2-Amino-4-methyl­pyridinium 2-hy­droxy­benzoate

Sivakumar, P.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616014437

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161443

doi:10.1107/S2414314616014437

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2-Amino-4-methylpyridinium 2-hydroxybenzoate

P. Sivakumar,^a,^b S. Israel ^c ^* and G. Chakkaravarthi ^b ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, and ^cPost Graduate and Research Department of Physics, The American College, Madurai 625 002, India
^*Correspondence e-mail: israel.samuel@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 September 2016; accepted 12 September 2016; online 16 September 2016)

The title molecular salt, C₆H₉N₂⁺·C₇H₅O₃⁻, contains two ion pairs in the asymmetric unit. Both anions feature an intramolecular O—H⋯O hydrogen bond, which closes an S(6) ring. In the crystal, N—H⋯O hydogen bonds link the components into [010] chains, which feature R₂²(8) loops. The crystal structure is consolidated by weak C—H⋯O and π–π [centroid-to-centroid distance = 3.7528 (16) Å] interactions, forming a three-dimensional network.

Keywords: molecular salt; crystal structure; hydrogen bonding.

CCDC reference: 1503875

Structure description

As part of our ongoing studies of pyridinium molecular salts (Sivakumar et al., 2016a ,b ), we now report the synthesis and the crystal structure of the title molecular salt (Fig. 1), whose asymmetric unit contains two 2-amino-4-methylpyridinium cations and two 2-hydroxybenzoate anions. The cations are protonated at the pyridine N (N1 and N3) atoms as usual. In both anions, intramolecular O1—H1A⋯O3 and O4—H4C⋯O6 hydrogen bonds (Table 1) generate S(6) rings.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3	0.83 (1)	1.81 (2)	2.546 (3)	149 (4)
O4—H4C⋯O6	0.83 (1)	1.74 (2)	2.508 (3)	154 (4)
N1—H1⋯O3ⁱ	0.86	1.79	2.648 (3)	173
N2—H2B⋯O2ⁱ	0.86 (1)	2.00 (1)	2.858 (4)	175 (3)
N2—H2A⋯O5ⁱⁱ	0.85 (1)	2.05 (1)	2.890 (3)	168 (3)
N3—H3A⋯O5ⁱⁱ	0.86 (1)	1.89 (1)	2.743 (3)	172 (3)
N4—H4A⋯O6ⁱⁱ	0.86 (1)	1.96 (1)	2.814 (4)	177 (3)
N4—H4B⋯O2ⁱⁱ	0.86 (1)	2.05 (1)	2.891 (4)	170 (4)
C12—H12⋯O4ⁱⁱⁱ	0.93	2.52	3.390 (4)	156
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) -x+1, -y+1, -z.

Figure 1
The molecular structure of the title molecular salt, with atom labelling and 30% probability displacement ellipsoids.

In the crystal, N1—H1⋯O3ⁱ, N2—H2B⋯O2ⁱ, N3—H3A⋯O5ⁱⁱ and N4—H4A⋯O6ⁱⁱ hydrogen bonds link adjacent anions and cations, generating $[R_{2}^{2}]$ (8) ring-set motifs (Fig. 2); these units are further connected by N4—H4B⋯O2 (Table 1) hydrogen bonds into chains propagating along [010]. The crystal structure also features weak C12—H12⋯O4ⁱⁱⁱ (Table 1) and π–π [Cg1⋯Cg1^iv = 3.7528 (16) Å; symmetry code: (iv) 1 − x, 1 − y, −z; Cg1 is the centroid of the N1/C8–C12 ring] interactions, which cross-link the chains, forming a three-dimensional network (Fig. 3).

Figure 2
A partial view of the crystal packing showing the ring motifs.

