3-Methyl-5,6-diphenyl-1H-pyrazolo­[1,2-a]cinnolin-1-one

Mayakrishnan, S.; Arun, Y.; Maheswari, N.U.

doi:10.1107/S241431461700534X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170534

https://doi.org/10.1107/S241431461700534X

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access

3-Methyl-5,6-diphenyl-1H-pyrazolo[1,2-a]cinnolin-1-one

Sivakalai Mayakrishnan,^a Y. Arun ^a and Narayanan Uma Maheswari ^a ^*

^aOrganic & Bio-organic Chemistry, CSIR Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: umanarayanclri@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 March 2017; accepted 10 April 2017; online 21 April 2017)

The asymmetric unit of the title compound, C₂₄H₁₈N₂O, comprises two crystallographically independent molecules (A and B), with slightly different conformations. In each molecule, there is an intramolecular C—H⋯O hydrogen bond forming an S(6) ring motif. The pyridazine rings of the pyrazolo[1,2-a]cinnoline units have screw-boat conformations. Their mean planes are inclined to the phenyl rings by 83.81 (8) and 74.19 (8)° in molecule A, and 89.72 (8) and 71.07 (8)° in molecule B. In the crystal, the A and B molecules are linked by a pair of C—H⋯O hydrogen bonds, forming an A–B dimer with an R₂²(14) ring motif. These dimers are linked by further C—H⋯O hydrogen bonds, forming ribbons propagating along the b-axis direction. The ribbons are linked by a number of C—H⋯π interactions, forming a three-dimensional structure.

Keywords: crystal structure; cinnoline; pyrazole; pyridazine; hydrogen bonding; C—H⋯π interactions.

CCDC reference: 1026268

Structure description

Pyrazole derivatives are reported to possess varied biological activities, such as anti-inflammatory (Windholz 2003 ), analgesic (Windholz 2003), hypoglycemic, sedative (Burger & Iorio, 1979 ), hypnotic (Burger & Iorio, 1980 ), antifungal and antibacterial (Kalluraya & Ramesh, 2001 ).

The asymmetric unit of the title compound, is composed of two crystallographically independent molecules (A and B), with slightly different conformations (Fig. 1). Intramolecular C—H⋯O hydrogen bonds generate six-membered rings, producing S(6) ring motifs (Fig1, Table 1). The dihedral angles between the mean plane of the central pyridazine ring (which has a screw-boat conformation in both molecules) and the two outer phenyl rings are 83.81 (8) and 74.19 (8)° in molecule A, and 89.72 (8) and 71.07 (8)° in molecule B.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg3, Cg4, Cg11 and Cg12 are the centroids of the N1/N2/C21–C24, C1–C6, C8–C13, C1′–C6′ and C8′–C13′ rings, respectively

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1	0.93	2.22	2.862 (2)	125
C2′—H2′⋯O1′	0.93	2.22	2.865 (2)	126
C3—H3⋯O1′ⁱ	0.93	2.49	3.381 (2)	162
C3′—H3′⋯O1ⁱ	0.93	2.54	3.456 (2)	170
C11—H11⋯O1ⁱⁱ	0.93	2.49	3.274 (2)	142
C9—H9⋯Cg1ⁱⁱⁱ	0.93	2.92	3.796 (2)	158
C16—H16⋯Cg3ⁱⁱⁱ	0.93	3.00	3.822 (2)	149
C18—H18⋯Cg12^iv	0.93	2.95	3.869 (2)	169
C18′—H18′⋯Cg4^iv	0.93	2.98	3.867 (2)	161
C19—H19⋯Cg3^v	0.93	2.90	3.685 (2)	143
C19′—H19′⋯Cg11^vi	0.93	2.78	3.604 (2)	149
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y-1, z; (iii) -x, -y, -z+1; (iv) -x+1, -y, -z; (v) -x+1, -y, -z+1; (vi) -x+1, -y+1, -z.

Figure 1
The molecular structure of the two independent molecules (A and B) of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

In the crystal, the A and B molecules are linked by a pair of C—H⋯O hydrogen bonds, forming an A–B dimer with an $[R_{2}^{2}]$ (14) ring motif (Fig. 2 and Table 1). These dimers are linked by further C—H⋯O hydrogen bonds, forming ribbons propagating along the b-axis direction (Fig. 3 and Table 1). The ribbons are linked by a number of C—H⋯π interactions, forming a three-dimensional structure (Table 1).

Figure 2
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

; colour code: molecule A black, molecule B orange).

Figure 3
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

; colour code: molecule A black, molecule B orange).

