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In the closely related quinoline compounds 8-nitro-2-(tri­chloro­methyl)quinoline, (I), 6-nitro-2-(trichloro­methyl)­quino­line, (II), and 5-nitro-2-(trichloro­methyl)quinoline, (III), all C10H5Cl3N2O2, which are of both reactivity and pharmaco­logical inter­est, and for which the biological activity and cytotoxicity appear to be based on the positions of the CCl3 and nitro substituents, the nitro group is only coplanar with its aromatic substrate in (II). The deviation of the nitro group from coplanarity is concluded to be a function of both its position with respect to the trichloro­methyl group and the inter­molecular contacts in which it participates. The discrepancies between the crystal structures and the mol­ecular shapes predicted by ab initio calculations are also explained in these terms. The quinoline ring is not rigorously planar in any of the structures, which may be explained by stress produced by the CCl3 substituent.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108020374/fa3148sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108020374/fa3148Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108020374/fa3148IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108020374/fa3148IIIsup4.hkl
Contains datablock III

CCDC references: 700030; 700031; 700032

Comment top

The quinoline nucleus presents a broad spectrum of pharmacological activities. It is part of the chemotherapeutic arsenal in various medical specialities, mainly in infectiology (chloroquine, mefloquine), but also in cardiology (quinidine), and it can present analgesic properties (floctafenine). Recent research has evaluated its potential in other pharmaceutical areas, such as the central nervous system (Bromidge et al., 2001), haematology (Clasby et al., 2006) or virology (Polanski et al., 2002). The trichloromethyl group in a position α to the sp2 N atom of various heteroaromatic rings has also demonstrated its own specific pharmacological activities (Liu et al., 2003; Tiwari et al., 2002; Sielecki et al., 2001; Verhaeghe et al., 2008). Furthermore, the trichloromethyl group offers interesting synthetic pathways to further products. It leads easily to the amidine function, is the main synthetic trifluoromethyl precursor and has recently been reacted with aromatic aldehydes through TDAE-initiated reactions [TDAE is tetrakis(dimethylamino)ethylene], generating α-chloroketone derivatives (Montana et al., 2006). It is also possible to involve 8- and 6-nitro-2-(trichloromethyl)quinolines, (I) and (II), in consecutive SRN1 and ERC1 reactions, leading to novel vinylic chloride derivatives (Verhaeghe, Rathelot, Rault & Vanelle, 2006) (SRN1 is a nucleophilic radical substitution mechanism and ERC1 is a unimolecular radical chain elimination reaction).

For both reaction studies and therapeutic purposes, it appeared important to establish the structures of these isomeric compounds, which were prepared efficiently in two steps from 2-methylquinoline, via successive nitration and microwave-assisted chlorination reactions (Verhaeghe, Rathelot, Gellis et al., 2006). From a reactivity point of view, in the nitrobenzyl chloride series, Kerber et al. (1965) suggested that the nitro group of the aromatic substrates involved in SRN1 reactions had to be coplanar with the benzene ring in order for the reaction to proceed correctly. However, when we reacted compounds (I) and (II) with nitroalkane salts, under single electron-transfer reaction conditions, the corresponding vinyl chloride products were obtained in similar very good yields (Verhaeghe, Rathelot, Rault & Vanelle, 2006), although the nitro group in (I) is perpendicular to the quinoline ring while the nitro group of (II) is nearly coplanar with the same quinoline ring.

Fig. 1 shows views of the asymmetric units of compounds (I), (II) and (III). The asymmetric units of compounds (I) and (II) contain one molecule, while for (III) Z' = 2.

In the 8-nitro isomer, (I), the nitro group is nearly perpendicular to the quinoline ring, as was initially supposed [dihedral angle 68.42 (5)°]. An ab initio calculation of potential energy as a function of nitro group torsion angle [GAUSSIAN98 (Frisch et al., 2001); basis set HF/3-21 G] showed that the most stable nitro group conformations are those with a deviation of about ±30° from coplanarity. The larger deviation observed in the crystal structure of (I) seems to be a consequence of intermolecular interactions. Atom O1 crowds atom O2i from a neighbouring molecule [2.952 (2) Å; symmetry code: (i) 1 - x, 1/2 + y, 1/2 - z]. At the same time, atom O1 also contacts two H atoms from aromatic C—H groups, H5ii [2.613 Å; symmetry code: (ii) +x, 3/2 - y, -1/2 + z] and H6ii (2.552 Å), and these electrostatic contacts are favourable to an out-of-plane twist of the nitro group.

In the 5-nitro isomer, (III), the nitro group deviates from coplanarity with the quinoline ring [dihedral angles 36.05 (6) and 35.74 (5)°]. An ab inito calculation proposed, as the most stable conformation, a coplanar position for the nitro group, but with a broad minimum and only a small energy penalty of about 1 kcal mol-1 (1 kcal mol-1 = 4.184 kJ mol-1) for a twist of 30°. A short contact exists between atom O12 of the nitro group of one molecule and a pyridyl H atom of a neighbouring molecule [C14iii—H14iii···O12 = 2.510 Å; symmetry code: (iii) 1 - x, -y, 1 - z], a favourable out-of-plane interaction which may be the origin of the deviation of the nitro group. The second molecule in the asymmetric unit is involved in a similar contact [C23iv—H23iv···O21 = 2.406 Å; symmetry code: (iv) 2 - x,-y,1 - z].

