (14)	0.0315 (11)	0.0304 (11)	−0.0045 (11)	−0.0015 (10)	0.0009 (9)
C6B	0.087 (2)	0.0351 (13)	0.0634 (18)	0.0036 (15)	−0.0107 (17)	0.0064 (12)
C7B	0.0478 (17)	0.080 (2)	0.0655 (18)	0.0241 (15)	0.0008 (15)	−0.0043 (16)
C8B	0.0565 (17)	0.0619 (17)	0.0479 (15)	−0.0260 (14)	−0.0065 (13)	0.0104 (13)
C9B	0.078 (2)	0.0407 (14)	0.0420 (13)	0.0089 (14)	0.0001 (14)	−0.0058 (11)

Geometric parameters (Å, º)

O100—H100	0.89 (1)	C9A—H9AB	0.9800
O100—H101	0.89 (1)	C9A—H9AC	0.9800
O101—H102	0.89 (1)	O1B—C1B	1.216 (3)
O101—H103	0.89 (1)	N1B—C4B	1.480 (3)
O1A—C1A	1.223 (3)	N1B—C5B	1.484 (3)
N1A—C4A	1.476 (3)	N1B—H1NB	0.92 (3)
N1A—C5A	1.478 (3)	C1B—C3B	1.489 (3)
N1A—H1NA	0.86 (3)	C1B—C2B	1.497 (3)
C1A—C2A	1.476 (4)	C2B—C4B	1.550 (3)
C1A—C3A	1.494 (4)	C2B—H2BA	0.9900
C2A—C4A	1.557 (3)	C2B—H2BB	0.9900
C2A—H2AA	0.9900	C3B—C5B	1.550 (3)
C2A—H2AB	0.9900	C3B—H3BA	0.9900
C3A—C5A	1.558 (3)	C3B—H3BB	0.9900
C3A—H3AA	0.9900	C4B—C6B	1.523 (4)
C3A—H3AB	0.9900	C4B—C7B	1.534 (4)
C4A—C7A	1.526 (4)	C5B—C9B	1.523 (3)
C4A—C6A	1.530 (3)	C5B—C8B	1.524 (3)
C5A—C8A	1.517 (4)	C6B—H6BA	0.9800
C5A—C9A	1.540 (4)	C6B—H6BB	0.9800
C6A—H6AA	0.9800	C6B—H6BC	0.9800
C6A—H6AB	0.9800	C7B—H7BA	0.9800
C6A—H6AC	0.9800	C7B—H7BB	0.9800
C7A—H7AA	0.9800	C7B—H7BC	0.9800
C7A—H7AB	0.9800	C8B—H8BA	0.9800
C7A—H7AC	0.9800	C8B—H8BB	0.9800
C8A—H8AA	0.9800	C8B—H8BC	0.9800
C8A—H8AB	0.9800	C9B—H9BA	0.9800
C8A—H8AC	0.9800	C9B—H9BB	0.9800
C9A—H9AA	0.9800	C9B—H9BC	0.9800
H100—O100—H101	109.9 (13)	H9AB—C9A—H9AC	109.5
H102—O101—H103	109.1 (12)	C4B—N1B—C5B	118.80 (18)
C4A—N1A—C5A	119.49 (19)	C4B—N1B—H1NB	109.5 (15)
C4A—N1A—H1NA	106.2 (17)	C5B—N1B—H1NB	103.1 (15)
C5A—N1A—H1NA	105.4 (17)	O1B—C1B—C3B	122.2 (2)
O1A—C1A—C2A	122.2 (3)	O1B—C1B—C2B	123.9 (2)
O1A—C1A—C3A	123.3 (3)	C3B—C1B—C2B	113.8 (2)
C2A—C1A—C3A	114.5 (2)	C1B—C2B—C4B	111.1 (2)
C1A—C2A—C4A	110.5 (2)	C1B—C2B—H2BA	109.4
C1A—C2A—H2AA	109.5	C4B—C2B—H2BA	109.4
C4A—C2A—H2AA	109.5	C1B—C2B—H2BB	109.4
C1A—C2A—H2AB	109.5	C4B—C2B—H2BB	109.4
C4A—C2A—H2AB	109.5	H2BA—C2B—H2BB	108.0
H2AA—C2A—H2AB	108.1	C1B—C3B—C5B	111.58 (19)
C1A—C3A—C5A	109.7 (2)	C1B—C3B—H3BA	109.3
C1A—C3A—H3AA	109.7	C5B—C3B—H3BA	109.3
C5A—C3A—H3AA	109.7	C1B—C3B—H3BB	109.3
C1A—C3A—H3AB	109.7	C5B—C3B—H3BB	109.3
C5A—C3A—H3AB	109.7	H3BA—C3B—H3BB	108.0
H3AA—C3A—H3AB	108.2	N1B—C4B—C6B	106.0 (2)
N1A—C4A—C7A	105.86 (18)	N1B—C4B—C7B	111.3 (2)
N1A—C4A—C6A	112.9 (2)	C6B—C4B—C7B	109.2 (2)
C7A—C4A—C6A	108.4 (2)	N1B—C4B—C2B	110.61 (19)
N1A—C4A—C2A	110.97 (18)	C6B—C4B—C2B	109.6 (2)
C7A—C4A—C2A	109.2 (2)	C7B—C4B—C2B	109.9 (2)
