Cinnarizinium picrate

Song, Y.; Chidan Kumar, C.S.; Nethravathi, G.B.; Naveen, S.; Li, H.

doi:10.1107/S1600536812020764

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1747

doi:10.1107/S1600536812020764

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Cinnarizinium picrate

Yanxi Song,^a C. S. Chidan Kumar,^b G. B. Nethravathi,^c S. Naveen ^d and Hongqi Li ^e ^*

^aSchool of Environmental Science and Engineering, Donghua University, Shanghai 201620, People's Republic of China, ^bDepartment of Chemistry, G. Madegowda Institute of Technology, Bharathi Nagar 571 422, India, ^cDepartment of Chemistry, B.E.T. Academy of Higher Education, Bharathi Nagar 571 422, India, ^dDepartment of Physics, School of Engineering and Technology, Jain University, Bangalore 562 112, India, and ^eKey Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, People's Republic of China
^*Correspondence e-mail: hongqili@dhu.edu.cn

(Received 1 May 2012; accepted 8 May 2012; online 16 May 2012)

In the title salt {systematic name: 4-diphenylmethyl-1-[(E)-3-phenylprop-2-en-1-yl]piperazin-1-ium 2,4,6-trinitrophenolate), C₂₆H₂₉N₂⁺·C₆H₂N₃O₇⁻, the cinnarizinium cation is protonated at the piperazine N atom connected to the styrenylmethyl group; the piperazine ring adopts a distorted chair conformaiton. In the crystal, bifurcated N—H⋯(O,O) hydrogen bonds link the components into two-ion aggregates.

Related literature

For background to the anti-histamine cinnarizine, see: Towse (1980 ); Barrett & Zolov (1960 ). For related structures, see: Mouillé et al. (1975 ); Bertolasi et al. (1980 ); Jasinski et al. (2011 ). For additional conformational analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₆H₂₉N₂⁺·C₆H₂N₃O₇⁻
M_r = 597.62
Monoclinic, P 2₁ /c
a = 14.5906 (19) Å
b = 12.7720 (17) Å
c = 16.441 (2) Å
β = 103.114 (2)°
V = 2984.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.16 × 0.16 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.985, T_max = 0.993
15196 measured reflections
5262 independent reflections
3181 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.143
S = 1.03
5262 reflections
401 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O7ⁱ	0.94 (3)	2.59 (2)	3.119 (3)	116.6 (18)
N2—H2A⋯O1ⁱ	0.94 (3)	1.79 (3)	2.710 (3)	168 (2)
Symmetry code: (i) x-1, y, z-1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020764/tk5091sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020764/tk5091Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020764/tk5091Isup3.cml

checkCIF report

Comment top

Cinnarizine (Stugeron, Stunarone) is an anti-histamine which is mainly used for the control of nausea and vomiting due to motion sickness. Cinnarizine could be also viewed as a nootropic drug because of its vasorelaxating abilities (due to calcium channel blockage) and as a labyrinthine sedative (Towse et al., 1980). A clinical evaluation of cinnarizine in various allergic disorders has been reported earlier (Barrett et al., 1960). Cinnarizine can be used in scuba divers without an increased risk of central nervous system oxygen toxicity. The crystal structures of some related compounds viz. cinnarizine (Mouillé et al., 1975) and cyclizine hydrochloride (Bertolasi et al., 1980) have been reported. In view of the above, and as a part of our studies on the salts of the piperazines, the title compound was synthesized and herein we report its crystal structure.

