l-Histidinium p-toluene-sulfonate.

In the title salt, C6H10N3O2 (+)·C7H7O3S(-), the imidazole ring makes a dihedral angle of 70.93 (12)° with the plane of the toluene ring. In the crystal, the ions are linked via N-H⋯O and weak C-H⋯O hydrogen bonds forming two-dimensional networks lying parallel to (001). These networks are linked via C-H⋯π inter-actions, forming a three-dimensional structure.

Related literature

For related structures of 4-toluene­sulfonate salts, see: Koshima et al. (2004 ▶); Biradha & Mahata (2005 ▶); Sivakumar et al. (2012 ▶). For the structure of l-histidine, see: Madden et al. (1972 ▶); Andra et al. (2010 ▶).

Experimental

Crystal data

C6H10N3O2 +·C7H7O3S−

M = 327.36

Orthorhombic,

a = 5.2700 (2) Å

b = 7.3691 (3) Å

c = 38.2042 (14) Å

V = 1483.67 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.930, T max = 0.952

8400 measured reflections

3638 independent reflections

3533 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.094

S = 1.20

3638 reflections

212 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 1479 Friedel pairs

Flack parameter: 0.07 (7)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011161/su2589sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011161/su2589Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011161/su2589Isup3.cml

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

C6H10N3O2+·C7H7O3S−	F(000) = 688
Mr = 327.36	Dx = 1.466 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3638 reflections
a = 5.2700 (2) Å	θ = 2.1–28.3°
b = 7.3691 (3) Å	µ = 0.25 mm−1
c = 38.2042 (14) Å	T = 293 K
V = 1483.67 (10) Å3	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Bruker SMART APEXII area-detector diffractometer	3638 independent reflections
Radiation source: fine-focus sealed tube	3533 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω and φ scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
Tmin = 0.930, Tmax = 0.952	k = −9→6
8400 measured reflections	l = −41→50

