2-Amino­pyridinium 2,4-di­nitro­phenolate

Devi, S.R.; Akilan, R.; Kumar, R.M.; Ganesh, T.; Chakkaravarthi, G.

doi:10.1107/S2414314616014899

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161489

doi:10.1107/S2414314616014899

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2-Aminopyridinium 2,4-dinitrophenolate

S. Reena Devi,^a R. Akilan,^b R. Mohan Kumar,^a T. Ganesh ^a ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: ntganesh@yahoo.co.in, chakkaravarthi_2005@yahoo.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 26 August 2016; accepted 21 September 2016; online 23 September 2016)

The asymmetric unit of the title organic salt, C₅H₇N₂⁺·C₆H₃N₂O₅⁻, comprises two 2-aminopyridinium cations and two 2,4-dinitrophenolate anions. The cations are protonated at the pyridine N atoms, while the anions are deprotonated at hydroxyl O atoms. In the crystal, bifurcated N—H⋯O hydrogen bonds generate two R¹₂(6), two R²₁(6), and one R²₁(4) ring motifs. Adjacent anions and cations are linked by N—H⋯O hydrogen bonds into infinite chains along [110]. Weak C—H⋯O contacts and π–π interactions further link the components, forming a complex three-dimensional supramolecular network.

Keywords: crystal structure; organic salt; pyridinium; phenolate; hydrogen bonding.

CCDC reference: 1505554

Structure description

In order to investigate if pyridine derivatives exhibit biological activities such as antiviral (Hamdouchi et al., 1999 ) or antibacterial activity (Rival et al., 1992 ), we synthesized and determined the crystal structure of the title organic salt (Fig. 1). The geometric parameters are in good agreement with those reported for similar structures (Hemamalini & Fun, 2010 ; Sivakumar et al., 2016 ). There are two independent 2-aminopyridinium cations and two 2,4-dinitrophenolate anions in the asymmetric unit. The cations are protonated at the pyridine N atoms (N5 and N7) and the anions are deprotonated at the hydroxyl O atoms (O1 and O6).

Figure 1
The molecular structure of the title compound, with 30% probability displacement ellipsoids.

In the crystal, pairs of bifurcated hydrogen bonds N6—H6A⋯O1ⁱ, N5—H5⋯O1ⁱ and N8—H8A⋯O6ⁱⁱⁱ, N7—H7⋯O6ⁱⁱⁱ generate two R₂¹(6) ring motifs. Pairs of hydrogen bonds N5—H5⋯O1ⁱ, N5—H5⋯O2ⁱ and N7—H7⋯O6ⁱⁱⁱ, N7—H7⋯O10ⁱⁱⁱ generate two R₁²(6) ring motifs. Finally, the N8—H8B⋯O2ⁱ and N8—H8B⋯O3ⁱ hydrogen bonds generate an R₁²(4) ring motif (Figs. 2 and 3). Adjacent anions and cations are linked by N—H⋯O hydrogen bonds (Table 1) into infinite chains along [110]. The crystal also features weak C—H⋯O hydrogen bonds and π–π interactions between symmetry-related C7–C12 benzene rings [centroid-to-centroid distance: 3.4949 (7) Å; symmetry code: 2 − x, 1 − y, −z], leading to the formation of a three-dimensional network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O1ⁱ	0.88 (1)	1.92 (1)	2.7304 (16)	152 (2)
N5—H5⋯O2ⁱ	0.88 (1)	2.31 (2)	2.9553 (17)	130 (2)
N6—H6A⋯O1ⁱ	0.86	2.02	2.7712 (19)	145
N6—H6B⋯O4ⁱⁱ	0.86	2.15	2.9849 (18)	162
N7—H7⋯O6ⁱⁱⁱ	0.88 (1)	1.83 (1)	2.6627 (15)	157 (2)
N7—H7⋯O10ⁱⁱⁱ	0.88 (1)	2.31 (2)	2.8975 (17)	124 (2)
N8—H8A⋯O6ⁱⁱⁱ	0.86	2.04	2.7727 (16)	143
N8—H8B⋯O2ⁱ	0.86	2.42	3.2740 (17)	175
N8—H8B⋯O3ⁱ	0.86	2.50	3.1445 (17)	132
C3—H3⋯O8	0.93	2.56	3.1944 (18)	126
C18—H18⋯O10ⁱⁱⁱ	0.93	2.51	3.034 (2)	116
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+3, -y+2, -z+1; (iii) -x+1, -y+1, -z.

