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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].

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CCDC references: 1033499; 1033498; 1033497; 1033496

Introduction top

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 Caryl—NH2 bonds with the N atom in sp2- and sp3-hybridized states, respectively.

Experimental top

Synthesis and crystallization top

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.

Refinement top

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 Uiso(H) = 1.2Ueq(C). The primary amine H atoms were restrained to N—H = 0.880 (1) Å and the isotropic displacement parameters set at Uiso(H) = 1.2Ueq(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 Robs = 0.0276, wRobs = 0.0749, Rall = 0.0295, wRall = 0.0761, Sall = 2.20, Sobs = 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.

Results and discussion top

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.

RA = 0.0361 and RA = 0.0710 for the low-temperature phases of (I) and (II), respectively, while RD = 1.0003 and RA = 1.0000 for the respective structures. (The factors RA and RD 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 top

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 top

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 top
[Figure 1] 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).
[Figure 2] 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).
[Figure 3] 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.
[Figure 4] Fig. 4. The molecules of the low-temperature phase of (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 5] 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.
[Figure 6] 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.
[Figure 7] 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.
[Figure 8] 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.
[Figure 9] 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.
[Figure 10] 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.
[Figure 11] 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.
[Figure 12] 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.
[Figure 13] 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.)
[Figure 14] 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.
[Figure 15] 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.
[Figure 16] 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 top
Crystal data top
C6H5ClN2O2F(000) = 352
Mr = 172.6Dx = 1.551 Mg m3
Monoclinic, P21/nMelting point: 378 K
Hall symbol: -P 2ynCu Kα radiation, λ = 1.5418 Å
a = 12.8800 (9) ÅCell parameters from 2275 reflections
b = 4.0398 (3) Åθ = 3.8–66.0°
c = 15.2317 (11) ŵ = 4.19 mm1
β = 111.263 (7)°T = 293 K
V = 738.59 (10) Å3Prism, yellow
Z = 40.45 × 0.25 × 0.20 mm
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
1298 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source975 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.046
Detector resolution: 5.1892 pixels mm-1θmax = 67.2°, θmin = 3.9°
ω scansh = 1511
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
k = 44
Tmin = 0.327, Tmax = 0.433l = 1618
4809 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.045Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.111(Δ/σ)max = 0.042
S = 1.92Δρmax = 0.33 e Å3
1298 reflectionsΔρmin = 0.24 e Å3
125 parametersExtinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
2 restraintsExtinction coefficient: 690 (180)
14 constraints
Crystal data top
C6H5ClN2O2V = 738.59 (10) Å3
Mr = 172.6Z = 4
Monoclinic, P21/nCu Kα radiation
a = 12.8800 (9) ŵ = 4.19 mm1
b = 4.0398 (3) ÅT = 293 K
c = 15.2317 (11) Å0.45 × 0.25 × 0.20 mm
β = 111.263 (7)°
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
1298 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
975 reflections with I > 3σ(I)
Tmin = 0.327, Tmax = 0.433Rint = 0.046
4809 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0452 restraints
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.92Δρmax = 0.33 e Å3
1298 reflectionsΔρmin = 0.24 e Å3
125 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl1a0.30128 (8)0.3087 (2)0.36231 (6)0.0945 (4)
C1a0.32455 (19)0.1016 (6)0.64561 (16)0.0537 (10)
C2a0.2251 (2)0.1268 (6)0.56950 (17)0.0562 (10)
H1c2a0.1640020.2288850.576840.0674*
C3a0.2162 (2)0.0013 (6)0.48293 (17)0.0575 (10)
C4a0.3054 (2)0.1498 (6)0.46879 (18)0.0607 (11)
C5a0.4041 (2)0.1750 (7)0.54566 (19)0.0626 (11)
H1c5a0.4652080.2775120.5384780.0715*
C6a0.4136 (2)0.0522 (7)0.63187 (18)0.0596 (10)
H1c6a0.4809760.0723450.6821870.0752*
N1a0.3323 (2)0.2150 (7)0.73375 (16)0.0705 (10)
H1n1a0.286 (2)0.377 (5)0.732 (2)0.0846*
H2n1a0.4023 (8)0.248 (7)0.7701 (18)0.0846*
N2a0.1075 (2)0.0389 (9)0.40661 (19)0.0833 (13)
O1a0.0671 (6)0.187 (2)0.3629 (6)0.170 (4)0.5
O2a0.0605 (5)0.3049 (17)0.4061 (5)0.119 (3)0.5
O1d0.1014 (4)0.0481 (15)0.3223 (3)0.091 (2)0.5
O2d0.0244 (4)0.066 (2)0.4256 (4)0.120 (3)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl1a0.1369 (8)0.0901 (7)0.0635 (5)0.0083 (5)0.0446 (5)0.0114 (4)
