Supra­molecular architecture in a co-crystal of the N(7)—H tautomeric form of N6-benzoyl­adenine with adipic acid (1/0.5)

Swinton Darious, R.; Thomas Muthiah, P.; Perdih, F.

doi:10.1107/S2056989016007581

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Volume 72| Part 6| June 2016| Pages 805-808

https://doi.org/10.1107/S2056989016007581

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Supramolecular architecture in a co-crystal of the N(7)—H tautomeric form of N⁶-benzoyladenine with adipic acid (1/0.5)

Robert Swinton Darious,^a Packianathan Thomas Muthiah ^a ^* and Franc Perdih ^b

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, and ^bFaculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, PO Box 537, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: tommtrichy@yahoo.co.in

Edited by P. C. Healy, Griffith University, Australia (Received 22 April 2016; accepted 6 May 2016; online 13 May 2016)

The asymmetric unit of the title co-crystal, C₁₂H₉N₅O·0.5C₆H₁₀O₄, consists of one molecule of N⁶-benzoyladenine (BA) and one half-molecule of adipic acid (AA), the other half being generated by inversion symmetry. The dihedral angle between the adenine and phenyl ring planes is 26.71 (7)°. The N⁶-benzoyladenine molecule crystallizes in the N(7)—H tautomeric form with three non-protonated N atoms. This tautomeric form is stabilized by intramolecular N—H⋯O hydrogen bonding between the carbonyl (C=O) group and the N(7)—H hydrogen atom on the Hoogsteen face of the purine ring, forming an S(7) ring motif. The two carboxyl groups of adipic acid interact with the Watson–Crick face of the BA molecules through O—H⋯N and N—H⋯O hydrogen bonds, generating an R₂²(8) ring motif. The latter units are linked by N—H⋯N hydrogen bonds, forming layers parallel to (10-5). A weak C—H⋯O hydrogen bond is also present, linking adipic acid molecules in neighbouring layers, enclosing R²₂(10) ring motifs and forming a three-dimensional structure. C=O⋯π and C—H⋯π interactions are also present in the structure.

Keywords: crystal structure; N⁶-benzoyladenine; adipic acid; hydrogen bond; supramolecular sheet; π–π stacking; co-crystal.

CCDC reference: 1478504

1. Chemical context

Adipic acid has been widely used in controlled-release formulations of many drugs and food additives (Roew et al., 2009 ). N⁶-benzoyladenine is a synthetic analogue of a group of naturally occurring N⁶-substituted adenines having plant-growth-stimulating activity (cytokinins) (McHugh & Erxleben, 2011 ). A number of co-crystals involving adipic acid have been reported in the literature (Lemmerer et al., 2012 ; Lin et al., 2012 ; Matulková et al., 2014 ; Thanigaimani et al., 2012 ). This paper deals with a co-crystal formed between N⁶-benzoyladenine and adipic acid (I).

2. Structural commentary

The asymmetric unit of (I) contains one N⁶-benzoyladenine (BA) molecule and a half-molecule of adipic acid (AA). As evident from the angles at N7 [C8—N7—C5 = 106.82 (11)°] and N9 [C8—N9—C4 = 103.90 (11)°], the N⁶-benzoyladenine moiety exists in the N(7)—H tautomeric form with non-protonated N1, N3 and N9 atoms. In addition, the C8—N7 bond [1.3415 (17) Å)] is longer than C8—N9 [1.3175 (19) Å]. These values are similar to those in neutral N⁶-benzoyladenine (Raghunathan & Pattabhi, 1981 ). An intramolecular hydrogen bond in the Hoogsteen face between N7—H7 and the benzoyl oxygen atom O1 forms a S(7) ring motif. The dihedral angle between the adenine and phenyl ring plane is 26.71 (7)° and the C6—N6—C10—C11 torsion angle is 173.08 (14)°. The bond lengths and bond angles of AA are in the range of values reported (Srinivasa Gopalan et al., 1999 ; 2000 ). The values for the torsion angles C18—C19—C19a—C18a [180.00 (13)°] and C17—C18—C19—C19a [–176.09 (14)°] indicate that the carbon chain of AA is fully extended.

