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In the mol­ecules of both methyl (1RS,3SR,3aRS,6aSR)-1-methyl-3-(3-methyl-1-phenyl-1H-pyrazol-4-yl)-4,6-dioxo-5-phenyl­octa­hydro­pyrrolo­[3,4-c]pyrrole-1-carboxyl­ate, C25H24N4O4, (I), and methyl (1RS,3SR,3aRS,6aSR)-5-(4-chlorophen­yl)-1-methyl-3-(3-methyl-1-phenyl-1H-pyrazol-4-yl)-4,6-dioxo­octa­hydro­pyrrolo­[3,4-c]pyrrole-1-carboxyl­ate, C25H23ClN4O4, (II), the two rings of the pyrrolo­pyrrole fragment are both nonplanar, with conformations close to half-chair forms. The overall conformations of the mol­ecules of (I) and (II) are very similar, apart from the orientation of the ester function. The mol­ecules of (I) are linked into sheets by a combination of an N-H...[pi](pyrrole) hydrogen bond and three independent C-H...O hydrogen bonds. The mol­ecules of (II) are also linked into sheets, which are generated by a combination of an N-H...N hydrogen bond and two inde­pendent C-H...O hydrogen bonds, weakly augmented by a C-H...[pi](arene) hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017563/sf3204sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017563/sf3204Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017563/sf3204IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017563/sf3204Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017563/sf3204IIsup5.cml
Supplementary material

CCDC references: 964801; 964802

Introduction top

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.

Experimental top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Synthesis and crystallization top

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).

Refinement top

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.

Results and discussion top

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 >CO···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.

Related literature top

For related literature, see: Allen et al. (1998); Bernstein et al. (1995); Brammer et al. (2001); Chauhan et al. (2011); Cremer & Pople (1975); Ferguson et al. (1998a, 1998b); Fustero et al. (2011); Georgiou et al. (2012); Gregson et al. (2000); Hassan et al. (2011); Hofmann (2002); Quiroga et al. (2008, 2010); Quiroga, Gálvez, Pérez, Valencia, Abonía & Insuasty (2011); Quiroga, Portillo, Pérez, Gálvez, Abonía & Insuasty (2011); Rotstein (2010); Rowland & Taylor (1996); Sharma et al. (2010); Spek (2009); Thallapally & Nangia (2001); Wood et al. (2009); Zhang et al. (2010).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the (1R,3S,3aR,6aS) enantiomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecular structure of the (1R,3S,3aR,6aS) enantiomer of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of rings running parallel to [101]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a C(11)C(11)[R22(20)] chain of rings running parallel to [001]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of a C(7) chain running parallel to [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-x + 3/2, y + 1/2, -z + 1/2), (-x + 3/2, y - 1/2, -z + 1/2), (x, y + 1, z) and (x, y - 1, z), respectively.
[Figure 6] Fig. 6. Part of the crystal structure of (II), showing the formation of a C(6)C(6)[R33(17)] chain of rings running parallel to [010]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-x + 1/2, y + 1/2, -z + 1/2), (-x + 1/2, y - 1/2, -z + 1/2), (x, y + 1, z) and (x, y - 1, z), respectively.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (001). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
(I) Methyl (1RS,3SR,3aRS,6aSR)-1-methyl-3-(3-methyl-1-phenyl-1H-pyrazol-4-yl)-4,6-dioxo-5-phenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate top
Crystal data top