Figure 3
The crystal packing of the title molecular salt viewed along the bc plane. Hydrogen bonds are shown as dashed lines. H atoms not involving in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

An equimolar ratio of 2-hydroxy benzoic acid (0.69 g) and 2-amino-4-methylpyridine (0.54 g) was dissolved in 10 ml of methanol and a white precipitate formed. The precipitate was dissolved in 20 ml of water and kept at room temperature for slow evaporation. After 30 days, colourless blocks of the title salt were isolated.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₇H₅O₃⁻
M_r	246.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.6615 (9), 13.8008 (11), 15.4039 (14)
β (°)	111.225 (2)
V (Å³)	2509.1 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.678, 0.745
No. of measured, independent and observed reflections	27359, 5010, 2989
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.621

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.161, 1.08
No. of reflections	5010
No. of parameters	359
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1503875

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616014437/hb4080sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014437/hb4080Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014437/hb4080Isup3.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: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

2-Amino-4-methylpyridinium 2-hydroxybenzoate top

Crystal data top

C₆H₉N₂⁺·C₇H₅O₃⁻	F(000) = 1040
M_r = 246.26	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6615 (9) Å	Cell parameters from 6612 reflections
b = 13.8008 (11) Å	θ = 2.3–23.6°
c = 15.4039 (14) Å	µ = 0.09 mm⁻¹
β = 111.225 (2)°	T = 295 K
V = 2509.1 (4) Å³	Block, colourless
Z = 8	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	R_int = 0.034
ω and φ scan	θ_max = 26.2°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→15
T_min = 0.678, T_max = 0.745	k = −17→17
27359 measured reflections	l = −19→18
5010 independent reflections

