Weak hy­dro­gen bonding in the structures of three double-acyl­ated amino­anti­pyrines

The structures of three doubly-acyl­ated 4-amino­anti­pyrine (AP) com­pounds where the aryl substituent is varied are reported and analysed in terms of their relative conformation, inter­molecular inter­actions and overall packing; these are N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)-4-methyl-N-[(4-methyl­phen­yl)carbon­yl]benzamide, C₂₇H₂₅N₃O₃, N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)-N-[(furan-2-yl)carbon­yl]furan-2-carbox­am­ide, C₂₁H₁₇N₃O₅, and N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-py­ra­zol-4-yl)-N-[(thio­phen-2-yl)carbon­yl]thio­phene-2-carboxamide, C₂₁H₁₇N₃O₃S₂. The com­pounds were crystallized using the encapsulated nanodroplet crystallization (ENaCt) protocol. Where previous singly-acyl­ated AP com­pounds pro­duced structures with obvious classical hy­dro­gen-bonding motifs, the doubly-acyl­ated derivatives lack classical donors and therefore exhibit weak C—H hy­dro­gen bonds and inter­actions involving the π-system. All three AP com­pounds form bifurcated C—H⋯O inter­actions having either dimer or chain motifs, with the other structure-directing inter­actions being dependant on the nature of the aryl substituent.

1. Introduction

The 4-amino­anti­pyrine (AP) moiety has been studied extensively due to its historic use as analgesic/anti-inflammatory medi­cation (Ampyrone), albeit with potentially serious side effects, with safer variants (e.g. Metamizole) typically involving modification of the pendant amino group (Brogden, 1986). Although APs are still of inter­est due to their biological activity (Kurdekar et al., 2012), more recently, pyrazolo­nes, such as AP, have been employed as N,O-bidentate directing groups, finding use in Ru-catalysed C(sp²)—H bond aryl­ation reactions (Al Mamari et al., 2021, 2024).

In addition, there have been a great many structural studies of com­pounds bearing the AP moiety (Singh et al., 2020; Erturk, 2020; Shankar et al., 2023), with analysis of the supra­molecular structure providing insights into their potential use in non-linear optics (Montalvo-González & Ariza-Castolo, 2003; Arumugam et al., 2023). These studies have often focused on AP derivatives with obvious strong hy­dro­gen bonding, where common motifs were identified, and some C—H⋯O, C—H⋯π and π–π inter­actions are also observed (Mnguni & Lemmerer, 2015; Narayana et al., 2016).

During the preparation of acyl­ated AP derivatives for use in directed Ru-catalyzed C—H aryl­ation chemistry (Al Mamari et al., 2021), over-acyl­ation of the pendant amino group was observed in a number of cases. This led to the formation of a set of double-acyl­ated APs (com­pounds 1–3; Scheme 1), con­taining para-toluoyl, 2-furoyl and 2-thenoyl groups, respectively, which are the focus of this study.

One consequence of this double acyl­ation is that, com­pared to where only a single acyl­ation occurs, the com­pounds lack classical hy­dro­gen-bond donors. As a result, without the formation of these rather obvious inter­actions, the packing is likely to be dominated by weak hy­dro­gen bonds incorporating C—H donor protons and/or inter­actions involving the π-systems of the aromatic substituents.

To com­plement previous studies into hy­dro­gen-bonding net­works in these com­pounds, this work looks into which inter­actions form in the absence of classical hy­dro­gen bonds and how this affects the packing in a series of related doubly-acyl­ated AP mol­ecules where the aryl substituent is varied.

2. Experimental

2.1. Synthesis

Double-acyl­ated AP derivatives were prepared through the reaction of 2.5–3.0 equivalents of the corresponding acyl chlo­ride with 4-amino­anti­pyrine, in the presence of an excess of Et₃N, in CH₂Cl₂ at 0 °C for 17 h. Following work-up and purification, all three com­pounds were obtained in reasonable yield (Scheme 1 shows the structures of the double-acyl­ated AP derivatives, with the AP core structure highlighted in red). Detailed synthetic protocols can be found in the supporting information.

2.2. Crystallization by ENaCt

Single crystals suitable for single-crystal X-ray diffraction (SCXRD) analysis were grown using a high-throughput solution-phase approach, known as encapsulated nanodroplet crystallization or ENaCt (Tyler et al., 2020; Metherall et al., 2023). ENaCt has been used successfully in the discovery of crystal forms of a wide range of small mol­ecules (Straker et al., 2023; Metherall et al., 2024), including recent applications in cocrystal and polymorph discovery (Metherall et al., 2025; Weatherston et al., 2025). Thus, near saturated solutions of com­pounds 1–3 were prepared, using 12 different solvents, through portionwise solvent addition to solid samples until dissolution was achieved. An SPT Labtech mosquito liquid handling robot was then used to dispense 50 nl droplets of these solutions into pre-dispensed 200 nl oil droplets, within a 96-well SWISSCI LCP glass plate. This resulted in 288 crystallization experiments per com­pound, with the combination of 12 solvents and four encapsulation oils (including no-oil conditions) resulting in 60 unique crystallization conditions. Plates were then sealed with a glass cover plate and crystallization monitored by cross-polarized optical microscopy. After 14 d, crystallization outcomes were recorded and suit­able single crystals retrieved for SCXRD analysis.

Compound 3 showed the highest levels of crystallinity in these experiments, with 31 from a total of 288 wells (11%) giving crystals likely suitable for SCXRD analysis. Next most crystalline was com­pound 1 (15 wells from 288, 5.2%), with com­pound 2 showing only 2 hits from the total screen (0.69%). Inter­estingly, all three com­pounds showed the best crystallization outcomes from ENaCt experiments using dimethyl sulfoxide (DMSO) as solvent, with only com­pound 3 showing significant `hits' outside of this solvent (Fig. 1).

Figure 1 Experimental ENaCt outcomes for each com­pound, showing the total number of crystals identified as suitable for SCXRD versus experimental conditions {solvent (a = DMSO, b = DMF, c = MeOH, d = TFE, e = toluene, f = DCE, g = 2-MeTHF, h = 1,4-dioxane, i = EtOAc, j = MeCN, k = MIBK and l = NM) and oil [no oil (dark blue), PDMSO (orange), FC-40 (grey), FY (yellow) and MO (light blue)]}.

2.3. SCXRD

Crystal data, data collection and structure refinement details for 1–3 are summarized in Table 1. All structures (Fig. 2) were solved using SHELXT (Sheldrick, 2015a) and refined by SHELXL (Sheldrick, 2015b) using the OLEX2 inter­face (Dolomanov et al., 2009). All non-H atoms were refined anisotropically and H atoms were positioned with idealized geometry. The displacement parameters of the H atoms were constrained using a riding model with U_iso(H) set to be an appropriate multiple of the U_eq value of the parent atom.

Table 1
Experimental details

For all structures: monoclinic, P2₁/c, Z = 4. Experiments were carried out at 150 K with Cu Kα radiation using a Rigaku XtaLAB Synergy single-source diffractometer with a HyPix-Arc 100 detector. The absorption correction was analytical (CrysAlis PRO; Rigaku OD, 2023). Intensities were corrected for absorption using a multifaceted crystal model created by indexing the faces of the crystal for which data were collected (Clark & Reid, 1995). H-atom parameters were constrained.

	1	2	3
Crystal data
Chemical formula	C27H25N3O3	C21H17N3O5	C21H17N3O3S2
Mr	439.50	391.38	423.49
a, b, c (Å)	6.2325 (3), 22.6949 (11), 16.6898 (6)	10.3627 (4), 18.8249 (8), 10.6795 (5)	19.4242 (8), 7.2670 (3), 15.0756 (6)
β (°)	100.739 (4)	116.126 (5)	111.415 (4)
V (Å^3)	2319.36 (18)	1870.46 (16)	1981.09 (15)
μ (mm^−1)	0.67	0.84	2.68
Crystal size (mm)	0.33 × 0.03 × 0.02	0.18 × 0.03 × 0.01	0.26 × 0.1 × 0.04
Data collection
Tmin, Tmax	0.892, 0.988	0.935, 0.991	0.652, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	22144, 4503, 3840	17540, 3685, 3280	19584, 3961, 3417
Rint	0.032	0.030	0.032
(sin θ/λ)max (Å^−1)	0.632	0.632	0.633
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.037, 0.100, 1.02	0.037, 0.091, 1.04	0.034, 0.091, 1.05
No. of reflections	4503	3685	3961
No. of parameters	303	265	337
No. of restraints	0	0	496
Δρmax, Δρmin (e Å^−3)	0.22, −0.20	0.26, −0.22	0.34, −0.30
Computer programs: CrysAlis PRO (Rigaku OD, 2023), SHELXT2018 (Sheldrick, 2015a), SHELXL2019/1 (Sheldrick 2015b), SHELXL2019 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).

Figure 2 The crystal structures of 1–3 (left to right), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.

3. Results and discussion

The three structures of the double-acyl­ated AP com­pounds, though differing only in the identity of the aryl R group of the acid chloride starting material and crystallizing in the same space group (P2₁/c), differed very starkly in terms of their conformation and packing. Each asymmetric unit comprises one molecule (Z′ = 1) and although the AP moiety is consistent across the three structures with respect to conformation, as only a slight variation in the angle of the phenyl group is observed, when the five-membered rings of all three molecules are overlayed, the difference in the conformation about the tertiary amine N atom between 1, 2 and 3 becomes apparent (Fig. 3).

Figure 3 Overlay of the crystal structures of 1–3.

In all three structures, the conformation can be described with respect to three torsion angles corresponding to three distinct degrees of freedom. Firstly, by the orientation of the substituents relative to the asymmetrically-substituted five-membered ring, represented qu­anti­tatively by the C3—C1—N1—C12 torsion angle, and secondly, by the torsion angles about the amide bonds (Table 2).

Table 2
Selected geometric parameters (°) for 1–3

	1	2	3
C3—C1—N1—C12	105.06 (14)	35.13 (17)	70.91 (18)
C1—N1—C12—O2	25.20 (17)	133.18 (13)	24.9 (2)
C1—N1—C17/20—O3/4	145.58 (13)	12.94 (19)	145.96 (14)

Considering the C3—C1—N1—C12 torsion angle, the greater the steric bulk of the substituent (tolyl > thio­phenyl > furan­yl) the greater the value of the torsion angle: 1 > 3 > 2. It is likely that this results from the minimization of steric inter­actions between the aforementioned substituent and the O1 atom and C11 methyl group of the AP moiety. In terms of the torsion angles about the amide bond, all three structures exhibit a similar pattern, with one acute and one obtuse angle. The values observed for 1 and 3 are essentially identical, whereas those of 2 are slightly shallower and are reversed relative to the other two structures, with the carbonyl group orientated in the opposite directions with respect to the AP moiety.

