The title compound, C
6H
10N
22+·2C
7H
7O
3S
−, is a proton-transfer compound obtained from 1,4-phenylenediamine and toluene-4-sulfonic acid. The cations and anions are linked by intermolecular N—H
O hydrogen bonds, forming a three-dimensional network.
Supporting information
CCDC reference: 628076
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.003 Å
- R factor = 0.039
- wR factor = 0.140
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O2 .. 2.84 Ang.
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.68 mm
PLAT430_ALERT_2_C Short Inter D...A Contact O1 .. O1 .. 2.85 Ang.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Siemens, 1991); software used to prepare material for publication: SHELXTL/PC.
1,4-Phenylenediaminium bis(toluene-4-sulfonate)
top
Crystal data top
C6H10N22+·2C7H7O3S− | F(000) = 952 |
Mr = 452.53 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 16364 reflections |
a = 15.6885 (6) Å | θ = 3.1–27.5° |
b = 7.0857 (2) Å | µ = 0.31 mm−1 |
c = 18.3270 (6) Å | T = 153 K |
β = 96.800 (1)° | Prism, red |
V = 2022.97 (12) Å3 | 0.68 × 0.56 × 0.36 mm |
Z = 4 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4639 independent reflections |
Radiation source: Rotating Anode | 3765 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −20→16 |
Tmin = 0.819, Tmax = 0.898 | k = −9→9 |
18493 measured reflections | l = −23→23 |
Refinement top
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0869P)2 + 1.197P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
4639 reflections | Δρmax = 0.44 e Å−3 |
276 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0145 (15) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.12378 (3) | 0.23186 (6) | 0.53770 (2) | 0.01220 (15) | |
S2 | 0.53295 (3) | 0.24479 (6) | 0.73086 (2) | 0.01341 (15) | |
O1 | 0.08693 (8) | 0.06134 (19) | 0.50251 (7) | 0.0189 (3) | |
O2 | 0.07902 (8) | 0.40057 (19) | 0.50844 (7) | 0.0185 (3) | |
O3 | 0.13193 (9) | 0.2210 (2) | 0.61769 (8) | 0.0238 (4) | |
O4 | 0.48907 (9) | 0.4151 (2) | 0.70131 (8) | 0.0216 (3) | |
O5 | 0.49077 (9) | 0.0742 (2) | 0.69934 (8) | 0.0205 (3) | |
O6 | 0.54578 (10) | 0.2423 (2) | 0.81086 (8) | 0.0246 (4) | |
C1 | 0.48157 (13) | 0.2839 (3) | 0.44439 (12) | 0.0237 (4) | |
H1D | 0.5250 | 0.2850 | 0.4875 | 0.028* | |
H1E | 0.4861 | 0.3999 | 0.4160 | 0.028* | |
H1F | 0.4909 | 0.1744 | 0.4136 | 0.028* | |
C2 | 0.39323 (12) | 0.2719 (3) | 0.46916 (11) | 0.0159 (4) | |
