Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106023754/ln3011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011IIIsup4.hkl |
CCDC references: 618633; 618634; 618635
The title compound was obtained from the chemical collection of the Chemistry Department of the University of Minnesota. Polymorph (I) was obtained by recrystallization from methanol, benzene or chloroform. Polymorph (I) and the 0.25-hydrate, (III), were obtained simultaneously by recrystallization from acetone or propan-2-ol. Both (II) and (III) were obtained simultaneously by recrystallization from acetonitrile. [Likely source of water?]
Twelve crystals of (I) were examined and all were twinned. Data were collected on a non-merohedrally twinned crystal grown from methanol. The crystal used was indexed using GEMINI (Sparks, 2000). The major twin component fitted 112 reflections, while the minor twin component fitted 90 of the overall 138 reflections used. The twin law was determined to be [100/010/-0.551,-0.039,1], which corresponds to 180° rotation around the c* axis. The data were integrated with SAINT (Bruker, 2003) and corrected for absorption and scaling with TWINABS (Sheldrick, 2003; Blessing, 1995). Twenty-eight redundant reflections were eliminated from the final data file with STRIP REDUNDANT (Brennessel & Young, 2003). The ratio of the major and minor twin components was 0.570 (2):0.430 (2) based on refinement using SHELXTL (Sheldrick, 1997); the twinning necessitated the inclusion of the intensity data for both twin fractions in one file in the HKLF5 format (Sheldrick, 1997).
In each compound, the carboxylic acid H atoms were constrained to an ideal geometry, with O—H = 0.84 Å, but were allowed to rotate freely about the C—O bonds, with Uiso(H) = 1.5Ueq(O) for (I) and (III) or 1.2Ueq(O) for (II). In each case, these H atoms were disordered between the two carboxylic acid O atoms and the site-occupancy factors of the two positions for each H atom were constrained to sum to 1.00. H atoms attached to C atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C). In (III), there is a water molecule located near a centre of symmetry, with two half-occupancy O atoms and four half-occupancy H atoms expected within the solvent cavity. The water O atom was refined with an isotropic displacement parameter. Only one independent peak that seemed to correspond to an H atom was found in the difference map. When this peak was assumed to represent H, the site-occupancy factor refined to 0.95 (3) rather than 0.50. This suggested that two pairs of H-atom positions were too near each other to be separated in the difference Fourier map. The initial model for the refinement had one H atom on a particular O atom located near each of the two disordered H-atom peaks. The final refinement had the O—H distances in the water molecule restrained tightly to 0.840 (1) Å and the H—O—H angle restrained to 109.5 (2)°, with Uiso(H) = 1.5Ueq(O). In view of the expected precision of the H-atom positions, these are effectively [Text missing? No?] constraints.
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C8H3Cl2NO2 | Z = 4 |
Mr = 216.01 | F(000) = 432 |
Triclinic, P1 | Dx = 1.611 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8859 (17) Å | Cell parameters from 1911 reflections |
b = 11.658 (4) Å | θ = 2.6–25.1° |
c = 15.891 (6) Å | µ = 0.69 mm−1 |
α = 88.39 (1)° | T = 174 K |
β = 84.79 (1)° | Prism, pale yellow |
γ = 81.23 (1)° | 0.25 × 0.20 × 0.10 mm |
V = 890.8 (6) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 3178 independent reflections |
Radiation source: fine-focus sealed tube | 2660 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
ω scans | θmax = 25.1°, θmin = 1.3° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2003; Blessing, 1995) | h = −5→5 |
Tmin = 0.85, Tmax = 0.93 | k = −13→13 |
11344 measured reflections | l = −18→18 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.053P)2 + 1.6P] where P = (Fo2 + 2Fc2)/3 |
3178 reflections | (Δ/σ)max = 0.001 |
242 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C8H3Cl2NO2 | γ = 81.23 (1)° |
Mr = 216.01 | V = 890.8 (6) Å3 |
Triclinic, P1 | Z = 4 |
a = 4.8859 (17) Å | Mo Kα radiation |
b = 11.658 (4) Å | µ = 0.69 mm−1 |
c = 15.891 (6) Å | T = 174 K |
α = 88.39 (1)° | 0.25 × 0.20 × 0.10 mm |
β = 84.79 (1)° |
Bruker SMART 1K CCD area-detector diffractometer | 3178 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2003; Blessing, 1995) | 2660 reflections with I > 2σ(I) |