The variation in these torsion angles produces three very different conformations, which have a drastic effect on the packing in the structures, particularly in terms of the orientations of the aryl groups and the inter­actions between them.

The packing in the structure of 1 is unique among this group, as the mol­ecules crystallize as dimers formed of C—H⋯O hy­dro­gen bonds (Desiraju, 1991, 1996), where the two mol­ecules of the dimer are related by inversion symmetry (Fig. 4). The C—H⋯O inter­actions form as bifurcated hy­dro­gen bonds between the two methyl groups of the AP moiety and the carbonyl O atom of one of the aryl groups, with donor–acceptor distances of ca 3.3 Å (Table 3). As such, the structure is best described in terms of the packing of these dimer units.

Table 3
Selected inter­molecular distances (Å, °) for 1

Cg indicates a ring centroid.

	C—H	H⋯O	C⋯O	C—H⋯O
C10—H10B⋯O2^i	0.98	2.49	3.2995 (17)	140
C11—H11A⋯O2^ii	0.98	2.45	3.3128 (18)	146
	C—H	C⋯Cg	H⋯Cg	C—H⋯Cg
C5—H5phen­yl⋯Cgtol­yl^i	0.95	3.17	3.8154 (18)	127
C8—H8phen­yl⋯Cgtol­yl^ii	0.95	2.85	3.6723 (16)	146
Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 2, y − , −z + .

Figure 4 The weak hy­dro­gen-bonded dimer in the crystal structure of 1. Hydrogen bonds are denoted by dashed lines and H atoms of groups not involved in hy­dro­gen bonding have been omitted for clarity.

This bifurcated C—H⋯O hy­dro­gen-bond motif is apparent in approximately 20% of AP structures in the Cambridge Structural Database (CSD; 70 out of 340; Groom et al., 2016) and appears to be most prevalent among structures with no classical hy­dro­gen-bond donors (Montalvo-González & Ariza-Castolo, 2003; Singh et al., 2020).

In addition to the weak hy­dro­gen bonding, the tolyl rings of adjacent dimer units are observed to arrange themselves in a face-to-face orientation, but, as the centroid–centroid dis­tances are not within the accepted range for π–π inter­actions (Avasthi et al., 2014), the orientation of the rings is likely to be to minimize steric inter­actions.

The crystal structure of 1 is observed to form layers of dimer units coplanar to the crystallographic (001) plane (Fig. 5). Between the layers, there appear to be edge-to-face inter­actions (Nishio, 2004; Brunner et al., 2014) between the phenyl and tolyl groups (Table 3). These inter­actions link the dimer units to form a chain motif along the [02] direction and, when considered along with the slightly longer intra-dimer contacts of the same type, form a continuous chain of C—H⋯π contacts in this direction.

Figure 5 Views highlighting the layered structure (left) and the C—H⋯π hy­dro­gen-bonded chain (right) in the crystal structure of 1. Hydrogen bonds are denoted by dashed lines, ring centroids as grey spheres and H atoms have been omitted for clarity with the exception of those of the phenyl groups involved in C—H⋯π bonding.

The structure of 2 exhibits similar bifurcated C—H⋯O inter­actions to those observed for 1 (Table 4); however, in this case, instead of discrete dimers, these inter­actions form con­tinuous chains in the [001] direction, with each mol­ecule related to the next by the symmetry of the c-glide (Fig. 6). The formation of these chains is aided by inter­actions involving the furanyl group. This is observed in an additional C—H⋯O inter­action between a C—H hy­dro­gen-bond donor on the furanyl group and the carbonyl group of the AP moiety. The formation of this inter­action as a result of the introduction of the hy­dro­gen-bond-accepting furanyl group in contrast to the tolyl groups in 1 rationalizes both the formation of the chain and the mol­ecular conformation of 2 in the crystal structure.

Table 4
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O4^i	0.98	2.61	3.418 (2)	140
C11—H11A⋯O4^i	0.98	2.50	3.4478 (19)	163
C14—H14⋯O1^i	0.95	2.35	3.197 (2)	148
C15—H15⋯O3^i	0.95	2.64	3.318 (2)	129
C16—H16⋯O4^ii	0.95	2.38	3.2680 (17)	156
Symmetry codes: (i) ; (ii) .

Figure 6 The C—H⋯O hy­dro­gen-bonded chain in the crystal structure of 2. Hydrogen bonds are denoted by dashed lines and H atoms of groups not involved in hy­dro­gen bonding have been omitted for clarity.

There also appear to be C—H⋯O hy­dro­gen bonds of a similar distance between furanyl groups orientated along the [100] axis relative to the AP moiety that also extend along the length of the chain. Though the C—H⋯O hy­dro­gen-bond angle suggests that this inter­action is somewhat weaker than the Me⋯O inter­actions, it is still likely that it is having an effect on the orientations of the furanyl rings along the chain.

The phenyl and the other furanyl groups of the mol­ecule of 2 are orientated along the [010] direction relative to the AP moiety in an edge-to-face manner and, though one carbon–centroid distance is observed to be slightly below 4 Å, do not appear to form any salient inter­actions. It is likely that they are orientated to minimize steric inter­actions in much the same way as the tolyl and phenyl groups in the structure of 1.

This notion of minimizing steric inter­actions is also clear in the orientation of the rings between the chains, as they also tend to exhibit an edge-to-face arrangement but with no inter­molecular distances that would indicate attractive inter­actions. In the [100] direction, the chains are connected by further C—H⋯O inter­actions between the furanyl group and the amide carbonyl group involved in the inter­actions that propagate along the chain.

The crystal structure of 3 combines features of both 1 and 2. Like 1, it has a layered structure, yet also exhibits chains of mol­ecules reminiscent of those in 2 (Fig. 7) formed of bifurcated C—H⋯O hy­dro­gen-bond inter­actions, though in this case the two distances are more uneven than those observed for either 1 or 2 (Table 5). Along the chain, each consecutive mol­ecule is related by pure translation symmetry in the [010] direction and, beyond the ubiquitous C—H⋯O inter­actions, there are no other potentially structure-directing inter­actions in this direction.

Table 5
Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O1^i	0.98	2.71	3.600 (2)	151
C11—H11C⋯O1^i	0.98	2.39	3.281 (2)	150
Symmetry code: (i) .

Figure 7 The C—H⋯O hy­dro­gen-bonded chain in the crystal structure of 3. Hydrogen bonds are denoted by dashed lines and H atoms of groups not involved in hy­dro­gen bonding have been omitted for clarity.

The layers observed in this structure are best described as bilayers coplanar with the crystallographic (100) plane (Fig. 8). The thio­phene rings of the mol­ecules of 3 are directed towards the boundary of the bilayers in an edge-to-face arrangement across the inter­face. The disorder in these rings indicates that there are likely no strong inter­actions across the layer boundary. Inter­estingly, the structure of 3 is the only one studied herein where the phenyl and aryl groups do not form motifs in which these rings alternate. In addition to the thio­phenes being directed toward the layer boundaries, the phenyl rings form an edge-to-face herringbone arrangement in the centre of the bilayer, such that the thio­phene and phenyl rings do not come into contact with each other.

Figure 8 View highlighting the bilayers in the structure of 3. H atoms have been omitted for clarity.

4. Conclusion

The three double-acyl­ated AP mol­ecules reported in this study all lack classical hy­dro­gen-bond donors and as such their crystal packing is directed by weak hy­dro­gen bonds incorporating C—H donors. As these inter­actions are weak, minor structural variations can have drastic effects on the crystal structures and this can be observed in the conformation and packing as a result of the change in aryl group (tolyl, furanyl or thio­phen­yl).

All three structures exhibit the same bifurcated C—H⋯O inter­actions between the methyl groups of the AP moiety and an amide carbonyl, but the symmetry relationship between the mol­ecules involved in this inter­action is different in each case. The larger tolyl group in 1 leads to the formation of a layered structure of discrete dimers where the packing is dictated by the steric bulk of the tolyl group and the need for unfavourable inter­actions between them to be minimized. In contrast, the smaller furanyl group of 2 has extra hy­dro­gen-bond-acceptor functionality, forming a chain motif with additional inter­actions between the furanyl groups. The thio­phenyl ana­logue, 3, has an aryl group similar to the furanyl com­pound though slightly larger and with decreased hy­dro­gen-bond-acceptor ability. The result is a structure seemingly halfway between 1 and 2, with inter­mediate torsion angles and both layers and chain motifs, though these differ from those of the other analogues forming as bilayers and a chain formed solely of bifurcated C—H⋯O inter­actions.

The insights provided here should surely be of inter­est to crystal engineers or anyone working in a field where solid-state structure has been shown to be important. As a case study, these serendipitous products show the effects of varying the substituents on mol­ecules of this kind can have on the packing in the absence of truly structure-directing inter­actions and classical hy­dro­gen bonds.

Supporting information

Computing details

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-N-[(thiophen-2-yl)carbonyl]thiophene-2-carboxamide (3)

Crystal data

C21H17N3O3S2	F(000) = 880
Mr = 423.49	Dx = 1.420 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 19.4242 (8) Å	Cell parameters from 10875 reflections
b = 7.2670 (3) Å	θ = 2.4–77.1°
c = 15.0756 (6) Å	µ = 2.68 mm^−1
β = 111.415 (4)°	T = 150 K
V = 1981.09 (15) Å^3	Prism, colourless
Z = 4	0.26 × 0.1 × 0.04 mm

Data collection

Rigaku XtaLAB Synergy single-source diffractometer with a HyPix-Arc 100 detector	3961 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	3417 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 10.0000 pixels mm^-1	θmax = 77.5°, θmin = 2.4°
ω scans	h = −24→22
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −6→8
Tmin = 0.652, Tmax = 0.905	l = −17→19
19584 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.6804P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.091	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.34 e Å^−3
3961 reflections	Δρmin = −0.30 e Å^−3
337 parameters	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
496 restraints	Extinction coefficient: 0.00094 (16)
Primary atom site location: dual

Special details

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.

