Cinnarizinium 3,5-dinitro­salicylate

Dayananda, A.S.; Yathirajan, H.S.; Gerber, T.; Hosten, E.; Betz, R.

doi:10.1107/S1600536812011518

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages o1165-o1166

doi:10.1107/S1600536812011518

Open

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Cinnarizinium 3,5-dinitrosalicylate

Alaloor S. Dayananda,^a Hemmige S. Yathirajan,^a Thomas Gerber,^b Eric Hosten ^b and Richard Betz ^b ^*

^aUniversity of Mysore, Department of Studies in Chemistry, Manasagangotri, Mysore 570 006, India, and ^bNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 6 February 2012; accepted 16 March 2012; online 24 March 2012)

The title compound [systematic name: 4-diphenylmethyl-1-(3-phenylprop-2-en-1-yl)-piperazin-1-ium 2-carboxy-4,6-dinitrophenolate], C₂₆H₂₉N₂⁺·C₇H₃N₂O₇⁻, is the dinitrosalicylate salt of a tertiary amine. Deprotonation of the carboxylic acid group occurred on the phenolic hydroxy group. The diazacyclohexane ring adopts a chair conformation. Intramolecular O—H⋯O and intermolecular C—H⋯O and N—H⋯O hydrogen bonds are observed. The N—H⋯O hydrogen bonds are bifurcated at the H atom and connect the cinnarizinium and 3,5-dinitrosalicylate ions together. Intermolecular C—H⋯O hydrogen bonds connect the components into layers perpendicular to the crystallographic a axis.

Related literature

For pharmaceutical background to cinnarizine, see: Barrett & Zolov (1960 ). For related structures, see: Bertolasi et al. (1980 ); Smith et al. (2001 ); Jasinski et al. (2011 ). For puckering analysis, see: Cremer & Pople (1975 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₆H₂₉N₂⁺·C₇H₃N₂O₇⁻
M_r = 596.63
Monoclinic, P 2₁ /c
a = 14.5648 (3) Å
b = 12.9374 (3) Å
c = 16.1619 (3) Å
β = 103.900 (1)°
V = 2956.22 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.51 × 0.26 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.932, T_max = 1.000
29552 measured reflections
7344 independent reflections
6023 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.148
S = 1.03
7344 reflections
401 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H71⋯O1ⁱ	0.89 (2)	1.99 (2)	2.8105 (18)	153.5 (17)
N1—H71⋯O2ⁱ	0.89 (2)	2.36 (2)	3.037 (2)	132.4 (16)
O7—H7⋯O1	0.84	1.75	2.507 (2)	149
C3—H3A⋯O6ⁱⁱ	0.99	2.40	3.341 (2)	160
C32—H32⋯O5	0.95	2.52	3.453 (2)	166
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011518/rn2101sup1.cif

Supporting information file. DOI: 10.1107/S1600536812011518/rn2101Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011518/rn2101Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812011518/rn2101Isup4.cml

checkCIF report

Comment top

Cinnarizine is an antihistamine which is mainly used for the control of nausea and vomiting due to motion sickness. A clinical evaluation of cinnarizine in various allergic disorders is published (Barrett & Zolov, 1960). The crystal structures of some related compounds such as cyclizine hydrochloride (Bertolasi et al., 1980), guanidinium 3,5-dinitrosalicylate (Smith et al., 2001) and cinnarizine dipicrate (Jasinski et al., 2011) have been reported.

Deprotonation occurred at the phenolic hydroxy group while the carboxyl group remains in its protonated state. Protonation occurred on the nitrogen atom bearing the vinylic substituent. The 1,4-diazacyclohexane moiety adopts a ⁴C₁ (^N2C_N1) conformation (Cremer & Pople, 1975). The least-squares planes defined by the carbon atoms of the aromatic moieties on the diphenylmethyl substituent enclose an angle of 66.06 (8)° and intersect with the plane defined by the phenyl group bonded to the vinylic substituent at angles of 16.76 (9)° and 72.01 (9)°, respectively. The least-squares planes defined by the individual phenyl groups of the cation enclose angles of 37.54 (9)°, 53.70 (8)° and 79.26 (8)° with the corresponding plane of the carboxylic acid (Fig. 1).