Figure 2
The crystal packing of the title compound viewed along b axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
A partial view of the crystal packing of the title compound, showing the ring motifs.

Synthesis and crystallization

The title salt was synthesized from the raw materials 2-aminopyridine (2.353 g) and 2,4-dinitrophenol (4.603 g), which were taken in 1:1 ratio and dissolved in a mixture of water and ethanol, at room temperature. After a period of three weeks, good quality crystals suitable for X-ray diffraction were harvested.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. In the last least-squares cycles, pyridinium N5—H5 and N7—H7 bond lengths were restrained to 0.88 (1) Å.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₃N₂O₅·C₅H₇N₂
M_r	278.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	7.6303 (2), 9.3142 (3), 17.2518 (5)
α, β, γ (°)	90.339 (2), 99.468 (2), 99.556 (3)
V (Å³)	1191.91 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.26 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD Diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.963, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	44716, 10159, 5393
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.823

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.157, 1.01
No. of reflections	10159
No. of parameters	370
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.26
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1505554

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616014899/bh4014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014899/bh4014Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014899/bh4014Isup3.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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2015) and PLATON.

2-Aminopyridinium 2,4-dinitrophenolate top

Crystal data top

C₅H₇N₂⁺·C₆H₃N₂O₅⁻	Z = 4
M_r = 278.23	F(000) = 576
Triclinic, P1	D_x = 1.550 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6303 (2) Å	Cell parameters from 9905 reflections
b = 9.3142 (3) Å	θ = 2.3–32.4°
c = 17.2518 (5) Å	µ = 0.13 mm⁻¹
α = 90.339 (2)°	T = 295 K
β = 99.468 (2)°	Block, colourless
γ = 99.556 (3)°	0.30 × 0.26 × 0.20 mm
V = 1191.91 (6) Å³

Data collection top

Bruker APEXII CCD Diffractometer	10159 independent reflections
Radiation source: fine-focus sealed tube	5393 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and φ scan	θ_max = 35.8°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→12
T_min = 0.963, T_max = 0.975	k = −15→15
44716 measured reflections	l = −28→26

