The crystal structure of 3-chloro-2-(4-methyl­phenyl)-2H-pyrazolo­[3,4-b]quinoline

Sowmya, H.B.V.; Suresha Kumara, T.H.; Jasinski, J.P.; Millikan, S.P.; Yathirajan, H.S.; Glidewell, C.

doi:10.1107/S205698901500818X

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages 567-570

https://doi.org/10.1107/S205698901500818X

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The crystal structure of 3-chloro-2-(4-methylphenyl)-2H-pyrazolo[3,4-b]quinoline

Haliwana B. V. Sowmya,^a Tholappanavara H. Suresha Kumara,^b Jerry P. Jasinski,^c ^* Sean P. Millikan,^c Hemmige S. Yathirajan ^d and Christopher Glidewell ^e

^aPG Department of Chemistry, Jain University, 52 Bellary Road, Hebbal, Bangalore 560 024, India, ^bUniversity B.D.T. College of Engineering, (a Constituent College of VTU, Belgaum), Davanagere 577 004, India, ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^dDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^eSchool of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: jjasinski@keene.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 18 April 2015; accepted 24 April 2015; online 30 April 2015)

In the molecule of 3-chloro-2-(4-methylphenyl)-2H-pyrazolo[3,4-b]quinoline, C₁₇H₁₂ClN₃, (I), the dihedral angle between the planes of the pyrazole ring and the methylated phenyl ring is 54.25 (9)°. The bond distances in the fused tricyclic system provide evidence for 10-π delocalization in the pyrazolopyridine portion of the molecule, with diene character in the fused carbocyclic ring. In the crystal, molecules of (I) are linked by two independent C—H⋯N hydrogen bonds, forming sheets containing centrosymmetric R₂²(16) and R₆⁴(28) rings, and these sheets are all linked together by π–π stacking interactions with a ring-centroid separation of 3.5891 (9) Å.

Keywords: crystal structure; pyrazoloquinoline; hydrogen bonding; π–π stacking interactions.

CCDC reference: 1012361

1. Chemical context

Quinoline exhibits antimalarial, anti-bacterial, antifungal, anthelmintic, cardiotonic, anticonvulsant, anti-inflammatory and analgesic activity (Marella et al., 2013 ). Quinoline and its fused heterocyclic derivatives constitute an important class of compounds for new drug development (Kumar et al., 2009 ), and the medicinal applications of pyrazolo[3,4-b]quinolines have been summarized, along with an efficient synthetic method (Afghan et al., 2009 ). Recently, we have reported the synthesis of a number of novel pyrazolo[3,4-b]quinoline derivatives, including that of the title compound (I), and molecular docking studies of their binding affinity to the active sites of human telomerase (Sowmya et al., 2014 ). In a continuation of that study, we now report the crystal and molecular structure of one such example, the title compound 3-chloro-2-p-tolyl-2H-pyrazolo[3,4-b]quinoline, (I).

2. Structural commentary

Within the molecule of compound (I) (Fig. 1), the pendent phenyl group is twisted out of the plane of the fused heterocyclic ring system, as indicated by the relevant torsional angles (Table 1): the dihedral angle between the mean planes of the pyrazole and the methylated phenyl rings is 54.25 (9)°. The molecules of (I) exhibit no internal symmetry and thus they are conformationally chiral: however, the centrosymmetric space group accommodates equal numbers of both of the conformational enantiomers. The non-planar character of the molecular skeleton may be plausibly ascribed to the combined effects of the intramolecular non-bonded repulsion between the Cl substituent and the nearest H atom of the methylated phenyl ring, and of the direction-specific intermolecular interactions, in particular the hydrogen bonds.

