Syntheses and X-ray structural investigations have been carried out for (
E)-(4-hydroxyphenyl)(4-nitrophenyl)diazene, C
12H
9N
3O
3, (I
a), (
E)-(4-methoxyphenyl)(4-nitrophenyl)diazene, C
13H
11N
3O
3, (III
a), and (
E)-[4-(6-bromohexyloxy)phenyl](4-cyanophenyl)diazene, C
19H
20BrN
3O, (III
c). In all of these compounds, the molecules are almost planar and the azobenzene core has a
trans geometry. Compound (I
a) contains four and compound (III
c) contains two independent molecules in the asymmetric unit, both in space group
P (No. 2). In compound (I
a), the independent molecules are almost identical, whereas in crystal (III
c), the two independent molecules differ significantly due to different conformations of the alkyl tails. In the crystals of (I
a) and (III
a), the molecules are arranged in almost planar sheets. In the crystal of (III
c), the molecules are packed with a marked separation of the azobenzene cores and alkyl tails, which is common for the solid crystalline precursors of mesogens.
Supporting information
CCDC references: 197344; 197345; 197346
Compounds (Ia) and (Ib) were synthesized according to the method of Ringsdorf &
Schmidt (1984). Product (Ia) was recrystallized from methanol (m.p. 486 K;
yield 92%). Compounds (IIIa)-(IIIc) were obtained using the following general
procedure. Mixtures of (Ia) or (Ib) (10 mmol), K2CO3 (10 mmol), absolute
acetone (30 ml), CH3I [10 mmol, (IIa)], 1,4-dibromobutane [Amount?, (IIb)]
or 1,6-dibromohexane [Amount?, (IIc)], and a trace amount of KI were refluxed
for 1–3 d. The precipitates (KI or KBr) were filtered off and the filtrates
were evaporated. CHCl3 was added and extracted three times with water, and
evaporated. The products were recrystallized from acetone. For (IIIa), m.p.
421 K, yield 1.85 g, 72%; for (IIIb), m.p. 403 K, yield 2.05 g, 57%; for
(IIIc), m.p. 376 K, yield 2.42 g, 73%. All crystals for X-ray analysis were
obtained by slow isothermal evaporation from ethanol solutions.
H atoms were treated as riding, with O—H distances of 0.84 Å and C—H
distances in the range 0.93–0.99 Å. Is this added text OK?
Data collection: SMART (Bruker, 1998) for (Ia), (IIIc); CAD-4 Software (Enraf-Nonius, 1989) for (IIIa). Cell refinement: SMART for (Ia), (IIIc); CAD-4 Software for (IIIa). Data reduction: SAINT (Bruker, 1998) for (Ia), (IIIc); SHELXTL-Plus (Sheldrick, 1994) for (IIIa). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: SHELXTL-Plus (Sheldrick, 1994) for (Ia), (IIIc); SHELXTL-Plus for (IIIa). Software used to prepare material for publication: SHELXTL-Plus for (Ia), (IIIc); SHELXL97 for (IIIa).
(Ia) (
E)-(4-hydroxyphenyl)(4-nitrophenyl)diazene
top
Crystal data top
C12H9N3O3 | Z = 8 |
Mr = 243.22 | F(000) = 1008 |
Triclinic, P1 | Dx = 1.505 Mg m−3 |
Hall symbol: -P1 | Melting point: 486 K |
a = 7.290 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.648 (6) Å | Cell parameters from 320 reflections |
c = 28.353 (16) Å | θ = 4–24° |
α = 93.685 (10)° | µ = 0.11 mm−1 |
β = 94.922 (11)° | T = 110 K |
γ = 100.811 (10)° | Plate, yellow |
V = 2147 (2) Å3 | 0.50 × 0.40 × 0.15 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 6579 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 30.1°, θmin = 2.0° |
ϕ and ω scans | h = −10→10 |
24813 measured reflections | k = −14→14 |
12208 independent reflections | l = −39→38 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
12208 reflections | (Δ/σ)max < 0.001 |
649 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C12H9N3O3 | γ = 100.811 (10)° |
Mr = 243.22 | V = 2147 (2) Å3 |
Triclinic, P1 | Z = 8 |
a = 7.290 (4) Å | Mo Kα radiation |
b = 10.648 (6) Å | µ = 0.11 mm−1 |
c = 28.353 (16) Å | T = 110 K |
α = 93.685 (10)° | 0.50 × 0.40 × 0.15 mm |
β = 94.922 (11)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 6579 reflections with I > 2σ(I) |
24813 measured reflections | Rint = 0.031 |
12208 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.47 e Å−3 |
12208 reflections | Δρmin = −0.27 e Å−3 |
649 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. All H atoms were placed in geometrically calculated positions and
refined using a riding model. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.0637 (2) | 0.49990 (12) | 0.23558 (4) | 0.0399 (4) | |
H1A | −0.0305 | 0.4579 | 0.2185 | 0.060* | |
O2A | 0.0480 (2) | 0.23444 (12) | 0.65306 (5) | 0.0371 (3) | |
O3A | 0.2984 (2) | 0.37848 (14) | 0.67052 (5) | 0.0424 (4) | |
N1A | 0.1713 (2) | 0.31876 (14) | 0.64195 (5) | 0.0288 (3) | |
N2A | 0.1735 (2) | 0.44213 (13) | 0.45204 (5) | 0.0240 (3) | |
N3A | 0.0589 (2) | 0.36998 (13) | 0.42149 (5) | 0.0245 (3) | |
C1A | 0.1656 (2) | 0.34923 (15) | 0.59218 (6) | 0.0228 (4) | |
C2A | 0.0250 (2) | 0.27990 (15) | 0.55950 (6) | 0.0246 (4) | |
H2A | −0.0677 | 0.2139 | 0.5690 | 0.029* | |
C3A | 0.0230 (2) | 0.30914 (16) | 0.51268 (6) | 0.0245 (4) | |
H3A | −0.0721 | 0.2631 | 0.4896 | 0.029* | |
C4A | 0.1604 (2) | 0.40613 (15) | 0.49923 (6) | 0.0217 (4) | |
C5A | 0.2970 (2) | 0.47610 (16) | 0.53331 (6) | 0.0247 (4) | |
H5A | 0.3877 | 0.5444 | 0.5243 | 0.030* | |
C6A | 0.3012 (2) | 0.44666 (16) | 0.57998 (6) | 0.0257 (4) | |
H6A | 0.3956 | 0.4927 | 0.6032 | 0.031* | |
C7A | 0.0682 (2) | 0.40578 (16) | 0.37445 (6) | 0.0222 (4) | |
C8A | −0.0566 (2) | 0.32882 (16) | 0.33966 (6) | 0.0255 (4) | |
H8A | −0.1390 | 0.2555 | 0.3482 | 0.031* | |
C9A | −0.0620 (3) | 0.35770 (17) | 0.29293 (6) | 0.0273 (4) | |
H9A | −0.1479 | 0.3048 | 0.2694 | 0.033* | |
C10A | 0.0591 (3) | 0.46460 (17) | 0.28055 (6) | 0.0272 (4) | |
C11A | 0.1864 (3) | 0.54063 (17) | 0.31486 (6) | 0.0298 (4) | |
H11A | 0.2710 | 0.6125 | 0.3060 | 0.036* | |
C12A | 0.1909 (3) | 0.51272 (16) | 0.36155 (6) | 0.0262 (4) | |
H12A | 0.2771 | 0.5658 | 0.3850 | 0.031* | |
O1B | 0.09328 (19) | 0.13282 (12) | 0.74147 (4) | 0.0350 (3) | |
H1B | 0.1118 | 0.1938 | 0.7240 | 0.052* | |
O2B | 0.83062 (18) | 0.42569 (11) | 1.15294 (4) | 0.0314 (3) | |
O3B | 0.7259 (2) | 0.23105 (12) | 1.16776 (4) | 0.0379 (3) | |
N1B | 0.7416 (2) | 0.31699 (13) | 1.14099 (5) | 0.0246 (3) | |
N2B | 0.40260 (19) | 0.19248 (13) | 0.95398 (5) | 0.0235 (3) | |
N3B | 0.42434 (19) | 0.27785 (13) | 0.92494 (5) | 0.0231 (3) | |
C1B | 0.6539 (2) | 0.28942 (15) | 1.09206 (6) | 0.0202 (3) | |
C2B | 0.6722 (2) | 0.38609 (15) | 1.06129 (6) | 0.0224 (4) | |
H2B | 0.7392 | 0.4701 | 1.0716 | 0.027* | |
C3B | 0.5903 (2) | 0.35657 (15) | 1.01511 (6) | 0.0222 (4) | |
H3B | 0.6023 | 0.4206 | 0.9931 | 0.027* | |
C4B | 0.4901 (2) | 0.23332 (15) | 1.00069 (6) | 0.0201 (3) | |
C5B | 0.4724 (2) | 0.13947 (15) | 1.03265 (6) | 0.0229 (4) | |
H5B | 0.4022 | 0.0560 | 1.0229 | 0.027* | |
C6B | 0.5564 (2) | 0.16702 (15) | 1.07855 (6) | 0.0231 (4) | |
H6B | 0.5471 | 0.1027 | 1.1004 | 0.028* | |
C7B | 0.3386 (2) | 0.23651 (15) | 0.87840 (6) | 0.0214 (3) | |
C8B | 0.3606 (2) | 0.32641 (16) | 0.84480 (6) | 0.0239 (4) | |
H8B | 0.4313 | 0.4102 | 0.8537 | 0.029* | |
C9B | 0.2808 (2) | 0.29516 (16) | 0.79858 (6) | 0.0260 (4) | |
H9B | 0.2957 | 0.3571 | 0.7758 | 0.031* | |
C10B | 0.1785 (2) | 0.17226 (16) | 0.78575 (6) | 0.0253 (4) | |
C11B | 0.1595 (2) | 0.08048 (16) | 0.81882 (6) | 0.0257 (4) | |
H11B | 0.0926 | −0.0042 | 0.8095 | 0.031* | |
C12B | 0.2372 (2) | 0.11226 (16) | 0.86492 (6) | 0.0235 (4) | |
H12B | 0.2222 | 0.0501 | 0.8876 | 0.028* | |
O1C | 0.68874 (18) | 0.99896 (12) | 0.34847 (4) | 0.0330 (3) | |
H1C | 0.6105 | 0.9533 | 0.3278 | 0.049* | |
O2C | 0.53167 (19) | 0.65258 (13) | 0.75292 (5) | 0.0404 (4) | |
O3C | 0.78189 (19) | 0.79158 (12) | 0.77738 (4) | 0.0351 (3) | |
N1C | 0.6586 (2) | 0.73978 (14) | 0.74582 (5) | 0.0275 (3) | |
N2C | 0.7027 (2) | 0.90688 (13) | 0.56232 (5) | 0.0226 (3) | |
N3C | 0.5955 (2) | 0.84019 (13) | 0.52913 (5) | 0.0226 (3) | |
C1C | 0.6661 (2) | 0.78405 (16) | 0.69812 (6) | 0.0230 (4) | |
C2C | 0.5330 (2) | 0.72046 (15) | 0.66252 (6) | 0.0230 (4) | |
H2C | 0.4391 | 0.6508 | 0.6691 | 0.028* | |
C3C | 0.5396 (2) | 0.76056 (16) | 0.61732 (6) | 0.0240 (4) | |
H3C | 0.4486 | 0.7190 | 0.5924 | 0.029* | |