Refinement top

Refinement on F²	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0343P)² + 2.845P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
5010 reflections	Δρ_max = 0.27 e Å⁻³
359 parameters	Δρ_min = −0.22 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
C1	0.3683 (3)	0.1420 (2)	0.0863 (2)	0.0459 (7)
C6	0.2754 (3)	0.1418 (2)	0.0040 (3)	0.0673 (10)
H6	0.203120	0.146580	0.006113	0.081*
C5	0.2876 (5)	0.1348 (3)	−0.0803 (3)	0.0926 (14)
H5	0.224383	0.135931	−0.135172	0.111*
C4	0.3943 (6)	0.1260 (3)	−0.0829 (3)	0.1019 (17)
H4	0.402933	0.120288	−0.140142	0.122*
C3	0.4884 (4)	0.1255 (3)	−0.0027 (3)	0.0886 (13)
H3	0.560097	0.119550	−0.005858	0.106*
C2	0.4768 (3)	0.1339 (2)	0.0828 (2)	0.0574 (9)
C7	0.3514 (2)	0.1503 (2)	0.1759 (2)	0.0495 (8)
C8	0.3182 (2)	0.3869 (2)	−0.0761 (2)	0.0429 (7)
C9	0.3187 (2)	0.4032 (2)	0.0137 (2)	0.0454 (7)
H9	0.250654	0.414888	0.022009	0.055*
C10	0.4166 (2)	0.4021 (2)	0.0888 (2)	0.0465 (7)
C11	0.5197 (3)	0.3858 (2)	0.0753 (2)	0.0504 (8)
C12	0.5169 (2)	0.3711 (2)	−0.0118 (2)	0.0505 (8)
H12	0.584292	0.359920	−0.021349	0.061*
C13	0.4198 (3)	0.4157 (3)	0.1863 (2)	0.0668 (10)
H13A	0.345547	0.432604	0.184730	0.100*
H13B	0.472013	0.466614	0.216086	0.100*
H13C	0.443824	0.356553	0.220642	0.100*
C14	0.1061 (2)	0.6973 (2)	0.1147 (2)	0.0439 (7)
C15	0.0309 (3)	0.7700 (3)	0.1141 (3)	0.0623 (9)
H15	−0.040918	0.753619	0.112752	0.075*
C16	0.0598 (4)	0.8659 (3)	0.1155 (3)	0.0831 (12)
H16	0.007493	0.913827	0.114029	0.100*
C17	0.1663 (4)	0.8908 (3)	0.1192 (3)	0.0840 (12)
H17	0.186402	0.955820	0.121303	0.101*
C18	0.2425 (3)	0.8214 (3)	0.1198 (3)	0.0737 (11)
H18	0.314367	0.839136	0.122314	0.088*
C19	0.2136 (3)	0.7240 (3)	0.1167 (2)	0.0536 (8)
C20	0.0747 (2)	0.5936 (2)	0.1145 (2)	0.0474 (7)
C21	−0.0130 (2)	0.6937 (2)	−0.1326 (2)	0.0460 (7)
C22	0.0192 (2)	0.7896 (2)	−0.1379 (2)	0.0484 (8)
H22	−0.031505	0.839371	−0.141032	0.058*
C23	0.1235 (2)	0.8113 (2)	−0.1388 (2)	0.0486 (8)
C24	0.1985 (2)	0.7350 (2)	−0.1345 (2)	0.0562 (9)
H24	0.270064	0.747788	−0.135866	0.067*
C25	0.1660 (2)	0.6435 (2)	−0.1286 (3)	0.0595 (9)
H25	0.215866	0.592996	−0.125625	0.071*
C26	0.1601 (3)	0.9135 (2)	−0.1424 (3)	0.0679 (10)
H26A	0.095063	0.952753	−0.174757	0.102*
H26B	0.212228	0.915961	−0.174700	0.102*
H26C	0.196441	0.937671	−0.080238	0.102*
N1	0.41871 (18)	0.37204 (17)	−0.08565 (18)	0.0449 (6)
H1	0.420195	0.362938	−0.140423	0.054*
N2	0.2249 (2)	0.3872 (2)	−0.1522 (2)	0.0576 (7)
N3	0.0624 (2)	0.62292 (19)	−0.12671 (19)	0.0492 (6)
N4	−0.1142 (2)	0.6683 (2)	−0.1317 (3)	0.0685 (9)
O1	0.5718 (2)	0.1361 (2)	0.1601 (2)	0.0791 (8)
O2	0.25347 (17)	0.15946 (19)	0.17682 (17)	0.0679 (7)
O3	0.43864 (17)	0.1485 (2)	0.25005 (16)	0.0690 (7)
O4	0.2911 (2)	0.6573 (2)	0.1163 (2)	0.0736 (8)
O5	−0.01976 (16)	0.57100 (16)	0.11794 (16)	0.0586 (6)
O6	0.14672 (18)	0.53092 (16)	0.11156 (18)	0.0660 (7)
H1A	0.552 (3)	0.140 (3)	0.2055 (19)	0.103 (16)*
H2A	0.1614 (15)	0.391 (2)	−0.145 (2)	0.061 (10)*
