Seven 5-benzyl­amino-3-tert-butyl-1-phenyl-1H-pyrazoles: unexpected isomorphisms, and hydrogen-bonded supra­molecular structures in zero, one and two dimensions

5-Benzyl­amino-3-tert-butyl-1-phenyl-1H-pyrazole, C₂₀H₂₃N₃, (I), and its 5-[4-(trifluoro­meth­yl)benz­yl]-, C₂₁H₂₂F₃N₃, (III), and 5-(4-bromo­benz­yl)-, C₂₀H₂₂BrN₃, (V), analogues, are isomorphous in the space group C2/c, but not strictly isostructural; mol­ecules of (I) form hydrogen-bonded chains, while those of (III) and (V) form hydrogen-bonded sheets, albeit with slightly different architectures. Mol­ecules of 3-tert-butyl-5-(4-methyl­benzyl­amino)-1-phenyl-1H-pyrazole, C₂₁H₂₅N₃, (II), are linked into hydrogen-bonded dimers by a combination of N-H...[pi](arene) and C-H...[pi](arene) hydrogen bonds, while those of 3-tert-butyl-5-(4-chloro­benzyl­amino)-1-phenyl-1H-pyrazole, C₂₀H₂₂ClN₃, (IV), form hy­dro­gen-bonded chains of rings which are themselves linked into sheets by an aromatic [pi]-[pi] stacking inter­action. Simple hydrogen-bonded chains built from a single N-H...O hydrogen bond are formed in 3-tert-butyl-5-(4-nitro­benzyl­amino)-1-phenyl-1H-pyrazole, C₂₀H₂₂N₄O₂, (VI), while in 3-tert-butyl-5-(3,4,5-trimethoxy­benzyl­amino)-1-phenyl-1H-pyra­zole, C₂₃H₂₉N₃O₃, (VII), which crystallizes with Z' = 2 in the space group P, pairs of mol­ecules are linked into two independent centrosymmetric dimers, one generated by a three-centre N-H...(O)₂ hydrogen bond and the other by a two-centre N-H...O hydrogen bond.

S1. Comment

Pyrazoles are a class of heterocyclic compounds whose members exhibit a wide range of interesting properties, including drug and pesticide activity, as well as forming the basis for new materials (Elguero, 1984, 1996). We have recently determined the structures of a number of new (E)-5-arylidenamino-3-tert-butyl-1-phenyl-1H-pyrazoles, which are the first intermediates isolated in a synthetic pathway developed as a route to new fused heterocyclic compounds containing the pyrazole unit (Castillo et al., 2009). The next step in this pathway requires the reduction of the imine derivatives to give the corresponding 5-arylmethylamino-3-tert-butyl-1-phenyl-1H-pyrazoles, and here we report the molecular and supramolecular structures of seven compounds of this type, namely 5-benzylamino-3-tert-butyl-1-phenyl-1H-pyrazole, (I), and its 4-methylbenzyl, 4-(trifluoromethyl)benzyl, 4-chlorobenzyl, 4-bromobenzyl and 4-nitrobenzyl analogues, compounds (II)–(VI), and the 3,4,5-trimethoxybenzyl analogue, (VII), which we compare with the 4-methoxybenzyl derivative, (VIII), whose structure was reported several years ago (Abonía et al., 2007) (see scheme and Fig. 1).

The crystallization characteristics of the benzylamino series, compounds (I)–(VII), show some unexpected features. It is not infrequently found that the corresponding 4-methylphenyl and 4-chlorophenyl derivatives in a particular series are isomorphous and isostructural; likewise the corresponding 4-chlorophenyl and 4-bromophenyl analogues in other series and not infrequently found to be isomorphous. However, in the present series of compounds, no two of these derivatives, viz. compounds (II), (IV) and (V), are isomorphous. By contrast, and somewhat unexpectedly, the unsubstituted benzyl compound, (I), was found to be isomorphous with both the 4-trifluorobenzyl, (III), and 4-bromobenzyl, (V), compounds. These three compounds all crystallize in the space group C2/c with very similar cell dimensions and very similar values for the coordinates for corresponding atoms. However, the 4-chlorobenzyl analogue, (IV), in the space group P1, is isomorphous neither with 4-methylbenzyl compound (II) nor 4-bromobenzyl compound (V).

4-Methylbenzyl compound (II) and its 4-methoxy analogue, (VIII) (Abonía et al., 2007), are effectively isomorphous, with close correspondence between the two sets of atomic coordinates, although the cell dimensions are slightly larger for (VIII) [a = 10.9665 (14)Å and c = 30.976 (6)Å]. For neither of these compounds was it possible to establish whether the correct space group for the crystal selected for data collection was P4₁2₁2 or P4₃2₁2, and hence the correct conformational enantiomorphs present in these crystals could not be determined, although this identification has no chemical significance. For (VIII), the authors concluded that the distribution between the two space groups was probably statistical, as was the distribution of the two conformational enantiomorphs. Since compound (I) and compounds (III)–(VII) all crystallize in centrosymmetric space groups as racemic mixtures of conformational enantiomorphs, this conclusion concerning the space groups seems appropriate for compound (II) also.

All of the compounds studied here crystallize with Z' = 1, with the exception of 3,4,5-trimethoxybenzyl derivative (VII), which crystallizes in P1 with Z' = 2. The various ADDSYM routines in PLATON (Spek, 2009) all showed that no additional symmetry was present. However, the two molecules in the selected asymmetric unit, which were chosen to have the same orientation of the 1-phenyl group relative to the pyrazole ring, are approximately related by a noncrystallographic translation of (1/2, 0, 1/2). As discussed below, the conformations adopted by the tert-butyl groups in the two independent molecules definitively rule out the possibility of any further crystallographic symmetry.

With the exception of the polyatomic substituent groups in the benzyl unit, the overall molecular conformations of compounds (I)–(VII) can be defined in terms of just five torsion angles (Table 1). The orientation of the unsubstituted phenyl ring, as defined by the torsional angles Nx2—Nx1—Cx11—Cx12 and the location of the benzyl methylene unit, as defined by the torsion angles Nx1—Cx5—Nx51—Cx57, show only modest variation across the whole series, In all compounds except (IV) and (VII), there is an intrmolecular C—H···N contact from atom C12 (Table 2): however, the orientation of the unsubstituted phenyl ring does not seem to be significantly influenced by the presence or absence of this contact. The other torsion angles show some interesting variations: in particular, both the position of the substituted aryl ring, as defined by Cx5—Nx51—Cx57—Cx51, and the orientation of this ring, as defined by Nx51—Cx57—Cx51—Cx52, differ markedly in compounds (IV) and (VI) from those in the remainder. In a similar manner, the orientation of the tert-butyl groups in compounds (I), (III) and (V) is such that one methyl group is fairly close to the plane of the pyrazole ring, although by no means coincident with it, while in the other compounds, the projection of one of the C—C bonds in this group is almost normal to the plane of the pyrazole ring. The two independent molecules in compound (VII) have almost identical conformations, apart from their tert-butyl groups, which are rotated in the opposite senses relative to the pyrazole ring. The tert-butyl groups in compounds (I)–(VII) are directly bonded to a planar ring, so that the rotational barriers about the exocyclic C—C bonds will be a close approximation to an idealized sixfold barrier, long known to be extremely low, ca a few tens of J mol^-1 (Tannenbaum et al., 1956; Naylor & Wilson, 1957); accordingly, the tert-butyl groups may be acting here essentially as space fillers, adopting whatever orientations are best adapted to the spaces available between the molecules, once the direction-specific intermolecular forces have been accommodated.

A variety of direction-specific intermolecular interactions are present in the structures of compounds (I)–(VII), in particular X—H···π(arene) and X—H···π(pyrazole) hydrogen bonds, both for X = C and N, as well as N—H..O hydrogen bonds in both (VI) and (VII) (Table 2). These interactions link the molecules into supramolecular aggregations ranging from finite (zero-dimensional) dimer units in each of (II) and (VII), via simple chains in (I) and (VI), and chains of rings π-stacked into sheets in (IV), to hydrogen-bonded sheets in each of (III) and (V).

Compounds (I), (III) and (V) are isomorphous, and in each compound molecules related by a 2₁ screw axis along (3/4, y, 1/4) are linked into chains by an N—H···π(pyrazole) hydrogen bond. While the molecules of the three compounds are arranged almost identically in their unit cells, the weak intermolecular forces show some differences from one compound to another. Thus, in (III), a C—H···π(arene) interaction involving the C11–C16 ring links the initial chains into sheets parallel to (001) (Fig. 2), while in (V), the (001) sheet is generated by a C—H···π(arene) hydrogen bond involving the C51–C56 ring (Fig. 3). In each of (III) and (V), the reference sheet lies in the domain 0 < z < 0.5 with a further sheet, which is related to the first by inversion, lying in the domain 0.5 < z < 1.0: however, there are no direction-specific interactions between adjacent sheets.

Minor changes in the unit-cell dimensions from one compound to another in this group are apparently sufficient to bring different weak interactions into play: this does not, however, detract from the fact that the overall molecular arrangements within this group are effectively the same. Thus, while this group can be regarded as isostructural in terms of the overall molecular arrangement, they are not strictly isostructural in terms of the direction-specific intermolecular interactions which appear to be operative. We have recently reported (Acosta et al., 2009) another series of compounds which similarly are isomorphous in terms of only small changes in their unit-cell dimensions, as well as in their atomic coordinates, but where these changes in cell dimension are sufficient to influence which of the intermolecular interactions are structurally significant, so that those compounds are not strictly isostructural.