C4C | 0.6794 (2) | 0.86190 (15) | 0.60802 (6) | 0.0213 (3) | |
C5C | 0.8083 (2) | 0.92530 (16) | 0.64476 (6) | 0.0247 (4) | |
H5C | 0.9014 | 0.9959 | 0.6385 | 0.030* | |
C6C | 0.8025 (2) | 0.88667 (16) | 0.69025 (6) | 0.0260 (4) | |
H6C | 0.8904 | 0.9298 | 0.7155 | 0.031* | |
C7C | 0.6225 (2) | 0.88454 (15) | 0.48366 (6) | 0.0213 (3) | |
C8C | 0.5019 (2) | 0.81909 (16) | 0.44566 (6) | 0.0243 (4) | |
H8C | 0.4071 | 0.7486 | 0.4510 | 0.029* | |
C9C | 0.5188 (2) | 0.85594 (16) | 0.39991 (6) | 0.0259 (4) | |
H9C | 0.4346 | 0.8117 | 0.3742 | 0.031* | |
C10C | 0.6593 (3) | 0.95760 (16) | 0.39189 (6) | 0.0250 (4) | |
C11C | 0.7805 (2) | 1.02350 (16) | 0.43001 (6) | 0.0252 (4) | |
H11C | 0.8762 | 1.0934 | 0.4246 | 0.030* | |
C12C | 0.7622 (2) | 0.98780 (16) | 0.47530 (6) | 0.0247 (4) | |
H12C | 0.8447 | 1.0335 | 0.5011 | 0.030* | |
O1D | −0.27924 (18) | 0.62093 (12) | −0.14721 (4) | 0.0319 (3) | |
H1D | −0.2564 | 0.6743 | −0.1675 | 0.048* | |
O2D | 0.52516 (18) | 1.02984 (12) | 0.24777 (4) | 0.0327 (3) | |
O3D | 0.4248 (2) | 0.84703 (13) | 0.27445 (4) | 0.0374 (3) | |
N1D | 0.4331 (2) | 0.92001 (14) | 0.24240 (5) | 0.0267 (3) | |
N2D | 0.06133 (19) | 0.73462 (13) | 0.06276 (5) | 0.0214 (3) | |
N3D | 0.07701 (19) | 0.81176 (13) | 0.03072 (5) | 0.0212 (3) | |
C1D | 0.3314 (2) | 0.87379 (16) | 0.19604 (6) | 0.0218 (4) | |
C2D | 0.3369 (2) | 0.95936 (16) | 0.16096 (6) | 0.0233 (4) | |
H2D | 0.4008 | 1.0459 | 0.1674 | 0.028* | |
C3D | 0.2473 (2) | 0.91523 (15) | 0.11663 (6) | 0.0224 (4) | |
H3D | 0.2491 | 0.9716 | 0.0920 | 0.027* | |
C4D | 0.1539 (2) | 0.78815 (15) | 0.10784 (6) | 0.0203 (3) | |
C5D | 0.1480 (2) | 0.70543 (15) | 0.14368 (6) | 0.0232 (4) | |
H5D | 0.0821 | 0.6193 | 0.1376 | 0.028* | |
C6D | 0.2385 (2) | 0.74848 (16) | 0.18852 (6) | 0.0245 (4) | |
H6D | 0.2362 | 0.6926 | 0.2134 | 0.029* | |
C7D | −0.0135 (2) | 0.75893 (15) | −0.01440 (6) | 0.0204 (3) | |
C8D | −0.0038 (2) | 0.84056 (15) | −0.05084 (6) | 0.0225 (4) | |
H8D | 0.0612 | 0.9269 | −0.0448 | 0.027* | |
C9D | −0.0889 (2) | 0.79619 (16) | −0.09601 (6) | 0.0233 (4) | |
H9D | −0.0802 | 0.8516 | −0.1210 | 0.028* | |
C10D | −0.1868 (2) | 0.67081 (16) | −0.10459 (6) | 0.0233 (4) | |
C11D | −0.1945 (2) | 0.58811 (16) | −0.06830 (6) | 0.0239 (4) | |
H11D | −0.2590 | 0.5016 | −0.0744 | 0.029* | |
C12D | −0.1088 (2) | 0.63200 (15) | −0.02368 (6) | 0.0226 (4) | |
H12D | −0.1144 | 0.5756 | 0.0010 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0514 (9) | 0.0385 (8) | 0.0216 (7) | −0.0093 (6) | −0.0081 (6) | 0.0098 (6) |
O2A | 0.0529 (9) | 0.0296 (7) | 0.0277 (7) | 0.0018 (6) | 0.0056 (6) | 0.0096 (5) |
O3A | 0.0502 (9) | 0.0481 (9) | 0.0235 (7) | −0.0005 (7) | −0.0067 (6) | 0.0050 (6) |
N1A | 0.0396 (9) | 0.0252 (8) | 0.0231 (8) | 0.0090 (7) | 0.0028 (7) | 0.0052 (6) |
N2A | 0.0289 (8) | 0.0247 (7) | 0.0191 (7) | 0.0057 (6) | 0.0033 (6) | 0.0046 (6) |
N3A | 0.0285 (8) | 0.0244 (7) | 0.0216 (8) | 0.0061 (6) | 0.0037 (6) | 0.0043 (6) |
C1A | 0.0309 (9) | 0.0226 (8) | 0.0170 (8) | 0.0101 (7) | 0.0029 (7) | 0.0032 (6) |
C2A | 0.0284 (9) | 0.0214 (8) | 0.0239 (9) | 0.0032 (7) | 0.0028 (7) | 0.0062 (7) |
C3A | 0.0307 (10) | 0.0232 (8) | 0.0183 (8) | 0.0041 (7) | −0.0008 (7) | 0.0007 (6) |
C4A | 0.0289 (9) | 0.0198 (8) | 0.0185 (8) | 0.0080 (7) | 0.0045 (7) | 0.0040 (6) |
C5A | 0.0253 (9) | 0.0230 (8) | 0.0252 (9) | 0.0019 (7) | 0.0037 (7) | 0.0039 (7) |
C6A | 0.0300 (10) | 0.0246 (9) | 0.0215 (9) | 0.0046 (7) | −0.0005 (7) | 0.0001 (7) |
C7A | 0.0253 (9) | 0.0240 (8) | 0.0190 (8) | 0.0074 (7) | 0.0038 (7) | 0.0037 (6) |
C8A | 0.0263 (9) | 0.0261 (9) | 0.0244 (9) | 0.0036 (7) | 0.0032 (7) | 0.0071 (7) |
C9A | 0.0294 (10) | 0.0289 (9) | 0.0222 (9) | 0.0042 (7) | −0.0015 (8) | 0.0023 (7) |
C10A | 0.0334 (10) | 0.0294 (9) | 0.0201 (9) | 0.0078 (8) | 0.0017 (8) | 0.0079 (7) |
C11A | 0.0360 (11) | 0.0252 (9) | 0.0269 (10) | 0.0011 (8) | 0.0033 (8) | 0.0065 (7) |
C12A | 0.0324 (10) | 0.0245 (9) | 0.0212 (9) | 0.0048 (7) | 0.0009 (8) | 0.0029 (7) |
O1B | 0.0466 (8) | 0.0331 (7) | 0.0204 (7) | −0.0016 (6) | −0.0058 (6) | 0.0049 (5) |
O2B | 0.0383 (8) | 0.0249 (6) | 0.0254 (7) | −0.0036 (5) | −0.0050 (6) | −0.0001 (5) |
O3B | 0.0535 (9) | 0.0314 (7) | 0.0231 (7) | −0.0046 (6) | −0.0050 (6) | 0.0099 (5) |
N1B | 0.0242 (8) | 0.0280 (8) | 0.0202 (7) | 0.0024 (6) | 0.0001 (6) | 0.0032 (6) |
N2B | 0.0219 (7) | 0.0272 (8) | 0.0202 (7) | 0.0027 (6) | 0.0003 (6) | 0.0005 (6) |
N3B | 0.0225 (7) | 0.0254 (7) | 0.0206 (7) | 0.0033 (6) | 0.0006 (6) | 0.0021 (6) |
C1B | 0.0195 (8) | 0.0238 (8) | 0.0170 (8) | 0.0035 (6) | 0.0010 (6) | 0.0013 (6) |
C2B | 0.0224 (9) | 0.0215 (8) | 0.0214 (9) | 0.0001 (6) | 0.0013 (7) | 0.0000 (6) |
C3B | 0.0243 (9) | 0.0212 (8) | 0.0210 (8) | 0.0027 (7) | 0.0025 (7) | 0.0048 (6) |
C4B | 0.0174 (8) | 0.0241 (8) | 0.0186 (8) | 0.0040 (6) | 0.0015 (6) | 0.0003 (6) |
C5B | 0.0216 (9) | 0.0214 (8) | 0.0234 (9) | −0.0002 (6) | 0.0002 (7) | −0.0005 (6) |
C6B | 0.0247 (9) | 0.0234 (8) | 0.0213 (9) | 0.0028 (7) | 0.0034 (7) | 0.0058 (6) |
C7B | 0.0212 (8) | 0.0254 (8) | 0.0169 (8) | 0.0041 (6) | −0.0003 (7) | 0.0013 (6) |
C8B | 0.0247 (9) | 0.0227 (8) | 0.0232 (9) | 0.0027 (7) | −0.0006 (7) | 0.0027 (7) |
C9B | 0.0288 (10) | 0.0279 (9) | 0.0218 (9) | 0.0055 (7) | 0.0016 (7) | 0.0076 (7) |
C10B | 0.0248 (9) | 0.0307 (9) | 0.0204 (9) | 0.0069 (7) | 0.0003 (7) | 0.0004 (7) |
C11B | 0.0248 (9) | 0.0270 (9) | 0.0233 (9) | 0.0019 (7) | 0.0000 (7) | 0.0001 (7) |
C12B | 0.0244 (9) | 0.0250 (8) | 0.0201 (9) | 0.0025 (7) | 0.0007 (7) | 0.0043 (7) |
O1C | 0.0415 (8) | 0.0352 (7) | 0.0198 (6) | 0.0019 (6) | 0.0000 (6) | 0.0044 (5) |
O2C | 0.0429 (8) | 0.0451 (8) | 0.0289 (7) | −0.0069 (7) | 0.0026 (6) | 0.0162 (6) |
O3C | 0.0439 (8) | 0.0386 (8) | 0.0194 (7) | 0.0024 (6) | −0.0044 (6) | 0.0033 (5) |
N1C | 0.0355 (9) | 0.0301 (8) | 0.0178 (7) | 0.0088 (7) | 0.0004 (6) | 0.0038 (6) |
N2C | 0.0282 (8) | 0.0226 (7) | 0.0175 (7) | 0.0057 (6) | 0.0016 (6) | 0.0044 (5) |
N3C | 0.0273 (8) | 0.0224 (7) | 0.0189 (7) | 0.0065 (6) | 0.0014 (6) | 0.0033 (5) |
C1C | 0.0285 (9) | 0.0259 (9) | 0.0158 (8) | 0.0078 (7) | 0.0017 (7) | 0.0043 (6) |
C2C | 0.0256 (9) | 0.0219 (8) | 0.0206 (9) | 0.0015 (7) | 0.0012 (7) | 0.0048 (6) |
C3C | 0.0267 (9) | 0.0247 (8) | 0.0184 (8) | 0.0013 (7) | −0.0019 (7) | 0.0020 (6) |
C4C | 0.0267 (9) | 0.0206 (8) | 0.0182 (8) | 0.0080 (7) | 0.0022 (7) | 0.0035 (6) |
C5C | 0.0263 (9) | 0.0220 (8) | 0.0240 (9) | −0.0002 (7) | 0.0010 (7) | 0.0036 (7) |
C6C | 0.0289 (10) | 0.0257 (9) | 0.0208 (9) | 0.0018 (7) | −0.0008 (7) | −0.0015 (7) |
C7C | 0.0262 (9) | 0.0226 (8) | 0.0161 (8) | 0.0082 (7) | 0.0005 (7) | 0.0014 (6) |
C8C | 0.0266 (9) | 0.0226 (8) | 0.0229 (9) | 0.0046 (7) | −0.0007 (7) | 0.0016 (7) |
C9C | 0.0301 (10) | 0.0255 (9) | 0.0206 (9) | 0.0055 (7) | −0.0042 (7) | −0.0004 (7) |
C10C | 0.0320 (10) | 0.0281 (9) | 0.0175 (8) | 0.0117 (7) | 0.0022 (7) | 0.0040 (7) |
C11C | 0.0278 (9) | 0.0244 (9) | 0.0230 (9) | 0.0029 (7) | 0.0038 (7) | 0.0045 (7) |
C12C | 0.0292 (9) | 0.0240 (9) | 0.0205 (9) | 0.0051 (7) | −0.0004 (7) | 0.0023 (7) |
O1D | 0.0405 (8) | 0.0319 (7) | 0.0187 (6) | −0.0022 (6) | −0.0038 (6) | 0.0035 (5) |
O2D | 0.0359 (7) | 0.0304 (7) | 0.0271 (7) | 0.0002 (6) | −0.0044 (6) | −0.0045 (5) |
O3D | 0.0469 (8) | 0.0423 (8) | 0.0198 (7) | 0.0017 (6) | −0.0033 (6) | 0.0073 (6) |
N1D | 0.0269 (8) | 0.0326 (8) | 0.0203 (8) | 0.0062 (6) | 0.0006 (6) | 0.0014 (6) |
N2D | 0.0220 (7) | 0.0229 (7) | 0.0179 (7) | 0.0018 (6) | −0.0007 (6) | 0.0027 (5) |
N3D | 0.0208 (7) | 0.0231 (7) | 0.0187 (7) | 0.0024 (5) | 0.0008 (6) | 0.0028 (5) |
C1D | 0.0210 (8) | 0.0275 (9) | 0.0162 (8) | 0.0047 (7) | −0.0012 (7) | 0.0000 (6) |
C2D | 0.0245 (9) | 0.0221 (8) | 0.0218 (9) | 0.0018 (7) | 0.0003 (7) | 0.0016 (6) |
C3D | 0.0259 (9) | 0.0214 (8) | 0.0188 (8) | 0.0015 (7) | 0.0003 (7) | 0.0041 (6) |
C4D | 0.0184 (8) | 0.0230 (8) | 0.0188 (8) | 0.0028 (6) | 0.0011 (6) | 0.0015 (6) |
C5D | 0.0251 (9) | 0.0202 (8) | 0.0231 (9) | 0.0011 (6) | 0.0018 (7) | 0.0032 (6) |
C6D | 0.0280 (9) | 0.0250 (9) | 0.0213 (9) | 0.0052 (7) | 0.0040 (7) | 0.0068 (7) |