Synthesis and crystallization

To a dried 50 ml round-bottom flask, fitted with a reflux condenser, were added 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one 1 (0.3 mmol), diphenyl acetylene (0.3 mmol), [RuCl₂(p-cymene)]₂ (5 mol%), Cu(OAc)₂ (2 eq.) and AgSbF₆ (20 mol%) in toluene. The reaction mixture was refluxed for 16 h. After cooling to room temperature, the reaction mixture was diluted with CH₂Cl₂, filtered through Celite and the filtrate concentrated under reduced pressure. The crude product was purified through a silica gel column, using hexane and ethyl acetate as eluent, giving the title compound in 70% yield. Colourless block-like crystals were obtained by slow evaporation of a solution in ethanol.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₈N₂O
M_r	350.40
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	9.9251 (4), 12.2293 (4), 15.1738 (5)
α, β, γ (°)	84.318 (2), 78.538 (2), 89.880 (2)
V (Å³)	1795.86 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 20014)
T_min, T_max	0.984, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	26244, 7471, 5339
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.125, 1.01
No. of reflections	7471
No. of parameters	490
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1026268

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461700534X/su4146sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700534X/su4146Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461700534X/su4146Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

3-Methyl-5,6-diphenyl-1H-pyrazolo[1,2-a]cinnolin-1-one top

Crystal data top

C₂₄H₁₈N₂O	Z = 4
M_r = 350.40	F(000) = 736
Triclinic, P1	D_x = 1.296 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.9251 (4) Å	Cell parameters from 7471 reflections
b = 12.2293 (4) Å	θ = 1.4–26.6°
c = 15.1738 (5) Å	µ = 0.08 mm⁻¹
α = 84.318 (2)°	T = 293 K
β = 78.538 (2)°	Block, colourless
γ = 89.880 (2)°	0.20 × 0.15 × 0.10 mm
V = 1795.86 (11) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	7471 independent reflections
Radiation source: fine-focus sealed tube	5339 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and φ scans	θ_max = 26.6°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 20014)	h = −12→12
T_min = 0.984, T_max = 0.992	k = −15→13
26244 measured reflections	l = −17→19

