Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107041546/bm3036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107041546/bm3036Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107041546/bm3036IIsup3.hkl |
CCDC references: 669176; 669177
For the synthesis of (I), chloral hydrate (16.5 g, 0.1 mol) and 4-methoxyaniline (0.2 mol) were mixed in ethyl acetate (25–30 ml) and heated until dissolution of the solid occurred. Cooling of the hot solution, followed by slow evaporation of the solvent at room temperature, yielded the crude product (yield 86%). Single crystals of (I) were obtained by recrystallization from CH2Cl2. Spectroscopic analysis: 1H NMR (DMSO, 400 MHz, δ, p.p.m.): 6.71 (m, 8H, 2Ar), 5.63 (d, J = 8.8 Hz, 2H, 2NH), 5.42 (t, J = 8.7 Hz, 1H, CH), 3.59 (s, 6H, 2CH3).
Compound (II) was synthesized by heating, with stirring, a mixture of chloral hydrate (16.5 g, 0.1 mol), freshly distilled 4-chloroaniline (0.2 mol) and ethyl acetate (25–30 ml) until dissolution of the solid occurred. Cooling of the hot solution and then slow evaporation of the solvent at room temperature yielded a crystalline product (yield 82%). Single crystals of (II) were obtained by recrystallization from hot DMSO. Spectroscopic analysis: 1H NMR (DMSO, 400 MHz, δ, p.p.m.): 6.93 (m, 8H, 2Ar), 6.32 (d, J = 8.4 Hz, 2H, 2NH), 5.73 (t, J = 8.4 Hz, 1H, CH).
H atoms were placed in idealized positions and allowed to ride on their respective parent atoms, with C—H = 0.98 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(carrier atom).
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
C16H17Cl3N2O2 | Dx = 1.438 Mg m−3 |
Mr = 375.67 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 5641 reflections |
a = 9.717 (2) Å | θ = 2.4–24.9° |
b = 10.575 (3) Å | µ = 0.54 mm−1 |
c = 33.772 (8) Å | T = 291 K |
V = 3470.3 (14) Å3 | Block, colourless |
Z = 8 | 0.38 × 0.29 × 0.25 mm |
F(000) = 1552 |
Nonius KappaCCD area-detector diffractometer | 3233 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.822, Tmax = 0.876 | k = −12→12 |
23826 measured reflections | l = −40→40 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0324P)2 + 3.5039P] where P = (Fo2 + 2Fc2)/3 |
3233 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C16H17Cl3N2O2 | V = 3470.3 (14) Å3 |
Mr = 375.67 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.717 (2) Å | µ = 0.54 mm−1 |
b = 10.575 (3) Å | T = 291 K |
c = 33.772 (8) Å | 0.38 × 0.29 × 0.25 mm |
Nonius KappaCCD area-detector diffractometer | 3233 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2571 reflections with I > 2σ(I) |
Tmin = 0.822, Tmax = 0.876 | Rint = 0.066 |
23826 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.36 e Å−3 |
3233 reflections | Δρmin = −0.39 e Å−3 |
210 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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.10056 (9) | 0.11368 (7) | 0.47142 (2) | 0.0566 (2) | |
Cl2 | 0.18966 (8) | 0.34925 (7) | 0.50681 (2) | 0.0508 (2) | |
Cl3 | 0.36487 (8) | 0.21912 (9) | 0.45195 (3) | 0.0651 (3) | |
O1 | −0.3595 (2) | 0.67992 (19) | 0.35315 (6) | 0.0534 (5) | |
