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Two 1:1 proton-transfer complexes of sulfobenzoic acids with aromatic amines, namely 4-[2-(4-pyridyl)ethenyl]pyridinium 2-carboxybenzenesulfonate, C
12H
11N
2+·C
7H
5O
5S
-, (I), and 1,10-phenanthrolin-1-ium 4-carboxybenzenesulfonate dihydrate, C
12H
9N
2+·C
7H
5O
5S
-·2H
2O, (II), have very different hydrogen-bonding patterns compared with reported organic sulfobenzoic acid complexes. In (I), two cations and two anions form a four-molecule loop, in which
-
interactions occur. In (II), the anions and water molecules form a three-dimensional hydrogen-bonding network, while the cations only act as pendant components. The water molecules play a central role in the formation of the abundant hydrogen-bonding architecture in (II). The relative poorness and richness of hydrogen bonds in (I) and (II), respectively, give rise to novel hydrogen-bonding patterns.
Supporting information
CCDC references: 659141; 659142
A mixture of 2-sulfobenzoic acid (0.051 g, 0.25 mmol), 1,2-di-4-pyridylethylene (0.046 g, 029 mmol) and water (10 ml) was refluxed for 5 h. After cooling to room temperature, pale-yellow brick-shaped crystals of (I) were obtained by filtration. Analysis calculated for C19H16N2O5S: C 59.37, H 4.20, N 7.29%; found: C 59.35, H 4.15, N 6.90%. A mixture of SnSO4 (0.086 g, 0.40 mmol), potassium hydrogen 4-sulfobenzoate (0.096 g, 0.40 mmol), 1,10-phenanthroline monohydrate (0.079 g, 0.40 mmol), 12 M HNO3 (0.1 ml) and water (15 ml) was sealed in a 30 ml Teflon-lined stainless steel autoclave and heated at 433 K for 72 h. After cooling to room temperature, the colorless solid was filtered off and washed with water. Crystals were obtained by recrystallization in water. The synthetic procedure without SnSO4 did not lead to the formation of complex (II). Analysis calculated for C19H18N2O7S: C 54.54, H 4.34, N 6.70%; found: C 54.77, H 4.35, N 6.96%. TGA analysis revealed that a weight loss in the temperature range 298 to 375 K corresponds to the release of two water molecules (calculated 8.61%, found 8.80%).
H atoms on C atoms were placed in idealized positions and refined as riding atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. H atoms involved in hydrogen-bonding interactions (pyridinium, carboxyl and water) were located from difference Fourier maps and refined with distance restraints [O—H = 0.85 (1) Å and N—H = 0.82 (1) Å] and fixed isotropic displacement parameters [Uiso(H) = 0.08 Å2].
For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) 4-[2-(4-pyridyl)ethenyl]pyridinium 2-carboxybenzenesulfonate
top
Crystal data top
C12H11N2+·C7H5O5S− | Z = 2 |
Mr = 384.40 | F(000) = 400 |
Triclinic, P1 | Dx = 1.459 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7451 (11) Å | Cell parameters from 2034 reflections |
b = 10.0346 (13) Å | θ = 2.5–26.6° |
c = 10.7877 (14) Å | µ = 0.22 mm−1 |
α = 95.377 (1)° | T = 295 K |
β = 104.954 (1)° | Brick, pale yellow |
γ = 104.047 (2)° | 0.31 × 0.24 × 0.22 mm |
V = 874.82 (19) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3095 independent reflections |
Radiation source: fine-focus sealed tube | 2534 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
phi and ω scans | θmax = 25.2°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→10 |
Tmin = 0.935, Tmax = 0.953 | k = −11→11 |
4632 measured reflections | l = −12→12 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0654P)2 + 0.5901P] where P = (Fo2 + 2Fc2)/3 |
3095 reflections | (Δ/σ)max = 0.001 |
250 parameters | Δρmax = 0.18 e Å−3 |
2 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C12H11N2+·C7H5O5S− | γ = 104.047 (2)° |
Mr = 384.40 | V = 874.82 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7451 (11) Å | Mo Kα radiation |
b = 10.0346 (13) Å | µ = 0.22 mm−1 |
c = 10.7877 (14) Å | T = 295 K |
α = 95.377 (1)° | 0.31 × 0.24 × 0.22 mm |
β = 104.954 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3095 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2534 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.953 | Rint = 0.015 |