For the 6-nitro isomer, (II), the nitro group is nearly coplanar with the quinoline ring [dihedral angle 7.49 (9)°]. The small deviation appears to be related to a contact between atom O1 of the nitro group and a neighbouring C8v—H8v group [symmetry code: (v) x, -1/2 - y, -1/2 + z].

In none of the three structures is the quinoline ring rigorously planar; they are all somewhat bent. The dihedral angles between the fused rings are 5.65 (5)° for the 8-nitro isomer, 5.23 (4)° for the 6-nitro isomer, and 1.80 (5) and 4.74 (4)° for the two molecules of the 5-nitro isomer. A search of quinoline structures deposited in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002) indicates that the quinoline ring is usually planar, even if it is substituted at position 2. [Two structures with 2-chloromethyl substitution were found, namely 2-(trichloromethyl)quinoline and 2-dichloromethylquinoline (Kaluski & Golankiewicz, 1965), but no coordinates are present.] We recently reported crystal structures (Sopková-de Oliveira Santos et al., 2007) in which the quinoline rings were substituted by a nitro group at position 8 and by vinyl or 1-chloro-2-methylpropenyl at position 2. In both cases the quinoline ring was planar. Based on this comparison, it seems that it is the trichloromethyl group at position 2 that induces tension within the quinoline system.

In conclusion, the theoretical simulation predicts that the nitro group should be coplanar with the quinoline ring for the 5- and 6-nitro isomers, and twisted by about ±30° from coplanarity in the 8-nitro isomer. However, the observed deviations are about 35° for the 5-nitro isomer, 7° for the 6-nitro isomer and 68° for the 8-nitro isomer. Our ab initio simulations show that the deviation of 35° for the 5-nitro system involves less than a 1 kcal mol-1 penalty and that the deviation of about 68° in the 8-nitro compound introduces about 2.5 kcal mol-1 of penalty. These energy disadvantages are compensated for in the crystal structures by the intermolecular interactions involving the nitro groups.

Experimental top

2-Methyl-5, -6- or -8-nitroquinolines, obtained from commercial 2-methylquinoline through a classical nitration reaction, were reacted with a mixture of phosphorus pentachloride (4–5 equivalents) and phosphorus oxychloride, used as a solvent. The reaction was conducted under 800 W microwave irradiation in a multimode microwave reactor for 5–20 min. The crude residue was added to a solution of sodium carbonate and extracted with chloroform. Purification was performed by flash chromatography on a silica gel column, eluting with dichloromethane–petroleum ether (1:1 v/v), leading to the chlorinated products in 83–98% yield (Verhaeghe, Rathelot, Gellis et al., 2006).

Refinement top

All H atoms were determined via difference Fourier maps and refined with isotropic atomic displacement parameters. [Range of refined C—H distances?]

