1,3-Bis(4-methyl­phen­yl)triazene, 1-(4-chloro­phen­yl)-3-(4-fluoro­phen­yl)triazene and 1-(4-fluoro­phen­yl)-3-(4-methyl­phen­yl)triazene

The title 4,4'-disubstituted diphen­yl-1,3-triazines, C₁₄H₁₅N₃, (I), C₁₂H₉ClFN₃, (II), and C₁₃H₁₂FN₃, (III), each contain a triazene group (-N=N-NH-) having an extended conformation. The dihedral angles between the two benzene rings in (I), (II) and (III) are 4.3, 3.4 and 6.5°, respectively. The mol­ecules are almost entirely planar, with maximum deviations from the mean planes of 0.1087 (2), -0.1072 (7) and 0.1401 (3) Å, respectively. In each compound, the molecules are linked by N-H...N hydrogen bonds to form chains and pack similarly in the crystal structures.

S1. Comment

Triazene compounds containing a diazoamine group have important industrial and medical applications. The substituted triazenes (RN═N—NH–) find wide-ranging applications as initiators of radical polymerization (Rapta et al., 1996), as efficient chelating agents (Leman et al., 1992; Cotton et al., 1992) and as antitumor drugs (Wilman, 1988). These compounds, characterized by having a diazoamine group, commonly adopt the trans configuration in the ground state. They are also known to undergo reversible changes in double-bond configuration as a result of photoinduced and thermally induced trans–cis–trans isomerization (Baro et al., 1983; Le Fevre & Liddicoet, 1951; Barra & Chen, 2000). Photochromic materials of this type are of interest for potential applications, among others, in molecular electronic devices (Martin et al., 1995). The results of the present X-ray analysis are in agreement with those of the structure analyses of similar substituted triazenes (Anulewicz, 1997; Zhang et al., 1999; Hörner et al., 2004, 2002). In this paper, we report the structures of the three title 4,4'-disubstituted diphenyl-1,3-triazines.

Compounds (I), (II) and (III) differ only in the substituents at atoms C4 and C10; the substituents are methyl groups in (I), Cl and F atoms in (II), and a methyl group and an F atom in (III). The angles between the phenyl rings are 4.28 (1)° for (I), 3.42 (4)° for (II) and 6.53 (2)° for (III). These angles are in close agreement with the value observed in another open-ring intermediate for the synthesis of triazane [6.2 (2)°; Zhang et al., 1999].

The molecular structures of (I), (II) and (III) are shown in Fig.1, and the geometric parameters are compared in Table 1. For (I), within the limits of accuracy, the bond lengths and angles of the two methylphenyl rings are in agreement with one another. The N3═N2 bond is longer than the value expected for a double bond, the N2—N1 bond is shorter than expected for a single bond, and the C1—N1 and C7—N3 bonds are both short for single C_ar—N bonds. These values (Table 1) are in good agreement with those found in related compounds (Anulewicz, 1997; Walton et al., 1991; Zhang et al., 1999). The dihedral angle between the two phenyl rings and the C1—N1—N2—N3 and N1—N2—N3—C7 torsion angles are 177.21 (15) and 177.97 (14)°, respectively, showing the near coplanarity of the whole molecule. The crystal structure of (I) has been reported by Kondrashev (1964). The b axis of the monoclinic cell lies along the axis of the needles. The development of the four planes hkl (k = 0–3) and of the planes hk0 was obtained with a Weissenberg goniometer, and from these the space group P2₁/n was established. From the rotation X-ray photograph and the development of h0l, taken with NaCl as standard, the following lattice parameters were determined: a = 17.83 (2) Å, b = 4.83 (1) Å, c = 14.40 (2) Å and β = 88.40 (10)°]. The molecular structures of (II) and (III) are similar to that of (I), with small differences for some bond lengths due to the F and Cl atoms attached to the phenyl rings (Figs. 1b and 1c). The N3═N2 bond lengths [1.2777 (17) Å in (I) and 1.280 (3) Å in (III)] are somewhat shorter than the value of 1.317 (8) Å in (II).

Molecules of (I), (II) and (III) pack similarly in the unit cell, as shown in Fig. 2, and all have intermolecular N—H···N hydrogen bonds (Table 2). These hydrogen bonds are somewhat longer than the analogous interaction in the spiral of the β modification of 1-phenyl-3-(4-bromophenyl)triazine, (IV) (3.206 Å; Omel'chenko & Kondrashev, 1973). This difference is due to the different packing characters, where in the case of the flat parallel molecules the smallest N—H···N distance should be 3.60 Å. The shortening is achieved as a result of strong bending of the molecules ?of (IV), which form dimers in which the molecules are bent towards one another?, and of the deviation of the N atoms from the plane of the molecule to the same side (same as what?); this configuration? provides additional evidence for the existence of strong interaction between the molecules in the dimer (Omel'chenko & Kondrashev, 1973).

