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Two polymorphs of 3,5-dichloro-4-cyano­benzoic acid, C8H3Cl2NO2, viz. triclinic and monoclinic, and its 0.25-hydrate, C8H3Cl2NO2·0.25H2O, form crystals in which hydrogen bonding and Cl...N inter­actions appear to be equally important to the structures. In all three structures, there are hydrogen-bonded (COOH) dimers of the well known cyclic type, but in the hydrate there are also dimers in which the two opposing COOH groups are separated by a water mol­ecule. In the monoclinic polymorph and in the hydrate, the inter­molecular inter­actions form two-dimensional nets inter­woven three at a time. For both the triclinic and monoclinic polymorphs, Z′= 2.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106023754/ln3011sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106023754/ln3011IIIsup4.hkl
Contains datablock III

CCDC references: 618633; 618634; 618635

Comment top

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).

Experimental top

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?]

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the two symmetry-independent molecules. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Both partially occupied carboxylic acid H atom positions are shown on each molecule; site occupancies are 0.71 (10) for O1A and 0.69 (9) for O1B.
[Figure 2] Fig. 2. One layer of (I), viewed normal to (131). The top and bottom ribbons are composed of molecules A, and the central ribbon is composed of molecules B. The heavy dotted lines show the H···O and Cl···N interactions within the ribbons and the light dotted lines show the Cl···O interactions between the ribbons. The symmetry operations for the symmetry-related molecules involved in the cyclic interactions are (2 − x, −y, 2 − z) for atoms O1A and O2A, (−x, 1 − y, 1 − z) for O1B and O2B, (−1 − x, 1 − y, 2 − z) for Cl5A and N1A and (3 − x, −y, 1 − z) for Cl5B and N1B.
[Figure 3] Fig. 3. A molecule of (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The carboxylic acid H atoms are disordered with an occupancy on O1 of 0.67 (3).
[Figure 4] Fig. 4. The asymmetric unit of (III), showing the two symmetry-independent molecules and the water molecule. Displacement ellipsoids are sdrawn at the 50% probability level. The water molecule is disordered across a centre of symmetry. Both partially occupied carboxylic acid H-atom positions are shown on each molecule, with occupancies of 0.69 (3) for O1A and 0.5 for O1B (fixed by the disorder).
[Figure 5] Fig. 5. A layer of (II), viewed normal to (001). Only the predominant carboxylic acid H atoms are shown for D [Meaning? For clarity?]. Only one orientation of O1W is shown at each position. The heavy dotted lines show the H···O and Cl···N interactions. The symmetry operations for the symmetry-related molecules involved in the cyclic interactions are (1 − x, 2 − y, 1 − z) for O1 and O2, (x, 1/2 − y, −1/2 + z) for Cl3 and N1, and (x, 1/2 − y, 1/2 + z) for Cl5 and N1.
[Figure 6] Fig. 6. A layer of (III), viewed normal to (100). Only the predominant carboxylic acid H atoms are shown. The heavy dotted lines show the H···O and Cl···N interactions. The symmetry operations for the symmetry-related molecules involved in the cyclic interactions are (1 − x, 2 − y, 1 − z) for O1A and O2A, (1 + x, y, z) for Cl3A and N1B, and (−1 + x, y, z) for Cl3B and N1A. Atom O2B connected to O1W is at (−x, −1 − y, 1 − z).
[Figure 7] Fig. 7. A stereoview of a triple layer of three interwoven nets of (II). For clarity, the view is tilted 30° away from the view in Fig. 5. The vertices connected by heavy lines correspond to the centres of the phenyl rings in Fig. 5; the lines join rings connected through intermolecular interactions. The dashed and dotted patterns correspond to moving the original pattern one unit-cell length in either directon along the b axis. The corresponding view for (III) would be virtually identical.
