Hydrogen bonding in C-substituted nitro­anilines: [pi]-stacked sheets of R(20) and R(28) rings in 2-cyano-4-nitroaniline

In the title compound, C₇H₅N₃O₂, which crystallizes with Z' = 2 in space group P2₁/c, the two independent mol­ecules both exhibit positional disorder, with refined site-occupancy factors of 0.947 (2) and 0.053 (2) for the major and minor components, respectively. The major components have polarized molecular electronic structures. The two major components are linked into sheets of alternating R(20) and R(28) rings by two N-H...O hydrogen bonds [H...O = 2.18 and 2.21 Å, N...O = 3.022 (2) and 3.043 (2) Å and N-H...O both 159°] and two N-H...N hydrogen bonds [H...N = 2.14 and 2.17 Å, N...N = 2.990 (2) and 3.001 (2) Å, and N-H...N = 162 and 158°]. The sheets are linked into a three-dimensional framework by a single aromatic [pi]-[pi] stacking interaction.

S1. Comment

We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), which provides an interesting comparison with the bromo-substituted analogue, (II) (Glidewell et al., 2002). In compound (II), the molecules are linked by paired N—H···N hydrogen bonds, in which the cyano N atom acts as the acceptor, into centrosymmetric dimers characterized by an R₂²(12) motif (Bernstein et al., 1995), and these dimers are linked by a single N—H···O hydrogen bond into essentially planar sheets built from alternating R₂²(12) and R₆⁶(36) rings, where both ring types are centrosymmetric (Glidewell et al., 2002). Within the larger of these rings, there are centrosymmetrically related pairs of fairly short intermolecular Br···O contacts, involving the nitro O atom which is not engaged in the hydrogen bonding, and this raises the possibility that these Br and O atoms may be acting as an effective template for the formation of the R₆⁶(36) rings. It is thus of interest to investigate the analogue, (I), from which the Br substituent is absent. \sch

The molecules of (I) exhibit positional disorder (see Experimental). In both major components, molecules A and B (Fig. 1), the bond distances (Table 1) provide evidence for polarized molecular electronic structures. The C—NH₂ and C—NO₂ distances are both short for their types (Allen et al., 1987), while the N—O distances are all long, and the bonds C2X—C3X, C3X—C4X and C5X—C6X (X is A or B) are all significantly shorter than the remaining ring bonds, consistent with quinonoid bond fixation. These values thus indicate a contribution to the overall molecular electronic structure from the canonical forms (Ia) and (Ib). Entirely similar forms also contribute to the molecular electronic structure of (II) (Glidewell et al., 2002).

However, the supramolecular structure of (I) is entirely different from that of (II). Since the pattern of hydrogen bonds linking the major components, molecules A and B, is identical to that linking the minor components, molecules C and D (Table 2), we discuss in detail only the supramolecular aggregation of the major components. Each of the N—H···O hydrogen bonds involves only a single type of molecule, A—D respectively, while the N—H···N hydrogen bonds link molecules either of types A and B, or of types C and D.

Amino atom N1A in the type A molecule at (x, y, z), acts as hydrogen-bond donor, via atom H11A, to atom O41A in the type A molecule at (-x, 1/2 + y, 1/2 − z), so producing a C(8) spiral chain of type A molecules only, running parallel to the [010] direction and generated by the 2₁ screw axis along (0, y, 1/4) (Fig. 2). Similarly, atom N1B in the type B molecule at (x, y, z) acts as hydrogen-bond donor, via atom H11B, to atom O41B in the type B molecule at (1 − x, y − 1/2, 3/2 − z), so producing a second C(8) chain parallel to [010], this time of type B molecules only and generated by the 2₁ screw axis along (1/2, y, 3/4) (Fig. 2).

