A comparative study of intermolecular interactions in the crystal structures of phenyl/phenyl end-capped oligoanilines

Three crystal structures have been analysed from the point of view of intermolecular interactions: N,N′-di­phenyl-1,4-benzo­quinone di­imine, C₁₈H₁₄N₂, (I), its reduced form N,N′-di­phenyl-1,4-phenyl­enedi­amine, C₁₈H₁₆N₂, (II), and N,N′-di­phenyl-1,4-phenyl­enedi­ammonium bis(p-toluene­sulfonate), C₁₈H₁₈N₂²⁺·2C₇H₇O₃S⁻, (III), which contains fully protonated (II) with p-toluene­sulfonic acid. The local molecular C_i symmetry is preserved in all three structures and the packing seems to be dominated by the mutual arrangement of the simple polyaniline oligomers in the different protonation states. In (I), the most significant molecular interactions are stacking forces, forming columns of mol­ecules along [001]. Close packing of the columns results in C-centring of the structure. In (II), only van der Waals interactions can be observed. In the structure of (III), the p-toluene­sulfonate ions serve as acceptors in relatively strong N—H...O hydrogen bonds. The N,N′-di­phenyl-1,4-phenyl­enedi­ammonium cation intercalates between two anions related by a centre of symmetry.

S1. Comment

Polyaniline oligomers containing alternating benzoid and quinoid rings with amine and/or imine groups in between are very interesting subjects for research. Detailed analysis of their crystal structures can help the understanding of the spectral behaviour of the compounds and explain a possible mechanism for their electrical conductivity (Hadek, 1968; Hadek et al., 1969).

The mutual interaction of polyaniline oligomers in the crystalline state seems to be a significant key for the prediction of their properties. Investigations of intermolecular interactions in the crystal structures of polyaniline oligomers are important because single crystals of polyaniline itself, suitable for X-ray diffraction, are extremely difficult to obtain, and usually only powder data from thin films are available [e.g. polyaniline 10-camphorsulfonate, either from an m-cresol solution (Łużny et al., 1997) or from 1,1,1,3,3,3-hexafluoro-2-propanol (Gawlicka, 1997)]. Here, we report the crystal structures of the title compounds, (I), (II), and (III), considered as examples of simple phenyl/phenyl end-capped polyaniline oligomers. \sch

The molecular geometry of (I) was found to be similar to that previously described by Baughman et al. (1988), with its structural, optical and electrochemical properties published separately by Shacklette et al. (1988). The structure of orthorhombic (II) appeared to be essentially the same as described earlier in an isotropic approximation by Povet'eva et al. (1976). We were not able to obtain the triclinic polymorph of (II) reported by Boyer et al. (2000), with its spectroscopic properties recently described by Quillard et al. (2001). The structure of (III) has not been published previously.

Obviously, there is a significant difference in the geometry of the molecules depending on the protonation states (Figs. 1–3). In (I), the imine N atoms have a planar configuration. The amine N atoms of (II) have a pyramidal configuration and those of (III) show a tetrahedral configuration. The most indicative descriptor of the N-atom configuration is the value of the C1—N1—C7 angle. The essential geometric details of the molecules, which allow the recognition of the protonation states of the oligomers, are given in Tables 1, 2 and 3.

The lone electron pair of the imine N atom of (I) makes the N—C single and double bonds shorter. Its influence on the terminal benzene ring is counteracted by the opposing effect of the quinoid system, as can be seen from the value of the C2—C1—C6 angle in Table 1.

The geometry of the molecule of (II) is influenced by an interaction between the lone electron pair of the N atom and the π-electron systems of both neighbouring benzene rings, which causes a shortening of the N—C bonds and a diminution of the appropriate endocyclic C—C—C angles, to 118.2 (2) and 117.7 (2)°, respectively.

The –NH₂⁺– group of (III) has a withdrawing effect on the benzene rings, enlarging the endocyclic C—C—C angles to 122.0 (3) and 121.6 (2)°. The geometry of the p-toluenesufonate anion is typical, apart from the relatively long S1—O11 bond, caused by atom O11 acting as the acceptor in an N—H.·O-type hydrogen-bond interaction.

The conformation of the molecules of (I), (II) and (III), described by the C1—N1—C7—C9 and C7—N1—C1—C2 torsion angles, depends on both the molecular configuration and the packing in the crystal structures.

The packing in the crystal structure of (I) is shown in Fig. 4(a) as a projection onto the (010) plane. A stacking of the molecules along [001] can be considered, resulting in a distance of 3.505 (2) Å between parallel quinoid rings with a centroid offset of 1.219 (3) Å. The mutual arrangement of the rings in the stack is presented in Fig. 4(b). Between such columns, shown in Fig. 4(c) in one possible close packing, there are only van der Waals interactions.

