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An unexpected global disorder (co-existing rotational disorder and glide disorder) has been observed during an X-ray investigation of the crystal structure of (E)-[1-(biphenyl-4-yl)ethylidene]hydrazine, C14H14N2, at room temperature. When the temperature decreases to 273 K, the disorder disappears, but the quality of the data set is low. The diffraction data were collected again at 110 K. Differential scanning calorimetry (DSC) analysis and polarizing-microscopy experiments, as well as a fourth set of single-crystal data collected at 283 K, proved that the order–disorder transformation occurs continuously. The analyses of these crystal structures and full-range relaxed potential energy surface scans showed that this kind of global disorder is not very difficult to achieve inside the crystal. Experimental and theoretical studies via UV–Vis and fluorescence spectra impart an understanding on the prediction methods of optical properties, which are essential for the rational design of biphenyl-based materials with pre-defined properties.
Supporting information
CCDC references: 1835377; 1842281
For both structures, data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b). Molecular graphics: SHELXTL (Bruker, 2000), PLATON (Spek, 2009) WinGX2014 (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 1999) for o-BEH-110; SHELXTL (Bruker, 2000) and PLATON (Spek, 2009) for dBEH. For both structures, software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).
(
E)-[1-(Biphenyl-4-yl)ethylidene]hydrazine (o-BEH-110)
top
Crystal data top
C14H14N2 | Dx = 1.264 Mg m−3 |
Mr = 210.27 | Melting point: 422.7(4) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.740 (2) Å | Cell parameters from 380 reflections |
b = 5.5154 (6) Å | θ = 2.5–26.0° |
c = 8.1367 (8) Å | µ = 0.08 mm−1 |
β = 95.727 (9)° | T = 110 K |
V = 1104.71 (19) Å3 | Plate, colorless |
Z = 4 | 0.6 × 0.4 × 0.05 mm |
F(000) = 448 | |
Data collection top
Bruker SMART CCD area detector diffractometer | 2249 independent reflections |
Radiation source: fine-focus sealed tube | 1283 reflections with I > 2σ(I) |
Detector resolution: 10.10 pixels mm-1 | Rint = 0.036 |
phi and ω scans | θmax = 26.4°, θmin = 3.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −30→30 |
Tmin = 0.976, Tmax = 0.991 | k = −6→6 |
6798 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | All H-atom parameters refined |
wR(F2) = 0.133 | w = 1/[σ2(Fo2) + (0.0556P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
2249 reflections | Δρmax = 0.13 e Å−3 |
201 parameters | Δρmin = −0.15 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. The structures were solved by SHELXL-97 [Sheldrick, 2015].