These independent C(8) chains built from N—H···O hydrogen bonds are linked into (101) sheets by the N—H···N hydrogen bonds. Amino atom N1B acts as hydrogen-bond donor, via atom H12B, to cyano atom N21A within the asymmetric unit (Fig. 1), while atom N1A in the type A molecule at (x, y, z) similarly acts as donor, via atom H12A, to cyano atom N21B in the type B molecule at (x − 1, y, z − 1). The combination of these two N—H···N hydrogen bonds generates by translation a C₂²(12) chain running parallel to the [101] direction, and the combination of this chain and the two independent [010] chains generates a (101) sheet built of R₄⁴(20) and R₄⁴(28) rings, alternating in a chess-board fashion (Fig. 2).

Two sheets of this type pass through each unit cell and each sheet is weakly linked to the two adjacent sheets by means of a single aromatic π–π stacking interaction involving the type B molecules only. The aryl ring of the type B molecule at (x, y, z) makes angles of only ca 0.5° with those of the type B molecules at (x, 3/2 − y, 1/2 + z) and (x, 3/2 − y, z − 1/2). The corresponding interplanar spacings are ca 3.295 Å, with centroid separations of 3.574 (2) Å, corresponding to centroid offsets of ca 1.384 Å. Propagation of this interaction forms a π-stacked chain of type B molecules running parallel to the [001] direction, generated by the c-glide plane at y = 3/4 (Fig. 3). The absence of an analogous interaction involving the type A molecules is sufficient to preclude the possibility of any additional symmetry in the structure.

The supramolecular structure of (I) thus differs from that of (II) in a number of significant respects. There are no centrosymmetric dimer motifs present in (I) of the type found in (II), although such motifs are, in fact, absent from the structure of 2-cyanoaniline (Laine et al., 1996). The hydrogen-bonded sheets exhibit different chess-board patterns in the two structures, with R₄⁴(20) and R₄⁴(28) rings present in (I), and R₂²(12) and R₆⁶(36) rings present in (II), and in particular the absence of a Br substituent in (I) is accompanied by the absence of the large rings found in (II)·Finally, adjacent sheets in (I) are linked by an aromatic π–π stacking interaction, whereas such interactions are absent from the structure of (II), where the aggregation dependent upon direction-specific interactions is strictly two-dimensional.

S2. Experimental

A sample of (I) was obtained from Bayer, and purified by preparative thin-layer chromatography on alumina using ethyl acetate as eluent. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.

S3. Refinement

Space group P2₁/c was assigned from the systematic absences. At an early stage of the refinement it became apparent that both independent molecules, labelled A and B (Fig. 1), exhibited a modest degree of positional disorder, giving rise to two further independent molecules, labelled C and D. The h0l reflections having l even are all weak to very weak when h is odd, and in (010) projection the coordinates of molecules A and B are approximately related by the transformation (1/2 + x, 1/2 + z). Those of molecules C and D are similarly related, implying an approximate n-glide present only in the (010) projection. The disorder was satisfactorily modelled by assigning one common site-occupancy factor to molecules A and B, and a second common factor to molecules C and D. The refined values are 0.947 (2) and 0.053 (2), respectively. Because of the very low occupancy of the C and D sites, the non-H atoms in these sites were assigned a common isotropic displacement parameter, and their phenyl rings were constrained to be rigid planar hexagons with a C—C distance of 1.39 Å. In addition, the remaining intramolecular parameters for molecules C and D were all restrained, using DFIX commands, to values based upon the average values of the corresponding parameters in molecules A and B; attempted free refinement of molecules C and D led to some unrealistic geometric parameters for these molecules. All the H atoms of the major components were located from difference maps, and all H atoms were included in the refinements as riding atoms, with C—H distances of 0.95 and N—H distances of 0.88 Å.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The independent molecular components of compound (I), showing the atom-labelling scheme. (a) The major components, molecules A and B. (b) The minor components, molecules C and D (see text). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing formation of a (101) sheet of R4^4(20) and R4^4(28) rings built from molecules of types A and B only (see text). For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#), a dollar sign (?), an ampersand (?) or an `at' sign (@) are at the symmetry positions (x − 1, y, z − 1), (-x, 1/2 + y, 1/2 − z), (-x, y − 1/2, 1/2 − z), (1 − x, 1/2 + y, 3/2 − z) and (1 − x, y − 1/2, 3/2 − z), respectively.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing formation of a π-stacked chain of type B molecules along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted.

