Supporting information
CCDC references: 1033499; 1033498; 1033497; 1033496
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.
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.
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.
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).
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).
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) Å3 | Prism, yellow |
Z = 4 | 0.45 × 0.25 × 0.20 mm |
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 on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.045 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 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 |
C6H5ClN2O2 | V = 738.59 (10) Å3 |
Mr = 172.6 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 12.8800 (9) Å | µ = 4.19 mm−1 |
b = 4.0398 (3) Å | T = 293 K |
c = 15.2317 (11) Å | 0.45 × 0.25 × 0.20 mm |
β = 111.263 (7)° |
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 = 0.433 | Rint = 0.046 |
4809 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 2 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.92 | Δρmax = 0.33 e Å−3 |
1298 reflections | Δρmin = −0.24 e Å−3 |
125 parameters |
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 |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ai | 0.88 (3) | 2.25 (3) | 3.096 (4) | 162 (3) |
N1a—H2n1a···O1aii | 0.880 (12) | 2.73 (2) | 3.512 (8) | 148 (2) |
N1a—H2n1a···O2aii | 0.880 (12) | 2.330 (18) | 3.153 (6) | 156 (2) |
N1a—H2n1a···O1dii | 0.880 (12) | 2.531 (15) | 3.369 (5) | 159 (2) |
N1a—H2n1a···O2dii | 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. |
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) Å3 | Plate, brown |
Z = 8 | 0.45 × 0.13 × 0.06 mm |
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 on F2 | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
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) |
C6H5ClN2O2 | V = 1427.73 (7) Å3 |
Mr = 172.6 | Z = 8 |
Monoclinic, Pn | Cu Kα radiation |
a = 12.7260 (4) Å | µ = 4.34 mm−1 |
b = 7.9721 (2) Å | T = 120 K |
c = 15.0098 (4) Å | 0.45 × 0.13 × 0.06 mm |
β = 110.352 (3)° |
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 = 0.781 | Rint = 0.025 |
23718 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | Δρmax = 0.17 e Å−3 |
S = 1.94 | Δρmin = −0.16 e Å−3 |
5014 reflections | Absolute structure: 2479 of Friedel pairs used in the refinement |
423 parameters | Absolute structure parameter: 0.504 (15) |
8 restraints |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ci | 0.880 (17) | 2.28 (2) | 3.060 (5) | 147 (2) |
N1a—H2n1a···O1aii | 0.880 (13) | 2.808 (19) | 3.468 (4) | 133 (2) |
N1a—H2n1a···O2aii | 0.880 (12) | 2.201 (13) | 3.079 (3) | 175.2 (19) |
N1b—H1n1b···N1aiii | 0.88 (2) | 2.21 (2) | 3.085 (5) | 176.7 (19) |
N1b—H2n1b···O1biv | 0.880 (13) | 3.112 (19) | 3.562 (4) | 114.0 (17) |
N1b—H2n1b···O1civ | 0.880 (13) | 2.410 (13) | 3.260 (3) | 163 (2) |