Refinement. Both thiophene groups in this structure have been modelled as disordered over two positions. The occupancies of the disordered sites were refined independently of the atomic displacement parameters. The geometry of the thiophene rings were restrained using the SADI card and the displacement parameters of all partially-occupied non- hydrogen atoms were restrained using the SIMU card.

Single-crystal diffraction on an XtaLAB Synergy HyPix-Arc 100 diffractometer using Cu Kα radiation (λ = 1.54184 Å). Data were collected at 150 K using an Oxford Cryosystems CryostreamPlus open-flow N₂ cooling device.

Intensities were corrected for absorption using a multifaceted crystal model created by indexing the faces of the crystal for which data were collected (Clark & Reid, 1995). Cell refinement, data collection and data reduction were undertaken via the software CrysAlis PRO (Rigaku OD, 2023).

All structures (Fig. 2) were solved using SHELXT (Sheldrick, 2015a) and refined by SHELXL (Sheldrick, 2015b) using the OLEX2 interface (Dolomanov et al., 2009). All non-H atoms were refined anisotropically and H atoms were positioned with idealized geometry. The displacement parameters of the H atoms were constrained using a riding model with U_iso(H) set to be an appropriate multiple of the U_eq value of the parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.71690 (6)	0.43033 (15)	0.61115 (8)	0.0369 (3)
O2	0.69520 (6)	0.5425 (3)	0.37082 (9)	0.0672 (5)
O3	0.88092 (6)	0.79242 (15)	0.47154 (8)	0.0356 (3)
N1	0.78265 (6)	0.67237 (17)	0.50084 (8)	0.0283 (3)
N2	0.64782 (6)	0.69201 (16)	0.61265 (8)	0.0274 (3)
N3	0.63802 (6)	0.86554 (16)	0.56889 (8)	0.0285 (3)
C1	0.72789 (7)	0.7207 (2)	0.53881 (10)	0.0266 (3)
C2	0.69059 (8)	0.8820 (2)	0.52847 (10)	0.0288 (3)
C3	0.70100 (7)	0.5924 (2)	0.59045 (10)	0.0270 (3)
C4	0.59031 (7)	0.6094 (2)	0.63590 (10)	0.0272 (3)
C5	0.51625 (8)	0.6477 (2)	0.58412 (10)	0.0312 (3)
H5	0.502967	0.737095	0.534730	0.037*
C6	0.46206 (8)	0.5539 (2)	0.60546 (11)	0.0374 (4)
H6	0.411412	0.581052	0.571149	0.045*
C7	0.48085 (9)	0.4219 (2)	0.67583 (13)	0.0421 (4)
H7	0.443357	0.356829	0.689252	0.051*
C8	0.55470 (10)	0.3845 (2)	0.72693 (13)	0.0434 (4)
H8	0.567795	0.292652	0.775093	0.052*
C9	0.60970 (9)	0.4803 (2)	0.70823 (11)	0.0352 (3)
H9	0.660303	0.457403	0.744859	0.042*
C10	0.61765 (9)	1.0160 (2)	0.61901 (11)	0.0360 (4)
H10A	0.564771	1.008405	0.607886	0.054*
H10B	0.628222	1.134107	0.595255	0.054*
H10C	0.646322	1.006362	0.687469	0.054*
C11	0.70133 (10)	1.0561 (2)	0.48355 (13)	0.0417 (4)
H11A	0.653351	1.101357	0.440078	0.063*
H11B	0.733728	1.033519	0.447827	0.063*
H11C	0.724005	1.148233	0.533113	0.063*
C12	0.75976 (8)	0.5504 (3)	0.42158 (11)	0.0373 (4)
C13	0.81439 (8)	0.4254 (2)	0.40971 (11)	0.0342 (3)
C17	0.84995 (8)	0.76774 (19)	0.52752 (10)	0.0271 (3)
C18	0.88195 (7)	0.83319 (19)	0.62656 (10)	0.0265 (3)
S1A	0.79162 (7)	0.3091 (2)	0.30402 (8)	0.0472 (3)	0.7849
S2A	0.94847 (9)	1.0003 (2)	0.65270 (11)	0.0324 (3)	0.628
C14A	0.8821 (4)	0.3666 (12)	0.4716 (5)	0.0537 (16)	0.7849
H14A	0.902684	0.411384	0.535046	0.064*	0.7849
C15A	0.9193 (2)	0.2385 (6)	0.4369 (3)	0.0414 (9)	0.7849
H15A	0.967544	0.191975	0.470637	0.050*	0.7849
C16A	0.8752 (2)	0.1909 (7)	0.3469 (3)	0.0416 (9)	0.7849
H16A	0.888803	0.100935	0.310567	0.050*	0.7849
C19A	0.8743 (4)	0.7642 (13)	0.7057 (5)	0.0408 (14)	0.628
H19A	0.841453	0.666550	0.704593	0.049*	0.628
C20A	0.9204 (6)	0.8527 (16)	0.7907 (7)	0.0326 (14)	0.628
H20A	0.920877	0.825506	0.852538	0.039*	0.628
C21A	0.9640 (6)	0.9822 (18)	0.7715 (5)	0.0316 (14)	0.628
H21A	0.999286	1.054610	0.819179	0.038*	0.628
S1B	0.8901 (4)	0.3733 (10)	0.4945 (5)	0.0502 (12)	0.2151
S2B	0.86117 (15)	0.7563 (5)	0.72158 (19)	0.0307 (4)	0.372
C14B	0.7973 (9)	0.314 (2)	0.3273 (9)	0.028 (3)	0.2151
H14B	0.750493	0.317309	0.276680	0.034*	0.2151
C15B	0.8521 (7)	0.204 (3)	0.3261 (12)	0.039 (3)	0.2151
H15B	0.856489	0.138971	0.273666	0.047*	0.2151
C16B	0.8996 (8)	0.207 (2)	0.4173 (12)	0.040 (3)	0.2151
H16B	0.938220	0.118751	0.439224	0.048*	0.2151
C19B	0.9379 (7)	0.9569 (16)	0.6568 (9)	0.041 (2)	0.372
H19B	0.956242	1.018708	0.614428	0.049*	0.372
C20B	0.9669 (11)	0.987 (3)	0.7562 (9)	0.036 (3)	0.372
H20B	1.006063	1.069194	0.788069	0.043*	0.372
C21B	0.9310 (10)	0.881 (3)	0.7999 (12)	0.032 (2)	0.372
H21B	0.943570	0.876546	0.867022	0.039*	0.372

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0360 (6)	0.0249 (6)	0.0558 (7)	0.0061 (4)	0.0239 (5)	0.0072 (5)
O2	0.0270 (6)	0.1190 (13)	0.0517 (8)	−0.0069 (7)	0.0098 (5)	−0.0390 (8)
O3	0.0422 (6)	0.0329 (6)	0.0395 (6)	−0.0091 (5)	0.0242 (5)	−0.0040 (5)
N1	0.0255 (6)	0.0298 (6)	0.0308 (6)	−0.0020 (5)	0.0119 (5)	−0.0028 (5)
N2	0.0261 (6)	0.0233 (6)	0.0342 (6)	0.0030 (5)	0.0126 (5)	0.0050 (5)
N3	0.0301 (6)	0.0222 (6)	0.0340 (6)	0.0042 (5)	0.0125 (5)	0.0029 (5)
C1	0.0236 (6)	0.0269 (7)	0.0284 (7)	−0.0005 (5)	0.0084 (5)	−0.0002 (6)
C2	0.0287 (7)	0.0282 (8)	0.0274 (7)	0.0001 (6)	0.0079 (5)	0.0008 (6)
C3	0.0225 (6)	0.0266 (7)	0.0322 (7)	0.0013 (5)	0.0102 (5)	0.0004 (6)
C4	0.0263 (7)	0.0263 (7)	0.0309 (7)	0.0005 (6)	0.0126 (5)	−0.0034 (6)
C5	0.0285 (7)	0.0330 (8)	0.0322 (7)	0.0017 (6)	0.0111 (6)	−0.0058 (6)
C6	0.0271 (7)	0.0448 (10)	0.0420 (8)	−0.0028 (7)	0.0145 (6)	−0.0150 (7)
C7	0.0407 (9)	0.0418 (10)	0.0540 (10)	−0.0104 (7)	0.0294 (8)	−0.0121 (8)
C8	0.0470 (9)	0.0391 (9)	0.0521 (10)	−0.0010 (8)	0.0276 (8)	0.0060 (8)
C9	0.0321 (8)	0.0351 (9)	0.0404 (8)	0.0028 (6)	0.0155 (6)	0.0051 (7)
C10	0.0444 (9)	0.0259 (8)	0.0402 (8)	0.0041 (7)	0.0184 (7)	−0.0016 (6)
C11	0.0520 (10)	0.0310 (9)	0.0484 (9)	0.0055 (7)	0.0258 (8)	0.0105 (7)
C12	0.0292 (7)	0.0490 (10)	0.0350 (8)	−0.0081 (7)	0.0132 (6)	−0.0112 (7)
C13	0.0365 (8)	0.0319 (8)	0.0383 (8)	−0.0113 (6)	0.0186 (6)	−0.0097 (6)
C17	0.0281 (7)	0.0221 (7)	0.0328 (7)	−0.0004 (6)	0.0131 (6)	0.0014 (6)
C18	0.0247 (6)	0.0235 (7)	0.0322 (7)	0.0013 (6)	0.0114 (5)	0.0019 (6)
S1A	0.0449 (5)	0.0549 (5)	0.0486 (6)	−0.0238 (4)	0.0251 (4)	−0.0302 (4)
S2A	0.0312 (5)	0.0311 (6)	0.0341 (4)	−0.0104 (4)	0.0110 (3)	−0.0037 (4)
C14A	0.072 (3)	0.042 (2)	0.053 (3)	−0.0056 (19)	0.031 (2)	−0.008 (2)
C15A	0.051 (2)	0.0287 (18)	0.0473 (19)	−0.0010 (15)	0.0208 (14)	−0.0012 (13)
C16A	0.051 (2)	0.0280 (15)	0.051 (2)	−0.0016 (17)	0.0248 (19)	−0.0073 (15)
C19A	0.033 (3)	0.041 (2)	0.046 (3)	0.0041 (18)	0.0121 (16)	−0.001 (2)
C20A	0.026 (3)	0.039 (4)	0.035 (3)	0.005 (2)	0.014 (2)	0.004 (2)
C21A	0.031 (3)	0.035 (3)	0.0259 (19)	0.0000 (19)	0.0076 (16)	−0.0039 (17)
S1B	0.059 (2)	0.0356 (19)	0.060 (3)	0.0193 (16)	0.0265 (18)	0.0031 (17)
S2B	0.0303 (9)	0.0307 (7)	0.0304 (8)	−0.0006 (7)	0.0103 (6)	0.0006 (6)
C14B	0.034 (5)	0.022 (5)	0.032 (5)	0.009 (4)	0.017 (4)	0.006 (3)
C15B	0.037 (6)	0.032 (5)	0.051 (6)	0.004 (4)	0.021 (5)	−0.009 (4)
C16B	0.053 (6)	0.018 (5)	0.052 (7)	−0.002 (5)	0.022 (5)	−0.004 (4)
C19B	0.038 (4)	0.046 (6)	0.043 (3)	−0.008 (3)	0.020 (3)	0.002 (3)
C20B	0.030 (3)	0.033 (4)	0.047 (5)	−0.007 (3)	0.017 (4)	−0.003 (4)
C21B	0.025 (4)	0.037 (5)	0.030 (3)	−0.003 (3)	0.004 (3)	−0.002 (3)

