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Crystal structures of N2,N3,N5,N6-tetrakis(pyridin-2-ylmethyl)pyrazine-2,3,5,6-tetracarboxamide and N2,N3,N5,N6-tetrakis(pyridin-4-ylmethyl)pyrazine-2,3,5,6-tetracarboxamide
aDebiopharm International S.A., Chemin Messidor 5-7, CP 5911, CH-1002 Lausanne, Switzerland, and bInsitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
*Correspondence e-mail: helen.stoeckli-evans@unine.ch
The title compounds, C32H28N10O4· unknown solvent, (I), and C32H28N10O4, (II), are pyrazine-2,3,5,6-tetracarboxamide derivatives. In (I), the substituents are (pyridin-2-ylmethyl)carboxamide, while in (II), the substituents are (pyridin-4-ylmethyl)carboxamide. Both compounds crystallize in the monoclinic P21/n, with Z′ = 1 for (I), and Z′ = 0.5 for (II). The whole molecule of (II) is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I), the four pyridine rings are inclined to the pyrazine ring by 83.9 (2), 82.16 (18), 82.73 (19) and 17.65 (19)°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intramolecular C—H⋯O hydrogen bond. In compound (II), the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°. There are two symmetrical intramolecular C—H⋯O hydrogen bonds present in (II). In the crystal of (I), molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, forming layers parallel to (10-1). The layers are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II), molecules are linked by N—H⋯N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N—H⋯N hydrogen bond, forming layers parallel to the (101) plane, which are in turn linked by C—H⋯O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I), a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015). Acta Cryst. C71, 9–18]. Their contribution was not taken into account during In compound (II), one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car—Car—Npy atoms is 0.58 (3):0.42 (3).
Keywords: crystal structure; pyrazine; pyridine; tetracarboxamide; hydrogen bonding.
1. Chemical context
Tetrakis-substituted pyrazine ligands for coordination chemistry, excluding tetramethylpyrazine or pyrazine-2,3,5,6-tetracarbonitrile, are almost exclusively limited to tetrakis(2′-pyridyl)pyrazine (tppz) and tetrakis(carboxylic acid)pyrazine (H4pztc). Tppz was first synthesized by Goodwin & Lions (1959). The of the first coordination compound of tppz to be reported was a binucluear copper(II) complex, bis{diaqua[μ2-2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N′,N′′,N′′′,N′′′′,N′′′′′]copper(II)} tetraperchlorate dihydrate, with the ligand coordinating in a bis-tridentate manner (Graf et al., 1993
). H4pztc is a much older compound, whose synthesis was first reported by Wolf (1887
, 1893
). The first published complex of H4pztc is a one-dimensional iron(II) coordination polymer, catena-[μ2-(2,5-dicarboxypyrazine-3,6-dicarboxylato-N,O)-trans-diaquadiiron(II)] dihydrate (Marioni et al., 1986
), in which the ligand coordinates in a bis-bidentate manner. There are of course a number of complexes in which H4pztc coordinates in a bis-tridentate manner (Cambridge Structural Database; Groom et al., 2016
). Recently, the first pyrazine-2,3,5,6-tetracarboxamide ligand was reported, namely, N,N′,N′′,N′′′-tetraethylpyrazine-2,3,5,6-tetracarboxamide, together with its binculear palladium(II) acetate complex (Lohrman et al., 2016
), in which the ligand coordinates in a bis-tridentate manner.
The title compounds are part of a series of mono-, bis- and tetrakis-substituted carboxamide pyrazine ligands synthesized in order to study their coordination chemistry with first row transition metals and the magnetic exchange properties of the complexes (Cati, 2002; Cati et al., 2004
). One such ligand is N,N′-bis(2-pyridylmethyl)pyrazine-2,3-dicarboxamide, for which two polymorphs have been reported: orthorhombic (Cati & Stoeckli-Evans, 2004
) and triclinic (Cati et al., 2004
). The reaction of this ligand with copper perchlorate and nickel chloride lead to the formation of [2×2] grid-like structures (Cati et al., 2004
), with multiple encapsulation of the anions. Klingele et al. (2007
) have also reported the crystal structures of Cu(BF4)2 and Ni(BF4)2 complexes of the same ligand, which also form [2×2] grid-like structures, but this time no encapsulation of the anions was observed. Herein, we report on the synthesis and crystal structures of the title pyrazine-2,3,5,6-tetracarboxamide derivatives, N2,N3,N5,N6-tetrakis(pyridin-2-ylmethyl)pyrazine-2,3,5,6-tetracarboxamide (I)
and N2,N3,N5,N6-tetrakis(pyridin-4-ylmethyl)pyrazine-2,3,5,6-tetracarboxamide (II)
, potential bis-tridentate coordinating ligands.
2. Structural commentary
Both title compounds, (I) and (II)
, crystallize in the monoclinic P21/n, with Z′ = 1 for (I)
, and Z′ = 0.5 for (II)
. The whole molecule of (II)
is generated by inversion symmetry; the pyrazine ring being situated about a center of inversion.
The molecular structure of compound (I), in which the substituents are (pyridin-2-ylmethyl)carboxamide, is illustrated in Fig. 1
. Pyridine rings N4/C7–C11, N6/C14–C18 and N8/C21–C25 are inclined to the pyrazine ring by 83.9 (2), 82.16 (18) and 82.73 (19)°, respectively. Pyridine ring N10/C28–C32 is inclined to the pyrazine ring by only 17.65 (19)°, and it is involved in an intramolecular C29—H20⋯O3 hydrogen bond (Fig. 1
, Table 1
). Adjacent pyridine rings are inclined to one another by 13.7 (2)° for rings N4/C7–C11 and N6/C14–C18, and by 84.5 (2)° for rings N8/C21–C25 and N10/C28–C32.
|
![]() | Figure 1 A view of the molecular structure of compound (I) ![]() ![]() |
The molecular structure of compound (II), in which the substituents are (pyridin-4-ylmethyl)carboxamide, is shown in Fig. 2
. Here, the unique pyridine rings N3A/C5–C7/C8A/C9A [A indicates the major component of the disordered atoms] and N5/C12–C16 are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°, respectively, and by 68.4 (3)° to one another. In (II)
there are also intramolecular C—H⋯O hydrogen bonds present, as shown in Fig. 2
(see also Table 2
).
|
![]() | Figure 2 A view of the molecular structure of compound (II) ![]() ![]() |
There are no intramolecular N—H⋯O hydrogen bonds present in either structure and the shortest O⋯O distances, involving adjacent carboxamide groups, are O1⋯O2 = 3.039 (3) Å in (I), and O1⋯O2(−x, −y + 1, −z + 2) = 3.088 (2) Å in (II)
. In (I)
, the amide groups in positions 2- and 6- (N3—C5=O1 and N9—C26=O4) are inclined to the pyrazine ring by 67.1 (4) and 83.7 (4)°, respectively, while those in positions 3- and 5- (N5—C12=O2 and N7—C19=O3) are inclined to the pyrazine ring by 14.2 (4) and 21.6 (4)°, respectively.
In (II), the amide group N2—C3=O1, in position 2- (and 5- by symmetry), is inclined to the pyrazine ring by 81.0 (3)°, while the amide group N4—C10=O2, in position 3- (and 6- by symmetry), lies in the plane of the pyrazine ring [dihedral angle = 1.91 (2)°]. Hence, from the various dihedral angles commented on above it can be seen that the conformations of the two molecules are significantly different (cf. Fig. 1
and Fig. 2
).
3. Supramolecular features
In the crystal of (I), molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, forming layers parallel to (10
); see Fig. 3
and Table 1
. The layers are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional framework (Table 1
, Fig. 4
).
