The crystal structures of 4-(phenyldiazenyl)naphthalen-1-amine, C16H13N3, (I), and its hydrochloride, (4-aminonaphthalen-1-yl)phenyldiazenium chloride, C16H14N3+·Cl-, (II), have been determined from X-ray single-crystal and powder data, respectively. The effect of the crystal environment on the molecular electronic structure was analysed on the AM1 level. One of the two symmetry-independent molecules in (I) is involved in intermolecular hydrogen bonding, so that its dipole moment is twice as large as that of the other molecule. The cations in (II) form stacks along [100], with the Cl- anions forming hydrogen bonds to all three H atoms attached to N atoms.
Supporting information
CCDC references: 162571; 162572
Original source of both compounds? Single crystals of (I) were grown by slow
evaporation of an acetone solution. The UV-visible spectra were recorded on a
Specord M-40 spectrophotometer (Carl Zeiss, Jena).
For (I), all H atoms except those belonging to the amino group of (Ib) (H4A and
H4B) were refined isotropically. Amino-H atoms were refined assuming ideal
120° angles at the N4 atoms (AFIX 94 in SHELXL97; Sheldrick, 1997) The
monoclinic cell dimensions of (II) were determined with TREOR90 (Werner et
al., 1985) and refined to M20 = 41 and F30 = 76 (0.007,56)
using the first 75 peaks. The positions of the cation and anion were
determined by combining the grid-search (Chernyshev & Schenk, 1998) and
simulated-annealing (Zhukov et al., 2000) procedures. The initial
molecular model was built with MOPAC7.0 (Stewart, 1993) on the AM1 level. The
X-ray diffraction profile and the difference between the measured and
calculated profiles after the Rietveld refinement are shown in Fig. 3, with
the final RB = 0.076. A l l atoms were refined isotropically, with an
overall Uiso parameter for the C and N atoms. H atoms were placed in
geometrically calculated positions, with a common isotropic displacement
parameter Uiso fixed at 0.05 Å2. The planarity of the phenyl and
naphthalene groups was restrained. The anisotropy of diffraction-line
broadening was approximated by a quartic form in hkl (Popa, 1998). The
self-consistent electrostatic field produced by the crystal environment of a
molecule was calculated, taking into account atomic point charges and
hybridization dipoles, and the resulting electrostatic potentials and
gradients in the positions of the atomic nuclei were used to modify the
diagonal elements of the Hcore matrix and the off-diagonals Hµν, where
the indices µν denote atomic orbitals centred at the same atom (Yatsenko &
Paseshnichenko, 2000).
Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (I); local program for (II). Cell refinement: CAD-4 Software for (I); LSPAID (Visser, 1986) for (II). Data reduction: PROFIT (Streltsov & Zavodnik, 1989) for (I). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); MRIA (Zlokazov & Chernyshev, 1992) for (II). Program(s) used to refine structure: SHELXL97 for (I); MRIA for (II). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (I); PLUTON92 (Spek, 1992) for (II). Software used to prepare material for publication: SHELXL97 for (I); PARST (Nardelli, 1983) for (II).
(I) 4-(phenyldiazenyl)naphthalen-1-amine
top
Crystal data top
C16H13N3 | Dx = 1.312 Mg m−3 |
Mr = 247.29 | Melting point: 396 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
a = 26.120 (5) Å | Cell parameters from 22 reflections |
b = 18.473 (4) Å | θ = 14.7–16.5° |
c = 10.379 (3) Å | µ = 0.08 mm−1 |
V = 5008 (2) Å3 | T = 293 K |
