research communications
Weak interactions in the crystal structures of two indole derivatives
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and bFundação Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: l.trembleau@abdn.ac.uk, w.harrison@abdn.ac.uk
We describe the syntheses and crystal structures of two indole derivatives, namely a second monoclinic polymorph of ethyl 5-chloro-1H-indole-2-carboxylate C11H10ClNO2, (I), and ethyl 5-chloro-3-iodo-1H-indole-2-carboxylate, C11H9ClINO2, (II). In their crystal structures, both compounds form inversion dimers linked by pairs of N—H⋯O hydrogen bonds, which generate R22(10) loops. The dimers are linked into double chains in (I) and sheets in (II) by a variety of weak interactions, including π–π stacking, C—I⋯π, C—Cl—π interactions and I⋯Cl halogen bonds.
1. Chemical context
As part of our ongoing synthetic, biological (Kerr, 2013) and structural studies (Kerr et al., 2016) of variously substituted indole derivatives, we now report the syntheses and crystal structures of ethyl 5-chloro-1H-indole-2-carboxylate (I) and ethyl 5-chloro-3-iodo-1H-indole-2-carboxylate (II), which differ in the substituent (H or I) at the 3-position of the ring system. Compound (I) is a second monoclinic polymorph of the recently described 5-chloro-1H-indole-2-carboxylate (Wu et al., 2013).
2. Structural commentary
Compound (I) crystallizes in P21/n with one molecule in the (Fig. 1). The dihedral angle between the mean plane of the N1/C1–C8 indole ring system (r.m.s. deviation = 0.010 Å) and the C9/O1/O2 grouping is 2.4 (2)°. The chlorine atom deviates from the indole plane by 0.0625 (14) Å. The C8—C9—O1—C10 torsion angle of −178.86 (11)° indicates an anti conformation about the C9—O1 bond, whereas the C9—O1—C10—C11 torsion angle is −81.73 (14)° and C11 projects from the mean plane of the other non-hydrogen atoms by 1.298 (2) Å.
In the structure reported by Wu et al. (2013), (CCDC refcode VIHMUW), the same molecule also crystallizes in P21/n [a = 10.570 (3), b = 5.6165 (15), c = 18.091 (5) Å, β = 105.681 (4)°, V = 1034.0 (5) Å3, Z = 4]: the only significant conformational difference compared to (I) is (using our atom-labelling scheme) the C9—O1—C10—C11 torsion angle of 173.19 (12)°, which indicates that the molecule in the Wu et al. polymorph is almost planar (r.m.s. deviation = 0.031 Å for 15 non-hydrogen atoms). The densities of (I) [ρ = 1.438 g cm−1] and the Wu polymorph [ρ = 1.437 g cm−1] are essentially identical.
There is one molecule in the , which crystallizes in P, as shown in Fig. 2. The C9/O1/O2 grouping is almost coplanar with the mean-plane of the indole ring system (r.m.s. deviation = 0.009 Å), as indicated by the dihedral angle of 3.95 (7)° between C1–C8/N1 and C9/O1/O2. Atoms Cl1 and I1 deviate from the indole plane by −0.106 (2) and 0.081 (2) Å, respectively. The conformation of the C8—C9—O1—C10 bond in (II) [torsion angle = −177.42 (16)°] is almost the same as the equivalent grouping in (I), but the C9—O1—C10—C11 torsion angle of −178.33 (17)° is quite different, and indeed, the complete molecule of (II) is almost planar (r.m.s. deviation = 0.033 Å for 16 non-hydrogen atoms).