In the crystal, intramolecular O—H···O and intermolecular C—H···O and N—H···O hydrogen bonds in are observed. The N–H···O hydrogen bonds are bifurcated at H7. A graphical representation in terms of donor and acceptor atoms for a selection of these contacts is given in Figure 2. In terms of graph-set analysis, (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the hydrogen bonds is S(6)DD on the unary level while the C–H···O contacts necessitate a DD descriptor on the same level. The C–H···O hydrogen bonds connect the components together into layers perpendicular to the crystallographic a axis (Fig. 2). The shortest intercentroid distance between two aromatic systems was measured at 4.2848 (11) Å and is apparent between the phenyl group conjugated to the vinylic system and the aromatic ring of the dinitrosalicylate anion.

Related literature top

For pharmaceutical background to cinnarizine, see: Barrett & Zolov (1960). For related structures, see: Bertolasi et al. (1980); Smith et al. (2001); Jasinski et al. (2011). For puckering analysis, see: Cremer & Pople (1975). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

Cinnarizine (3.68 g, 0.01 mol) and 3,5-dinitrosalicylic acid (2.28 g, 0.01 mol) were dissolved in hot acetone and stirred over a heating magnetic stirrer for few minutes (330 K). The resulting solution was allowed to cool slowly at room temperature. The salt formed was filtered and dried in a vaccum desiccator over phosphorous pentoxide. The compound was recrystallized from a mixture of DMSO and acetonitrile (v:v = 1:1) by slow evaporation (m.p.: 383 K).

Structure description top

For pharmaceutical background to cinnarizine, see: Barrett & Zolov (1960). For related structures, see: Bertolasi et al. (1980); Smith et al. (2001); Jasinski et al. (2011). For puckering analysis, see: Cremer & Pople (1975). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
	Fig. 2. Intermolecular contacts, viewed approximately along [1 1 1]. For clarity, only a selection of intra- and intermolecular contacts is depicted. Yellow dashed lines denote intramolecular hydrogen bonds, blue dashed lines denote intermolecular hydrogen bonds and green dashed lines indicate C–H···O contacts. Symmetry operators: ⁱ -x + 1, -y + 1, -z + 1; ⁱⁱ -x + 1, y + 1/2, -z + 1/2.

4-diphenylmethyl-1-(3-phenylprop-2-en-1-yl)piperazin-1-ium 2-carboxy-4,6-dinitrophenolate top

Crystal data top

C₂₆H₂₉N₂⁺·C₇H₃N₂O₇⁻	F(000) = 1256
M_r = 596.63	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 383 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.5648 (3) Å	Cell parameters from 9909 reflections
b = 12.9374 (3) Å	θ = 2.3–28.3°
c = 16.1619 (3) Å	µ = 0.10 mm⁻¹
β = 103.900 (1)°	T = 200 K
V = 2956.22 (11) Å³	Block, yellow
Z = 4	0.51 × 0.26 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	7344 independent reflections
Radiation source: fine-focus sealed tube	6023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
φ and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
T_min = 0.932, T_max = 1.000	k = −17→17
29552 measured reflections	l = −21→15

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.070P)² + 1.6929P] where P = (F_o² + 2F_c²)/3
7344 reflections	(Δ/σ)_max < 0.001
401 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₂₆H₂₉N₂⁺·C₇H₃N₂O₇⁻	V = 2956.22 (11) Å³
M_r = 596.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.5648 (3) Å	µ = 0.10 mm⁻¹
b = 12.9374 (3) Å	T = 200 K
c = 16.1619 (3) Å	0.51 × 0.26 × 0.17 mm
β = 103.900 (1)°

