Nitrated isomers of 2-(trichloro­methyl)­quinoline

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.

S1. Comment

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 S_RN1 and E_RC1 reactions, leading to novel vinylic chloride derivatives (Verhaeghe, Rathelot, Rault & Vanelle, 2006) (S_RN1 is a nucleophilic radical substitution mechanism and E_RC1 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 S_RN1 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 [C23^iv—H23^iv···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 C8^v—H8^v 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.

S2. Experimental

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).

S3. Refinement

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

Computing details

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

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

Crystal data

C10H5Cl3N2O2	F(000) = 584
Mr = 291.51	Dx = 1.761 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9918 reflections
a = 15.1941 (14) Å	θ = 2.7–40.5°
b = 5.5843 (5) Å	µ = 0.82 mm^−1
c = 12.9620 (12) Å	T = 150 K
β = 91.693 (5)°	Prism, translucent pale brown
V = 1099.33 (17) Å^3	0.58 × 0.34 × 0.31 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	5214 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.028
Graphite monochromator	θmax = 39.4°, θmin = 2.7°
ϕ and ω scans	h = −27→27
42809 measured reflections	k = −9→9
6463 independent reflections	l = −23→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: difference Fourier map
wR(F^2) = 0.083	All H-atom parameters refined
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0322P)^2 + 0.4692P] where P = (Fo^2 + 2Fc^2)/3
6463 reflections	(Δ/σ)max = 0.002
174 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.25586 (5)	0.13830 (12)	0.38627 (5)	0.01198 (11)
C2	0.19037 (5)	0.04973 (14)	0.43786 (6)	0.01207 (12)
C3	0.17025 (6)	0.11502 (16)	0.53996 (7)	0.01553 (13)
H3	0.1234 (11)	0.042 (3)	0.5734 (13)	0.030 (4)*
C4	0.21938 (6)	0.29098 (16)	0.58703 (7)	0.01604 (14)
H4	0.2074 (11)	0.341 (3)	0.6565 (12)	0.028 (4)*
C4A	0.28789 (5)	0.40223 (15)	0.53319 (6)	0.01318 (12)
C5	0.33666 (6)	0.59993 (16)	0.57266 (7)	0.01620 (14)
H5	0.3260 (11)	0.652 (3)	0.6398 (12)	0.026 (4)*
C6	0.39971 (6)	0.70626 (16)	0.51478 (7)	0.01674 (14)
H6	0.4306 (11)	0.842 (3)	0.5415 (14)	0.035 (5)*
C7	0.41971 (6)	0.61457 (15)	0.41662 (7)	0.01485 (13)
H7	0.4650 (11)	0.679 (3)	0.3806 (13)	0.027 (4)*
C8	0.37476 (5)	0.41900 (14)	0.38058 (6)	0.01223 (12)
C8A	0.30532 (5)	0.31090 (14)	0.43403 (6)	0.01135 (11)
C21	0.12911 (5)	−0.11660 (14)	0.37547 (6)	0.01346 (12)
Cl1	0.050976 (14)	0.06787 (4)	0.307478 (18)	0.01832 (5)
Cl2	0.186136 (15)	−0.28881 (4)	0.284842 (18)	0.01848 (5)
Cl3	0.071609 (17)	−0.31494 (4)	0.45575 (2)	0.02278 (5)
N2	0.39872 (5)	0.31463 (13)	0.28171 (6)	0.01413 (12)
O1	0.38648 (6)	0.43392 (14)	0.20358 (5)	0.02407 (15)
O2	0.43089 (6)	0.11444 (14)	0.28351 (6)	0.02433 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0115 (3)	0.0135 (2)	0.0111 (3)	−0.0009 (2)	0.0014 (2)	0.0016 (2)
C2	0.0108 (3)	0.0134 (3)	0.0120 (3)	−0.0002 (2)	0.0006 (2)	0.0029 (2)
C3	0.0138 (3)	0.0195 (3)	0.0136 (3)	−0.0012 (3)	0.0041 (2)	0.0025 (3)
C4	0.0159 (3)	0.0208 (3)	0.0116 (3)	−0.0002 (3)	0.0038 (3)	0.0003 (3)
C4A	0.0128 (3)	0.0161 (3)	0.0107 (3)	0.0005 (2)	0.0011 (2)	0.0004 (2)
C5	0.0164 (3)	0.0190 (3)	0.0133 (3)	0.0000 (3)	0.0011 (3)	−0.0030 (3)
C6	0.0161 (3)	0.0168 (3)	0.0173 (3)	−0.0019 (3)	0.0003 (3)	−0.0032 (3)
C7	0.0138 (3)	0.0149 (3)	0.0159 (3)	−0.0023 (2)	0.0018 (3)	0.0003 (2)
C8	0.0122 (3)	0.0140 (3)	0.0106 (3)	−0.0007 (2)	0.0021 (2)	0.0008 (2)
C8A	0.0107 (3)	0.0135 (3)	0.0099 (3)	0.0001 (2)	0.0009 (2)	0.0017 (2)
C21	0.0119 (3)	0.0130 (3)	0.0156 (3)	−0.0008 (2)	0.0015 (2)	0.0029 (2)
Cl1	0.01499 (8)	0.01778 (8)	0.02189 (10)	0.00236 (6)	−0.00444 (7)	0.00126 (7)
Cl2	0.01698 (9)	0.01522 (8)	0.02337 (10)	0.00038 (6)	0.00260 (7)	−0.00368 (7)
Cl3	0.02302 (10)	0.02102 (9)	0.02449 (11)	−0.00943 (7)	0.00384 (8)	0.00649 (7)
N2	0.0135 (3)	0.0170 (3)	0.0121 (3)	−0.0031 (2)	0.0028 (2)	0.0002 (2)
O1	0.0356 (4)	0.0250 (3)	0.0115 (3)	−0.0027 (3)	−0.0002 (3)	0.0039 (2)
O2	0.0313 (4)	0.0212 (3)	0.0210 (3)	0.0073 (3)	0.0087 (3)	−0.0008 (2)