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0499P)² + 0.4013P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
7471 reflections	Δρ_max = 0.31 e Å⁻³
490 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0046 (7)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.15479 (14)	0.09128 (12)	0.61216 (10)	0.0482 (3)
C1'	0.13725 (15)	0.56650 (12)	0.09148 (10)	0.0498 (4)
C2'	0.06903 (17)	0.60730 (14)	0.16999 (11)	0.0618 (4)
H2'	0.0647	0.6827	0.1736	0.074*
C2	0.09775 (17)	0.13502 (14)	0.69203 (11)	0.0594 (4)
H2	0.0962	0.2107	0.6943	0.071*
C3'	0.00711 (18)	0.53485 (15)	0.24336 (12)	0.0698 (5)
H3'	−0.0384	0.5621	0.2961	0.084*
C3	0.04332 (18)	0.06529 (15)	0.76824 (11)	0.0652 (4)
H3	0.0041	0.0945	0.8215	0.078*
C4'	0.01280 (19)	0.42348 (16)	0.23837 (12)	0.0728 (5)
H4'	−0.0289	0.3754	0.2875	0.087*
C4	0.04671 (18)	−0.04632 (15)	0.76597 (11)	0.0687 (5)
H4	0.0095	−0.0925	0.8175	0.082*
C5	0.10524 (18)	−0.09005 (14)	0.68738 (11)	0.0627 (4)
H5	0.1081	−0.1660	0.6866	0.075*
C5'	0.08075 (17)	0.38318 (14)	0.16001 (11)	0.0641 (4)
H5'	0.0834	0.3076	0.1569	0.077*
C6	0.16065 (15)	−0.02226 (12)	0.60856 (10)	0.0485 (3)
C6'	0.14578 (15)	0.45328 (12)	0.08511 (10)	0.0499 (4)
C7	0.22899 (14)	−0.06595 (11)	0.52486 (9)	0.0462 (3)
C7'	0.22902 (15)	0.41255 (11)	0.00459 (10)	0.0466 (3)
C8'	0.25727 (15)	0.29247 (11)	0.00764 (9)	0.0463 (3)
C8	0.25278 (16)	−0.18661 (11)	0.52569 (9)	0.0483 (3)
C9'	0.16563 (18)	0.21977 (14)	−0.01398 (12)	0.0646 (4)
H9'	0.0895	0.2464	−0.0358	0.078*
C9	0.14860 (19)	−0.25754 (14)	0.51906 (13)	0.0714 (5)
H9	0.0644	−0.2297	0.5104	0.086*
C10	0.1679 (2)	−0.37019 (16)	0.52519 (14)	0.0842 (6)
H10	0.0965	−0.4173	0.5209	0.101*
C10'	0.1860 (2)	0.10750 (15)	−0.00343 (13)	0.0736 (5)
H10'	0.1235	0.0593	−0.0181	0.088*
C11	0.2905 (3)	−0.41224 (14)	0.53747 (12)	0.0785 (6)
H11	0.3024	−0.4879	0.5426	0.094*
C11'	0.2976 (2)	0.06734 (14)	0.02845 (11)	0.0698 (5)
H11'	0.3102	−0.0081	0.0366	0.084*
C12'	0.3904 (2)	0.13831 (13)	0.04833 (12)	0.0689 (5)
H12'	0.4671	0.1111	0.0692	0.083*
C12	0.3954 (2)	−0.34339 (14)	0.54221 (12)	0.0751 (5)
H12	0.4798	−0.3721	0.5496	0.090*
C13'	0.37103 (18)	0.25057 (12)	0.03771 (11)	0.0573 (4)
H13'	0.4354	0.2982	0.0510	0.069*
C13	0.37763 (19)	−0.23078 (13)	0.53616 (11)	0.0600 (4)
H13	0.4504	−0.1844	0.5392	0.072*
C14'	0.28439 (14)	0.48240 (11)	−0.06700 (9)	0.0458 (3)
C14	0.27179 (14)	0.00173 (11)	0.44925 (9)	0.0450 (3)
C15	0.34601 (15)	−0.03659 (11)	0.36324 (9)	0.0454 (3)
C15'	0.37988 (15)	0.44902 (11)	−0.14754 (9)	0.0471 (3)
C16'	0.33317 (18)	0.39598 (13)	−0.21222 (11)	0.0612 (4)
H16'	0.2401	0.3787	−0.2048	0.073*
C16	0.27580 (18)	−0.08795 (14)	0.30889 (11)	0.0611 (4)
H16	0.1811	−0.0985	0.3260	0.073*
C17'	0.4235 (2)	0.36848 (16)	−0.28764 (12)	0.0784 (6)
H17'	0.3913	0.3340	−0.3315	0.094*
C17	0.3451 (2)	−0.12393 (15)	0.22904 (12)	0.0777 (6)
