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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 82| Part 8| August 2026|
https://doi.org/10.1107/S205698902600681X

Crystal structures of 2-meth­­oxy-5-nitro­aniline N-alkyl derivatives support color-center creation by a dipole-stacking mechanism

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Jonathan Filleya* and Ethan J. Craceb

aOligometrics, Inc., 2510 47th Street, Suite 208, Boulder, CO 80301, USA, and bAnalytical Resources Core, Colorado State University, Fort Collins, CO 80523, USA
*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 May 2026; accepted 27 June 2026; online 10 July 2026)

Two N-alkyl derivatives of 2-meth­oxy-5-nitro­aniline, namely, 2-meth­oxy-N-(4-methyl­benz­yl)-5-nitro­aniline ethanol quatersolvate (C15H16N2O3·0.25C2H5OH, orange crystals) and 2-meth­oxy-5-nitro-N-(tri­phenyl­meth­yl)aniline (C26H22N2O3, yellow crystals), have been prepared and analyzed by single-crystal X-ray diffraction to determine if these compounds display the same face-to-face π-stacking arrangement as observed in the un-alkyl­ated parent compound. The tri­phenyl­methyl derivative crystallizes with 0.25 ethanol mol­ecules, the contribution of which has been modeled with a solvent mask due to a high degree of disorder. The UV-Vis spectra show that the benzyl derivative displays concentration-dependent shifts in the visible portion of the spectrum, shifting to longer wavelengths with higher concentration, which is attributed to aggregation in solution. This behavior is similar to that observed for the parent compound. In contrast, the tri­phenyl­methyl derivative shows an attenuated concentration dependence on visible absorption, which does not display as great a red shift, and therefore represents a lesser tendency for aggregation in solution. The crystal packing for these compounds is distinguishing, with the benzyl derivative π-stacking in a face-to-face manner with dipole moments oriented anti-parallel, while the sterically demanding tri­phenyl­methyl group prevents direct π-stacking for this compound. The packing observed for these compounds supports the hypothesis that an inter­molecular charge-transfer process is responsible for the orange color of crystals of the benzyl derivative. It is concluded that sterically undemanding groups attached at the amino group could deliver materials which mimic the color center formation hypothesized for the parent compound. These types of structural changes may have useful applications in the field of organic semiconductors.

CCDC references: 2546245; 2546246

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1. Chemical context

In a prior communication from this laboratory (Filley, 2024View full citation), it was established that the crystal structure of 2-meth­oxy-5-nitro­aniline consists of hydrogen-bonded arrays of π-stacked mol­ecules with dipole moments oriented anti-parallel, where the hydrogen bonds are between both hydrogen atoms of the amine group and only one of the oxygen atoms of the nitro group. The close contacts of the aromatic rings, as well as the concentration-dependent red shift of the visible absorption spectra, were used to hypothesize that the orange–red color of the crystals, with light absorption near 490 nm, arises from an inter­molecular charge-transfer mechanism, similar to that seen in certain colored semiconductors. In order to probe the likelihood of this possibility, N-alkyl derivatives of 2-meth­oxy-5-nitro­aniline (hereinafter referred to as the parent) were prepared: 2-meth­oxy-N-(4-methyl­benz­yl)-5-nitro­aniline (1) and 2-meth­oxy-5-nitro-N-(tri­phenyl­methyl)­aniline (2). While the benzyl derivative forms orange crystals from ethanol, the tri­phenyl­methyl derivative forms yellow crystals, with both being suitable for single-crystal X-ray diffraction analysis. A UV-Vis analysis of both compounds reveals they have similar spectra in the UV region, with absorption maxima ranging from 380 to 392 nm (Table 1[link]), but the orange benzyl derivative has concentration-dependent spectra in the visible region, fully analogous to the spectra reported for the parent compound. The results are displayed in Fig. 1[link]. Aggregation of organic dyes, and the accompanying changes to spectral properties, is of inter­est to those seeking to advance the topic of organic electronics (González-Sánchez et al., 2026View full citation; Heyne, 2016View full citation). Other work has focused on the effects of packing on fluorescence emission from crystals (Zhang et al., 2022View full citation) and on the effects of co-crystallized mol­ecules (Tarai & Baruah, 2018View full citation). A motivation for making compounds 1 and 2 is the possibility that modifications of the parent could lead to compounds that will be suitable for specific needs or applications. In the realm of inorganic semiconductors, one is required to modify the crystal by modifying the elements or their composition, with no real anti­cipation of how the changes will affect the overall properties. If one contemplates exploiting the properties of the parent by modifying its mol­ecular structure, then data regarding how changes to the mol­ecule will affect its crystal structure and color become crucial. The results reported here show that modifying the amine with a benzyl group does not inter­fere with the ability of the aromatic rings of the aniline mol­ecules to approach each other and maintain the putative charge-transfer mechanism and color center formation. The more sterically demanding tri­phenyl­methyl group, on the other hand, does inter­fere with stacking and prevents formation of an orange color center. It is also noteworthy that the core color of both compounds arises from the tail of the UV spectrum into the visible region to give yellow solutions, and that aggregation and concentration-dependent spectral changes into regions of the visible spectrum close to 490 nm are only observed for the sterically unencumbered compound 1. Using the suite of organic reactions available for modifying amines, it is possible to imagine a host of derivatives capable of binding to surfaces, forming polymers, taking on liquid crystalline properties, or partaking in amphiphilic inter­actions, to name a few, with due consideration of the steric demand around the amine nitro­gen atom. The results reported here could help inform future endeavors along these lines.

[Scheme 1]

Table 1
Planarity of amine nitro­gen atoms for the compounds considered here

Torsion angles using the four atoms indicated in the Scheme. Uncertainties are +/- 0.2°. Spectroscopic data for each compound dissolved in acetone, 0.1 mM.
Compound Atoms used Torsion angle λmax (nm)
1 C4—C5—N2—C8 172.31 (13)° 392
2 C4—C5—N2—C8, C30—C31—N4—C34a,b –157.32 (19)°, 168.5 (2)° 383
Parentc C2—C1—N1—H1B –159.3° 380
Note: (a). The second value is for the second crystallographically independent mol­ecule. (b). The authors are indebted to a reviewer for pointing out the only other significant differences between the independent mol­ecules are in the tri­phenyl­methyl groups. (c). Taken from Filley (2024View full citation).
[Figure 1]
Figure 1
UV-visible region spectra for compound 1 (red), and compound 2 (black). Concentrations in acetone: solid, 20 mM, dashed, 2 mM.

2. Structural commentary

The molecular structures of compound 1 is shown in Fig. 2[link], and the two crystallographically independent molecules of compound 2 are shown in Figs. 3[link] and 4[link], respectively. Note that compound 2 crystallizes as two crystallographically independent mol­ecules, but the second mol­ecule is not displayed in Fig. 3[link] to help facilitate visual comparison to that of compound 1. Compounds 1 and 2 adopt a conformation in which the attached alkyl group is trans with respect to the meth­oxy group about the aromatic-amine C—N bond, with similar crystallographically determined distances for both compounds of 2.23 (3) Å (O3⋯H2) and 4.04 (3) Å (O3⋯C8). This conformation is most likely favored due to steric effects. The near-planarity of the amine nitro­gen atom suggests some delocalization of the lone-pair electrons on the nitro­gen atom into the aromatic ring, although the amine group is meta to the nitro group and therefore not directly conjugated to it. The planarity of the nitro­gen atoms here is compared to that of the parent compound in Table 1[link]. It is evident that the mol­ecule with its amine nitro­gen atom closest to planar (180°) is the less hindered compound 1, while the tri­phenyl­methyl derivative and the parent have comparably pyramidal amine N atoms. Based on these data, it appears the main factor controlling the geometry at the amine nitro­gen atom is crystal packing for these compounds, and not strong electronic effects that contribute to, or prevent, delocalization of the nitro­gen lone pair.

[Figure 2]
Figure 2
Mol­ecular structure of compound 1 with atoms displayed as displacement ellipsoids at the 50% probability level.
[Figure 3]
Figure 3
Molecular structure of the first crystallographically independent molecule of compound 2 with atoms displayed as displacement ellipsoids at the 50% probability level.
[Figure 4]
Figure 4
Molecular structure of the second crystallographically independent molecule of compound 2 with atoms displayed as displacement ellipsoids at the 50% probability level.