Diagrams and
publication material were prepared using PLATON [Spek, 2009].
WinGX-2014
[Farrugia, 2012] and DIAMOND (crystal packing diagram)
[Brandenburg & Putz,
1999] were also used. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.87333 (7) | 0.6786 (3) | 0.4854 (2) | 0.0502 (5) | |
C2 | 0.92711 (7) | 0.6754 (4) | 0.5540 (2) | 0.0569 (5) | |
C3 | 0.94541 (7) | 0.4964 (3) | 0.6609 (2) | 0.0513 (5) | |
C4 | 0.91024 (7) | 0.3212 (4) | 0.7026 (2) | 0.0581 (5) | |
C5 | 0.85648 (7) | 0.3229 (3) | 0.6346 (2) | 0.0486 (5) | |
C6 | 0.83701 (6) | 0.5017 (3) | 0.52435 (17) | 0.0356 (4) | |
C7 | 0.77929 (6) | 0.5012 (2) | 0.44764 (17) | 0.0332 (4) | |
C8 | 0.74336 (7) | 0.3197 (3) | 0.4809 (2) | 0.0499 (5) | |
C9 | 0.69049 (7) | 0.3165 (3) | 0.4096 (2) | 0.0499 (5) | |
C10 | 0.67029 (6) | 0.4953 (2) | 0.30037 (17) | 0.0344 (4) | |
C11 | 0.70597 (7) | 0.6775 (3) | 0.2679 (2) | 0.0504 (5) | |
C12 | 0.75911 (7) | 0.6797 (3) | 0.3400 (2) | 0.0483 (4) | |
C13 | 0.61364 (6) | 0.4869 (3) | 0.21933 (18) | 0.0378 (4) | |
C14 | 0.59471 (9) | 0.6695 (4) | 0.0922 (3) | 0.0564 (5) | |
N1 | 0.58372 (5) | 0.3143 (2) | 0.26501 (17) | 0.0471 (4) | |
N2 | 0.53027 (6) | 0.3034 (3) | 0.1868 (2) | 0.0564 (4) | |
H1 | 0.8610 (7) | 0.808 (3) | 0.407 (2) | 0.069 (6)* | |
H2 | 0.9521 (8) | 0.801 (3) | 0.525 (2) | 0.072 (6)* | |
H3 | 0.9819 (8) | 0.493 (3) | 0.706 (2) | 0.069 (5)* | |
H4 | 0.9212 (8) | 0.199 (3) | 0.780 (2) | 0.076 (6)* | |
H5 | 0.8320 (7) | 0.195 (3) | 0.662 (2) | 0.061 (5)* | |
H8 | 0.7540 (8) | 0.192 (3) | 0.558 (2) | 0.077 (6)* | |
H9 | 0.6656 (8) | 0.184 (3) | 0.437 (2) | 0.077 (6)* | |
H11 | 0.6939 (8) | 0.802 (3) | 0.192 (2) | 0.072 (6)* | |
H12 | 0.7813 (7) | 0.808 (3) | 0.311 (2) | 0.068 (6)* | |
H14A | 0.6175 (10) | 0.796 (4) | 0.084 (3) | 0.102 (8)* | |
H14B | 0.5573 (9) | 0.726 (3) | 0.106 (2) | 0.084 (6)* | |
H14C | 0.5906 (9) | 0.600 (4) | −0.015 (3) | 0.105 (8)* | |
H15A | 0.5151 (7) | 0.144 (4) | 0.209 (2) | 0.069 (6)* | |
H15B | 0.5285 (8) | 0.323 (4) | 0.079 (3) | 0.076 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0435 (10) | 0.0475 (11) | 0.0577 (10) | −0.0082 (8) | −0.0044 (8) | 0.0084 (9) |
C2 | 0.0461 (11) | 0.0601 (12) | 0.0632 (11) | −0.0162 (9) | −0.0015 (8) | 0.0036 (10) |
C3 | 0.0358 (9) | 0.0609 (12) | 0.0561 (11) | −0.0012 (9) | −0.0013 (8) | −0.0037 (10) |
C4 | 0.0459 (11) | 0.0603 (12) | 0.0666 (11) | 0.0061 (9) | −0.0019 (9) | 0.0138 (10) |
C5 | 0.0393 (9) | 0.0469 (10) | 0.0595 (10) | 0.0007 (8) | 0.0045 (8) | 0.0138 (9) |
C6 | 0.0366 (8) | 0.0352 (9) | 0.0358 (8) | −0.0003 (7) | 0.0080 (6) | −0.0038 (7) |
