4-Meth­oxy­benzamidinium 2,6-dimeth­oxy­benzoate

Portalone, G.

doi:10.1107/S160053681105519X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o268-o269

doi:10.1107/S160053681105519X

Open

access

4-Methoxybenzamidinium 2,6-dimethoxybenzoate

Gustavo Portalone ^a ^*

^aChemistry Department, "Sapienza" University of Rome, P.le A. Moro, 5, I-00185 Rome, Italy
^*Correspondence e-mail: g.portalone@caspur.it

(Received 16 December 2011; accepted 22 December 2011; online 7 January 2012)

The title compound, C₈H₁₁N₂O⁺·C₉H₉O₄⁻, was synthesized by the reaction of 4-methoxybenzamidine (4-amidinoanisole) and 2,6-dimethoxybenzoic acid. The structure consists of non-planar pairs of hydrogen-bonded 4-methoxybenzamidinium cations and 2,6-dimethoxybenzoate anions. In the cation, the amidinium group is tilted by 27.94 (10)° with respect to the benzene ring. In the anion, the sterically bulky ortho-methoxy substituents force the carboxyate group to be twisted away from the plane of the benzene ring by 73.24 (6)°. The ions are further associated in the crystal into chains along the b-axis direction by intermolecular N—H⋯O hydrogen bonds.

Related literature

For the biological and pharmacological relevance of benzamidine, see: Marquart et al. (1983 ); Sprang et al. (1987 ); Bode et al. (1990 ); Powers & Harper (1999 ); Grzesiak et al. (2000 ). For the structure of benzamidine, see: Barker et al. (1996 ). For supramolecular association in proton-transfer adducts containing benzamidinium cations, see; Papoutsakis et al. (1999 ); Portalone (2008 , 2010 ). For the structure of benzdiamidine, see: Jokić et al. (2001). For the orthorhombic and tetragonal polymorphs of 2,6-dimethoxybenzoic acid, see: Swaminathan et al. (1976 ); Bryan & White (1982 ); Portalone (2009 , 2011 ). For the analysis of benzene ring deformations induced by substitution, see: Schultz et al. (1993 ); Portalone et al. (1998 ); For computation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990 ); Bernstein et al. (1995 ); Motherwell et al. (1999 ).

Experimental

Crystal data

C₈H₁₁N₂O⁺·C₉H₉O₄⁻
M_r = 332.35
Monoclinic, P 2₁ /c
a = 12.6594 (3) Å
b = 9.6754 (2) Å
c = 13.7923 (4) Å
β = 99.241 (2)°
V = 1667.42 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.30 × 0.30 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.971, T_max = 0.976
76316 measured reflections
4217 independent reflections
3914 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.131
S = 1.17
4217 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.93 (2)	1.84 (2)	2.7576 (18)	169 (2)
N1—H1B⋯O2ⁱ	0.88 (2)	1.91 (2)	2.7166 (18)	152 (2)
N2—H2B⋯O1ⁱⁱ	0.86 (3)	2.31 (2)	2.868 (2)	123 (2)
N2—H2A⋯O2	0.91 (3)	2.08 (3)	2.976 (2)	170 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: WinGX (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681105519X/rz2691sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105519X/rz2691Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681105519X/rz2691Isup3.cml

checkCIF report

Comment top

This Laboratory is currently engaged in the systematic structural analysis of molecular salts of benzamidine (Portalone, 2008, 2010). Benzamidine is a strong Lewis base and its cation can be easily anchored onto numerous inorganic and organic anions and polyanions, largely because of the presence of four potential donor sites for hydrogen-bonding. Consequently, benzamidinium ions appear to be very promising building blocks in supramolecular chemistry as multiple hydrogen bonding donor. Benzamidine has biological and pharmacological relevance (Powers & Harper, 1999; Grzesiak et al., 2000). Its cation has also been included in a number of protein structures (Marquart et al., 1983; Sprang et al., 1987; Bode et al., 1990).

