Doxyl­amine hydrogen succinate

Parvez, M.; Dalrymple, S.; Cote, A.

doi:10.1107/S160053680100085X

Doxylamine hydrogen succinate

The crystal structure of doxylamine hydrogen succinate or dimethyl{[1-phenyl-1-(2-pyridyl)ethoxy]ethyl]ammonium hydrogen succinate, C₁₇H₂₃N₂O⁺·C₄H₅O₄⁻, contains two independent protonated molecules of doxylamine with different conformations and two succinate anions in an asymmetric unit. The structure is stabilized by hydrogen bonds involving the cations and the anions, with O

O and N

O distances in the range 2.536 (5)–2.853 (5) Å.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100085X/ya6001sup1.cif Contains datablocks Global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680100085X/ya6001Isup2.hkl Contains datablock I

CCDC reference: 159754

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.009 Å
R factor = 0.067
wR factor = 0.243
Data-to-parameter ratio = 19.3

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No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSMU_01  Alert C The ratio of given/expected absorption coefficient lies
          outside the range 0.99 <> 1.01
          Calculated value of mu =     0.087
          Value of mu given      =     0.090


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Doxylamine [dimethylaminoethoxy(methyl)benzylpyridine] is a chiral tertiary aminoalkyl ether, with antihistaminic actions on the H₁-receptor site (Casy, 1991). The crystal structures of the tetrachlorozincate(II), tetrachlorocobaltate(II) (Parvez & Sabir, 1998) and tetrachlorocuprate(II) (Braitenbach & Parvez, 2000) salts of doxylamine have been reported from our laboratory. The crystal structures of a number of compounds belonging to this class of ethers which possess antiallergic activities have been reported, e.g. diphenhydramine hydrochloride (Glaser & Maartmann-Moe, 1990), diphenhydramine thiourea complex (Wiedenfeld & Knoch, 1987), carbinoxamine maleate (Bertolasi et al., 1980) and clemastine hydrogen fumarate (Parvez & Wendling, 1991). The crystal structure of orphenadrine hydrochloride, a skeletal muscle relaxant, which is closely related to these compounds has also been reported (Glaser et al., 1992). Continuing our investigations on the conformation of this important antiallergic drug, we now report the crystal structure of doxylamine hydrogen succinate, (I).

The asymmetric unit of (I) is composed of two cations of the antihistamine with different conformations and two hydrogen succinate ions (Fig. 1). The C9A–C12A atoms in one of the phenyl rings and the O3A atom had large displacement displacement parameters possibly reflecting a degree of disorder.

In both cations in (I), the pyridine rings are planar; they are inclined by 84.6 (2) and 85.9 (2)° to the phenyl rings. The corresponding angles in the tetrachlorozincate(II), tetrachlorocobaltate(II) (Parvez & Sabir, 1998) and tetrachlorocuprate(II) (Braitenbach & Parvez, 2000) salts of doxylamine were 87.68 (14), 88.1 (2) and 82.9 (3)°, respectively.

The orientations of the pyridyl rings in both cations in (I) are different from their conformations in the dihydrocationic salts of doxylamine mentioned above, wherein both lone electron pairs of ethereal O atoms were oriented towards ammonium and pyridinium H atoms. This difference in orientation is due to a lack of interactions between ethereal O and pyridyl N atoms in (I) and results in a rotation of approximately 180° about the C5—C6 and C5A—C6A bonds in both cations of (I) as compared with those in the doxylamine moiety in the dihydrocationic salts. Furthermore, the cations in (I) differ in the orientation of the aminomethyl groups; the ammonium H atom of one of the cations has switched positions with a methyl group as compared to the other cation resulting in significantly different intramolecular separations between the ethereal O and ammonium N atoms: N2···O1 3.095 (6) versus N2A···O1A 2.870 (6) Å. The difference in the orientation of the aminomethyl groups in the two cations is evident from a comparison of the torsion angles O1—C14—C15—N2 76.9 (6)° and O1A—C14A—C15A—N2A 58.4 (6)°, and C14—C15—N2—C17 - 62.0 (6)° and C14A—C15A—N2A—C17A 51.5 (6)°. The torsion angles corresponding to C5—C6—O1—C14, C6—-O1–C14—C15 and C14—C15—N2—C17 in the two molecules are close to 180° with values in the range 173.2 (4)–179.5 (5)°, with the exception of C6—O1—C14—C15 of 155.7 (5)° in one of the cations.