![]() | Figure 3 A view along the b axis, of the crystal packing of compound (I) ![]() ![]() |
![]() | Figure 4 A view along the b axis, of the crystal packing of compound (I) ![]() ![]() |
In the crystal of (II), molecules are linked by N—H⋯N hydrogen bonds (Table 2
), forming chains propagating along [010], as shown in Fig. 5
. The chains are linked by weaker N—H⋯N hydrogen bonds, forming layers (Table 2
, Fig. 6
), parallel to (101). The layers are in turn linked by C—H⋯O hydrogen bonds, forming a three-dimensional framework (Table 2
, Fig. 7
).
![]() | Figure 5 A partial view along the c axis, of the crystal packing of compound (II) ![]() ![]() |
![]() | Figure 6 A view normal to plane (101), of the crystal packing of compound (II) ![]() ![]() |
![]() | Figure 7 A view along the a axis of the crystal packing of compound (II) ![]() ![]() |
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.38, first update November 2016; Groom et al., 2016) for tetrakis-substituted pyrazines, excluding tetramethylpyrazine or pyrazine-2,3,5,6-tetracarbonitrile, gave over 550 hits. 255 of these structures concern the ligand tppz, while 88 concern the ligand H4pztc. As noted above, only one example of a pyrazine-2,3,5,6-tetracarboxamide compound has been reported, viz. N,N′,N′′,N′′′-tetraethylpyrazine-2,3,5,6-tetracarboxamide (CSD refcode: OSUTIH; Lohrman et al., 2016
). It crystallizes in the triclinic P
, with eleven independent molecules in the It is interesting to note that the general orientation of the amide groups resembles that observed in compound (I)
. Those in positions 2- and 6- are inclined to the pyrazine ring by more than ca 60 °, while those at positions 3- and 5- lie close to the plane of the pyrazine ring.
5. Synthesis and crystallization
Tetramethyl pyrazine-2,3,5,6-tetracarboxylate (L) was synthesized by the method of Mager & Berends (1960).
Compound (I): A mixture of L (0.16 g, 0.5 mmol) and an excess of 2-(aminomethyl)pyridine (0.27 g, 2.5 mmol) in 20 ml of methanol were refluxed for 6 h in a two-necked flask (50 ml). The ligand H4L8 precipitated as a white solid during the reaction. The suspension was cooled to room temperature and then filtered and washed with 10 ml of cold methanol [yield 90%, m.p. 497 K(decomposition)] . 1H NMR (400 MHz, DMSO-d6): 9.52 (t, 1H, Jhg = 6.1, Hh); 8.53 (ddd, 1H, Jbc = 4.8, Jbd = 1.8, Jbe = 0.9, Hb); 7.76 (td, 1H, Jdc = 7.7, Jdb = 1.8, Hd); 7.51 (d, 1H, Jed = 7.8, He); 7.29 (ddd, 1H, Jcd = 7.7, Jcb = 4.8, Jce = 1.0, Hc); 4.64 (d, 2H, Jgh = 6.1, Hg). 13C NMR (400 MHz, DMSO-d6): 164.5, 158.9, 149.7, 146.3, 137.6, 123.2, 122.2, 45.3. IR (KBr pellet, cm−1): 3279 (s), 3054 (m), 1672 (vs), 1592 (vs), 1571 (vs), 1548 (vs), 1477 (s), 1437 (vs), 1354 (m), 1290 (m), 1247 (s), 1179 (m), 1157 (s), 1099 (w), 1049 (w), 996 (m), 799 (w), 754 (s), 684 (m), 632 (m), 608 (m), 544 (w), 521 (w). Analysis for [C32H28N10O4]·H2O (Mr = 634.65 g mol−1): calculated (%) C: 60.56 H: 4.76 N: 22.07, found (%) C: 60.46 H: 4.58 N: 21.79.
Compound (II): This compound was synthesized following the same procedure as used to prepare compound (I)
. A mixture of L (0.5 g, 1.36 mmol) and an excess of 4-(aminomethyl)pyridine (1.17 g, 10.8 mmol) were refluxed in 20 ml of methanol for 44 h in a two-necked flask (50 ml). The solution was red when hot and then turned to a brown–yellow colour on cooling to rt. The brown–yellow solid crystallized out, was filtered off and washed with cold acetonitrile (m.p. 508 K, yield 90%). 1H NMR (400 MHz, DMSO-d6): 9.50 (t, 1H, Jhg = 6.2, Hh); 8.50 (dd, 2H, Jba = 4.5, Jbe = 1.6, Hb = Hd); 7.41 (dd, 2H, Jab = 4.5, Jad = Jeb = 1.6, Ha = He); 4.59 (d, 2H, Jgh = 6.2, Hg). 13C NMR (400 MHz, DMSO-d6): 164.7, 150.4, 148.7, 146.4, 123.1, 42.3. IR (KBr pellet, cm−1): 3238 (s), 3033 (m), 1677 (vs), 1604 (vs), 1521 (vs), 1418 (vs), 1364 (s), 1317 (s), 1239 (s), 1174 (s), 1151 (s), 1069 (s), 994 (s), 781 (s), 616 (s), 501 (w), 475 (s). Analysis for [C32H28N10O4]·0.5CH3OH (Mr = 648.68 g mol−1): calculated (%) C: 61.10 H: 4.97 N: 21.59, found (%) C: 61.42 H: 4.62 N: 22.27.
Colourless block-like crystals of both compounds were obtained by slow evaporation of methanol solutions of the respective compounds. The elemental analysis for compound (I) required the addition of a water molecule, which possibly explains the region of disordered electron density in the crystal, and half a molecule of methanol for (II)
, which was not detected in the final difference Fourier map of the crystal used for the X-ray diffraction analysis.
6. Refinement
Crystal data, data collection and structure . For both molecules the NH H atoms were located in difference-Fourier maps and freely refined. The C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.2Ueq(C). In the crystal of compound (I)
, a region of disordered electron density was treated with the SQUEEZE routine in PLATON (Spek, 2015
). Their contribution (93 electrons for a solvent-accessible volume of 268 Å3) was not taken into account during The crystal of (I)
did not diffract significantly beyond 20 ° in θ and hence the Rint value is high (> 0.2), and only 35% of the data can be considered to be observed [I > 2σ(I)]. In compound (II)
, pyridine ring (N3/C5–C9) is positionally disordered (see Fig. 2
), and the refined occupancy ratio for the disordered atoms, N3A:N3B, C8A:C8B, C9A:C9B is 0.58 (3):0.42 (3).
