Hydrogen-bonded structures of the isomeric compounds of quinoline with 2-chloro-5-nitro­benzoic acid, 3-chloro-2-nitro­benzoic acid, 4-chloro-2-nitro­benzoic acid and 5-chloro-2-nitro­benzoic acid

The structures of four isomeric compounds, all C₇H₄ClNO₄·C₉H₇N, of quinoline with chloro- and nitro-substituted benzoic acid, namely, 2-chloro-5-nitro­benzoic acid–quinoline (1/1), (I), 3-chloro-2-nitro­benzoic acid–quinoline (1/1), (II), 4-chloro-2-nitro­benzoic acid–quinoline (1/1), (III), and 5-chloro-2-nitro­benzoic acid–quinoline (1/1), (IV), have been determined at 185 K. In each compound, a short hydrogen bond is observed between the pyridine N atom and a carboxyl O atom. The N...O distances are 2.6476 (13), 2.5610 (13), 2.5569 (12) and 2.5429 (12) Å for (I), (II), (III) and (IV), respectively. Although in (I) the H atom in the hydrogen bond is located at the O site, in (II), (III) and (IV) the H atom is disordered in the hydrogen bond over two positions with (N site):(O site) occupancies of 0.39 (3):0.61 (3), 0.47 (3):0.53 (3) and 0.65 (3):0.35 (3), respectively.

S1. Comment

Solid hydrogen-bonded compounds of 2-chloro-4-nitrobenzoic acid with amines and pyridine derivatives were studied by Kalenik et al. (1989), Habeeb & Awad (1995) and Awad & Habeeb (1996) using ³⁵Cl NQR and IR techniques. They reported that the hydrogen bonds formed between the acid and the bases vary from an O—H···N to an O···H—N type with increasing pK_a or proton affinities (PA) of the bases, and that the critical (inversion) point at 50% proton transfer, where a quite [relatively] short hydrogen bond and a broad single minimum potential energy curve for the H atom or a double-minimum potential would be expected, exists in the compound of 3,5-dimethylpyridine (pK_a 6.15, PA 218 kcal mol^-1). However, there is not yet any crystallographic evidence supporting these findings. Moreover, the shapes of the proton donor and acceptor molecules may be as important as the pK_a or PA in determining the critical point. This has prompted us to carry out continuous studies on the structure of chloro- and nitro-substituted benzoic acid compounds with amines and pyridine derivatives (Ishida et al., 2001a, 2002a,b,c; Ishida & Fukunaga, 2004; Gotoh & Ishida, 2007). In addition, the chloro- and nitro-substituted benzoic acid compounds with amine and pyridine systems are of interest in crystal engineering for the formation of chiral two-component molecular crystals (Koshima et al., 1996; Ishida et al., 2001b,c; Sugiyama et al., 2002a,b). Previously, we have analysed the crystal structure of the 2-chloro-4-nitrobenzoic acid–3,5-dimethylpyridine system, but this compound consisted of a 2-chloro-4-nitrobenzoic acid molecule, a 2-chloro-4-nitrobenzate anion and a 3,5-dimethylpyridininum cation in the asymmetric unit, and the hydrogen bond between the acid and the base was an N—H···O type (Ishida et al., 2004).

In this communication, we report the four isomeric compounds, C₇H₄ClNO₄.C₉H₇N, 2-chloro-5-nitrobenzoic acid–quinoline (1/1), (I), 3-chloro-2-nitrobenzoic acid–quinoline (1/1), (II), 4-chloro-2-nitrobenzoic acid–quinoline (1/1), (III), 5-chloro-2-nitrobenzoic acid–quinoline (1/1), (IV). The values of pK_a are 4.90, 2.22, 1.82, 1.97 and 1.86, respectively, for quinoline, 2-chloro-5-nitrobenzoic acid, 3-chloro-2-nitrobenzoic acid, 4-chloro-2-nitrbenzoic acid and 5-chloro-2-nitrobenzoic acid. The ΔpK_a [pK_a(base) - pK_a(acid)] values are 2.68, 3.08, 2.93 and 3.04, respectively, for (I), (II), (III) and (IV), which are smaller than that of 4.18 for the 2-chloro-4-nitrobenzoic acid–3,5-dimethylpyridine system.

The molecular structures of the four compounds, (I), (II), (III) and (IV), are shown in Figs. 1, 2, 3 and 4, respectively. The base and the acid in each compound are held together by a short hydrogen bond between the N atom of the base and the carboxyl group of the acid. In (I), no acid–base interaction is observed and the H atom in the hydrogen bond is located at the O site (Table 1). In (II), (III) and (IV), quite [relatively] short hydrogen bonds between the acid and the base are observed; the N···O distances are 2.5610 (13), 2.5569 (12) and 2.5429 (12) Å, respectively, for (II), (III) and (IV) (Tables 2–4), which are much shorter than that of 2.6476 (13) Å in (I). In the short hydrogen bonds, the H atoms are disordered. This feature is clearly shown in difference Fourier maps (Fig. 5). In (I), only one peak is observed between the acid and base, while in (II), (III) and (IV), two distinct peaks are observed, indicating that the H atom is disordered over two positions. The occupancies of the N site and the O site were refined to 0.39 (3):0.61 (3), 0.47 (3):0.53 (3) and 0.65 (3):0.35 (3), respectively, for (II), (III) and (IV). The benzene C1–C6 ring and the quinoline N2/C8–C16 ring system are approximately coplanar in (I) and (II) with dihedral angles of 1.92 (4) and 4.71 (5)°, respectively, between them, while in (III) and (IV), the two ring planes are twisted out with dihedral angles of 31.65 (4) and 54.43 (5)°, probably due to steric repulsion between the nitro group and the quinoline ring. On the other hand, the dihedral angle between the CO₂ plane and the quinoline ring system in (I) is 22.48 (14)°, which is larger than the dihedral angles of 6.18 (16), 18.77 (13) and 5.41 (15)° in (II), (III) and (IV), respectively. It is of note that compound (I) differs from (II), (III) and (IV) in the orientation of the carboxyl group with respect to the quinoline molecule; in (I), the carbonyl C7O2 group points to the C15—H15 group, but in (II), (III) and (IV), it points to the C8—H8 group, forming a weak C—H···O hydrogen bond (C8—H8···O2; Tables 2–4). In the C10···N2···O1 angle, which may be a measure of the N···H···O hydrogen-bond strength, (I) also differs from the other compounds; the angles are 165.01 (15), 177.33 (5), 173.02 (4) and 176.76 (5)°, respectively, for (I), (II), (III) and (IV).

The packing diagram of the four compounds are given in Figs. 6–9. In (I), the acid and base units held by the hydrogen bond are stacked in an antiparallel manner along the a axis through π–π stacking interactions between the benzene C1–C6 ring and the quinoline N2/C8–C16 ring system (Fig. 6). The centroid–centroid distances are in the range 3.6269 (8)–3.7302 (8) Å. The detailed geometries are given in Table 5. In (II), the acid and base units are linked by a C—H···O hydrogen bond [C5—H5···O2ⁱ; Table 2], forming a molecular tape running along the b axis (Fig. 7). A short Cl···O contact [Cl1···O4ⁱⁱ 3.0389 (10) Å; symmetry code; (ii) -x, -y + 1, -z] is observed between the tapes. Furthermore, the acid and base are alternately stacked along the a axis through π–π stacking interactions between the benzene ring and the quinoline ring system (Table 5). In (III), the hydrogen-bonded acid and base units related to each other by an inversion centre are linked by a C—H···O hydrogen bond [C9—H9···O2ⁱ; Table 3], forming a centrosymmetric 2 + 2 aggregate (Fig. 8). Furthermore, the two components are separately stacked in columns in an antiparallel manner along the b axis through π–π interactions (Table 5). In (IV), the acid molecules are connected by a C—H···O hydrogen bond [C4—H4···O1ⁱ; Table 4] into a chain running along the c axis (Fig. 9). A π–π interaction between the quinoline ring systems is observed (Table 5). A short Cl···O contact [Cl1···O4ⁱⁱ 2.9953 (12) Å; symmetry code: (ii) x - 1, -y + 1/2, z + 1/2] is also present between the chains.