The molecular structure and atom numbering scheme of the title compound are shown in Fig 1. In the structure, the piperazine ring adopts a slightly distorted chair conformation with the puckering parameters Q, θ and ϕ having values of 0.584 (2)°, 174.3 (2)° and 179 (2)°, respectively (Cremer & Pople, 1975). These values slightly different from those reported earlier for cinnarizinium dipicrate (Jasinski et al., 2011). For an ideal chair conformation, θ has a value of 0 or 180°. The sum of the bond angles around the piperazine-N atoms N1 and N2 are 328.94° and 332.45°, respectively, indicating that they are sp³ hybridized. The bonds N1—C7 and N2—C18 connecting the diphenylmethyl and the phenyl-but-2-ene groups make an angle of 74.44 (14)° and 70.28 (14)°, respectively, with the Cremer and Pople (1975) plane of the piperazine ring and thus the substituents are in the equatorial plane. The dihedral angle between the piperazine ring and the phenyl ring (C21–C26) bridged by the but-2-ene group is 63.50 (12)° whereas the dihedral angles between the piperazine ring and the diphenyl methyl rings (C1–C6) and (C8–C13) are 77.63 (11)° and 89.85 (15)°, respectively. In the crystal structure, N—H···O hydrogen bonds link the ions into two ion aggregates.

Related literature top

For background to the anti-histamine cinnarizine (systematic name: 1-benzhydryl-4-cinnamyl-piperazine), see: Towse (1980); Barrett & Zolov (1960). For related structures, see: Mouillé et al. (1975); Bertolasi et al. (1980); Jasinski et al. (2011). For additional conformational analysis, see: Cremer & Pople (1975).

Experimental top

Cinnarizine (3.68 g, 0.01 mol) and picric acid (2.99 g, 0.01 mol) were dissolved separately in methanol. The solutions were mixed and stirred for a few minutes at room temperature. The precipitate was collected by filtration and purified by recrystallization from methanol. On recrystallization with DMF after 15 days, good quality single crystals were obtained; M.pt: 463–465 K.

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, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecule structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Cinnarizinium picrate top

Crystal data top

C₂₆H₂₉N₂⁺·C₆H₂N₃O₇⁻	F(000) = 1256
M_r = 597.62	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 465–463 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.5906 (19) Å	Cell parameters from 2307 reflections
b = 12.7720 (17) Å	θ = 2.3–22.0°
c = 16.441 (2) Å	µ = 0.10 mm⁻¹
β = 103.114 (2)°	T = 296 K
V = 2984.0 (7) Å³	Block, yellow
Z = 4	0.16 × 0.16 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	5262 independent reflections
Radiation source: fine-focus sealed tube	3181 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −14→17
T_min = 0.985, T_max = 0.993	k = −15→15
15196 measured reflections	l = −19→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) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0606P)² + 0.4273P] where P = (F_o² + 2F_c²)/3
5262 reflections	(Δ/σ)_max < 0.001
401 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₆H₂₉N₂⁺·C₆H₂N₃O₇⁻	V = 2984.0 (7) Å³
M_r = 597.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.5906 (19) Å	µ = 0.10 mm⁻¹
b = 12.7720 (17) Å	T = 296 K
c = 16.441 (2) Å	0.16 × 0.16 × 0.07 mm
β = 103.114 (2)°