O2 | 0.4760 (3) | 0.3681 (2) | 0.26119 (7) | 0.0859 (9) | |
N1 | 0.1410 (2) | 0.2639 (2) | 0.39127 (7) | 0.0449 (6) | |
H1D | 0.0904 | 0.1979 | 0.3882 | 0.054* | |
N2 | −0.0136 (2) | 0.3574 (2) | 0.43759 (7) | 0.0472 (6) | |
H2D | −0.0499 | 0.3204 | 0.4577 | 0.057* | |
C1 | 0.1277 (3) | 0.3321 (3) | 0.42794 (7) | 0.0390 (6) | |
H1 | 0.1761 | 0.4130 | 0.4253 | 0.047* | |
C2 | 0.1923 (3) | 0.2579 (3) | 0.46285 (8) | 0.0413 (6) | |
C3 | −0.0938 (3) | 0.4405 (2) | 0.41514 (7) | 0.0370 (6) | |
C4 | −0.2359 (3) | 0.4420 (3) | 0.42149 (7) | 0.0394 (6) | |
H4 | −0.2744 | 0.3873 | 0.4400 | 0.047* | |
C5 | −0.3196 (3) | 0.5231 (3) | 0.40079 (8) | 0.0424 (6) | |
H5 | −0.4138 | 0.5229 | 0.4056 | 0.051* | |
C6 | −0.2654 (3) | 0.6050 (2) | 0.37292 (8) | 0.0401 (6) | |
C7 | −0.1244 (3) | 0.6051 (3) | 0.36631 (9) | 0.0449 (7) | |
H7 | −0.0864 | 0.6602 | 0.3478 | 0.054* | |
C8 | −0.0400 (3) | 0.5228 (3) | 0.38728 (8) | 0.0436 (7) | |
H8 | 0.0543 | 0.5231 | 0.3825 | 0.052* | |
C9 | −0.3070 (4) | 0.7699 (3) | 0.32570 (10) | 0.0611 (9) | |
H9A | −0.2474 | 0.8280 | 0.3393 | 0.092* | |
H9B | −0.3820 | 0.8155 | 0.3139 | 0.092* | |
H9C | −0.2561 | 0.7269 | 0.3054 | 0.092* | |
C10 | 0.2297 (3) | 0.2963 (3) | 0.36023 (7) | 0.0390 (6) | |
C11 | 0.2102 (3) | 0.2366 (3) | 0.32402 (9) | 0.0568 (8) | |
H11 | 0.1395 | 0.1780 | 0.3213 | 0.068* | |
C12 | 0.2933 (4) | 0.2623 (3) | 0.29208 (9) | 0.0668 (10) | |
H12 | 0.2787 | 0.2201 | 0.2683 | 0.080* | |
C13 | 0.3983 (3) | 0.3501 (3) | 0.29492 (9) | 0.0534 (8) | |
C14 | 0.4200 (3) | 0.4092 (3) | 0.33029 (9) | 0.0490 (7) | |
H14 | 0.4908 | 0.4679 | 0.3328 | 0.059* | |
C15 | 0.3360 (3) | 0.3817 (3) | 0.36278 (9) | 0.0493 (7) | |
H15 | 0.3525 | 0.4223 | 0.3867 | 0.059* | |
C16 | 0.5531 (5) | 0.4790 (4) | 0.25775 (13) | 0.0967 (15) | |
H16A | 0.4940 | 0.5509 | 0.2614 | 0.145* | |
H16B | 0.5941 | 0.4828 | 0.2319 | 0.145* | |
H16C | 0.6241 | 0.4797 | 0.2775 | 0.145* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0679 (5) | 0.0386 (4) | 0.0633 (5) | −0.0023 (4) | −0.0127 (4) | 0.0072 (3) |
Cl2 | 0.0584 (4) | 0.0514 (4) | 0.0425 (4) | −0.0059 (3) | −0.0021 (3) | −0.0034 (3) |
Cl3 | 0.0420 (4) | 0.0849 (6) | 0.0686 (5) | 0.0206 (4) | −0.0057 (4) | −0.0013 (5) |
O1 | 0.0479 (12) | 0.0478 (12) | 0.0645 (13) | 0.0113 (10) | −0.0061 (10) | 0.0135 (10) |
O2 | 0.108 (2) | 0.0882 (19) | 0.0618 (16) | −0.0328 (17) | 0.0367 (14) | −0.0137 (13) |
N1 | 0.0440 (13) | 0.0482 (14) | 0.0426 (13) | −0.0119 (11) | 0.0007 (10) | −0.0031 (11) |
N2 | 0.0359 (13) | 0.0601 (15) | 0.0457 (13) | 0.0101 (11) | 0.0055 (10) | 0.0160 (12) |
C1 | 0.0363 (14) | 0.0417 (15) | 0.0391 (14) | 0.0016 (12) | −0.0006 (11) | 0.0015 (12) |
C2 | 0.0368 (14) | 0.0406 (15) | 0.0466 (15) | 0.0016 (12) | −0.0051 (12) | −0.0012 (12) |
C3 | 0.0387 (14) | 0.0363 (14) | 0.0361 (14) | 0.0037 (11) | −0.0022 (11) | 0.0008 (11) |
C4 | 0.0351 (14) | 0.0433 (15) | 0.0399 (14) | 0.0005 (12) | 0.0051 (12) | 0.0052 (12) |
C5 | 0.0324 (14) | 0.0486 (16) | 0.0462 (16) | 0.0046 (12) | 0.0032 (12) | −0.0006 (13) |
C6 | 0.0421 (15) | 0.0338 (14) | 0.0443 (15) | 0.0058 (12) | −0.0035 (12) | −0.0005 (12) |
