Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108001017/ln3085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108001017/ln3085Isup2.hkl |
CCDC reference: 682806
The compound was obtained from the Diamond Shamrock Corporation. The crystal used was from the original sample.
The solution and refinement were straightforward. The H-atom positions and isotropic displacement parameters were refined.
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 (ClCCC≡N)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···N2i≡C8i 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···N≡C 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).
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).
C8H3Cl3N2O2 | Z = 2 |
Mr = 265.47 | F(000) = 264 |
Triclinic, P1 | Dx = 1.830 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.3020 (6) Å | Cell parameters from 2326 reflections |
b = 9.0437 (8) Å | θ = 2.3–27.4° |
c = 9.3822 (9) Å | µ = 0.93 mm−1 |
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 |
Bruker SMART 1K CCD area-detector diffractometer | 2164 independent reflections |
Radiation source: fine-focus sealed tube | 2036 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan [SADABS (Sheldrick, 2003; Blessing, 1995)] | h = −8→8 |
Tmin = 0.74, Tmax = 0.79 | k = −11→11 |
5659 measured reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | All 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 reflections | Δρmax = 0.43 e Å−3 |
149 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.023 (2) |
C8H3Cl3N2O2 | γ = 104.076 (1)° |
Mr = 265.47 | V = 481.72 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.3020 (6) Å | Mo Kα radiation |
b = 9.0437 (8) Å | µ = 0.93 mm−1 |
c = 9.3822 (9) Å | T = 174 K |
α = 109.196 (1)° | 0.45 × 0.30 × 0.25 mm |
β = 94.937 (1)° |
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 = 0.79 | Rint = 0.017 |
5659 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.063 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.43 e Å−3 |
2164 reflections | Δρmin = −0.22 e Å−3 |
149 parameters |
x | y | z | Uiso*/Ueq | ||
Cl3 | 0.37098 (6) | 1.18489 (4) | 0.80299 (4) | 0.02742 (11) | |
Cl4 | 0.75184 (5) | 1.08721 (4) | 0.62495 (4) | 0.02395 (10) | |
Cl6 | 0.58111 (6) | 0.52885 (4) | 0.72883 (4) | 0.02654 (11) | |
O1 | 0.10836 (16) | 0.70392 (12) | 1.00184 (11) | 0.0247 (2) | |
O2 | 0.15037 (17) | 0.94932 (12) | 0.91936 (11) | 0.0235 (2) | |
H2 | 0.109 (3) | 0.883 (2) | 0.962 (2) | 0.040 (5)* | |
N1 | 0.1264 (2) | 0.47587 (14) | 0.81978 (14) | 0.0248 (3) | |
H11 | 0.037 (3) | 0.416 (2) | 0.861 (2) | 0.032 (4)* | |
H12 | 0.156 (3) | 0.432 (2) | 0.735 (2) | 0.033 (5)* | |
N2 | 0.9345 (2) | 0.72514 (16) | 0.53256 (14) | 0.0294 (3) | |
C1 | 0.3346 (2) | 0.74280 (15) | 0.82112 (13) | 0.0166 (2) | |
C2 | 0.3022 (2) | 0.89712 (15) | 0.84156 (14) | 0.0176 (2) | |
C3 | 0.4274 (2) | 1.00282 (15) | 0.77880 (14) | 0.0186 (2) | |
C4 | 0.5929 (2) | 0.95968 (15) | 0.70084 (14) | 0.0182 (2) | |
C5 | 0.6338 (2) | 0.80989 (15) | 0.68383 (14) | 0.0182 (3) | |
C6 | 0.5062 (2) | 0.70427 (15) | 0.74507 (14) | 0.0175 (2) | |
C7 | 0.1831 (2) | 0.63648 (16) | 0.88678 (14) | 0.0183 (2) | |
C8 | 0.8037 (2) | 0.76415 (16) | 0.60143 (15) | 0.0213 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl3 | 0.03132 (19) | 0.02051 (17) | 0.0373 (2) | 0.01134 (13) | 0.00961 (14) | 0.01559 (14) |
Cl4 | 0.02459 (17) | 0.02381 (17) | 0.02327 (17) | −0.00040 (13) | 0.00747 (12) | 0.01283 (13) |
Cl6 | 0.02574 (18) | 0.02134 (17) | 0.0402 (2) | 0.01189 (13) | 0.01471 (14) | 0.01511 (14) |
O1 | 0.0302 (5) | 0.0209 (5) | 0.0235 (5) | 0.0048 (4) | 0.0154 (4) | 0.0082 (4) |
O2 | 0.0253 (5) | 0.0230 (5) | 0.0290 (5) | 0.0119 (4) | 0.0160 (4) | 0.0119 (4) |
N1 | 0.0310 (6) | 0.0178 (5) | 0.0258 (6) | 0.0035 (5) | 0.0160 (5) | 0.0082 (5) |