S2. Experimental

The title compounds (I) (m.p. 388–389 K), (II) (m.p. 402–403 K) and (III) (m.p. 385–386 K) were prepared as described by Hörner et al. (2004), using 4-methylaniline, 4-fluoroaniline and 4-chloroaniline as starting materials. The products were recrystallized from tetrahydrofuran (THF), and well shaped crystals were obtained by slow evaporation of an n-hexane/THF (1:1, v/v) solution.

S3. Refinement

For (I), H atoms of methyl groups were refined using a riding model, with fixed C—H distances of 0.96 Å [Uiso(H) = 1.5U_eq(C_methyl)]. All other H atoms were refined freely [C—H = 0.922 (17)–1.001 (19) Å and U_iso(H) = 0.063 (6)–0.096 (7) Ų]. For (II), all H atoms were refined using a riding model, with fixed C—H distances of 0.93 Å [U_iso(H) = 1.2U_eq(C,N)]. For (III), the H atoms of the methyl group and those attached to atoms C3 and N were refined with fixed displacement parameters [Uiso(H) = 1.5U_eq(C_methyl) and 1.2U_eq(C,N)] using a riding model [C—H(methyl) = 0.96 Å and C3—H3 = 0.93 = Å]. All other H atoms were refined freely [C—H = 0.88 (3)–0.97 (3) Å and U_iso(H) = 0.063 (9)–0.116 (14) Å].

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (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)and PLUTON (Spek, 1997) for (I); ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 1997) for (II), (III). For all compounds, software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) drawings of the title compounds, showing the atomic numbering schemes and 50% probability displacement ellipsoids for (a) (I), (b) (II) and (c) (III).
	Fig. 2. A perspective view of the packing in (I). The relationship between the molecules in (II) and (III) is similar. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 3/2 − x, y − 1/2, 3/2 − z.]

(I) 1,3-Bis(4-methylphenyl)triazene

Crystal data

C14H15N3	F(000) = 480
Mr = 225.29	Dx = 1.209 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10083 reflections
a = 14.4024 (19) Å	θ = 1.8–28.6°
b = 4.8171 (4) Å	µ = 0.07 mm^−1
c = 17.840 (2) Å	T = 296 K
β = 91.510 (11)°	Plate, light brown
V = 1237.3 (3) Å^3	0.44 × 0.29 × 0.09 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	2184 independent reflections
Radiation source: fine-focus sealed tube	1091 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.000
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −17→17
Tmin = 0.976, Tmax = 0.994	k = 0→5
2184 measured reflections	l = 0→21

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0204P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.003
2184 reflections	Δρmax = 0.10 e Å^−3
194 parameters	Δρmin = −0.10 e Å^−3
5 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0063 (11)

