Hydrogen bonding in C-methylated nitroanilines: three triclinic examples with Z' = 2 or 4

4-Methyl-2-nitro­aniline, (I), C₇H₈N₂O₂, crystallizes with two mol­ecules in the asymmetric unit. The mol­ecules both form intramolecular N-H...O hydrogen bonds and they are linked into hydrogen-bonded C₂²(12) chains in which the two independent mol­ecules alternate. 4,5-Di­methyl-2-nitro­aniline, (II), C₈H₁₀N₂O₂, also has Z' = 2 and the two independent mol­ecules each form hydrogen-bonded C(6) chains. In 4-­methyl-3-nitro­aniline, (III), C₇H₈N₂O₂, there are four mol­ecules in the asymmetric unit. Molecules of two of these types are linked by N-H...O hydrogen bonds into molecular ladders containing R₄³(18) rings and the other two types independently form single C(7) chains.

S1. Comment

The three isomers of nitroaniline, O₂NC₆H₄NH₂, exhibit markedly different patterns of supramolecular aggregation. Thus, in the 1,4-isomer [Cambridge Structural Database (CSD; Allen & Kennard, 1993) code NANILI02; Tonogaki et al., 1993], each molecule acts as a double donor and a double acceptor of N—H···O hydrogen bonds, and the molecules are thereby linked into (4,4) nets (Batten & Robson, 1998) in which the nodes are single molecules. The resulting sheets, built from a single type of R₄⁴(22) ring (Bernstein et al., 1995), are weakly linked by aromatic π···π stacking interactions.

Molecules of the 1,3-isomer (CSD code MNIANL01; Ploug-Sørensen & Andersen, 1986) also act as double donors and double acceptors but now the molecules are linked by equal numbers of N—H···O and N—H···N hydrogen bonds, with only one of the nitro O atoms involved. The molecules form (4,4) nets built from R₄⁴(18) rings, with no significant π···π stacking interactions between neighbouring sheets.

The 1,2-isomer (CSD code ONITAN; Dhaneshwar et al., 1978) crystallizes in space group P2₁/a with Z' = 2. Each of the independent molecules forms an intramolecular N—H···O hydrogen bond, generating an S(6) motif, and the molecules are linked by further N—H···O hydrogen bonds into continuous C₂²(12) chains in which the two independent molecules alternate. These chains run parallel to the [011] direction in the domain -0.34 < x < 0.34 and parallel to [011] in the domain 0.16 < x < 0.84, so that the entire structure is a criss-cross stack, with chains in alternate layers inclined to one another by ca 81°. As in the 1,3-isomer, there are no π···π stacking interactions between the chains.

In view of this wide disparity of structural types, it is of interest to investigate the supramolecular aggregation of C-methylated nitroanilines to determine the effects of substituents of modest steric bulk. We present here the structures of three such C-methylated nitroanilines, 4-methyl-2-nitroaniline, (I), 4,5-dimethyl-2-nitroaniline, (II) and 4-methyl-3-nitroaniline, (III). \sch

The crystals of (I) are triclinic, P1, with Z' = 2. In each of the independent molecules (Fig. 1) there is an intramolecular N—H···O hydrogen bond forming an S(6) motif, and the molecules are linked into C₂²(12) chains running parallel to the [001] direction, in which molecules of the two types alternate (Fig. 2), as in ONITAN. However, the chain-forming hydrogen bonds (Table 2) differ from those in ONITAN. While N11 at (x, y, z) acts as donor, via H12, to O22ⁱ [symmetry code: (i) x, y, z - 1], by contrast N21 acts as donor, via H22, to both O11 and O22 in an almost planar three-centre system, forming an R₁²(4) motif (Fig. 2). This asymmetric bifurcated type of hydrogen bond, although absent from the three isomers of nitroaniline, is, in fact, the commonest mode of hydrogen bonding to C-nitro groups (Allen et al., 1997). In addition, C16 at (x, y, z) acts as donor to O21ⁱ, forming a rather weak C—H···O hydrogen bond and so completing an R₂²(8) motif. Thus, there are alternating R₁²(4) and R₂²(8) rings embedded in the C₂²(12) chain (Fig. 2). In compound (I), all of the C₂²(12) chains are parallel with one another, in contrast with the criss-cross arrangement in ONITAN. Thus (I) differs from its unsubstituted analogue, 2-nitroaniline, both in the form of the hydrogen bonding and in the stacking of the resulting chains: there are no π···π stacking interactions in either compound. The CSD records a polymorph of (I) (CSD code TEHGUI; Ellena et al., 1996) crystallized from acetone [cf. (I) crystallized from ethanol]. This second form is monoclinic, C2/c, with Z = 8. Each molecule forms an intramolecular N—H···O hydrogen bond in the usual S(6) motif, and they are linked by a single type of unbifurcated N—H···O hydrogen bond into zig-zig C(6) chains along [001] generated by glide planes. These chains are weakly coupled into pairs by means of aromatic π···π stacking interactions.

The introduction of a second C-methyl group into 2-nitroaniline to give (II) generates a pattern of intermolecular aggregation different from that in (I). Each of the two independent molecules in (II) forms an intramolecular S(6) motif (Fig. 3) and each type of molecule separately forms C(6) chains built from N—H···O hydrogen bonds (Table 4). These chains are generated by translation and run parallel to [100] (Fig. 4). There is, in addition, a C—H···O hydrogen bond in one of the chains (Table 4) which reinforces the effect of the intermolecular N—H···O hydrogen bond by forming an R₂¹(6) ring. The chains formed by the two independent molecules occupy different domains of z: that formed by molecule A (containing N11) lies in the domain 0.29 < z < 0.71, with the chain lying approximately along the line (x,1/4,1/2), while that formed by molecule B (containing N21) lies in the domain -0.21 < z < 0.21, approximately along the line (x,1/4,0). In addition, the chains of each type are weakly linked by aromatic π···π stacking interactions. For molecules of type A, the ring at (x, y, z) forms π···π interactions with those at (-x, 1 - y, 1 - z) [interplanar spacing 3.448 (3) Å and centroid offset 1.442 (3) Å] and at (1 - x, -y 1 - z) [interplanar spacing 3.407 (3) Å and centroid offset 1.739 (3) Å], so linking the neighbouring chains of A-type molecules into an (001) sheet. Similarly for molecules of type B, the ring at (x, y, z) is linked to those at (1 - x, 1 - y, -z) [interplanar spacing 3.405 (3) Å and centroid offset 1.323 (3) Å] and at (2 - x, -y, -z) [interplanar spacing 3.463 (3) Å and centroid offset 1.732 (3) Å], producing a similar sheet in the other domain of z. The overall `millefeuille' structure thus consists of alternating sheets of A and B molecules, each comprising hydrogen-bonded chains linked by π···π stacking interactions.

There are four independent molecules in 4-methyl-3-nitroaniline, (III), (Fig. 5), conveniently characterized as types n = 1–4, where type n contains atom Nn1. Molecules of types 1, 2 and 3 act as single donors of N—H···O hydrogen bonds, and molecules of types 1, 3 and 4 act as single acceptors. Type 4 molecules are double donors and type 2 molecules are double acceptors (Table 6). Each type of molecule forms, by translation, a C(7) chain containing a single type of N—H···O hydrogen bond and running parallel to the [010] direction. There are thus eight chains passing through each unit cell. There are chains aligned approximately along (0.57, y, 0.31) and (0.07, y, 0.19) comprising molecules of types 1 and 2, respectively, in which the N—H···O hydrogen bonds are directed along the positive and negative directions of b, respectively (Table 6), and a similar pair containing molecules of types 3 and 4 aligned approximately along (0.17, y, 0.43) and (0.67, y, 0.07). In addition, there is a further set of four chains generated from the first set by the centres of inversion. The chains built of type 2 and type 4 molecules are linked in pairs by a further N—H···O hydrogen bond: N41 at (x, y, z) acts as donor, via H41A, to O21^v [symmetry code: (v) 1 - x, 1 - y, -z], while N41^v similarly acts as donor to O21 at (x, y, z). Hence molecules of types 2 and 4 form a molecular ladder built of R₄³(18) rings (Fig. 6). The molecules of types 1 and 3, on the other hand, form isolated single chains of the type C(7). The CSD records a monoclinic polymorph of (III) (CSD code ZZZJIQ; Nigam & Murty, 1965), space group A2/a or Aa, whose cell dimensions are consistent with Z = 8. However, atomic coordinates were not determined and the crystallization solvent was not recorded.

