In the title compound, C
10H
9N
2+·C
9H
5INO
4S
−·2H
2O, the 4,4′-bipyridine molecule is protonated at one of the pyridine N atoms. These moieties self-assemble into a supramolecular chain along the
a axis through N—H
N hydrogen bonds. The quinolinol OH group acts as a donor with respect to a sulfonate O atom [O—H
O(sulfonate)] and acts as an acceptor with respect to a C—H group of ferron [C—H
O(hydroxy)], forming a supramolecular chain along the
b axis. These two types of supramolecular chains (one type made up of bipyridine motifs and the other made up of sulfoxine motifs) interact
via π–π stacking, generating a three-dimensional framework. These chains are further crosslinked by C—H
O hydrogen bonds and O—H
O hydrogen bonds involving water molecules.
Supporting information
CCDC reference: 200584
Hot aqueous solutions of 4,4'-bipyridine (39.05 mg) and ferron (87.80 mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed over a water bath for half an hour and kept at room temperature for crystallization. After a few days, plate-like yellow crystals were obtained.
One of the H atoms (H11W) of water molecule O1W and one of the H atoms (H22W) of water molecule O2W were located from a difference Fourier map and allowed for but not refined in subsequent calculations. The remaining H atom of each water molecule could not be located. All other H atoms were refined using a riding model; Uiso values were set at 1.2eq(parent). The various O···O interactions are as follows: O1W···O1W(-x + 1, −y, −z) = 2.8164 (7) Å, O1W···O2W(-x + 1, y − 1/2, −z + 1/2) = 2.8113 (7) Å and O2W···O2W(-x + 2, −y + 1, −z + 1) = 2.7961 (8) Å.
Data collection: FEBO (Belleti, 1996); cell refinement: MolEN (Fair, 1990); data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: PLATON97.
4,4'-bipyridinium 8-hydroxy-7-iodoquinoline-5-sulfonate dihydrate
top
Crystal data top
C10H9N2+·C9H5INO4S−·2H2O | F(000) = 1072 |
Mr = 541.32 | Dx = 1.735 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 9.657 (3) Å | θ = 3.0–27.0° |
b = 15.213 (3) Å | µ = 1.69 mm−1 |
c = 14.679 (2) Å | T = 293 K |
β = 106.01 (3)° | Plate, yellow |
V = 2072.9 (9) Å3 | 0.29 × 0.20 × 0.19 mm |
Z = 4 | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.065 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 3.0° |
Graphite monochromator | h = −12→11 |
ω scans | k = 0→19 |
4690 measured reflections | l = 0→18 |
4526 independent reflections | 1 standard reflections every 100 reflections |
3101 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0974P)2 where P = (Fo2 + 2Fc2)/3 |
4526 reflections | (Δ/σ)max < 0.001 |
272 parameters | Δρmax = 2.43 e Å−3 |
0 restraints | Δρmin = −2.49 e Å−3 |
Crystal data top
C10H9N2+·C9H5INO4S−·2H2O | V = 2072.9 (9) Å3 |
Mr = 541.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.657 (3) Å | µ = 1.69 mm−1 |