Geometric parameters (Å, º)

N1—C2	1.3121 (10)	C6—C7	1.4129 (12)
N1—C8A	1.3600 (11)	C6—H6	0.950 (18)
C2—C3	1.4148 (12)	C7—C8	1.3633 (12)
C2—C21	1.5293 (12)	C7—H7	0.916 (17)
C3—C4	1.3667 (13)	C8—C8A	1.4145 (11)
C3—H3	0.939 (17)	C8—N2	1.4636 (11)
C4—C4A	1.4139 (12)	C21—Cl2	1.7651 (9)
C4—H4	0.965 (16)	C21—Cl3	1.7682 (8)
C4A—C8A	1.4151 (11)	C21—Cl1	1.7848 (8)
C4A—C5	1.4169 (12)	N2—O2	1.2201 (11)
C5—C6	1.3695 (13)	N2—O1	1.2219 (10)
C5—H5	0.935 (16)
C2—N1—C8A	116.89 (7)	C8—C7—C6	118.68 (8)
N1—C2—C3	124.59 (8)	C8—C7—H7	121.0 (10)
N1—C2—C21	114.73 (7)	C6—C7—H7	120.1 (10)
C3—C2—C21	120.42 (7)	C7—C8—C8A	123.19 (7)
C4—C3—C2	118.20 (7)	C7—C8—N2	118.95 (7)
C4—C3—H3	121.2 (10)	C8A—C8—N2	117.86 (7)
C2—C3—H3	120.5 (10)	N1—C8A—C8	119.31 (7)
C3—C4—C4A	119.73 (8)	N1—C8A—C4A	123.59 (7)
C3—C4—H4	120.6 (10)	C8—C8A—C4A	116.96 (7)
C4A—C4—H4	119.7 (10)	C2—C21—Cl2	112.32 (6)
C4—C4A—C8A	116.76 (8)	C2—C21—Cl3	111.89 (6)
C4—C4A—C5	123.30 (8)	Cl2—C21—Cl3	108.13 (4)
C8A—C4A—C5	119.93 (7)	C2—C21—Cl1	107.22 (5)
C6—C5—C4A	120.46 (8)	Cl2—C21—Cl1	108.56 (5)
C6—C5—H5	121.3 (10)	Cl3—C21—Cl1	108.61 (4)
C4A—C5—H5	118.2 (10)	O2—N2—O1	124.50 (8)
C5—C6—C7	120.58 (8)	O2—N2—C8	117.27 (7)
C5—C6—H6	119.4 (11)	O1—N2—C8	118.23 (7)
C7—C6—H6	120.0 (11)