Z = 16 | Plate, red |
F(000) = 2080 | 0.45 × 0.38 × 0.14 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 1.6° |
Graphite monochromator | h = 0→32 |
ω scans | k = 0→22 |
4915 measured reflections | l = 0→12 |
4915 independent reflections | 3 standard reflections every 120 min |
2908 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.053 | All H-atom parameters refined |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.28 | (Δ/σ)max = 0.021 |
4915 reflections | Δρmax = 0.33 e Å−3 |
443 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0045 (3) |
Crystal data top
C16H13N3 | V = 5008 (2) Å3 |
Mr = 247.29 | Z = 16 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 26.120 (5) Å | µ = 0.08 mm−1 |
b = 18.473 (4) Å | T = 293 K |
c = 10.379 (3) Å | 0.45 × 0.38 × 0.14 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
4915 measured reflections | 3 standard reflections every 120 min |
4915 independent reflections | intensity decay: none |
2908 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.28 | Δρmax = 0.33 e Å−3 |
4915 reflections | Δρmin = −0.15 e Å−3 |
443 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 | 0.19711 (8) | −0.11543 (10) | 0.07824 (18) | 0.0555 (5) | |
N2 | 0.14729 (6) | 0.07504 (9) | 0.47727 (14) | 0.0442 (4) | |
N3 | 0.18239 (6) | 0.11234 (8) | 0.52983 (14) | 0.0438 (4) | |
N4 | 0.16634 (14) | −0.25577 (13) | 0.3546 (2) | 0.0938 (8) | |
H4A | 0.1966 (8) | −0.25980 (16) | 0.3334 (6) | 0.142 (17)* | |
H4B | 0.1443 (5) | −0.2808 (6) | 0.3195 (9) | 0.19 (2)* | |
N5 | 0.10966 (6) | −0.06221 (9) | 0.74285 (17) | 0.0540 (5) | |
N6 | 0.14443 (7) | −0.02607 (10) | 0.79748 (17) | 0.0624 (5) | |
C1 | 0.18467 (7) | −0.06957 (10) | 0.17689 (18) | 0.0422 (5) | |
C2 | 0.22244 (7) | −0.02806 (11) | 0.2337 (2) | 0.0458 (5) | |
C3 | 0.21107 (7) | 0.01979 (11) | 0.33204 (19) | 0.0449 (5) | |
C4 | 0.16209 (7) | 0.02764 (10) | 0.37888 (18) | 0.0401 (5) | |
C5 | 0.07036 (8) | −0.01017 (12) | 0.3671 (2) | 0.0500 (5) | |
C6 | 0.03282 (8) | −0.05146 (13) | 0.3139 (2) | 0.0581 (6) | |
C7 | 0.04427 (8) | −0.10059 (13) | 0.2161 (2) | 0.0600 (6) | |
C8 | 0.09341 (8) | −0.10744 (12) | 0.1717 (2) | 0.0509 (5) | |
C9 | 0.13320 (7) | −0.06496 (10) | 0.22341 (18) | 0.0405 (5) | |
C10 | 0.12189 (7) | −0.01509 (10) | 0.32454 (17) | 0.0397 (5) | |
C11 | 0.16327 (7) | 0.15787 (10) | 0.63115 (18) | 0.0417 (5) | |
C12 | 0.11381 (8) | 0.15559 (12) | 0.6772 (2) | 0.0512 (5) | |
C13 | 0.09934 (9) | 0.20058 (12) | 0.7769 (2) | 0.0561 (6) | |
C14 | 0.13384 (9) | 0.24739 (13) | 0.8317 (2) | 0.0562 (6) | |
C15 | 0.18267 (9) | 0.25047 (13) | 0.7866 (2) | 0.0606 (6) | |
C16 | 0.19809 (8) | 0.20549 (12) | 0.6858 (2) | 0.0543 (6) | |
C21 | 0.15272 (10) | −0.20762 (13) | 0.4478 (2) | 0.0667 (7) | |
C22 | 0.18927 (10) | −0.16590 (13) | 0.5063 (2) | 0.0638 (6) | |
C23 | 0.17667 (9) | −0.11757 (13) | 0.6031 (2) | 0.0595 (6) | |
C24 | 0.12661 (8) | −0.10946 (11) | 0.6448 (2) | 0.0545 (6) | |
C25 | 0.03485 (9) | −0.14348 (14) | 0.6250 (3) | 0.0646 (7) | |
C26 | −0.00117 (11) | −0.18438 (15) | 0.5662 (3) | 0.0747 (7) | |
C27 | 0.01101 (13) | −0.23589 (17) | 0.4715 (3) | 0.0902 (10) | |
C28 | 0.06034 (14) | −0.24409 (16) | 0.4349 (3) | 0.0818 (9) | |
C29 | 0.09980 (9) | −0.20238 (11) | 0.4886 (2) | 0.0549 (6) | |
C30 | 0.08807 (9) | −0.15150 (11) | 0.5868 (2) | 0.0569 (6) | |
C31 | 0.12692 (9) | 0.02105 (11) | 0.8972 (2) | 0.0531 (5) | |
C32 | 0.07563 (9) | 0.02685 (13) | 0.9341 (2) | 0.0636 (6) | |
C33 | 0.06304 (11) | 0.07348 (15) | 1.0318 (3) | 0.0724 (7) | |