N1b—H2n1b···O2civ | 0.880 (13) | 2.389 (19) | 3.144 (3) | 144 (2) |
N1c—H1n1c···N1diii | 0.88 (2) | 2.17 (2) | 3.046 (5) | 174.5 (17) |
N1c—H2n1c···O1biv | 0.880 (13) | 2.745 (18) | 3.563 (3) | 155.3 (19) |
N1c—H2n1c···O2biv | 0.880 (13) | 2.307 (15) | 3.108 (3) | 151 (2) |
N1d—H1n1d···N1bv | 0.880 (18) | 2.23 (2) | 3.041 (5) | 153 (2) |
N1d—H2n1d···O1dvi | 0.880 (13) | 2.569 (14) | 3.323 (3) | 144 (2) |
N1d—H2n1d···O2dvi | 0.880 (13) | 2.421 (19) | 3.183 (3) | 145 (2) |
N1d—H2n1d···O1avi | 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. |
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) Å3 | Plate, brown |
Z = 4 | 0.50 × 0.24 × 0.05 mm |
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 on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.053 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 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 |
C6H5IN2O2 | V = 793.86 (9) Å3 |
Mr = 264 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 12.5219 (8) Å | µ = 31.34 mm−1 |
b = 4.2601 (3) Å | T = 293 K |
c = 16.0008 (9) Å | 0.50 × 0.24 × 0.05 mm |
β = 111.556 (6)° |
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 = 0.361 | Rint = 0.062 |
5100 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 2 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 2.31 | Δρmax = 1.90 e Å−3 |
1380 reflections | Δρmin = −0.85 e Å−3 |
125 parameters |
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 |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ai | 0.88 (11) | 2.27 (14) | 3.088 (17) | 155 (13) |
N1a—H2n1a···O1aii | 0.88 (6) | 2.67 (11) | 3.33 (2) | 133 (12) |
N1a—H2n1a···O2aii | 0.88 (6) | 2.46 (8) | 3.30 (2) | 159 (9) |
N1a—H2n1a···O1dii | 0.88 (6) | 2.40 (8) | 3.16 (2) | 145 (12) |
N1a—H2n1a···O2dii | 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. |
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) Å3 | Plate, brown |
Z = 8 | 0.3 × 0.15 × 0.05 mm |
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 on F2 | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.048 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F2) = 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 |
C6H5IN2O2 | V = 1542.86 (19) Å3 |
Mr = 264 | Z = 8 |
Monoclinic, Pn | Mo Kα radiation |
a = 12.5188 (9) Å | µ = 4.1 mm−1 |
b = 8.2955 (5) Å | T = 120 K |
c = 15.9287 (10) Å | 0.3 × 0.15 × 0.05 mm |
β = 111.141 (6)° |
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 = 0.815 | Rint = 0.079 |
27795 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | Δρmax = 2.58 e Å−3 |
S = 1.32 | Δρmin = −2.00 e Å−3 |
9998 reflections | Absolute structure: 3424 of Friedel pairs used in the refinement |
224 parameters | Absolute structure parameter: 0.41 (13) |
4 restraints |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ci | 0.88 (5) | 2.21 (7) | 3.03 (2) | 155 (7) |
N1a—H2n1a···O1aii | 0.88 (3) | 2.56 (5) | 3.269 (13) | 139 (5) |