Compound (IV) (CSD code TIXQUM01; Ellena et al., 1999) differs from (III) only in the location of its methyl group. Compound (IV) crystallizes in space group P2₁/n with Z' = 1, and each molecule acts as a double donor and a double acceptor of N—H···O hydrogen bonds. The structure generated by these interactions comprises continuous sheets built from centrosymmetric R₂²(14) and R₆⁶(26) rings (Fig. 7) arranged in a chessboard fashion. The elegance and simplicity of this structure formed by N—H···O hydrogen bonds is unfortunately obscured in the original report by the inclusion of a large number of very weak C—H.·O interactions, some of doubtful significance.

Compound (V) (CSD code BAJCIY; Lipscomb et al., 1981) differs from (IV) only in the location of the nitro group. The crystals are monoclinic, space group Cc, but no atomic coordinates are recorded either in the original report or in the CSD.

Isomeric with (II) is the N-methyl compound (VI) (CSD code MNOMAN10; Chiaroni, 1971), in which the N-methyl group is cisoid to the nitro group. The molecules are linked by a single N—H···O hydrogen bond into C(7) chains generated by translation (Fig. 8).

In both (I) and (II) the C—C bond distances in the aryl rings (Tables 1 and 3) show marked quinonoid bond fixation, which is absent in (III). Moreover, both the C—NH₂ and C—NO₂ bond lengths in (I) and (II) are significantly shorter than the corresponding bonds in (III), whereas the N—O distances in (I) and (II) are significantly longer than those in (III) (Table 5). Thus, the canonical form (VIIa) is a much more significant contributor in both (I) and (II) than in (III), which is itself better represented by (VIIb).

Related literature

For related literature, see: Allen & Kennard (1993); Allen et al. (1997); Batten & Robson (1998); Bernstein et al. (1995); Chiaroni (1971); Dhaneshwar et al. (1978); Ellena et al. (1996, 1999); Lipscomb et al. (1981); Nigam & Murty (1965); Ploug-Sørensen & Andersen (1986); Spek (2000); Tonogaki et al. (1993).

S2. Experimental

Samples of compounds (I)-(III) were obtained from Aldrich. Crystals suitable for single-crystal X-ray diffraction were grown from solutions in ethanol.

S3. Refinement

Compounds (I)-(III) are all triclinic at 150 K; for each, the space group P1 was assumed and confirmed by the analysis. H atoms were treated as riding, with C—H 0.95 Å (aromatic) or 0.98 Å (methyl), and N—H 0.88 Å. For compound (I), it was evident that the methyl groups exhibited rotational disorder, and they were modelled using six half-occupancy sites, offset from one another by 60° rotations. Examination of the structures with PLATON (Spek, 2000) showed that there were no solvent-accessible voids.

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The two independent molecules in (I), showing the atom-labelling scheme. 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 C2^2(12) chain parallel to [001] [symmetry code: (i) x, y, z - 1].
	Fig. 3. The two independent molecules in (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. Part of the crystal structure of (II), showing the two independent chains parallel to [100] [symmetry code: (ii) x - 1, y, z].
	Fig. 5. The four independent molecules in (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 6. Part of the crystal structure of (III), showing formation of a molecular ladder of R4^3(18) rings parallel to [010] and containing molecules of types 2 and 4. The unit-cell box is omitted for the sake of clarity [symmetry codes: (iv) x, y - 1, z; (v) 1 - x, 1 - y, -z].
	Fig. 7. Part of the crystal structure of (IV), showing the formation of the R2^2(14) and R6^6(26) rings which generate the chessboard pattern. For the sake of clarity, H atoms bonded to C have been omitted [symmetry codes: (vi) 1/2 + x, 1/2 - y, z - 1/2; (vii) 2 - x, 1 - y, 1 - z].
	Fig. 8. Part of the crystal structure of (VI) showing the formation of a C(7) chain [symmetry code: (viii) 1 + x, y, z)]

(I) 4-Methyl-2-nitroaniline

Crystal data

C7H8N2O2	Z = 4
Mr = 152.15	F(000) = 320
Triclinic, P1	Dx = 1.422 Mg m^−3
a = 7.8329 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.990 (2) Å	Cell parameters from 11810 reflections
c = 12.369 (3) Å	θ = 3.0–26.5°
α = 79.766 (17)°	µ = 0.11 mm^−1
β = 81.257 (19)°	T = 150 K
γ = 69.646 (8)°	Block, red
V = 710.8 (3) Å^3	0.10 × 0.05 × 0.05 mm

Data collection

KappaCCD diffractometer	2849 independent reflections
Radiation source: fine-focus sealed X-ray tube	988 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ϕ scans and ω scans with κ offsets	θmax = 26.5°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −9→8
Tmin = 0.989, Tmax = 0.995	k = −8→10
22499 measured reflections	l = −15→13