Tmin = 0.85, Tmax = 0.93 | Rint = 0.059 |
11344 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.46 e Å−3 |
3178 reflections | Δρmin = −0.34 e Å−3 |
242 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl3A | 0.2281 (4) | 0.32026 (16) | 0.70770 (10) | 0.0509 (5) | |
Cl5A | −0.1965 (3) | 0.39102 (12) | 1.03210 (9) | 0.0313 (4) | |
O1A | 0.8788 (8) | 0.0554 (4) | 0.8999 (3) | 0.0340 (10) | |
H1A | 1.0094 | 0.0130 | 0.9217 | 0.051* | 0.71 (10) |
O2A | 0.7062 (9) | 0.0799 (4) | 1.0352 (2) | 0.0323 (10) | |
H2A | 0.8678 | 0.0490 | 1.0443 | 0.049* | 0.29 (10) |
N1A | −0.3472 (11) | 0.5046 (5) | 0.8221 (4) | 0.0451 (14) | |
C1A | 0.4634 (11) | 0.1847 (5) | 0.9264 (4) | 0.0260 (12) | |
C2A | 0.4493 (11) | 0.2062 (5) | 0.8411 (4) | 0.0280 (13) | |
H2A' | 0.5819 | 0.1648 | 0.8011 | 0.034* | |
C3A | 0.2389 (12) | 0.2890 (5) | 0.8144 (4) | 0.0327 (13) | |
C4A | 0.0391 (11) | 0.3477 (5) | 0.8726 (4) | 0.0268 (12) | |
C5A | 0.0536 (11) | 0.3228 (4) | 0.9586 (4) | 0.0236 (12) | |
C6A | 0.2679 (11) | 0.2427 (5) | 0.9867 (4) | 0.0242 (12) | |
H6A | 0.2814 | 0.2277 | 1.0454 | 0.029* | |
C7A | 0.6960 (11) | 0.1006 (4) | 0.9595 (4) | 0.0250 (13) | |
C8A | −0.1740 (12) | 0.4353 (5) | 0.8443 (4) | 0.0311 (13) | |
Cl3B | 0.9586 (4) | 0.19421 (17) | 0.20901 (10) | 0.0568 (6) | |
Cl5B | 1.1722 (3) | 0.11078 (12) | 0.53543 (9) | 0.0326 (4) | |
O1B | 0.1863 (8) | 0.4529 (4) | 0.3966 (2) | 0.0339 (10) | |
H1B | 0.0361 | 0.4900 | 0.4178 | 0.051* | 0.69 (9) |
O2B | 0.2681 (8) | 0.4204 (3) | 0.5326 (2) | 0.0296 (10) | |
H2B | 0.2045 | 0.4907 | 0.5406 | 0.044* | 0.31 (9) |
N1B | 1.4569 (12) | 0.0040 (5) | 0.3254 (4) | 0.0507 (15) | |
C1B | 0.5837 (11) | 0.3219 (5) | 0.4266 (4) | 0.0266 (13) | |
C2B | 0.6495 (12) | 0.3026 (5) | 0.3401 (4) | 0.0299 (13) | |
H2B' | 0.5409 | 0.3445 | 0.2995 | 0.036* | |
C3B | 0.8771 (12) | 0.2209 (5) | 0.3153 (4) | 0.0307 (13) | |
C4B | 1.0389 (11) | 0.1584 (5) | 0.3750 (4) | 0.0278 (13) | |
C5B | 0.9694 (12) | 0.1831 (5) | 0.4608 (4) | 0.0254 (12) | |
C6B | 0.7422 (11) | 0.2630 (5) | 0.4869 (4) | 0.0279 (13) | |
H6B | 0.6946 | 0.2776 | 0.5453 | 0.033* | |
C7B | 0.3315 (11) | 0.4048 (5) | 0.4571 (4) | 0.0254 (13) | |
C8B | 1.2695 (12) | 0.0721 (5) | 0.3481 (4) | 0.0354 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl3A | 0.0619 (11) | 0.0530 (11) | 0.0291 (9) | 0.0205 (9) | −0.0068 (7) | 0.0005 (7) |
Cl5A | 0.0273 (8) | 0.0259 (9) | 0.0385 (9) | 0.0015 (6) | 0.0008 (6) | −0.0022 (6) |
O1A | 0.028 (2) | 0.032 (2) | 0.040 (2) | 0.0045 (19) | −0.0071 (19) | −0.0030 (19) |
O2A | 0.032 (2) | 0.029 (2) | 0.035 (2) | 0.0018 (19) | −0.0109 (18) | 0.0051 (18) |
N1A | 0.039 (3) | 0.042 (3) | 0.050 (3) | 0.010 (3) | −0.006 (3) | 0.003 (3) |
C1A | 0.028 (3) | 0.018 (3) | 0.033 (3) | −0.006 (2) | −0.005 (2) | 0.001 (2) |
C2A | 0.029 (3) | 0.019 (3) | 0.035 (3) | 0.002 (2) | −0.006 (2) | −0.003 (2) |
C3A | 0.039 (3) | 0.027 (3) | 0.032 (3) | −0.005 (3) | −0.003 (3) | 0.000 (3) |
C4A | 0.024 (3) | 0.019 (3) | 0.037 (3) | 0.000 (2) | −0.006 (2) | −0.002 (2) |
C5A | 0.021 (3) | 0.009 (3) | 0.039 (3) | 0.002 (2) | −0.001 (2) | −0.004 (2) |
C6A | 0.027 (3) | 0.020 (3) | 0.028 (3) | −0.009 (2) | −0.006 (2) | 0.002 (2) |
C7A | 0.022 (3) | 0.013 (3) | 0.040 (4) | −0.005 (2) | −0.006 (2) | −0.001 (2) |
C8A | 0.033 (3) | 0.021 (3) | 0.038 (3) | 0.002 (3) | −0.003 (3) | −0.005 (3) |
Cl3B | 0.0701 (13) | 0.0587 (13) | 0.0305 (10) | 0.0205 (10) | 0.0050 (8) | −0.0037 (8) |
Cl5B | 0.0311 (8) | 0.0273 (9) | 0.0390 (9) | 0.0009 (7) | −0.0107 (6) | 0.0026 (6) |
O1B | 0.030 (2) | 0.037 (2) | 0.030 (2) | 0.0113 (18) | −0.0039 (17) | 0.0014 (18) |
O2B | 0.028 (2) | 0.026 (2) | 0.032 (2) | 0.0051 (18) | −0.0001 (17) | 0.0011 (17) |
N1B | 0.051 (4) | 0.048 (4) | 0.046 (3) | 0.017 (3) | −0.002 (3) | −0.006 (3) |
C1B | 0.020 (3) | 0.023 (3) | 0.036 (3) | 0.000 (2) | −0.005 (2) | 0.002 (2) |
C2B | 0.030 (3) | 0.027 (3) | 0.031 (3) | 0.002 (2) | −0.006 (2) | 0.004 (2) |
C3B | 0.031 (3) | 0.027 (3) | 0.031 (3) | 0.003 (2) | 0.001 (2) | −0.001 (2) |
C4B | 0.024 (3) | 0.024 (3) | 0.035 (3) | −0.005 (2) | 0.002 (2) | −0.001 (2) |
C5B | 0.025 (3) | 0.021 (3) | 0.030 (3) | −0.007 (2) | −0.004 (2) | 0.005 (2) |
C6B | 0.028 (3) | 0.024 (3) | 0.030 (3) | 0.000 (2) | −0.001 (2) | −0.005 (2) |
C7B | 0.025 (3) | 0.021 (3) | 0.030 (3) | −0.003 (2) | −0.002 (2) | 0.004 (2) |
C8B | 0.029 (3) | 0.032 (3) | 0.042 (4) | 0.005 (3) | 0.000 (3) | 0.002 (3) |
Cl3A—C3A | 1.728 (6) | Cl3B—C3B | 1.725 (6) |
Cl5A—C5A | 1.728 (5) | Cl5B—C5B | 1.733 (6) |
O1A—C7A | 1.305 (7) | O1B—C7B | 1.309 (7) |