b = 15.213 (3) Å | T = 293 K |
c = 14.679 (2) Å | 0.29 × 0.20 × 0.19 mm |
β = 106.01 (3)° | |
Data collection top
Philips PW 1100 diffractometer | Rint = 0.065 |
4690 measured reflections | 1 standard reflections every 100 reflections |
4526 independent reflections | intensity decay: none |
3101 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.97 | Δρmax = 2.43 e Å−3 |
4526 reflections | Δρmin = −2.49 e Å−3 |
272 parameters | |
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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | |
I1 | 0.08594 (4) | 0.38215 (2) | 0.21492 (3) | 0.0414 (1) | |
S2 | 0.27537 (14) | 0.02379 (8) | 0.25072 (10) | 0.0320 (4) | |
O1 | 0.3959 (5) | 0.3968 (2) | 0.1775 (4) | 0.0483 (14) | |
O2 | 0.3026 (5) | −0.0260 (3) | 0.1742 (3) | 0.0493 (16) | |
O3 | 0.3712 (5) | 0.0013 (3) | 0.3429 (3) | 0.0448 (12) | |
O4 | 0.1246 (4) | 0.0242 (3) | 0.2502 (3) | 0.0436 (14) | |
N1 | 0.6050 (5) | 0.2779 (3) | 0.1862 (3) | 0.0376 (16) | |
C2 | 0.7075 (6) | 0.2200 (4) | 0.1906 (4) | 0.0412 (19) | |
C3 | 0.6962 (6) | 0.1316 (4) | 0.2090 (4) | 0.0397 (19) | |
C4 | 0.5705 (6) | 0.0992 (4) | 0.2225 (4) | 0.0365 (17) | |
C5 | 0.3167 (5) | 0.1352 (3) | 0.2293 (4) | 0.0290 (16) | |
C6 | 0.2157 (6) | 0.1988 (3) | 0.2264 (4) | 0.0313 (17) | |
C7 | 0.2421 (6) | 0.2881 (3) | 0.2109 (4) | 0.0317 (17) | |
C8 | 0.3712 (6) | 0.3119 (3) | 0.1956 (4) | 0.0333 (17) | |
C9 | 0.4790 (5) | 0.2479 (3) | 0.1990 (4) | 0.0296 (17) | |
C10 | 0.4545 (5) | 0.1585 (3) | 0.2176 (4) | 0.0291 (16) | |
N1A | 0.4789 (4) | 0.2124 (3) | 0.4575 (3) | 0.0391 (16) | |
N10A | 1.2034 (5) | 0.2090 (4) | 0.4578 (3) | 0.0431 (16) | |
C2A | 0.5366 (6) | 0.2850 (4) | 0.4338 (4) | 0.042 (2) | |
C3A | 0.6773 (6) | 0.2862 (4) | 0.4316 (4) | 0.0368 (17) | |
C4A | 0.7612 (5) | 0.2105 (3) | 0.4550 (4) | 0.0298 (16) | |
C5A | 0.6987 (6) | 0.1366 (4) | 0.4815 (4) | 0.0383 (19) | |
C6A | 0.5560 (6) | 0.1393 (4) | 0.4821 (5) | 0.0418 (19) | |
C7A | 0.9151 (5) | 0.2099 (4) | 0.4541 (4) | 0.0308 (16) | |
C8A | 0.9803 (6) | 0.1342 (4) | 0.4341 (4) | 0.0395 (19) | |
C9A | 1.1231 (6) | 0.1360 (4) | 0.4368 (4) | 0.0429 (19) | |
C11A | 1.1404 (6) | 0.2823 (4) | 0.4756 (5) | 0.048 (2) | |
C12A | 0.9971 (6) | 0.2859 (4) | 0.4747 (5) | 0.0427 (19) | |
O1W | 0.3631 (5) | 0.0293 (3) | 0.0032 (3) | 0.0601 (17) | |
O2W | 0.9254 (5) | 0.4751 (4) | 0.5651 (3) | 0.0699 (19) | |
H1 | 0.48290 | 0.40610 | 0.19290 | 0.0580* | |
H2 | 0.79330 | 0.23980 | 0.18080 | 0.0500* | |
H3 | 0.77350 | 0.09410 | 0.21220 | 0.0480* | |
H4 | 0.56130 | 0.03970 | 0.23460 | 0.0440* | |
H6 | 0.12710 | 0.18290 | 0.23480 | 0.0380* | |
H1A | 0.38960 | 0.21250 | 0.45690 | 0.0470* | |
H2A | 0.48090 | 0.33550 | 0.41850 | 0.0500* | |
H3A | 0.71700 | 0.33720 | 0.41460 | 0.0440* | |
H5A | 0.75220 | 0.08550 | 0.49880 | 0.0470* | |
