Crystal structure and hydrogen-bonding patterns in 5-fluoro­cytosinium picrate

Mohana, M.; Thomas Muthiah, P.; McMillen, C.D.

doi:10.1107/S205698901700216X

research communications

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ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 361-364

https://doi.org/10.1107/S205698901700216X

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Crystal structure and hydrogen-bonding patterns in 5-fluorocytosinium picrate

Marimuthu Mohana,^a Packianathan Thomas Muthiah ^a ^* and Colin D. McMillen ^b

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu, India, and ^bDepartment of Chemistry, Clemson University, 379 H.L. Hunter Laboratories, Clemson, SC 29634, USA
^*Correspondence e-mail: tommtrichy@yahoo.co.in

Edited by G. Smith, Queensland University of Technology, Australia (Received 24 January 2017; accepted 9 February 2017; online 14 February 2017)

In the crystal structure of the title compound, 5-fluorocytosinium picrate, C₄H₅FN₃O⁺·C₆H₂N₃O₇⁻, one N heteroatom of the 5-fluorocytosine (5FC) ring is protonated. The 5FC ring forms a dihedral angle of 19.97 (11)° with the ring of the picrate (PA⁻) anion. In the crystal, the 5FC⁺ cation interacts with the PA⁻ anion through three-centre N—H⋯O hydrogen bonds, forming two conjoined rings having R₂¹(6) and R₁²(6) motifs, and is extended by N—H⋯O hydrogen bonds and C—H⋯O interactions into a two-dimensional sheet structure lying parallel to (001). Also present in the crystal structure are weak C—F⋯π interactions.

Keywords: crystal structure; 5-fluorocytosine; picrate; hydrogen bonding; bifurcated interactions.

CCDC reference: 1531927

1. Chemical context

Crystal engineering is defined as the rational design of crystalline solids through control of intermolecular interactions (hydrogen bonding, hydrophobic forces, van der Waals forces, π–π interactions and electrostatic forces). New solid forms of pharmaceuticals are designed using the crystal engineering approach. These engineered solids have technological and legal importance. Among the intermolecular interactions, hydrogen bonding is the master key for molecular recognition in biological systems because of its strength and directionality (Almarsson & Zaworoko, 2004 ; Desiraju, 1995 ). It plays a dominant role in molecular aggregates (Samuel, 1997 ; Tutughamiarso & Egert, 2012 ) and three-dimensional structure, stability and function of biomacromolecules (Gould, 1986 ). In particular, pyrimidine derivatives are used in the treatment of antiviral, antifungal, antitumor and cardiovascular diseases. 5-fluorocytosine (5FC) is a synthetic antimycotic compound, first synthesized in 1957 and widely used as an antitumor agent it is also active against fungal infection (Heidelberger et al., 1957 ; Portalone & Colapietro, 2007 ; Vermes et al., 2000 ). It becomes active by deamination of 5FC into 5-fluorouracil by the enzyme cytosine deaminase (CD) and inhibits RNA and DNA synthesis (Morschhäuser, 2003 ). Picric acid forms charge-transfer complexes with many organic compounds. It functions not only as an acceptor to form π-stacking complexes with aromatic biomolecules, but also as an acidic ligand to form salts with polar biomolecules through specific electrostatic hydrogen-bonding interactions (In et al., 1997 ). The present work is focused on the understanding of supramolecular hydrogen-bonding patterns exhibited by the interaction of 5FC and picric acid, giving the (1:1) title salt, C₄H₅FN₃O⁺·C₆H₂N₃O₇⁻ whose structure and hydrogen-bonding patterns are reported on herein.

