Crystal structures of iso­quinoline–3-chloro-2-nitro­benzoic acid (1/1) and isoquinolinium 4-chloro-2-nitro­benzoate

Gotoh, K.; Ishida, H.

doi:10.1107/S2056989014026152

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages 31-34

https://doi.org/10.1107/S2056989014026152

Open

access

Crystal structures of isoquinoline–3-chloro-2-nitrobenzoic acid (1/1) and isoquinolinium 4-chloro-2-nitrobenzoate

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 A. J. Lough, University of Toronto, Canada (Received 17 November 2014; accepted 28 November 2014; online 1 January 2015)

In each of the title isomeric compounds, C₉H_7.3N·C₇H_3.7ClNO₄, (I), and C₉H₈N·C₇H₃ClNO₄, (II), of isoquinoline with 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid, the two components are linked by a short hydrogen bond between a base N atom and a carboxy O atom. In the hydrogen-bonded unit of (I), the H atom is disordered over two positions with N and O site occupancies of 0.30 (3) and 0.70 (3), respectively, while in (II), an acid–base interaction involving H-atom transfer occurs and the H atom is located at the N site. In the crystal of (I), the acid–base units are connected through C—H⋯O hydrogen bonds into a tape structure along the b-axis direction. Inversion-related adjacent tapes are further linked through π–π interactions [centroid–centroid distances = 3.6389 (7)–3.7501 (7) Å], forming a layer parallel to (001). In the crystal of (II), the acid–base units are connected through C—H⋯O hydrogen bonds into a ladder structure along the a-axis direction. The ladders are further linked by another C—H⋯O hydrogen bond into a layer parallel to (001).

Keywords: crystal structure; short hydrogen bond; chloro- and nitro-substituted benzoic acid; isoquinoline.

CCDC references: 1036583; 1036582

1. Chemical context

The hydrogen bonds formed between organic acids and organic bases vary from an O—H⋯N to an O⁻⋯H—N⁺ type with increasing ΔpK_a [pK_a(base) − pK_a(acid)], and at an appropriate ΔpK_a value, a short strong hydrogen bond with a broad single minimum potential energy curve for the H atom or a double-minimum potential is observed (Jerzykiewicz et al., 1998 ; Kalenik et al., 1989 ; Steiner et al., 2001 ; Schmidtmann & Wilson, 2008 ; Gilli & Gilli, 2009 ). For the system of pyridine derivative–chloro- and nitro-substituted benzoic acid (1/1), 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, and two compounds of phthalazine with 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid have a short double-well N⋯H⋯O hydrogen bond between the aromatic N atom and the carboxy O atom (Gotoh & Ishida, 2009 , 2011a ).

We report here two isomeric compounds of isoquinoline with chloro- and nitro-substituted benzoic acids, namely, isoquinoline–3-chloro-2-nitrobenzoic acid (1/1), (I), and 4-chloro-2-nitrobenzoate isoquinolinium, (II), in order to extend our studies of hydrogen bonding in the system of pyridine derivative–chloro- and nitro-substituted benzoic acid (Gotoh & Ishida, 2011b ,c ).

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1. The base and acid molecules are held together by a short hydrogen bond between the N atom of the base and the carboxy O atom. The H atom in the hydrogen bond is disordered over two positions with the N and O sites occupancies refined to 0.30 (3) and 0.70 (3), respectively. In addition, a C—H⋯O hydrogen bond (C8—H8⋯O2; Table 1) is observed in the hydrogen-bonded acid–base unit. In the unit, the isoquinoline ring system, the carboxy group and the benzene ring of the acid molecule are almost coplanar with each other; the carboxy group makes dihedral angles of 5.35 (15) and 5.91 (15)°, respectively, with the isoquinoline ring system and the benzene ring, and the dihedral angle between the isoquinoline ring system and the benzene ring is 1.21 (4)°. On the other hand, the nitro group and the benzene ring are almost perpendicular with a dihedral angle of 83.71 (13)°.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.84 (2)	1.74 (2)	2.5725 (12)	177 (2)
N2—H2⋯O1	0.88 (2)	1.69 (5)	2.5725 (12)	172 (5)
C5—H5⋯O2ⁱ	0.95	2.49	3.3427 (14)	149
C8—H8⋯O2	0.95	2.53	3.1977 (14)	128
Symmetry code: (i) x, y-1, z.

Figure 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 disordered O—H⋯N/N—H⋯O hydrogen bond and the C—H⋯O interaction are indicated by dashed lines.

The molecular structure of (II) is shown in Fig. 2. An acid–base interaction involving H-atom transfer occurs and the base and acid molecules are linked by an N⁺—H⋯O⁻ hydrogen bond. In the hydrogen-bonded unit, the isoquinoline ring system make dihedral angles of 54.12 (15) and 71.89 (5)°, respectively, with the carboxy group and the benzene ring of the acid. In the acid molecule, the benzene ring makes dihedral angles of 26.59 (15) and 67.69 (15)°, respectively, with the carboxy and nitro groups.