O1A—H1A | 0.8400 | O1B—H1B | 0.8400 |
O2A—C7A | 1.225 (7) | O2B—C7B | 1.223 (7) |
O2A—H2A | 0.8400 | O2B—H2B | 0.8400 |
N1A—C8A | 1.150 (7) | N1B—C8B | 1.154 (8) |
C1A—C2A | 1.378 (8) | C1B—C6B | 1.388 (8) |
C1A—C6A | 1.400 (8) | C1B—C2B | 1.399 (8) |
C1A—C7A | 1.506 (8) | C1B—C7B | 1.497 (7) |
C2A—C3A | 1.386 (8) | C2B—C3B | 1.385 (8) |
C2A—H2A' | 0.9500 | C2B—H2B' | 0.9500 |
C3A—C4A | 1.395 (8) | C3B—C4B | 1.406 (8) |
C4A—C5A | 1.395 (8) | C4B—C5B | 1.403 (8) |
C4A—C8A | 1.436 (8) | C4B—C8B | 1.434 (8) |
C5A—C6A | 1.389 (7) | C5B—C6B | 1.376 (8) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—O1A—H1A | 109.5 | C7B—O1B—H1B | 109.5 |
C7A—O2A—H2A | 109.5 | C7B—O2B—H2B | 109.5 |
C2A—C1A—C6A | 121.8 (5) | C6B—C1B—C2B | 121.8 (5) |
C2A—C1A—C7A | 121.5 (5) | C6B—C1B—C7B | 117.7 (5) |
C6A—C1A—C7A | 116.7 (5) | C2B—C1B—C7B | 120.5 (5) |
C1A—C2A—C3A | 119.0 (5) | C3B—C2B—C1B | 118.3 (5) |
C1A—C2A—H2A' | 120.5 | C3B—C2B—H2B' | 120.8 |
C3A—C2A—H2A' | 120.5 | C1B—C2B—H2B' | 120.8 |
C2A—C3A—C4A | 120.8 (5) | C2B—C3B—C4B | 121.2 (5) |
C2A—C3A—Cl3A | 119.2 (5) | C2B—C3B—Cl3B | 119.0 (5) |
C4A—C3A—Cl3A | 120.0 (4) | C4B—C3B—Cl3B | 119.7 (4) |
C3A—C4A—C5A | 119.2 (5) | C5B—C4B—C3B | 118.4 (5) |
C3A—C4A—C8A | 120.3 (5) | C5B—C4B—C8B | 121.2 (5) |
C5A—C4A—C8A | 120.5 (5) | C3B—C4B—C8B | 120.4 (5) |
C6A—C5A—C4A | 120.8 (5) | C6B—C5B—C4B | 121.3 (5) |
C6A—C5A—Cl5A | 118.8 (4) | C6B—C5B—Cl5B | 119.4 (4) |
C4A—C5A—Cl5A | 120.3 (4) | C4B—C5B—Cl5B | 119.3 (4) |
C5A—C6A—C1A | 118.3 (5) | C5B—C6B—C1B | 119.0 (5) |
C5A—C6A—H6A | 120.8 | C5B—C6B—H6B | 120.5 |
C1A—C6A—H6A | 120.8 | C1B—C6B—H6B | 120.5 |
O2A—C7A—O1A | 125.3 (5) | O2B—C7B—O1B | 124.8 (5) |
O2A—C7A—C1A | 121.6 (5) | O2B—C7B—C1B | 121.2 (5) |
O1A—C7A—C1A | 113.2 (5) | O1B—C7B—C1B | 114.0 (5) |
N1A—C8A—C4A | 179.2 (7) | N1B—C8B—C4B | 178.8 (8) |
C6A—C1A—C2A—C3A | 1.2 (8) | C6B—C1B—C2B—C3B | 1.1 (9) |
C7A—C1A—C2A—C3A | −176.6 (5) | C7B—C1B—C2B—C3B | −176.8 (5) |
C1A—C2A—C3A—C4A | −1.8 (9) | C1B—C2B—C3B—C4B | 0.0 (9) |
C1A—C2A—C3A—Cl3A | 177.5 (4) | C1B—C2B—C3B—Cl3B | 179.0 (4) |
C2A—C3A—C4A—C5A | 0.3 (9) | C2B—C3B—C4B—C5B | −1.8 (9) |
Cl3A—C3A—C4A—C5A | −178.9 (4) | Cl3B—C3B—C4B—C5B | 179.2 (4) |
C2A—C3A—C4A—C8A | 178.5 (6) | C2B—C3B—C4B—C8B | 178.4 (6) |
Cl3A—C3A—C4A—C8A | −0.7 (8) | Cl3B—C3B—C4B—C8B | −0.6 (8) |
C3A—C4A—C5A—C6A | 1.7 (8) | C3B—C4B—C5B—C6B | 2.6 (8) |
C8A—C4A—C5A—C6A | −176.5 (5) | C8B—C4B—C5B—C6B | −177.6 (6) |
C3A—C4A—C5A—Cl5A | −178.1 (4) | C3B—C4B—C5B—Cl5B | −177.9 (4) |
C8A—C4A—C5A—Cl5A | 3.7 (8) | C8B—C4B—C5B—Cl5B | 1.8 (8) |
C4A—C5A—C6A—C1A | −2.2 (8) | C4B—C5B—C6B—C1B | −1.6 (8) |
Cl5A—C5A—C6A—C1A | 177.6 (4) | Cl5B—C5B—C6B—C1B | 178.9 (4) |
C2A—C1A—C6A—C5A | 0.7 (8) | C2B—C1B—C6B—C5B | −0.3 (8) |
C7A—C1A—C6A—C5A | 178.7 (5) | C7B—C1B—C6B—C5B | 177.6 (5) |
C2A—C1A—C7A—O2A | −178.7 (5) | C6B—C1B—C7B—O2B | 0.3 (8) |
C6A—C1A—C7A—O2A | 3.3 (8) | C2B—C1B—C7B—O2B | 178.3 (6) |
C2A—C1A—C7A—O1A | 1.9 (7) | C6B—C1B—C7B—O1B | −177.1 (5) |
C6A—C1A—C7A—O1A | −176.0 (5) | C2B—C1B—C7B—O1B | 0.9 (8) |
C8H3Cl2NO2 | F(000) = 432 |
Mr = 216.01 | Dx = 1.720 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3170 reflections |
a = 7.3429 (18) Å | θ = 2.7–27.5° |
b = 10.378 (3) Å | µ = 0.74 mm−1 |
c = 11.826 (3) Å | T = 174 K |
β = 112.22 (1)° | Plate, colourless |
V = 834.3 (4) Å3 | 0.50 × 0.50 × 0.05 mm |
Z = 4 |
Bruker SMART 1K CCD area-detector diffractometer | 1915 independent reflections |
Radiation source: fine-focus sealed tube | 1754 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.6°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) | h = −9→9 |
Tmin = 0.70, Tmax = 0.96 | k = −13→13 |
9369 measured reflections | l = −15→15 |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.044P)2 + 0.252P] where P = (Fo2 + 2Fc2)/3 |
1915 reflections | (Δ/σ)max = 0.001 |
119 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C8H3Cl2NO2 | V = 834.3 (4) Å3 |
Mr = 216.01 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3429 (18) Å | µ = 0.74 mm−1 |
b = 10.378 (3) Å | T = 174 K |
c = 11.826 (3) Å | 0.50 × 0.50 × 0.05 mm |
β = 112.22 (1)° |
Bruker SMART 1K CCD area-detector diffractometer | 1915 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) | 1754 reflections with I > 2σ(I) |
Tmin = 0.70, Tmax = 0.96 | Rint = 0.030 |
9369 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.30 e Å−3 |
1915 reflections | Δρmin = −0.30 e Å−3 |
119 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.31648 (17) | 0.69293 (11) | 0.44975 (11) | 0.0218 (2) | |