2. Structural commentary

The asymmetric unit contains one 5-fluorocytosinium cation (5FC⁺) and one picrate anion (PA⁻) (Fig. 1). The 5-fluorocytosine cation is protonated at the N3 atom, as is evident from the widening of the corresponding internal angle from 120.8 (5)° to 125.37 (17)° compared to neutral 5FC (Louis et al., 1982 ). The dihedral angle between the planes of the rigs in the cation and anion is 19.97 (11)°. In the picrate (PA⁻) anion, the nitro groups lie variously out of the parent benzene ring, with torsion angles C9—C8—N5—O4, C9—C10—N6—O7 and C11—C12—N7—O9 of 166.2 (2), −171.7 (2) and 147.2 (2)°, respectively.

Figure 1
The naming scheme for the 5FC⁺ cation and the PA⁻ anion in the title compound, showing 30% probability level displacement ellipsoids. Dashed lines represent hydrogen bonds.

3. Supramolecular features

In this crystal structure, the N4-amino group and protonated N3 atom of the 5FC⁺ cation interact with atoms O3 and O9 of the picrate anion through three-centre N—H⋯O hydrogen bonds, forming two fused-ring motifs with graph-sets $[R_{1}^{2}]$ (6) and $[R_{2}^{1}]$ (6) (Fig. 1). One of the N4-amino hydrogen atoms of the 5FC⁺ cation acts as a three-centre donor and the O3 atom of the PA⁻ anion acts as a three-centre acceptor. This type of interaction has also been reported in the crystal structures of 2-amino-4,6-dimethylpyrimidinium picrate (Subashini et al., 2006 ) and 2-amino-4,6- dimethoxypyrimidinium picrate, pyrimethaminium picrate dimethyl sulfoxide (Thanigaimani et al., 2009 ). Similarly, the other hetero nitrogen atom (N1) of the cation and both the phenolate O3ⁱ and a nitro O4ⁱ atom of a PA⁻ anion form an $[R_{1}^{2}]$ (6) ring motif through N—H⋯O hydrogen bonds with a second C—H⋯O4ⁱ interaction, closing an $[R_{2}^{1}]$ (5) ring (Table 1). A similar type of interaction has also been observed in the crystal structure of cytosinium hydrogen chloroanilate monohydrate (Gotoh et al., 2006 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.88	1.92	2.794 (3)	175
N1—H1⋯O4ⁱ	0.88	2.56	3.021 (3)	114
N3—H3⋯O3	0.88	2.22	2.915 (2)	136
N4—H4A⋯O3	0.88	2.10	2.828 (2)	139
N4—H4A⋯O9	0.88	2.18	2.782 (3)	125
N4—H4B⋯O2ⁱⁱ	0.88	1.96	2.832 (3)	171
C6—H6⋯O4ⁱ	0.95	2.51	3.003 (3)	113
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x-{\script{1\over 2}}, y-{\script{3\over 2}}, z]$ .

Further, the symmetry-related O2ⁱⁱ atom and the amino group of the 5FC⁺ cation are connected through an N—H⋯O hydrogen bond, forming a two-dimensional supramolecular network lying parallel to (001) (Fig. 2). Also present in the crystal structure is a weak C5—F5⋯π interaction (Fig. 3) between 5FC⁺ cations [C5⋯Cg^iv = 3.4002 (19) Å; C—F⋯Cg = 88.34 (12)°, where Cg is the centroid of the N1–C6 ring; symmetry code: (iv) −x, −y, −z + 1]. A similar angle [90.5 (2)°] has been reported for a C—F⋯Cg interaction in an acridinium trifluoromethane sulfonate compound (Sikorski et al., 2005 ).

Figure 2
A view of the supramolecular network formed via N—H⋯O and C—H⋯O interactions. Dashed lines represent hydrogen bonds. For symmetry codes, see Table 1

Figure 3
A view of the C5—F5⋯π interaction between 5FC⁺ cations.

