N-Butyl-4-butyl­imino-2-methyl­pentan-2-aminium (E)-quercetinate

Grosu, I.-G.; Borodi, G.; Pop, M.M.

doi:10.1107/S1600536812031170

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2450

https://doi.org/10.1107/S1600536812031170

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N-Butyl-4-butylimino-2-methylpentan-2-aminium (E)-quercetinate

Ioana-Georgeta Grosu,^a Gheorghe Borodi ^a and Mihaela Maria Pop ^a ^*

^aNational Institute for R&D of Isotopic and Molecular Technologies, PO Box 700, Cluj-Napoca R-400293, Romania
^*Correspondence e-mail: mihaela.pop@itim-cj.ro

(Received 6 June 2012; accepted 9 July 2012; online 14 July 2012)

The title salt, C₁₄H₃₁N₂⁺·C₁₅H₉O₇⁻, was obtained in the reaction of quercetin with n-butylamine in a mixture of acetone and hexane. The crystal structure determination shows that the quercetin donates one of its phenol H atoms to the N-butyl-4-butylimino-2-methylpentan-2-amine molecule. The crystal structure of the salt is stabilized by intramolecular (N—H⋯N for the cation and O—H⋯O for the anion) and intermolecular hydrogen bonding (N—H⋯O between cation–anion pairs and O—H⋯O between anions). Quercetin molecules form dimers connected into a two-dimensional network. The dihedral angle between the quercetin ring systems is 19.61 (8)°.

Related literature

For the antioxidant activity of quercetin, see: Young et al. (1999 ). For related co-crystal structures, see: Clarke et al. (2010 ); Kavuru et al. (2010 ).

Experimental

Crystal data

C₁₄H₃₁N₂⁺·C₁₅H₉O₇⁻
M_r = 528.63
Monoclinic, P 2₁ /n
a = 11.4017 (7) Å
b = 13.1730 (5) Å
c = 19.1961 (9) Å
β = 104.438 (6)°
V = 2792.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ). T_min = 0.647, T_max = 1.000
25155 measured reflections
6574 independent reflections
4881 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.233
S = 1.57
6574 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2B—H2BA⋯O6A	0.9	1.87	2.765 (2)	171
N2B—H2BB⋯N1B	0.9	2.05	2.749 (3)	134
O7A—H7A⋯O5A	0.82	1.92	2.642 (2)	147
O1A—H1A⋯O6Aⁱ	0.82	1.73	2.544 (2)	172
O2A—H2A⋯O6Aⁱ	0.82	1.85	2.6637 (19)	173
O4A—H4A⋯O2Aⁱⁱ	0.82	2.01	2.771 (2)	154
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031170/kj2204sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031170/kj2204Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031170/kj2204Isup3.cml

checkCIF report

Comment top

Quercetin belongs to the class of flavonoids which are naturally existing polyphenols possessing anti-oxidant activity (Young et al., 1999). Co-crystal forms of quercetin with theobromine and isonicotinic acid were reported (Clarke et al., 2010 and Kavuru et al., 2010). We present here the crystal structure of the title compound (Fig. 1). Quercetin molecules form nearly planar dimers through hydroxyl-hydroxyl (O4A—H4A···O2Aⁱⁱ, Table 1) supra-molecular homosynthon. The dihedral angle between the quercetin ring systems is 19.61 (8) degrees. The quercetin dimers are further connected via OH···O intermolecular hydrogen bonding involving the phenyl moieties into an infinite two-dimensional network (base vectors [1 0 - 1], [0 - 1 0]), extending parallel to (1 0 1) as shown in Fig. 2. One phenolic OH of quercetin is engaged in hydrogen bonding with one molecule of N-butyl-4-(butylimino)-2-methylpentane-2-amine and it transfers the proton to the basic moiety. Therefore, the title compound is a salt and not a co-crystal as the ones reported for quercetin so far.

Related literature top

For the antioxidant activity of quercetin, see: Young et al. (1999). For related co-crystal structures, see: Clarke et al. (2010); Kavuru et al. (2010).