C1a0.0508 (13)0.0582 (16)0.0494 (14)0.0061 (11)0.0147 (11)0.0049 (11)
C2a0.0485 (13)0.0614 (16)0.0573 (15)0.0025 (11)0.0176 (11)0.0039 (12)
C3a0.0537 (14)0.0592 (16)0.0494 (14)0.0113 (12)0.0064 (11)0.0078 (11)
C4a0.0795 (18)0.0517 (16)0.0532 (15)0.0078 (12)0.0268 (14)0.0015 (11)
C5a0.0638 (16)0.0608 (17)0.0673 (17)0.0065 (12)0.0286 (14)0.0075 (13)
C6a0.0502 (14)0.0668 (18)0.0560 (15)0.0005 (11)0.0124 (12)0.0100 (12)
N1a0.0654 (15)0.0917 (19)0.0500 (13)0.0038 (12)0.0158 (11)0.0075 (12)
N2a0.0701 (18)0.091 (2)0.0667 (18)0.0124 (16)0.0012 (14)0.0060 (15)
O1a0.130 (5)0.142 (6)0.154 (7)0.017 (5)0.047 (5)0.073 (6)
O2a0.083 (4)0.105 (5)0.117 (5)0.003 (4)0.026 (3)0.007 (4)
O1d0.092 (3)0.113 (4)0.043 (2)0.010 (3)0.005 (2)0.005 (2)
O2d0.052 (3)0.197 (8)0.092 (4)0.011 (3)0.005 (3)0.027 (4)
Geometric parameters (Å, º) top
Cl1a—C4a1.727 (3)C5a—H1c5a0.93
C1a—C2a1.385 (3)C5a—C6a1.367 (4)
C1a—C6a1.385 (4)C6a—H1c6a0.93
C1a—N1a1.387 (4)N1a—H1n1a0.88 (3)
C2a—H1c2a0.93N1a—H2n1a0.880 (12)
C2a—C3a1.378 (4)N2a—O1a1.137 (8)
C3a—C4a1.385 (4)N2a—O2a1.231 (8)
C3a—N2a1.468 (3)N2a—O1d1.259 (6)
C4a—C5a1.385 (3)N2a—O2d1.210 (7)
Cl1a—C4a—C3a124.43 (18)H1c5a—C5a—C6a119.34
Cl1a—C4a—C5a118.2 (2)C1a—C6a—C5a121.2 (2)
C2a—C1a—C6a118.1 (2)C1a—C6a—H1c6a119.42
C2a—C1a—N1a120.4 (2)C5a—C6a—H1c6a119.42
C6a—C1a—N1a121.4 (2)C1a—N1a—H1n1a114 (2)
C1a—C2a—H1c2a119.86C1a—N1a—H2n1a110.9 (18)
C1a—C2a—C3a120.3 (3)H1n1a—N1a—H2n1a116 (2)
H1c2a—C2a—C3a119.86C3a—N2a—O1a118.9 (5)
C2a—C3a—C4a121.7 (2)C3a—N2a—O2a114.9 (4)
C2a—C3a—N2a116.3 (3)C3a—N2a—O1d120.0 (4)
C4a—C3a—N2a122.0 (2)C3a—N2a—O2d119.5 (3)
C3a—C4a—C5a117.4 (3)O1a—N2a—O2a125.2 (5)
C4a—C5a—H1c5a119.34O1d—N2a—O2d120.5 (4)
C4a—C5a—C6a121.3 (3)
H1n1a—N1a—C1a—C2a28 (2)H2n1a—N1a—C1a—C6a22 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ai0.88 (3)2.25 (3)3.096 (4)162 (3)
N1a—H2n1a···O1aii0.880 (12)2.73 (2)3.512 (8)148 (2)
N1a—H2n1a···O2aii0.880 (12)2.330 (18)3.153 (6)156 (2)
N1a—H2n1a···O1dii0.880 (12)2.531 (15)3.369 (5)159 (2)
N1a—H2n1a···O2dii0.880 (12)2.44 (2)3.193 (6)144 (2)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
(Ib) 4-Chloro-3-nitroaniline top
Crystal data top
C6H5ClN2O2F(000) = 704
Mr = 172.6Dx = 1.605 Mg m3
Monoclinic, PnMelting point: 378 K
Hall symbol: P -2yacCu Kα radiation, λ = 1.5418 Å
a = 12.7260 (4) ÅCell parameters from 14208 reflections
b = 7.9721 (2) Åθ = 3.1–67.0°
c = 15.0098 (4) ŵ = 4.34 mm1
β = 110.352 (3)°T = 120 K
V = 1427.73 (7) Å3Plate, brown
Z = 80.45 × 0.13 × 0.06 mm
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
5014 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source4733 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.025
Detector resolution: 10.3784 pixels mm-1θmax = 67.1°, θmin = 3.9°
ω scansh = 1515
Absorption correction: analytical
CrysAlis PRO (Agilent Technologies, 2012)
k = 98
Tmin = 0.362, Tmax = 0.781l = 1717
23718 measured reflections
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
S = 1.94(Δ/σ)max = 0.050
5014 reflectionsΔρmax = 0.17 e Å3
423 parametersΔρmin = 0.16 e Å3
8 restraintsExtinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
58 constraintsExtinction coefficient: 960 (90)
Primary atom site location: structure-invariant direct methodsAbsolute structure: 2479 of Friedel pairs used in the refinement
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.504 (15)
Crystal data top
C6H5ClN2O2V = 1427.73 (7) Å3
Mr = 172.6Z = 8
Monoclinic, PnCu Kα radiation
a = 12.7260 (4) ŵ = 4.34 mm1
b = 7.9721 (2) ÅT = 120 K
c = 15.0098 (4) Å0.45 × 0.13 × 0.06 mm
β = 110.352 (3)°
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
5014 independent reflections
Absorption correction: analytical
CrysAlis PRO (Agilent Technologies, 2012)
4733 reflections with I > 3σ(I)
Tmin = 0.362, Tmax = 0.781Rint = 0.025
23718 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066Δρmax = 0.17 e Å3
S = 1.94Δρmin = 0.16 e Å3
5014 reflectionsAbsolute structure: 2479 of Friedel pairs used in the refinement
423 parametersAbsolute structure parameter: 0.504 (15)
8 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl1a0.28699 (7)0.28021 (9)0.37138 (6)0.0321 (3)
C1a0.3155 (3)0.0653 (4)0.6595 (2)0.0191 (10)
C2a0.2150 (3)0.0498 (3)0.5829 (2)0.0190 (10)
H1c2a0.1535660.0090850.590150.0228*
C3a0.2056 (2)0.1196 (4)0.4978 (2)0.0205 (9)
C4a0.2957 (3)0.2023 (3)0.4824 (2)0.0224 (11)
C5a0.3940 (3)0.2134 (3)0.5585 (3)0.0244 (12)
H1c5a0.4566250.2675980.5505340.0261*
C6a0.4044 (2)0.1488 (4)0.6455 (2)0.0217 (9)
H1c6a0.4731910.1609820.6970110.0293*
N1a0.3216 (2)0.0066 (5)0.74874 (19)0.0253 (8)
H1n1a0.2812 (18)0.0858 (18)0.7380 (18)0.0304*
H2n1a0.3889 (9)0.013 (3)0.7923 (14)0.0304*
N2a0.0954 (2)0.1050 (3)0.41968 (18)0.0257 (9)
O1a0.05508 (18)0.2288 (2)0.37495 (16)0.0438 (6)
O2a0.05060 (18)0.03283 (19)0.40980 (15)0.0348 (5)
Cl1b0.68085 (8)0.46899 (9)0.64354 (6)0.0312 (3)
C1b0.6525 (3)0.6864 (4)0.3560 (2)0.0194 (10)
C2b0.7534 (3)0.6969 (4)0.4320 (2)0.0211 (10)
H1c2b0.8160950.7516250.4244620.0253*