C34 | 0.09943 (12) | 0.11322 (14) | 1.0925 (2) | 0.0694 (7) | |
C35 | 0.14975 (11) | 0.10847 (13) | 1.0569 (2) | 0.0653 (7) | |
C36 | 0.16350 (10) | 0.06231 (13) | 0.9593 (2) | 0.0584 (6) | |
H10 | 0.2301 (7) | −0.1135 (10) | 0.0494 (18) | 0.051 (6)* | |
H11 | 0.1733 (8) | −0.1366 (11) | 0.033 (2) | 0.069 (8)* | |
H2 | 0.2584 (7) | −0.0316 (9) | 0.2029 (17) | 0.060 (6)* | |
H3 | 0.2372 (6) | 0.0510 (8) | 0.3672 (16) | 0.040 (5)* | |
H5 | 0.0621 (7) | 0.0260 (10) | 0.4320 (18) | 0.052 (6)* | |
H6 | −0.0011 (8) | −0.0466 (10) | 0.3445 (19) | 0.072 (7)* | |
H7 | 0.0194 (7) | −0.1312 (10) | 0.1789 (19) | 0.062 (6)* | |
H8 | 0.1015 (7) | −0.1431 (10) | 0.1107 (18) | 0.047 (6)* | |
H12 | 0.0918 (7) | 0.1206 (10) | 0.643 (2) | 0.066 (7)* | |
H13 | 0.0645 (8) | 0.1997 (10) | 0.8108 (18) | 0.067 (7)* | |
H14 | 0.1233 (8) | 0.2771 (11) | 0.899 (2) | 0.069 (7)* | |
H15 | 0.2066 (8) | 0.2838 (10) | 0.8210 (19) | 0.068 (7)* | |
H16 | 0.2332 (7) | 0.2037 (9) | 0.6536 (18) | 0.058 (6)* | |
H22 | 0.2238 (8) | −0.1697 (11) | 0.484 (2) | 0.073 (7)* | |
H23 | 0.2047 (9) | −0.0847 (12) | 0.643 (2) | 0.093 (8)* | |
H25 | 0.0262 (9) | −0.1066 (13) | 0.685 (2) | 0.092 (9)* | |
H26 | −0.0400 (10) | −0.1802 (12) | 0.592 (2) | 0.105 (9)* | |
H27 | −0.0092 (9) | −0.2693 (13) | 0.417 (2) | 0.101 (9)* | |
H28 | 0.0707 (10) | −0.2824 (14) | 0.376 (3) | 0.104 (10)* | |
H32 | 0.0585 (10) | −0.0173 (14) | 0.871 (3) | 0.121 (9)* | |
H33 | 0.0260 (10) | 0.0753 (12) | 1.057 (2) | 0.095 (8)* | |
H34 | 0.0905 (8) | 0.1446 (12) | 1.154 (2) | 0.073 (8)* | |
H35 | 0.1745 (7) | 0.1384 (11) | 1.101 (2) | 0.067 (7)* | |
H36 | 0.1980 (8) | 0.0572 (10) | 0.9376 (18) | 0.060 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0499 (12) | 0.0659 (13) | 0.0507 (12) | 0.0034 (10) | −0.0021 (10) | −0.0130 (10) |
N2 | 0.0438 (9) | 0.0511 (10) | 0.0376 (9) | 0.0030 (8) | −0.0019 (8) | 0.0007 (8) |
N3 | 0.0454 (9) | 0.0497 (10) | 0.0362 (9) | 0.0042 (8) | −0.0031 (8) | −0.0024 (8) |
N4 | 0.119 (2) | 0.0844 (17) | 0.0775 (16) | 0.0169 (16) | −0.0081 (16) | −0.0253 (14) |
N5 | 0.0533 (10) | 0.0587 (11) | 0.0501 (11) | −0.0069 (9) | −0.0057 (9) | −0.0025 (10) |
N6 | 0.0625 (12) | 0.0675 (12) | 0.0572 (12) | 0.0004 (10) | −0.0013 (10) | −0.0005 (10) |
C1 | 0.0451 (11) | 0.0419 (11) | 0.0394 (11) | 0.0067 (9) | −0.0022 (9) | 0.0007 (9) |
C2 | 0.0375 (11) | 0.0521 (12) | 0.0477 (12) | 0.0028 (10) | 0.0018 (10) | −0.0006 (10) |
C3 | 0.0415 (11) | 0.0502 (12) | 0.0429 (12) | −0.0032 (10) | −0.0048 (10) | −0.0046 (10) |
C4 | 0.0395 (11) | 0.0453 (11) | 0.0357 (10) | 0.0039 (9) | −0.0001 (9) | 0.0010 (9) |
C5 | 0.0450 (12) | 0.0595 (14) | 0.0454 (13) | −0.0001 (11) | 0.0032 (10) | 0.0046 (12) |
C6 | 0.0371 (12) | 0.0747 (16) | 0.0626 (15) | −0.0040 (12) | 0.0021 (12) | 0.0079 (14) |
C7 | 0.0466 (13) | 0.0663 (15) | 0.0671 (16) | −0.0145 (12) | −0.0126 (12) | 0.0059 (13) |
C8 | 0.0534 (14) | 0.0494 (13) | 0.0498 (13) | −0.0050 (11) | −0.0092 (11) | 0.0008 (12) |
C9 | 0.0414 (11) | 0.0413 (11) | 0.0387 (11) | 0.0006 (9) | −0.0065 (9) | 0.0056 (9) |
C10 | 0.0366 (10) | 0.0450 (11) | 0.0376 (11) | 0.0018 (9) | −0.0024 (9) | 0.0058 (9) |
C11 | 0.0446 (11) | 0.0444 (11) | 0.0363 (11) | 0.0063 (9) | −0.0044 (9) | 0.0033 (10) |
C12 | 0.0544 (13) | 0.0541 (14) | 0.0450 (13) | −0.0021 (11) | −0.0011 (11) | −0.0032 (11) |
C13 | 0.0549 (14) | 0.0635 (14) | 0.0500 (14) | 0.0011 (12) | 0.0054 (12) | −0.0072 (12) |
C14 | 0.0613 (15) | 0.0613 (15) | 0.0459 (13) | 0.0101 (13) | −0.0038 (12) | −0.0106 (12) |