In the crystal structures of N⁶-benzyladenine (Raghunathan & Pattabhi, 1981), N⁶-furfuryladenine (Soriano-Garcia & Parthasarathy, 1977 ), N⁶-benzyladenine hydrobromide (Umadevi et al., 2001 ), N⁶-furfuryladenine hydrochloride (Stanley et al., 2003 ), N⁶-benzyladeninium p-toluenesulfonate (Tamilselvi & Muthiah, 2011 ), N⁶-benzyladeninium nitrate, N⁶-benzyladeninium 3-hydroxy picolinate (Nirmalram et al., 2011 ) and the hydrate adduct of N⁶-benzyladenine-5-sulfosalicylic acid (Xia et al., 2010 ), the N⁶-substituent is distal to the N7 position, whereas in the crystal structures of N⁶-benzoyladenine (Raghunathan et al., 1983 ), N⁶-benzoyladenine-3-hydroxypyridinium-2-carboxylate (1:1), N⁶-benzoyladenine-DL-tartaric acid (1:1) (Karthikeyan et al., 2015 ), N⁶-benzoyladeninium nitrate (Karthikeyan et al., 2015) and the title compound, the N⁶-substituent is distal to N1 and syn to adenine nitrogen atom N7. In the present structure, this may be attributed to the presence of the N7—H7⋯O1A intramolecular hydrogen bond (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C11–C16 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1ⁱ	0.82	1.92	2.7327 (19)	175
N6—H6⋯O3Aⁱⁱ	0.86	2.09	2.904 (11)	157
N7—H7⋯O1A	0.86	2.04	2.616 (16)	124
N7—H7⋯N9ⁱⁱⁱ	0.86	2.17	2.9271 (17)	146
C19—H19B⋯O3A^iv	0.97	2.54	3.481 (11)	164
C2—H2⋯Cg3^v	0.93	2.94	3.4611 (16)	117
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+2, -y+1, -z; (v) x, y-1, z.

3. Supramolecular features

Each of the two carboxyl groups of adipic acid interacts with the Watson–Crick face (atoms N1 and N6) of the corresponding BA through O—H⋯N and N—H⋯O hydrogen bonds, generating an R₂²(8) ring motif (Fig. 1). Thus each adipic acid molecule bridges two BA molecules. The latter units are linked by N7—H7⋯N9ⁱⁱⁱ hydrogen bonds (Table 1) forming layers parallel to plane (10 $[\overline{5}]$ ). A weak C—H⋯O hydrogen bond (C19—H19B⋯O3A^iv) is also present (Table 1 and Fig. 2), linking adipic acid molecules in neighbouring layers, enclosing R₂²(10) ring motifs and forming a three-dimensional structure. Thus atom O3A functions as a bifurcated hydrogen-bond acceptor whereas N7—H is a bifurcated hydrogen-bond donor.

Figure 1
A Mercury (Macrae et al., 2008

) view of the title compound (I)

, showing the atom-numbering scheme. Disordered oxygen atoms are omitted for clarity. H atoms not involved in hydrogen bonding have been omitted for clarity. Unlabelled atoms are related by the symmetry operation 1 − x, 1 − y, −z.

Figure 2
A view of the sheet-like supramolecular architecture generated via C19—H19B⋯O3A hydrogen bonds (black dotted lines). Phenyl rings are indicated as yellow balls. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes are as given in Table 1

The crystal structure also features C2—H2⋯π interactions between purine and phenyl rings (Fig. 3a) and C10=O1B⋯π interactions between the carbonyl oxygen O1B and the centroid of the (N1/C2/N3/C4/C5/C6) pyrimidine ring [O⋯centroid = 3.407 (10) Å; symmetry code: 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; Fig. 3b] (Safaei-Ghomi et al., 2009 ).

Figure 3
(a) A view of the C—H⋯π interaction in compound (I)

. Cg3 is the centroid of the phenyl ring of the BA molecule (symmetry code: x, −1 + y, z). (b) A view of the C=O⋯π interaction. Cg2 is the centroid of the pyrimidine ring of the BA molecule (symmetry code: 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z).