The asymmetric unit of the title compound comprises a non-planar R²₂(8) hydrogen-bonded pair formed by one 4-methoxybenzamidinium cation and one 2,6-dimethoxybenzoate anion (Fig. 1). In the anion, the o-methoxy substituents force the carboxy group to be twisted away from the plane of the phenyl ring by 73.24 (6)°. The C—O distances of the carboxylate group range from 1.2440 (18) to 1.2509 (18) Å, indicating the delocalization of the negative charge. The pattern of bond lengths and bond angles of the phenyl ring is consistent with that reported in the structure determination of the two polymorphs of 2,6-dimethoxybenzoic acid (Swaminathan et al., 1976; Bryan & White, 1982; Portalone, 2009, 2011), and a comparison of the present results with those obtained for similar benzene derivatives in the gas phase (Schultz et al., 1993; Portalone et al., 1998) shows no appreciable effects of the crystal environment on the ring deformation induced by substituents. In the cation, the amidinium group forms a dihedral angle of 27.94 (10)° with the phenyl ring, which is close to the values observed in neutral benzamidine (22.8°, Barker et al., 1996) as well as in protonated benzamidinium (20.7°, Papoutsakis et al., 1999; 28.5 and 31.9°, Portalone, 2008, 2010) and benzdiamidine (24.5°, Jokić et al., 2001). The lack of planarity in all these systems is obviously caused by steric hindrances between the H atoms of the aromatic ring and the amidine moiety. The pattern of bond lengths and bond angles of the benzamidinium cation agrees with that reported in previous structural investigations (Papoutsakis et al., 1999; Portalone, 2008, 2010). In particular the amidinium group, true to one's expectations, features similar C-N bonds [1.299 (2) and 1.316 (2) Å], evidencing the delocalization of the π electrons and double-bond character.

Analysis of the crystal packing (Fig. 2) shows that the pairs are associated in the crystal by extensive hydrogen bonding. Those pairs of cations and anions are joined by intermolecular R⁴₄(8) N—H···O interactions (Etter et al., 1990; Bernstein et al., 1995; Motherwell et al., 1999) (Table 1) leading to a chain structure running along the b direction.

Related literature top

For the biological and pharmacological relevance of benzamidine, see: Marquart et al. (1983); Sprang et al. (1987); Bode et al. (1990); Powers & Harper (1999); Grzesiak et al. (2000). For the structure of benzamidine, see: Barker et al. (1996). For supramolecular association in proton-transfer adducts containing benzamidinium cations, see; Papoutsakis et al. (1999); Portalone (2008, 2010). For the structure of benzdiamidine, see: Jokić et al. (2001). For the orthorhombic and tetragonal polymorphs of 2,6-dimethoxybenzoic acid, see: Swaminathan et al. (1976); Bryan & White (1982); Portalone (2009, 2011). For the analysis of benzene ring deformations induced by substitution, see: Schultz et al. (1993); Portalone et al. (1998); For computation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990); Bernstein et al. (1995); Motherwell et al. (1999).

Experimental top

The title compound was formed during cocrystallization in a 1:1 molar ratio of 2,6-dimethoxybenzoic acid (1 mmol, Aldrich at 98% purity) and 4-methoxybenzamidine (1 mmol, Fluka at 96% purity). The two components were dissolved in water (10 ml) and gently heated under reflux for 3 h. After cooling the solution to an ambient temperature, colourless crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of the solvent after two weeks.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing displacements ellipsoids drawn the 50% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Crystal packing diagram for the title compound. Displacements ellipsoids are at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, H atoms not involved in hydrogen bonding (dashed lines) have been omitted.

[amino(4-methoxyphenyl)methylidene]azanium 2,6-dimethoxybenzoate top

Crystal data top

C₈H₁₁N₂O⁺·C₉H₉O₄⁻	F(000) = 704
M_r = 332.35	D_x = 1.324 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 41031 reflections
a = 12.6594 (3) Å	θ = 2.9–34.8°
b = 9.6754 (2) Å	µ = 0.10 mm⁻¹
c = 13.7923 (4) Å	T = 298 K
β = 99.241 (2)°	Tablets, colourless
V = 1667.42 (7) Å³	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	4217 independent reflections
Radiation source: Enhance (Mo) X-ray source	3914 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 16.0696 pixels mm^-1	θ_max = 28.5°, θ_min = 2.9°
ω and ϕ scans	h = −16→16
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −12→12
T_min = 0.971, T_max = 0.976	l = −18→18
76316 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0405P)² + 0.878P] where P = (F_o² + 2F_c²)/3
4217 reflections	(Δ/σ)_max < 0.001
239 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₈H₁₁N₂O⁺·C₉H₉O₄⁻	V = 1667.42 (7) Å³
M_r = 332.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6594 (3) Å	µ = 0.10 mm⁻¹
b = 9.6754 (2) Å	T = 298 K
c = 13.7923 (4) Å	0.30 × 0.30 × 0.25 mm
β = 99.241 (2)°