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)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.157	w = 1/[σ²(F_o²) + (0.0596P)² + 0.2916P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
10159 reflections	Δρ_max = 0.30 e Å⁻³
370 parameters	Δρ_min = −0.26 e Å⁻³
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.026 (2)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	U_iso*/U_eq
C1	1.37352 (17)	0.62615 (14)	0.36601 (8)	0.0331 (3)
C2	1.25635 (19)	0.51343 (16)	0.32011 (8)	0.0394 (3)
H2	1.2510	0.5088	0.2659	0.047*
C3	1.1515 (2)	0.41180 (17)	0.35563 (8)	0.0424 (3)
H3	1.0741	0.3383	0.3244	0.051*
C4	1.15318 (18)	0.41126 (15)	0.43895 (8)	0.0360 (3)
C5	1.27290 (17)	0.53107 (14)	0.48189 (7)	0.0317 (3)
C6	1.38030 (18)	0.63512 (14)	0.44565 (8)	0.0332 (3)
H6	1.4570	0.7110	0.4754	0.040*
C7	0.92604 (16)	0.28396 (13)	0.06858 (7)	0.0306 (2)
C8	0.89794 (17)	0.41705 (13)	0.09385 (7)	0.0307 (2)
H8	0.9471	0.4525	0.1446	0.037*
C9	0.79599 (16)	0.49808 (13)	0.04331 (7)	0.0291 (2)
C10	0.71871 (17)	0.44915 (13)	−0.03568 (7)	0.0316 (2)
C11	0.75481 (19)	0.30915 (14)	−0.05728 (8)	0.0366 (3)
H11	0.7077	0.2714	−0.1078	0.044*
C12	0.85390 (18)	0.22925 (14)	−0.00781 (8)	0.0352 (3)
H12	0.8738	0.1390	−0.0244	0.042*
C13	1.1666 (2)	0.92922 (16)	0.43826 (10)	0.0431 (3)
C14	1.2566 (2)	1.03100 (18)	0.39219 (12)	0.0578 (4)
H14	1.3414	1.1086	0.4161	0.069*
C15	1.2192 (3)	1.0155 (2)	0.31277 (13)	0.0631 (5)
H15	1.2790	1.0829	0.2824	0.076*
C16	1.0930 (2)	0.9006 (2)	0.27611 (11)	0.0572 (4)
H16	1.0683	0.8900	0.2216	0.069*
C17	1.0067 (2)	0.80451 (18)	0.32117 (9)	0.0458 (3)
H17	0.9213	0.7269	0.2976	0.055*
C18	0.4901 (2)	0.10146 (16)	0.09284 (10)	0.0461 (3)
H18	0.4265	0.0764	0.0425	0.055*
C19	0.5773 (2)	0.00349 (16)	0.13340 (11)	0.0519 (4)
H19	0.5766	−0.0879	0.1113	0.062*
C20	0.6681 (2)	0.04270 (17)	0.20908 (11)	0.0500 (4)
H20	0.7276	−0.0238	0.2382	0.060*
C21	0.6711 (2)	0.17668 (17)	0.24104 (9)	0.0454 (3)
H21	0.7319	0.2018	0.2918	0.055*
C22	0.58139 (18)	0.27768 (15)	0.19663 (8)	0.0355 (3)
N1	1.29096 (16)	0.54893 (13)	0.56547 (6)	0.0377 (3)
N2	1.49156 (17)	0.73176 (13)	0.33004 (7)	0.0404 (3)
N3	1.03421 (16)	0.20195 (13)	0.12121 (7)	0.0384 (3)
N4	0.77467 (16)	0.63762 (12)	0.07403 (7)	0.0365 (2)
N5	1.04392 (16)	0.82054 (13)	0.40076 (7)	0.0392 (3)
N6	1.1972 (2)	0.93352 (16)	0.51656 (9)	0.0579 (4)
H6A	1.1389	0.8676	0.5418	0.069*
H6B	1.2752	1.0022	0.5419	0.069*
N7	0.49370 (16)	0.23546 (12)	0.12421 (7)	0.0354 (2)
N8	0.5821 (2)	0.41215 (14)	0.22250 (7)	0.0487 (3)
H8A	0.5269	0.4704	0.1929	0.058*
H8B	0.6377	0.4411	0.2688	0.058*
O1	1.05465 (16)	0.31141 (13)	0.46840 (6)	0.0534 (3)
O2	1.21387 (16)	0.45502 (13)	0.60378 (6)	0.0512 (3)
O3	1.38712 (18)	0.65870 (13)	0.59828 (6)	0.0585 (3)
O4	1.58993 (18)	0.83193 (13)	0.37099 (7)	0.0587 (3)
O5	1.4934 (2)	0.71793 (14)	0.25978 (7)	0.0644 (4)
O6	0.62580 (15)	0.51757 (11)	−0.08511 (6)	0.0467 (3)
O7	1.05377 (18)	0.08143 (13)	0.09936 (7)	0.0594 (3)
O8	1.10477 (18)	0.25497 (14)	0.18655 (7)	0.0577 (3)
O9	0.82825 (19)	0.66899 (13)	0.14377 (7)	0.0600 (3)