C25H24N4O4F(000) = 936
Mr = 444.48Dx = 1.327 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5110 reflections
a = 11.355 (2) Åθ = 2.8–27.5°
b = 20.025 (4) ŵ = 0.09 mm1
c = 10.4124 (8) ÅT = 120 K
β = 110.030 (9)°Block, colourless
V = 2224.4 (6) Å30.39 × 0.35 × 0.29 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
5110 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3436 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2626
Tmin = 0.965, Tmax = 0.974l = 1313
32624 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-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 parametersΔρmax = 0.69 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C25H24N4O4V = 2224.4 (6) Å3
Mr = 444.48Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.355 (2) ŵ = 0.09 mm1
b = 20.025 (4) ÅT = 120 K
c = 10.4124 (8) Å0.39 × 0.35 × 0.29 mm
β = 110.030 (9)°
Data collection top
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 = 0.974Rint = 0.050
32624 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.06Δρmax = 0.69 e Å3
5110 reflectionsΔρmin = 0.30 e Å3
301 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.81247 (16)0.47889 (9)0.24951 (17)0.0226 (4)
N20.69738 (13)0.51195 (8)0.16270 (15)0.0236 (3)
H20.66570.49980.06790.028*
C30.59880 (16)0.49657 (9)0.22061 (17)0.0224 (4)
H30.56740.45010.19420.027*
C3a0.67267 (16)0.49918 (9)0.37913 (18)0.0224 (4)
H3A0.65270.45990.42730.027*
C40.65195 (17)0.56427 (9)0.44155 (17)0.0235 (4)
O40.56144 (12)0.58101 (7)0.47009 (13)0.0302 (3)
N50.75628 (13)0.60466 (7)0.45921 (15)0.0245 (3)
C60.84983 (16)0.57253 (9)0.42512 (17)0.0232 (4)
O60.94503 (12)0.59949 (6)0.42344 (13)0.0294 (3)
C6a0.81146 (16)0.50014 (9)0.39187 (17)0.0217 (4)
H6A0.86270.46930.46530.026*
C110.92879 (17)0.50372 (9)0.22231 (18)0.0238 (4)
O111.03271 (11)0.48262 (7)0.28212 (13)0.0305 (3)
O120.90233 (11)0.54852 (6)0.12176 (13)0.0285 (3)
C121.00987 (19)0.57678 (11)0.0964 (2)0.0356 (5)
H12A1.06240.60070.17800.053*
H12B0.98120.60780.01910.053*
H12C1.05870.54090.07490.053*
C130.81225 (18)0.40234 (9)0.2380 (2)0.0290 (4)
H13A0.73880.38420.25510.043*
H13B0.88870.38430.30560.043*
H13C0.80910.38960.14600.043*
N310.37723 (14)0.63502 (8)0.10243 (15)0.0260 (3)
N320.29998 (14)0.59009 (8)0.13204 (16)0.0265 (3)
C330.36931 (16)0.53532 (9)0.17361 (17)0.0238 (4)
C340.49182 (16)0.54447 (9)0.17040 (17)0.0230 (4)
C350.49289 (16)0.60883 (9)0.12406 (18)0.0250 (4)
H350.56160.63080.10990.030*
C3110.33015 (18)0.69943 (9)0.05190 (19)0.0284 (4)
C3120.3976 (2)0.74051 (11)0.0042 (2)0.0437 (5)
H3120.47670.72670.00700.052*
C3130.3480 (2)0.80269 (11)0.0569 (3)0.0494 (6)
H3130.39390.83130.09520.059*
C3140.2334 (2)0.82252 (11)0.0536 (2)0.0438 (6)
H3140.19950.86450.09080.053*
C3150.1679 (2)0.78164 (10)0.0036 (2)0.0402 (5)
H3150.08880.79560.00620.048*
C3160.21615 (19)0.72002 (10)0.0576 (2)0.0340 (5)
H3160.17090.69220.09830.041*
C3310.31533 (18)0.47364 (10)0.2132 (2)0.0319 (4)
H33A0.24500.48590.24260.048*
H33B0.38000.45110.28830.048*
H33C0.28570.44350.13450.048*
C510.76736 (18)0.67194 (10)0.5100 (2)0.0318 (4)
C520.8451 (2)0.68468 (13)0.6418 (3)0.0492 (6)
H520.88980.64940.69880.059*
C530.8571 (3)0.74986 (15)0.6902 (3)0.0683 (9)
H530.91040.75950.78080.082*
C540.7915 (3)0.80061 (14)0.6064 (4)0.0685 (9)
H540.79980.84520.63970.082*
C550.7147 (3)0.78732 (12)0.4760 (3)0.0618 (8)
H550.67000.82260.41910.074*
C560.7017 (2)0.72221 (11)0.4261 (3)0.0458 (6)
H560.64820.71270.33550.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0191 (9)0.0242 (9)0.0225 (9)0.0010 (7)0.0046 (7)0.0011 (7)
N20.0185 (7)0.0306 (8)0.0202 (7)0.0009 (6)0.0048 (6)0.0007 (6)
C30.0181 (8)0.0253 (9)0.0235 (9)0.0010 (7)0.0068 (7)0.0005 (7)
C3a0.0204 (9)0.0235 (9)0.0228 (9)0.0001 (7)0.0068 (7)0.0013 (7)