C15 | 0.0588 (14) | 0.0609 (14) | 0.0621 (15) | 0.0026 (13) | −0.0145 (13) | −0.0152 (12) |
C16 | 0.0418 (12) | 0.0605 (13) | 0.0605 (15) | 0.0044 (11) | −0.0015 (11) | −0.0073 (12) |
C21 | 0.0892 (19) | 0.0554 (15) | 0.0554 (15) | 0.0073 (14) | −0.0067 (14) | 0.0043 (12) |
C22 | 0.0639 (16) | 0.0636 (15) | 0.0639 (16) | −0.0022 (14) | −0.0094 (14) | 0.0018 (13) |
C23 | 0.0553 (14) | 0.0652 (15) | 0.0580 (15) | −0.0015 (13) | −0.0008 (12) | 0.0068 (13) |
C24 | 0.0647 (15) | 0.0511 (13) | 0.0479 (13) | −0.0023 (11) | −0.0047 (11) | 0.0050 (11) |
C25 | 0.0599 (15) | 0.0722 (17) | 0.0618 (16) | −0.0145 (13) | −0.0040 (13) | 0.0151 (14) |
C26 | 0.0712 (18) | 0.0825 (19) | 0.0703 (18) | −0.0244 (15) | −0.0087 (15) | 0.0139 (16) |
C27 | 0.098 (2) | 0.081 (2) | 0.092 (2) | −0.0350 (19) | −0.030 (2) | 0.0264 (19) |
C28 | 0.110 (2) | 0.0634 (18) | 0.0717 (19) | −0.0235 (18) | −0.0301 (18) | 0.0136 (15) |
C29 | 0.0731 (16) | 0.0468 (12) | 0.0448 (13) | −0.0052 (12) | −0.0117 (12) | 0.0084 (11) |
C30 | 0.0708 (15) | 0.0509 (13) | 0.0490 (13) | −0.0161 (11) | −0.0161 (12) | 0.0168 (11) |
C31 | 0.0717 (15) | 0.0474 (12) | 0.0402 (12) | 0.0076 (11) | −0.0019 (11) | 0.0013 (10) |
C32 | 0.0676 (16) | 0.0637 (16) | 0.0596 (16) | −0.0055 (13) | −0.0062 (13) | 0.0063 (13) |
C33 | 0.0687 (17) | 0.0811 (19) | 0.0673 (18) | 0.0110 (15) | 0.0140 (15) | 0.0112 (15) |
C34 | 0.095 (2) | 0.0644 (17) | 0.0487 (16) | 0.0130 (16) | 0.0007 (15) | −0.0026 (13) |
C35 | 0.0782 (18) | 0.0591 (16) | 0.0585 (16) | 0.0000 (14) | −0.0142 (14) | −0.0042 (13) |
C36 | 0.0539 (14) | 0.0628 (15) | 0.0586 (15) | 0.0051 (12) | −0.0039 (13) | 0.0067 (13) |
Geometric parameters (Å, º) top
N1—C1 | 1.368 (2) | C12—C13 | 1.380 (3) |
C1—C2 | 1.381 (3) | C12—H12 | 0.933 (19) |
C2—C3 | 1.383 (3) | C13—C14 | 1.373 (3) |
C3—C4 | 1.376 (2) | C13—H13 | 0.98 (2) |
C4—N2 | 1.400 (2) | C14—C15 | 1.360 (3) |
N2—N3 | 1.270 (2) | C14—H14 | 0.93 (2) |
N4—C21 | 1.362 (3) | C15—C16 | 1.396 (3) |
C21—C22 | 1.369 (3) | C15—H15 | 0.947 (19) |
C22—C23 | 1.384 (3) | C16—H16 | 0.976 (18) |
C23—C24 | 1.386 (3) | C21—C29 | 1.449 (3) |
C24—N5 | 1.412 (3) | C22—H22 | 0.93 (2) |
N5—N6 | 1.262 (2) | C23—H23 | 1.04 (2) |
N1—H10 | 0.912 (18) | C24—C30 | 1.407 (3) |
N1—H11 | 0.87 (2) | C25—C26 | 1.352 (3) |
N3—C11 | 1.436 (2) | C25—C30 | 1.453 (3) |
N4—H4A | 0.8230 | C25—H25 | 0.95 (2) |
N4—H4B | 0.8230 | C26—C27 | 1.405 (4) |
N6—C31 | 1.427 (3) | C26—H26 | 1.05 (2) |
C1—C9 | 1.431 (2) | C27—C28 | 1.352 (4) |
C2—H2 | 0.995 (18) | C27—H27 | 0.99 (2) |
C3—H3 | 0.965 (16) | C28—C29 | 1.402 (3) |
C4—C10 | 1.430 (2) | C28—H28 | 0.97 (3) |
C5—C6 | 1.359 (3) | C29—C30 | 1.420 (3) |
C5—C10 | 1.420 (3) | C31—C36 | 1.382 (3) |
C5—H5 | 0.973 (18) | C31—C32 | 1.398 (3) |
C6—C7 | 1.394 (3) | C32—C33 | 1.370 (3) |
C6—H6 | 0.95 (2) | C32—H32 | 1.14 (3) |
C7—C8 | 1.370 (3) | C33—C34 | 1.356 (4) |
C7—H7 | 0.944 (19) | C33—H33 | 1.00 (2) |
C8—C9 | 1.409 (3) | C34—C35 | 1.368 (3) |
C8—H8 | 0.938 (18) | C34—H34 | 0.89 (2) |
C9—C10 | 1.427 (2) | C35—C36 | 1.372 (3) |
C11—C12 | 1.378 (3) | C35—H35 | 0.96 (2) |
C11—C16 | 1.386 (3) | C36—H36 | 0.933 (19) |
| | | |
C1—N1—H10 | 116.4 (12) | C14—C15—H15 | 121.1 (12) |
C1—N1—H11 | 120.8 (14) | C16—C15—H15 | 118.6 (12) |
H10—N1—H11 | 120.9 (19) | C11—C16—C15 | 119.7 (2) |
N3—N2—C4 | 116.97 (15) | C11—C16—H16 | 117.0 (11) |
N2—N3—C11 | 112.42 (15) | C15—C16—H16 | 123.2 (11) |
C21—N4—H4A | 120.0 | N4—C21—C22 | 120.0 (3) |
C21—N4—H4B | 120.0 | N4—C21—C29 | 120.0 (3) |
H4A—N4—H4B | 120.0 | C22—C21—C29 | 119.9 (2) |
N6—N5—C24 | 115.17 (17) | C21—C22—C23 | 121.3 (3) |
