Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032370/bt2427sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032370/bt2427Isup2.hkl |
CCDC reference: 657691
2-Iodo-5-bromoaniline (596 mg, 2.55 mmol) was added to DCM (5 ml) with triethylamine (0.7 ml, 5 mmol), and the mixture stirred magnetically whilst chilled in an ice bath. Once cool, cyclopentane carbonyl chloride (0.4 ml, 3 mmol) was added dropwise, and the mixture stirred for 2 hr during which time a precipitate was produced. Water (10 ml) was added to the flask, then the DCM layer was separated and washed with saturated sodium hydrogen carbonate (15 ml) and brine (15 ml), during which time the mixture emulsified. The DCM layer was filtered to yield a pure white filtrate and a yellow liquor which was dried (MgSO4), and the solvent removed to yield colourless plates of cyclopentanecarboxylic acid (5-bromo-2-iodo-phenyl)-amide, (III).
Compound (III) (750 mg, 1.8 mmol) was dissolved in dry THF (10 ml), then injected into a pre-dried flask containing sodium hydride (40 mg, 1.8 mmol) in dry THF (10 ml) and the mixture stirred magnetically. When bubbling of the mixture ceased, methyl iodide (0.12 ml, 1.98 mmol) was added and the reaction left stirring overnight. Ammonium carbonate solution (10 ml) was then added and the mixture allowed to stir for 10 min, during which time a white precipitate formed which redissolved on the addition of water (15 ml). An extraction was performed into ethyl acetate (3 × 20 ml). Purification by flash column chromatography (10:1 v/v hexane:ethyl acetate) yielded 385 mg (51%) of the title compound with Rf = 0.20. Recrystallization from ethyl acetate afforded colourless prisms of (I).
The disordered atoms were refined isotropically. The hydrogen atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The highest difference peak is 1.20Å from H25A and the deepest difference hole is 0.84Å from I1.
The title compound, (I), complements the recently reported cyclohexanecarboxylic acid (5-bromo-2-iodo-phenyl)-methyl-amide, (II), (Slawin et al., 2007), with a cyclopentane ring in (I) replacing a cyclohexane ring in (II).
There are two molecules in the asymmetric unit of (I) and their geometrical parameters fall within the expected ranges, allowing for the uncertainties arising from the disordered cyclopentane rings (Allen et al., 1995).
For the first (C1) molecule, the dihedral angle between the mean planes of the aromatic ring and the methylated amide (C7/C8/N1/O1) group is 85.4 (2)°. A dihedral angle of 82.35 (17)° occurs for the equivalent atoms in the second (C14) molecule. In both molecules the methyl C atom and the O atom of the amide are in cis conformation.
In the crystal, the molecules of (I) form dimers (Fig. 1) by way of two very short C—I···O interactions (Allen et al., 1997; Glidewell et al., 2005) with the iodine···oxygen separations for C1—I1···O2 and C14—I2···O1 being 3.044 (4)Å and 2.998 (4) Å, respectively. The Bondi (1964) van der Waals' separation for I and O is 3.50 Å. The C1—I1···O2 and C14—I2···O1 angles are 171.12 (14)° and 174.44 (14), respectively.
A dimerization of the two asymmetric molecules via two very short C—I···O interactions [I···O = 3.038 (4) and 3.082 (4) Å]. also occurs in (II) (Slawin et al., 2007).
For a related structure, see Slawin et al. (2007). For background on C—I···O interactions, see: Allen et al. (1997); Glidewell et al. (2005). For crystallographic reference data, see: Bondi (1964); Allen et al. (1995).
Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C13H15BrINO | V = 1423.6 (4) Å3 |
Mr = 408.07 | Z = 4 |
Triclinic, P1 | F(000) = 784 |
Hall symbol: -P 1 | Dx = 1.904 Mg m−3 |
a = 9.0116 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.8073 (18) Å | µ = 5.04 mm−1 |
c = 13.697 (2) Å | T = 93 K |
α = 86.430 (12)° | Block, colourless |
β = 85.395 (13)° | 0.30 × 0.20 × 0.10 mm |
γ = 78.849 (11)° |
Rigaku Mercury CCD diffractometer | 5099 independent reflections |
Radiation source: rotating anode | 4616 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.033 |
ω and φ scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | h = −9→11 |
Tmin = 0.313, Tmax = 0.633 | k = −14→14 |
9341 measured reflections | l = −13→16 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0565P)2 + 4.5633P] where P = (Fo2 + 2Fc2)/3 |
5099 reflections | (Δ/σ)max = 0.002 |
305 parameters | Δρmax = 1.28 e Å−3 |
0 restraints | Δρmin = −1.51 e Å−3 |
C13H15BrINO | γ = 78.849 (11)° |
Mr = 408.07 | V = 1423.6 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.0116 (14) Å | Mo Kα radiation |
b = 11.8073 (18) Å | µ = 5.04 mm−1 |
c = 13.697 (2) Å | T = 93 K |
α = 86.430 (12)° | 0.30 × 0.20 × 0.10 mm |
β = 85.395 (13)° |
Rigaku Mercury CCD diffractometer | 5099 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | 4616 reflections with I > 2σ(I) |
Tmin = 0.313, Tmax = 0.633 | Rint = 0.033 |
9341 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.28 e Å−3 |
5099 reflections | Δρmin = −1.51 e Å−3 |
305 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 1.1153 (5) | −0.1887 (4) | 0.2547 (3) | 0.0124 (9) | |
C2 | 1.2706 (5) | −0.2157 (4) | 0.2354 (4) | 0.0161 (10) | |
H2 | 1.3310 | −0.1606 | 0.2462 | 0.019* | |
C3 | 1.3396 (5) | −0.3226 (4) | 0.2003 (3) | 0.0160 (10) | |
H3 | 1.4463 | −0.3408 | 0.1868 | 0.019* | |
C4 | 1.2494 (5) | −0.4020 (4) | 0.1854 (3) | 0.0132 (9) | |
C5 | 1.0937 (5) | −0.3760 (4) | 0.2046 (3) | 0.0121 (9) | |
H5 | 1.0338 | −0.4317 | 0.1945 | 0.015* | |
C6 | 1.0248 (5) | −0.2686 (4) | 0.2387 (3) | 0.0115 (9) | |
C7 | 0.8129 (6) | −0.2720 (5) | 0.3635 (4) | 0.0272 (12) | |
H7A | 0.9010 | −0.2976 | 0.4023 | 0.041* | |
H7B | 0.7536 | −0.3335 | 0.3650 | 0.041* | |
H7C | 0.7497 | −0.2027 | 0.3910 | 0.041* | |
C8 | 0.7602 (5) | −0.2074 (4) | 0.1952 (4) | 0.0161 (10) | |
C9 | 0.8155 (6) | −0.1777 (5) | 0.0919 (4) | 0.0285 (12) | |
H9 | 0.9286 | −0.1913 | 0.0913 | 0.034* | |
C10 | 0.7655 (14) | −0.0507 (6) | 0.0590 (6) | 0.086 (4) | |
H10A | 0.6569 | −0.0246 | 0.0793 | 0.103* | |
H10B | 0.8246 | −0.0026 | 0.0908 | 0.103* | |
C11 | 0.787 (2) | −0.0374 (16) | −0.0402 (13) | 0.058 (5)* | 0.54 (2) |