C7 | 0.0346 (8) | 0.0316 (8) | 0.0338 (8) | 0.0007 (6) | 0.0062 (6) | −0.0023 (7) |
C8 | 0.0441 (10) | 0.0455 (10) | 0.0575 (10) | −0.0072 (8) | −0.0082 (8) | 0.0223 (9) |
C9 | 0.0415 (10) | 0.0470 (10) | 0.0594 (10) | −0.0106 (8) | −0.0035 (8) | 0.0171 (9) |
C10 | 0.0349 (8) | 0.0344 (8) | 0.0346 (8) | 0.0017 (7) | 0.0072 (6) | −0.0012 (7) |
C11 | 0.0416 (10) | 0.0457 (10) | 0.0628 (11) | −0.0009 (8) | −0.0011 (8) | 0.0190 (9) |
C12 | 0.0383 (9) | 0.0439 (10) | 0.0620 (10) | −0.0085 (7) | 0.0012 (8) | 0.0190 (9) |
C13 | 0.0355 (8) | 0.0406 (9) | 0.0376 (8) | 0.0028 (7) | 0.0061 (6) | −0.0041 (8) |
C14 | 0.0407 (10) | 0.0642 (14) | 0.0635 (12) | 0.0055 (10) | 0.0009 (9) | 0.0135 (11) |
N1 | 0.0365 (7) | 0.0477 (8) | 0.0562 (8) | −0.0025 (6) | −0.0004 (6) | 0.0000 (7) |
N2 | 0.0370 (8) | 0.0564 (11) | 0.0732 (11) | −0.0045 (7) | −0.0074 (7) | −0.0013 (9) |
Geometric parameters (Å, º) top
C1—C6 | 1.384 (2) | C9—C10 | 1.387 (2) |
C1—C2 | 1.391 (2) | C9—H9 | 0.994 (19) |
C1—H1 | 0.983 (18) | C10—C11 | 1.380 (2) |
C2—C3 | 1.363 (2) | C10—C13 | 1.489 (2) |
C2—H2 | 0.973 (19) | C11—C12 | 1.385 (2) |
C3—C4 | 1.366 (2) | C11—H11 | 0.950 (19) |
C3—H3 | 0.939 (18) | C12—H12 | 0.942 (18) |
C4—C5 | 1.389 (2) | C13—N1 | 1.2835 (18) |
C4—H4 | 0.94 (2) | C13—C14 | 1.486 (2) |
C5—C6 | 1.387 (2) | C14—H14A | 0.91 (2) |
C5—H5 | 0.970 (17) | C14—H14B | 0.99 (2) |
C6—C7 | 1.5003 (19) | C14—H14C | 0.95 (2) |
C7—C12 | 1.378 (2) | N1—N2 | 1.4104 (18) |
C7—C8 | 1.383 (2) | N2—H15A | 0.98 (2) |
C8—C9 | 1.377 (2) | N2—H15B | 0.88 (2) |
C8—H8 | 0.960 (19) | | |
| | | |
C6—C1—C2 | 121.06 (17) | C8—C9—H9 | 119.9 (11) |
C6—C1—H1 | 119.5 (10) | C10—C9—H9 | 118.3 (11) |
C2—C1—H1 | 119.5 (10) | C11—C10—C9 | 116.35 (15) |
C3—C2—C1 | 120.60 (17) | C11—C10—C13 | 121.98 (14) |
C3—C2—H2 | 119.5 (11) | C9—C10—C13 | 121.64 (13) |
C1—C2—H2 | 119.9 (11) | C10—C11—C12 | 121.57 (16) |
C2—C3—C4 | 119.46 (17) | C10—C11—H11 | 119.0 (11) |
C2—C3—H3 | 120.6 (11) | C12—C11—H11 | 119.4 (11) |
C4—C3—H3 | 120.0 (11) | C7—C12—C11 | 122.08 (15) |
C3—C4—C5 | 120.32 (18) | C7—C12—H12 | 120.9 (11) |
C3—C4—H4 | 121.6 (12) | C11—C12—H12 | 117.0 (11) |
C5—C4—H4 | 118.0 (12) | N1—C13—C14 | 123.62 (15) |
C6—C5—C4 | 121.31 (16) | N1—C13—C10 | 116.07 (13) |
C6—C5—H5 | 118.8 (10) | C14—C13—C10 | 120.30 (14) |
C4—C5—H5 | 119.9 (10) | C13—C14—H14A | 114.9 (15) |
C1—C6—C5 | 117.24 (15) | C13—C14—H14B | 111.4 (10) |
C1—C6—C7 | 121.23 (14) | H14A—C14—H14B | 111.2 (18) |
C5—C6—C7 | 121.52 (13) | C13—C14—H14C | 111.4 (14) |
C12—C7—C8 | 116.26 (15) | H14A—C14—H14C | 104 (2) |
C12—C7—C6 | 122.19 (13) | H14B—C14—H14C | 102.6 (17) |
C8—C7—C6 | 121.56 (13) | C13—N1—N2 | 116.27 (14) |
C9—C8—C7 | 121.93 (15) | N1—N2—H15A | 108.2 (11) |