N5—N6—C31 | 114.70 (18) | C21—C22—H22 | 121.3 (13) |
N1—C1—C2 | 119.57 (19) | C23—C22—H22 | 117.4 (13) |
N1—C1—C9 | 120.83 (18) | C22—C23—C24 | 121.4 (2) |
C2—C1—C9 | 119.60 (18) | C22—C23—H23 | 120.0 (13) |
C1—C2—C3 | 121.10 (18) | C24—C23—H23 | 118.5 (13) |
C1—C2—H2 | 120.0 (11) | C23—C24—C30 | 118.8 (2) |
C3—C2—H2 | 118.8 (11) | C23—C24—N5 | 126.0 (2) |
C4—C3—C2 | 121.85 (19) | C30—C24—N5 | 115.2 (2) |
C4—C3—H3 | 117.5 (10) | C26—C25—C30 | 119.0 (3) |
C2—C3—H3 | 120.6 (10) | C26—C25—H25 | 122.1 (15) |
C3—C4—N2 | 125.48 (17) | C30—C25—H25 | 118.7 (15) |
C3—C4—C10 | 119.03 (18) | C25—C26—C27 | 122.5 (3) |
N2—C4—C10 | 115.49 (16) | C25—C26—H26 | 121.2 (14) |
C6—C5—C10 | 121.4 (2) | C27—C26—H26 | 116.3 (14) |
C6—C5—H5 | 120.5 (11) | C28—C27—C26 | 119.2 (3) |
C10—C5—H5 | 118.0 (11) | C28—C27—H27 | 106.2 (15) |
C5—C6—C7 | 120.4 (2) | C26—C27—H27 | 134.5 (15) |
C5—C6—H6 | 119.1 (13) | C27—C28—C29 | 121.8 (3) |
C7—C6—H6 | 120.5 (12) | C27—C28—H28 | 121.6 (16) |
C8—C7—C6 | 120.4 (2) | C29—C28—H28 | 116.3 (17) |
C8—C7—H7 | 116.9 (12) | C28—C29—C30 | 119.4 (3) |
C6—C7—H7 | 122.7 (12) | C28—C29—C21 | 123.3 (3) |
C7—C8—C9 | 120.8 (2) | C30—C29—C21 | 117.4 (2) |
C7—C8—H8 | 120.3 (11) | C24—C30—C29 | 121.2 (2) |
C9—C8—H8 | 118.8 (11) | C24—C30—C25 | 120.7 (2) |
C8—C9—C10 | 119.15 (18) | C29—C30—C25 | 118.0 (2) |
C8—C9—C1 | 122.10 (18) | C36—C31—C32 | 119.5 (2) |
C10—C9—C1 | 118.74 (16) | C36—C31—N6 | 116.9 (2) |
C5—C10—C9 | 117.80 (18) | C32—C31—N6 | 123.6 (2) |
C5—C10—C4 | 122.57 (19) | C33—C32—C31 | 118.8 (2) |
C9—C10—C4 | 119.63 (16) | C33—C32—H32 | 141.6 (13) |
C12—C11—C16 | 119.50 (19) | C31—C32—H32 | 99.4 (13) |
C12—C11—N3 | 124.19 (18) | C34—C33—C32 | 121.1 (3) |
C16—C11—N3 | 116.30 (17) | C34—C33—H33 | 122.5 (14) |
C11—C12—C13 | 119.9 (2) | C32—C33—H33 | 116.4 (14) |
C11—C12—H12 | 117.9 (13) | C33—C34—C35 | 120.8 (3) |
C13—C12—H12 | 122.0 (13) | C33—C34—H34 | 120.0 (15) |
C14—C13—C12 | 120.7 (2) | C35—C34—H34 | 119.1 (15) |
C14—C13—H13 | 118.2 (12) | C34—C35—C36 | 119.4 (3) |
C12—C13—H13 | 121.1 (12) | C34—C35—H35 | 118.7 (12) |
C15—C14—C13 | 120.0 (2) | C36—C35—H35 | 121.9 (12) |
C15—C14—H14 | 120.7 (13) | C35—C36—C31 | 120.4 (2) |
C13—C14—H14 | 119.3 (13) | C35—C36—H36 | 119.6 (12) |
C14—C15—C16 | 120.2 (2) | C31—C36—H36 | 119.9 (12) |
(II) [4-(phenyldiazenyl)naphthalen-1-yl]ammonium chloride
top
Crystal data top
C16H14N3+·Cl− | Z = 4 |
Mr = 283.76 | F(000) = 592 |
Monoclinic, P21/c | Dx = 1.366 Mg m−3 |
a = 7.426 (3) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 13.305 (4) Å | T = 295 K |
c = 14.027 (4) Å | Particle morphology: plates |
β = 95.32 (2)° | dark blue |
V = 1380 (1) Å3 | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 8.5°, 2θmax = 68.5°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder. Specimen was rotated in its
plane | |
Refinement top
Refinement on Inet | 107 parameters |
Least-squares matrix: full with fixed elements per cycle | 10 restraints |
Rp = 0.042 | 0 constraints |
Rwp = 0.052 | H-atom parameters not refined |
Rexp = 0.032 | Weighting scheme based on measured s.u.'s |
χ2 = 2.560 | (Δ/σ)max = 0.04 |
3226 data points | Background function: Chebyshev polynomial up to the 5th order |
Excluded region(s): 5.50-8.48 | Preferred orientation correction: March-Dollase (Dollase, 1986) along [100], G1 = 1.4883(9) |
Profile function: split-type pseudo-Voigt | |
Crystal data top
C16H14N3+·Cl− | β = 95.32 (2)° |
Mr = 283.76 | V = 1380 (1) Å3 |
Monoclinic, P21/c | Z = 4 |