4. Database survey

The crystal structures of 5-fluorocytosine monohydrates (Louis et al., 1982; Portalone & Colapietro, 2006 ; Portalone & Colapietro, 2007; Portalone, 2011 ), polymorphs (Hulme & Tocher, 2006 ; Tutughamiarso & Egert, 2012 ), salts (Perumalla et al., 2013 ) and co-crystals (Tutughamiarso et al., 2012; da Silva et al., 2014 ) have been reported in the literature. From our laboratory, 5-fluorocytosinium salicylate (Prabakaran et al., 2001 ), 5-fluorocytosinium 3-hydroxypicolinate (Karthikeyan et al., 2014 ) and 5-fluorocytosine melamine (Mohana et al., 2016 ) have been reported. Various salts and co-crystals of picric acid have also been reported in the literature (Subashini et al., 2006; Thanigaimani et al., 2009; Nagata et al., 1995 ; Smith et al., 2004 ; Gotoh et al., 2004 ).

5. Synthesis and crystallization

A hot aqueous solution of 5-fluorocytosine (32 mg) and picric acid (57 mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed to 353 K wrong symmetry description - inversion centre in central benzene ring over a water bath for half an hour and kept for slow evaporation. After a week, colourless prismatic crystals were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were positioned geometrically (C—H = 0.95 Å and N—H = 0.88 Å) and were refined using a riding model with U_iso(H) = 1.2U_eq(parent atom).

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₅FN₃O⁺·C₆H₂N₃O₇⁻
M_r	358.22
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	7.7463 (15), 13.235 (3), 25.642 (5)
V (Å³)	2628.9 (9)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.17
Crystal size (mm)	0.65 × 0.58 × 0.20

Data collection
Diffractometer	Rigaku AFC-8S
Absorption correction	Multi-scan multi-scan
T_min, T_max	0.899, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	21815, 2779, 2367
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.174, 1.09
No. of reflections	2779
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.36
Computer programs: CrystalClear (Rigaku/MSC, 2008 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2008 ), POVRay (Cason, 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1531927

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901700216X/zs2375sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700216X/zs2375Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901700216X/zs2375Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and POVRay (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

5-Fluorocytosinium picrate top

Crystal data top

C₄H₅FN₃O⁺·C₆H₂N₃O₇⁻	D_x = 1.810 Mg m⁻³
M_r = 358.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2779 reflections
a = 7.7463 (15) Å	θ = 3.1–26.7°
b = 13.235 (3) Å	µ = 0.17 mm⁻¹
c = 25.642 (5) Å	T = 200 K
V = 2628.9 (9) Å³	Prism, colorless
Z = 8	0.65 × 0.58 × 0.20 mm
F(000) = 1456

Data collection top

Rigaku AFC-8S diffractometer	2779 independent reflections
Radiation source: fine focus sealed tube	2367 reflections with I > 2σ(I)
Detector resolution: 14.6199 pixels mm^-1	R_int = 0.041
ω scans	θ_max = 26.7°, θ_min = 3.1°
Absorption correction: multi-scan multi-scan	h = −9→7
T_min = 0.899, T_max = 0.967	k = −16→16
21815 measured reflections	l = −32→32

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.174	w = 1/[σ²(F_o²) + (0.1025P)² + 1.2366P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2779 reflections	Δρ_max = 0.28 e Å⁻³
226 parameters	Δρ_min = −0.36 e Å⁻³