N1a—H2n1a···O2aii | 0.88 (3) | 2.46 (5) | 3.229 (13) | 147 (5) |
N1b—H1n1b···N1aiii | 0.88 (6) | 2.28 (7) | 3.10 (2) | 156 (7) |
N1b—H2n1b···O1biv | 0.88 (4) | 3.23 (6) | 3.83 (2) | 127 (5) |
N1b—H2n1b···O1civ | 0.88 (3) | 2.25 (4) | 3.088 (19) | 159 (6) |
N1b—H2n1b···O2civ | 0.88 (3) | 2.64 (6) | 3.308 (14) | 133 (5) |
N1c—H1n1c···N1diii | 0.88 (6) | 2.23 (7) | 3.07 (3) | 160 (6) |
N1c—H2n1c···O1biv | 0.88 (3) | 2.62 (5) | 3.36 (2) | 143 (5) |
N1c—H2n1c···O2biv | 0.88 (3) | 2.41 (4) | 3.248 (17) | 159 (5) |
N1d—H1n1d···N1bv | 0.88 (6) | 2.18 (7) | 3.02 (3) | 160 (6) |
N1d—H2n1d···O1dvi | 0.88 (4) | 2.28 (4) | 3.11 (2) | 157 (6) |
N1d—H2n1d···O2dvi | 0.88 (4) | 2.56 (5) | 3.320 (19) | 145 (5) |
N1d—H2n1d···O1avi | 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. |
Experimental details
(Ia) | (Ib) | (IIa) | (IIb) | |
Crystal data | ||||
Chemical formula | C6H5ClN2O2 | C6H5ClN2O2 | C6H5IN2O2 | C6H5IN2O2 |
Mr | 172.6 | 172.6 | 264 | 264 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, Pn | Monoclinic, P21/n | Monoclinic, Pn |
Temperature (K) | 293 | 120 | 293 | 120 |
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) |
V (Å3) | 738.59 (10) | 1427.73 (7) | 793.86 (9) | 1542.86 (19) |
Z | 4 | 8 | 4 | 8 |
Radiation type | Cu Kα | Cu Kα | Cu Kα | Mo Kα |
µ (mm−1) | 4.19 | 4.34 | 31.34 | 4.1 |
Crystal size (mm) | 0.45 × 0.25 × 0.20 | 0.45 × 0.13 × 0.06 | 0.50 × 0.24 × 0.05 | 0.3 × 0.15 × 0.05 |
Data collection | ||||
Diffractometer | Oxford 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 correction | Multi-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, Tmax | 0.327, 0.433 | 0.362, 0.781 | 0.002, 0.361 | 0.483, 0.815 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 4809, 1298, 975 | 23718, 5014, 4733 | 5100, 1380, 1093 | 27795, 9998, 4208 |
Rint | 0.046 | 0.025 | 0.062 | 0.079 |
(sin θ/λ)max (Å−1) | 0.598 | 0.597 | 0.597 | 0.735 |
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 reflections | 1298 | 5014 | 1380 | 9998 |
No. of parameters | 125 | 423 | 125 | 224 |
No. of restraints | 2 | 8 | 2 | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.24 | 0.17, −0.16 | 1.90, −0.85 | 2.58, −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).
Compound | C—N (Å) | N—H (Å) | Average C—N—H (°) | H—N—H (°) |
(I)-HT | 1.387 (4) | 0.88 (3)/0.880 (12) | 112(2.7) | 116 (2) |
(I)-LT, molecule a | 1.395 (5) | 0.880 (17)/0.880 (12) | 110.0 (2) | 122 (2) |
(I)-LT, molecule b | 1.373 (5) | 0.88 (2)/0.880 (13) | 117.2 (2) | 112.4 (19) |
(I)-LT, molecule c | 1.371 (5) | 0.88 (2)/0.880 (13) | 117.5 (2) | 112 (2) |
(I)-LT, molecule d | 1.398 (5) | 0.880 (18)/0.880 (13) | 110.5 (2) | 126 (2) |
(II)-HT | 1.384 (12) | 0.88 (11)/0.88 (6) | 113 (11) | 122 (12) |
(II)-LT, molecule a | 1.389 (14) | 0.88 (5)/0.88 (3) | 109.5(6.4) | 124 (6) |
(II)-LT, molecule b | 1.39 (2) | 0.88 (6)/0.88 (4) | 115.0(7.1) | 124 (6) |