of (II)3. Supramolecular features
In the crystal of (I), inversion dimers linked by pairs of N—H⋯Oi [symmetry code: (i) 1 − x, 2 − y, 1 − z] hydrogen bonds (Table 1, Fig. 1) generate R22(10) loops. The first weak interaction to consider is aromatic π–π stacking between the C1–C6 (π6) ring and the C1/C6/C7/C8/N1 (π5) five-membered ring displaced by translation in the b-axis direction (Fig. 3). The π6–π5ii [symmetry code: (ii) x, 1 + y, z] centroid–centroid separation is 3.7668 (9) Å and the inter-plane angle is 1.30 (7)°. This interaction appears to be reinforced by a weak C—Cl⋯π5ii bond (Chifotides & Dunbar, 2013); the chlorine atom lies almost directly above the centre of the six-membered ring displaced in [010] with Cl⋯π = 3.5363 (7) Å and C—Cl⋯π = 86.35 (5)°. This is very slightly shorter than the contact distance of 3.55 Å for a chlorine atom and a benzene ring, assuming a radius of 1.75 Å for Cl and a half-thickness of 1.8 Å for a benzene ring. Thus, each benzene ring faces a chlorine atom on one face and a five-membered ring on the other (Cl⋯π6⋯π5 = 154.5°). The carbonyl oxygen atom (O2) of the ester group lies in a reasonable orientation to partake in a C=O⋯π5 bond (Gao et al., 2009) but here the O⋯π5iii [symmetry code: (iii) x, y − 1, z] separation of 3.4068 (11) Å is significantly greater than the van der Waals' radius sum of 3.32 Å [C=O⋯π5 = 88.40 (8)° and O⋯π5⋯π6 = 153.9°] and can hardly be considered to be a bond. Taken together, the strong (N—H⋯O) and weak (π–π, Cl⋯π) bonds lead to [010] double chains in the extended structure of (I).
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Despite the fact that (I) and the Wu et al. (2013) polymorph of the same phase crystallize in the same their packing motifs are completely different. In the Wu dimers linked by pairs of N—H⋯O hydrogen bonds also occur but there is no aromatic π–π stacking (the shortest centroid–centroid separation is greater than 4.75 Å) and no C—Cl⋯π contacts. The only significant interaction indicated by a PLATON (Spek, 2009) analysis of the structure is a weak C—H⋯π5 bond (H⋯π = 2.72 Å). Considered by itself, this interaction links the molecules into [010] chains; taken together, the N—H⋯O and C—H⋯π interactions generate (110) sheets.
The crystal of (II) also features inversion dimers linked by pairs of N—H⋯Oi [symmetry code: (i) −x, 2 − y, 1 − z] hydrogen bonds (Table 2, Fig. 2) involving the equivalent atoms to (I) with the same graph-set motif. Aromatic π–π stacking also occurs in the crystal of (II), but this time the molecules are related by inversion, rather than translation, symmetry: this operation `flips' one of the molecules such that the six-membered ring in each molecule overlaps the five-membered ring in the other (Fig. 6): the π6–π5ii [symmetry code: (ii) −x, 1 − y, 1 − z] separation of the centroids of the six- and five-membered rings is 3.6365 (14) Å and the inter-planar angle is 0.92 (13)°. The iodine atom of a molecule displaced in the [100] direction lies above the inversion-generated five-membered ring to form a C—I⋯π5 bond with I1⋯π5iii [symmetry code: (iii) 1 − x, 1 − y, 1 − z] = 3.6543 (11) Å and C7—I1⋯π5iii = 87.00 (7)°. Thus, the five-membered ring faces a six-membered ring on one face and an I atom on the other (I⋯π5⋯π6 = 148.6°). The I atom also participates in a halogen bond (Desiraju et al., 2013) to the chlorine atom of an inversion-related molecule with I1⋯Cl1iv [symmetry code: (iv) 1 − x, −y, 1 − z] = 3.6477 (6) Å (van der Waals contact distance = 3.73 Å), C7—I1⋯Cl1iv = 173.28 (5)° and C4iv—Cl1iv⋯I1 = 104.34 (5)°. These angles clearly define this interaction as a type-II halogen bond (Pedireddi et al., 1994). Taken together, the weak and strong interactions lead to (001) sheets, with the centrosymmetric pairs of I⋯Cl halogen bonds and pairs of N—H⋯O hydrogen bonds alternating with respect to the [100] direction (Fig. 4).
4. Database survey
A search of the Cambridge Structural Database (CSD; Groom et al., 2016) revealed 24 indole derivatives with an ester group at the 2-position of the ring system. In terms of halogen substitution, there were 58 5-chloro and just two 3-iodo derivatives. As noted above, VIHMUW (Wu et al., 2013) is a polymorph of (I): crystals of this phase in the form of colourless prisms were obtained by recrystallization from ethanol solution at room temperature, compared to colourless needles obtained from methanol solution at room temperature in the present study.
There has recently been debate on the significance – or otherwise – of weak intermolecular interactions in establishing the packing in molecular crystals (Dunitz, 2015; Thakur et al., 2015). The latter authors mentioned the role of weak interactions in establishing the structures of polymorphs and it is striking to us how different the packing motifs of (I) and VIHMUW are.