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0658P)^2] where P = (Fo^2 + 2Fc^2)/3
2849 reflections	(Δ/σ)max = 0.016
201 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C11	0.5024 (5)	0.7393 (5)	−0.1528 (3)	0.0377 (10)
N11	0.3515 (4)	0.8855 (4)	−0.1645 (2)	0.0500 (10)
C12	0.5877 (5)	0.6730 (5)	−0.0541 (3)	0.0341 (10)
N12	0.5215 (5)	0.7586 (4)	0.0417 (3)	0.0431 (9)
O11	0.3786 (4)	0.8923 (4)	0.0435 (2)	0.0488 (8)
O12	0.6058 (4)	0.6990 (4)	0.1257 (2)	0.0563 (9)
C13	0.7437 (5)	0.5176 (5)	−0.0483 (3)	0.0384 (10)
C14	0.8159 (5)	0.4226 (5)	−0.1342 (3)	0.0426 (11)
C141	0.9803 (6)	0.2544 (5)	−0.1284 (3)	0.0568 (13)
C15	0.7272 (6)	0.4917 (5)	−0.2330 (3)	0.0466 (11)
C16	0.5794 (6)	0.6414 (5)	−0.2416 (3)	0.0443 (11)
N21	0.3364 (5)	0.9081 (4)	0.3057 (3)	0.0555 (11)
C21	0.1956 (6)	1.0524 (5)	0.3327 (3)	0.0415 (11)
C22	0.1502 (5)	1.1104 (5)	0.4374 (3)	0.0346 (10)
N22	0.2575 (5)	1.0122 (4)	0.5270 (3)	0.0443 (9)
O21	0.3909 (4)	0.8738 (4)	0.5130 (2)	0.0529 (8)
O22	0.2122 (4)	1.0671 (4)	0.6182 (2)	0.0571 (9)
C23	0.0009 (5)	1.2626 (5)	0.4590 (3)	0.0413 (11)
C24	−0.1107 (6)	1.3626 (5)	0.3805 (3)	0.0412 (11)
C241	−0.2750 (6)	1.5240 (5)	0.4047 (4)	0.0595 (13)
C25	−0.0677 (6)	1.3065 (5)	0.2759 (3)	0.0462 (11)
C26	0.0769 (6)	1.1604 (5)	0.2528 (3)	0.0460 (12)
H12	0.3022	0.9186	−0.2276	0.060*
H11	0.3022	0.9479	−0.1091	0.060*
H13	0.8006	0.4780	0.0185	0.046*
H14A	1.0437	0.2397	−0.2025	0.085*	0.50
H14B	0.9410	0.1500	−0.0990	0.085*	0.50
H14C	1.0635	0.2640	−0.0799	0.085*	0.50
H14D	0.9885	0.1961	−0.0518	0.085*	0.50
H14E	1.0911	0.2858	−0.1553	0.085*	0.50
H14F	0.9687	0.1717	−0.1744	0.085*	0.50
H15	0.7746	0.4295	−0.2954	0.056*
H16	0.5260	0.6815	−0.3096	0.053*
H21	0.4096	0.8408	0.3556	0.067*
H22	0.3556	0.8808	0.2380	0.067*
H23	−0.0233	1.2973	0.5309	0.050*
H24A	−0.3467	1.5673	0.3409	0.089*	0.50
H24B	−0.2342	1.6198	0.4195	0.089*	0.50
H24C	−0.3510	1.4897	0.4694	0.089*	0.50
H24D	−0.2746	1.5506	0.4790	0.089*	0.50
H24E	−0.3870	1.4980	0.4003	0.089*	0.50
H24F	−0.2703	1.6282	0.3504	0.089*	0.50
H25	−0.1429	1.3737	0.2190	0.055*
H26	0.0998	1.1290	0.1801	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.039 (3)	0.031 (2)	0.042 (2)	−0.011 (2)	−0.003 (2)	−0.0031 (18)
N11	0.046 (3)	0.049 (2)	0.045 (2)	0.002 (2)	−0.0157 (17)	−0.0081 (16)
C12	0.031 (3)	0.031 (2)	0.038 (2)	−0.008 (2)	−0.0004 (19)	−0.0084 (18)
N12	0.045 (3)	0.045 (2)	0.038 (2)	−0.013 (2)	−0.0040 (18)	−0.0042 (17)
O11	0.045 (2)	0.0441 (18)	0.0491 (17)	−0.0020 (16)	−0.0033 (14)	−0.0134 (13)
O12	0.059 (2)	0.066 (2)	0.0405 (17)	−0.0111 (17)	−0.0116 (15)	−0.0109 (14)
C13	0.034 (3)	0.040 (3)	0.041 (2)	−0.012 (2)	−0.004 (2)	−0.0064 (19)
C14	0.034 (3)	0.042 (3)	0.048 (3)	−0.011 (2)	0.007 (2)	−0.007 (2)
C141	0.041 (3)	0.047 (3)	0.074 (3)	−0.004 (2)	0.003 (2)	−0.016 (2)
C15	0.050 (3)	0.051 (3)	0.042 (3)	−0.019 (2)	0.005 (2)	−0.017 (2)
C16	0.050 (3)	0.045 (3)	0.036 (2)	−0.011 (2)	−0.007 (2)	−0.0083 (19)
N21	0.057 (3)	0.046 (2)	0.056 (2)	−0.003 (2)	−0.0042 (19)	−0.0162 (17)
C21	0.043 (3)	0.032 (3)	0.046 (3)	−0.013 (2)	0.002 (2)	−0.0045 (19)
C22	0.034 (3)	0.037 (2)	0.034 (2)	−0.015 (2)	−0.0042 (19)	−0.0021 (18)
N22	0.044 (3)	0.040 (2)	0.045 (2)	−0.0093 (19)	−0.0091 (18)	−0.0012 (17)
O21	0.039 (2)	0.0386 (18)	0.068 (2)	0.0043 (16)	−0.0109 (15)	−0.0034 (14)
O22	0.065 (2)	0.061 (2)	0.0401 (17)	−0.0120 (16)	−0.0124 (15)	−0.0082 (15)
C23	0.038 (3)	0.043 (3)	0.038 (2)	−0.006 (2)	−0.005 (2)	−0.0068 (19)
C24	0.040 (3)	0.041 (3)	0.042 (3)	−0.014 (2)	−0.005 (2)	−0.003 (2)
C241	0.041 (3)	0.048 (3)	0.078 (3)	0.000 (2)	−0.007 (2)	−0.010 (2)
C25	0.046 (3)	0.044 (3)	0.047 (3)	−0.011 (2)	−0.016 (2)	−0.001 (2)
C26	0.051 (3)	0.050 (3)	0.038 (2)	−0.018 (3)	−0.005 (2)	−0.006 (2)

Geometric parameters (Å, º)

C11—C12	1.411 (5)	C21—C22	1.406 (5)