In compound (II), the combination of one N—H···π(arene) hydrogen bond and one C—H···π(arene) hydrogen bond, each involving a different arene ring, links pairs of molecules related by the twofold rotation axis along x = y at z = 0.5 into a finite dimeric unit (Fig. 4). The are four of these dimeric units in each unit cell, each lying across a different rotation axis, but there are no direction-specific interactions between the dimers; in particular, aromatic π–π stacking interactions are absent. The supramolecular aggregation in compound (II) is thus significantly different from that in the isomorphous 4-methoxybenzyl analogue (VIII) (Abonía et al., 2007), where a single C—H···N hydrogen bond links molecules related by translation into simple C(9) chains: N—H···π and C—H···π interactions are, however, absent from the structure of (VIII).

The only possible acceptor within hydrogen bonding range of the N—H bond in compound (IV) is the Cl atom of the molecule at (1-x, 1-y, -z). However, it has been concluded that such contacts involving covalently bound Cl are probably no more than van der Waals contacts, and that geometrically they are certainly at the outer limit of what could conceivably be described as a hydrogen bond (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001). Accordingly, we have discounted this contact as it seems unlikely to be of structural significance.

A C—H···N hydrogen bond links molecules of (IV) which are related by translation into a C(9) (Bernstein et al., 1995) chain running parallel to the [001] direction (Fig. 5). Antiparallel pairs of such chains, related by inversion and then linked into a chain of edge-fused rings along (1/2, 0, z) (Fig. 5). The 4-chlorophenyl rings of the molecules at (x, y, z) and (1-x, 1-y, 2-z) are strictly parallel within an interplanar spacing of 3.474 (2)Å; the ring-centroid separation is 3.773 (2)Å, corresponding to a near-ideal ring-centroid offset of 1.472 (2)Å (Fig. 6). The two molecules involved in this π-stacking interaction forms parts of the hydrogen-bonded chains along (1/2, 0, z) and (1/2, 1, z), so that this interactions links hydrogen-bonded chains of rings into a sheet parallel to (100). By contrast, the supramolecular aggregation in compound (VI) depends upon just a single N—H···O hydrogen bond, which links molecules related by translation into a simple chain running parallel to the [100] direction (Fig. 7).

The supramolecular aggregation in 3,4,5-trimethoxybenzyl derivative (VII) depends solely upon N—H···O hydrogen bonds, which generate two independent centrosymmetric dimers. The dimer formed by the type 1 molecules contains an asymmetric three-centre N—H···(O)₂ interaction, which generates a centrosymmetric R₂²(14) ring flanked by two symmetry-related R₁²(5) rings, while the dimer formed by the type 2 molecules contains a single R₂²(16) ring (Fig. 8). These two dimers are centred respectively across (1/2, 0, 1/2) and (1, 0, 1), illustrating again the pseudo-translational relationship between the two independent molecules in this structure. As with the conformations of the tert-butyl groups discussed above, so too the different N—H···O interactions within the two independent dimers rules out the possibility of any additional crystallographic symmetry.

Related literature

For related literature, see: Aakeröy et al. (1999); Abonía et al. (2007); Acosta et al. (2009); Bernstein et al. (1995); Brammer et al. (2001); Castillo et al. (2009); Naylor & Wilson (1957); Spek (2009); Tannenbaum et al. (1956); Thallapally & Nangia (2001).

S2. Experimental

To a solution of the appropriate (E)-5-arylidenamino-3-tert-butyl-1-phenyl-1H-pyrazole (100 mg) in methanol (3–4 ml) solid sodium borohydride (2.5 mmol) was added portionwise with stirring during 5 min, and after 1 h at ambient temperature, the volume of the reaction mixture was reduced under reduced pressure to 1 ml, followed by the addition of 5 ml of water. The aqueous solution was extracted with ethyl acetate (2 × 5 ml), and the combined organic extracts were dried over anhydrous sodium sulfate; after removal of the solvent the resulting products were crystallized from ethanol, except for (I) which was crystallized from hexane. (I): colourless, 91% yield, m.p. 351 K; MS (70 eV) m/z (%): 305 (100) [M⁺], 290 (59) [M-15], 263 (69) [M-42], 91 (34), 77 (13) [Ph]; analysis found: C 78.5, H 7.8, N 13.7%; C₂₀H₂₃N₃ requires C 78.7, H 7.6, N 13.8%. (II): colourless, 85% yield, m.p. 372–373 K; MS (70 eV) m/z (%): 319 (76) [M⁺], 304 (18) [M-15], 277 (30) [M-42], 105 (100) [C₈H₉], 77 (8) [Ph]; analysis found: C 78.7, H 8.1, N 12.9%; C₂₁H₂₅N₃ requires C 79.0, H 7.9, N 13.2%. (III): yellow, 77% yield, m.p. 370–371 K; MS 70 (eV) m/z (%): 373 (100) [M⁺], 358 (84) [M-15], 331 (98) [M-42], 214 (19), 159 (38) [C₈H₆F₃], 77 (10); analysis found: C 67.4, H 5.9, N 11.2%; C₂₁H₂₂F₃N₃ requires C 67.6, H 5.9, N 11.3%. (IV) colourless, 89% yield, m.p. 386–388 K; MS (70 eV) m/z (%): 341/339 (28/84) [M⁺], 326/324 (13/35) [M-15], 299/297 (20/58) [M-42], 214 (37), 158 (38), 127/125 (29/100) [C₇H₆Cl], 77 (63) [Ph]; analysis found: C 70.5, H 6.7, N 12.3%; C₂₀H₂₂ClN₃ requires C 70.7, H 6.5, N 12.4%. (V): yellow, 83% yield, m.p. 365–366 K; MS (70 eV) m/z (%): 385/383 (96/100) [M⁺], 370/368 (45/44) [M-15], 343/341 (70/73) [M-42], 214 (70), 171/169 (72/67) [C₇H₆Br]; analysis found: C 62.3, H 5.9, N 11.0%; C₂₀H₂₂BrN₃ requires C 62.5, H 5.8, N 10.9%. (VI): yellow, 84% yield, m.p. 375–377 K; MS (70 eV) m/z (%): 350 (95) [M⁺], 335 (85) [M-15], 308 (100) [M-42], 214 (15), 158 (15); analysis found: C 68.2, H 6.3, N 16.0%; C₂₀H₂₂N₄O₂ requires C 68.6, H 6.3, N 16.0%. (VII): colourless, 83% yield, m.p. 392–394 K; MS 70 (eV) m/z (%): 395 (8) [M⁺], 181 (100) [C₁₀H₁₃O₃]; analysis found: C 69.9, H 7.3, N 10.7%; C₂₃H₂₉N₃O₃ requires C 69.9, H 7.4, N 10.6%.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms with distances C—H = 0.95 (aromatic and pyrazole), 0.98 (CH₃) or 0.99Å (CH₂) and N—H = 0.88Å, with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and k = 1.2 for all other H atoms. For the compounds which crystallize in centrosymmetric space groups, the reference molecules were all selected to have the same orientation of the 1-phenyl group, as defined by the sign of the torsion angle N2—N1—C11—C12. In the absence of significant resonant scattering, it was not possible, for compound (II), to distinguish between the possible enantiomeric space groups P4₁2₁2 and P4₃2₁2; for consistency of configuration, P4₃2₁2 was selected and the Friedel-equivalent reflections were merged prior to the final refinements. In compound (VI), the largest maxima in the final difference maps, with heights 0.65, 0.62 and 0.40 e Å^-3 were located, respectively, 1.37Å from C33, 1.07Å from C34 and 1.12Å from C32, consistent with some librational motion of this group about the C3—C31 bond.

Computing details

For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structures of compounds (I)–(VIII) showing the atom-labelling schemes: (a) compound (I), (b) compound (II), (c) compound (III), (d) compound (IV), (e) compound (V), (f) compound (VI) and (g) the two independent molecules of compound (VII). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of compound (III), showing the formation of a sheet parallel to (001) containing N—H···π(pyrazole) and C—H···π(arene) interactions. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of compound (V), showing the formation of a sheet parallel to (001) containing N—H···π(pyrazole) and C—H···π(arene) interactions. For the sake of clarity, H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 4. Part of the crystal structure of compound (II), showing the formation of a dimeric aggregate of molecules related by a twofold rotation axis. For the sake of clarity, the unit-cell outline and H atoms bonded to C atoms not involved in the motifs shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (y, x, 1-z).
	Fig. 5. A stereoview of part of the crystal structure of compound (IV), showing the formation of a chain of centrosymmetric ring running parallel to the [001] direction and containing C—H···N and C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motifs shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (IV), showing the aromatic π–π stacking interaction which links chains of rings into sheets parallel to ((100). For the sake of clarity, H atoms bonded to C or N atoms not involved in the motifs shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of compound (VI), showing the formation of a hydrogen-bonded C(9) chain running parallel to the [100] direction and containing N—H···O hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have all been omitted.
	Fig. 8. A stereoview of part of the crystal structure of compound (VII), showing the location of the two independent hydrogen-bonded dimers within the unit cell. For the sake of clarity, H atoms bonded to C atoms have all been omitted.