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
N1	0.76182 (10)	0.3666 (4)	0.65211 (9)	0.0583 (4)
N2	0.82941 (9)	0.5493 (3)	0.64085 (8)	0.0545 (4)
N3	0.84986 (9)	0.6884 (3)	0.69997 (8)	0.0569 (4)
C1	0.72730 (11)	0.2041 (4)	0.59313 (9)	0.0513 (5)
C2	0.65634 (13)	0.0215 (4)	0.60676 (12)	0.0611 (5)
C3	0.61809 (14)	−0.1348 (4)	0.54998 (12)	0.0656 (5)
C4	0.64924 (12)	−0.1197 (4)	0.47783 (10)	0.0572 (5)
C5	0.72186 (14)	0.0581 (4)	0.46526 (12)	0.0657 (6)
C6	0.76146 (14)	0.2196 (4)	0.52108 (11)	0.0646 (6)
C7	0.92459 (11)	0.8788 (4)	0.68937 (10)	0.0506 (4)
C8	0.95837 (13)	1.0089 (4)	0.75245 (11)	0.0611 (5)
C9	1.03130 (14)	1.1946 (4)	0.74933 (12)	0.0681 (6)
C10	1.07154 (12)	1.2559 (4)	0.68237 (12)	0.0618 (5)
C11	1.03599 (14)	1.1294 (5)	0.61887 (12)	0.0712 (6)
C12	0.96349 (14)	0.9412 (5)	0.62148 (11)	0.0662 (6)
H1	0.7405 (12)	0.344 (4)	0.7039 (10)	0.093 (7)*
H2	0.6377 (11)	0.010 (4)	0.6584 (10)	0.076 (6)*
H3	0.5638 (13)	−0.254 (4)	0.5607 (10)	0.085 (6)*
H5	0.7451 (11)	0.077 (4)	0.4152 (9)	0.074 (6)*
H6	0.8120 (11)	0.332 (4)	0.5125 (9)	0.063 (6)*
H8	0.9318 (11)	0.960 (4)	0.7985 (9)	0.068 (5)*
H9	1.0555 (12)	1.277 (4)	0.7973 (10)	0.080 (6)*
H11	1.0625 (12)	1.177 (4)	0.5692 (11)	0.096 (7)*
H12	0.9390 (12)	0.855 (4)	0.5744 (10)	0.080 (6)*
C13	1.15161 (13)	1.4597 (4)	0.67949 (13)	0.0881 (7)
H13A	1.1762	1.4607	0.6300	0.132*
H13B	1.1994	1.4051	0.7150	0.132*
H13C	1.1299	1.6422	0.6917	0.132*
C14	0.60445 (13)	−0.2891 (4)	0.41577 (11)	0.0798 (6)
H14A	0.6090	−0.4827	0.4280	0.120*
H14B	0.6356	−0.2545	0.3698	0.120*
H14C	0.5402	−0.2379	0.4099	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0574 (9)	0.0602 (11)	0.0574 (10)	−0.0041 (8)	0.0030 (8)	−0.0020 (8)
N2	0.0508 (8)	0.0490 (10)	0.0636 (10)	0.0003 (8)	−0.0022 (7)	0.0018 (8)
N3	0.0565 (9)	0.0585 (10)	0.0555 (9)	−0.0020 (8)	0.0005 (7)	−0.0014 (8)
C1	0.0515 (10)	0.0472 (12)	0.0549 (11)	0.0066 (9)	−0.0035 (8)	0.0002 (8)
C2	0.0609 (12)	0.0590 (14)	0.0637 (13)	−0.0021 (11)	0.0082 (11)	0.0035 (11)
C3	0.0587 (12)	0.0600 (14)	0.0782 (14)	−0.0044 (11)	0.0029 (12)	−0.0018 (12)
C4	0.0567 (11)	0.0496 (12)	0.0648 (12)	0.0048 (10)	−0.0049 (9)	−0.0013 (10)
C5	0.0764 (14)	0.0651 (14)	0.0558 (12)	−0.0051 (12)	0.0022 (11)	−0.0042 (12)
C6	0.0650 (13)	0.0641 (14)	0.0649 (13)	−0.0141 (11)	0.0053 (11)	0.0011 (11)
C7	0.0505 (10)	0.0485 (11)	0.0525 (10)	0.0044 (9)	−0.0004 (9)	−0.0002 (10)
C8	0.0666 (12)	0.0604 (14)	0.0564 (12)	−0.0073 (11)	0.0056 (11)	−0.0019 (11)
C9	0.0741 (13)	0.0622 (14)	0.0678 (14)	−0.0081 (11)	−0.0001 (12)	−0.0066 (12)
C10	0.0554 (11)	0.0486 (12)	0.0816 (14)	0.0010 (9)	0.0039 (11)	0.0032 (11)
C11	0.0688 (13)	0.0782 (16)	0.0671 (14)	−0.0073 (12)	0.0125 (12)	0.0075 (13)
C12	0.0682 (13)	0.0733 (15)	0.0573 (13)	−0.0032 (12)	0.0035 (11)	−0.0037 (12)
C13	0.0737 (13)	0.0693 (16)	0.1221 (19)	−0.0126 (12)	0.0156 (13)	0.0049 (14)
C14	0.0775 (14)	0.0719 (15)	0.0890 (14)	−0.0012 (11)	−0.0147 (11)	−0.0121 (12)

Geometric parameters (Å, º)

