High- and low-temperature phases in isostructural 4-chloro-3-nitro­aniline and 4-iodo-3-nitro­aniline

The structures of 4-chloro-3-nitro­aniline, C₆H₅ClN₂O₂, (I), and 4-iodo-3-nitro­aniline, C₆H₅IN₂O₂, (II), are isomorphs and both undergo continuous (second order) phase transitions at 237 and 200 K, respectively. The structures, as well as their phase transitions, have been studied by single-crystal X-ray diffraction, Raman spectroscopy and difference scanning calorimetry experiments. Both high-temperature phases (293 K) show disorder of the nitro substituents, which are inclined towards the benzene-ring planes at two different orientations. In the low-temperature phases (120 K), both inclination angles are well maintained, while the disorder is removed. Concomitantly, the b axis doubles with respect to the room-temperature cell. Each of the low-temperature phases of (I) and (II) contains two pairs of independent mol­ecules, where the mol­ecules in each pair are related by noncrystallographic inversion centres. The mol­ecules within each pair have the same absolute value of the inclination angle. The Flack parameter of the low-temperature phases is very close to 0.5, indicating inversion twinning. This can be envisaged as stacking faults in the low-temperature phases. It seems that competition between the primary amine–nitro N—H...O hydrogen bonds which form three-centred hydrogen bonds is the reason for the disorder of the nitro groups, as well as for the phase transition in both (I) and (II). The backbones of the structures are formed by N—H...N hydrogen bonding of mod­erate strength which results in the graph-set motif C(3). This graph-set motif forms a zigzag chain parallel to the monoclinic b axis and is maintained in both the high- and the low-temperature structures. The primary amine groups are pyramidal, with similar geometric values in all four determinations. The high-temperature phase of (II) has been described previously [Garden et al. (2004). Acta Cryst. C60, o328–o330].

S1. Introduction

The title structures have been selected as suitable candidates for the determination of criteria for the geometric constraints of primary amine groups (Cooper et al., 2010). The configuration of the primary amine substituent, including the C atom to which it is attached, may be either planar or pyramidal. The C—N distance correlates with the valence angles C—N—H and H—N—H of the primary amine group (Figs. 1 and 2). With a short C—N distance of about 1.32 Å, the primary amine group tends to be coplanar with the plane of the aromatic ring to which the amine group is attached. For such cases, the N atom can be considered to be in the pure sp²-hydridized state. On the other hand, the primary amine group tends to be pyramidal for longer C—N distances (about 1.38 Å and longer) which corresponds to an increasing sp³ character of the N atom. Allen et al. (1987) have listed somewhat larger values [1.36 (2) and 1.394 (11) Å] for the C_aryl—NH₂ bonds with the N atom in sp²- and sp³-hybridized states, respectively.

S2. Experimental

S2.1. Synthesis and crystallization

All the compounds are commercially available (Sigma–Aldrich). In each case, 100 mg was dissolved in 3 ml of a 50% (v/v) ethanol solution at 323 K in a probe with a diameter of 12 mm tapped with cotton wool. Yellow–brown plates with an elongated direction were obtained for each compound over the course of 3 d at room temperature. The elongated directions of the crystals of (I) and (II) coincided with the direction of the monoclinic axis. The limiting faces were (101), (101), (102), (102), (010) and (010). In the case of the low-temperature phase of (I), the measured crystal seemed to have been split. Processing the diffraction images with a broad integration mask resulted in reasonable data.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All the H atoms could be discerned in difference electron-density maps. Nevertheless, the aryl H atoms have been constrained in the riding-atom approximation, with aryl C—H = 0.93 or 0.95 Å for the room- and low-temperature phases, respectively, with U_iso(H) = 1.2U_eq(C). The primary amine H atoms were restrained to N—H = 0.880 (1) Å and the isotropic displacement parameters set at U_iso(H) = 1.2U_eq(N).

The low-temperature phases of (I) and (II) are composed of four independent molecules. These molecules can be grouped into two pairs related by noncrystallographic inversion centres. Such a model has been applied for the refinement of the low-temperature structure of (II) because the alternative refinement of all the independent molecules resulted in some nonpositive definite displacement parameters. Therefore, the atomic parameters of just one molecule from each pair have been refined together with the positional parameters of the molecules. Thus, the atomic parameters were common to the pairs of the molecules a and b as well as for the molecules c and d (Fig. 8).

In the case of the low-temperature phase of (I), the preference was given to the independent refinement of all four independent molecules (Fig. 7) on the basis of the Hamilton test: R = 1.158, dimension of the hypothesis = 198; number of degrees of freedom = 4593 (Hamilton, 1965; Inter­national Tables for X-ray Crystallography, Vol. IV, 1974). [The constrained refinement with two independent molecules converged to the indicators of the refinement R_obs = 0.0276, wR_obs = 0.0749, R_all = 0.0295, wR_all = 0.0761, S_all = 2.20, S_obs = 2.23, number of parameters = 223.]

The Raman spectra of the single-crystal samples (Figs. 15 and 16) were collected using a Renishaw microscope spectrometer with a 788 and 633 nm excitation for (I) and (II), respectively, in a standard backscattering configuration for the range of 100–2000 cm^-1. The excitation power at the sample was 15 mW for each compound. The spectra were recorded using polarized laser light and with an analyzer perpendicular (VH) or parallel (VV) to the polarization of the incident light.

(I) and (II) were measured by differential scanning calorimetry several times both on heating and on cooling at a rate of 10 K min^-1. We used Perkin–Elmer DSC 7 and Perkin–Elmer Pyris Diamond DSC for the temperature ranges from 93 to 323 K and from 213 K to the melting temperatures, respectively. A tiny reproducible hump was observed for (I) at 237 K both on heating and on cooling. The shape of the anomaly has indicated a second order phase transition. (I) melts at 378 K. In the case of (II), no reproducible anomalies were observed; it melts at 413 K.

S3. Results and discussion

It turned out that the primary amine groups in the title structures (Figs. 3, 4, 5 and 6) have pyramidal configurations which fit well with the dependence of the average valence angles C—N—H on the C—N distance in the primary amine group (Fig. 1).

The dependence of the H—N—H angle on the C—N distance is somewhat less clear (Fig. 2). In the case of the low-temperature phase of (I), the C—N distances are split into two categories which differ by about 0.02 Å (Table 2). The molecules within the columns along the b axis (Fig. 7) belong to the same category irrespective of the inclination of the nitro group towards the benzene ring (see below). The C4x—Clx distances (where x is a, b, c or d) can also be divided into the same categories (Table 2).

The peculiarity of the low-temperature phases of (I) and (II) follows from presence of four symmetry-independent molecules in these structures (Figs. 7, 8, 9 and 10). These four independent molecules can be grouped into two pairs of the conformers which involve the N atoms N1a—N1b and N1c—N1d (Fig. 7). The conformers differ significantly by the inclination of the nitro group with respect to the benzene ring (Fig. 7 and Table 3). The conformers with the specific absolute value of the inclination angle of the nitro group are related by the noncrystallographic inversion centres.

These noncrystallographic inversion centres are situated at the approximate locations (1/2, 3/8, 1/2), (1/2, 7/8, 1/2), (0, 1/8, 0), (0, 5/8, 0), (0, 1/8, 1/2), (0, 5/8, 1/2), (1/2, 1/8, 0) and (1/2, 5/8, 0).

Provided that the b axis is halved with respect to the unit cell of the low-temperature phases of (I) and (II), the positions of these inversion centres convert to the orbit which is pertinent to P2₁/n. (This transformation is accompanied by the shift by 0, 1/4, 0 with respect of the origin of the unit cell of the low-temperature phase.) Halving the unit-cell axis b means that the diffractions with k = 2n+1 are either not observable or they are ignored. Such a description of the structure in the unit-cell axis with b halved might result in a model with the disordered nitro groups since the respective halves of the large unit cell with 0 〈 y and y 〉 are overlapped. Indeed, this is the case with the room-temperature structure of the iodo isomer reported by Garden et al. (2004), as well as with the present room-temperature structures of (I) (Fig. 11) and (II) (Fig. 12) [cf. the room-temperature phases and gradual development of the diffractions with k = 2n+1 in (I) and (II) (Figs. 13 and 14)].

In addition, there are further noncrystallographic inversion centres present in the title low-temperature structures of (I) and (II) at the approximate locations (3/4, 0.1, 3/4), (3/4, 0.6, 3/4), (3/4, 0.1, 1/4), (3/4, 0.6, 1/4), (1/4, 0.4, 1/4), (1/4, 0.9, 1/4), (1/4, 0.4, 3/4) and (1/4, 0.9, 3/4).

There are just two preferred positions of the disordered nitro groups in both room-temperature phases. The inclination angles of the nitro groups with regard to the benzene-ring planes change minutely during the phase transitions both in (I) and (II) (Table 3). The driving force for the resolution of both conformers in the low-temperature phase seems to be the competition of the three-centreed hydrogen bonds between the primary amine H atom and both O atoms of the nitro­gen group (cf. Figs. 9–12 and Tables 4–7). During cooling, both alternatives resolve while forming longer chains as it can be judged from gradual development of the Bragg diffractions during cooling (Figs. 13 and 14). The inversion twinning in the low-temperature phases is equivalent to the stacking faults. For example, when instead of N1d follows the molecule which has the same conformation of the nitro group as in N1a (Fig. 7). This suggested mechanism agrees with the value of the Flack parameters close to 0.5 in both compounds.

The Raman spectra are shown in Figs. 15 and 16 for (I) and (II), respectively. The slight changes in intensity and positions of the spectral lines also reveal gradual structural change during cooling. The spectra show that for (II), a larger temperature inter­val is spanned during which the diffractions with k = 2n+1 develop in comparison with (I); cf. Figs. 13 and 14.