Table 1
Selected geometric parameters (Å, °)

N1—N2	1.3644 (18)	C7—C8	1.358 (2)
N2—C3	1.346 (2)	C8—C8A	1.432 (2)
C3—C3A	1.398 (2)	C8A—N9	1.342 (2)
C3A—C4	1.388 (2)	N9—C9A	1.346 (2)
C4—C4A	1.394 (2)	C9A—N1	1.349 (2)
C4A—C5	1.429 (2)	C3A—C9A	1.430 (2)
C5—C6	1.357 (3)	C4A—C8A	1.446 (2)
C6—C7	1.419 (3)	C3—Cl3	1.6993 (16)

N1—N2—C21—C22	−53.7 (2)	C3—N2—C21—C22	125.08 (17)
N1—N2—C21—C26	126.42 (16)	C3—N2—C21—C26	−54.8 (2)

Figure 1
The molecular structure of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

The bond distances in compound (I) (Table 1) show some interesting features. Within the pyrazole ring, the bond distances N1—C9A and N2—C3 (Fig. 1) are identical within experimental uncertainty, although these two bonds are formally double and single bonds, respectively. In the fused carbocyclic ring, the bonds C5—C6 and C7—C8 are much shorted than any other C—C bonds in the molecule. However, in the central pyridine ring, within each of the pairs of corresponding bonds C3A—C4 and C4—C4A, C8A—N9 and N9—C9A, and C3A—C9A and C4A—C8A, the two distances are very similar. These observations taken together are fully consistent with a 10-π delocalized system in the pyrazolopyridine portion of the molecule, comparable to those found in naphthalene and azulene (Glidewell & Lloyd, 1984 ), while the fused carbocyclic ring has more the character of an isolated diene (cf. Glidewell & Lloyd, 1986 ).

3. Supramolecular features

The supramolecular assembly in compound (I) is determined by two independent C—H⋯N hydrogen bonds (Table 2) and a π–π stacking interaction, which together link the molecules into a three-dimensional framework structure. The formation of this framework is readily analysed in terms of three simpler sub-structures (Ferguson et al., 1998a ,b ; Gregson et al., 2000 ). In the simplest sub-structure, the C—H⋯N hydrogen bond having atom C23 as the donor links an inversion-related pair of molecules, forming a cyclic centrosymmetric dimer characterized by an R₂²(16) (Bernstein et al., 1995 ) motif (Fig. 2), and this dimeric unit can be regarded as the basic building block in the supramolecular assembly. The second C—H⋯N hydrogen bond, having atom C26 as the donor, directly links the reference dimer, which is centred at (0, ½, ½) to four symmetry-related dimers centred at (0, 0, 0), (0 1, 0), (0, 0, 1) and (0, 1, 1), thereby leading to the formation of a hydrogen-bonded sheet lying parallel to (100), in which centrosymmetric R₂²(16) rings alternate with R₆⁴(28) rings (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

Cg1 represents the centroid of the C21–C26 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯N9ⁱ	0.95	2.50	3.393 (2)	157
C26—H26⋯N9ⁱⁱ	0.95	2.50	3.449 (2)	174
C27—H27A⋯Cg1ⁱⁱⁱ	0.98	2.84	3.653 (2)	140
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+2.

Figure 2
Part of the crystal structure of compound (I)

showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, the unit-cell outline and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (−x, 1 − y, 1 − z).

Figure 3
A stereoview of part of the crystal structure of compound (I)

showing the formation of a hydrogen-bonded sheet lying parallel to (100) and containing alternating R₂²(16) and R₆⁴(28) rings. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Only one hydrogen-bonded sheet passes through each unit cell, but the sheets are linked by the π–π stacking interaction which is associated with the extensive overlap between the tricyclic ring systems of inversion-related pairs of molecules in adjacent sheets (Fig. 4). The pyridine rings of the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which lie in adjacent sheets, are strictly parallel with an interplanar spacing of 3.3819 (6) Å. The ring-centroid separation is 3.5891 (9) Å, corresponding to a ring-centroid offset of ca 1.202 Å (Fig. 4). The effect of this interaction is to link all of the hydrogen-bonded sheets into a single three-dimensional array.

