Conversion of substituted 5-aryl­oxypyrazole­carbaldehydes into reduced 3,4′-bi­pyrazoles: synthesis and characterization, and the structures of four precursors and two products, and their supra­molecular assembly in zero, one and two dimensions

Kiran Kumar, H.; Yathirajan, H.S.; Manju, N.; Kalluraya, B.; Rathore, R.S.; Glidewell, C.

doi:10.1107/S2053229619006752

Conversion of substituted 5-aryloxypyrazolecarbaldehydes into reduced 3,4′-bipyrazoles: synthesis and characterization, and the structures of four precursors and two products, and their supramolecular assembly in zero, one and two dimensions

H. Kiran Kumar, H. S. Yathirajan, N. Manju, B. Kalluraya, R. S. Rathore and C. Glidewell

The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with phenols under basic conditions yields the corresponding 5-aryloxy derivatives; the subsequent reaction of these carbaldehydes with substituted acetophenones yields the corresponding chalcones, which in turn undergo cyclocondensation reactions with hydrazine in the presence of acetic acid to form N-acetylated reduced bipyrazoles. Structures are reported for three 5-aryloxycarbaldehydes and the 5-piperidino analogue, and for two reduced bipyrazole products. 5-(2-Chlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, C₁₇H₁₃ClN₂O₂, (II), which crystallizes with Z′ = 2 in the space group P $\overline{1}$ , exhibits orientational disorder of the carbaldehyde group in each of the two independent molecules. Each of 3-methyl-5-(4-nitrophenoxy)-1-phenyl-1H-pyrazole-4-carbaldehyde, C₁₇H₁₃N₃O₄, (IV), 3-methyl-5-(naphthalen-2-yloxy)-1-phenyl-1H-pyrazole-4-carbaldehyde, C₂₁H₁₆N₂O₂, (V), and 3-methyl-1-phenyl-5-(piperidin-1-yl)-1H-pyrazole-4-carbaldehyde, C₁₆H₁₉N₃O, (VI), (3RS)-2-acetyl-5-(4-azidophenyl)-5′-(2-chlorophenoxy)-3′-methyl-1′-phenyl-3,4-dihydro-1′H,2H-[3,4′-bipyrazole] C₂₇H₂₂ClN₇O₂, (IX) and (3RS)-2-acetyl-5-(4-azidophenyl)-3′-methyl-5′-(naphthalen-2-yloxy)-1′-phenyl-3,4-dihydro-1′H,2H-[3,4′-bipyrazole] C₃₁H₂₅N₇O₂, (X), has Z′ = 1, and each is fully ordered. The new compounds have all been fully characterized by analysis, namely IR spectroscopy, ¹H and ¹³C NMR spectroscopy, and mass spectrometry. In each of (II), (V) and (IX), the molecules are linked into ribbons, generated respectively by combinations of C—H

N, C—H

π and C—Cl

π interactions in (II), C—H

O and C—H

π hydrogen bonds in (V), and C—H

N and C—H

O hydrogen bonds in (IX). The molecules of compounds (IV) and (IX) are both linked into sheets, by multiple C—H

O and C—H

π hydrogen bonds in (IV), and by two C—H

π hydrogen bonds in (IX). A single C—H

N hydrogen bond links the molecules of (X) into centrosymmetric dimers. Comparisons are made with the structures of some related compounds.

Keywords: synthesis; heterocyclic compounds; bipyrazoles; crystal structure; disorder; hydrogen bonding; supramolecular assembly.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619006752/ky3177sup1.cif Contains datablocks global, II, IV, V, VI, IX, X
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177IIsup2.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177IVsup3.hkl Contains datablock IV
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177Vsup4.hkl Contains datablock V
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177VIsup5.hkl Contains datablock VI
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177IXsup6.hkl Contains datablock IX
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619006752/ky3177Xsup7.hkl Contains datablock X
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229619006752/ky3177IIsup8.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229619006752/ky3177Vsup9.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229619006752/ky3177VIsup10.cml Supplementary material

CCDC references: 1915426; 1915425; 1915424; 1915423; 1915422; 1915421

Computing details top

For all structures, data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).

5-(2-Chlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (II) top

Crystal data top

C₁₇H₁₃ClN₂O₂	Z = 4
M_r = 312.74	F(000) = 648
Triclinic, P1	D_x = 1.376 Mg m⁻³
a = 10.3034 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4856 (4) Å	Cell parameters from 7620 reflections
c = 14.4725 (5) Å	θ = 1.5–28.5°
α = 81.013 (2)°	µ = 0.26 mm⁻¹
β = 69.861 (2)°	T = 296 K
γ = 69.990 (2)°	Block, colourless
V = 1509.47 (10) Å³	0.19 × 0.16 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	6296 independent reflections
Radiation source: fine focus sealed tube	4051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 0.3333 pixels mm^-1	θ_max = 26.6°, θ_min = 1.5°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −14→14
T_min = 0.902, T_max = 0.967	l = −18→18
35720 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0353P)² + 0.7109P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
6296 reflections	Δρ_max = 0.20 e Å⁻³
425 parameters	Δρ_min = −0.26 e Å⁻³

Special details top

Experimental. Characterisation data for compounds (II) and (IV) - (X).

Compound (II). . IR (KBr, cm^-1) 1717 (C=O), 1566 (C=N). NMR (CDCl₃) δ(¹H) 2.56 (s, 3H, CH₃), 6.92 (dd, 1H, J=0.80 Hz, J= 6.44 Hz, H2 of 2-chlorophenyl), 7.09 (m, 1H, 2-chlorophenyl), 7.17 (m, 1H, 2-chlorophenyl), 7.34 (t, 1H, 2-chlorophenyl), 7.43 (t, 3H, H3,H4,H5 of N-phenyl), 7.69 (d, 2H, J=6.40 Hz, H2, H6 of N-phenyl), 9.54 (s, 1H, aldehyde); δ(¹³C) 14.60 (CH₃), 108.77, 117.17, 122.87, 122.87, 123.58, 125.79, 128.12, 128.27, 129.28, 131.25, 136.80, 150.86, 151.88, 152.21, 182.73 (aldehyde). MS (m/z) 313/315 (M⁺ + 1). Analysis: found C 65.3, H 4.3, N 8.9%; C₁₇H₁₃ClN₂O₂ requires C 65.3, H 4.2, N 9.0%.

Compound (IV). IR (KBr, cm^-1) 1667 (C=O), 1610 (C=N), 1545 (NO₂), 1340 (NO₂). NMR (CDCl₃) δ(¹H) 2.61 (s, 3H, CH₃), 7.12 (d, 2H, J= 4.44 Hz, H2,H6 of N-phenyl), 7.43-7.46 (m, 3H, H3,H4,H5 of N-phenyl), 7.59 (d, 2H, J=7.42 Hz) and 8.23 (d, 2H, J= 7.42 Hz) (AB, 4-nitrophenyl), 9.78 (s, 1H, aldehyde); δ(¹³C) 13.96 (CH₃), 109.36, 116.17, 122.85, 126.25, 128.62, 129.50, 136.34, 144.16, 149.16, 151.30, 160.70, 182.43 (aldehyde). MS (m/z) 324 (M⁺ + 1). Analysis: found C 63.3, H 4.0, N 12.7%; C₁₇H₁₃N₃O₄ requires C 63.2, H 4.1, N 13.0%.

Compound (V). IR (KBr, cm^-1) 1719 (C=O), 1555 (C=N). NMR (CDCl₃) δ(¹H) 2.31 (s, 3H, CH₃), 7.28 (m, 3H, Ar-H), 7.40 (m, 4H, Ar-H), 7.68 (d, 2H, J=6.80 Hz, Ar-H), 7.71 (d, 1H, J=6.40 Hz, Ar-H), 7.83 (d, 1H, J=6.40 Hz, Ar-H), 7.85 (d, 1H, J=7.20 Hz, Ar-H), 9.65 (s, 1H, aldehyde); δ(¹³C) 14.62 (CH₃), 109.09, 111.60, 116.87, 122.77, 125.57, 127.25, 127.32, 127.86, 128.07, 129.29, 130.61, 130.77, 133.90, 136.92, 150.93, 152.39, 154.88, 183.09 (aldehyde). MS (m/z) 329 (M⁺ + 1). Analysis: found C 76.8, H 5.0, N 8.6%; C₂₁H₁₆N₂O₂ requires C 76.8, H 4.9, N 8.5%.

Compound (VI). IR (KBr, cm^-1) 1722 (C=O), 1534 (C=N). NMR (CDCl₃) δ(¹H) 2.32 (s, 3H, CH₃), 2.98-3.67 (m, 10H, piperidine), 6.97 (d, 2H, J= 7.87 Hz, H2,H6 of N-phenyl), 7.24 (m, 3H, H3,H4,H5 of N-phenyl), 9.70 (s, 1H, aldehyde); δ(¹³C) 12.97 (CH₃), 45.65 (CH₂), 57.51(CH₂), 125.76, 126.8,127.43, 128.69, 129.86, 136.43, 145.39, 148.21, 151.27, 183.43 (aldehyde). MS (m/z) 270 (M⁺ + 1). Analysis: found C 71.4, H 7.0, N 15.5%; C₁₆H₁₉N₃O requires C 71.3, H 7.1, N 15.6%.

Compound (VII). IR (KBr, cm^-1) 2359 (azide), 1650 (C=O), 1592 (C=N). NMR (CDCl₃) δ(¹H) 2.52 (s, 3H, CH₃), 6.62 (d, 1H, Ar-H), 6.90 (d, 1H, J= 15.80 Hz, oalkenic H), 6.98 (d, 2H, J=8.64 Hz, H2, H6 of azidophenyl), 7.03 (m, 2H, Ar-H), 7.28 (d, 2H, J= 8.64 Hz, H3,H5 of azidophenyl), 7.36 (m, 2H, Ar-H), 7.55 (d, 1H, J=15.80 Hz, alkenic H), 7.60 (m, 4H, Ar-H). MS (m/z) 456 (M⁺ + 1) for C₂₅H₁₈³⁵ClN₅O₂. Analysis: found C 66.0, H 4.0, N 15.5%; C₂₅H₁₈ClN₅O₂ requires C 65.9, H 4.0, N 15.4%.

Compound (VIII). IR (KBr, cm^-1) 2354 (azide), 1676 (C=O), 1565 (C=N). NMR (CDCl₃) δ(¹H) : 2.56 (s, 3H, CH₃), 6.67 (m, 2H, Ar-H), 6.96 (d, 1H, J= 15.80 Hz, alkenic H), 7.06 (d, 2H, J=8.58 Hz, H2,H6 of azidophenyl), 7.10 (m, 3H, Ar-H), 7.26 (d, 2H, J= 8.64 Hz, H3,H5 of azidophenyl), 7.43 (m, 2H, Ar-H), 7.58 (d, 1H, J=15.80 Hz, alkenic H), 7.60 (m, 5H, Ar-H). MS (m/z) 472 (M⁺ + 1). Analysis: found C 74.0, H 4.4, N 14.7%; C₂₉H₂₁N₅O₂ requires C 73.9, H 6.5, N 14.9%.

Compound (IX). IR (KBr, cm^-1) 2359 (azide), 1650 (C=O), 1592 (C=N). NMR (CDCl₃) δ(¹H) 2.02 (s, 3H, acyl CH₃), 2.42 (s,3H, CH₃), 3.26 (dd, J=5.1 Hz & 17.4 Hz, 1H, -CH₂), 3.57 (dd, J=12.3 Hz and 17.4 Hz, 1H, -CH₂), 5.37 (dd, J=5.1 Hz and 12.3 Hz, 1H, -CH), 6.62 (d, J=8.1 Hz, 1H, Ar-H), 7.18 (d, J= 7.8 Hz, 2H, H2 and H6 of azidophenyl), 7.32 (m, 4H, Ar-H), 7.38 (m, 4H, Ar-H), 7.44(d, J= 7.8 Hz, 2H, H3 and H5 of azidophenyl); δ(¹³C) 12.93 (CH₃, acetyl), 22.46 (CH₃, pyrazole), 52.18 (CH₂, pyrazoline), 54.91 (-CH, pyrazoline), 109.09, 111.60, 116.87, 122.77, 125.57, 127.25, 127.32, 127.86, 128.07, 129.29, 130.61, 130.77, 131.28 133.90, 136.92, 138.54, 150.93, 152.39, 155.87, 158.92, 171.24 (C=O). MS (m/z) 512/514 (M⁺ + 1). Analysis: found C 63.4, H 4.3, N 19.2%; C₂₇H₂₂ClN₇O₂ requires C 63.3, H 4.4, N 19.2%.