C7 | 0.0441 (16) | 0.0397 (15) | 0.0509 (17) | −0.0031 (13) | 0.0016 (13) | 0.0080 (13) |
C8 | 0.0314 (14) | 0.0470 (16) | 0.0524 (17) | 0.0015 (12) | 0.0017 (12) | 0.0093 (13) |
C9 | 0.071 (2) | 0.0511 (19) | 0.061 (2) | 0.0108 (16) | −0.0066 (17) | 0.0149 (16) |
C10 | 0.0389 (15) | 0.0390 (14) | 0.0392 (14) | 0.0024 (12) | −0.0027 (11) | 0.0002 (12) |
C11 | 0.066 (2) | 0.0528 (18) | 0.0513 (18) | −0.0212 (16) | 0.0036 (15) | −0.0083 (15) |
C12 | 0.091 (3) | 0.066 (2) | 0.0430 (17) | −0.023 (2) | 0.0117 (17) | −0.0151 (16) |
C13 | 0.0590 (19) | 0.0536 (18) | 0.0476 (17) | −0.0063 (16) | 0.0130 (14) | −0.0011 (14) |
C14 | 0.0421 (16) | 0.0509 (17) | 0.0539 (18) | −0.0076 (14) | 0.0036 (14) | −0.0042 (14) |
C15 | 0.0443 (16) | 0.0583 (18) | 0.0451 (16) | −0.0064 (14) | 0.0035 (13) | −0.0125 (14) |
C16 | 0.118 (4) | 0.081 (3) | 0.091 (3) | −0.025 (3) | 0.045 (3) | 0.010 (2) |
Cl1—C2 | 1.790 (3) | C6—C7 | 1.388 (4) |
Cl2—C2 | 1.771 (3) | C7—C8 | 1.390 (4) |
Cl3—C2 | 1.765 (3) | C7—H7 | 0.9300 |
O1—C6 | 1.383 (3) | C8—H8 | 0.9300 |
O1—C9 | 1.423 (4) | C9—H9A | 0.9600 |
O2—C13 | 1.380 (3) | C9—H9B | 0.9600 |
O2—C16 | 1.396 (4) | C9—H9C | 0.9600 |
N1—C10 | 1.400 (3) | C10—C15 | 1.375 (4) |
N1—C1 | 1.439 (3) | C10—C11 | 1.389 (4) |
N1—H1D | 0.8600 | C11—C12 | 1.374 (4) |
N2—C3 | 1.397 (3) | C11—H11 | 0.9300 |
N2—C1 | 1.437 (3) | C12—C13 | 1.383 (4) |
N2—H2D | 0.8600 | C12—H12 | 0.9300 |
C1—C2 | 1.549 (4) | C13—C14 | 1.365 (4) |
C1—H1 | 0.9800 | C14—C15 | 1.398 (4) |
C3—C8 | 1.385 (4) | C14—H14 | 0.9300 |
C3—C4 | 1.398 (4) | C15—H15 | 0.9300 |
C4—C5 | 1.373 (4) | C16—H16A | 0.9600 |
C4—H4 | 0.9300 | C16—H16B | 0.9600 |
C5—C6 | 1.383 (4) | C16—H16C | 0.9600 |
C5—H5 | 0.9300 | ||
C6—O1—C9 | 117.4 (2) | C8—C7—H7 | 120.0 |
C13—O2—C16 | 118.6 (3) | C3—C8—C7 | 121.2 (2) |
C10—N1—C1 | 125.2 (2) | C3—C8—H8 | 119.4 |
C10—N1—H1D | 117.4 | C7—C8—H8 | 119.4 |
C1—N1—H1D | 117.4 | O1—C9—H9A | 109.5 |
C3—N2—C1 | 121.8 (2) | O1—C9—H9B | 109.5 |
C3—N2—H2D | 119.1 | H9A—C9—H9B | 109.5 |
C1—N2—H2D | 119.1 | O1—C9—H9C | 109.5 |
C1—C2—Cl3 | 110.13 (19) | H9A—C9—H9C | 109.5 |
C1—C2—Cl2 | 110.85 (18) | H9B—C9—H9C | 109.5 |
Cl3—C2—Cl2 | 108.39 (14) | C15—C10—C11 | 117.1 (3) |
C1—C2—Cl1 | 110.64 (18) | C15—C10—N1 | 125.2 (2) |
Cl3—C2—Cl1 | 107.98 (15) | C11—C10—N1 | 117.6 (2) |
Cl2—C2—Cl1 | 108.76 (15) | C12—C11—C10 | 121.4 (3) |
N2—C1—N1 | 112.0 (2) | C12—C11—H11 | 119.3 |
N2—C1—C2 | 108.0 (2) | C10—C11—H11 | 119.3 |
N1—C1—C2 | 111.4 (2) | C11—C12—C13 | 120.8 (3) |
N2—C1—H1 | 108.4 | C11—C12—H12 | 119.6 |
N1—C1—H1 | 108.4 | C13—C12—H12 | 119.6 |
C2—C1—H1 | 108.4 | C14—C13—O2 | 125.1 (3) |
C8—C3—N2 | 123.6 (2) | C14—C13—C12 | 118.8 (3) |
C8—C3—C4 | 118.0 (2) | O2—C13—C12 | 116.1 (3) |
N2—C3—C4 | 118.4 (2) | C13—C14—C15 | 120.1 (3) |
C5—C4—C3 | 120.9 (2) | C13—C14—H14 | 119.9 |
C5—C4—H4 | 119.5 | C15—C14—H14 | 119.9 |
C3—C4—H4 | 119.5 | C10—C15—C14 | 121.7 (3) |
C4—C5—C6 | 120.8 (3) | C10—C15—H15 | 119.1 |
C4—C5—H5 | 119.6 | C14—C15—H15 | 119.1 |
C6—C5—H5 | 119.6 | O2—C16—H16A | 109.5 |
O1—C6—C5 | 115.8 (2) | O2—C16—H16B | 109.5 |
O1—C6—C7 | 125.1 (2) | H16A—C16—H16B | 109.5 |
