Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methyl­quinoline with 2-chloro-4-nitro­benzoic acid, 2-chloro-5-nitro­benzoic acid, 3-chloro-2-nitro­benzoic acid and 4-chloro-2-nitro­benzoic acid

Gotoh, K.; Ishida, H.

doi:10.1107/S2056989020013134

research communications

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ISSN: 2056-9890

Volume 76| Part 11| November 2020| Pages 1701-1707

https://doi.org/10.1107/S2056989020013134

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Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methylquinoline with 2-chloro-4-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid, 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid

Kazuma Gotoh ^a and Hiroyuki Ishida ^a ^*

^aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 26 September 2020; accepted 29 September 2020; online 6 October 2020)

The structures of the four isomeric compounds of 6-methylquinoline with chloro- and nitro-substituted benzoic acids, C₇H₄ClNO₄·C₁₀H₉N, namely, 2-chloro-4-nitrobenzoic acid–6-methylquinoline (1/1), (I), 2-chloro-5-nitrobenzoic acid–6-methylquinoline (1/1), (II), 3-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (III), and 4-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (IV), have been determined at 185–190 K. In each compound, the acid and base molecules are linked by a short hydrogen bond between a carboxyl O atom and an N atom of the base. The O⋯N distances are 2.5452 (12), 2.6569 (13), 2.5640 (17) and 2.514 (2) Å, respectively, for compounds (I)–(IV). In the hydrogen-bonded acid–base units of (I), (III) and (IV), the H atoms are each disordered over two positions with O site:N site occupancies of 0.65 (3):0.35 (3), 0.59 (4):0.41 (4) and 0.48 (5):0.52 (5), respectively, for (I), (III) and (IV). The H atom in the hydrogen-bonded unit of (II) is located at the O-atom site. In all of the crystals of (I)–(IV), π–π interactions between the quinoline ring system and the benzene ring of the acid molecule are observed. In addition, a π–π interaction between the benzene rings of adjacent acid molecules and a C—H⋯O hydrogen bond are observed in the crystal of (I), and C—H⋯O hydrogen bonds and O⋯Cl contacts occur in the crystals of (III) and (IV). These intermolecular interactions connect the acid and base molecules, forming a layer structure parallel to the bc plane in (I), a column along the a-axis direction in (II), a layer parallel to the ab plane in (III) and a three-dimensional network in (IV). Hirshfeld surfaces for the title compounds mapped over d_norm and shape index were generated to visualize the weak intermolecular interactions.

Keywords: crystal structure; 2-chloro-4-nitrobenzoic acid; 2-chloro-5-nitrobenzoic acid; 3-chloro-2-nitrobenzoic acid; 4-chloro-2-nitrobenzoic acid; 6-methylquinoline; hydrogen bond; disorder; Hirshfeld surface.

CCDC references: 2034476; 2034475; 2034474; 2034473

1. Chemical context

Properties of hydrogen bonds formed between organic acids and organic bases depend on the pK_a values of the acids and bases as well as intermolecular interactions in the crystals. In our ongoing study on crystal structures of the system of quinoline derivatives–chloro- and nitro-substituted benzoic acids, we have shown that three compounds of quinoline with 3-chloro-2-nitrobenzoic acid, 4-chloro-2-nitrobenzoic acid and 5-chloro-2-nitrobenzoic acid, the ΔpK_a [pK_a(base) − pK_a(acid)] values of which are 3.08, 2.93 and 3.04, respectively, have a short double-well O—H⋯N/O⋯H—N hydrogen bond between the carboxy O atom and the aromatic N atom (Gotoh & Ishida, 2009 ). On the other hand, in 2-chloro-5-nitrobenzoic acid–quinoline (1/1) (ΔpK_a = 2.68; Gotoh & Ishida, 2009), 2-chloro-4-nitrobenzoic acid–quinoline (1/1) (ΔpK_a = 2.86; Gotoh & Ishida, 2011 ), 3-chloro-2-nitrobenzoic acid–6-nitroquinolune (1/1) (ΔpK_a = 1.42), 8-hydroxyquinolinium 3-chloro-2-nitrobenzoate (ΔpK_a = 3.02) and 3-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1) (ΔpK_a = 0.98) (Gotoh & Ishida, 2019a ), 2-chloro-4-nitrobenzoic acid–5-nitroquinoline (1/1) (ΔpK_a = 0.76), 5-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1) (ΔpK_a = 0.94) (Gotoh & Ishida, 2019b ), such a short disordered hydrogen bond was not observed. We report here crystal structures of title four isomeric compounds, namely, 2-chloro-4-nitrobenzoic acid–6-methylquinoline (1/1), (I), 2-chloro-5-nitrobenzoic acid–6-methylquinoline (1/1), (II), 3-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (III), and 4-chloro-2-nitrobenzoic acid–6-methylquinoline (1/1), (IV), in order to extend our studies of short hydrogen bonding and weak intermolecular interactions in the system of quinoline derivatives–chloro- and nitro-substituted benzoic acids. The ΔpK_a values are 3.16, 2.98, 3.38 and 3.23, respectively, for (I)–(IV).

2. Structural commentary

The molecular structures of compounds (I)–(IV) are shown in Fig. 1. In each compound, the acid and base molecules are linked by a hydrogen bond between the carboxy group and the N atom of the base. In (I), (III) and (IV), short hydrogen bonds are observed with N⋯O distances of 2.5452 (12), 2.5640 (17) and 2.515 (2) Å, respectively. (Tables 1, 3 and 4). In these hydrogen bonds, the H atoms are each disordered over two sites; the occupancies of the O site and the N site refined to 0.65 (3) and 0.35 (3), 0.59 (4) and 0.41 (4), and 0.48 (5) and 0.52 (5), respectively, for (I), (III) and (IV). In (II), the H atom in the hydrogen bond is located at the O site with an N⋯O distance of 2.6569 (13) Å (Table 2), being longer than those in (I), (III) and (IV). Weak C—H⋯O hydrogen bonds are each observed in the acid–base unit of (II) (C15—H15⋯O2; Table 2) and the unit of (III) (C8—H8⋯O2; Table 3).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.85 (2)	1.70 (2)	2.5452 (12)	174 (3)
N2—H2⋯O1	0.88 (3)	1.66 (3)	2.5452 (12)	176 (3)
C8—H8⋯O4ⁱ	0.95	2.59	3.2307 (13)	125
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Table 3
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.85 (3)	1.72 (3)	2.5640 (17)	174 (3)
N2—H2⋯O1	0.88 (4)	1.69 (4)	2.5640 (17)	170 (4)
C5—H5⋯.O2ⁱ	0.95	2.44	3.3245 (19)	155
C8—H8⋯.O2	0.95	2.46	3.1438 (19)	129
Symmetry code: (i) x, y+1, z.

Table 4
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.84 (7)	1.70 (6)	2.514 (2)	163 (7)
N2—H2⋯O1	0.87 (4)	1.67 (5)	2.514 (2)	162 (4)
C10—H10⋯O2ⁱ	0.95	2.54	3.364 (3)	145
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.89 (2)	1.78 (2)	2.6569 (13)	169 (2)
C15—H15⋯O2	0.95	2.46	3.3211 (14)	151

Figure 1
Molecular structures of the title compounds (I)–(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. In the hydrogen bonds between the carboxy group and the N atom of the base of compounds (I)

, (III)

and (IV)

, the H atoms are each disordered over two positions. Dashed lines in (II)

and (III)

indicate the O—H⋯N and C—H⋯O hydrogen bonds.

In the hydrogen-bonded acid–base unit of compound (I), the quinoline ring system (N2/C8–C16) and the benzene ring (C1–C6) are almost coplanar with a dihedral angle of 1.11 (4)°, while the quinoline ring system and the carboxy group (O1/C7/O2) of the acid are twisted to each other with a dihedral angle of 28.59 (12)°. In the acid molecule, the benzene ring makes dihedral angles of 29.36 (12) and 8.24 (11)°, respectively, with the carboxy group and the nitro group (O3/N1/O4).

Similar to (I), the quinoline ring system (N2/C8–C16) in the hydrogen-bonded acid–base unit of (II) makes dihedral angles of 2.15 (4) and 24.51 (15)°, respectively, with the benzene ring and the carboxy group. The benzene ring makes dihedral angles of 22.63 (15) and 0.77 (14)°, respectively, with the carboxy group and the nitro group.

Compound (III) crystallizes in the non-centrosymmetric space group P2₁2₁2₁. In the acid–base unit, the quinoline ring system and the benzene ring of the acid are slightly twisted to each other with a dihedral angle of 14.50 (5)°. The quinoline ring system and the carboxy group are also slightly twisted with a dihedral angle of 12.55 (18)°. The benzene ring makes dihedral angles of 3.14 (18) and 85.04 (11)°, respectively, with the carboxy group and the nitro group.

Compound (IV) crystallizes in the non-centrosymmetric space group Cc. In the acid–base unit, the quinoline ring system and the benzene ring of the acid are twisted to each other with a dihedral angle of 30.39 (9)°. The quinoline ring system and the carboxy group are also twisted with a dihedral angle of 21.7 (3)°. The benzene ring makes dihedral angles of 16.4 (3) and 74.4 (3)°, respectively, with the carboxy group and the nitro group.

3. Supramolecular features

In the crystal of (I), the hydrogen–bonded acid-base units are linked by a C—H⋯O hydrogen bond (C8—H8⋯O4ⁱ; symmetry code as given in Table 1), forming a zigzag chain propagating along the c-axis direction (Fig. 2). The acid–base units, which are related to each other by an inversion center, are linked together via π–π interactions between the quinoline ring system and the benzene ring of the acid molecule, forming a centrosymmetric dimeric unit (Fig. 3); the centroid–centroid distances are 3.7217 (6) and 3.7216 (6) Å, respectively, for Cg1⋯Cg2ⁱⁱⁱ and Cg1⋯Cg3ⁱⁱⁱ, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively [symmetry code: (iii) −x + 1, −y + 1, −z + 1]. The dimeric units are further linked into a column structure stacked along the b-axis direction through a weak π–π interaction between the benzene rings with Cg1⋯Cg1^iv = 3.9401 (6) Å [symmetry code: (iv) −x + 1, −y + 2, −z + 1]. The molecular chains are thus stacked into a layer parallel to the bc plane via these π–π interactions.

