A structural study of 4-amino­anti­pyrine and six of its Schiff base derivatives

Six derivatives of 4-amino-1,5-dimethyl-2-phenyl-2,3-di­hydro-1H-pyrazol-3-one (4-amino­anti­pyrine), C₁₁H₁₃N₃O, (I), have been synthesized and structurally characterized to investigate the changes in the observed hydrogen-bonding motifs compared to the original 4-amino­anti­pyrine. The derivatives were synthesized from the reactions of 4-amino­anti­pyrine with various aldehyde-, ketone- and ester-containing mol­ecules, producing (Z)-methyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)amino]­but-2-enoate, C₁₆H₁₉N₃O₃, (II), (Z)-ethyl 3-[(1,5-di­methyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyra­zol-4-yl)amino]­but-2-enoate, C₁₇H₂₁N₃O₃, (III), ethyl 2-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)amino]­cyclo­hex-1-ene­carboxyl­ate, C₂₀H₂₅N₃O₃, (IV), (Z)-ethyl 3-[(1,5-di­methyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)amino]-3-phenyl­acrylate, C₂₂H₂₃N₃O₃, (V), 2-cyano-N-(1,5-di­methyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)acetamide, C₁₄H₁₄N₄O₂, (VI), and (E)-methyl 4-{[(1,5-dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)amino]­meth­yl}ben­zoate, C₂₀H₁₉N₃O₃, (VII). The asymmetric units of all these compounds have one mol­ecule on a general position. The hydrogen bonding in (I) forms chains of molecules via inter­molecular N—H...O hydrogen bonds around a crystallographic sixfold screw axis. In contrast, the formation of enamines for all derived compounds except (VII) favours the formation of a six-membered intra­molecular N—H...O hydrogen-bonded ring in (II)–(V) and an inter­molecular N—H...O hydrogen bond in (VI), whereas there is an intra­molecular C—H...O hydrogen bond in the structure of imine (VII). All the reported compounds, except for (II), feature π–π inter­actions, while C—H...π inter­actions are observed in (II), C—H...O inter­actions are observed in (I), (III), (V) and (VI), and a C—O...π inter­action is observed in (II).

S1. Introduction

4-Amino­anti­pyrine (4-AAP), (I), is an anti-inflammatory agent which is mainly used as a reagent to detect phenols and peroxides (Adam, 2013). The use of 4-AAP as a nonsteroidal anti-inflammatory drug is rare because the drug causes agranulocytosis, i.e. a drop in the number of infection-fighting white blood cells (Adam, 2013). Some derivatives of 4-amino­anti­pyrines, such as dipyrone – an anti-inflammatory which is still in use – have medicinal properties (Li et al., 2013, and references therein). 4-AAP can be modified easily by reacting it with either an aldehyde, ketone or ester functional group to form Schiff bases and the prepared derivatives then show increased biological activities, such as anti­tumor, fungicidal, bactericidal, anti­viral, anti-inflammatory, anti­pyretic, analgesic, anti­proliferative and anti­oxidant activities (Cunha et al., 2005; Schilf et al., 2013). Metal complexes of 4-AAP-derived Schiff bases have been prepared and tested for biological activity also (Leelavathy & Antony, 2013; El-Bindary et al., 2013). Molecular salt complexes have also been prepared with quinol and picric acid (Adam, 2013). We synthesized six derivatives of 4-AAP, (II)–(VII) (see Scheme 1), and discuss the changes in molecular packing and hydrogen bonding compared to the parent 4-AAP, (I) (Scheme 1), and to related compounds in the Cambridge Structural Database (CSD, Version 5.34, with a May 2013 update; Groom & Allen, 2014). The derivatization is carried out with the molecules shown in Scheme 2. This report is a continuation of structural studies that look at how the hydrogen bonding changes in a series of related structures by varying the substituents on an organic backbone (Omondi et al., 2009; Lemmerer & Michael, 2010a,b, 2011).

S2. Experimental

S2.1. Synthesis and crystallization

All chemicals were purchased from commercial sources and used as received. Crystals where grown by slow evaporation under ambient conditions of a methanol solution containing a 1:1 ratio of 4-amino­anti­pyrine and the aldehyde/ketone and ester rea­ctant. The solutions were stirred and heated gently overnight to allow for complete reaction. Detailed masses and volumes are as follows: for (II), 4-AAP (0.100 g, 0.492 mmol) and methyl 3-oxo­butano­ate (see A in Scheme 2; 0.058 g, 0.500 mmol) in 8 ml methanol; for (III), 4-AAP (0.100 g, 0.492 mmol) and ethyl 3-oxo­butano­ate (B; 0.065 g, 0.500 mmol) in 8 ml methanol; for (IV), 4-AAP (0.100 g, 0.492 mmol) and ethyl 2-oxo­cyclo­hexane­carboxyl­ate (C; 0.085 g, 0.500 mmol) in 8 ml methanol; for (V), 4-AAP (0.100 g, 0.492 mmol) and ethyl 3-oxo-3-phenyl­propano­ate (D; 0.096 g, 0.500 mmol) in 8 ml methanol; for (VI), 4-AAP (0.100 g, 0.492 mmol) and 4-formyl­benzoate (E; 0.082 g, 0.500 mmol) in 8 ml methanol; for (VI), 4-AAP (0.100 g, 0.492 mmol) and ethyl cyano­acetate (F; 0.057 g, 0.500 mmol) in 8 ml methanol.

S2.2. Refinement

Cell determination, data collection and structure refinement details are summarized in Table 1. For all compounds, C-bound H atoms were placed geometrically [C—H = C—H = 0.95 (alkene), 0.98 (methyl­ene and CH₃), 0.99 (ethyl­ene, –CH₂–) or 0.95 Å (aromatic)] and refined as riding, with U_iso(H) = 1.2U_eq(C). N-bound H atoms were located in difference maps and their coordinates allowed to refine freely, with U_iso(H) = 1.5U_eq(N).

In (I), the absolute structure was chosen arbitrarily, and refinement of the absolute structure parameter (Flack & Bernardinelli, 2000) was not posible as molybdenum radiation was used. The Friedel pairs of reflections were thus merged prior to the final refinements. In addition, the crystals of (I) showed twinning, and the twin law (1 0 0 1 1 0 0 0 ¯), with the batch scale factor refining to 0.42502, resulted in a significant improvement of the refinement statistics.

S3. Results and discussion

The molecular structures and atomic numbering schemes of the asymmetric units of compounds (I)–(VII) are shown in Fig. 1, and the packing diagrams are shown in Figs. 2–4.

Recently, the room-temperature crystal structure of 4-AAP, (I), was reported (Li et al., 2013; CCDC deposition number 801822). The crystallographic indicators show a poor-quality data set [R_int = 0.097 and R1 (all data) = 0.0992] with low redundancy. Crystals grown from propan-2-ol by us showed bipyramidal crystal habits, and were observed as twinned under polarized light microscopy. We collected a low-temperature data set with the same unit cell as reported previously, with higher redundancy, and after applying a twin law, a much improved set of crystallographic discrepancy factors was obtained. Comparable bond lengths and angles are observed. The asymmetric unit consists of one 4-AAP molecule on a general position in the hexagonal space group P6₁. The hydrogen bonding involves only one of the H atoms on the amine N3 atom (H3A). This forms a hydrogen bond to carbonyl atom O1ⁱ of an adjacent molecule to form an infinite chain with graph set C(4) (Bernstein et al., 1995) (Fig. 2; see Table 2 for hydrogen-bond geometry and symmetry code). Ultimately, by virtue of the sixfold screw axis that defines the chain, a symmetrically pleasing helical form results down the crystallographic c axis (Fig. 3). Adjacent 4-AAP moleclues inter­act along the b axis by C8—H8···O1 hydrogen bonding [not in Table 2?], and along the a axis, there is a π–π inter­action between the benzene (atoms C6–C11) and pyrazole (atoms C1–N1) rings, with a centroid–centroid (Cg···Cg^viii) distance of 3.9705 (15) Å [symmetry code: (viii) y, -x+y+1, z+1/6].

The reaction of the ketone group of methyl 3-oxo­butano­ate with the amine group of 4-AAP produced enamine (II). The formation of an enamine favours the formation of an intra­molecular six-membered hydrogen-bonded ring with graph set S(6) (Etter, 1990) involving amine atom H3 to ester carbonyl atom O2 (Fig. 1; see Table 3 for hydrogen-bond geometry). The molecules pack in a head-to-tail fashion along the a axis, with two inter­molecular inter­actions involving π systems (Fig. 4a). Firstly, atom C10 inter­acts with the centroid (Cg1) of the benzene ring through atom H10 [C10—H10···Cg1^ix = 2.75 Å and C10—H10···Cg1^viii = 172°; symmetry code: (ix) -x+1, y+1/2, -z+3/2]. Secondly, the five-membered pyrazole ring forms a close contact with the O1 ketone group of a neighbouring inversion-related molecule, such that the centroid of the pyrazole ring (Cg2) has an O1···Cg2^iv distance of 3.7581 (12) Å [symmetry code: (iv) -x+1, -y+1, -z+1].

The reaction of the ketone group of ethyl 3-oxo­butano­ate with the amine group of 4-AAP produced enamine (III). Amine atom H3 forms an inter­molecular hydrogen bond with graph set S(6) to ester carbonyl atom O2, similar to (II) (Fig. 1). However, it has additional C—H···O hydrogen-bond inter­actions, viz. C11—H11···O1ⁱⁱ, forming an R₂²(12) hydrogen-bonded ring, and C8—H8···O3ⁱⁱⁱ, forming an R₄⁴(28) ring (Fig. 4b; see Table 4 for hydrogen-bond geometry and symmetry codes). Additionally, the molecules pack anti­parallel along the c axis, stabilized by centrosymmtric π–π inter­actions between adjacent pyrazole rings [Cg···Cg^iv = 3.9668 (9) Å].

The reaction of the ketone group of ethyl 2-oxo­cyclo­hexane­carboxyl­ate with the amine group of 4-AAP produced enamine (IV). Amine atom H3 forms an inter­molecular hydrogen bond with graph set S(6) to ester carbonyl atom O2 (Fig. 1 and Table 5). The molecules pack anti­parallel along the c axis, stabilized again by centrosymmtric π–π inter­actions between adjacent pyrazole rings [Cg···Cg^iv = 4.3240 (7) Å] (Fig. 4c).

The reaction of the ketone group of ethyl 3-oxo-3-phenyl­propano­ate with the amine group of 4-AAP produced enamine (V). Amine atom H3 forms an inter­molecular hydrogen bond with graph set S(6) to ester carbonyl atom O2, similar to (II) (Fig. 1). However, it has an additional N3—H3···O2^iv hydrogen-bond inter­action between neighbouring molecules, thus forming also an R₂²(4) hydrogen-bonded ring dimer (Fig. 4d; see Table 6 for hydrogen-bond geometry and symmetry codes). The dimers are connected via a weak C8—H8···O1^v hydrogen bond along the a axis. Along the c axis, molecules are stabilized again by centrosymmtric π–π inter­actions, this time between adjacent benzene rings [Cg···Cg^x = 4.3681 (8) Å; symmetry code: (x) -x+2, -y, -z+1] (Fig. 4d).

The reaction of the ester group of ethyl cyano­acetate with the amine group of 4-AAP produced enamine (VI). Amine atom H3 forms an inter­molecular N—H···O hydrogen bond to ring carbonyl atom O1^vi of a neighbouring molecule producing an R₂²(10) hydrogen-bonded ring dimer (Fig. 1; see Table 7 for hydrogen-bond geometry and symmetry codes). In addition, there is an inter­molecular C9—H9···O2^vii hydrogen bond between translationally related molecules along the b axis. A π–π inter­action is observed along the a axis between pyrazole rings [Cg···Cg^xi = 4.2438 (8) Å; symmetry code: (xi) -x, -y+1, -z] (Fig. 4e).

The reaction of the aldehyde group of methyl 4-formyl­benzoate with the amine group of 4-AAP produced imine (VII), in contrast to the tautomerization to an enamine seen in the other compounds. Alkene atom H12 forms an intra­molecular C—H···O hydrogen bond with graph set S(6) to ring carbonyl atom O1 (Fig. 1), which is different to the intra­molecular hydrogen bonds observed in all the other compounds. The packing diagram of (VII) (Fig. 4f; see Table 8 for hydrogen-bond geometry and symmetry codes) shows a head-to tail arrangement and the π–π inter­actions between the pyrazole and benzene rings of adjacent molecules along the c axis. The centroid of the pyrazole ring (Cg1) is 3.6772 (7) Å from the centroid of the benzene ring at (-x+1/2, -y+1/2, -z+1). [No H-bond data for (VII) is included in the CIF]

Comparatively, there is similarity and some variation in the hydrogen-bonding inter­actions that derivatives (II)–(VII) of 4-AAP show compared to the parent compound, (I). There are four intra­molecular N—H···O hydrogen bonds that form between the enamine N3 and ester carbonyl O2 atoms in (II) and (IV)–(VI). However, in (V), the pattern is slightly different due to the bifurcated nature of the H3···O2 inter­action. The bifurcation of the three-centred inter­action was confirmed by summing the angles around atom H3 and the sum was 356°. In the one structure that does not form the enamine tautomer, but rather the imine tautomer, i.e. (VII), an intra­molecular S(6) hydrogen bond is formed, but this time a weaker C—H···O-type inter­action is observed. The molecule in the crystal of (VII) is an imine because the formation of an enamine would have required the removal of the aromaticity of the benzene ring, which is unfavourable. Since the molecule is in the imine form, it does not possess the amine hydrogen-bond donor. The presence of two different aromatic-ring systems, viz. pyrazole and benzene, in all the compounds results in numerous π–π inter­actions. In terms of significant inter­molecular inter­actions involving weak hydrogen bonding, there are two C—H···O inter­actions and one C—H···π inter­action in addition to the stronger N—H···O hydrogen bonds.

Compared to other derivatized structures that have the 4-amino­anti­pyrine backbone, there are 146 (136 neither solvated nor hydrated) structures in the CSD that all crystallize in the imine form and only six that crystallize in the enamine form. Unsurprisingly, all 136 of the imine structures have the intra­molecular C—H···O S(6) hydrogen bond, as seen in (VII). Similarly, for the five unsolvated enamine structures of the original six, all have the intra­molecular N—H···O hydrogen bond. However, if one adds the criteria of having a C═O carbonyl group three C atoms away, as is seen for the derivatized compounds (II)–(VII), then the number of resulting compounds without any solvent that have the imine tautomer decreases to only one. The five enamines found in the literature all contain a carbonyl group, indicating that the presence of a second carbonyl group favours the formation of an enamine over an imine.

