Imipraminium picrate

Harrison, W.T.A.; Bindya, S.; Ashok, M.A.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536807026050

Imipraminium picrate

W. T. A. Harrison, S. Bindya, M. A. Ashok, H. S. Yathirajan and B. Narayana

The title compound, C₁₉H₂₅N₂⁺·C₆H₂N₃O₇⁻, is a molecular salt arising from the reaction of imipramine and picric acid. The tertiary N atom of the side chain of the cation is protonated and forms a bifurcated N—H

(O,O) hydrogen bond to the anion. One of the acceptor O atoms is the deprotonated phenol O atom and the other is part of a nitro group. The dihedral angle between the mean planes of the benzene rings in the cation is 56.13 (6)° and the two bridging methylene groups in the central seven-membered ring are probably disordered. In the crystal structure, π–π stacking occurs [ring centroid separations = 3.6805 (12) and 3.7726 (14) Å], resulting in centrosymmetric associations of two cations and two anions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026050/lh2401sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026050/lh2401Isup2.hkl Contains datablock I

CCDC reference: 654904

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.003 Å
R factor = 0.049
wR factor = 0.127
Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C7     -   C8      ..       9.05 su
PLAT432_ALERT_2_B Short Inter X...Y Contact  O1     ..  C18     ..       2.90 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C6     -   C7      ..       5.34 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O5     -   N4      ..       5.43 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N5     -   C25     ..       5.25 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N5

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Imipramine, C₁₉H₂₀N₂, a tricyclic molecule containing two tertiary amine moieties, inhibits the re-uptake of serotonin more effectively than most secondary amine tricyclics, meaning that it blocks the re-uptake of the neurotransmitters serotonin and noradrenaline almost equally. It has been widely used to treat depression and neurosis for the past 50 years and is still under intensive study (Zanoveli et al., 2007).

Here we describe the title compound, (I), (Fig. 1), C₁₉H₂₅N₂·C₆H₂N₃O₇, a molecular salt of imipramine and picric acid.

Compound (I) formally arises via proton transfer from the phenol group of the picric acid to the tertiary N atom of the imipramine side chain. The resulting cation and anion interact via a bifurcated N—H···(O,O) hydrogen bond (Table 1). One of the acceptor oxygen atoms is the deprotonated phenolic O atom, and the other is part of a nitro group.

The dihedral angle between the aromatic rings in the cation is 56.13 (6)°. The conformation of the seven-membered ring in (I) is uncertain because of probable disorder of the bridging methylene C6 and C7 species. The bond angle sum at N1 of 351.0° is ambiguous with respect to the hybridization of this nitrogen atom (nominal values for sp² and sp³ hybridization = 360 and 328°, respectively). The N1—C15—C16—C17 and C15—C16—C17—N2 conformations in the side chain in (I) are both gauche [torsion angles = 53.8 (2) and 57.8 (2)°, respectively].

In the crystal of (I), π-π stacking is evident. The C20—C25 aromatic ring (centroid = Cg1) of the anion interacts with a symmetry related partner [Cg1···Cg1ⁱ = 3.6805 (12) Å, i = 1 - x, 1 - y, 1 - z) and also with the C1—C6 ring (centroid = Cg2) of the cation [Cg1···Cg2 = 3.7726 (14) Å].

The structure of imipramine hydrochloride, (II), was determined by Post et al. (1975). They also found unresolvable disorder for the bridging methylene groups in the seven-membered rings of the two unique cations. The dihedral angles between the aromatic rings in the cations in (II) were calculated to be 49.7° and 57° (standard uncertainties not stated). One cation in (II) has a gauche-gauche conformation in its side chain, the other a gauche-trans conformation.

Related literature top

For the crystal structure of impramine hydrochloride, see: Post et al. (1975). For recent background on the neurochemistry of imapramine, see: Zanoveli et al. (2007).

Experimental top

Two solutions were made up: imipramine hydrochloride (0.95 g, 0.03 mol) in 50 ml of water and picric acid (1.1 g, 0.03 mol) in 50 ml of water. The solutions were mixed and stirred for few minutes. The resulting salt was filtered off and dried over P₂O₅. Red-orange chunks of (I) were recrystallized from methylethylketone (m.p.: 415 K).

