2-Amino-3-(hy­droxy­meth­yl)pyridinium 2-benzoyl­benzoate monohydrate

Odabaşoğlu, H.Y.; Büyükgüngör, O.; Avinç, O.O.; Odabaşoğlu, M.

doi:10.1107/S1600536812005612

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o707-o708

doi:10.1107/S1600536812005612

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2-Amino-3-(hydroxymethyl)pyridinium 2-benzoylbenzoate monohydrate

Hakkı Yasin Odabaşoğlu,^a Orhan Büyükgüngör,^b ^* Osman Ozan Avinç ^a and Mustafa Odabaşoğlu ^c

^aDepartment of Textile Engineering, Faculty of Engineering, Pamukkale University, TR-20070 Kınıklı Denizli, Turkey, ^bDepartment of Physics, Faculty of Arts and Science, Ondokuz Mayıs University, TR-55139 Kurupelit Samsun, Turkey, and ^cChemistry Programme, Denizli Higher Vocational School, Pamukkale University, TR-20159 Denizli, Turkey
^*Correspondence e-mail: orhanb@omu.edu.tr

(Received 11 January 2012; accepted 8 February 2012; online 17 February 2012)

In the title hydrated salt, C₆H₉N₂O⁺·C₁₄H₉O₃⁻·H₂O, the dihedral angle between the benzene rings of the 2-benzoylbenzoate anion is 82.04 (14)°, while the angles between the aromatic ring of the pyridinium cation and each of the benzene rings of the anion are 4.42 (14) and 82.04 (14)°. In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating a three-dimensional network with R₂²(8), R₆⁶(16) and R₄⁴(6) motifs. The crystal packing is further stabilized by two π–π interactions, one between pyridinium rings, and another between the benzene benzoate and pyridinium rings of neighbouring molecules, with centroid-to-centroid distances of 3.559 (2) and 3.606 (2) Å, respectively.

Related literature

For general background, see: Lehn (1990 ); Mrozek & Glowiak (2004 ); Yang et al. (1995 ); Goswami & Ghosh (1997 ); Goswami et al. (1998 ); Lah et al. (2001 ); Hong & Sun (2008 ). For related structures, see: Büyükgüngör & Odabaşoğlu (2002 ); Büyükgüngör et al. (2004 ); Odabaşoğlu & Büyükgüngör (2007 , 2008 ); Odabaşoğlu et al. (2003b ,c ). For the synthesis of the title compound, see: Odabaşoğlu et al. (2003a ). For ring-motif details, see: Bernstein et al. (1995 ); Etter (1990 ).

Experimental

Crystal data

C₆H₉N₂O⁺·C₁₄H₉O₃⁻·H₂O
M_r = 368.38
Monoclinic, C 2/c
a = 15.9259 (11) Å
b = 8.4898 (4) Å
c = 27.6362 (19) Å
β = 93.468 (5)°
V = 3729.8 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.26 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.967, T_max = 0.976
9399 measured reflections
3523 independent reflections
1792 reflections with I > 2σ(I)
R_int = 0.117

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.156
S = 0.95
3503 reflections
254 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.93	2.775 (3)	167
N1—H1⋯O2ⁱ	0.86	2.62	3.303 (3)	137
N2—H2A⋯O2ⁱ	0.86	2.04	2.845 (3)	156
N2—H2B⋯O5ⁱⁱ	0.86	2.11	2.942 (4)	162
O4—H4A⋯O2ⁱⁱⁱ	0.86 (2)	1.92 (2)	2.765 (3)	168 (4)
O5—H5A⋯O4	0.86 (2)	1.96 (2)	2.807 (3)	167 (4)
O5—H5B⋯O1	0.86 (2)	2.28 (4)	2.964 (4)	136 (4)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005612/lr2047sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005612/lr2047Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005612/lr2047Isup3.cml