Computing details

For all compounds, data collection: APEX3 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures

	Fig. 1. Perspective views of compounds (I)–(VII), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. View of the one-dimensional hydrogen-bonded chain down the sixfold screw axis in (I). Note the lack of any hydrogen-bond interactions of the second amine H facing towards the centre of the helix. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity. The hydrogen bonds are displayed as in Fig. 2.
	Fig. 3. (a) Packing diagram of (II). (b) View of the intermolecular C—H···O hydrogen bonds forming a sequence of R2^2(12) and R4^4(28) rings in (III). (c) Packing diagram of (IV); note the absence of any intermolecular hydrogen-bond interactions. (d) View of the inter- and intramolecular N—H···O hydrogen bonds forming an R2^2(4) ring and an S(6) ring in (V). (e) Packing diagram of (VI); note the absence of any intermolecular hydrogen-bond interactions. (f) View of the intermolecular N—H···O hydrogen bonds forming an R2^2(10) ring and a chain of C—H···O hydrogen bonds in (VII). H atoms not involved in hydrogen-bond interactions have been omitted for clarity. The hydrogen bonds are displayed as in Fig. 2.

(I) 4-Amino-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

Crystal data

C11H13N3O	Dx = 1.321 Mg m^−3
Mr = 203.24	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P61	Cell parameters from 5670 reflections
Hall symbol: P 61	θ = 3.2–25.2°
a = 7.4519 (1) Å	µ = 0.09 mm^−1
c = 31.8705 (7) Å	T = 173 K
V = 1532.69 (5) Å^3	Prism, colourless
Z = 6	0.45 × 0.18 × 0.15 mm
F(000) = 648

Data collection

Bruker D8 Venture Photon CMOS diffractometer	2353 reflections with I > 2σ(I)
ω scans	Rint = 0.031
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 1.3°
Tmin = 0.95, Tmax = 0.96	h = −9→9
13962 measured reflections	k = −9→9
2455 independent reflections	l = −42→42

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 0.0558P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.033	(Δ/σ)max = 0.026
wR(F^2) = 0.083	Δρmax = 0.16 e Å^−3
S = 1.07	Δρmin = −0.15 e Å^−3
2455 reflections	Absolute structure: Flack x determined using 1076 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
147 parameters	Absolute structure parameter: 0.2 (10)
1 restraint

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.6930 (4)	0.2346 (4)	0.15103 (7)	0.0282 (5)
C2	0.6318 (4)	0.1598 (4)	0.19357 (8)	0.0305 (5)
C3	0.4930 (4)	0.2136 (4)	0.20641 (7)	0.0291 (5)
C4	0.3883 (4)	0.1794 (4)	0.24802 (8)	0.0384 (6)
H4A	0.4364	0.1081	0.2668	0.058*
H4B	0.2379	0.0944	0.2443	0.058*
H4C	0.4218	0.3133	0.2602	0.058*
C5	0.2424 (4)	0.2541 (4)	0.16340 (9)	0.0355 (5)
H5A	0.2387	0.3398	0.1405	0.053*
H5B	0.1676	0.2648	0.1877	0.053*
H5C	0.1768	0.1094	0.1542	0.053*
C6	0.6124 (4)	0.4585 (4)	0.10609 (7)	0.0271 (5)
C7	0.6249 (4)	0.6488 (4)	0.11171 (9)	0.0332 (5)
H7	0.6065	0.6903	0.1388	0.04*
C8	0.6649 (4)	0.7790 (4)	0.07719 (10)	0.0403 (6)
H8	0.6741	0.91	0.0808	0.048*
C9	0.6909 (4)	0.7174 (5)	0.03793 (9)	0.0437 (7)
H9	0.7174	0.8059	0.0145	0.052*
C10	0.6784 (4)	0.5272 (5)	0.03254 (8)	0.0395 (6)
H10	0.6986	0.4867	0.0055	0.047*
C11	0.6369 (4)	0.3960 (4)	0.06634 (7)	0.0319 (5)
H11	0.625	0.2641	0.0625	0.038*
N1	0.5751 (3)	0.3231 (3)	0.14030 (6)	0.0280 (4)
N2	0.4599 (3)	0.3271 (4)	0.17519 (6)	0.0291 (4)
N3	0.7274 (4)	0.0677 (5)	0.21505 (9)	0.0508 (7)
H3A	0.675 (5)	−0.001 (5)	0.2376 (11)	0.036 (8)*
H3B	0.797 (6)	0.040 (5)	0.2010 (11)	0.042 (9)*
O1	0.8267 (3)	0.2302 (3)	0.12882 (6)	0.0356 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0287 (11)	0.0295 (11)	0.0257 (10)	0.0140 (9)	0.0007 (9)	0.0023 (9)
C2	0.0296 (12)	0.0312 (11)	0.0265 (11)	0.0121 (10)	0.0026 (9)	0.0047 (9)
C3	0.0280 (10)	0.0294 (10)	0.0231 (10)	0.0093 (9)	0.0018 (9)	0.0005 (9)
C4	0.0437 (14)	0.0404 (14)	0.0260 (12)	0.0172 (11)	0.0086 (11)	0.0020 (11)
C5	0.0274 (12)	0.0381 (13)	0.0403 (12)	0.0159 (11)	0.0031 (10)	−0.0030 (12)
C6	0.0222 (10)	0.0326 (12)	0.0254 (10)	0.0130 (9)	−0.0011 (9)	0.0018 (9)
C7	0.0303 (11)	0.0365 (13)	0.0354 (12)	0.0187 (11)	−0.0018 (10)	0.0009 (10)
C8	0.0312 (12)	0.0366 (13)	0.0546 (16)	0.0181 (11)	−0.0011 (12)	0.0111 (13)
C9	0.0352 (13)	0.0501 (17)	0.0418 (14)	0.0184 (13)	−0.0011 (13)	0.0200 (13)
C10	0.0365 (14)	0.0532 (16)	0.0260 (11)	0.0203 (12)	−0.0026 (11)	0.0054 (12)
C11	0.0308 (11)	0.0364 (12)	0.0270 (11)	0.0156 (10)	−0.0032 (10)	0.0012 (10)
N1	0.0305 (10)	0.0345 (10)	0.0225 (8)	0.0189 (8)	0.0030 (7)	0.0025 (8)
N2	0.0288 (10)	0.0324 (11)	0.0249 (9)	0.0143 (8)	0.0047 (7)	0.0010 (8)
N3	0.0520 (15)	0.0734 (19)	0.0419 (14)	0.0425 (15)	0.0166 (13)	0.0307 (15)
O1	0.0382 (10)	0.0463 (10)	0.0307 (9)	0.0274 (8)	0.0096 (8)	0.0096 (8)

Geometric parameters (Å, º)

C1—O1	1.236 (3)	C6—C11	1.393 (3)
C1—N1	1.380 (3)	C6—N1	1.416 (3)
C1—C2	1.450 (3)	C7—C8	1.397 (4)
C2—C3	1.346 (3)	C7—H7	0.95
C2—N3	1.391 (4)	C8—C9	1.380 (5)
C3—N2	1.405 (3)	C8—H8	0.95
C3—C4	1.495 (3)	C9—C10	1.384 (5)
C4—H4A	0.98	C9—H9	0.95
C4—H4B	0.98	C10—C11	1.382 (4)
C4—H4C	0.98	C10—H10	0.95
C5—N2	1.477 (3)	C11—H11	0.95
C5—H5A	0.98	N1—N2	1.414 (3)
C5—H5B	0.98	N3—H3A	0.86 (4)
C5—H5C	0.98	N3—H3B	0.79 (4)
C6—C7	1.385 (4)
O1—C1—N1	125.8 (2)	C6—C7—C8	119.4 (3)
O1—C1—C2	128.9 (2)	C6—C7—H7	120.3
N1—C1—C2	105.22 (19)	C8—C7—H7	120.3
C3—C2—N3	131.0 (2)	C9—C8—C7	120.0 (3)
C3—C2—C1	108.1 (2)	C9—C8—H8	120
N3—C2—C1	120.6 (2)	C7—C8—H8	120
C2—C3—N2	110.87 (19)	C8—C9—C10	120.3 (2)
C2—C3—C4	129.2 (2)	C8—C9—H9	119.8
N2—C3—C4	119.8 (2)	C10—C9—H9	119.8
C3—C4—H4A	109.5	C11—C10—C9	120.3 (3)
C3—C4—H4B	109.5	C11—C10—H10	119.9
H4A—C4—H4B	109.5	C9—C10—H10	119.9
C3—C4—H4C	109.5	C10—C11—C6	119.5 (2)
H4A—C4—H4C	109.5	C10—C11—H11	120.2
H4B—C4—H4C	109.5	C6—C11—H11	120.2
N2—C5—H5A	109.5	C1—N1—N2	110.69 (18)
N2—C5—H5B	109.5	C1—N1—C6	125.93 (19)
H5A—C5—H5B	109.5	N2—N1—C6	119.71 (19)
N2—C5—H5C	109.5	C3—N2—N1	104.66 (18)
H5A—C5—H5C	109.5	C3—N2—C5	116.7 (2)
H5B—C5—H5C	109.5	N1—N2—C5	110.97 (18)
C7—C6—C11	120.5 (2)	C2—N3—H3A	121 (2)
C7—C6—N1	121.2 (2)	C2—N3—H3B	115 (2)
C11—C6—N1	118.3 (2)	H3A—N3—H3B	119 (3)
O1—C1—C2—C3	174.7 (3)	O1—C1—N1—N2	−171.4 (2)
N1—C1—C2—C3	−2.7 (3)	C2—C1—N1—N2	6.1 (3)
O1—C1—C2—N3	−0.1 (4)	O1—C1—N1—C6	−13.3 (4)
N1—C1—C2—N3	−177.5 (2)	C2—C1—N1—C6	164.3 (2)
N3—C2—C3—N2	172.3 (3)	C7—C6—N1—C1	−127.3 (3)
C1—C2—C3—N2	−1.7 (3)	C11—C6—N1—C1	52.5 (3)
N3—C2—C3—C4	−3.7 (5)	C7—C6—N1—N2	29.0 (3)
C1—C2—C3—C4	−177.8 (3)	C11—C6—N1—N2	−151.1 (2)
C11—C6—C7—C8	−0.8 (4)	C2—C3—N2—N1	5.3 (3)
N1—C6—C7—C8	179.1 (2)	C4—C3—N2—N1	−178.2 (2)
C6—C7—C8—C9	0.2 (4)	C2—C3—N2—C5	128.4 (2)
C7—C8—C9—C10	−0.3 (4)	C4—C3—N2—C5	−55.1 (3)
C8—C9—C10—C11	0.9 (4)	C1—N1—N2—C3	−7.1 (3)
C9—C10—C11—C6	−1.5 (4)	C6—N1—N2—C3	−166.8 (2)
C7—C6—C11—C10	1.4 (4)	C1—N1—N2—C5	−133.8 (2)
N1—C6—C11—C10	−178.4 (2)	C6—N1—N2—C5	66.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1^i	0.86 (4)	2.15 (4)	2.999 (3)	170 (3)

Symmetry code: (i) x−y, x−1, z+1/6.

(II) (Z)-Methyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]but-2-enoate

Crystal data

C16H19N3O3	F(000) = 640
Mr = 301.34	Dx = 1.312 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6999 reflections
a = 11.2061 (14) Å	θ = 3.3–28.3°
b = 7.4638 (8) Å	µ = 0.09 mm^−1
c = 19.044 (2) Å	T = 173 K
β = 106.655 (4)°	Plate, colourless
V = 1526.0 (3) Å^3	0.42 × 0.33 × 0.13 mm
Z = 4

Data collection

Bruker D8 Venture Photon diffractometer	3114 reflections with I > 2σ(I)
ω scans	Rint = 0.018
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 3.5°
Tmin = 0.96, Tmax = 0.99	h = −14→14
12126 measured reflections	k = −9→8
3670 independent reflections	l = −23→25

