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The title compound, C8H3Cl3N2O2, forms crystals in which hydrogen-bonding and Cl...N inter­actions appear to be equally important to the structure. The mol­ecules form ribbons held together alternately by cyclic (CONH)2 and cyclic (ClCCC[triple bond]N)2 inter­actions. The ribbons assemble into layers through Cl...Cl inter­actions. The layers are held together by NH...N[triple bond]C hydrogen bonds, as well as by π–π inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108001017/ln3085sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108001017/ln3085Isup2.hkl
Contains datablock I

CCDC reference: 682806

Comment top

In 3,5-dichloro-4-cyanobenzoic acid (Britton, 2006), the molecules are involved in cyclic (COOH)2 interactions, graph set R22(8) (Etter, 1990), as well as in cyclic (ClCCCN)2 interactions. Bernstein et al. (1995) have suggested that graph-set analysis might be extended to other systems than hydrogen bonding. In this spirit, cyclic Cl···N interactions can be described by the graph set R22(10), with the electron acceptor Cl replacing H. The title compound, (I), was studied in search of another example of the same phenomenon.

Fig. 1 shows the atom labelling and the anisotropic displacement ellipsoids of (I). The bond lengths and angles are normal. The plane of the benzamide group, excluding the H atoms, is rotated 31.2 (10)° out of the plane of the C6 ring, while the plane of the NH2 group is rotated another 10 (2)° out of the plane of the benzamide group. The hydroxy group is intramolecularly hydrogen bonded to atom O1, graph set S(6); geometric details are given in Table 1.

One layer of the packing in (I) is shown in Fig. 2. The molecules form ribbons along the [211] direction, held together by the anticipated (CONH)2 cyclic hydrogen bonds and Cl···N interactions. Geometric data for the hydrogen bond are given in Table 1. Data for the Cl···N interaction are: C4—Cl4···N2i 171.66 (5)°, Cl4···N2i 3.0809 (13) Å and Cl4···N2iC8i 129.09 (11)° [symmetry code: (i) 2 - x, 2 - y, 1 - z]. The ribbons assemble into layers parallel to the (102) plane, held together by Cl···Cl interactions: C3—Cl3···Cl6ii 138.11 (5)°, Cl3···Cl6ii 3.3900 (5) Å and Cl3···Cl6ii—C6ii 136.03 (4)° [symmetry code: (ii) x, 1 + y, z].

The layers are held together by N—H···NC hydrogen bonds. Fig. 3 shows the hydrogen bonds between two molecules in adjacent layers; geometric details are given in Table 1. Pairs of molecules form cyclic dimers, graph set R22(16). In a single layer, alternate molecules form such dimers with adjacent layers on opposite sides of the original sheet.

It would be of interest to determine the structure of the corresponding carboxylic acid. It seems reasonable to suppose that similar layers of molecules might form, but that the stacking of the layers would be different in the absence of interlayer hydrogen bonds.

Related literature top

For related literature, see: Bernstein et al. (1995); Britton (2006); Etter (1990).

Experimental top

The compound was obtained from the Diamond Shamrock Corporation. The crystal used was from the original sample.

Refinement top

The solution and refinement were straightforward. The H-atom positions and isotropic displacement parameters were refined.

Structure description top

In 3,5-dichloro-4-cyanobenzoic acid (Britton, 2006), the molecules are involved in cyclic (COOH)2 interactions, graph set R22(8) (Etter, 1990), as well as in cyclic (ClCCCN)2 interactions. Bernstein et al. (1995) have suggested that graph-set analysis might be extended to other systems than hydrogen bonding. In this spirit, cyclic Cl···N interactions can be described by the graph set R22(10), with the electron acceptor Cl replacing H. The title compound, (I), was studied in search of another example of the same phenomenon.