C5—C6—C7 | 119.1 (2) | O2—C16—H16C | 109.5 |
C6—C7—C8 | 120.0 (3) | H16A—C16—H16C | 109.5 |
C6—C7—H7 | 120.0 | H16B—C16—H16C | 109.5 |
C3—N2—C1—N1 | −67.7 (3) | O1—C6—C7—C8 | −178.2 (3) |
C3—N2—C1—C2 | 169.3 (2) | C5—C6—C7—C8 | 0.6 (4) |
C10—N1—C1—N2 | 131.0 (3) | N2—C3—C8—C7 | −178.8 (3) |
C10—N1—C1—C2 | −107.9 (3) | C4—C3—C8—C7 | 0.3 (4) |
Cl3—C2—C1—N2 | 177.96 (18) | C6—C7—C8—C3 | −0.5 (4) |
Cl2—C2—C1—N2 | −62.1 (3) | C1—N1—C10—C15 | 13.6 (4) |
Cl1—C2—C1—N2 | 58.7 (3) | C1—N1—C10—C11 | −167.2 (3) |
Cl3—C2—C1—N1 | 54.6 (3) | C15—C10—C11—C12 | −0.3 (5) |
Cl2—C2—C1—N1 | 174.51 (18) | N1—C10—C11—C12 | −179.6 (3) |
Cl1—C2—C1—N1 | −64.7 (2) | C10—C11—C12—C13 | −0.8 (6) |
C1—N2—C3—C8 | −13.1 (4) | C16—O2—C13—C14 | −21.3 (5) |
C1—N2—C3—C4 | 167.9 (2) | C16—O2—C13—C12 | 160.5 (4) |
C8—C3—C4—C5 | −0.2 (4) | C11—C12—C13—C14 | 1.3 (5) |
N2—C3—C4—C5 | 178.9 (2) | C11—C12—C13—O2 | 179.6 (3) |
C3—C4—C5—C6 | 0.4 (4) | O2—C13—C14—C15 | −178.8 (3) |
C9—O1—C6—C5 | 176.9 (3) | C12—C13—C14—C15 | −0.7 (5) |
C9—O1—C6—C7 | −4.3 (4) | C11—C10—C15—C14 | 0.9 (4) |
C4—C5—C6—O1 | 178.4 (2) | N1—C10—C15—C14 | −179.8 (3) |
C4—C5—C6—C7 | −0.6 (4) | C13—C14—C15—C10 | −0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl1 | 0.86 | 2.67 | 3.030 (3) | 107 |
N1—H1D···O1i | 0.86 | 2.54 | 3.150 (3) | 128 |
Symmetry code: (i) −x−1/2, y−1/2, z. |
C14H11Cl5N2 | Dx = 1.591 Mg m−3 |
Mr = 384.50 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 6611 reflections |
a = 6.0186 (6) Å | θ = 2.5–28.0° |
b = 8.0624 (8) Å | µ = 0.90 mm−1 |
c = 33.082 (3) Å | T = 291 K |
V = 1605.3 (3) Å3 | Block, colourless |
Z = 4 | 0.42 × 0.31 × 0.28 mm |
F(000) = 776 |
Nonius KappaCCD area-detector diffractometer | 2990 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2898 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.706, Tmax = 0.791 | k = −9→9 |
11400 measured reflections | l = −40→40 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.3399P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
2990 reflections | Δρmax = 0.18 e Å−3 |
190 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (5) |
C14H11Cl5N2 | V = 1605.3 (3) Å3 |
Mr = 384.50 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0186 (6) Å | µ = 0.90 mm−1 |
b = 8.0624 (8) Å | T = 291 K |
c = 33.082 (3) Å | 0.42 × 0.31 × 0.28 mm |
Nonius KappaCCD area-detector diffractometer | 2990 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2898 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.791 | Rint = 0.016 |
11400 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.063 | Δρmax = 0.18 e Å−3 |
S = 1.03 | Δρmin = −0.23 e Å−3 |
2990 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
190 parameters | Absolute structure parameter: −0.02 (5) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.26273 (9) | 1.06659 (7) | 0.16704 (2) | 0.05758 (16) | |
Cl2 | 0.82360 (10) | 1.20078 (7) | 0.161908 (19) | 0.05598 (16) | |
Cl3 | 1.10707 (12) | 1.20059 (7) | 0.091570 (19) | 0.06127 (17) | |
Cl4 | 1.50835 (9) | 0.34965 (7) | 0.241841 (16) | 0.04864 (14) | |
Cl5 | 0.30846 (13) | 0.38658 (8) | 0.009030 (19) | 0.0690 (2) | |
N1 | 0.7472 (3) | 0.9328 (2) | 0.09838 (5) | 0.0464 (4) | |
H1D | 0.6879 | 1.0296 | 0.0965 | 0.056* | |
N2 | 0.8963 (3) | 0.8106 (2) | 0.15779 (5) | 0.0409 (4) | |
H2D | 0.7673 | 0.8207 | 0.1687 | 0.049* | |
C1 | 0.9412 (3) | 0.9122 (2) | 0.12323 (6) | 0.0345 (4) | |
H1 | 1.0560 | 0.8573 | 0.1070 | 0.041* | |
C2 | 1.0281 (3) | 1.0873 (3) | 0.13526 (6) | 0.0397 (4) | |
C3 | 1.0416 (3) | 0.6968 (2) | 0.17554 (5) | 0.0314 (4) | |
C4 | 1.2440 (3) | 0.6489 (3) | 0.15813 (6) | 0.0420 (4) | |
H4 | 1.2848 | 0.6907 | 0.1330 | 0.050* | |
C5 | 1.3839 (3) | 0.5396 (2) | 0.17816 (6) | 0.0399 (4) | |
H5 | 1.5177 | 0.5080 | 0.1664 | 0.048* | |
C6 | 1.3247 (3) | 0.4778 (2) | 0.21539 (6) | 0.0347 (4) | |
C7 | 1.1223 (4) | 0.5186 (2) | 0.23231 (6) | 0.0369 (4) | |
H7 | 1.0807 | 0.4733 | 0.2570 | 0.044* | |
C8 | 0.9824 (3) | 0.6261 (2) | 0.21260 (6) | 0.0360 (4) | |
H8 | 0.8458 | 0.6524 | 0.2241 | 0.043* | |
C9 | 0.6522 (3) | 0.8008 (3) | 0.07725 (6) | 0.0385 (4) | |
C10 | 0.4571 (3) | 0.8298 (3) | 0.05510 (6) | 0.0403 (5) | |
H10 | 0.3971 | 0.9361 | 0.0545 | 0.048* | |
C11 | 0.3530 (4) | 0.7045 (3) | 0.03428 (6) | 0.0444 (5) | |
H11 | 0.2233 | 0.7257 | 0.0199 | 0.053* | |
C12 | 0.4423 (4) | 0.5469 (3) | 0.03485 (6) | 0.0457 (5) | |
C13 | 0.6356 (5) | 0.5148 (3) | 0.05606 (7) | 0.0544 (6) | |
H13 | 0.6957 | 0.4086 | 0.0561 | 0.065* | |
C14 | 0.7395 (4) | 0.6408 (3) | 0.07729 (6) | 0.0483 (5) | |
H14 | 0.8687 | 0.6184 | 0.0917 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0415 (3) | 0.0548 (3) | 0.0764 (4) | −0.0025 (3) | −0.0181 (3) | −0.0039 (3) |
Cl2 | 0.0472 (3) | 0.0543 (3) | 0.0664 (3) | 0.0096 (2) | 0.0069 (3) | −0.0172 (3) |
Cl3 | 0.0742 (4) | 0.0474 (3) | 0.0622 (3) | 0.0003 (3) | 0.0158 (3) | 0.0148 (3) |
Cl4 | 0.0418 (2) | 0.0480 (3) | 0.0561 (3) | 0.0050 (2) | −0.0062 (2) | 0.0165 (2) |
Cl5 | 0.0904 (5) | 0.0637 (4) | 0.0528 (3) | −0.0218 (4) | −0.0111 (3) | −0.0065 (3) |
N1 | 0.0480 (10) | 0.0386 (9) | 0.0525 (10) | 0.0105 (8) | −0.0159 (8) | −0.0004 (8) |
N2 | 0.0301 (8) | 0.0476 (9) | 0.0450 (9) | 0.0053 (7) | 0.0041 (7) | 0.0107 (8) |
C1 | 0.0336 (10) | 0.0351 (9) | 0.0350 (9) | 0.0042 (8) | −0.0012 (7) | 0.0026 (8) |
C2 | 0.0366 (10) | 0.0420 (10) | 0.0405 (10) | 0.0034 (9) | 0.0029 (8) | −0.0008 (8) |
C3 | 0.0298 (9) | 0.0309 (8) | 0.0335 (8) | 0.0000 (7) | −0.0018 (7) | −0.0003 (7) |
C4 | 0.0388 (10) | 0.0493 (11) | 0.0378 (10) | 0.0049 (9) | 0.0049 (8) | 0.0091 (9) |
C5 | 0.0332 (10) | 0.0424 (11) | 0.0442 (10) | 0.0078 (9) | 0.0054 (9) | 0.0039 (9) |
C6 | 0.0358 (10) | 0.0292 (9) | 0.0391 (9) | 0.0005 (8) | −0.0072 (8) | 0.0019 (7) |
C7 | 0.0427 (11) | 0.0360 (10) | 0.0320 (9) | −0.0008 (9) | 0.0032 (8) | 0.0036 (7) |
C8 | 0.0344 (9) | 0.0337 (9) | 0.0399 (9) | 0.0011 (8) | 0.0065 (8) | −0.0017 (8) |
C9 | 0.0394 (10) | 0.0433 (11) | 0.0330 (9) | 0.0028 (9) | −0.0011 (8) | 0.0014 (8) |
C10 | 0.0369 (11) | 0.0475 (11) | 0.0366 (10) | 0.0083 (9) | 0.0000 (8) | 0.0021 (9) |
C11 | 0.0381 (11) | 0.0596 (13) | 0.0355 (10) | 0.0007 (10) | −0.0031 (8) | 0.0017 (9) |
C12 | 0.0518 (13) | 0.0535 (13) | 0.0317 (10) | −0.0111 (10) | 0.0018 (9) | −0.0021 (9) |
C13 | 0.0653 (16) | 0.0421 (12) | 0.0559 (13) | 0.0077 (12) | −0.0063 (12) | −0.0034 (10) |
C14 | 0.0482 (12) | 0.0464 (12) | 0.0503 (12) | 0.0099 (11) | −0.0122 (10) | −0.0008 (9) |
Cl1—C2 | 1.768 (2) | C5—C6 | 1.375 (3) |
Cl2—C2 | 1.769 (2) | C5—H5 | 0.9300 |
Cl3—C2 | 1.775 (2) | C6—C7 | 1.380 (3) |
Cl4—C6 | 1.7480 (19) | C7—C8 | 1.373 (3) |
Cl5—C12 | 1.746 (2) | C7—H7 | 0.9300 |
N1—C9 | 1.396 (3) | C8—H8 | 0.9300 |
N1—C1 | 1.437 (2) | C9—C14 | 1.393 (3) |
N1—H1D | 0.8600 | C9—C10 | 1.404 (3) |
N2—C3 | 1.397 (2) | C10—C11 | 1.374 (3) |
N2—C1 | 1.432 (2) | C10—H10 | 0.9300 |
N2—H2D | 0.8600 | C11—C12 | 1.380 (3) |
C1—C2 | 1.558 (3) | C11—H11 | 0.9300 |
C1—H1 | 0.9800 | C12—C13 | 1.383 (3) |
C3—C8 | 1.398 (3) | C13—C14 | 1.384 (3) |
C3—C4 | 1.402 (3) | C13—H13 | 0.9300 |
C4—C5 | 1.387 (3) | C14—H14 | 0.9300 |
C4—H4 | 0.9300 | ||
C9—N1—C1 | 122.06 (17) | C5—C6—C7 | 120.37 (18) |
C9—N1—H1D | 119.0 | C5—C6—Cl4 | 119.90 (15) |
C1—N1—H1D | 119.0 | C7—C6—Cl4 | 119.72 (15) |
C3—N2—C1 | 126.37 (16) | C8—C7—C6 | 119.93 (18) |
C3—N2—H2D | 116.8 | C8—C7—H7 | 120.0 |
C1—N2—H2D | 116.8 | C6—C7—H7 | 120.0 |
C1—C2—Cl1 | 109.54 (13) | C7—C8—C3 | 121.14 (17) |
C1—C2—Cl2 | 111.26 (14) | C7—C8—H8 | 119.4 |
Cl1—C2—Cl2 | 107.96 (11) | C3—C8—H8 | 119.4 |
C1—C2—Cl3 | 110.38 (13) | N1—C9—C14 | 123.45 (18) |
Cl1—C2—Cl3 | 108.60 (11) | N1—C9—C10 | 118.52 (19) |
Cl2—C2—Cl3 | 109.03 (11) | C14—C9—C10 | 118.03 (19) |
N2—C1—N1 | 111.68 (16) | C11—C10—C9 | 121.39 (19) |
N2—C1—C2 | 112.18 (16) | C11—C10—H10 | 119.3 |
N1—C1—C2 | 108.28 (16) | C9—C10—H10 | 119.3 |
N2—C1—H1 | 108.2 | C10—C11—C12 | 119.51 (19) |
N1—C1—H1 | 108.2 | C10—C11—H11 | 120.2 |
C2—C1—H1 | 108.2 | C12—C11—H11 | 120.2 |
N2—C3—C8 | 118.46 (16) | C11—C12—C13 | 120.5 (2) |
N2—C3—C4 | 123.51 (17) | C11—C12—Cl5 | 119.68 (17) |
C8—C3—C4 | 118.03 (17) | C13—C12—Cl5 | 119.85 (18) |
C5—C4—C3 | 120.39 (18) | C14—C13—C12 | 120.0 (2) |
C5—C4—H4 | 119.8 | C14—C13—H13 | 120.0 |
C3—C4—H4 | 119.8 | C12—C13—H13 | 120.0 |
C6—C5—C4 | 120.04 (18) | C13—C14—C9 | 120.6 (2) |
C6—C5—H5 | 120.0 | C13—C14—H14 | 119.7 |
C4—C5—H5 | 120.0 | C9—C14—H14 | 119.7 |
C3—N2—C1—N1 | 144.05 (18) | C5—C6—C7—C8 | −2.4 (3) |
C3—N2—C1—C2 | −94.2 (2) | Cl4—C6—C7—C8 | 176.60 (15) |
C9—N1—C1—N2 | −66.9 (2) | C6—C7—C8—C3 | −0.4 (3) |
C9—N1—C1—C2 | 169.13 (18) | N2—C3—C8—C7 | −177.36 (18) |
Cl1—C2—C1—N2 | 54.71 (19) | C4—C3—C8—C7 | 2.8 (3) |
Cl2—C2—C1—N2 | −64.57 (19) | C1—N1—C9—C14 | −2.1 (3) |
Cl3—C2—C1—N2 | 174.24 (13) | C1—N1—C9—C10 | 177.20 (17) |
Cl1—C2—C1—N1 | 178.41 (13) | N1—C9—C10—C11 | −178.74 (19) |
Cl2—C2—C1—N1 | 59.13 (18) | C14—C9—C10—C11 | 0.6 (3) |
Cl3—C2—C1—N1 | −62.06 (18) | C9—C10—C11—C12 | −0.5 (3) |
C1—N2—C3—C8 | 170.73 (18) | C10—C11—C12—C13 | −0.2 (3) |
C1—N2—C3—C4 | −9.5 (3) | C10—C11—C12—Cl5 | 179.09 (15) |
N2—C3—C4—C5 | 177.69 (19) | C11—C12—C13—C14 | 0.7 (3) |
C8—C3—C4—C5 | −2.5 (3) | Cl5—C12—C13—C14 | −178.59 (18) |
C3—C4—C5—C6 | −0.2 (3) | C12—C13—C14—C9 | −0.6 (4) |
C4—C5—C6—C7 | 2.7 (3) | N1—C9—C14—C13 | 179.2 (2) |
C4—C5—C6—Cl4 | −176.29 (16) | C10—C9—C14—C13 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···Cl2 | 0.86 | 2.69 | 3.049 (2) | 106 |
C8—H8···Cl4i | 0.93 | 2.89 | 3.774 (3) | 160 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H17Cl3N2O2 | C14H11Cl5N2 |
Mr | 375.67 | 384.50 |
Crystal system, space group | Orthorhombic, Pbca | Orthorhombic, P212121 |
Temperature (K) | 291 | 291 |
a, b, c (Å) | 9.717 (2), 10.575 (3), 33.772 (8) | 6.0186 (6), 8.0624 (8), 33.082 (3) |
V (Å3) | 3470.3 (14) | 1605.3 (3) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.54 | 0.90 |
Crystal size (mm) | 0.38 × 0.29 × 0.25 | 0.42 × 0.31 × 0.28 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.822, 0.876 | 0.706, 0.791 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23826, 3233, 2571 | 11400, 2990, 2898 |
Rint | 0.066 | 0.016 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.109, 1.05 | 0.024, 0.063, 1.03 |
No. of reflections | 3233 | 2990 |
No. of parameters | 210 | 190 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.39 | 0.18, −0.23 |
Absolute structure | ? | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | ? | −0.02 (5) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Cl1—C2 | 1.790 (3) | O2—C16 | 1.396 (4) |
C10—N1—C1 | 125.2 (2) | O1—C6—C7 | 125.1 (2) |
C3—N2—C1 | 121.8 (2) | C15—C10—N1 | 125.2 (2) |
N1—C1—C2 | 111.4 (2) | C11—C10—N1 | 117.6 (2) |
C8—C3—N2 | 123.6 (2) | C14—C13—O2 | 125.1 (3) |
O1—C6—C5 | 115.8 (2) | O2—C13—C12 | 116.1 (3) |
C3—N2—C1—N1 | −67.7 (3) | C9—O1—C6—C7 | −4.3 (4) |
Cl3—C2—C1—N2 | 177.96 (18) | C1—N1—C10—C15 | 13.6 (4) |
Cl2—C2—C1—N1 | 174.51 (18) | N1—C10—C11—C12 | −179.6 (3) |
C1—N2—C3—C8 | −13.1 (4) | C11—C12—C13—O2 | 179.6 (3) |
N2—C3—C4—C5 | 178.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl1 | 0.86 | 2.67 | 3.030 (3) | 107 |
N1—H1D···O1i | 0.86 | 2.54 | 3.150 (3) | 128 |
Symmetry code: (i) −x−1/2, y−1/2, z. |
C9—C10 | 1.404 (3) | ||
C3—N2—C1 | 126.37 (16) | N1—C9—C14 | 123.45 (18) |
N2—C3—C4 | 123.51 (17) | ||
C3—N2—C1—N1 | 144.05 (18) | C1—N1—C9—C14 | −2.1 (3) |
C1—N2—C3—C4 | −9.5 (3) | N1—C9—C14—C13 | 179.2 (2) |
N2—C3—C4—C5 | 177.69 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···Cl2 | 0.86 | 2.69 | 3.049 (2) | 106 |
C8—H8···Cl4i | 0.93 | 2.89 | 3.774 (3) | 160 |
Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
As a continuation of our structural studies of bis(arylamino)trichloromethylmethanes (Zhang et al., 2007), we report here the molecular and supramolecular structures of 2,2,2-trichloro-N,N'-bis(4-methoxyphenyl)ethane-1,1-diamine, (I) (Fig. 1), and 2,2,2-trichloro-N,N'-bis(4-chlorophenyl)ethane-1,1-diamine, (II) (Fig. 2), where the supramolecular aggregations prove to be different from those in 2,2,2-trichloro-N,N'-diphenylethane-1,1-diamine, (III), and 2,2,2-trichloro-N,N'-bis(4-methylphenyl)ethane-1,1-diamine, (IV), which we reported recently (Zhang et al., 2007). In (III), the two-dimensional supramolecular structure is built from C—H···Cl and C—H···π(arene) contacts, while the crystal structure of (IV) exhibits one-dimensional double columns formed by a combination of two independent C—H···Cl hydrogen bonds and one Cl···Cl interaction.