2-Cyano-4-nitroaniline

Crystal data

C7H5N3O2	F(000) = 672
Mr = 163.14	Dx = 1.536 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3216 reflections
a = 11.2316 (4) Å	θ = 2.9–27.5°
b = 17.7275 (7) Å	µ = 0.12 mm^−1
c = 7.1078 (2) Å	T = 120 K
β = 94.630 (3)°	Block, orange
V = 1410.60 (9) Å^3	0.30 × 0.30 × 0.30 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	3216 independent reflections
Radiation source: rotating anode	2067 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −14→14
Tmin = 0.928, Tmax = 0.958	k = −22→23
19532 measured 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0739P)^2] where P = (Fo^2 + 2Fc^2)/3
3216 reflections	(Δ/σ)max < 0.001
267 parameters	Δρmax = 0.22 e Å^−3
13 restraints	Δρmin = −0.27 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1A	−0.05690 (15)	0.49793 (10)	0.20668 (19)	0.0180 (3)	0.947 (2)
C2A	0.05489 (16)	0.47591 (9)	0.2973 (2)	0.0177 (3)	0.947 (2)
C3A	0.08480 (13)	0.40048 (9)	0.3210 (2)	0.0202 (4)	0.947 (2)
C4A	0.0065 (4)	0.34652 (14)	0.2497 (3)	0.0225 (6)	0.947 (2)
C5A	−0.10426 (15)	0.36609 (9)	0.1569 (2)	0.0219 (4)	0.947 (2)
C6A	−0.13497 (13)	0.44045 (10)	0.1349 (2)	0.0200 (4)	0.947 (2)
N1A	−0.08841 (11)	0.57101 (9)	0.19106 (18)	0.0220 (3)	0.947 (2)
C21A	0.13736 (13)	0.53359 (11)	0.3631 (2)	0.0202 (4)	0.947 (2)
N21A	0.20032 (12)	0.58151 (8)	0.41345 (19)	0.0275 (3)	0.947 (2)
N4A	0.03668 (12)	0.26791 (8)	0.27533 (19)	0.0274 (3)	0.947 (2)
O41A	−0.03612 (13)	0.21997 (7)	0.2106 (2)	0.0396 (4)	0.947 (2)
O42A	0.13312 (10)	0.25085 (7)	0.35930 (18)	0.0364 (3)	0.947 (2)
C1B	0.44251 (12)	0.68416 (8)	0.71306 (18)	0.0182 (3)	0.947 (2)
C2B	0.55571 (13)	0.70527 (10)	0.8003 (2)	0.0183 (3)	0.947 (2)
C3B	0.58787 (14)	0.78049 (10)	0.8255 (2)	0.0203 (4)	0.947 (2)
C4B	0.50670 (15)	0.83556 (9)	0.7634 (2)	0.0207 (3)	0.947 (2)
C5B	0.39360 (14)	0.81672 (9)	0.6783 (2)	0.0207 (4)	0.947 (2)
C6B	0.36284 (13)	0.74274 (9)	0.6527 (2)	0.0196 (3)	0.947 (2)
N1B	0.41120 (12)	0.61171 (8)	0.69011 (19)	0.0235 (3)	0.947 (2)
C21B	0.63585 (13)	0.64705 (9)	0.8686 (2)	0.0209 (4)	0.947 (2)
N21B	0.69583 (12)	0.59841 (8)	0.92508 (19)	0.0283 (3)	0.947 (2)