H17	0.2969	−0.1579	0.1923	0.093*
C18	0.4851 (2)	−0.10957 (16)	0.20403 (12)	0.0797 (6)
H18	0.5318	−0.1337	0.1502	0.096*
C18'	0.5605 (2)	0.39185 (18)	−0.29805 (13)	0.0832 (6)
H18'	0.6216	0.3729	−0.3489	0.100*
C19'	0.60834 (19)	0.44324 (18)	−0.23369 (13)	0.0783 (6)
H19'	0.7017	0.4591	−0.2411	0.094*
C19	0.5559 (2)	−0.05984 (16)	0.25822 (12)	0.0739 (5)
H19	0.6508	−0.0505	0.2412	0.089*
C20	0.48752 (16)	−0.02358 (14)	0.33765 (11)	0.0586 (4)
H20	0.5364	0.0098	0.3743	0.070*
C20'	0.51909 (17)	0.47125 (14)	−0.15853 (11)	0.0613 (4)
H20'	0.5522	0.5053	−0.1148	0.074*
C21'	0.28812 (17)	0.68383 (13)	−0.12931 (11)	0.0566 (4)
C21	0.26618 (16)	0.20089 (13)	0.38316 (11)	0.0574 (4)
C22'	0.3399 (2)	0.67642 (15)	−0.22668 (12)	0.0765 (5)
H22A	0.3379	0.7477	−0.2592	0.115*
H22B	0.2829	0.6260	−0.2482	0.115*
H22C	0.4327	0.6508	−0.2360	0.115*
C22	0.2999 (2)	0.18924 (15)	0.28496 (12)	0.0785 (6)
H22D	0.3919	0.1631	0.2691	0.118*
H22E	0.2928	0.2593	0.2517	0.118*
H22F	0.2367	0.1378	0.2705	0.118*
C23'	0.25706 (18)	0.77768 (13)	−0.08866 (12)	0.0623 (4)
H23'	0.2702	0.8484	−0.1180	0.075*
C23	0.24147 (19)	0.29558 (14)	0.42277 (13)	0.0684 (5)
H23	0.2488	0.3654	0.3915	0.082*
C24	0.20346 (18)	0.27457 (13)	0.51675 (13)	0.0644 (4)
C24'	0.20272 (17)	0.75271 (12)	0.00338 (12)	0.0570 (4)
N1'	0.20321 (13)	0.63712 (10)	0.01742 (9)	0.0528 (3)
N1	0.20948 (13)	0.15955 (10)	0.53328 (9)	0.0533 (3)
N2	0.24796 (13)	0.11533 (9)	0.44992 (8)	0.0507 (3)
N2'	0.25753 (13)	0.59608 (9)	−0.06569 (8)	0.0515 (3)
O1	0.16919 (17)	0.33509 (10)	0.57734 (10)	0.0944 (5)
O1'	0.15812 (14)	0.81121 (9)	0.06473 (9)	0.0781 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0416 (8)	0.0506 (8)	0.0524 (9)	0.0037 (6)	−0.0093 (6)	−0.0049 (7)
C1'	0.0439 (8)	0.0501 (8)	0.0539 (9)	0.0086 (6)	−0.0078 (7)	−0.0020 (7)
C2'	0.0593 (10)	0.0597 (10)	0.0626 (10)	0.0165 (8)	−0.0026 (8)	−0.0075 (8)
C2	0.0602 (10)	0.0574 (9)	0.0614 (10)	0.0112 (8)	−0.0100 (8)	−0.0145 (8)
C3'	0.0644 (11)	0.0756 (12)	0.0605 (10)	0.0169 (9)	0.0063 (8)	−0.0024 (9)
C3	0.0647 (11)	0.0761 (12)	0.0531 (10)	0.0166 (9)	−0.0047 (8)	−0.0135 (8)
C4'	0.0691 (12)	0.0745 (12)	0.0607 (11)	0.0063 (9)	0.0129 (9)	0.0093 (9)
C4	0.0726 (12)	0.0734 (12)	0.0505 (9)	0.0114 (9)	0.0058 (8)	0.0027 (8)
C5	0.0715 (11)	0.0561 (9)	0.0531 (9)	0.0072 (8)	0.0024 (8)	−0.0002 (7)
C5'	0.0628 (10)	0.0613 (10)	0.0594 (10)	0.0054 (8)	0.0053 (8)	0.0019 (8)
C6	0.0452 (8)	0.0482 (8)	0.0500 (8)	0.0040 (6)	−0.0052 (6)	−0.0036 (6)
C6'	0.0454 (8)	0.0482 (8)	0.0541 (9)	0.0066 (6)	−0.0064 (7)	−0.0026 (7)
C7	0.0458 (8)	0.0440 (8)	0.0465 (8)	−0.0002 (6)	−0.0049 (6)	−0.0025 (6)
C7'	0.0471 (8)	0.0428 (7)	0.0484 (8)	0.0020 (6)	−0.0075 (6)	−0.0014 (6)
C8'	0.0520 (8)	0.0429 (7)	0.0402 (7)	−0.0017 (6)	−0.0013 (6)	−0.0022 (6)
C8	0.0597 (9)	0.0431 (8)	0.0376 (7)	−0.0032 (7)	0.0004 (6)	−0.0022 (6)
C9'	0.0611 (10)	0.0590 (10)	0.0739 (11)	−0.0073 (8)	−0.0144 (8)	−0.0048 (8)