|
Supporting information
https://doi.org/10.1107/S205698901700127X/lh5836sup1.cif
contains datablocks I, II, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700127X/lh5836Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698901700127X/lh5836IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698901700127X/lh5836Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S205698901700127X/lh5836IIsup5.cml
For both compounds, data collection: EXPOSE in IPDS-I (Stoe & Cie, 2000); cell
CELL in IPDS-I (Stoe & Cie, 2000); data reduction: INTEGRATE in IPDS-I (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).C32H28N10O4 | F(000) = 1288 |
Mr = 616.64 | Dx = 1.287 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.0754 (19) Å | Cell parameters from 6905 reflections |
b = 11.8602 (10) Å | θ = 2.1–26.0° |
c = 18.495 (2) Å | µ = 0.09 mm−1 |
β = 115.503 (13)° | T = 153 K |
V = 3182.6 (7) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Stoe IPDS 1 diffractometer | 6150 independent reflections |
Radiation source: fine-focus sealed tube | 2219 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.211 |
φ rotation scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −19→19 |
Tmin = 0.865, Tmax = 1.000 | k = −14→14 |
26683 measured reflections | l = −22→22 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0393P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.72 | (Δ/σ)max < 0.001 |
6150 reflections | Δρmax = 0.28 e Å−3 |
432 parameters | Δρmin = −0.30 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: 0.0015 (3) |
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 | ||
O1 | 0.17252 (16) | 0.2650 (2) | 0.25371 (13) | 0.0262 (6) | |
O2 | 0.11731 (16) | 0.4901 (2) | 0.29838 (13) | 0.0270 (6) | |
O3 | 0.15003 (16) | 0.6495 (2) | −0.05042 (13) | 0.0248 (6) | |
O4 | 0.03328 (16) | 0.4184 (2) | −0.10516 (13) | 0.0296 (7) | |
N1 | 0.10335 (18) | 0.3788 (2) | 0.07667 (15) | 0.0209 (7) | |
N2 | 0.17209 (18) | 0.5881 (2) | 0.14404 (15) | 0.0196 (7) | |
N3 | 0.0179 (2) | 0.2690 (3) | 0.17069 (17) | 0.0238 (7) | |
H3N | −0.029 (3) | 0.307 (4) | 0.125 (3) | 0.084 (17)* | |
N4 | −0.0867 (2) | 0.0255 (3) | 0.10199 (18) | 0.0424 (10) | |
N5 | 0.1965 (2) | 0.6453 (3) | 0.29048 (18) | 0.0235 (8) | |
H5N | 0.222 (2) | 0.680 (3) | 0.269 (2) | 0.019 (11)* | |
N6 | 0.1542 (2) | 0.8767 (3) | 0.39734 (17) | 0.0260 (8) | |
N7 | 0.2429 (2) | 0.7300 (3) | 0.07033 (18) | 0.0225 (7) | |
H7N | 0.265 (3) | 0.723 (4) | 0.121 (2) | 0.053 (14)* | |
N8 | 0.3666 (2) | 0.7102 (3) | −0.02182 (18) | 0.0329 (8) | |
N9 | 0.1864 (2) | 0.3770 (3) | −0.04837 (17) | 0.0216 (7) | |
H9N | 0.236 (3) | 0.367 (4) | 0.000 (3) | 0.082 (17)* | |
N10 | 0.2190 (2) | 0.3237 (3) | −0.23133 (17) | 0.0308 (8) | |
C1 | 0.1173 (2) | 0.4044 (3) | 0.15150 (18) | 0.0184 (8) | |
C2 | 0.1486 (2) | 0.5109 (3) | 0.18446 (18) | 0.0187 (8) | |
C3 | 0.1582 (2) | 0.5635 (3) | 0.06870 (19) | 0.0197 (8) | |
C4 | 0.1232 (2) | 0.4582 (3) | 0.03481 (19) | 0.0175 (8) | |
C5 | 0.1034 (2) | 0.3081 (3) | 0.19780 (19) | 0.0207 (8) | |
C6 | −0.0042 (3) | 0.1650 (3) | 0.2026 (2) | 0.0279 (9) | |
H6A | −0.065750 | 0.172843 | 0.202155 | 0.033* | |
H6B | 0.041504 | 0.154238 | 0.258835 | 0.033* | |
C7 | −0.0039 (3) | 0.0627 (3) | 0.1541 (2) | 0.0294 (10) | |
C8 | 0.0768 (3) | 0.0094 (4) | 0.1648 (3) | 0.0503 (12) | |
H8 | 0.134532 | 0.036800 | 0.203162 | 0.060* | |
C9 | 0.0729 (4) | −0.0836 (4) | 0.1195 (3) | 0.0677 (16) | |
H9 | 0.127695 | −0.121059 | 0.125562 | 0.081* | |
C10 | −0.0118 (5) | −0.1218 (4) | 0.0652 (3) | 0.0646 (16) | |
H10 | −0.016508 | −0.186399 | 0.033254 | 0.078* | |
C11 | −0.0891 (4) | −0.0651 (4) | 0.0579 (3) | 0.0578 (15) | |
H11 | −0.147385 | −0.091176 | 0.019642 | 0.069* | |
C12 | 0.1531 (2) | 0.5463 (3) | 0.26412 (19) | 0.0221 (9) | |
C13 | 0.2021 (2) | 0.6979 (3) | 0.36311 (19) | 0.0245 (9) | |
H13A | 0.263666 | 0.732720 | 0.391842 | 0.029* | |
H13B | 0.195560 | 0.639111 | 0.398331 | 0.029* | |
C14 | 0.1290 (2) | 0.7871 (3) | 0.34741 (19) | 0.0229 (9) | |
C15 | 0.0409 (3) | 0.7782 (4) | 0.2867 (2) | 0.0392 (11) | |
H15 | 0.024542 | 0.715957 | 0.250896 | 0.047* | |
C16 | −0.0228 (3) | 0.8602 (4) | 0.2787 (2) | 0.0408 (12) | |
H16 | −0.084386 | 0.853260 | 0.238703 | 0.049* | |
C17 | 0.0024 (2) | 0.9522 (3) | 0.3285 (2) | 0.0269 (9) | |
H17 | −0.040291 | 1.010774 | 0.322741 | 0.032* | |
C18 | 0.0917 (3) | 0.9572 (3) | 0.3872 (2) | 0.0300 (10) | |
H18 | 0.109726 | 1.020517 | 0.421982 | 0.036* | |
C19 | 0.1827 (2) | 0.6525 (3) | 0.0241 (2) | 0.0223 (9) | |
C20 | 0.2835 (2) | 0.8163 (3) | 0.0381 (2) | 0.0240 (9) | |
H20A | 0.294428 | 0.886330 | 0.070075 | 0.029* | |