C12—C13	1.407 (5)	C22—C23	1.396 (5)
C13—C14	1.352 (5)	C23—C24	1.357 (5)
C13—H13	0.9500	C23—H23	0.9500
C14—C15	1.426 (5)	C24—C25	1.399 (5)
C14—C141	1.503 (5)	C24—C241	1.508 (5)
C141—H14A	0.9800	C241—H24A	0.9800
C141—H14B	0.9800	C241—H24B	0.9800
C141—H14C	0.9800	C241—H24C	0.9800
C141—H14D	0.9800	C241—H24D	0.9800
C141—H14E	0.9800	C241—H24E	0.9800
C141—H14F	0.9800	C241—H24F	0.9800
C15—C16	1.346 (5)	C25—C26	1.352 (5)
C15—H15	0.9500	C25—H25	0.9500
C16—C11	1.399 (5)	C26—C21	1.416 (5)
C16—H16	0.9500	C26—H26	0.9500
C11—N11	1.347 (4)	C21—N21	1.341 (5)
N11—H12	0.8800	N21—H21	0.8800
N11—H11	0.8800	N21—H22	0.8800
C12—N12	1.413 (4)	C22—N22	1.437 (5)
N12—O11	1.250 (4)	N22—O21	1.247 (4)
N12—O12	1.247 (4)	N22—O22	1.239 (4)
N11—C11—C16	119.4 (4)	C21—N21—H21	120.0
N11—C11—C12	124.0 (4)	C21—N21—H22	120.0
C16—C11—C12	116.6 (4)	H21—N21—H22	120.0
C11—N11—H11	120.0	N21—C21—C22	125.6 (4)
C11—N11—H12	120.0	N21—C21—C26	120.1 (4)
H11—N11—H12	120.0	C22—C21—C26	114.3 (4)
C13—C12—C11	120.5 (4)	C23—C22—C21	122.1 (4)
C13—C12—N12	117.6 (3)	C23—C22—N22	117.5 (3)
C11—C12—N12	121.9 (4)	C21—C22—N22	120.4 (4)
O12—N12—O11	119.8 (3)	O22—N22—O21	121.3 (3)
O12—N12—C12	119.5 (3)	O22—N22—C22	118.3 (3)
O11—N12—C12	120.7 (3)	O21—N22—C22	120.3 (3)
C14—C13—C12	122.6 (4)	C24—C23—C22	122.0 (4)
C14—C13—H13	118.7	C24—C23—H23	119.0
C12—C13—H13	118.7	C22—C23—H23	119.0
C13—C14—C15	116.0 (4)	C23—C24—C25	116.6 (4)
C13—C14—C141	123.1 (4)	C23—C24—C241	122.0 (4)
C15—C14—C141	120.9 (4)	C25—C24—C241	121.4 (4)
C14—C141—H14A	109.5	C24—C241—H24A	109.5
C14—C141—H14B	109.5	C24—C241—H24B	109.5
H14A—C141—H14B	109.5	H24A—C241—H24B	109.5
C14—C141—H14C	109.5	C24—C241—H24C	109.5
H14A—C141—H14C	109.5	H24A—C241—H24C	109.5
H14B—C141—H14C	109.5	H24B—C241—H24C	109.5
C14—C141—H14D	109.5	C24—C241—H24D	109.5
H14A—C141—H14D	141.1	H24A—C241—H24D	141.1
H14B—C141—H14D	56.3	H24B—C241—H24D	56.3
H14C—C141—H14D	56.3	H24C—C241—H24D	56.3
C14—C141—H14E	109.5	C24—C241—H24E	109.5
H14A—C141—H14E	56.3	H24A—C241—H24E	56.3
H14B—C141—H14E	141.1	H24B—C241—H24E	141.1
H14C—C141—H14E	56.3	H24C—C241—H24E	56.3
H14D—C141—H14E	109.5	H24D—C241—H24E	109.5
C14—C141—H14F	109.5	C24—C241—H24F	109.5
H14A—C141—H14F	56.3	H24A—C241—H24F	56.3
H14B—C141—H14F	56.3	H24B—C241—H24F	56.3
H14C—C141—H14F	141.1	H24C—C241—H24F	141.1
H14D—C141—H14F	109.5	H24D—C241—H24F	109.5
H14E—C141—H14F	109.5	H24E—C241—H24F	109.5
C16—C15—C14	122.9 (4)	C26—C25—C24	122.5 (4)
C16—C15—H15	118.6	C26—C25—H25	118.8
C14—C15—H15	118.6	C24—C25—H25	118.8
C15—C16—C11	121.5 (4)	C25—C26—C21	122.5 (4)
C15—C16—H16	119.2	C25—C26—H26	118.8
C11—C16—H16	119.2	C21—C26—H26	118.8
N11—C11—C12—C13	179.0 (4)	N21—C21—C22—C23	180.0 (19)
C16—C11—C12—C13	1.0 (6)	C26—C21—C22—C23	−0.4 (5)
N11—C11—C12—N12	−1.1 (6)	N21—C21—C22—N22	−0.4 (6)
C16—C11—C12—N12	−179.2 (3)	C26—C21—C22—N22	179.2 (3)
C13—C12—N12—O12	2.7 (5)	C23—C22—N22—O22	0.1 (5)
C11—C12—N12—O12	−177.2 (3)	C21—C22—N22—O22	−179.5 (3)
C13—C12—N12—O11	−176.7 (3)	C23—C22—N22—O21	179.0 (4)
C11—C12—N12—O11	3.4 (6)	C21—C22—N22—O21	−0.6 (5)
C11—C12—C13—C14	−1.9 (6)	C21—C22—C23—C24	0.8 (6)
N12—C12—C13—C14	178.3 (4)	N22—C22—C23—C24	−178.9 (3)
C12—C13—C14—C15	1.6 (6)	C22—C23—C24—C25	−0.6 (6)
C12—C13—C14—C141	−178.8 (4)	C22—C23—C24—C241	178.2 (4)
C13—C14—C15—C16	−0.6 (6)	C23—C24—C25—C26	0.1 (6)
C141—C14—C15—C16	179.8 (4)	C241—C24—C25—C26	−178.7 (4)
C14—C15—C16—C11	−0.1 (6)	C24—C25—C26—C21	0.2 (6)
N11—C11—C16—C15	−178.2 (4)	N21—C21—C26—C25	179.6 (4)
C12—C11—C16—C15	0.0 (6)	C22—C21—C26—C25	−0.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O11	0.88	1.99	2.625 (4)	128
N21—H21···O21	0.88	1.99	2.614 (4)	127
N11—H12···O22^i	0.88	2.14	2.987 (4)	162
N21—H22···O11	0.88	2.37	3.230 (4)	165
N21—H22···O12	0.88	2.41	3.105 (5)	137
C16—H16···O21^i	0.95	2.58	3.505 (5)	164

