research communications
Synthesis and crystal structures of three new benzotriazolylpropanamides
aChemistry Department, James Madison University, Harrisonburg, VA 22807, USA, and bChemisches Institut der Otto-von-Guericke-Universität Magdeburg, Universitätsplatz 2, 39106 Magdeburg, Germany
*Correspondence e-mail: giljejw@jmu.edu, frank.edelmann@ovgu.de
The base-catalyzed Michael addition of 2-methylacrylamide to benzotriazole afforded 3-(1H-benzotriazol-1-yl)-2-methylpropanamide, C10H12N4O (1), in 32% yield in addition to small amounts of isomeric 3-(2H-benzotriazol-2-yl)-2-methylpropanamide, C10H12N4O (2). In a similar manner, 3-(1H-benzotriazol-1-yl)-N,N-dimethylpropanamide, C11H14N4O (3), was prepared from benzotriazole and N,N-dimethylacrylamide. All three products have been structurally characterized by single-crystal X-ray diffraction. The crystal structures of 1 and 2 comprise infinite arrays formed by N—H⋯O and N—H⋯N bridges, as well as π–π interactions, while the molecules of 3 are aggregated to simple π-dimers in the crystal.
1. Chemical context
Di- and tridentate pyrazolyl-based ligands play an important role in the design of supramolecular assemblies of metal complexes. Particularly notable among the large variety of such ligands are Trofimenko's famous poly(pyrazolyl)borates (`scorpionates') (Trofimenko, 1993, 2004; Marques et al., 2002; Paulo et al., 2004; Smith, 2008) and the poly(pyrazolyl)methane ligands (Bassanetti et al., 2016; Bigmore et al., 2005; Krieck et al., 2016; Otero et al., 2013; Semeniuc & Reger, 2016). In a series of previous studies, we reported the synthesis and supramolecular coordination chemistry of the simple, functionalized pyrazolyl-based ligand 3-(pyrazol-1-yl)propanamide. This ligand is readily available in one step via base-catalyzed Michael addition of pyrazole to acrylamide (Girma et al., 2008). In combination with various first- and second-row transition metals (e.g. Mn, Fe, Ru, Co, Ni), 3-(1H-pyrazol-1-yl)propanamide allows the design of a variety of hydrogen-bonded supramolecular assemblies, including different chains, sheets, and three-dimensional arrays (D'Amico et al., 2015). As an additional advantage, the pyrazolylpropanamide ligand system can be easily modified either by attachment of substituents to the propanamide backbone (D'Amico et al., 2015) or by replacing the pyrazole ring by other N-heterocycles such as triazole (D'Amico et al., 2015; Wagner et al., 2012). In our most recent study, we investigated the structural influence of benzotriazolyl as a hydrophobic which imparts character to the ligand and forms the basis of novel supramolecular assemblies. In the course of this work, the solid-state structures of 3-(1H-benzotriazol-1-yl)-propaneamide (= `BTPA') and of several first-row transition metal complexes (Mn, Co, Cu) derived thereof have been described (Wang et al., 2017). We report here the synthesis and structural characterization of three new potentially useful benzotriazolylpropanamide ligands.
The title compounds were prepared by base-catalyzed Michael addition of benzotriazole to methyl-substituted acrylamides, namely 2-methylacrylamide and N,N-dimethylacrylamide. As shown in the reaction scheme (Fig. 1), benzotriazole exists in two tautomeric forms A and B. Spectroscopic data (UV, IR and 1H NMR) (Negri & Caminati, 1996; Nesmeyanov et al., 1969; Poznański et al., 2007) and measurements (Mauret et al., 1974) revealed that the 1H-tautomer A is the predominant species at room temperature.
The thermal reaction of benzotriazole with 2-methylacrylamide was carried out in the usual manner (D'Amico et al., 2015; Wagner et al., 2012; Wang et al., 2017) in the presence of Triton B (= benzyltrimethylammonium hydroxide) as basic catalyst. Repeated recrystallization of the crude product from ethanol afforded 3-(1H-benzotriazol-1-yl)-2-methylpropanamide (1) in 32% isolated yield. The compound was characterized through elemental analysis as well as IR and NMR (1H, 13C) spectroscopy. In the 13C NMR spectrum, the amide carbonyl C atom gives a characteristic resonance at 175.2 ppm. The formation of 1 as the main reaction product corresponds to the predominant presence of tautomer A in the starting benzotriazole. From the mother liquor of the recrystallization of 1, a small amount of colorless crystals could be isolated, which were found to be the isomer 3-(2H-benzotriazol-2-yl)-2-methylpropanamide (2) resulting from the reaction of the 2H-tautomer B with 2-methylacrylamide. Compound 2 could also be fully characterized by elemental analysis as well as IR and NMR data.
In a similar manner, a reaction of benzotriazole with neat N,N-dimethylacrylamide in the presence of Triton B afforded a yellow oil which was shown to be an approximate 2:1 mixture of 3 and 4. Once again, the main component was the Michael addition product resulting from the 1H-tautomer A of benzotriazole. Thus far, only isomer 3 could be isolated in pure form by recrystallization of the oily crude product from ethanol. The identity of 3-(1H-benzotriazol-1-yl)-N,N-dimethylpropanamide 3 was confirmed by elemental analysis and spectroscopic data (IR, 1H and 13C NMR). In the 13C NMR spectrum, the NMe2 group gives rise to two resonances at δ 33.2 and 35.5 ppm, whereas the signal of the amide carbonyl C atom is found at δ 169.5 ppm.
2. Structural commentary
Compounds 1–3 exist as well-defined monomeric molecules in the crystal, without any solvent of crystallization (Figs. 2–4). The C=O separations are in a narrow range around 1.24 Å and are therefore virtually equal with those observed in related functionalized propanamides (Girma et al. 2008; Wagner et al. 2012; D'Amico et al. 2015; Wang et al. 2017). Thus, the C=O distance is not markedly influenced by hydrogen bonding, as there are N—H⋯O bridges in 1 and 2, but not in 3 (see Supramolecular features section). The same applies to the amide C—N separation, which is around 1.33 Å in all compounds. The torsion angle C1—C2—C3—N between the amide group and the 1H-benzotriazol-1-yl residue is 71.0 (1)° (1) and −72.2 (2)° (3), respectively, which is close to the value observed in the unsubstituted BTPA (71.3 (1)°; Wang et al., 2017). By contrast, the same torsion angle in the 2H-benzotriazole-derived compound 2 is considerably smaller at 59.7 (1)°.