H20B | 0.240326 | 0.833907 | −0.017922 | 0.029* | |
C21 | 0.3727 (2) | 0.7740 (3) | 0.04113 (19) | 0.0215 (8) | |
C22 | 0.4560 (3) | 0.7938 (3) | 0.1066 (2) | 0.0312 (10) | |
H22 | 0.458295 | 0.838750 | 0.149923 | 0.037* | |
C23 | 0.5354 (3) | 0.7478 (4) | 0.1084 (2) | 0.0377 (11) | |
H23 | 0.593158 | 0.761289 | 0.152609 | 0.045* | |
C24 | 0.5298 (3) | 0.6823 (4) | 0.0454 (2) | 0.0389 (11) | |
H24 | 0.583563 | 0.649171 | 0.045208 | 0.047* | |
C25 | 0.4446 (3) | 0.6654 (4) | −0.0177 (2) | 0.0391 (11) | |
H25 | 0.441200 | 0.619099 | −0.060761 | 0.047* | |
C26 | 0.1097 (2) | 0.4191 (3) | −0.04760 (19) | 0.0223 (8) | |
C27 | 0.1859 (3) | 0.3171 (3) | −0.1166 (2) | 0.0271 (9) | |
H27A | 0.123425 | 0.285802 | −0.147570 | 0.033* | |
H27B | 0.228937 | 0.252544 | −0.096491 | 0.033* | |
C28 | 0.2120 (2) | 0.3846 (3) | −0.17289 (19) | 0.0227 (9) | |
C29 | 0.2268 (3) | 0.5004 (3) | −0.1660 (2) | 0.0320 (10) | |
H29 | 0.221046 | 0.541781 | −0.124359 | 0.038* | |
C30 | 0.2501 (3) | 0.5542 (4) | −0.2215 (2) | 0.0387 (11) | |
H30 | 0.261980 | 0.632934 | −0.217523 | 0.046* | |
C31 | 0.2560 (3) | 0.4926 (4) | −0.2820 (2) | 0.0361 (11) | |
H31 | 0.270793 | 0.527869 | −0.321149 | 0.043* | |
C32 | 0.2399 (3) | 0.3788 (4) | −0.2844 (2) | 0.0341 (10) | |
H32 | 0.243853 | 0.336422 | −0.326373 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0257 (14) | 0.0249 (16) | 0.0236 (13) | 0.0019 (12) | 0.0064 (11) | 0.0010 (11) |
O2 | 0.0316 (15) | 0.0256 (16) | 0.0252 (13) | −0.0051 (13) | 0.0135 (12) | 0.0022 (12) |
O3 | 0.0269 (14) | 0.0254 (16) | 0.0177 (13) | −0.0006 (12) | 0.0053 (11) | 0.0021 (11) |
O4 | 0.0226 (14) | 0.0369 (17) | 0.0216 (13) | 0.0002 (12) | 0.0021 (11) | −0.0022 (11) |
N1 | 0.0173 (15) | 0.0232 (19) | 0.0199 (15) | 0.0024 (14) | 0.0059 (12) | 0.0000 (13) |
N2 | 0.0152 (15) | 0.0207 (18) | 0.0209 (15) | 0.0015 (13) | 0.0059 (12) | −0.0024 (13) |
N3 | 0.0235 (17) | 0.0194 (19) | 0.0245 (16) | −0.0016 (15) | 0.0067 (14) | 0.0016 (14) |
N4 | 0.046 (2) | 0.029 (2) | 0.0347 (19) | −0.0138 (18) | 0.0013 (17) | −0.0013 (16) |
N5 | 0.0273 (18) | 0.022 (2) | 0.0244 (17) | −0.0036 (16) | 0.0138 (15) | −0.0035 (15) |
N6 | 0.0277 (17) | 0.0223 (19) | 0.0279 (16) | 0.0003 (15) | 0.0119 (14) | −0.0080 (14) |
N7 | 0.0257 (17) | 0.0192 (19) | 0.0218 (17) | −0.0020 (15) | 0.0095 (14) | 0.0009 (14) |
N8 | 0.037 (2) | 0.029 (2) | 0.0394 (19) | −0.0022 (17) | 0.0225 (16) | −0.0027 (15) |
N9 | 0.0240 (17) | 0.0223 (19) | 0.0192 (16) | 0.0021 (15) | 0.0101 (14) | −0.0003 (13) |
N10 | 0.0328 (19) | 0.034 (2) | 0.0282 (17) | −0.0031 (16) | 0.0155 (15) | −0.0050 (15) |
C1 | 0.0132 (17) | 0.022 (2) | 0.0170 (17) | 0.0016 (16) | 0.0038 (14) | 0.0009 (15) |
C2 | 0.0160 (18) | 0.018 (2) | 0.0207 (18) | 0.0020 (16) | 0.0064 (14) | −0.0011 (16) |
C3 | 0.0160 (18) | 0.020 (2) | 0.0206 (18) | 0.0017 (16) | 0.0050 (14) | 0.0021 (15) |
C4 | 0.0155 (18) | 0.016 (2) | 0.0209 (18) | 0.0001 (16) | 0.0075 (14) | 0.0000 (15) |
C5 | 0.024 (2) | 0.015 (2) | 0.0237 (19) | 0.0059 (17) | 0.0107 (17) | −0.0020 (15) |
C6 | 0.035 (2) | 0.023 (2) | 0.0256 (19) | −0.0068 (19) | 0.0124 (18) | −0.0025 (16) |
C7 | 0.035 (2) | 0.025 (2) | 0.026 (2) | −0.011 (2) | 0.0107 (17) | −0.0034 (17) |
C8 | 0.046 (3) | 0.037 (3) | 0.078 (3) | −0.008 (2) | 0.037 (2) | −0.018 (3) |
C9 | 0.089 (4) | 0.032 (3) | 0.110 (4) | −0.007 (3) | 0.070 (4) | −0.019 (3) |
C10 | 0.121 (5) | 0.025 (3) | 0.062 (3) | −0.030 (3) | 0.052 (3) | −0.020 (2) |
C11 | 0.083 (4) | 0.036 (3) | 0.041 (3) | −0.020 (3) | 0.015 (3) | −0.011 (2) |
C12 | 0.0189 (18) | 0.025 (2) | 0.0177 (18) | 0.0023 (17) | 0.0034 (15) | −0.0007 (16) |
C13 | 0.025 (2) | 0.028 (2) | 0.0184 (18) | −0.0028 (17) | 0.0075 (15) | −0.0034 (15) |
C14 | 0.024 (2) | 0.022 (2) | 0.0224 (18) | −0.0007 (17) | 0.0094 (15) | −0.0014 (16) |
C15 | 0.034 (2) | 0.032 (3) | 0.037 (2) | 0.005 (2) | 0.0007 (19) | −0.0133 (19) |
C16 | 0.027 (2) | 0.038 (3) | 0.039 (2) | 0.005 (2) | −0.0025 (18) | −0.014 (2) |
C17 | 0.027 (2) | 0.024 (2) | 0.0287 (19) | −0.0009 (18) | 0.0104 (17) | 0.0002 (17) |
C18 | 0.032 (2) | 0.026 (2) | 0.032 (2) | 0.003 (2) | 0.0143 (18) | −0.0066 (17) |
C19 | 0.0191 (19) | 0.022 (2) | 0.024 (2) | 0.0024 (17) | 0.0075 (16) | −0.0022 (16) |
C20 | 0.029 (2) | 0.020 (2) | 0.0253 (19) | −0.0029 (17) | 0.0137 (17) | −0.0028 (16) |
C21 | 0.027 (2) | 0.015 (2) | 0.0255 (19) | −0.0026 (17) | 0.0144 (16) | 0.0014 (16) |
C22 | 0.033 (2) | 0.025 (2) | 0.033 (2) | −0.0001 (19) | 0.0120 (18) | 0.0038 (17) |
C23 | 0.029 (2) | 0.041 (3) | 0.043 (2) | −0.003 (2) | 0.0160 (18) | 0.005 (2) |
C24 | 0.036 (2) | 0.034 (3) | 0.056 (3) | 0.006 (2) | 0.029 (2) | 0.011 (2) |