The packing of the molecules of (II), in the orthorhombic polymorph studied here, is shown in Fig. 5(a). The H1 atoms of the NH groups point in opposite directions from the diamine moiety towards the π-electron systems of adjacent molecules. The distance of atom H1 from the centroid of the C7/C8—C9 ring at (-x, y + 1/2, 1/2 - z) is 2.97 (2) Å, whereas its distance from the best plane of the ring is 2.93 (3) Å. Fig. 5(b) shows the mutual arrangement of the molecules along [100].

In the structure of (III), close-packed layers built of the oligomer cations can be distinguished (Fig. 6a), with the shortest distance of 2.90 (4) Å being between atom H8 and the best plane of the C1/C2—C6 ring of the adjacent molecule at (5/2 - x, y - 1/2, 1 - z). Each amine layer is linked to p-toluenesulfonate anions through π–π interactions, in such a way that the benzoid ring of the cation intercalates between the benzene rings of two p-toluenesulfonate anions (Fig. 6 b). Additionally, relatively strong intermolecular N—H···O hydrogen bonds are formed (Table 4).

In conclusion, the packing in the crystal structures of (I), (II) and (III) seems to be dominated by a mutual arrangement of the molecules of the polyaniline oligomers. In (I), the most significant intermolecular interactions are stacking forces between parallel quinoid rings. The columns of molecules parallel to [001] are close-packed, resulting in a C-centred three-dimensional structure. In (II), the reduced form of (I), only the molecular shape and van der Waals interactions determine the packing. In the structure of (III), the salt of fully protonated (II), in addition to the hydrophobic interactions in the oligomer layers, the p-toluenesulfonate ions act as acceptors in relatively strong N—H···O hydrogen bonds.

S2. Experimental

N,N'-diphenyl-1,4-phenylenediamine (ex Aldrich), (II), without further purification, was recrystallized from benzene by slow evaporation at room temperature. A mixture of (II) and 4-toluenesulfonic acid, in a 1:2 stoichiometric ratio, was finely ground and then dissolved in acetonitrile. Crystals of the salt, (III), were obtained by slow evaporation at room temperature. N,N'-diphenyl-1,4-benzoquinonediimine, (I), was prepared by oxidation of (II) in toluene with the use of 1.2 equivalents of dibenzoyl peroxide, as suggested by MacDiarmid et al. (1999). Crystals of (I) were grown from a saturated toluene solution.

S3. Refinement

In all of three structures, the H atoms were located from the difference Fourier map, and were included in the refinement without constraints and with isotropic displacement factors. The ranges and average values of the refined C—H distances were, respectively, as follows: 0.96–1.02 Å and 0.99 (2) Å for (I), 0.89–0.99 Å and 0.95 (4) Å for (II), and 0.89–1.06 Å and 0.97 (5) Å for (III). N—H distances were found of 0.91 (3) Å in (II), and 0.86 (4) and 0.95 (4) Å in (III).

Computing details

Data collection: COLLECT (Nonius, 1998) for (I), (III); KM-4 Software (Kuma Diffraction, 1995) for (II). Cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997) for (I), (III); KM-4 Software for (II). Data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK for (I), (III); DATAPROC (Gałdecki et al., 1995) for (II). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 2. A view of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 3. A view of the the two ions in the salt of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 4. (a) The packing in the crystal structure of (I) projected onto (010). (b) The stacking of the molecules viewed along a direction close to [001]. (c) A view of the crystal structure along [001], showing the close packing of the stacks. Fig. 5. (a) The packing in the crystal structure of (II), viewed along [001]. (b) The arrangement of the molecules along [100]. The thickness of the projected layer is between a/4 and 3a/4. Fig. 6. (a) The mutual arrangement of oligomer-cation layers observed in the structure of (III). (b) The intercalation of the benzoid ring of the cation in between the rings of two p-toluenesulfonate anions, related by a centre of symmetry, seen in an (001) projection.