C9	0.0637 (11)	0.0624 (11)	0.0825 (13)	−0.0136 (9)	0.0004 (9)	−0.0097 (9)
C10	0.0969 (16)	0.0608 (12)	0.0820 (13)	−0.0337 (11)	0.0169 (12)	−0.0143 (10)
C10'	0.0861 (14)	0.0561 (10)	0.0740 (12)	−0.0243 (10)	−0.0017 (10)	−0.0122 (9)
C11	0.1251 (19)	0.0445 (9)	0.0549 (10)	−0.0006 (11)	0.0083 (11)	−0.0053 (8)
C11'	0.1054 (15)	0.0416 (9)	0.0559 (10)	0.0016 (9)	−0.0014 (10)	−0.0024 (7)
C12'	0.0926 (13)	0.0501 (9)	0.0675 (11)	0.0167 (9)	−0.0236 (10)	−0.0081 (8)
C12	0.1071 (15)	0.0523 (10)	0.0682 (11)	0.0205 (10)	−0.0210 (10)	−0.0112 (8)
C13'	0.0688 (10)	0.0462 (8)	0.0607 (10)	0.0050 (7)	−0.0203 (8)	−0.0093 (7)
C13	0.0759 (11)	0.0492 (9)	0.0579 (10)	0.0065 (8)	−0.0181 (8)	−0.0101 (7)
C14'	0.0462 (8)	0.0428 (7)	0.0483 (8)	0.0037 (6)	−0.0097 (6)	−0.0030 (6)
C14	0.0425 (8)	0.0428 (7)	0.0493 (8)	0.0000 (6)	−0.0089 (6)	−0.0037 (6)
C15	0.0501 (8)	0.0428 (7)	0.0417 (7)	−0.0005 (6)	−0.0080 (6)	0.0011 (6)
C15'	0.0512 (9)	0.0449 (8)	0.0432 (8)	0.0018 (6)	−0.0082 (6)	0.0025 (6)
C16'	0.0658 (10)	0.0636 (10)	0.0555 (10)	−0.0019 (8)	−0.0153 (8)	−0.0055 (8)
C16	0.0643 (10)	0.0670 (10)	0.0528 (9)	−0.0109 (8)	−0.0150 (8)	−0.0027 (8)
C17'	0.1082 (17)	0.0792 (13)	0.0503 (10)	0.0105 (11)	−0.0180 (10)	−0.0149 (9)
C17	0.1137 (18)	0.0716 (12)	0.0523 (10)	−0.0074 (11)	−0.0253 (11)	−0.0102 (9)
C18	0.1079 (17)	0.0764 (13)	0.0472 (10)	0.0192 (12)	0.0021 (10)	−0.0057 (9)
C18'	0.0907 (16)	0.0978 (15)	0.0504 (11)	0.0261 (12)	0.0074 (10)	0.0000 (10)
C19'	0.0547 (10)	0.1083 (15)	0.0637 (12)	0.0098 (10)	−0.0003 (9)	0.0070 (11)
C19	0.0629 (11)	0.0847 (13)	0.0644 (11)	0.0144 (10)	0.0055 (9)	0.0026 (10)
C20	0.0508 (9)	0.0670 (10)	0.0561 (9)	0.0002 (8)	−0.0075 (7)	−0.0042 (8)
C20'	0.0540 (10)	0.0767 (11)	0.0519 (9)	−0.0005 (8)	−0.0096 (7)	−0.0019 (8)
C21'	0.0596 (10)	0.0503 (9)	0.0579 (9)	−0.0009 (7)	−0.0142 (7)	0.0097 (7)
C21	0.0536 (9)	0.0503 (9)	0.0644 (10)	−0.0013 (7)	−0.0104 (7)	0.0097 (7)
C22'	0.0976 (15)	0.0638 (11)	0.0606 (11)	0.0032 (10)	−0.0077 (10)	0.0136 (8)
C22	0.1015 (15)	0.0645 (11)	0.0625 (11)	0.0042 (10)	−0.0113 (10)	0.0177 (9)
C23'	0.0667 (11)	0.0463 (9)	0.0728 (11)	−0.0015 (7)	−0.0160 (9)	0.0036 (8)
C23	0.0709 (11)	0.0463 (9)	0.0822 (13)	−0.0048 (8)	−0.0094 (9)	0.0093 (8)
C24	0.0689 (11)	0.0429 (9)	0.0784 (12)	−0.0070 (8)	−0.0073 (9)	−0.0056 (8)
C24'	0.0586 (10)	0.0428 (8)	0.0698 (11)	0.0020 (7)	−0.0128 (8)	−0.0061 (7)
N1'	0.0562 (8)	0.0447 (7)	0.0556 (8)	0.0068 (6)	−0.0059 (6)	−0.0071 (6)
N1	0.0580 (8)	0.0427 (7)	0.0574 (8)	−0.0003 (6)	−0.0065 (6)	−0.0071 (6)
N2	0.0557 (8)	0.0441 (7)	0.0497 (7)	0.0024 (5)	−0.0062 (6)	−0.0004 (5)
N2'	0.0579 (8)	0.0435 (7)	0.0497 (7)	0.0058 (6)	−0.0057 (6)	0.0013 (5)
O1	0.1340 (13)	0.0476 (7)	0.0939 (10)	−0.0064 (7)	0.0012 (9)	−0.0177 (7)
O1'	0.0954 (10)	0.0518 (7)	0.0843 (9)	0.0024 (6)	−0.0063 (7)	−0.0170 (6)

