1-Methyl­piperazine-1,4-diium dipicrate

Dutkiewicz, G.; Samshuddin, S.; Narayana, B.; Yathirajan, H.S.; Kubicki, M.

doi:10.1107/S1600536811001024

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages o390-o391

doi:10.1107/S1600536811001024

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1-Methylpiperazine-1,4-diium dipicrate

Grzegorz Dutkiewicz,^a S. Samshuddin,^b B. Narayana,^b H. S. Yathirajan ^c and Maciej Kubicki ^a ^*

^aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland, ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: mkubicki@amu.edu.pl

(Received 20 December 2010; accepted 7 January 2011; online 15 January 2011)

In the crystal structure of the title compound [systematic name: 1-methylpiperazine-1,4-diium bis(2,4,6-trinitrophenolate)], C₅H₁₄N₂²⁺·2C₆H₂N₃O₇⁻, the ionic components are connected by relatively strong N—H⋯O hydrogen bonds into centrosymmetric six-membered conglomerates, which comprise two dications and four anions. Besides Coulombic interactions, only weak C—H⋯O interactions and some stacking between picrates (separation between the planes of ca. 3.4 Å but only a small overlapping) can be identified between these `building blocks' of the crystal structure. The piperazine ring adopts a chair conformation with the methyl substituent in the equatorial position. In the picrate anions, the twist angles of the nitro groups depend on their positions relative to the phenolate O atom: it is much smaller for the NO₂ groups para to the C—O⁻ group [15.23 (9)and 3.92 (14)°] than for the groups in the ortho positions [28.76 (13)–39.84 (11)°].

Related literature

For examples of the biological activity of piperazines: Brockunier et al. (2004 ); Bogatcheva et al. (2006 ). For the crystal structures of simple piperidinium picrates, see: Fun et al. (2010 ); Li et al. (2009 ); Verdonk et al. (1997 ); Wang & Jia (2008 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For asymmetry parameters, see: Duax & Norton (1975 ).

Experimental

Crystal data

C₅H₁₄N₂²⁺·2C₆H₂N₃O₇⁻
M_r = 558.39
Triclinic, $[P \overline 1]$
a = 8.2001 (12) Å
b = 10.1780 (15) Å
c = 13.7399 (18) Å
α = 89.798 (12)°
β = 78.130 (11)°
γ = 81.558 (12)°
V = 1109.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 295 K
0.4 × 0.15 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.936, T_max = 1.000
21056 measured reflections
4891 independent reflections
3624 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.123
S = 0.95
4891 reflections
424 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O1A	0.892 (18)	1.831 (18)	2.6305 (17)	148.1 (16)
N11—H11⋯O22A	0.892 (18)	2.356 (18)	2.996 (2)	128.8 (14)
N14—H14B⋯O1Bⁱ	0.88 (2)	1.98 (2)	2.8181 (19)	157.3 (17)
N14—H14A⋯O1B	0.92 (2)	1.99 (2)	2.7962 (18)	146.4 (18)
N14—H14A⋯O22B	0.92 (2)	2.28 (2)	2.992 (2)	133.9 (16)
C5A—H5A⋯O21Aⁱⁱ	0.917 (19)	2.476 (19)	3.383 (2)	170.3 (16)
C5B—H5B⋯O21Bⁱⁱⁱ	0.913 (18)	2.487 (18)	3.394 (2)	172.3 (15)
C11A—H11C⋯O41A^iv	0.93 (3)	2.48 (3)	3.345 (2)	155 (2)
C11A—H11A⋯O62Aⁱⁱⁱ	0.94 (3)	2.57 (3)	3.496 (3)	168 (2)
C13—H13A⋯O62B^v	0.96 (2)	2.46 (2)	3.386 (2)	162.9 (17)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y, z; (iv) x+1, y-1, z; (v) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001024/fl2330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001024/fl2330Isup2.hkl

checkCIF report

Comment top

Piperazines are among the most important building blocks in today's drug discovery. They are found in biologically active compounds across a number of different therapeutic areas such as antifungal, antibacterial, antimalarial, antipsychotic, antidepressant and antitumour activity against colon, prostate, breast, lung and leukemia tumors (for instance, Brockunier et al., 2004, Bogatcheva et al., 2006). A small number of piperazinium picrates or piperazinediium dipicrates have been structurally characterized, however generally the cations were heavily substituted. On the other hand, picric acid (pK_a=0.38) has been studied for its ability to form salts which display wide spectrum of intermolecular interactions, for instance hydrogen bonds of different strengths and/or π···π stacking interactions. In the course of our studies of picrates of simple organic cations we have determined the crystal and molecular structure of the title compound (I: 1-methylpiprazinediium di(2,4,6-trinitrophenolate), Scheme 1).