C40.0221 (9)0.0281 (9)0.0188 (8)0.0006 (7)0.0051 (7)0.0015 (7)
O40.0254 (7)0.0377 (8)0.0295 (7)0.0033 (6)0.0120 (6)0.0021 (6)
N50.0214 (8)0.0242 (8)0.0270 (8)0.0009 (6)0.0070 (6)0.0040 (6)
C60.0213 (9)0.0266 (9)0.0191 (8)0.0013 (7)0.0037 (7)0.0011 (7)
O60.0229 (7)0.0298 (7)0.0345 (7)0.0045 (6)0.0085 (6)0.0046 (6)
C6a0.0197 (8)0.0224 (9)0.0211 (8)0.0009 (7)0.0045 (7)0.0006 (7)
C110.0236 (9)0.0250 (9)0.0219 (9)0.0009 (7)0.0065 (7)0.0035 (7)
O110.0201 (7)0.0388 (8)0.0316 (7)0.0048 (6)0.0075 (6)0.0021 (6)
O120.0221 (7)0.0327 (7)0.0314 (7)0.0014 (6)0.0100 (5)0.0051 (6)
C120.0274 (10)0.0410 (12)0.0412 (12)0.0062 (9)0.0157 (9)0.0035 (10)
C130.0276 (10)0.0273 (10)0.0311 (10)0.0005 (8)0.0088 (8)0.0040 (8)
N310.0202 (8)0.0265 (8)0.0297 (8)0.0009 (6)0.0063 (6)0.0018 (6)
N320.0205 (8)0.0292 (8)0.0288 (8)0.0006 (6)0.0072 (6)0.0026 (7)
C330.0200 (9)0.0296 (10)0.0206 (9)0.0013 (7)0.0053 (7)0.0007 (7)
C340.0184 (8)0.0292 (9)0.0193 (8)0.0007 (7)0.0040 (7)0.0016 (7)
C350.0189 (9)0.0294 (10)0.0247 (9)0.0002 (7)0.0051 (7)0.0002 (7)
C3110.0280 (10)0.0244 (9)0.0276 (10)0.0001 (8)0.0027 (8)0.0001 (8)
C3120.0360 (12)0.0366 (12)0.0576 (14)0.0018 (10)0.0148 (11)0.0115 (11)
C3130.0488 (15)0.0337 (12)0.0604 (15)0.0039 (11)0.0120 (12)0.0125 (11)
C3140.0501 (14)0.0263 (11)0.0418 (12)0.0058 (10)0.0014 (10)0.0024 (9)
C3150.0381 (12)0.0327 (11)0.0426 (12)0.0070 (9)0.0047 (10)0.0058 (10)
C3160.0302 (11)0.0312 (11)0.0382 (11)0.0037 (9)0.0084 (9)0.0022 (9)
C3310.0264 (10)0.0344 (11)0.0359 (11)0.0001 (8)0.0118 (8)0.0085 (9)
C510.0294 (10)0.0279 (10)0.0431 (12)0.0033 (8)0.0190 (9)0.0109 (9)
C520.0343 (12)0.0529 (14)0.0556 (15)0.0006 (11)0.0091 (11)0.0265 (12)
C530.0448 (15)0.071 (2)0.090 (2)0.0115 (14)0.0244 (15)0.0553 (18)
C540.0625 (18)0.0399 (15)0.127 (3)0.0212 (14)0.0632 (19)0.0405 (17)
C550.084 (2)0.0276 (12)0.098 (2)0.0022 (13)0.0621 (19)0.0000 (14)
C560.0611 (16)0.0295 (11)0.0553 (14)0.0031 (11)0.0307 (12)0.0003 (10)
Geometric parameters (Å, º) top
C1—N21.468 (2)N32—C331.333 (2)
C1—C111.526 (2)C33—C341.415 (2)
C1—C131.538 (2)C33—C3311.498 (3)
C1—C6a1.546 (2)C34—C351.378 (3)
N2—C31.474 (2)C35—H350.9500
N2—H20.9590C311—C3161.379 (3)
C3—C341.495 (2)C311—C3121.382 (3)
C3—C3a1.575 (2)C312—C3131.399 (3)
C3—H31.0000C312—H3120.9500
C3a—C41.510 (3)C313—C3141.373 (3)
C3a—C6a1.536 (2)C313—H3130.9500
C3a—H3A1.0000C314—C3151.371 (3)
C4—O41.211 (2)C314—H3140.9500
C4—N51.394 (2)C315—C3161.389 (3)
N5—C61.388 (2)C315—H3150.9500
N5—C511.437 (2)C316—H3160.9500
C6—O61.214 (2)C331—H33A0.9800
C6—C6a1.519 (2)C331—H33B0.9800
C6a—H6A1.0000C331—H33C0.9800
C11—O111.206 (2)C51—C561.374 (3)
C11—O121.332 (2)C51—C521.378 (3)
O12—C121.450 (2)C52—C531.389 (3)
C12—H12A0.9800C52—H520.9500
C12—H12B0.9800C53—C541.380 (4)
C12—H12C0.9800C53—H530.9500
C13—H13A0.9800C54—C551.365 (4)
C13—H13B0.9800C54—H540.9500
C13—H13C0.9800C55—C561.393 (3)
N31—C351.359 (2)C55—H550.9500
N31—N321.363 (2)C56—H560.9500
N31—C3111.426 (2)
N2—C1—C11112.55 (15)N32—N31—C311119.42 (15)
N2—C1—C13115.11 (14)C33—N32—N31105.20 (14)
C11—C1—C13106.79 (14)N32—C33—C34111.22 (16)
N2—C1—C6a99.72 (13)N32—C33—C331121.06 (16)
C11—C1—C6a112.30 (14)C34—C33—C331127.70 (17)
C13—C1—C6a110.41 (14)C35—C34—C33104.84 (16)
C1—N2—C3107.13 (14)C35—C34—C3128.26 (16)
C1—N2—H2117.4C33—C34—C3126.62 (16)
C3—N2—H2107.4N31—C35—C34107.16 (16)
N2—C3—C34111.28 (14)N31—C35—H35126.4
N2—C3—C3a102.42 (13)C34—C35—H35126.4
C34—C3—C3a114.99 (14)C316—C311—C312120.28 (19)
N2—C3—H3109.3C316—C311—N31119.56 (17)
C34—C3—H3109.3C312—C311—N31120.16 (18)
C3a—C3—H3109.3C311—C312—C313119.3 (2)
C4—C3a—C6a104.98 (14)C311—C312—H312120.4
C4—C3a—C3111.95 (14)C313—C312—H312120.4
C6a—C3a—C3104.67 (13)C314—C313—C312120.3 (2)
C4—C3a—H3A111.6C314—C313—H313119.8