O10	0.70515 (18)	0.72215 (12)	0.02972 (7)	0.0575 (3)
H5	0.993 (2)	0.7560 (17)	0.4309 (10)	0.062 (6)*
H7	0.441 (2)	0.3037 (17)	0.0994 (10)	0.061 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0341 (6)	0.0327 (6)	0.0338 (6)	0.0077 (5)	0.0072 (5)	0.0015 (5)
C2	0.0420 (7)	0.0463 (8)	0.0291 (6)	0.0057 (6)	0.0059 (5)	−0.0037 (5)
C3	0.0403 (7)	0.0467 (8)	0.0361 (7)	−0.0020 (6)	0.0039 (6)	−0.0083 (6)
C4	0.0329 (6)	0.0400 (7)	0.0351 (6)	0.0052 (5)	0.0062 (5)	−0.0006 (5)
C5	0.0327 (6)	0.0373 (6)	0.0260 (5)	0.0119 (5)	0.0021 (5)	−0.0002 (5)
C6	0.0347 (6)	0.0324 (6)	0.0321 (6)	0.0098 (5)	0.0005 (5)	−0.0021 (5)
C7	0.0297 (6)	0.0315 (6)	0.0311 (6)	0.0059 (5)	0.0058 (5)	0.0055 (5)
C8	0.0319 (6)	0.0329 (6)	0.0269 (5)	0.0038 (5)	0.0055 (5)	0.0006 (4)
C9	0.0309 (6)	0.0270 (5)	0.0298 (6)	0.0049 (4)	0.0062 (5)	−0.0008 (4)
C10	0.0306 (6)	0.0306 (6)	0.0320 (6)	0.0042 (5)	0.0020 (5)	0.0007 (5)
C11	0.0420 (7)	0.0334 (6)	0.0311 (6)	0.0041 (5)	−0.0009 (5)	−0.0043 (5)
C12	0.0402 (7)	0.0285 (6)	0.0364 (6)	0.0057 (5)	0.0053 (5)	−0.0021 (5)
C13	0.0402 (7)	0.0353 (7)	0.0533 (9)	0.0097 (6)	0.0031 (6)	0.0023 (6)
C14	0.0493 (9)	0.0417 (8)	0.0791 (13)	0.0018 (7)	0.0064 (9)	0.0119 (8)
C15	0.0569 (11)	0.0608 (11)	0.0753 (13)	0.0133 (9)	0.0178 (9)	0.0323 (10)
C16	0.0553 (10)	0.0705 (11)	0.0495 (9)	0.0182 (9)	0.0107 (8)	0.0196 (8)
C17	0.0432 (8)	0.0506 (8)	0.0433 (8)	0.0104 (6)	0.0037 (6)	0.0052 (6)
C18	0.0510 (9)	0.0380 (7)	0.0481 (8)	0.0072 (6)	0.0057 (7)	−0.0044 (6)
C19	0.0586 (10)	0.0324 (7)	0.0671 (11)	0.0108 (7)	0.0143 (8)	0.0026 (7)
C20	0.0476 (9)	0.0439 (8)	0.0628 (10)	0.0149 (7)	0.0138 (7)	0.0207 (7)
C21	0.0465 (8)	0.0513 (8)	0.0400 (7)	0.0138 (7)	0.0057 (6)	0.0130 (6)
C22	0.0367 (7)	0.0397 (7)	0.0322 (6)	0.0083 (5)	0.0098 (5)	0.0059 (5)
N1	0.0418 (6)	0.0428 (6)	0.0289 (5)	0.0126 (5)	0.0017 (5)	0.0020 (5)
N2	0.0474 (7)	0.0342 (6)	0.0405 (6)	0.0065 (5)	0.0099 (5)	0.0018 (5)
N3	0.0412 (6)	0.0394 (6)	0.0365 (6)	0.0121 (5)	0.0067 (5)	0.0080 (5)
N4	0.0408 (6)	0.0334 (5)	0.0363 (6)	0.0081 (5)	0.0071 (5)	−0.0035 (4)
N5	0.0383 (6)	0.0377 (6)	0.0418 (6)	0.0079 (5)	0.0055 (5)	0.0044 (5)
N6	0.0649 (9)	0.0474 (8)	0.0534 (8)	−0.0024 (7)	−0.0011 (7)	−0.0038 (6)
N7	0.0373 (6)	0.0340 (5)	0.0361 (6)	0.0102 (4)	0.0055 (5)	0.0019 (4)
N8	0.0681 (9)	0.0452 (7)	0.0327 (6)	0.0187 (6)	−0.0007 (6)	−0.0024 (5)
O1	0.0567 (7)	0.0550 (7)	0.0433 (6)	−0.0106 (5)	0.0131 (5)	0.0001 (5)
O2	0.0595 (7)	0.0593 (7)	0.0341 (5)	0.0055 (5)	0.0098 (5)	0.0095 (5)
O3	0.0782 (9)	0.0574 (7)	0.0315 (5)	−0.0041 (6)	0.0004 (5)	−0.0069 (5)
O4	0.0673 (8)	0.0462 (6)	0.0553 (7)	−0.0109 (5)	0.0102 (6)	−0.0036 (5)
O5	0.0933 (10)	0.0556 (7)	0.0434 (6)	−0.0069 (6)	0.0284 (6)	0.0014 (5)
O6	0.0559 (6)	0.0421 (5)	0.0390 (5)	0.0170 (5)	−0.0097 (5)	−0.0001 (4)
O7	0.0781 (8)	0.0454 (6)	0.0590 (7)	0.0306 (6)	0.0033 (6)	0.0051 (5)
O8	0.0703 (8)	0.0623 (7)	0.0386 (6)	0.0235 (6)	−0.0084 (5)	0.0035 (5)
O9	0.0920 (10)	0.0498 (6)	0.0380 (6)	0.0194 (6)	0.0027 (6)	−0.0121 (5)
O10	0.0790 (8)	0.0413 (6)	0.0545 (7)	0.0296 (6)	−0.0014 (6)	−0.0027 (5)