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	4217 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	3914 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.976	R_int = 0.026
76316 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.32 e Å⁻³
4217 reflections	Δρ_min = −0.18 e Å⁻³
239 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O5	0.10799 (10)	−0.11594 (17)	−0.24016 (10)	0.0540 (4)
N1	0.44446 (13)	−0.09706 (15)	0.15597 (11)	0.0413 (4)
H1A	0.4973 (17)	−0.110 (2)	0.2099 (16)	0.049 (6)*
H1B	0.4294 (17)	−0.011 (2)	0.1385 (15)	0.045 (5)*
N2	0.39964 (14)	−0.32294 (16)	0.15666 (14)	0.0467 (4)
H2A	0.442 (2)	−0.329 (3)	0.2161 (19)	0.063 (7)*
H2B	0.3761 (19)	−0.396 (3)	0.1250 (18)	0.059 (7)*
C1	0.31657 (12)	−0.17948 (16)	0.02049 (11)	0.0303 (3)
C2	0.33754 (13)	−0.07531 (19)	−0.04288 (12)	0.0376 (4)
H2	0.4006	−0.0181	−0.0250	0.045*
C3	0.27065 (13)	−0.0509 (2)	−0.13109 (13)	0.0408 (4)
H3	0.2871	0.0216	−0.1749	0.049*
C4	0.17991 (13)	−0.13163 (19)	−0.15559 (12)	0.0375 (4)
C5	0.15748 (13)	−0.2361 (2)	−0.09328 (14)	0.0426 (4)
H5	0.0939	−0.2924	−0.1109	0.051*
C6	0.22544 (13)	−0.26050 (18)	−0.00599 (13)	0.0388 (4)
H6	0.2096	−0.3344	0.0370	0.047*
C7	0.38977 (12)	−0.20070 (15)	0.11435 (12)	0.0316 (3)
C17	0.12111 (18)	0.0003 (3)	−0.30073 (15)	0.0591 (6)
H17A	0.1146 (14)	0.0864 (14)	−0.2636 (7)	0.089*
H17B	0.0653 (12)	−0.0014 (10)	−0.3597 (11)	0.089*
H17C	0.1925 (12)	−0.0034 (10)	−0.3209 (11)	0.089*
O1	0.61718 (10)	−0.11290 (12)	0.30539 (9)	0.0400 (3)
O2	0.55414 (10)	−0.31629 (12)	0.34359 (10)	0.0421 (3)
O3	0.63894 (11)	−0.06691 (15)	0.52149 (10)	0.0517 (4)
O4	0.78817 (10)	−0.40567 (14)	0.34411 (9)	0.0447 (3)
C8	0.71797 (11)	−0.23514 (15)	0.43547 (11)	0.0276 (3)
C9	0.72422 (14)	−0.15283 (17)	0.51889 (12)	0.0366 (4)
C10	0.81319 (17)	−0.1596 (2)	0.59275 (14)	0.0523 (5)
H10	0.8165	−0.1042	0.6518	0.063*
C11	0.89636 (15)	−0.2462 (2)	0.58046 (15)	0.0524 (5)
H11	0.9593	−0.2491	0.6308	0.063*
C12	0.89261 (13)	−0.3286 (2)	0.49875 (13)	0.0425 (4)
H12	0.9522	−0.3885	0.4914	0.051*
C13	0.80189 (12)	−0.32480 (16)	0.42671 (11)	0.0315 (3)
C14	0.62180 (11)	−0.22199 (15)	0.35457 (10)	0.0270 (3)
C15	0.62678 (17)	−0.0059 (2)	0.61327 (15)	0.0523 (5)
H15A	0.6294 (13)	−0.0783 (10)	0.6634 (8)	0.078*
H15B	0.5577 (11)	0.0421 (16)	0.6066 (3)	0.078*
H15C	0.6849 (11)	0.0606 (15)	0.6329 (7)	0.078*
C16	0.86484 (16)	−0.5108 (2)	0.33788 (14)	0.0477 (5)
H16A	0.9338 (10)	−0.4683 (6)	0.3302 (11)	0.071*
H16B	0.8399 (7)	−0.5704 (12)	0.2808 (10)	0.071*
H16C	0.8742 (9)	−0.5669 (13)	0.3984 (9)	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.0399 (7)	0.0729 (10)	0.0426 (7)	−0.0057 (7)	−0.0136 (6)	−0.0001 (7)
N1	0.0484 (8)	0.0244 (7)	0.0428 (8)	0.0029 (6)	−0.0181 (7)	0.0010 (6)
N2	0.0499 (9)	0.0259 (7)	0.0573 (10)	0.0001 (6)	−0.0121 (8)	0.0043 (7)
C1	0.0278 (7)	0.0275 (7)	0.0339 (7)	0.0028 (6)	−0.0002 (6)	−0.0054 (6)
C2	0.0279 (7)	0.0432 (9)	0.0391 (9)	−0.0068 (7)	−0.0025 (6)	0.0002 (7)
C3	0.0344 (8)	0.0496 (10)	0.0363 (8)	−0.0056 (7)	−0.0002 (6)	0.0046 (7)
C4	0.0280 (7)	0.0481 (10)	0.0340 (8)	0.0026 (7)	−0.0022 (6)	−0.0077 (7)
C5	0.0310 (8)	0.0456 (10)	0.0478 (10)	−0.0105 (7)	−0.0042 (7)	−0.0070 (8)
C6	0.0371 (8)	0.0335 (8)	0.0440 (9)	−0.0063 (7)	0.0005 (7)	−0.0015 (7)
C7	0.0307 (7)	0.0247 (7)	0.0372 (8)	0.0049 (6)	−0.0013 (6)	−0.0019 (6)
C17	0.0533 (12)	0.0791 (16)	0.0397 (10)	0.0039 (11)	−0.0081 (8)	0.0063 (10)
O1	0.0410 (6)	0.0318 (6)	0.0416 (6)	−0.0013 (5)	−0.0104 (5)	0.0114 (5)
O2	0.0363 (6)	0.0267 (6)	0.0568 (8)	−0.0032 (5)	−0.0126 (5)	0.0046 (5)
O3	0.0525 (8)	0.0551 (8)	0.0425 (7)	0.0201 (6)	−0.0072 (6)	−0.0171 (6)
O4	0.0446 (7)	0.0508 (7)	0.0354 (6)	0.0217 (6)	−0.0034 (5)	−0.0049 (5)
C8	0.0273 (7)	0.0251 (7)	0.0279 (7)	−0.0004 (5)	−0.0027 (5)	0.0048 (5)
C9	0.0378 (8)	0.0331 (8)	0.0356 (8)	0.0037 (6)	−0.0043 (6)	−0.0027 (6)
C10	0.0547 (11)	0.0540 (12)	0.0405 (10)	0.0065 (9)	−0.0154 (8)	−0.0128 (9)
C11	0.0418 (10)	0.0579 (12)	0.0486 (11)	0.0046 (9)	−0.0204 (8)	−0.0008 (9)
C12	0.0302 (8)	0.0475 (10)	0.0459 (10)	0.0094 (7)	−0.0052 (7)	0.0060 (8)
C13	0.0310 (7)	0.0326 (8)	0.0295 (7)	0.0035 (6)	−0.0001 (6)	0.0054 (6)
C14	0.0272 (7)	0.0237 (7)	0.0281 (7)	0.0064 (5)	−0.0018 (5)	−0.0015 (5)
C15	0.0532 (11)	0.0604 (12)	0.0452 (10)	0.0034 (9)	0.0133 (9)	−0.0112 (9)
C16	0.0494 (10)	0.0501 (11)	0.0445 (10)	0.0213 (9)	0.0103 (8)	0.0032 (8)