Compound (X). IR (KBr, cm^-1) 2365 (azide), 1698 (C=O),1587 (C=N). NMR (CDCl₃) δ(¹H) 2.12 (s, 3H, acyl CH₃), 2.42 (s, 3H, CH₃), 3.27 (dd, J=5.2 Hz and 17.1 Hz, 1H, -CH₂), 3.53 (dd, J=12.4 Hz and 17.1 Hz, 1H, -CH₂), 5.33 (dd, J=5.0 Hz and 12.4 Hz, 1H, -CH), 6.62 (m, 3H, Ar-H), 7.13 (d, J=7.7 Hz, 2H, H2,H6 of azidophenyl), 7.28 (m, 4H, Ar-H), 7.39 (m, 5H, Ar-H), 7.40 (d, J=7.6 Hz, 2H, H3,H5 of azidophenyl); δ(¹³C) 12.28 (CH₃ acetyl), 22.40 (CH₃, pyrazole), 51.12 (CH₂, pyrazoline), 53.78 (-CH, pyrazoline), 108.13, 111.60, 117.85, 121.77, 127.56, 127.88, 128.42, 128.68, 128.97, 129.39, 130.68, 131.54, 132.23, 132.69, 133.77, 134.28 135.87, 136.72, 137.54, 149.93, 152.22, 155.86, 157.92, 172.30 (C=O). MS (m/z) 528 (M⁺ + 1). Analysis: found C 70.4, H 4.6, N 18.8%; C₃₁H₂₅N₇O₂ requires C 70.6, H 4.8, N 18.6%.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N11	0.46537 (19)	0.20203 (16)	0.97485 (11)	0.0428 (4)
N12	0.4865 (2)	0.14789 (18)	1.06314 (12)	0.0481 (5)
C13	0.6283 (3)	0.1122 (2)	1.04671 (15)	0.0471 (5)
C14	0.7027 (2)	0.1431 (2)	0.94887 (15)	0.0478 (5)
C15	0.5939 (2)	0.1991 (2)	0.90689 (14)	0.0436 (5)
C111	0.3208 (2)	0.2481 (2)	0.96916 (14)	0.0427 (5)
C112	0.2864 (3)	0.3315 (3)	0.8960 (2)	0.0814 (9)
H112	0.3575	0.3598	0.8483	0.098*
C113	0.1451 (3)	0.3729 (4)	0.8937 (2)	0.1052 (13)
H113	0.1222	0.4283	0.8432	0.126*
C114	0.0389 (3)	0.3349 (3)	0.9633 (2)	0.0826 (9)
H114	−0.0562	0.3641	0.9612	0.099*
C115	0.0738 (3)	0.2535 (3)	1.0363 (2)	0.0741 (8)
H115	0.0016	0.2271	1.0847	0.089*
C116	0.2138 (3)	0.2094 (2)	1.03989 (17)	0.0596 (7)
H116	0.2360	0.1534	1.0903	0.072*
C131	0.6907 (3)	0.0485 (3)	1.12701 (17)	0.0652 (7)
H13A	0.6134	0.0426	1.1862	0.098*
H13B	0.7447	0.0952	1.1386	0.098*
H13C	0.7541	−0.0332	1.1079	0.098*
O151	0.60317 (16)	0.24826 (13)	0.81410 (10)	0.0502 (4)
C151	0.6655 (2)	0.1640 (2)	0.73937 (14)	0.0392 (5)
C152	0.7316 (2)	0.2059 (2)	0.64638 (15)	0.0437 (5)
Cl12	0.74176 (7)	0.35534 (6)	0.62745 (5)	0.0646 (2)
C153	0.7915 (3)	0.1277 (3)	0.56909 (17)	0.0627 (7)
H153	0.8371	0.1554	0.5063	0.075*
C154	0.7838 (3)	0.0093 (3)	0.5845 (2)	0.0704 (8)
H154	0.8236	−0.0431	0.5322	0.085*
C155	0.7176 (3)	−0.0324 (2)	0.6772 (2)	0.0604 (7)
H155	0.7133	−0.1132	0.6875	0.072*
C156	0.6578 (2)	0.0449 (2)	0.75491 (17)	0.0486 (5)
H156	0.6123	0.0169	0.8176	0.058*
C141	0.8530 (8)	0.1221 (15)	0.9098 (7)	0.056 (2)	0.682 (6)
H141	0.9112	0.0811	0.9492	0.067*	0.682 (6)
O141	0.9129 (3)	0.1571 (3)	0.8223 (2)	0.0759 (12)	0.682 (6)
C341	0.865 (2)	0.133 (4)	0.886 (2)	0.056 (2)	0.318 (6)
H341	0.8920	0.1666	0.8217	0.067*	0.318 (6)
O341	0.9538 (8)	0.0736 (8)	0.9322 (6)	0.108 (3)	0.318 (6)
N21	0.35991 (17)	0.30621 (16)	0.36519 (12)	0.0399 (4)
N22	0.25244 (19)	0.36825 (17)	0.32225 (13)	0.0464 (4)
C23	0.3205 (2)	0.4062 (2)	0.23383 (16)	0.0466 (5)
C24	0.4720 (2)	0.3700 (2)	0.21647 (16)	0.0470 (5)
C25	0.4906 (2)	0.30728 (19)	0.30224 (16)	0.0412 (5)
C211	0.3173 (2)	0.25752 (19)	0.46428 (15)	0.0414 (5)
C212	0.4180 (3)	0.1774 (2)	0.50657 (19)	0.0653 (7)
H212	0.5163	0.1524	0.4705	0.078*
C213	0.3710 (3)	0.1348 (3)	0.6031 (2)	0.0796 (9)
H213	0.4389	0.0821	0.6320	0.096*
C214	0.2275 (3)	0.1683 (3)	0.65666 (19)	0.0686 (7)
H214	0.1974	0.1383	0.7214	0.082*
C215	0.1287 (3)	0.2464 (3)	0.61408 (18)	0.0627 (7)
H215	0.0303	0.2693	0.6502	0.075*
C216	0.1720 (2)	0.2920 (2)	0.51849 (17)	0.0525 (6)
H216	0.1034	0.3459	0.4906	0.063*
C231	0.2365 (3)	0.4796 (3)	0.16684 (19)	0.0674 (7)
H23A	0.2393	0.5633	0.1593	0.101*
H23B	0.1374	0.4795	0.1944	0.101*
H23C	0.2787	0.4432	0.1037	0.101*
O251	0.61405 (15)	0.24538 (14)	0.32537 (12)	0.0525 (4)
C251	0.6978 (2)	0.3141 (2)	0.33282 (15)	0.0417 (5)
C252	0.8440 (2)	0.2532 (2)	0.31538 (14)	0.0414 (5)
Cl22	0.91523 (7)	0.10054 (6)	0.28375 (5)	0.06481 (19)
C253	0.9323 (2)	0.3149 (2)	0.32515 (16)	0.0532 (6)
H253	1.0313	0.2744	0.3131	0.064*
C254	0.8744 (3)	0.4354 (2)	0.35251 (18)	0.0579 (6)
H254	0.9342	0.4764	0.3593	0.070*
C255	0.7287 (3)	0.4961 (2)	0.36995 (19)	0.0615 (7)
H255	0.6899	0.5782	0.3882	0.074*
C256	0.6397 (3)	0.4354 (2)	0.36030 (18)	0.0551 (6)
H256	0.5408	0.4762	0.3723	0.066*
C241	0.5717 (19)	0.386 (3)	0.1239 (9)	0.056 (2)	0.536 (5)
H241	0.5400	0.4223	0.0703	0.067*	0.536 (5)
O241	0.7078 (4)	0.3480 (4)	0.1156 (3)	0.0786 (15)	0.536 (5)
C441	0.599 (2)	0.392 (3)	0.1335 (10)	0.056 (2)	0.464 (5)
H441	0.6916	0.3673	0.1403	0.067*	0.464 (5)
O441	0.5767 (6)	0.4465 (6)	0.0535 (4)	0.113 (2)	0.464 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0443 (10)	0.0524 (11)	0.0300 (9)	−0.0158 (9)	−0.0112 (8)	0.0035 (8)
N12	0.0519 (12)	0.0614 (12)	0.0318 (9)	−0.0195 (10)	−0.0155 (8)	0.0057 (8)
C13	0.0515 (14)	0.0541 (14)	0.0388 (12)	−0.0170 (11)	−0.0174 (10)	−0.0015 (10)
C14	0.0457 (13)	0.0535 (14)	0.0423 (12)	−0.0145 (11)	−0.0118 (10)	−0.0034 (10)
C15	0.0487 (13)	0.0452 (13)	0.0325 (11)	−0.0145 (10)	−0.0077 (10)	−0.0011 (9)
C111	0.0422 (12)	0.0479 (13)	0.0356 (11)	−0.0110 (10)	−0.0129 (9)	−0.0005 (9)
C112	0.0538 (16)	0.103 (2)	0.0669 (18)	−0.0174 (16)	−0.0176 (14)	0.0357 (16)
C113	0.064 (2)	0.143 (3)	0.078 (2)	−0.012 (2)	−0.0293 (17)	0.050 (2)
C114	0.0500 (16)	0.113 (3)	0.0722 (19)	−0.0116 (16)	−0.0251 (15)	0.0127 (18)
C115	0.0460 (15)	0.102 (2)	0.0664 (17)	−0.0250 (15)	−0.0129 (13)	0.0129 (16)
C116	0.0484 (14)	0.0775 (18)	0.0460 (13)	−0.0194 (13)	−0.0133 (11)	0.0129 (12)
C131	0.0687 (17)	0.0828 (19)	0.0498 (14)	−0.0209 (15)	−0.0307 (13)	0.0031 (13)
O151	0.0590 (10)	0.0459 (9)	0.0311 (7)	−0.0088 (7)	−0.0052 (7)	0.0018 (6)
C151	0.0341 (11)	0.0475 (13)	0.0320 (10)	−0.0079 (9)	−0.0111 (9)	0.0005 (9)
C152	0.0381 (12)	0.0499 (13)	0.0367 (11)	−0.0085 (10)	−0.0112 (9)	0.0032 (9)
Cl12	0.0620 (4)	0.0567 (4)	0.0602 (4)	−0.0174 (3)	−0.0106 (3)	0.0168 (3)
C153	0.0635 (16)	0.080 (2)	0.0361 (13)	−0.0148 (14)	−0.0116 (11)	−0.0040 (12)
C154	0.0738 (19)	0.077 (2)	0.0599 (17)	−0.0080 (15)	−0.0254 (14)	−0.0264 (15)
C155	0.0668 (17)	0.0510 (15)	0.0746 (18)	−0.0167 (13)	−0.0360 (14)	−0.0057 (13)
C156	0.0488 (13)	0.0539 (14)	0.0459 (12)	−0.0179 (11)	−0.0192 (11)	0.0044 (11)
C141	0.048 (2)	0.072 (4)	0.042 (6)	−0.021 (2)	−0.009 (3)	0.008 (4)
O141	0.0554 (18)	0.098 (2)	0.059 (2)	−0.0294 (16)	0.0018 (14)	0.0044 (16)
C341	0.048 (2)	0.072 (4)	0.042 (6)	−0.021 (2)	−0.009 (3)	0.008 (4)
O341	0.059 (5)	0.133 (7)	0.128 (7)	−0.015 (4)	−0.039 (4)	−0.006 (5)
N21	0.0334 (9)	0.0457 (10)	0.0446 (10)	−0.0131 (8)	−0.0175 (8)	0.0005 (8)
N22	0.0387 (10)	0.0550 (12)	0.0527 (11)	−0.0157 (9)	−0.0249 (9)	0.0045 (9)
C23	0.0479 (13)	0.0491 (13)	0.0492 (13)	−0.0172 (11)	−0.0216 (11)	0.0000 (10)
C24	0.0467 (13)	0.0522 (14)	0.0446 (12)	−0.0192 (11)	−0.0142 (10)	−0.0010 (10)
C25	0.0333 (11)	0.0424 (12)	0.0511 (12)	−0.0118 (9)	−0.0153 (10)	−0.0062 (10)
C211	0.0394 (12)	0.0421 (12)	0.0467 (12)	−0.0150 (10)	−0.0168 (10)	−0.0004 (9)
C212	0.0447 (14)	0.0747 (18)	0.0599 (15)	−0.0051 (13)	−0.0168 (12)	0.0132 (13)
C213	0.0627 (18)	0.089 (2)	0.0703 (18)	−0.0095 (16)	−0.0279 (15)	0.0285 (16)
C214	0.0727 (19)	0.0770 (19)	0.0540 (15)	−0.0289 (15)	−0.0204 (14)	0.0171 (13)
C215	0.0492 (15)	0.0786 (19)	0.0573 (15)	−0.0269 (14)	−0.0099 (12)	0.0060 (13)
C216	0.0411 (13)	0.0624 (15)	0.0563 (14)	−0.0176 (11)	−0.0192 (11)	0.0036 (11)
C231	0.0672 (17)	0.0818 (19)	0.0606 (16)	−0.0228 (15)	−0.0361 (14)	0.0128 (14)
O251	0.0354 (8)	0.0493 (9)	0.0780 (11)	−0.0147 (7)	−0.0248 (8)	0.0028 (8)
C251	0.0347 (11)	0.0538 (14)	0.0396 (11)	−0.0187 (10)	−0.0134 (9)	0.0049 (10)
C252	0.0334 (11)	0.0525 (13)	0.0358 (11)	−0.0128 (10)	−0.0105 (9)	0.0031 (9)
Cl22	0.0488 (4)	0.0603 (4)	0.0825 (5)	−0.0051 (3)	−0.0261 (3)	−0.0094 (3)
C253	0.0371 (12)	0.0729 (18)	0.0538 (14)	−0.0200 (12)	−0.0199 (11)	0.0049 (12)
C254	0.0547 (15)	0.0691 (18)	0.0645 (16)	−0.0314 (14)	−0.0263 (13)	0.0019 (13)
C255	0.0649 (17)	0.0568 (16)	0.0699 (17)	−0.0198 (13)	−0.0263 (13)	−0.0094 (13)
C256	0.0394 (13)	0.0600 (16)	0.0645 (15)	−0.0101 (11)	−0.0181 (11)	−0.0068 (12)
C241	0.045 (6)	0.081 (3)	0.053 (3)	−0.031 (5)	−0.022 (3)	0.004 (3)
O241	0.045 (2)	0.109 (3)	0.073 (2)	−0.032 (2)	−0.0038 (18)	0.003 (2)
C441	0.045 (6)	0.081 (3)	0.053 (3)	−0.031 (5)	−0.022 (3)	0.004 (3)
O441	0.110 (4)	0.153 (5)	0.066 (3)	−0.057 (4)	−0.020 (3)	0.044 (3)

Geometric parameters (Å, º) top

N11—C15	1.344 (3)	N21—C25	1.344 (3)
N11—N12	1.385 (2)	N21—N22	1.384 (2)
N11—C111	1.428 (3)	N21—C211	1.430 (3)
N12—C13	1.319 (3)	N22—C23	1.318 (3)
C13—C14	1.414 (3)	C23—C24	1.411 (3)
C13—C131	1.492 (3)	C23—C231	1.491 (3)
C14—C15	1.375 (3)	C24—C25	1.374 (3)
C14—C141	1.400 (8)	C24—C241	1.410 (11)
C14—C341	1.58 (2)	C24—C441	1.508 (13)
C15—O151	1.357 (2)	C25—O251	1.354 (2)
C111—C112	1.368 (3)	C211—C216	1.377 (3)
C111—C116	1.370 (3)	C211—C212	1.380 (3)
C112—C113	1.378 (4)	C212—C213	1.381 (3)
C112—H112	0.9300	C212—H212	0.9300
C113—C114	1.354 (4)	C213—C214	1.360 (4)
C113—H113	0.9300	C213—H213	0.9300
C114—C115	1.357 (4)	C214—C215	1.363 (3)
C114—H114	0.9300	C214—H214	0.9300
C115—C116	1.372 (3)	C215—C216	1.377 (3)
C115—H115	0.9300	C215—H215	0.9300
C116—H116	0.9300	C216—H216	0.9300
C131—H13A	0.9600	C231—H23A	0.9600
C131—H13B	0.9600	C231—H23B	0.9600
C131—H13C	0.9600	C231—H23C	0.9600
O151—C151	1.394 (2)	O251—C251	1.392 (2)
C151—C156	1.376 (3)	C251—C252	1.376 (3)
C151—C152	1.378 (3)	C251—C256	1.376 (3)
C152—C153	1.378 (3)	C252—C253	1.383 (3)
C152—Cl12	1.728 (2)	C252—Cl22	1.721 (2)
C153—C154	1.369 (4)	C253—C254	1.368 (3)
C153—H153	0.9300	C253—H253	0.9300
C154—C155	1.374 (4)	C254—C255	1.372 (3)
C154—H154	0.9300	C254—H254	0.9300
C155—C156	1.376 (3)	C255—C256	1.379 (3)
C155—H155	0.9300	C255—H255	0.9300
C156—H156	0.9300	C256—H256	0.9300
C141—O141	1.272 (10)	C241—O241	1.286 (17)
C141—H141	0.9300	C241—H241	0.9300
C341—O341	1.271 (13)	C441—O441	1.283 (17)
C341—H341	0.9300	C441—H441	0.9300