5. Synthesis and crystallization
To prepare (I), a mixture of ethyl 2-(2-[4-chlorophenyl]hydrazono)propanoate (2.29 g, 9.51 mmol), prepared from p-chlorophenylhydrazine hydrochloride and ethyl pyruvate according to a published method (Zhang et al., 2011) and PPA (22.54 g) were refluxed in toluene (40 ml) for 3 h. After cooling, the solvent was decanted off and the solid residue was washed with toluene (3 × 50 ml). Evaporation of the combined organic phases under reduced pressure gave a yellow solid, flash of which (1:6 ethyl acetate, hexanes) afforded ethyl 5-chloro-1H-indole-2-carboxylate as a yellow solid (1.34 g, 63%). Colourless needles of (I) were recrystallized from methanol solution at room temperature. δC(101 MHz; CDCl3) 162.0 (Cq), 135.2 (Cq), 128.9 (Cq), 128.6 (Cq), 126.7 (Cq), 126.0 (CH), 121.9 (CH), 113.1 (CH), 108.1 (CH), 61.5 (CH2) and 14.5 (CH3); δH(400 MHz; CDCl3) 8.91 (1 H, br s), 7.67 (1 H, s), 7.35–7.28 (2 H, m), 7.15 (1 H, s), 4.41 (2 H, q, J 7.1) and 1.41 (3 H, t, J 7.1); Rf 0.29 (1:6 EtOAc, hexanes); m.p. 440–441 K; IR (Nujol, cm−1) 3310, 1728, 1697, 1264, 1080 and 877; HRMS (ESI) for C11H1135ClNO2 [M + H]+ calculated 224.0479, found 224.0466.
To prepare (II), potassium hydroxide (1.804 g, 32.2 mmol) was added to a solution of (I) (1.215 g, 5.43 mmol) in dry DMF (6.0 ml) at 273 K and stirred for 10 min. Separately, a solution of iodine (1.710 g, 6.74 mmol) in dry DMF (6.75 ml) was prepared. The two liquids were combined and stirred over ice for 90 min. Pouring the reaction mixture into a saturated aqueous solution of ammonium chloride and sodium thiosulfate (60 ml) precipitated a brown solid. This was collected by filtration and purified by flash (1:8 ethyl acetate, hexanes) to afford ethyl 5-chloro-3-iodo-1H-indole-2-carboxylate as a yellow solid (1.825 g, 80%). Pale-yellow plates of (II) were recrystallized from methanol solution at room temperature. δC(101 MHz; DMSO-d6) 160.5 (Cq), 135.8 (Cq), 132.1 (Cq), 128.9 (Cq), 126.5 (CH), 126.3 (Cq), 121.8 (CH), 115.4 (CH), 65.2 (Cq), 61.4 (CH2) and 14.6 (CH3); δH(400 MHz; DMSO-d6) 12.42 (1 H, br s), 7.47 (1 H, d, J 8.4), 7.39 (1 H, d, J 1.6), 7.31 (1 H, dd, J 2.0, 9.2), 4.36 (2 H, q, J 7.2) and 1.36 (3 H, t, J 7.0); Rf 0.13 (1:8 ethyl acetate, hexanes); m.p. 412 K, IR (KBr, cm−1) 3291, 2977, 1744, 1683, 1514, 1332, 1115, 1080, 772, 749 and 604; HRMS (ESI) for C11H1035ClINO2 [M + H]+ calculated 349.9445, found 349.9453.
