2,2',3,3',4,4',5,5',6,6'-Decafluoro­diphenyl­amine and its 1:1 cocrystal with diphenyl­amine

In the structures of deca­fluoro­diphenyl­amine, C₁₂HF₁₀N, and its 1:1 cocrystal with diphenyl­amine, C₁₂HF₁₀N·C₁₂H₁₁N, the mol­ecules are located on special positions of C₂ symmetry. The NH groups are not involved in hydrogen bonding and the usual face-to-face stacking inter­actions between phenyl and penta­fluoro­phenyl rings are not observed in the cocrystal.

S1. Comment

2,2',3,3',4,4',5,5',6,6'-Decafluorodiphenylamine, (I), belongs to the family of strong N—H acids and its pK_a has been determined to be very similar to those of trifluoroacetic acid and pentafluorobenzoic acid (Koppel et al., 1994). The highly electron-withdrawing properties of the (C₆F₅)₂N ligand have recently been employed in organolanthanide (Click et al., 1999), transition metal (Giesbrecht et al., 2003) and lithium chemistry (Khvorost et al., 2004). The structural studies of (I) and its co-crystal with diphenylamine, (II), reported in this paper originate from our interest in organic fluorine as an acceptor in hydrogen bonding (Pham et al., 1998), as well as from our exploitation of phenyl–perfluorophenyl interactions for crystal engineering (Gdaniec et al., 2003).

The low propensity of organic fluorine to participate in hydrogen bonding has been the subject of several reports and is now well documented and recognized (Shimoni & Glusker, 1994; Howard et al., 1996; Dunitz & Taylor, 1997; Dunitz, 2004). In compound (I), there is only one strongly acidic hydrogen-bond donor and as many as ten weak F acceptors, with no other accepting groups to compete with F for hydrogen bonding. The crystal structure reveals that, as in previous cases, intermolecular N—H···F hydrogen bonds do not contribute to the stabilization energy of the crystal lattice because all intermolecular H···F contacts are longer than 2.9 Å.

A view of the molecular structure of (I) is shown in Fig. 1. The molecule has crystallographic C₂ symmetry, with the N—H group situated on the twofold axis. The pentafluorophenyl rings are twisted by 31.54 (8)° in opposite directions relative to the plane of the amino group defined by atoms C1, N1 and C1(−x, y, 1 − z). This twist brings two symmetry-related F6 atoms into close contact at 2.767 (3) Å, i.e. a distance slightly shorter than the sum of the van der Waals radii of two F atoms (1.46 Å; Rowland & Taylor, 1996). This molecular conformation also orients the local N^δ−–H^δ+ dipole and two closely situated C2^δ+–F2^δ− dipoles nearly antiparallel (H1···F2 = 2.46 Å, N1—H1···F2 = 97°), thus providing some electrostatic stabilization to the conformation adopted by the molecule of (I). The F2 and F2(−x, y, 1 − z) atoms in the molecule hinder access to the N—H group by other potential acceptors and therefore no intermolecular N—H···F hydrogen bonds are formed.

The crystal packing of (I) is shown in Fig. 2. The pentafluorophenyl rings related by translation along [001] are arranged into stacks with a large offset (Fig. 2a), which brings atoms F3 and F6 from adjacent molecules along the stack directly above and below the centroid of an electron-deficient phenyl ring, with F···centroid distances of 3.26 and 3.22 Å, respectively. Additionally, the stacks of (I) along [001] assemble into (100) layers, where pentafluorophenyl rings related by unit translations along [011] or [011], and situated on one side of the layer, are nearly coplanar and contact via their edges with a shortest F···F distance of 2.826 (3) Å (Fig. 2b).

We expected that (I), with its two pentafluorophenyl rings, should be prone to form molecular complexes via phenyl–perfluorophenyl interactions, but our attempts to obtain its benzene solvate were unsuccessful. However, when an equimolar mixture of (I) and diphenylamine was disolved in ethanol, plate-like 1:1 co-crystals of (II) (m.p. 335 K) precipitated. These crystals have the same space group as (I) and very similar unit-cell parameters, with the exception that the parameter c was nearly twice as long as in (I).