Experimental top

The title compound (C₁₅H₉O₇) (C₁₄H₃₁N₂) was obtained in the reaction of quercetin with n-butylamine in a mixture of acetone/hexane. A suspension of quercetin dihydrate (0.044 mmol) in a mixture of acetone (2 ml) and hexane (1 ml) was stirred at 333 K for 30 minutes. The suspension was filtered and the clear solution was placed in a vial. The vial containing the quercetin solution was placed in a larger vial containing n-butylamine (2.5 ml). The vial was sealed to allow the slow diffusion of the amine vapors into the acetone/hexane quercetin solution. Yellow crystals of (I) were obtained after three days.

Structure description top

For the antioxidant activity of quercetin, see: Young et al. (1999). For related co-crystal structures, see: Clarke et al. (2010); Kavuru et al. (2010).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoid. The C-bound H atoms are omitted for clarity.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines and the H atoms have been omitted for clarity.

N-Butyl-4-butylimino-2-methylpentan-2-aminium 2-(3,4-dihydroxyphenyl)-3,5-dihydroxy-4-oxo-4H-1-benzopyran-7-olate top

Crystal data top

C₁₄H₃₁N₂⁺·C₁₅H₉O₇⁻	F(000) = 1136
M_r = 528.63	D_x = 1.258 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 11.4017 (7) Å	Cell parameters from 9486 reflections
b = 13.1730 (5) Å	θ = 3.1–28.9°
c = 19.1961 (9) Å	µ = 0.09 mm⁻¹
β = 104.438 (6)°	T = 293 K
V = 2792.1 (2) Å³	Prism, yellow
Z = 4	0.3 × 0.2 × 0.1 mm

Data collection top

SuperNova, Dual, Cu at zero, Eos diffractometer	6574 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4881 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 16.4335 pixels mm^-1	θ_max = 29.0°, θ_min = 3.1°
ω scans	h = −14→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010).	k = −16→17
T_min = 0.647, T_max = 1.000	l = −24→26
25155 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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.233	H-atom parameters constrained
S = 1.57	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
6574 reflections	(Δ/σ)_max < 0.001
352 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₄H₃₁N₂⁺·C₁₅H₉O₇⁻	V = 2792.1 (2) Å³
M_r = 528.63	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.4017 (7) Å	µ = 0.09 mm⁻¹
b = 13.1730 (5) Å	T = 293 K
c = 19.1961 (9) Å	0.3 × 0.2 × 0.1 mm
β = 104.438 (6)°

