Reduced 3,4′-bi­pyrazoles from a simple pyrazole precursor: synthetic sequence, mol­ecular structures and supra­molecular assembly

The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and N-benzyl­methyl­amine under microwave irradiation gives 5-[benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, C₁₉H₁₉N₃O, (I). Subsequent reactions under basic conditions, between (I) and a range of aceto­phenones, yield the corresponding chalcones. These undergo cyclocondensation reactions with hydrazine to produce reduced bi­pyrazoles which can be N-formyl­ated with formic acid or N-acetyl­ated with acetic anhydride. The structures of (I) and of representative examples from this reaction sequence are reported, namely the chalcone (E)-3-{5-[benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazol-4-yl}-1-(4-bromo­phenyl)prop-2-en-1-one, C₂₇H₂₄BrN₃O, (II), the N-formyl derivative (3RS)-5′-[benzyl(methyl)amino]-3′-methyl-1′,5-diphenyl-3,4-di­hydro-1′H,2H-[3,4′-bi­pyrazole]-2-carbaldehyde, C₂₈H₂₇N₅O, (III), and the N-acetyl derivative (3RS)-2-acetyl-5′-[benzyl(methyl)amino]-5-(4-meth­oxy­phenyl)-3′-methyl-1′-phenyl-3,4-di­hydro-1′H,2H-[3,4′-bi­pyrazole], which crystallizes as the ethanol 0.945-solvate, C₃₀H₃₁N₅O₂·0.945C₂H₆O, (IV). There is significant delocalization of charge from the benzyl(methyl)amino substituent onto the carbonyl group in (I), but not in (II). In each of (III) and (IV), the reduced pyrazole ring is modestly puckered into an envelope conformation. The mol­ecules of (I) are linked by a combination of C—H...N and C—H...π(arene) hydrogen bonds to form a simple chain of rings; those of (III) are linked by a combination of C—H...O and C—H...N hydrogen bonds to form sheets of R²₂(8) and R⁶₆(42) rings, and those of (IV) are linked by a combination of O—H...N and C—H...O hydrogen bonds to form a ribbon of edge-fused R²₄(16) and R⁴₄(24) rings.

Computing details

For all structures, data collection: APEX3 (Bruker2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

5-[Benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (I)

Crystal data

C19H19N3O	F(000) = 648
Mr = 305.37	Dx = 1.269 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.811 (4) Å	Cell parameters from 3698 reflections
b = 17.951 (9) Å	θ = 2.3–27.6°
c = 11.405 (6) Å	µ = 0.08 mm^−1
β = 92.36 (2)°	T = 100 K
V = 1597.8 (14) Å^3	Block, yellow
Z = 4	0.32 × 0.27 × 0.12 mm

Data collection

Bruker D8 Venture diffractometer	3695 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3267 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.037
φ and ω scans	θmax = 27.6°, θmin = 2.6°
Absorption correction: multi-scan (SADABS-2016/2; Bruker, 2016)	h = −10→10
Tmin = 0.969, Tmax = 0.990	k = −23→23
51127 measured reflections	l = −14→14

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0407P)^2 + 0.8359P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.102	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.32 e Å^−3
3695 reflections	Δρmin = −0.22 e Å^−3
211 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0228 (18)

Special details

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

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

	x	y	z	Uiso*/Ueq
N1	0.42676 (12)	0.39892 (5)	0.43035 (9)	0.0148 (2)
N2	0.55934 (12)	0.41928 (6)	0.35885 (9)	0.0171 (2)
C3	0.48214 (15)	0.44267 (6)	0.26119 (10)	0.0161 (2)
C4	0.30058 (14)	0.43969 (6)	0.26622 (10)	0.0142 (2)
C5	0.26987 (14)	0.41160 (6)	0.37866 (10)	0.0131 (2)
C11	0.47210 (14)	0.35779 (6)	0.53391 (10)	0.0147 (2)
C12	0.58714 (16)	0.38847 (7)	0.61571 (11)	0.0193 (3)
H12	0.6323	0.4369	0.6042	0.023*
C13	0.63574 (17)	0.34765 (8)	0.71461 (11)	0.0251 (3)
H13	0.7145	0.3683	0.7714	0.030*
C14	0.57062 (17)	0.27723 (8)	0.73124 (12)	0.0254 (3)
H14	0.6041	0.2495	0.7994	0.031*
C15	0.45633 (16)	0.24705 (8)	0.64838 (12)	0.0242 (3)
H15	0.4112	0.1986	0.6600	0.029*
C16	0.40716 (15)	0.28694 (7)	0.54868 (11)	0.0192 (3)
H16	0.3299	0.2659	0.4913	0.023*
C31	0.58601 (16)	0.47034 (8)	0.16327 (12)	0.0238 (3)
H31C	0.7081	0.4668	0.1860	0.036*
H31A	0.5563	0.5224	0.1463	0.036*
H31B	0.5618	0.4400	0.0931	0.036*
C41	0.18260 (15)	0.47438 (6)	0.18354 (10)	0.0165 (2)
H41	0.2296	0.4943	0.1147	0.020*
O41	0.02824 (11)	0.48099 (5)	0.19223 (8)	0.0208 (2)
N51	0.11994 (12)	0.40354 (6)	0.43358 (9)	0.0152 (2)
C51	0.11004 (16)	0.41319 (7)	0.55967 (11)	0.0197 (3)
H51A	0.2043	0.4451	0.5886	0.029*
H51C	0.1187	0.3645	0.5983	0.029*
H51B	0.0004	0.4364	0.5770	0.029*
C52	−0.02353 (15)	0.36432 (7)	0.37385 (11)	0.0183 (3)
H52B	−0.0188	0.3722	0.2881	0.022*
H52A	−0.1329	0.3853	0.3998	0.022*
C521	−0.01818 (14)	0.28206 (7)	0.39978 (10)	0.0166 (2)
C522	0.07510 (16)	0.23446 (7)	0.33113 (11)	0.0217 (3)
H522	0.1299	0.2533	0.2644	0.026*
C523	0.0888 (2)	0.15969 (8)	0.35925 (12)	0.0295 (3)
H523	0.1540	0.1275	0.3123	0.035*
C524	0.0080 (2)	0.13174 (8)	0.45545 (13)	0.0330 (4)
H524	0.0179	0.0804	0.4748	0.040*
C525	−0.0868 (2)	0.17837 (8)	0.52316 (12)	0.0302 (3)
H525	−0.1429	0.1591	0.5890	0.036*
C526	−0.10069 (16)	0.25322 (7)	0.49549 (11)	0.0221 (3)
H526	−0.1670	0.2851	0.5422	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0113 (4)	0.0153 (5)	0.0177 (5)	0.0007 (4)	0.0002 (4)	0.0029 (4)
N2	0.0134 (5)	0.0181 (5)	0.0198 (5)	0.0003 (4)	0.0017 (4)	0.0028 (4)
C3	0.0155 (5)	0.0137 (5)	0.0191 (6)	0.0010 (4)	0.0008 (4)	0.0004 (4)
C4	0.0145 (5)	0.0112 (5)	0.0170 (5)	−0.0002 (4)	0.0000 (4)	−0.0007 (4)
C5	0.0132 (5)	0.0089 (5)	0.0171 (5)	0.0005 (4)	−0.0018 (4)	−0.0011 (4)
C11	0.0127 (5)	0.0154 (5)	0.0161 (5)	0.0038 (4)	−0.0005 (4)	0.0017 (4)
C12	0.0187 (6)	0.0185 (6)	0.0203 (6)	0.0014 (4)	−0.0024 (4)	−0.0028 (5)
C13	0.0232 (6)	0.0333 (7)	0.0181 (6)	0.0054 (5)	−0.0056 (5)	−0.0038 (5)
C14	0.0225 (6)	0.0346 (7)	0.0192 (6)	0.0089 (5)	0.0007 (5)	0.0091 (5)
C15	0.0196 (6)	0.0220 (6)	0.0312 (7)	0.0026 (5)	0.0020 (5)	0.0104 (5)
C16	0.0153 (5)	0.0179 (6)	0.0240 (6)	0.0006 (4)	−0.0031 (4)	0.0026 (5)
C31	0.0188 (6)	0.0289 (7)	0.0239 (6)	0.0007 (5)	0.0046 (5)	0.0061 (5)
C41	0.0195 (6)	0.0135 (5)	0.0162 (5)	−0.0016 (4)	−0.0014 (4)	0.0014 (4)
O41	0.0175 (4)	0.0191 (4)	0.0253 (5)	0.0017 (3)	−0.0032 (3)	0.0055 (4)
N51	0.0123 (5)	0.0172 (5)	0.0162 (5)	0.0004 (4)	0.0002 (4)	0.0014 (4)
C51	0.0201 (6)	0.0213 (6)	0.0178 (6)	0.0034 (5)	0.0037 (4)	0.0001 (5)
C52	0.0120 (5)	0.0190 (6)	0.0236 (6)	−0.0016 (4)	−0.0034 (4)	0.0058 (5)
C521	0.0122 (5)	0.0191 (6)	0.0181 (6)	−0.0025 (4)	−0.0046 (4)	0.0022 (4)
C522	0.0214 (6)	0.0272 (7)	0.0160 (6)	0.0004 (5)	−0.0036 (4)	−0.0019 (5)
C523	0.0391 (8)	0.0244 (7)	0.0239 (7)	0.0087 (6)	−0.0125 (6)	−0.0106 (5)
C524	0.0547 (10)	0.0159 (6)	0.0264 (7)	−0.0019 (6)	−0.0225 (6)	−0.0005 (5)
C525	0.0427 (8)	0.0256 (7)	0.0216 (7)	−0.0126 (6)	−0.0071 (6)	0.0074 (5)
C526	0.0226 (6)	0.0224 (6)	0.0214 (6)	−0.0036 (5)	0.0014 (5)	0.0015 (5)

Geometric parameters (Å, º)