C7D | 0.0181 (8) | 0.0237 (8) | 0.0191 (8) | 0.0039 (6) | 0.0007 (6) | 0.0021 (6) |
C8D | 0.0239 (9) | 0.0201 (8) | 0.0236 (9) | 0.0033 (6) | 0.0025 (7) | 0.0047 (6) |
C9D | 0.0257 (9) | 0.0247 (8) | 0.0204 (9) | 0.0053 (7) | 0.0025 (7) | 0.0074 (7) |
C10D | 0.0226 (9) | 0.0288 (9) | 0.0186 (8) | 0.0058 (7) | 0.0007 (7) | 0.0015 (7) |
C11D | 0.0256 (9) | 0.0218 (8) | 0.0219 (9) | −0.0004 (7) | −0.0002 (7) | 0.0015 (6) |
C12D | 0.0241 (9) | 0.0230 (8) | 0.0199 (9) | 0.0020 (7) | 0.0018 (7) | 0.0052 (6) |
Geometric parameters (Å, º) top
O1A—C10A | 1.354 (2) | O1C—C10C | 1.355 (2) |
O1A—H1A | 0.8400 | O1C—H1C | 0.8400 |
O2A—N1A | 1.223 (2) | O2C—N1C | 1.222 (2) |
O3A—N1A | 1.2258 (19) | O3C—N1C | 1.2351 (18) |
N1A—C1A | 1.467 (2) | N1C—C1C | 1.463 (2) |
N2A—N3A | 1.2601 (19) | N2C—N3C | 1.2571 (19) |
N2A—C4A | 1.421 (2) | N2C—C4C | 1.423 (2) |
N3A—C7A | 1.414 (2) | N3C—C7C | 1.418 (2) |
C1A—C6A | 1.376 (2) | C1C—C6C | 1.376 (2) |
C1A—C2A | 1.385 (2) | C1C—C2C | 1.385 (2) |
C2A—C3A | 1.383 (2) | C2C—C3C | 1.379 (2) |
C2A—H2A | 0.9500 | C2C—H2C | 0.9500 |
C3A—C4A | 1.394 (2) | C3C—C4C | 1.394 (2) |
C3A—H3A | 0.9500 | C3C—H3C | 0.9500 |
C4A—C5A | 1.394 (2) | C4C—C5C | 1.388 (2) |
C5A—C6A | 1.378 (2) | C5C—C6C | 1.380 (2) |
C5A—H5A | 0.9500 | C5C—H5C | 0.9500 |
C6A—H6A | 0.9500 | C6C—H6C | 0.9500 |
C7A—C8A | 1.391 (2) | C7C—C8C | 1.390 (2) |
C7A—C12A | 1.399 (2) | C7C—C12C | 1.399 (2) |
C8A—C9A | 1.378 (2) | C8C—C9C | 1.388 (2) |
C8A—H8A | 0.9500 | C8C—H8C | 0.9500 |
C9A—C10A | 1.388 (2) | C9C—C10C | 1.388 (3) |
C9A—H9A | 0.9500 | C9C—H9C | 0.9500 |
C10A—C11A | 1.387 (2) | C10C—C11C | 1.396 (2) |
C11A—C12A | 1.374 (3) | C11C—C12C | 1.373 (2) |
C11A—H11A | 0.9500 | C11C—H11C | 0.9500 |
C12A—H12A | 0.9500 | C12C—H12C | 0.9500 |
O1B—C10B | 1.356 (2) | O1D—C10D | 1.357 (2) |
O1B—H1B | 0.8400 | O1D—H1D | 0.8400 |
O2B—N1B | 1.2271 (18) | O2D—N1D | 1.2274 (19) |
O3B—N1B | 1.2212 (18) | O3D—N1D | 1.2311 (19) |
N1B—C1B | 1.465 (2) | N1D—C1D | 1.460 (2) |
N2B—N3B | 1.263 (2) | N2D—N3D | 1.2616 (19) |
N2B—C4B | 1.424 (2) | N2D—C4D | 1.424 (2) |
N3B—C7B | 1.416 (2) | N3D—C7D | 1.418 (2) |
C1B—C6B | 1.376 (2) | C1D—C6D | 1.373 (2) |
C1B—C2B | 1.386 (2) | C1D—C2D | 1.389 (2) |
C2B—C3B | 1.383 (2) | C2D—C3D | 1.377 (2) |
C2B—H2B | 0.9500 | C2D—H2D | 0.9500 |
C3B—C4B | 1.394 (2) | C3D—C4D | 1.392 (2) |
C3B—H3B | 0.9500 | C3D—H3D | 0.9500 |
C4B—C5B | 1.387 (2) | C4D—C5D | 1.385 (2) |
C5B—C6B | 1.379 (2) | C5D—C6D | 1.389 (2) |
C5B—H5B | 0.9500 | C5D—H5D | 0.9500 |
C6B—H6B | 0.9500 | C6D—H6D | 0.9500 |
C7B—C8B | 1.391 (2) | C7D—C8D | 1.390 (2) |
C7B—C12B | 1.401 (2) | C7D—C12D | 1.396 (2) |
C8B—C9B | 1.381 (2) | C8D—C9D | 1.387 (2) |
C8B—H8B | 0.9500 | C8D—H8D | 0.9500 |
C9B—C10B | 1.388 (2) | C9D—C10D | 1.386 (2) |
C9B—H9B | 0.9500 | C9D—H9D | 0.9500 |
C10B—C11B | 1.394 (2) | C10D—C11D | 1.395 (2) |
C11B—C12B | 1.374 (2) | C11D—C12D | 1.374 (2) |
C11B—H11B | 0.9500 | C11D—H11D | 0.9500 |
C12B—H12B | 0.9500 | C12D—H12D | 0.9500 |
| | | |
C10A—O1A—H1A | 109.5 | C10C—O1C—H1C | 109.5 |
O2A—N1A—O3A | 122.86 (15) | O2C—N1C—O3C | 122.45 (15) |
O2A—N1A—C1A | 118.17 (15) | O2C—N1C—C1C | 118.94 (14) |
O3A—N1A—C1A | 118.97 (15) | O3C—N1C—C1C | 118.60 (15) |
N3A—N2A—C4A | 113.87 (14) | N3C—N2C—C4C | 114.31 (14) |
N2A—N3A—C7A | 114.54 (14) | N2C—N3C—C7C | 113.77 (14) |
C6A—C1A—C2A | 122.65 (16) | C6C—C1C—C2C | 122.56 (15) |
C6A—C1A—N1A | 118.13 (15) | C6C—C1C—N1C | 119.49 (15) |
C2A—C1A—N1A | 119.22 (16) | C2C—C1C—N1C | 117.95 (15) |
C3A—C2A—C1A | 118.39 (16) | C3C—C2C—C1C | 118.51 (16) |
C3A—C2A—H2A | 120.8 | C3C—C2C—H2C | 120.7 |
C1A—C2A—H2A | 120.8 | C1C—C2C—H2C | 120.7 |
C2A—C3A—C4A | 120.11 (16) | C2C—C3C—C4C | 120.16 (15) |
C2A—C3A—H3A | 119.9 | C2C—C3C—H3C | 119.9 |
C4A—C3A—H3A | 119.9 | C4C—C3C—H3C | 119.9 |
C3A—C4A—C5A | 119.91 (16) | C5C—C4C—C3C | 119.81 (15) |
C3A—C4A—N2A | 124.68 (15) | C5C—C4C—N2C | 115.78 (15) |
C5A—C4A—N2A | 115.41 (15) | C3C—C4C—N2C | 124.40 (15) |
C6A—C5A—C4A | 120.31 (16) | C6C—C5C—C4C | 120.58 (16) |
C6A—C5A—H5A | 119.8 | C6C—C5C—H5C | 119.7 |
C4A—C5A—H5A | 119.8 | C4C—C5C—H5C | 119.7 |
C1A—C6A—C5A | 118.59 (16) | C1C—C6C—C5C | 118.33 (15) |
C1A—C6A—H6A | 120.7 | C1C—C6C—H6C | 120.8 |
C5A—C6A—H6A | 120.7 | C5C—C6C—H6C | 120.8 |
C8A—C7A—C12A | 119.36 (16) | C8C—C7C—C12C | 119.27 (16) |
C8A—C7A—N3A | 116.34 (15) | C8C—C7C—N3C | 116.71 (15) |
C12A—C7A—N3A | 124.29 (15) | C12C—C7C—N3C | 124.02 (15) |
C9A—C8A—C7A | 120.75 (16) | C9C—C8C—C7C | 120.48 (16) |
C9A—C8A—H8A | 119.6 | C9C—C8C—H8C | 119.8 |
C7A—C8A—H8A | 119.6 | C7C—C8C—H8C | 119.8 |
C8A—C9A—C10A | 119.47 (16) | C8C—C9C—C10C | 119.81 (16) |
C8A—C9A—H9A | 120.3 | C8C—C9C—H9C | 120.1 |
C10A—C9A—H9A | 120.3 | C10C—C9C—H9C | 120.1 |
O1A—C10A—C11A | 116.36 (16) | O1C—C10C—C9C | 124.03 (16) |
O1A—C10A—C9A | 123.43 (16) | O1C—C10C—C11C | 116.20 (16) |
C11A—C10A—C9A | 120.20 (16) | C9C—C10C—C11C | 119.77 (16) |
C12A—C11A—C10A | 120.45 (17) | C12C—C11C—C10C | 120.31 (16) |
C12A—C11A—H11A | 119.8 | C12C—C11C—H11C | 119.8 |
C10A—C11A—H11A | 119.8 | C10C—C11C—H11C | 119.8 |
C11A—C12A—C7A | 119.76 (16) | C11C—C12C—C7C | 120.34 (16) |
C11A—C12A—H12A | 120.1 | C11C—C12C—H12C | 119.8 |
C7A—C12A—H12A | 120.1 | C7C—C12C—H12C | 119.8 |
C10B—O1B—H1B | 109.5 | C10D—O1D—H1D | 109.5 |
O3B—N1B—O2B | 122.98 (15) | O2D—N1D—O3D | 122.52 (15) |
O3B—N1B—C1B | 118.97 (14) | O2D—N1D—C1D | 118.65 (14) |
O2B—N1B—C1B | 118.04 (14) | O3D—N1D—C1D | 118.82 (15) |
N3B—N2B—C4B | 114.43 (14) | N3D—N2D—C4D | 113.83 (13) |
N2B—N3B—C7B | 114.25 (14) | N2D—N3D—C7D | 114.22 (14) |
C6B—C1B—C2B | 122.66 (15) | C6D—C1D—C2D | 122.86 (15) |
C6B—C1B—N1B | 117.94 (14) | C6D—C1D—N1D | 119.32 (15) |
C2B—C1B—N1B | 119.40 (14) | C2D—C1D—N1D | 117.81 (15) |
C3B—C2B—C1B | 118.04 (15) | C3D—C2D—C1D | 118.17 (15) |
C3B—C2B—H2B | 121.0 | C3D—C2D—H2D | 120.9 |
C1B—C2B—H2B | 121.0 | C1D—C2D—H2D | 120.9 |
C2B—C3B—C4B | 120.28 (15) | C2D—C3D—C4D | 120.19 (15) |
C2B—C3B—H3B | 119.9 | C2D—C3D—H3D | 119.9 |
C4B—C3B—H3B | 119.9 | C4D—C3D—H3D | 119.9 |
C5B—C4B—C3B | 120.08 (15) | C5D—C4D—C3D | 120.44 (15) |
C5B—C4B—N2B | 115.11 (14) | C5D—C4D—N2D | 116.00 (14) |
C3B—C4B—N2B | 124.80 (15) | C3D—C4D—N2D | 123.55 (14) |
C6B—C5B—C4B | 120.20 (15) | C4D—C5D—C6D | 119.99 (15) |
C6B—C5B—H5B | 119.9 | C4D—C5D—H5D | 120.0 |
C4B—C5B—H5B | 119.9 | C6D—C5D—H5D | 120.0 |
C1B—C6B—C5B | 118.72 (15) | C1D—C6D—C5D | 118.33 (15) |
C1B—C6B—H6B | 120.6 | C1D—C6D—H6D | 120.8 |
C5B—C6B—H6B | 120.6 | C5D—C6D—H6D | 120.8 |
C8B—C7B—C12B | 119.54 (15) | C8D—C7D—C12D | 119.50 (15) |
C8B—C7B—N3B | 116.60 (15) | C8D—C7D—N3D | 116.65 (15) |
C12B—C7B—N3B | 123.86 (15) | C12D—C7D—N3D | 123.85 (14) |
C9B—C8B—C7B | 120.73 (16) | C9D—C8D—C7D | 120.17 (15) |
C9B—C8B—H8B | 119.6 | C9D—C8D—H8D | 119.9 |
C7B—C8B—H8B | 119.6 | C7D—C8D—H8D | 119.9 |
C8B—C9B—C10B | 119.26 (16) | C10D—C9D—C8D | 119.86 (15) |
C8B—C9B—H9B | 120.4 | C10D—C9D—H9D | 120.1 |
C10B—C9B—H9B | 120.4 | C8D—C9D—H9D | 120.1 |
O1B—C10B—C9B | 123.66 (16) | O1D—C10D—C9D | 123.71 (15) |
O1B—C10B—C11B | 115.84 (15) | O1D—C10D—C11D | 116.16 (15) |
C9B—C10B—C11B | 120.51 (16) | C9D—C10D—C11D | 120.12 (15) |
C12B—C11B—C10B | 120.10 (16) | C12D—C11D—C10D | 119.87 (15) |
C12B—C11B—H11B | 120.0 | C12D—C11D—H11D | 120.1 |
C10B—C11B—H11B | 120.0 | C10D—C11D—H11D | 120.1 |
C11B—C12B—C7B | 119.84 (15) | C11D—C12D—C7D | 120.45 (15) |
C11B—C12B—H12B | 120.1 | C11D—C12D—H12D | 119.8 |
C7B—C12B—H12B | 120.1 | C7D—C12D—H12D | 119.8 |
| | | |
C4A—N2A—N3A—C7A | 179.04 (14) | C4C—N2C—N3C—C7C | −178.84 (14) |
O2A—N1A—C1A—C6A | 178.12 (16) | O2C—N1C—C1C—C6C | 176.57 (17) |
O3A—N1A—C1A—C6A | −1.8 (2) | O3C—N1C—C1C—C6C | −3.9 (2) |
O2A—N1A—C1A—C2A | −1.7 (2) | O2C—N1C—C1C—C2C | −3.0 (2) |
O3A—N1A—C1A—C2A | 178.42 (16) | O3C—N1C—C1C—C2C | 176.54 (15) |
C6A—C1A—C2A—C3A | 0.9 (3) | C6C—C1C—C2C—C3C | 1.0 (3) |
N1A—C1A—C2A—C3A | −179.37 (15) | N1C—C1C—C2C—C3C | −179.44 (15) |
C1A—C2A—C3A—C4A | 0.1 (3) | C1C—C2C—C3C—C4C | 0.8 (3) |
C2A—C3A—C4A—C5A | −1.7 (3) | C2C—C3C—C4C—C5C | −2.2 (3) |
C2A—C3A—C4A—N2A | 178.71 (16) | C2C—C3C—C4C—N2C | 177.34 (16) |