C2 | 0.27108 (17) | 0.63436 (12) | 0.33691 (11) | 0.0231 (2) | |
H22 | 0.2776 | 0.6818 | 0.2698 | 0.028* | |
C3 | 0.21615 (17) | 0.50585 (12) | 0.32326 (11) | 0.0224 (2) | |
C4 | 0.20786 (16) | 0.43559 (11) | 0.42170 (11) | 0.0222 (3) | |
C5 | 0.25307 (17) | 0.49691 (11) | 0.53426 (11) | 0.0220 (2) | |
C6 | 0.30724 (17) | 0.62510 (12) | 0.54902 (11) | 0.0227 (2) | |
H6 | 0.3377 | 0.6664 | 0.6257 | 0.027* | |
C7 | 0.38701 (17) | 0.82972 (12) | 0.46921 (11) | 0.0241 (2) | |
C8 | 0.15813 (19) | 0.30118 (13) | 0.40912 (12) | 0.0278 (3) | |
N1 | 0.1238 (2) | 0.19362 (12) | 0.40143 (13) | 0.0430 (3) | |
O1 | 0.41088 (16) | 0.88360 (9) | 0.37833 (9) | 0.0350 (2) | |
H1 | 0.4630 | 0.9563 | 0.3995 | 0.042* | 0.67 (3) |
O2 | 0.42118 (15) | 0.88103 (9) | 0.56960 (9) | 0.0335 (2) | |
H2 | 0.4646 | 0.9559 | 0.5693 | 0.040* | 0.33 (3) |
Cl3 | 0.16398 (5) | 0.42967 (3) | 0.18567 (3) | 0.03295 (12) | |
Cl5 | 0.24506 (5) | 0.40927 (3) | 0.65576 (3) | 0.02927 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0208 (5) | 0.0172 (5) | 0.0264 (6) | 0.0008 (4) | 0.0077 (4) | 0.0008 (4) |
C2 | 0.0240 (6) | 0.0201 (6) | 0.0255 (6) | 0.0013 (4) | 0.0097 (5) | 0.0024 (4) |
C3 | 0.0224 (5) | 0.0200 (6) | 0.0246 (6) | 0.0017 (4) | 0.0085 (4) | −0.0025 (4) |
C4 | 0.0198 (5) | 0.0173 (5) | 0.0285 (6) | 0.0017 (4) | 0.0081 (5) | 0.0012 (4) |
C5 | 0.0200 (5) | 0.0210 (5) | 0.0244 (6) | 0.0021 (4) | 0.0078 (4) | 0.0046 (4) |
C6 | 0.0222 (5) | 0.0211 (6) | 0.0237 (6) | 0.0004 (4) | 0.0073 (4) | −0.0010 (5) |
C7 | 0.0246 (6) | 0.0194 (6) | 0.0266 (6) | −0.0001 (4) | 0.0078 (5) | 0.0004 (5) |
C8 | 0.0279 (6) | 0.0233 (6) | 0.0299 (6) | −0.0012 (5) | 0.0084 (5) | 0.0007 (5) |
N1 | 0.0520 (8) | 0.0241 (6) | 0.0468 (8) | −0.0076 (5) | 0.0117 (6) | −0.0008 (5) |
O1 | 0.0513 (6) | 0.0220 (5) | 0.0330 (5) | −0.0095 (4) | 0.0175 (5) | 0.0004 (4) |
O2 | 0.0459 (6) | 0.0223 (5) | 0.0316 (5) | −0.0074 (4) | 0.0139 (4) | −0.0054 (4) |
Cl3 | 0.0479 (2) | 0.02443 (18) | 0.02905 (19) | −0.00132 (13) | 0.01745 (15) | −0.00642 (11) |
Cl5 | 0.03435 (19) | 0.02669 (18) | 0.02689 (18) | −0.00203 (11) | 0.01171 (14) | 0.00652 (11) |
C1—C2 | 1.3875 (17) | C5—C6 | 1.3806 (17) |
C1—C6 | 1.3923 (17) | C5—Cl5 | 1.7201 (12) |
C1—C7 | 1.4987 (17) | C6—H6 | 0.9500 |
C2—C3 | 1.3850 (17) | C7—O2 | 1.2372 (16) |
C2—H22 | 0.9500 | C7—O1 | 1.2810 (16) |
C3—C4 | 1.3945 (17) | C8—N1 | 1.1404 (19) |
C3—Cl3 | 1.7170 (13) | O1—H1 | 0.8400 |
C4—C5 | 1.3975 (17) | O2—H2 | 0.8400 |
C4—C8 | 1.4353 (18) | ||
C2—C1—C6 | 121.26 (11) | C6—C5—C4 | 120.83 (11) |
C2—C1—C7 | 120.40 (11) | C6—C5—Cl5 | 120.21 (9) |
C6—C1—C7 | 118.27 (11) | C4—C5—Cl5 | 118.95 (9) |
C3—C2—C1 | 119.17 (11) | C5—C6—C1 | 118.96 (11) |
C3—C2—H22 | 120.4 | C5—C6—H6 | 120.5 |
C1—C2—H22 | 120.4 | C1—C6—H6 | 120.5 |
C2—C3—C4 | 120.60 (11) | O2—C7—O1 | 125.08 (12) |
C2—C3—Cl3 | 120.31 (9) | O2—C7—C1 | 119.20 (11) |
C4—C3—Cl3 | 119.07 (10) | O1—C7—C1 | 115.70 (11) |
C3—C4—C5 | 119.17 (11) | N1—C8—C4 | 178.08 (15) |
C3—C4—C8 | 120.75 (11) | C7—O1—H1 | 109.5 |
C5—C4—C8 | 120.06 (11) | C7—O2—H2 | 109.5 |
C6—C1—C2—C3 | −0.19 (18) | C3—C4—C5—Cl5 | −179.33 (9) |
C7—C1—C2—C3 | 176.64 (10) | C8—C4—C5—Cl5 | −0.77 (16) |
C1—C2—C3—C4 | −0.49 (18) | C4—C5—C6—C1 | −0.06 (17) |
C1—C2—C3—Cl3 | −178.65 (9) | Cl5—C5—C6—C1 | 178.65 (9) |
C2—C3—C4—C5 | 0.89 (17) | C2—C1—C6—C5 | 0.46 (17) |
Cl3—C3—C4—C5 | 179.07 (9) | C7—C1—C6—C5 | −176.44 (10) |
C2—C3—C4—C8 | −177.66 (11) | C2—C1—C7—O2 | 177.94 (11) |
Cl3—C3—C4—C8 | 0.52 (16) | C6—C1—C7—O2 | −5.13 (17) |
C3—C4—C5—C6 | −0.61 (17) | C2—C1—C7—O1 | −3.44 (16) |
C8—C4—C5—C6 | 177.94 (11) | C6—C1—C7—O1 | 173.49 (11) |
C8H3Cl2NO2·0.25H2O | F(000) = 884 |
Mr = 220.52 | Dx = 1.698 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2775 reflections |
a = 11.237 (3) Å | θ = 2.2–27.5° |
b = 11.410 (3) Å | µ = 0.72 mm−1 |
c = 14.566 (4) Å | T = 174 K |
β = 112.50 (1)° | Prism, colourless |
V = 1725.4 (8) Å3 | 0.35 × 0.25 × 0.25 mm |
Z = 8 |
Bruker SMART 1K CCD area-detector diffractometer | 3893 independent reflections |
Radiation source: fine-focus sealed tube | 3265 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) | h = −14→14 |
Tmin = 0.76, Tmax = 0.84 | k = −14→14 |
19254 measured reflections | l = −18→18 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.92P] where P = (Fo2 + 2Fc2)/3 |
3893 reflections | (Δ/σ)max = 0.002 |
251 parameters | Δρmax = 0.41 e Å−3 |
3 restraints | Δρmin = −0.46 e Å−3 |
C8H3Cl2NO2·0.25H2O | V = 1725.4 (8) Å3 |
Mr = 220.52 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.237 (3) Å | µ = 0.72 mm−1 |