a = 7.426 (3) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 13.305 (4) Å | T = 295 K |
c = 14.027 (4) Å | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Scan method: step |
Specimen mounting: pressed as a thin layer in the specimen holder. Specimen was rotated in its
plane | 2θmin = 8.5°, 2θmax = 68.5°, 2θstep = 0.02° |
Data collection mode: reflection | |
Refinement top
Rp = 0.042 | 3226 data points |
Rwp = 0.052 | 107 parameters |
Rexp = 0.032 | 10 restraints |
χ2 = 2.560 | H-atom parameters not refined |
Special details top
Experimental. The specimen was rotated in its plane |
Refinement. H atoms were constrained at calculated positions, and the planarity of the
phenyl ring and the naphthalene residue was restrained. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.3811 (9) | 0.5299 (3) | 0.8182 (3) | 0.074 (2)* | |
N1 | 0.4054 (12) | 0.1384 (7) | 0.4964 (8) | 0.063 (2)* | |
N2 | 0.2439 (15) | 0.5384 (9) | 0.5196 (8) | 0.063 (2)* | |
N3 | 0.2760 (15) | 0.5956 (9) | 0.5977 (7) | 0.063 (2)* | |
C1 | 0.3643 (13) | 0.2355 (9) | 0.4987 (9) | 0.063 (2)* | |
C2 | 0.4113 (14) | 0.2870 (8) | 0.5875 (8) | 0.063 (2)* | |
C3 | 0.3731 (14) | 0.3865 (9) | 0.5961 (8) | 0.063 (2)* | |
C4 | 0.2856 (11) | 0.4439 (5) | 0.5191 (9) | 0.063 (2)* | |
C5 | 0.1450 (15) | 0.4436 (8) | 0.3467 (9) | 0.063 (2)* | |
C6 | 0.1001 (14) | 0.3913 (9) | 0.2627 (8) | 0.063 (2)* | |
C7 | 0.1409 (12) | 0.2894 (9) | 0.2549 (8) | 0.063 (2)* | |
C8 | 0.2274 (17) | 0.2371 (8) | 0.3316 (9) | 0.063 (2)* | |
C9 | 0.2744 (15) | 0.2891 (8) | 0.4183 (7) | 0.063 (2)* | |
C10 | 0.2342 (18) | 0.3928 (9) | 0.4268 (8) | 0.063 (2)* | |
C11 | 0.2413 (18) | 0.6960 (8) | 0.5910 (9) | 0.063 (2)* | |
C12 | 0.1678 (19) | 0.7394 (9) | 0.5069 (9) | 0.063 (2)* | |
C13 | 0.1325 (16) | 0.8416 (8) | 0.5044 (8) | 0.063 (2)* | |
C14 | 0.1703 (15) | 0.9008 (8) | 0.5864 (9) | 0.063 (2)* | |
C15 | 0.2454 (15) | 0.8596 (6) | 0.6702 (8) | 0.063 (2)* | |
C16 | 0.2817 (19) | 0.7541 (9) | 0.6733 (9) | 0.063 (2)* | |
H10 | 0.3796 | 0.0917 | 0.4389 | 0.05* | |
H11 | 0.4699 | 0.1059 | 0.5585 | 0.05* | |
H22 | 0.4783 | 0.2442 | 0.6462 | 0.05* | |
H23 | 0.4135 | 0.4227 | 0.6659 | 0.05* | |
H24 | 0.2547 | 0.1583 | 0.3225 | 0.05* | |
H25 | 0.1057 | 0.2473 | 0.1885 | 0.05* | |
H26 | 0.0331 | 0.4323 | 0.2014 | 0.05* | |
H27 | 0.1148 | 0.5222 | 0.3532 | 0.05* | |
H28 | 0.3367 | 0.7186 | 0.7388 | 0.05* | |
H29 | 0.2788 | 0.9035 | 0.7347 | 0.05* | |
H30 | 0.1426 | 0.9821 | 0.5821 | 0.05* | |
H31 | 0.0753 | 0.8766 | 0.4381 | 0.05* | |
H32 | 0.1358 | 0.6931 | 0.4425 | 0.05* | |
H33 | 0.3294 | 0.5646 | 0.6617 | 0.05* | |
Geometric parameters (Å, º) top
N1—C1 | 1.329 (15) | C6—H26 | 1.098 |
N1—H10 | 1.022 | C7—C8 | 1.388 (16) |
N1—H11 | 1.048 | C7—H25 | 1.098 |
N2—N3 | 1.337 (16) | C8—C9 | 1.415 (16) |
N2—C4 | 1.295 (14) | C8—H24 | 1.078 |
N3—C11 | 1.362 (16) | C9—C10 | 1.419 (16) |
N3—H33 | 1.034 | C11—C12 | 1.380 (17) |
C1—C2 | 1.436 (16) | C11—C16 | 1.399 (17) |
C1—C9 | 1.445 (15) | C12—C13 | 1.385 (16) |
C2—C3 | 1.362 (16) | C12—H32 | 1.101 |
C2—H22 | 1.083 | C13—C14 | 1.401 (16) |
C3—C4 | 1.429 (15) | C13—H31 | 1.090 |
C3—H23 | 1.107 | C14—C15 | 1.368 (16) |
C4—C10 | 1.481 (16) | C14—H30 | 1.102 |
C5—C6 | 1.383 (16) | C15—C16 | 1.430 (15) |
C5—C10 | 1.422 (16) | C15—H29 | 1.086 |
C5—H27 | 1.076 | C16—H28 | 1.079 |
C6—C7 | 1.396 (17) | | |
| | | |
H10—N1—H11 | 116 | C7—C8—H24 | 118 |
C1—N1—H11 | 118 | C7—C8—C9 | 119 (1) |
C1—N1—H10 | 126 | C9—C8—H24 | 123 |
N3—N2—C4 | 122 (1) | C1—C9—C8 | 119 (1) |
N2—N3—H33 | 121 | C8—C9—C10 | 121 (1) |
