2-Amino-6-methyl­pyridinium 3-(4-hydroxy-3-methoxy­phen­yl)prop-2-enoate monohydrate

Ni, S.-F.; Feng, W.-J.; Guo, H.; Jin, Z.-M.

doi:10.1107/S160053680704038X

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2-Amino-6-methylpyridinium 3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate monohydrate

S.-F. Ni, W.-J. Feng, H. Guo and Z.-M. Jin

In the title salt, C₆H₉N₂⁺·C₁₀H₉O₄⁻·H₂O, the cation, anion and solvent molecule are held together by N—H

O hydrogen bonds. A one-dimensional chiral chain along the c axis is formed by O—H

O hydrogen bonds. The chirality of the supramolecular chain-like arrangement is extended into layers parallel to the (101) plane by additional O—H

O hydrogen bonds. The structure is further stabilized by π–π interactions between benzene and pyridine rings [centroid-to-centroid distances = 3.813 (4) and 3.658 (3) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704038X/im2026sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680704038X/im2026Isup2.hkl Contains datablock I

CCDC reference: 660330

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.033
wR factor = 0.075
Data-to-parameter ratio = 8.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.06
PLAT731_ALERT_1_C Bond    Calc     0.82(4), Rep   0.819(10) ......       4.00 su-Ra
              O5   -H5A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(3), Rep   0.824(10) ......       3.00 su-Ra
              O5   -H5B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(4), Rep   0.820(10) ......       4.00 su-Ra
              O5   -H5A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(3), Rep   0.820(10) ......       3.00 su-Ra
              O5   -H5B     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.12(4), Rep   2.130(10) ......       4.00 su-Ra
              H5A  -O1      1.555   3.444
PLAT736_ALERT_1_C H...A   Calc     1.97(3), Rep   1.970(10) ......       3.00 su-Ra
              H5B  -O4      1.555   4.454
PLAT748_ALERT_1_C D-H..A  Calc   175.3(19), Rep      175.00 ......    Missing su
              N1   -H1N  -O4      1.555   1.555   1.555
PLAT748_ALERT_1_C D-H..A  Calc      166(2), Rep      166.00 ......    Missing su
              N2   -H2A  -O5      1.555   1.555   1.555
PLAT748_ALERT_1_C D-H..A  Calc      173(3), Rep      173.00 ......    Missing su
              N2   -H2B  -O3      1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.00
           From the CIF: _reflns_number_total               1920
           Count of symmetry unique reflns         1920
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

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

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

Comment top

As reported, the synthesis and characterization of noncentrosymmetric supramolecular systems have attracted a great of interest in th past few years (Sarma et al., 1997; Thalladi et al., 1999; Kaminskii et al., 2006; Kiebacha et al., 2006; Kaminskii et al., 2007). Herein, we report a novel noncentrosymmetric crystal of the title complex (Fig. 3), (I), and discuss the structure (Table 1).

In the structure, 2-amino-6-methylpyridinium (AMP) and 3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (ferulate) are linked through hydrogen bonding of N1—H1N···O4 and N2—H2B···O3 to produce an eight-membered hydrogen bonded ring system of R₂²(8) arrangement (Etter, 1990). This component shows an interaction with the water molecule by a N2—H2A···O5 hydrogen bond (Fig. 1 & Table 2). This is different from the componentially similar complex 2-amino-5-methylpyridinium ferulate monohydrate (Xuan et al., 2003), where the water molecule is incorporated with AMP by an O—H···O hydrogen bond.

Protonation of 2-aminopyridine always induces aminium-iminium tautomerism (Scheme 2) (Inuzuka & Fujimoto, 1986 and 1990). Obvious features of the iminium tautomer in (I) are revealed by the following bond length comparison. First, the N2—C1 [1.330 (3) Å] bond is slightly but significantly shorter than the N1—C1 [1.349 (3) Å] and N1—C5 [1.361 (3) Å] bonds (Table 1). Second, the C2—C3 [1.352 (4) Å] and C4—C5 [1.353 (4) Å] bonds are shorter than the C1—C2 [1.410 (3) Å] and C3—C4 [1.386 (4) Å] bonds. That means the imimium tautomer makes a great contribution to the structure. This situation is similiar to those observed in 2-amino-5-methylpyridinium ferulate (Xuan et al., 2003), 2-aminopyridinium acetate (Ishikawa et al., 2002), 2-amino-3-methylpyridinium maleate (Jin et al., 2002) and AMP neoabietate (Jin et al., 2000).