C3b0.7617 (3)0.6258 (4)0.5197 (2)0.0199 (9)
C4b0.6739 (3)0.5467 (3)0.5348 (2)0.0210 (10)
C5b0.5715 (3)0.5377 (3)0.4586 (2)0.0215 (11)
H1c5b0.508750.4853370.4673080.0273*
C6b0.5615 (2)0.6050 (4)0.3705 (2)0.0227 (10)
H1c6b0.4921970.5959030.3192520.0257*
N1b0.6437 (2)0.7475 (5)0.2682 (2)0.0231 (8)
H1n1b0.6961 (15)0.814 (2)0.2624 (17)0.0277*
H2n1b0.5758 (9)0.780 (3)0.2332 (16)0.0277*
N2b0.8713 (2)0.6389 (3)0.59283 (18)0.0254 (9)
O1b0.91371 (19)0.5118 (2)0.63758 (16)0.0428 (6)
O2b0.91796 (19)0.77623 (19)0.60795 (15)0.0370 (5)
Cl1c0.67829 (7)0.04585 (9)0.64328 (6)0.0290 (3)
C1c0.6569 (3)0.1806 (4)0.3591 (2)0.0196 (10)
C2c0.7574 (3)0.1892 (4)0.4359 (2)0.0210 (10)
H1c2c0.8211890.2401980.4281760.0252*
C3c0.7649 (2)0.1231 (3)0.5244 (2)0.0191 (9)
C4c0.6753 (3)0.0461 (3)0.5388 (3)0.0201 (10)
C5c0.5742 (3)0.0347 (3)0.4609 (2)0.0206 (10)
H1c5c0.5112890.0190180.4686340.0272*
C6c0.5651 (2)0.1006 (4)0.3733 (2)0.0227 (10)
H1c6c0.49590.09190.3218950.0247*
N1c0.6488 (2)0.2408 (5)0.2715 (2)0.0240 (8)
H1n1c0.6990 (16)0.311 (2)0.2649 (18)0.0288*
H2n1c0.5804 (10)0.269 (3)0.2356 (16)0.0288*
N2c0.8742 (2)0.1387 (3)0.59792 (18)0.0254 (9)
O1c0.88096 (18)0.14124 (18)0.68251 (14)0.0318 (5)
O2c0.95769 (18)0.1515 (2)0.57504 (16)0.0355 (6)
Cl1d0.28099 (7)0.78868 (9)0.36544 (6)0.0280 (3)
C1d0.3034 (3)0.5644 (4)0.6503 (2)0.0189 (9)
C2d0.2020 (3)0.5556 (3)0.5741 (2)0.0183 (10)
H1c2d0.1387550.5042410.5825470.022*
C3d0.1931 (2)0.6205 (4)0.4873 (2)0.0199 (9)
C4d0.2849 (3)0.6988 (3)0.4724 (2)0.0217 (10)
C5d0.3827 (3)0.7096 (3)0.5493 (3)0.0227 (11)
H1c5d0.4453570.7646340.5418220.0249*
C6d0.3933 (2)0.6439 (4)0.6366 (2)0.0207 (10)
H1c6d0.4626110.6530880.687780.0272*
N1d0.3092 (2)0.5026 (5)0.73903 (18)0.0241 (8)
H1n1d0.2639 (17)0.416 (2)0.7300 (17)0.029*
H2n1d0.3771 (9)0.510 (3)0.7817 (15)0.029*
N2d0.0832 (2)0.6031 (3)0.40978 (17)0.0220 (8)
O1d0.07890 (18)0.59989 (19)0.32793 (15)0.0319 (5)
O2d0.00109 (18)0.5888 (2)0.43467 (15)0.0356 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl1a0.0431 (5)0.0311 (4)0.0249 (4)0.0013 (3)0.0154 (3)0.0033 (3)
C1a0.0152 (14)0.0211 (12)0.0208 (16)0.0042 (10)0.0059 (12)0.0016 (10)
C2a0.0165 (13)0.0177 (14)0.0219 (16)0.0014 (9)0.0055 (12)0.0024 (9)
C3a0.0158 (13)0.0204 (13)0.0218 (16)0.0014 (10)0.0021 (11)0.0041 (10)
C4a0.0325 (17)0.0172 (15)0.0189 (16)0.0026 (10)0.0107 (14)0.0002 (9)
C5a0.0234 (16)0.0206 (17)0.0328 (19)0.0033 (10)0.0142 (14)0.0059 (9)
C6a0.0191 (14)0.0256 (14)0.0186 (14)0.0020 (11)0.0041 (11)0.0037 (10)
N1a0.0241 (12)0.0338 (13)0.0166 (13)0.0015 (11)0.0053 (10)0.0065 (10)
N2a0.0264 (14)0.0249 (13)0.0208 (13)0.0059 (10)0.0020 (11)0.0013 (9)
O1a0.0366 (9)0.0361 (10)0.0411 (9)0.0041 (7)0.0088 (7)0.0130 (7)
O2a0.0275 (8)0.0275 (9)0.0368 (8)0.0031 (7)0.0048 (6)0.0048 (6)
Cl1b0.0435 (5)0.0308 (4)0.0221 (4)0.0008 (3)0.0149 (3)0.0051 (3)
C1b0.0236 (16)0.0191 (13)0.0155 (14)0.0034 (10)0.0070 (12)0.0026 (10)
C2b0.0187 (14)0.0216 (15)0.0235 (16)0.0050 (10)0.0080 (12)0.0009 (10)
C3b0.0254 (14)0.0155 (13)0.0160 (13)0.0049 (10)0.0039 (11)0.0008 (9)
C4b0.0241 (15)0.0188 (15)0.0213 (15)0.0018 (10)0.0095 (13)0.0015 (9)
C5b0.0218 (16)0.0229 (17)0.0212 (15)0.0016 (10)0.0094 (13)0.0036 (9)
C6b0.0167 (14)0.0229 (15)0.0279 (16)0.0002 (11)0.0069 (12)0.0040 (11)
N1b0.0159 (11)0.0309 (12)0.0198 (13)0.0008 (10)0.0027 (9)0.0010 (11)
N2b0.0255 (13)0.0274 (13)0.0204 (13)0.0007 (10)0.0044 (10)0.0009 (9)
O1b0.0384 (9)0.0368 (9)0.0395 (9)0.0071 (7)0.0040 (7)0.0153 (7)
O2b0.0307 (7)0.0286 (9)0.0384 (8)0.0022 (7)0.0049 (6)0.0043 (7)
Cl1c0.0363 (4)0.0307 (4)0.0223 (3)0.0000 (3)0.0131 (3)0.0018 (3)
C1c0.0224 (16)0.0188 (12)0.0171 (14)0.0037 (10)0.0062 (12)0.0032 (10)
C2c0.0180 (14)0.0217 (14)0.0244 (16)0.0037 (10)0.0087 (12)0.0002 (11)
C3c0.0224 (14)0.0171 (13)0.0157 (13)0.0039 (10)0.0039 (10)0.0019 (9)
C4c0.0200 (14)0.0190 (15)0.0223 (15)0.0018 (10)0.0088 (12)0.0014 (9)
C5c0.0194 (15)0.0221 (17)0.0213 (15)0.0014 (10)0.0084 (13)0.0032 (9)
C6c0.0171 (14)0.0230 (15)0.0268 (16)0.0002 (11)0.0061 (12)0.0043 (11)
N1c0.0167 (11)0.0302 (13)0.0222 (13)0.0005 (10)0.0032 (9)0.0008 (11)
N2c0.0252 (13)0.0224 (13)0.0253 (14)0.0014 (10)0.0043 (10)0.0015 (9)
O1c0.0347 (8)0.0350 (9)0.0187 (7)0.0014 (6)0.0006 (6)0.0009 (6)
O2c0.0194 (7)0.0493 (10)0.0342 (8)0.0008 (7)0.0049 (6)0.0036 (7)
Cl1d0.0360 (4)0.0301 (4)0.0197 (4)0.0011 (3)0.0121 (3)0.0043 (3)
C1d0.0193 (15)0.0176 (12)0.0196 (15)0.0038 (10)0.0064 (12)0.0013 (10)
C2d0.0185 (15)0.0163 (14)0.0201 (15)0.0035 (10)0.0067 (12)0.0026 (10)
C3d0.0135 (13)0.0213 (13)0.0219 (14)0.0007 (10)0.0024 (11)0.0033 (10)
C4d0.0321 (16)0.0180 (15)0.0175 (15)0.0038 (11)0.0119 (13)0.0013 (9)
C5d0.0194 (15)0.0192 (17)0.0322 (17)0.0026 (10)0.0127 (13)0.0037 (10)
C6d0.0194 (15)0.0236 (14)0.0166 (15)0.0024 (11)0.0031 (12)0.0040 (10)
N1d0.0249 (13)0.0315 (12)0.0153 (13)0.0007 (11)0.0061 (10)0.0079 (11)
N2d0.0203 (13)0.0211 (12)0.0181 (13)0.0063 (9)0.0017 (9)0.0000 (9)
O1d0.0351 (8)0.0331 (9)0.0197 (8)0.0007 (6)0.0001 (6)0.0004 (6)
O2d0.0206 (8)0.0471 (10)0.0349 (8)0.0016 (7)0.0044 (6)0.0037 (7)
Geometric parameters (Å, º) top
