The crystal structure of the anhydrous 1:1 proton-transfer compound of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with 4-aminobenzoic acid, viz. 4-carboxyanilinium 3-carboxy-4-hydroxybenzenesulfonate, C7H8NO2+·C7H5O6S−, displays a hydrogen-bonded polymeric network structure involving primarily all aminium H-atom donors and sulfonate O-atom acceptors, and is propagated through homomolecular cyclic tail-to-tail interactions between the carboxylic acid substituent groups of both cation and anion species. In addition, there are some cation–anion π–π stacking associations.
Supporting information
CCDC reference: 263689
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.002 Å
- R factor = 0.040
- wR factor = 0.117
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for O711 - C71 .. 12.97 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C11 - C61 .. 10.40 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C41 - C51 .. 15.58 su
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S5
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
2 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
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
4-carboxyanilinium 3-carboxy-4-hydroxybenzenesulfonate
top
Crystal data top
C7H8NO2+·C7H5O6S− | F(000) = 1472 |
Mr = 355.31 | Dx = 1.591 Mg m−3 |
Monoclinic, C2/c | Melting point: 520.2–522.0 (decomposition) K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 32.264 (3) Å | Cell parameters from 5543 reflections |
b = 7.6517 (7) Å | θ = 2.2–27.5° |
c = 12.0672 (11) Å | µ = 0.26 mm−1 |
β = 95.242 (2)° | T = 295 K |
V = 2966.6 (5) Å3 | Cut block, pale brown |
Z = 8 | 0.40 × 0.30 × 0.30 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3011 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.058 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
φ and ω scans | h = −32→41 |
8997 measured reflections | k = −9→9 |
3361 independent reflections | l = −13→15 |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0727P)2 + 1.1096P] where P = (Fo2 + 2Fc2)/3 |
3361 reflections | (Δ/σ)max = 0.001 |
241 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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 | |
S5 | 0.286144 (10) | 1.04900 (4) | 0.36352 (3) | 0.0278 (1) | |
O2 | 0.44023 (4) | 0.74973 (18) | 0.21549 (10) | 0.0446 (4) | |
O51 | 0.29822 (4) | 1.18682 (16) | 0.44260 (11) | 0.0473 (4) | |
O52 | 0.26749 (4) | 0.90349 (16) | 0.41780 (11) | 0.0481 (4) | |
O53 | 0.26144 (4) | 1.1087 (2) | 0.26601 (11) | 0.0607 (5) | |
O71 | 0.48044 (3) | 0.90583 (18) | 0.38494 (10) | 0.0450 (4) | |
O72 | 0.44446 (4) | 1.05993 (19) | 0.50015 (11) | 0.0520 (5) | |