3. Supramolecular features
In 1 and 2, the molecules are interconnected to dimeric subunits by R22(8)-type N—H⋯O bridges, which is a very typical motif (Bernstein et al., 1995). These amide dimers are again interconnected by N—H⋯N bridges (Tables 1 and 2) between the remaining amide N—H moiety and the benzotriazolyl group, resulting in an infinite chain of rings in both cases. In 1, the dimeric subunits are linked by a R22(16) bridge to N4 (Fig. 5), while a C(7) bridge involving N2 is realized in compound 2 (Fig. 7). The latter leads to an R44(18) motif at the binary level. The hydrogen-bridge pattern in 1 and 2 is therefore entirely different than in the unbridged BTPA, where supramolecular layers are formed exclusively by N—H⋯O bridges (Wang et al., 2017). As has been discussed for BTPA and its metal complexes, the N—H⋯N bonds are significantly weaker than the N—H⋯O bonds. Both the N⋯O separation [1: N1⋯O 2.897 (1) Å; 2: N1⋯O 2.875 (2) Å] and the N⋯N separations [1: N1⋯N4 3.002 (1) Å; 2: N1⋯N2 3.085 (2) Å] are in the typical range. In the of 3, no hydrogen bonds are present as the amide H atoms are replaced by methyl groups.
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In both 1 and 2, the supramolecular chains are further aggregated by π–π interactions between the benzotriazolyl rings. In 1, a three-dimensional framework is present (Fig. 6), where two different types of π interactions can be distinguished. First, the C6 rings of each two adjoining benzotriazolyl groups are stacked in a typical parallel-displaced fashion (cf. Fig. 10a). The shortest C⋯C contact is 3.364 (2) Å between C7 and C9 and the distance between the C6 ring centroids is 3.655 (2) Å, which is in the range of strong π interactions (McGaughey et al., 1998). The so-formed π dimers are interconnected by another π interaction to an infinite chain, where an attractive interaction seems to exist between the whole bicyclic C6N3 system rather than between the C6 rings only (cf. Fig. 10c). The closest intermolecular separations are 3.308 (2) Å (C9⋯N2) and 3.403 (2) Å (C5⋯C10), and therefore in the same range as in the former mentioned interaction. In the case of 2, a layer structure parallel to (001) is formed (Fig. 8). The geometry of the interaction between the C6 rings is similar as in 1, but the closest C⋯C contact exists between C5 and C9 with 3.521 (2) Å, and the corresponding separation between the C6 centroids is considerably larger at 3.933 (2) Å (cf. Fig. 10b). In 3, only two molecules are stacked together to a simple π dimer (Fig. 9), with participation of the whole C6N3 bicycle similar as described above for 1 (cf. Fig. 10c). Here, the closest intermolecular contacts are 3.468 (2) Å (C8⋯N2) and 3.509 (2) Å (C4⋯C9), which is significantly larger than in 1. Comparable π interactions as in 1–3 have not been observed in the unbridged BTPA, but in its metal complexes [MCl2(BTPA)2] (M = Mn, Co, Cu; min. C⋯C 3.45 Å; Wang et al., 2017). The arrangement of the benzotriazolyl groups in the latter compounds is similar to that in 3 (cf. Fig. 10c).
4. Database survey
For reviews on di- and tridentate pyrazolyl-based ligands, see Bassanetti et al. (2016), Bigmore et al. (2005), Krieck et al. (2016), Marques et al. (2002), Otero et al. (2013), Paulo et al. (2004), Semeniuc & Reger (2016), Smith (2008), Trofimenko (1993, 2004).
For the et al. (1974), Negri & Caminati (1996); Nesmeyanov et al. (1969), Poznański et al. (2007).
of benzotriazole, see MauretFor other structurally characterized 3-pyrazolylpropanamide-derived ligands, see D'Amico et al. (2015), Girma et al. (2008), Wagner et al. (2012), Wang et al. (2017).
5. Synthesis and crystallization
All manipulations were performed under inert nitrogen or argon atmospheres using standard Schlenk techniques or in a Vacuum Atmospheres −1 and 400 cm−1.
The starting materials were obtained from commercial sources and used as received. Solvents were dried using an Innovative Technology, Inc, solvent purification system. Microanalysis was performed by Galbraith Laboratories, Inc, Knoxville, TN, USA. NMR spectra were obtained using Bruker Avance 300 MHz and 400 MHz NMR Spectrometers. IR spectra were recorded using KBr pellets with a ThermoNicolet Avatar 370 FT–IR between 4000 cmPreparation of 2-methyl-3-(1H-benzotriazol-1-yl)propanamide (1) and 2-methyl-3-(2H-benzotriazol-2-yl)propanamide (2):
In a 150 mL three-neck flask, a mixture of benzotriazole (5.032 g, 42.24 mmol), 2-methyl acrylamide (3.731 g, 43.84 mmol) and 2 mL of Triton B was heated for 6.5 h in a boiling water bath. The mixture solidified upon cooling. The crude product was slurried with 95% ethanol and the remaining solid recrystallized three times from 95% ethanol to yield 2.841g (13.91 mmol, 32%) of spectroscopically pure 1. Single crystals suitable for X-ray diffraction were obtained from these recrystallizations. M.p. 476–479 K. Analysis calculated for C10H12N4O, M = 204.20 g mol−1: C 58.82; H 5.92; N 27.44. Found: C 58.73; H 5.96; N 27.72. IR (KBr, cm−1): 3307 vs, 3208 s, 3155 vs, 2968 m, 2930 w, 1685 vs, 1442 m, 1315 m, 1226 s, 780 m, 742 vs. 1H NMR (400 MHz, DMSO-d6): 1.07 (d, J2-4 = 7 Hz, 3H; CH3), 3.06 (sext, J2-4 = 7 Hz, J2-3 = 7 Hz, 1H; 2-CH), 4.61 (dd, J2-3 = 7 Hz, J2-2′ = 14 Hz, 1H; CH2), 4.86 (dd, J2-3 = 7 Hz, J2-2′ = 14 Hz, 1H; CH2), 6.88 (s br, 1H; NH), 7.39 (m, 1H; 8-CH or 9-CH), 7.42 (s br, 1H; NH) 7.54 (m, 1H; 8-CH or 9-CH), 7.87 (m, 1H; 7-CH or 10-CH), 8.02 (m, 1H; 7-CH or 10-CH) ppm. The resonances for positions 7–10 appear as multiplets that can be interpreted if the coupling constants between adjacent protons are 7–8 Hz, with longer range couplings of about 1 Hz. 13C{1H} NMR (100 MHz, DMSO-d6): 16.2 (CH3), 40.6 (2-CH), 50.6 (CH2), 111.5 (10-CH), 119.4 (7-CH), 124.3 (8-CH), 127.5 (9-CH), 133.5 (5-C), 145.4 (6-C), 175.3 (CO) (for numbering scheme cf. Fig. 2).