Figure 4
Part of the crystal structure of compound (I)

showing the overlap of an inversion-related pair of molecules. For the sake of clarity, the unit-cell outline and all of the H atoms have been omitted. The molecules are viewed normal to the planes of the fused heterocyclic ring system and atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Despite the large number of aromatic C—H bonds in the molecule of compound (I), the only short C—H⋯π contact involves one of the C—H bonds of the methyl group. Not only are such bonds of low acidity but, perhaps more important, such a methyl group will be undergoing very rapid rotation about the adjacent C—C bond. When a group having local C₃ symmetry, such as a methyl group, is directly bonded to another group having local C₂ symmetry, such as a phenyl group, as in (I), the rotational barrier about the bond between them is very low, generally of the order of J mol⁻¹ rather than the usual kJ mol⁻¹ (Naylor & Wilson, 1957 ; Tannenbaum et al., 1956 ). Moreover, it has been shown that simple hydrocarbyl substituents undergo rapid rotation about C—C bonds in the solid state, even at reduced temperatures (Riddell & Rogerson, 1996 , 1997 ). Therefore, while such a C—H⋯π intermolecular interaction may not be regarded as structurally significant, we report it here for completeness (Table 2).

4. Database survey

Structural information on un-reduced pyrazolo[3,4-b]quinolines carrying a substituent at the N2 position but not at N1, is sparse. In a series of pyrazolo[3,4-b]quinolin-5-ones, each carrying a substituent at N2, the central heterocyclic ring is in reduced form, carrying H atoms at positions 4 and 8 (Cannon et al., 2001a ,b ,c ,d ). By contrast, in a series of less highly reduced pyrazolo[3,4-b]quinolin-5-ones which each carry a substituent at N1 but not at N2, the central fused ring is fully aromatic (Mera et al., 2005 ; Cruz et al., 2006 ; Portilla et al., 2007 ). Similarly, in a series of benzo[f]pyrazolo[3,4-b]quinolines, in each of which there is a substituent at position 1, but not at position 2, the pyridine ring is fully aromatic (Portilla, Quiroga et al., 2005 ; Portilla, Serrano et al., 2005 ; Portilla et al., 2008 ).

5. Synthesis and crystallization

A sample of the title compound was prepared using the recently published procedure (Sowmya et al., 2014). Crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation, at ambient temperature and in the presence of air, of a solution in hexane–ethyl acetate (19:1, v/v).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were located in difference maps, and then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 Å (aromatic) or 0.98 Å (methyl) and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₇H₁₂ClN₃
M_r	293.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	10.2194 (4), 13.4661 (5), 10.4600 (4)
β (°)	102.780 (4)
V (Å³)	1403.80 (10)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.36
Crystal size (mm)	0.42 × 0.28 × 0.12

Data collection
Diffractometer	Agilent Eos Gemini
Absorption correction	Multi-scan (CrysAlis RED; Agilent, 2012 )
T_min, T_max	0.554, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	8443, 2738, 2479
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.114, 1.05
No. of reflections	2738
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.22
Computer programs: CrysAlis PRO and CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1012361

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S205698901500818X/sj5454sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901500818X/sj5454Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901500818X/sj5454Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

3-Chloro-2-(4-methylphenyl)-2H-pyrazolo[3,4-b]quinoline top

Crystal data top

C₁₇H₁₂ClN₃	F(000) = 608
M_r = 293.75	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.2194 (4) Å	Cell parameters from 2738 reflections
b = 13.4661 (5) Å	θ = 4.4–72.6°
c = 10.4600 (4) Å	µ = 2.36 mm⁻¹
β = 102.780 (4)°	T = 173 K
V = 1403.80 (10) Å³	Block, yellow
Z = 4	0.42 × 0.28 × 0.12 mm

Data collection top

Agilent Eos Gemini diffractometer	2479 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.032
ω scans	θ_max = 72.6°, θ_min = 4.4°
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	h = −12→12
T_min = 0.554, T_max = 0.753	k = −12→16
8443 measured reflections	l = −12→11
2738 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0702P)² + 0.2814P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2738 reflections	Δρ_max = 0.36 e Å⁻³
191 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.