C15—N11—N12	109.92 (17)	C25—N21—N22	109.99 (16)
C15—N11—C111	131.34 (17)	C25—N21—C211	131.70 (17)
N12—N11—C111	118.73 (16)	N22—N21—C211	118.27 (16)
C13—N12—N11	105.69 (16)	C23—N22—N21	105.52 (17)
N12—C13—C14	111.49 (19)	N22—C23—C24	111.66 (18)
N12—C13—C131	120.3 (2)	N22—C23—C231	120.1 (2)
C14—C13—C131	128.3 (2)	C24—C23—C231	128.2 (2)
C15—C14—C141	130.6 (4)	C25—C24—C241	132.2 (9)
C15—C14—C13	104.06 (19)	C25—C24—C23	104.14 (18)
C141—C14—C13	125.3 (4)	C241—C24—C23	123.1 (8)
C15—C14—C341	119.0 (8)	C25—C24—C441	120.9 (9)
C13—C14—C341	136.8 (8)	C23—C24—C441	134.9 (9)
N11—C15—O151	121.68 (19)	N21—C25—O251	120.89 (18)
N11—C15—C14	108.84 (18)	N21—C25—C24	108.69 (18)
O151—C15—C14	129.5 (2)	O251—C25—C24	130.25 (19)
C112—C111—C116	119.5 (2)	C216—C211—C212	119.5 (2)
C112—C111—N11	121.6 (2)	C216—C211—N21	118.85 (18)
C116—C111—N11	118.93 (18)	C212—C211—N21	121.68 (19)
C111—C112—C113	119.3 (3)	C211—C212—C213	119.2 (2)
C111—C112—H112	120.4	C211—C212—H212	120.4
C113—C112—H112	120.4	C213—C212—H212	120.4
C114—C113—C112	121.5 (3)	C214—C213—C212	121.4 (2)
C114—C113—H113	119.2	C214—C213—H213	119.3
C112—C113—H113	119.2	C212—C213—H213	119.3
C113—C114—C115	118.7 (3)	C213—C214—C215	119.0 (2)
C113—C114—H114	120.7	C213—C214—H214	120.5
C115—C114—H114	120.7	C215—C214—H214	120.5
C114—C115—C116	121.1 (3)	C214—C215—C216	121.1 (2)
C114—C115—H115	119.4	C214—C215—H215	119.5
C116—C115—H115	119.4	C216—C215—H215	119.5
C111—C116—C115	119.9 (2)	C215—C216—C211	119.8 (2)
C111—C116—H116	120.1	C215—C216—H216	120.1
C115—C116—H116	120.1	C211—C216—H216	120.1
C13—C131—H13A	109.5	C23—C231—H23A	109.5
C13—C131—H13B	109.5	C23—C231—H23B	109.5
H13A—C131—H13B	109.5	H23A—C231—H23B	109.5
C13—C131—H13C	109.5	C23—C231—H23C	109.5
H13A—C131—H13C	109.5	H23A—C231—H23C	109.5
H13B—C131—H13C	109.5	H23B—C231—H23C	109.5
C15—O151—C151	116.19 (16)	C25—O251—C251	117.88 (16)
C156—C151—C152	120.2 (2)	C252—C251—C256	120.3 (2)
C156—C151—O151	122.55 (18)	C252—C251—O251	116.61 (19)
C152—C151—O151	117.18 (19)	C256—C251—O251	123.02 (19)
C151—C152—C153	119.7 (2)	C251—C252—C253	119.5 (2)
C151—C152—Cl12	119.99 (17)	C251—C252—Cl22	120.09 (17)
C153—C152—Cl12	120.30 (18)	C253—C252—Cl22	120.40 (17)
C154—C153—C152	120.1 (2)	C254—C253—C252	120.1 (2)
C154—C153—H153	120.0	C254—C253—H253	119.9
C152—C153—H153	120.0	C252—C253—H253	119.9
C153—C154—C155	120.2 (2)	C253—C254—C255	120.3 (2)
C153—C154—H154	119.9	C253—C254—H254	119.8
C155—C154—H154	119.9	C255—C254—H254	119.8
C154—C155—C156	120.2 (2)	C254—C255—C256	119.9 (2)
C154—C155—H155	119.9	C254—C255—H255	120.0
C156—C155—H155	119.9	C256—C255—H255	120.0
C151—C156—C155	119.6 (2)	C251—C256—C255	119.8 (2)
C151—C156—H156	120.2	C251—C256—H256	120.1
C155—C156—H156	120.2	C255—C256—H256	120.1
O141—C141—C14	122.4 (5)	O241—C241—C24	118.2 (12)
O141—C141—H141	118.8	O241—C241—H241	120.9
C14—C141—H141	118.8	C24—C241—H241	120.9
O341—C341—C14	112.0 (19)	O441—C441—C24	118.2 (15)
O341—C341—H341	124.0	O441—C441—H441	120.9
C14—C341—H341	124.0	C24—C441—H441	120.9

C15—N11—N12—C13	−0.5 (2)	C25—N21—N22—C23	−0.2 (2)
C111—N11—N12—C13	178.80 (18)	C211—N21—N22—C23	177.93 (18)
N11—N12—C13—C14	0.8 (3)	N21—N22—C23—C24	0.3 (2)
N11—N12—C13—C131	−179.6 (2)	N21—N22—C23—C231	−178.8 (2)
N12—C13—C14—C15	−0.8 (3)	N22—C23—C24—C25	−0.4 (3)
C131—C13—C14—C15	179.6 (2)	C231—C23—C24—C25	178.7 (2)
N12—C13—C14—C141	177.3 (9)	N22—C23—C24—C241	172.2 (13)
C131—C13—C14—C141	−2.3 (10)	C231—C23—C24—C241	−8.8 (14)
N12—C13—C14—C341	176 (2)	N22—C23—C24—C441	−176.2 (17)
C131—C13—C14—C341	−3 (2)	C231—C23—C24—C441	2.9 (17)
N12—N11—C15—O151	−178.96 (18)	N22—N21—C25—O251	−175.75 (17)
C111—N11—C15—O151	1.9 (3)	C211—N21—C25—O251	6.5 (3)
N12—N11—C15—C14	0.0 (2)	N22—N21—C25—C24	0.0 (2)
C111—N11—C15—C14	−179.2 (2)	C211—N21—C25—C24	−177.8 (2)
C141—C14—C15—N11	−177.5 (10)	C241—C24—C25—N21	−171.4 (14)
C13—C14—C15—N11	0.5 (2)	C23—C24—C25—N21	0.2 (2)
C341—C14—C15—N11	−177.4 (18)	C441—C24—C25—N21	176.8 (15)
C141—C14—C15—O151	1.3 (11)	C241—C24—C25—O251	3.8 (14)
C13—C14—C15—O151	179.3 (2)	C23—C24—C25—O251	175.4 (2)
C341—C14—C15—O151	1.4 (19)	C441—C24—C25—O251	−8.0 (15)
C15—N11—C111—C112	−19.3 (4)	C25—N21—C211—C216	166.6 (2)
N12—N11—C111—C112	161.6 (2)	N22—N21—C211—C216	−11.1 (3)
C15—N11—C111—C116	161.9 (2)	C25—N21—C211—C212	−13.3 (3)
N12—N11—C111—C116	−17.2 (3)	N22—N21—C211—C212	169.0 (2)
C116—C111—C112—C113	−1.4 (5)	C216—C211—C212—C213	−0.9 (4)
N11—C111—C112—C113	179.9 (3)	N21—C211—C212—C213	178.9 (2)
C111—C112—C113—C114	1.3 (6)	C211—C212—C213—C214	1.3 (5)
C112—C113—C114—C115	−0.4 (6)	C212—C213—C214—C215	−0.6 (5)
C113—C114—C115—C116	−0.3 (5)	C213—C214—C215—C216	−0.4 (4)
C112—C111—C116—C115	0.6 (4)	C214—C215—C216—C211	0.6 (4)
N11—C111—C116—C115	179.4 (2)	C212—C211—C216—C215	0.0 (4)
C114—C115—C116—C111	0.2 (5)	N21—C211—C216—C215	−179.9 (2)
N11—C15—O151—C151	−110.9 (2)	N21—C25—O251—C251	−117.7 (2)
C14—C15—O151—C151	70.4 (3)	C24—C25—O251—C251	67.6 (3)
C15—O151—C151—C156	29.1 (3)	C25—O251—C251—C252	−153.77 (19)
C15—O151—C151—C152	−153.42 (19)	C25—O251—C251—C256	29.0 (3)
C156—C151—C152—C153	−0.7 (3)	C256—C251—C252—C253	−0.3 (3)
O151—C151—C152—C153	−178.17 (19)	O251—C251—C252—C253	−177.63 (18)
C156—C151—C152—Cl12	−179.69 (16)	C256—C251—C252—Cl22	178.53 (17)
O151—C151—C152—Cl12	2.8 (3)	O251—C251—C252—Cl22	1.3 (2)
C151—C152—C153—C154	0.6 (4)	C251—C252—C253—C254	0.4 (3)
Cl12—C152—C153—C154	179.7 (2)	Cl22—C252—C253—C254	−178.51 (17)
C152—C153—C154—C155	−0.5 (4)	C252—C253—C254—C255	−0.3 (4)
C153—C154—C155—C156	0.4 (4)	C253—C254—C255—C256	0.3 (4)
C152—C151—C156—C155	0.6 (3)	C252—C251—C256—C255	0.3 (3)
O151—C151—C156—C155	177.94 (19)	O251—C251—C256—C255	177.4 (2)
C154—C155—C156—C151	−0.5 (4)	C254—C255—C256—C251	−0.3 (4)
C15—C14—C141—O141	1 (2)	C25—C24—C241—O241	−9 (3)
C13—C14—C141—O141	−176.7 (9)	C23—C24—C241—O241	−179.1 (12)
C341—C14—C141—O141	0 (10)	C441—C24—C241—O241	35 (8)
C15—C14—C341—O341	−176.6 (18)	C25—C24—C441—O441	177.0 (16)
C141—C14—C341—O341	3 (9)	C241—C24—C441—O441	34 (8)
C13—C14—C341—O341	6 (4)	C23—C24—C441—O441	−8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C156—H156···N12ⁱ	0.93	2.59	3.433 (3)	152
C255—H255···Cg3ⁱⁱ	0.93	2.80	3.635 (3)	140

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

3-Methyl-5-(4-nitrophenoxy)-1-phenyl-1H-pyrazole-4-carbaldehyde (IV) top

Crystal data top

C₁₇H₁₃N₃O₄	F(000) = 672
M_r = 323.30	D_x = 1.384 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.1163 (9) Å	Cell parameters from 4821 reflections
b = 11.7268 (7) Å	θ = 1.4–30.8°
c = 9.3982 (5) Å	µ = 0.10 mm⁻¹
β = 94.259 (3)°	T = 296 K
V = 1551.47 (16) Å³	Block, colourless
Z = 4	0.20 × 0.15 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	3956 independent reflections
Radiation source: fine focus sealed tube	2361 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 0.3333 pixels mm^-1	θ_max = 28.6°, θ_min = 2.3°
φ and ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −15→15
T_min = 0.945, T_max = 0.985	l = −12→12
28186 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0385P)² + 0.5804P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.121	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 0.19 e Å⁻³
3956 reflections	Δρ_min = −0.15 e Å⁻³
219 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0064 (11)
Primary atom site location: difference Fourier map

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.86994 (10)	0.04307 (11)	0.28782 (14)	0.0439 (3)
N2	0.96335 (10)	0.07594 (12)	0.28157 (15)	0.0467 (4)
C3	0.98509 (13)	0.12942 (14)	0.40292 (19)	0.0463 (4)
C4	0.90857 (13)	0.13138 (14)	0.49144 (18)	0.0471 (4)
C5	0.83639 (13)	0.07652 (14)	0.41151 (18)	0.0457 (4)
C11	0.82349 (12)	−0.01374 (14)	0.16813 (18)	0.0442 (4)
C12	0.75167 (13)	−0.09122 (16)	0.1842 (2)	0.0552 (5)
H12	0.7326	−0.1081	0.2745	0.066*
C13	0.70832 (15)	−0.14363 (18)	0.0648 (2)	0.0674 (6)
H13	0.6590	−0.1950	0.0747	0.081*
C14	0.73745 (17)	−0.1204 (2)	−0.0681 (2)	0.0711 (6)
H14	0.7083	−0.1564	−0.1479	0.085*
C15	0.80937 (17)	−0.04447 (18)	−0.0831 (2)	0.0680 (6)
H15	0.8290	−0.0291	−0.1735	0.082*
C16	0.85318 (15)	0.00968 (16)	0.03427 (19)	0.0561 (5)
H16	0.9021	0.0614	0.0235	0.067*
C31	1.08136 (14)	0.18030 (18)	0.4311 (2)	0.0648 (5)
H31A	1.1212	0.1570	0.3580	0.097*
H31B	1.1086	0.1548	0.5223	0.097*
H31C	1.0763	0.2619	0.4314	0.097*
C41	0.91097 (17)	0.17425 (17)	0.6348 (2)	0.0625 (5)
H41	0.9677	0.2070	0.6710	0.075*
O41	0.84724 (12)	0.17227 (14)	0.71320 (15)	0.0781 (5)
O51	0.74717 (9)	0.04733 (10)	0.43900 (14)	0.0592 (4)
C51	0.68931 (12)	0.12862 (15)	0.49678 (18)	0.0463 (4)
C52	0.69553 (13)	0.24277 (15)	0.46518 (18)	0.0496 (4)
H52	0.7389	0.2687	0.4028	0.060*
C53	0.63630 (13)	0.31763 (15)	0.52768 (19)	0.0512 (4)
H53	0.6394	0.3954	0.5091	0.061*
C54	0.57244 (12)	0.27586 (16)	0.61811 (18)	0.0484 (4)
C55	0.56359 (13)	0.16141 (17)	0.6451 (2)	0.0544 (5)
H55	0.5183	0.1352	0.7042	0.065*
C56	0.62287 (13)	0.08639 (16)	0.5831 (2)	0.0536 (5)
H56	0.6182	0.0084	0.5991	0.064*
N54	0.51327 (12)	0.35609 (18)	0.69134 (19)	0.0662 (5)
O411	0.52206 (15)	0.45668 (17)	0.6681 (2)	0.1137 (7)
O412	0.45836 (11)	0.31846 (16)	0.77356 (18)	0.0883 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0479 (8)	0.0408 (7)	0.0444 (8)	−0.0016 (6)	0.0128 (6)	−0.0032 (6)
N2	0.0457 (8)	0.0458 (8)	0.0497 (8)	0.0006 (6)	0.0112 (7)	0.0000 (7)
C3	0.0540 (10)	0.0347 (8)	0.0504 (10)	0.0017 (7)	0.0051 (8)	0.0018 (8)
C4	0.0629 (11)	0.0341 (8)	0.0452 (9)	−0.0001 (8)	0.0097 (8)	−0.0014 (7)
C5	0.0568 (11)	0.0336 (8)	0.0488 (10)	−0.0012 (7)	0.0182 (8)	−0.0013 (7)
C11	0.0487 (10)	0.0370 (9)	0.0474 (9)	0.0063 (7)	0.0067 (8)	−0.0055 (7)
C12	0.0553 (11)	0.0525 (11)	0.0588 (11)	−0.0019 (9)	0.0108 (9)	−0.0076 (9)
C13	0.0568 (12)	0.0620 (13)	0.0828 (16)	−0.0055 (10)	0.0017 (11)	−0.0178 (11)
C14	0.0757 (15)	0.0687 (14)	0.0666 (14)	0.0113 (12)	−0.0108 (11)	−0.0214 (11)
C15	0.0945 (17)	0.0621 (13)	0.0476 (11)	0.0078 (12)	0.0066 (11)	−0.0088 (10)
C16	0.0712 (13)	0.0485 (10)	0.0500 (11)	−0.0004 (9)	0.0147 (9)	−0.0047 (9)
C31	0.0585 (12)	0.0596 (12)	0.0754 (14)	−0.0064 (10)	−0.0015 (10)	−0.0040 (10)
C41	0.0826 (15)	0.0513 (11)	0.0542 (12)	−0.0012 (10)	0.0087 (11)	−0.0119 (9)
O41	0.1000 (12)	0.0851 (11)	0.0520 (8)	−0.0015 (9)	0.0233 (8)	−0.0131 (7)
O51	0.0639 (8)	0.0432 (7)	0.0748 (9)	−0.0105 (6)	0.0349 (7)	−0.0144 (6)
C51	0.0511 (10)	0.0438 (9)	0.0458 (9)	−0.0049 (8)	0.0155 (8)	−0.0075 (8)
C52	0.0542 (10)	0.0474 (10)	0.0496 (10)	−0.0046 (8)	0.0188 (8)	0.0022 (8)
C53	0.0523 (11)	0.0437 (10)	0.0582 (11)	−0.0008 (8)	0.0083 (9)	0.0008 (8)
C54	0.0418 (9)	0.0554 (11)	0.0486 (10)	0.0040 (8)	0.0074 (8)	−0.0060 (8)
C55	0.0486 (10)	0.0624 (12)	0.0547 (11)	−0.0048 (9)	0.0196 (9)	0.0025 (9)
C56	0.0583 (11)	0.0445 (10)	0.0603 (11)	−0.0086 (8)	0.0202 (9)	0.0012 (9)
N54	0.0526 (10)	0.0765 (13)	0.0705 (11)	0.0135 (9)	0.0111 (9)	−0.0097 (10)
O411	0.1183 (16)	0.0660 (12)	0.1644 (19)	0.0205 (11)	0.0609 (14)	−0.0166 (12)
O412	0.0690 (10)	0.1129 (14)	0.0875 (11)	0.0230 (9)	0.0358 (9)	0.0012 (10)

Geometric parameters (Å, º) top

N1—C5	1.346 (2)	C31—H31A	0.9600
N1—N2	1.3792 (19)	C31—H31B	0.9600
N1—C11	1.425 (2)	C31—H31C	0.9600
N2—C3	1.318 (2)	C41—O41	1.205 (2)
C3—C4	1.412 (2)	C41—H41	0.9300
C3—C31	1.490 (3)	O51—C51	1.392 (2)
C4—C5	1.379 (2)	C51—C52	1.375 (2)
C4—C41	1.436 (3)	C51—C56	1.377 (2)
C5—O51	1.349 (2)	C52—C53	1.374 (2)
C11—C12	1.378 (2)	C52—H52	0.9300
C11—C16	1.383 (2)	C53—C54	1.374 (2)
C12—C13	1.382 (3)	C53—H53	0.9300
C12—H12	0.9300	C54—C55	1.373 (3)
C13—C14	1.371 (3)	C54—N54	1.464 (2)
C13—H13	0.9300	C55—C56	1.373 (2)
C14—C15	1.366 (3)	C55—H55	0.9300
C14—H14	0.9300	C56—H56	0.9300
C15—C16	1.379 (3)	N54—O411	1.208 (2)
C15—H15	0.9300	N54—O412	1.217 (2)
C16—H16	0.9300