A view of the molecular structure of (II) is shown in Fig. 3 and a view of the crystal packing along [001] is presented in Fig. 4. The crystal structure is very similar to that of (I), with the exception that the homomolecular stacks in (I) are substituted in (II) by heteromolecular stacks, with fluorinated and non-fluorinated molecules alternating (Fig. 4a). Both molecules posses crystallographic C₂ symmetry, with the N atom situated on the twofold axis. The amino group N atoms are slightly pyramidal because the H atoms of the N—H groups are not located on the twofold axis but are displaced from it and are, in effect, disordered over two positions. As in (I), the amino groups are not involved in hydrogen bonding because the closest (N)H···F distance is 2.75 Å.

Interestingly, in this co-crystal there are negligible face-to-face aromatic ring interactions, typical for this type of molecular complex (Collings et al., 2002, and references therein; Gdaniec et al., 2003). Here, a large slip angle of the phenyl–pentafluorophenyl stacks leaves the centroids of adjacent rings more than 4 Å apart, i.e. there is practically no overlap of the aromatic π-systems (Fig. 4b). Instead, lateral interactions between the fluorinated and non-fluorinated rings of neighbouring stacks seem to play a more important role in (II), because each phenyl-ring H atom makes a conact shorter than 3 Å with an F atom situated close to the plane of the phenyl ring.

S2. Experimental

Compound (I) was prepared according to the literature procedure of Koppang (1971) [and was recrystallized from what solvent?]. Compound (II) was prepared from an equimolar mixture of (I) and diphenylamine, dissolved in ethanol, by slow evaporation of the solvent at room temperature.

S3. Refinement

All H atoms of N—H groups were located in electron-density difference maps and refined as riding, with N—H = 0.82–0.91 Å [Please check added text] and U_iso(H) = 1.2U_eq(N). In (II), the H atoms of the N—H groups were disordered over two symmetry-related positions [Site-occupancy factors?]. All H atoms bonded to C were placed in calculated positions, with C—H = 0.93 Å, and were refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal structure of (I). (a) The packing of the molecules viewed down the c axis, with the shortest F···F contacts shown as dashed lines. (b) The arrangement of pentafluorophenyl rings on a surface of the (100) layer.
	Fig. 3. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. T crystal structure of (II). (a) The packing of the molecules projected down the c axis, with the shortest F···F contacts shown as dashed lines. (b) The arrangement of pentafluorophenyl and phenyl rings on a surface of the (100) layer.

(I) 2,2',3,3',4,4',5,5',6,6'-decafluorodiphenylamine

Crystal data

C12HF10N	F(000) = 340
Mr = 349.14	Dx = 2.104 Mg m^−3
Monoclinic, C2	Melting point = 357–359 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 21.293 (3) Å	Cell parameters from 1850 reflections
b = 5.9659 (8) Å	θ = 4–25°
c = 4.4306 (6) Å	µ = 0.24 mm^−1
β = 101.702 (11)°	T = 130 K
V = 551.13 (13) Å^3	Plate, colourless
Z = 2	0.3 × 0.3 × 0.03 mm

Data collection

Kuma KM4 CCD κ geometry diffractometer	513 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 25.0°, θmin = 3.6°
ω scans	h = −24→25
1458 measured reflections	k = −7→5
532 independent reflections	l = −5→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 0.0243P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
532 reflections	Δρmax = 0.25 e Å^−3
106 parameters	Δρmin = −0.17 e Å^−3
1 restraint	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: 0.009 (1)