Data collection top

Bruker APEXII CCD diffractometer	7344 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6023 reflections with I > 2σ(I)
T_min = 0.932, T_max = 1.000	R_int = 0.015
29552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.85 e Å⁻³
7344 reflections	Δρ_min = −0.35 e Å⁻³
401 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.25623 (8)	0.71175 (10)	0.31330 (8)	0.0251 (2)
H71	0.2998 (14)	0.6749 (15)	0.3494 (13)	0.034 (5)*
N2	0.10014 (8)	0.56688 (9)	0.26578 (7)	0.0238 (2)
C1	0.29863 (11)	0.95171 (13)	0.41663 (10)	0.0338 (3)
H1A	0.2459	0.9812	0.3774	0.041*
C2	0.33475 (11)	0.86690 (12)	0.39167 (10)	0.0326 (3)
H2	0.3869	0.8355	0.4301	0.039*
C3	0.29836 (12)	0.81760 (12)	0.30658 (10)	0.0341 (3)
H3A	0.3508	0.8110	0.2777	0.041*
H3B	0.2495	0.8628	0.2711	0.041*
C4	0.17100 (10)	0.71680 (12)	0.34936 (10)	0.0287 (3)
H4A	0.1231	0.7629	0.3138	0.034*
H4B	0.1889	0.7459	0.4077	0.034*
C5	0.12940 (10)	0.61023 (12)	0.35209 (9)	0.0279 (3)
H5A	0.1770	0.5644	0.3883	0.034*
H5B	0.0741	0.6143	0.3775	0.034*
C6	0.18554 (10)	0.55568 (12)	0.23334 (9)	0.0267 (3)
H6A	0.1686	0.5236	0.1761	0.032*
H6B	0.2310	0.5095	0.2716	0.032*
C7	0.23147 (11)	0.65942 (12)	0.22794 (9)	0.0285 (3)
H7A	0.2895	0.6497	0.2072	0.034*
H7B	0.1877	0.7039	0.1866	0.034*
C8	0.05330 (9)	0.46543 (11)	0.26749 (9)	0.0234 (3)
H8	0.0999	0.4178	0.3043	0.028*
C11	0.33137 (12)	1.00538 (12)	0.49873 (10)	0.0328 (3)
C12	0.41578 (13)	0.97939 (14)	0.55689 (11)	0.0393 (4)
H12	0.4549	0.9265	0.5432	0.047*
C13	0.44279 (15)	1.03042 (18)	0.63443 (12)	0.0502 (5)
H13	0.4998	1.0115	0.6739	0.060*
C14	0.38744 (17)	1.10827 (18)	0.65452 (13)	0.0555 (5)
H14	0.4068	1.1435	0.7074	0.067*
C15	0.30396 (16)	1.13519 (17)	0.59790 (14)	0.0521 (5)
H15	0.2657	1.1887	0.6119	0.062*
C16	0.27599 (13)	1.08397 (14)	0.52044 (12)	0.0407 (4)
H16	0.2184	1.1027	0.4817	0.049*
C21	−0.03163 (10)	0.47510 (11)	0.30648 (9)	0.0246 (3)
C22	−0.04283 (11)	0.40380 (12)	0.36751 (10)	0.0323 (3)
H22	0.0030	0.3509	0.3849	0.039*
C23	−0.12068 (13)	0.40914 (14)	0.40346 (11)	0.0397 (4)
H23	−0.1275	0.3601	0.4454	0.048*
C24	−0.18792 (12)	0.48540 (14)	0.37840 (12)	0.0388 (4)
H24	−0.2414	0.4885	0.4024	0.047*
C25	−0.17702 (11)	0.55719 (13)	0.31830 (11)	0.0352 (3)
H25	−0.2231	0.6099	0.3011	0.042*
C26	−0.09910 (10)	0.55295 (12)	0.28272 (10)	0.0294 (3)
H26	−0.0918	0.6033	0.2420	0.035*