4632 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | Δρmax = 0.18 e Å−3 |
3095 reflections | Δρmin = −0.35 e Å−3 |
250 parameters | |
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 | 0.42777 (7) | 0.78017 (5) | 0.80645 (5) | 0.03731 (17) | |
O1 | 0.0436 (2) | 0.45903 (17) | 0.68689 (17) | 0.0557 (5) | |
O2 | 0.2524 (2) | 0.45248 (16) | 0.85457 (16) | 0.0515 (4) | |
O3 | 0.54928 (18) | 0.73581 (16) | 0.90142 (14) | 0.0443 (4) | |
O4 | 0.4846 (2) | 0.92381 (17) | 0.79259 (18) | 0.0593 (5) | |
O5 | 0.3627 (2) | 0.68389 (17) | 0.68485 (14) | 0.0501 (4) | |
C1 | 0.1534 (3) | 0.5088 (2) | 0.7994 (2) | 0.0385 (5) | |
C2 | 0.1417 (3) | 0.6458 (2) | 0.86118 (19) | 0.0357 (5) | |
C3 | 0.2594 (3) | 0.7712 (2) | 0.87205 (18) | 0.0346 (5) | |
C4 | 0.2484 (3) | 0.8932 (2) | 0.9374 (2) | 0.0452 (5) | |
H4 | 0.3260 | 0.9773 | 0.9437 | 0.054* | |
C5 | 0.1222 (3) | 0.8891 (3) | 0.9928 (2) | 0.0563 (7) | |
H5 | 0.1175 | 0.9703 | 1.0390 | 0.068* | |
C6 | 0.0037 (3) | 0.7669 (3) | 0.9807 (2) | 0.0575 (7) | |
H6 | −0.0821 | 0.7654 | 1.0171 | 0.069* | |
C7 | 0.0126 (3) | 0.6453 (3) | 0.9138 (2) | 0.0480 (6) | |
H7 | −0.0689 | 0.5627 | 0.9040 | 0.058* | |
N1 | 0.8844 (2) | −0.2544 (2) | 0.4335 (2) | 0.0487 (5) | |
N2 | 0.5713 (2) | 0.4792 (2) | 0.79293 (17) | 0.0412 (4) | |
C8 | 0.8208 (3) | −0.1638 (2) | 0.3702 (2) | 0.0487 (6) | |
H8 | 0.8111 | −0.1695 | 0.2818 | 0.058* | |
C9 | 0.7684 (3) | −0.0619 (2) | 0.4281 (2) | 0.0437 (5) | |
H9 | 0.7257 | −0.0004 | 0.3798 | 0.052* | |
C10 | 0.7803 (3) | −0.0525 (2) | 0.5594 (2) | 0.0400 (5) | |
C11 | 0.8444 (3) | −0.1490 (2) | 0.6244 (2) | 0.0539 (6) | |
H11 | 0.8528 | −0.1480 | 0.7122 | 0.065* | |
C12 | 0.8954 (3) | −0.2457 (3) | 0.5592 (3) | 0.0560 (6) | |
H12 | 0.9397 | −0.3081 | 0.6052 | 0.067* | |
C13 | 0.7306 (3) | 0.0539 (2) | 0.6308 (2) | 0.0426 (5) | |
H13 | 0.7207 | 0.0406 | 0.7129 | 0.051* | |
C14 | 0.6987 (3) | 0.1666 (2) | 0.5887 (2) | 0.0429 (5) | |
H14 | 0.7065 | 0.1794 | 0.5060 | 0.051* | |
C15 | 0.6522 (2) | 0.2728 (2) | 0.66169 (19) | 0.0362 (5) | |
C16 | 0.6112 (3) | 0.2570 (2) | 0.7770 (2) | 0.0394 (5) | |
H16 | 0.6110 | 0.1750 | 0.8106 | 0.047* | |
C17 | 0.5712 (3) | 0.3618 (2) | 0.8410 (2) | 0.0411 (5) | |
H17 | 0.5439 | 0.3509 | 0.9179 | 0.049* | |
C18 | 0.6486 (3) | 0.3971 (2) | 0.6148 (2) | 0.0425 (5) | |
H18 | 0.6740 | 0.4109 | 0.5376 | 0.051* | |
C19 | 0.6080 (3) | 0.4984 (2) | 0.6820 (2) | 0.0463 (5) | |
H19 | 0.6057 | 0.5813 | 0.6505 | 0.056* | |
H1A | 0.062 (4) | 0.389 (2) | 0.647 (3) | 0.080* | |
H2A | 0.548 (4) | 0.543 (2) | 0.833 (3) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0474 (3) | 0.0328 (3) | 0.0353 (3) | 0.0128 (2) | 0.0155 (2) | 0.0092 (2) |
O1 | 0.0479 (10) | 0.0453 (10) | 0.0647 (11) | 0.0187 (8) | 0.0038 (8) | −0.0151 (8) |
O2 | 0.0583 (10) | 0.0423 (9) | 0.0610 (10) | 0.0274 (8) | 0.0156 (8) | 0.0127 (8) |
O3 | 0.0440 (9) | 0.0494 (9) | 0.0445 (9) | 0.0201 (7) | 0.0140 (7) | 0.0102 (7) |
O4 | 0.0713 (12) | 0.0380 (9) | 0.0739 (12) | 0.0118 (8) | 0.0294 (10) | 0.0213 (8) |
O5 | 0.0653 (11) | 0.0538 (10) | 0.0345 (8) | 0.0178 (8) | 0.0203 (8) | 0.0031 (7) |
C1 | 0.0378 (11) | 0.0323 (11) | 0.0480 (12) | 0.0109 (9) | 0.0161 (10) | 0.0068 (9) |
C2 | 0.0388 (11) | 0.0375 (12) | 0.0340 (10) | 0.0173 (9) | 0.0094 (9) | 0.0071 (9) |
C3 | 0.0400 (11) | 0.0352 (11) | 0.0292 (10) | 0.0175 (9) | 0.0048 (8) | 0.0035 (8) |
C4 | 0.0527 (14) | 0.0379 (12) | 0.0441 (12) | 0.0223 (11) | 0.0055 (10) | 0.0002 (10) |
C5 | 0.0642 (16) | 0.0591 (16) | 0.0497 (14) | 0.0404 (14) | 0.0081 (12) | −0.0079 (12) |
C6 | 0.0557 (15) | 0.0772 (19) | 0.0543 (15) | 0.0389 (15) | 0.0226 (12) | 0.0082 (13) |
C7 | 0.0423 (13) | 0.0547 (15) | 0.0536 (14) | 0.0220 (11) | 0.0165 (11) | 0.0107 (11) |
N1 | 0.0473 (11) | 0.0369 (11) | 0.0588 (12) | 0.0142 (9) | 0.0116 (9) | −0.0031 (9) |
N2 | 0.0459 (11) | 0.0448 (11) | 0.0387 (10) | 0.0211 (9) | 0.0152 (8) | 0.0039 (8) |
C8 | 0.0518 (14) | 0.0488 (14) | 0.0432 (13) | 0.0156 (11) | 0.0120 (11) | −0.0032 (10) |