C6A—C4A—C2A	109.3 (2)	N1B—C5B—C9B	105.74 (18)
N1A—C5A—C8A	106.5 (2)	N1B—C5B—C8B	112.39 (19)
N1A—C5A—C9A	111.5 (2)	C9B—C5B—C8B	108.4 (2)
C8A—C5A—C9A	109.6 (2)	N1B—C5B—C3B	111.20 (17)
N1A—C5A—C3A	110.31 (19)	C9B—C5B—C3B	109.00 (19)
C8A—C5A—C3A	109.5 (2)	C8B—C5B—C3B	109.98 (18)
C9A—C5A—C3A	109.3 (2)	C4B—C6B—H6BA	109.5
C4A—C6A—H6AA	109.5	C4B—C6B—H6BB	109.5
C4A—C6A—H6AB	109.5	H6BA—C6B—H6BB	109.5
H6AA—C6A—H6AB	109.5	C4B—C6B—H6BC	109.5
C4A—C6A—H6AC	109.5	H6BA—C6B—H6BC	109.5
H6AA—C6A—H6AC	109.5	H6BB—C6B—H6BC	109.5
H6AB—C6A—H6AC	109.5	C4B—C7B—H7BA	109.5
C4A—C7A—H7AA	109.5	C4B—C7B—H7BB	109.5
C4A—C7A—H7AB	109.5	H7BA—C7B—H7BB	109.5
H7AA—C7A—H7AB	109.5	C4B—C7B—H7BC	109.5
C4A—C7A—H7AC	109.5	H7BA—C7B—H7BC	109.5
H7AA—C7A—H7AC	109.5	H7BB—C7B—H7BC	109.5
H7AB—C7A—H7AC	109.5	C5B—C8B—H8BA	109.5
C5A—C8A—H8AA	109.5	C5B—C8B—H8BB	109.5
C5A—C8A—H8AB	109.5	H8BA—C8B—H8BB	109.5
H8AA—C8A—H8AB	109.5	C5B—C8B—H8BC	109.5
C5A—C8A—H8AC	109.5	H8BA—C8B—H8BC	109.5
H8AA—C8A—H8AC	109.5	H8BB—C8B—H8BC	109.5
H8AB—C8A—H8AC	109.5	C5B—C9B—H9BA	109.5
C5A—C9A—H9AA	109.5	C5B—C9B—H9BB	109.5
C5A—C9A—H9AB	109.5	H9BA—C9B—H9BB	109.5
H9AA—C9A—H9AB	109.5	C5B—C9B—H9BC	109.5
C5A—C9A—H9AC	109.5	H9BA—C9B—H9BC	109.5
H9AA—C9A—H9AC	109.5	H9BB—C9B—H9BC	109.5
O1A—C1A—C2A—C4A	121.2 (3)	O1B—C1B—C2B—C4B	122.6 (2)
C3A—C1A—C2A—C4A	−57.0 (3)	C3B—C1B—C2B—C4B	−56.0 (3)
O1A—C1A—C3A—C5A	−119.9 (3)	O1B—C1B—C3B—C5B	−123.9 (2)
C2A—C1A—C3A—C5A	58.3 (3)	C2B—C1B—C3B—C5B	54.8 (3)
C5A—N1A—C4A—C7A	−164.7 (2)	C5B—N1B—C4B—C6B	−166.5 (2)
C5A—N1A—C4A—C6A	76.9 (3)	C5B—N1B—C4B—C7B	74.8 (3)
C5A—N1A—C4A—C2A	−46.3 (3)	C5B—N1B—C4B—C2B	−47.7 (3)
C1A—C2A—C4A—N1A	47.6 (3)	C1B—C2B—C4B—N1B	49.8 (3)
C1A—C2A—C4A—C7A	164.0 (2)	C1B—C2B—C4B—C6B	166.3 (2)
C1A—C2A—C4A—C6A	−77.6 (3)	C1B—C2B—C4B—C7B	−73.6 (3)
C4A—N1A—C5A—C8A	166.5 (2)	C4B—N1B—C5B—C9B	164.7 (2)
C4A—N1A—C5A—C9A	−74.0 (3)	C4B—N1B—C5B—C8B	−77.2 (3)
C4A—N1A—C5A—C3A	47.7 (3)	C4B—N1B—C5B—C3B	46.6 (3)
C1A—C3A—C5A—N1A	−50.0 (3)	C1B—C3B—C5B—N1B	−47.5 (3)
C1A—C3A—C5A—C8A	−167.0 (2)	C1B—C3B—C5B—C9B	−163.7 (2)
C1A—C3A—C5A—C9A	72.9 (3)	C1B—C3B—C5B—C8B	77.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O100—H100···N1A^i	0.89 (1)	1.98 (1)	2.861 (3)	171 (3)
O100—H101···O1A	0.89 (1)	1.95 (1)	2.824 (3)	170 (3)
O101—H102···O1B	0.89 (1)	2.05 (1)	2.914 (3)	166 (3)
O101—H103···N1B^ii	0.89 (1)	2.01 (1)	2.888 (3)	171 (3)
N1A—H1NA···O101	0.86 (3)	2.31 (3)	3.136 (3)	163 (2)
N1B—H1NB···O100^iii	0.92 (3)	2.19 (3)	3.082 (3)	162 (2)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x−1, y, z.