H11A | 0.8888 | −0.0190 | −0.0589 | 0.069* | 0.54 (2) |
H11B | 0.7094 | 0.0256 | −0.0663 | 0.069* | 0.54 (2) |
C12 | 0.773 (2) | −0.1645 (12) | −0.0832 (10) | 0.042 (4)* | 0.54 (2) |
H12A | 0.6762 | −0.1593 | −0.1138 | 0.051* | 0.54 (2) |
H12B | 0.8583 | −0.1915 | −0.1317 | 0.051* | 0.54 (2) |
C13 | 0.7807 (15) | −0.2456 (8) | 0.0118 (7) | 0.018 (3)* | 0.54 (2) |
H13A | 0.6825 | −0.2706 | 0.0277 | 0.022* | 0.54 (2) |
H13B | 0.8608 | −0.3151 | 0.0025 | 0.022* | 0.54 (2) |
C11A | 0.748 (2) | −0.0505 (15) | −0.0543 (13) | 0.042 (4)* | 0.46 (2) |
H11C | 0.6714 | 0.0165 | −0.0759 | 0.051* | 0.46 (2) |
H11D | 0.8456 | −0.0482 | −0.0922 | 0.051* | 0.46 (2) |
C12A | 0.704 (3) | −0.1467 (18) | −0.0650 (16) | 0.063 (6)* | 0.46 (2) |
H12C | 0.7723 | −0.1910 | −0.1152 | 0.075* | 0.46 (2) |
H12D | 0.6005 | −0.1296 | −0.0888 | 0.075* | 0.46 (2) |
C13A | 0.702 (3) | −0.2148 (16) | 0.0228 (12) | 0.045 (5)* | 0.46 (2) |
H13C | 0.7340 | −0.2977 | 0.0090 | 0.054* | 0.46 (2) |
H13D | 0.5984 | −0.2030 | 0.0552 | 0.054* | 0.46 (2) |
N1 | 0.8644 (4) | −0.2453 (3) | 0.2616 (3) | 0.0134 (8) | |
O1 | 0.6240 (4) | −0.1954 (3) | 0.2193 (3) | 0.0228 (8) | |
Br1 | 1.33872 (5) | −0.54869 (4) | 0.13779 (3) | 0.01845 (13) | |
I1 | 1.01734 (3) | −0.02584 (2) | 0.30608 (2) | 0.01834 (11) | |
C14 | 0.4091 (5) | 0.1964 (4) | 0.3579 (3) | 0.0116 (9) | |
C15 | 0.2554 (5) | 0.2366 (4) | 0.3541 (3) | 0.0132 (9) | |
H15 | 0.1942 | 0.1892 | 0.3296 | 0.016* | |
C16 | 0.1887 (5) | 0.3460 (4) | 0.3858 (3) | 0.0148 (9) | |
H16 | 0.0826 | 0.3734 | 0.3837 | 0.018* | |
C17 | 0.2814 (5) | 0.4141 (4) | 0.4205 (3) | 0.0105 (9) | |
C18 | 0.4349 (5) | 0.3751 (4) | 0.4247 (3) | 0.0111 (9) | |
H18 | 0.4959 | 0.4227 | 0.4491 | 0.013* | |
C19 | 0.5009 (5) | 0.2656 (4) | 0.3930 (3) | 0.0115 (9) | |
C20 | 0.7014 (6) | 0.1548 (4) | 0.4922 (4) | 0.0197 (10) | |
H20A | 0.6094 | 0.1398 | 0.5298 | 0.030* | |
H20B | 0.7564 | 0.1966 | 0.5321 | 0.030* | |
H20C | 0.7661 | 0.0813 | 0.4745 | 0.030* | |
C21 | 0.7703 (5) | 0.2563 (4) | 0.3387 (3) | 0.0137 (9) | |
C22 | 0.7215 (5) | 0.3257 (4) | 0.2463 (4) | 0.0177 (10) | |
H22 | 0.6125 | 0.3639 | 0.2557 | 0.021* | |
C23 | 0.8186 (10) | 0.4167 (6) | 0.2159 (5) | 0.059 (2) | |
H23A | 0.7582 | 0.4958 | 0.2221 | 0.071* | |
H23B | 0.9065 | 0.4074 | 0.2566 | 0.071* | |
C24A | 0.870 (2) | 0.3936 (16) | 0.1089 (11) | 0.038 (5)* | 0.41 (2) |
H24A | 0.8656 | 0.4677 | 0.0701 | 0.045* | 0.41 (2) |
H24B | 0.9766 | 0.3510 | 0.1041 | 0.045* | 0.41 (2) |
C24B | 0.7931 (14) | 0.4481 (10) | 0.1136 (7) | 0.031 (3)* | 0.59 (2) |
H24C | 0.8806 | 0.4769 | 0.0795 | 0.038* | 0.59 (2) |
H24D | 0.7003 | 0.5077 | 0.1070 | 0.038* | 0.59 (2) |