Figure 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.

3. Supramolecular features

In the crystal of (I), the hydrogen-bonded acid-base units are linked by a C—H⋯O hydrogen bond (C5—H5⋯O2ⁱ; Table 1), forming a tape structure along the b-axis direction (Fig. 3). Adjacent tapes, which are related by an inversion center, are further linked through π–π interactions between the benzene ring of the acid and the isoquinoline ring system (Fig. 4), forming a layer parallel to the (001) plane. The centroid–centroid distances are in the range 3.6389 (7)–3.7501 (7) Å [Cg1⋯Cg2ⁱⁱⁱ = 3.7501 (7), Cg1⋯Cg2^iv = 3.6674 (7), Cg1⋯Cg3ⁱⁱⁱ = 3.6637 (7) and Cg1⋯Cg3^iv = 3.6389 (7) Å, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6 benzene ring of the acid, and the N2/C8–C10/C15/C16 rings of the base, respectively. Symmetry codes: (iii) −x, −y + 1, −z + 1; (iv) −x + 1, −y + 1, −z + 1.]

Figure 3
A packing diagram of (I)

, showing the hydrogen-bonded tape structure along the b axis. The dashed lines indicate disordered O—H⋯N/N—H⋯O hydrogen bonds and the C—H⋯O interactions. [Symmetry codes: (i) x, y − 1, z; (ii) x, y + 1, z.]

Figure 4
A packing diagram of (I)

, showing the π–π stacking structure along the a axis. The dashed lines indicate disordered O—H⋯N/N—H⋯O hydrogen bonds and H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (iii) −x, −y + 1, −z + 1; (iv) −x + 1, −y + 1, −z + 1.]

In the crystal of (II), the acid–base units are connected through C—H⋯O hydrogen bonds (C3—H3⋯O2ⁱ and C13—H13⋯O3ⁱⁱ; Table 2) into a ladder structure along the a-axis direction (Fig. 5). Adjacent ladders are further linked by another C—H⋯O hydrogen bond (C16—H16⋯O1ⁱⁱⁱ; Table 2), forming a layer parallel to the (001) plane.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.91 (2)	1.67 (2)	2.5738 (14)	169 (2)
C3—H3⋯O2ⁱ	0.95	2.21	3.1580 (15)	174
C13—H13⋯O3ⁱⁱ	0.95	2.52	3.3405 (19)	145
C16—H16⋯O1ⁱⁱⁱ	0.95	2.43	3.3477 (15)	163
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1.

Figure 5
A packing diagram of (II)

, showing the hydrogen-bonded ladder structure along the a axis. The dashed lines indicate N—H⋯O and C—H⋯O hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) x + 1, y, z; (ii) −x + 1, −y, −z + 1.]

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014 ) showed 49 structures of co-crystals/salts of pyridine (or amine) derivative–chloro- and nitro-substituted benzoic acid: 16 structures containing 2-chloro-4-nitrobenzoic acid, nine for 2-chloro-5-nitrobenzoic acid, three for 3-chloro-2-nitrobenzoic acid, five for 3-chloro-6-nitrobenzoic acid, eight for 4-chloro-2-nitrobenzoic acid and eight for 4-chloro-3-nitrobenzoic acid. On the other hand, there were eight structures of co-crystals/salts of isoquinoline with organic acids. The N⋯O distances of the N—H⋯O/O—H⋯N hydrogen bonds are in the range 2.578 (2)–2.8718 (17) Å. No disordered H atoms were observed in the hydrogen bonds.

5. Synthesis and crystallization

Crystals of compounds (I) and (II) were obtained by slow evaporation from acetonitrile solutions of isoquinoline with the corresponding chloro- and nitro-substituted benzoic acid in a 1:1 molar ratio at room temperature [50 ml acetonitrile solution of isoquinoline (0.202 g) and 3-chloro-2-nitrobenzoic acid (0.315 g) for (I), and 150 ml solution of isoquinoline (0.204 g) and 4-chloro-2-nitrobenzoic acid (0.318 g) for (II)].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms in compounds (I) and (II) were found in difference Fourier maps. The H atom in (I), which is involved in the N⋯H⋯O hydrogen bonds, was found to be disordered over two positions in a difference Fourier map. Since the site-occupancy factors and isotropic displacement parameters were strongly correlated, the occupancy factors were refined, with U_iso(H) = 1.5U_eq(N or O). The positional parameters were refined with bond restraints of O—H = 0.84 (2) Å and N—H = 0.88 (2) Å. Atom H2 in (II) was refined freely [refined distance N2—H2 = 0.91 (2) Å]. Other H atoms of compounds (I) and (II) were positioned geometrically (C—H = 0.95 Å) and treated as riding, with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₉H_7.3N·C₇H_3.7ClNO₄	C₉H₈N⁺·C₇H₃ClNO₄⁻
M_r	330.73	330.73
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	190	190
a, b, c (Å)	6.93986 (15), 7.6629 (5), 13.9475 (5)	7.5916 (3), 7.7607 (3), 13.0456 (4)
α, β, γ (°)	83.945 (3), 87.6039 (16), 85.117 (4)	74.8360 (11), 80.1736 (10), 80.3642 (13)
V (Å³)	734.50 (6)	724.84 (4)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.28	0.29
Crystal size (mm)	0.35 × 0.28 × 0.10	0.39 × 0.32 × 0.23