N1—N2	1.332 (2)	C7—C12	1.381 (2)
N1—C1	1.393 (2)	C8—C9	1.382 (3)
N1—H1	0.987 (19)	C8—H8	0.946 (17)
N2—N3	1.2777 (17)	C9—C10	1.373 (3)
N3—C7	1.430 (2)	C9—H9	0.999 (17)
C1—C2	1.375 (2)	C10—C11	1.373 (3)
C1—C6	1.390 (2)	C10—C13	1.516 (2)
C2—C3	1.366 (3)	C11—C12	1.385 (3)
C2—H2	0.968 (17)	C11—H11	1.001 (19)
C3—C4	1.376 (3)	C12—H12	0.994 (17)
C3—H3	0.993 (19)	C13—H13A	0.9600
C4—C5	1.375 (3)	C13—H13B	0.9600
C4—C14	1.507 (2)	C13—H13C	0.9600
C5—C6	1.376 (3)	C14—H14A	0.9600
C5—H5	0.966 (16)	C14—H14B	0.9600
C6—H6	0.922 (17)	C14—H14C	0.9600
C7—C8	1.366 (2)
N2—N1—C1	120.35 (17)	C7—C8—H8	117.2 (10)
N2—N1—H1	117.5 (11)	C9—C8—H8	121.5 (10)
C1—N1—H1	122.1 (11)	C10—C9—C8	120.8 (2)
N3—N2—N1	112.07 (15)	C10—C9—H9	120.9 (11)
N2—N3—C7	112.65 (14)	C8—C9—H9	118.2 (11)
C2—C1—C6	118.73 (19)	C11—C10—C9	117.73 (19)
C2—C1—N1	118.56 (17)	C11—C10—C13	121.8 (2)
C6—C1—N1	122.71 (18)	C9—C10—C13	120.49 (19)
C3—C2—C1	120.6 (2)	C10—C11—C12	121.9 (2)
C3—C2—H2	123.9 (11)	C10—C11—H11	119.1 (11)
C1—C2—H2	115.6 (10)	C12—C11—H11	119.1 (11)
C2—C3—C4	122.0 (2)	C7—C12—C11	119.7 (2)
C2—C3—H3	118.7 (11)	C7—C12—H12	120.5 (11)
C4—C3—H3	119.2 (11)	C11—C12—H12	119.8 (10)
C5—C4—C3	116.98 (19)	C10—C13—H13A	109.5
C5—C4—C14	122.02 (18)	C10—C13—H13B	109.5
C3—C4—C14	121.00 (18)	H13A—C13—H13B	109.5
C4—C5—C6	122.5 (2)	C10—C13—H13C	109.5
C4—C5—H5	119.5 (10)	H13A—C13—H13C	109.5
C6—C5—H5	118.0 (10)	H13B—C13—H13C	109.5
C5—C6—C1	119.3 (2)	C4—C14—H14A	109.5
C5—C6—H6	121.6 (11)	C4—C14—H14B	109.5
C1—C6—H6	119.0 (11)	H14A—C14—H14B	109.5
C8—C7—C12	118.61 (19)	C4—C14—H14C	109.5
C8—C7—N3	115.97 (17)	H14A—C14—H14C	109.5
C12—C7—N3	125.41 (18)	H14B—C14—H14C	109.5
C7—C8—C9	121.2 (2)
C1—N1—N2—N3	177.21 (15)	N1—C1—C6—C5	−178.09 (17)
N1—N2—N3—C7	177.97 (14)	N2—N3—C7—C8	−171.83 (16)
N2—N1—C1—C2	−178.84 (16)	N2—N3—C7—C12	8.8 (2)
N2—N1—C1—C6	1.0 (3)	C12—C7—C8—C9	−1.4 (3)
C6—C1—C2—C3	−2.2 (3)	N3—C7—C8—C9	179.17 (17)
N1—C1—C2—C3	177.64 (18)	C7—C8—C9—C10	0.6 (3)
C1—C2—C3—C4	0.9 (3)	C8—C9—C10—C11	0.9 (3)
C2—C3—C4—C5	0.8 (3)	C8—C9—C10—C13	−179.93 (18)
C2—C3—C4—C14	−178.52 (18)	C9—C10—C11—C12	−1.4 (3)
C3—C4—C5—C6	−1.3 (3)	C13—C10—C11—C12	179.4 (2)
C14—C4—C5—C6	178.0 (2)	C8—C7—C12—C11	0.9 (3)
C4—C5—C6—C1	0.0 (3)	N3—C7—C12—C11	−179.82 (18)
C2—C1—C6—C5	1.7 (3)	C10—C11—C12—C7	0.6 (3)

(II) 1-(4-chlorophenyl)-3-(4-fluorophenyl)triazene

Crystal data

C12H9ClFN3	F(000) = 512
Mr = 249.67	Dx = 1.353 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4244 reflections
a = 14.500 (3) Å	θ = 1.8–24.4°
b = 4.7385 (5) Å	µ = 0.30 mm^−1
c = 17.848 (3) Å	T = 296 K
β = 92.298 (16)°	Plate, brown
V = 1225.3 (4) Å^3	0.50 × 0.29 × 0.06 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	2157 independent reflections
Radiation source: fine-focus sealed tube	978 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.078
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: integration (X-RED32; Stoe&Cie, 2002)	h = −17→17
Tmin = 0.886, Tmax = 0.981	k = −5→5
8654 measured reflections	l = −21→21