Geometric parameters (Å, º) top

C1—C2	1.389 (2)	C13—H13	0.9300
C1—C6	1.396 (2)	C14'—N2'	1.4164 (17)
C1—N1	1.4036 (19)	C14'—C15'	1.4817 (19)
C1'—C2'	1.386 (2)	C14—N2	1.4094 (17)
C1'—N1'	1.3982 (19)	C14—C15	1.4844 (19)
C1'—C6'	1.399 (2)	C15—C16	1.376 (2)
C2'—C3'	1.392 (2)	C15—C20	1.386 (2)
C2'—H2'	0.9300	C15'—C16'	1.381 (2)
C2—C3	1.384 (2)	C15'—C20'	1.383 (2)
C2—H2	0.9300	C16'—C17'	1.376 (2)
C3'—C4'	1.372 (2)	C16'—H16'	0.9300
C3'—H3'	0.9300	C16—C17	1.381 (2)
C3—C4	1.369 (2)	C16—H16	0.9300
C3—H3	0.9300	C17'—C18'	1.365 (3)
C4'—C5'	1.381 (2)	C17'—H17'	0.9300
C4'—H4'	0.9300	C17—C18	1.373 (3)
C4—C5	1.377 (2)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.367 (3)
C5—C6	1.402 (2)	C18—H18	0.9300
C5—H5	0.9300	C18'—C19'	1.371 (3)
C5'—C6'	1.400 (2)	C18'—H18'	0.9300
C5'—H5'	0.9300	C19'—C20'	1.370 (2)
C6—C7	1.4660 (19)	C19'—H19'	0.9300
C6'—C7'	1.463 (2)	C19—C20	1.374 (2)
C7—C14	1.3422 (19)	C19—H19	0.9300
C7—C8	1.4931 (19)	C20—H20	0.9300
C7'—C14'	1.3388 (19)	C20'—H20'	0.9300
C7'—C8'	1.4924 (19)	C21'—C23'	1.362 (2)
C8'—C13'	1.379 (2)	C21'—N2'	1.3621 (18)
C8'—C9'	1.380 (2)	C21'—C22'	1.476 (2)
C8—C9	1.376 (2)	C21—C23	1.357 (2)
C8—C13	1.382 (2)	C21—N2	1.3682 (18)
C9'—C10'	1.386 (2)	C21—C22	1.482 (2)
C9'—H9'	0.9300	C22'—H22A	0.9600
C9—C10	1.387 (3)	C22'—H22B	0.9600
C9—H9	0.9300	C22'—H22C	0.9600
C10—C11	1.359 (3)	C22—H22D	0.9600
C10—H10	0.9300	C22—H22E	0.9600
C10'—C11'	1.365 (3)	C22—H22F	0.9600
C10'—H10'	0.9300	C23'—C24'	1.397 (2)
C11—C12	1.358 (3)	C23'—H23'	0.9300
C11—H11	0.9300	C23—C24	1.399 (3)
C11'—C12'	1.363 (3)	C23—H23	0.9300
C11'—H11'	0.9300	C24—O1	1.232 (2)
C12'—C13'	1.384 (2)	C24—N1	1.4074 (19)
C12'—H12'	0.9300	C24'—O1'	1.2415 (19)
C12—C13	1.384 (2)	C24'—N1'	1.4087 (19)
C12—H12	0.9300	N1'—N2'	1.4095 (17)
C13'—H13'	0.9300	N1—N2	1.4075 (17)

