4-(Cyano-meth-yl)anilinium 4-methyl-benzene-sulfonate monohydrate.

In the title salt, C(8)H(9)N(2) (+)·C(7)H(7)O(3)S(-)·H(2)O, the dihedral angle between the cation and anion benzene rings is 50.1 (4)°. In the cation, the cyano-methyl group is twisted from the plane of the benzene ring [C-C-C-N = -86 (12)°]. In the crystal, the cations, anions and water mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds, forming a chain along the c axis.

Related literature

For phase transition materials and metal-organic coordination compounds, see: Zhang et al. (2009 ▶); Li et al. (2008 ▶); Liu et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C8H9N2 +·C7H7O3S−·H2O

M = 322.38

Tetragonal,

a = 22.931 (2) Å

c = 5.946 (2) Å

V = 3126.6 (11) Å3

Z = 8

Mo Kα radiation

μ = 0.23 mm−1

T = 293 K

0.45 × 0.40 × 0.25 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.903, T max = 0.945

15184 measured reflections

3089 independent reflections

2723 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.196

S = 1.05

3089 reflections

200 parameters

5 restraints

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶), 1383 Friedel pairs

Flack parameter: 0.05 (16)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020180/jj2033sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020180/jj2033Isup2.hkl

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

C8H9N2+·C7H7O3S−·H2O	Dx = 1.370 Mg m−3
Mr = 322.38	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 5655 reflections
Hall symbol: I -4	θ = 3.5–27.5°
a = 22.931 (2) Å	µ = 0.23 mm−1
c = 5.946 (2) Å	T = 293 K
V = 3126.6 (11) Å3	Prism, orange
Z = 8	0.45 × 0.40 × 0.25 mm
F(000) = 1360

Rigaku SCXmini diffractometer	3089 independent reflections
Radiation source: fine-focus sealed tube	2723 reflections with I > 2σ(I)
graphite	Rint = 0.068
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 3.5°
CCD_Profile_fitting scans	h = −28→28
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −28→28
Tmin = 0.903, Tmax = 0.945	l = −7→7
15184 measured reflections

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)] = 0.072	H-atom parameters constrained
wR(F2) = 0.196	w = 1/[σ2(Fo2) + (0.120P)2 + 1.4624P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3089 reflections	Δρmax = 0.54 e Å−3
200 parameters	Δρmin = −0.24 e Å−3
5 restraints	Absolute structure: Flack (1983), 1383 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (16)

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.

	x	y	z	Uiso*/Ueq
C9	0.80554 (19)	0.68688 (19)	0.6159 (9)	0.0451 (10)
C10	0.7993 (2)	0.6601 (2)	0.4099 (9)	0.0509 (12)
H10A	0.8321	0.6557	0.3195	0.061*
C11	0.74716 (19)	0.6397 (2)	0.3328 (8)	0.0444 (11)
H11A	0.7449	0.6211	0.1942	0.053*
C12	0.69775 (19)	0.64693 (18)	0.4622 (7)	0.0368 (9)
C13	0.7012 (2)	0.6746 (2)	0.6699 (8)	0.0451 (11)
H13A	0.6680	0.6802	0.7575	0.054*
C14	0.7554 (2)	0.6937 (2)	0.7428 (9)	0.0486 (11)
H14A	0.7581	0.7118	0.8823	0.058*
C15	0.8629 (3)	0.7090 (3)	0.7022 (12)	0.0718 (17)
H15A	0.8929	0.7011	0.5937	0.086*
H15B	0.8722	0.6898	0.8412	0.086*
H15C	0.8604	0.7503	0.7269	0.086*
O1	0.58469 (14)	0.65351 (15)	0.4733 (6)	0.0567 (10)
O2	0.62991 (15)	0.62234 (19)	0.1289 (6)	0.0679 (10)
O3	0.62786 (15)	0.55881 (15)	0.4448 (7)	0.0608 (10)
O4	0.5601 (2)	0.5210 (3)	0.7965 (10)	0.112 (2)
H4D	0.5808	0.5324	0.6864	0.168*
H4B	0.5707	0.5387	0.9153	0.168*
S1	0.62993 (5)	0.61860 (5)	0.37106 (18)	0.0416 (3)
C1	0.7116 (2)	0.49056 (19)	1.0648 (8)	0.0409 (10)
C2	0.7262 (2)	0.51689 (19)	0.8664 (9)	0.0468 (10)
H2B	0.6985	0.5227	0.7546	0.056*
C3	0.7830 (2)	0.5346 (2)	0.8365 (9)	0.0512 (12)
H3B	0.7934	0.5536	0.7042	0.061*
C4	0.8251 (2)	0.5248 (2)	0.9986 (9)	0.0451 (11)
C5	0.8087 (2)	0.4970 (2)	1.1943 (9)	0.0499 (12)
H5A	0.8365	0.4896	1.3044	0.060*
C6	0.7516 (2)	0.4798 (2)	1.2302 (8)	0.0495 (11)
H6A	0.7407	0.4614	1.3631	0.059*
C7	0.8871 (2)	0.5456 (3)	0.9678 (10)	0.0616 (15)
H7A	0.8908	0.5843	1.0322	0.074*
H7B	0.9130	0.5199	1.0501	0.074*
C8	0.9054 (3)	0.5476 (3)	0.7358 (13)	0.0763 (18)
N1	0.65068 (16)	0.47274 (18)	1.1017 (8)	0.0531 (10)
H1A	0.6316	0.5013	1.1716	0.080*
H1B	0.6499	0.4407	1.1861	0.080*
H1C	0.6338	0.4655	0.9699	0.080*
N2	0.9217 (3)	0.5462 (3)	0.5409 (11)	0.0937 (19)