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.4578P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.108	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.32 e Å^−3
3670 reflections	Δρmin = −0.25 e Å^−3
207 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.33084 (10)	0.54325 (15)	0.48152 (6)	0.0223 (2)
C2	0.27364 (10)	0.42379 (15)	0.42209 (6)	0.0222 (2)
C3	0.27806 (10)	0.25393 (15)	0.44904 (6)	0.0215 (2)
C4	0.23794 (12)	0.08445 (16)	0.40829 (7)	0.0300 (3)
H4A	0.1794	0.1114	0.3604	0.045*
H4B	0.1971	0.0077	0.4362	0.045*
H4C	0.3108	0.0224	0.4014	0.045*
C5	0.40900 (12)	0.11438 (15)	0.56482 (6)	0.0274 (3)
H5A	0.3791	−0.0026	0.5436	0.041*
H5B	0.4079	0.1176	0.6161	0.041*
H5C	0.4943	0.1336	0.5624	0.041*
C6	0.36757 (10)	0.49332 (14)	0.61445 (6)	0.0210 (2)
C7	0.28437 (11)	0.42183 (16)	0.64849 (6)	0.0258 (2)
H7	0.2311	0.3258	0.6264	0.031*
C8	0.27954 (12)	0.49164 (18)	0.71511 (7)	0.0310 (3)
H8	0.223	0.4426	0.7388	0.037*
C9	0.35629 (12)	0.63190 (17)	0.74739 (7)	0.0311 (3)
H9	0.3514	0.6807	0.7926	0.037*
C10	0.44014 (12)	0.70079 (17)	0.71360 (7)	0.0320 (3)
H10	0.4935	0.7964	0.736	0.038*
C11	0.44716 (11)	0.63159 (16)	0.64722 (7)	0.0271 (3)
H11	0.5057	0.6783	0.6245	0.032*
C12	0.11810 (10)	0.58614 (15)	0.32668 (6)	0.0229 (2)
C13	0.05629 (12)	0.64069 (17)	0.38326 (7)	0.0295 (3)
H13A	0.0234	0.5343	0.4014	0.044*
H13B	−0.0121	0.7235	0.3614	0.044*
H13C	0.1171	0.7	0.424	0.044*
C14	0.07240 (11)	0.64379 (16)	0.25596 (6)	0.0255 (2)
H14	0.0037	0.724	0.2444	0.031*
C15	0.12353 (11)	0.58856 (16)	0.19846 (6)	0.0263 (3)
C16	0.11845 (15)	0.6344 (2)	0.07489 (7)	0.0453 (4)
H16A	0.204	0.6798	0.0868	0.068*
H16B	0.0677	0.6926	0.0302	0.068*
H16C	0.1185	0.5046	0.0671	0.068*
N1	0.36827 (9)	0.43209 (12)	0.54355 (5)	0.0218 (2)
N2	0.32779 (9)	0.25576 (12)	0.52354 (5)	0.0216 (2)
N3	0.21884 (10)	0.47652 (13)	0.34857 (5)	0.0253 (2)
H3	0.2528 (14)	0.447 (2)	0.3147 (9)	0.035 (4)*
O1	0.34267 (8)	0.70732 (11)	0.48366 (5)	0.0302 (2)
O2	0.20659 (9)	0.47876 (12)	0.20326 (5)	0.0332 (2)
O3	0.06747 (9)	0.67266 (14)	0.13427 (5)	0.0355 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0243 (5)	0.0195 (5)	0.0241 (5)	0.0012 (4)	0.0086 (4)	0.0031 (4)
C2	0.0260 (5)	0.0209 (5)	0.0202 (5)	0.0036 (4)	0.0073 (4)	0.0026 (4)
C3	0.0229 (5)	0.0204 (5)	0.0212 (5)	0.0033 (4)	0.0063 (4)	0.0003 (4)
C4	0.0391 (7)	0.0209 (5)	0.0253 (6)	0.0030 (5)	0.0015 (5)	−0.0028 (4)
C5	0.0337 (6)	0.0195 (5)	0.0260 (6)	0.0054 (5)	0.0035 (5)	0.0041 (4)
C6	0.0216 (5)	0.0188 (5)	0.0203 (5)	0.0033 (4)	0.0026 (4)	0.0004 (4)
C7	0.0251 (5)	0.0259 (6)	0.0252 (6)	−0.0028 (4)	0.0054 (4)	−0.0021 (4)
C8	0.0312 (6)	0.0364 (7)	0.0273 (6)	0.0017 (5)	0.0111 (5)	0.0001 (5)
C9	0.0352 (6)	0.0337 (6)	0.0217 (6)	0.0075 (5)	0.0036 (5)	−0.0046 (5)
C10	0.0334 (6)	0.0281 (6)	0.0288 (6)	−0.0026 (5)	−0.0002 (5)	−0.0064 (5)
C11	0.0254 (6)	0.0255 (6)	0.0289 (6)	−0.0031 (4)	0.0056 (5)	−0.0014 (5)
C12	0.0247 (5)	0.0184 (5)	0.0248 (6)	−0.0021 (4)	0.0056 (4)	0.0002 (4)
C13	0.0282 (6)	0.0330 (6)	0.0280 (6)	0.0030 (5)	0.0094 (5)	−0.0002 (5)
C14	0.0245 (5)	0.0240 (5)	0.0256 (6)	0.0018 (4)	0.0037 (4)	0.0035 (4)
C15	0.0289 (6)	0.0250 (6)	0.0220 (6)	−0.0058 (5)	0.0026 (4)	0.0021 (4)
C16	0.0520 (9)	0.0604 (10)	0.0236 (6)	−0.0095 (7)	0.0108 (6)	0.0056 (6)
N1	0.0281 (5)	0.0153 (4)	0.0215 (5)	−0.0012 (4)	0.0065 (4)	−0.0003 (3)
N2	0.0292 (5)	0.0146 (4)	0.0198 (4)	0.0006 (4)	0.0048 (4)	0.0006 (3)
N3	0.0329 (5)	0.0249 (5)	0.0190 (5)	0.0084 (4)	0.0087 (4)	0.0040 (4)
O1	0.0402 (5)	0.0173 (4)	0.0325 (5)	−0.0024 (3)	0.0092 (4)	0.0034 (3)
O2	0.0425 (5)	0.0301 (5)	0.0275 (4)	0.0053 (4)	0.0111 (4)	−0.0002 (4)
O3	0.0349 (5)	0.0464 (6)	0.0231 (4)	−0.0012 (4)	0.0048 (4)	0.0098 (4)

Geometric parameters (Å, º)

C1—O1	1.2312 (14)	C9—C10	1.3812 (19)
C1—N1	1.4057 (14)	C9—H9	0.95
C1—C2	1.4390 (16)	C10—C11	1.3887 (18)
C2—C3	1.3633 (15)	C10—H10	0.95
C2—N3	1.4141 (14)	C11—H11	0.95
C3—N2	1.3677 (14)	C12—N3	1.3593 (15)
C3—C4	1.4848 (16)	C12—C14	1.3659 (16)
C4—H4A	0.98	C12—C13	1.4948 (16)
C4—H4B	0.98	C13—H13A	0.98
C4—H4C	0.98	C13—H13B	0.98
C5—N2	1.4662 (14)	C13—H13C	0.98
C5—H5A	0.98	C14—C15	1.4343 (17)
C5—H5B	0.98	C14—H14	0.95
C5—H5C	0.98	C15—O2	1.2237 (15)
C6—C7	1.3860 (16)	C15—O3	1.3575 (14)
C6—C11	1.3895 (16)	C16—O3	1.4343 (17)
C6—N1	1.4276 (14)	C16—H16A	0.98
C7—C8	1.3868 (17)	C16—H16B	0.98
C7—H7	0.95	C16—H16C	0.98
C8—C9	1.3822 (18)	N1—N2	1.4086 (12)
C8—H8	0.95	N3—H3	0.865 (15)
O1—C1—N1	123.77 (10)	C11—C10—H10	119.7
O1—C1—C2	131.43 (11)	C10—C11—C6	119.24 (11)
N1—C1—C2	104.70 (9)	C10—C11—H11	120.4
C3—C2—N3	126.17 (10)	C6—C11—H11	120.4
C3—C2—C1	108.67 (10)	N3—C12—C14	122.39 (11)
N3—C2—C1	125.13 (10)	N3—C12—C13	117.29 (10)
C2—C3—N2	109.96 (10)	C14—C12—C13	120.31 (11)
C2—C3—C4	128.51 (10)	C12—C13—H13A	109.5
N2—C3—C4	121.53 (10)	C12—C13—H13B	109.5
C3—C4—H4A	109.5	H13A—C13—H13B	109.5
C3—C4—H4B	109.5	C12—C13—H13C	109.5
H4A—C4—H4B	109.5	H13A—C13—H13C	109.5
C3—C4—H4C	109.5	H13B—C13—H13C	109.5
H4A—C4—H4C	109.5	C12—C14—C15	122.91 (11)
H4B—C4—H4C	109.5	C12—C14—H14	118.5
N2—C5—H5A	109.5	C15—C14—H14	118.5
N2—C5—H5B	109.5	O2—C15—O3	121.51 (11)
H5A—C5—H5B	109.5	O2—C15—C14	126.67 (11)
N2—C5—H5C	109.5	O3—C15—C14	111.82 (11)
H5A—C5—H5C	109.5	O3—C16—H16A	109.5
H5B—C5—H5C	109.5	O3—C16—H16B	109.5
C7—C6—C11	120.47 (11)	H16A—C16—H16B	109.5
C7—C6—N1	120.39 (10)	O3—C16—H16C	109.5
C11—C6—N1	119.06 (10)	H16A—C16—H16C	109.5
C6—C7—C8	119.41 (11)	H16B—C16—H16C	109.5
C6—C7—H7	120.3	C1—N1—N2	109.19 (8)
C8—C7—H7	120.3	C1—N1—C6	121.65 (9)
C9—C8—C7	120.59 (12)	N2—N1—C6	117.80 (9)
C9—C8—H8	119.7	C3—N2—N1	107.09 (8)
C7—C8—H8	119.7	C3—N2—C5	123.70 (9)
C10—C9—C8	119.64 (11)	N1—N2—C5	115.16 (9)
C10—C9—H9	120.2	C12—N3—C2	123.92 (10)
C8—C9—H9	120.2	C12—N3—H3	115.2 (10)
C9—C10—C11	120.61 (12)	C2—N3—H3	120.6 (10)
C9—C10—H10	119.7	C15—O3—C16	115.58 (11)
O1—C1—C2—C3	−176.21 (12)	C2—C1—N1—N2	−3.94 (11)
N1—C1—C2—C3	0.18 (12)	O1—C1—N1—C6	30.18 (16)
O1—C1—C2—N3	2.0 (2)	C2—C1—N1—C6	−146.57 (10)
N1—C1—C2—N3	178.38 (10)	C7—C6—N1—C1	112.10 (12)
N3—C2—C3—N2	−174.40 (10)	C11—C6—N1—C1	−64.76 (14)
C1—C2—C3—N2	3.78 (13)	C7—C6—N1—N2	−27.50 (14)
N3—C2—C3—C4	5.9 (2)	C11—C6—N1—N2	155.64 (10)
C1—C2—C3—C4	−175.94 (11)	C2—C3—N2—N1	−6.19 (12)
C11—C6—C7—C8	1.14 (17)	C4—C3—N2—N1	173.56 (10)
N1—C6—C7—C8	−175.67 (10)	C2—C3—N2—C5	−143.89 (11)
C6—C7—C8—C9	0.34 (18)	C4—C3—N2—C5	35.87 (16)
C7—C8—C9—C10	−1.23 (19)	C1—N1—N2—C3	6.29 (12)
C8—C9—C10—C11	0.63 (19)	C6—N1—N2—C3	150.55 (9)
C9—C10—C11—C6	0.83 (19)	C1—N1—N2—C5	148.07 (10)
C7—C6—C11—C10	−1.73 (17)	C6—N1—N2—C5	−67.67 (12)
N1—C6—C11—C10	175.13 (11)	C14—C12—N3—C2	175.65 (11)
N3—C12—C14—C15	2.42 (18)	C13—C12—N3—C2	−5.27 (17)
C13—C12—C14—C15	−176.63 (11)	C3—C2—N3—C12	115.01 (14)
C12—C14—C15—O2	4.5 (2)	C1—C2—N3—C12	−62.89 (16)
C12—C14—C15—O3	−176.07 (11)	O2—C15—O3—C16	−4.56 (17)
O1—C1—N1—N2	172.80 (10)	C14—C15—O3—C16	176.01 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.865 (15)	2.048 (16)	2.7312 (13)	135 (1)

(III) (Z)-Ethyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]but-2-enoate

Crystal data

C17H21N3O3	F(000) = 672
Mr = 315.37	Dx = 1.283 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by ?
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9952 reflections
a = 13.427 (2) Å	θ = 3.4–28.3°
b = 10.1086 (14) Å	µ = 0.09 mm^−1
c = 12.2801 (18) Å	T = 173 K
β = 101.690 (5)°	Block, brown
V = 1632.2 (4) Å^3	0.42 × 0.39 × 0.31 mm
Z = 4