H2B	0.230 (3)	0.371 (2)	−0.2043 (13)	0.067 (11)*
H3A	0.044 (3)	0.5637 (10)	−0.122 (2)	0.058 (10)*
H4A	−0.127 (3)	0.6079 (10)	−0.126 (3)	0.080 (13)*
H4B	−0.160 (2)	0.7161 (18)	−0.141 (3)	0.081 (13)*
H4C	0.259 (3)	0.6048 (17)	0.114 (3)	0.108 (18)*
H11	0.593 (2)	0.384 (2)	0.131 (2)	0.046 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0556 (18)	0.0360 (16)	0.0472 (19)	−0.0029 (14)	0.0200 (15)	0.0055 (14)
C6	0.079 (2)	0.057 (2)	0.058 (2)	−0.0116 (19)	0.014 (2)	0.0039 (18)
C5	0.135 (4)	0.072 (3)	0.058 (3)	−0.035 (3)	0.021 (3)	−0.005 (2)
C4	0.177 (5)	0.082 (3)	0.065 (3)	−0.035 (4)	0.066 (4)	−0.016 (3)
C3	0.119 (4)	0.089 (3)	0.088 (3)	−0.012 (3)	0.073 (3)	−0.002 (3)
C2	0.069 (2)	0.053 (2)	0.060 (2)	−0.0050 (17)	0.0352 (19)	0.0029 (17)
C7	0.0419 (17)	0.0506 (19)	0.058 (2)	0.0062 (14)	0.0198 (16)	0.0095 (16)
C8	0.0367 (15)	0.0387 (16)	0.059 (2)	−0.0004 (13)	0.0240 (15)	−0.0010 (14)
C9	0.0358 (15)	0.0468 (17)	0.062 (2)	0.0011 (13)	0.0271 (15)	0.0003 (15)
C10	0.0499 (17)	0.0398 (16)	0.058 (2)	0.0008 (14)	0.0291 (16)	0.0024 (15)
C11	0.0403 (17)	0.0522 (19)	0.060 (2)	0.0037 (15)	0.0191 (16)	0.0012 (16)
C12	0.0336 (15)	0.0514 (19)	0.073 (2)	0.0040 (14)	0.0264 (16)	−0.0015 (17)
C13	0.063 (2)	0.078 (3)	0.067 (2)	0.0048 (19)	0.0328 (19)	0.002 (2)
C14	0.0360 (15)	0.0543 (19)	0.0413 (17)	−0.0023 (14)	0.0139 (13)	−0.0021 (14)
C15	0.0512 (19)	0.058 (2)	0.080 (3)	−0.0002 (17)	0.0265 (18)	−0.0047 (19)
C16	0.082 (3)	0.059 (2)	0.113 (4)	0.003 (2)	0.040 (3)	−0.006 (2)
C17	0.098 (3)	0.055 (2)	0.101 (3)	−0.020 (2)	0.037 (3)	−0.009 (2)
C18	0.062 (2)	0.080 (3)	0.082 (3)	−0.025 (2)	0.029 (2)	−0.004 (2)
C19	0.0444 (17)	0.068 (2)	0.051 (2)	−0.0070 (16)	0.0192 (15)	−0.0012 (17)
C20	0.0392 (16)	0.0555 (19)	0.0497 (19)	0.0003 (15)	0.0187 (14)	−0.0012 (15)
C21	0.0357 (15)	0.0540 (19)	0.0486 (19)	0.0037 (14)	0.0156 (14)	0.0019 (15)
C22	0.0392 (16)	0.0510 (19)	0.055 (2)	0.0090 (14)	0.0172 (14)	0.0030 (15)
C23	0.0423 (16)	0.0520 (19)	0.0492 (19)	0.0001 (14)	0.0138 (14)	0.0012 (15)
C24	0.0350 (15)	0.057 (2)	0.079 (2)	−0.0003 (15)	0.0241 (16)	−0.0008 (18)
C25	0.0378 (16)	0.056 (2)	0.088 (3)	0.0065 (15)	0.0273 (17)	−0.0015 (19)
C26	0.060 (2)	0.054 (2)	0.091 (3)	−0.0061 (17)	0.028 (2)	0.0001 (19)
N1	0.0391 (13)	0.0483 (15)	0.0545 (16)	0.0014 (11)	0.0257 (12)	−0.0031 (12)
N2	0.0388 (15)	0.079 (2)	0.060 (2)	0.0019 (14)	0.0237 (15)	−0.0076 (16)
N3	0.0386 (13)	0.0442 (16)	0.0672 (18)	0.0021 (12)	0.0221 (12)	0.0026 (14)
N4	0.0442 (16)	0.058 (2)	0.112 (3)	0.0045 (16)	0.0378 (17)	0.010 (2)
O1	0.0539 (15)	0.117 (2)	0.082 (2)	0.0055 (15)	0.0422 (15)	0.0129 (18)
O2	0.0421 (12)	0.0922 (18)	0.0738 (17)	0.0151 (12)	0.0262 (12)	0.0163 (14)
O3	0.0417 (12)	0.115 (2)	0.0534 (15)	0.0081 (13)	0.0213 (11)	0.0109 (14)
O4	0.0451 (13)	0.088 (2)	0.099 (2)	−0.0021 (14)	0.0388 (14)	0.0017 (17)
O5	0.0394 (11)	0.0574 (14)	0.0850 (17)	−0.0045 (10)	0.0296 (11)	−0.0071 (12)
O6	0.0515 (13)	0.0573 (14)	0.103 (2)	0.0036 (11)	0.0444 (13)	−0.0021 (13)

