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The title 4,4'-disubstituted diphenyl-1,3-triazines, C
14H
15N
3, (I), C
12H
9ClFN
3, (II), and C
13H
12FN
3, (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.
Supporting information
CCDC references: 273051; 273052; 273053
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.
For (I), H atoms of methyl groups were refined using a riding model, with fixed C—H distances of 0.96 Å [Uiso(H) = 1.5Ueq(Cmethyl)]. All other H atoms were refined freely [C—H = 0.922 (17)–1.001 (19) Å and Uiso(H) = 0.063 (6)–0.096 (7) Å2]. For (II), all H atoms were refined using a riding model, with fixed C—H distances of 0.93 Å [Uiso(H) = 1.2Ueq(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) = 1.5Ueq(Cmethyl) and 1.2Ueq(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 Uiso(H) = 0.063 (9)–0.116 (14) Å].
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).
(I) 1,3-Bis(4-methylphenyl)triazene
top
Crystal data top
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) Å3 | 0.44 × 0.29 × 0.09 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0204P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (11) |
Crystal data top
C14H15N3 | V = 1237.3 (3) Å3 |
Mr = 225.29 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.4024 (19) Å | µ = 0.07 mm−1 |
b = 4.8171 (4) Å | T = 296 K |
c = 17.840 (2) Å | 0.44 × 0.29 × 0.09 mm |
β = 91.510 (11)° | |
Data collection top
Stoe IPDS-II diffractometer | 2184 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1091 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.994 | Rint = 0.000 |
2184 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 5 restraints |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.10 e Å−3 |
2184 reflections | Δρmin = −0.10 e Å−3 |
194 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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
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Crystal data top
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) Å3 | 0.50 × 0.29 × 0.06 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.087 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.253 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1152P)2] where P = (Fo2 + 2Fc2)/3 |
2157 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.33 e Å−3 |
1 restraint | Δρmin = −0.44 e Å−3 |
Crystal data top
C12H9ClFN3 | V = 1225.3 (4) Å3 |
Mr = 249.67 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.500 (3) Å | µ = 0.30 mm−1 |
b = 4.7385 (5) Å | T = 296 K |
c = 17.848 (3) Å | 0.50 × 0.29 × 0.06 mm |
β = 92.298 (16)° | |
Data collection top
Stoe IPDS-II diffractometer | 2157 independent reflections |
Absorption correction: integration (X-RED32; Stoe&Cie, 2002) | 978 reflections with I > 2σ(I) |
Tmin = 0.886, Tmax = 0.981 | Rint = 0.078 |
8654 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.087 | 1 restraint |
wR(F2) = 0.253 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.33 e Å−3 |
2157 reflections | Δρmin = −0.44 e Å−3 |
154 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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
top
Crystal data top
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) Å3 | 0.50 × 0.28 × 0.06 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0316P)2] where P = (Fo2 + 2Fc2)/3 |
2019 reflections | (Δ/σ)max = 0.009 |