C9 | 0.0469 (13) | 0.0404 (12) | 0.0430 (12) | 0.0166 (10) | 0.0090 (10) | 0.0036 (10) |
C10 | 0.0421 (12) | 0.0323 (11) | 0.0448 (12) | 0.0082 (9) | 0.0142 (10) | 0.0032 (9) |
C11 | 0.0777 (18) | 0.0427 (14) | 0.0490 (14) | 0.0261 (13) | 0.0215 (13) | 0.0117 (11) |
C12 | 0.0707 (17) | 0.0400 (14) | 0.0613 (16) | 0.0241 (12) | 0.0173 (13) | 0.0101 (11) |
C13 | 0.0519 (13) | 0.0414 (13) | 0.0390 (12) | 0.0151 (10) | 0.0190 (10) | 0.0068 (9) |
C14 | 0.0522 (13) | 0.0430 (13) | 0.0392 (12) | 0.0177 (11) | 0.0191 (10) | 0.0065 (10) |
C15 | 0.0360 (11) | 0.0387 (12) | 0.0363 (11) | 0.0136 (9) | 0.0114 (9) | 0.0058 (9) |
C16 | 0.0457 (12) | 0.0393 (12) | 0.0404 (11) | 0.0187 (10) | 0.0160 (10) | 0.0126 (9) |
C17 | 0.0431 (12) | 0.0528 (14) | 0.0348 (11) | 0.0201 (10) | 0.0158 (9) | 0.0119 (10) |
C18 | 0.0546 (13) | 0.0462 (13) | 0.0373 (11) | 0.0226 (11) | 0.0212 (10) | 0.0139 (9) |
C19 | 0.0593 (14) | 0.0430 (13) | 0.0493 (13) | 0.0250 (11) | 0.0244 (11) | 0.0159 (10) |
Geometric parameters (Å, º) top
S1—O4 | 1.4414 (17) | N2—H2A | 0.83 (3) |
S1—O5 | 1.4451 (16) | C8—C9 | 1.379 (3) |
S1—O3 | 1.4596 (15) | C8—H8 | 0.9300 |
S1—C3 | 1.778 (2) | C9—C10 | 1.385 (3) |
O1—C1 | 1.303 (3) | C9—H9 | 0.9300 |
O1—H1A | 0.86 (3) | C10—C11 | 1.390 (3) |
O2—C1 | 1.207 (2) | C10—C13 | 1.471 (3) |
C1—C2 | 1.509 (3) | C11—C12 | 1.370 (3) |
C2—C7 | 1.388 (3) | C11—H11 | 0.9300 |
C2—C3 | 1.393 (3) | C12—H12 | 0.9300 |
C3—C4 | 1.391 (3) | C13—C14 | 1.322 (3) |
C4—C5 | 1.378 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.463 (3) |
C5—C6 | 1.371 (4) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—C16 | 1.393 (3) |
C6—C7 | 1.387 (3) | C15—C18 | 1.394 (3) |
C6—H6 | 0.9300 | C16—C17 | 1.368 (3) |
C7—H7 | 0.9300 | C16—H16 | 0.9300 |
N1—C12 | 1.328 (3) | C17—H17 | 0.9300 |
N1—C8 | 1.329 (3) | C18—C19 | 1.362 (3) |
N2—C17 | 1.331 (3) | C18—H18 | 0.9300 |
N2—C19 | 1.335 (3) | C19—H19 | 0.9300 |
| | | |
O4—S1—O5 | 114.20 (10) | C9—C8—H8 | 118.1 |
O4—S1—O3 | 112.94 (11) | C8—C9—C10 | 119.1 (2) |
O5—S1—O3 | 111.78 (9) | C8—C9—H9 | 120.5 |
O4—S1—C3 | 105.51 (10) | C10—C9—H9 | 120.5 |
O5—S1—C3 | 105.87 (10) | C9—C10—C11 | 116.8 (2) |
O3—S1—C3 | 105.69 (9) | C9—C10—C13 | 123.3 (2) |
C1—O1—H1A | 112 (2) | C11—C10—C13 | 119.8 (2) |
O2—C1—O1 | 125.7 (2) | C12—C11—C10 | 120.1 (2) |
O2—C1—C2 | 121.3 (2) | C12—C11—H11 | 120.0 |
O1—C1—C2 | 113.00 (18) | C10—C11—H11 | 120.0 |
C7—C2—C3 | 119.1 (2) | N1—C12—C11 | 123.0 (2) |
C7—C2—C1 | 118.6 (2) | N1—C12—H12 | 118.5 |
C3—C2—C1 | 122.31 (18) | C11—C12—H12 | 118.5 |
C4—C3—C2 | 119.9 (2) | C14—C13—C10 | 125.8 (2) |
C4—C3—S1 | 118.40 (18) | C14—C13—H13 | 117.1 |
C2—C3—S1 | 121.66 (15) | C10—C13—H13 | 117.1 |
C5—C4—C3 | 119.9 (2) | C13—C14—C15 | 125.2 (2) |
C5—C4—H4 | 120.1 | C13—C14—H14 | 117.4 |
C3—C4—H4 | 120.1 | C15—C14—H14 | 117.4 |
C6—C5—C4 | 120.8 (2) | C16—C15—C18 | 117.54 (18) |
C6—C5—H5 | 119.6 | C16—C15—C14 | 123.51 (19) |
C4—C5—H5 | 119.6 | C18—C15—C14 | 118.95 (18) |
C5—C6—C7 | 119.6 (2) | C17—C16—C15 | 120.3 (2) |
C5—C6—H6 | 120.2 | C17—C16—H16 | 119.9 |
C7—C6—H6 | 120.2 | C15—C16—H16 | 119.9 |
C6—C7—C2 | 120.7 (2) | N2—C17—C16 | 119.92 (19) |
C6—C7—H7 | 119.6 | N2—C17—H17 | 120.0 |
C2—C7—H7 | 119.6 | C16—C17—H17 | 120.0 |
C12—N1—C8 | 117.2 (2) | C19—C18—C15 | 120.04 (19) |
C17—N2—C19 | 121.94 (18) | C19—C18—H18 | 120.0 |
C17—N2—H2A | 119 (2) | C15—C18—H18 | 120.0 |
C19—N2—H2A | 119 (2) | N2—C19—C18 | 120.3 (2) |
N1—C8—C9 | 123.7 (2) | N2—C19—H19 | 119.9 |
N1—C8—H8 | 118.1 | C18—C19—H19 | 119.9 |
| | | |
O2—C1—C2—C7 | −103.8 (3) | C12—N1—C8—C9 | 0.8 (4) |
O1—C1—C2—C7 | 73.7 (3) | N1—C8—C9—C10 | −0.6 (4) |
O2—C1—C2—C3 | 73.5 (3) | C8—C9—C10—C11 | −0.4 (3) |
O1—C1—C2—C3 | −109.1 (2) | C8—C9—C10—C13 | 178.9 (2) |
C7—C2—C3—C4 | 1.4 (3) | C9—C10—C11—C12 | 1.3 (4) |
C1—C2—C3—C4 | −175.81 (18) | C13—C10—C11—C12 | −178.1 (2) |
C7—C2—C3—S1 | −179.68 (16) | C8—N1—C12—C11 | 0.1 (4) |
C1—C2—C3—S1 | 3.1 (3) | C10—C11—C12—N1 | −1.1 (4) |
O4—S1—C3—C4 | −21.65 (19) | C9—C10—C13—C14 | −13.3 (4) |
O5—S1—C3—C4 | −143.06 (16) | C11—C10—C13—C14 | 166.0 (2) |