3. Supra­molecular features

The π-stacking observed for compound 1 is displayed in Fig. 5[link], which shows the unit cell and two additional mol­ecules at the bottom of the figure to highlight the stacking. While the central aromatic rings bearing the polar meth­oxy groups and the nitro groups stack in pairs with their dipole moments oriented anti-parallel, the next pair of mol­ecules is offset by an amount equivalent to the dimensions of the benzyl groups, which is about 6.5 Å. Pairs of face-to-face stacked benzyl groups stack against the central aromatic ring in an edge-to-face manner at an angle of 65.8 (3)°. A second set of benzyl groups exist, shown on the outermost mol­ecules to the right and left in Fig. 5[link], which also stack in a pair-wise fashion against the central aromatic rings at 66.2 (3)°, making the angle between the benzyl groups 48.6 (3)°. These angles constitute an isosceles triangle with the plane defined by the central aromatic ring as its base. All of the central aromatic rings are parallel in the crystal to within about 1°. This is in contrast to crystals of the parent compound, where each pair of π-stacked rings is face-to-face π-stacked to the next pair, and separate columns of stacked rings are angled with respect to each other. In addition, no hydrogen-bonding is observed here, while in the case of the parent compound the stacks are hydrogen-bonded together. For compound 1, the hypothesized color center formation due to charge transfer could be facilitated by overlap of delocalized electrons on the benzyl groups with the π-system of the central rings.

[Figure 5]
Figure 5
Unit cell and stacking arrangement in crystals of compound 1.

The packing observed for compound 2 in Fig. 6[link], with the unit cell depicted as well as three additional mol­ecules, shows the lack of direct π-stacking between the central aromatic rings bearing the meth­oxy and the nitro groups, but does show the dipole moments are oriented anti-parallel. The two sets of crystallographically independent molecules are distinctive: one set has its nitro groups directed at each other but offset by about 3.1 Å, and the other set has molecules which lie side-by-side. The former set has nitro groups which are about 2.6 Å from a meth­oxy hydrogen atom, while the latter set has nitro groups which are about 2.9 Å from the aniline NH group, which constitutes a weak hydrogen bond for only one set of mol­ecules. The angle between the two sets of central aromatic rings is 49.4 (2)°. The sterically bulky tri­phenyl­methyl group prevents direct face-to-face contact of the central aromatic rings, which gives rise to the yellow color of the crystals. The lower wavelength absorption indicates there is a higher-energy charge-transfer mechanism in crystals of compound 2, and further supports the existence of a more favorable charge-transfer process in crystals of compound 1.

[Figure 6]
Figure 6
Unit cell and stacking arrangement in crystals of compound 2.

4. Database survey

The authors are unaware of examples in the literature of simple anilines which have been alkyl­ated with the express purpose of changing the crystal π-stacking arrangement, and as a result, the color of the crystal. A red anthracene derivative has been studied as a potential organic semiconductor with the emphasis on intra­molecular charge transfer (Zaini et al., 2019View full citation). The stacking in these crystals could lend itself to inter­molecular charge transfer, but was not discussed by the authors. Crystals of N-(4-methyl­benz­yl)-3-nitro­aniline (Đaković et al., 2012View full citation) show the mol­ecule has a near planar amino group with a C—C—N—C torsion angle of 179.2°. In spite of intra­molecular hydrogen bonding in an N-(4-methyl­benz­yl)-substituted amino­coumarin, the amino group participates in a C—C—N—C torsion angle of 171.8° (Rambabu et al., 2010View full citation). Both these values can be compared to compound 1 in Table 1[link]. In N-trityl-2-(tritylsulfan­yl)aniline, the amino group has a similar pyramidal N atom of the amino group to compound 2, with no strong electron demand on the central aromatic ring (Neuba et al., 2011View full citation). A tri­phenyl­methyl-substituted Schiff base crystallizes in two crystallographically independent mol­ecules (Theppitak et al., 2014View full citation) similar to compound 2, but with analogous torsion angles that differ much less from each other (138.6 and −137.1°) than those in Table 1[link].

5. Synthesis and crystallization

Reagents were obtained from Aldrich and used as received except 2-meth­oxy-5-nitro­aniline, which was recrystallized from 95% v/v ethanol. Tri­phenyl­methyl ­chloride was stored in a desiccator.

Compound 1: A 9 ml vial was charged with 250 mg (1.5 mmol) 2-meth­oxy-5-nitro­aniline, 400 mg (4.8 mmol) NaHCO3, 2 ml tri­ethyl­eneglycol monomethyl ether and 220 µl (1.7 mmol) 4-methyl­benzyl chloride. The slurry was stirred and heated to 438±2 K for 5 min while monitoring with a thermocouple. The mixture was cooled to room temperature, poured into 30 ml water, and stirred at room temperature for 30 min. After filtration, the red filter cake was allowed to air dry; yield 275 mg (67%). This material was boiled in 10 ml 95% v/v ethanol, filtered, and allowed to crystallize overnight at 273 K. Filtration and washing with cold ethanol afforded orange crystals suitable for X-ray diffraction experiments; yield 125 mg (31%). 1H NMR (400 MHz, CDCl3): 2.40 (s, 3H), 3.98 (s, 3H), 4.39 (s, 2H), 4.80 (bs, 1H), 6.79–7.69 (m, 7H). 13C NMR (CDCl3): 21.1, 47.5, 56.0, 103.9, 107.9, 113.4, 127.9, 129.5, 135.1, 137.3, 138.2, 142.4, 151.6.

Compound 2: A slurry of 250 mg (1.5 mmol) 2-meth­oxy-5-nitro­aniline and 500 mg (6.0 mmol) NaHCO3 in 5 ml acetone was treated at room temperature with solid tri­phenyl­methyl­chloride (415 mg, 1.5 mmol) with stirring. After 2 h the mixture turned lemon yellow. The mixture was poured into 30 ml water to produce a gooey solid which could be triturated with a little ethanol to give a granular solid. After stirring for 1 h, the solids were filtered off and air dried overnight to give a yellow solid; yield, 542 mg (89%). This material was dissolved by boiling in a mixture of 10 ml 95% v/v ethanol + 10 ml acetone and filtered. After boiling to reduce the volume by 10-20%, cooling and seeding gave yellow diamond-shaped crystals; yield 382 mg (62%). 1H NMR (400 MHz, CDCl3): 4.00 (s, 3H), 5.95 (s, 1H), 6.73–7.53 (m, 18H). 13C NMR (CDCl3): 56.2, 71.3, 107.6, 109.3, 113.3, 126.8, 127.8, 128.4, 136.0, 141.3, 144.5, 151.9.

6. Refinement

Details of data collection and structure refinement are given in Table 2[link]. General refinement notes: Hydrogen atoms were inserted at idealized positions and refined using a riding model with isotropic parameters except for those on the amine nitro­gen atoms. The hydrogen atoms for the amine nitro­gen atoms were introduced with the AFIX 23 command in SHELXL (Sheldrick, 2015bView full citation) and then one of the hydrogen atoms was deleted from each amine. The remaining hydrogen-atom positions were then refined freely while still being restrained to idealized bond lengths. Specific additional procedures for each compound are found below.

Table 2
Experimental details

  1 2
Crystal data
Chemical formula C15H16N2O3 2C26H22N2O3·0.5C2H6O
Mr 272.31 843.99
Crystal system, space group Monoclinic, P21/c Triclinic, PMathematical equation
Temperature (K) 130 100
a, b, c (Å) 9.5017 (4), 15.7855 (7), 8.9908 (4) 9.0068 (3), 14.1142 (5), 18.2135 (6)
α, β, γ (°) 90, 95.230 (2), 90 103.152 (2), 98.267 (2), 106.000 (2)
V (Å3) 1342.91 (10) 2113.90 (13)
Z 4 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.10 0.09
Crystal size (mm) 0.29 × 0.17 × 0.05 0.14 × 0.05 × 0.03
 
Data collection
Diffractometer Bruker APEXII CCD Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Krause et al., 2015View full citation) Multi-scan (SADABS; Krause et al., 2015View full citation)
Tmin, Tmax 0.657, 0.746 0.654, 0.745
No. of measured, independent and observed [I ≥ 2u(I)] reflections 30573, 3078, 2497 35447, 8768, 6044
Rint 0.050 0.065
(sin θ/λ)max (Å−1) 0.649 0.628
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.136, 1.08 0.051, 0.120, 1.04
No. of reflections 3078 8768
No. of parameters 245 568
H-atom treatment All H-atom parameters refined H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.33, −0.38 0.40, −0.41
Computer programs: APEX5 and SAINT (Bruker, 2024View full citation), OLEX2.solve and OLEX2.refine (Bourhis et al., 2015View full citation), SHELXT (Sheldrick, 2015aView full citation), OLEX2 (Dolomanov et al., 2009View full citation) and publCIF (Westrip, 2010View full citation).