C5—N1—N2	110.74 (14)	C3—C31—H31A	109.5
C5—N1—C11	130.35 (14)	C3—C31—H31B	109.5
N2—N1—C11	118.85 (13)	H31A—C31—H31B	109.5
C3—N2—N1	104.96 (13)	C3—C31—H31C	109.5
N2—C3—C4	112.24 (16)	H31A—C31—H31C	109.5
N2—C3—C31	119.70 (16)	H31B—C31—H31C	109.5
C4—C3—C31	128.05 (17)	O41—C41—C4	126.9 (2)
C5—C4—C3	103.77 (15)	O41—C41—H41	116.5
C5—C4—C41	129.73 (17)	C4—C41—H41	116.5
C3—C4—C41	126.36 (18)	C5—O51—C51	118.98 (13)
N1—C5—O51	119.02 (15)	C52—C51—C56	122.32 (16)
N1—C5—C4	108.26 (15)	C52—C51—O51	122.25 (15)
O51—C5—C4	132.58 (15)	C56—C51—O51	115.38 (15)
C12—C11—C16	120.40 (17)	C53—C52—C51	118.61 (16)
C12—C11—N1	121.39 (15)	C53—C52—H52	120.7
C16—C11—N1	118.21 (16)	C51—C52—H52	120.7
C11—C12—C13	119.28 (19)	C52—C53—C54	118.99 (17)
C11—C12—H12	120.4	C52—C53—H53	120.5
C13—C12—H12	120.4	C54—C53—H53	120.5
C14—C13—C12	120.5 (2)	C55—C54—C53	122.36 (16)
C14—C13—H13	119.8	C55—C54—N54	118.60 (17)
C12—C13—H13	119.8	C53—C54—N54	119.02 (18)
C15—C14—C13	120.0 (2)	C54—C55—C56	118.77 (16)
C15—C14—H14	120.0	C54—C55—H55	120.6
C13—C14—H14	120.0	C56—C55—H55	120.6
C14—C15—C16	120.7 (2)	C55—C56—C51	118.85 (17)
C14—C15—H15	119.7	C55—C56—H56	120.6
C16—C15—H15	119.7	C51—C56—H56	120.6
C15—C16—C11	119.23 (19)	O411—N54—O412	123.20 (19)
C15—C16—H16	120.4	O411—N54—C54	118.24 (18)
C11—C16—H16	120.4	O412—N54—C54	118.56 (19)

C5—N1—N2—C3	−0.03 (18)	C13—C14—C15—C16	−0.2 (3)
C11—N1—N2—C3	177.50 (14)	C14—C15—C16—C11	0.0 (3)
N1—N2—C3—C4	0.99 (19)	C12—C11—C16—C15	0.7 (3)
N1—N2—C3—C31	−178.18 (15)	N1—C11—C16—C15	179.87 (17)
N2—C3—C4—C5	−1.54 (19)	C5—C4—C41—O41	−1.9 (3)
C31—C3—C4—C5	177.54 (18)	C3—C4—C41—O41	−176.9 (2)
N2—C3—C4—C41	174.50 (17)	N1—C5—O51—C51	−136.63 (16)
C31—C3—C4—C41	−6.4 (3)	C4—C5—O51—C51	48.3 (3)
N2—N1—C5—O51	−177.14 (14)	C5—O51—C51—C52	32.7 (3)
C11—N1—C5—O51	5.7 (3)	C5—O51—C51—C56	−149.82 (17)
N2—N1—C5—C4	−0.94 (19)	C56—C51—C52—C53	3.2 (3)
C11—N1—C5—C4	−178.10 (16)	O51—C51—C52—C53	−179.48 (16)
C3—C4—C5—N1	1.44 (18)	C51—C52—C53—C54	−0.7 (3)
C41—C4—C5—N1	−174.41 (18)	C52—C53—C54—C55	−2.0 (3)
C3—C4—C5—O51	176.93 (18)	C52—C53—C54—N54	176.39 (16)
C41—C4—C5—O51	1.1 (3)	C53—C54—C55—C56	2.2 (3)
C5—N1—C11—C12	−32.5 (3)	N54—C54—C55—C56	−176.22 (17)
N2—N1—C11—C12	150.56 (16)	C54—C55—C56—C51	0.3 (3)
C5—N1—C11—C16	148.36 (18)	C52—C51—C56—C55	−3.1 (3)
N2—N1—C11—C16	−28.6 (2)	O51—C51—C56—C55	179.48 (17)
C16—C11—C12—C13	−1.3 (3)	C55—C54—N54—O411	179.3 (2)
N1—C11—C12—C13	179.59 (17)	C53—C54—N54—O411	0.8 (3)
C11—C12—C13—C14	1.1 (3)	C55—C54—N54—O412	0.0 (3)
C12—C13—C14—C15	−0.4 (3)	C53—C54—N54—O412	−178.45 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O412ⁱ	0.93	2.57	3.330 (3)	139
C52—H52···O41ⁱⁱ	0.93	2.53	3.456 (2)	174
C55—H55···O411ⁱⁱⁱ	0.93	2.50	3.259 (3)	139
C53—H53···Cg2^iv	0.93	2.84	3.564 (2)	135

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2.

3-Methyl-5-(naphthalen-2-yloxy)-1-phenyl-1H-pyrazole-4-carbaldehyde (V) top

Crystal data top

C₂₁H₁₆N₂O₂	F(000) = 688
M_r = 328.36	D_x = 1.289 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.7302 (6) Å	Cell parameters from 4456 reflections
b = 17.2550 (16) Å	θ = 2.0–29.0°
c = 13.1989 (11) Å	µ = 0.08 mm⁻¹
β = 106.079 (2)°	T = 296 K
V = 1691.7 (2) Å³	Block, brown
Z = 4	0.20 × 0.16 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	4311 independent reflections
Radiation source: fine focus sealed tube	2711 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
Detector resolution: 0.3333 pixels mm^-1	θ_max = 28.6°, θ_min = 2.4°
φ and ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −23→23
T_min = 0.954, T_max = 0.988	l = −17→17
34394 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0511P)² + 0.449P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4311 reflections	Δρ_max = 0.17 e Å⁻³
227 parameters	Δρ_min = −0.25 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.49965 (16)	0.38271 (8)	0.43857 (10)	0.0354 (3)
N2	0.32134 (17)	0.36741 (8)	0.38728 (10)	0.0415 (3)
C3	0.2601 (2)	0.32861 (10)	0.45616 (13)	0.0404 (4)
C4	0.3964 (2)	0.31630 (10)	0.55195 (13)	0.0393 (4)
C5	0.5463 (2)	0.35199 (9)	0.53568 (12)	0.0356 (3)
C11	0.60936 (19)	0.42022 (9)	0.38274 (11)	0.0328 (3)
C12	0.7251 (2)	0.47936 (9)	0.42849 (13)	0.0411 (4)
H12	0.7348	0.4949	0.4973	0.049*
C13	0.8265 (2)	0.51508 (11)	0.37058 (16)	0.0522 (5)
H13	0.9065	0.5544	0.4010	0.063*
C14	0.8099 (3)	0.49299 (12)	0.26867 (17)	0.0616 (6)
H14	0.8775	0.5176	0.2298	0.074*
C15	0.6933 (3)	0.43438 (12)	0.22374 (15)	0.0598 (5)
H15	0.6820	0.4197	0.1544	0.072*
C16	0.5936 (2)	0.39740 (10)	0.28053 (13)	0.0447 (4)
H16	0.5160	0.3573	0.2503	0.054*
C31	0.0691 (2)	0.30215 (13)	0.42740 (16)	0.0597 (5)
H31A	0.0073	0.3213	0.3586	0.090*
H31B	0.0115	0.3216	0.4780	0.090*
H31C	0.0654	0.2465	0.4270	0.090*
C41	0.3834 (3)	0.27328 (11)	0.64338 (15)	0.0526 (5)
H41	0.4890	0.2654	0.6969	0.063*
O41	0.2458 (2)	0.24671 (9)	0.65573 (13)	0.0737 (5)
O51	0.72116 (14)	0.35620 (8)	0.59018 (8)	0.0467 (3)
C51	0.9302 (2)	0.33196 (9)	0.75230 (12)	0.0358 (3)
H51	0.9925	0.3013	0.7163	0.043*
C52	0.7727 (2)	0.36509 (9)	0.69996 (12)	0.0362 (4)
C53	0.6730 (2)	0.41139 (11)	0.75088 (14)	0.0492 (4)
H53	0.5655	0.4342	0.7130	0.059*
C54	0.7369 (2)	0.42215 (11)	0.85672 (14)	0.0522 (5)
H54	0.6702	0.4517	0.8914	0.063*
C54A	0.9017 (2)	0.38972 (10)	0.91541 (12)	0.0401 (4)
C55	0.9757 (3)	0.40256 (12)	1.02489 (14)	0.0530 (5)
H55	0.9116	0.4319	1.0614	0.064*
C56	1.1380 (3)	0.37294 (13)	1.07740 (14)	0.0588 (5)
H56	1.1842	0.3820	1.1493	0.071*
C57	1.2360 (3)	0.32887 (12)	1.02410 (15)	0.0577 (5)
H57	1.3483	0.3096	1.0605	0.069*
C58	1.1689 (2)	0.31377 (11)	0.91914 (14)	0.0486 (4)
H58	1.2346	0.2833	0.8849	0.058*
C58A	1.0003 (2)	0.34402 (9)	0.86189 (12)	0.0357 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0282 (7)	0.0455 (8)	0.0302 (7)	−0.0012 (5)	0.0041 (5)	0.0019 (6)
N2	0.0287 (7)	0.0557 (9)	0.0367 (7)	−0.0034 (6)	0.0036 (6)	−0.0029 (6)
C3	0.0342 (8)	0.0449 (9)	0.0429 (9)	−0.0035 (7)	0.0120 (7)	−0.0081 (7)
C4	0.0386 (9)	0.0423 (9)	0.0402 (9)	0.0018 (7)	0.0166 (7)	−0.0001 (7)
C5	0.0313 (8)	0.0443 (9)	0.0309 (8)	0.0048 (7)	0.0082 (6)	0.0022 (6)
C11	0.0296 (7)	0.0358 (8)	0.0318 (8)	0.0015 (6)	0.0068 (6)	0.0027 (6)
C12	0.0413 (9)	0.0420 (9)	0.0383 (9)	0.0001 (7)	0.0084 (7)	−0.0052 (7)
C13	0.0493 (10)	0.0455 (10)	0.0625 (12)	−0.0127 (8)	0.0166 (9)	−0.0026 (9)
C14	0.0722 (14)	0.0593 (12)	0.0655 (13)	−0.0135 (10)	0.0393 (11)	0.0030 (10)
C15	0.0767 (14)	0.0670 (13)	0.0451 (10)	−0.0114 (11)	0.0327 (10)	−0.0055 (9)
C16	0.0494 (10)	0.0473 (10)	0.0380 (9)	−0.0078 (8)	0.0131 (8)	−0.0056 (7)
C31	0.0395 (10)	0.0760 (14)	0.0642 (13)	−0.0148 (9)	0.0153 (9)	−0.0146 (11)
C41	0.0580 (11)	0.0540 (11)	0.0537 (11)	0.0038 (9)	0.0284 (9)	0.0080 (9)
O41	0.0737 (10)	0.0734 (10)	0.0916 (12)	−0.0013 (8)	0.0523 (9)	0.0165 (8)
O51	0.0296 (6)	0.0782 (9)	0.0297 (6)	0.0051 (5)	0.0039 (5)	0.0068 (5)
C51	0.0315 (8)	0.0417 (9)	0.0333 (8)	0.0025 (6)	0.0076 (6)	0.0016 (7)
C52	0.0329 (8)	0.0453 (9)	0.0291 (8)	0.0013 (7)	0.0061 (6)	0.0050 (7)
C53	0.0374 (9)	0.0583 (11)	0.0470 (10)	0.0154 (8)	0.0034 (8)	0.0015 (8)
C54	0.0450 (10)	0.0606 (12)	0.0514 (11)	0.0110 (8)	0.0139 (9)	−0.0113 (9)
C54A	0.0398 (9)	0.0454 (9)	0.0348 (8)	−0.0031 (7)	0.0098 (7)	−0.0009 (7)
C55	0.0565 (12)	0.0643 (12)	0.0392 (10)	−0.0084 (9)	0.0149 (9)	−0.0089 (9)
C56	0.0611 (12)	0.0744 (14)	0.0329 (9)	−0.0137 (10)	−0.0004 (9)	0.0020 (9)
C57	0.0466 (11)	0.0665 (13)	0.0476 (11)	0.0001 (9)	−0.0076 (9)	0.0077 (9)
C58	0.0409 (9)	0.0554 (11)	0.0432 (10)	0.0068 (8)	0.0009 (8)	0.0033 (8)
C58A	0.0326 (8)	0.0377 (8)	0.0350 (8)	−0.0019 (6)	0.0061 (7)	0.0056 (6)

Geometric parameters (Å, º) top

N1—C5	1.3408 (19)	C31—H31C	0.9600
N1—N2	1.3824 (17)	C41—O41	1.210 (2)
N1—C11	1.4240 (19)	C41—H41	0.9300
N2—C3	1.318 (2)	O51—C52	1.4008 (18)
C3—C4	1.420 (2)	C51—C52	1.350 (2)
C3—C31	1.491 (2)	C51—C58A	1.412 (2)
C4—C5	1.381 (2)	C51—H51	0.9300
C4—C41	1.444 (2)	C52—C53	1.404 (2)
C5—O51	1.3455 (18)	C53—C54	1.359 (2)
C11—C16	1.378 (2)	C53—H53	0.9300
C11—C12	1.381 (2)	C54—C54A	1.411 (2)
C12—C13	1.382 (2)	C54—H54	0.9300
C12—H12	0.9300	C54A—C58A	1.414 (2)
C13—C14	1.370 (3)	C54A—C55	1.416 (2)
C13—H13	0.9300	C55—C56	1.354 (3)
C14—C15	1.375 (3)	C55—H55	0.9300
C14—H14	0.9300	C56—C57	1.394 (3)
C15—C16	1.373 (2)	C56—H56	0.9300
C15—H15	0.9300	C57—C58	1.363 (2)
C16—H16	0.9300	C57—H57	0.9300
C31—H31A	0.9600	C58—C58A	1.413 (2)
C31—H31B	0.9600	C58—H58	0.9300