Data collection top

SuperNova, Dual, Cu at zero, Eos diffractometer	6574 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010).	4881 reflections with I > 2σ(I)
T_min = 0.647, T_max = 1.000	R_int = 0.030
25155 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.233	H-atom parameters constrained
S = 1.57	Δρ_max = 0.41 e Å⁻³
6574 reflections	Δρ_min = −0.38 e Å⁻³
352 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
O3A	0.72169 (12)	0.32311 (9)	0.12724 (7)	0.0363 (3)
O6A	0.46443 (12)	0.32713 (10)	0.28345 (7)	0.0406 (3)
C12A	0.59541 (17)	0.32353 (14)	0.20600 (9)	0.0348 (4)
H12A	0.5636	0.2617	0.1867	0.042*
O4A	0.94607 (14)	0.49703 (10)	0.09262 (8)	0.0487 (4)
H4A	0.9538	0.5572	0.1038	0.073*
C7A	0.80878 (16)	0.36415 (13)	0.09754 (9)	0.0331 (4)
C5A	0.83343 (17)	0.29650 (12)	0.04206 (9)	0.0325 (4)
O5A	0.87994 (14)	0.59111 (10)	0.20140 (8)	0.0507 (4)
O2A	0.96400 (16)	0.30683 (10)	−0.11267 (8)	0.0557 (5)
H2A	0.9692	0.2635	−0.1424	0.084*
C10A	0.73580 (17)	0.46380 (13)	0.20802 (9)	0.0351 (4)
O7A	0.73998 (17)	0.59868 (12)	0.29219 (9)	0.0643 (5)
H7A	0.7868	0.6201	0.2694	0.097*
C11A	0.68442 (16)	0.37099 (13)	0.18113 (9)	0.0321 (4)
C9A	0.82744 (17)	0.50911 (13)	0.17907 (10)	0.0365 (4)
C14A	0.60419 (19)	0.46257 (15)	0.28970 (10)	0.0423 (5)
H14A	0.5774	0.4929	0.3267	0.051*
C8A	0.85987 (17)	0.45473 (13)	0.12110 (10)	0.0348 (4)
C6A	0.89019 (16)	0.33040 (13)	−0.01056 (9)	0.0332 (4)
H6A	0.9152	0.3977	−0.0100	0.040*
C13A	0.55355 (17)	0.36998 (14)	0.26088 (9)	0.0352 (4)
C1A	0.90966 (17)	0.26601 (13)	−0.06322 (9)	0.0347 (4)
C2A	0.87269 (19)	0.16429 (14)	−0.06480 (10)	0.0407 (5)
C4A	0.79879 (19)	0.19478 (14)	0.04075 (11)	0.0411 (5)
H4AA	0.7619	0.1701	0.0754	0.049*
C15A	0.69287 (19)	0.50915 (15)	0.26400 (10)	0.0421 (5)
C3A	0.8190 (2)	0.13110 (14)	−0.01161 (11)	0.0454 (5)
H3A	0.7960	0.0634	−0.0114	0.054*
N2B	0.27813 (17)	0.27896 (12)	0.16548 (11)	0.0500 (5)
H2BA	0.3331	0.2946	0.2065	0.060*
H2BB	0.3193	0.2632	0.1326	0.060*
N1B	0.39679 (19)	0.13238 (17)	0.10738 (12)	0.0644 (6)
C8B	0.2110 (2)	0.18603 (17)	0.17890 (15)	0.0600 (6)
C12B	0.2816 (3)	0.46167 (19)	0.13476 (16)	0.0687 (7)
H12B	0.2315	0.5220	0.1301	0.082*
H12C	0.3435	0.4675	0.1796	0.082*
C7B	0.3047 (2)	0.10201 (17)	0.20315 (14)	0.0590 (6)