Figure 2
A packing diagram of (I)

, showing the hydrogen-bonded chain structure formed via the O—H⋯N/O⋯·H—N and C—H⋯O hydrogen bonds (dashed lines). H atoms not involved in the hydrogen bonds are omitted for clarity. Symmetry codes: (i) x, −y + $[{2\over 3}]$ , z − $[{1\over 2}]$ ; (ii) x, −y + $[{3\over 2}]$ , −z + $[{1\over 2}]$ .

Figure 3
A packing diagram of (I)

, showing the column structure formed via the π–π interactions (magenta dashed lines). H atoms except for in the O—H⋯N/O⋯·H—N hydrogen bonds (green dashed lines) are omitted for clarity. Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively. Symmetry codes: (iii) −x + 1, −y + 1, −z + 1; (iv) −x + 1, −y + 2, −z + 1.

In the crystal of (II), the acid and base molecules are alternately stacked in a column via π–π interactions between the acid benzene ring and the quinoline ring system, so that the hydrogen-bonded acid–base units related by an inversion center are linked into a column structure along the a-axis direction (Fig. 4). The centroid–centroid distances are 3.6438 (6), 3.5745 (6), 3.6560 (6) and 3.7375 (6) Å, respectively, for Cg1⋯Cg2ⁱ, Cg1⋯Cg2ⁱⁱ, Cg1⋯Cg3ⁱ and Cg1⋯Cg3ⁱⁱ, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively [symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1]. There are no significant interactions between the columns.

Figure 4
A packing diagram of (II)

, showing the column structure formed via the π–π interactions (magenta dashed lines). H atoms not involved in the O—H⋯N and C—H⋯O hydrogen bonds (green dashed lines) are omitted for clarity. Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively. Symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1.

In the crystal of (III), the hydrogen-bonded acid–base units are linked by a C—H⋯O hydrogen bond (C5—H5⋯O2ⁱ; symmetry code as in Table 3), forming a tape structure propagating along the b-axis direction (Fig. 5). The acid and base molecules are alternately stacked in a column along the a axis direction via π–π interactions between the acid ring and the quinoline ring system (Fig. 6), and thus the hydrogen-bonded acid–base units form a layer lying parallel to the ab plane. The centroid–centroid distances are 3.6415 (8), 3.6126 (8) and 3.6393 (8) Å, respectively, for Cg1⋯Cg2ⁱⁱⁱ, Cg1⋯Cg3ⁱⁱⁱ and Cg1⋯Cg3^iv, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively [symmetry codes: (iii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. A short O⋯Cl contact [O3⋯Cl1^v = 3.0934 (14) Å; symmetry code: (v) x − $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z] is observed between the layers.

Figure 5
A packing diagram of (III)

, showing two tape structures (top and bottom) related by an inversion symmetry to each other, formed by O—H⋯N/O⋯·H—N and C—H⋯O hydrogen bonds (dashed lines). H atoms not involved in the hydrogen bonds are omitted for clarity. Symmetry codes: (i) x, y + 1, z; (ii) x, y − 1, z.

Figure 6
A packing diagram of (III)

, showing the column structure formed via the π–π interactions (magenta dashed lines). H atoms not involved in the O—H⋯·N/O⋯H—N and C—H⋯O hydrogen bonds (green dashed lines) are omitted for clarity. Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively. Symmetry codes: (iii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .

In the crystal of (IV), the hydrogen-bonded acid–base units are linked into a zigzag chain structure propagating along the c-axis direction (Fig. 7) via C—H⋯O hydrogen bonds (C10—H10⋯O2ⁱ; symmetry code as in Table 4). The chains are further linked into a sheet parallel to the bc plane via an O⋯Cl short contact [O4⋯Cl1ⁱⁱ = 3.017 (3) Å; (ii) x, −y, z + $[{1\over 2}]$ ]. Similar to (III), the acid and base molecules are alternately stacked in a column along the a-axis direction via π–π interactions between the acid ring and the quinoline ring system (Fig. 8), and thus the above sheets form a three-dimensional network. The centroid–centroid distances are 3.5813 (13), 3.7987 (14) and 3.7382 (14) Å, respectively, for Cg1⋯Cg2ⁱⁱⁱ, Cg1⋯Cg3ⁱⁱⁱ and Cg1⋯Cg3^iv, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively [symmetry codes: (iii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iv) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

Figure 7
A packing diagram of (IV)

, showing the zigzag chain structure along the c axis via O—H⋯N/O⋯·H—N and C—H⋯O hydrogen bonds. H atoms not involved in the hydrogen bonds are omitted for clarity. Symmetry code: (i) x, −y + 1, z + $[{1\over 2}]$ .

Figure 8
A packing diagram of (IV)

, showing the column structure formed via the π–π interactions (magenta dashed lines). H atoms not involved in the O—H⋯·N/O⋯H—N hydrogen bonds (green dashed lines) are omitted for clarity. Cg1, Cg2 and Cg3 are the centroids of the C1–C6, N2/C8–C11/C16 and C11–C16 rings, respectively. Symmetry codes: (iii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iv) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − 1/2: (v) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (vi) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .

Hirshfeld surfaces for compounds (I)–(IV) mapped over d_norm and shape index (Turner et al., 2017 ; McKinnon et al., 2004 , 2007 ) are shown in Fig. 9. The C—H⋯O interactions in (I), (III) and (IV) are viewed as faint-red spots on the d_norm surfaces (black arrows in Fig. 9). In addition to these interactions, the O⋯Cl contacts in (III) and (IV) are shown as faint-red spots (magenta arrows). The π–π interactions between the acid ring and the quinoline ring system in (I)–(IV) are indicated by blue and red triangles on the shape index surfaces (white circles in Fig. 9).

Figure 9
Hirshfeld surfaces [front (top) and back (bottom) views] for the compounds of (I)–(IV) mapped over d_norm and shape index, indicating the C—H⋯O interactions (black arrows), O⋯Cl contacts (magenta arrows) and π–π interactions (white circles).

4. Database survey

A search of the Cambridge Structural Database (Version 5.41, last update May 2020; Groom et al., 2016 ) for organic co-crystals/salts of 6-methylquinoline with carboxylic acid derivatives showed two structures, namely, 6-methylquinoline hemikis(trans-but-2-enedioic acid) (Cambridge Structural Database refcode LASGUJ; Bekö et al., 2012 ), sesquikis(6-methylquinoline) hemikis(quinoline) trans-but-2-enedioic acid (LASHAQ; Beko et al., 2012). A search for organic co-crystals/salts of 2-chloro-4-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid, 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid gave 61, 12, 9 and 9 structures, respectively. Limiting the search for quinoline derivatives of these compounds gave 3, 2, 4 and 2 compounds, namely, for 2-chloro-4-nitrobenzoic acid: 2-chloro-4-nitrobenzoic acid–5-nitroquinoline (NUBHEA; Gotoh & Ishida, 2019b), 8-hydroxyquinolinium 2-chloro-4-nitrobenzoate (WOPDEM; Babu & Chandrasekaran, 2014 ), 2-chloro-4-nitrobenzoic acid–quinoline (1/1) (YAGFAP; Gotoh & Ishida, 2011), for 2-chloro-5-nitrobenzoic acid: 2-chloro-5-nitrobenzoic acid–quinoline (1/1) (AJIWIA; Gotoh & Ishida, 2009), 8-hydroxy-2-methylquinolinium 2-chloro-5-nitrobenzoate dihydrate (HIHPIY; Tan, 2007 ), for 3-chloro-2-nitrobenzoic acid: 3-chloro-2-nitrobenzoic acid–quinoline (1/1) (AJIWOG, Gotoh & Ishida, 2009), 3-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1) (XOWVUD; Gotoh & Ishida, 2019a), 3-chloro-2-nitrobenzoic acid–6-nitroquinoline (1/1) (XOWWAK, Gotoh & Ishida, 2019a), 8-hydroxyquinolin-1-ium 3-chloro-2-nitrobenzoate (XOWWEO; Gotoh & Ishida, 2019a), and for 4-chloro-2-nitrobenzoic acid: 4-chloro-2-nitrobenzoic acid–quinoline (AJIWUM; Gotoh & Ishida, 2009), 4-hydroxyquinolin-1-ium 4-chloro-2-nitrobenzoate (WOVZOZ; Gotoh & Ishida, 2019c ). Of these compounds, AJIWOG and AJIWUM show disordered O—H⋯N/O⋯H—N hydrogen bonds, while WOVZOZ shows a disorder structure in the O—H⋯O hydrogen bond accompanied by a keto–enol tautomerization in the base molecule.

5. Synthesis and crystallization

Single crystals of the title compounds (I)–(IV) were obtained by slow evaporation from acetonitrile solutions of 6-methylquinoline with chloro-nitrobenzoic acids in a 1:1 molar ratio at room temperature [80 ml acetonitrile solution of 6-methylquinoline (0.20 g) and chloro-nitrobenzoic acid (0.28 g for each acid)].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. All H atoms in compounds (I)–(IV) were found in difference-Fourier maps. The O-bound H atom in (II) was refined freely; the refined distance is given in Table 2. For (I), (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 are strongly collated, the positional parameters and occupancy factors were refined, with bond length restraints of N—H = 0.88 (1) Å and O—H = 0.84 (1) Å, and with U_iso(H) = 1.5U_eq(N or O); the refined distances are given in Tables 1, 3 and 4. Other H atoms were positioned geometrically (C—H = 0.95 Å) and treated as riding, with U_iso(H) = 1.2 or 1.5U_eq(C).