In this communication, we show that the compounds (II), (III) and (IV) have a short double-well N···H···O hydrogen bond. Although these compounds have ΔpK_a of 2.93–3.08, larger than that of 2.68 in (I), more systematic structural studies are required to confirm whether this ΔpK_a range is appropriate to determine the critical point in the chloro- and nitro-substituted benzoic acid–pyridine systems.

Related literature

For related literature, see: Awad & Habeeb (1996); Habeeb & Awad (1995); Ishida & Fukunaga (2004); Ishida et al. (2001a, 2001b, 2001c, 2002a, 2002b, 2002c); Ishida, Rahman & Kashino (2004); Kalenik et al. (1989); Koshima et al. (1996); Sugiyama et al. (2002a, 2002b).

S2. Experimental

Crystals of all compounds were obtained by slow evaporation from acetonitrile solutions of quinoline with corresponding chloro- and nitro-substituted benzoic acid in a 1:1 molar ratio at room temperature [150 ml acetonitrile solution of quinoline (0.455 g) and 2-chloro-5-nitrobenzoic acid (0.709 g) for (I), 30 ml solution of quinoline (0.204 g) and 3-chloro-2-nitrobenzoic acid (0.318 g) for (II), 20 ml solution of quinoline (0.205 g) and 4-chloro-2-nitrobenzoic acid (0.320 g) for (III), and 30 ml solution of quinoline (0.288 g) and 5-chloro-2-nitrobenzoic acid (0.449 g) for (IV)].

S3. Refinement

For (I), the H atom of the carboxyl group was found in a difference Fourier map and refined isotropically. The refined distance is given in Table 1. For (II), (III) and (IV), H atoms in the N···H···O hydrogen bonds were found to be disordered over two positions in difference Fourier maps. Since the site-occupancy factors and isotropic displacement parameters were strongly correlated, the positional parameters and occupancy factors were refined, with U_iso(H) = 1.2U_eq(N or O). The refined distances are given in Tables 2, 3 and 4. Other H atoms of all compounds were positioned geometrically (C—H = 0.95 Å) and treated as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

For all compounds, data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures

	Fig. 1. A molecular view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The O—H···N hydrogen bond is indicated by a dashed line.
	Fig. 2. A molecular view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The N···H···O hydrogen bond is indicated by a dashed line.
	Fig. 3. A molecular view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The N···H···O hydrogen bond is indicated by a dashed line.
	Fig. 4. A molecular view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The N···H···O hydrogen bond is indicated by a dashed line.
	Fig. 5. Difference Fourier maps of (I), (II), (III) and (IV) associated with the N···H···O hydrogen bond between the acid and the base. Maps were calculated on the mean plane of O1/N2/C8/C16 from a model containing all atoms apart from the H atom in the hydrogen bond.
	Fig. 6. A packing diagram of (I), showing π–π interactions between the benzene ring and the quinoline ring system. Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively. H atoms not involved in the O—H···N hydrogen bond have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 2, -y + 1, -z + 1.].
	Fig. 7. A packing diagram of (II), viewed down the a axis. Dashed lines show N···H···O and C—H···O hydrogen bonds, and Cl···O short contacts. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) x, y + 1, z; (ii) -x, -y + 1, -z.].
	Fig. 8. A packing diagram of (III), showing a centrosymmetric 2 + 2 aggregate. N···H···O and C—H···O hydrogen bonds are shown by dashed lines. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (i) -x + 1, -y + 1, -z.].
	Fig. 9. A packing diagram of (IV), viewed approximately down the a axis, showing a molecular chain running along the c axis. N···H···O and C—H···O hydrogen bonds are shown by dashed lines. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry code: (i) x, -y + 1/2, z + 1/2.]

(I) 2-chloro-5-nitrobenzoic acid–quinoline (1/1)

Crystal data

C7H4ClNO4·C9H7N	Z = 2
Mr = 330.73	F(000) = 340.00
Triclinic, P1	Dx = 1.554 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 6.9254 (10) Å	Cell parameters from 13073 reflections
b = 7.4746 (11) Å	θ = 3.3–30.1°
c = 14.310 (2) Å	µ = 0.29 mm^−1
α = 75.861 (4)°	T = 185 K
β = 89.207 (3)°	Block, colourless
γ = 79.842 (4)°	0.33 × 0.28 × 0.20 mm
V = 706.71 (17) Å^3

Data collection

Rigaku RAXIS-RAPIDII diffractometer	3703 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.019
ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.932, Tmax = 0.943	k = −10→10
14562 measured reflections	l = −20→20
4109 independent reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0549P)^2 + 0.1631P] where P = (Fo^2 + 2Fc^2)/3
4109 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.25 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
Cl1	0.89847 (4)	−0.10086 (4)	0.623531 (19)	0.03206 (9)
O1	0.78199 (16)	0.52083 (12)	0.54961 (6)	0.0400 (2)
O2	0.72799 (16)	0.27161 (13)	0.50107 (6)	0.0410 (2)
O3	0.80941 (16)	0.28751 (13)	0.99105 (6)	0.0411 (2)
O4	0.73704 (15)	0.53965 (11)	0.87597 (6)	0.0383 (2)
N1	0.78272 (13)	0.36891 (12)	0.90536 (6)	0.02517 (17)
N2	0.70282 (13)	0.75824 (12)	0.37861 (6)	0.02605 (17)
C1	0.80281 (13)	0.24022 (13)	0.66829 (6)	0.02067 (17)
C2	0.85561 (13)	0.04479 (13)	0.70085 (7)	0.02144 (17)
C3	0.88318 (14)	−0.04260 (13)	0.79921 (7)	0.02355 (18)
H3	0.9187	−0.1752	0.8195	0.028*
C4	0.85911 (14)	0.06253 (13)	0.86688 (7)	0.02261 (18)
H4	0.8774	0.0043	0.9338	0.027*
C5	0.80750 (13)	0.25573 (13)	0.83436 (6)	0.02017 (17)
C6	0.78006 (14)	0.34545 (13)	0.73740 (6)	0.02125 (17)
H6	0.7458	0.4782	0.7179	0.025*
C7	0.76746 (15)	0.34347 (14)	0.56340 (7)	0.02508 (19)
C8	0.65425 (16)	0.92705 (16)	0.39399 (7)	0.0286 (2)
H8	0.6552	0.9382	0.4587	0.034*
C9	0.60095 (16)	1.09191 (15)	0.32017 (8)	0.0292 (2)
H9	0.5669	1.2104	0.3351	0.035*
C10	0.59913 (15)	1.07817 (14)	0.22679 (8)	0.0265 (2)
H10	0.5635	1.1873	0.1758	0.032*
C11	0.65070 (13)	0.90007 (13)	0.20670 (7)	0.02105 (17)
C12	0.65327 (16)	0.87471 (16)	0.11190 (7)	0.0280 (2)
H12	0.6203	0.9804	0.0587	0.034*
C13	0.70285 (16)	0.69915 (18)	0.09610 (8)	0.0318 (2)
H13	0.7039	0.6833	0.0322	0.038*
C14	0.75246 (16)	0.54171 (16)	0.17486 (9)	0.0322 (2)
H14	0.7860	0.4203	0.1633	0.039*
C15	0.75301 (16)	0.56097 (14)	0.26779 (8)	0.0281 (2)
H15	0.7876	0.4538	0.3200	0.034*
C16	0.70185 (13)	0.74116 (13)	0.28540 (6)	0.02089 (17)
H1	0.757 (3)	0.581 (3)	0.4912 (16)	0.073 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.03734 (15)	0.03113 (14)	0.03126 (14)	0.00075 (10)	−0.00146 (10)	−0.01912 (10)
O1	0.0712 (6)	0.0286 (4)	0.0192 (3)	−0.0123 (4)	−0.0077 (4)	−0.0013 (3)
O2	0.0678 (6)	0.0381 (4)	0.0204 (4)	−0.0134 (4)	−0.0035 (4)	−0.0101 (3)
O3	0.0700 (6)	0.0351 (4)	0.0177 (3)	−0.0052 (4)	−0.0012 (4)	−0.0084 (3)
O4	0.0626 (6)	0.0229 (4)	0.0298 (4)	−0.0019 (4)	0.0009 (4)	−0.0111 (3)
N1	0.0327 (4)	0.0245 (4)	0.0200 (4)	−0.0051 (3)	0.0015 (3)	−0.0086 (3)
N2	0.0304 (4)	0.0283 (4)	0.0190 (4)	−0.0053 (3)	−0.0005 (3)	−0.0048 (3)
C1	0.0221 (4)	0.0233 (4)	0.0177 (4)	−0.0044 (3)	0.0010 (3)	−0.0068 (3)
C2	0.0208 (4)	0.0233 (4)	0.0227 (4)	−0.0038 (3)	0.0008 (3)	−0.0103 (3)
C3	0.0266 (4)	0.0191 (4)	0.0246 (4)	−0.0026 (3)	−0.0005 (3)	−0.0058 (3)
C4	0.0262 (4)	0.0220 (4)	0.0190 (4)	−0.0038 (3)	−0.0002 (3)	−0.0041 (3)
C5	0.0232 (4)	0.0209 (4)	0.0178 (4)	−0.0042 (3)	0.0010 (3)	−0.0072 (3)
C6	0.0255 (4)	0.0200 (4)	0.0187 (4)	−0.0039 (3)	0.0008 (3)	−0.0057 (3)
C7	0.0287 (4)	0.0283 (5)	0.0181 (4)	−0.0041 (4)	0.0013 (3)	−0.0062 (3)
C8	0.0310 (5)	0.0352 (5)	0.0235 (4)	−0.0074 (4)	0.0015 (4)	−0.0135 (4)
C9	0.0291 (5)	0.0255 (5)	0.0373 (5)	−0.0051 (4)	0.0008 (4)	−0.0154 (4)
C10	0.0275 (4)	0.0208 (4)	0.0302 (5)	−0.0040 (3)	−0.0031 (4)	−0.0043 (4)
C11	0.0210 (4)	0.0228 (4)	0.0199 (4)	−0.0062 (3)	−0.0004 (3)	−0.0045 (3)
C12	0.0303 (5)	0.0355 (5)	0.0190 (4)	−0.0099 (4)	−0.0005 (4)	−0.0055 (4)
C13	0.0317 (5)	0.0450 (6)	0.0260 (5)	−0.0125 (4)	0.0042 (4)	−0.0185 (4)
C14	0.0314 (5)	0.0311 (5)	0.0404 (6)	−0.0072 (4)	0.0051 (4)	−0.0201 (4)
C15	0.0304 (5)	0.0212 (4)	0.0324 (5)	−0.0035 (4)	0.0005 (4)	−0.0066 (4)
C16	0.0217 (4)	0.0218 (4)	0.0196 (4)	−0.0049 (3)	0.0005 (3)	−0.0052 (3)