C25 | 0.040 (3) | 0.037 (3) | 0.048 (3) | −0.002 (2) | 0.025 (2) | −0.007 (2) |
C26 | 0.022 (2) | 0.024 (2) | 0.0205 (18) | −0.0008 (18) | 0.0086 (16) | −0.0017 (16) |
C27 | 0.030 (2) | 0.025 (2) | 0.025 (2) | 0.0003 (18) | 0.0103 (17) | −0.0021 (16) |
C28 | 0.0208 (19) | 0.022 (2) | 0.0223 (18) | 0.0013 (17) | 0.0062 (15) | 0.0027 (16) |
C29 | 0.037 (2) | 0.027 (3) | 0.033 (2) | −0.006 (2) | 0.0155 (18) | −0.0059 (19) |
C30 | 0.041 (3) | 0.031 (3) | 0.041 (2) | −0.007 (2) | 0.014 (2) | 0.002 (2) |
C31 | 0.033 (2) | 0.043 (3) | 0.030 (2) | −0.007 (2) | 0.0113 (18) | 0.003 (2) |
C32 | 0.037 (2) | 0.043 (3) | 0.028 (2) | −0.007 (2) | 0.0195 (18) | −0.0001 (19) |
O1—C5 | 1.256 (4) | C8—H8 | 0.9500 |
O2—C12 | 1.220 (4) | C9—C10 | 1.375 (7) |
O3—C19 | 1.246 (4) | C9—H9 | 0.9500 |
O4—C26 | 1.231 (4) | C10—C11 | 1.368 (7) |
N1—C1 | 1.338 (4) | C10—H10 | 0.9500 |
N1—C4 | 1.342 (4) | C11—H11 | 0.9500 |
N2—C2 | 1.336 (4) | C13—C14 | 1.513 (5) |
N2—C3 | 1.345 (4) | C13—H13A | 0.9900 |
N3—C5 | 1.327 (4) | C13—H13B | 0.9900 |
N3—C6 | 1.475 (5) | C14—C15 | 1.382 (5) |
N3—H3N | 0.97 (5) | C15—C16 | 1.374 (5) |
N4—C7 | 1.338 (5) | C15—H15 | 0.9500 |
N4—C11 | 1.339 (6) | C16—C17 | 1.372 (5) |
N5—C12 | 1.346 (5) | C16—H16 | 0.9500 |
N5—C13 | 1.448 (4) | C17—C18 | 1.378 (5) |
N5—H5N | 0.79 (4) | C17—H17 | 0.9500 |
N6—C18 | 1.339 (5) | C18—H18 | 0.9500 |
N6—C14 | 1.350 (4) | C20—C21 | 1.498 (5) |
N7—C19 | 1.342 (4) | C20—H20A | 0.9900 |
N7—C20 | 1.470 (5) | C20—H20B | 0.9900 |
N7—H7N | 0.86 (4) | C21—C22 | 1.385 (5) |
N8—C25 | 1.333 (5) | C22—C23 | 1.374 (6) |
N8—C21 | 1.356 (5) | C22—H22 | 0.9500 |
N9—C26 | 1.336 (4) | C23—C24 | 1.372 (6) |
N9—C27 | 1.445 (4) | C23—H23 | 0.9500 |
N9—H9N | 0.92 (4) | C24—C25 | 1.380 (5) |
N10—C32 | 1.336 (5) | C24—H24 | 0.9500 |
N10—C28 | 1.345 (5) | C25—H25 | 0.9500 |
C1—C2 | 1.399 (5) | C27—C28 | 1.509 (5) |
C1—C5 | 1.501 (5) | C27—H27A | 0.9900 |
C2—C12 | 1.504 (5) | C27—H27B | 0.9900 |
C3—C4 | 1.402 (5) | C28—C29 | 1.391 (5) |
C3—C19 | 1.494 (5) | C29—C30 | 1.390 (5) |
C4—C26 | 1.516 (5) | C29—H29 | 0.9500 |
C6—C7 | 1.511 (5) | C30—C31 | 1.374 (6) |
C6—H6A | 0.9900 | C30—H30 | 0.9500 |
C6—H6B | 0.9900 | C31—C32 | 1.372 (6) |
C7—C8 | 1.379 (6) | C31—H31 | 0.9500 |
C8—C9 | 1.369 (6) | C32—H32 | 0.9500 |
C1—N1—C4 | 117.5 (3) | N6—C14—C15 | 121.1 (4) |
C2—N2—C3 | 118.0 (3) | N6—C14—C13 | 116.1 (3) |
C5—N3—C6 | 122.0 (3) | C15—C14—C13 | 122.8 (3) |
C5—N3—H3N | 117 (3) | C16—C15—C14 | 119.3 (4) |
C6—N3—H3N | 120 (3) | C16—C15—H15 | 120.4 |
C7—N4—C11 | 117.5 (4) | C14—C15—H15 | 120.4 |
C12—N5—C13 | 121.8 (3) | C17—C16—C15 | 119.9 (4) |
C12—N5—H5N | 124 (3) | C17—C16—H16 | 120.0 |
C13—N5—H5N | 114 (3) | C15—C16—H16 | 120.0 |
C18—N6—C14 | 118.6 (3) | C16—C17—C18 | 118.0 (4) |
C19—N7—C20 | 122.9 (3) | C16—C17—H17 | 121.0 |
C19—N7—H7N | 119 (3) | C18—C17—H17 | 121.0 |
C20—N7—H7N | 118 (3) | N6—C18—C17 | 123.0 (4) |
C25—N8—C21 | 117.0 (3) | N6—C18—H18 | 118.5 |
C26—N9—C27 | 122.3 (3) | C17—C18—H18 | 118.5 |
C26—N9—H9N | 117 (3) | O3—C19—N7 | 124.7 (3) |
C27—N9—H9N | 118 (3) | O3—C19—C3 | 120.3 (3) |
C32—N10—C28 | 117.5 (4) | N7—C19—C3 | 114.9 (3) |
N1—C1—C2 | 121.6 (3) | N7—C20—C21 | 109.7 (3) |
N1—C1—C5 | 114.7 (3) | N7—C20—H20A | 109.7 |
C2—C1—C5 | 123.5 (3) | C21—C20—H20A | 109.7 |
N2—C2—C1 | 120.7 (3) | N7—C20—H20B | 109.7 |
N2—C2—C12 | 116.8 (3) | C21—C20—H20B | 109.7 |
C1—C2—C12 | 122.4 (3) | H20A—C20—H20B | 108.2 |
N2—C3—C4 | 120.8 (3) | N8—C21—C22 | 122.0 (4) |
N2—C3—C19 | 117.0 (3) | N8—C21—C20 | 116.1 (3) |
C4—C3—C19 | 122.2 (3) | C22—C21—C20 | 121.7 (3) |
N1—C4—C3 | 121.1 (3) | C23—C22—C21 | 119.5 (4) |
N1—C4—C26 | 113.5 (3) | C23—C22—H22 | 120.3 |
C3—C4—C26 | 125.3 (3) | C21—C22—H22 | 120.3 |
O1—C5—N3 | 125.0 (3) | C24—C23—C22 | 119.0 (4) |
O1—C5—C1 | 118.9 (3) | C24—C23—H23 | 120.5 |
N3—C5—C1 | 115.8 (3) | C22—C23—H23 | 120.5 |
N3—C6—C7 | 111.8 (3) | C23—C24—C25 | 118.5 (4) |
N3—C6—H6A | 109.3 | C23—C24—H24 | 120.7 |
C7—C6—H6A | 109.3 | C25—C24—H24 | 120.7 |
N3—C6—H6B | 109.3 | N8—C25—C24 | 123.9 (4) |
C7—C6—H6B | 109.3 | N8—C25—H25 | 118.0 |
H6A—C6—H6B | 107.9 | C24—C25—H25 | 118.0 |
N4—C7—C8 | 122.4 (4) | O4—C26—N9 | 124.8 (3) |
N4—C7—C6 | 115.8 (4) | O4—C26—C4 | 122.0 (3) |
C8—C7—C6 | 121.8 (3) | N9—C26—C4 | 113.0 (3) |
C9—C8—C7 | 119.2 (4) | N9—C27—C28 | 116.3 (3) |
C9—C8—H8 | 120.4 | N9—C27—H27A | 108.2 |
C7—C8—H8 | 120.4 | C28—C27—H27A | 108.2 |
C8—C9—C10 | 118.9 (5) | N9—C27—H27B | 108.2 |
C8—C9—H9 | 120.5 | C28—C27—H27B | 108.2 |
C10—C9—H9 | 120.5 | H27A—C27—H27B | 107.4 |
C11—C10—C9 | 118.8 (5) | N10—C28—C29 | 122.3 (3) |
C11—C10—H10 | 120.6 | N10—C28—C27 | 114.5 (3) |
C9—C10—H10 | 120.6 | C29—C28—C27 | 123.2 (3) |