(II) 6-nitro-2-(trichloromethyl)quinoline

Crystal data

C10H5Cl3N2O2	F(000) = 584
Mr = 291.51	Dx = 1.758 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8836 reflections
a = 16.764 (3) Å	θ = 2.5–53.8°
b = 5.5177 (11) Å	µ = 0.82 mm^−1
c = 12.313 (3) Å	T = 150 K
β = 104.73 (3)°	Prism, translucent pale brown
V = 1101.5 (4) Å^3	0.41 × 0.32 × 0.28 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	8836 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.049
Graphite monochromator	θmax = 53.8°, θmin = 2.5°
ω scans	h = −32→37
53399 measured reflections	k = −12→10
13343 independent reflections	l = −27→27

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: difference Fourier map
wR(F^2) = 0.087	All H-atom parameters refined
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0446P)^2] where P = (Fo^2 + 2Fc^2)/3
13343 reflections	(Δ/σ)max = 0.005
174 parameters	Δρmax = 0.77 e Å^−3
0 restraints	Δρmin = −0.78 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.25457 (2)	0.36278 (7)	1.05209 (3)	0.01255 (5)
C2	0.31384 (3)	0.44511 (8)	1.00987 (3)	0.01115 (5)
C3	0.32622 (3)	0.37458 (9)	0.90491 (4)	0.01402 (6)
H3	0.3708 (8)	0.440 (2)	0.8783 (12)	0.039 (3)*
C4	0.27365 (3)	0.20520 (9)	0.84305 (4)	0.01436 (7)
H4	0.2789 (7)	0.153 (2)	0.7726 (10)	0.028 (3)*
C4A	0.21140 (3)	0.10199 (8)	0.88766 (3)	0.01160 (6)
C5	0.16004 (3)	−0.09001 (8)	0.83381 (4)	0.01318 (6)
H5	0.1625 (7)	−0.145 (2)	0.7635 (9)	0.023 (2)*
C6	0.10486 (3)	−0.18769 (8)	0.88700 (4)	0.01255 (6)
C7	0.09477 (3)	−0.10170 (9)	0.99071 (4)	0.01477 (7)
H7	0.0558 (8)	−0.183 (2)	1.0220 (12)	0.038 (3)*
C8	0.14274 (3)	0.08850 (9)	1.04182 (4)	0.01531 (7)
H8	0.1371 (7)	0.153 (2)	1.1083 (9)	0.022 (2)*
C8A	0.20313 (3)	0.18986 (8)	0.99273 (3)	0.01164 (6)
C20	0.37587 (3)	0.61146 (8)	1.08827 (4)	0.01233 (6)
Cl1	0.448950 (8)	0.42092 (2)	1.180552 (11)	0.01867 (3)
Cl2	0.327846 (8)	0.79726 (2)	1.170061 (13)	0.01959 (3)
Cl3	0.429127 (10)	0.80096 (3)	1.014289 (12)	0.02308 (3)
N2	0.05360 (3)	−0.39323 (7)	0.83412 (4)	0.01431 (6)
O2	−0.00084 (3)	−0.46332 (8)	0.87691 (4)	0.02082 (7)
O1	0.06805 (3)	−0.48497 (9)	0.75024 (4)	0.02212 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.01289 (13)	0.01453 (13)	0.01053 (11)	−0.00299 (11)	0.00352 (10)	−0.00112 (10)
C2	0.01118 (13)	0.01190 (13)	0.00996 (12)	−0.00069 (11)	0.00190 (10)	0.00118 (10)
C3	0.01461 (15)	0.01685 (16)	0.01150 (14)	−0.00327 (13)	0.00497 (12)	0.00008 (12)
C4	0.01551 (16)	0.01805 (16)	0.01050 (13)	−0.00309 (13)	0.00511 (12)	−0.00102 (12)
C4A	0.01160 (13)	0.01384 (14)	0.00937 (12)	−0.00079 (11)	0.00271 (10)	−0.00021 (10)
C5	0.01322 (14)	0.01510 (15)	0.01100 (13)	−0.00128 (12)	0.00267 (11)	−0.00153 (11)
C6	0.01149 (13)	0.01284 (14)	0.01256 (14)	−0.00132 (12)	0.00167 (11)	−0.00077 (11)
C7	0.01345 (15)	0.01751 (16)	0.01420 (15)	−0.00376 (13)	0.00507 (12)	−0.00146 (12)
C8	0.01483 (16)	0.01944 (17)	0.01328 (15)	−0.00500 (14)	0.00658 (13)	−0.00324 (13)
C8A	0.01119 (13)	0.01393 (14)	0.01012 (12)	−0.00163 (11)	0.00327 (10)	−0.00082 (10)
C20	0.01242 (14)	0.01115 (13)	0.01290 (14)	−0.00107 (11)	0.00225 (11)	0.00067 (10)
Cl1	0.01609 (5)	0.01582 (4)	0.01943 (5)	0.00211 (3)	−0.00406 (3)	0.00031 (3)
Cl2	0.01840 (5)	0.01531 (4)	0.02536 (6)	−0.00044 (4)	0.00613 (4)	−0.00751 (4)
Cl3	0.02756 (6)	0.02171 (5)	0.02065 (5)	−0.01311 (5)	0.00736 (5)	0.00128 (4)
N2	0.01378 (14)	0.01258 (12)	0.01511 (14)	−0.00145 (11)	0.00094 (11)	−0.00038 (10)
O2	0.02175 (17)	0.02142 (16)	0.01935 (16)	−0.00950 (14)	0.00536 (13)	0.00019 (13)
O1	0.02192 (17)	0.02151 (17)	0.02371 (18)	−0.00429 (14)	0.00726 (14)	−0.01054 (14)