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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.253	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.1152P)^2] where P = (Fo^2 + 2Fc^2)/3
2157 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.33 e Å^−3
1 restraint	Δρmin = −0.44 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.59926 (18)	−0.3008 (6)	0.40352 (15)	0.1056 (11)
F1	1.1636 (3)	1.4616 (11)	0.6800 (3)	0.1030 (18)
N1	0.7594 (4)	0.3764 (14)	0.6514 (3)	0.0663 (17)
N2	0.8269 (4)	0.5565 (12)	0.6397 (4)	0.0584 (16)
N3	0.8480 (4)	0.7023 (13)	0.7008 (3)	0.0586 (15)
C1	0.7251 (5)	0.2108 (14)	0.5920 (4)	0.0515 (17)
C2	0.6540 (5)	0.0309 (16)	0.6034 (4)	0.066 (2)
C3	0.6152 (5)	−0.1239 (17)	0.5473 (4)	0.067 (2)
C4	0.6490 (5)	−0.1087 (15)	0.4770 (4)	0.0573 (18)
C5	0.7222 (5)	0.0627 (16)	0.4628 (4)	0.066 (2)
C6	0.7609 (5)	0.2270 (15)	0.5195 (4)	0.066 (2)
C7	0.9237 (4)	0.8901 (14)	0.6902 (4)	0.0484 (16)
C8	0.9579 (5)	1.0271 (16)	0.7524 (4)	0.063 (2)
C9	1.0311 (5)	1.2078 (16)	0.7500 (4)	0.065 (2)
C10	1.0765 (5)	1.2662 (14)	0.6839 (4)	0.0568 (18)
C11	1.0376 (6)	1.1284 (17)	0.6210 (4)	0.071 (2)
C12	0.9648 (5)	0.9467 (16)	0.6230 (4)	0.062 (2)
H1	0.7369	0.3615	0.6951	0.080*
H2	0.6316	0.0144	0.6513	0.080*
H3	0.5655	−0.2412	0.5564	0.080*
H5	0.7457	0.0684	0.4151	0.079*
H6	0.8099	0.3469	0.5103	0.079*
H8	0.9305	0.9966	0.7979	0.076*
H9	1.0517	1.2958	0.7942	0.078*
H11	1.0630	1.1629	0.5749	0.085*
H12	0.9427	0.8603	0.5790	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1044 (19)	0.1028 (19)	0.1079 (19)	−0.0084 (15)	−0.0183 (14)	−0.0142 (15)
F1	0.090 (3)	0.080 (3)	0.138 (4)	−0.028 (3)	0.005 (3)	0.006 (3)
N1	0.063 (4)	0.076 (4)	0.060 (4)	0.002 (4)	0.004 (3)	0.003 (3)
N2	0.047 (3)	0.047 (3)	0.080 (4)	0.002 (3)	−0.011 (3)	0.017 (3)
N3	0.053 (3)	0.072 (4)	0.051 (3)	−0.001 (3)	−0.005 (3)	0.002 (3)
C1	0.058 (4)	0.046 (4)	0.049 (4)	0.014 (4)	−0.011 (3)	−0.008 (3)
C2	0.066 (5)	0.067 (5)	0.066 (5)	−0.001 (4)	0.005 (4)	0.007 (4)
C3	0.058 (5)	0.070 (5)	0.073 (5)	−0.003 (4)	0.003 (4)	0.001 (4)
C4	0.058 (4)	0.049 (4)	0.064 (5)	0.008 (4)	−0.004 (4)	0.000 (4)
C5	0.079 (5)	0.066 (5)	0.052 (4)	−0.002 (5)	0.001 (4)	−0.005 (4)
C6	0.069 (5)	0.053 (4)	0.076 (5)	−0.013 (4)	0.004 (4)	0.002 (4)
C7	0.049 (4)	0.044 (4)	0.052 (4)	0.012 (3)	−0.001 (3)	−0.004 (3)
C8	0.064 (5)	0.063 (5)	0.064 (5)	−0.007 (4)	0.008 (4)	0.000 (4)
C9	0.075 (5)	0.058 (5)	0.061 (4)	−0.006 (4)	−0.011 (4)	−0.003 (4)
C10	0.057 (4)	0.042 (4)	0.072 (5)	−0.001 (3)	0.002 (4)	0.007 (4)
C11	0.076 (5)	0.075 (6)	0.065 (5)	−0.006 (5)	0.022 (4)	0.009 (4)
C12	0.067 (5)	0.074 (5)	0.045 (4)	−0.010 (4)	0.003 (3)	−0.010 (4)