C9—C8—H8 | 116.8 (12) | N1—N2—H15B | 113.3 (13) |
C7—C8—H8 | 121.2 (12) | H15A—N2—H15B | 108.3 (17) |
C8—C9—C10 | 121.81 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H15A···N2i | 0.98 (2) | 2.39 (2) | 3.349 (2) | 167.0 (14) |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
(
E)-[1-(Biphenyl-4-yl)ethylidene]hydrazine (dBEH)
top
Crystal data top
C14H14N2 | Dx = 1.258 Mg m−3 |
Mr = 210.27 | Melting point: 422.7(4) K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.8153 (19) Å | Cell parameters from 380 reflections |
b = 5.5146 (4) Å | θ = 2.5–26.0° |
c = 8.1513 (9) Å | µ = 0.08 mm−1 |
β = 95.719 (9)° | T = 298 K |
V = 1109.92 (17) Å3 | Plate, colorless |
Z = 4 | 0.30 × 0.25 × 0.06 mm |
F(000) = 448 | |
Data collection top
Bruker SMART CCD area detector diffractometer | 2643 independent reflections |
Radiation source: fine-focus sealed tube | 1328 reflections with I > 2σ(I) |
Detector resolution: 10.13 pixels mm-1 | Rint = 0.040 |
phi and ω scans | θmax = 29.0°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −33→33 |
Tmin = 0.976, Tmax = 0.991 | k = −7→6 |
7644 measured reflections | l = −7→10 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.243 | w = 1/[σ2(Fo2) + (0.1217P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2643 reflections | Δρmax = 0.19 e Å−3 |
339 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.058 (11) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1A | 0.3306 (2) | 0.3201 (9) | 0.5939 (6) | 0.0939 (15) | 0.587 (2) |
H1A | 0.3071 | 0.1973 | 0.6191 | 0.109 (16)* | 0.587 (2) |
C2A | 0.3836 (2) | 0.3115 (19) | 0.6653 (11) | 0.053 (2) | 0.587 (2) |
H2A | 0.3957 | 0.1847 | 0.7347 | 0.16 (2)* | 0.587 (2) |
C3A | 0.41696 (19) | 0.4930 (9) | 0.6308 (6) | 0.0814 (13) | 0.587 (2) |
H3A | 0.4524 | 0.4955 | 0.6805 | 0.12 (3)* | 0.587 (2) |
C4A | 0.3989 (3) | 0.6794 (11) | 0.5201 (10) | 0.0403 (14) | 0.587 (2) |
H4A | 0.4231 | 0.7971 | 0.4915 | 0.34 (8)* | 0.587 (2) |
C5A | 0.3474 (3) | 0.6881 (11) | 0.4563 (8) | 0.1256 (2) | 0.587 (2) |
H5A | 0.3348 | 0.8171 | 0.3898 | 0.13 (2)* | 0.587 (2) |
C6A | 0.3116 (5) | 0.493 (3) | 0.492 (2) | 0.042 (3) | 0.587 (2) |
C7A | 0.2523 (2) | 0.4981 (9) | 0.4070 (6) | 0.0891 (14) | 0.587 (2) |
C8A | 0.2332 (4) | 0.6777 (12) | 0.3093 (15) | 0.045 (2) | 0.587 (2) |
H8A | 0.2553 | 0.8075 | 0.2870 | 0.14 (2)* | 0.587 (2) |
C9A | 0.1797 (2) | 0.6680 (10) | 0.2410 (6) | 0.0942 (15) | 0.587 (2) |
H9A | 0.1668 | 0.7978 | 0.1755 | 0.14 (2)* | 0.587 (2) |
C10A | 0.1435 (4) | 0.4789 (19) | 0.2625 (8) | 0.0257 (11) | 0.587 (2) |
C11A | 0.1625 (3) | 0.3111 (11) | 0.3787 (8) | 0.1095 (18) | 0.587 (2) |