Geometric parameters (Å, º)

N1—C2	1.3140 (6)	C6—C7	1.4121 (7)
N1—C8A	1.3666 (6)	C6—N2	1.4711 (7)
C2—C3	1.4147 (7)	C7—C8	1.3736 (7)
C2—C20	1.5314 (7)	C7—H7	0.950 (14)
C3—C4	1.3743 (7)	C8—C8A	1.4193 (7)
C3—H3	0.961 (14)	C8—H8	0.919 (11)
C4—C4A	1.4167 (7)	C20—Cl2	1.7679 (6)
C4—H4	0.939 (12)	C20—Cl3	1.7703 (5)
C4A—C5	1.4187 (7)	C20—Cl1	1.7859 (6)
C4A—C8A	1.4209 (6)	N2—O2	1.2266 (7)
C5—C6	1.3724 (7)	N2—O1	1.2284 (6)
C5—H5	0.928 (11)
C2—N1—C8A	117.87 (4)	C8—C7—C6	118.71 (4)
N1—C2—C3	124.59 (4)	C8—C7—H7	123.8 (8)
N1—C2—C20	114.73 (4)	C6—C7—H7	117.5 (8)
C3—C2—C20	120.46 (4)	C7—C8—C8A	120.25 (4)
C4—C3—C2	118.10 (4)	C7—C8—H8	121.5 (7)
C4—C3—H3	120.9 (8)	C8A—C8—H8	118.2 (7)
C2—C3—H3	121.0 (8)	N1—C8A—C8	117.95 (4)
C3—C4—C4A	119.36 (4)	N1—C8A—C4A	122.06 (4)
C3—C4—H4	121.6 (8)	C8—C8A—C4A	119.90 (4)
C4A—C4—H4	119.0 (8)	C2—C20—Cl2	111.85 (3)
C4—C4A—C5	122.56 (4)	C2—C20—Cl3	112.34 (3)
C4—C4A—C8A	117.90 (4)	Cl2—C20—Cl3	108.24 (3)
C5—C4A—C8A	119.49 (4)	C2—C20—Cl1	107.11 (4)
C6—C5—C4A	118.22 (4)	Cl2—C20—Cl1	108.48 (3)
C6—C5—H5	120.9 (7)	Cl3—C20—Cl1	108.72 (3)
C4A—C5—H5	120.9 (7)	O2—N2—O1	123.96 (5)
C5—C6—C7	123.35 (4)	O2—N2—C6	117.88 (4)
C5—C6—N2	118.71 (4)	O1—N2—C6	118.16 (4)
C7—C6—N2	117.94 (4)

