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The molecules of 2,2,2-trichloro-
N,
N′-diphenylethane-1,1-diamine, C
14H
13Cl
3N
2, are linked into (040) sheets by a combination of C—H
Cl and C—H
π(arene) hydrogen bonds. In 2,2,2-trichloro-
N,
N′-bis(4-methylphenyl)ethane-1,1-diamine, C
16H
17Cl
3N
2, the molecules are linked into
C(7) chains by two independent C—H
Cl hydrogen bonds and one Cl
Cl contact.
Supporting information
CCDC references: 636105; 636106
Compound (I) was synthesized by heating with stirring a mixture of chloral
hydrate (16.5 g, 0.1 mol), freshly distilled aniline (0.2 mol) and ethyl
acetate (25–30 ml) until dissolution of the solid. Cooling of the hot
solution and then slow evaporation of the solvent at room temperature yielded
a crystalline product (yield 72%). Single crystals of (I) were obtained by
recrystallization from ethyl acetate. 1H NMR (DMSO, 400 MHz): δ 6.85
(m, 10H, 2Ar), 6.05 (d, J = 7.2 Hz, 2H, 2NH), 5.69
(t, J = 7.2 Hz, 1H, CH). For the synthesis of (II), chloral
hydrate (33.1 g, 0.2 mol) was added at room temperature to a stirred solution
of paratoluidine (43.2 g, 0.4 mol) in ethanol (40 ml). The mixure was then
heated at about 323 K with stirring for 30 min. Natural cooling of the
reaction mixture overnight gave a crystalline product, (II) (yield 25 g, 75%).
Single crystals of (II) were obtained by recrystallization from ethyl acetate.
1H NMR (DMSO, 400 MHz): δ 6.79 (m, 8H, 2 C6H4), 5.79 (d,
J = 8.4 Hz, 2H, 2NH), 5.55 (t, J = 8.4 Hz, 1H, CH), 2.105
(s, 6H, 2CH3).
H atoms in (I) were placed in idealized positions and allowed to ride on the
respective parent atoms with C—H distances of 0.93–0.98 Å and N—H of
0.86 Å, and with Uiso(H) values of 1.2Ueq(carrier atom).
In (II), H atoms bonded to N atoms were refined with an N—H distance
restraint of 0.87 (2) Å, and with Uiso(H) values of
1.2Ueq(N,O). Other H atoms were positioned geometrically and
allowed to ride on the respective parent atoms, with C—H distances of
0.93–0.98 Å and with Uiso(H) values of 1.2 (1.5 for methyl groups)
times Ueq(C).
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(I) 2,2,2-trichloro-
N,
N'-diphenylethane-1,1-diamine
top
Crystal data top
C14H13Cl3N2 | F(000) = 648 |
Mr = 315.61 | Dx = 1.437 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1225 (7) Å | Cell parameters from 2776 reflections |
b = 15.7539 (17) Å | θ = 2.6–22.8° |
c = 15.2020 (16) Å | µ = 0.62 mm−1 |
β = 95.936 (1)° | T = 291 K |
V = 1458.4 (3) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.17 × 0.14 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2717 independent reflections |
Radiation source: fine-focus sealed tube | 2041 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
phi and ω scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | h = −7→7 |
Tmin = 0.863, Tmax = 0.917 | k = −19→18 |
10979 measured reflections | l = −18→18 |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0288P)2 + 0.8125P] where P = (Fo2 + 2Fc2)/3 |
2717 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
C14H13Cl3N2 | V = 1458.4 (3) Å3 |