As shown in Fig. 2, one-dimensional C₂ chains along the (101) direction are formed by O1—H1O···O3ⁱ hydrogen bonds. The presence of water molecules in the structure causes the following hydrogen bonds: N2—H2A···O5, O5—H5A···O1ⁱⁱ, O5—H5B···O4ⁱⁱⁱ and C6—H6A···O5^iv (Table 2). These chains link into chiral layers parallel to the (101) plane via the O5—H5B···O4ⁱⁱⁱ hydrogen bonds. Neighbouring enantiomeric layers, which are mutual images on the plane of (101) are associated via the O5—H5A···O1ⁱⁱ hydrogen bonds. The whole noncentrosymmetric structure is stablized by π–π interactions between neighboring layers, with the relevant centroid···centroid separations between the pyridine and the benzene rings at (x, 1 - y, z + 1/2), 3.813 (4) Å and (x - 1/2, -y + 1/2, z - 1/2), 3.658 (3) Å.

Related literature top

For related literature, see: Etter (1990); Inuzuka & Fujimoto (1986, 1990); Ishikawa et al. (2002); Jin et al. (2000, 2002); Kaminskii et al. (2006, 2007); Kiebacha et al. (2006); Sarma et al. (1997); Thalladi et al. (1999); Xuan et al. (2003).

Experimental top

The title compound was synthesized from a mixture of 2-amino-6-methylpyridine (1 mmol, 0.11 g) and ferulic acid (1 mmol, 0.19 g). The mixture was dissolved in 10 ml water, then heated to 373 K and stirred for half an hour. After the reaction system was cooled to room temperature after five days the colorless crystals were collected.

Structure description top

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The cell unit of (I) with atom labels, showing 40% probability displacement ellipsoids. The thin lines denote the hydrogen bonds.
	Fig. 2. The chiral hydrogen bond chain of (I) along the [101] direction. Hydrogen bonds are shown by thin lines, All H atoms are omitted for clarity. The superscripts, * and #, indicate the symmetry positions of (x + 1/2, - y + 3/2, z + 1/2) and (x - 1/2, - y + 1/2, z - 1/2), respectively.
	Fig. 3. The preparation of thetitle compound.

2-Amino-6-methylpyridinium 3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate monohydrate top

Crystal data top

C₆H₉N₂⁺·C₁₀H₉O₄⁻·H₂O	F(000) = 680
M_r = 320.34	D_x = 1.337 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 30 reflections
a = 11.266 (2) Å	θ = 3.7–12.0°
b = 9.711 (1) Å	µ = 0.10 mm⁻¹
c = 15.024 (2) Å	T = 296 K
β = 104.547 (8)°	Block, colourless
V = 1591.0 (4) Å³	0.40 × 0.40 × 0.36 mm
Z = 4

Data collection top

Siemens P4 diffractometer	1571 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 28.0°, θ_min = 2.8°
ω scans	h = 0→14
Absorption correction: empirical (using intensity measurements) (SHELXTL; Bruker, 1998)	k = 0→12
T_min = 0.955, T_max = 0.960	l = −19→19
2235 measured reflections	3 standard reflections every 97 reflections
1920 independent reflections	intensity decay: 1.4%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
1920 reflections	Δρ_max = 0.16 e Å⁻³
234 parameters	Δρ_min = −0.13 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0225 (15)