Structure description top

Here we describe the title compound, (I), (Fig. 1), C₁₉H₂₅N₂·C₆H₂N₃O₇, a molecular salt of imipramine and picric acid.

For the crystal structure of impramine hydrochloride, see: Post et al. (1975). For recent background on the neurochemistry of imapramine, see: Zanoveli et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. View of the molecular structure of (I) showing 30% displacement ellipsoids (arbitrary spheres for the H atom). The hydrogen bonds are shown as double-dashed lines. All C-bound H atoms omitted for clarity.
	Fig. 2. π-π Stacking interactions in (I) shown as open lines between the centroids of C20—C25 (Cg1) and C1—C6 (Cg2). Symmetry code: (i) 1 - x, 1 - y, 1 - z. All H atoms omitted for clarity.

Imipraminium picrate top

Crystal data top

C₁₉H₂₅N₂⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 509.52	F(000) = 536
Triclinic, P1	D_x = 1.369 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5204 (10) Å	Cell parameters from 2120 reflections
b = 10.6661 (10) Å	θ = 4.4–25.7°
c = 11.7603 (11) Å	µ = 0.10 mm⁻¹
α = 77.292 (1)°	T = 295 K
β = 73.862 (1)°	Chunk, red-orange
γ = 84.590 (1)°	0.40 × 0.30 × 0.30 mm
V = 1235.8 (2) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	2818 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 26.0°, θ_min = 4.3°
ω scans	h = −12→12
7898 measured reflections	k = −13→13
4674 independent reflections	l = −14→13