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Views of the title compounds, (a) (I), (b) (II), (c) (IIIA) and (d) (IIIB), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
(I) 8-nitro-2-(trichloromethyl)quinoline top
Crystal data top
C10H5Cl3N2O2F(000) = 584
Mr = 291.51Dx = 1.761 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9918 reflections
a = 15.1941 (14) Åθ = 2.7–40.5°
b = 5.5843 (5) ŵ = 0.82 mm1
c = 12.9620 (12) ÅT = 150 K
β = 91.693 (5)°Prism, translucent pale brown
V = 1099.33 (17) Å30.58 × 0.34 × 0.31 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5214 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.028
Graphite monochromatorθmax = 39.4°, θmin = 2.7°
ϕ and ω scansh = 2727
42809 measured reflectionsk = 99
6463 independent reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.083All H-atom parameters refined
S = 1.11 w = 1/[σ2(Fo2) + (0.0322P)2 + 0.4692P]
where P = (Fo2 + 2Fc2)/3
6463 reflections(Δ/σ)max = 0.002
174 parametersΔρmax = 0.71 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C10H5Cl3N2O2V = 1099.33 (17) Å3
Mr = 291.51Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.1941 (14) ŵ = 0.82 mm1
b = 5.5843 (5) ÅT = 150 K
c = 12.9620 (12) Å0.58 × 0.34 × 0.31 mm
β = 91.693 (5)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5214 reflections with I > 2σ(I)
42809 measured reflectionsRint = 0.028
6463 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.083All H-atom parameters refined
S = 1.11Δρmax = 0.71 e Å3
6463 reflectionsΔρmin = 0.32 e Å3
174 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.25586 (5)0.13830 (12)0.38627 (5)0.01198 (11)
C20.19037 (5)0.04973 (14)0.43786 (6)0.01207 (12)
C30.17025 (6)0.11502 (16)0.53996 (7)0.01553 (13)
H30.1234 (11)0.042 (3)0.5734 (13)0.030 (4)*
C40.21938 (6)0.29098 (16)0.58703 (7)0.01604 (14)
H40.2074 (11)0.341 (3)0.6565 (12)0.028 (4)*
C4A0.28789 (5)0.40223 (15)0.53319 (6)0.01318 (12)
C50.33666 (6)0.59993 (16)0.57266 (7)0.01620 (14)
H50.3260 (11)0.652 (3)0.6398 (12)0.026 (4)*
C60.39971 (6)0.70626 (16)0.51478 (7)0.01674 (14)
H60.4306 (11)0.842 (3)0.5415 (14)0.035 (5)*
C70.41971 (6)0.61457 (15)0.41662 (7)0.01485 (13)
H70.4650 (11)0.679 (3)0.3806 (13)0.027 (4)*
C80.37476 (5)0.41900 (14)0.38058 (6)0.01223 (12)
C8A0.30532 (5)0.31090 (14)0.43403 (6)0.01135 (11)
C210.12911 (5)0.11660 (14)0.37547 (6)0.01346 (12)
Cl10.050976 (14)0.06787 (4)0.307478 (18)0.01832 (5)
Cl20.186136 (15)0.28881 (4)0.284842 (18)0.01848 (5)
Cl30.071609 (17)0.31494 (4)0.45575 (2)0.02278 (5)
N20.39872 (5)0.31463 (13)0.28171 (6)0.01413 (12)
O10.38648 (6)0.43392 (14)0.20358 (5)0.02407 (15)
O20.43089 (6)0.11444 (14)0.28351 (6)0.02433 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0115 (3)0.0135 (2)0.0111 (3)0.0009 (2)0.0014 (2)0.0016 (2)
C20.0108 (3)0.0134 (3)0.0120 (3)0.0002 (2)0.0006 (2)0.0029 (2)
C30.0138 (3)0.0195 (3)0.0136 (3)0.0012 (3)0.0041 (2)0.0025 (3)
C40.0159 (3)0.0208 (3)0.0116 (3)0.0002 (3)0.0038 (3)0.0003 (3)
C4A0.0128 (3)0.0161 (3)0.0107 (3)0.0005 (2)0.0011 (2)0.0004 (2)
C50.0164 (3)0.0190 (3)0.0133 (3)0.0000 (3)0.0011 (3)0.0030 (3)
C60.0161 (3)0.0168 (3)0.0173 (3)0.0019 (3)0.0003 (3)0.0032 (3)
C70.0138 (3)0.0149 (3)0.0159 (3)0.0023 (2)0.0018 (3)0.0003 (2)
C80.0122 (3)0.0140 (3)0.0106 (3)0.0007 (2)0.0021 (2)0.0008 (2)