N1—C5	1.3571 (16)	C31—H31B	0.9800
N1—N2	1.3931 (15)	C41—O41	1.2196 (16)
N1—C11	1.4252 (16)	C41—H41	0.9500
N2—C3	1.3135 (16)	N51—C51	1.4536 (17)
C3—C4	1.4227 (17)	N51—C52	1.4672 (16)
C3—C31	1.4922 (17)	C51—H51A	0.9800
C4—C5	1.4077 (17)	C51—H51C	0.9800
C4—C41	1.4334 (16)	C51—H51B	0.9800
C5—N51	1.3584 (16)	C52—C521	1.5061 (18)
C11—C16	1.3820 (18)	C52—H52B	0.9900
C11—C12	1.3827 (17)	C52—H52A	0.9900
C12—C13	1.3850 (19)	C521—C522	1.3860 (18)
C12—H12	0.9500	C521—C526	1.3903 (18)
C13—C14	1.379 (2)	C522—C523	1.383 (2)
C13—H13	0.9500	C522—H522	0.9500
C14—C15	1.384 (2)	C523—C524	1.383 (2)
C14—H14	0.9500	C523—H523	0.9500
C15—C16	1.3846 (18)	C524—C525	1.376 (2)
C15—H15	0.9500	C524—H524	0.9500
C16—H16	0.9500	C525—C526	1.383 (2)
C31—H31C	0.9800	C525—H525	0.9500
C31—H31A	0.9800	C526—H526	0.9500
C5—N1—N2	112.42 (10)	O41—C41—C4	126.85 (11)
C5—N1—C11	129.50 (10)	O41—C41—H41	116.6
N2—N1—C11	117.11 (9)	C4—C41—H41	116.6
C3—N2—N1	104.71 (10)	C5—N51—C51	121.70 (10)
N2—C3—C4	112.17 (11)	C5—N51—C52	119.57 (10)
N2—C3—C31	119.75 (11)	C51—N51—C52	116.48 (10)
C4—C3—C31	128.05 (11)	N51—C51—H51A	109.5
C5—C4—C3	104.94 (10)	N51—C51—H51C	109.5
C5—C4—C41	128.74 (11)	H51A—C51—H51C	109.5
C3—C4—C41	124.89 (11)	N51—C51—H51B	109.5
N1—C5—N51	124.20 (11)	H51A—C51—H51B	109.5
N1—C5—C4	105.73 (10)	H51C—C51—H51B	109.5
N51—C5—C4	129.84 (10)	N51—C52—C521	111.40 (10)
C16—C11—C12	121.05 (11)	N51—C52—H52B	109.3
C16—C11—N1	119.86 (11)	C521—C52—H52B	109.3
C12—C11—N1	119.02 (11)	N51—C52—H52A	109.3
C11—C12—C13	119.17 (12)	C521—C52—H52A	109.3
C11—C12—H12	120.4	H52B—C52—H52A	108.0
C13—C12—H12	120.4	C522—C521—C526	119.04 (12)
C14—C13—C12	120.46 (12)	C522—C521—C52	120.29 (11)
C14—C13—H13	119.8	C526—C521—C52	120.62 (11)
C12—C13—H13	119.8	C523—C522—C521	120.32 (13)
C13—C14—C15	119.76 (12)	C523—C522—H522	119.8
C13—C14—H14	120.1	C521—C522—H522	119.8
C15—C14—H14	120.1	C524—C523—C522	120.18 (13)
C14—C15—C16	120.51 (13)	C524—C523—H523	119.9
C14—C15—H15	119.7	C522—C523—H523	119.9
C16—C15—H15	119.7	C525—C524—C523	119.91 (13)
C11—C16—C15	119.03 (12)	C525—C524—H524	120.0
C11—C16—H16	120.5	C523—C524—H524	120.0
C15—C16—H16	120.5	C524—C525—C526	120.12 (14)
C3—C31—H31C	109.5	C524—C525—H525	119.9
C3—C31—H31A	109.5	C526—C525—H525	119.9
H31C—C31—H31A	109.5	C525—C526—C521	120.43 (13)
C3—C31—H31B	109.5	C525—C526—H526	119.8
H31C—C31—H31B	109.5	C521—C526—H526	119.8
H31A—C31—H31B	109.5
C5—N1—N2—C3	−1.74 (13)	C12—C13—C14—C15	0.2 (2)
C11—N1—N2—C3	168.09 (10)	C13—C14—C15—C16	0.2 (2)
N1—N2—C3—C4	1.02 (13)	C12—C11—C16—C15	1.25 (18)
N1—N2—C3—C31	179.18 (11)	N1—C11—C16—C15	178.26 (11)
N2—C3—C4—C5	−0.01 (13)	C14—C15—C16—C11	−0.88 (19)
C31—C3—C4—C5	−177.99 (12)	C5—C4—C41—O41	−6.0 (2)
N2—C3—C4—C41	167.35 (11)	C3—C4—C41—O41	−170.30 (12)
C31—C3—C4—C41	−10.63 (19)	N1—C5—N51—C51	28.02 (17)
N2—N1—C5—N51	−173.27 (10)	C4—C5—N51—C51	−145.73 (12)
C11—N1—C5—N51	18.48 (18)	N1—C5—N51—C52	−134.32 (12)
N2—N1—C5—C4	1.75 (12)	C4—C5—N51—C52	51.93 (17)
C11—N1—C5—C4	−166.50 (11)	C5—N51—C52—C521	89.82 (13)
C3—C4—C5—N1	−1.03 (12)	C51—N51—C52—C521	−73.42 (13)
C41—C4—C5—N1	−167.73 (11)	N51—C52—C521—C522	−87.50 (14)
C3—C4—C5—N51	173.60 (11)	N51—C52—C521—C526	89.88 (14)
C41—C4—C5—N51	6.9 (2)	C526—C521—C522—C523	−1.45 (18)
C5—N1—C11—C16	49.04 (17)	C52—C521—C522—C523	175.97 (11)
N2—N1—C11—C16	−118.75 (12)	C521—C522—C523—C524	0.68 (19)
C5—N1—C11—C12	−133.89 (13)	C522—C523—C524—C525	0.2 (2)
N2—N1—C11—C12	58.32 (15)	C523—C524—C525—C526	−0.3 (2)
C16—C11—C12—C13	−0.89 (18)	C524—C525—C526—C521	−0.5 (2)
N1—C11—C12—C13	−177.92 (11)	C522—C521—C526—C525	1.34 (18)
C11—C12—C13—C14	0.16 (19)	C52—C521—C526—C525	−176.06 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52A···N2^i	0.99	2.51	3.402 (2)	150
C526—H526···Cg1^i	0.95	2.74	3.584 (2)	148

Symmetry code: (i) x−1, y, z.

(E)-3-{5-[Benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazol-4-yl}-1-(4-bromophenyl)prop-2-en-1-one (II)

Crystal data

C27H24BrN3O	F(000) = 2000
Mr = 486.39	Dx = 1.384 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 31.172 (16) Å	Cell parameters from 5344 reflections
b = 10.039 (6) Å	θ = 2.2–27.5°
c = 17.861 (10) Å	µ = 1.79 mm^−1
β = 123.334 (14)°	T = 100 K
V = 4670 (5) Å^3	Block, yellow
Z = 8	0.37 × 0.28 × 0.17 mm