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 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
N1	0.0000	1.0895 (6)	0.5000	0.0203 (7)
H1	0.0000	1.2404	0.5000	0.024*
C1	0.05645 (12)	0.9851 (5)	0.4595 (5)	0.0178 (5)
C2	0.09514 (12)	1.0922 (5)	0.2841 (5)	0.0197 (7)
C3	0.15264 (12)	1.0022 (5)	0.2434 (5)	0.0205 (6)
C4	0.17280 (12)	0.7971 (5)	0.3731 (6)	0.0190 (6)
C5	0.13549 (12)	0.6873 (5)	0.5499 (5)	0.0196 (6)
C6	0.07903 (12)	0.7815 (4)	0.5924 (5)	0.0170 (5)
F2	0.07585 (7)	1.2895 (3)	0.1532 (3)	0.0258 (4)
F3	0.18781 (7)	1.1090 (3)	0.0706 (4)	0.0305 (5)
F4	0.22759 (7)	0.7053 (3)	0.3283 (4)	0.0309 (5)
F5	0.15518 (7)	0.4913 (3)	0.6823 (3)	0.0258 (4)
F6	0.04479 (7)	0.6711 (2)	0.7740 (3)	0.0227 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0215 (16)	0.0105 (15)	0.0300 (16)	0.000	0.0079 (13)	0.000
C1	0.0178 (11)	0.0201 (13)	0.0147 (10)	−0.0027 (11)	0.0012 (9)	−0.0009 (12)
C2	0.0271 (16)	0.0161 (14)	0.0151 (12)	−0.0032 (12)	0.0022 (11)	0.0014 (10)
C3	0.0192 (12)	0.0287 (15)	0.0139 (10)	−0.0086 (11)	0.0042 (9)	−0.0004 (13)
C4	0.0171 (12)	0.0230 (14)	0.0168 (12)	0.0004 (11)	0.0031 (10)	−0.0041 (10)
C5	0.0218 (13)	0.0190 (14)	0.0155 (12)	−0.0001 (12)	−0.0021 (9)	−0.0002 (11)
C6	0.0179 (11)	0.0184 (13)	0.0152 (10)	−0.0032 (11)	0.0043 (9)	0.0026 (11)
F2	0.0293 (8)	0.0195 (8)	0.0268 (8)	−0.0028 (7)	0.0014 (6)	0.0090 (6)
F3	0.0283 (9)	0.0401 (11)	0.0249 (8)	−0.0088 (8)	0.0098 (7)	0.0087 (8)
F4	0.0204 (7)	0.0418 (11)	0.0323 (9)	0.0047 (8)	0.0092 (6)	−0.0012 (8)
F5	0.0270 (8)	0.0201 (8)	0.0288 (8)	0.0054 (7)	0.0019 (6)	0.0060 (7)
F6	0.0233 (8)	0.0235 (9)	0.0230 (8)	0.0000 (7)	0.0085 (6)	0.0075 (6)

Geometric parameters (Å, º)

N1—C1^i	1.397 (3)	C3—F3	1.336 (3)
N1—C1	1.397 (3)	C3—C4	1.382 (4)
N1—H1	0.8999	C4—F4	1.340 (3)
C1—C6	1.392 (4)	C4—C5	1.388 (3)
C1—C2	1.396 (3)	C5—F5	1.337 (4)
C2—F2	1.340 (3)	C5—C6	1.374 (4)
C2—C3	1.382 (4)	C6—F6	1.360 (3)
C1^i—N1—C1	127.0 (4)	C2—C3—C4	119.9 (2)
C1^i—N1—H1	116.5	F4—C4—C3	120.4 (2)
C1—N1—H1	116.5	F4—C4—C5	120.4 (2)
C6—C1—C2	116.3 (2)	C3—C4—C5	119.2 (2)
C6—C1—N1	124.5 (2)	F5—C5—C6	120.2 (2)
C2—C1—N1	119.2 (3)	F5—C5—C4	119.7 (2)
F2—C2—C3	119.1 (2)	C6—C5—C4	120.1 (3)
F2—C2—C1	118.6 (2)	F6—C6—C5	118.1 (2)
C3—C2—C1	122.2 (3)	F6—C6—C1	119.5 (2)
F3—C3—C2	120.3 (3)	C5—C6—C1	122.4 (2)
F3—C3—C4	119.8 (2)
C1^i—N1—C1—C6	−32.8 (2)	C1^i—N1—C1—C2	149.7 (2)

Symmetry code: (i) −x, y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F2	0.90	2.46	2.720 (2)	97

(II) 2,2',3,3',4,4',5,5',6,6'-Decafluorodiphenylamine–diphenylamine (1/1)

Crystal data

C12HF10N·C12H11N	F(000) = 520
Mr = 518.36	Dx = 1.704 Mg m^−3
Monoclinic, C2	Melting point = 333–335 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 21.417 (3) Å	Cell parameters from 1678 reflections
b = 5.7778 (11) Å	θ = 4–25°
c = 8.1895 (14) Å	µ = 0.17 mm^−1
β = 94.312 (13)°	T = 130 K
V = 1010.5 (3) Å^3	Plate, colourless
Z = 2	0.50 × 0.25 × 0.02 mm