C5—N1—N2	111.14 (12)	H31B—C31—H31C	109.5
C5—N1—C11	129.29 (12)	O41—C41—C4	125.07 (19)
N2—N1—C11	119.30 (12)	O41—C41—H41	117.5
C3—N2—N1	105.01 (13)	C4—C41—H41	117.5
N2—C3—C4	111.76 (14)	C5—O51—C52	120.97 (12)
N2—C3—C31	119.97 (16)	C52—C51—C58A	119.83 (14)
C4—C3—C31	128.26 (16)	C52—C51—H51	120.1
C5—C4—C3	104.03 (14)	C58A—C51—H51	120.1
C5—C4—C41	127.95 (16)	C51—C52—O51	116.15 (13)
C3—C4—C41	127.96 (16)	C51—C52—C53	122.23 (15)
N1—C5—O51	117.02 (13)	O51—C52—C53	121.41 (14)
N1—C5—C4	108.04 (13)	C54—C53—C52	118.57 (15)
O51—C5—C4	134.67 (14)	C54—C53—H53	120.7
C16—C11—C12	120.67 (14)	C52—C53—H53	120.7
C16—C11—N1	118.22 (14)	C53—C54—C54A	121.75 (16)
C12—C11—N1	121.09 (13)	C53—C54—H54	119.1
C11—C12—C13	119.06 (15)	C54A—C54—H54	119.1
C11—C12—H12	120.5	C54—C54A—C58A	118.46 (14)
C13—C12—H12	120.5	C54—C54A—C55	123.10 (16)
C14—C13—C12	120.38 (17)	C58A—C54A—C55	118.41 (15)
C14—C13—H13	119.8	C56—C55—C54A	121.20 (17)
C12—C13—H13	119.8	C56—C55—H55	119.4
C13—C14—C15	120.02 (17)	C54A—C55—H55	119.4
C13—C14—H14	120.0	C55—C56—C57	120.24 (17)
C15—C14—H14	120.0	C55—C56—H56	119.9
C16—C15—C14	120.44 (17)	C57—C56—H56	119.9
C16—C15—H15	119.8	C58—C57—C56	120.69 (18)
C14—C15—H15	119.8	C58—C57—H57	119.7
C15—C16—C11	119.40 (16)	C56—C57—H57	119.7
C15—C16—H16	120.3	C57—C58—C58A	120.52 (17)
C11—C16—H16	120.3	C57—C58—H58	119.7
C3—C31—H31A	109.5	C58A—C58—H58	119.7
C3—C31—H31B	109.5	C51—C58A—C58	121.90 (15)
H31A—C31—H31B	109.5	C51—C58A—C54A	119.14 (14)
C3—C31—H31C	109.5	C58—C58A—C54A	118.93 (15)
H31A—C31—H31C	109.5

C5—N1—N2—C3	1.54 (17)	N1—C11—C16—C15	177.84 (16)
C11—N1—N2—C3	176.03 (13)	C5—C4—C41—O41	175.77 (19)
N1—N2—C3—C4	−1.31 (18)	C3—C4—C41—O41	−7.5 (3)
N1—N2—C3—C31	179.93 (15)	N1—C5—O51—C52	146.36 (14)
N2—C3—C4—C5	0.64 (19)	C4—C5—O51—C52	−40.5 (3)
C31—C3—C4—C5	179.27 (17)	C58A—C51—C52—O51	174.26 (13)
N2—C3—C4—C41	−176.73 (16)	C58A—C51—C52—C53	−0.5 (2)
C31—C3—C4—C41	1.9 (3)	C5—O51—C52—C51	148.23 (15)
N2—N1—C5—O51	173.68 (13)	C5—O51—C52—C53	−37.0 (2)
C11—N1—C5—O51	−0.1 (2)	C51—C52—C53—C54	−0.9 (3)
N2—N1—C5—C4	−1.17 (18)	O51—C52—C53—C54	−175.35 (16)
C11—N1—C5—C4	−174.96 (14)	C52—C53—C54—C54A	1.6 (3)
C3—C4—C5—N1	0.34 (17)	C53—C54—C54A—C58A	−0.9 (3)
C41—C4—C5—N1	177.71 (16)	C53—C54—C54A—C55	177.24 (18)
C3—C4—C5—O51	−173.21 (17)	C54—C54A—C55—C56	−177.22 (18)
C41—C4—C5—O51	4.2 (3)	C58A—C54A—C55—C56	0.9 (3)
C5—N1—C11—C16	131.39 (17)	C54A—C55—C56—C57	0.0 (3)
N2—N1—C11—C16	−42.0 (2)	C55—C56—C57—C58	−1.2 (3)
C5—N1—C11—C12	−50.3 (2)	C56—C57—C58—C58A	1.4 (3)
N2—N1—C11—C12	136.31 (15)	C52—C51—C58A—C58	−176.80 (16)
C16—C11—C12—C13	−0.5 (2)	C52—C51—C58A—C54A	1.1 (2)
N1—C11—C12—C13	−178.77 (15)	C57—C58—C58A—C51	177.50 (17)
C11—C12—C13—C14	1.1 (3)	C57—C58—C58A—C54A	−0.5 (3)
C12—C13—C14—C15	−0.7 (3)	C54—C54A—C58A—C51	−0.5 (2)
C13—C14—C15—C16	−0.3 (3)	C55—C54A—C58A—C51	−178.71 (15)
C14—C15—C16—C11	0.9 (3)	C54—C54A—C58A—C58	177.54 (16)
C12—C11—C16—C15	−0.4 (3)	C55—C54A—C58A—C58	−0.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C51—H51···O41ⁱ	0.93	2.50	3.386 (2)	160
C12—H12···Cg1ⁱⁱ	0.93	2.96	3.4804 (17)	117
C53—H53···Cg2ⁱⁱ	0.93	2.78	3.6477 (19)	155

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

3-Methyl-1-phenyl-5-(piperidin-1-yl)-1H-pyrazole-4-carbaldehyde (VI) top

Crystal data top

C₁₆H₁₉N₃O	F(000) = 576
M_r = 269.34	D_x = 1.243 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.9432 (7) Å	Cell parameters from 3504 reflections
b = 16.0546 (14) Å	θ = 2.4–28.1°
c = 10.1155 (8) Å	µ = 0.08 mm⁻¹
β = 97.777 (2)°	T = 296 K
V = 1439.0 (2) Å³	Block, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3000 independent reflections
Radiation source: fine focus sealed tube	1869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 0.3333 pixels mm^-1	θ_max = 26.6°, θ_min = 2.4°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −20→20
T_min = 0.950, T_max = 0.992	l = −12→12
27358 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0563P)² + 0.4589P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.141	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.29 e Å⁻³
3000 reflections	Δρ_min = −0.18 e Å⁻³
183 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.011 (2)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.35185 (18)	0.62845 (10)	0.68452 (15)	0.0453 (4)
N2	0.39911 (19)	0.66723 (12)	0.57496 (17)	0.0531 (5)
C3	0.3664 (2)	0.61450 (15)	0.4763 (2)	0.0522 (5)
C4	0.3031 (2)	0.53927 (13)	0.51801 (18)	0.0479 (5)
C5	0.2954 (2)	0.55100 (12)	0.65407 (18)	0.0427 (5)
C11	0.3634 (2)	0.67370 (12)	0.80659 (19)	0.0448 (5)
C12	0.2377 (2)	0.68566 (13)	0.8697 (2)	0.0520 (5)
H12	0.1447	0.6644	0.8324	0.062*
C13	0.2501 (3)	0.72930 (14)	0.9883 (2)	0.0618 (6)
H13	0.1656	0.7373	1.0312	0.074*
C14	0.3876 (3)	0.76093 (15)	1.0431 (2)	0.0674 (7)
H14	0.3962	0.7897	1.1235	0.081*
C15	0.5118 (3)	0.75014 (15)	0.9793 (2)	0.0685 (7)
H15	0.6040	0.7727	1.0158	0.082*
C16	0.5011 (2)	0.70600 (14)	0.8610 (2)	0.0574 (6)
H16	0.5860	0.6981	0.8185	0.069*
C31	0.3991 (3)	0.63675 (19)	0.3393 (2)	0.0774 (8)
H31A	0.4450	0.6909	0.3412	0.116*
H31B	0.3067	0.6373	0.2787	0.116*
H31C	0.4666	0.5963	0.3100	0.116*
C41	0.2749 (3)	0.46445 (16)	0.4411 (2)	0.0646 (6)
H41	0.2456	0.4179	0.4859	0.078*
O41	0.2855 (2)	0.45590 (13)	0.32399 (16)	0.0913 (6)
N51	0.24068 (18)	0.50265 (10)	0.74926 (15)	0.0456 (4)
C52	0.1312 (3)	0.43642 (16)	0.7089 (2)	0.0616 (6)
H52A	0.1842	0.3857	0.6916	0.074*
H52B	0.0682	0.4524	0.6272	0.074*
C53	0.0347 (3)	0.42096 (16)	0.8158 (2)	0.0653 (6)
H53A	−0.0323	0.3745	0.7900	0.078*
H53B	−0.0269	0.4697	0.8254	0.078*
C54	0.1283 (3)	0.40178 (14)	0.9484 (2)	0.0596 (6)
H54A	0.1778	0.3483	0.9432	0.071*
H54B	0.0629	0.3982	1.0173	0.071*
C55	0.2464 (2)	0.46891 (15)	0.9851 (2)	0.0560 (6)
H55A	0.1969	0.5204	1.0045	0.067*
H55B	0.3124	0.4523	1.0648	0.067*
C56	0.3381 (2)	0.48331 (13)	0.87430 (19)	0.0489 (5)
H56A	0.4074	0.5291	0.8975	0.059*
H56B	0.3972	0.4339	0.8621	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0486 (9)	0.0487 (10)	0.0407 (9)	−0.0008 (8)	0.0135 (7)	0.0070 (7)
N2	0.0523 (10)	0.0596 (11)	0.0498 (10)	0.0034 (8)	0.0161 (8)	0.0169 (9)
C3	0.0477 (12)	0.0675 (14)	0.0430 (11)	0.0110 (10)	0.0123 (9)	0.0149 (11)
C4	0.0496 (12)	0.0587 (13)	0.0356 (10)	0.0092 (10)	0.0067 (8)	0.0054 (9)
C5	0.0402 (10)	0.0497 (12)	0.0383 (10)	0.0035 (9)	0.0059 (8)	0.0056 (8)
C11	0.0491 (12)	0.0418 (11)	0.0434 (11)	−0.0002 (9)	0.0055 (9)	0.0065 (9)
C12	0.0516 (12)	0.0548 (13)	0.0508 (12)	−0.0007 (10)	0.0110 (10)	0.0015 (10)
C13	0.0809 (17)	0.0562 (14)	0.0508 (13)	0.0075 (12)	0.0180 (12)	0.0024 (11)
C14	0.102 (2)	0.0501 (14)	0.0471 (13)	0.0009 (13)	−0.0025 (13)	0.0030 (10)
C15	0.0754 (17)	0.0559 (14)	0.0676 (16)	−0.0100 (13)	−0.0150 (13)	0.0043 (12)
C16	0.0505 (13)	0.0552 (14)	0.0655 (14)	−0.0028 (10)	0.0049 (10)	0.0091 (11)
C31	0.0787 (17)	0.108 (2)	0.0483 (14)	0.0014 (15)	0.0186 (12)	0.0238 (14)
C41	0.0819 (16)	0.0713 (16)	0.0397 (12)	0.0097 (13)	0.0041 (11)	−0.0009 (11)
O41	0.1297 (16)	0.1042 (15)	0.0387 (10)	0.0246 (12)	0.0068 (9)	−0.0075 (9)
N51	0.0496 (9)	0.0509 (10)	0.0355 (8)	−0.0103 (8)	0.0035 (7)	0.0041 (7)
C52	0.0649 (14)	0.0685 (15)	0.0503 (13)	−0.0166 (12)	0.0039 (11)	−0.0052 (11)
C53	0.0580 (13)	0.0693 (16)	0.0700 (15)	−0.0159 (12)	0.0142 (11)	−0.0012 (12)
C54	0.0655 (14)	0.0564 (14)	0.0611 (14)	−0.0045 (11)	0.0247 (11)	0.0074 (11)
C55	0.0619 (13)	0.0641 (14)	0.0427 (12)	−0.0004 (11)	0.0098 (10)	0.0079 (10)
C56	0.0515 (11)	0.0534 (12)	0.0414 (11)	−0.0026 (10)	0.0044 (9)	0.0101 (9)

Geometric parameters (Å, º) top

N1—C5	1.361 (3)	C31—H31B	0.9600
N1—N2	1.386 (2)	C31—H31C	0.9600
N1—C11	1.424 (2)	C41—O41	1.209 (3)
N2—C3	1.311 (3)	C41—H41	0.9300
C3—C4	1.422 (3)	N51—C52	1.465 (3)
C3—C31	1.498 (3)	N51—C56	1.469 (2)
C4—C5	1.400 (3)	C52—C53	1.493 (3)
C4—C41	1.434 (3)	C52—H52A	0.9700
C5—N51	1.377 (2)	C52—H52B	0.9700
C11—C12	1.380 (3)	C53—C54	1.514 (3)
C11—C16	1.380 (3)	C53—H53A	0.9700
C12—C13	1.381 (3)	C53—H53B	0.9700
C12—H12	0.9300	C54—C55	1.519 (3)
C13—C14	1.375 (3)	C54—H54A	0.9700
C13—H13	0.9300	C54—H54B	0.9700
C14—C15	1.369 (4)	C55—C56	1.493 (3)
C14—H14	0.9300	C55—H55A	0.9700
C15—C16	1.383 (3)	C55—H55B	0.9700
C15—H15	0.9300	C56—H56A	0.9700
C16—H16	0.9300	C56—H56B	0.9700
C31—H31A	0.9600

C5—N1—N2	111.91 (16)	O41—C41—C4	126.5 (2)
C5—N1—C11	130.03 (15)	O41—C41—H41	116.7
N2—N1—C11	118.02 (16)	C4—C41—H41	116.7
C3—N2—N1	104.94 (17)	C5—N51—C52	120.08 (16)
N2—C3—C4	112.29 (17)	C5—N51—C56	119.72 (15)
N2—C3—C31	119.9 (2)	C52—N51—C56	112.51 (16)
C4—C3—C31	127.8 (2)	N51—C52—C53	110.39 (18)
C5—C4—C3	104.59 (18)	N51—C52—H52A	109.6
C5—C4—C41	128.1 (2)	C53—C52—H52A	109.6
C3—C4—C41	126.73 (19)	N51—C52—H52B	109.6
N1—C5—N51	120.83 (16)	C53—C52—H52B	109.6
N1—C5—C4	106.22 (16)	H52A—C52—H52B	108.1
N51—C5—C4	132.91 (19)	C52—C53—C54	111.81 (19)
C12—C11—C16	120.2 (2)	C52—C53—H53A	109.3
C12—C11—N1	120.24 (18)	C54—C53—H53A	109.3
C16—C11—N1	119.60 (18)	C52—C53—H53B	109.3
C11—C12—C13	119.8 (2)	C54—C53—H53B	109.3
C11—C12—H12	120.1	H53A—C53—H53B	107.9
C13—C12—H12	120.1	C53—C54—C55	110.77 (18)
C14—C13—C12	120.0 (2)	C53—C54—H54A	109.5
C14—C13—H13	120.0	C55—C54—H54A	109.5
C12—C13—H13	120.0	C53—C54—H54B	109.5
C15—C14—C13	120.1 (2)	C55—C54—H54B	109.5
C15—C14—H14	119.9	H54A—C54—H54B	108.1
C13—C14—H14	119.9	C56—C55—C54	111.16 (18)
C14—C15—C16	120.5 (2)	C56—C55—H55A	109.4
C14—C15—H15	119.8	C54—C55—H55A	109.4
C16—C15—H15	119.8	C56—C55—H55B	109.4
C11—C16—C15	119.4 (2)	C54—C55—H55B	109.4
C11—C16—H16	120.3	H55A—C55—H55B	108.0
C15—C16—H16	120.3	N51—C56—C55	110.90 (17)
C3—C31—H31A	109.5	N51—C56—H56A	109.5
C3—C31—H31B	109.5	C55—C56—H56A	109.5
H31A—C31—H31B	109.5	N51—C56—H56B	109.5
C3—C31—H31C	109.5	C55—C56—H56B	109.5
H31A—C31—H31C	109.5	H56A—C56—H56B	108.0
H31B—C31—H31C	109.5

C5—N1—N2—C3	2.2 (2)	N1—C11—C12—C13	179.70 (19)
C11—N1—N2—C3	−175.79 (16)	C11—C12—C13—C14	0.2 (3)
N1—N2—C3—C4	−2.3 (2)	C12—C13—C14—C15	0.8 (3)
N1—N2—C3—C31	178.66 (18)	C13—C14—C15—C16	−1.3 (4)
N2—C3—C4—C5	1.5 (2)	C12—C11—C16—C15	0.2 (3)
C31—C3—C4—C5	−179.5 (2)	N1—C11—C16—C15	179.78 (18)
N2—C3—C4—C41	−170.3 (2)	C14—C15—C16—C11	0.8 (3)
C31—C3—C4—C41	8.7 (3)	C5—C4—C41—O41	−178.4 (2)
N2—N1—C5—N51	−179.19 (16)	C3—C4—C41—O41	−8.4 (4)
C11—N1—C5—N51	−1.5 (3)	N1—C5—N51—C52	156.64 (19)
N2—N1—C5—C4	−1.3 (2)	C4—C5—N51—C52	−20.6 (3)
C11—N1—C5—C4	176.41 (18)	N1—C5—N51—C56	−56.2 (3)
C3—C4—C5—N1	−0.1 (2)	C4—C5—N51—C56	126.5 (2)
C41—C4—C5—N1	171.6 (2)	C5—N51—C52—C53	−152.67 (19)
C3—C4—C5—N51	177.5 (2)	C56—N51—C52—C53	58.0 (3)
C41—C4—C5—N51	−10.8 (4)	N51—C52—C53—C54	−55.2 (3)
C5—N1—C11—C12	−53.6 (3)	C52—C53—C54—C55	52.9 (3)
N2—N1—C11—C12	124.00 (19)	C53—C54—C55—C56	−52.5 (3)
C5—N1—C11—C16	126.9 (2)	C5—N51—C56—C55	152.27 (18)
N2—N1—C11—C16	−55.6 (2)	C52—N51—C56—C55	−58.3 (2)
C16—C11—C12—C13	−0.7 (3)	C54—C55—C56—N51	54.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Cg1ⁱ	0.93	2.97	3.848 (3)	159
C52—H52A···Cg2ⁱⁱ	0.97	2.96	3.761 (3)	140

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y−1/2, −z+3/2.