Data collection

Bruker D8 Venture diffractometer	5343 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3912 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.117
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS-2016/2; Bruker, 2016)	h = −35→40
Tmin = 0.717, Tmax = 0.738	k = −13→12
49556 measured reflections	l = −23→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 18.3538P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5343 reflections	Δρmax = 0.63 e Å^−3
291 parameters	Δρmin = −0.71 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
N1	0.31616 (9)	0.7080 (2)	0.19362 (17)	0.0204 (5)
N2	0.30659 (9)	0.8281 (2)	0.14792 (17)	0.0196 (5)
C3	0.35258 (11)	0.8829 (3)	0.1831 (2)	0.0185 (6)
C4	0.39294 (11)	0.8001 (3)	0.2501 (2)	0.0178 (6)
C5	0.36735 (11)	0.6881 (3)	0.2548 (2)	0.0191 (6)
C11	0.27401 (11)	0.6341 (3)	0.1846 (2)	0.0201 (6)
C12	0.23830 (11)	0.5731 (3)	0.1027 (2)	0.0229 (7)
H12	0.2409	0.5831	0.0524	0.028*
C13	0.19889 (12)	0.4972 (3)	0.0963 (2)	0.0258 (7)
H13	0.1743	0.4555	0.0412	0.031*
C14	0.19541 (11)	0.4824 (3)	0.1701 (2)	0.0244 (7)
H14	0.1691	0.4284	0.1658	0.029*
C15	0.23042 (12)	0.5465 (3)	0.2505 (2)	0.0274 (7)
H15	0.2276	0.5376	0.3005	0.033*
C16	0.26946 (12)	0.6233 (3)	0.2572 (2)	0.0246 (7)
H16	0.2930	0.6684	0.3115	0.030*
C31	0.35817 (11)	1.0175 (3)	0.1531 (2)	0.0230 (7)
H31A	0.3244	1.0495	0.1046	0.034*
H31B	0.3810	1.0110	0.1316	0.034*
H31C	0.3728	1.0798	0.2036	0.034*
C41	0.44734 (11)	0.8243 (3)	0.29311 (19)	0.0187 (6)
H41	0.4567	0.9106	0.2851	0.022*
C42	0.48651 (11)	0.7384 (3)	0.3435 (2)	0.0218 (6)
H42	0.4794	0.6517	0.3553	0.026*
C43	0.54010 (11)	0.7781 (3)	0.3804 (2)	0.0199 (6)
O43	0.55314 (8)	0.8956 (2)	0.38735 (15)	0.0247 (5)
C431	0.57969 (11)	0.6699 (3)	0.41018 (19)	0.0191 (6)
C432	0.63165 (11)	0.7039 (3)	0.4637 (2)	0.0227 (6)
H432	0.6409	0.7943	0.4806	0.027*
C433	0.67023 (11)	0.6087 (3)	0.4929 (2)	0.0228 (6)
H433	0.7054	0.6328	0.5300	0.027*
C434	0.65561 (11)	0.4764 (3)	0.4660 (2)	0.0202 (6)
Br44	0.70677 (2)	0.34263 (3)	0.50516 (2)	0.02657 (11)
C435	0.60448 (12)	0.4399 (3)	0.4115 (2)	0.0252 (7)
H435	0.5953	0.3499	0.3931	0.030*
C436	0.56662 (11)	0.5365 (3)	0.3840 (2)	0.0228 (7)
H436	0.5315	0.5118	0.3471	0.027*
N51	0.38907 (9)	0.5756 (2)	0.30942 (17)	0.0214 (5)
C51	0.41273 (13)	0.5978 (3)	0.4060 (2)	0.0280 (7)
H51A	0.3861	0.5952	0.4192	0.042*
H51B	0.4297	0.6850	0.4228	0.042*
H51C	0.4382	0.5280	0.4401	0.042*
C52	0.36431 (11)	0.4447 (3)	0.2763 (2)	0.0244 (7)
H52A	0.3470	0.4409	0.2104	0.029*
H52B	0.3379	0.4325	0.2903	0.029*
C521	0.40390 (11)	0.3335 (3)	0.3196 (2)	0.0218 (6)
C522	0.44605 (12)	0.3300 (3)	0.3122 (2)	0.0261 (7)
H522	0.4505	0.3985	0.2804	0.031*
C523	0.48183 (13)	0.2269 (3)	0.3510 (2)	0.0311 (8)
H523	0.5102	0.2246	0.3450	0.037*
C524	0.47571 (13)	0.1271 (3)	0.3989 (2)	0.0327 (8)
H524	0.5002	0.0571	0.4259	0.039*
C525	0.43416 (14)	0.1301 (3)	0.4069 (2)	0.0314 (8)
H525	0.4300	0.0620	0.4394	0.038*
C526	0.39795 (13)	0.2333 (3)	0.3672 (2)	0.0255 (7)
H526	0.3694	0.2349	0.3729	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0157 (12)	0.0142 (11)	0.0290 (14)	0.0005 (9)	0.0107 (11)	0.0023 (10)
N2	0.0182 (12)	0.0129 (11)	0.0278 (13)	0.0032 (9)	0.0128 (11)	0.0033 (10)
C3	0.0152 (14)	0.0142 (13)	0.0242 (15)	0.0032 (10)	0.0098 (12)	0.0020 (11)
C4	0.0153 (14)	0.0125 (12)	0.0240 (15)	0.0021 (10)	0.0099 (12)	0.0000 (11)
C5	0.0176 (14)	0.0134 (13)	0.0260 (15)	0.0014 (10)	0.0118 (12)	0.0013 (11)
C11	0.0126 (14)	0.0123 (13)	0.0317 (16)	0.0016 (10)	0.0099 (12)	0.0023 (11)
C12	0.0197 (15)	0.0149 (13)	0.0294 (17)	0.0030 (11)	0.0105 (13)	0.0036 (12)
C13	0.0193 (16)	0.0148 (14)	0.0332 (18)	−0.0014 (11)	0.0080 (14)	−0.0013 (12)
C14	0.0147 (14)	0.0158 (13)	0.0396 (19)	−0.0013 (11)	0.0130 (14)	0.0012 (13)
C15	0.0254 (17)	0.0217 (15)	0.0363 (19)	−0.0017 (12)	0.0177 (15)	0.0002 (13)
C16	0.0220 (16)	0.0215 (15)	0.0290 (17)	−0.0037 (12)	0.0131 (13)	−0.0028 (12)
C31	0.0183 (15)	0.0155 (13)	0.0328 (17)	0.0027 (11)	0.0126 (13)	0.0029 (12)
C41	0.0166 (14)	0.0140 (13)	0.0244 (15)	−0.0012 (10)	0.0104 (12)	−0.0014 (11)
C42	0.0178 (15)	0.0141 (13)	0.0316 (17)	0.0002 (11)	0.0123 (13)	0.0007 (12)
C43	0.0192 (15)	0.0141 (13)	0.0237 (15)	0.0030 (11)	0.0101 (12)	0.0008 (11)
O43	0.0199 (11)	0.0139 (10)	0.0376 (13)	−0.0010 (8)	0.0142 (10)	−0.0003 (9)
C431	0.0162 (14)	0.0160 (13)	0.0240 (15)	0.0012 (11)	0.0105 (12)	0.0008 (11)
C432	0.0185 (15)	0.0136 (13)	0.0346 (17)	−0.0015 (11)	0.0137 (13)	−0.0005 (12)
C433	0.0136 (14)	0.0194 (14)	0.0312 (17)	−0.0025 (11)	0.0097 (13)	−0.0020 (12)
C434	0.0180 (14)	0.0135 (13)	0.0288 (16)	0.0038 (11)	0.0127 (13)	0.0015 (12)
Br44	0.01821 (16)	0.01703 (15)	0.03877 (19)	0.00509 (12)	0.01204 (13)	0.00039 (13)
C435	0.0213 (16)	0.0153 (14)	0.0334 (18)	−0.0006 (11)	0.0114 (14)	−0.0033 (12)
C436	0.0116 (14)	0.0194 (14)	0.0321 (17)	−0.0018 (11)	0.0086 (12)	−0.0024 (12)
N51	0.0190 (13)	0.0106 (11)	0.0278 (14)	0.0006 (9)	0.0086 (11)	0.0022 (10)
C51	0.0268 (17)	0.0218 (15)	0.0292 (17)	0.0032 (13)	0.0115 (14)	0.0034 (13)
C52	0.0174 (15)	0.0110 (13)	0.0366 (18)	0.0009 (11)	0.0096 (13)	0.0022 (12)
C521	0.0192 (15)	0.0119 (13)	0.0278 (16)	0.0010 (11)	0.0088 (12)	0.0013 (12)
C522	0.0212 (16)	0.0194 (15)	0.0339 (17)	−0.0003 (12)	0.0127 (14)	0.0028 (13)
C523	0.0182 (16)	0.0306 (18)	0.039 (2)	0.0021 (13)	0.0122 (15)	−0.0041 (15)
C524	0.0264 (18)	0.0179 (15)	0.0348 (19)	0.0076 (12)	0.0048 (15)	−0.0022 (13)
C525	0.039 (2)	0.0164 (15)	0.0294 (18)	0.0032 (13)	0.0126 (15)	0.0045 (12)
C526	0.0274 (17)	0.0192 (15)	0.0293 (17)	−0.0004 (12)	0.0151 (14)	−0.0016 (12)

Geometric parameters (Å, º)