The mother liquor remaining after the isolation of 1 was concentrated, and two additional crops of crystals were obtained. The second crop was several milligrams of nearly pure 2 and contained crystals suitable for X-ray diffraction. M.p. 476–479 K. Analysis calculated for C10H12N4O, M = 204.20 g mol−1: C 58.82; H 5.92; N 27.44. Found: C 58.92; H 6.20; N 27.50. IR (KBr, cm−1): 3307 vs, 3208 s, 3155 vs, 2968 m, 2930 w, 1685 vs, 1442 m, 1315 m, 1226 s, 780 m, 742 vs. 1H NMR (400 MHz, DMSO-d6): 1.06 (d, J2-4 = 7.0 Hz, 3H; CH3), 3.06 (sext, J2-4 = 7.0 Hz, J2-3 = 7.0 Hz, J2-3′ = 7.7 Hz, 1H; 2-CH), 4.64 (dd, J2-3 = 7.0 Hz, J3-3′ = 13.3 Hz, 1H; CH2), 4.93 (dd, J2-3 = 7.7 Hz, J3-3′ = 13.3 Hz, 1H; CH2), 6.91 (s br, 1H; NH), 7.43 (m, 2H; 6,9-CH), 7.48 (s br; NH), 7.91 (m, 2H; 7,8-CH). The resonances for 6-CH, 7-CH, 8-CH and 9-CH appear as an AA'BB' pattern. While there is no unique solution for AA′BB′ spectra, the 1H spectrum of the aromatic region of 2 can be duplicated using reasonable values of the coupling constants: J7-8 = 6.8 Hz, J6-7 = J8-9 = 8.6 Hz, J6-8 = J7-9 = 1.0 Hz, and J6-9 = 1.0 Hz. 13C{1H} NMR (100 MHz, DMSO-d6): 16.2 (CH3), 40.5 (2-CH), 58.5 (CH2), 118.3 (6,9-CH), 126.8 (7,8-CH), 144.1 (5,10-C), 175.0 (CO) (for numbering scheme cf. Fig. 3).
Preparation of N,N-dimethyl-3-(1H-benzotriazol-1-yl)propanamide (3):
In a 150 mL three-neck flask, a mixture of benzotriazole (5.99 g, 50.0 mmol), N,N-dimethylacrylamide (4.78 g, 48.8 mmol) and 2 mL of Triton B was heated for 6.5 h in a boiling water bath under nitrogen. Upon cooling to 278 K, a yellow oil was obtained. This mixture was an approximate 2:1 mixture of 3 and 4. After recrystallization from ethanol, samples of pure 3 could be obtained. Single crystals suitable for X-ray diffraction were obtained from recrystallization from a CHCl3/hexanes mixture. M.p. 338–339 K. Analysis calculated for C10H12N4O, M = 218.26 g mol−1: C 60.53; H 6.47; N 25.60. Found: C 60.48; H 6.27; N 25.87. IR (KBr, cm−1): 3082 w, 3050 w, 3015 w, 2967 m, 2939 m, 2911 m, 1644 vs, 1496 s, 1452 s, 1414 s, 1396 s, 1338 m, 1298 m, 1216 s, 1151 s, 1092 s, 942 m, 761 s, 743 vs. 1H NMR (300 MHz, CDCl3): 2.92 (s, 3H; NCH3), 2.94 (s; NCH3), 3.14 (t, J2-3 = 7 Hz, 2H; 2-CH2), 4.98 (t, J2-3 = 7 Hz, 2H; 3-CH2), 7.38 (m, 2H; 7-CH or 8-CH), 7.51 (m, 2H; 7-CH or 8-CH), 7.20 (m, 2H; 6-CH or 9-CH), 8.05 (m, 2H; 6-CH or 9-CH). The resonances for positions 6–9 appear as multiplets that can be interpreted if the coupling constants between adjacent protons are 7–8 Hz, with longer range couplings of about 1 Hz. 13C{1H} NMR (100 MHz, CDCl3): 33.2 (NCH3), 35.5 (NCH3), 37.0 (2-CH2), 43.9 (3-CH2), 110.0 (9-CH), 119.7 (6-CH), 123.9 (7-CH), 127.4 (8-CH), 133.3 (4-C), 145.8 (5-C), 169.5 (CO) (for numbering scheme cf. Fig. 4).
6. Refinement
Crystal data, data collection and structure . All H atoms were fixed geometrically using a riding model with Uiso(H) = 1.2 Ueq(X) (X = C, N). The CH3 groups were allowed to rotate freely around the C—X vector (X = C, N) (AFIX 137 in SHELXL), and the amide NH2 groups in 1 and 2 were constrained to be planar (AFIX 93 in SHELXL). C—H distances in CH3 groups were constrained to 0.98 Å, those in CH2 groups to 0.99 Å and those in CH groups to 1.00 Å. N—H distances in 1 and 2 were constrained to 0.88 Å. For compound 2, reflection (62) strongly disagreed with the structural model and was therefore omitted from the In the case of compound 3, one N-bonded methyl group (C11) was refined as rotationally disordered over two positions. Site occupancy factors were refined freely to 0.59 (2) for H12A, H13A and H14A, and to 0.41 (2) for H12B, H13B and H14B.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989017007472/zl2702sup1.cif
contains datablocks 1, 2, 3. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989017007472/zl27021sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989017007472/zl27022sup3.hkl
Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2056989017007472/zl27023sup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017007472/zl27021sup5.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989017007472/zl27022sup6.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989017007472/zl27023sup7.cml