C8A0.0107 (3)0.0135 (3)0.0099 (3)0.0001 (2)0.0009 (2)0.0017 (2)
C210.0119 (3)0.0130 (3)0.0156 (3)0.0008 (2)0.0015 (2)0.0029 (2)
Cl10.01499 (8)0.01778 (8)0.02189 (10)0.00236 (6)0.00444 (7)0.00126 (7)
Cl20.01698 (9)0.01522 (8)0.02337 (10)0.00038 (6)0.00260 (7)0.00368 (7)
Cl30.02302 (10)0.02102 (9)0.02449 (11)0.00943 (7)0.00384 (8)0.00649 (7)
N20.0135 (3)0.0170 (3)0.0121 (3)0.0031 (2)0.0028 (2)0.0002 (2)
O10.0356 (4)0.0250 (3)0.0115 (3)0.0027 (3)0.0002 (3)0.0039 (2)
O20.0313 (4)0.0212 (3)0.0210 (3)0.0073 (3)0.0087 (3)0.0008 (2)
Geometric parameters (Å, º) top
N1—C21.3121 (10)C6—C71.4129 (12)
N1—C8A1.3600 (11)C6—H60.950 (18)
C2—C31.4148 (12)C7—C81.3633 (12)
C2—C211.5293 (12)C7—H70.916 (17)
C3—C41.3667 (13)C8—C8A1.4145 (11)
C3—H30.939 (17)C8—N21.4636 (11)
C4—C4A1.4139 (12)C21—Cl21.7651 (9)
C4—H40.965 (16)C21—Cl31.7682 (8)
C4A—C8A1.4151 (11)C21—Cl11.7848 (8)
C4A—C51.4169 (12)N2—O21.2201 (11)
C5—C61.3695 (13)N2—O11.2219 (10)
C5—H50.935 (16)
C2—N1—C8A116.89 (7)C8—C7—C6118.68 (8)
N1—C2—C3124.59 (8)C8—C7—H7121.0 (10)
N1—C2—C21114.73 (7)C6—C7—H7120.1 (10)
C3—C2—C21120.42 (7)C7—C8—C8A123.19 (7)
C4—C3—C2118.20 (7)C7—C8—N2118.95 (7)
C4—C3—H3121.2 (10)C8A—C8—N2117.86 (7)
C2—C3—H3120.5 (10)N1—C8A—C8119.31 (7)
C3—C4—C4A119.73 (8)N1—C8A—C4A123.59 (7)
C3—C4—H4120.6 (10)C8—C8A—C4A116.96 (7)
C4A—C4—H4119.7 (10)C2—C21—Cl2112.32 (6)
C4—C4A—C8A116.76 (8)C2—C21—Cl3111.89 (6)
C4—C4A—C5123.30 (8)Cl2—C21—Cl3108.13 (4)
C8A—C4A—C5119.93 (7)C2—C21—Cl1107.22 (5)
C6—C5—C4A120.46 (8)Cl2—C21—Cl1108.56 (5)
C6—C5—H5121.3 (10)Cl3—C21—Cl1108.61 (4)
C4A—C5—H5118.2 (10)O2—N2—O1124.50 (8)
C5—C6—C7120.58 (8)O2—N2—C8117.27 (7)
C5—C6—H6119.4 (11)O1—N2—C8118.23 (7)
C7—C6—H6120.0 (11)
(II) 6-nitro-2-(trichloromethyl)quinoline top
Crystal data top
C10H5Cl3N2O2F(000) = 584
Mr = 291.51Dx = 1.758 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8836 reflections
a = 16.764 (3) Åθ = 2.5–53.8°
b = 5.5177 (11) ŵ = 0.82 mm1
c = 12.313 (3) ÅT = 150 K
β = 104.73 (3)°Prism, translucent pale brown
V = 1101.5 (4) Å30.41 × 0.32 × 0.28 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
8836 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.049
Graphite monochromatorθmax = 53.8°, θmin = 2.5°
ω scansh = 3237
53399 measured reflectionsk = 1210
13343 independent reflectionsl = 2727
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: difference Fourier map
wR(F2) = 0.087All H-atom parameters refined
S = 0.94 w = 1/[σ2(Fo2) + (0.0446P)2]
where P = (Fo2 + 2Fc2)/3
13343 reflections(Δ/σ)max = 0.005
174 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = 0.78 e Å3
Crystal data top
C10H5Cl3N2O2V = 1101.5 (4) Å3
Mr = 291.51Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.764 (3) ŵ = 0.82 mm1
b = 5.5177 (11) ÅT = 150 K
c = 12.313 (3) Å0.41 × 0.32 × 0.28 mm
β = 104.73 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
8836 reflections with I > 2σ(I)
53399 measured reflectionsRint = 0.049
13343 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.087All H-atom parameters refined
S = 0.94Δρmax = 0.77 e Å3
13343 reflectionsΔρmin = 0.78 e Å3
174 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.25457 (2)0.36278 (7)1.05209 (3)0.01255 (5)
C20.31384 (3)0.44511 (8)1.00987 (3)0.01115 (5)
C30.32622 (3)0.37458 (9)0.90491 (4)0.01402 (6)