checkCIF report

Comment top

The cotton fabrics which have been treated with benzophenone derivatives have powerful antibacterial properties against S. aureus and E. coli, and benzoylbenzoic acid derivatives treated cotton fabric demonstrated pesticide degradation ability, under UV irradiation (Hong & Sun, 2008). Furthermore, the copper(II) complexes of 2-aminopyridinium carboxylates have important properties in the applications of pharmaceuticals, fungicides, oxygen transfer, oxidative addition, homogenous hydrogenation, gas occlusion compounds, and solvent extractions processes (Yang et al., 1995; Lah et al., 2001). Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997) and crystal engineering research (Goswami et al., 1998). The design of highly specific solid-state structures is of considerable significance in organic chemistry due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1990). With this in mind, we had aimed the synthesis of (E)-2-(3-(hydroxymethyl)pyridin-2-ylimino)(phenyl) methyl)benzoic acid by reaction of 2-Amino-3-hydroxymethylpyridine and 2-benzoylbenzoic acid. But this compound can not be produced in the reaction conditions (Odabaşoǧlu et al., 2003a), instead the title compound was obtained (Scheme 1, Fig. 1).

The crystal structure of the title compound exhibit four N—H···O, three O—H···O hydrogen bonds and two π–π interactions. The C—H···O hydrogen bonds generate R₆⁶(16) hydrogen bonded motifs (Fig. 2) (Bernstein et al., 1995; Etter, 1990). Pyridinium ions, H₂O molecules and carboxylate ions give edge fused R₄⁴(16) R₂²(8) hydrogen bonded rings by O—H···O and N—H···O hydrogen bonds (Fig. 3).

The dihedral angle between the benzene rings B:(C1–C6) and C:(C9–C14) of the 2-benzoylbenzoate fragment is 82.04 (14)°, while the angles between the aromatic ring A:(C15,C16,N1,C17,C18,C19) of the 2-amino-3-hydroxymethylpiridinium fragment with each of them are 4.42 (14)° and 82.04 (14)° respectively. There are also stacking interactions between the A–A and A–B rings of symmetry-related molecules, with centroid–centroid distance of 3.559 (2) Å and 3.606 (2) Å, respectively (Fig. 4). The bond distance and angles in (I) are expected value and consistent with the literature (Mrozek & Glowiak, 2004; Büyükgüngör & Odabaşoǧlu, 2002; Odabaşoğlu et al., 2003b,c; Büyükgüngör et al., 2004; Odabaşoğlu & Büyükgüngör, 2007, 2008).

Related literature top

For general background, see: Lehn (1990); Mrozek & Glowiak (2004); Yang et al. (1995); Goswami & Ghosh (1997); Goswami et al. (1998); Lah et al. (2001); Hong & Sun (2008). For related structures, see: Büyükgüngör & Odabaşoǧlu (2002); Büyükgüngör et al. (2004); Odabaşoğlu & Büyükgüngör (2007, 2008); Odabaşoğlu et al. (2003b,c). For the synthesis of the title compound, see: Odabaşoǧlu et al. (2003a). For ring-motif details, see: Bernstein et al. (1995); Etter (1990).

Experimental top

The title compound is obtained by reaction of 2-Amino-3-hydroxymethylpyridine and 2-benzoylbenzoic acid under the experimental condition previously described (Odabaşoǧlu et al. 2003a). Suitable crystal of the title compound were obtained by slow evaporation from a solution of the reaction mixture in ethanol.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A partial view of the packing of (I), showing the formation of O—H···O bonded R₆⁶(16) motif [Symmetry code:(i) 1 - x, 1 - y, 1 - z]
	Fig. 3. A partial view of the packing of (I) with hydrogen bonded R₂²(8) and R₄⁴(16) motifs [Symmetry codes:(i) 3/2 - x, 3/2 - y, 1 - z; (ii) x + 1/2, y - 1/2, z].
	Fig. 4. A partial view of the packing of (I), showing the formation of π–π interactions. [Symmetry codes:(i) 1 - x, 3/2 - y, 1 - z; (ii) 1 - x, 1 - y, 1 - z].

2-Amino-3-(hydroxymethyl)pyridinium 2-benzoylbenzoate monohydrate top

Crystal data top

C₆H₉N₂O⁺·C₁₄H₉O₃⁻·H₂O	F(000) = 1552
M_r = 368.38	D_x = 1.312 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8608 reflections
a = 15.9259 (11) Å	θ = 1.5–26.1°
b = 8.4898 (4) Å	µ = 0.10 mm⁻¹
c = 27.6362 (19) Å	T = 296 K
β = 93.468 (5)°	Block, colourless
V = 3729.8 (4) Å³	0.35 × 0.30 × 0.26 mm
Z = 8