Geometric parameters (Å, º)

O1—C3	1.2283 (18)	C13—C14A	1.374 (8)
O2—C12	1.2085 (19)	C13—S1B	1.602 (6)
O3—C17	1.2153 (17)	C13—C14B	1.418 (12)
N1—C1	1.4237 (17)	C17—C18	1.471 (2)
N1—C12	1.4222 (19)	C18—S2A	1.7112 (18)
N1—C17	1.4026 (18)	C18—C19A	1.351 (6)
N2—N3	1.4036 (16)	C18—S2B	1.717 (3)
N2—C3	1.3987 (17)	C18—C19B	1.355 (9)
N2—C4	1.4201 (18)	S1A—C16A	1.739 (4)
N3—C2	1.3722 (18)	S2A—C21A	1.709 (7)
N3—C10	1.4636 (19)	C14A—H14A	0.9500
C1—C2	1.357 (2)	C14A—C15A	1.391 (8)
C1—C3	1.430 (2)	C15A—H15A	0.9500
C2—C11	1.485 (2)	C15A—C16A	1.359 (4)
C4—C5	1.391 (2)	C16A—H16A	0.9500
C4—C9	1.382 (2)	C19A—H19A	0.9500
C5—H5	0.9500	C19A—C20A	1.422 (10)
C5—C6	1.387 (2)	C20A—H20A	0.9500
C6—H6	0.9500	C20A—C21A	1.366 (8)
C6—C7	1.377 (3)	C21A—H21A	0.9500
C7—H7	0.9500	S1B—C16B	1.734 (14)
C7—C8	1.385 (2)	S2B—C21B	1.697 (13)
C8—H8	0.9500	C14B—H14B	0.9500
C8—C9	1.388 (2)	C14B—C15B	1.337 (15)
C9—H9	0.9500	C15B—H15B	0.9500
C10—H10A	0.9800	C15B—C16B	1.348 (14)
C10—H10B	0.9800	C16B—H16B	0.9500
C10—H10C	0.9800	C19B—H19B	0.9500
C11—H11A	0.9800	C19B—C20B	1.411 (15)
C11—H11B	0.9800	C20B—H20B	0.9500
C11—H11C	0.9800	C20B—C21B	1.362 (12)
C12—C13	1.457 (2)	C21B—H21B	0.9500
C13—S1A	1.7130 (18)
C12—N1—C1	116.18 (11)	C14A—C13—C12	132.1 (3)
C17—N1—C1	121.19 (12)	C14A—C13—S1A	109.6 (3)
C17—N1—C12	121.44 (11)	C14B—C13—C12	121.1 (6)
N3—N2—C4	120.78 (11)	C14B—C13—S1B	114.7 (6)
C3—N2—N3	109.75 (11)	O3—C17—N1	121.31 (13)
C3—N2—C4	123.82 (12)	O3—C17—C18	121.62 (13)
N2—N3—C10	116.39 (11)	N1—C17—C18	117.07 (12)
C2—N3—N2	106.96 (11)	C17—C18—S2A	117.84 (11)
C2—N3—C10	123.33 (12)	C17—C18—S2B	126.91 (15)
N1—C1—C3	122.22 (13)	C19A—C18—C17	129.3 (4)
C2—C1—N1	127.79 (13)	C19A—C18—S2A	112.2 (4)
C2—C1—C3	109.88 (12)	C19B—C18—C17	123.1 (5)
N3—C2—C11	121.86 (13)	C19B—C18—S2B	109.8 (5)
C1—C2—N3	109.06 (13)	C13—S1A—C16A	90.52 (18)
C1—C2—C11	129.08 (14)	C21A—S2A—C18	90.9 (4)
O1—C3—N2	125.07 (13)	C13—C14A—H14A	121.5
O1—C3—C1	130.95 (13)	C13—C14A—C15A	117.0 (6)
N2—C3—C1	103.96 (12)	C15A—C14A—H14A	121.5
C5—C4—N2	121.48 (13)	C14A—C15A—H15A	125.6
C9—C4—N2	117.98 (12)	C16A—C15A—C14A	108.7 (5)
C9—C4—C5	120.42 (14)	C16A—C15A—H15A	125.6
C4—C5—H5	120.4	S1A—C16A—H16A	123.0
C6—C5—C4	119.23 (15)	C15A—C16A—S1A	114.1 (3)
C6—C5—H5	120.4	C15A—C16A—H16A	123.0
C5—C6—H6	119.6	C18—C19A—H19A	123.5
C7—C6—C5	120.72 (15)	C18—C19A—C20A	113.0 (7)
C7—C6—H6	119.6	C20A—C19A—H19A	123.5
C6—C7—H7	120.2	C19A—C20A—H20A	124.6
C6—C7—C8	119.64 (15)	C21A—C20A—C19A	110.9 (8)
C8—C7—H7	120.2	C21A—C20A—H20A	124.6
C7—C8—H8	119.8	S2A—C21A—H21A	123.6
C7—C8—C9	120.42 (16)	C20A—C21A—S2A	112.9 (8)
C9—C8—H8	119.8	C20A—C21A—H21A	123.6
C4—C9—C8	119.51 (15)	C13—S1B—C16B	85.5 (6)
C4—C9—H9	120.2	C21B—S2B—C18	92.1 (6)
C8—C9—H9	120.2	C13—C14B—H14B	122.5
N3—C10—H10A	109.5	C15B—C14B—C13	114.9 (13)
N3—C10—H10B	109.5	C15B—C14B—H14B	122.5
N3—C10—H10C	109.5	C14B—C15B—H15B	128.4
H10A—C10—H10B	109.5	C14B—C15B—C16B	103.2 (14)
H10A—C10—H10C	109.5	C16B—C15B—H15B	128.4
H10B—C10—H10C	109.5	S1B—C16B—H16B	120.1
C2—C11—H11A	109.5	C15B—C16B—S1B	119.8 (12)
C2—C11—H11B	109.5	C15B—C16B—H16B	120.1
C2—C11—H11C	109.5	C18—C19B—H19B	122.6
H11A—C11—H11B	109.5	C18—C19B—C20B	114.8 (10)
H11A—C11—H11C	109.5	C20B—C19B—H19B	122.6
H11B—C11—H11C	109.5	C19B—C20B—H20B	124.7
O2—C12—N1	119.71 (14)	C21B—C20B—C19B	110.6 (15)
O2—C12—C13	121.76 (15)	C21B—C20B—H20B	124.7
N1—C12—C13	118.26 (13)	S2B—C21B—H21B	123.7
C12—C13—S1A	118.02 (12)	C20B—C21B—S2B	112.6 (14)
C12—C13—S1B	123.1 (3)	C20B—C21B—H21B	123.7
O2—C12—C13—S1A	17.6 (2)	C4—C5—C6—C7	−1.1 (2)
O2—C12—C13—C14A	−156.2 (6)	C5—C4—C9—C8	2.1 (2)
O2—C12—C13—S1B	−154.8 (4)	C5—C6—C7—C8	1.1 (2)
O2—C12—C13—C14B	12.6 (9)	C6—C7—C8—C9	0.6 (3)
O3—C17—C18—S2A	18.7 (2)	C7—C8—C9—C4	−2.2 (3)
O3—C17—C18—C19A	−151.2 (4)	C9—C4—C5—C6	−0.4 (2)
O3—C17—C18—S2B	−159.82 (18)	C10—N3—C2—C1	144.20 (14)
O3—C17—C18—C19B	14.7 (7)	C10—N3—C2—C11	−34.9 (2)
N1—C1—C2—N3	174.44 (13)	C12—N1—C1—C2	−104.82 (18)
N1—C1—C2—C11	−6.5 (3)	C12—N1—C1—C3	70.91 (18)
N1—C1—C3—O1	−0.2 (2)	C12—N1—C17—O3	21.1 (2)
N1—C1—C3—N2	−178.69 (12)	C12—N1—C17—C18	−157.80 (14)
N1—C12—C13—S1A	−168.46 (13)	C12—C13—S1A—C16A	−176.4 (2)
N1—C12—C13—C14A	17.7 (6)	C12—C13—C14A—C15A	177.5 (4)
N1—C12—C13—S1B	19.2 (5)	C12—C13—S1B—C16B	169.8 (7)
N1—C12—C13—C14B	−173.4 (9)	C12—C13—C14B—C15B	−179.1 (13)
N1—C17—C18—S2A	−162.42 (12)	C13—S1A—C16A—C15A	−0.9 (4)
N1—C17—C18—C19A	27.6 (5)	C13—C14A—C15A—C16A	−3.9 (9)
N1—C17—C18—S2B	19.0 (2)	C13—S1B—C16B—C15B	7.7 (16)
N1—C17—C18—C19B	−166.4 (7)	C13—C14B—C15B—C16B	15 (2)
N2—N3—C2—C1	5.02 (15)	C17—N1—C1—C2	62.8 (2)
N2—N3—C2—C11	−174.12 (13)	C17—N1—C1—C3	−121.44 (15)
N2—C4—C5—C6	175.55 (13)	C17—N1—C12—O2	−142.72 (17)
N2—C4—C9—C8	−174.05 (14)	C17—N1—C12—C13	43.2 (2)
N3—N2—C3—O1	−173.20 (14)	C17—C18—S2A—C21A	−173.5 (5)
N3—N2—C3—C1	5.38 (14)	C17—C18—C19A—C20A	173.3 (6)
N3—N2—C4—C5	28.2 (2)	C17—C18—S2B—C21B	171.8 (9)
N3—N2—C4—C9	−155.71 (13)	C17—C18—C19B—C20B	−173.0 (13)
C1—N1—C12—O2	24.9 (2)	C18—S2A—C21A—C20A	0.3 (10)
C1—N1—C12—C13	−149.19 (14)	C18—C19A—C20A—C21A	−2.6 (13)
C1—N1—C17—O3	−145.96 (14)	C18—S2B—C21B—C20B	3.5 (18)
C1—N1—C17—C18	35.19 (19)	C18—C19B—C20B—C21B	0 (2)
C2—C1—C3—O1	176.18 (15)	S1A—C13—C14A—C15A	3.3 (8)
C2—C1—C3—N2	−2.29 (15)	S2A—C18—C19A—C20A	2.9 (9)
C3—N2—N3—C2	−6.58 (15)	C14A—C13—S1A—C16A	−1.3 (5)
C3—N2—N3—C10	−149.02 (13)	C14A—C15A—C16A—S1A	2.7 (6)
C3—N2—C4—C5	−122.55 (15)	C19A—C18—S2A—C21A	−1.9 (6)
C3—N2—C4—C9	53.54 (19)	C19A—C20A—C21A—S2A	1.2 (14)
C3—C1—C2—N3	−1.71 (16)	S1B—C13—C14B—C15B	−10.8 (19)
C3—C1—C2—C11	177.35 (15)	S2B—C18—C19B—C20B	2.4 (16)
C4—N2—N3—C2	−161.03 (12)	C14B—C13—S1B—C16B	1.7 (12)
C4—N2—N3—C10	56.53 (17)	C14B—C15B—C16B—S1B	−14 (2)
C4—N2—C3—O1	−19.7 (2)	C19B—C18—S2B—C21B	−3.3 (11)
C4—N2—C3—C1	158.89 (12)	C19B—C20B—C21B—S2B	−3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O1^i	0.98	2.71	3.600 (2)	151
C11—H11C···O1^i	0.98	2.39	3.281 (2)	150