Geometric parameters (Å, º) top

C1—C6	1.3679 (18)	C15—H15	0.9300
C1—C2	1.4050 (19)	C16—C17	1.349 (2)
C1—N2	1.4356 (18)	C16—H16	0.9300
C2—C3	1.352 (2)	C17—N5	1.3579 (19)
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.4354 (19)	C18—C19	1.349 (2)
C3—H3	0.9300	C18—N7	1.3517 (18)
C4—O1	1.2600 (17)	C18—H18	0.9300
C4—C5	1.4344 (18)	C19—C20	1.390 (2)
C5—C6	1.3834 (19)	C19—H19	0.9300
C5—N1	1.4317 (16)	C20—C21	1.356 (2)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.3731 (17)	C21—C22	1.4109 (19)
C7—C12	1.3999 (18)	C21—H21	0.9300
C7—N3	1.4353 (16)	C22—N8	1.3260 (18)
C8—C9	1.3837 (17)	C22—N7	1.3398 (17)
C8—H8	0.9300	N1—O3	1.2294 (16)
C9—C10	1.4324 (17)	N1—O2	1.2296 (15)
C9—N4	1.4446 (15)	N2—O5	1.2207 (16)
C10—O6	1.2623 (16)	N2—O4	1.2322 (16)
C10—C11	1.4361 (18)	N3—O7	1.2222 (16)
C11—C12	1.3550 (18)	N3—O8	1.2288 (16)
C11—H11	0.9300	N4—O9	1.2224 (15)
C12—H12	0.9300	N4—O10	1.2240 (16)
C13—N6	1.332 (2)	N5—H5	0.882 (9)
C13—N5	1.3406 (19)	N6—H6A	0.8600
C13—C14	1.405 (2)	N6—H6B	0.8600
C14—C15	1.355 (3)	N7—H7	0.883 (9)
C14—H14	0.9300	N8—H8A	0.8600
C15—C16	1.386 (3)	N8—H8B	0.8600