Data collection top

Bruker APEXII CCD diffractometer	5262 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	3181 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.993	R_int = 0.033
15196 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.21 e Å⁻³
5262 reflections	Δρ_min = −0.17 e Å⁻³
401 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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
C1	0.52622 (15)	1.01467 (17)	0.19638 (13)	0.0431 (5)
C2	0.59492 (16)	0.93827 (18)	0.21939 (14)	0.0507 (6)
H2	0.5911	0.8916	0.2619	0.061*
C3	0.66912 (17)	0.9304 (2)	0.18004 (17)	0.0616 (7)
H3	0.7152	0.8796	0.1968	0.074*
C4	0.67436 (19)	0.9977 (2)	0.11638 (18)	0.0688 (8)
H4	0.7240	0.9924	0.0898	0.083*
C5	0.6071 (2)	1.0725 (2)	0.09190 (16)	0.0714 (8)
H5	0.6107	1.1175	0.0483	0.086*
C6	0.53323 (18)	1.0819 (2)	0.13170 (15)	0.0596 (7)
H6	0.4880	1.1336	0.1149	0.072*
C7	0.44424 (14)	1.02478 (16)	0.23909 (13)	0.0427 (5)
H7	0.3976	1.0715	0.2049	0.051*
C8	0.47390 (15)	1.07319 (17)	0.32545 (13)	0.0425 (5)
C9	0.54277 (16)	1.02889 (19)	0.38803 (14)	0.0535 (6)
H9	0.5714	0.9667	0.3778	0.064*
C10	0.56926 (18)	1.0761 (2)	0.46534 (15)	0.0637 (7)
H10	0.6164	1.0461	0.5064	0.076*
C11	0.52685 (19)	1.1666 (2)	0.48211 (16)	0.0638 (7)
H11	0.5447	1.1979	0.5344	0.077*
C12	0.45798 (19)	1.2107 (2)	0.42127 (16)	0.0666 (7)
H12	0.4283	1.2718	0.4324	0.080*
C13	0.43233 (17)	1.16465 (18)	0.34333 (15)	0.0575 (7)
H13	0.3862	1.1960	0.3022	0.069*
C14	0.31810 (15)	0.92742 (18)	0.27987 (13)	0.0478 (6)
H14A	0.2709	0.9733	0.2470	0.057*
H14B	0.3377	0.9570	0.3355	0.057*
C15	0.27606 (16)	0.82031 (18)	0.28533 (13)	0.0510 (6)
H15A	0.3223	0.7757	0.3208	0.061*
H15B	0.2223	0.8264	0.3106	0.061*
C16	0.32487 (15)	0.77316 (18)	0.15764 (14)	0.0507 (6)
H16A	0.3026	0.7485	0.1008	0.061*
H16B	0.3740	0.7260	0.1859	0.061*
C17	0.36469 (15)	0.88150 (18)	0.15634 (13)	0.0496 (6)
H17A	0.4160	0.8801	0.1278	0.060*
H17B	0.3164	0.9280	0.1257	0.060*
C18	0.20741 (18)	0.66271 (18)	0.20475 (15)	0.0573 (6)
H18A	0.2580	0.6161	0.2309	0.069*
H18B	0.1609	0.6630	0.2385	0.069*
C19	0.16375 (17)	0.62381 (19)	0.11991 (16)	0.0589 (7)
H19	0.1098	0.6581	0.0912	0.071*
C20	0.19386 (17)	0.5462 (2)	0.08192 (16)	0.0634 (7)
H20	0.2454	0.5100	0.1128	0.076*
C21	0.15677 (19)	0.5088 (2)	−0.00331 (16)	0.0634 (7)
C22	0.0751 (2)	0.5494 (2)	−0.05376 (18)	0.0794 (9)
H22	0.0409	0.5996	−0.0322	0.095*