6. Refinement
Crystal data, data collection and structure . The N-bound H atoms were located in difference maps and their positions freely refined. The C-bound H atoms were placed geometrically (C—H = 0.93–0.98 Å) and refined as riding atoms. The constraint Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied in all cases. The –CH3 groups were allowed to rotate, but not to tip, to best fit the electron density.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989016008616/sj5499sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016008616/sj5499Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989016008616/sj5499IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016008616/sj5499Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989016008616/sj5499IIsup5.cml
For both compounds, data collection: CrystalClear (Rigaku, 2012); cell
CrystalClear (Rigaku, 2012); data reduction: CrystalClear (Rigaku, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C11H10ClNO2 | F(000) = 464 |
Mr = 223.65 | Dx = 1.438 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7168 (6) Å | Cell parameters from 6396 reflections |
b = 4.5783 (1) Å | θ = 3.0–27.5° |
c = 16.5929 (11) Å | µ = 0.35 mm−1 |
β = 97.464 (7)° | T = 100 K |
V = 1033.20 (9) Å3 | Rod, colourless |
Z = 4 | 0.70 × 0.04 × 0.03 mm |
Rigaku Mercury CCD diffractometer | 2051 reflections with I > 2σ(I) |
ω scans | Rint = 0.022 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2012) | θmax = 27.5°, θmin = 3.0° |
Tmin = 0.793, Tmax = 0.990 | h = −17→17 |
7035 measured reflections | k = −4→5 |
2340 independent reflections | l = −19→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0408P)2 + 0.4177P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2340 reflections | Δρmax = 0.33 e Å−3 |
139 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.52594 (9) | 0.5040 (3) | 0.35005 (8) | 0.0142 (3) | |
C2 | 0.62255 (10) | 0.4033 (3) | 0.35004 (8) | 0.0176 (3) | |
H2 | 0.6742 | 0.4669 | 0.3899 | 0.021* | |
C3 | 0.63988 (9) | 0.2090 (3) | 0.29013 (8) | 0.0171 (3) | |
H3 | 0.7044 | 0.1360 | 0.2883 | 0.021* | |
C4 | 0.56188 (10) | 0.1181 (3) | 0.23127 (8) | 0.0153 (3) | |
C5 | 0.46670 (9) | 0.2127 (3) | 0.23045 (8) | 0.0146 (3) | |
H5 | 0.4157 | 0.1459 | 0.1905 | 0.017* | |
C6 | 0.44761 (9) | 0.4121 (3) | 0.29091 (8) | 0.0134 (3) | |
C7 | 0.36151 (9) | 0.5605 (3) | 0.30827 (8) | 0.0136 (3) | |
H7 | 0.2972 | 0.5434 | 0.2795 | 0.016* | |
C8 | 0.38999 (9) | 0.7341 (3) | 0.37519 (7) | 0.0135 (3) | |
C9 | 0.33337 (9) | 0.9388 (3) | 0.41806 (7) | 0.0133 (3) | |
C10 | 0.17639 (10) | 1.1516 (3) | 0.42258 (8) | 0.0174 (3) | |
H10A | 0.1186 | 1.2025 | 0.3829 | 0.021* | |
H10B | 0.2134 | 1.3334 | 0.4376 | 0.021* | |