C1 | 0.40719 (4) | 0.92840 (19) | 0.34718 (11) | 0.0288 (4) | |
C2 | 0.40597 (5) | 0.82465 (19) | 0.25054 (12) | 0.0313 (4) | |
C3 | 0.36806 (5) | 0.7956 (2) | 0.18831 (12) | 0.0354 (4) | |
C4 | 0.33189 (5) | 0.8656 (2) | 0.22140 (12) | 0.0323 (4) | |
C5 | 0.33285 (4) | 0.96546 (17) | 0.31868 (11) | 0.0266 (4) | |
C6 | 0.37011 (4) | 0.99681 (19) | 0.38061 (11) | 0.0283 (4) | |
C7 | 0.44717 (5) | 0.9632 (2) | 0.41168 (12) | 0.0345 (4) | |
O711 | 0.44997 (4) | 0.6931 (2) | 0.76322 (11) | 0.0545 (4) | |
O721 | 0.48067 (4) | 0.6443 (2) | 0.60826 (11) | 0.0598 (5) | |
N41 | 0.28955 (4) | 0.53986 (18) | 0.42905 (12) | 0.0326 (4) | |
C11 | 0.40746 (4) | 0.6362 (2) | 0.59709 (12) | 0.0328 (4) | |
C21 | 0.40444 (5) | 0.5516 (2) | 0.49460 (13) | 0.0352 (4) | |
C31 | 0.36569 (5) | 0.5224 (2) | 0.43884 (12) | 0.0335 (4) | |
C41 | 0.33058 (4) | 0.57955 (17) | 0.48501 (11) | 0.0283 (4) | |
C51 | 0.33299 (5) | 0.6678 (2) | 0.58549 (13) | 0.0346 (4) | |
C61 | 0.37182 (5) | 0.6950 (2) | 0.64159 (13) | 0.0361 (4) | |
C71 | 0.44815 (5) | 0.6608 (2) | 0.66330 (14) | 0.0389 (5) | |
H2 | 0.4589 (8) | 0.773 (3) | 0.259 (2) | 0.063 (7)* | |
H3 | 0.367200 | 0.728400 | 0.123900 | 0.0430* | |
H4 | 0.306800 | 0.846400 | 0.179000 | 0.0390* | |
H6 | 0.370600 | 1.063800 | 0.445000 | 0.0340* | |
H72 | 0.4665 (9) | 1.072 (3) | 0.530 (2) | 0.070 (8)* | |
H21 | 0.428400 | 0.514900 | 0.463800 | 0.0420* | |
H31 | 0.363300 | 0.464600 | 0.370800 | 0.0400* | |
H41A | 0.2706 (7) | 0.564 (3) | 0.4700 (19) | 0.050 (6)* | |
H41B | 0.2838 (8) | 0.592 (4) | 0.366 (2) | 0.073 (8)* | |
H41C | 0.2878 (7) | 0.420 (3) | 0.4147 (18) | 0.058 (6)* | |
H51 | 0.309100 | 0.708000 | 0.614700 | 0.0420* | |
H61 | 0.374000 | 0.753000 | 0.709600 | 0.0430* | |
H721 | 0.5061 (11) | 0.652 (4) | 0.659 (3) | 0.112 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5 | 0.0243 (2) | 0.0266 (2) | 0.0314 (2) | 0.0019 (1) | −0.0040 (1) | 0.0000 (1) |
O2 | 0.0341 (6) | 0.0599 (8) | 0.0398 (6) | 0.0057 (5) | 0.0036 (5) | −0.0134 (5) |
O51 | 0.0396 (6) | 0.0375 (6) | 0.0634 (8) | 0.0023 (5) | −0.0033 (5) | −0.0201 (5) |
O52 | 0.0428 (7) | 0.0337 (6) | 0.0711 (8) | −0.0002 (5) | 0.0227 (6) | 0.0022 (5) |
O53 | 0.0478 (8) | 0.0881 (10) | 0.0430 (7) | 0.0271 (7) | −0.0132 (6) | 0.0071 (7) |
O71 | 0.0259 (5) | 0.0666 (8) | 0.0415 (6) | 0.0038 (5) | −0.0030 (5) | −0.0112 (6) |
O72 | 0.0284 (6) | 0.0808 (10) | 0.0448 (7) | 0.0029 (6) | −0.0082 (5) | −0.0268 (6) |
C1 | 0.0263 (7) | 0.0335 (7) | 0.0260 (7) | −0.0019 (5) | −0.0014 (5) | 0.0013 (5) |
C2 | 0.0315 (7) | 0.0342 (7) | 0.0283 (7) | 0.0002 (6) | 0.0034 (5) | 0.0009 (5) |