Fig. 1 shows the atom labelling and the anisotropic displacement ellipsoids of (I). The bond lengths and angles are normal. The plane of the benzamide group, excluding the H atoms, is rotated 31.2 (10)° out of the plane of the C6 ring, while the plane of the NH2 group is rotated another 10 (2)° out of the plane of the benzamide group. The hydroxy group is intramolecularly hydrogen bonded to atom O1, graph set S(6); geometric details are given in Table 1.

One layer of the packing in (I) is shown in Fig. 2. The molecules form ribbons along the [211] direction, held together by the anticipated (CONH)2 cyclic hydrogen bonds and Cl···N interactions. Geometric data for the hydrogen bond are given in Table 1. Data for the Cl···N interaction are: C4—Cl4···N2i 171.66 (5)°, Cl4···N2i 3.0809 (13) Å and Cl4···N2iC8i 129.09 (11)° [symmetry code: (i) 2 - x, 2 - y, 1 - z]. The ribbons assemble into layers parallel to the (102) plane, held together by Cl···Cl interactions: C3—Cl3···Cl6ii 138.11 (5)°, Cl3···Cl6ii 3.3900 (5) Å and Cl3···Cl6ii—C6ii 136.03 (4)° [symmetry code: (ii) x, 1 + y, z].

The layers are held together by N—H···NC hydrogen bonds. Fig. 3 shows the hydrogen bonds between two molecules in adjacent layers; geometric details are given in Table 1. Pairs of molecules form cyclic dimers, graph set R22(16). In a single layer, alternate molecules form such dimers with adjacent layers on opposite sides of the original sheet.

It would be of interest to determine the structure of the corresponding carboxylic acid. It seems reasonable to suppose that similar layers of molecules might form, but that the stacking of the layers would be different in the absence of interlayer hydrogen bonds.