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII	Rigaku R-AXIS RAPIDII
Absorption correction	Numerical (NUMABS; Higashi, 1999 )	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.918, 0.972	0.903, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	15432, 4278, 3729	21510, 4224, 3559
R_int	0.022	0.024
(sin θ/λ)_max (Å⁻¹)	0.704	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.098, 1.08	0.039, 0.117, 1.07
No. of reflections	4278	4224
No. of parameters	219	212
No. of restraints	2	0
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
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.22	0.42, −0.16
Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004 ), SHELXS97 and SHELXL2014 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), CrystalStructure (Rigaku, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1036583; 1036582

Crystal structure: contains datablocks General, I, II. DOI: https://doi.org/10.1107/S2056989014026152/lh5740sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026152/lh5740Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989014026152/lh5740IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989014026152/lh5740Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989014026152/lh5740IIsup5.cml

checkCIF report

Computing details top

For both compounds, data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2010) and PLATON (Spek, 2009).

(I) Isoquinoline113-chloro-2-nitrobenzoic acid (1/1) top

Crystal data top

C₉H_7.3N·C₇H_3.7ClNO₄	Z = 2
M_r = 330.73	F(000) = 340.00
Triclinic, P1	D_x = 1.495 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 6.93986 (15) Å	Cell parameters from 13329 reflections
b = 7.6629 (5) Å	θ = 3.2–30.1°
c = 13.9475 (5) Å	µ = 0.28 mm⁻¹
α = 83.945 (3)°	T = 190 K
β = 87.6039 (16)°	Prism, colorless
γ = 85.117 (4)°	0.35 × 0.28 × 0.10 mm
V = 734.50 (6) Å³

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3729 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 30.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −9→9
T_min = 0.918, T_max = 0.972	k = −10→10
15432 measured reflections	l = −19→19
4278 independent reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0487P)² + 0.1994P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
4278 reflections	Δρ_max = 0.41 e Å⁻³
219 parameters	Δρ_min = −0.22 e Å⁻³