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
O3	0.4311 (2)	0.65661 (11)	0.61738 (6)	0.0381 (4)
O9	0.5493 (2)	0.46460 (13)	0.62650 (7)	0.0440 (4)
O7	0.5646 (3)	0.58196 (18)	0.85486 (7)	0.0566 (5)
O8	0.7432 (2)	0.45799 (14)	0.68664 (7)	0.0469 (4)
C7	0.4418 (3)	0.65628 (15)	0.66650 (8)	0.0317 (5)
N7	0.6116 (2)	0.49512 (14)	0.66734 (7)	0.0353 (4)
C12	0.5282 (3)	0.57726 (16)	0.69555 (8)	0.0317 (4)
C8	0.3714 (3)	0.73340 (16)	0.70030 (8)	0.0338 (5)
C10	0.4631 (3)	0.65060 (18)	0.77790 (8)	0.0365 (5)
O4	0.2970 (3)	0.83845 (18)	0.63172 (8)	0.0664 (7)
N5	0.2811 (3)	0.81933 (15)	0.67800 (8)	0.0390 (4)
O5	0.1900 (3)	0.87035 (16)	0.70710 (7)	0.0595 (6)
C11	0.5410 (3)	0.57451 (16)	0.74889 (8)	0.0344 (5)
H11	0.601989	0.521474	0.765720	0.041*
O6	0.3831 (4)	0.70675 (18)	0.85946 (8)	0.0733 (7)
N6	0.4708 (3)	0.64684 (16)	0.83447 (8)	0.0448 (5)
C9	0.3783 (3)	0.72956 (17)	0.75414 (9)	0.0366 (5)
H9	0.325057	0.780799	0.774507	0.044*
F5	0.2136 (2)	0.44284 (10)	0.45073 (6)	0.0484 (4)
O2	0.0618 (2)	0.81443 (11)	0.51702 (7)	0.0412 (4)
N3	0.1841 (2)	0.66094 (13)	0.53164 (6)	0.0320 (4)
H3	0.209477	0.679151	0.563747	0.038*
N1	0.0672 (3)	0.69947 (14)	0.45092 (7)	0.0371 (4)
H1	0.019456	0.742373	0.429023	0.044*
N4	0.3114 (3)	0.50588 (14)	0.54809 (7)	0.0383 (4)
H4A	0.338817	0.526201	0.579703	0.046*
H4B	0.339680	0.444694	0.537710	0.046*
C2	0.1011 (3)	0.73142 (15)	0.50045 (8)	0.0325 (5)
C4	0.2293 (3)	0.56620 (15)	0.51674 (8)	0.0316 (4)
C5	0.1785 (3)	0.53785 (16)	0.46564 (8)	0.0348 (5)
C6	0.1035 (3)	0.60450 (18)	0.43367 (9)	0.0392 (5)
H6	0.075454	0.585605	0.398941	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0529 (10)	0.0359 (8)	0.0256 (7)	−0.0065 (7)	−0.0044 (6)	0.0023 (6)
O9	0.0528 (10)	0.0445 (9)	0.0347 (8)	0.0036 (7)	−0.0071 (7)	−0.0055 (7)