Compound 1: To eliminate residual electron density on bonds, the refinement was completed using NoSpherA2 using non-spherical scattering factors (Kleemiss et al., 2021View full citation). The density functional theory calculations used to obtain mol­ecular wavefunctions were calculated using ORCA 5.0 (Neese, 2012View full citation, 2022View full citation). The r2SCAN method was used with the cc-pVTZ basis set. Hydrogen atoms were refined isotropically.

Compound 2: A solvent mask was employed to model the electron density within a void that was partially occupied by ethanol (the solvent in the crystallization). The void is on a special position and the solvent appears to be disordered: 29 electrons were found in a volume of 116 Å3 in one void per unit cell. This is consistent with the presence of 0.5(C2H6O) per asymmetric unit, which accounts for 52 electrons per unit cell. Hence, there are 0.25 ethanol mol­ecules per one mol­ecule of analyte.

Supporting information

CCDC references: 2546245; 2546246

Crystal structure: contains datablocks 2, 1. DOI: https://doi.org/10.1107/S205698902600681X/wm5804sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S205698902600681X/wm58041sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S205698902600681X/wm58042sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902600681X/wm58042sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S205698902600681X/wm58041sup5.cml

checkCIF report


Computing details top

2-Methoxy-N-(4-methylbenzyl)-5-nitroaniline ethanol quatersolvate (2) top
Crystal data top
2C26H22N2O3·0.5C2H6OZ = 2
Mr = 843.99F(000) = 890.568
Triclinic, P1Dx = 1.326 Mg m−3
a = 9.0068 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.1142 (5) ÅCell parameters from 8823 reflections
c = 18.2135 (6) Åθ = 2.4–26.4°
α = 103.152 (2)°µ = 0.09 mm−1
β = 98.267 (2)°T = 100 K
γ = 106.000 (2)°Plate, clear light yellow
V = 2113.90 (13) Å30.14 × 0.05 × 0.03 mm
Data collection top
Bruker APEXII CCD
diffractometer		6044 reflections with I ≥ 2u(I)
φ and ω scansRint = 0.065
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		θmax = 26.5°, θmin = 1.6°
Tmin = 0.654, Tmax = 0.745h = −11→11
35447 measured reflectionsk = −17→17
8768 independent reflectionsl = −22→22
Refinement top
Refinement on F282 constraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.051 w = 1/[σ2(Fo2) + (0.0403P)2 + 1.2162P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120(Δ/σ)max = 0.0004
S = 1.04Δρmax = 0.40 e Å−3
8768 reflectionsΔρmin = −0.41 e Å−3
568 parametersExtinction correction: olex2.refine (Bourhis et al., 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0061 (7)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O6−0.05185 (16)0.86210 (10)0.63110 (8)0.0188 (3)
O50.2701 (2)0.54837 (12)0.70856 (10)0.0403 (5)
O40.11966 (19)0.45576 (11)0.59889 (8)0.0288 (4)
N40.1770 (2)0.89214 (13)0.74752 (9)0.0189 (4)
N30.1689 (2)0.53550 (13)0.65170 (10)0.0203 (4)
C340.2845 (2)0.92603 (14)0.82444 (11)0.0165 (4)
C350.2581 (2)1.02686 (15)0.86641 (11)0.0171 (4)
C360.2895 (3)1.10858 (15)0.83358 (12)0.0236 (5)
H360.3262 (3)1.10157 (15)0.78693 (12)0.0283 (6)*
C370.2669 (3)1.20014 (17)0.86905 (13)0.0312 (6)
H370.2857 (3)1.25488 (17)0.84578 (13)0.0375 (7)*
C380.2172 (3)1.21211 (17)0.93803 (13)0.0312 (5)
H380.2028 (3)1.27504 (17)0.96232 (13)0.0375 (7)*
C390.1886 (3)1.13228 (17)0.97133 (12)0.0273 (5)
H390.1551 (3)1.14043 (17)1.01887 (12)0.0328 (6)*
C400.2085 (2)1.03972 (16)0.93556 (11)0.0216 (5)
H400.1879 (2)0.98494 (16)0.95874 (11)0.0260 (5)*
C470.4591 (2)0.95285 (14)0.81814 (11)0.0167 (4)
C480.5783 (2)1.01270 (15)0.88356 (11)0.0200 (4)
H480.5504 (2)1.03492 (15)0.93140 (11)0.0241 (5)*
C490.7362 (3)1.03999 (16)0.87956 (12)0.0241 (5)
H490.8155 (3)1.08026 (16)0.92463 (12)0.0290 (6)*
C500.7793 (3)1.00897 (16)0.81028 (13)0.0266 (5)
H500.8877 (3)1.02721 (16)0.80765 (13)0.0319 (6)*
C510.6627 (3)0.95120 (16)0.74510 (12)0.0242 (5)
H510.6913 (3)0.93016 (16)0.69726 (12)0.0290 (6)*
C520.5041 (2)0.92349 (15)0.74876 (11)0.0194 (4)
H520.4253 (2)0.88402 (15)0.70329 (11)0.0233 (5)*
C410.2371 (2)0.84455 (14)0.86806 (11)0.0173 (4)
C420.3467 (3)0.82005 (15)0.91590 (11)0.0197 (4)
H420.4567 (3)0.85281 (15)0.92159 (11)0.0236 (5)*
C430.2966 (3)0.74791 (16)0.95556 (12)0.0242 (5)
H430.3727 (3)0.73284 (16)0.98890 (12)0.0291 (6)*
C440.1374 (3)0.69810 (16)0.94685 (12)0.0270 (5)
H440.1039 (3)0.64784 (16)0.97318 (12)0.0324 (6)*
C450.0268 (3)0.72190 (16)0.89944 (12)0.0247 (5)
H45−0.0831 (3)0.68799 (16)0.89318 (12)0.0296 (6)*
C460.0765 (2)0.79508 (15)0.86126 (11)0.0212 (5)
H46−0.0002 (2)0.81202 (15)0.82978 (11)0.0254 (5)*
C310.1201 (2)0.79496 (15)0.69631 (11)0.0168 (4)
C30−0.0050 (2)0.77825 (14)0.63240 (11)0.0157 (4)
C29−0.0699 (2)0.68361 (15)0.57784 (11)0.0176 (4)