In the CSD (Allen, 2002; Version 5.31 of Nov. 2009, updated August 2010) there are only a few picrates of simple piperazinium derivatives, for instance 4-(4-carboxybenzyl)-1-methylpiperazin-1-ium picrate (Li et al., 2009), 1-(2-methoxyphenyl)piperazinium picrate (Verdonk et al., 1997) or piperazine-1,4-diium–dipicrate piperazine complex (Wang & Jia, 2008). Also some more complicated structures were reported, for instance 4-(3-Carboxy-1-ethyl-6-fluoro-4-oxo-1,4- dihydro-7-quinolyl)-1-methylpiperazinium picrate (Fun et al., 2010).

In the crystal structure I there are two picrate anions and 1-methylpiperidinediium dication (Fig. 1); the presence of ionic species is supported by the successful location and refinement of the hydrogen atoms at both nitrogen atoms in the piperidine ring as well as by inspection of the pattern of bond distances and angles. The piperazine ring adopts an almost ideal chair conformation; the values of asymmetry parameters (Duax & Norton, 1975), which measure the deviations from the ideal symmetry (in the case D₃ _d), are very small, less than 1.6°. The methyl substituent is in the equatorial position as can be seen from the torsion angles C13—C12—C11—C11A: 176.60 (15)° and C15—C16—C11—C11A: -176.72 (14)°. Both aromatic rings are in a good approximation planar, maximum deviation from the least-squares plane calculated by the six ring atoms is 0.0248 (11)Å in the anion A and 0.0297 (10)Å in anion B. The nitro groups are twisted with respect to the ring planes, for the groups ortho with respect to the C—O^- group (at C2 and C6) this twist is of course significantly larger (ranging from 28.76 (13)° to 39.84 (11)°) than for the groups in para positions, at C4 (15.23 (9)° in anion A, only 3.92 (14)° in B).

In the crystal structure the building block is made up of a centrosymetric pair of hydrogen bonded ionic components: two dications and four anions (Table 1, Fig. 2). Using graph set notation one can identify - taking into account the primary interactions only - the centrosymmetric ring R²₄(8) and dimeric D motifs. Interestingly no strong hydrogen bonds are observed between these structures; besides the coulombic interactions only weak C—H···O and some stacking between picrates (Fig. 3) organize the crystal packing.

Related literature top

For examples of the biological activity of piperazines: Brockunier et al. (2004); Bogatcheva et al. (2006). For the crystal structures of simple piperidinium picrates, see: Fun et al. (2010); Li et al. (2009); Verdonk et al. (1997); Wang & Jia (2008). For a description of the Cambridge Structural Database, see: Allen (2002). For asymmetry parameters, see: Duax & Norton (1975).

Experimental top

1-Methyl piperazine (1.00 g, 0.01 mol) was dissolved in 20 ml of alcohol. Picric acid (4.58 g, 0.02 mol) was dissolved in 50 ml of water. Both the solutions were mixed and to this, 5 ml of 3M HCl was added and stirred for few minutes. The formed complex was filtered and dried, crystals appropriate for X-ray data collection were found without further recrystallization (m. p. >523 K). Composition: Found (Calculated): C: 36.48 (36.57); H: 3.20 (3.25); N:19.98 (20.07).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Anisotropic ellipsoid representation of the ionic components of I together with atom labelling scheme. The ellipsoids are drawn at 50% probability level, hydrogen atoms are depicted as spheres with arbitrary radii; hydrogen bonds are shown as dashed lines.
	Fig. 2. The centrosymmetric dimer of salt I; hydrogen bonds are shown as dashed lines. Symmetry codes: (i) -x,1 - y,1 - z.
	Fig. 3. The crystal packing as seen approximately along y-direction. Hydrogen bonds are shown as dashed lines.