Geometric parameters (Å, º)

Cl1—C2	1.7213 (9)	C6—H6	0.9500
O1—C7	1.3134 (13)	C8—C9	1.4089 (16)
O1—H1	0.85 (2)	C8—H8	0.9500
O2—C7	1.2046 (13)	C9—C10	1.3653 (15)
O3—N1	1.2288 (12)	C9—H9	0.9500
O4—N1	1.2267 (12)	C10—C11	1.4138 (13)
N1—C5	1.4633 (11)	C10—H10	0.9500
N2—C8	1.3182 (14)	C11—C12	1.4143 (13)
N2—C16	1.3709 (12)	C11—C16	1.4190 (13)
C1—C6	1.3977 (12)	C12—C13	1.3692 (16)
C1—C2	1.4029 (13)	C12—H12	0.9500
C1—C7	1.5120 (13)	C13—C14	1.4118 (18)
C2—C3	1.3995 (13)	C13—H13	0.9500
C3—C4	1.3799 (13)	C14—C15	1.3722 (15)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.3871 (13)	C15—C16	1.4135 (13)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.3852 (12)
C7—O1—H1	112.2 (14)	N2—C8—H8	118.1
O4—N1—O3	123.72 (9)	C9—C8—H8	118.1
O4—N1—C5	118.16 (8)	C10—C9—C8	118.74 (9)
O3—N1—C5	118.12 (8)	C10—C9—H9	120.6
C8—N2—C16	118.35 (9)	C8—C9—H9	120.6
C6—C1—C2	117.78 (8)	C9—C10—C11	119.42 (9)
C6—C1—C7	118.12 (8)	C9—C10—H10	120.3
C2—C1—C7	124.10 (8)	C11—C10—H10	120.3
C3—C2—C1	121.31 (8)	C10—C11—C12	122.70 (9)
C3—C2—Cl1	115.98 (7)	C10—C11—C16	118.18 (9)
C1—C2—Cl1	122.68 (7)	C12—C11—C16	119.12 (9)
C4—C3—C2	120.44 (9)	C13—C12—C11	120.57 (10)
C4—C3—H3	119.8	C13—C12—H12	119.7
C2—C3—H3	119.8	C11—C12—H12	119.7
C3—C4—C5	118.06 (9)	C12—C13—C14	119.93 (10)
C3—C4—H4	121.0	C12—C13—H13	120.0
C5—C4—H4	121.0	C14—C13—H13	120.0
C6—C5—C4	122.55 (8)	C15—C14—C13	121.16 (10)
C6—C5—N1	118.85 (8)	C15—C14—H14	119.4
C4—C5—N1	118.59 (8)	C13—C14—H14	119.4
C5—C6—C1	119.86 (8)	C14—C15—C16	119.65 (10)
C5—C6—H6	120.1	C14—C15—H15	120.2
C1—C6—H6	120.1	C16—C15—H15	120.2
O2—C7—O1	124.69 (10)	N2—C16—C15	119.00 (9)
O2—C7—C1	123.85 (9)	N2—C16—C11	121.42 (9)
O1—C7—C1	111.46 (8)	C15—C16—C11	119.57 (9)
N2—C8—C9	123.89 (9)
C6—C1—C2—C3	0.51 (14)	C2—C1—C7—O1	−159.84 (10)
C7—C1—C2—C3	−178.95 (9)	C16—N2—C8—C9	0.05 (16)
C6—C1—C2—Cl1	−177.22 (7)	N2—C8—C9—C10	−0.10 (17)
C7—C1—C2—Cl1	3.31 (13)	C8—C9—C10—C11	−0.09 (15)
C1—C2—C3—C4	−0.11 (15)	C9—C10—C11—C12	−179.66 (10)
Cl1—C2—C3—C4	177.77 (7)	C9—C10—C11—C16	0.31 (14)
C2—C3—C4—C5	−0.09 (14)	C10—C11—C12—C13	−179.51 (10)
C3—C4—C5—C6	−0.13 (14)	C16—C11—C12—C13	0.52 (15)
C3—C4—C5—N1	−179.63 (8)	C11—C12—C13—C14	−0.17 (16)
O4—N1—C5—C6	0.49 (14)	C12—C13—C14—C15	−0.32 (17)
O3—N1—C5—C6	−179.30 (9)	C13—C14—C15—C16	0.43 (16)
O4—N1—C5—C4	−179.99 (10)	C8—N2—C16—C15	−179.81 (9)
O3—N1—C5—C4	0.22 (14)	C8—N2—C16—C11	0.18 (14)
C4—C5—C6—C1	0.55 (15)	C14—C15—C16—N2	179.92 (9)
N1—C5—C6—C1	−179.96 (8)	C14—C15—C16—C11	−0.07 (15)
C2—C1—C6—C5	−0.72 (14)	C10—C11—C16—N2	−0.36 (14)
C7—C1—C6—C5	178.78 (8)	C12—C11—C16—N2	179.61 (9)
C6—C1—C7—O2	−158.22 (11)	C10—C11—C16—C15	179.63 (9)
C2—C1—C7—O2	21.24 (16)	C12—C11—C16—C15	−0.41 (14)
C6—C1—C7—O1	20.70 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.85 (2)	1.81 (2)	2.6476 (13)	166 (2)