(III) 5-nitro-2-(trichloromethyl)quinoline

Crystal data

C10H5Cl3N2O2	Z = 4
Mr = 291.51	F(000) = 584
Triclinic, P1	Dx = 1.752 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7551 (6) Å	Cell parameters from 5806 reflections
b = 11.3903 (9) Å	θ = 2.9–29.2°
c = 13.6023 (11) Å	µ = 0.82 mm^−1
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) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	5286 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.023
Graphite monochromator	θmax = 29.2°, θmin = 2.7°
ϕ and ω scans	h = −7→10
21169 measured reflections	k = −14→15
5900 independent reflections	l = −16→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.062	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0268P)^2 + 0.485P] where P = (Fo^2 + 2Fc^2)/3
5900 reflections	(Δ/σ)max = 0.001
347 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N11	0.43438 (13)	0.22960 (10)	0.80972 (8)	0.01453 (18)
C12	0.48445 (15)	0.31467 (11)	0.72662 (9)	0.0143 (2)
C13	0.53389 (16)	0.29276 (12)	0.63196 (9)	0.0178 (2)
H13	0.562 (2)	0.3587 (18)	0.5721 (14)	0.024 (4)*
C14	0.53711 (16)	0.17438 (12)	0.62628 (9)	0.0178 (2)
H14	0.570 (2)	0.1567 (18)	0.5654 (14)	0.024 (4)*
C14A	0.48951 (15)	0.07755 (11)	0.71504 (9)	0.0143 (2)
C15	0.48221 (15)	−0.04903 (11)	0.72199 (9)	0.0156 (2)
C16	0.42602 (16)	−0.13497 (12)	0.80916 (10)	0.0171 (2)
H16	0.426 (2)	−0.2197 (18)	0.8094 (13)	0.022 (4)*
C17	0.37405 (16)	−0.09917 (12)	0.89726 (9)	0.0169 (2)
H17	0.338 (2)	−0.1603 (19)	0.9568 (15)	0.027 (4)*
C18	0.37622 (15)	0.02161 (12)	0.89528 (9)	0.0158 (2)
H18	0.341 (2)	0.0465 (18)	0.9518 (14)	0.023 (4)*
C18A	0.43444 (14)	0.11120 (11)	0.80541 (9)	0.0138 (2)
C120	0.47421 (15)	0.44671 (11)	0.73498 (9)	0.0154 (2)
Cl11	0.52356 (4)	0.43612 (3)	0.86399 (2)	0.01923 (7)
Cl12	0.62116 (4)	0.53249 (3)	0.64921 (2)	0.01945 (6)
Cl13	0.25585 (4)	0.53581 (3)	0.69886 (3)	0.02495 (7)
N12	0.53457 (15)	−0.09447 (10)	0.63356 (8)	0.0191 (2)