(3RS)-2-Acetyl-5-(4-azidophenyl)-5'-(2-chlorophenoxy)-3'-methyl-1'-phenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole] (IX) top

Crystal data top

C₂₇H₂₂ClN₇O₂	Z = 2
M_r = 511.97	F(000) = 532
Triclinic, P1	D_x = 1.361 Mg m⁻³
a = 10.8804 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3363 (4) Å	Cell parameters from 5359 reflections
c = 11.5737 (4) Å	θ = 2.1–26.9°
α = 97.294 (2)°	µ = 0.19 mm⁻¹
β = 90.050 (2)°	T = 296 K
γ = 117.840 (2)°	Block, brown
V = 1249.15 (8) Å³	0.19 × 0.17 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	5197 independent reflections
Radiation source: fine focus sealed tube	3299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 0.3333 pixels mm^-1	θ_max = 26.6°, θ_min = 2.2°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −14→14
T_min = 0.930, T_max = 0.973	l = −14→14
31603 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0469P)² + 0.5649P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
5197 reflections	Δρ_max = 0.26 e Å⁻³
336 parameters	Δρ_min = −0.26 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.71807 (17)	0.56761 (16)	0.43542 (14)	0.0402 (4)
N2	0.76299 (18)	0.58772 (17)	0.55073 (15)	0.0440 (4)
C3	0.7240 (2)	0.6740 (2)	0.60408 (18)	0.0421 (5)
C4	0.6537 (2)	0.71218 (19)	0.52591 (17)	0.0389 (5)
C5	0.6526 (2)	0.64192 (19)	0.42071 (17)	0.0386 (5)
C11	0.7491 (2)	0.4825 (2)	0.35347 (19)	0.0440 (5)
C12	0.6618 (3)	0.4089 (3)	0.2551 (2)	0.0624 (7)
H12	0.5830	0.4175	0.2385	0.075*
C13	0.6939 (4)	0.3223 (3)	0.1819 (3)	0.0841 (9)
H13	0.6368	0.2732	0.1149	0.101*
C14	0.8090 (4)	0.3079 (3)	0.2070 (3)	0.0861 (10)
H14	0.8276	0.2468	0.1588	0.103*
C15	0.8964 (3)	0.3838 (3)	0.3033 (3)	0.0732 (8)
H15	0.9758	0.3759	0.3192	0.088*
C16	0.8672 (3)	0.4714 (2)	0.3765 (2)	0.0548 (6)
H16	0.9271	0.5232	0.4415	0.066*
C31	0.7568 (3)	0.7191 (3)	0.73259 (19)	0.0600 (7)
H31A	0.8224	0.6925	0.7594	0.090*
H31B	0.6729	0.6784	0.7726	0.090*
H31C	0.7962	0.8155	0.7483	0.090*
N41	0.61493 (18)	0.95120 (17)	0.40567 (16)	0.0445 (4)
N42	0.68480 (18)	0.93628 (16)	0.49793 (16)	0.0455 (4)
C43	0.5997 (2)	0.8120 (2)	0.55003 (19)	0.0438 (5)
H43	0.5992	0.8350	0.6345	0.053*
C44	0.4552 (2)	0.7677 (2)	0.4914 (2)	0.0470 (5)
H44A	0.4112	0.6733	0.4578	0.056*
H44B	0.3950	0.7826	0.5464	0.056*
C45	0.4878 (2)	0.8570 (2)	0.39832 (19)	0.0419 (5)
C421	0.8207 (2)	1.0215 (2)	0.5319 (2)	0.0518 (6)
O421	0.87539 (17)	1.00095 (17)	0.61378 (16)	0.0665 (5)
C422	0.8969 (3)	1.1362 (2)	0.4651 (3)	0.0672 (7)
H42A	0.9713	1.2091	0.5146	0.101*
H42B	0.8338	1.1661	0.4387	0.101*
H42C	0.9344	1.1074	0.3990	0.101*
C451	0.3863 (2)	0.8423 (2)	0.30793 (19)	0.0438 (5)
C452	0.4201 (2)	0.9316 (2)	0.2269 (2)	0.0548 (6)
H432	0.5096	1.0035	0.2303	0.066*
C453	0.3229 (3)	0.9152 (3)	0.1418 (2)	0.0618 (7)
H453	0.3470	0.9759	0.0883	0.074*
C454	0.1896 (2)	0.8088 (3)	0.1354 (2)	0.0547 (6)
C455	0.1541 (3)	0.7189 (3)	0.2142 (2)	0.0601 (7)
H455	0.0645	0.6470	0.2100	0.072*
C456	0.2518 (2)	0.7356 (2)	0.2994 (2)	0.0550 (6)
H456	0.2271	0.6742	0.3522	0.066*
O51	0.59236 (14)	0.63452 (14)	0.31443 (12)	0.0439 (4)
C51	0.6722 (2)	0.7221 (2)	0.23830 (17)	0.0385 (5)
C52	0.6039 (2)	0.7120 (2)	0.13389 (18)	0.0456 (5)
Cl52	0.43183 (6)	0.59396 (7)	0.10230 (5)	0.0642 (2)
C53	0.6747 (3)	0.7974 (3)	0.0551 (2)	0.0687 (8)
H53	0.6296	0.7910	−0.0155	0.082*
C54	0.8119 (3)	0.8921 (3)	0.0802 (2)	0.0785 (9)
H54	0.8589	0.9505	0.0271	0.094*
C55	0.8794 (3)	0.9006 (3)	0.1834 (2)	0.0636 (7)
H55	0.9724	0.9644	0.1998	0.076*
C56	0.8105 (2)	0.8153 (2)	0.26297 (19)	0.0480 (5)
H56	0.8567	0.8205	0.3326	0.058*
N451	0.0955 (3)	0.8005 (3)	0.0454 (2)	0.0742 (7)
N452	−0.0178 (3)	0.6960 (3)	0.0307 (2)	0.0877 (8)
N453	−0.1227 (4)	0.6080 (4)	0.0081 (3)	0.1355 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0418 (10)	0.0384 (9)	0.0397 (10)	0.0174 (8)	−0.0021 (7)	0.0100 (7)
N2	0.0451 (10)	0.0426 (10)	0.0416 (10)	0.0167 (8)	−0.0031 (8)	0.0136 (8)
C3	0.0400 (12)	0.0384 (11)	0.0407 (12)	0.0109 (10)	0.0001 (9)	0.0119 (9)
C4	0.0391 (11)	0.0337 (10)	0.0387 (11)	0.0115 (9)	0.0015 (9)	0.0109 (9)
C5	0.0357 (11)	0.0347 (11)	0.0403 (11)	0.0109 (9)	−0.0020 (9)	0.0117 (9)
C11	0.0487 (13)	0.0374 (11)	0.0463 (12)	0.0182 (10)	0.0078 (10)	0.0158 (10)
C12	0.0735 (17)	0.0608 (15)	0.0554 (15)	0.0354 (14)	−0.0052 (13)	0.0016 (12)
C13	0.121 (3)	0.079 (2)	0.0584 (18)	0.057 (2)	−0.0056 (17)	−0.0079 (15)
C14	0.130 (3)	0.086 (2)	0.072 (2)	0.074 (2)	0.030 (2)	0.0143 (17)
C15	0.082 (2)	0.0752 (19)	0.087 (2)	0.0523 (17)	0.0281 (17)	0.0313 (17)
C16	0.0554 (15)	0.0517 (14)	0.0643 (15)	0.0287 (12)	0.0084 (12)	0.0175 (12)
C31	0.0672 (16)	0.0641 (16)	0.0424 (13)	0.0250 (13)	−0.0017 (11)	0.0104 (11)
N41	0.0434 (10)	0.0365 (9)	0.0544 (11)	0.0186 (8)	0.0051 (8)	0.0110 (8)
N42	0.0397 (10)	0.0341 (9)	0.0574 (12)	0.0118 (8)	0.0002 (8)	0.0116 (8)
C43	0.0445 (12)	0.0377 (11)	0.0463 (12)	0.0159 (10)	0.0050 (10)	0.0103 (9)
C44	0.0413 (12)	0.0416 (12)	0.0575 (14)	0.0171 (10)	0.0074 (10)	0.0155 (10)
C45	0.0401 (12)	0.0333 (11)	0.0527 (13)	0.0174 (10)	0.0078 (10)	0.0072 (9)
C421	0.0443 (13)	0.0400 (12)	0.0657 (16)	0.0166 (11)	0.0009 (12)	0.0034 (11)
O421	0.0530 (10)	0.0554 (10)	0.0780 (12)	0.0154 (9)	−0.0141 (9)	0.0071 (9)
C422	0.0487 (14)	0.0424 (13)	0.097 (2)	0.0082 (11)	0.0075 (13)	0.0173 (13)
C451	0.0418 (12)	0.0371 (11)	0.0530 (13)	0.0189 (10)	0.0057 (10)	0.0068 (10)
C452	0.0473 (13)	0.0476 (13)	0.0644 (16)	0.0159 (11)	0.0038 (11)	0.0170 (12)
C453	0.0617 (16)	0.0609 (16)	0.0640 (16)	0.0263 (14)	0.0049 (13)	0.0235 (13)
C454	0.0501 (14)	0.0638 (15)	0.0510 (14)	0.0278 (13)	0.0019 (11)	0.0073 (12)
C455	0.0433 (13)	0.0607 (15)	0.0644 (16)	0.0140 (12)	0.0027 (12)	0.0121 (13)
C456	0.0470 (14)	0.0545 (14)	0.0593 (15)	0.0179 (12)	0.0062 (11)	0.0184 (11)
O51	0.0410 (8)	0.0437 (8)	0.0401 (8)	0.0123 (7)	−0.0050 (6)	0.0148 (6)
C51	0.0421 (12)	0.0388 (11)	0.0356 (11)	0.0190 (10)	0.0035 (9)	0.0094 (9)
C52	0.0457 (12)	0.0528 (13)	0.0386 (12)	0.0229 (11)	−0.0004 (9)	0.0087 (10)
Cl52	0.0497 (4)	0.0759 (4)	0.0539 (4)	0.0191 (3)	−0.0120 (3)	0.0076 (3)
C53	0.0667 (17)	0.090 (2)	0.0464 (14)	0.0300 (16)	−0.0002 (12)	0.0273 (14)
C54	0.0714 (19)	0.086 (2)	0.0658 (18)	0.0193 (16)	0.0135 (15)	0.0425 (16)
C55	0.0487 (14)	0.0633 (16)	0.0617 (16)	0.0098 (12)	0.0057 (12)	0.0189 (13)
C56	0.0449 (13)	0.0504 (13)	0.0438 (12)	0.0178 (11)	−0.0009 (10)	0.0090 (10)
N451	0.0607 (15)	0.0910 (18)	0.0658 (15)	0.0306 (14)	−0.0037 (12)	0.0147 (13)
N452	0.0718 (18)	0.105 (2)	0.0770 (18)	0.0341 (18)	−0.0142 (14)	0.0112 (15)
N453	0.084 (2)	0.129 (3)	0.141 (3)	0.009 (2)	−0.044 (2)	0.014 (2)

Geometric parameters (Å, º) top

N1—C5	1.358 (3)	C45—C451	1.457 (3)
N1—N2	1.375 (2)	C421—O421	1.221 (3)
N1—C11	1.420 (3)	C421—C422	1.492 (3)
N2—C3	1.324 (3)	C422—H42A	0.9600
C3—C4	1.413 (3)	C422—H42B	0.9600
C3—C31	1.496 (3)	C422—H42C	0.9600
C4—C5	1.364 (3)	C451—C456	1.390 (3)
C4—C43	1.498 (3)	C451—C452	1.391 (3)
C5—O51	1.368 (2)	C452—C453	1.375 (3)
C11—C16	1.377 (3)	C452—H432	0.9300
C11—C12	1.382 (3)	C453—C454	1.381 (3)
C12—C13	1.383 (4)	C453—H453	0.9300
C12—H12	0.9300	C454—C455	1.374 (3)
C13—C14	1.371 (4)	C454—N451	1.423 (3)
C13—H13	0.9300	C455—C456	1.378 (3)
C14—C15	1.370 (4)	C455—H455	0.9300
C14—H14	0.9300	C456—H456	0.9300
C15—C16	1.374 (3)	O51—C51	1.391 (2)
C15—H15	0.9300	C51—C56	1.378 (3)
C16—H16	0.9300	C51—C52	1.382 (3)
C31—H31A	0.9600	C52—C53	1.376 (3)
C31—H31B	0.9600	C52—Cl52	1.721 (2)
C31—H31C	0.9600	C53—C54	1.374 (4)
N41—C45	1.288 (3)	C53—H53	0.9300
N41—N42	1.382 (2)	C54—C55	1.371 (4)
N42—C421	1.357 (3)	C54—H54	0.9300
N42—C43	1.485 (3)	C55—C56	1.377 (3)
C43—C44	1.536 (3)	C55—H55	0.9300
C43—H43	0.9800	C56—H56	0.9300
C44—C45	1.500 (3)	N451—N452	1.239 (3)
C44—H44A	0.9700	N452—N453	1.112 (4)
C44—H44B	0.9700