H11A | 0.1393 | 0.1925 | 0.4118 | 0.14 (2)* | 0.587 (2) |
C12A | 0.21717 (15) | 0.3166 (7) | 0.4487 (6) | 0.0325 (9) | 0.587 (2) |
H12A | 0.2297 | 0.1971 | 0.5234 | 0.069 (13)* | 0.587 (2) |
C13A | 0.08530 (18) | 0.4874 (8) | 0.1799 (5) | 0.0786 (12) | 0.587 (2) |
C14A | 0.0682 (7) | 0.659 (2) | 0.0592 (16) | 0.081 (3) | 0.587 (2) |
H14A | 0.0345 | 0.7287 | 0.0841 | 0.095* | 0.587 (2) |
H14B | 0.0632 | 0.5807 | −0.0466 | 0.16 (2)* | 0.587 (2) |
H14C | 0.0950 | 0.7836 | 0.0573 | 0.098* | 0.587 (2) |
N1A | 0.05682 (7) | 0.3088 (3) | 0.2274 (3) | 0.0319 (6) | 0.587 (2) |
N2A | 0.00263 (15) | 0.3039 (9) | 0.1401 (6) | 0.0851 (12) | 0.587 (2) |
C1B | 0.3822 (6) | 0.340 (3) | 0.6724 (16) | 0.069 (5) | 0.413 (2) |
H1B | 0.3578 | 0.2284 | 0.7085 | 0.14 (3)* | 0.413 (2) |
C2B | 0.4359 (3) | 0.3351 (12) | 0.7403 (10) | 0.088 (2) | 0.413 (2) |
H2B | 0.4473 | 0.2184 | 0.8186 | 0.18 (4)* | 0.413 (2) |
C3B | 0.4719 (2) | 0.5008 (7) | 0.6927 (5) | 0.0451 (12) | 0.413 (2) |
H3B | 0.5085 | 0.4907 | 0.7301 | 0.13 (2)* | 0.413 (2) |
C4B | 0.4527 (3) | 0.6842 (11) | 0.5873 (8) | 0.0784 (17) | 0.413 (2) |
H4B | 0.4751 | 0.8130 | 0.5650 | 0.083 (18)* | 0.413 (2) |
C5B | 0.4051 (8) | 0.675 (3) | 0.522 (2) | 0.103 (5) | 0.413 (2) |
H5B | 0.3947 | 0.7939 | 0.4444 | 0.109* | 0.413 (2) |
C6B | 0.3648 (2) | 0.5017 (10) | 0.5554 (7) | 0.0673 (16) | 0.413 (2) |
C7B | 0.3051 (6) | 0.517 (4) | 0.483 (3) | 0.026 (3) | 0.413 (2) |
C8B | 0.2840 (2) | 0.6726 (8) | 0.3711 (7) | 0.0624 (14) | 0.413 (2) |
H8B | 0.3077 | 0.7928 | 0.3425 | 0.12 (2)* | 0.413 (2) |
C9B | 0.2321 (6) | 0.686 (3) | 0.289 (3) | 0.072 (5) | 0.413 (2) |
H9B | 0.2215 | 0.8025 | 0.2106 | 0.18 (4)* | 0.413 (2) |
C10B | 0.1975 (2) | 0.5039 (9) | 0.3383 (6) | 0.0540 (13) | 0.413 (2) |
C11B | 0.2168 (9) | 0.320 (3) | 0.436 (2) | 0.1518 (7) | 0.413 (2) |
H11B | 0.1948 | 0.1850 | 0.4465 | 0.252* | 0.413 (2) |
C12B | 0.2696 (2) | 0.3231 (9) | 0.5225 (7) | 0.0678 (15) | 0.413 (2) |
H12B | 0.2806 | 0.2062 | 0.6010 | 0.22 (5)* | 0.413 (2) |
C13B | 0.1403 (8) | 0.528 (3) | 0.2582 (19) | 0.060 (5) | 0.413 (2) |
C14B | 0.11061 (16) | 0.3231 (7) | 0.3007 (6) | 0.0457 (11) | 0.413 (2) |
H14D | 0.1102 | 0.3164 | 0.4182 | 0.205* | 0.413 (2) |
H14E | 0.1273 | 0.1788 | 0.2632 | 0.12 (2)* | 0.413 (2) |
H14F | 0.0741 | 0.3346 | 0.2495 | 0.123* | 0.413 (2) |
N1B | 0.12152 (18) | 0.6649 (7) | 0.1208 (5) | 0.0656 (13) | 0.413 (2) |
N2B | 0.0690 (8) | 0.727 (3) | 0.101 (2) | 0.098 (4) | 0.413 (2) |
H2M | −0.006 (2) | 0.417 (11) | 0.068 (6) | 0.12 (2)* | 0.587 (2) |
H2N | −0.016 (2) | 0.199 (8) | 0.171 (6) | 0.097 (18)* | 0.587 (2) |
H2O | 0.047 (3) | 0.673 (14) | 0.174 (11) | 0.11 (3)* | 0.413 (2) |