Data collection

Bruker D8 Venture Photon diffractometer	3494 reflections with I > 2σ(I)
ω scans	Rint = 0.021
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 3.4°
Tmin = 0.96, Tmax = 0.97	h = −17→17
20796 measured reflections	k = −13→13
3921 independent reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 0.4416P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.115	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.30 e Å^−3
3921 reflections	Δρmin = −0.26 e Å^−3
216 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.50682 (8)	0.24189 (10)	0.49565 (8)	0.0220 (2)
C2	0.56615 (8)	0.34047 (10)	0.45208 (8)	0.0224 (2)
C3	0.50318 (8)	0.41389 (10)	0.37465 (8)	0.0230 (2)
C4	0.52683 (9)	0.52616 (11)	0.30537 (10)	0.0307 (2)
H4A	0.5958	0.5584	0.3353	0.046*
H4B	0.4779	0.5978	0.3066	0.046*
H4C	0.5223	0.496	0.2287	0.046*
C5	0.33522 (9)	0.36253 (12)	0.25646 (9)	0.0298 (2)
H5A	0.3317	0.449	0.2197	0.045*
H5B	0.2673	0.3373	0.267	0.045*
H5C	0.3601	0.2962	0.2102	0.045*
C6	0.31891 (8)	0.20442 (10)	0.45872 (8)	0.0218 (2)
C7	0.24395 (8)	0.28769 (11)	0.48285 (9)	0.0262 (2)
H7	0.2516	0.381	0.48	0.031*
C8	0.15768 (9)	0.23323 (13)	0.51115 (10)	0.0326 (3)
H8	0.1057	0.2893	0.5273	0.039*
C9	0.14749 (9)	0.09698 (14)	0.51584 (10)	0.0357 (3)
H9	0.0889	0.0598	0.5361	0.043*
C10	0.22245 (10)	0.01499 (12)	0.49106 (10)	0.0342 (3)
H10	0.2146	−0.0783	0.4939	0.041*
C11	0.30883 (9)	0.06761 (11)	0.46209 (9)	0.0273 (2)
H11	0.3602	0.0113	0.4449	0.033*
C12	0.74722 (8)	0.34228 (10)	0.44013 (9)	0.0248 (2)
C13	0.72015 (10)	0.29611 (16)	0.32186 (11)	0.0412 (3)
H13A	0.6707	0.2239	0.3158	0.062*
H13B	0.7815	0.2646	0.2984	0.062*
H13C	0.6905	0.3697	0.2741	0.062*
C14	0.84661 (8)	0.36475 (11)	0.48936 (9)	0.0265 (2)
H14	0.8971	0.353	0.4461	0.032*
C15	0.87833 (8)	0.40522 (10)	0.60321 (9)	0.0235 (2)
C16	1.02030 (9)	0.46559 (14)	0.74458 (10)	0.0371 (3)
H16A	1.0937	0.4438	0.7636	0.044*
H16B	0.9857	0.4142	0.7947	0.044*
C17	1.00661 (11)	0.61014 (14)	0.76352 (12)	0.0419 (3)
H17A	1.0376	0.6615	0.7114	0.063*
H17B	1.0394	0.633	0.8399	0.063*
H17C	0.9339	0.6306	0.7517	0.063*
N1	0.40925 (7)	0.25677 (9)	0.43186 (7)	0.0237 (2)
N2	0.40470 (7)	0.37017 (9)	0.36466 (7)	0.0229 (2)
N3	0.67072 (7)	0.35975 (10)	0.49527 (8)	0.0250 (2)
H3	0.6905 (13)	0.3796 (17)	0.5667 (15)	0.049 (4)*
O1	0.53027 (6)	0.16475 (8)	0.57443 (6)	0.02857 (19)
O2	0.82303 (6)	0.41981 (8)	0.67041 (6)	0.02946 (19)
O3	0.97998 (6)	0.42703 (9)	0.63075 (7)	0.0325 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0195 (5)	0.0245 (5)	0.0215 (4)	0.0030 (4)	0.0030 (4)	−0.0016 (4)
C2	0.0207 (5)	0.0253 (5)	0.0215 (4)	0.0001 (4)	0.0048 (4)	−0.0035 (4)
C3	0.0244 (5)	0.0239 (5)	0.0214 (5)	0.0012 (4)	0.0066 (4)	−0.0027 (4)
C4	0.0361 (6)	0.0269 (5)	0.0300 (5)	−0.0004 (4)	0.0093 (5)	0.0033 (4)
C5	0.0282 (6)	0.0387 (6)	0.0201 (5)	0.0037 (4)	−0.0009 (4)	0.0012 (4)
C6	0.0187 (5)	0.0265 (5)	0.0191 (4)	0.0003 (4)	0.0011 (4)	0.0006 (4)
C7	0.0238 (5)	0.0271 (5)	0.0267 (5)	0.0033 (4)	0.0028 (4)	−0.0004 (4)
C8	0.0209 (5)	0.0469 (7)	0.0299 (6)	0.0038 (5)	0.0049 (4)	−0.0014 (5)
C9	0.0252 (6)	0.0515 (7)	0.0295 (6)	−0.0124 (5)	0.0030 (4)	0.0033 (5)
C10	0.0366 (6)	0.0303 (6)	0.0326 (6)	−0.0097 (5)	−0.0007 (5)	0.0026 (5)
C11	0.0275 (5)	0.0261 (5)	0.0264 (5)	0.0018 (4)	0.0011 (4)	−0.0011 (4)
C12	0.0247 (5)	0.0247 (5)	0.0256 (5)	0.0008 (4)	0.0062 (4)	−0.0040 (4)
C13	0.0280 (6)	0.0633 (9)	0.0321 (6)	0.0019 (6)	0.0058 (5)	−0.0218 (6)
C14	0.0222 (5)	0.0315 (5)	0.0268 (5)	0.0000 (4)	0.0074 (4)	−0.0044 (4)
C15	0.0217 (5)	0.0218 (5)	0.0264 (5)	0.0001 (4)	0.0033 (4)	0.0020 (4)
C16	0.0283 (6)	0.0457 (7)	0.0326 (6)	−0.0014 (5)	−0.0047 (5)	−0.0058 (5)
C17	0.0436 (7)	0.0443 (7)	0.0383 (7)	−0.0091 (6)	0.0095 (6)	−0.0053 (6)
N1	0.0194 (4)	0.0267 (4)	0.0242 (4)	0.0026 (3)	0.0025 (3)	0.0058 (3)
N2	0.0233 (4)	0.0255 (4)	0.0194 (4)	0.0023 (3)	0.0028 (3)	0.0034 (3)
N3	0.0198 (4)	0.0335 (5)	0.0215 (4)	−0.0023 (3)	0.0035 (3)	−0.0047 (3)
O1	0.0248 (4)	0.0322 (4)	0.0275 (4)	0.0056 (3)	0.0024 (3)	0.0074 (3)
O2	0.0265 (4)	0.0387 (5)	0.0237 (4)	−0.0019 (3)	0.0061 (3)	0.0003 (3)
O3	0.0213 (4)	0.0433 (5)	0.0315 (4)	−0.0017 (3)	0.0018 (3)	−0.0070 (3)

Geometric parameters (Å, º)

C1—O1	1.2328 (13)	C10—C11	1.3864 (17)
C1—N1	1.3916 (13)	C10—H10	0.95
C1—C2	1.4446 (14)	C11—H11	0.95
C2—C3	1.3579 (15)	C12—N3	1.3515 (14)
C2—N3	1.4102 (14)	C12—C14	1.3679 (16)
C3—N2	1.3759 (14)	C12—C13	1.4985 (15)
C3—C4	1.4906 (15)	C13—H13A	0.98
C4—H4A	0.98	C13—H13B	0.98
C4—H4B	0.98	C13—H13C	0.98
C4—H4C	0.98	C14—C15	1.4360 (15)
C5—N2	1.4627 (13)	C14—H14	0.95
C5—H5A	0.98	C15—O2	1.2258 (13)
C5—H5B	0.98	C15—O3	1.3559 (13)
C5—H5C	0.98	C16—O3	1.4464 (14)
C6—C7	1.3893 (15)	C16—C17	1.4967 (19)
C6—C11	1.3910 (15)	C16—H16A	0.99
C6—N1	1.4220 (13)	C16—H16B	0.99
C7—C8	1.3887 (16)	C17—H17A	0.98
C7—H7	0.95	C17—H17B	0.98
C8—C9	1.3864 (19)	C17—H17C	0.98
C8—H8	0.95	N1—N2	1.4066 (12)
C9—C10	1.3844 (19)	N3—H3	0.886 (18)
C9—H9	0.95
O1—C1—N1	124.87 (10)	C6—C11—H11	120.6
O1—C1—C2	130.90 (10)	N3—C12—C14	121.96 (10)
N1—C1—C2	104.11 (9)	N3—C12—C13	117.81 (10)
C3—C2—N3	128.24 (10)	C14—C12—C13	120.22 (10)
C3—C2—C1	108.94 (9)	C12—C13—H13A	109.5
N3—C2—C1	122.53 (9)	C12—C13—H13B	109.5
C2—C3—N2	109.74 (9)	H13A—C13—H13B	109.5
C2—C3—C4	129.89 (10)	C12—C13—H13C	109.5
N2—C3—C4	120.37 (9)	H13A—C13—H13C	109.5
C3—C4—H4A	109.5	H13B—C13—H13C	109.5
C3—C4—H4B	109.5	C12—C14—C15	123.23 (10)
H4A—C4—H4B	109.5	C12—C14—H14	118.4
C3—C4—H4C	109.5	C15—C14—H14	118.4
H4A—C4—H4C	109.5	O2—C15—O3	121.93 (10)
H4B—C4—H4C	109.5	O2—C15—C14	126.09 (10)
N2—C5—H5A	109.5	O3—C15—C14	111.98 (9)
N2—C5—H5B	109.5	O3—C16—C17	112.31 (11)
H5A—C5—H5B	109.5	O3—C16—H16A	109.1
N2—C5—H5C	109.5	C17—C16—H16A	109.1
H5A—C5—H5C	109.5	O3—C16—H16B	109.1
H5B—C5—H5C	109.5	C17—C16—H16B	109.1
C7—C6—C11	121.12 (10)	H16A—C16—H16B	107.9
C7—C6—N1	120.86 (10)	C16—C17—H17A	109.5
C11—C6—N1	118.00 (9)	C16—C17—H17B	109.5
C8—C7—C6	119.36 (11)	H17A—C17—H17B	109.5
C8—C7—H7	120.3	C16—C17—H17C	109.5
C6—C7—H7	120.3	H17A—C17—H17C	109.5
C9—C8—C7	119.90 (11)	H17B—C17—H17C	109.5
C9—C8—H8	120	C1—N1—N2	110.02 (8)
C7—C8—H8	120	C1—N1—C6	125.40 (9)
C10—C9—C8	120.22 (11)	N2—N1—C6	120.11 (8)
C10—C9—H9	119.9	C3—N2—N1	106.42 (8)
C8—C9—H9	119.9	C3—N2—C5	121.50 (9)
C9—C10—C11	120.66 (11)	N1—N2—C5	115.71 (9)
C9—C10—H10	119.7	C12—N3—C2	126.39 (9)
C11—C10—H10	119.7	C12—N3—H3	114.8 (11)
C10—C11—C6	118.73 (10)	C2—N3—H3	118.6 (11)
C10—C11—H11	120.6	C15—O3—C16	116.46 (9)
O1—C1—C2—C3	−171.19 (11)	O1—C1—N1—C6	11.97 (17)
N1—C1—C2—C3	4.94 (11)	C2—C1—N1—C6	−164.46 (9)
O1—C1—C2—N3	3.12 (17)	C7—C6—N1—C1	114.34 (12)
N1—C1—C2—N3	179.25 (9)	C11—C6—N1—C1	−64.49 (14)
N3—C2—C3—N2	−173.49 (9)	C7—C6—N1—N2	−39.49 (14)
C1—C2—C3—N2	0.40 (11)	C11—C6—N1—N2	141.68 (10)
N3—C2—C3—C4	6.68 (18)	C2—C3—N2—N1	−5.57 (11)
C1—C2—C3—C4	−179.43 (10)	C4—C3—N2—N1	174.28 (9)
C11—C6—C7—C8	0.22 (16)	C2—C3—N2—C5	−140.90 (10)
N1—C6—C7—C8	−178.58 (9)	C4—C3—N2—C5	38.95 (14)
C6—C7—C8—C9	0.46 (17)	C1—N1—N2—C3	8.90 (11)
C7—C8—C9—C10	−0.80 (18)	C6—N1—N2—C3	166.40 (9)
C8—C9—C10—C11	0.47 (18)	C1—N1—N2—C5	147.19 (9)
C9—C10—C11—C6	0.20 (17)	C6—N1—N2—C5	−55.31 (12)
C7—C6—C11—C10	−0.54 (16)	C14—C12—N3—C2	179.44 (10)
N1—C6—C11—C10	178.29 (9)	C13—C12—N3—C2	−0.92 (17)
N3—C12—C14—C15	1.55 (18)	C3—C2—N3—C12	−69.82 (16)
C13—C12—C14—C15	−178.08 (11)	C1—C2—N3—C12	117.04 (12)
C12—C14—C15—O2	2.80 (18)	O2—C15—O3—C16	1.37 (16)
C12—C14—C15—O3	−177.10 (10)	C14—C15—O3—C16	−178.72 (10)
O1—C1—N1—N2	168.01 (10)	C17—C16—O3—C15	−81.62 (13)
C2—C1—N1—N2	−8.42 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.886 (18)	2.009 (18)	2.7192 (12)	136 (1)
C11—H11···O1^i	0.95	2.35	3.2829 (14)	167
C8—H8···O3^ii	0.95	2.7	3.6206 (15)	164

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

(IV) Ethyl 2-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]cyclohex-1-enecarboxylate

Crystal data

C20H25N3O3	Z = 2
Mr = 355.43	F(000) = 380
Triclinic, P1	Dx = 1.274 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3857 (2) Å	Cell parameters from 8186 reflections
b = 9.2159 (3) Å	θ = 2.2–28.3°
c = 13.7494 (4) Å	µ = 0.09 mm^−1
α = 85.898 (1)°	T = 173 K
β = 84.499 (1)°	Plate, colourless
γ = 85.210 (1)°	0.3 × 0.3 × 0.19 mm
V = 926.40 (5) Å^3

Data collection

Bruker D8 Venture Photon diffractometer	3628 reflections with I > 2σ(I)
ω scans	Rint = 0.043
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 1.5°
Tmin = 0.95, Tmax = 0.96	h = −9→9
20559 measured reflections	k = −12→11
4466 independent reflections	l = −18→18