Mr = 315.61 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.1225 (7) Å | µ = 0.62 mm−1 |
b = 15.7539 (17) Å | T = 291 K |
c = 15.2020 (16) Å | 0.25 × 0.17 × 0.14 mm |
β = 95.936 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2717 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | 2041 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 0.917 | Rint = 0.029 |
10979 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.35 e Å−3 |
2717 reflections | Δρmin = −0.34 e Å−3 |
172 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 1.11696 (13) | 0.49239 (4) | 0.79205 (5) | 0.0714 (2) | |
Cl2 | 0.81810 (11) | 0.47878 (5) | 0.63491 (5) | 0.0700 (2) | |
Cl3 | 1.25641 (12) | 0.41168 (5) | 0.63853 (6) | 0.0755 (2) | |
N1 | 0.7747 (3) | 0.35121 (12) | 0.78349 (13) | 0.0527 (5) | |
H1D | 0.7081 | 0.3993 | 0.7803 | 0.063* | |
N2 | 0.9075 (3) | 0.28057 (12) | 0.66137 (13) | 0.0510 (5) | |
H2D | 0.7816 | 0.2862 | 0.6312 | 0.061* | |
C1 | 0.7018 (3) | 0.28814 (14) | 0.83771 (14) | 0.0417 (5) | |
C2 | 0.5175 (4) | 0.30378 (16) | 0.88191 (15) | 0.0490 (6) | |
H2 | 0.4469 | 0.3560 | 0.8752 | 0.059* | |
C3 | 0.4389 (4) | 0.24291 (18) | 0.93537 (16) | 0.0584 (7) | |
H3 | 0.3145 | 0.2540 | 0.9637 | 0.070* | |
C4 | 0.5431 (5) | 0.16586 (18) | 0.94712 (18) | 0.0651 (7) | |
H4 | 0.4889 | 0.1245 | 0.9828 | 0.078* | |
C5 | 0.7286 (5) | 0.15053 (17) | 0.90555 (18) | 0.0644 (7) | |
H5 | 0.8024 | 0.0992 | 0.9149 | 0.077* | |
C6 | 0.8064 (4) | 0.21017 (15) | 0.85023 (16) | 0.0533 (6) | |
H6 | 0.9293 | 0.1982 | 0.8212 | 0.064* | |
C7 | 0.9569 (3) | 0.33852 (14) | 0.73291 (14) | 0.0418 (5) | |
H7 | 1.0777 | 0.3144 | 0.7724 | 0.050* | |
C8 | 1.0420 (4) | 0.21589 (14) | 0.63544 (14) | 0.0426 (5) | |
C9 | 0.9689 (4) | 0.16890 (15) | 0.56090 (15) | 0.0528 (6) | |
H9 | 0.8338 | 0.1816 | 0.5299 | 0.063* | |
C10 | 1.0929 (6) | 0.10412 (17) | 0.53236 (18) | 0.0689 (8) | |
H10 | 1.0412 | 0.0737 | 0.4820 | 0.083* | |
C11 | 1.2923 (6) | 0.08332 (17) | 0.5769 (2) | 0.0742 (9) | |
H11 | 1.3752 | 0.0390 | 0.5574 | 0.089* | |
C12 | 1.3669 (5) | 0.12922 (18) | 0.65069 (19) | 0.0670 (8) | |
H12 | 1.5015 | 0.1157 | 0.6816 | 0.080* | |
C13 | 1.2446 (4) | 0.19519 (16) | 0.67957 (17) | 0.0553 (6) | |
H13 | 1.2986 | 0.2262 | 0.7292 | 0.066* | |
C14 | 1.0326 (4) | 0.42616 (15) | 0.70098 (15) | 0.0467 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0838 (5) | 0.0532 (4) | 0.0746 (5) | −0.0113 (3) | −0.0037 (4) | −0.0104 (3) |
Cl2 | 0.0578 (4) | 0.0690 (5) | 0.0808 (5) | 0.0039 (3) | −0.0049 (3) | 0.0234 (4) |
Cl3 | 0.0644 (4) | 0.0694 (5) | 0.0994 (6) | 0.0016 (4) | 0.0412 (4) | 0.0093 (4) |
N1 | 0.0516 (12) | 0.0430 (11) | 0.0669 (13) | 0.0096 (9) | 0.0218 (10) | 0.0048 (10) |
N2 | 0.0392 (10) | 0.0562 (12) | 0.0553 (12) | 0.0044 (9) | −0.0056 (9) | −0.0109 (10) |
C1 | 0.0387 (12) | 0.0465 (13) | 0.0400 (12) | −0.0028 (10) | 0.0046 (10) | −0.0065 (10) |
C2 | 0.0412 (13) | 0.0598 (15) | 0.0459 (13) | 0.0040 (11) | 0.0035 (10) | −0.0065 (12) |
C3 | 0.0473 (14) | 0.080 (2) | 0.0494 (15) | −0.0056 (14) | 0.0132 (12) | −0.0079 (14) |
C4 | 0.0748 (19) | 0.0636 (18) | 0.0603 (17) | −0.0180 (15) | 0.0231 (14) | −0.0015 (14) |