H2P | 0.057 (3) | 0.802 (14) | 0.013 (10) | 0.10 (3)* | 0.413 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.085 (3) | 0.107 (4) | 0.088 (3) | −0.022 (3) | 0.000 (3) | 0.029 (3) |
C2A | 0.021 (2) | 0.060 (4) | 0.075 (5) | 0.002 (2) | −0.007 (2) | 0.001 (3) |
C3A | 0.064 (3) | 0.094 (3) | 0.087 (3) | 0.007 (2) | 0.011 (2) | −0.012 (3) |
C4A | 0.032 (2) | 0.037 (3) | 0.050 (3) | −0.0163 (19) | −0.005 (2) | 0.007 (2) |
C5A | 0.107 | 0.130 | 0.139 | 0.008 (3) | 0.012 (4) | 0.061 (4) |
C6A | 0.055 (7) | 0.024 (2) | 0.051 (5) | 0.015 (3) | 0.017 (4) | −0.003 (3) |
C7A | 0.083 (3) | 0.084 (3) | 0.103 (4) | 0.000 (3) | 0.023 (3) | −0.019 (3) |
C8A | 0.056 (5) | 0.028 (2) | 0.052 (3) | 0.004 (3) | 0.003 (3) | 0.023 (2) |
C9A | 0.090 (3) | 0.100 (4) | 0.091 (3) | −0.002 (3) | −0.004 (3) | 0.009 (3) |
C10A | 0.029 (2) | 0.019 (3) | 0.029 (2) | 0.0075 (19) | 0.0030 (14) | 0.0027 (14) |
C11A | 0.107 (5) | 0.111 (4) | 0.110 (4) | −0.011 (4) | 0.009 (4) | −0.005 (3) |
C12A | 0.0202 (12) | 0.0282 (14) | 0.0471 (18) | −0.0088 (14) | −0.0057 (15) | 0.0236 (18) |
C13A | 0.092 (3) | 0.082 (3) | 0.063 (3) | −0.001 (2) | 0.008 (2) | −0.010 (2) |
C14A | 0.087 (4) | 0.086 (6) | 0.069 (6) | −0.007 (4) | 0.001 (4) | −0.022 (4) |
N1A | 0.0156 (9) | 0.0306 (11) | 0.0472 (13) | −0.0020 (7) | −0.0078 (8) | 0.0054 (9) |
N2A | 0.060 (2) | 0.084 (3) | 0.107 (3) | −0.0024 (19) | −0.009 (2) | −0.001 (3) |
C1B | 0.096 (9) | 0.045 (5) | 0.074 (7) | 0.016 (4) | 0.054 (6) | 0.022 (4) |
C2B | 0.063 (4) | 0.076 (4) | 0.117 (5) | 0.001 (3) | −0.029 (3) | 0.003 (4) |
C3B | 0.028 (2) | 0.054 (3) | 0.051 (3) | −0.0027 (16) | −0.0084 (17) | −0.0028 (19) |
C4B | 0.068 (4) | 0.084 (4) | 0.082 (4) | −0.019 (3) | −0.003 (3) | 0.009 (3) |
C5B | 0.098 (11) | 0.131 (11) | 0.083 (10) | 0.033 (8) | 0.026 (8) | 0.016 (8) |
C6B | 0.065 (4) | 0.078 (4) | 0.060 (3) | −0.015 (3) | 0.013 (3) | −0.015 (3) |
C7B | 0.011 (2) | 0.036 (7) | 0.032 (4) | 0.000 (4) | 0.0003 (19) | 0.000 (4) |
C8B | 0.048 (3) | 0.041 (3) | 0.099 (4) | −0.001 (2) | 0.011 (3) | 0.018 (2) |
C9B | 0.049 (6) | 0.098 (8) | 0.066 (7) | −0.040 (5) | −0.004 (4) | 0.018 (6) |
C10B | 0.075 (4) | 0.045 (3) | 0.045 (3) | −0.005 (2) | 0.019 (2) | 0.010 (2) |
C11B | 0.159 | 0.152 | 0.153 | −0.037 (12) | 0.059 (10) | −0.032 (12) |
C12B | 0.063 (3) | 0.059 (3) | 0.079 (4) | −0.009 (2) | −0.006 (3) | 0.029 (3) |
C13B | 0.051 (5) | 0.039 (8) | 0.094 (8) | 0.019 (4) | 0.024 (4) | 0.004 (4) |
C14B | 0.033 (2) | 0.038 (2) | 0.067 (3) | −0.0043 (17) | 0.0081 (19) | −0.0040 (19) |
N1B | 0.061 (3) | 0.066 (3) | 0.069 (3) | 0.011 (2) | 0.006 (2) | 0.018 (2) |
N2B | 0.092 (6) | 0.107 (10) | 0.095 (10) | 0.005 (7) | 0.006 (7) | −0.003 (6) |