N3A—N2A—C4A—C3A | −6.4 (2) | N3C—N2C—C4C—C5C | 173.60 (15) |
N3A—N2A—C4A—C5A | 173.98 (14) | N3C—N2C—C4C—C3C | −5.9 (2) |
C3A—C4A—C5A—C6A | 2.4 (3) | C3C—C4C—C5C—C6C | 1.7 (3) |
N2A—C4A—C5A—C6A | −177.98 (16) | N2C—C4C—C5C—C6C | −177.81 (16) |
C2A—C1A—C6A—C5A | −0.2 (3) | C2C—C1C—C6C—C5C | −1.5 (3) |
N1A—C1A—C6A—C5A | −179.97 (15) | N1C—C1C—C6C—C5C | 179.03 (15) |
C4A—C5A—C6A—C1A | −1.5 (3) | C4C—C5C—C6C—C1C | 0.0 (3) |
N2A—N3A—C7A—C8A | −179.77 (15) | N2C—N3C—C7C—C8C | −176.74 (14) |
N2A—N3A—C7A—C12A | −0.8 (2) | N2C—N3C—C7C—C12C | 3.7 (2) |
C12A—C7A—C8A—C9A | −0.8 (3) | C12C—C7C—C8C—C9C | −0.3 (3) |
N3A—C7A—C8A—C9A | 178.24 (16) | N3C—C7C—C8C—C9C | −179.83 (15) |
C7A—C8A—C9A—C10A | 0.2 (3) | C7C—C8C—C9C—C10C | 1.0 (3) |
C8A—C9A—C10A—O1A | 179.82 (17) | C8C—C9C—C10C—O1C | 178.82 (16) |
C8A—C9A—C10A—C11A | 1.0 (3) | C8C—C9C—C10C—C11C | −1.1 (3) |
O1A—C10A—C11A—C12A | 179.50 (17) | O1C—C10C—C11C—C12C | −179.54 (16) |
C9A—C10A—C11A—C12A | −1.6 (3) | C9C—C10C—C11C—C12C | 0.4 (3) |
C10A—C11A—C12A—C7A | 1.0 (3) | C10C—C11C—C12C—C7C | 0.4 (3) |
C8A—C7A—C12A—C11A | 0.2 (3) | C8C—C7C—C12C—C11C | −0.4 (3) |
N3A—C7A—C12A—C11A | −178.75 (16) | N3C—C7C—C12C—C11C | 179.07 (16) |
C4B—N2B—N3B—C7B | 179.42 (13) | C4D—N2D—N3D—C7D | 179.51 (13) |
O3B—N1B—C1B—C6B | 0.3 (2) | O2D—N1D—C1D—C6D | 175.51 (16) |
O2B—N1B—C1B—C6B | 179.10 (16) | O3D—N1D—C1D—C6D | −3.7 (2) |
O3B—N1B—C1B—C2B | −179.46 (16) | O2D—N1D—C1D—C2D | −3.2 (2) |
O2B—N1B—C1B—C2B | −0.7 (2) | O3D—N1D—C1D—C2D | 177.59 (16) |
C6B—C1B—C2B—C3B | −0.7 (3) | C6D—C1D—C2D—C3D | −1.0 (3) |
N1B—C1B—C2B—C3B | 179.03 (15) | N1D—C1D—C2D—C3D | 177.63 (15) |
C1B—C2B—C3B—C4B | 1.0 (3) | C1D—C2D—C3D—C4D | 0.2 (3) |
C2B—C3B—C4B—C5B | −0.1 (3) | C2D—C3D—C4D—C5D | 0.9 (3) |
C2B—C3B—C4B—N2B | −179.14 (16) | C2D—C3D—C4D—N2D | −178.64 (16) |
N3B—N2B—C4B—C5B | −178.09 (15) | N3D—N2D—C4D—C5D | −177.15 (15) |
N3B—N2B—C4B—C3B | 1.0 (2) | N3D—N2D—C4D—C3D | 2.4 (2) |
C3B—C4B—C5B—C6B | −1.1 (3) | C3D—C4D—C5D—C6D | −1.2 (3) |
N2B—C4B—C5B—C6B | 178.03 (15) | N2D—C4D—C5D—C6D | 178.40 (15) |
C2B—C1B—C6B—C5B | −0.4 (3) | C2D—C1D—C6D—C5D | 0.7 (3) |
N1B—C1B—C6B—C5B | 179.80 (15) | N1D—C1D—C6D—C5D | −177.89 (15) |
C4B—C5B—C6B—C1B | 1.4 (3) | C4D—C5D—C6D—C1D | 0.4 (3) |
N2B—N3B—C7B—C8B | −179.12 (15) | N2D—N3D—C7D—C8D | 178.77 (15) |
N2B—N3B—C7B—C12B | 0.2 (2) | N2D—N3D—C7D—C12D | −1.4 (2) |
C12B—C7B—C8B—C9B | 1.2 (3) | C12D—C7D—C8D—C9D | 0.2 (3) |
N3B—C7B—C8B—C9B | −179.48 (15) | N3D—C7D—C8D—C9D | −179.93 (15) |
C7B—C8B—C9B—C10B | −0.3 (3) | C7D—C8D—C9D—C10D | 1.2 (3) |
C8B—C9B—C10B—O1B | 179.28 (16) | C8D—C9D—C10D—O1D | 177.74 (16) |
C8B—C9B—C10B—C11B | −1.2 (3) | C8D—C9D—C10D—C11D | −2.1 (3) |
O1B—C10B—C11B—C12B | −178.47 (15) | O1D—C10D—C11D—C12D | −178.29 (15) |
C9B—C10B—C11B—C12B | 2.0 (3) | C9D—C10D—C11D—C12D | 1.6 (3) |
C10B—C11B—C12B—C7B | −1.2 (3) | C10D—C11D—C12D—C7D | −0.1 (3) |
C8B—C7B—C12B—C11B | −0.4 (3) | C8D—C7D—C12D—C11D | −0.8 (3) |
N3B—C7B—C12B—C11B | −179.70 (16) | N3D—C7D—C12D—C11D | 179.40 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O2Bi | 0.84 | 2.02 | 2.753 (2) | 146 |
O1B—H1B···O2A | 0.84 | 2.12 | 2.811 (2) | 140 |
O1C—H1C···O3D | 0.84 | 2.06 | 2.903 (2) | 177 |
O1D—H1D···O3Ci | 0.84 | 2.07 | 2.904 (2) | 174 |
Symmetry code: (i) x−1, y, z−1. |
(IIIa) (
E)-(4-methoxyphenyl)(4-nitrophenyl)diazene
top
Crystal data top
C13H11N3O3 | Z = 2 |
Mr = 257.25 | F(000) = 268 |
Triclinic, P1 | Dx = 1.406 Mg m−3 |
Hall symbol: -P1 | Melting point: 421 K |
a = 6.1530 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.5500 (15) Å | Cell parameters from 24 reflections |
c = 13.683 (3) Å | θ = 11–12° |
α = 100.80 (3)° | µ = 0.10 mm−1 |
β = 102.68 (3)° | T = 298 K |
γ = 91.74 (3)° | Parallelepiped prism, yellow |
V = 607.5 (2) Å3 | 0.45 × 0.35 × 0.30 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.058 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.8° |
Graphite monochromator | h = 0→7 |
θ/2θ scans | k = −9→9 |
2618 measured reflections | l = −16→16 |
2382 independent reflections | 3 standard reflections every 97 reflections |
1717 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.079P)2 + 0.0794P] where P = (Fo2 + 2Fc2)/3 |
2382 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C13H11N3O3 | γ = 91.74 (3)° |
Mr = 257.25 | V = 607.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.1530 (12) Å | Mo Kα radiation |
b = 7.5500 (15) Å | µ = 0.10 mm−1 |
c = 13.683 (3) Å | T = 298 K |
α = 100.80 (3)° | 0.45 × 0.35 × 0.30 mm |
β = 102.68 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.058 |
2618 measured reflections | 3 standard reflections every 97 reflections |
2382 independent reflections | intensity decay: 3% |
1717 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.16 e Å−3 |
2382 reflections | Δρmin = −0.19 e Å−3 |
173 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. All H atoms were placed in geometrically calculeted positions and
refined using a riding model. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.24178 (19) | −0.11783 (17) | 0.16573 (9) | 0.0648 (4) | |
O2 | 1.3612 (2) | 0.66378 (19) | 0.83739 (9) | 0.0787 (4) | |
O3 | 1.1712 (2) | 0.6266 (2) | 0.94592 (9) | 0.0886 (5) | |
N1 | 1.1933 (2) | 0.60681 (18) | 0.85842 (10) | 0.0532 (3) | |
N2 | 0.47598 (19) | 0.25706 (16) | 0.54580 (9) | 0.0461 (3) | |
N3 | 0.49461 (19) | 0.23619 (15) | 0.45539 (9) | 0.0443 (3) | |
C1 | 1.0110 (2) | 0.51416 (18) | 0.77543 (10) | 0.0433 (3) | |
C2 | 1.0340 (2) | 0.49594 (19) | 0.67598 (11) | 0.0459 (4) | |
H2A | 1.1643 | 0.5400 | 0.6620 | 0.055* | |
C3 | 0.8599 (2) | 0.4111 (2) | 0.59786 (11) | 0.0460 (4) | |
H3A | 0.8717 | 0.3975 | 0.5303 | 0.055* | |
C4 | 0.6661 (2) | 0.34566 (17) | 0.62027 (10) | 0.0416 (3) | |
C5 | 0.6484 (2) | 0.3642 (2) | 0.72077 (11) | 0.0490 (4) | |
H5A | 0.5193 | 0.3188 | 0.7352 | 0.059* | |
C6 | 0.8215 (3) | 0.4496 (2) | 0.79974 (11) | 0.0504 (4) | |
H6A | 0.8105 | 0.4633 | 0.8674 | 0.060* | |
C7 | 0.3032 (2) | 0.14801 (17) | 0.38274 (10) | 0.0409 (3) | |
C8 | 0.3135 (2) | 0.1157 (2) | 0.28108 (11) | 0.0484 (4) | |
H8A | 0.4424 | 0.1529 | 0.2632 | 0.058* | |
C9 | 0.1339 (3) | 0.0283 (2) | 0.20552 (11) | 0.0522 (4) | |
H9A | 0.1420 | 0.0073 | 0.1373 | 0.063* | |
C10 | −0.0577 (2) | −0.0275 (2) | 0.23241 (11) | 0.0471 (4) | |
C11 | −0.0697 (2) | 0.0070 (2) | 0.33423 (11) | 0.0488 (4) | |
H11A | −0.1991 | −0.0291 | 0.3521 | 0.059* | |
C12 | 0.1078 (2) | 0.0939 (2) | 0.40852 (11) | 0.0456 (4) | |
H12A | 0.0981 | 0.1169 | 0.4766 | 0.055* | |
C13 | −0.2495 (4) | −0.1463 (3) | 0.05961 (13) | 0.0806 (6) | |
H13B | −0.3905 | −0.2075 | 0.0220 | 0.121* | |
H13A | −0.1308 | −0.2188 | 0.0449 | 0.121* | |
H13C | −0.2324 | −0.0319 | 0.0401 | 0.121* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0535 (7) | 0.0752 (8) | 0.0525 (7) | −0.0132 (6) | −0.0047 (5) | 0.0021 (6) |
O2 | 0.0544 (7) | 0.1048 (10) | 0.0650 (7) | −0.0289 (7) | 0.0065 (6) | 0.0009 (7) |
O3 | 0.0788 (9) | 0.1285 (13) | 0.0445 (7) | −0.0347 (8) | 0.0069 (6) | −0.0025 (7) |
N1 | 0.0506 (7) | 0.0551 (8) | 0.0469 (7) | −0.0062 (6) | 0.0040 (6) | 0.0030 (6) |
N2 | 0.0443 (7) | 0.0448 (7) | 0.0455 (7) | −0.0046 (5) | 0.0058 (5) | 0.0060 (5) |
N3 | 0.0440 (7) | 0.0408 (7) | 0.0457 (7) | −0.0021 (5) | 0.0069 (5) | 0.0074 (5) |
C1 | 0.0431 (8) | 0.0375 (7) | 0.0446 (8) | −0.0001 (6) | 0.0039 (6) | 0.0040 (6) |
C2 | 0.0417 (7) | 0.0449 (8) | 0.0491 (8) | −0.0037 (6) | 0.0086 (6) | 0.0080 (6) |
C3 | 0.0482 (8) | 0.0465 (8) | 0.0418 (7) | −0.0030 (6) | 0.0088 (6) | 0.0075 (6) |
C4 | 0.0416 (7) | 0.0344 (7) | 0.0452 (8) | 0.0000 (5) | 0.0049 (6) | 0.0056 (6) |
C5 | 0.0431 (8) | 0.0513 (8) | 0.0517 (8) | −0.0058 (6) | 0.0121 (6) | 0.0080 (6) |
C6 | 0.0527 (8) | 0.0550 (9) | 0.0418 (7) | −0.0027 (7) | 0.0112 (6) | 0.0063 (6) |
C7 | 0.0417 (7) | 0.0348 (7) | 0.0443 (7) | −0.0003 (5) | 0.0058 (6) | 0.0083 (6) |
C8 | 0.0443 (8) | 0.0524 (9) | 0.0491 (8) | −0.0024 (6) | 0.0119 (6) | 0.0114 (7) |
C9 | 0.0557 (9) | 0.0596 (9) | 0.0393 (7) | −0.0001 (7) | 0.0087 (6) | 0.0080 (7) |
C10 | 0.0451 (8) | 0.0432 (8) | 0.0467 (8) | 0.0004 (6) | −0.0003 (6) | 0.0066 (6) |
