Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107025772/sf3040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107025772/sf3040Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107025772/sf3040IIsup3.hkl |
CCDC references: 655539; 655540
The title compounds were synthesized by heating solutions containing 8-hydroxy-7-iodoquinoline-5-sulfonic acid (ferron) (1 mmol) and, respectively, 4-chloroaniline (1 mmol) or 4-bromoaniline (1 mmol) in 50% ethanol–water (50 ml) for 10 min under reflux. After concentration to ca 40 ml, partial room-temperature evaporation of the hot-filtered solutions gave pale-brown [Brown below?] flat prisms of (I) (m.p. 460.6–462.3 K) and large brown flat plates of (II) (m.p. 512.4–513.3 K).
H atoms involved in hydrogen-bonding interactions (H8, H11A, H11B, H11C, H1W and H2W) were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinements in calculated positions, with C—H = 0.95 Å, and were treated as riding atoms, with Uiso(H) = 1.2Ueq(C). In the case of (I), large residual difference electron-density peaks (maximum 1.20 e Å-3) were located adjacent to the iodo-substituent of the ferron anion.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
C6H7ClN+·C9H5INO4S−·H2O | F(000) = 1952 |
Mr = 496.70 | Dx = 1.843 Mg m−3 |
Monoclinic, C2/c | Melting point = 460.6–462.3 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 33.403 (10) Å | Cell parameters from 25 reflections |
b = 5.902 (5) Å | θ = 13.1–16.9° |
c = 19.970 (7) Å | µ = 2.08 mm−1 |
β = 114.56 (2)° | T = 297 K |
V = 3581 (4) Å3 | Prism, brown |
Z = 8 | 0.40 × 0.25 × 0.20 mm |
Rigaku AFC 7R diffractometer | 3356 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.047 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ω/2θ scans | h = −18→43 |
Absorption correction: ψ scan TEXSAN for Windows (Molecular Structure Corporation, 1999) | k = −7→3 |
Tmin = 0.541, Tmax = 0.660 | l = −25→23 |
4800 measured reflections | 25 standard reflections every 150 min |
4108 independent reflections | intensity decay: 0.7% |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.116P)2] where P = (Fo2 + 2Fc2)/3 |
4108 reflections | (Δ/σ)max = 0.002 |
250 parameters | Δρmax = 1.20 e Å−3 |
0 restraints | Δρmin = −1.09 e Å−3 |
C6H7ClN+·C9H5INO4S−·H2O | V = 3581 (4) Å3 |
Mr = 496.70 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.403 (10) Å | µ = 2.08 mm−1 |
b = 5.902 (5) Å | T = 297 K |
c = 19.970 (7) Å | 0.40 × 0.25 × 0.20 mm |
β = 114.56 (2)° |
Rigaku AFC 7R diffractometer | 3356 reflections with I > 2σ(I) |
Absorption correction: ψ scan TEXSAN for Windows (Molecular Structure Corporation, 1999) | Rint = 0.047 |
Tmin = 0.541, Tmax = 0.660 | 25 standard reflections every 150 min |
4800 measured reflections | intensity decay: 0.7% |
4108 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 1.20 e Å−3 |
4108 reflections | Δρmin = −1.09 e Å−3 |
250 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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. |
x | y | z | Uiso*/Ueq | ||
I7 | 0.02926 (1) | −0.21272 (6) | 0.37113 (2) | 0.0502 (1) | |
S5 | 0.20169 (3) | 0.09466 (18) | 0.56351 (5) | 0.0332 (3) | |
O8 | 0.00843 (10) | 0.2083 (6) | 0.4477 (2) | 0.0497 (11) | |
O51 | 0.20815 (9) | −0.0879 (7) | 0.51997 (18) | 0.0493 (10) | |
O52 | 0.21910 (9) | 0.0315 (6) | 0.64119 (15) | 0.0461 (9) | |
O53 | 0.21916 (10) | 0.3089 (6) | 0.55289 (18) | 0.0428 (10) | |
N1 | 0.06015 (10) | 0.5056 (7) | 0.55118 (19) | 0.0410 (10) | |
C2 | 0.08514 (14) | 0.6540 (9) | 0.6000 (3) | 0.0470 (14) | |
C3 | 0.13131 (14) | 0.6415 (10) | 0.6321 (3) | 0.0472 (14) | |
C4 | 0.15222 (12) | 0.4728 (8) | 0.6123 (2) | 0.0407 (13) | |
C5 | 0.14393 (11) | 0.1285 (7) | 0.53214 (19) | 0.0311 (10) | |
