Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017563/sf3204sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017563/sf3204Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017563/sf3204IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017563/sf3204Isup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017563/sf3204IIsup5.cml |
CCDC references: 964801; 964802
Pyrazole derivatives have wide application in the chemistry of pharmaceuticals, pesticides and lubricants (Quiroga et al., 2008; Sharma et al., 2010; Chauhan et al., 2011; Fustero et al., 2011; Hassan et al., 2011), while pyrrolo[3,4-c]pyrroles have diverse applications in materials chemistry, pharmaceuticals and agrochemicals (Rotstein et al., 2010; Zhang et al., 2010; Georgiou et al., 2012). As part of a programme on the synthesis of nitrogen-based heterocycles involving the development of new methodologies which are both selective and environmentally friendly (Quiroga et al., 2010; Quiroga, Gálvez et al., 2011; Quiroga, Portillo et al., 2011), we have developed a catalyst-free three-component 1,3-dipolar cycloaddition reaction to produce pyrazolylpyrrolidine derivatives which incorporate both of these important heterocyclic systems. The representative title compounds, (I) and (II) (Figs. 1 and 2), the structures of which are reported here, were obtained in good yields via reactions between electron-deficient alkenes and azomethine ylides generated in situ in diastereoselective reactions between N-aryl maleimides, a formylpyrazole and alanine methyl ester.
Crystal data, data collection and structure refinement details are summarized in Table 1.
For the synthesis of (I) and (II), a mixture of 3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (0.2 mmol), the corresponding N-arylmaleimide (0.2 mmol) and alanine methyl ester hydrochloride (0.2 mmol) in toluene (8 ml) was heated under reflux for 8–10 h. The reaction mixture was then cooled to ambient temperature and the resulting solid product was collected by filtration and washed with hexane–toluene (1:1 v/v) to obtain the pure compound. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, from solutions in toluene–dimethylformamide (7:3 v/v). For (I), yield 68%, m.p. 479–481 K; MS (EI, 70 eV) m/z (% relative abundance): 445 (M + 1, 1), 271 (97), 211 (100), 170 (56). For (II), yield 62%, m.p. 433–435 K; MS (EI, 70 eV) m/z (% relative abundance): 479 (M+, 1), 271 (91), 211 (100), 170 (62), 129 (23).
All H atoms were located in difference maps. C-bound H atoms were then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic and pyrazole), 0.98 (CH3) or 1.00 Å (aliphatic), and with Uiso(H) = kUeq (C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other C-bound H atoms. N-bound H atoms were permitted ro ride at the positions located in difference maps, with Uiso(H) = 1.2Ueq(N), giving the N—H distances shown in Tables 2 and . Examination of the refined structure of (I) using PLATON (Spek, 2009) revealed a total void volume of ca 36 Å3 per unit cell, distributed over four sites, centred at (0.442, 0.818, 1/4) and the symmetry-related positions, with each site having a volume of ca 9 Å3. This volume is far too small to accommodate any solvent molecule but, despite this, the location of the highest residual peak in the final difference map, of height 0.69 e Å-3 at (0.506, 0.840, 0.211), was quite close to the centre of the void space. However, investigation using the SQUEEZE option in PLATON revealed an additional electron count of only two electrons per unit cell. In view of the very small volume of the individual voids, both the residual peak and the excess electron count must be regarded as artefacts. For (II), the bad outlier reflection 317 was omitted from the final refinements.
In the molecules of each of (I) and (II), there are four stereogenic centres, at atoms C1, C3, C3a and C6a. For each compound, the reference molecule was selected to have the R configuration at atom C1 and, on this basis, the configurations of the reference molecules are (1R,3S,3aR,6aS), but the centrosymmetric space group for each compound confirms that (I) and (II) both crystallize as racemic mixtures. Although the molecular constitutions of (I) and (II) differ only by the presence of the single chloro substituent in (II), the unit-cell dimensions are markedly different, with the b repeat vectors differing by a factor of nearly three. Nonetheless, as expected (Hofmann, 2002), the unit-cell volumes differ by only ca 2.0%.
In the molecules of (I) and (II), the fused five-membered rings are both nonplanar, as indicated by the ring-puckering parameters (Cremer & Pople, 1975) in Table 4. These rings all adopt conformations close to the half-chair form, for which the idealized value of θ2 is (36k + 18)°, where k represents an integer. In both compounds, the puckering is significantly larger in the ring containing atom N2, where the twist is about a line between atom C3a and the mid-point of the C1—N2 bond, than it is for the ring containing atom N5, where the twist is about a line through atom N5 and the mid-point of the C3a—C6a bond. The dihedral angles between the mean planes of these two rings are 73.4 (2)° in (I) and 74.9 (2)° in (II). The torsion angles defining the relative orientations of the ring systems are fairly similar in (I) and (II) (Table 5), although the orientations of the C51–C56 rings differ by ca 50°. The principal point of difference in the molecular conformations lies in the orientation of the ester group, which differs in the two compounds by a rotation of almost 180° about the C1—C11 bond (Table 5, and Figs. 1 and 2). These conformational differences are most simply interpreted in terms of the different hydrogen-bonding interaction in the two compounds (Tables 2 and 3). Thus, in (II) but not in (I), carbonyl atom O11 is an acceptor, while atoms C55 and C56 act as donors in (II) but not in (I).
Within the pyrazole rings, the lengths of the two N—C bonds (Table 5) differ by only 0.026 Å in each compound, despite the fact that the N31—C35 and N32—C33 bonds are formally single and double bonds, respectively. Similarly, the two C—C bonds within the pyrazole ring differ in length in each case by less than 0.04 Å, despite the C33—C34 and C34—C35 bonds being formally single and double bonds, respectively. These observations point to a degree of aromatic-type electron delocalization within the pyrazole rings.
The supramolecular assembly in (I) is determined by a combination of three C—H···O hydrogen bonds and an N—H···π(pyrazole) hydrogen bond (Table 2), but N—H···N, N—H···O and N—H···π(arene) hydrogen bonds are all absent from the structure of (I). The C—H···O hydrogen bond having atom O6 as the acceptor and the N—H···π(pyrazole) hydrogen bond combine to link molecules related by inversion into a chain of rings running parallel to the [101] direction. In this chain, R22(8) rings (Bernstein et al., 1995) generated by paired C—H···O hydrogen bonds, which are centred at (n, 1/2, n - 1/2), alternate with rings generated by paired N—H···π(pyrazole) hydrogen bonds, which are centred at (n + 1/2, 1/2, n), where n represents an integer in each case (Fig. 3). The two C—H···O hydrogen bonds having atoms O4 and O12 as the acceptors link molecules related by the c-glide plane at y = 3/4 to form a C(11)C(11)[R22(20)] chain of rings running parallel to the [001] direction (Fig. 4). The combination of the two chains of rings along [001] and [101] gives rise to a sheet lying parallel to (101).
The molecules of (II) are linked into complex sheets by a combination of four hydrogen bonds, one each of N—H···N and C—H···π(arene) types and two of C—H···O type (Table 3). The formation of the sheet is readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). In the simpler of the two substructures, molecules of (II) related by the 21 screw axis along (3/4, y, 1/4) are linked by a further C—H···O hydrogen bond into a C(7) chain, also running parallel to the [010] direction (Fig. 5), which is weakly reinforced by the C—H···π(arene) interaction. In the second substructure, each of the two hydrogen bonds having atoms N1 and C3a as the donors, acting individually, generates a C(6) chain, while together they generate a chain of edge-fused R33(17) rings running parallel to the [010] direction and built from molecules related by the 21 screw axis along (1/4, y, 1/4) (Fig. 6). The combination of these two chain motifs generates a sheet lying parallel to (001) in the domain 0 < z < 1/2 (Fig. 7). A second sheet of this type, related to the first by inversion, lies in the domain 1/2 < z < 1.0, but the only direction-specific interaction between adjacent sheets is a C—H···O contact having an angle of only 134° (Table 3), which is unlikely to be structurally significant (Wood et al., 2009).