C31	0.02530 (10)	0.41884 (11)	0.17808 (9)	0.0251 (3)
C32	0.06680 (12)	0.32722 (12)	0.16047 (11)	0.0337 (3)
H32	0.1122	0.2937	0.2044	0.040*
C33	0.04250 (13)	0.28413 (13)	0.07907 (12)	0.0394 (4)
H33	0.0719	0.2220	0.0676	0.047*
C34	−0.02374 (13)	0.33119 (14)	0.01544 (11)	0.0386 (4)
H34	−0.0400	0.3019	−0.0401	0.046*
C35	−0.06687 (13)	0.42141 (15)	0.03242 (10)	0.0390 (4)
H35	−0.1138	0.4532	−0.0112	0.047*
C36	−0.04164 (11)	0.46560 (13)	0.11309 (10)	0.0322 (3)
H36	−0.0705	0.5284	0.1239	0.039*
O1	0.63343 (8)	0.37345 (10)	0.53526 (8)	0.0398 (3)
O2	0.58174 (10)	0.44031 (15)	0.67150 (9)	0.0619 (4)
O3	0.43582 (10)	0.48104 (13)	0.65686 (9)	0.0557 (4)
O4	0.19460 (9)	0.32142 (13)	0.44738 (11)	0.0578 (4)
O5	0.22771 (11)	0.24235 (14)	0.34093 (10)	0.0635 (4)
O6	0.54743 (11)	0.23538 (12)	0.30218 (9)	0.0525 (4)
O7	0.66612 (10)	0.28953 (12)	0.40548 (10)	0.0517 (4)
H7	0.6736	0.3061	0.4569	0.078*
N3	0.49860 (10)	0.43821 (12)	0.63196 (9)	0.0388 (3)
N4	0.25126 (10)	0.29137 (13)	0.40744 (10)	0.0436 (4)
C9	0.57578 (13)	0.27360 (14)	0.37134 (12)	0.0402 (4)
C41	0.54463 (10)	0.35631 (12)	0.50730 (10)	0.0305 (3)
C42	0.50991 (11)	0.30575 (12)	0.42633 (10)	0.0321 (3)
C43	0.41582 (12)	0.28489 (13)	0.39505 (10)	0.0332 (3)
H43	0.3951	0.2501	0.3421	0.040*
C44	0.35102 (11)	0.31446 (12)	0.44044 (10)	0.0318 (3)
C45	0.37853 (11)	0.36483 (12)	0.51759 (10)	0.0310 (3)
H45	0.3329	0.3856	0.5476	0.037*
C46	0.47329 (11)	0.38454 (12)	0.55055 (10)	0.0297 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0223 (6)	0.0289 (6)	0.0240 (6)	−0.0037 (5)	0.0053 (5)	−0.0023 (5)
N2	0.0211 (5)	0.0270 (6)	0.0237 (5)	−0.0032 (4)	0.0064 (4)	−0.0032 (4)
C1	0.0304 (7)	0.0359 (8)	0.0317 (8)	−0.0039 (6)	0.0011 (6)	−0.0002 (6)
C2	0.0314 (7)	0.0309 (7)	0.0331 (8)	−0.0073 (6)	0.0030 (6)	0.0005 (6)
C3	0.0400 (8)	0.0311 (8)	0.0322 (8)	−0.0112 (6)	0.0105 (6)	−0.0016 (6)
C4	0.0231 (6)	0.0334 (7)	0.0307 (7)	−0.0026 (5)	0.0087 (6)	−0.0078 (6)
C5	0.0251 (7)	0.0345 (7)	0.0254 (7)	−0.0053 (6)	0.0083 (5)	−0.0053 (6)
C6	0.0240 (6)	0.0307 (7)	0.0272 (7)	−0.0035 (5)	0.0095 (5)	−0.0048 (5)
C7	0.0287 (7)	0.0342 (7)	0.0235 (6)	−0.0061 (6)	0.0080 (5)	−0.0042 (6)
C8	0.0205 (6)	0.0252 (6)	0.0246 (6)	0.0003 (5)	0.0058 (5)	0.0008 (5)
C11	0.0354 (8)	0.0313 (7)	0.0310 (7)	−0.0078 (6)	0.0064 (6)	−0.0001 (6)
C12	0.0396 (9)	0.0414 (9)	0.0344 (8)	−0.0059 (7)	0.0040 (7)	0.0005 (7)