C23	0.0439 (3)	0.5168 (3)	−0.1347 (2)	0.1061 (13)
H23	−0.0114	0.5440	−0.1675	0.127*
C24	0.0947 (4)	0.4441 (4)	−0.1668 (2)	0.1206 (17)
H24	0.0742	0.4231	−0.2221	0.145*
C25	0.1749 (3)	0.4018 (3)	−0.1191 (3)	0.1079 (13)
H25	0.2086	0.3520	−0.1415	0.129*
C26	0.2056 (2)	0.4338 (2)	−0.0368 (2)	0.0829 (9)
H26	0.2597	0.4044	−0.0038	0.099*
C27	1.04152 (17)	0.86358 (18)	1.05005 (17)	0.0566 (7)
C28	0.95804 (17)	0.84392 (19)	1.08034 (16)	0.0564 (6)
C29	0.87055 (17)	0.8270 (2)	1.02945 (17)	0.0631 (7)
H29	0.8182	0.8190	1.0523	0.076*
C30	0.86144 (18)	0.8220 (2)	0.94491 (17)	0.0639 (7)
C31	0.93837 (19)	0.8327 (2)	0.91018 (17)	0.0682 (8)
H31	0.9317	0.8274	0.8527	0.082*
C32	1.02445 (17)	0.85131 (19)	0.96112 (17)	0.0589 (7)
N1	0.39904 (11)	0.92136 (13)	0.24143 (10)	0.0418 (4)
N2	0.24573 (13)	0.77163 (15)	0.20113 (11)	0.0458 (5)
N3	0.96429 (18)	0.83694 (19)	1.16985 (15)	0.0744 (7)
N4	0.77007 (19)	0.8000 (2)	0.89112 (19)	0.0919 (8)
N5	1.10421 (19)	0.8585 (2)	0.92183 (18)	0.0847 (8)
O1	1.11914 (12)	0.89116 (14)	1.09451 (12)	0.0783 (6)
O2	1.17777 (18)	0.8186 (2)	0.95562 (19)	0.1361 (11)
O3	1.09238 (17)	0.9046 (2)	0.85521 (15)	0.1185 (9)
O4	0.76491 (17)	0.7930 (2)	0.81627 (17)	0.1279 (10)
O5	0.70246 (16)	0.7909 (2)	0.92284 (17)	0.1272 (10)
O6	0.89418 (16)	0.8534 (2)	1.19597 (13)	0.1050 (8)
O7	1.03892 (16)	0.81087 (19)	1.21524 (12)	0.1012 (8)
H2A	0.1979 (18)	0.8141 (19)	0.1706 (15)	0.071 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0374 (12)	0.0451 (13)	0.0457 (13)	−0.0046 (10)	0.0073 (10)	−0.0056 (10)
C2	0.0455 (14)	0.0493 (14)	0.0577 (15)	−0.0011 (11)	0.0124 (11)	−0.0023 (12)
C3	0.0470 (15)	0.0614 (16)	0.0783 (18)	−0.0019 (13)	0.0180 (14)	−0.0155 (15)
C4	0.0629 (18)	0.0650 (18)	0.089 (2)	−0.0131 (15)	0.0395 (16)	−0.0199 (16)
C5	0.087 (2)	0.0680 (18)	0.0700 (18)	−0.0081 (17)	0.0415 (16)	0.0043 (15)
C6	0.0658 (17)	0.0579 (16)	0.0580 (16)	0.0000 (13)	0.0199 (13)	0.0037 (13)
C7	0.0376 (12)	0.0453 (13)	0.0440 (13)	0.0005 (10)	0.0069 (10)	0.0003 (10)
C8	0.0412 (12)	0.0425 (12)	0.0436 (13)	−0.0055 (10)	0.0092 (10)	−0.0015 (10)
C9	0.0498 (14)	0.0611 (15)	0.0471 (14)	0.0071 (12)	0.0058 (11)	−0.0013 (12)
C10	0.0603 (17)	0.0786 (19)	0.0466 (15)	0.0038 (14)	0.0002 (12)	0.0007 (13)
C11	0.0782 (19)	0.0606 (17)	0.0502 (15)	−0.0116 (15)	0.0097 (14)	−0.0115 (13)
C12	0.084 (2)	0.0510 (15)	0.0606 (17)	0.0058 (14)	0.0072 (15)	−0.0100 (13)