All the hydrogen bonds in (I) and (II) are weak–moderate or weak (Gilli & Gilli, 2009; Tables 4–7). In the high- as well as in the low-temperature phases of (I) and (II), the primary amine–primary amine N—H···N hydrogen bonds form chains with the graph-set motif C(3) (Etter et al., 1990; Figs. 9–12). The chains are oriented along the b axis. This hydrogen-bond pattern is a backbone of the structure. The zigzag chain which is formed by this hydrogen-bond pattern is oriented along theb axis. The remaining hydrogen bonds are of the N—H···O type. They are either two- or three-centred (bifurcated; Jeffrey, 1995).

In the low-temperature phase of (I), 4958 Friedel (noncentrosymmetric) pairs were measured; 56 measured diffractions did not have the corresponding counterpart -h,-k,-l or h,-k,l or -h,k,-l. The Friedel coverage is thus 4198/[(4198 + 56) = 0.99 (Flack et al., 2006; Spek, 2009).

In the low-temperature phase of (II), 4883 Friedel (noncentrosymmetric) pairs were measured; 232 measured diffractions did not have the corresponding counterpart as given above. The Friedel coverage is thus 4883/[(4883 + 232) = 0.95.

Flack et al. (2006), as well as Flack & Bernardinelli (2008), found estimation of the value of the standard uncertainty of the Flack parameter from the calculated value of Friedif. Because of the presence of the pseudo-inversion centres that link every second molecule a half of the content of the unit cell can be considered as centrosymmetric and, as a consequence, would lower the value of Friedif. Then the value of Friedif-centro (Flack & Bernardinelli, 2008) would be 465 for the low-temperature chloro (Cu Kα radiation) and 284 for the iodo (Mo Kα radiation) isomers. However, the other set of the inversion centres (~3/4, ~0.1, ~3/4 etc., see the text above) is present in the structure which would also decrease the value of Friedif-centro. Moreover, translational pseudosymmetry is also present in the low-temperature phases of (I) and (II). This translational pseudosymmetry is dominantly disturbed by the differently inclined nitro groups that alternate along the b axis. Thus it is just one half of the O atoms pertinent to the nitro groups that is considered to be the part of the noncentrosymmetric substructure. Then, Friedif-centro = 195 for the chloro (Cu Kα radiation) and 123 for the iodo isomers (Mo Kα radiation). The corresponding standard uncertainties would be 0.041 and 0.065 (Flack et al., 2006; Flack & Bernardinelli, 2008). The refined values of the Flack parameter converged to the values 0.504 (15) and 0.41 (13) for the chloro and iodo compounds, respectively. While the standard uncertainty of the Flack parameter in the low-temperature phase of (I) is considerably lower than the expe­cta­tion the opposite is true for the low-temperature phase of (II). The standard uncertainty of the low-temperature phase of (I) indicates reliable determination of the Flack parameter (Flack & Bernardinelli, 2000), while it is not the case for the isomer (II). On the other hand, chemical similarity between both isomers, especially the hydrogen-bond pattern, rather supports the view that even the low-temperature iodo isomer is an inversion twin with about equal volume proportions of the inversion-related twin domain states.

R_A = 0.0361 and R_A = 0.0710 for the low-temperature phases of (I) and (II), respectively, while R_D = 1.0003 and R_A = 1.0000 for the respective structures. (The factors R_A and R_D were defined by Flack et al., 2011.)

4-Bromo-3-nitro­aniline is most probably isostructural with the title structures and an analogous phase transition is expected to be present in this compound. On the other hand, the structure of 4-fluoro-3-nitro­aniline differs from the title compounds as it has been discovered recently (Fábry et al., 2014).

Related literature

For related literature, see: Allen et al. (1987); Cooper et al. (2010); Etter et al. (1990); Fábry et al. (2014); Flack & Bernardinelli (2000, 2008); Flack et al. (2006, 2011); Garden et al. (2004); Gilli & Gilli (2009); Hamilton (1965); Jeffrey (1995); Spek (2009).

Computing details

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: JANA2006 (Petříček et al., 2014). Molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2010) for (Ia), (Ib), (IIa); PLATON (Spek, 2009) and DIAMOND(Brandenburg & Putz, 2010) for (IIb).

Figures

	Fig. 1. The C—N distance (Å) versus average C—N—H angle (°) in the structures retrieved from the Cambridge Structural Database [CSD; Version 5.34 of November 2012, with addenda from February and May 2013 (Allen, 2002); 547174 hits], as well as in the title structures. The horizontal lines about 109.54 and 120° are a clear geometry constraint artifact. The title structures are indicated by coloured symbols. The plot was constructed using Origin6.1 (OriginLab Corporation, 2000).
	Fig. 2. The average C—N distance (Å) versus H—N—H angle (°) in the structures retrieved from the CSD, as well as in the title structures. The horizontal lines about 109.54 and 120° are a clear geometry constraint artifact. The title structures are indicated by coloured symbols. The plot was constructed using Origin6.1 (OriginLab Corporation, 2000).
	Fig. 3. The molecule of the room-temperature phase of (I). The nitro substituent is disordered over two orientations. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The molecules of the low-temperature phase of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. The molecules of the room-temperature phase of (II). The nitro substituent is disordered over two orientations. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 6. The molecules of the low-temperature phase of (II). The pairs of molecules which bear the labels "A", "B" and "C", "D" are related by pseudo-inversion centres of symmetry. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 7. The four independent molecules of the low-temperature phase of (I) and their location in the unit cell. The molecules are discerned by the labels of the representative amine N atoms. Note that the molecules which differ by the inclination of the nitro group alternate above each other in the direction of the b axis. Colour code: C grey, Cl green, N blue, O red and H grey.
	Fig. 8. The four independent molecules of the low-temperature phase of (II) and their location in the unit cell. Colour code: C grey, I magenta, N blue, O red and H grey.
	Fig. 9. The contents of the unit-cell of the low-temperature phase of (I), showing the hydrogen-bond pattern. Colour code: C grey, Cl green, N blue, O red and H grey.
	Fig. 10. The contents of the unit-cell of the low-temperature phase of (II), showing the hydrogen-bond pattern. Colour code: C grey, I magenta, N blue, O red and H grey.
	Fig. 11. The contents of the unit-cell of the room-temperature phase of (I), showing the hydrogen-bond pattern. Colour code: C grey, Cl green, N blue, O red and H grey.
	Fig. 12. The contents of the unit-cell of the room-temperature phase of (II), showing the hydrogen-bond pattern. Colour code: C grey, I magenta, N blue, O red and H grey.
	Fig. 13. The gradual development of the diffractions h1l during cooling at (a) 260, (b) 255, (c) 250, (d) 245, (e) 240 and (f) 235 K in (I). (The indices h1l are related to the unit cell of the low-temperature phase.)
	Fig. 14. The gradual development of the diffractions h1l during cooling at (a) 230, (b) 225, (c) 220, (d 215, (e) 210, (f) 205, (g) 200, (h) 195 and (i) 190 K in (II). (The indices h1l are related to the unit cell of the low-temperature phase; there are also present diffractions from a parasitic crystal.) The onset of the diffractions h1l takes place about 200 K.
	Fig. 15. The Raman spectrum of (I). The spectrum has been detected at HV geometry (polarization of excitation light was in the mirror plane while analyzer was parallel to the monoclinic axis). The spectrum is divided into intervals because of strong luminiscence background.
	Fig. 16. The Raman spectrum of (II). The spectrum has been detected at HV geometry (polarization of excitation light was in the mirror plane while analyzer was parallel to the monoclinic axis). The spectrum is divided into intervals because of strong luminiscence background.