(I) N,N'-diphenyl-1,4-benzoquinonediamine

Crystal data

C18H14N2	F(000) = 544
Mr = 258.31	Dx = 1.243 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.4797 (2) Å	Cell parameters from 3078 reflections
b = 6.7734 (2) Å	θ = 1.0–32.6°
c = 7.4212 (5) Å	µ = 0.07 mm^−1
β = 92.026 (1)°	T = 293 K
V = 1380.5 (1) Å^3	Needle, orange
Z = 4	0.25 × 0.07 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1868 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Horizontally mounted graphite crystal monochromator	θmax = 32.4°, θmin = 5.6°
Detector resolution: 9 pixels mm^-1	h = 0→41
ϕ and ω scans to fill Ewald sphere	k = −10→8
7175 measured reflections	l = −11→11
2457 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: difference Fourier map
wR(F^2) = 0.170	All H-atom parameters refined
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0711P)^2 + 0.6075P] where P = (Fo^2 + 2Fc^2)/3
2457 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.06460 (4)	0.29667 (17)	0.07751 (16)	0.0391 (3)
C1	0.11349 (5)	0.26713 (18)	0.13680 (18)	0.0355 (3)
C2	0.14654 (5)	0.1549 (2)	0.04172 (19)	0.0409 (3)
C3	0.19499 (5)	0.1459 (2)	0.1012 (2)	0.0465 (3)
C4	0.21068 (5)	0.2464 (3)	0.2544 (2)	0.0502 (4)
C5	0.17807 (6)	0.3577 (3)	0.3486 (2)	0.0518 (4)
C6	0.12982 (5)	0.3711 (2)	0.2890 (2)	0.0447 (3)
C7	0.03550 (4)	0.14969 (17)	0.04270 (16)	0.0322 (3)
C8	−0.01346 (4)	0.19858 (19)	−0.02702 (18)	0.0367 (3)
C9	0.04658 (4)	−0.05971 (19)	0.06856 (17)	0.0351 (3)
H2	0.1358 (6)	0.086 (3)	−0.071 (2)	0.051 (5)*
H3	0.2183 (7)	0.067 (3)	0.028 (3)	0.057 (5)*
H4	0.2463 (8)	0.239 (3)	0.296 (3)	0.061 (5)*
H5	0.1881 (8)	0.430 (3)	0.461 (3)	0.072 (6)*
H6	0.1066 (7)	0.449 (3)	0.354 (3)	0.060 (5)*
H8	−0.0220 (6)	0.334 (3)	−0.044 (2)	0.045 (4)*
H9	0.0793 (6)	−0.093 (3)	0.118 (2)	0.046 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0318 (5)	0.0334 (5)	0.0516 (6)	−0.0026 (4)	−0.0036 (4)	−0.0025 (4)
C1	0.0311 (6)	0.0309 (5)	0.0443 (6)	−0.0047 (4)	−0.0022 (4)	0.0009 (5)
C2	0.0364 (7)	0.0415 (7)	0.0448 (7)	−0.0027 (5)	−0.0006 (5)	−0.0047 (5)
C3	0.0339 (7)	0.0473 (8)	0.0582 (8)	0.0006 (6)	0.0018 (6)	−0.0015 (6)
C4	0.0348 (7)	0.0528 (9)	0.0621 (9)	−0.0039 (6)	−0.0100 (6)	0.0032 (7)
C5	0.0454 (8)	0.0538 (9)	0.0553 (8)	−0.0062 (7)	−0.0126 (6)	−0.0096 (7)
C6	0.0390 (7)	0.0421 (7)	0.0530 (8)	−0.0034 (6)	−0.0021 (5)	−0.0110 (6)
C7	0.0291 (5)	0.0321 (6)	0.0353 (5)	−0.0011 (4)	−0.0010 (4)	−0.0009 (4)
C8	0.0301 (6)	0.0310 (6)	0.0489 (7)	0.0010 (5)	−0.0029 (5)	0.0017 (5)
C9	0.0287 (5)	0.0337 (6)	0.0426 (6)	0.0005 (4)	−0.0032 (4)	0.0018 (5)

Geometric parameters (Å, º)