N4B	0.53929 (12)	0.91385 (8)	0.78906 (18)	0.0260 (3)	0.947 (2)
O41B	0.46890 (12)	0.96206 (7)	0.7193 (2)	0.0374 (4)	0.947 (2)
O42B	0.63482 (11)	0.92994 (7)	0.87734 (18)	0.0371 (4)	0.947 (2)
C1C	−0.0569 (16)	0.1347 (6)	0.207 (2)	0.017 (2)*	0.053 (2)
C2C	0.0529 (14)	0.1142 (10)	0.297 (2)	0.017 (2)*	0.053 (2)
C3C	0.0821 (15)	0.0384 (12)	0.321 (3)	0.017 (2)*	0.053 (2)
C4C	0.002 (2)	−0.0169 (7)	0.255 (3)	0.017 (2)*	0.053 (2)
C5C	−0.108 (2)	0.0036 (9)	0.165 (3)	0.017 (2)*	0.053 (2)
C6C	−0.1374 (12)	0.0794 (11)	0.141 (2)	0.017 (2)*	0.053 (2)
N1C	−0.087 (2)	0.2071 (7)	0.174 (3)	0.017 (2)*	0.053 (2)
C21C	0.1329 (17)	0.1721 (11)	0.368 (3)	0.017 (2)*	0.053 (2)
N21C	0.1982 (16)	0.2177 (10)	0.426 (3)	0.017 (2)*	0.053 (2)
N4C	0.0356 (14)	−0.0941 (7)	0.293 (3)	0.017 (2)*	0.053 (2)
O41C	−0.012 (5)	−0.1494 (18)	0.212 (5)	0.017 (2)*	0.053 (2)
O42C	0.1296 (15)	−0.1110 (16)	0.385 (3)	0.017 (2)*	0.053 (2)
C1D	0.4482 (17)	0.3183 (6)	0.703 (3)	0.017 (2)*	0.053 (2)
C2D	0.5565 (15)	0.3388 (9)	0.797 (3)	0.017 (2)*	0.053 (2)
C3D	0.5839 (13)	0.4146 (10)	0.826 (3)	0.017 (2)*	0.053 (2)
C4D	0.5030 (18)	0.4698 (7)	0.761 (3)	0.017 (2)*	0.053 (2)
C5D	0.3947 (16)	0.4493 (8)	0.666 (3)	0.017 (2)*	0.053 (2)
C6D	0.3673 (13)	0.3735 (10)	0.637 (2)	0.017 (2)*	0.053 (2)
N1D	0.425 (3)	0.2441 (7)	0.687 (4)	0.017 (2)*	0.053 (2)
C21D	0.6373 (18)	0.2787 (10)	0.850 (4)	0.017 (2)*	0.053 (2)
N21D	0.7064 (16)	0.2336 (10)	0.897 (3)	0.017 (2)*	0.053 (2)
N4D	0.5328 (12)	0.5488 (6)	0.775 (3)	0.017 (2)*	0.053 (2)
O41D	0.4580 (16)	0.5965 (10)	0.718 (3)	0.017 (2)*	0.053 (2)
O42D	0.6282 (12)	0.5668 (10)	0.862 (2)	0.017 (2)*	0.053 (2)
H3A	0.1587	0.3864	0.3859	0.024*	0.947 (2)
H5A	−0.1577	0.3278	0.1094	0.026*	0.947 (2)
H6A	−0.2096	0.4536	0.0707	0.024*	0.947 (2)
H11A	−0.0390	0.6063	0.2364	0.026*	0.947 (2)
H12A	−0.1585	0.5835	0.1355	0.026*	0.947 (2)
H3B	0.6640	0.7938	0.8842	0.024*	0.947 (2)
H5B	0.3386	0.8554	0.6387	0.025*	0.947 (2)
H6B	0.2866	0.7304	0.5932	0.024*	0.947 (2)
H11B	0.4616	0.5758	0.7283	0.028*	0.947 (2)
H12B	0.3402	0.5999	0.6368	0.028*	0.947 (2)
H3C	0.1572	0.0244	0.3821	0.020*	0.053 (2)
H5C	−0.1632	−0.0342	0.1195	0.020*	0.053 (2)