Compounds (I) and (II) differ not only in their unit-cell dimensions, albeit in the same space group, as noted earlier, but also in their molecular conformations and in their modes of supramolecular assembly, despite the fact that their molecular constitutions differ only in the presence of a single Cl substituent in (II). It is therefore of interest to consider whether the specific intermolecular contacts made by the Cl atom offer any simple explanation of the structural differences already noted. There is a C—H···Cl contact in (II) (Table 3), which cannot, of course, be present in the structure of (I). However, the H···Cl distance is only marginally shorter than the sum of the van der Waals radii for H and Cl (2.83 Å; Rowland & Taylor, 1996). The C—H···Cl angle is small, and Wood et al. (2009) have shown that the interaction energies for D—H···A contacts diminish rapidly with the D—H···A angle, becoming very small when this angle is less than 140°, so that in the present example the interaction energy is probably negligible. Finally, it is now well established that Cl atoms bonded to C atoms are very poor acceptors of hydrogen bonds, even from good donors such as O or N (Brammer et al., 2001; Thallapally & Nangia, 2001). For all of these reasons, this contact cannot be regarded as structurally significant. Howeer, even if it were significant, this contact would have no influence on the overall supramolecular assembly, as it lies within the sheet defined by the genuine hydrogen bonds. There are also short contacts between the Cl atom in the molecule at (x, y, z) and carbonyl atoms C6 and O6 in the molecule at (-x + 3/2, y + 1/2, -z + 1/2), with distances Cl54···C6i = 3.359 (3) Å and Cl54···O6i = 3.743 (3) Å [symmetry code: (i) -x + 3/2, y + 1/2, -z + 1/2], and with a geometry somewhat reminiscent of the perpendicular motif found in dipolar carbonyl–carbonyl interactions (Allen et al., 1998). While the significance of interactions of the general type >C═O···Cl—C has not yet been established, we again note that this contact lies within the sheet defined by the hydrogen bonds. It must be concluded therefore that, while the presence of the Cl atom in (II) undoubtedly influences several aspects of the crystal structure, the interpretation of the structural differences between (I) and (II) is far from simple.
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR2004 (Burla et al., 2005) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C25H24N4O4 | F(000) = 936 |
Mr = 444.48 | Dx = 1.327 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5110 reflections |
a = 11.355 (2) Å | θ = 2.8–27.5° |
b = 20.025 (4) Å | µ = 0.09 mm−1 |
c = 10.4124 (8) Å | T = 120 K |
β = 110.030 (9)° | Block, colourless |
V = 2224.4 (6) Å3 | 0.39 × 0.35 × 0.29 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 5110 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3436 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −26→26 |
Tmin = 0.965, Tmax = 0.974 | l = −13→13 |
32624 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0575P)2 + 1.1153P] where P = (Fo2 + 2Fc2)/3 |
5110 reflections | (Δ/σ)max = 0.001 |
301 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C25H24N4O4 | V = 2224.4 (6) Å3 |
Mr = 444.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.355 (2) Å | µ = 0.09 mm−1 |
b = 20.025 (4) Å | T = 120 K |
c = 10.4124 (8) Å | 0.39 × 0.35 × 0.29 mm |
β = 110.030 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 5110 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3436 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.974 | Rint = 0.050 |
32624 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.69 e Å−3 |
5110 reflections | Δρmin = −0.30 e Å−3 |
301 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.81247 (16) | 0.47889 (9) | 0.24951 (17) | 0.0226 (4) | |
N2 | 0.69738 (13) | 0.51195 (8) | 0.16270 (15) | 0.0236 (3) | |
H2 | 0.6657 | 0.4998 | 0.0679 | 0.028* | |
C3 | 0.59880 (16) | 0.49657 (9) | 0.22061 (17) | 0.0224 (4) | |
H3 | 0.5674 | 0.4501 | 0.1942 | 0.027* | |
C3a | 0.67267 (16) | 0.49918 (9) | 0.37913 (18) | 0.0224 (4) | |
H3A | 0.6527 | 0.4599 | 0.4273 | 0.027* | |
C4 | 0.65195 (17) | 0.56427 (9) | 0.44155 (17) | 0.0235 (4) | |
O4 | 0.56144 (12) | 0.58101 (7) | 0.47009 (13) | 0.0302 (3) | |
N5 | 0.75628 (13) | 0.60466 (7) | 0.45921 (15) | 0.0245 (3) | |
C6 | 0.84983 (16) | 0.57253 (9) | 0.42512 (17) | 0.0232 (4) | |
O6 | 0.94503 (12) | 0.59949 (6) | 0.42344 (13) | 0.0294 (3) | |
C6a | 0.81146 (16) | 0.50014 (9) | 0.39187 (17) | 0.0217 (4) | |
H6A | 0.8627 | 0.4693 | 0.4653 | 0.026* | |
C11 | 0.92879 (17) | 0.50372 (9) | 0.22231 (18) | 0.0238 (4) | |
O11 | 1.03271 (11) | 0.48262 (7) | 0.28212 (13) | 0.0305 (3) | |
O12 | 0.90233 (11) | 0.54852 (6) | 0.12176 (13) | 0.0285 (3) | |