Geometric parameters (Å, º)

F1—C10	1.569 (8)	C5—C6	1.379 (10)
N1—N2	1.321 (7)	C5—H5	0.9300
N1—C1	1.394 (8)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.361 (9)
N2—N3	1.317 (8)	C7—C12	1.388 (9)
N3—C7	1.431 (9)	C8—C9	1.366 (10)
Cl1—C4	1.731 (7)	C8—H8	0.9300
C1—C2	1.359 (10)	C9—C10	1.403 (10)
C1—C6	1.415 (10)	C9—H9	0.9300
C2—C3	1.345 (10)	C10—C11	1.397 (10)
C2—H2	0.9300	C11—C12	1.364 (10)
C3—C4	1.367 (10)	C11—H11	0.9300
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.369 (10)
N2—N1—C1	119.2 (6)	C5—C6—H6	120.4
N2—N1—H1	120.4	C1—C6—H6	120.4
C1—N1—H1	120.4	C8—C7—C12	117.2 (7)
N3—N2—N1	110.9 (6)	C8—C7—N3	116.5 (6)
N2—N3—C7	111.8 (5)	C12—C7—N3	126.4 (6)
C2—C1—N1	119.3 (7)	C7—C8—C9	122.2 (7)
C2—C1—C6	118.6 (7)	C7—C8—H8	118.9
N1—C1—C6	122.1 (7)	C9—C8—H8	118.9
C3—C2—C1	121.9 (8)	C8—C9—C10	122.8 (7)
C3—C2—H2	119.1	C8—C9—H9	118.6
C1—C2—H2	119.1	C10—C9—H9	118.6
C2—C3—C4	119.9 (8)	C11—C10—C9	113.3 (7)
C2—C3—H3	120.0	C11—C10—F1	122.7 (6)
C4—C3—H3	120.0	C9—C10—F1	124.0 (6)
C3—C4—C5	120.7 (7)	C12—C11—C10	124.3 (7)
C3—C4—Cl1	121.0 (6)	C12—C11—H11	117.9
C5—C4—Cl1	118.3 (6)	C10—C11—H11	117.9
C4—C5—C6	119.6 (7)	C11—C12—C7	120.2 (7)
C4—C5—H5	120.2	C11—C12—H12	119.9
C6—C5—H5	120.2	C7—C12—H12	119.9
C5—C6—C1	119.2 (7)
C1—N1—N2—N3	177.5 (5)	N1—C1—C6—C5	−178.3 (6)
N1—N2—N3—C7	177.5 (5)	N2—N3—C7—C8	−172.7 (6)
N2—N1—C1—C2	−178.3 (6)	N2—N3—C7—C12	7.7 (9)
N2—N1—C1—C6	0.7 (9)	C12—C7—C8—C9	−1.6 (10)
N1—C1—C2—C3	176.8 (7)	N3—C7—C8—C9	178.7 (6)
C6—C1—C2—C3	−2.2 (11)	C7—C8—C9—C10	0.0 (12)
C1—C2—C3—C4	1.9 (12)	C8—C9—C10—C11	1.8 (11)
C2—C3—C4—C5	0.1 (11)	C8—C9—C10—F1	−177.0 (6)
C2—C3—C4—Cl1	−178.9 (6)	C9—C10—C11—C12	−2.2 (11)
C3—C4—C5—C6	−1.6 (11)	F1—C10—C11—C12	176.7 (6)
Cl1—C4—C5—C6	177.4 (5)	C10—C11—C12—C7	0.7 (12)
C4—C5—C6—C1	1.2 (11)	C8—C7—C12—C11	1.3 (10)
C2—C1—C6—C5	0.7 (10)	N3—C7—C12—C11	−179.1 (7)

(III) 1-(4-fluorophenyl)-3-(4-methylphenyl)triazene

Crystal data

C13H12FN3	F(000) = 480
Mr = 229.26	Dx = 1.316 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3288 reflections
a = 13.683 (3) Å	θ = 1.8–27.7°
b = 4.7712 (6) Å	µ = 0.09 mm^−1
c = 17.742 (4) Å	T = 296 K
β = 92.512 (18)°	Plate, brown
V = 1157.2 (4) Å^3	0.50 × 0.28 × 0.06 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	757 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.081
Plane graphite monochromator	θmax = 25.0°, θmin = 1.8°
ω scans	h = −16→16
6441 measured reflections	k = −5→5
2019 independent reflections	l = −21→21

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0316P)^2] where P = (Fo^2 + 2Fc^2)/3
2019 reflections	(Δ/σ)max = 0.009
183 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