O3—S1—C3—C4 | 98.22 (17) | C10—C13—C14—C15 | −178.8 (2) |
O4—S1—C3—C2 | 159.40 (17) | C13—C14—C15—C16 | −10.3 (4) |
O5—S1—C3—C2 | 38.00 (19) | C13—C14—C15—C18 | 169.5 (2) |
O3—S1—C3—C2 | −80.73 (18) | C18—C15—C16—C17 | −0.8 (3) |
C2—C3—C4—C5 | 0.9 (3) | C14—C15—C16—C17 | 179.1 (2) |
S1—C3—C4—C5 | −178.04 (17) | C19—N2—C17—C16 | 0.7 (3) |
C3—C4—C5—C6 | −2.2 (4) | C15—C16—C17—N2 | 0.0 (3) |
C4—C5—C6—C7 | 1.1 (4) | C16—C15—C18—C19 | 0.8 (3) |
C5—C6—C7—C2 | 1.2 (4) | C14—C15—C18—C19 | −179.1 (2) |
C3—C2—C7—C6 | −2.5 (3) | C17—N2—C19—C18 | −0.7 (4) |
C1—C2—C7—C6 | 174.8 (2) | C15—C18—C19—N2 | 0.0 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.83 (3) | 2.00 (1) | 2.798 (2) | 160 (3) |
O1—H1A···N1i | 0.86 (3) | 1.76 (3) | 2.617 (2) | 175 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
(II) 1,10-phenanthrolin-1-ium 4-carboxybenzenesulfonate dihydrate
top
Crystal data top
C12H9N2+·C7H5O5S−·2H2O | Dx = 1.490 Mg m−3 |
Mr = 418.41 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P41 | Cell parameters from 5906 reflections |
Hall symbol: P 4w | θ = 2.3–27.4° |
a = 7.1807 (6) Å | µ = 0.22 mm−1 |
c = 36.171 (3) Å | T = 295 K |
V = 1865.1 (3) Å3 | Prism, colorless |
Z = 4 | 0.33 × 0.31 × 0.25 mm |
F(000) = 872 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4269 independent reflections |
Radiation source: fine-focus sealed tube | 3975 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
phi and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→9 |
Tmin = 0.931, Tmax = 0.947 | k = −6→9 |
11629 measured reflections | l = −46→46 |
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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0707P)2 + 0.2329P] where P = (Fo2 + 2Fc2)/3 |
S = 0.80 | (Δ/σ)max < 0.001 |
4269 reflections | Δρmax = 0.16 e Å−3 |
280 parameters | Δρmin = −0.29 e Å−3 |
9 restraints | Absolute structure: Flack (1983), 2097 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (6) |
Crystal data top
C12H9N2+·C7H5O5S−·2H2O | Z = 4 |
Mr = 418.41 | Mo Kα radiation |
Tetragonal, P41 | µ = 0.22 mm−1 |
a = 7.1807 (6) Å | T = 295 K |
c = 36.171 (3) Å | 0.33 × 0.31 × 0.25 mm |
V = 1865.1 (3) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4269 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3975 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.947 | Rint = 0.021 |
11629 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | Δρmax = 0.16 e Å−3 |
S = 0.80 | Δρmin = −0.29 e Å−3 |
4269 reflections | Absolute structure: Flack (1983), 2097 Friedel pairs |
280 parameters | Absolute structure parameter: 0.04 (6) |
9 restraints | |
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 | 0.68024 (7) | 0.71642 (7) | 0.397327 (13) | 0.03826 (12) | |
O1 | 1.1848 (3) | 0.8081 (3) | 0.24149 (4) | 0.0565 (4) | |
O2 | 1.3954 (2) | 0.8938 (2) | 0.28284 (4) | 0.0500 (4) | |
O3 | 0.5662 (2) | 0.8832 (3) | 0.39467 (5) | 0.0605 (4) | |
O4 | 0.5788 (3) | 0.5473 (3) | 0.38904 (5) | 0.0596 (5) | |
O5 | 0.7784 (2) | 0.7071 (3) | 0.43204 (4) | 0.0588 (5) | |
H6B | 0.978 (2) | 0.726 (4) | 0.2103 (9) | 0.080* | |
H6A | 0.889 (4) | 0.604 (3) | 0.1870 (7) | 0.080* | |
O6 | 0.8735 (3) | 0.6959 (4) | 0.20144 (7) | 0.0785 (6) | |
H7B | 0.682 (4) | 0.847 (3) | 0.2161 (8) | 0.080* | |
H7A | 0.614 (4) | 1.027 (2) | 0.2132 (8) | 0.080* | |
O7 | 0.6064 (3) | 0.9260 (3) | 0.22518 (5) | 0.0649 (5) | |
C1 | 1.2287 (3) | 0.8332 (3) | 0.27332 (5) | 0.0381 (4) | |
C2 | 1.1013 (3) | 0.7981 (3) | 0.30504 (5) | 0.0343 (4) | |
C3 | 0.9188 (3) | 0.7442 (3) | 0.29738 (6) | 0.0401 (4) | |
H3 | 0.8814 | 0.7277 | 0.2730 | 0.048* | |
C4 | 0.7939 (3) | 0.7152 (3) | 0.32552 (5) | 0.0390 (4) | |
H4 | 0.6725 | 0.6789 | 0.3202 | 0.047* | |
C5 | 0.8499 (3) | 0.7405 (3) | 0.36198 (5) | 0.0327 (4) | |
C6 | 1.0315 (3) | 0.7901 (3) | 0.37011 (5) | 0.0371 (4) | |
H6 | 1.0689 | 0.8037 | 0.3946 | 0.044* | |
C7 | 1.1577 (3) | 0.8193 (3) | 0.34169 (5) | 0.0355 (4) | |
H7 | 1.2798 | 0.8530 | 0.3471 | 0.043* | |
N1 | 0.2547 (2) | 0.3657 (3) | 0.36506 (5) | 0.0408 (4) | |