H6C	−0.2124	0.0934	0.0799	0.020*	0.053 (2)
H11C	−0.0360	0.2433	0.2096	0.020*	0.053 (2)
H12C	−0.1568	0.2184	0.1171	0.020*	0.053 (2)
H3D	0.6580	0.4286	0.8910	0.020*	0.053 (2)
H5D	0.3394	0.4871	0.6218	0.020*	0.053 (2)
H6D	0.2933	0.3595	0.5727	0.020*	0.053 (2)
H11D	0.4771	0.2111	0.7361	0.020*	0.053 (2)
H12D	0.3574	0.2286	0.6286	0.020*	0.053 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0193 (8)	0.0175 (9)	0.0174 (7)	−0.0006 (6)	0.0024 (5)	0.0017 (6)
C2A	0.0164 (8)	0.0195 (9)	0.0171 (7)	−0.0010 (6)	0.0002 (5)	0.0002 (6)
C3A	0.0174 (8)	0.0229 (9)	0.0203 (7)	0.0018 (6)	0.0011 (6)	0.0018 (6)
C4A	0.0294 (10)	0.0159 (9)	0.0224 (14)	0.0038 (8)	0.0029 (12)	0.0018 (9)
C5A	0.0246 (9)	0.0177 (10)	0.0230 (9)	−0.0039 (7)	−0.0010 (6)	0.0003 (6)
C6A	0.0171 (8)	0.0199 (10)	0.0224 (8)	−0.0013 (6)	−0.0021 (6)	−0.0013 (6)
N1A	0.0202 (7)	0.0167 (8)	0.0281 (7)	0.0016 (6)	−0.0043 (5)	−0.0002 (5)
C21A	0.0191 (8)	0.0207 (9)	0.0206 (7)	−0.0018 (7)	−0.0003 (6)	0.0009 (6)
N21A	0.0252 (7)	0.0268 (8)	0.0295 (7)	−0.0032 (6)	−0.0031 (6)	0.0011 (6)
N4A	0.0307 (8)	0.0175 (7)	0.0335 (8)	0.0020 (6)	−0.0007 (6)	0.0008 (5)
O41A	0.0424 (8)	0.0174 (7)	0.0568 (9)	−0.0030 (6)	−0.0091 (7)	−0.0023 (5)
O42A	0.0335 (7)	0.0246 (7)	0.0492 (8)	0.0078 (6)	−0.0084 (6)	0.0025 (5)
C1B	0.0191 (8)	0.0192 (9)	0.0164 (7)	−0.0002 (6)	0.0019 (5)	−0.0003 (5)
C2B	0.0184 (8)	0.0185 (9)	0.0180 (7)	0.0017 (7)	0.0012 (6)	−0.0002 (6)
C3B	0.0185 (8)	0.0242 (10)	0.0181 (7)	−0.0052 (8)	0.0012 (6)	−0.0016 (7)
C4B	0.0257 (9)	0.0164 (8)	0.0204 (7)	−0.0010 (7)	0.0042 (6)	−0.0009 (6)
C5B	0.0217 (8)	0.0196 (9)	0.0212 (8)	0.0042 (7)	0.0030 (6)	0.0032 (6)
C6B	0.0175 (8)	0.0199 (9)	0.0210 (7)	0.0000 (7)	−0.0016 (6)	0.0010 (7)
N1B	0.0190 (7)	0.0180 (8)	0.0323 (8)	−0.0005 (6)	−0.0053 (6)	0.0015 (6)
C21B	0.0176 (8)	0.0229 (9)	0.0220 (8)	−0.0016 (6)	−0.0002 (6)	−0.0015 (6)
N21B	0.0221 (7)	0.0301 (8)	0.0317 (7)	0.0036 (6)	−0.0032 (6)	0.0017 (6)
N4B	0.0294 (8)	0.0188 (8)	0.0299 (7)	−0.0023 (6)	0.0027 (6)	−0.0024 (5)
O41B	0.0409 (9)	0.0186 (7)	0.0519 (9)	0.0013 (6)	−0.0012 (7)	0.0020 (5)
O42B	0.0357 (8)	0.0291 (8)	0.0446 (8)	−0.0086 (6)	−0.0079 (6)	−0.0058 (6)