Data collection top

Stoe IPDS 2 diffractometer	3523 independent reflections
Radiation source: fine-focus sealed tube	1792 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.117
Detector resolution: 6.67 pixels mm^-1	θ_max = 25.7°, θ_min = 1.5°
ω–scan rotation method	h = −19→15
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −9→10
T_min = 0.967, T_max = 0.976	l = −33→33
9399 measured reflections

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)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.0625P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
3503 reflections	Δρ_max = 0.18 e Å⁻³
254 parameters	Δρ_min = −0.21 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (5)

Crystal data top

C₆H₉N₂O⁺·C₁₄H₉O₃⁻·H₂O	V = 3729.8 (4) Å³
M_r = 368.38	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.9259 (11) Å	µ = 0.10 mm⁻¹
b = 8.4898 (4) Å	T = 296 K
c = 27.6362 (19) Å	0.35 × 0.30 × 0.26 mm
β = 93.468 (5)°

Data collection top

Stoe IPDS 2 diffractometer	3523 independent reflections
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	1792 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.976	R_int = 0.117
9399 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	4 restraints
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.18 e Å⁻³
3503 reflections	Δρ_min = −0.21 e Å⁻³
254 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	0.40651 (19)	0.3876 (3)	0.66050 (9)	0.0562 (7)
C2	0.4022 (2)	0.2387 (4)	0.68081 (10)	0.0692 (9)
H2	0.3510	0.2001	0.6902	0.083*
C3	0.4738 (3)	0.1478 (4)	0.68716 (11)	0.0788 (10)
H3	0.4705	0.0477	0.7006	0.095*
C4	0.5489 (2)	0.2034 (4)	0.67396 (11)	0.0755 (10)
H4	0.5970	0.1420	0.6788	0.091*
C5	0.5540 (2)	0.3510 (4)	0.65331 (10)	0.0653 (8)
H5	0.6058	0.3881	0.6443	0.078*
C6	0.48330 (18)	0.4444 (3)	0.64586 (8)	0.0542 (7)
C7	0.4857 (2)	0.5976 (4)	0.61819 (9)	0.0591 (8)
C8	0.32807 (19)	0.4875 (4)	0.65745 (9)	0.0595 (8)
C9	0.32802 (18)	0.6335 (4)	0.68740 (9)	0.0553 (7)
C10	0.27551 (19)	0.7577 (4)	0.67355 (11)	0.0652 (8)
H10	0.2441	0.7532	0.6441	0.078*
C11	0.2694 (2)	0.8874 (4)	0.70280 (13)	0.0767 (10)
H11	0.2342	0.9705	0.6931	0.092*
C12	0.3152 (2)	0.8940 (5)	0.74628 (13)	0.0819 (10)
H12	0.3106	0.9812	0.7663	0.098*
C13	0.3682 (2)	0.7722 (5)	0.76063 (11)	0.0818 (10)
H13	0.3990	0.7771	0.7903	0.098*
C14	0.3757 (2)	0.6423 (4)	0.73080 (10)	0.0689 (9)
H14	0.4126	0.5613	0.7400	0.083*
O1	0.55266 (16)	0.6753 (3)	0.61989 (8)	0.0810 (7)
O2	0.41975 (14)	0.6353 (2)	0.59401 (7)	0.0673 (6)
O3	0.26539 (15)	0.4449 (3)	0.63399 (8)	0.0821 (7)
C15	0.5523 (2)	0.8106 (3)	0.45397 (9)	0.0591 (8)
C16	0.5503 (2)	0.9647 (4)	0.43366 (9)	0.0580 (7)
C17	0.4025 (2)	0.9701 (5)	0.43705 (11)	0.0734 (9)
H17	0.3523	1.0245	0.4307	0.088*
C18	0.4010 (2)	0.8251 (5)	0.45727 (12)	0.0778 (10)