Geometric parameters (Å, º) top
C1A—C6A | 1.316 (17) | C1B—C2B | 1.393 (15) |
C1A—C2A | 1.386 (9) | C1B—C6B | 1.346 (15) |
C1A—H1A | 0.9300 | C1B—H1B | 0.9300 |
C2A—C3A | 1.347 (10) | C2B—C3B | 1.361 (8) |
C2A—H2A | 0.9300 | C2B—H2B | 0.9300 |
C3A—C4A | 1.412 (10) | C3B—C4B | 1.381 (8) |
C3A—H3A | 0.9300 | C3B—H3B | 0.9300 |
C4A—C5A | 1.330 (10) | C4B—C5B | 1.247 (19) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—C6A | 1.446 (15) | C5B—C6B | 1.429 (19) |
C5A—H5A | 0.9300 | C5B—H5B | 0.9300 |
C6A—C7A | 1.565 (14) | C6B—C7B | 1.542 (17) |
C7A—C8A | 1.328 (11) | C7B—C8B | 1.32 (2) |
C7A—C12A | 1.392 (7) | C7B—C12B | 1.444 (17) |
C8A—C9A | 1.390 (11) | C8B—C9B | 1.392 (18) |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C9A—C10A | 1.398 (12) | C9B—C10B | 1.403 (15) |
C9A—H9A | 0.9300 | C9B—H9B | 0.9300 |
C10A—C11A | 1.373 (12) | C10B—C11B | 1.35 (2) |
C10A—C13A | 1.532 (10) | C10B—C13B | 1.509 (18) |
C11A—C12A | 1.419 (8) | C11B—C12B | 1.43 (2) |
C11A—H11A | 0.9300 | C11B—H11B | 0.9300 |
C12A—H12A | 0.9300 | C12B—H12B | 0.9300 |
C13A—N1A | 1.294 (4) | C13B—N1B | 1.393 (17) |
C13A—C14A | 1.399 (17) | C13B—C14B | 1.409 (18) |
C14A—H14A | 0.9600 | C14B—H14D | 0.9600 |
C14A—H14B | 0.9600 | C14B—H14E | 0.9600 |
C14A—H14C | 0.9600 | C14B—H14F | 0.9600 |
N1A—N2A | 1.458 (4) | N1B—N2B | 1.34 (2) |
N2A—H2M | 0.87 (5) | N2B—H2O | 0.89 (9) |
N2A—H2N | 0.79 (5) | N2B—H2P | 0.86 (8) |
| | | |
C6A—C1A—C2A | 123.6 (8) | C2B—C1B—C6B | 121.3 (10) |
C6A—C1A—H1A | 118.2 | C2B—C1B—H1B | 119.3 |
C2A—C1A—H1A | 118.2 | C6B—C1B—H1B | 119.3 |
C3A—C2A—C1A | 117.7 (7) | C3B—C2B—C1B | 120.3 (8) |
C3A—C2A—H2A | 121.2 | C3B—C2B—H2B | 119.9 |
C1A—C2A—H2A | 121.2 | C1B—C2B—H2B | 119.9 |
C2A—C3A—C4A | 120.8 (5) | C2B—C3B—C4B | 118.3 (6) |
C2A—C3A—H3A | 119.6 | C2B—C3B—H3B | 120.9 |
C4A—C3A—H3A | 119.6 | C4B—C3B—H3B | 120.9 |
C5A—C4A—C3A | 120.5 (5) | C3B—C4B—C5B | 119.3 (11) |
C5A—C4A—H4A | 119.7 | C3B—C4B—H4B | 120.4 |
C3A—C4A—H4A | 119.7 | C5B—C4B—H4B | 120.4 |
C4A—C5A—C6A | 118.6 (8) | C6B—C5B—C4B | 126.7 (17) |
C4A—C5A—H5A | 120.7 | C6B—C5B—H5B | 116.7 |
C6A—C5A—H5A | 120.7 | C4B—C5B—H5B | 116.7 |
C1A—C6A—C5A | 118.6 (10) | C5B—C6B—C1B | 113.5 (12) |
C1A—C6A—C7A | 123.7 (10) | C5B—C6B—C7B | 123.6 (12) |
C5A—C6A—C7A | 117.7 (12) | C1B—C6B—C7B | 122.4 (10) |
C8A—C7A—C12A | 119.2 (6) | C8B—C7B—C12B | 115.3 (12) |
C8A—C7A—C6A | 123.0 (8) | C8B—C7B—C6B | 126.9 (11) |
C12A—C7A—C6A | 117.5 (7) | C12B—C7B—C6B | 117.2 (15) |
C7A—C8A—C9A | 118.8 (7) | C7B—C8B—C9B | 130.4 (10) |
C7A—C8A—H8A | 120.6 | C7B—C8B—H8B | 114.8 |
C9A—C8A—H8A | 120.6 | C9B—C8B—H8B | 114.8 |
C8A—C9A—C10A | 125.3 (6) | C8B—C9B—C10B | 113.0 (13) |
C8A—C9A—H9A | 117.3 | C8B—C9B—H9B | 123.5 |