H30.3708 (8)0.440 (2)0.8783 (12)0.039 (3)*
C40.27365 (3)0.20520 (9)0.84305 (4)0.01436 (7)
H40.2789 (7)0.153 (2)0.7726 (10)0.028 (3)*
C4A0.21140 (3)0.10199 (8)0.88766 (3)0.01160 (6)
C50.16004 (3)0.09001 (8)0.83381 (4)0.01318 (6)
H50.1625 (7)0.145 (2)0.7635 (9)0.023 (2)*
C60.10486 (3)0.18769 (8)0.88700 (4)0.01255 (6)
C70.09477 (3)0.10170 (9)0.99071 (4)0.01477 (7)
H70.0558 (8)0.183 (2)1.0220 (12)0.038 (3)*
C80.14274 (3)0.08850 (9)1.04182 (4)0.01531 (7)
H80.1371 (7)0.153 (2)1.1083 (9)0.022 (2)*
C8A0.20313 (3)0.18986 (8)0.99273 (3)0.01164 (6)
C200.37587 (3)0.61146 (8)1.08827 (4)0.01233 (6)
Cl10.448950 (8)0.42092 (2)1.180552 (11)0.01867 (3)
Cl20.327846 (8)0.79726 (2)1.170061 (13)0.01959 (3)
Cl30.429127 (10)0.80096 (3)1.014289 (12)0.02308 (3)
N20.05360 (3)0.39323 (7)0.83412 (4)0.01431 (6)
O20.00084 (3)0.46332 (8)0.87691 (4)0.02082 (7)
O10.06805 (3)0.48497 (9)0.75024 (4)0.02212 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.01289 (13)0.01453 (13)0.01053 (11)0.00299 (11)0.00352 (10)0.00112 (10)
C20.01118 (13)0.01190 (13)0.00996 (12)0.00069 (11)0.00190 (10)0.00118 (10)
C30.01461 (15)0.01685 (16)0.01150 (14)0.00327 (13)0.00497 (12)0.00008 (12)
C40.01551 (16)0.01805 (16)0.01050 (13)0.00309 (13)0.00511 (12)0.00102 (12)
C4A0.01160 (13)0.01384 (14)0.00937 (12)0.00079 (11)0.00271 (10)0.00021 (10)
C50.01322 (14)0.01510 (15)0.01100 (13)0.00128 (12)0.00267 (11)0.00153 (11)
C60.01149 (13)0.01284 (14)0.01256 (14)0.00132 (12)0.00167 (11)0.00077 (11)
C70.01345 (15)0.01751 (16)0.01420 (15)0.00376 (13)0.00507 (12)0.00146 (12)
C80.01483 (16)0.01944 (17)0.01328 (15)0.00500 (14)0.00658 (13)0.00324 (13)
C8A0.01119 (13)0.01393 (14)0.01012 (12)0.00163 (11)0.00327 (10)0.00082 (10)
C200.01242 (14)0.01115 (13)0.01290 (14)0.00107 (11)0.00225 (11)0.00067 (10)
Cl10.01609 (5)0.01582 (4)0.01943 (5)0.00211 (3)0.00406 (3)0.00031 (3)
Cl20.01840 (5)0.01531 (4)0.02536 (6)0.00044 (4)0.00613 (4)0.00751 (4)
Cl30.02756 (6)0.02171 (5)0.02065 (5)0.01311 (5)0.00736 (5)0.00128 (4)
N20.01378 (14)0.01258 (12)0.01511 (14)0.00145 (11)0.00094 (11)0.00038 (10)
O20.02175 (17)0.02142 (16)0.01935 (16)0.00950 (14)0.00536 (13)0.00019 (13)
O10.02192 (17)0.02151 (17)0.02371 (18)0.00429 (14)0.00726 (14)0.01054 (14)
Geometric parameters (Å, º) top
N1—C21.3140 (6)C6—C71.4121 (7)
N1—C8A1.3666 (6)C6—N21.4711 (7)
C2—C31.4147 (7)C7—C81.3736 (7)
C2—C201.5314 (7)C7—H70.950 (14)
C3—C41.3743 (7)C8—C8A1.4193 (7)
C3—H30.961 (14)C8—H80.919 (11)
C4—C4A1.4167 (7)C20—Cl21.7679 (6)
C4—H40.939 (12)C20—Cl31.7703 (5)
C4A—C51.4187 (7)C20—Cl11.7859 (6)
C4A—C8A1.4209 (6)N2—O21.2266 (7)
C5—C61.3724 (7)N2—O11.2284 (6)
C5—H50.928 (11)
C2—N1—C8A117.87 (4)C8—C7—C6118.71 (4)
N1—C2—C3124.59 (4)C8—C7—H7123.8 (8)
N1—C2—C20114.73 (4)C6—C7—H7117.5 (8)
C3—C2—C20120.46 (4)C7—C8—C8A120.25 (4)
C4—C3—C2118.10 (4)C7—C8—H8121.5 (7)
C4—C3—H3120.9 (8)C8A—C8—H8118.2 (7)
C2—C3—H3121.0 (8)N1—C8A—C8117.95 (4)
C3—C4—C4A119.36 (4)N1—C8A—C4A122.06 (4)
C3—C4—H4121.6 (8)C8—C8A—C4A119.90 (4)
C4A—C4—H4119.0 (8)C2—C20—Cl2111.85 (3)
C4—C4A—C5122.56 (4)C2—C20—Cl3112.34 (3)
C4—C4A—C8A117.90 (4)Cl2—C20—Cl3108.24 (3)
C5—C4A—C8A119.49 (4)C2—C20—Cl1107.11 (4)
C6—C5—C4A118.22 (4)Cl2—C20—Cl1108.48 (3)
C6—C5—H5120.9 (7)Cl3—C20—Cl1108.72 (3)
C4A—C5—H5120.9 (7)O2—N2—O1123.96 (5)
