4-Meth-oxy-benzamidinium hydrogen sulfate.

The title salt, C(8)H(11)N(2)O(+)·HSO(4) (-), has been synthesized by the reaction between 4-meth-oxy-benzamidine and sulfuric acid. The asymmetric unit comprises a nonplanar 4-meth-oxy-benzamidinium cation and one hydrogen sulfate anion. In the cation, the amidinium group has two identical C-N bonds [1.306 (2) and 1.308 (2) Å], and its plane forms a dihedral angle of 6.49 (8)° with the mean plane of the benzene ring. The ionic components are associated in the crystal via N-H(+)⋯O(-), resulting in chains running approximately along the b-axis direction whicg are interconnected by O-H⋯O(-) hydrogen bonds.

Related literature

For the biological and pharmacological relevance of benzamidine, see: Powers & Harper (1999 ▶); Grzesiak et al. (2000 ▶). For structural analysis of proton-transfer adducts containing mol­ecules of biological inter­est, see: Portalone (2011a ▶); Portalone & Irrera (2011 ▶). For the supra­molecular association in proton-transfer adducts containing benzamidinium cations, see: Portalone (2010 ▶, 2011b ▶, 2012 ▶); Irrera & Portalone (2012 ▶); Irrera et al. (2012 ▶). For hydrogen-bond motifs, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C8H11N2O+·HSO4 −

M = 248.26

Monoclinic,

a = 14.2608 (14) Å

b = 10.1844 (9) Å

c = 7.5723 (9) Å

β = 94.206 (10)°

V = 1096.83 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 298 K

0.31 × 0.25 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.912, T max = 0.956

16529 measured reflections

2626 independent reflections

2133 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.114

S = 1.04

2626 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.34 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: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044327/rz5020sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044327/rz5020Isup2.hkl

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

C8H11N2O+·HSO4−	F(000) = 520
Mr = 248.26	Dx = 1.503 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 4647 reflections
a = 14.2608 (14) Å	θ = 2.9–29.7°
b = 10.1844 (9) Å	µ = 0.30 mm−1
c = 7.5723 (9) Å	T = 298 K
β = 94.206 (10)°	Tablets, colourless
V = 1096.83 (19) Å3	0.31 × 0.25 × 0.15 mm
Z = 4

Oxford Diffraction Xcalibur S CCD diffractometer	2626 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2133 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 16.0696 pixels mm-1	θmax = 28.0°, θmin = 2.9°
ω and φ scans	h = −18→18
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −13→13
Tmin = 0.912, Tmax = 0.956	l = −9→9
16529 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0582P)2 + 0.2957P] where P = (Fo2 + 2Fc2)/3
2626 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Experimental. Absorption correction: [CrysAlis RED (Oxford Diffraction, 2006); 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
S1	−0.16129 (3)	0.16203 (4)	0.84884 (6)	0.03448 (15)
O2	−0.20315 (10)	0.11649 (13)	1.00664 (17)	0.0514 (4)
O3	−0.24735 (9)	0.20809 (15)	0.7284 (2)	0.0498 (4)
H3A	−0.2287 (18)	0.259 (3)	0.662 (4)	0.064 (8)*
O4	−0.09972 (9)	0.27365 (12)	0.87891 (18)	0.0467 (3)
O5	−0.11706 (9)	0.05608 (12)	0.75864 (19)	0.0485 (3)
O1	0.49301 (10)	0.19362 (16)	0.4667 (3)	0.0684 (5)
N1	0.07593 (12)	0.28008 (15)	0.6992 (3)	0.0452 (4)
H1A	0.0189 (18)	0.280 (2)	0.730 (3)	0.053 (6)*
H1B	0.1027 (17)	0.354 (2)	0.693 (3)	0.061 (7)*
N2	0.07598 (14)	0.06125 (17)	0.6593 (3)	0.0595 (5)
H2A	0.0212 (18)	0.058 (2)	0.692 (3)	0.057 (7)*
H2B	0.107 (2)	−0.009 (3)	0.647 (4)	0.087 (9)*
C1	0.21780 (12)	0.18063 (15)	0.6067 (2)	0.0346 (4)
C2	0.26115 (13)	0.30028 (17)	0.5855 (3)	0.0465 (5)
H2	0.2275	0.3770	0.6020	0.056*
C3	0.35275 (14)	0.30917 (18)	0.5407 (3)	0.0497 (5)
H3	0.3806	0.3910	0.5288	0.060*
C4	0.40279 (13)	0.19663 (19)	0.5136 (3)	0.0465 (5)
C5	0.36028 (15)	0.0754 (2)	0.5315 (3)	0.0595 (6)
H5	0.3937	−0.0010	0.5123	0.071*
C6	0.26906 (14)	0.06751 (18)	0.5775 (3)	0.0493 (5)
H6	0.2413	−0.0143	0.5892	0.059*
C7	0.12029 (12)	0.17365 (15)	0.6575 (2)	0.0365 (4)
C8	0.54205 (16)	0.3152 (3)	0.4575 (4)	0.0749 (8)
H8A	0.5094 (10)	0.3716 (13)	0.369 (2)	0.112*
H8B	0.6058 (12)	0.2988 (4)	0.425 (3)	0.112*
H8C	0.5445 (13)	0.3583 (13)	0.573 (2)	0.112*