H7BA	0.3593	0.1235	0.2480	0.071*
H7BB	0.2624	0.0423	0.2137	0.071*
C5B	0.3785 (2)	0.07113 (18)	0.15472 (14)	0.0602 (6)
C3B	0.4607 (3)	0.1825 (3)	−0.00001 (18)	0.0922 (10)
H3BA	0.5218	0.1684	−0.0260	0.111*
H3BB	0.4758	0.2498	0.0207	0.111*
C9B	0.1187 (2)	0.1555 (2)	0.11018 (18)	0.0795 (9)
H9BA	0.0567	0.2065	0.0981	0.119*
H9BB	0.0829	0.0917	0.1174	0.119*
H9BC	0.1583	0.1492	0.0717	0.119*
C13B	0.3421 (3)	0.4609 (3)	0.0749 (2)	0.0939 (10)
H13A	0.2810	0.4594	0.0295	0.113*
H13B	0.3906	0.3998	0.0779	0.113*
C6B	0.4337 (3)	−0.0340 (2)	0.16675 (19)	0.0844 (9)
H6BA	0.3785	−0.0825	0.1389	0.127*
H6BB	0.4492	−0.0512	0.2168	0.127*
H6BC	0.5083	−0.0351	0.1522	0.127*
C11B	0.2045 (3)	0.37186 (18)	0.14017 (18)	0.0738 (8)
H11A	0.1504	0.3585	0.0934	0.089*
H11B	0.1551	0.3872	0.1733	0.089*
C10B	0.1493 (3)	0.2091 (2)	0.2401 (2)	0.0884 (10)
H10A	0.2089	0.2323	0.2817	0.133*
H10B	0.1115	0.1486	0.2519	0.133*
H10C	0.0891	0.2609	0.2247	0.133*
C4B	0.4711 (3)	0.1058 (3)	0.05941 (18)	0.0874 (9)
H4BA	0.4468	0.0396	0.0385	0.105*
H4BB	0.5549	0.1012	0.0866	0.105*
C14B	0.4228 (4)	0.5531 (3)	0.0763 (3)	0.1369 (19)
H14B	0.3809	0.6130	0.0854	0.205*
H14C	0.4425	0.5596	0.0307	0.205*
H14D	0.4958	0.5450	0.1136	0.205*
C1B	0.3270 (6)	0.2454 (5)	−0.1144 (3)	0.175 (3)
H1BA	0.3371	0.3149	−0.0990	0.263*
H1BB	0.2487	0.2368	−0.1469	0.263*
H1BC	0.3887	0.2276	−0.1383	0.263*
C2B	0.3368 (4)	0.1799 (4)	−0.0518 (3)	0.1251 (14)
H2BC	0.3185	0.1106	−0.0682	0.150*
H2BD	0.2769	0.2007	−0.0266	0.150*
O1A	0.88657 (18)	0.09668 (11)	−0.11484 (9)	0.0658 (5)
H1A	0.9087	0.1263	−0.1469	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3A	0.0456 (8)	0.0369 (7)	0.0352 (7)	−0.0082 (5)	0.0265 (6)	−0.0079 (5)
O6A	0.0461 (8)	0.0475 (7)	0.0370 (7)	−0.0029 (6)	0.0267 (6)	0.0032 (5)
C12A	0.0403 (11)	0.0365 (9)	0.0325 (9)	−0.0025 (7)	0.0181 (8)	−0.0008 (7)
O4A	0.0599 (10)	0.0430 (8)	0.0573 (9)	−0.0183 (6)	0.0415 (8)	−0.0152 (6)
C7A	0.0378 (10)	0.0378 (9)	0.0294 (8)	−0.0020 (7)	0.0192 (7)	−0.0010 (7)
C5A	0.0363 (10)	0.0352 (9)	0.0305 (8)	−0.0023 (7)	0.0171 (7)	−0.0029 (7)
O5A	0.0632 (10)	0.0441 (8)	0.0543 (9)	−0.0195 (7)	0.0325 (7)	−0.0165 (6)
O2A	0.0947 (12)	0.0401 (7)	0.0511 (9)	−0.0205 (7)	0.0534 (9)	−0.0132 (6)