Cl1a—C4a1.745 (4)Cl1c—C4c1.720 (4)
C1a—C2a1.397 (4)C1c—C2c1.394 (4)
C1a—C6a1.391 (5)C1c—C6c1.411 (5)
C1a—N1a1.395 (5)C1c—N1c1.371 (5)
C2a—H1c2a0.95C2c—H1c2c0.95
C2a—C3a1.360 (5)C2c—C3c1.401 (5)
C3a—C4a1.410 (5)C3c—C4c1.376 (5)
C3a—N2a1.486 (3)C3c—N2c1.450 (3)
C4a—C5a1.372 (4)C4c—C5c1.409 (4)
C5a—H1c5a0.95C5c—H1c5c0.95
C5a—C6a1.367 (5)C5c—C6c1.382 (5)
C6a—H1c6a0.95C6c—H1c6c0.95
N1a—H1n1a0.880 (17)N1c—H1n1c0.88 (2)
N1a—H2n1a0.880 (12)N1c—H2n1c0.880 (13)
H1n1a—H2n1a1.54 (2)H1n1c—H2n1c1.46 (2)
N2a—O1a1.204 (3)N2c—O1c1.243 (4)
N2a—O2a1.223 (3)N2c—O2c1.229 (4)
Cl1b—C4b1.719 (4)Cl1d—C4d1.742 (4)
C1b—C2b1.392 (4)C1d—C2d1.397 (4)
C1b—C6b1.408 (5)C1d—C6d1.385 (5)
C1b—N1b1.373 (5)C1d—N1d1.398 (5)
C2b—H1c2b0.95C2d—H1c2d0.95
C2b—C3b1.404 (5)C2d—C3d1.370 (5)
C3b—C4b1.368 (5)C3d—C4d1.410 (5)
C3b—N2b1.447 (3)C3d—N2d1.483 (3)
C4b—C5b1.405 (4)C4d—C5d1.375 (4)
C5b—H1c5b0.95C5d—H1c5d0.95
C5b—C6b1.392 (5)C5d—C6d1.373 (5)
C6b—H1c6b0.95C6d—H1c6d0.95
N1b—H1n1b0.88 (2)N1d—H1n1d0.880 (18)
N1b—H2n1b0.880 (13)N1d—H2n1d0.880 (13)
H1n1b—H2n1b1.46 (2)H1n1d—H2n1d1.57 (2)
N2b—O1b1.232 (3)N2d—O1d1.211 (4)
N2b—O2b1.228 (3)N2d—O2d1.231 (4)
Cl1a—C4a—C3a122.5 (2)H1n1b—N1b—H2n1b112.4 (19)
Cl1a—C4a—C5a120.6 (3)C3b—N2b—O1b118.6 (2)
Cl1b—C4b—C3b123.2 (2)C3b—N2b—O2b118.8 (2)
Cl1b—C4b—C5b118.8 (3)O1b—N2b—O2b122.7 (2)
Cl1c—C4c—C3c125.2 (2)C2c—C1c—C6c117.9 (3)
Cl1c—C4c—C5c117.0 (3)C2c—C1c—N1c121.1 (3)
Cl1d—C4d—C3d124.6 (3)C6c—C1c—N1c120.9 (3)
Cl1d—C4d—C5d118.4 (3)C1c—C2c—H1c2c119.84
C2a—C1a—C6a118.5 (3)C1c—C2c—C3c120.3 (3)
C2a—C1a—N1a119.4 (3)H1c2c—C2c—C3c119.8335
C6a—C1a—N1a121.9 (3)C2c—C3c—C4c122.0 (3)
C1a—C2a—H1c2a120.2115C2c—C3c—N2c114.8 (3)
C1a—C2a—C3a119.6 (3)C4c—C3c—N2c123.2 (3)
H1c2a—C2a—C3a120.2C3c—C4c—C5c117.8 (3)
C2a—C3a—C4a122.3 (3)C4c—C5c—H1c5c119.51
C2a—C3a—N2a117.3 (3)C4c—C5c—C6c121.0 (3)
C4a—C3a—N2a120.4 (3)H1c5c—C5c—C6c119.51
C3a—C4a—C5a116.9 (3)C1c—C6c—C5c121.0 (3)
C4a—C5a—H1c5a119.05C1c—C6c—H1c6c119.5
C4a—C5a—C6a121.9 (4)C5c—C6c—H1c6c119.5
H1c5a—C5a—C6a119.0481C1c—N1c—H1n1c121.0 (16)
C1a—C6a—C5a120.8 (3)C1c—N1c—H2n1c113.9 (16)
C1a—C6a—H1c6a119.62H1n1c—N1c—H2n1c112 (2)
C5a—C6a—H1c6a119.62C3c—N2c—O1c119.1 (3)
C1a—N1a—H1n1a105.7 (18)C3c—N2c—O2c119.2 (3)
C1a—N1a—H2n1a114.2 (15)O1c—N2c—O2c121.7 (3)
H1n1a—N1a—H2n1a122 (2)C2d—C1d—C6d118.5 (3)
C3a—N2a—O1a118.6 (2)C2d—C1d—N1d119.4 (3)
C3a—N2a—O2a116.0 (2)C6d—C1d—N1d122.0 (2)
O1a—N2a—O2a125.3 (2)C1d—C2d—H1c2d119.77
C2b—C1b—C6b118.4 (3)C1d—C2d—C3d120.5 (3)
C2b—C1b—N1b120.6 (3)H1c2d—C2d—C3d119.77
C6b—C1b—N1b121.0 (3)C2d—C3d—C4d121.3 (3)
C1b—C2b—H1c2b120.3C2d—C3d—N2d117.0 (3)
C1b—C2b—C3b119.4 (3)C4d—C3d—N2d121.7 (3)
H1c2b—C2b—C3b120.29C3d—C4d—C5d116.9 (3)
C2b—C3b—C4b122.8 (3)C4d—C5d—H1c5d118.75
C2b—C3b—N2b114.9 (3)C4d—C5d—C6d122.5 (3)
C4b—C3b—N2b122.3 (3)H1c5d—C5d—C6d118.75
C3b—C4b—C5b117.9 (3)C1d—C6d—C5d120.3 (3)
C4b—C5b—H1c5b119.79C1d—C6d—H1c6d119.85
C4b—C5b—C6b120.4 (4)C5d—C6d—H1c6d119.86
H1c5b—C5b—C6b119.79C1d—N1d—H1n1d108.4 (16)
C1b—C6b—C5b121.0 (3)C1d—N1d—H2n1d112.6 (15)
C1b—C6b—H1c6b119.49H1n1d—N1d—H2n1d126 (2)
C5b—C6b—H1c6b119.48C3d—N2d—O1d119.7 (3)
C1b—N1b—H1n1b119.8 (15)C3d—N2d—O2d116.1 (3)
C1b—N1b—H2n1b114.5 (15)O1d—N2d—O2d124.2 (2)
H1n1a—N1a—C1a—C2a37.4 (15)H1n1c—N1c—C1c—C2c17.9 (17)
H2n1a—N1a—C1a—C2a174.9 (18)H2n1c—N1a—C1c—C2c157.0 (9)
H1n1b—N1b—C1b—C2b14.4 (17)H1n1d—N1d—C1d—C2d33.5 (15)
H2n1b—N1b—C1b—C2b152.4 (16)H2n1d—N1d—C1d—C2d177.4 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ci0.880 (17)2.28 (2)3.060 (5)147 (2)
N1a—H2n1a···O1aii0.880 (13)2.808 (19)3.468 (4)133 (2)
N1a—H2n1a···O2aii0.880 (12)2.201 (13)3.079 (3)175.2 (19)
N1b—H1n1b···N1aiii0.88 (2)2.21 (2)3.085 (5)176.7 (19)
N1b—H2n1b···O1biv0.880 (13)3.112 (19)3.562 (4)114.0 (17)
N1b—H2n1b···O1civ0.880 (13)2.410 (13)3.260 (3)163 (2)
N1b—H2n1b···O2civ0.880 (13)2.389 (19)3.144 (3)144 (2)
N1c—H1n1c···N1diii0.88 (2)2.17 (2)3.046 (5)174.5 (17)
N1c—H2n1c···O1biv0.880 (13)2.745 (18)3.563 (3)155.3 (19)
N1c—H2n1c···O2biv0.880 (13)2.307 (15)3.108 (3)151 (2)
N1d—H1n1d···N1bv0.880 (18)2.23 (2)3.041 (5)153 (2)
N1d—H2n1d···O1dvi0.880 (13)2.569 (14)3.323 (3)144 (2)
N1d—H2n1d···O2dvi0.880 (13)2.421 (19)3.183 (3)145 (2)
N1d—H2n1d···O1avi0.880 (13)3.04 (2)3.754 (3)140 (2)
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1, z1/2; (iv) x1/2, y+1, z1/2; (v) x1/2, y+1, z+1/2; (vi) x+1/2, y+1, z+1/2.
(IIa) 4-Iodo-3-nitroaniline top
Crystal data top
C6H5IN2O2F(000) = 496
Mr = 264Dx = 2.208 Mg m3
Monoclinic, P21/nMelting point: 413 K
Hall symbol: -P 2ynCu Kα radiation, λ = 1.5418 Å
a = 12.5219 (8) ÅCell parameters from 3022 reflections
b = 4.2601 (3) Åθ = 3.9–66.7°
c = 16.0008 (9) ŵ = 31.34 mm1
β = 111.556 (6)°T = 293 K
V = 793.86 (9) Å3Plate, brown
Z = 40.50 × 0.24 × 0.05 mm
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
1380 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source1093 reflections with I > 3σ(I)
Mirror monochromatorRint = 0.062
Detector resolution: 5.1892 pixels mm-1θmax = 67.0°, θmin = 3.9°
ω scansh = 1414
Absorption correction: gaussian
(CrysAlis PRO; Oxford Diffraction, 2010)
k = 44