C12 | 1.00987 (19) | 0.57678 (11) | 0.0964 (2) | 0.0356 (5) | |
H12A | 1.0624 | 0.6007 | 0.1780 | 0.053* | |
H12B | 0.9812 | 0.6078 | 0.0191 | 0.053* | |
H12C | 1.0587 | 0.5409 | 0.0749 | 0.053* | |
C13 | 0.81225 (18) | 0.40234 (9) | 0.2380 (2) | 0.0290 (4) | |
H13A | 0.7388 | 0.3842 | 0.2551 | 0.043* | |
H13B | 0.8887 | 0.3843 | 0.3056 | 0.043* | |
H13C | 0.8091 | 0.3896 | 0.1460 | 0.043* | |
N31 | 0.37723 (14) | 0.63502 (8) | 0.10243 (15) | 0.0260 (3) | |
N32 | 0.29998 (14) | 0.59009 (8) | 0.13204 (16) | 0.0265 (3) | |
C33 | 0.36931 (16) | 0.53532 (9) | 0.17361 (17) | 0.0238 (4) | |
C34 | 0.49182 (16) | 0.54447 (9) | 0.17040 (17) | 0.0230 (4) | |
C35 | 0.49289 (16) | 0.60883 (9) | 0.12406 (18) | 0.0250 (4) | |
H35 | 0.5616 | 0.6308 | 0.1099 | 0.030* | |
C311 | 0.33015 (18) | 0.69943 (9) | 0.05190 (19) | 0.0284 (4) | |
C312 | 0.3976 (2) | 0.74051 (11) | −0.0042 (2) | 0.0437 (5) | |
H312 | 0.4767 | 0.7267 | −0.0070 | 0.052* | |
C313 | 0.3480 (2) | 0.80269 (11) | −0.0569 (3) | 0.0494 (6) | |
H313 | 0.3939 | 0.8313 | −0.0952 | 0.059* | |
C314 | 0.2334 (2) | 0.82252 (11) | −0.0536 (2) | 0.0438 (6) | |
H314 | 0.1995 | 0.8645 | −0.0908 | 0.053* | |
C315 | 0.1679 (2) | 0.78164 (10) | 0.0036 (2) | 0.0402 (5) | |
H315 | 0.0888 | 0.7956 | 0.0062 | 0.048* | |
C316 | 0.21615 (19) | 0.72002 (10) | 0.0576 (2) | 0.0340 (5) | |
H316 | 0.1709 | 0.6922 | 0.0983 | 0.041* | |
C331 | 0.31533 (18) | 0.47364 (10) | 0.2132 (2) | 0.0319 (4) | |
H33A | 0.2450 | 0.4859 | 0.2426 | 0.048* | |
H33B | 0.3800 | 0.4511 | 0.2883 | 0.048* | |
H33C | 0.2857 | 0.4435 | 0.1345 | 0.048* | |
C51 | 0.76736 (18) | 0.67194 (10) | 0.5100 (2) | 0.0318 (4) | |
C52 | 0.8451 (2) | 0.68468 (13) | 0.6418 (3) | 0.0492 (6) | |
H52 | 0.8898 | 0.6494 | 0.6988 | 0.059* | |
C53 | 0.8571 (3) | 0.74986 (15) | 0.6902 (3) | 0.0683 (9) | |
H53 | 0.9104 | 0.7595 | 0.7808 | 0.082* | |
C54 | 0.7915 (3) | 0.80061 (14) | 0.6064 (4) | 0.0685 (9) | |
H54 | 0.7998 | 0.8452 | 0.6397 | 0.082* | |
C55 | 0.7147 (3) | 0.78732 (12) | 0.4760 (3) | 0.0618 (8) | |
H55 | 0.6700 | 0.8226 | 0.4191 | 0.074* | |
C56 | 0.7017 (2) | 0.72221 (11) | 0.4261 (3) | 0.0458 (6) | |
H56 | 0.6482 | 0.7127 | 0.3355 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0191 (9) | 0.0242 (9) | 0.0225 (9) | 0.0010 (7) | 0.0046 (7) | −0.0011 (7) |
N2 | 0.0185 (7) | 0.0306 (8) | 0.0202 (7) | 0.0009 (6) | 0.0048 (6) | 0.0007 (6) |
C3 | 0.0181 (8) | 0.0253 (9) | 0.0235 (9) | −0.0010 (7) | 0.0068 (7) | −0.0005 (7) |
C3a | 0.0204 (9) | 0.0235 (9) | 0.0228 (9) | 0.0001 (7) | 0.0068 (7) | 0.0013 (7) |
C4 | 0.0221 (9) | 0.0281 (9) | 0.0188 (8) | 0.0006 (7) | 0.0051 (7) | 0.0015 (7) |
O4 | 0.0254 (7) | 0.0377 (8) | 0.0295 (7) | 0.0033 (6) | 0.0120 (6) | −0.0021 (6) |
N5 | 0.0214 (8) | 0.0242 (8) | 0.0270 (8) | −0.0009 (6) | 0.0070 (6) | −0.0040 (6) |
C6 | 0.0213 (9) | 0.0266 (9) | 0.0191 (8) | 0.0013 (7) | 0.0037 (7) | −0.0011 (7) |
O6 | 0.0229 (7) | 0.0298 (7) | 0.0345 (7) | −0.0045 (6) | 0.0085 (6) | −0.0046 (6) |
C6a | 0.0197 (8) | 0.0224 (9) | 0.0211 (8) | 0.0009 (7) | 0.0045 (7) | 0.0006 (7) |
C11 | 0.0236 (9) | 0.0250 (9) | 0.0219 (9) | 0.0009 (7) | 0.0065 (7) | −0.0035 (7) |
O11 | 0.0201 (7) | 0.0388 (8) | 0.0316 (7) | 0.0048 (6) | 0.0075 (6) | 0.0021 (6) |
O12 | 0.0221 (7) | 0.0327 (7) | 0.0314 (7) | −0.0014 (6) | 0.0100 (5) | 0.0051 (6) |
C12 | 0.0274 (10) | 0.0410 (12) | 0.0412 (12) | −0.0062 (9) | 0.0157 (9) | 0.0035 (10) |
C13 | 0.0276 (10) | 0.0273 (10) | 0.0311 (10) | 0.0005 (8) | 0.0088 (8) | −0.0040 (8) |
N31 | 0.0202 (8) | 0.0265 (8) | 0.0297 (8) | −0.0009 (6) | 0.0063 (6) | 0.0018 (6) |
N32 | 0.0205 (8) | 0.0292 (8) | 0.0288 (8) | −0.0006 (6) | 0.0072 (6) | 0.0026 (7) |
C33 | 0.0200 (9) | 0.0296 (10) | 0.0206 (9) | −0.0013 (7) | 0.0053 (7) | −0.0007 (7) |
C34 | 0.0184 (8) | 0.0292 (9) | 0.0193 (8) | −0.0007 (7) | 0.0040 (7) | −0.0016 (7) |
C35 | 0.0189 (9) | 0.0294 (10) | 0.0247 (9) | −0.0002 (7) | 0.0051 (7) | 0.0002 (7) |
C311 | 0.0280 (10) | 0.0244 (9) | 0.0276 (10) | 0.0001 (8) | 0.0027 (8) | 0.0001 (8) |
C312 | 0.0360 (12) | 0.0366 (12) | 0.0576 (14) | 0.0018 (10) | 0.0148 (11) | 0.0115 (11) |
C313 | 0.0488 (15) | 0.0337 (12) | 0.0604 (15) | −0.0039 (11) | 0.0120 (12) | 0.0125 (11) |
C314 | 0.0501 (14) | 0.0263 (11) | 0.0418 (12) | 0.0058 (10) | −0.0014 (10) | 0.0024 (9) |
C315 | 0.0381 (12) | 0.0327 (11) | 0.0426 (12) | 0.0070 (9) | 0.0047 (10) | −0.0058 (10) |
C316 | 0.0302 (11) | 0.0312 (11) | 0.0382 (11) | 0.0037 (9) | 0.0084 (9) | −0.0022 (9) |
C331 | 0.0264 (10) | 0.0344 (11) | 0.0359 (11) | −0.0001 (8) | 0.0118 (8) | 0.0085 (9) |
C51 | 0.0294 (10) | 0.0279 (10) | 0.0431 (12) | −0.0033 (8) | 0.0190 (9) | −0.0109 (9) |
C52 | 0.0343 (12) | 0.0529 (14) | 0.0556 (15) | −0.0006 (11) | 0.0091 (11) | −0.0265 (12) |
C53 | 0.0448 (15) | 0.071 (2) | 0.090 (2) | −0.0115 (14) | 0.0244 (15) | −0.0553 (18) |