C11 | 0.14202 (11) | 1.0204 (4) | 0.49746 (9) | 0.0271 (3) | |
H11A | 0.1002 | 1.1610 | 0.5214 | 0.041* | |
H11B | 0.1044 | 0.8421 | 0.4825 | 0.041* | |
H11C | 0.1991 | 0.9728 | 0.5371 | 0.041* | |
N1 | 0.48871 (8) | 0.6981 (3) | 0.40047 (7) | 0.0147 (2) | |
H1 | 0.5235 (12) | 0.789 (4) | 0.4411 (10) | 0.018* | |
O1 | 0.23886 (6) | 0.9493 (2) | 0.38517 (5) | 0.0152 (2) | |
O2 | 0.36753 (7) | 1.0841 (2) | 0.47654 (6) | 0.0184 (2) | |
Cl1 | 0.58935 (2) | −0.12275 (8) | 0.15557 (2) | 0.01929 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0137 (6) | 0.0138 (6) | 0.0147 (6) | −0.0016 (5) | −0.0002 (5) | 0.0003 (5) |
C2 | 0.0128 (6) | 0.0196 (7) | 0.0193 (6) | −0.0010 (5) | −0.0026 (5) | −0.0010 (5) |
C3 | 0.0123 (6) | 0.0175 (7) | 0.0213 (7) | 0.0013 (5) | 0.0012 (5) | 0.0009 (6) |
C4 | 0.0175 (6) | 0.0126 (6) | 0.0164 (6) | −0.0001 (5) | 0.0040 (5) | −0.0007 (5) |
C5 | 0.0144 (6) | 0.0146 (6) | 0.0140 (6) | −0.0017 (5) | −0.0008 (5) | 0.0004 (5) |
C6 | 0.0134 (6) | 0.0126 (6) | 0.0135 (6) | −0.0014 (5) | −0.0007 (5) | 0.0020 (5) |
C7 | 0.0130 (6) | 0.0140 (6) | 0.0134 (6) | −0.0011 (5) | −0.0004 (4) | 0.0008 (5) |
C8 | 0.0122 (6) | 0.0149 (6) | 0.0129 (6) | −0.0012 (5) | −0.0007 (4) | 0.0014 (5) |
C9 | 0.0142 (6) | 0.0132 (6) | 0.0122 (6) | −0.0014 (5) | 0.0007 (4) | 0.0025 (5) |
C10 | 0.0149 (6) | 0.0169 (7) | 0.0203 (7) | 0.0043 (5) | 0.0013 (5) | −0.0010 (5) |
C11 | 0.0248 (7) | 0.0318 (9) | 0.0265 (8) | 0.0035 (7) | 0.0106 (6) | 0.0017 (7) |
N1 | 0.0125 (5) | 0.0175 (6) | 0.0130 (5) | −0.0004 (5) | −0.0023 (4) | −0.0027 (4) |
O1 | 0.0126 (4) | 0.0171 (5) | 0.0154 (4) | 0.0015 (4) | −0.0005 (3) | −0.0023 (4) |
O2 | 0.0164 (5) | 0.0218 (5) | 0.0158 (5) | −0.0001 (4) | −0.0018 (4) | −0.0050 (4) |
Cl1 | 0.01786 (17) | 0.01983 (19) | 0.02054 (18) | 0.00168 (13) | 0.00388 (12) | −0.00493 (13) |
C1—N1 | 1.3644 (18) | C7—H7 | 0.9500 |
C1—C2 | 1.4032 (18) | C8—N1 | 1.3744 (16) |
C1—C6 | 1.4215 (17) | C8—C9 | 1.4599 (19) |
C2—C3 | 1.3774 (19) | C9—O2 | 1.2187 (16) |
C2—H2 | 0.9500 | C9—O1 | 1.3405 (15) |
C3—C4 | 1.4145 (19) | C10—O1 | 1.4543 (16) |
C3—H3 | 0.9500 | C10—C11 | 1.5098 (19) |
C4—C5 | 1.3739 (18) | C10—H10A | 0.9900 |
C4—Cl1 | 1.7488 (14) | C10—H10B | 0.9900 |
C5—C6 | 1.4059 (18) | C11—H11A | 0.9800 |
C5—H5 | 0.9500 | C11—H11B | 0.9800 |
C6—C7 | 1.4240 (18) | C11—H11C | 0.9800 |
C7—C8 | 1.3800 (18) | N1—H1 | 0.878 (17) |
N1—C1—C2 | 130.00 (12) | N1—C8—C9 | 119.57 (11) |
N1—C1—C6 | 107.86 (11) | C7—C8—C9 | 130.46 (12) |
C2—C1—C6 | 122.13 (13) | O2—C9—O1 | 123.78 (12) |
C3—C2—C1 | 117.63 (12) | O2—C9—C8 | 124.37 (12) |
C3—C2—H2 | 121.2 | O1—C9—C8 | 111.85 (11) |
C1—C2—H2 | 121.2 | O1—C10—C11 | 111.24 (12) |
C2—C3—C4 | 120.17 (12) | O1—C10—H10A | 109.4 |