	U11	U22	U33	U12	U13	U23
C9	0.045 (2)	0.037 (2)	0.053 (3)	−0.0032 (18)	0.004 (2)	0.001 (2)
C10	0.043 (2)	0.056 (3)	0.054 (3)	0.001 (2)	0.015 (2)	−0.003 (2)
C11	0.048 (3)	0.045 (2)	0.041 (2)	0.001 (2)	0.009 (2)	−0.006 (2)
C12	0.043 (2)	0.031 (2)	0.036 (2)	0.0017 (18)	0.0014 (18)	0.0012 (17)
C13	0.050 (3)	0.046 (2)	0.039 (3)	0.004 (2)	0.005 (2)	−0.007 (2)
C14	0.056 (3)	0.043 (2)	0.048 (3)	0.000 (2)	0.005 (2)	−0.003 (2)
C15	0.056 (3)	0.069 (4)	0.091 (5)	−0.015 (3)	−0.005 (3)	−0.005 (3)
O1	0.0433 (18)	0.059 (2)	0.068 (2)	0.0101 (16)	0.0096 (17)	−0.0105 (18)
O2	0.051 (2)	0.111 (3)	0.0417 (18)	0.009 (2)	0.0004 (18)	−0.007 (2)
O3	0.059 (2)	0.0404 (18)	0.083 (3)	−0.0032 (16)	−0.0072 (19)	0.0012 (17)
O4	0.107 (4)	0.118 (4)	0.110 (5)	0.026 (3)	0.014 (3)	0.029 (4)
S1	0.0416 (6)	0.0415 (6)	0.0416 (5)	0.0043 (5)	0.0002 (5)	−0.0030 (5)
C1	0.041 (2)	0.037 (2)	0.044 (3)	0.0030 (18)	0.0073 (19)	−0.0069 (19)
C2	0.052 (3)	0.042 (2)	0.047 (3)	0.001 (2)	−0.005 (2)	0.000 (2)
C3	0.063 (3)	0.045 (3)	0.046 (3)	−0.003 (2)	0.008 (2)	0.001 (2)
C4	0.040 (2)	0.045 (3)	0.050 (3)	−0.0037 (19)	0.001 (2)	−0.012 (2)
C5	0.049 (3)	0.053 (3)	0.048 (3)	0.003 (2)	−0.005 (2)	−0.008 (2)
C6	0.060 (3)	0.052 (3)	0.036 (2)	0.000 (2)	−0.001 (2)	0.006 (2)
C7	0.052 (3)	0.070 (4)	0.062 (3)	−0.006 (3)	0.005 (3)	−0.027 (3)
C8	0.056 (4)	0.095 (5)	0.078 (5)	−0.012 (3)	0.001 (3)	0.003 (4)
N1	0.042 (2)	0.058 (2)	0.059 (3)	−0.0061 (18)	0.005 (2)	−0.009 (2)
N2	0.077 (4)	0.124 (5)	0.080 (4)	−0.016 (4)	−0.012 (3)	0.005 (4)