(I) 3,5-dichloro-4-cyanobenzoic acid top
Crystal data top
C8H3Cl2NO2Z = 4
Mr = 216.01F(000) = 432
Triclinic, P1Dx = 1.611 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.8859 (17) ÅCell parameters from 1911 reflections
b = 11.658 (4) Åθ = 2.6–25.1°
c = 15.891 (6) ŵ = 0.69 mm1
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
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3178 independent reflections
Radiation source: fine-focus sealed tube2660 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
ω scansθmax = 25.1°, θmin = 1.3°
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2003; Blessing, 1995)
h = 55
Tmin = 0.85, Tmax = 0.93k = 1313
11344 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-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 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C8H3Cl2NO2γ = 81.23 (1)°
Mr = 216.01V = 890.8 (6) Å3
Triclinic, P1Z = 4
a = 4.8859 (17) ÅMo Kα radiation
b = 11.658 (4) ŵ = 0.69 mm1
c = 15.891 (6) ÅT = 174 K
α = 88.39 (1)°0.25 × 0.20 × 0.10 mm
β = 84.79 (1)°
Data collection top
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 = 0.93Rint = 0.059
11344 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.15Δρmax = 0.46 e Å3
3178 reflectionsΔρmin = 0.34 e Å3
242 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl3A0.2281 (4)0.32026 (16)0.70770 (10)0.0509 (5)
Cl5A0.1965 (3)0.39102 (12)1.03210 (9)0.0313 (4)
O1A0.8788 (8)0.0554 (4)0.8999 (3)0.0340 (10)
H1A1.00940.01300.92170.051*0.71 (10)
O2A0.7062 (9)0.0799 (4)1.0352 (2)0.0323 (10)
H2A0.86780.04901.04430.049*0.29 (10)
N1A0.3472 (11)0.5046 (5)0.8221 (4)0.0451 (14)
C1A0.4634 (11)0.1847 (5)0.9264 (4)0.0260 (12)
C2A0.4493 (11)0.2062 (5)0.8411 (4)0.0280 (13)
H2A'0.58190.16480.80110.034*
C3A0.2389 (12)0.2890 (5)0.8144 (4)0.0327 (13)
C4A0.0391 (11)0.3477 (5)0.8726 (4)0.0268 (12)
C5A0.0536 (11)0.3228 (4)0.9586 (4)0.0236 (12)
C6A0.2679 (11)0.2427 (5)0.9867 (4)0.0242 (12)
H6A0.28140.22771.04540.029*
C7A0.6960 (11)0.1006 (4)0.9595 (4)0.0250 (13)
C8A0.1740 (12)0.4353 (5)0.8443 (4)0.0311 (13)
Cl3B0.9586 (4)0.19421 (17)0.20901 (10)0.0568 (6)
Cl5B1.1722 (3)0.11078 (12)0.53543 (9)0.0326 (4)
O1B0.1863 (8)0.4529 (4)0.3966 (2)0.0339 (10)
H1B0.03610.49000.41780.051*0.69 (9)
O2B0.2681 (8)0.4204 (3)0.5326 (2)0.0296 (10)
H2B0.20450.49070.54060.044*0.31 (9)
N1B1.4569 (12)0.0040 (5)0.3254 (4)0.0507 (15)
C1B0.5837 (11)0.3219 (5)0.4266 (4)0.0266 (13)
C2B0.6495 (12)0.3026 (5)0.3401 (4)0.0299 (13)
H2B'0.54090.34450.29950.036*
C3B0.8771 (12)0.2209 (5)0.3153 (4)0.0307 (13)
C4B1.0389 (11)0.1584 (5)0.3750 (4)0.0278 (13)
C5B0.9694 (12)0.1831 (5)0.4608 (4)0.0254 (12)
C6B0.7422 (11)0.2630 (5)0.4869 (4)0.0279 (13)
H6B0.69460.27760.54530.033*
C7B0.3315 (11)0.4048 (5)0.4571 (4)0.0254 (13)
C8B1.2695 (12)0.0721 (5)0.3481 (4)0.0354 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl3A0.0619 (11)0.0530 (11)0.0291 (9)0.0205 (9)0.0068 (7)0.0005 (7)
Cl5A0.0273 (8)0.0259 (9)0.0385 (9)0.0015 (6)0.0008 (6)0.0022 (6)
O1A0.028 (2)0.032 (2)0.040 (2)0.0045 (19)0.0071 (19)0.0030 (19)