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)] = 0.049	Hydrogen site location: difmap (N-H) and geom (C-H)
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0649P)²] where P = (F_o² + 2F_c²)/3
4674 reflections	(Δ/σ)_max < 0.001
339 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₉H₂₅N₂⁺·C₆H₂N₃O₇⁻	γ = 84.590 (1)°
M_r = 509.52	V = 1235.8 (2) Å³
Triclinic, P1	Z = 2
a = 10.5204 (10) Å	Mo Kα radiation
b = 10.6661 (10) Å	µ = 0.10 mm⁻¹
c = 11.7603 (11) Å	T = 295 K
α = 77.292 (1)°	0.40 × 0.30 × 0.30 mm
β = 73.862 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2818 reflections with I > 2σ(I)
7898 measured reflections	R_int = 0.021
4674 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.17 e Å⁻³
4674 reflections	Δρ_min = −0.19 e Å⁻³
339 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	0.19775 (18)	0.83478 (18)	0.27495 (19)	0.0455 (5)
C2	0.1915 (2)	0.9091 (2)	0.1636 (2)	0.0557 (6)
H2	0.2345	0.9867	0.1359	0.067*
C3	0.1235 (2)	0.8713 (3)	0.0929 (2)	0.0760 (8)
H3	0.1214	0.9228	0.0185	0.091*
C4	0.0589 (2)	0.7578 (3)	0.1327 (3)	0.0913 (10)
H4	0.0126	0.7314	0.0858	0.110*
C5	0.0636 (2)	0.6838 (3)	0.2424 (3)	0.0819 (9)
H5	0.0189	0.6072	0.2689	0.098*
C6	0.1323 (2)	0.7176 (2)	0.3168 (2)	0.0613 (6)
C7	0.1284 (3)	0.6248 (2)	0.4349 (3)	0.0854 (9)
H7A	0.1469	0.5390	0.4178	0.102*
H7B	0.0385	0.6265	0.4859	0.102*
C8	0.2204 (3)	0.6445 (2)	0.5079 (2)	0.0761 (8)
H8A	0.2139	0.5735	0.5766	0.091*
H8B	0.3111	0.6461	0.4582	0.091*
C9	0.1852 (2)	0.7681 (2)	0.5516 (2)	0.0595 (6)
C10	0.1256 (3)	0.7721 (3)	0.6715 (2)	0.0825 (8)
H10	0.1110	0.6958	0.7287	0.099*
C11	0.0875 (3)	0.8877 (3)	0.7073 (2)	0.0803 (8)
H11	0.0475	0.8890	0.7883	0.096*
C12	0.1085 (2)	0.9995 (2)	0.6245 (2)	0.0612 (6)
H12	0.0831	1.0774	0.6489	0.073*
C13	0.16742 (19)	0.99837 (19)	0.50393 (19)	0.0475 (5)
H13	0.1811	1.0754	0.4475	0.057*
C14	0.20606 (18)	0.88278 (18)	0.46723 (18)	0.0426 (5)
C15	0.36804 (18)	0.97595 (17)	0.27865 (17)	0.0409 (5)
H15A	0.3221	1.0591	0.2668	0.049*
H15B	0.4122	0.9577	0.1996	0.049*
C16	0.47105 (18)	0.98213 (17)	0.34556 (18)	0.0444 (5)
H16A	0.5360	1.0440	0.2952	0.053*
H16B	0.4278	1.0140	0.4185	0.053*
C17	0.54306 (19)	0.85605 (19)	0.38034 (17)	0.0471 (5)
H17A	0.6065	0.8710	0.4216	0.056*
H17B	0.4793	0.7969	0.4373	0.056*
C18	0.6879 (2)	0.6759 (2)	0.3248 (2)	0.0674 (7)
H18A	0.6273	0.6209	0.3884	0.101*
H18B	0.7551	0.7003	0.3559	0.101*
H18C	0.7284	0.6309	0.2608	0.101*
C19	0.7051 (2)	0.8795 (2)	0.17754 (19)	0.0585 (6)
H19A	0.6545	0.9491	0.1421	0.088*
H19B	0.7523	0.8320	0.1172	0.088*
H19C	0.7670	0.9132	0.2086	0.088*
N1	0.27124 (15)	0.87742 (13)	0.34391 (14)	0.0404 (4)
N2	0.61469 (17)	0.79317 (14)	0.27744 (15)	0.0444 (4)
H1	0.555 (2)	0.7628 (18)	0.2485 (18)	0.053*
C20	0.41881 (19)	0.57369 (17)	0.17240 (18)	0.0422 (5)
C21	0.3622 (2)	0.44759 (17)	0.21547 (17)	0.0447 (5)
C22	0.2846 (2)	0.39896 (18)	0.16199 (18)	0.0471 (5)
H22	0.2469	0.3195	0.1971	0.057*
C23	0.26218 (19)	0.46791 (18)	0.05557 (18)	0.0447 (5)
C24	0.31935 (19)	0.58543 (18)	0.00231 (17)	0.0443 (5)
H24	0.3059	0.6306	−0.0709	0.053*
C25	0.39595 (18)	0.63523 (16)	0.05766 (17)	0.0406 (4)
N3	0.3867 (2)	0.36765 (17)	0.32566 (18)	0.0648 (5)
N4	0.18039 (18)	0.4167 (2)	−0.00232 (19)	0.0618 (5)
N5	0.45440 (18)	0.75804 (16)	−0.00482 (17)	0.0538 (5)