In general, carboxylic acids tend to form cyclic dimers via hydrogen bonding. The crystal structure of (I) displays an extensive network of hydrogenbonding wherein the succinate ions are linked into chains in a zigzag fashion along the c axis, with O5···O2A and O5A···O2 being 2.538 (5) and 2.536 (5) Å, respectively. Only a few carboxylic acids appear to adopt this arrangement (Bernstein et al., 1994), e.g. L-lysine succinate (Prasad & Vijayan, 1991). The cations are attached to the anion chains via ammonium H atoms involved in the N—H···O interactions with N2···O2 and N2A···O2A distances of 2.744 (5) and 2.853 (5) Å, respectively (see Table 1).

Experimental top

Crystals of (I) (Sigma Inc.) were grown from a solution in ethanol by slow evaporation at room temperature.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. ORTEPII (Johnson, 1976) drawings of the two independent cations and anions in (I). Displacement ellipsoids have been plotted at the 50% probability level.

Dimethylammoniumethoxy(methyl)benzylpyridine hydrogensuccinate top

Crystal data top

C₁₇H₂₃N₂O⁺·C₄H₅O₄⁻	F(000) = 1664
M_r = 388.45	D_x = 1.220 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
a = 8.901 (3) Å	Cell parameters from 25 reflections
b = 21.075 (4) Å	θ = 10.0–15.0°
c = 22.721 (5) Å	µ = 0.09 mm⁻¹
β = 97.22 (2)°	T = 293 K
V = 4228.4 (19) Å³	Prism, colourless
Z = 8	0.40 × 0.30 × 0.30 mm

Data collection top

Rigaku AFC-6S diffractometer	R_int = 0.06
Radiation source: fine-focus sealed tube	θ_max = 27.5°, θ_min = 2.0°
Graphite monochromator	h = 0→11
ω/2θ scans	k = 0→27
10376 measured reflections	l = −29→29
9763 independent reflections	3 standard reflections every 200 reflections
2872 reflections with I > 2σ(I)	intensity decay: <0.1%

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.243	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0479P)² + 9.25P] where P = (F_o² + 2F_c²)/3
9763 reflections	(Δ/σ)_max < 0.001
507 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₇H₂₃N₂O⁺·C₄H₅O₄⁻	V = 4228.4 (19) Å³
M_r = 388.45	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.901 (3) Å	µ = 0.09 mm⁻¹
b = 21.075 (4) Å	T = 293 K
c = 22.721 (5) Å	0.40 × 0.30 × 0.30 mm
β = 97.22 (2)°

Data collection top

Rigaku AFC-6S diffractometer	R_int = 0.06
10376 measured reflections	3 standard reflections every 200 reflections
9763 independent reflections	intensity decay: <0.1%
2872 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.243	H-atom parameters constrained
S = 1.04	Δρ_max = 0.42 e Å⁻³
9763 reflections	Δρ_min = −0.31 e Å⁻³
507 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.