O2A0.032 (2)0.029 (2)0.035 (2)0.0018 (19)0.0109 (18)0.0051 (18)
N1A0.039 (3)0.042 (3)0.050 (3)0.010 (3)0.006 (3)0.003 (3)
C1A0.028 (3)0.018 (3)0.033 (3)0.006 (2)0.005 (2)0.001 (2)
C2A0.029 (3)0.019 (3)0.035 (3)0.002 (2)0.006 (2)0.003 (2)
C3A0.039 (3)0.027 (3)0.032 (3)0.005 (3)0.003 (3)0.000 (3)
C4A0.024 (3)0.019 (3)0.037 (3)0.000 (2)0.006 (2)0.002 (2)
C5A0.021 (3)0.009 (3)0.039 (3)0.002 (2)0.001 (2)0.004 (2)
C6A0.027 (3)0.020 (3)0.028 (3)0.009 (2)0.006 (2)0.002 (2)
C7A0.022 (3)0.013 (3)0.040 (4)0.005 (2)0.006 (2)0.001 (2)
C8A0.033 (3)0.021 (3)0.038 (3)0.002 (3)0.003 (3)0.005 (3)
Cl3B0.0701 (13)0.0587 (13)0.0305 (10)0.0205 (10)0.0050 (8)0.0037 (8)
Cl5B0.0311 (8)0.0273 (9)0.0390 (9)0.0009 (7)0.0107 (6)0.0026 (6)
O1B0.030 (2)0.037 (2)0.030 (2)0.0113 (18)0.0039 (17)0.0014 (18)
O2B0.028 (2)0.026 (2)0.032 (2)0.0051 (18)0.0001 (17)0.0011 (17)
N1B0.051 (4)0.048 (4)0.046 (3)0.017 (3)0.002 (3)0.006 (3)
C1B0.020 (3)0.023 (3)0.036 (3)0.000 (2)0.005 (2)0.002 (2)
C2B0.030 (3)0.027 (3)0.031 (3)0.002 (2)0.006 (2)0.004 (2)
C3B0.031 (3)0.027 (3)0.031 (3)0.003 (2)0.001 (2)0.001 (2)
C4B0.024 (3)0.024 (3)0.035 (3)0.005 (2)0.002 (2)0.001 (2)
C5B0.025 (3)0.021 (3)0.030 (3)0.007 (2)0.004 (2)0.005 (2)
C6B0.028 (3)0.024 (3)0.030 (3)0.000 (2)0.001 (2)0.005 (2)
C7B0.025 (3)0.021 (3)0.030 (3)0.003 (2)0.002 (2)0.004 (2)
C8B0.029 (3)0.032 (3)0.042 (4)0.005 (3)0.000 (3)0.002 (3)
Geometric parameters (Å, º) top
Cl3A—C3A1.728 (6)Cl3B—C3B1.725 (6)
Cl5A—C5A1.728 (5)Cl5B—C5B1.733 (6)
O1A—C7A1.305 (7)O1B—C7B1.309 (7)
O1A—H1A0.8400O1B—H1B0.8400
O2A—C7A1.225 (7)O2B—C7B1.223 (7)
O2A—H2A0.8400O2B—H2B0.8400
N1A—C8A1.150 (7)N1B—C8B1.154 (8)
C1A—C2A1.378 (8)C1B—C6B1.388 (8)
C1A—C6A1.400 (8)C1B—C2B1.399 (8)
C1A—C7A1.506 (8)C1B—C7B1.497 (7)
C2A—C3A1.386 (8)C2B—C3B1.385 (8)
C2A—H2A'0.9500C2B—H2B'0.9500
C3A—C4A1.395 (8)C3B—C4B1.406 (8)
C4A—C5A1.395 (8)C4B—C5B1.403 (8)
C4A—C8A1.436 (8)C4B—C8B1.434 (8)
C5A—C6A1.389 (7)C5B—C6B1.376 (8)
C6A—H6A0.9500C6B—H6B0.9500
C7A—O1A—H1A109.5C7B—O1B—H1B109.5
C7A—O2A—H2A109.5C7B—O2B—H2B109.5
C2A—C1A—C6A121.8 (5)C6B—C1B—C2B121.8 (5)
C2A—C1A—C7A121.5 (5)C6B—C1B—C7B117.7 (5)
C6A—C1A—C7A116.7 (5)C2B—C1B—C7B120.5 (5)
C1A—C2A—C3A119.0 (5)C3B—C2B—C1B118.3 (5)
C1A—C2A—H2A'120.5C3B—C2B—H2B'120.8
C3A—C2A—H2A'120.5C1B—C2B—H2B'120.8
C2A—C3A—C4A120.8 (5)C2B—C3B—C4B121.2 (5)
C2A—C3A—Cl3A119.2 (5)C2B—C3B—Cl3B119.0 (5)
C4A—C3A—Cl3A120.0 (4)C4B—C3B—Cl3B119.7 (4)
C3A—C4A—C5A119.2 (5)C5B—C4B—C3B118.4 (5)
C3A—C4A—C8A120.3 (5)C5B—C4B—C8B121.2 (5)
C5A—C4A—C8A120.5 (5)C3B—C4B—C8B120.4 (5)
C6A—C5A—C4A120.8 (5)C6B—C5B—C4B121.3 (5)
C6A—C5A—Cl5A118.8 (4)C6B—C5B—Cl5B119.4 (4)
C4A—C5A—Cl5A120.3 (4)C4B—C5B—Cl5B119.3 (4)
C5A—C6A—C1A118.3 (5)C5B—C6B—C1B119.0 (5)
C5A—C6A—H6A120.8C5B—C6B—H6B120.5
C1A—C6A—H6A120.8C1B—C6B—H6B120.5
O2A—C7A—O1A125.3 (5)O2B—C7B—O1B124.8 (5)
O2A—C7A—C1A121.6 (5)O2B—C7B—C1B121.2 (5)
O1A—C7A—C1A113.2 (5)O1B—C7B—C1B114.0 (5)
N1A—C8A—C4A179.2 (7)N1B—C8B—C4B178.8 (8)
C6A—C1A—C2A—C3A1.2 (8)C6B—C1B—C2B—C3B1.1 (9)
C7A—C1A—C2A—C3A176.6 (5)C7B—C1B—C2B—C3B176.8 (5)