C25 | 0.7743 (9) | 0.3274 (7) | 0.0718 (5) | 0.0525 (18) | |
H25A | 0.8259 | 0.2816 | 0.0164 | 0.063* | |
H25B | 0.6797 | 0.3768 | 0.0503 | 0.063* | |
C26 | 0.7441 (10) | 0.2519 (6) | 0.1590 (4) | 0.055 (2) | |
H26A | 0.8308 | 0.1871 | 0.1667 | 0.066* | |
H26B | 0.6522 | 0.2197 | 0.1519 | 0.066* | |
N2 | 0.6596 (4) | 0.2249 (3) | 0.4027 (3) | 0.0113 (8) | |
O2 | 0.9042 (4) | 0.2256 (3) | 0.3547 (3) | 0.0205 (7) | |
Br2 | 0.19457 (5) | 0.56264 (4) | 0.46655 (3) | 0.01497 (13) | |
I2 | 0.50529 (3) | 0.03337 (2) | 0.30769 (2) | 0.01627 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.011 (2) | 0.0097 (19) | 0.015 (2) | 0.0024 (17) | −0.0031 (18) | 0.0017 (17) |
C2 | 0.012 (2) | 0.016 (2) | 0.021 (2) | −0.0048 (19) | −0.0006 (19) | −0.0012 (19) |
C3 | 0.010 (2) | 0.019 (2) | 0.019 (2) | −0.0029 (19) | −0.0014 (19) | −0.0002 (19) |
C4 | 0.015 (2) | 0.012 (2) | 0.012 (2) | −0.0010 (18) | −0.0008 (18) | −0.0021 (17) |
C5 | 0.010 (2) | 0.015 (2) | 0.012 (2) | −0.0055 (18) | −0.0017 (18) | 0.0001 (17) |
C6 | 0.010 (2) | 0.016 (2) | 0.008 (2) | −0.0016 (17) | −0.0004 (17) | 0.0027 (17) |
C7 | 0.021 (3) | 0.035 (3) | 0.020 (3) | 0.003 (2) | 0.006 (2) | 0.012 (2) |
C8 | 0.011 (3) | 0.016 (2) | 0.022 (2) | −0.0010 (18) | −0.006 (2) | −0.0051 (19) |
C9 | 0.017 (3) | 0.050 (3) | 0.014 (2) | 0.007 (2) | −0.004 (2) | −0.006 (2) |
C10 | 0.183 (11) | 0.039 (4) | 0.042 (4) | −0.056 (6) | 0.039 (6) | −0.013 (3) |
N1 | 0.0090 (19) | 0.0192 (19) | 0.0115 (19) | −0.0042 (15) | 0.0019 (15) | 0.0050 (15) |
O1 | 0.0085 (18) | 0.0267 (18) | 0.034 (2) | −0.0042 (14) | −0.0009 (15) | −0.0075 (16) |
Br1 | 0.0197 (3) | 0.0146 (2) | 0.0195 (3) | 0.00165 (19) | −0.0020 (2) | −0.00340 (18) |
I1 | 0.01572 (19) | 0.01515 (17) | 0.02395 (19) | −0.00073 (13) | −0.00382 (13) | −0.00309 (12) |
C14 | 0.011 (2) | 0.012 (2) | 0.011 (2) | −0.0020 (17) | 0.0024 (18) | 0.0001 (17) |
C15 | 0.011 (2) | 0.016 (2) | 0.014 (2) | −0.0075 (18) | 0.0018 (18) | −0.0025 (18) |
C16 | 0.008 (2) | 0.024 (2) | 0.013 (2) | −0.0030 (18) | 0.0013 (18) | 0.0006 (18) |
C17 | 0.010 (2) | 0.014 (2) | 0.006 (2) | −0.0004 (17) | 0.0021 (17) | 0.0011 (16) |
C18 | 0.009 (2) | 0.015 (2) | 0.010 (2) | −0.0051 (18) | −0.0003 (17) | −0.0005 (17) |
C19 | 0.011 (2) | 0.016 (2) | 0.008 (2) | −0.0048 (18) | 0.0004 (17) | 0.0015 (17) |
C20 | 0.020 (3) | 0.023 (2) | 0.017 (2) | −0.005 (2) | −0.008 (2) | 0.006 (2) |
C21 | 0.009 (2) | 0.014 (2) | 0.019 (2) | −0.0034 (18) | 0.0004 (19) | −0.0053 (18) |
C22 | 0.012 (2) | 0.021 (2) | 0.019 (2) | −0.0021 (19) | 0.0021 (19) | 0.0022 (19) |
C23 | 0.097 (6) | 0.047 (4) | 0.051 (4) | −0.051 (4) | −0.024 (4) | 0.012 (3) |