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

	x	y	z	Uiso*/Ueq
F1	0.59689 (18)	−0.2842 (5)	0.41441 (11)	0.1179 (9)
N1	0.7588 (2)	0.3437 (6)	0.65048 (13)	0.0690 (8)
N2	0.8287 (2)	0.5281 (6)	0.64092 (15)	0.0612 (7)
N3	0.8525 (2)	0.6608 (6)	0.70168 (13)	0.0646 (8)
C1	0.7201 (3)	0.1830 (7)	0.59027 (15)	0.0605 (9)
C2	0.6487 (3)	−0.0110 (8)	0.6024 (2)	0.0704 (11)
C3	0.6081 (3)	−0.1655 (8)	0.5441 (2)	0.0800 (11)
C4	0.6405 (3)	−0.1262 (8)	0.47375 (18)	0.0713 (10)
C5	0.7111 (3)	0.0606 (9)	0.4589 (2)	0.0764 (11)
C6	0.7531 (3)	0.2209 (8)	0.51692 (18)	0.0740 (11)
C7	0.9297 (2)	0.8534 (7)	0.69146 (15)	0.0610 (9)
C8	0.9712 (3)	0.9756 (8)	0.7551 (2)	0.0731 (11)
C9	1.0464 (3)	1.1635 (9)	0.7525 (2)	0.0799 (11)
C10	1.0837 (2)	1.2405 (7)	0.6842 (2)	0.0705 (10)
C11	1.0410 (3)	1.1238 (9)	0.6199 (2)	0.0773 (11)
C12	0.9664 (3)	0.9370 (9)	0.62253 (19)	0.0728 (11)
C13	1.1642 (2)	1.4475 (7)	0.68079 (18)	0.0750 (11)
H1	0.7365	0.3214	0.6946	0.083*
H2	0.635 (3)	−0.038 (8)	0.651 (2)	0.116 (14)*
H3	0.5591	−0.2954	0.5526	0.096*
H5	0.728 (3)	0.097 (8)	0.4075 (19)	0.115 (13)*
H6	0.805 (2)	0.352 (6)	0.5094 (15)	0.063 (9)*
H8	0.956 (2)	0.915 (8)	0.8017 (19)	0.104 (13)*
H9	1.080 (2)	1.238 (6)	0.7958 (15)	0.067 (10)*
H11	1.061 (2)	1.189 (6)	0.5717 (16)	0.086 (11)*
H12	0.936 (2)	0.852 (6)	0.5843 (15)	0.069 (11)*
H13A	1.1614	1.5744	0.7226	0.112*
H13B	1.1574	1.5509	0.6344	0.112*
H13C	1.2259	1.3513	0.6831	0.112*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.1283 (19)	0.128 (2)	0.0957 (14)	−0.0044 (16)	−0.0166 (13)	−0.0346 (14)
N1	0.078 (2)	0.079 (2)	0.0508 (16)	−0.0005 (18)	0.0108 (15)	0.0000 (15)
N2	0.0632 (19)	0.0591 (19)	0.0613 (17)	0.0049 (16)	0.0033 (14)	0.0049 (14)
N3	0.074 (2)	0.072 (2)	0.0472 (14)	−0.0041 (17)	0.0018 (13)	0.0000 (15)
C1	0.078 (2)	0.059 (2)	0.0438 (18)	0.016 (2)	−0.0024 (17)	−0.0039 (17)
C2	0.084 (3)	0.063 (3)	0.064 (3)	0.001 (2)	0.009 (2)	0.005 (2)
C3	0.086 (3)	0.077 (3)	0.077 (2)	0.007 (2)	0.003 (2)	−0.004 (2)
C4	0.090 (3)	0.069 (3)	0.054 (2)	0.008 (2)	−0.007 (2)	−0.0101 (19)
C5	0.098 (3)	0.079 (3)	0.052 (2)	0.007 (3)	0.001 (2)	−0.008 (2)
C6	0.087 (3)	0.073 (3)	0.063 (2)	−0.005 (2)	0.012 (2)	0.003 (2)
C7	0.075 (2)	0.061 (2)	0.0473 (18)	0.011 (2)	0.0035 (17)	−0.0001 (17)
C8	0.089 (3)	0.078 (3)	0.053 (2)	−0.008 (2)	0.005 (2)	−0.004 (2)
C9	0.092 (3)	0.087 (3)	0.061 (2)	−0.009 (3)	−0.002 (2)	−0.012 (2)
C10	0.068 (2)	0.061 (3)	0.083 (2)	0.002 (2)	0.004 (2)	0.0044 (19)
C11	0.081 (3)	0.087 (3)	0.065 (2)	0.003 (3)	0.014 (2)	0.008 (2)
C12	0.083 (3)	0.085 (3)	0.050 (2)	−0.002 (2)	0.004 (2)	−0.002 (2)
C13	0.067 (2)	0.060 (2)	0.098 (3)	−0.0110 (19)	0.014 (2)	0.0039 (18)