Data collection: CrysAlis PRO (Agilent, 2003) for (1); X-AREA (Stoe & Cie, 2002) for (2), (3). Cell
CrysAlis PRO (Agilent, 2003) for (1); X-AREA (Stoe & Cie, 2002) for (2), (3). Data reduction: CrysAlis PRO (Agilent, 2003) for (1); X-AREA and X-RED (Stoe & Cie, 2002) for (2), (3). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (1), (2); SIR97 (Altomare et al., 1999) for (3). For all compounds, program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015).C10H12N4O | Z = 2 |
Mr = 204.24 | F(000) = 216 |
Triclinic, P1 | Dx = 1.356 Mg m−3 |
a = 7.3885 (9) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 8.072 (1) Å | Cell parameters from 21215 reflections |
c = 9.2976 (13) Å | θ = 5.1–76.1° |
α = 69.039 (12)° | µ = 0.76 mm−1 |
β = 89.498 (10)° | T = 100 K |
γ = 75.915 (10)° | Prism, colorless |
V = 500.37 (12) Å3 | 0.15 × 0.10 × 0.08 mm |
Agilent Xcalibur, Atlas, Nova diffractometer | 2053 independent reflections |
Radiation source: fine-focus sealed tube | 2012 reflections with I > 2σ(I) |
Detector resolution: 10.3543 pixels mm-1 | Rint = 0.026 |
ω scans | θmax = 75.0°, θmin = 5.1° |
Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2003) | h = −9→9 |
Tmin = 0.919, Tmax = 1.000 | k = −10→10 |
28193 measured reflections | l = −9→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0349P)2 + 0.1806P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2053 reflections | Δρmax = 0.33 e Å−3 |
138 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0117 (12) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.15133 (14) | 0.68751 (14) | 0.89673 (11) | 0.0176 (2) | |
C2 | 0.25594 (14) | 0.83380 (13) | 0.82012 (11) | 0.0179 (2) | |
H3 | 0.165006 | 0.949315 | 0.752342 | 0.022* | |
C3 | 0.40506 (14) | 0.76911 (14) | 0.72364 (11) | 0.0184 (2) | |
H4 | 0.488091 | 0.853320 | 0.694399 | 0.022* | |
H5 | 0.482564 | 0.645326 | 0.787098 | 0.022* | |
C4 | 0.35221 (17) | 0.87131 (16) | 0.94623 (13) | 0.0262 (3) | |
H8 | 0.258168 | 0.911025 | 1.010223 | 0.031* | |
H6 | 0.416372 | 0.967988 | 0.898144 | 0.031* | |
H7 | 0.443677 | 0.758907 | 1.011003 | 0.031* | |
C5 | 0.29153 (13) | 0.61763 (14) | 0.55521 (12) | 0.0167 (2) | |
C6 | 0.21574 (14) | 0.69407 (14) | 0.40143 (12) | 0.0181 (2) | |
C7 | 0.16602 (14) | 0.58415 (15) | 0.32859 (12) | 0.0213 (2) | |
H9 | 0.113426 | 0.634772 | 0.224400 | 0.026* | |
C8 | 0.19688 (14) | 0.40025 (15) | 0.41480 (13) | 0.0220 (2) | |
H10 | 0.165146 | 0.321802 | 0.369143 | 0.026* | |
C9 | 0.27490 (14) | 0.32485 (14) | 0.57016 (13) | 0.0214 (2) | |
H11 | 0.294873 | 0.196704 | 0.625394 | 0.026* | |
C10 | 0.32283 (14) | 0.43018 (14) | 0.64405 (12) | 0.0191 (2) | |
H12 | 0.373910 | 0.379176 | 0.748680 | 0.023* | |
N1 | −0.03436 (12) | 0.74707 (12) | 0.89024 (10) | 0.0209 (2) | |
H2 | −0.101453 | 0.669647 | 0.936062 | 0.025* | |
H1 | −0.089861 | 0.863817 | 0.840137 | 0.025* | |
N2 | 0.32450 (12) | 0.76231 (11) | 0.58395 (10) | 0.0173 (2) | |
N3 | 0.27302 (13) | 0.91737 (12) | 0.45699 (10) | 0.0209 (2) | |
N4 | 0.20701 (13) | 0.87851 (12) | 0.34604 (10) | 0.0213 (2) | |
O | 0.23854 (10) | 0.52560 (10) | 0.96498 (9) | 0.02255 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0225 (5) | 0.0179 (5) | 0.0130 (4) | −0.0063 (4) | 0.0019 (4) | −0.0056 (4) |
C2 | 0.0214 (5) | 0.0164 (5) | 0.0158 (5) | −0.0061 (4) | 0.0012 (4) | −0.0049 (4) |
C3 | 0.0195 (5) | 0.0197 (5) | 0.0171 (5) | −0.0071 (4) | 0.0007 (4) | −0.0065 (4) |
C4 | 0.0344 (6) | 0.0286 (6) | 0.0207 (5) | −0.0144 (5) | 0.0023 (4) | −0.0110 (4) |
C5 | 0.0152 (4) | 0.0180 (5) | 0.0173 (5) | −0.0046 (4) | 0.0030 (4) | −0.0068 (4) |
C6 | 0.0171 (5) | 0.0187 (5) | 0.0163 (5) | −0.0030 (4) | 0.0026 (4) | −0.0048 (4) |
C7 | 0.0190 (5) | 0.0278 (6) | 0.0182 (5) | −0.0050 (4) | 0.0021 (4) | −0.0103 (4) |
C8 | 0.0200 (5) | 0.0259 (5) | 0.0258 (6) | −0.0083 (4) | 0.0055 (4) | −0.0148 (4) |
C9 | 0.0209 (5) | 0.0178 (5) | 0.0256 (5) | −0.0063 (4) | 0.0053 (4) | −0.0071 (4) |
C10 | 0.0187 (5) | 0.0182 (5) | 0.0178 (5) | −0.0049 (4) | 0.0021 (4) | −0.0035 (4) |
N1 | 0.0207 (4) | 0.0165 (4) | 0.0213 (4) | −0.0050 (3) | 0.0022 (3) | −0.0018 (3) |