O11	0.65414 (13)	−0.05422 (10)	0.57750 (7)	0.02397 (19)
O12	0.45554 (16)	−0.17240 (10)	0.62212 (8)	0.0282 (2)
N21	0.92776 (13)	−0.05485 (9)	0.86257 (7)	0.01364 (18)
C22	0.95423 (14)	−0.14273 (11)	0.81846 (8)	0.01277 (19)
C23	1.01433 (16)	−0.12367 (12)	0.71524 (9)	0.0161 (2)
H23	1.042 (2)	−0.1905 (18)	0.6896 (14)	0.026 (4)*
C24	1.03456 (16)	−0.00416 (12)	0.65354 (9)	0.0160 (2)
H24	1.078 (2)	0.0113 (18)	0.5838 (14)	0.024 (4)*
C24A	0.99908 (14)	0.09597 (11)	0.69532 (8)	0.01308 (19)
C25	1.01413 (15)	0.22490 (11)	0.64227 (9)	0.0148 (2)
C26	0.99756 (16)	0.31334 (12)	0.69108 (9)	0.0168 (2)
H26	1.011 (2)	0.3977 (18)	0.6500 (14)	0.024 (4)*
C27	0.95829 (17)	0.27823 (12)	0.79842 (10)	0.0180 (2)
H27	0.948 (2)	0.3418 (18)	0.8301 (14)	0.022 (4)*
C28	0.93461 (16)	0.15684 (11)	0.85296 (9)	0.0164 (2)
H28	0.908 (2)	0.1290 (17)	0.9240 (14)	0.021 (4)*
C28A	0.95347 (14)	0.06419 (11)	0.80293 (8)	0.01293 (19)
C220	0.92828 (15)	−0.27577 (11)	0.88714 (9)	0.0140 (2)
Cl21	0.79043 (4)	−0.27363 (3)	0.99337 (2)	0.01697 (6)
Cl22	1.14003 (4)	−0.37009 (3)	0.93662 (2)	0.01873 (6)
Cl23	0.83655 (4)	−0.34963 (3)	0.81128 (2)	0.01901 (6)
N22	1.03808 (15)	0.27163 (11)	0.52829 (8)	0.0209 (2)
O21	0.97422 (16)	0.22181 (10)	0.47560 (7)	0.0301 (2)
O22	1.11331 (16)	0.36176 (11)	0.49120 (9)	0.0352 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0148 (4)	0.0135 (5)	0.0164 (4)	−0.0036 (3)	0.0009 (3)	−0.0061 (4)
C12	0.0139 (5)	0.0134 (5)	0.0165 (5)	−0.0032 (4)	−0.0005 (4)	−0.0056 (4)
C13	0.0221 (5)	0.0168 (5)	0.0144 (5)	−0.0060 (4)	0.0019 (4)	−0.0042 (4)
C14	0.0217 (5)	0.0181 (6)	0.0146 (5)	−0.0042 (4)	0.0012 (4)	−0.0068 (4)
C14A	0.0143 (5)	0.0136 (5)	0.0154 (5)	−0.0016 (4)	−0.0016 (4)	−0.0059 (4)
C15	0.0158 (5)	0.0149 (5)	0.0169 (5)	−0.0004 (4)	−0.0023 (4)	−0.0078 (4)
C16	0.0167 (5)	0.0135 (5)	0.0212 (5)	−0.0021 (4)	−0.0019 (4)	−0.0063 (4)
C17	0.0166 (5)	0.0148 (5)	0.0183 (5)	−0.0035 (4)	0.0008 (4)	−0.0040 (4)
C18	0.0154 (5)	0.0165 (5)	0.0157 (5)	−0.0034 (4)	0.0010 (4)	−0.0056 (4)