N4—C11—C10 | 123.2 (5) | C30—C29—C28 | 118.4 (4) |
N4—C11—H11 | 118.4 | C30—C29—H29 | 120.8 |
C10—C11—H11 | 118.4 | C28—C29—H29 | 120.8 |
O2—C12—N5 | 125.1 (3) | C31—C30—C29 | 119.6 (4) |
O2—C12—C2 | 121.5 (3) | C31—C30—H30 | 120.2 |
N5—C12—C2 | 113.4 (3) | C29—C30—H30 | 120.2 |
N5—C13—C14 | 113.0 (3) | C32—C31—C30 | 118.0 (4) |
N5—C13—H13A | 109.0 | C32—C31—H31 | 121.0 |
C14—C13—H13A | 109.0 | C30—C31—H31 | 121.0 |
N5—C13—H13B | 109.0 | N10—C32—C31 | 124.2 (4) |
C14—C13—H13B | 109.0 | N10—C32—H32 | 117.9 |
H13A—C13—H13B | 107.8 | C31—C32—H32 | 117.9 |
C4—N1—C1—C2 | 2.1 (5) | N5—C13—C14—N6 | −145.5 (3) |
C4—N1—C1—C5 | −173.8 (3) | N5—C13—C14—C15 | 35.5 (5) |
C3—N2—C2—C1 | 4.9 (5) | N6—C14—C15—C16 | −2.0 (6) |
C3—N2—C2—C12 | −172.1 (3) | C13—C14—C15—C16 | 176.9 (4) |
N1—C1—C2—N2 | −5.0 (5) | C14—C15—C16—C17 | 2.8 (7) |
C5—C1—C2—N2 | 170.5 (3) | C15—C16—C17—C18 | −1.9 (6) |
N1—C1—C2—C12 | 171.9 (3) | C14—N6—C18—C17 | 0.7 (6) |
C5—C1—C2—C12 | −12.7 (5) | C16—C17—C18—N6 | 0.1 (6) |
C2—N2—C3—C4 | −2.3 (5) | C20—N7—C19—O3 | −5.1 (5) |
C2—N2—C3—C19 | 178.5 (3) | C20—N7—C19—C3 | 172.8 (3) |
C1—N1—C4—C3 | 0.5 (5) | N2—C3—C19—O3 | −160.7 (3) |
C1—N1—C4—C26 | 177.1 (3) | C4—C3—C19—O3 | 20.1 (5) |
N2—C3—C4—N1 | −0.4 (5) | N2—C3—C19—N7 | 21.3 (5) |
C19—C3—C4—N1 | 178.7 (3) | C4—C3—C19—N7 | −157.9 (3) |
N2—C3—C4—C26 | −176.5 (3) | C19—N7—C20—C21 | −92.0 (4) |
C19—C3—C4—C26 | 2.6 (5) | C25—N8—C21—C22 | 0.9 (6) |
C6—N3—C5—O1 | −2.6 (5) | C25—N8—C21—C20 | −175.6 (3) |
C6—N3—C5—C1 | 171.2 (3) | N7—C20—C21—N8 | 85.3 (4) |
N1—C1—C5—O1 | 108.5 (4) | N7—C20—C21—C22 | −91.2 (4) |
C2—C1—C5—O1 | −67.2 (5) | N8—C21—C22—C23 | 0.1 (6) |
N1—C1—C5—N3 | −65.6 (4) | C20—C21—C22—C23 | 176.4 (4) |
C2—C1—C5—N3 | 118.6 (4) | C21—C22—C23—C24 | −0.7 (6) |
C5—N3—C6—C7 | −93.0 (4) | C22—C23—C24—C25 | 0.3 (6) |
C11—N4—C7—C8 | −1.9 (6) | C21—N8—C25—C24 | −1.4 (6) |
C11—N4—C7—C6 | 180.0 (4) | C23—C24—C25—N8 | 0.8 (7) |
N3—C6—C7—N4 | −101.2 (4) | C27—N9—C26—O4 | −5.2 (6) |
N3—C6—C7—C8 | 80.6 (5) | C27—N9—C26—C4 | 168.9 (3) |
N4—C7—C8—C9 | 1.5 (7) | N1—C4—C26—O4 | 81.6 (4) |
C6—C7—C8—C9 | 179.5 (4) | C3—C4—C26—O4 | −102.1 (4) |
C7—C8—C9—C10 | −0.7 (8) | N1—C4—C26—N9 | −92.6 (4) |
C8—C9—C10—C11 | 0.4 (8) | C3—C4—C26—N9 | 83.7 (4) |
C7—N4—C11—C10 | 1.6 (7) | C26—N9—C27—C28 | 97.9 (4) |
C9—C10—C11—N4 | −0.9 (8) | C32—N10—C28—C29 | −0.9 (5) |
C13—N5—C12—O2 | −2.3 (5) | C32—N10—C28—C27 | 178.6 (3) |
C13—N5—C12—C2 | 175.4 (3) | N9—C27—C28—N10 | 174.1 (3) |
N2—C2—C12—O2 | 166.2 (3) | N9—C27—C28—C29 | −6.4 (5) |
C1—C2—C12—O2 | −10.7 (5) | N10—C28—C29—C30 | −0.4 (5) |
N2—C2—C12—N5 | −11.6 (4) | C27—C28—C29—C30 | −179.8 (3) |
C1—C2—C12—N5 | 171.5 (3) | C28—C29—C30—C31 | 1.4 (6) |
C12—N5—C13—C14 | −97.1 (4) | C29—C30—C31—C32 | −1.1 (6) |
C18—N6—C14—C15 | 0.3 (5) | C28—N10—C32—C31 | 1.2 (6) |
C18—N6—C14—C13 | −178.7 (3) | C30—C31—C32—N10 | −0.2 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C29—H29···O3 | 0.95 | 2.48 | 3.389 (5) | 160 |
N3—H3N···O3i | 0.97 (5) | 1.91 (5) | 2.829 (4) | 158 (4) |
N5—H5N···O1ii | 0.79 (4) | 2.17 (4) | 2.932 (4) | 162 (3) |
N7—H7N···O1ii | 0.86 (4) | 2.14 (4) | 2.967 (4) | 161 (4) |
N9—H9N···N6iii | 0.92 (4) | 1.96 (5) | 2.864 (4) | 169 (5) |
C13—H13A···N1ii | 0.99 | 2.62 | 3.554 (5) | 158 |
C20—H20A···O2ii | 0.99 | 2.54 | 3.433 (4) | 149 |
C22—H22···O2ii | 0.95 | 2.57 | 3.418 (5) | 149 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2. |
C32H28N10O4 | F(000) = 644 |
Mr = 616.64 | Dx = 1.348 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8592 (6) Å | Cell parameters from 7048 reflections |
b = 10.6511 (6) Å | θ = 2.3–25.9° |
c = 14.8089 (9) Å | µ = 0.09 mm−1 |
β = 102.306 (7)° | T = 153 K |
V = 1519.37 (16) Å3 | Block, colourless |
Z = 2 | 0.45 × 0.35 × 0.20 mm |
Stoe IPDS 1 diffractometer | 2924 independent reflections |
Radiation source: fine-focus sealed tube | 1815 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.090 |
φ rotation scans | θmax = 25.9°, θmin = 2.3° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −12→12 |
Tmin = 0.666, Tmax = 1.000 | k = −13→13 |
11450 measured reflections | l = −18→18 |
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)] = 0.051 | Hydrogen site location: mixed |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0843P)2] where P = (Fo2 + 2Fc2)/3 |
2924 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
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) | |
N1 | −0.03421 (18) | 0.58335 (15) | 0.92721 (11) | 0.0272 (4) | |
N2 | 0.22670 (19) | 0.60099 (18) | 0.84892 (13) | 0.0302 (4) | |
H2N | 0.244 (3) | 0.658 (3) | 0.898 (2) | 0.055 (8)* | |
N4 | −0.2443 (2) | 0.74564 (17) | 0.91134 (12) | 0.0299 (4) | |