C1A—C2A—C3A—C4A1.8 (9)C1B—C2B—C3B—C4B0.0 (9)
C1A—C2A—C3A—Cl3A177.5 (4)C1B—C2B—C3B—Cl3B179.0 (4)
C2A—C3A—C4A—C5A0.3 (9)C2B—C3B—C4B—C5B1.8 (9)
Cl3A—C3A—C4A—C5A178.9 (4)Cl3B—C3B—C4B—C5B179.2 (4)
C2A—C3A—C4A—C8A178.5 (6)C2B—C3B—C4B—C8B178.4 (6)
Cl3A—C3A—C4A—C8A0.7 (8)Cl3B—C3B—C4B—C8B0.6 (8)
C3A—C4A—C5A—C6A1.7 (8)C3B—C4B—C5B—C6B2.6 (8)
C8A—C4A—C5A—C6A176.5 (5)C8B—C4B—C5B—C6B177.6 (6)
C3A—C4A—C5A—Cl5A178.1 (4)C3B—C4B—C5B—Cl5B177.9 (4)
C8A—C4A—C5A—Cl5A3.7 (8)C8B—C4B—C5B—Cl5B1.8 (8)
C4A—C5A—C6A—C1A2.2 (8)C4B—C5B—C6B—C1B1.6 (8)
Cl5A—C5A—C6A—C1A177.6 (4)Cl5B—C5B—C6B—C1B178.9 (4)
C2A—C1A—C6A—C5A0.7 (8)C2B—C1B—C6B—C5B0.3 (8)
C7A—C1A—C6A—C5A178.7 (5)C7B—C1B—C6B—C5B177.6 (5)
C2A—C1A—C7A—O2A178.7 (5)C6B—C1B—C7B—O2B0.3 (8)
C6A—C1A—C7A—O2A3.3 (8)C2B—C1B—C7B—O2B178.3 (6)
C2A—C1A—C7A—O1A1.9 (7)C6B—C1B—C7B—O1B177.1 (5)
C6A—C1A—C7A—O1A176.0 (5)C2B—C1B—C7B—O1B0.9 (8)
(II) 3,5-dichloro-4-cyano-benzoic acid top
Crystal data top
C8H3Cl2NO2F(000) = 432
Mr = 216.01Dx = 1.720 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3170 reflections
a = 7.3429 (18) Åθ = 2.7–27.5°
b = 10.378 (3) ŵ = 0.74 mm1
c = 11.826 (3) ÅT = 174 K
β = 112.22 (1)°Plate, colourless
V = 834.3 (4) Å30.50 × 0.50 × 0.05 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1915 independent reflections
Radiation source: fine-focus sealed tube1754 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 27.6°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
h = 99
Tmin = 0.70, Tmax = 0.96k = 1313
9369 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-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 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C8H3Cl2NO2V = 834.3 (4) Å3
Mr = 216.01Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3429 (18) ŵ = 0.74 mm1
b = 10.378 (3) ÅT = 174 K
c = 11.826 (3) Å0.50 × 0.50 × 0.05 mm
β = 112.22 (1)°
Data collection top
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 = 0.96Rint = 0.030
9369 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.075H-atom parameters constrained
S = 1.05Δρmax = 0.30 e Å3
1915 reflectionsΔρmin = 0.30 e Å3
119 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.31648 (17)0.69293 (11)0.44975 (11)0.0218 (2)
C20.27108 (17)0.63436 (12)0.33691 (11)0.0231 (2)
H220.27760.68180.26980.028*
C30.21615 (17)0.50585 (12)0.32326 (11)0.0224 (2)
C40.20786 (16)0.43559 (11)0.42170 (11)0.0222 (3)
C50.25307 (17)0.49691 (11)0.53426 (11)0.0220 (2)
C60.30724 (17)0.62510 (12)0.54902 (11)0.0227 (2)
H60.33770.66640.62570.027*
C70.38701 (17)0.82972 (12)0.46921 (11)0.0241 (2)
C80.15813 (19)0.30118 (13)0.40912 (12)0.0278 (3)
N10.1238 (2)0.19362 (12)0.40143 (13)0.0430 (3)
O10.41088 (16)0.88360 (9)0.37833 (9)0.0350 (2)
H10.46300.95630.39950.042*0.67 (3)
O20.42118 (15)0.88103 (9)0.56960 (9)0.0335 (2)
H20.46460.95590.56930.040*0.33 (3)
Cl30.16398 (5)0.42967 (3)0.18567 (3)0.03295 (12)
Cl50.24506 (5)0.40927 (3)0.65576 (3)0.02927 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0208 (5)0.0172 (5)0.0264 (6)0.0008 (4)0.0077 (4)0.0008 (4)