C5—C6—C7123.35 (4)O2—N2—C6117.88 (4)
C5—C6—N2118.71 (4)O1—N2—C6118.16 (4)
C7—C6—N2117.94 (4)
(III) 5-nitro-2-(trichloromethyl)quinoline top
Crystal data top
C10H5Cl3N2O2Z = 4
Mr = 291.51F(000) = 584
Triclinic, P1Dx = 1.752 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7551 (6) ÅCell parameters from 5806 reflections
b = 11.3903 (9) Åθ = 2.9–29.2°
c = 13.6023 (11) ŵ = 0.82 mm1
α = 69.927 (5)°T = 150 K
β = 87.071 (5)°Plate, translucent pale brown
γ = 78.391 (5)°0.38 × 0.28 × 0.25 mm
V = 1105.25 (15) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5286 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.023
Graphite monochromatorθmax = 29.2°, θmin = 2.7°
ϕ and ω scansh = 710
21169 measured reflectionsk = 1415
5900 independent reflectionsl = 1618
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: difference Fourier map
wR(F2) = 0.062All H-atom parameters refined
S = 1.07 w = 1/[σ2(Fo2) + (0.0268P)2 + 0.485P]
where P = (Fo2 + 2Fc2)/3
5900 reflections(Δ/σ)max = 0.001
347 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C10H5Cl3N2O2γ = 78.391 (5)°
Mr = 291.51V = 1105.25 (15) Å3
Triclinic, P1Z = 4
a = 7.7551 (6) ÅMo Kα radiation
b = 11.3903 (9) ŵ = 0.82 mm1
c = 13.6023 (11) ÅT = 150 K
α = 69.927 (5)°0.38 × 0.28 × 0.25 mm
β = 87.071 (5)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5286 reflections with I > 2σ(I)
21169 measured reflectionsRint = 0.023
5900 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.062All H-atom parameters refined
S = 1.07Δρmax = 0.47 e Å3
5900 reflectionsΔρmin = 0.26 e Å3
347 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.43438 (13)0.22960 (10)0.80972 (8)0.01453 (18)
C120.48445 (15)0.31467 (11)0.72662 (9)0.0143 (2)
C130.53389 (16)0.29276 (12)0.63196 (9)0.0178 (2)
H130.562 (2)0.3587 (18)0.5721 (14)0.024 (4)*
C140.53711 (16)0.17438 (12)0.62628 (9)0.0178 (2)
H140.570 (2)0.1567 (18)0.5654 (14)0.024 (4)*
C14A0.48951 (15)0.07755 (11)0.71504 (9)0.0143 (2)
C150.48221 (15)0.04903 (11)0.72199 (9)0.0156 (2)
C160.42602 (16)0.13497 (12)0.80916 (10)0.0171 (2)
H160.426 (2)0.2197 (18)0.8094 (13)0.022 (4)*
C170.37405 (16)0.09917 (12)0.89726 (9)0.0169 (2)
H170.338 (2)0.1603 (19)0.9568 (15)0.027 (4)*
C180.37622 (15)0.02161 (12)0.89528 (9)0.0158 (2)
H180.341 (2)0.0465 (18)0.9518 (14)0.023 (4)*
C18A0.43444 (14)0.11120 (11)0.80541 (9)0.0138 (2)
C1200.47421 (15)0.44671 (11)0.73498 (9)0.0154 (2)
Cl110.52356 (4)0.43612 (3)0.86399 (2)0.01923 (7)
Cl120.62116 (4)0.53249 (3)0.64921 (2)0.01945 (6)
Cl130.25585 (4)0.53581 (3)0.69886 (3)0.02495 (7)
N120.53457 (15)0.09447 (10)0.63356 (8)0.0191 (2)
O110.65414 (13)0.05422 (10)0.57750 (7)0.02397 (19)
O120.45554 (16)0.17240 (10)0.62212 (8)0.0282 (2)
N210.92776 (13)0.05485 (9)0.86257 (7)0.01364 (18)
C220.95423 (14)0.14273 (11)0.81846 (8)0.01277 (19)
C231.01433 (16)0.12367 (12)0.71524 (9)0.0161 (2)
H231.042 (2)0.1905 (18)0.6896 (14)0.026 (4)*
C241.03456 (16)0.00416 (12)0.65354 (9)0.0160 (2)
H241.078 (2)0.0113 (18)0.5838 (14)0.024 (4)*
C24A0.99908 (14)0.09597 (11)0.69532 (8)0.01308 (19)
C251.01413 (15)0.22490 (11)0.64227 (9)0.0148 (2)
C260.99756 (16)0.31334 (12)0.69108 (9)0.0168 (2)
H261.011 (2)0.3977 (18)0.6500 (14)0.024 (4)*
C270.95829 (17)0.27823 (12)0.79842 (10)0.0180 (2)
H270.948 (2)0.3418 (18)0.8301 (14)0.022 (4)*