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

	x	y	z	U_iso*/U_eq
N1	0.18699 (13)	0.38247 (10)	0.54035 (13)	0.0290 (3)
N2	0.21652 (13)	0.38697 (10)	0.67397 (13)	0.0269 (3)
C3	0.34907 (16)	0.38742 (11)	0.72750 (16)	0.0271 (3)
Cl3	0.41552 (4)	0.39736 (3)	0.89093 (3)	0.03435 (15)
C3A	0.41587 (16)	0.38246 (11)	0.62459 (15)	0.0257 (3)
C4	0.54815 (16)	0.37944 (11)	0.61183 (15)	0.0280 (3)
H4	0.6210	0.3825	0.6860	0.034*
C4A	0.56909 (16)	0.37163 (11)	0.48495 (16)	0.0287 (3)
C5	0.70051 (17)	0.36552 (13)	0.45927 (18)	0.0356 (4)
H5	0.7767	0.3680	0.5302	0.043*
C6	0.71795 (19)	0.35618 (14)	0.33496 (19)	0.0401 (4)
H6	0.8060	0.3516	0.3197	0.048*
C7	0.60533 (19)	0.35325 (13)	0.22768 (18)	0.0390 (4)
H7	0.6191	0.3472	0.1411	0.047*
C8	0.47823 (19)	0.35900 (12)	0.24644 (16)	0.0352 (4)
H8	0.4045	0.3569	0.1730	0.042*
C8A	0.45426 (17)	0.36816 (11)	0.37577 (15)	0.0282 (3)
N9	0.32609 (13)	0.37210 (10)	0.38697 (13)	0.0283 (3)
C9A	0.30883 (16)	0.37944 (11)	0.51055 (15)	0.0264 (3)
C21	0.10959 (16)	0.39242 (12)	0.74232 (16)	0.0283 (3)
C22	0.01295 (16)	0.46631 (12)	0.70896 (16)	0.0318 (3)
H22	0.0147	0.5109	0.6390	0.038*
C23	−0.08594 (16)	0.47332 (13)	0.78014 (17)	0.0356 (4)
H23	−0.1520	0.5239	0.7588	0.043*
C24	−0.09102 (16)	0.40803 (14)	0.88226 (17)	0.0353 (4)
C25	0.00467 (17)	0.33313 (14)	0.90984 (18)	0.0393 (4)
H25	0.0016	0.2870	0.9779	0.047*
C26	0.10438 (17)	0.32453 (13)	0.83996 (17)	0.0360 (4)
H26	0.1685	0.2725	0.8590	0.043*
C27	−0.19679 (19)	0.41851 (18)	0.9614 (2)	0.0476 (5)
H27A	−0.1545	0.4387	1.0510	0.071*
H27B	−0.2424	0.3547	0.9636	0.071*
H27C	−0.2623	0.4689	0.9212	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0265 (7)	0.0343 (7)	0.0250 (7)	−0.0008 (5)	0.0028 (5)	−0.0009 (5)
N2	0.0244 (7)	0.0303 (7)	0.0251 (7)	0.0004 (5)	0.0035 (5)	−0.0002 (5)
C3	0.0251 (8)	0.0298 (8)	0.0251 (8)	0.0001 (6)	0.0026 (6)	−0.0006 (6)
Cl3	0.0305 (2)	0.0482 (3)	0.0228 (2)	0.00019 (15)	0.00256 (16)	−0.00138 (14)
C3A	0.0272 (8)	0.0244 (7)	0.0243 (8)	−0.0007 (5)	0.0034 (6)	−0.0001 (6)
C4	0.0261 (8)	0.0288 (7)	0.0278 (8)	−0.0013 (6)	0.0033 (6)	−0.0009 (6)
C4A	0.0298 (8)	0.0243 (7)	0.0322 (8)	−0.0025 (6)	0.0074 (7)	−0.0008 (6)
C5	0.0304 (9)	0.0361 (9)	0.0411 (9)	−0.0026 (7)	0.0093 (7)	−0.0028 (7)
C6	0.0366 (9)	0.0391 (9)	0.0503 (11)	−0.0026 (7)	0.0220 (8)	−0.0036 (8)
C7	0.0500 (11)	0.0363 (9)	0.0359 (9)	−0.0041 (8)	0.0204 (8)	−0.0028 (7)
C8	0.0445 (10)	0.0335 (9)	0.0288 (8)	−0.0032 (7)	0.0109 (7)	−0.0009 (7)
C8A	0.0336 (8)	0.0226 (7)	0.0287 (8)	−0.0014 (6)	0.0078 (6)	0.0003 (6)
N9	0.0306 (7)	0.0293 (7)	0.0243 (7)	−0.0020 (5)	0.0042 (5)	−0.0003 (5)
C9A	0.0270 (8)	0.0246 (7)	0.0267 (8)	−0.0008 (6)	0.0038 (6)	−0.0002 (6)
C21	0.0230 (7)	0.0330 (8)	0.0283 (8)	0.0005 (6)	0.0045 (6)	−0.0020 (6)
C22	0.0266 (8)	0.0352 (8)	0.0305 (8)	0.0015 (6)	−0.0003 (6)	0.0016 (7)
C23	0.0230 (8)	0.0413 (9)	0.0397 (9)	0.0047 (6)	0.0005 (7)	−0.0042 (7)
C24	0.0236 (8)	0.0463 (10)	0.0355 (9)	−0.0018 (6)	0.0053 (7)	−0.0075 (7)
C25	0.0320 (9)	0.0486 (10)	0.0388 (9)	0.0009 (7)	0.0111 (7)	0.0095 (8)
C26	0.0300 (8)	0.0378 (9)	0.0418 (10)	0.0067 (7)	0.0114 (7)	0.0084 (7)
C27	0.0302 (9)	0.0671 (13)	0.0483 (11)	−0.0017 (8)	0.0145 (8)	−0.0121 (10)