4. Database survey

The neutral molecule N⁶-benzoyladenine was reported by Raghunathan & Pattabhi (1981). Co-crystals have also been reported: N⁶-benzoyladenine-3-hydroxypyridinium-2-carboxylate (1:1), N⁶-benzoyladenine-DL-tartaric acid (1:1) (Karthikeyan et al., 2015) and N⁶-benzoyladeninium nitrate (Karthikeyan et al., 2016 ). Similarly, co-crystals of adipic acid with pyrimidine derivatives [adenine (Byres et al., 2009 ), caffeine (Bučar et al., 2007 ), cytosine (Das & Baruah, 2011 ), bis-pyrimidine-amine-linked xylene spacer (Goswami et al., 2010 )] have also been reported.

5. Synthesis and crystallization

The title co-crystal was synthesized by mixing a DMF solution of N⁶-benzoyladenine (30 mg) and adipic acid (19 mg) (total volume = 10 mL). The mixture was warmed in a water bath for 20 min. After cooling to room temperature, colourless plate-like crystals were collected from the mother liquor after a few days (m.p. 438 K).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Atoms O1 and O3 are disordered over two positions with refined occupancy ratios of 0.57 (3):0.43 (3) and 0.63 (3):0.37 (3), respectively. Hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 (aromatic) or 0.97 (methylene), N—H = 0.86, and O—H = 0.82 Å, and with U_iso(H) = kU_eq(C,N,O), where k = 1.5 for hydroxy and 1.2 for all other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉N₅O·0.5C₆H₁₀O₄
M_r	312.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.1776 (4), 9.2296 (4), 25.7480 (15)
β (°)	97.117 (6)
V (Å³)	1456.76 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.60 × 0.40

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.756, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9480, 3325, 2755
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.122, 1.05
No. of reflections	3325
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22
Computer programs: CrysAlis PRO (Agilent, 2013), SUPERFLIP (Palatinus & Chapuis, 2007 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1478504

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007581/hg5474sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007581/hg5474Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016007581/hg5474Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

N⁶-Benzoyladenine–adipic acid (1/0.5) top

Crystal data top

C₁₂H₉N₅O·0.5C₆H₁₀O₄	F(000) = 652
M_r = 312.31	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1776 (4) Å	Cell parameters from 4139 reflections
b = 9.2296 (4) Å	θ = 3.3–30.1°
c = 25.7480 (15) Å	µ = 0.10 mm⁻¹
β = 97.117 (6)°	T = 293 K
V = 1456.76 (14) Å³	Prism, colorless
Z = 4	0.60 × 0.60 × 0.40 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3325 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2755 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
Detector resolution: 10.4933 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→11
T_min = 0.756, T_max = 1.000	l = −33→31
9480 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0541P)² + 0.3295P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.122	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.25 e Å⁻³
3325 reflections	Δρ_min = −0.22 e Å⁻³
230 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0130 (18)