C18A	0.0130 (5)	0.0134 (5)	0.0155 (5)	−0.0028 (4)	−0.0012 (4)	−0.0051 (4)
C120	0.0153 (5)	0.0145 (5)	0.0169 (5)	−0.0042 (4)	0.0009 (4)	−0.0053 (4)
Cl11	0.02483 (14)	0.01957 (14)	0.01781 (12)	−0.01082 (11)	0.00290 (10)	−0.00874 (10)
Cl12	0.02378 (14)	0.01470 (13)	0.01952 (13)	−0.00819 (10)	0.00423 (10)	−0.00341 (10)
Cl13	0.01733 (13)	0.01935 (15)	0.04036 (18)	0.00048 (11)	−0.00507 (12)	−0.01443 (13)
N12	0.0248 (5)	0.0142 (5)	0.0178 (5)	0.0009 (4)	−0.0024 (4)	−0.0068 (4)
O11	0.0236 (4)	0.0260 (5)	0.0223 (4)	−0.0008 (4)	0.0032 (3)	−0.0109 (4)
O12	0.0469 (6)	0.0193 (5)	0.0244 (5)	−0.0110 (4)	0.0003 (4)	−0.0121 (4)
N21	0.0156 (4)	0.0124 (4)	0.0132 (4)	−0.0041 (3)	0.0007 (3)	−0.0040 (3)
C22	0.0130 (5)	0.0122 (5)	0.0131 (5)	−0.0034 (4)	−0.0004 (4)	−0.0036 (4)
C23	0.0208 (5)	0.0147 (5)	0.0138 (5)	−0.0031 (4)	0.0008 (4)	−0.0063 (4)
C24	0.0189 (5)	0.0167 (5)	0.0121 (5)	−0.0024 (4)	0.0010 (4)	−0.0050 (4)
C24A	0.0126 (5)	0.0132 (5)	0.0127 (4)	−0.0029 (4)	−0.0001 (4)	−0.0031 (4)
C25	0.0143 (5)	0.0151 (5)	0.0129 (5)	−0.0036 (4)	0.0011 (4)	−0.0018 (4)
C26	0.0163 (5)	0.0132 (5)	0.0194 (5)	−0.0045 (4)	−0.0013 (4)	−0.0027 (4)
C27	0.0221 (5)	0.0138 (5)	0.0193 (5)	−0.0042 (4)	−0.0011 (4)	−0.0064 (4)
C28	0.0214 (5)	0.0143 (5)	0.0145 (5)	−0.0039 (4)	0.0008 (4)	−0.0060 (4)
C28A	0.0141 (5)	0.0121 (5)	0.0124 (5)	−0.0033 (4)	0.0002 (4)	−0.0035 (4)
C220	0.0148 (5)	0.0124 (5)	0.0152 (5)	−0.0031 (4)	−0.0004 (4)	−0.0051 (4)
Cl21	0.01962 (13)	0.01458 (13)	0.01654 (12)	−0.00577 (10)	0.00467 (9)	−0.00435 (9)
Cl22	0.01613 (12)	0.01392 (13)	0.02257 (13)	−0.00129 (10)	−0.00191 (10)	−0.00231 (10)
Cl23	0.02259 (13)	0.01585 (13)	0.02247 (13)	−0.00699 (10)	−0.00148 (10)	−0.00935 (10)
N22	0.0249 (5)	0.0169 (5)	0.0155 (5)	−0.0016 (4)	0.0044 (4)	−0.0006 (4)
O21	0.0501 (6)	0.0231 (5)	0.0140 (4)	−0.0028 (4)	−0.0021 (4)	−0.0046 (4)
O22	0.0426 (6)	0.0292 (6)	0.0283 (5)	−0.0161 (5)	0.0146 (5)	0.0003 (4)