183 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C13H12FN3 | V = 1157.2 (4) Å3 |
Mr = 229.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.683 (3) Å | µ = 0.09 mm−1 |
b = 4.7712 (6) Å | T = 296 K |
c = 17.742 (4) Å | 0.50 × 0.28 × 0.06 mm |
β = 92.512 (18)° | |
Data collection top
Stoe IPDS-II diffractometer | 757 reflections with I > 2σ(I) |
6441 measured reflections | Rint = 0.081 |
2019 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.15 e Å−3 |
2019 reflections | Δρmin = −0.16 e Å−3 |
183 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C14H15N3 | C12H9ClFN3 | C13H12FN3 |
Mr | 225.29 | 249.67 | 229.26 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 296 | 296 | 296 |
a, b, c (Å) | 14.4024 (19), 4.8171 (4), 17.840 (2) | 14.500 (3), 4.7385 (5), 17.848 (3) | 13.683 (3), 4.7712 (6), 17.742 (4) |
β (°) | 91.510 (11) | 92.298 (16) | 92.512 (18) |
V (Å3) | 1237.3 (3) | 1225.3 (4) | 1157.2 (4) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.30 | 0.09 |
Crystal size (mm) | 0.44 × 0.29 × 0.09 | 0.50 × 0.29 × 0.06 | 0.50 × 0.28 × 0.06 |
|
Data collection |
Diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) | Integration (X-RED32; Stoe&Cie, 2002) | – |
Tmin, Tmax | 0.976, 0.994 | 0.886, 0.981 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2184, 2184, 1091 | 8654, 2157, 978 | 6441, 2019, 757 |
Rint | 0.000 | 0.078 | 0.081 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.066, 0.99 | 0.087, 0.253, 1.08 | 0.052, 0.110, 0.85 |
No. of reflections | 2184 | 2157 | 2019 |
No. of parameters | 194 | 154 | 183 |
No. of restraints | 5 | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.10, −0.10 | 0.33, −0.44 | 0.15, −0.16 |
Comparative selected geometric parameters (Å, °). top | (F)a | (I) | (II) | (III) |
N1—N2 | 1.334 (4) | 1.332 (2) | 1.321 (7) | 1.316 (3) |
C1—C2 | 1.378 (4) | 1.375 (2) | 1.359 (10) | 1.370 (4) |
C1—C6 | 1.399 (5) | 1.390 (2) | 1.415 (10) | 1.408 (4) |
C7—C8 | 1.386 (5) | 1.366 (2) | 1.361 (9) | 1.372 (4) |
C7—C12 | 1.385 (5) | 1.381 (2) | 1.388 (9) | 1.400 (4) |
C4—C14 | - | 1.507 (2) | - | - |
C10—C13 | - | 1.516 (2) | - | 1.483 (4) |
Cl1—C4 | - | - | 1.731 (7) | - |
| | | | |
N2—N1—C1 | 119.0 (3) | 120.35 (17) | 119.2 (6) | 121.4 (3) |
N3—N2—N1 | 112.9 (2) | 112.07 (15) | 110.9 (6) | 112.4 (3) |
N2—N3—C7 | 111.9 (3) | 112.65 (14) | 111.8 (5) | 112.1 (2) |
C2—C1—N1 | 118.6 (3) | 118.56 (17) | 119.3 (7) | 119.9 (3) |
N1—C1—C6 | 121.1 (3) | 122.71 (18) | 122.1 (7) | 120.6 (3) |
C8—C7—N3 | 115.9 (3) | 115.97 (17) | 116.5 (6) | 117.0 (3) |
C12—C7—N3 | 125.0 (3) | 125.41 (18) | 126.4 (6) | 126.5 (3) |
| | | | |
N1—C1—C2—C3 | 179.9 (3) | 177.64 (18) | 176.8 (7) | 178.4 (3) |
N3—C7—C8—C9 | 179.1 (3) | 179.17 (17) | 178.7 (6) | 179.7 (3) |
N1—N2—N3—C7 | 178.8 (3) | 177.97 (14) | 177.5 (5) | 178.3 (3) |
C1—N1—N2—N3 | 179.0 (3) | 177.21 (15) | 177.5 (5) | 177.9 (3) |
Note: (a) 1,3-bis(p-fluorophenyl)triazine (Anulewicz, 1997). |
Hydrogen-bonding geometry (Å, °). top | D—H···A | | D—H | H···A | D···A | D—H···A |
(I) | N1—H1···N3i | | 0.99 (2) | 2.31 (2) | 3.242 (2) | 158.1 (15) |
(II) | N1—H1···N3i | | 0.86 | 2.39 | 3.223 (8) | 163 |
(III) | N1—H1···N3i | | 0.86 | 2.38 | 3.211 (3) | 164 |
Symmetry code: (i) 3/2 − x, y − 1/2, 3/2 − z. |
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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 Car—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).