N1—C5	1.365 (4)	C431—C436	1.403 (4)
N1—N2	1.393 (3)	C432—C433	1.394 (4)
N1—C11	1.439 (4)	C432—H432	0.9500
N2—C3	1.327 (4)	C433—C434	1.400 (4)
C3—C4	1.432 (4)	C433—H433	0.9500
C3—C31	1.499 (4)	C434—C435	1.385 (4)
C4—C5	1.408 (4)	C434—Br44	1.900 (3)
C4—C41	1.447 (4)	C435—C436	1.392 (4)
C5—N51	1.399 (4)	C435—H435	0.9500
C11—C16	1.384 (5)	C436—H436	0.9500
C11—C12	1.402 (4)	N51—C51	1.473 (4)
C12—C13	1.396 (4)	N51—C52	1.473 (4)
C12—H12	0.9500	C51—H51A	0.9800
C13—C14	1.388 (5)	C51—H51B	0.9800
C13—H13	0.9500	C51—H51C	0.9800
C14—C15	1.395 (5)	C52—C521	1.523 (4)
C14—H14	0.9500	C52—H52A	0.9900
C15—C16	1.389 (4)	C52—H52B	0.9900
C15—H15	0.9500	C521—C522	1.391 (5)
C16—H16	0.9500	C521—C526	1.394 (4)
C31—H31A	0.9800	C522—C523	1.395 (4)
C31—H31B	0.9800	C522—H522	0.9500
C31—H31C	0.9800	C523—C524	1.396 (5)
C41—C42	1.355 (4)	C523—H523	0.9500
C41—H41	0.9500	C524—C525	1.380 (5)
C42—C43	1.475 (4)	C524—H524	0.9500
C42—H42	0.9500	C525—C526	1.404 (4)
C43—O43	1.231 (3)	C525—H525	0.9500
C43—C431	1.505 (4)	C526—H526	0.9500
C431—C432	1.397 (4)
C5—N1—N2	112.1 (2)	C433—C432—C431	121.7 (3)
C5—N1—C11	127.4 (2)	C433—C432—H432	119.1
N2—N1—C11	119.5 (2)	C431—C432—H432	119.1
C3—N2—N1	104.6 (2)	C432—C433—C434	118.1 (3)
N2—C3—C4	112.4 (2)	C432—C433—H433	121.0
N2—C3—C31	120.8 (2)	C434—C433—H433	121.0
C4—C3—C31	126.9 (3)	C435—C434—C433	121.6 (3)
C5—C4—C3	104.3 (2)	C435—C434—Br44	118.7 (2)
C5—C4—C41	129.8 (3)	C433—C434—Br44	119.7 (2)
C3—C4—C41	125.6 (3)	C434—C435—C436	119.3 (3)
N1—C5—N51	125.5 (3)	C434—C435—H435	120.4
N1—C5—C4	106.6 (2)	C436—C435—H435	120.4
N51—C5—C4	127.8 (3)	C435—C436—C431	120.9 (3)
C16—C11—C12	120.8 (3)	C435—C436—H436	119.6
C16—C11—N1	119.5 (3)	C431—C436—H436	119.6
C12—C11—N1	119.7 (3)	C5—N51—C51	115.7 (2)
C13—C12—C11	118.9 (3)	C5—N51—C52	119.6 (2)
C13—C12—H12	120.6	C51—N51—C52	114.8 (2)
C11—C12—H12	120.6	N51—C51—H51A	109.5
C14—C13—C12	120.4 (3)	N51—C51—H51B	109.5
C14—C13—H13	119.8	H51A—C51—H51B	109.5
C12—C13—H13	119.8	N51—C51—H51C	109.5
C13—C14—C15	120.2 (3)	H51A—C51—H51C	109.5
C13—C14—H14	119.9	H51B—C51—H51C	109.5
C15—C14—H14	119.9	N51—C52—C521	110.5 (2)
C16—C15—C14	119.8 (3)	N51—C52—H52A	109.5
C16—C15—H15	120.1	C521—C52—H52A	109.5
C14—C15—H15	120.1	N51—C52—H52B	109.5
C11—C16—C15	119.9 (3)	C521—C52—H52B	109.5
C11—C16—H16	120.0	H52A—C52—H52B	108.1
C15—C16—H16	120.0	C522—C521—C526	119.3 (3)
C3—C31—H31A	109.5	C522—C521—C52	121.0 (3)
C3—C31—H31B	109.5	C526—C521—C52	119.7 (3)
H31A—C31—H31B	109.5	C521—C522—C523	120.7 (3)
C3—C31—H31C	109.5	C521—C522—H522	119.6
H31A—C31—H31C	109.5	C523—C522—H522	119.6
H31B—C31—H31C	109.5	C522—C523—C524	119.7 (3)
C42—C41—C4	127.7 (3)	C522—C523—H523	120.1
C42—C41—H41	116.2	C524—C523—H523	120.1
C4—C41—H41	116.2	C525—C524—C523	120.0 (3)
C41—C42—C43	120.7 (3)	C525—C524—H524	120.0
C41—C42—H42	119.6	C523—C524—H524	120.0
C43—C42—H42	119.6	C524—C525—C526	120.3 (3)
O43—C43—C42	122.3 (3)	C524—C525—H525	119.9
O43—C43—C431	119.6 (3)	C526—C525—H525	119.9
C42—C43—C431	118.1 (2)	C521—C526—C525	120.0 (3)
C432—C431—C436	118.4 (3)	C521—C526—H526	120.0
C432—C431—C43	118.9 (3)	C525—C526—H526	120.0
C436—C431—C43	122.7 (3)
C5—N1—N2—C3	−1.1 (3)	C41—C42—C43—C431	−161.2 (3)
C11—N1—N2—C3	168.1 (3)	O43—C43—C431—C432	14.7 (4)
N1—N2—C3—C4	1.5 (3)	C42—C43—C431—C432	−165.3 (3)
N1—N2—C3—C31	−177.9 (3)	O43—C43—C431—C436	−163.2 (3)
N2—C3—C4—C5	−1.3 (3)	C42—C43—C431—C436	16.9 (4)
C31—C3—C4—C5	178.0 (3)	C436—C431—C432—C433	−1.5 (5)
N2—C3—C4—C41	172.4 (3)	C43—C431—C432—C433	−179.4 (3)
C31—C3—C4—C41	−8.3 (5)	C431—C432—C433—C434	0.9 (5)
N2—N1—C5—N51	−178.4 (3)	C432—C433—C434—C435	0.4 (5)
C11—N1—C5—N51	13.4 (5)	C432—C433—C434—Br44	−179.3 (2)
N2—N1—C5—C4	0.4 (3)	C433—C434—C435—C436	−1.1 (5)
C11—N1—C5—C4	−167.8 (3)	Br44—C434—C435—C436	178.6 (2)
C3—C4—C5—N1	0.5 (3)	C434—C435—C436—C431	0.5 (5)
C41—C4—C5—N1	−172.8 (3)	C432—C431—C436—C435	0.8 (5)
C3—C4—C5—N51	179.2 (3)	C43—C431—C436—C435	178.6 (3)
C41—C4—C5—N51	6.0 (5)	N1—C5—N51—C51	−112.2 (3)
C5—N1—C11—C16	56.2 (4)	C4—C5—N51—C51	69.3 (4)
N2—N1—C11—C16	−111.3 (3)	N1—C5—N51—C52	31.7 (4)
C5—N1—C11—C12	−123.3 (3)	C4—C5—N51—C52	−146.8 (3)
N2—N1—C11—C12	69.2 (3)	C5—N51—C52—C521	152.0 (3)
C16—C11—C12—C13	−2.1 (4)	C51—N51—C52—C521	−63.8 (4)
N1—C11—C12—C13	177.4 (2)	N51—C52—C521—C522	−57.3 (4)
C11—C12—C13—C14	−0.2 (4)	N51—C52—C521—C526	122.8 (3)
C12—C13—C14—C15	1.9 (4)	C526—C521—C522—C523	0.7 (5)
C13—C14—C15—C16	−1.2 (5)	C52—C521—C522—C523	−179.2 (3)
C12—C11—C16—C15	2.8 (4)	C521—C522—C523—C524	−0.9 (5)
N1—C11—C16—C15	−176.7 (3)	C522—C523—C524—C525	0.6 (5)
C14—C15—C16—C11	−1.1 (5)	C523—C524—C525—C526	−0.1 (5)
C5—C4—C41—C42	5.4 (5)	C522—C521—C526—C525	−0.3 (5)
C3—C4—C41—C42	−166.5 (3)	C52—C521—C526—C525	179.7 (3)
C4—C41—C42—C43	178.0 (3)	C524—C525—C526—C521	−0.1 (5)
C41—C42—C43—O43	18.8 (5)

(3RS)-5'-[Benzyl(methyl)amino]-3'-methyl-1',5-diphenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole]-2-carbaldehyde (III)

Crystal data

C28H27N5O	F(000) = 952
Mr = 449.55	Dx = 1.292 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.321 (5) Å	Cell parameters from 5340 reflections
b = 21.572 (13) Å	θ = 2.4–27.6°
c = 9.550 (5) Å	µ = 0.08 mm^−1
β = 97.711 (18)°	T = 100 K
V = 2311 (2) Å^3	Block, colourless
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection

Bruker D8 Venture diffractometer	5340 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	4632 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.044
φ and ω scans	θmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS-2016/2; Bruker, 2016)	h = −14→14
Tmin = 0.958, Tmax = 0.992	k = −28→28
55209 measured reflections	l = −12→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0445P)^2 + 1.086P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5340 reflections	Δρmax = 0.30 e Å^−3
309 parameters	Δρmin = −0.29 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
N1	0.80264 (8)	0.37886 (4)	0.45145 (10)	0.01130 (19)
N2	0.89302 (8)	0.40971 (5)	0.39852 (10)	0.0131 (2)
C3	0.84320 (10)	0.43370 (5)	0.27671 (12)	0.0124 (2)
C4	0.72041 (10)	0.41987 (5)	0.25019 (11)	0.0112 (2)
C5	0.69607 (9)	0.38489 (5)	0.36443 (11)	0.0106 (2)
C11	0.83393 (9)	0.34601 (5)	0.58063 (11)	0.0117 (2)
C12	0.91643 (10)	0.37292 (6)	0.68399 (12)	0.0157 (2)
H12	0.9445	0.4138	0.6715	0.019*
C13	0.95754 (11)	0.33982 (6)	0.80550 (13)	0.0211 (3)
H13	1.0144	0.3579	0.8759	0.025*
C14	0.91545 (11)	0.28030 (7)	0.82398 (14)	0.0237 (3)
H14	0.9443	0.2574	0.9065	0.028*
C15	0.83127 (11)	0.25443 (6)	0.72181 (14)	0.0215 (3)
H15	0.8014	0.2141	0.7358	0.026*
C16	0.79004 (10)	0.28685 (5)	0.59898 (12)	0.0150 (2)
H16	0.7328	0.2688	0.5289	0.018*
C31	0.91846 (10)	0.47178 (6)	0.19176 (13)	0.0175 (2)
H31A	1.0003	0.4734	0.2403	0.026*
H31C	0.8861	0.5139	0.1811	0.026*
H31B	0.9181	0.4530	0.0983	0.026*
N41	0.70245 (9)	0.48378 (5)	−0.07521 (10)	0.0148 (2)
N42	0.66402 (9)	0.43154 (4)	−0.00832 (10)	0.0140 (2)
C42	0.66466 (11)	0.37542 (5)	−0.07026 (12)	0.0159 (2)
H42	0.6951	0.3722	−0.1579	0.019*
O42	0.62793 (8)	0.32863 (4)	−0.01887 (10)	0.0210 (2)
C43	0.63066 (10)	0.44466 (5)	0.13454 (11)	0.0121 (2)
H43	0.5499	0.4274	0.1427	0.015*
C44	0.62607 (10)	0.51618 (5)	0.13055 (12)	0.0136 (2)
H44A	0.5429	0.5314	0.1207	0.016*
H44B	0.6714	0.5343	0.2167	0.016*
C45	0.68405 (10)	0.53129 (5)	0.00081 (12)	0.0133 (2)
C451	0.72318 (10)	0.59351 (5)	−0.03545 (12)	0.0151 (2)
C452	0.80060 (11)	0.60095 (6)	−0.13649 (13)	0.0186 (2)
H452	0.8254	0.5656	−0.1843	0.022*
C453	0.84159 (12)	0.65907 (6)	−0.16787 (14)	0.0231 (3)
H453	0.8936	0.6637	−0.2374	0.028*
C454	0.80620 (12)	0.71070 (6)	−0.09689 (14)	0.0244 (3)
H454	0.8351	0.7506	−0.1170	0.029*
C455	0.72883 (13)	0.70409 (6)	0.00313 (14)	0.0238 (3)
H455	0.7044	0.7396	0.0508	0.029*
C456	0.68696 (12)	0.64578 (6)	0.03389 (13)	0.0194 (3)
H456	0.6337	0.6415	0.1021	0.023*
N51	0.58691 (8)	0.36254 (5)	0.39252 (10)	0.0136 (2)
C51	0.52849 (10)	0.31290 (6)	0.30513 (13)	0.0165 (2)
H51C	0.5577	0.3127	0.2131	0.025*
H51B	0.4421	0.3197	0.2916	0.025*
H51A	0.5464	0.2729	0.3521	0.025*
C52	0.55016 (10)	0.36967 (6)	0.53234 (12)	0.0151 (2)
H52A	0.6043	0.3992	0.5883	0.018*
H52B	0.5569	0.3292	0.5817	0.018*
C521	0.42311 (10)	0.39300 (5)	0.52380 (12)	0.0135 (2)
C522	0.38815 (11)	0.44714 (6)	0.44973 (13)	0.0172 (2)
H522	0.4435	0.4686	0.4010	0.021*
C523	0.27323 (11)	0.46987 (6)	0.44673 (13)	0.0190 (3)
H523	0.2509	0.5074	0.3980	0.023*
C524	0.19055 (11)	0.43807 (6)	0.51468 (13)	0.0197 (3)
H524	0.1118	0.4536	0.5123	0.024*
C525	0.22356 (11)	0.38368 (6)	0.58575 (14)	0.0191 (3)
H525	0.1670	0.3614	0.6310	0.023*
C526	0.33977 (10)	0.36144 (5)	0.59120 (13)	0.0154 (2)
H526	0.3622	0.3243	0.6415	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0079 (4)	0.0134 (4)	0.0125 (4)	−0.0015 (3)	0.0012 (3)	0.0018 (4)
N2	0.0097 (4)	0.0147 (5)	0.0151 (5)	−0.0014 (4)	0.0023 (4)	0.0023 (4)
C3	0.0116 (5)	0.0119 (5)	0.0136 (5)	0.0010 (4)	0.0017 (4)	0.0000 (4)
C4	0.0107 (5)	0.0110 (5)	0.0115 (5)	0.0007 (4)	0.0006 (4)	−0.0011 (4)
C5	0.0091 (5)	0.0110 (5)	0.0115 (5)	0.0001 (4)	0.0003 (4)	−0.0023 (4)
C11	0.0091 (5)	0.0148 (5)	0.0112 (5)	0.0027 (4)	0.0022 (4)	0.0013 (4)
C12	0.0121 (5)	0.0191 (6)	0.0156 (5)	−0.0023 (4)	0.0013 (4)	0.0007 (4)
C13	0.0137 (5)	0.0338 (7)	0.0148 (6)	−0.0018 (5)	−0.0016 (4)	0.0036 (5)
C14	0.0176 (6)	0.0346 (7)	0.0184 (6)	0.0019 (5)	0.0010 (5)	0.0137 (5)
C15	0.0177 (6)	0.0225 (6)	0.0248 (6)	−0.0007 (5)	0.0048 (5)	0.0100 (5)
C16	0.0119 (5)	0.0160 (5)	0.0170 (6)	−0.0003 (4)	0.0021 (4)	0.0013 (4)
C31	0.0127 (5)	0.0214 (6)	0.0183 (6)	−0.0018 (4)	0.0019 (4)	0.0055 (5)
N41	0.0167 (5)	0.0142 (5)	0.0128 (5)	0.0015 (4)	−0.0003 (4)	0.0019 (4)
N42	0.0178 (5)	0.0130 (5)	0.0109 (4)	0.0011 (4)	0.0012 (4)	0.0004 (4)
C42	0.0169 (6)	0.0161 (6)	0.0139 (5)	0.0036 (4)	−0.0004 (4)	−0.0024 (4)
O42	0.0266 (5)	0.0142 (4)	0.0223 (5)	0.0004 (3)	0.0035 (4)	−0.0015 (3)
C43	0.0113 (5)	0.0138 (5)	0.0110 (5)	0.0019 (4)	0.0005 (4)	−0.0009 (4)
C44	0.0138 (5)	0.0130 (5)	0.0134 (5)	0.0031 (4)	0.0001 (4)	−0.0001 (4)
C45	0.0122 (5)	0.0154 (5)	0.0113 (5)	0.0030 (4)	−0.0024 (4)	0.0012 (4)
C451	0.0154 (5)	0.0150 (5)	0.0134 (5)	0.0019 (4)	−0.0036 (4)	0.0014 (4)
C452	0.0174 (6)	0.0188 (6)	0.0190 (6)	0.0002 (5)	0.0005 (5)	−0.0005 (5)
C453	0.0214 (6)	0.0249 (7)	0.0227 (6)	−0.0028 (5)	0.0020 (5)	0.0047 (5)
C454	0.0278 (7)	0.0170 (6)	0.0265 (7)	−0.0032 (5)	−0.0034 (5)	0.0068 (5)
C455	0.0331 (7)	0.0144 (6)	0.0224 (6)	0.0043 (5)	−0.0019 (5)	0.0007 (5)
C456	0.0249 (6)	0.0169 (6)	0.0157 (6)	0.0039 (5)	0.0007 (5)	0.0022 (5)
N51	0.0097 (4)	0.0189 (5)	0.0126 (5)	−0.0042 (4)	0.0027 (4)	−0.0031 (4)
C51	0.0140 (5)	0.0168 (6)	0.0185 (6)	−0.0045 (4)	0.0013 (4)	−0.0029 (4)
C52	0.0114 (5)	0.0219 (6)	0.0122 (5)	−0.0007 (4)	0.0021 (4)	0.0000 (4)
C521	0.0110 (5)	0.0172 (5)	0.0123 (5)	−0.0020 (4)	0.0013 (4)	−0.0045 (4)
C522	0.0154 (5)	0.0192 (6)	0.0170 (6)	−0.0041 (4)	0.0017 (4)	−0.0003 (5)
C523	0.0183 (6)	0.0176 (6)	0.0200 (6)	0.0012 (5)	−0.0021 (5)	−0.0024 (5)
C524	0.0122 (5)	0.0239 (6)	0.0226 (6)	0.0012 (5)	0.0009 (5)	−0.0103 (5)
C525	0.0147 (6)	0.0206 (6)	0.0236 (6)	−0.0048 (5)	0.0082 (5)	−0.0066 (5)
C526	0.0155 (5)	0.0142 (5)	0.0172 (5)	−0.0025 (4)	0.0049 (4)	−0.0035 (4)

Geometric parameters (Å, º)