Geometric parameters (Å, º) top

N1—N2	1.3644 (18)	C7—H7	0.9500
N2—C3	1.346 (2)	C8—H8	0.9500
C3—C3A	1.398 (2)	N2—C21	1.434 (2)
C3A—C4	1.388 (2)	C3—Cl3	1.6993 (16)
C4—C4A	1.394 (2)	C21—C26	1.380 (2)
C4A—C5	1.429 (2)	C21—C22	1.391 (2)
C5—C6	1.357 (3)	C22—C23	1.385 (2)
C6—C7	1.419 (3)	C22—H22	0.9500
C7—C8	1.358 (2)	C23—C24	1.393 (3)
C8—C8A	1.432 (2)	C23—H23	0.9500
C8A—N9	1.342 (2)	C24—C25	1.390 (3)
N9—C9A	1.346 (2)	C24—C27	1.507 (2)
C9A—N1	1.349 (2)	C25—C26	1.384 (2)
C3A—C9A	1.430 (2)	C25—H25	0.9500
C4A—C8A	1.446 (2)	C26—H26	0.9500
C4—H4	0.9500	C27—H27A	0.9800
C5—H5	0.9500	C27—H27B	0.9800
C6—H6	0.9500	C27—H27C	0.9800

C9A—N1—N2	103.40 (12)	C8—C8A—C4A	118.05 (15)
C3—N2—N1	113.60 (13)	C8A—N9—C9A	115.12 (14)
C3—N2—C21	126.87 (14)	N9—C9A—N1	123.20 (14)
N1—N2—C21	119.52 (12)	N9—C9A—C3A	124.38 (14)
N2—C3—C3A	107.30 (14)	N1—C9A—C3A	112.41 (14)
N2—C3—Cl3	124.06 (12)	C26—C21—C22	121.19 (15)
C3A—C3—Cl3	128.59 (13)	C26—C21—N2	119.56 (14)
C4—C3A—C3	136.66 (15)	C22—C21—N2	119.25 (14)
C4—C3A—C9A	120.04 (14)	C23—C22—C21	118.42 (16)
C3—C3A—C9A	103.30 (14)	C23—C22—H22	120.8
C3A—C4—C4A	116.84 (15)	C21—C22—H22	120.8
C3A—C4—H4	121.6	C22—C23—C24	121.64 (15)
C4A—C4—H4	121.6	C22—C23—H23	119.2
C4—C4A—C5	122.13 (16)	C24—C23—H23	119.2
C4—C4A—C8A	119.06 (15)	C25—C24—C23	118.24 (15)
C5—C4A—C8A	118.81 (15)	C25—C24—C27	120.74 (17)
C6—C5—C4A	120.91 (17)	C23—C24—C27	121.02 (17)
C6—C5—H5	119.5	C26—C25—C24	121.16 (16)
C4A—C5—H5	119.5	C26—C25—H25	119.4
C5—C6—C7	120.32 (17)	C24—C25—H25	119.4
C5—C6—H6	119.8	C21—C26—C25	119.26 (16)
C7—C6—H6	119.8	C21—C26—H26	120.4
C8—C7—C6	121.22 (16)	C25—C26—H26	120.4
C8—C7—H7	119.4	C24—C27—H27A	109.5
C6—C7—H7	119.4	C24—C27—H27B	109.5
C7—C8—C8A	120.68 (17)	H27A—C27—H27B	109.5
C7—C8—H8	119.7	C24—C27—H27C	109.5
C8A—C8—H8	119.7	H27A—C27—H27C	109.5
N9—C8A—C8	117.40 (15)	H27B—C27—H27C	109.5
N9—C8A—C4A	124.55 (14)