C6—C1—C2	120.75 (12)	C17—C16—C15	118.64 (17)
C6—C1—N2	118.96 (12)	C17—C16—H16	120.7
C2—C1—N2	120.27 (12)	C15—C16—H16	120.7
C3—C2—C1	119.28 (12)	C16—C17—N5	120.29 (16)
C3—C2—H2	120.4	C16—C17—H17	119.9
C1—C2—H2	120.4	N5—C17—H17	119.9
C2—C3—C4	123.55 (13)	C19—C18—N7	121.02 (15)
C2—C3—H3	118.2	C19—C18—H18	119.5
C4—C3—H3	118.2	N7—C18—H18	119.5
O1—C4—C5	125.60 (13)	C18—C19—C20	118.29 (14)
O1—C4—C3	120.25 (13)	C18—C19—H19	120.9
C5—C4—C3	114.14 (12)	C20—C19—H19	120.9
C6—C5—N1	115.74 (11)	C21—C20—C19	120.91 (14)
C6—C5—C4	122.36 (12)	C21—C20—H20	119.5
N1—C5—C4	121.89 (12)	C19—C20—H20	119.5
C1—C6—C5	119.88 (12)	C20—C21—C22	119.47 (15)
C1—C6—H6	120.1	C20—C21—H21	120.3
C5—C6—H6	120.1	C22—C21—H21	120.3
C8—C7—C12	120.97 (11)	N8—C22—N7	118.71 (12)
C8—C7—N3	119.05 (11)	N8—C22—C21	123.35 (13)
C12—C7—N3	119.97 (11)	N7—C22—C21	117.93 (13)
C7—C8—C9	119.61 (11)	O3—N1—O2	120.69 (12)
C7—C8—H8	120.2	O3—N1—C5	118.79 (12)
C9—C8—H8	120.2	O2—N1—C5	120.52 (12)
C8—C9—C10	122.42 (11)	O5—N2—O4	121.99 (13)
C8—C9—N4	116.20 (11)	O5—N2—C1	118.74 (12)
C10—C9—N4	121.36 (11)	O4—N2—C1	119.26 (12)
O6—C10—C9	125.87 (11)	O7—N3—O8	122.03 (12)
O6—C10—C11	119.81 (12)	O7—N3—C7	118.77 (12)
C9—C10—C11	114.31 (11)	O8—N3—C7	119.19 (11)
C12—C11—C10	123.39 (12)	O9—N4—O10	121.52 (12)
C12—C11—H11	118.3	O9—N4—C9	119.03 (11)
C10—C11—H11	118.3	O10—N4—C9	119.45 (11)
C11—C12—C7	119.28 (12)	C13—N5—C17	122.72 (14)
C11—C12—H12	120.4	C13—N5—H5	116.1 (13)
C7—C12—H12	120.4	C17—N5—H5	121.1 (13)
N6—C13—N5	118.30 (14)	C13—N6—H6A	120.0
N6—C13—C14	123.98 (16)	C13—N6—H6B	120.0
N5—C13—C14	117.71 (15)	H6A—N6—H6B	120.0
C15—C14—C13	119.64 (17)	C22—N7—C18	122.36 (12)
C15—C14—H14	120.2	C22—N7—H7	113.5 (13)
C13—C14—H14	120.2	C18—N7—H7	124.1 (13)
C14—C15—C16	120.98 (17)	C22—N8—H8A	120.0
C14—C15—H15	119.5	C22—N8—H8B	120.0
C16—C15—H15	119.5	H8A—N8—H8B	120.0