Crystal data top

C₆H₉N₂⁺·C₁₀H₉O₄⁻·H₂O	V = 1591.0 (4) Å³
M_r = 320.34	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 11.266 (2) Å	µ = 0.10 mm⁻¹
b = 9.711 (1) Å	T = 296 K
c = 15.024 (2) Å	0.40 × 0.40 × 0.36 mm
β = 104.547 (8)°

Data collection top

Siemens P4 diffractometer	1571 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) (SHELXTL; Bruker, 1998)	R_int = 0.012
T_min = 0.955, T_max = 0.960	3 standard reflections every 97 reflections
2235 measured reflections	intensity decay: 1.4%
1920 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	4 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.16 e Å⁻³
1920 reflections	Δρ_min = −0.13 e Å⁻³
234 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	Occ. (<1)
O1	0.63139 (17)	0.81309 (17)	0.79651 (11)	0.0505 (5)
O2	0.55462 (15)	0.56111 (16)	0.80161 (10)	0.0480 (5)
O3	0.21872 (16)	0.43919 (16)	0.29836 (10)	0.0488 (4)
O4	0.29544 (17)	0.24240 (15)	0.36111 (11)	0.0446 (4)
O5	0.0234 (2)	0.3630 (3)	−0.04758 (14)	0.0691 (6)
N1	0.26566 (16)	0.09244 (19)	0.20202 (13)	0.0365 (4)
N2	0.1546 (2)	0.2764 (2)	0.12847 (16)	0.0472 (5)
C1	0.2028 (2)	0.1526 (2)	0.12329 (15)	0.0377 (5)
C2	0.1912 (2)	0.0791 (3)	0.04057 (16)	0.0472 (6)
H2	0.1486	0.1168	−0.0152	0.057*
C3	0.2429 (3)	−0.0470 (3)	0.04365 (19)	0.0556 (7)
H3	0.2364	−0.0955	−0.0107	0.067*
C4	0.3054 (3)	−0.1052 (3)	0.1264 (2)	0.0579 (7)
H4	0.3401	−0.1922	0.1272	0.069*
C5	0.3159 (2)	−0.0355 (2)	0.20598 (17)	0.0450 (6)
C6	0.3764 (3)	−0.0885 (3)	0.2995 (2)	0.0630 (8)
H6A	0.3721	−0.0198	0.3446	0.076*	0.50
H6B	0.4607	−0.1093	0.3029	0.076*	0.50
H6C	0.3352	−0.1704	0.3114	0.076*	0.50
H6D	0.4065	−0.1799	0.2947	0.076*	0.50
H6E	0.3180	−0.0904	0.3364	0.076*	0.50
H6F	0.4434	−0.0292	0.3279	0.076*	0.50
C7	0.4530 (2)	0.5648 (2)	0.63826 (15)	0.0355 (5)
H7	0.4247	0.4752	0.6404	0.043*
C8	0.5218 (2)	0.6252 (2)	0.71738 (14)	0.0356 (5)
C9	0.56482 (19)	0.7597 (2)	0.71563 (14)	0.0366 (5)
C10	0.5380 (2)	0.8308 (2)	0.63346 (15)	0.0409 (5)
H10	0.5667	0.9202	0.6313	0.049*
C11	0.4682 (2)	0.7693 (2)	0.55374 (15)	0.0386 (5)
H11	0.4502	0.8186	0.4989	0.046*
C12	0.42502 (19)	0.6361 (2)	0.55453 (14)	0.0334 (5)
C13	0.3556 (2)	0.5708 (2)	0.46945 (13)	0.0348 (5)
H13	0.3198	0.6293	0.4211	0.042*
C14	0.3384 (2)	0.4371 (2)	0.45420 (14)	0.0416 (5)
H14	0.3665	0.3790	0.5043	0.050*
