Crystal structure and Hirshfeld surface analysis of 2-amino-4-meth­oxy-6-methyl­pyrimidinium 2-hy­droxy­benzoate

Jeevaraj, M.; Sivajeyanthi, P.; Edison, B.; Thanigaimani, K.; Balasubramani, K.; Razak, I.A.

doi:10.1107/S2056989017011252

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 73| Part 9| September 2017| Pages 1305-1307

https://doi.org/10.1107/S2056989017011252

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Crystal structure and Hirshfeld surface analysis of 2-amino-4-methoxy-6-methylpyrimidinium 2-hydroxybenzoate

Muthaiah Jeevaraj,^a Palaniyappan Sivajeyanthi,^a Bellarmin Edison,^a Kaliyaperumal Thanigaimani,^b Kasthuri Balasubramani ^a ^* and Ibrahim Abdul Razak ^c ‡

^aDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, ^bDepartment of Chemistry, Government Arts College, Tiruchirappalli 620 022, Tamil Nadu, India, and ^cSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: manavaibala@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 July 2017; accepted 31 July 2017; online 8 August 2017)

In the title molecular salt, C₆H₁₀N₃O⁺·C₇H₅O₃⁻, the cation is protonated at the N atom lying between the amine and methyl substituents and the dihedral angle between the carboxyl group and its attached ring in the anion is 4.0 (2)°. The anion features an intramolecular O—H⋯O hydrogen bond, which closes an S(6) ring. The cation and anion are linked by two N—H⋯O hydrogen bonds [R₂²(8) motif] to generate an ion pair in which the dihedral angle between the aromatic rings is 8.34 (9)°. Crystal symmetry relates two ion pairs bridged by further N—H⋯O hydrogen bonds into a tetrameric DDAA array. The tetramers are linked by pairs of C—H⋯O hydrogen bonds to generate [100] chains. Hirshfeld surface and fingerprint plot analyses are presented.

Keywords: crystal structure; Hirshfeld surface analysis; hydrogen bonding.

CCDC reference: 1559280

1. chemical context

Pyrimidine and aminopyrimidine derivatives have many applications as pesticides and pharmaceutical agents (Condon et al., 1993 ). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990 ). Pyrimidine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely-used anti-AIDS drug (Gilchrist, 1997 ). Hydrogen bonding plays a vital role in molecular recognition. Supramolecular chemistry plays a pivotal role in biological systems and in artificial systems. It refers to the specific interaction between two or more motifs through non-covalent interactions such as hydrogen bonding, hydrophobic forces, van der Waals forces, π–π interactions etc. The generating of supramolecular architectures is correlated to the positions and properties of the active groups in molecules (Desiraju et al., 1989 ; Steiner et al., 2002 ) As part of our studies in these areas, the synthesis and structure of the title molecular salt, (I), is presented here.

2. structural commentary

The molecular structure of (I) is shown in Fig. 1. The asymmetric unit contains a 2-amino-4-methoxy-6-methylpyrimidinium cation and a 2-hydroxybenzoate anion. The cation is protonated at N1, which lies between the amine and methyl substituents: this protonation is reflected by an increase in the bond angle at N1 [C1—N1—C2 = 121.09 (15)°], when compared with the unprotonated atom N3 [C1—N3—C4 = 116.52 (18)°], and the corresponding angle of 116.01 (18)° in neutral 2-amino-4-methoxy-6-methylpyrimidine (Glidewell et al., 2003 ). An intramolecular O—H⋯O hydrogen bond occurs within the anion (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.84	2.7033 (19)	176
N2—H2A⋯O3ⁱ	0.86	2.00	2.816 (3)	158
N2—H2B⋯O3	0.86	1.99	2.830 (2)	165
O4—H4⋯O2	0.82	1.81	2.534 (2)	147
C3—H3⋯O1ⁱⁱ	0.93	2.48	3.374 (3)	160
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+3, -y+1, -z+2.