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0378P)2 + 0.5138P] where P = (Fo2 + 2Fc2)/3
S = 1.20	(Δ/σ)max = 0.014
3638 reflections	Δρmax = 0.22 e Å−3
212 parameters	Δρmin = −0.29 e Å−3
0 restraints	Absolute structure: Flack (1983), 1479 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (7)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.5686 (4)	0.8856 (3)	0.08354 (5)	0.0267 (4)
C2	0.3546 (5)	0.8904 (3)	0.06249 (6)	0.0378 (5)
H2	0.2447	0.9891	0.0633	0.045*
C3	0.3067 (5)	0.7455 (4)	0.04012 (6)	0.0445 (6)
H3	0.1645	0.7493	0.0257	0.053*
C4	0.4653 (5)	0.5955 (3)	0.03871 (6)	0.0410 (5)
C5	0.6786 (5)	0.5940 (3)	0.05970 (6)	0.0413 (5)
H5	0.7888	0.4956	0.0588	0.050*
C6	0.7307 (4)	0.7383 (3)	0.08214 (6)	0.0352 (5)
H6	0.8747	0.7355	0.0962	0.042*
C7	0.4046 (8)	0.4355 (4)	0.01540 (8)	0.0698 (9)
H7A	0.2604	0.4640	0.0010	0.105*
H7B	0.3667	0.3315	0.0296	0.105*
H7C	0.5479	0.4093	0.0007	0.105*
C8	1.2390 (4)	0.5424 (3)	0.13142 (5)	0.0305 (4)
H8	1.3637	0.5258	0.1145	0.037*
C9	1.0008 (4)	0.6656 (3)	0.17226 (5)	0.0312 (4)
H9	0.9349	0.7496	0.1880	0.037*
C10	0.9162 (4)	0.4935 (2)	0.16686 (5)	0.0240 (4)
C11	0.7122 (4)	0.3892 (2)	0.18479 (5)	0.0242 (4)
H11A	0.6039	0.3330	0.1673	0.029*
H11B	0.6089	0.4719	0.1985	0.029*
C12	0.8209 (3)	0.2411 (2)	0.20905 (4)	0.0190 (3)
H12	0.9473	0.1693	0.1963	0.023*
C13	0.9463 (3)	0.3308 (2)	0.24112 (5)	0.0217 (4)
N1	1.0671 (3)	0.4207 (2)	0.14111 (4)	0.0261 (3)
H1	1.0525	0.3132	0.1326	0.031*
N2	1.2021 (4)	0.6914 (2)	0.15002 (5)	0.0325 (4)
H2A	1.2904	0.7892	0.1484	0.039*
N3	0.6079 (3)	0.1216 (2)	0.22022 (4)	0.0227 (3)
O1	0.4968 (4)	1.2199 (2)	0.10150 (5)	0.0513 (5)
O2	0.8939 (3)	1.0777 (2)	0.11806 (5)	0.0564 (5)
O3	0.5067 (4)	0.9933 (2)	0.14701 (4)	0.0448 (4)
O4	1.1834 (3)	0.3507 (2)	0.23929 (4)	0.0344 (4)
O5	0.8051 (3)	0.3822 (2)	0.26480 (4)	0.0340 (3)
S1	0.62131 (10)	1.05973 (6)	0.114496 (13)	0.02896 (12)
H3D	0.534 (4)	0.064 (3)	0.2015 (6)	0.027 (5)*
H3B	0.673 (5)	0.024 (4)	0.2341 (7)	0.037 (7)*
H3C	0.487 (5)	0.173 (4)	0.2300 (6)	0.036 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0301 (10)	0.0217 (8)	0.0283 (8)	−0.0061 (8)	0.0041 (8)	−0.0026 (7)
C2	0.0372 (12)	0.0342 (10)	0.0421 (11)	0.0033 (9)	−0.0061 (10)	−0.0038 (9)
C3	0.0450 (14)	0.0514 (14)	0.0372 (11)	−0.0084 (12)	−0.0092 (10)	−0.0068 (10)
C4	0.0515 (14)	0.0352 (12)	0.0363 (11)	−0.0120 (10)	0.0078 (10)	−0.0102 (9)
C5	0.0457 (13)	0.0272 (10)	0.0509 (13)	0.0019 (9)	0.0099 (11)	−0.0077 (9)
C6	0.0312 (11)	0.0306 (10)	0.0437 (11)	−0.0002 (9)	−0.0012 (9)	−0.0043 (9)
C7	0.095 (3)	0.0578 (17)	0.0570 (16)	−0.0227 (19)	0.0094 (17)	−0.0293 (14)
C8	0.0280 (10)	0.0273 (9)	0.0361 (10)	−0.0045 (9)	0.0013 (8)	0.0055 (8)
C9	0.0449 (12)	0.0186 (8)	0.0302 (10)	−0.0051 (8)	−0.0014 (9)	−0.0016 (7)
C10	0.0275 (9)	0.0202 (8)	0.0244 (8)	−0.0024 (7)	−0.0016 (8)	0.0021 (6)
C11	0.0245 (9)	0.0210 (8)	0.0273 (8)	−0.0011 (7)	−0.0025 (7)	0.0032 (7)
C12	0.0161 (8)	0.0176 (7)	0.0234 (8)	−0.0030 (6)	0.0006 (6)	0.0000 (6)
C13	0.0214 (9)	0.0139 (7)	0.0300 (9)	0.0024 (6)	−0.0055 (7)	0.0004 (6)
N1	0.0307 (9)	0.0176 (7)	0.0301 (7)	−0.0037 (6)	0.0013 (6)	0.0002 (6)
N2	0.0392 (10)	0.0221 (8)	0.0362 (9)	−0.0119 (7)	−0.0043 (8)	0.0049 (7)
N3	0.0188 (7)	0.0202 (7)	0.0290 (8)	−0.0031 (7)	−0.0001 (7)	0.0008 (6)
O1	0.0761 (14)	0.0229 (7)	0.0550 (10)	0.0084 (8)	−0.0015 (10)	−0.0024 (7)
O2	0.0336 (9)	0.0439 (9)	0.0917 (14)	−0.0153 (8)	0.0063 (9)	−0.0324 (10)
O3	0.0614 (11)	0.0379 (8)	0.0350 (8)	−0.0244 (8)	0.0022 (8)	−0.0085 (6)
O4	0.0192 (7)	0.0312 (7)	0.0529 (9)	−0.0031 (6)	−0.0052 (6)	−0.0140 (6)
O5	0.0322 (8)	0.0386 (8)	0.0312 (7)	0.0045 (6)	−0.0018 (6)	−0.0095 (6)
S1	0.0314 (3)	0.0191 (2)	0.0364 (2)	−0.00777 (18)	0.0038 (2)	−0.00459 (18)