Tmin = 0.002, Tmax = 0.361l = 1918
5100 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.053Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.120(Δ/σ)max = 0.015
S = 2.31Δρmax = 1.90 e Å3
1380 reflectionsΔρmin = 0.85 e Å3
125 parametersExtinction correction: B–C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
2 restraintsExtinction coefficient: 220 (50)
14 constraints
Crystal data top
C6H5IN2O2V = 793.86 (9) Å3
Mr = 264Z = 4
Monoclinic, P21/nCu Kα radiation
a = 12.5219 (8) ŵ = 31.34 mm1
b = 4.2601 (3) ÅT = 293 K
c = 16.0008 (9) Å0.50 × 0.24 × 0.05 mm
β = 111.556 (6)°
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
1380 independent reflections
Absorption correction: gaussian
(CrysAlis PRO; Oxford Diffraction, 2010)
1093 reflections with I > 3σ(I)
Tmin = 0.002, Tmax = 0.361Rint = 0.062
5100 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0532 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 2.31Δρmax = 1.90 e Å3
1380 reflectionsΔρmin = 0.85 e Å3
125 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
I1a0.28645 (6)0.33319 (17)0.35667 (3)0.0691 (3)
C1a0.3183 (8)0.108 (2)0.6483 (5)0.058 (4)
C2a0.2169 (8)0.150 (3)0.5759 (5)0.058 (4)
H1c2a0.1568030.2610370.5829120.0692*
C3a0.2049 (7)0.026 (3)0.4927 (5)0.053 (3)
C4a0.2914 (8)0.141 (2)0.4785 (5)0.056 (3)
C5a0.3940 (9)0.178 (3)0.5511 (6)0.065 (4)
H1c5a0.4548370.2841680.5436790.082*
C6a0.4059 (8)0.058 (3)0.6348 (5)0.068 (4)
H1c6a0.4745160.0894480.682990.0783*
N1a0.3285 (9)0.217 (3)0.7324 (5)0.082 (4)
H1n1a0.285 (11)0.38 (2)0.726 (9)0.0978*
H2n1a0.397 (5)0.20 (3)0.774 (6)0.0978*
N2a0.0925 (7)0.080 (2)0.4212 (5)0.065 (4)
O1a0.0511 (16)0.130 (7)0.3672 (13)0.093 (9)0.5
O2a0.046 (2)0.330 (6)0.4264 (15)0.085 (9)0.5
O1d0.0794 (16)0.041 (6)0.3431 (11)0.086 (9)0.5
O2d0.012 (2)0.172 (8)0.4381 (15)0.094 (11)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I1a0.1026 (6)0.0537 (5)0.0606 (4)0.0049 (4)0.0412 (3)0.0015 (2)
C1a0.056 (5)0.070 (8)0.048 (4)0.015 (5)0.017 (3)0.004 (3)
C2a0.057 (5)0.062 (7)0.057 (4)0.007 (5)0.024 (4)0.002 (4)
C3a0.055 (5)0.054 (6)0.049 (3)0.005 (4)0.017 (3)0.004 (3)
C4a0.064 (5)0.063 (7)0.043 (3)0.002 (5)0.023 (3)0.000 (3)
C5a0.063 (6)0.070 (8)0.066 (5)0.010 (5)0.028 (4)0.013 (4)
C6a0.055 (5)0.086 (9)0.054 (4)0.003 (5)0.008 (4)0.006 (4)
N1a0.076 (6)0.108 (9)0.052 (4)0.011 (5)0.013 (4)0.015 (4)
N2a0.056 (5)0.080 (8)0.052 (4)0.004 (5)0.012 (3)0.000 (3)
O1a0.064 (11)0.12 (2)0.078 (10)0.016 (11)0.002 (8)0.023 (11)
O2a0.061 (13)0.083 (19)0.090 (11)0.014 (11)0.004 (9)0.002 (11)
O1d0.063 (11)0.11 (2)0.066 (9)0.016 (11)0.001 (7)0.009 (9)
O2d0.064 (13)0.13 (3)0.086 (10)0.001 (13)0.020 (8)0.010 (13)
Geometric parameters (Å, º) top
I1a—C4a2.095 (8)C5a—C6a1.389 (14)
C1a—C2a1.380 (11)C6a—H1c6a0.93
C1a—C6a1.387 (16)N1a—H1n1a0.88 (11)
C1a—N1a1.384 (12)N1a—H2n1a0.88 (6)
C2a—H1c2a0.93N2a—O1a1.22 (3)
C2a—C3a1.388 (12)N2a—O2a1.23 (3)
C3a—C4a1.383 (15)N2a—O1d1.21 (2)
C3a—N2a1.469 (10)N2a—O2d1.20 (3)
C4a—C5a1.388 (11)O2a—O2d0.85 (4)
C5a—H1c5a0.93
I1a—C4a—C3a126.7 (5)C1a—C6a—C5a121.8 (8)
I1a—C4a—C5a115.8 (8)C1a—C6a—H1c6a119.08
C6a—C1a—N1a121.9 (8)C5a—C6a—H1c6a119.08
C1a—C2a—H1c2a120.08C1a—N1a—H1n1a110 (9)
C1a—C2a—C3a119.8 (10)C1a—N1a—H2n1a116 (7)
H1c2a—C2a—C3a120.08H1n1a—N1a—H2n1a122 (12)
C2a—C3a—C4a122.5 (7)C3a—N2a—O1a118.3 (13)
C2a—C3a—N2a115.0 (9)C3a—N2a—O2a115.2 (12)
C4a—C3a—N2a122.4 (7)C3a—N2a—O1d120.7 (13)
C3a—C4a—C5a117.5 (8)C3a—N2a—O2d121.2 (12)
C4a—C5a—H1c5a119.92O1a—N2a—O2a126.3 (15)
C4a—C5a—C6a120.2 (10)O1d—N2a—O2d118.1 (15)
H1c5a—C5a—C6a119.91
H1n1a—N1a—C1a—C2a30 (9)H2n1a—N1a—C1a—C6a10 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ai0.88 (11)2.27 (14)3.088 (17)155 (13)
N1a—H2n1a···O1aii0.88 (6)2.67 (11)3.33 (2)133 (12)
N1a—H2n1a···O2aii0.88 (6)2.46 (8)3.30 (2)159 (9)
N1a—H2n1a···O1dii0.88 (6)2.40 (8)3.16 (2)145 (12)
N1a—H2n1a···O2dii0.88 (6)2.54 (9)3.29 (2)143 (9)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
(IIb) 4-Iodo-3-nitroaniline top
Crystal data top
C6H5IN2O2F(000) = 992
Mr = 264Dx = 2.273 Mg m3
Monoclinic, PnMelting point: 413 K
Hall symbol: P -2yacMo Kα radiation, λ = 0.71069 Å
a = 12.5188 (9) ÅCell parameters from 5556 reflections
b = 8.2955 (5) Åθ = 3.0–32.6°
c = 15.9287 (10) ŵ = 4.1 mm1
β = 111.141 (6)°T = 120 K
V = 1542.86 (19) Å3Plate, brown
Z = 80.3 × 0.15 × 0.05 mm
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
9998 independent reflections
Radiation source: Enhance (Mo) X-ray Source4208 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.079
Detector resolution: 10.3784 pixels mm-1θmax = 31.5°, θmin = 3.0°
ω scansh = 1818
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
k = 1212
Tmin = 0.483, Tmax = 0.815l = 2323
27795 measured reflections
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.048Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2)
wR(F2) = 0.118(Δ/σ)max = 0.020
S = 1.32Δρmax = 2.58 e Å3
9998 reflectionsΔρmin = 2.00 e Å3
224 parametersAbsolute structure: 3424 of Friedel pairs used in the refinement
4 restraintsAbsolute structure parameter: 0.41 (13)
30 constraints