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

	x	y	z	U_iso*/U_eq
O1	0.3343 (4)	0.47810 (18)	0.33285 (15)	0.0509 (10)
N1	0.4549 (6)	0.3162 (2)	0.3206 (2)	0.0599 (14)
N2	0.1845 (4)	0.6074 (2)	0.29755 (18)	0.0390 (11)
H1	0.0969	0.6050	0.3142	0.047*
C1	0.4878 (7)	0.2783 (3)	0.2761 (3)	0.0607 (18)
H1A	0.5174	0.2368	0.2854	0.073*
C2	0.4803 (7)	0.2974 (3)	0.2175 (3)	0.0585 (17)
H2A	0.5018	0.2695	0.1879	0.070*
C3	0.4403 (8)	0.3585 (3)	0.2050 (3)	0.070 (2)
H3A	0.4342	0.3731	0.1661	0.084*
C4	0.4084 (8)	0.3995 (3)	0.2495 (3)	0.0651 (19)
H4A	0.3825	0.4415	0.2410	0.078*
C5	0.4158 (6)	0.3768 (3)	0.3065 (2)	0.0416 (14)
C6	0.3850 (6)	0.4185 (3)	0.3589 (2)	0.0432 (14)
C7	0.5347 (7)	0.4286 (3)	0.3989 (2)	0.0429 (14)
C8	0.6468 (7)	0.4650 (3)	0.3784 (3)	0.0565 (17)
H8A	0.6287	0.4839	0.3412	0.068*
C9	0.7847 (8)	0.4735 (3)	0.4123 (3)	0.074 (2)
H9	0.8577	0.4990	0.3982	0.088*
C10	0.8152 (9)	0.4446 (4)	0.4667 (3)	0.076 (2)
H10A	0.9090	0.4496	0.4893	0.091*
C11	0.7057 (10)	0.4087 (3)	0.4867 (3)	0.070 (2)
H11A	0.7258	0.3895	0.5236	0.084*
C12	0.5650 (8)	0.3997 (3)	0.4540 (2)	0.0543 (16)
H12A	0.4922	0.3748	0.4688	0.065*
C13	0.2621 (7)	0.3887 (3)	0.3914 (3)	0.0654 (19)
H13A	0.2439	0.4154	0.4240	0.098*
H13B	0.2948	0.3476	0.4061	0.098*
H13C	0.1705	0.3845	0.3645	0.098*
C14	0.2963 (7)	0.5258 (3)	0.3720 (2)	0.0553 (17)
H14A	0.3629	0.5232	0.4091	0.066*
H14B	0.1930	0.5198	0.3803	0.066*
C15	0.3116 (6)	0.5902 (3)	0.3443 (2)	0.0469 (15)
H15A	0.3181	0.6221	0.3753	0.056*
H15B	0.4057	0.5914	0.3269	0.056*
C16	0.2011 (7)	0.6733 (3)	0.2778 (3)	0.0616 (18)
H16A	0.1183	0.6838	0.2482	0.092*
H16B	0.2948	0.6776	0.2614	0.092*
H16C	0.2011	0.7014	0.3111	0.092*
C17	0.1705 (6)	0.5638 (3)	0.2458 (2)	0.0454 (14)
H17A	0.0861	0.5765	0.2177	0.068*
H17B	0.1546	0.5213	0.2588	0.068*
H17C	0.2617	0.5654	0.2273	0.068*
O1A	−0.0540 (4)	0.15355 (18)	0.55067 (15)	0.0434 (9)
N1A	0.1792 (6)	0.0219 (2)	0.6138 (2)	0.0602 (14)
N2A	−0.1818 (5)	0.2214 (2)	0.44678 (19)	0.0444 (12)
H2	−0.0861	0.2061	0.4471	0.053*
C1A	0.3225 (7)	0.0007 (3)	0.6089 (3)	0.0503 (15)
H1B	0.3588	−0.0339	0.6318	0.060*
C2A	0.4149 (6)	0.0276 (3)	0.5724 (3)	0.0522 (16)
H2B	0.5109	0.0112	0.5698	0.063*
C3A	0.3620 (6)	0.0797 (3)	0.5393 (3)	0.0533 (16)
H3B	0.4235	0.0991	0.5144	0.064*
C4A	0.2186 (6)	0.1032 (2)	0.5428 (2)	0.0388 (13)
H4B	0.1834	0.1386	0.5209	0.047*
C5A	0.1280 (6)	0.0732 (2)	0.5797 (2)	0.0363 (13)
C6A	−0.0359 (6)	0.0951 (3)	0.5835 (2)	0.0441 (14)
C7A	−0.0557 (7)	0.1076 (3)	0.6478 (3)	0.0566 (17)
C8A	0.0160 (9)	0.1556 (4)	0.6780 (3)	0.082 (2)
H8B	0.0791	0.1819	0.6593	0.098*
C9A	−0.0030 (13)	0.1670 (5)	0.7386 (5)	0.122 (4)
H9B	0.0462	0.1999	0.7604	0.147*
C10A	−0.0992 (14)	0.1258 (7)	0.7623 (4)	0.118 (5)
H10B	−0.1201	0.1324	0.8009	0.142*
C11A	−0.1640 (13)	0.0762 (6)	0.7316 (6)	0.143 (5)
H11B	−0.2231	0.0481	0.7504	0.172*