b = 11.410 (3) Å | T = 174 K |
c = 14.566 (4) Å | 0.35 × 0.25 × 0.25 mm |
β = 112.50 (1)° |
Bruker SMART 1K CCD area-detector diffractometer | 3893 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) | 3265 reflections with I > 2σ(I) |
Tmin = 0.76, Tmax = 0.84 | Rint = 0.024 |
19254 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 3 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.41 e Å−3 |
3893 reflections | Δρmin = −0.46 e Å−3 |
251 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1A | 0.54957 (14) | 0.71878 (12) | 0.58559 (11) | 0.0197 (3) | |
C2A | 0.66894 (14) | 0.66522 (13) | 0.60880 (11) | 0.0214 (3) | |
H22A | 0.7399 | 0.7081 | 0.6060 | 0.026* | |
C3A | 0.68210 (14) | 0.54794 (13) | 0.63604 (11) | 0.0215 (3) | |
C4A | 0.57732 (14) | 0.48353 (13) | 0.63842 (10) | 0.0199 (3) | |
C5A | 0.45824 (14) | 0.53993 (13) | 0.61441 (11) | 0.0197 (3) | |
C6A | 0.44383 (14) | 0.65740 (13) | 0.58859 (11) | 0.0204 (3) | |
H6A | 0.3633 | 0.6955 | 0.5732 | 0.024* | |
C7A | 0.53193 (14) | 0.84520 (13) | 0.55480 (11) | 0.0211 (3) | |
C8A | 0.59125 (14) | 0.36091 (14) | 0.66526 (11) | 0.0236 (3) | |
N1A | 0.60130 (14) | 0.26377 (13) | 0.68548 (12) | 0.0344 (3) | |
O1A | 0.62902 (11) | 0.89574 (10) | 0.54596 (10) | 0.0330 (3) | |
H1A | 0.6074 | 0.9628 | 0.5214 | 0.050* | 0.68 (3) |
O2A | 0.42704 (11) | 0.89358 (10) | 0.53945 (10) | 0.0312 (3) | |
H2A | 0.4293 | 0.9629 | 0.5208 | 0.047* | 0.32 (3) |
Cl3A | 0.82934 (4) | 0.47983 (4) | 0.66758 (3) | 0.03258 (11) | |
Cl5A | 0.32945 (3) | 0.46085 (3) | 0.61848 (3) | 0.02533 (10) | |
C1B | 0.06234 (14) | −0.10519 (13) | 0.60934 (11) | 0.0211 (3) | |
C2B | −0.04191 (14) | −0.04466 (13) | 0.61537 (11) | 0.0213 (3) | |
H22B | −0.1208 | −0.0840 | 0.6040 | 0.026* | |
C3B | −0.02904 (14) | 0.07377 (13) | 0.63820 (10) | 0.0202 (3) | |
C4B | 0.08763 (14) | 0.13191 (13) | 0.65608 (10) | 0.0205 (3) | |
C5B | 0.19199 (14) | 0.06850 (13) | 0.65129 (11) | 0.0219 (3) | |
C6B | 0.17925 (15) | −0.04944 (13) | 0.62687 (11) | 0.0223 (3) | |
H6B | 0.2495 | −0.0918 | 0.6221 | 0.027* | |
C7B | 0.04671 (19) | −0.23218 (14) | 0.58112 (12) | 0.0333 (4) | |
C8B | 0.09636 (15) | 0.25641 (14) | 0.67463 (11) | 0.0247 (3) | |
N1B | 0.09872 (14) | 0.35550 (12) | 0.68511 (12) | 0.0339 (3) | |
O1B | −0.06216 (12) | −0.27837 (10) | 0.56165 (10) | 0.0359 (3) | |
H1B | −0.0593 | −0.3494 | 0.5475 | 0.054* | 0.50 |
O2B | 0.14256 (13) | −0.28594 (11) | 0.57635 (11) | 0.0396 (3) | |
H2B | 0.1206 | −0.3543 | 0.5552 | 0.059* | 0.50 |
Cl3B | −0.15812 (4) | 0.15081 (3) | 0.64354 (3) | 0.02737 (10) | |
Cl5B | 0.33611 (4) | 0.13857 (4) | 0.67439 (3) | 0.03325 (11) | |
O1W | −0.0197 (2) | −0.4994 (3) | 0.5060 (2) | 0.0302 (6)* | 0.50 |
H1W | −0.004 (4) | −0.490 (2) | 0.4546 (15) | 0.045* | 0.50 |
H2W | 0.0489 (19) | −0.515 (4) | 0.5543 (17) | 0.045* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0211 (7) | 0.0161 (7) | 0.0214 (7) | 0.0013 (5) | 0.0076 (6) | 0.0008 (5) |
C2A | 0.0196 (7) | 0.0194 (7) | 0.0261 (7) | −0.0006 (6) | 0.0098 (6) | 0.0007 (6) |
C3A | 0.0188 (7) | 0.0213 (7) | 0.0251 (7) | 0.0043 (6) | 0.0091 (6) | 0.0011 (6) |
C4A | 0.0228 (7) | 0.0166 (7) | 0.0200 (7) | 0.0011 (5) | 0.0078 (6) | 0.0002 (5) |
C5A | 0.0183 (7) | 0.0197 (7) | 0.0212 (7) | −0.0028 (5) | 0.0077 (6) | −0.0006 (5) |
C6A | 0.0181 (7) | 0.0196 (7) | 0.0231 (7) | 0.0020 (6) | 0.0075 (6) | 0.0004 (5) |
C7A | 0.0207 (7) | 0.0180 (7) | 0.0241 (7) | 0.0007 (6) | 0.0080 (6) | 0.0014 (6) |
C8A | 0.0215 (7) | 0.0220 (8) | 0.0275 (8) | 0.0009 (6) | 0.0096 (6) | 0.0018 (6) |
N1A | 0.0314 (8) | 0.0236 (7) | 0.0478 (9) | 0.0029 (6) | 0.0147 (7) | 0.0077 (6) |
O1A | 0.0278 (6) | 0.0205 (6) | 0.0551 (8) | 0.0012 (5) | 0.0208 (6) | 0.0104 (5) |
O2A | 0.0236 (6) | 0.0198 (6) | 0.0497 (7) | 0.0042 (5) | 0.0135 (5) | 0.0069 (5) |
Cl3A | 0.02181 (19) | 0.0250 (2) | 0.0535 (3) | 0.00805 (15) | 0.01726 (18) | 0.00917 (17) |
Cl5A | 0.02018 (18) | 0.02221 (18) | 0.0340 (2) | −0.00373 (13) | 0.01081 (15) | 0.00271 (14) |
C1B | 0.0263 (7) | 0.0172 (7) | 0.0189 (7) | 0.0009 (6) | 0.0074 (6) | 0.0012 (5) |
C2B | 0.0214 (7) | 0.0198 (7) | 0.0216 (7) | −0.0018 (6) | 0.0069 (6) | 0.0005 (5) |
C3B | 0.0199 (7) | 0.0202 (7) | 0.0196 (7) | 0.0038 (6) | 0.0066 (6) | 0.0012 (5) |
C4B | 0.0249 (7) | 0.0168 (7) | 0.0179 (7) | −0.0013 (6) | 0.0060 (6) | 0.0004 (5) |
C5B | 0.0203 (7) | 0.0237 (7) | 0.0210 (7) | −0.0028 (6) | 0.0069 (6) | 0.0012 (6) |
C6B | 0.0229 (7) | 0.0225 (7) | 0.0217 (7) | 0.0046 (6) | 0.0087 (6) | 0.0016 (6) |