Table 5
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C₇H_3.65ClNO₄·C₁₀H_9.35N	C₇H₄ClNO₄·C₁₀H₉N	C₇H_3.59ClNO₄·C₁₀H_9.41N	C₇H_3.48ClNO₄·C₁₀H_9.52N
M_r	344.74	344.74	344.75	344.75
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$	Orthorhombic, P2₁2₁2₁	Monoclinic, Cc
Temperature (K)	185	186	190	185
a, b, c (Å)	9.5055 (2), 8.3019 (4), 19.5865 (4)	6.8693 (3), 7.6482 (4), 15.1195 (4)	7.1156 (4), 7.5854 (4), 28.8599 (14)	7.4271 (6), 14.4348 (6), 16.2208 (7)
α, β, γ (°)	90, 95.7214 (7), 90	78.218 (3), 81.1923 (18), 77.754 (3)	90, 90, 90	90, 113.203 (3), 90
V (Å³)	1537.94 (8)	754.89 (6)	1557.70 (14)	1598.35 (16)
Z	4	2	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.27	0.28	0.27	0.26
Crystal size (mm)	0.40 × 0.35 × 0.35	0.45 × 0.35 × 0.30	0.30 × 0.30 × 0.17	0.28 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII	Rigaku R-AXIS RAPIDII	Rigaku R-AXIS RAPIDII	Rigaku R-AXIS RAPIDII
Absorption correction	Numerical (NUMABS; Higashi, 1999 )	Numerical (NUMABS; Higashi, 1999)	Numerical (NUMABS; Higashi, 1999)	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.887, 0.909	0.891, 0.920	0.938, 0.955	0.931, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	30539, 4487, 4065	15404, 4381, 3868	30061, 4532, 4365	16695, 4645, 4158
R_int	0.025	0.023	0.017	0.015
(sin θ/λ)_max (Å⁻¹)	0.704	0.703	0.703	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.096, 1.06	0.036, 0.108, 1.05	0.028, 0.079, 1.06	0.030, 0.081, 1.09
No. of reflections	4487	4381	4532	4645
No. of parameters	225	222	225	225
No. of restraints	2	0	2	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.22	0.48, −0.26	0.31, −0.26	0.35, −0.16
Absolute structure	–	–	Flack x determined using 1821 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	Flack x determined using 1899 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	–	–	−0.014 (8)	−0.023 (9)
Computer programs: PROCESS-AUTO (Rigaku, 2006 ), SHELXT (Sheldrick, 2015a ), SHELXS97 (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2020 ), CrystalStructure (Rigaku, 2018 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 2034476; 2034475; 2034474; 2034473

Crystal structure: contains datablocks global, I, II, III, IV. DOI: https://doi.org/10.1107/S2056989020013134/hb7946sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020013134/hb7946Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IIIsup4.hkl

Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IVsup5.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020013134/hb7946Isup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IIsup7.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IIIsup8.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989020013134/hb7946IVsup9.cml

checkCIF report

Computing details top

For all structures, data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: PROCESS-AUTO (Rigaku, 2006). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for (I), (II); SHELXS97 (Sheldrick, 2008) for (III), (IV). Program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b) for (I); SHELXL-2018/3 (Sheldrick, 2015b) for (II); SHELXL2016/6 (Sheldrick, 2015b) for (III); SHELXL2016/6 (Sheldrick, 2015b) for (IV). For all structures, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: CrystalStructure (Rigaku, 2018) and PLATON (Spek, 2020).

2-Chloro-4-nitrobenzoic acid–6-methylquinoline (1/1) (I) top

Crystal data top

C₇H_3.65ClNO₄·C₁₀H_9.35N	F(000) = 712.00
M_r = 344.74	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 9.5055 (2) Å	Cell parameters from 26323 reflections
b = 8.3019 (4) Å	θ = 3.1–30.2°
c = 19.5865 (4) Å	µ = 0.27 mm⁻¹
β = 95.7214 (7)°	T = 185 K
V = 1537.94 (8) Å³	Block, colorless
Z = 4	0.40 × 0.35 × 0.35 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	4065 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 30.0°, θ_min = 3.2°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −13→12
T_min = 0.887, T_max = 0.909	k = −11→11
30539 measured reflections	l = −27→26
4487 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: mixed
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0572P)² + 0.329P] where P = (F_o² + 2F_c²)/3
4487 reflections	(Δ/σ)_max = 0.001
225 parameters	Δρ_max = 0.43 e Å⁻³
2 restraints	Δρ_min = −0.22 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.87370 (3)	0.79426 (3)	0.44087 (2)	0.03134 (8)
O1	0.42961 (8)	0.64577 (11)	0.42646 (5)	0.03635 (19)
H1	0.401 (3)	0.576 (3)	0.3967 (11)	0.055*	0.65 (3)
O2	0.64551 (9)	0.55323 (11)	0.41332 (5)	0.0415 (2)
O3	0.85703 (9)	1.17879 (11)	0.64471 (4)	0.03715 (19)
O4	0.67137 (9)	1.12532 (11)	0.69548 (4)	0.03875 (19)
N1	0.74667 (9)	1.10600 (10)	0.64913 (4)	0.02564 (17)
N2	0.32928 (9)	0.44919 (10)	0.33444 (4)	0.02445 (16)
H2	0.364 (4)	0.521 (4)	0.3649 (17)	0.037*	0.35 (3)
C1	0.61850 (9)	0.76377 (11)	0.49454 (4)	0.02042 (16)
C2	0.75219 (9)	0.83696 (11)	0.49820 (4)	0.02126 (17)
C3	0.79336 (9)	0.95089 (11)	0.54813 (5)	0.02240 (17)
H3	0.883075	1.001906	0.549641	0.027*
C4	0.70028 (10)	0.98778 (11)	0.59541 (4)	0.02162 (17)
C5	0.56791 (10)	0.91744 (12)	0.59456 (5)	0.02394 (18)
H5	0.506368	0.944280	0.628184	0.029*
C6	0.52786 (10)	0.80690 (11)	0.54331 (5)	0.02350 (18)
H6	0.436619	0.759387	0.541313	0.028*
C7	0.56641 (10)	0.64206 (11)	0.44026 (5)	0.02361 (17)
C8	0.40800 (11)	0.39905 (13)	0.28726 (5)	0.0284 (2)
H8	0.500827	0.441308	0.287010	0.034*
C9	0.36003 (12)	0.28509 (13)	0.23709 (5)	0.0314 (2)
H9	0.418985	0.252719	0.203149	0.038*
C10	0.22700 (12)	0.22130 (12)	0.23779 (5)	0.0291 (2)
H10	0.193332	0.143923	0.204340	0.035*
C11	0.14049 (10)	0.27092 (11)	0.28827 (5)	0.02387 (18)
C12	0.00279 (11)	0.20841 (12)	0.29329 (5)	0.0285 (2)
H12	−0.034075	0.128787	0.261562	0.034*
C13	−0.07753 (11)	0.26074 (13)	0.34293 (6)	0.0294 (2)
C14	−0.02173 (11)	0.38120 (13)	0.38945 (6)	0.0299 (2)
H14	−0.078279	0.419813	0.423309	0.036*
C15	0.11154 (11)	0.44368 (12)	0.38702 (5)	0.02705 (19)
H15	0.146830	0.523118	0.419192	0.032*
C16	0.19535 (10)	0.38878 (11)	0.33634 (5)	0.02220 (17)
C17	−0.22358 (12)	0.19441 (16)	0.34909 (8)	0.0408 (3)
H17A	−0.290638	0.283656	0.350772	0.061*
H17B	−0.222599	0.130421	0.391184	0.061*
H17C	−0.252335	0.126106	0.309332	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02668 (13)	0.03764 (15)	0.03157 (13)	−0.00822 (9)	0.01214 (9)	−0.01037 (9)
O1	0.0247 (4)	0.0378 (4)	0.0445 (4)	0.0002 (3)	−0.0067 (3)	−0.0172 (3)
O2	0.0293 (4)	0.0412 (5)	0.0547 (5)	−0.0052 (3)	0.0083 (3)	−0.0239 (4)
O3	0.0343 (4)	0.0387 (4)	0.0387 (4)	−0.0130 (3)	0.0050 (3)	−0.0133 (3)
O4	0.0452 (5)	0.0433 (5)	0.0297 (4)	−0.0057 (4)	0.0133 (3)	−0.0115 (3)
N1	0.0282 (4)	0.0247 (4)	0.0239 (4)	−0.0008 (3)	0.0022 (3)	−0.0028 (3)
N2	0.0244 (4)	0.0227 (4)	0.0254 (4)	−0.0023 (3)	−0.0015 (3)	−0.0010 (3)
C1	0.0196 (4)	0.0194 (4)	0.0219 (4)	−0.0016 (3)	0.0006 (3)	0.0011 (3)
C2	0.0195 (4)	0.0228 (4)	0.0219 (4)	−0.0016 (3)	0.0043 (3)	−0.0005 (3)
C3	0.0197 (4)	0.0235 (4)	0.0241 (4)	−0.0042 (3)	0.0024 (3)	−0.0010 (3)
C4	0.0235 (4)	0.0200 (4)	0.0211 (4)	−0.0012 (3)	0.0011 (3)	−0.0012 (3)
C5	0.0219 (4)	0.0258 (4)	0.0247 (4)	−0.0006 (3)	0.0055 (3)	−0.0004 (3)
C6	0.0193 (4)	0.0246 (4)	0.0268 (4)	−0.0033 (3)	0.0034 (3)	0.0000 (3)
C7	0.0247 (4)	0.0213 (4)	0.0247 (4)	−0.0042 (3)	0.0019 (3)	−0.0004 (3)
C8	0.0274 (4)	0.0280 (5)	0.0297 (5)	−0.0020 (4)	0.0029 (4)	0.0016 (4)
C9	0.0375 (5)	0.0320 (5)	0.0256 (4)	0.0002 (4)	0.0072 (4)	−0.0014 (4)
C10	0.0389 (5)	0.0267 (5)	0.0212 (4)	−0.0027 (4)	0.0000 (4)	−0.0031 (3)
C11	0.0276 (4)	0.0214 (4)	0.0214 (4)	−0.0014 (3)	−0.0038 (3)	0.0008 (3)
C12	0.0286 (5)	0.0257 (4)	0.0295 (5)	−0.0047 (3)	−0.0060 (4)	0.0000 (3)
C13	0.0238 (4)	0.0268 (4)	0.0366 (5)	−0.0010 (4)	−0.0017 (4)	0.0065 (4)
C14	0.0280 (5)	0.0274 (5)	0.0346 (5)	0.0035 (4)	0.0052 (4)	0.0015 (4)
C15	0.0292 (5)	0.0234 (4)	0.0282 (4)	0.0006 (3)	0.0011 (3)	−0.0032 (3)
C16	0.0237 (4)	0.0197 (4)	0.0223 (4)	−0.0004 (3)	−0.0023 (3)	0.0003 (3)
C17	0.0269 (5)	0.0399 (6)	0.0553 (7)	−0.0065 (4)	0.0026 (5)	0.0073 (5)