H29−0.1521 (2)0.67426 (15)0.53519 (11)0.0211 (5)*
C28−0.0164 (2)0.60232 (15)0.58474 (11)0.0178 (4)
H28−0.0627 (2)0.53666 (15)0.54819 (11)0.0213 (5)*
C270.1062 (2)0.61928 (14)0.64617 (11)0.0163 (4)
C320.1759 (2)0.71389 (15)0.70176 (11)0.0183 (4)
H320.2608 (2)0.72280 (15)0.74298 (11)0.0219 (5)*
C33−0.1686 (3)0.85354 (16)0.56545 (12)0.0240 (5)
H33a−0.1305 (8)0.8348 (11)0.51819 (14)0.0360 (7)*
H33b−0.2674 (6)0.8005 (8)0.5630 (5)0.0360 (7)*
H33c−0.1878 (13)0.9195 (3)0.5703 (4)0.0360 (7)*
O30.16017 (17)0.25537 (11)0.69151 (8)0.0245 (3)
O20.67154 (18)0.06046 (11)0.60283 (9)0.0287 (4)
O10.46758 (19)−0.07656 (11)0.56056 (9)0.0297 (4)
N20.4656 (2)0.34466 (13)0.71727 (10)0.0230 (4)
N10.5281 (2)0.01637 (13)0.59118 (10)0.0225 (4)
C80.6181 (2)0.41256 (15)0.71099 (12)0.0197 (4)
C90.6202 (2)0.52349 (15)0.74515 (12)0.0192 (4)
C100.6793 (2)0.60141 (15)0.71176 (12)0.0207 (4)
H100.7179 (2)0.58612 (15)0.66608 (12)0.0248 (5)*
C110.6826 (2)0.70096 (15)0.74425 (12)0.0228 (5)
H110.7214 (2)0.75298 (15)0.72019 (12)0.0274 (6)*
C120.6298 (3)0.72491 (16)0.81120 (12)0.0244 (5)
H120.6316 (3)0.79315 (16)0.83320 (12)0.0293 (6)*
C130.5742 (3)0.64900 (16)0.84627 (13)0.0261 (5)
H130.5389 (3)0.66523 (16)0.89284 (13)0.0313 (6)*
C140.5700 (3)0.54874 (15)0.81331 (12)0.0234 (5)
H140.5323 (3)0.49707 (15)0.83784 (12)0.0280 (6)*
C210.7579 (3)0.40003 (15)0.76359 (12)0.0227 (5)
C220.9109 (3)0.46387 (16)0.77062 (12)0.0253 (5)
H220.9277 (3)0.51224 (16)0.74144 (12)0.0303 (6)*
C231.0391 (3)0.45803 (18)0.81951 (14)0.0362 (6)
H231.1428 (3)0.50184 (18)0.82349 (14)0.0435 (7)*
C241.0152 (4)0.3881 (2)0.86250 (15)0.0441 (7)
H241.1027 (4)0.3838 (2)0.89605 (15)0.0530 (8)*
H40.132 (3)0.937 (2)0.7371 (16)0.0530 (8)*
H20.391 (3)0.377 (2)0.7204 (16)0.0530 (8)*
C250.8645 (4)0.32474 (19)0.85655 (14)0.0424 (7)
H250.8484 (4)0.27654 (19)0.88588 (14)0.0508 (8)*
C260.7358 (3)0.33096 (17)0.80789 (13)0.0309 (5)
H260.6321 (3)0.28779 (17)0.80484 (13)0.0371 (7)*
C150.6266 (2)0.39124 (14)0.62520 (12)0.0188 (4)
C160.7381 (2)0.35243 (15)0.59517 (12)0.0208 (4)
H160.8210 (2)0.34427 (15)0.62920 (12)0.0250 (5)*
C170.7298 (3)0.32537 (16)0.51600 (13)0.0258 (5)
H170.8052 (3)0.29715 (16)0.49632 (13)0.0310 (6)*
C180.6129 (3)0.33928 (16)0.46598 (12)0.0263 (5)
H180.6073 (3)0.32081 (16)0.41190 (12)0.0315 (6)*
C190.5037 (3)0.38041 (15)0.49526 (12)0.0246 (5)
H190.4248 (3)0.39219 (15)0.46121 (12)0.0295 (6)*
C200.5085 (2)0.40457 (15)0.57389 (12)0.0208 (4)
H200.4306 (2)0.43049 (15)0.59303 (12)0.0249 (5)*
C50.4060 (2)0.24086 (15)0.67691 (11)0.0197 (4)
C40.2406 (3)0.19186 (15)0.66358 (11)0.0207 (4)
C30.1729 (3)0.08827 (16)0.62569 (12)0.0238 (5)
H30.0615 (3)0.05735 (16)0.61644 (12)0.0285 (6)*
C20.2658 (3)0.02902 (16)0.60106 (12)0.0230 (5)
H2a0.2198 (3)−0.04222 (16)0.57532 (12)0.0276 (6)*
C10.4264 (2)0.07654 (15)0.61505 (11)0.0195 (4)
C60.4986 (3)0.18088 (15)0.65251 (12)0.0215 (5)
H60.6101 (3)0.21076 (15)0.66129 (12)0.0258 (5)*
C7−0.0070 (3)0.21186 (18)0.68010 (14)0.0299 (5)
H7a−0.0547 (3)0.1865 (11)0.62459 (14)0.0448 (8)*
H7b−0.0308 (3)0.1548 (8)0.7033 (8)0.0448 (8)*
H7c−0.0505 (3)0.2644 (4)0.7045 (8)0.0448 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O60.0195 (7)0.0163 (7)0.0175 (7)0.0048 (6)−0.0009 (6)0.0028 (5)
O50.0435 (11)0.0264 (9)0.0399 (10)0.0161 (8)−0.0183 (8)−0.0008 (7)
O40.0369 (9)0.0187 (8)0.0250 (8)0.0111 (7)−0.0002 (7)−0.0030 (6)
N40.0222 (9)0.0148 (8)0.0158 (8)0.0056 (7)−0.0025 (7)0.0013 (7)
N30.0192 (9)0.0180 (9)0.0201 (9)0.0037 (7)0.0021 (7)0.0024 (7)
C340.0174 (10)0.0148 (10)0.0142 (9)0.0043 (8)−0.0001 (8)0.0015 (7)
C350.0146 (10)0.0159 (10)0.0166 (10)0.0048 (8)−0.0030 (8)0.0003 (8)
C360.0323 (12)0.0197 (11)0.0160 (10)0.0074 (9)0.0013 (9)0.0032 (8)
C370.0451 (15)0.0219 (12)0.0262 (12)0.0133 (11)0.0001 (11)0.0074 (9)
C380.0430 (15)0.0229 (12)0.0270 (12)0.0181 (11)0.0015 (10)0.0000 (9)
C390.0319 (13)0.0275 (12)0.0192 (11)0.0112 (10)0.0044 (9)−0.0010 (9)
C400.0232 (11)0.0215 (11)0.0180 (10)0.0074 (9)0.0015 (8)0.0029 (8)
C470.0205 (11)0.0124 (9)0.0176 (10)0.0049 (8)0.0038 (8)0.0060 (8)
C480.0218 (11)0.0201 (10)0.0178 (10)0.0058 (9)0.0033 (8)0.0063 (8)
C490.0202 (11)0.0212 (11)0.0259 (11)0.0008 (9)−0.0013 (9)0.0078 (9)
C500.0222 (12)0.0253 (12)0.0360 (13)0.0062 (9)0.0082 (10)0.0166 (10)
C510.0293 (12)0.0228 (11)0.0262 (11)0.0101 (9)0.0125 (9)0.0117 (9)
C520.0237 (11)0.0145 (10)0.0191 (10)0.0048 (9)0.0035 (8)0.0050 (8)
C410.0218 (11)0.0131 (10)0.0137 (9)0.0043 (8)0.0037 (8)−0.0007 (7)
C420.0225 (11)0.0178 (10)0.0193 (10)0.0078 (9)0.0067 (8)0.0032 (8)
C430.0352 (13)0.0221 (11)0.0177 (10)0.0121 (10)0.0069 (9)0.0059 (8)
C440.0416 (14)0.0170 (11)0.0230 (11)0.0063 (10)0.0142 (10)0.0060 (9)
C450.0240 (12)0.0195 (11)0.0254 (11)−0.0002 (9)0.0086 (9)0.0030 (9)
C460.0205 (11)0.0209 (11)0.0187 (10)0.0044 (9)0.0042 (8)0.0017 (8)