C11 | 0.0415 (7) | 0.0513 (8) | 0.0524 (8) | −0.0058 (6) | 0.0091 (6) | 0.0107 (7) |
C12 | 0.0482 (8) | 0.0472 (8) | 0.0401 (7) | −0.0026 (6) | 0.0097 (6) | 0.0071 (6) |
C13 | 0.0763 (13) | 0.0940 (15) | 0.0508 (10) | −0.0076 (11) | −0.0108 (9) | −0.0053 (9) |
Geometric parameters (Å, º) top
O1—C10 | 1.3591 (18) | C5—C6 | 1.382 (2) |
O1—C13 | 1.417 (2) | C5—H5A | 0.9300 |
O1—C13 | 1.417 (2) | C6—H6A | 0.9300 |
O2—N1 | 1.2186 (17) | C7—C8 | 1.3826 (19) |
O3—N1 | 1.2166 (17) | C7—C12 | 1.3954 (19) |
N1—C1 | 1.4604 (19) | C8—C9 | 1.387 (2) |
N2—N3 | 1.2485 (17) | C8—H8A | 0.9300 |
N2—C4 | 1.4242 (18) | C9—C10 | 1.386 (2) |
N3—C7 | 1.4175 (18) | C9—H9A | 0.9300 |
C1—C6 | 1.380 (2) | C10—C11 | 1.387 (2) |
C1—C2 | 1.381 (2) | C11—C12 | 1.370 (2) |
C2—C3 | 1.379 (2) | C11—H11A | 0.9300 |
C2—H2A | 0.9300 | C12—H12A | 0.9300 |
C3—C4 | 1.393 (2) | C13—H13B | 0.9600 |
C3—H3A | 0.9300 | C13—H13A | 0.9600 |
C4—C5 | 1.385 (2) | C13—H13C | 0.9600 |
| | | |
C10—O1—C13 | 118.66 (14) | C8—C7—C12 | 119.10 (13) |
O3—N1—O2 | 122.30 (14) | C8—C7—N3 | 117.27 (12) |
O3—N1—C1 | 118.94 (13) | C12—C7—N3 | 123.63 (13) |
O2—N1—C1 | 118.75 (13) | C7—C8—C9 | 120.71 (13) |
N3—N2—C4 | 114.99 (12) | C7—C8—H8A | 119.6 |
N2—N3—C7 | 113.92 (12) | C9—C8—H8A | 119.6 |
C6—C1—C2 | 122.66 (14) | C10—C9—C8 | 119.56 (14) |
C6—C1—N1 | 118.48 (13) | C10—C9—H9A | 120.2 |
C2—C1—N1 | 118.85 (13) | C8—C9—H9A | 120.2 |
C3—C2—C1 | 118.60 (13) | O1—C10—C9 | 124.94 (14) |
C3—C2—H2A | 120.7 | O1—C10—C11 | 115.20 (13) |
C1—C2—H2A | 120.7 | C9—C10—C11 | 119.86 (14) |
C2—C3—C4 | 119.90 (14) | C12—C11—C10 | 120.36 (13) |
C2—C3—H3A | 120.1 | C12—C11—H11A | 119.8 |
C4—C3—H3A | 120.1 | C10—C11—H11A | 119.8 |
C5—C4—C3 | 120.28 (13) | C11—C12—C7 | 120.39 (13) |
C5—C4—N2 | 115.10 (12) | C11—C12—H12A | 119.8 |
C3—C4—N2 | 124.62 (13) | C7—C12—H12A | 119.8 |
C6—C5—C4 | 120.38 (13) | O1—C13—H13B | 109.5 |
C6—C5—H5A | 119.8 | O1—C13—H13A | 109.5 |
C4—C5—H5A | 119.8 | H13B—C13—H13A | 109.5 |
C1—C6—C5 | 118.18 (14) | O1—C13—H13C | 109.5 |
C1—C6—H6A | 120.9 | H13B—C13—H13C | 109.5 |
C5—C6—H6A | 120.9 | H13A—C13—H13C | 109.5 |
| | | |
C4—N2—N3—C7 | −179.90 (10) | C4—C5—C6—C1 | −0.4 (2) |
O3—N1—C1—C6 | −1.1 (2) | N2—N3—C7—C8 | −178.29 (13) |
O2—N1—C1—C6 | 179.87 (15) | N2—N3—C7—C12 | 2.0 (2) |
O3—N1—C1—C2 | 178.34 (15) | C12—C7—C8—C9 | −0.9 (2) |
O2—N1—C1—C2 | −0.7 (2) | N3—C7—C8—C9 | 179.31 (13) |
C6—C1—C2—C3 | 0.5 (2) | C7—C8—C9—C10 | −0.2 (2) |
N1—C1—C2—C3 | −178.91 (13) | C13—O1—C10—C9 | −5.3 (3) |
C1—C2—C3—C4 | −0.1 (2) | C13—O1—C10—C11 | 175.30 (15) |
C2—C3—C4—C5 | −0.5 (2) | C8—C9—C10—O1 | −178.36 (14) |
C2—C3—C4—N2 | 179.60 (12) | C8—C9—C10—C11 | 1.0 (2) |
N3—N2—C4—C5 | −178.17 (13) | O1—C10—C11—C12 | 178.63 (13) |
N3—N2—C4—C3 | 1.7 (2) | C9—C10—C11—C12 | −0.8 (2) |
C3—C4—C5—C6 | 0.8 (2) | C10—C11—C12—C7 | −0.3 (2) |
N2—C4—C5—C6 | −179.32 (13) | C8—C7—C12—C11 | 1.1 (2) |
C2—C1—C6—C5 | −0.3 (2) | N3—C7—C12—C11 | −179.11 (13) |
N1—C1—C6—C5 | 179.17 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 0.93 | 2.57 | 3.412 (2) | 150 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
(IIIc) (
E)-[4-(6-bromohexyloxy)phenyl](4-cyanophenyl)diazene
top
Crystal data top
C19H20BrN3O | Z = 4 |
Mr = 386.29 | F(000) = 792 |
Triclinic, P1 | Dx = 1.495 Mg m−3 |
Hall symbol: -P1 | Melting point: 376 K |
a = 7.4279 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.009 (3) Å | Cell parameters from 320 reflections |
c = 19.552 (5) Å | θ = 4–24° |
α = 86.502 (5)° | µ = 2.41 mm−1 |
β = 80.511 (5)° | T = 110 K |
γ = 87.604 (5)° | Plate, yellow |
V = 1716.2 (7) Å3 | 0.50 × 0.35 × 0.15 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 9845 independent reflections |
Radiation source: fine-focus sealed tube | 3353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
ϕ and ω scans | θmax = 30.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
Tmin = 0.403, Tmax = 0.697 | k = −16→16 |
20166 measured reflections | l = −26→27 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.68 | w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3 |
9845 reflections | (Δ/σ)max < 0.001 |
433 parameters | Δρmax = 1.17 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
C19H20BrN3O | γ = 87.604 (5)° |
Mr = 386.29 | V = 1716.2 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.4279 (18) Å | Mo Kα radiation |
b = 12.009 (3) Å | µ = 2.41 mm−1 |
c = 19.552 (5) Å | T = 110 K |
α = 86.502 (5)° | 0.50 × 0.35 × 0.15 mm |
β = 80.511 (5)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 9845 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3353 reflections with I > 2σ(I) |
Tmin = 0.403, Tmax = 0.697 | Rint = 0.083 |
20166 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.68 | Δρmax = 1.17 e Å−3 |
9845 reflections | Δρmin = −0.48 e Å−3 |
433 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. All H atoms were placed in geometrically calculated positions and
refined using a riding model. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1A | 0.06933 (6) | −0.11321 (3) | 0.07294 (2) | 0.03930 (14) | |
O1A | 0.5947 (3) | 0.25090 (19) | 0.25472 (13) | 0.0287 (6) | |
N1A | −0.1448 (5) | 0.8239 (3) | 0.77340 (17) | 0.0388 (9) | |
N2A | 0.2520 (4) | 0.4768 (2) | 0.52729 (16) | 0.0232 (7) | |
N3A | 0.2536 (4) | 0.5135 (2) | 0.46568 (16) | 0.0225 (7) | |
C1A | 0.0073 (5) | 0.6891 (3) | 0.68080 (18) | 0.0222 (9) | |
C2A | 0.0242 (5) | 0.7274 (3) | 0.61082 (18) | 0.0233 (9) | |
H2AB | −0.0189 | 0.8004 | 0.5988 | 0.028* | |
C3A | 0.1027 (5) | 0.6595 (3) | 0.56028 (18) | 0.0232 (9) | |
H3AB | 0.1132 | 0.6852 | 0.5129 | 0.028* | |
C4A | 0.1677 (5) | 0.5529 (3) | 0.57728 (19) | 0.0220 (9) | |
C5A | 0.1530 (5) | 0.5149 (3) | 0.64745 (19) | 0.0257 (9) | |
H5AA | 0.1997 | 0.4428 | 0.6594 | 0.031* | |
C6A | 0.0707 (5) | 0.5827 (3) | 0.69868 (19) | 0.0258 (9) | |
H6AA | 0.0573 | 0.5567 | 0.7461 | 0.031* | |
C7A | 0.3367 (5) | 0.4415 (3) | 0.41379 (19) | 0.0211 (9) | |
C8A | 0.3483 (5) | 0.4841 (3) | 0.34616 (19) | 0.0234 (9) | |
H8AA | 0.2998 | 0.5569 | 0.3371 | 0.028* | |
C9A | 0.4303 (5) | 0.4219 (3) | 0.29110 (19) | 0.0250 (9) | |
H9AA | 0.4355 | 0.4513 | 0.2446 | 0.030* | |
C10A | 0.5043 (5) | 0.3164 (3) | 0.30449 (19) | 0.0243 (9) | |
C11A | 0.4877 (5) | 0.2714 (3) | 0.37308 (19) | 0.0259 (9) | |
H11A | 0.5331 | 0.1977 | 0.3822 | 0.031* | |
C12A | 0.4057 (5) | 0.3337 (3) | 0.42727 (19) | 0.0234 (9) | |
H12A | 0.3961 | 0.3035 | 0.4737 | 0.028* | |
C13A | −0.0769 (5) | 0.7636 (3) | 0.7332 (2) | 0.0269 (9) | |
C14A | 0.6199 (5) | 0.2953 (3) | 0.18423 (18) | 0.0273 (9) | |
H14A | 0.6842 | 0.3666 | 0.1802 | 0.033* | |
H14B | 0.5000 | 0.3098 | 0.1690 | 0.033* | |
C15A | 0.7316 (5) | 0.2108 (3) | 0.1394 (2) | 0.0347 (10) | |
H15A | 0.7619 | 0.2439 | 0.0915 | 0.042* | |
H15B | 0.8477 | 0.1941 | 0.1571 | 0.042* | |
C16A | 0.6353 (5) | 0.1029 (3) | 0.13753 (19) | 0.0295 (10) | |
H16A | 0.5849 | 0.0770 | 0.1856 | 0.035* | |
H16B | 0.7258 | 0.0455 | 0.1181 | 0.035* | |
C17A | 0.4806 (5) | 0.1130 (3) | 0.09452 (19) | 0.0286 (9) | |
H17A | 0.5329 | 0.1281 | 0.0450 | 0.034* | |
H17B | 0.3988 | 0.1772 | 0.1096 | 0.034* | |
C18A | 0.3691 (5) | 0.0075 (3) | 0.10173 (19) | 0.0282 (9) | |
H18A | 0.4483 | −0.0559 | 0.0834 | 0.034* | |
H18B | 0.3230 | −0.0107 | 0.1514 | 0.034* | |
C19A | 0.2112 (5) | 0.0234 (3) | 0.0628 (2) | 0.0322 (10) | |
H19A | 0.2570 | 0.0413 | 0.0131 | 0.039* | |
H19B | 0.1317 | 0.0867 | 0.0811 | 0.039* | |
Br1B | 0.90469 (5) | 0.58117 (3) | 0.90418 (2) | 0.03685 (14) | |
O1B | 0.4040 (3) | 0.27510 (19) | 0.72551 (12) | 0.0265 (6) | |
N1B | 1.1512 (4) | −0.3268 (3) | 0.22147 (16) | 0.0334 (9) | |
N2B | 0.7523 (4) | 0.0223 (2) | 0.46623 (16) | 0.0241 (7) | |
N3B | 0.7438 (4) | −0.0135 (2) | 0.52915 (16) | 0.0241 (7) | |
C1B | 0.9971 (4) | −0.1935 (3) | 0.31539 (19) | 0.0223 (9) | |
C2B | 0.9820 (5) | −0.2303 (3) | 0.38463 (18) | 0.0219 (9) | |
H2BB | 1.0272 | −0.3027 | 0.3969 | 0.026* | |
C3B | 0.9017 (5) | −0.1619 (3) | 0.43503 (18) | 0.0236 (9) | |
H3BB | 0.8889 | −0.1876 | 0.4825 | 0.028* | |