H4N | −0.182 (3) | 0.738 (2) | 0.8753 (18) | 0.040 (7)* | |
N5 | −0.2772 (2) | 1.19617 (19) | 1.02333 (13) | 0.0430 (5) | |
O1 | 0.09946 (16) | 0.43306 (14) | 0.78401 (10) | 0.0357 (4) | |
O2 | −0.29807 (17) | 0.67310 (16) | 1.04302 (10) | 0.0435 (5) | |
C1 | 0.0706 (2) | 0.50299 (19) | 0.93128 (13) | 0.0251 (5) | |
C2 | −0.1056 (2) | 0.58116 (19) | 0.99495 (13) | 0.0257 (5) | |
C3 | 0.1375 (2) | 0.5078 (2) | 0.84783 (13) | 0.0264 (5) | |
C4 | 0.2840 (2) | 0.6340 (2) | 0.76899 (15) | 0.0350 (5) | |
H4A | 0.298850 | 0.725974 | 0.769395 | 0.042* | |
H4B | 0.214362 | 0.613342 | 0.712270 | 0.042* | |
C5 | 0.4176 (2) | 0.5708 (2) | 0.76382 (14) | 0.0369 (6) | |
C6 | 0.5084 (2) | 0.6284 (3) | 0.71674 (16) | 0.0428 (6) | |
H6 | 0.488582 | 0.710018 | 0.691424 | 0.051* | |
C7 | 0.6260 (3) | 0.5674 (4) | 0.7070 (2) | 0.0638 (9) | |
H7 | 0.695836 | 0.611527 | 0.684660 | 0.077* | |
N3A | 0.6459 (12) | 0.4293 (17) | 0.7318 (7) | 0.061 (3) | 0.58 (3) |
C8A | 0.5525 (14) | 0.3778 (16) | 0.7738 (7) | 0.057 (3) | 0.58 (3) |
H8A | 0.565436 | 0.293085 | 0.793745 | 0.068* | 0.58 (3) |
C9A | 0.4378 (16) | 0.4420 (15) | 0.7897 (9) | 0.049 (2) | 0.58 (3) |
H9A | 0.372404 | 0.400153 | 0.817822 | 0.059* | 0.58 (3) |
N3B | 0.6817 (19) | 0.4827 (19) | 0.7509 (12) | 0.055 (4) | 0.42 (3) |
C8B | 0.603 (2) | 0.429 (2) | 0.8028 (15) | 0.061 (5) | 0.42 (3) |
H8B | 0.638613 | 0.355212 | 0.835676 | 0.073* | 0.42 (3) |
C9B | 0.474 (2) | 0.469 (2) | 0.8135 (13) | 0.045 (4) | 0.42 (3) |
H9B | 0.426497 | 0.427346 | 0.854273 | 0.054* | 0.42 (3) |
C10 | −0.2250 (2) | 0.67050 (19) | 0.98583 (14) | 0.0292 (5) | |
C11 | −0.3563 (2) | 0.8358 (2) | 0.89116 (14) | 0.0302 (5) | |
H11A | −0.439256 | 0.798804 | 0.908574 | 0.036* | |
H11B | −0.379534 | 0.850972 | 0.823670 | 0.036* | |
C12 | −0.3255 (2) | 0.9596 (2) | 0.93967 (13) | 0.0280 (5) | |
C13 | −0.4219 (2) | 1.0556 (2) | 0.91948 (15) | 0.0335 (5) | |
H13 | −0.506721 | 1.042206 | 0.876122 | 0.040* | |
C14 | −0.3951 (2) | 1.1701 (2) | 0.96208 (16) | 0.0377 (6) | |
H14 | −0.463442 | 1.234122 | 0.947499 | 0.045* | |
C15 | −0.1850 (3) | 1.1033 (2) | 1.04220 (17) | 0.0462 (6) | |
H15 | −0.100541 | 1.119381 | 1.085262 | 0.055* | |
C16 | −0.2041 (2) | 0.9855 (2) | 1.00334 (15) | 0.0374 (6) | |
H16 | −0.134841 | 0.922753 | 1.020004 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0310 (9) | 0.0273 (10) | 0.0236 (8) | 0.0014 (8) | 0.0069 (7) | −0.0008 (7) |
N2 | 0.0327 (10) | 0.0303 (11) | 0.0297 (9) | −0.0008 (8) | 0.0114 (8) | −0.0023 (8) |
N4 | 0.0361 (10) | 0.0311 (11) | 0.0236 (9) | 0.0061 (8) | 0.0087 (8) | 0.0028 (7) |
N5 | 0.0529 (13) | 0.0374 (12) | 0.0396 (11) | 0.0010 (10) | 0.0121 (10) | −0.0045 (9) |
O1 | 0.0419 (9) | 0.0411 (9) | 0.0250 (8) | −0.0056 (7) | 0.0090 (6) | −0.0069 (7) |
O2 | 0.0489 (10) | 0.0523 (11) | 0.0356 (9) | 0.0206 (8) | 0.0228 (8) | 0.0139 (7) |
C1 | 0.0293 (11) | 0.0238 (11) | 0.0224 (10) | −0.0008 (9) | 0.0060 (8) | −0.0023 (8) |
C2 | 0.0294 (11) | 0.0252 (11) | 0.0230 (10) | 0.0006 (9) | 0.0063 (8) | −0.0019 (8) |
C3 | 0.0269 (11) | 0.0284 (12) | 0.0244 (10) | 0.0051 (9) | 0.0063 (8) | 0.0011 (8) |
C4 | 0.0346 (12) | 0.0404 (13) | 0.0321 (11) | −0.0008 (11) | 0.0113 (9) | 0.0066 (10) |
C5 | 0.0378 (13) | 0.0516 (16) | 0.0224 (11) | 0.0022 (11) | 0.0088 (9) | −0.0042 (10) |
C6 | 0.0399 (13) | 0.0584 (16) | 0.0330 (12) | −0.0071 (12) | 0.0138 (10) | −0.0140 (11) |
C7 | 0.0480 (17) | 0.107 (3) | 0.0429 (16) | 0.0061 (18) | 0.0232 (13) | −0.0043 (17) |
N3A | 0.053 (4) | 0.085 (7) | 0.052 (4) | 0.023 (4) | 0.027 (3) | 0.000 (4) |
C8A | 0.063 (5) | 0.074 (6) | 0.039 (4) | 0.026 (5) | 0.024 (4) | 0.011 (4) |
C9A | 0.045 (6) | 0.072 (6) | 0.031 (5) | 0.017 (4) | 0.011 (4) | 0.005 (4) |
N3B | 0.062 (7) | 0.062 (8) | 0.052 (6) | 0.019 (6) | 0.035 (5) | 0.013 (5) |
C8B | 0.066 (8) | 0.070 (9) | 0.055 (8) | 0.032 (7) | 0.029 (7) | 0.027 (7) |
C9B | 0.048 (8) | 0.068 (9) | 0.025 (6) | 0.023 (6) | 0.019 (5) | 0.022 (6) |
C10 | 0.0352 (12) | 0.0274 (12) | 0.0258 (10) | 0.0036 (9) | 0.0082 (9) | 0.0012 (8) |
C11 | 0.0312 (11) | 0.0311 (12) | 0.0266 (10) | 0.0047 (9) | 0.0023 (8) | 0.0034 (9) |
C12 | 0.0313 (12) | 0.0313 (12) | 0.0223 (10) | 0.0032 (9) | 0.0074 (8) | 0.0037 (8) |
C13 | 0.0308 (12) | 0.0345 (13) | 0.0347 (12) | 0.0047 (10) | 0.0059 (9) | 0.0042 (10) |
C14 | 0.0401 (13) | 0.0349 (13) | 0.0413 (12) | 0.0090 (11) | 0.0158 (10) | 0.0047 (10) |
C15 | 0.0470 (15) | 0.0456 (16) | 0.0408 (14) | 0.0020 (12) | −0.0021 (11) | −0.0085 (11) |
C16 | 0.0375 (13) | 0.0367 (14) | 0.0337 (12) | 0.0078 (11) | −0.0018 (10) | −0.0019 (10) |
N1—C1 | 1.333 (3) | C7—N3B | 1.177 (12) |