(II) 3-chloro-2-nitrobenzoic acid–quinoline (1/1)

Crystal data

C7H3.61ClNO4·C9H7.39N	Z = 2
Mr = 330.73	F(000) = 340.00
Triclinic, P1	Dx = 1.523 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.6022 (3) Å	Cell parameters from 15293 reflections
b = 7.6251 (4) Å	θ = 3.3–30.1°
c = 12.9978 (5) Å	µ = 0.29 mm^−1
α = 82.300 (2)°	T = 185 K
β = 75.1792 (12)°	Block, colourless
γ = 85.3277 (19)°	0.37 × 0.20 × 0.16 mm
V = 720.94 (5) Å^3

Data collection

Rigaku RAXIS-RAPID diffractometer	3577 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.021
ω scans	θmax = 30.0°, θmin = 3.3°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −10→10
Tmin = 0.932, Tmax = 0.955	k = −10→10
18189 measured reflections	l = −18→17
4204 independent reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0623P)^2 + 0.102P] where P = (Fo^2 + 2Fc^2)/3
4204 reflections	(Δ/σ)max = 0.001
215 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.27 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	Occ. (<1)
Cl1	0.09948 (4)	0.70840 (4)	0.01727 (2)	0.03763 (10)
O1	0.24102 (14)	0.47705 (11)	0.47472 (7)	0.0418 (2)
H1	0.264 (4)	0.374 (4)	0.517 (2)	0.050*	0.61 (3)
O2	0.18112 (19)	0.29600 (11)	0.36934 (8)	0.0613 (3)
O3	0.31375 (15)	0.35291 (13)	0.13335 (9)	0.0542 (3)
O4	0.01995 (13)	0.34379 (11)	0.18207 (8)	0.0431 (2)
N1	0.16239 (14)	0.41318 (11)	0.17418 (7)	0.0323 (2)
N2	0.29206 (15)	0.18802 (13)	0.59096 (8)	0.0334 (2)
H2	0.274 (6)	0.269 (6)	0.567 (4)	0.040*	0.39 (3)
C1	0.17248 (15)	0.60366 (13)	0.31381 (8)	0.0282 (2)
C2	0.15183 (14)	0.58771 (12)	0.21242 (8)	0.0263 (2)
C3	0.12482 (14)	0.73432 (13)	0.14239 (8)	0.0272 (2)
C4	0.11837 (15)	0.90228 (13)	0.17275 (9)	0.0310 (2)
H4	0.0993	1.0038	0.1252	0.037*
C5	0.13999 (16)	0.92066 (14)	0.27306 (10)	0.0341 (2)
H5	0.1367	1.0356	0.2943	0.041*
C6	0.16636 (17)	0.77302 (14)	0.34269 (9)	0.0330 (2)
H6	0.1805	0.7878	0.4115	0.040*
C7	0.19938 (17)	0.44310 (14)	0.38938 (9)	0.0337 (2)
C8	0.28180 (19)	0.03692 (16)	0.55550 (10)	0.0412 (3)
H8	0.2531	0.0394	0.4883	0.049*
C9	0.3111 (2)	−0.12728 (16)	0.61202 (11)	0.0455 (3)
H9	0.3014	−0.2342	0.5842	0.055*
C10	0.35369 (18)	−0.13093 (15)	0.70764 (11)	0.0406 (3)
H10	0.3771	−0.2413	0.7465	0.049*
C11	0.36323 (15)	0.02816 (14)	0.74940 (9)	0.0310 (2)
C12	0.40007 (17)	0.03508 (17)	0.84986 (10)	0.0388 (3)
H12	0.4248	−0.0716	0.8917	0.047*
C13	0.40033 (18)	0.19334 (19)	0.88711 (10)	0.0423 (3)
H13	0.4241	0.1964	0.9551	0.051*
C14	0.36574 (18)	0.35207 (17)	0.82578 (10)	0.0403 (3)
H14	0.3652	0.4617	0.8530	0.048*
C15	0.33282 (16)	0.35105 (15)	0.72764 (10)	0.0346 (2)
H15	0.3119	0.4595	0.6862	0.042*
C16	0.33003 (14)	0.18897 (14)	0.68804 (8)	0.0284 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.05550 (19)	0.03204 (14)	0.02944 (14)	−0.00563 (11)	−0.01797 (12)	−0.00142 (10)
O1	0.0729 (6)	0.0259 (4)	0.0359 (4)	−0.0021 (4)	−0.0300 (4)	−0.0041 (3)
O2	0.1274 (10)	0.0215 (4)	0.0534 (6)	0.0011 (5)	−0.0564 (6)	−0.0057 (4)
O3	0.0614 (6)	0.0401 (5)	0.0622 (6)	0.0122 (4)	−0.0118 (5)	−0.0260 (5)
O4	0.0630 (6)	0.0253 (4)	0.0508 (5)	−0.0107 (4)	−0.0300 (4)	−0.0031 (3)
N1	0.0508 (6)	0.0204 (4)	0.0308 (4)	0.0016 (4)	−0.0189 (4)	−0.0062 (3)
N2	0.0460 (5)	0.0244 (4)	0.0323 (5)	−0.0016 (4)	−0.0155 (4)	−0.0003 (3)
C1	0.0374 (5)	0.0204 (4)	0.0302 (5)	−0.0007 (4)	−0.0134 (4)	−0.0057 (4)
C2	0.0328 (5)	0.0188 (4)	0.0302 (5)	−0.0009 (3)	−0.0114 (4)	−0.0065 (3)
C3	0.0321 (5)	0.0233 (4)	0.0285 (5)	−0.0029 (4)	−0.0113 (4)	−0.0029 (3)
C4	0.0377 (5)	0.0200 (4)	0.0363 (5)	−0.0031 (4)	−0.0119 (4)	−0.0008 (4)
C5	0.0460 (6)	0.0193 (4)	0.0404 (6)	−0.0028 (4)	−0.0141 (5)	−0.0078 (4)
C6	0.0479 (6)	0.0229 (5)	0.0334 (5)	−0.0013 (4)	−0.0170 (5)	−0.0086 (4)
C7	0.0506 (6)	0.0231 (5)	0.0327 (5)	0.0014 (4)	−0.0196 (5)	−0.0059 (4)
C8	0.0606 (8)	0.0296 (6)	0.0385 (6)	−0.0024 (5)	−0.0212 (6)	−0.0044 (4)
C9	0.0685 (9)	0.0245 (5)	0.0473 (7)	−0.0030 (5)	−0.0212 (6)	−0.0044 (5)
C10	0.0524 (7)	0.0249 (5)	0.0440 (6)	−0.0001 (5)	−0.0150 (6)	0.0028 (4)
C11	0.0315 (5)	0.0286 (5)	0.0318 (5)	−0.0010 (4)	−0.0080 (4)	0.0008 (4)
C12	0.0417 (6)	0.0403 (6)	0.0338 (6)	0.0003 (5)	−0.0132 (5)	0.0042 (5)
C13	0.0465 (7)	0.0519 (7)	0.0313 (5)	−0.0012 (6)	−0.0148 (5)	−0.0052 (5)
C14	0.0477 (7)	0.0385 (6)	0.0375 (6)	−0.0033 (5)	−0.0125 (5)	−0.0105 (5)
C15	0.0417 (6)	0.0273 (5)	0.0359 (5)	−0.0018 (4)	−0.0119 (5)	−0.0032 (4)
C16	0.0297 (5)	0.0265 (5)	0.0289 (5)	−0.0021 (4)	−0.0081 (4)	−0.0006 (4)

Geometric parameters (Å, º)