C3 | 0.32116 (12) | 0.3293 (3) | 0.42191 (10) | 0.0169 (4) | |
H3 | 0.3283 | 0.3774 | 0.3746 | 0.020* | |
C4 | 0.23951 (12) | 0.3169 (3) | 0.44337 (10) | 0.0153 (4) | |
H4 | 0.1910 | 0.3553 | 0.4108 | 0.018* | |
C5 | 0.22900 (11) | 0.2477 (2) | 0.51280 (10) | 0.0115 (4) | |
C6 | 0.29973 (11) | 0.1898 (3) | 0.56073 (10) | 0.0150 (4) | |
H6 | 0.2925 | 0.1429 | 0.6082 | 0.018* | |
C7 | 0.38116 (12) | 0.2018 (3) | 0.53809 (10) | 0.0177 (4) | |
H7 | 0.4295 | 0.1613 | 0.5704 | 0.021* | |
C8 | 0.88894 (14) | 0.2468 (3) | 0.63150 (13) | 0.0237 (5) | |
H8A | 0.9176 | 0.1284 | 0.6473 | 0.028* | |
H8B | 0.9221 | 0.3534 | 0.6541 | 0.028* | |
H8C | 0.8849 | 0.2572 | 0.5779 | 0.028* | |
C9 | 0.80010 (13) | 0.2492 (2) | 0.65498 (11) | 0.0158 (4) | |
C10 | 0.78632 (12) | 0.3198 (3) | 0.72362 (10) | 0.0168 (4) | |
H10 | 0.8335 | 0.3690 | 0.7551 | 0.020* | |
C11 | 0.70544 (12) | 0.3200 (3) | 0.74702 (10) | 0.0156 (4) | |
H11 | 0.6974 | 0.3697 | 0.7939 | 0.019* | |
C12 | 0.63614 (12) | 0.2466 (2) | 0.70117 (10) | 0.0131 (4) | |
C13 | 0.64816 (12) | 0.1749 (3) | 0.63244 (10) | 0.0154 (4) | |
H13 | 0.6009 | 0.1250 | 0.6012 | 0.018* | |
C14 | 0.72948 (12) | 0.1766 (3) | 0.60970 (10) | 0.0165 (4) | |
H14 | 0.7374 | 0.1278 | 0.5627 | 0.020* | |
N1 | 0.42517 (10) | 0.2427 (2) | 0.91410 (9) | 0.0136 (3) | |
H1A | 0.4328 | 0.1353 | 0.9414 | 0.016* | |
H1B | 0.4322 | 0.3449 | 0.9443 | 0.016* | |
H1C | 0.4644 | 0.2466 | 0.8813 | 0.016* | |
N2 | 0.08850 (10) | 0.2509 (2) | 0.75958 (9) | 0.0132 (3) | |
H2A | 0.0607 | 0.3578 | 0.7708 | 0.016* | |
H2B | 0.0588 | 0.1482 | 0.7724 | 0.016* | |
H2C | 0.0924 | 0.2479 | 0.7104 | 0.016* | |
C15 | 0.33835 (12) | 0.2444 (2) | 0.87438 (10) | 0.0125 (4) | |
C16 | 0.32571 (11) | 0.3107 (3) | 0.80296 (10) | 0.0145 (4) | |
H16 | 0.3731 | 0.3537 | 0.7797 | 0.017* | |
C17 | 0.24328 (12) | 0.3142 (3) | 0.76540 (10) | 0.0142 (4) | |
H17 | 0.2337 | 0.3609 | 0.7165 | 0.017* | |
C18 | 0.17532 (11) | 0.2487 (2) | 0.80014 (10) | 0.0118 (4) | |
C19 | 0.18746 (11) | 0.1829 (3) | 0.87163 (10) | 0.0148 (4) | |
H19 | 0.1401 | 0.1389 | 0.8947 | 0.018* | |
C20 | 0.26989 (11) | 0.1818 (3) | 0.90953 (10) | 0.0144 (4) | |
H20 | 0.2792 | 0.1387 | 0.9589 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0093 (2) | 0.0145 (2) | 0.0124 (2) | −0.00015 (15) | −0.00017 (16) | −0.00054 (16) |
S2 | 0.0146 (2) | 0.0127 (2) | 0.0131 (2) | 0.00018 (15) | 0.00242 (17) | 0.00123 (16) |