H18	0.3508	0.7790	0.4653	0.093*
C19	0.4776 (2)	0.7474 (4)	0.46559 (10)	0.0730 (9)
H19	0.4776	0.6480	0.4797	0.088*
C20	0.6347 (2)	0.7288 (4)	0.46227 (11)	0.0695 (9)
H20A	0.6627	0.7266	0.4321	0.083*
H20B	0.6698	0.7890	0.4855	0.083*
N1	0.47595 (17)	1.0371 (3)	0.42587 (8)	0.0639 (7)
H1	0.4748	1.1297	0.4133	0.077*
N2	0.61927 (17)	1.0410 (3)	0.42175 (8)	0.0683 (7)
H2A	0.6152	1.1340	0.4094	0.082*
H2B	0.6678	0.9973	0.4264	0.082*
O4	0.62787 (17)	0.5725 (3)	0.47963 (7)	0.0814 (7)
H4A	0.619 (3)	0.514 (4)	0.4545 (11)	0.122*
O5	0.70194 (16)	0.5481 (4)	0.57409 (9)	0.0921 (8)
H5A	0.673 (3)	0.560 (5)	0.5473 (9)	0.138*
H5B	0.682 (3)	0.614 (5)	0.5941 (12)	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0573 (19)	0.0569 (18)	0.0540 (14)	0.0035 (15)	−0.0003 (12)	−0.0019 (13)
C2	0.071 (2)	0.064 (2)	0.0729 (18)	−0.0044 (19)	0.0066 (16)	0.0111 (15)
C3	0.099 (3)	0.065 (2)	0.0708 (19)	0.008 (2)	−0.0016 (18)	0.0184 (16)
C4	0.077 (3)	0.077 (2)	0.0709 (18)	0.019 (2)	−0.0068 (17)	0.0096 (17)
C5	0.060 (2)	0.073 (2)	0.0624 (16)	0.0054 (18)	−0.0011 (14)	0.0028 (15)
C6	0.0581 (19)	0.0530 (17)	0.0508 (13)	0.0011 (16)	−0.0013 (12)	0.0000 (12)
C7	0.060 (2)	0.065 (2)	0.0524 (14)	−0.0022 (18)	0.0044 (14)	−0.0041 (13)
C8	0.0519 (19)	0.069 (2)	0.0577 (15)	−0.0028 (16)	0.0015 (14)	0.0013 (14)
C9	0.0474 (17)	0.0605 (18)	0.0587 (15)	−0.0024 (15)	0.0077 (12)	−0.0002 (13)
C10	0.0555 (19)	0.070 (2)	0.0700 (17)	0.0042 (18)	0.0025 (14)	−0.0030 (16)
C11	0.064 (2)	0.065 (2)	0.102 (3)	0.0034 (18)	0.0106 (18)	−0.0143 (18)
C12	0.077 (3)	0.080 (2)	0.090 (2)	−0.004 (2)	0.0145 (19)	−0.0252 (19)
C13	0.086 (3)	0.098 (3)	0.0616 (17)	−0.011 (2)	0.0015 (17)	−0.0127 (19)
C14	0.072 (2)	0.072 (2)	0.0623 (17)	0.0015 (18)	−0.0006 (15)	0.0027 (16)
O1	0.0715 (16)	0.0775 (16)	0.0936 (15)	−0.0159 (14)	0.0010 (12)	0.0102 (12)
O2	0.0696 (15)	0.0594 (13)	0.0715 (11)	0.0024 (11)	−0.0063 (11)	0.0074 (10)
O3	0.0630 (15)	0.0853 (16)	0.0960 (15)	0.0009 (14)	−0.0107 (12)	−0.0177 (13)
C15	0.074 (2)	0.0551 (17)	0.0477 (13)	−0.0081 (17)	−0.0011 (13)	0.0004 (13)
C16	0.065 (2)	0.0583 (19)	0.0498 (14)	−0.0058 (18)	0.0005 (13)	−0.0007 (13)
C17	0.064 (2)	0.087 (3)	0.0703 (18)	−0.003 (2)	0.0061 (15)	−0.0099 (18)
C18	0.073 (3)	0.082 (3)	0.0789 (19)	−0.019 (2)	0.0095 (17)	−0.0024 (19)
C19	0.088 (3)	0.069 (2)	0.0620 (17)	−0.013 (2)	0.0050 (16)	0.0052 (15)
C20	0.088 (2)	0.0548 (19)	0.0637 (16)	−0.0058 (18)	−0.0081 (16)	0.0051 (14)
N1	0.0685 (18)	0.0597 (16)	0.0633 (13)	−0.0001 (15)	0.0019 (12)	0.0000 (12)
N2	0.0722 (18)	0.0584 (16)	0.0741 (15)	−0.0010 (15)	0.0036 (13)	0.0116 (13)
O4	0.118 (2)	0.0554 (13)	0.0679 (12)	−0.0034 (14)	−0.0144 (13)	0.0085 (10)
O5	0.0718 (17)	0.113 (2)	0.0909 (16)	0.0031 (16)	0.0009 (13)	0.0184 (15)