C5 | 0.083 (2) | 0.0454 (15) | 0.0680 (18) | 0.0036 (14) | 0.0243 (15) | 0.0007 (13) |
C6 | 0.0554 (15) | 0.0488 (14) | 0.0587 (15) | 0.0045 (12) | 0.0203 (12) | −0.0028 (12) |
C7 | 0.0371 (12) | 0.0440 (13) | 0.0447 (13) | 0.0024 (10) | 0.0066 (10) | −0.0024 (10) |
C8 | 0.0469 (13) | 0.0412 (12) | 0.0401 (12) | −0.0043 (10) | 0.0065 (10) | −0.0010 (10) |
C9 | 0.0696 (16) | 0.0464 (14) | 0.0414 (13) | −0.0109 (12) | 0.0007 (12) | 0.0010 (11) |
C10 | 0.111 (3) | 0.0470 (16) | 0.0500 (16) | −0.0135 (16) | 0.0153 (16) | −0.0121 (13) |
C11 | 0.106 (3) | 0.0452 (16) | 0.077 (2) | 0.0096 (16) | 0.0374 (19) | −0.0070 (15) |
C12 | 0.0600 (17) | 0.0671 (18) | 0.075 (2) | 0.0155 (14) | 0.0112 (14) | −0.0052 (15) |
C13 | 0.0529 (14) | 0.0588 (16) | 0.0533 (15) | 0.0069 (12) | 0.0015 (12) | −0.0156 (12) |
C14 | 0.0401 (12) | 0.0481 (14) | 0.0522 (14) | 0.0023 (10) | 0.0060 (10) | 0.0009 (11) |
Geometric parameters (Å, º) top
Cl1—C14 | 1.768 (2) | C5—C6 | 1.378 (3) |
Cl2—C14 | 1.774 (2) | C5—H5 | 0.9300 |
Cl3—C14 | 1.761 (2) | C6—H6 | 0.9300 |
N1—C1 | 1.393 (3) | C7—C14 | 1.550 (3) |
N1—C7 | 1.433 (3) | C7—H7 | 0.9800 |
N1—H1D | 0.8600 | C8—C13 | 1.387 (3) |
N2—C8 | 1.392 (3) | C8—C9 | 1.388 (3) |
N2—C7 | 1.428 (3) | C9—C10 | 1.369 (4) |
N2—H2D | 0.8600 | C9—H9 | 0.9300 |
C1—C6 | 1.389 (3) | C10—C11 | 1.373 (4) |
C1—C2 | 1.393 (3) | C10—H10 | 0.9300 |
C2—C3 | 1.376 (3) | C11—C12 | 1.373 (4) |
C2—H2 | 0.9300 | C11—H11 | 0.9300 |
C3—C4 | 1.374 (4) | C12—C13 | 1.379 (3) |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.377 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | | |
| | | |
C1—N1—C7 | 122.18 (19) | N2—C7—H7 | 107.8 |
C1—N1—H1D | 118.9 | N1—C7—H7 | 107.8 |
C7—N1—H1D | 118.9 | C14—C7—H7 | 107.8 |
C8—N2—C7 | 126.77 (19) | C13—C8—C9 | 117.8 (2) |
C8—N2—H2D | 116.6 | C13—C8—N2 | 124.1 (2) |
C7—N2—H2D | 116.6 | C9—C8—N2 | 118.1 (2) |
C6—C1—C2 | 118.4 (2) | C10—C9—C8 | 120.9 (3) |
C6—C1—N1 | 122.7 (2) | C10—C9—H9 | 119.5 |
C2—C1—N1 | 118.9 (2) | C8—C9—H9 | 119.5 |
C3—C2—C1 | 120.8 (2) | C9—C10—C11 | 121.0 (3) |
C3—C2—H2 | 119.6 | C9—C10—H10 | 119.5 |
C1—C2—H2 | 119.6 | C11—C10—H10 | 119.5 |
C4—C3—C2 | 120.4 (2) | C10—C11—C12 | 118.8 (3) |
C4—C3—H3 | 119.8 | C10—C11—H11 | 120.6 |
C2—C3—H3 | 119.8 | C12—C11—H11 | 120.6 |
C3—C4—C5 | 119.3 (3) | C11—C12—C13 | 120.8 (3) |
C3—C4—H4 | 120.4 | C11—C12—H12 | 119.6 |
C5—C4—H4 | 120.4 | C13—C12—H12 | 119.6 |
C4—C5—C6 | 120.9 (3) | C12—C13—C8 | 120.7 (2) |
C4—C5—H5 | 119.5 | C12—C13—H13 | 119.6 |
C6—C5—H5 | 119.5 | C8—C13—H13 | 119.6 |
C5—C6—C1 | 120.2 (2) | C7—C14—Cl3 | 109.15 (15) |
C5—C6—H6 | 119.9 | C7—C14—Cl1 | 110.68 (16) |
C1—C6—H6 | 119.9 | Cl3—C14—Cl1 | 108.56 (12) |
N2—C7—N1 | 112.50 (18) | C7—C14—Cl2 | 111.44 (15) |
N2—C7—C14 | 112.18 (18) | Cl3—C14—Cl2 | 109.09 (13) |
N1—C7—C14 | 108.56 (18) | Cl1—C14—Cl2 | 107.87 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···Cl2 | 0.86 | 2.69 | 3.055 (2) | 107 |
N1—H1D···Cl1 | 0.86 | 2.89 | 3.049 (2) | 92 |
C4—H4···Cl3i | 0.93 | 2.94 | 3.755 (3) | 147 |
C9—H9···Mii | 0.93 | 2.74 | 3.547 (3) | 145 |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
(II) 2,2,2-trichloro-
N,
N'-bis(4-methylphenyl)ethane-1,1-diamine
top
Crystal data top
C16H17Cl3N2 | F(000) = 712 |
Mr = 343.67 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3912 reflections |
a = 5.9238 (7) Å | θ = 2.6–26.6° |
b = 14.6193 (16) Å | µ = 0.55 mm−1 |
c = 19.093 (2) Å | T = 291 K |
β = 96.992 (1)° | Flake, colourless |
V = 1641.2 (3) Å3 | 0.44 × 0.35 × 0.26 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3756 independent reflections |
Radiation source: fine-focus sealed tube | 2955 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
phi and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | h = −7→7 |
Tmin = 0.793, Tmax = 0.871 | k = −18→18 |
11838 measured reflections | l = −24→24 |
Refinement top
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.554P] where P = (Fo2 + 2Fc2)/3 |
3756 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
C16H17Cl3N2 | V = 1641.2 (3) Å3 |
Mr = 343.67 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.9238 (7) Å | µ = 0.55 mm−1 |
b = 14.6193 (16) Å | T = 291 K |
c = 19.093 (2) Å | 0.44 × 0.35 × 0.26 mm |
β = 96.992 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3756 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | 2955 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.871 | Rint = 0.021 |
11838 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.26 e Å−3 |
3756 reflections | Δρmin = −0.34 e Å−3 |
200 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | −0.08280 (9) | −0.09977 (4) | 0.04411 (3) | 0.05775 (16) | |
Cl2 | −0.19299 (8) | −0.13076 (4) | 0.18383 (3) | 0.05699 (16) | |
Cl3 | 0.23639 (8) | −0.19339 (3) | 0.14612 (4) | 0.06536 (18) | |
N1 | 0.2129 (3) | −0.01115 (12) | 0.23320 (9) | 0.0492 (4) | |
N2 | 0.3127 (3) | 0.01075 (12) | 0.11558 (10) | 0.0495 (4) | |
C1 | 0.1040 (3) | 0.03174 (12) | 0.28542 (10) | 0.0416 (4) | |
C2 | 0.2082 (3) | 0.03005 (14) | 0.35451 (11) | 0.0521 (5) | |
H2 | 0.3495 | 0.0021 | 0.3647 | 0.062* | |
C3 | 0.1062 (4) | 0.06897 (15) | 0.40834 (11) | 0.0581 (5) | |
H3 | 0.1805 | 0.0668 | 0.4541 | 0.070* | |
C4 | −0.1054 (4) | 0.11147 (13) | 0.39604 (11) | 0.0514 (5) | |
C5 | −0.2055 (3) | 0.11434 (14) | 0.32724 (11) | 0.0504 (5) | |
H5 | −0.3450 | 0.1436 | 0.3171 | 0.061* | |
C6 | −0.1062 (3) | 0.07528 (14) | 0.27245 (10) | 0.0483 (5) | |
H6 | −0.1802 | 0.0781 | 0.2267 | 0.058* | |
C7 | −0.2196 (5) | 0.15171 (19) | 0.45545 (13) | 0.0756 (7) | |
H7A | −0.1402 | 0.2060 | 0.4726 | 0.113* | |
H7B | −0.2169 | 0.1079 | 0.4930 | 0.113* | |
H7C | −0.3744 | 0.1668 | 0.4385 | 0.113* | |
C8 | 0.1371 (3) | −0.01025 (12) | 0.15874 (10) | 0.0416 (4) | |
H8 | 0.0182 | 0.0364 | 0.1499 | 0.050* | |
C9 | 0.0315 (3) | −0.10421 (12) | 0.13430 (10) | 0.0438 (4) | |
C10 | 0.4166 (3) | 0.09734 (12) | 0.11755 (9) | 0.0389 (4) | |
C11 | 0.3454 (3) | 0.17078 (13) | 0.15532 (10) | 0.0451 (4) | |
H11 | 0.2208 | 0.1645 | 0.1803 | 0.054* | |
C12 | 0.4596 (3) | 0.25352 (13) | 0.15593 (11) | 0.0477 (4) | |
H12 | 0.4086 | 0.3023 | 0.1810 | 0.057* | |
C13 | 0.6474 (3) | 0.26591 (13) | 0.12033 (10) | 0.0456 (4) | |
C14 | 0.7121 (3) | 0.19290 (13) | 0.08123 (11) | 0.0468 (4) | |
H14 | 0.8349 | 0.1997 | 0.0557 | 0.056* | |
C15 | 0.5991 (3) | 0.11015 (13) | 0.07915 (10) | 0.0434 (4) | |
H15 | 0.6454 | 0.0626 | 0.0519 | 0.052* | |
C16 | 0.7805 (4) | 0.35437 (15) | 0.12444 (14) | 0.0679 (6) | |
H16A | 0.8958 | 0.3525 | 0.1644 | 0.102* | |
H16B | 0.6796 | 0.4047 | 0.1295 | 0.102* | |
H16C | 0.8507 | 0.3621 | 0.0821 | 0.102* | |
H1D | 0.344 (4) | −0.0256 (15) | 0.2444 (11) | 0.057 (6)* | |
H2D | 0.386 (4) | −0.0291 (17) | 0.1064 (12) | 0.062 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0666 (3) | 0.0514 (3) | 0.0537 (3) | −0.0001 (2) | 0.0010 (2) | −0.0102 (2) |
Cl2 | 0.0428 (3) | 0.0583 (3) | 0.0709 (4) | −0.0075 (2) | 0.0113 (2) | 0.0059 (2) |
Cl3 | 0.0437 (3) | 0.0412 (3) | 0.1098 (5) | 0.0067 (2) | 0.0038 (3) | 0.0014 (3) |
N1 | 0.0354 (8) | 0.0605 (10) | 0.0502 (10) | 0.0077 (7) | −0.0008 (7) | −0.0031 (8) |
N2 | 0.0464 (9) | 0.0396 (9) | 0.0656 (11) | −0.0041 (7) | 0.0195 (8) | −0.0110 (8) |
C1 | 0.0385 (9) | 0.0384 (9) | 0.0468 (10) | −0.0020 (7) | 0.0006 (8) | 0.0007 (8) |
C2 | 0.0464 (10) | 0.0526 (11) | 0.0540 (12) | 0.0081 (9) | −0.0067 (9) | 0.0011 (9) |
C3 | 0.0649 (13) | 0.0597 (13) | 0.0458 (11) | 0.0069 (10) | −0.0091 (10) | −0.0010 (10) |
C4 | 0.0625 (12) | 0.0429 (10) | 0.0481 (11) | 0.0039 (9) | 0.0041 (9) | −0.0027 (9) |
C5 | 0.0473 (10) | 0.0475 (11) | 0.0560 (12) | 0.0086 (8) | 0.0044 (9) | 0.0037 (9) |
C6 | 0.0445 (10) | 0.0561 (11) | 0.0428 (10) | 0.0067 (8) | −0.0015 (8) | 0.0032 (9) |
C7 | 0.0898 (18) | 0.0788 (17) | 0.0581 (14) | 0.0217 (14) | 0.0086 (13) | −0.0107 (12) |
C8 | 0.0372 (9) | 0.0392 (9) | 0.0484 (11) | 0.0003 (7) | 0.0049 (8) | −0.0022 (8) |
C9 | 0.0361 (9) | 0.0399 (9) | 0.0549 (11) | 0.0020 (7) | 0.0038 (8) | 0.0010 (8) |
C10 | 0.0350 (8) | 0.0401 (9) | 0.0408 (9) | −0.0006 (7) | 0.0011 (7) | −0.0037 (7) |
C11 | 0.0401 (9) | 0.0454 (10) | 0.0512 (11) | −0.0016 (8) | 0.0110 (8) | −0.0061 (8) |
C12 | 0.0481 (10) | 0.0425 (10) | 0.0531 (11) | 0.0005 (8) | 0.0083 (9) | −0.0098 (8) |
C13 | 0.0451 (10) | 0.0420 (10) | 0.0490 (11) | −0.0045 (8) | 0.0027 (8) | −0.0013 (8) |
C14 | 0.0410 (9) | 0.0508 (11) | 0.0499 (11) | −0.0028 (8) | 0.0107 (8) | −0.0004 (9) |
C15 | 0.0429 (9) | 0.0430 (10) | 0.0450 (10) | 0.0030 (8) | 0.0080 (8) | −0.0073 (8) |
C16 | 0.0730 (15) | 0.0508 (13) | 0.0829 (17) | −0.0169 (11) | 0.0213 (13) | −0.0089 (12) |
Geometric parameters (Å, º) top
Cl1—C9 | 1.773 (2) | C7—H7A | 0.9600 |
Cl2—C9 | 1.7661 (19) | C7—H7B | 0.9600 |
Cl3—C9 | 1.7770 (18) | C7—H7C | 0.9600 |
N1—C1 | 1.400 (2) | C8—C9 | 1.557 (2) |
N1—C8 | 1.438 (2) | C8—H8 | 0.9800 |
N1—H1D | 0.81 (2) | C10—C11 | 1.387 (2) |
N2—C10 | 1.406 (2) | C10—C15 | 1.391 (3) |
N2—C8 | 1.437 (2) | C11—C12 | 1.385 (3) |
N2—H2D | 0.76 (2) | C11—H11 | 0.9300 |
C1—C2 | 1.387 (3) | C12—C13 | 1.384 (3) |
C1—C6 | 1.393 (2) | C12—H12 | 0.9300 |
C2—C3 | 1.377 (3) | C13—C14 | 1.383 (3) |
C2—H2 | 0.9300 | C13—C16 | 1.512 (3) |
C3—C4 | 1.393 (3) | C14—C15 | 1.381 (3) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.375 (3) | C15—H15 | 0.9300 |
C4—C7 | 1.509 (3) | C16—H16A | 0.9600 |
C5—C6 | 1.384 (3) | C16—H16B | 0.9600 |
C5—H5 | 0.9300 | C16—H16C | 0.9600 |
C6—H6 | 0.9300 | | |
| | | |