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)
O1A	0.7104 (15)	0.6427 (14)	0.1669 (8)	0.094 (4)	0.57 (3)
O1B	0.6582 (19)	0.6621 (6)	0.1877 (4)	0.054 (2)	0.43 (3)
N1	0.3308 (2)	0.27081 (12)	0.16588 (5)	0.0415 (3)
N3	0.5648 (2)	0.09828 (13)	0.21438 (5)	0.0477 (3)
N6	0.39990 (19)	0.51100 (12)	0.15270 (5)	0.0391 (3)
H6	0.2702	0.5109	0.1361	0.047*
N7	0.85319 (19)	0.42515 (12)	0.22672 (5)	0.0402 (3)
H7	0.8790	0.5157	0.2226	0.048*
N9	0.9054 (2)	0.19667 (13)	0.25397 (5)	0.0470 (3)
C2	0.3848 (3)	0.13827 (15)	0.18545 (6)	0.0468 (4)
H2	0.2811	0.0660	0.1774	0.056*
C4	0.7054 (2)	0.20808 (14)	0.22480 (5)	0.0389 (3)
C5	0.6683 (2)	0.35149 (13)	0.20707 (5)	0.0352 (3)
C6	0.4717 (2)	0.38085 (13)	0.17619 (5)	0.0347 (3)
C8	0.9855 (3)	0.32896 (15)	0.25376 (6)	0.0451 (4)
H8	1.1219	0.3535	0.2709	0.054*
C10	0.5100 (3)	0.63803 (16)	0.15283 (7)	0.0493 (4)
C11	0.4104 (2)	0.75951 (14)	0.11985 (6)	0.0412 (3)
C12	0.5550 (3)	0.86137 (17)	0.10534 (7)	0.0544 (4)
H12	0.7028	0.8527	0.1173	0.065*
C13	0.4831 (3)	0.97575 (19)	0.07333 (8)	0.0627 (5)
H13	0.5825	1.0423	0.0630	0.075*
C14	0.2660 (3)	0.99109 (19)	0.05686 (7)	0.0628 (5)
H14	0.2168	1.0681	0.0353	0.075*
C15	0.1208 (3)	0.8931 (2)	0.07213 (8)	0.0655 (5)
H15	−0.0274	0.9047	0.0611	0.079*
C16	0.1909 (3)	0.77622 (18)	0.10389 (7)	0.0538 (4)
H16	0.0908	0.7102	0.1142	0.065*
O2	0.9399 (2)	0.25032 (13)	0.10377 (6)	0.0694 (4)
H2A	1.0565	0.2620	0.1223	0.104*
O3A	1.0228 (15)	0.4644 (11)	0.0753 (5)	0.072 (2)	0.63 (3)
O3B	0.951 (3)	0.4828 (6)	0.0985 (9)	0.070 (5)	0.37 (3)
C17	0.8870 (3)	0.36824 (17)	0.07825 (6)	0.0494 (4)
C18	0.6762 (3)	0.36172 (16)	0.04285 (6)	0.0491 (4)
H18A	0.5619	0.3312	0.0631	0.059*
H18B	0.6882	0.2888	0.0162	0.059*
C19	0.6100 (3)	0.50345 (16)	0.01626 (6)	0.0494 (4)
H19A	0.6069	0.5781	0.0427	0.059*
H19B	0.7188	0.5308	−0.0060	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.047 (3)	0.085 (4)	0.138 (8)	−0.023 (2)	−0.033 (4)	0.071 (4)
O1B	0.052 (3)	0.028 (2)	0.073 (4)	−0.0097 (15)	−0.024 (2)	0.011 (2)
N1	0.0423 (6)	0.0333 (6)	0.0467 (7)	−0.0045 (5)	−0.0037 (5)	0.0046 (5)
N3	0.0559 (8)	0.0299 (6)	0.0536 (7)	−0.0047 (5)	−0.0074 (6)	0.0067 (5)
N6	0.0365 (6)	0.0308 (6)	0.0470 (6)	0.0002 (4)	−0.0071 (5)	0.0062 (5)
N7	0.0399 (6)	0.0269 (5)	0.0503 (7)	0.0015 (5)	−0.0079 (5)	0.0000 (5)
N9	0.0495 (7)	0.0310 (6)	0.0561 (7)	0.0051 (5)	−0.0108 (6)	0.0036 (5)
C2	0.0519 (9)	0.0325 (7)	0.0528 (8)	−0.0091 (6)	−0.0060 (7)	0.0062 (6)
C4	0.0444 (8)	0.0292 (6)	0.0412 (7)	0.0023 (5)	−0.0023 (6)	0.0017 (5)
C5	0.0381 (7)	0.0280 (6)	0.0383 (7)	0.0015 (5)	−0.0002 (6)	−0.0008 (5)
C6	0.0380 (7)	0.0290 (6)	0.0362 (6)	0.0006 (5)	0.0007 (6)	0.0015 (5)
C8	0.0423 (8)	0.0341 (7)	0.0550 (8)	0.0045 (6)	−0.0101 (7)	−0.0007 (6)
C10	0.0461 (8)	0.0357 (7)	0.0611 (9)	−0.0047 (6)	−0.0131 (7)	0.0124 (7)
C11	0.0472 (8)	0.0303 (6)	0.0441 (7)	0.0017 (6)	−0.0019 (6)	0.0044 (5)
C12	0.0510 (9)	0.0398 (8)	0.0710 (11)	−0.0011 (7)	0.0017 (8)	0.0131 (7)
C13	0.0716 (12)	0.0437 (9)	0.0746 (12)	0.0012 (8)	0.0155 (10)	0.0202 (8)
C14	0.0809 (13)	0.0479 (9)	0.0590 (10)	0.0163 (9)	0.0061 (9)	0.0205 (8)
C15	0.0542 (10)	0.0617 (11)	0.0771 (12)	0.0142 (9)	−0.0059 (9)	0.0204 (9)
C16	0.0464 (9)	0.0455 (8)	0.0672 (10)	0.0021 (7)	−0.0019 (8)	0.0146 (7)
O2	0.0568 (7)	0.0461 (6)	0.0963 (10)	−0.0026 (5)	−0.0264 (7)	0.0128 (6)
O3A	0.061 (3)	0.072 (2)	0.076 (4)	−0.026 (2)	−0.024 (3)	0.027 (2)
O3B	0.069 (5)	0.037 (2)	0.092 (8)	−0.006 (2)	−0.035 (5)	0.002 (2)
C17	0.0477 (9)	0.0428 (8)	0.0544 (9)	−0.0017 (7)	−0.0073 (7)	0.0029 (7)
C18	0.0472 (8)	0.0408 (8)	0.0558 (9)	−0.0017 (6)	−0.0071 (7)	−0.0016 (7)
C19	0.0481 (9)	0.0411 (8)	0.0554 (9)	−0.0023 (6)	−0.0070 (7)	0.0023 (7)

