Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057856/sj2414sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057856/sj2414Isup2.hkl |
CCDC reference: 672965
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.104
- Data-to-parameter ratio = 11.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT480_ALERT_4_C Long H...A H-Bond Reported H4 .. S1 .. 2.96 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A .. S1 .. 3.00 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For information on the role of water in self-assembly processes, see: Smith et al. (2007). For reference structural data, see: Allen et al. (1987).
2-hydroxy-5-sulfobenzoic acid (2.18 g, 10 mmol) and piperazine (0.86 g, 10 mmol) were dissolved in warm H2O (20 ml). Crystals of the title compound were obtained by slow evaporation of this solution.
The H atoms of the water molecule and those on the N atoms were located in difference Fourier maps; their the parameters were freely refined. All other H atoms were positioned geometrically and refined using a riding model, with O—H = 0.82 Å for hydroxy H atoms, C—H = 0.93 Å for aromatic H atoms, and 0.97 Å for methylene H atoms, respectively, and with Uiso(H) = 1.5Ueq(O) for hydroxy and Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
C4H12N22+·2C7H5O6S−·2H2O | Z = 1 |
Mr = 558.52 | F(000) = 292 |
Triclinic, P1 | Dx = 1.607 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8980 (13) Å | Cell parameters from 2045 reflections |
b = 7.2012 (14) Å | θ = 3.1–26.3° |
c = 12.800 (2) Å | µ = 0.31 mm−1 |
α = 100.280 (3)° | T = 294 K |
β = 93.084 (3)° | Block, colourless |
γ = 111.459 (3)° | 0.24 × 0.20 × 0.18 mm |
V = 577.31 (19) Å3 |
Bruker SMART CCD area-detector diffractometer | 2016 independent reflections |
Radiation source: fine-focus sealed tube | 1786 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS;Bruker, 2000) | h = −8→8 |
Tmin = 0.930, Tmax = 0.947 | k = −8→5 |
2992 measured reflections | l = −13→15 |
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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.226P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2016 reflections | Δρmax = 0.29 e Å−3 |
182 parameters | Δρmin = −0.33 e Å−3 |
6 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.056 (7) |
C4H12N22+·2C7H5O6S−·2H2O | γ = 111.459 (3)° |
Mr = 558.52 | V = 577.31 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8980 (13) Å | Mo Kα radiation |
b = 7.2012 (14) Å | µ = 0.31 mm−1 |
c = 12.800 (2) Å | T = 294 K |
α = 100.280 (3)° | 0.24 × 0.20 × 0.18 mm |
β = 93.084 (3)° |
Bruker SMART CCD area-detector diffractometer | 2016 independent reflections |
Absorption correction: multi-scan (SADABS;Bruker, 2000) | 1786 reflections with I > 2σ(I) |
Tmin = 0.930, Tmax = 0.947 | Rint = 0.021 |
2992 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 6 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2016 reflections | Δρmin = −0.33 e Å−3 |
182 parameters |
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 | ||
S1 | 0.18428 (7) | 0.46867 (7) | 0.70639 (4) | 0.0325 (2) | |