Geometric parameters (Å, º) top

O5—C4	1.3680 (19)	O1—C14	1.2509 (18)
O5—C17	1.427 (3)	O2—C14	1.2440 (18)
N1—C7	1.299 (2)	O3—C9	1.368 (2)
N1—H1A	0.93 (2)	O3—C15	1.427 (2)
N1—H1B	0.88 (2)	O4—C13	1.370 (2)
N2—C7	1.316 (2)	O4—C16	1.418 (2)
N2—H2A	0.91 (3)	C8—C9	1.391 (2)
N2—H2B	0.86 (3)	C8—C13	1.392 (2)
C1—C2	1.387 (2)	C8—C14	1.5189 (18)
C1—C6	1.394 (2)	C9—C10	1.394 (2)
C1—C7	1.480 (2)	C10—C11	1.377 (3)
C2—C3	1.386 (2)	C10—H10	0.9700
C2—H2	0.9700	C11—C12	1.375 (3)
C3—C4	1.386 (2)	C11—H11	0.9700
C3—H3	0.9700	C12—C13	1.393 (2)
C4—C5	1.385 (3)	C12—H12	0.9700
C5—C6	1.383 (2)	C15—H15A	0.9817
C5—H5	0.9700	C15—H15B	0.9817
C6—H6	0.9700	C15—H15C	0.9817
C17—H17A	0.9877	C16—H16A	0.9865
C17—H17B	0.9877	C16—H16B	0.9865
C17—H17C	0.9877	C16—H16C	0.9865