C280.93461 (16)0.15684 (11)0.85296 (9)0.0164 (2)
H280.908 (2)0.1290 (17)0.9240 (14)0.021 (4)*
C28A0.95347 (14)0.06419 (11)0.80293 (8)0.01293 (19)
C2200.92828 (15)0.27577 (11)0.88714 (9)0.0140 (2)
Cl210.79043 (4)0.27363 (3)0.99337 (2)0.01697 (6)
Cl221.14003 (4)0.37009 (3)0.93662 (2)0.01873 (6)
Cl230.83655 (4)0.34963 (3)0.81128 (2)0.01901 (6)
N221.03808 (15)0.27163 (11)0.52829 (8)0.0209 (2)
O210.97422 (16)0.22181 (10)0.47560 (7)0.0301 (2)
O221.11331 (16)0.36176 (11)0.49120 (9)0.0352 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0148 (4)0.0135 (5)0.0164 (4)0.0036 (3)0.0009 (3)0.0061 (4)
C120.0139 (5)0.0134 (5)0.0165 (5)0.0032 (4)0.0005 (4)0.0056 (4)
C130.0221 (5)0.0168 (5)0.0144 (5)0.0060 (4)0.0019 (4)0.0042 (4)
C140.0217 (5)0.0181 (6)0.0146 (5)0.0042 (4)0.0012 (4)0.0068 (4)
C14A0.0143 (5)0.0136 (5)0.0154 (5)0.0016 (4)0.0016 (4)0.0059 (4)
C150.0158 (5)0.0149 (5)0.0169 (5)0.0004 (4)0.0023 (4)0.0078 (4)
C160.0167 (5)0.0135 (5)0.0212 (5)0.0021 (4)0.0019 (4)0.0063 (4)
C170.0166 (5)0.0148 (5)0.0183 (5)0.0035 (4)0.0008 (4)0.0040 (4)
C180.0154 (5)0.0165 (5)0.0157 (5)0.0034 (4)0.0010 (4)0.0056 (4)
C18A0.0130 (5)0.0134 (5)0.0155 (5)0.0028 (4)0.0012 (4)0.0051 (4)
C1200.0153 (5)0.0145 (5)0.0169 (5)0.0042 (4)0.0009 (4)0.0053 (4)
Cl110.02483 (14)0.01957 (14)0.01781 (12)0.01082 (11)0.00290 (10)0.00874 (10)
Cl120.02378 (14)0.01470 (13)0.01952 (13)0.00819 (10)0.00423 (10)0.00341 (10)
Cl130.01733 (13)0.01935 (15)0.04036 (18)0.00048 (11)0.00507 (12)0.01443 (13)
N120.0248 (5)0.0142 (5)0.0178 (5)0.0009 (4)0.0024 (4)0.0068 (4)
O110.0236 (4)0.0260 (5)0.0223 (4)0.0008 (4)0.0032 (3)0.0109 (4)
O120.0469 (6)0.0193 (5)0.0244 (5)0.0110 (4)0.0003 (4)0.0121 (4)
N210.0156 (4)0.0124 (4)0.0132 (4)0.0041 (3)0.0007 (3)0.0040 (3)
C220.0130 (5)0.0122 (5)0.0131 (5)0.0034 (4)0.0004 (4)0.0036 (4)
C230.0208 (5)0.0147 (5)0.0138 (5)0.0031 (4)0.0008 (4)0.0063 (4)
C240.0189 (5)0.0167 (5)0.0121 (5)0.0024 (4)0.0010 (4)0.0050 (4)
C24A0.0126 (5)0.0132 (5)0.0127 (4)0.0029 (4)0.0001 (4)0.0031 (4)
C250.0143 (5)0.0151 (5)0.0129 (5)0.0036 (4)0.0011 (4)0.0018 (4)
C260.0163 (5)0.0132 (5)0.0194 (5)0.0045 (4)0.0013 (4)0.0027 (4)
C270.0221 (5)0.0138 (5)0.0193 (5)0.0042 (4)0.0011 (4)0.0064 (4)
C280.0214 (5)0.0143 (5)0.0145 (5)0.0039 (4)0.0008 (4)0.0060 (4)
C28A0.0141 (5)0.0121 (5)0.0124 (5)0.0033 (4)0.0002 (4)0.0035 (4)
C2200.0148 (5)0.0124 (5)0.0152 (5)0.0031 (4)0.0004 (4)0.0051 (4)
Cl210.01962 (13)0.01458 (13)0.01654 (12)0.00577 (10)0.00467 (9)0.00435 (9)
Cl220.01613 (12)0.01392 (13)0.02257 (13)0.00129 (10)0.00191 (10)0.00231 (10)
Cl230.02259 (13)0.01585 (13)0.02247 (13)0.00699 (10)0.00148 (10)0.00935 (10)
N220.0249 (5)0.0169 (5)0.0155 (5)0.0016 (4)0.0044 (4)0.0006 (4)
O210.0501 (6)0.0231 (5)0.0140 (4)0.0028 (4)0.0021 (4)0.0046 (4)
O220.0426 (6)0.0292 (6)0.0283 (5)0.0161 (5)0.0146 (5)0.0003 (4)
Geometric parameters (Å, º) top
N11—C121.3123 (15)N21—C221.3119 (14)
N11—C18A1.3697 (15)N21—C28A1.3688 (14)
C12—C131.4138 (16)C22—C231.4144 (15)
C12—C1201.5328 (16)C22—C2201.5302 (16)
C13—C141.3721 (17)C23—C241.3675 (17)
C13—H130.951 (19)C23—H230.926 (19)
C14—C14A1.4194 (16)C24—C24A1.4149 (16)
C14—H140.930 (18)C24—H240.959 (18)
C14A—C151.4246 (16)C24A—C251.4227 (16)
C14A—C18A1.4298 (15)C24A—C28A1.4261 (15)
C15—C161.3697 (17)C25—C261.3675 (17)