C2—C3—H3 | 119.9 | C11—C10—H10A | 109.4 |
C4—C3—H3 | 119.9 | O1—C10—H10B | 109.4 |
C5—C4—C3 | 123.13 (12) | C11—C10—H10B | 109.4 |
C5—C4—Cl1 | 119.00 (10) | H10A—C10—H10B | 108.0 |
C3—C4—Cl1 | 117.87 (10) | C10—C11—H11A | 109.5 |
C4—C5—C6 | 117.55 (12) | C10—C11—H11B | 109.5 |
C4—C5—H5 | 121.2 | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 121.2 | C10—C11—H11C | 109.5 |
C5—C6—C1 | 119.38 (12) | H11A—C11—H11C | 109.5 |
C5—C6—C7 | 133.66 (12) | H11B—C11—H11C | 109.5 |
C1—C6—C7 | 106.95 (11) | C1—N1—C8 | 108.85 (11) |
C8—C7—C6 | 106.38 (11) | C1—N1—H1 | 124.7 (11) |
C8—C7—H7 | 126.8 | C8—N1—H1 | 126.4 (11) |
C6—C7—H7 | 126.8 | C9—O1—C10 | 116.19 (10) |
N1—C8—C7 | 109.96 (12) | ||
N1—C1—C2—C3 | −178.66 (14) | C1—C6—C7—C8 | 0.37 (15) |
C6—C1—C2—C3 | −0.1 (2) | C6—C7—C8—N1 | −0.63 (15) |
C1—C2—C3—C4 | 0.2 (2) | C6—C7—C8—C9 | 178.10 (13) |
C2—C3—C4—C5 | −0.5 (2) | N1—C8—C9—O2 | −0.4 (2) |
C2—C3—C4—Cl1 | 178.63 (11) | C7—C8—C9—O2 | −178.99 (14) |
C3—C4—C5—C6 | 0.8 (2) | N1—C8—C9—O1 | 179.38 (11) |
Cl1—C4—C5—C6 | −178.38 (10) | C7—C8—C9—O1 | 0.8 (2) |
C4—C5—C6—C1 | −0.67 (19) | C2—C1—N1—C8 | 178.35 (14) |
C4—C5—C6—C7 | 178.26 (14) | C6—C1—N1—C8 | −0.40 (15) |
N1—C1—C6—C5 | 179.20 (11) | C7—C8—N1—C1 | 0.65 (15) |
C2—C1—C6—C5 | 0.3 (2) | C9—C8—N1—C1 | −178.23 (12) |
N1—C1—C6—C7 | 0.01 (15) | O2—C9—O1—C10 | 0.89 (18) |
C2—C1—C6—C7 | −178.85 (12) | C8—C9—O1—C10 | −178.86 (11) |
C5—C6—C7—C8 | −178.65 (14) | C11—C10—O1—C9 | −81.73 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.878 (17) | 1.977 (17) | 2.8288 (15) | 163.0 (15) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
C11H9ClINO2 | Z = 2 |
Mr = 349.54 | F(000) = 336 |
Triclinic, P1 | Dx = 1.953 Mg m−3 |
a = 7.7733 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.8240 (5) Å | Cell parameters from 7985 reflections |
c = 10.4594 (7) Å | θ = 2.7–27.5° |
α = 86.085 (8)° | µ = 2.90 mm−1 |
β = 80.575 (7)° | T = 100 K |
γ = 71.308 (6)° | Plate, colourless |
V = 594.35 (7) Å3 | 0.17 × 0.10 × 0.02 mm |
Rigaku Mercury CCD diffractometer | 2640 reflections with I > 2σ(I) |
ω scans | Rint = 0.031 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2012) | θmax = 27.5°, θmin = 2.8° |
Tmin = 0.638, Tmax = 0.944 | h = −8→10 |
7837 measured reflections | k = −10→10 |
2739 independent reflections | l = −12→13 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.022 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0409P)2 + 0.1325P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
2739 reflections | Δρmax = 1.18 e Å−3 |
149 parameters | Δρmin = −0.44 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0847 (3) | 0.5746 (3) | 0.6457 (2) | 0.0165 (4) | |