1-methylpiperazine-1,4-diium bis(2,4,6-trinitrophenolate) top

Crystal data top

C₅H₁₄N₂²⁺·2C₆H₂N₃O₇⁻	Z = 2
M_r = 558.39	F(000) = 576
Triclinic, P1	D_x = 1.671 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2001 (12) Å	Cell parameters from 12041 reflections
b = 10.1780 (15) Å	θ = 3.0–28.0°
c = 13.7399 (18) Å	µ = 0.15 mm⁻¹
α = 89.798 (12)°	T = 295 K
β = 78.130 (11)°	Block, yellow
γ = 81.558 (12)°	0.4 × 0.15 × 0.07 mm
V = 1109.6 (3) Å³

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	4891 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.1544 pixels mm^-1	θ_max = 28.0°, θ_min = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→12
T_min = 0.936, T_max = 1.000	l = −18→18
21056 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0725P)² + 0.3607P] where P = (F_o² + 2F_c²)/3
4891 reflections	(Δ/σ)_max < 0.001
424 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₅H₁₄N₂²⁺·2C₆H₂N₃O₇⁻	γ = 81.558 (12)°
M_r = 558.39	V = 1109.6 (3) Å³
Triclinic, P1	Z = 2
a = 8.2001 (12) Å	Mo Kα radiation
b = 10.1780 (15) Å	µ = 0.15 mm⁻¹
c = 13.7399 (18) Å	T = 295 K
α = 89.798 (12)°	0.4 × 0.15 × 0.07 mm
β = 78.130 (11)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	4891 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	3624 reflections with I > 2σ(I)
T_min = 0.936, T_max = 1.000	R_int = 0.021
21056 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.24 e Å⁻³
4891 reflections	Δρ_min = −0.30 e Å⁻³
424 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