(I) 5-Benzylamino-3-tert-butyl-1-phenyl-1H-pyrazole

Crystal data

C20H23N3	F(000) = 1312
Mr = 305.41	Dx = 1.219 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3813 reflections
a = 20.038 (4) Å	θ = 3.0–27.5°
b = 7.3732 (12) Å	µ = 0.07 mm^−1
c = 23.444 (3) Å	T = 120 K
β = 106.007 (13)°	Block, colourless
V = 3329.4 (10) Å^3	0.31 × 0.26 × 0.21 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	3813 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2464 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −25→26
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→8
Tmin = 0.967, Tmax = 0.985	l = −30→30
30597 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 3.306P] where P = (Fo^2 + 2Fc^2)/3
3813 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.80088 (7)	0.5329 (2)	0.26985 (6)	0.0230 (3)
N2	0.84668 (7)	0.5054 (2)	0.32481 (6)	0.0241 (3)
C3	0.80690 (9)	0.4923 (2)	0.36096 (7)	0.0233 (4)
C4	0.73622 (9)	0.5123 (2)	0.33111 (8)	0.0252 (4)
H4	0.6980	0.5071	0.3477	0.030*
C5	0.73429 (9)	0.5410 (2)	0.27302 (7)	0.0225 (4)
C11	0.82814 (9)	0.5552 (2)	0.22082 (7)	0.0223 (4)
C12	0.79363 (9)	0.4875 (2)	0.16575 (7)	0.0234 (4)
H12	0.7509	0.4249	0.1602	0.028*
C13	0.82168 (10)	0.5117 (2)	0.11892 (8)	0.0271 (4)
H13	0.7977	0.4666	0.0808	0.033*
C14	0.88396 (10)	0.6003 (3)	0.12662 (8)	0.0292 (4)
H14	0.9029	0.6167	0.0940	0.035*
C15	0.91864 (10)	0.6648 (3)	0.18190 (8)	0.0306 (4)
H15	0.9618	0.7253	0.1875	0.037*
C16	0.89114 (9)	0.6424 (3)	0.22916 (8)	0.0277 (4)
H16	0.9154	0.6867	0.2673	0.033*
C31	0.83925 (9)	0.4710 (2)	0.42670 (7)	0.0251 (4)
C32	0.91643 (10)	0.4319 (3)	0.44016 (8)	0.0335 (5)
H32A	0.9233	0.3150	0.4227	0.050*
H32B	0.9369	0.4274	0.4832	0.050*
H32C	0.9389	0.5280	0.4232	0.050*
C33	0.82778 (11)	0.6468 (3)	0.45687 (8)	0.0349 (5)
H33A	0.8476	0.7483	0.4400	0.052*
H33B	0.8505	0.6384	0.4995	0.052*
H33C	0.7779	0.6666	0.4504	0.052*
C34	0.80419 (11)	0.3155 (3)	0.45023 (9)	0.0394 (5)
H34A	0.7543	0.3398	0.4417	0.059*
H34B	0.8243	0.3046	0.4932	0.059*
H34C	0.8114	0.2021	0.4310	0.059*
N51	0.67992 (7)	0.5687 (2)	0.22328 (6)	0.0246 (4)
H51	0.6899	0.6431	0.1975	0.029*
C51	0.55559 (9)	0.5726 (2)	0.17444 (7)	0.0227 (4)
C52	0.49507 (9)	0.6717 (3)	0.16277 (8)	0.0279 (4)
H52	0.4897	0.7611	0.1904	0.034*
C53	0.44235 (10)	0.6436 (3)	0.11191 (9)	0.0340 (5)
H53	0.4005	0.7111	0.1051	0.041*
C54	0.44987 (10)	0.5183 (3)	0.07089 (8)	0.0318 (5)
H54	0.4136	0.4999	0.0355	0.038*
C55	0.51016 (10)	0.4197 (3)	0.08137 (8)	0.0298 (4)
H55	0.5159	0.3343	0.0528	0.036*
C56	0.56229 (9)	0.4441 (2)	0.13307 (8)	0.0261 (4)
H56	0.6032	0.3724	0.1405	0.031*
C57	0.61154 (9)	0.6008 (3)	0.23129 (8)	0.0253 (4)
H571	0.6090	0.7265	0.2454	0.030*
H572	0.6039	0.5172	0.2619	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0215 (8)	0.0296 (8)	0.0167 (7)	0.0000 (6)	0.0032 (6)	0.0011 (6)
N2	0.0247 (8)	0.0283 (8)	0.0167 (7)	−0.0008 (7)	0.0013 (6)	0.0002 (6)
C3	0.0261 (9)	0.0221 (9)	0.0207 (9)	−0.0029 (8)	0.0050 (7)	−0.0008 (7)
C4	0.0253 (10)	0.0275 (10)	0.0228 (9)	−0.0043 (8)	0.0069 (7)	−0.0003 (7)
C5	0.0237 (9)	0.0203 (9)	0.0227 (9)	−0.0009 (7)	0.0047 (7)	−0.0016 (7)
C11	0.0231 (9)	0.0235 (9)	0.0203 (8)	0.0039 (7)	0.0060 (7)	0.0036 (7)
C12	0.0228 (9)	0.0241 (9)	0.0227 (9)	0.0008 (8)	0.0053 (7)	0.0005 (7)
C13	0.0296 (10)	0.0306 (10)	0.0199 (9)	0.0047 (8)	0.0051 (7)	−0.0010 (7)
C14	0.0298 (10)	0.0358 (11)	0.0245 (9)	0.0041 (9)	0.0119 (8)	0.0032 (8)
C15	0.0247 (10)	0.0344 (11)	0.0322 (10)	−0.0023 (8)	0.0070 (8)	0.0022 (8)
C16	0.0258 (10)	0.0319 (10)	0.0235 (9)	−0.0007 (8)	0.0037 (8)	0.0002 (8)
C31	0.0273 (10)	0.0281 (10)	0.0178 (8)	−0.0052 (8)	0.0029 (7)	0.0008 (7)
C32	0.0334 (11)	0.0392 (12)	0.0240 (10)	−0.0012 (9)	0.0014 (8)	0.0011 (8)
C33	0.0435 (12)	0.0370 (12)	0.0233 (10)	−0.0016 (9)	0.0076 (9)	−0.0034 (8)
C34	0.0456 (12)	0.0427 (13)	0.0247 (10)	−0.0158 (10)	0.0008 (9)	0.0055 (9)
N51	0.0204 (8)	0.0326 (9)	0.0201 (7)	0.0003 (7)	0.0047 (6)	0.0040 (6)
C51	0.0224 (9)	0.0243 (9)	0.0219 (9)	−0.0005 (8)	0.0068 (7)	0.0043 (7)
C52	0.0280 (10)	0.0294 (10)	0.0277 (10)	0.0042 (8)	0.0099 (8)	−0.0004 (8)
C53	0.0261 (10)	0.0369 (12)	0.0371 (11)	0.0069 (9)	0.0056 (9)	0.0045 (9)
C54	0.0265 (10)	0.0362 (11)	0.0276 (10)	−0.0014 (9)	−0.0012 (8)	0.0014 (8)
C55	0.0334 (11)	0.0273 (10)	0.0265 (10)	0.0000 (9)	0.0046 (8)	−0.0031 (8)
C56	0.0248 (9)	0.0279 (10)	0.0247 (9)	0.0012 (8)	0.0056 (8)	0.0008 (8)
C57	0.0241 (9)	0.0296 (10)	0.0231 (9)	−0.0005 (8)	0.0081 (7)	−0.0023 (7)

Geometric parameters (Å, º)

