Hydrogen-bonded chains in 2,2,2-trichloro-N,N′-bis­(4-methoxy­phenyl)­ethane-1,1-diamine and a three-dimensional hydrogen-bonded framework in 2,2,2-trichloro-N,N′-bis­(4-chloro­phenyl)­ethane-1,1-diamine

In 2,2,2-trichloro-N,N′-bis­(4-methoxy­phenyl)­ethane-1,1-di­amine, C₁₆H₁₇Cl₃N₂O₂, mol­ecules are linked into helical chains by N—H...O hydrogen bonds. Mol­ecules of 2,2,2-trichloro-N,N′-bis­(4-chloro­phenyl)­ethane-1,1-diamine, C₁₄H₁₁­Cl₅N₂, are connected into a three-dimensional framework by two independent Cl...Cl inter­actions and one C—H...Cl hydrogen bond.

S1. Comment

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.

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(carrier atom).

Computing details

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).

Figures

	Fig. 1. The molecule of (I), showing the the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), showing the the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C(9) helical chain parallel to the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or ampersand (&) are at the symmetry positions (−1/2 − x, y − 1/2, z) and (−1/2 − x, 1/2 + y, z), respectively.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a C(9) chain parallel to the [110] direction. Atoms marked with an asterisk (*) or ampersand (&) are at the symmetry positions (x − 1, y − 1, z) and (x + 1, y + 1, z), respectively.
	Fig. 5. Part of the crystal structure of (II), showing the formation of a C(9) chain parallel to the [1, y, 1/4] direction. Atoms marked with an asterisk (*) or ampersand (&) are at the symmetry positions (x + 1, y − 1, z) and (x − 1, y + 1, z), respectively.
	Fig. 6. Part of the crystal structure of (II), showing the formation of a C(5) chain of rings along the [010] direction. Atoms marked with an asterisk (*) or ampersand (&) are at the symmetry positions (2 − x, 1/2 + y, 1/2 − z) and (2 − x, −1/2 + y, 1/2 − z), respectively.

(I) 2,2,2-trichloro-N,N'-bis(4-methoxyphenyl)ethane-1,1-diamine

Crystal data

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) Å^3	Block, colourless
Z = 8	0.38 × 0.29 × 0.25 mm
F(000) = 1552

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 3.5039P] where P = (Fo^2 + 2Fc^2)/3
3233 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O1^i	0.86	2.54	3.150 (3)	128

Symmetry code: (i) −x−1/2, y−1/2, z.

(II) 2,2,2-trichloro-N,N'-bis(4-chlorophenyl)ethane-1,1-diamine

Crystal data

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) Å^3	Block, colourless
Z = 4	0.42 × 0.31 × 0.28 mm
F(000) = 776

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.036P)^2 + 0.3399P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···Cl4^i	0.93	2.89	3.774 (3)	160

Symmetry code: (i) −x+2, y+1/2, −z+1/2.