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 > σ(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
C1A	−0.10838 (19)	0.86643 (15)	0.10686 (11)	0.0303 (3)
O1A	−0.02003 (16)	0.75573 (12)	0.08429 (10)	0.0469 (3)
C2A	−0.04660 (18)	0.98367 (16)	0.13439 (12)	0.0309 (3)
N2A	0.12392 (16)	0.97199 (15)	0.15030 (11)	0.0394 (3)
O21A	0.19522 (16)	1.07010 (15)	0.13867 (13)	0.0601 (4)
O22A	0.18805 (16)	0.86647 (14)	0.17951 (12)	0.0568 (4)
C3A	−0.1404 (2)	1.10787 (16)	0.14843 (12)	0.0314 (3)
H3A	−0.091 (3)	1.179 (2)	0.1651 (16)	0.052 (6)*
C4A	−0.30793 (18)	1.12289 (14)	0.14285 (11)	0.0284 (3)
N4A	−0.40990 (18)	1.25160 (13)	0.16554 (10)	0.0350 (3)
O41A	−0.56396 (15)	1.25745 (13)	0.18252 (10)	0.0474 (3)
O42A	−0.33873 (18)	1.34906 (12)	0.16819 (12)	0.0566 (4)
C5A	−0.38244 (19)	1.01553 (15)	0.12063 (11)	0.0288 (3)
H5A	−0.495 (2)	1.0237 (18)	0.1186 (13)	0.036 (5)*
C6A	−0.28521 (19)	0.89319 (14)	0.10388 (11)	0.0294 (3)
N6A	−0.36772 (18)	0.78285 (13)	0.08081 (11)	0.0370 (3)
O61A	−0.3268 (2)	0.67315 (13)	0.11180 (13)	0.0662 (5)
O62A	−0.47823 (18)	0.80553 (14)	0.03359 (11)	0.0557 (4)
C1B	0.29112 (18)	0.24867 (15)	0.41703 (11)	0.0270 (3)
O1B	0.19899 (13)	0.35763 (11)	0.44572 (8)	0.0353 (3)
C2B	0.23173 (18)	0.13264 (16)	0.38650 (12)	0.0299 (3)
N2B	0.05928 (16)	0.14283 (15)	0.37308 (12)	0.0404 (3)
O21B	−0.00902 (16)	0.04406 (15)	0.38274 (15)	0.0690 (5)
O22B	−0.00859 (16)	0.24821 (14)	0.34659 (12)	0.0576 (4)
C3B	0.32794 (19)	0.00995 (16)	0.36639 (12)	0.0315 (3)
H3B	0.279 (2)	−0.0637 (19)	0.3481 (14)	0.040 (5)*
C4B	0.49633 (19)	−0.00422 (15)	0.37139 (11)	0.0301 (3)
N4B	0.59846 (18)	−0.13327 (14)	0.34997 (11)	0.0389 (3)
O41B	0.74541 (16)	−0.14586 (14)	0.35957 (12)	0.0558 (4)
O42B	0.53534 (19)	−0.22459 (14)	0.32327 (14)	0.0652 (4)
C5B	0.56874 (19)	0.10308 (16)	0.39575 (11)	0.0303 (3)
H5B	0.681 (2)	0.0949 (17)	0.3956 (13)	0.033 (4)*
C6B	0.46974 (18)	0.22393 (16)	0.41531 (11)	0.0295 (3)
N6B	0.55497 (17)	0.33587 (15)	0.43280 (12)	0.0414 (4)
O61B	0.5170 (2)	0.44149 (14)	0.39533 (12)	0.0590 (4)
O62B	0.66595 (18)	0.31520 (16)	0.47993 (14)	0.0699 (5)
N11	0.16733 (15)	0.57565 (13)	0.16779 (10)	0.0291 (3)
H11	0.114 (2)	0.6554 (18)	0.1567 (13)	0.030 (4)*
C11A	0.2986 (3)	0.5363 (2)	0.07575 (15)	0.0456 (5)
H11C	0.346 (3)	0.450 (3)	0.0848 (19)	0.071 (7)*
H11B	0.243 (3)	0.539 (2)	0.024 (2)	0.068 (7)*
H11A	0.372 (3)	0.600 (3)	0.068 (2)	0.079 (8)*
C12	0.2433 (2)	0.58588 (17)	0.25660 (13)	0.0348 (4)
H12B	0.300 (2)	0.498 (2)	0.2664 (14)	0.041 (5)*
H12A	0.322 (3)	0.647 (2)	0.2416 (16)	0.053 (6)*
C13	0.1088 (2)	0.63356 (18)	0.34660 (13)	0.0387 (4)
H13B	0.054 (2)	0.7194 (19)	0.3366 (13)	0.035 (5)*
H13A	0.157 (2)	0.636 (2)	0.4042 (16)	0.049 (5)*
N14	−0.02066 (18)	0.54247 (15)	0.36518 (11)	0.0361 (3)
H14B	−0.100 (3)	0.576 (2)	0.4161 (16)	0.044 (5)*
H14A	0.031 (3)	0.460 (2)	0.3783 (15)	0.048 (5)*
C15	−0.0961 (2)	0.52998 (19)	0.27659 (13)	0.0364 (4)
H15B	−0.153 (2)	0.616 (2)	0.2644 (15)	0.042 (5)*
H15A	−0.171 (3)	0.471 (2)	0.2906 (15)	0.047 (5)*
C16	0.0398 (2)	0.48330 (17)	0.18685 (13)	0.0338 (3)