C12A	−0.1458 (8)	0.0665 (4)	0.6753 (4)	0.086 (2)
H12B	−0.1931	0.0325	0.6545	0.103*
C13A	−0.1420 (7)	0.0442 (3)	0.5536 (3)	0.077 (2)
H13D	−0.2452	0.0567	0.5550	0.115*
H13E	−0.1229	0.0046	0.5741	0.115*
H13F	−0.1244	0.0394	0.5130	0.115*
C14A	−0.1949 (6)	0.1853 (3)	0.5515 (2)	0.0506 (16)
H14C	−0.2042	0.2004	0.5912	0.061*
H14D	−0.2781	0.1565	0.5394	0.061*
C15A	−0.1993 (6)	0.2406 (3)	0.5090 (2)	0.0439 (14)
H15C	−0.2948	0.2627	0.5090	0.053*
H15D	−0.1188	0.2699	0.5231	0.053*
C16A	−0.1953 (8)	0.2785 (3)	0.4073 (3)	0.078 (2)
H16D	−0.1834	0.2660	0.3675	0.117*
H16E	−0.1180	0.3086	0.4213	0.117*
H16F	−0.2931	0.2975	0.4078	0.117*
C17A	−0.2867 (7)	0.1707 (4)	0.4233 (3)	0.078 (2)
H17D	−0.2753	0.1348	0.4495	0.117*
H17E	−0.2642	0.1582	0.3847	0.117*
H17F	−0.3890	0.1860	0.4204	0.117*
O2	−0.1021 (4)	0.60452 (18)	0.32998 (15)	0.0422 (9)
O3	0.0240 (4)	0.6541 (2)	0.40586 (18)	0.0684 (14)
O4	−0.5046 (4)	0.7175 (2)	0.42707 (17)	0.0600 (12)
O5	−0.3921 (4)	0.7613 (2)	0.50865 (16)	0.0468 (10)
H3	−0.3054	0.7656	0.5252	0.070*
C18	−0.0953 (6)	0.6392 (3)	0.3759 (2)	0.0390 (13)
C19	−0.2458 (5)	0.6617 (3)	0.3933 (2)	0.0470 (15)
H19A	−0.3005	0.6836	0.3597	0.056*
H19B	−0.3048	0.6248	0.4014	0.056*
C20	−0.2360 (5)	0.7052 (3)	0.4464 (2)	0.0408 (14)
H20A	−0.1730	0.7414	0.4396	0.049*
H20B	−0.1875	0.6827	0.4809	0.049*
C21	−0.3894 (6)	0.7288 (3)	0.4591 (2)	0.0368 (13)
O2A	0.1334 (4)	0.21418 (19)	0.43556 (15)	0.0474 (10)
O3A	0.0024 (5)	0.1691 (3)	0.3592 (2)	0.123 (3)
O4A	0.5079 (4)	0.1128 (2)	0.30771 (16)	0.0513 (11)
O5A	0.3624 (4)	0.08584 (19)	0.22668 (16)	0.0448 (10)
H4	0.2765	0.0943	0.2112	0.067*
C18A	0.1233 (6)	0.1823 (3)	0.3878 (3)	0.0546 (17)
C19A	0.2684 (6)	0.1619 (3)	0.3656 (2)	0.0494 (16)
H19C	0.3215	0.1325	0.3937	0.059*
H19D	0.3327	0.1987	0.3632	0.059*
C20A	0.2417 (6)	0.1305 (3)	0.3054 (2)	0.0590 (19)
H20C	0.1876	0.1601	0.2777	0.071*
H20D	0.1767	0.0940	0.3082	0.071*
C21A	0.3829 (6)	0.1089 (3)	0.2802 (2)	0.0370 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.071 (3)	0.044 (2)	0.038 (2)	0.027 (2)	0.0075 (19)	0.0015 (19)
N1	0.078 (4)	0.037 (3)	0.065 (3)	0.012 (3)	0.009 (3)	−0.002 (3)
N2	0.029 (2)	0.041 (3)	0.049 (3)	0.006 (2)	0.016 (2)	0.004 (2)
C1	0.077 (5)	0.034 (4)	0.070 (5)	0.013 (3)	0.009 (4)	−0.008 (4)
C2	0.072 (4)	0.053 (4)	0.049 (4)	0.014 (4)	0.002 (3)	−0.013 (3)
C3	0.095 (5)	0.066 (5)	0.048 (4)	0.032 (4)	0.007 (4)	−0.004 (4)
C4	0.097 (5)	0.055 (4)	0.043 (4)	0.027 (4)	0.008 (3)	0.002 (3)
C5	0.047 (3)	0.037 (3)	0.039 (3)	0.003 (3)	−0.002 (3)	0.000 (3)
C6	0.056 (4)	0.037 (3)	0.037 (3)	0.011 (3)	0.009 (3)	0.004 (3)
C7	0.060 (4)	0.036 (3)	0.033 (3)	0.012 (3)	0.010 (3)	0.003 (3)
C8	0.065 (4)	0.050 (4)	0.052 (4)	0.006 (3)	−0.001 (3)	0.008 (3)
C9	0.074 (5)	0.066 (5)	0.078 (5)	−0.005 (4)	−0.005 (4)	0.004 (4)
C10	0.088 (6)	0.062 (5)	0.070 (5)	0.006 (4)	−0.022 (4)	−0.014 (4)
C11	0.116 (6)	0.062 (5)	0.028 (3)	0.027 (5)	−0.005 (4)	−0.009 (3)