Cl1—C3	1.7244 (11)	C5—H5	0.9500
O1—C7	1.2913 (13)	C6—H6	0.9500
O1—H1	0.93 (3)	C8—C9	1.3960 (17)
O2—C7	1.2113 (13)	C8—H8	0.9500
O3—N1	1.2181 (14)	C9—C10	1.3586 (19)
O4—N1	1.2186 (13)	C9—H9	0.9500
N1—C2	1.4711 (13)	C10—C11	1.4079 (17)
N2—C8	1.3120 (15)	C10—H10	0.9500
N2—C16	1.3655 (14)	C11—C16	1.4120 (14)
N2—H2	0.68 (5)	C11—C12	1.4122 (16)
C1—C6	1.3864 (13)	C12—C13	1.3594 (19)
C1—C2	1.3885 (14)	C12—H12	0.9500
C1—C7	1.4985 (14)	C13—C14	1.4023 (19)
C2—C3	1.3805 (14)	C13—H13	0.9500
C3—C4	1.3834 (14)	C14—C15	1.3623 (17)
C4—C5	1.3816 (16)	C14—H14	0.9500
C4—H4	0.9500	C15—C16	1.4047 (15)
C5—C6	1.3819 (15)	C15—H15	0.9500
C7—O1—H1	111.3 (18)	N2—C8—C9	122.96 (12)
O3—N1—O4	125.30 (10)	N2—C8—H8	118.5
O3—N1—C2	116.80 (10)	C9—C8—H8	118.5
O4—N1—C2	117.83 (9)	C10—C9—C8	118.57 (11)
C8—N2—C16	119.94 (10)	C10—C9—H9	120.7
C8—N2—H2	126 (4)	C8—C9—H9	120.7
C16—N2—H2	114 (4)	C9—C10—C11	120.27 (11)
C6—C1—C2	117.68 (9)	C9—C10—H10	119.9
C6—C1—C7	121.30 (9)	C11—C10—H10	119.9
C2—C1—C7	121.02 (9)	C10—C11—C16	117.83 (10)
C3—C2—C1	121.68 (9)	C10—C11—C12	123.60 (10)
C3—C2—N1	117.16 (9)	C16—C11—C12	118.55 (10)
C1—C2—N1	121.14 (9)	C13—C12—C11	120.48 (11)
C2—C3—C4	119.84 (10)	C13—C12—H12	119.8
C2—C3—Cl1	120.14 (8)	C11—C12—H12	119.8
C4—C3—Cl1	120.02 (8)	C12—C13—C14	120.42 (11)
C5—C4—C3	119.25 (10)	C12—C13—H13	119.8
C5—C4—H4	120.4	C14—C13—H13	119.8
C3—C4—H4	120.4	C15—C14—C13	120.84 (11)
C4—C5—C6	120.46 (10)	C15—C14—H14	119.6
C4—C5—H5	119.8	C13—C14—H14	119.6
C6—C5—H5	119.8	C14—C15—C16	119.71 (11)
C5—C6—C1	121.09 (10)	C14—C15—H15	120.1
C5—C6—H6	119.5	C16—C15—H15	120.1
C1—C6—H6	119.5	N2—C16—C15	119.62 (10)
O2—C7—O1	124.74 (11)	N2—C16—C11	120.39 (10)
O2—C7—C1	120.85 (10)	C15—C16—C11	119.98 (10)
O1—C7—C1	114.41 (9)
C6—C1—C2—C3	−0.44 (16)	C6—C1—C7—O1	−9.21 (17)
C7—C1—C2—C3	179.23 (10)	C2—C1—C7—O1	171.14 (11)
C6—C1—C2—N1	178.05 (10)	C16—N2—C8—C9	−1.1 (2)
C7—C1—C2—N1	−2.28 (16)	N2—C8—C9—C10	−0.6 (2)
O3—N1—C2—C3	93.08 (12)	C8—C9—C10—C11	1.6 (2)
O4—N1—C2—C3	−84.24 (12)	C9—C10—C11—C16	−0.95 (19)
O3—N1—C2—C1	−85.47 (13)	C9—C10—C11—C12	177.61 (12)
O4—N1—C2—C1	97.21 (12)	C10—C11—C12—C13	−177.45 (12)
C1—C2—C3—C4	0.19 (16)	C16—C11—C12—C13	1.10 (18)
N1—C2—C3—C4	−178.35 (9)	C11—C12—C13—C14	−0.62 (19)
C1—C2—C3—Cl1	−179.90 (8)	C12—C13—C14—C15	−0.6 (2)
N1—C2—C3—Cl1	1.56 (13)	C13—C14—C15—C16	1.21 (19)
C2—C3—C4—C5	0.29 (16)	C8—N2—C16—C15	−177.19 (12)
Cl1—C3—C4—C5	−179.62 (9)	C8—N2—C16—C11	1.70 (17)
C3—C4—C5—C6	−0.50 (17)	C14—C15—C16—N2	178.20 (11)
C4—C5—C6—C1	0.25 (18)	C14—C15—C16—C11	−0.69 (17)
C2—C1—C6—C5	0.22 (17)	C10—C11—C16—N2	−0.70 (16)
C7—C1—C6—C5	−179.45 (11)	C12—C11—C16—N2	−179.33 (10)
C6—C1—C7—O2	170.35 (13)	C10—C11—C16—C15	178.18 (10)
C2—C1—C7—O2	−9.30 (19)	C12—C11—C16—C15	−0.45 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.93 (3)	1.63 (3)	2.5610 (13)	176 (3)
N2—H2···O1	0.68 (4)	1.89 (4)	2.5610 (13)	169 (5)
C5—H5···O2^i	0.95	2.41	3.3408 (15)	167
C8—H8···O2	0.95	2.44	3.1247 (17)	129

Symmetry code: (i) x, y+1, z.

(III) 4-chloro-2-nitrobenzoic acid–quinoline (1/1)

Crystal data

C7H3.53ClNO4·C9H7.47N	Z = 2
Mr = 330.73	F(000) = 340.00
Triclinic, P1	Dx = 1.488 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.9684 (8) Å	Cell parameters from 9812 reflections
b = 8.6178 (7) Å	θ = 3.0–30.0°
c = 11.1202 (9) Å	µ = 0.28 mm^−1
α = 88.959 (2)°	T = 185 K
β = 80.348 (3)°	Block, colourless
γ = 78.671 (3)°	0.45 × 0.45 × 0.35 mm
V = 738.06 (11) Å^3