C4B | 0.8382 (5) | −0.0547 (3) | 0.41744 (19) | 0.0217 (9) | |
C5B | 0.8551 (5) | −0.0185 (3) | 0.34788 (19) | 0.0239 (9) | |
H5BA | 0.8103 | 0.0541 | 0.3358 | 0.029* | |
C6B | 0.9354 (5) | −0.0856 (3) | 0.29638 (19) | 0.0250 (9) | |
H6BA | 0.9490 | −0.0598 | 0.2490 | 0.030* | |
C7B | 0.6596 (5) | 0.0621 (3) | 0.57813 (19) | 0.0208 (9) | |
C8B | 0.6449 (5) | 0.0283 (3) | 0.64709 (19) | 0.0252 (9) | |
H8BA | 0.6927 | −0.0432 | 0.6599 | 0.030* | |
C9B | 0.5607 (5) | 0.0975 (3) | 0.69883 (19) | 0.0243 (9) | |
H9BA | 0.5504 | 0.0736 | 0.7465 | 0.029* | |
C10B | 0.4924 (5) | 0.2016 (3) | 0.67924 (19) | 0.0234 (9) | |
C11B | 0.5102 (5) | 0.2373 (3) | 0.60966 (18) | 0.0214 (9) | |
H11B | 0.4658 | 0.3095 | 0.5967 | 0.026* | |
C12B | 0.5915 (5) | 0.1686 (3) | 0.55995 (18) | 0.0223 (9) | |
H12B | 0.6022 | 0.1931 | 0.5124 | 0.027* | |
C13B | 1.0837 (5) | −0.2672 (3) | 0.2627 (2) | 0.0258 (9) | |
C14B | 0.3921 (5) | 0.2462 (3) | 0.79858 (18) | 0.0275 (9) | |
H14C | 0.5156 | 0.2308 | 0.8104 | 0.033* | |
H14D | 0.3193 | 0.1787 | 0.8115 | 0.033* | |
C15B | 0.3010 (5) | 0.3444 (3) | 0.83716 (18) | 0.0271 (9) | |
H15C | 0.3627 | 0.4134 | 0.8174 | 0.033* | |
H15D | 0.1723 | 0.3519 | 0.8298 | 0.033* | |
C16B | 0.3054 (5) | 0.3335 (3) | 0.91401 (19) | 0.0323 (10) | |
H16C | 0.2497 | 0.2622 | 0.9328 | 0.039* | |
H16D | 0.2280 | 0.3946 | 0.9363 | 0.039* | |
C17B | 0.4943 (5) | 0.3365 (3) | 0.93525 (19) | 0.0282 (9) | |
H17C | 0.4812 | 0.3259 | 0.9864 | 0.034* | |
H17D | 0.5710 | 0.2736 | 0.9149 | 0.034* | |
C18B | 0.5911 (5) | 0.4451 (3) | 0.91217 (19) | 0.0262 (9) | |
H18C | 0.6046 | 0.4567 | 0.8610 | 0.031* | |
H18D | 0.5169 | 0.5085 | 0.9331 | 0.031* | |
C19B | 0.7783 (5) | 0.4415 (3) | 0.93413 (19) | 0.0297 (9) | |
H19C | 0.8522 | 0.3779 | 0.9133 | 0.036* | |
H19D | 0.7647 | 0.4302 | 0.9853 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1A | 0.0309 (3) | 0.0316 (3) | 0.0571 (3) | −0.0023 (2) | −0.0119 (2) | −0.0021 (2) |
O1A | 0.0300 (16) | 0.0271 (15) | 0.0306 (16) | 0.0037 (12) | −0.0064 (13) | −0.0139 (13) |
N1A | 0.049 (2) | 0.035 (2) | 0.028 (2) | 0.0147 (18) | 0.0047 (19) | −0.0083 (17) |
N2A | 0.0214 (18) | 0.0230 (18) | 0.0249 (19) | 0.0009 (14) | −0.0026 (15) | −0.0024 (15) |
N3A | 0.0187 (17) | 0.0226 (18) | 0.0261 (19) | 0.0002 (14) | −0.0022 (15) | −0.0059 (15) |
C1A | 0.018 (2) | 0.020 (2) | 0.028 (2) | −0.0020 (16) | −0.0001 (18) | −0.0052 (18) |
C2A | 0.019 (2) | 0.020 (2) | 0.032 (2) | −0.0025 (16) | −0.0052 (19) | −0.0041 (18) |
C3A | 0.023 (2) | 0.023 (2) | 0.024 (2) | 0.0001 (17) | −0.0069 (19) | −0.0032 (18) |
C4A | 0.015 (2) | 0.021 (2) | 0.028 (2) | −0.0012 (16) | 0.0012 (18) | −0.0064 (18) |
C5A | 0.022 (2) | 0.018 (2) | 0.037 (2) | 0.0019 (16) | −0.006 (2) | −0.0047 (19) |
C6A | 0.032 (2) | 0.026 (2) | 0.020 (2) | −0.0012 (18) | −0.0044 (19) | −0.0028 (18) |
C7A | 0.015 (2) | 0.021 (2) | 0.028 (2) | −0.0022 (16) | −0.0037 (18) | −0.0066 (18) |
C8A | 0.019 (2) | 0.018 (2) | 0.033 (2) | 0.0021 (16) | −0.0062 (19) | −0.0037 (18) |
C9A | 0.029 (2) | 0.025 (2) | 0.020 (2) | −0.0013 (17) | −0.0024 (18) | −0.0002 (18) |
C10A | 0.019 (2) | 0.027 (2) | 0.026 (2) | −0.0031 (17) | 0.0013 (18) | −0.0076 (19) |
C11A | 0.022 (2) | 0.022 (2) | 0.036 (2) | 0.0057 (17) | −0.0095 (19) | −0.0075 (19) |
C12A | 0.022 (2) | 0.024 (2) | 0.025 (2) | 0.0030 (17) | −0.0062 (18) | −0.0027 (18) |
C13A | 0.024 (2) | 0.029 (2) | 0.029 (2) | −0.0039 (18) | −0.009 (2) | 0.0016 (19) |
C14A | 0.032 (2) | 0.028 (2) | 0.022 (2) | −0.0082 (18) | 0.0005 (19) | −0.0077 (18) |
C15A | 0.023 (2) | 0.040 (3) | 0.041 (3) | −0.0014 (19) | −0.001 (2) | −0.010 (2) |
C16A | 0.034 (2) | 0.023 (2) | 0.033 (2) | 0.0057 (18) | −0.006 (2) | −0.0102 (18) |
C17A | 0.026 (2) | 0.027 (2) | 0.033 (2) | 0.0046 (17) | −0.004 (2) | −0.0096 (18) |
C18A | 0.023 (2) | 0.027 (2) | 0.036 (2) | 0.0025 (17) | −0.009 (2) | −0.0058 (19) |
C19A | 0.026 (2) | 0.027 (2) | 0.044 (3) | 0.0019 (17) | −0.007 (2) | −0.0076 (19) |
Br1B | 0.0338 (3) | 0.0364 (3) | 0.0393 (3) | −0.0085 (2) | 0.0007 (2) | −0.0060 (2) |
O1B | 0.0245 (15) | 0.0263 (15) | 0.0284 (15) | 0.0026 (11) | −0.0007 (13) | −0.0122 (12) |
N1B | 0.038 (2) | 0.034 (2) | 0.028 (2) | 0.0033 (16) | −0.0022 (18) | −0.0039 (17) |
N2B | 0.0229 (18) | 0.0219 (18) | 0.0271 (19) | 0.0004 (14) | −0.0031 (16) | −0.0034 (15) |
N3B | 0.0192 (18) | 0.0212 (18) | 0.032 (2) | 0.0016 (14) | −0.0021 (16) | −0.0072 (16) |
C1B | 0.014 (2) | 0.022 (2) | 0.031 (2) | −0.0006 (16) | −0.0016 (18) | −0.0075 (18) |
C2B | 0.020 (2) | 0.021 (2) | 0.025 (2) | 0.0035 (16) | −0.0050 (18) | −0.0029 (18) |
C3B | 0.022 (2) | 0.027 (2) | 0.023 (2) | 0.0007 (17) | −0.0067 (19) | −0.0023 (19) |
C4B | 0.016 (2) | 0.019 (2) | 0.030 (2) | 0.0004 (16) | −0.0020 (18) | −0.0043 (18) |
C5B | 0.023 (2) | 0.019 (2) | 0.030 (2) | 0.0006 (17) | −0.0061 (19) | −0.0025 (18) |
C6B | 0.026 (2) | 0.026 (2) | 0.023 (2) | −0.0019 (18) | −0.0052 (19) | −0.0016 (18) |
C7B | 0.015 (2) | 0.023 (2) | 0.025 (2) | 0.0011 (16) | −0.0037 (17) | −0.0067 (18) |
C8B | 0.023 (2) | 0.020 (2) | 0.034 (2) | 0.0008 (17) | −0.010 (2) | −0.0023 (19) |
C9B | 0.023 (2) | 0.024 (2) | 0.026 (2) | −0.0033 (17) | −0.0027 (18) | −0.0014 (18) |
C10B | 0.016 (2) | 0.023 (2) | 0.032 (2) | 0.0017 (16) | −0.0048 (18) | −0.0109 (19) |
C11B | 0.018 (2) | 0.018 (2) | 0.028 (2) | 0.0025 (16) | −0.0044 (18) | −0.0017 (18) |
C12B | 0.025 (2) | 0.018 (2) | 0.024 (2) | 0.0036 (16) | −0.0049 (19) | −0.0029 (17) |
C13B | 0.026 (2) | 0.028 (2) | 0.025 (2) | −0.0019 (18) | −0.0077 (19) | 0.0035 (19) |
C14B | 0.032 (2) | 0.027 (2) | 0.024 (2) | 0.0040 (18) | −0.0055 (19) | −0.0117 (18) |
C15B | 0.024 (2) | 0.031 (2) | 0.026 (2) | 0.0007 (18) | −0.0037 (19) | −0.0058 (19) |
C16B | 0.025 (2) | 0.033 (2) | 0.037 (3) | −0.0014 (18) | 0.002 (2) | −0.011 (2) |
C17B | 0.030 (2) | 0.028 (2) | 0.028 (2) | 0.0043 (18) | −0.0039 (19) | −0.0120 (18) |
C18B | 0.024 (2) | 0.024 (2) | 0.031 (2) | 0.0071 (16) | −0.0049 (19) | −0.0063 (18) |
C19B | 0.032 (2) | 0.024 (2) | 0.034 (2) | −0.0040 (17) | −0.008 (2) | −0.0034 (18) |
Geometric parameters (Å, º) top
Br1A—C19A | 1.970 (3) | Br1B—C19B | 1.966 (3) |
O1A—C10A | 1.360 (4) | O1B—C10B | 1.372 (4) |
O1A—C14A | 1.433 (4) | O1B—C14B | 1.439 (4) |
N1A—C13A | 1.143 (4) | N1B—C13B | 1.150 (4) |
N2A—N3A | 1.256 (4) | N2B—N3B | 1.271 (4) |
N2A—C4A | 1.430 (4) | N2B—C4B | 1.425 (4) |
N3A—C7A | 1.420 (4) | N3B—C7B | 1.412 (4) |
C1A—C6A | 1.388 (5) | C1B—C2B | 1.386 (5) |
C1A—C2A | 1.404 (5) | C1B—C6B | 1.405 (5) |
C1A—C13A | 1.447 (5) | C1B—C13B | 1.450 (5) |
C2A—C3A | 1.360 (4) | C2B—C3B | 1.366 (4) |
C2A—H2AB | 0.9500 | C2B—H2BB | 0.9500 |
C3A—C4A | 1.390 (5) | C3B—C4B | 1.396 (5) |
C3A—H3AB | 0.9500 | C3B—H3BB | 0.9500 |
C4A—C5A | 1.407 (5) | C4B—C5B | 1.389 (5) |
C5A—C6A | 1.377 (4) | C5B—C6B | 1.371 (4) |
C5A—H5AA | 0.9500 | C5B—H5BA | 0.9500 |
C6A—H6AA | 0.9500 | C6B—H6BA | 0.9500 |
C7A—C8A | 1.379 (5) | C7B—C8B | 1.373 (5) |
C7A—C12A | 1.398 (5) | C7B—C12B | 1.403 (5) |
C8A—C9A | 1.390 (4) | C8B—C9B | 1.399 (5) |
C8A—H8AA | 0.9500 | C8B—H8BA | 0.9500 |
C9A—C10A | 1.387 (5) | C9B—C10B | 1.386 (5) |
C9A—H9AA | 0.9500 | C9B—H9BA | 0.9500 |
C10A—C11A | 1.403 (5) | C10B—C11B | 1.388 (5) |
C11A—C12A | 1.379 (4) | C11B—C12B | 1.361 (4) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C14A—C15A | 1.512 (5) | C14B—C15B | 1.513 (4) |
C14A—H14A | 0.9900 | C14B—H14C | 0.9900 |
C14A—H14B | 0.9900 | C14B—H14D | 0.9900 |
C15A—C16A | 1.511 (5) | C15B—C16B | 1.506 (5) |
C15A—H15A | 0.9900 | C15B—H15C | 0.9900 |
C15A—H15B | 0.9900 | C15B—H15D | 0.9900 |
C16A—C17A | 1.529 (5) | C16B—C17B | 1.530 (5) |
C16A—H16A | 0.9900 | C16B—H16C | 0.9900 |
C16A—H16B | 0.9900 | C16B—H16D | 0.9900 |
C17A—C18A | 1.530 (4) | C17B—C18B | 1.523 (5) |
C17A—H17A | 0.9900 | C17B—H17C | 0.9900 |
C17A—H17B | 0.9900 | C17B—H17D | 0.9900 |
C18A—C19A | 1.499 (5) | C18B—C19B | 1.520 (5) |
C18A—H18A | 0.9900 | C18B—H18C | 0.9900 |
C18A—H18B | 0.9900 | C18B—H18D | 0.9900 |
C19A—H19A | 0.9900 | C19B—H19C | 0.9900 |
C19A—H19B | 0.9900 | C19B—H19D | 0.9900 |
| | | |