N1—C1	1.413 (2)	C5—C6	1.386 (2)
N1—C7	1.297 (2)	C5—H5	1.00 (2)
C1—C2	1.395 (2)	C6—H6	0.97 (2)
C1—C6	1.392 (2)	C7—C8	1.462 (2)
C2—C3	1.389 (2)	C7—C9	1.462 (2)
C2—H2	0.99 (2)	C8—C9^i	1.337 (2)
C3—C4	1.381 (2)	C8—H8	0.96 (2)
C3—H3	1.01 (2)	C9—C8^i	1.337 (2)
C4—C5	1.380 (2)	C9—H9	0.99 (2)
C4—H4	1.02 (2)
C7—N1—C1	121.7 (1)	C6—C5—H5	117.8 (12)
C2—C1—C6	119.3 (1)	C4—C5—H5	121.8 (12)
C2—C1—N1	123.3 (1)	C5—C6—C1	120.2 (1)
C6—C1—N1	117.2 (1)	C5—C6—H6	121.1 (12)
C1—C2—C3	119.8 (1)	C1—C6—H6	118.7 (12)
C1—C2—H2	120.2 (10)	C9—C7—C8	116.8 (1)
C3—C2—H2	120.0 (10)	C9—C7—N1	126.5 (1)
C4—C3—C2	120.5 (1)	C8—C7—N1	116.7 (1)
C4—C3—H3	121.1 (11)	C9^i—C8—C7	122.2 (1)
C2—C3—H3	118.3 (11)	C7—C8—H8	119.0 (10)
C3—C4—C5	119.8 (1)	C9^i—C8—H8	118.8 (10)
C3—C4—H4	119.5 (11)	C8^i—C9—C7	121.0 (1)
C5—C4—H4	120.7 (11)	C7—C9—H9	117.1 (10)
C6—C5—C4	120.3 (1)	C8^i—C9—H9	121.9 (10)
C7—N1—C1—C2	55.8 (2)	C2—C1—C6—C5	−2.1 (2)
C7—N1—C1—C6	−130.2 (1)	N1—C1—C6—C5	−176.4 (1)
C6—C1—C2—C3	0.9 (2)	C1—N1—C7—C9	4.1 (2)
N1—C1—C2—C3	174.8 (1)	C1—N1—C7—C8	−176.8 (1)
C1—C2—C3—C4	0.4 (2)	C9—C7—C8—C9^i	−1.1 (2)
C2—C3—C4—C5	−0.4 (3)	N1—C7—C8—C9^i	179.7 (1)
C3—C4—C5—C6	−0.8 (3)	C8—C7—C9—C8^i	1.1 (2)
C4—C5—C6—C1	2.1 (3)	N1—C7—C9—C8^i	−179.8 (1)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1^ii	0.97 (2)	2.68 (2)	3.624 (2)	164 (2)

Symmetry code: (ii) x, −y+1, z+1/2.

(II) N,N'-diphenyl-1,4-phenylenediamine

Crystal data

C18H16N2	Dx = 1.293 Mg m^−3
Mr = 260.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 38 reflections
a = 25.678 (4) Å	θ = 1.6–11.1°
b = 7.4815 (13) Å	µ = 0.08 mm^−1
c = 6.9588 (12) Å	T = 295 K
V = 1336.9 (4) Å^3	Plate, colourless
Z = 4	0.40 × 0.28 × 0.08 mm
F(000) = 552

Data collection

Kuma KM-4 four-circle diffractometer	Rint = 0.036
Radiation source: fine-focus sealed tube	θmax = 25.7°, θmin = 1.6°
Graphite monochromator	h = −31→31
θ/2θ scans	k = −9→9
6410 measured reflections	l = −4→8
1269 independent reflections	3 standard reflections every 50 reflections
931 reflections with I > 2σ(I)	intensity decay: 0.1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: difference Fourier map
wR(F^2) = 0.133	All H-atom parameters refined
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0391P)^2 + 0.8676P] where P = (Fo^2 + 2Fc^2)/3
1269 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.55620 (8)	0.4452 (3)	0.1576 (3)	0.0509 (6)
C1	0.60827 (9)	0.4780 (3)	0.1085 (3)	0.0405 (6)
C2	0.63875 (10)	0.6114 (4)	0.1871 (3)	0.0456 (6)
C3	0.68990 (10)	0.6322 (4)	0.1263 (4)	0.0522 (7)
C4	0.71117 (10)	0.5234 (4)	−0.0113 (4)	0.0567 (8)
C5	0.67998 (11)	0.3961 (4)	−0.0962 (4)	0.0564 (8)
C6	0.62949 (11)	0.3733 (4)	−0.0374 (4)	0.0506 (7)
C7	0.52980 (9)	0.4772 (3)	0.3319 (3)	0.0390 (6)
C8	0.47676 (9)	0.4446 (4)	0.3342 (3)	0.0424 (6)
C9	0.55274 (9)	0.5347 (4)	0.5006 (3)	0.0461 (6)
H1	0.5385 (10)	0.366 (4)	0.083 (4)	0.052 (8)*
H2	0.6248 (10)	0.699 (4)	0.269 (4)	0.059 (8)*
H3	0.7108 (9)	0.724 (4)	0.183 (4)	0.052 (7)*
H4	0.7480 (12)	0.537 (4)	−0.048 (4)	0.062 (8)*
H5	0.6917 (11)	0.314 (4)	−0.198 (5)	0.083 (10)*
H6	0.6091 (10)	0.292 (4)	−0.092 (4)	0.063 (9)*
H8	0.4617 (8)	0.409 (3)	0.223 (3)	0.038 (6)*
H9	0.5901 (10)	0.560 (4)	0.512 (4)	0.063 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0440 (12)	0.0741 (16)	0.0345 (11)	−0.0116 (11)	0.0032 (9)	−0.0149 (11)
C1	0.0396 (13)	0.0514 (14)	0.0303 (11)	0.0049 (11)	0.0003 (10)	0.0049 (11)
C2	0.0478 (15)	0.0531 (16)	0.0358 (13)	0.0012 (12)	0.0017 (11)	−0.0037 (12)
C3	0.0480 (15)	0.0648 (18)	0.0438 (15)	−0.0076 (14)	−0.0033 (12)	0.0012 (13)
C4	0.0434 (14)	0.078 (2)	0.0491 (16)	0.0015 (14)	0.0059 (13)	0.0058 (15)
C5	0.0559 (17)	0.0675 (19)	0.0458 (15)	0.0054 (14)	0.0108 (13)	−0.0066 (14)
C6	0.0541 (16)	0.0580 (17)	0.0396 (14)	−0.0055 (13)	0.0032 (12)	−0.0084 (13)
C7	0.0418 (13)	0.0434 (13)	0.0319 (11)	0.0006 (10)	0.0018 (10)	−0.0005 (11)
C8	0.0434 (14)	0.0525 (15)	0.0313 (12)	−0.0047 (11)	−0.0048 (10)	−0.0041 (12)
C9	0.0360 (13)	0.0652 (17)	0.0372 (12)	−0.0059 (12)	−0.0033 (11)	−0.0033 (12)