N2—N3—C11 | 119 (1) | C1—C9—C10 | 120 (1) |
C11—N3—H33 | 120 | C5—C10—C9 | 119 (1) |
N1—C1—C9 | 123 (1) | C4—C10—C9 | 118.7 (9) |
N1—C1—C2 | 117 (1) | C4—C10—C5 | 122 (1) |
C2—C1—C9 | 120 (1) | N3—C11—C16 | 117 (1) |
C1—C2—H22 | 118 | N3—C11—C12 | 122 (1) |
C1—C2—C3 | 120 (1) | C12—C11—C16 | 121 (1) |
C3—C2—H22 | 122 | C11—C12—H32 | 120 |
C2—C3—H23 | 117 | C11—C12—C13 | 119 (1) |
C2—C3—C4 | 122 (1) | C13—C12—H32 | 120 |
C4—C3—H23 | 120 | C12—C13—H31 | 120 |
N2—C4—C3 | 127.4 (9) | C12—C13—C14 | 121 (1) |
C3—C4—C10 | 119 (1) | C14—C13—H31 | 120 |
N2—C4—C10 | 114.1 (9) | C13—C14—H30 | 119 |
C10—C5—H27 | 119 | C13—C14—C15 | 121 (1) |
C6—C5—H27 | 122 | C15—C14—H30 | 120 |
C6—C5—C10 | 119 (1) | C14—C15—H29 | 123 |
C5—C6—H26 | 118 | C14—C15—C16 | 118.7 (9) |
C5—C6—C7 | 121 (1) | C16—C15—H29 | 118 |
C7—C6—H26 | 120 | C11—C16—C15 | 119 (1) |
C6—C7—H25 | 122 | C15—C16—H28 | 121 |
C6—C7—C8 | 121 (1) | C11—C16—H28 | 120 |
C8—C7—H25 | 117 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | H···A | D···A | D—H···A |
N1—H10···Cl1i | 2.34 | 3.35 (1) | 168 |
N1—H11···Cl1ii | 2.21 | 3.26 (1) | 175 |
N3—H33···Cl1 | 2.24 | 3.24 (1) | 162 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C16H13N3 | C16H14N3+·Cl− |
Mr | 247.29 | 283.76 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 293 | 295 |
a, b, c (Å) | 26.120 (5), 18.473 (4), 10.379 (3) | 7.426 (3), 13.305 (4), 14.027 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 95.32 (2), 90 |
V (Å3) | 5008 (2) | 1380 (1) |
Z | 16 | 4 |
Radiation type | Mo Kα | Cu Kα, λ = 1.5418 Å |
µ (mm−1) | 0.08 | – |
Specimen shape, size (mm) | 0.45 × 0.38 × 0.14 | Flat_sheet, 25 × 25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | DRON-3M diffractometer (Burevestnik, Russia) |
Specimen mounting | – | Pressed as a thin layer in the specimen holder. Specimen was rotated in its
plane |
Data collection mode | – | Reflection |
Data collection method | ω scans | Step |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4915, 4915, 2908 | – |
Rint | 0.000 | – |
θ values (°) | θmax = 26.0, θmin = 1.6 | 2θmin = 8.5 2θmax = 68.5 2θstep = 0.02 |
(sin θ/λ)max (Å−1) | 0.616 | – |
|
Refinement |
R factors and goodness of fit | R[F2 > 2σ(F2)] = 0.053, wR(F2) = 0.118, S = 1.28 | Rp = 0.042, Rwp = 0.052, Rexp = 0.032, χ2 = 2.560 |
No. of reflections/data points | 4915 | 3226 |
No. of parameters | 443 | 107 |
No. of restraints | 0 | 10 |
H-atom treatment | All H-atom parameters refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.15 | – |
Selected bond lengths (Å) for (I) topN1—C1 | 1.368 (2) | N4—C21 | 1.362 (3) |
C1—C2 | 1.381 (3) | C21—C22 | 1.369 (3) |
C2—C3 | 1.383 (3) | C22—C23 | 1.384 (3) |
C3—C4 | 1.376 (2) | C23—C24 | 1.386 (3) |
C4—N2 | 1.400 (2) | C24—N5 | 1.412 (3) |
N2—N3 | 1.270 (2) | N5—N6 | 1.262 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | H···A | D···A | D—H···A |
N1—H10···Cl1i | 2.34 | 3.35 (1) | 168 |
N1—H11···Cl1ii | 2.21 | 3.26 (1) | 175 |
N3—H33···Cl1 | 2.24 | 3.24 (1) | 162 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2. |
Azoderivatives of α-naphthylamine form a family of widely used dyes. However, the structure of only one representative of this family has been determined up to now (Foitzik et al., 1991). Solvent Yellow 4, (I), is the simplest molecule of this class. \sch