C15—N121.4740 (15)C25—N221.4715 (15)
C16—C171.4088 (16)C26—C271.4098 (17)
C16—H160.965 (18)C26—H260.954 (19)
C17—C181.3703 (17)C27—C281.3711 (17)
C17—H170.943 (19)C27—H270.950 (18)
C18—C18A1.4185 (16)C28—C28A1.4208 (15)
C18—H180.918 (18)C28—H280.935 (18)
C120—Cl121.7732 (12)C220—Cl211.7570 (12)
C120—Cl111.7734 (12)C220—Cl231.7861 (11)
C120—Cl131.7860 (12)C220—Cl221.7917 (12)
N12—O111.2290 (15)N22—O221.2266 (16)
N12—O121.2292 (15)N22—O211.2286 (16)
C12—N11—C18A117.98 (10)C22—N21—C28A117.49 (10)
N11—C12—C13124.04 (11)N21—C22—C23124.26 (11)
N11—C12—C120115.35 (10)N21—C22—C220116.64 (10)
C13—C12—C120120.48 (10)C23—C22—C220118.99 (10)
C14—C13—C12118.97 (11)C24—C23—C22118.80 (11)
C14—C13—H13119.7 (11)C24—C23—H23119.9 (11)
C12—C13—H13121.4 (11)C22—C23—H23121.3 (11)
C13—C14—C14A119.29 (11)C23—C24—C24A119.28 (10)
C13—C14—H14121.0 (11)C23—C24—H24120.7 (11)
C14A—C14—H14119.7 (11)C24A—C24—H24120.0 (11)
C14—C14A—C15126.63 (10)C24—C24A—C25126.44 (10)
C14—C14A—C18A117.25 (10)C24—C24A—C28A117.34 (10)
C15—C14A—C18A116.04 (10)C25—C24A—C28A116.11 (10)
C16—C15—C14A122.96 (11)C26—C25—C24A123.18 (10)
C16—C15—N12116.03 (10)C26—C25—N22116.29 (11)
C14A—C15—N12121.00 (11)C24A—C25—N22120.42 (10)
C15—C16—C17119.60 (11)C25—C26—C27119.45 (11)
C15—C16—H16118.9 (10)C25—C26—H26118.0 (11)
C17—C16—H16121.5 (11)C27—C26—H26122.6 (11)
C18—C17—C16120.35 (11)C28—C27—C26120.17 (11)
C18—C17—H17121.5 (12)C28—C27—H27122.4 (11)
C16—C17—H17118.2 (12)C26—C27—H27117.4 (11)
C17—C18—C18A120.43 (11)C27—C28—C28A120.61 (11)
C17—C18—H18121.2 (11)C27—C28—H28123.5 (11)
C18A—C18—H18118.4 (11)C28A—C28—H28115.9 (11)
N11—C18A—C18117.02 (10)N21—C28A—C28117.17 (10)
N11—C18A—C14A122.37 (10)N21—C28A—C24A122.48 (10)
C18—C18A—C14A120.60 (10)C28—C28A—C24A120.35 (10)
C12—C120—Cl12112.11 (8)C22—C220—Cl21112.84 (8)
C12—C120—Cl11111.62 (8)C22—C220—Cl23110.31 (7)
Cl12—C120—Cl11107.88 (6)Cl21—C220—Cl23108.49 (6)
C12—C120—Cl13108.18 (8)C22—C220—Cl22107.97 (7)
Cl12—C120—Cl13107.72 (6)Cl21—C220—Cl22108.77 (6)
Cl11—C120—Cl13109.23 (6)Cl23—C220—Cl22108.36 (6)
O11—N12—O12124.45 (11)O22—N22—O21123.95 (11)
O11—N12—C15118.72 (10)O22—N22—C25118.04 (11)
O12—N12—C15116.82 (11)O21—N22—C25117.92 (11)

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC10H5Cl3N2O2C10H5Cl3N2O2C10H5Cl3N2O2
Mr291.51291.51291.51
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cTriclinic, P1
Temperature (K)150150150
a, b, c (Å)15.1941 (14), 5.5843 (5), 12.9620 (12)16.764 (3), 5.5177 (11), 12.313 (3)7.7551 (6), 11.3903 (9), 13.6023 (11)
α, β, γ (°)90, 91.693 (5), 9090, 104.73 (3), 9069.927 (5), 87.071 (5), 78.391 (5)
V3)1099.33 (17)1101.5 (4)1105.25 (15)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.820.820.82
Crystal size (mm)0.58 × 0.34 × 0.310.41 × 0.32 × 0.280.38 × 0.28 × 0.25
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
42809, 6463, 5214 53399, 13343, 8836 21169, 5900, 5286
Rint0.0280.0490.023
(sin θ/λ)max1)0.8941.1350.686
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.083, 1.11 0.031, 0.087, 0.94 0.022, 0.062, 1.07
No. of reflections6463133435900
No. of parameters174174347
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.71, 0.320.77, 0.780.47, 0.26

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

 

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