C25 | 0.061 (5) | 0.063 (5) | 0.029 (4) | −0.007 (4) | 0.007 (3) | 0.001 (3) |
C26 | 0.106 (6) | 0.033 (3) | 0.022 (3) | 0.004 (4) | −0.019 (4) | −0.003 (3) |
N2 | 0.0058 (19) | 0.0151 (18) | 0.0124 (18) | −0.0011 (15) | −0.0011 (15) | 0.0016 (15) |
O2 | 0.0095 (17) | 0.0194 (17) | 0.033 (2) | −0.0031 (13) | −0.0052 (15) | −0.0016 (15) |
Br2 | 0.0117 (3) | 0.0145 (2) | 0.0182 (2) | 0.00015 (18) | −0.00163 (19) | −0.00392 (18) |
I2 | 0.01425 (19) | 0.01533 (16) | 0.02016 (18) | −0.00486 (12) | −0.00063 (13) | −0.00245 (12) |
C1—C2 | 1.382 (7) | C12A—H12D | 0.9900 |
C1—C6 | 1.398 (6) | C13A—H13C | 0.9900 |
C1—I1 | 2.093 (4) | C13A—H13D | 0.9900 |
C2—C3 | 1.391 (7) | C14—C15 | 1.379 (6) |
C2—H2 | 0.9500 | C14—C19 | 1.399 (6) |
C3—C4 | 1.388 (6) | C14—I2 | 2.086 (4) |
C3—H3 | 0.9500 | C15—C16 | 1.395 (6) |
C4—C5 | 1.384 (7) | C15—H15 | 0.9500 |
C4—Br1 | 1.895 (4) | C16—C17 | 1.394 (6) |
C5—C6 | 1.391 (6) | C16—H16 | 0.9500 |
C5—H5 | 0.9500 | C17—C18 | 1.375 (6) |
C6—N1 | 1.431 (6) | C17—Br2 | 1.901 (4) |
C7—N1 | 1.470 (6) | C18—C19 | 1.394 (6) |
C7—H7A | 0.9800 | C18—H18 | 0.9500 |
C7—H7B | 0.9800 | C19—N2 | 1.432 (6) |
C7—H7C | 0.9800 | C20—N2 | 1.469 (6) |
C8—O1 | 1.228 (6) | C20—H20A | 0.9800 |
C8—N1 | 1.353 (6) | C20—H20B | 0.9800 |
C8—C9 | 1.506 (7) | C20—H20C | 0.9800 |
C9—C13 | 1.486 (10) | C21—O2 | 1.225 (6) |
C9—C10 | 1.530 (10) | C21—N2 | 1.365 (6) |
C9—C13A | 1.586 (17) | C21—C22 | 1.512 (6) |
C9—H9 | 1.0000 | C22—C26 | 1.501 (8) |
C10—C11 | 1.361 (19) | C22—C23 | 1.531 (7) |
C10—C11A | 1.57 (2) | C22—H22 | 1.0000 |
C10—H10A | 0.9900 | C23—C24B | 1.451 (12) |
C10—H10B | 0.9900 | C23—C24A | 1.527 (18) |
C11—C12 | 1.68 (2) | C23—H23A | 0.9900 |
C11—H11A | 0.9900 | C23—H23B | 0.9900 |
C11—H11B | 0.9900 | C24A—C25 | 1.415 (16) |
C12—C13 | 1.565 (16) | C24A—H24A | 0.9900 |
C12—H12A | 0.9900 | C24A—H24B | 0.9900 |
C12—H12B | 0.9900 | C24B—C25 | 1.612 (13) |
C13—H13A | 0.9900 | C24B—H24C | 0.9900 |
C13—H13B | 0.9900 | C24B—H24D | 0.9900 |
C11A—C12A | 1.29 (3) | C25—C26 | 1.485 (9) |
C11A—H11C | 0.9900 | C25—H25A | 0.9900 |
C11A—H11D | 0.9900 | C25—H25B | 0.9900 |
C12A—C13A | 1.40 (2) | C26—H26A | 0.9900 |
C12A—H12C | 0.9900 | C26—H26B | 0.9900 |
C2—C1—C6 | 120.3 (4) | C12A—C13A—H13D | 110.1 |
C2—C1—I1 | 119.1 (3) | C9—C13A—H13D | 110.1 |
C6—C1—I1 | 120.6 (3) | H13C—C13A—H13D | 108.4 |
C1—C2—C3 | 120.8 (4) | C8—N1—C6 | 124.5 (4) |
C1—C2—H2 | 119.6 | C8—N1—C7 | 119.2 (4) |
C3—C2—H2 | 119.6 | C6—N1—C7 | 116.2 (4) |
C4—C3—C2 | 118.7 (4) | C15—C14—C19 | 120.2 (4) |
C4—C3—H3 | 120.6 | C15—C14—I2 | 119.7 (3) |
C2—C3—H3 | 120.6 | C19—C14—I2 | 120.1 (3) |
C5—C4—C3 | 121.1 (4) | C14—C15—C16 | 120.8 (4) |
C5—C4—Br1 | 118.8 (3) | C14—C15—H15 | 119.6 |