C6a—C3a—H3A111.6C312—C313—H313119.8
C3—C3a—H3A111.6C315—C314—C313119.9 (2)
O4—C4—N5124.16 (17)C315—C314—H314120.1
O4—C4—C3a127.95 (17)C313—C314—H314120.1
N5—C4—C3a107.87 (14)C314—C315—C316120.6 (2)
C6—N5—C4112.81 (15)C314—C315—H315119.7
C6—N5—C51123.40 (15)C316—C315—H315119.7
C4—N5—C51123.78 (15)C311—C316—C315119.6 (2)
O6—C6—N5124.12 (17)C311—C316—H316120.2
O6—C6—C6a127.48 (16)C315—C316—H316120.2
N5—C6—C6a108.40 (15)C33—C331—H33A109.5
C6—C6a—C3a103.73 (14)C33—C331—H33B109.5
C6—C6a—C1112.67 (14)H33A—C331—H33B109.5
C3a—C6a—C1104.96 (13)C33—C331—H33C109.5
C6—C6a—H6A111.7H33A—C331—H33C109.5
C3a—C6a—H6A111.7H33B—C331—H33C109.5
C1—C6a—H6A111.7C56—C51—C52121.4 (2)
O11—C11—O12123.98 (17)C56—C51—N5119.55 (19)
O11—C11—C1123.08 (17)C52—C51—N5119.06 (19)
O12—C11—C1112.87 (15)C51—C52—C53119.0 (3)
C11—O12—C12115.38 (14)C51—C52—H52120.5
O12—C12—H12A109.5C53—C52—H52120.5
O12—C12—H12B109.5C54—C53—C52119.9 (3)
H12A—C12—H12B109.5C54—C53—H53120.1
O12—C12—H12C109.5C52—C53—H53120.1
H12A—C12—H12C109.5C55—C54—C53120.5 (2)
H12B—C12—H12C109.5C55—C54—H54119.7
C1—C13—H13A109.5C53—C54—H54119.7
C1—C13—H13B109.5C54—C55—C56120.3 (3)
H13A—C13—H13B109.5C54—C55—H55119.9
C1—C13—H13C109.5C56—C55—H55119.9
H13A—C13—H13C109.5C51—C56—C55118.9 (2)
H13B—C13—H13C109.5C51—C56—H56120.5
C35—N31—N32111.59 (15)C55—C56—H56120.5
C35—N31—C311128.97 (16)
C11—C1—N2—C3166.37 (14)C1—C11—O12—C12176.65 (15)
C13—C1—N2—C370.94 (18)C35—N31—N32—C330.43 (19)
C6a—C1—N2—C347.16 (16)C311—N31—N32—C33178.80 (15)
C1—N2—C3—C34161.32 (14)N31—N32—C33—C340.31 (19)
C1—N2—C3—C3a37.95 (17)N31—N32—C33—C331178.82 (16)
N2—C3—C3a—C4100.65 (16)N32—C33—C34—C350.1 (2)
C34—C3—C3a—C420.2 (2)C331—C33—C34—C35178.48 (18)
N2—C3—C3a—C6a12.54 (17)N32—C33—C34—C3174.41 (16)
C34—C3—C3a—C6a133.38 (15)C331—C33—C34—C37.2 (3)
C6a—C3a—C4—O4169.30 (17)N2—C3—C34—C3525.2 (2)
C3—C3a—C4—O477.7 (2)C3a—C3—C34—C3590.7 (2)
C6a—C3a—C4—N512.14 (18)N2—C3—C34—C33161.83 (16)
C3—C3a—C4—N5100.85 (16)C3a—C3—C34—C3382.3 (2)
O4—C4—N5—C6176.93 (16)N32—N31—C35—C340.4 (2)
C3a—C4—N5—C64.45 (19)C311—N31—C35—C34178.56 (17)
O4—C4—N5—C511.8 (3)C33—C34—C35—N310.18 (19)
C3a—C4—N5—C51176.78 (16)C3—C34—C35—N31174.02 (16)
C4—N5—C6—O6174.64 (16)C35—N31—C311—C316169.88 (18)
C51—N5—C6—O66.6 (3)N32—N31—C311—C31612.1 (3)
C4—N5—C6—C6a5.41 (19)C35—N31—C311—C31211.1 (3)
C51—N5—C6—C6a173.37 (16)N32—N31—C311—C312167.00 (18)
O6—C6—C6a—C3a167.48 (17)C316—C311—C312—C3130.9 (3)
N5—C6—C6a—C3a12.57 (18)N31—C311—C312—C313178.1 (2)
O6—C6—C6a—C154.5 (2)C311—C312—C313—C3140.3 (4)
N5—C6—C6a—C1125.53 (15)C312—C313—C314—C3151.0 (4)
C4—C3a—C6a—C614.60 (17)C313—C314—C315—C3160.3 (3)
C3—C3a—C6a—C6103.44 (15)C312—C311—C316—C3151.6 (3)
C4—C3a—C6a—C1133.02 (14)N31—C311—C316—C315177.48 (17)
C3—C3a—C6a—C114.98 (17)C314—C315—C316—C3110.9 (3)
N2—C1—C6a—C675.37 (16)C6—N5—C51—C56106.2 (2)
C11—C1—C6a—C644.0 (2)C4—N5—C51—C5675.2 (2)
C13—C1—C6a—C6163.09 (14)C6—N5—C51—C5273.1 (2)
N2—C1—C6a—C3a36.83 (16)C4—N5—C51—C52105.5 (2)
C11—C1—C6a—C3a156.23 (14)C56—C51—C52—C530.2 (3)
C13—C1—C6a—C3a84.71 (16)N5—C51—C52—C53179.1 (2)
N2—C1—C11—O11179.46 (16)C51—C52—C53—C540.1 (4)
C13—C1—C11—O1152.2 (2)C52—C53—C54—C550.0 (4)
C6a—C1—C11—O1168.9 (2)C53—C54—C55—C560.1 (4)
N2—C1—C11—O122.4 (2)C52—C51—C56—C550.2 (3)
C13—C1—C11—O12124.83 (16)N5—C51—C56—C55179.08 (19)
C6a—C1—C11—O12114.01 (16)C54—C55—C56—C510.1 (4)
O11—C11—O12—C126.3 (3)
Hydrogen-bond geometry (Å, º) top
Cg3 represents the centroid of the N31/N32/C33–C35 ring.
D—H···AD—HH···AD···AD—H···A
C6a—H6A···O6i1.002.503.418 (2)152
C54—H54···O12ii0.952.463.256 (3)141
C313—H313···O4iii0.952.513.303 (3)142
N2—H2···Cg3iv0.962.633.522 (2)156
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+3/2, z+1/2; (iii) x, y+3/2, z1/2; (iv) x+1, y+1, z.