C54 | 0.0625 (18) | 0.0399 (15) | 0.127 (3) | −0.0212 (14) | 0.0632 (19) | −0.0405 (17) |
C55 | 0.084 (2) | 0.0276 (12) | 0.098 (2) | 0.0022 (13) | 0.0621 (19) | 0.0000 (14) |
C56 | 0.0611 (16) | 0.0295 (11) | 0.0553 (14) | 0.0031 (11) | 0.0307 (12) | 0.0003 (10) |
C1—N2 | 1.468 (2) | N32—C33 | 1.333 (2) |
C1—C11 | 1.526 (2) | C33—C34 | 1.415 (2) |
C1—C13 | 1.538 (2) | C33—C331 | 1.498 (3) |
C1—C6a | 1.546 (2) | C34—C35 | 1.378 (3) |
N2—C3 | 1.474 (2) | C35—H35 | 0.9500 |
N2—H2 | 0.9590 | C311—C316 | 1.379 (3) |
C3—C34 | 1.495 (2) | C311—C312 | 1.382 (3) |
C3—C3a | 1.575 (2) | C312—C313 | 1.399 (3) |
C3—H3 | 1.0000 | C312—H312 | 0.9500 |
C3a—C4 | 1.510 (3) | C313—C314 | 1.373 (3) |
C3a—C6a | 1.536 (2) | C313—H313 | 0.9500 |
C3a—H3A | 1.0000 | C314—C315 | 1.371 (3) |
C4—O4 | 1.211 (2) | C314—H314 | 0.9500 |
C4—N5 | 1.394 (2) | C315—C316 | 1.389 (3) |
N5—C6 | 1.388 (2) | C315—H315 | 0.9500 |
N5—C51 | 1.437 (2) | C316—H316 | 0.9500 |
C6—O6 | 1.214 (2) | C331—H33A | 0.9800 |
C6—C6a | 1.519 (2) | C331—H33B | 0.9800 |
C6a—H6A | 1.0000 | C331—H33C | 0.9800 |
C11—O11 | 1.206 (2) | C51—C56 | 1.374 (3) |
C11—O12 | 1.332 (2) | C51—C52 | 1.378 (3) |
O12—C12 | 1.450 (2) | C52—C53 | 1.389 (3) |
C12—H12A | 0.9800 | C52—H52 | 0.9500 |
C12—H12B | 0.9800 | C53—C54 | 1.380 (4) |
C12—H12C | 0.9800 | C53—H53 | 0.9500 |
C13—H13A | 0.9800 | C54—C55 | 1.365 (4) |
C13—H13B | 0.9800 | C54—H54 | 0.9500 |
C13—H13C | 0.9800 | C55—C56 | 1.393 (3) |
N31—C35 | 1.359 (2) | C55—H55 | 0.9500 |
N31—N32 | 1.363 (2) | C56—H56 | 0.9500 |
N31—C311 | 1.426 (2) | ||
N2—C1—C11 | 112.55 (15) | N32—N31—C311 | 119.42 (15) |
N2—C1—C13 | 115.11 (14) | C33—N32—N31 | 105.20 (14) |
C11—C1—C13 | 106.79 (14) | N32—C33—C34 | 111.22 (16) |
N2—C1—C6a | 99.72 (13) | N32—C33—C331 | 121.06 (16) |
C11—C1—C6a | 112.30 (14) | C34—C33—C331 | 127.70 (17) |
C13—C1—C6a | 110.41 (14) | C35—C34—C33 | 104.84 (16) |
C1—N2—C3 | 107.13 (14) | C35—C34—C3 | 128.26 (16) |
C1—N2—H2 | 117.4 | C33—C34—C3 | 126.62 (16) |
C3—N2—H2 | 107.4 | N31—C35—C34 | 107.16 (16) |
N2—C3—C34 | 111.28 (14) | N31—C35—H35 | 126.4 |
N2—C3—C3a | 102.42 (13) | C34—C35—H35 | 126.4 |
C34—C3—C3a | 114.99 (14) | C316—C311—C312 | 120.28 (19) |
N2—C3—H3 | 109.3 | C316—C311—N31 | 119.56 (17) |
C34—C3—H3 | 109.3 | C312—C311—N31 | 120.16 (18) |
C3a—C3—H3 | 109.3 | C311—C312—C313 | 119.3 (2) |
C4—C3a—C6a | 104.98 (14) | C311—C312—H312 | 120.4 |
C4—C3a—C3 | 111.95 (14) | C313—C312—H312 | 120.4 |
C6a—C3a—C3 | 104.67 (13) | C314—C313—C312 | 120.3 (2) |
C4—C3a—H3A | 111.6 | C314—C313—H313 | 119.8 |
C6a—C3a—H3A | 111.6 | C312—C313—H313 | 119.8 |
C3—C3a—H3A | 111.6 | C315—C314—C313 | 119.9 (2) |
O4—C4—N5 | 124.16 (17) | C315—C314—H314 | 120.1 |
O4—C4—C3a | 127.95 (17) | C313—C314—H314 | 120.1 |
N5—C4—C3a | 107.87 (14) | C314—C315—C316 | 120.6 (2) |
C6—N5—C4 | 112.81 (15) | C314—C315—H315 | 119.7 |
C6—N5—C51 | 123.40 (15) | C316—C315—H315 | 119.7 |
C4—N5—C51 | 123.78 (15) | C311—C316—C315 | 119.6 (2) |
O6—C6—N5 | 124.12 (17) | C311—C316—H316 | 120.2 |
O6—C6—C6a | 127.48 (16) | C315—C316—H316 | 120.2 |
N5—C6—C6a | 108.40 (15) | C33—C331—H33A | 109.5 |
C6—C6a—C3a | 103.73 (14) | C33—C331—H33B | 109.5 |
C6—C6a—C1 | 112.67 (14) | H33A—C331—H33B | 109.5 |
C3a—C6a—C1 | 104.96 (13) | C33—C331—H33C | 109.5 |
C6—C6a—H6A | 111.7 | H33A—C331—H33C | 109.5 |
C3a—C6a—H6A | 111.7 | H33B—C331—H33C | 109.5 |
C1—C6a—H6A | 111.7 | C56—C51—C52 | 121.4 (2) |
O11—C11—O12 | 123.98 (17) | C56—C51—N5 | 119.55 (19) |
O11—C11—C1 | 123.08 (17) | C52—C51—N5 | 119.06 (19) |
O12—C11—C1 | 112.87 (15) | C51—C52—C53 | 119.0 (3) |
C11—O12—C12 | 115.38 (14) | C51—C52—H52 | 120.5 |
O12—C12—H12A | 109.5 | C53—C52—H52 | 120.5 |
O12—C12—H12B | 109.5 | C54—C53—C52 | 119.9 (3) |
H12A—C12—H12B | 109.5 | C54—C53—H53 | 120.1 |
O12—C12—H12C | 109.5 | C52—C53—H53 | 120.1 |
H12A—C12—H12C | 109.5 | C55—C54—C53 | 120.5 (2) |
H12B—C12—H12C | 109.5 | C55—C54—H54 | 119.7 |
C1—C13—H13A | 109.5 | C53—C54—H54 | 119.7 |
C1—C13—H13B | 109.5 | C54—C55—C56 | 120.3 (3) |
H13A—C13—H13B | 109.5 | C54—C55—H55 | 119.9 |
C1—C13—H13C | 109.5 | C56—C55—H55 | 119.9 |
H13A—C13—H13C | 109.5 | C51—C56—C55 | 118.9 (2) |
H13B—C13—H13C | 109.5 | C51—C56—H56 | 120.5 |
C35—N31—N32 | 111.59 (15) | C55—C56—H56 | 120.5 |
C35—N31—C311 | 128.97 (16) | ||
C11—C1—N2—C3 | −166.37 (14) | C1—C11—O12—C12 | 176.65 (15) |
C13—C1—N2—C3 | 70.94 (18) | C35—N31—N32—C33 | 0.43 (19) |
C6a—C1—N2—C3 | −47.16 (16) | C311—N31—N32—C33 | 178.80 (15) |
C1—N2—C3—C34 | 161.32 (14) | N31—N32—C33—C34 | −0.31 (19) |
C1—N2—C3—C3a | 37.95 (17) | N31—N32—C33—C331 | −178.82 (16) |
N2—C3—C3a—C4 | 100.65 (16) | N32—C33—C34—C35 | 0.1 (2) |
C34—C3—C3a—C4 | −20.2 (2) | C331—C33—C34—C35 | 178.48 (18) |
N2—C3—C3a—C6a | −12.54 (17) | N32—C33—C34—C3 | 174.41 (16) |
C34—C3—C3a—C6a | −133.38 (15) | C331—C33—C34—C3 | −7.2 (3) |