C310.0167 (10)0.0161 (10)0.0131 (9)−0.0004 (8)0.0037 (8)0.0019 (8)
C300.0146 (10)0.0163 (10)0.0166 (10)0.0038 (8)0.0056 (8)0.0055 (8)
C290.0152 (10)0.0192 (10)0.0165 (10)0.0038 (8)0.0027 (8)0.0039 (8)
C280.0159 (10)0.0151 (10)0.0163 (10)0.0004 (8)0.0029 (8)−0.0013 (8)
C270.0165 (10)0.0136 (9)0.0185 (10)0.0038 (8)0.0057 (8)0.0044 (8)
C320.0182 (10)0.0180 (10)0.0158 (10)0.0037 (8)0.0019 (8)0.0030 (8)
C330.0244 (12)0.0201 (11)0.0232 (11)0.0065 (9)−0.0045 (9)0.0049 (9)
O30.0236 (8)0.0186 (7)0.0306 (8)0.0057 (6)0.0082 (6)0.0055 (6)
O20.0256 (9)0.0227 (8)0.0357 (9)0.0057 (7)0.0078 (7)0.0057 (7)
O10.0381 (10)0.0139 (8)0.0311 (9)0.0066 (7)0.0040 (7)−0.0009 (6)
N20.0233 (10)0.0130 (9)0.0303 (10)0.0014 (7)0.0132 (8)0.0024 (7)
N10.0302 (11)0.0165 (9)0.0191 (9)0.0057 (8)0.0039 (8)0.0049 (7)
C80.0188 (11)0.0142 (10)0.0257 (11)0.0030 (8)0.0091 (9)0.0053 (8)
C90.0159 (10)0.0140 (10)0.0248 (11)0.0031 (8)0.0033 (8)0.0027 (8)
C100.0178 (11)0.0182 (10)0.0237 (11)0.0037 (8)0.0055 (8)0.0032 (8)
C110.0213 (11)0.0154 (10)0.0292 (12)0.0030 (9)0.0034 (9)0.0062 (9)
C120.0240 (12)0.0145 (10)0.0303 (12)0.0069 (9)0.0016 (9)−0.0003 (9)
C130.0266 (12)0.0222 (11)0.0265 (12)0.0084 (9)0.0077 (9)−0.0006 (9)
C140.0237 (11)0.0170 (10)0.0275 (11)0.0033 (9)0.0080 (9)0.0049 (9)
C210.0336 (13)0.0140 (10)0.0204 (11)0.0083 (9)0.0074 (9)0.0026 (8)
C220.0296 (12)0.0167 (11)0.0269 (12)0.0086 (9)0.0020 (9)0.0025 (9)
C230.0375 (15)0.0266 (13)0.0365 (14)0.0139 (11)−0.0050 (11)−0.0031 (10)
C240.0617 (19)0.0322 (14)0.0345 (14)0.0269 (14)−0.0113 (13)0.0007 (11)
C250.078 (2)0.0257 (13)0.0254 (13)0.0236 (14)0.0033 (13)0.0074 (10)
C260.0480 (15)0.0200 (11)0.0238 (11)0.0098 (11)0.0094 (11)0.0049 (9)
C150.0210 (11)0.0100 (9)0.0237 (10)0.0019 (8)0.0075 (8)0.0041 (8)
C160.0209 (11)0.0141 (10)0.0278 (11)0.0041 (8)0.0081 (9)0.0066 (8)
C170.0281 (12)0.0191 (11)0.0316 (12)0.0061 (9)0.0167 (10)0.0052 (9)
C180.0310 (13)0.0190 (11)0.0215 (11)−0.0020 (9)0.0090 (9)0.0020 (9)
C190.0225 (12)0.0175 (10)0.0271 (12)−0.0011 (9)0.0003 (9)0.0060 (9)
C200.0175 (11)0.0142 (10)0.0288 (11)0.0012 (8)0.0085 (9)0.0055 (8)
C50.0255 (11)0.0149 (10)0.0186 (10)0.0035 (8)0.0084 (9)0.0057 (8)
C40.0265 (12)0.0198 (10)0.0174 (10)0.0069 (9)0.0076 (9)0.0072 (8)
C30.0244 (12)0.0187 (11)0.0237 (11)0.0009 (9)0.0020 (9)0.0066 (9)
C20.0277 (12)0.0156 (10)0.0211 (11)0.0019 (9)0.0022 (9)0.0043 (8)
C10.0260 (11)0.0157 (10)0.0181 (10)0.0060 (9)0.0080 (9)0.0063 (8)
C60.0265 (12)0.0151 (10)0.0215 (10)0.0012 (9)0.0097 (9)0.0063 (8)
C70.0196 (12)0.0292 (12)0.0385 (13)0.0069 (10)0.0057 (10)0.0065 (10)
Geometric parameters (Å, º) top
O6—C301.365 (2)O3—C41.357 (2)
O6—C331.433 (2)O3—C71.424 (3)
O5—N31.220 (2)O2—N11.233 (2)
O4—N31.224 (2)O1—N11.230 (2)
N4—C341.476 (2)N2—C81.479 (3)
N4—C311.381 (2)N2—H20.91 (3)
N4—H40.88 (3)N2—C51.392 (2)
N3—C271.460 (3)N1—C11.457 (3)
C34—C351.552 (3)C8—C91.541 (3)
C34—C471.541 (3)C8—C211.545 (3)
C34—C411.542 (3)C8—C151.540 (3)
C35—C361.397 (3)C9—C101.392 (3)
C35—C401.386 (3)C9—C141.386 (3)
C36—H360.9500C10—H100.9500
C36—C371.390 (3)C10—C111.385 (3)
C37—H370.9500C11—H110.9500
C37—C381.384 (3)C11—C121.376 (3)
C38—H380.9500C12—H120.9500
C38—C391.378 (3)C12—C131.384 (3)
C39—H390.9500C13—H130.9500
C39—C401.392 (3)C13—C141.393 (3)
C40—H400.9500C14—H140.9500
C47—C481.400 (3)C21—C221.392 (3)
C47—C521.391 (3)C21—C261.392 (3)
C48—H480.9500C22—H220.9500
C48—C491.385 (3)C22—C231.387 (3)
C49—H490.9500C23—H230.9500
C49—C501.385 (3)C23—C241.384 (4)
C50—H500.9500C24—H240.9500
C50—C511.380 (3)C24—C251.378 (4)
C51—H510.9500C25—H250.9500
C51—C521.390 (3)C25—C261.390 (4)
C52—H520.9500C26—H260.9500
C41—C421.390 (3)C15—C161.389 (3)
C41—C461.396 (3)C15—C201.395 (3)
C42—H420.9500C16—H160.9500
C42—C431.392 (3)C16—C171.390 (3)
C43—H430.9500C17—H170.9500
C43—C441.380 (3)C17—C181.377 (3)
C44—H440.9500C18—H180.9500
C44—C451.386 (3)C18—C191.383 (3)
C45—H450.9500C19—H190.9500
C45—C461.383 (3)C19—C201.386 (3)
C46—H460.9500C20—H200.9500
C31—C301.426 (3)C5—C41.417 (3)
C31—C321.388 (3)C5—C61.391 (3)
C30—C291.383 (3)C4—C31.383 (3)
C29—H290.9500C3—H30.9500
C29—C281.385 (3)C3—C21.387 (3)
C28—H280.9500C2—H2a0.9500
C28—C271.380 (3)C2—C11.375 (3)
C27—C321.394 (3)C1—C61.394 (3)
C32—H320.9500C6—H60.9500
C33—H33a0.9800C7—H7a0.9800
C33—H33b0.9800C7—H7b0.9800
C33—H33c0.9800C7—H7c0.9800
C33—O6—C30117.50 (15)C7—O3—C4117.24 (16)
C31—N4—C34127.94 (17)H2—N2—C8112.6 (18)
H4—N4—C34114.7 (18)C5—N2—C8122.36 (17)
H4—N4—C31116.5 (18)C5—N2—H2114.2 (18)
O4—N3—O5122.52 (18)O1—N1—O2122.52 (18)
C27—N3—O5118.50 (16)C1—N1—O2118.72 (16)
C27—N3—O4118.97 (16)C1—N1—O1118.76 (17)
C35—C34—N4104.61 (15)C9—C8—N2106.31 (16)
C47—C34—N4111.29 (16)C21—C8—N2110.58 (17)
C47—C34—C35107.52 (15)C21—C8—C9105.36 (16)
C41—C34—N4109.74 (15)C15—C8—N2108.77 (16)
C41—C34—C35110.01 (16)C15—C8—C9111.68 (16)