N2 | 0.0206 (4) | 0.0152 (4) | 0.0148 (4) | −0.0053 (3) | 0.0018 (3) | −0.0037 (3) |
N3 | 0.0255 (5) | 0.0170 (4) | 0.0170 (4) | −0.0046 (3) | 0.0022 (3) | −0.0032 (3) |
N4 | 0.0247 (5) | 0.0195 (4) | 0.0170 (4) | −0.0037 (4) | 0.0007 (3) | −0.0050 (3) |
O | 0.0222 (4) | 0.0172 (4) | 0.0234 (4) | −0.0045 (3) | 0.0025 (3) | −0.0020 (3) |
C1—O | 1.2369 (13) | C5—C10 | 1.4014 (14) |
C1—N1 | 1.3329 (14) | C6—N4 | 1.3752 (13) |
C1—C2 | 1.5271 (14) | C6—C7 | 1.4049 (15) |
C2—C3 | 1.5261 (14) | C7—C8 | 1.3730 (15) |
C2—C4 | 1.5316 (14) | C7—H9 | 0.9500 |
C2—H3 | 1.0000 | C8—C9 | 1.4157 (16) |
C3—N2 | 1.4576 (13) | C8—H10 | 0.9500 |
C3—H4 | 0.9900 | C9—C10 | 1.3744 (15) |
C3—H5 | 0.9900 | C9—H11 | 0.9500 |
C4—H8 | 0.9800 | C10—H12 | 0.9500 |
C4—H6 | 0.9800 | N1—H2 | 0.8800 |
C4—H7 | 0.9800 | N1—H1 | 0.8800 |
C5—N2 | 1.3628 (13) | N2—N3 | 1.3505 (12) |
C5—C6 | 1.3977 (14) | N3—N4 | 1.3096 (13) |
O—C1—N1 | 123.48 (9) | N4—C6—C5 | 108.40 (9) |
O—C1—C2 | 120.43 (9) | N4—C6—C7 | 130.82 (10) |
N1—C1—C2 | 116.03 (9) | C5—C6—C7 | 120.77 (10) |
C3—C2—C1 | 110.96 (8) | C8—C7—C6 | 116.99 (10) |
C3—C2—C4 | 108.61 (9) | C8—C7—H9 | 121.5 |
C1—C2—C4 | 108.83 (8) | C6—C7—H9 | 121.5 |
C3—C2—H3 | 109.5 | C7—C8—C9 | 121.51 (10) |
C1—C2—H3 | 109.5 | C7—C8—H10 | 119.2 |
C4—C2—H3 | 109.5 | C9—C8—H10 | 119.2 |
N2—C3—C2 | 112.50 (8) | C10—C9—C8 | 122.44 (10) |
N2—C3—H4 | 109.1 | C10—C9—H11 | 118.8 |
C2—C3—H4 | 109.1 | C8—C9—H11 | 118.8 |
N2—C3—H5 | 109.1 | C9—C10—C5 | 115.74 (10) |
C2—C3—H5 | 109.1 | C9—C10—H12 | 122.1 |
H4—C3—H5 | 107.8 | C5—C10—H12 | 122.1 |
C2—C4—H8 | 109.5 | C1—N1—H2 | 120.0 |
C2—C4—H6 | 109.5 | C1—N1—H1 | 120.0 |
H8—C4—H6 | 109.5 | H2—N1—H1 | 120.0 |
C2—C4—H7 | 109.5 | N3—N2—C5 | 110.44 (8) |
H8—C4—H7 | 109.5 | N3—N2—C3 | 119.41 (8) |
H6—C4—H7 | 109.5 | C5—N2—C3 | 130.14 (8) |
N2—C5—C6 | 104.07 (9) | N4—N3—N2 | 108.81 (8) |
N2—C5—C10 | 133.36 (9) | N3—N4—C6 | 108.28 (8) |
C6—C5—C10 | 122.55 (10) | ||
O—C1—C2—C3 | 47.10 (12) | C8—C9—C10—C5 | −0.69 (15) |
N1—C1—C2—C3 | −135.56 (9) | N2—C5—C10—C9 | −177.82 (10) |
O—C1—C2—C4 | −72.35 (12) | C6—C5—C10—C9 | 0.27 (15) |
N1—C1—C2—C4 | 104.99 (10) | C6—C5—N2—N3 | −0.07 (11) |
C1—C2—C3—N2 | 70.99 (10) | C10—C5—N2—N3 | 178.28 (11) |
C4—C2—C3—N2 | −169.42 (8) | C6—C5—N2—C3 | −179.08 (9) |
N2—C5—C6—N4 | 0.01 (11) | C10—C5—N2—C3 | −0.74 (18) |
C10—C5—C6—N4 | −178.56 (9) | C2—C3—N2—N3 | 82.84 (11) |
N2—C5—C6—C7 | 178.91 (9) | C2—C3—N2—C5 | −98.22 (12) |
C10—C5—C6—C7 | 0.34 (15) | C5—N2—N3—N4 | 0.11 (11) |
N4—C6—C7—C8 | 178.10 (10) | C3—N2—N3—N4 | 179.24 (8) |
C5—C6—C7—C8 | −0.53 (15) | N2—N3—N4—C6 | −0.10 (11) |
C6—C7—C8—C9 | 0.13 (15) | C5—C6—N4—N3 | 0.06 (11) |
C7—C8—C9—C10 | 0.51 (16) | C7—C6—N4—N3 | −178.70 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···Oi | 0.88 | 2.02 | 2.8970 (12) | 175 |
N1—H1···N4ii | 0.88 | 2.16 | 3.0017 (14) | 161 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+1. |
C10H12N4O | Z = 2 |
Mr = 204.24 | F(000) = 216 |
Triclinic, P1 | Dx = 1.329 Mg m−3 |
a = 5.5961 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3462 (19) Å | Cell parameters from 5587 reflections |
c = 10.472 (2) Å | θ = 2.1–29.2° |
α = 109.83 (3)° | µ = 0.09 mm−1 |
β = 90.93 (3)° | T = 133 K |
γ = 97.14 (3)° | Prism, colorless |
V = 510.2 (2) Å3 | 0.48 × 0.33 × 0.25 mm |
Stoe IPDS 2T diffractometer | 1653 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.056 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
area detector scans | h = −6→6 |
3731 measured reflections | k = −11→11 |
1774 independent reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.028P)2 + 0.190P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1774 reflections | Δρmax = 0.25 e Å−3 |
138 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.11 (2) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0227 (2) | 0.64543 (13) | 0.69653 (13) | 0.0214 (3) | |
C2 | 0.0204 (2) | 0.74112 (14) | 0.84610 (13) | 0.0225 (3) | |
H3 | −0.098923 | 0.815190 | 0.857903 | 0.027* | |
C3 | 0.2682 (3) | 0.82849 (15) | 0.90085 (13) | 0.0252 (3) | |
H5 | 0.262252 | 0.888303 | 0.998666 | 0.030* | |
H4 | 0.383837 | 0.754250 | 0.892496 | 0.030* | |