O1	0.47543 (16)	0.62008 (13)	0.23215 (14)	0.0649 (4)
O2	0.2998 (2)	0.29774 (18)	0.39253 (17)	0.0990 (7)
O3	0.4926 (2)	0.3707 (2)	0.3451 (2)	0.1137 (8)
O4	0.13910 (18)	0.30810 (18)	0.04328 (17)	0.0885 (6)
O5	0.15606 (18)	0.48256 (19)	−0.09388 (17)	0.0863 (6)
O6	0.52913 (19)	0.80446 (16)	0.03556 (17)	0.0852 (6)
O7	0.4274 (2)	0.81032 (16)	−0.09792 (17)	0.0897 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0343 (11)	0.0464 (11)	0.0570 (14)	−0.0002 (9)	−0.0054 (10)	−0.0225 (10)
C2	0.0436 (12)	0.0712 (14)	0.0598 (15)	0.0016 (10)	−0.0185 (11)	−0.0241 (12)
C3	0.0506 (15)	0.117 (2)	0.0771 (18)	0.0103 (15)	−0.0275 (14)	−0.0464 (16)
C4	0.0429 (15)	0.138 (3)	0.122 (3)	0.0032 (16)	−0.0239 (17)	−0.087 (2)
C5	0.0435 (14)	0.0834 (18)	0.128 (3)	−0.0160 (13)	0.0009 (16)	−0.0647 (19)
C6	0.0419 (12)	0.0521 (13)	0.0879 (18)	−0.0065 (10)	0.0039 (12)	−0.0348 (13)
C7	0.0818 (19)	0.0418 (13)	0.110 (2)	−0.0195 (12)	0.0233 (17)	−0.0223 (14)
C8	0.0834 (18)	0.0413 (13)	0.0789 (18)	0.0003 (12)	0.0023 (16)	0.0076 (12)
C9	0.0602 (14)	0.0513 (13)	0.0524 (15)	0.0020 (10)	−0.0015 (12)	0.0012 (10)
C10	0.090 (2)	0.0821 (19)	0.0527 (17)	−0.0011 (15)	−0.0016 (15)	0.0109 (14)
C11	0.0763 (18)	0.105 (2)	0.0515 (16)	0.0011 (16)	−0.0019 (14)	−0.0205 (16)
C12	0.0508 (13)	0.0760 (16)	0.0637 (17)	0.0054 (12)	−0.0131 (12)	−0.0346 (13)
C13	0.0428 (12)	0.0480 (11)	0.0548 (14)	0.0029 (9)	−0.0160 (11)	−0.0148 (10)
C14	0.0387 (11)	0.0449 (11)	0.0413 (12)	0.0015 (8)	−0.0086 (9)	−0.0066 (9)
C15	0.0438 (11)	0.0377 (10)	0.0406 (11)	−0.0035 (8)	−0.0121 (9)	−0.0047 (8)
C16	0.0472 (12)	0.0440 (11)	0.0439 (12)	−0.0050 (9)	−0.0115 (10)	−0.0122 (9)
C17	0.0488 (12)	0.0575 (12)	0.0373 (12)	−0.0015 (10)	−0.0148 (10)	−0.0104 (9)
C18	0.0751 (16)	0.0605 (14)	0.0795 (18)	0.0191 (12)	−0.0425 (15)	−0.0218 (12)
C19	0.0501 (13)	0.0732 (15)	0.0520 (14)	−0.0097 (11)	−0.0062 (11)	−0.0185 (11)
N1	0.0435 (9)	0.0365 (8)	0.0400 (10)	−0.0080 (7)	−0.0083 (8)	−0.0065 (7)
N2	0.0483 (10)	0.0426 (9)	0.0504 (11)	0.0004 (8)	−0.0235 (9)	−0.0136 (8)
C20	0.0453 (11)	0.0380 (10)	0.0457 (12)	−0.0003 (8)	−0.0128 (10)	−0.0133 (9)
C21	0.0580 (13)	0.0396 (10)	0.0365 (11)	−0.0012 (9)	−0.0129 (10)	−0.0073 (8)
C22	0.0574 (13)	0.0390 (10)	0.0447 (13)	−0.0085 (9)	−0.0090 (10)	−0.0110 (9)
C23	0.0468 (12)	0.0507 (11)	0.0404 (12)	−0.0071 (9)	−0.0102 (10)	−0.0168 (9)
C24	0.0477 (12)	0.0493 (11)	0.0344 (11)	0.0047 (9)	−0.0098 (10)	−0.0092 (9)
C25	0.0441 (11)	0.0334 (10)	0.0418 (12)	−0.0023 (8)	−0.0072 (9)	−0.0069 (8)
N3	0.0959 (16)	0.0504 (11)	0.0547 (13)	−0.0132 (11)	−0.0340 (12)	−0.0017 (9)
N4	0.0588 (12)	0.0745 (13)	0.0596 (13)	−0.0115 (10)	−0.0158 (11)	−0.0253 (11)
N5	0.0604 (12)	0.0436 (10)	0.0505 (12)	−0.0037 (8)	−0.0067 (10)	−0.0047 (9)
O1	0.0853 (11)	0.0562 (9)	0.0676 (10)	−0.0135 (8)	−0.0376 (9)	−0.0155 (7)
O2	0.1468 (18)	0.0813 (12)	0.0686 (12)	−0.0507 (13)	−0.0436 (13)	0.0244 (10)
O3	0.1231 (17)	0.1125 (16)	0.1131 (17)	−0.0232 (13)	−0.0787 (15)	0.0300 (13)
O4	0.1012 (14)	0.0870 (13)	0.0932 (14)	−0.0402 (11)	−0.0334 (12)	−0.0256 (10)
O5	0.0975 (14)	0.1118 (14)	0.0655 (12)	−0.0157 (11)	−0.0453 (11)	−0.0157 (10)
O6	0.1030 (14)	0.0667 (11)	0.0918 (14)	−0.0421 (10)	−0.0330 (12)	−0.0026 (9)
O7	0.1236 (16)	0.0688 (11)	0.0703 (13)	−0.0279 (10)	−0.0366 (12)	0.0238 (9)