Geometric parameters (Å, º)

C1A—C2A	1.419 (2)	C1C—N1C	1.3430 (10)
C2A—C3A	1.386 (2)	C1C—C2C	1.39
C3A—C4A	1.369 (4)	C1C—C6C	1.39
C4A—C5A	1.404 (4)	C2C—C3C	1.39
C5A—C6A	1.368 (2)	C2C—C21C	1.4291 (10)
C6A—C1A	1.412 (2)	C3C—C4C	1.39
C1A—N1A	1.345 (2)	C3C—H3C	0.95
C2A—C21A	1.432 (2)	C4C—C5C	1.39
C21A—N21A	1.144 (2)	C4C—N4C	1.4409 (10)
C4A—N4A	1.442 (2)	C5C—C6C	1.39
N4A—O41A	1.242 (2)	C5C—H5C	0.95
N4A—O42A	1.232 (2)	C6C—H6C	0.95
C3A—H3A	0.95	N1C—H11C	0.88
C5A—H5A	0.95	N1C—H12C	0.88
C6A—H6A	0.95	C21C—N21C	1.1451 (10)
N1A—H11A	0.88	N4C—O42C	1.2348 (10)
N1A—H12A	0.88	N4C—O41C	1.2350 (10)
C1B—C2B	1.419 (2)	C1D—N1D	1.3431 (10)
C2B—C3B	1.389 (2)	C1D—C2D	1.39
C3B—C4B	1.384 (2)	C1D—C6D	1.39
C4B—C5B	1.402 (2)	C2D—C3D	1.39
C5B—C6B	1.365 (2)	C2D—C21D	1.4298
C6B—C1B	1.415 (2)	C3D—C4D	1.39
C1B—N1B	1.338 (2)	C3D—H3D	0.95
C2B—C21B	1.428 (2)	C4D—C5D	1.39
C21B—N21B	1.147 (2)	C4D—N4D	1.4410 (10)
C4B—N4B	1.443 (2)	C5D—C6D	1.39
N4B—O41B	1.240 (2)	C5D—H5D	0.95
N4B—O42B	1.232 (2)	C6D—H6D	0.95
C3B—H3B	0.95	N1D—H11D	0.88
C5B—H5B	0.95	N1D—H12D	0.88
C6B—H6B	0.95	C21D—N21D	1.1459 (10)
N1B—H11B	0.88	N4D—O42D	1.2349 (11)
N1B—H12B	0.88	N4D—O41D	1.2350 (10)
N1A—C1A—C6A	120.89 (17)	N1C—C1C—C2C	122.0 (18)
N1A—C1A—C2A	121.30 (13)	N1C—C1C—C6C	117.9 (18)
C6A—C1A—C2A	117.80 (17)	C2C—C1C—C6C	120.0
C3A—C2A—C1A	121.16 (17)	C1C—C2C—C3C	120.0
C3A—C2A—C21A	120.34 (17)	C1C—C2C—C21C	118.9 (17)
C1A—C2A—C21A	118.49 (14)	C3C—C2C—C21C	121.1 (17)
C4A—C3A—C2A	119.15 (17)	C2C—C3C—C4C	120.0
C4A—C3A—H3A	120.4	C2C—C3C—H3C	120.0
C2A—C3A—H3A	120.4	C4C—C3C—H3C	120.0
C3A—C4A—C5A	121.32 (18)	C5C—C4C—C3C	120.0
C3A—C4A—N4A	119.4 (2)	C5C—C4C—N4C	123.1 (19)
C5A—C4A—N4A	119.3 (3)	C3C—C4C—N4C	116.8 (19)
C6A—C5A—C4A	119.83 (18)	C6C—C5C—C4C	120.0
C6A—C5A—H5A	120.1	C6C—C5C—H5C	120.0
C4A—C5A—H5A	120.1	C4C—C5C—H5C	120.0
C5A—C6A—C1A	120.69 (15)	C5C—C6C—C1C	120.0