C4 | −0.0516 (3) | 0.63442 (17) | 0.92572 (15) | 0.0341 (4) | |
H6 | −0.215805 | 0.581749 | 0.895255 | 0.041* | |
H8 | −0.045568 | 0.694636 | 1.022969 | 0.041* | |
H7 | 0.060441 | 0.558341 | 0.910078 | 0.041* | |
C5 | 0.5730 (2) | 1.03192 (15) | 0.71230 (13) | 0.0223 (3) | |
C6 | 0.3863 (2) | 1.11949 (15) | 0.75999 (13) | 0.0232 (3) | |
C7 | 0.3662 (3) | 1.25214 (16) | 0.72735 (15) | 0.0298 (3) | |
H9 | 0.239683 | 1.311962 | 0.758654 | 0.036* | |
C8 | 0.5363 (3) | 1.29041 (17) | 0.64894 (15) | 0.0325 (4) | |
H10 | 0.528050 | 1.379345 | 0.625352 | 0.039* | |
C9 | 0.7253 (3) | 1.20216 (18) | 0.60133 (15) | 0.0347 (4) | |
H11 | 0.840016 | 1.233870 | 0.547020 | 0.042* | |
C10 | 0.7479 (3) | 1.07309 (17) | 0.63095 (15) | 0.0311 (4) | |
H12 | 0.874723 | 1.014003 | 0.598479 | 0.037* | |
N1 | −0.1609 (2) | 0.64790 (12) | 0.61694 (11) | 0.0250 (3) | |
H1 | −0.170803 | 0.591949 | 0.529944 | 0.030* | |
H2 | −0.273477 | 0.705494 | 0.650863 | 0.030* | |
N2 | 0.5490 (2) | 0.91227 (12) | 0.75780 (11) | 0.0239 (3) | |
N3 | 0.3548 (2) | 0.93272 (12) | 0.82946 (11) | 0.0220 (3) | |
N4 | 0.2480 (2) | 1.05296 (13) | 0.83583 (12) | 0.0258 (3) | |
O | 0.18732 (19) | 0.56749 (11) | 0.65622 (10) | 0.0320 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0270 (7) | 0.0161 (6) | 0.0212 (7) | 0.0033 (5) | 0.0079 (5) | 0.0062 (5) |
C2 | 0.0281 (7) | 0.0205 (6) | 0.0194 (7) | 0.0058 (5) | 0.0064 (5) | 0.0065 (5) |
C3 | 0.0304 (7) | 0.0262 (7) | 0.0195 (6) | 0.0050 (6) | 0.0012 (5) | 0.0084 (5) |
C4 | 0.0497 (10) | 0.0282 (7) | 0.0268 (7) | 0.0063 (7) | 0.0146 (7) | 0.0116 (6) |
C5 | 0.0203 (7) | 0.0247 (6) | 0.0197 (6) | 0.0020 (5) | −0.0010 (5) | 0.0053 (5) |
C6 | 0.0207 (7) | 0.0240 (6) | 0.0221 (7) | 0.0005 (5) | 0.0007 (5) | 0.0050 (5) |
C7 | 0.0279 (8) | 0.0265 (7) | 0.0351 (8) | 0.0044 (6) | 0.0017 (6) | 0.0104 (6) |
C8 | 0.0330 (8) | 0.0294 (7) | 0.0361 (8) | −0.0040 (6) | −0.0060 (6) | 0.0157 (6) |
C9 | 0.0273 (8) | 0.0466 (9) | 0.0323 (8) | −0.0058 (7) | 0.0017 (6) | 0.0198 (7) |
C10 | 0.0230 (7) | 0.0412 (8) | 0.0296 (7) | 0.0047 (6) | 0.0062 (6) | 0.0124 (6) |
N1 | 0.0286 (6) | 0.0252 (6) | 0.0203 (6) | 0.0096 (5) | 0.0050 (5) | 0.0042 (4) |
N2 | 0.0226 (6) | 0.0267 (6) | 0.0210 (6) | 0.0050 (5) | 0.0029 (4) | 0.0057 (4) |
N3 | 0.0230 (6) | 0.0212 (5) | 0.0203 (6) | 0.0029 (4) | 0.0010 (4) | 0.0051 (4) |
N4 | 0.0250 (6) | 0.0246 (6) | 0.0276 (6) | 0.0045 (5) | 0.0050 (5) | 0.0080 (5) |
O | 0.0331 (6) | 0.0341 (6) | 0.0240 (5) | 0.0136 (5) | 0.0027 (4) | 0.0008 (4) |
C1—O | 1.2364 (16) | C5—C10 | 1.410 (2) |
C1—N1 | 1.3199 (18) | C6—N4 | 1.3607 (18) |
C1—C2 | 1.5187 (18) | C6—C7 | 1.4098 (19) |
C2—C3 | 1.514 (2) | C7—C8 | 1.360 (2) |
C2—C4 | 1.5255 (18) | C7—H9 | 0.9500 |
C2—H3 | 1.0000 | C8—C9 | 1.415 (2) |
C3—N3 | 1.4598 (17) | C8—H10 | 0.9500 |
C3—H5 | 0.9900 | C9—C10 | 1.363 (2) |
C3—H4 | 0.9900 | C9—H11 | 0.9500 |
C4—H6 | 0.9800 | C10—H12 | 0.9500 |
C4—H8 | 0.9800 | N1—H1 | 0.8800 |
C4—H7 | 0.9800 | N1—H2 | 0.8800 |
C5—N2 | 1.3498 (18) | N2—N3 | 1.3276 (16) |
C5—C6 | 1.4013 (19) | N3—N4 | 1.3198 (16) |
O—C1—N1 | 123.67 (12) | N4—C6—C5 | 108.31 (12) |
O—C1—C2 | 119.91 (12) | N4—C6—C7 | 130.81 (13) |
N1—C1—C2 | 116.40 (11) | C5—C6—C7 | 120.88 (13) |
C3—C2—C1 | 110.76 (11) | C8—C7—C6 | 116.86 (13) |
C3—C2—C4 | 108.52 (12) | C8—C7—H9 | 121.6 |
C1—C2—C4 | 108.88 (11) | C6—C7—H9 | 121.6 |
C3—C2—H3 | 109.6 | C7—C8—C9 | 122.17 (13) |
C1—C2—H3 | 109.6 | C7—C8—H10 | 118.9 |
C4—C2—H3 | 109.6 | C9—C8—H10 | 118.9 |
N3—C3—C2 | 112.65 (11) | C10—C9—C8 | 122.07 (14) |
N3—C3—H5 | 109.1 | C10—C9—H11 | 119.0 |
C2—C3—H5 | 109.1 | C8—C9—H11 | 119.0 |
N3—C3—H4 | 109.1 | C9—C10—C5 | 116.47 (14) |
C2—C3—H4 | 109.1 | C9—C10—H12 | 121.8 |
H5—C3—H4 | 107.8 | C5—C10—H12 | 121.8 |
C2—C4—H6 | 109.5 | C1—N1—H1 | 120.0 |
C2—C4—H8 | 109.5 | C1—N1—H2 | 120.0 |
H6—C4—H8 | 109.5 | H1—N1—H2 | 120.0 |
C2—C4—H7 | 109.5 | N3—N2—C5 | 103.09 (11) |
H6—C4—H7 | 109.5 | N4—N3—N2 | 117.11 (11) |
H8—C4—H7 | 109.5 | N4—N3—C3 | 121.80 (11) |
N2—C5—C6 | 108.57 (12) | N2—N3—C3 | 121.07 (11) |
N2—C5—C10 | 129.88 (13) | N3—N4—C6 | 102.93 (11) |
C6—C5—C10 | 121.56 (13) | ||
O—C1—C2—C3 | 45.53 (16) | C8—C9—C10—C5 | −0.2 (2) |