C6a—C3a—C4—O4 | −169.30 (17) | N2—C3—C34—C35 | −25.2 (2) |
C3—C3a—C4—O4 | 77.7 (2) | C3a—C3—C34—C35 | 90.7 (2) |
C6a—C3a—C4—N5 | 12.14 (18) | N2—C3—C34—C33 | 161.83 (16) |
C3—C3a—C4—N5 | −100.85 (16) | C3a—C3—C34—C33 | −82.3 (2) |
O4—C4—N5—C6 | 176.93 (16) | N32—N31—C35—C34 | −0.4 (2) |
C3a—C4—N5—C6 | −4.45 (19) | C311—N31—C35—C34 | −178.56 (17) |
O4—C4—N5—C51 | −1.8 (3) | C33—C34—C35—N31 | 0.18 (19) |
C3a—C4—N5—C51 | 176.78 (16) | C3—C34—C35—N31 | −174.02 (16) |
C4—N5—C6—O6 | 174.64 (16) | C35—N31—C311—C316 | −169.88 (18) |
C51—N5—C6—O6 | −6.6 (3) | N32—N31—C311—C316 | 12.1 (3) |
C4—N5—C6—C6a | −5.41 (19) | C35—N31—C311—C312 | 11.1 (3) |
C51—N5—C6—C6a | 173.37 (16) | N32—N31—C311—C312 | −167.00 (18) |
O6—C6—C6a—C3a | −167.48 (17) | C316—C311—C312—C313 | −0.9 (3) |
N5—C6—C6a—C3a | 12.57 (18) | N31—C311—C312—C313 | 178.1 (2) |
O6—C6—C6a—C1 | −54.5 (2) | C311—C312—C313—C314 | −0.3 (4) |
N5—C6—C6a—C1 | 125.53 (15) | C312—C313—C314—C315 | 1.0 (4) |
C4—C3a—C6a—C6 | −14.60 (17) | C313—C314—C315—C316 | −0.3 (3) |
C3—C3a—C6a—C6 | 103.44 (15) | C312—C311—C316—C315 | 1.6 (3) |
C4—C3a—C6a—C1 | −133.02 (14) | N31—C311—C316—C315 | −177.48 (17) |
C3—C3a—C6a—C1 | −14.98 (17) | C314—C315—C316—C311 | −0.9 (3) |
N2—C1—C6a—C6 | −75.37 (16) | C6—N5—C51—C56 | 106.2 (2) |
C11—C1—C6a—C6 | 44.0 (2) | C4—N5—C51—C56 | −75.2 (2) |
C13—C1—C6a—C6 | 163.09 (14) | C6—N5—C51—C52 | −73.1 (2) |
N2—C1—C6a—C3a | 36.83 (16) | C4—N5—C51—C52 | 105.5 (2) |
C11—C1—C6a—C3a | 156.23 (14) | C56—C51—C52—C53 | −0.2 (3) |
C13—C1—C6a—C3a | −84.71 (16) | N5—C51—C52—C53 | 179.1 (2) |
N2—C1—C11—O11 | −179.46 (16) | C51—C52—C53—C54 | 0.1 (4) |
C13—C1—C11—O11 | −52.2 (2) | C52—C53—C54—C55 | 0.0 (4) |
C6a—C1—C11—O11 | 68.9 (2) | C53—C54—C55—C56 | 0.1 (4) |
N2—C1—C11—O12 | −2.4 (2) | C52—C51—C56—C55 | 0.2 (3) |
C13—C1—C11—O12 | 124.83 (16) | N5—C51—C56—C55 | −179.08 (19) |
C6a—C1—C11—O12 | −114.01 (16) | C54—C55—C56—C51 | −0.1 (4) |
O11—C11—O12—C12 | −6.3 (3) |
Cg3 represents the centroid of the N31/N32/C33–C35 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6a—H6A···O6i | 1.00 | 2.50 | 3.418 (2) | 152 |
C54—H54···O12ii | 0.95 | 2.46 | 3.256 (3) | 141 |
C313—H313···O4iii | 0.95 | 2.51 | 3.303 (3) | 142 |
N2—H2···Cg3iv | 0.96 | 2.63 | 3.522 (2) | 156 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+1, −z. |
C25H23ClN4O4 | F(000) = 1000 |
Mr = 478.92 | Dx = 1.403 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5200 reflections |
a = 16.565 (3) Å | θ = 2.6–27.5° |
b = 6.9529 (5) Å | µ = 0.21 mm−1 |
c = 21.010 (4) Å | T = 120 K |
β = 110.465 (11)° | Block, colourless |
V = 2267.1 (5) Å3 | 0.42 × 0.25 × 0.18 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 5200 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3101 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.917, Tmax = 0.963 | l = −27→27 |
32234 measured reflections |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0317P)2 + 1.7606P] where P = (Fo2 + 2Fc2)/3 |
5200 reflections | (Δ/σ)max = 0.001 |
311 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C25H23ClN4O4 | V = 2267.1 (5) Å3 |
Mr = 478.92 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.565 (3) Å | µ = 0.21 mm−1 |
b = 6.9529 (5) Å | T = 120 K |
c = 21.010 (4) Å | 0.42 × 0.25 × 0.18 mm |
β = 110.465 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 5200 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3101 reflections with I > 2σ(I) |
Tmin = 0.917, Tmax = 0.963 | Rint = 0.085 |
32234 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.27 e Å−3 |
5200 reflections | Δρmin = −0.31 e Å−3 |
311 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.35429 (15) | 0.7010 (3) | 0.10761 (12) | 0.0208 (5) | |
N2 | 0.34712 (13) | 0.6924 (3) | 0.17521 (10) | 0.0236 (5) | |
H2 | 0.2947 | 0.7289 | 0.1712 | 0.022 (7)* | |
C3 | 0.36586 (15) | 0.4901 (4) | 0.19713 (12) | 0.0223 (6) | |
H3 | 0.3161 | 0.4095 | 0.1692 | 0.027* | |
C3a | 0.44474 (15) | 0.4440 (3) | 0.17453 (12) | 0.0210 (5) | |
H3A | 0.4389 | 0.3144 | 0.1527 | 0.025* | |
C4 | 0.53022 (15) | 0.4654 (4) | 0.23134 (12) | 0.0222 (6) | |
O4 | 0.56438 (11) | 0.3528 (2) | 0.27668 (9) | 0.0280 (4) | |
N5 | 0.56479 (12) | 0.6446 (3) | 0.22407 (10) | 0.0208 (5) | |
C6 | 0.51698 (15) | 0.7371 (4) | 0.16334 (13) | 0.0229 (6) | |
O6 | 0.53425 (11) | 0.8941 (3) | 0.14657 (9) | 0.0298 (4) | |
C6a | 0.44278 (14) | 0.6058 (3) | 0.12374 (12) | 0.0204 (5) | |
H6A | 0.4506 | 0.5541 | 0.0819 | 0.025* | |
C11 | 0.35230 (15) | 0.9074 (4) | 0.08365 (13) | 0.0238 (6) | |
O11 | 0.33582 (11) | 1.0481 (3) | 0.11079 (9) | 0.0293 (4) | |
O12 | 0.36961 (11) | 0.9140 (2) | 0.02571 (9) | 0.0287 (4) | |
C12 | 0.3740 (2) | 1.1032 (4) | −0.00083 (14) | 0.0383 (7) | |
H12A | 0.4179 | 1.1793 | 0.0334 | 0.057* | |
H12B | 0.3178 | 1.1666 | −0.0122 | 0.057* | |