(Ia) 4-Chloro-3-nitroaniline

Crystal data

C6H5ClN2O2	F(000) = 352
Mr = 172.6	Dx = 1.551 Mg m^−3
Monoclinic, P21/n	Melting point: 378 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.5418 Å
a = 12.8800 (9) Å	Cell parameters from 2275 reflections
b = 4.0398 (3) Å	θ = 3.8–66.0°
c = 15.2317 (11) Å	µ = 4.19 mm^−1
β = 111.263 (7)°	T = 293 K
V = 738.59 (10) Å^3	Prism, yellow
Z = 4	0.45 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Gemini ultra) diffractometer	1298 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	975 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 5.1892 pixels mm^-1	θmax = 67.2°, θmin = 3.9°
ω scans	h = −15→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −4→4
Tmin = 0.327, Tmax = 0.433	l = −16→18
4809 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
wR(F^2) = 0.111	(Δ/σ)max = 0.042
S = 1.92	Δρmax = 0.33 e Å^−3
1298 reflections	Δρmin = −0.24 e Å^−3
125 parameters	Extinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
2 restraints	Extinction coefficient: 690 (180)
14 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1a	0.30128 (8)	0.3087 (2)	0.36231 (6)	0.0945 (4)
C1a	0.32455 (19)	−0.1016 (6)	0.64561 (16)	0.0537 (10)
C2a	0.2251 (2)	−0.1268 (6)	0.56950 (17)	0.0562 (10)
H1c2a	0.164002	−0.228885	0.57684	0.0674*
C3a	0.2162 (2)	−0.0013 (6)	0.48293 (17)	0.0575 (10)
C4a	0.3054 (2)	0.1498 (6)	0.46879 (18)	0.0607 (11)
C5a	0.4041 (2)	0.1750 (7)	0.54566 (19)	0.0626 (11)
H1c5a	0.465208	0.277512	0.538478	0.0715*
C6a	0.4136 (2)	0.0522 (7)	0.63187 (18)	0.0596 (10)
H1c6a	0.480976	0.072345	0.682187	0.0752*
N1a	0.3323 (2)	−0.2150 (7)	0.73375 (16)	0.0705 (10)
H1n1a	0.286 (2)	−0.377 (5)	0.732 (2)	0.0846*
H2n1a	0.4023 (8)	−0.248 (7)	0.7701 (18)	0.0846*
N2a	0.1075 (2)	−0.0389 (9)	0.40661 (19)	0.0833 (13)
O1a	0.0671 (6)	0.187 (2)	0.3629 (6)	0.170 (4)	0.5
O2a	0.0605 (5)	−0.3049 (17)	0.4061 (5)	0.119 (3)	0.5
O1d	0.1014 (4)	−0.0481 (15)	0.3223 (3)	0.091 (2)	0.5
O2d	0.0244 (4)	−0.066 (2)	0.4256 (4)	0.120 (3)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1a	0.1369 (8)	0.0901 (7)	0.0635 (5)	0.0083 (5)	0.0446 (5)	0.0114 (4)
C1a	0.0508 (13)	0.0582 (16)	0.0494 (14)	0.0061 (11)	0.0147 (11)	−0.0049 (11)
C2a	0.0485 (13)	0.0614 (16)	0.0573 (15)	0.0025 (11)	0.0176 (11)	−0.0039 (12)
C3a	0.0537 (14)	0.0592 (16)	0.0494 (14)	0.0113 (12)	0.0064 (11)	−0.0078 (11)
C4a	0.0795 (18)	0.0517 (16)	0.0532 (15)	0.0078 (12)	0.0268 (14)	−0.0015 (11)
C5a	0.0638 (16)	0.0608 (17)	0.0673 (17)	−0.0065 (12)	0.0286 (14)	−0.0075 (13)
C6a	0.0502 (14)	0.0668 (18)	0.0560 (15)	−0.0005 (11)	0.0124 (12)	−0.0100 (12)
N1a	0.0654 (15)	0.0917 (19)	0.0500 (13)	0.0038 (12)	0.0158 (11)	0.0075 (12)
N2a	0.0701 (18)	0.091 (2)	0.0667 (18)	0.0124 (16)	−0.0012 (14)	−0.0060 (15)
O1a	0.130 (5)	0.142 (6)	0.154 (7)	0.017 (5)	−0.047 (5)	0.073 (6)
O2a	0.083 (4)	0.105 (5)	0.117 (5)	−0.003 (4)	−0.026 (3)	−0.007 (4)
O1d	0.092 (3)	0.113 (4)	0.043 (2)	0.010 (3)	−0.005 (2)	−0.005 (2)
O2d	0.052 (3)	0.197 (8)	0.092 (4)	0.011 (3)	0.005 (3)	−0.027 (4)

Geometric parameters (Å, º)

Cl1a—C4a	1.727 (3)	C5a—H1c5a	0.93
C1a—C2a	1.385 (3)	C5a—C6a	1.367 (4)
C1a—C6a	1.385 (4)	C6a—H1c6a	0.93
C1a—N1a	1.387 (4)	N1a—H1n1a	0.88 (3)
C2a—H1c2a	0.93	N1a—H2n1a	0.880 (12)
C2a—C3a	1.378 (4)	N2a—O1a	1.137 (8)
C3a—C4a	1.385 (4)	N2a—O2a	1.231 (8)
C3a—N2a	1.468 (3)	N2a—O1d	1.259 (6)
C4a—C5a	1.385 (3)	N2a—O2d	1.210 (7)
Cl1a—C4a—C3a	124.43 (18)	H1c5a—C5a—C6a	119.34
Cl1a—C4a—C5a	118.2 (2)	C1a—C6a—C5a	121.2 (2)
C2a—C1a—C6a	118.1 (2)	C1a—C6a—H1c6a	119.42
C2a—C1a—N1a	120.4 (2)	C5a—C6a—H1c6a	119.42
C6a—C1a—N1a	121.4 (2)	C1a—N1a—H1n1a	114 (2)
C1a—C2a—H1c2a	119.86	C1a—N1a—H2n1a	110.9 (18)
C1a—C2a—C3a	120.3 (3)	H1n1a—N1a—H2n1a	116 (2)
H1c2a—C2a—C3a	119.86	C3a—N2a—O1a	118.9 (5)
C2a—C3a—C4a	121.7 (2)	C3a—N2a—O2a	114.9 (4)
C2a—C3a—N2a	116.3 (3)	C3a—N2a—O1d	120.0 (4)
C4a—C3a—N2a	122.0 (2)	C3a—N2a—O2d	119.5 (3)
C3a—C4a—C5a	117.4 (3)	O1a—N2a—O2a	125.2 (5)
C4a—C5a—H1c5a	119.34	O1d—N2a—O2d	120.5 (4)
C4a—C5a—C6a	121.3 (3)
H1n1a—N1a—C1a—C2a	28 (2)	H2n1a—N1a—C1a—C6a	−22 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1a—H1n1a···N1a^i	0.88 (3)	2.25 (3)	3.096 (4)	162 (3)
N1a—H2n1a···O1a^ii	0.880 (12)	2.73 (2)	3.512 (8)	148 (2)
N1a—H2n1a···O2a^ii	0.880 (12)	2.330 (18)	3.153 (6)	156 (2)
N1a—H2n1a···O1d^ii	0.880 (12)	2.531 (15)	3.369 (5)	159 (2)
N1a—H2n1a···O2d^ii	0.880 (12)	2.44 (2)	3.193 (6)	144 (2)

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

(Ib) 4-Chloro-3-nitroaniline

Crystal data

C6H5ClN2O2	F(000) = 704
Mr = 172.6	Dx = 1.605 Mg m^−3
Monoclinic, Pn	Melting point: 378 K
Hall symbol: P -2yac	Cu Kα radiation, λ = 1.5418 Å
a = 12.7260 (4) Å	Cell parameters from 14208 reflections
b = 7.9721 (2) Å	θ = 3.1–67.0°
c = 15.0098 (4) Å	µ = 4.34 mm^−1
β = 110.352 (3)°	T = 120 K
V = 1427.73 (7) Å^3	Plate, brown
Z = 8	0.45 × 0.13 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Gemini ultra) diffractometer	5014 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	4733 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 10.3784 pixels mm^-1	θmax = 67.1°, θmin = 3.9°
ω scans	h = −15→15
Absorption correction: analytical CrysAlis PRO (Agilent Technologies, 2012)	k = −9→8
Tmin = 0.362, Tmax = 0.781	l = −17→17
23718 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
S = 1.94	(Δ/σ)max = 0.050
5014 reflections	Δρmax = 0.17 e Å^−3
423 parameters	Δρmin = −0.16 e Å^−3
8 restraints	Extinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
58 constraints	Extinction coefficient: 960 (90)
Primary atom site location: structure-invariant direct methods	Absolute structure: 2479 of Friedel pairs used in the refinement
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.504 (15)