	U11	U22	U33	U12	U13	U23
S1	0.0360 (3)	0.0244 (2)	0.0440 (3)	−0.00176 (15)	0.00969 (18)	−0.00018 (16)
O2	0.0718 (9)	0.0368 (7)	0.0477 (8)	−0.0093 (6)	0.0198 (7)	0.0026 (6)
O3	0.0352 (7)	0.0531 (8)	0.0616 (9)	−0.0021 (6)	0.0082 (6)	0.0112 (7)
O4	0.0456 (7)	0.0321 (7)	0.0627 (9)	−0.0101 (5)	0.0068 (6)	−0.0029 (6)
O5	0.0488 (7)	0.0302 (6)	0.0688 (9)	0.0022 (5)	0.0193 (6)	−0.0041 (6)
O1	0.0351 (8)	0.0586 (9)	0.1145 (14)	0.0038 (7)	0.0259 (8)	−0.0054 (9)
N1	0.0333 (8)	0.0306 (8)	0.0735 (12)	−0.0025 (6)	0.0154 (8)	−0.0090 (7)
N2	0.0389 (10)	0.0285 (8)	0.1137 (17)	−0.0032 (7)	0.0232 (10)	−0.0039 (9)
C1	0.0304 (8)	0.0282 (8)	0.0454 (9)	0.0011 (6)	0.0031 (7)	−0.0015 (7)
C2	0.0367 (9)	0.0277 (8)	0.0763 (14)	0.0020 (7)	0.0133 (9)	−0.0030 (8)
C3	0.0395 (10)	0.0335 (9)	0.0775 (14)	−0.0050 (8)	0.0137 (9)	−0.0031 (9)
C4	0.0309 (9)	0.0457 (10)	0.0639 (12)	0.0020 (8)	0.0097 (8)	−0.0032 (9)
C5	0.0448 (11)	0.0352 (10)	0.1007 (17)	0.0089 (8)	0.0210 (11)	−0.0056 (10)
C6	0.0423 (10)	0.0277 (8)	0.0793 (14)	0.0008 (7)	0.0132 (9)	−0.0048 (9)
C7	0.0328 (9)	0.0283 (8)	0.0483 (10)	−0.0003 (6)	0.0023 (7)	−0.0020 (7)
C8	0.0381 (12)	0.0773 (17)	0.112 (2)	−0.0104 (11)	0.0238 (13)	−0.0012 (15)