Geometric parameters (Å, º)

N1—C1	1.402 (3)	C4—H4	0.99 (3)
N1—C7	1.410 (3)	C5—C6	1.370 (4)
N1—H1	0.91 (3)	C5—H5	0.98 (3)
C1—C2	1.381 (3)	C6—H6	0.89 (3)
C1—C6	1.393 (3)	C7—C8	1.384 (3)
C2—C3	1.389 (4)	C7—C9	1.382 (3)
C2—H2	0.94 (3)	C8—C9^i	1.386 (3)
C3—C4	1.370 (4)	C8—H8	0.90 (2)
C3—H3	0.96 (3)	C9—C8^i	1.386 (3)
C4—C5	1.377 (4)	C9—H9	0.98 (3)
C1—N1—C7	129.7 (2)	C6—C5—C4	120.5 (3)
C1—N1—H1	117 (2)	C6—C5—H5	115 (2)
C7—N1—H1	111 (2)	C4—C5—H5	124 (2)
C2—C1—C6	118.2 (2)	C5—C6—C1	121.2 (3)
C2—C1—N1	124.8 (2)	C5—C6—H6	121 (2)
C6—C1—N1	116.9 (2)	C1—C6—H6	118 (2)
C1—C2—C3	119.7 (2)	C9—C7—C8	117.7 (2)
C1—C2—H2	122 (2)	C9—C7—N1	125.4 (2)
C3—C2—H2	118 (2)	C8—C7—N1	117.0 (2)
C4—C3—C2	121.6 (3)	C7—C8—C9^i	121.9 (2)
C4—C3—H3	120 (2)	C7—C8—H8	118 (1)
C2—C3—H3	119 (2)	C9^i—C8—H8	121 (1)
C3—C4—C5	118.6 (3)	C7—C9—C8^i	120.4 (2)
C3—C4—H4	120 (2)	C7—C9—H9	123 (2)
C5—C4—H4	121 (2)	C8^i—C9—H9	117 (2)
C7—N1—C1—C2	−28.5 (4)	C2—C1—C6—C5	2.8 (4)
C7—N1—C1—C6	154.9 (3)	N1—C1—C6—C5	179.6 (3)
C6—C1—C2—C3	−3.0 (4)	C1—N1—C7—C9	−6.6 (4)
N1—C1—C2—C3	−179.6 (2)	C1—N1—C7—C8	174.8 (3)
C1—C2—C3—C4	0.2 (4)	C9—C7—C8—C9^i	−1.1 (4)
C2—C3—C4—C5	2.9 (4)	N1—C7—C8—C9^i	177.6 (2)
C3—C4—C5—C6	−3.2 (4)	C8—C7—C9—C8^i	1.1 (4)
C4—C5—C6—C1	0.3 (4)	N1—C7—C9—C8^i	−177.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···C7^ii	0.91 (3)	3.45 (3)	4.140 (3)	135 (2)
N1—H1···C8^ii	0.91 (3)	3.23 (3)	3.840 (4)	127 (2)
N1—H1···C9^ii	0.91 (3)	3.46 (3)	4.297 (3)	154 (2)
N1—H1···C9^iii	0.91 (3)	3.08 (3)	3.754 (4)	133 (2)
N1—H1···C8^iii	0.91 (3)	3.31 (3)	4.211 (3)	176 (2)
N1—H1···C7^iii	0.91 (3)	3.12 (3)	3.947 (3)	153 (2)