H6A | 0.51350 | 0.08970 | 0.49990 | 0.0500* | |
H8A | 0.92770 | 0.08240 | 0.41930 | 0.0480* | |
H9A | 1.16590 | 0.08470 | 0.42330 | 0.0520* | |
H11A | 1.19510 | 0.33340 | 0.48930 | 0.0580* | |
H12A | 0.95640 | 0.33820 | 0.48770 | 0.0510* | |
H11W | 0.37790 | −0.01050 | 0.05380 | 0.0480* | |
H22W | 0.96540 | 0.48350 | 0.63090 | 0.0480* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0318 (2) | 0.0336 (2) | 0.0554 (3) | 0.0072 (2) | 0.0065 (2) | −0.0018 (2) |
S2 | 0.0277 (6) | 0.0247 (6) | 0.0419 (8) | −0.0047 (5) | 0.0068 (6) | 0.0000 (6) |
O1 | 0.037 (2) | 0.025 (2) | 0.082 (3) | −0.0042 (17) | 0.015 (2) | 0.001 (2) |
O2 | 0.058 (3) | 0.035 (2) | 0.060 (3) | −0.006 (2) | 0.025 (2) | −0.010 (2) |
O3 | 0.041 (2) | 0.037 (2) | 0.048 (2) | −0.0031 (18) | −0.0016 (19) | 0.0074 (18) |
O4 | 0.0228 (19) | 0.041 (2) | 0.067 (3) | −0.0124 (17) | 0.0126 (18) | −0.004 (2) |
N1 | 0.033 (3) | 0.031 (2) | 0.047 (3) | −0.0102 (19) | 0.008 (2) | −0.002 (2) |
C2 | 0.027 (3) | 0.046 (3) | 0.052 (4) | −0.005 (2) | 0.013 (3) | 0.004 (3) |
C3 | 0.024 (3) | 0.046 (3) | 0.048 (4) | 0.005 (2) | 0.008 (2) | −0.001 (3) |
C4 | 0.027 (3) | 0.033 (3) | 0.046 (3) | 0.000 (2) | 0.004 (2) | −0.001 (2) |
C5 | 0.021 (2) | 0.028 (3) | 0.034 (3) | −0.005 (2) | 0.001 (2) | 0.002 (2) |
C6 | 0.025 (3) | 0.031 (3) | 0.037 (3) | −0.002 (2) | 0.007 (2) | 0.002 (2) |
C7 | 0.026 (3) | 0.028 (3) | 0.037 (3) | 0.002 (2) | 0.002 (2) | −0.003 (2) |
C8 | 0.030 (3) | 0.028 (3) | 0.038 (3) | −0.009 (2) | 0.003 (2) | −0.007 (2) |
C9 | 0.026 (3) | 0.029 (3) | 0.032 (3) | −0.005 (2) | 0.005 (2) | −0.005 (2) |
C10 | 0.023 (2) | 0.029 (3) | 0.032 (3) | −0.002 (2) | 0.002 (2) | −0.001 (2) |
N1A | 0.012 (2) | 0.058 (3) | 0.044 (3) | 0.000 (2) | 0.0021 (18) | −0.003 (2) |
N10A | 0.018 (2) | 0.064 (3) | 0.045 (3) | 0.000 (2) | 0.005 (2) | −0.001 (3) |
C2A | 0.021 (3) | 0.049 (4) | 0.050 (4) | 0.010 (3) | 0.002 (2) | 0.002 (3) |
C3A | 0.021 (3) | 0.037 (3) | 0.050 (3) | −0.001 (2) | 0.006 (2) | 0.004 (3) |
C4A | 0.014 (2) | 0.035 (3) | 0.038 (3) | 0.000 (2) | 0.003 (2) | −0.002 (2) |
C5A | 0.023 (3) | 0.036 (3) | 0.056 (4) | 0.004 (2) | 0.011 (3) | 0.002 (3) |
C6A | 0.024 (3) | 0.047 (3) | 0.054 (4) | −0.008 (2) | 0.010 (3) | −0.001 (3) |
C7A | 0.014 (2) | 0.039 (3) | 0.037 (3) | 0.000 (2) | 0.003 (2) | 0.002 (2) |
C8A | 0.022 (3) | 0.046 (3) | 0.050 (4) | −0.001 (2) | 0.009 (2) | −0.004 (3) |
C9A | 0.023 (3) | 0.057 (4) | 0.046 (3) | 0.013 (3) | 0.005 (2) | 0.001 (3) |
C11A | 0.026 (3) | 0.057 (4) | 0.058 (4) | −0.012 (3) | 0.008 (3) | −0.006 (3) |
C12A | 0.021 (3) | 0.042 (3) | 0.063 (4) | −0.001 (2) | 0.008 (3) | −0.004 (3) |
O1W | 0.040 (3) | 0.079 (3) | 0.059 (3) | −0.003 (2) | 0.010 (2) | 0.010 (3) |
O2W | 0.046 (3) | 0.095 (4) | 0.059 (3) | 0.012 (3) | −0.002 (2) | −0.019 (3) |