Crystal data top
C6H5IN2O2V = 1542.86 (19) Å3
Mr = 264Z = 8
Monoclinic, PnMo Kα radiation
a = 12.5188 (9) ŵ = 4.1 mm1
b = 8.2955 (5) ÅT = 120 K
c = 15.9287 (10) Å0.3 × 0.15 × 0.05 mm
β = 111.141 (6)°
Data collection top
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
9998 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
4208 reflections with I > 3σ(I)
Tmin = 0.483, Tmax = 0.815Rint = 0.079
27795 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118Δρmax = 2.58 e Å3
S = 1.32Δρmin = 2.00 e Å3
9998 reflectionsAbsolute structure: 3424 of Friedel pairs used in the refinement
224 parametersAbsolute structure parameter: 0.41 (13)
4 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I1a0.2870 (4)0.28757 (11)0.37137 (18)0.0245 (2)
C1a0.3234 (10)0.0570 (12)0.6651 (6)0.020 (3)
C2a0.2225 (10)0.0383 (11)0.5932 (6)0.022 (3)
H1c2a0.1616380.0216420.6003010.0262*
C3a0.2086 (8)0.1059 (9)0.5105 (6)0.020 (3)
C4a0.2946 (8)0.1906 (9)0.4956 (5)0.021 (3)
C5a0.3977 (9)0.2070 (11)0.5677 (5)0.024 (3)
H1c5a0.4595030.262480.5593670.0332*
C6a0.4117 (10)0.1441 (12)0.6514 (6)0.028 (3)
H1c6a0.4820630.1600350.7001350.0284*
N1a0.3343 (12)0.0001 (14)0.7498 (6)0.029 (3)
H1n1a0.288 (5)0.083 (5)0.744 (5)0.0347*
H2n1a0.407 (2)0.000 (8)0.785 (4)0.0347*
N2a0.0949 (7)0.0821 (9)0.4391 (6)0.025 (3)
O1a0.0540 (6)0.1949 (9)0.3888 (5)0.042 (2)
O2a0.0488 (7)0.0471 (8)0.4362 (6)0.039 (2)
I1b0.7090 (15)0.4609 (19)0.6568 (6)0.0245 (2)
C1b0.6764 (13)0.6934 (19)0.3643 (6)0.020 (3)
C2b0.7768 (12)0.7118 (16)0.4368 (7)0.022 (3)
H1c2b0.8379290.7719160.4303710.0262*
C3b0.7896 (11)0.6436 (16)0.5192 (7)0.020 (3)
C4b0.7030 (11)0.5587 (16)0.5332 (6)0.021 (3)
C5b0.6005 (11)0.5426 (17)0.4604 (8)0.024 (3)
H1c5b0.5383590.4870010.4681220.0332*
C6b0.5876 (13)0.6061 (19)0.3771 (8)0.028 (3)
H1c6b0.5176220.5903870.3279080.0284*
N1b0.6666 (17)0.751 (2)0.2800 (8)0.029 (3)
H1n1b0.713 (5)0.834 (6)0.287 (5)0.0347*
H2n1b0.594 (2)0.751 (8)0.244 (4)0.0347*
N2b0.9027 (13)0.667 (2)0.5913 (10)0.025 (3)
O1b0.9431 (15)0.554 (2)0.6416 (11)0.042 (2)
O2b0.9490 (14)0.796 (2)0.5949 (11)0.039 (2)
I1c0.7083 (4)0.04553 (11)0.65628 (18)0.0241 (2)
C1c0.6790 (11)0.1841 (12)0.3641 (6)0.025 (3)
C2c0.7818 (10)0.2030 (10)0.4366 (6)0.020 (2)
H1c2c0.8440750.2586340.4289720.0236*
C3c0.7925 (8)0.1406 (9)0.5193 (6)0.018 (3)
C4c0.7033 (8)0.0601 (8)0.5361 (5)0.018 (3)
C5c0.6018 (9)0.0418 (10)0.4623 (6)0.024 (3)
H1c5c0.5397110.0140510.4700180.0271*
C6c0.5883 (10)0.1028 (12)0.3775 (5)0.023 (3)
H1c6c0.5176540.0891980.3287220.0293*
N1c0.6697 (12)0.2410 (14)0.2799 (6)0.029 (3)
H1n1c0.725 (4)0.308 (6)0.283 (5)0.0351*
H2n1c0.601 (3)0.245 (8)0.238 (3)0.0351*
N2c0.9051 (7)0.1649 (8)0.5921 (6)0.024 (2)
O1c0.9162 (6)0.1538 (7)0.6713 (5)0.0361 (18)
O2c0.9880 (7)0.1987 (9)0.5703 (6)0.0381 (18)
I1d0.2833 (6)0.7914 (8)0.3687 (3)0.0241 (2)
C1d0.3120 (15)0.5560 (19)0.6594 (8)0.025 (3)
C2d0.2090 (12)0.5389 (15)0.5869 (7)0.020 (2)
H1c2d0.1465240.4834690.5942670.0236*
C3d0.1984 (8)0.6030 (11)0.5046 (6)0.018 (3)
C4d0.2880 (7)0.6835 (10)0.4882 (5)0.018 (3)
C5d0.3897 (10)0.6999 (14)0.5620 (7)0.024 (3)
H1c5d0.4519910.7555630.5546160.0271*
C6d0.4030 (14)0.6371 (19)0.6465 (8)0.023 (3)
H1c6d0.4738130.6494660.6952650.0293*
N1d0.321 (2)0.497 (2)0.7433 (9)0.029 (3)
H1n1d0.265 (4)0.430 (6)0.740 (5)0.0351*
H2n1d0.390 (3)0.492 (8)0.785 (3)0.0351*
N2d0.0856 (7)0.5806 (11)0.4318 (8)0.024 (2)
O1d0.0745 (8)0.5934 (13)0.3526 (8)0.0361 (18)
O2d0.0027 (8)0.5468 (14)0.4535 (11)0.0381 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I1a0.0334 (4)0.0190 (3)0.0269 (4)0.0012 (2)0.0179 (3)0.0005 (2)
C1a0.018 (3)0.024 (4)0.015 (4)0.006 (3)0.004 (3)0.002 (3)
C2a0.021 (4)0.019 (3)0.030 (5)0.005 (3)0.014 (4)0.000 (4)
C3a0.020 (4)0.020 (3)0.021 (4)0.002 (3)0.008 (4)0.004 (3)
C4a0.027 (4)0.019 (4)0.019 (4)0.007 (3)0.010 (3)0.001 (3)
C5a0.022 (4)0.021 (3)0.033 (5)0.001 (3)0.015 (4)0.004 (4)
C6a0.022 (4)0.032 (4)0.029 (5)0.003 (3)0.009 (4)0.003 (4)
N1a0.020 (4)0.044 (4)0.022 (4)0.005 (3)0.008 (3)0.004 (3)
N2a0.020 (3)0.025 (3)0.033 (4)0.001 (3)0.011 (3)0.001 (3)
O1a0.034 (3)0.053 (3)0.034 (3)0.008 (3)0.005 (2)0.018 (3)
O2a0.030 (3)0.035 (3)0.048 (3)0.009 (2)0.009 (2)0.002 (2)
I1b0.0332 (4)0.0190 (3)0.0271 (4)0.0013 (2)0.0180 (3)0.0005 (2)
C1b0.018 (4)0.024 (4)0.015 (4)0.006 (3)0.004 (3)0.002 (3)
C2b0.021 (4)0.019 (3)0.030 (5)0.005 (3)0.014 (4)0.000 (4)
C3b0.020 (4)0.020 (3)0.021 (4)0.002 (3)0.008 (4)0.004 (3)
C4b0.027 (4)0.019 (4)0.019 (4)0.007 (3)0.010 (3)0.001 (3)
C5b0.022 (4)0.021 (3)0.033 (5)0.001 (3)0.015 (4)0.004 (4)
C6b0.022 (4)0.032 (4)0.029 (5)0.003 (3)0.009 (4)0.003 (4)
N1b0.020 (4)0.044 (4)0.022 (4)0.005 (3)0.008 (3)0.004 (3)
N2b0.020 (3)0.025 (3)0.033 (4)0.001 (3)0.011 (3)0.001 (3)
O1b0.035 (3)0.053 (3)0.034 (3)0.008 (3)0.005 (2)0.018 (3)
O2b0.030 (3)0.035 (3)0.048 (3)0.009 (2)0.008 (2)0.003 (2)
I1c0.0330 (4)0.0191 (3)0.0259 (4)0.0010 (2)0.0176 (3)0.0006 (2)
C1c0.028 (4)0.020 (4)0.032 (5)0.006 (3)0.019 (4)0.001 (3)
C2c0.018 (3)0.022 (3)0.020 (4)0.001 (3)0.008 (3)0.000 (3)
C3c0.016 (4)0.018 (3)0.022 (4)0.004 (3)0.007 (3)0.001 (3)