In the crystal, the two independent molecules of (I) form pairs, as shown in Fig. 1. Both molecules are close to planar, the dihedral angles formed by the least-squares planes through the naphthalene and phenyl moieties being 5.19 (6) and 2.12 (5)° in molecules (Ia) and (Ib), respectively. The C1—N1 and C21—N4 bond lengths fall in between the values for planar and pyramidal amino groups (Yatsenko & Paseshnichenko, 1999). The shortest intermolecular distance within a pair (C12···C31) is 3.392 (3) Å, and the dihedral angle between the least-squares planes of (Ia) and (Ib) is 3.31 (3)°.
The molecular pairs in (I) are packed in a herringbone manner into layers perpendicular to [100]. In addition, molecules (Ia) are linked by weak N1—H10···N3i hydrogen bonds: N1···N3i 3.188 (3) Å and N1—H10···N3i 166 (2)° [symmetry code: (i) 1/2 - x, -y, z - 1/2]. The polarization of molecule (Ia) under the effect of this bond does not cause any noticeable difference in bond lengths in the aminoazo chains of (Ia) and (Ib) (Table 1). However, the AM1 calculations, in which the polarization effect of the surrounding molecules in the crystal was modelled via the incorporation of an electrostatic field into the Hamiltonian of a molecule, indicate the pronounced nonequivalence of (Ia) and (Ib): their calculated dipole moments were 6.09 and 2.95 D, respectively, whereas for an isolated molecule of (I) the calculations yield 2.69 D. It is noteworthy that the polarization effect of the crystal environment on the electronic structure of (Ia) is stronger than the possible effect of polar solvent modelled with COSMO (Klamt & Schüürmann, 1993): the calculated dipole moment of molecule of (I) placed into a medium with a relative? dielectric permittivity ε = 81 is 5.10 D.
The crystal-packing motif adopted by (II) is presented in Fig. 2, with the dotted lines representing the hydrogen bonds (Table 2). The cation is close to planar: the phenyl ring is twisted by 4.4 (2)° with respect to the naphthalene residue. Neighbouring cations within the stack are related by inversion centres, with interplanar distances of 3.42 (1) and 3.48 (1) Å. The very close packing motif - columns of inversion-related cations with the Cl- anions in the intercolumnar channels - has been observed in the structure of p-phenylazoaniline hydrochloride (Yatsenko et al., 2000), and in the structure of 2,4-diaminoazobenzene hydrochloride dihydrate (Moreiras et al., 1981) the cations also form stacks, although they are not parallel. The cation-anion and cation-cation interactions facilitate charge transfer from the amino group to the azonium linkage: according to the AM1 calculations, the total effective charges on the amino group in an isolated cation and in the cation in the crystal environment are 0.24 and 0.39 e, respectively, and the effective charges on the azonium linkage are 0.27 and 0.19 e, respectively.
The first ππ*-excitation of (I) and (II) is almost pure HOMO → LUMO (highest occupied molecular orbital → lowest unoccupied molecular orbital) one-electron excitation. Thus, in order to study the properties of the frontier orbitals, we modelled the effect of the crystal environment on the HOMO-LUMO energy gap. For (II), the gap extends from 5.95 eV for an isolated cation to 6.33 eV for a cation in the crystal lattice, whereas in (I) the two non-equivalent molecules behave in different ways: in (Ia) this gap decreases from 7.10 to 6.79 eV, and in (Ib) it remains essentially unchanged (7.16 and 7.14 eV, respectively). In line with these calculations, (I) and (II) demonstrate red and blue shifts, respectively, on transfer from alcohol solution to the solid state: from 22800 cm-1 to 21350 cm-1 for (I), and from 18850 cm-1 to 19400 cm-1 for (II).