Geometric parameters (Å, º) top
I1—C7 | 2.091 (5) | C8—C9 | 1.416 (7) |
S2—O2 | 1.438 (5) | C9—C10 | 1.420 (7) |
S2—O3 | 1.454 (5) | C2—H2 | 0.9294 |
S2—O4 | 1.454 (4) | C3—H3 | 0.9304 |
S2—C5 | 1.789 (5) | C4—H4 | 0.9314 |
O1—C8 | 1.353 (6) | C6—H6 | 0.9295 |
O1—H1 | 0.8199 | C2A—C3A | 1.368 (9) |
O1W—H11W | 0.9382 | C3A—C4A | 1.395 (8) |
O2W—H22W | 0.9448 | C4A—C7A | 1.490 (7) |
N1—C9 | 1.360 (7) | C4A—C5A | 1.382 (8) |
N1—C2 | 1.313 (8) | C5A—C6A | 1.381 (9) |
N1A—C2A | 1.326 (8) | C7A—C12A | 1.387 (8) |
N1A—C6A | 1.332 (8) | C7A—C8A | 1.382 (8) |
N10A—C9A | 1.341 (8) | C8A—C9A | 1.369 (9) |
N10A—C11A | 1.330 (8) | C11A—C12A | 1.381 (9) |
N1A—H1A | 0.8600 | C2A—H2A | 0.9292 |
C2—C3 | 1.382 (9) | C3A—H3A | 0.9295 |
C3—C4 | 1.374 (9) | C5A—H5A | 0.9292 |
C4—C10 | 1.425 (8) | C6A—H6A | 0.9302 |
C5—C10 | 1.433 (7) | C8A—H8A | 0.9302 |
C5—C6 | 1.366 (7) | C9A—H9A | 0.9297 |
C6—C7 | 1.412 (7) | C11A—H11A | 0.9302 |
C7—C8 | 1.375 (8) | C12A—H12A | 0.9302 |
| | | |
I1···O1 | 3.197 (5) | C6···C9Aiii | 3.574 (8) |
I1···O4i | 3.105 (4) | C6···C11Av | 3.562 (9) |
I1···H22Wii | 3.1881 | C6···N10Aiii | 3.435 (7) |
S2···H4 | 2.8459 | C6A···O3 | 3.123 (8) |
S2···H9Aiii | 3.1418 | C6A···N1xiii | 3.163 (8) |
S2···H1iv | 2.8765 | C6A···O3x | 3.267 (8) |
S2···H22Wv | 3.0269 | C7···C11Av | 3.489 (9) |
O1···I1 | 3.197 (5) | C8···N10Av | 3.434 (7) |
O1···N1 | 2.688 (6) | C8···C2A | 3.444 (8) |
O1···O3vi | 2.837 (7) | C9···C3A | 3.472 (8) |
O1···C4vi | 3.388 (7) | C9···C2A | 3.384 (8) |
O1W···O2Wiv | 2.812 (7) | C9A···O4xiv | 3.228 (7) |
O1W···O1Wvii | 2.816 (7) | C9A···C6xiv | 3.574 (8) |
O1W···O2 | 2.856 (6) | C11A···C7viii | 3.489 (9) |
O2···O1W | 2.856 (6) | C11A···C6viii | 3.562 (9) |
O2···C3Aiv | 3.283 (8) | C12A···O2W | 3.321 (9) |
O2···C4 | 3.132 (8) | C3A···H12A | 2.7100 |
O2W···O4viii | 2.864 (6) | C5A···H8A | 2.7419 |
O2W···O1Wvi | 2.812 (7) | C8A···H5A | 2.7308 |
O2W···O2Wix | 2.797 (7) | C9A···H6xiv | 3.0604 |
O2W···C12A | 3.321 (9) | C9A···H1Axiv | 2.7651 |
O3···C6Ax | 3.267 (8) | C11A···H1Axiv | 2.7127 |
O3···C4 | 3.305 (8) | C12A···H3A | 2.7180 |
O3···C6A | 3.123 (8) | H1···O2vi | 2.6333 |
O3···O1iv | 2.837 (7) | H1···S2vi | 2.8765 |
O4···C9Aiii | 3.228 (7) | H1···N1 | 2.2951 |
O4···I1xi | 3.105 (4) | H1···O3vi | 2.1834 |
O4···O2Wv | 2.864 (6) | H1···H4vi | 2.3867 |
O1···H4vi | 2.5035 | H1A···C9Aiii | 2.7651 |
O1W···H11Av | 2.6180 | H1A···N10Aiii | 1.8026 |
O1W···H2Axii | 2.8019 | H1A···C11Aiii | 2.7127 |
O1W···H11Wvii | 2.8622 | H2A···O1Wxiii | 2.8019 |
O2···H4 | 2.6086 | H3A···O2vi | 2.4352 |
O2···H11W | 2.1016 | H3A···H12A | 2.2645 |
O2···H3Aiv | 2.4352 | H3A···H11Wvi | 2.5803 |
O2···H1iv | 2.6333 | H3A···C12A | 2.7180 |
O2W···H12A | 2.4301 | H4···O1iv | 2.5035 |
O3···H4 | 2.8015 | H4···H1iv | 2.3867 |
O3···H6Ax | 2.6578 | H4···O2 | 2.6086 |
O3···H9Aiii | 2.8677 | H4···O3 | 2.8015 |