N1—N2	1.3726 (14)	C44—H44B	0.9900
N1—C5	1.3762 (15)	C45—C451	1.4691 (18)
N1—C11	1.4256 (15)	C451—C456	1.3968 (18)
N2—C3	1.3279 (16)	C451—C452	1.3972 (18)
C3—C4	1.4111 (16)	C452—C453	1.3835 (19)
C3—C31	1.4981 (16)	C452—H452	0.9500
C4—C5	1.3844 (16)	C453—C454	1.390 (2)
C4—C43	1.4957 (16)	C453—H453	0.9500
C5—N51	1.3859 (15)	C454—C455	1.387 (2)
C11—C16	1.3890 (17)	C454—H454	0.9500
C11—C12	1.3915 (17)	C455—C456	1.3895 (19)
C12—C13	1.3886 (18)	C455—H455	0.9500
C12—H12	0.9500	C456—H456	0.9500
C13—C14	1.389 (2)	N51—C52	1.4591 (16)
C13—H13	0.9500	N51—C51	1.4604 (16)
C14—C15	1.386 (2)	C51—H51C	0.9800
C14—H14	0.9500	C51—H51B	0.9800
C15—C16	1.3914 (18)	C51—H51A	0.9800
C15—H15	0.9500	C52—C521	1.5156 (17)
C16—H16	0.9500	C52—H52A	0.9900
C31—H31A	0.9800	C52—H52B	0.9900
C31—H31C	0.9800	C521—C526	1.3895 (17)
C31—H31B	0.9800	C521—C522	1.3950 (18)
N41—C45	1.2890 (16)	C522—C523	1.3871 (18)
N41—N42	1.3934 (15)	C522—H522	0.9500
N42—C42	1.3480 (16)	C523—C524	1.3895 (19)
N42—C43	1.4908 (16)	C523—H523	0.9500
C42—O42	1.2195 (16)	C524—C525	1.382 (2)
C42—H42	0.9500	C524—H524	0.9500
C43—C44	1.5440 (18)	C525—C526	1.3947 (18)
C43—H43	1.0000	C525—H525	0.9500
C44—C45	1.5135 (17)	C526—H526	0.9500
C44—H44A	0.9900
N2—N1—C5	111.60 (9)	H44A—C44—H44B	109.2
N2—N1—C11	116.66 (9)	N41—C45—C451	121.14 (11)
C5—N1—C11	131.72 (9)	N41—C45—C44	114.23 (11)
C3—N2—N1	105.17 (9)	C451—C45—C44	124.56 (10)
N2—C3—C4	111.54 (10)	C456—C451—C452	119.07 (12)
N2—C3—C31	118.85 (10)	C456—C451—C45	120.58 (11)
C4—C3—C31	129.56 (10)	C452—C451—C45	120.31 (11)
C5—C4—C3	105.62 (10)	C453—C452—C451	120.90 (12)
C5—C4—C43	126.12 (10)	C453—C452—H452	119.6
C3—C4—C43	127.75 (10)	C451—C452—H452	119.6
N1—C5—C4	106.04 (10)	C452—C453—C454	119.56 (13)
N1—C5—N51	125.63 (10)	C452—C453—H453	120.2
C4—C5—N51	128.25 (10)	C454—C453—H453	120.2
C16—C11—C12	120.74 (11)	C455—C454—C453	120.21 (12)
C16—C11—N1	120.95 (10)	C455—C454—H454	119.9
C12—C11—N1	118.14 (11)	C453—C454—H454	119.9
C13—C12—C11	119.73 (12)	C454—C455—C456	120.22 (12)
C13—C12—H12	120.1	C454—C455—H455	119.9
C11—C12—H12	120.1	C456—C455—H455	119.9
C12—C13—C14	119.96 (12)	C455—C456—C451	120.03 (12)
C12—C13—H13	120.0	C455—C456—H456	120.0
C14—C13—H13	120.0	C451—C456—H456	120.0
C15—C14—C13	119.85 (12)	C5—N51—C52	120.77 (9)
C15—C14—H14	120.1	C5—N51—C51	119.46 (9)
C13—C14—H14	120.1	C52—N51—C51	115.94 (9)
C14—C15—C16	120.80 (12)	N51—C51—H51C	109.5
C14—C15—H15	119.6	N51—C51—H51B	109.5
C16—C15—H15	119.6	H51C—C51—H51B	109.5
C11—C16—C15	118.88 (11)	N51—C51—H51A	109.5
C11—C16—H16	120.6	H51C—C51—H51A	109.5
C15—C16—H16	120.6	H51B—C51—H51A	109.5
C3—C31—H31A	109.5	N51—C52—C521	111.77 (10)
C3—C31—H31C	109.5	N51—C52—H52A	109.3
H31A—C31—H31C	109.5	C521—C52—H52A	109.3
C3—C31—H31B	109.5	N51—C52—H52B	109.3
H31A—C31—H31B	109.5	C521—C52—H52B	109.3
H31C—C31—H31B	109.5	H52A—C52—H52B	107.9
C45—N41—N42	107.51 (10)	C526—C521—C522	118.75 (11)
C42—N42—N41	120.32 (10)	C526—C521—C52	120.73 (11)
C42—N42—C43	126.09 (10)	C522—C521—C52	120.52 (10)
N41—N42—C43	113.52 (9)	C523—C522—C521	120.53 (11)
O42—C42—N42	122.99 (12)	C523—C522—H522	119.7
O42—C42—H42	118.5	C521—C522—H522	119.7
N42—C42—H42	118.5	C522—C523—C524	120.30 (12)
N42—C43—C4	112.18 (9)	C522—C523—H523	119.8
N42—C43—C44	100.30 (9)	C524—C523—H523	119.8
C4—C43—C44	113.13 (9)	C525—C524—C523	119.59 (11)
N42—C43—H43	110.3	C525—C524—H524	120.2
C4—C43—H43	110.3	C523—C524—H524	120.2
C44—C43—H43	110.3	C524—C525—C526	120.14 (11)
C45—C44—C43	102.63 (9)	C524—C525—H525	119.9
C45—C44—H44A	111.2	C526—C525—H525	119.9
C43—C44—H44A	111.2	C521—C526—C525	120.66 (12)
C45—C44—H44B	111.2	C521—C526—H526	119.7
C43—C44—H44B	111.2	C525—C526—H526	119.7
C5—N1—N2—C3	−1.47 (12)	C3—C4—C43—N42	57.71 (15)
C11—N1—N2—C3	177.20 (9)	C5—C4—C43—C44	115.77 (12)
N1—N2—C3—C4	1.05 (12)	C3—C4—C43—C44	−54.88 (15)
N1—N2—C3—C31	178.99 (10)	N42—C43—C44—C45	−12.20 (10)
N2—C3—C4—C5	−0.29 (13)	C4—C43—C44—C45	107.47 (11)
C31—C3—C4—C5	−177.94 (11)	N42—N41—C45—C451	175.48 (10)
N2—C3—C4—C43	171.88 (10)	N42—N41—C45—C44	−1.53 (13)
C31—C3—C4—C43	−5.77 (19)	C43—C44—C45—N41	9.44 (13)
N2—N1—C5—C4	1.31 (12)	C43—C44—C45—C451	−167.45 (10)
C11—N1—C5—C4	−177.10 (11)	N41—C45—C451—C456	170.03 (11)
N2—N1—C5—N51	−175.71 (10)	C44—C45—C451—C456	−13.28 (17)
C11—N1—C5—N51	5.89 (19)	N41—C45—C451—C452	−12.20 (17)
C3—C4—C5—N1	−0.60 (12)	C44—C45—C451—C452	164.49 (11)
C43—C4—C5—N1	−172.94 (10)	C456—C451—C452—C453	0.19 (18)
C3—C4—C5—N51	176.31 (11)	C45—C451—C452—C453	−177.61 (11)
C43—C4—C5—N51	3.97 (19)	C451—C452—C453—C454	0.64 (19)
N2—N1—C11—C16	−136.73 (11)	C452—C453—C454—C455	−1.0 (2)
C5—N1—C11—C16	41.61 (17)	C453—C454—C455—C456	0.5 (2)
N2—N1—C11—C12	38.68 (14)	C454—C455—C456—C451	0.31 (19)
C5—N1—C11—C12	−142.99 (12)	C452—C451—C456—C455	−0.66 (18)
C16—C11—C12—C13	1.50 (17)	C45—C451—C456—C455	177.13 (11)
N1—C11—C12—C13	−173.92 (10)	N1—C5—N51—C52	43.55 (16)
C11—C12—C13—C14	−0.60 (18)	C4—C5—N51—C52	−132.80 (13)
C12—C13—C14—C15	−0.84 (19)	N1—C5—N51—C51	−113.52 (13)
C13—C14—C15—C16	1.4 (2)	C4—C5—N51—C51	70.13 (16)
C12—C11—C16—C15	−0.94 (17)	C5—N51—C52—C521	133.46 (11)
N1—C11—C16—C15	174.34 (10)	C51—N51—C52—C521	−68.70 (13)
C14—C15—C16—C11	−0.51 (18)	N51—C52—C521—C526	126.73 (12)
C45—N41—N42—C42	175.13 (10)	N51—C52—C521—C522	−54.22 (15)
C45—N41—N42—C43	−7.81 (13)	C526—C521—C522—C523	1.72 (17)
N41—N42—C42—O42	−177.22 (11)	C52—C521—C522—C523	−177.35 (11)
C43—N42—C42—O42	6.11 (19)	C521—C522—C523—C524	−1.62 (18)
C42—N42—C43—C4	69.45 (14)	C522—C523—C524—C525	0.19 (18)
N41—N42—C43—C4	−107.41 (11)	C523—C524—C525—C526	1.09 (18)
C42—N42—C43—C44	−170.20 (11)	C522—C521—C526—C525	−0.43 (17)
N41—N42—C43—C44	12.94 (11)	C52—C521—C526—C525	178.63 (11)
C5—C4—C43—N42	−131.64 (12)	C524—C525—C526—C521	−0.97 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O42^i	0.95	2.43	3.207 (2)	139
C44—H44A···N42^ii	0.99	2.57	3.520 (3)	161
C44—H44B···Cg2^iii	0.99	2.73	3.646 (3)	154

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

(3RS)-2-acetyl-5'-[Benzyl(methyl)amino]- 5-(4-methoxyphenyl)-3'-methyl-1'-phenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole] ethanol 0.945-solvate (IV)

Crystal data

C30H31N5O2·0.945C2H6O	F(000) = 1146.3
Mr = 537.13	Dx = 1.262 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.363 (6) Å	Cell parameters from 6555 reflections
b = 28.238 (18) Å	θ = 2.3–27.6°
c = 10.775 (7) Å	µ = 0.08 mm^−1
β = 97.04 (2)°	T = 100 K
V = 2827 (3) Å^3	Plate, colourless
Z = 4	0.42 × 0.28 × 0.21 mm