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

	x	y	z	Uiso*/Ueq
Cl1a	0.28699 (7)	0.28021 (9)	0.37138 (6)	0.0321 (3)
C1a	0.3155 (3)	0.0653 (4)	0.6595 (2)	0.0191 (10)
C2a	0.2150 (3)	0.0498 (3)	0.5829 (2)	0.0190 (10)
H1c2a	0.153566	−0.009085	0.59015	0.0228*
C3a	0.2056 (2)	0.1196 (4)	0.4978 (2)	0.0205 (9)
C4a	0.2957 (3)	0.2023 (3)	0.4824 (2)	0.0224 (11)
C5a	0.3940 (3)	0.2134 (3)	0.5585 (3)	0.0244 (12)
H1c5a	0.456625	0.267598	0.550534	0.0261*
C6a	0.4044 (2)	0.1488 (4)	0.6455 (2)	0.0217 (9)
H1c6a	0.473191	0.160982	0.697011	0.0293*
N1a	0.3216 (2)	0.0066 (5)	0.74874 (19)	0.0253 (8)
H1n1a	0.2812 (18)	−0.0858 (18)	0.7380 (18)	0.0304*
H2n1a	0.3889 (9)	0.013 (3)	0.7923 (14)	0.0304*
N2a	0.0954 (2)	0.1050 (3)	0.41968 (18)	0.0257 (9)
O1a	0.05508 (18)	0.2288 (2)	0.37495 (16)	0.0438 (6)
O2a	0.05060 (18)	−0.03283 (19)	0.40980 (15)	0.0348 (5)
Cl1b	0.68085 (8)	0.46899 (9)	0.64354 (6)	0.0312 (3)
C1b	0.6525 (3)	0.6864 (4)	0.3560 (2)	0.0194 (10)
C2b	0.7534 (3)	0.6969 (4)	0.4320 (2)	0.0211 (10)
H1c2b	0.816095	0.751625	0.424462	0.0253*
C3b	0.7617 (3)	0.6258 (4)	0.5197 (2)	0.0199 (9)
C4b	0.6739 (3)	0.5467 (3)	0.5348 (2)	0.0210 (10)
C5b	0.5715 (3)	0.5377 (3)	0.4586 (2)	0.0215 (11)
H1c5b	0.50875	0.485337	0.467308	0.0273*
C6b	0.5615 (2)	0.6050 (4)	0.3705 (2)	0.0227 (10)
H1c6b	0.492197	0.595903	0.319252	0.0257*
N1b	0.6437 (2)	0.7475 (5)	0.2682 (2)	0.0231 (8)
H1n1b	0.6961 (15)	0.814 (2)	0.2624 (17)	0.0277*
H2n1b	0.5758 (9)	0.780 (3)	0.2332 (16)	0.0277*
N2b	0.8713 (2)	0.6389 (3)	0.59283 (18)	0.0254 (9)
O1b	0.91371 (19)	0.5118 (2)	0.63758 (16)	0.0428 (6)
O2b	0.91796 (19)	0.77623 (19)	0.60795 (15)	0.0370 (5)
Cl1c	0.67829 (7)	−0.04585 (9)	0.64328 (6)	0.0290 (3)
C1c	0.6569 (3)	0.1806 (4)	0.3591 (2)	0.0196 (10)
C2c	0.7574 (3)	0.1892 (4)	0.4359 (2)	0.0210 (10)
H1c2c	0.821189	0.240198	0.428176	0.0252*
C3c	0.7649 (2)	0.1231 (3)	0.5244 (2)	0.0191 (9)
C4c	0.6753 (3)	0.0461 (3)	0.5388 (3)	0.0201 (10)
C5c	0.5742 (3)	0.0347 (3)	0.4609 (2)	0.0206 (10)
H1c5c	0.511289	−0.019018	0.468634	0.0272*
C6c	0.5651 (2)	0.1006 (4)	0.3733 (2)	0.0227 (10)
H1c6c	0.4959	0.0919	0.321895	0.0247*
N1c	0.6488 (2)	0.2408 (5)	0.2715 (2)	0.0240 (8)
H1n1c	0.6990 (16)	0.311 (2)	0.2649 (18)	0.0288*
H2n1c	0.5804 (10)	0.269 (3)	0.2356 (16)	0.0288*
N2c	0.8742 (2)	0.1387 (3)	0.59792 (18)	0.0254 (9)
O1c	0.88096 (18)	0.14124 (18)	0.68251 (14)	0.0318 (5)
O2c	0.95769 (18)	0.1515 (2)	0.57504 (16)	0.0355 (6)
Cl1d	0.28099 (7)	0.78868 (9)	0.36544 (6)	0.0280 (3)
C1d	0.3034 (3)	0.5644 (4)	0.6503 (2)	0.0189 (9)
C2d	0.2020 (3)	0.5556 (3)	0.5741 (2)	0.0183 (10)
H1c2d	0.138755	0.504241	0.582547	0.022*
C3d	0.1931 (2)	0.6205 (4)	0.4873 (2)	0.0199 (9)
C4d	0.2849 (3)	0.6988 (3)	0.4724 (2)	0.0217 (10)
C5d	0.3827 (3)	0.7096 (3)	0.5493 (3)	0.0227 (11)
H1c5d	0.445357	0.764634	0.541822	0.0249*
C6d	0.3933 (2)	0.6439 (4)	0.6366 (2)	0.0207 (10)
H1c6d	0.462611	0.653088	0.68778	0.0272*
N1d	0.3092 (2)	0.5026 (5)	0.73903 (18)	0.0241 (8)
H1n1d	0.2639 (17)	0.416 (2)	0.7300 (17)	0.029*
H2n1d	0.3771 (9)	0.510 (3)	0.7817 (15)	0.029*
N2d	0.0832 (2)	0.6031 (3)	0.40978 (17)	0.0220 (8)
O1d	0.07890 (18)	0.59989 (19)	0.32793 (15)	0.0319 (5)
O2d	0.00109 (18)	0.5888 (2)	0.43467 (15)	0.0356 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1a	0.0431 (5)	0.0311 (4)	0.0249 (4)	0.0013 (3)	0.0154 (3)	0.0033 (3)
C1a	0.0152 (14)	0.0211 (12)	0.0208 (16)	0.0042 (10)	0.0059 (12)	−0.0016 (10)
C2a	0.0165 (13)	0.0177 (14)	0.0219 (16)	−0.0014 (9)	0.0055 (12)	−0.0024 (9)
C3a	0.0158 (13)	0.0204 (13)	0.0218 (16)	0.0014 (10)	0.0021 (11)	−0.0041 (10)
C4a	0.0325 (17)	0.0172 (15)	0.0189 (16)	0.0026 (10)	0.0107 (14)	−0.0002 (9)
C5a	0.0234 (16)	0.0206 (17)	0.0328 (19)	−0.0033 (10)	0.0142 (14)	−0.0059 (9)
C6a	0.0191 (14)	0.0256 (14)	0.0186 (14)	0.0020 (11)	0.0041 (11)	−0.0037 (10)
N1a	0.0241 (12)	0.0338 (13)	0.0166 (13)	0.0015 (11)	0.0053 (10)	0.0065 (10)
N2a	0.0264 (14)	0.0249 (13)	0.0208 (13)	0.0059 (10)	0.0020 (11)	−0.0013 (9)
O1a	0.0366 (9)	0.0361 (10)	0.0411 (9)	0.0041 (7)	−0.0088 (7)	0.0130 (7)
O2a	0.0275 (8)	0.0275 (9)	0.0368 (8)	−0.0031 (7)	−0.0048 (6)	−0.0048 (6)
Cl1b	0.0435 (5)	0.0308 (4)	0.0221 (4)	0.0008 (3)	0.0149 (3)	0.0051 (3)
C1b	0.0236 (16)	0.0191 (13)	0.0155 (14)	0.0034 (10)	0.0070 (12)	−0.0026 (10)
C2b	0.0187 (14)	0.0216 (15)	0.0235 (16)	0.0050 (10)	0.0080 (12)	0.0009 (10)
C3b	0.0254 (14)	0.0155 (13)	0.0160 (13)	0.0049 (10)	0.0039 (11)	−0.0008 (9)
C4b	0.0241 (15)	0.0188 (15)	0.0213 (15)	0.0018 (10)	0.0095 (13)	−0.0015 (9)
C5b	0.0218 (16)	0.0229 (17)	0.0212 (15)	−0.0016 (10)	0.0094 (13)	−0.0036 (9)
C6b	0.0167 (14)	0.0229 (15)	0.0279 (16)	−0.0002 (11)	0.0069 (12)	−0.0040 (11)
N1b	0.0159 (11)	0.0309 (12)	0.0198 (13)	0.0008 (10)	0.0027 (9)	−0.0010 (11)
N2b	0.0255 (13)	0.0274 (13)	0.0204 (13)	0.0007 (10)	0.0044 (10)	0.0009 (9)
O1b	0.0384 (9)	0.0368 (9)	0.0395 (9)	0.0071 (7)	−0.0040 (7)	0.0153 (7)
O2b	0.0307 (7)	0.0286 (9)	0.0384 (8)	−0.0022 (7)	−0.0049 (6)	−0.0043 (7)
Cl1c	0.0363 (4)	0.0307 (4)	0.0223 (3)	0.0000 (3)	0.0131 (3)	0.0018 (3)
C1c	0.0224 (16)	0.0188 (12)	0.0171 (14)	0.0037 (10)	0.0062 (12)	−0.0032 (10)
C2c	0.0180 (14)	0.0217 (14)	0.0244 (16)	0.0037 (10)	0.0087 (12)	−0.0002 (11)
C3c	0.0224 (14)	0.0171 (13)	0.0157 (13)	0.0039 (10)	0.0039 (10)	−0.0019 (9)
C4c	0.0200 (14)	0.0190 (15)	0.0223 (15)	0.0018 (10)	0.0088 (12)	−0.0014 (9)
C5c	0.0194 (15)	0.0221 (17)	0.0213 (15)	−0.0014 (10)	0.0084 (13)	−0.0032 (9)
C6c	0.0171 (14)	0.0230 (15)	0.0268 (16)	−0.0002 (11)	0.0061 (12)	−0.0043 (11)
N1c	0.0167 (11)	0.0302 (13)	0.0222 (13)	0.0005 (10)	0.0032 (9)	−0.0008 (11)
N2c	0.0252 (13)	0.0224 (13)	0.0253 (14)	−0.0014 (10)	0.0043 (10)	−0.0015 (9)
O1c	0.0347 (8)	0.0350 (9)	0.0187 (7)	−0.0014 (6)	0.0006 (6)	0.0009 (6)
O2c	0.0194 (7)	0.0493 (10)	0.0342 (8)	0.0008 (7)	0.0049 (6)	−0.0036 (7)
Cl1d	0.0360 (4)	0.0301 (4)	0.0197 (4)	−0.0011 (3)	0.0121 (3)	0.0043 (3)
C1d	0.0193 (15)	0.0176 (12)	0.0196 (15)	0.0038 (10)	0.0064 (12)	−0.0013 (10)
C2d	0.0185 (15)	0.0163 (14)	0.0201 (15)	−0.0035 (10)	0.0067 (12)	−0.0026 (10)
C3d	0.0135 (13)	0.0213 (13)	0.0219 (14)	0.0007 (10)	0.0024 (11)	−0.0033 (10)
C4d	0.0321 (16)	0.0180 (15)	0.0175 (15)	0.0038 (11)	0.0119 (13)	0.0013 (9)
C5d	0.0194 (15)	0.0192 (17)	0.0322 (17)	−0.0026 (10)	0.0127 (13)	−0.0037 (10)
C6d	0.0194 (15)	0.0236 (14)	0.0166 (15)	0.0024 (11)	0.0031 (12)	−0.0040 (10)
N1d	0.0249 (13)	0.0315 (12)	0.0153 (13)	0.0007 (11)	0.0061 (10)	0.0079 (11)
N2d	0.0203 (13)	0.0211 (12)	0.0181 (13)	0.0063 (9)	−0.0017 (9)	0.0000 (9)
O1d	0.0351 (8)	0.0331 (9)	0.0197 (8)	−0.0007 (6)	−0.0001 (6)	0.0004 (6)
O2d	0.0206 (8)	0.0471 (10)	0.0349 (8)	0.0016 (7)	0.0044 (6)	−0.0037 (7)