Geometric parameters (Å, º) top

C1—C6	1.397 (4)	C13—C14	1.386 (5)
C1—C2	1.386 (4)	C13—H13	0.9300
C1—C8	1.508 (4)	C14—H14	0.9300
C2—C3	1.379 (5)	C15—C19	1.361 (4)
C2—H2	0.9300	C15—C16	1.423 (4)
C3—C4	1.356 (5)	C15—C20	1.491 (5)
C3—H3	0.9300	C16—N2	1.333 (4)
C4—C5	1.382 (5)	C16—N1	1.340 (4)
C4—H4	0.9300	C17—N1	1.353 (4)
C5—C6	1.383 (4)	C17—C18	1.353 (5)
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.511 (4)	C18—C19	1.393 (5)
C7—O1	1.252 (4)	C18—H18	0.9300
C7—O2	1.252 (3)	C19—H19	0.9300
C8—O3	1.212 (3)	C20—O4	1.417 (4)
C8—C9	1.490 (4)	C20—H20A	0.9700
C9—C14	1.382 (4)	C20—H20B	0.9700
C9—C10	1.385 (4)	N1—H1	0.8600
C10—C11	1.373 (4)	N2—H2A	0.8600
C10—H10	0.9300	N2—H2B	0.8600
C11—C12	1.369 (5)	O4—H4A	0.859 (19)
C11—H11	0.9300	O5—H5A	0.858 (18)
C12—C13	1.378 (5)	O5—H5B	0.858 (19)
C12—H12	0.9300

C6—C1—C2	119.8 (3)	C12—C13—C14	119.9 (3)
C6—C1—C8	121.8 (3)	C12—C13—H13	120.0
C2—C1—C8	118.3 (3)	C14—C13—H13	120.0
C3—C2—C1	120.1 (3)	C9—C14—C13	119.8 (3)
C3—C2—H2	120.0	C9—C14—H14	120.1
C1—C2—H2	120.0	C13—C14—H14	120.1
C4—C3—C2	120.4 (3)	C19—C15—C16	117.2 (3)
C4—C3—H3	119.8	C19—C15—C20	123.7 (3)
C2—C3—H3	119.8	C16—C15—C20	119.1 (3)
C3—C4—C5	120.1 (3)	N2—C16—N1	118.1 (3)
C3—C4—H4	119.9	N2—C16—C15	123.1 (3)
C5—C4—H4	119.9	N1—C16—C15	118.8 (3)
C4—C5—C6	120.9 (3)	N1—C17—C18	120.9 (3)
C4—C5—H5	119.6	N1—C17—H17	119.5
C6—C5—H5	119.6	C18—C17—H17	119.5
C1—C6—C5	118.6 (3)	C17—C18—C19	117.5 (4)
C1—C6—C7	119.6 (3)	C17—C18—H18	121.2
C5—C6—C7	121.6 (3)	C19—C18—H18	121.2
O1—C7—O2	124.8 (3)	C15—C19—C18	122.9 (3)
O1—C7—C6	118.8 (3)	C15—C19—H19	118.5
O2—C7—C6	116.3 (3)	C18—C19—H19	118.5
O3—C8—C9	121.2 (3)	O4—C20—C15	113.8 (3)
O3—C8—C1	121.0 (3)	O4—C20—H20A	108.8
C9—C8—C1	117.7 (2)	C15—C20—H20A	108.8
C14—C9—C10	119.3 (3)	O4—C20—H20B	108.8
C14—C9—C8	120.5 (3)	C15—C20—H20B	108.8
C10—C9—C8	120.0 (3)	H20A—C20—H20B	107.7
C11—C10—C9	120.7 (3)	C16—N1—C17	122.6 (3)
C11—C10—H10	119.6	C16—N1—H1	118.7
C9—C10—H10	119.6	C17—N1—H1	118.7
C12—C11—C10	119.7 (3)	C16—N2—H2A	120.0
C12—C11—H11	120.1	C16—N2—H2B	120.0
C10—C11—H11	120.1	H2A—N2—H2B	120.0
C11—C12—C13	120.5 (3)	C20—O4—H4A	106 (3)
C11—C12—H12	119.8	H5A—O5—H5B	106 (3)
C13—C12—H12	119.8