C7B | 0.0572 (12) | 0.0179 (8) | 0.0247 (8) | 0.0022 (8) | 0.0157 (8) | 0.0013 (6) |
C8B | 0.0244 (8) | 0.0234 (8) | 0.0227 (7) | −0.0011 (6) | 0.0050 (6) | −0.0010 (6) |
N1B | 0.0335 (8) | 0.0222 (7) | 0.0391 (8) | −0.0016 (6) | 0.0062 (6) | −0.0027 (6) |
O1B | 0.0394 (7) | 0.0191 (6) | 0.0513 (8) | −0.0066 (5) | 0.0195 (6) | −0.0071 (5) |
O2B | 0.0424 (7) | 0.0216 (6) | 0.0602 (9) | 0.0028 (5) | 0.0256 (7) | −0.0087 (6) |
Cl3B | 0.02284 (19) | 0.0254 (2) | 0.0332 (2) | 0.00641 (14) | 0.00988 (15) | 0.00020 (15) |
Cl5B | 0.0245 (2) | 0.0335 (2) | 0.0433 (2) | −0.00822 (16) | 0.01460 (17) | −0.00342 (17) |
C1A—C2A | 1.393 (2) | C1B—C6B | 1.392 (2) |
C1A—C6A | 1.394 (2) | C1B—C7B | 1.498 (2) |
C1A—C7A | 1.501 (2) | C2B—C3B | 1.386 (2) |
C2A—C3A | 1.388 (2) | C2B—H22B | 0.9500 |
C2A—H22A | 0.9500 | C3B—C4B | 1.402 (2) |
C3A—C4A | 1.400 (2) | C3B—Cl3B | 1.7231 (15) |
C3A—Cl3A | 1.7236 (15) | C4B—C5B | 1.402 (2) |
C4A—C5A | 1.403 (2) | C4B—C8B | 1.442 (2) |
C4A—C8A | 1.445 (2) | C5B—C6B | 1.385 (2) |
C5A—C6A | 1.385 (2) | C5B—Cl5B | 1.7200 (15) |
C5A—Cl5A | 1.7256 (15) | C6B—H6B | 0.9500 |
C6A—H6A | 0.9500 | C7B—O1B | 1.261 (2) |
C7A—O2A | 1.2419 (18) | C7B—O2B | 1.264 (2) |
C7A—O1A | 1.2833 (18) | C8B—N1B | 1.140 (2) |
C8A—N1A | 1.141 (2) | O1B—H1B | 0.8400 |
O1A—H1A | 0.8400 | O2B—H2B | 0.8400 |
O2A—H2A | 0.8400 | O1W—H1W | 0.8400 (2) |
C1B—C2B | 1.391 (2) | O1W—H2W | 0.8400 (2) |
C2A—C1A—C6A | 121.68 (13) | C2B—C1B—C7B | 118.97 (14) |
C2A—C1A—C7A | 119.93 (13) | C6B—C1B—C7B | 119.70 (14) |
C6A—C1A—C7A | 118.38 (13) | C3B—C2B—C1B | 119.08 (14) |
C3A—C2A—C1A | 118.68 (14) | C3B—C2B—H22B | 120.5 |
C3A—C2A—H22A | 120.7 | C1B—C2B—H22B | 120.5 |
C1A—C2A—H22A | 120.7 | C2B—C3B—C4B | 120.68 (13) |
C2A—C3A—C4A | 120.99 (14) | C2B—C3B—Cl3B | 119.73 (11) |
C2A—C3A—Cl3A | 119.83 (12) | C4B—C3B—Cl3B | 119.59 (11) |
C4A—C3A—Cl3A | 119.18 (11) | C3B—C4B—C5B | 119.14 (14) |
C3A—C4A—C5A | 118.95 (13) | C3B—C4B—C8B | 119.51 (13) |
C3A—C4A—C8A | 120.67 (13) | C5B—C4B—C8B | 121.29 (14) |
C5A—C4A—C8A | 120.38 (13) | C6B—C5B—C4B | 120.52 (14) |
C6A—C5A—C4A | 120.85 (13) | C6B—C5B—Cl5B | 119.92 (12) |
C6A—C5A—Cl5A | 120.20 (11) | C4B—C5B—Cl5B | 119.55 (12) |
C4A—C5A—Cl5A | 118.95 (11) | C5B—C6B—C1B | 119.23 (14) |
C5A—C6A—C1A | 118.83 (13) | C5B—C6B—H6B | 120.4 |
C5A—C6A—H6A | 120.6 | C1B—C6B—H6B | 120.4 |
C1A—C6A—H6A | 120.6 | O1B—C7B—O2B | 123.96 (15) |
O2A—C7A—O1A | 124.53 (14) | O1B—C7B—C1B | 117.90 (16) |
O2A—C7A—C1A | 119.26 (13) | O2B—C7B—C1B | 118.13 (16) |
O1A—C7A—C1A | 116.21 (13) | N1B—C8B—C4B | 176.82 (17) |
N1A—C8A—C4A | 179.3 (2) | C7B—O1B—H1B | 109.5 |
C7A—O1A—H1A | 109.5 | C7B—O2B—H2B | 109.5 |
C7A—O2A—H2A | 109.5 | H1W—O1W—H2W | 109.47 (3) |
C2B—C1B—C6B | 121.32 (14) | ||
C6A—C1A—C2A—C3A | −0.4 (2) | C6B—C1B—C2B—C3B | 0.7 (2) |
C7A—C1A—C2A—C3A | −179.35 (14) | C7B—C1B—C2B—C3B | −177.86 (14) |
C1A—C2A—C3A—C4A | 1.3 (2) | C1B—C2B—C3B—C4B | −0.7 (2) |
C1A—C2A—C3A—Cl3A | −178.73 (11) | C1B—C2B—C3B—Cl3B | 178.71 (11) |
C2A—C3A—C4A—C5A | −1.1 (2) | C2B—C3B—C4B—C5B | −0.5 (2) |
Cl3A—C3A—C4A—C5A | 178.87 (11) | Cl3B—C3B—C4B—C5B | −179.83 (11) |
C2A—C3A—C4A—C8A | 178.95 (14) | C2B—C3B—C4B—C8B | 176.82 (14) |
Cl3A—C3A—C4A—C8A | −1.1 (2) | Cl3B—C3B—C4B—C8B | −2.56 (19) |
C3A—C4A—C5A—C6A | 0.1 (2) | C3B—C4B—C5B—C6B | 1.6 (2) |
C8A—C4A—C5A—C6A | 180.00 (14) | C8B—C4B—C5B—C6B | −175.67 (14) |
C3A—C4A—C5A—Cl5A | −179.40 (11) | C3B—C4B—C5B—Cl5B | −179.31 (11) |
C8A—C4A—C5A—Cl5A | 0.54 (19) | C8B—C4B—C5B—Cl5B | 3.5 (2) |
C4A—C5A—C6A—C1A | 0.8 (2) | C4B—C5B—C6B—C1B | −1.5 (2) |
Cl5A—C5A—C6A—C1A | −179.74 (11) | Cl5B—C5B—C6B—C1B | 179.37 (11) |
C2A—C1A—C6A—C5A | −0.7 (2) | C2B—C1B—C6B—C5B | 0.3 (2) |
C7A—C1A—C6A—C5A | 178.35 (13) | C7B—C1B—C6B—C5B | 178.92 (14) |
C2A—C1A—C7A—O2A | −176.18 (14) | C2B—C1B—C7B—O1B | 1.6 (2) |
C6A—C1A—C7A—O2A | 4.8 (2) | C6B—C1B—C7B—O1B | −177.00 (14) |
C2A—C1A—C7A—O1A | 4.0 (2) | C2B—C1B—C7B—O2B | −179.75 (15) |
C6A—C1A—C7A—O1A | −175.00 (14) | C6B—C1B—C7B—O2B | 1.6 (2) |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C8H3Cl2NO2 | C8H3Cl2NO2 | C8H3Cl2NO2·0.25H2O |
Mr | 216.01 | 216.01 | 220.52 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 174 | 174 | 174 |
a, b, c (Å) | 4.8859 (17), 11.658 (4), 15.891 (6) | 7.3429 (18), 10.378 (3), 11.826 (3) | 11.237 (3), 11.410 (3), 14.566 (4) |
α, β, γ (°) | 88.39 (1), 84.79 (1), 81.23 (1) | 90, 112.22 (1), 90 | 90, 112.50 (1), 90 |
V (Å3) | 890.8 (6) | 834.3 (4) | 1725.4 (8) |
Z | 4 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.69 | 0.74 | 0.72 |