C13	0.0625 (16)	0.0507 (14)	0.0543 (15)	0.0088 (12)	0.0026 (12)	−0.0052 (12)
C14	0.0430 (13)	0.0548 (14)	0.0463 (13)	−0.0033 (11)	0.0117 (11)	−0.0078 (11)
C15	0.0471 (14)	0.0617 (15)	0.0447 (13)	−0.0070 (12)	0.0113 (11)	−0.0056 (11)
C16	0.0409 (13)	0.0591 (15)	0.0533 (14)	−0.0048 (11)	0.0132 (11)	−0.0115 (12)
C17	0.0404 (13)	0.0605 (15)	0.0490 (14)	−0.0080 (11)	0.0124 (11)	−0.0116 (11)
C18	0.0587 (15)	0.0462 (14)	0.0661 (17)	−0.0088 (12)	0.0120 (13)	0.0013 (12)
C19	0.0508 (15)	0.0489 (14)	0.0696 (17)	−0.0067 (12)	−0.0019 (13)	−0.0012 (13)
C20	0.0555 (16)	0.0620 (17)	0.0680 (17)	−0.0004 (13)	0.0041 (13)	−0.0009 (14)
C21	0.0639 (17)	0.0642 (17)	0.0604 (17)	−0.0202 (14)	0.0104 (14)	−0.0037 (14)
C22	0.079 (2)	0.089 (2)	0.0653 (19)	−0.0205 (17)	0.0050 (16)	0.0063 (16)
C23	0.109 (3)	0.136 (3)	0.064 (2)	−0.053 (3)	−0.001 (2)	0.021 (2)
C24	0.156 (4)	0.143 (4)	0.065 (2)	−0.085 (4)	0.031 (3)	−0.023 (3)
C25	0.132 (4)	0.106 (3)	0.101 (3)	−0.051 (3)	0.057 (3)	−0.033 (2)
C26	0.086 (2)	0.074 (2)	0.092 (2)	−0.0284 (17)	0.0263 (18)	−0.0186 (18)
C27	0.0428 (15)	0.0475 (14)	0.0742 (18)	0.0036 (11)	0.0022 (13)	0.0119 (13)
C28	0.0469 (15)	0.0597 (16)	0.0597 (16)	0.0076 (12)	0.0061 (12)	−0.0017 (12)
C29	0.0436 (15)	0.0696 (18)	0.0748 (19)	0.0071 (13)	0.0110 (13)	0.0028 (14)
C30	0.0440 (15)	0.0724 (18)	0.0671 (18)	0.0045 (13)	−0.0044 (13)	0.0109 (14)
C31	0.0667 (19)	0.0738 (18)	0.0592 (17)	0.0046 (15)	0.0042 (15)	0.0179 (14)
C32	0.0489 (15)	0.0607 (16)	0.0679 (18)	0.0020 (12)	0.0148 (13)	0.0167 (13)
N1	0.0365 (10)	0.0470 (11)	0.0418 (10)	−0.0038 (8)	0.0084 (8)	−0.0065 (8)
N2	0.0396 (11)	0.0494 (12)	0.0470 (12)	−0.0025 (9)	0.0069 (9)	−0.0044 (9)
N3	0.0598 (16)	0.0925 (18)	0.0698 (17)	0.0040 (14)	0.0123 (14)	−0.0179 (13)
N4	0.0593 (18)	0.112 (2)	0.088 (2)	0.0053 (16)	−0.0179 (16)	0.0149 (17)
N5	0.0690 (18)	0.098 (2)	0.091 (2)	−0.0080 (15)	0.0273 (16)	0.0238 (16)
O1	0.0501 (11)	0.0683 (12)	0.1024 (15)	−0.0069 (9)	−0.0123 (10)	0.0134 (10)
O2	0.0716 (16)	0.177 (3)	0.174 (3)	0.0305 (17)	0.0569 (17)	0.071 (2)
O3	0.1133 (19)	0.164 (2)	0.0846 (16)	−0.0169 (17)	0.0360 (14)	0.0298 (17)
O4	0.0950 (18)	0.180 (3)	0.0842 (17)	0.0107 (17)	−0.0297 (14)	−0.0095 (18)
O5	0.0481 (13)	0.188 (3)	0.131 (2)	−0.0046 (16)	−0.0087 (14)	0.0326 (19)
O6	0.0751 (15)	0.160 (2)	0.0868 (15)	0.0011 (15)	0.0321 (13)	−0.0238 (14)
O7	0.0840 (15)	0.152 (2)	0.0609 (13)	0.0327 (15)	0.0013 (11)	−0.0123 (13)