Figure 1
The asymmetric unit of (I)

, with 50% probability displacement ellipsoids. The hydrogen bonds are indicated by dashed lines.

3. supramolecular features

The protonated N atom (N1) and 2-amino group (N2) of the cation interacts with the O1 and O2 oxygen atoms of the carboxylate anion through a pair of N—H⋯O hydrogen bonds (Table 1), forming an eight-membered ring motif R₂²(8). Inversion-related R₂²(8) ring motifs are further bridged by N—H⋯O hydrogen bonds thereby forming a DDAA tetramer (D stands for hydrogen-bond donor and A stands for hydrogen-bond acceptor). This set of fused rings can be represented by the graph-set notations R₂²(8), R₄²(8) and R₂²(8). This type of motif has been reported previously in the crystal structures of trimethoprim hydrogen glutarate (Robert et al., 2001 ) and 2-amino-4-methoxy-6-methylpyridinium trifluoroacetate (Jeevaraj et al., 2016 ). These arrays are further linked via pairwise C—H⋯O hydrogen bonds to generate another R₂²(8) ring motif as part of a [100] chain (Fig. 2).

Figure 2
A [100] chain in the crystal of (I)

incorporating R₂²(8), R₄²(8) and R₄²(12) ring motifs.

4. Hirshfeld surface analysis

The d_norm parameter takes negative or positive values depending on whether the inter-molecular contact is shorter or longer, respectively, than the van der Waals radii (Spackman & Jayatilaka et al., 2009 ; McKinnon et al., 2007 ). The d_norm surface of the ion-pair in (I) is shown in Fig. 3: this naturally neglects hydrogen bonds (intra-anion O—H⋯O and N—H⋯O cation-to-anion) that occur within the asymmetric unit. The red points represent closer contacts and negative d_norm values on the surface corresponding to the N—H⋯O and C—H⋯O interactions are light red in colour. Two-dimensional fingerprint plots from the Hirshfeld surface analysis, as shown in Fig. 4, give a break-down of different contacts as follows: H⋯H (44.2%), C⋯H/H⋯C (19.6%), O⋯H/H⋯O (20.9%), C⋯O/O⋯C (3.0%), C⋯C (2.9%), N⋯H/H⋯N (8.1%) and O⋯O (1.0%). Two `wingtips' in the fingerprint plot are related to the strong H⋯O and O⋯H interactions.

Figure 3
Three-dimensional Hirshfeld surface of (I)

Figure 4
Fingerprint plots for (I)

5. Database survey

A search of the Cambridge Structural Database (Version 5.37, update February 2017; Groom et al., 2016 ) for 2-amino-4-methoxy-6-methylpyrimidine yielded seven structures: VAQSOW, VAQSUC, VAQSEM, VAQSIQ, VAQRUB and VAQSAI (Aakeroy et al., 2003 ) and NUQTOJ (Jasinski et al. (2010 ).

6. Synthesis and crystallization

The title compound was synthesized by mixing hot methanolic solutions (20 ml) of 2-amino-4-methoxy-6-methylpyrimidine (0.139 mg) and 2-hydroxybenzoic acid (0.156 mg) in a 1:1 molar ratio. The mixed solutions were warmed few minutes over a waterbath and then cooled and kept at room temperature for slow evaporation. After a few days, colourless block-shaped crystals of (I) were obtained (yield = 65%).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms were positioned geometrically (N—H = 0.86, O—H = 0.82 and C—H = 0.96 or 0.93 Å) and were refined using a riding model, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). A rotating-group model was used for the methyl group.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₃O⁺·C₇H₅O₃⁻
M_r	277.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.4291 (12), 15.0620 (19), 12.1595 (11)
β (°)	128.252 (6)
V (Å³)	1356.1 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.55 × 0.33 × 0.16

Data collection
Diffractometer	Bruker KappaCCD APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.960, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	33325, 4033, 2373
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.164, 1.02
No. of reflections	4033
No. of parameters	183
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1559280