(II) Methyl (1RS,3SR,3aRS,6aSR)-5-(4-chlorophenyl)-1-methyl-3-(3-methyl-1-phenyl-1H-pyrazol-4-yl)-4,6-dioxooctahydropyrrolo[3,4-c]pyrrole-1-carboxylate top
Crystal data top
C25H23ClN4O4F(000) = 1000
Mr = 478.92Dx = 1.403 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5200 reflections
a = 16.565 (3) Åθ = 2.6–27.5°
b = 6.9529 (5) ŵ = 0.21 mm1
c = 21.010 (4) ÅT = 120 K
β = 110.465 (11)°Block, colourless
V = 2267.1 (5) Å30.42 × 0.25 × 0.18 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
5200 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode3101 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.6°
ϕ and ω scansh = 2121
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 99
Tmin = 0.917, Tmax = 0.963l = 2727
32234 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C25H23ClN4O4V = 2267.1 (5) Å3
Mr = 478.92Z = 4
Monoclinic, P21/nMo Kα radiation
a = 16.565 (3) ŵ = 0.21 mm1
b = 6.9529 (5) ÅT = 120 K
c = 21.010 (4) Å0.42 × 0.25 × 0.18 mm
β = 110.465 (11)°
Data collection top
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 = 0.963Rint = 0.085
32234 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.04Δρmax = 0.27 e Å3
5200 reflectionsΔρmin = 0.31 e Å3
311 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.35429 (15)0.7010 (3)0.10761 (12)0.0208 (5)
N20.34712 (13)0.6924 (3)0.17521 (10)0.0236 (5)
H20.29470.72890.17120.022 (7)*
C30.36586 (15)0.4901 (4)0.19713 (12)0.0223 (6)
H30.31610.40950.16920.027*
C3a0.44474 (15)0.4440 (3)0.17453 (12)0.0210 (5)
H3A0.43890.31440.15270.025*
C40.53022 (15)0.4654 (4)0.23134 (12)0.0222 (6)
O40.56438 (11)0.3528 (2)0.27668 (9)0.0280 (4)
N50.56479 (12)0.6446 (3)0.22407 (10)0.0208 (5)
C60.51698 (15)0.7371 (4)0.16334 (13)0.0229 (6)
O60.53425 (11)0.8941 (3)0.14657 (9)0.0298 (4)
C6a0.44278 (14)0.6058 (3)0.12374 (12)0.0204 (5)
H6A0.45060.55410.08190.025*
C110.35230 (15)0.9074 (4)0.08365 (13)0.0238 (6)
O110.33582 (11)1.0481 (3)0.11079 (9)0.0293 (4)
O120.36961 (11)0.9140 (2)0.02571 (9)0.0287 (4)
C120.3740 (2)1.1032 (4)0.00083 (14)0.0383 (7)
H12A0.41791.17930.03340.057*
H12B0.31781.16660.01220.057*
H12C0.38911.09250.04180.057*
C130.28379 (15)0.5859 (4)0.05309 (13)0.0266 (6)
H13A0.22690.62710.05240.040*
H13B0.29130.44840.06380.040*
H13C0.28840.60920.00850.040*
N310.38357 (12)0.5120 (3)0.37596 (10)0.0234 (5)
N320.36345 (13)0.3215 (3)0.36376 (11)0.0245 (5)
C330.35929 (15)0.2937 (4)0.29990 (13)0.0227 (6)
C340.37592 (15)0.4644 (4)0.27026 (12)0.0215 (5)
C350.39208 (15)0.5996 (4)0.32083 (13)0.0241 (6)
H320.40660.73060.31780.029*
C3110.39255 (15)0.5921 (4)0.44039 (12)0.0240 (6)
C3120.40523 (16)0.7889 (4)0.45170 (13)0.0298 (6)
H3120.40630.87160.41600.036*
C3130.41640 (17)0.8636 (4)0.51575 (14)0.0346 (7)
H3130.42620.99750.52390.042*
C3140.41331 (16)0.7439 (4)0.56778 (14)0.0323 (7)
H3140.42070.79520.61140.039*
C3150.39936 (17)0.5493 (4)0.55546 (14)0.0341 (7)
H3150.39610.46710.59060.041*
C3160.39006 (16)0.4729 (4)0.49255 (13)0.0297 (6)
H3160.38190.33840.48500.036*
C3310.34076 (17)0.0990 (4)0.26810 (14)0.0297 (6)
H31A0.32090.01380.29680.045*
H31B0.39330.04610.26350.045*
H31C0.29590.10930.22310.045*
C510.64288 (15)0.7205 (4)0.27240 (12)0.0219 (6)
C520.64221 (16)0.9032 (4)0.29895 (13)0.0242 (6)
H520.59070.97690.28530.029*
C530.71749 (16)0.9771 (4)0.34558 (13)0.0256 (6)
H530.71801.10130.36460.031*
C540.79175 (15)0.8673 (4)0.36395 (12)0.0240 (6)
Cl540.88721 (4)0.96263 (10)0.42116 (3)0.03272 (19)