N2 | 0.3836 (3) | 0.4006 (3) | 0.29415 (5) | 0.0479 (4) | |
C8 | 0.2033 (3) | 0.3484 (3) | 0.40028 (6) | 0.0501 (5) | |
H8 | 0.2851 | 0.3824 | 0.4190 | 0.060* | |
C9 | 0.0292 (3) | 0.2802 (3) | 0.40900 (7) | 0.0520 (5) | |
H9 | −0.0053 | 0.2630 | 0.4336 | 0.062* | |
C10 | −0.0926 (3) | 0.2379 (3) | 0.38099 (7) | 0.0487 (5) | |
H10 | −0.2115 | 0.1950 | 0.3866 | 0.058* | |
C11 | −0.0394 (3) | 0.2590 (3) | 0.34404 (6) | 0.0404 (4) | |
C12 | −0.1598 (3) | 0.2159 (3) | 0.31366 (8) | 0.0535 (6) | |
H12 | −0.2808 | 0.1757 | 0.3182 | 0.064* | |
C13 | −0.0991 (4) | 0.2330 (3) | 0.27843 (8) | 0.0573 (6) | |
H13 | −0.1791 | 0.2039 | 0.2591 | 0.069* | |
C14 | 0.0846 (3) | 0.2947 (3) | 0.27044 (7) | 0.0485 (5) | |
C15 | 0.1549 (5) | 0.3147 (4) | 0.23409 (7) | 0.0634 (7) | |
H15 | 0.0796 | 0.2882 | 0.2138 | 0.076* | |
C16 | 0.3323 (5) | 0.3726 (4) | 0.22901 (7) | 0.0662 (8) | |
H16 | 0.3808 | 0.3838 | 0.2053 | 0.079* | |
C18 | 0.1414 (3) | 0.3215 (2) | 0.33640 (5) | 0.0365 (4) | |
C17 | 0.4418 (4) | 0.4151 (4) | 0.25969 (7) | 0.0594 (6) | |
H17 | 0.5629 | 0.4562 | 0.2556 | 0.071* | |
C19 | 0.2081 (3) | 0.3401 (3) | 0.29933 (6) | 0.0407 (4) | |
H1A | 0.362 (2) | 0.402 (4) | 0.3611 (10) | 0.080* | |
H2A | 1.465 (4) | 0.918 (5) | 0.2641 (6) | 0.080* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0355 (2) | 0.0478 (3) | 0.0315 (2) | −0.00295 (19) | 0.00165 (18) | 0.00395 (19) |
O1 | 0.0543 (9) | 0.0826 (13) | 0.0326 (8) | −0.0121 (8) | 0.0057 (6) | −0.0032 (7) |
O2 | 0.0421 (8) | 0.0673 (10) | 0.0407 (8) | −0.0067 (7) | 0.0054 (6) | 0.0041 (7) |
O3 | 0.0585 (10) | 0.0650 (10) | 0.0581 (10) | 0.0170 (8) | 0.0180 (8) | 0.0098 (9) |
O4 | 0.0566 (10) | 0.0670 (11) | 0.0553 (10) | −0.0234 (8) | 0.0074 (7) | 0.0015 (8) |
O5 | 0.0468 (9) | 0.0939 (14) | 0.0357 (8) | −0.0049 (9) | −0.0014 (7) | 0.0093 (8) |
O6 | 0.0716 (13) | 0.0919 (16) | 0.0722 (13) | 0.0193 (11) | −0.0204 (10) | −0.0422 (12) |
O7 | 0.0578 (10) | 0.0750 (13) | 0.0619 (11) | 0.0080 (9) | 0.0202 (8) | 0.0218 (9) |
C1 | 0.0419 (10) | 0.0351 (9) | 0.0373 (10) | 0.0028 (7) | 0.0038 (8) | 0.0010 (8) |
C2 | 0.0391 (9) | 0.0320 (8) | 0.0318 (9) | 0.0037 (7) | 0.0027 (7) | 0.0021 (7) |
C3 | 0.0412 (10) | 0.0506 (11) | 0.0284 (8) | −0.0032 (8) | −0.0028 (7) | 0.0010 (8) |
C4 | 0.0354 (9) | 0.0468 (11) | 0.0348 (9) | −0.0056 (8) | −0.0028 (7) | 0.0011 (8) |
C5 | 0.0347 (9) | 0.0330 (8) | 0.0303 (9) | 0.0005 (7) | 0.0003 (7) | 0.0032 (7) |
C6 | 0.0396 (10) | 0.0406 (10) | 0.0310 (9) | −0.0007 (7) | −0.0033 (7) | −0.0010 (7) |
C7 | 0.0316 (9) | 0.0378 (9) | 0.0372 (9) | −0.0006 (7) | −0.0029 (7) | 0.0000 (8) |
N1 | 0.0382 (8) | 0.0437 (9) | 0.0406 (9) | −0.0003 (7) | −0.0030 (7) | 0.0032 (7) |
N2 | 0.0465 (10) | 0.0485 (10) | 0.0488 (10) | 0.0071 (8) | 0.0055 (8) | 0.0035 (8) |
C8 | 0.0542 (12) | 0.0537 (12) | 0.0423 (11) | −0.0041 (9) | −0.0047 (10) | 0.0028 (10) |
C9 | 0.0585 (14) | 0.0519 (13) | 0.0455 (12) | −0.0016 (10) | 0.0103 (10) | 0.0044 (10) |
C10 | 0.0410 (11) | 0.0410 (11) | 0.0641 (14) | −0.0026 (8) | 0.0102 (10) | 0.0014 (10) |
C11 | 0.0363 (9) | 0.0303 (9) | 0.0547 (12) | 0.0043 (7) | −0.0040 (9) | −0.0057 (8) |
C12 | 0.0391 (11) | 0.0448 (12) | 0.0765 (17) | 0.0030 (9) | −0.0121 (11) | −0.0123 (11) |
C13 | 0.0575 (14) | 0.0511 (12) | 0.0634 (15) | 0.0118 (10) | −0.0208 (12) | −0.0206 (11) |
C14 | 0.0581 (13) | 0.0381 (10) | 0.0495 (11) | 0.0189 (9) | −0.0093 (10) | −0.0102 (9) |
C15 | 0.091 (2) | 0.0559 (15) | 0.0429 (12) | 0.0331 (14) | −0.0108 (13) | −0.0148 (11) |
C16 | 0.091 (2) | 0.0651 (16) | 0.0421 (13) | 0.0329 (15) | 0.0164 (13) | 0.0042 (11) |
C18 | 0.0389 (9) | 0.0303 (9) | 0.0402 (10) | 0.0058 (7) | −0.0040 (8) | −0.0023 (7) |
C17 | 0.0619 (15) | 0.0584 (14) | 0.0580 (15) | 0.0180 (11) | 0.0167 (12) | 0.0084 (11) |
C19 | 0.0472 (11) | 0.0332 (9) | 0.0417 (10) | 0.0109 (8) | −0.0007 (9) | −0.0010 (8) |
Geometric parameters (Å, º) top
S1—O5 | 1.4416 (16) | N1—H1A | 0.825 (10) |
S1—O4 | 1.4480 (18) | N2—C17 | 1.319 (3) |
S1—O3 | 1.4538 (18) | N2—C19 | 1.345 (3) |
S1—C5 | 1.7741 (19) | C8—C9 | 1.380 (3) |