C10A	0.0397 (11)	0.0392 (9)	0.0309 (9)	−0.0024 (7)	0.0172 (7)	−0.0040 (7)
O7A	0.0866 (13)	0.0574 (9)	0.0655 (10)	−0.0290 (8)	0.0499 (9)	−0.0337 (8)
C11A	0.0389 (10)	0.0346 (9)	0.0272 (8)	0.0015 (7)	0.0163 (7)	−0.0011 (6)
C9A	0.0418 (11)	0.0376 (9)	0.0339 (9)	−0.0057 (7)	0.0167 (8)	−0.0051 (7)
C14A	0.0524 (13)	0.0477 (10)	0.0352 (9)	−0.0020 (9)	0.0265 (9)	−0.0090 (8)
C8A	0.0381 (10)	0.0372 (9)	0.0350 (9)	−0.0030 (7)	0.0204 (8)	−0.0028 (7)
C6A	0.0420 (11)	0.0308 (8)	0.0319 (9)	−0.0040 (7)	0.0184 (7)	−0.0021 (7)
C13A	0.0403 (11)	0.0421 (9)	0.0286 (8)	0.0024 (8)	0.0186 (7)	0.0049 (7)
C1A	0.0433 (11)	0.0345 (8)	0.0329 (9)	−0.0043 (7)	0.0220 (8)	−0.0007 (7)
C2A	0.0545 (13)	0.0367 (9)	0.0389 (10)	−0.0092 (8)	0.0265 (9)	−0.0097 (7)
C4A	0.0515 (12)	0.0404 (9)	0.0404 (10)	−0.0108 (8)	0.0283 (9)	−0.0051 (8)
C15A	0.0517 (13)	0.0438 (10)	0.0369 (9)	−0.0076 (8)	0.0223 (9)	−0.0103 (8)
C3A	0.0644 (14)	0.0340 (9)	0.0480 (11)	−0.0142 (8)	0.0335 (10)	−0.0080 (8)
N2B	0.0492 (11)	0.0421 (9)	0.0576 (11)	0.0029 (7)	0.0115 (8)	0.0013 (8)
N1B	0.0646 (14)	0.0664 (13)	0.0640 (13)	0.0019 (10)	0.0192 (11)	−0.0097 (11)
C8B	0.0535 (15)	0.0461 (12)	0.0791 (17)	−0.0036 (10)	0.0140 (12)	0.0046 (11)
C12B	0.0732 (18)	0.0513 (13)	0.0774 (18)	0.0080 (12)	0.0106 (14)	0.0126 (12)
C7B	0.0611 (16)	0.0458 (12)	0.0670 (15)	−0.0023 (10)	0.0103 (12)	0.0027 (10)
C5B	0.0614 (16)	0.0512 (13)	0.0614 (15)	−0.0032 (10)	0.0031 (12)	−0.0038 (11)
C3B	0.088 (2)	0.121 (3)	0.0681 (19)	0.0099 (19)	0.0205 (17)	−0.0051 (18)
C9B	0.0555 (17)	0.0577 (14)	0.111 (2)	−0.0062 (12)	−0.0055 (15)	−0.0007 (15)
C13B	0.103 (2)	0.093 (2)	0.089 (2)	0.0237 (19)	0.0301 (19)	0.0281 (18)
C6B	0.093 (2)	0.0599 (16)	0.093 (2)	0.0146 (15)	0.0105 (17)	−0.0055 (15)
C11B	0.0647 (17)	0.0482 (13)	0.104 (2)	0.0104 (11)	0.0132 (15)	0.0108 (13)
C10B	0.093 (2)	0.0713 (18)	0.118 (3)	0.0025 (16)	0.059 (2)	0.0081 (18)
C4B	0.093 (2)	0.097 (2)	0.0758 (19)	0.0072 (18)	0.0288 (17)	−0.0140 (17)
C14B	0.108 (3)	0.126 (3)	0.183 (5)	−0.001 (2)	0.046 (3)	0.079 (3)
C1B	0.190 (6)	0.140 (4)	0.143 (5)	−0.015 (4)	−0.059 (4)	0.032 (4)
C2B	0.123 (3)	0.143 (4)	0.101 (3)	−0.001 (3)	0.014 (3)	0.024 (3)
O1A	0.1151 (15)	0.0414 (8)	0.0631 (10)	−0.0239 (8)	0.0637 (11)	−0.0208 (7)