C9A—N1—N2—C3	0.34 (16)	C8—C8A—N9—C9A	179.20 (14)
C9A—N1—N2—C21	179.24 (13)	C4A—C8A—N9—C9A	−0.2 (2)
N1—N2—C3—C3A	−0.29 (17)	C8A—N9—C9A—N1	−178.78 (14)
C21—N2—C3—C3A	−179.08 (14)	C8A—N9—C9A—C3A	−0.4 (2)
N1—N2—C3—Cl3	177.38 (11)	N2—N1—C9A—N9	178.30 (14)
C21—N2—C3—Cl3	−1.4 (2)	N2—N1—C9A—C3A	−0.27 (16)
N2—C3—C3A—C4	−179.33 (17)	C4—C3A—C9A—N9	1.1 (2)
Cl3—C3—C3A—C4	3.1 (3)	C3—C3A—C9A—N9	−178.44 (14)
N2—C3—C3A—C9A	0.10 (16)	C4—C3A—C9A—N1	179.66 (14)
Cl3—C3—C3A—C9A	−177.43 (12)	C3—C3A—C9A—N1	0.11 (17)
C3—C3A—C4—C4A	178.21 (17)	N1—N2—C21—C22	−53.7 (2)
C9A—C3A—C4—C4A	−1.1 (2)	N1—N2—C21—C26	126.42 (16)
C3A—C4—C4A—C5	−178.51 (14)	C3—N2—C21—C22	125.08 (17)
C3A—C4—C4A—C8A	0.6 (2)	C3—N2—C21—C26	−54.8 (2)
C4—C4A—C5—C6	178.81 (16)	C26—C21—C22—C23	2.9 (2)
C8A—C4A—C5—C6	−0.3 (2)	N2—C21—C22—C23	−177.01 (14)
C4A—C5—C6—C7	0.6 (3)	C21—C22—C23—C24	−0.6 (3)
C5—C6—C7—C8	−0.4 (3)	C22—C23—C24—C25	−1.5 (3)
C6—C7—C8—C8A	0.0 (3)	C22—C23—C24—C27	178.15 (16)
C7—C8—C8A—N9	−179.12 (15)	C23—C24—C25—C26	1.4 (3)
C7—C8—C8A—C4A	0.3 (2)	C27—C24—C25—C26	−178.25 (17)
C4—C4A—C8A—N9	0.1 (2)	C22—C21—C26—C25	−3.0 (3)
C5—C4A—C8A—N9	179.25 (14)	N2—C21—C26—C25	176.89 (16)
C4—C4A—C8A—C8	−179.31 (14)	C24—C25—C26—C21	0.8 (3)
C5—C4A—C8A—C8	−0.2 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 represents the centroid of the C21–C26 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···N9ⁱ	0.95	2.50	3.393 (2)	157
C26—H26···N9ⁱⁱ	0.95	2.50	3.449 (2)	174
C27—H27A···Cg1ⁱⁱⁱ	0.98	2.84	3.653 (2)	140

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+2.

Acknowledgements

THSK thanks the authorities of Jain University for their support and encouragement. JPJ acknowledges the NSF–MRI program (grant No. 1039027) for funds to purchase the X-ray diffractometer.

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

The crystal structure of 3-chloro-2-(4-methyl­phenyl)-2H-pyrazolo­[3,4-b]quinoline

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

The crystal structure of 3-chloro-2-(4-methylphenyl)-2H-pyrazolo[3,4-b]quinoline

3. Supramolecular features