C5—N1—N2	109.94 (17)	H44A—C44—H44B	109.1
C5—N1—C11	131.03 (17)	N41—C45—C451	121.9 (2)
N2—N1—C11	118.97 (17)	N41—C45—C44	114.0 (2)
C3—N2—N1	105.22 (16)	C451—C45—C44	124.14 (18)
N2—C3—C4	112.06 (18)	O421—C421—N42	119.4 (2)
N2—C3—C31	119.7 (2)	O421—C421—C422	123.0 (2)
C4—C3—C31	128.3 (2)	N42—C421—C422	117.5 (2)
C5—C4—C3	103.77 (19)	C421—C422—H42A	109.5
C5—C4—C43	127.47 (19)	C421—C422—H42B	109.5
C3—C4—C43	128.67 (19)	H42A—C422—H42B	109.5
N1—C5—C4	109.00 (18)	C421—C422—H42C	109.5
N1—C5—O51	121.29 (18)	H42A—C422—H42C	109.5
C4—C5—O51	129.63 (19)	H42B—C422—H42C	109.5
C16—C11—C12	120.3 (2)	C456—C451—C452	117.9 (2)
C16—C11—N1	118.1 (2)	C456—C451—C45	120.2 (2)
C12—C11—N1	121.5 (2)	C452—C451—C45	121.93 (19)
C11—C12—C13	118.8 (3)	C453—C452—C451	120.9 (2)
C11—C12—H12	120.6	C453—C452—H432	119.5
C13—C12—H12	120.6	C451—C452—H432	119.5
C14—C13—C12	120.8 (3)	C452—C453—C454	120.2 (2)
C14—C13—H13	119.6	C452—C453—H453	119.9
C12—C13—H13	119.6	C454—C453—H453	119.9
C15—C14—C13	119.8 (3)	C455—C454—C453	119.9 (2)
C15—C14—H14	120.1	C455—C454—N451	123.8 (2)
C13—C14—H14	120.1	C453—C454—N451	116.3 (2)
C14—C15—C16	120.3 (3)	C454—C455—C456	119.8 (2)
C14—C15—H15	119.9	C454—C455—H455	120.1
C16—C15—H15	119.9	C456—C455—H455	120.1
C15—C16—C11	119.9 (3)	C455—C456—C451	121.4 (2)
C15—C16—H16	120.0	C455—C456—H456	119.3
C11—C16—H16	120.0	C451—C456—H456	119.3
C3—C31—H31A	109.5	C5—O51—C51	118.76 (15)
C3—C31—H31B	109.5	C56—C51—C52	120.60 (19)
H31A—C31—H31B	109.5	C56—C51—O51	123.61 (18)
C3—C31—H31C	109.5	C52—C51—O51	115.78 (17)
H31A—C31—H31C	109.5	C53—C52—C51	119.3 (2)
H31B—C31—H31C	109.5	C53—C52—Cl52	120.11 (18)
C45—N41—N42	107.91 (17)	C51—C52—Cl52	120.55 (16)
C421—N42—N41	123.31 (18)	C54—C53—C52	120.3 (2)
C421—N42—C43	123.29 (19)	C54—C53—H53	119.9
N41—N42—C43	113.24 (16)	C52—C53—H53	119.9
N42—C43—C4	111.51 (17)	C55—C54—C53	120.1 (2)
N42—C43—C44	100.58 (16)	C55—C54—H54	120.0
C4—C43—C44	115.07 (17)	C53—C54—H54	120.0
N42—C43—H43	109.8	C54—C55—C56	120.5 (2)
C4—C43—H43	109.8	C54—C55—H55	119.8
C44—C43—H43	109.8	C56—C55—H55	119.8
C45—C44—C43	102.78 (17)	C55—C56—C51	119.2 (2)
C45—C44—H44A	111.2	C55—C56—H56	120.4
C43—C44—H44A	111.2	C51—C56—H56	120.4
C45—C44—H44B	111.2	N452—N451—C454	115.9 (2)
C43—C44—H44B	111.2	N453—N452—N451	172.5 (4)

C5—N1—N2—C3	0.0 (2)	N42—N41—C45—C451	−178.72 (18)
C11—N1—N2—C3	177.67 (17)	N42—N41—C45—C44	2.3 (2)
N1—N2—C3—C4	−0.1 (2)	C43—C44—C45—N41	−9.3 (2)
N1—N2—C3—C31	−179.89 (18)	C43—C44—C45—C451	171.76 (19)
N2—C3—C4—C5	0.2 (2)	N41—N42—C421—O421	−179.4 (2)
C31—C3—C4—C5	179.9 (2)	C43—N42—C421—O421	−4.4 (3)
N2—C3—C4—C43	−176.68 (18)	N41—N42—C421—C422	−0.1 (3)
C31—C3—C4—C43	3.1 (3)	C43—N42—C421—C422	174.9 (2)
N2—N1—C5—C4	0.1 (2)	N41—C45—C451—C456	177.0 (2)
C11—N1—C5—C4	−177.18 (19)	C44—C45—C451—C456	−4.2 (3)
N2—N1—C5—O51	−176.85 (16)	N41—C45—C451—C452	−2.0 (3)
C11—N1—C5—O51	5.8 (3)	C44—C45—C451—C452	176.9 (2)
C3—C4—C5—N1	−0.2 (2)	C456—C451—C452—C453	0.5 (4)
C43—C4—C5—N1	176.73 (18)	C45—C451—C452—C453	179.5 (2)
C3—C4—C5—O51	176.47 (19)	C451—C452—C453—C454	−0.2 (4)
C43—C4—C5—O51	−6.6 (3)	C452—C453—C454—C455	−0.2 (4)
C5—N1—C11—C16	149.1 (2)	C452—C453—C454—N451	179.3 (2)
N2—N1—C11—C16	−28.0 (3)	C453—C454—C455—C456	0.2 (4)
C5—N1—C11—C12	−33.1 (3)	N451—C454—C455—C456	−179.3 (2)
N2—N1—C11—C12	149.8 (2)	C454—C455—C456—C451	0.2 (4)
C16—C11—C12—C13	1.3 (4)	C452—C451—C456—C455	−0.6 (3)
N1—C11—C12—C13	−176.5 (2)	C45—C451—C456—C455	−179.5 (2)
C11—C12—C13—C14	0.9 (4)	N1—C5—O51—C51	−90.0 (2)
C12—C13—C14—C15	−2.5 (5)	C4—C5—O51—C51	93.7 (2)
C13—C14—C15—C16	1.8 (5)	C5—O51—C51—C56	1.2 (3)
C14—C15—C16—C11	0.4 (4)	C5—O51—C51—C52	−178.15 (19)
C12—C11—C16—C15	−2.0 (3)	C56—C51—C52—C53	−0.9 (3)
N1—C11—C16—C15	175.9 (2)	O51—C51—C52—C53	178.4 (2)
C45—N41—N42—C421	−178.2 (2)	C56—C51—C52—Cl52	179.07 (17)
C45—N41—N42—C43	6.3 (2)	O51—C51—C52—Cl52	−1.6 (3)
C421—N42—C43—C4	−64.4 (3)	C51—C52—C53—C54	−0.2 (4)
N41—N42—C43—C4	111.03 (19)	Cl52—C52—C53—C54	179.7 (2)
C421—N42—C43—C44	173.1 (2)	C52—C53—C54—C55	0.9 (5)
N41—N42—C43—C44	−11.4 (2)	C53—C54—C55—C56	−0.5 (5)
C5—C4—C43—N42	−67.9 (3)	C54—C55—C56—C51	−0.7 (4)
C3—C4—C43—N42	108.3 (2)	C52—C51—C56—C55	1.4 (3)
C5—C4—C43—C44	45.8 (3)	O51—C51—C56—C55	−177.9 (2)
C3—C4—C43—C44	−138.0 (2)	C455—C454—N451—N452	−9.4 (4)
N42—C43—C44—C45	11.3 (2)	C453—C454—N451—N452	171.1 (3)
C4—C43—C44—C45	−108.61 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···N451ⁱ	0.93	2.58	3.378 (5)	144
C55—H55···O421ⁱⁱ	0.93	2.59	3.228 (4)	126

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

(3RS)-2-Acetyl-5-(4-azidophenyl)-3'-methyl-5'-(naphthalen-2-yloxy)-1'-phenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole] (X) top

Crystal data top

C₃₁H₂₅N₇O₂	Z = 2
M_r = 527.58	F(000) = 552
Triclinic, P1	D_x = 1.312 Mg m⁻³
a = 10.4911 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2048 (12) Å	Cell parameters from 5566 reflections
c = 13.5943 (17) Å	θ = 2.2–27.0°
α = 105.323 (3)°	µ = 0.09 mm⁻¹
β = 93.505 (3)°	T = 296 K
γ = 117.460 (3)°	Block, orange
V = 1335.9 (3) Å³	0.15 × 0.13 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	5470 independent reflections
Radiation source: fine focus sealed tube	2883 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 0.3333 pixels mm^-1	θ_max = 26.6°, θ_min = 2.2°
φ and ω scans	h = −12→13
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −13→14
T_min = 0.926, T_max = 0.990	l = −17→17
16901 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.178	w = 1/[σ²(F_o²) + (0.0878P)² + 0.1031P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
5470 reflections	Δρ_max = 0.25 e Å⁻³
363 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6651 (2)	0.45791 (19)	0.57177 (15)	0.0416 (5)
N2	0.6648 (2)	0.41194 (19)	0.46756 (15)	0.0432 (5)
C3	0.5257 (3)	0.3161 (2)	0.42124 (18)	0.0409 (6)
C4	0.4331 (2)	0.2966 (2)	0.49356 (17)	0.0391 (5)
C5	0.5259 (2)	0.3892 (2)	0.58743 (18)	0.0392 (5)
C11	0.8015 (3)	0.5485 (2)	0.64502 (19)	0.0457 (6)
C12	0.8116 (3)	0.6256 (4)	0.7444 (3)	0.0944 (12)
H12	0.7279	0.6222	0.7660	0.113*
C13	0.9477 (4)	0.7090 (4)	0.8131 (3)	0.1192 (15)
H13	0.9540	0.7593	0.8814	0.143*
C14	1.0715 (3)	0.7182 (4)	0.7824 (3)	0.0908 (11)
H14	1.1624	0.7765	0.8285	0.109*
C15	1.0613 (3)	0.6411 (3)	0.6831 (3)	0.0735 (9)
H15	1.1455	0.6460	0.6615	0.088*
C16	0.9265 (3)	0.5558 (3)	0.6146 (2)	0.0579 (7)
H16	0.9203	0.5029	0.5473	0.069*
C31	0.4869 (3)	0.2469 (3)	0.30552 (18)	0.0582 (7)
H31A	0.4656	0.3036	0.2728	0.087*
H31B	0.4021	0.1537	0.2869	0.087*
H31C	0.5681	0.2387	0.2824	0.087*
N41	0.1695 (2)	0.06485 (19)	0.59131 (15)	0.0437 (5)
N42	0.2441 (2)	0.07050 (19)	0.51032 (15)	0.0441 (5)
C43	0.2714 (2)	0.1920 (2)	0.47299 (19)	0.0436 (6)
H43	0.2298	0.1557	0.3979	0.052*
C44	0.1791 (3)	0.2468 (3)	0.5328 (2)	0.0494 (6)
H44A	0.2369	0.3483	0.5702	0.059*
H44B	0.0936	0.2279	0.4858	0.059*
C45	0.1347 (2)	0.1634 (2)	0.60715 (18)	0.0409 (6)
C421	0.2925 (3)	−0.0227 (2)	0.4726 (2)	0.0473 (6)
O421	0.3548 (2)	−0.01416 (18)	0.39939 (15)	0.0622 (5)
C422	0.2662 (3)	−0.1327 (3)	0.5239 (2)	0.0611 (7)
H42A	0.1856	−0.2230	0.4805	0.092*
H42B	0.2432	−0.1049	0.5904	0.092*
H42C	0.3531	−0.1407	0.5336	0.092*
C451	0.0576 (2)	0.1863 (2)	0.68995 (19)	0.0451 (6)
C452	0.0181 (3)	0.1030 (3)	0.7542 (2)	0.0547 (7)
H452	0.0400	0.0297	0.7442	0.066*
C453	−0.0529 (3)	0.1269 (3)	0.8323 (2)	0.0611 (7)
H453	−0.0790	0.0695	0.8743	0.073*
C454	−0.0857 (3)	0.2361 (3)	0.8491 (2)	0.0565 (7)
C455	−0.0469 (3)	0.3205 (3)	0.7863 (2)	0.0595 (7)
H455	−0.0689	0.3938	0.7969	0.071*
C456	0.0244 (3)	0.2966 (3)	0.7078 (2)	0.0532 (7)
H456	0.0507	0.3545	0.6662	0.064*
N451	−0.1584 (3)	0.2531 (3)	0.9322 (2)	0.0777 (7)
N452	−0.1799 (3)	0.3563 (4)	0.9520 (2)	0.0815 (8)
N453	−0.2067 (3)	0.4447 (4)	0.9772 (3)	0.1105 (12)
O51	0.49499 (18)	0.42237 (16)	0.68363 (12)	0.0487 (4)
C51	0.4200 (2)	0.3517 (2)	0.82738 (17)	0.0442 (6)
H51	0.3925	0.4213	0.8433	0.053*
C52	0.4813 (2)	0.3339 (2)	0.74396 (17)	0.0406 (6)
C53	0.5294 (2)	0.2343 (2)	0.71852 (17)	0.0453 (6)
H53	0.5742	0.2262	0.6621	0.054*
C54	0.5090 (3)	0.1493 (3)	0.77839 (18)	0.0469 (6)
H54	0.5402	0.0825	0.7621	0.056*
C54A	0.4420 (3)	0.1604 (2)	0.86413 (18)	0.0438 (6)
C55	0.4151 (3)	0.0699 (3)	0.9256 (2)	0.0589 (7)
H55	0.4434	0.0009	0.9095	0.071*
C56	0.3490 (3)	0.0824 (3)	1.0070 (2)	0.0694 (8)
H56	0.3323	0.0221	1.0463	0.083*
C57	0.3056 (3)	0.1853 (3)	1.0325 (2)	0.0702 (8)
H57	0.2597	0.1926	1.0884	0.084*
C58	0.3298 (3)	0.2748 (3)	0.9765 (2)	0.0605 (7)
H58	0.3013	0.3436	0.9950	0.073*
C58A	0.3978 (2)	0.2648 (2)	0.89043 (17)	0.0426 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0408 (12)	0.0393 (11)	0.0473 (12)	0.0199 (10)	0.0116 (9)	0.0174 (9)
N2	0.0464 (12)	0.0413 (11)	0.0473 (12)	0.0217 (10)	0.0164 (10)	0.0215 (9)
C3	0.0443 (14)	0.0364 (13)	0.0481 (14)	0.0203 (12)	0.0117 (12)	0.0218 (11)
C4	0.0415 (13)	0.0334 (12)	0.0476 (14)	0.0194 (11)	0.0115 (11)	0.0190 (11)
C5	0.0441 (14)	0.0385 (13)	0.0449 (14)	0.0239 (12)	0.0173 (11)	0.0205 (11)
C11	0.0410 (14)	0.0374 (13)	0.0563 (16)	0.0173 (11)	0.0081 (12)	0.0164 (12)
C12	0.0551 (19)	0.102 (3)	0.084 (2)	0.0367 (19)	−0.0005 (17)	−0.026 (2)
C13	0.070 (2)	0.120 (3)	0.099 (3)	0.037 (2)	−0.015 (2)	−0.040 (2)
C14	0.051 (2)	0.079 (2)	0.095 (3)	0.0118 (17)	−0.0135 (18)	0.002 (2)
C15	0.0410 (16)	0.077 (2)	0.092 (2)	0.0178 (15)	0.0115 (16)	0.0335 (19)
C16	0.0437 (16)	0.0615 (17)	0.0608 (17)	0.0181 (14)	0.0144 (13)	0.0230 (14)
C31	0.0644 (17)	0.0618 (17)	0.0491 (16)	0.0312 (15)	0.0116 (13)	0.0198 (13)
N41	0.0374 (11)	0.0353 (11)	0.0577 (13)	0.0146 (9)	0.0101 (9)	0.0208 (9)
N42	0.0424 (11)	0.0344 (11)	0.0598 (13)	0.0186 (9)	0.0162 (10)	0.0216 (9)
C43	0.0391 (13)	0.0401 (13)	0.0548 (15)	0.0179 (11)	0.0114 (11)	0.0236 (11)
C44	0.0419 (14)	0.0420 (14)	0.0704 (17)	0.0205 (12)	0.0146 (12)	0.0274 (13)
C45	0.0324 (12)	0.0305 (12)	0.0541 (15)	0.0103 (10)	0.0050 (11)	0.0167 (11)
C421	0.0350 (13)	0.0373 (14)	0.0636 (17)	0.0156 (11)	0.0085 (12)	0.0130 (12)
O421	0.0629 (12)	0.0537 (11)	0.0772 (13)	0.0328 (10)	0.0268 (11)	0.0227 (10)
C422	0.0575 (16)	0.0433 (15)	0.089 (2)	0.0266 (13)	0.0149 (15)	0.0283 (14)
C451	0.0370 (13)	0.0407 (14)	0.0529 (15)	0.0163 (11)	0.0062 (11)	0.0148 (12)
C452	0.0532 (16)	0.0551 (16)	0.0636 (18)	0.0280 (14)	0.0171 (14)	0.0280 (14)
C453	0.0571 (17)	0.0638 (18)	0.0662 (19)	0.0262 (15)	0.0187 (14)	0.0328 (15)
C454	0.0471 (15)	0.0652 (18)	0.0528 (16)	0.0263 (14)	0.0129 (13)	0.0154 (14)
C455	0.0566 (17)	0.0575 (17)	0.0649 (18)	0.0320 (15)	0.0132 (14)	0.0139 (15)
C456	0.0529 (16)	0.0476 (15)	0.0609 (17)	0.0255 (13)	0.0135 (13)	0.0196 (13)
N451	0.0809 (18)	0.091 (2)	0.0712 (17)	0.0503 (17)	0.0300 (14)	0.0251 (15)
N452	0.0605 (16)	0.088 (2)	0.0682 (18)	0.0283 (16)	0.0139 (13)	0.0004 (16)
N453	0.097 (2)	0.097 (2)	0.111 (3)	0.051 (2)	0.0219 (18)	−0.0110 (19)
O51	0.0650 (11)	0.0464 (10)	0.0478 (10)	0.0340 (9)	0.0224 (8)	0.0206 (8)
C51	0.0475 (14)	0.0432 (14)	0.0431 (14)	0.0258 (12)	0.0098 (11)	0.0096 (11)
C52	0.0415 (13)	0.0411 (13)	0.0382 (13)	0.0201 (11)	0.0072 (11)	0.0129 (11)
C53	0.0489 (14)	0.0511 (15)	0.0420 (14)	0.0294 (13)	0.0130 (11)	0.0150 (12)
C54	0.0547 (15)	0.0474 (15)	0.0464 (15)	0.0325 (13)	0.0093 (12)	0.0137 (12)
C54A	0.0446 (14)	0.0444 (14)	0.0388 (13)	0.0206 (12)	0.0056 (11)	0.0118 (11)
C55	0.0701 (18)	0.0610 (17)	0.0538 (17)	0.0349 (15)	0.0145 (14)	0.0263 (14)
C56	0.082 (2)	0.080 (2)	0.0593 (18)	0.0407 (18)	0.0253 (16)	0.0394 (16)
C57	0.078 (2)	0.091 (2)	0.0538 (17)	0.0450 (19)	0.0273 (15)	0.0314 (17)
C58	0.0674 (18)	0.0701 (19)	0.0484 (16)	0.0382 (16)	0.0194 (14)	0.0169 (14)
C58A	0.0408 (13)	0.0448 (14)	0.0363 (13)	0.0187 (11)	0.0053 (11)	0.0099 (11)