O3···H6A | 2.6947 | H4···S2 | 2.8459 |
O3···H1iv | 2.1834 | H5A···C8A | 2.7308 |
O4···H9Aiii | 2.6275 | H5A···H8A | 2.3081 |
O4···H22Wv | 1.9897 | H6···C9Aiii | 3.0604 |
O4···H6 | 2.4256 | H6···O4 | 2.4256 |
N1···N1Axii | 3.243 (6) | H6A···O3x | 2.6578 |
N1···C6Axii | 3.163 (8) | H6A···O3 | 2.6947 |
N1···O1 | 2.688 (6) | H8A···C5A | 2.7419 |
N1A···N1xiii | 3.243 (6) | H8A···H5A | 2.3081 |
N1A···N10Aiii | 2.662 (6) | H9A···S2xiv | 3.1418 |
N10A···C6xiv | 3.435 (7) | H9A···O3xiv | 2.8677 |
N10A···N1Axiv | 2.662 (6) | H9A···O4xiv | 2.6275 |
N10A···C8viii | 3.434 (7) | H11A···O1Wviii | 2.6180 |
N1···H1 | 2.2951 | H11W···O2 | 2.1016 |
N10A···H1Axiv | 1.8026 | H11W···H3Aiv | 2.5803 |
C2A···C8 | 3.444 (8) | H11W···O1Wvii | 2.8622 |
C2A···C9 | 3.384 (8) | H12A···H3A | 2.2645 |
C3A···C9 | 3.472 (8) | H12A···O2W | 2.4301 |
C3A···O2vi | 3.283 (8) | H12A···C3A | 2.7100 |
C4···O1iv | 3.388 (7) | H22W···I1ii | 3.1881 |
C4···O2 | 3.132 (8) | H22W···S2viii | 3.0269 |
C4···O3 | 3.305 (8) | H22W···O4viii | 1.9897 |
| | | |
O2—S2—O3 | 113.4 (3) | C3—C4—H4 | 120.70 |
O2—S2—O4 | 113.4 (3) | C10—C4—H4 | 120.67 |
O2—S2—C5 | 105.3 (3) | C5—C6—H6 | 119.14 |
O3—S2—O4 | 112.7 (3) | C7—C6—H6 | 119.04 |
O3—S2—C5 | 105.7 (3) | N1A—C2A—C3A | 120.6 (5) |
O4—S2—C5 | 105.5 (3) | C2A—C3A—C4A | 119.7 (5) |
C8—O1—H1 | 109.47 | C3A—C4A—C7A | 121.0 (5) |
C2—N1—C9 | 117.3 (5) | C3A—C4A—C5A | 118.1 (5) |
C2A—N1A—C6A | 121.5 (5) | C5A—C4A—C7A | 120.8 (5) |
C9A—N10A—C11A | 118.2 (5) | C4A—C5A—C6A | 119.5 (5) |
C6A—N1A—H1A | 119.23 | N1A—C6A—C5A | 120.5 (5) |
C2A—N1A—H1A | 119.25 | C8A—C7A—C12A | 118.3 (5) |
N1—C2—C3 | 124.3 (6) | C4A—C7A—C8A | 121.4 (5) |
C2—C3—C4 | 119.9 (6) | C4A—C7A—C12A | 120.3 (5) |
C3—C4—C10 | 118.6 (5) | C7A—C8A—C9A | 119.4 (6) |
S2—C5—C6 | 119.0 (4) | N10A—C9A—C8A | 122.5 (6) |
S2—C5—C10 | 121.0 (4) | N10A—C11A—C12A | 122.9 (6) |
C6—C5—C10 | 120.0 (4) | C7A—C12A—C11A | 118.6 (6) |
C5—C6—C7 | 121.8 (5) | N1A—C2A—H2A | 119.67 |
C6—C7—C8 | 119.5 (5) | C3A—C2A—H2A | 119.72 |
I1—C7—C8 | 121.2 (3) | C2A—C3A—H3A | 120.22 |
I1—C7—C6 | 119.3 (4) | C4A—C3A—H3A | 120.03 |
O1—C8—C7 | 120.0 (5) | C4A—C5A—H5A | 120.30 |
O1—C8—C9 | 119.7 (5) | C6A—C5A—H5A | 120.25 |
C7—C8—C9 | 120.3 (4) | N1A—C6A—H6A | 119.78 |
N1—C9—C8 | 116.2 (4) | C5A—C6A—H6A | 119.74 |
N1—C9—C10 | 123.4 (5) | C7A—C8A—H8A | 120.26 |
C8—C9—C10 | 120.4 (5) | C9A—C8A—H8A | 120.30 |
C4—C10—C9 | 116.5 (5) | N10A—C9A—H9A | 118.77 |
C5—C10—C9 | 118.0 (4) | C8A—C9A—H9A | 118.72 |
C4—C10—C5 | 125.5 (5) | N10A—C11A—H11A | 118.67 |
N1—C2—H2 | 117.85 | C12A—C11A—H11A | 118.46 |
C3—C2—H2 | 117.87 | C7A—C12A—H12A | 120.64 |
C2—C3—H3 | 120.07 | C11A—C12A—H12A | 120.72 |
C4—C3—H3 | 120.08 | | |
| | | |
O2—S2—C5—C6 | 126.6 (5) | C6—C7—C8—C9 | −2.4 (8) |
O2—S2—C5—C10 | −54.9 (5) | I1—C7—C8—C9 | 176.1 (4) |