C13	0.0517 (11)	0.0614 (12)	0.0325 (9)	−0.0141 (9)	0.0000 (8)	0.0007 (8)
C14	0.0685 (14)	0.0629 (13)	0.0365 (9)	−0.0230 (11)	0.0154 (9)	−0.0156 (9)
C15	0.0600 (12)	0.0464 (11)	0.0552 (12)	−0.0103 (9)	0.0244 (10)	−0.0147 (9)
C16	0.0402 (9)	0.0359 (8)	0.0456 (9)	−0.0052 (7)	0.0095 (7)	−0.0041 (7)
C21	0.0217 (6)	0.0264 (6)	0.0253 (6)	−0.0019 (5)	0.0052 (5)	−0.0023 (5)
C22	0.0320 (7)	0.0331 (8)	0.0340 (8)	0.0033 (6)	0.0120 (6)	0.0052 (6)
C23	0.0436 (9)	0.0399 (9)	0.0423 (9)	0.0008 (7)	0.0236 (8)	0.0059 (7)
C24	0.0347 (8)	0.0390 (9)	0.0497 (10)	−0.0022 (7)	0.0241 (7)	−0.0077 (7)
C25	0.0279 (7)	0.0339 (8)	0.0446 (9)	0.0044 (6)	0.0105 (6)	−0.0057 (7)
C26	0.0281 (7)	0.0280 (7)	0.0325 (7)	0.0014 (6)	0.0084 (6)	0.0003 (6)
C31	0.0231 (6)	0.0258 (6)	0.0279 (7)	−0.0047 (5)	0.0089 (5)	−0.0018 (5)
C32	0.0337 (8)	0.0301 (7)	0.0373 (8)	0.0019 (6)	0.0084 (6)	−0.0025 (6)
C33	0.0452 (9)	0.0304 (8)	0.0451 (9)	−0.0014 (7)	0.0156 (8)	−0.0096 (7)
C34	0.0467 (9)	0.0383 (9)	0.0322 (8)	−0.0107 (7)	0.0122 (7)	−0.0100 (7)
C35	0.0401 (9)	0.0457 (9)	0.0285 (8)	−0.0005 (7)	0.0031 (7)	−0.0022 (7)
C36	0.0321 (7)	0.0341 (8)	0.0300 (7)	0.0026 (6)	0.0066 (6)	−0.0019 (6)
O1	0.0252 (5)	0.0475 (7)	0.0449 (7)	−0.0019 (5)	0.0047 (5)	0.0070 (5)
O2	0.0369 (7)	0.0965 (13)	0.0456 (8)	0.0019 (7)	−0.0034 (6)	−0.0231 (8)
O3	0.0473 (8)	0.0700 (10)	0.0462 (8)	0.0148 (7)	0.0041 (6)	−0.0177 (7)
O4	0.0247 (6)	0.0743 (10)	0.0719 (10)	0.0057 (6)	0.0065 (6)	0.0004 (8)
O5	0.0467 (8)	0.0779 (11)	0.0535 (9)	−0.0096 (8)	−0.0122 (7)	−0.0138 (8)
O6	0.0609 (9)	0.0615 (9)	0.0405 (7)	0.0067 (7)	0.0230 (7)	−0.0021 (6)
O7	0.0400 (7)	0.0633 (9)	0.0579 (8)	0.0010 (6)	0.0236 (6)	−0.0020 (7)
N3	0.0367 (7)	0.0409 (8)	0.0361 (7)	0.0042 (6)	0.0037 (6)	−0.0025 (6)
N4	0.0309 (7)	0.0474 (9)	0.0452 (8)	−0.0006 (6)	−0.0051 (6)	0.0038 (7)
C9	0.0398 (9)	0.0360 (8)	0.0489 (10)	0.0046 (7)	0.0188 (8)	0.0090 (7)
C41	0.0246 (7)	0.0280 (7)	0.0373 (8)	0.0023 (5)	0.0045 (6)	0.0099 (6)
C42	0.0336 (8)	0.0300 (7)	0.0354 (8)	0.0049 (6)	0.0135 (6)	0.0076 (6)
C43	0.0378 (8)	0.0321 (8)	0.0287 (7)	0.0010 (6)	0.0059 (6)	0.0027 (6)
C44	0.0245 (7)	0.0338 (8)	0.0338 (8)	0.0008 (6)	0.0003 (6)	0.0030 (6)
C45	0.0261 (7)	0.0327 (7)	0.0341 (8)	0.0058 (6)	0.0069 (6)	0.0022 (6)
C46	0.0292 (7)	0.0287 (7)	0.0286 (7)	0.0025 (6)	0.0018 (6)	0.0018 (6)