Geometric parameters (Å, º) top

N1—C5	1.363 (3)	C422—H42A	0.9600
N1—N2	1.373 (2)	C422—H42B	0.9600
N1—C11	1.422 (3)	C422—H42C	0.9600
N2—C3	1.328 (3)	C451—C452	1.387 (3)
C3—C4	1.411 (3)	C451—C456	1.399 (3)
C3—C31	1.493 (3)	C452—C453	1.373 (3)
C4—C5	1.368 (3)	C452—H452	0.9300
C4—C43	1.505 (3)	C453—C454	1.384 (4)
C5—O51	1.364 (2)	C453—H453	0.9300
C11—C12	1.366 (4)	C454—C455	1.380 (4)
C11—C16	1.372 (3)	C454—N451	1.422 (3)
C12—C13	1.389 (4)	C455—C456	1.378 (3)
C12—H12	0.9300	C455—H455	0.9300
C13—C14	1.356 (5)	C456—H456	0.9300
C13—H13	0.9300	N451—N452	1.243 (4)
C14—C15	1.365 (4)	N452—N453	1.125 (4)
C14—H14	0.9300	O51—C52	1.411 (3)
C15—C16	1.379 (4)	C51—C52	1.352 (3)
C15—H15	0.9300	C51—C58A	1.411 (3)
C16—H16	0.9300	C51—H51	0.9300
C31—H31A	0.9600	C52—C53	1.398 (3)
C31—H31B	0.9600	C53—C54	1.363 (3)
C31—H31C	0.9600	C53—H53	0.9300
N41—C45	1.286 (3)	C54—C54A	1.404 (3)
N41—N42	1.387 (3)	C54—H54	0.9300
N42—C421	1.360 (3)	C54A—C58A	1.419 (3)
N42—C43	1.488 (3)	C54A—C55	1.420 (3)
C43—C44	1.535 (3)	C55—C56	1.352 (3)
C43—H43	0.9800	C55—H55	0.9300
C44—C45	1.506 (3)	C56—C57	1.396 (4)
C44—H44A	0.9700	C56—H56	0.9300
C44—H44B	0.9700	C57—C58	1.357 (4)
C45—C451	1.462 (3)	C57—H57	0.9300
C421—O421	1.224 (3)	C58—C58A	1.413 (3)
C421—C422	1.499 (4)	C58—H58	0.9300

C5—N1—N2	109.79 (18)	N42—C421—C422	117.4 (2)
C5—N1—C11	130.2 (2)	C421—C422—H42A	109.5
N2—N1—C11	119.39 (18)	C421—C422—H42B	109.5
C3—N2—N1	105.52 (18)	H42A—C422—H42B	109.5
N2—C3—C4	111.9 (2)	C421—C422—H42C	109.5
N2—C3—C31	119.0 (2)	H42A—C422—H42C	109.5
C4—C3—C31	129.1 (2)	H42B—C422—H42C	109.5
C5—C4—C3	104.0 (2)	C452—C451—C456	118.0 (2)
C5—C4—C43	128.0 (2)	C452—C451—C45	121.9 (2)
C3—C4—C43	128.0 (2)	C456—C451—C45	120.1 (2)
N1—C5—O51	121.4 (2)	C453—C452—C451	121.1 (2)
N1—C5—C4	108.9 (2)	C453—C452—H452	119.4
O51—C5—C4	129.7 (2)	C451—C452—H452	119.4
C12—C11—C16	119.3 (2)	C452—C453—C454	120.4 (3)
C12—C11—N1	122.4 (2)	C452—C453—H453	119.8
C16—C11—N1	118.3 (2)	C454—C453—H453	119.8
C11—C12—C13	119.5 (3)	C455—C454—C453	119.4 (2)
C11—C12—H12	120.2	C455—C454—N451	124.3 (3)
C13—C12—H12	120.2	C453—C454—N451	116.3 (3)
C14—C13—C12	121.1 (3)	C456—C455—C454	120.2 (2)
C14—C13—H13	119.4	C456—C455—H455	119.9
C12—C13—H13	119.4	C454—C455—H455	119.9
C13—C14—C15	119.3 (3)	C455—C456—C451	120.8 (3)
C13—C14—H14	120.4	C455—C456—H456	119.6
C15—C14—H14	120.4	C451—C456—H456	119.6
C14—C15—C16	120.2 (3)	N452—N451—C454	116.6 (3)
C14—C15—H15	119.9	N453—N452—N451	173.0 (4)
C16—C15—H15	119.9	C5—O51—C52	118.44 (16)
C11—C16—C15	120.6 (3)	C52—C51—C58A	120.1 (2)
C11—C16—H16	119.7	C52—C51—H51	119.9
C15—C16—H16	119.7	C58A—C51—H51	119.9
C3—C31—H31A	109.5	C51—C52—C53	122.4 (2)
C3—C31—H31B	109.5	C51—C52—O51	116.1 (2)
H31A—C31—H31B	109.5	C53—C52—O51	121.5 (2)
C3—C31—H31C	109.5	C54—C53—C52	118.4 (2)
H31A—C31—H31C	109.5	C54—C53—H53	120.8
H31B—C31—H31C	109.5	C52—C53—H53	120.8
C45—N41—N42	108.22 (19)	C53—C54—C54A	121.6 (2)
C421—N42—N41	122.79 (19)	C53—C54—H54	119.2
C421—N42—C43	123.8 (2)	C54A—C54—H54	119.2
N41—N42—C43	113.33 (17)	C54—C54A—C58A	119.1 (2)
N42—C43—C4	111.61 (17)	C54—C54A—C55	122.6 (2)
N42—C43—C44	100.55 (18)	C58A—C54A—C55	118.3 (2)
C4—C43—C44	116.11 (19)	C56—C55—C54A	121.2 (3)
N42—C43—H43	109.4	C56—C55—H55	119.4
C4—C43—H43	109.4	C54A—C55—H55	119.4
C44—C43—H43	109.4	C55—C56—C57	120.3 (3)
C45—C44—C43	103.33 (18)	C55—C56—H56	119.8
C45—C44—H44A	111.1	C57—C56—H56	119.8
C43—C44—H44A	111.1	C58—C57—C56	120.7 (3)
C45—C44—H44B	111.1	C58—C57—H57	119.7
C43—C44—H44B	111.1	C56—C57—H57	119.7
H44A—C44—H44B	109.1	C57—C58—C58A	120.8 (3)
N41—C45—C451	121.0 (2)	C57—C58—H58	119.6
N41—C45—C44	113.7 (2)	C58A—C58—H58	119.6
C451—C45—C44	125.3 (2)	C51—C58A—C58	122.9 (2)
O421—C421—N42	119.7 (2)	C51—C58A—C54A	118.3 (2)
O421—C421—C422	122.9 (2)	C58—C58A—C54A	118.8 (2)

C5—N1—N2—C3	0.0 (2)	N41—N42—C421—O421	178.4 (2)
C11—N1—N2—C3	172.04 (18)	C43—N42—C421—O421	−4.6 (3)
N1—N2—C3—C4	−0.5 (2)	N41—N42—C421—C422	−1.6 (3)
N1—N2—C3—C31	178.74 (18)	C43—N42—C421—C422	175.4 (2)
N2—C3—C4—C5	0.8 (2)	N41—C45—C451—C452	−0.4 (3)
C31—C3—C4—C5	−178.4 (2)	C44—C45—C451—C452	178.8 (2)
N2—C3—C4—C43	−175.98 (19)	N41—C45—C451—C456	178.2 (2)
C31—C3—C4—C43	4.9 (4)	C44—C45—C451—C456	−2.6 (3)
N2—N1—C5—O51	−175.81 (17)	C456—C451—C452—C453	0.6 (4)
C11—N1—C5—O51	13.3 (3)	C45—C451—C452—C453	179.3 (2)
N2—N1—C5—C4	0.5 (2)	C451—C452—C453—C454	−0.4 (4)
C11—N1—C5—C4	−170.4 (2)	C452—C453—C454—C455	0.2 (4)
C3—C4—C5—N1	−0.7 (2)	C452—C453—C454—N451	−179.6 (2)
C43—C4—C5—N1	176.04 (19)	C453—C454—C455—C456	−0.2 (4)
C3—C4—C5—O51	175.1 (2)	N451—C454—C455—C456	179.6 (2)
C43—C4—C5—O51	−8.1 (4)	C454—C455—C456—C451	0.4 (4)
C5—N1—C11—C12	−26.2 (4)	C452—C451—C456—C455	−0.7 (4)
N2—N1—C11—C12	163.7 (3)	C45—C451—C456—C455	−179.3 (2)
C5—N1—C11—C16	152.5 (2)	C455—C454—N451—N452	−4.2 (4)
N2—N1—C11—C16	−17.6 (3)	C453—C454—N451—N452	175.6 (2)
C16—C11—C12—C13	−0.5 (5)	N1—C5—O51—C52	−100.0 (2)
N1—C11—C12—C13	178.2 (3)	C4—C5—O51—C52	84.6 (3)
C11—C12—C13—C14	1.8 (7)	C58A—C51—C52—C53	−2.2 (3)
C12—C13—C14—C15	−1.8 (7)	C58A—C51—C52—O51	178.06 (19)
C13—C14—C15—C16	0.6 (5)	C5—O51—C52—C51	−166.12 (19)
C12—C11—C16—C15	−0.7 (4)	C5—O51—C52—C53	14.2 (3)
N1—C11—C16—C15	−179.4 (2)	C51—C52—C53—C54	2.2 (3)
C14—C15—C16—C11	0.6 (5)	O51—C52—C53—C54	−178.1 (2)
C45—N41—N42—C421	−178.16 (19)	C52—C53—C54—C54A	−0.2 (3)
C45—N41—N42—C43	4.6 (2)	C53—C54—C54A—C58A	−1.6 (3)
C421—N42—C43—C4	−62.2 (3)	C53—C54—C54A—C55	177.8 (2)
N41—N42—C43—C4	115.0 (2)	C54—C54A—C55—C56	−179.3 (2)
C421—N42—C43—C44	174.0 (2)	C58A—C54A—C55—C56	0.1 (4)
N41—N42—C43—C44	−8.7 (2)	C54A—C55—C56—C57	0.0 (4)
C5—C4—C43—N42	−71.3 (3)	C55—C56—C57—C58	−0.4 (4)
C3—C4—C43—N42	104.7 (2)	C56—C57—C58—C58A	0.8 (4)
C5—C4—C43—C44	43.1 (3)	C52—C51—C58A—C58	−177.8 (2)
C3—C4—C43—C44	−140.9 (2)	C52—C51—C58A—C54A	0.3 (3)
N42—C43—C44—C45	8.9 (2)	C57—C58—C58A—C51	177.4 (2)
C4—C43—C44—C45	−111.7 (2)	C57—C58—C58A—C54A	−0.7 (4)
N42—N41—C45—C451	−178.57 (18)	C54—C54A—C58A—C51	1.5 (3)
N42—N41—C45—C44	2.2 (2)	C55—C54A—C58A—C51	−177.9 (2)
C43—C44—C45—N41	−7.5 (2)	C54—C54A—C58A—C58	179.7 (2)
C43—C44—C45—C451	173.2 (2)	C55—C54A—C58A—C58	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C44—H44A···N2ⁱ	0.97	2.60	3.397 (4)	139

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond parameters (Å, °) top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(II)	C156—H156···N12ⁱ	0.93	2.59	3.433 (3)	152
	C255—H255···Cg1ⁱⁱ	0.93	2.80	3.635 (3)	140
(III)	C52—H52···O41ⁱⁱⁱ	0.93	2.59	3.509 (3)	171
	C56—H56···Cg2ⁱⁱ	0.93	2.64	3.483 (3)	152
(IV)	C14—H14···O412^iv	0.93	2.57	3.330 (3)	139
	C52—H52···O41^v	0.93	2.53	3.456 (2)	174
	C55—H55···O411^vi	0.93	2.50	3.259 (3)	139
	C53—H53···Cg2^vii	0.93	2.84	3.564 (2)	135
(V)	C51—H51···O41^viii	0.93	2.50	3.386 (2)	160
	C12—H12···Cg3ⁱⁱ	0.93	2.96	3.4804 (17)	117
	C53—H53···Cg2ⁱⁱ	0.93	2.78	3.6477 (19)	155
(VI)	C15—H15···Cg3^ix	0.93	2.97	3.848 (3)	159
	C52—H52A···Cg2^x	0.97	2.96	3.761 (3)	140
(IX)	C14—H14···N451^xi	0.93	2.58	3.378 (5)	144
	C55—H55···O421^xii	0.93	2.59	3.228 (4)	126
(X)	C44—H44A···N2ⁱⁱ	0.97	2.60	3.397 (4)	139

Symmetry codes: (i) -x+1, y, -z+2; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z; (iv) -x+1, y-1/2, -z+1/2; (v) x, -y+1/2, z-1/2; (vi) -x+1, y-1/2, -z+3/2; (vii) x, -y+1/2, z+1/2; (viii) x+1, y, z; (ix) x+1/2, -y+3/2, z+1/2; (x) -x+1/2, y-1/2, -z+3/2; (xi) -x+1, -y+1, -z; (xii) -x+2, -y+2, -z+1.

Cg1 represents the centroid of the C211–C216 ring, Cg2 represents the centroid of the C11–C16 ring and Cg3 represents the centroid of the N1/N2/C3–C5 ring.

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Conversion of substituted 5-aryl­oxypyrazole­carbaldehydes into reduced 3,4′-bi­pyrazoles: synthesis and characterization, and the structures of four precursors and two products, and their supra­molecular assembly in zero, one and two dimensions

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Conversion of substituted 5-aryloxypyrazolecarbaldehydes into reduced 3,4′-bipyrazoles: synthesis and characterization, and the structures of four precursors and two products, and their supramolecular assembly in zero, one and two dimensions