Geometric parameters (Å, º) top

O3A—C7A	1.373 (2)	C8B—C10B	1.542 (4)
O3A—C11A	1.3667 (19)	C12B—H12B	0.9700
O6A—C13A	1.326 (2)	C12B—H12C	0.9700
C12A—H12A	0.9300	C12B—C13B	1.481 (4)
C12A—C11A	1.375 (2)	C12B—C11B	1.493 (4)
C12A—C13A	1.401 (2)	C7B—H7BA	0.9700
O4A—H4A	0.8200	C7B—H7BB	0.9700
O4A—C8A	1.358 (2)	C7B—C5B	1.458 (4)
C7A—C5A	1.468 (2)	C5B—C6B	1.515 (4)
C7A—C8A	1.355 (2)	C3B—H3BA	0.9700
C5A—C6A	1.402 (2)	C3B—H3BB	0.9700
C5A—C4A	1.395 (2)	C3B—C4B	1.506 (5)
O5A—C9A	1.257 (2)	C3B—C2B	1.512 (6)
O2A—H2A	0.8200	C9B—H9BA	0.9600
O2A—C1A	1.366 (2)	C9B—H9BB	0.9600
C10A—C11A	1.398 (2)	C9B—H9BC	0.9600
C10A—C9A	1.430 (2)	C13B—H13A	0.9700
C10A—C15A	1.419 (2)	C13B—H13B	0.9700
O7A—H7A	0.8200	C13B—C14B	1.520 (5)
O7A—C15A	1.352 (2)	C6B—H6BA	0.9600
C9A—C8A	1.447 (2)	C6B—H6BB	0.9600
C14A—H14A	0.9300	C6B—H6BC	0.9600
C14A—C13A	1.403 (3)	C11B—H11A	0.9700
C14A—C15A	1.375 (3)	C11B—H11B	0.9700
C6A—H6A	0.9300	C10B—H10A	0.9600
C6A—C1A	1.379 (2)	C10B—H10B	0.9600
C1A—C2A	1.403 (2)	C10B—H10C	0.9600
C2A—C3A	1.385 (2)	C4B—H4BA	0.9700
C2A—O1A	1.348 (2)	C4B—H4BB	0.9700
C4A—H4AA	0.9300	C14B—H14B	0.9600
C4A—C3A	1.372 (3)	C14B—H14C	0.9600
C3A—H3A	0.9300	C14B—H14D	0.9600
N2B—H2BA	0.9000	C1B—H1BA	0.9600
N2B—H2BB	0.9000	C1B—H1BB	0.9600
N2B—C8B	1.500 (3)	C1B—H1BC	0.9600
N2B—C11B	1.495 (3)	C1B—C2B	1.460 (7)
N1B—C5B	1.271 (3)	C2B—H2BC	0.9700
N1B—C4B	1.441 (4)	C2B—H2BD	0.9700
C8B—C7B	1.528 (3)	O1A—H1A	0.8200
C8B—C9B	1.522 (4)