C20.0240 (6)0.0201 (6)0.0255 (6)0.0013 (4)0.0097 (5)0.0024 (4)
C30.0224 (5)0.0200 (6)0.0246 (6)0.0017 (4)0.0085 (4)0.0025 (4)
C40.0198 (5)0.0173 (5)0.0285 (6)0.0017 (4)0.0081 (5)0.0012 (4)
C50.0200 (5)0.0210 (5)0.0244 (6)0.0021 (4)0.0078 (4)0.0046 (4)
C60.0222 (5)0.0211 (6)0.0237 (6)0.0004 (4)0.0073 (4)0.0010 (5)
C70.0246 (6)0.0194 (6)0.0266 (6)0.0001 (4)0.0078 (5)0.0004 (5)
C80.0279 (6)0.0233 (6)0.0299 (6)0.0012 (5)0.0084 (5)0.0007 (5)
N10.0520 (8)0.0241 (6)0.0468 (8)0.0076 (5)0.0117 (6)0.0008 (5)
O10.0513 (6)0.0220 (5)0.0330 (5)0.0095 (4)0.0175 (5)0.0004 (4)
O20.0459 (6)0.0223 (5)0.0316 (5)0.0074 (4)0.0139 (4)0.0054 (4)
Cl30.0479 (2)0.02443 (18)0.02905 (19)0.00132 (13)0.01745 (15)0.00642 (11)
Cl50.03435 (19)0.02669 (18)0.02689 (18)0.00203 (11)0.01171 (14)0.00652 (11)
Geometric parameters (Å, º) top
C1—C21.3875 (17)C5—C61.3806 (17)
C1—C61.3923 (17)C5—Cl51.7201 (12)
C1—C71.4987 (17)C6—H60.9500
C2—C31.3850 (17)C7—O21.2372 (16)
C2—H220.9500C7—O11.2810 (16)
C3—C41.3945 (17)C8—N11.1404 (19)
C3—Cl31.7170 (13)O1—H10.8400
C4—C51.3975 (17)O2—H20.8400
C4—C81.4353 (18)
C2—C1—C6121.26 (11)C6—C5—C4120.83 (11)
C2—C1—C7120.40 (11)C6—C5—Cl5120.21 (9)
C6—C1—C7118.27 (11)C4—C5—Cl5118.95 (9)
C3—C2—C1119.17 (11)C5—C6—C1118.96 (11)
C3—C2—H22120.4C5—C6—H6120.5
C1—C2—H22120.4C1—C6—H6120.5
C2—C3—C4120.60 (11)O2—C7—O1125.08 (12)
C2—C3—Cl3120.31 (9)O2—C7—C1119.20 (11)
C4—C3—Cl3119.07 (10)O1—C7—C1115.70 (11)
C3—C4—C5119.17 (11)N1—C8—C4178.08 (15)
C3—C4—C8120.75 (11)C7—O1—H1109.5
C5—C4—C8120.06 (11)C7—O2—H2109.5
C6—C1—C2—C30.19 (18)C3—C4—C5—Cl5179.33 (9)
C7—C1—C2—C3176.64 (10)C8—C4—C5—Cl50.77 (16)
C1—C2—C3—C40.49 (18)C4—C5—C6—C10.06 (17)
C1—C2—C3—Cl3178.65 (9)Cl5—C5—C6—C1178.65 (9)
C2—C3—C4—C50.89 (17)C2—C1—C6—C50.46 (17)
Cl3—C3—C4—C5179.07 (9)C7—C1—C6—C5176.44 (10)
C2—C3—C4—C8177.66 (11)C2—C1—C7—O2177.94 (11)
Cl3—C3—C4—C80.52 (16)C6—C1—C7—O25.13 (17)
C3—C4—C5—C60.61 (17)C2—C1—C7—O13.44 (16)
C8—C4—C5—C6177.94 (11)C6—C1—C7—O1173.49 (11)
(III) 3,5-dichloro-4-cyanobenzoicacid 0.25-hydrate top
Crystal data top
C8H3Cl2NO2·0.25H2OF(000) = 884
Mr = 220.52Dx = 1.698 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2775 reflections
a = 11.237 (3) Åθ = 2.2–27.5°
b = 11.410 (3) ŵ = 0.72 mm1
c = 14.566 (4) ÅT = 174 K
β = 112.50 (1)°Prism, colourless
V = 1725.4 (8) Å30.35 × 0.25 × 0.25 mm
Z = 8
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3893 independent reflections
Radiation source: fine-focus sealed tube3265 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
h = 1414
Tmin = 0.76, Tmax = 0.84k = 1414
19254 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-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 parametersΔρmax = 0.41 e Å3
3 restraintsΔρmin = 0.46 e Å3
Crystal data top
C8H3Cl2NO2·0.25H2OV = 1725.4 (8) Å3
Mr = 220.52Z = 8
Monoclinic, P21/nMo Kα radiation
a = 11.237 (3) ŵ = 0.72 mm1
b = 11.410 (3) ÅT = 174 K
c = 14.566 (4) Å0.35 × 0.25 × 0.25 mm
β = 112.50 (1)°
Data collection top
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 = 0.84Rint = 0.024