O7	0.0523 (11)	0.0861 (15)	0.0315 (9)	−0.0037 (10)	−0.0075 (8)	0.0120 (9)
O8	0.0448 (9)	0.0477 (10)	0.0483 (10)	0.0065 (7)	−0.0101 (8)	0.0000 (8)
C7	0.0347 (10)	0.0337 (10)	0.0268 (10)	−0.0097 (8)	−0.0011 (8)	0.0030 (7)
N7	0.0386 (10)	0.0369 (9)	0.0305 (9)	−0.0042 (7)	−0.0001 (7)	0.0035 (7)
C12	0.0335 (10)	0.0331 (10)	0.0286 (10)	−0.0057 (8)	−0.0010 (8)	0.0025 (8)
C8	0.0373 (11)	0.0315 (10)	0.0327 (10)	−0.0057 (8)	−0.0022 (8)	0.0014 (8)
C10	0.0408 (12)	0.0434 (12)	0.0252 (10)	−0.0119 (9)	−0.0015 (8)	0.0014 (8)
O4	0.0806 (15)	0.0708 (14)	0.0478 (11)	0.0296 (11)	0.0199 (10)	0.0262 (10)
N5	0.0424 (10)	0.0379 (10)	0.0368 (10)	−0.0034 (8)	0.0003 (8)	0.0009 (8)
O5	0.0814 (15)	0.0547 (12)	0.0424 (10)	0.0228 (10)	−0.0041 (9)	−0.0079 (8)
C11	0.0357 (11)	0.0380 (10)	0.0296 (10)	−0.0076 (8)	−0.0047 (8)	0.0058 (8)
O6	0.122 (2)	0.0654 (13)	0.0320 (9)	0.0087 (13)	0.0120 (11)	−0.0020 (9)
N6	0.0538 (12)	0.0518 (12)	0.0287 (10)	−0.0135 (10)	−0.0011 (9)	0.0027 (8)
C9	0.0396 (12)	0.0386 (11)	0.0317 (11)	−0.0097 (9)	0.0015 (8)	−0.0019 (8)
F5	0.0673 (10)	0.0373 (7)	0.0404 (8)	0.0123 (6)	−0.0140 (7)	−0.0128 (6)
O2	0.0538 (10)	0.0292 (8)	0.0406 (9)	0.0029 (7)	−0.0023 (7)	−0.0004 (6)
N3	0.0404 (10)	0.0302 (9)	0.0252 (8)	0.0019 (7)	−0.0033 (7)	−0.0028 (6)
N1	0.0491 (11)	0.0347 (9)	0.0274 (9)	0.0077 (8)	−0.0028 (8)	0.0032 (7)
N4	0.0514 (11)	0.0310 (9)	0.0324 (9)	0.0053 (8)	−0.0094 (8)	−0.0031 (7)
C2	0.0380 (11)	0.0308 (11)	0.0288 (10)	−0.0023 (8)	0.0005 (8)	0.0012 (8)
C4	0.0360 (10)	0.0303 (10)	0.0285 (10)	−0.0039 (8)	−0.0006 (8)	0.0000 (8)
C5	0.0439 (11)	0.0312 (10)	0.0294 (10)	0.0031 (8)	−0.0032 (9)	−0.0057 (8)
C6	0.0473 (12)	0.0418 (12)	0.0284 (10)	0.0055 (10)	−0.0053 (9)	−0.0049 (8)