O1 | 0.3025 (3) | 0.4558 (3) | 0.61877 (12) | 0.0540 (5) | |
O2 | 0.0505 (3) | 0.5810 (3) | 0.69897 (13) | 0.0549 (5) | |
O3 | 0.0567 (2) | 0.2658 (2) | 0.72449 (10) | 0.0366 (4) | |
O4 | 0.1360 (2) | 0.7404 (3) | 1.09825 (12) | 0.0498 (4) | |
H4 | 0.0971 | 0.7675 | 1.1564 | 0.075* | |
O5 | 0.4490 (3) | 0.8749 (3) | 1.19742 (12) | 0.0526 (4) | |
O6 | 0.7792 (2) | 0.9051 (3) | 1.09761 (12) | 0.0512 (4) | |
H6 | 0.7159 | 0.9232 | 1.1484 | 0.077* | |
N1 | 0.7087 (3) | 0.0786 (3) | 0.55348 (14) | 0.0383 (4) | |
C1 | 0.3649 (3) | 0.5961 (3) | 0.82344 (15) | 0.0304 (4) | |
C2 | 0.2889 (3) | 0.6465 (3) | 0.91627 (15) | 0.0308 (4) | |
H2 | 0.1452 | 0.6130 | 0.9160 | 0.037* | |
C3 | 0.4238 (3) | 0.7473 (3) | 1.01111 (15) | 0.0307 (4) | |
C4 | 0.6405 (3) | 0.8012 (3) | 1.00941 (16) | 0.0353 (5) | |
C5 | 0.7156 (3) | 0.7501 (3) | 0.91494 (18) | 0.0405 (5) | |
H5 | 0.8594 | 0.7859 | 0.9140 | 0.049* | |
C6 | 0.5800 (3) | 0.6470 (3) | 0.82266 (17) | 0.0367 (5) | |
H6A | 0.6315 | 0.6112 | 0.7597 | 0.044* | |
C7 | 0.3409 (3) | 0.7940 (3) | 1.11070 (16) | 0.0364 (5) | |
C8 | 0.5938 (3) | 0.2154 (3) | 0.54583 (17) | 0.0402 (5) | |
H8A | 0.6926 | 0.3507 | 0.5437 | 0.048* | |
H8B | 0.5224 | 0.2265 | 0.6085 | 0.048* | |
C9 | 0.5640 (3) | −0.1322 (3) | 0.55349 (17) | 0.0383 (5) | |
H9A | 0.4917 | −0.1324 | 0.6164 | 0.046* | |
H9B | 0.6435 | −0.2184 | 0.5560 | 0.046* | |
O7 | 0.0665 (3) | 0.9051 (3) | 0.61474 (14) | 0.0545 (4) | |
H1A | 0.779 (3) | 0.077 (4) | 0.4952 (11) | 0.048 (7)* | |
H1B | 0.802 (3) | 0.129 (4) | 0.6142 (10) | 0.068 (8)* | |
H7A | 0.092 (5) | 1.019 (2) | 0.6563 (17) | 0.074 (10)* | |
H7B | 0.063 (5) | 0.808 (3) | 0.6449 (19) | 0.079 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0353 (3) | 0.0313 (3) | 0.0238 (3) | 0.0054 (2) | 0.00128 (19) | 0.00453 (19) |
O1 | 0.0540 (9) | 0.0603 (10) | 0.0288 (8) | 0.0014 (8) | 0.0137 (7) | 0.0040 (7) |
O2 | 0.0631 (10) | 0.0487 (9) | 0.0510 (10) | 0.0232 (8) | −0.0133 (8) | 0.0082 (8) |
O3 | 0.0381 (7) | 0.0324 (7) | 0.0271 (7) | 0.0018 (6) | 0.0016 (6) | 0.0019 (5) |
O4 | 0.0404 (9) | 0.0569 (10) | 0.0330 (8) | 0.0032 (7) | 0.0099 (6) | −0.0059 (7) |
O5 | 0.0569 (10) | 0.0558 (10) | 0.0293 (8) | 0.0104 (8) | −0.0054 (7) | −0.0026 (7) |
O6 | 0.0372 (8) | 0.0585 (10) | 0.0429 (9) | 0.0085 (7) | −0.0128 (7) | 0.0004 (8) |
N1 | 0.0303 (8) | 0.0426 (10) | 0.0324 (9) | 0.0065 (8) | −0.0060 (7) | 0.0032 (8) |
C1 | 0.0311 (10) | 0.0249 (9) | 0.0295 (10) | 0.0051 (8) | 0.0019 (8) | 0.0042 (7) |
C2 | 0.0265 (9) | 0.0264 (9) | 0.0315 (10) | 0.0025 (7) | 0.0021 (7) | 0.0031 (7) |
C3 | 0.0320 (10) | 0.0245 (9) | 0.0291 (10) | 0.0041 (8) | 0.0005 (8) | 0.0052 (7) |
C4 | 0.0325 (10) | 0.0285 (10) | 0.0379 (11) | 0.0051 (8) | −0.0059 (8) | 0.0070 (8) |
C5 | 0.0254 (9) | 0.0421 (12) | 0.0492 (12) | 0.0077 (9) | 0.0033 (9) | 0.0095 (9) |
C6 | 0.0333 (10) | 0.0359 (11) | 0.0378 (11) | 0.0096 (9) | 0.0088 (8) | 0.0063 (9) |
C7 | 0.0412 (11) | 0.0280 (10) | 0.0296 (10) | 0.0036 (8) | 0.0009 (8) | 0.0024 (8) |