Special details top

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

Refinement. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.34388 (4)	0.30344 (4)	0.03598 (2)	0.03254 (9)
O1	0.27369 (15)	0.39376 (11)	0.48183 (6)	0.0351 (2)
H1	0.250 (4)	0.474 (3)	0.5180 (18)	0.053*	0.70 (3)
O2	0.22586 (17)	0.61166 (11)	0.36405 (6)	0.0439 (2)
O3	0.43819 (15)	0.63013 (11)	0.17433 (7)	0.0412 (2)
O4	0.13125 (16)	0.61492 (13)	0.15530 (8)	0.0469 (3)
N1	0.28995 (15)	0.55342 (12)	0.18246 (6)	0.0290 (2)
N2	0.21395 (14)	0.63768 (12)	0.59551 (6)	0.02651 (19)
H2	0.234 (8)	0.547 (5)	0.561 (4)	0.040*	0.30 (3)
C1	0.30225 (15)	0.32097 (13)	0.32234 (7)	0.02176 (19)
C2	0.30705 (14)	0.36753 (12)	0.22318 (7)	0.02149 (18)
C3	0.33329 (15)	0.24164 (13)	0.15844 (7)	0.02282 (19)
C4	0.35608 (16)	0.06470 (13)	0.19197 (8)	0.0257 (2)
H4	0.3727	−0.0222	0.1479	0.031*
C5	0.35442 (17)	0.01595 (13)	0.29030 (8)	0.0276 (2)
H5	0.3711	−0.1051	0.3139	0.033*
C6	0.32847 (16)	0.14294 (13)	0.35468 (7)	0.0248 (2)
H6	0.3286	0.1076	0.4220	0.030*
C7	0.26468 (17)	0.45769 (14)	0.39226 (8)	0.0261 (2)
C8	0.18964 (17)	0.80800 (15)	0.55602 (8)	0.0284 (2)
H8	0.1919	0.8317	0.4878	0.034*
C9	0.16227 (17)	0.94575 (15)	0.61069 (8)	0.0288 (2)
H9	0.1455	1.0629	0.5806	0.035*
C10	0.15886 (15)	0.91357 (14)	0.71228 (8)	0.0248 (2)
C11	0.13139 (18)	1.04938 (16)	0.77399 (9)	0.0337 (2)
H11	0.1108	1.1687	0.7477	0.040*
C12	0.13459 (18)	1.00797 (19)	0.87164 (9)	0.0383 (3)
H12	0.1176	1.0995	0.9129	0.046*
C13	0.16253 (18)	0.8323 (2)	0.91205 (9)	0.0374 (3)
H13	0.165 (3)	0.808 (2)	0.9796 (14)	0.051 (5)*
C14	0.18547 (17)	0.69811 (17)	0.85431 (8)	0.0322 (2)
H14	0.2017	0.5794	0.8822	0.039*
C15	0.18491 (15)	0.73674 (14)	0.75304 (7)	0.02394 (19)
C16	0.21142 (17)	0.60377 (14)	0.68986 (8)	0.0266 (2)
H16	0.2282	0.4845	0.7167	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.04465 (17)	0.03447 (15)	0.01898 (12)	−0.00229 (11)	−0.00104 (10)	−0.00566 (9)
O1	0.0583 (6)	0.0276 (4)	0.0198 (4)	−0.0007 (4)	0.0001 (4)	−0.0063 (3)
O2	0.0840 (7)	0.0222 (4)	0.0253 (4)	−0.0024 (4)	0.0070 (4)	−0.0062 (3)
O3	0.0578 (6)	0.0236 (4)	0.0419 (5)	−0.0106 (4)	0.0128 (4)	−0.0012 (3)
O4	0.0582 (6)	0.0335 (5)	0.0460 (5)	0.0162 (4)	−0.0114 (5)	−0.0023 (4)
N1	0.0455 (5)	0.0197 (4)	0.0207 (4)	0.0021 (4)	0.0034 (4)	−0.0031 (3)
N2	0.0320 (5)	0.0275 (4)	0.0212 (4)	−0.0033 (3)	0.0002 (3)	−0.0076 (3)
C1	0.0250 (5)	0.0208 (4)	0.0202 (4)	−0.0041 (3)	0.0027 (3)	−0.0048 (3)
C2	0.0256 (5)	0.0177 (4)	0.0212 (4)	−0.0019 (3)	0.0010 (3)	−0.0029 (3)
C3	0.0262 (5)	0.0235 (4)	0.0195 (4)	−0.0033 (3)	0.0010 (3)	−0.0055 (3)
C4	0.0299 (5)	0.0207 (4)	0.0278 (5)	−0.0043 (4)	0.0028 (4)	−0.0082 (4)
C5	0.0347 (5)	0.0189 (4)	0.0293 (5)	−0.0041 (4)	0.0047 (4)	−0.0027 (4)
C6	0.0296 (5)	0.0224 (4)	0.0224 (4)	−0.0050 (4)	0.0037 (4)	−0.0015 (3)
C7	0.0342 (5)	0.0236 (4)	0.0215 (4)	−0.0060 (4)	0.0039 (4)	−0.0063 (4)
C8	0.0354 (6)	0.0310 (5)	0.0189 (4)	−0.0026 (4)	0.0004 (4)	−0.0027 (4)
C9	0.0350 (6)	0.0257 (5)	0.0251 (5)	−0.0005 (4)	0.0010 (4)	−0.0023 (4)
C10	0.0235 (5)	0.0281 (5)	0.0237 (5)	−0.0013 (4)	0.0008 (4)	−0.0081 (4)
C11	0.0348 (6)	0.0321 (6)	0.0361 (6)	−0.0004 (4)	0.0026 (5)	−0.0153 (5)
C12	0.0317 (6)	0.0526 (7)	0.0341 (6)	0.0009 (5)	0.0010 (5)	−0.0256 (6)
C13	0.0297 (6)	0.0622 (8)	0.0212 (5)	0.0028 (5)	−0.0004 (4)	−0.0141 (5)
C14	0.0320 (6)	0.0433 (6)	0.0204 (5)	0.0017 (5)	−0.0008 (4)	−0.0033 (4)
C15	0.0236 (5)	0.0294 (5)	0.0192 (4)	−0.0013 (4)	−0.0003 (3)	−0.0051 (4)
C16	0.0330 (5)	0.0246 (5)	0.0225 (5)	−0.0021 (4)	0.0000 (4)	−0.0041 (4)

Geometric parameters (Å, º) top

Cl1—C3	1.7240 (10)	C5—H5	0.9500
O1—C7	1.2948 (13)	C6—H6	0.9500
O1—H1	0.840 (17)	C8—C9	1.3621 (15)
O2—C7	1.2150 (14)	C8—H8	0.9500
O3—N1	1.2230 (14)	C9—C10	1.4119 (15)
O4—N1	1.2196 (14)	C9—H9	0.9500
N1—C2	1.4738 (13)	C10—C15	1.4129 (15)
N2—C16	1.3138 (13)	C10—C11	1.4147 (14)
N2—C8	1.3616 (14)	C11—C12	1.3661 (18)
N2—H2	0.88 (2)	C11—H11	0.9500
C1—C6	1.3901 (14)	C12—C13	1.404 (2)
C1—C2	1.3911 (13)	C12—H12	0.9500
C1—C7	1.5048 (14)	C13—C14	1.3667 (17)
C2—C3	1.3853 (13)	C13—H13	0.941 (19)
C3—C4	1.3849 (14)	C14—C15	1.4124 (14)
C4—C5	1.3827 (15)	C14—H14	0.9500
C4—H4	0.9500	C15—C16	1.4116 (14)
C5—C6	1.3880 (14)	C16—H16	0.9500