19254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0273 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.04Δρmax = 0.41 e Å3
3893 reflectionsΔρmin = 0.46 e Å3
251 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.54957 (14)0.71878 (12)0.58559 (11)0.0197 (3)
C2A0.66894 (14)0.66522 (13)0.60880 (11)0.0214 (3)
H22A0.73990.70810.60600.026*
C3A0.68210 (14)0.54794 (13)0.63604 (11)0.0215 (3)
C4A0.57732 (14)0.48353 (13)0.63842 (10)0.0199 (3)
C5A0.45824 (14)0.53993 (13)0.61441 (11)0.0197 (3)
C6A0.44383 (14)0.65740 (13)0.58859 (11)0.0204 (3)
H6A0.36330.69550.57320.024*
C7A0.53193 (14)0.84520 (13)0.55480 (11)0.0211 (3)
C8A0.59125 (14)0.36091 (14)0.66526 (11)0.0236 (3)
N1A0.60130 (14)0.26377 (13)0.68548 (12)0.0344 (3)
O1A0.62902 (11)0.89574 (10)0.54596 (10)0.0330 (3)
H1A0.60740.96280.52140.050*0.68 (3)
O2A0.42704 (11)0.89358 (10)0.53945 (10)0.0312 (3)
H2A0.42930.96290.52080.047*0.32 (3)
Cl3A0.82934 (4)0.47983 (4)0.66758 (3)0.03258 (11)
Cl5A0.32945 (3)0.46085 (3)0.61848 (3)0.02533 (10)
C1B0.06234 (14)0.10519 (13)0.60934 (11)0.0211 (3)
C2B0.04191 (14)0.04466 (13)0.61537 (11)0.0213 (3)
H22B0.12080.08400.60400.026*
C3B0.02904 (14)0.07377 (13)0.63820 (10)0.0202 (3)
C4B0.08763 (14)0.13191 (13)0.65608 (10)0.0205 (3)
C5B0.19199 (14)0.06850 (13)0.65129 (11)0.0219 (3)
C6B0.17925 (15)0.04944 (13)0.62687 (11)0.0223 (3)
H6B0.24950.09180.62210.027*
C7B0.04671 (19)0.23218 (14)0.58112 (12)0.0333 (4)
C8B0.09636 (15)0.25641 (14)0.67463 (11)0.0247 (3)
N1B0.09872 (14)0.35550 (12)0.68511 (12)0.0339 (3)
O1B0.06216 (12)0.27837 (10)0.56165 (10)0.0359 (3)
H1B0.05930.34940.54750.054*0.50
O2B0.14256 (13)0.28594 (11)0.57635 (11)0.0396 (3)
H2B0.12060.35430.55520.059*0.50
Cl3B0.15812 (4)0.15081 (3)0.64354 (3)0.02737 (10)
Cl5B0.33611 (4)0.13857 (4)0.67439 (3)0.03325 (11)
O1W0.0197 (2)0.4994 (3)0.5060 (2)0.0302 (6)*0.50
H1W0.004 (4)0.490 (2)0.4546 (15)0.045*0.50
H2W0.0489 (19)0.515 (4)0.5543 (17)0.045*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0211 (7)0.0161 (7)0.0214 (7)0.0013 (5)0.0076 (6)0.0008 (5)
C2A0.0196 (7)0.0194 (7)0.0261 (7)0.0006 (6)0.0098 (6)0.0007 (6)
C3A0.0188 (7)0.0213 (7)0.0251 (7)0.0043 (6)0.0091 (6)0.0011 (6)
C4A0.0228 (7)0.0166 (7)0.0200 (7)0.0011 (5)0.0078 (6)0.0002 (5)
C5A0.0183 (7)0.0197 (7)0.0212 (7)0.0028 (5)0.0077 (6)0.0006 (5)
C6A0.0181 (7)0.0196 (7)0.0231 (7)0.0020 (6)0.0075 (6)0.0004 (5)
C7A0.0207 (7)0.0180 (7)0.0241 (7)0.0007 (6)0.0080 (6)0.0014 (6)
C8A0.0215 (7)0.0220 (8)0.0275 (8)0.0009 (6)0.0096 (6)0.0018 (6)
N1A0.0314 (8)0.0236 (7)0.0478 (9)0.0029 (6)0.0147 (7)0.0077 (6)
O1A0.0278 (6)0.0205 (6)0.0551 (8)0.0012 (5)0.0208 (6)0.0104 (5)
O2A0.0236 (6)0.0198 (6)0.0497 (7)0.0042 (5)0.0135 (5)0.0069 (5)
Cl3A0.02181 (19)0.0250 (2)0.0535 (3)0.00805 (15)0.01726 (18)0.00917 (17)
Cl5A0.02018 (18)0.02221 (18)0.0340 (2)0.00373 (13)0.01081 (15)0.00271 (14)
C1B0.0263 (7)0.0172 (7)0.0189 (7)0.0009 (6)0.0074 (6)0.0012 (5)
C2B0.0214 (7)0.0198 (7)0.0216 (7)0.0018 (6)0.0069 (6)0.0005 (5)
C3B0.0199 (7)0.0202 (7)0.0196 (7)0.0038 (6)0.0066 (6)0.0012 (5)