C6—C1—C2—C3	0.9 (4)	C1—C8—C9—C10	155.1 (3)
C8—C1—C2—C3	−175.8 (3)	C14—C9—C10—C11	−1.1 (5)
C1—C2—C3—C4	0.5 (5)	C8—C9—C10—C11	174.4 (3)
C2—C3—C4—C5	−1.0 (5)	C9—C10—C11—C12	−0.4 (5)
C3—C4—C5—C6	0.1 (5)	C10—C11—C12—C13	0.8 (5)
C2—C1—C6—C5	−1.7 (4)	C11—C12—C13—C14	0.3 (5)
C8—C1—C6—C5	174.8 (2)	C10—C9—C14—C13	2.2 (5)
C2—C1—C6—C7	172.4 (3)	C8—C9—C14—C13	−173.3 (3)
C8—C1—C6—C7	−11.0 (4)	C12—C13—C14—C9	−1.9 (5)
C4—C5—C6—C1	1.2 (4)	C19—C15—C16—N2	178.5 (3)
C4—C5—C6—C7	−172.8 (3)	C20—C15—C16—N2	−0.4 (4)
C1—C6—C7—O1	155.1 (3)	C19—C15—C16—N1	−1.8 (4)
C5—C6—C7—O1	−30.9 (4)	C20—C15—C16—N1	179.4 (2)
C1—C6—C7—O2	−26.5 (4)	N1—C17—C18—C19	−0.7 (5)
C5—C6—C7—O2	147.4 (3)	C16—C15—C19—C18	1.7 (4)
C6—C1—C8—O3	121.8 (3)	C20—C15—C19—C18	−179.6 (3)
C2—C1—C8—O3	−61.6 (4)	C17—C18—C19—C15	−0.5 (5)
C6—C1—C8—C9	−63.1 (3)	C19—C15—C20—O4	5.2 (4)
C2—C1—C8—C9	113.5 (3)	C16—C15—C20—O4	−176.1 (2)
O3—C8—C9—C14	145.7 (3)	N2—C16—N1—C17	−179.5 (2)
C1—C8—C9—C14	−29.5 (4)	C15—C16—N1—C17	0.8 (4)
O3—C8—C9—C10	−29.8 (4)	C18—C17—N1—C16	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.93	2.775 (3)	167
N1—H1···O2ⁱ	0.86	2.62	3.303 (3)	137
N2—H2A···O2ⁱ	0.86	2.04	2.845 (3)	156
N2—H2B···O5ⁱⁱ	0.86	2.11	2.942 (4)	162
O4—H4A···O2ⁱⁱⁱ	0.86 (2)	1.92 (2)	2.765 (3)	168 (4)
O5—H5A···O4	0.86 (2)	1.96 (2)	2.807 (3)	167 (4)
O5—H5B···O1	0.86 (2)	2.28 (4)	2.964 (4)	136 (4)

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂O⁺·C₁₄H₉O₃⁻·H₂O
M_r	368.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	15.9259 (11), 8.4898 (4), 27.6362 (19)
β (°)	93.468 (5)
V (Å³)	3729.8 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.30 × 0.26

Data collection
Diffractometer	Stoe IPDS 2 diffractometer
Absorption correction	Integration (X-RED; Stoe & Cie, 2002)
T_min, T_max	0.967, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	9399, 3523, 1792
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.156, 0.95
No. of reflections	3503
No. of parameters	254
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)	0.18, −0.21

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.93	2.775 (3)	167.3
N1—H1···O2ⁱ	0.86	2.62	3.303 (3)	136.8
N2—H2A···O2ⁱ	0.86	2.04	2.845 (3)	156.1
N2—H2B···O5ⁱⁱ	0.86	2.11	2.942 (4)	162.3
O4—H4A···O2ⁱⁱⁱ	0.859 (19)	1.92 (2)	2.765 (3)	168 (4)
O5—H5A···O4	0.858 (18)	1.963 (19)	2.807 (3)	167 (4)
O5—H5B···O1	0.858 (19)	2.28 (4)	2.964 (4)	136 (4)

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

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund).

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