Symmetry code: (i) x, y, z−1.

(II) 4,5-Dimethyl-2-nitroaniline

Crystal data

C8H10N2O2	Z = 4
Mr = 166.18	F(000) = 352
Triclinic, P1	Dx = 1.398 Mg m^−3
a = 7.1422 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4564 (15) Å	Cell parameters from 3468 reflections
c = 17.044 (3) Å	θ = 3.1–27.4°
α = 81.43 (3)°	µ = 0.10 mm^−1
β = 89.27 (3)°	T = 150 K
γ = 61.84 (3)°	Plate, orange
V = 789.6 (3) Å^3	0.14 × 0.12 × 0.03 mm

Data collection

KappaCCD diffractometer	3468 independent reflections
Radiation source: fine-focus sealed X-ray tube	1988 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ϕ scans and ω scans with κ offsets	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −9→9
Tmin = 0.986, Tmax = 0.997	k = −9→9
9952 measured reflections	l = −21→21

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0797P)^2] where P = (Fo^2 + 2Fc^2)/3
3468 reflections	(Δ/σ)max < 0.001
221 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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

	x	y	z	Uiso*/Ueq
C11	0.1776 (3)	0.2439 (3)	0.43577 (13)	0.0248 (5)
N11	0.0998 (3)	0.2384 (3)	0.36530 (11)	0.0344 (5)
C12	0.3601 (3)	0.2648 (3)	0.44836 (12)	0.0245 (5)
N12	0.4881 (3)	0.2767 (3)	0.38443 (11)	0.0279 (5)
O11	0.4327 (2)	0.2760 (2)	0.31550 (9)	0.0378 (4)
O12	0.6506 (2)	0.2893 (2)	0.39840 (10)	0.0399 (5)
C13	0.4285 (3)	0.2688 (3)	0.52446 (13)	0.0251 (5)
C14	0.3224 (3)	0.2513 (3)	0.59004 (13)	0.0262 (5)
C141	0.3980 (4)	0.2544 (4)	0.67129 (14)	0.0363 (6)
C15	0.1386 (3)	0.2287 (3)	0.57891 (13)	0.0264 (5)
C151	0.0158 (4)	0.2084 (4)	0.64872 (14)	0.0374 (6)
C16	0.0710 (3)	0.2268 (3)	0.50424 (13)	0.0259 (5)
C21	0.6658 (3)	0.2342 (3)	0.08580 (13)	0.0242 (5)
N21	0.5849 (3)	0.2189 (3)	0.15665 (11)	0.0306 (5)
C22	0.8492 (3)	0.2572 (3)	0.07220 (13)	0.0233 (5)
N22	0.9730 (3)	0.2610 (3)	0.13588 (11)	0.0281 (5)
O21	0.9171 (2)	0.2496 (2)	0.20502 (9)	0.0384 (4)
O22	1.1372 (2)	0.2745 (3)	0.12186 (10)	0.0414 (5)
C23	0.9179 (3)	0.2737 (3)	−0.00477 (13)	0.0259 (5)
C24	0.8125 (3)	0.2672 (3)	−0.06986 (13)	0.0273 (5)
C241	0.8899 (4)	0.2839 (3)	−0.15149 (14)	0.0358 (6)
C25	0.6289 (3)	0.2425 (3)	−0.05741 (13)	0.0255 (5)
C251	0.5056 (4)	0.2374 (3)	−0.12683 (14)	0.0353 (6)
C26	0.5616 (3)	0.2273 (3)	0.01757 (13)	0.0262 (5)
H11	0.1643	0.2484	0.3218	0.041*
H12	−0.0158	0.2249	0.3626	0.041*
H13	0.5519	0.2841	0.5307	0.030*
H141	0.5283	0.2673	0.6677	0.054*
H142	0.4273	0.1261	0.7064	0.054*
H143	0.2878	0.3719	0.6929	0.054*
H151	−0.1003	0.1858	0.6310	0.056*
H152	−0.0433	0.3349	0.6722	0.056*
H153	0.1108	0.0912	0.6885	0.056*
H16	−0.0536	0.2132	0.4984	0.031*
H22	0.4693	0.2050	0.1597	0.037*
H21	0.6477	0.2229	0.2000	0.037*
H23	1.0415	0.2898	−0.0119	0.031*
H241	1.0158	0.3036	−0.1485	0.054*
H242	0.7774	0.4018	−0.1863	0.054*
H243	0.9270	0.1573	−0.1730	0.054*
H251	0.3868	0.2154	−0.1078	0.053*
H252	0.5992	0.1248	−0.1548	0.053*
H253	0.4502	0.3688	−0.1633	0.053*
H26	0.4377	0.2113	0.0240	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0258 (11)	0.0273 (11)	0.0221 (13)	−0.0126 (9)	0.0016 (9)	−0.0065 (9)
N11	0.0351 (10)	0.0518 (12)	0.0251 (12)	−0.0268 (10)	0.0040 (8)	−0.0099 (9)
C12	0.0279 (11)	0.0256 (11)	0.0214 (13)	−0.0138 (10)	0.0069 (9)	−0.0047 (9)
N12	0.0272 (10)	0.0301 (10)	0.0260 (12)	−0.0135 (9)	0.0055 (8)	−0.0043 (8)
O11	0.0416 (10)	0.0523 (10)	0.0212 (10)	−0.0232 (8)	0.0052 (7)	−0.0080 (8)
O12	0.0343 (9)	0.0550 (11)	0.0401 (11)	−0.0294 (9)	0.0076 (8)	−0.0070 (8)
C13	0.0200 (10)	0.0287 (11)	0.0259 (13)	−0.0111 (9)	−0.0017 (9)	−0.0045 (9)
C14	0.0274 (11)	0.0268 (11)	0.0221 (13)	−0.0108 (10)	−0.0024 (9)	−0.0042 (9)
C141	0.0415 (14)	0.0436 (14)	0.0255 (14)	−0.0212 (12)	0.0011 (10)	−0.0068 (11)
C15	0.0249 (11)	0.0235 (11)	0.0261 (14)	−0.0079 (9)	0.0041 (9)	−0.0032 (9)
C151	0.0408 (14)	0.0440 (14)	0.0301 (15)	−0.0224 (12)	0.0111 (11)	−0.0067 (11)
C16	0.0229 (11)	0.0282 (11)	0.0280 (13)	−0.0136 (9)	0.0005 (9)	−0.0037 (9)
C21	0.0263 (11)	0.0243 (11)	0.0219 (13)	−0.0117 (9)	0.0044 (9)	−0.0050 (9)
N21	0.0331 (10)	0.0462 (11)	0.0210 (11)	−0.0255 (9)	0.0056 (8)	−0.0067 (9)
C22	0.0233 (11)	0.0230 (11)	0.0229 (12)	−0.0103 (9)	−0.0018 (9)	−0.0038 (9)
N22	0.0245 (10)	0.0299 (10)	0.0282 (12)	−0.0116 (8)	−0.0018 (8)	−0.0040 (8)
O21	0.0410 (9)	0.0559 (10)	0.0222 (10)	−0.0262 (8)	−0.0021 (7)	−0.0061 (8)
O22	0.0305 (9)	0.0565 (11)	0.0452 (11)	−0.0271 (8)	−0.0010 (8)	−0.0084 (8)
C23	0.0224 (11)	0.0259 (11)	0.0289 (13)	−0.0112 (9)	0.0047 (9)	−0.0044 (9)
C24	0.0306 (12)	0.0244 (11)	0.0240 (13)	−0.0107 (10)	0.0054 (10)	−0.0047 (9)
C241	0.0413 (14)	0.0378 (13)	0.0264 (14)	−0.0174 (11)	0.0085 (10)	−0.0055 (10)
C25	0.0285 (12)	0.0232 (11)	0.0224 (13)	−0.0099 (10)	0.0002 (9)	−0.0052 (9)
C251	0.0361 (13)	0.0392 (13)	0.0293 (14)	−0.0162 (11)	−0.0028 (10)	−0.0077 (10)
C26	0.0233 (11)	0.0277 (11)	0.0280 (14)	−0.0122 (10)	0.0018 (9)	−0.0054 (9)