C550.79328 (16)0.6856 (4)0.33733 (12)0.0255 (6)
H550.84510.61310.35040.031*
C560.71774 (16)0.6117 (4)0.29127 (12)0.0243 (6)
H560.71720.48700.27270.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0236 (13)0.0213 (14)0.0182 (13)0.0011 (11)0.0079 (10)0.0022 (11)
N20.0274 (12)0.0220 (12)0.0235 (12)0.0013 (10)0.0117 (9)0.0005 (10)
C30.0225 (13)0.0196 (14)0.0251 (14)0.0026 (11)0.0086 (10)0.0014 (11)
C3a0.0261 (13)0.0165 (13)0.0210 (13)0.0005 (11)0.0088 (10)0.0021 (11)
C40.0274 (13)0.0192 (14)0.0232 (14)0.0012 (11)0.0128 (11)0.0018 (12)
O40.0319 (10)0.0230 (10)0.0287 (11)0.0036 (8)0.0101 (8)0.0061 (8)
N50.0242 (11)0.0190 (11)0.0176 (11)0.0020 (9)0.0051 (8)0.0012 (9)
C60.0230 (13)0.0253 (15)0.0211 (14)0.0013 (11)0.0087 (10)0.0001 (12)
O60.0294 (10)0.0265 (11)0.0293 (11)0.0056 (8)0.0051 (8)0.0084 (9)
C6a0.0221 (13)0.0205 (13)0.0193 (13)0.0029 (11)0.0080 (10)0.0026 (11)
C110.0229 (13)0.0262 (15)0.0191 (13)0.0028 (11)0.0036 (10)0.0027 (12)
O110.0379 (11)0.0228 (10)0.0275 (10)0.0006 (8)0.0120 (8)0.0032 (9)
O120.0440 (11)0.0233 (10)0.0200 (10)0.0002 (8)0.0127 (8)0.0025 (8)
C120.062 (2)0.0264 (16)0.0286 (16)0.0041 (15)0.0188 (14)0.0033 (13)
C130.0259 (14)0.0276 (15)0.0245 (14)0.0024 (11)0.0066 (11)0.0028 (12)
N310.0235 (11)0.0258 (12)0.0217 (11)0.0001 (9)0.0087 (9)0.0001 (10)
N320.0278 (11)0.0202 (12)0.0280 (13)0.0001 (9)0.0126 (10)0.0020 (10)
C330.0223 (13)0.0220 (14)0.0254 (14)0.0015 (11)0.0101 (11)0.0020 (12)
C340.0209 (12)0.0213 (14)0.0238 (13)0.0000 (11)0.0096 (10)0.0009 (12)
C350.0285 (14)0.0206 (14)0.0241 (14)0.0002 (11)0.0105 (11)0.0049 (12)
C3110.0209 (13)0.0313 (15)0.0202 (13)0.0008 (11)0.0078 (10)0.0003 (12)
C3120.0337 (15)0.0285 (16)0.0247 (15)0.0047 (12)0.0071 (12)0.0018 (12)
C3130.0355 (16)0.0337 (17)0.0297 (16)0.0101 (13)0.0052 (12)0.0038 (14)
C3140.0276 (15)0.0464 (19)0.0208 (14)0.0078 (13)0.0059 (11)0.0026 (14)
C3150.0325 (15)0.0448 (19)0.0264 (15)0.0005 (14)0.0122 (12)0.0033 (14)
C3160.0287 (14)0.0317 (16)0.0289 (15)0.0029 (12)0.0104 (11)0.0005 (13)
C3310.0385 (16)0.0244 (15)0.0292 (15)0.0003 (12)0.0154 (12)0.0005 (12)
C510.0227 (13)0.0229 (14)0.0190 (13)0.0017 (11)0.0060 (10)0.0014 (11)
C520.0231 (13)0.0228 (14)0.0274 (14)0.0011 (11)0.0096 (11)0.0003 (12)
C530.0305 (14)0.0239 (14)0.0249 (14)0.0015 (12)0.0127 (11)0.0041 (12)
C540.0214 (13)0.0306 (16)0.0200 (13)0.0026 (11)0.0074 (10)0.0014 (12)
Cl540.0254 (3)0.0430 (4)0.0276 (4)0.0090 (3)0.0066 (3)0.0036 (3)
C550.0249 (14)0.0306 (16)0.0208 (14)0.0030 (12)0.0078 (11)0.0024 (12)
C560.0292 (14)0.0218 (14)0.0224 (14)0.0023 (11)0.0097 (11)0.0001 (11)
Geometric parameters (Å, º) top
C1—N21.467 (3)N32—C331.333 (3)
C1—C111.517 (4)C33—C341.412 (3)
C1—C6a1.534 (3)C33—C3311.493 (4)
C1—C131.543 (3)C34—C351.373 (3)
N2—C31.479 (3)C35—H320.9500
N2—H20.8799C311—C3161.386 (4)
C3—C341.497 (3)C311—C3121.392 (4)
C3—C3a1.572 (3)C312—C3131.393 (4)
C3—H31.0000C312—H3120.9500
C3a—C41.507 (3)C313—C3141.389 (4)
C3a—C6a1.543 (3)C313—H3130.9500
C3a—H3A1.0000C314—C3151.382 (4)
C4—O41.210 (3)C314—H3140.9500
C4—N51.402 (3)C315—C3161.382 (4)
N5—C61.401 (3)C315—H3150.9500
N5—C511.437 (3)C316—H3160.9500
C6—O61.212 (3)C331—H31A0.9800
C6—C6a1.523 (3)C331—H31B0.9800
C6a—H6A1.0000C331—H31C0.9800
C11—O111.211 (3)C51—C561.387 (3)
C11—O121.345 (3)C51—C521.389 (3)
O12—C121.440 (3)C52—C531.387 (3)
C12—H12A0.9800C52—H520.9500
C12—H12B0.9800C53—C541.383 (3)
C12—H12C0.9800C53—H530.9500
C13—H13A0.9800C54—C551.385 (4)
C13—H13B0.9800C54—Cl541.748 (2)