Data collection

Rigaku RAXIS-RAPID diffractometer	3681 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.032
ω scans	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
Tmin = 0.804, Tmax = 0.906	k = −12→12
11936 measured reflections	l = −15→15
4237 independent reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0635P)^2 + 0.1264P] where P = (Fo^2 + 2Fc^2)/3
4237 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.42 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	Occ. (<1)
Cl1	0.44149 (4)	0.01184 (3)	0.78073 (2)	0.03670 (10)
O1	0.75936 (10)	0.41131 (10)	0.30316 (8)	0.03226 (18)
H1	0.766 (4)	0.465 (4)	0.249 (4)	0.039*	0.53 (3)
O2	0.48528 (12)	0.44258 (13)	0.27182 (9)	0.0448 (2)
O3	0.93926 (13)	0.09385 (14)	0.35728 (11)	0.0573 (3)
O4	0.96626 (15)	0.2538 (2)	0.49643 (12)	0.0776 (5)
N1	0.88154 (12)	0.18311 (14)	0.44458 (10)	0.0396 (3)
N2	0.80002 (11)	0.59677 (10)	0.12311 (8)	0.02490 (17)
H2	0.792 (4)	0.529 (4)	0.194 (3)	0.030*	0.47 (3)
C1	0.56693 (12)	0.28796 (11)	0.43825 (9)	0.02345 (19)
C2	0.69549 (12)	0.19857 (12)	0.49544 (9)	0.02463 (19)
C3	0.66070 (13)	0.11225 (12)	0.59936 (9)	0.0262 (2)
H3	0.7519	0.0526	0.6359	0.031*
C4	0.48841 (13)	0.11573 (12)	0.64835 (9)	0.02481 (19)
C5	0.35483 (13)	0.19985 (13)	0.59393 (10)	0.0282 (2)
H5	0.2372	0.1992	0.6275	0.034*
C6	0.39571 (13)	0.28507 (12)	0.48970 (10)	0.0269 (2)
H6	0.3044	0.3431	0.4524	0.032*
C7	0.60165 (14)	0.38830 (12)	0.32806 (10)	0.0265 (2)
C8	0.69009 (14)	0.61092 (12)	0.04541 (10)	0.0280 (2)
H8	0.5922	0.5618	0.0641	0.034*
C9	0.71070 (15)	0.69512 (13)	−0.06374 (10)	0.0303 (2)
H9	0.6286	0.7024	−0.1175	0.036*
C10	0.85079 (15)	0.76620 (13)	−0.09110 (10)	0.0297 (2)
H10	0.8675	0.8234	−0.1646	0.036*
C11	0.97095 (13)	0.75437 (11)	−0.00960 (9)	0.02514 (19)
C12	1.12012 (15)	0.82365 (13)	−0.03319 (12)	0.0338 (2)
H12	1.1420	0.8816	−0.1057	0.041*
C13	1.23235 (15)	0.80694 (15)	0.04862 (14)	0.0392 (3)
H13	1.3316	0.8545	0.0330	0.047*
C14	1.20253 (15)	0.71999 (15)	0.15591 (13)	0.0378 (3)
H14	1.2828	0.7088	0.2113	0.045*
C15	1.05948 (15)	0.65113 (13)	0.18181 (10)	0.0309 (2)
H15	1.0402	0.5932	0.2546	0.037*
C16	0.94107 (12)	0.66765 (11)	0.09858 (9)	0.02343 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.04098 (17)	0.03931 (16)	0.02862 (14)	−0.01142 (12)	0.00060 (11)	0.01079 (11)
O1	0.0267 (4)	0.0366 (4)	0.0342 (4)	−0.0082 (3)	−0.0063 (3)	0.0155 (3)
O2	0.0353 (4)	0.0601 (6)	0.0460 (5)	−0.0164 (4)	−0.0209 (4)	0.0284 (5)
O3	0.0368 (5)	0.0538 (6)	0.0633 (7)	0.0098 (4)	0.0191 (5)	0.0145 (5)
O4	0.0409 (6)	0.1516 (14)	0.0573 (7)	−0.0523 (8)	−0.0204 (5)	0.0261 (8)
N1	0.0210 (4)	0.0571 (6)	0.0394 (5)	−0.0061 (4)	−0.0060 (4)	0.0257 (5)
N2	0.0244 (4)	0.0236 (4)	0.0256 (4)	−0.0042 (3)	−0.0022 (3)	0.0040 (3)
C1	0.0223 (4)	0.0255 (4)	0.0233 (4)	−0.0053 (3)	−0.0056 (3)	0.0035 (3)
C2	0.0192 (4)	0.0300 (5)	0.0249 (4)	−0.0052 (3)	−0.0044 (3)	0.0048 (4)
C3	0.0239 (4)	0.0293 (5)	0.0252 (4)	−0.0036 (4)	−0.0055 (4)	0.0050 (4)
C4	0.0277 (5)	0.0245 (4)	0.0219 (4)	−0.0069 (4)	−0.0013 (3)	0.0023 (3)
C5	0.0219 (4)	0.0322 (5)	0.0293 (5)	−0.0055 (4)	−0.0009 (4)	0.0011 (4)
C6	0.0208 (4)	0.0301 (5)	0.0298 (5)	−0.0034 (4)	−0.0059 (4)	0.0031 (4)
C7	0.0280 (5)	0.0266 (4)	0.0261 (4)	−0.0058 (4)	−0.0077 (4)	0.0049 (4)
C8	0.0251 (5)	0.0271 (5)	0.0319 (5)	−0.0054 (4)	−0.0051 (4)	0.0024 (4)
C9	0.0302 (5)	0.0328 (5)	0.0287 (5)	−0.0041 (4)	−0.0101 (4)	0.0029 (4)
C10	0.0331 (5)	0.0295 (5)	0.0250 (5)	−0.0038 (4)	−0.0037 (4)	0.0069 (4)
C11	0.0241 (4)	0.0218 (4)	0.0274 (5)	−0.0030 (3)	−0.0003 (4)	0.0014 (4)
C12	0.0279 (5)	0.0285 (5)	0.0432 (6)	−0.0081 (4)	0.0018 (4)	0.0034 (4)
C13	0.0267 (5)	0.0332 (5)	0.0582 (8)	−0.0088 (4)	−0.0040 (5)	−0.0053 (5)
C14	0.0290 (5)	0.0377 (6)	0.0477 (7)	−0.0012 (4)	−0.0148 (5)	−0.0095 (5)
C15	0.0307 (5)	0.0315 (5)	0.0296 (5)	−0.0011 (4)	−0.0086 (4)	−0.0008 (4)
C16	0.0231 (4)	0.0211 (4)	0.0246 (4)	−0.0018 (3)	−0.0025 (3)	0.0000 (3)

Geometric parameters (Å, º)