C8 | 0.0429 (11) | 0.0323 (10) | 0.0371 (11) | 0.0087 (9) | −0.0028 (9) | 0.0012 (8) |
C9 | 0.0394 (11) | 0.0367 (11) | 0.0358 (11) | 0.0121 (9) | −0.0018 (9) | 0.0074 (9) |
O7 | 0.0682 (11) | 0.0440 (10) | 0.0561 (10) | 0.0247 (9) | 0.0157 (9) | 0.0133 (9) |
S1—O1 | 1.4310 (16) | C2—H2 | 0.9300 |
S1—O2 | 1.4419 (17) | C3—C4 | 1.403 (3) |
S1—O3 | 1.4713 (14) | C3—C7 | 1.460 (3) |
S1—C1 | 1.7640 (19) | C4—C5 | 1.384 (3) |
O4—C7 | 1.314 (3) | C5—C6 | 1.372 (3) |
O4—H4 | 0.8200 | C5—H5 | 0.9300 |
O5—C7 | 1.221 (2) | C6—H6A | 0.9300 |
O6—C4 | 1.345 (2) | C8—C9i | 1.504 (3) |
O6—H6 | 0.8200 | C8—H8A | 0.9700 |
N1—C9 | 1.481 (3) | C8—H8B | 0.9700 |
N1—C8 | 1.485 (3) | C9—C8i | 1.504 (3) |
N1—H1A | 0.914 (9) | C9—H9A | 0.9700 |
N1—H1B | 0.907 (10) | C9—H9B | 0.9700 |
C1—C2 | 1.368 (3) | O7—H7A | 0.848 (10) |
C1—C6 | 1.393 (3) | O7—H7B | 0.849 (10) |
C2—C3 | 1.391 (3) | ||
O1—S1—O2 | 115.38 (11) | O6—C4—C3 | 121.52 (19) |
O1—S1—O3 | 111.98 (9) | C5—C4—C3 | 119.85 (18) |
O2—S1—O3 | 108.58 (10) | C6—C5—C4 | 120.59 (18) |
O1—S1—C1 | 107.58 (10) | C6—C5—H5 | 119.7 |
O2—S1—C1 | 106.66 (9) | C4—C5—H5 | 119.7 |
O3—S1—C1 | 106.12 (8) | C5—C6—C1 | 119.82 (19) |
C7—O4—H4 | 109.5 | C5—C6—H6A | 120.1 |
C4—O6—H6 | 109.5 | C1—C6—H6A | 120.1 |
C9—N1—C8 | 111.79 (16) | O5—C7—O4 | 122.67 (19) |
C9—N1—H1A | 109.3 (15) | O5—C7—C3 | 124.08 (19) |
C8—N1—H1A | 107.1 (15) | O4—C7—C3 | 113.26 (16) |
C9—N1—H1B | 109.5 (17) | N1—C8—C9i | 110.16 (16) |
C8—N1—H1B | 109.5 (17) | N1—C8—H8A | 109.6 |
H1A—N1—H1B | 109.7 (14) | C9i—C8—H8A | 109.6 |
C2—C1—C6 | 120.10 (18) | N1—C8—H8B | 109.6 |
C2—C1—S1 | 118.23 (14) | C9i—C8—H8B | 109.6 |
C6—C1—S1 | 121.67 (15) | H8A—C8—H8B | 108.1 |
C1—C2—C3 | 120.86 (18) | N1—C9—C8i | 109.94 (16) |
C1—C2—H2 | 119.6 | N1—C9—H9A | 109.7 |
C3—C2—H2 | 119.6 | C8i—C9—H9A | 109.7 |
C2—C3—C4 | 118.76 (18) | N1—C9—H9B | 109.7 |
C2—C3—C7 | 120.57 (17) | C8i—C9—H9B | 109.7 |
C4—C3—C7 | 120.67 (17) | H9A—C9—H9B | 108.2 |
O6—C4—C5 | 118.62 (18) | H7A—O7—H7B | 115.9 (17) |
O1—S1—C1—C2 | 172.95 (15) | C7—C3—C4—C5 | 178.02 (18) |
O2—S1—C1—C2 | 48.60 (18) | O6—C4—C5—C6 | −178.95 (19) |
O3—S1—C1—C2 | −67.04 (17) | C3—C4—C5—C6 | 0.0 (3) |
O1—S1—C1—C6 | −6.4 (2) | C4—C5—C6—C1 | 1.1 (3) |
O2—S1—C1—C6 | −130.77 (17) | C2—C1—C6—C5 | −0.8 (3) |
O3—S1—C1—C6 | 113.59 (17) | S1—C1—C6—C5 | 178.56 (15) |
C6—C1—C2—C3 | −0.5 (3) | C2—C3—C7—O5 | 177.08 (19) |
S1—C1—C2—C3 | −179.92 (14) | C4—C3—C7—O5 | −2.2 (3) |
C1—C2—C3—C4 | 1.6 (3) | C2—C3—C7—O4 | −3.0 (3) |
C1—C2—C3—C7 | −177.75 (17) | C4—C3—C7—O4 | 177.72 (18) |
C2—C3—C4—O6 | 177.61 (17) | C9—N1—C8—C9i | −57.5 (2) |
C7—C3—C4—O6 | −3.1 (3) | C8—N1—C9—C8i | 57.3 (2) |
C2—C3—C4—C5 | −1.3 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3ii | 0.82 | 1.90 | 2.690 (2) | 160 |
O4—H4···S1ii | 0.82 | 2.96 | 3.5926 (16) | 136 |
N1—H1A···O7iii | 0.91 (1) | 1.80 (1) | 2.715 (3) | 175 (2) |
N1—H1B···O3iv | 0.91 (1) | 2.01 (1) | 2.895 (2) | 166 (2) |
N1—H1B···S1iv | 0.91 (1) | 2.87 (2) | 3.6176 (17) | 140 (2) |
O7—H7A···O3v | 0.85 (1) | 1.94 (1) | 2.750 (2) | 160 (3) |
O7—H7A···S1v | 0.85 (1) | 3.00 (1) | 3.781 (2) | 154 (2) |