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

(III) N,N'-diphenyl-1,4-phenylenediammonium bis(4-toluenesulfonate)

Crystal data

C18H18N2^2+·2C7H7O3S^−	Z = 2
Mr = 604.72	F(000) = 636
Monoclinic, P21/a	Dx = 1.344 Mg m^−3
a = 10.9886 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3322 (4) Å	µ = 0.23 mm^−1
c = 11.9612 (5) Å	T = 293 K
β = 112.8293 (2)°	Plate, green
V = 1493.93 (10) Å^3	0.39 × 0.37 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer	2635 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.090
Horizontally mounted graphite crystal monochromator	θmax = 27.4°, θmin = 3.3°
Detector resolution: 9 pixels mm^-1	h = −14→14
ϕ and ω scans to fill Ewald sphere	k = −15→15
11246 measured reflections	l = −15→15
3325 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.066	Hydrogen site location: difference Fourier map
wR(F^2) = 0.196	All H-atom parameters refined
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1076P)^2 + 1.0838P] where P = (Fo^2 + 2Fc^2)/3
3325 reflections	(Δ/σ)max = 0.003
254 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	1.1633 (2)	0.67698 (18)	0.4933 (2)	0.0457 (5)
C1	1.1522 (2)	0.7095 (2)	0.3712 (2)	0.0469 (6)
C2	1.0797 (3)	0.8003 (2)	0.3172 (3)	0.0565 (7)
C3	1.0688 (4)	0.8287 (3)	0.2015 (3)	0.0702 (9)
C4	1.1301 (4)	0.7664 (4)	0.1427 (3)	0.0758 (10)
C5	1.2046 (4)	0.6775 (3)	0.1990 (4)	0.0726 (9)
C6	1.2174 (3)	0.6476 (3)	0.3143 (3)	0.0596 (7)
C7	1.0783 (2)	0.58455 (19)	0.4960 (2)	0.0423 (5)
C8	1.1360 (2)	0.4934 (2)	0.5606 (3)	0.0542 (7)
C9	0.9428 (3)	0.5927 (2)	0.4352 (3)	0.0558 (7)
S1	0.94584 (6)	0.12864 (5)	0.32255 (6)	0.0466 (2)
O11	0.8789 (4)	0.1400 (2)	0.4046 (3)	0.0940 (10)
O12	0.8850 (4)	0.0439 (2)	0.2382 (3)	0.0947 (10)
O13	1.0849 (3)	0.1158 (3)	0.3807 (4)	0.1260 (16)
C11	0.9187 (2)	0.2527 (2)	0.2414 (2)	0.0444 (5)
C12	0.7906 (3)	0.2818 (3)	0.1659 (3)	0.0562 (7)
C13	0.7693 (3)	0.3807 (3)	0.1067 (3)	0.0645 (8)
C14	0.8727 (3)	0.4508 (2)	0.1198 (3)	0.0581 (7)
C15	0.9990 (3)	0.4201 (3)	0.1946 (3)	0.0639 (8)
C16	1.0217 (3)	0.3221 (3)	0.2554 (3)	0.0578 (7)
C17	0.8502 (6)	0.5590 (4)	0.0549 (5)	0.0865 (12)
H10	1.140 (3)	0.731 (3)	0.526 (3)	0.058 (9)*
H11	1.252 (4)	0.661 (3)	0.543 (3)	0.062 (9)*
H2	1.044 (4)	0.844 (3)	0.360 (3)	0.060 (9)*