C41—C34—C47113.28 (16)C15—C8—C21113.87 (17)
C36—C35—C34118.19 (18)C10—C9—C8121.87 (18)
C40—C35—C34122.85 (18)C14—C9—C8119.73 (18)
C40—C35—C36118.94 (19)C14—C9—C10118.31 (18)
H36—C36—C35119.94 (12)H10—C10—C9119.57 (12)
C37—C36—C35120.1 (2)C11—C10—C9120.9 (2)
C37—C36—H36119.94 (13)C11—C10—H10119.57 (13)
H37—C37—C36119.79 (13)H11—C11—C10119.82 (13)
C38—C37—C36120.4 (2)C12—C11—C10120.4 (2)
C38—C37—H37119.79 (13)C12—C11—H11119.82 (12)
H38—C38—C37120.16 (13)H12—C12—C11120.20 (12)
C39—C38—C37119.7 (2)C13—C12—C11119.61 (19)
C39—C38—H38120.16 (13)C13—C12—H12120.20 (13)
H39—C39—C38119.88 (13)H13—C13—C12120.00 (13)
C40—C39—C38120.2 (2)C14—C13—C12120.0 (2)
C40—C39—H39119.88 (13)C14—C13—H13120.00 (13)
C39—C40—C35120.6 (2)C13—C14—C9120.8 (2)
H40—C40—C35119.72 (12)H14—C14—C9119.60 (12)
H40—C40—C39119.72 (13)H14—C14—C13119.60 (13)
C48—C47—C34119.47 (17)C22—C21—C8119.17 (18)
C52—C47—C34122.54 (17)C26—C21—C8122.3 (2)
C52—C47—C48117.94 (19)C26—C21—C22118.4 (2)
H48—C48—C47119.52 (12)H22—C22—C21119.45 (12)
C49—C48—C47120.96 (19)C23—C22—C21121.1 (2)
C49—C48—H48119.52 (12)C23—C22—H22119.45 (15)
H49—C49—C48119.79 (12)H23—C23—C22120.13 (15)
C50—C49—C48120.4 (2)C24—C23—C22119.7 (3)
C50—C49—H49119.79 (13)C24—C23—H23120.13 (16)
H50—C50—C49120.41 (13)H24—C24—C23120.05 (16)
C51—C50—C49119.2 (2)C25—C24—C23119.9 (2)
C51—C50—H50120.41 (13)C25—C24—H24120.05 (14)
H51—C51—C50119.67 (13)H25—C25—C24119.81 (14)
C52—C51—C50120.7 (2)C26—C25—C24120.4 (2)
C52—C51—H51119.67 (12)C26—C25—H25119.81 (15)
C51—C52—C47120.81 (19)C25—C26—C21120.5 (2)
H52—C52—C47119.59 (12)H26—C26—C21119.77 (14)
H52—C52—C51119.59 (12)H26—C26—C25119.77 (16)
C42—C41—C34123.17 (18)C16—C15—C8123.83 (18)
C46—C41—C34118.65 (18)C20—C15—C8117.86 (18)
C46—C41—C42118.15 (18)C20—C15—C16118.14 (19)
H42—C42—C41119.72 (12)H16—C16—C15119.54 (12)
C43—C42—C41120.6 (2)C17—C16—C15120.9 (2)
C43—C42—H42119.72 (13)C17—C16—H16119.54 (13)
H43—C43—C42119.74 (13)H17—C17—C16119.84 (13)
C44—C43—C42120.5 (2)C18—C17—C16120.3 (2)
C44—C43—H43119.74 (13)C18—C17—H17119.84 (13)
H44—C44—C43120.23 (13)H18—C18—C17120.32 (13)
C45—C44—C43119.5 (2)C19—C18—C17119.4 (2)
C45—C44—H44120.23 (13)C19—C18—H18120.32 (13)
H45—C45—C44120.04 (13)H19—C19—C18119.75 (13)
C46—C45—C44119.9 (2)C20—C19—C18120.5 (2)
C46—C45—H45120.04 (13)C20—C19—H19119.75 (13)
C45—C46—C41121.3 (2)C19—C20—C15120.7 (2)
H46—C46—C41119.35 (12)H20—C20—C15119.65 (12)
H46—C46—C45119.35 (13)H20—C20—C19119.65 (13)
C30—C31—N4116.45 (18)C4—C5—N2117.61 (18)
C32—C31—N4125.42 (18)C6—C5—N2124.45 (19)
C32—C31—C30118.12 (17)C6—C5—C4117.85 (18)
C31—C30—O6114.33 (16)C5—C4—O3113.88 (17)
C29—C30—O6124.80 (17)C3—C4—O3125.07 (19)
C29—C30—C31120.88 (18)C3—C4—C5121.0 (2)
H29—C29—C30119.67 (12)H3—C3—C4119.59 (13)
C28—C29—C30120.67 (18)C2—C3—C4120.8 (2)
C28—C29—H29119.67 (11)C2—C3—H3119.59 (12)
H28—C28—C29120.90 (11)H2a—C2—C3121.03 (12)
C27—C28—C29118.21 (18)C1—C2—C3117.95 (19)
C27—C28—H28120.90 (11)C1—C2—H2a121.03 (12)
C28—C27—N3118.57 (17)C2—C1—N1119.50 (18)
C32—C27—N3118.63 (17)C6—C1—N1117.66 (18)
C32—C27—C28122.76 (18)C6—C1—C2122.8 (2)
C27—C32—C31119.33 (18)C1—C6—C5119.5 (2)
H32—C32—C31120.33 (11)H6—C6—C5120.26 (12)
H32—C32—C27120.33 (12)H6—C6—C1120.26 (13)
H33a—C33—O6109.5H7a—C7—O3109.5
H33b—C33—O6109.5H7b—C7—O3109.5
H33b—C33—H33a109.5H7b—C7—H7a109.5
H33c—C33—O6109.5H7c—C7—O3109.5
H33c—C33—H33a109.5H7c—C7—H7a109.5
H33c—C33—H33b109.5H7c—C7—H7b109.5
O6—C30—C31—N4−0.19 (19)O3—C4—C5—N21.3 (2)
O6—C30—C31—C32−179.47 (16)O3—C4—C5—C6177.91 (17)
O6—C30—C29—C28−178.88 (19)O3—C4—C3—C2−178.2 (2)
O5—N3—C27—C28−175.33 (19)O2—N1—C1—C2178.66 (18)
O5—N3—C27—C326.6 (2)O2—N1—C1—C6−2.2 (2)
O4—N3—C27—C285.6 (2)O1—N1—C1—C2−1.7 (2)
O4—N3—C27—C32−172.43 (18)O1—N1—C1—C6177.38 (18)
N4—C34—C35—C36−59.97 (18)N2—C8—C9—C10−139.86 (16)
N4—C34—C35—C40121.49 (16)N2—C8—C9—C1443.7 (2)
N4—C34—C47—C48162.14 (16)N2—C8—C21—C22−174.68 (16)
N4—C34—C47—C52−15.09 (19)N2—C8—C21—C261.6 (2)
N4—C34—C41—C42142.93 (16)N2—C8—C15—C16−116.44 (17)
N4—C34—C41—C46−39.12 (19)N2—C8—C15—C2058.65 (18)
N4—C31—C30—C29179.90 (17)N2—C5—C4—C3−178.29 (18)
N4—C31—C32—C27179.4 (2)N2—C5—C6—C1177.5 (2)
N3—C27—C28—C29−176.91 (17)N1—C1—C2—C3178.96 (18)
N3—C27—C32—C31178.54 (17)N1—C1—C6—C5−179.38 (17)
C34—N4—C31—C30168.5 (2)C8—N2—C5—C4−157.32 (19)
C34—N4—C31—C32−12.2 (2)C8—N2—C5—C626.3 (2)
C34—C35—C36—C37179.74 (19)C8—C9—C10—C11−178.86 (19)
C34—C35—C40—C39179.20 (19)C8—C9—C14—C13178.52 (19)
C34—C47—C48—C49−178.65 (18)C8—C21—C22—C23177.44 (19)
C34—C47—C52—C51178.52 (18)C8—C21—C26—C25−177.7 (2)
C34—C41—C42—C43178.11 (18)C8—C15—C16—C17173.58 (18)
C34—C41—C46—C45−179.53 (17)C8—C15—C20—C19−175.86 (17)
C35—C34—N4—C31−159.77 (15)C9—C8—N2—C5165.03 (15)
C35—C34—C47—C4848.13 (18)C9—C8—C21—C22−60.21 (18)
C35—C34—C47—C52−129.10 (15)C9—C8—C21—C26116.02 (17)