C1—C6	1.382 (3)	C9—H9	0.9300
C1—C2	1.386 (3)	C10—N1	1.374 (2)
C1—S1	1.7671 (19)	C10—C11	1.488 (3)
C2—C3	1.391 (3)	C11—C12	1.542 (2)
C2—H2	0.9300	C11—H11A	0.9700
C3—C4	1.387 (4)	C11—H11B	0.9700
C3—H3	0.9300	C12—N3	1.490 (2)
C4—C5	1.381 (4)	C12—C13	1.541 (2)
C4—C7	1.512 (3)	C12—H12	0.9800
C5—C6	1.393 (3)	C13—O5	1.231 (2)
C5—H5	0.9300	C13—O4	1.260 (2)
C6—H6	0.9300	N1—H1	0.8600
C7—H7A	0.9600	N2—H2A	0.8600
C7—H7B	0.9600	N3—H3D	0.92 (2)
C7—H7C	0.9600	N3—H3B	0.96 (3)
C8—N2	1.322 (3)	N3—H3C	0.83 (3)
C8—N1	1.327 (2)	O1—S1	1.4391 (17)
C8—H8	0.9300	O2—S1	1.4490 (18)
C9—C10	1.360 (3)	O3—S1	1.4652 (17)
C9—N2	1.372 (3)
C6—C1—C2	120.04 (18)	C10—C11—C12	111.95 (15)
C6—C1—S1	119.94 (16)	C10—C11—H11A	109.2
C2—C1—S1	119.85 (16)	C12—C11—H11A	109.2
C1—C2—C3	119.0 (2)	C10—C11—H11B	109.2
C1—C2—H2	120.5	C12—C11—H11B	109.2
C3—C2—H2	120.5	H11A—C11—H11B	107.9
C4—C3—C2	121.8 (2)	N3—C12—C13	110.43 (14)
C4—C3—H3	119.1	N3—C12—C11	108.10 (14)
C2—C3—H3	119.1	C13—C12—C11	109.47 (14)
C5—C4—C3	118.3 (2)	N3—C12—H12	109.6
C5—C4—C7	120.5 (2)	C13—C12—H12	109.6
C3—C4—C7	121.1 (3)	C11—C12—H12	109.6
C4—C5—C6	120.8 (2)	O5—C13—O4	127.17 (18)
C4—C5—H5	119.6	O5—C13—C12	117.22 (16)
C6—C5—H5	119.6	O4—C13—C12	115.52 (17)
C1—C6—C5	120.1 (2)	C8—N1—C10	109.33 (16)
C1—C6—H6	119.9	C8—N1—H1	125.3
C5—C6—H6	119.9	C10—N1—H1	125.3
C4—C7—H7A	109.5	C8—N2—C9	109.36 (17)
C4—C7—H7B	109.5	C8—N2—H2A	125.3
H7A—C7—H7B	109.5	C9—N2—H2A	125.3
C4—C7—H7C	109.5	C12—N3—H3D	111.8 (14)
H7A—C7—H7C	109.5	C12—N3—H3B	109.6 (15)
H7B—C7—H7C	109.5	H3D—N3—H3B	104 (2)
N2—C8—N1	108.10 (18)	C12—N3—H3C	115.8 (18)
N2—C8—H8	125.9	H3D—N3—H3C	104 (2)
N1—C8—H8	125.9	H3B—N3—H3C	112 (2)
C10—C9—N2	106.77 (19)	O1—S1—O2	114.19 (12)
C10—C9—H9	126.6	O1—S1—O3	112.24 (12)
N2—C9—H9	126.6	O2—S1—O3	111.07 (12)
C9—C10—N1	106.42 (17)	O1—S1—C1	107.04 (10)