C12	0.087 (5)	0.039 (4)	0.037 (3)	0.011 (3)	0.011 (3)	0.004 (3)
C13	0.061 (4)	0.070 (5)	0.067 (4)	−0.001 (4)	0.017 (3)	0.010 (4)
C14	0.073 (4)	0.054 (4)	0.041 (3)	0.023 (3)	0.017 (3)	0.001 (3)
C15	0.039 (3)	0.060 (4)	0.041 (3)	0.009 (3)	0.005 (3)	−0.008 (3)
C16	0.067 (4)	0.047 (4)	0.073 (5)	0.007 (3)	0.020 (4)	0.008 (4)
C17	0.040 (3)	0.039 (3)	0.058 (4)	0.005 (3)	0.007 (3)	−0.008 (3)
O1A	0.032 (2)	0.054 (3)	0.045 (2)	0.0058 (18)	0.0074 (16)	0.000 (2)
N1A	0.063 (4)	0.055 (4)	0.062 (3)	0.005 (3)	0.006 (3)	−0.002 (3)
N2A	0.029 (2)	0.064 (3)	0.039 (3)	0.014 (2)	0.0016 (19)	−0.005 (3)
C1A	0.058 (4)	0.041 (4)	0.051 (4)	0.013 (3)	0.000 (3)	0.005 (3)
C2A	0.039 (3)	0.057 (4)	0.061 (4)	0.011 (3)	0.006 (3)	−0.002 (3)
C3A	0.036 (3)	0.067 (5)	0.059 (4)	−0.001 (3)	0.012 (3)	0.002 (3)
C4A	0.037 (3)	0.030 (3)	0.049 (3)	0.002 (3)	0.004 (3)	0.004 (3)
C5A	0.038 (3)	0.034 (3)	0.038 (3)	0.005 (3)	0.006 (2)	−0.003 (3)
C6A	0.034 (3)	0.046 (4)	0.054 (4)	−0.003 (3)	0.012 (3)	−0.002 (3)
C7A	0.059 (4)	0.068 (5)	0.046 (4)	0.026 (4)	0.018 (3)	0.007 (4)
C8A	0.107 (6)	0.098 (7)	0.037 (4)	0.037 (5)	−0.002 (4)	−0.012 (4)
C9A	0.137 (9)	0.128 (10)	0.095 (8)	0.064 (8)	−0.008 (7)	0.006 (7)
C10A	0.156 (11)	0.152 (12)	0.052 (6)	0.081 (9)	0.032 (6)	−0.003 (6)
C11A	0.158 (11)	0.158 (12)	0.133 (10)	0.040 (9)	0.096 (9)	0.049 (9)
C12A	0.080 (5)	0.101 (6)	0.088 (6)	−0.008 (5)	0.049 (5)	0.019 (5)
C13A	0.053 (4)	0.054 (5)	0.125 (7)	−0.018 (4)	0.018 (4)	−0.023 (4)
C14A	0.034 (3)	0.072 (5)	0.046 (3)	0.016 (3)	0.007 (3)	−0.003 (3)
C15A	0.031 (3)	0.059 (4)	0.040 (3)	0.012 (3)	−0.002 (2)	−0.005 (3)
C16A	0.096 (6)	0.084 (6)	0.058 (4)	0.038 (5)	0.020 (4)	0.012 (4)
C17A	0.057 (4)	0.108 (6)	0.066 (5)	−0.011 (4)	−0.007 (4)	−0.043 (4)
O2	0.0319 (19)	0.058 (3)	0.038 (2)	0.0026 (18)	0.0084 (16)	−0.0145 (19)
O3	0.029 (2)	0.115 (4)	0.058 (3)	0.012 (2)	−0.0071 (19)	−0.040 (3)
O4	0.027 (2)	0.096 (4)	0.056 (3)	0.003 (2)	0.0038 (19)	−0.026 (2)
O5	0.033 (2)	0.068 (3)	0.042 (2)	0.002 (2)	0.0118 (18)	−0.014 (2)
C18	0.035 (3)	0.047 (4)	0.035 (3)	0.005 (3)	0.003 (2)	−0.007 (3)
C19	0.028 (3)	0.062 (4)	0.051 (4)	0.002 (3)	0.006 (3)	−0.022 (3)
C20	0.028 (3)	0.054 (4)	0.040 (3)	0.005 (3)	0.005 (2)	−0.015 (3)
C21	0.031 (3)	0.047 (4)	0.034 (3)	0.001 (3)	0.011 (2)	−0.007 (3)
O2A	0.040 (2)	0.068 (3)	0.035 (2)	0.005 (2)	0.0076 (17)	−0.016 (2)
O3A	0.035 (3)	0.205 (7)	0.129 (5)	0.003 (3)	0.007 (3)	−0.120 (5)
O4A	0.030 (2)	0.073 (3)	0.049 (2)	0.012 (2)	−0.0050 (18)	−0.010 (2)
O5A	0.033 (2)	0.062 (3)	0.039 (2)	0.010 (2)	0.0056 (16)	−0.007 (2)
C18A	0.032 (3)	0.082 (5)	0.050 (4)	0.003 (3)	0.002 (3)	−0.021 (4)
C19A	0.031 (3)	0.073 (5)	0.044 (3)	0.007 (3)	0.005 (2)	−0.018 (3)
C20A	0.030 (3)	0.108 (6)	0.039 (3)	0.012 (3)	0.006 (2)	−0.025 (4)
C21A	0.035 (3)	0.043 (3)	0.033 (3)	0.008 (3)	0.004 (2)	−0.001 (3)