In compounds (I) and (II), the trichloroethane-1,1-diamine fragments adopt a gauche conformation with respect to the C1—C2 bonds, similar to the situation in (III) and (IV). In (II), the dihedral angle between the planes of the two aromatic rings is 88.01 (2)°, indicating that these phenyl rings are perpendicular to one another. The orientation of the two rings is different from that in (I), where the dihedral angle is 76.37 (3)°. Selected geometric parameters for (I) and (II) are listed in Tables 1 and 3, respectively. The C2—Cl1 bond in (I) is longer than the other C—Cl bonds in compounds (I)–(IV), probably due to the presence of a relatively strong intramolecular N2—H2D···Cl1 hydrogen bond (Table 2). The same variation of ca 9° occurs within each pair of exocyclic C—C—O valence angles in (I), as is well established for 4-methoxyphenyl units (Seip & Seip, 1973). These deviations suggest the presence of repulsive interactions between O2—CH3 and atom H14 (distance between methyl C atom and H14 = 2.61 Å) or O1—CH3 and H7 (distance between methyl C atom and H7 = 2.55 Å). The methoxy group on C6 is effectively coplanar with the C3–C8 ring, as shown by the C7—C6—O1—C9 torsion angle of −4.3 (4)°. The situation is, however, different for the methoxy group on C13, where the torsion angle is −21.3 (5)° and the methyl C atom is displaced from the plane of the C10–C15 aryl ring by 0.408 (4) Å. In compound (II), the C1—N1—C9—C14 and C1—N2—C3—C4 torsion angles are −2.1 (3) and −9.5 (3)°, respectively, indicating that atom C1 lies near the N1/C9–C14 plane. However, atom C1 in (I) is displaced by 0.249 (3) and 0.265 (4) Å from the N2/C3–C8 and N1/C10–C15 planes, respectively.
The two NH H atoms in each molecule have very similar chemical shifts and coupling constants with the adjacent CH H atom [J = 8.8 Hz in (I) and 8.4 Hz in (II)], suggesting that, in solution at room temperature on the NMR timescale, the molecules relax to a conformation where the two H—N—C—H torsion angles have similar average magnitudes, though the two H—N—C—H torsion angles in each molecule in the solid state are different [−169 and −128° for H1D—N1—C1—H1 and H2D—N2—C1—H1, respectively, in (I), and −155 and −128° for H2D—N2—C—H1 and H1D—N1—C1—H1, respectively, in (II)].
In compound (I), the molecules are linked into helical chains by a single N—H···O hydrogen bond (Table 2). Atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to methoxy atom O1 in the molecule at (−1/2 − x, y − 1/2, z). Propagation by an a-glide plane at x = −1/4 then generates a C(9) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 3). Eight chains of this type pass through each unit cell; four of these, running along the (−1/4, y, 3/8), (3/4, y, 3/8), (−1/4, y, 7/8) and (3/4, y, 7/8) directions, are related to each other by translational symmetry operations, and they are related by an a-glide plane to the other four chains running along the (−1/4, y, 1/8), (3/4, y, 1/8), (−1/4, y, 5/8) and (3/4, y, 5/8) directions. There are no direction-specific interactions between adjacent chains.
There are no aromatic π–π stacking interactions in the structure of (II); instead, the molecules are linked into a complex three-dimensional framework by a combination of two independent Cl···Cl interactions and one C—H···Cl hydrogen bond (Table 4). However, the formation of the structure of (II) can be easily analysed in terms of three one-dimensional substrutures. In the first substructure, atom Cl5 in the molecule at (x, y, z) forms an intermolecular interaction with trichloromethyl atom Cl3 [Cl5···Cl3 = 3.343 (2) Å] in the molecule at (x + 1, y, z). Propagation by translation then generates a C(9) chain running along the [110] direction (Fig. 4). In the same way, the second substructure is constructed by way of a Cl···Cl interaction: atom Cl4 in the molecule at (x, y, z) forms another independent intermolecular interaction with trichloromethyl atom Cl2 [Cl4···Cl2 = 3.469 (2) Å] in the molecule at (x + 1, y − 1, z), so forming by translation a C(9) chain parallel to the [110] direction (Fig. 5). In the third substructure, atom H8 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom Cl4 in the molecule at (−x + 2, y + 1/2, − z + 1/2), thus generating a C(5) chain along the (1, y, 1/4) direction and generated by a 21 screw axis along (1, y, 1/4) (Fig. 6). The combination of these three chain motifs links molecules of (II) into a three-dimensional framework.