C13—H13C0.9800C55—C561.385 (3)
N31—C351.359 (3)C55—H550.9500
N31—N321.368 (3)C56—H560.9500
N31—C3111.423 (3)
N2—C1—C11111.1 (2)N32—N31—C311119.7 (2)
N2—C1—C6a99.39 (18)C33—N32—N31104.6 (2)
C11—C1—C6a112.92 (19)N32—C33—C34111.9 (2)
N2—C1—C13113.65 (19)N32—C33—C331120.8 (2)
C11—C1—C13108.7 (2)C34—C33—C331127.3 (2)
C6a—C1—C13110.9 (2)C35—C34—C33104.4 (2)
C1—N2—C3105.12 (18)C35—C34—C3129.4 (2)
C1—N2—H2107.9C33—C34—C3125.7 (2)
C3—N2—H2113.3N31—C35—C34107.6 (2)
N2—C3—C34111.6 (2)N31—C35—H32126.2
N2—C3—C3a101.90 (19)C34—C35—H32126.2
C34—C3—C3a118.7 (2)C316—C311—C312119.8 (2)
N2—C3—H3108.0C316—C311—N31119.7 (2)
C34—C3—H3108.0C312—C311—N31120.4 (2)
C3a—C3—H3108.0C311—C312—C313119.5 (3)
C4—C3a—C6a105.21 (19)C311—C312—H312120.2
C4—C3a—C3113.00 (19)C313—C312—H312120.2
C6a—C3a—C3103.97 (19)C314—C313—C312120.5 (3)
C4—C3a—H3A111.4C314—C313—H313119.7
C6a—C3a—H3A111.4C312—C313—H313119.7
C3—C3a—H3A111.4C315—C314—C313119.3 (3)
O4—C4—N5124.4 (2)C315—C314—H314120.4
O4—C4—C3a127.7 (2)C313—C314—H314120.4
N5—C4—C3a107.9 (2)C314—C315—C316120.7 (3)
C6—N5—C4112.6 (2)C314—C315—H315119.6
C6—N5—C51123.9 (2)C316—C315—H315119.6
C4—N5—C51123.4 (2)C315—C316—C311120.1 (3)
O6—C6—N5124.2 (2)C315—C316—H316119.9
O6—C6—C6a127.5 (2)C311—C316—H316119.9
N5—C6—C6a108.3 (2)C33—C331—H31A109.5
C6—C6a—C1112.8 (2)C33—C331—H31B109.5
C6—C6a—C3a103.96 (19)H31A—C331—H31B109.5
C1—C6a—C3a104.76 (18)C33—C331—H31C109.5
C6—C6a—H6A111.6H31A—C331—H31C109.5
C1—C6a—H6A111.6H31B—C331—H31C109.5
C3a—C6a—H6A111.6C56—C51—C52121.1 (2)
O11—C11—O12123.6 (2)C56—C51—N5119.7 (2)
O11—C11—C1126.2 (2)C52—C51—N5119.2 (2)
O12—C11—C1110.2 (2)C53—C52—C51119.4 (2)
C11—O12—C12115.9 (2)C53—C52—H52120.3
O12—C12—H12A109.5C51—C52—H52120.3
O12—C12—H12B109.5C54—C53—C52119.0 (2)
H12A—C12—H12B109.5C54—C53—H53120.5
O12—C12—H12C109.5C52—C53—H53120.5
H12A—C12—H12C109.5C53—C54—C55122.1 (2)
H12B—C12—H12C109.5C53—C54—Cl54119.0 (2)
C1—C13—H13A109.5C55—C54—Cl54118.92 (19)
C1—C13—H13B109.5C54—C55—C56118.7 (2)
H13A—C13—H13B109.5C54—C55—H55120.6
C1—C13—H13C109.5C56—C55—H55120.6
H13A—C13—H13C109.5C55—C56—C51119.8 (2)
H13B—C13—H13C109.5C55—C56—H56120.1
C35—N31—N32111.4 (2)C51—C56—H56120.1
C35—N31—C311128.9 (2)
C11—C1—N2—C3169.94 (19)C35—N31—N32—C330.3 (3)
C6a—C1—N2—C350.8 (2)C311—N31—N32—C33179.5 (2)
C13—C1—N2—C367.1 (2)N31—N32—C33—C340.4 (3)
C1—N2—C3—C34170.28 (18)N31—N32—C33—C331178.4 (2)
C1—N2—C3—C3a42.6 (2)N32—C33—C34—C350.9 (3)
N2—C3—C3a—C496.9 (2)C331—C33—C34—C35177.7 (2)
C34—C3—C3a—C426.1 (3)N32—C33—C34—C3172.0 (2)
N2—C3—C3a—C6a16.6 (2)C331—C33—C34—C39.3 (4)
C34—C3—C3a—C6a139.6 (2)N2—C3—C34—C3518.6 (3)
C6a—C3a—C4—O4167.9 (2)C3a—C3—C34—C3599.5 (3)
C3—C3a—C4—O479.3 (3)N2—C3—C34—C33152.6 (2)
C6a—C3a—C4—N513.2 (2)C3a—C3—C34—C3389.4 (3)
C3—C3a—C4—N599.6 (2)N32—N31—C35—C340.9 (3)
O4—C4—N5—C6173.5 (2)C311—N31—C35—C34178.9 (2)
C3a—C4—N5—C67.6 (3)C33—C34—C35—N311.1 (3)
O4—C4—N5—C514.0 (4)C3—C34—C35—N31171.5 (2)
C3a—C4—N5—C51174.9 (2)C35—N31—C311—C316173.2 (2)
C4—N5—C6—O6179.2 (2)N32—N31—C311—C3166.9 (3)
C51—N5—C6—O63.3 (4)C35—N31—C311—C3125.7 (4)
C4—N5—C6—C6a1.5 (3)N32—N31—C311—C312174.1 (2)
C51—N5—C6—C6a176.0 (2)C316—C311—C312—C3130.8 (4)
O6—C6—C6a—C158.3 (3)N31—C311—C312—C313178.1 (2)
N5—C6—C6a—C1122.5 (2)C311—C312—C313—C3141.2 (4)
O6—C6—C6a—C3a171.2 (2)C312—C313—C314—C3150.3 (4)
N5—C6—C6a—C3a9.5 (2)C313—C314—C315—C3161.2 (4)
N2—C1—C6a—C674.4 (2)C314—C315—C316—C3111.6 (4)
C11—C1—C6a—C643.4 (3)C312—C311—C316—C3150.6 (4)