C3—C4—Br1 | 120.1 (3) | C16—C15—H15 | 119.6 |
C4—C5—C6 | 120.1 (4) | C17—C16—C15 | 118.4 (4) |
C4—C5—H5 | 120.0 | C17—C16—H16 | 120.8 |
C6—C5—H5 | 120.0 | C15—C16—H16 | 120.8 |
C5—C6—C1 | 119.0 (4) | C18—C17—C16 | 121.4 (4) |
C5—C6—N1 | 119.1 (4) | C18—C17—Br2 | 118.8 (3) |
C1—C6—N1 | 121.7 (4) | C16—C17—Br2 | 119.7 (3) |
N1—C7—H7A | 109.5 | C17—C18—C19 | 120.0 (4) |
N1—C7—H7B | 109.5 | C17—C18—H18 | 120.0 |
H7A—C7—H7B | 109.5 | C19—C18—H18 | 120.0 |
N1—C7—H7C | 109.5 | C18—C19—C14 | 119.2 (4) |
H7A—C7—H7C | 109.5 | C18—C19—N2 | 118.8 (4) |
H7B—C7—H7C | 109.5 | C14—C19—N2 | 121.9 (4) |
O1—C8—N1 | 120.8 (4) | N2—C20—H20A | 109.5 |
O1—C8—C9 | 120.9 (4) | N2—C20—H20B | 109.5 |
N1—C8—C9 | 118.3 (4) | H20A—C20—H20B | 109.5 |
C13—C9—C8 | 118.1 (6) | N2—C20—H20C | 109.5 |
C13—C9—C10 | 105.8 (6) | H20A—C20—H20C | 109.5 |
C8—C9—C10 | 114.2 (5) | H20B—C20—H20C | 109.5 |
C13—C9—C13A | 27.6 (6) | O2—C21—N2 | 120.5 (4) |
C8—C9—C13A | 106.1 (7) | O2—C21—C22 | 121.8 (4) |
C10—C9—C13A | 90.8 (8) | N2—C21—C22 | 117.6 (4) |
C13—C9—H9 | 106.0 | C26—C22—C21 | 111.8 (4) |
C8—C9—H9 | 106.0 | C26—C22—C23 | 102.9 (5) |
C10—C9—H9 | 106.0 | C21—C22—C23 | 112.6 (4) |
C13A—C9—H9 | 133.2 | C26—C22—H22 | 109.8 |
C11—C10—C9 | 110.0 (9) | C21—C22—H22 | 109.8 |
C11—C10—C11A | 16.7 (10) | C23—C22—H22 | 109.8 |
C9—C10—C11A | 105.5 (8) | C24B—C23—C24A | 33.2 (7) |
C11—C10—H10A | 109.7 | C24B—C23—C22 | 105.7 (6) |
C9—C10—H10A | 109.7 | C24A—C23—C22 | 104.0 (7) |
C11A—C10—H10A | 97.3 | C24B—C23—H23A | 80.0 |
C11—C10—H10B | 109.7 | C24A—C23—H23A | 110.9 |
C9—C10—H10B | 109.7 | C22—C23—H23A | 110.9 |
C11A—C10—H10B | 125.4 | C24B—C23—H23B | 135.2 |
H10A—C10—H10B | 108.2 | C24A—C23—H23B | 110.9 |
C10—C11—C12 | 105.3 (12) | C22—C23—H23B | 110.9 |
C10—C11—H11A | 110.7 | H23A—C23—H23B | 109.0 |
C12—C11—H11A | 110.7 | C25—C24A—C23 | 108.7 (11) |
C10—C11—H11B | 110.7 | C25—C24A—H24A | 110.0 |
C12—C11—H11B | 110.7 | C23—C24A—H24A | 110.0 |
H11A—C11—H11B | 108.8 | C25—C24A—H24B | 110.0 |
C13—C12—C11 | 102.4 (10) | C23—C24A—H24B | 110.0 |
C13—C12—H12A | 111.3 | H24A—C24A—H24B | 108.3 |
C11—C12—H12A | 111.3 | C23—C24B—C25 | 102.5 (7) |
C13—C12—H12B | 111.3 | C23—C24B—H24C | 111.3 |
C11—C12—H12B | 111.3 | C25—C24B—H24C | 111.3 |
H12A—C12—H12B | 109.2 | C23—C24B—H24D | 111.3 |
C9—C13—C12 | 106.7 (7) | C25—C24B—H24D | 111.3 |
C9—C13—H13A | 110.4 | H24C—C24B—H24D | 109.2 |
C12—C13—H13A | 110.4 | C24A—C25—C26 | 101.4 (8) |
C9—C13—H13B | 110.4 | C24A—C25—C24B | 31.9 (7) |
C12—C13—H13B | 110.4 | C26—C25—C24B | 105.9 (6) |
H13A—C13—H13B | 108.6 | C24A—C25—H25A | 111.5 |
C12A—C11A—C10 | 103.7 (15) | C26—C25—H25A | 111.5 |
C12A—C11A—H11C | 111.0 | C24B—C25—H25A | 133.1 |