Geometric parameters (Å, º)

C11—C12	1.407 (3)	N12—O12	1.237 (2)
C12—C13	1.401 (3)	C21—C22	1.411 (3)
C12—N12	1.433 (3)	C22—C23	1.403 (3)
N12—O12	1.237 (2)	C23—C24	1.368 (3)
N12—O11	1.246 (2)	C23—H23	0.9500
C13—C14	1.367 (3)	C24—C25	1.417 (3)
C13—H13	0.9500	C24—C241	1.500 (3)
C14—C15	1.419 (3)	C241—H241	0.9800
C14—C141	1.500 (3)	C241—H242	0.9800
C141—H141	0.9800	C241—H243	0.9800
C141—H142	0.9800	C25—C26	1.367 (3)
C141—H143	0.9800	C25—C251	1.499 (3)
C15—C16	1.371 (3)	C251—H251	0.9800
C15—C151	1.501 (3)	C251—H252	0.9800
C151—H151	0.9800	C251—H253	0.9800
C151—H152	0.9800	C26—C21	1.409 (3)
C151—H153	0.9800	C26—H26	0.9500
C16—C11	1.408 (3)	C21—N21	1.345 (3)
C16—H16	0.9500	N21—H22	0.8800
C11—N11	1.344 (3)	N21—H21	0.8800
N11—H11	0.8800	C22—N22	1.420 (3)
N11—H12	0.8800	N22—O21	1.243 (2)
C12—N12	1.433 (3)	N22—O22	1.241 (2)
N12—O11	1.246 (2)
N11—C11—C12	125.78 (19)	N21—C21—C26	118.60 (19)
N11—C11—C16	118.62 (19)	N21—C21—C22	126.0 (2)
C12—C11—C16	115.6 (2)	C26—C21—C22	115.35 (19)
C11—N11—H11	120.0	C21—N21—H22	120.0
C11—N11—H12	120.0	C21—N21—H21	120.0
H11—N11—H12	120.0	H22—N21—H21	120.0
C13—C12—C11	121.42 (18)	C23—C22—C21	121.1 (2)
C13—C12—N12	116.98 (18)	C23—C22—N22	117.57 (18)
C11—C12—N12	121.56 (19)	C21—C22—N22	121.35 (19)
O12—N12—O11	121.06 (18)	O22—N22—O21	120.60 (19)
O12—N12—C12	119.53 (19)	O22—N22—C22	119.46 (18)
O11—N12—C12	119.41 (17)	O21—N22—C22	119.94 (18)
C14—C13—C12	121.81 (19)	C24—C23—C22	122.1 (2)
C14—C13—H13	119.1	C24—C23—H23	118.9
C12—C13—H13	119.1	C22—C23—H23	118.9
C13—C14—C15	117.8 (2)	C23—C24—C25	117.7 (2)
C13—C14—C141	121.3 (2)	C23—C24—C241	121.1 (2)
C15—C14—C141	120.89 (19)	C25—C24—C241	121.2 (2)
C14—C141—H141	109.5	C24—C241—H241	109.5
C14—C141—H142	109.5	C24—C241—H242	109.5
H141—C141—H142	109.5	H241—C241—H242	109.5
C14—C141—H143	109.5	C24—C241—H243	109.5
H141—C141—H143	109.5	H241—C241—H243	109.5
H142—C141—H143	109.5	H242—C241—H243	109.5
C16—C15—C14	120.23 (19)	C26—C25—C24	120.1 (2)
C16—C15—C151	119.6 (2)	C26—C25—C251	119.96 (19)
C14—C15—C151	120.2 (2)	C24—C25—C251	119.9 (2)
C15—C151—H151	109.5	C25—C251—H251	109.5
C15—C151—H152	109.5	C25—C251—H252	109.5
H151—C151—H152	109.5	H251—C251—H252	109.5
C15—C151—H153	109.5	C25—C251—H253	109.5
H151—C151—H153	109.5	H251—C251—H253	109.5
H152—C151—H153	109.5	H252—C251—H253	109.5
C15—C16—C11	123.1 (2)	C25—C26—C21	123.63 (19)
C15—C16—H16	118.4	C25—C26—H26	118.2
C11—C16—H16	118.4	C21—C26—H26	118.2
N11—C11—C12—C13	180.00 (19)	N21—C21—C22—C23	−179.37 (18)
C16—C11—C12—C13	−0.2 (3)	C26—C21—C22—C23	0.6 (3)
N11—C11—C12—N12	−1.9 (3)	N21—C21—C22—N22	1.7 (3)
C16—C11—C12—N12	177.86 (17)	C26—C21—C22—N22	−178.33 (17)
C13—C12—N12—O12	0.2 (3)	C23—C22—N22—O22	−1.4 (3)
C11—C12—N12—O12	−177.98 (18)	C21—C22—N22—O22	177.60 (18)
C13—C12—N12—O11	−179.22 (17)	C23—C22—N22—O21	179.04 (17)
C11—C12—N12—O11	2.6 (3)	C21—C22—N22—O21	−2.0 (3)
C11—C12—C13—C14	0.4 (3)	C21—C22—C23—C24	−0.4 (3)
N12—C12—C13—C14	−177.74 (18)	N22—C22—C23—C24	178.58 (18)
C12—C13—C14—C15	0.0 (3)	C22—C23—C24—C25	−0.1 (3)
C12—C13—C14—C141	179.58 (18)	C22—C23—C24—C241	−179.64 (18)
C13—C14—C15—C16	−0.6 (3)	C23—C24—C25—C26	0.4 (3)
C141—C14—C15—C16	179.81 (18)	C241—C24—C25—C26	179.92 (19)
C13—C14—C15—C151	179.88 (18)	C23—C24—C25—C251	179.13 (18)
C141—C14—C15—C151	0.3 (3)	C241—C24—C25—C251	−1.4 (3)
C14—C15—C16—C11	0.8 (3)	C24—C25—C26—C21	−0.2 (3)
C151—C15—C16—C11	−179.65 (19)	C251—C25—C26—C21	−178.90 (18)
N11—C11—C16—C15	179.39 (18)	N21—C21—C26—C25	179.65 (18)
C12—C11—C16—C15	−0.4 (3)	C22—C21—C26—C25	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O11	0.88	2.02	2.638 (3)	126
N21—H21···O21	0.88	2.03	2.642 (3)	126
N11—H12···O12^i	0.88	2.29	3.102 (3)	153
N21—H22···O22^i	0.88	2.26	3.078 (3)	155
C16—H16···O12^i	0.95	2.52	3.325 (3)	142

Symmetry code: (i) x−1, y, z.