Data collection

Bruker D8 Venture diffractometer	6550 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	5518 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.047
φ and ω scans	θmax = 27.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS-2016/2; Bruker, 2016)	h = −12→12
Tmin = 0.940, Tmax = 0.983	k = −36→36
65713 measured reflections	l = −14→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.4625P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
6550 reflections	Δρmax = 0.39 e Å^−3
370 parameters	Δρmin = −0.31 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.45887 (11)	0.66068 (4)	0.55283 (10)	0.0118 (2)
N2	0.60332 (11)	0.65210 (4)	0.57673 (10)	0.0131 (2)
C3	0.61856 (13)	0.62404 (4)	0.67664 (11)	0.0120 (2)
C4	0.48428 (13)	0.61354 (4)	0.71737 (11)	0.0117 (2)
C5	0.38381 (13)	0.63719 (4)	0.63553 (11)	0.0113 (2)
C11	0.40917 (13)	0.69361 (4)	0.45724 (11)	0.0120 (2)
C12	0.47304 (14)	0.69383 (4)	0.34750 (12)	0.0160 (3)
H12	0.5446	0.6711	0.3350	0.019*
C13	0.43171 (15)	0.72751 (5)	0.25611 (13)	0.0198 (3)
H13	0.4762	0.7281	0.1815	0.024*
C14	0.32558 (15)	0.76031 (5)	0.27366 (13)	0.0193 (3)
H14	0.2971	0.7832	0.2109	0.023*
C15	0.26125 (14)	0.75956 (4)	0.38278 (13)	0.0168 (3)
H15	0.1880	0.7818	0.3942	0.020*
C16	0.30301 (13)	0.72644 (4)	0.47576 (12)	0.0141 (2)
H16	0.2596	0.7262	0.5510	0.017*
C31	0.76666 (13)	0.60815 (5)	0.72900 (12)	0.0162 (3)
H31A	0.8355	0.6174	0.6718	0.024*
H31B	0.7676	0.5736	0.7388	0.024*
H31C	0.7936	0.6231	0.8106	0.024*
N41	0.65277 (11)	0.55646 (4)	0.97537 (10)	0.0141 (2)
N42	0.55980 (11)	0.59324 (4)	0.93773 (10)	0.0139 (2)
C42	0.56746 (14)	0.63518 (4)	0.99967 (12)	0.0152 (3)
O42	0.48177 (10)	0.66698 (3)	0.96734 (9)	0.0198 (2)
C421	0.68645 (16)	0.63970 (5)	1.10638 (13)	0.0211 (3)
H42A	0.6810	0.6708	1.1456	0.032*
H42B	0.7797	0.6363	1.0747	0.032*
H42C	0.6761	0.6149	1.1682	0.032*
C43	0.45776 (13)	0.58227 (4)	0.82489 (11)	0.0129 (2)
H43	0.3565	0.5862	0.8437	0.015*
C44	0.49061 (13)	0.52927 (4)	0.80662 (12)	0.0141 (2)
H44A	0.4080	0.5092	0.8221	0.017*
H44B	0.5150	0.5230	0.7213	0.017*
C45	0.61830 (13)	0.52086 (4)	0.90363 (11)	0.0127 (2)
C451	0.70203 (13)	0.47705 (4)	0.91853 (12)	0.0133 (2)
C452	0.83001 (14)	0.47552 (4)	1.00111 (12)	0.0155 (3)
H452	0.8622	0.5032	1.0464	0.019*
C453	0.90954 (14)	0.43456 (5)	1.01745 (13)	0.0174 (3)
H453	0.9972	0.4343	1.0722	0.021*
C454	0.86160 (14)	0.39350 (4)	0.95366 (13)	0.0169 (3)
O454	0.94401 (11)	0.35436 (3)	0.98203 (10)	0.0232 (2)
C457	0.88438 (18)	0.31013 (5)	0.93698 (17)	0.0315 (4)
H47A	0.7878	0.3065	0.9619	0.047*
H47B	0.9459	0.2842	0.9725	0.047*
H47C	0.8785	0.3093	0.8456	0.047*
C455	0.73640 (14)	0.39432 (4)	0.86971 (13)	0.0177 (3)
H455	0.7047	0.3666	0.8246	0.021*
C456	0.65808 (14)	0.43616 (4)	0.85248 (12)	0.0152 (3)
H456	0.5730	0.4368	0.7946	0.018*
N51	0.23382 (11)	0.63971 (4)	0.62052 (10)	0.0137 (2)
C51	0.16379 (14)	0.64632 (5)	0.73287 (13)	0.0184 (3)
H51A	0.1438	0.6154	0.7680	0.028*
H51B	0.0733	0.6636	0.7116	0.028*
H51C	0.2272	0.6645	0.7945	0.028*
C52	0.16039 (14)	0.60761 (5)	0.52478 (12)	0.0167 (3)
H52B	0.1954	0.6146	0.4437	0.020*
H52A	0.0560	0.6145	0.5155	0.020*
C521	0.18179 (14)	0.55537 (5)	0.55248 (12)	0.0164 (3)
C522	0.28431 (15)	0.52961 (5)	0.49705 (13)	0.0203 (3)
H522	0.3419	0.5452	0.4429	0.024*
C523	0.30349 (16)	0.48159 (5)	0.51976 (14)	0.0248 (3)
H523	0.3736	0.4646	0.4811	0.030*
C524	0.22047 (17)	0.45832 (5)	0.59887 (14)	0.0252 (3)
H524	0.2332	0.4254	0.6143	0.030*
C525	0.11873 (16)	0.48346 (5)	0.65534 (14)	0.0241 (3)
H525	0.0624	0.4678	0.7103	0.029*
C526	0.09895 (15)	0.53146 (5)	0.63177 (13)	0.0199 (3)
H526	0.0281	0.5483	0.6701	0.024*
O61	0.83673 (12)	0.66224 (4)	0.43191 (11)	0.0236 (3)	0.945 (3)
H61	0.767 (2)	0.6631 (7)	0.473 (2)	0.035*	0.945 (3)
C61	0.89741 (19)	0.70840 (6)	0.43365 (16)	0.0317 (4)	0.945 (3)
H61A	1.0031	0.7059	0.4540	0.038*	0.945 (3)
H61B	0.8606	0.7271	0.5007	0.038*	0.945 (3)
C62	0.86449 (18)	0.73404 (5)	0.31345 (15)	0.0253 (4)	0.945 (3)
H62A	0.8984	0.7154	0.2461	0.038*	0.945 (3)
H62B	0.9130	0.7649	0.3192	0.038*	0.945 (3)
H62C	0.7603	0.7388	0.2956	0.038*	0.945 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0090 (5)	0.0128 (5)	0.0136 (5)	0.0001 (4)	0.0013 (4)	0.0025 (4)
N2	0.0089 (5)	0.0149 (5)	0.0152 (5)	0.0008 (4)	0.0007 (4)	0.0019 (4)
C3	0.0116 (6)	0.0117 (5)	0.0126 (6)	0.0002 (4)	0.0015 (4)	0.0000 (4)
C4	0.0113 (6)	0.0109 (5)	0.0130 (6)	−0.0001 (4)	0.0016 (4)	0.0001 (4)
C5	0.0111 (6)	0.0099 (5)	0.0130 (6)	−0.0006 (4)	0.0022 (4)	0.0001 (4)
C11	0.0116 (6)	0.0102 (5)	0.0136 (6)	−0.0021 (4)	−0.0008 (5)	0.0011 (4)
C12	0.0158 (6)	0.0160 (6)	0.0162 (6)	0.0029 (5)	0.0026 (5)	0.0014 (5)
C13	0.0223 (7)	0.0221 (7)	0.0157 (6)	0.0028 (5)	0.0046 (5)	0.0053 (5)
C14	0.0225 (7)	0.0157 (6)	0.0187 (6)	0.0020 (5)	−0.0011 (5)	0.0063 (5)
C15	0.0166 (6)	0.0112 (6)	0.0222 (7)	0.0023 (5)	0.0002 (5)	−0.0009 (5)
C16	0.0149 (6)	0.0127 (6)	0.0150 (6)	−0.0004 (5)	0.0025 (5)	−0.0014 (5)
C31	0.0108 (6)	0.0194 (6)	0.0180 (6)	0.0013 (5)	0.0010 (5)	0.0045 (5)
N41	0.0156 (5)	0.0128 (5)	0.0137 (5)	0.0012 (4)	0.0013 (4)	0.0036 (4)
N42	0.0154 (5)	0.0130 (5)	0.0129 (5)	0.0022 (4)	0.0001 (4)	0.0017 (4)
C42	0.0181 (6)	0.0145 (6)	0.0144 (6)	−0.0021 (5)	0.0074 (5)	0.0005 (5)
O42	0.0230 (5)	0.0143 (4)	0.0230 (5)	0.0026 (4)	0.0063 (4)	0.0014 (4)
C421	0.0253 (7)	0.0192 (6)	0.0183 (7)	−0.0013 (5)	0.0011 (5)	−0.0048 (5)
C43	0.0118 (6)	0.0139 (6)	0.0129 (6)	−0.0009 (4)	0.0012 (5)	0.0022 (4)
C44	0.0151 (6)	0.0125 (6)	0.0143 (6)	−0.0007 (4)	−0.0002 (5)	0.0023 (4)
C45	0.0134 (6)	0.0128 (6)	0.0123 (6)	−0.0019 (4)	0.0029 (5)	0.0034 (4)
C451	0.0136 (6)	0.0129 (6)	0.0137 (6)	−0.0004 (5)	0.0032 (5)	0.0035 (4)
C452	0.0153 (6)	0.0133 (6)	0.0177 (6)	−0.0022 (5)	0.0007 (5)	0.0025 (5)
C453	0.0127 (6)	0.0178 (6)	0.0210 (7)	−0.0005 (5)	−0.0002 (5)	0.0049 (5)
C454	0.0157 (6)	0.0139 (6)	0.0219 (7)	0.0030 (5)	0.0062 (5)	0.0045 (5)
O454	0.0191 (5)	0.0149 (5)	0.0350 (6)	0.0054 (4)	0.0018 (4)	0.0017 (4)
C457	0.0303 (8)	0.0144 (7)	0.0486 (10)	0.0068 (6)	−0.0002 (7)	−0.0032 (6)
C455	0.0200 (6)	0.0135 (6)	0.0199 (6)	−0.0013 (5)	0.0039 (5)	−0.0013 (5)
C456	0.0146 (6)	0.0163 (6)	0.0144 (6)	−0.0010 (5)	0.0007 (5)	0.0019 (5)
N51	0.0086 (5)	0.0152 (5)	0.0172 (5)	−0.0001 (4)	0.0009 (4)	0.0015 (4)
C51	0.0130 (6)	0.0185 (6)	0.0248 (7)	−0.0001 (5)	0.0065 (5)	−0.0012 (5)
C52	0.0113 (6)	0.0199 (6)	0.0181 (6)	−0.0021 (5)	−0.0021 (5)	0.0024 (5)
C521	0.0134 (6)	0.0190 (6)	0.0153 (6)	−0.0025 (5)	−0.0035 (5)	−0.0015 (5)
C522	0.0170 (6)	0.0265 (7)	0.0170 (6)	−0.0006 (5)	0.0002 (5)	−0.0034 (5)
C523	0.0242 (7)	0.0264 (7)	0.0223 (7)	0.0056 (6)	−0.0034 (6)	−0.0094 (6)
C524	0.0318 (8)	0.0164 (6)	0.0241 (7)	0.0002 (6)	−0.0093 (6)	−0.0040 (5)
C525	0.0288 (8)	0.0209 (7)	0.0216 (7)	−0.0086 (6)	−0.0005 (6)	−0.0007 (5)
C526	0.0192 (7)	0.0197 (6)	0.0208 (7)	−0.0039 (5)	0.0024 (5)	−0.0036 (5)
O61	0.0191 (6)	0.0207 (6)	0.0333 (7)	0.0006 (4)	0.0125 (5)	0.0068 (4)
C61	0.0342 (9)	0.0342 (9)	0.0248 (8)	−0.0177 (7)	−0.0048 (7)	0.0063 (7)
C62	0.0276 (8)	0.0189 (7)	0.0277 (8)	−0.0060 (6)	−0.0031 (6)	0.0013 (6)

Geometric parameters (Å, º)