For related literature, see: Bernstein et al. (1995); Britton (2006); Etter (1990).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. One layer of the crystal packing of (I). Hydrogen bonds and Cl···N C interactions are shown as dashed lines. The Cl···Cl interactions are shown as dotted lines.
[Figure 3] Fig. 3. Adjacent molecules of (I) from two different layers. Hydrogen bonds are shown as dashed lines.
3,4,6-Trichloro-5-cyano-2-hydroxybenzamide top
Crystal data top
C8H3Cl3N2O2Z = 2
Mr = 265.47F(000) = 264
Triclinic, P1Dx = 1.830 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.3020 (6) ÅCell parameters from 2326 reflections
b = 9.0437 (8) Åθ = 2.3–27.4°
c = 9.3822 (9) ŵ = 0.93 mm1
α = 109.196 (1)°T = 174 K
β = 94.937 (1)°Prism, colourless
γ = 104.076 (1)°0.45 × 0.30 × 0.25 mm
V = 481.72 (8) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2164 independent reflections
Radiation source: fine-focus sealed tube2036 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
[SADABS (Sheldrick, 2003; Blessing, 1995)]
h = 88
Tmin = 0.74, Tmax = 0.79k = 1111
5659 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022All H-atom parameters refined
wR(F2) = 0.063 w = 1/[σ2(Fo2) + (0.031P)2 + 0.208P],
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2164 reflectionsΔρmax = 0.43 e Å3
149 parametersΔρmin = 0.22 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.023 (2)
Crystal data top
C8H3Cl3N2O2γ = 104.076 (1)°
Mr = 265.47V = 481.72 (8) Å3
Triclinic, P1Z = 2
a = 6.3020 (6) ÅMo Kα radiation
b = 9.0437 (8) ŵ = 0.93 mm1
c = 9.3822 (9) ÅT = 174 K
α = 109.196 (1)°0.45 × 0.30 × 0.25 mm
β = 94.937 (1)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
2164 independent reflections
Absorption correction: multi-scan
[SADABS (Sheldrick, 2003; Blessing, 1995)]
2036 reflections with I > 2σ(I)
Tmin = 0.74, Tmax = 0.79Rint = 0.017
5659 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.063All H-atom parameters refined
S = 1.07Δρmax = 0.43 e Å3
2164 reflectionsΔρmin = 0.22 e Å3
149 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl30.37098 (6)1.18489 (4)0.80299 (4)0.02742 (11)
Cl40.75184 (5)1.08721 (4)0.62495 (4)0.02395 (10)
Cl60.58111 (6)0.52885 (4)0.72883 (4)0.02654 (11)
O10.10836 (16)0.70392 (12)1.00184 (11)0.0247 (2)
O20.15037 (17)0.94932 (12)0.91936 (11)0.0235 (2)
H20.109 (3)0.883 (2)0.962 (2)0.040 (5)*
N10.1264 (2)0.47587 (14)0.81978 (14)0.0248 (3)
H110.037 (3)0.416 (2)0.861 (2)0.032 (4)*
H120.156 (3)0.432 (2)0.735 (2)0.033 (5)*
N20.9345 (2)0.72514 (16)0.53256 (14)0.0294 (3)
C10.3346 (2)0.74280 (15)0.82112 (13)0.0166 (2)
C20.3022 (2)0.89712 (15)0.84156 (14)0.0176 (2)
C30.4274 (2)1.00282 (15)0.77880 (14)0.0186 (2)
C40.5929 (2)0.95968 (15)0.70084 (14)0.0182 (2)
C50.6338 (2)0.80989 (15)0.68383 (14)0.0182 (3)
C60.5062 (2)0.70427 (15)0.74507 (14)0.0175 (2)
C70.1831 (2)0.63648 (16)0.88678 (14)0.0183 (2)
C80.8037 (2)0.76415 (16)0.60143 (15)0.0213 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl30.03132 (19)0.02051 (17)0.0373 (2)0.01134 (13)0.00961 (14)0.01559 (14)
Cl40.02459 (17)0.02381 (17)0.02327 (17)0.00040 (13)0.00747 (12)0.01283 (13)
Cl60.02574 (18)0.02134 (17)0.0402 (2)0.01189 (13)0.01471 (14)0.01511 (14)
O10.0302 (5)0.0209 (5)0.0235 (5)0.0048 (4)0.0154 (4)0.0082 (4)
O20.0253 (5)0.0230 (5)0.0290 (5)0.0119 (4)0.0160 (4)0.0119 (4)
N10.0310 (6)0.0178 (5)0.0258 (6)0.0035 (5)0.0160 (5)0.0082 (5)
N20.0275 (6)0.0319 (7)0.0285 (6)0.0076 (5)0.0134 (5)0.0090 (5)
C10.0169 (6)0.0176 (6)0.0161 (5)0.0039 (5)0.0057 (4)0.0074 (5)
C20.0169 (6)0.0191 (6)0.0170 (6)0.0053 (5)0.0051 (5)0.0063 (5)
C30.0204 (6)0.0170 (6)0.0204 (6)0.0056 (5)0.0044 (5)0.0087 (5)
C40.0182 (6)0.0192 (6)0.0165 (5)0.0010 (5)0.0040 (5)0.0085 (5)
C50.0166 (6)0.0206 (6)0.0168 (6)0.0037 (5)0.0062 (5)0.0064 (5)
C60.0181 (6)0.0163 (6)0.0184 (6)0.0054 (5)0.0047 (5)0.0061 (5)
C70.0178 (6)0.0198 (6)0.0187 (6)0.0035 (5)0.0061 (5)0.0095 (5)
C80.0203 (6)0.0219 (6)0.0195 (6)0.0025 (5)0.0059 (5)0.0068 (5)
Geometric parameters (Å, º) top
Cl3—C31.7153 (13)N2—C81.1424 (17)
Cl4—C41.7151 (12)C1—C61.3975 (17)
Cl6—C61.7263 (13)C1—C21.4127 (17)
O1—C71.2464 (15)C1—C71.5033 (16)
O2—C21.3360 (15)C2—C31.4023 (18)
O2—H20.83 (2)C3—C41.3841 (18)
N1—C71.3194 (17)C4—C51.4006 (18)
N1—H110.891 (19)C5—C61.3983 (17)
N1—H120.823 (19)C5—C81.4362 (17)
C2—O2—H2104.4 (13)C3—C4—C5119.89 (11)
C7—N1—H11118.0 (11)C3—C4—Cl4121.23 (10)
C7—N1—H12121.6 (13)C5—C4—Cl4118.87 (10)
H11—N1—H12119.7 (17)C6—C5—C4119.76 (11)
C6—C1—C2117.43 (11)C6—C5—C8120.28 (12)
C6—C1—C7126.05 (11)C4—C5—C8119.94 (11)
C2—C1—C7116.51 (11)C1—C6—C5121.61 (11)
O2—C2—C3116.57 (11)C1—C6—Cl6122.11 (10)
O2—C2—C1122.22 (11)C5—C6—Cl6116.21 (9)
C3—C2—C1121.20 (11)O1—C7—N1121.54 (12)
C4—C3—C2119.98 (12)O1—C7—C1118.40 (11)
C4—C3—Cl3121.72 (10)N1—C7—C1120.02 (11)
C2—C3—Cl3118.30 (10)N2—C8—C5178.17 (15)
C6—C1—C2—O2176.57 (12)C3—C4—C5—C8179.27 (12)
C7—C1—C2—O22.15 (18)Cl4—C4—C5—C81.16 (17)
C6—C1—C2—C34.26 (18)C2—C1—C6—C53.44 (18)
C7—C1—C2—C3177.02 (11)C7—C1—C6—C5177.98 (12)
O2—C2—C3—C4177.93 (12)C2—C1—C6—Cl6173.60 (9)
C1—C2—C3—C42.85 (19)C7—C1—C6—Cl64.99 (18)
O2—C2—C3—Cl31.53 (16)C4—C5—C6—C11.21 (19)
C1—C2—C3—Cl3177.69 (10)C8—C5—C6—C1177.72 (12)
C2—C3—C4—C50.48 (19)C4—C5—C6—Cl6175.99 (10)
Cl3—C3—C4—C5179.92 (10)C8—C5—C6—Cl65.08 (16)
C2—C3—C4—Cl4179.07 (9)C6—C1—C7—O1149.53 (13)
Cl3—C3—C4—Cl40.37 (16)C2—C1—C7—O129.06 (17)
C3—C4—C5—C60.34 (19)C6—C1—C7—N132.67 (19)
Cl4—C4—C5—C6179.90 (10)C2—C1—C7—N1148.73 (13)

