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The mol­ecules of 2,2,2-trichloro-N,N′-diphenyl­ethane-1,1-diamine, C14H13Cl3N2, 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, C16H17Cl3N2, the mol­ecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107034956/hj3039sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034956/hj3039Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034956/hj3039IIsup3.hkl
Contains datablock II

CCDC references: 636105; 636106

Comment top

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 We have prepared several novel chloral derivatives (Z.-F. Zhang, D.-C. Wang, S.-Q. Wang & G.-R. Qu, unpublished).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.

Related literature top

For related literature, see: Bernstein et al. (1995); Hartung et al. (2005); Katritzky & Fan (1990); Krishnaiah et al. (2007); Mak et al. (2002); Stumerford & Dalton (1944); Wang et al. (2005).

Experimental top

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).

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a C22(8) chain along the (3/4, 1/4, y) direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, -y + 1/2, z - 1/2) and (x, -y + 1/2, z + 1/2), respectively.
[Figure 4] Fig. 4. Part of the crystal structure of (I), viewed along the (010) direction, showing the formation of a (040) sheet. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Intermolecular interactions are represented by dashed lines. Selected atoms are labelled. [Symmetry codes: (i) x - 1, -y + 1/2, z + 1/2; (ii) x, -y + 1/2, z - 1/2; Cg is the centroid of the C1–C6 ring.]
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of a R22(16) dimer centred at (1/2, 0, 0) and a C(7) chain along the (100) direction. Atoms marked with an asterisk (*), a hash (#) or an `at' symbol (@) are at the symmetry positions (x + 1, y, z), (-x + 2, -y, -z) and (-x + 1, -y, -z), respectively.
(I) 2,2,2-trichloro-N,N'-diphenylethane-1,1-diamine top
Crystal data top
C14H13Cl3N2F(000) = 648
Mr = 315.61Dx = 1.437 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.1225 (7) ÅCell parameters from 2776 reflections
b = 15.7539 (17) Åθ = 2.6–22.8°
c = 15.2020 (16) ŵ = 0.62 mm1
β = 95.936 (1)°T = 291 K
V = 1458.4 (3) Å3Block, colourless
Z = 40.25 × 0.17 × 0.14 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2717 independent reflections
Radiation source: fine-focus sealed tube2041 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
phi and ω scansθmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997a)
h = 77
Tmin = 0.863, Tmax = 0.917k = 1918
10979 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-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 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C14H13Cl3N2V = 1458.4 (3) Å3
Mr = 315.61Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.1225 (7) ŵ = 0.62 mm1
b = 15.7539 (17) ÅT = 291 K
c = 15.2020 (16) Å0.25 × 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 = 0.917Rint = 0.029
10979 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.04Δρmax = 0.35 e Å3
2717 reflectionsΔρmin = 0.34 e Å3
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
xyzUiso*/Ueq
Cl11.11696 (13)0.49239 (4)0.79205 (5)0.0714 (2)
Cl20.81810 (11)0.47878 (5)0.63491 (5)0.0700 (2)
Cl31.25641 (12)0.41168 (5)0.63853 (6)0.0755 (2)
N10.7747 (3)0.35121 (12)0.78349 (13)0.0527 (5)
H1D0.70810.39930.78030.063*
N20.9075 (3)0.28057 (12)0.66137 (13)0.0510 (5)
H2D0.78160.28620.63120.061*
C10.7018 (3)0.28814 (14)0.83771 (14)0.0417 (5)
C20.5175 (4)0.30378 (16)0.88191 (15)0.0490 (6)
H20.44690.35600.87520.059*
C30.4389 (4)0.24291 (18)0.93537 (16)0.0584 (7)
H30.31450.25400.96370.070*
C40.5431 (5)0.16586 (18)0.94712 (18)0.0651 (7)
H40.48890.12450.98280.078*
C50.7286 (5)0.15053 (17)0.90555 (18)0.0644 (7)
H50.80240.09920.91490.077*
C60.8064 (4)0.21017 (15)0.85023 (16)0.0533 (6)
H60.92930.19820.82120.064*
C70.9569 (3)0.33852 (14)0.73291 (14)0.0418 (5)
H71.07770.31440.77240.050*
C81.0420 (4)0.21589 (14)0.63544 (14)0.0426 (5)
C90.9689 (4)0.16890 (15)0.56090 (15)0.0528 (6)
H90.83380.18160.52990.063*
C101.0929 (6)0.10412 (17)0.53236 (18)0.0689 (8)
H101.04120.07370.48200.083*
C111.2923 (6)0.08332 (17)0.5769 (2)0.0742 (9)
H111.37520.03900.55740.089*
C121.3669 (5)0.12922 (18)0.65069 (19)0.0670 (8)
H121.50150.11570.68160.080*
C131.2446 (4)0.19519 (16)0.67957 (17)0.0553 (6)
H131.29860.22620.72920.066*
C141.0326 (4)0.42616 (15)0.70098 (15)0.0467 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0838 (5)0.0532 (4)0.0746 (5)0.0113 (3)0.0037 (4)0.0104 (3)
Cl20.0578 (4)0.0690 (5)0.0808 (5)0.0039 (3)0.0049 (3)0.0234 (4)
Cl30.0644 (4)0.0694 (5)0.0994 (6)0.0016 (4)0.0412 (4)0.0093 (4)
N10.0516 (12)0.0430 (11)0.0669 (13)0.0096 (9)0.0218 (10)0.0048 (10)
N20.0392 (10)0.0562 (12)0.0553 (12)0.0044 (9)0.0056 (9)0.0109 (10)
C10.0387 (12)0.0465 (13)0.0400 (12)0.0028 (10)0.0046 (10)0.0065 (10)
C20.0412 (13)0.0598 (15)0.0459 (13)0.0040 (11)0.0035 (10)0.0065 (12)
C30.0473 (14)0.080 (2)0.0494 (15)0.0056 (14)0.0132 (12)0.0079 (14)
C40.0748 (19)0.0636 (18)0.0603 (17)0.0180 (15)0.0231 (14)0.0015 (14)
C50.083 (2)0.0454 (15)0.0680 (18)0.0036 (14)0.0243 (15)0.0007 (13)
C60.0554 (15)0.0488 (14)0.0587 (15)0.0045 (12)0.0203 (12)0.0028 (12)
C70.0371 (12)0.0440 (13)0.0447 (13)0.0024 (10)0.0066 (10)0.0024 (10)
C80.0469 (13)0.0412 (12)0.0401 (12)0.0043 (10)0.0065 (10)0.0010 (10)
C90.0696 (16)0.0464 (14)0.0414 (13)0.0109 (12)0.0007 (12)0.0010 (11)
C100.111 (3)0.0470 (16)0.0500 (16)0.0135 (16)0.0153 (16)0.0121 (13)
C110.106 (3)0.0452 (16)0.077 (2)0.0096 (16)0.0374 (19)0.0070 (15)
C120.0600 (17)0.0671 (18)0.075 (2)0.0155 (14)0.0112 (14)0.0052 (15)
C130.0529 (14)0.0588 (16)0.0533 (15)0.0069 (12)0.0015 (12)0.0156 (12)
C140.0401 (12)0.0481 (14)0.0522 (14)0.0023 (10)0.0060 (10)0.0009 (11)
Geometric parameters (Å, º) top
Cl1—C141.768 (2)C5—C61.378 (3)
Cl2—C141.774 (2)C5—H50.9300
Cl3—C141.761 (2)C6—H60.9300
N1—C11.393 (3)C7—C141.550 (3)
N1—C71.433 (3)C7—H70.9800
N1—H1D0.8600C8—C131.387 (3)
N2—C81.392 (3)C8—C91.388 (3)
N2—C71.428 (3)C9—C101.369 (4)
N2—H2D0.8600C9—H90.9300
C1—C61.389 (3)C10—C111.373 (4)
C1—C21.393 (3)C10—H100.9300
C2—C31.376 (3)C11—C121.373 (4)
C2—H20.9300C11—H110.9300
C3—C41.374 (4)C12—C131.379 (3)
C3—H30.9300C12—H120.9300
C4—C51.377 (4)C13—H130.9300
C4—H40.9300
C1—N1—C7122.18 (19)N2—C7—H7107.8
C1—N1—H1D118.9N1—C7—H7107.8
C7—N1—H1D118.9C14—C7—H7107.8
C8—N2—C7126.77 (19)C13—C8—C9117.8 (2)
C8—N2—H2D116.6C13—C8—N2124.1 (2)
C7—N2—H2D116.6C9—C8—N2118.1 (2)
C6—C1—C2118.4 (2)C10—C9—C8120.9 (3)
C6—C1—N1122.7 (2)C10—C9—H9119.5
C2—C1—N1118.9 (2)C8—C9—H9119.5
C3—C2—C1120.8 (2)C9—C10—C11121.0 (3)
C3—C2—H2119.6C9—C10—H10119.5
C1—C2—H2119.6C11—C10—H10119.5
C4—C3—C2120.4 (2)C10—C11—C12118.8 (3)
C4—C3—H3119.8C10—C11—H11120.6
C2—C3—H3119.8C12—C11—H11120.6
C3—C4—C5119.3 (3)C11—C12—C13120.8 (3)
C3—C4—H4120.4C11—C12—H12119.6
C5—C4—H4120.4C13—C12—H12119.6
C4—C5—C6120.9 (3)C12—C13—C8120.7 (2)
C4—C5—H5119.5C12—C13—H13119.6
C6—C5—H5119.5C8—C13—H13119.6
C5—C6—C1120.2 (2)C7—C14—Cl3109.15 (15)
C5—C6—H6119.9C7—C14—Cl1110.68 (16)
C1—C6—H6119.9Cl3—C14—Cl1108.56 (12)
N2—C7—N1112.50 (18)C7—C14—Cl2111.44 (15)
N2—C7—C14112.18 (18)Cl3—C14—Cl2109.09 (13)