C5A—C6A—H6A	119.7	C5C—C6C—H6C	120.0
C1A—C6A—H6A	119.7	C1C—C6C—H6C	120.0
C1A—N1A—H11A	120.0	C1C—N1C—H11C	120.0
C1A—N1A—H12A	120.0	C1C—N1C—H12C	120.0
H11A—N1A—H12A	120.0	H11C—N1C—H12C	120.0
N21A—C21A—C2A	177.6 (2)	N21C—C21C—C2C	179 (3)
O42A—N4A—O41A	122.58 (14)	O42C—N4C—O41C	112 (3)
O42A—N4A—C4A	119.16 (18)	O42C—N4C—C4C	122 (2)
O41A—N4A—C4A	118.26 (19)	O41C—N4C—C4C	125 (3)
N1B—C1B—C6B	120.93 (14)	N1D—C1D—C2D	117 (2)
N1B—C1B—C2B	121.58 (14)	N1D—C1D—C6D	123 (2)
C6B—C1B—C2B	117.48 (14)	C2D—C1D—C6D	120.0
C3B—C2B—C1B	121.60 (14)	C1D—C2D—C3D	120.0
C3B—C2B—C21B	119.96 (14)	C1D—C2D—C21D	116.3 (14)
C1B—C2B—C21B	118.41 (15)	C3D—C2D—C21D	123.6 (14)
C4B—C3B—C2B	118.57 (14)	C4D—C3D—C2D	120.0
C4B—C3B—H3B	120.7	C4D—C3D—H3D	120.0
C2B—C3B—H3B	120.7	C2D—C3D—H3D	120.0
C3B—C4B—C5B	121.35 (15)	C3D—C4D—C5D	120.0
C3B—C4B—N4B	118.97 (15)	C3D—C4D—N4D	121.3 (14)
C5B—C4B—N4B	119.68 (16)	C5D—C4D—N4D	118.5 (14)
C6B—C5B—C4B	119.80 (14)	C6D—C5D—C4D	120.0
C6B—C5B—H5B	120.1	C6D—C5D—H5D	120.0
C4B—C5B—H5B	120.1	C4D—C5D—H5D	120.0
C5B—C6B—C1B	121.19 (14)	C5D—C6D—C1D	120.0
C5B—C6B—H6B	119.4	C5D—C6D—H6D	120.0
C1B—C6B—H6B	119.4	C1D—C6D—H6D	120.0
C1B—N1B—H11B	120.0	C1D—N1D—H11D	120.0
C1B—N1B—H12B	120.0	C1D—N1D—H12D	120.0
H11B—N1B—H12B	120.0	H11D—N1D—H12D	120.0
N21B—C21B—C2B	176.93 (16)	N21D—C21D—C2D	176.0 (19)
O42B—N4B—O41B	123.02 (14)	O42D—N4D—O41D	121.7 (16)
O42B—N4B—C4B	119.25 (14)	O42D—N4D—C4D	118.2 (15)
O41B—N4B—C4B	117.73 (14)	O41D—N4D—C4D	119.6 (16)
N1A—C1A—C2A—C3A	176.94 (13)	N1C—C1C—C2C—C3C	−177 (2)
C6A—C1A—C2A—C3A	−2.35 (19)	C6C—C1C—C2C—C3C	0.0
N1A—C1A—C2A—C21A	−3.6 (2)	N1C—C1C—C2C—C21C	5 (2)
C6A—C1A—C2A—C21A	177.14 (12)	C6C—C1C—C2C—C21C	−178.4 (18)
C1A—C2A—C3A—C4A	2.3 (2)	C1C—C2C—C3C—C4C	0.0
C21A—C2A—C3A—C4A	−177.22 (19)	C21C—C2C—C3C—C4C	178.4 (18)
C2A—C3A—C4A—C5A	−1.4 (3)	C2C—C3C—C4C—C5C	0.0