C10A—C9A—H9A | 117.3 | C10B—C9B—H9B | 123.5 |
C11A—C10A—C9A | 114.1 (7) | C11B—C10B—C9B | 121.0 (12) |
C11A—C10A—C13A | 124.6 (7) | C11B—C10B—C13B | 125.7 (12) |
C9A—C10A—C13A | 120.7 (7) | C9B—C10B—C13B | 113.1 (11) |
C10A—C11A—C12A | 120.8 (6) | C10B—C11B—C12B | 122.5 (15) |
C10A—C11A—H11A | 119.6 | C10B—C11B—H11B | 118.8 |
C12A—C11A—H11A | 119.6 | C12B—C11B—H11B | 118.8 |
C7A—C12A—C11A | 121.0 (4) | C11B—C12B—C7B | 116.7 (13) |
C7A—C12A—H12A | 119.5 | C11B—C12B—H12B | 121.6 |
C11A—C12A—H12A | 119.5 | C7B—C12B—H12B | 121.6 |
N1A—C13A—C14A | 126.0 (7) | N1B—C13B—C14B | 119.4 (13) |
N1A—C13A—C10A | 111.3 (5) | N1B—C13B—C10B | 128.3 (13) |
C14A—C13A—C10A | 122.5 (8) | C14B—C13B—C10B | 108.5 (11) |
C13A—C14A—H14A | 109.5 | C13B—C14B—H14D | 109.5 |
C13A—C14A—H14B | 109.5 | C13B—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
C13A—C14A—H14C | 109.5 | C13B—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
C13A—N1A—N2A | 111.9 (3) | N2B—N1B—C13B | 118.4 (12) |
N1A—N2A—H2M | 118 (4) | N1B—N2B—H2O | 119 (5) |
N1A—N2A—H2N | 113 (4) | N1B—N2B—H2P | 119 (6) |
H2M—N2A—H2N | 129 (6) | H2O—N2B—H2P | 122 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2M···N2Ai | 0.87 (5) | 2.30 (5) | 3.139 (12) | 163 (5) |
N2A—H2N···N1Aii | 0.79 (5) | 2.56 (5) | 3.334 (6) | 168 (5) |
C14A—H14A···N2Aiii | 0.96 | 2.55 | 3.255 (14) | 131 |
C14A—H14B···N2Ai | 0.96 | 1.85 | 2.280 (16) | 104 |
C14B—H14F···N2B | 0.96 | 2.47 | 2.89 (2) | 106 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2. |
Comparison of calculated UV–Vis characteristic peaks and predicted
transitions topTheoretical methods | λ (f)i | MO transitions (configurations)ii |
B3LYP | 310.23 (0.8955) | H-0 → L+0(+98%) |
PBE1PBE | 303.27 (0.9293) | H-0 → L+0(+98%) |
M062X | 273.69 (0.9760) | H-0 → L+0(+93%) |
MP2 | 247.97 (0.9885) | H-0→ L+1(+70%) |
Notes: (i) calculated results in methanol solution [the unit of wavelength
(λ) is nm and f means oscillator strength];
(ii) contour plots and energies of frontier molecular orbitals
(see Fig. 6c). |
Comparison of calculated fluorescence characteristic peaks and predicted
transitions topTheoretical methods | λ (f)i | MO transitions (configurations)ii |
B3LYP | 422.97 (1.3216) | L+0 → H-0 (+99%) |
PBE1PBE | 412.66 (1.3484) | L+0 → H-0 (+98%) |
M062X | 394.71 (1.2891) | L+0 → H-0 (+93%) |
MP2 | 405.37 (1.5108) | L+0 → H-0 (+90%) |
CIS | 382.67 (1.0978) | L+0 → H-0 (+99%) |
Notes: (i) calculated results in methanol solution [the unit of wavelength
(λ) is nm and f means oscillator strength];
(ii) contour plots and energies of frontier molecular orbitals
(see Fig. 7c). |
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