Crystal structure: contains datablocks global, I, 1. DOI: https://doi.org/10.1107/S2056989017011252/hb7693sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011252/hb7693Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017011252/hb7693Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

2-Amino-4-methoxy-6-methylpyrimidinium 2-hydroxybenzoate top

Crystal data top

C₆H₁₀N₃O⁺·C₇H₅O₃⁻	F(000) = 584
M_r = 277.28	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4033 reflections
a = 9.4291 (12) Å	θ = 2.5–27.5°
b = 15.0620 (19) Å	µ = 0.10 mm⁻¹
c = 12.1595 (11) Å	T = 296 K
β = 128.252 (6)°	Block, colourless
V = 1356.1 (3) Å³	0.55 × 0.33 × 0.16 mm
Z = 4

Data collection top

Bruker KappaCCD APEXII diffractometer	4033 independent reflections
Radiation source: fine-focus sealed tube	2373 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω and φ scans	θ_max = 30.2°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
T_min = 0.960, T_max = 0.984	k = −21→21
33325 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0587P)² + 0.4004P] where P = (F_o² + 2F_c²)/3
4033 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
O1	1.29929 (16)	0.42997 (10)	1.00372 (13)	0.0632 (4)
N1	0.97381 (17)	0.55436 (9)	0.63943 (14)	0.0475 (4)
N2	0.72932 (19)	0.50804 (12)	0.62236 (17)	0.0659 (6)
N3	1.01155 (18)	0.46656 (10)	0.81604 (14)	0.0486 (4)
C1	0.9058 (2)	0.50922 (12)	0.69373 (17)	0.0482 (5)
C2	1.1545 (2)	0.55729 (11)	0.70701 (17)	0.0465 (5)
C3	1.2648 (2)	0.51464 (12)	0.82987 (18)	0.0510 (5)
C4	1.1868 (2)	0.46995 (11)	0.88151 (17)	0.0472 (5)
C5	1.2254 (3)	0.38111 (18)	1.0601 (3)	0.0863 (9)
C6	1.2148 (3)	0.60934 (14)	0.6387 (2)	0.0620 (7)
O2	0.75239 (17)	0.63571 (9)	0.38790 (13)	0.0593 (4)
O3	0.51173 (16)	0.57024 (9)	0.34276 (13)	0.0597 (4)
O4	0.7259 (2)	0.72936 (11)	0.20277 (15)	0.0756 (6)
C7	0.5836 (2)	0.62036 (11)	0.30856 (17)	0.0459 (5)
C8	0.4695 (2)	0.66507 (10)	0.16945 (16)	0.0445 (5)
C9	0.5463 (3)	0.71779 (12)	0.12434 (19)	0.0554 (6)
C10	0.4349 (4)	0.75988 (14)	−0.0047 (2)	0.0723 (8)
C11	0.2513 (3)	0.74946 (14)	−0.0879 (2)	0.0719 (8)
C12	0.1737 (3)	0.69718 (14)	−0.0458 (2)	0.0649 (7)