H12C | 0.3891 | 1.0925 | −0.0418 | 0.057* | |
C13 | 0.28379 (15) | 0.5859 (4) | 0.05309 (13) | 0.0266 (6) | |
H13A | 0.2269 | 0.6271 | 0.0524 | 0.040* | |
H13B | 0.2913 | 0.4484 | 0.0638 | 0.040* | |
H13C | 0.2884 | 0.6092 | 0.0085 | 0.040* | |
N31 | 0.38357 (12) | 0.5120 (3) | 0.37596 (10) | 0.0234 (5) | |
N32 | 0.36345 (13) | 0.3215 (3) | 0.36376 (11) | 0.0245 (5) | |
C33 | 0.35929 (15) | 0.2937 (4) | 0.29990 (13) | 0.0227 (6) | |
C34 | 0.37592 (15) | 0.4644 (4) | 0.27026 (12) | 0.0215 (5) | |
C35 | 0.39208 (15) | 0.5996 (4) | 0.32083 (13) | 0.0241 (6) | |
H32 | 0.4066 | 0.7306 | 0.3178 | 0.029* | |
C311 | 0.39255 (15) | 0.5921 (4) | 0.44039 (12) | 0.0240 (6) | |
C312 | 0.40523 (16) | 0.7889 (4) | 0.45170 (13) | 0.0298 (6) | |
H312 | 0.4063 | 0.8716 | 0.4160 | 0.036* | |
C313 | 0.41640 (17) | 0.8636 (4) | 0.51575 (14) | 0.0346 (7) | |
H313 | 0.4262 | 0.9975 | 0.5239 | 0.042* | |
C314 | 0.41331 (16) | 0.7439 (4) | 0.56778 (14) | 0.0323 (7) | |
H314 | 0.4207 | 0.7952 | 0.6114 | 0.039* | |
C315 | 0.39936 (17) | 0.5493 (4) | 0.55546 (14) | 0.0341 (7) | |
H315 | 0.3961 | 0.4671 | 0.5906 | 0.041* | |
C316 | 0.39006 (16) | 0.4729 (4) | 0.49255 (13) | 0.0297 (6) | |
H316 | 0.3819 | 0.3384 | 0.4850 | 0.036* | |
C331 | 0.34076 (17) | 0.0990 (4) | 0.26810 (14) | 0.0297 (6) | |
H31A | 0.3209 | 0.0138 | 0.2968 | 0.045* | |
H31B | 0.3933 | 0.0461 | 0.2635 | 0.045* | |
H31C | 0.2959 | 0.1093 | 0.2231 | 0.045* | |
C51 | 0.64288 (15) | 0.7205 (4) | 0.27240 (12) | 0.0219 (6) | |
C52 | 0.64221 (16) | 0.9032 (4) | 0.29895 (13) | 0.0242 (6) | |
H52 | 0.5907 | 0.9769 | 0.2853 | 0.029* | |
C53 | 0.71749 (16) | 0.9771 (4) | 0.34558 (13) | 0.0256 (6) | |
H53 | 0.7180 | 1.1013 | 0.3646 | 0.031* | |
C54 | 0.79175 (15) | 0.8673 (4) | 0.36395 (12) | 0.0240 (6) | |
Cl54 | 0.88721 (4) | 0.96263 (10) | 0.42116 (3) | 0.03272 (19) | |
C55 | 0.79328 (16) | 0.6856 (4) | 0.33733 (12) | 0.0255 (6) | |
H55 | 0.8451 | 0.6131 | 0.3504 | 0.031* | |
C56 | 0.71774 (16) | 0.6117 (4) | 0.29127 (12) | 0.0243 (6) | |
H56 | 0.7172 | 0.4870 | 0.2727 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0236 (13) | 0.0213 (14) | 0.0182 (13) | −0.0011 (11) | 0.0079 (10) | −0.0022 (11) |
N2 | 0.0274 (12) | 0.0220 (12) | 0.0235 (12) | 0.0013 (10) | 0.0117 (9) | 0.0005 (10) |
C3 | 0.0225 (13) | 0.0196 (14) | 0.0251 (14) | −0.0026 (11) | 0.0086 (10) | −0.0014 (11) |
C3a | 0.0261 (13) | 0.0165 (13) | 0.0210 (13) | −0.0005 (11) | 0.0088 (10) | −0.0021 (11) |
C4 | 0.0274 (13) | 0.0192 (14) | 0.0232 (14) | 0.0012 (11) | 0.0128 (11) | −0.0018 (12) |
O4 | 0.0319 (10) | 0.0230 (10) | 0.0287 (11) | 0.0036 (8) | 0.0101 (8) | 0.0061 (8) |
N5 | 0.0242 (11) | 0.0190 (11) | 0.0176 (11) | −0.0020 (9) | 0.0051 (8) | 0.0012 (9) |
C6 | 0.0230 (13) | 0.0253 (15) | 0.0211 (14) | −0.0013 (11) | 0.0087 (10) | −0.0001 (12) |
O6 | 0.0294 (10) | 0.0265 (11) | 0.0293 (11) | −0.0056 (8) | 0.0051 (8) | 0.0084 (9) |
C6a | 0.0221 (13) | 0.0205 (13) | 0.0193 (13) | −0.0029 (11) | 0.0080 (10) | −0.0026 (11) |
C11 | 0.0229 (13) | 0.0262 (15) | 0.0191 (13) | −0.0028 (11) | 0.0036 (10) | −0.0027 (12) |
O11 | 0.0379 (11) | 0.0228 (10) | 0.0275 (10) | 0.0006 (8) | 0.0120 (8) | −0.0032 (9) |
O12 | 0.0440 (11) | 0.0233 (10) | 0.0200 (10) | 0.0002 (8) | 0.0127 (8) | 0.0025 (8) |
C12 | 0.062 (2) | 0.0264 (16) | 0.0286 (16) | −0.0041 (15) | 0.0188 (14) | 0.0033 (13) |
C13 | 0.0259 (14) | 0.0276 (15) | 0.0245 (14) | −0.0024 (11) | 0.0066 (11) | −0.0028 (12) |
N31 | 0.0235 (11) | 0.0258 (12) | 0.0217 (11) | −0.0001 (9) | 0.0087 (9) | 0.0001 (10) |
N32 | 0.0278 (11) | 0.0202 (12) | 0.0280 (13) | −0.0001 (9) | 0.0126 (10) | 0.0020 (10) |
C33 | 0.0223 (13) | 0.0220 (14) | 0.0254 (14) | 0.0015 (11) | 0.0101 (11) | 0.0020 (12) |
C34 | 0.0209 (12) | 0.0213 (14) | 0.0238 (13) | 0.0000 (11) | 0.0096 (10) | 0.0009 (12) |
C35 | 0.0285 (14) | 0.0206 (14) | 0.0241 (14) | 0.0002 (11) | 0.0105 (11) | 0.0049 (12) |
C311 | 0.0209 (13) | 0.0313 (15) | 0.0202 (13) | 0.0008 (11) | 0.0078 (10) | −0.0003 (12) |
C312 | 0.0337 (15) | 0.0285 (16) | 0.0247 (15) | 0.0047 (12) | 0.0071 (12) | 0.0018 (12) |
C313 | 0.0355 (16) | 0.0337 (17) | 0.0297 (16) | 0.0101 (13) | 0.0052 (12) | −0.0038 (14) |
C314 | 0.0276 (15) | 0.0464 (19) | 0.0208 (14) | 0.0078 (13) | 0.0059 (11) | −0.0026 (14) |
C315 | 0.0325 (15) | 0.0448 (19) | 0.0264 (15) | −0.0005 (14) | 0.0122 (12) | 0.0033 (14) |
C316 | 0.0287 (14) | 0.0317 (16) | 0.0289 (15) | −0.0029 (12) | 0.0104 (11) | 0.0005 (13) |
C331 | 0.0385 (16) | 0.0244 (15) | 0.0292 (15) | −0.0003 (12) | 0.0154 (12) | −0.0005 (12) |
C51 | 0.0227 (13) | 0.0229 (14) | 0.0190 (13) | −0.0017 (11) | 0.0060 (10) | 0.0014 (11) |
C52 | 0.0231 (13) | 0.0228 (14) | 0.0274 (14) | 0.0011 (11) | 0.0096 (11) | 0.0003 (12) |
C53 | 0.0305 (14) | 0.0239 (14) | 0.0249 (14) | −0.0015 (12) | 0.0127 (11) | −0.0041 (12) |