C2A—C3A—C4A—N4A	−179.49 (18)	C2C—C3C—C4C—N4C	−176.9 (17)
C3A—C4A—C5A—C6A	0.6 (4)	C3C—C4C—C5C—C6C	0.0
N4A—C4A—C5A—C6A	178.74 (19)	N4C—C4C—C5C—C6C	176.7 (18)
C4A—C5A—C6A—C1A	−0.7 (3)	C4C—C5C—C6C—C1C	0.0
N1A—C1A—C6A—C5A	−177.73 (14)	N1C—C1C—C6C—C5C	177.1 (19)
C2A—C1A—C6A—C5A	1.6 (2)	C2C—C1C—C6C—C5C	0.0
C3A—C4A—N4A—O42A	−0.8 (3)	C5C—C4C—N4C—O42C	−174.3 (18)
C5A—C4A—N4A—O42A	−178.93 (19)	C3C—C4C—N4C—O42C	3 (3)
C3A—C4A—N4A—O41A	179.5 (2)	C5C—C4C—N4C—O41C	19 (4)
C5A—C4A—N4A—O41A	1.3 (3)	C3C—C4C—N4C—O41C	−164 (3)
N1B—C1B—C2B—C3B	−179.47 (13)	N1D—C1D—C2D—C3D	−177 (2)
C6B—C1B—C2B—C3B	−0.2 (2)	C6D—C1D—C2D—C3D	0.0
N1B—C1B—C2B—C21B	−1.6 (2)	N1D—C1D—C2D—C21D	7 (2)
C6B—C1B—C2B—C21B	177.73 (12)	C6D—C1D—C2D—C21D	−177 (2)
C1B—C2B—C3B—C4B	0.0 (2)	C1D—C2D—C3D—C4D	0.0
C21B—C2B—C3B—C4B	−177.87 (14)	C21D—C2D—C3D—C4D	176 (2)
C2B—C3B—C4B—C5B	0.7 (2)	C2D—C3D—C4D—C5D	0.0
C2B—C3B—C4B—N4B	179.98 (13)	C2D—C3D—C4D—N4D	−175 (2)
C3B—C4B—C5B—C6B	−1.1 (2)	C3D—C4D—C5D—C6D	0.0
N4B—C4B—C5B—C6B	179.54 (14)	N4D—C4D—C5D—C6D	175 (2)
C4B—C5B—C6B—C1B	1.0 (2)	C4D—C5D—C6D—C1D	0.0
N1B—C1B—C6B—C5B	178.99 (14)	N1D—C1D—C6D—C5D	177 (2)
C2B—C1B—C6B—C5B	−0.3 (2)	C2D—C1D—C6D—C5D	0.0
C3B—C4B—N4B—O42B	−5.1 (2)	C3D—C4D—N4D—O42D	−6 (3)
C5B—C4B—N4B—O42B	174.20 (14)	C5D—C4D—N4D—O42D	178.9 (15)
C3B—C4B—N4B—O41B	174.55 (15)	C3D—C4D—N4D—O41D	−178.7 (17)
C5B—C4B—N4B—O41B	−6.1 (2)	C5D—C4D—N4D—O41D	6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O41A^i	0.88	2.21	3.043 (2)	159
N1B—H11B···O41B^ii	0.88	2.18	3.022 (2)	159
N1C—H11C···O41C^i	0.88	2.04	2.86 (5)	155
N1D—H11D···O41D^ii	0.88	2.17	2.95 (3)	152
N1A—H12A···N21B^iii	0.88	2.14	2.990 (2)	162
N1B—H12B···N21A	0.88	2.17	3.001 (2)	158
N1C—H12C···N21D^iii	0.88	2.12	2.96 (3)	160
N1D—H12D···N21C	0.88	2.21	3.06 (3)	163

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x−1, y, z−1.