N1—C2 | 1.343 (3) | C7—N3A | 1.518 (17) |
N2—C3 | 1.324 (3) | C7—H7 | 0.9500 |
N2—C4 | 1.459 (3) | N3A—C8A | 1.334 (12) |
N2—H2N | 0.93 (3) | C8A—C9A | 1.384 (16) |
N4—C10 | 1.343 (3) | C8A—H8A | 0.9500 |
N4—C11 | 1.446 (3) | C9A—H9A | 0.9500 |
N4—H4N | 0.90 (3) | N3B—C8B | 1.336 (16) |
N5—C15 | 1.333 (3) | C8B—C9B | 1.38 (2) |
N5—C14 | 1.342 (3) | C8B—H8B | 0.9500 |
O1—C3 | 1.232 (2) | C9B—H9B | 0.9500 |
O2—C10 | 1.224 (3) | C11—C12 | 1.502 (3) |
C1—C2i | 1.398 (3) | C11—H11A | 0.9900 |
C1—C3 | 1.521 (3) | C11—H11B | 0.9900 |
C2—C10 | 1.497 (3) | C12—C16 | 1.384 (3) |
C4—C5 | 1.495 (3) | C12—C13 | 1.385 (3) |
C4—H4A | 0.9900 | C13—C14 | 1.373 (3) |
C4—H4B | 0.9900 | C13—H13 | 0.9500 |
C5—C9B | 1.360 (18) | C14—H14 | 0.9500 |
C5—C6 | 1.389 (3) | C15—C16 | 1.376 (3) |
C5—C9A | 1.427 (16) | C15—H15 | 0.9500 |
C6—C7 | 1.363 (4) | C16—H16 | 0.9500 |
C6—H6 | 0.9500 | ||
C1—N1—C2 | 118.66 (17) | N3A—C8A—H8A | 118.4 |
C3—N2—C4 | 122.83 (19) | C9A—C8A—H8A | 118.4 |
C3—N2—H2N | 120.4 (17) | C8A—C9A—C5 | 120.1 (12) |
C4—N2—H2N | 115.9 (17) | C8A—C9A—H9A | 120.0 |
C10—N4—C11 | 122.25 (19) | C5—C9A—H9A | 120.0 |
C10—N4—H4N | 116.1 (16) | C7—N3B—C8B | 112.7 (11) |
C11—N4—H4N | 121.6 (16) | N3B—C8B—C9B | 126.5 (12) |
C15—N5—C14 | 116.3 (2) | N3B—C8B—H8B | 116.7 |
N1—C1—C2i | 120.44 (19) | C9B—C8B—H8B | 116.7 |
N1—C1—C3 | 114.06 (17) | C5—C9B—C8B | 117.8 (13) |
C2i—C1—C3 | 125.39 (18) | C5—C9B—H9B | 121.1 |
N1—C2—C1i | 120.89 (19) | C8B—C9B—H9B | 121.1 |
N1—C2—C10 | 116.66 (17) | O2—C10—N4 | 123.6 (2) |
C1i—C2—C10 | 122.44 (18) | O2—C10—C2 | 121.30 (18) |
O1—C3—N2 | 125.93 (19) | N4—C10—C2 | 115.08 (19) |
O1—C3—C1 | 119.20 (19) | N4—C11—C12 | 114.61 (17) |
N2—C3—C1 | 114.69 (18) | N4—C11—H11A | 108.6 |
N2—C4—C5 | 115.50 (18) | C12—C11—H11A | 108.6 |
N2—C4—H4A | 108.4 | N4—C11—H11B | 108.6 |
C5—C4—H4A | 108.4 | C12—C11—H11B | 108.6 |
N2—C4—H4B | 108.4 | H11A—C11—H11B | 107.6 |
C5—C4—H4B | 108.4 | C16—C12—C13 | 117.0 (2) |
H4A—C4—H4B | 107.5 | C16—C12—C11 | 123.95 (19) |
C9B—C5—C6 | 113.0 (8) | C13—C12—C11 | 119.04 (18) |
C6—C5—C9A | 119.4 (6) | C14—C13—C12 | 120.0 (2) |
C9B—C5—C4 | 126.4 (8) | C14—C13—H13 | 120.0 |
C6—C5—C4 | 119.7 (2) | C12—C13—H13 | 120.0 |
C9A—C5—C4 | 119.6 (6) | N5—C14—C13 | 123.2 (2) |
C7—C6—C5 | 119.7 (3) | N5—C14—H14 | 118.4 |
C7—C6—H6 | 120.1 | C13—C14—H14 | 118.4 |
C5—C6—H6 | 120.1 | N5—C15—C16 | 124.2 (2) |
N3B—C7—C6 | 128.0 (6) | N5—C15—H15 | 117.9 |
C6—C7—N3A | 120.4 (5) | C16—C15—H15 | 117.9 |
C6—C7—H7 | 119.8 | C15—C16—C12 | 119.2 (2) |
N3A—C7—H7 | 119.8 | C15—C16—H16 | 120.4 |
C8A—N3A—C7 | 116.4 (7) | C12—C16—H16 | 120.4 |
N3A—C8A—C9A | 123.1 (10) | ||
C2—N1—C1—C2i | −0.4 (3) | C4—C5—C9A—C8A | 171.5 (5) |
C2—N1—C1—C3 | 176.06 (18) | C6—C7—N3B—C8B | 13.7 (16) |
C1—N1—C2—C1i | 0.4 (3) | C7—N3B—C8B—C9B | −5.4 (18) |
C1—N1—C2—C10 | −178.23 (17) | C6—C5—C9B—C8B | −7.3 (13) |
C4—N2—C3—O1 | 5.4 (3) | C4—C5—C9B—C8B | −176.3 (10) |
C4—N2—C3—C1 | −169.63 (18) | N3B—C8B—C9B—C5 | 3.0 (19) |
N1—C1—C3—O1 | −95.4 (2) | C11—N4—C10—O2 | −1.2 (3) |
C2i—C1—C3—O1 | 80.8 (3) | C11—N4—C10—C2 | 178.84 (18) |
N1—C1—C3—N2 | 80.0 (2) | N1—C2—C10—O2 | 178.2 (2) |
C2i—C1—C3—N2 | −103.8 (2) | C1i—C2—C10—O2 | −0.4 (3) |
C3—N2—C4—C5 | −91.4 (2) | N1—C2—C10—N4 | −1.8 (3) |
N2—C4—C5—C9B | 14.7 (13) | C1i—C2—C10—N4 | 179.59 (19) |
N2—C4—C5—C6 | −153.7 (2) | C10—N4—C11—C12 | 84.7 (3) |
N2—C4—C5—C9A | 39.5 (7) | N4—C11—C12—C16 | −3.9 (3) |
C9B—C5—C6—C7 | 14.2 (11) | N4—C11—C12—C13 | 175.06 (19) |
C9A—C5—C6—C7 | −9.1 (7) | C16—C12—C13—C14 | −0.1 (3) |
C4—C5—C6—C7 | −175.9 (2) | C11—C12—C13—C14 | −179.1 (2) |
C5—C6—C7—N3B | −19.6 (17) | C15—N5—C14—C13 | −0.5 (4) |
C5—C6—C7—N3A | 11.0 (7) | C12—C13—C14—N5 | 0.6 (4) |
C6—C7—N3A—C8A | −8.4 (9) | C14—N5—C15—C16 | −0.1 (4) |
C7—N3A—C8A—C9A | 4.0 (11) | N5—C15—C16—C12 | 0.6 (4) |
N3A—C8A—C9A—C5 | −2.3 (11) | C13—C12—C16—C15 | −0.5 (3) |
C6—C5—C9A—C8A | 4.6 (9) | C11—C12—C16—C15 | 178.5 (2) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9A—H9A···O2i | 0.95 | 2.46 | 3.316 (15) | 150 |
[C9B—H9B···O2]i | 0.95 | 2.43 | 3.375 (18) | 178 |
N2—H2N···N5ii | 0.93 (3) | 1.93 (3) | 2.845 (3) | 167 (2) |
N4—H4N···N3Aiii | 0.90 (3) | 2.65 (3) | 3.184 (13) | 119 (2) |
C6—H6···O1iii | 0.95 | 2.58 | 3.414 (3) | 146 |
C11—H11B···O1iv | 0.99 | 2.56 | 3.301 (2) | 132 |
C14—H14···O2v | 0.95 | 2.58 | 3.442 (3) | 151 |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+2, −z+2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x−1/2, y+1/2, −z+3/2; (v) −x−1, −y+2, −z+2. |
Funding information
Funding for this research was provided by: Swiss National Science FoundationUniversity of Neuchâtel
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