Geometric parameters (Å, º)

F1—C4	1.406 (4)	C6—H6	0.96 (3)
N1—N2	1.316 (3)	C7—C8	1.372 (4)
N1—C1	1.400 (4)	C7—C12	1.400 (4)
N1—H1	0.8600	C8—C9	1.367 (5)
N2—N3	1.280 (3)	C8—H8	0.91 (3)
N3—C7	1.417 (4)	C9—C10	1.385 (5)
C1—C2	1.370 (4)	C9—H9	0.95 (3)
C1—C6	1.408 (4)	C10—C11	1.376 (5)
C2—C3	1.369 (4)	C10—C13	1.483 (4)
C2—H2	0.90 (4)	C11—C12	1.357 (5)
C3—C4	1.355 (4)	C11—H11	0.96 (3)
C3—H3	0.9300	C12—H12	0.88 (3)
C4—C5	1.350 (5)	C13—H13A	0.9600
C5—C6	1.387 (5)	C13—H13B	0.9600
C5—H5	0.97 (3)	C13—H13C	0.9600
N2—N1—C1	121.4 (3)	C8—C7—N3	117.0 (3)
N2—N1—H1	119.3	C12—C7—N3	126.5 (3)
C1—N1—H1	119.3	C9—C8—C7	122.4 (4)
N3—N2—N1	112.4 (3)	C9—C8—H8	116 (2)
N2—N3—C7	112.1 (2)	C7—C8—H8	121 (2)
C2—C1—N1	119.9 (3)	C8—C9—C10	120.7 (4)
C2—C1—C6	119.5 (3)	C8—C9—H9	124.1 (18)
N1—C1—C6	120.6 (3)	C10—C9—H9	115.0 (18)
C3—C2—C1	120.9 (4)	C11—C10—C9	117.3 (4)
C3—C2—H2	124 (2)	C11—C10—C13	121.7 (4)
C1—C2—H2	115 (2)	C9—C10—C13	121.0 (4)
C4—C3—C2	118.9 (4)	C12—C11—C10	122.0 (4)
C4—C3—H3	120.5	C12—C11—H11	119.2 (18)
C2—C3—H3	120.5	C10—C11—H11	118.6 (18)
C5—C4—C3	122.5 (4)	C11—C12—C7	121.0 (4)
C5—C4—F1	119.4 (3)	C11—C12—H12	127.5 (19)
C3—C4—F1	118.1 (4)	C7—C12—H12	111.4 (19)
C4—C5—C6	119.7 (4)	C10—C13—H13A	109.5
C4—C5—H5	121 (2)	C10—C13—H13B	109.5
C6—C5—H5	119 (2)	H13A—C13—H13B	109.5
C5—C6—C1	118.5 (4)	C10—C13—H13C	109.5
C5—C6—H6	122.8 (17)	H13A—C13—H13C	109.5
C1—C6—H6	118.7 (17)	H13B—C13—H13C	109.5
C8—C7—C12	116.5 (4)
C1—N1—N2—N3	177.9 (3)	N1—C1—C6—C5	−178.7 (3)
N1—N2—N3—C7	178.3 (3)	N2—N3—C7—C8	−170.3 (3)
N2—N1—C1—C2	178.8 (3)	N2—N3—C7—C12	11.4 (4)
N2—N1—C1—C6	−2.0 (4)	C12—C7—C8—C9	−1.9 (5)
N1—C1—C2—C3	178.4 (3)	N3—C7—C8—C9	179.7 (3)
C6—C1—C2—C3	−0.9 (5)	C7—C8—C9—C10	0.6 (6)
C1—C2—C3—C4	0.7 (5)	C8—C9—C10—C11	0.9 (5)
C2—C3—C4—C5	−0.2 (5)	C8—C9—C10—C13	179.0 (3)
C2—C3—C4—F1	−179.1 (3)	C9—C10—C11—C12	−1.0 (5)
C3—C4—C5—C6	−0.1 (6)	C13—C10—C11—C12	−179.1 (3)
F1—C4—C5—C6	178.8 (3)	C10—C11—C12—C7	−0.3 (6)
C4—C5—C6—C1	0.0 (5)	C8—C7—C12—C11	1.7 (5)
C2—C1—C6—C5	0.5 (5)	N3—C7—C12—C11	−179.9 (3)