Symmetry code: (i) x, y−1, z.

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-methyl-N-[(4-methylphenyl)carbonyl]benzamide (1)

Crystal data

C27H25N3O3	F(000) = 928
Mr = 439.50	Dx = 1.259 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 6.2325 (3) Å	Cell parameters from 9606 reflections
b = 22.6949 (11) Å	θ = 3.3–74.3°
c = 16.6898 (6) Å	µ = 0.67 mm^−1
β = 100.739 (4)°	T = 150 K
V = 2319.36 (18) Å^3	Needle, colourless
Z = 4	0.33 × 0.03 × 0.02 mm

Data collection

Rigaku XtaLAB Synergy single-source diffractometer with a HyPix-Arc 100 detector	3840 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	Rint = 0.032
ω scans	θmax = 77.1°, θmin = 3.3°
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	h = −6→7
Tmin = 0.892, Tmax = 0.988	k = −27→26
22144 measured reflections	l = −20→19
4503 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.6691P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.22 e Å^−3
4503 reflections	Δρmin = −0.20 e Å^−3
303 parameters	Extinction correction: SHELXL2019/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00108 (19)
Primary atom site location: dual

Special details

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.

Refinement. Single-crystal diffraction on an XtaLAB Synergy HyPix-Arc 100 diffractometer using Cu Kα radiation (λ = 1.54184 Å). Data were collected at 150 K using an Oxford Cryosystems CryostreamPlus open-flow N₂ cooling device.

Intensities were corrected for absorption using a multifaceted crystal model created by indexing the faces of the crystal for which data were collected (Clark & Reid, 1995). Cell refinement, data collection and data reduction were undertaken via the software CrysAlis PRO (Rigaku OD, 2023).

All structures (Fig. 2) were solved using SHELXT (Sheldrick, 2015a) and refined by SHELXL (Sheldrick, 2015b) using the OLEX2 interface (Dolomanov et al., 2009). All non-H atoms were refined anisotropically and H atoms were positioned with idealized geometry. The displacement parameters of the H atoms were constrained using a riding model with U_iso(H) set to be an appropriate multiple of the U_eq value of the parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.99284 (14)	0.40653 (4)	0.71872 (6)	0.0328 (2)
O2	0.85692 (16)	0.55702 (4)	0.59817 (6)	0.0357 (2)
O3	0.93725 (16)	0.56167 (5)	0.82381 (6)	0.0374 (3)
N1	0.73124 (17)	0.52184 (5)	0.70938 (6)	0.0264 (2)
N2	0.49646 (16)	0.40116 (5)	0.58239 (6)	0.0258 (2)
N3	0.68542 (17)	0.37413 (5)	0.62710 (6)	0.0254 (2)
C1	0.6726 (2)	0.46692 (6)	0.67069 (7)	0.0253 (3)
C2	0.4889 (2)	0.45675 (6)	0.61461 (8)	0.0263 (3)
C3	0.8088 (2)	0.41530 (6)	0.67870 (7)	0.0251 (3)
C4	0.7662 (2)	0.32241 (6)	0.59503 (8)	0.0259 (3)
C5	0.7255 (2)	0.31167 (6)	0.51139 (8)	0.0311 (3)
H5	0.647619	0.339600	0.474649	0.037*
C6	0.8001 (2)	0.25974 (7)	0.48235 (10)	0.0389 (3)
H6	0.771130	0.251857	0.425450	0.047*
C7	0.9163 (2)	0.21926 (7)	0.53560 (11)	0.0424 (4)
H7	0.966375	0.183735	0.515237	0.051*
C8	0.9595 (2)	0.23066 (7)	0.61860 (10)	0.0401 (4)
H8	1.041004	0.203123	0.654993	0.048*
C9	0.8844 (2)	0.28202 (6)	0.64877 (9)	0.0320 (3)
H9	0.913263	0.289655	0.705739	0.038*
C10	0.2979 (2)	0.36450 (7)	0.56904 (8)	0.0317 (3)
H10A	0.330597	0.325945	0.547754	0.047*
H10B	0.183432	0.383932	0.529662	0.047*
H10C	0.247525	0.359246	0.620808	0.047*
C11	0.2969 (2)	0.49575 (7)	0.58879 (9)	0.0365 (3)
H11A	0.262446	0.497686	0.529111	0.055*
H11B	0.330388	0.535371	0.610955	0.055*
H11C	0.171112	0.479893	0.609277	0.055*
C12	0.7876 (2)	0.56820 (6)	0.65984 (8)	0.0271 (3)
C13	0.7341 (2)	0.62919 (6)	0.68089 (7)	0.0272 (3)
C14	0.5665 (2)	0.64186 (6)	0.72323 (8)	0.0309 (3)
H14	0.493052	0.610709	0.744929	0.037*
C15	0.5072 (2)	0.69978 (6)	0.73367 (8)	0.0336 (3)
H15	0.392435	0.707841	0.762394	0.040*
C16	0.6124 (2)	0.74645 (6)	0.70288 (8)	0.0328 (3)
C17	0.7806 (2)	0.73311 (6)	0.66106 (8)	0.0340 (3)
H17	0.855176	0.764248	0.639827	0.041*
C18	0.8404 (2)	0.67560 (6)	0.64998 (8)	0.0316 (3)
H18	0.954844	0.667575	0.621094	0.038*
C19	0.5459 (3)	0.80927 (7)	0.71280 (10)	0.0429 (4)
H19A	0.676631	0.833745	0.728053	0.064*
H19B	0.457683	0.811513	0.755567	0.064*
H19C	0.459878	0.823514	0.661235	0.064*
C20	0.7991 (2)	0.52582 (6)	0.79504 (8)	0.0280 (3)
C21	0.6907 (2)	0.48638 (6)	0.84630 (8)	0.0271 (3)
C22	0.4707 (2)	0.47136 (6)	0.82718 (8)	0.0308 (3)
H22	0.385098	0.483254	0.776592	0.037*
C23	0.3765 (2)	0.43903 (7)	0.88198 (9)	0.0340 (3)
H23	0.226055	0.429061	0.868373	0.041*
C24	0.4977 (2)	0.42081 (6)	0.95669 (9)	0.0331 (3)
C25	0.7175 (2)	0.43634 (6)	0.97558 (8)	0.0320 (3)
H25	0.802891	0.424607	1.026289	0.038*
C26	0.8127 (2)	0.46866 (6)	0.92128 (8)	0.0290 (3)
H26	0.962783	0.478937	0.935128	0.035*
C27	0.3955 (3)	0.38467 (8)	1.01547 (10)	0.0465 (4)
H27A	0.374264	0.344147	0.995282	0.070*
H27B	0.254073	0.401764	1.020256	0.070*
H27C	0.491842	0.384625	1.069067	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0278 (5)	0.0327 (5)	0.0342 (5)	0.0037 (4)	−0.0040 (4)	−0.0032 (4)
O2	0.0447 (6)	0.0339 (6)	0.0314 (5)	0.0058 (4)	0.0140 (4)	−0.0016 (4)
O3	0.0419 (6)	0.0362 (6)	0.0301 (5)	−0.0105 (5)	−0.0038 (4)	0.0003 (4)
N1	0.0312 (6)	0.0239 (6)	0.0231 (5)	0.0009 (4)	0.0023 (4)	−0.0020 (4)
N2	0.0219 (5)	0.0260 (6)	0.0278 (5)	0.0013 (4)	0.0001 (4)	−0.0016 (4)
N3	0.0239 (5)	0.0236 (6)	0.0272 (5)	0.0018 (4)	0.0008 (4)	−0.0014 (4)
C1	0.0281 (6)	0.0243 (7)	0.0232 (6)	0.0011 (5)	0.0040 (5)	−0.0016 (5)
C2	0.0260 (6)	0.0272 (7)	0.0257 (6)	0.0019 (5)	0.0050 (5)	−0.0009 (5)
C3	0.0256 (6)	0.0267 (7)	0.0227 (6)	−0.0008 (5)	0.0039 (5)	0.0005 (5)
C4	0.0224 (6)	0.0226 (6)	0.0332 (7)	−0.0031 (5)	0.0061 (5)	−0.0020 (5)
C5	0.0295 (7)	0.0314 (7)	0.0322 (7)	−0.0017 (6)	0.0048 (5)	−0.0025 (6)
C6	0.0355 (8)	0.0391 (8)	0.0429 (8)	−0.0023 (6)	0.0089 (6)	−0.0136 (7)
C7	0.0348 (8)	0.0303 (8)	0.0625 (10)	0.0013 (6)	0.0104 (7)	−0.0143 (7)
C8	0.0334 (7)	0.0271 (8)	0.0578 (9)	0.0042 (6)	0.0035 (7)	0.0017 (7)
C9	0.0296 (7)	0.0288 (7)	0.0366 (7)	−0.0008 (6)	0.0037 (5)	0.0008 (6)
C10	0.0253 (6)	0.0351 (8)	0.0332 (7)	−0.0044 (6)	0.0020 (5)	−0.0007 (6)
C11	0.0324 (7)	0.0345 (8)	0.0387 (8)	0.0077 (6)	−0.0038 (6)	−0.0063 (6)
C12	0.0256 (6)	0.0287 (7)	0.0256 (6)	0.0021 (5)	0.0012 (5)	−0.0006 (5)
C13	0.0300 (6)	0.0271 (7)	0.0233 (6)	0.0001 (5)	0.0024 (5)	−0.0011 (5)
C14	0.0358 (7)	0.0270 (7)	0.0306 (7)	−0.0008 (6)	0.0082 (5)	−0.0004 (6)
C15	0.0391 (7)	0.0301 (8)	0.0329 (7)	0.0018 (6)	0.0102 (6)	−0.0027 (6)
C16	0.0422 (8)	0.0275 (7)	0.0270 (6)	−0.0008 (6)	0.0023 (6)	−0.0028 (6)
C17	0.0439 (8)	0.0295 (7)	0.0286 (7)	−0.0073 (6)	0.0074 (6)	−0.0010 (6)
C18	0.0354 (7)	0.0329 (8)	0.0271 (6)	−0.0030 (6)	0.0076 (5)	−0.0013 (6)
C19	0.0584 (10)	0.0275 (8)	0.0427 (8)	−0.0001 (7)	0.0094 (7)	−0.0049 (7)
C20	0.0302 (7)	0.0266 (7)	0.0253 (6)	0.0019 (5)	0.0004 (5)	−0.0015 (5)
C21	0.0315 (7)	0.0243 (7)	0.0247 (6)	0.0017 (5)	0.0033 (5)	−0.0039 (5)
C22	0.0314 (7)	0.0319 (7)	0.0276 (6)	0.0032 (6)	0.0019 (5)	−0.0051 (6)
C23	0.0295 (7)	0.0352 (8)	0.0380 (7)	−0.0019 (6)	0.0081 (6)	−0.0092 (6)
C24	0.0402 (8)	0.0272 (7)	0.0342 (7)	−0.0020 (6)	0.0128 (6)	−0.0062 (6)
C25	0.0400 (7)	0.0286 (7)	0.0264 (6)	0.0015 (6)	0.0037 (5)	−0.0011 (6)
C26	0.0312 (7)	0.0283 (7)	0.0263 (6)	−0.0017 (6)	0.0020 (5)	−0.0043 (5)
C27	0.0525 (9)	0.0428 (9)	0.0482 (9)	−0.0078 (8)	0.0194 (7)	0.0008 (8)