N1—C1—C2—C3 | −136.47 (12) | N2—C5—C10—C9 | −179.87 (13) |
O—C1—C2—C4 | −73.73 (16) | C6—C5—C10—C9 | 0.0 (2) |
N1—C1—C2—C4 | 104.27 (14) | C6—C5—N2—N3 | −0.24 (13) |
C1—C2—C3—N3 | 59.74 (14) | C10—C5—N2—N3 | 179.62 (14) |
C4—C2—C3—N3 | 179.22 (10) | C5—N2—N3—N4 | 0.10 (14) |
N2—C5—C6—N4 | 0.30 (14) | C5—N2—N3—C3 | −178.27 (11) |
C10—C5—C6—N4 | −179.57 (12) | C2—C3—N3—N4 | 65.73 (15) |
N2—C5—C6—C7 | −179.77 (12) | C2—C3—N3—N2 | −115.97 (13) |
C10—C5—C6—C7 | 0.4 (2) | N2—N3—N4—C6 | 0.08 (15) |
N4—C6—C7—C8 | 179.50 (14) | C3—N3—N4—C6 | 178.44 (11) |
C5—C6—C7—C8 | −0.41 (19) | C5—C6—N4—N3 | −0.23 (14) |
C6—C7—C8—C9 | 0.2 (2) | C7—C6—N4—N3 | 179.86 (13) |
C7—C8—C9—C10 | 0.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Oi | 0.88 | 2.00 | 2.8745 (18) | 170 |
N1—H2···N2ii | 0.88 | 2.24 | 3.0850 (18) | 161 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z. |
C11H14N4O | Z = 2 |
Mr = 218.26 | F(000) = 232 |
Triclinic, P1 | Dx = 1.342 Mg m−3 |
a = 7.1732 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.9945 (6) Å | Cell parameters from 6240 reflections |
c = 9.5912 (7) Å | θ = 2.1–29.2° |
α = 83.910 (6)° | µ = 0.09 mm−1 |
β = 86.247 (6)° | T = 153 K |
γ = 81.528 (6)° | Block, colorless |
V = 540.25 (7) Å3 | 0.34 × 0.32 × 0.28 mm |
Stoe IPDS 2T diffractometer | 1596 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
area detector scans | h = −8→8 |
4194 measured reflections | k = −9→9 |
1904 independent reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0794P)2 + 0.073P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
1904 reflections | Δρmax = 0.22 e Å−3 |
149 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.062 (15) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.2374 (2) | 0.1609 (2) | 0.89843 (17) | 0.0317 (4) | |
C2 | 0.2225 (3) | 0.3473 (2) | 0.91977 (18) | 0.0357 (4) | |
H2 | 0.312766 | 0.361341 | 0.990012 | 0.043* | |
H1 | 0.093801 | 0.387131 | 0.957760 | 0.043* | |
C3 | 0.2629 (3) | 0.4566 (2) | 0.78541 (18) | 0.0363 (4) | |
H4 | 0.187972 | 0.427798 | 0.710496 | 0.044* | |
H3 | 0.221528 | 0.577397 | 0.800163 | 0.044* | |
C4 | 0.5548 (2) | 0.34481 (19) | 0.63744 (16) | 0.0308 (4) | |
C5 | 0.7407 (3) | 0.3710 (2) | 0.64288 (17) | 0.0356 (4) | |
C6 | 0.8817 (3) | 0.2937 (2) | 0.5534 (2) | 0.0441 (5) | |
H5 | 1.009954 | 0.309393 | 0.557083 | 0.053* | |
C7 | 0.8268 (3) | 0.1947 (2) | 0.46046 (19) | 0.0441 (5) | |
H6 | 0.919384 | 0.139249 | 0.398995 | 0.053* | |
C8 | 0.6372 (3) | 0.1724 (2) | 0.45317 (18) | 0.0397 (5) | |
H7 | 0.604940 | 0.104362 | 0.385487 | 0.048* | |
C9 | 0.4981 (3) | 0.2455 (2) | 0.54036 (17) | 0.0352 (4) | |
H8 | 0.370003 | 0.230034 | 0.535556 | 0.042* | |
C10 | 0.2411 (3) | 0.0869 (3) | 1.15684 (19) | 0.0505 (5) | |
H10 | 0.138000 | 0.036749 | 1.209814 | 0.061* | |
H9 | 0.219291 | 0.210450 | 1.159458 | 0.061* | |
H11 | 0.360994 | 0.040258 | 1.198882 | 0.061* | |
C11 | 0.2605 (3) | −0.1321 (2) | 0.9926 (2) | 0.0454 (5) | |
H13A | 0.386119 | −0.190604 | 1.015826 | 0.054* | 0.59 (2) |
H14A | 0.238741 | −0.144173 | 0.894596 | 0.054* | 0.59 (2) |
H12A | 0.164666 | −0.182399 | 1.054197 | 0.054* | 0.59 (2) |
H12B | 0.140231 | −0.154180 | 0.960587 | 0.054* | 0.41 (2) |
H13B | 0.287609 | −0.200611 | 1.081816 | 0.054* | 0.41 (2) |
H14B | 0.361685 | −0.162385 | 0.922216 | 0.054* | 0.41 (2) |
N1 | 0.2484 (2) | 0.04712 (18) | 1.01231 (15) | 0.0362 (4) | |
N2 | 0.4605 (2) | 0.43518 (16) | 0.73920 (14) | 0.0327 (4) | |
N3 | 0.5824 (2) | 0.51402 (18) | 0.80163 (15) | 0.0390 (4) | |
N4 | 0.7510 (2) | 0.4768 (2) | 0.74587 (16) | 0.0422 (4) | |
O | 0.2366 (2) | 0.11687 (15) | 0.77971 (13) | 0.0442 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0305 (8) | 0.0308 (8) | 0.0359 (9) | −0.0073 (6) | −0.0002 (7) | −0.0095 (7) |
C2 | 0.0391 (10) | 0.0295 (8) | 0.0404 (9) | −0.0059 (7) | 0.0002 (7) | −0.0114 (7) |
C3 | 0.0403 (10) | 0.0251 (8) | 0.0446 (9) | −0.0027 (7) | −0.0055 (8) | −0.0088 (7) |
C4 | 0.0403 (9) | 0.0226 (7) | 0.0307 (8) | −0.0074 (7) | −0.0052 (7) | −0.0021 (6) |
C5 | 0.0421 (10) | 0.0325 (8) | 0.0345 (8) | −0.0118 (7) | −0.0058 (7) | −0.0020 (7) |
C6 | 0.0380 (10) | 0.0498 (11) | 0.0452 (10) | −0.0101 (8) | −0.0022 (8) | −0.0020 (8) |