C9—C10—C11	130.43 (19)	O2—S1—C1	106.56 (10)
N1—C10—C11	123.10 (16)	O3—S1—C1	105.06 (9)
C6—C1—C2—C3	0.0 (3)	N3—C12—C13—O5	−39.4 (2)
S1—C1—C2—C3	−175.30 (18)	C11—C12—C13—O5	79.5 (2)
C1—C2—C3—C4	0.9 (4)	N3—C12—C13—O4	143.72 (16)
C2—C3—C4—C5	−1.4 (4)	C11—C12—C13—O4	−97.38 (19)
C2—C3—C4—C7	177.3 (2)	N2—C8—N1—C10	−0.4 (2)
C3—C4—C5—C6	1.0 (4)	C9—C10—N1—C8	0.7 (2)
C7—C4—C5—C6	−177.7 (2)	C11—C10—N1—C8	−176.84 (17)
C2—C1—C6—C5	−0.3 (3)	N1—C8—N2—C9	−0.1 (2)
S1—C1—C6—C5	174.95 (17)	C10—C9—N2—C8	0.6 (2)
C4—C5—C6—C1	−0.2 (3)	C6—C1—S1—O1	157.65 (17)
N2—C9—C10—N1	−0.8 (2)	C2—C1—S1—O1	−27.0 (2)
N2—C9—C10—C11	176.54 (19)	C6—C1—S1—O2	35.1 (2)
C9—C10—C11—C12	−106.9 (2)	C2—C1—S1—O2	−149.61 (18)
N1—C10—C11—C12	70.1 (2)	C6—C1—S1—O3	−82.85 (19)
C10—C11—C12—N3	−169.02 (15)	C2—C1—S1—O3	92.46 (19)
C10—C11—C12—C13	70.64 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	2.00	2.828 (2)	160
N2—H2A···O3ii	0.86	1.89	2.746 (2)	175
N3—H3B···O4iii	0.96 (3)	1.80 (3)	2.755 (2)	176 (2)
N3—H3C···O4iv	0.83 (3)	2.10 (3)	2.896 (2)	161 (2)
N3—H3D···O3i	0.92 (2)	2.15 (2)	3.000 (2)	153.4 (19)
C8—H8···O1v	0.93	2.41	2.967 (3)	118
C9—H9···O5vi	0.93	2.47	3.062 (3)	122
C6—H6···Cg2	0.93	2.73	3.515 (2)	143
C8—H8···Cg1ii	0.93	2.71	3.394 (2)	131

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids the C1–C6 and N1/N2/C8–C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	2.00	2.828 (2)	160
N2—H2A⋯O3ii	0.86	1.89	2.746 (2)	175
N3—H3B⋯O4iii	0.96 (3)	1.80 (3)	2.755 (2)	176 (2)
N3—H3C⋯O4iv	0.83 (3)	2.10 (3)	2.896 (2)	161 (2)
N3—H3D⋯O3i	0.92 (2)	2.15 (2)	3.000 (2)	153.4 (19)
C8—H8⋯O1v	0.93	2.41	2.967 (3)	118
C9—H9⋯O5vi	0.93	2.47	3.062 (3)	122
C6—H6⋯Cg2	0.93	2.73	3.515 (2)	143
C8—H8⋯Cg1ii	0.93	2.71	3.394 (2)	131

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .