Three 1,2,4-triazole derivatives containing subtituted benzyl and benzyl­amino groups

The title compounds, 4-benzyl­amino-3-(4-methyl­benzyl)-1H-1,2,4-triazol-5(4H)-one, C₁₇H₁₈N₄O, (I), 3-(4-methyl­benzyl)-4-(4-methyl­benzyl­amino)-1H-1,2,4-tri­azol-5(4H)-one, C₁₈H₂₀N₄O, (II), and 3-(4-chloro­benzyl)-4-(4-methyl­benzyl­amino)-1H-1,2,4-triazol-5(4H)-one, C₁₇H₁₇ClN₄O, (III), were obtained from the corresponding Schiff base in the presence of diglyme and NaBH₄. Each compound contains a 1,2,4-triazole ring and two benzene rings, which are essentially planar. The molecules are linked by a combination of intermolecular N—H...O and N—H...N hydrogen bonds. Additionally, there is a weak π–π stacking interaction in (I), involving the benzene ring of the amino­benzyl group and the partially aromatic 1,2,4-triazole moiety, with a centroid–centroid distance of 3.7397 (10) Å.

S1. Comment

1,2,4-Triazole and its derivatives have been used as starting materials for the synthesis of many heterocycles (Desenko, 1995). Substituted 1,2,4-triazoles have also been used as ligands to obtain metal complexes with specific properties (Kaszuwara et al., 1992; Prins et al., 1996; Drabent et al., 2004). Studies indicate that the 1,2,4-triazole moiety is associated with anticorrosion (Al-Kharafi et al., 1986) and anti-inflammatory action (Gupta & Bhargava, 1978), and with pharmacological activities, such as antiviral, analgesic, antimicrobial, antidepressant and antifungal effects (Jones et al., 1965; Sughen & Yoloye, 1978; Cansiz et al., 2001; Kane et al., 1988; Massa et al., 1992). As a contination of our studies of the structural analysis of Schiff-base-containing substituted 1,2,4-triazole derivatives (Arslan et al., 2004; Yilmaz et al., 2004), we report here the crystal and molecular structures of three substituted 1,2,4-triazole compounds, 3 − p-methylbenzyl-4-benzylamino-4,5-dihydro-1H-1,2,4-triazol-5-one, (I), 3 − p-methylbenzyl-4-(p-methylbenzylamino)-4,5-dihydro-1H-1,2,4-triazol-5-one, (II), and 3 − p-chlorobenzyl-4-(p-methylbenzylamino)-4,5-dihydro-1H-1,2,4-triazol-5-one, (III), which are expected to exhibit pharmacological properties and to act as suitable ligands in coordination chemistry. The title compounds were obtained from the corresponding Schiff base in the presence of diglyme and NaBH₄.

Views of the molecules of compounds (I)–(III), including the atom-numbering schemes, are shown in Figs. 1–3. Compounds (I)-(III) consist mainly of three bonded planar rings, namely a triazole ring (A), a benzyl ring (B) and a benzylamino ring (C). The r.m.s. deviations for rings A, B and C are 0.007, 0.004 and 0.001 Å, respectively, in (I), 0.002, 0.002 and 0.007 Å, respectively, in (II), and 0.001, 0.005 and 0.002 Å, respectively, in (III). The molecules of (I)-(III) adopt similar conformations (Figs. 1–3). The dihedral angles between rings A/B and A/C are 62.05 (5) and 46.44 (5)°, respectively, in (I), 69.99 (10) and 44.89 (10)°, respectively, in (II), and 67.58 (12) and 49.48 (10)°, respectively, in (III). A non-planar disposition of the three rings has been observed in similar 1,2,4-triazole derivatives (Zhu et al., 2000; Bruno et al., 2003; Arslan et al., 2004; Yilmaz et al., 2004). The slightly different rotations of these rings may be due to stacking interactions of the 1,2,4-triazole moiety. The orientation of the rings obviously leaves atom N2 available as a possible metal coordination site, together with the adjacent atoms N1, N3 and N4. The coordinating and pharmacologically active fragments are connected to an aromatic spacer (the benzyl group), controlling the distance between the sites and also allowing a possible electronic coupling. However, the C8—C9 bonds in (I) and (II), [C7—C8 in (III)], are almost the same length, thus confirming the absence of important conjugation effects.

The five-membered triazole rings in (I)–(III) have the same planar geometry as all similar fragments reported in the Cambridge Structural Database (Version?; Allen, 2002). The interatomic distances within the triazole cycles of (I)–(III) are not equal, ranging from 1.287 (4) to 1.394 (3) Å, but similar bonds display comparable bond lengths and angles, as listed in Tables 1–3. The C9—N2 bond in (I) and (II), [C8—N2 in (III)], is the only double bond, being much shorter than the other C—N bonds in the triazole cycle. On the other hand, the C11—N4 bond in (I) and (II), [C10—N4 in (III)], has single-bond character and is significantly longer than the C—N bonds in the ring. The remaining bond lengths in (I)–(III) show no unusual values. The N3—N4—C11—C12 methylamine system in (I) and (II) [N3—N4—C10—C11 in (III)] is not planar, as evidenced by the torsion angles, with an mean value of 75 (1)°. However, the same fragment with a C═N double bond in a 1,2,4-triazole derivative was reported to be planar (Bruno et al., 2003).

The packing of the molecules in (I)–(III) is shown in Figs. 4–6. Analysis of crystal packing of the title compounds reveals that the molecules are linked by means of similar intermolecular N—H···O and N—H···N hydrogen bonds (Tables 4–6). It seems that the N—H···O hydrogen bonds are stronger than the N—H···N interactions. In contrast with (II) and (III), in (I), a weak π–π stacking interaction between the phenyl ring of the aminobenzyl group and the partially aromatic 1,2,4-triazole cycle is observed [Cg···Cg(x, 3/2 − y, 1/2 + z) 3.7397 (10) Å]. Similar interactions in (II) and (III) are longer than 4.5 Å.

S2. Experimental

The synthesis and characterization of the title compounds has been reported elsewhere by Kahveci & Ikizler (2000). Single crystals suitable for X-ray measurements were obtained by crystallization from ethyl acetate.

S3. Refinement

The amine H atoms in (I) were refined freely, whereas in (II) and (III), the H atom on N1 was placed in a calculated position, while the H atom on N4 was refined freely. Other H atoms were placed in calculated positions, with C—H distances in the range 0.93–0.97 Å Please check amended text and with U_iso(H) = 1.2U_eq(C).

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A packing diagram for (I). H atoms bound to C atoms have been omitted for clarity.
	Fig. 5. A packing diagram for (II). H atoms bound to C atoms have been omitted for clarity.
	Fig. 6. A packing diagram for (III). H atoms bound to C atoms have been omitted for clarity.

(I) 4-Benzylamino-3-(4-methylbenzyl)-4,5-dihydro-1H-1,2,4-triazol-5-one

Crystal data

C17H18N4O	F(000) = 624
Mr = 294.35	Dx = 1.285 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12405 reflections
a = 17.0906 (13) Å	θ = 1.3–26.0°
b = 5.9866 (3) Å	µ = 0.08 mm^−1
c = 15.6784 (15) Å	T = 293 K
β = 108.496 (7)°	Prismatic, colourless
V = 1521.3 (2) Å^3	0.49 × 0.43 × 0.19 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	2054 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
Graphite monochromator	θmax = 26.1°, θmin = 1.3°
Detector resolution: 6.67 pixels mm^-1	h = −21→21
rotation scans	k = −7→7
20832 measured reflections	l = −19→19
3008 independent reflections

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0697P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.008
3008 reflections	Δρmax = 0.15 e Å^−3
209 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (2)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.57217 (11)	0.6733 (4)	0.93832 (13)	0.0849 (6)
H1A	0.5642	0.6610	0.9961	0.102*
H1B	0.6155	0.7785	0.9419	0.102*
H1C	0.5870	0.5300	0.9206	0.102*
C2	0.49347 (9)	0.7526 (3)	0.86998 (11)	0.0585 (4)
C3	0.46243 (10)	0.9645 (3)	0.87452 (11)	0.0619 (4)
H3	0.4905	1.0601	0.9209	0.074*
C4	0.39017 (9)	1.0364 (3)	0.81101 (11)	0.0558 (4)
H4	0.3700	1.1784	0.8161	0.067*
C5	0.34760 (8)	0.9009 (2)	0.74039 (10)	0.0463 (3)
C6	0.37900 (9)	0.6908 (3)	0.73539 (11)	0.0564 (4)
H6	0.3514	0.5963	0.6884	0.068*
C7	0.45080 (10)	0.6179 (3)	0.79909 (12)	0.0610 (4)
H7	0.4706	0.4755	0.7940	0.073*
C8	0.27072 (8)	0.9855 (2)	0.66970 (10)	0.0480 (3)
H8A	0.2759	1.1456	0.6637	0.058*
H8B	0.2677	0.9181	0.6125	0.058*
C9	0.19207 (8)	0.9396 (2)	0.68817 (9)	0.0424 (3)
C10	0.07857 (8)	0.7662 (2)	0.69513 (9)	0.0467 (3)
C11	0.12621 (10)	0.5108 (3)	0.54312 (11)	0.0611 (4)
H11A	0.0682	0.5376	0.5342	0.073*
H11B	0.1323	0.3573	0.5265	0.073*
C12	0.15530 (9)	0.6651 (3)	0.48429 (10)	0.0533 (4)
C13	0.22901 (10)	0.6247 (3)	0.46771 (11)	0.0626 (4)
H13	0.2582	0.4943	0.4892	0.075*
C14	0.25978 (12)	0.7760 (4)	0.41962 (12)	0.0761 (5)
H14	0.3095	0.7472	0.4093	0.091*
C15	0.21718 (14)	0.9675 (4)	0.38727 (12)	0.0803 (6)
H15	0.2382	1.0705	0.3558	0.096*
C16	0.14365 (14)	1.0070 (3)	0.40136 (13)	0.0794 (6)
H16	0.1141	1.1359	0.3784	0.095*
C17	0.11291 (11)	0.8574 (3)	0.44934 (11)	0.0672 (5)
H17	0.0627	0.8867	0.4583	0.081*
N1	0.08248 (7)	0.9776 (2)	0.72416 (9)	0.0530 (3)
N2	0.15298 (7)	1.08727 (19)	0.72013 (9)	0.0508 (3)
N3	0.14967 (6)	0.74315 (18)	0.67181 (7)	0.0424 (3)
N4	0.17394 (7)	0.5454 (2)	0.63873 (9)	0.0485 (3)
O1	0.02578 (6)	0.62074 (18)	0.68820 (8)	0.0600 (3)
H1	0.0438 (12)	1.044 (3)	0.7510 (13)	0.088 (6)*
H4A	0.1644 (10)	0.432 (3)	0.6707 (11)	0.061 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0568 (10)	0.1134 (16)	0.0812 (13)	0.0188 (11)	0.0172 (9)	0.0021 (12)
C2	0.0465 (8)	0.0716 (11)	0.0616 (9)	0.0025 (8)	0.0231 (7)	0.0043 (8)
C3	0.0562 (9)	0.0700 (11)	0.0596 (9)	−0.0034 (8)	0.0187 (8)	−0.0119 (8)
C4	0.0540 (8)	0.0517 (9)	0.0651 (9)	−0.0007 (7)	0.0234 (7)	−0.0078 (8)
C5	0.0421 (7)	0.0454 (8)	0.0574 (8)	−0.0047 (6)	0.0241 (6)	−0.0007 (6)
C6	0.0500 (8)	0.0511 (9)	0.0696 (10)	−0.0030 (7)	0.0208 (7)	−0.0096 (7)
C7	0.0525 (9)	0.0524 (9)	0.0828 (11)	0.0065 (7)	0.0281 (8)	−0.0003 (8)
C8	0.0456 (7)	0.0471 (8)	0.0562 (8)	−0.0037 (6)	0.0229 (6)	0.0017 (7)
C9	0.0428 (7)	0.0379 (7)	0.0498 (7)	0.0003 (6)	0.0193 (6)	0.0029 (6)
C10	0.0424 (7)	0.0477 (8)	0.0558 (8)	0.0010 (6)	0.0237 (6)	0.0055 (7)
C11	0.0574 (9)	0.0595 (10)	0.0669 (10)	−0.0113 (8)	0.0204 (8)	−0.0148 (8)
C12	0.0525 (8)	0.0567 (9)	0.0489 (8)	−0.0014 (7)	0.0137 (7)	−0.0115 (7)
C13	0.0636 (10)	0.0655 (10)	0.0621 (10)	0.0087 (8)	0.0246 (8)	−0.0061 (8)
C14	0.0792 (12)	0.0955 (15)	0.0639 (11)	−0.0051 (11)	0.0372 (10)	−0.0102 (10)
C15	0.1042 (15)	0.0807 (14)	0.0571 (10)	−0.0123 (12)	0.0273 (10)	−0.0001 (10)
C16	0.0996 (15)	0.0676 (12)	0.0585 (10)	0.0108 (11)	0.0072 (10)	0.0035 (9)
C17	0.0626 (10)	0.0721 (11)	0.0606 (10)	0.0109 (9)	0.0106 (8)	−0.0073 (9)
N1	0.0490 (7)	0.0490 (7)	0.0704 (8)	0.0009 (6)	0.0321 (6)	−0.0025 (6)
N2	0.0486 (6)	0.0444 (7)	0.0659 (8)	−0.0006 (5)	0.0273 (6)	−0.0019 (6)
N3	0.0411 (6)	0.0376 (6)	0.0547 (7)	0.0002 (5)	0.0238 (5)	0.0004 (5)
N4	0.0534 (7)	0.0374 (6)	0.0610 (7)	0.0006 (5)	0.0270 (6)	−0.0013 (6)
O1	0.0521 (6)	0.0580 (6)	0.0802 (7)	−0.0098 (5)	0.0355 (5)	0.0002 (5)

Geometric parameters (Å, º)

C1—C2	1.506 (2)	C10—N1	1.3390 (19)
C1—H1A	0.9600	C10—N3	1.3825 (16)
C1—H1B	0.9600	C11—N4	1.476 (2)
C1—H1C	0.9600	C11—C12	1.497 (2)
C2—C7	1.379 (2)	C11—H11A	0.9700
C2—C3	1.386 (2)	C11—H11B	0.9700
C3—C4	1.386 (2)	C12—C17	1.378 (2)
C3—H3	0.9300	C12—C13	1.386 (2)
C4—C5	1.379 (2)	C13—C14	1.384 (2)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.380 (2)	C14—C15	1.367 (3)
C5—C8	1.512 (2)	C14—H14	0.9300
C6—C7	1.384 (2)	C15—C16	1.364 (3)
C6—H6	0.9300	C15—H15	0.9300
C7—H7	0.9300	C16—C17	1.376 (3)
C8—C9	1.4875 (18)	C16—H16	0.9300
C8—H8A	0.9700	C17—H17	0.9300
C8—H8B	0.9700	N1—N2	1.3911 (17)
C9—N2	1.3004 (17)	N1—H1	0.97 (2)
C9—N3	1.3625 (17)	N3—N4	1.4069 (16)
C10—O1	1.2338 (17)	N4—H4A	0.888 (18)
C2—C1—H1A	109.5	N1—C10—N3	103.36 (11)
C2—C1—H1B	109.5	N4—C11—C12	110.77 (12)
H1A—C1—H1B	109.5	N4—C11—H11A	109.5
C2—C1—H1C	109.5	C12—C11—H11A	109.5
H1A—C1—H1C	109.5	N4—C11—H11B	109.5
H1B—C1—H1C	109.5	C12—C11—H11B	109.5
C7—C2—C3	117.61 (15)	H11A—C11—H11B	108.1
C7—C2—C1	120.92 (16)	C17—C12—C13	117.76 (16)
C3—C2—C1	121.46 (17)	C17—C12—C11	121.66 (15)
C2—C3—C4	121.04 (16)	C13—C12—C11	120.47 (15)
C2—C3—H3	119.5	C14—C13—C12	120.86 (17)
C4—C3—H3	119.5	C14—C13—H13	119.6
C5—C4—C3	121.13 (15)	C12—C13—H13	119.6
C5—C4—H4	119.4	C15—C14—C13	120.09 (18)
C3—C4—H4	119.4	C15—C14—H14	120.0
C4—C5—C6	117.80 (14)	C13—C14—H14	120.0
C4—C5—C8	120.39 (13)	C16—C15—C14	119.66 (19)
C6—C5—C8	121.78 (13)	C16—C15—H15	120.2
C5—C6—C7	121.21 (15)	C14—C15—H15	120.2
C5—C6—H6	119.4	C15—C16—C17	120.46 (19)
C7—C6—H6	119.4	C15—C16—H16	119.8
C2—C7—C6	121.21 (15)	C17—C16—H16	119.8
C2—C7—H7	119.4	C16—C17—C12	121.15 (17)
C6—C7—H7	119.4	C16—C17—H17	119.4
C9—C8—C5	115.10 (11)	C12—C17—H17	119.4
C9—C8—H8A	108.5	C10—N1—N2	112.41 (11)
C5—C8—H8A	108.5	C10—N1—H1	124.3 (12)
C9—C8—H8B	108.5	N2—N1—H1	123.0 (12)
C5—C8—H8B	108.5	C9—N2—N1	104.76 (11)
H8A—C8—H8B	107.5	C9—N3—C10	108.87 (11)
N2—C9—N3	110.59 (11)	C9—N3—N4	126.48 (10)
N2—C9—C8	123.78 (12)	C10—N3—N4	124.63 (11)
N3—C9—C8	125.59 (12)	N3—N4—C11	111.08 (12)
O1—C10—N1	130.79 (13)	N3—N4—H4A	107.8 (11)
O1—C10—N3	125.85 (13)	C11—N4—H4A	108.9 (11)
C7—C2—C3—C4	1.3 (2)	C14—C15—C16—C17	1.2 (3)
C1—C2—C3—C4	179.65 (16)	C15—C16—C17—C12	0.1 (3)
C2—C3—C4—C5	−1.2 (2)	C13—C12—C17—C16	−1.5 (2)
C3—C4—C5—C6	0.5 (2)	C11—C12—C17—C16	174.72 (15)
C3—C4—C5—C8	−177.57 (13)	O1—C10—N1—N2	−179.27 (15)
C4—C5—C6—C7	0.1 (2)	N3—C10—N1—N2	−0.11 (16)
C8—C5—C6—C7	178.04 (13)	N3—C9—N2—N1	0.10 (15)
C3—C2—C7—C6	−0.8 (2)	C8—C9—N2—N1	178.19 (12)
C1—C2—C7—C6	−179.15 (16)	C10—N1—N2—C9	0.01 (16)
C5—C6—C7—C2	0.1 (2)	N2—C9—N3—C10	−0.17 (16)
C4—C5—C8—C9	−91.23 (16)	C8—C9—N3—C10	−178.22 (13)
C6—C5—C8—C9	90.83 (16)	N2—C9—N3—N4	−178.74 (12)
C5—C8—C9—N2	100.90 (16)	C8—C9—N3—N4	3.2 (2)
C5—C8—C9—N3	−81.30 (17)	O1—C10—N3—C9	179.38 (14)
N4—C11—C12—C17	−101.01 (17)	N1—C10—N3—C9	0.17 (15)
N4—C11—C12—C13	75.09 (18)	O1—C10—N3—N4	−2.0 (2)
C17—C12—C13—C14	1.7 (2)	N1—C10—N3—N4	178.76 (12)
C11—C12—C13—C14	−174.60 (15)	C9—N3—N4—C11	−104.49 (15)
C12—C13—C14—C15	−0.4 (3)	C10—N3—N4—C11	77.16 (16)
C13—C14—C15—C16	−1.1 (3)	C12—C11—N4—N3	75.04 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.97 (2)	1.81 (2)	2.7676 (15)	169.9 (18)
N4—H4A···N2^ii	0.888 (18)	2.236 (19)	3.0933 (18)	162.2 (15)

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x, y−1, z.

(II) 3-(4-Methylbenzyl)-4-(4-methylbenzylamino)-4,5-dihydro-1H-1,2,4-triazol-5-one

Crystal data

C18H20N4O	F(000) = 656
Mr = 308.38	Dx = 1.218 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9419 reflections
a = 16.8511 (19) Å	θ = 1.2–25.0°
b = 5.996 (5) Å	µ = 0.08 mm^−1
c = 17.650 (2) Å	T = 293 K
β = 109.403 (9)°	Prismatic, colourless
V = 1682.0 (14) Å^3	0.50 × 0.44 × 0.40 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	3284 independent reflections
Radiation source: fine-focus sealed tube	1482 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.3°
rotation scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −7→7
Tmin = 0.962, Tmax = 0.987	l = −21→21
22631 measured reflections

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.021P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
3284 reflections	Δρmax = 0.12 e Å^−3
214 parameters	Δρmin = −0.14 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0090 (7)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.56717 (16)	0.1175 (6)	0.93177 (16)	0.1327 (12)
H1A	0.5702	−0.0420	0.9290	0.199*
H1B	0.5633	0.1600	0.9829	0.199*
H1C	0.6168	0.1821	0.9256	0.199*
C2	0.49010 (16)	0.2003 (5)	0.86519 (16)	0.0837 (8)
C3	0.45448 (15)	0.0787 (4)	0.79585 (17)	0.0809 (7)
H3	0.4782	−0.0576	0.7901	0.097*
C4	0.38500 (14)	0.1530 (3)	0.73514 (15)	0.0672 (6)
H4	0.3624	0.0661	0.6894	0.081*
C5	0.34808 (12)	0.3553 (3)	0.74107 (13)	0.0520 (5)
C6	0.38355 (15)	0.4781 (4)	0.81008 (15)	0.0735 (7)
H6	0.3599	0.6147	0.8157	0.088*
C7	0.45348 (16)	0.4025 (5)	0.87107 (15)	0.0882 (8)
H7	0.4762	0.4894	0.9168	0.106*
C8	0.27235 (11)	0.4413 (3)	0.67453 (12)	0.0564 (5)
H8A	0.2794	0.5998	0.6677	0.068*
H8B	0.2693	0.3676	0.6247	0.068*
C9	0.19211 (11)	0.4044 (3)	0.69040 (11)	0.0463 (5)
C10	0.07853 (13)	0.2335 (3)	0.70195 (12)	0.0549 (6)
C11	0.11872 (13)	−0.0315 (3)	0.56658 (12)	0.0630 (6)
H11A	0.0606	0.0020	0.5605	0.076*
H11B	0.1220	−0.1871	0.5528	0.076*
C12	0.14679 (13)	0.1134 (3)	0.51052 (12)	0.0571 (5)
C13	0.21907 (14)	0.0608 (4)	0.49412 (13)	0.0718 (7)
H13	0.2471	−0.0712	0.5143	0.086*
C14	0.25073 (16)	0.1983 (4)	0.44875 (14)	0.0798 (7)
H14	0.2998	0.1577	0.4391	0.096*
C15	0.21139 (16)	0.3945 (4)	0.41744 (13)	0.0707 (6)
C16	0.13764 (16)	0.4463 (4)	0.43168 (14)	0.0773 (7)
H16	0.1088	0.5761	0.4099	0.093*
C17	0.10591 (14)	0.3078 (4)	0.47789 (14)	0.0723 (6)
H17	0.0564	0.3468	0.4870	0.087*
C18	0.24811 (18)	0.5488 (4)	0.36959 (14)	0.1037 (9)
H18A	0.2121	0.6761	0.3521	0.156*
H18B	0.2525	0.4708	0.3236	0.156*
H18C	0.3030	0.5972	0.4027	0.156*
N1	0.08284 (10)	0.4486 (3)	0.72416 (10)	0.0623 (5)
H1	0.0460	0.5130	0.7407	0.075*
N2	0.15317 (9)	0.5553 (2)	0.71749 (10)	0.0572 (5)
N3	0.14931 (9)	0.2064 (2)	0.67991 (9)	0.0466 (4)
N4	0.17211 (10)	0.0067 (3)	0.65069 (11)	0.0510 (4)
O1	0.02609 (9)	0.0889 (2)	0.69989 (9)	0.0750 (5)
H4A	0.1626 (12)	−0.108 (3)	0.6841 (12)	0.089 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0678 (19)	0.209 (4)	0.113 (2)	0.030 (2)	0.0192 (18)	0.042 (2)
C2	0.0521 (17)	0.119 (2)	0.0826 (19)	0.0087 (15)	0.0255 (15)	0.0161 (16)
C3	0.0568 (17)	0.0746 (17)	0.117 (2)	0.0126 (13)	0.0363 (16)	0.0102 (15)
C4	0.0534 (15)	0.0586 (15)	0.0950 (18)	−0.0003 (11)	0.0319 (14)	−0.0089 (13)
C5	0.0437 (13)	0.0535 (13)	0.0677 (15)	−0.0044 (11)	0.0302 (12)	−0.0032 (11)
C6	0.0619 (16)	0.0779 (16)	0.0863 (17)	0.0027 (13)	0.0320 (14)	−0.0169 (15)
C7	0.0640 (18)	0.122 (2)	0.0771 (19)	−0.0064 (17)	0.0214 (15)	−0.0202 (17)
C8	0.0489 (13)	0.0497 (13)	0.0795 (15)	−0.0065 (10)	0.0333 (12)	0.0021 (11)
C9	0.0426 (12)	0.0398 (11)	0.0601 (13)	−0.0010 (9)	0.0220 (10)	0.0026 (10)
C10	0.0537 (14)	0.0452 (13)	0.0763 (15)	0.0015 (10)	0.0355 (12)	0.0017 (11)
C11	0.0638 (14)	0.0561 (14)	0.0697 (16)	−0.0096 (11)	0.0231 (13)	−0.0082 (12)
C12	0.0598 (14)	0.0517 (13)	0.0572 (14)	−0.0049 (11)	0.0160 (11)	−0.0067 (11)
C13	0.0890 (18)	0.0606 (15)	0.0751 (16)	0.0103 (13)	0.0397 (14)	0.0054 (13)
C14	0.100 (2)	0.0749 (17)	0.0803 (18)	0.0035 (15)	0.0506 (16)	0.0016 (14)
C15	0.093 (2)	0.0697 (17)	0.0480 (14)	−0.0096 (14)	0.0213 (13)	−0.0045 (12)
C16	0.0829 (19)	0.0608 (15)	0.0730 (16)	0.0004 (14)	0.0055 (14)	0.0086 (13)
C17	0.0582 (16)	0.0693 (16)	0.0840 (17)	0.0006 (13)	0.0162 (13)	−0.0021 (14)
C18	0.155 (3)	0.0932 (19)	0.0707 (16)	−0.0322 (18)	0.0474 (17)	0.0045 (15)
N1	0.0519 (11)	0.0488 (11)	0.1001 (14)	0.0020 (8)	0.0437 (10)	−0.0028 (10)
N2	0.0509 (11)	0.0437 (10)	0.0863 (13)	−0.0025 (8)	0.0350 (10)	−0.0003 (9)
N3	0.0449 (10)	0.0359 (9)	0.0665 (11)	−0.0009 (7)	0.0285 (9)	−0.0026 (8)
N4	0.0581 (11)	0.0381 (10)	0.0631 (12)	0.0011 (8)	0.0288 (9)	−0.0026 (9)
O1	0.0681 (10)	0.0602 (10)	0.1153 (13)	−0.0190 (8)	0.0551 (9)	−0.0081 (9)

Geometric parameters (Å, º)

C1—C2	1.517 (3)	C11—N4	1.476 (2)
C1—H1A	0.9600	C11—C12	1.506 (3)
C1—H1B	0.9600	C11—H11A	0.9700
C1—H1C	0.9600	C11—H11B	0.9700
C2—C7	1.380 (3)	C12—C13	1.379 (3)
C2—C3	1.379 (3)	C12—C17	1.379 (3)
C3—C4	1.373 (3)	C13—C14	1.375 (3)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.383 (3)	C14—C15	1.373 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.378 (3)	C15—C16	1.383 (3)
C5—C8	1.509 (3)	C15—C18	1.516 (3)
C6—C7	1.382 (3)	C16—C17	1.389 (3)
C6—H6	0.9300	C16—H16	0.9300
C7—H7	0.9300	C17—H17	0.9300
C8—C9	1.486 (2)	C18—H18A	0.9600
C8—H8A	0.9700	C18—H18B	0.9600
C8—H8B	0.9700	C18—H18C	0.9600
C9—N2	1.298 (2)	N1—N2	1.3858 (18)
C9—N3	1.369 (2)	N1—H1	0.8600
C10—O1	1.230 (2)	N3—N4	1.407 (2)
C10—N1	1.342 (2)	N4—H4A	0.95 (2)
C10—N3	1.382 (2)
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	N4—C11—H11B	109.5
H1A—C1—H1B	109.5	C12—C11—H11B	109.5
C2—C1—H1C	109.5	H11A—C11—H11B	108.1
H1A—C1—H1C	109.5	C13—C12—C17	117.3 (2)
H1B—C1—H1C	109.5	C13—C12—C11	119.9 (2)
C7—C2—C3	117.2 (2)	C17—C12—C11	122.7 (2)
C7—C2—C1	121.2 (3)	C14—C13—C12	121.7 (2)
C3—C2—C1	121.5 (3)	C14—C13—H13	119.1
C4—C3—C2	121.9 (2)	C12—C13—H13	119.1
C4—C3—H3	119.1	C15—C14—C13	121.3 (2)
C2—C3—H3	119.1	C15—C14—H14	119.3
C3—C4—C5	120.9 (2)	C13—C14—H14	119.3
C3—C4—H4	119.5	C14—C15—C16	117.5 (2)
C5—C4—H4	119.5	C14—C15—C18	121.0 (2)
C6—C5—C4	117.5 (2)	C16—C15—C18	121.4 (2)
C6—C5—C8	120.74 (19)	C15—C16—C17	121.1 (2)
C4—C5—C8	121.8 (2)	C15—C16—H16	119.4
C5—C6—C7	121.3 (2)	C17—C16—H16	119.4
C5—C6—H6	119.3	C12—C17—C16	120.9 (2)
C7—C6—H6	119.3	C12—C17—H17	119.5
C2—C7—C6	121.1 (2)	C16—C17—H17	119.5
C2—C7—H7	119.4	C15—C18—H18A	109.5
C6—C7—H7	119.4	C15—C18—H18B	109.5
C9—C8—C5	112.92 (16)	H18A—C18—H18B	109.5
C9—C8—H8A	109.0	C15—C18—H18C	109.5
C5—C8—H8A	109.0	H18A—C18—H18C	109.5
C9—C8—H8B	109.0	H18B—C18—H18C	109.5
C5—C8—H8B	109.0	C10—N1—N2	112.55 (15)
H8A—C8—H8B	107.8	C10—N1—H1	123.7
N2—C9—N3	110.23 (16)	N2—N1—H1	123.7
N2—C9—C8	124.65 (17)	C9—N2—N1	105.11 (15)
N3—C9—C8	125.11 (16)	C9—N3—C10	108.97 (15)
O1—C10—N1	130.88 (18)	C9—N3—N4	126.28 (15)
O1—C10—N3	125.99 (18)	C10—N3—N4	124.75 (15)
N1—C10—N3	103.13 (16)	N3—N4—C11	110.56 (15)
N4—C11—C12	110.60 (16)	N3—N4—H4A	105.4 (12)
N4—C11—H11A	109.5	C11—N4—H4A	109.8 (12)
C7—C2—C3—C4	−0.6 (4)	C14—C15—C16—C17	1.8 (3)
C1—C2—C3—C4	−179.7 (2)	C18—C15—C16—C17	−177.8 (2)
C2—C3—C4—C5	0.4 (3)	C13—C12—C17—C16	−1.2 (3)
C3—C4—C5—C6	−0.2 (3)	C11—C12—C17—C16	174.72 (19)
C3—C4—C5—C8	179.19 (19)	C15—C16—C17—C12	−0.5 (3)
C4—C5—C6—C7	0.1 (3)	O1—C10—N1—N2	180.0 (2)
C8—C5—C6—C7	−179.24 (19)	N3—C10—N1—N2	−0.5 (2)
C3—C2—C7—C6	0.5 (4)	N3—C9—N2—N1	−0.2 (2)
C1—C2—C7—C6	179.6 (2)	C8—C9—N2—N1	−179.20 (17)
C5—C6—C7—C2	−0.3 (4)	C10—N1—N2—C9	0.4 (2)
C6—C5—C8—C9	−80.4 (2)	N2—C9—N3—C10	−0.1 (2)
C4—C5—C8—C9	100.2 (2)	C8—C9—N3—C10	178.92 (18)
C5—C8—C9—N2	99.9 (2)	N2—C9—N3—N4	179.26 (17)
C5—C8—C9—N3	−79.0 (2)	C8—C9—N3—N4	−1.7 (3)
N4—C11—C12—C13	74.7 (2)	O1—C10—N3—C9	179.9 (2)
N4—C11—C12—C17	−101.1 (2)	N1—C10—N3—C9	0.3 (2)
C17—C12—C13—C14	1.6 (3)	O1—C10—N3—N4	0.5 (3)
C11—C12—C13—C14	−174.5 (2)	N1—C10—N3—N4	−179.04 (17)
C12—C13—C14—C15	−0.2 (4)	C9—N3—N4—C11	−103.8 (2)
C13—C14—C15—C16	−1.4 (3)	C10—N3—N4—C11	75.4 (2)
C13—C14—C15—C18	178.1 (2)	C12—C11—N4—N3	77.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	1.91	2.740 (2)	163
N4—H4A···N2^ii	0.95 (2)	2.12 (2)	3.011 (3)	154.3 (17)

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) x, y−1, z.

(III) 3-(4-Chlorobenzyl)-4-(4-methylbenzylamino)-4,5-dihydro-1H-1,2,4-triazol-5-one

Crystal data

C17H17ClN4O	F(000) = 688
Mr = 328.80	Dx = 1.282 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 18401 reflections
a = 16.5043 (10) Å	θ = 1.2–25.9°
b = 17.4355 (13) Å	µ = 0.23 mm^−1
c = 5.919 (3) Å	T = 293 K
V = 1703.1 (9) Å^3	Prism, colourless
Z = 4	0.50 × 0.38 × 0.17 mm

Data collection

Stoe IPDS 2 diffractometer	1815 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.117
Graphite monochromator	θmax = 25.9°, θmin = 1.7°
Detector resolution: 6.67 pixels mm^-1	h = −20→20
rotation scans	k = −21→21
22931 measured reflections	l = −6→7
3228 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0002P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.053	(Δ/σ)max = 0.005
S = 0.74	Δρmax = 0.14 e Å^−3
3228 reflections	Δρmin = −0.13 e Å^−3
213 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0251 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1395 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.12 (7)

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.45108 (12)	0.61045 (16)	0.3799 (5)	0.0695 (8)
C2	0.44065 (11)	0.54486 (17)	0.2543 (4)	0.0691 (7)
H2A	0.4664	0.5396	0.1154	0.083*
C3	0.39200 (11)	0.48722 (15)	0.3352 (4)	0.0599 (7)
H3	0.3852	0.4428	0.2502	0.072*
C4	0.35274 (10)	0.49397 (13)	0.5414 (4)	0.0477 (6)
C5	0.36340 (12)	0.56074 (15)	0.6608 (4)	0.0609 (6)
H5	0.3366	0.5670	0.7979	0.073*
C6	0.41280 (14)	0.61884 (16)	0.5827 (5)	0.0738 (8)
H6	0.4199	0.6632	0.6674	0.089*
C7	0.30183 (9)	0.42941 (13)	0.6342 (4)	0.0537 (6)
H7A	0.3168	0.3821	0.5587	0.064*
H7B	0.3136	0.4233	0.7938	0.064*
C8	0.21323 (10)	0.44228 (12)	0.6052 (3)	0.0404 (5)
C9	0.09132 (12)	0.44641 (12)	0.4440 (4)	0.0422 (5)
C10	0.18221 (11)	0.32027 (12)	0.1625 (4)	0.0596 (6)
H10A	0.1917	0.3086	0.0045	0.071*
H10B	0.1249	0.3136	0.1928	0.071*
C11	0.22998 (11)	0.26604 (12)	0.3067 (4)	0.0490 (5)
C12	0.30819 (12)	0.24693 (12)	0.2477 (4)	0.0626 (7)
H12	0.3300	0.2658	0.1139	0.075*
C13	0.35484 (15)	0.19994 (15)	0.3853 (4)	0.0697 (7)
H13	0.4075	0.1879	0.3425	0.084*
C14	0.32446 (16)	0.17114 (15)	0.5829 (5)	0.0675 (7)
C15	0.24647 (15)	0.19020 (13)	0.6410 (4)	0.0679 (7)
H15	0.2246	0.1711	0.7744	0.081*
C16	0.20001 (14)	0.23695 (14)	0.5061 (4)	0.0623 (7)
H16	0.1475	0.2491	0.5502	0.075*
C17	0.37582 (16)	0.11984 (15)	0.7309 (5)	0.1043 (10)
H17A	0.4239	0.1469	0.7759	0.156*
H17B	0.3907	0.0746	0.6481	0.156*
H17C	0.3455	0.1054	0.8627	0.156*
N1	0.09017 (9)	0.47153 (9)	0.6565 (3)	0.0490 (5)
H1	0.0470	0.4872	0.7235	0.059*
N2	0.16598 (8)	0.46972 (9)	0.7584 (3)	0.0484 (5)
N3	0.17190 (8)	0.42675 (10)	0.4108 (3)	0.0381 (4)
N4	0.20524 (10)	0.40047 (11)	0.2075 (3)	0.0475 (5)
O1	0.03673 (7)	0.44047 (7)	0.3017 (3)	0.0555 (4)
Cl1	0.51366 (3)	0.68248 (4)	0.2755 (2)	0.1181 (3)
H4	0.1860 (11)	0.4321 (13)	0.096 (4)	0.064 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0389 (12)	0.073 (2)	0.097 (2)	0.0016 (13)	−0.0010 (14)	0.0095 (17)
C2	0.0387 (11)	0.110 (2)	0.0583 (18)	0.0030 (13)	0.0048 (13)	0.0032 (18)
C3	0.0394 (11)	0.0857 (19)	0.0545 (18)	−0.0017 (12)	0.0003 (12)	−0.0139 (14)
C4	0.0293 (11)	0.0685 (17)	0.0453 (14)	0.0098 (10)	−0.0032 (11)	−0.0033 (13)
C5	0.0532 (13)	0.0731 (17)	0.0564 (15)	0.0074 (13)	0.0056 (12)	−0.0148 (16)
C6	0.0602 (14)	0.0674 (19)	0.094 (2)	0.0051 (14)	−0.0012 (16)	−0.0263 (17)
C7	0.0397 (10)	0.0720 (16)	0.0492 (15)	0.0116 (11)	−0.0054 (10)	0.0026 (13)
C8	0.0348 (10)	0.0492 (13)	0.0371 (14)	0.0087 (10)	0.0004 (10)	0.0061 (11)
C9	0.0377 (12)	0.0443 (14)	0.0445 (15)	0.0058 (10)	0.0016 (11)	0.0095 (12)
C10	0.0619 (13)	0.0593 (17)	0.0575 (16)	0.0120 (11)	−0.0126 (12)	−0.0179 (13)
C11	0.0556 (12)	0.0442 (13)	0.0473 (13)	0.0057 (10)	−0.0021 (11)	−0.0095 (12)
C12	0.0656 (14)	0.0642 (15)	0.0581 (18)	0.0152 (12)	0.0122 (14)	0.0047 (15)
C13	0.0695 (15)	0.0679 (18)	0.072 (2)	0.0217 (14)	0.0028 (15)	−0.0007 (15)
C14	0.0918 (18)	0.0463 (15)	0.0645 (19)	0.0125 (14)	−0.0083 (16)	−0.0006 (13)
C15	0.0893 (18)	0.0554 (16)	0.0590 (17)	−0.0065 (14)	0.0018 (15)	0.0053 (15)
C16	0.0593 (13)	0.0611 (16)	0.0665 (17)	−0.0022 (13)	0.0093 (13)	−0.0105 (14)
C17	0.146 (2)	0.0749 (19)	0.092 (2)	0.0412 (17)	−0.019 (2)	0.013 (2)
N1	0.0339 (9)	0.0665 (13)	0.0465 (12)	0.0094 (8)	0.0066 (8)	0.0022 (11)
N2	0.0389 (8)	0.0672 (12)	0.0391 (11)	0.0091 (8)	0.0014 (9)	0.0028 (10)
N3	0.0322 (9)	0.0493 (11)	0.0328 (10)	0.0083 (9)	−0.0002 (8)	0.0012 (8)
N4	0.0516 (10)	0.0529 (12)	0.0380 (12)	0.0133 (9)	0.0027 (9)	0.0006 (10)
O1	0.0423 (8)	0.0646 (10)	0.0596 (9)	0.0077 (7)	−0.0130 (8)	0.0024 (10)
Cl1	0.0659 (4)	0.1037 (6)	0.1847 (8)	−0.0123 (4)	0.0121 (6)	0.0368 (7)

Geometric parameters (Å, º)

C1—C6	1.364 (3)	C10—C11	1.498 (3)
C1—C2	1.375 (3)	C10—H10A	0.9700
C1—Cl1	1.739 (2)	C10—H10B	0.9700
C2—C3	1.373 (3)	C11—C16	1.376 (3)
C2—H2A	0.9300	C11—C12	1.378 (2)
C3—C4	1.387 (3)	C12—C13	1.388 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.373 (3)	C13—C14	1.368 (3)
C4—C7	1.508 (3)	C13—H13	0.9300
C5—C6	1.380 (3)	C14—C15	1.373 (3)
C5—H5	0.9300	C14—C17	1.512 (3)
C6—H6	0.9300	C15—C16	1.375 (3)
C7—C8	1.489 (2)	C15—H15	0.9300
C7—H7A	0.9700	C16—H16	0.9300
C7—H7B	0.9700	C17—H17A	0.9600
C8—N2	1.288 (2)	C17—H17B	0.9600
C8—N3	1.365 (2)	C17—H17C	0.9600
C9—O1	1.237 (2)	N1—N2	1.389 (2)
C9—N1	1.332 (2)	N1—H1	0.8600
C9—N3	1.387 (2)	N3—N4	1.400 (2)
C10—N4	1.473 (3)	N4—H4	0.92 (2)
C6—C1—C2	120.5 (2)	H10A—C10—H10B	108.0
C6—C1—Cl1	120.7 (2)	C16—C11—C12	117.7 (2)
C2—C1—Cl1	118.9 (2)	C16—C11—C10	122.14 (19)
C3—C2—C1	119.6 (2)	C12—C11—C10	120.1 (2)
C3—C2—H2A	120.2	C11—C12—C13	120.9 (2)
C1—C2—H2A	120.2	C11—C12—H12	119.5
C2—C3—C4	121.2 (2)	C13—C12—H12	119.5
C2—C3—H3	119.4	C14—C13—C12	121.0 (2)
C4—C3—H3	119.4	C14—C13—H13	119.5
C5—C4—C3	117.7 (2)	C12—C13—H13	119.5
C5—C4—C7	121.1 (2)	C13—C14—C15	118.0 (2)
C3—C4—C7	121.2 (2)	C13—C14—C17	120.5 (2)
C4—C5—C6	121.7 (2)	C15—C14—C17	121.6 (3)
C4—C5—H5	119.2	C14—C15—C16	121.4 (2)
C6—C5—H5	119.2	C14—C15—H15	119.3
C1—C6—C5	119.3 (2)	C16—C15—H15	119.3
C1—C6—H6	120.3	C15—C16—C11	121.1 (2)
C5—C6—H6	120.3	C15—C16—H16	119.5
C8—C7—C4	113.11 (16)	C11—C16—H16	119.5
C8—C7—H7A	109.0	C14—C17—H17A	109.5
C4—C7—H7A	109.0	C14—C17—H17B	109.5
C8—C7—H7B	109.0	H17A—C17—H17B	109.5
C4—C7—H7B	109.0	C14—C17—H17C	109.5
H7A—C7—H7B	107.8	H17A—C17—H17C	109.5
N2—C8—N3	111.39 (15)	H17B—C17—H17C	109.5
N2—C8—C7	124.68 (18)	C9—N1—N2	112.95 (16)
N3—C8—C7	123.94 (18)	C9—N1—H1	123.5
O1—C9—N1	131.26 (19)	N2—N1—H1	123.5
O1—C9—N3	125.5 (2)	C8—N2—N1	104.34 (16)
N1—C9—N3	103.22 (18)	C8—N3—C9	108.10 (17)
N4—C10—C11	111.12 (16)	C8—N3—N4	126.37 (14)
N4—C10—H10A	109.4	C9—N3—N4	125.40 (16)
C11—C10—H10A	109.4	N3—N4—C10	111.39 (16)
N4—C10—H10B	109.4	N3—N4—H4	106.6 (13)
C11—C10—H10B	109.4	C10—N4—H4	110.6 (14)
C6—C1—C2—C3	−0.7 (3)	C13—C14—C15—C16	−0.2 (4)
Cl1—C1—C2—C3	179.45 (16)	C17—C14—C15—C16	179.9 (2)
C1—C2—C3—C4	0.3 (3)	C14—C15—C16—C11	0.4 (4)
C2—C3—C4—C5	0.8 (3)	C12—C11—C16—C15	−0.3 (3)
C2—C3—C4—C7	−177.67 (18)	C10—C11—C16—C15	−176.8 (2)
C3—C4—C5—C6	−1.5 (3)	O1—C9—N1—N2	−179.2 (2)
C7—C4—C5—C6	176.98 (19)	N3—C9—N1—N2	0.8 (2)
C2—C1—C6—C5	0.0 (3)	N3—C8—N2—N1	0.2 (2)
Cl1—C1—C6—C5	179.87 (17)	C7—C8—N2—N1	179.86 (19)
C4—C5—C6—C1	1.1 (3)	C9—N1—N2—C8	−0.7 (2)
C5—C4—C7—C8	79.4 (2)	N2—C8—N3—C9	0.2 (2)
C3—C4—C7—C8	−102.2 (2)	C7—C8—N3—C9	−179.40 (19)
C4—C7—C8—N2	−97.1 (2)	N2—C8—N3—N4	176.28 (18)
C4—C7—C8—N3	82.5 (3)	C7—C8—N3—N4	−3.3 (3)
N4—C10—C11—C16	97.0 (2)	O1—C9—N3—C8	179.4 (2)
N4—C10—C11—C12	−79.5 (2)	N1—C9—N3—C8	−0.6 (2)
C16—C11—C12—C13	0.0 (3)	O1—C9—N3—N4	3.3 (3)
C10—C11—C12—C13	176.6 (2)	N1—C9—N3—N4	−176.70 (18)
C11—C12—C13—C14	0.2 (3)	C8—N3—N4—C10	109.8 (2)
C12—C13—C14—C15	−0.1 (4)	C9—N3—N4—C10	−74.8 (2)
C12—C13—C14—C17	179.8 (2)	C11—C10—N4—N3	−76.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	1.93	2.7349 (19)	156
N4—H4···N2^ii	0.92 (2)	2.13 (2)	2.990 (3)	156.2 (19)

Symmetry codes: (i) −x, −y+1, z+1/2; (ii) x, y, z−1.