H3	1.028 (4)	0.898 (4)	0.167 (4)	0.084 (12)*
H4	1.127 (4)	0.791 (3)	0.057 (4)	0.089 (12)*
H5	1.248 (6)	0.635 (4)	0.152 (6)	0.119 (17)*
H6	1.271 (4)	0.583 (3)	0.357 (4)	0.075 (11)*
H8	1.231 (4)	0.486 (3)	0.608 (4)	0.076 (11)*
H9	0.904 (4)	0.650 (3)	0.383 (3)	0.068 (10)*
H12	0.724 (4)	0.241 (3)	0.166 (3)	0.056 (9)*
H13	0.679 (5)	0.395 (4)	0.058 (4)	0.092 (13)*
H15	1.071 (5)	0.476 (4)	0.204 (4)	0.087 (12)*
H16	1.110 (4)	0.305 (3)	0.306 (4)	0.077 (11)*
H171	0.867 (6)	0.623 (5)	0.110 (6)	0.13 (2)*
H172	0.759 (6)	0.556 (4)	0.004 (5)	0.108 (17)*
H173	0.897 (8)	0.567 (7)	0.009 (7)	0.16 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0369 (10)	0.0419 (11)	0.0580 (13)	−0.0028 (8)	0.0182 (10)	−0.0038 (9)
C1	0.0377 (11)	0.0460 (12)	0.0585 (14)	−0.0083 (10)	0.0203 (11)	−0.0058 (10)
C2	0.0520 (15)	0.0521 (14)	0.0667 (17)	−0.0022 (12)	0.0244 (14)	−0.0015 (13)
C3	0.074 (2)	0.0651 (19)	0.0690 (19)	−0.0076 (16)	0.0243 (17)	0.0086 (16)
C4	0.082 (2)	0.088 (2)	0.064 (2)	−0.020 (2)	0.0354 (19)	−0.0030 (17)
C5	0.075 (2)	0.078 (2)	0.080 (2)	−0.0160 (18)	0.0472 (19)	−0.0197 (18)
C6	0.0543 (16)	0.0567 (16)	0.0763 (19)	−0.0074 (13)	0.0345 (15)	−0.0125 (14)
C7	0.0326 (11)	0.0419 (11)	0.0519 (13)	−0.0013 (9)	0.0158 (10)	−0.0030 (10)
C8	0.0287 (11)	0.0530 (14)	0.0717 (17)	0.0025 (10)	0.0093 (11)	0.0085 (13)
C9	0.0335 (12)	0.0491 (14)	0.0758 (18)	0.0064 (10)	0.0115 (12)	0.0152 (13)
S1	0.0372 (4)	0.0442 (4)	0.0542 (4)	0.0020 (2)	0.0131 (3)	−0.0022 (2)
O11	0.159 (3)	0.0579 (13)	0.102 (2)	0.0244 (16)	0.090 (2)	0.0137 (13)
O12	0.133 (3)	0.0531 (13)	0.0793 (16)	−0.0122 (15)	0.0206 (17)	−0.0119 (12)
O13	0.0349 (12)	0.102 (2)	0.193 (4)	−0.0036 (12)	−0.0091 (16)	0.073 (2)
C11	0.0397 (12)	0.0466 (12)	0.0453 (12)	0.0020 (10)	0.0149 (10)	−0.0035 (10)
C12	0.0378 (13)	0.0605 (16)	0.0608 (16)	−0.0022 (12)	0.0088 (12)	−0.0001 (12)
C13	0.0492 (16)	0.0707 (19)	0.0610 (17)	0.0132 (14)	0.0077 (14)	0.0050 (14)
C14	0.0690 (18)	0.0516 (14)	0.0524 (14)	0.0043 (13)	0.0219 (13)	0.0006 (12)
C15	0.0579 (17)	0.0601 (17)	0.0702 (18)	−0.0099 (14)	0.0211 (15)	0.0047 (14)
C16	0.0389 (13)	0.0624 (16)	0.0645 (17)	−0.0029 (12)	0.0118 (12)	0.0078 (13)
C17	0.108 (4)	0.062 (2)	0.086 (3)	0.014 (2)	0.034 (3)	0.020 (2)