C35—C34—C41—C42−102.49 (17)C9—C8—C15—C16126.54 (17)
C35—C34—C41—C4675.46 (17)C9—C8—C15—C20−58.37 (18)
C35—C36—C37—C381.6 (3)C9—C10—C11—C121.2 (2)
C35—C40—C39—C380.4 (2)C9—C14—C13—C12−0.4 (3)
C36—C35—C34—C4758.44 (19)C10—C9—C8—C21102.7 (2)
C36—C35—C34—C41−177.77 (19)C10—C9—C8—C15−21.4 (2)
C36—C35—C40—C390.7 (2)C10—C9—C14—C131.9 (2)
C36—C37—C38—C39−0.6 (3)C10—C11—C12—C130.4 (2)
C37—C36—C35—C40−1.7 (3)C11—C10—C9—C14−2.3 (2)
C37—C38—C39—C40−0.4 (3)C11—C12—C13—C14−0.8 (2)
C40—C35—C34—C47−120.1 (2)C14—C9—C8—C21−73.7 (2)
C40—C35—C34—C413.7 (2)C14—C9—C8—C15162.2 (2)
C47—C34—N4—C3184.41 (18)C21—C8—N2—C5−81.10 (18)
C47—C34—C41—C4217.87 (19)C21—C8—C15—C167.4 (2)
C47—C34—C41—C46−164.18 (16)C21—C8—C15—C20−177.56 (16)
C47—C48—C49—C500.4 (2)C21—C22—C23—C24−0.3 (3)
C47—C52—C51—C50−0.3 (2)C21—C26—C25—C241.1 (3)
C48—C47—C34—C41−73.64 (19)C22—C21—C8—C1562.5 (2)
C48—C47—C52—C511.3 (2)C22—C21—C26—C25−1.4 (2)
C48—C49—C50—C510.5 (2)C22—C23—C24—C250.0 (3)
C49—C48—C47—C52−1.3 (2)C23—C22—C21—C261.1 (3)
C49—C50—C51—C52−0.6 (2)C23—C24—C25—C26−0.3 (3)
C52—C47—C34—C41109.13 (19)C26—C21—C8—C15−121.3 (2)
C41—C34—N4—C31−41.8 (2)C15—C8—N2—C544.6 (2)
C41—C42—C43—C441.3 (2)C15—C16—C17—C181.8 (2)
C41—C46—C45—C441.4 (2)C15—C20—C19—C182.2 (2)
C42—C41—C46—C45−1.5 (2)C16—C15—C20—C19−0.5 (2)
C42—C43—C44—C45−1.4 (2)C16—C17—C18—C190.0 (2)
C43—C42—C41—C460.2 (2)C17—C16—C15—C20−1.5 (2)
C43—C44—C45—C460.0 (2)C17—C18—C19—C20−2.0 (2)
C31—C30—O6—C33175.28 (16)C5—C4—O3—C7179.77 (17)
C31—C30—C29—C281.0 (2)C5—C4—C3—C21.3 (2)
C31—C32—C27—C280.6 (2)C5—C6—C1—C2−0.3 (2)
C30—C31—C32—C27−1.4 (2)C4—C5—C6—C11.2 (2)
C30—C29—C28—C27−1.8 (2)C4—C3—C2—C1−0.4 (2)
C29—C30—O6—C33−4.8 (2)C3—C4—O3—C7−0.7 (3)
C29—C30—C31—C320.6 (2)C3—C4—C5—C6−1.7 (2)
C29—C28—C27—C321.1 (2)C3—C2—C1—C6−0.1 (2)
2-Methoxy-5-nitro-N-(triphenylmethyl)aniline (1) top
Crystal data top
C15H16N2O3F(000) = 576.366
Mr = 272.31Dx = 1.347 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.5017 (4) ÅCell parameters from 9923 reflections
b = 15.7855 (7) Åθ = 2.5–27.6°
c = 8.9908 (4) ŵ = 0.10 mm−1
β = 95.230 (2)°T = 130 K
V = 1342.91 (10) Å3Plate, orange
Z = 40.29 × 0.17 × 0.05 mm
Data collection top
Bruker APEXII CCD
diffractometer		2497 reflections with I ≥ 2u(I)
φ and ω scansRint = 0.050
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		θmax = 27.5°, θmin = 2.5°
Tmin = 0.657, Tmax = 0.746h = −12→12
30573 measured reflectionsk = −20→20
3078 independent reflectionsl = −11→11
Refinement top
Refinement on F20 restraints
Least-squares matrix: full0 constraints
R[F2 > 2σ(F2)] = 0.048All H-atom parameters refined
wR(F2) = 0.136 w = 1/[σ2(Fo2) + (0.0791P)2 + 0.4263P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3078 reflectionsΔρmax = 0.33 e Å−3
245 parametersΔρmin = −0.38 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O30.76030 (11)0.38217 (6)0.01780 (12)0.0242 (3)
O20.97647 (13)0.70533 (7)−0.28049 (13)0.0322 (3)
O11.08131 (13)0.61179 (8)−0.40737 (13)0.0365 (3)
N11.00248 (13)0.63104 (8)−0.31186 (14)0.0244 (3)
N20.71393 (13)0.54099 (8)0.07966 (15)0.0246 (3)
C40.82050 (14)0.43825 (9)−0.07203 (15)0.0197 (3)
C90.63647 (15)0.62833 (8)0.28127 (16)0.0214 (3)
C50.79528 (14)0.52434 (8)−0.03534 (15)0.0190 (3)
C20.96011 (15)0.48079 (9)−0.26923 (16)0.0222 (3)
C10.93668 (14)0.56407 (9)−0.23134 (15)0.0205 (3)
C60.85415 (15)0.58710 (9)−0.11750 (15)0.0207 (3)
C100.50011 (16)0.59885 (9)0.29420 (17)0.0251 (3)
C140.71353 (15)0.65970 (9)0.40830 (17)0.0240 (3)
C30.89990 (15)0.41751 (9)−0.18848 (16)0.0222 (3)
C130.65483 (16)0.66165 (9)0.54449 (17)0.0245 (3)
C110.44275 (16)0.60007 (10)0.43046 (18)0.0268 (3)
C80.69961 (17)0.62703 (9)0.13353 (17)0.0242 (3)
C120.51903 (16)0.63175 (9)0.55794 (16)0.0236 (3)
C150.45916 (19)0.63335 (11)0.70754 (19)0.0310 (4)
C70.7786 (2)0.29380 (9)−0.0128 (2)0.0321 (4)
H30.913 (2)0.3603 (13)−0.211 (2)0.032 (5)*
H2a1.0174 (18)0.4693 (12)−0.3504 (19)0.025 (4)*
H60.8408 (19)0.6453 (13)−0.094 (2)0.029 (5)*
H140.810 (2)0.6791 (12)0.403 (2)0.028 (4)*
H130.711 (2)0.6824 (12)0.632 (2)0.028 (4)*
H110.346 (2)0.5786 (13)0.437 (2)0.037 (5)*
H100.4443 (19)0.5769 (12)0.208 (2)0.027 (4)*
H8a0.795 (2)0.6540 (12)0.1458 (19)0.026 (4)*
H8b0.641 (2)0.6586 (12)0.057 (2)0.028 (4)*
H15a0.505 (2)0.5891 (14)0.775 (2)0.044 (6)*
H15b0.479 (2)0.6901 (14)0.758 (2)0.044 (6)*
H15c0.359 (2)0.6207 (13)0.695 (2)0.035 (5)*
H7a0.738 (2)0.2788 (14)−0.116 (2)0.039 (5)*
H7b0.878 (2)0.2780 (13)0.000 (2)0.039 (5)*
H7c0.729 (2)0.2645 (14)0.063 (2)0.042 (5)*
H20.698 (2)0.5003 (14)0.138 (2)0.036 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0304 (6)0.0152 (5)0.0282 (5)−0.0020 (4)0.0089 (4)−0.0017 (4)
O20.0386 (6)0.0208 (5)0.0386 (6)−0.0037 (5)0.0115 (5)0.0021 (5)
O10.0446 (7)0.0356 (6)0.0323 (6)−0.0083 (5)0.0198 (5)−0.0028 (5)
N10.0256 (6)0.0254 (6)0.0224 (6)−0.0045 (5)0.0034 (5)0.0008 (5)