Geometric parameters (Å, º) top

N1—C4	1.4940 (18)	C22—C23	1.395 (2)
N1—C7	1.5009 (18)	C22—H22	0.9500
N1—C3	1.5151 (19)	C23—C24	1.381 (3)
N1—H71	0.89 (2)	C23—H23	0.9500
N2—C6	1.4683 (17)	C24—C25	1.380 (3)
N2—C5	1.4685 (17)	C24—H24	0.9500
N2—C8	1.4826 (17)	C25—C26	1.391 (2)
C1—C2	1.321 (2)	C25—H25	0.9500
C1—C11	1.472 (2)	C26—H26	0.9500
C1—H1A	0.9500	C31—C36	1.388 (2)
C2—C3	1.493 (2)	C31—C32	1.391 (2)
C2—H2	0.9500	C32—C33	1.394 (2)
C3—H3A	0.9900	C32—H32	0.9500
C3—H3B	0.9900	C33—C34	1.372 (3)
C4—C5	1.511 (2)	C33—H33	0.9500
C4—H4A	0.9900	C34—C35	1.384 (3)
C4—H4B	0.9900	C34—H34	0.9500
C5—H5A	0.9900	C35—C36	1.390 (2)
C5—H5B	0.9900	C35—H35	0.9500
C6—C7	1.511 (2)	C36—H36	0.9500
C6—H6A	0.9900	O1—C41	1.2826 (19)
C6—H6B	0.9900	O2—N3	1.226 (2)
C7—H7A	0.9900	O3—N3	1.217 (2)
C7—H7B	0.9900	O4—N4	1.227 (2)
C8—C21	1.5224 (18)	O5—N4	1.224 (2)
C8—C31	1.5279 (19)	O6—C9	1.201 (2)
C8—H8	1.0000	O7—C9	1.315 (2)
C11—C16	1.394 (2)	O7—H7	0.8399
C11—C12	1.397 (2)	N3—C46	1.455 (2)
C12—C13	1.387 (3)	N4—C44	1.453 (2)
C12—H12	0.9500	C9—C42	1.514 (2)
C13—C14	1.377 (3)	C41—C46	1.432 (2)
C13—H13	0.9500	C41—C42	1.442 (2)
C14—C15	1.379 (3)	C42—C43	1.369 (2)
C14—H14	0.9500	C43—C44	1.381 (2)
C15—C16	1.388 (3)	C43—H43	0.9500
C15—H15	0.9500	C44—C45	1.378 (2)
C16—H16	0.9500	C45—C46	1.379 (2)
C21—C22	1.388 (2)	C45—H45	0.9500
C21—C26	1.395 (2)