C4c0.024 (4)0.014 (3)0.022 (4)0.002 (3)0.016 (3)0.000 (3)
C5c0.024 (4)0.024 (4)0.031 (5)0.002 (4)0.017 (4)0.001 (4)
C6c0.022 (4)0.024 (4)0.022 (5)0.006 (3)0.007 (4)0.004 (3)
N1c0.025 (4)0.042 (4)0.020 (4)0.003 (3)0.007 (3)0.005 (3)
N2c0.024 (3)0.029 (3)0.020 (4)0.005 (3)0.012 (3)0.000 (3)
O1c0.029 (2)0.048 (3)0.026 (3)0.009 (2)0.004 (2)0.000 (2)
O2c0.021 (2)0.061 (3)0.034 (3)0.003 (2)0.012 (2)0.002 (2)
I1d0.0330 (4)0.0191 (3)0.0259 (4)0.0011 (2)0.0176 (3)0.0007 (2)
C1d0.028 (4)0.020 (4)0.032 (5)0.006 (3)0.019 (4)0.001 (3)
C2d0.018 (3)0.022 (3)0.020 (4)0.001 (3)0.008 (3)0.000 (3)
C3d0.016 (4)0.018 (3)0.022 (4)0.004 (3)0.007 (3)0.001 (3)
C4d0.024 (4)0.014 (3)0.022 (4)0.002 (3)0.016 (3)0.000 (3)
C5d0.024 (4)0.024 (4)0.031 (5)0.002 (4)0.017 (4)0.001 (4)
C6d0.022 (4)0.024 (4)0.022 (5)0.006 (3)0.008 (4)0.004 (3)
N1d0.025 (4)0.042 (4)0.020 (4)0.003 (3)0.007 (3)0.005 (3)
N2d0.024 (3)0.029 (3)0.020 (4)0.005 (3)0.012 (3)0.000 (3)
O1d0.029 (2)0.048 (3)0.026 (3)0.009 (2)0.004 (2)0.001 (2)
O2d0.021 (2)0.060 (3)0.034 (3)0.003 (2)0.012 (2)0.002 (2)
Geometric parameters (Å, º) top
I1a—C4a2.106 (9)N2b—O2b1.21 (2)
I1b—C4b2.106 (16)C1c—C2c1.393 (13)
I1c—C4c2.085 (9)C1c—C6c1.401 (18)
I1d—C4d2.085 (11)C1c—N1c1.387 (15)
C1a—C2a1.374 (13)C2c—H1c2c0.95
C1a—C6a1.403 (18)C2c—C3c1.376 (13)
C1a—N1a1.389 (14)C3c—C4c1.408 (14)
C2a—H1c2a0.95C3c—N2c1.481 (11)
C2a—C3a1.383 (14)C4c—C5c1.394 (11)
C3a—C4a1.376 (15)C5c—H1c5c0.95
C3a—N2a1.480 (11)C5c—C6c1.395 (13)
C4a—C5a1.391 (11)C6c—H1c6c0.95
C5a—H1c5a0.95N1c—H1n1c0.88 (6)
C5a—C6a1.382 (13)N1c—H2n1c0.88 (3)
C6a—H1c6a0.95H1n1c—H2n1c1.55 (6)
N1a—H1n1a0.88 (5)N2c—O1c1.222 (13)
N1a—H2n1a0.88 (3)N2c—O2c1.238 (15)
H1n1a—H2n1a1.55 (6)C1d—C2d1.393 (17)
N2a—O1a1.219 (10)C1d—C6d1.40 (3)
N2a—O2a1.210 (11)C1d—N1d1.39 (2)
C1b—C2b1.374 (16)C2d—H1c2d0.95
C1b—N1b1.389 (18)C2d—C3d1.376 (15)
C2b—H1c2b0.95C3d—C4d1.408 (14)
C2b—C3b1.383 (17)C3d—N2d1.481 (12)
C3b—C4b1.38 (2)C4d—C5d1.394 (12)
C3b—N2b1.480 (17)C5d—H1c5d0.95
C4b—C5b1.391 (15)C5d—C6d1.395 (18)
C5b—H1c5b0.95C6d—H1c6d0.95
C5b—C6b1.382 (19)N1d—H1n1d0.88 (6)
C6b—H1c6b0.95N1d—H2n1d0.88 (4)
N1b—H1n1b0.88 (6)H1n1d—H2n1d1.55 (6)
N1b—H2n1b0.88 (3)N2d—O1d1.222 (19)
H1n1b—H2n1b1.55 (7)N2d—O2d1.238 (18)
N2b—O1b1.22 (2)
C2a—C1a—C6a117.9 (9)C2c—C1c—C6c119.1 (9)
C2a—C1a—N1a120.6 (12)C2c—C1c—N1c119.6 (12)
C6a—C1a—N1a121.4 (9)C6c—C1c—N1c121.4 (9)
C1a—C2a—H1c2a119.68C1c—C2c—H1c2c120.25
C1a—C2a—C3a120.6 (11)C1c—C2c—C3c119.5 (11)
H1c2a—C2a—C3a119.68H1c2c—C2c—C3c120.25
C2a—C3a—C4a122.3 (8)C2c—C3c—C4c123.4 (8)
C2a—C3a—N2a115.7 (9)C2c—C3c—N2c115.8 (9)
C4a—C3a—N2a122.1 (8)C4c—C3c—N2c120.8 (8)
C3a—C4a—C5a117.2 (8)C3c—C4c—C5c115.8 (8)
C4a—C5a—H1c5a119.43C4c—C5c—H1c5c118.9
C4a—C5a—C6a121.1 (10)C4c—C5c—C6c122.2 (10)
H1c5a—C5a—C6a119.43H1c5c—C5c—C6c118.9
C1a—C6a—C5a120.8 (8)C1c—C6c—C5c120.0 (8)
C1a—C6a—H1c6a119.61C1c—C6c—H1c6c120
C5a—C6a—H1c6a119.61C5c—C6c—H1c6c120.01
C1a—N1a—H1n1a109 (5)C1c—N1c—H1n1c112 (5)
C1a—N1a—H2n1a110 (4)C1c—N1c—H2n1c118 (4)
H1n1a—N1a—H2n1a124 (6)H1n1c—N1c—H2n1c124 (6)
C3a—N2a—O1a117.6 (7)C3c—N2c—O1c121.2 (9)
C3a—N2a—O2a117.5 (7)C3c—N2c—O2c117.9 (9)
O1a—N2a—O2a125.0 (8)O1c—N2c—O2c120.8 (8)
C2b—C1b—C6b117.9 (11)C2d—C1d—C6d119.1 (12)
C2b—C1b—N1b120.6 (16)C2d—C1d—N1d119.6 (18)
C6b—C1b—N1b121.4 (12)C6d—C1d—N1d121.4 (14)
C1b—C2b—H1c2b119.68C1d—C2d—H1c2d120.25
C1b—C2b—C3b120.6 (14)C1d—C2d—C3d119.5 (13)
H1c2b—C2b—C3b119.68H1c2d—C2d—C3d120.25
C2b—C3b—C4b122.3 (10)C2d—C3d—C4d123.4 (9)
C2b—C3b—N2b115.7 (13)C2d—C3d—N2d115.8 (10)
C4b—C3b—N2b122.1 (11)C4d—C3d—N2d120.8 (9)
C3b—C4b—C5b117.2 (11)C3d—C4d—C5d115.8 (9)
C4b—C5b—H1c5b119.43C4d—C5d—H1c5d118.9
C4b—C5b—C6b121.1 (14)C4d—C5d—C6d122.2 (12)
H1c5b—C5b—C6b119.43H1c5d—C5d—C6d118.9
C1b—C6b—C5b120.8 (11)C1d—C6d—C5d120.0 (11)
C1b—C6b—H1c6b119.61C1d—C6d—H1c6d120
C5b—C6b—H1c6b119.61C5d—C6d—H1c6d120.01
C1b—N1b—H1n1b109 (5)C1d—N1d—H1n1d112 (5)
C1b—N1b—H2n1b110 (5)C1d—N1d—H2n1d118 (5)
H1n1b—N1b—H2n1b124 (6)H1n1d—N1d—H2n1d124 (6)
C3b—N2b—O1b117.6 (15)C3d—N2d—O1d121.2 (11)
C3b—N2b—O2b117.5 (14)C3d—N2d—O2d117.9 (13)
O1b—N2b—O2b125.0 (15)O1d—N2d—O2d120.8 (11)
H1n1d—N1d—C1d—C2d15 (5)H1n1a—N1a—C1a—C2a28 (4)
H2n1d—N1d—C1d—C2d168 (5)H2n1a—N1a—C1a—C2a166 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ci0.88 (5)2.21 (7)3.03 (2)155 (7)
N1a—H2n1a···O1aii0.88 (3)2.56 (5)3.269 (13)139 (5)
N1a—H2n1a···O2aii0.88 (3)2.46 (5)3.229 (13)147 (5)
N1b—H1n1b···N1aiii0.88 (6)2.28 (7)3.10 (2)156 (7)
N1b—H2n1b···O1biv0.88 (4)3.23 (6)3.83 (2)127 (5)
N1b—H2n1b···O1civ0.88 (3)2.25 (4)3.088 (19)159 (6)
N1b—H2n1b···O2civ0.88 (3)2.64 (6)3.308 (14)133 (5)
N1c—H1n1c···N1diii0.88 (6)2.23 (7)3.07 (3)160 (6)
N1c—H2n1c···O1biv0.88 (3)2.62 (5)3.36 (2)143 (5)
N1c—H2n1c···O2biv0.88 (3)2.41 (4)3.248 (17)159 (5)
N1d—H1n1d···N1bv0.88 (6)2.18 (7)3.02 (3)160 (6)
N1d—H2n1d···O1dvi0.88 (4)2.28 (4)3.11 (2)157 (6)
N1d—H2n1d···O2dvi0.88 (4)2.56 (5)3.320 (19)145 (5)
N1d—H2n1d···O1avi0.88 (4)3.35 (6)3.94 (2)127 (5)
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1, z1/2; (iv) x1/2, y+1, z1/2; (v) x1/2, y+1, z+1/2; (vi) x+1/2, y+1, z+1/2.