O1 | 0.0172 (7) | 0.0158 (7) | 0.0230 (7) | −0.0050 (5) | −0.0003 (5) | −0.0002 (6) |
O2 | 0.0131 (6) | 0.0164 (7) | 0.0252 (7) | 0.0034 (5) | −0.0020 (5) | −0.0026 (6) |
O3 | 0.0164 (7) | 0.0424 (9) | 0.0128 (7) | 0.0009 (6) | 0.0024 (5) | −0.0004 (6) |
O4 | 0.0211 (7) | 0.0163 (7) | 0.0282 (8) | 0.0052 (6) | 0.0059 (6) | 0.0039 (6) |
O5 | 0.0208 (7) | 0.0162 (7) | 0.0247 (7) | −0.0059 (5) | 0.0036 (5) | −0.0003 (6) |
O6 | 0.0204 (7) | 0.0405 (9) | 0.0133 (7) | 0.0009 (6) | 0.0041 (5) | 0.0011 (6) |
C1 | 0.0170 (10) | 0.0271 (11) | 0.0282 (11) | −0.0015 (8) | 0.0082 (8) | −0.0001 (9) |
C2 | 0.0140 (9) | 0.0138 (9) | 0.0203 (9) | −0.0009 (7) | 0.0036 (7) | −0.0022 (7) |
C3 | 0.0207 (9) | 0.0154 (9) | 0.0149 (8) | 0.0000 (7) | 0.0038 (7) | 0.0030 (8) |
C4 | 0.0159 (9) | 0.0151 (9) | 0.0142 (8) | 0.0023 (7) | −0.0008 (7) | 0.0013 (7) |
C5 | 0.0095 (8) | 0.0102 (8) | 0.0147 (8) | −0.0001 (6) | 0.0003 (6) | −0.0017 (7) |
C6 | 0.0139 (8) | 0.0174 (9) | 0.0133 (8) | 0.0019 (7) | −0.0005 (6) | 0.0013 (7) |
C7 | 0.0124 (8) | 0.0222 (10) | 0.0177 (9) | 0.0028 (7) | −0.0017 (7) | 0.0006 (8) |
C8 | 0.0182 (10) | 0.0249 (11) | 0.0288 (11) | 0.0014 (8) | 0.0062 (8) | −0.0003 (9) |
C9 | 0.0168 (9) | 0.0105 (8) | 0.0202 (9) | 0.0010 (6) | 0.0033 (7) | 0.0018 (7) |
C10 | 0.0177 (9) | 0.0129 (9) | 0.0189 (9) | −0.0021 (7) | −0.0013 (7) | −0.0013 (8) |
C11 | 0.0208 (9) | 0.0115 (9) | 0.0142 (8) | −0.0001 (7) | 0.0009 (7) | −0.0025 (7) |
C12 | 0.0151 (9) | 0.0101 (8) | 0.0141 (8) | 0.0007 (6) | 0.0018 (7) | 0.0017 (7) |
C13 | 0.0182 (9) | 0.0137 (9) | 0.0136 (8) | −0.0017 (7) | −0.0008 (7) | −0.0004 (7) |
C14 | 0.0227 (10) | 0.0142 (9) | 0.0128 (8) | 0.0010 (7) | 0.0029 (7) | 0.0001 (7) |
N1 | 0.0129 (7) | 0.0136 (8) | 0.0136 (7) | 0.0004 (5) | −0.0007 (6) | 0.0003 (6) |
N2 | 0.0105 (7) | 0.0139 (8) | 0.0151 (7) | 0.0001 (5) | 0.0008 (6) | −0.0011 (6) |
C15 | 0.0121 (8) | 0.0101 (8) | 0.0149 (8) | 0.0009 (6) | −0.0002 (7) | −0.0013 (7) |
C16 | 0.0130 (8) | 0.0145 (8) | 0.0162 (9) | −0.0024 (7) | 0.0022 (6) | 0.0027 (7) |
C17 | 0.0152 (8) | 0.0136 (8) | 0.0132 (8) | −0.0015 (7) | 0.0000 (6) | 0.0027 (7) |
C18 | 0.0101 (8) | 0.0090 (8) | 0.0157 (9) | 0.0008 (6) | −0.0008 (6) | −0.0021 (7) |
C19 | 0.0132 (8) | 0.0151 (9) | 0.0166 (9) | 0.0004 (7) | 0.0043 (7) | −0.0002 (7) |
C20 | 0.0166 (9) | 0.0141 (9) | 0.0125 (8) | 0.0023 (7) | 0.0019 (6) | 0.0021 (7) |