Geometric parameters (Å, º) top

C1—C2	1.389 (3)	C16—C17	1.512 (3)
C1—C6	1.408 (3)	C16—H16A	0.9700
C1—N1	1.428 (2)	C16—H16B	0.9700
C2—C3	1.377 (3)	C17—N2	1.496 (2)
C2—H2	0.9300	C17—H17A	0.9700
C3—C4	1.370 (4)	C17—H17B	0.9700
C3—H3	0.9300	C18—N2	1.489 (2)
C4—C5	1.367 (4)	C18—H18A	0.9600
C4—H4	0.9300	C18—H18B	0.9600
C5—C6	1.398 (3)	C18—H18C	0.9600
C5—H5	0.9300	C19—N2	1.483 (3)
C6—C7	1.511 (4)	C19—H19A	0.9600
C7—C8	1.516 (4)	C19—H19B	0.9600
C7—H7A	0.9700	C19—H19C	0.9600
C7—H7B	0.9700	N2—H1	0.90 (2)
C8—C9	1.496 (3)	C20—O1	1.239 (2)
C8—H8A	0.9700	C20—C25	1.439 (3)
C8—H8B	0.9700	C20—C21	1.451 (2)
C9—C10	1.383 (3)	C21—C22	1.356 (2)
C9—C14	1.388 (3)	C21—N3	1.460 (2)
C10—C11	1.378 (4)	C22—C23	1.375 (3)
C10—H10	0.9300	C22—H22	0.9300
C11—C12	1.356 (3)	C23—C24	1.383 (3)
C11—H11	0.9300	C23—N4	1.442 (2)
C12—C13	1.383 (3)	C24—C25	1.371 (2)
C12—H12	0.9300	C24—H24	0.9300
C13—C14	1.383 (3)	C25—N5	1.453 (2)
C13—H13	0.9300	N3—O3	1.203 (2)
C14—N1	1.433 (2)	N3—O2	1.217 (2)
C15—N1	1.464 (2)	N4—O5	1.227 (2)
C15—C16	1.519 (2)	N4—O4	1.229 (2)
C15—H15A	0.9700	N5—O7	1.210 (2)
C15—H15B	0.9700	N5—O6	1.214 (2)