Geometric parameters (Å, º)

N11—C12	1.3123 (15)	N21—C22	1.3119 (14)
N11—C18A	1.3697 (15)	N21—C28A	1.3688 (14)
C12—C13	1.4138 (16)	C22—C23	1.4144 (15)
C12—C120	1.5328 (16)	C22—C220	1.5302 (16)
C13—C14	1.3721 (17)	C23—C24	1.3675 (17)
C13—H13	0.951 (19)	C23—H23	0.926 (19)
C14—C14A	1.4194 (16)	C24—C24A	1.4149 (16)
C14—H14	0.930 (18)	C24—H24	0.959 (18)
C14A—C15	1.4246 (16)	C24A—C25	1.4227 (16)
C14A—C18A	1.4298 (15)	C24A—C28A	1.4261 (15)
C15—C16	1.3697 (17)	C25—C26	1.3675 (17)
C15—N12	1.4740 (15)	C25—N22	1.4715 (15)
C16—C17	1.4088 (16)	C26—C27	1.4098 (17)
C16—H16	0.965 (18)	C26—H26	0.954 (19)
C17—C18	1.3703 (17)	C27—C28	1.3711 (17)
C17—H17	0.943 (19)	C27—H27	0.950 (18)
C18—C18A	1.4185 (16)	C28—C28A	1.4208 (15)
C18—H18	0.918 (18)	C28—H28	0.935 (18)
C120—Cl12	1.7732 (12)	C220—Cl21	1.7570 (12)
C120—Cl11	1.7734 (12)	C220—Cl23	1.7861 (11)
C120—Cl13	1.7860 (12)	C220—Cl22	1.7917 (12)
N12—O11	1.2290 (15)	N22—O22	1.2266 (16)
N12—O12	1.2292 (15)	N22—O21	1.2286 (16)
C12—N11—C18A	117.98 (10)	C22—N21—C28A	117.49 (10)
N11—C12—C13	124.04 (11)	N21—C22—C23	124.26 (11)
N11—C12—C120	115.35 (10)	N21—C22—C220	116.64 (10)
C13—C12—C120	120.48 (10)	C23—C22—C220	118.99 (10)
C14—C13—C12	118.97 (11)	C24—C23—C22	118.80 (11)
C14—C13—H13	119.7 (11)	C24—C23—H23	119.9 (11)
C12—C13—H13	121.4 (11)	C22—C23—H23	121.3 (11)
C13—C14—C14A	119.29 (11)	C23—C24—C24A	119.28 (10)
C13—C14—H14	121.0 (11)	C23—C24—H24	120.7 (11)
C14A—C14—H14	119.7 (11)	C24A—C24—H24	120.0 (11)
C14—C14A—C15	126.63 (10)	C24—C24A—C25	126.44 (10)
C14—C14A—C18A	117.25 (10)	C24—C24A—C28A	117.34 (10)
C15—C14A—C18A	116.04 (10)	C25—C24A—C28A	116.11 (10)
C16—C15—C14A	122.96 (11)	C26—C25—C24A	123.18 (10)
C16—C15—N12	116.03 (10)	C26—C25—N22	116.29 (11)
C14A—C15—N12	121.00 (11)	C24A—C25—N22	120.42 (10)
C15—C16—C17	119.60 (11)	C25—C26—C27	119.45 (11)
C15—C16—H16	118.9 (10)	C25—C26—H26	118.0 (11)
C17—C16—H16	121.5 (11)	C27—C26—H26	122.6 (11)
C18—C17—C16	120.35 (11)	C28—C27—C26	120.17 (11)
C18—C17—H17	121.5 (12)	C28—C27—H27	122.4 (11)
C16—C17—H17	118.2 (12)	C26—C27—H27	117.4 (11)
C17—C18—C18A	120.43 (11)	C27—C28—C28A	120.61 (11)
C17—C18—H18	121.2 (11)	C27—C28—H28	123.5 (11)
C18A—C18—H18	118.4 (11)	C28A—C28—H28	115.9 (11)
N11—C18A—C18	117.02 (10)	N21—C28A—C28	117.17 (10)
N11—C18A—C14A	122.37 (10)	N21—C28A—C24A	122.48 (10)
C18—C18A—C14A	120.60 (10)	C28—C28A—C24A	120.35 (10)
C12—C120—Cl12	112.11 (8)	C22—C220—Cl21	112.84 (8)
C12—C120—Cl11	111.62 (8)	C22—C220—Cl23	110.31 (7)
Cl12—C120—Cl11	107.88 (6)	Cl21—C220—Cl23	108.49 (6)
C12—C120—Cl13	108.18 (8)	C22—C220—Cl22	107.97 (7)
Cl12—C120—Cl13	107.72 (6)	Cl21—C220—Cl22	108.77 (6)
Cl11—C120—Cl13	109.23 (6)	Cl23—C220—Cl22	108.36 (6)
O11—N12—O12	124.45 (11)	O22—N22—O21	123.95 (11)
O11—N12—C15	118.72 (10)	O22—N22—C25	118.04 (11)
O12—N12—C15	116.82 (11)	O21—N22—C25	117.92 (11)