C11A—O3A—C7A	121.74 (13)	C8B—C7B—H7BB	107.7
C11A—C12A—H12A	120.6	H7BA—C7B—H7BB	107.1
C11A—C12A—C13A	118.81 (16)	C5B—C7B—C8B	118.6 (2)
C13A—C12A—H12A	120.6	C5B—C7B—H7BA	107.7
C8A—O4A—H4A	109.5	C5B—C7B—H7BB	107.7
O3A—C7A—C5A	110.56 (14)	N1B—C5B—C7B	120.2 (2)
C8A—C7A—O3A	120.22 (15)	N1B—C5B—C6B	123.6 (3)
C8A—C7A—C5A	129.22 (15)	C7B—C5B—C6B	116.2 (2)
C6A—C5A—C7A	122.38 (15)	H3BA—C3B—H3BB	108.0
C4A—C5A—C7A	119.43 (15)	C4B—C3B—H3BA	109.3
C4A—C5A—C6A	118.19 (15)	C4B—C3B—H3BB	109.3
C1A—O2A—H2A	109.5	C4B—C3B—C2B	111.5 (3)
C11A—C10A—C9A	120.06 (15)	C2B—C3B—H3BA	109.3
C11A—C10A—C15A	117.13 (16)	C2B—C3B—H3BB	109.3
C15A—C10A—C9A	122.81 (16)	C8B—C9B—H9BA	109.5
C15A—O7A—H7A	109.5	C8B—C9B—H9BB	109.5
O3A—C11A—C12A	116.66 (15)	C8B—C9B—H9BC	109.5
O3A—C11A—C10A	120.16 (15)	H9BA—C9B—H9BB	109.5
C12A—C11A—C10A	123.18 (15)	H9BA—C9B—H9BC	109.5
O5A—C9A—C10A	123.90 (16)	H9BB—C9B—H9BC	109.5
O5A—C9A—C8A	119.76 (16)	C12B—C13B—H13A	109.2
C10A—C9A—C8A	116.34 (15)	C12B—C13B—H13B	109.2
C13A—C14A—H14A	119.5	C12B—C13B—C14B	112.2 (4)
C15A—C14A—H14A	119.5	H13A—C13B—H13B	107.9
C15A—C14A—C13A	120.90 (16)	C14B—C13B—H13A	109.2
O4A—C8A—C9A	117.12 (15)	C14B—C13B—H13B	109.2
C7A—C8A—O4A	121.41 (15)	C5B—C6B—H6BA	109.5
C7A—C8A—C9A	121.44 (16)	C5B—C6B—H6BB	109.5
C5A—C6A—H6A	119.3	C5B—C6B—H6BC	109.5
C1A—C6A—C5A	121.33 (15)	H6BA—C6B—H6BB	109.5
C1A—C6A—H6A	119.3	H6BA—C6B—H6BC	109.5
O6A—C13A—C12A	119.50 (17)	H6BB—C6B—H6BC	109.5
O6A—C13A—C14A	120.98 (15)	N2B—C11B—H11A	109.2
C12A—C13A—C14A	119.50 (16)	N2B—C11B—H11B	109.2
O2A—C1A—C6A	116.80 (15)	C12B—C11B—N2B	112.2 (2)
O2A—C1A—C2A	123.14 (15)	C12B—C11B—H11A	109.2
C6A—C1A—C2A	120.06 (15)	C12B—C11B—H11B	109.2
C3A—C2A—C1A	118.10 (16)	H11A—C11B—H11B	107.9
O1A—C2A—C1A	123.96 (16)	C8B—C10B—H10A	109.5
O1A—C2A—C3A	117.94 (16)	C8B—C10B—H10B	109.5
C5A—C4A—H4AA	119.9	C8B—C10B—H10C	109.5
C3A—C4A—C5A	120.12 (16)	H10A—C10B—H10B	109.5
C3A—C4A—H4AA	119.9	H10A—C10B—H10C	109.5
O7A—C15A—C10A	119.52 (17)	H10B—C10B—H10C	109.5
O7A—C15A—C14A	120.01 (16)	N1B—C4B—C3B	111.9 (3)
C14A—C15A—C10A	120.47 (17)	N1B—C4B—H4BA	109.2
C2A—C3A—H3A	118.9	N1B—C4B—H4BB	109.2
C4A—C3A—C2A	122.19 (17)	C3B—C4B—H4BA	109.2
C4A—C3A—H3A	118.9	C3B—C4B—H4BB	109.2
H2BA—N2B—H2BB	107.3	H4BA—C4B—H4BB	107.9
C8B—N2B—H2BA	108.0	C13B—C14B—H14B	109.5
C8B—N2B—H2BB	108.0	C13B—C14B—H14C	109.5
C11B—N2B—H2BA	108.0	C13B—C14B—H14D	109.5
C11B—N2B—H2BB	108.0	H14B—C14B—H14C	109.5
C11B—N2B—C8B	117.04 (19)	H14B—C14B—H14D	109.5
C5B—N1B—C4B	122.0 (2)	H14C—C14B—H14D	109.5
N2B—C8B—C7B	107.19 (19)	H1BA—C1B—H1BB	109.5
N2B—C8B—C9B	109.8 (2)	H1BA—C1B—H1BC	109.5
N2B—C8B—C10B	108.6 (2)	H1BB—C1B—H1BC	109.5
C7B—C8B—C10B	109.1 (2)	C2B—C1B—H1BA	109.5
C9B—C8B—C7B	110.7 (2)	C2B—C1B—H1BB	109.5
C9B—C8B—C10B	111.3 (2)	C2B—C1B—H1BC	109.5
H12B—C12B—H12C	107.3	C3B—C2B—H2BC	108.9
C13B—C12B—H12B	108.2	C3B—C2B—H2BD	108.9
C13B—C12B—H12C	108.2	C1B—C2B—C3B	113.3 (4)
C13B—C12B—C11B	116.4 (3)	C1B—C2B—H2BC	108.9
C11B—C12B—H12B	108.2	C1B—C2B—H2BD	108.9
C11B—C12B—H12C	108.2	H2BC—C2B—H2BD	107.7
C8B—C7B—H7BA	107.7	C2A—O1A—H1A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2B—H2BA···O6A	0.9	1.87	2.765 (2)	171
N2B—H2BB···N1B	0.9	2.05	2.749 (3)	134
O7A—H7A···O5A	0.82	1.92	2.642 (2)	147
O1A—H1A···O6Aⁱ	0.82	1.73	2.544 (2)	172
O2A—H2A···O6Aⁱ	0.82	1.85	2.6637 (19)	173
O4A—H4A···O2Aⁱⁱ	0.82	2.01	2.771 (2)	154

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

Experimental details

Crystal data
Chemical formula	C₁₄H₃₁N₂⁺·C₁₅H₉O₇⁻
M_r	528.63
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.4017 (7), 13.1730 (5), 19.1961 (9)
β (°)	104.438 (6)
V (Å³)	2792.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	SuperNova, Dual, Cu at zero, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010).
T_min, T_max	0.647, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25155, 6574, 4881
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.233, 1.57
No. of reflections	6574
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.38

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2B—H2BA···O6A	0.9	1.87	2.765 (2)	171
N2B—H2BB···N1B	0.9	2.05	2.749 (3)	134
O7A—H7A···O5A	0.82	1.92	2.642 (2)	147
O1A—H1A···O6Aⁱ	0.82	1.73	2.544 (2)	172
O2A—H2A···O6Aⁱ	0.82	1.85	2.6637 (19)	173
O4A—H4A···O2Aⁱⁱ	0.82	2.01	2.771 (2)	154

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

Acknowledgements

This work was supported by ANCS, project No. POSCCE ID536.

References

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