C10—C11A—H11C | 111.0 | C24A—C25—H25B | 111.5 |
C12A—C11A—H11D | 111.0 | C26—C25—H25B | 111.5 |
C10—C11A—H11D | 111.0 | C24B—C25—H25B | 80.8 |
H11C—C11A—H11D | 109.0 | H25A—C25—H25B | 109.3 |
C11A—C12A—C13A | 112.4 (18) | C25—C26—C22 | 106.9 (5) |
C11A—C12A—H12C | 109.1 | C25—C26—H26A | 110.3 |
C13A—C12A—H12C | 109.1 | C22—C26—H26A | 110.3 |
C11A—C12A—H12D | 109.1 | C25—C26—H26B | 110.3 |
C13A—C12A—H12D | 109.1 | C22—C26—H26B | 110.3 |
H12C—C12A—H12D | 107.9 | H26A—C26—H26B | 108.6 |
C12A—C13A—C9 | 108.1 (13) | C21—N2—C19 | 123.6 (4) |
C12A—C13A—H13C | 110.1 | C21—N2—C20 | 119.8 (4) |
C9—C13A—H13C | 110.1 | C19—N2—C20 | 116.4 (3) |
C6—C1—C2—C3 | −0.3 (7) | C1—C6—N1—C8 | 98.8 (5) |
I1—C1—C2—C3 | −179.4 (3) | C5—C6—N1—C7 | 91.4 (5) |
C1—C2—C3—C4 | −0.3 (7) | C1—C6—N1—C7 | −85.1 (5) |
C2—C3—C4—C5 | 0.2 (7) | C19—C14—C15—C16 | −0.5 (7) |
C2—C3—C4—Br1 | −179.9 (3) | I2—C14—C15—C16 | −179.0 (3) |
C3—C4—C5—C6 | 0.5 (7) | C14—C15—C16—C17 | 0.6 (7) |
Br1—C4—C5—C6 | −179.4 (3) | C15—C16—C17—C18 | −0.6 (7) |
C4—C5—C6—C1 | −1.1 (7) | C15—C16—C17—Br2 | −178.9 (3) |
C4—C5—C6—N1 | −177.7 (4) | C16—C17—C18—C19 | 0.5 (6) |
C2—C1—C6—C5 | 1.0 (7) | Br2—C17—C18—C19 | 178.8 (3) |
I1—C1—C6—C5 | −180.0 (3) | C17—C18—C19—C14 | −0.4 (6) |
C2—C1—C6—N1 | 177.5 (4) | C17—C18—C19—N2 | −176.9 (4) |
I1—C1—C6—N1 | −3.5 (6) | C15—C14—C19—C18 | 0.4 (6) |
O1—C8—C9—C13 | −63.9 (8) | I2—C14—C19—C18 | 178.9 (3) |
N1—C8—C9—C13 | 117.6 (7) | C15—C14—C19—N2 | 176.8 (4) |
O1—C8—C9—C10 | 61.4 (8) | I2—C14—C19—N2 | −4.6 (6) |
N1—C8—C9—C10 | −117.2 (7) | O2—C21—C22—C26 | 76.3 (6) |
O1—C8—C9—C13A | −37.0 (10) | N2—C21—C22—C26 | −101.3 (6) |
N1—C8—C9—C13A | 144.5 (9) | O2—C21—C22—C23 | −39.1 (7) |
C13—C9—C10—C11 | −33.6 (13) | N2—C21—C22—C23 | 143.3 (5) |
C8—C9—C10—C11 | −165.1 (12) | C26—C22—C23—C24B | 41.2 (9) |
C13A—C9—C10—C11 | −57.1 (13) | C21—C22—C23—C24B | 161.8 (7) |
C13—C9—C10—C11A | −16.7 (11) | C26—C22—C23—C24A | 6.8 (10) |
C8—C9—C10—C11A | −148.2 (9) | C21—C22—C23—C24A | 127.5 (9) |
C13A—C9—C10—C11A | −40.2 (12) | C24B—C23—C24A—C25 | −78.8 (15) |
C9—C10—C11—C12 | 28.0 (16) | C22—C23—C24A—C25 | 18.5 (15) |
C11A—C10—C11—C12 | −49 (4) | C24A—C23—C24B—C25 | 56.7 (12) |
C10—C11—C12—C13 | −13.1 (16) | C22—C23—C24B—C25 | −35.1 (9) |
C8—C9—C13—C12 | 151.9 (8) | C23—C24A—C25—C26 | −35.9 (14) |
C10—C9—C13—C12 | 22.5 (10) | C23—C24A—C25—C24B | 66.1 (14) |
C13A—C9—C13—C12 | 82.0 (16) | C23—C24B—C25—C24A | −69.0 (14) |
C11—C12—C13—C9 | −6.8 (13) | C23—C24B—C25—C26 | 16.9 (10) |
C11—C10—C11A—C12A | 141 (5) | C24A—C25—C26—C22 | 40.7 (11) |
C9—C10—C11A—C12A | 32.5 (18) | C24B—C25—C26—C22 | 8.2 (9) |
C10—C11A—C12A—C13A | −5 (2) | C21—C22—C26—C25 | −150.2 (5) |