O1—C1 | 1.207 (3) | C8—H8 | 0.9300 |
O2—C1 | 1.320 (3) | C9—C10 | 1.372 (4) |
O2—H2A | 0.86 (3) | C9—H9 | 0.9300 |
O6—H6B | 0.844 (10) | C10—C11 | 1.398 (3) |
O6—H6A | 0.851 (10) | C10—H10 | 0.9300 |
O7—H7B | 0.85 (3) | C11—C18 | 1.401 (3) |
O7—H7A | 0.848 (10) | C11—C12 | 1.432 (3) |
C1—C2 | 1.489 (3) | C12—C13 | 1.352 (4) |
C2—C3 | 1.394 (3) | C12—H12 | 0.9300 |
C2—C7 | 1.395 (3) | C13—C14 | 1.421 (4) |
C3—C4 | 1.372 (3) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—C19 | 1.409 (3) |
C4—C5 | 1.391 (3) | C14—C15 | 1.415 (4) |
C4—H4 | 0.9300 | C15—C16 | 1.353 (5) |
C5—C6 | 1.384 (3) | C15—H15 | 0.9300 |
C6—C7 | 1.386 (3) | C16—C17 | 1.394 (4) |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
C7—H7 | 0.9300 | C18—C19 | 1.430 (3) |
N1—C8 | 1.332 (3) | C17—H17 | 0.9300 |
N1—C18 | 1.356 (3) | | |
| | | |
O5—S1—O4 | 112.79 (11) | N1—C8—H8 | 119.9 |
O5—S1—O3 | 111.82 (12) | C9—C8—H8 | 119.9 |
O4—S1—O3 | 113.18 (12) | C10—C9—C8 | 119.2 (2) |
O5—S1—C5 | 107.25 (9) | C10—C9—H9 | 120.4 |
O4—S1—C5 | 106.15 (10) | C8—C9—H9 | 120.4 |
O3—S1—C5 | 105.00 (9) | C9—C10—C11 | 120.5 (2) |
C1—O2—H2A | 113 (2) | C9—C10—H10 | 119.7 |
H6B—O6—H6A | 108.6 (16) | C11—C10—H10 | 119.7 |
H7B—O7—H7A | 109.4 (16) | C10—C11—C18 | 118.5 (2) |
O1—C1—O2 | 122.35 (19) | C10—C11—C12 | 123.0 (2) |
O1—C1—C2 | 123.30 (19) | C18—C11—C12 | 118.5 (2) |
O2—C1—C2 | 114.35 (17) | C13—C12—C11 | 120.6 (2) |
C3—C2—C7 | 119.48 (18) | C13—C12—H12 | 119.7 |
C3—C2—C1 | 118.13 (17) | C11—C12—H12 | 119.7 |
C7—C2—C1 | 122.38 (17) | C12—C13—C14 | 121.3 (2) |
C4—C3—C2 | 120.60 (18) | C12—C13—H13 | 119.4 |
C4—C3—H3 | 119.7 | C14—C13—H13 | 119.4 |
C2—C3—H3 | 119.7 | C19—C14—C15 | 116.2 (2) |
C3—C4—C5 | 119.66 (18) | C19—C14—C13 | 120.4 (2) |
C3—C4—H4 | 120.2 | C15—C14—C13 | 123.5 (2) |
C5—C4—H4 | 120.2 | C16—C15—C14 | 119.5 (2) |
C6—C5—C4 | 120.48 (17) | C16—C15—H15 | 120.2 |
C6—C5—S1 | 121.28 (14) | C14—C15—H15 | 120.2 |
C4—C5—S1 | 118.19 (14) | C15—C16—C17 | 119.4 (2) |
C5—C6—C7 | 119.84 (17) | C15—C16—H16 | 120.3 |
C5—C6—H6 | 120.1 | C17—C16—H16 | 120.3 |
C7—C6—H6 | 120.1 | N1—C18—C11 | 118.69 (19) |
C6—C7—C2 | 119.91 (18) | N1—C18—C19 | 119.60 (18) |
C6—C7—H7 | 120.0 | C11—C18—C19 | 121.71 (18) |
C2—C7—H7 | 120.0 | N2—C17—C16 | 123.8 (3) |
C8—N1—C18 | 122.93 (19) | N2—C17—H17 | 118.1 |
C8—N1—H1A | 117 (3) | C16—C17—H17 | 118.1 |
C18—N1—H1A | 120 (3) | N2—C19—C14 | 124.1 (2) |
C17—N2—C19 | 117.0 (2) | N2—C19—C18 | 118.33 (18) |
N1—C8—C9 | 120.2 (2) | C14—C19—C18 | 117.6 (2) |
| | | |
O1—C1—C2—C3 | −3.9 (3) | C18—C11—C12—C13 | 0.8 (3) |
O2—C1—C2—C3 | 176.30 (18) | C11—C12—C13—C14 | −0.3 (4) |
O1—C1—C2—C7 | 176.8 (2) | C12—C13—C14—C19 | −0.2 (3) |
O2—C1—C2—C7 | −3.0 (3) | C12—C13—C14—C15 | 179.9 (2) |
C7—C2—C3—C4 | 1.2 (3) | C19—C14—C15—C16 | 0.7 (3) |
C1—C2—C3—C4 | −178.11 (19) | C13—C14—C15—C16 | −179.4 (2) |
C2—C3—C4—C5 | 0.2 (3) | C14—C15—C16—C17 | −1.3 (4) |
C3—C4—C5—C6 | −1.6 (3) | C8—N1—C18—C11 | 1.6 (3) |
C3—C4—C5—S1 | 175.97 (16) | C8—N1—C18—C19 | −178.6 (2) |
O5—S1—C5—C6 | −15.1 (2) | C10—C11—C18—N1 | −2.5 (3) |
O4—S1—C5—C6 | −135.92 (17) | C12—C11—C18—N1 | 178.81 (18) |
O3—S1—C5—C6 | 103.96 (18) | C10—C11—C18—C19 | 177.72 (18) |
O5—S1—C5—C4 | 167.31 (17) | C12—C11—C18—C19 | −1.0 (3) |
O4—S1—C5—C4 | 46.50 (19) | C19—N2—C17—C16 | 0.3 (4) |
O3—S1—C5—C4 | −73.62 (19) | C15—C16—C17—N2 | 0.8 (4) |
C4—C5—C6—C7 | 1.6 (3) | C17—N2—C19—C14 | −0.9 (3) |
S1—C5—C6—C7 | −175.90 (15) | C17—N2—C19—C18 | 179.6 (2) |
C5—C6—C7—C2 | −0.2 (3) | C15—C14—C19—N2 | 0.4 (3) |
C3—C2—C7—C6 | −1.2 (3) | C13—C14—C19—N2 | −179.53 (19) |
C1—C2—C7—C6 | 178.08 (17) | C15—C14—C19—C18 | 179.95 (18) |
C18—N1—C8—C9 | 1.0 (3) | C13—C14—C19—C18 | 0.0 (3) |
N1—C8—C9—C10 | −2.7 (4) | N1—C18—C19—N2 | 0.4 (3) |
C8—C9—C10—C11 | 1.7 (3) | C11—C18—C19—N2 | −179.83 (17) |
C9—C10—C11—C18 | 0.9 (3) | N1—C18—C19—C14 | −179.24 (17) |
C9—C10—C11—C12 | 179.5 (2) | C11—C18—C19—C14 | 0.6 (3) |
C10—C11—C12—C13 | −177.8 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O1 | 0.84 (1) | 1.96 (1) | 2.783 (3) | 166 (3) |