Geometric parameters (Å, º)

Cl1a—C4a	1.745 (4)	Cl1c—C4c	1.720 (4)
C1a—C2a	1.397 (4)	C1c—C2c	1.394 (4)
C1a—C6a	1.391 (5)	C1c—C6c	1.411 (5)
C1a—N1a	1.395 (5)	C1c—N1c	1.371 (5)
C2a—H1c2a	0.95	C2c—H1c2c	0.95
C2a—C3a	1.360 (5)	C2c—C3c	1.401 (5)
C3a—C4a	1.410 (5)	C3c—C4c	1.376 (5)
C3a—N2a	1.486 (3)	C3c—N2c	1.450 (3)
C4a—C5a	1.372 (4)	C4c—C5c	1.409 (4)
C5a—H1c5a	0.95	C5c—H1c5c	0.95
C5a—C6a	1.367 (5)	C5c—C6c	1.382 (5)
C6a—H1c6a	0.95	C6c—H1c6c	0.95
N1a—H1n1a	0.880 (17)	N1c—H1n1c	0.88 (2)
N1a—H2n1a	0.880 (12)	N1c—H2n1c	0.880 (13)
H1n1a—H2n1a	1.54 (2)	H1n1c—H2n1c	1.46 (2)
N2a—O1a	1.204 (3)	N2c—O1c	1.243 (4)
N2a—O2a	1.223 (3)	N2c—O2c	1.229 (4)
Cl1b—C4b	1.719 (4)	Cl1d—C4d	1.742 (4)
C1b—C2b	1.392 (4)	C1d—C2d	1.397 (4)
C1b—C6b	1.408 (5)	C1d—C6d	1.385 (5)
C1b—N1b	1.373 (5)	C1d—N1d	1.398 (5)
C2b—H1c2b	0.95	C2d—H1c2d	0.95
C2b—C3b	1.404 (5)	C2d—C3d	1.370 (5)
C3b—C4b	1.368 (5)	C3d—C4d	1.410 (5)
C3b—N2b	1.447 (3)	C3d—N2d	1.483 (3)
C4b—C5b	1.405 (4)	C4d—C5d	1.375 (4)
C5b—H1c5b	0.95	C5d—H1c5d	0.95
C5b—C6b	1.392 (5)	C5d—C6d	1.373 (5)
C6b—H1c6b	0.95	C6d—H1c6d	0.95
N1b—H1n1b	0.88 (2)	N1d—H1n1d	0.880 (18)
N1b—H2n1b	0.880 (13)	N1d—H2n1d	0.880 (13)
H1n1b—H2n1b	1.46 (2)	H1n1d—H2n1d	1.57 (2)
N2b—O1b	1.232 (3)	N2d—O1d	1.211 (4)
N2b—O2b	1.228 (3)	N2d—O2d	1.231 (4)
Cl1a—C4a—C3a	122.5 (2)	H1n1b—N1b—H2n1b	112.4 (19)
Cl1a—C4a—C5a	120.6 (3)	C3b—N2b—O1b	118.6 (2)
Cl1b—C4b—C3b	123.2 (2)	C3b—N2b—O2b	118.8 (2)
Cl1b—C4b—C5b	118.8 (3)	O1b—N2b—O2b	122.7 (2)
Cl1c—C4c—C3c	125.2 (2)	C2c—C1c—C6c	117.9 (3)
Cl1c—C4c—C5c	117.0 (3)	C2c—C1c—N1c	121.1 (3)
Cl1d—C4d—C3d	124.6 (3)	C6c—C1c—N1c	120.9 (3)
Cl1d—C4d—C5d	118.4 (3)	C1c—C2c—H1c2c	119.84
C2a—C1a—C6a	118.5 (3)	C1c—C2c—C3c	120.3 (3)
C2a—C1a—N1a	119.4 (3)	H1c2c—C2c—C3c	119.8335
C6a—C1a—N1a	121.9 (3)	C2c—C3c—C4c	122.0 (3)
C1a—C2a—H1c2a	120.2115	C2c—C3c—N2c	114.8 (3)
C1a—C2a—C3a	119.6 (3)	C4c—C3c—N2c	123.2 (3)
H1c2a—C2a—C3a	120.2	C3c—C4c—C5c	117.8 (3)
C2a—C3a—C4a	122.3 (3)	C4c—C5c—H1c5c	119.51
C2a—C3a—N2a	117.3 (3)	C4c—C5c—C6c	121.0 (3)
C4a—C3a—N2a	120.4 (3)	H1c5c—C5c—C6c	119.51
C3a—C4a—C5a	116.9 (3)	C1c—C6c—C5c	121.0 (3)
C4a—C5a—H1c5a	119.05	C1c—C6c—H1c6c	119.5
C4a—C5a—C6a	121.9 (4)	C5c—C6c—H1c6c	119.5
H1c5a—C5a—C6a	119.0481	C1c—N1c—H1n1c	121.0 (16)
C1a—C6a—C5a	120.8 (3)	C1c—N1c—H2n1c	113.9 (16)
C1a—C6a—H1c6a	119.62	H1n1c—N1c—H2n1c	112 (2)
C5a—C6a—H1c6a	119.62	C3c—N2c—O1c	119.1 (3)
C1a—N1a—H1n1a	105.7 (18)	C3c—N2c—O2c	119.2 (3)
C1a—N1a—H2n1a	114.2 (15)	O1c—N2c—O2c	121.7 (3)
H1n1a—N1a—H2n1a	122 (2)	C2d—C1d—C6d	118.5 (3)
C3a—N2a—O1a	118.6 (2)	C2d—C1d—N1d	119.4 (3)
C3a—N2a—O2a	116.0 (2)	C6d—C1d—N1d	122.0 (2)
O1a—N2a—O2a	125.3 (2)	C1d—C2d—H1c2d	119.77
C2b—C1b—C6b	118.4 (3)	C1d—C2d—C3d	120.5 (3)
C2b—C1b—N1b	120.6 (3)	H1c2d—C2d—C3d	119.77
C6b—C1b—N1b	121.0 (3)	C2d—C3d—C4d	121.3 (3)
C1b—C2b—H1c2b	120.3	C2d—C3d—N2d	117.0 (3)
C1b—C2b—C3b	119.4 (3)	C4d—C3d—N2d	121.7 (3)
H1c2b—C2b—C3b	120.29	C3d—C4d—C5d	116.9 (3)
C2b—C3b—C4b	122.8 (3)	C4d—C5d—H1c5d	118.75
C2b—C3b—N2b	114.9 (3)	C4d—C5d—C6d	122.5 (3)
C4b—C3b—N2b	122.3 (3)	H1c5d—C5d—C6d	118.75
C3b—C4b—C5b	117.9 (3)	C1d—C6d—C5d	120.3 (3)
C4b—C5b—H1c5b	119.79	C1d—C6d—H1c6d	119.85
C4b—C5b—C6b	120.4 (4)	C5d—C6d—H1c6d	119.86
H1c5b—C5b—C6b	119.79	C1d—N1d—H1n1d	108.4 (16)
C1b—C6b—C5b	121.0 (3)	C1d—N1d—H2n1d	112.6 (15)
C1b—C6b—H1c6b	119.49	H1n1d—N1d—H2n1d	126 (2)
C5b—C6b—H1c6b	119.48	C3d—N2d—O1d	119.7 (3)
C1b—N1b—H1n1b	119.8 (15)	C3d—N2d—O2d	116.1 (3)
C1b—N1b—H2n1b	114.5 (15)	O1d—N2d—O2d	124.2 (2)
H1n1a—N1a—C1a—C2a	37.4 (15)	H1n1c—N1c—C1c—C2c	−17.9 (17)
H2n1a—N1a—C1a—C2a	174.9 (18)	H2n1c—N1a—C1c—C2c	157.0 (9)
H1n1b—N1b—C1b—C2b	−14.4 (17)	H1n1d—N1d—C1d—C2d	33.5 (15)
H2n1b—N1b—C1b—C2b	−152.4 (16)	H2n1d—N1d—C1d—C2d	177.4 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1a—H1n1a···N1c^i	0.880 (17)	2.28 (2)	3.060 (5)	147 (2)
N1a—H2n1a···O1a^ii	0.880 (13)	2.808 (19)	3.468 (4)	133 (2)
N1a—H2n1a···O2a^ii	0.880 (12)	2.201 (13)	3.079 (3)	175.2 (19)
N1b—H1n1b···N1a^iii	0.88 (2)	2.21 (2)	3.085 (5)	176.7 (19)
N1b—H2n1b···O1b^iv	0.880 (13)	3.112 (19)	3.562 (4)	114.0 (17)
N1b—H2n1b···O1c^iv	0.880 (13)	2.410 (13)	3.260 (3)	163 (2)
N1b—H2n1b···O2c^iv	0.880 (13)	2.389 (19)	3.144 (3)	144 (2)
N1c—H1n1c···N1d^iii	0.88 (2)	2.17 (2)	3.046 (5)	174.5 (17)
N1c—H2n1c···O1b^iv	0.880 (13)	2.745 (18)	3.563 (3)	155.3 (19)
N1c—H2n1c···O2b^iv	0.880 (13)	2.307 (15)	3.108 (3)	151 (2)
N1d—H1n1d···N1b^v	0.880 (18)	2.23 (2)	3.041 (5)	153 (2)
N1d—H2n1d···O1d^vi	0.880 (13)	2.569 (14)	3.323 (3)	144 (2)
N1d—H2n1d···O2d^vi	0.880 (13)	2.421 (19)	3.183 (3)	145 (2)
N1d—H2n1d···O1a^vi	0.880 (13)	3.04 (2)	3.754 (3)	140 (2)