Data collection

Kuma KM4 CCD κ geometry diffractometer	924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 25.0°, θmin = 3.3°
ω scans	h = −25→25
2852 measured reflections	k = −5→6
965 independent reflections	l = −9→8

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0692P)^2] where P = (Fo^2 + 2Fc^2)/3
965 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.23 e Å^−3
1 restraint	Δρmin = −0.29 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 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	Occ. (<1)
C1	0.05709 (16)	0.4372 (6)	−0.0251 (4)	0.0221 (8)
C2	0.07709 (17)	0.2278 (6)	0.0431 (4)	0.0237 (8)
C3	0.13523 (18)	0.1395 (7)	0.0205 (4)	0.0257 (9)
C4	0.17629 (17)	0.2589 (7)	−0.0711 (4)	0.0286 (9)
C5	0.15826 (19)	0.4704 (7)	−0.1378 (4)	0.0275 (9)
C6	0.09934 (17)	0.5538 (6)	−0.1161 (4)	0.0260 (9)
N1	0.0000	0.5425 (8)	0.0000	0.0275 (10)
H1	0.0000	0.6748	−0.0350	0.033*	0.50
F2	0.03961 (9)	0.1070 (3)	0.1380 (2)	0.0300 (6)
F3	0.15293 (11)	−0.0623 (4)	0.0894 (2)	0.0343 (6)
F4	0.23294 (10)	0.1710 (5)	−0.0950 (3)	0.0395 (7)
F5	0.19729 (10)	0.5907 (4)	−0.2255 (3)	0.0390 (6)
F6	0.08185 (11)	0.7588 (4)	−0.1843 (2)	0.0319 (6)
C1A	0.0575 (2)	0.4324 (7)	0.4765 (4)	0.0333 (10)
C2A	0.07417 (19)	0.2163 (7)	0.5439 (4)	0.0318 (9)
H2A	0.0457	0.1336	0.6013	0.038*
C3A	0.1329 (2)	0.1258 (9)	0.5251 (5)	0.0393 (11)
H3A	0.1437	−0.0172	0.5710	0.047*
C4A	0.1759 (2)	0.2450 (10)	0.4390 (5)	0.0462 (12)
H4A	0.2151	0.1817	0.4256	0.055*
C5A	0.1600 (2)	0.4570 (11)	0.3738 (5)	0.0523 (14)
H5A	0.1889	0.5394	0.3176	0.063*
C6A	0.1009 (2)	0.5505 (9)	0.3907 (5)	0.0441 (13)
H6A	0.0905	0.6934	0.3440	0.053*
N1A	0.0000	0.5384 (9)	0.5000	0.0450 (13)
H1A	0.0018	0.6893	0.4697	0.054*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.027 (2)	0.0165 (18)	0.0221 (15)	−0.0014 (16)	−0.0037 (13)	−0.0056 (16)
C2	0.026 (2)	0.0190 (19)	0.0261 (17)	−0.0059 (16)	0.0004 (14)	−0.0052 (16)
C3	0.032 (2)	0.0176 (19)	0.0259 (18)	−0.0004 (16)	−0.0061 (15)	−0.0036 (15)
C4	0.025 (2)	0.032 (2)	0.0290 (17)	−0.0008 (18)	−0.0038 (14)	−0.0101 (19)
C5	0.034 (2)	0.025 (2)	0.0231 (16)	−0.0102 (17)	0.0013 (14)	−0.0002 (17)
C6	0.032 (2)	0.0180 (19)	0.0273 (18)	−0.0052 (17)	−0.0044 (16)	−0.0003 (16)
N1	0.029 (3)	0.011 (2)	0.042 (2)	0.000	0.0029 (19)	0.000
F2	0.0321 (12)	0.0250 (12)	0.0329 (11)	−0.0023 (10)	0.0034 (9)	0.0040 (10)
F3	0.0385 (13)	0.0227 (12)	0.0398 (12)	0.0056 (11)	−0.0098 (10)	−0.0005 (10)
F4	0.0262 (12)	0.0481 (16)	0.0440 (12)	0.0044 (11)	0.0009 (9)	−0.0064 (11)
F5	0.0378 (14)	0.0443 (15)	0.0354 (11)	−0.0120 (12)	0.0056 (9)	0.0027 (11)
F6	0.0410 (13)	0.0200 (11)	0.0340 (10)	−0.0065 (10)	−0.0013 (9)	0.0062 (9)
C1A	0.046 (3)	0.025 (2)	0.0266 (17)	−0.005 (2)	−0.0105 (16)	−0.0036 (17)
C2A	0.039 (2)	0.027 (2)	0.0278 (18)	−0.0047 (19)	−0.0027 (15)	−0.0031 (18)
C3A	0.047 (3)	0.035 (3)	0.034 (2)	0.002 (2)	−0.0030 (18)	−0.0114 (18)
C4A	0.044 (3)	0.056 (3)	0.038 (2)	−0.006 (2)	0.0003 (19)	−0.017 (2)
C5A	0.059 (3)	0.065 (3)	0.033 (2)	−0.030 (3)	0.001 (2)	−0.005 (2)
C6A	0.069 (4)	0.034 (2)	0.0278 (19)	−0.020 (2)	−0.011 (2)	0.0045 (19)
N1A	0.048 (3)	0.021 (3)	0.064 (3)	0.000	−0.008 (3)	0.000