C10A—O1A—C14A | 117.7 (3) | C10B—O1B—C14B | 118.5 (3) |
N3A—N2A—C4A | 113.2 (3) | N3B—N2B—C4B | 113.8 (3) |
N2A—N3A—C7A | 115.6 (3) | N2B—N3B—C7B | 114.4 (3) |
C6A—C1A—C2A | 120.4 (3) | C2B—C1B—C6B | 120.9 (3) |
C6A—C1A—C13A | 121.4 (3) | C2B—C1B—C13B | 118.7 (3) |
C2A—C1A—C13A | 118.2 (3) | C6B—C1B—C13B | 120.4 (3) |
C3A—C2A—C1A | 119.7 (3) | C3B—C2B—C1B | 119.6 (3) |
C3A—C2A—H2AB | 120.2 | C3B—C2B—H2BB | 120.2 |
C1A—C2A—H2AB | 120.2 | C1B—C2B—H2BB | 120.2 |
C2A—C3A—C4A | 120.6 (3) | C2B—C3B—C4B | 120.6 (3) |
C2A—C3A—H3AB | 119.7 | C2B—C3B—H3BB | 119.7 |
C4A—C3A—H3AB | 119.7 | C4B—C3B—H3BB | 119.7 |
C3A—C4A—C5A | 119.8 (3) | C5B—C4B—C3B | 119.3 (3) |
C3A—C4A—N2A | 124.0 (3) | C5B—C4B—N2B | 116.1 (3) |
C5A—C4A—N2A | 116.2 (3) | C3B—C4B—N2B | 124.6 (3) |
C6A—C5A—C4A | 119.7 (3) | C6B—C5B—C4B | 121.2 (4) |
C6A—C5A—H5AA | 120.1 | C6B—C5B—H5BA | 119.4 |
C4A—C5A—H5AA | 120.1 | C4B—C5B—H5BA | 119.4 |
C5A—C6A—C1A | 119.7 (3) | C5B—C6B—C1B | 118.4 (3) |
C5A—C6A—H6AA | 120.1 | C5B—C6B—H6BA | 120.8 |
C1A—C6A—H6AA | 120.1 | C1B—C6B—H6BA | 120.8 |
C8A—C7A—C12A | 119.7 (3) | C8B—C7B—C12B | 119.0 (3) |
C8A—C7A—N3A | 115.8 (3) | C8B—C7B—N3B | 117.4 (3) |
C12A—C7A—N3A | 124.5 (3) | C12B—C7B—N3B | 123.6 (3) |
C7A—C8A—C9A | 120.8 (3) | C7B—C8B—C9B | 120.9 (3) |
C7A—C8A—H8AA | 119.6 | C7B—C8B—H8BA | 119.5 |
C9A—C8A—H8AA | 119.6 | C9B—C8B—H8BA | 119.5 |
C10A—C9A—C8A | 119.5 (3) | C10B—C9B—C8B | 118.7 (3) |
C10A—C9A—H9AA | 120.2 | C10B—C9B—H9BA | 120.6 |
C8A—C9A—H9AA | 120.2 | C8B—C9B—H9BA | 120.6 |
O1A—C10A—C9A | 124.2 (3) | O1B—C10B—C9B | 123.6 (3) |
O1A—C10A—C11A | 116.0 (3) | O1B—C10B—C11B | 115.9 (3) |
C9A—C10A—C11A | 119.8 (3) | C9B—C10B—C11B | 120.6 (3) |
C12A—C11A—C10A | 120.1 (3) | C12B—C11B—C10B | 119.9 (3) |
C12A—C11A—H11A | 119.9 | C12B—C11B—H11B | 120.0 |
C10A—C11A—H11A | 119.9 | C10B—C11B—H11B | 120.0 |
C11A—C12A—C7A | 119.9 (3) | C11B—C12B—C7B | 120.8 (3) |
C11A—C12A—H12A | 120.0 | C11B—C12B—H12B | 119.6 |
C7A—C12A—H12A | 120.0 | C7B—C12B—H12B | 119.6 |
N1A—C13A—C1A | 178.5 (4) | N1B—C13B—C1B | 179.1 (4) |
O1A—C14A—C15A | 108.1 (3) | O1B—C14B—C15B | 107.4 (3) |
O1A—C14A—H14A | 110.1 | O1B—C14B—H14C | 110.2 |
C15A—C14A—H14A | 110.1 | C15B—C14B—H14C | 110.2 |
O1A—C14A—H14B | 110.1 | O1B—C14B—H14D | 110.2 |
C15A—C14A—H14B | 110.1 | C15B—C14B—H14D | 110.2 |
H14A—C14A—H14B | 108.4 | H14C—C14B—H14D | 108.5 |
C16A—C15A—C14A | 113.5 (3) | C16B—C15B—C14B | 113.3 (3) |
C16A—C15A—H15A | 108.9 | C16B—C15B—H15C | 108.9 |
C14A—C15A—H15A | 108.9 | C14B—C15B—H15C | 108.9 |
C16A—C15A—H15B | 108.9 | C16B—C15B—H15D | 108.9 |
C14A—C15A—H15B | 108.9 | C14B—C15B—H15D | 108.9 |
H15A—C15A—H15B | 107.7 | H15C—C15B—H15D | 107.7 |
C15A—C16A—C17A | 113.6 (3) | C15B—C16B—C17B | 115.9 (3) |
C15A—C16A—H16A | 108.8 | C15B—C16B—H16C | 108.3 |
C17A—C16A—H16A | 108.8 | C17B—C16B—H16C | 108.3 |
C15A—C16A—H16B | 108.8 | C15B—C16B—H16D | 108.3 |
C17A—C16A—H16B | 108.8 | C17B—C16B—H16D | 108.3 |
H16A—C16A—H16B | 107.7 | H16C—C16B—H16D | 107.4 |
C16A—C17A—C18A | 112.4 (3) | C18B—C17B—C16B | 113.4 (3) |
C16A—C17A—H17A | 109.1 | C18B—C17B—H17C | 108.9 |
C18A—C17A—H17A | 109.1 | C16B—C17B—H17C | 108.9 |
C16A—C17A—H17B | 109.1 | C18B—C17B—H17D | 108.9 |
C18A—C17A—H17B | 109.1 | C16B—C17B—H17D | 108.9 |
H17A—C17A—H17B | 107.9 | H17C—C17B—H17D | 107.7 |
C19A—C18A—C17A | 110.8 (3) | C19B—C18B—C17B | 110.4 (3) |
C19A—C18A—H18A | 109.5 | C19B—C18B—H18C | 109.6 |
C17A—C18A—H18A | 109.5 | C17B—C18B—H18C | 109.6 |
C19A—C18A—H18B | 109.5 | C19B—C18B—H18D | 109.6 |
C17A—C18A—H18B | 109.5 | C17B—C18B—H18D | 109.6 |
H18A—C18A—H18B | 108.1 | H18C—C18B—H18D | 108.1 |
C18A—C19A—Br1A | 110.1 (2) | C18B—C19B—Br1B | 110.7 (2) |
C18A—C19A—H19A | 109.6 | C18B—C19B—H19C | 109.5 |
Br1A—C19A—H19A | 109.6 | Br1B—C19B—H19C | 109.5 |
C18A—C19A—H19B | 109.6 | C18B—C19B—H19D | 109.5 |
Br1A—C19A—H19B | 109.6 | Br1B—C19B—H19D | 109.5 |
H19A—C19A—H19B | 108.2 | H19C—C19B—H19D | 108.1 |
| | | |
C4A—N2A—N3A—C7A | 179.7 (3) | C4B—N2B—N3B—C7B | 179.8 (3) |
C6A—C1A—C2A—C3A | 0.2 (5) | C6B—C1B—C2B—C3B | 1.7 (5) |
C13A—C1A—C2A—C3A | −180.0 (3) | C13B—C1B—C2B—C3B | 179.7 (3) |
C1A—C2A—C3A—C4A | −0.5 (5) | C1B—C2B—C3B—C4B | −1.3 (5) |
C2A—C3A—C4A—C5A | −0.3 (5) | C2B—C3B—C4B—C5B | 0.9 (5) |
C2A—C3A—C4A—N2A | −179.9 (3) | C2B—C3B—C4B—N2B | 179.8 (3) |
N3A—N2A—C4A—C3A | −3.4 (5) | N3B—N2B—C4B—C5B | −178.4 (3) |
N3A—N2A—C4A—C5A | 176.9 (3) | N3B—N2B—C4B—C3B | 2.6 (5) |
C3A—C4A—C5A—C6A | 1.4 (5) | C3B—C4B—C5B—C6B | −1.0 (5) |
N2A—C4A—C5A—C6A | −178.9 (3) | N2B—C4B—C5B—C6B | −180.0 (3) |
C4A—C5A—C6A—C1A | −1.7 (5) | C4B—C5B—C6B—C1B | 1.4 (5) |
C2A—C1A—C6A—C5A | 0.9 (5) | C2B—C1B—C6B—C5B | −1.8 (5) |
C13A—C1A—C6A—C5A | −178.9 (3) | C13B—C1B—C6B—C5B | −179.7 (3) |
N2A—N3A—C7A—C8A | −176.3 (3) | N2B—N3B—C7B—C8B | 179.6 (3) |
N2A—N3A—C7A—C12A | 3.3 (5) | N2B—N3B—C7B—C12B | −0.5 (5) |
C12A—C7A—C8A—C9A | −0.9 (5) | C12B—C7B—C8B—C9B | 1.1 (5) |
N3A—C7A—C8A—C9A | 178.7 (3) | N3B—C7B—C8B—C9B | −178.9 (3) |
C7A—C8A—C9A—C10A | −1.3 (5) | C7B—C8B—C9B—C10B | −0.2 (5) |
C14A—O1A—C10A—C9A | 2.1 (5) | C14B—O1B—C10B—C9B | 4.4 (5) |
C14A—O1A—C10A—C11A | −178.0 (3) | C14B—O1B—C10B—C11B | −175.8 (3) |
C8A—C9A—C10A—O1A | −176.9 (3) | C8B—C9B—C10B—O1B | 178.6 (3) |
C8A—C9A—C10A—C11A | 3.2 (5) | C8B—C9B—C10B—C11B | −1.1 (5) |
O1A—C10A—C11A—C12A | 177.0 (3) | O1B—C10B—C11B—C12B | −178.2 (3) |
C9A—C10A—C11A—C12A | −3.1 (5) | C9B—C10B—C11B—C12B | 1.6 (5) |
C10A—C11A—C12A—C7A | 0.9 (5) | C10B—C11B—C12B—C7B | −0.7 (5) |
C8A—C7A—C12A—C11A | 1.1 (5) | C8B—C7B—C12B—C11B | −0.7 (5) |
N3A—C7A—C12A—C11A | −178.5 (3) | N3B—C7B—C12B—C11B | 179.4 (3) |
C10A—O1A—C14A—C15A | 177.0 (3) | C10B—O1B—C14B—C15B | 176.0 (3) |
O1A—C14A—C15A—C16A | 65.0 (4) | O1B—C14B—C15B—C16B | −171.0 (3) |
C14A—C15A—C16A—C17A | 73.2 (4) | C14B—C15B—C16B—C17B | 66.4 (4) |
C15A—C16A—C17A—C18A | −172.0 (3) | C15B—C16B—C17B—C18B | 60.7 (4) |
C16A—C17A—C18A—C19A | 176.1 (3) | C16B—C17B—C18B—C19B | −179.2 (3) |
C17A—C18A—C19A—Br1A | −179.9 (2) | C17B—C18B—C19B—Br1B | 179.8 (2) |
Experimental details
| (Ia) | (IIIa) | (IIIc) |
Crystal data |
Chemical formula | C12H9N3O3 | C13H11N3O3 | C19H20BrN3O |
Mr | 243.22 | 257.25 | 386.29 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 110 | 298 | 110 |
a, b, c (Å) | 7.290 (4), 10.648 (6), 28.353 (16) | 6.1530 (12), 7.5500 (15), 13.683 (3) | 7.4279 (18), 12.009 (3), 19.552 (5) |
α, β, γ (°) | 93.685 (10), 94.922 (11), 100.811 (10) | 100.80 (3), 102.68 (3), 91.74 (3) | 86.502 (5), 80.511 (5), 87.604 (5) |
V (Å3) | 2147 (2) | 607.5 (2) | 1716.2 (7) |
Z | 8 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.10 | 2.41 |
Crystal size (mm) | 0.50 × 0.40 × 0.15 | 0.45 × 0.35 × 0.30 | 0.50 × 0.35 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Enraf-Nonius CAD-4 diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | – | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | – | – | 0.403, 0.697 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24813, 12208, 6579 | 2618, 2382, 1717 | 20166, 9845, 3353 |
Rint | 0.031 | 0.058 | 0.083 |
(sin θ/λ)max (Å−1) | 0.706 | 0.617 | 0.705 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.143, 0.89 | 0.046, 0.144, 1.04 | 0.047, 0.094, 0.68 |
No. of reflections | 12208 | 2382 | 9845 |
No. of parameters | 649 | 173 | 433 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.27 | 0.16, −0.19 | 1.17, −0.48 |
Selected geometric parameters (Å, º) for (Ia) topN2A—N3A | 1.2601 (19) | N2C—N3C | 1.2571 (19) |
N2A—C4A | 1.421 (2) | N2C—C4C | 1.423 (2) |
N3A—C7A | 1.414 (2) | N3C—C7C | 1.418 (2) |
N2B—N3B | 1.263 (2) | N2D—N3D | 1.2616 (19) |
N2B—C4B | 1.424 (2) | N2D—C4D | 1.424 (2) |
N3B—C7B | 1.416 (2) | N3D—C7D | 1.418 (2) |
| | | |
N3A—N2A—C4A | 113.87 (14) | N3C—N2C—C4C | 114.31 (14) |
N2A—N3A—C7A | 114.54 (14) | N2C—N3C—C7C | 113.77 (14) |
N3B—N2B—C4B | 114.43 (14) | N3D—N2D—C4D | 113.83 (13) |
N2B—N3B—C7B | 114.25 (14) | N2D—N3D—C7D | 114.22 (14) |
| | | |
C4A—N2A—N3A—C7A | 179.04 (14) | C4C—N2C—N3C—C7C | −178.84 (14) |
N3A—N2A—C4A—C3A | −6.4 (2) | N3C—N2C—C4C—C3C | −5.9 (2) |
N2A—N3A—C7A—C8A | −179.77 (15) | N2C—N3C—C7C—C8C | −176.74 (14) |