N1—C5	1.358 (2)	C32—H32B	0.9800
N1—N2	1.3752 (19)	C32—H32C	0.9800
N1—C11	1.412 (2)	C33—H33A	0.9800
N2—C3	1.318 (2)	C33—H33B	0.9800
C3—C4	1.404 (2)	C33—H33C	0.9800
C3—C31	1.506 (2)	C34—H34A	0.9800
C4—C5	1.368 (2)	C34—H34B	0.9800
C4—H4	0.9500	C34—H34C	0.9800
C5—N51	1.374 (2)	N51—C57	1.453 (2)
C11—C12	1.379 (2)	N51—H51	0.8799
C11—C16	1.382 (2)	C57—C51	1.501 (2)
C12—C13	1.376 (2)	C57—H571	0.9900
C12—H12	0.9500	C57—H572	0.9900
C13—C14	1.376 (3)	C51—C52	1.377 (2)
C13—H13	0.9500	C51—C56	1.388 (3)
C14—C15	1.376 (3)	C52—C53	1.373 (3)
C14—H14	0.9500	C52—H52	0.9500
C15—C16	1.377 (3)	C53—C54	1.371 (3)
C15—H15	0.9500	C53—H53	0.9500
C16—H16	0.9500	C54—C55	1.373 (3)
C31—C32	1.518 (3)	C54—H54	0.9500
C31—C33	1.524 (3)	C55—C56	1.376 (2)
C31—C34	1.525 (3)	C55—H55	0.9500
C32—H32A	0.9800	C56—H56	0.9500
C5—N1—N2	111.53 (13)	H32A—C32—H32C	109.5
C5—N1—C11	130.25 (14)	H32B—C32—H32C	109.5
N2—N1—C11	118.16 (14)	C31—C33—H33A	109.5
C3—N2—N1	104.34 (14)	C31—C33—H33B	109.5
N2—C3—C4	112.19 (15)	H33A—C33—H33B	109.5
N2—C3—C31	119.99 (16)	C31—C33—H33C	109.5
C4—C3—C31	127.69 (16)	H33A—C33—H33C	109.5
C5—C4—C3	105.09 (16)	H33B—C33—H33C	109.5
C5—C4—H4	127.5	C31—C34—H34A	109.5
C3—C4—H4	127.5	C31—C34—H34B	109.5
N1—C5—C4	106.81 (15)	H34A—C34—H34B	109.5
N1—C5—N51	121.40 (15)	C31—C34—H34C	109.5
C4—C5—N51	131.77 (17)	H34A—C34—H34C	109.5
C12—C11—C16	120.23 (16)	H34B—C34—H34C	109.5
C12—C11—N1	120.89 (16)	C5—N51—C57	118.02 (14)
C16—C11—N1	118.86 (16)	C5—N51—H51	113.5
C13—C12—C11	119.37 (17)	C57—N51—H51	112.9
C13—C12—H12	120.3	N51—C57—C51	111.28 (14)
C11—C12—H12	120.3	N51—C57—H571	109.4
C14—C13—C12	120.81 (17)	C51—C57—H571	109.4
C14—C13—H13	119.6	N51—C57—H572	109.4
C12—C13—H13	119.6	C51—C57—H572	109.4
C13—C14—C15	119.49 (17)	H571—C57—H572	108.0
C13—C14—H14	120.3	C52—C51—C56	118.22 (16)
C15—C14—H14	120.3	C52—C51—C57	120.26 (16)
C14—C15—C16	120.41 (18)	C56—C51—C57	121.50 (16)
C14—C15—H15	119.8	C53—C52—C51	121.10 (18)
C16—C15—H15	119.8	C53—C52—H52	119.5
C15—C16—C11	119.67 (17)	C51—C52—H52	119.5
C15—C16—H16	120.2	C54—C53—C52	120.25 (18)
C11—C16—H16	120.2	C54—C53—H53	119.9
C3—C31—C32	111.01 (15)	C52—C53—H53	119.9
C3—C31—C33	107.99 (15)	C53—C54—C55	119.51 (18)
C32—C31—C33	109.91 (16)	C53—C54—H54	120.2
C3—C31—C34	109.70 (15)	C55—C54—H54	120.2
C32—C31—C34	109.05 (16)	C54—C55—C56	120.34 (18)
C33—C31—C34	109.15 (16)	C54—C55—H55	119.8
C31—C32—H32A	109.5	C56—C55—H55	119.8
C31—C32—H32B	109.5	C55—C56—C51	120.55 (17)
H32A—C32—H32B	109.5	C55—C56—H56	119.7
C31—C32—H32C	109.5	C51—C56—H56	119.7
C5—N1—N2—C3	1.60 (19)	C12—C11—C16—C15	1.4 (3)
C11—N1—N2—C3	179.13 (15)	N1—C11—C16—C15	179.77 (17)
N1—N2—C3—C4	−0.62 (19)	N2—C3—C31—C32	−10.9 (2)
N1—N2—C3—C31	−176.80 (15)	C4—C3—C31—C32	173.57 (18)
N2—C3—C4—C5	−0.5 (2)	N2—C3—C31—C33	109.65 (19)
C31—C3—C4—C5	175.30 (17)	C4—C3—C31—C33	−65.9 (2)
N2—N1—C5—C4	−2.0 (2)	N2—C3—C31—C34	−131.50 (18)
C11—N1—C5—C4	−179.10 (17)	C4—C3—C31—C34	53.0 (2)
N2—N1—C5—N51	179.60 (15)	N1—C5—N51—C57	−171.61 (16)
C11—N1—C5—N51	2.5 (3)	C4—C5—N51—C57	10.4 (3)
C3—C4—C5—N1	1.46 (19)	C5—N51—C57—C51	−162.80 (15)
C3—C4—C5—N51	179.68 (18)	N51—C57—C51—C52	−148.74 (17)
C5—N1—C11—C12	−38.7 (3)	N51—C57—C51—C56	32.9 (2)
N2—N1—C11—C12	144.31 (16)	C56—C51—C52—C53	0.6 (3)
C5—N1—C11—C16	142.90 (19)	C57—C51—C52—C53	−177.82 (17)
N2—N1—C11—C16	−34.1 (2)	C51—C52—C53—C54	−1.6 (3)
C16—C11—C12—C13	−1.6 (3)	C52—C53—C54—C55	0.8 (3)
N1—C11—C12—C13	−179.98 (16)	C53—C54—C55—C56	1.1 (3)
C11—C12—C13—C14	0.8 (3)	C54—C55—C56—C51	−2.1 (3)
C12—C13—C14—C15	0.2 (3)	C52—C51—C56—C55	1.2 (3)
C13—C14—C15—C16	−0.5 (3)	C57—C51—C56—C55	179.63 (17)
C14—C15—C16—C11	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.55	3.011 (2)	110
N51—H51···Cg1^i	0.88	2.82	3.523 (2)	138

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

(II) 3-tert-butyl-5-(4-methylbenzylamino)-1-phenyl-1H-pyrazole

Crystal data

C21H25N3	Dx = 1.184 Mg m^−3
Mr = 319.44	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 2412 reflections
Hall symbol: P 4nw 2abw	θ = 3.0–27.5°
a = 10.7749 (13) Å	µ = 0.07 mm^−1
c = 30.868 (3) Å	T = 120 K
V = 3583.6 (7) Å^3	Block, colourless
Z = 8	0.37 × 0.27 × 0.24 mm
F(000) = 1376

Data collection

Bruker–Nonius KappaCCD diffractometer	2412 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1598 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.949, Tmax = 0.983	l = −27→40
22266 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0473P)^2 + 0.8586P] where P = (Fo^2 + 2Fc^2)/3
2412 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.6755 (2)	0.1622 (2)	0.46533 (7)	0.0207 (6)
N2	0.7693 (2)	0.0822 (2)	0.45423 (7)	0.0206 (6)
C3	0.7206 (3)	0.0090 (3)	0.42443 (8)	0.0202 (7)
C4	0.5959 (3)	0.0387 (3)	0.41657 (9)	0.0221 (7)
H4	0.5414	−0.0005	0.3966	0.026*
C5	0.5690 (3)	0.1356 (3)	0.44345 (8)	0.0190 (6)
C11	0.6954 (3)	0.2449 (3)	0.50004 (8)	0.0197 (7)
C12	0.6366 (3)	0.3584 (3)	0.50237 (9)	0.0234 (7)
H12	0.5832	0.3848	0.4797	0.028*
C13	0.6562 (3)	0.4331 (3)	0.53798 (9)	0.0291 (8)
H13	0.6145	0.5106	0.5400	0.035*
C14	0.7349 (3)	0.3968 (3)	0.57046 (9)	0.0300 (8)
H14	0.7471	0.4485	0.5950	0.036*
C15	0.7958 (3)	0.2859 (3)	0.56735 (9)	0.0293 (8)
H15	0.8514	0.2613	0.5897	0.035*
C16	0.7774 (3)	0.2094 (3)	0.53224 (8)	0.0256 (7)
H16	0.8207	0.1328	0.5301	0.031*
C31	0.8006 (3)	−0.0872 (3)	0.40309 (8)	0.0218 (7)
C32	0.7220 (3)	−0.1920 (3)	0.38577 (11)	0.0366 (9)
H32A	0.6773	−0.2315	0.4097	0.055*
H32B	0.7754	−0.2533	0.3716	0.055*
H32C	0.6622	−0.1591	0.3648	0.055*
C33	0.8954 (4)	−0.1373 (4)	0.43462 (10)	0.0441 (10)
H33A	0.9448	−0.0685	0.4463	0.066*
H33B	0.9502	−0.1959	0.4197	0.066*
H33C	0.8528	−0.1798	0.4584	0.066*
C34	0.8705 (3)	−0.0266 (3)	0.36534 (10)	0.0383 (9)
H34A	0.8107	0.0076	0.3446	0.057*
H34B	0.9222	−0.0890	0.3509	0.057*
H34C	0.9234	0.0403	0.3764	0.057*
N51	0.4617 (2)	0.2027 (2)	0.44928 (7)	0.0221 (6)
H51	0.4505	0.2182	0.4770	0.027*
C51	0.2467 (3)	0.2452 (3)	0.43416 (9)	0.0228 (7)
C52	0.1322 (3)	0.2013 (3)	0.44692 (9)	0.0281 (8)
H52	0.1201	0.1146	0.4505	0.034*
C53	0.0347 (3)	0.2821 (3)	0.45460 (9)	0.0292 (8)
H53	−0.0434	0.2500	0.4634	0.035*
C54	0.0491 (3)	0.4084 (3)	0.44962 (9)	0.0255 (8)
C55	0.1625 (3)	0.4516 (3)	0.43583 (8)	0.0246 (7)
H55	0.1738	0.5381	0.4314	0.030*
C56	0.2606 (3)	0.3714 (3)	0.42826 (9)	0.0257 (8)
H56	0.3382	0.4036	0.4189	0.031*
C57	0.3535 (3)	0.1596 (3)	0.42651 (10)	0.0286 (8)
H571	0.3318	0.0752	0.4366	0.034*
H572	0.3716	0.1553	0.3951	0.034*
C58	−0.0538 (3)	0.4969 (4)	0.46037 (11)	0.0385 (9)
H58A	−0.0282	0.5503	0.4845	0.058*
H58B	−0.1280	0.4500	0.4687	0.058*
H58C	−0.0723	0.5483	0.4350	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0201 (15)	0.0219 (14)	0.0200 (11)	0.0023 (12)	−0.0001 (11)	−0.0044 (11)
N2	0.0201 (14)	0.0200 (14)	0.0218 (11)	0.0045 (12)	0.0013 (11)	−0.0034 (11)
C3	0.0248 (18)	0.0164 (16)	0.0193 (12)	0.0008 (14)	−0.0010 (13)	0.0012 (12)
C4	0.0222 (17)	0.0239 (18)	0.0201 (13)	−0.0012 (15)	−0.0010 (13)	0.0017 (14)
C5	0.0192 (17)	0.0184 (17)	0.0193 (12)	0.0012 (14)	−0.0004 (13)	0.0016 (13)
C11	0.0211 (16)	0.0203 (16)	0.0177 (12)	−0.0019 (14)	0.0025 (13)	−0.0019 (13)
C12	0.0215 (18)	0.0265 (19)	0.0223 (14)	0.0005 (14)	0.0008 (14)	−0.0009 (14)
C13	0.0313 (19)	0.0220 (18)	0.0339 (16)	−0.0005 (16)	0.0039 (16)	−0.0082 (15)
C14	0.030 (2)	0.034 (2)	0.0264 (14)	−0.0061 (17)	0.0012 (15)	−0.0131 (16)
C15	0.0271 (19)	0.041 (2)	0.0197 (13)	−0.0043 (17)	−0.0018 (14)	−0.0034 (15)
C16	0.0217 (18)	0.0305 (19)	0.0245 (14)	0.0037 (15)	0.0030 (14)	0.0002 (15)
C31	0.0228 (18)	0.0177 (17)	0.0247 (13)	0.0031 (15)	0.0009 (13)	0.0006 (13)
C32	0.032 (2)	0.028 (2)	0.0492 (19)	−0.0014 (17)	0.0068 (17)	−0.0153 (17)
C33	0.050 (2)	0.046 (2)	0.0363 (18)	0.027 (2)	−0.0096 (18)	−0.0141 (18)
C34	0.038 (2)	0.036 (2)	0.0410 (18)	0.0035 (18)	0.0176 (18)	−0.0029 (17)
N51	0.0196 (14)	0.0258 (15)	0.0208 (11)	0.0022 (12)	0.0003 (11)	−0.0052 (11)
C51	0.0196 (17)	0.0254 (18)	0.0234 (13)	0.0007 (14)	−0.0035 (13)	−0.0023 (14)
C52	0.028 (2)	0.0236 (19)	0.0330 (16)	−0.0048 (16)	−0.0043 (15)	0.0029 (15)
C53	0.0192 (18)	0.038 (2)	0.0302 (15)	−0.0023 (17)	0.0010 (14)	0.0012 (16)
C54	0.0202 (18)	0.037 (2)	0.0192 (13)	0.0052 (16)	−0.0027 (13)	−0.0060 (15)
C55	0.0270 (19)	0.0241 (18)	0.0227 (13)	0.0001 (16)	−0.0031 (14)	−0.0049 (14)
C56	0.0233 (18)	0.034 (2)	0.0201 (13)	−0.0031 (16)	−0.0007 (14)	−0.0065 (14)
C57	0.0249 (18)	0.0279 (19)	0.0330 (16)	0.0030 (16)	−0.0061 (15)	−0.0092 (16)
C58	0.024 (2)	0.053 (2)	0.0382 (18)	0.0081 (18)	−0.0015 (16)	−0.0089 (18)