O3—S2—C5—C6 | −113.1 (5) | O1—C8—C9—N1 | 1.9 (8) |
O3—S2—C5—C10 | 65.4 (5) | C7—C8—C9—C10 | 0.4 (8) |
O4—S2—C5—C6 | 6.5 (5) | O1—C8—C9—C10 | −179.8 (5) |
O4—S2—C5—C10 | −175.1 (5) | C7—C8—C9—N1 | −177.8 (5) |
C2—N1—C9—C8 | 178.9 (5) | C8—C9—C10—C4 | −178.2 (5) |
C9—N1—C2—C3 | −1.2 (8) | C8—C9—C10—C5 | 2.1 (8) |
C2—N1—C9—C10 | 0.7 (8) | N1—C9—C10—C5 | −179.7 (5) |
C6A—N1A—C2A—C3A | 1.7 (8) | N1—C9—C10—C4 | 0.0 (8) |
C2A—N1A—C6A—C5A | −1.5 (9) | N1A—C2A—C3A—C4A | −0.4 (9) |
C9A—N10A—C11A—C12A | 1.0 (9) | C2A—C3A—C4A—C5A | −1.1 (8) |
C11A—N10A—C9A—C8A | −0.7 (8) | C2A—C3A—C4A—C7A | −179.5 (5) |
N1—C2—C3—C4 | 1.1 (9) | C3A—C4A—C5A—C6A | 1.3 (9) |
C2—C3—C4—C10 | −0.4 (8) | C7A—C4A—C5A—C6A | 179.7 (6) |
C3—C4—C10—C9 | −0.1 (8) | C3A—C4A—C7A—C8A | −150.1 (6) |
C3—C4—C10—C5 | 179.5 (5) | C3A—C4A—C7A—C12A | 30.7 (8) |
S2—C5—C10—C9 | 178.8 (4) | C5A—C4A—C7A—C8A | 31.6 (8) |
S2—C5—C10—C4 | −0.8 (8) | C5A—C4A—C7A—C12A | −147.6 (6) |
S2—C5—C6—C7 | 179.3 (4) | C4A—C5A—C6A—N1A | −0.1 (9) |
C10—C5—C6—C7 | 0.8 (9) | C12A—C7A—C8A—C9A | 1.1 (9) |
C6—C5—C10—C9 | −2.7 (8) | C4A—C7A—C12A—C11A | 178.3 (6) |
C6—C5—C10—C4 | 177.6 (6) | C4A—C7A—C8A—C9A | −178.1 (5) |
C5—C6—C7—I1 | −176.7 (4) | C8A—C7A—C12A—C11A | −0.9 (9) |
C5—C6—C7—C8 | 1.9 (9) | C7A—C8A—C9A—N10A | −0.3 (9) |
C6—C7—C8—O1 | 177.8 (5) | N10A—C11A—C12A—C7A | −0.2 (10) |
I1—C7—C8—O1 | −3.7 (8) | | |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) x−1, −y+1/2, z−1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y, −z; (viii) x+1, −y+1/2, z+1/2; (ix) −x+2, −y+1, −z+1; (x) −x+1, −y, −z+1; (xi) −x, y−1/2, −z+1/2; (xii) x, −y+1/2, z−1/2; (xiii) x, −y+1/2, z+1/2; (xiv) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 2.30 | 2.688 (6) | 110 |
O1—H1···O3vi | 0.82 | 2.18 | 2.837 (7) | 137 |
N1A—H1A···N10Aiii | 0.86 | 1.80 | 2.662 (6) | 178 |
O1W—H11W···O2 | 0.94 | 2.10 | 2.856 (6) | 137 |
O2W—H22W···O4viii | 0.94 | 1.99 | 2.864 (6) | 153 |
C3A—H3A···O2vi | 0.93 | 2.44 | 3.283 (8) | 152 |
C4—H4···O1iv | 0.93 | 2.50 | 3.388 (7) | 159 |
C6—H6···O4 | 0.93 | 2.43 | 2.850 (7) | 108 |
C12A—H12A···O2W | 0.93 | 2.43 | 3.321 (9) | 160 |
Symmetry codes: (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2; (viii) x+1, −y+1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C10H9N2+·C9H5INO4S−·2H2O |
Mr | 541.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.657 (3), 15.213 (3), 14.679 (2) |
β (°) | 106.01 (3) |
V (Å3) | 2072.9 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.69 |
Crystal size (mm) | 0.29 × 0.20 × 0.19 |
|
Data collection |
Diffractometer | Philips PW 1100 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4690, 4526, 3101 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.152, 0.97 |
No. of reflections | 4526 |
No. of parameters | 272 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.43, −2.49 |