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0494P)^2 + 0.2134P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.24 e Å^−3
4466 reflections	Δρmin = −0.23 e Å^−3
242 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.69149 (16)	0.77040 (13)	0.44703 (8)	0.0257 (2)
C2	0.56088 (16)	0.70172 (13)	0.39711 (8)	0.0253 (2)
C3	0.41466 (16)	0.67442 (12)	0.46160 (8)	0.0252 (2)
C4	0.24182 (17)	0.61259 (14)	0.44459 (9)	0.0325 (3)
H4A	0.2502	0.5807	0.3777	0.049*
H4B	0.1402	0.6873	0.4535	0.049*
H4C	0.2211	0.529	0.4913	0.049*
C5	0.29521 (17)	0.78324 (14)	0.61675 (9)	0.0302 (3)
H5A	0.2666	0.8836	0.5909	0.045*
H5B	0.3322	0.7843	0.6833	0.045*
H5C	0.187	0.7281	0.6182	0.045*
C6	0.70009 (16)	0.81214 (13)	0.62319 (8)	0.0249 (2)
C7	0.69056 (18)	0.71728 (13)	0.70625 (8)	0.0292 (3)
H7	0.6208	0.6348	0.709	0.035*
C8	0.78386 (19)	0.74410 (14)	0.78510 (9)	0.0341 (3)
H8	0.7779	0.6797	0.8422	0.041*
C9	0.88554 (19)	0.86411 (15)	0.78110 (9)	0.0345 (3)
H9	0.9494	0.8818	0.8353	0.041*
C10	0.89427 (17)	0.95840 (14)	0.69818 (9)	0.0320 (3)
H10	0.9639	1.041	0.6957	0.038*
C11	0.80186 (17)	0.93284 (13)	0.61877 (9)	0.0285 (3)
H11	0.8081	0.9974	0.5617	0.034*
C12	0.63541 (15)	0.74644 (12)	0.22002 (8)	0.0239 (2)
C13	0.68815 (15)	0.69490 (12)	0.12974 (8)	0.0236 (2)
C14	0.73716 (17)	0.79641 (13)	0.04140 (8)	0.0268 (3)
H14A	0.6382	0.8023	−0.0028	0.032*
H14B	0.8499	0.7551	0.0053	0.032*
C15	0.7664 (2)	0.94900 (14)	0.06831 (9)	0.0339 (3)
H15A	0.8841	0.9481	0.0974	0.041*
H15B	0.7713	1.0159	0.0086	0.041*
C16	0.6127 (2)	1.00262 (14)	0.14074 (9)	0.0346 (3)
H16A	0.4944	0.9992	0.113	0.042*
H16B	0.6271	1.105	0.1539	0.042*
C17	0.61487 (18)	0.90701 (13)	0.23578 (8)	0.0292 (3)
H17A	0.7169	0.9316	0.2718	0.035*
H17B	0.4999	0.9291	0.2771	0.035*
C18	0.69463 (16)	0.54040 (13)	0.11583 (8)	0.0253 (2)
C19	0.74116 (19)	0.35824 (13)	0.00053 (9)	0.0318 (3)
H19A	0.6193	0.3218	0.0185	0.038*
H19B	0.8307	0.2988	0.0388	0.038*
C20	0.7937 (2)	0.34768 (15)	−0.10745 (10)	0.0365 (3)
H20A	0.7042	0.407	−0.1446	0.055*
H20B	0.7963	0.2457	−0.1238	0.055*
H20C	0.9148	0.3835	−0.1243	0.055*
N1	0.60598 (13)	0.78805 (11)	0.54063 (7)	0.0262 (2)
N2	0.44476 (13)	0.71398 (11)	0.55359 (7)	0.0256 (2)
N3	0.59282 (14)	0.65599 (12)	0.30077 (7)	0.0273 (2)
H3	0.608 (2)	0.5608 (18)	0.2902 (11)	0.043 (4)*
O1	0.84587 (12)	0.80604 (10)	0.41948 (6)	0.0331 (2)
O2	0.66354 (13)	0.44227 (9)	0.17906 (6)	0.0339 (2)
O3	0.73861 (12)	0.50993 (9)	0.02103 (6)	0.0285 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0294 (6)	0.0280 (6)	0.0186 (5)	−0.0005 (5)	−0.0004 (4)	0.0019 (4)
C2	0.0295 (6)	0.0264 (6)	0.0192 (5)	−0.0004 (5)	−0.0007 (4)	0.0004 (4)
C3	0.0281 (6)	0.0235 (5)	0.0235 (5)	0.0003 (5)	−0.0025 (4)	−0.0013 (4)
C4	0.0302 (7)	0.0350 (7)	0.0330 (6)	−0.0043 (5)	−0.0030 (5)	−0.0048 (5)
C5	0.0310 (6)	0.0336 (6)	0.0248 (6)	−0.0015 (5)	0.0049 (5)	−0.0048 (5)
C6	0.0273 (6)	0.0282 (6)	0.0191 (5)	−0.0024 (5)	0.0002 (4)	−0.0031 (4)
C7	0.0403 (7)	0.0270 (6)	0.0208 (5)	−0.0090 (5)	0.0002 (5)	−0.0023 (4)
C8	0.0487 (8)	0.0343 (7)	0.0200 (5)	−0.0080 (6)	−0.0041 (5)	0.0002 (5)
C9	0.0396 (7)	0.0406 (7)	0.0255 (6)	−0.0087 (6)	−0.0060 (5)	−0.0064 (5)
C10	0.0315 (7)	0.0335 (7)	0.0320 (6)	−0.0109 (5)	0.0017 (5)	−0.0048 (5)
C11	0.0306 (6)	0.0289 (6)	0.0252 (6)	−0.0048 (5)	0.0016 (5)	0.0022 (5)
C12	0.0230 (6)	0.0277 (6)	0.0207 (5)	−0.0016 (5)	−0.0029 (4)	0.0010 (4)
C13	0.0250 (6)	0.0259 (6)	0.0200 (5)	−0.0034 (4)	−0.0022 (4)	0.0000 (4)
C14	0.0329 (6)	0.0278 (6)	0.0197 (5)	−0.0048 (5)	−0.0017 (4)	−0.0002 (4)
C15	0.0485 (8)	0.0283 (6)	0.0249 (6)	−0.0096 (6)	−0.0002 (5)	0.0010 (5)
C16	0.0519 (8)	0.0255 (6)	0.0257 (6)	0.0014 (6)	−0.0043 (5)	−0.0001 (5)
C17	0.0378 (7)	0.0272 (6)	0.0219 (5)	0.0015 (5)	−0.0020 (5)	−0.0023 (4)
C18	0.0252 (6)	0.0288 (6)	0.0218 (5)	−0.0020 (5)	−0.0009 (4)	−0.0015 (4)
C19	0.0383 (7)	0.0245 (6)	0.0326 (6)	−0.0015 (5)	−0.0018 (5)	−0.0051 (5)
C20	0.0421 (8)	0.0344 (7)	0.0333 (7)	−0.0002 (6)	−0.0021 (6)	−0.0097 (5)
N1	0.0273 (5)	0.0334 (5)	0.0181 (4)	−0.0078 (4)	0.0008 (4)	−0.0008 (4)
N2	0.0250 (5)	0.0302 (5)	0.0215 (5)	−0.0047 (4)	0.0020 (4)	−0.0032 (4)
N3	0.0367 (6)	0.0263 (5)	0.0181 (5)	−0.0020 (4)	0.0005 (4)	−0.0010 (4)
O1	0.0283 (5)	0.0460 (5)	0.0241 (4)	−0.0077 (4)	0.0016 (3)	0.0034 (4)
O2	0.0481 (6)	0.0267 (4)	0.0258 (4)	−0.0057 (4)	0.0022 (4)	0.0016 (3)
O3	0.0378 (5)	0.0250 (4)	0.0225 (4)	−0.0034 (4)	0.0010 (3)	−0.0040 (3)

Geometric parameters (Å, º)

C1—O1	1.2302 (14)	C12—C13	1.3707 (15)
C1—N1	1.3924 (14)	C12—C17	1.5040 (16)
C1—C2	1.4468 (17)	C13—C18	1.4464 (16)
C2—C3	1.3586 (17)	C13—C14	1.5137 (15)
C2—N3	1.4110 (14)	C14—C15	1.5171 (17)
C3—N2	1.3840 (14)	C14—H14A	0.99
C3—C4	1.4856 (17)	C14—H14B	0.99
C4—H4A	0.98	C15—C16	1.5115 (19)
C4—H4B	0.98	C15—H15A	0.99
C4—H4C	0.98	C15—H15B	0.99
C5—N2	1.4694 (15)	C16—C17	1.5235 (16)
C5—H5A	0.98	C16—H16A	0.99
C5—H5B	0.98	C16—H16B	0.99
C5—H5C	0.98	C17—H17A	0.99
C6—C7	1.3876 (16)	C17—H17B	0.99
C6—C11	1.3882 (16)	C18—O2	1.2289 (14)
C6—N1	1.4261 (14)	C18—O3	1.3562 (13)
C7—C8	1.3862 (17)	C19—O3	1.4439 (14)
C7—H7	0.95	C19—C20	1.5061 (18)
C8—C9	1.3828 (18)	C19—H19A	0.99
C8—H8	0.95	C19—H19B	0.99
C9—C10	1.3830 (18)	C20—H20A	0.98
C9—H9	0.95	C20—H20B	0.98
C10—C11	1.3856 (17)	C20—H20C	0.98
C10—H10	0.95	N1—N2	1.4118 (13)
C11—H11	0.95	N3—H3	0.896 (16)
C12—N3	1.3679 (15)
O1—C1—N1	124.35 (11)	C15—C14—H14A	109
O1—C1—C2	131.25 (11)	C13—C14—H14B	109
N1—C1—C2	104.39 (10)	C15—C14—H14B	109
C3—C2—N3	126.34 (11)	H14A—C14—H14B	107.8
C3—C2—C1	108.72 (10)	C16—C15—C14	110.09 (11)
N3—C2—C1	124.54 (10)	C16—C15—H15A	109.6
C2—C3—N2	109.92 (10)	C14—C15—H15A	109.6
C2—C3—C4	129.23 (11)	C16—C15—H15B	109.6
N2—C3—C4	120.85 (10)	C14—C15—H15B	109.6
C3—C4—H4A	109.5	H15A—C15—H15B	108.2
C3—C4—H4B	109.5	C15—C16—C17	109.66 (11)
H4A—C4—H4B	109.5	C15—C16—H16A	109.7
C3—C4—H4C	109.5	C17—C16—H16A	109.7
H4A—C4—H4C	109.5	C15—C16—H16B	109.7
H4B—C4—H4C	109.5	C17—C16—H16B	109.7
N2—C5—H5A	109.5	H16A—C16—H16B	108.2
N2—C5—H5B	109.5	C12—C17—C16	113.24 (10)
H5A—C5—H5B	109.5	C12—C17—H17A	108.9
N2—C5—H5C	109.5	C16—C17—H17A	108.9
H5A—C5—H5C	109.5	C12—C17—H17B	108.9
H5B—C5—H5C	109.5	C16—C17—H17B	108.9
C7—C6—C11	120.54 (11)	H17A—C17—H17B	107.7
C7—C6—N1	120.92 (10)	O2—C18—O3	120.68 (10)
C11—C6—N1	118.55 (10)	O2—C18—C13	126.86 (10)
C8—C7—C6	119.34 (11)	O3—C18—C13	112.46 (9)
C8—C7—H7	120.3	O3—C19—C20	107.49 (10)
C6—C7—H7	120.3	O3—C19—H19A	110.2
C9—C8—C7	120.38 (11)	C20—C19—H19A	110.2
C9—C8—H8	119.8	O3—C19—H19B	110.2
C7—C8—H8	119.8	C20—C19—H19B	110.2
C8—C9—C10	120.01 (11)	H19A—C19—H19B	108.5
C8—C9—H9	120	C19—C20—H20A	109.5
C10—C9—H9	120	C19—C20—H20B	109.5
C9—C10—C11	120.22 (11)	H20A—C20—H20B	109.5
C9—C10—H10	119.9	C19—C20—H20C	109.5
C11—C10—H10	119.9	H20A—C20—H20C	109.5
C10—C11—C6	119.51 (11)	H20B—C20—H20C	109.5
C10—C11—H11	120.2	C1—N1—N2	109.98 (9)
C6—C11—H11	120.2	C1—N1—C6	123.86 (10)
N3—C12—C13	122.39 (10)	N2—N1—C6	120.08 (9)
N3—C12—C17	115.68 (10)	C3—N2—N1	105.89 (9)
C13—C12—C17	121.90 (10)	C3—N2—C5	120.39 (10)
C12—C13—C18	120.43 (10)	N1—N2—C5	115.15 (9)
C12—C13—C14	121.70 (10)	C12—N3—C2	124.33 (10)
C18—C13—C14	117.85 (10)	C12—N3—H3	114.4 (10)
C13—C14—C15	112.91 (9)	C2—N3—H3	120.3 (10)
C13—C14—H14A	109	C18—O3—C19	115.81 (9)
O1—C1—C2—C3	175.21 (12)	C12—C13—C18—O2	−3.08 (19)
N1—C1—C2—C3	−3.53 (13)	C14—C13—C18—O2	178.25 (11)
O1—C1—C2—N3	2.1 (2)	C12—C13—C18—O3	176.17 (10)
N1—C1—C2—N3	−176.63 (10)	C14—C13—C18—O3	−2.50 (15)
N3—C2—C3—N2	169.71 (11)	O1—C1—N1—N2	−169.93 (11)
C1—C2—C3—N2	−3.24 (13)	C2—C1—N1—N2	8.92 (12)
N3—C2—C3—C4	−10.5 (2)	O1—C1—N1—C6	−17.55 (18)
C1—C2—C3—C4	176.55 (12)	C2—C1—N1—C6	161.30 (10)
C11—C6—C7—C8	0.00 (19)	C7—C6—N1—C1	−121.50 (13)
N1—C6—C7—C8	179.98 (11)	C11—C6—N1—C1	58.49 (16)
C6—C7—C8—C9	0.0 (2)	C7—C6—N1—N2	28.28 (16)
C7—C8—C9—C10	0.1 (2)	C11—C6—N1—N2	−151.74 (11)
C8—C9—C10—C11	−0.2 (2)	C2—C3—N2—N1	8.61 (13)
C9—C10—C11—C6	0.18 (19)	C4—C3—N2—N1	−171.21 (10)
C7—C6—C11—C10	−0.07 (19)	C2—C3—N2—C5	141.38 (11)
N1—C6—C11—C10	179.95 (11)	C4—C3—N2—C5	−38.44 (16)
N3—C12—C13—C18	2.18 (17)	C1—N1—N2—C3	−11.00 (12)
C17—C12—C13—C18	−175.80 (11)	C6—N1—N2—C3	−164.59 (10)
N3—C12—C13—C14	−179.20 (10)	C1—N1—N2—C5	−146.61 (10)
C17—C12—C13—C14	2.82 (17)	C6—N1—N2—C5	59.80 (14)
C12—C13—C14—C15	14.10 (16)	C13—C12—N3—C2	171.45 (11)
C18—C13—C14—C15	−167.24 (11)	C17—C12—N3—C2	−10.46 (16)
C13—C14—C15—C16	−47.09 (14)	C3—C2—N3—C12	129.14 (13)
C14—C15—C16—C17	63.96 (14)	C1—C2—N3—C12	−58.97 (17)
N3—C12—C17—C16	−164.18 (11)	O2—C18—O3—C19	1.53 (16)
C13—C12—C17—C16	13.92 (17)	C13—C18—O3—C19	−177.77 (10)
C15—C16—C17—C12	−46.68 (15)	C20—C19—O3—C18	−179.63 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.896 (16)	1.934 (16)	2.6618 (13)	137 (1)

(V) (Z)-Ethyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]-3-phenylacrylate

Crystal data

C22H23N3O3	F(000) = 800
Mr = 377.43	Dx = 1.32 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9961 reflections
a = 8.4851 (7) Å	θ = 3.2–28.2°
b = 12.4253 (10) Å	µ = 0.09 mm^−1
c = 18.0314 (18) Å	T = 173 K
β = 92.282 (3)°	Plate, yellow
V = 1899.5 (3) Å^3	0.44 × 0.34 × 0.11 mm
Z = 4