Cl1—C4	1.7342 (10)	C5—H5	0.9500
O1—C7	1.2940 (13)	C6—H6	0.9500
O1—H1	0.75 (4)	C8—C9	1.4052 (15)
O2—C7	1.2179 (13)	C8—H8	0.9500
O3—N1	1.2183 (17)	C9—C10	1.3645 (16)
O4—N1	1.2102 (18)	C9—H9	0.9500
N1—C2	1.4762 (13)	C10—C11	1.4135 (15)
N2—C8	1.3178 (14)	C10—H10	0.9500
N2—C16	1.3681 (13)	C11—C16	1.4154 (14)
N2—H2	0.97 (4)	C11—C12	1.4166 (15)
C1—C2	1.3921 (13)	C12—C13	1.3658 (19)
C1—C6	1.3930 (14)	C12—H12	0.9500
C1—C7	1.5058 (14)	C13—C14	1.408 (2)
C2—C3	1.3813 (14)	C13—H13	0.9500
C3—C4	1.3843 (14)	C14—C15	1.3725 (17)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.3862 (15)	C15—C16	1.4151 (14)
C5—C6	1.3877 (15)	C15—H15	0.9500
C7—O1—H1	108 (2)	N2—C8—C9	123.16 (10)
O4—N1—O3	125.17 (12)	N2—C8—H8	118.4
O4—N1—C2	117.50 (12)	C9—C8—H8	118.4
O3—N1—C2	117.22 (11)	C10—C9—C8	118.77 (10)
C8—N2—C16	119.42 (9)	C10—C9—H9	120.6
C8—N2—H2	122.4 (19)	C8—C9—H9	120.6
C16—N2—H2	117.9 (19)	C9—C10—C11	119.67 (10)
C2—C1—C6	116.61 (9)	C9—C10—H10	120.2
C2—C1—C7	124.38 (9)	C11—C10—H10	120.2
C6—C1—C7	119.00 (9)	C10—C11—C16	118.19 (9)
C3—C2—C1	123.46 (9)	C10—C11—C12	122.53 (10)
C3—C2—N1	114.83 (9)	C16—C11—C12	119.27 (10)
C1—C2—N1	121.63 (9)	C13—C12—C11	119.82 (11)
C2—C3—C4	117.70 (9)	C13—C12—H12	120.1
C2—C3—H3	121.2	C11—C12—H12	120.1
C4—C3—H3	121.2	C12—C13—C14	120.73 (11)
C3—C4—C5	121.43 (9)	C12—C13—H13	119.6
C3—C4—Cl1	118.53 (8)	C14—C13—H13	119.6
C5—C4—Cl1	120.04 (8)	C15—C14—C13	121.09 (11)
C4—C5—C6	118.92 (10)	C15—C14—H14	119.5
C4—C5—H5	120.5	C13—C14—H14	119.5
C6—C5—H5	120.5	C14—C15—C16	119.10 (11)
C5—C6—C1	121.84 (9)	C14—C15—H15	120.4
C5—C6—H6	119.1	C16—C15—H15	120.4
C1—C6—H6	119.1	N2—C16—C15	119.22 (9)
O2—C7—O1	125.42 (10)	N2—C16—C11	120.79 (9)
O2—C7—C1	120.23 (10)	C15—C16—C11	119.98 (10)
O1—C7—C1	114.34 (9)
C6—C1—C2—C3	−1.24 (16)	C6—C1—C7—O1	165.55 (10)
C7—C1—C2—C3	177.33 (10)	C16—N2—C8—C9	0.57 (15)
C6—C1—C2—N1	175.61 (10)	N2—C8—C9—C10	−0.12 (16)
C7—C1—C2—N1	−5.82 (17)	C8—C9—C10—C11	−0.26 (16)
O4—N1—C2—C3	−75.93 (15)	C9—C10—C11—C16	0.17 (15)
O3—N1—C2—C3	100.52 (12)	C9—C10—C11—C12	179.21 (10)
O4—N1—C2—C1	106.96 (14)	C10—C11—C12—C13	−179.42 (10)
O3—N1—C2—C1	−76.59 (14)	C16—C11—C12—C13	−0.40 (16)
C1—C2—C3—C4	0.01 (16)	C11—C12—C13—C14	0.67 (18)
N1—C2—C3—C4	−177.04 (10)	C12—C13—C14—C15	−0.65 (18)
C2—C3—C4—C5	1.40 (16)	C13—C14—C15—C16	0.32 (17)
C2—C3—C4—Cl1	−178.58 (8)	C8—N2—C16—C15	−179.52 (9)
C3—C4—C5—C6	−1.50 (16)	C8—N2—C16—C11	−0.64 (14)
Cl1—C4—C5—C6	178.48 (8)	C14—C15—C16—N2	178.85 (10)
C4—C5—C6—C1	0.18 (16)	C14—C15—C16—C11	−0.04 (15)
C2—C1—C6—C5	1.13 (16)	C10—C11—C16—N2	0.27 (14)
C7—C1—C6—C5	−177.52 (10)	C12—C11—C16—N2	−178.79 (9)
C2—C1—C7—O2	168.26 (11)	C10—C11—C16—C15	179.15 (9)
C6—C1—C7—O2	−13.20 (16)	C12—C11—C16—C15	0.08 (15)
C2—C1—C7—O1	−13.00 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.75 (4)	1.81 (4)	2.5569 (12)	175 (3)
N2—H2···O1	0.97 (3)	1.59 (3)	2.5569 (12)	173 (3)
C8—H8···O2	0.95	2.59	3.2445 (15)	126
C9—H9···O2^i	0.95	2.52	3.3527 (16)	146

Symmetry code: (i) −x+1, −y+1, −z.

(IV) 5-chloro-2-nitrobenzoic acid–quinoline (1/1)

Crystal data

C7H3.35ClNO4·C9H7.65N	F(000) = 680.00
Mr = 330.73	Dx = 1.488 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 14851 reflections
a = 7.0456 (4) Å	θ = 3.0–30.0°
b = 22.6829 (13) Å	µ = 0.28 mm^−1
c = 9.6273 (6) Å	T = 185 K
β = 106.3182 (18)°	Needle, colourless
V = 1476.61 (15) Å^3	0.33 × 0.25 × 0.16 mm
Z = 4

Data collection

Rigaku RAXIS-RAPIDII diffractometer	3709 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.022
ω scans	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
Tmin = 0.831, Tmax = 0.956	k = −31→31
19004 measured reflections	l = −13→13
4277 independent reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0512P)^2 + 0.3728P] where P = (Fo^2 + 2Fc^2)/3
4277 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.20 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	Occ. (<1)
Cl1	0.43606 (4)	0.247752 (12)	0.67740 (3)	0.02656 (8)
O1	0.78505 (14)	0.10343 (4)	0.27660 (9)	0.02784 (18)
H1	0.785 (7)	0.076 (3)	0.251 (5)	0.033*	0.35 (3)
O2	0.78570 (17)	0.06199 (4)	0.48733 (10)	0.0406 (2)
O3	1.15435 (13)	0.15440 (5)	0.42372 (11)	0.0416 (2)
O4	1.12136 (16)	0.24239 (5)	0.33042 (11)	0.0451 (3)
N1	1.06974 (14)	0.20202 (5)	0.39705 (10)	0.0306 (2)
N2	0.77466 (14)	−0.00154 (4)	0.18202 (10)	0.02455 (19)
H2	0.784 (3)	0.0399 (13)	0.221 (3)	0.029*	0.65 (3)
C1	0.78003 (15)	0.16587 (5)	0.47057 (11)	0.02072 (19)
C2	0.90034 (15)	0.21271 (5)	0.45437 (11)	0.0234 (2)
C3	0.87565 (17)	0.26945 (5)	0.49860 (13)	0.0282 (2)
H3	0.9581	0.3004	0.4830	0.034*
C4	0.72958 (17)	0.28074 (5)	0.56591 (12)	0.0267 (2)
H4	0.7099	0.3194	0.5970	0.032*
C5	0.61298 (15)	0.23436 (5)	0.58689 (11)	0.02139 (19)
C6	0.63462 (15)	0.17766 (5)	0.53938 (11)	0.02142 (19)
H6	0.5504	0.1469	0.5538	0.026*
C7	0.78717 (16)	0.10454 (5)	0.41008 (11)	0.0231 (2)
C8	0.78470 (19)	−0.04613 (5)	0.27095 (13)	0.0305 (2)
H8	0.8029	−0.0385	0.3709	0.037*
C9	0.7692 (2)	−0.10471 (5)	0.22223 (15)	0.0345 (3)
H9	0.7782	−0.1364	0.2883	0.041*
C10	0.74088 (19)	−0.11544 (5)	0.07822 (15)	0.0331 (3)
H10	0.7255	−0.1548	0.0432	0.040*
C11	0.73437 (16)	−0.06815 (5)	−0.01933 (13)	0.0268 (2)
C12	0.71506 (19)	−0.07595 (6)	−0.16837 (14)	0.0368 (3)
H12	0.7017	−0.1145	−0.2087	0.044*
C13	0.7156 (2)	−0.02829 (7)	−0.25406 (14)	0.0416 (3)
H13	0.7041	−0.0339	−0.3539	0.050*
C14	0.73280 (19)	0.02933 (6)	−0.19694 (14)	0.0355 (3)
H14	0.7320	0.0620	−0.2587	0.043*
C15	0.75066 (17)	0.03866 (5)	−0.05328 (13)	0.0286 (2)
H15	0.7615	0.0776	−0.0154	0.034*
C16	0.75274 (15)	−0.01041 (5)	0.03818 (11)	0.0224 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02649 (14)	0.03043 (14)	0.02693 (13)	0.00097 (9)	0.01434 (10)	−0.00486 (9)
O1	0.0421 (5)	0.0215 (4)	0.0218 (4)	−0.0017 (3)	0.0120 (3)	−0.0037 (3)
O2	0.0711 (7)	0.0258 (4)	0.0293 (4)	0.0078 (4)	0.0216 (4)	0.0037 (3)
O3	0.0269 (4)	0.0507 (6)	0.0498 (6)	0.0006 (4)	0.0150 (4)	−0.0200 (5)
O4	0.0392 (5)	0.0659 (7)	0.0383 (5)	−0.0152 (5)	0.0243 (4)	−0.0035 (5)
N1	0.0230 (4)	0.0459 (6)	0.0253 (4)	−0.0081 (4)	0.0109 (4)	−0.0130 (4)
N2	0.0271 (4)	0.0226 (4)	0.0249 (4)	−0.0002 (3)	0.0089 (3)	−0.0032 (3)
C1	0.0216 (4)	0.0230 (5)	0.0174 (4)	0.0007 (4)	0.0052 (3)	−0.0025 (3)
C2	0.0210 (5)	0.0309 (5)	0.0204 (4)	−0.0038 (4)	0.0091 (4)	−0.0054 (4)
C3	0.0300 (5)	0.0286 (5)	0.0295 (5)	−0.0105 (4)	0.0138 (4)	−0.0068 (4)
C4	0.0308 (5)	0.0236 (5)	0.0280 (5)	−0.0042 (4)	0.0121 (4)	−0.0068 (4)
C5	0.0208 (4)	0.0256 (5)	0.0193 (4)	0.0006 (4)	0.0083 (4)	−0.0030 (4)
C6	0.0223 (5)	0.0224 (5)	0.0210 (4)	−0.0012 (4)	0.0085 (4)	−0.0007 (4)
C7	0.0252 (5)	0.0225 (5)	0.0220 (5)	0.0021 (4)	0.0074 (4)	−0.0022 (4)
C8	0.0349 (6)	0.0281 (5)	0.0288 (5)	0.0007 (5)	0.0095 (5)	0.0009 (4)
C9	0.0396 (7)	0.0235 (5)	0.0403 (6)	0.0013 (5)	0.0112 (5)	0.0057 (5)
C10	0.0318 (6)	0.0226 (5)	0.0455 (7)	0.0007 (4)	0.0118 (5)	−0.0061 (5)
C11	0.0218 (5)	0.0268 (5)	0.0324 (5)	0.0004 (4)	0.0086 (4)	−0.0083 (4)
C12	0.0345 (6)	0.0424 (7)	0.0352 (6)	−0.0025 (5)	0.0123 (5)	−0.0168 (5)
C13	0.0384 (7)	0.0608 (9)	0.0273 (6)	−0.0020 (6)	0.0121 (5)	−0.0083 (6)
C14	0.0335 (6)	0.0461 (7)	0.0290 (6)	0.0020 (5)	0.0119 (5)	0.0070 (5)
C15	0.0278 (5)	0.0291 (5)	0.0307 (5)	0.0021 (4)	0.0111 (4)	0.0018 (4)
C16	0.0190 (4)	0.0238 (5)	0.0251 (5)	0.0012 (4)	0.0072 (4)	−0.0040 (4)