O6—H6A···O3i | 0.85 (1) | 1.96 (1) | 2.786 (3) | 164 (3) |
O7—H7B···O6 | 0.85 (3) | 1.83 (3) | 2.674 (3) | 170 (4) |
O7—H7A···O5ii | 0.85 (1) | 1.92 (2) | 2.731 (3) | 161 (3) |
N1—H1A···O4 | 0.83 (1) | 2.13 (2) | 2.805 (2) | 139 (3) |
O2—H2A···O7iii | 0.86 (3) | 1.74 (1) | 2.588 (2) | 171 (3) |
Symmetry codes: (i) y, −x+1, z−1/4; (ii) y, −x+2, z−1/4; (iii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C12H11N2+·C7H5O5S− | C12H9N2+·C7H5O5S−·2H2O |
Mr | 384.40 | 418.41 |
Crystal system, space group | Triclinic, P1 | Tetragonal, P41 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 8.7451 (11), 10.0346 (13), 10.7877 (14) | 7.1807 (6), 7.1807 (6), 36.171 (3) |
α, β, γ (°) | 95.377 (1), 104.954 (1), 104.047 (2) | 90, 90, 90 |
V (Å3) | 874.82 (19) | 1865.1 (3) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.22 | 0.22 |
Crystal size (mm) | 0.31 × 0.24 × 0.22 | 0.33 × 0.31 × 0.25 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.935, 0.953 | 0.931, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4632, 3095, 2534 | 11629, 4269, 3975 |
Rint | 0.015 | 0.021 |
(sin θ/λ)max (Å−1) | 0.599 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.111, 0.86 | 0.036, 0.099, 0.80 |
No. of reflections | 3095 | 4269 |
No. of parameters | 250 | 280 |
No. of restraints | 2 | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.35 | 0.16, −0.29 |
Absolute structure | ? | Flack (1983), 2097 Friedel pairs |
Absolute structure parameter | ? | 0.04 (6) |
Selected geometric parameters (Å, º) for (I) topN1—C12 | 1.328 (3) | N2—C17 | 1.331 (3) |
N1—C8 | 1.329 (3) | N2—C19 | 1.335 (3) |
| | | |
C12—N1—C8 | 117.2 (2) | C17—N2—C19 | 121.94 (18) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.83 (3) | 2.004 (14) | 2.798 (2) | 160 (3) |
O1—H1A···N1i | 0.86 (3) | 1.76 (3) | 2.617 (2) | 175 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Selected geometric parameters (Å, º) for (II) topN1—C8 | 1.332 (3) | N2—C17 | 1.319 (3) |
N1—C18 | 1.356 (3) | N2—C19 | 1.345 (3) |
| | | |
C8—N1—C18 | 122.93 (19) | C17—N2—C19 | 117.0 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6B···O1 | 0.844 (10) | 1.956 (12) | 2.783 (3) | 166 (3) |
O6—H6A···O3i | 0.851 (10) | 1.957 (12) | 2.786 (3) | 164 (3) |
O7—H7B···O6 | 0.85 (3) | 1.83 (3) | 2.674 (3) | 170 (4) |
O7—H7A···O5ii | 0.848 (10) | 1.915 (15) | 2.731 (3) | 161 (3) |
N1—H1A···O4 | 0.825 (10) | 2.13 (2) | 2.805 (2) | 139 (3) |
O2—H2A···O7iii | 0.86 (3) | 1.737 (11) | 2.588 (2) | 171 (3) |
Symmetry codes: (i) y, −x+1, z−1/4; (ii) y, −x+2, z−1/4; (iii) x+1, y, z. |
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Intermolecular interactions such as hydrogen bonds and π–π stacking play an essential role in the formation of supramolecular organic complexes (Lehn, 2007; Egli & Sarkhel, 2007). In the supramolecular systems constructed by organic synthons, carboxylic acids and protonated amines are commonly used as donors or acceptors for hydrogen bonds (Raj et al., 2003). Recently, 5-sulfosalicylic acid supramolecular systems containing both sulfonate and carboxylate groups have been extensively explored (Smith, 2005; Smith et al., 2006a,b,c; Fan et al., 2005; Smith, 2005), while investigations of sulfobenzoic acid organic complexes are sparse. A search of the Cambridge Structural Database (CSD; January 2007 update; Allen, 2002) only gave six sulfobenzoic organic complexes, viz. two guanidinium complexes [guanidinium 4-carboxybenzenesulfonate and guanidinium 3-carboxybenzenesulfonate (Videnova-Adrabinska et al., 2001)], 4,4'-bipyridinium bis(2-carboxybenzenesulfonate dihydrate (Li et al., 2004), bis{4-[(4-pyridyl)ethenyl]pyridinium} 4-sulfonatobenzoate trihydrate (Zhang & Zhu, 2006), tetraphenylphosphonium 2-sulfobenzoic acid (Ferrer et al., 2002), and dicyclohexylammonium 2-carboxybenzenesulfonate dihydrate (Ng, 1995). The sulfobenzoic acid has five potential sites for hydrogen bonds: (i) two carboxyl O atoms and (ii) three sulfonate O atoms. Therefore, further exploration of the sulfobenzoic acid organic systems will provide abundant supramolecular architectures. We report here two novel sulfobenzoic acid organic complexes, (I) and (II), in which the poor and rich properties of formation of hydrogen bonds occur, respectively.