Selected geometric parameters (Å, º) topI1—C7 | 2.091 (5) | N1—C9 | 1.360 (7) |
S2—O2 | 1.438 (5) | N1—C2 | 1.313 (8) |
S2—O3 | 1.454 (5) | N1A—C2A | 1.326 (8) |
S2—O4 | 1.454 (4) | N1A—C6A | 1.332 (8) |
S2—C5 | 1.789 (5) | N10A—C9A | 1.341 (8) |
O1—C8 | 1.353 (6) | N10A—C11A | 1.330 (8) |
| | | |
O2—S2—O3 | 113.4 (3) | S2—C5—C10 | 121.0 (4) |
O2—S2—O4 | 113.4 (3) | I1—C7—C8 | 121.2 (3) |
O2—S2—C5 | 105.3 (3) | I1—C7—C6 | 119.3 (4) |
O3—S2—O4 | 112.7 (3) | O1—C8—C7 | 120.0 (5) |
O3—S2—C5 | 105.7 (3) | O1—C8—C9 | 119.7 (5) |
O4—S2—C5 | 105.5 (3) | N1—C9—C8 | 116.2 (4) |
C2—N1—C9 | 117.3 (5) | N1—C9—C10 | 123.4 (5) |
C2A—N1A—C6A | 121.5 (5) | N1A—C2A—C3A | 120.6 (5) |
C9A—N10A—C11A | 118.2 (5) | N1A—C6A—C5A | 120.5 (5) |
N1—C2—C3 | 124.3 (6) | N10A—C9A—C8A | 122.5 (6) |
S2—C5—C6 | 119.0 (4) | N10A—C11A—C12A | 122.9 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 2.30 | 2.688 (6) | 110 |
O1—H1···O3i | 0.82 | 2.18 | 2.837 (7) | 137 |
N1A—H1A···N10Aii | 0.86 | 1.80 | 2.662 (6) | 178 |
O1W—H11W···O2 | 0.94 | 2.10 | 2.856 (6) | 137 |
O2W—H22W···O4iii | 0.94 | 1.99 | 2.864 (6) | 153 |
C3A—H3A···O2i | 0.93 | 2.44 | 3.283 (8) | 152 |
C4—H4···O1iv | 0.93 | 2.50 | 3.388 (7) | 159 |
C6—H6···O4 | 0.93 | 2.43 | 2.850 (7) | 108 |
C12A—H12A···O2W | 0.93 | 2.43 | 3.321 (9) | 160 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x+1, −y+1/2, z+1/2; (iv) −x+1, y−1/2, −z+1/2. |
Derivatives of 8-hydroxyquinoline (oxine) are known for their antiamoebic, antibacterial and antifungal activities, which are correlated to their metal-chelating ability (Banerjee & Saha, 1986). The introduction of sulfonic acid into the oxine moiety offers additional metal-binding and hydrogen-bonding sites/modes. This type of ligand is called sulfoxine (sulfonic acid + oxine). Hydrogen bonds are primarily electrostatic and are formed with both strong and weak donors and acceptors (Desiraju & Steiner, 1999). Hydrogen-bonding patterns and metal-binding modes of sulfoxinates are of current interest (Cai, Chen, Liao et al., 2001; Cai, Chen, Feng et al., 2001). The crystal structures of 8-hydroxy-7-iodoquinoline-5-sulfonic acid (ferron; Balasubramanian & Muthiah, 1996), a cobalt complex of ferron (Balasubramanian, 1995), a nickel(II) complex of ferron (Raj et al., 2003) and a zinc(II) complex of ferron (Francis et al., 2003) have recently been reported from our laboratory. 4,4'-Bipyridine is an excellent synthon in preparing novel supramolecular structures, owing to its rigidity and aptness to form strong hydrogen bonds/coordination bonds via its two N atoms. The supramolecular structures made up of many 4,4'-bipyridine have been reported (Lough et al., 2000). In this paper, the hydrogen-bonding patterns of 4,4'-bipyridinium 8-hydroxy-7-iodoquinoline-5-sulfonate dihydrate, (I), are discussed.