Geometric parameters (Å, º)

N1—C5	1.362 (4)	C33—H33A	0.9800
N1—N2	1.371 (3)	C33—H33B	0.9800
N1—C11	1.410 (3)	C33—H33C	0.9800
N2—C3	1.320 (3)	C34—H34A	0.9800
C3—C4	1.402 (4)	C34—H34B	0.9800
C3—C31	1.501 (4)	C34—H34C	0.9800
C4—C5	1.365 (4)	N51—C57	1.438 (4)
C4—H4	0.9500	N51—H51	0.8800
C5—N51	1.376 (4)	C57—C51	1.493 (4)
C11—C12	1.379 (4)	C57—H571	0.9900
C11—C16	1.384 (4)	C57—H572	0.9900
C12—C13	1.378 (4)	C51—C52	1.379 (4)
C12—H12	0.9500	C51—C56	1.380 (4)
C13—C14	1.370 (4)	C52—C53	1.385 (5)
C13—H13	0.9500	C52—H52	0.9500
C14—C15	1.367 (5)	C53—C54	1.378 (4)
C14—H14	0.9500	C53—H53	0.9500
C15—C16	1.376 (4)	C54—C55	1.375 (4)
C15—H15	0.9500	C54—C58	1.500 (4)
C16—H16	0.9500	C55—C56	1.385 (4)
C31—C32	1.509 (4)	C55—H55	0.9500
C31—C33	1.510 (4)	C56—H56	0.9500
C31—C34	1.534 (4)	C58—H58A	0.9800
C32—H32A	0.9800	C58—H58B	0.9800
C32—H32B	0.9800	C58—H58C	0.9800
C32—H32C	0.9800
C5—N1—N2	111.4 (2)	C31—C33—H33B	109.5
C5—N1—C11	129.6 (2)	H33A—C33—H33B	109.5
N2—N1—C11	118.3 (2)	C31—C33—H33C	109.5
C3—N2—N1	104.9 (2)	H33A—C33—H33C	109.5
N2—C3—C4	111.4 (3)	H33B—C33—H33C	109.5
N2—C3—C31	119.4 (3)	C31—C34—H34A	109.5
C4—C3—C31	129.2 (3)	C31—C34—H34B	109.5
C5—C4—C3	105.8 (3)	H34A—C34—H34B	109.5
C5—C4—H4	127.1	C31—C34—H34C	109.5
C3—C4—H4	127.1	H34A—C34—H34C	109.5
N1—C5—C4	106.4 (3)	H34B—C34—H34C	109.5
N1—C5—N51	122.2 (2)	C5—N51—C57	116.6 (2)
C4—C5—N51	131.3 (3)	C5—N51—H51	110.0
C12—C11—C16	120.1 (3)	C57—N51—H51	115.2
C12—C11—N1	122.0 (3)	N51—C57—C51	110.4 (2)
C16—C11—N1	117.9 (3)	N51—C57—H571	109.6
C11—C12—C13	119.3 (3)	C51—C57—H571	109.6
C11—C12—H12	120.4	N51—C57—H572	109.6
C13—C12—H12	120.4	C51—C57—H572	109.6
C14—C13—C12	120.8 (3)	H571—C57—H572	108.1
C14—C13—H13	119.6	C52—C51—C56	118.2 (3)
C12—C13—H13	119.6	C52—C51—C57	121.5 (3)
C15—C14—C13	119.7 (3)	C56—C51—C57	120.3 (3)
C15—C14—H14	120.2	C51—C52—C53	120.8 (3)
C13—C14—H14	120.2	C51—C52—H52	119.6
C14—C15—C16	120.7 (3)	C53—C52—H52	119.6
C14—C15—H15	119.7	C54—C53—C52	121.0 (3)
C16—C15—H15	119.7	C54—C53—H53	119.5
C15—C16—C11	119.5 (3)	C52—C53—H53	119.5
C15—C16—H16	120.3	C55—C54—C53	118.0 (3)
C11—C16—H16	120.3	C55—C54—C58	120.6 (3)
C3—C31—C32	110.5 (3)	C53—C54—C58	121.3 (3)
C3—C31—C33	110.6 (2)	C54—C55—C56	121.3 (3)
C32—C31—C33	109.9 (3)	C54—C55—H55	119.4
C3—C31—C34	108.8 (2)	C56—C55—H55	119.4
C32—C31—C34	109.0 (2)	C51—C56—C55	120.7 (3)
C33—C31—C34	108.0 (3)	C51—C56—H56	119.7
C31—C32—H32A	109.5	C55—C56—H56	119.7
C31—C32—H32B	109.5	C54—C58—H58A	109.5
H32A—C32—H32B	109.5	C54—C58—H58B	109.5
C31—C32—H32C	109.5	H58A—C58—H58B	109.5
H32A—C32—H32C	109.5	C54—C58—H58C	109.5
H32B—C32—H32C	109.5	H58A—C58—H58C	109.5
C31—C33—H33A	109.5	H58B—C58—H58C	109.5
C5—N1—N2—C3	1.9 (3)	N1—C11—C16—C15	−177.7 (3)
C11—N1—N2—C3	173.7 (2)	N2—C3—C31—C32	155.9 (3)
N1—N2—C3—C4	−1.1 (3)	C4—C3—C31—C32	−26.5 (4)
N1—N2—C3—C31	176.9 (2)	N2—C3—C31—C33	33.9 (4)
N2—C3—C4—C5	−0.1 (3)	C4—C3—C31—C33	−148.5 (3)
C31—C3—C4—C5	−177.8 (3)	N2—C3—C31—C34	−84.6 (3)
N2—N1—C5—C4	−1.9 (3)	C4—C3—C31—C34	93.0 (4)
C11—N1—C5—C4	−172.6 (3)	N1—C5—N51—C57	−175.7 (3)
N2—N1—C5—N51	179.7 (2)	C4—C5—N51—C57	6.3 (4)
C11—N1—C5—N51	9.0 (4)	C5—N51—C57—C51	−177.0 (3)
C3—C4—C5—N1	1.2 (3)	N51—C57—C51—C52	−130.1 (3)
C3—C4—C5—N51	179.4 (3)	N51—C57—C51—C56	50.4 (4)
C5—N1—C11—C12	−38.2 (4)	C56—C51—C52—C53	−1.5 (5)
N2—N1—C11—C12	151.7 (3)	C57—C51—C52—C53	178.9 (3)
C5—N1—C11—C16	142.2 (3)	C51—C52—C53—C54	0.2 (5)
N2—N1—C11—C16	−28.0 (4)	C52—C53—C54—C55	1.5 (5)
C16—C11—C12—C13	−2.9 (4)	C52—C53—C54—C58	−176.4 (3)
N1—C11—C12—C13	177.4 (3)	C53—C54—C55—C56	−1.7 (4)
C11—C12—C13—C14	1.3 (5)	C58—C54—C55—C56	176.1 (3)
C12—C13—C14—C15	0.7 (5)	C52—C51—C56—C55	1.3 (4)
C13—C14—C15—C16	−1.0 (5)	C57—C51—C56—C55	−179.2 (2)
C14—C15—C16—C11	−0.7 (5)	C54—C55—C56—C51	0.4 (4)
C12—C11—C16—C15	2.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.54	3.009 (4)	111
N51—H51···Cg3^i	0.88	2.95	3.718 (2)	147
C55—H55···Cg2^i	0.95	2.70	3.444 (3)	136

Symmetry code: (i) y, x, −z+1.