C9—C10	1.378 (7)	C1—C2	1.367 (7)
C9—C14	1.384 (7)	C1—C6	1.367 (7)
C9—C15	1.500 (7)	C1—N1	1.473 (6)
C10—C11	1.363 (7)	C2—C3	1.376 (7)
C10—H10A	0.9300	C2—H2B	0.9300
C11—C12	1.379 (6)	C3—C4	1.383 (7)
C11—H11A	0.9300	C3—H3B	0.9300
C12—C13	1.391 (6)	C4—C5	1.380 (7)
C12—S1	1.771 (4)	C4—C7	1.511 (7)
C13—C14	1.388 (7)	C5—C6	1.384 (7)
C13—H13A	0.9300	C5—H5A	0.9300
C14—H14A	0.9300	C6—H6A	0.9300
C15—H15A	0.9600	C7—C8	1.442 (9)
C15—H15B	0.9600	C7—H7A	0.9700
C15—H15C	0.9600	C7—H7B	0.9700
O1—S1	1.445 (3)	C8—N2	1.218 (9)
O2—S1	1.443 (4)	N1—H1A	0.8900
O3—S1	1.440 (4)	N1—H1B	0.8900
O4—H4D	0.8500	N1—H1C	0.8900
O4—H4B	0.8499
C10—C9—C14	116.6 (4)	C2—C1—C6	122.5 (4)
C10—C9—C15	123.1 (5)	C2—C1—N1	118.9 (4)
C14—C9—C15	120.2 (5)	C6—C1—N1	118.6 (4)
C11—C10—C9	122.9 (4)	C1—C2—C3	118.3 (5)
C11—C10—H10A	118.5	C1—C2—H2B	120.9
C9—C10—H10A	118.5	C3—C2—H2B	120.9
C10—C11—C12	119.4 (5)	C2—C3—C4	121.5 (5)
C10—C11—H11A	120.3	C2—C3—H3B	119.3
C12—C11—H11A	120.3	C4—C3—H3B	119.3
C11—C12—C13	120.3 (4)	C3—C4—C5	118.2 (4)
C11—C12—S1	120.4 (3)	C3—C4—C7	121.4 (5)
C13—C12—S1	119.3 (3)	C5—C4—C7	120.4 (5)
C14—C13—C12	118.2 (4)	C6—C5—C4	121.4 (5)
C14—C13—H13A	120.9	C6—C5—H5A	119.3
C12—C13—H13A	120.9	C4—C5—H5A	119.3
C9—C14—C13	122.6 (5)	C1—C6—C5	118.1 (4)
C9—C14—H14A	118.7	C1—C6—H6A	120.9
C13—C14—H14A	118.7	C5—C6—H6A	120.9
C9—C15—H15A	109.5	C8—C7—C4	113.6 (5)
C9—C15—H15B	109.5	C8—C7—H7A	108.9
H15A—C15—H15B	109.5	C4—C7—H7A	108.9
C9—C15—H15C	109.5	C8—C7—H7B	108.9
H15A—C15—H15C	109.5	C4—C7—H7B	108.9
H15B—C15—H15C	109.5	H7A—C7—H7B	107.7
H4D—O4—H4B	109.5	N2—C8—C7	176.5 (9)
O3—S1—O2	111.1 (3)	C1—N1—H1A	109.5
O3—S1—O1	112.1 (2)	C1—N1—H1B	109.5
O2—S1—O1	112.8 (2)	H1A—N1—H1B	109.5
O3—S1—C12	106.6 (2)	C1—N1—H1C	109.5
O2—S1—C12	106.5 (2)	H1A—N1—H1C	109.5
O1—S1—C12	107.4 (2)	H1B—N1—H1C	109.5
C14—C9—C10—C11	−1.5 (7)	C13—C12—S1—O1	28.4 (4)
C15—C9—C10—C11	179.5 (5)	C6—C1—C2—C3	−2.0 (7)
C9—C10—C11—C12	1.5 (8)	N1—C1—C2—C3	178.4 (4)
C10—C11—C12—C13	−0.2 (7)	C1—C2—C3—C4	1.9 (7)
C10—C11—C12—S1	−177.7 (4)	C2—C3—C4—C5	−0.5 (7)
C11—C12—C13—C14	−0.9 (7)	C2—C3—C4—C7	−178.5 (5)
S1—C12—C13—C14	176.7 (4)	C3—C4—C5—C6	−0.8 (7)
C10—C9—C14—C13	0.3 (7)	C7—C4—C5—C6	177.2 (5)
C15—C9—C14—C13	179.3 (5)	C2—C1—C6—C5	0.8 (7)
C12—C13—C14—C9	0.8 (7)	N1—C1—C6—C5	−179.6 (4)
C11—C12—S1—O3	85.7 (4)	C4—C5—C6—C1	0.7 (7)
C13—C12—S1—O3	−91.8 (4)	C3—C4—C7—C8	−30.1 (8)
C11—C12—S1—O2	−33.0 (4)	C5—C4—C7—C8	152.0 (6)
C13—C12—S1—O2	149.5 (4)	C4—C7—C8—N2	−86 (12)
C11—C12—S1—O1	−154.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4D···O3	0.85	1.90	2.746 (7)	179
N1—H1A···O3i	0.89	2.09	2.886 (6)	148
N1—H1B···O1ii	0.89	2.11	2.850 (6)	140
N1—H1C···O4	0.89	2.35	2.972 (6)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4D⋯O3	0.85	1.90	2.746 (7)	179
N1—H1A⋯O3i	0.89	2.09	2.886 (6)	148
N1—H1B⋯O1ii	0.89	2.11	2.850 (6)	140
N1—H1C⋯O4	0.89	2.35	2.972 (6)	127

Symmetry codes: (i) ; (ii) .