Geometric parameters (Å, º) top

O1—C14	1.411 (6)	C1A—C2A	1.363 (8)
O1—C6	1.437 (6)	C2A—C3A	1.380 (8)
N1—C1	1.349 (7)	C3A—C4A	1.381 (7)
N1—C5	1.353 (7)	C4A—C5A	1.385 (7)
N2—C16	1.472 (7)	C5A—C6A	1.543 (7)
N2—C17	1.486 (6)	C6A—C7A	1.517 (8)
N2—C15	1.496 (6)	C6A—C13A	1.530 (8)
C1—C2	1.385 (8)	C7A—C8A	1.339 (9)
C2—C3	1.357 (8)	C7A—C12A	1.381 (9)
C3—C4	1.385 (8)	C8A—C9A	1.426 (11)
C4—C5	1.373 (8)	C9A—C10A	1.376 (14)
C5—C6	1.533 (7)	C10A—C11A	1.345 (15)
C6—C13	1.528 (8)	C11A—C12A	1.327 (12)
C6—C7	1.531 (8)	C14A—C15A	1.509 (8)
C7—C8	1.385 (8)	O2—C18	1.270 (6)
C7—C12	1.387 (7)	O3—C18	1.227 (6)
C8—C9	1.375 (8)	O4—C21	1.204 (6)
C9—C10	1.374 (9)	O5—C21	1.320 (6)
C10—C11	1.355 (10)	C18—C19	1.519 (7)
C11—C12	1.386 (9)	C19—C20	1.508 (7)
C14—C15	1.509 (8)	C20—C21	1.515 (7)
O1A—C14A	1.424 (6)	O2A—C18A	1.269 (6)
O1A—C6A	1.438 (6)	O3A—C18A	1.218 (6)
N1A—C1A	1.369 (7)	O4A—C21A	1.209 (6)
N1A—C5A	1.375 (7)	O5A—C21A	1.301 (6)
N2A—C17A	1.474 (7)	C18A—C19A	1.508 (7)
N2A—C16A	1.497 (7)	C19A—C20A	1.510 (7)
N2A—C15A	1.498 (6)	C20A—C21A	1.515 (7)

C14—O1—C6	116.8 (4)	C3A—C4A—C5A	118.9 (5)
C1—N1—C5	117.0 (5)	N1A—C5A—C4A	121.6 (5)
C16—N2—C17	110.1 (4)	N1A—C5A—C6A	116.9 (5)
C16—N2—C15	110.4 (4)	C4A—C5A—C6A	121.6 (5)
C17—N2—C15	113.2 (4)	O1A—C6A—C7A	109.4 (5)
N1—C1—C2	124.1 (6)	O1A—C6A—C13A	110.3 (5)
C3—C2—C1	117.1 (6)	C7A—C6A—C13A	114.1 (5)
C2—C3—C4	120.7 (6)	O1A—C6A—C5A	105.8 (4)
C5—C4—C3	118.8 (6)	C7A—C6A—C5A	109.4 (5)
N1—C5—C4	122.2 (5)	C13A—C6A—C5A	107.5 (5)
N1—C5—C6	115.0 (5)	C8A—C7A—C12A	120.5 (7)
C4—C5—C6	122.8 (5)	C8A—C7A—C6A	121.3 (6)
O1—C6—C13	110.5 (5)	C12A—C7A—C6A	118.1 (7)
O1—C6—C7	109.1 (5)	C7A—C8A—C9A	121.0 (9)
C13—C6—C7	113.1 (5)	C10A—C9A—C8A	115.3 (11)
O1—C6—C5	104.9 (4)	C11A—C10A—C9A	122.3 (10)
C13—C6—C5	110.5 (5)	C12A—C11A—C10A	121.5 (11)
C7—C6—C5	108.3 (4)	C11A—C12A—C7A	119.3 (9)
C8—C7—C12	118.6 (6)	O1A—C14A—C15A	107.8 (4)
C8—C7—C6	119.2 (5)	N2A—C15A—C14A	113.5 (5)
C12—C7—C6	122.1 (6)	O3—C18—O2	123.4 (5)
C9—C8—C7	120.9 (6)	O3—C18—C19	120.4 (5)
C10—C9—C8	120.5 (7)	O2—C18—C19	116.2 (4)
C11—C10—C9	118.6 (7)	C20—C19—C18	115.7 (4)
C10—C11—C12	122.5 (6)	C19—C20—C21	112.9 (4)
C11—C12—C7	118.9 (6)	O4—C21—O5	120.9 (5)
O1—C14—C15	109.7 (4)	O4—C21—C20	122.6 (5)
N2—C15—C14	114.4 (5)	O5—C21—C20	116.5 (4)
C14A—O1A—C6A	116.0 (4)	O3A—C18A—O2A	122.7 (5)
C1A—N1A—C5A	117.1 (5)	O3A—C18A—C19A	119.5 (5)
C17A—N2A—C16A	111.5 (5)	O2A—C18A—C19A	117.8 (5)
C17A—N2A—C15A	113.6 (5)	C18A—C19A—C20A	112.6 (4)
C16A—N2A—C15A	109.8 (4)	C19A—C20A—C21A	115.5 (4)
C2A—C1A—N1A	123.7 (6)	O4A—C21A—O5A	121.4 (5)
C1A—C2A—C3A	118.1 (5)	O4A—C21A—C20A	122.5 (5)
C2A—C3A—C4A	120.6 (6)	O5A—C21A—C20A	116.1 (4)