(III) 3-tert-butyl-1-phenyl-5-[4-(trifluoromethyl)benzyl]-1H-pyrazole

Crystal data

C21H22F3N3	F(000) = 1568
Mr = 373.42	Dx = 1.350 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4218 reflections
a = 20.824 (3) Å	θ = 2.9–27.5°
b = 7.3429 (11) Å	µ = 0.10 mm^−1
c = 24.225 (4) Å	T = 120 K
β = 97.275 (11)°	Needle, colourless
V = 3674.3 (10) Å^3	0.36 × 0.09 × 0.04 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	4218 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2014 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.151
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −26→26
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.946, Tmax = 0.996	l = −31→31
21869 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.083	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.196	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0791P)^2] where P = (Fo^2 + 2Fc^2)/3
4218 reflections	(Δ/σ)max = 0.001
247 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.80598 (14)	0.5223 (4)	0.26474 (12)	0.0208 (7)
N2	0.84366 (14)	0.5000 (4)	0.31528 (11)	0.0214 (7)
C3	0.80213 (17)	0.4853 (4)	0.35142 (14)	0.0202 (8)
C4	0.73816 (17)	0.5000 (5)	0.32628 (14)	0.0224 (8)
H4	0.6999	0.4927	0.3438	0.027*
C5	0.74238 (17)	0.5270 (5)	0.27133 (14)	0.0204 (8)
C11	0.83698 (18)	0.5484 (4)	0.21710 (14)	0.0211 (8)
C12	0.80881 (17)	0.4881 (5)	0.16545 (14)	0.0231 (8)
H12	0.7684	0.4266	0.1619	0.028*
C13	0.83955 (19)	0.5176 (5)	0.11938 (15)	0.0280 (9)
H13	0.8198	0.4790	0.0838	0.034*
C14	0.8991 (2)	0.6031 (5)	0.12449 (17)	0.0313 (10)
H14	0.9202	0.6252	0.0926	0.038*
C15	0.92733 (19)	0.6554 (5)	0.17605 (17)	0.0296 (10)
H15	0.9687	0.7120	0.1799	0.036*
C16	0.89719 (18)	0.6278 (5)	0.22198 (16)	0.0260 (9)
H16	0.9178	0.6636	0.2576	0.031*
C31	0.82464 (17)	0.4647 (5)	0.41273 (14)	0.0230 (8)
C32	0.89773 (17)	0.4476 (5)	0.42395 (15)	0.0264 (9)
H32A	0.9114	0.3355	0.4069	0.040*
H32B	0.9111	0.4435	0.4642	0.040*
H32C	0.9178	0.5527	0.4080	0.040*
C33	0.80282 (19)	0.6331 (5)	0.44218 (16)	0.0303 (10)
H33A	0.8228	0.7418	0.4282	0.045*
H33B	0.8160	0.6219	0.4823	0.045*
H33C	0.7556	0.6439	0.4349	0.045*
C34	0.7936 (2)	0.2971 (5)	0.43503 (17)	0.0360 (11)
H34A	0.7464	0.3087	0.4283	0.054*
H34B	0.8074	0.2862	0.4751	0.054*
H34C	0.8070	0.1883	0.4160	0.054*
N51	0.69471 (13)	0.5515 (4)	0.22687 (12)	0.0229 (7)
H51	0.7091	0.6275	0.2032	0.027*
C51	0.57982 (17)	0.5726 (5)	0.19126 (14)	0.0197 (8)
C52	0.52900 (18)	0.6943 (5)	0.18628 (16)	0.0256 (9)
H52	0.5278	0.7873	0.2134	0.031*
C53	0.48006 (18)	0.6831 (5)	0.14272 (16)	0.0271 (9)
H53	0.4444	0.7645	0.1406	0.033*
C54	0.48295 (17)	0.5532 (5)	0.10209 (15)	0.0230 (8)
C55	0.53430 (17)	0.4343 (5)	0.10571 (15)	0.0231 (8)
H55	0.5368	0.3466	0.0772	0.028*
C56	0.58201 (17)	0.4420 (5)	0.15044 (14)	0.0217 (8)
H56	0.6167	0.3571	0.1533	0.026*
C57	0.63008 (16)	0.5817 (5)	0.24123 (14)	0.0207 (8)
H571	0.6283	0.7027	0.2590	0.025*
H572	0.6204	0.4886	0.2686	0.025*
C58	0.43125 (19)	0.5515 (5)	0.05461 (16)	0.0298 (9)
F1	0.37230 (10)	0.5426 (4)	0.07037 (10)	0.0488 (7)
F2	0.43146 (12)	0.7029 (3)	0.02396 (10)	0.0433 (7)
F3	0.43564 (11)	0.4136 (3)	0.02004 (9)	0.0388 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0201 (17)	0.0217 (16)	0.0195 (17)	0.0011 (13)	−0.0011 (13)	0.0019 (13)
N2	0.0204 (17)	0.0239 (17)	0.0185 (17)	0.0017 (13)	−0.0027 (13)	0.0025 (13)
C3	0.023 (2)	0.0175 (19)	0.0202 (19)	−0.0021 (15)	0.0018 (16)	0.0007 (15)
C4	0.020 (2)	0.026 (2)	0.022 (2)	−0.0027 (16)	0.0051 (15)	−0.0011 (16)
C5	0.021 (2)	0.0174 (19)	0.022 (2)	−0.0004 (15)	−0.0005 (15)	−0.0008 (15)
C11	0.026 (2)	0.0177 (18)	0.020 (2)	0.0097 (16)	0.0038 (16)	0.0047 (15)
C12	0.023 (2)	0.020 (2)	0.025 (2)	0.0041 (16)	−0.0003 (16)	0.0033 (16)
C13	0.038 (2)	0.026 (2)	0.021 (2)	0.0126 (18)	0.0053 (18)	0.0047 (16)
C14	0.034 (3)	0.034 (2)	0.028 (2)	0.0079 (19)	0.0140 (19)	0.0083 (18)
C15	0.025 (2)	0.030 (2)	0.036 (3)	0.0019 (17)	0.0116 (19)	0.0048 (18)
C16	0.025 (2)	0.023 (2)	0.030 (2)	0.0008 (16)	0.0011 (18)	0.0041 (17)
C31	0.022 (2)	0.026 (2)	0.020 (2)	−0.0042 (16)	−0.0020 (15)	−0.0003 (16)
C32	0.026 (2)	0.028 (2)	0.024 (2)	−0.0056 (17)	−0.0030 (16)	0.0008 (17)
C33	0.026 (2)	0.042 (2)	0.023 (2)	−0.0038 (18)	0.0009 (17)	−0.0073 (18)
C34	0.036 (3)	0.040 (2)	0.030 (2)	−0.009 (2)	−0.001 (2)	0.0087 (19)
N51	0.0170 (17)	0.0307 (17)	0.0202 (16)	−0.0008 (13)	−0.0003 (13)	0.0053 (13)
C51	0.0172 (19)	0.0211 (19)	0.022 (2)	−0.0009 (15)	0.0060 (15)	0.0054 (16)
C52	0.027 (2)	0.022 (2)	0.028 (2)	0.0025 (17)	0.0025 (18)	−0.0041 (16)
C53	0.017 (2)	0.030 (2)	0.035 (2)	0.0081 (16)	0.0049 (18)	0.0028 (18)
C54	0.018 (2)	0.026 (2)	0.024 (2)	0.0005 (16)	0.0002 (16)	0.0047 (16)
C55	0.027 (2)	0.0209 (19)	0.021 (2)	−0.0036 (17)	0.0019 (16)	−0.0009 (16)
C56	0.0159 (19)	0.025 (2)	0.025 (2)	0.0032 (16)	0.0034 (16)	0.0010 (16)
C57	0.020 (2)	0.0208 (19)	0.021 (2)	−0.0046 (15)	0.0003 (15)	0.0001 (15)
C58	0.024 (2)	0.037 (2)	0.028 (2)	0.0015 (18)	0.0003 (17)	0.005 (2)
F1	0.0160 (13)	0.0835 (19)	0.0454 (16)	0.0012 (12)	−0.0018 (11)	0.0038 (13)
F2	0.0476 (16)	0.0418 (14)	0.0362 (15)	0.0078 (11)	−0.0111 (12)	0.0145 (11)
F3	0.0352 (14)	0.0436 (14)	0.0335 (13)	−0.0014 (11)	−0.0116 (10)	−0.0036 (11)

Geometric parameters (Å, º)