C7 | 0.0528 (12) | 0.0388 (10) | 0.0387 (10) | −0.0024 (8) | 0.0040 (8) | −0.0046 (7) |
C8 | 0.0592 (12) | 0.0289 (8) | 0.0330 (9) | −0.0102 (8) | −0.0031 (8) | −0.0066 (7) |
C9 | 0.0453 (10) | 0.0281 (8) | 0.0352 (9) | −0.0111 (7) | −0.0066 (7) | −0.0064 (7) |
C10 | 0.0641 (13) | 0.0521 (12) | 0.0382 (10) | −0.0184 (10) | −0.0010 (9) | −0.0050 (8) |
C11 | 0.0473 (11) | 0.0292 (9) | 0.0601 (12) | −0.0079 (8) | −0.0025 (9) | −0.0032 (8) |
N1 | 0.0405 (8) | 0.0313 (7) | 0.0386 (8) | −0.0088 (6) | −0.0016 (6) | −0.0065 (6) |
N2 | 0.0418 (8) | 0.0245 (6) | 0.0349 (7) | −0.0102 (6) | −0.0056 (6) | −0.0071 (5) |
N3 | 0.0482 (9) | 0.0340 (7) | 0.0401 (8) | −0.0164 (7) | −0.0093 (7) | −0.0090 (6) |
N4 | 0.0446 (9) | 0.0438 (9) | 0.0429 (8) | −0.0166 (7) | −0.0073 (7) | −0.0092 (7) |
O | 0.0648 (9) | 0.0330 (7) | 0.0382 (7) | −0.0126 (6) | −0.0033 (6) | −0.0111 (5) |
C1—O | 1.228 (2) | C7—H6 | 0.9500 |
C1—N1 | 1.344 (2) | C8—C9 | 1.364 (3) |
C1—C2 | 1.513 (2) | C8—H7 | 0.9500 |
C2—C3 | 1.515 (2) | C9—H8 | 0.9500 |
C2—H2 | 0.9900 | C10—N1 | 1.451 (2) |
C2—H1 | 0.9900 | C10—H10 | 0.9800 |
C3—N2 | 1.448 (2) | C10—H9 | 0.9800 |
C3—H4 | 0.9900 | C10—H11 | 0.9800 |
C3—H3 | 0.9900 | C11—N1 | 1.455 (2) |
C4—N2 | 1.361 (2) | C11—H13A | 0.9800 |
C4—C5 | 1.385 (3) | C11—H14A | 0.9800 |
C4—C9 | 1.401 (2) | C11—H12A | 0.9800 |
C5—N4 | 1.379 (2) | C11—H12B | 0.9800 |
C5—C6 | 1.399 (3) | C11—H13B | 0.9800 |
C6—C7 | 1.365 (3) | C11—H14B | 0.9800 |
C6—H5 | 0.9500 | N2—N3 | 1.3535 (19) |
C7—C8 | 1.404 (3) | N3—N4 | 1.296 (2) |
O—C1—N1 | 121.60 (14) | N1—C10—H9 | 109.5 |
O—C1—C2 | 120.14 (15) | H10—C10—H9 | 109.5 |
N1—C1—C2 | 118.25 (14) | N1—C10—H11 | 109.5 |
C1—C2—C3 | 112.71 (13) | H10—C10—H11 | 109.5 |
C1—C2—H2 | 109.1 | H9—C10—H11 | 109.5 |
C3—C2—H2 | 109.1 | N1—C11—H13A | 109.5 |
C1—C2—H1 | 109.1 | N1—C11—H14A | 109.5 |
C3—C2—H1 | 109.1 | H13A—C11—H14A | 109.5 |
H2—C2—H1 | 107.8 | N1—C11—H12A | 109.5 |
N2—C3—C2 | 113.14 (14) | H13A—C11—H12A | 109.5 |
N2—C3—H4 | 109.0 | H14A—C11—H12A | 109.5 |
C2—C3—H4 | 109.0 | N1—C11—H12B | 109.5 |
N2—C3—H3 | 109.0 | H13A—C11—H12B | 141.1 |
C2—C3—H3 | 109.0 | H14A—C11—H12B | 56.3 |
H4—C3—H3 | 107.8 | H12A—C11—H12B | 56.3 |
N2—C4—C5 | 104.46 (14) | N1—C11—H13B | 109.5 |
N2—C4—C9 | 133.38 (16) | H13A—C11—H13B | 56.3 |
C5—C4—C9 | 122.15 (16) | H14A—C11—H13B | 141.1 |
N4—C5—C4 | 108.56 (16) | H12A—C11—H13B | 56.3 |
N4—C5—C6 | 130.69 (17) | H12B—C11—H13B | 109.5 |
C4—C5—C6 | 120.75 (16) | N1—C11—H14B | 109.5 |
C7—C6—C5 | 117.01 (17) | H13A—C11—H14B | 56.3 |
C7—C6—H5 | 121.5 | H14A—C11—H14B | 56.3 |
C5—C6—H5 | 121.5 | H12A—C11—H14B | 141.1 |
C6—C7—C8 | 121.86 (18) | H12B—C11—H14B | 109.5 |
C6—C7—H6 | 119.1 | H13B—C11—H14B | 109.5 |
C8—C7—H6 | 119.1 | C1—N1—C10 | 125.72 (14) |
C9—C8—C7 | 121.95 (16) | C1—N1—C11 | 118.52 (14) |
C9—C8—H7 | 119.0 | C10—N1—C11 | 115.70 (15) |
C7—C8—H7 | 119.0 | N3—N2—C4 | 109.63 (14) |
C8—C9—C4 | 116.25 (16) | N3—N2—C3 | 119.52 (13) |
C8—C9—H8 | 121.9 | C4—N2—C3 | 130.85 (14) |
C4—C9—H8 | 121.9 | N4—N3—N2 | 109.52 (13) |
N1—C10—H10 | 109.5 | N3—N4—C5 | 107.81 (14) |
O—C1—C2—C3 | −16.2 (2) | C2—C1—N1—C10 | 2.2 (3) |
N1—C1—C2—C3 | 164.77 (15) | O—C1—N1—C11 | 0.2 (3) |
C1—C2—C3—N2 | −72.24 (18) | C2—C1—N1—C11 | 179.27 (15) |
N2—C4—C5—N4 | −0.66 (18) | C5—C4—N2—N3 | 0.86 (18) |
C9—C4—C5—N4 | 178.42 (14) | C9—C4—N2—N3 | −178.07 (17) |
N2—C4—C5—C6 | 178.83 (15) | C5—C4—N2—C3 | −179.29 (15) |
C9—C4—C5—C6 | −2.1 (3) | C9—C4—N2—C3 | 1.8 (3) |
N4—C5—C6—C7 | −179.73 (18) | C2—C3—N2—N3 | −78.81 (17) |
C4—C5—C6—C7 | 0.9 (3) | C2—C3—N2—C4 | 101.35 (19) |
C5—C6—C7—C8 | 0.8 (3) | C4—N2—N3—N4 | −0.77 (19) |
C6—C7—C8—C9 | −1.4 (3) | C3—N2—N3—N4 | 179.36 (14) |
C7—C8—C9—C4 | 0.2 (2) | N2—N3—N4—C5 | 0.32 (18) |
N2—C4—C9—C8 | −179.75 (17) | C4—C5—N4—N3 | 0.23 (19) |
C5—C4—C9—C8 | 1.5 (2) | C6—C5—N4—N3 | −179.20 (18) |
O—C1—N1—C10 | −176.82 (17) |
Acknowledgements
The material is based on work supported by the National Science Foundation under CHE-1461175. General financial support by the Otto-von-Guericke-Universität Magdeburg is also gratefully acknowledged.
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