Crystal size (mm) | 0.25 × 0.20 × 0.10 | 0.50 × 0.50 × 0.05 | 0.35 × 0.25 × 0.25 |
Data collection | |||
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer | Bruker SMART 1K CCD area-detector diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (TWINABS; Sheldrick, 2003; Blessing, 1995) | Multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) | Multi-scan (SADABS; Sheldrick, 2003; Blessing, 1995) |
Tmin, Tmax | 0.85, 0.93 | 0.70, 0.96 | 0.76, 0.84 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11344, 3178, 2660 | 9369, 1915, 1754 | 19254, 3893, 3265 |
Rint | 0.059 | 0.030 | 0.024 |
(sin θ/λ)max (Å−1) | 0.597 | 0.651 | 0.649 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.136, 1.15 | 0.026, 0.075, 1.05 | 0.027, 0.076, 1.04 |
No. of reflections | 3178 | 1915 | 3893 |
No. of parameters | 242 | 119 | 251 |
No. of restraints | 0 | 0 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.34 | 0.30, −0.30 | 0.41, −0.46 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.
Compound | O—H···X—Y | O—H···X | H···X | H···X—Y | O···X |
(I) | O1A—H1A···O2Ai-C7Ai | 178 | 1.80 | 123 | 2.641 (7) |
(I) | O2A—H2A···O1Ai-C7Ai | 153 | 1.87 | 105 | 2.641 (7) |
(I) | O1B—H1B···O2Bii-C7Bii | 175 | 1.81 | 128 | 2.648 (7) |
(I) | O2B—H2B···O2Aii-C7Bii | 123 | 2.09 | 103 | 2.648 (7) |
(II) | O1—H1···O2iii-C7iii | 174 | 1.86 | 119 | 2.700 (2) |
(II) | O2—H2···O1iii-C7iii | 162 | 1.89 | 108 | 2.700 (2) |
(III) | O1A—H1A···O2Aiii-C7Aiii | 173 | 1.83 | 120 | 2.669 (2) |
(III) | O2A—H2A···O1Aiii-C7Aiii | 159 | 1.87 | 107 | 2.669 (2) |
(III) | O1B—H1B···O1W···O2Biv | 166 | 1.92 | 136 | 2.746 (4) |
(III) | O2B—H2B···O1Wiv···O1Biv | 165 | 2.02 | 136 | 2.843 (4) |
(III)b | O1W—H1W···N1Bv-C8Bv | 130 | 2.45 | 122 | 3.056 (4) |
(III)b | O1W—H2W···N1Bvi-C8Bv | 133 | 2.30 | 123 | 2.943 (4) |
Notes: (a) all O—H distances are 0.84 Å; (b) these entries describe contacts between layers and are not shown in any of the figures. Symmetry codes: (i) 2 − x, −y, 2 − z; (ii) −x, 1 − y, 1 − z; (iii) 1 − x, 2 − y, 1 − z; (iv) −x, −1 − y, 1 − z; (v) −x, −y, 1 − z; (vi) x, −1 + y, z. |
Compound | Cl···X | C—Cl···X | Cl···X | Cl···X—C |
(I) | Cl5A···N1Ai | 174.7 (6) | 3.195 (6) | 115.0 (4) |
(I) | Cl5B···N1Bii | 176.2 (6) | 3.128 (6) | 116.4 (4) |
(I) | Cl3A···O2B | 167.1 (3) | 2.989 (6) | 148.3 (4) |
(II) | Cl3···N1iii | 170.1 (2) | 3.503 (2) | 110.2 (1) |
(II) | Cl5···N1iv | 162.0 (2) | 3.512 (2) | 104.2 (1) |
(II)b | Cl3···N1v | 78.8 (1) | 3.374 (2) | 155.9 (1) |
(II)b | Cl5···O1vi | 101.9 (1) | 3.257 (2) | 147.0 (2) |
(II)b | Cl5···O2vii | 129.0 (1) | 3.259 (2) | 143.0 (2) |
(III) | Cl3A···N1Bviii | 169.7 (2) | 3.263 (2) | 116.6 (1) |
(III) | Cl5A···N1B | 163.3 (2) | 3.322 (2) | 107.5 (1) |
(III) | Cl3B···N1Aix | 169.7 (2) | 3.257 (2) | 110.1 (1) |
(III) | Cl5B···N1A | 171.9 (2) | 3.252 (2) | 114.5 (1) |
(III)b | Cl3A···O1Wx | 117.8 (1) | 3.396 (3) | |
(III)b | Cl3A···O1Bx | 89.3 (1) | 3.594 (2) | 133.1 (1) |
(III)b | Cl5A···O1Wxi | 129.6 (1) | 3.282 (3) | |
(III)b | Cl5A···O2Bxii | 91.0 (1) | 3.485 (2) | 149.4 (2) |
(III)b | Cl3B···O2Axiii | 115.0 (1) | 3.214 (2) | 127.3 (1) |
(III)b | Cl5B···O1Axiv | 101.6 (1) | 3.402 (2) | 116.9 (1) |
Notes: (a) for comparison, the van der Waals contact distances (Bondi, 1964; Rowland & Taylor, 1996) are Cl···N = 3.30 Å and Cl···O = 3.27 Å; (b) these entries describe bonds between layers and are not shown in any of the figures. Symmetry codes: (i) −1 − x, 1 − y, 2 − z; (ii) 3 − x, −y, 1 − z; (iii) x, 1/2 − y, −1/2 + z; (iv) x, 1/2 − y, 1/2 + z; (v) −x, 1/2 + y, 1/2 − z; (vi) x, 3/2 − y, 1/2 + z; (vii) 1 − x, −1/2 + y, 3/2 − z; (viii) 1 + x, y, z; (ix) −1 + x, y, z; (x) 1 + x, 1 + y, z; (xi) −x, −y, 1 − z; (xii) x, 1 + y, z; (xiii) −x, 1 − y, 1 − z; (xiv) 1 − x, 1 − y, 1 − z. |
In 2,3,5,6-tetrachloro-1,4-dicyanobenzene (Britton, 1981) and its charge-transfer complexes with hexamethylbenzene (Britton, 2002), clearly recognizable Cl···N interactions occur. Reddy et al. (1993) have pointed out the usefulness of Cl···N interactions in the construction of molecular tapes. In the title compound, it was expected that the molecules would form dimers through cooperative cyclic hydrogen bonds between the carboxylic acid groups of pairs of molecules to give the graph set R22(8) (Etter, 1990). The question of interest was how important the Cl···N interactions would be. When the crystals were grown, two polymorphs of the pure acid, (I) and (II), and a 0.25-hydrate, (III), were obtained. The structures of all three are reported here.