N2 | 0.0275 (6) | 0.0319 (7) | 0.0285 (6) | 0.0076 (5) | 0.0134 (5) | 0.0090 (5) |
C1 | 0.0169 (6) | 0.0176 (6) | 0.0161 (5) | 0.0039 (5) | 0.0057 (4) | 0.0074 (5) |
C2 | 0.0169 (6) | 0.0191 (6) | 0.0170 (6) | 0.0053 (5) | 0.0051 (5) | 0.0063 (5) |
C3 | 0.0204 (6) | 0.0170 (6) | 0.0204 (6) | 0.0056 (5) | 0.0044 (5) | 0.0087 (5) |
C4 | 0.0182 (6) | 0.0192 (6) | 0.0165 (5) | 0.0010 (5) | 0.0040 (5) | 0.0085 (5) |
C5 | 0.0166 (6) | 0.0206 (6) | 0.0168 (6) | 0.0037 (5) | 0.0062 (5) | 0.0064 (5) |
C6 | 0.0181 (6) | 0.0163 (6) | 0.0184 (6) | 0.0054 (5) | 0.0047 (5) | 0.0061 (5) |
C7 | 0.0178 (6) | 0.0198 (6) | 0.0187 (6) | 0.0035 (5) | 0.0061 (5) | 0.0095 (5) |
C8 | 0.0203 (6) | 0.0219 (6) | 0.0195 (6) | 0.0025 (5) | 0.0059 (5) | 0.0068 (5) |
Cl3—C3 | 1.7153 (13) | N2—C8 | 1.1424 (17) |
Cl4—C4 | 1.7151 (12) | C1—C6 | 1.3975 (17) |
Cl6—C6 | 1.7263 (13) | C1—C2 | 1.4127 (17) |
O1—C7 | 1.2464 (15) | C1—C7 | 1.5033 (16) |
O2—C2 | 1.3360 (15) | C2—C3 | 1.4023 (18) |
O2—H2 | 0.83 (2) | C3—C4 | 1.3841 (18) |
N1—C7 | 1.3194 (17) | C4—C5 | 1.4006 (18) |
N1—H11 | 0.891 (19) | C5—C6 | 1.3983 (17) |
N1—H12 | 0.823 (19) | C5—C8 | 1.4362 (17) |
C2—O2—H2 | 104.4 (13) | C3—C4—C5 | 119.89 (11) |
C7—N1—H11 | 118.0 (11) | C3—C4—Cl4 | 121.23 (10) |
C7—N1—H12 | 121.6 (13) | C5—C4—Cl4 | 118.87 (10) |
H11—N1—H12 | 119.7 (17) | C6—C5—C4 | 119.76 (11) |
C6—C1—C2 | 117.43 (11) | C6—C5—C8 | 120.28 (12) |
C6—C1—C7 | 126.05 (11) | C4—C5—C8 | 119.94 (11) |
C2—C1—C7 | 116.51 (11) | C1—C6—C5 | 121.61 (11) |
O2—C2—C3 | 116.57 (11) | C1—C6—Cl6 | 122.11 (10) |
O2—C2—C1 | 122.22 (11) | C5—C6—Cl6 | 116.21 (9) |
C3—C2—C1 | 121.20 (11) | O1—C7—N1 | 121.54 (12) |
C4—C3—C2 | 119.98 (12) | O1—C7—C1 | 118.40 (11) |
C4—C3—Cl3 | 121.72 (10) | N1—C7—C1 | 120.02 (11) |
C2—C3—Cl3 | 118.30 (10) | N2—C8—C5 | 178.17 (15) |
C6—C1—C2—O2 | −176.57 (12) | C3—C4—C5—C8 | 179.27 (12) |
C7—C1—C2—O2 | 2.15 (18) | Cl4—C4—C5—C8 | −1.16 (17) |
C6—C1—C2—C3 | 4.26 (18) | C2—C1—C6—C5 | −3.44 (18) |
C7—C1—C2—C3 | −177.02 (11) | C7—C1—C6—C5 | 177.98 (12) |
O2—C2—C3—C4 | 177.93 (12) | C2—C1—C6—Cl6 | 173.60 (9) |
C1—C2—C3—C4 | −2.85 (19) | C7—C1—C6—Cl6 | −4.99 (18) |
O2—C2—C3—Cl3 | −1.53 (16) | C4—C5—C6—C1 | 1.21 (19) |
C1—C2—C3—Cl3 | 177.69 (10) | C8—C5—C6—C1 | −177.72 (12) |
C2—C3—C4—C5 | 0.48 (19) | C4—C5—C6—Cl6 | −175.99 (10) |
Cl3—C3—C4—C5 | 179.92 (10) | C8—C5—C6—Cl6 | 5.08 (16) |
C2—C3—C4—Cl4 | −179.07 (9) | C6—C1—C7—O1 | 149.53 (13) |
Cl3—C3—C4—Cl4 | 0.37 (16) | C2—C1—C7—O1 | −29.06 (17) |
C3—C4—C5—C6 | 0.34 (19) | C6—C1—C7—N1 | −32.67 (19) |
Cl4—C4—C5—C6 | 179.90 (10) | C2—C1—C7—N1 | 148.73 (13) |
Experimental details
Crystal data | |
Chemical formula | C8H3Cl3N2O2 |
Mr | 265.47 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 481.72 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.45 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector |
Absorption correction | Multi-scan [SADABS (Sheldrick, 2003; Blessing, 1995)] |
Tmin, Tmax | 0.74, 0.79 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5659, 2164, 2036 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.063, 1.07 |
No. of reflections | 2164 |
No. of parameters | 149 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.43, −0.22 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).
X—H···Y—Z | X—H | X—H···Y | H···Y | H···Y—Z | X···Y |
O2—H2···O1-C7 | 0.83 (2) | 154 (2) | 1.77 (2) | 96.4 (6) | 2.5542 (14) |
N1—H11···O1i—C71 | 0.89 (2) | 167 (2) | 2.07 (2) | 123.6 (5) | 2.9461 (15) |
N1—H12···N2ii—C81 | 0.82 (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. |
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 (ClCCC≡N)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···N2i≡C8i 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···N≡C 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.