(III) 4-Methyl-3-nitroaniline

Crystal data

C7H8N2O2	Z = 8
Mr = 152.15	F(000) = 640
Triclinic, P1	Dx = 1.419 Mg m^−3
a = 7.3814 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2085 (3) Å	Cell parameters from 5933 reflections
c = 23.5355 (9) Å	θ = 2.9–42.1°
α = 87.9310 (13)°	µ = 0.11 mm^−1
β = 89.8880 (12)°	T = 150 K
γ = 88.371 (2)°	Plate, orange
V = 1424.52 (8) Å^3	0.45 × 0.20 × 0.02 mm

Data collection

KappaCCD diffractometer	6812 independent reflections
Radiation source: fine-focus sealed X-ray tube	3517 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ϕ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −9→9
Tmin = 0.954, Tmax = 0.999	k = −10→10
14564 measured reflections	l = −30→30

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0972P)^2] where P = (Fo^2 + 2Fc^2)/3
6812 reflections	(Δ/σ)max = 0.001
401 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

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

	x	y	z	Uiso*/Ueq
C11	0.56474 (18)	0.86353 (17)	0.35323 (6)	0.0314 (4)
N11	0.53317 (17)	0.97841 (15)	0.39364 (6)	0.0403 (4)
C12	0.53661 (18)	0.69945 (17)	0.36455 (6)	0.0300 (4)
C13	0.56699 (17)	0.58859 (16)	0.32220 (6)	0.0288 (4)
N13	0.52948 (16)	0.41871 (15)	0.33812 (6)	0.0371 (3)
O11	0.55196 (15)	0.37198 (13)	0.38791 (5)	0.0468 (3)
O12	0.47637 (17)	0.32950 (14)	0.30145 (6)	0.0590 (4)
C14	0.62959 (17)	0.62960 (17)	0.26776 (6)	0.0303 (4)
C141	0.6623 (2)	0.51338 (19)	0.22092 (7)	0.0420 (4)
C15	0.66299 (18)	0.79488 (18)	0.25902 (7)	0.0342 (4)
C16	0.63206 (19)	0.90821 (18)	0.29961 (7)	0.0332 (4)
C21	0.07558 (18)	−0.35053 (17)	0.14782 (6)	0.0308 (4)
N21	0.04961 (17)	−0.46572 (15)	0.10789 (6)	0.0417 (4)
C22	0.04596 (18)	−0.18566 (17)	0.13501 (6)	0.0296 (4)
C23	0.06983 (17)	−0.07392 (16)	0.17661 (7)	0.0292 (4)
N23	0.03456 (16)	0.09718 (15)	0.15865 (6)	0.0365 (3)
O21	0.05719 (15)	0.13749 (13)	0.10834 (5)	0.0481 (3)
O22	−0.01548 (17)	0.19462 (14)	0.19403 (6)	0.0595 (4)
C24	0.12629 (18)	−0.11310 (18)	0.23207 (6)	0.0299 (4)
C241	0.1525 (2)	0.00382 (19)	0.27840 (7)	0.0406 (4)
C25	0.16208 (18)	−0.27956 (18)	0.24247 (7)	0.0341 (4)
C26	0.13699 (19)	−0.39476 (18)	0.20244 (7)	0.0343 (4)
C31	0.17567 (19)	0.75218 (18)	0.47215 (7)	0.0347 (4)
N31	0.2312 (2)	0.87271 (17)	0.50703 (7)	0.0611 (5)
C32	0.22739 (18)	0.59087 (17)	0.48274 (6)	0.0320 (4)
C33	0.17436 (18)	0.47341 (17)	0.44621 (7)	0.0317 (4)
N33	0.23562 (17)	0.30612 (16)	0.46143 (6)	0.0412 (4)
O31	0.17802 (19)	0.19418 (15)	0.43514 (7)	0.0745 (5)
O32	0.34353 (17)	0.28293 (15)	0.50014 (6)	0.0569 (4)
C34	0.06883 (18)	0.50611 (18)	0.39773 (7)	0.0333 (4)
C341	0.0114 (2)	0.3859 (2)	0.35488 (8)	0.0462 (5)
C35	0.01686 (18)	0.67065 (18)	0.38913 (7)	0.0340 (4)
C36	0.06698 (19)	0.78939 (19)	0.42482 (7)	0.0350 (4)
C41	0.6822 (2)	0.77143 (19)	0.02979 (7)	0.0385 (4)
N41	0.7432 (2)	0.65100 (18)	−0.00485 (7)	0.0778 (6)
C42	0.7289 (2)	0.93232 (19)	0.01955 (7)	0.0402 (4)
C43	0.67149 (19)	1.05069 (18)	0.05635 (7)	0.0361 (4)
N43	0.72699 (18)	1.21696 (17)	0.04090 (7)	0.0487 (4)
O41	0.6734 (2)	1.32797 (17)	0.06923 (9)	0.1218 (7)
O42	0.8274 (2)	1.23829 (16)	0.00100 (6)	0.0684 (4)
C44	0.56794 (19)	1.01953 (18)	0.10478 (7)	0.0359 (4)
C441	0.5070 (2)	1.1402 (2)	0.14802 (8)	0.0502 (5)
C45	0.52115 (19)	0.85592 (19)	0.11306 (7)	0.0358 (4)
C46	0.57408 (19)	0.73627 (19)	0.07713 (7)	0.0353 (4)
H11A	0.4941	0.9482	0.4277	0.048*
H11B	0.5521	1.0820	0.3854	0.048*
H12	0.4967	0.6630	0.4011	0.036*
H4A	0.5459	0.4767	0.2069	0.063*
H4B	0.7347	0.4190	0.2354	0.063*
H41C	0.7277	0.5684	0.1898	0.063*
H15	0.7095	0.8308	0.2232	0.041*
H16	0.6569	1.0193	0.2911	0.040*
H21A	0.0135	−0.4354	0.0734	0.050*
H21B	0.0691	−0.5698	0.1168	0.050*
H22	0.0095	−0.1499	0.0978	0.036*
H41D	0.2275	0.0933	0.2643	0.061*
H41E	0.2128	−0.0530	0.3108	0.061*
H41F	0.0343	0.0478	0.2905	0.061*
H25	0.2058	−0.3148	0.2789	0.041*
H26	0.1619	−0.5065	0.2121	0.041*
H31A	0.3006	0.8474	0.5366	0.073*
H31B	0.1971	0.9749	0.4997	0.073*
H32	0.2993	0.5609	0.5151	0.038*
H41G	0.1183	0.3260	0.3410	0.069*
H41H	−0.0493	0.4444	0.3229	0.069*
H41I	−0.0724	0.3090	0.3728	0.069*
H35	−0.0564	0.7011	0.3571	0.041*
H36	0.0270	0.8990	0.4172	0.042*
H41A	0.8130	0.6752	−0.0341	0.093*
H41B	0.7125	0.5494	0.0022	0.093*
H42	0.8002	0.9611	−0.0127	0.048*
H41J	0.6126	1.1944	0.1629	0.075*
H41K	0.4446	1.0830	0.1793	0.075*
H41L	0.4239	1.2218	0.1300	0.075*
H45	0.4492	0.8269	0.1452	0.043*
H46	0.5368	0.6277	0.0845	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0327 (7)	0.0258 (8)	0.0354 (9)	0.0004 (6)	−0.0024 (6)	0.0004 (7)
N11	0.0593 (8)	0.0244 (7)	0.0376 (8)	−0.0028 (6)	0.0021 (6)	−0.0037 (6)
C12	0.0321 (7)	0.0255 (8)	0.0319 (8)	0.0000 (6)	0.0026 (6)	0.0028 (7)
C13	0.0298 (7)	0.0197 (7)	0.0367 (9)	−0.0009 (5)	0.0003 (6)	−0.0001 (7)
N13	0.0390 (6)	0.0244 (7)	0.0477 (8)	0.0000 (5)	0.0081 (6)	−0.0035 (6)
O11	0.0591 (7)	0.0306 (6)	0.0497 (7)	0.0017 (5)	0.0086 (6)	0.0106 (6)
O12	0.0779 (8)	0.0353 (6)	0.0655 (9)	−0.0200 (6)	0.0042 (7)	−0.0122 (6)
C14	0.0272 (7)	0.0309 (8)	0.0327 (8)	−0.0012 (6)	−0.0010 (6)	−0.0003 (7)
C141	0.0418 (8)	0.0475 (10)	0.0373 (9)	−0.0011 (7)	0.0047 (7)	−0.0100 (8)
C15	0.0339 (7)	0.0366 (9)	0.0315 (8)	−0.0042 (6)	0.0027 (6)	0.0081 (7)
C16	0.0371 (7)	0.0222 (8)	0.0401 (9)	−0.0044 (6)	−0.0031 (6)	0.0045 (7)
C21	0.0313 (7)	0.0273 (8)	0.0337 (8)	−0.0010 (6)	0.0027 (6)	−0.0021 (7)
N21	0.0632 (8)	0.0231 (7)	0.0388 (8)	−0.0006 (6)	−0.0004 (6)	−0.0017 (6)
C22	0.0310 (7)	0.0282 (8)	0.0294 (8)	−0.0035 (6)	−0.0019 (6)	0.0049 (7)
C23	0.0269 (7)	0.0216 (7)	0.0391 (9)	−0.0007 (5)	0.0015 (6)	0.0002 (7)
N23	0.0394 (7)	0.0261 (7)	0.0442 (8)	−0.0019 (5)	−0.0061 (6)	−0.0008 (6)
O21	0.0665 (7)	0.0298 (6)	0.0475 (7)	−0.0048 (5)	−0.0085 (6)	0.0100 (6)
O22	0.0836 (9)	0.0331 (7)	0.0617 (9)	0.0152 (6)	−0.0037 (7)	−0.0126 (6)
C24	0.0263 (7)	0.0328 (8)	0.0309 (8)	−0.0019 (6)	0.0016 (6)	−0.0018 (7)
C241	0.0404 (8)	0.0461 (10)	0.0357 (9)	−0.0013 (7)	−0.0031 (7)	−0.0083 (8)
C25	0.0308 (7)	0.0392 (9)	0.0316 (9)	0.0015 (6)	−0.0019 (6)	0.0053 (7)
C26	0.0375 (8)	0.0258 (8)	0.0390 (9)	0.0014 (6)	0.0026 (7)	0.0042 (7)
C31	0.0387 (8)	0.0310 (8)	0.0345 (9)	−0.0050 (6)	0.0023 (6)	−0.0008 (7)
N31	0.0885 (11)	0.0317 (8)	0.0639 (11)	−0.0037 (7)	−0.0272 (9)	−0.0092 (8)
C32	0.0316 (7)	0.0309 (8)	0.0331 (9)	−0.0031 (6)	−0.0021 (6)	0.0041 (7)
C33	0.0302 (7)	0.0248 (8)	0.0398 (9)	0.0004 (6)	0.0049 (6)	0.0036 (7)
N33	0.0396 (7)	0.0304 (7)	0.0530 (9)	−0.0004 (6)	0.0042 (6)	0.0059 (7)
O31	0.0850 (9)	0.0256 (7)	0.1136 (12)	−0.0026 (6)	−0.0296 (8)	−0.0093 (7)
O32	0.0700 (8)	0.0420 (7)	0.0571 (8)	0.0096 (6)	−0.0094 (6)	0.0138 (6)
C34	0.0267 (7)	0.0328 (8)	0.0407 (9)	−0.0031 (6)	0.0042 (6)	−0.0046 (7)
C341	0.0384 (8)	0.0447 (10)	0.0564 (11)	−0.0020 (7)	−0.0023 (8)	−0.0140 (9)
C35	0.0293 (7)	0.0367 (9)	0.0357 (9)	0.0033 (6)	−0.0024 (6)	0.0009 (7)
C36	0.0335 (7)	0.0281 (8)	0.0427 (9)	0.0049 (6)	0.0014 (7)	0.0033 (7)
C41	0.0465 (8)	0.0311 (9)	0.0375 (9)	0.0032 (7)	0.0015 (7)	0.0005 (8)
N41	0.1300 (14)	0.0332 (9)	0.0701 (11)	0.0013 (9)	0.0514 (10)	−0.0063 (8)
C42	0.0437 (8)	0.0367 (9)	0.0394 (10)	0.0008 (7)	0.0058 (7)	0.0097 (8)
C43	0.0341 (7)	0.0245 (8)	0.0491 (10)	−0.0003 (6)	−0.0028 (7)	0.0054 (7)
N43	0.0428 (7)	0.0327 (8)	0.0699 (11)	−0.0020 (6)	−0.0005 (7)	0.0078 (7)
O41	0.1295 (11)	0.0258 (8)	0.2105 (18)	−0.0023 (8)	0.0974 (12)	−0.0136 (10)
O42	0.1024 (10)	0.0506 (8)	0.0526 (9)	−0.0283 (7)	0.0062 (7)	0.0137 (7)
C44	0.0299 (7)	0.0323 (8)	0.0457 (10)	0.0004 (6)	−0.0045 (7)	−0.0048 (8)
C441	0.0492 (9)	0.0417 (10)	0.0605 (12)	−0.0019 (8)	0.0007 (8)	−0.0138 (9)
C45	0.0314 (7)	0.0405 (9)	0.0355 (9)	−0.0056 (6)	0.0001 (6)	0.0002 (7)
C46	0.0371 (8)	0.0286 (8)	0.0401 (9)	−0.0035 (6)	−0.0022 (7)	0.0038 (7)