C2—C1—C6	120.69 (14)	C7—C14—N2	119.67 (13)
C2—C1—N1	121.18 (13)	C7—C14—C15	123.21 (13)
C6—C1—N1	118.12 (13)	N2—C14—C15	117.11 (12)
C2'—C1'—N1'	121.02 (14)	C16—C15—C20	119.05 (14)
C2'—C1'—C6'	120.91 (14)	C16—C15—C14	120.50 (14)
N1'—C1'—C6'	118.03 (13)	C20—C15—C14	120.42 (13)
C1'—C2'—C3'	119.71 (16)	C16'—C15'—C20'	118.99 (15)
C1'—C2'—H2'	120.1	C16'—C15'—C14'	121.52 (14)
C3'—C2'—H2'	120.1	C20'—C15'—C14'	119.49 (13)
C3—C2—C1	119.63 (15)	C17'—C16'—C15'	120.37 (17)
C3—C2—H2	120.2	C17'—C16'—H16'	119.8
C1—C2—H2	120.2	C15'—C16'—H16'	119.8
C4'—C3'—C2'	120.44 (16)	C15—C16—C17	120.42 (17)
C4'—C3'—H3'	119.8	C15—C16—H16	119.8
C2'—C3'—H3'	119.8	C17—C16—H16	119.8
C4—C3—C2	120.64 (15)	C18'—C17'—C16'	120.01 (18)
C4—C3—H3	119.7	C18'—C17'—H17'	120.0
C2—C3—H3	119.7	C16'—C17'—H17'	120.0
C3'—C4'—C5'	119.67 (16)	C18—C17—C16	119.95 (17)
C3'—C4'—H4'	120.2	C18—C17—H17	120.0
C5'—C4'—H4'	120.2	C16—C17—H17	120.0
C3—C4—C5	119.92 (16)	C19—C18—C17	119.99 (17)
C3—C4—H4	120.0	C19—C18—H18	120.0
C5—C4—H4	120.0	C17—C18—H18	120.0
C4—C5—C6	121.22 (15)	C17'—C18'—C19'	120.12 (17)
C4—C5—H5	119.4	C17'—C18'—H18'	119.9
C6—C5—H5	119.4	C19'—C18'—H18'	119.9
C4'—C5'—C6'	121.63 (16)	C20'—C19'—C18'	120.29 (18)
C4'—C5'—H5'	119.2	C20'—C19'—H19'	119.9
C6'—C5'—H5'	119.2	C18'—C19'—H19'	119.9
C1—C6—C5	117.89 (14)	C18—C19—C20	120.38 (18)
C1—C6—C7	119.40 (13)	C18—C19—H19	119.8
C5—C6—C7	122.66 (13)	C20—C19—H19	119.8
C1'—C6'—C5'	117.62 (14)	C19—C20—C15	120.20 (16)
C1'—C6'—C7'	119.61 (13)	C19—C20—H20	119.9
C5'—C6'—C7'	122.62 (13)	C15—C20—H20	119.9
C14—C7—C6	120.49 (13)	C19'—C20'—C15'	120.20 (16)
C14—C7—C8	120.62 (13)	C19'—C20'—H20'	119.9
C6—C7—C8	118.88 (12)	C15'—C20'—H20'	119.9
C14'—C7'—C6'	120.53 (13)	C23'—C21'—N2'	108.69 (14)
C14'—C7'—C8'	121.55 (13)	C23'—C21'—C22'	126.36 (15)
C6'—C7'—C8'	117.81 (12)	N2'—C21'—C22'	124.89 (15)
C13'—C8'—C9'	118.28 (14)	C23—C21—N2	108.06 (15)
C13'—C8'—C7'	120.80 (13)	C23—C21—C22	126.95 (15)
C9'—C8'—C7'	120.79 (14)	N2—C21—C22	124.91 (15)
C9—C8—C13	118.08 (15)	C21'—C22'—H22A	109.5
C9—C8—C7	120.53 (15)	C21'—C22'—H22B	109.5
C13—C8—C7	121.36 (14)	H22A—C22'—H22B	109.5
C8'—C9'—C10'	120.64 (17)	C21'—C22'—H22C	109.5
C8'—C9'—H9'	119.7	H22A—C22'—H22C	109.5
C10'—C9'—H9'	119.7	H22B—C22'—H22C	109.5
C8—C9—C10	120.65 (19)	C21—C22—H22D	109.5
C8—C9—H9	119.7	C21—C22—H22E	109.5
C10—C9—H9	119.7	H22D—C22—H22E	109.5
C11—C10—C9	120.41 (18)	C21—C22—H22F	109.5
C11—C10—H10	119.8	H22D—C22—H22F	109.5
C9—C10—H10	119.8	H22E—C22—H22F	109.5
C11'—C10'—C9'	120.26 (17)	C21'—C23'—C24'	110.44 (14)
C11'—C10'—H10'	119.9	C21'—C23'—H23'	124.8
C9'—C10'—H10'	119.9	C24'—C23'—H23'	124.8
C12—C11—C10	119.77 (17)	C21—C23—C24	111.16 (15)
C12—C11—H11	120.1	C21—C23—H23	124.4
C10—C11—H11	120.1	C24—C23—H23	124.4
C12'—C11'—C10'	119.70 (16)	O1—C24—C23	132.52 (16)
C12'—C11'—H11'	120.1	O1—C24—N1	123.03 (16)
C10'—C11'—H11'	120.1	C23—C24—N1	104.44 (14)
C11'—C12'—C13'	120.41 (17)	O1'—C24'—C23'	132.34 (15)
C11'—C12'—H12'	119.8	O1'—C24'—N1'	122.78 (15)
C13'—C12'—H12'	119.8	C23'—C24'—N1'	104.86 (14)
C11—C12—C13	120.43 (19)	C1'—N1'—C24'	129.65 (13)
C11—C12—H12	119.8	C1'—N1'—N2'	120.51 (11)
C13—C12—H12	119.8	C24'—N1'—N2'	108.48 (12)
C8'—C13'—C12'	120.68 (16)	C1—N1—N2	120.48 (11)
C8'—C13'—H13'	119.7	C1—N1—C24	129.01 (13)
C12'—C13'—H13'	119.7	N2—N1—C24	108.60 (12)
C8—C13—C12	120.63 (17)	C21—N2—N1	107.72 (12)
C8—C13—H13	119.7	C21—N2—C14	132.80 (13)
C12—C13—H13	119.7	N1—N2—C14	119.19 (11)
C7'—C14'—N2'	119.45 (13)	C21'—N2'—N1'	107.52 (12)
C7'—C14'—C15'	123.80 (13)	C21'—N2'—C14'	132.91 (13)
N2'—C14'—C15'	116.67 (12)	N1'—N2'—C14'	119.08 (11)