N1—C5	1.354 (4)	C33—H33A	0.9800
N1—N2	1.378 (4)	C33—H33B	0.9800
N1—C11	1.405 (4)	C33—H33C	0.9800
N2—C3	1.311 (4)	C34—H34A	0.9800
C3—C4	1.397 (5)	C34—H34B	0.9800
C3—C31	1.507 (5)	C34—H34C	0.9800
C4—C5	1.360 (5)	N51—C57	1.449 (4)
C4—H4	0.9500	N51—H51	0.8797
C5—N51	1.381 (4)	C57—C51	1.498 (5)
C11—C16	1.374 (5)	C57—H571	0.9900
C11—C12	1.386 (5)	C57—H572	0.9900
C12—C13	1.372 (5)	C51—C52	1.378 (5)
C12—H12	0.9500	C51—C56	1.382 (5)
C13—C14	1.382 (5)	C52—C53	1.373 (5)
C13—H13	0.9500	C52—H52	0.9500
C14—C15	1.366 (5)	C53—C54	1.377 (5)
C14—H14	0.9500	C53—H53	0.9500
C15—C16	1.360 (5)	C54—C55	1.375 (5)
C15—H15	0.9500	C54—C58	1.473 (5)
C16—H16	0.9500	C55—C56	1.375 (5)
C31—C32	1.517 (5)	C55—H55	0.9500
C31—C34	1.521 (5)	C56—H56	0.9500
C31—C33	1.525 (5)	C58—F3	1.324 (4)
C32—H32A	0.9800	C58—F1	1.332 (4)
C32—H32B	0.9800	C58—F2	1.337 (4)
C32—H32C	0.9800
C5—N1—N2	110.7 (3)	C31—C33—H33B	109.5
C5—N1—C11	130.6 (3)	H33A—C33—H33B	109.5
N2—N1—C11	118.5 (3)	C31—C33—H33C	109.5
C3—N2—N1	104.7 (3)	H33A—C33—H33C	109.5
N2—C3—C4	112.1 (3)	H33B—C33—H33C	109.5
N2—C3—C31	121.1 (3)	C31—C34—H34A	109.5
C4—C3—C31	126.7 (3)	C31—C34—H34B	109.5
C5—C4—C3	105.2 (3)	H34A—C34—H34B	109.5
C5—C4—H4	127.4	C31—C34—H34C	109.5
C3—C4—H4	127.4	H34A—C34—H34C	109.5
N1—C5—C4	107.3 (3)	H34B—C34—H34C	109.5
N1—C5—N51	121.9 (3)	C5—N51—C57	115.5 (3)
C4—C5—N51	130.8 (3)	C5—N51—H51	108.7
C16—C11—C12	119.4 (3)	C57—N51—H51	117.6
C16—C11—N1	119.8 (3)	N51—C57—C51	112.0 (3)
C12—C11—N1	120.8 (3)	N51—C57—H571	109.2
C13—C12—C11	119.8 (4)	C51—C57—H571	109.2
C13—C12—H12	120.1	N51—C57—H572	109.2
C11—C12—H12	120.1	C51—C57—H572	109.2
C12—C13—C14	120.3 (4)	H571—C57—H572	107.9
C12—C13—H13	119.8	C52—C51—C56	118.8 (3)
C14—C13—H13	119.8	C52—C51—C57	119.5 (3)
C15—C14—C13	119.1 (4)	C56—C51—C57	121.7 (3)
C15—C14—H14	120.4	C53—C52—C51	121.0 (4)
C13—C14—H14	120.4	C53—C52—H52	119.5
C16—C15—C14	121.1 (4)	C51—C52—H52	119.5
C16—C15—H15	119.5	C52—C53—C54	119.7 (3)
C14—C15—H15	119.5	C52—C53—H53	120.2
C15—C16—C11	120.2 (4)	C54—C53—H53	120.2
C15—C16—H16	119.9	C55—C54—C53	119.9 (3)
C11—C16—H16	119.9	C55—C54—C58	122.0 (3)
C3—C31—C32	111.4 (3)	C53—C54—C58	118.0 (3)
C3—C31—C34	109.7 (3)	C54—C55—C56	120.2 (3)
C32—C31—C34	109.3 (3)	C54—C55—H55	119.9
C3—C31—C33	107.8 (3)	C56—C55—H55	119.9
C32—C31—C33	109.6 (3)	C55—C56—C51	120.4 (3)
C34—C31—C33	108.9 (3)	C55—C56—H56	119.8
C31—C32—H32A	109.5	C51—C56—H56	119.8
C31—C32—H32B	109.5	F3—C58—F1	106.5 (3)
H32A—C32—H32B	109.5	F3—C58—F2	106.2 (3)
C31—C32—H32C	109.5	F1—C58—F2	105.5 (3)
H32A—C32—H32C	109.5	F3—C58—C54	113.5 (3)
H32B—C32—H32C	109.5	F1—C58—C54	112.7 (3)
C31—C33—H33A	109.5	F2—C58—C54	111.9 (3)
C5—N1—N2—C3	2.1 (3)	N2—C3—C31—C34	−126.2 (3)
C11—N1—N2—C3	177.9 (3)	C4—C3—C31—C34	57.2 (5)
N1—N2—C3—C4	−0.9 (4)	N2—C3—C31—C33	115.3 (3)
N1—N2—C3—C31	−178.0 (3)	C4—C3—C31—C33	−61.4 (4)
N2—C3—C4—C5	−0.6 (4)	N1—C5—N51—C57	−170.8 (3)
C31—C3—C4—C5	176.4 (3)	C4—C5—N51—C57	10.9 (5)
N2—N1—C5—C4	−2.5 (4)	C5—N51—C57—C51	−169.5 (3)
C11—N1—C5—C4	−177.6 (3)	N51—C57—C51—C52	−140.2 (3)
N2—N1—C5—N51	178.8 (3)	N51—C57—C51—C56	41.6 (5)
C11—N1—C5—N51	3.7 (5)	C56—C51—C52—C53	2.2 (5)
C3—C4—C5—N1	1.8 (4)	C57—C51—C52—C53	−176.1 (3)
C3—C4—C5—N51	−179.7 (3)	C51—C52—C53—C54	−2.7 (6)
C5—N1—C11—C16	146.7 (3)	C52—C53—C54—C55	0.8 (6)
N2—N1—C11—C16	−28.1 (4)	C52—C53—C54—C58	−177.0 (3)
C5—N1—C11—C12	−36.0 (5)	C53—C54—C55—C56	1.5 (5)
N2—N1—C11—C12	149.2 (3)	C58—C54—C55—C56	179.2 (3)
C16—C11—C12—C13	−3.7 (5)	C54—C55—C56—C51	−1.9 (5)
N1—C11—C12—C13	179.0 (3)	C52—C51—C56—C55	0.1 (5)
C11—C12—C13—C14	1.6 (5)	C57—C51—C56—C55	178.4 (3)
C12—C13—C14—C15	0.9 (5)	C55—C54—C58—F3	7.1 (5)
C13—C14—C15—C16	−1.3 (6)	C53—C54—C58—F3	−175.2 (3)
C14—C15—C16—C11	−0.9 (6)	C55—C54—C58—F1	128.2 (4)
C12—C11—C16—C15	3.4 (5)	C53—C54—C58—F1	−54.1 (5)
N1—C11—C16—C15	−179.3 (3)	C55—C54—C58—F2	−113.1 (4)
N2—C3—C31—C32	−4.9 (4)	C53—C54—C58—F2	64.6 (5)
C4—C3—C31—C32	178.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.51	2.995 (5)	112
N51—H51···Cg1^i	0.88	2.80	3.470 (3)	134
C53—H53···Cg2^ii	0.95	2.91	3.809 (4)	157