Geometric parameters (Å, º)

C1—C2	1.387 (5)	C1A—C6A	1.386 (6)
C1—C6	1.389 (5)	C1A—C2A	1.400 (6)
C1—N1	1.395 (4)	C1A—N1A	1.402 (5)
C2—F2	1.353 (4)	C2A—C3A	1.382 (6)
C2—C3	1.371 (5)	C2A—H2A	0.9300
C3—F3	1.338 (5)	C3A—C4A	1.385 (6)
C3—C4	1.382 (5)	C3A—H3A	0.9300
C4—F4	1.343 (4)	C4A—C5A	1.369 (8)
C4—C5	1.382 (6)	C4A—H4A	0.9300
C5—F5	1.337 (4)	C5A—C6A	1.392 (7)
C5—C6	1.375 (6)	C5A—H5A	0.9300
C6—F6	1.350 (4)	C6A—H6A	0.9300
N1—H1	0.8164	N1A—H1A	0.9083
C2—C1—C6	116.4 (3)	C6A—C1A—C2A	118.6 (4)
C2—C1—N1	124.7 (3)	C6A—C1A—N1A	118.9 (4)
C6—C1—N1	118.7 (3)	C2A—C1A—N1A	122.4 (4)
F2—C2—C3	118.0 (3)	C3A—C2A—C1A	120.0 (4)
F2—C2—C1	120.2 (3)	C3A—C2A—H2A	120.0
C3—C2—C1	121.8 (3)	C1A—C2A—H2A	120.0
F3—C3—C2	119.9 (3)	C2A—C3A—C4A	121.0 (4)
F3—C3—C4	119.5 (4)	C2A—C3A—H3A	119.5
C2—C3—C4	120.6 (3)	C4A—C3A—H3A	119.5
F4—C4—C5	120.4 (4)	C5A—C4A—C3A	119.2 (5)
F4—C4—C3	120.6 (4)	C5A—C4A—H4A	120.4
C5—C4—C3	119.0 (4)	C3A—C4A—H4A	120.4
F5—C5—C6	120.3 (4)	C4A—C5A—C6A	120.7 (5)
F5—C5—C4	120.3 (4)	C4A—C5A—H5A	119.7
C6—C5—C4	119.4 (4)	C6A—C5A—H5A	119.7
F6—C6—C5	118.9 (3)	C1A—C6A—C5A	120.5 (5)
F6—C6—C1	118.4 (3)	C1A—C6A—H6A	119.7
C5—C6—C1	122.7 (3)	C5A—C6A—H6A	119.7
C1^i—N1—C1	128.3 (4)	C1A^ii—N1A—C1A	128.2 (5)
C1^i—N1—H1	118.9	C1A^ii—N1A—H1A	120.9
C1—N1—H1	109.5	C1A—N1A—H1A	109.0
C2—C1—N1—C1^i	−32.4 (3)	C6A—C1A—N1A—C1A^ii	153.4 (4)
C6—C1—N1—C1^i	151.7 (3)	C2A—C1A—N1A—C1A^ii	−30.0 (3)

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