C4—N1—C7	109.85 (11)	C15—C16—H16	119.6
C4—N1—C3	112.16 (12)	C11—C16—H16	119.6
C7—N1—C3	110.73 (11)	C22—C21—C26	118.69 (13)
C4—N1—H71	107.2 (12)	C22—C21—C8	119.03 (13)
C7—N1—H71	109.6 (12)	C26—C21—C8	122.28 (13)
C3—N1—H71	107.1 (13)	C21—C22—C23	120.60 (15)
C6—N2—C5	107.43 (11)	C21—C22—H22	119.7
C6—N2—C8	110.63 (11)	C23—C22—H22	119.7
C5—N2—C8	110.50 (11)	C24—C23—C22	120.24 (15)
C2—C1—C11	126.91 (15)	C24—C23—H23	119.9
C2—C1—H1A	116.5	C22—C23—H23	119.9
C11—C1—H1A	116.5	C25—C24—C23	119.60 (14)
C1—C2—C3	123.84 (15)	C25—C24—H24	120.2
C1—C2—H2	118.1	C23—C24—H24	120.2
C3—C2—H2	118.1	C24—C25—C26	120.50 (15)
C2—C3—N1	112.36 (12)	C24—C25—H25	119.8
C2—C3—H3A	109.1	C26—C25—H25	119.8
N1—C3—H3A	109.1	C25—C26—C21	120.35 (14)
C2—C3—H3B	109.1	C25—C26—H26	119.8
N1—C3—H3B	109.1	C21—C26—H26	119.8
H3A—C3—H3B	107.9	C36—C31—C32	118.51 (14)
N1—C4—C5	110.38 (12)	C36—C31—C8	121.53 (13)
N1—C4—H4A	109.6	C32—C31—C8	119.96 (13)
C5—C4—H4A	109.6	C31—C32—C33	120.64 (15)
N1—C4—H4B	109.6	C31—C32—H32	119.7
C5—C4—H4B	109.6	C33—C32—H32	119.7
H4A—C4—H4B	108.1	C34—C33—C32	120.22 (16)
N2—C5—C4	110.34 (12)	C34—C33—H33	119.9
N2—C5—H5A	109.6	C32—C33—H33	119.9
C4—C5—H5A	109.6	C33—C34—C35	119.77 (15)
N2—C5—H5B	109.6	C33—C34—H34	120.1
C4—C5—H5B	109.6	C35—C34—H34	120.1
H5A—C5—H5B	108.1	C34—C35—C36	120.18 (16)
N2—C6—C7	110.95 (12)	C34—C35—H35	119.9
N2—C6—H6A	109.4	C36—C35—H35	119.9
C7—C6—H6A	109.4	C31—C36—C35	120.65 (15)
N2—C6—H6B	109.4	C31—C36—H36	119.7
C7—C6—H6B	109.4	C35—C36—H36	119.7
H6A—C6—H6B	108.0	C9—O7—H7	109.5
N1—C7—C6	111.07 (11)	O3—N3—O2	122.94 (16)
N1—C7—H7A	109.4	O3—N3—C46	117.98 (14)
C6—C7—H7A	109.4	O2—N3—C46	119.07 (14)
N1—C7—H7B	109.4	O5—N4—O4	122.97 (16)
C6—C7—H7B	109.4	O5—N4—C44	118.25 (16)
H7A—C7—H7B	108.0	O4—N4—C44	118.78 (15)
N2—C8—C21	110.99 (11)	O6—C9—O7	122.73 (17)
N2—C8—C31	110.55 (11)	O6—C9—C42	122.32 (17)
C21—C8—C31	111.42 (11)	O7—C9—C42	114.95 (16)
N2—C8—H8	107.9	O1—C41—C46	124.92 (15)
C21—C8—H8	107.9	O1—C41—C42	120.16 (15)
C31—C8—H8	107.9	C46—C41—C42	114.92 (13)
C16—C11—C12	118.36 (16)	C43—C42—C41	121.77 (14)
C16—C11—C1	119.29 (15)	C43—C42—C9	116.64 (15)
C12—C11—C1	122.35 (16)	C41—C42—C9	121.59 (15)
C13—C12—C11	120.39 (18)	C42—C43—C44	120.03 (15)
C13—C12—H12	119.8	C42—C43—H43	120.0
C11—C12—H12	119.8	C44—C43—H43	120.0
C14—C13—C12	120.41 (19)	C45—C44—C43	121.62 (14)
C14—C13—H13	119.8	C45—C44—N4	118.47 (15)
C12—C13—H13	119.8	C43—C44—N4	119.91 (15)
C13—C14—C15	120.06 (18)	C44—C45—C46	118.90 (14)
C13—C14—H14	120.0	C44—C45—H45	120.5
C15—C14—H14	120.0	C46—C45—H45	120.5
C14—C15—C16	119.9 (2)	C45—C46—C41	122.74 (14)
C14—C15—H15	120.0	C45—C46—N3	116.77 (14)
C16—C15—H15	120.0	C41—C46—N3	120.48 (14)
C15—C16—C11	120.85 (18)