C6 | 0.11651 (12) | −0.0163 (7) | 0.4803 (2) | 0.0366 (11) | |
C7 | 0.07029 (12) | 0.0112 (8) | 0.4514 (2) | 0.0371 (10) | |
C8 | 0.05199 (13) | 0.1829 (7) | 0.4755 (2) | 0.0368 (11) | |
C9 | 0.08046 (12) | 0.3368 (8) | 0.5305 (2) | 0.0346 (10) | |
C10 | 0.12683 (12) | 0.3114 (7) | 0.5590 (2) | 0.0345 (11) | |
Cl41 | 0.44704 (5) | 1.1799 (3) | 0.74998 (10) | 0.0731 (6) | |
N11 | 0.28307 (12) | 0.6416 (8) | 0.6137 (2) | 0.0393 (11) | |
C11 | 0.32303 (13) | 0.7778 (8) | 0.6477 (2) | 0.0376 (11) | |
C21 | 0.35688 (16) | 0.6993 (8) | 0.7113 (3) | 0.0501 (16) | |
C31 | 0.39506 (16) | 0.8242 (10) | 0.7431 (3) | 0.0561 (16) | |
C41 | 0.39909 (14) | 1.0216 (9) | 0.7099 (3) | 0.0475 (14) | |
C51 | 0.36571 (17) | 1.0976 (10) | 0.6467 (3) | 0.0552 (17) | |
C61 | 0.32727 (15) | 0.9732 (9) | 0.6146 (2) | 0.0491 (14) | |
O1W | 0.27696 (14) | 0.3768 (9) | 0.7239 (2) | 0.0619 (15) | |
H2 | 0.07140 | 0.77430 | 0.61410 | 0.0560* | |
H3 | 0.14800 | 0.75080 | 0.66770 | 0.0570* | |
H4 | 0.18340 | 0.46390 | 0.63390 | 0.0490* | |
H6 | 0.12860 | −0.13750 | 0.46340 | 0.0440* | |
H8 | 0.001 (2) | 0.350 (12) | 0.467 (5) | 0.063 (19)* | |
H11A | 0.2837 (15) | 0.542 (9) | 0.582 (3) | 0.044 (13)* | |
H11B | 0.262 (2) | 0.735 (12) | 0.598 (4) | 0.048 (15)* | |
H11C | 0.2812 (19) | 0.555 (12) | 0.650 (3) | 0.062 (17)* | |
H21 | 0.35380 | 0.56060 | 0.73280 | 0.0600* | |
H31 | 0.41830 | 0.77440 | 0.78750 | 0.0670* | |
H51 | 0.36890 | 1.23540 | 0.62480 | 0.0660* | |
H61 | 0.30410 | 1.02320 | 0.57010 | 0.0590* | |
H1W | 0.2808 (17) | 0.402 (11) | 0.763 (3) | 0.079 (15)* | |
H2W | 0.2630 (18) | 0.260 (12) | 0.701 (4) | 0.075 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I7 | 0.0403 (2) | 0.0591 (3) | 0.0459 (2) | −0.0052 (1) | 0.0126 (2) | −0.0171 (1) |
S5 | 0.0270 (4) | 0.0473 (6) | 0.0273 (4) | 0.0021 (4) | 0.0133 (3) | 0.0003 (4) |
O8 | 0.0258 (14) | 0.063 (2) | 0.055 (2) | −0.0005 (13) | 0.0116 (13) | −0.0168 (16) |
O51 | 0.0345 (14) | 0.065 (2) | 0.0494 (17) | 0.0043 (14) | 0.0183 (13) | −0.0164 (16) |
O52 | 0.0403 (15) | 0.065 (2) | 0.0294 (13) | −0.0006 (14) | 0.0109 (11) | 0.0116 (14) |
O53 | 0.0353 (14) | 0.057 (2) | 0.0391 (15) | −0.0044 (13) | 0.0184 (12) | 0.0044 (13) |
N1 | 0.0314 (16) | 0.053 (2) | 0.0416 (18) | −0.0019 (14) | 0.0183 (14) | −0.0101 (16) |
C2 | 0.040 (2) | 0.059 (3) | 0.047 (2) | 0.003 (2) | 0.0230 (19) | −0.012 (2) |
C3 | 0.039 (2) | 0.060 (3) | 0.043 (2) | −0.008 (2) | 0.0174 (18) | −0.022 (2) |
C4 | 0.0290 (17) | 0.055 (3) | 0.038 (2) | −0.0036 (17) | 0.0137 (15) | −0.0082 (18) |
C5 | 0.0255 (15) | 0.043 (2) | 0.0269 (16) | −0.0006 (14) | 0.0129 (13) | 0.0006 (15) |
C6 | 0.0376 (19) | 0.045 (2) | 0.0330 (18) | 0.0036 (16) | 0.0205 (15) | 0.0001 (16) |
C7 | 0.0298 (17) | 0.050 (2) | 0.0283 (17) | −0.0033 (15) | 0.0090 (13) | −0.0070 (16) |
C8 | 0.0297 (18) | 0.046 (2) | 0.0344 (19) | −0.0004 (15) | 0.0131 (15) | −0.0005 (16) |
C9 | 0.0285 (17) | 0.046 (2) | 0.0315 (17) | 0.0009 (15) | 0.0147 (14) | −0.0030 (16) |
C10 | 0.0303 (18) | 0.047 (2) | 0.0300 (18) | 0.0005 (15) | 0.0162 (15) | 0.0007 (16) |
Cl41 | 0.0551 (8) | 0.0905 (12) | 0.0747 (10) | −0.0295 (7) | 0.0279 (7) | −0.0180 (8) |
N11 | 0.0344 (17) | 0.047 (2) | 0.0366 (18) | 0.0021 (15) | 0.0150 (15) | −0.0004 (18) |
C11 | 0.0331 (18) | 0.052 (2) | 0.0307 (19) | −0.0004 (16) | 0.0164 (16) | −0.0035 (16) |
C21 | 0.043 (2) | 0.050 (3) | 0.049 (3) | 0.0005 (19) | 0.011 (2) | 0.012 (2) |
C31 | 0.038 (2) | 0.066 (3) | 0.049 (3) | −0.001 (2) | 0.003 (2) | 0.005 (2) |
C41 | 0.041 (2) | 0.057 (3) | 0.047 (2) | −0.0084 (19) | 0.0208 (18) | −0.012 (2) |
C51 | 0.063 (3) | 0.059 (3) | 0.050 (3) | −0.010 (2) | 0.030 (2) | 0.005 (2) |
C61 | 0.047 (2) | 0.060 (3) | 0.035 (2) | −0.001 (2) | 0.0117 (18) | 0.010 (2) |