C7—O1—H1	110.2 (19)	N2—C8—C9	122.49 (10)
O4—N1—O3	125.54 (10)	N2—C8—H8	118.8
O4—N1—C2	117.20 (10)	C9—C8—H8	118.8
O3—N1—C2	117.14 (9)	C8—C9—C10	119.69 (10)
C16—N2—C8	119.17 (9)	C8—C9—H9	120.2
C16—N2—H2	117 (4)	C10—C9—H9	120.2
C8—N2—H2	124 (4)	C9—C10—C15	117.69 (9)
C6—C1—C2	117.62 (9)	C9—C10—C11	123.08 (11)
C6—C1—C7	121.03 (9)	C15—C10—C11	119.23 (10)
C2—C1—C7	121.33 (9)	C12—C11—C10	119.63 (12)
C3—C2—C1	121.56 (9)	C12—C11—H11	120.2
C3—C2—N1	117.06 (9)	C10—C11—H11	120.2
C1—C2—N1	121.36 (8)	C11—C12—C13	121.09 (11)
C4—C3—C2	120.01 (9)	C11—C12—H12	119.5
C4—C3—Cl1	119.44 (8)	C13—C12—H12	119.5
C2—C3—Cl1	120.53 (8)	C14—C13—C12	120.59 (11)
C5—C4—C3	119.28 (9)	C14—C13—H13	120.3 (11)
C5—C4—H4	120.4	C12—C13—H13	119.1 (11)
C3—C4—H4	120.4	C13—C14—C15	119.68 (12)
C4—C5—C6	120.34 (9)	C13—C14—H14	120.2
C4—C5—H5	119.8	C15—C14—H14	120.2
C6—C5—H5	119.8	C16—C15—C14	122.15 (10)
C5—C6—C1	121.18 (10)	C16—C15—C10	118.08 (9)
C5—C6—H6	119.4	C14—C15—C10	119.77 (10)
C1—C6—H6	119.4	N2—C16—C15	122.89 (10)
O2—C7—O1	125.26 (10)	N2—C16—H16	118.6
O2—C7—C1	121.07 (10)	C15—C16—H16	118.6
O1—C7—C1	113.66 (9)

C6—C1—C2—C3	1.20 (15)	C6—C1—C7—O1	4.66 (15)
C7—C1—C2—C3	−177.18 (9)	C2—C1—C7—O1	−177.02 (10)
C6—C1—C2—N1	−177.04 (9)	C16—N2—C8—C9	−0.12 (17)
C7—C1—C2—N1	4.58 (15)	N2—C8—C9—C10	0.13 (18)
O4—N1—C2—C3	82.77 (12)	C8—C9—C10—C15	0.13 (16)
O3—N1—C2—C3	−93.64 (12)	C8—C9—C10—C11	179.94 (11)
O4—N1—C2—C1	−98.92 (12)	C9—C10—C11—C12	−178.41 (11)
O3—N1—C2—C1	84.67 (12)	C15—C10—C11—C12	1.40 (17)
C1—C2—C3—C4	−0.19 (16)	C10—C11—C12—C13	−0.74 (19)
N1—C2—C3—C4	178.12 (10)	C11—C12—C13—C14	−0.6 (2)
C1—C2—C3—Cl1	−178.58 (8)	C12—C13—C14—C15	1.27 (18)
N1—C2—C3—Cl1	−0.28 (13)	C13—C14—C15—C16	178.85 (11)
C2—C3—C4—C5	−0.70 (16)	C13—C14—C15—C10	−0.58 (17)
Cl1—C3—C4—C5	177.70 (8)	C9—C10—C15—C16	−0.38 (15)
C3—C4—C5—C6	0.56 (17)	C11—C10—C15—C16	179.81 (10)
C4—C5—C6—C1	0.48 (17)	C9—C10—C15—C14	179.07 (10)
C2—C1—C6—C5	−1.33 (16)	C11—C10—C15—C14	−0.74 (16)
C7—C1—C6—C5	177.05 (10)	C8—N2—C16—C15	−0.16 (17)
C6—C1—C7—O2	−173.83 (12)	C14—C15—C16—N2	−179.03 (11)
C2—C1—C7—O2	4.49 (17)	C10—C15—C16—N2	0.41 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.84 (2)	1.74 (2)	2.5725 (12)	177 (2)
N2—H2···O1	0.88 (2)	1.69 (5)	2.5725 (12)	172 (5)
C5—H5···O2ⁱ	0.95	2.49	3.3427 (14)	149
C8—H8···O2	0.95	2.53	3.1977 (14)	128

Symmetry code: (i) x, y−1, z.