C6—C1—C2—C3	−1.0 (2)	C14—C15—C16—C17	0.4 (3)
N2—C1—C2—C3	177.39 (13)	C15—C16—C17—N5	−0.2 (2)
C1—C2—C3—C4	−0.4 (2)	N7—C18—C19—C20	1.3 (2)
C2—C3—C4—O1	−178.48 (14)	C18—C19—C20—C21	−0.9 (3)
C2—C3—C4—C5	1.7 (2)	C19—C20—C21—C22	−0.2 (2)
O1—C4—C5—C6	178.49 (13)	C20—C21—C22—N8	−177.98 (15)
C3—C4—C5—C6	−1.68 (19)	C20—C21—C22—N7	0.9 (2)
O1—C4—C5—N1	−0.4 (2)	C6—C5—N1—O3	5.60 (18)
C3—C4—C5—N1	179.45 (12)	C4—C5—N1—O3	−175.45 (13)
C2—C1—C6—C5	1.00 (19)	C6—C5—N1—O2	−173.28 (12)
N2—C1—C6—C5	−177.42 (11)	C4—C5—N1—O2	5.67 (19)
N1—C5—C6—C1	179.36 (11)	C6—C1—N2—O5	175.34 (13)
C4—C5—C6—C1	0.42 (19)	C2—C1—N2—O5	−3.1 (2)
C12—C7—C8—C9	0.38 (19)	C6—C1—N2—O4	−3.44 (19)
N3—C7—C8—C9	179.11 (11)	C2—C1—N2—O4	178.14 (13)
C7—C8—C9—C10	−0.63 (19)	C8—C7—N3—O7	177.56 (13)
C7—C8—C9—N4	−179.24 (11)	C12—C7—N3—O7	−3.70 (19)
C8—C9—C10—O6	−179.39 (13)	C8—C7—N3—O8	−2.72 (19)
N4—C9—C10—O6	−0.8 (2)	C12—C7—N3—O8	176.02 (13)
C8—C9—C10—C11	0.54 (18)	C8—C9—N4—O9	−8.16 (18)
N4—C9—C10—C11	179.09 (11)	C10—C9—N4—O9	173.21 (13)
O6—C10—C11—C12	179.70 (13)	C8—C9—N4—O10	171.16 (13)
C9—C10—C11—C12	−0.2 (2)	C10—C9—N4—O10	−7.47 (19)
C10—C11—C12—C7	0.0 (2)	N6—C13—N5—C17	−178.19 (14)
C8—C7—C12—C11	−0.1 (2)	C14—C13—N5—C17	1.1 (2)
N3—C7—C12—C11	−178.80 (12)	C16—C17—N5—C13	−0.6 (2)
N6—C13—C14—C15	178.41 (16)	N8—C22—N7—C18	178.45 (14)
N5—C13—C14—C15	−0.8 (2)	C21—C22—N7—C18	−0.5 (2)
C13—C14—C15—C16	0.1 (3)	C19—C18—N7—C22	−0.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O1ⁱ	0.88 (1)	1.92 (1)	2.7304 (16)	152 (2)
N5—H5···O2ⁱ	0.88 (1)	2.31 (2)	2.9553 (17)	130 (2)
N6—H6A···O1ⁱ	0.86	2.02	2.7712 (19)	145
N6—H6B···O4ⁱⁱ	0.86	2.15	2.9849 (18)	162
N7—H7···O6ⁱⁱⁱ	0.88 (1)	1.83 (1)	2.6627 (15)	157 (2)
N7—H7···O10ⁱⁱⁱ	0.88 (1)	2.31 (2)	2.8975 (17)	124 (2)
N8—H8A···O6ⁱⁱⁱ	0.86	2.04	2.7727 (16)	143
N8—H8B···O2ⁱ	0.86	2.42	3.2740 (17)	175
N8—H8B···O3ⁱ	0.86	2.50	3.1445 (17)	132
C3—H3···O8	0.93	2.56	3.1944 (18)	126
C18—H18···O10ⁱⁱⁱ	0.93	2.51	3.034 (2)	116

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

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras for the data collection.

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