C4B0.0249 (7)0.0168 (7)0.0179 (7)0.0013 (6)0.0060 (6)0.0004 (5)
C5B0.0203 (7)0.0237 (7)0.0210 (7)0.0028 (6)0.0069 (6)0.0012 (6)
C6B0.0229 (7)0.0225 (7)0.0217 (7)0.0046 (6)0.0087 (6)0.0016 (6)
C7B0.0572 (12)0.0179 (8)0.0247 (8)0.0022 (8)0.0157 (8)0.0013 (6)
C8B0.0244 (8)0.0234 (8)0.0227 (7)0.0011 (6)0.0050 (6)0.0010 (6)
N1B0.0335 (8)0.0222 (7)0.0391 (8)0.0016 (6)0.0062 (6)0.0027 (6)
O1B0.0394 (7)0.0191 (6)0.0513 (8)0.0066 (5)0.0195 (6)0.0071 (5)
O2B0.0424 (7)0.0216 (6)0.0602 (9)0.0028 (5)0.0256 (7)0.0087 (6)
Cl3B0.02284 (19)0.0254 (2)0.0332 (2)0.00641 (14)0.00988 (15)0.00020 (15)
Cl5B0.0245 (2)0.0335 (2)0.0433 (2)0.00822 (16)0.01460 (17)0.00342 (17)
Geometric parameters (Å, º) top
C1A—C2A1.393 (2)C1B—C6B1.392 (2)
C1A—C6A1.394 (2)C1B—C7B1.498 (2)
C1A—C7A1.501 (2)C2B—C3B1.386 (2)
C2A—C3A1.388 (2)C2B—H22B0.9500
C2A—H22A0.9500C3B—C4B1.402 (2)
C3A—C4A1.400 (2)C3B—Cl3B1.7231 (15)
C3A—Cl3A1.7236 (15)C4B—C5B1.402 (2)
C4A—C5A1.403 (2)C4B—C8B1.442 (2)
C4A—C8A1.445 (2)C5B—C6B1.385 (2)
C5A—C6A1.385 (2)C5B—Cl5B1.7200 (15)
C5A—Cl5A1.7256 (15)C6B—H6B0.9500
C6A—H6A0.9500C7B—O1B1.261 (2)
C7A—O2A1.2419 (18)C7B—O2B1.264 (2)
C7A—O1A1.2833 (18)C8B—N1B1.140 (2)
C8A—N1A1.141 (2)O1B—H1B0.8400
O1A—H1A0.8400O2B—H2B0.8400
O2A—H2A0.8400O1W—H1W0.8400 (2)
C1B—C2B1.391 (2)O1W—H2W0.8400 (2)
C2A—C1A—C6A121.68 (13)C2B—C1B—C7B118.97 (14)
C2A—C1A—C7A119.93 (13)C6B—C1B—C7B119.70 (14)
C6A—C1A—C7A118.38 (13)C3B—C2B—C1B119.08 (14)
C3A—C2A—C1A118.68 (14)C3B—C2B—H22B120.5
C3A—C2A—H22A120.7C1B—C2B—H22B120.5
C1A—C2A—H22A120.7C2B—C3B—C4B120.68 (13)
C2A—C3A—C4A120.99 (14)C2B—C3B—Cl3B119.73 (11)
C2A—C3A—Cl3A119.83 (12)C4B—C3B—Cl3B119.59 (11)
C4A—C3A—Cl3A119.18 (11)C3B—C4B—C5B119.14 (14)
C3A—C4A—C5A118.95 (13)C3B—C4B—C8B119.51 (13)
C3A—C4A—C8A120.67 (13)C5B—C4B—C8B121.29 (14)
C5A—C4A—C8A120.38 (13)C6B—C5B—C4B120.52 (14)
C6A—C5A—C4A120.85 (13)C6B—C5B—Cl5B119.92 (12)
C6A—C5A—Cl5A120.20 (11)C4B—C5B—Cl5B119.55 (12)
C4A—C5A—Cl5A118.95 (11)C5B—C6B—C1B119.23 (14)
C5A—C6A—C1A118.83 (13)C5B—C6B—H6B120.4
C5A—C6A—H6A120.6C1B—C6B—H6B120.4
C1A—C6A—H6A120.6O1B—C7B—O2B123.96 (15)
O2A—C7A—O1A124.53 (14)O1B—C7B—C1B117.90 (16)
O2A—C7A—C1A119.26 (13)O2B—C7B—C1B118.13 (16)
O1A—C7A—C1A116.21 (13)N1B—C8B—C4B176.82 (17)
N1A—C8A—C4A179.3 (2)C7B—O1B—H1B109.5
C7A—O1A—H1A109.5C7B—O2B—H2B109.5
C7A—O2A—H2A109.5H1W—O1W—H2W109.47 (3)
C2B—C1B—C6B121.32 (14)
C6A—C1A—C2A—C3A0.4 (2)C6B—C1B—C2B—C3B0.7 (2)
C7A—C1A—C2A—C3A179.35 (14)C7B—C1B—C2B—C3B177.86 (14)
C1A—C2A—C3A—C4A1.3 (2)C1B—C2B—C3B—C4B0.7 (2)
C1A—C2A—C3A—Cl3A178.73 (11)C1B—C2B—C3B—Cl3B178.71 (11)
C2A—C3A—C4A—C5A1.1 (2)C2B—C3B—C4B—C5B0.5 (2)
Cl3A—C3A—C4A—C5A178.87 (11)Cl3B—C3B—C4B—C5B179.83 (11)
C2A—C3A—C4A—C8A178.95 (14)C2B—C3B—C4B—C8B176.82 (14)
Cl3A—C3A—C4A—C8A1.1 (2)Cl3B—C3B—C4B—C8B2.56 (19)
C3A—C4A—C5A—C6A0.1 (2)C3B—C4B—C5B—C6B1.6 (2)
C8A—C4A—C5A—C6A180.00 (14)C8B—C4B—C5B—C6B175.67 (14)
C3A—C4A—C5A—Cl5A179.40 (11)C3B—C4B—C5B—Cl5B179.31 (11)
C8A—C4A—C5A—Cl5A0.54 (19)C8B—C4B—C5B—Cl5B3.5 (2)
C4A—C5A—C6A—C1A0.8 (2)C4B—C5B—C6B—C1B1.5 (2)
Cl5A—C5A—C6A—C1A179.74 (11)Cl5B—C5B—C6B—C1B179.37 (11)