(II) Isoquinolinium 4-chloro-2-nitrobenzoate top

Crystal data top

C₉H₈N⁺·C₇H₃ClNO₄⁻	Z = 2
M_r = 330.73	F(000) = 340.00
Triclinic, P1	D_x = 1.515 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.5916 (3) Å	Cell parameters from 17960 reflections
b = 7.7607 (3) Å	θ = 3.0–30.1°
c = 13.0456 (4) Å	µ = 0.29 mm⁻¹
α = 74.8360 (11)°	T = 190 K
β = 80.1736 (10)°	Block, colorless
γ = 80.3642 (13)°	0.39 × 0.32 × 0.23 mm
V = 724.84 (4) Å³

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3559 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 30.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −10→10
T_min = 0.903, T_max = 0.936	k = −10→10
21510 measured reflections	l = −18→18
4224 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0699P)² + 0.126P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4224 reflections	Δρ_max = 0.42 e Å⁻³
212 parameters	Δρ_min = −0.16 e Å⁻³

Special details top

Refinement. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

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

	x	y	z	U_iso*/U_eq
Cl1	0.89304 (5)	0.83272 (5)	0.98941 (3)	0.04513 (12)
O1	0.49156 (12)	0.48077 (13)	0.69271 (7)	0.0359 (2)
O2	0.25649 (12)	0.50987 (15)	0.81971 (8)	0.0427 (2)
O3	0.78736 (17)	0.25408 (13)	0.80657 (10)	0.0503 (3)
O4	0.91034 (13)	0.46177 (16)	0.68317 (9)	0.0465 (3)
N1	0.81282 (13)	0.40954 (14)	0.76667 (9)	0.0328 (2)
N2	0.31990 (13)	0.26809 (14)	0.63693 (8)	0.0313 (2)
C1	0.53627 (14)	0.58384 (14)	0.83982 (8)	0.0253 (2)
C2	0.72336 (14)	0.54307 (14)	0.82731 (8)	0.0257 (2)
C3	0.83671 (15)	0.61582 (16)	0.87214 (9)	0.0293 (2)
H3	0.9639	0.5862	0.8608	0.035*
C4	0.75517 (17)	0.73430 (15)	0.93451 (9)	0.0310 (2)
C5	0.56930 (18)	0.77436 (16)	0.95367 (10)	0.0338 (2)
H5	0.5166	0.8522	0.9992	0.041*
C6	0.46123 (16)	0.69972 (15)	0.90582 (9)	0.0299 (2)
H6	0.3339	0.7281	0.9182	0.036*
C7	0.41584 (15)	0.51806 (15)	0.78102 (9)	0.0281 (2)
C8	0.24974 (17)	0.14032 (19)	0.71997 (10)	0.0357 (3)
H8	0.2368	0.1551	0.7910	0.043*
C9	0.19825 (16)	−0.00741 (18)	0.70253 (10)	0.0344 (2)
H9	0.1497	−0.0957	0.7610	0.041*
C10	0.21705 (14)	−0.02954 (15)	0.59708 (9)	0.0282 (2)
C11	0.17073 (17)	−0.18170 (17)	0.57248 (12)	0.0363 (3)
H11	0.1257	−0.2761	0.6282	0.044*
C12	0.19101 (18)	−0.19246 (19)	0.46842 (13)	0.0417 (3)
H12	0.1586	−0.2946	0.4524	0.050*
C13	0.25903 (18)	−0.0555 (2)	0.38392 (11)	0.0404 (3)
H13	0.2719	−0.0664	0.3121	0.048*
C14	0.30629 (16)	0.09202 (18)	0.40472 (9)	0.0339 (2)
H14	0.3528	0.1839	0.3478	0.041*
C15	0.28566 (14)	0.10747 (15)	0.51186 (9)	0.0264 (2)
C16	0.33645 (15)	0.25579 (16)	0.53682 (9)	0.0294 (2)
H16	0.3834	0.3486	0.4808	0.035*
H2	0.369 (3)	0.354 (3)	0.6545 (17)	0.060 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0583 (2)	0.0493 (2)	0.03860 (18)	−0.02822 (16)	−0.00558 (14)	−0.01675 (14)
O1	0.0312 (4)	0.0486 (5)	0.0341 (4)	−0.0119 (4)	−0.0042 (3)	−0.0166 (4)
O2	0.0260 (4)	0.0626 (6)	0.0428 (5)	−0.0125 (4)	−0.0022 (3)	−0.0155 (4)
O3	0.0648 (7)	0.0320 (5)	0.0575 (6)	0.0025 (4)	−0.0139 (5)	−0.0187 (4)
O4	0.0342 (5)	0.0670 (7)	0.0459 (5)	−0.0106 (4)	0.0058 (4)	−0.0311 (5)
N1	0.0273 (4)	0.0377 (5)	0.0386 (5)	0.0004 (4)	−0.0087 (4)	−0.0185 (4)
N2	0.0251 (4)	0.0361 (5)	0.0365 (5)	−0.0036 (4)	−0.0051 (4)	−0.0146 (4)
C1	0.0255 (5)	0.0250 (5)	0.0250 (5)	−0.0044 (4)	−0.0037 (4)	−0.0044 (4)
C2	0.0260 (5)	0.0265 (5)	0.0258 (5)	−0.0040 (4)	−0.0029 (4)	−0.0085 (4)
C3	0.0278 (5)	0.0340 (5)	0.0286 (5)	−0.0085 (4)	−0.0039 (4)	−0.0090 (4)
C4	0.0404 (6)	0.0285 (5)	0.0281 (5)	−0.0131 (4)	−0.0055 (4)	−0.0078 (4)
C5	0.0436 (6)	0.0274 (5)	0.0317 (5)	−0.0042 (4)	−0.0024 (5)	−0.0114 (4)
C6	0.0295 (5)	0.0287 (5)	0.0298 (5)	−0.0013 (4)	−0.0021 (4)	−0.0070 (4)
C7	0.0257 (5)	0.0289 (5)	0.0304 (5)	−0.0061 (4)	−0.0070 (4)	−0.0045 (4)
C8	0.0319 (6)	0.0482 (7)	0.0287 (5)	−0.0040 (5)	−0.0029 (4)	−0.0133 (5)
C9	0.0311 (5)	0.0417 (6)	0.0274 (5)	−0.0074 (5)	−0.0014 (4)	−0.0028 (4)
C10	0.0220 (5)	0.0308 (5)	0.0309 (5)	−0.0021 (4)	−0.0054 (4)	−0.0052 (4)
C11	0.0296 (5)	0.0312 (5)	0.0491 (7)	−0.0039 (4)	−0.0098 (5)	−0.0082 (5)
C12	0.0349 (6)	0.0391 (6)	0.0602 (8)	0.0020 (5)	−0.0175 (6)	−0.0247 (6)
C13	0.0360 (6)	0.0527 (8)	0.0381 (6)	0.0052 (5)	−0.0128 (5)	−0.0227 (6)
C14	0.0298 (5)	0.0430 (6)	0.0278 (5)	0.0002 (5)	−0.0062 (4)	−0.0080 (4)
C15	0.0207 (4)	0.0313 (5)	0.0267 (5)	−0.0012 (4)	−0.0048 (4)	−0.0063 (4)
C16	0.0228 (5)	0.0328 (5)	0.0323 (5)	−0.0035 (4)	−0.0044 (4)	−0.0068 (4)