Compound/molecule | C3—N2 (Å) | O1—N2—O2/C1–C6 (°) | C—Cl/I (Å) |
(I)-HT | 1.468 (3) | 45.3 (4)/25.5 (3) | 1.727 (3) |
(I)-LT, molecule a | 1.486 (4) | 48.86 (13) | 1.745 (4) |
(I)-LT, molecule b | 1.447 (4) | 49.17 (13) | 1.719 (4) |
(I)-LT, molecule c | 1.450 (4) | 25.82 (10) | 1.720 (4) |
(I)-LT, molecule d | 1.483 (3) | 25.93 (10) | 1.742 (4) |
(II)-HT | 1.469 (10) | 35.7 (10)/14.3 (12) | 2.095 (8) |
(II)-LT, molecule a | 1.480 (11) | 39.2 (4) | 2.106 (9) |
(II)-LT, molecule d | 1.481 (12) | 18.5 (3) | 2.085 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ai | 0.88 (3) | 2.25 (3) | 3.096 (4) | 162 (3) |
N1a—H2n1a···O1aii | 0.880 (12) | 2.73 (2) | 3.512 (8) | 148 (2) |
N1a—H2n1a···O2aii | 0.880 (12) | 2.330 (18) | 3.153 (6) | 156 (2) |
N1a—H2n1a···O1dii | 0.880 (12) | 2.531 (15) | 3.369 (5) | 159 (2) |
N1a—H2n1a···O2dii | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ci | 0.880 (17) | 2.28 (2) | 3.060 (5) | 147 (2) |
N1a—H2n1a···O1aii | 0.880 (13) | 2.808 (19) | 3.468 (4) | 133 (2) |
N1a—H2n1a···O2aii | 0.880 (12) | 2.201 (13) | 3.079 (3) | 175.2 (19) |
N1b—H1n1b···N1aiii | 0.88 (2) | 2.21 (2) | 3.085 (5) | 176.7 (19) |
N1b—H2n1b···O1civ | 0.880 (13) | 2.410 (13) | 3.260 (3) | 163 (2) |
N1b—H2n1b···O2civ | 0.880 (13) | 2.389 (19) | 3.144 (3) | 144 (2) |
N1c—H1n1c···N1diii | 0.88 (2) | 2.17 (2) | 3.046 (5) | 174.5 (17) |
N1c—H2n1c···O1biv | 0.880 (13) | 2.745 (18) | 3.563 (3) | 155.3 (19) |
N1c—H2n1c···O2biv | 0.880 (13) | 2.307 (15) | 3.108 (3) | 151 (2) |
N1d—H1n1d···N1bv | 0.880 (18) | 2.23 (2) | 3.041 (5) | 153 (2) |
N1d—H2n1d···O1dvi | 0.880 (13) | 2.569 (14) | 3.323 (3) | 144 (2) |
N1d—H2n1d···O2dvi | 0.880 (13) | 2.421 (19) | 3.183 (3) | 145 (2) |
N1d—H2n1d···O1avi | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ci | 0.88 (5) | 2.21 (7) | 3.03 (2) | 155 (7) |
N1a—H2n1a···O1aii | 0.88 (3) | 2.56 (5) | 3.269 (13) | 139 (5) |
N1a—H2n1a···O2aii | 0.88 (3) | 2.46 (5) | 3.229 (13) | 147 (5) |
N1b—H1n1b···N1aiii | 0.88 (6) | 2.28 (7) | 3.10 (2) | 156 (7) |
N1b—H2n1b···O1civ | 0.88 (3) | 2.25 (4) | 3.088 (19) | 159 (6) |
N1b—H2n1b···O2civ | 0.88 (3) | 2.64 (6) | 3.308 (14) | 133 (5) |
N1c—H1n1c···N1diii | 0.88 (6) | 2.23 (7) | 3.07 (3) | 160 (6) |
N1c—H2n1c···O1biv | 0.88 (3) | 2.62 (5) | 3.36 (2) | 143 (5) |
N1c—H2n1c···O2biv | 0.88 (3) | 2.41 (4) | 3.248 (17) | 159 (5) |
N1d—H1n1d···N1bv | 0.88 (6) | 2.18 (7) | 3.02 (3) | 160 (6) |
N1d—H2n1d···O1dvi | 0.88 (4) | 2.28 (4) | 3.11 (2) | 157 (6) |
N1d—H2n1d···O2dvi | 0.88 (4) | 2.56 (5) | 3.320 (19) | 145 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1a—H1n1a···N1ai | 0.88 (11) | 2.27 (14) | 3.088 (17) | 155 (13) |
N1a—H2n1a···O1aii | 0.88 (6) | 2.67 (11) | 3.33 (2) | 133 (12) |
N1a—H2n1a···O2aii | 0.88 (6) | 2.46 (8) | 3.30 (2) | 159 (9) |
N1a—H2n1a···O1dii | 0.88 (6) | 2.40 (8) | 3.16 (2) | 145 (12) |
N1a—H2n1a···O2dii | 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. |