Experimental details

Crystal data
Chemical formulaC8H3Cl3N2O2
Mr265.47
Crystal system, space groupTriclinic, P1
Temperature (K)174
a, b, c (Å)6.3020 (6), 9.0437 (8), 9.3822 (9)
α, β, γ (°)109.196 (1), 94.937 (1), 104.076 (1)
V3)481.72 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.93
Crystal size (mm)0.45 × 0.30 × 0.25
Data collection
DiffractometerBruker SMART 1K CCD area-detector
Absorption correctionMulti-scan
[SADABS (Sheldrick, 2003; Blessing, 1995)]
Tmin, Tmax0.74, 0.79
No. of measured, independent and
observed [I > 2σ(I)] reflections
5659, 2164, 2036
Rint0.017
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.063, 1.07
No. of reflections2164
No. of parameters149
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.43, 0.22

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Distances and angles (Å, °) in the hydrogen bonds of (I) top
X—H···Y—ZX—HX—H···YH···YH···Y—ZX···Y
O2—H2···O1-C70.83 (2)154 (2)1.77 (2)96.4 (6)2.5542 (14)
N1—H11···O1i—C710.89 (2)167 (2)2.07 (2)123.6 (5)2.9461 (15)
N1—H12···N2ii—C810.82 (2)154 (2)2.38 (2)122.1 (5)3.1417 (17)
Symmetry codes: (i) -x, 1-y, 2-z; (ii) 1-x, 1-y, 1-z.
 

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