Both (I) and (II) are 1:1 proton transfer organic complexes and each contains one protonated amine cation and one deprotonated acid anion. Complex (I) is an anhydrous species, while complex (II) contains two water molecules. As expected, the sulfonic H atoms from 2-sulfobenzoic acid or 4-sulfobenzoic acid are transferred to the protonation sites on N atoms of 1,2-di-4-pyridylethylene or 1,10-phenanthroline in complexes (I) and (II), respectively (Figs. 1 and 2). The protonations on the N atoms in both structures are further confirmed by the C—N bond distances and C—N—C bond angles in the amine cations. According to the investigation by Athimoolam & Natarajan (2007) of the CSD, generally the protonation of the amine N atom results in a slight deformation of the ring and consequently a slightly larger C—N—C bond angle (> 120°), which phenomenon can be also observed in our two structures in that both C17—N2—C19 in (I) and C8—N1—C18 in (II) are larger than 120° (Tables 1 and 3). The carboxyl group in (I) has an interplanar angle of 74.0 (1)° with its attached benzyl ring due to the neighboring steric effect of the sulfonate group, while in (II) the carboxyl group is nearly coplanar with the benzyl ring [3.8 (1)°].
Three anhydrous 1:1 sulfonatobenzoic acid complexes have been reported, and their structures are zero-dimensional species without extended hydrogen bonding (Ferrer et al., 2002) or three-dimensional networks (Videnova-Adrabinska et al., 2001). Complex (I) forms a four-molecule loop (Fig. 3) via N···H—O and O—H···N hydrogen bonds (Table 2). Only one sulfonate O atom and one carboxyl O atom are involved in the hydrogen bonds. In this loop, there is a π–π stacking effect between two protonated 1,2-di-4-pyridylethylene molecules, with a Cg1···Cg2(1 − x, −y, 1 − z) separation of 3.9739 (15) Å and with a dihedral angle of 23.8 (1)° [where Cg1 and Cg2 are the centroids of atoms N1/C8–C12 and N2/C15–C19]. Moreover, significant π–π interactions exist between loops [Cg1···Cg1(2 − x, −y, 1 − z) = 3.6914 (16) Å]. This hydrogen-bonding loop is the first such unit reported in sulfobenzoic organic systems.
The hydrogen-bonding pattern in complex (II) is also novel and very different from those of reported sulfobenzoic acid organic complexes, in which hydrogen-bonding networks are formed by both cations and anions. In (II), the anions and water molecules form a three-dimensional hydrogen-bonding network with large cavities (Fig. 4 and Table 4), in which the cations are hydrogen- bonded as pendant components and occupy the cavities of the networks. Compared with the more limited hydrogen-bonding characteristic in complex (I), abundant hydrogen bonding is observed in complex (II). All five O atoms of the 4-sulfobenzoic acid unit are involved in the formation of hydrogen bonds. It is obvious that water molecules also play a crucial role in the formation of the three-dimensional hydrogen-bonded network. Each of the two water molecules forms three hydrogen bonds with carboxyl and sulfonate groups and another water molecule, resulting in the hydrogen bonding extending in three directions. There are also strong π–π stacking interactions involving protonated 1,10-phenanthroline and 4-sulfonatobenzoic acid. The centroid-to-centroid distances are 3.7109 (13), 3.6668 (13) and 3.7976 (13) Å for Cg1···Cg2(x, 1 + y,z), Cg2···Cg3(x, −1 + y,z) and Cg2···Cg3(1 + x, −1 + y, z), respectively (Cg1, Cg2 and Cg3 are the centroids of atoms N1/C8–C11/C18, C2–C7 and C11–C14/C18–C19).
In conclusion, these two organic complexes have hydrogen-bonding, π–π stacking and charge-transfer interactions, assembling the molecular structures into supramolecular architectures, and both hydrogen-bonding patterns in (I) and (II) are novel and very different form those reported sulfobenzoic organic systems.