C4B—N2B—N3B—C7B | 179.42 (13) | C4D—N2D—N3D—C7D | 179.51 (13) |
N3B—N2B—C4B—C3B | 1.0 (2) | N3D—N2D—C4D—C3D | 2.4 (2) |
N2B—N3B—C7B—C8B | −179.12 (15) | N2D—N3D—C7D—C8D | 178.77 (15) |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O2Bi | 0.84 | 2.02 | 2.753 (2) | 146 |
O1B—H1B···O2A | 0.84 | 2.12 | 2.811 (2) | 140 |
O1C—H1C···O3D | 0.84 | 2.06 | 2.903 (2) | 177 |
O1D—H1D···O3Ci | 0.84 | 2.07 | 2.904 (2) | 174 |
Symmetry code: (i) x−1, y, z−1. |
Selected geometric parameters (Å, º) for (IIIa) topN2—N3 | 1.2485 (17) | N3—C7 | 1.4175 (18) |
N2—C4 | 1.4242 (18) | | |
| | | |
N3—N2—C4 | 114.99 (12) | N2—N3—C7 | 113.92 (12) |
| | | |
C4—N2—N3—C7 | −179.90 (10) | N2—N3—C7—C8 | −178.29 (13) |
N3—N2—C4—C3 | 1.7 (2) | | |
Hydrogen-bond geometry (Å, º) for (IIIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 0.93 | 2.57 | 3.412 (2) | 150 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (IIIc) topN2A—N3A | 1.256 (4) | N2B—N3B | 1.271 (4) |
N2A—C4A | 1.430 (4) | N2B—C4B | 1.425 (4) |
N3A—C7A | 1.420 (4) | N3B—C7B | 1.412 (4) |
| | | |
N3A—N2A—C4A | 113.2 (3) | N3B—N2B—C4B | 113.8 (3) |
N2A—N3A—C7A | 115.6 (3) | N2B—N3B—C7B | 114.4 (3) |
| | | |
C4A—N2A—N3A—C7A | 179.7 (3) | C4B—N2B—N3B—C7B | 179.8 (3) |
N3A—N2A—C4A—C3A | −3.4 (5) | N3B—N2B—C4B—C3B | 2.6 (5) |
N2A—N3A—C7A—C8A | −176.3 (3) | N2B—N3B—C7B—C8B | 179.6 (3) |
C14A—O1A—C10A—C9A | 2.1 (5) | C14B—O1B—C10B—C9B | 4.4 (5) |
C10A—O1A—C14A—C15A | 177.0 (3) | C10B—O1B—C14B—C15B | 176.0 (3) |
O1A—C14A—C15A—C16A | 65.0 (4) | O1B—C14B—C15B—C16B | −171.0 (3) |
C14A—C15A—C16A—C17A | 73.2 (4) | C14B—C15B—C16B—C17B | 66.4 (4) |
C15A—C16A—C17A—C18A | −172.0 (3) | C15B—C16B—C17B—C18B | 60.7 (4) |
C16A—C17A—C18A—C19A | 176.1 (3) | C16B—C17B—C18B—C19B | −179.2 (3) |
C17A—C18A—C19A—Br1A | −179.9 (2) | C17B—C18B—C19B—Br1B | 179.8 (2) |
Optically active azobenzene polymers are very important functional materials because of their photoresponsive properties. The pendant azobenzene moieties in these materials behave as both photoresponsive chromophores and mesogens (Rochon et al., 1995; Kim et al., 1995; Labarthet et al., 1999). Recently, the formation of holographic gratings with polymeric azobenzene liquid crystals (LC) containing only azobenzene moieties, where each moiety is mesogenic and photoresponsive, was reported (Yamamoto et al., 2000, 2001). The formation of optically active gratings by such polymers is related to the trans-cis isomerization of the chromophores, which leads to a nematic-isotropic phase transition, and thence to a real-time holographic grating (Hasegawa at al., 1999).
The present investigation is a continuation of a project that includes the synthesis, structural study and property evaluation of organic compounds for potential optical applications (Antipin et al., 1997, 1998, 2001; Nesterov et al., 1998; Timofeeva et al., 2000). Recently, we began the synthesis of new photorefractive LC polymers containing mesogenic polar azobenzene pendants. Despite the fact that the structures of many substituted azobenzenes are known, several basic compounds and LC azobenzene pendants have not been studied before now. Our goal was to investigate the influence of the substituent on the azobenzene core and to correlate the structure of the alkyl-tail pendant compound with its probable mesogenic activity.
In this paper, we present the results of the syntheses and structural investigations of three azobenzene derivatives, (E)-(4-hydroxyphenyl)(4-nitrophenyl)diazene, (Ia), (E)-(4-methoxyphenyl)(4-nitrophenyl)diazene, (IIIa), and (E)-[4-(6-bromohexyloxy)phenyl](4-cyanophenyl)diazene, (IIIc), and a description of the mesogenic properties of (IIIc). The synthetic route for the compounds investigated here and their general molecular structures are shown in the Scheme below. We were unable to crystallize compound (Ib) for X-ray analysis. Crystals of (IIIb) were of poor quality, so the data from the X-ray analysis of (IIIb) are not presented here. \sch
The X-ray analysis revealed that two of the crystals studied comprise more than one symmetrically independent molecule. Crystals of (Ia) contain four molecules in the asymmetric unit (A, B, C and D), and crystals of (IIIc) contain two molecules (A and B). The atom-labelling scheme for these molecules includes the letter corresponding to the independent molecule.
In all of the crystals, the azobenzene fragments have the trans conformation. The geometric parameters of the azobenzene cores in all three compounds (Tables 1, 3 and 5) do not differ from standard values (Allen et al., 1987), and they are very close to the literature data for other azobenzene derivatives (Howard et al., 1994; Zhang et al., 1997, 1998). In all three compounds, the azobenzene cores are almost planar. The dihedral angles between the two phenyl rings are 6.9, 2.5, 4.1 and 1.8° for (Ia) (molecules A—D, respectively), 3.5° for (IIIa), and 1.0 and 1.4° for molecules A and B, respectively, of (IIIc); torsion angle data are given in Tables 1, 3 and 5. The structures of molecules A—D in (Ia) are almost identical, and are presented in Fig. 1. The molecular structure of (IIIa) is shown in Fig. 2.
In crystal (IIIc), molecules A and B (Fig. 3) have different conformations of the Br-substituted alkyl tails (see torsion angles in Table 5). In both molecules, the tails do not have the standard all-trans conformation. In molecule A, two atoms of the alkyl tail (C14 and C15) lie in the plane of the azobenzene core, while in molecule B, three C atoms of the tail (C14—C16) belong to the planar fragment (Fig. 3). The angles between the rest of the C atoms of the tail and the planar core are 103.1 and 91.8° in molecules A and B, respectively. These observations demonstrate the flexibility of alkyl tails, not only in LC phases (Zorky et al., 1989), but also in their solid-state precursors.
Analysis of the bond lengths in the benzene rings of molecules (Ia), (IIIa) and (IIIc) did not demonstrate the quinoid character of bond distribution that is often observed in donor-acceptor substituted conjugated polar molecules.
In the crystal structure of (Ia), the planar molecules form molecular sheets parallel to the unit-cell diagonal plane (110). Within these sheets, molecules A and B and molecules B and C are connected into infinite hydrogen-bonded chains (Table 2). In the crystal structure of (IIIa), the molecules also form sheets that are parallel to the (210) diagonal plane, where molecules are held together by weak C—H···O hydrogen bonds (Table 4). A similar type of hydrogen bond was found in 4'-(dimethylamino)-2-nitroazobenzene (Zhang et al., 1998). Superposition of these sheets leads to the formation of centrosymmetric molecular stacks parallel to the b axis. Within these stacks, the molecules have a head-to-tail orientation and interplanar separations of 3.52 and 3.48 Å.
The molecules in (IIIc) also have a head-to-tail orientation, and form separate stacks of molecules A and B along the a axis, with an interplanar separation of about 3.45 Å in both stacks. A fragment of the molecular packing in the crystal of (IIIc) (Fig. 4) shows a marked separation of the azobenzene cores and alkyl tails, which is quite common for the crystal structures of LC precursors.
The short length of the alkyl tails suggests that (IIIc) may form a nematic phase on heating. This suggestion was confirmed by the results of a differential scanning calorimetry (DSC) analysis, which showed that (IIIc) melts at 374.1 K, with the formation of a nematic phase, and isotropization occurs at 376.4 K. The existence of a nematic mesophase in a narrow temperature interval was supported by observations of a texture change in (IIIc) on heating. We believe that, in this case, the nematic-isotropic transition might be related only to changes of tail conformation, without a change of conformation of the azobenzene core.
Parts of the text have been extensively reworded. Please check carefully to make sure the sense has not been altered.