Geometric parameters (Å, º) top

O1A—C10	1.247 (6)	C12—C13	1.378 (2)
O1B—C10	1.221 (6)	C12—H12	0.9300
N1—C6	1.3424 (17)	C13—C14	1.363 (3)
N1—C2	1.3489 (17)	C13—H13	0.9300
N3—C2	1.3125 (19)	C14—C15	1.365 (3)
N3—C4	1.3401 (18)	C14—H14	0.9300
N6—C10	1.3551 (18)	C15—C16	1.390 (2)
N6—C6	1.3926 (16)	C15—H15	0.9300
N6—H6	0.8600	C16—H16	0.9300
N7—C8	1.3415 (17)	O2—C17	1.2923 (18)
N7—C5	1.3712 (17)	O2—H2A	0.8200
N7—H7	0.8601	O3A—C17	1.230 (4)
N9—C8	1.3175 (19)	O3B—C17	1.223 (6)
N9—C4	1.3684 (18)	C17—C18	1.495 (2)
C2—H2	0.9300	C18—C19	1.509 (2)
C4—C5	1.4096 (17)	C18—H18A	0.9700
C5—C6	1.3931 (18)	C18—H18B	0.9700
C8—H8	0.9300	C19—C19ⁱ	1.506 (3)
C10—C11	1.4924 (18)	C19—H19A	0.9700
C11—C16	1.376 (2)	C19—H19B	0.9700
C11—C12	1.380 (2)