Geometric parameters (Å, º) top

Cl1—C4	1.7326 (12)	C6—H6	0.9500
O1—C7	1.2784 (15)	C8—C9	1.3550 (19)
O2—C7	1.2340 (14)	C8—H8	0.9500
O3—N1	1.2162 (15)	C9—C10	1.4108 (17)
O4—N1	1.2220 (15)	C9—H9	0.9500
N1—C2	1.4734 (14)	C10—C11	1.4131 (17)
N2—C16	1.3176 (16)	C10—C15	1.4168 (15)
N2—C8	1.3632 (17)	C11—C12	1.363 (2)
N2—H2	0.91 (2)	C11—H11	0.9500
C1—C6	1.3931 (15)	C12—C13	1.410 (2)
C1—C2	1.3933 (15)	C12—H12	0.9500
C1—C7	1.5118 (15)	C13—C14	1.3590 (19)
C2—C3	1.3814 (15)	C13—H13	0.9500
C3—C4	1.3855 (16)	C14—C15	1.4140 (16)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.3869 (18)	C15—C16	1.4025 (16)
C5—C6	1.3862 (17)	C16—H16	0.9500
C5—H5	0.9500

O3—N1—O4	125.41 (11)	C9—C8—N2	120.89 (11)
O3—N1—C2	116.47 (10)	C9—C8—H8	119.6
O4—N1—C2	118.08 (10)	N2—C8—H8	119.6
C16—N2—C8	121.77 (11)	C8—C9—C10	119.69 (11)
C16—N2—H2	121.1 (13)	C8—C9—H9	120.2
C8—N2—H2	116.6 (13)	C10—C9—H9	120.2
C6—C1—C2	116.80 (10)	C9—C10—C11	123.14 (11)
C6—C1—C7	119.68 (10)	C9—C10—C15	118.36 (11)
C2—C1—C7	123.42 (10)	C11—C10—C15	118.50 (11)
C3—C2—C1	124.21 (10)	C12—C11—C10	119.70 (12)
C3—C2—N1	115.37 (9)	C12—C11—H11	120.2
C1—C2—N1	120.38 (9)	C10—C11—H11	120.2
C2—C3—C4	116.52 (10)	C11—C12—C13	121.55 (12)
C2—C3—H3	121.7	C11—C12—H12	119.2
C4—C3—H3	121.7	C13—C12—H12	119.2
C3—C4—C5	121.97 (10)	C14—C13—C12	120.33 (12)
C3—C4—Cl1	117.91 (9)	C14—C13—H13	119.8
C5—C4—Cl1	120.12 (9)	C12—C13—H13	119.8
C6—C5—C4	119.35 (11)	C13—C14—C15	119.39 (12)
C6—C5—H5	120.3	C13—C14—H14	120.3
C4—C5—H5	120.3	C15—C14—H14	120.3
C5—C6—C1	121.06 (11)	C16—C15—C14	121.11 (11)
C5—C6—H6	119.5	C16—C15—C10	118.34 (10)
C1—C6—H6	119.5	C14—C15—C10	120.53 (11)
O2—C7—O1	126.47 (11)	N2—C16—C15	120.90 (11)
O2—C7—C1	118.47 (11)	N2—C16—H16	119.6
O1—C7—C1	115.02 (9)	C15—C16—H16	119.6