N1—N2	1.3671 (16)	C452—C453	1.3751 (19)
N1—C5	1.3716 (16)	C452—H452	0.9500
N1—C11	1.4228 (16)	C453—C454	1.394 (2)
N2—C3	1.3302 (17)	C453—H453	0.9500
C3—C4	1.4130 (18)	C454—O454	1.3610 (16)
C3—C31	1.5002 (19)	C454—C455	1.390 (2)
C4—C5	1.3803 (18)	O454—C457	1.4285 (19)
C4—C43	1.5014 (18)	C457—H47A	0.9800
C5—N51	1.3956 (18)	C457—H47B	0.9800
C11—C12	1.3889 (19)	C457—H47C	0.9800
C11—C16	1.3915 (18)	C455—C456	1.3909 (19)
C12—C13	1.3894 (19)	C455—H455	0.9500
C12—H12	0.9500	C456—H456	0.9500
C13—C14	1.388 (2)	N51—C51	1.4578 (18)
C13—H13	0.9500	N51—C52	1.4781 (18)
C14—C15	1.385 (2)	C51—H51A	0.9800
C14—H14	0.9500	C51—H51B	0.9800
C15—C16	1.3910 (19)	C51—H51C	0.9800
C15—H15	0.9500	C52—C521	1.513 (2)
C16—H16	0.9500	C52—H52B	0.9900
C31—H31A	0.9800	C52—H52A	0.9900
C31—H31B	0.9800	C521—C522	1.3956 (19)
C31—H31C	0.9800	C521—C526	1.3965 (19)
N41—C45	1.2849 (17)	C522—C523	1.386 (2)
N41—N42	1.3836 (15)	C522—H522	0.9500
N42—C42	1.3569 (17)	C523—C524	1.387 (2)
N42—C43	1.4840 (18)	C523—H523	0.9500
C42—O42	1.2261 (17)	C524—C525	1.387 (2)
C42—C421	1.505 (2)	C524—H524	0.9500
C421—H42A	0.9800	C525—C526	1.387 (2)
C421—H42B	0.9800	C525—H525	0.9500
C421—H42C	0.9800	C526—H526	0.9500
C43—C44	1.5453 (19)	O61—C61	1.421 (2)
C43—H43	1.0000	O61—H61	0.83 (2)
C44—C45	1.5074 (19)	C61—C62	1.483 (2)
C44—H44A	0.9900	C61—H61A	0.9900
C44—H44B	0.9900	C61—H61B	0.9900
C45—C451	1.4629 (18)	C62—H62A	0.9800
C451—C456	1.3918 (19)	C62—H62B	0.9800
C451—C452	1.4028 (19)	C62—H62C	0.9800
N2—N1—C5	111.46 (10)	C453—C452—C451	120.94 (12)
N2—N1—C11	118.71 (10)	C453—C452—H452	119.5
C5—N1—C11	129.65 (11)	C451—C452—H452	119.5
C3—N2—N1	105.28 (10)	C452—C453—C454	119.99 (13)
N2—C3—C4	111.41 (11)	C452—C453—H453	120.0
N2—C3—C31	119.01 (11)	C454—C453—H453	120.0
C4—C3—C31	129.57 (12)	O454—C454—C455	124.70 (12)
C5—C4—C3	105.23 (11)	O454—C454—C453	115.17 (12)
C5—C4—C43	127.83 (11)	C455—C454—C453	120.12 (12)
C3—C4—C43	126.92 (11)	C454—O454—C457	116.51 (12)
N1—C5—C4	106.60 (11)	O454—C457—H47A	109.5
N1—C5—N51	119.24 (11)	O454—C457—H47B	109.5
C4—C5—N51	134.10 (11)	H47A—C457—H47B	109.5
C12—C11—C16	120.57 (11)	O454—C457—H47C	109.5
C12—C11—N1	118.86 (11)	H47A—C457—H47C	109.5
C16—C11—N1	120.51 (11)	H47B—C457—H47C	109.5
C11—C12—C13	119.67 (12)	C454—C455—C456	119.32 (12)
C11—C12—H12	120.2	C454—C455—H455	120.3
C13—C12—H12	120.2	C456—C455—H455	120.3
C14—C13—C12	120.13 (13)	C455—C456—C451	121.22 (13)
C14—C13—H13	119.9	C455—C456—H456	119.4
C12—C13—H13	119.9	C451—C456—H456	119.4
C15—C14—C13	119.88 (12)	C5—N51—C51	117.32 (11)
C15—C14—H14	120.1	C5—N51—C52	115.16 (10)
C13—C14—H14	120.1	C51—N51—C52	116.11 (11)
C14—C15—C16	120.56 (12)	N51—C51—H51A	109.5
C14—C15—H15	119.7	N51—C51—H51B	109.5
C16—C15—H15	119.7	H51A—C51—H51B	109.5
C15—C16—C11	119.17 (12)	N51—C51—H51C	109.5
C15—C16—H16	120.4	H51A—C51—H51C	109.5
C11—C16—H16	120.4	H51B—C51—H51C	109.5
C3—C31—H31A	109.5	N51—C52—C521	114.90 (11)
C3—C31—H31B	109.5	N51—C52—H52B	108.5
H31A—C31—H31B	109.5	C521—C52—H52B	108.5
C3—C31—H31C	109.5	N51—C52—H52A	108.5
H31A—C31—H31C	109.5	C521—C52—H52A	108.5
H31B—C31—H31C	109.5	H52B—C52—H52A	107.5
C45—N41—N42	107.95 (11)	C522—C521—C526	118.19 (13)
C42—N42—N41	121.16 (11)	C522—C521—C52	120.33 (12)
C42—N42—C43	125.10 (11)	C526—C521—C52	121.46 (12)
N41—N42—C43	113.72 (10)	C523—C522—C521	121.03 (13)
O42—C42—N42	120.42 (13)	C523—C522—H522	119.5
O42—C42—C421	123.52 (12)	C521—C522—H522	119.5
N42—C42—C421	116.06 (11)	C522—C523—C524	120.12 (14)
C42—C421—H42A	109.5	C522—C523—H523	119.9
C42—C421—H42B	109.5	C524—C523—H523	119.9
H42A—C421—H42B	109.5	C525—C524—C523	119.58 (14)
C42—C421—H42C	109.5	C525—C524—H524	120.2
H42A—C421—H42C	109.5	C523—C524—H524	120.2
H42B—C421—H42C	109.5	C524—C525—C526	120.22 (14)
N42—C43—C4	111.02 (11)	C524—C525—H525	119.9
N42—C43—C44	100.86 (9)	C526—C525—H525	119.9
C4—C43—C44	114.64 (11)	C525—C526—C521	120.85 (13)
N42—C43—H43	110.0	C525—C526—H526	119.6
C4—C43—H43	110.0	C521—C526—H526	119.6
C44—C43—H43	110.0	C61—O61—H61	107.7 (14)
C45—C44—C43	102.56 (10)	O61—C61—C62	113.35 (13)
C45—C44—H44A	111.3	O61—C61—H61A	108.9
C43—C44—H44A	111.3	C62—C61—H61A	108.9
C45—C44—H44B	111.3	O61—C61—H61B	108.9
C43—C44—H44B	111.3	C62—C61—H61B	108.9
H44A—C44—H44B	109.2	H61A—C61—H61B	107.7
N41—C45—C451	120.26 (12)	C61—C62—H62A	109.5
N41—C45—C44	114.42 (11)	C61—C62—H62B	109.5
C451—C45—C44	125.32 (11)	H62A—C62—H62B	109.5
C456—C451—C452	118.35 (11)	C61—C62—H62C	109.5
C456—C451—C45	121.64 (12)	H62A—C62—H62C	109.5
C452—C451—C45	120.01 (11)	H62B—C62—H62C	109.5
C5—N1—N2—C3	−1.44 (13)	C5—C4—C43—C44	111.42 (14)
C11—N1—N2—C3	174.15 (10)	C3—C4—C43—C44	−66.88 (16)
N1—N2—C3—C4	0.91 (13)	N42—C43—C44—C45	−6.45 (11)
N1—N2—C3—C31	−179.33 (10)	C4—C43—C44—C45	112.88 (12)
N2—C3—C4—C5	−0.08 (14)	N42—N41—C45—C451	177.77 (10)
C31—C3—C4—C5	−179.80 (12)	N42—N41—C45—C44	−1.31 (14)
N2—C3—C4—C43	178.53 (11)	C43—C44—C45—N41	5.28 (14)
C31—C3—C4—C43	−1.2 (2)	C43—C44—C45—C451	−173.74 (11)
N2—N1—C5—C4	1.42 (13)	N41—C45—C451—C456	172.45 (12)
C11—N1—C5—C4	−173.56 (11)	C44—C45—C451—C456	−8.59 (18)
N2—N1—C5—N51	−176.32 (10)	N41—C45—C451—C452	−7.49 (18)
C11—N1—C5—N51	8.70 (18)	C44—C45—C451—C452	171.47 (11)
C3—C4—C5—N1	−0.79 (13)	C456—C451—C452—C453	−0.61 (18)
C43—C4—C5—N1	−179.38 (11)	C45—C451—C452—C453	179.33 (12)
C3—C4—C5—N51	176.46 (13)	C451—C452—C453—C454	−1.47 (19)
C43—C4—C5—N51	−2.1 (2)	C452—C453—C454—O454	−176.38 (12)
N2—N1—C11—C12	39.84 (16)	C452—C453—C454—C455	2.55 (19)
C5—N1—C11—C12	−145.49 (13)	C455—C454—O454—C457	−10.30 (19)
N2—N1—C11—C16	−137.24 (12)	C453—C454—O454—C457	168.58 (13)
C5—N1—C11—C16	37.43 (18)	O454—C454—C455—C456	177.30 (12)
C16—C11—C12—C13	0.77 (19)	C453—C454—C455—C456	−1.52 (19)
N1—C11—C12—C13	−176.30 (12)	C454—C455—C456—C451	−0.59 (19)
C11—C12—C13—C14	−1.0 (2)	C452—C451—C456—C455	1.65 (18)
C12—C13—C14—C15	0.3 (2)	C45—C451—C456—C455	−178.29 (12)
C13—C14—C15—C16	0.6 (2)	N1—C5—N51—C51	−137.53 (12)
C14—C15—C16—C11	−0.80 (19)	C4—C5—N51—C51	45.49 (19)
C12—C11—C16—C15	0.10 (18)	N1—C5—N51—C52	80.31 (14)
N1—C11—C16—C15	177.13 (11)	C4—C5—N51—C52	−96.67 (17)
C45—N41—N42—C42	177.72 (11)	C5—N51—C52—C521	64.11 (14)
C45—N41—N42—C43	−3.64 (14)	C51—N51—C52—C521	−78.52 (14)
N41—N42—C42—O42	−177.97 (11)	N51—C52—C521—C522	−98.83 (15)
C43—N42—C42—O42	3.55 (19)	N51—C52—C521—C526	82.24 (16)
N41—N42—C42—C421	2.79 (17)	C526—C521—C522—C523	0.1 (2)
C43—N42—C42—C421	−175.69 (11)	C52—C521—C522—C523	−178.88 (12)
C42—N42—C43—C4	63.24 (15)	C521—C522—C523—C524	−0.2 (2)
N41—N42—C43—C4	−115.34 (12)	C522—C523—C524—C525	−0.3 (2)
C42—N42—C43—C44	−174.86 (11)	C523—C524—C525—C526	0.7 (2)
N41—N42—C43—C44	6.57 (12)	C524—C525—C526—C521	−0.8 (2)
C5—C4—C43—N42	−135.11 (13)	C522—C521—C526—C525	0.4 (2)
C3—C4—C43—N42	46.59 (16)	C52—C521—C526—C525	179.34 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O61—H61···N2	0.83 (2)	2.03 (2)	2.851 (2)	169.4 (19)
C52—H52A···O61^i	0.99	2.53	3.438 (3)	153
C524—H524···O61^ii	0.95	2.59	3.456 (3)	151

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