Geometric parameters (Å, º) top
S1—O2 | 1.4562 (13) | C9—C14 | 1.401 (3) |
S1—O1 | 1.4566 (14) | C10—C11 | 1.387 (3) |
S1—O3 | 1.4583 (14) | C10—H10 | 0.9500 |
S1—C5 | 1.7675 (18) | C11—C12 | 1.394 (3) |
S2—O6 | 1.4561 (14) | C11—H11 | 0.9500 |
S2—O4 | 1.4614 (14) | C12—C13 | 1.392 (3) |
S2—O5 | 1.4637 (14) | C13—C14 | 1.388 (3) |
S2—C12 | 1.7680 (19) | C13—H13 | 0.9500 |
C1—C2 | 1.511 (3) | C14—H14 | 0.9500 |
C1—H1D | 0.9800 | N1—C15 | 1.467 (2) |
C1—H1E | 0.9800 | N1—H1A | 0.9100 |
C1—H1F | 0.9800 | N1—H1B | 0.9100 |
C2—C7 | 1.391 (3) | N1—H1C | 0.9100 |
C2—C3 | 1.401 (3) | N2—C18 | 1.472 (2) |
C3—C4 | 1.387 (3) | N2—H2A | 0.9100 |
C3—H3 | 0.9500 | N2—H2B | 0.9100 |
C4—C5 | 1.391 (3) | N2—H2C | 0.9100 |
C4—H4 | 0.9500 | C15—C16 | 1.383 (2) |
C5—C6 | 1.393 (2) | C15—C20 | 1.389 (3) |
C6—C7 | 1.392 (3) | C16—C17 | 1.391 (2) |
C6—H6 | 0.9500 | C16—H16 | 0.9500 |
C7—H7 | 0.9500 | C17—C18 | 1.385 (3) |
C8—C9 | 1.507 (3) | C17—H17 | 0.9500 |
C8—H8A | 0.9800 | C18—C19 | 1.383 (2) |
C8—H8B | 0.9800 | C19—C20 | 1.394 (2) |
C8—H8C | 0.9800 | C19—H19 | 0.9500 |
C9—C10 | 1.394 (3) | C20—H20 | 0.9500 |
| | | |
O2—S1—O1 | 111.66 (8) | C11—C10—C9 | 121.65 (17) |
O2—S1—O3 | 113.22 (9) | C11—C10—H10 | 119.2 |
O1—S1—O3 | 112.61 (9) | C9—C10—H10 | 119.2 |
O2—S1—C5 | 106.09 (8) | C10—C11—C12 | 119.35 (17) |
O1—S1—C5 | 105.80 (8) | C10—C11—H11 | 120.3 |
O3—S1—C5 | 106.82 (8) | C12—C11—H11 | 120.3 |
O6—S2—O4 | 112.70 (9) | C13—C12—C11 | 120.15 (17) |
O6—S2—O5 | 112.93 (9) | C13—C12—S2 | 120.20 (14) |
O4—S2—O5 | 111.40 (9) | C11—C12—S2 | 119.64 (14) |
O6—S2—C12 | 106.71 (9) | C14—C13—C12 | 119.77 (17) |
O4—S2—C12 | 106.74 (8) | C14—C13—H13 | 120.1 |
O5—S2—C12 | 105.80 (8) | C12—C13—H13 | 120.1 |
C2—C1—H1D | 109.5 | C13—C14—C9 | 121.04 (17) |
C2—C1—H1E | 109.5 | C13—C14—H14 | 119.5 |
H1D—C1—H1E | 109.5 | C9—C14—H14 | 119.5 |
C2—C1—H1F | 109.5 | C15—N1—H1A | 109.5 |
H1D—C1—H1F | 109.5 | C15—N1—H1B | 109.5 |
H1E—C1—H1F | 109.5 | H1A—N1—H1B | 109.5 |
C7—C2—C3 | 118.59 (17) | C15—N1—H1C | 109.5 |
C7—C2—C1 | 121.41 (17) | H1A—N1—H1C | 109.5 |
C3—C2—C1 | 120.00 (18) | H1B—N1—H1C | 109.5 |
C4—C3—C2 | 120.75 (17) | C18—N2—H2A | 109.5 |
C4—C3—H3 | 119.6 | C18—N2—H2B | 109.5 |
C2—C3—H3 | 119.6 | H2A—N2—H2B | 109.5 |
C3—C4—C5 | 119.69 (16) | C18—N2—H2C | 109.5 |
C3—C4—H4 | 120.2 | H2A—N2—H2C | 109.5 |
C5—C4—H4 | 120.2 | H2B—N2—H2C | 109.5 |
C4—C5—C6 | 120.56 (17) | C16—C15—C20 | 121.03 (16) |