N1—C7—C14108.56 (18)Cl1—C14—Cl2107.87 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1D···Cl20.862.693.055 (2)107
N1—H1D···Cl10.862.893.049 (2)92
C4—H4···Cl3i0.932.943.755 (3)147
C9—H9···Mii0.932.743.547 (3)145
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
(II) 2,2,2-trichloro-N,N'-bis(4-methylphenyl)ethane-1,1-diamine top
Crystal data top
C16H17Cl3N2F(000) = 712
Mr = 343.67Dx = 1.391 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3912 reflections
a = 5.9238 (7) Åθ = 2.6–26.6°
b = 14.6193 (16) ŵ = 0.55 mm1
c = 19.093 (2) ÅT = 291 K
β = 96.992 (1)°Flake, colourless
V = 1641.2 (3) Å30.44 × 0.35 × 0.26 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3756 independent reflections
Radiation source: fine-focus sealed tube2955 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
phi and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997a)
h = 77
Tmin = 0.793, Tmax = 0.871k = 1818
11838 measured reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H 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 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C16H17Cl3N2V = 1641.2 (3) Å3
Mr = 343.67Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.9238 (7) ŵ = 0.55 mm1
b = 14.6193 (16) ÅT = 291 K
c = 19.093 (2) Å0.44 × 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 = 0.871Rint = 0.021
11838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.26 e Å3
3756 reflectionsΔρmin = 0.34 e Å3
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
xyzUiso*/Ueq
Cl10.08280 (9)0.09977 (4)0.04411 (3)0.05775 (16)
Cl20.19299 (8)0.13076 (4)0.18383 (3)0.05699 (16)
Cl30.23639 (8)0.19339 (3)0.14612 (4)0.06536 (18)
N10.2129 (3)0.01115 (12)0.23320 (9)0.0492 (4)
N20.3127 (3)0.01075 (12)0.11558 (10)0.0495 (4)
C10.1040 (3)0.03174 (12)0.28542 (10)0.0416 (4)
C20.2082 (3)0.03005 (14)0.35451 (11)0.0521 (5)
H20.34950.00210.36470.062*
C30.1062 (4)0.06897 (15)0.40834 (11)0.0581 (5)
H30.18050.06680.45410.070*
C40.1054 (4)0.11147 (13)0.39604 (11)0.0514 (5)
C50.2055 (3)0.11434 (14)0.32724 (11)0.0504 (5)
H50.34500.14360.31710.061*
C60.1062 (3)0.07528 (14)0.27245 (10)0.0483 (5)
H60.18020.07810.22670.058*
C70.2196 (5)0.15171 (19)0.45545 (13)0.0756 (7)
H7A0.14020.20600.47260.113*
H7B0.21690.10790.49300.113*
H7C0.37440.16680.43850.113*
C80.1371 (3)0.01025 (12)0.15874 (10)0.0416 (4)
H80.01820.03640.14990.050*
C90.0315 (3)0.10421 (12)0.13430 (10)0.0438 (4)
C100.4166 (3)0.09734 (12)0.11755 (9)0.0389 (4)
C110.3454 (3)0.17078 (13)0.15532 (10)0.0451 (4)
H110.22080.16450.18030.054*
C120.4596 (3)0.25352 (13)0.15593 (11)0.0477 (4)
H120.40860.30230.18100.057*
C130.6474 (3)0.26591 (13)0.12033 (10)0.0456 (4)
C140.7121 (3)0.19290 (13)0.08123 (11)0.0468 (4)
H140.83490.19970.05570.056*
C150.5991 (3)0.11015 (13)0.07915 (10)0.0434 (4)
H150.64540.06260.05190.052*
C160.7805 (4)0.35437 (15)0.12444 (14)0.0679 (6)
H16A0.89580.35250.16440.102*
H16B0.67960.40470.12950.102*
H16C0.85070.36210.08210.102*
H1D0.344 (4)0.0256 (15)0.2444 (11)0.057 (6)*
H2D0.386 (4)0.0291 (17)0.1064 (12)0.062 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0666 (3)0.0514 (3)0.0537 (3)0.0001 (2)0.0010 (2)0.0102 (2)
Cl20.0428 (3)0.0583 (3)0.0709 (4)0.0075 (2)0.0113 (2)0.0059 (2)
Cl30.0437 (3)0.0412 (3)0.1098 (5)0.0067 (2)0.0038 (3)0.0014 (3)
N10.0354 (8)0.0605 (10)0.0502 (10)0.0077 (7)0.0008 (7)0.0031 (8)
N20.0464 (9)0.0396 (9)0.0656 (11)0.0041 (7)0.0195 (8)0.0110 (8)
C10.0385 (9)0.0384 (9)0.0468 (10)0.0020 (7)0.0006 (8)0.0007 (8)
C20.0464 (10)0.0526 (11)0.0540 (12)0.0081 (9)0.0067 (9)0.0011 (9)
C30.0649 (13)0.0597 (13)0.0458 (11)0.0069 (10)0.0091 (10)0.0010 (10)
C40.0625 (12)0.0429 (10)0.0481 (11)0.0039 (9)0.0041 (9)0.0027 (9)
C50.0473 (10)0.0475 (11)0.0560 (12)0.0086 (8)0.0044 (9)0.0037 (9)
C60.0445 (10)0.0561 (11)0.0428 (10)0.0067 (8)0.0015 (8)0.0032 (9)
C70.0898 (18)0.0788 (17)0.0581 (14)0.0217 (14)0.0086 (13)0.0107 (12)
C80.0372 (9)0.0392 (9)0.0484 (11)0.0003 (7)0.0049 (8)0.0022 (8)
C90.0361 (9)0.0399 (9)0.0549 (11)0.0020 (7)0.0038 (8)0.0010 (8)
C100.0350 (8)0.0401 (9)0.0408 (9)0.0006 (7)0.0011 (7)0.0037 (7)
C110.0401 (9)0.0454 (10)0.0512 (11)0.0016 (8)0.0110 (8)0.0061 (8)
C120.0481 (10)0.0425 (10)0.0531 (11)0.0005 (8)0.0083 (9)0.0098 (8)
C130.0451 (10)0.0420 (10)0.0490 (11)0.0045 (8)0.0027 (8)0.0013 (8)
C140.0410 (9)0.0508 (11)0.0499 (11)0.0028 (8)0.0107 (8)0.0004 (9)
C150.0429 (9)0.0430 (10)0.0450 (10)0.0030 (8)0.0080 (8)0.0073 (8)
C160.0730 (15)0.0508 (13)0.0829 (17)0.0169 (11)0.0213 (13)0.0089 (12)
Geometric parameters (Å, º) top
Cl1—C91.773 (2)C7—H7A0.9600
Cl2—C91.7661 (19)C7—H7B0.9600
Cl3—C91.7770 (18)C7—H7C0.9600
N1—C11.400 (2)C8—C91.557 (2)
N1—C81.438 (2)C8—H80.9800
N1—H1D0.81 (2)C10—C111.387 (2)
N2—C101.406 (2)C10—C151.391 (3)
N2—C81.437 (2)C11—C121.385 (3)
N2—H2D0.76 (2)C11—H110.9300
C1—C21.387 (3)C12—C131.384 (3)
C1—C61.393 (2)C12—H120.9300
C2—C31.377 (3)C13—C141.383 (3)
C2—H20.9300C13—C161.512 (3)
C3—C41.393 (3)C14—C151.381 (3)
C3—H30.9300C14—H140.9300
C4—C51.375 (3)C15—H150.9300
C4—C71.509 (3)C16—H16A0.9600
C5—C61.384 (3)C16—H16B0.9600
C5—H50.9300C16—H16C0.9600
C6—H60.9300
C1—N1—C8125.76 (16)N2—C8—H8107.9
C1—N1—H1D116.1 (16)N1—C8—H8107.9
C8—N1—H1D116.1 (16)C9—C8—H8107.9
C10—N2—C8121.48 (16)C8—C9—Cl2109.55 (13)
C10—N2—H2D115.7 (18)C8—C9—Cl1110.53 (13)
C8—N2—H2D116.4 (18)Cl2—C9—Cl1107.75 (9)
C2—C1—C6117.50 (18)C8—C9—Cl3111.45 (12)
C2—C1—N1118.62 (16)Cl2—C9—Cl3108.54 (10)
C6—C1—N1123.87 (17)Cl1—C9—Cl3108.93 (10)
C3—C2—C1121.16 (18)C11—C10—C15118.36 (16)
C3—C2—H2119.4C11—C10—N2123.42 (17)
C1—C2—H2119.4C15—C10—N2118.22 (16)
C2—C3—C4121.75 (19)C12—C11—C10120.05 (18)
C2—C3—H3119.1C12—C11—H11120.0
C4—C3—H3119.1C10—C11—H11120.0
C5—C4—C3116.69 (19)C13—C12—C11122.08 (18)
C5—C4—C7121.73 (19)C13—C12—H12119.0
C3—C4—C7121.58 (19)C11—C12—H12119.0
C4—C5—C6122.42 (18)C14—C13—C12117.13 (17)
C4—C5—H5118.8C14—C13—C16120.73 (18)
C6—C5—H5118.8C12—C13—C16122.12 (18)
C5—C6—C1120.46 (18)C15—C14—C13121.78 (17)
C5—C6—H6119.8C15—C14—H14119.1
C1—C6—H6119.8C13—C14—H14119.1
C4—C7—H7A109.5C14—C15—C10120.52 (17)
C4—C7—H7B109.5C14—C15—H15119.7
H7A—C7—H7B109.5C10—C15—H15119.7
C4—C7—H7C109.5C13—C16—H16A109.5
H7A—C7—H7C109.5C13—C16—H16B109.5
H7B—C7—H7C109.5H16A—C16—H16B109.5
N2—C8—N1114.08 (15)C13—C16—H16C109.5
N2—C8—C9108.01 (15)H16A—C16—H16C109.5
N1—C8—C9110.73 (15)H16B—C16—H16C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2D···Cl30.76 (2)2.70 (2)3.085 (2)113 (2)
C14—H14···Cl1i0.932.933.699 (2)141
C15—H15···Cl1ii0.932.883.705 (3)148
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H13Cl3N2C16H17Cl3N2
Mr315.61343.67
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)291291
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)
V3)1458.4 (3)1641.2 (3)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.620.55
Crystal size (mm)0.25 × 0.17 × 0.140.44 × 0.35 × 0.26
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997a)
Multi-scan
(SADABS; Sheldrick, 1997a)
Tmin, Tmax0.863, 0.9170.793, 0.871
No. of measured, independent and
observed [I > 2σ(I)] reflections
10979, 2717, 2041 11838, 3756, 2955
Rint0.0290.021
(sin θ/λ)max1)0.6060.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.090, 1.04 0.038, 0.099, 1.03
No. of reflections27173756
No. of parameters172200
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.340.26, 0.34

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Cl1—C141.768 (2)N1—C11.393 (3)
Cl2—C141.774 (2)N2—C81.392 (3)
Cl3—C141.761 (2)
C1—N1—C7122.18 (19)N2—C7—C14112.18 (18)
C8—N2—C7126.77 (19)C7—C14—Cl1110.68 (16)
N2—C7—N1112.50 (18)C7—C14—Cl2111.44 (15)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1D···Cl20.862.693.055 (2)107
N1—H1D···Cl10.862.893.049 (2)92
C4—H4···Cl3i0.932.943.755 (3)147
C9—H9···Mii0.932.743.547 (3)145
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
Selected geometric parameters (Å, º) for (II) top
Cl1—C91.773 (2)N1—H1D0.81 (2)
Cl2—C91.7661 (19)N2—C101.406 (2)
Cl3—C91.7770 (18)N2—C81.437 (2)
N1—C11.400 (2)N2—H2D0.76 (2)
N1—C81.438 (2)C8—C91.557 (2)
C1—N1—C8125.76 (16)C2—C1—N1118.62 (16)
C1—N1—H1D116.1 (16)C6—C1—N1123.87 (17)
C8—N1—H1D116.1 (16)N2—C8—N1114.08 (15)
C10—N2—C8121.48 (16)N2—C8—C9108.01 (15)
C10—N2—H2D115.7 (18)N1—C8—C9110.73 (15)
C8—N2—H2D116.4 (18)C15—C10—N2118.22 (16)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N2—H2D···Cl30.76 (2)2.70 (2)3.085 (2)113 (2)
C14—H14···Cl1i0.932.933.699 (2)141
C15—H15···Cl1ii0.932.883.705 (3)148
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z.
 

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