C6—C1—C2—C3	−2.85 (16)	C2—C1—C7—O1	−24.68 (15)
C7—C1—C2—C3	173.44 (10)	C16—N2—C8—C9	1.66 (18)
C6—C1—C2—N1	174.65 (10)	N2—C8—C9—C10	−0.10 (19)
C7—C1—C2—N1	−9.05 (16)	C8—C9—C10—C11	178.39 (11)
O3—N1—C2—C3	110.00 (12)	C8—C9—C10—C15	−1.62 (17)
O4—N1—C2—C3	−67.61 (14)	C9—C10—C11—C12	179.31 (11)
O3—N1—C2—C1	−67.71 (14)	C15—C10—C11—C12	−0.68 (17)
O4—N1—C2—C1	114.67 (12)	C10—C11—C12—C13	0.57 (19)
C1—C2—C3—C4	1.06 (17)	C11—C12—C13—C14	−0.04 (19)
N1—C2—C3—C4	−176.56 (10)	C12—C13—C14—C15	−0.36 (19)
C2—C3—C4—C5	1.76 (17)	C13—C14—C15—C16	178.64 (11)
C2—C3—C4—Cl1	−178.43 (8)	C13—C14—C15—C10	0.24 (17)
C3—C4—C5—C6	−2.62 (18)	C9—C10—C15—C16	1.85 (15)
Cl1—C4—C5—C6	177.57 (9)	C11—C10—C15—C16	−178.16 (10)
C4—C5—C6—C1	0.69 (18)	C9—C10—C15—C14	−179.71 (10)
C2—C1—C6—C5	1.91 (16)	C11—C10—C15—C14	0.28 (16)
C7—C1—C6—C5	−174.53 (10)	C8—N2—C16—C15	−1.40 (17)
C6—C1—C7—O2	−26.60 (16)	C14—C15—C16—N2	−178.81 (10)
C2—C1—C7—O2	157.21 (11)	C10—C15—C16—N2	−0.38 (16)
C6—C1—C7—O1	151.51 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.91 (2)	1.67 (2)	2.5738 (14)	169 (2)
C3—H3···O2ⁱ	0.95	2.21	3.1580 (15)	174
C13—H13···O3ⁱⁱ	0.95	2.52	3.3405 (19)	145
C16—H16···O1ⁱⁱⁱ	0.95	2.43	3.3477 (15)	163

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1.

References

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gilli, G. & Gilli, P. (2009). In The Nature of the Hydrogen Bond. Oxford University Press. Google Scholar
Gotoh, K. & Ishida, H. (2009). Acta Cryst. C65, o534–o538. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gotoh, K. & Ishida, H. (2011a). Acta Cryst. C67, o473–o478. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gotoh, K. & Ishida, H. (2011b). Acta Cryst. E67, o2883. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gotoh, K. & Ishida, H. (2011c). Acta Cryst. E67, o3222. Web of Science CSD CrossRef IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Jerzykiewicz, L. B., Malarski, Z., Sobczyk, L., Lis, T. & Grech, E. (1998). J. Mol. Struct. 440, 175–185. Web of Science CSD CrossRef CAS Google Scholar
Kalenik, J., Majerz, I., Sobczyk, L., Grech, E. & Habeeb, M. M. (1989). J. Chem. Soc. Faraday Trans. 1, 85, 3187–3193. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). PROCESS-AUTO. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Schmidtmann, M. & Wilson, C. C. (2008). CrystEngComm, 10, 177–183. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T., Majerz, I. & Wilson, C. C. (2001). Angew. Chem. Int. Ed. 40, 2651–2654 CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 1| January 2015| Pages 31-34

https://doi.org/10.1107/S2056989014026152

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Crystal structures of iso­quinoline–3-chloro-2-nitro­benzoic acid (1/1) and isoquinolinium 4-chloro-2-nitro­benzoate

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 isoquinoline–3-chloro-2-nitrobenzoic acid (1/1) and isoquinolinium 4-chloro-2-nitrobenzoate

3. Supramolecular features