H16B	0.098 (2)	0.3954 (19)	0.1948 (14)	0.036 (5)*
H16A	−0.012 (3)	0.481 (2)	0.1283 (17)	0.056 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0339 (8)	0.0278 (8)	0.0286 (8)	0.0045 (6)	−0.0116 (6)	0.0010 (6)
O1A	0.0507 (7)	0.0349 (6)	0.0543 (8)	0.0144 (5)	−0.0239 (6)	−0.0092 (6)
C2A	0.0257 (7)	0.0361 (8)	0.0310 (8)	−0.0019 (6)	−0.0081 (6)	0.0030 (6)
N2A	0.0275 (7)	0.0450 (8)	0.0462 (9)	−0.0034 (6)	−0.0097 (6)	−0.0010 (7)
O21A	0.0355 (7)	0.0566 (9)	0.0925 (12)	−0.0161 (6)	−0.0166 (7)	0.0067 (8)
O22A	0.0422 (7)	0.0511 (8)	0.0820 (11)	0.0035 (6)	−0.0320 (7)	0.0070 (7)
C3A	0.0342 (8)	0.0290 (8)	0.0324 (8)	−0.0068 (6)	−0.0088 (6)	0.0024 (6)
C4A	0.0311 (7)	0.0244 (7)	0.0284 (8)	0.0010 (6)	−0.0072 (6)	0.0014 (6)
N4A	0.0435 (8)	0.0274 (7)	0.0324 (7)	0.0029 (6)	−0.0099 (6)	−0.0003 (5)
O41A	0.0381 (7)	0.0415 (7)	0.0571 (8)	0.0112 (5)	−0.0094 (6)	−0.0042 (6)
O42A	0.0646 (9)	0.0267 (6)	0.0792 (11)	−0.0052 (6)	−0.0174 (8)	−0.0055 (6)
C5A	0.0280 (7)	0.0307 (8)	0.0287 (8)	−0.0012 (6)	−0.0102 (6)	0.0027 (6)
C6A	0.0357 (8)	0.0260 (7)	0.0289 (8)	−0.0037 (6)	−0.0130 (6)	0.0011 (6)
N6A	0.0453 (8)	0.0307 (7)	0.0387 (8)	−0.0068 (6)	−0.0163 (6)	−0.0020 (6)
O61A	0.0923 (11)	0.0293 (7)	0.0920 (12)	−0.0132 (7)	−0.0508 (10)	0.0087 (7)
O62A	0.0606 (8)	0.0531 (8)	0.0682 (9)	−0.0181 (7)	−0.0407 (8)	0.0056 (7)
C1B	0.0256 (7)	0.0315 (8)	0.0221 (7)	0.0001 (6)	−0.0036 (5)	−0.0009 (6)
O1B	0.0338 (6)	0.0350 (6)	0.0336 (6)	0.0054 (5)	−0.0061 (5)	−0.0059 (5)
C2B	0.0227 (7)	0.0359 (8)	0.0308 (8)	−0.0032 (6)	−0.0055 (6)	0.0006 (6)
N2B	0.0265 (7)	0.0434 (8)	0.0523 (9)	−0.0043 (6)	−0.0108 (6)	−0.0032 (7)
O21B	0.0357 (7)	0.0529 (9)	0.1243 (15)	−0.0158 (6)	−0.0236 (8)	0.0045 (9)
O22B	0.0400 (7)	0.0510 (8)	0.0875 (11)	0.0010 (6)	−0.0315 (7)	0.0076 (7)
C3B	0.0312 (8)	0.0310 (8)	0.0331 (8)	−0.0061 (6)	−0.0070 (6)	−0.0003 (6)
C4B	0.0288 (7)	0.0312 (8)	0.0278 (8)	0.0027 (6)	−0.0050 (6)	−0.0014 (6)
N4B	0.0388 (8)	0.0355 (8)	0.0370 (8)	0.0050 (6)	−0.0031 (6)	−0.0023 (6)
O41B	0.0365 (7)	0.0511 (8)	0.0751 (10)	0.0147 (6)	−0.0155 (6)	−0.0074 (7)
O42B	0.0597 (9)	0.0352 (7)	0.0992 (13)	0.0017 (6)	−0.0186 (8)	−0.0210 (8)
C5B	0.0227 (7)	0.0402 (9)	0.0264 (8)	0.0003 (6)	−0.0053 (6)	−0.0026 (6)
C6B	0.0273 (7)	0.0349 (8)	0.0264 (7)	−0.0051 (6)	−0.0056 (6)	−0.0037 (6)
N6B	0.0318 (7)	0.0453 (9)	0.0462 (9)	−0.0065 (6)	−0.0052 (6)	−0.0166 (7)
O61B	0.0718 (9)	0.0448 (8)	0.0644 (9)	−0.0235 (7)	−0.0133 (8)	0.0015 (7)
O62B	0.0495 (8)	0.0688 (10)	0.0995 (13)	0.0001 (7)	−0.0399 (9)	−0.0343 (9)
N11	0.0286 (6)	0.0248 (6)	0.0310 (7)	0.0034 (5)	−0.0047 (5)	−0.0002 (5)
C11A	0.0464 (10)	0.0415 (11)	0.0383 (10)	0.0077 (9)	0.0055 (8)	0.0011 (8)
C12	0.0280 (8)	0.0350 (9)	0.0423 (9)	−0.0012 (7)	−0.0122 (7)	−0.0009 (7)
C13	0.0431 (9)	0.0357 (9)	0.0386 (9)	0.0020 (7)	−0.0169 (8)	−0.0092 (7)
N14	0.0343 (7)	0.0384 (8)	0.0289 (7)	0.0082 (6)	−0.0010 (6)	−0.0024 (6)
C15	0.0271 (8)	0.0411 (9)	0.0403 (9)	−0.0024 (7)	−0.0073 (7)	0.0020 (7)
C16	0.0376 (8)	0.0309 (8)	0.0342 (9)	−0.0054 (7)	−0.0104 (7)	−0.0033 (7)