Geometric parameters (Å, º)

O1—C3	1.2312 (15)	C12—C13	1.4814 (18)
O2—C12	1.2149 (16)	C13—C14	1.3956 (18)
O3—C20	1.2164 (16)	C13—C18	1.3934 (19)
N1—C1	1.4200 (17)	C14—H14	0.9500
N1—C12	1.4221 (17)	C14—C15	1.3853 (19)
N1—C20	1.4162 (16)	C15—H15	0.9500
N2—N3	1.4116 (14)	C15—C16	1.393 (2)
N2—C2	1.3758 (17)	C16—C17	1.396 (2)
N2—C10	1.4733 (17)	C16—C19	1.502 (2)
N3—C3	1.3997 (16)	C17—H17	0.9500
N3—C4	1.4206 (16)	C17—C18	1.379 (2)
C1—C2	1.3567 (18)	C18—H18	0.9500
C1—C3	1.4382 (18)	C19—H19A	0.9800
C2—C11	1.4864 (18)	C19—H19B	0.9800
C4—C5	1.3930 (19)	C19—H19C	0.9800
C4—C9	1.3932 (19)	C20—C21	1.4850 (19)
C5—H5	0.9500	C21—C22	1.3910 (19)
C5—C6	1.387 (2)	C21—C26	1.3970 (18)
C6—H6	0.9500	C22—H22	0.9500
C6—C7	1.385 (2)	C22—C23	1.385 (2)
C7—H7	0.9500	C23—H23	0.9500
C7—C8	1.385 (2)	C23—C24	1.395 (2)
C8—H8	0.9500	C24—C25	1.392 (2)
C8—C9	1.386 (2)	C24—C27	1.508 (2)
C9—H9	0.9500	C25—H25	0.9500
C10—H10A	0.9800	C25—C26	1.383 (2)
C10—H10B	0.9800	C26—H26	0.9500
C10—H10C	0.9800	C27—H27A	0.9800
C11—H11A	0.9800	C27—H27B	0.9800
C11—H11B	0.9800	C27—H27C	0.9800
C11—H11C	0.9800
C1—N1—C12	117.09 (10)	C14—C13—C12	122.37 (12)
C20—N1—C1	121.22 (11)	C18—C13—C12	118.35 (12)
C20—N1—C12	118.70 (11)	C18—C13—C14	118.95 (13)
N3—N2—C10	115.42 (10)	C13—C14—H14	119.9
C2—N2—N3	106.13 (9)	C15—C14—C13	120.11 (13)
C2—N2—C10	119.21 (10)	C15—C14—H14	119.9
N2—N3—C4	118.63 (10)	C14—C15—H15	119.3
C3—N3—N2	110.11 (10)	C14—C15—C16	121.32 (13)
C3—N3—C4	126.21 (10)	C16—C15—H15	119.3
N1—C1—C3	125.12 (11)	C15—C16—C17	117.92 (13)
C2—C1—N1	125.14 (12)	C15—C16—C19	121.48 (13)
C2—C1—C3	109.47 (11)	C17—C16—C19	120.59 (13)
N2—C2—C11	121.13 (11)	C16—C17—H17	119.4
C1—C2—N2	109.86 (11)	C18—C17—C16	121.26 (13)
C1—C2—C11	128.99 (13)	C18—C17—H17	119.4
O1—C3—N3	125.13 (12)	C13—C18—H18	119.8
O1—C3—C1	131.00 (12)	C17—C18—C13	120.43 (13)
N3—C3—C1	103.85 (10)	C17—C18—H18	119.8
C5—C4—N3	120.74 (12)	C16—C19—H19A	109.5
C5—C4—C9	120.38 (12)	C16—C19—H19B	109.5
C9—C4—N3	118.87 (12)	C16—C19—H19C	109.5
C4—C5—H5	120.4	H19A—C19—H19B	109.5
C6—C5—C4	119.25 (13)	H19A—C19—H19C	109.5
C6—C5—H5	120.4	H19B—C19—H19C	109.5
C5—C6—H6	119.7	O3—C20—N1	119.83 (12)
C7—C6—C5	120.57 (14)	O3—C20—C21	122.71 (12)
C7—C6—H6	119.7	N1—C20—C21	117.44 (11)
C6—C7—H7	120.0	C22—C21—C20	123.40 (12)
C6—C7—C8	119.92 (14)	C22—C21—C26	118.92 (12)
C8—C7—H7	120.0	C26—C21—C20	117.35 (12)
C7—C8—H8	119.8	C21—C22—H22	120.0
C9—C8—C7	120.31 (14)	C23—C22—C21	119.95 (13)
C9—C8—H8	119.8	C23—C22—H22	120.0
C4—C9—H9	120.2	C22—C23—H23	119.3
C8—C9—C4	119.56 (13)	C22—C23—C24	121.43 (13)
C8—C9—H9	120.2	C24—C23—H23	119.3
N2—C10—H10A	109.5	C23—C24—C27	121.24 (14)
N2—C10—H10B	109.5	C25—C24—C23	118.27 (13)
N2—C10—H10C	109.5	C25—C24—C27	120.49 (14)
H10A—C10—H10B	109.5	C24—C25—H25	119.7
H10A—C10—H10C	109.5	C26—C25—C24	120.66 (13)
H10B—C10—H10C	109.5	C26—C25—H25	119.7
C2—C11—H11A	109.5	C21—C26—H26	119.6
C2—C11—H11B	109.5	C25—C26—C21	120.77 (13)
C2—C11—H11C	109.5	C25—C26—H26	119.6
H11A—C11—H11B	109.5	C24—C27—H27A	109.5
H11A—C11—H11C	109.5	C24—C27—H27B	109.5
H11B—C11—H11C	109.5	C24—C27—H27C	109.5
O2—C12—N1	120.23 (12)	H27A—C27—H27B	109.5
O2—C12—C13	121.83 (12)	H27A—C27—H27C	109.5
N1—C12—C13	117.54 (11)	H27B—C27—H27C	109.5
O2—C12—C13—C14	147.82 (13)	C5—C6—C7—C8	−0.2 (2)
O2—C12—C13—C18	−25.50 (19)	C6—C7—C8—C9	0.9 (2)
O3—C20—C21—C22	141.79 (14)	C7—C8—C9—C4	−0.4 (2)
O3—C20—C21—C26	−31.62 (19)	C9—C4—C5—C6	1.3 (2)
N1—C1—C2—N2	172.56 (11)	C10—N2—N3—C3	−142.42 (11)
N1—C1—C2—C11	−8.9 (2)	C10—N2—N3—C4	61.15 (14)
N1—C1—C3—O1	1.2 (2)	C10—N2—C2—C1	138.18 (12)
N1—C1—C3—N3	−177.44 (11)	C10—N2—C2—C11	−40.47 (18)
N1—C12—C13—C14	−24.98 (18)	C12—N1—C1—C2	−68.30 (17)
N1—C12—C13—C18	161.71 (11)	C12—N1—C1—C3	105.06 (14)
N1—C20—C21—C22	−36.31 (18)	C12—N1—C20—O3	−14.28 (18)
N1—C20—C21—C26	150.28 (12)	C12—N1—C20—C21	163.88 (11)
N2—N3—C3—O1	−171.90 (12)	C12—C13—C14—C15	−172.93 (12)
N2—N3—C3—C1	6.84 (13)	C12—C13—C18—C17	173.49 (12)
N2—N3—C4—C5	26.23 (17)	C13—C14—C15—C16	−0.3 (2)
N2—N3—C4—C9	−152.82 (12)	C14—C13—C18—C17	−0.1 (2)
N3—N2—C2—C1	5.84 (14)	C14—C15—C16—C17	−0.1 (2)
N3—N2—C2—C11	−172.82 (12)	C14—C15—C16—C19	178.91 (14)
N3—C4—C5—C6	−177.70 (12)	C15—C16—C17—C18	0.4 (2)
N3—C4—C9—C8	178.37 (12)	C16—C17—C18—C13	−0.3 (2)
C1—N1—C12—O2	−25.20 (17)	C18—C13—C14—C15	0.3 (2)
C1—N1—C12—C13	147.71 (11)	C19—C16—C17—C18	−178.63 (13)
C1—N1—C20—O3	145.58 (13)	C20—N1—C1—C2	131.54 (14)
C1—N1—C20—C21	−36.26 (17)	C20—N1—C1—C3	−55.11 (17)
C2—N2—N3—C3	−8.01 (13)	C20—N1—C12—O2	135.48 (13)
C2—N2—N3—C4	−164.43 (11)	C20—N1—C12—C13	−51.60 (16)
C2—C1—C3—O1	175.44 (13)	C20—C21—C22—C23	−173.68 (13)
C2—C1—C3—N3	−3.20 (14)	C20—C21—C26—C25	174.18 (12)
C3—N3—C4—C5	−126.03 (14)	C21—C22—C23—C24	−0.1 (2)
C3—N3—C4—C9	54.91 (17)	C22—C21—C26—C25	0.5 (2)
C3—C1—C2—N2	−1.67 (15)	C22—C23—C24—C25	0.5 (2)
C3—C1—C2—C11	176.84 (13)	C22—C23—C24—C27	−178.85 (14)
C4—N3—C3—O1	−17.7 (2)	C23—C24—C25—C26	−0.4 (2)
C4—N3—C3—C1	161.05 (11)	C24—C25—C26—C21	−0.1 (2)
C4—C5—C6—C7	−0.9 (2)	C26—C21—C22—C23	−0.4 (2)
C5—C4—C9—C8	−0.7 (2)	C27—C24—C25—C26	178.95 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O2^i	0.98	2.49	3.2995 (17)	140
C11—H11A···O2^i	0.98	2.45	3.3128 (18)	146