C54 | 0.0214 (13) | 0.0306 (16) | 0.0200 (13) | −0.0026 (11) | 0.0074 (10) | 0.0014 (12) |
Cl54 | 0.0254 (3) | 0.0430 (4) | 0.0276 (4) | −0.0090 (3) | 0.0066 (3) | −0.0036 (3) |
C55 | 0.0249 (14) | 0.0306 (16) | 0.0208 (14) | 0.0030 (12) | 0.0078 (11) | 0.0024 (12) |
C56 | 0.0292 (14) | 0.0218 (14) | 0.0224 (14) | 0.0023 (11) | 0.0097 (11) | 0.0001 (11) |
C1—N2 | 1.467 (3) | N32—C33 | 1.333 (3) |
C1—C11 | 1.517 (4) | C33—C34 | 1.412 (3) |
C1—C6a | 1.534 (3) | C33—C331 | 1.493 (4) |
C1—C13 | 1.543 (3) | C34—C35 | 1.373 (3) |
N2—C3 | 1.479 (3) | C35—H32 | 0.9500 |
N2—H2 | 0.8799 | C311—C316 | 1.386 (4) |
C3—C34 | 1.497 (3) | C311—C312 | 1.392 (4) |
C3—C3a | 1.572 (3) | C312—C313 | 1.393 (4) |
C3—H3 | 1.0000 | C312—H312 | 0.9500 |
C3a—C4 | 1.507 (3) | C313—C314 | 1.389 (4) |
C3a—C6a | 1.543 (3) | C313—H313 | 0.9500 |
C3a—H3A | 1.0000 | C314—C315 | 1.382 (4) |
C4—O4 | 1.210 (3) | C314—H314 | 0.9500 |
C4—N5 | 1.402 (3) | C315—C316 | 1.382 (4) |
N5—C6 | 1.401 (3) | C315—H315 | 0.9500 |
N5—C51 | 1.437 (3) | C316—H316 | 0.9500 |
C6—O6 | 1.212 (3) | C331—H31A | 0.9800 |
C6—C6a | 1.523 (3) | C331—H31B | 0.9800 |
C6a—H6A | 1.0000 | C331—H31C | 0.9800 |
C11—O11 | 1.211 (3) | C51—C56 | 1.387 (3) |
C11—O12 | 1.345 (3) | C51—C52 | 1.389 (3) |
O12—C12 | 1.440 (3) | C52—C53 | 1.387 (3) |
C12—H12A | 0.9800 | C52—H52 | 0.9500 |
C12—H12B | 0.9800 | C53—C54 | 1.383 (3) |
C12—H12C | 0.9800 | C53—H53 | 0.9500 |
C13—H13A | 0.9800 | C54—C55 | 1.385 (4) |
C13—H13B | 0.9800 | C54—Cl54 | 1.748 (2) |
C13—H13C | 0.9800 | C55—C56 | 1.385 (3) |
N31—C35 | 1.359 (3) | C55—H55 | 0.9500 |
N31—N32 | 1.368 (3) | C56—H56 | 0.9500 |
N31—C311 | 1.423 (3) | ||
N2—C1—C11 | 111.1 (2) | N32—N31—C311 | 119.7 (2) |
N2—C1—C6a | 99.39 (18) | C33—N32—N31 | 104.6 (2) |
C11—C1—C6a | 112.92 (19) | N32—C33—C34 | 111.9 (2) |
N2—C1—C13 | 113.65 (19) | N32—C33—C331 | 120.8 (2) |
C11—C1—C13 | 108.7 (2) | C34—C33—C331 | 127.3 (2) |
C6a—C1—C13 | 110.9 (2) | C35—C34—C33 | 104.4 (2) |
C1—N2—C3 | 105.12 (18) | C35—C34—C3 | 129.4 (2) |
C1—N2—H2 | 107.9 | C33—C34—C3 | 125.7 (2) |
C3—N2—H2 | 113.3 | N31—C35—C34 | 107.6 (2) |
N2—C3—C34 | 111.6 (2) | N31—C35—H32 | 126.2 |
N2—C3—C3a | 101.90 (19) | C34—C35—H32 | 126.2 |
C34—C3—C3a | 118.7 (2) | C316—C311—C312 | 119.8 (2) |
N2—C3—H3 | 108.0 | C316—C311—N31 | 119.7 (2) |
C34—C3—H3 | 108.0 | C312—C311—N31 | 120.4 (2) |
C3a—C3—H3 | 108.0 | C311—C312—C313 | 119.5 (3) |
C4—C3a—C6a | 105.21 (19) | C311—C312—H312 | 120.2 |
C4—C3a—C3 | 113.00 (19) | C313—C312—H312 | 120.2 |
C6a—C3a—C3 | 103.97 (19) | C314—C313—C312 | 120.5 (3) |
C4—C3a—H3A | 111.4 | C314—C313—H313 | 119.7 |
C6a—C3a—H3A | 111.4 | C312—C313—H313 | 119.7 |
C3—C3a—H3A | 111.4 | C315—C314—C313 | 119.3 (3) |
O4—C4—N5 | 124.4 (2) | C315—C314—H314 | 120.4 |
O4—C4—C3a | 127.7 (2) | C313—C314—H314 | 120.4 |
N5—C4—C3a | 107.9 (2) | C314—C315—C316 | 120.7 (3) |
C6—N5—C4 | 112.6 (2) | C314—C315—H315 | 119.6 |
C6—N5—C51 | 123.9 (2) | C316—C315—H315 | 119.6 |
C4—N5—C51 | 123.4 (2) | C315—C316—C311 | 120.1 (3) |
O6—C6—N5 | 124.2 (2) | C315—C316—H316 | 119.9 |
O6—C6—C6a | 127.5 (2) | C311—C316—H316 | 119.9 |
N5—C6—C6a | 108.3 (2) | C33—C331—H31A | 109.5 |
C6—C6a—C1 | 112.8 (2) | C33—C331—H31B | 109.5 |
C6—C6a—C3a | 103.96 (19) | H31A—C331—H31B | 109.5 |
C1—C6a—C3a | 104.76 (18) | C33—C331—H31C | 109.5 |
C6—C6a—H6A | 111.6 | H31A—C331—H31C | 109.5 |
C1—C6a—H6A | 111.6 | H31B—C331—H31C | 109.5 |
C3a—C6a—H6A | 111.6 | C56—C51—C52 | 121.1 (2) |
O11—C11—O12 | 123.6 (2) | C56—C51—N5 | 119.7 (2) |
O11—C11—C1 | 126.2 (2) | C52—C51—N5 | 119.2 (2) |
O12—C11—C1 | 110.2 (2) | C53—C52—C51 | 119.4 (2) |
C11—O12—C12 | 115.9 (2) | C53—C52—H52 | 120.3 |
O12—C12—H12A | 109.5 | C51—C52—H52 | 120.3 |
O12—C12—H12B | 109.5 | C54—C53—C52 | 119.0 (2) |
H12A—C12—H12B | 109.5 | C54—C53—H53 | 120.5 |
O12—C12—H12C | 109.5 | C52—C53—H53 | 120.5 |
H12A—C12—H12C | 109.5 | C53—C54—C55 | 122.1 (2) |
H12B—C12—H12C | 109.5 | C53—C54—Cl54 | 119.0 (2) |
C1—C13—H13A | 109.5 | C55—C54—Cl54 | 118.92 (19) |
C1—C13—H13B | 109.5 | C54—C55—C56 | 118.7 (2) |
H13A—C13—H13B | 109.5 | C54—C55—H55 | 120.6 |
C1—C13—H13C | 109.5 | C56—C55—H55 | 120.6 |
H13A—C13—H13C | 109.5 | C55—C56—C51 | 119.8 (2) |
H13B—C13—H13C | 109.5 | C55—C56—H56 | 120.1 |
C35—N31—N32 | 111.4 (2) | C51—C56—H56 | 120.1 |
C35—N31—C311 | 128.9 (2) | ||
C11—C1—N2—C3 | −169.94 (19) | C35—N31—N32—C33 | −0.3 (3) |
C6a—C1—N2—C3 | −50.8 (2) | C311—N31—N32—C33 | 179.5 (2) |
C13—C1—N2—C3 | 67.1 (2) | N31—N32—C33—C34 | −0.4 (3) |
C1—N2—C3—C34 | 170.28 (18) | N31—N32—C33—C331 | 178.4 (2) |
C1—N2—C3—C3a | 42.6 (2) | N32—C33—C34—C35 | 0.9 (3) |
N2—C3—C3a—C4 | 96.9 (2) | C331—C33—C34—C35 | −177.7 (2) |
C34—C3—C3a—C4 | −26.1 (3) | N32—C33—C34—C3 | −172.0 (2) |
N2—C3—C3a—C6a | −16.6 (2) | C331—C33—C34—C3 | 9.3 (4) |
C34—C3—C3a—C6a | −139.6 (2) | N2—C3—C34—C35 | −18.6 (3) |