S1—O4	1.4442 (13)	C1—C6	1.391 (2)
S1—O5	1.4464 (13)	C1—C7	1.471 (2)
S1—O2	1.4504 (13)	C2—C3	1.377 (3)
S1—O3	1.5470 (15)	C2—H2	0.9300
O3—H3A	0.78 (3)	C3—C4	1.374 (3)
O1—C4	1.360 (2)	C3—H3	0.9300
O1—C8	1.427 (3)	C4—C5	1.386 (3)
N1—C7	1.306 (2)	C5—C6	1.374 (3)
N1—H1A	0.86 (2)	C5—H5	0.9300
N1—H1B	0.84 (2)	C6—H6	0.9300
N2—C7	1.308 (2)	C8—H8A	0.9739
N2—H2A	0.84 (2)	C8—H8B	0.9739
N2—H2B	0.86 (3)	C8—H8C	0.9739
C1—C2	1.381 (2)
O4—S1—O5	112.37 (8)	C4—C3—H3	120.2
O4—S1—O2	113.83 (8)	C2—C3—H3	120.2
O5—S1—O2	111.75 (8)	O1—C4—C3	124.73 (18)
O4—S1—O3	107.52 (8)	O1—C4—C5	115.75 (17)
O5—S1—O3	107.60 (8)	C3—C4—C5	119.52 (17)
O2—S1—O3	103.05 (9)	C6—C5—C4	120.42 (17)
S1—O3—H3A	106.6 (19)	C6—C5—H5	119.8
C4—O1—C8	118.01 (17)	C4—C5—H5	119.8
C7—N1—H1A	123.0 (15)	C5—C6—C1	120.68 (17)
C7—N1—H1B	119.6 (16)	C5—C6—H6	119.7
H1A—N1—H1B	117 (2)	C1—C6—H6	119.7
C7—N2—H2A	120.2 (16)	N1—C7—N2	118.74 (18)
C7—N2—H2B	118.6 (19)	N1—C7—C1	120.48 (15)
H2A—N2—H2B	120 (2)	N2—C7—C1	120.77 (16)
C2—C1—C6	117.86 (16)	O1—C8—H8A	109.5
C2—C1—C7	120.84 (15)	O1—C8—H8B	109.5
C6—C1—C7	121.29 (15)	H8A—C8—H8B	109.5
C3—C2—C1	121.85 (16)	O1—C8—H8C	109.5
C3—C2—H2	119.1	H8A—C8—H8C	109.5
C1—C2—H2	119.1	H8B—C8—H8C	109.5
C4—C3—C2	119.65 (17)
C6—C1—C2—C3	−1.4 (3)	C3—C4—C5—C6	−0.5 (4)
C7—C1—C2—C3	179.01 (19)	C4—C5—C6—C1	0.0 (4)
C1—C2—C3—C4	0.9 (3)	C2—C1—C6—C5	0.9 (3)
C8—O1—C4—C3	4.9 (3)	C7—C1—C6—C5	−179.5 (2)
C8—O1—C4—C5	−176.0 (2)	C2—C1—C7—N1	−6.3 (3)
C2—C3—C4—O1	179.1 (2)	C6—C1—C7—N1	174.06 (19)
C2—C3—C4—C5	0.1 (3)	C2—C1—C7—N2	172.7 (2)
O1—C4—C5—C6	−179.6 (2)	C6—C1—C7—N2	−6.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2i	0.78 (3)	1.79 (3)	2.562 (2)	172 (3)
N1—H1A···O4	0.86 (2)	2.10 (2)	2.938 (2)	163 (2)
N1—H1B···O5ii	0.84 (2)	2.10 (2)	2.884 (2)	154 (2)
N2—H2A···O5	0.84 (2)	2.07 (3)	2.907 (2)	177 (2)
N2—H2B···O4iii	0.86 (3)	2.22 (3)	2.965 (2)	145 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2i	0.78 (3)	1.79 (3)	2.562 (2)	172 (3)
N1—H1A⋯O4	0.86 (2)	2.10 (2)	2.938 (2)	163 (2)
N1—H1B⋯O5ii	0.84 (2)	2.10 (2)	2.884 (2)	154 (2)
N2—H2A⋯O5	0.84 (2)	2.07 (3)	2.907 (2)	177 (2)
N2—H2B⋯O4iii	0.86 (3)	2.22 (3)	2.965 (2)	145 (3)

Symmetry codes: (i) ; (ii) ; (iii) .