The asymmetric unit of (I) contains one 4,4'-bipyridinium cation, a 8-hydroxy-7-iodoquinoline-5-sulfonate (ferron) anion, and two water molecules (Fig. 1). The bipyridine moiety is protonated at one of the ring N atoms (N1A), as is evident from the increase of the internal angle at nitrogen (C2A—N1A—C6A) from 115.45 (19)° in neutral 4,4'-bipyridine (Boag et al., 1999) to 121.5 (5)° in the present study. This increase of the internal angle has also been observed in many 4,4'-bipyridinium salts (Iyere et al., 2002). In the 4,4'-bipyridinium cation, the two rings are twisted by 31.05(X)° about the C7A—C4A bond; this angle normally ranges from 17 (1) to 38.4 (9)° (Subbotin & Aslanov, 1986). The sulfonic acid group is deprotonated. In the 8-hydroxy-7-iodoquinoline system, the hydroxy H atom forms an intramolecular hydrogen bond with the quinoline N atom, leading to a hydrogen-bonded ring with graph-set notation S(5), as also observed in the neutral 8-hydroxyquinoline system. The quinolinol O1 atom is hydrogen bonded to the sulfonate O3 atom and the C4 atom of a screw-related ligand; it is also hydrogen bonded to the quinolinol oxygen (O1), forming a hydrogen-bonded ring, with graph-set notation R22(8) (Etter, 1990; Bernstein et al., 1995). The 4,4'-bipyridinium moieties self-assemble into a supramolecular chain along the a axis through N—H···N hydrogen bonds involving the protonated and the unprotonated N atoms. These two types of supramolecular chains (one type made up of bipyridine motifs and the other made up of sulfoxine motifs) interact via π–π stacking, generating a three-dimensional framework. These chains are further crosslinked by C—H···O and O—H···O hydrogen bonds involving water molecules (Table 2 and Fig 2).
In the structure of (I), π–π interactions between the aromatic rings are observed. The N1/C2–C4/C9/C10 pyridine ring of ferron has stacking interactions with the N1A/C2A–C6A pyridine ring of the 4,4'-bipyridinium cation, with a perpendicular separation of 3.498(X)Å, a centroid-to-centroid distance of 3.653 (3) Å and a slip angle (the angle between the centroid vector and the normal to the plane) of 16.48(X)°. The C5–C10 phenyl ring of ferron is positioned over the N1A/C2A–C6A pyridine ring of the 4,4'-bipyridinium cation, with a perpendicular separation of 3.521(X)Å, a centroid-to-centroid distance of 3.813 (3) Å and a slip angle of 31.23(X)°. These values are close to those reported for aromatic π–π stacking interactions (Hunter, 1994). The I1 atom is in contact with the sulfonate O4 atom [I1···O4(-x, y + 1/2, −z + 1/2) = 3.105 (4) Å; van der Waals distance = 3.50 Å; C7—I1···O4 = 172.2(X)°]; this I···O interaction was also observed in the crystal structure of ferron (Balasubramanian & Muthiah, 1996). This type of halogen–oxygen interaction has been recognized in the literature and is widely used in crystal engineering (Thalladi et al., 1996).