C11—C1—C2—C3	−179.12 (15)	N2—C8—C31—C36	−64.73 (17)
C1—C2—C3—N1	−114.54 (17)	C21—C8—C31—C36	59.19 (17)
C4—N1—C3—C2	63.88 (17)	N2—C8—C31—C32	115.63 (14)
C7—N1—C3—C2	−173.02 (13)	C21—C8—C31—C32	−120.45 (14)
C7—N1—C4—C5	54.46 (16)	C36—C31—C32—C33	0.8 (2)
C3—N1—C4—C5	178.06 (12)	C8—C31—C32—C33	−179.55 (14)
C6—N2—C5—C4	63.12 (15)	C31—C32—C33—C34	−0.8 (3)
C8—N2—C5—C4	−176.12 (11)	C32—C33—C34—C35	−0.4 (3)
N1—C4—C5—N2	−60.74 (15)	C33—C34—C35—C36	1.5 (3)
C5—N2—C6—C7	−61.67 (15)	C32—C31—C36—C35	0.3 (2)
C8—N2—C6—C7	177.64 (11)	C8—C31—C36—C35	−179.31 (14)
C4—N1—C7—C6	−53.14 (16)	C34—C35—C36—C31	−1.5 (3)
C3—N1—C7—C6	−177.57 (12)	O1—C41—C42—C43	179.06 (15)
N2—C6—C7—N1	57.82 (16)	C46—C41—C42—C43	−1.4 (2)
C6—N2—C8—C21	176.26 (11)	O1—C41—C42—C9	−1.3 (2)
C5—N2—C8—C21	57.42 (14)	C46—C41—C42—C9	178.26 (14)
C6—N2—C8—C31	−59.58 (14)	O6—C9—C42—C43	2.9 (2)
C5—N2—C8—C31	−178.42 (11)	O7—C9—C42—C43	−176.34 (15)
C2—C1—C11—C16	−169.51 (17)	O6—C9—C42—C41	−176.79 (16)
C2—C1—C11—C12	9.5 (3)	O7—C9—C42—C41	4.0 (2)
C16—C11—C12—C13	0.5 (3)	C41—C42—C43—C44	1.4 (2)
C1—C11—C12—C13	−178.46 (16)	C9—C42—C43—C44	−178.21 (14)
C11—C12—C13—C14	−0.9 (3)	C42—C43—C44—C45	−0.2 (2)
C12—C13—C14—C15	0.8 (3)	C42—C43—C44—N4	−179.44 (15)
C13—C14—C15—C16	−0.3 (3)	O5—N4—C44—C45	−176.60 (17)
C14—C15—C16—C11	−0.1 (3)	O4—N4—C44—C45	3.2 (2)
C12—C11—C16—C15	0.0 (3)	O5—N4—C44—C43	2.7 (2)
C1—C11—C16—C15	179.02 (17)	O4—N4—C44—C43	−177.57 (16)
N2—C8—C21—C22	−133.38 (14)	C43—C44—C45—C46	−1.0 (2)
C31—C8—C21—C22	102.95 (15)	N4—C44—C45—C46	178.23 (14)
N2—C8—C21—C26	46.96 (17)	C44—C45—C46—C41	1.0 (2)
C31—C8—C21—C26	−76.71 (17)	C44—C45—C46—N3	179.78 (14)
C26—C21—C22—C23	0.8 (2)	O1—C41—C46—C45	179.67 (15)
C8—C21—C22—C23	−178.82 (15)	C42—C41—C46—C45	0.1 (2)
C21—C22—C23—C24	0.3 (3)	O1—C41—C46—N3	1.0 (2)
C22—C23—C24—C25	−0.8 (3)	C42—C41—C46—N3	−178.57 (13)
C23—C24—C25—C26	0.2 (3)	O3—N3—C46—C45	−15.1 (2)
C24—C25—C26—C21	0.9 (2)	O2—N3—C46—C45	166.34 (17)
C22—C21—C26—C25	−1.4 (2)	O3—N3—C46—C41	163.64 (16)
C8—C21—C26—C25	178.21 (14)	O2—N3—C46—C41	−14.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···O1ⁱ	0.89 (2)	1.99 (2)	2.8105 (18)	153.5 (17)
N1—H71···O2ⁱ	0.89 (2)	2.36 (2)	3.037 (2)	132.4 (16)
O7—H7···O1	0.84	1.75	2.507 (2)	149
C3—H3A···O6ⁱⁱ	0.99	2.40	3.341 (2)	160
C32—H32···O5	0.95	2.52	3.453 (2)	166

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₉N₂⁺·C₇H₃N₂O₇⁻
M_r	596.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	14.5648 (3), 12.9374 (3), 16.1619 (3)
β (°)	103.900 (1)
V (Å³)	2956.22 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.51 × 0.26 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.932, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	29552, 7344, 6023
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.148, 1.03
No. of reflections	7344
No. of parameters	401
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.35

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···O1ⁱ	0.89 (2)	1.99 (2)	2.8105 (18)	153.5 (17)
N1—H71···O2ⁱ	0.89 (2)	2.36 (2)	3.037 (2)	132.4 (16)
O7—H7···O1	0.84	1.75	2.507 (2)	149.0
C3—H3A···O6ⁱⁱ	0.99	2.40	3.341 (2)	159.5
C32—H32···O5	0.95	2.52	3.453 (2)	166.3

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

Acknowledgements

ASD thanks University of Mysore for research facilities

References

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