Symmetry code: (i) −x+1, −y+1, −z+1.

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-N-[(furan-2-yl)carbonyl]furan-2-carboxamide (2)

Crystal data

C21H17N3O5	F(000) = 816
Mr = 391.38	Dx = 1.390 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.3627 (4) Å	Cell parameters from 8707 reflections
b = 18.8249 (8) Å	θ = 4.7–76.1°
c = 10.6795 (5) Å	µ = 0.84 mm^−1
β = 116.126 (5)°	T = 150 K
V = 1870.46 (16) Å^3	Needle, colourless
Z = 4	0.18 × 0.03 × 0.01 mm

Data collection

Rigaku XtaLAB Synergy single-source diffractometer with a HyPix-Arc 100 detector	3685 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	3280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 10.0000 pixels mm^-1	θmax = 77.1°, θmin = 4.7°
ω scans	h = −13→12
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2023)	k = −21→22
Tmin = 0.935, Tmax = 0.991	l = −8→13
17540 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.7212P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.091	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.26 e Å^−3
3685 reflections	Δρmin = −0.22 e Å^−3
265 parameters	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00067 (16)
Primary atom site location: dual

Special details

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.

Refinement. Single-crystal diffraction on an XtaLAB Synergy HyPix-Arc 100 diffractometer using Cu Kα radiation (λ = 1.54184 Å). Data were collected at 150 K using an Oxford Cryosystems CryostreamPlus open-flow N₂ cooling device.

Intensities were corrected for absorption using a multifaceted crystal model created by indexing the faces of the crystal for which data were collected (Clark & Reid, 1995). Cell refinement, data collection and data reduction were undertaken via the software CrysAlis PRO (Rigaku OD, 2023).

All structures (Fig. 2) were solved using SHELXT (Sheldrick, 2015a) and refined by SHELXL (Sheldrick, 2015b) using the OLEX2 interface (Dolomanov et al., 2009). All non-H atoms were refined anisotropically and H atoms were positioned with idealized geometry. The displacement parameters of the H atoms were constrained using a riding model with U_iso(H) set to be an appropriate multiple of the U_eq value of the parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.66606 (10)	0.31953 (5)	0.62504 (10)	0.0278 (2)
O2	0.58231 (10)	0.13920 (5)	0.59737 (10)	0.0294 (2)
O3	0.36640 (9)	0.22430 (5)	0.40707 (10)	0.0282 (2)
O4	0.97932 (10)	0.14956 (5)	0.66191 (10)	0.0286 (2)
O5	0.68200 (10)	0.03980 (5)	0.46445 (11)	0.0339 (3)
N1	0.74665 (11)	0.18432 (6)	0.52712 (11)	0.0218 (2)
N2	0.88099 (11)	0.34916 (6)	0.45588 (12)	0.0228 (2)
N3	0.80906 (12)	0.37305 (6)	0.53370 (12)	0.0242 (2)
C1	0.79055 (13)	0.25458 (7)	0.51516 (13)	0.0211 (3)
C2	0.87458 (13)	0.27588 (7)	0.45470 (13)	0.0209 (3)
C3	0.74533 (13)	0.31554 (7)	0.56718 (14)	0.0222 (3)
C4	0.74926 (13)	0.44320 (7)	0.50941 (15)	0.0242 (3)
C5	0.70393 (14)	0.47511 (8)	0.37987 (15)	0.0286 (3)
H5	0.714138	0.451237	0.306359	0.034*
C6	0.64330 (15)	0.54259 (8)	0.35917 (17)	0.0335 (3)
H6	0.612810	0.565109	0.271093	0.040*
C7	0.62694 (16)	0.57723 (8)	0.46549 (18)	0.0362 (4)
H7	0.585103	0.623240	0.450423	0.043*
C8	0.67189 (16)	0.54449 (8)	0.59414 (18)	0.0353 (4)
H8	0.660426	0.568142	0.667179	0.042*
C9	0.73364 (15)	0.47727 (8)	0.61703 (16)	0.0295 (3)
H9	0.764765	0.454953	0.705362	0.035*
C10	1.01834 (14)	0.38511 (8)	0.49092 (16)	0.0300 (3)
H10A	1.002792	0.436567	0.481027	0.045*
H10B	1.057934	0.368853	0.427774	0.045*
H10C	1.085987	0.373919	0.587335	0.045*
C11	0.95668 (14)	0.23252 (7)	0.39848 (14)	0.0256 (3)
H11A	0.958775	0.256891	0.318310	0.038*
H11B	0.910341	0.186092	0.369030	0.038*
H11C	1.055166	0.225933	0.470966	0.038*
C12	0.60446 (13)	0.17527 (7)	0.51521 (14)	0.0226 (3)
C13	0.49305 (13)	0.21330 (7)	0.39848 (14)	0.0223 (3)
C14	0.48585 (14)	0.24152 (8)	0.27906 (14)	0.0262 (3)
H14	0.558894	0.240661	0.248132	0.031*
C15	0.34736 (15)	0.27270 (8)	0.20912 (15)	0.0310 (3)
H15	0.309492	0.296917	0.122203	0.037*
C16	0.28058 (15)	0.26118 (8)	0.29015 (15)	0.0309 (3)
H16	0.185919	0.276717	0.268748	0.037*
C17	0.85389 (13)	0.13298 (7)	0.59418 (14)	0.0230 (3)
C18	0.81092 (14)	0.05837 (7)	0.57132 (14)	0.0261 (3)
C19	0.88151 (18)	−0.00019 (8)	0.64181 (17)	0.0371 (4)
H19	0.973669	−0.001818	0.719385	0.044*
C20	0.7901 (2)	−0.05864 (9)	0.57646 (19)	0.0451 (4)
H20	0.808666	−0.107194	0.602480	0.054*
C21	0.67257 (18)	−0.03212 (8)	0.47101 (19)	0.0406 (4)
H21	0.593371	−0.059735	0.409181	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0292 (5)	0.0236 (5)	0.0369 (5)	0.0010 (4)	0.0204 (4)	0.0014 (4)
O2	0.0280 (5)	0.0263 (5)	0.0366 (5)	−0.0008 (4)	0.0165 (4)	0.0078 (4)
O3	0.0211 (4)	0.0328 (6)	0.0329 (5)	0.0040 (4)	0.0140 (4)	0.0056 (4)
O4	0.0203 (5)	0.0240 (5)	0.0353 (5)	−0.0012 (4)	0.0066 (4)	−0.0008 (4)
O5	0.0273 (5)	0.0216 (5)	0.0442 (6)	−0.0048 (4)	0.0079 (4)	−0.0047 (4)
N1	0.0193 (5)	0.0159 (6)	0.0291 (6)	−0.0012 (4)	0.0096 (4)	0.0016 (4)
N2	0.0216 (5)	0.0177 (6)	0.0320 (6)	−0.0025 (4)	0.0145 (5)	−0.0013 (5)
N3	0.0258 (5)	0.0170 (6)	0.0344 (6)	−0.0007 (4)	0.0175 (5)	−0.0008 (5)
C1	0.0184 (6)	0.0162 (6)	0.0265 (6)	−0.0005 (5)	0.0079 (5)	0.0004 (5)
C2	0.0178 (6)	0.0195 (7)	0.0230 (6)	−0.0004 (5)	0.0067 (5)	−0.0003 (5)
C3	0.0195 (6)	0.0190 (7)	0.0266 (6)	−0.0013 (5)	0.0088 (5)	0.0010 (5)
C4	0.0201 (6)	0.0169 (7)	0.0350 (7)	−0.0037 (5)	0.0117 (5)	−0.0024 (5)
C5	0.0271 (7)	0.0233 (7)	0.0338 (7)	−0.0024 (5)	0.0119 (6)	−0.0018 (6)
C6	0.0270 (7)	0.0252 (8)	0.0429 (8)	−0.0004 (6)	0.0103 (6)	0.0054 (6)
C7	0.0279 (7)	0.0199 (7)	0.0608 (10)	0.0013 (6)	0.0196 (7)	0.0004 (7)
C8	0.0364 (8)	0.0232 (8)	0.0524 (9)	−0.0028 (6)	0.0252 (7)	−0.0086 (7)
C9	0.0308 (7)	0.0232 (7)	0.0364 (8)	−0.0024 (6)	0.0166 (6)	−0.0028 (6)
C10	0.0249 (7)	0.0257 (7)	0.0422 (8)	−0.0077 (6)	0.0172 (6)	−0.0030 (6)
C11	0.0233 (6)	0.0240 (7)	0.0302 (7)	0.0011 (5)	0.0125 (5)	−0.0007 (6)
C12	0.0218 (6)	0.0179 (6)	0.0291 (7)	−0.0024 (5)	0.0121 (5)	−0.0017 (5)
C13	0.0182 (6)	0.0198 (7)	0.0298 (7)	−0.0014 (5)	0.0114 (5)	−0.0027 (5)
C14	0.0230 (6)	0.0296 (7)	0.0268 (7)	−0.0015 (5)	0.0116 (5)	−0.0020 (6)
C15	0.0262 (7)	0.0351 (8)	0.0272 (7)	0.0033 (6)	0.0077 (6)	0.0042 (6)
C16	0.0215 (6)	0.0342 (8)	0.0348 (8)	0.0070 (6)	0.0103 (6)	0.0044 (6)
C17	0.0212 (6)	0.0204 (7)	0.0265 (6)	0.0006 (5)	0.0098 (5)	0.0005 (5)
C18	0.0226 (6)	0.0215 (7)	0.0326 (7)	−0.0007 (5)	0.0107 (5)	−0.0006 (6)
C19	0.0404 (8)	0.0227 (8)	0.0425 (9)	0.0050 (6)	0.0131 (7)	0.0014 (7)
C20	0.0604 (11)	0.0178 (8)	0.0581 (11)	−0.0012 (7)	0.0270 (9)	0.0000 (7)
C21	0.0437 (9)	0.0221 (8)	0.0593 (10)	−0.0126 (7)	0.0257 (8)	−0.0112 (7)