O1W | 0.079 (3) | 0.077 (3) | 0.0312 (16) | 0.025 (2) | 0.0243 (17) | 0.0093 (18) |
I7—C7 | 2.090 (5) | C5—C6 | 1.361 (6) |
Cl41—C41 | 1.736 (6) | C6—C7 | 1.415 (6) |
S5—O52 | 1.461 (3) | C7—C8 | 1.370 (6) |
S5—O53 | 1.445 (4) | C8—C9 | 1.438 (6) |
S5—O51 | 1.456 (4) | C9—C10 | 1.419 (6) |
S5—C5 | 1.775 (4) | C2—H2 | 0.9500 |
O8—C8 | 1.333 (6) | C3—H3 | 0.9500 |
O8—H8 | 1.00 (8) | C4—H4 | 0.9500 |
O1W—H1W | 0.75 (6) | C6—H6 | 0.9500 |
O1W—H2W | 0.85 (7) | C11—C61 | 1.366 (7) |
N1—C2 | 1.318 (7) | C11—C21 | 1.383 (7) |
N1—C9 | 1.362 (6) | C21—C31 | 1.378 (8) |
N11—C11 | 1.461 (6) | C31—C41 | 1.375 (8) |
N11—H11C | 0.91 (6) | C41—C51 | 1.367 (8) |
N11—H11B | 0.85 (7) | C51—C61 | 1.384 (8) |
N11—H11A | 0.87 (5) | C21—H21 | 0.9500 |
C2—C3 | 1.405 (8) | C31—H31 | 0.9500 |
C3—C4 | 1.366 (7) | C51—H51 | 0.9500 |
C4—C10 | 1.418 (6) | C61—H61 | 0.9500 |
C5—C10 | 1.426 (6) | ||
O51—S5—O52 | 110.7 (2) | N1—C9—C8 | 116.0 (4) |
O51—S5—O53 | 113.0 (2) | C4—C10—C9 | 116.3 (4) |
O51—S5—C5 | 106.36 (19) | C5—C10—C9 | 118.1 (4) |
O52—S5—O53 | 111.9 (2) | C4—C10—C5 | 125.7 (4) |
O52—S5—C5 | 107.34 (18) | N1—C2—H2 | 119.00 |
O53—S5—C5 | 107.2 (2) | C3—C2—H2 | 119.00 |
C8—O8—H8 | 110 (5) | C2—C3—H3 | 120.00 |
H1W—O1W—H2W | 123 (7) | C4—C3—H3 | 120.00 |
C2—N1—C9 | 117.9 (4) | C3—C4—H4 | 120.00 |
C11—N11—H11C | 107 (4) | C10—C4—H4 | 120.00 |
C11—N11—H11A | 115 (4) | C7—C6—H6 | 120.00 |
C11—N11—H11B | 106 (5) | C5—C6—H6 | 119.00 |
H11B—N11—H11C | 110 (7) | N11—C11—C61 | 119.9 (4) |
H11A—N11—H11B | 116 (6) | N11—C11—C21 | 118.9 (4) |
H11A—N11—H11C | 103 (6) | C21—C11—C61 | 121.2 (4) |
N1—C2—C3 | 122.7 (5) | C11—C21—C31 | 119.4 (5) |
C2—C3—C4 | 120.2 (5) | C21—C31—C41 | 119.2 (5) |
C3—C4—C10 | 119.3 (4) | Cl41—C41—C31 | 119.4 (4) |
S5—C5—C6 | 119.1 (3) | Cl41—C41—C51 | 119.4 (4) |
C6—C5—C10 | 120.9 (4) | C31—C41—C51 | 121.2 (5) |
S5—C5—C10 | 119.9 (3) | C41—C51—C61 | 119.8 (5) |
C5—C6—C7 | 120.9 (4) | C11—C61—C51 | 119.1 (4) |
C6—C7—C8 | 120.8 (4) | C11—C21—H21 | 120.00 |
I7—C7—C6 | 119.8 (3) | C31—C21—H21 | 120.00 |
I7—C7—C8 | 119.4 (3) | C41—C31—H31 | 120.00 |
C7—C8—C9 | 119.1 (4) | C21—C31—H31 | 120.00 |
O8—C8—C9 | 120.5 (4) | C41—C51—H51 | 120.00 |
O8—C8—C7 | 120.4 (4) | C61—C51—H51 | 120.00 |
C8—C9—C10 | 120.3 (4) | C11—C61—H61 | 120.00 |
N1—C9—C10 | 123.6 (4) | C51—C61—H61 | 120.00 |
O51—S5—C5—C6 | 3.9 (4) | I7—C7—C8—C9 | −179.7 (3) |
O51—S5—C5—C10 | −173.5 (3) | C6—C7—C8—O8 | 179.6 (4) |
O52—S5—C5—C6 | −114.6 (3) | C6—C7—C8—C9 | 0.4 (6) |
O52—S5—C5—C10 | 68.0 (4) | O8—C8—C9—N1 | −0.2 (6) |
O53—S5—C5—C6 | 125.0 (3) | O8—C8—C9—C10 | −178.9 (4) |
O53—S5—C5—C10 | −52.4 (4) | C7—C8—C9—N1 | 179.0 (4) |
C9—N1—C2—C3 | −1.3 (7) | C7—C8—C9—C10 | 0.3 (6) |
C2—N1—C9—C8 | −178.2 (4) | N1—C9—C10—C4 | 0.6 (6) |
C2—N1—C9—C10 | 0.5 (6) | N1—C9—C10—C5 | −179.4 (4) |
N1—C2—C3—C4 | 1.0 (8) | C8—C9—C10—C4 | 179.2 (4) |
C2—C3—C4—C10 | 0.2 (7) | C8—C9—C10—C5 | −0.8 (6) |
C3—C4—C10—C5 | 179.1 (4) | N11—C11—C21—C31 | 178.8 (5) |
C3—C4—C10—C9 | −0.9 (6) | C61—C11—C21—C31 | 2.0 (8) |
S5—C5—C6—C7 | −177.1 (3) | N11—C11—C61—C51 | −178.6 (5) |
C10—C5—C6—C7 | 0.3 (6) | C21—C11—C61—C51 | −1.9 (7) |
S5—C5—C10—C4 | −2.2 (6) | C11—C21—C31—C41 | −1.6 (8) |
S5—C5—C10—C9 | 177.8 (3) | C21—C31—C41—Cl41 | 179.8 (4) |
C6—C5—C10—C4 | −179.5 (4) | C21—C31—C41—C51 | 1.0 (9) |
C6—C5—C10—C9 | 0.5 (6) | Cl41—C41—C51—C61 | −179.6 (4) |
C5—C6—C7—I7 | 179.4 (3) | C31—C41—C51—C61 | −0.9 (9) |
C5—C6—C7—C8 | −0.7 (6) | C41—C51—C61—C11 | 1.3 (8) |
I7—C7—C8—O8 | −0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···N1 | 1.00 (8) | 2.19 (8) | 2.714 (6) | 111 (6) |
O8—H8···N1i | 1.00 (8) | 2.10 (8) | 2.853 (6) | 131 (7) |
O1W—H1W···O52ii | 0.75 (6) | 2.06 (6) | 2.796 (5) | 167 (6) |
O1W—H2W···O52 | 0.85 (7) | 1.99 (7) | 2.822 (6) | 168 (7) |
N11—H11A···O53 | 0.87 (5) | 2.42 (6) | 2.781 (6) | 106 (4) |
N11—H11A···O51iii | 0.87 (5) | 2.18 (5) | 2.822 (6) | 130 (5) |
N11—H11B···O51iv | 0.85 (7) | 2.10 (7) | 2.902 (6) | 157 (7) |
N11—H11C···O1W | 0.91 (6) | 1.87 (6) | 2.775 (7) | 180 (9) |
C2—H2···O8i | 0.95 | 2.43 | 2.977 (7) | 116 |
C4—H4···O53 | 0.95 | 2.55 | 3.090 (6) | 117 |
C6—H6···O51 | 0.95 | 2.43 | 2.857 (6) | 107 |
C61—H61···O53v | 0.95 | 2.46 | 3.307 (6) | 149 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) x, y+1, z; (v) −x+1/2, −y+3/2, −z+1. |
C6H7BrN+·C9H5INO4S−·H2O | F(000) = 2096 |
Mr = 541.15 | Dx = 1.990 Mg m−3 |
Monoclinic, C2/c | Melting point = 463.2–469.2 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 33.494 (9) Å | Cell parameters from 25 reflections |
b = 5.927 (4) Å | θ = 12.9–16.8° |
c = 19.963 (7) Å | µ = 4.13 mm−1 |
β = 114.29 (2)° | T = 297 K |
V = 3612 (3) Å3 | Block, brown |
Z = 8 | 0.25 × 0.20 × 0.20 mm |
Rigaku AFC 7R diffractometer | 3149 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.015 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ω/2θ scans | h = −18→43 |
Absorption correction: ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999) | k = −7→3 |
Tmin = 0.368, Tmax = 0.436 | l = −25→23 |
4852 measured reflections | 3 standard reflections every 150 min |
4153 independent reflections | intensity decay: 3.1% |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | w = 1/[σ2(Fo2) + (0.1P)2 + 13.3208P] where P = (Fo2 + 2Fc2)/3 |
4153 reflections | (Δ/σ)max = 0.002 |
250 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
C6H7BrN+·C9H5INO4S−·H2O | V = 3612 (3) Å3 |
Mr = 541.15 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.494 (9) Å | µ = 4.13 mm−1 |
b = 5.927 (4) Å | T = 297 K |
c = 19.963 (7) Å | 0.25 × 0.20 × 0.20 mm |
β = 114.29 (2)° |
Rigaku AFC 7R diffractometer | 3149 reflections with I > 2σ(I) |
Absorption correction: ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999) | Rint = 0.015 |
Tmin = 0.368, Tmax = 0.436 | 3 standard reflections every 150 min |
4852 measured reflections | intensity decay: 3.1% |
4153 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | w = 1/[σ2(Fo2) + (0.1P)2 + 13.3208P] where P = (Fo2 + 2Fc2)/3 |
4153 reflections | Δρmax = 0.60 e Å−3 |
250 parameters | Δρmin = −0.63 e Å−3 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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. |
x | y | z | Uiso*/Ueq | ||
I7 | 0.028595 (8) | −0.21563 (5) | 0.371205 (15) | 0.0455 (1) | |
S5 | 0.20058 (2) | 0.08583 (16) | 0.56328 (4) | 0.0314 (2) | |
O8 | 0.00823 (8) | 0.2062 (5) | 0.44780 (18) | 0.0473 (9) | |
O51 | 0.20683 (8) | −0.0996 (6) | 0.52057 (16) | 0.0495 (9) | |
O53 | 0.21825 (8) | 0.2966 (5) | 0.55159 (16) | 0.0425 (9) | |
O52 | 0.21712 (8) | 0.0272 (5) | 0.64096 (14) | 0.0441 (8) | |
N1 | 0.06000 (9) | 0.5033 (6) | 0.54939 (17) | 0.0381 (9) | |
C2 | 0.08518 (12) | 0.6511 (7) | 0.5980 (2) | 0.0422 (11) | |
C3 | 0.13122 (12) | 0.6372 (8) | 0.6299 (2) | 0.0449 (11) | |
C4 | 0.15153 (11) | 0.4668 (7) | 0.6109 (2) | 0.0391 (10) | |
C5 | 0.14306 (10) | 0.1226 (6) | 0.53133 (18) | 0.0304 (9) | |
C6 | 0.11553 (10) | −0.0213 (6) | 0.47922 (18) | 0.0323 (9) | |
C7 | 0.06962 (10) | 0.0071 (6) | 0.45071 (18) | 0.0321 (9) | |
C8 | 0.05197 (10) | 0.1804 (6) | 0.47527 (19) | 0.0322 (10) | |
C9 | 0.08003 (11) | 0.3334 (6) | 0.52942 (19) | 0.0319 (9) | |
C10 | 0.12606 (10) | 0.3069 (6) | 0.55802 (18) | 0.0300 (9) | |
Br41 | 0.445912 (16) | 1.20232 (10) | 0.74928 (3) | 0.0645 (2) | |
N11 | 0.28112 (10) | 0.6306 (7) | 0.6121 (2) | 0.0388 (10) | |
C11 | 0.32062 (12) | 0.7707 (6) | 0.6457 (2) | 0.0346 (10) | |
C21 | 0.35410 (13) | 0.6969 (7) | 0.7091 (2) | 0.0466 (12) | |
C31 | 0.39208 (13) | 0.8250 (8) | 0.7401 (2) | 0.0506 (14) | |
C41 | 0.39474 (12) | 1.0231 (7) | 0.7069 (2) | 0.0425 (11) | |
C51 | 0.36113 (14) | 1.0949 (8) | 0.6430 (2) | 0.0487 (12) | |
C61 | 0.32347 (13) | 0.9666 (7) | 0.6117 (2) | 0.0433 (11) | |
O1W | 0.27665 (13) | 0.3667 (8) | 0.7232 (2) | 0.0623 (13) | |
H2 | 0.071600 | 0.771800 | 0.612000 | 0.0510* | |
H3 | 0.148100 | 0.747200 | 0.664600 | 0.0540* | |
H4 | 0.182500 | 0.454700 | 0.633000 | 0.0470* | |
H6 | 0.127400 | −0.141600 | 0.461800 | 0.0390* | |
H8 | 0.004 (2) | 0.320 (11) | 0.469 (3) | 0.06 (2)* | |
H11A | 0.2830 (13) | 0.540 (8) | 0.580 (2) | 0.044 (12)* | |
H11B | 0.2586 (19) | 0.702 (9) | 0.595 (3) | 0.060 (16)* | |
H11C | 0.2782 (14) | 0.546 (9) | 0.648 (3) | 0.049 (13)* | |
H21 | 0.351400 | 0.559400 | 0.731400 | 0.0560* | |
H31 | 0.415800 | 0.775700 | 0.783600 | 0.0610* | |
H51 | 0.363800 | 1.232000 | 0.620500 | 0.0580* | |
H61 | 0.300100 | 1.013500 | 0.567300 | 0.0520* | |
H1W | 0.2779 (18) | 0.402 (11) | 0.768 (3) | 0.064 (19)* | |
H2W | 0.2615 (16) | 0.260 (9) | 0.704 (3) | 0.074 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I7 | 0.0355 (2) | 0.0474 (2) | 0.0429 (2) | −0.0056 (1) | 0.0054 (1) | −0.0130 (1) |
S5 | 0.0223 (3) | 0.0402 (5) | 0.0286 (4) | 0.0020 (3) | 0.0073 (3) | −0.0006 (3) |
O8 | 0.0221 (12) | 0.0509 (17) | 0.0580 (18) | 0.0028 (11) | 0.0056 (12) | −0.0154 (14) |
O51 | 0.0295 (12) | 0.063 (2) | 0.0509 (16) | 0.0069 (13) | 0.0113 (11) | −0.0188 (15) |
O53 | 0.0302 (13) | 0.0526 (17) | 0.0424 (15) | −0.0044 (11) | 0.0127 (11) | 0.0076 (12) |
O52 | 0.0350 (13) | 0.0550 (17) | 0.0343 (13) | 0.0006 (12) | 0.0063 (11) | 0.0120 (12) |
N1 | 0.0276 (14) | 0.0470 (18) | 0.0370 (15) | 0.0004 (13) | 0.0105 (12) | −0.0066 (14) |
C2 | 0.0324 (18) | 0.047 (2) | 0.045 (2) | 0.0014 (16) | 0.0137 (16) | −0.0128 (18) |
C3 | 0.0307 (17) | 0.055 (2) | 0.043 (2) | −0.0054 (17) | 0.0092 (15) | −0.0211 (19) |
C4 | 0.0231 (15) | 0.050 (2) | 0.0399 (19) | −0.0016 (15) | 0.0087 (14) | −0.0075 (17) |
C5 | 0.0242 (14) | 0.0362 (17) | 0.0281 (15) | 0.0013 (13) | 0.0081 (12) | −0.0011 (14) |
C6 | 0.0266 (15) | 0.0390 (18) | 0.0297 (16) | 0.0022 (13) | 0.0100 (13) | −0.0019 (14) |
C7 | 0.0244 (14) | 0.0373 (18) | 0.0284 (15) | −0.0050 (13) | 0.0047 (12) | −0.0034 (13) |
C8 | 0.0199 (14) | 0.0392 (19) | 0.0329 (16) | −0.0001 (13) | 0.0061 (12) | 0.0007 (14) |
C9 | 0.0260 (15) | 0.0367 (18) | 0.0325 (16) | 0.0013 (13) | 0.0114 (13) | −0.0005 (14) |
C10 | 0.0240 (15) | 0.0371 (18) | 0.0278 (15) | −0.0002 (13) | 0.0095 (12) | 0.0004 (13) |
Br41 | 0.0451 (3) | 0.0761 (4) | 0.0687 (3) | −0.0256 (2) | 0.0199 (2) | −0.0150 (3) |
N11 | 0.0279 (15) | 0.0420 (18) | 0.0396 (18) | −0.0032 (14) | 0.0069 (13) | −0.0051 (16) |
C11 | 0.0302 (17) | 0.0383 (19) | 0.0325 (17) | −0.0022 (14) | 0.0100 (14) | −0.0014 (14) |
C21 | 0.038 (2) | 0.043 (2) | 0.047 (2) | −0.0037 (16) | 0.0056 (17) | 0.0077 (18) |
C31 | 0.0346 (19) | 0.054 (3) | 0.045 (2) | −0.0017 (18) | −0.0019 (16) | 0.0078 (19) |
C41 | 0.0321 (17) | 0.051 (2) | 0.045 (2) | −0.0068 (16) | 0.0165 (15) | −0.0073 (18) |
C51 | 0.050 (2) | 0.048 (2) | 0.045 (2) | −0.0083 (19) | 0.0164 (18) | 0.0061 (19) |
C61 | 0.0391 (19) | 0.045 (2) | 0.0384 (19) | −0.0029 (17) | 0.0086 (16) | 0.0068 (17) |
O1W | 0.077 (2) | 0.072 (3) | 0.0342 (16) | 0.025 (2) | 0.0192 (16) | 0.0093 (17) |
I7—C7 | 2.087 (4) | C5—C6 | 1.368 (5) |
Br41—C41 | 1.894 (4) | C6—C7 | 1.413 (5) |
S5—O53 | 1.442 (3) | C7—C8 | 1.372 (5) |
S5—O52 | 1.458 (3) | C8—C9 | 1.428 (5) |
S5—O51 | 1.458 (4) | C9—C10 | 1.415 (5) |
S5—C5 | 1.776 (4) | C2—H2 | 0.9500 |
O8—C8 | 1.345 (5) | C3—H3 | 0.9500 |
O8—H8 | 0.84 (6) | C4—H4 | 0.9500 |
O1W—H1W | 0.90 (6) | C6—H6 | 0.9500 |
O1W—H2W | 0.80 (5) | C11—C61 | 1.368 (6) |
N1—C2 | 1.322 (5) | C11—C21 | 1.372 (6) |
N1—C9 | 1.358 (5) | C21—C31 | 1.389 (6) |
N11—C11 | 1.470 (6) | C31—C41 | 1.369 (6) |
N11—H11C | 0.91 (5) | C41—C51 | 1.376 (6) |
N11—H11B | 0.81 (6) | C51—C61 | 1.383 (6) |
N11—H11A | 0.86 (4) | C21—H21 | 0.9500 |
C2—C3 | 1.408 (6) | C31—H31 | 0.9500 |
C3—C4 | 1.356 (6) | C51—H51 | 0.9500 |
C4—C10 | 1.414 (5) | C61—H61 | 0.9500 |
C5—C10 | 1.432 (5) | ||
O51—S5—O53 | 113.03 (18) | N1—C9—C8 | 116.3 (3) |
O51—S5—O52 | 111.05 (18) | C4—C10—C9 | 116.7 (3) |
O51—S5—C5 | 106.14 (17) | C5—C10—C9 | 117.9 (3) |
O52—S5—O53 | 112.15 (17) | C4—C10—C5 | 125.4 (3) |
O53—S5—C5 | 107.00 (17) | N1—C2—H2 | 119.00 |
O52—S5—C5 | 107.02 (16) | C3—C2—H2 | 119.00 |
C8—O8—H8 | 106 (5) | C2—C3—H3 | 120.00 |
H1W—O1W—H2W | 115 (6) | C4—C3—H3 | 120.00 |
C2—N1—C9 | 117.7 (3) | C3—C4—H4 | 120.00 |
C11—N11—H11C | 109 (3) | C10—C4—H4 | 120.00 |
C11—N11—H11A | 111 (3) | C7—C6—H6 | 119.00 |
C11—N11—H11B | 114 (4) | C5—C6—H6 | 120.00 |
H11B—N11—H11C | 104 (6) | N11—C11—C61 | 119.1 (4) |
H11A—N11—H11B | 111 (5) | N11—C11—C21 | 118.8 (3) |
H11A—N11—H11C | 108 (5) | C21—C11—C61 | 122.1 (4) |
N1—C2—C3 | 122.9 (4) | C11—C21—C31 | 119.2 (4) |
C2—C3—C4 | 120.0 (4) | C21—C31—C41 | 118.9 (4) |
C3—C4—C10 | 119.3 (4) | Br41—C41—C31 | 119.5 (3) |
S5—C5—C6 | 119.3 (3) | Br41—C41—C51 | 119.0 (3) |
C6—C5—C10 | 120.8 (3) | C31—C41—C51 | 121.5 (4) |
S5—C5—C10 | 119.9 (3) | C41—C51—C61 | 119.7 (4) |
C5—C6—C7 | 120.9 (3) | C11—C61—C51 | 118.7 (4) |
C6—C7—C8 | 120.2 (3) | C11—C21—H21 | 120.00 |
I7—C7—C6 | 119.9 (3) | C31—C21—H21 | 120.00 |
I7—C7—C8 | 120.0 (3) | C41—C31—H31 | 121.00 |
C7—C8—C9 | 120.0 (3) | C21—C31—H31 | 120.00 |
O8—C8—C9 | 120.3 (3) | C41—C51—H51 | 120.00 |
O8—C8—C7 | 119.8 (3) | C61—C51—H51 | 120.00 |
C8—C9—C10 | 120.2 (3) | C11—C61—H61 | 121.00 |
N1—C9—C10 | 123.5 (3) | C51—C61—H61 | 121.00 |
O51—S5—C5—C6 | 3.1 (3) | I7—C7—C8—C9 | −179.7 (3) |
O51—S5—C5—C10 | −174.4 (3) | C6—C7—C8—O8 | 180.0 (3) |
O53—S5—C5—C6 | 124.1 (3) | C6—C7—C8—C9 | 0.4 (5) |
O53—S5—C5—C10 | −53.4 (3) | O8—C8—C9—N1 | −1.2 (5) |
O52—S5—C5—C6 | −115.5 (3) | O8—C8—C9—C10 | −179.7 (3) |
O52—S5—C5—C10 | 67.0 (3) | C7—C8—C9—N1 | 178.4 (3) |
C9—N1—C2—C3 | −0.8 (6) | C7—C8—C9—C10 | −0.1 (5) |
C2—N1—C9—C8 | −178.3 (3) | N1—C9—C10—C4 | 1.0 (5) |
C2—N1—C9—C10 | 0.2 (5) | N1—C9—C10—C5 | −178.9 (3) |
N1—C2—C3—C4 | 0.1 (6) | C8—C9—C10—C4 | 179.4 (3) |
C2—C3—C4—C10 | 1.1 (6) | C8—C9—C10—C5 | −0.5 (5) |
C3—C4—C10—C5 | 178.2 (4) | N11—C11—C21—C31 | 178.2 (4) |
C3—C4—C10—C9 | −1.6 (5) | C61—C11—C21—C31 | 0.3 (6) |
S5—C5—C6—C7 | −177.9 (3) | N11—C11—C61—C51 | −178.7 (4) |
C10—C5—C6—C7 | −0.4 (5) | C21—C11—C61—C51 | −0.8 (6) |
S5—C5—C10—C4 | −1.7 (5) | C11—C21—C31—C41 | 0.9 (6) |
S5—C5—C10—C9 | 178.2 (3) | C21—C31—C41—Br41 | 179.0 (3) |
C6—C5—C10—C4 | −179.1 (4) | C21—C31—C41—C51 | −1.4 (7) |
C6—C5—C10—C9 | 0.7 (5) | Br41—C41—C51—C61 | −179.6 (3) |
C5—C6—C7—I7 | 180.0 (3) | C31—C41—C51—C61 | 0.8 (7) |
C5—C6—C7—C8 | −0.2 (5) | C41—C51—C61—C11 | 0.3 (6) |
I7—C7—C8—O8 | −0.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···N1 | 0.84 (6) | 2.19 (6) | 2.707 (5) | 120 (6) |
O8—H8···N1i | 0.84 (6) | 2.28 (7) | 2.880 (5) | 129 (6) |
O1W—H1W···O52ii | 0.90 (6) | 1.91 (6) | 2.799 (5) | 170 (6) |
O1W—H2W···O52 | 0.80 (5) | 2.04 (6) | 2.833 (6) | 170 (6) |
N11—H11A···O53 | 0.86 (4) | 2.47 (5) | 2.778 (5) | 102 (3) |
N11—H11A···O51iii | 0.86 (4) | 2.20 (4) | 2.844 (5) | 132 (4) |
N11—H11B···O51iv | 0.81 (6) | 2.12 (6) | 2.889 (5) | 160 (6) |
N11—H11C···O1W | 0.91 (5) | 1.86 (5) | 2.768 (6) | 176 (5) |
C2—H2···O8i | 0.95 | 2.44 | 2.998 (6) | 117 |
C4—H4···O53 | 0.95 | 2.56 | 3.097 (5) | 116 |
C6—H6···O51 | 0.95 | 2.44 | 2.859 (5) | 107 |
C61—H61···O53v | 0.95 | 2.47 | 3.287 (5) | 145 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) x, y+1, z; (v) −x+1/2, −y+3/2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C6H7ClN+·C9H5INO4S−·H2O | C6H7BrN+·C9H5INO4S−·H2O |
Mr | 496.70 | 541.15 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 297 | 297 |
a, b, c (Å) | 33.403 (10), 5.902 (5), 19.970 (7) | 33.494 (9), 5.927 (4), 19.963 (7) |
β (°) | 114.56 (2) | 114.29 (2) |
V (Å3) | 3581 (4) | 3612 (3) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.08 | 4.13 |
Crystal size (mm) | 0.40 × 0.25 × 0.20 | 0.25 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Rigaku AFC 7R diffractometer | Rigaku AFC 7R diffractometer |
Absorption correction | ψ scan TEXSAN for Windows (Molecular Structure Corporation, 1999) | ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999) |
Tmin, Tmax | 0.541, 0.660 | 0.368, 0.436 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4800, 4108, 3356 | 4852, 4153, 3149 |
Rint | 0.047 | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.163, 1.10 | 0.028, 0.110, 0.81 |
No. of reflections | 4108 | 4153 |
No. of parameters | 250 | 250 |
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 |
w = 1/[σ2(Fo2) + (0.116P)2] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.1P)2 + 13.3208P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.20, −1.09 | 0.60, −0.63 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999), MSC/AFC Diffractometer Control Software, TEXSAN for Windows, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···N1 | 1.00 (8) | 2.19 (8) | 2.714 (6) | 111 (6) |
O8—H8···N1i | 1.00 (8) | 2.10 (8) | 2.853 (6) | 131 (7) |
O1W—H1W···O52ii | 0.75 (6) | 2.06 (6) | 2.796 (5) | 167 (6) |
O1W—H2W···O52 | 0.85 (7) | 1.99 (7) | 2.822 (6) | 168 (7) |
N11—H11A···O53 | 0.87 (5) | 2.42 (6) | 2.781 (6) | 106 (4) |
N11—H11A···O51iii | 0.87 (5) | 2.18 (5) | 2.822 (6) | 130 (5) |
N11—H11B···O51iv | 0.85 (7) | 2.10 (7) | 2.902 (6) | 157 (7) |
N11—H11C···O1W | 0.91 (6) | 1.87 (6) | 2.775 (7) | 180 (9) |
C2—H2···O8i | 0.95 | 2.43 | 2.977 (7) | 116 |
C4—H4···O53 | 0.95 | 2.55 | 3.090 (6) | 117 |
C6—H6···O51 | 0.95 | 2.43 | 2.857 (6) | 107 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···N1 | 0.84 (6) | 2.19 (6) | 2.707 (5) | 120 (6) |
O8—H8···N1i | 0.84 (6) | 2.28 (7) | 2.880 (5) | 129 (6) |
O1W—H1W···O52ii | 0.90 (6) | 1.91 (6) | 2.799 (5) | 170 (6) |
O1W—H2W···O52 | 0.80 (5) | 2.04 (6) | 2.833 (6) | 170 (6) |
N11—H11A···O53 | 0.86 (4) | 2.47 (5) | 2.778 (5) | 102 (3) |
N11—H11A···O51iii | 0.86 (4) | 2.20 (4) | 2.844 (5) | 132 (4) |
N11—H11B···O51iv | 0.81 (6) | 2.12 (6) | 2.889 (5) | 160 (6) |
N11—H11C···O1W | 0.91 (5) | 1.86 (5) | 2.768 (6) | 176 (5) |
C2—H2···O8i | 0.95 | 2.44 | 2.998 (6) | 117 |
C4—H4···O53 | 0.95 | 2.56 | 3.097 (5) | 116 |
C6—H6···O51 | 0.95 | 2.44 | 2.859 (5) | 107 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) x, y+1, z. |
Ferron (8-hydroxy-7-iodoquinoline-5-sulfonic acid) is a bidentate complexing agent which has analytical applications as a selective colour reagent for the detection of iron(III) but not iron(II) (Vogel, 1964). The crystal structure of ferron (Merritt & Duffin, 1970; Balasubramanian & Muthiah, 1996) has shown the molecule to exist as a sulfonate–quinolinium zwitterion. This is also the case in the structure of the 1:1:1 adduct hydrate of ferron with urea (Smith et al., 2004b). As a sulfonic acid, ferron is potentially capable of protonating most Lewis bases, but the crystal structures of only a small number of such salts have been reported to date. With 8-hydroxyquinoline, a 1:1 sesquihydrate is formed (Smith et al., 2004a), while with bifunctional 4,4'-bipyridine a