Geometric parameters (Å, º) top

O3—C7	1.262 (3)	O6—N6	1.225 (3)
O9—N7	1.222 (3)	C9—H9	0.9500
O7—N6	1.240 (3)	F5—C5	1.342 (2)
O8—N7	1.235 (3)	O2—C2	1.217 (3)
C7—C8	1.446 (3)	N3—C4	1.357 (3)
C7—C12	1.448 (3)	N3—C2	1.387 (3)
N7—C12	1.457 (3)	N3—H3	0.8800
C12—C11	1.372 (3)	N1—C6	1.362 (3)
C8—C9	1.383 (3)	N1—C2	1.364 (3)
C8—N5	1.452 (3)	N1—H1	0.8800
C10—C9	1.377 (3)	N4—C4	1.299 (3)
C10—C11	1.389 (3)	N4—H4A	0.8800
C10—N6	1.453 (3)	N4—H4B	0.8800
O4—N5	1.219 (3)	C4—C5	1.419 (3)
N5—O5	1.229 (3)	C5—C6	1.337 (3)
C11—H11	0.9500	C6—H6	0.9500

O3—C7—C8	124.81 (19)	C10—C9—C8	119.2 (2)
O3—C7—C12	123.1 (2)	C10—C9—H9	120.4
C8—C7—C12	112.08 (18)	C8—C9—H9	120.4
O9—N7—O8	122.5 (2)	C4—N3—C2	125.37 (17)
O9—N7—C12	119.83 (18)	C4—N3—H3	117.3
O8—N7—C12	117.63 (18)	C2—N3—H3	117.3
C11—C12—C7	124.4 (2)	C6—N1—C2	123.29 (18)
C11—C12—N7	116.32 (18)	C6—N1—H1	118.4
C7—C12—N7	119.24 (18)	C2—N1—H1	118.4
C9—C8—C7	123.9 (2)	C4—N4—H4A	120.0
C9—C8—N5	116.14 (19)	C4—N4—H4B	120.0
C7—C8—N5	119.89 (18)	H4A—N4—H4B	120.0
C9—C10—C11	121.4 (2)	O2—C2—N1	123.8 (2)
C9—C10—N6	119.2 (2)	O2—C2—N3	121.46 (19)
C11—C10—N6	119.5 (2)	N1—C2—N3	114.70 (18)
O4—N5—O5	122.3 (2)	N4—C4—N3	121.33 (19)
O4—N5—C8	119.8 (2)	N4—C4—C5	123.0 (2)
O5—N5—C8	117.87 (19)	N3—C4—C5	115.65 (19)
C12—C11—C10	118.9 (2)	C6—C5—F5	122.10 (19)
C12—C11—H11	120.6	C6—C5—C4	120.8 (2)
C10—C11—H11	120.6	F5—C5—C4	117.05 (19)
O6—N6—O7	123.5 (2)	C5—C6—N1	120.0 (2)
O6—N6—C10	118.5 (2)	C5—C6—H6	120.0
O7—N6—C10	117.9 (2)	N1—C6—H6	120.0

O4—N5—C8—C7	−16.2 (3)	O3—C7—C8—C9	177.2 (2)
O4—N5—C8—C9	166.2 (2)	C12—C7—C8—N5	179.5 (2)
O5—N5—C8—C7	163.6 (2)	C12—C7—C8—C9	−3.0 (3)
O5—N5—C8—C9	−14.0 (3)	O3—C7—C12—N7	1.8 (3)
O6—N6—C10—C9	9.2 (4)	O3—C7—C12—C11	−179.6 (2)
O6—N6—C10—C11	−170.7 (2)	C8—C7—C12—N7	−178.00 (19)
O7—N6—C10—C9	−171.7 (2)	N5—C8—C9—C10	−179.5 (2)
O7—N6—C10—C11	8.4 (3)	C7—C8—C9—C10	3.0 (4)
O8—N7—C12—C7	147.0 (2)	C8—C9—C10—N6	179.8 (2)
O8—N7—C12—C11	−31.8 (3)	C8—C9—C10—C11	−0.3 (4)
O9—N7—C12—C7	−34.0 (3)	N6—C10—C11—C12	178.0 (2)
O9—N7—C12—C11	147.2 (2)	C9—C10—C11—C12	−1.9 (3)
C2—N1—C6—C5	−1.1 (4)	C10—C11—C12—N7	−179.6 (2)
C6—N1—C2—O2	−176.4 (2)	C10—C11—C12—C7	1.7 (4)
C6—N1—C2—N3	3.1 (3)	N3—C4—C5—F5	−176.70 (18)
C2—N3—C4—C5	−3.0 (3)	N3—C4—C5—C6	5.1 (3)
C4—N3—C2—O2	178.6 (2)	N4—C4—C5—F5	2.2 (3)
C4—N3—C2—N1	−0.9 (3)	N4—C4—C5—C6	−175.9 (2)
C2—N3—C4—N4	178.0 (2)	F5—C5—C6—N1	178.7 (2)
O3—C7—C8—N5	−0.2 (3)	C4—C5—C6—N1	−3.3 (4)
C8—C7—C12—C11	0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.88	1.92	2.794 (3)	175
N1—H1···O4ⁱ	0.88	2.56	3.021 (3)	114
N3—H3···O3	0.88	2.22	2.915 (2)	136
N4—H4A···O3	0.88	2.10	2.828 (2)	139
N4—H4A···O9	0.88	2.18	2.782 (3)	125
N4—H4B···O2ⁱⁱ	0.88	1.96	2.832 (3)	171
C6—H6···O4ⁱ	0.95	2.51	3.003 (3)	113

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

Acknowledgements

MM thanks UGC-BSR, India, for the award of an RFSMS. PTM thanks the UGC for a one-time BSR–faculty grant.

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