C13—C1—C6a—C6165.7 (2)N31—C311—C316—C315179.5 (2)
N2—C1—C6a—C3a38.1 (2)C6—N5—C51—C56123.6 (3)
C11—C1—C6a—C3a155.8 (2)C4—N5—C51—C5653.6 (3)
C13—C1—C6a—C3a81.8 (2)C6—N5—C51—C5255.7 (3)
C4—C3a—C6a—C613.5 (2)C4—N5—C51—C52127.1 (2)
C3—C3a—C6a—C6105.5 (2)C56—C51—C52—C530.6 (4)
C4—C3a—C6a—C1132.1 (2)N5—C51—C52—C53179.9 (2)
C3—C3a—C6a—C113.1 (2)C51—C52—C53—C540.7 (4)
N2—C1—C11—O119.2 (3)C52—C53—C54—C550.1 (4)
C6a—C1—C11—O11119.8 (3)C52—C53—C54—Cl54178.49 (19)
C13—C1—C11—O11116.6 (3)C53—C54—C55—C560.5 (4)
N2—C1—C11—O12172.39 (18)Cl54—C54—C55—C56179.10 (19)
C6a—C1—C11—O1261.7 (3)C54—C55—C56—C510.5 (4)
C13—C1—C11—O1261.8 (3)C52—C51—C56—C550.0 (4)
O11—C11—O12—C124.5 (3)N5—C51—C56—C55179.3 (2)
C1—C11—O12—C12177.0 (2)
Hydrogen-bond geometry (Å, º) top
Cg1 represents the centroid of the C51–C56 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2···N32i0.882.543.413 (3)169
C3a—H3A···O11ii1.002.463.307 (3)142
C6a—H6A···Cl54iii1.002.783.416 (3)122
C55—H55···O6iii0.952.503.422 (3)165
C56—H56···Cg1iii0.952.843.611 (3)139
C314—H314···O4iv0.952.503.229 (3)134
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y1, z; (iii) x+3/2, y1/2, z+1/2; (iv) x+1, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC25H24N4O4C25H23ClN4O4
Mr444.48478.92
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/n
Temperature (K)120120
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)
V3)2224.4 (6)2267.1 (5)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.090.21
Crystal size (mm)0.39 × 0.35 × 0.290.42 × 0.25 × 0.18
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.965, 0.9740.917, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
32624, 5110, 3436 32234, 5200, 3101
Rint0.0500.085
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.136, 1.06 0.054, 0.114, 1.04
No. of reflections51105200
No. of parameters301311
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.300.27, 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).

Hydrogen-bond geometry (Å, º) for (I) top
Cg3 represents the centroid of the N31/N32/C33–C35 ring.
D—H···AD—HH···AD···AD—H···A
C6a—H6A···O6i1.002.503.418 (2)152
C54—H54···O12ii0.952.463.256 (3)141
C313—H313···O4iii0.952.513.303 (3)142
N2—H2···Cg3iv0.962.633.522 (2)156
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+3/2, z+1/2; (iii) x, y+3/2, z1/2; (iv) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
Cg1 represents the centroid of the C51–C56 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2···N32i0.882.543.413 (3)169
C3a—H3A···O11ii1.002.463.307 (3)142
C6a—H6A···Cl54iii1.002.783.416 (3)122
C55—H55···O6iii0.952.503.422 (3)165
C56—H56···Cg1iii0.952.843.611 (3)139
C314—H314···O4iv0.952.503.229 (3)134
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y1, z; (iii) x+3/2, y1/2, z+1/2; (iv) x+1, y+1, z+1.
Ring-puckering parameters (Å, °) for the fused five-membered rings in (I) and (II) top
(I)(II)
Q2ϕ2Q2ϕ2
Ring A0.435 (2)19.7 (3)0.470 (3)15.7 (3)
Ring B0.146 (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.
Selected bond distances (Å) and torsion angles (°) for (I) and (II) top
Parameter(I)(II)
N31—N321.363 (2)1.368 (3)
N32—C331.333 (2)1.333 (3)
C33—C341.415 (2)1.412 (3)
C34—C351.378 (3)1.373 (3)
C35—N311.359 (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—C12176.65 (15)-177.0 (2)
N2—C3—C34—C35-25.2 (2)-18.6 (3)
C35—N31—C311—C31211.1 (3)5.7 (4)
C4—N5—C51—C52105.5 (2)-127.1 (2)
 

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