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

(IIa) 4-Iodo-3-nitroaniline

Crystal data

C6H5IN2O2	F(000) = 496
Mr = 264	Dx = 2.208 Mg m^−3
Monoclinic, P21/n	Melting point: 413 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.5418 Å
a = 12.5219 (8) Å	Cell parameters from 3022 reflections
b = 4.2601 (3) Å	θ = 3.9–66.7°
c = 16.0008 (9) Å	µ = 31.34 mm^−1
β = 111.556 (6)°	T = 293 K
V = 793.86 (9) Å^3	Plate, brown
Z = 4	0.50 × 0.24 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Gemini ultra) diffractometer	1380 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1093 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.062
Detector resolution: 5.1892 pixels mm^-1	θmax = 67.0°, θmin = 3.9°
ω scans	h = −14→14
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010)	k = −4→4
Tmin = 0.002, Tmax = 0.361	l = −19→18
5100 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.053	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
wR(F^2) = 0.120	(Δ/σ)max = 0.015
S = 2.31	Δρmax = 1.90 e Å^−3
1380 reflections	Δρmin = −0.85 e Å^−3
125 parameters	Extinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
2 restraints	Extinction coefficient: 220 (50)
14 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
I1a	0.28645 (6)	0.33319 (17)	0.35667 (3)	0.0691 (3)
C1a	0.3183 (8)	−0.108 (2)	0.6483 (5)	0.058 (4)
C2a	0.2169 (8)	−0.150 (3)	0.5759 (5)	0.058 (4)
H1c2a	0.156803	−0.261037	0.582912	0.0692*
C3a	0.2049 (7)	−0.026 (3)	0.4927 (5)	0.053 (3)
C4a	0.2914 (8)	0.141 (2)	0.4785 (5)	0.056 (3)
C5a	0.3940 (9)	0.178 (3)	0.5511 (6)	0.065 (4)
H1c5a	0.454837	0.284168	0.543679	0.082*
C6a	0.4059 (8)	0.058 (3)	0.6348 (5)	0.068 (4)
H1c6a	0.474516	0.089448	0.68299	0.0783*
N1a	0.3285 (9)	−0.217 (3)	0.7324 (5)	0.082 (4)
H1n1a	0.285 (11)	−0.38 (2)	0.726 (9)	0.0978*
H2n1a	0.397 (5)	−0.20 (3)	0.774 (6)	0.0978*
N2a	0.0925 (7)	−0.080 (2)	0.4212 (5)	0.065 (4)
O1a	0.0511 (16)	0.130 (7)	0.3672 (13)	0.093 (9)	0.5
O2a	0.046 (2)	−0.330 (6)	0.4264 (15)	0.085 (9)	0.5
O1d	0.0794 (16)	−0.041 (6)	0.3431 (11)	0.086 (9)	0.5
O2d	0.012 (2)	−0.172 (8)	0.4381 (15)	0.094 (11)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1a	0.1026 (6)	0.0537 (5)	0.0606 (4)	−0.0049 (4)	0.0412 (3)	−0.0015 (2)
C1a	0.056 (5)	0.070 (8)	0.048 (4)	0.015 (5)	0.017 (3)	0.004 (3)
C2a	0.057 (5)	0.062 (7)	0.057 (4)	0.007 (5)	0.024 (4)	0.002 (4)
C3a	0.055 (5)	0.054 (6)	0.049 (3)	0.005 (4)	0.017 (3)	−0.004 (3)
C4a	0.064 (5)	0.063 (7)	0.043 (3)	−0.002 (5)	0.023 (3)	0.000 (3)
C5a	0.063 (6)	0.070 (8)	0.066 (5)	−0.010 (5)	0.028 (4)	−0.013 (4)
C6a	0.055 (5)	0.086 (9)	0.054 (4)	0.003 (5)	0.008 (4)	−0.006 (4)
N1a	0.076 (6)	0.108 (9)	0.052 (4)	0.011 (5)	0.013 (4)	0.015 (4)
N2a	0.056 (5)	0.080 (8)	0.052 (4)	0.004 (5)	0.012 (3)	0.000 (3)
O1a	0.064 (11)	0.12 (2)	0.078 (10)	0.016 (11)	0.002 (8)	0.023 (11)
O2a	0.061 (13)	0.083 (19)	0.090 (11)	−0.014 (11)	0.004 (9)	−0.002 (11)
O1d	0.063 (11)	0.11 (2)	0.066 (9)	−0.016 (11)	0.001 (7)	0.009 (9)
O2d	0.064 (13)	0.13 (3)	0.086 (10)	−0.001 (13)	0.020 (8)	0.010 (13)

Geometric parameters (Å, º)

I1a—C4a	2.095 (8)	C5a—C6a	1.389 (14)
C1a—C2a	1.380 (11)	C6a—H1c6a	0.93
C1a—C6a	1.387 (16)	N1a—H1n1a	0.88 (11)
C1a—N1a	1.384 (12)	N1a—H2n1a	0.88 (6)
C2a—H1c2a	0.93	N2a—O1a	1.22 (3)
C2a—C3a	1.388 (12)	N2a—O2a	1.23 (3)
C3a—C4a	1.383 (15)	N2a—O1d	1.21 (2)
C3a—N2a	1.469 (10)	N2a—O2d	1.20 (3)
C4a—C5a	1.388 (11)	O2a—O2d	0.85 (4)
C5a—H1c5a	0.93
I1a—C4a—C3a	126.7 (5)	C1a—C6a—C5a	121.8 (8)
I1a—C4a—C5a	115.8 (8)	C1a—C6a—H1c6a	119.08
C6a—C1a—N1a	121.9 (8)	C5a—C6a—H1c6a	119.08
C1a—C2a—H1c2a	120.08	C1a—N1a—H1n1a	110 (9)
C1a—C2a—C3a	119.8 (10)	C1a—N1a—H2n1a	116 (7)
H1c2a—C2a—C3a	120.08	H1n1a—N1a—H2n1a	122 (12)
C2a—C3a—C4a	122.5 (7)	C3a—N2a—O1a	118.3 (13)
C2a—C3a—N2a	115.0 (9)	C3a—N2a—O2a	115.2 (12)
C4a—C3a—N2a	122.4 (7)	C3a—N2a—O1d	120.7 (13)
C3a—C4a—C5a	117.5 (8)	C3a—N2a—O2d	121.2 (12)
C4a—C5a—H1c5a	119.92	O1a—N2a—O2a	126.3 (15)
C4a—C5a—C6a	120.2 (10)	O1d—N2a—O2d	118.1 (15)
H1c5a—C5a—C6a	119.91
H1n1a—N1a—C1a—C2a	30 (9)	H2n1a—N1a—C1a—C6a	−10 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1a—H1n1a···N1a^i	0.88 (11)	2.27 (14)	3.088 (17)	155 (13)
N1a—H2n1a···O1a^ii	0.88 (6)	2.67 (11)	3.33 (2)	133 (12)
N1a—H2n1a···O2a^ii	0.88 (6)	2.46 (8)	3.30 (2)	159 (9)
N1a—H2n1a···O1d^ii	0.88 (6)	2.40 (8)	3.16 (2)	145 (12)
N1a—H2n1a···O2d^ii	0.88 (6)	2.54 (9)	3.29 (2)	143 (9)

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

(IIb) 4-Iodo-3-nitroaniline

Crystal data

C6H5IN2O2	F(000) = 992
Mr = 264	Dx = 2.273 Mg m^−3
Monoclinic, Pn	Melting point: 413 K
Hall symbol: P -2yac	Mo Kα radiation, λ = 0.71069 Å
a = 12.5188 (9) Å	Cell parameters from 5556 reflections
b = 8.2955 (5) Å	θ = 3.0–32.6°
c = 15.9287 (10) Å	µ = 4.1 mm^−1
β = 111.141 (6)°	T = 120 K
V = 1542.86 (19) Å^3	Plate, brown
Z = 8	0.3 × 0.15 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Gemini ultra) diffractometer	9998 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4208 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.079
Detector resolution: 10.3784 pixels mm^-1	θmax = 31.5°, θmin = 3.0°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −12→12
Tmin = 0.483, Tmax = 0.815	l = −23→23
27795 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.048	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0004I^2)
wR(F^2) = 0.118	(Δ/σ)max = 0.020
S = 1.32	Δρmax = 2.58 e Å^−3
9998 reflections	Δρmin = −2.00 e Å^−3
224 parameters	Absolute structure: 3424 of Friedel pairs used in the refinement
4 restraints	Absolute structure parameter: 0.41 (13)
30 constraints