Geometric parameters (Å, º) top

Cl1—C2	1.7262 (9)	C8—C9	1.4069 (14)
O1—C7	1.3019 (12)	C8—H8	0.9500
O1—H1	0.847 (10)	C9—C10	1.3722 (16)
O2—C7	1.2111 (13)	C9—H9	0.9500
O3—N1	1.2211 (12)	C10—C11	1.4091 (14)
O4—N1	1.2215 (11)	C10—H10	0.9500
N1—C4	1.4739 (12)	C11—C12	1.4206 (14)
N2—C8	1.3134 (13)	C11—C16	1.4205 (12)
N2—C16	1.3722 (12)	C12—C13	1.3656 (16)
N2—H2	0.883 (10)	C12—H12	0.9500
C1—C6	1.3954 (13)	C13—C14	1.4196 (15)
C1—C2	1.4039 (12)	C13—C17	1.5096 (15)
C1—C7	1.5137 (12)	C14—C15	1.3741 (15)
C2—C3	1.3884 (12)	C14—H14	0.9500
C3—C4	1.3774 (13)	C15—C16	1.4090 (14)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.3857 (13)	C17—H17A	0.9800
C5—C6	1.3851 (13)	C17—H17B	0.9800
C5—H5	0.9500	C17—H17C	0.9800
C6—H6	0.9500

C7—O1—H1	112.0 (19)	C10—C9—C8	119.17 (10)
O3—N1—O4	123.98 (9)	C10—C9—H9	120.4
O3—N1—C4	118.49 (8)	C8—C9—H9	120.4
O4—N1—C4	117.53 (8)	C9—C10—C11	119.80 (9)
C8—N2—C16	119.89 (8)	C9—C10—H10	120.1
C8—N2—H2	119 (3)	C11—C10—H10	120.1
C16—N2—H2	121 (3)	C10—C11—C12	123.23 (9)
C6—C1—C2	118.13 (8)	C10—C11—C16	117.72 (9)
C6—C1—C7	118.10 (8)	C12—C11—C16	119.05 (9)
C2—C1—C7	123.77 (8)	C13—C12—C11	121.16 (9)
C3—C2—C1	121.40 (8)	C13—C12—H12	119.4
C3—C2—Cl1	115.99 (7)	C11—C12—H12	119.4
C1—C2—Cl1	122.60 (7)	C12—C13—C14	118.79 (9)
C4—C3—C2	118.04 (8)	C12—C13—C17	121.65 (10)
C4—C3—H3	121.0	C14—C13—C17	119.56 (10)
C2—C3—H3	121.0	C15—C14—C13	122.03 (10)
C3—C4—C5	122.79 (8)	C15—C14—H14	119.0
C3—C4—N1	117.48 (8)	C13—C14—H14	119.0
C5—C4—N1	119.73 (8)	C14—C15—C16	119.36 (9)
C6—C5—C4	118.14 (8)	C14—C15—H15	120.3
C6—C5—H5	120.9	C16—C15—H15	120.3
C4—C5—H5	120.9	N2—C16—C15	119.48 (8)
C5—C6—C1	121.48 (8)	N2—C16—C11	120.93 (9)
C5—C6—H6	119.3	C15—C16—C11	119.59 (9)
C1—C6—H6	119.3	C13—C17—H17A	109.5
O2—C7—O1	125.07 (9)	C13—C17—H17B	109.5
O2—C7—C1	122.59 (9)	H17A—C17—H17B	109.5
O1—C7—C1	112.34 (8)	C13—C17—H17C	109.5
N2—C8—C9	122.47 (9)	H17A—C17—H17C	109.5
N2—C8—H8	118.8	H17B—C17—H17C	109.5
C9—C8—H8	118.8

C6—C1—C2—C3	−0.91 (13)	C16—N2—C8—C9	0.66 (15)
C7—C1—C2—C3	178.41 (8)	N2—C8—C9—C10	−1.13 (16)
C6—C1—C2—Cl1	−179.86 (7)	C8—C9—C10—C11	0.25 (16)
C7—C1—C2—Cl1	−0.55 (13)	C9—C10—C11—C12	−178.73 (9)
C1—C2—C3—C4	1.56 (14)	C9—C10—C11—C16	0.97 (14)
Cl1—C2—C3—C4	−179.42 (7)	C10—C11—C12—C13	−179.69 (9)
C2—C3—C4—C5	−0.70 (14)	C16—C11—C12—C13	0.62 (14)
C2—C3—C4—N1	178.55 (8)	C11—C12—C13—C14	0.77 (15)
O3—N1—C4—C3	8.31 (13)	C11—C12—C13—C17	−179.57 (9)
O4—N1—C4—C3	−171.89 (9)	C12—C13—C14—C15	−1.57 (16)
O3—N1—C4—C5	−172.41 (9)	C17—C13—C14—C15	178.76 (10)
O4—N1—C4—C5	7.39 (13)	C13—C14—C15—C16	0.91 (15)
C3—C4—C5—C6	−0.78 (14)	C8—N2—C16—C15	−179.81 (9)
N1—C4—C5—C6	179.98 (8)	C8—N2—C16—C11	0.65 (14)
C4—C5—C6—C1	1.46 (14)	C14—C15—C16—N2	−179.02 (9)
C2—C1—C6—C5	−0.64 (14)	C14—C15—C16—C11	0.53 (14)
C7—C1—C6—C5	180.00 (8)	C10—C11—C16—N2	−1.45 (13)
C6—C1—C7—O2	−151.53 (10)	C12—C11—C16—N2	178.26 (9)
C2—C1—C7—O2	29.15 (15)	C10—C11—C16—C15	179.01 (9)
C6—C1—C7—O1	28.79 (12)	C12—C11—C16—C15	−1.28 (13)
C2—C1—C7—O1	−150.52 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.85 (2)	1.70 (2)	2.5452 (12)	174 (3)
N2—H2···O1	0.88 (3)	1.66 (3)	2.5452 (12)	176 (3)
C8—H8···O4ⁱ	0.95	2.59	3.2307 (13)	125

Symmetry code: (i) x, −y+3/2, z−1/2.