Geometric parameters (Å, º) top

C1—C6	1.389 (3)	C17—H17B	0.9700
C1—C2	1.388 (3)	C18—C19	1.482 (3)
C1—C7	1.524 (3)	C18—N2	1.506 (3)
C2—C3	1.385 (3)	C18—H18A	0.9700
C2—H2	0.9300	C18—H18B	0.9700
C3—C4	1.370 (3)	C19—C20	1.300 (3)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.364 (4)	C20—C21	1.463 (3)
C4—H4	0.9300	C20—H20	0.9300
C5—C6	1.387 (3)	C21—C26	1.381 (4)
C5—H5	0.9300	C21—C22	1.389 (4)
C6—H6	0.9300	C22—C23	1.369 (4)
C7—N1	1.481 (3)	C22—H22	0.9300
C7—C8	1.519 (3)	C23—C24	1.366 (6)
C7—H7	0.9800	C23—H23	0.9300
C8—C13	1.378 (3)	C24—C25	1.364 (6)
C8—C9	1.385 (3)	C24—H24	0.9300
C9—C10	1.380 (3)	C25—C26	1.387 (4)
C9—H9	0.9300	C25—H25	0.9300
C10—C11	1.369 (3)	C26—H26	0.9300
C10—H10	0.9300	C27—O1	1.251 (3)
C11—C12	1.368 (3)	C27—C32	1.435 (3)
C11—H11	0.9300	C27—C28	1.439 (3)
C12—C13	1.382 (3)	C28—C29	1.375 (3)
C12—H12	0.9300	C28—N3	1.456 (3)
C13—H13	0.9300	C29—C30	1.367 (3)
C14—N1	1.462 (3)	C29—H29	0.9300
C14—C15	1.510 (3)	C30—C31	1.377 (4)
C14—H14A	0.9700	C30—N4	1.450 (3)
C14—H14B	0.9700	C31—C32	1.363 (3)
C15—N2	1.490 (3)	C31—H31	0.9300
C15—H15A	0.9700	C32—N5	1.456 (3)
C15—H15B	0.9700	N2—H2A	0.94 (3)
C16—N2	1.490 (3)	N3—O6	1.214 (3)
C16—C17	1.503 (3)	N3—O7	1.218 (3)
C16—H16A	0.9700	N4—O4	1.219 (3)
C16—H16B	0.9700	N4—O5	1.222 (3)
C17—N1	1.466 (2)	N5—O2	1.204 (3)
C17—H17A	0.9700	N5—O3	1.221 (3)