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

	x	y	z	Uiso*/Ueq
I1a	0.2870 (4)	0.28757 (11)	0.37137 (18)	0.0245 (2)
C1a	0.3234 (10)	0.0570 (12)	0.6651 (6)	0.020 (3)
C2a	0.2225 (10)	0.0383 (11)	0.5932 (6)	0.022 (3)
H1c2a	0.161638	−0.021642	0.600301	0.0262*
C3a	0.2086 (8)	0.1059 (9)	0.5105 (6)	0.020 (3)
C4a	0.2946 (8)	0.1906 (9)	0.4956 (5)	0.021 (3)
C5a	0.3977 (9)	0.2070 (11)	0.5677 (5)	0.024 (3)
H1c5a	0.459503	0.26248	0.559367	0.0332*
C6a	0.4117 (10)	0.1441 (12)	0.6514 (6)	0.028 (3)
H1c6a	0.482063	0.160035	0.700135	0.0284*
N1a	0.3343 (12)	−0.0001 (14)	0.7498 (6)	0.029 (3)
H1n1a	0.288 (5)	−0.083 (5)	0.744 (5)	0.0347*
H2n1a	0.407 (2)	0.000 (8)	0.785 (4)	0.0347*
N2a	0.0949 (7)	0.0821 (9)	0.4391 (6)	0.025 (3)
O1a	0.0540 (6)	0.1949 (9)	0.3888 (5)	0.042 (2)
O2a	0.0488 (7)	−0.0471 (8)	0.4362 (6)	0.039 (2)
I1b	0.7090 (15)	0.4609 (19)	0.6568 (6)	0.0245 (2)
C1b	0.6764 (13)	0.6934 (19)	0.3643 (6)	0.020 (3)
C2b	0.7768 (12)	0.7118 (16)	0.4368 (7)	0.022 (3)
H1c2b	0.837929	0.771916	0.430371	0.0262*
C3b	0.7896 (11)	0.6436 (16)	0.5192 (7)	0.020 (3)
C4b	0.7030 (11)	0.5587 (16)	0.5332 (6)	0.021 (3)
C5b	0.6005 (11)	0.5426 (17)	0.4604 (8)	0.024 (3)
H1c5b	0.538359	0.487001	0.468122	0.0332*
C6b	0.5876 (13)	0.6061 (19)	0.3771 (8)	0.028 (3)
H1c6b	0.517622	0.590387	0.327908	0.0284*
N1b	0.6666 (17)	0.751 (2)	0.2800 (8)	0.029 (3)
H1n1b	0.713 (5)	0.834 (6)	0.287 (5)	0.0347*
H2n1b	0.594 (2)	0.751 (8)	0.244 (4)	0.0347*
N2b	0.9027 (13)	0.667 (2)	0.5913 (10)	0.025 (3)
O1b	0.9431 (15)	0.554 (2)	0.6416 (11)	0.042 (2)
O2b	0.9490 (14)	0.796 (2)	0.5949 (11)	0.039 (2)
I1c	0.7083 (4)	−0.04553 (11)	0.65628 (18)	0.0241 (2)
C1c	0.6790 (11)	0.1841 (12)	0.3641 (6)	0.025 (3)
C2c	0.7818 (10)	0.2030 (10)	0.4366 (6)	0.020 (2)
H1c2c	0.844075	0.258634	0.428972	0.0236*
C3c	0.7925 (8)	0.1406 (9)	0.5193 (6)	0.018 (3)
C4c	0.7033 (8)	0.0601 (8)	0.5361 (5)	0.018 (3)
C5c	0.6018 (9)	0.0418 (10)	0.4623 (6)	0.024 (3)
H1c5c	0.539711	−0.014051	0.470018	0.0271*
C6c	0.5883 (10)	0.1028 (12)	0.3775 (5)	0.023 (3)
H1c6c	0.517654	0.089198	0.328722	0.0293*
N1c	0.6697 (12)	0.2410 (14)	0.2799 (6)	0.029 (3)
H1n1c	0.725 (4)	0.308 (6)	0.283 (5)	0.0351*
H2n1c	0.601 (3)	0.245 (8)	0.238 (3)	0.0351*
N2c	0.9051 (7)	0.1649 (8)	0.5921 (6)	0.024 (2)
O1c	0.9162 (6)	0.1538 (7)	0.6713 (5)	0.0361 (18)
O2c	0.9880 (7)	0.1987 (9)	0.5703 (6)	0.0381 (18)
I1d	0.2833 (6)	0.7914 (8)	0.3687 (3)	0.0241 (2)
C1d	0.3120 (15)	0.5560 (19)	0.6594 (8)	0.025 (3)
C2d	0.2090 (12)	0.5389 (15)	0.5869 (7)	0.020 (2)
H1c2d	0.146524	0.483469	0.594267	0.0236*
C3d	0.1984 (8)	0.6030 (11)	0.5046 (6)	0.018 (3)
C4d	0.2880 (7)	0.6835 (10)	0.4882 (5)	0.018 (3)
C5d	0.3897 (10)	0.6999 (14)	0.5620 (7)	0.024 (3)
H1c5d	0.451991	0.755563	0.554616	0.0271*
C6d	0.4030 (14)	0.6371 (19)	0.6465 (8)	0.023 (3)
H1c6d	0.473813	0.649466	0.695265	0.0293*
N1d	0.321 (2)	0.497 (2)	0.7433 (9)	0.029 (3)
H1n1d	0.265 (4)	0.430 (6)	0.740 (5)	0.0351*
H2n1d	0.390 (3)	0.492 (8)	0.785 (3)	0.0351*
N2d	0.0856 (7)	0.5806 (11)	0.4318 (8)	0.024 (2)
O1d	0.0745 (8)	0.5934 (13)	0.3526 (8)	0.0361 (18)
O2d	0.0027 (8)	0.5468 (14)	0.4535 (11)	0.0381 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1a	0.0334 (4)	0.0190 (3)	0.0269 (4)	−0.0012 (2)	0.0179 (3)	−0.0005 (2)
C1a	0.018 (3)	0.024 (4)	0.015 (4)	0.006 (3)	0.004 (3)	0.002 (3)
C2a	0.021 (4)	0.019 (3)	0.030 (5)	0.005 (3)	0.014 (4)	0.000 (4)
C3a	0.020 (4)	0.020 (3)	0.021 (4)	0.002 (3)	0.008 (4)	−0.004 (3)
C4a	0.027 (4)	0.019 (4)	0.019 (4)	0.007 (3)	0.010 (3)	−0.001 (3)
C5a	0.022 (4)	0.021 (3)	0.033 (5)	0.001 (3)	0.015 (4)	−0.004 (4)
C6a	0.022 (4)	0.032 (4)	0.029 (5)	0.003 (3)	0.009 (4)	−0.003 (4)
N1a	0.020 (4)	0.044 (4)	0.022 (4)	0.005 (3)	0.008 (3)	0.004 (3)
N2a	0.020 (3)	0.025 (3)	0.033 (4)	0.001 (3)	0.011 (3)	−0.001 (3)
O1a	0.034 (3)	0.053 (3)	0.034 (3)	0.008 (3)	0.005 (2)	0.018 (3)
O2a	0.030 (3)	0.035 (3)	0.048 (3)	−0.009 (2)	0.009 (2)	−0.002 (2)
I1b	0.0332 (4)	0.0190 (3)	0.0271 (4)	−0.0013 (2)	0.0180 (3)	−0.0005 (2)
C1b	0.018 (4)	0.024 (4)	0.015 (4)	0.006 (3)	0.004 (3)	0.002 (3)
C2b	0.021 (4)	0.019 (3)	0.030 (5)	0.005 (3)	0.014 (4)	0.000 (4)
C3b	0.020 (4)	0.020 (3)	0.021 (4)	0.002 (3)	0.008 (4)	−0.004 (3)
C4b	0.027 (4)	0.019 (4)	0.019 (4)	0.007 (3)	0.010 (3)	−0.001 (3)
C5b	0.022 (4)	0.021 (3)	0.033 (5)	0.001 (3)	0.015 (4)	−0.004 (4)
C6b	0.022 (4)	0.032 (4)	0.029 (5)	0.003 (3)	0.009 (4)	−0.003 (4)
N1b	0.020 (4)	0.044 (4)	0.022 (4)	0.005 (3)	0.008 (3)	0.004 (3)
N2b	0.020 (3)	0.025 (3)	0.033 (4)	0.001 (3)	0.011 (3)	−0.001 (3)
O1b	0.035 (3)	0.053 (3)	0.034 (3)	0.008 (3)	0.005 (2)	0.018 (3)
O2b	0.030 (3)	0.035 (3)	0.048 (3)	−0.009 (2)	0.008 (2)	−0.003 (2)
I1c	0.0330 (4)	0.0191 (3)	0.0259 (4)	−0.0010 (2)	0.0176 (3)	−0.0006 (2)
C1c	0.028 (4)	0.020 (4)	0.032 (5)	0.006 (3)	0.019 (4)	−0.001 (3)
C2c	0.018 (3)	0.022 (3)	0.020 (4)	−0.001 (3)	0.008 (3)	0.000 (3)
C3c	0.016 (4)	0.018 (3)	0.022 (4)	0.004 (3)	0.007 (3)	−0.001 (3)
C4c	0.024 (4)	0.014 (3)	0.022 (4)	0.002 (3)	0.016 (3)	0.000 (3)
C5c	0.024 (4)	0.024 (4)	0.031 (5)	−0.002 (4)	0.017 (4)	0.001 (4)
C6c	0.022 (4)	0.024 (4)	0.022 (5)	0.006 (3)	0.007 (4)	0.004 (3)
N1c	0.025 (4)	0.042 (4)	0.020 (4)	−0.003 (3)	0.007 (3)	0.005 (3)
N2c	0.024 (3)	0.029 (3)	0.020 (4)	0.005 (3)	0.012 (3)	0.000 (3)
O1c	0.029 (2)	0.048 (3)	0.026 (3)	−0.009 (2)	0.004 (2)	0.000 (2)
O2c	0.021 (2)	0.061 (3)	0.034 (3)	−0.003 (2)	0.012 (2)	0.002 (2)
I1d	0.0330 (4)	0.0191 (3)	0.0259 (4)	−0.0011 (2)	0.0176 (3)	−0.0007 (2)
C1d	0.028 (4)	0.020 (4)	0.032 (5)	0.006 (3)	0.019 (4)	−0.001 (3)
C2d	0.018 (3)	0.022 (3)	0.020 (4)	−0.001 (3)	0.008 (3)	0.000 (3)
C3d	0.016 (4)	0.018 (3)	0.022 (4)	0.004 (3)	0.007 (3)	−0.001 (3)
C4d	0.024 (4)	0.014 (3)	0.022 (4)	0.002 (3)	0.016 (3)	0.000 (3)
C5d	0.024 (4)	0.024 (4)	0.031 (5)	−0.002 (4)	0.017 (4)	0.001 (4)
C6d	0.022 (4)	0.024 (4)	0.022 (5)	0.006 (3)	0.008 (4)	0.004 (3)
N1d	0.025 (4)	0.042 (4)	0.020 (4)	−0.003 (3)	0.007 (3)	0.005 (3)
N2d	0.024 (3)	0.029 (3)	0.020 (4)	0.005 (3)	0.012 (3)	0.000 (3)
O1d	0.029 (2)	0.048 (3)	0.026 (3)	−0.009 (2)	0.004 (2)	0.001 (2)
O2d	0.021 (2)	0.060 (3)	0.034 (3)	−0.003 (2)	0.012 (2)	0.002 (2)