C15	0.2784 (2)	0.3701 (2)	0.36480 (14)	0.0357 (5)
C16	0.5134 (2)	0.4233 (2)	0.80484 (16)	0.0434 (5)
H16A	0.4254	0.4214	0.7876	0.052*
H16B	0.5427	0.3880	0.8661	0.052*
H16C	0.5444	0.3676	0.7629	0.052*
H2A	0.121 (2)	0.316 (2)	0.0782 (17)	0.038 (7)*
H1N	0.274 (2)	0.135 (2)	0.2531 (17)	0.036 (6)*
H2B	0.173 (2)	0.318 (3)	0.181 (2)	0.055 (8)*
H1O	0.659 (3)	0.896 (3)	0.7919 (19)	0.058 (8)*
H5A	0.061 (4)	0.348 (5)	−0.087 (2)	0.13 (2)*
H5B	−0.0448 (18)	0.329 (4)	−0.069 (2)	0.091 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0690 (12)	0.0358 (9)	0.0363 (8)	−0.0158 (9)	−0.0058 (8)	−0.0049 (7)
O2	0.0680 (12)	0.0397 (9)	0.0286 (7)	−0.0130 (8)	−0.0022 (7)	0.0024 (7)
O3	0.0656 (11)	0.0393 (9)	0.0310 (8)	0.0093 (9)	−0.0077 (7)	−0.0041 (7)
O4	0.0623 (10)	0.0338 (8)	0.0308 (8)	0.0009 (8)	−0.0011 (7)	−0.0031 (7)
O5	0.0660 (14)	0.0864 (16)	0.0450 (11)	−0.0116 (13)	−0.0045 (11)	0.0133 (10)
N1	0.0411 (10)	0.0338 (10)	0.0331 (10)	−0.0021 (8)	0.0064 (8)	−0.0079 (8)
N2	0.0603 (14)	0.0447 (11)	0.0302 (10)	0.0074 (10)	−0.0007 (10)	−0.0028 (10)
C1	0.0381 (12)	0.0400 (12)	0.0331 (11)	−0.0055 (10)	0.0054 (9)	−0.0052 (10)
C2	0.0497 (14)	0.0563 (15)	0.0344 (12)	−0.0096 (13)	0.0082 (10)	−0.0123 (11)
C3	0.0592 (16)	0.0570 (17)	0.0514 (15)	−0.0077 (13)	0.0152 (13)	−0.0268 (13)
C4	0.0633 (18)	0.0416 (13)	0.0672 (18)	0.0029 (12)	0.0137 (14)	−0.0182 (13)
C5	0.0450 (15)	0.0340 (11)	0.0523 (14)	−0.0024 (10)	0.0054 (12)	−0.0078 (10)
C6	0.0729 (19)	0.0411 (14)	0.0640 (17)	0.0115 (14)	−0.0035 (14)	0.0022 (13)
C7	0.0441 (12)	0.0287 (10)	0.0307 (9)	−0.0034 (9)	0.0038 (9)	−0.0033 (9)
C8	0.0432 (12)	0.0327 (11)	0.0283 (10)	0.0004 (9)	0.0041 (9)	0.0005 (8)
C9	0.0411 (13)	0.0308 (11)	0.0338 (10)	−0.0014 (10)	0.0016 (9)	−0.0053 (9)
C10	0.0530 (14)	0.0256 (11)	0.0394 (12)	−0.0011 (10)	0.0031 (10)	−0.0001 (9)
C11	0.0505 (13)	0.0321 (11)	0.0291 (10)	0.0057 (10)	0.0025 (9)	0.0035 (8)
C12	0.0379 (12)	0.0305 (10)	0.0297 (10)	0.0046 (9)	0.0047 (9)	−0.0031 (8)
C13	0.0419 (12)	0.0344 (11)	0.0238 (9)	0.0045 (9)	0.0004 (8)	0.0012 (8)
C14	0.0559 (14)	0.0391 (13)	0.0248 (10)	−0.0011 (11)	0.0008 (10)	−0.0005 (9)
C15	0.0441 (12)	0.0346 (11)	0.0253 (10)	−0.0012 (10)	0.0028 (9)	−0.0020 (9)
C16	0.0550 (14)	0.0403 (12)	0.0338 (11)	−0.0027 (11)	0.0091 (10)	0.0045 (10)