C4—O5—C17	117.56 (15)	C13—O4—C16	117.61 (13)
C7—N1—H1A	120.8 (13)	C9—C8—C13	119.07 (13)
C7—N1—H1B	122.1 (14)	C9—C8—C14	119.47 (13)
H1A—N1—H1B	116.8 (19)	C13—C8—C14	121.43 (13)
C7—N2—H2A	117.3 (16)	O3—C9—C8	115.43 (13)
C7—N2—H2B	120.8 (16)	O3—C9—C10	123.91 (16)
H2A—N2—H2B	121 (2)	C8—C9—C10	120.65 (16)
C2—C1—C6	118.52 (14)	C11—C10—C9	118.85 (17)
C2—C1—C7	119.69 (14)	C11—C10—H10	120.6
C6—C1—C7	121.78 (15)	C9—C10—H10	120.6
C3—C2—C1	121.67 (15)	C12—C11—C10	121.83 (16)
C3—C2—H2	119.2	C12—C11—H11	119.1
C1—C2—H2	119.2	C10—C11—H11	119.1
C4—C3—C2	118.91 (16)	C11—C12—C13	119.02 (16)
C4—C3—H3	120.5	C11—C12—H12	120.5
C2—C3—H3	120.5	C13—C12—H12	120.5
O5—C4—C5	115.80 (15)	O4—C13—C8	115.57 (13)
O5—C4—C3	123.89 (17)	O4—C13—C12	123.92 (15)
C5—C4—C3	120.31 (15)	C8—C13—C12	120.52 (15)
C6—C5—C4	120.24 (15)	O2—C14—O1	125.56 (13)
C6—C5—H5	119.9	O2—C14—C8	118.88 (13)
C4—C5—H5	119.9	O1—C14—C8	115.54 (13)
C5—C6—C1	120.34 (16)	O3—C15—H15A	109.5
C5—C6—H6	119.8	O3—C15—H15B	109.5
C1—C6—H6	119.8	H15A—C15—H15B	109.5
N1—C7—N2	119.47 (15)	O3—C15—H15C	109.5
N1—C7—C1	119.60 (14)	H15A—C15—H15C	109.5
N2—C7—C1	120.93 (15)	H15B—C15—H15C	109.5
O5—C17—H17A	109.5	O4—C16—H16A	109.5
O5—C17—H17B	109.5	O4—C16—H16B	109.5
H17A—C17—H17B	109.5	H16A—C16—H16B	109.5
O5—C17—H17C	109.5	O4—C16—H16C	109.5
H17A—C17—H17C	109.5	H16A—C16—H16C	109.5
H17B—C17—H17C	109.5	H16B—C16—H16C	109.5
C9—O3—C15	118.21 (14)