Geometric parameters (Å, º)

I1a—C4a	2.106 (9)	N2b—O2b	1.21 (2)
I1b—C4b	2.106 (16)	C1c—C2c	1.393 (13)
I1c—C4c	2.085 (9)	C1c—C6c	1.401 (18)
I1d—C4d	2.085 (11)	C1c—N1c	1.387 (15)
C1a—C2a	1.374 (13)	C2c—H1c2c	0.95
C1a—C6a	1.403 (18)	C2c—C3c	1.376 (13)
C1a—N1a	1.389 (14)	C3c—C4c	1.408 (14)
C2a—H1c2a	0.95	C3c—N2c	1.481 (11)
C2a—C3a	1.383 (14)	C4c—C5c	1.394 (11)
C3a—C4a	1.376 (15)	C5c—H1c5c	0.95
C3a—N2a	1.480 (11)	C5c—C6c	1.395 (13)
C4a—C5a	1.391 (11)	C6c—H1c6c	0.95
C5a—H1c5a	0.95	N1c—H1n1c	0.88 (6)
C5a—C6a	1.382 (13)	N1c—H2n1c	0.88 (3)
C6a—H1c6a	0.95	H1n1c—H2n1c	1.55 (6)
N1a—H1n1a	0.88 (5)	N2c—O1c	1.222 (13)
N1a—H2n1a	0.88 (3)	N2c—O2c	1.238 (15)
H1n1a—H2n1a	1.55 (6)	C1d—C2d	1.393 (17)
N2a—O1a	1.219 (10)	C1d—C6d	1.40 (3)
N2a—O2a	1.210 (11)	C1d—N1d	1.39 (2)
C1b—C2b	1.374 (16)	C2d—H1c2d	0.95
C1b—N1b	1.389 (18)	C2d—C3d	1.376 (15)
C2b—H1c2b	0.95	C3d—C4d	1.408 (14)
C2b—C3b	1.383 (17)	C3d—N2d	1.481 (12)
C3b—C4b	1.38 (2)	C4d—C5d	1.394 (12)
C3b—N2b	1.480 (17)	C5d—H1c5d	0.95
C4b—C5b	1.391 (15)	C5d—C6d	1.395 (18)
C5b—H1c5b	0.95	C6d—H1c6d	0.95
C5b—C6b	1.382 (19)	N1d—H1n1d	0.88 (6)
C6b—H1c6b	0.95	N1d—H2n1d	0.88 (4)
N1b—H1n1b	0.88 (6)	H1n1d—H2n1d	1.55 (6)
N1b—H2n1b	0.88 (3)	N2d—O1d	1.222 (19)
H1n1b—H2n1b	1.55 (7)	N2d—O2d	1.238 (18)
N2b—O1b	1.22 (2)
C2a—C1a—C6a	117.9 (9)	C2c—C1c—C6c	119.1 (9)
C2a—C1a—N1a	120.6 (12)	C2c—C1c—N1c	119.6 (12)
C6a—C1a—N1a	121.4 (9)	C6c—C1c—N1c	121.4 (9)
C1a—C2a—H1c2a	119.68	C1c—C2c—H1c2c	120.25
C1a—C2a—C3a	120.6 (11)	C1c—C2c—C3c	119.5 (11)
H1c2a—C2a—C3a	119.68	H1c2c—C2c—C3c	120.25
C2a—C3a—C4a	122.3 (8)	C2c—C3c—C4c	123.4 (8)
C2a—C3a—N2a	115.7 (9)	C2c—C3c—N2c	115.8 (9)
C4a—C3a—N2a	122.1 (8)	C4c—C3c—N2c	120.8 (8)
C3a—C4a—C5a	117.2 (8)	C3c—C4c—C5c	115.8 (8)
C4a—C5a—H1c5a	119.43	C4c—C5c—H1c5c	118.9
C4a—C5a—C6a	121.1 (10)	C4c—C5c—C6c	122.2 (10)
H1c5a—C5a—C6a	119.43	H1c5c—C5c—C6c	118.9
C1a—C6a—C5a	120.8 (8)	C1c—C6c—C5c	120.0 (8)
C1a—C6a—H1c6a	119.61	C1c—C6c—H1c6c	120
C5a—C6a—H1c6a	119.61	C5c—C6c—H1c6c	120.01
C1a—N1a—H1n1a	109 (5)	C1c—N1c—H1n1c	112 (5)
C1a—N1a—H2n1a	110 (4)	C1c—N1c—H2n1c	118 (4)
H1n1a—N1a—H2n1a	124 (6)	H1n1c—N1c—H2n1c	124 (6)
C3a—N2a—O1a	117.6 (7)	C3c—N2c—O1c	121.2 (9)
C3a—N2a—O2a	117.5 (7)	C3c—N2c—O2c	117.9 (9)
O1a—N2a—O2a	125.0 (8)	O1c—N2c—O2c	120.8 (8)
C2b—C1b—C6b	117.9 (11)	C2d—C1d—C6d	119.1 (12)
C2b—C1b—N1b	120.6 (16)	C2d—C1d—N1d	119.6 (18)
C6b—C1b—N1b	121.4 (12)	C6d—C1d—N1d	121.4 (14)
C1b—C2b—H1c2b	119.68	C1d—C2d—H1c2d	120.25
C1b—C2b—C3b	120.6 (14)	C1d—C2d—C3d	119.5 (13)
H1c2b—C2b—C3b	119.68	H1c2d—C2d—C3d	120.25
C2b—C3b—C4b	122.3 (10)	C2d—C3d—C4d	123.4 (9)
C2b—C3b—N2b	115.7 (13)	C2d—C3d—N2d	115.8 (10)
C4b—C3b—N2b	122.1 (11)	C4d—C3d—N2d	120.8 (9)
C3b—C4b—C5b	117.2 (11)	C3d—C4d—C5d	115.8 (9)
C4b—C5b—H1c5b	119.43	C4d—C5d—H1c5d	118.9
C4b—C5b—C6b	121.1 (14)	C4d—C5d—C6d	122.2 (12)
H1c5b—C5b—C6b	119.43	H1c5d—C5d—C6d	118.9
C1b—C6b—C5b	120.8 (11)	C1d—C6d—C5d	120.0 (11)
C1b—C6b—H1c6b	119.61	C1d—C6d—H1c6d	120
C5b—C6b—H1c6b	119.61	C5d—C6d—H1c6d	120.01
C1b—N1b—H1n1b	109 (5)	C1d—N1d—H1n1d	112 (5)
C1b—N1b—H2n1b	110 (5)	C1d—N1d—H2n1d	118 (5)
H1n1b—N1b—H2n1b	124 (6)	H1n1d—N1d—H2n1d	124 (6)
C3b—N2b—O1b	117.6 (15)	C3d—N2d—O1d	121.2 (11)
C3b—N2b—O2b	117.5 (14)	C3d—N2d—O2d	117.9 (13)
O1b—N2b—O2b	125.0 (15)	O1d—N2d—O2d	120.8 (11)
H1n1d—N1d—C1d—C2d	15 (5)	H1n1a—N1a—C1a—C2a	28 (4)
H2n1d—N1d—C1d—C2d	168 (5)	H2n1a—N1a—C1a—C2a	166 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1a—H1n1a···N1c^i	0.88 (5)	2.21 (7)	3.03 (2)	155 (7)
N1a—H2n1a···O1a^ii	0.88 (3)	2.56 (5)	3.269 (13)	139 (5)
N1a—H2n1a···O2a^ii	0.88 (3)	2.46 (5)	3.229 (13)	147 (5)
N1b—H1n1b···N1a^iii	0.88 (6)	2.28 (7)	3.10 (2)	156 (7)
N1b—H2n1b···O1b^iv	0.88 (4)	3.23 (6)	3.83 (2)	127 (5)
N1b—H2n1b···O1c^iv	0.88 (3)	2.25 (4)	3.088 (19)	159 (6)
N1b—H2n1b···O2c^iv	0.88 (3)	2.64 (6)	3.308 (14)	133 (5)
N1c—H1n1c···N1d^iii	0.88 (6)	2.23 (7)	3.07 (3)	160 (6)
N1c—H2n1c···O1b^iv	0.88 (3)	2.62 (5)	3.36 (2)	143 (5)
N1c—H2n1c···O2b^iv	0.88 (3)	2.41 (4)	3.248 (17)	159 (5)
N1d—H1n1d···N1b^v	0.88 (6)	2.18 (7)	3.02 (3)	160 (6)
N1d—H2n1d···O1d^vi	0.88 (4)	2.28 (4)	3.11 (2)	157 (6)
N1d—H2n1d···O2d^vi	0.88 (4)	2.56 (5)	3.320 (19)	145 (5)
N1d—H2n1d···O1a^vi	0.88 (4)	3.35 (6)	3.94 (2)	127 (5)

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