C2A—C1A—C6A—C5A0.7 (2)C2B—C1B—C6B—C5B0.3 (2)
C7A—C1A—C6A—C5A178.35 (13)C7B—C1B—C6B—C5B178.92 (14)
C2A—C1A—C7A—O2A176.18 (14)C2B—C1B—C7B—O1B1.6 (2)
C6A—C1A—C7A—O2A4.8 (2)C6B—C1B—C7B—O1B177.00 (14)
C2A—C1A—C7A—O1A4.0 (2)C2B—C1B—C7B—O2B179.75 (15)
C6A—C1A—C7A—O1A175.00 (14)C6B—C1B—C7B—O2B1.6 (2)

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC8H3Cl2NO2C8H3Cl2NO2C8H3Cl2NO2·0.25H2O
Mr216.01216.01220.52
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/n
Temperature (K)174174174
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), 9090, 112.50 (1), 90
V3)890.8 (6)834.3 (4)1725.4 (8)
Z448
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.690.740.72
Crystal size (mm)0.25 × 0.20 × 0.100.50 × 0.50 × 0.050.35 × 0.25 × 0.25
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(TWINABS; Sheldrick, 2003; Blessing, 1995)
Multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Tmin, Tmax0.85, 0.930.70, 0.960.76, 0.84
No. of measured, independent and
observed [I > 2σ(I)] reflections
11344, 3178, 2660 9369, 1915, 1754 19254, 3893, 3265
Rint0.0590.0300.024
(sin θ/λ)max1)0.5970.6510.649
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 reflections317819153893
No. of parameters242119251
No. of restraints003
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.340.30, 0.300.41, 0.46

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.

Distancesa and angles (Å, °) in the hydrogen bonds top
CompoundO—H···X—YO—H···XH···XH···X—YO···X
(I)O1A—H1A···O2Ai-C7Ai1781.801232.641 (7)
(I)O2A—H2A···O1Ai-C7Ai1531.871052.641 (7)
(I)O1B—H1B···O2Bii-C7Bii1751.811282.648 (7)
(I)O2B—H2B···O2Aii-C7Bii1232.091032.648 (7)
(II)O1—H1···O2iii-C7iii1741.861192.700 (2)
(II)O2—H2···O1iii-C7iii1621.891082.700 (2)
(III)O1A—H1A···O2Aiii-C7Aiii1731.831202.669 (2)
(III)O2A—H2A···O1Aiii-C7Aiii1591.871072.669 (2)
(III)O1B—H1B···O1W···O2Biv1661.921362.746 (4)
(III)O2B—H2B···O1Wiv···O1Biv1652.021362.843 (4)
(III)bO1W—H1W···N1Bv-C8Bv1302.451223.056 (4)
(III)bO1W—H2W···N1Bvi-C8Bv1332.301232.943 (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.
Distances and angles (Å, °) in the Cl···X contactsa top
CompoundCl···XC—Cl···XCl···XCl···X—C
(I)Cl5A···N1Ai174.7 (6)3.195 (6)115.0 (4)
(I)Cl5B···N1Bii176.2 (6)3.128 (6)116.4 (4)
(I)Cl3A···O2B167.1 (3)2.989 (6)148.3 (4)
(II)Cl3···N1iii170.1 (2)3.503 (2)110.2 (1)
(II)Cl5···N1iv162.0 (2)3.512 (2)104.2 (1)
(II)bCl3···N1v78.8 (1)3.374 (2)155.9 (1)
(II)bCl5···O1vi101.9 (1)3.257 (2)147.0 (2)
(II)bCl5···O2vii129.0 (1)3.259 (2)143.0 (2)
(III)Cl3A···N1Bviii169.7 (2)3.263 (2)116.6 (1)
(III)Cl5A···N1B163.3 (2)3.322 (2)107.5 (1)
(III)Cl3B···N1Aix169.7 (2)3.257 (2)110.1 (1)
(III)Cl5B···N1A171.9 (2)3.252 (2)114.5 (1)
(III)bCl3A···O1Wx117.8 (1)3.396 (3)
(III)bCl3A···O1Bx89.3 (1)3.594 (2)133.1 (1)
(III)bCl5A···O1Wxi129.6 (1)3.282 (3)
(III)bCl5A···O2Bxii91.0 (1)3.485 (2)149.4 (2)
(III)bCl3B···O2Axiii115.0 (1)3.214 (2)127.3 (1)
(III)bCl5B···O1Axiv101.6 (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.
 

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