Geometric parameters (Å, º) top

C1A—O1A	1.2494 (18)	N4B—O42B	1.220 (2)
C1A—C2A	1.443 (2)	N4B—O41B	1.2271 (19)
C1A—C6A	1.445 (2)	C5B—C6B	1.365 (2)
C2A—C3A	1.372 (2)	C5B—H5B	0.913 (18)
C2A—N2A	1.4470 (19)	C6B—N6B	1.466 (2)
N2A—O21A	1.2233 (19)	N6B—O62B	1.215 (2)
N2A—O22A	1.2283 (19)	N6B—O61B	1.217 (2)
C3A—C4A	1.378 (2)	N11—C16	1.490 (2)
C3A—H3A	0.93 (2)	N11—C12	1.490 (2)
C4A—C5A	1.391 (2)	N11—C11A	1.495 (2)
C4A—N4A	1.4445 (19)	N11—H11	0.892 (18)
N4A—O42A	1.2267 (19)	C11A—H11C	0.93 (3)
N4A—O41A	1.2291 (18)	C11A—H11B	0.92 (3)
C5A—C6A	1.369 (2)	C11A—H11A	0.94 (3)
C5A—H5A	0.917 (19)	C12—C13	1.505 (2)
C6A—N6A	1.4605 (19)	C12—H12B	0.97 (2)
N6A—O62A	1.2144 (18)	C12—H12A	0.96 (2)
N6A—O61A	1.2190 (19)	C13—N14	1.493 (2)
C1B—O1B	1.2612 (18)	C13—H13B	0.946 (19)
C1B—C2B	1.437 (2)	C13—H13A	0.96 (2)
C1B—C6B	1.445 (2)	N14—C15	1.488 (2)
C2B—C3B	1.372 (2)	N14—H14B	0.88 (2)
C2B—N2B	1.4521 (19)	N14—H14A	0.92 (2)
N2B—O21B	1.215 (2)	C15—C16	1.507 (2)
N2B—O22B	1.2238 (19)	C15—H15B	0.96 (2)
C3B—C4B	1.383 (2)	C15—H15A	0.92 (2)
C3B—H3B	0.959 (19)	C16—H16B	0.965 (18)
C4B—C5B	1.390 (2)	C16—H16A	0.99 (2)
C4B—N4B	1.446 (2)

O1A—C1A—C2A	124.85 (14)	C5B—C6B—C1B	124.82 (14)
O1A—C1A—C6A	123.25 (15)	C5B—C6B—N6B	116.40 (13)
C2A—C1A—C6A	111.84 (13)	C1B—C6B—N6B	118.76 (13)
C3A—C2A—C1A	124.24 (13)	O62B—N6B—O61B	123.87 (16)
C3A—C2A—N2A	116.59 (14)	O62B—N6B—C6B	117.52 (16)
C1A—C2A—N2A	119.16 (13)	O61B—N6B—C6B	118.50 (14)
O21A—N2A—O22A	122.68 (14)	C16—N11—C12	110.14 (13)
O21A—N2A—C2A	118.32 (14)	C16—N11—C11A	111.97 (14)
O22A—N2A—C2A	118.91 (14)	C12—N11—C11A	111.84 (14)
C2A—C3A—C4A	119.12 (15)	C16—N11—H11	107.5 (11)
C2A—C3A—H3A	118.9 (13)	C12—N11—H11	109.0 (11)
C4A—C3A—H3A	121.8 (13)	C11A—N11—H11	106.2 (11)
C3A—C4A—C5A	121.40 (14)	N11—C11A—H11C	106.1 (16)
C3A—C4A—N4A	119.07 (14)	N11—C11A—H11B	106.3 (15)
C5A—C4A—N4A	119.46 (13)	H11C—C11A—H11B	110 (2)
O42A—N4A—O41A	123.36 (14)	N11—C11A—H11A	106.9 (17)
O42A—N4A—C4A	118.51 (14)	H11C—C11A—H11A	116 (2)
O41A—N4A—C4A	118.12 (14)	H11B—C11A—H11A	111 (2)
C6A—C5A—C4A	118.49 (14)	N11—C12—C13	110.48 (13)
C6A—C5A—H5A	119.2 (11)	N11—C12—H12B	106.7 (11)
C4A—C5A—H5A	122.3 (11)	C13—C12—H12B	110.9 (11)
C5A—C6A—C1A	124.74 (14)	N11—C12—H12A	107.2 (13)
C5A—C6A—N6A	116.96 (13)	C13—C12—H12A	110.5 (13)
C1A—C6A—N6A	118.30 (13)	H12B—C12—H12A	110.9 (16)
O62A—N6A—O61A	122.69 (14)	N14—C13—C12	110.29 (14)
O62A—N6A—C6A	118.18 (13)	N14—C13—H13B	107.8 (11)
O61A—N6A—C6A	119.09 (13)	C12—C13—H13B	110.5 (11)
O1B—C1B—C2B	124.76 (13)	N14—C13—H13A	108.6 (12)
O1B—C1B—C6B	123.54 (14)	C12—C13—H13A	110.3 (12)
C2B—C1B—C6B	111.65 (13)	H13B—C13—H13A	109.3 (16)
C3B—C2B—C1B	124.68 (13)	C15—N14—C13	111.26 (14)
C3B—C2B—N2B	115.96 (14)	C15—N14—H14B	109.5 (13)
C1B—C2B—N2B	119.34 (13)	C13—N14—H14B	107.5 (13)
O21B—N2B—O22B	122.20 (14)	C15—N14—H14A	108.4 (13)
O21B—N2B—C2B	118.69 (14)	C13—N14—H14A	108.3 (12)
O22B—N2B—C2B	118.96 (14)	H14B—N14—H14A	111.8 (18)
C2B—C3B—C4B	118.77 (15)	N14—C15—C16	110.20 (13)
C2B—C3B—H3B	120.1 (11)	N14—C15—H15B	108.1 (12)
C4B—C3B—H3B	121.1 (11)	C16—C15—H15B	109.3 (12)
C3B—C4B—C5B	121.27 (14)	N14—C15—H15A	108.0 (13)
C3B—C4B—N4B	119.00 (14)	C16—C15—H15A	110.7 (13)
C5B—C4B—N4B	119.73 (13)	H15B—C15—H15A	110.4 (16)
O42B—N4B—O41B	122.89 (14)	N11—C16—C15	110.70 (13)
O42B—N4B—C4B	118.86 (14)	N11—C16—H16B	108.1 (10)
O41B—N4B—C4B	118.24 (14)	C15—C16—H16B	112.1 (11)
C6B—C5B—C4B	118.58 (14)	N11—C16—H16A	108.9 (13)
C6B—C5B—H5B	120.0 (11)	C15—C16—H16A	108.8 (13)
C4B—C5B—H5B	121.3 (11)	H16B—C16—H16A	108.2 (16)