C13	0.2822 (2)	0.65538 (12)	0.08200 (19)	0.0529 (6)
H1	0.90150	0.58160	0.56090	0.0570*
H2A	0.68270	0.47990	0.65460	0.0790*
H2B	0.66070	0.53540	0.54350	0.0790*
H3	1.38930	0.51480	0.87920	0.0610*
H5A	1.14960	0.41960	1.06650	0.1290*
H5B	1.32220	0.35930	1.15160	0.1290*
H5C	1.15550	0.33200	0.99970	0.1290*
H6A	1.22890	0.67050	0.66590	0.0930*
H6B	1.12630	0.60460	0.53890	0.0930*
H6C	1.32820	0.58650	0.66740	0.0930*
H4	0.77590	0.70480	0.27870	0.1130*
H10	0.48530	0.79540	−0.03500	0.0870*
H11	0.17840	0.77820	−0.17400	0.0860*
H12	0.04900	0.69010	−0.10300	0.0780*
H13	0.22980	0.61990	0.11070	0.0640*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0472 (7)	0.0777 (9)	0.0528 (7)	0.0025 (6)	0.0250 (6)	0.0194 (6)
N1	0.0436 (7)	0.0531 (8)	0.0423 (7)	−0.0014 (6)	0.0249 (6)	0.0067 (6)
N2	0.0418 (8)	0.0915 (12)	0.0561 (9)	0.0001 (8)	0.0262 (7)	0.0254 (9)
N3	0.0426 (7)	0.0549 (8)	0.0442 (8)	−0.0032 (6)	0.0249 (6)	0.0054 (6)
C1	0.0433 (8)	0.0543 (10)	0.0446 (9)	−0.0026 (7)	0.0260 (8)	0.0036 (7)
C2	0.0468 (9)	0.0486 (9)	0.0478 (9)	−0.0061 (7)	0.0311 (8)	−0.0041 (7)
C3	0.0417 (8)	0.0597 (10)	0.0492 (9)	−0.0022 (7)	0.0269 (8)	0.0016 (8)
C4	0.0447 (9)	0.0496 (9)	0.0428 (9)	0.0003 (7)	0.0248 (7)	0.0021 (7)
C5	0.0666 (13)	0.1089 (19)	0.0698 (14)	−0.0019 (12)	0.0355 (12)	0.0374 (13)
C6	0.0594 (11)	0.0715 (12)	0.0613 (11)	−0.0109 (9)	0.0405 (10)	0.0042 (9)
O2	0.0508 (7)	0.0703 (8)	0.0485 (7)	−0.0047 (6)	0.0266 (6)	0.0078 (6)
O3	0.0537 (7)	0.0726 (9)	0.0564 (7)	0.0029 (6)	0.0359 (6)	0.0161 (6)
O4	0.0751 (9)	0.0866 (11)	0.0666 (9)	−0.0209 (8)	0.0446 (8)	0.0052 (8)
C7	0.0511 (9)	0.0460 (9)	0.0460 (9)	0.0039 (7)	0.0328 (8)	0.0010 (7)
C8	0.0540 (9)	0.0387 (8)	0.0421 (8)	0.0046 (7)	0.0304 (8)	0.0002 (6)
C9	0.0703 (12)	0.0485 (9)	0.0518 (10)	−0.0050 (8)	0.0400 (10)	−0.0011 (8)
C10	0.1055 (18)	0.0579 (12)	0.0625 (13)	−0.0020 (11)	0.0565 (13)	0.0097 (10)
C11	0.0920 (16)	0.0589 (12)	0.0491 (11)	0.0191 (11)	0.0359 (12)	0.0094 (9)
C12	0.0653 (12)	0.0627 (12)	0.0528 (11)	0.0186 (9)	0.0296 (10)	0.0042 (9)
C13	0.0571 (10)	0.0490 (10)	0.0502 (10)	0.0100 (8)	0.0320 (9)	0.0026 (8)