C3 | 0.0374 (8) | 0.0403 (8) | 0.0278 (7) | −0.0032 (6) | −0.0012 (6) | −0.0079 (6) |
C4 | 0.0308 (7) | 0.0353 (7) | 0.0293 (7) | −0.0039 (6) | −0.0054 (5) | −0.0023 (5) |
C5 | 0.0251 (6) | 0.0278 (7) | 0.0266 (6) | −0.0006 (5) | 0.0001 (5) | 0.0022 (5) |
C6 | 0.0277 (7) | 0.0321 (7) | 0.0244 (6) | −0.0018 (5) | −0.0008 (5) | −0.0008 (5) |
C7 | 0.0276 (7) | 0.0447 (9) | 0.0305 (7) | −0.0013 (6) | −0.0012 (6) | −0.0014 (6) |
O711 | 0.0363 (6) | 0.0782 (9) | 0.0462 (7) | −0.0100 (6) | −0.0110 (5) | 0.0186 (6) |
O721 | 0.0300 (6) | 0.1024 (12) | 0.0461 (7) | 0.0077 (7) | −0.0016 (5) | −0.0036 (7) |
N41 | 0.0296 (7) | 0.0325 (7) | 0.0343 (7) | −0.0011 (5) | −0.0046 (5) | 0.0003 (5) |
C11 | 0.0298 (7) | 0.0335 (7) | 0.0341 (7) | 0.0020 (6) | −0.0028 (6) | −0.0019 (6) |
C21 | 0.0301 (7) | 0.0423 (8) | 0.0335 (8) | −0.0010 (6) | 0.0047 (6) | −0.0004 (6) |
C31 | 0.0358 (8) | 0.0365 (8) | 0.0281 (7) | 0.0007 (6) | 0.0026 (6) | 0.0021 (5) |
C41 | 0.0290 (7) | 0.0251 (6) | 0.0298 (7) | 0.0003 (5) | −0.0033 (5) | −0.0044 (5) |
C51 | 0.0291 (7) | 0.0369 (8) | 0.0371 (7) | −0.0059 (6) | −0.0002 (6) | 0.0040 (6) |
C61 | 0.0361 (8) | 0.0379 (8) | 0.0332 (7) | −0.0021 (6) | −0.0033 (6) | 0.0070 (6) |
C71 | 0.0320 (8) | 0.0415 (8) | 0.0421 (8) | 0.0005 (6) | −0.0033 (6) | −0.0016 (6) |
Geometric parameters (Å, º) top
S5—O51 | 1.4514 (13) | C2—C3 | 1.393 (2) |
S5—O52 | 1.4502 (13) | C3—C4 | 1.376 (2) |
S5—O53 | 1.4343 (14) | C4—C5 | 1.399 (2) |
S5—C5 | 1.7667 (14) | C5—C6 | 1.3773 (19) |
O2—C2 | 1.347 (2) | C3—H3 | 0.9302 |
O71—C7 | 1.2298 (19) | C4—H4 | 0.9290 |
O72—C7 | 1.309 (2) | C6—H6 | 0.9298 |
O2—H2 | 0.78 (2) | C11—C21 | 1.391 (2) |
O72—H72 | 0.77 (3) | C11—C61 | 1.388 (2) |
O711—C71 | 1.227 (2) | C11—C71 | 1.485 (2) |
O721—C71 | 1.298 (2) | C21—C31 | 1.383 (2) |
O721—H721 | 0.98 (4) | C31—C41 | 1.378 (2) |
N41—C41 | 1.4620 (19) | C41—C51 | 1.384 (2) |
N41—H41C | 0.93 (2) | C51—C61 | 1.384 (2) |
N41—H41B | 0.86 (3) | C21—H21 | 0.9312 |
N41—H41A | 0.84 (2) | C31—H31 | 0.9296 |
C1—C7 | 1.469 (2) | C51—H51 | 0.9288 |
C1—C2 | 1.408 (2) | C61—H61 | 0.9300 |
C1—C6 | 1.3986 (19) | | |
| | | |
O51—S5—O52 | 111.00 (8) | O71—C7—O72 | 122.75 (15) |
O51—S5—O53 | 113.81 (8) | C2—C3—H3 | 119.75 |
O51—S5—C5 | 106.20 (7) | C4—C3—H3 | 119.75 |
O52—S5—O53 | 113.12 (8) | C3—C4—H4 | 119.87 |
O52—S5—C5 | 105.15 (7) | C5—C4—H4 | 120.00 |
O53—S5—C5 | 106.83 (7) | C1—C6—H6 | 119.85 |
C2—O2—H2 | 107.2 (18) | C5—C6—H6 | 119.79 |
C7—O72—H72 | 108.7 (18) | C21—C11—C61 | 120.10 (13) |
C71—O721—H721 | 110 (2) | C21—C11—C71 | 121.59 (13) |
H41A—N41—H41C | 107 (2) | C61—C11—C71 | 118.28 (14) |