2-Chloro-5-nitrobenzoic acid–6-methylquinoline (1/1) (II) top

Crystal data top

C₇H₄ClNO₄·C₁₀H₉N	Z = 2
M_r = 344.74	F(000) = 356.00
Triclinic, P1	D_x = 1.517 Mg m⁻³
a = 6.8693 (3) Å	Mo Kα radiation, λ = 0.71075 Å
b = 7.6482 (4) Å	Cell parameters from 13517 reflections
c = 15.1195 (4) Å	θ = 3.1–30.1°
α = 78.218 (3)°	µ = 0.28 mm⁻¹
β = 81.1923 (18)°	T = 186 K
γ = 77.754 (3)°	Block, colorless
V = 754.89 (6) Å³	0.45 × 0.35 × 0.30 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3868 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.023
ω scans	θ_max = 30.0°, θ_min = 3.1°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −9→9
T_min = 0.891, T_max = 0.920	k = −10→10
15404 measured reflections	l = −20→21
4381 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: mixed
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0662P)² + 0.1585P] where P = (F_o² + 2F_c²)/3
4381 reflections	(Δ/σ)_max = 0.001
222 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.11678 (4)	0.98086 (4)	0.61864 (2)	0.03561 (10)
O1	0.21038 (15)	0.43541 (12)	0.54709 (6)	0.0366 (2)
O2	0.28610 (18)	0.71213 (14)	0.49895 (6)	0.0478 (3)
O3	0.18489 (15)	0.29378 (13)	0.96192 (6)	0.0392 (2)
O4	0.25163 (16)	0.14131 (12)	0.85221 (6)	0.0405 (2)
N1	0.20962 (14)	0.28451 (13)	0.88057 (6)	0.02681 (18)
N2	0.29763 (14)	0.34416 (12)	0.38322 (6)	0.02569 (18)
C1	0.19890 (14)	0.60827 (13)	0.65842 (7)	0.02253 (19)
C2	0.15118 (15)	0.77299 (14)	0.69035 (7)	0.02393 (19)
C3	0.12289 (16)	0.77660 (14)	0.78333 (7)	0.0264 (2)
H3	0.091426	0.890115	0.803551	0.032*
C4	0.14004 (15)	0.61713 (14)	0.84642 (7)	0.0254 (2)
H4	0.119312	0.619066	0.909822	0.030*
C5	0.18819 (14)	0.45521 (13)	0.81441 (6)	0.02191 (18)
C6	0.21638 (15)	0.44738 (13)	0.72259 (7)	0.02259 (19)
H6	0.247515	0.333038	0.703216	0.027*
C7	0.23535 (16)	0.59389 (15)	0.55899 (7)	0.0274 (2)
C8	0.34550 (16)	0.16678 (15)	0.38795 (7)	0.0279 (2)
H8	0.346849	0.091817	0.446377	0.033*
C9	0.39475 (17)	0.08253 (14)	0.31103 (8)	0.0284 (2)
H9	0.429397	−0.046122	0.317664	0.034*
C10	0.39200 (16)	0.18891 (14)	0.22624 (7)	0.0267 (2)
H10	0.424134	0.134301	0.173486	0.032*
C11	0.34115 (14)	0.38015 (13)	0.21768 (7)	0.02121 (18)
C12	0.33604 (15)	0.50006 (14)	0.13253 (7)	0.02423 (19)
H12	0.364652	0.451051	0.078062	0.029*
C13	0.29069 (15)	0.68496 (14)	0.12730 (7)	0.02410 (19)
C14	0.24533 (16)	0.75428 (14)	0.20953 (8)	0.0271 (2)
H14	0.212931	0.882237	0.206693	0.032*
C15	0.24652 (16)	0.64331 (14)	0.29307 (7)	0.0264 (2)
H15	0.214505	0.694420	0.346914	0.032*
C16	0.29544 (14)	0.45298 (13)	0.29885 (6)	0.02121 (18)
C17	0.28690 (19)	0.81553 (17)	0.03801 (8)	0.0341 (2)
H17A	0.323370	0.747133	−0.012173	0.051*
H17B	0.382979	0.895687	0.034211	0.051*
H17C	0.151890	0.888699	0.033913	0.051*
H1	0.243 (3)	0.420 (3)	0.4899 (15)	0.064 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03973 (16)	0.02267 (14)	0.03659 (16)	−0.00175 (10)	−0.00100 (11)	0.00595 (10)
O1	0.0568 (6)	0.0320 (4)	0.0209 (4)	−0.0110 (4)	0.0014 (3)	−0.0059 (3)
O2	0.0815 (8)	0.0429 (5)	0.0220 (4)	−0.0271 (5)	−0.0024 (4)	0.0010 (4)
O3	0.0584 (6)	0.0364 (5)	0.0194 (4)	−0.0069 (4)	−0.0037 (3)	0.0005 (3)
O4	0.0648 (6)	0.0216 (4)	0.0315 (4)	−0.0031 (4)	−0.0064 (4)	−0.0010 (3)
N1	0.0315 (4)	0.0243 (4)	0.0227 (4)	−0.0046 (3)	−0.0038 (3)	0.0002 (3)
N2	0.0299 (4)	0.0250 (4)	0.0208 (4)	−0.0049 (3)	−0.0029 (3)	−0.0012 (3)
C1	0.0227 (4)	0.0234 (5)	0.0203 (4)	−0.0042 (3)	−0.0029 (3)	−0.0012 (3)
C2	0.0222 (4)	0.0215 (4)	0.0262 (5)	−0.0043 (3)	−0.0032 (3)	0.0007 (3)
C3	0.0291 (5)	0.0209 (4)	0.0292 (5)	−0.0040 (4)	−0.0023 (4)	−0.0061 (4)
C4	0.0278 (5)	0.0265 (5)	0.0221 (4)	−0.0054 (4)	−0.0022 (3)	−0.0050 (4)
C5	0.0233 (4)	0.0213 (4)	0.0202 (4)	−0.0048 (3)	−0.0034 (3)	−0.0001 (3)
C6	0.0250 (4)	0.0213 (4)	0.0208 (4)	−0.0038 (3)	−0.0027 (3)	−0.0028 (3)
C7	0.0303 (5)	0.0297 (5)	0.0212 (5)	−0.0052 (4)	−0.0042 (4)	−0.0016 (4)
C8	0.0298 (5)	0.0249 (5)	0.0269 (5)	−0.0066 (4)	−0.0042 (4)	0.0027 (4)
C9	0.0310 (5)	0.0183 (4)	0.0347 (5)	−0.0046 (4)	−0.0040 (4)	−0.0015 (4)
C10	0.0308 (5)	0.0201 (4)	0.0293 (5)	−0.0050 (4)	−0.0006 (4)	−0.0065 (4)
C11	0.0217 (4)	0.0193 (4)	0.0226 (4)	−0.0049 (3)	−0.0014 (3)	−0.0035 (3)
C12	0.0274 (5)	0.0250 (5)	0.0203 (4)	−0.0060 (4)	−0.0013 (3)	−0.0039 (3)
C13	0.0252 (4)	0.0234 (5)	0.0230 (5)	−0.0067 (4)	−0.0047 (3)	0.0010 (3)
C14	0.0326 (5)	0.0188 (4)	0.0298 (5)	−0.0035 (4)	−0.0067 (4)	−0.0033 (4)
C15	0.0335 (5)	0.0209 (5)	0.0249 (5)	−0.0023 (4)	−0.0043 (4)	−0.0064 (4)
C16	0.0223 (4)	0.0204 (4)	0.0206 (4)	−0.0042 (3)	−0.0024 (3)	−0.0028 (3)
C17	0.0424 (6)	0.0308 (5)	0.0268 (5)	−0.0099 (5)	−0.0071 (4)	0.0059 (4)

Geometric parameters (Å, º) top

Cl1—C2	1.7245 (10)	C8—C9	1.4055 (16)
O1—C7	1.3106 (14)	C8—H8	0.9500
O1—H1	0.89 (2)	C9—C10	1.3713 (15)
O2—C7	1.2104 (14)	C9—H9	0.9500
O3—N1	1.2302 (12)	C10—C11	1.4134 (13)
O4—N1	1.2192 (13)	C10—H10	0.9500
N1—C5	1.4686 (13)	C11—C16	1.4149 (13)
N2—C8	1.3161 (14)	C11—C12	1.4205 (13)
N2—C16	1.3737 (12)	C12—C13	1.3705 (14)
C1—C2	1.3972 (14)	C12—H12	0.9500
C1—C6	1.3984 (13)	C13—C14	1.4157 (15)
C1—C7	1.5084 (14)	C13—C17	1.5066 (14)
C2—C3	1.3946 (15)	C14—C15	1.3706 (15)
C3—C4	1.3819 (15)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.4103 (14)
C4—C5	1.3781 (14)	C15—H15	0.9500
C4—H4	0.9500	C17—H17A	0.9800
C5—C6	1.3838 (14)	C17—H17B	0.9800
C6—H6	0.9500	C17—H17C	0.9800

C7—O1—H1	112.6 (13)	C10—C9—H9	120.5
O4—N1—O3	123.42 (10)	C8—C9—H9	120.5
O4—N1—C5	118.51 (9)	C9—C10—C11	119.73 (10)
O3—N1—C5	118.07 (9)	C9—C10—H10	120.1
C8—N2—C16	118.47 (9)	C11—C10—H10	120.1
C2—C1—C6	117.92 (9)	C10—C11—C16	117.36 (9)
C2—C1—C7	123.90 (9)	C10—C11—C12	123.30 (9)
C6—C1—C7	118.17 (9)	C16—C11—C12	119.33 (9)
C3—C2—C1	120.97 (9)	C13—C12—C11	121.38 (9)
C3—C2—Cl1	116.41 (8)	C13—C12—H12	119.3
C1—C2—Cl1	122.59 (8)	C11—C12—H12	119.3
C4—C3—C2	120.83 (10)	C12—C13—C14	118.14 (9)
C4—C3—H3	119.6	C12—C13—C17	122.58 (10)
C2—C3—H3	119.6	C14—C13—C17	119.27 (10)
C5—C4—C3	117.86 (9)	C15—C14—C13	122.32 (9)
C5—C4—H4	121.1	C15—C14—H14	118.8
C3—C4—H4	121.1	C13—C14—H14	118.8
C4—C5—C6	122.59 (9)	C14—C15—C16	119.78 (9)
C4—C5—N1	118.54 (9)	C14—C15—H15	120.1
C6—C5—N1	118.86 (9)	C16—C15—H15	120.1
C5—C6—C1	119.81 (9)	N2—C16—C15	118.88 (9)
C5—C6—H6	120.1	N2—C16—C11	122.08 (9)
C1—C6—H6	120.1	C15—C16—C11	119.03 (9)
O2—C7—O1	124.98 (10)	C13—C17—H17A	109.5
O2—C7—C1	123.97 (10)	C13—C17—H17B	109.5
O1—C7—C1	111.02 (9)	H17A—C17—H17B	109.5
N2—C8—C9	123.38 (10)	C13—C17—H17C	109.5
N2—C8—H8	118.3	H17A—C17—H17C	109.5
C9—C8—H8	118.3	H17B—C17—H17C	109.5
C10—C9—C8	118.97 (10)