Geometric parameters (Å, º)

O1—C3	1.2285 (16)	C7—C8	1.386 (2)
O2—C12	1.2087 (16)	C8—H8	0.9500
O3—C13	1.3711 (15)	C8—C9	1.390 (2)
O3—C16	1.3616 (17)	C9—H9	0.9500
O4—C17	1.2174 (16)	C10—H10A	0.9800
O5—C18	1.3662 (16)	C10—H10B	0.9800
O5—C21	1.3614 (18)	C10—H10C	0.9800
N1—C1	1.4225 (16)	C11—H11A	0.9800
N1—C12	1.4323 (16)	C11—H11B	0.9800
N1—C17	1.4075 (17)	C11—H11C	0.9800
N2—N3	1.4122 (15)	C12—C13	1.4601 (19)
N2—C2	1.3809 (17)	C13—C14	1.3529 (19)
N2—C10	1.4680 (16)	C14—H14	0.9500
N3—C3	1.3943 (17)	C14—C15	1.4206 (19)
N3—C4	1.4331 (17)	C15—H15	0.9500
C1—C2	1.3532 (18)	C15—C16	1.343 (2)
C1—C3	1.4404 (18)	C16—H16	0.9500
C2—C11	1.4833 (18)	C17—C18	1.4611 (19)
C4—C5	1.387 (2)	C18—C19	1.353 (2)
C4—C9	1.386 (2)	C19—H19	0.9500
C5—H5	0.9500	C19—C20	1.419 (2)
C5—C6	1.391 (2)	C20—H20	0.9500
C6—H6	0.9500	C20—C21	1.339 (3)
C6—C7	1.383 (2)	C21—H21	0.9500
C7—H7	0.9500
C16—O3—C13	105.88 (10)	N2—C10—H10C	109.5
C21—O5—C18	106.10 (12)	H10A—C10—H10B	109.5
C1—N1—C12	117.37 (10)	H10A—C10—H10C	109.5
C17—N1—C1	118.17 (10)	H10B—C10—H10C	109.5
C17—N1—C12	120.96 (11)	C2—C11—H11A	109.5
N3—N2—C10	114.01 (11)	C2—C11—H11B	109.5
C2—N2—N3	106.73 (10)	C2—C11—H11C	109.5
C2—N2—C10	120.02 (11)	H11A—C11—H11B	109.5
N2—N3—C4	119.03 (11)	H11A—C11—H11C	109.5
C3—N3—N2	109.63 (10)	H11B—C11—H11C	109.5
C3—N3—C4	123.10 (10)	O2—C12—N1	121.27 (12)
N1—C1—C3	122.34 (11)	O2—C12—C13	124.32 (12)
C2—C1—N1	128.08 (12)	N1—C12—C13	114.41 (11)
C2—C1—C3	109.57 (11)	O3—C13—C12	115.92 (11)
N2—C2—C11	121.30 (11)	C14—C13—O3	110.28 (11)
C1—C2—N2	109.28 (11)	C14—C13—C12	133.79 (12)
C1—C2—C11	129.37 (12)	C13—C14—H14	126.8
O1—C3—N3	125.35 (12)	C13—C14—C15	106.35 (12)
O1—C3—C1	130.24 (12)	C15—C14—H14	126.8
N3—C3—C1	104.38 (11)	C14—C15—H15	126.8
C5—C4—N3	120.61 (12)	C16—C15—C14	106.41 (12)
C9—C4—N3	118.38 (13)	C16—C15—H15	126.8
C9—C4—C5	120.98 (13)	O3—C16—H16	124.5
C4—C5—H5	120.5	C15—C16—O3	111.08 (12)
C4—C5—C6	119.01 (14)	C15—C16—H16	124.5
C6—C5—H5	120.5	O4—C17—N1	121.56 (12)
C5—C6—H6	119.7	O4—C17—C18	120.86 (12)
C7—C6—C5	120.68 (15)	N1—C17—C18	117.44 (11)
C7—C6—H6	119.7	O5—C18—C17	119.96 (12)
C6—C7—H7	120.2	C19—C18—O5	110.27 (13)
C6—C7—C8	119.66 (14)	C19—C18—C17	129.76 (13)
C8—C7—H7	120.2	C18—C19—H19	126.9
C7—C8—H8	119.8	C18—C19—C20	106.12 (15)
C7—C8—C9	120.46 (14)	C20—C19—H19	126.9
C9—C8—H8	119.8	C19—C20—H20	126.6
C4—C9—C8	119.21 (14)	C21—C20—C19	106.71 (15)
C4—C9—H9	120.4	C21—C20—H20	126.6
C8—C9—H9	120.4	O5—C21—H21	124.6
N2—C10—H10A	109.5	C20—C21—O5	110.78 (14)
N2—C10—H10B	109.5	C20—C21—H21	124.6
O2—C12—C13—O3	18.7 (2)	C3—C1—C2—C11	173.76 (13)
O2—C12—C13—C14	−161.51 (15)	C4—N3—C3—O1	−26.2 (2)
O3—C13—C14—C15	0.61 (16)	C4—N3—C3—C1	152.07 (12)
O4—C17—C18—O5	−160.53 (13)	C4—C5—C6—C7	−0.6 (2)
O4—C17—C18—C19	19.0 (2)	C5—C4—C9—C8	−0.2 (2)
O5—C18—C19—C20	−1.02 (18)	C5—C6—C7—C8	0.2 (2)
N1—C1—C2—N2	175.15 (12)	C6—C7—C8—C9	0.2 (2)
N1—C1—C2—C11	−7.4 (2)	C7—C8—C9—C4	−0.2 (2)
N1—C1—C3—O1	−1.0 (2)	C9—C4—C5—C6	0.6 (2)
N1—C1—C3—N3	−179.23 (11)	C10—N2—N3—C3	−141.31 (12)
N1—C12—C13—O3	−160.73 (11)	C10—N2—N3—C4	69.27 (15)
N1—C12—C13—C14	19.0 (2)	C10—N2—C2—C1	137.78 (12)
N1—C17—C18—O5	15.18 (19)	C10—N2—C2—C11	−39.90 (18)
N1—C17—C18—C19	−165.26 (15)	C12—N1—C1—C2	−143.56 (13)
N2—N3—C3—O1	−174.17 (12)	C12—N1—C1—C3	35.13 (17)
N2—N3—C3—C1	4.13 (14)	C12—N1—C17—O4	−145.41 (13)
N2—N3—C4—C5	28.47 (17)	C12—N1—C17—C18	38.92 (17)
N2—N3—C4—C9	−153.61 (12)	C12—C13—C14—C15	−179.16 (15)
N3—N2—C2—C1	6.14 (14)	C13—O3—C16—C15	0.76 (17)
N3—N2—C2—C11	−171.54 (11)	C13—C14—C15—C16	−0.14 (17)
N3—C4—C5—C6	178.49 (12)	C14—C15—C16—O3	−0.39 (18)
N3—C4—C9—C8	−178.10 (12)	C16—O3—C13—C12	178.98 (12)
C1—N1—C12—O2	−133.18 (13)	C16—O3—C13—C14	−0.84 (15)
C1—N1—C12—C13	46.31 (16)	C17—N1—C1—C2	57.32 (18)
C1—N1—C17—O4	12.94 (19)	C17—N1—C1—C3	−123.99 (13)
C1—N1—C17—C18	−162.74 (12)	C17—N1—C12—O2	25.34 (19)
C2—N2—N3—C3	−6.41 (14)	C17—N1—C12—C13	−155.18 (12)
C2—N2—N3—C4	−155.84 (11)	C17—C18—C19—C20	179.39 (15)
C2—C1—C3—O1	177.86 (13)	C18—O5—C21—C20	−0.36 (18)
C2—C1—C3—N3	−0.33 (14)	C18—C19—C20—C21	0.8 (2)
C3—N3—C4—C5	−116.66 (14)	C19—C20—C21—O5	−0.3 (2)
C3—N3—C4—C9	61.27 (17)	C21—O5—C18—C17	−179.49 (13)
C3—C1—C2—N2	−3.68 (15)	C21—O5—C18—C19	0.87 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O4^i	0.98	2.61	3.418 (2)	140
C11—H11A···O4^i	0.98	2.50	3.4478 (19)	163
C14—H14···O1^i	0.95	2.35	3.197 (2)	148
C15—H15···O3^i	0.95	2.64	3.318 (2)	129
C16—H16···O4^ii	0.95	2.38	3.2680 (17)	156

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, −y+1/2, z−1/2.