4-Meth-oxy-benzamidinium 2,6-dimeth-oxy-benzoate.

The title compound, C(8)H(11)N(2)O(+)·C(9)H(9)O(4) (-), was synthesized by the reaction of 4-meth-oxy-benzamidine (4-amidino-anisole) and 2,6-dimeth-oxy-benzoic acid. The structure consists of non-planar pairs of hydrogen-bonded 4-meth-oxy-benzamidinium cations and 2,6-dimeth-oxy-benzoate 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-meth-oxy substituents force the carb-oxy-ate 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 inter-molecular 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 = 332.35

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.131

S = 1.17

4217 reflections

239 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.18 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); 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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681105519X/rz2691sup1.cif

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

Supplementary material file. DOI: 10.1107/S160053681105519X/rz2691Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H11N2O+·C9H9O4−	F(000) = 704
Mr = 332.35	Dx = 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

Oxford Diffraction Xcalibur S CCD diffractometer	4217 independent reflections
Radiation source: Enhance (Mo) X-ray source	3914 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 16.0696 pixels mm-1	θmax = 28.5°, θmin = 2.9°
ω and φ scans	h = −16→16
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −12→12
Tmin = 0.971, Tmax = 0.976	l = −18→18
76316 measured reflections

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(Fo2) + (0.0405P)2 + 0.878P] where P = (Fo2 + 2Fc2)/3
4217 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) ; (ii) .