C6—N1—C2	119.23 (11)	C13—C12—H12	119.6
C2—N3—C4	112.56 (12)	C11—C12—H12	119.6
C10—N6—C6	127.77 (11)	C14—C13—C12	119.81 (17)
C10—N6—H6	116.0	C14—C13—H13	120.1
C6—N6—H6	116.2	C12—C13—H13	120.1
C8—N7—C5	106.82 (11)	C13—C14—C15	119.86 (15)
C8—N7—H7	126.7	C13—C14—H14	120.1
C5—N7—H7	126.5	C15—C14—H14	120.1
C8—N9—C4	103.90 (11)	C14—C15—C16	121.01 (16)
N3—C2—N1	128.29 (13)	C14—C15—H15	119.5
N3—C2—H2	115.9	C16—C15—H15	119.5
N1—C2—H2	115.9	C11—C16—C15	119.12 (16)
N3—C4—N9	124.79 (12)	C11—C16—H16	120.4
N3—C4—C5	124.74 (12)	C15—C16—H16	120.4
N9—C4—C5	110.47 (12)	C17—O2—H2A	109.5
N7—C5—C6	137.86 (12)	O3B—C17—O2	117.6 (6)
N7—C5—C4	104.56 (11)	O3A—C17—O2	120.5 (3)
C6—C5—C4	117.57 (12)	O3B—C17—C18	120.5 (3)
N1—C6—N6	113.77 (11)	O3A—C17—C18	122.7 (2)
N1—C6—C5	117.61 (11)	O2—C17—C18	114.98 (13)
N6—C6—C5	128.60 (12)	C17—C18—C19	114.09 (13)
N9—C8—N7	114.25 (12)	C17—C18—H18A	108.7
N9—C8—H8	122.9	C19—C18—H18A	108.7
N7—C8—H8	122.9	C17—C18—H18B	108.7
O1B—C10—N6	119.4 (5)	C19—C18—H18B	108.7
O1A—C10—N6	120.7 (5)	H18A—C18—H18B	107.6
O1B—C10—C11	120.0 (3)	C19ⁱ—C19—C18	112.99 (16)
O1A—C10—C11	117.6 (3)	C19ⁱ—C19—H19A	109.0
N6—C10—C11	118.50 (12)	C18—C19—H19A	109.0
C16—C11—C12	119.33 (13)	C19ⁱ—C19—H19B	109.0
C16—C11—C10	125.15 (14)	C18—C19—H19B	109.0
C12—C11—C10	115.52 (13)	H19A—C19—H19B	107.8
C13—C12—C11	120.82 (16)

C4—N3—C2—N1	0.6 (3)	C6—N6—C10—O1B	−23.5 (8)
C6—N1—C2—N3	−0.5 (3)	C6—N6—C10—O1A	13.7 (14)
C2—N3—C4—N9	−179.85 (15)	C6—N6—C10—C11	173.08 (14)
C2—N3—C4—C5	−0.1 (2)	O1B—C10—C11—C16	−138.8 (8)
C8—N9—C4—N3	179.82 (16)	O1A—C10—C11—C16	−175.5 (14)
C8—N9—C4—C5	0.06 (18)	N6—C10—C11—C16	24.5 (3)
C8—N7—C5—C6	−179.15 (18)	O1B—C10—C11—C12	40.7 (9)
C8—N7—C5—C4	−0.01 (16)	O1A—C10—C11—C12	4.0 (14)
N3—C4—C5—N7	−179.79 (15)	N6—C10—C11—C12	−156.02 (16)
N9—C4—C5—N7	−0.03 (17)	C16—C11—C12—C13	−2.8 (3)
N3—C4—C5—C6	−0.4 (2)	C10—C11—C12—C13	177.68 (17)
N9—C4—C5—C6	179.31 (13)	C11—C12—C13—C14	1.8 (3)
C2—N1—C6—N6	178.40 (13)	C12—C13—C14—C15	0.0 (3)
C2—N1—C6—C5	−0.2 (2)	C13—C14—C15—C16	−0.7 (3)
C10—N6—C6—N1	−175.34 (15)	C12—C11—C16—C15	2.0 (3)
C10—N6—C6—C5	3.0 (3)	C10—C11—C16—C15	−178.52 (16)
N7—C5—C6—N1	179.62 (16)	C14—C15—C16—C11	−0.3 (3)
C4—C5—C6—N1	0.6 (2)	O3B—C17—C18—C19	26.0 (16)
N7—C5—C6—N6	1.3 (3)	O3A—C17—C18—C19	−19.2 (10)
C4—C5—C6—N6	−177.74 (14)	O2—C17—C18—C19	176.05 (16)
C4—N9—C8—N7	−0.08 (19)	C17—C18—C19—C19ⁱ	−176.11 (18)
C5—N7—C8—N9	0.06 (19)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C11–C16 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ⁱⁱ	0.82	1.92	2.7327 (19)	175
N6—H6···O3Aⁱⁱⁱ	0.86	2.09	2.904 (11)	157
N7—H7···O1A	0.86	2.04	2.616 (16)	124
N7—H7···N9^iv	0.86	2.17	2.9271 (17)	146
C19—H19B···O3A^v	0.97	2.54	3.481 (11)	164
C2—H2···Cg3^vi	0.93	2.94	3.4611 (16)	117

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

Acknowledgements

RSD thanks the UGC–BSR India for the award of an RFSMS. PTM is thankful to the UGC, New Delhi, for a UGC–BSR one-time grant to Faculty. FP thanks the Slovenian Research Agency for financial support (P1–0230-0175), as well as the EN–FIST Centre of Excellence, Ljubljana, Slovenia, for the use of the SuperNova diffractometer.