Geometric parameters (Å, º) top

O1—C4	1.321 (2)	C5—H5A	0.9600
O1—C5	1.445 (4)	C5—H5C	0.9600
O2—C7	1.271 (3)	C5—H5B	0.9600
O3—C7	1.245 (3)	C6—H6B	0.9600
O4—C9	1.345 (3)	C6—H6C	0.9600
O4—H4	0.8200	C6—H6A	0.9600
N1—C2	1.359 (3)	C7—C8	1.490 (2)
N1—C1	1.354 (3)	C8—C13	1.395 (3)
N2—C1	1.317 (3)	C8—C9	1.396 (3)
N3—C1	1.335 (2)	C9—C10	1.388 (3)
N3—C4	1.318 (3)	C10—C11	1.370 (4)
N1—H1	0.8600	C11—C12	1.372 (4)
N2—H2B	0.8600	C12—C13	1.375 (3)
N2—H2A	0.8600	C10—H10	0.9300
C2—C6	1.488 (3)	C11—H11	0.9300
C2—C3	1.343 (2)	C12—H12	0.9300
C3—C4	1.400 (3)	C13—H13	0.9300
C3—H3	0.9300

O1···C3ⁱ	3.374 (3)	C7···H10^iv	2.8800
O2···C3ⁱⁱ	3.411 (2)	C7···H2B	2.7800
O2···N1	2.7033 (19)	C7···H1	2.7100
O2···O4	2.534 (2)	C7···H4	2.4200
O3···N2ⁱⁱⁱ	2.816 (3)	C9···H5B^vi	3.0500
O3···N2	2.830 (2)	C12···H6A^ix	3.0300
O4···O2	2.534 (2)	C13···H6A^ix	2.9700
O1···H3ⁱ	2.4800	H1···O2	1.8400
O2···H4	1.8100	H1···O3	2.9200
O2···H6B	2.8300	H1···C7	2.7100
O2···H1	1.8400	H1···H2B	2.2600
O3···H2B	1.9900	H1···H6B	2.3200
O3···H13	2.5100	H2A···O3ⁱⁱⁱ	2.0000
O3···H1	2.9200	H2A···H2Bⁱⁱⁱ	2.5800
O3···H2Aⁱⁱⁱ	2.0000	H2B···O3	1.9900
O3···H6Cⁱⁱ	2.8500	H2B···C7	2.7800
O3···H10^iv	2.6100	H2B···H1	2.2600
O4···H12^v	2.7200	H2B···H2Aⁱⁱⁱ	2.5800
O4···H5B^vi	2.8600	H3···H6C	2.5100
N1···O2	2.7033 (19)	H3···O1ⁱ	2.4800
N2···O3	2.830 (2)	H3···C3ⁱ	3.0100
N2···O3ⁱⁱⁱ	2.816 (3)	H3···H3ⁱ	2.3600
N3···H5C	2.6800	H4···O2	1.8100
N3···H5A	2.5600	H4···C7	2.4200
C2···C11^vii	3.551 (3)	H4···H12^v	2.5700
C2···C12^vii	3.582 (3)	H5A···N3	2.5600
C3···O1ⁱ	3.374 (3)	H5B···O4^x	2.8600
C3···C12^vii	3.492 (3)	H5B···C9^x	3.0500
C3···C7ⁱⁱ	3.463 (3)	H5C···N3	2.6800
C3···O2ⁱⁱ	3.411 (2)	H6A···C13^v	2.9700
C4···C12^vii	3.556 (3)	H6A···C12^v	3.0300
C4···C13^vii	3.441 (3)	H6B···O2	2.8300
C6···C12^v	3.550 (3)	H6B···H1	2.3200
C7···C3ⁱⁱ	3.463 (3)	H6C···H3	2.5100
C11···C2^viii	3.551 (3)	H6C···O3ⁱⁱ	2.8500
C12···C3^viii	3.492 (3)	H10···O3^xi	2.6100
C12···C2^viii	3.582 (3)	H10···C7^xi	2.8800
C12···C4^viii	3.556 (3)	H12···O4^ix	2.7200
C12···C6^ix	3.550 (3)	H12···H4^ix	2.5700
C13···C4^viii	3.441 (3)	H13···O3	2.5100
C3···H3ⁱ	3.0100