Geometric parameters (Å, º) top

O1—C9	1.360 (2)	C6—H6B	0.9600
O1—H1O	0.87 (3)	C6—H6C	0.9600
O2—C8	1.375 (3)	C6—H6D	0.9600
O2—C16	1.421 (2)	C6—H6E	0.9600
O3—C15	1.250 (3)	C6—H6F	0.9600
O4—C15	1.258 (3)	C7—C8	1.376 (3)
O5—H5A	0.819 (10)	C7—C12	1.401 (3)
O5—H5B	0.824 (10)	C7—H7	0.9300
N1—C1	1.349 (3)	C8—C9	1.396 (3)
N1—C5	1.361 (3)	C9—C10	1.380 (3)
N1—H1N	0.86 (2)	C10—C11	1.392 (3)
N2—C1	1.330 (3)	C10—H10	0.9300
N2—H2A	0.85 (2)	C11—C12	1.383 (3)
N2—H2B	0.86 (3)	C11—H11	0.9300
C1—C2	1.410 (3)	C12—C13	1.465 (3)
C2—C3	1.352 (4)	C13—C14	1.324 (3)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.386 (4)	C14—C15	1.493 (3)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.353 (4)	C16—H16A	0.9600
C4—H4	0.9300	C16—H16B	0.9600
C5—C6	1.491 (4)	C16—H16C	0.9600
C6—H6A	0.9600

C9—O1—H1O	114.1 (19)	C5—C6—H6F	109.5
C8—O2—C16	116.29 (16)	H6A—C6—H6F	56.3
H5A—O5—H5B	105 (4)	H6B—C6—H6F	56.3
C1—N1—C5	123.7 (2)	H6C—C6—H6F	141.1
C1—N1—H1N	119.1 (16)	H6D—C6—H6F	109.5
C5—N1—H1N	117.2 (16)	H6E—C6—H6F	109.5
C1—N2—H2A	117.2 (16)	C8—C7—C12	121.08 (19)
C1—N2—H2B	118.0 (18)	C8—C7—H7	119.5
H2A—N2—H2B	123 (2)	C12—C7—H7	119.5
N2—C1—N1	118.2 (2)	O2—C8—C7	124.40 (19)
N2—C1—C2	124.1 (2)	O2—C8—C9	115.24 (18)
N1—C1—C2	117.8 (2)	C7—C8—C9	120.35 (19)
C3—C2—C1	119.0 (2)	O1—C9—C10	123.83 (19)
C3—C2—H2	120.5	O1—C9—C8	117.13 (19)
C1—C2—H2	120.5	C10—C9—C8	119.04 (19)
C2—C3—C4	121.2 (2)	C9—C10—C11	120.3 (2)
C2—C3—H3	119.4	C9—C10—H10	119.8
C4—C3—H3	119.4	C11—C10—H10	119.8
C5—C4—C3	120.1 (2)	C12—C11—C10	121.2 (2)
C5—C4—H4	120.0	C12—C11—H11	119.4
C3—C4—H4	120.0	C10—C11—H11	119.4
C4—C5—N1	118.3 (2)	C11—C12—C7	118.00 (19)
C4—C5—C6	125.4 (2)	C11—C12—C13	120.61 (19)
N1—C5—C6	116.3 (2)	C7—C12—C13	121.36 (18)
C5—C6—H6A	109.5	C14—C13—C12	126.75 (18)
C5—C6—H6B	109.5	C14—C13—H13	116.6
H6A—C6—H6B	109.5	C12—C13—H13	116.6
C5—C6—H6C	109.5	C13—C14—C15	126.62 (19)
H6A—C6—H6C	109.5	C13—C14—H14	116.7
H6B—C6—H6C	109.5	C15—C14—H14	116.7
C5—C6—H6D	109.5	O3—C15—O4	123.49 (19)
H6A—C6—H6D	141.1	O3—C15—C14	121.05 (19)
H6B—C6—H6D	56.3	O4—C15—C14	115.43 (19)
H6C—C6—H6D	56.3	O2—C16—H16A	109.5
C5—C6—H6E	109.5	O2—C16—H16B	109.5
H6A—C6—H6E	56.3	H16A—C16—H16B	109.5
H6B—C6—H6E	141.1	O2—C16—H16C	109.5
H6C—C6—H6E	56.3	H16A—C16—H16C	109.5
H6D—C6—H6E	109.5	H16B—C16—H16C	109.5