Geometric parameters (Å, º)

Cl1—C5	1.7366 (10)	C5—C6	1.3876 (14)
O1—C7	1.2811 (13)	C6—H6	0.9500
O1—H1	0.67 (6)	C8—C9	1.4030 (17)
O2—C7	1.2202 (14)	C8—H8	0.9500
O3—N1	1.2255 (15)	C9—C10	1.3660 (19)
O4—N1	1.2302 (15)	C9—H9	0.9500
N1—C2	1.4690 (14)	C10—C11	1.4181 (18)
N2—C8	1.3142 (15)	C10—H10	0.9500
N2—C16	1.3645 (14)	C11—C16	1.4135 (15)
N2—H2	1.01 (3)	C11—C12	1.4138 (17)
C1—C6	1.3934 (14)	C12—C13	1.360 (2)
C1—C2	1.3950 (15)	C12—H12	0.9500
C1—C7	1.5144 (14)	C13—C14	1.410 (2)
C2—C3	1.3819 (16)	C13—H13	0.9500
C3—C4	1.3855 (16)	C14—C15	1.3695 (17)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.3841 (15)	C15—C16	1.4167 (16)
C4—H4	0.9500	C15—H15	0.9500
C7—O1—H1	113 (4)	N2—C8—C9	121.75 (11)
O3—N1—O4	124.59 (11)	N2—C8—H8	119.1
O3—N1—C2	117.75 (10)	C9—C8—H8	119.1
O4—N1—C2	117.60 (11)	C10—C9—C8	118.92 (11)
C8—N2—C16	121.18 (10)	C10—C9—H9	120.5
C8—N2—H2	119.5 (13)	C8—C9—H9	120.5
C16—N2—H2	119.3 (13)	C9—C10—C11	120.38 (11)
C6—C1—C2	117.26 (9)	C9—C10—H10	119.8
C6—C1—C7	117.87 (9)	C11—C10—H10	119.8
C2—C1—C7	124.73 (9)	C16—C11—C12	119.05 (11)
C3—C2—C1	122.81 (10)	C16—C11—C10	117.33 (10)
C3—C2—N1	117.10 (10)	C12—C11—C10	123.61 (11)
C1—C2—N1	119.97 (10)	C13—C12—C11	120.01 (12)
C2—C3—C4	119.38 (10)	C13—C12—H12	120.0
C2—C3—H3	120.3	C11—C12—H12	120.0
C4—C3—H3	120.3	C12—C13—C14	120.97 (12)
C5—C4—C3	118.50 (10)	C12—C13—H13	119.5
C5—C4—H4	120.8	C14—C13—H13	119.5
C3—C4—H4	120.8	C15—C14—C13	120.69 (12)
C4—C5—C6	122.12 (10)	C15—C14—H14	119.7
C4—C5—Cl1	118.64 (8)	C13—C14—H14	119.7
C6—C5—Cl1	119.23 (8)	C14—C15—C16	119.23 (11)
C5—C6—C1	119.88 (9)	C14—C15—H15	120.4
C5—C6—H6	120.1	C16—C15—H15	120.4
C1—C6—H6	120.1	N2—C16—C11	120.40 (10)
O2—C7—O1	126.59 (10)	N2—C16—C15	119.56 (10)
O2—C7—C1	119.03 (9)	C11—C16—C15	120.04 (10)
O1—C7—C1	114.30 (9)
C6—C1—C2—C3	−2.38 (16)	C2—C1—C7—O1	−48.59 (14)
C7—C1—C2—C3	173.28 (10)	C16—N2—C8—C9	−1.39 (18)
C6—C1—C2—N1	173.45 (9)	N2—C8—C9—C10	−0.7 (2)
C7—C1—C2—N1	−10.90 (16)	C8—C9—C10—C11	2.20 (19)
O3—N1—C2—C3	144.34 (11)	C9—C10—C11—C16	−1.69 (17)
O4—N1—C2—C3	−32.90 (15)	C9—C10—C11—C12	176.88 (12)
O3—N1—C2—C1	−31.71 (14)	C16—C11—C12—C13	0.40 (18)
O4—N1—C2—C1	151.04 (11)	C10—C11—C12—C13	−178.15 (12)
C1—C2—C3—C4	1.94 (18)	C11—C12—C13—C14	−0.8 (2)
N1—C2—C3—C4	−173.99 (10)	C12—C13—C14—C15	0.4 (2)
C2—C3—C4—C5	0.14 (17)	C13—C14—C15—C16	0.34 (19)
C3—C4—C5—C6	−1.73 (17)	C8—N2—C16—C11	1.89 (16)
C3—C4—C5—Cl1	177.56 (9)	C8—N2—C16—C15	−177.42 (11)
C4—C5—C6—C1	1.26 (16)	C12—C11—C16—N2	−178.99 (10)
Cl1—C5—C6—C1	−178.02 (8)	C10—C11—C16—N2	−0.35 (15)
C2—C1—C6—C5	0.76 (15)	C12—C11—C16—C15	0.32 (16)
C7—C1—C6—C5	−175.20 (9)	C10—C11—C16—C15	178.96 (10)
C6—C1—C7—O2	−49.88 (15)	C14—C15—C16—N2	178.63 (10)
C2—C1—C7—O2	134.49 (12)	C14—C15—C16—C11	−0.68 (16)
C6—C1—C7—O1	127.04 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.67 (5)	1.88 (5)	2.5429 (12)	177 (6)
N2—H2···O1	1.01 (3)	1.54 (3)	2.5429 (13)	177 (3)
C4—H4···O1^i	0.95	2.41	3.2748 (14)	151
C8—H8···O2	0.95	2.56	3.2165 (15)	127

Symmetry code: (i) x, −y+1/2, z+1/2.