C1—N1—C8 | 125.76 (16) | N2—C8—H8 | 107.9 |
C1—N1—H1D | 116.1 (16) | N1—C8—H8 | 107.9 |
C8—N1—H1D | 116.1 (16) | C9—C8—H8 | 107.9 |
C10—N2—C8 | 121.48 (16) | C8—C9—Cl2 | 109.55 (13) |
C10—N2—H2D | 115.7 (18) | C8—C9—Cl1 | 110.53 (13) |
C8—N2—H2D | 116.4 (18) | Cl2—C9—Cl1 | 107.75 (9) |
C2—C1—C6 | 117.50 (18) | C8—C9—Cl3 | 111.45 (12) |
C2—C1—N1 | 118.62 (16) | Cl2—C9—Cl3 | 108.54 (10) |
C6—C1—N1 | 123.87 (17) | Cl1—C9—Cl3 | 108.93 (10) |
C3—C2—C1 | 121.16 (18) | C11—C10—C15 | 118.36 (16) |
C3—C2—H2 | 119.4 | C11—C10—N2 | 123.42 (17) |
C1—C2—H2 | 119.4 | C15—C10—N2 | 118.22 (16) |
C2—C3—C4 | 121.75 (19) | C12—C11—C10 | 120.05 (18) |
C2—C3—H3 | 119.1 | C12—C11—H11 | 120.0 |
C4—C3—H3 | 119.1 | C10—C11—H11 | 120.0 |
C5—C4—C3 | 116.69 (19) | C13—C12—C11 | 122.08 (18) |
C5—C4—C7 | 121.73 (19) | C13—C12—H12 | 119.0 |
C3—C4—C7 | 121.58 (19) | C11—C12—H12 | 119.0 |
C4—C5—C6 | 122.42 (18) | C14—C13—C12 | 117.13 (17) |
C4—C5—H5 | 118.8 | C14—C13—C16 | 120.73 (18) |
C6—C5—H5 | 118.8 | C12—C13—C16 | 122.12 (18) |
C5—C6—C1 | 120.46 (18) | C15—C14—C13 | 121.78 (17) |
C5—C6—H6 | 119.8 | C15—C14—H14 | 119.1 |
C1—C6—H6 | 119.8 | C13—C14—H14 | 119.1 |
C4—C7—H7A | 109.5 | C14—C15—C10 | 120.52 (17) |
C4—C7—H7B | 109.5 | C14—C15—H15 | 119.7 |
H7A—C7—H7B | 109.5 | C10—C15—H15 | 119.7 |
C4—C7—H7C | 109.5 | C13—C16—H16A | 109.5 |
H7A—C7—H7C | 109.5 | C13—C16—H16B | 109.5 |
H7B—C7—H7C | 109.5 | H16A—C16—H16B | 109.5 |
N2—C8—N1 | 114.08 (15) | C13—C16—H16C | 109.5 |
N2—C8—C9 | 108.01 (15) | H16A—C16—H16C | 109.5 |
N1—C8—C9 | 110.73 (15) | H16B—C16—H16C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl3 | 0.76 (2) | 2.70 (2) | 3.085 (2) | 113 (2) |
C14—H14···Cl1i | 0.93 | 2.93 | 3.699 (2) | 141 |
C15—H15···Cl1ii | 0.93 | 2.88 | 3.705 (3) | 148 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C14H13Cl3N2 | C16H17Cl3N2 |
Mr | 315.61 | 343.67 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 291 | 291 |
a, b, c (Å) | 6.1225 (7), 15.7539 (17), 15.2020 (16) | 5.9238 (7), 14.6193 (16), 19.093 (2) |
β (°) | 95.936 (1) | 96.992 (1) |
V (Å3) | 1458.4 (3) | 1641.2 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.62 | 0.55 |
Crystal size (mm) | 0.25 × 0.17 × 0.14 | 0.44 × 0.35 × 0.26 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997a) | Multi-scan (SADABS; Sheldrick, 1997a) |
Tmin, Tmax | 0.863, 0.917 | 0.793, 0.871 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10979, 2717, 2041 | 11838, 3756, 2955 |
Rint | 0.029 | 0.021 |
(sin θ/λ)max (Å−1) | 0.606 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.090, 1.04 | 0.038, 0.099, 1.03 |
No. of reflections | 2717 | 3756 |
No. of parameters | 172 | 200 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.34 | 0.26, −0.34 |
Selected geometric parameters (Å, º) for (I) topCl1—C14 | 1.768 (2) | N1—C1 | 1.393 (3) |
Cl2—C14 | 1.774 (2) | N2—C8 | 1.392 (3) |
Cl3—C14 | 1.761 (2) | | |
| | | |
C1—N1—C7 | 122.18 (19) | N2—C7—C14 | 112.18 (18) |
C8—N2—C7 | 126.77 (19) | C7—C14—Cl1 | 110.68 (16) |
N2—C7—N1 | 112.50 (18) | C7—C14—Cl2 | 111.44 (15) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···Cl2 | 0.86 | 2.69 | 3.055 (2) | 107 |
N1—H1D···Cl1 | 0.86 | 2.89 | 3.049 (2) | 92 |
C4—H4···Cl3i | 0.93 | 2.94 | 3.755 (3) | 147 |
C9—H9···Mii | 0.93 | 2.74 | 3.547 (3) | 145 |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Selected geometric parameters (Å, º) for (II) topCl1—C9 | 1.773 (2) | N1—H1D | 0.81 (2) |
Cl2—C9 | 1.7661 (19) | N2—C10 | 1.406 (2) |
Cl3—C9 | 1.7770 (18) | N2—C8 | 1.437 (2) |
N1—C1 | 1.400 (2) | N2—H2D | 0.76 (2) |
N1—C8 | 1.438 (2) | C8—C9 | 1.557 (2) |
| | | |
C1—N1—C8 | 125.76 (16) | C2—C1—N1 | 118.62 (16) |
C1—N1—H1D | 116.1 (16) | C6—C1—N1 | 123.87 (17) |
C8—N1—H1D | 116.1 (16) | N2—C8—N1 | 114.08 (15) |
C10—N2—C8 | 121.48 (16) | N2—C8—C9 | 108.01 (15) |
C10—N2—H2D | 115.7 (18) | N1—C8—C9 | 110.73 (15) |
C8—N2—H2D | 116.4 (18) | C15—C10—N2 | 118.22 (16) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl3 | 0.76 (2) | 2.70 (2) | 3.085 (2) | 113 (2) |
C14—H14···Cl1i | 0.93 | 2.93 | 3.699 (2) | 141 |
C15—H15···Cl1ii | 0.93 | 2.88 | 3.705 (3) | 148 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z. |
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Some chloral derivatives with amides have found some use as hypnotics and sedatives as substitutes for chloral hydrate. However, chloral has been combined with amides to give only a few `aldehyde ammonia'-type compounds for which therapeutic merit is claimed. In addition to the `chloral amines', some bis(arylamino)trichloromethylmethanes have been prepared by condensing two molecules of aromatic primary amine with one molecule of chloral hydrate (Stumerford & Dalton, 1944).
Our interest in chloral derivatives with aromatic primary amines stems from their possible use as important intermediates in the construction of five-membered ring compounds (Katritzky & Fan, 1990). We have prepared several novel chloral derivatives (Z.-F. Zhang, D.-C. Wang, S.-Q. Wang & G.-R. Qu, unpublished). As part of our synthetic and structural studies, the structures of the title compounds, (I) and (II), have been determined.
The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. The trichloroethane-1,1-diamine fragments in the two molecules adopt a low-energy gauche conformation with respect to the C7—C14 and C8—C9 bonds, respectively. This is similar to the situation in analogous compounds containing the trichloromethyl group (Krishnaiah et al., 2007; Hartung et al., 2005). The two molecules take up `twist' conformations with N1—C7—C14—Cl2 and N2—C7—C14—Cl2 torsion angles of -59.37 (2) and 65.57 (2)°, respectively, for (I). The corresponding torsion angles, N1—C8—C9—Cl3 and N2—C8—C9—Cl3, in structure (II) are -63.52 (2) and 62.07 (2)°, respectively. In (I) and (II), the dihedral angles between the two aromatic rings are 87.2 (2) and 82.5 (1)°, respectively, indicating that the phenyl rings are almost perpendicular to one another (Figs.1 and 2). The orientations are mainly attributed to a pair of intramolecular bifurcated donor hydrogen bonds (N1—H1D···Cl1 and N1—H1D···Cl2) for (I), and an intramolecular interaction (N2—H2D···Cl3) and a van der Waals repulsion effect between the trichloromethyl group and the two aromatic rings for (II) (Tables 2 and 4).
Selected geometric parameters for the two molecules are given in Tables 1 and 3. The N1—C1 and N2—C8 distances in (I) and the corresponding N1—C1 and N2—C10 bond lengths in (II) are shorter than the standard N—C bond length (1.47 Å; Mak et al., 2002). This is similar to what has been found in diphenylamine (Wang et al., 2005). This difference is considered to be the result of π conjugation between the N atom and the aromatic ring. In (I), the C2—C1—N1—C7 and C9—C8—N2—C7 torsion angles (-177.2 and -176.6°, respectively) are consistent with the equivalent angles in (II) (-175.3 and -6.2°), showing that the N atoms lie approximately in the same plane as the aromatic rings to which they are bonded. However, as compared with the ideal value of 120°, the C7—N2—C8 bond angle in (I) and the C1—N1—C8 angle in (II) are strikingly large. The deviation is due to a van der Waals repulsion between atoms H7 and H13 in (I), and H6 and H8 in (II).
The two NH H atoms in each molecule gave identical chemical shifts and identical coupling constants with the adjacent CH H atom [J = 7.2 Hz in (I) and 8.4 Hz in (II)], suggesting that in solution 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 [131.5 and 161.7° for H1D—N1—C7—H7 and H2D—N2—C7—H7, respectively, in (I), and 149.9 and 155.5° for H1D—N1—C8—H8 and H2D—N2—C8—H8, respectively, in (II)].
The molecules of (I) (Fig. 1) are linked into sheets by two hydrogen bonds, one of C—H···Cl and one of C—H···π(arene) type (Table 2), the formation of which is readily analysed in terms of two one-dimensional substructures, one formed by a C—H···π hydrogen bond and one formed by a C—H···Cl hydrogen bond. For the sake of simplicity, we shall omit any further consideration of the C—H···C hydrogen bonds, which are too weak to influence the overall dimensionality of the supramolecular structure. In the first substructure, atom C9 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C1–C6 ring in the molecule at (x, -y + 1/2, z - 1/2), thus forming a C22(8) chain running along the (3/4, 1/4, y) direction and generated by 21 screw axis along (3/4, 1/4, z) (Fig. 3). In the second substructure, atom C4 in the molecule at (x, y, z) acts as a hydrogen-bond donor to trichloromethyl atom Cl3 in the molecule at (x - 1, -y + 1/2, z + 1/2), so forming a C22(9) chain running parallel to the (1/2, 0, 3/4) direction and generated by a 21 screw axis along (x, 1/4, 1/2) (Fig. 4) [please check; symmcodes in Table 2 do not match those in text in figures]·The combination of the two chain motifs is sufficient to link all the molecules into a two-dimensional sheet parallel to (040) (Fig. 4). Two such sheets pass through each unit cell, in the domains 0 < y < 1/2 and 1/2 < y < 1.
The crystal structure of (II) takes on a simple one-dimensional double-columnar packing along the [100] direction via a combination of two independent C—H···Cl hydrogen bonds (Table 3) and one Cl···Cl interaction. Atom C14 in the molecule at (x, y, z) acts as a hydrogen-bond donor to trichloromethyl atom Cl1 in the molecule at (-x + 1, -y, -z), so generating by inversion a dimer centred at (1/2, 0, 0) and characterized by the usual R22(16) (Bernstein et al., 1995) motif (Fig. 5). This dimer can be regarded as the back building unit within the structure, from which the one-dimensional double-columnar structure is built. The one-dimensional structure involves a C—H···Cl hydrogen bond and a Cl···Cl interaction. Atoms C15 and Cl3 in the molecule at (x, y, z), parts of the dimer centred at (1/2, 0, 0), act as a hydrogen-bond donor and an intermolecular approach, respectively, to trichloromethyl atoms Cl1 and Cl2 [Cl3···Cl2 = 3.491 (3) Å] in the molecule at (x + 1, y, z), which is part of the dimer centred at (3/2, 0, 0). Propagation by inversion then generates a C(7) chain (Bernstein et al., 1995) along the a axis.
There are no classical intermolecular hydrogen bonds present in either structure, though the NH groups could have taken on the role of active donor or acceptor groups in intermolecular interactions. The absence of classical hydrogen bonds can be attributed to steric control by the bulky groups nearby.