Data collection

Bruker D8 Venture Photon diffractometer	3838 reflections with I > 2σ(I)
ω scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 3.3°
Tmin = 0.95, Tmax = 0.96	h = −10→11
28673 measured reflections	k = −16→16
4570 independent reflections	l = −23→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.6436P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.28 e Å^−3
4570 reflections	Δρmin = −0.19 e Å^−3
260 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.73101 (12)	0.24095 (9)	0.38575 (6)	0.0235 (2)
C2	0.68561 (12)	0.34800 (9)	0.36110 (6)	0.0228 (2)
C3	0.79944 (12)	0.38855 (9)	0.31873 (6)	0.0220 (2)
C4	0.80437 (14)	0.49224 (9)	0.27788 (7)	0.0277 (2)
H4A	0.7825	0.4793	0.2248	0.042*
H4B	0.9091	0.5247	0.2852	0.042*
H4C	0.7247	0.5412	0.2967	0.042*
C5	0.98523 (15)	0.29227 (10)	0.24187 (6)	0.0289 (3)
H5A	0.9037	0.2555	0.2113	0.043*
H5B	1.0782	0.2458	0.2478	0.043*
H5C	1.0147	0.3595	0.2176	0.043*
C6	0.99274 (12)	0.14792 (9)	0.37750 (6)	0.0210 (2)
C7	1.15038 (13)	0.17856 (9)	0.38681 (6)	0.0238 (2)
H7	1.1819	0.2497	0.3751	0.029*
C8	1.26092 (13)	0.10407 (10)	0.41337 (6)	0.0285 (2)
H8	1.3687	0.1242	0.4194	0.034*
C9	1.21484 (15)	0.00056 (10)	0.43107 (6)	0.0305 (3)
H9	1.2902	−0.0496	0.4505	0.037*
C10	1.05869 (15)	−0.02949 (9)	0.42031 (6)	0.0289 (3)
H10	1.0275	−0.1008	0.4319	0.035*
C11	0.94718 (13)	0.04313 (9)	0.39279 (6)	0.0250 (2)
H11	0.8406	0.0215	0.3844	0.03*
C12	0.42177 (12)	0.41268 (8)	0.32552 (6)	0.0226 (2)
C13	0.43943 (12)	0.36614 (9)	0.25002 (6)	0.0235 (2)
C14	0.46922 (13)	0.25684 (10)	0.23929 (7)	0.0287 (2)
H14	0.48	0.21	0.2808	0.034*
C15	0.48312 (14)	0.21660 (10)	0.16805 (8)	0.0343 (3)
H15	0.5039	0.1422	0.1612	0.041*
C16	0.46709 (14)	0.28360 (11)	0.10689 (7)	0.0356 (3)
H16	0.4784	0.2556	0.0584	0.043*
C17	0.43452 (14)	0.39154 (11)	0.11684 (7)	0.0323 (3)
H17	0.421	0.4376	0.075	0.039*
C18	0.42150 (13)	0.43263 (10)	0.18807 (7)	0.0275 (2)
H18	0.4001	0.507	0.1946	0.033*
C19	0.28782 (13)	0.46926 (9)	0.33825 (6)	0.0256 (2)
H19	0.2096	0.4728	0.2991	0.031*
C20	0.25582 (12)	0.52413 (9)	0.40659 (6)	0.0249 (2)
C21	0.06614 (15)	0.63645 (11)	0.46383 (7)	0.0336 (3)
H21A	0.1338	0.701	0.4698	0.04*
H21B	0.0747	0.5937	0.5102	0.04*
C22	−0.10227 (15)	0.66841 (12)	0.44690 (7)	0.0376 (3)
H22A	−0.1097	0.7066	0.3993	0.056*
H22B	−0.1384	0.7156	0.4863	0.056*
H22C	−0.1685	0.6038	0.444	0.056*
N1	0.87573 (10)	0.22321 (7)	0.35321 (5)	0.0233 (2)
N2	0.92385 (10)	0.31639 (7)	0.31523 (5)	0.02214 (19)
N3	0.54052 (11)	0.39661 (8)	0.37760 (6)	0.0269 (2)
H3	0.5283 (17)	0.4200 (12)	0.4223 (9)	0.036 (4)*
O1	0.66500 (9)	0.17733 (7)	0.42638 (5)	0.0320 (2)
O2	0.34206 (10)	0.52933 (8)	0.46196 (5)	0.0347 (2)
O3	0.11324 (10)	0.57275 (7)	0.40133 (5)	0.0329 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0181 (5)	0.0287 (6)	0.0236 (5)	0.0013 (4)	−0.0002 (4)	0.0024 (4)
C2	0.0199 (5)	0.0268 (5)	0.0215 (5)	0.0039 (4)	−0.0006 (4)	0.0012 (4)
C3	0.0213 (5)	0.0244 (5)	0.0199 (5)	0.0033 (4)	−0.0027 (4)	0.0004 (4)
C4	0.0283 (6)	0.0258 (6)	0.0292 (6)	0.0036 (5)	0.0016 (4)	0.0055 (5)
C5	0.0313 (6)	0.0319 (6)	0.0240 (6)	0.0048 (5)	0.0058 (4)	0.0021 (5)
C6	0.0208 (5)	0.0234 (5)	0.0188 (5)	0.0044 (4)	0.0009 (4)	−0.0001 (4)
C7	0.0224 (5)	0.0250 (5)	0.0239 (5)	0.0017 (4)	0.0014 (4)	−0.0008 (4)
C8	0.0213 (5)	0.0389 (6)	0.0252 (5)	0.0063 (5)	0.0000 (4)	−0.0011 (5)
C9	0.0328 (6)	0.0344 (6)	0.0245 (5)	0.0153 (5)	0.0026 (5)	0.0029 (5)
C10	0.0396 (6)	0.0223 (5)	0.0251 (5)	0.0055 (5)	0.0057 (5)	0.0025 (4)
C11	0.0266 (5)	0.0249 (5)	0.0236 (5)	−0.0003 (4)	0.0020 (4)	−0.0001 (4)
C12	0.0192 (5)	0.0197 (5)	0.0290 (6)	−0.0008 (4)	0.0012 (4)	0.0028 (4)
C13	0.0155 (5)	0.0251 (5)	0.0296 (6)	−0.0002 (4)	−0.0004 (4)	−0.0016 (4)
C14	0.0235 (5)	0.0247 (6)	0.0378 (6)	0.0002 (4)	0.0012 (5)	0.0006 (5)
C15	0.0272 (6)	0.0277 (6)	0.0482 (8)	0.0001 (5)	0.0039 (5)	−0.0099 (5)
C16	0.0265 (6)	0.0462 (8)	0.0341 (7)	−0.0036 (5)	0.0026 (5)	−0.0121 (6)
C17	0.0257 (6)	0.0413 (7)	0.0296 (6)	−0.0025 (5)	−0.0026 (5)	0.0020 (5)
C18	0.0220 (5)	0.0264 (6)	0.0337 (6)	0.0008 (4)	−0.0027 (4)	−0.0002 (5)
C19	0.0194 (5)	0.0260 (5)	0.0310 (6)	0.0020 (4)	−0.0027 (4)	−0.0022 (4)
C20	0.0190 (5)	0.0249 (5)	0.0307 (6)	0.0019 (4)	0.0000 (4)	0.0025 (4)
C21	0.0328 (6)	0.0391 (7)	0.0286 (6)	0.0108 (5)	−0.0015 (5)	−0.0093 (5)
C22	0.0329 (7)	0.0473 (8)	0.0328 (7)	0.0130 (6)	0.0033 (5)	−0.0082 (6)
N1	0.0193 (4)	0.0233 (5)	0.0275 (5)	0.0018 (4)	0.0025 (3)	0.0065 (4)
N2	0.0212 (4)	0.0226 (4)	0.0228 (4)	0.0023 (4)	0.0028 (3)	0.0048 (3)
N3	0.0224 (5)	0.0351 (5)	0.0231 (5)	0.0094 (4)	0.0017 (4)	0.0018 (4)
O1	0.0240 (4)	0.0344 (5)	0.0380 (5)	0.0014 (3)	0.0071 (3)	0.0121 (4)
O2	0.0266 (4)	0.0490 (5)	0.0282 (4)	0.0089 (4)	−0.0028 (3)	−0.0001 (4)
O3	0.0251 (4)	0.0415 (5)	0.0317 (4)	0.0127 (4)	−0.0039 (3)	−0.0110 (4)

Geometric parameters (Å, º)

C1—O1	1.2280 (14)	C12—N3	1.3645 (14)
C1—N1	1.3994 (14)	C12—C13	1.4920 (16)
C1—C2	1.4497 (15)	C13—C18	1.3929 (16)
C2—C3	1.3526 (15)	C13—C14	1.3963 (16)
C2—N3	1.4135 (14)	C14—C15	1.3878 (18)
C3—N2	1.3884 (14)	C14—H14	0.95
C3—C4	1.4855 (15)	C15—C16	1.384 (2)
C4—H4A	0.98	C15—H15	0.95
C4—H4B	0.98	C16—C17	1.3825 (19)
C4—H4C	0.98	C16—H16	0.95
C5—N2	1.4716 (14)	C17—C18	1.3905 (17)
C5—H5A	0.98	C17—H17	0.95
C5—H5B	0.98	C18—H18	0.95
C5—H5C	0.98	C19—C20	1.4435 (16)
C6—C11	1.3890 (15)	C19—H19	0.95
C6—C7	1.3945 (15)	C20—O2	1.2159 (14)
C6—N1	1.4206 (13)	C20—O3	1.3522 (13)
C7—C8	1.3892 (16)	C21—O3	1.4465 (14)
C7—H7	0.95	C21—C22	1.5027 (17)
C8—C9	1.3852 (18)	C21—H21A	0.99
C8—H8	0.95	C21—H21B	0.99
C9—C10	1.3828 (18)	C22—H22A	0.98
C9—H9	0.95	C22—H22B	0.98
C10—C11	1.3850 (16)	C22—H22C	0.98
C10—H10	0.95	N1—N2	1.4136 (12)
C11—H11	0.95	N3—H3	0.867 (16)
C12—C19	1.3637 (15)
O1—C1—N1	125.27 (10)	C14—C13—C12	121.92 (10)
O1—C1—C2	130.66 (10)	C15—C14—C13	120.08 (12)
N1—C1—C2	104.05 (9)	C15—C14—H14	120
C3—C2—N3	127.39 (10)	C13—C14—H14	120
C3—C2—C1	109.14 (9)	C16—C15—C14	120.76 (12)
N3—C2—C1	123.41 (10)	C16—C15—H15	119.6
C2—C3—N2	110.27 (10)	C14—C15—H15	119.6
C2—C3—C4	129.64 (10)	C17—C16—C15	119.60 (12)
N2—C3—C4	120.08 (10)	C17—C16—H16	120.2
C3—C4—H4A	109.5	C15—C16—H16	120.2
C3—C4—H4B	109.5	C16—C17—C18	119.98 (12)
H4A—C4—H4B	109.5	C16—C17—H17	120
C3—C4—H4C	109.5	C18—C17—H17	120
H4A—C4—H4C	109.5	C17—C18—C13	120.86 (11)
H4B—C4—H4C	109.5	C17—C18—H18	119.6
N2—C5—H5A	109.5	C13—C18—H18	119.6
N2—C5—H5B	109.5	C12—C19—C20	125.00 (10)
H5A—C5—H5B	109.5	C12—C19—H19	117.5
N2—C5—H5C	109.5	C20—C19—H19	117.5
H5A—C5—H5C	109.5	O2—C20—O3	122.78 (11)
H5B—C5—H5C	109.5	O2—C20—C19	126.77 (10)
C11—C6—C7	120.35 (10)	O3—C20—C19	110.44 (9)
C11—C6—N1	118.81 (10)	O3—C21—C22	106.03 (10)
C7—C6—N1	120.84 (10)	O3—C21—H21A	110.5
C8—C7—C6	119.40 (11)	C22—C21—H21A	110.5
C8—C7—H7	120.3	O3—C21—H21B	110.5
C6—C7—H7	120.3	C22—C21—H21B	110.5
C9—C8—C7	120.34 (11)	H21A—C21—H21B	108.7
C9—C8—H8	119.8	C21—C22—H22A	109.5
C7—C8—H8	119.8	C21—C22—H22B	109.5
C10—C9—C8	119.74 (11)	H22A—C22—H22B	109.5
C10—C9—H9	120.1	C21—C22—H22C	109.5
C8—C9—H9	120.1	H22A—C22—H22C	109.5
C9—C10—C11	120.76 (11)	H22B—C22—H22C	109.5
C9—C10—H10	119.6	C1—N1—N2	110.45 (8)
C11—C10—H10	119.6	C1—N1—C6	126.06 (9)
C10—C11—C6	119.36 (11)	N2—N1—C6	118.48 (8)
C10—C11—H11	120.3	C3—N2—N1	105.79 (8)
C6—C11—H11	120.3	C3—N2—C5	117.99 (9)
C19—C12—N3	123.86 (11)	N1—N2—C5	112.84 (9)
C19—C12—C13	117.91 (10)	C12—N3—C2	122.90 (10)
N3—C12—C13	118.23 (9)	C12—N3—H3	118.6 (10)
C18—C13—C14	118.70 (11)	C2—N3—H3	118.4 (10)
C18—C13—C12	119.35 (10)	C20—O3—C21	117.64 (9)
O1—C1—C2—C3	177.76 (12)	N3—C12—C19—C20	3.14 (18)
N1—C1—C2—C3	−1.23 (12)	C13—C12—C19—C20	−176.56 (10)
O1—C1—C2—N3	−4.83 (19)	C12—C19—C20—O2	0.8 (2)
N1—C1—C2—N3	176.18 (10)	C12—C19—C20—O3	179.86 (11)
N3—C2—C3—N2	−179.52 (10)	O1—C1—N1—N2	−174.85 (11)
C1—C2—C3—N2	−2.24 (13)	C2—C1—N1—N2	4.21 (11)
N3—C2—C3—C4	−0.6 (2)	O1—C1—N1—C6	−20.54 (18)
C1—C2—C3—C4	176.65 (11)	C2—C1—N1—C6	158.52 (10)
C11—C6—C7—C8	−1.65 (16)	C11—C6—N1—C1	47.88 (15)
N1—C6—C7—C8	177.53 (10)	C7—C6—N1—C1	−131.33 (12)
C6—C7—C8—C9	−0.57 (17)	C11—C6—N1—N2	−159.65 (10)
C7—C8—C9—C10	1.77 (17)	C7—C6—N1—N2	21.15 (15)
C8—C9—C10—C11	−0.75 (17)	C2—C3—N2—N1	4.75 (12)
C9—C10—C11—C6	−1.46 (17)	C4—C3—N2—N1	−174.26 (9)
C7—C6—C11—C10	2.66 (16)	C2—C3—N2—C5	132.13 (10)
N1—C6—C11—C10	−176.55 (10)	C4—C3—N2—C5	−46.89 (14)
C19—C12—C13—C18	52.83 (14)	C1—N1—N2—C3	−5.60 (11)
N3—C12—C13—C18	−126.89 (11)	C6—N1—N2—C3	−162.10 (9)
C19—C12—C13—C14	−125.36 (12)	C1—N1—N2—C5	−136.01 (9)
N3—C12—C13—C14	54.92 (15)	C6—N1—N2—C5	67.49 (12)
C18—C13—C14—C15	1.09 (16)	C19—C12—N3—C2	−172.86 (11)
C12—C13—C14—C15	179.29 (10)	C13—C12—N3—C2	6.85 (16)
C13—C14—C15—C16	−0.29 (18)	C3—C2—N3—C12	68.10 (17)
C14—C15—C16—C17	−0.97 (18)	C1—C2—N3—C12	−108.82 (13)
C15—C16—C17—C18	1.41 (18)	O2—C20—O3—C21	2.31 (17)
C16—C17—C18—C13	−0.60 (17)	C19—C20—O3—C21	−176.77 (10)
C14—C13—C18—C17	−0.65 (16)	C22—C21—O3—C20	−173.01 (11)
C12—C13—C18—C17	−178.90 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.867 (16)	2.224 (15)	2.8413 (13)	128 (1)
N3—H3···O2^i	0.867 (16)	2.404 (16)	3.1590 (14)	146 (1)
C8—H8···O1^ii	0.95	2.6	3.5462 (15)	176