O1A—C1A—C2A—C3A	172.55 (16)	C3B—C2B—N2B—O21B	27.4 (2)
C6A—C1A—C2A—C3A	−4.8 (2)	C1B—C2B—N2B—O21B	−153.91 (17)
O1A—C1A—C2A—N2A	−8.5 (2)	C3B—C2B—N2B—O22B	−148.21 (17)
C6A—C1A—C2A—N2A	174.11 (14)	C1B—C2B—N2B—O22B	30.5 (2)
C3A—C2A—N2A—O21A	−26.5 (2)	C1B—C2B—C3B—C4B	−2.8 (2)
C1A—C2A—N2A—O21A	154.53 (16)	N2B—C2B—C3B—C4B	175.80 (14)
C3A—C2A—N2A—O22A	150.03 (16)	C2B—C3B—C4B—C5B	−0.3 (2)
C1A—C2A—N2A—O22A	−29.0 (2)	C2B—C3B—C4B—N4B	−179.82 (14)
C1A—C2A—C3A—C4A	4.6 (2)	C3B—C4B—N4B—O42B	3.6 (2)
N2A—C2A—C3A—C4A	−174.39 (14)	C5B—C4B—N4B—O42B	−175.90 (16)
C2A—C3A—C4A—C5A	−1.8 (2)	C3B—C4B—N4B—O41B	−176.40 (15)
C2A—C3A—C4A—N4A	175.04 (14)	C5B—C4B—N4B—O41B	4.1 (2)
C3A—C4A—N4A—O42A	15.4 (2)	C3B—C4B—C5B—C6B	0.3 (2)
C5A—C4A—N4A—O42A	−167.73 (15)	N4B—C4B—C5B—C6B	179.78 (14)
C3A—C4A—N4A—O41A	−163.68 (14)	C4B—C5B—C6B—C1B	2.9 (2)
C5A—C4A—N4A—O41A	13.2 (2)	C4B—C5B—C6B—N6B	−175.30 (14)
C3A—C4A—C5A—C6A	−0.2 (2)	O1B—C1B—C6B—C5B	172.05 (15)
N4A—C4A—C5A—C6A	−177.01 (14)	C2B—C1B—C6B—C5B	−5.4 (2)
C4A—C5A—C6A—C1A	−0.4 (2)	O1B—C1B—C6B—N6B	−9.8 (2)
C4A—C5A—C6A—N6A	179.97 (13)	C2B—C1B—C6B—N6B	172.77 (14)
O1A—C1A—C6A—C5A	−174.70 (15)	C5B—C6B—N6B—O62B	−38.6 (2)
C2A—C1A—C6A—C5A	2.7 (2)	C1B—C6B—N6B—O62B	143.11 (16)
O1A—C1A—C6A—N6A	4.9 (2)	C5B—C6B—N6B—O61B	137.68 (16)
C2A—C1A—C6A—N6A	−177.70 (13)	C1B—C6B—N6B—O61B	−40.6 (2)
C5A—C6A—N6A—O62A	33.9 (2)	C16—N11—C12—C13	−58.20 (17)
C1A—C6A—N6A—O62A	−145.77 (16)	C11A—N11—C12—C13	176.60 (15)
C5A—C6A—N6A—O61A	−144.12 (17)	N11—C12—C13—N14	57.33 (18)
C1A—C6A—N6A—O61A	36.3 (2)	C12—C13—N14—C15	−56.74 (18)
O1B—C1B—C2B—C3B	−172.05 (15)	C13—N14—C15—C16	56.51 (19)
C6B—C1B—C2B—C3B	5.3 (2)	C12—N11—C16—C15	58.16 (17)
O1B—C1B—C2B—N2B	9.4 (2)	C11A—N11—C16—C15	−176.72 (14)
C6B—C1B—C2B—N2B	−173.25 (14)	N14—C15—C16—N11	−57.15 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O1A	0.892 (18)	1.831 (18)	2.6305 (17)	148.1 (16)
N11—H11···O22A	0.892 (18)	2.356 (18)	2.996 (2)	128.8 (14)
N14—H14B···O1Bⁱ	0.88 (2)	1.98 (2)	2.8181 (19)	157.3 (17)
N14—H14A···O1B	0.92 (2)	1.99 (2)	2.7962 (18)	146.4 (18)
N14—H14A···O22B	0.92 (2)	2.28 (2)	2.992 (2)	133.9 (16)
C5A—H5A···O21Aⁱⁱ	0.917 (19)	2.476 (19)	3.383 (2)	170.3 (16)
C5B—H5B···O21Bⁱⁱⁱ	0.913 (18)	2.487 (18)	3.394 (2)	172.3 (15)
C11A—H11C···O41A^iv	0.93 (3)	2.48 (3)	3.345 (2)	155 (2)
C11A—H11A···O62Aⁱⁱⁱ	0.94 (3)	2.57 (3)	3.496 (3)	168 (2)
C12—H12A···O22A	0.96 (2)	2.56 (2)	3.046 (2)	111.6 (15)
C13—H13A···O62B^v	0.96 (2)	2.46 (2)	3.386 (2)	162.9 (17)