C5—N1—C1—C2	−1.6 (9)	C1A—N1A—C5A—C6A	177.6 (5)
N1—C1—C2—C3	1.5 (10)	C3A—C4A—C5A—N1A	1.9 (8)
C1—C2—C3—C4	−0.1 (10)	C3A—C4A—C5A—C6A	−177.2 (5)
C2—C3—C4—C5	−1.0 (11)	C14A—O1A—C6A—C7A	−58.1 (6)
C1—N1—C5—C4	0.4 (9)	C14A—O1A—C6A—C13A	68.3 (6)
C1—N1—C5—C6	−177.9 (5)	C14A—O1A—C6A—C5A	−175.8 (4)
C3—C4—C5—N1	0.8 (10)	N1A—C5A—C6A—O1A	172.3 (4)
C3—C4—C5—C6	179.0 (6)	C4A—C5A—C6A—O1A	−8.6 (7)
C14—O1—C6—C13	60.4 (6)	N1A—C5A—C6A—C7A	54.6 (7)
C14—O1—C6—C7	−64.6 (6)	C4A—C5A—C6A—C7A	−126.3 (6)
C14—O1—C6—C5	179.5 (5)	N1A—C5A—C6A—C13A	−69.8 (6)
N1—C5—C6—O1	−175.4 (5)	C4A—C5A—C6A—C13A	109.3 (6)
C4—C5—C6—O1	6.2 (7)	O1A—C6A—C7A—C8A	−48.1 (7)
N1—C5—C6—C13	−56.3 (6)	C13A—C6A—C7A—C8A	−172.2 (6)
C4—C5—C6—C13	125.3 (6)	C5A—C6A—C7A—C8A	67.4 (7)
N1—C5—C6—C7	68.1 (6)	O1A—C6A—C7A—C12A	134.3 (6)
C4—C5—C6—C7	−110.2 (6)	C13A—C6A—C7A—C12A	10.1 (8)
O1—C6—C7—C8	−45.3 (7)	C5A—C6A—C7A—C12A	−110.3 (6)
C13—C6—C7—C8	−168.8 (5)	C12A—C7A—C8A—C9A	−2.3 (11)
C5—C6—C7—C8	68.4 (7)	C6A—C7A—C8A—C9A	−179.9 (6)
O1—C6—C7—C12	138.2 (5)	C7A—C8A—C9A—C10A	−0.4 (12)
C13—C6—C7—C12	14.7 (8)	C8A—C9A—C10A—C11A	3.5 (15)
C5—C6—C7—C12	−108.1 (6)	C9A—C10A—C11A—C12A	−4.1 (18)
C12—C7—C8—C9	−1.3 (9)	C10A—C11A—C12A—C7A	1.3 (16)
C6—C7—C8—C9	−177.9 (6)	C8A—C7A—C12A—C11A	1.9 (12)
C7—C8—C9—C10	1.7 (10)	C6A—C7A—C12A—C11A	179.6 (8)
C8—C9—C10—C11	−1.3 (11)	C6A—O1A—C14A—C15A	−173.2 (4)
C9—C10—C11—C12	0.6 (11)	C17A—N2A—C15A—C14A	51.5 (6)
C10—C11—C12—C7	−0.2 (10)	C16A—N2A—C15A—C14A	177.1 (5)
C8—C7—C12—C11	0.5 (8)	O1A—C14A—C15A—N2A	58.4 (6)
C6—C7—C12—C11	177.1 (5)	O3—C18—C19—C20	3.1 (8)
C6—O1—C14—C15	155.7 (5)	O2—C18—C19—C20	−177.5 (5)
C16—N2—C15—C14	174.0 (4)	C18—C19—C20—C21	176.7 (5)
C17—N2—C15—C14	−62.0 (6)	C19—C20—C21—O4	−5.3 (8)
O1—C14—C15—N2	76.9 (6)	C19—C20—C21—O5	172.7 (5)
C5A—N1A—C1A—C2A	−0.1 (9)	O3A—C18A—C19A—C20A	4.5 (10)
N1A—C1A—C2A—C3A	1.2 (9)	O2A—C18A—C19A—C20A	−173.9 (6)
C1A—C2A—C3A—C4A	−0.8 (9)	C18A—C19A—C20A—C21A	179.9 (6)
C2A—C3A—C4A—C5A	−0.7 (9)	C19A—C20A—C21A—O4A	4.3 (9)
C1A—N1A—C5A—C4A	−1.5 (8)	C19A—C20A—C21A—O5A	−175.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2	0.91	1.85	2.744 (5)	166
N2A—H2···O2A	0.91	2.01	2.853 (5)	153
O5—H3···O2Aⁱ	0.82	1.73	2.538 (5)	171
O5A—H4···O2ⁱⁱ	0.82	1.72	2.536 (5)	171

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₃N₂O⁺·C₄H₅O₄⁻
M_r	388.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.901 (3), 21.075 (4), 22.721 (5)
β (°)	97.22 (2)
V (Å³)	4228.4 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Rigaku AFC-6S diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10376, 9763, 2872
R_int	0.06
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.243, 1.04
No. of reflections	9763
No. of parameters	507
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.31

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN.