The crystal structures of three proton-transfer compounds of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with 4-
X-substituted anilines (
X = F, Cl and Br), namely 4-fluoroanilinium 5-sulfosalicylate (3-carboxy-4-hydroxybenzenesulfonate) monohydrate, C
6H
7FN
+·C
7H
5O
6S
-·H
2O, (I), 4-chloroanilinium 5-sulfosalicylate hemihydrate, C
6H
7ClN
+·C
7H
5O
6S
-·0.5H
2O, (II), and 4-bromoanilinium 5-sulfosalicylate monohydrate, C
6H
7BrN
+·C
7H
5O
6S
-·H
2O, (III), have been determined. The asymmetric unit in (II) contains two formula units. All three compounds have three-dimensional hydrogen-bonded polymeric structures in which both the water molecule and the carboxylic acid group are involved in structure extension. With both (II) and (III), which are structurally similar, the common cyclic
(8) dimeric carboxylic acid association is present, whereas in (I), an unusual cyclic
(8) association involving all three hetero-species is found.
Supporting information
CCDC references: 264810; 264811; 264812
The title compounds were synthesized by heating under reflux, for 10 min, 1 mmol quantities of 5-SSA and, respectively, 4-fluoroaniline (FAN), 4-chloroaniline (CLAN) and 4-bromoaniline (BRAN) in 50% ethanol/water (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave violet blocks of (I) (m.p. 517.0–518.5 K) and colourless flat prisms of (II) (m.p. 511.6–513.0 K) and (III) (m.p. 514.2–515.7 K).
H atoms involved in hydrogen-bonding interactions (anilinium, carboxylic, phenol and water) were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the respective refinements at calculated positions (C—H = 0.93 Å) as riding atoms [with Uiso(H) = 1.2Ueq(C)].
For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
(I) 4-fluoroanilinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate
top
Crystal data top
C6H7FN+·C7H5O6S−·H2O | F(000) = 360 |
Mr = 347.31 | Dx = 1.595 Mg m−3 |
Monoclinic, P21 | Melting point: 517.0–518.5 (dec.) K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7978 (7) Å | Cell parameters from 2628 reflections |
b = 12.5513 (12) Å | θ = 2.9–27.5° |
c = 8.5306 (8) Å | µ = 0.27 mm−1 |
β = 96.529 (2)° | T = 295 K |
V = 723.12 (12) Å3 | Block, violet |
Z = 2 | 0.30 × 0.30 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2275 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
ϕ and ω scans | h = −8→7 |
3741 measured reflections | k = −14→14 |
2360 independent reflections | l = −7→10 |
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0465P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2360 reflections | Δρmax = 0.19 e Å−3 |
237 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1029 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (3) |
Crystal data top
C6H7FN+·C7H5O6S−·H2O | V = 723.12 (12) Å3 |
Mr = 347.31 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.7978 (7) Å | µ = 0.27 mm−1 |
b = 12.5513 (12) Å | T = 295 K |
c = 8.5306 (8) Å | 0.30 × 0.30 × 0.20 mm |
β = 96.529 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2275 reflections with I > 2σ(I) |
3741 measured reflections | Rint = 0.026 |
2360 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.073 | Δρmax = 0.19 e Å−3 |
S = 1.03 | Δρmin = −0.22 e Å−3 |
2360 reflections | Absolute structure: Flack (1983), 1029 Friedel pairs |
237 parameters | Absolute structure parameter: 0.03 (3) |
1 restraint | |
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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S5 | 0.96121 (7) | 0.21358 (4) | 0.44485 (6) | 0.0276 (2) | |
O2 | 0.8290 (3) | −0.13345 (14) | −0.0200 (2) | 0.0429 (6) | |
O51 | 1.1305 (2) | 0.17912 (13) | 0.55238 (18) | 0.0382 (5) | |
O52 | 0.7843 (2) | 0.22430 (15) | 0.52530 (16) | 0.0363 (5) | |
O53 | 1.0007 (3) | 0.31023 (13) | 0.35849 (19) | 0.0391 (6) | |
O71 | 0.8246 (3) | 0.18239 (13) | −0.1704 (2) | 0.0417 (6) | |
O72 | 0.8297 (3) | 0.01163 (13) | −0.24153 (18) | 0.0439 (6) | |
C1 | 0.8648 (3) | 0.05471 (17) | 0.0316 (3) | 0.0258 (7) | |
C2 | 0.8526 (3) | −0.05107 (18) | 0.0815 (3) | 0.0301 (7) | |
C3 | 0.8631 (3) | −0.07365 (19) | 0.2431 (3) | 0.0350 (8) | |
C4 | 0.8901 (3) | 0.00675 (18) | 0.3517 (3) | 0.0319 (7) | |
C5 | 0.9116 (3) | 0.11223 (17) | 0.3019 (3) | 0.0269 (7) | |
C6 | 0.8986 (3) | 0.13554 (18) | 0.1444 (2) | 0.0265 (6) | |
C7 | 0.8395 (3) | 0.08030 (18) | −0.1378 (3) | 0.0295 (7) | |
F41 | 0.5887 (3) | 0.55890 (18) | −0.3366 (2) | 0.0669 (6) | |
N11 | 0.7149 (3) | 0.48293 (18) | 0.3078 (2) | 0.0412 (7) | |
C11 | 0.6783 (3) | 0.5042 (2) | 0.1366 (3) | 0.0356 (7) | |
C21 | 0.6660 (3) | 0.4190 (2) | 0.0348 (3) | 0.0423 (9) | |
C31 | 0.6357 (4) | 0.4376 (2) | −0.1264 (3) | 0.0464 (9) | |
C41 | 0.6173 (4) | 0.5401 (2) | −0.1784 (3) | 0.0451 (9) | |
C51 | 0.6278 (3) | 0.6267 (2) | −0.0776 (3) | 0.0442 (9) | |
C61 | 0.6589 (3) | 0.6078 (2) | 0.0832 (3) | 0.0399 (8) | |
O1W | 0.4444 (4) | 0.3384 (2) | 0.3885 (4) | 0.0733 (10) | |
H2 | 0.821 (4) | −0.112 (3) | −0.109 (4) | 0.053 (10)* | |
H3 | 0.8516 | −0.1436 | 0.2767 | 0.0420* | |
H4 | 0.8941 | −0.0085 | 0.4587 | 0.0380* | |
H6 | 0.9122 | 0.2057 | 0.1120 | 0.0320* | |
H71 | 0.807 (5) | 0.196 (4) | −0.262 (5) | 0.087 (13)* | |
H11A | 0.748 (4) | 0.543 (4) | 0.359 (4) | 0.062 (10)* | |
H11B | 0.810 (4) | 0.435 (4) | 0.327 (4) | 0.060 (9)* | |
H11C | 0.604 (4) | 0.455 (4) | 0.340 (4) | 0.058 (10)* | |
H21 | 0.6779 | 0.3497 | 0.0735 | 0.0510* | |
H31 | 0.6280 | 0.3812 | −0.1975 | 0.0560* | |
H51 | 0.6143 | 0.6958 | −0.1167 | 0.0530* | |
H61 | 0.6665 | 0.6642 | 0.1542 | 0.0480* | |
H1A | 0.322 (6) | 0.333 (3) | 0.381 (5) | 0.082 (13)* | |
H1B | 0.496 (5) | 0.294 (4) | 0.445 (5) | 0.088 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5 | 0.0385 (3) | 0.0245 (3) | 0.0195 (2) | 0.0000 (2) | 0.0021 (2) | 0.0008 (2) |
O2 | 0.0684 (13) | 0.0267 (9) | 0.0322 (11) | 0.0031 (8) | −0.0001 (9) | 0.0056 (8) |
O51 | 0.0448 (9) | 0.0378 (10) | 0.0300 (9) | −0.0021 (7) | −0.0049 (7) | 0.0054 (7) |
O52 | 0.0454 (9) | 0.0409 (9) | 0.0231 (7) | −0.0074 (8) | 0.0062 (6) | −0.0004 (8) |
O53 | 0.0624 (11) | 0.0268 (9) | 0.0290 (9) | 0.0066 (8) | 0.0094 (8) | 0.0013 (7) |
O71 | 0.0735 (12) | 0.0321 (10) | 0.0200 (9) | −0.0032 (8) | 0.0073 (8) | −0.0013 (7) |
O72 | 0.0717 (11) | 0.0353 (10) | 0.0245 (9) | −0.0011 (8) | 0.0052 (8) | 0.0055 (7) |
C1 | 0.0288 (11) | 0.0264 (12) | 0.0223 (11) | −0.0007 (8) | 0.0035 (8) | −0.0009 (9) |
C2 | 0.0327 (12) | 0.0275 (12) | 0.0294 (12) | 0.0003 (9) | 0.0011 (10) | 0.0032 (10) |
C3 | 0.0469 (14) | 0.0234 (12) | 0.0337 (13) | 0.0031 (10) | 0.0001 (11) | −0.0058 (9) |
C4 | 0.0407 (12) | 0.0326 (13) | 0.0220 (11) | 0.0045 (10) | 0.0015 (9) | −0.0054 (9) |
C5 | 0.0301 (11) | 0.0255 (12) | 0.0249 (12) | 0.0001 (9) | 0.0019 (9) | 0.0005 (9) |
C6 | 0.0316 (10) | 0.0246 (11) | 0.0236 (11) | −0.0006 (9) | 0.0044 (9) | −0.0010 (8) |
C7 | 0.0372 (12) | 0.0289 (13) | 0.0227 (11) | 0.0009 (9) | 0.0046 (9) | 0.0028 (9) |
F41 | 0.0653 (10) | 0.0938 (14) | 0.0408 (9) | −0.0072 (10) | 0.0028 (8) | 0.0101 (9) |
N11 | 0.0420 (12) | 0.0374 (12) | 0.0438 (12) | −0.0050 (9) | 0.0030 (9) | 0.0035 (10) |
C11 | 0.0301 (11) | 0.0371 (14) | 0.0388 (13) | −0.0036 (10) | 0.0008 (10) | 0.0038 (10) |
C21 | 0.0404 (13) | 0.0315 (14) | 0.0537 (17) | −0.0013 (11) | 0.0003 (12) | 0.0012 (11) |
C31 | 0.0419 (15) | 0.0528 (17) | 0.0436 (16) | −0.0018 (12) | 0.0015 (12) | −0.0105 (13) |
C41 | 0.0343 (13) | 0.0612 (18) | 0.0388 (15) | −0.0030 (12) | 0.0001 (11) | 0.0064 (13) |
C51 | 0.0373 (13) | 0.0433 (16) | 0.0513 (17) | −0.0033 (12) | 0.0016 (11) | 0.0112 (13) |
C61 | 0.0364 (12) | 0.0335 (14) | 0.0495 (16) | −0.0035 (10) | 0.0030 (11) | −0.0019 (11) |
O1W | 0.0461 (13) | 0.0627 (17) | 0.111 (2) | 0.0001 (11) | 0.0080 (13) | 0.0397 (15) |
Geometric parameters (Å, º) top
S5—O51 | 1.4535 (15) | C1—C2 | 1.400 (3) |
S5—O52 | 1.4571 (15) | C2—C3 | 1.401 (4) |
S5—O53 | 1.4599 (17) | C3—C4 | 1.368 (3) |
S5—C5 | 1.768 (2) | C4—C5 | 1.403 (3) |
F41—C41 | 1.362 (3) | C5—C6 | 1.368 (3) |
O2—C2 | 1.346 (3) | C3—H3 | 0.9296 |
O71—C7 | 1.313 (3) | C4—H4 | 0.9300 |
O72—C7 | 1.232 (3) | C6—H6 | 0.9307 |
O2—H2 | 0.80 (3) | C11—C61 | 1.379 (4) |
O71—H71 | 0.80 (4) | C11—C21 | 1.374 (4) |
O1W—H1B | 0.79 (5) | C21—C31 | 1.387 (4) |
O1W—H1A | 0.83 (4) | C31—C41 | 1.362 (4) |
N11—C11 | 1.478 (3) | C41—C51 | 1.383 (4) |
N11—H11C | 0.90 (3) | C51—C61 | 1.384 (4) |
N11—H11A | 0.89 (5) | C21—H21 | 0.9306 |
N11—H11B | 0.88 (4) | C31—H31 | 0.9298 |
C1—C6 | 1.399 (3) | C51—H51 | 0.9300 |
C1—C7 | 1.471 (4) | C61—H61 | 0.9292 |
| | | |
O51—S5—O52 | 111.52 (9) | O72—C7—C1 | 122.9 (2) |
O51—S5—O53 | 112.82 (10) | O71—C7—O72 | 122.3 (2) |
O51—S5—C5 | 107.24 (10) | O71—C7—C1 | 114.8 (2) |
O52—S5—O53 | 111.71 (11) | C2—C3—H3 | 119.85 |
O52—S5—C5 | 106.76 (10) | C4—C3—H3 | 119.83 |
O53—S5—C5 | 106.34 (10) | C3—C4—H4 | 119.97 |
C2—O2—H2 | 110 (3) | C5—C4—H4 | 119.93 |
C7—O71—H71 | 115 (4) | C5—C6—H6 | 119.77 |
H1A—O1W—H1B | 111 (4) | C1—C6—H6 | 119.73 |
C11—N11—H11B | 110 (2) | N11—C11—C61 | 119.7 (2) |
C11—N11—H11C | 109 (2) | N11—C11—C21 | 118.4 (2) |
H11A—N11—H11B | 110 (3) | C21—C11—C61 | 121.9 (2) |
H11A—N11—H11C | 111 (3) | C11—C21—C31 | 119.2 (2) |
H11B—N11—H11C | 107 (4) | C21—C31—C41 | 118.7 (2) |
C11—N11—H11A | 110 (2) | F41—C41—C31 | 118.9 (2) |
C2—C1—C6 | 119.3 (2) | F41—C41—C51 | 118.1 (2) |
C2—C1—C7 | 120.1 (2) | C31—C41—C51 | 122.9 (2) |
C6—C1—C7 | 120.59 (19) | C41—C51—C61 | 118.2 (2) |
O2—C2—C1 | 122.7 (2) | C11—C61—C51 | 119.1 (2) |
O2—C2—C3 | 117.8 (2) | C11—C21—H21 | 120.44 |
C1—C2—C3 | 119.5 (2) | C31—C21—H21 | 120.41 |
C2—C3—C4 | 120.3 (2) | C41—C31—H31 | 120.69 |
C3—C4—C5 | 120.1 (2) | C21—C31—H31 | 120.64 |
C4—C5—C6 | 120.1 (2) | C41—C51—H51 | 120.93 |
S5—C5—C6 | 120.63 (17) | C61—C51—H51 | 120.86 |
S5—C5—C4 | 119.23 (19) | C11—C61—H61 | 120.45 |
C1—C6—C5 | 120.5 (2) | C51—C61—H61 | 120.41 |
| | | |
O51—S5—C5—C4 | 51.89 (19) | C1—C2—C3—C4 | −1.6 (3) |
O52—S5—C5—C4 | −67.76 (19) | C2—C3—C4—C5 | −1.3 (3) |
O53—S5—C5—C4 | 172.84 (17) | C3—C4—C5—C6 | 2.3 (3) |
O51—S5—C5—C6 | −126.64 (18) | C3—C4—C5—S5 | −176.21 (16) |
O52—S5—C5—C6 | 113.71 (18) | C4—C5—C6—C1 | −0.3 (3) |
O53—S5—C5—C6 | −5.7 (2) | S5—C5—C6—C1 | 178.21 (16) |
C6—C1—C2—C3 | 3.6 (3) | N11—C11—C61—C51 | 178.98 (19) |
C7—C1—C2—O2 | 3.8 (3) | C61—C11—C21—C31 | 0.8 (3) |
C6—C1—C7—O72 | 172.4 (2) | N11—C11—C21—C31 | −178.7 (2) |
C7—C1—C2—C3 | −175.55 (19) | C21—C11—C61—C51 | −0.6 (3) |
C2—C1—C6—C5 | −2.7 (3) | C11—C21—C31—C41 | −0.6 (4) |
C6—C1—C7—O71 | −8.8 (3) | C21—C31—C41—F41 | 179.6 (2) |
C6—C1—C2—O2 | −177.0 (2) | C21—C31—C41—C51 | 0.1 (4) |
C2—C1—C7—O71 | 170.4 (2) | C31—C41—C51—C61 | 0.2 (4) |
C7—C1—C6—C5 | 176.51 (19) | F41—C41—C51—C61 | −179.3 (2) |
C2—C1—C7—O72 | −8.5 (3) | C41—C51—C61—C11 | 0.1 (3) |
O2—C2—C3—C4 | 179.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O72 | 0.80 (3) | 1.92 (4) | 2.625 (2) | 145 (4) |
O1W—H1A···O53i | 0.83 (4) | 2.19 (4) | 3.019 (3) | 177 (4) |
O1W—H1B···O52 | 0.79 (5) | 2.18 (4) | 2.853 (3) | 142 (4) |
N11—H11A···O51ii | 0.89 (5) | 2.01 (5) | 2.882 (3) | 168 (3) |
N11—H11B···O53 | 0.88 (4) | 2.03 (4) | 2.910 (3) | 172 (4) |
N11—H11C···O1W | 0.90 (3) | 1.90 (4) | 2.726 (3) | 152 (4) |
O71—H71···O52iii | 0.80 (4) | 1.84 (4) | 2.632 (2) | 176 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y+1/2, −z+1; (iii) x, y, z−1. |
(II) 4-chloroanilinium 3-carboxy-4-hydroxybenzenesulfonate hemihydrate
top
Crystal data top
C6H7ClN+·C7H5O6S−·0.5H2O | F(000) = 1464 |
Mr = 354.77 | Dx = 1.576 Mg m−3 |
Monoclinic, P21/c | Melting point = 511.6–513.3.0 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.7107 Å |
a = 7.455 (4) Å | Cell parameters from 3985 reflections |
b = 11.849 (7) Å | θ = 2.4–27.6° |
c = 33.848 (19) Å | µ = 0.43 mm−1 |
β = 90.817 (12)° | T = 295 K |
V = 2990 (3) Å3 | Block, colourless |
Z = 8 | 0.45 × 0.30 × 0.15 mm |
Data collection top
Bruker SMART CCD area detector diffractometer | 4133 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
ϕ and ω scans | h = −8→8 |
11861 measured reflections | k = −14→10 |
5220 independent reflections | l = −39→40 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | w = 1/[σ2(Fo2) + (0.0713P)2] where P = (Fo2 + 2Fc2)/3 |
5220 reflections | (Δ/σ)max = 0.009 |
444 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
C6H7ClN+·C7H5O6S−·0.5H2O | V = 2990 (3) Å3 |
Mr = 354.77 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.455 (4) Å | µ = 0.43 mm−1 |
b = 11.849 (7) Å | T = 295 K |
c = 33.848 (19) Å | 0.45 × 0.30 × 0.15 mm |
β = 90.817 (12)° | |
Data collection top
Bruker SMART CCD area detector diffractometer | 4133 reflections with I > 2σ(I) |
11861 measured reflections | Rint = 0.028 |
5220 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | Δρmax = 0.41 e Å−3 |
5220 reflections | Δρmin = −0.54 e Å−3 |
444 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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S5A | 0.24091 (10) | 0.42594 (5) | 0.048951 (16) | 0.0298 (2) | |
O2A | 0.4975 (3) | 0.69127 (17) | 0.18525 (5) | 0.0528 (8) | |
O51A | 0.0899 (3) | 0.49596 (16) | 0.03683 (5) | 0.0430 (7) | |
O52A | 0.3818 (3) | 0.42376 (16) | 0.01997 (5) | 0.0423 (7) | |
O53A | 0.1838 (3) | 0.31643 (14) | 0.06214 (5) | 0.0421 (5)* | |
O71A | 0.1948 (3) | 0.40020 (16) | 0.20242 (5) | 0.0501 (8) | |
O72A | 0.3446 (3) | 0.54215 (16) | 0.23032 (5) | 0.0475 (8) | |
C1A | 0.3432 (4) | 0.5254 (2) | 0.16093 (7) | 0.0299 (9) | |
C2A | 0.4406 (4) | 0.6245 (2) | 0.15523 (7) | 0.0333 (9) | |
C3A | 0.4810 (4) | 0.6585 (2) | 0.11718 (7) | 0.0380 (10) | |
C4A | 0.4266 (4) | 0.5961 (2) | 0.08543 (7) | 0.0335 (9) | |
C5A | 0.3305 (4) | 0.49675 (19) | 0.09081 (7) | 0.0270 (8) | |
C6A | 0.2897 (4) | 0.46204 (19) | 0.12809 (7) | 0.0276 (8) | |
C7A | 0.2949 (4) | 0.4901 (2) | 0.20068 (7) | 0.0350 (9) | |
S5B | 0.28878 (10) | 0.44097 (5) | 0.456715 (17) | 0.0298 (2) | |
O2B | −0.0095 (3) | 0.18868 (18) | 0.32133 (5) | 0.0549 (8) | |
O51B | 0.1495 (3) | 0.51788 (17) | 0.46989 (6) | 0.0497 (8) | |
O52B | 0.3311 (3) | 0.35715 (17) | 0.48601 (5) | 0.0536 (8) | |
O53B | 0.4447 (3) | 0.50017 (16) | 0.44251 (5) | 0.0409 (7) | |
O71B | 0.2983 (3) | 0.47718 (16) | 0.30390 (5) | 0.0466 (8) | |
O72B | 0.1474 (3) | 0.33540 (16) | 0.27594 (5) | 0.0478 (8) | |
C1B | 0.1618 (4) | 0.3473 (2) | 0.34553 (6) | 0.0290 (9) | |
C2B | 0.0571 (4) | 0.2513 (2) | 0.35121 (7) | 0.0346 (9) | |
C3B | 0.0184 (4) | 0.2173 (2) | 0.38963 (7) | 0.0374 (10) | |
C4B | 0.0862 (4) | 0.2743 (2) | 0.42123 (7) | 0.0340 (9) | |
C5B | 0.1936 (4) | 0.36865 (19) | 0.41585 (7) | 0.0272 (8) | |
C6B | 0.2292 (4) | 0.40597 (19) | 0.37819 (7) | 0.0277 (8) | |
C7B | 0.2027 (4) | 0.3858 (2) | 0.30559 (7) | 0.0336 (9) | |
Cl4C | 0.18989 (18) | 0.46444 (10) | 0.73684 (2) | 0.0892 (5) | |
N1C | 0.1900 (3) | 0.41885 (18) | 0.56285 (6) | 0.0357 (8) | |
C1C | 0.1839 (4) | 0.4342 (2) | 0.60556 (7) | 0.0307 (9) | |
C2C | 0.0969 (4) | 0.3552 (2) | 0.62791 (8) | 0.0402 (10) | |
C3C | 0.0968 (5) | 0.3657 (2) | 0.66835 (8) | 0.0474 (12) | |
C4C | 0.1836 (5) | 0.4547 (3) | 0.68580 (8) | 0.0498 (13) | |
C5C | 0.2647 (5) | 0.5360 (3) | 0.66353 (9) | 0.0515 (11) | |
C6C | 0.2643 (4) | 0.5261 (2) | 0.62290 (8) | 0.0425 (10) | |
Cl4D | 0.35328 (17) | 0.77313 (9) | 0.29620 (2) | 0.0829 (5) | |
N1D | 0.2463 (3) | 0.88873 (18) | 0.46442 (6) | 0.0381 (8) | |
C1D | 0.2694 (4) | 0.8581 (2) | 0.42311 (7) | 0.0336 (9) | |
C2D | 0.3588 (4) | 0.7606 (2) | 0.41341 (8) | 0.0416 (10) | |
C3D | 0.3836 (5) | 0.7348 (2) | 0.37428 (9) | 0.0488 (13) | |
C4D | 0.3188 (5) | 0.8056 (3) | 0.34568 (8) | 0.0478 (10) | |
C5D | 0.2277 (5) | 0.9020 (3) | 0.35511 (9) | 0.0492 (11) | |
C6D | 0.2043 (4) | 0.9286 (2) | 0.39396 (8) | 0.0427 (10) | |
O1W | 0.2885 (5) | 0.7015 (2) | 0.51330 (7) | 0.0575 (10) | |
H2A | 0.473 (7) | 0.662 (4) | 0.2061 (16) | 0.079 (14)* | |
H3A | 0.5458 | 0.7245 | 0.1133 | 0.0450* | |
H4A | 0.4539 | 0.6199 | 0.0600 | 0.0400* | |
H6A | 0.2257 | 0.3955 | 0.1316 | 0.0330* | |
H71A | 0.178 (6) | 0.384 (4) | 0.2260 (15) | 0.075 (15)* | |
H2B | 0.016 (7) | 0.218 (4) | 0.3001 (16) | 0.082 (15)* | |
H3B | −0.0548 | 0.1549 | 0.3936 | 0.0450* | |
H4B | 0.0607 | 0.2499 | 0.4467 | 0.0410* | |
H6B | 0.2983 | 0.4704 | 0.3746 | 0.0330* | |
H71B | 0.302 (7) | 0.499 (4) | 0.2812 (15) | 0.070 (14)* | |
H2C | 0.0383 | 0.2949 | 0.6158 | 0.0480* | |
H3C | 0.0380 | 0.3126 | 0.6837 | 0.0570* | |
H5C | 0.3197 | 0.5976 | 0.6757 | 0.0620* | |
H6C | 0.3180 | 0.5811 | 0.6075 | 0.0510* | |
H11C | 0.091 (7) | 0.447 (4) | 0.5518 (16) | 0.053 (15)* | |
H12C | 0.196 (7) | 0.345 (4) | 0.5573 (17) | 0.063 (15)* | |
H13C | 0.285 (6) | 0.454 (4) | 0.5531 (16) | 0.057 (16)* | |
H2D | 0.4020 | 0.7126 | 0.4331 | 0.0500* | |
H3D | 0.4444 | 0.6694 | 0.3673 | 0.0590* | |
H5D | 0.1822 | 0.9489 | 0.3353 | 0.0590* | |
H6D | 0.1443 | 0.9944 | 0.4007 | 0.0510* | |
H11D | 0.333 (6) | 0.933 (4) | 0.4725 (16) | 0.057 (15)* | |
H12D | 0.251 (6) | 0.827 (4) | 0.4793 (17) | 0.061 (16)* | |
H13D | 0.140 (6) | 0.920 (4) | 0.4676 (16) | 0.053 (15)* | |
H1W | 0.244 (7) | 0.643 (4) | 0.4995 (13) | 0.077 (17)* | |
H2W | 0.414 (8) | 0.685 (4) | 0.5121 (14) | 0.120 (19)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5A | 0.0280 (5) | 0.0377 (4) | 0.0237 (3) | −0.0082 (3) | −0.0011 (3) | 0.0045 (2) |
O2A | 0.0708 (19) | 0.0506 (12) | 0.0370 (10) | −0.0274 (11) | −0.0009 (11) | −0.0055 (9) |
O51A | 0.0289 (15) | 0.0557 (12) | 0.0439 (10) | −0.0051 (9) | −0.0120 (9) | 0.0124 (9) |
O52A | 0.0352 (15) | 0.0624 (13) | 0.0295 (9) | −0.0103 (9) | 0.0054 (9) | −0.0022 (8) |
O53A | 0.0586 (16) | 0.0357 (10) | 0.0321 (9) | −0.0151 (9) | 0.0027 (9) | 0.0002 (7) |
O71A | 0.0750 (19) | 0.0499 (12) | 0.0253 (9) | −0.0301 (11) | 0.0006 (10) | 0.0020 (8) |
O72A | 0.0648 (18) | 0.0492 (12) | 0.0283 (10) | −0.0192 (10) | −0.0022 (9) | −0.0015 (8) |
C1A | 0.0316 (19) | 0.0301 (13) | 0.0281 (12) | 0.0009 (11) | −0.0010 (11) | 0.0017 (10) |
C2A | 0.034 (2) | 0.0320 (14) | 0.0339 (13) | −0.0019 (11) | −0.0030 (12) | −0.0027 (10) |
C3A | 0.041 (2) | 0.0307 (14) | 0.0423 (15) | −0.0122 (12) | 0.0020 (13) | 0.0041 (11) |
C4A | 0.032 (2) | 0.0366 (14) | 0.0319 (13) | −0.0037 (11) | 0.0011 (12) | 0.0071 (10) |
C5A | 0.0225 (18) | 0.0293 (13) | 0.0291 (12) | 0.0013 (10) | −0.0041 (11) | 0.0029 (9) |
C6A | 0.0254 (17) | 0.0283 (12) | 0.0289 (12) | −0.0022 (10) | −0.0019 (11) | 0.0026 (9) |
C7A | 0.038 (2) | 0.0363 (15) | 0.0308 (13) | −0.0010 (12) | 0.0001 (12) | 0.0004 (11) |
S5B | 0.0295 (5) | 0.0355 (4) | 0.0246 (3) | 0.0018 (3) | 0.0023 (3) | 0.0000 (2) |
O2B | 0.0725 (19) | 0.0539 (12) | 0.0382 (11) | −0.0315 (11) | −0.0026 (11) | −0.0050 (9) |
O51B | 0.0342 (16) | 0.0614 (13) | 0.0537 (12) | 0.0045 (9) | 0.0036 (10) | −0.0263 (10) |
O52B | 0.0739 (19) | 0.0529 (12) | 0.0338 (10) | −0.0054 (11) | −0.0112 (10) | 0.0117 (9) |
O53B | 0.0319 (14) | 0.0533 (12) | 0.0377 (10) | −0.0073 (8) | 0.0031 (9) | −0.0033 (8) |
O71B | 0.0647 (18) | 0.0473 (12) | 0.0278 (9) | −0.0223 (10) | −0.0015 (9) | 0.0056 (8) |
O72B | 0.0674 (18) | 0.0479 (11) | 0.0281 (9) | −0.0184 (10) | −0.0042 (9) | −0.0006 (8) |
C1B | 0.0307 (19) | 0.0304 (13) | 0.0258 (12) | 0.0024 (11) | −0.0011 (11) | 0.0018 (9) |
C2B | 0.034 (2) | 0.0340 (14) | 0.0358 (13) | −0.0033 (11) | −0.0009 (12) | −0.0026 (10) |
C3B | 0.036 (2) | 0.0332 (14) | 0.0432 (15) | −0.0060 (11) | 0.0064 (13) | 0.0044 (11) |
C4B | 0.034 (2) | 0.0359 (14) | 0.0322 (13) | 0.0009 (11) | 0.0070 (12) | 0.0070 (10) |
C5B | 0.0242 (18) | 0.0306 (13) | 0.0270 (12) | 0.0046 (10) | 0.0024 (10) | −0.0002 (9) |
C6B | 0.0261 (18) | 0.0264 (12) | 0.0307 (12) | 0.0021 (10) | −0.0003 (11) | 0.0015 (9) |
C7B | 0.035 (2) | 0.0350 (14) | 0.0307 (13) | −0.0015 (11) | −0.0019 (12) | 0.0017 (10) |
Cl4C | 0.1095 (11) | 0.1205 (9) | 0.0371 (4) | 0.0268 (7) | −0.0118 (5) | −0.0154 (5) |
N1C | 0.0318 (17) | 0.0413 (13) | 0.0339 (11) | 0.0031 (10) | 0.0012 (10) | 0.0010 (9) |
C1C | 0.0257 (19) | 0.0348 (14) | 0.0317 (13) | 0.0072 (11) | 0.0004 (11) | −0.0023 (10) |
C2C | 0.046 (2) | 0.0323 (14) | 0.0424 (15) | −0.0022 (12) | 0.0053 (14) | −0.0051 (11) |
C3C | 0.059 (3) | 0.0430 (16) | 0.0406 (15) | 0.0078 (14) | 0.0103 (15) | 0.0042 (12) |
C4C | 0.052 (3) | 0.060 (2) | 0.0374 (15) | 0.0181 (16) | −0.0035 (15) | −0.0068 (14) |
C5C | 0.043 (2) | 0.0545 (19) | 0.0569 (18) | 0.0020 (15) | −0.0053 (16) | −0.0240 (15) |
C6C | 0.034 (2) | 0.0382 (15) | 0.0553 (17) | −0.0003 (12) | 0.0047 (14) | −0.0047 (12) |
Cl4D | 0.1152 (11) | 0.0857 (7) | 0.0482 (5) | −0.0177 (6) | 0.0197 (5) | −0.0067 (4) |
N1D | 0.0293 (17) | 0.0393 (13) | 0.0455 (13) | 0.0020 (10) | −0.0032 (11) | −0.0063 (10) |
C1D | 0.0273 (19) | 0.0325 (14) | 0.0410 (14) | −0.0026 (11) | −0.0001 (12) | −0.0019 (10) |
C2D | 0.041 (2) | 0.0353 (15) | 0.0486 (16) | 0.0033 (12) | 0.0006 (14) | 0.0045 (12) |
C3D | 0.054 (3) | 0.0348 (15) | 0.0580 (18) | −0.0023 (13) | 0.0121 (16) | −0.0057 (13) |
C4D | 0.050 (2) | 0.0488 (17) | 0.0447 (16) | −0.0138 (15) | 0.0067 (15) | −0.0018 (13) |
C5D | 0.042 (2) | 0.0532 (18) | 0.0524 (18) | −0.0048 (14) | −0.0038 (15) | 0.0116 (14) |
C6D | 0.036 (2) | 0.0359 (15) | 0.0563 (18) | 0.0047 (12) | 0.0001 (15) | 0.0044 (12) |
O1W | 0.068 (2) | 0.0478 (15) | 0.0564 (14) | 0.0117 (13) | −0.0104 (13) | −0.0113 (11) |
Geometric parameters (Å, º) top
Cl4C—C4C | 1.731 (3) | C4A—C5A | 1.391 (4) |
Cl4D—C4D | 1.741 (3) | C5A—C6A | 1.366 (3) |
S5A—O53A | 1.439 (2) | C3A—H3A | 0.9295 |
S5A—C5A | 1.769 (3) | C4A—H4A | 0.9310 |
S5A—O51A | 1.453 (2) | C6A—H6A | 0.9301 |
S5A—O52A | 1.448 (2) | C1B—C6B | 1.394 (3) |
S5B—O53B | 1.446 (2) | C1B—C2B | 1.394 (4) |
S5B—O51B | 1.456 (2) | C1B—C7B | 1.463 (3) |
S5B—O52B | 1.435 (2) | C2B—C3B | 1.395 (3) |
S5B—C5B | 1.767 (3) | C3B—C4B | 1.357 (4) |
O2A—C2A | 1.351 (3) | C4B—C5B | 1.389 (4) |
O71A—C7A | 1.302 (3) | C5B—C6B | 1.379 (3) |
O72A—C7A | 1.230 (3) | C3B—H3B | 0.9299 |
O2A—H2A | 0.81 (5) | C4B—H4B | 0.9315 |
O71A—H71A | 0.83 (5) | C6B—H6B | 0.9299 |
O2B—C2B | 1.344 (3) | C1C—C6C | 1.371 (4) |
O71B—C7B | 1.298 (3) | C1C—C2C | 1.372 (4) |
O72B—C7B | 1.234 (3) | C2C—C3C | 1.374 (4) |
O2B—H2B | 0.82 (5) | C3C—C4C | 1.367 (5) |
O71B—H71B | 0.81 (5) | C4C—C5C | 1.369 (5) |
O1W—H2W | 0.96 (6) | C5C—C6C | 1.380 (4) |
O1W—H1W | 0.90 (5) | C2C—H2C | 0.9297 |
N1C—C1C | 1.458 (3) | C3C—H3C | 0.9298 |
N1C—H11C | 0.89 (5) | C5C—H5C | 0.9305 |
N1C—H13C | 0.89 (5) | C6C—H6C | 0.9288 |
N1C—H12C | 0.90 (5) | C1D—C6D | 1.376 (4) |
N1D—C1D | 1.457 (3) | C1D—C2D | 1.376 (4) |
N1D—H13D | 0.88 (5) | C2D—C3D | 1.374 (4) |
N1D—H11D | 0.87 (5) | C3D—C4D | 1.364 (4) |
N1D—H12D | 0.89 (5) | C4D—C5D | 1.369 (5) |
C1A—C2A | 1.395 (4) | C5D—C6D | 1.366 (4) |
C1A—C6A | 1.395 (4) | C2D—H2D | 0.9302 |
C1A—C7A | 1.459 (4) | C3D—H3D | 0.9300 |
C2A—C3A | 1.387 (3) | C5D—H5D | 0.9311 |
C3A—C4A | 1.361 (4) | C6D—H6D | 0.9289 |
| | | |
O51A—S5A—O52A | 112.68 (11) | O2B—C2B—C1B | 123.2 (2) |
O51A—S5A—O53A | 111.79 (13) | C1B—C2B—C3B | 119.2 (2) |
O51A—S5A—C5A | 103.74 (12) | C2B—C3B—C4B | 120.8 (2) |
O52A—S5A—O53A | 114.52 (12) | C3B—C4B—C5B | 120.4 (2) |
O52A—S5A—C5A | 106.37 (13) | C4B—C5B—C6B | 119.9 (2) |
O53A—S5A—C5A | 106.81 (11) | S5B—C5B—C6B | 119.19 (19) |
O51B—S5B—C5B | 105.25 (13) | S5B—C5B—C4B | 120.90 (18) |
O51B—S5B—O52B | 111.85 (12) | C1B—C6B—C5B | 120.1 (2) |
O51B—S5B—O53B | 112.23 (12) | O71B—C7B—O72B | 123.0 (2) |
O53B—S5B—C5B | 106.90 (12) | O71B—C7B—C1B | 115.0 (2) |
O52B—S5B—O53B | 113.30 (13) | O72B—C7B—C1B | 121.9 (2) |
O52B—S5B—C5B | 106.68 (11) | C2B—C3B—H3B | 119.59 |
C2A—O2A—H2A | 109 (4) | C4B—C3B—H3B | 119.66 |
C7A—O71A—H71A | 109 (3) | C3B—C4B—H4B | 119.77 |
C2B—O2B—H2B | 110 (3) | C5B—C4B—H4B | 119.80 |
C7B—O71B—H71B | 109 (3) | C5B—C6B—H6B | 119.90 |
H1W—O1W—H2W | 100 (4) | C1B—C6B—H6B | 120.00 |
H11C—N1C—H12C | 109 (5) | N1C—C1C—C2C | 118.9 (2) |
C1C—N1C—H12C | 109 (4) | N1C—C1C—C6C | 120.3 (2) |
H11C—N1C—H13C | 109 (5) | C2C—C1C—C6C | 120.9 (2) |
H12C—N1C—H13C | 110 (5) | C1C—C2C—C3C | 119.6 (2) |
C1C—N1C—H13C | 110 (3) | C2C—C3C—C4C | 119.5 (3) |
C1C—N1C—H11C | 109 (3) | C3C—C4C—C5C | 121.0 (3) |
C1D—N1D—H12D | 110 (3) | Cl4C—C4C—C3C | 119.2 (2) |
C1D—N1D—H11D | 111 (3) | Cl4C—C4C—C5C | 119.8 (3) |
H12D—N1D—H13D | 108 (4) | C4C—C5C—C6C | 119.6 (3) |
C1D—N1D—H13D | 110 (4) | C1C—C6C—C5C | 119.3 (3) |
H11D—N1D—H13D | 112 (4) | C1C—C2C—H2C | 120.27 |
H11D—N1D—H12D | 107 (5) | C3C—C2C—H2C | 120.12 |
C2A—C1A—C6A | 119.1 (2) | C2C—C3C—H3C | 120.15 |
C6A—C1A—C7A | 120.6 (2) | C4C—C3C—H3C | 120.31 |
C2A—C1A—C7A | 120.3 (2) | C4C—C5C—H5C | 120.23 |
O2A—C2A—C3A | 117.3 (2) | C6C—C5C—H5C | 120.16 |
O2A—C2A—C1A | 123.2 (2) | C5C—C6C—H6C | 120.31 |
C1A—C2A—C3A | 119.6 (2) | C1C—C6C—H6C | 120.42 |
C2A—C3A—C4A | 120.6 (2) | N1D—C1D—C6D | 119.4 (2) |
C3A—C4A—C5A | 120.3 (2) | N1D—C1D—C2D | 120.2 (2) |
S5A—C5A—C6A | 120.7 (2) | C2D—C1D—C6D | 120.4 (2) |
S5A—C5A—C4A | 119.05 (18) | C1D—C2D—C3D | 119.3 (2) |
C4A—C5A—C6A | 119.8 (2) | C2D—C3D—C4D | 119.7 (3) |
C1A—C6A—C5A | 120.6 (2) | Cl4D—C4D—C3D | 119.4 (3) |
O71A—C7A—O72A | 122.6 (2) | Cl4D—C4D—C5D | 119.3 (2) |
O71A—C7A—C1A | 115.2 (2) | C3D—C4D—C5D | 121.3 (3) |
O72A—C7A—C1A | 122.2 (2) | C4D—C5D—C6D | 119.2 (3) |
C2A—C3A—H3A | 119.73 | C1D—C6D—C5D | 120.1 (3) |
C4A—C3A—H3A | 119.67 | C1D—C2D—H2D | 120.42 |
C5A—C4A—H4A | 119.80 | C3D—C2D—H2D | 120.30 |
C3A—C4A—H4A | 119.91 | C4D—C3D—H3D | 120.07 |
C1A—C6A—H6A | 119.73 | C2D—C3D—H3D | 120.19 |
C5A—C6A—H6A | 119.65 | C4D—C5D—H5D | 120.46 |
C2B—C1B—C6B | 119.6 (2) | C6D—C5D—H5D | 120.36 |
C2B—C1B—C7B | 120.4 (2) | C1D—C6D—H6D | 119.97 |
C6B—C1B—C7B | 120.0 (2) | C5D—C6D—H6D | 119.91 |
O2B—C2B—C3B | 117.6 (2) | | |
| | | |
O51A—S5A—C5A—C4A | −73.8 (3) | C2B—C1B—C7B—O71B | 178.8 (3) |
O51A—S5A—C5A—C6A | 98.9 (2) | C2B—C1B—C7B—O72B | −0.2 (4) |
O52A—S5A—C5A—C4A | 45.3 (3) | C6B—C1B—C7B—O71B | −1.9 (4) |
O52A—S5A—C5A—C6A | −142.0 (2) | C6B—C1B—C2B—O2B | −178.5 (3) |
O53A—S5A—C5A—C4A | 168.0 (2) | C7B—C1B—C6B—C5B | −178.8 (3) |
O53A—S5A—C5A—C6A | −19.3 (3) | C6B—C1B—C7B—O72B | 179.1 (3) |
O52B—S5B—C5B—C4B | 35.0 (3) | C1B—C2B—C3B—C4B | −2.2 (4) |
O51B—S5B—C5B—C4B | −84.0 (2) | O2B—C2B—C3B—C4B | 177.8 (3) |
O51B—S5B—C5B—C6B | 96.9 (2) | C2B—C3B—C4B—C5B | 0.9 (4) |
O53B—S5B—C5B—C6B | −22.6 (3) | C3B—C4B—C5B—S5B | −177.9 (2) |
O52B—S5B—C5B—C6B | −144.1 (2) | C3B—C4B—C5B—C6B | 1.1 (4) |
O53B—S5B—C5B—C4B | 156.5 (2) | C4B—C5B—C6B—C1B | −1.8 (4) |
C6A—C1A—C2A—O2A | 179.8 (2) | S5B—C5B—C6B—C1B | 177.2 (2) |
C6A—C1A—C2A—C3A | 0.5 (4) | N1C—C1C—C6C—C5C | −176.8 (3) |
C6A—C1A—C7A—O72A | 177.7 (3) | C2C—C1C—C6C—C5C | 3.1 (4) |
C7A—C1A—C2A—C3A | −178.2 (3) | C6C—C1C—C2C—C3C | −2.8 (4) |
C7A—C1A—C2A—O2A | 1.1 (4) | N1C—C1C—C2C—C3C | 177.1 (3) |
C2A—C1A—C7A—O72A | −3.6 (4) | C1C—C2C—C3C—C4C | −0.1 (5) |
C2A—C1A—C7A—O71A | 176.0 (3) | C2C—C3C—C4C—C5C | 2.6 (5) |
C6A—C1A—C7A—O71A | −2.7 (4) | C2C—C3C—C4C—Cl4C | −177.6 (3) |
C7A—C1A—C6A—C5A | 178.1 (3) | Cl4C—C4C—C5C—C6C | 178.0 (3) |
C2A—C1A—C6A—C5A | −0.6 (4) | C3C—C4C—C5C—C6C | −2.2 (5) |
C1A—C2A—C3A—C4A | 0.0 (4) | C4C—C5C—C6C—C1C | −0.6 (5) |
O2A—C2A—C3A—C4A | −179.4 (3) | N1D—C1D—C6D—C5D | 178.9 (3) |
C2A—C3A—C4A—C5A | −0.4 (4) | C6D—C1D—C2D—C3D | 0.5 (4) |
C3A—C4A—C5A—C6A | 0.4 (4) | N1D—C1D—C2D—C3D | −178.2 (3) |
C3A—C4A—C5A—S5A | 173.2 (2) | C2D—C1D—C6D—C5D | 0.2 (4) |
S5A—C5A—C6A—C1A | −172.6 (2) | C1D—C2D—C3D—C4D | −0.3 (5) |
C4A—C5A—C6A—C1A | 0.1 (4) | C2D—C3D—C4D—Cl4D | 179.2 (3) |
C6B—C1B—C2B—C3B | 1.5 (4) | C2D—C3D—C4D—C5D | −0.5 (5) |
C7B—C1B—C2B—O2B | 0.8 (4) | C3D—C4D—C5D—C6D | 1.2 (5) |
C7B—C1B—C2B—C3B | −179.2 (3) | Cl4D—C4D—C5D—C6D | −178.5 (3) |
C2B—C1B—C6B—C5B | 0.5 (4) | C4D—C5D—C6D—C1D | −1.0 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O71A—H71A···O72B | 0.83 (5) | 1.80 (5) | 2.633 (3) | 175 (5) |
O71B—H71B···O72A | 0.81 (5) | 1.83 (5) | 2.634 (3) | 172 (5) |
O1W—H1W···O51B | 0.90 (5) | 1.92 (5) | 2.815 (4) | 180 (4) |
O2A—H2A···O72A | 0.81 (5) | 1.90 (5) | 2.607 (3) | 145 (5) |
O2B—H2B···O72B | 0.82 (5) | 1.89 (5) | 2.608 (3) | 145 (5) |
O1W—H2W···O52Bi | 0.96 (6) | 1.96 (6) | 2.920 (5) | 175 (4) |
N1C—H11C···O51Bii | 0.89 (5) | 1.97 (5) | 2.849 (4) | 169 (5) |
N1D—H11D···O52Aiii | 0.87 (5) | 2.14 (4) | 2.845 (4) | 137 (4) |
N1D—H11D···O52Aiv | 0.87 (5) | 2.36 (5) | 3.072 (3) | 139 (4) |
N1C—H12C···O53Av | 0.90 (5) | 1.92 (5) | 2.788 (3) | 162 (5) |
N1D—H12D···O1W | 0.89 (5) | 1.90 (5) | 2.783 (4) | 173 (4) |
N1C—H13C···O53Bi | 0.89 (5) | 2.09 (5) | 2.896 (4) | 152 (5) |
N1C—H13C···O52B | 0.89 (5) | 2.57 (5) | 2.913 (4) | 104 (5) |
N1D—H13D···O51Avi | 0.88 (5) | 1.94 (5) | 2.810 (4) | 168 (5) |
N1D—H13D···O51Aiv | 0.88 (5) | 2.58 (5) | 3.052 (3) | 115 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2; (v) x, −y+1/2, z+1/2; (vi) −x, y+1/2, −z+1/2. |
(III) 4-bromoanilinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate
top
Crystal data top
C6H7BrN+·C7H5O6S−·H2O | Dx = 1.713 Mg m−3 |
Mr = 408.22 | Melting point = 514.2–515.7 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4362 reflections |
a = 12.7810 (19) Å | θ = 2.3–27.0° |
b = 6.986 (1) Å | µ = 2.76 mm−1 |
c = 35.454 (5) Å | T = 295 K |
V = 3165.6 (8) Å3 | Block, colourless |
Z = 8 | 0.45 × 0.30 × 0.30 mm |
F(000) = 1648 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2788 independent reflections |
Radiation source: sealed tube | 2203 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −15→15 |
Tmin = 0.350, Tmax = 0.436 | k = −8→4 |
14778 measured reflections | l = −42→41 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0657P)2 + 0.9744P] where P = (Fo2 + 2Fc2)/3 |
2842 reflections | (Δ/σ)max = 0.003 |
237 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
Crystal data top
C6H7BrN+·C7H5O6S−·H2O | V = 3165.6 (8) Å3 |
Mr = 408.22 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.7810 (19) Å | µ = 2.76 mm−1 |
b = 6.986 (1) Å | T = 295 K |
c = 35.454 (5) Å | 0.45 × 0.30 × 0.30 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2788 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2203 reflections with I > 2σ(I) |
Tmin = 0.350, Tmax = 0.436 | Rint = 0.032 |
14778 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.59 e Å−3 |
2842 reflections | Δρmin = −0.55 e Å−3 |
237 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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S5 | 0.47157 (5) | 0.96199 (10) | 0.696416 (18) | 0.0337 (2) | |
O2 | 0.24796 (17) | 0.7489 (3) | 0.55712 (6) | 0.0519 (8) | |
O51 | 0.57779 (17) | 1.0167 (3) | 0.68714 (6) | 0.0519 (8) | |
O52 | 0.41149 (17) | 1.1239 (3) | 0.70977 (5) | 0.0475 (7) | |
O53 | 0.46616 (16) | 0.7984 (3) | 0.72161 (5) | 0.0455 (6) | |
O71 | 0.53666 (17) | 1.0287 (3) | 0.55021 (6) | 0.0504 (8) | |
O72 | 0.40158 (17) | 0.8994 (3) | 0.51939 (5) | 0.0490 (7) | |
C1 | 0.4033 (2) | 0.8850 (4) | 0.58601 (7) | 0.0319 (8) | |
C2 | 0.3054 (2) | 0.7953 (4) | 0.58797 (7) | 0.0340 (8) | |
C3 | 0.2631 (2) | 0.7498 (4) | 0.62296 (8) | 0.0370 (8) | |
C4 | 0.3146 (2) | 0.7966 (4) | 0.65550 (7) | 0.0357 (8) | |
C5 | 0.4118 (2) | 0.8882 (4) | 0.65387 (7) | 0.0295 (8) | |
C6 | 0.4561 (2) | 0.9302 (3) | 0.61935 (7) | 0.0306 (8) | |
C7 | 0.4472 (2) | 0.9386 (4) | 0.54897 (8) | 0.0367 (9) | |
Br41 | 0.86288 (4) | 1.03786 (7) | 0.534233 (11) | 0.0840 (2) | |
N11 | 0.9246 (2) | 0.9495 (3) | 0.70380 (7) | 0.0432 (8) | |
C11 | 0.9090 (2) | 0.9728 (4) | 0.66345 (8) | 0.0375 (8) | |
C21 | 0.8155 (3) | 1.0409 (5) | 0.64965 (9) | 0.0511 (11) | |
C31 | 0.8019 (3) | 1.0618 (5) | 0.61127 (10) | 0.0561 (11) | |
C41 | 0.8822 (3) | 1.0138 (4) | 0.58725 (9) | 0.0505 (10) | |
C51 | 0.9759 (3) | 0.9469 (4) | 0.60075 (10) | 0.0506 (11) | |
C61 | 0.9894 (2) | 0.9270 (4) | 0.63919 (9) | 0.0460 (10) | |
O1W | 0.7294 (3) | 0.8389 (8) | 0.73346 (11) | 0.0891 (14) | |
H2 | 0.283 (3) | 0.784 (6) | 0.5384 (11) | 0.069 (13)* | |
H3 | 0.1991 | 0.6868 | 0.6243 | 0.0440* | |
H4 | 0.2850 | 0.7673 | 0.6788 | 0.0430* | |
H6 | 0.5214 | 0.9888 | 0.6183 | 0.0370* | |
H72 | 0.555 (3) | 1.056 (4) | 0.5292 (10) | 0.048 (10)* | |
H11A | 0.951 (3) | 1.059 (4) | 0.7140 (10) | 0.068 (11)* | |
H11B | 0.970 (3) | 0.856 (4) | 0.7080 (10) | 0.066 (10)* | |
H11C | 0.864 (3) | 0.920 (4) | 0.7150 (10) | 0.064 (11)* | |
H21 | 0.7616 | 1.0727 | 0.6661 | 0.0610* | |
H31 | 0.7389 | 1.1078 | 0.6017 | 0.0670* | |
H51 | 1.0297 | 0.9154 | 0.5842 | 0.0610* | |
H61 | 1.0528 | 0.8828 | 0.6487 | 0.0550* | |
H1A | 0.708 (4) | 0.779 (8) | 0.7487 (18) | 0.11 (2)* | |
H1B | 0.684 (4) | 0.892 (7) | 0.7201 (17) | 0.10 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S5 | 0.0443 (4) | 0.0357 (4) | 0.0211 (3) | 0.0017 (3) | −0.0037 (3) | 0.0004 (3) |
O2 | 0.0601 (13) | 0.0662 (15) | 0.0293 (11) | −0.0235 (12) | −0.0087 (10) | −0.0016 (10) |
O51 | 0.0463 (12) | 0.0726 (15) | 0.0367 (12) | −0.0118 (11) | −0.0091 (9) | 0.0033 (10) |
O52 | 0.0673 (14) | 0.0414 (11) | 0.0337 (11) | 0.0092 (10) | −0.0048 (9) | −0.0115 (9) |
O53 | 0.0682 (13) | 0.0455 (11) | 0.0228 (9) | 0.0081 (10) | −0.0026 (8) | 0.0069 (8) |
O71 | 0.0582 (14) | 0.0701 (15) | 0.0228 (11) | −0.0234 (12) | 0.0074 (9) | −0.0008 (10) |
O72 | 0.0586 (12) | 0.0678 (13) | 0.0206 (10) | −0.0136 (11) | 0.0016 (9) | −0.0035 (10) |
C1 | 0.0410 (14) | 0.0317 (13) | 0.0230 (13) | 0.0007 (12) | 0.0025 (11) | −0.0005 (11) |
C2 | 0.0429 (15) | 0.0325 (14) | 0.0266 (13) | −0.0034 (12) | −0.0042 (11) | −0.0030 (11) |
C3 | 0.0388 (14) | 0.0376 (15) | 0.0345 (15) | −0.0103 (12) | 0.0011 (11) | −0.0004 (11) |
C4 | 0.0452 (16) | 0.0348 (14) | 0.0271 (13) | −0.0028 (12) | 0.0069 (11) | 0.0029 (11) |
C5 | 0.0376 (14) | 0.0273 (12) | 0.0236 (13) | 0.0022 (11) | −0.0007 (10) | 0.0014 (10) |
C6 | 0.0356 (14) | 0.0284 (13) | 0.0279 (13) | 0.0002 (11) | 0.0010 (10) | −0.0012 (10) |
C7 | 0.0457 (16) | 0.0380 (16) | 0.0265 (14) | −0.0028 (13) | 0.0043 (12) | −0.0056 (11) |
Br41 | 0.1346 (5) | 0.0798 (4) | 0.0375 (3) | −0.0063 (3) | −0.0071 (2) | 0.0017 (2) |
N11 | 0.0547 (15) | 0.0372 (13) | 0.0378 (14) | −0.0001 (12) | −0.0040 (11) | −0.0028 (10) |
C11 | 0.0467 (16) | 0.0299 (13) | 0.0358 (15) | −0.0036 (13) | 0.0015 (12) | 0.0009 (12) |
C21 | 0.0500 (18) | 0.058 (2) | 0.0453 (19) | 0.0065 (15) | 0.0051 (14) | 0.0051 (15) |
C31 | 0.0553 (19) | 0.062 (2) | 0.051 (2) | 0.0043 (16) | −0.0072 (16) | 0.0047 (16) |
C41 | 0.077 (2) | 0.0375 (16) | 0.0371 (17) | −0.0077 (16) | −0.0058 (16) | −0.0025 (13) |
C51 | 0.062 (2) | 0.0412 (17) | 0.0487 (19) | −0.0014 (15) | 0.0146 (16) | −0.0010 (14) |
C61 | 0.0488 (17) | 0.0385 (17) | 0.0506 (19) | 0.0008 (13) | 0.0021 (14) | 0.0000 (14) |
O1W | 0.0653 (19) | 0.119 (3) | 0.083 (2) | −0.005 (2) | −0.0007 (15) | 0.045 (3) |
Geometric parameters (Å, º) top
Br41—C41 | 1.903 (3) | C1—C2 | 1.401 (4) |
S5—O51 | 1.448 (2) | C2—C3 | 1.390 (4) |
S5—O53 | 1.452 (2) | C3—C4 | 1.368 (4) |
S5—C5 | 1.768 (3) | C4—C5 | 1.399 (4) |
S5—O52 | 1.447 (2) | C5—C6 | 1.380 (4) |
O2—C2 | 1.357 (3) | C3—H3 | 0.9301 |
O71—C7 | 1.306 (3) | C4—H4 | 0.9314 |
O72—C7 | 1.231 (3) | C6—H6 | 0.9303 |
O2—H2 | 0.84 (4) | C11—C61 | 1.378 (4) |
O71—H72 | 0.80 (4) | C11—C21 | 1.376 (5) |
O1W—H1B | 0.84 (5) | C21—C31 | 1.380 (5) |
O1W—H1A | 0.74 (6) | C31—C41 | 1.375 (5) |
N11—C11 | 1.454 (4) | C41—C51 | 1.372 (5) |
N11—H11C | 0.89 (4) | C51—C61 | 1.381 (5) |
N11—H11A | 0.91 (3) | C21—H21 | 0.9296 |
N11—H11B | 0.89 (3) | C31—H31 | 0.9310 |
C1—C6 | 1.397 (4) | C51—H51 | 0.9303 |
C1—C7 | 1.476 (4) | C61—H61 | 0.9304 |
| | | |
O51—S5—O52 | 111.44 (13) | O72—C7—C1 | 121.4 (2) |
O51—S5—O53 | 113.08 (12) | O71—C7—O72 | 123.4 (3) |
O51—S5—C5 | 106.76 (12) | O71—C7—C1 | 115.2 (2) |
O52—S5—O53 | 112.87 (12) | C2—C3—H3 | 119.73 |
O52—S5—C5 | 106.13 (12) | C4—C3—H3 | 119.55 |
O53—S5—C5 | 105.95 (12) | C3—C4—H4 | 120.01 |
C2—O2—H2 | 106 (3) | C5—C4—H4 | 119.87 |
C7—O71—H72 | 110 (3) | C5—C6—H6 | 119.81 |
H1A—O1W—H1B | 114 (6) | C1—C6—H6 | 119.92 |
C11—N11—H11B | 110 (2) | N11—C11—C61 | 119.1 (2) |
C11—N11—H11C | 110 (2) | N11—C11—C21 | 120.5 (3) |
H11A—N11—H11B | 108 (3) | C21—C11—C61 | 120.4 (3) |
H11A—N11—H11C | 110 (3) | C11—C21—C31 | 119.8 (3) |
H11B—N11—H11C | 109 (3) | C21—C31—C41 | 119.4 (3) |
C11—N11—H11A | 110 (2) | Br41—C41—C31 | 119.6 (3) |
C2—C1—C6 | 119.4 (2) | Br41—C41—C51 | 119.2 (3) |
C2—C1—C7 | 119.8 (2) | C31—C41—C51 | 121.2 (3) |
C6—C1—C7 | 120.8 (2) | C41—C51—C61 | 119.2 (3) |
O2—C2—C1 | 123.4 (2) | C11—C61—C51 | 120.0 (3) |
O2—C2—C3 | 117.0 (2) | C11—C21—H21 | 120.21 |
C1—C2—C3 | 119.6 (2) | C31—C21—H21 | 120.01 |
C2—C3—C4 | 120.7 (2) | C41—C31—H31 | 120.26 |
C3—C4—C5 | 120.1 (2) | C21—C31—H31 | 120.33 |
C4—C5—C6 | 119.9 (2) | C41—C51—H51 | 120.38 |
S5—C5—C6 | 121.2 (2) | C61—C51—H51 | 120.42 |
S5—C5—C4 | 118.82 (19) | C11—C61—H61 | 120.03 |
C1—C6—C5 | 120.3 (2) | C51—C61—H61 | 120.00 |
| | | |
O51—S5—C5—C4 | 169.1 (2) | C1—C2—C3—C4 | 1.9 (4) |
O52—S5—C5—C4 | −71.9 (2) | C2—C3—C4—C5 | −1.1 (4) |
O53—S5—C5—C4 | 48.3 (3) | C3—C4—C5—C6 | −0.4 (4) |
O51—S5—C5—C6 | −15.0 (3) | C3—C4—C5—S5 | 175.5 (2) |
O52—S5—C5—C6 | 103.9 (2) | C4—C5—C6—C1 | 1.3 (4) |
O53—S5—C5—C6 | −135.8 (2) | S5—C5—C6—C1 | −174.5 (2) |
C6—C1—C2—C3 | −1.1 (4) | N11—C11—C61—C51 | 179.6 (3) |
C7—C1—C2—O2 | 1.8 (4) | C61—C11—C21—C31 | 0.6 (5) |
C6—C1—C7—O72 | 179.9 (2) | N11—C11—C21—C31 | −179.9 (3) |
C7—C1—C2—C3 | −178.3 (3) | C21—C11—C61—C51 | −0.9 (4) |
C2—C1—C6—C5 | −0.5 (4) | C11—C21—C31—C41 | 0.1 (5) |
C6—C1—C7—O71 | 0.0 (4) | C21—C31—C41—Br41 | 178.8 (3) |
C6—C1—C2—O2 | 179.0 (2) | C21—C31—C41—C51 | −0.5 (5) |
C2—C1—C7—O71 | 177.2 (2) | C31—C41—C51—C61 | 0.2 (4) |
C7—C1—C6—C5 | 176.7 (2) | Br41—C41—C51—C61 | −179.1 (2) |
C2—C1—C7—O72 | −3.0 (4) | C41—C51—C61—C11 | 0.5 (4) |
O2—C2—C3—C4 | −178.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O72 | 0.84 (4) | 1.84 (4) | 2.598 (3) | 149 (4) |
O71—H72···O72i | 0.80 (4) | 1.84 (4) | 2.639 (3) | 176 (3) |
O1W—H1A···O52ii | 0.74 (6) | 2.38 (6) | 3.090 (5) | 162 (5) |
O1W—H1B···O51 | 0.84 (5) | 1.99 (5) | 2.827 (5) | 179 (6) |
N11—H11A···O53iii | 0.91 (3) | 2.00 (3) | 2.879 (3) | 162 (3) |
N11—H11B···O53iv | 0.89 (3) | 2.53 (4) | 2.897 (3) | 106 (3) |
N11—H11B···O51v | 0.89 (3) | 2.56 (3) | 3.081 (3) | 119 (3) |
N11—H11B···O52v | 0.89 (3) | 2.22 (3) | 3.100 (3) | 172 (3) |
N11—H11C···O1W | 0.89 (4) | 1.93 (4) | 2.815 (5) | 173 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+3/2, y+1/2, z; (iv) x+1/2, y, −z+3/2; (v) −x+3/2, y−1/2, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C6H7FN+·C7H5O6S−·H2O | C6H7ClN+·C7H5O6S−·0.5H2O | C6H7BrN+·C7H5O6S−·H2O |
Mr | 347.31 | 354.77 | 408.22 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 6.7978 (7), 12.5513 (12), 8.5306 (8) | 7.455 (4), 11.849 (7), 33.848 (19) | 12.7810 (19), 6.986 (1), 35.454 (5) |
α, β, γ (°) | 90, 96.529 (2), 90 | 90, 90.817 (12), 90 | 90, 90, 90 |
V (Å3) | 723.12 (12) | 2990 (3) | 3165.6 (8) |
Z | 2 | 8 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.43 | 2.76 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 | 0.45 × 0.30 × 0.15 | 0.45 × 0.30 × 0.30 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | – | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | – | – | 0.350, 0.436 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3741, 2360, 2275 | 11861, 5220, 4133 | 14778, 2788, 2203 |
Rint | 0.026 | 0.028 | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.073, 1.03 | 0.049, 0.132, 1.21 | 0.038, 0.112, 1.07 |
No. of reflections | 2360 | 5220 | 2842 |
No. of parameters | 237 | 444 | 237 |
No. of restraints | 1 | 0 | 0 |
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 | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.22 | 0.41, −0.54 | 0.59, −0.55 |
Absolute structure | Flack (1983), 1029 Friedel pairs | ? | ? |
Absolute structure parameter | 0.03 (3) | ? | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O72 | 0.80 (3) | 1.92 (4) | 2.625 (2) | 145 (4) |
O1W—H1A···O53i | 0.83 (4) | 2.19 (4) | 3.019 (3) | 177 (4) |
O1W—H1B···O52 | 0.79 (5) | 2.18 (4) | 2.853 (3) | 142 (4) |
N11—H11A···O51ii | 0.89 (5) | 2.01 (5) | 2.882 (3) | 168 (3) |
N11—H11B···O53 | 0.88 (4) | 2.03 (4) | 2.910 (3) | 172 (4) |
N11—H11C···O1W | 0.90 (3) | 1.90 (4) | 2.726 (3) | 152 (4) |
O71—H71···O52iii | 0.80 (4) | 1.84 (4) | 2.632 (2) | 176 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y+1/2, −z+1; (iii) x, y, z−1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O71A—H71A···O72B | 0.83 (5) | 1.80 (5) | 2.633 (3) | 175 (5) |
O71B—H71B···O72A | 0.81 (5) | 1.83 (5) | 2.634 (3) | 172 (5) |
O1W—H1W···O51B | 0.90 (5) | 1.92 (5) | 2.815 (4) | 180 (4) |
O2A—H2A···O72A | 0.81 (5) | 1.90 (5) | 2.607 (3) | 145 (5) |
O2B—H2B···O72B | 0.82 (5) | 1.89 (5) | 2.608 (3) | 145 (5) |
O1W—H2W···O52Bi | 0.96 (6) | 1.96 (6) | 2.920 (5) | 175 (4) |
N1C—H11C···O51Bii | 0.89 (5) | 1.97 (5) | 2.849 (4) | 169 (5) |
N1D—H11D···O52Aiii | 0.87 (5) | 2.14 (4) | 2.845 (4) | 137 (4) |
N1D—H11D···O52Aiv | 0.87 (5) | 2.36 (5) | 3.072 (3) | 139 (4) |
N1C—H12C···O53Av | 0.90 (5) | 1.92 (5) | 2.788 (3) | 162 (5) |
N1D—H12D···O1W | 0.89 (5) | 1.90 (5) | 2.783 (4) | 173 (4) |
N1C—H13C···O53Bi | 0.89 (5) | 2.09 (5) | 2.896 (4) | 152 (5) |
N1C—H13C···O52B | 0.89 (5) | 2.57 (5) | 2.913 (4) | 104 (5) |
N1D—H13D···O51Avi | 0.88 (5) | 1.94 (5) | 2.810 (4) | 168 (5) |
N1D—H13D···O51Aiv | 0.88 (5) | 2.58 (5) | 3.052 (3) | 115 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2; (v) x, −y+1/2, z+1/2; (vi) −x, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O72 | 0.84 (4) | 1.84 (4) | 2.598 (3) | 149 (4) |
O71—H72···O72i | 0.80 (4) | 1.84 (4) | 2.639 (3) | 176 (3) |
O1W—H1A···O52ii | 0.74 (6) | 2.38 (6) | 3.090 (5) | 162 (5) |
O1W—H1B···O51 | 0.84 (5) | 1.99 (5) | 2.827 (5) | 179 (6) |
N11—H11A···O53iii | 0.91 (3) | 2.00 (3) | 2.879 (3) | 162 (3) |
N11—H11B···O53iv | 0.89 (3) | 2.53 (4) | 2.897 (3) | 106 (3) |
N11—H11B···O51v | 0.89 (3) | 2.56 (3) | 3.081 (3) | 119 (3) |
N11—H11B···O52v | 0.89 (3) | 2.22 (3) | 3.100 (3) | 172 (3) |
N11—H11C···O1W | 0.89 (4) | 1.93 (4) | 2.815 (5) | 173 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+3/2, y+1/2, z; (iv) x+1/2, y, −z+3/2; (v) −x+3/2, y−1/2, z. |
Selected bond lengths and angles (Å, °) for (I), (II)a and (III) top | (I) | (II)A,C | (II)B,D | III |
S5—O51 | 1.4535 (15) | 1.453 (2) | 1.456 (2) | 1.448 (2) |
S5—O52 | 1.4571 (15) | 1.448 (2) | 1.435 (2) | 1.447 (2) |
S5—O53 | 1.4599 (17) | 1.439 (2) | 1.446 (2) | 1.452 (2) |
S5—C5 | 1.768 (2) | 1.769 (3) | 1.767 (3) | 1.768 (3) |
F41—C41b | 1.362 (3) | 1.731 (3) | 1.741 (3) | 1.903 (3) |
O2—C2 | 1.346 (3) | 1.351 (3) | 1.344 (3) | 1.357 (3) |
O71—C7 | 1.313 (3) | 1.302 (3) | 1.298 (3) | 1.306 (3) |
O72—C7 | 1.232 (3) | 1.230 (3) | 1.234 (3) | 1.231 (3) |
N11—C11 | 1.478 (3) | 1.458 (3) | 1.457 (3) | 1.454 (4) |
| | | | |
O51—S5—O52 | 111.52 (9) | 112.68 (11) | 111.85 (12) | 111.44 (13) |
O51—S5—O53 | 112.82 (10) | 111.79 (13) | 112.23 (12) | 113.08 (12) |
O51—S5—C5 | 107.24 (10) | 103.74 (12) | 105.25 (13) | 106.76 (12) |
O52—S5—O53 | 111.71 (11) | 114.52 (12) | 113.30 (13) | 112.87 (12) |
O52—S5—C5 | 106.76 (10) | 106.37 (13) | 106.68 (11) | 106.13 (12) |
O53—S5—C5 | 106.34 (10) | 106.81 (11) | 106.90 (12) | 105.95 (12) |
O2—C2—C1 | 122.7 (2) | 123.2 (2) | 123.2 (2) | 123.4 (2) |
O2—C2—C3 | 117.8 (2) | 117.3 (2) | 117.6 (2) | 117.0 (2) |
S5—C5—C6 | 120.63 (17) | 120.7 (2) | 119.19 (19) | 121.2 (2) |
S5—C5—C4 | 119.23 (19) | 119.05 (18) | 120.90 (18) | 118.82 (19) |
O72—C7—C1 | 122.9 (2) | 122.1 (2) | 121.9 (2) | 121.4 (2) |
O71—C7—O72 | 122.3 (2) | 122.6 (2) | 123.0 (2) | 123.4 (3) |
O71—C7—C1 | 114.8 (2) | 115.2 (2) | 115.0 (2) | 115.2 (2) |
N11—C11—C61 | 119.7 (2) | 120.3 (2) | 119.4 (2) | 119.1 (2) |
N11—C11—C21 | 118.4 (2) | 118.9 (2) | 120.2 (2) | 120.5 (3) |
F41—C41—C31 | 118.9 (2) | 119.2 (2) | 119.4 (3) | 119.6 (3) |
F41—C41—C51 | 118.1 (2) | 119.8 (3) | 119.3 (2) | 119.2 (3) |
| | | | |
O51—S5—C5—C4 | 51.89 (19) | -73.8 (3) | -84.0 (2) | 169.1 (2) |
O52—S5—C5—C4 | -67.76 (19) | 45.3 (3) | 35.0 (3) | -71.9 (2) |
O53—S5—C5—C4 | 172.84 (17) | 168.0 (2) | 156.5 (2) | 48.3 (3) |
O51—S5—C5—C6 | -126.64 (18) | 98.9 (2) | 96.9 (2) | -15.0 (3) |
O52—S5—C5—C6 | 113.71 (18) | -142.0 (2) | -144.1 (2) | 103.9 (2) |
O53—S5—C5—C6 | -5.7 (2) | -19.3 (3) | -22.6 (3) | -135.8 (2) |
C2—C1—C7—O71 | 170.4 (2) | 176.0 (3) | 178.8 (3) | 177.2 (2) |
C6—C1—C7—O71 | -8.8 (3) | -2.7 (4) | -1.9 (4) | 0.0 (4) |
C6—C1—C7—O72 | 172.4 (2) | 177.7 (3) | 179.1 (3) | 179.9 (2) |
C2—C1—C7—O72 | -8.5 (3) | -3.6 (4) | -0.2 (4) | -3.0 (4) |
a Data for anion with atom label suffix A and cation with atom label suffix C are in column 3 and data for anion with atom label suffix B and cation with atom label suffix D are in column 4.
b For F41 read Cl4C, Cl4D and Br41 in columns 3, 4 and 5, respectively. |
3-Carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) has proved a particularly useful synthon for molecular assembly through hydrogen bonding, having, in addition to the primary sulfonic acid functional group, interactive carboxylic acid and phenol substituent groups. In the 5-SSA anion formed in the reaction of 5-SSA with Lewis bases, all of these substituent groups provide hydrogen-bonding donor or acceptor atoms with potential for both primary and secondary structure extension. In a previous study of the proton-transfer compounds of 5-SSA with a series of quinolines (Smith, Wermuth & White, 2004), we reviewed the structural systematics of 5-SSA compounds with Lewis bases, including those with aniline (1:1) (Bakasova et al., 1991), guanidine [both a 1:1 anhydrate (Zhang et al., 2004) and a 2:1 monohydrate (Smith, Wermuth & Healy, 2004)], theophylline (a 1:1 monohydrate) (Madarasz et al., 2002), trimethoprim (a 1:1 dihydrate) (Raj et al., 2003) and 4,4'-bipyridine (a 1:2 dihydrate) (Muthiah et al., 2003). It was observed that, with the majority of compounds, water was incorporated into the crystal structure and was involved in primary direct hydrogen-bonding interactions with the aminium groups, whereas with the anhydrous compounds, the primary interaction involved the aminium H atoms and sulfonate O-atom acceptors. In some examples, particularly those with the polycyclic heteroaromatic amines (Smith, Wermuth & White, 2004), the structures featured π–π hetero- and homomolecular interactions.
The crystal structures reported here are those of 5-SSA with the 4-halo-substituted anilines 4-fluoroaniline (FAN) [4-fluoroanilinium 5-sulfosalicylate monohydrate, C6H7FN+·C7H5O2S−·H2O, (I)], 4-chloroaniline (CLAN) [4-chloroanilinium 5-sulfosalicylate hemihydrate, C6H7ClN+·C7H5O2S−·0.5H2O, (II)] and 4-bromoaniline (BRAN) [4-bromoanilinium 5-sulfosalicylate monohydrate, C6H7BrN+·C7H5O2S−·H2O, (III)]. Fig. 1 shows the atom-numbering scheme used for the substituted anilinium cation, the 5-sulfosalicylate anion and the water molecules of solvation in (I); the same scheme is employed for (II) and (III) and has previously been employed in 5-SSA structures reported by this group (Smith, Wermuth & Healy, 2004; Smith, Wermuth & White, 2004). Table 1 lists the selected bond distances and angles for (I)–(III). All three examples involve proton transfer from the sulfonic acid group to the amine groups of the aniline molecule, with subsequent hydrogen bonding (Tables 2a–2c) involving also the water molecule, giving in all cases three-dimensional network structures. The hydrogen bonding includes one type not encountered before in 5-SSA Lewis base compounds, namely a rare cyclic R33(8) association in (I), involving both an anilinium N+—H···O(sulfonate) and an N+—H···O(water) interaction (Fig. 1). There is no occurrence of the anilinium–sulfonate R22(8) dimer interaction commonly found in the anhydrous guanidinium sulfonates (Russell et al., 1994; Zhang et al., 2004; Haynes et al., 2004) but absent in tris(guanidinium) 5-sulfosalicylate hydrate (Smith, Wermuth & Healy, 2004) and the quinolinium 5-sulfosalicylate structures (Smith, Wermuth & White, 2004). However, the common homomolecular cyclic R22(8) carboxylic acid association is found in both (II) and (III).
With the 5-SSA anion species in (I)–(III), structural and conformational features similar to those previously observed (Smith, Wermuth & White, 2004) are found. The usual intramolecular hydrogen bond is found between the phenol OH group and a carboxylate O atom (O2—H2···O72) [2.598 (3)–2.625 (2) Å], essentially giving coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2—C1—C7—O71, range 176.0 (3)–178.9 (2)°]. However, in only one compound, (I), is the carboxylic acid group involved in the strong single heteromolecular O—H···O(sulfonate) hydrogen-bonding interaction [2.632 (2) Å], such as is found in most 5-SSA compounds. With (II) and (III) this group participates in the equally strong but cyclic homo-intermolecular interaction, while in none of the structures is there any intermolecular phenol O-atom participation.
## AUTHOR: Please check Figure numbers in all Comment text. ## AUTHOR: Please supply symmetry codes as noted below.
Compound (I) with 4-fluoroaniline, [FAN+.5-SSA−·H2O] (Fig. 1), comprises layers of cation and anion pairs which propagate along the 21 screw axis in the cell, linked by hydrogen- bonding interactions both within and between the layers (Table 2). The anilinium group is involved in three hydrogen-bonding interactions, two of which comprise direct N+—H···O(sulfonate) links, [N11···O53 and N11···O51ii; symmetry code: (ii) ??????], the third being a link to the water molecule (N11···O1W). One of the water H atoms completes an unusual R33(8) cyclic association with a second sulfonate O atom (O1W···O52), while the second forms an interlayer bridge with another sulfonate O atom [O53i; symmetry code: (i) ????????]. The result is that the water molecule effectively links together the cation/anion layers that form along the a cell direction. The carboxylate group of 5-SSA also gives a link along the c cell direction [O71···O52iii; symmetry code: (iii) ??????], resulting in a three-dimensional hydrogen-bonded network structure (Fig. 2).
Although (II) is a hemihydrate, both compound (II) with 4-chloroaniline, [CLAN+.5-SSA−·0.5H2O], and compound (III), with 4-bromoaniline, [BRAN+ 5-SSA−·H2O], are structurally similar. This similarity may be seen in Figs. 5 and 6. In both examples, the common R22(8) hydrogen- bonded cyclic carboxylic acid dimer is found, which in the case of (III) lies across a crystallographic inversion centre [O71···O72i = 2.639 (3) Å; symmetry code: (i) ?????], while in (II) the dimer is pseudo-centrosymmetric [O71A···O72B = 2.633 (3) Å and O71B···O72A = 2.634 (3) Å]. In both compounds, the aminium H atoms form direct links to the sulfonate O-atom donors as well as to the water O atom [in (II), four for cation C, five for cation D; in (III), five in total; Tables 2b and 2c]. The water molecule also acts as a bridging donor group in structure extension via the sulfonate groups. The result in both (I) and (II) is the formation of extensive hydrogen-bonded network polymeric structures. An anomalous unexplained feature in the structure of (II) is the presence of some short non-bonding contacts between inversion-related sulfonate O atoms [O51A···O51Avii = 2.815 (3) Å, O52A···O52Aviii = 2.875 (3) Å and O51B···O51Bix = 3.071 (3) Å; symmetry codes: (vii) −x, 1 − y, −z; (viii) 1 − x, 1 − y, −z; (ix) −x, 1 − y, 1 − z].