N20.0310 (7)0.0147 (6)0.0299 (6)−0.0007 (5)0.0130 (5)−0.0006 (5)
C40.0193 (6)0.0174 (6)0.0220 (6)−0.0013 (5)0.0002 (5)−0.0002 (5)
C90.0245 (7)0.0132 (6)0.0271 (7)0.0028 (5)0.0057 (5)0.0004 (5)
C50.0182 (6)0.0177 (6)0.0211 (6)−0.0009 (5)0.0014 (5)−0.0023 (5)
C20.0230 (7)0.0242 (7)0.0197 (6)0.0003 (5)0.0025 (5)−0.0019 (5)
C10.0207 (6)0.0213 (7)0.0193 (6)−0.0029 (5)0.0011 (5)0.0008 (5)
C60.0229 (7)0.0169 (6)0.0225 (7)−0.0006 (5)0.0024 (5)−0.0006 (5)
C100.0236 (7)0.0231 (7)0.0284 (7)0.0002 (5)0.0013 (6)−0.0038 (6)
C140.0223 (7)0.0181 (6)0.0320 (8)−0.0011 (5)0.0043 (6)−0.0011 (5)
C30.0250 (7)0.0183 (6)0.0233 (7)−0.0003 (5)0.0021 (5)−0.0034 (5)
C130.0275 (7)0.0180 (6)0.0277 (7)0.0014 (5)0.0004 (6)−0.0019 (5)
C110.0211 (7)0.0260 (7)0.0338 (8)−0.0008 (6)0.0056 (6)0.0002 (6)
C80.0306 (8)0.0156 (6)0.0276 (7)0.0002 (5)0.0083 (6)−0.0010 (5)
C120.0272 (7)0.0171 (6)0.0274 (7)0.0057 (5)0.0066 (6)0.0025 (5)
C150.0349 (9)0.0296 (8)0.0302 (8)0.0042 (7)0.0114 (7)0.0036 (6)
C70.0456 (10)0.0154 (7)0.0367 (9)−0.0030 (6)0.0115 (7)−0.0037 (6)
Geometric parameters (Å, º) top
O3—C41.3591 (16)C10—C111.386 (2)
O3—C71.4354 (17)C10—H100.962 (18)
O2—N11.2364 (17)C14—C131.391 (2)
O1—N11.2280 (17)C14—H140.969 (19)
N1—C11.4543 (17)C3—H30.94 (2)
N2—C51.3716 (17)C13—C121.389 (2)
N2—C81.4526 (17)C13—H130.968 (19)
N2—H20.85 (2)C11—C121.392 (2)
C4—C51.4238 (18)C11—H110.99 (2)
C4—C31.3844 (19)C8—H8a1.000 (19)
C9—C101.391 (2)C8—H8b0.986 (19)
C9—C141.390 (2)C12—C151.508 (2)
C9—C81.5067 (19)C15—H15a1.00 (2)
C5—C61.3841 (19)C15—H15b1.01 (2)
C2—C11.3811 (19)C15—H15c0.96 (2)
C2—C31.388 (2)C7—H7a1.00 (2)
C2—H2a0.967 (17)C7—H7b0.98 (2)
C1—C61.3931 (19)C7—H7c0.98 (2)
C6—H60.95 (2)
C7—O3—C4117.02 (11)C2—C3—C4120.28 (13)
O1—N1—O2122.79 (12)H3—C3—C4118.9 (12)
C1—N1—O2118.16 (12)H3—C3—C2120.8 (12)
C1—N1—O1119.05 (12)C12—C13—C14121.27 (14)
C8—N2—C5120.46 (12)H13—C13—C14119.2 (11)
H2—N2—C5117.8 (13)H13—C13—C12119.5 (11)
H2—N2—C8118.0 (13)C12—C11—C10121.05 (14)
C5—C4—O3113.27 (12)H11—C11—C10119.7 (11)
C3—C4—O3125.68 (12)H11—C11—C12119.3 (11)
C3—C4—C5121.05 (12)C9—C8—N2111.32 (11)
C14—C9—C10118.37 (13)H8a—C8—N2108.9 (10)
C8—C9—C10121.18 (13)H8a—C8—C9109.1 (10)
C8—C9—C14120.45 (13)H8b—C8—N2107.7 (11)
C4—C5—N2118.42 (12)H8b—C8—C9111.4 (11)
C6—C5—N2123.24 (12)H8b—C8—H8a108.4 (14)
C6—C5—C4118.34 (12)C11—C12—C13117.92 (14)
C3—C2—C1118.19 (13)C15—C12—C13120.06 (14)
H2a—C2—C1118.6 (11)C15—C12—C11122.01 (14)
H2a—C2—C3123.2 (11)H15a—C15—C12110.5 (12)
C2—C1—N1118.87 (12)H15b—C15—C12110.1 (12)
C6—C1—N1118.18 (12)H15b—C15—H15a107.2 (17)
C6—C1—C2122.94 (13)H15c—C15—C12110.0 (12)
C1—C6—C5119.16 (13)H15c—C15—H15a106.9 (17)
H6—C6—C5120.2 (11)H15c—C15—H15b112.0 (17)
H6—C6—C1120.6 (11)H7a—C7—O3111.3 (12)
C11—C10—C9120.89 (14)H7b—C7—O3111.1 (13)
H10—C10—C9120.2 (10)H7b—C7—H7a109.7 (17)
H10—C10—C11118.9 (10)H7c—C7—O3104.4 (13)
C13—C14—C9120.49 (13)H7c—C7—H7a111.3 (17)
H14—C14—C9120.3 (11)H7c—C7—H7b108.8 (17)
H14—C14—C13119.2 (11)
O3—C4—C5—N2−1.32 (14)C9—C14—C13—C120.66 (16)
O3—C4—C5—C6178.65 (11)C9—C8—N2—C5−166.23 (12)
O3—C4—C3—C2−177.79 (14)C5—C4—O3—C7179.06 (13)
O2—N1—C1—C2177.42 (13)C5—C4—C3—C21.88 (16)
O2—N1—C1—C6−3.49 (15)C5—C6—C1—C21.67 (16)
O1—N1—C1—C2−2.74 (15)C6—C5—N2—C8−7.66 (17)
O1—N1—C1—C6176.35 (13)C6—C5—C4—C3−1.06 (15)
N1—C1—C2—C3178.17 (13)C6—C1—C2—C3−0.87 (16)
N1—C1—C6—C5−177.38 (12)C10—C9—C14—C13−0.23 (15)
N2—C5—C4—C3178.97 (13)C10—C11—C12—C13−0.38 (17)
N2—C5—C6—C1179.29 (14)C10—C11—C12—C15−179.69 (14)
N2—C8—C9—C10−63.40 (15)C14—C9—C10—C11−0.48 (15)
N2—C8—C9—C14116.98 (13)C14—C13—C12—C11−0.34 (16)
C4—C5—N2—C8172.31 (13)C14—C13—C12—C15178.98 (13)
C4—C5—C6—C1−0.68 (15)C3—C4—O3—C7−1.25 (18)
C4—C3—C2—C1−0.92 (16)C13—C14—C9—C8179.40 (13)
C9—C10—C11—C120.80 (17)C11—C10—C9—C8179.88 (13)
Planarity of amine nitrogen atoms for compounds considered here top
Torsion angles using the four atoms indicated in the Scheme. Uncertainties are +/- 0.2°. Spectroscopic data for each compound dissolved in acetone, 0.1 mM.
CompoundAtoms usedTorsion angleλmax (nm)
1C4—C5—N2—C8172.31 (13)°392
2C4—C5—N2—C8, C30—C31—N4—C34a,b–157.32 (19)°, 168.5 (2)°383
ParentcC2—C1—N1—H1B–159.3°380
Note: (a). The second value is for the second crystallographically independent molecule. (b). The authors are indebted to a reviewer for pointing out the only other significant differences between the independent molecules are in the triphenylmethyl groups. (c). Taken from Filley (2024).
 

Acknowledgements

X-ray crystallography experiments were performed at Colorado State University's Analytical Resources Core (RRID: SCR_021758).

References

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ISSN: 2056-9890
Volume 82| Part 8| August 2026|
https://doi.org/10.1107/S205698902600681X
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