monoprotonated 1:1 dihydrate is found (Hemamalini et al., 2004). However, with guanidine carbonate, a dianionic ferron species is found in the hydrated compound [2(gu+)ferron2-]·H2O (Smith et al., 2003). Since no compounds of ferron with aniline-type Lewis bases have been reported so far, and considering that anilines are particularly effective in giving stable crystalline salts with aromatic sulfonic acids, e.g. the 1:1 compounds of 5-sulfosalicylic acid with aniline (Bakasova et al., 1991) and the 4-X-substituted anilines (X = F, Cl or Br) (Smith et al., 2005), we attempted the preparation of compounds of the same Lewis base set with ferron in 50% ethanol–water solvent. The chemically stable 1:1 monohydrated crystalline title compounds C6H7ClN+·C9H5INO4S-·H2O, (I), and C6H7BrN+·C9H5INO4S-·H2O, (II), were obtained using 4-chloroaniline and 4-bromoaniline, and their crystal structures are reported here. The reaction with 4-fluoroaniline resulted in the previously observed deiodination reaction of ferron, giving 8-hydroxyquinoline-5-sulfonic acid.
The crystal structure determinations of (I) and (II) show the presence of three-dimensional hydrogen-bonded framework structures and confirm that these two compounds are isomorphous, which is consistent with previous observations (Dey & Desiraju, 2004) that, within the structures of both the 4-X-substituted anilines and 4-(4-X-phenoxy)-substituted anilines (X = Cl, Br, I and ethynyl), with only one exception (4-iodoaniline), all series members are isomorphous. Although the 4-chloro- and 4-bromoanilinium compounds with 5-sulfosalicylic acid are not isomorphous, they are found to be similar structurally (Smith et al., 2005).
In (I) and (II), the anilinium group of the cation and the sulfonate O acceptors of the anion interact head-to-tail and, together with the water molecule, give a cyclic hydrogen-bonded R33(8) (Bernstein et al., 1995) association (the asymmetric unit) (Figs. 1 and 2). Further aminium···sulfonate and water···sulfonate interactions (Tables 1 and 2) form sheets which extend across the bc planes in the cell. These sheets are linked across the a cell direction through centrosymmetric R22(10) cyclic hydrogen-bonded ferron···ferron dimer interactions between the 8-hydroxy donor and hetero-N acceptor groups (Figs. 3 and 4). This represents the first observed occurrence of this type of association in ferron structures, although a similar type of interaction is known in some of the adduct structures of the parent 8-hydroxyquinoline (oxine) (Hughes & Truter, 1979). It is usually precluded in ferron and its neutral adducts because of the presence of the sulfonate–quinolinium group zwitterion. In (I) and (II), three-dimensional framework structures are formed. Also found in the peripheral structure extension in (I) are Cl···Cl contacts [Cl41···Cl41v 3.538 (5) Å; symmetry code: (v) -x + 1, y, -z + 3/2]. In the isomorphous structure of (II), similar short Br···Br contacts [Br41···Br41i 3.612 (3) Å; symmetry code: (i) -x, -y + 1, -z + 1 Please check relocated symmetry code] are also found. Interionic aromatic ferron C2—H···O8i interactions are also present [2.977 (7) Å in (I) and 2.998 (6) Å in (II)].
With the ferron anion, the intraionic O8—H8···N1 hydrogen bond which is present in other non-zwitterionic compounds of ferron (Hemamalini et al., 2004; Smith et al., 2004b) is also found in both (I) and (II) [2.714 (6) and 2.707 (5) Å in (I) and (II), respectively]. Also, the common aromatic ring C6—H6···O51(sulfonate) association [2.857 (6) Å in (I) and 2.859 (5) in (II)] maintains the S5—O51 bond close to the plane of the aromatic ring [torsion angle C6–C5–S5–O51 3.8 (4)° in (I) and 3.1 (3)° in (II)].