References

Agilent (2013). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England. Google Scholar
Bučar, D. K., Henry, R. F., Lou, X., Borchardt, T. & Zhang, G. G. Z. (2007). Chem. Commun. pp. 525–527. Google Scholar
Byres, M., Cox, P. J., Kay, G. & Nixon, E. (2009). CrystEngComm, 11, 135–142. Web of Science CSD CrossRef CAS Google Scholar
Das, B. & Baruah, J. B. (2011). J. Mol. Struct. 1001, 134–138. Web of Science CSD CrossRef CAS Google Scholar
Goswami, S., Hazra, A. & Fun, H.-K. (2010). J. Incl Phenom. Macrocycl Chem. 68, 461–466. Web of Science CSD CrossRef CAS Google Scholar
Karthikeyan, A., Jeeva Jasmine, N., Thomas Muthiah, P. & Perdih, F. (2016). Acta Cryst. E72, 140–143. Web of Science CSD CrossRef IUCr Journals Google Scholar
Karthikeyan, A., Swinton Darious, R., Thomas Muthiah, P. & Perdih, F. (2015). Acta Cryst. C71, 985–990. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lemmerer, A., Bernstein, J. & Kahlenberg, V. (2012). Acta Cryst. E68, o190. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lin, S., Jia, R., Gao, F. & Zhou, X. (2012). Acta Cryst. E68, o3457. CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Matulková, I., Císařová, I., Němec, I. & Fábry, J. (2014). Acta Cryst. C70, 927–933. Web of Science CSD CrossRef IUCr Journals Google Scholar
McHugh, C. & Erxleben, A. (2011). Cryst. Growth Des. 11, 5096–5104. Web of Science CSD CrossRef CAS Google Scholar
Nirmalram, J. S., Tamilselvi, D. & Muthiah, P. T. (2011). J. Chem. Crystallogr. 41, 864–867. Web of Science CSD CrossRef CAS Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Raghunathan, S. & Pattabhi, V. (1981). Acta Cryst. B37, 1670–1673. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Raghunathan, S., Sinha, B. K., Pattabhi, V. & Gabe, E. J. (1983). Acta Cryst. C39, 1545–1547. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Roew, R., Sheskey, P. & Quinn, M. (2009). Adipic Acid, Handbook of Pharmaceutical Excipients, pp. 11–12. Google Scholar
Safaei-Ghomi, J., Aghabozorg, H., Motyeian, E. & Ghadermazi, M. (2009). Acta Cryst. E65, m2–m3. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soriano-Garcia, M. & Parthasarathy, R. (1977). Acta Cryst. B33, 2674–2677. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Srinivasa Gopalan, R., Kumaradhas, P. & Kulkarni, G. U. (1999). J. Solid State Chem. 148, 129–134. CSD CrossRef CAS Google Scholar
Srinivasa Gopalan, R., Kumaradhas, P., Kulkarni, G. U. & Rao, C. N. R. (2000). J. Mol. Struct. 521, 97–106. CSD CrossRef CAS Google Scholar
Stanley, N., Muthiah, P. T. & Geib, S. J. (2003). Acta Cryst. C59, o27–o29. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Tamilselvi, D. & Muthiah, P. T. (2011). Acta Cryst. C67, o192–o194. Web of Science CSD CrossRef IUCr Journals Google Scholar
Thanigaimani, K., Razak, I. A., Arshad, S., Jagatheesan, R. & Santhanaraj, K. J. (2012). Acta Cryst. E68, o2938–o2939. CSD CrossRef IUCr Journals Google Scholar
Umadevi, B., Stanley, N., Muthiah, P. T., Bocelli, G. & Cantoni, A. (2001). Acta Cryst. E57, o881–o883. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xia, M., Ma, K. & Zhu, Y. (2010). J. Chem. Crystallogr. 40, 634–638. Web of Science CSD CrossRef CAS Google Scholar

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