Experimental details

(Ia)(Ib)(IIa)(IIb)
Crystal data
Chemical formulaC6H5ClN2O2C6H5ClN2O2C6H5IN2O2C6H5IN2O2
Mr172.6172.6264264
Crystal system, space groupMonoclinic, P21/nMonoclinic, PnMonoclinic, P21/nMonoclinic, Pn
Temperature (K)293120293120
a, b, c (Å)12.8800 (9), 4.0398 (3), 15.2317 (11)12.7260 (4), 7.9721 (2), 15.0098 (4)12.5219 (8), 4.2601 (3), 16.0008 (9)12.5188 (9), 8.2955 (5), 15.9287 (10)
β (°) 111.263 (7) 110.352 (3) 111.556 (6) 111.141 (6)
V3)738.59 (10)1427.73 (7)793.86 (9)1542.86 (19)
Z4848
Radiation typeCu KαCu KαCu KαMo Kα
µ (mm1)4.194.3431.344.1
Crystal size (mm)0.45 × 0.25 × 0.200.45 × 0.13 × 0.060.50 × 0.24 × 0.050.3 × 0.15 × 0.05
Data collection
DiffractometerOxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
Oxford Diffraction Xcalibur (Atlas, Gemini ultra)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Analytical
CrysAlis PRO (Agilent Technologies, 2012)
Gaussian
(CrysAlis PRO; Oxford Diffraction, 2010)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Tmin, Tmax0.327, 0.4330.362, 0.7810.002, 0.3610.483, 0.815
No. of measured, independent and
observed [I > 3σ(I)] reflections
4809, 1298, 975 23718, 5014, 4733 5100, 1380, 1093 27795, 9998, 4208
Rint0.0460.0250.0620.079
(sin θ/λ)max1)0.5980.5970.5970.735
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.111, 1.92 0.024, 0.066, 1.94 0.053, 0.120, 2.31 0.048, 0.118, 1.32
No. of reflections1298501413809998
No. of parameters125423125224
No. of restraints2824
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.240.17, 0.161.90, 0.852.58, 2.00
Absolute structure?2479 of Friedel pairs used in the refinement?3424 of Friedel pairs used in the refinement
Absolute structure parameter?0.504 (15)?0.41 (13)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR97 (Altomare et al., 1997), JANA2006 (Petříček et al., 2014), PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2010), PLATON (Spek, 2009) and DIAMOND(Brandenburg & Putz, 2010).

Geometric parameters regarding the primary amine groups in the title structures (HT and LT refer to the respective high- and low-temperature phases). top
CompoundC—N (Å)N—H (Å)Average C—N—H (°)H—N—H (°)
(I)-HT1.387 (4)0.88 (3)/0.880 (12)112(2.7)116 (2)
(I)-LT, molecule a1.395 (5)0.880 (17)/0.880 (12)110.0 (2)122 (2)
(I)-LT, molecule b1.373 (5)0.88 (2)/0.880 (13)117.2 (2)112.4 (19)
(I)-LT, molecule c1.371 (5)0.88 (2)/0.880 (13)117.5 (2)112 (2)
(I)-LT, molecule d1.398 (5)0.880 (18)/0.880 (13)110.5 (2)126 (2)
(II)-HT1.384 (12)0.88 (11)/0.88 (6)113 (11)122 (12)
(II)-LT, molecule a1.389 (14)0.88 (5)/0.88 (3)109.5(6.4)124 (6)
(II)-LT, molecule b1.39 (2)0.88 (6)/0.88 (4)115.0(7.1)124 (6)
Geometric parameters (aryl–nitro C—N bond length and the interplanar angle between the nitro and aryl groups) regarding the nitro groups in the title structures (HT and LT refer to the respective room- and low-temperature phases). The C—Cl distances are also included for comparison. top
Compound/moleculeC3—N2 (Å)O1—N2—O2/C1–C6 (°)C—Cl/I (Å)
(I)-HT1.468 (3)45.3 (4)/25.5 (3)1.727 (3)
(I)-LT, molecule a1.486 (4)48.86 (13)1.745 (4)
(I)-LT, molecule b1.447 (4)49.17 (13)1.719 (4)
(I)-LT, molecule c1.450 (4)25.82 (10)1.720 (4)
(I)-LT, molecule d1.483 (3)25.93 (10)1.742 (4)
(II)-HT1.469 (10)35.7 (10)/14.3 (12)2.095 (8)
(II)-LT, molecule a1.480 (11)39.2 (4)2.106 (9)
(II)-LT, molecule d1.481 (12)18.5 (3)2.085 (11)
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ai0.88 (3)2.25 (3)3.096 (4)162 (3)
N1a—H2n1a···O1aii0.880 (12)2.73 (2)3.512 (8)148 (2)
N1a—H2n1a···O2aii0.880 (12)2.330 (18)3.153 (6)156 (2)
N1a—H2n1a···O1dii0.880 (12)2.531 (15)3.369 (5)159 (2)
N1a—H2n1a···O2dii0.880 (12)2.44 (2)3.193 (6)144 (2)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ci0.880 (17)2.28 (2)3.060 (5)147 (2)
N1a—H2n1a···O1aii0.880 (13)2.808 (19)3.468 (4)133 (2)
N1a—H2n1a···O2aii0.880 (12)2.201 (13)3.079 (3)175.2 (19)
N1b—H1n1b···N1aiii0.88 (2)2.21 (2)3.085 (5)176.7 (19)
N1b—H2n1b···O1civ0.880 (13)2.410 (13)3.260 (3)163 (2)
N1b—H2n1b···O2civ0.880 (13)2.389 (19)3.144 (3)144 (2)
N1c—H1n1c···N1diii0.88 (2)2.17 (2)3.046 (5)174.5 (17)
N1c—H2n1c···O1biv0.880 (13)2.745 (18)3.563 (3)155.3 (19)
N1c—H2n1c···O2biv0.880 (13)2.307 (15)3.108 (3)151 (2)
N1d—H1n1d···N1bv0.880 (18)2.23 (2)3.041 (5)153 (2)
N1d—H2n1d···O1dvi0.880 (13)2.569 (14)3.323 (3)144 (2)
N1d—H2n1d···O2dvi0.880 (13)2.421 (19)3.183 (3)145 (2)
N1d—H2n1d···O1avi0.880 (13)3.04 (2)3.754 (3)140 (2)
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1, z1/2; (iv) x1/2, y+1, z1/2; (v) x1/2, y+1, z+1/2; (vi) x+1/2, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ci0.88 (5)2.21 (7)3.03 (2)155 (7)
N1a—H2n1a···O1aii0.88 (3)2.56 (5)3.269 (13)139 (5)
N1a—H2n1a···O2aii0.88 (3)2.46 (5)3.229 (13)147 (5)
N1b—H1n1b···N1aiii0.88 (6)2.28 (7)3.10 (2)156 (7)
N1b—H2n1b···O1civ0.88 (3)2.25 (4)3.088 (19)159 (6)
N1b—H2n1b···O2civ0.88 (3)2.64 (6)3.308 (14)133 (5)
N1c—H1n1c···N1diii0.88 (6)2.23 (7)3.07 (3)160 (6)
N1c—H2n1c···O1biv0.88 (3)2.62 (5)3.36 (2)143 (5)
N1c—H2n1c···O2biv0.88 (3)2.41 (4)3.248 (17)159 (5)
N1d—H1n1d···N1bv0.88 (6)2.18 (7)3.02 (3)160 (6)
N1d—H2n1d···O1dvi0.88 (4)2.28 (4)3.11 (2)157 (6)
N1d—H2n1d···O2dvi0.88 (4)2.56 (5)3.320 (19)145 (5)
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1, z1/2; (iv) x1/2, y+1, z1/2; (v) x1/2, y+1, z+1/2; (vi) x+1/2, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···AD—HH···AD···AD—H···A
N1a—H1n1a···N1ai0.88 (11)2.27 (14)3.088 (17)155 (13)
N1a—H2n1a···O1aii0.88 (6)2.67 (11)3.33 (2)133 (12)
N1a—H2n1a···O2aii0.88 (6)2.46 (8)3.30 (2)159 (9)
N1a—H2n1a···O1dii0.88 (6)2.40 (8)3.16 (2)145 (12)
N1a—H2n1a···O2dii0.88 (6)2.54 (9)3.29 (2)143 (9)
Symmetry codes: (i) x+1/2, y1/2, z+3/2; (ii) x+1/2, y1/2, z+1/2.
 

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