Geometric parameters (Å, º) top

C1—C6	1.382 (4)	C15—H15	0.9300
C1—C2	1.398 (4)	C16—C17	1.373 (5)
C1—C7	1.477 (4)	C16—H16	0.9300
C6—C5	1.365 (5)	C17—C18	1.357 (5)
C6—H6	0.9300	C17—H17	0.9300
C5—C4	1.371 (7)	C18—C19	1.389 (5)
C5—H5	0.9300	C18—H18	0.9300
C4—C3	1.372 (6)	C19—O4	1.348 (4)
C4—H4	0.9300	C20—O5	1.255 (3)
C3—C2	1.382 (5)	C20—O6	1.271 (3)
C3—H3	0.9300	C21—N4	1.333 (4)
C2—O1	1.352 (4)	C21—N3	1.345 (4)
C7—O2	1.252 (3)	C21—C22	1.396 (4)
C7—O3	1.269 (4)	C22—C23	1.359 (4)
C8—N2	1.329 (4)	C22—H22	0.9300
C8—N1	1.349 (3)	C23—C24	1.403 (4)
C8—C9	1.399 (4)	C23—C26	1.493 (4)
C9—C10	1.355 (4)	C24—C25	1.343 (4)
C9—H9	0.9300	C24—H24	0.9300
C10—C11	1.413 (4)	C25—N3	1.352 (4)
C10—C13	1.501 (4)	C25—H25	0.9300
C11—C12	1.345 (4)	C26—H26A	0.9600
C11—H11	1.01 (3)	C26—H26B	0.9600
C12—N1	1.347 (4)	C26—H26C	0.9600
C12—H12	0.9300	N1—H1	0.8600
C13—H13A	0.9600	N2—H2A	0.853 (10)
C13—H13B	0.9600	N2—H2B	0.859 (10)
C13—H13C	0.9600	N3—H3A	0.861 (10)
C14—C15	1.381 (4)	N4—H4A	0.860 (10)
C14—C19	1.400 (4)	N4—H4B	0.855 (10)
C14—C20	1.484 (4)	O1—H1A	0.825 (10)
C15—C16	1.371 (5)	O4—H4C	0.826 (10)

C6—C1—C2	119.2 (3)	C15—C16—H16	120.2
C6—C1—C7	119.6 (3)	C17—C16—H16	120.2
C2—C1—C7	121.2 (3)	C18—C17—C16	120.6 (4)
C5—C6—C1	121.4 (4)	C18—C17—H17	119.7
C5—C6—H6	119.3	C16—C17—H17	119.7
C1—C6—H6	119.3	C17—C18—C19	120.3 (3)
C6—C5—C4	119.1 (4)	C17—C18—H18	119.8
C6—C5—H5	120.5	C19—C18—H18	119.8
C4—C5—H5	120.5	O4—C19—C18	118.6 (3)
C5—C4—C3	121.2 (4)	O4—C19—C14	121.6 (3)
C5—C4—H4	119.4	C18—C19—C14	119.8 (3)
C3—C4—H4	119.4	O5—C20—O6	122.6 (3)
C4—C3—C2	120.0 (4)	O5—C20—C14	119.9 (3)
C4—C3—H3	120.0	O6—C20—C14	117.5 (2)
C2—C3—H3	120.0	N4—C21—N3	118.0 (3)
O1—C2—C3	118.3 (4)	N4—C21—C22	123.5 (3)
O1—C2—C1	122.5 (3)	N3—C21—C22	118.5 (3)
C3—C2—C1	119.2 (4)	C23—C22—C21	121.0 (3)
O2—C7—O3	122.4 (3)	C23—C22—H22	119.5
O2—C7—C1	119.9 (3)	C21—C22—H22	119.5
O3—C7—C1	117.8 (3)	C22—C23—C24	118.6 (3)
N2—C8—N1	118.5 (3)	C22—C23—C26	121.6 (3)
N2—C8—C9	123.8 (3)	C24—C23—C26	119.8 (3)
N1—C8—C9	117.7 (3)	C25—C24—C23	119.3 (3)
C10—C9—C8	121.2 (3)	C25—C24—H24	120.3
C10—C9—H9	119.4	C23—C24—H24	120.3
C8—C9—H9	119.4	C24—C25—N3	121.5 (3)
C9—C10—C11	119.0 (3)	C24—C25—H25	119.2
C9—C10—C13	122.6 (3)	N3—C25—H25	119.2
C11—C10—C13	118.4 (3)	C23—C26—H26A	109.5
C12—C11—C10	118.6 (3)	C23—C26—H26B	109.5
C12—C11—H11	122.1 (16)	H26A—C26—H26B	109.5
C10—C11—H11	119.3 (16)	C23—C26—H26C	109.5
C11—C12—N1	121.6 (3)	H26A—C26—H26C	109.5
C11—C12—H12	119.2	H26B—C26—H26C	109.5
N1—C12—H12	119.2	C12—N1—C8	121.9 (3)
C10—C13—H13A	109.5	C12—N1—H1	119.1
C10—C13—H13B	109.5	C8—N1—H1	119.1
H13A—C13—H13B	109.5	C8—N2—H2A	118 (2)
C10—C13—H13C	109.5	C8—N2—H2B	119 (2)
H13A—C13—H13C	109.5	H2A—N2—H2B	122 (3)
H13B—C13—H13C	109.5	C21—N3—C25	121.1 (3)
C15—C14—C19	118.1 (3)	C21—N3—H3A	119 (2)
C15—C14—C20	121.1 (3)	C25—N3—H3A	120 (2)
C19—C14—C20	120.8 (3)	C21—N4—H4A	118 (2)
C16—C15—C14	121.5 (3)	C21—N4—H4B	113 (3)
C16—C15—H15	119.2	H4A—N4—H4B	129 (3)
C14—C15—H15	119.2	C2—O1—H1A	108 (3)
C15—C16—C17	119.6 (4)	C19—O4—H4C	105 (3)