C5—N1—C1—N2	177.9 (2)	C7—C8—C9—O1	179.5 (2)
C5—N1—C1—C2	−1.3 (3)	O2—C8—C9—C10	178.8 (2)
N2—C1—C2—C3	−179.2 (2)	C7—C8—C9—C10	−0.3 (3)
N1—C1—C2—C3	0.0 (3)	O1—C9—C10—C11	−179.4 (2)
C1—C2—C3—C4	0.8 (4)	C8—C9—C10—C11	0.5 (3)
C2—C3—C4—C5	−0.3 (4)	C9—C10—C11—C12	−0.5 (3)
C3—C4—C5—N1	−1.0 (4)	C10—C11—C12—C7	0.4 (3)
C3—C4—C5—C6	177.5 (3)	C10—C11—C12—C13	−177.7 (2)
C1—N1—C5—C4	1.8 (4)	C8—C7—C12—C11	−0.2 (3)
C1—N1—C5—C6	−176.8 (2)	C8—C7—C12—C13	177.8 (2)
C16—O2—C8—C7	0.1 (3)	C11—C12—C13—C14	159.9 (2)
C16—O2—C8—C9	−179.1 (2)	C7—C12—C13—C14	−18.2 (3)
C12—C7—C8—O2	−178.9 (2)	C12—C13—C14—C15	−173.4 (2)
C12—C7—C8—C9	0.2 (3)	C13—C14—C15—O3	−12.9 (4)
O2—C8—C9—O1	−1.3 (3)	C13—C14—C15—O4	165.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.86 (2)	1.89 (3)	2.746 (2)	175
N2—H2A···O5	0.85 (2)	1.99 (2)	2.815 (3)	166
N2—H2B···O3	0.86 (2)	2.08 (3)	2.934 (4)	173
O1—H1O···O3ⁱ	0.87 (3)	1.73 (3)	2.596 (3)	172
O5—H5A···O1ⁱⁱ	0.82 (1)	2.13 (1)	2.938 (5)	171
O5—H5B···O4ⁱⁱⁱ	0.82 (1)	1.97 (1)	2.785 (2)	171
C6—H6A···O5^iv	0.96	2.54	3.302 (3)	136
C13—H13···O1^v	0.93	2.52	3.332 (2)	147

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, y−1/2, z−1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₁₀H₉O₄⁻·H₂O
M_r	320.34
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	11.266 (2), 9.711 (1), 15.024 (2)
β (°)	104.547 (8)
V (Å³)	1591.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.40 × 0.36

Data collection
Diffractometer	Siemens P4
Absorption correction	Empirical (using intensity measurements) (SHELXTL; Bruker, 1998)
T_min, T_max	0.955, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	2235, 1920, 1571
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.075, 0.98
No. of reflections	1920
No. of parameters	234
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.13

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.86 (2)	1.89 (3)	2.746 (2)	175
N2—H2A···O5	0.85 (2)	1.99 (2)	2.815 (3)	166
N2—H2B···O3	0.86 (2)	2.08 (3)	2.934 (4)	173
O1—H1O···O3ⁱ	0.87 (3)	1.73 (3)	2.596 (3)	172
O5—H5A···O1ⁱⁱ	0.82 (1)	2.13 (1)	2.938 (5)	171
O5—H5B···O4ⁱⁱⁱ	0.82 (1)	1.97 (1)	2.785 (2)	171
C6—H6A···O5^iv	0.96	2.54	3.302 (3)	136
C13—H13···O1^v	0.93	2.52	3.332 (2)	147

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x−1/2, y−1/2, z−1; (iii) x−1/2, −y+1/2, z−1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1/2, −y+3/2, z−1/2.

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