C6—C1—C2—C3	0.31 (15)	C16—N2—C8—C9	0.03 (16)
C7—C1—C2—C3	−178.82 (10)	N2—C8—C9—C10	−0.48 (17)
C6—C1—C2—Cl1	−177.73 (7)	C8—C9—C10—C11	0.35 (16)
C7—C1—C2—Cl1	3.14 (14)	C9—C10—C11—C16	0.19 (15)
C1—C2—C3—C4	−0.43 (16)	C9—C10—C11—C12	179.57 (10)
Cl1—C2—C3—C4	177.73 (8)	C10—C11—C12—C13	−178.37 (10)
C2—C3—C4—C5	0.75 (16)	C16—C11—C12—C13	0.99 (15)
C3—C4—C5—C6	−1.02 (16)	C11—C12—C13—C14	−1.05 (15)
C3—C4—C5—N1	179.20 (9)	C11—C12—C13—C17	179.13 (9)
O4—N1—C5—C4	179.79 (10)	C12—C13—C14—C15	0.36 (16)
O3—N1—C5—C4	−0.50 (15)	C17—C13—C14—C15	−179.82 (10)
O4—N1—C5—C6	−0.01 (15)	C13—C14—C15—C16	0.40 (16)
O3—N1—C5—C6	179.71 (10)	C8—N2—C16—C15	−179.29 (10)
C4—C5—C6—C1	0.93 (16)	C8—N2—C16—C11	0.55 (15)
N1—C5—C6—C1	−179.29 (8)	C14—C15—C16—N2	179.39 (9)
C2—C1—C6—C5	−0.54 (15)	C14—C15—C16—C11	−0.45 (15)
C7—C1—C6—C5	178.64 (9)	C10—C11—C16—N2	−0.65 (14)
C2—C1—C7—O2	23.08 (17)	C12—C11—C16—N2	179.94 (9)
C6—C1—C7—O2	−156.05 (12)	C10—C11—C16—C15	179.19 (9)
C2—C1—C7—O1	−158.73 (10)	C12—C11—C16—C15	−0.22 (14)
C6—C1—C7—O1	22.14 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.89 (2)	1.78 (2)	2.6569 (13)	169 (2)
C15—H15···O2	0.95	2.46	3.3211 (14)	151

3-Chloro-2-nitrobenzoic acid–6-methylquinoline (1/1) (III) top

Crystal data top

C₇H_3.59ClNO₄·C₁₀H_9.41N	D_x = 1.470 Mg m⁻³
M_r = 344.75	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 28109 reflections
a = 7.1156 (4) Å	θ = 3.0–30.0°
b = 7.5854 (4) Å	µ = 0.27 mm⁻¹
c = 28.8599 (14) Å	T = 190 K
V = 1557.70 (14) Å³	Block, colorless
Z = 4	0.30 × 0.30 × 0.17 mm
F(000) = 712.00

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	4365 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.017
ω scans	θ_max = 30.0°, θ_min = 3.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −10→9
T_min = 0.938, T_max = 0.955	k = −10→10
30061 measured reflections	l = −39→40
4532 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0546P)² + 0.1455P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4532 reflections	Δρ_max = 0.31 e Å⁻³
225 parameters	Δρ_min = −0.26 e Å⁻³
2 restraints	Absolute structure: Flack x determined using 1821 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.014 (8)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.53139 (7)	0.88067 (5)	0.01741 (2)	0.03788 (11)
O1	0.27295 (18)	0.75649 (15)	0.22566 (4)	0.0324 (2)
H1	0.236 (6)	0.671 (4)	0.2421 (12)	0.049*	0.59 (4)
O2	0.3168 (2)	0.54391 (16)	0.17307 (4)	0.0419 (3)
O3	0.2617 (2)	0.56590 (17)	0.07241 (4)	0.0410 (3)
O4	0.55968 (19)	0.53587 (15)	0.08592 (5)	0.0385 (3)
N1	0.41299 (18)	0.61877 (16)	0.08702 (4)	0.0263 (2)
N2	0.18381 (18)	0.49896 (17)	0.27884 (4)	0.0260 (2)
H2	0.203 (8)	0.585 (5)	0.2590 (16)	0.039*	0.41 (4)
C1	0.37616 (18)	0.84027 (16)	0.15112 (4)	0.0210 (2)
C2	0.42073 (19)	0.80125 (17)	0.10505 (4)	0.0216 (2)
C3	0.4747 (2)	0.93226 (17)	0.07416 (4)	0.0240 (2)
C4	0.4842 (2)	1.10660 (18)	0.08878 (5)	0.0265 (3)
H4	0.520281	1.196857	0.067766	0.032*
C5	0.4404 (2)	1.14758 (18)	0.13447 (5)	0.0272 (3)
H5	0.446936	1.266384	0.144760	0.033*
C6	0.38715 (19)	1.01549 (18)	0.16517 (5)	0.0246 (2)
H6	0.357703	1.045362	0.196302	0.030*
C7	0.3188 (2)	0.69810 (18)	0.18471 (5)	0.0245 (3)
C8	0.2211 (2)	0.3372 (2)	0.26449 (5)	0.0297 (3)
H8	0.261320	0.320660	0.233404	0.036*
C9	0.2039 (2)	0.18918 (19)	0.29319 (5)	0.0307 (3)
H9	0.229500	0.074532	0.281546	0.037*
C10	0.1493 (2)	0.21234 (19)	0.33840 (5)	0.0282 (3)
H10	0.138409	0.113530	0.358444	0.034*
C11	0.10940 (18)	0.38383 (19)	0.35510 (4)	0.0234 (2)
C12	0.0566 (2)	0.4191 (2)	0.40170 (5)	0.0269 (3)
H12	0.046576	0.324225	0.423028	0.032*
C13	0.0200 (2)	0.5876 (2)	0.41648 (5)	0.0283 (3)
C14	0.0319 (2)	0.7280 (2)	0.38397 (5)	0.0311 (3)
H14	0.003183	0.844465	0.393774	0.037*
C15	0.0841 (2)	0.69943 (19)	0.33867 (5)	0.0292 (3)
H15	0.091762	0.795472	0.317624	0.035*
C16	0.12609 (19)	0.52672 (18)	0.32360 (5)	0.0233 (2)
C17	−0.0287 (3)	0.6272 (3)	0.46621 (5)	0.0399 (4)
H17A	−0.128360	0.716224	0.467272	0.060*
H17B	0.082912	0.671801	0.482279	0.060*
H17C	−0.072283	0.519138	0.481428	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0610 (2)	0.03165 (18)	0.02096 (15)	−0.00237 (17)	0.01009 (15)	0.00035 (13)
O1	0.0498 (7)	0.0250 (5)	0.0223 (5)	−0.0041 (5)	0.0099 (5)	−0.0005 (4)
O2	0.0751 (9)	0.0223 (5)	0.0282 (5)	−0.0037 (5)	0.0160 (6)	0.0008 (4)
O3	0.0507 (7)	0.0332 (6)	0.0390 (6)	−0.0137 (5)	−0.0115 (5)	−0.0032 (5)
O4	0.0478 (6)	0.0249 (5)	0.0427 (6)	0.0058 (5)	0.0072 (5)	−0.0060 (5)
N1	0.0391 (6)	0.0201 (5)	0.0197 (5)	−0.0037 (5)	0.0015 (4)	−0.0007 (4)
N2	0.0325 (6)	0.0245 (5)	0.0209 (5)	−0.0020 (5)	0.0034 (4)	0.0025 (4)
C1	0.0240 (5)	0.0193 (5)	0.0199 (5)	−0.0003 (4)	0.0020 (4)	0.0011 (4)
C2	0.0258 (5)	0.0173 (5)	0.0215 (5)	−0.0005 (4)	0.0004 (4)	−0.0006 (4)
C3	0.0298 (6)	0.0222 (5)	0.0198 (5)	0.0002 (5)	0.0032 (5)	0.0012 (4)
C4	0.0324 (6)	0.0197 (5)	0.0274 (6)	−0.0006 (5)	0.0027 (5)	0.0033 (5)
C5	0.0341 (7)	0.0187 (5)	0.0289 (6)	0.0012 (5)	0.0029 (5)	−0.0017 (5)
C6	0.0300 (6)	0.0210 (5)	0.0228 (6)	0.0017 (5)	0.0037 (5)	−0.0021 (5)
C7	0.0302 (6)	0.0226 (6)	0.0209 (6)	−0.0012 (5)	0.0038 (5)	0.0029 (5)
C8	0.0375 (7)	0.0289 (7)	0.0227 (6)	−0.0030 (6)	0.0033 (5)	−0.0012 (5)
C9	0.0409 (8)	0.0219 (6)	0.0292 (7)	−0.0017 (6)	0.0016 (6)	−0.0021 (5)
C10	0.0349 (7)	0.0229 (6)	0.0268 (6)	−0.0034 (5)	0.0005 (5)	0.0030 (5)
C11	0.0247 (5)	0.0238 (5)	0.0218 (5)	−0.0027 (5)	−0.0009 (4)	0.0023 (5)
C12	0.0293 (6)	0.0307 (7)	0.0207 (6)	−0.0033 (5)	0.0006 (5)	0.0043 (5)
C13	0.0275 (6)	0.0346 (7)	0.0228 (6)	−0.0013 (5)	0.0025 (5)	−0.0005 (5)
C14	0.0346 (7)	0.0273 (6)	0.0313 (7)	0.0020 (6)	0.0062 (6)	−0.0014 (5)
C15	0.0356 (7)	0.0229 (6)	0.0291 (6)	0.0008 (5)	0.0051 (6)	0.0034 (5)
C16	0.0246 (5)	0.0234 (6)	0.0220 (6)	−0.0013 (4)	0.0012 (5)	0.0022 (5)
C17	0.0464 (9)	0.0483 (9)	0.0251 (7)	0.0006 (8)	0.0071 (6)	−0.0055 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7316 (13)	C8—C9	1.401 (2)
O1—C7	1.3035 (17)	C8—H8	0.9500
O1—H1	0.847 (13)	C9—C10	1.372 (2)
O2—C7	1.2170 (18)	C9—H9	0.9500
O3—N1	1.2238 (18)	C10—C11	1.416 (2)
O4—N1	1.2189 (18)	C10—H10	0.9500
N1—C2	1.4797 (17)	C11—C16	1.4197 (18)
N2—C8	1.322 (2)	C11—C12	1.4217 (18)
N2—C16	1.3717 (17)	C12—C13	1.372 (2)
N2—H2	0.879 (14)	C12—H12	0.9500
C1—C6	1.3918 (18)	C13—C14	1.421 (2)
C1—C2	1.3986 (17)	C13—C17	1.507 (2)
C1—C7	1.5065 (18)	C14—C15	1.376 (2)
C2—C3	1.3890 (17)	C14—H14	0.9500
C3—C4	1.3899 (19)	C15—C16	1.4124 (19)
C4—C5	1.3900 (19)	C15—H15	0.9500
C4—H4	0.9500	C17—H17A	0.9800
C5—C6	1.3902 (19)	C17—H17B	0.9800
C5—H5	0.9500	C17—H17C	0.9800
C6—H6	0.9500