C6—C1—C2	118.0 (2)	C19—C18—N2	110.90 (19)
C6—C1—C7	120.2 (2)	C19—C18—H18A	109.5
C2—C1—C7	121.8 (2)	N2—C18—H18A	109.5
C3—C2—C1	121.1 (2)	C19—C18—H18B	109.5
C3—C2—H2	119.5	N2—C18—H18B	109.5
C1—C2—H2	119.5	H18A—C18—H18B	108.0
C4—C3—C2	119.7 (2)	C20—C19—C18	126.0 (2)
C4—C3—H3	120.1	C20—C19—H19	117.0
C2—C3—H3	120.1	C18—C19—H19	117.0
C5—C4—C3	120.3 (3)	C19—C20—C21	128.1 (3)
C5—C4—H4	119.9	C19—C20—H20	115.9
C3—C4—H4	119.9	C21—C20—H20	115.9
C4—C5—C6	120.4 (3)	C26—C21—C22	118.1 (3)
C4—C5—H5	119.8	C26—C21—C20	119.7 (3)
C6—C5—H5	119.8	C22—C21—C20	122.1 (3)
C5—C6—C1	120.5 (2)	C23—C22—C21	121.2 (3)
C5—C6—H6	119.7	C23—C22—H22	119.4
C1—C6—H6	119.7	C21—C22—H22	119.4
N1—C7—C8	111.90 (16)	C24—C23—C22	119.5 (4)
N1—C7—C1	109.71 (17)	C24—C23—H23	120.2
C8—C7—C1	112.23 (17)	C22—C23—H23	120.3
N1—C7—H7	107.6	C25—C24—C23	121.1 (4)
C8—C7—H7	107.6	C25—C24—H24	119.4
C1—C7—H7	107.6	C23—C24—H24	119.4
C13—C8—C9	117.9 (2)	C24—C25—C26	119.3 (4)
C13—C8—C7	119.9 (2)	C24—C25—H25	120.4
C9—C8—C7	122.2 (2)	C26—C25—H25	120.4
C10—C9—C8	120.7 (2)	C21—C26—C25	120.8 (3)
C10—C9—H9	119.7	C21—C26—H26	119.6
C8—C9—H9	119.7	C25—C26—H26	119.6
C11—C10—C9	120.6 (2)	O1—C27—C32	123.4 (3)
C11—C10—H10	119.7	O1—C27—C28	124.9 (3)
C9—C10—H10	119.7	C32—C27—C28	111.6 (2)
C12—C11—C10	119.4 (2)	C29—C28—C27	124.0 (2)
C12—C11—H11	120.3	C29—C28—N3	116.2 (2)
C10—C11—H11	120.3	C27—C28—N3	119.8 (2)
C11—C12—C13	120.2 (2)	C30—C29—C28	119.2 (3)
C11—C12—H12	119.9	C30—C29—H29	120.4
C13—C12—H12	119.9	C28—C29—H29	120.4
C8—C13—C12	121.2 (2)	C29—C30—C31	121.1 (2)
C8—C13—H13	119.4	C29—C30—N4	119.5 (3)
C12—C13—H13	119.4	C31—C30—N4	119.3 (3)
N1—C14—C15	110.89 (18)	C32—C31—C30	119.1 (3)
N1—C14—H14A	109.5	C32—C31—H31	120.4
C15—C14—H14A	109.5	C30—C31—H31	120.4
N1—C14—H14B	109.5	C31—C32—C27	124.6 (3)
C15—C14—H14B	109.5	C31—C32—N5	117.1 (3)
H14A—C14—H14B	108.0	C27—C32—N5	118.3 (2)
N2—C15—C14	111.20 (18)	C14—N1—C17	107.22 (16)
N2—C15—H15A	109.4	C14—N1—C7	111.85 (16)
C14—C15—H15A	109.4	C17—N1—C7	110.05 (16)
N2—C15—H15B	109.4	C16—N2—C15	109.96 (17)
C14—C15—H15B	109.4	C16—N2—C18	111.49 (18)
H15A—C15—H15B	108.0	C15—N2—C18	112.54 (18)
N2—C16—C17	111.29 (18)	C16—N2—H2A	107.5 (15)
N2—C16—H16A	109.4	C15—N2—H2A	106.5 (15)
C17—C16—H16A	109.4	C18—N2—H2A	108.5 (15)
N2—C16—H16B	109.4	O6—N3—O7	122.6 (3)
C17—C16—H16B	109.4	O6—N3—C28	118.8 (2)
H16A—C16—H16B	108.0	O7—N3—C28	118.6 (2)
N1—C17—C16	110.84 (18)	O4—N4—O5	123.6 (3)
N1—C17—H17A	109.5	O4—N4—C30	117.9 (3)
C16—C17—H17A	109.5	O5—N4—C30	118.5 (3)
N1—C17—H17B	109.5	O2—N5—O3	123.2 (3)
C16—C17—H17B	109.5	O2—N5—C32	119.1 (3)
H17A—C17—H17B	108.1	O3—N5—C32	117.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7ⁱ	0.94 (3)	2.59 (2)	3.119 (3)	116.6 (18)
N2—H2A···O1ⁱ	0.94 (3)	1.79 (3)	2.710 (3)	168 (2)

Symmetry code: (i) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₉N₂⁺·C₆H₂N₃O₇⁻
M_r	597.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.5906 (19), 12.7720 (17), 16.441 (2)
β (°)	103.114 (2)
V (Å³)	2984.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.16 × 0.16 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.985, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	15196, 5262, 3181
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.143, 1.03
No. of reflections	5262
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)	0.21, −0.17

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7ⁱ	0.94 (3)	2.59 (2)	3.119 (3)	116.6 (18)
N2—H2A···O1ⁱ	0.94 (3)	1.79 (3)	2.710 (3)	168 (2)

Symmetry code: (i) x−1, y, z−1.

Acknowledgements

This work was supported in part (ALS) by the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO). YS and HL acknowledge financial support by the Fundamental Research Funds for the Central Universities.

References

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