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

(VI) 2-Cyano-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)acetamide

Crystal data

C14H14N4O2	F(000) = 568
Mr = 270.29	Dx = 1.332 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9915 reflections
a = 6.9996 (8) Å	θ = 3.1–28.3°
b = 12.3350 (16) Å	µ = 0.09 mm^−1
c = 15.8345 (19) Å	T = 173 K
β = 99.666 (4)°	Needle, colourless
V = 1347.7 (3) Å^3	0.67 × 0.16 × 0.11 mm
Z = 4

Data collection

Bruker D8 Venture Photon diffractometer	2737 reflections with I > 2σ(I)
ω scans	Rint = 0.023
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 3.4°
Tmin = 0.98, Tmax = 0.99	h = −9→8
19472 measured reflections	k = −16→16
3252 independent reflections	l = −20→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.3708P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.27 e Å^−3
3252 reflections	Δρmin = −0.18 e Å^−3
187 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.34738 (14)	0.45507 (8)	0.10778 (6)	0.0226 (2)
C2	0.23701 (14)	0.55169 (8)	0.08681 (7)	0.0231 (2)
C3	0.05925 (15)	0.53893 (8)	0.11050 (7)	0.0246 (2)
C4	−0.10439 (16)	0.61652 (10)	0.10627 (8)	0.0327 (3)
H4A	−0.1001	0.6511	0.1623	0.049*
H4B	−0.2273	0.5776	0.0907	0.049*
H4C	−0.0937	0.6721	0.0631	0.049*
C5	−0.05781 (17)	0.41025 (11)	0.21283 (8)	0.0349 (3)
H5A	0.012	0.4399	0.2667	0.052*
H5B	−0.068	0.3313	0.2178	0.052*
H5C	−0.188	0.4419	0.2007	0.052*
C6	0.25170 (15)	0.27381 (9)	0.15402 (7)	0.0251 (2)
C7	0.11104 (18)	0.20547 (10)	0.11078 (8)	0.0346 (3)
H7	−0.0041	0.2344	0.0783	0.041*
C8	0.1407 (2)	0.09414 (11)	0.11558 (9)	0.0438 (3)
H8	0.044	0.0465	0.0873	0.053*
C9	0.3095 (2)	0.05252 (10)	0.16110 (9)	0.0436 (3)
H9	0.3303	−0.0236	0.1631	0.052*
C10	0.4488 (2)	0.12139 (11)	0.20388 (9)	0.0408 (3)
H10	0.5653	0.0923	0.2351	0.049*
C11	0.42005 (17)	0.23284 (10)	0.20169 (7)	0.0311 (2)
H11	0.5142	0.2801	0.2324	0.037*
C12	0.32054 (15)	0.74122 (9)	0.06778 (7)	0.0258 (2)
C13	0.41768 (18)	0.81538 (9)	0.00944 (8)	0.0327 (3)
H13A	0.4643	0.7711	−0.0351	0.039*
H13B	0.3212	0.8677	−0.0197	0.039*
C14	0.58016 (17)	0.87440 (10)	0.05817 (8)	0.0339 (3)
N1	0.22982 (12)	0.38856 (7)	0.14719 (6)	0.0247 (2)
N2	0.04759 (12)	0.43659 (7)	0.14307 (6)	0.0255 (2)
N3	0.30922 (13)	0.63698 (7)	0.04169 (6)	0.0252 (2)
H3	0.375 (2)	0.6174 (12)	−0.0003 (9)	0.036 (4)*
N4	0.70659 (18)	0.92148 (12)	0.09499 (9)	0.0551 (3)
O1	0.51052 (10)	0.42821 (6)	0.09377 (5)	0.02694 (18)
O2	0.25709 (13)	0.77685 (7)	0.12907 (5)	0.0345 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0215 (5)	0.0229 (5)	0.0232 (5)	−0.0034 (4)	0.0033 (4)	−0.0020 (4)
C2	0.0218 (5)	0.0207 (5)	0.0265 (5)	−0.0024 (4)	0.0037 (4)	−0.0016 (4)
C3	0.0224 (5)	0.0242 (5)	0.0267 (5)	−0.0022 (4)	0.0024 (4)	−0.0028 (4)
C4	0.0240 (5)	0.0304 (6)	0.0441 (7)	0.0030 (4)	0.0075 (5)	−0.0004 (5)
C5	0.0271 (5)	0.0451 (7)	0.0349 (6)	0.0021 (5)	0.0127 (5)	0.0062 (5)
C6	0.0273 (5)	0.0230 (5)	0.0262 (5)	−0.0017 (4)	0.0080 (4)	0.0028 (4)
C7	0.0336 (6)	0.0318 (6)	0.0374 (6)	−0.0078 (5)	0.0034 (5)	0.0018 (5)
C8	0.0554 (8)	0.0291 (6)	0.0493 (8)	−0.0148 (6)	0.0162 (6)	−0.0043 (5)
C9	0.0616 (9)	0.0229 (5)	0.0538 (8)	0.0021 (6)	0.0315 (7)	0.0066 (5)
C10	0.0448 (7)	0.0367 (7)	0.0438 (7)	0.0114 (5)	0.0159 (6)	0.0160 (6)
C11	0.0307 (5)	0.0324 (6)	0.0299 (6)	0.0007 (5)	0.0048 (4)	0.0054 (5)
C12	0.0241 (5)	0.0230 (5)	0.0288 (5)	−0.0017 (4)	0.0000 (4)	0.0009 (4)
C13	0.0382 (6)	0.0260 (5)	0.0332 (6)	−0.0068 (5)	0.0039 (5)	0.0036 (5)
C14	0.0301 (6)	0.0305 (6)	0.0424 (7)	−0.0026 (5)	0.0104 (5)	0.0031 (5)
N1	0.0193 (4)	0.0234 (4)	0.0321 (5)	−0.0004 (3)	0.0065 (3)	0.0018 (4)
N2	0.0189 (4)	0.0263 (4)	0.0323 (5)	−0.0001 (3)	0.0069 (3)	0.0017 (4)
N3	0.0258 (4)	0.0214 (4)	0.0295 (5)	−0.0026 (3)	0.0078 (4)	0.0001 (4)
N4	0.0384 (6)	0.0614 (8)	0.0645 (8)	−0.0176 (6)	0.0056 (6)	−0.0012 (7)
O1	0.0205 (3)	0.0281 (4)	0.0333 (4)	0.0005 (3)	0.0078 (3)	0.0015 (3)
O2	0.0416 (5)	0.0268 (4)	0.0365 (4)	−0.0031 (3)	0.0109 (4)	−0.0052 (3)

Geometric parameters (Å, º)

C1—O1	1.2442 (12)	C7—H7	0.95
C1—N1	1.3828 (13)	C8—C9	1.376 (2)
C1—C2	1.4288 (15)	C8—H8	0.95
C2—C3	1.3676 (14)	C9—C10	1.382 (2)
C2—N3	1.4120 (13)	C9—H9	0.95
C3—N2	1.3713 (14)	C10—C11	1.3889 (18)
C3—C4	1.4855 (15)	C10—H10	0.95
C4—H4A	0.98	C11—H11	0.95
C4—H4B	0.98	C12—O2	1.2153 (14)
C4—H4C	0.98	C12—N3	1.3489 (14)
C5—N2	1.4641 (14)	C12—C13	1.5373 (15)
C5—H5A	0.98	C13—C14	1.4575 (17)
C5—H5B	0.98	C13—H13A	0.99
C5—H5C	0.98	C13—H13B	0.99
C6—C11	1.3839 (16)	C14—N4	1.1345 (17)
C6—C7	1.3865 (16)	N1—N2	1.3980 (12)
C6—N1	1.4258 (14)	N3—H3	0.903 (15)
C7—C8	1.3890 (18)
O1—C1—N1	123.78 (9)	C7—C8—H8	119.8
O1—C1—C2	131.09 (10)	C8—C9—C10	120.05 (12)
N1—C1—C2	105.09 (8)	C8—C9—H9	120
C3—C2—N3	130.09 (10)	C10—C9—H9	120
C3—C2—C1	108.75 (9)	C9—C10—C11	120.57 (12)
N3—C2—C1	120.90 (9)	C9—C10—H10	119.7
C2—C3—N2	108.87 (9)	C11—C10—H10	119.7
C2—C3—C4	130.06 (10)	C6—C11—C10	118.80 (12)
N2—C3—C4	121.06 (9)	C6—C11—H11	120.6
C3—C4—H4A	109.5	C10—C11—H11	120.6
C3—C4—H4B	109.5	O2—C12—N3	125.37 (10)
H4A—C4—H4B	109.5	O2—C12—C13	121.50 (10)
C3—C4—H4C	109.5	N3—C12—C13	113.10 (10)
H4A—C4—H4C	109.5	C14—C13—C12	111.32 (10)
H4B—C4—H4C	109.5	C14—C13—H13A	109.4
N2—C5—H5A	109.5	C12—C13—H13A	109.4
N2—C5—H5B	109.5	C14—C13—H13B	109.4
H5A—C5—H5B	109.5	C12—C13—H13B	109.4
N2—C5—H5C	109.5	H13A—C13—H13B	108
H5A—C5—H5C	109.5	N4—C14—C13	178.86 (14)
H5B—C5—H5C	109.5	C1—N1—N2	109.57 (8)
C11—C6—C7	121.09 (11)	C1—N1—C6	123.96 (9)
C11—C6—N1	118.34 (10)	N2—N1—C6	120.65 (8)
C7—C6—N1	120.52 (10)	C3—N2—N1	107.23 (8)
C6—C7—C8	119.13 (12)	C3—N2—C5	123.88 (9)
C6—C7—H7	120.4	N1—N2—C5	116.24 (9)
C8—C7—H7	120.4	C12—N3—C2	124.25 (9)
C9—C8—C7	120.33 (13)	C12—N3—H3	118.1 (9)
C9—C8—H8	119.8	C2—N3—H3	116.3 (9)
O1—C1—C2—C3	175.50 (11)	C2—C1—N1—N2	5.83 (11)
N1—C1—C2—C3	−2.28 (11)	O1—C1—N1—C6	−19.06 (16)
O1—C1—C2—N3	0.73 (17)	C2—C1—N1—C6	158.93 (9)
N1—C1—C2—N3	−177.05 (9)	C11—C6—N1—C1	64.08 (14)
N3—C2—C3—N2	171.96 (10)	C7—C6—N1—C1	−113.18 (12)
C1—C2—C3—N2	−2.17 (12)	C11—C6—N1—N2	−145.63 (10)
N3—C2—C3—C4	−8.91 (19)	C7—C6—N1—N2	37.12 (15)
C1—C2—C3—C4	176.96 (11)	C2—C3—N2—N1	5.73 (11)
C11—C6—C7—C8	−0.10 (18)	C4—C3—N2—N1	−173.49 (10)
N1—C6—C7—C8	177.09 (11)	C2—C3—N2—C5	145.71 (10)
C6—C7—C8—C9	−1.4 (2)	C4—C3—N2—C5	−33.51 (15)
C7—C8—C9—C10	1.4 (2)	C1—N1—N2—C3	−7.30 (11)
C8—C9—C10—C11	0.21 (19)	C6—N1—N2—C3	−161.43 (9)
C7—C6—C11—C10	1.66 (17)	C1—N1—N2—C5	−150.77 (10)
N1—C6—C11—C10	−175.58 (10)	C6—N1—N2—C5	55.10 (13)
C9—C10—C11—C6	−1.72 (18)	O2—C12—N3—C2	−6.09 (17)
O2—C12—C13—C14	56.70 (15)	C13—C12—N3—C2	176.09 (9)
N3—C12—C13—C14	−125.39 (11)	C3—C2—N3—C12	58.82 (16)
O1—C1—N1—N2	−172.16 (9)	C1—C2—N3—C12	−127.66 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^i	0.903 (15)	1.884 (15)	2.7835 (12)	174 (1)
C9—H9···O2^ii	0.95	2.55	3.4485 (16)	157

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

(VII) Methyl 4-{[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]methyl}benzoate

Crystal data

C20H19N3O3	F(000) = 1472
Mr = 349.38	Dx = 1.298 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8137 reflections
a = 32.7563 (10) Å	θ = 2.6–28.0°
b = 6.9258 (2) Å	µ = 0.09 mm^−1
c = 16.4002 (5) Å	T = 173 K
β = 106.032 (1)°	Plate, yellow
V = 3575.90 (19) Å^3	0.68 × 0.24 × 0.09 mm
Z = 8

Data collection

Bruker D8 Venture Photon diffractometer	3539 reflections with I > 2σ(I)
ω scans	Rint = 0.040
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 28.0°, θmin = 2.6°
Tmin = 0.95, Tmax = 0.99	h = −41→43
31732 measured reflections	k = −9→8
4312 independent reflections	l = −21→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 2.065P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.110	(Δ/σ)max = 0.002
S = 1.03	Δρmax = 0.24 e Å^−3
4312 reflections	Δρmin = −0.30 e Å^−3
238 parameters