N1'—C1'—C2'—C3'	−178.48 (15)	N2'—C14'—C15'—C16'	−106.61 (16)
C6'—C1'—C2'—C3'	−0.5 (2)	C7'—C14'—C15'—C20'	−103.33 (18)
C6—C1—C2—C3	−1.5 (2)	N2'—C14'—C15'—C20'	73.41 (18)
N1—C1—C2—C3	179.25 (14)	C20'—C15'—C16'—C17'	−1.8 (2)
C1'—C2'—C3'—C4'	−0.2 (3)	C14'—C15'—C16'—C17'	178.25 (15)
C1—C2—C3—C4	0.8 (3)	C20—C15—C16—C17	−1.3 (2)
C2'—C3'—C4'—C5'	0.1 (3)	C14—C15—C16—C17	−179.75 (14)
C2—C3—C4—C5	0.3 (3)	C15'—C16'—C17'—C18'	1.2 (3)
C3—C4—C5—C6	−0.7 (3)	C15—C16—C17—C18	0.7 (3)
C3'—C4'—C5'—C6'	0.6 (3)	C16—C17—C18—C19	0.1 (3)
C2—C1—C6—C5	1.1 (2)	C16'—C17'—C18'—C19'	−0.3 (3)
N1—C1—C6—C5	−179.67 (14)	C17'—C18'—C19'—C20'	0.1 (3)
C2—C1—C6—C7	−176.28 (13)	C17—C18—C19—C20	−0.3 (3)
N1—C1—C6—C7	3.0 (2)	C18—C19—C20—C15	−0.4 (3)
C4—C5—C6—C1	0.1 (2)	C16—C15—C20—C19	1.2 (2)
C4—C5—C6—C7	177.30 (15)	C14—C15—C20—C19	179.58 (14)
C2'—C1'—C6'—C5'	1.2 (2)	C18'—C19'—C20'—C15'	−0.7 (3)
N1'—C1'—C6'—C5'	179.27 (14)	C16'—C15'—C20'—C19'	1.6 (2)
C2'—C1'—C6'—C7'	−174.41 (14)	C14'—C15'—C20'—C19'	−178.47 (15)
N1'—C1'—C6'—C7'	3.6 (2)	N2'—C21'—C23'—C24'	−0.97 (19)
C4'—C5'—C6'—C1'	−1.3 (2)	C22'—C21'—C23'—C24'	176.27 (16)
C4'—C5'—C6'—C7'	174.20 (16)	N2—C21—C23—C24	−1.2 (2)
C1—C6—C7—C14	−7.5 (2)	C22—C21—C23—C24	175.78 (17)
C5—C6—C7—C14	175.24 (15)	C21—C23—C24—O1	−177.8 (2)
C1—C6—C7—C8	171.18 (13)	C21—C23—C24—N1	1.4 (2)
C5—C6—C7—C8	−6.0 (2)	C21'—C23'—C24'—O1'	−177.99 (18)
C1'—C6'—C7'—C14'	−7.5 (2)	C21'—C23'—C24'—N1'	0.52 (19)
C5'—C6'—C7'—C14'	177.10 (15)	C2'—C1'—N1'—C24'	−7.1 (2)
C1'—C6'—C7'—C8'	168.57 (13)	C6'—C1'—N1'—C24'	174.87 (14)
C5'—C6'—C7'—C8'	−6.9 (2)	C2'—C1'—N1'—N2'	−172.14 (13)
C14'—C7'—C8'—C13'	86.48 (19)	C6'—C1'—N1'—N2'	9.8 (2)
C6'—C7'—C8'—C13'	−89.52 (18)	O1'—C24'—N1'—C1'	12.4 (3)
C14'—C7'—C8'—C9'	−97.74 (18)	C23'—C24'—N1'—C1'	−166.32 (15)
C6'—C7'—C8'—C9'	86.27 (18)	O1'—C24'—N1'—N2'	178.79 (15)
C14—C7—C8—C9	−100.48 (18)	C23'—C24'—N1'—N2'	0.10 (16)
C6—C7—C8—C9	80.80 (18)	C2—C1—N1—N2	−170.43 (13)
C14—C7—C8—C13	81.75 (19)	C6—C1—N1—N2	10.3 (2)
C6—C7—C8—C13	−96.97 (17)	C2—C1—N1—C24	−8.1 (2)
C13'—C8'—C9'—C10'	1.6 (2)	C6—C1—N1—C24	172.68 (15)
C7'—C8'—C9'—C10'	−174.26 (15)	O1—C24—N1—C1	14.2 (3)
C13—C8—C9—C10	1.7 (2)	C23—C24—N1—C1	−165.04 (15)
C7—C8—C9—C10	−176.15 (15)	O1—C24—N1—N2	178.26 (17)
C8—C9—C10—C11	−0.3 (3)	C23—C24—N1—N2	−1.02 (17)
C8'—C9'—C10'—C11'	−0.1 (3)	C23—C21—N2—N1	0.54 (17)
C9—C10—C11—C12	−1.1 (3)	C22—C21—N2—N1	−176.55 (16)
C9'—C10'—C11'—C12'	−1.2 (3)	C23—C21—N2—C14	−173.02 (15)
C10'—C11'—C12'—C13'	1.0 (3)	C22—C21—N2—C14	9.9 (3)
C10—C11—C12—C13	1.1 (3)	C1—N1—N2—C21	165.95 (13)
C9'—C8'—C13'—C12'	−1.8 (2)	C24—N1—N2—C21	0.32 (16)
C7'—C8'—C13'—C12'	174.04 (14)	C1—N1—N2—C14	−19.45 (19)
C11'—C12'—C13'—C8'	0.6 (3)	C24—N1—N2—C14	174.92 (13)
C9—C8—C13—C12	−1.7 (2)	C7—C14—N2—C21	−172.29 (15)
C7—C8—C13—C12	176.11 (14)	C15—C14—N2—C21	8.5 (2)
C11—C12—C13—C8	0.3 (3)	C7—C14—N2—N1	14.7 (2)
C6'—C7'—C14'—N2'	−2.4 (2)	C15—C14—N2—N1	−164.52 (12)
C8'—C7'—C14'—N2'	−178.27 (13)	C23'—C21'—N2'—N1'	1.00 (17)
C6'—C7'—C14'—C15'	174.27 (13)	C22'—C21'—N2'—N1'	−176.29 (15)
C8'—C7'—C14'—C15'	−1.6 (2)	C23'—C21'—N2'—C14'	−170.62 (15)
C6—C7—C14—N2	−1.5 (2)	C22'—C21'—N2'—C14'	12.1 (3)
C8—C7—C14—N2	179.84 (13)	C1'—N1'—N2'—C21'	167.21 (13)
C6—C7—C14—C15	177.75 (13)	C24'—N1'—N2'—C21'	−0.68 (16)
C8—C7—C14—C15	−1.0 (2)	C1'—N1'—N2'—C14'	−19.80 (19)
C7—C14—C15—C16	77.33 (19)	C24'—N1'—N2'—C14'	172.30 (12)
N2—C14—C15—C16	−103.45 (16)	C7'—C14'—N2'—C21'	−173.38 (15)
C7—C14—C15—C20	−101.06 (17)	C15'—C14'—N2'—C21'	9.7 (2)
N2—C14—C15—C20	78.16 (17)	C7'—C14'—N2'—N1'	15.8 (2)
C7'—C14'—C15'—C16'	76.6 (2)	C15'—C14'—N2'—N1'	−161.12 (12)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg3, Cg4, Cg11 and Cg12 are the centroids of the N1/N2/C21–C24, C1–C6, C8–C13, C1'–C6' and C8'–C13' rings, respectively

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.93	2.22	2.862 (2)	125
C2′—H2′···O1′	0.93	2.22	2.865 (2)	126
C3—H3···O1′ⁱ	0.93	2.49	3.381 (2)	162
C3′—H3′···O1ⁱ	0.93	2.54	3.456 (2)	170
C11—H11···O1ⁱⁱ	0.93	2.49	3.274 (2)	142
C9—H9···Cg1ⁱⁱⁱ	0.93	2.92	3.796 (2)	158
C16—H16···Cg3ⁱⁱⁱ	0.93	3.00	3.822 (2)	149
C18—H18···Cg12^iv	0.93	2.95	3.869 (2)	169
C18′—H18′···Cg4^iv	0.93	2.98	3.867 (2)	161
C19—H19···Cg3^v	0.93	2.90	3.685 (2)	143
C19′—H19′···Cg11^vi	0.93	2.78	3.604 (2)	149

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

Acknowledgements

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

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