C7—O1—H1	109 (3)	C10—C9—C8	118.97 (14)
O4—N1—O3	125.11 (13)	C10—C9—H9	120.5
O4—N1—C2	117.38 (12)	C8—C9—H9	120.5
O3—N1—C2	117.42 (13)	C9—C10—C11	119.86 (13)
C8—N2—C16	119.84 (12)	C9—C10—H10	120.1
C8—N2—H2	117 (4)	C11—C10—H10	120.1
C16—N2—H2	123 (4)	C10—C11—C16	117.81 (12)
C6—C1—C2	117.80 (11)	C10—C11—C12	123.23 (13)
C6—C1—C7	120.75 (11)	C16—C11—C12	118.95 (13)
C2—C1—C7	121.45 (11)	C13—C12—C11	121.31 (13)
C3—C2—C1	121.42 (12)	C13—C12—H12	119.3
C3—C2—N1	117.00 (11)	C11—C12—H12	119.3
C1—C2—N1	121.58 (11)	C12—C13—C14	118.75 (13)
C2—C3—C4	119.96 (12)	C12—C13—C17	121.67 (14)
C2—C3—Cl1	120.65 (10)	C14—C13—C17	119.56 (15)
C4—C3—Cl1	119.39 (10)	C15—C14—C13	121.68 (14)
C3—C4—C5	119.33 (12)	C15—C14—H14	119.2
C3—C4—H4	120.3	C13—C14—H14	119.2
C5—C4—H4	120.3	C14—C15—C16	119.71 (13)
C4—C5—C6	120.30 (12)	C14—C15—H15	120.1
C4—C5—H5	119.9	C16—C15—H15	120.1
C6—C5—H5	119.9	N2—C16—C15	119.72 (12)
C5—C6—C1	121.19 (12)	N2—C16—C11	120.72 (12)
C5—C6—H6	119.4	C15—C16—C11	119.55 (12)
C1—C6—H6	119.4	C13—C17—H17A	109.5
O2—C7—O1	125.02 (13)	C13—C17—H17B	109.5
O2—C7—C1	120.90 (12)	H17A—C17—H17B	109.5
O1—C7—C1	114.08 (12)	C13—C17—H17C	109.5
N2—C8—C9	122.77 (13)	H17A—C17—H17C	109.5
N2—C8—H8	118.6	H17B—C17—H17C	109.5
C9—C8—H8	118.6

C6—C1—C2—C3	0.1 (2)	C2—C1—C7—O1	−176.81 (13)
C7—C1—C2—C3	−179.62 (13)	C16—N2—C8—C9	0.2 (2)
C6—C1—C2—N1	180.00 (13)	N2—C8—C9—C10	−1.2 (3)
C7—C1—C2—N1	0.25 (19)	C8—C9—C10—C11	0.8 (2)
O4—N1—C2—C3	83.25 (16)	C9—C10—C11—C16	0.6 (2)
O3—N1—C2—C3	−93.42 (16)	C9—C10—C11—C12	−178.41 (14)
O4—N1—C2—C1	−96.63 (16)	C10—C11—C12—C13	179.70 (14)
O3—N1—C2—C1	86.70 (17)	C16—C11—C12—C13	0.7 (2)
C1—C2—C3—C4	−0.4 (2)	C11—C12—C13—C14	1.2 (2)
N1—C2—C3—C4	179.77 (13)	C11—C12—C13—C17	−177.59 (14)
C1—C2—C3—Cl1	179.38 (10)	C12—C13—C14—C15	−1.8 (2)
N1—C2—C3—Cl1	−0.49 (18)	C17—C13—C14—C15	177.06 (15)
C2—C3—C4—C5	0.4 (2)	C13—C14—C15—C16	0.4 (2)
Cl1—C3—C4—C5	−179.37 (11)	C8—N2—C16—C15	−179.21 (15)
C3—C4—C5—C6	−0.2 (2)	C8—N2—C16—C11	1.3 (2)
C4—C5—C6—C1	0.0 (2)	C14—C15—C16—N2	−177.94 (14)
C2—C1—C6—C5	0.1 (2)	C14—C15—C16—C11	1.6 (2)
C7—C1—C6—C5	179.82 (13)	C10—C11—C16—N2	−1.7 (2)
C6—C1—C7—O2	−176.84 (16)	C12—C11—C16—N2	177.42 (13)
C2—C1—C7—O2	2.9 (2)	C10—C11—C16—C15	178.81 (14)
C6—C1—C7—O1	3.4 (2)	C12—C11—C16—C15	−2.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.85 (3)	1.72 (3)	2.5640 (17)	174 (3)
N2—H2···O1	0.88 (4)	1.69 (4)	2.5640 (17)	170 (4)
C5—H5···.O2ⁱ	0.95	2.44	3.3245 (19)	155
C8—H8···.O2	0.95	2.46	3.1438 (19)	129

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

4-Chloro-2-nitrobenzoic acid–6-methylquinoline (1/1) (IV) top

Crystal data top

C₇H_3.48ClNO₄·C₁₀H_9.52N	F(000) = 712.00
M_r = 344.75	D_x = 1.433 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71075 Å
a = 7.4271 (6) Å	Cell parameters from 14736 reflections
b = 14.4348 (6) Å	θ = 3.1–30.2°
c = 16.2208 (7) Å	µ = 0.26 mm⁻¹
β = 113.203 (3)°	T = 185 K
V = 1598.35 (16) Å³	Block, colorless
Z = 4	0.28 × 0.25 × 0.20 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	4158 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.015
ω scans	θ_max = 30.0°, θ_min = 3.1°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −10→10
T_min = 0.931, T_max = 0.949	k = −19→20
16695 measured reflections	l = −22→22
4645 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0529P)² + 0.1089P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4645 reflections	Δρ_max = 0.35 e Å⁻³
225 parameters	Δρ_min = −0.16 e Å⁻³
4 restraints	Absolute structure: Flack x determined using 1899 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.023 (9)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.60068 (7)	0.04982 (4)	0.11442 (3)	0.04410 (14)
O1	0.5629 (2)	0.26210 (10)	0.47141 (9)	0.0398 (3)
H1	0.543 (10)	0.290 (4)	0.512 (3)	0.060*	0.48 (5)
O2	0.5224 (3)	0.38723 (10)	0.38416 (11)	0.0448 (4)
O3	0.8822 (3)	0.13730 (13)	0.49214 (11)	0.0557 (5)
O4	0.6225 (5)	0.05352 (14)	0.45694 (15)	0.0794 (8)
N1	0.7212 (3)	0.11139 (11)	0.44056 (12)	0.0423 (4)
N2	0.5616 (2)	0.36395 (11)	0.59693 (10)	0.0297 (3)
H2	0.543 (8)	0.336 (3)	0.546 (2)	0.044*	0.52 (5)
C1	0.5733 (3)	0.23966 (12)	0.33064 (11)	0.0274 (3)
C2	0.6451 (3)	0.14958 (13)	0.34899 (12)	0.0292 (3)
C3	0.6568 (3)	0.09002 (13)	0.28407 (13)	0.0325 (4)
H3	0.708220	0.029174	0.298910	0.039*
C4	0.5909 (3)	0.12266 (15)	0.19705 (12)	0.0322 (4)
C5	0.5203 (3)	0.21248 (15)	0.17566 (12)	0.0339 (4)
H5	0.478690	0.234289	0.115740	0.041*
C6	0.5111 (3)	0.26997 (13)	0.24225 (12)	0.0311 (4)
H6	0.461428	0.331090	0.227361	0.037*
C7	0.5518 (3)	0.30391 (14)	0.39964 (12)	0.0306 (4)
C8	0.5951 (3)	0.45366 (13)	0.59630 (12)	0.0317 (4)
H8	0.593525	0.481201	0.542828	0.038*
C9	0.6328 (3)	0.50947 (13)	0.67162 (14)	0.0353 (4)
H9	0.653792	0.574126	0.669007	0.042*
C10	0.6390 (3)	0.46968 (13)	0.74905 (13)	0.0337 (4)
H10	0.666629	0.506454	0.801199	0.040*
C11	0.6041 (3)	0.37319 (12)	0.75145 (12)	0.0282 (3)
C12	0.6091 (3)	0.32621 (16)	0.82941 (12)	0.0350 (4)
H12	0.637854	0.360018	0.883369	0.042*
C13	0.5730 (3)	0.23282 (16)	0.82796 (15)	0.0391 (4)
C14	0.5312 (3)	0.18307 (15)	0.74760 (17)	0.0401 (4)
H14	0.506395	0.118429	0.746653	0.048*
C15	0.5253 (3)	0.22500 (13)	0.67141 (14)	0.0354 (4)
H15	0.496495	0.189993	0.618127	0.042*
C16	0.5625 (2)	0.32146 (13)	0.67232 (12)	0.0277 (3)
C17	0.5805 (4)	0.1813 (2)	0.9099 (2)	0.0549 (6)
H17A	0.456380	0.148651	0.896253	0.082*
H17B	0.601873	0.225362	0.958894	0.082*
H17C	0.688173	0.136438	0.928067	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0500 (3)	0.0567 (3)	0.0311 (2)	−0.0080 (2)	0.02182 (19)	−0.0170 (2)
O1	0.0611 (9)	0.0370 (7)	0.0260 (6)	0.0069 (7)	0.0223 (6)	−0.0011 (5)
O2	0.0707 (11)	0.0298 (7)	0.0430 (8)	−0.0030 (7)	0.0322 (8)	−0.0026 (6)
O3	0.0667 (11)	0.0593 (10)	0.0284 (7)	0.0180 (9)	0.0052 (7)	0.0040 (7)
O4	0.149 (2)	0.0547 (11)	0.0454 (10)	−0.0336 (13)	0.0493 (13)	0.0042 (9)
N1	0.0760 (13)	0.0273 (8)	0.0260 (7)	0.0026 (8)	0.0226 (8)	0.0006 (6)
N2	0.0320 (8)	0.0326 (7)	0.0246 (7)	0.0054 (6)	0.0113 (6)	−0.0020 (6)
C1	0.0325 (8)	0.0297 (8)	0.0230 (7)	−0.0069 (7)	0.0140 (6)	−0.0037 (6)
C2	0.0370 (9)	0.0307 (9)	0.0214 (7)	−0.0053 (7)	0.0133 (6)	−0.0006 (6)
C3	0.0390 (9)	0.0319 (9)	0.0300 (8)	−0.0065 (7)	0.0172 (7)	−0.0048 (7)
C4	0.0333 (9)	0.0428 (10)	0.0243 (8)	−0.0098 (7)	0.0154 (7)	−0.0110 (7)
C5	0.0347 (9)	0.0468 (10)	0.0216 (7)	−0.0056 (8)	0.0124 (7)	−0.0003 (7)
C6	0.0314 (9)	0.0365 (9)	0.0261 (8)	−0.0038 (7)	0.0122 (7)	0.0016 (7)
C7	0.0332 (9)	0.0344 (9)	0.0268 (8)	−0.0046 (7)	0.0145 (7)	−0.0047 (7)
C8	0.0341 (8)	0.0350 (9)	0.0271 (9)	0.0064 (7)	0.0133 (8)	0.0056 (7)
C9	0.0411 (10)	0.0260 (8)	0.0386 (9)	0.0021 (7)	0.0153 (8)	0.0004 (8)
C10	0.0389 (9)	0.0304 (8)	0.0304 (9)	0.0030 (7)	0.0120 (7)	−0.0064 (7)
C11	0.0293 (8)	0.0309 (8)	0.0249 (7)	0.0040 (6)	0.0113 (6)	−0.0001 (6)
C12	0.0363 (10)	0.0443 (10)	0.0258 (8)	0.0066 (8)	0.0137 (7)	0.0039 (8)
C13	0.0313 (9)	0.0474 (11)	0.0418 (10)	0.0093 (8)	0.0177 (8)	0.0178 (9)
C14	0.0342 (10)	0.0320 (9)	0.0546 (12)	0.0012 (8)	0.0180 (9)	0.0083 (9)
C15	0.0365 (10)	0.0286 (8)	0.0395 (10)	0.0007 (7)	0.0133 (8)	−0.0044 (7)
C16	0.0269 (8)	0.0289 (8)	0.0273 (8)	0.0037 (6)	0.0108 (6)	−0.0006 (7)
C17	0.0506 (13)	0.0653 (15)	0.0552 (14)	0.0110 (11)	0.0276 (11)	0.0320 (12)