C11A—C12A—C13A—C9 | −23 (2) | C23—C22—C26—C25 | −29.0 (8) |
C13—C9—C13A—C12A | −85.2 (19) | O2—C21—N2—C19 | 174.5 (4) |
C8—C9—C13A—C12A | 154.3 (13) | C22—C21—N2—C19 | −7.9 (6) |
C10—C9—C13A—C12A | 38.8 (15) | O2—C21—N2—C20 | 0.7 (6) |
O1—C8—N1—C6 | 175.9 (4) | C22—C21—N2—C20 | 178.4 (4) |
C9—C8—N1—C6 | −5.6 (7) | C18—C19—N2—C21 | −80.3 (5) |
O1—C8—N1—C7 | −0.1 (7) | C14—C19—N2—C21 | 103.3 (5) |
C9—C8—N1—C7 | 178.5 (4) | C18—C19—N2—C20 | 93.7 (5) |
C5—C6—N1—C8 | −84.7 (6) | C14—C19—N2—C20 | −82.8 (5) |
Experimental details
Crystal data | |
Chemical formula | C13H15BrINO |
Mr | 408.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 93 |
a, b, c (Å) | 9.0116 (14), 11.8073 (18), 13.697 (2) |
α, β, γ (°) | 86.430 (12), 85.395 (13), 78.849 (11) |
V (Å3) | 1423.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.04 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2004) |
Tmin, Tmax | 0.313, 0.633 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9341, 5099, 4616 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.102, 1.02 |
No. of reflections | 5099 |
No. of parameters | 305 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.28, −1.51 |
Computer programs: CrystalClear (Rigaku, 2004), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
The title compound, (I), complements the recently reported cyclohexanecarboxylic acid (5-bromo-2-iodo-phenyl)-methyl-amide, (II), (Slawin et al., 2007), with a cyclopentane ring in (I) replacing a cyclohexane ring in (II).
There are two molecules in the asymmetric unit of (I) and their geometrical parameters fall within the expected ranges, allowing for the uncertainties arising from the disordered cyclopentane rings (Allen et al., 1995).
For the first (C1) molecule, the dihedral angle between the mean planes of the aromatic ring and the methylated amide (C7/C8/N1/O1) group is 85.4 (2)°. A dihedral angle of 82.35 (17)° occurs for the equivalent atoms in the second (C14) molecule. In both molecules the methyl C atom and the O atom of the amide are in cis conformation.
In the crystal, the molecules of (I) form dimers (Fig. 1) by way of two very short C—I···O interactions (Allen et al., 1997; Glidewell et al., 2005) with the iodine···oxygen separations for C1—I1···O2 and C14—I2···O1 being 3.044 (4)Å and 2.998 (4) Å, respectively. The Bondi (1964) van der Waals' separation for I and O is 3.50 Å. The C1—I1···O2 and C14—I2···O1 angles are 171.12 (14)° and 174.44 (14), respectively.
A dimerization of the two asymmetric molecules via two very short C—I···O interactions [I···O = 3.038 (4) and 3.082 (4) Å]. also occurs in (II) (Slawin et al., 2007).