C4—C5—S1 | 118.29 (13) | C16—C15—N1 | 119.57 (16) |
C6—C5—S1 | 121.13 (14) | C20—C15—N1 | 119.40 (16) |
C7—C6—C5 | 119.00 (17) | C15—C16—C17 | 119.68 (16) |
C7—C6—H6 | 120.5 | C15—C16—H16 | 120.2 |
C5—C6—H6 | 120.5 | C17—C16—H16 | 120.2 |
C2—C7—C6 | 121.40 (17) | C18—C17—C16 | 119.18 (16) |
C2—C7—H7 | 119.3 | C18—C17—H17 | 120.4 |
C6—C7—H7 | 119.3 | C16—C17—H17 | 120.4 |
C9—C8—H8A | 109.5 | C19—C18—C17 | 121.44 (16) |
C9—C8—H8B | 109.5 | C19—C18—N2 | 119.81 (16) |
H8A—C8—H8B | 109.5 | C17—C18—N2 | 118.75 (16) |
C9—C8—H8C | 109.5 | C18—C19—C20 | 119.32 (16) |
H8A—C8—H8C | 109.5 | C18—C19—H19 | 120.3 |
H8B—C8—H8C | 109.5 | C20—C19—H19 | 120.3 |
C10—C9—C14 | 118.03 (18) | C15—C20—C19 | 119.34 (16) |
C10—C9—C8 | 120.61 (17) | C15—C20—H20 | 120.3 |
C14—C9—C8 | 121.34 (17) | C19—C20—H20 | 120.3 |
| | | |
C7—C2—C3—C4 | 0.1 (3) | O6—S2—C12—C13 | 154.14 (15) |
C1—C2—C3—C4 | 179.10 (17) | O4—S2—C12—C13 | −85.13 (16) |
C2—C3—C4—C5 | 0.4 (3) | O5—S2—C12—C13 | 33.63 (16) |
C3—C4—C5—C6 | −0.4 (3) | O6—S2—C12—C11 | −25.74 (17) |
C3—C4—C5—S1 | −179.38 (14) | O4—S2—C12—C11 | 94.99 (16) |
O2—S1—C5—C4 | −39.49 (16) | O5—S2—C12—C11 | −146.26 (15) |
O1—S1—C5—C4 | 79.25 (15) | C11—C12—C13—C14 | 0.0 (3) |
O3—S1—C5—C4 | −160.55 (15) | S2—C12—C13—C14 | −179.85 (14) |
O2—S1—C5—C6 | 141.54 (15) | C12—C13—C14—C9 | 0.2 (3) |
O1—S1—C5—C6 | −99.72 (16) | C10—C9—C14—C13 | 0.0 (3) |
O3—S1—C5—C6 | 20.48 (17) | C8—C9—C14—C13 | 178.38 (17) |
C4—C5—C6—C7 | −0.1 (3) | C20—C15—C16—C17 | −0.3 (3) |
S1—C5—C6—C7 | 178.82 (15) | N1—C15—C16—C17 | −179.39 (16) |
C3—C2—C7—C6 | −0.6 (3) | C15—C16—C17—C18 | −0.8 (3) |
C1—C2—C7—C6 | −179.63 (18) | C16—C17—C18—C19 | 1.0 (3) |
C5—C6—C7—C2 | 0.6 (3) | C16—C17—C18—N2 | −179.25 (16) |
C14—C9—C10—C11 | −0.3 (3) | C17—C18—C19—C20 | −0.2 (3) |
C8—C9—C10—C11 | −178.71 (18) | N2—C18—C19—C20 | −179.91 (16) |
C9—C10—C11—C12 | 0.5 (3) | C16—C15—C20—C19 | 1.1 (3) |
C10—C11—C12—C13 | −0.3 (3) | N1—C15—C20—C19 | −179.77 (16) |
C10—C11—C12—S2 | 179.53 (14) | C18—C19—C20—C15 | −0.9 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1i | 0.91 | 1.86 | 2.746 (2) | 164 |
N1—H1A···O2ii | 0.91 | 1.92 | 2.814 (2) | 167 |
N1—H1C···O6 | 0.91 | 1.92 | 2.830 (2) | 177 |
N2—H2C···O3 | 0.91 | 1.89 | 2.773 (2) | 164 |
N2—H2B···O4ii | 0.91 | 1.90 | 2.804 (2) | 172 |
N2—H2A···O5i | 0.91 | 1.85 | 2.754 (2) | 176 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2. |