C2—C1—C6	118.95 (19)	C17—C16—H16B	108.4
C2—C1—N1	119.71 (17)	C15—C16—H16B	108.4
C6—C1—N1	121.34 (19)	H16A—C16—H16B	107.5
C3—C2—C1	121.9 (2)	N2—C17—C16	115.19 (15)
C3—C2—H2	119.0	N2—C17—H17A	108.5
C1—C2—H2	119.0	C16—C17—H17A	108.5
C4—C3—C2	119.8 (3)	N2—C17—H17B	108.5
C4—C3—H3	120.1	C16—C17—H17B	108.5
C2—C3—H3	120.1	H17A—C17—H17B	107.5
C5—C4—C3	119.0 (2)	N2—C18—H18A	109.5
C5—C4—H4	120.5	N2—C18—H18B	109.5
C3—C4—H4	120.5	H18A—C18—H18B	109.5
C4—C5—C6	123.3 (2)	N2—C18—H18C	109.5
C4—C5—H5	118.3	H18A—C18—H18C	109.5
C6—C5—H5	118.3	H18B—C18—H18C	109.5
C5—C6—C1	117.1 (2)	N2—C19—H19A	109.5
C5—C6—C7	116.7 (2)	N2—C19—H19B	109.5
C1—C6—C7	126.2 (2)	H19A—C19—H19B	109.5
C6—C7—C8	118.57 (19)	N2—C19—H19C	109.5
C6—C7—H7A	107.7	H19A—C19—H19C	109.5
C8—C7—H7A	107.7	H19B—C19—H19C	109.5
C6—C7—H7B	107.7	C1—N1—C14	117.96 (15)
C8—C7—H7B	107.7	C1—N1—C15	116.68 (15)
H7A—C7—H7B	107.1	C14—N1—C15	116.36 (14)
C9—C8—C7	110.5 (2)	C19—N2—C18	110.88 (17)
C9—C8—H8A	109.5	C19—N2—C17	113.60 (15)
C7—C8—H8A	109.5	C18—N2—C17	108.74 (16)
C9—C8—H8B	109.5	C19—N2—H1	109.5 (13)
C7—C8—H8B	109.5	C18—N2—H1	104.2 (12)
H8A—C8—H8B	108.1	C17—N2—H1	109.5 (13)
C10—C9—C14	118.9 (2)	O1—C20—C25	126.36 (17)
C10—C9—C8	122.5 (2)	O1—C20—C21	122.04 (18)
C14—C9—C8	118.5 (2)	C25—C20—C21	111.57 (16)
C11—C10—C9	120.9 (2)	C22—C21—C20	124.55 (18)
C11—C10—H10	119.5	C22—C21—N3	117.02 (17)
C9—C10—H10	119.5	C20—C21—N3	118.42 (17)
C12—C11—C10	119.9 (2)	C21—C22—C23	119.55 (18)
C12—C11—H11	120.0	C21—C22—H22	120.2
C10—C11—H11	120.0	C23—C22—H22	120.2
C11—C12—C13	120.4 (2)	C22—C23—C24	120.44 (17)
C11—C12—H12	119.8	C22—C23—N4	119.96 (18)
C13—C12—H12	119.8	C24—C23—N4	119.59 (18)
C12—C13—C14	120.0 (2)	C25—C24—C23	119.82 (18)
C12—C13—H13	120.0	C25—C24—H24	120.1
C14—C13—H13	120.0	C23—C24—H24	120.1
C13—C14—C9	119.83 (19)	C24—C25—C20	123.72 (17)
C13—C14—N1	121.85 (17)	C24—C25—N5	116.59 (17)
C9—C14—N1	118.30 (17)	C20—C25—N5	119.68 (16)
N1—C15—C16	112.33 (15)	O3—N3—O2	122.7 (2)
N1—C15—H15A	109.1	O3—N3—C21	119.0 (2)
C16—C15—H15A	109.1	O2—N3—C21	118.3 (2)
N1—C15—H15B	109.1	O5—N4—O4	123.49 (19)
C16—C15—H15B	109.1	O5—N4—C23	118.9 (2)
H15A—C15—H15B	107.9	O4—N4—C23	117.6 (2)
C17—C16—C15	115.34 (15)	O7—N5—O6	121.92 (18)
C17—C16—H16A	108.4	O7—N5—C25	117.90 (18)
C15—C16—H16A	108.4	O6—N5—C25	120.17 (18)