C2—C1—C6—C5	−0.6 (5)	C15—C16—C17—C18	1.2 (7)
C7—C1—C6—C5	179.6 (3)	C16—C17—C18—C19	0.0 (6)
C1—C6—C5—C4	1.2 (6)	C17—C18—C19—O4	179.2 (4)
C6—C5—C4—C3	−0.9 (7)	C17—C18—C19—C14	−1.2 (6)
C5—C4—C3—C2	0.0 (7)	C15—C14—C19—O4	−179.2 (3)
C4—C3—C2—O1	−178.0 (4)	C20—C14—C19—O4	1.6 (5)
C4—C3—C2—C1	0.5 (6)	C15—C14—C19—C18	1.2 (5)
C6—C1—C2—O1	178.2 (3)	C20—C14—C19—C18	−178.0 (3)
C7—C1—C2—O1	−2.0 (5)	C15—C14—C20—O5	−3.1 (5)
C6—C1—C2—C3	−0.3 (5)	C19—C14—C20—O5	176.1 (3)
C7—C1—C2—C3	179.5 (3)	C15—C14—C20—O6	177.4 (3)
C6—C1—C7—O2	−1.7 (5)	C19—C14—C20—O6	−3.4 (4)
C2—C1—C7—O2	178.5 (3)	N4—C21—C22—C23	−179.9 (3)
C6—C1—C7—O3	178.8 (3)	N3—C21—C22—C23	1.0 (5)
C2—C1—C7—O3	−1.0 (4)	C21—C22—C23—C24	0.3 (5)
N2—C8—C9—C10	−179.9 (3)	C21—C22—C23—C26	−178.7 (3)
N1—C8—C9—C10	−1.3 (4)	C22—C23—C24—C25	−0.9 (5)
C8—C9—C10—C11	1.0 (4)	C26—C23—C24—C25	178.1 (3)
C8—C9—C10—C13	−177.7 (3)	C23—C24—C25—N3	0.1 (5)
C9—C10—C11—C12	−0.5 (5)	C11—C12—N1—C8	−0.6 (5)
C13—C10—C11—C12	178.3 (3)	N2—C8—N1—C12	179.7 (3)
C10—C11—C12—N1	0.3 (5)	C9—C8—N1—C12	1.1 (4)
C19—C14—C15—C16	−0.1 (5)	N4—C21—N3—C25	179.0 (3)
C20—C14—C15—C16	179.1 (3)	C22—C21—N3—C25	−1.8 (5)
C14—C15—C16—C17	−1.1 (6)	C24—C25—N3—C21	1.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.83 (1)	1.81 (2)	2.546 (3)	149 (4)
O4—H4C···O6	0.83 (1)	1.74 (2)	2.508 (3)	154 (4)
N1—H1···O3ⁱ	0.86	1.79	2.648 (3)	173
N2—H2B···O2ⁱ	0.86 (1)	2.00 (1)	2.858 (4)	175 (3)
N2—H2A···O5ⁱⁱ	0.85 (1)	2.05 (1)	2.890 (3)	168 (3)
N3—H3A···O5ⁱⁱ	0.86 (1)	1.89 (1)	2.743 (3)	172 (3)
N4—H4A···O6ⁱⁱ	0.86 (1)	1.96 (1)	2.814 (4)	177 (3)
N4—H4B···O2ⁱⁱ	0.86 (1)	2.05 (1)	2.891 (4)	170 (4)
C12—H12···O4ⁱⁱⁱ	0.93	2.52	3.390 (4)	156

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

Acknowledgements

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

References

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