H41B—N41—H41C | 107 (2) | C11—C21—C31 | 119.63 (14) |
H41A—N41—H41B | 108 (2) | C21—C31—C41 | 119.47 (14) |
C41—N41—H41A | 111.0 (16) | N41—C41—C31 | 119.36 (12) |
C41—N41—H41B | 115.0 (18) | N41—C41—C51 | 118.82 (13) |
C41—N41—H41C | 109.1 (14) | C31—C41—C51 | 121.77 (13) |
C6—C1—C7 | 120.81 (12) | C41—C51—C61 | 118.54 (14) |
C2—C1—C7 | 119.85 (13) | C11—C61—C51 | 120.46 (14) |
C2—C1—C6 | 119.33 (13) | O711—C71—O721 | 123.64 (16) |
O2—C2—C3 | 117.90 (13) | O711—C71—C11 | 120.98 (15) |
O2—C2—C1 | 122.56 (14) | O721—C71—C11 | 115.37 (14) |
C1—C2—C3 | 119.53 (14) | C11—C21—H21 | 120.12 |
C2—C3—C4 | 120.50 (14) | C31—C21—H21 | 120.25 |
C3—C4—C5 | 120.12 (14) | C21—C31—H31 | 120.33 |
C4—C5—C6 | 120.12 (13) | C41—C31—H31 | 120.20 |
S5—C5—C6 | 119.83 (10) | C41—C51—H51 | 120.80 |
S5—C5—C4 | 120.04 (11) | C61—C51—H51 | 120.66 |
C1—C6—C5 | 120.36 (12) | C11—C61—H61 | 119.84 |
O72—C7—C1 | 114.46 (14) | C51—C61—H61 | 119.70 |
O71—C7—C1 | 122.79 (13) | | |
| | | |
O51—S5—C5—C4 | −162.57 (12) | C3—C4—C5—C6 | 1.2 (2) |
O51—S5—C5—C6 | 18.36 (13) | C3—C4—C5—S5 | −177.86 (11) |
O52—S5—C5—C4 | 79.70 (13) | C4—C5—C6—C1 | −0.4 (2) |
O52—S5—C5—C6 | −99.37 (12) | S5—C5—C6—C1 | 178.70 (11) |
O53—S5—C5—C4 | −40.76 (14) | C21—C11—C61—C51 | 1.0 (2) |
O53—S5—C5—C6 | 140.17 (12) | C61—C11—C21—C31 | −1.7 (2) |
C7—C1—C2—O2 | 2.1 (2) | C71—C11—C61—C51 | −176.96 (14) |
C2—C1—C7—O71 | 0.3 (2) | C21—C11—C71—O711 | −161.05 (16) |
C2—C1—C7—O72 | −179.51 (14) | C21—C11—C71—O721 | 18.4 (2) |
C6—C1—C7—O71 | −179.83 (15) | C61—C11—C71—O711 | 16.9 (2) |
C6—C1—C7—O72 | 0.3 (2) | C61—C11—C71—O721 | −163.64 (15) |
C6—C1—C2—O2 | −177.72 (14) | C71—C11—C21—C31 | 176.18 (14) |
C7—C1—C2—C3 | −178.49 (14) | C11—C21—C31—C41 | 0.8 (2) |
C2—C1—C6—C5 | −1.1 (2) | C21—C31—C41—C51 | 0.8 (2) |
C7—C1—C6—C5 | 179.08 (13) | C21—C31—C41—N41 | −176.55 (13) |
C6—C1—C2—C3 | 1.6 (2) | C31—C41—C51—C61 | −1.5 (2) |
O2—C2—C3—C4 | 178.58 (14) | N41—C41—C51—C61 | 175.86 (13) |
C1—C2—C3—C4 | −0.8 (2) | C41—C51—C61—C11 | 0.6 (2) |
C2—C3—C4—C5 | −0.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O71 | 0.78 (2) | 1.91 (2) | 2.6089 (18) | 149 (2) |
N41—H41A···O52i | 0.84 (2) | 1.93 (2) | 2.7589 (19) | 170 (2) |
N41—H41B···O53ii | 0.86 (3) | 2.06 (2) | 2.7959 (19) | 142 (2) |
N41—H41B···O52 | 0.86 (3) | 2.53 (3) | 2.8721 (19) | 104 (2) |
N41—H41C···O51iii | 0.93 (2) | 1.84 (2) | 2.7192 (19) | 156 (2) |
O72—H72···O71iv | 0.77 (3) | 1.92 (3) | 2.6923 (17) | 175 (3) |
O721—H721···O711v | 0.98 (4) | 1.66 (4) | 2.6303 (19) | 172 (3) |
C6—H6···O51 | 0.93 | 2.52 | 2.8932 (19) | 105 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+1; (v) −x+1, y, −z+3/2. |