C6—C1—C2—C3	−0.1 (3)	C13—C14—N1—C15	38.7 (2)
N1—C1—C2—C3	179.10 (18)	C9—C14—N1—C15	−139.54 (18)
C1—C2—C3—C4	0.4 (3)	C16—C15—N1—C1	−160.55 (15)
C2—C3—C4—C5	−0.1 (4)	C16—C15—N1—C14	52.9 (2)
C3—C4—C5—C6	−0.5 (4)	C16—C17—N2—C19	52.0 (2)
C4—C5—C6—C1	0.7 (3)	C16—C17—N2—C18	176.04 (17)
C4—C5—C6—C7	−179.6 (2)	O1—C20—C21—C22	171.0 (2)
C2—C1—C6—C5	−0.4 (3)	C25—C20—C21—C22	−6.9 (3)
N1—C1—C6—C5	−179.61 (18)	O1—C20—C21—N3	−7.3 (3)
C2—C1—C6—C7	180.0 (2)	C25—C20—C21—N3	174.70 (18)
N1—C1—C6—C7	0.7 (3)	C20—C21—C22—C23	4.0 (3)
C5—C6—C7—C8	169.2 (2)	N3—C21—C22—C23	−177.59 (18)
C1—C6—C7—C8	−11.1 (3)	C21—C22—C23—C24	0.8 (3)
C6—C7—C8—C9	65.1 (3)	C21—C22—C23—N4	179.67 (18)
C7—C8—C9—C10	108.0 (3)	C22—C23—C24—C25	−1.8 (3)
C7—C8—C9—C14	−68.1 (3)	N4—C23—C24—C25	179.26 (17)
C14—C9—C10—C11	−0.1 (4)	C23—C24—C25—C20	−1.8 (3)
C8—C9—C10—C11	−176.2 (3)	C23—C24—C25—N5	179.00 (17)
C9—C10—C11—C12	0.0 (4)	O1—C20—C25—C24	−172.09 (19)
C10—C11—C12—C13	0.3 (4)	C21—C20—C25—C24	5.8 (3)
C11—C12—C13—C14	−0.4 (3)	O1—C20—C25—N5	7.1 (3)
C12—C13—C14—C9	0.2 (3)	C21—C20—C25—N5	−175.09 (16)
C12—C13—C14—N1	−177.97 (17)	C22—C21—N3—O3	145.3 (2)
C10—C9—C14—C13	0.0 (3)	C20—C21—N3—O3	−36.2 (3)
C8—C9—C14—C13	176.3 (2)	C22—C21—N3—O2	−32.7 (3)
C10—C9—C14—N1	178.3 (2)	C20—C21—N3—O2	145.8 (2)
C8—C9—C14—N1	−5.5 (3)	C22—C23—N4—O5	176.3 (2)
N1—C15—C16—C17	53.8 (2)	C24—C23—N4—O5	−4.8 (3)
C15—C16—C17—N2	57.8 (2)	C22—C23—N4—O4	−4.0 (3)
C2—C1—N1—C14	127.93 (19)	C24—C23—N4—O4	174.97 (19)
C6—C1—N1—C14	−52.8 (2)	C24—C25—N5—O7	3.0 (3)
C2—C1—N1—C15	−18.1 (2)	C20—C25—N5—O7	−176.15 (19)
C6—C1—N1—C15	161.15 (17)	C24—C25—N5—O6	−175.99 (19)
C13—C14—N1—C1	−107.4 (2)	C20—C25—N5—O6	4.8 (3)
C9—C14—N1—C1	74.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1	0.90 (2)	1.88 (2)	2.686 (2)	148.2 (17)
N2—H1···O6	0.90 (2)	2.53 (2)	3.189 (2)	130.0 (16)

Experimental details

Crystal data
Chemical formula	C₁₉H₂₅N₂⁺·C₆H₂N₃O₇⁻
M_r	509.52
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	10.5204 (10), 10.6661 (10), 11.7603 (11)
α, β, γ (°)	77.292 (1), 73.862 (1), 84.590 (1)
V (Å³)	1235.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7898, 4674, 2818
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.127, 0.95
No. of reflections	4674
No. of parameters	339
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1	0.90 (2)	1.88 (2)	2.686 (2)	148.2 (17)
N2—H1···O6	0.90 (2)	2.53 (2)	3.189 (2)	130.0 (16)

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