C2 | −0.0166 (3) | 0.5738 (3) | 0.7698 (2) | 0.0190 (4) | |
H2 | −0.0956 | 0.6824 | 0.8097 | 0.023* | |
C3 | 0.0037 (3) | 0.4078 (3) | 0.8316 (2) | 0.0204 (4) | |
H3 | −0.0631 | 0.4013 | 0.9154 | 0.024* | |
C4 | 0.1227 (3) | 0.2486 (3) | 0.7712 (2) | 0.0185 (4) | |
C5 | 0.2249 (3) | 0.2468 (3) | 0.6505 (2) | 0.0176 (4) | |
H5 | 0.3045 | 0.1374 | 0.6122 | 0.021* | |
C6 | 0.2064 (3) | 0.4142 (3) | 0.5863 (2) | 0.0160 (4) | |
C7 | 0.2860 (3) | 0.4665 (3) | 0.46397 (19) | 0.0144 (4) | |
C8 | 0.2117 (3) | 0.6518 (3) | 0.45207 (19) | 0.0155 (4) | |
C9 | 0.2427 (3) | 0.7849 (3) | 0.3534 (2) | 0.0162 (4) | |
C10 | 0.4005 (3) | 0.8407 (3) | 0.1517 (2) | 0.0196 (4) | |
H10A | 0.4584 | 0.9185 | 0.1879 | 0.023* | |
H10B | 0.2863 | 0.9183 | 0.1211 | 0.023* | |
C11 | 0.5308 (3) | 0.7311 (3) | 0.0411 (2) | 0.0260 (5) | |
H11A | 0.5687 | 0.8125 | −0.0247 | 0.039* | |
H11B | 0.4686 | 0.6612 | 0.0024 | 0.039* | |
H11C | 0.6392 | 0.6488 | 0.0740 | 0.039* | |
N1 | 0.0899 (2) | 0.7153 (2) | 0.56278 (17) | 0.0159 (3) | |
H1 | 0.030 (4) | 0.814 (4) | 0.576 (3) | 0.019* | |
O1 | 0.3601 (2) | 0.71212 (19) | 0.24936 (14) | 0.0179 (3) | |
O2 | 0.1685 (2) | 0.9465 (2) | 0.36622 (16) | 0.0232 (3) | |
Cl1 | 0.14126 (8) | 0.04416 (8) | 0.85625 (5) | 0.02534 (12) | |
I1 | 0.48122 (2) | 0.28666 (2) | 0.33716 (2) | 0.01543 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0128 (9) | 0.0169 (9) | 0.0192 (10) | −0.0027 (7) | −0.0041 (7) | −0.0020 (8) |
C2 | 0.0143 (9) | 0.0213 (10) | 0.0191 (10) | −0.0020 (8) | −0.0017 (7) | −0.0036 (8) |
C3 | 0.0156 (9) | 0.0278 (11) | 0.0163 (10) | −0.0053 (8) | −0.0015 (7) | 0.0002 (8) |
C4 | 0.0171 (9) | 0.0168 (9) | 0.0207 (10) | −0.0044 (8) | −0.0049 (8) | 0.0049 (8) |
C5 | 0.0139 (9) | 0.0160 (9) | 0.0207 (10) | −0.0013 (8) | −0.0038 (7) | 0.0001 (8) |
C6 | 0.0135 (9) | 0.0170 (9) | 0.0168 (9) | −0.0027 (7) | −0.0038 (7) | −0.0015 (7) |
C7 | 0.0126 (8) | 0.0125 (8) | 0.0171 (9) | −0.0024 (7) | −0.0021 (7) | −0.0009 (7) |
C8 | 0.0129 (8) | 0.0163 (9) | 0.0169 (9) | −0.0031 (7) | −0.0033 (7) | −0.0016 (7) |
C9 | 0.0144 (9) | 0.0143 (9) | 0.0195 (10) | −0.0038 (7) | −0.0025 (7) | −0.0004 (7) |
C10 | 0.0222 (10) | 0.0162 (9) | 0.0197 (10) | −0.0068 (8) | −0.0013 (8) | 0.0043 (8) |
C11 | 0.0347 (12) | 0.0227 (11) | 0.0205 (11) | −0.0121 (10) | 0.0024 (9) | −0.0009 (8) |
N1 | 0.0139 (8) | 0.0129 (8) | 0.0186 (8) | −0.0010 (6) | −0.0016 (6) | −0.0018 (6) |
O1 | 0.0206 (7) | 0.0125 (6) | 0.0188 (7) | −0.0044 (6) | −0.0001 (6) | 0.0020 (5) |
O2 | 0.0240 (8) | 0.0135 (7) | 0.0268 (8) | −0.0018 (6) | 0.0023 (6) | −0.0001 (6) |
Cl1 | 0.0254 (3) | 0.0228 (3) | 0.0242 (3) | −0.0060 (2) | −0.0008 (2) | 0.0092 (2) |
I1 | 0.01470 (9) | 0.01248 (9) | 0.01706 (9) | −0.00172 (6) | −0.00130 (6) | −0.00153 (6) |