O6—H6···O5 | 0.82 | 1.91 | 2.630 (2) | 147 |
O7—H7B···O2 | 0.85 (1) | 1.86 (1) | 2.710 (2) | 175 (3) |
Symmetry codes: (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z; (v) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C4H12N22+·2C7H5O6S−·2H2O |
Mr | 558.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 6.8980 (13), 7.2012 (14), 12.800 (2) |
α, β, γ (°) | 100.280 (3), 93.084 (3), 111.459 (3) |
V (Å3) | 577.31 (19) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.24 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS;Bruker, 2000) |
Tmin, Tmax | 0.930, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2992, 2016, 1786 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.104, 1.04 |
No. of reflections | 2016 |
No. of parameters | 182 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.33 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.82 | 1.90 | 2.690 (2) | 160.1 |
O4—H4···S1i | 0.82 | 2.96 | 3.5926 (16) | 135.7 |
N1—H1A···O7ii | 0.914 (9) | 1.803 (10) | 2.715 (3) | 175 (2) |
N1—H1B···O3iii | 0.907 (10) | 2.006 (12) | 2.895 (2) | 166 (2) |
N1—H1B···S1iii | 0.907 (10) | 2.874 (19) | 3.6176 (17) | 140 (2) |
O7—H7A···O3iv | 0.848 (10) | 1.938 (13) | 2.750 (2) | 160 (3) |
O7—H7A···S1iv | 0.848 (10) | 2.998 (13) | 3.781 (2) | 154 (2) |
O6—H6···O5 | 0.82 | 1.91 | 2.630 (2) | 146.5 |
O7—H7B···O2 | 0.849 (10) | 1.863 (10) | 2.710 (2) | 175 (3) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x, y+1, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
3-carboxy-4-hydroxy benzene sulfonate also known as 5-sulfosalicylic acid (SSA) has six potential donor sites in the three substituent groups (the sulfonic acid, the carboxylic acid and the phenolic groups), and it can form mono-, di- and trianionic ligand species through deprotonation. The presence of the numerous oxygen atoms in three substituent groups usually results in hydrogen-bonding associations, and the self-assembly process of crystallization often requires the incorporation of water molecules in the structures (Smith et al. 2007).
We report here the synthesis and structure of piperazine-1,4-diium 3-carboxyl-4-hydroxyl benzene sulfonate monohydrate, (I), Fig. 1 which was obtained from a solution of 2-hydroxy-5-sulfobenzoic acid and piperazine. Bond distances and angles in (I) are normal (Allen et al., 1987). The asymmetric unit of the title compound comprises one half of the piperazine-1,4-diium cation, which lies about an inversion centre, a 3-carboxy-4-hydroxybenzenesulfonate anion and a water solvate. In the crystal structure molecules were interlinked by hydrogen bonds, Table 1, involving oxygen atoms from the sulfonate and carboxylate groups of the 5-sulfosalicylate, and the nitrogen atoms of the piperazinediium cation. The water molecules function as a bridge between two anions and a cation producing a three-dimensional hydrogen-bonded framework structure. The hydroxyl group of the 5-sulfosalicylate forms an intramolecular O6—H6···O5 hydrogen bond but is not involved in the crystal packing.