Special details

Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.31423 (4)	0.32838 (17)	0.65668 (7)	0.0249 (2)
C2	0.27746 (4)	0.20497 (17)	0.64224 (7)	0.0241 (2)
C3	0.28930 (4)	0.03859 (17)	0.68905 (7)	0.0249 (2)
C4	0.26341 (4)	−0.13591 (19)	0.69093 (8)	0.0347 (3)
H4A	0.2742	−0.2437	0.6642	0.052*
H4B	0.2338	−0.1104	0.6599	0.052*
H4C	0.2652	−0.169	0.7499	0.052*
C5	0.35913 (4)	−0.11026 (18)	0.76603 (8)	0.0323 (3)
H5A	0.3425	−0.2272	0.7677	0.048*
H5B	0.3771	−0.0814	0.8232	0.048*
H5C	0.3771	−0.1307	0.7279	0.048*
C6	0.38177 (4)	0.31383 (17)	0.77103 (7)	0.0256 (2)
C7	0.38420 (4)	0.31516 (19)	0.85699 (8)	0.0315 (3)
H7	0.3631	0.2521	0.8771	0.038*
C8	0.41769 (5)	0.4094 (2)	0.91302 (8)	0.0371 (3)
H8	0.4198	0.4095	0.972	0.045*
C9	0.44812 (4)	0.5036 (2)	0.88369 (9)	0.0390 (3)
H9	0.471	0.5679	0.9224	0.047*
C10	0.44513 (4)	0.5039 (2)	0.79796 (9)	0.0368 (3)
H10	0.4658	0.5701	0.7779	0.044*
C11	0.41205 (4)	0.40798 (18)	0.74104 (8)	0.0307 (3)
H11	0.4102	0.4069	0.6822	0.037*
C12	0.22522 (4)	0.39995 (18)	0.55655 (7)	0.0265 (2)
H12	0.2467	0.4883	0.5522	0.032*
C13	0.18049 (4)	0.44398 (18)	0.51512 (7)	0.0256 (2)
C14	0.16980 (4)	0.62384 (18)	0.47654 (7)	0.0277 (3)
H14	0.1915	0.7145	0.4764	0.033*
C15	0.12782 (4)	0.67091 (18)	0.43851 (7)	0.0278 (3)
H15	0.1208	0.7938	0.4127	0.033*
C16	0.09584 (4)	0.53855 (18)	0.43809 (7)	0.0264 (2)
C17	0.10635 (4)	0.35766 (18)	0.47584 (8)	0.0293 (3)
H17	0.0846	0.2664	0.4753	0.035*
C18	0.14830 (4)	0.31137 (18)	0.51399 (7)	0.0294 (3)
H18	0.1553	0.1883	0.5396	0.035*
C19	0.05106 (4)	0.59546 (19)	0.39791 (8)	0.0309 (3)
C20	−0.02046 (5)	0.4949 (3)	0.35914 (14)	0.0618 (5)
H20A	−0.0302	0.581	0.3974	0.093*
H20B	−0.037	0.3753	0.3512	0.093*
H20C	−0.0243	0.5587	0.3042	0.093*
N1	0.34734 (3)	0.22117 (14)	0.71114 (6)	0.0262 (2)
N2	0.33035 (3)	0.05151 (14)	0.73522 (6)	0.0269 (2)
N3	0.23550 (3)	0.24258 (15)	0.59866 (6)	0.0261 (2)
O1	0.31896 (3)	0.49344 (13)	0.63305 (6)	0.0333 (2)
O2	0.03997 (3)	0.75497 (15)	0.37135 (7)	0.0445 (3)
O3	0.02396 (3)	0.45057 (14)	0.39547 (8)	0.0489 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0240 (6)	0.0246 (6)	0.0258 (5)	0.0030 (5)	0.0063 (4)	0.0011 (4)
C2	0.0237 (5)	0.0249 (6)	0.0247 (5)	0.0010 (5)	0.0084 (4)	−0.0007 (4)
C3	0.0268 (6)	0.0254 (6)	0.0241 (5)	−0.0001 (5)	0.0093 (4)	−0.0010 (4)
C4	0.0355 (7)	0.0312 (7)	0.0373 (6)	−0.0060 (6)	0.0100 (5)	0.0037 (5)
C5	0.0374 (7)	0.0244 (6)	0.0314 (6)	0.0058 (5)	0.0033 (5)	0.0048 (5)
C6	0.0231 (6)	0.0208 (6)	0.0312 (6)	0.0034 (4)	0.0044 (4)	0.0020 (4)
C7	0.0334 (6)	0.0282 (6)	0.0336 (6)	−0.0021 (5)	0.0102 (5)	0.0001 (5)
C8	0.0457 (8)	0.0318 (7)	0.0307 (6)	−0.0027 (6)	0.0051 (5)	−0.0016 (5)
C9	0.0376 (7)	0.0289 (7)	0.0427 (7)	−0.0064 (6)	−0.0019 (6)	−0.0001 (5)
C10	0.0303 (6)	0.0319 (7)	0.0465 (7)	−0.0051 (6)	0.0080 (5)	0.0058 (6)
C11	0.0296 (6)	0.0291 (6)	0.0331 (6)	0.0010 (5)	0.0080 (5)	0.0044 (5)
C12	0.0244 (6)	0.0292 (6)	0.0266 (5)	0.0008 (5)	0.0081 (4)	−0.0007 (4)
C13	0.0245 (6)	0.0297 (6)	0.0232 (5)	0.0029 (5)	0.0073 (4)	−0.0007 (4)
C14	0.0262 (6)	0.0294 (6)	0.0287 (5)	−0.0010 (5)	0.0095 (4)	0.0021 (5)
C15	0.0288 (6)	0.0269 (6)	0.0277 (5)	0.0026 (5)	0.0080 (5)	0.0036 (4)
C16	0.0255 (6)	0.0285 (6)	0.0246 (5)	0.0025 (5)	0.0062 (4)	0.0003 (4)
C17	0.0264 (6)	0.0269 (6)	0.0339 (6)	−0.0015 (5)	0.0075 (5)	0.0022 (5)
C18	0.0285 (6)	0.0272 (6)	0.0319 (6)	0.0024 (5)	0.0076 (5)	0.0042 (5)
C19	0.0270 (6)	0.0308 (7)	0.0323 (6)	0.0001 (5)	0.0040 (5)	0.0010 (5)
C20	0.0250 (7)	0.0426 (9)	0.1037 (14)	−0.0035 (7)	−0.0057 (8)	0.0077 (9)
N1	0.0250 (5)	0.0212 (5)	0.0305 (5)	−0.0009 (4)	0.0046 (4)	0.0045 (4)
N2	0.0279 (5)	0.0199 (5)	0.0312 (5)	−0.0002 (4)	0.0055 (4)	0.0041 (4)
N3	0.0231 (5)	0.0304 (5)	0.0248 (4)	0.0028 (4)	0.0066 (4)	−0.0009 (4)
O1	0.0306 (5)	0.0244 (5)	0.0417 (5)	−0.0001 (4)	0.0044 (4)	0.0087 (4)
O2	0.0296 (5)	0.0381 (6)	0.0599 (6)	0.0034 (4)	0.0024 (4)	0.0176 (5)
O3	0.0251 (5)	0.0311 (6)	0.0800 (8)	−0.0017 (4)	−0.0030 (5)	0.0054 (5)

Geometric parameters (Å, º)

C1—O1	1.2305 (14)	C10—H10	0.95
C1—N1	1.4109 (14)	C11—H11	0.95
C1—C2	1.4421 (16)	C12—N3	1.2844 (16)
C2—C3	1.3795 (16)	C12—C13	1.4670 (16)
C2—N3	1.3875 (14)	C12—H12	0.95
C3—N2	1.3518 (15)	C13—C18	1.3946 (17)
C3—C4	1.4815 (17)	C13—C14	1.3972 (17)
C4—H4A	0.98	C14—C15	1.3831 (16)
C4—H4B	0.98	C14—H14	0.95
C4—H4C	0.98	C15—C16	1.3904 (17)
C5—N2	1.4614 (15)	C15—H15	0.95
C5—H5A	0.98	C16—C17	1.3977 (17)
C5—H5B	0.98	C16—C19	1.4857 (16)
C5—H5C	0.98	C17—C18	1.3810 (17)
C6—C11	1.3859 (17)	C17—H17	0.95
C6—C7	1.3898 (17)	C18—H18	0.95
C6—N1	1.4271 (15)	C19—O2	1.2062 (16)
C7—C8	1.3846 (19)	C19—O3	1.3330 (16)
C7—H7	0.95	C20—O3	1.4449 (17)
C8—C9	1.384 (2)	C20—H20A	0.98
C8—H8	0.95	C20—H20B	0.98
C9—C10	1.382 (2)	C20—H20C	0.98
C9—H9	0.95	N1—N2	1.4028 (14)
C10—C11	1.3884 (18)
O1—C1—N1	123.13 (11)	N3—C12—C13	120.35 (11)
O1—C1—C2	132.14 (11)	N3—C12—H12	119.8
N1—C1—C2	104.67 (10)	C13—C12—H12	119.8
C3—C2—N3	121.99 (11)	C18—C13—C14	119.15 (11)
C3—C2—C1	108.06 (10)	C18—C13—C12	121.61 (11)
N3—C2—C1	129.56 (11)	C14—C13—C12	119.23 (11)
N2—C3—C2	109.86 (10)	C15—C14—C13	120.52 (11)
N2—C3—C4	121.93 (11)	C15—C14—H14	119.7
C2—C3—C4	128.20 (11)	C13—C14—H14	119.7
C3—C4—H4A	109.5	C14—C15—C16	120.04 (11)
C3—C4—H4B	109.5	C14—C15—H15	120
H4A—C4—H4B	109.5	C16—C15—H15	120
C3—C4—H4C	109.5	C15—C16—C17	119.72 (11)
H4A—C4—H4C	109.5	C15—C16—C19	118.51 (11)
H4B—C4—H4C	109.5	C17—C16—C19	121.77 (11)
N2—C5—H5A	109.5	C18—C17—C16	120.08 (11)
N2—C5—H5B	109.5	C18—C17—H17	120
H5A—C5—H5B	109.5	C16—C17—H17	120
N2—C5—H5C	109.5	C17—C18—C13	120.47 (12)
H5A—C5—H5C	109.5	C17—C18—H18	119.8
H5B—C5—H5C	109.5	C13—C18—H18	119.8
C11—C6—C7	120.72 (11)	O2—C19—O3	123.15 (11)
C11—C6—N1	118.31 (10)	O2—C19—C16	124.43 (12)
C7—C6—N1	120.94 (11)	O3—C19—C16	112.42 (11)
C8—C7—C6	119.29 (12)	O3—C20—H20A	109.5
C8—C7—H7	120.4	O3—C20—H20B	109.5
C6—C7—H7	120.4	H20A—C20—H20B	109.5
C9—C8—C7	120.40 (12)	O3—C20—H20C	109.5
C9—C8—H8	119.8	H20A—C20—H20C	109.5
C7—C8—H8	119.8	H20B—C20—H20C	109.5
C10—C9—C8	119.92 (12)	N2—N1—C1	108.88 (9)
C10—C9—H9	120	N2—N1—C6	118.85 (9)
C8—C9—H9	120	C1—N1—C6	121.49 (10)
C9—C10—C11	120.42 (12)	C3—N2—N1	107.96 (9)
C9—C10—H10	119.8	C3—N2—C5	126.14 (10)
C11—C10—H10	119.8	N1—N2—C5	118.12 (9)
C6—C11—C10	119.24 (12)	C12—N3—C2	120.76 (10)
C6—C11—H11	120.4	C19—O3—C20	116.02 (11)
C10—C11—H11	120.4
O1—C1—C2—C3	−175.46 (12)	C12—C13—C18—C17	178.86 (11)
N1—C1—C2—C3	1.93 (12)	C15—C16—C19—O2	−6.30 (19)
O1—C1—C2—N3	−2.7 (2)	C17—C16—C19—O2	173.01 (13)
N1—C1—C2—N3	174.70 (11)	C15—C16—C19—O3	174.72 (11)
N3—C2—C3—N2	−170.52 (10)	C17—C16—C19—O3	−5.97 (17)
C1—C2—C3—N2	2.91 (13)	O1—C1—N1—N2	171.78 (11)
N3—C2—C3—C4	10.72 (18)	C2—C1—N1—N2	−5.91 (12)
C1—C2—C3—C4	−175.85 (11)	O1—C1—N1—C6	27.94 (16)
C11—C6—C7—C8	−0.97 (19)	C2—C1—N1—C6	−149.75 (10)
N1—C6—C7—C8	−178.87 (12)	C11—C6—N1—N2	146.60 (11)
C6—C7—C8—C9	0.9 (2)	C7—C6—N1—N2	−35.45 (16)
C7—C8—C9—C10	0.1 (2)	C11—C6—N1—C1	−72.99 (14)
C8—C9—C10—C11	−0.9 (2)	C7—C6—N1—C1	104.96 (13)
C7—C6—C11—C10	0.17 (19)	C2—C3—N2—N1	−6.64 (12)
N1—C6—C11—C10	178.13 (11)	C4—C3—N2—N1	172.21 (10)
C9—C10—C11—C6	0.8 (2)	C2—C3—N2—C5	−154.88 (11)
N3—C12—C13—C18	−5.38 (17)	C4—C3—N2—C5	23.98 (17)
N3—C12—C13—C14	174.01 (10)	C1—N1—N2—C3	7.89 (12)
C18—C13—C14—C15	0.73 (17)	C6—N1—N2—C3	152.83 (10)
C12—C13—C14—C15	−178.67 (10)	C1—N1—N2—C5	159.07 (10)
C13—C14—C15—C16	−0.31 (17)	C6—N1—N2—C5	−55.98 (14)
C14—C15—C16—C17	−0.33 (17)	C13—C12—N3—C2	−176.14 (10)
C14—C15—C16—C19	178.99 (11)	C3—C2—N3—C12	178.95 (11)
C15—C16—C17—C18	0.54 (18)	C1—C2—N3—C12	7.07 (18)
C19—C16—C17—C18	−178.76 (11)	O2—C19—O3—C20	−0.4 (2)
C16—C17—C18—C13	−0.10 (18)	C16—C19—O3—C20	178.58 (13)
C14—C13—C18—C17	−0.53 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1	0.95	2.37	3.0486 (17)	128