Geometric parameters (Å, º) top

Cl1—C4	1.7273 (18)	C8—C9	1.397 (3)
O1—C7	1.285 (2)	C8—H8	0.9500
O1—H1	0.836 (15)	C9—C10	1.365 (3)
O2—C7	1.230 (3)	C9—H9	0.9500
O3—N1	1.217 (3)	C10—C11	1.420 (3)
O4—N1	1.208 (3)	C10—H10	0.9500
N1—C2	1.472 (2)	C11—C16	1.410 (2)
N2—C8	1.319 (2)	C11—C12	1.423 (3)
N2—C16	1.365 (2)	C12—C13	1.373 (3)
N2—H2	0.873 (14)	C12—H12	0.9500
C1—C6	1.392 (2)	C13—C14	1.411 (3)
C1—C2	1.392 (3)	C13—C17	1.505 (3)
C1—C7	1.510 (2)	C14—C15	1.361 (3)
C2—C3	1.389 (3)	C14—H14	0.9500
C3—C4	1.382 (3)	C15—C16	1.418 (3)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.390 (3)	C17—H17A	0.9800
C5—C6	1.385 (3)	C17—H17B	0.9800
C5—H5	0.9500	C17—H17C	0.9800
C6—H6	0.9500

C7—O1—H1	122 (5)	C10—C9—C8	118.99 (17)
O4—N1—O3	125.3 (2)	C10—C9—H9	120.5
O4—N1—C2	117.1 (2)	C8—C9—H9	120.5
O3—N1—C2	117.46 (18)	C9—C10—C11	119.82 (17)
C8—N2—C16	120.89 (15)	C9—C10—H10	120.1
C8—N2—H2	113 (4)	C11—C10—H10	120.1
C16—N2—H2	126 (4)	C16—C11—C10	118.13 (16)
C6—C1—C2	117.21 (16)	C16—C11—C12	118.45 (17)
C6—C1—C7	118.77 (16)	C10—C11—C12	123.42 (17)
C2—C1—C7	123.97 (16)	C13—C12—C11	121.08 (18)
C3—C2—C1	123.32 (17)	C13—C12—H12	119.5
C3—C2—N1	114.79 (16)	C11—C12—H12	119.5
C1—C2—N1	121.85 (16)	C12—C13—C14	119.07 (18)
C4—C3—C2	117.43 (18)	C12—C13—C17	122.1 (2)
C4—C3—H3	121.3	C14—C13—C17	118.9 (2)
C2—C3—H3	121.3	C15—C14—C13	121.93 (19)
C3—C4—C5	121.32 (17)	C15—C14—H14	119.0
C3—C4—Cl1	118.61 (16)	C13—C14—H14	119.0
C5—C4—Cl1	120.06 (14)	C14—C15—C16	119.38 (19)
C6—C5—C4	119.59 (16)	C14—C15—H15	120.3
C6—C5—H5	120.2	C16—C15—H15	120.3
C4—C5—H5	120.2	N2—C16—C11	119.95 (16)
C5—C6—C1	121.10 (18)	N2—C16—C15	119.96 (16)
C5—C6—H6	119.4	C11—C16—C15	120.08 (17)
C1—C6—H6	119.4	C13—C17—H17A	109.5
O2—C7—O1	125.94 (17)	C13—C17—H17B	109.5
O2—C7—C1	120.75 (16)	H17A—C17—H17B	109.5
O1—C7—C1	113.29 (16)	C13—C17—H17C	109.5
N2—C8—C9	122.19 (16)	H17A—C17—H17C	109.5
N2—C8—H8	118.9	H17B—C17—H17C	109.5
C9—C8—H8	118.9

C6—C1—C2—C3	0.0 (3)	C16—N2—C8—C9	0.0 (3)
C7—C1—C2—C3	177.39 (18)	N2—C8—C9—C10	1.3 (3)
C6—C1—C2—N1	177.83 (18)	C8—C9—C10—C11	−1.0 (3)
C7—C1—C2—N1	−4.8 (3)	C9—C10—C11—C16	−0.4 (3)
O4—N1—C2—C3	−73.6 (3)	C9—C10—C11—C12	179.57 (18)
O3—N1—C2—C3	102.9 (2)	C16—C11—C12—C13	−0.5 (3)
O4—N1—C2—C1	108.3 (2)	C10—C11—C12—C13	179.59 (19)
O3—N1—C2—C1	−75.1 (3)	C11—C12—C13—C14	0.3 (3)
C1—C2—C3—C4	−0.9 (3)	C11—C12—C13—C17	179.03 (19)
N1—C2—C3—C4	−178.83 (17)	C12—C13—C14—C15	−0.1 (3)
C2—C3—C4—C5	1.6 (3)	C17—C13—C14—C15	−178.90 (19)
C2—C3—C4—Cl1	−179.20 (14)	C13—C14—C15—C16	0.1 (3)
C3—C4—C5—C6	−1.6 (3)	C8—N2—C16—C11	−1.4 (3)
Cl1—C4—C5—C6	179.26 (14)	C8—N2—C16—C15	179.73 (18)
C4—C5—C6—C1	0.7 (3)	C10—C11—C16—N2	1.6 (3)
C2—C1—C6—C5	0.1 (3)	C12—C11—C16—N2	−178.32 (16)
C7—C1—C6—C5	−177.44 (17)	C10—C11—C16—C15	−179.54 (18)
C6—C1—C7—O2	−16.2 (3)	C12—C11—C16—C15	0.5 (3)
C2—C1—C7—O2	166.48 (19)	C14—C15—C16—N2	178.48 (17)
C6—C1—C7—O1	162.34 (17)	C14—C15—C16—C11	−0.4 (3)
C2—C1—C7—O1	−15.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.84 (7)	1.70 (6)	2.514 (2)	163 (7)
N2—H2···O1	0.87 (4)	1.67 (5)	2.514 (2)	162 (4)
C10—H10···O2ⁱ	0.95	2.54	3.364 (3)	145

Symmetry code: (i) x, −y+1, z+1/2.

References

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Volume 76| Part 11| November 2020| Pages 1701-1707

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methyl­quinoline with 2-chloro-4-nitro­benzoic acid, 2-chloro-5-nitro­benzoic acid, 3-chloro-2-nitro­benzoic acid and 4-chloro-2-nitro­benzoic acid

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structures of four isomeric hydrogen-bonded co-crystals of 6-methylquinoline with 2-chloro-4-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid, 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid

3. Supramolecular features