C1—N1 | 1.361 (3) | C7—I1 | 2.0660 (19) |
C1—C2 | 1.405 (3) | C8—N1 | 1.380 (3) |
C1—C6 | 1.417 (3) | C8—C9 | 1.463 (3) |
C2—C3 | 1.384 (3) | C9—O2 | 1.216 (3) |
C2—H2 | 0.9500 | C9—O1 | 1.330 (2) |
C3—C4 | 1.409 (3) | C10—O1 | 1.453 (2) |
C3—H3 | 0.9500 | C10—C11 | 1.515 (3) |
C4—C5 | 1.376 (3) | C10—H10A | 0.9900 |
C4—Cl1 | 1.752 (2) | C10—H10B | 0.9900 |
C5—C6 | 1.406 (3) | C11—H11A | 0.9800 |
C5—H5 | 0.9500 | C11—H11B | 0.9800 |
C6—C7 | 1.421 (3) | C11—H11C | 0.9800 |
C7—C8 | 1.383 (3) | N1—H1 | 0.77 (3) |
N1—C1—C2 | 129.80 (19) | N1—C8—C9 | 117.43 (17) |
N1—C1—C6 | 108.08 (18) | C7—C8—C9 | 133.80 (19) |
C2—C1—C6 | 122.11 (19) | O2—C9—O1 | 123.5 (2) |
C3—C2—C1 | 117.05 (19) | O2—C9—C8 | 122.96 (19) |
C3—C2—H2 | 121.5 | O1—C9—C8 | 113.50 (17) |
C1—C2—H2 | 121.5 | O1—C10—C11 | 106.61 (17) |
C2—C3—C4 | 120.58 (19) | O1—C10—H10A | 110.4 |
C2—C3—H3 | 119.7 | C11—C10—H10A | 110.4 |
C4—C3—H3 | 119.7 | O1—C10—H10B | 110.4 |
C5—C4—C3 | 123.23 (19) | C11—C10—H10B | 110.4 |
C5—C4—Cl1 | 119.08 (16) | H10A—C10—H10B | 108.6 |
C3—C4—Cl1 | 117.69 (16) | C10—C11—H11A | 109.5 |
C4—C5—C6 | 117.06 (19) | C10—C11—H11B | 109.5 |
C4—C5—H5 | 121.5 | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 121.5 | C10—C11—H11C | 109.5 |
C5—C6—C1 | 119.95 (19) | H11A—C11—H11C | 109.5 |
C5—C6—C7 | 133.51 (19) | H11B—C11—H11C | 109.5 |
C1—C6—C7 | 106.53 (18) | C1—N1—C8 | 109.37 (17) |
C8—C7—C6 | 107.32 (17) | C1—N1—H1 | 124 (2) |
C8—C7—I1 | 129.30 (15) | C8—N1—H1 | 127 (2) |
C6—C7—I1 | 123.36 (14) | C9—O1—C10 | 115.06 (16) |
N1—C8—C7 | 108.70 (18) | ||
N1—C1—C2—C3 | 179.0 (2) | C1—C6—C7—I1 | 178.14 (13) |
C6—C1—C2—C3 | −1.6 (3) | C6—C7—C8—N1 | 0.2 (2) |
C1—C2—C3—C4 | 0.5 (3) | I1—C7—C8—N1 | −178.26 (13) |
C2—C3—C4—C5 | 0.4 (3) | C6—C7—C8—C9 | 176.9 (2) |
C2—C3—C4—Cl1 | 179.75 (16) | I1—C7—C8—C9 | −1.5 (3) |
C3—C4—C5—C6 | −0.2 (3) | N1—C8—C9—O2 | 1.2 (3) |
Cl1—C4—C5—C6 | −179.59 (15) | C7—C8—C9—O2 | −175.3 (2) |
C4—C5—C6—C1 | −0.8 (3) | N1—C8—C9—O1 | −179.20 (16) |
C4—C5—C6—C7 | −179.7 (2) | C7—C8—C9—O1 | 4.3 (3) |
N1—C1—C6—C5 | −178.72 (18) | C2—C1—N1—C8 | 179.1 (2) |
C2—C1—C6—C5 | 1.7 (3) | C6—C1—N1—C8 | −0.4 (2) |
N1—C1—C6—C7 | 0.5 (2) | C7—C8—N1—C1 | 0.1 (2) |
C2—C1—C6—C7 | −179.05 (18) | C9—C8—N1—C1 | −177.20 (17) |
C5—C6—C7—C8 | 178.7 (2) | O2—C9—O1—C10 | 2.2 (3) |
C1—C6—C7—C8 | −0.4 (2) | C8—C9—O1—C10 | −177.42 (16) |
C5—C6—C7—I1 | −2.8 (3) | C11—C10—O1—C9 | −178.33 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.77 (3) | 2.06 (3) | 2.821 (2) | 168 (3) |
Symmetry code: (i) −x, −y+2, −z+1. |
Acknowledgements
We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National
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