C6a—C3a—C4—O4 | −167.9 (2) | C3a—C3—C34—C35 | 99.5 (3) |
C3—C3a—C4—O4 | 79.3 (3) | N2—C3—C34—C33 | 152.6 (2) |
C6a—C3a—C4—N5 | 13.2 (2) | C3a—C3—C34—C33 | −89.4 (3) |
C3—C3a—C4—N5 | −99.6 (2) | N32—N31—C35—C34 | 0.9 (3) |
O4—C4—N5—C6 | 173.5 (2) | C311—N31—C35—C34 | −178.9 (2) |
C3a—C4—N5—C6 | −7.6 (3) | C33—C34—C35—N31 | −1.1 (3) |
O4—C4—N5—C51 | −4.0 (4) | C3—C34—C35—N31 | 171.5 (2) |
C3a—C4—N5—C51 | 174.9 (2) | C35—N31—C311—C316 | −173.2 (2) |
C4—N5—C6—O6 | 179.2 (2) | N32—N31—C311—C316 | 6.9 (3) |
C51—N5—C6—O6 | −3.3 (4) | C35—N31—C311—C312 | 5.7 (4) |
C4—N5—C6—C6a | −1.5 (3) | N32—N31—C311—C312 | −174.1 (2) |
C51—N5—C6—C6a | 176.0 (2) | C316—C311—C312—C313 | 0.8 (4) |
O6—C6—C6a—C1 | −58.3 (3) | N31—C311—C312—C313 | −178.1 (2) |
N5—C6—C6a—C1 | 122.5 (2) | C311—C312—C313—C314 | −1.2 (4) |
O6—C6—C6a—C3a | −171.2 (2) | C312—C313—C314—C315 | 0.3 (4) |
N5—C6—C6a—C3a | 9.5 (2) | C313—C314—C315—C316 | 1.2 (4) |
N2—C1—C6a—C6 | −74.4 (2) | C314—C315—C316—C311 | −1.6 (4) |
C11—C1—C6a—C6 | 43.4 (3) | C312—C311—C316—C315 | 0.6 (4) |
C13—C1—C6a—C6 | 165.7 (2) | N31—C311—C316—C315 | 179.5 (2) |
N2—C1—C6a—C3a | 38.1 (2) | C6—N5—C51—C56 | −123.6 (3) |
C11—C1—C6a—C3a | 155.8 (2) | C4—N5—C51—C56 | 53.6 (3) |
C13—C1—C6a—C3a | −81.8 (2) | C6—N5—C51—C52 | 55.7 (3) |
C4—C3a—C6a—C6 | −13.5 (2) | C4—N5—C51—C52 | −127.1 (2) |
C3—C3a—C6a—C6 | 105.5 (2) | C56—C51—C52—C53 | −0.6 (4) |
C4—C3a—C6a—C1 | −132.1 (2) | N5—C51—C52—C53 | −179.9 (2) |
C3—C3a—C6a—C1 | −13.1 (2) | C51—C52—C53—C54 | 0.7 (4) |
N2—C1—C11—O11 | −9.2 (3) | C52—C53—C54—C55 | −0.1 (4) |
C6a—C1—C11—O11 | −119.8 (3) | C52—C53—C54—Cl54 | 178.49 (19) |
C13—C1—C11—O11 | 116.6 (3) | C53—C54—C55—C56 | −0.5 (4) |
N2—C1—C11—O12 | 172.39 (18) | Cl54—C54—C55—C56 | −179.10 (19) |
C6a—C1—C11—O12 | 61.7 (3) | C54—C55—C56—C51 | 0.5 (4) |
C13—C1—C11—O12 | −61.8 (3) | C52—C51—C56—C55 | 0.0 (4) |
O11—C11—O12—C12 | 4.5 (3) | N5—C51—C56—C55 | 179.3 (2) |
C1—C11—O12—C12 | −177.0 (2) |
Cg1 represents the centroid of the C51–C56 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N32i | 0.88 | 2.54 | 3.413 (3) | 169 |
C3a—H3A···O11ii | 1.00 | 2.46 | 3.307 (3) | 142 |
C6a—H6A···Cl54iii | 1.00 | 2.78 | 3.416 (3) | 122 |
C55—H55···O6iii | 0.95 | 2.50 | 3.422 (3) | 165 |
C56—H56···Cg1iii | 0.95 | 2.84 | 3.611 (3) | 139 |
C314—H314···O4iv | 0.95 | 2.50 | 3.229 (3) | 134 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C25H24N4O4 | C25H23ClN4O4 |
Mr | 444.48 | 478.92 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 11.355 (2), 20.025 (4), 10.4124 (8) | 16.565 (3), 6.9529 (5), 21.010 (4) |
β (°) | 110.030 (9) | 110.465 (11) |
V (Å3) | 2224.4 (6) | 2267.1 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.21 |
Crystal size (mm) | 0.39 × 0.35 × 0.29 | 0.42 × 0.25 × 0.18 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.965, 0.974 | 0.917, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32624, 5110, 3436 | 32234, 5200, 3101 |
Rint | 0.050 | 0.085 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.136, 1.06 | 0.054, 0.114, 1.04 |
No. of reflections | 5110 | 5200 |
No. of parameters | 301 | 311 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.30 | 0.27, −0.31 |
Computer programs: COLLECT (Nonius, 1998), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg3 represents the centroid of the N31/N32/C33–C35 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6a—H6A···O6i | 1.00 | 2.50 | 3.418 (2) | 152 |
C54—H54···O12ii | 0.95 | 2.46 | 3.256 (3) | 141 |
C313—H313···O4iii | 0.95 | 2.51 | 3.303 (3) | 142 |
N2—H2···Cg3iv | 0.96 | 2.63 | 3.522 (2) | 156 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+1, −z. |
Cg1 represents the centroid of the C51–C56 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N32i | 0.88 | 2.54 | 3.413 (3) | 169 |
C3a—H3A···O11ii | 1.00 | 2.46 | 3.307 (3) | 142 |
C6a—H6A···Cl54iii | 1.00 | 2.78 | 3.416 (3) | 122 |
C55—H55···O6iii | 0.95 | 2.50 | 3.422 (3) | 165 |
C56—H56···Cg1iii | 0.95 | 2.84 | 3.611 (3) | 139 |
C314—H314···O4iv | 0.95 | 2.50 | 3.229 (3) | 134 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z+1. |
(I) | (II) | |||
Q2 | ϕ2 | Q2 | ϕ2 | |
Ring A | 0.435 (2) | 19.7 (3) | 0.470 (3) | 15.7 (3) |
Ring B | 0.146 (2) | 91.6 (7) | 0.137 (3) | 78.7 (11) |
Ring A is defined by the atom sequence N2–C1–C6a–C3a–C3 and ring B is defined by the atom sequence N5–C4–C3a–C6a–C6. |
Parameter | (I) | (II) |
N31—N32 | 1.363 (2) | 1.368 (3) |
N32—C33 | 1.333 (2) | 1.333 (3) |
C33—C34 | 1.415 (2) | 1.412 (3) |
C34—C35 | 1.378 (3) | 1.373 (3) |
C35—N31 | 1.359 (2) | 1.359 (3) |
N2—C1—C11—O11 | -179.46 (16) | -18.6 (3) |
N2—C1—C11—O12 | -2.4 (2) | 172.39 (18) |
C1—C11—O11—C12 | 176.65 (15) | -177.0 (2) |
N2—C3—C34—C35 | -25.2 (2) | -18.6 (3) |
C35—N31—C311—C312 | 11.1 (3) | 5.7 (4) |
C4—N5—C51—C52 | 105.5 (2) | -127.1 (2) |