Geometric parameters (Å, º)

C11—N11	1.3782 (19)	C31—N31	1.380 (2)
C11—C12	1.385 (2)	C31—C32	1.382 (2)
C11—C16	1.396 (2)	C31—C36	1.394 (2)
N11—H11A	0.8800	N31—H31A	0.8800
N11—H11B	0.8800	N31—H31B	0.8800
C12—C13	1.388 (2)	C32—C33	1.380 (2)
C12—H12	0.9500	C32—H32	0.9500
C13—C14	1.394 (2)	C33—C34	1.396 (2)
C13—N13	1.4648 (18)	C33—N33	1.4657 (19)
N13—O11	1.2300 (17)	N33—O31	1.2134 (18)
N13—O12	1.2237 (17)	N33—O32	1.2177 (18)
C14—C15	1.394 (2)	C34—C35	1.401 (2)
C14—C141	1.499 (2)	C34—C341	1.506 (2)
C141—H4A	0.9800	C341—H41G	0.9800
C141—H4B	0.9800	C341—H41H	0.9800
C141—H41C	0.9800	C341—H41I	0.9800
C15—C16	1.372 (2)	C35—C36	1.369 (2)
C15—H15	0.9500	C35—H35	0.9500
C16—H16	0.9500	C36—H36	0.9500
C21—N21	1.3744 (19)	C41—N41	1.370 (2)
C21—C22	1.387 (2)	C41—C42	1.387 (2)
C21—C26	1.396 (2)	C41—C46	1.396 (2)
N21—H21A	0.8800	N41—H41A	0.8800
N21—H21B	0.8800	N41—H41B	0.8800
C22—C23	1.380 (2)	C42—C43	1.382 (2)
C22—H22	0.9500	C42—H42	0.9500
C23—C24	1.395 (2)	C43—C44	1.391 (2)
C23—N23	1.4682 (18)	C43—N43	1.469 (2)
N23—O21	1.2303 (17)	N43—O41	1.206 (2)
N23—O22	1.2246 (17)	N43—O42	1.2063 (19)
C24—C25	1.397 (2)	C44—C45	1.403 (2)
C24—C241	1.495 (2)	C44—C441	1.505 (2)
C241—H41D	0.9800	C441—H41J	0.9800
C241—H41E	0.9800	C441—H41K	0.9800
C241—H41F	0.9800	C441—H41L	0.9800
C25—C26	1.375 (2)	C45—C46	1.367 (2)
C25—H25	0.9500	C45—H45	0.9500
C26—H26	0.9500	C46—H46	0.9500
N11—C11—C12	121.68 (14)	N31—C31—C32	121.04 (15)
N11—C11—C16	120.91 (13)	N31—C31—C36	121.08 (14)
C12—C11—C16	117.38 (13)	C32—C31—C36	117.87 (14)
C11—N11—H11A	120.0	C31—N31—H31A	120.0
C11—N11—H11B	120.0	C31—N31—H31B	120.0
H11A—N11—H11B	120.0	H31A—N31—H31B	120.0
C11—C12—C13	119.64 (14)	C33—C32—C31	119.83 (14)
C11—C12—H12	120.2	C33—C32—H32	120.1
C13—C12—H12	120.2	C31—C32—H32	120.1
C12—C13—C14	124.41 (13)	C32—C33—C34	124.05 (14)
C12—C13—N13	115.35 (13)	C32—C33—N33	115.50 (13)
C14—C13—N13	120.23 (13)	C34—C33—N33	120.45 (13)
O12—N13—O11	122.77 (13)	O31—N33—O32	121.58 (14)
O12—N13—C13	118.72 (13)	O31—N33—C33	119.31 (14)
O11—N13—C13	118.51 (12)	O32—N33—C33	119.11 (13)
C15—C14—C13	113.94 (13)	C33—C34—C35	114.23 (14)
C15—C14—C141	120.27 (14)	C33—C34—C341	127.08 (14)
C13—C14—C141	125.79 (13)	C35—C34—C341	118.67 (14)
C14—C141—H4A	109.5	C34—C341—H41G	109.5
C14—C141—H4B	109.5	C34—C341—H41H	109.5
H4A—C141—H4B	109.5	H41G—C341—H41H	109.5
C14—C141—H41C	109.5	C34—C341—H41I	109.5
H4A—C141—H41C	109.5	H41G—C341—H41I	109.5
H4B—C141—H41C	109.5	H41H—C341—H41I	109.5
C16—C15—C14	123.22 (14)	C36—C35—C34	122.88 (14)
C16—C15—H15	118.4	C36—C35—H35	118.6
C14—C15—H15	118.4	C34—C35—H35	118.6
C15—C16—C11	121.32 (14)	C35—C36—C31	121.11 (14)
C15—C16—H16	119.3	C35—C36—H36	119.4
C11—C16—H16	119.3	C31—C36—H36	119.4
N21—C21—C22	121.32 (14)	N41—C41—C42	120.97 (15)
N21—C21—C26	121.23 (13)	N41—C41—C46	121.28 (15)
C22—C21—C26	117.43 (14)	C42—C41—C46	117.74 (15)
C21—N21—H21A	120.0	C41—N41—H41A	120.0
C21—N21—H21B	120.0	C41—N41—H41B	120.0
H21A—N21—H21B	120.0	H41A—N41—H41B	120.0
C23—C22—C21	119.62 (14)	C43—C42—C41	119.90 (15)
C23—C22—H22	120.2	C43—C42—H42	120.0
C21—C22—H22	120.2	C41—C42—H42	120.0
C22—C23—C24	124.79 (13)	C42—C43—C44	123.97 (14)
C22—C23—N23	115.23 (13)	C42—C43—N43	115.17 (14)
C24—C23—N23	119.96 (13)	C44—C43—N43	120.86 (14)
O22—N23—O21	122.34 (13)	O41—N43—O42	121.87 (15)
O22—N23—C23	119.19 (13)	O41—N43—C43	118.90 (15)
O21—N23—C23	118.47 (12)	O42—N43—C43	119.22 (14)
C23—C24—C25	113.72 (13)	C43—C44—C45	114.30 (14)
C23—C24—C241	126.46 (13)	C43—C44—C441	127.04 (14)
C25—C24—C241	119.82 (14)	C45—C44—C441	118.65 (14)
C24—C241—H41D	109.5	C44—C441—H41J	109.5
C24—C241—H41E	109.5	C44—C441—H41K	109.5
H41D—C241—H41E	109.5	H41J—C441—H41K	109.5
C24—C241—H41F	109.5	C44—C441—H41L	109.5
H41D—C241—H41F	109.5	H41J—C441—H41L	109.5
H41E—C241—H41F	109.5	H41K—C441—H41L	109.5
C26—C25—C24	123.14 (14)	C46—C45—C44	123.15 (14)
C26—C25—H25	118.4	C46—C45—H45	118.4
C24—C25—H25	118.4	C44—C45—H45	118.4
C25—C26—C21	121.21 (14)	C45—C46—C41	120.90 (14)
C25—C26—H26	119.4	C45—C46—H46	119.6
C21—C26—H26	119.4	C41—C46—H46	119.6
N11—C11—C12—C13	178.79 (13)	N31—C31—C32—C33	−178.08 (14)
C16—C11—C12—C13	−3.2 (2)	C36—C31—C32—C33	1.4 (2)
C11—C12—C13—C14	1.6 (2)	C31—C32—C33—C34	0.0 (2)
C11—C12—C13—N13	−178.72 (12)	C31—C32—C33—N33	−179.72 (12)
C12—C13—N13—O12	148.69 (13)	C32—C33—N33—O31	171.83 (14)
C14—C13—N13—O12	−31.61 (19)	C34—C33—N33—O31	−7.9 (2)
C12—C13—N13—O11	−30.97 (18)	C32—C33—N33—O32	−8.3 (2)
C14—C13—N13—O11	148.72 (13)	C34—C33—N33—O32	171.98 (14)
C12—C13—C14—C15	0.9 (2)	C32—C33—C34—C35	−1.0 (2)
N13—C13—C14—C15	−178.74 (12)	N33—C33—C34—C35	178.68 (12)
C12—C13—C14—C141	−179.44 (14)	C32—C33—C34—C341	177.66 (14)
N13—C13—C14—C141	0.9 (2)	N33—C33—C34—C341	−2.7 (2)
C13—C14—C15—C16	−1.9 (2)	C33—C34—C35—C36	0.7 (2)
C141—C14—C15—C16	178.47 (13)	C341—C34—C35—C36	−178.06 (13)
C14—C15—C16—C11	0.3 (2)	C34—C35—C36—C31	0.6 (2)
N11—C11—C16—C15	−179.65 (13)	N31—C31—C36—C35	177.80 (14)
C12—C11—C16—C15	2.3 (2)	C32—C31—C36—C35	−1.6 (2)
N21—C21—C22—C23	178.64 (12)	N41—C41—C42—C43	−177.50 (16)
C26—C21—C22—C23	−2.9 (2)	C46—C41—C42—C43	1.3 (2)
C21—C22—C23—C24	1.3 (2)	C41—C42—C43—C44	0.5 (2)
C21—C22—C23—N23	−179.86 (12)	C41—C42—C43—N43	−179.26 (14)
C22—C23—N23—O22	152.31 (13)	C42—C43—N43—O41	175.87 (17)
C24—C23—N23—O22	−28.77 (19)	C44—C43—N43—O41	−3.9 (2)
C22—C23—N23—O21	−27.94 (18)	C42—C43—N43—O42	−5.5 (2)
C24—C23—N23—O21	150.98 (13)	C44—C43—N43—O42	174.72 (15)
C22—C23—C24—C25	1.39 (19)	C42—C43—C44—C45	−1.5 (2)
N23—C23—C24—C25	−177.42 (12)	N43—C43—C44—C45	178.25 (13)
C22—C23—C24—C241	−179.54 (13)	C42—C43—C44—C441	177.30 (15)
N23—C23—C24—C241	1.7 (2)	N43—C43—C44—C441	−3.0 (2)
C23—C24—C25—C26	−2.5 (2)	C43—C44—C45—C46	0.7 (2)
C241—C24—C25—C26	178.37 (13)	C441—C44—C45—C46	−178.16 (14)
C24—C25—C26—C21	1.0 (2)	C44—C45—C46—C41	1.0 (2)
N21—C21—C26—C25	−179.67 (13)	N41—C41—C46—C45	176.78 (16)
C22—C21—C26—C25	1.8 (2)	C42—C41—C46—C45	−2.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O11^i	0.88	2.38	3.236 (2)	163
N21—H21B···O21^ii	0.88	2.42	3.256 (2)	158
N31—H31B···O31^i	0.88	2.31	3.099 (2)	148
N41—H41B···O41^ii	0.88	2.39	3.174 (2)	149
N41—H41A···O21^iii	0.88	2.49	3.308 (2)	154

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