C6—C1—C2—C3	−0.2 (3)	C14—C8—C9—O3	1.5 (2)
C7—C1—C2—C3	−179.38 (16)	C13—C8—C9—C10	0.1 (3)
C1—C2—C3—C4	0.9 (3)	C14—C8—C9—C10	−177.89 (17)
C17—O5—C4—C5	172.81 (18)	O3—C9—C10—C11	−177.5 (2)
C17—O5—C4—C3	−7.5 (3)	C8—C9—C10—C11	1.9 (3)
C2—C3—C4—O5	179.46 (17)	C9—C10—C11—C12	−1.8 (3)
C2—C3—C4—C5	−0.8 (3)	C10—C11—C12—C13	−0.3 (3)
O5—C4—C5—C6	179.86 (17)	C16—O4—C13—C8	−172.11 (15)
C3—C4—C5—C6	0.1 (3)	C16—O4—C13—C12	8.1 (3)
C4—C5—C6—C1	0.6 (3)	C9—C8—C13—O4	177.88 (15)
C2—C1—C6—C5	−0.5 (3)	C14—C8—C13—O4	−4.2 (2)
C7—C1—C6—C5	178.64 (16)	C9—C8—C13—C12	−2.3 (2)
C2—C1—C7—N1	27.6 (2)	C14—C8—C13—C12	175.68 (15)
C6—C1—C7—N1	−151.54 (17)	C11—C12—C13—O4	−177.78 (17)
C2—C1—C7—N2	−152.93 (18)	C11—C12—C13—C8	2.4 (3)
C6—C1—C7—N2	27.9 (2)	C9—C8—C14—O2	−107.53 (17)
C15—O3—C9—C8	164.66 (17)	C13—C8—C14—O2	74.5 (2)
C15—O3—C9—C10	−15.9 (3)	C9—C8—C14—O1	71.0 (2)
C13—C8—C9—O3	179.53 (15)	C13—C8—C14—O1	−106.91 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.93 (2)	1.84 (2)	2.7576 (18)	169 (2)
N1—H1B···O2ⁱ	0.88 (2)	1.91 (2)	2.7166 (18)	152 (2)
N2—H2B···O1ⁱⁱ	0.86 (3)	2.31 (2)	2.868 (2)	123 (2)
N2—H2A···O2	0.91 (3)	2.08 (3)	2.976 (2)	170 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₂O⁺·C₉H₉O₄⁻
M_r	332.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.6594 (3), 9.6754 (2), 13.7923 (4)
β (°)	99.241 (2)
V (Å³)	1667.42 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.971, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	76316, 4217, 3914
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.131, 1.17
No. of reflections	4217
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.93 (2)	1.84 (2)	2.7576 (18)	169 (2)
N1—H1B···O2ⁱ	0.88 (2)	1.91 (2)	2.7166 (18)	152 (2)
N2—H2B···O1ⁱⁱ	0.86 (3)	2.31 (2)	2.868 (2)	123 (2)
N2—H2A···O2	0.91 (3)	2.08 (3)	2.976 (2)	170 (2)

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

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Barker, J., Phillips, P. R., Wallbridge, M. G. H. & Powell, H. R. (1996). Acta Cryst. C52, 2617–2619. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bode, W., Turk, D. & Stürzebecher, J. (1990). Eur. J. Biochem. 193, 175–180. CrossRef CAS PubMed Web of Science Google Scholar
Bryan, R. F. & White, D. H. (1982). Acta Cryst. B38, 1014–1016. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Grzesiak, A., Helland, R., Smalas, A. O., Krowarsch, D., Dadlez, M. & Otlewski, J. (2000). J. Mol. Biol. 301, 205–217. Web of Science CrossRef PubMed CAS Google Scholar
Jokić, M., Bajić, M., Žinić, M., Perić, B. & Kojić-Prodić, B. (2001). Acta Cryst. C57, 1354–1355. Web of Science CSD CrossRef IUCr Journals Google Scholar
Marquart, M., Walter, J., Deisenhofer, J., Bode, W. & Huber, R. (1983). Acta Cryst. B39, 480–490. CrossRef CAS Web of Science IUCr Journals Google Scholar
Motherwell, W. D. S., Shields, G. P. & Allen, F. H. (1999). Acta Cryst. B55, 1044–1056. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Papoutsakis, D., Kirby, J. P., Jackson, J. E. & Nocera, D. G. (1999). Chem. Eur. J. 5, 1474–1480. CrossRef CAS Google Scholar
Portalone, G. (2008). Acta Cryst. E64, o1282–o1283. Web of Science CSD CrossRef IUCr Journals Google Scholar
Portalone, G. (2009). Acta Cryst. E65, o327–o328. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Portalone, G. (2010). Acta Cryst. C66, o295–o301. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Portalone, G. (2011). Acta Cryst. E67, o3394–o3395. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Portalone, G., Ramondo, F., Domenicano, A. & Hargittai, I. (1998). J. Organomet. Chem. 560, 183–190. Web of Science CrossRef CAS Google Scholar
Powers, J. C. & Harper, J. W. (1999). Proteinase inhibitors, edited by A. J. Barrett & G. Salvesen, pp. 55–152. Amsterdam: Elsevier. Google Scholar
Schultz, Gy., Nagy, T., Portalone, G., Ramondo, F., Hargittai, I. & Domenicano, A. (1993). Struct. Chem. 4, 183–190. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sprang, S., Standing, T., Fletterick, R. J., Strong, R. M., Finer-Moor, J., Xuong, N. H., Hamlin, N. R., Rutter, W. & Kreik, C. S. (1987). Science, 237, 905–909. CrossRef CAS PubMed Web of Science Google Scholar
Swaminathan, S., Vimala, T. M. & Lotter, H. (1976). Acta Cryst. B32, 1897–1900. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o268-o269

doi:10.1107/S160053681105519X

Open

access