In the structure of (I), Z' = 2, and a view of the asymmetric unit showing the atom labelling and anisotropic displacement parameters for both crystallographically independent molecules is given in Fig. 1. The bond lengths and angles are normal. The expected dimers formed by the cyclic cooperative hydrogen bonds between carboxylic acid groups are present and the dimers occur around centres of symmetry such that each molecule A dimerizes with a second molecule A and pairs of B molecules dimerize likewise. The carboxylic acid H atoms are disordered across the two carboxylic acid O atoms in each molecule, with site-occupancy factors of 0.71 (10) and 0.69 (9) for the H atoms on atoms O1A and O1B, respectively.
One layer of the packing in (I) is shown in Fig. 2. The A and B molecules form similar but crystallographically independent ribbons, which run parallel to the [310] direction. In each ribbon the molecules are held together, alternately, by the cyclic hydrogen-bonded dimeric interactions between the carboxylic acid groups, and by pairs of Cl···N interactions. These Cl···N interactions are such that two A molecules interact across one centre of symmetry and two B molecules interact across another. Bernstein et al. (1995) have suggested that graph-set analysis might be extended to other systems than hydrogen bonding. In this spirit, the cyclic Cl···N interactions can be described by the graph set R22(10), with the electron acceptor Cl replacing H. These ribbons are close to planar, with the A molecules tilted by 2.2 (1)° with respect to the mean plane of the ribbon and the B molecules tilted by 2.7 (1)°. The ribbons come together to form sheets normal to (131), held together by Cl···O interactions The ribbons deviate from coplanarity with the sheet, by 4.0 (1)° for the A ribbons and by 10.4 (1)° for the B ribbons. The geometric data for the H···O and Cl···X interactions are given in Tables 1 and 2, respectively.
The molecular structure of (II), showing the atom labelling and anisotropic displacement parameters, is presented in Fig. 3. The bond lengths and angles are normal. The carboxylic acid H atom is disordered across the two carboxylic acid O atoms, with a site-occupancy factor of 0.67 (3) for the H atom on atom O1.
The atom labelling and anisotropic displacement parameters for both crystallographically independent molecules and one orientation of the disordered water molecule of (III) are shown in Fig. 3. Bond lengths and angles are normal. The carboxylic acid H atoms in molecule A are disordered in the same way as in (I), with a site-occupancy factor of 0.66 (3) for the H atom on atom O1A. The site-occupancy factors for the H atoms on atoms O1B and O2B are exactly 1/2, as a consequence of the disordered arrangement of the bridging water molecules around centres of inversion.
The crystal packing in (II) and (III) is very similar (Figs. 5 and 6). The molecules in (II) and the A and B molecules in (III) dimerize with themselves through hydrogen bonding, which will be discussed further below, and then the dimers associate through Cl···N interactions, between the dimers in (II) and between the crystallographically independent dimers in (III), to form a `chickenwire' or (6,3) two-dimensional net. The Cl···N interactions are the same cyclic R22(10) interactions found in (I), except that now each N atom is involved in two such interactions, giving a second-level graph set R22(10)R22(10). Both the interactions in (I) and those in (II) and (III) are known in other structures. The distances and angles about the atoms involved in these interactions (Table 2) are similar to those found previously (Britton, 2002). It should also be noted that there are compounds containing ortho Cl and CN in which there are no Cl···N contacts, for example, 2,6-dichlorobenzonitrile (Britton et al., 2000). In order to fill the empty space in these nets, three of them form interpenetrating triple layers, as shown in Fig. 7. For an extensive discussion of such nets and further examples of similar triple layers, see Batten & Robson (1998).
The hydrogen bonds that form the dimers in (II) and the dimers involving A molecules in (III) are the familiar cyclic sort already seen in (I). Pairs of B molecules in (III) also form dimers, but in a less common way. One water molecule, disordered across a centre of symmetry, lies between the two carboxylic acid groups of opposing B molecules in such a way that both carboxylic acid groups are hydrogen-bond donors to the bridging water molecule (Fig. 6). These interactions are not cyclic, but the directionality is disordered because of the inversion symmetry (see Fig. 6 for the two orientations of the disorder). Whether the disorder is completely random or only varies from net to net cannot be determined. The water H atoms point towards and form hydrogen bonds with N atoms in adjacent nets. For this arrangement, the first level graph set is DD and the second level is D22(5) [for a description of graph-set levels, see Bernstein et al. (1995)]. The D22(5) arrangement is rare but not unknown. In the form found here, where the bridging water molecule acts twice as a hydrogen-bond acceptor, there are 34 examples in the November 2005 release of the Cambridge Structural Database (Allen, 2002).
In Table 2, short Cl···O distances are also given. These refer to interactions between atoms in different nets in the same triple layer. These are comparable in length with the longer Cl···N contacts discussed above, but have no special directional properties. They appear to be ordinary van der Waals contacts.
It is somewhat surprising that the triple layers in (II) and (III) are so similar, given that there are extra water molecules in each net in (III). The repeat distances in the nets for the vertical directions in Figs. 5 and 6 are 3b = 31.134 Å in (II) and 3b = 34.230 Å in (III); the additional 3.096 Å is approximately what would be expected from the extra water molecule. The repeat distances in the nets for the horizontal directions in Figs. 5 and 6 are c = 11.826 Å in (II) and a = 11.327 Å in (III). The difference in these latter distances leads to the Cl···N distances generally being longer in (II) than in (III) by about 0.2 Å. This increase in length means that the Cl···N distances in (II) are not shorter than the usual van der Waals distances. However, the similarity in geometries between the Cl···N cyclic dimers in (II) and those in (III) suggests that the same interaction takes place in both, but the tighter overall packing in (II) forces the molecules apart. The molecules are tilted with respect to the layers, by 14.8 (1)° in (II), and by 16.4 (1)° (A) and 13.7 (1)° (B) in (III).