C4—O1—C5	118.6 (2)	C2—C6—H6A	109.00
C9—O4—H4	109.00	C2—C6—H6C	109.00
C1—N1—C2	121.09 (15)	H6A—C6—H6B	109.00
C1—N3—C4	116.52 (18)	C2—C6—H6B	109.00
C1—N1—H1	119.00	H6B—C6—H6C	110.00
C2—N1—H1	119.00	H6A—C6—H6C	109.00
H2A—N2—H2B	120.00	O2—C7—C8	117.66 (18)
C1—N2—H2A	120.00	O3—C7—C8	119.57 (18)
C1—N2—H2B	120.00	O2—C7—O3	122.77 (16)
N2—C1—N3	119.68 (19)	C7—C8—C13	120.12 (18)
N1—C1—N3	122.16 (19)	C9—C8—C13	118.69 (16)
N1—C1—N2	118.17 (16)	C7—C8—C9	121.19 (19)
N1—C2—C6	116.68 (16)	O4—C9—C10	118.8 (3)
C3—C2—C6	125.0 (2)	C8—C9—C10	119.4 (3)
N1—C2—C3	118.35 (19)	O4—C9—C8	121.81 (17)
C2—C3—C4	118.0 (2)	C9—C10—C11	120.6 (3)
N3—C4—C3	123.91 (16)	C10—C11—C12	120.8 (2)
O1—C4—C3	116.42 (19)	C11—C12—C13	119.3 (2)
O1—C4—N3	119.67 (18)	C8—C13—C12	121.3 (2)
C2—C3—H3	121.00	C9—C10—H10	120.00
C4—C3—H3	121.00	C11—C10—H10	120.00
O1—C5—H5B	109.00	C10—C11—H11	120.00
O1—C5—H5C	109.00	C12—C11—H11	120.00
O1—C5—H5A	109.00	C11—C12—H12	120.00
H5A—C5—H5C	110.00	C13—C12—H12	120.00
H5B—C5—H5C	109.00	C8—C13—H13	119.00
H5A—C5—H5B	110.00	C12—C13—H13	119.00

C5—O1—C4—N3	1.9 (3)	O2—C7—C8—C13	−175.72 (17)
C5—O1—C4—C3	−178.55 (18)	O3—C7—C8—C9	−176.44 (18)
C2—N1—C1—N2	−179.22 (17)	O3—C7—C8—C13	4.1 (3)
C2—N1—C1—N3	0.8 (3)	C7—C8—C9—O4	1.2 (3)
C1—N1—C2—C3	−0.4 (2)	C7—C8—C9—C10	−178.58 (19)
C1—N1—C2—C6	−179.52 (16)	C13—C8—C9—O4	−179.40 (18)
C4—N3—C1—N1	−0.5 (3)	C13—C8—C9—C10	0.8 (3)
C4—N3—C1—N2	179.56 (17)	C7—C8—C13—C12	178.86 (18)
C1—N3—C4—O1	179.29 (16)	C9—C8—C13—C12	−0.6 (3)
C1—N3—C4—C3	−0.3 (3)	O4—C9—C10—C11	179.7 (2)
N1—C2—C3—C4	−0.3 (3)	C8—C9—C10—C11	−0.5 (3)
C6—C2—C3—C4	178.73 (18)	C9—C10—C11—C12	−0.2 (4)
C2—C3—C4—O1	−178.88 (16)	C10—C11—C12—C13	0.4 (4)
C2—C3—C4—N3	0.7 (3)	C11—C12—C13—C8	−0.1 (3)
O2—C7—C8—C9	3.7 (3)

Symmetry codes: (i) −x+3, −y+1, −z+2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z+1/2; (v) x+1, −y+3/2, z+1/2; (vi) −x+2, y+1/2, −z+3/2; (vii) x+1, y, z+1; (viii) x−1, y, z−1; (ix) x−1, −y+3/2, z−1/2; (x) −x+2, y−1/2, −z+3/2; (xi) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.84	2.7033 (19)	176
N2—H2A···O3ⁱⁱⁱ	0.86	2.00	2.816 (3)	158
N2—H2B···O3	0.86	1.99	2.830 (2)	165
O4—H4···O2	0.82	1.81	2.534 (2)	147
C3—H3···O1ⁱ	0.93	2.48	3.374 (3)	160

Symmetry codes: (i) −x+3, −y+1, −z+2; (iii) −x+1, −y+1, −z+1.

Footnotes

‡Thomson Reuters ResearcherID: A-5599-2009.

Funding information

PS and KB thank the Department of Science and Technology (DST-SERB), grant No. SB/FT/CS-058/2013, New Delhi, India, for financial support.

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