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

Experimental details

Crystal data
Chemical formula	C₅H₁₄N₂²⁺·2C₆H₂N₃O₇⁻
M_r	558.39
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.2001 (12), 10.1780 (15), 13.7399 (18)
α, β, γ (°)	89.798 (12), 78.130 (11), 81.558 (12)
V (Å³)	1109.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.4 × 0.15 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.936, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21056, 4891, 3624
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.123, 0.95
No. of reflections	4891
No. of parameters	424
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.30

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), Stereochemical Workstation Operation Manual (Siemens, 1989).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O1A	0.892 (18)	1.831 (18)	2.6305 (17)	148.1 (16)
N11—H11···O22A	0.892 (18)	2.356 (18)	2.996 (2)	128.8 (14)
N14—H14B···O1Bⁱ	0.88 (2)	1.98 (2)	2.8181 (19)	157.3 (17)
N14—H14A···O1B	0.92 (2)	1.99 (2)	2.7962 (18)	146.4 (18)
N14—H14A···O22B	0.92 (2)	2.28 (2)	2.992 (2)	133.9 (16)
C5A—H5A···O21Aⁱⁱ	0.917 (19)	2.476 (19)	3.383 (2)	170.3 (16)
C5B—H5B···O21Bⁱⁱⁱ	0.913 (18)	2.487 (18)	3.394 (2)	172.3 (15)
C11A—H11C···O41A^iv	0.93 (3)	2.48 (3)	3.345 (2)	155 (2)
C11A—H11A···O62Aⁱⁱⁱ	0.94 (3)	2.57 (3)	3.496 (3)	168 (2)
C12—H12A···O22A	0.96 (2)	2.56 (2)	3.046 (2)	111.6 (15)
C13—H13A···O62B^v	0.96 (2)	2.46 (2)	3.386 (2)	162.9 (17)

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

Acknowledgements

SS thanks Mangalore University for the research facilities.

References

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