Geometric parameters (Å, º)

N1—C1	1.473 (4)	C9—H9	0.93 (4)
N1—C7	1.482 (3)	S1—O13	1.421 (3)
N1—H10	0.86 (4)	S1—O12	1.426 (3)
N1—H11	0.95 (4)	S1—O11	1.443 (3)
C1—C2	1.381 (4)	S1—C11	1.774 (3)
C1—C6	1.392 (4)	C11—C16	1.376 (4)
C2—C3	1.387 (5)	C11—C12	1.392 (4)
C2—H2	0.92 (4)	C12—C13	1.384 (5)
C3—C4	1.381 (6)	C12—H12	0.89 (4)
C3—H3	0.98 (4)	C13—C14	1.388 (5)
C4—C5	1.377 (6)	C13—H13	0.96 (5)
C4—H4	1.06 (4)	C14—C15	1.380 (5)
C5—C6	1.382 (5)	C14—C17	1.515 (5)
C5—H5	1.01 (6)	C15—C16	1.384 (4)
C6—H6	1.00 (4)	C15—H15	1.02 (5)
C7—C8	1.372 (4)	C16—H16	0.95 (4)
C7—C9	1.384 (3)	C17—H171	1.00 (7)
C8—C9^i	1.383 (4)	C17—H172	0.95 (6)
C8—H8	0.97 (4)	C17—H173	0.89 (9)
C9—C8^i	1.383 (4)
C1—N1—C7	114.9 (2)	C8^i—C9—H9	118 (2)
C1—N1—H10	108 (2)	O13—S1—O12	112.6 (3)
C7—N1—H10	107 (2)	O13—S1—O11	114.4 (3)
C1—N1—H11	110 (2)	O12—S1—O11	109.2 (2)
C7—N1—H11	110 (2)	O13—S1—C11	106.5 (1)
H10—N1—H11	107 (3)	O12—S1—C11	108.1 (1)
C2—C1—C6	122.0 (3)	O11—S1—C11	105.5 (1)
C2—C1—N1	119.7 (2)	C16—C11—C12	119.7 (3)
C6—C1—N1	118.3 (3)	C16—C11—S1	120.9 (2)
C1—C2—C3	118.8 (3)	C12—C11—S1	119.4 (2)
C1—C2—H2	120 (2)	C13—C12—C11	119.1 (3)
C3—C2—H2	121 (2)	C13—C12—H12	122 (2)
C4—C3—C2	119.9 (4)	C11—C12—H12	119 (2)
C4—C3—H3	120 (2)	C12—C13—C14	121.5 (3)
C2—C3—H3	119 (2)	C12—C13—H13	114 (3)
C3—C4—C5	120.6 (3)	C14—C13—H13	124 (3)
C3—C4—H4	120 (2)	C15—C14—C13	118.4 (3)
C5—C4—H4	119 (2)	C15—C14—C17	119.8 (4)
C6—C5—C4	120.8 (3)	C13—C14—C17	121.8 (4)
C6—C5—H5	122 (3)	C14—C15—C16	120.7 (3)
C4—C5—H5	117 (3)	C14—C15—H15	115 (3)
C5—C6—C1	118.0 (3)	C16—C15—H15	124 (3)
C5—C6—H6	122 (2)	C11—C16—C15	120.5 (3)
C1—C6—H6	120 (2)	C11—C16—H16	122 (2)
C9—C7—C8	121.6 (2)	C15—C16—H16	118 (2)
C9—C7—N1	119.4 (2)	C14—C17—H171	114 (4)
C8—C7—N1	119.0 (2)	C14—C17—H172	102 (3)
C7—C8—C9^i	119.3 (2)	H171—C17—H172	109 (5)
C7—C8—H8	124 (2)	C14—C17—H173	113 (5)
C9^i—C8—H8	117 (2)	H171—C17—H173	108 (6)
C8^i—C9—C7	119.1 (2)	H172—C17—H173	109 (6)
C7—C9—H9	122 (2)
C7—N1—C1—C2	102.6 (3)	O13—S1—C11—C16	−8.3 (4)
C7—N1—C1—C6	−78.2 (3)	O12—S1—C11—C16	−129.6 (3)
C6—C1—C2—C3	1.8 (4)	O11—S1—C11—C16	113.6 (3)
N1—C1—C2—C3	−179.0 (3)	O13—S1—C11—C12	174.1 (3)
C1—C2—C3—C4	−0.1 (5)	O12—S1—C11—C12	52.8 (3)
C2—C3—C4—C5	−1.4 (6)	O11—S1—C11—C12	−64.0 (3)
C3—C4—C5—C6	1.3 (6)	C16—C11—C12—C13	−0.3 (4)
C4—C5—C6—C1	0.4 (5)	S1—C11—C12—C13	177.3 (2)
C2—C1—C6—C5	−2.0 (4)	C11—C12—C13—C14	0.7 (5)
N1—C1—C6—C5	178.9 (3)	C12—C13—C14—C15	−0.4 (5)
C1—N1—C7—C8	121.9 (3)	C12—C13—C14—C17	179.8 (4)
C1—N1—C7—C9	−59.1 (3)	C13—C14—C15—C16	−0.4 (5)
C9—C7—C8—C9^i	0.3 (5)	C17—C14—C15—C16	179.5 (4)
N1—C7—C8—C9^i	179.2 (3)	C12—C11—C16—C15	−0.4 (5)
C8—C7—C9—C8^i	−0.3 (5)	S1—C11—C16—C15	−178.0 (3)
N1—C7—C9—C8^i	−179.2 (3)	C14—C15—C16—C11	0.8 (5)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O13^ii	0.95 (4)	1.75 (4)	2.695 (4)	171 (3)
N1—H10···O11^i	0.86 (4)	1.84 (4)	2.691 (3)	169 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+5/2, y+1/2, −z+1.