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

(IV) 3-tert-butyl-5-(4-chlorobenzylamino)-1-phenyl-1H-pyrazole

Crystal data

C20H22ClN3	Z = 2
Mr = 339.86	F(000) = 360
Triclinic, P1	Dx = 1.298 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.385 (3) Å	Cell parameters from 3991 reflections
b = 9.7584 (19) Å	θ = 2.8–27.5°
c = 10.6014 (17) Å	µ = 0.23 mm^−1
α = 112.459 (13)°	T = 120 K
β = 95.721 (18)°	Lath, colourless
γ = 99.735 (19)°	0.25 × 0.10 × 0.05 mm
V = 869.8 (4) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	3991 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.958, Tmax = 0.989	l = −13→13
25011 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0483P)^2 + 0.3135P] where P = (Fo^2 + 2Fc^2)/3
3991 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.46276 (16)	0.21931 (17)	0.40900 (15)	0.0211 (3)
N2	0.34863 (16)	0.13933 (17)	0.29828 (15)	0.0222 (3)
C3	0.25146 (19)	0.0681 (2)	0.34731 (19)	0.0213 (4)
C4	0.3010 (2)	0.0982 (2)	0.48675 (19)	0.0231 (4)
H4	0.2510	0.0596	0.5440	0.028*
C5	0.43605 (19)	0.1942 (2)	0.52260 (18)	0.0203 (4)
C11	0.59165 (19)	0.3020 (2)	0.39085 (18)	0.0206 (4)
C12	0.66041 (19)	0.4440 (2)	0.49181 (18)	0.0224 (4)
H12	0.6205	0.4867	0.5733	0.027*
C13	0.7868 (2)	0.5232 (2)	0.4738 (2)	0.0272 (4)
H13	0.8346	0.6204	0.5436	0.033*
C14	0.8447 (2)	0.4632 (2)	0.3558 (2)	0.0286 (4)
H14	0.9322	0.5183	0.3440	0.034*
C15	0.7745 (2)	0.3225 (2)	0.2549 (2)	0.0279 (4)
H15	0.8137	0.2810	0.1727	0.033*
C16	0.6484 (2)	0.2413 (2)	0.27166 (18)	0.0238 (4)
H16	0.6007	0.1441	0.2016	0.029*
C31	0.1061 (2)	−0.0262 (2)	0.25749 (19)	0.0254 (4)
C32	0.0479 (2)	−0.1502 (2)	0.3052 (2)	0.0336 (5)
H32A	0.1201	−0.2127	0.3017	0.050*
H32B	−0.0446	−0.2143	0.2441	0.050*
H32C	0.0309	−0.1034	0.4006	0.050*
C33	0.1222 (2)	−0.0981 (2)	0.1058 (2)	0.0326 (5)
H33A	0.1631	−0.0182	0.0765	0.049*
H33B	0.0257	−0.1545	0.0483	0.049*
H33C	0.1883	−0.1680	0.0951	0.049*
C34	−0.0037 (2)	0.0753 (2)	0.2703 (2)	0.0353 (5)
H34A	−0.0156	0.1220	0.3674	0.053*
H34B	−0.0987	0.0139	0.2125	0.053*
H34C	0.0328	0.1553	0.2395	0.053*
N51	0.53524 (17)	0.25935 (18)	0.64426 (15)	0.0245 (4)
H51	0.6259	0.2972	0.6406	0.029*
C51	0.42418 (19)	0.2693 (2)	0.84934 (18)	0.0209 (4)
C52	0.35845 (19)	0.3835 (2)	0.84378 (18)	0.0218 (4)
H52	0.3723	0.4197	0.7734	0.026*
C53	0.2726 (2)	0.4458 (2)	0.93988 (18)	0.0236 (4)
H53	0.2263	0.5236	0.9353	0.028*
C54	0.2552 (2)	0.3938 (2)	1.04165 (18)	0.0251 (4)
Cl54	0.14512 (6)	0.47041 (6)	1.16049 (5)	0.03495 (16)
C55	0.3209 (2)	0.2817 (2)	1.05116 (19)	0.0266 (4)
H55	0.3088	0.2477	1.1231	0.032*
C56	0.4045 (2)	0.2202 (2)	0.95394 (19)	0.0257 (4)
H56	0.4499	0.1419	0.9587	0.031*
C57	0.5197 (2)	0.1986 (2)	0.74782 (18)	0.0257 (4)
H571	0.6186	0.2134	0.8001	0.031*
H572	0.4777	0.0877	0.7004	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0201 (8)	0.0217 (8)	0.0182 (7)	0.0007 (6)	0.0008 (6)	0.0068 (6)
N2	0.0210 (8)	0.0197 (8)	0.0189 (8)	0.0008 (6)	−0.0026 (6)	0.0036 (6)
C3	0.0202 (9)	0.0180 (9)	0.0243 (9)	0.0048 (7)	0.0026 (7)	0.0069 (7)
C4	0.0213 (9)	0.0231 (10)	0.0234 (9)	0.0039 (8)	0.0042 (7)	0.0081 (8)
C5	0.0199 (9)	0.0215 (9)	0.0178 (9)	0.0046 (7)	0.0032 (7)	0.0062 (7)
C11	0.0190 (9)	0.0215 (9)	0.0216 (9)	0.0055 (7)	0.0022 (7)	0.0091 (7)
C12	0.0207 (9)	0.0237 (10)	0.0201 (9)	0.0049 (8)	0.0041 (7)	0.0058 (7)
C13	0.0250 (10)	0.0241 (10)	0.0281 (10)	0.0007 (8)	−0.0002 (8)	0.0089 (8)
C14	0.0202 (9)	0.0360 (11)	0.0364 (11)	0.0059 (8)	0.0075 (8)	0.0217 (9)
C15	0.0296 (10)	0.0353 (11)	0.0268 (10)	0.0144 (9)	0.0121 (8)	0.0165 (9)
C16	0.0281 (10)	0.0221 (10)	0.0202 (9)	0.0070 (8)	0.0041 (8)	0.0070 (8)
C31	0.0213 (9)	0.0220 (10)	0.0257 (10)	0.0020 (8)	−0.0013 (8)	0.0045 (8)
C32	0.0300 (11)	0.0266 (11)	0.0348 (11)	−0.0046 (9)	0.0006 (9)	0.0083 (9)
C33	0.0273 (10)	0.0339 (11)	0.0250 (10)	0.0014 (9)	−0.0048 (8)	0.0040 (9)
C34	0.0233 (10)	0.0297 (11)	0.0411 (12)	0.0041 (9)	−0.0043 (9)	0.0050 (9)
N51	0.0189 (8)	0.0330 (9)	0.0185 (8)	0.0013 (7)	0.0013 (6)	0.0094 (7)
C51	0.0190 (9)	0.0210 (9)	0.0176 (9)	−0.0006 (7)	−0.0005 (7)	0.0055 (7)
C52	0.0211 (9)	0.0230 (10)	0.0183 (9)	0.0009 (8)	0.0007 (7)	0.0074 (7)
C53	0.0235 (9)	0.0215 (9)	0.0218 (9)	0.0030 (8)	−0.0002 (7)	0.0065 (8)
C54	0.0217 (9)	0.0251 (10)	0.0185 (9)	−0.0026 (8)	0.0027 (7)	0.0017 (8)
Cl54	0.0308 (3)	0.0383 (3)	0.0251 (3)	0.0021 (2)	0.0100 (2)	0.0027 (2)
C55	0.0317 (10)	0.0252 (10)	0.0195 (9)	−0.0015 (8)	0.0024 (8)	0.0093 (8)
C56	0.0289 (10)	0.0231 (10)	0.0248 (10)	0.0038 (8)	0.0003 (8)	0.0113 (8)
C57	0.0267 (10)	0.0322 (11)	0.0193 (9)	0.0092 (8)	0.0024 (8)	0.0111 (8)

Geometric parameters (Å, º)

N1—C5	1.356 (2)	C32—H32B	0.9800
N1—N2	1.379 (2)	C32—H32C	0.9800
N1—C11	1.410 (2)	C33—H33A	0.9800
N2—C3	1.319 (2)	C33—H33B	0.9800
C3—C4	1.405 (3)	C33—H33C	0.9800
C3—C31	1.504 (2)	C34—H34A	0.9800
C4—C5	1.363 (3)	C34—H34B	0.9800
C4—H4	0.9500	C34—H34C	0.9800
C5—N51	1.367 (2)	N51—C57	1.441 (2)
C11—C16	1.378 (3)	N51—H51	0.8796
C11—C12	1.382 (3)	C57—C51	1.507 (3)
C12—C13	1.374 (3)	C57—H571	0.9900
C12—H12	0.9500	C57—H572	0.9900
C13—C14	1.373 (3)	C51—C52	1.379 (3)
C13—H13	0.9500	C51—C56	1.382 (3)
C14—C15	1.377 (3)	C52—C53	1.383 (3)
C14—H14	0.9500	C52—H52	0.9500
C15—C16	1.376 (3)	C53—C54	1.369 (3)
C15—H15	0.9500	C53—H53	0.9500
C16—H16	0.9500	C54—C55	1.374 (3)
C31—C32	1.523 (3)	C54—Cl54	1.7361 (19)
C31—C33	1.524 (3)	C55—C56	1.374 (3)
C31—C34	1.526 (3)	C55—H55	0.9500
C32—H32A	0.9800	C56—H56	0.9500
C5—N1—N2	111.43 (14)	H32A—C32—H32C	109.5
C5—N1—C11	128.43 (15)	H32B—C32—H32C	109.5
N2—N1—C11	119.89 (14)	C31—C33—H33A	109.5
C3—N2—N1	104.48 (14)	C31—C33—H33B	109.5
N2—C3—C4	111.68 (16)	H33A—C33—H33B	109.5
N2—C3—C31	120.28 (16)	C31—C33—H33C	109.5
C4—C3—C31	128.00 (17)	H33A—C33—H33C	109.5
C5—C4—C3	105.55 (16)	H33B—C33—H33C	109.5
C5—C4—H4	127.2	C31—C34—H34A	109.5
C3—C4—H4	127.2	C31—C34—H34B	109.5
N1—C5—C4	106.84 (15)	H34A—C34—H34B	109.5
N1—C5—N51	121.89 (16)	C31—C34—H34C	109.5
C4—C5—N51	131.27 (17)	H34A—C34—H34C	109.5
C16—C11—C12	120.09 (17)	H34B—C34—H34C	109.5
C16—C11—N1	119.81 (16)	C5—N51—C57	119.01 (15)
C12—C11—N1	120.10 (16)	C5—N51—H51	117.2
C13—C12—C11	119.68 (17)	C57—N51—H51	115.6
C13—C12—H12	120.2	N51—C57—C51	114.45 (16)
C11—C12—H12	120.2	N51—C57—H571	108.6
C14—C13—C12	120.66 (18)	C51—C57—H571	108.6
C14—C13—H13	119.7	N51—C57—H572	108.6
C12—C13—H13	119.7	C51—C57—H572	108.6
C13—C14—C15	119.34 (18)	H571—C57—H572	107.6
C13—C14—H14	120.3	C52—C51—C56	118.76 (17)
C15—C14—H14	120.3	C52—C51—C57	122.52 (16)
C16—C15—C14	120.75 (18)	C56—C51—C57	118.71 (17)
C16—C15—H15	119.6	C51—C52—C53	120.49 (17)
C14—C15—H15	119.6	C51—C52—H52	119.8
C15—C16—C11	119.48 (17)	C53—C52—H52	119.8
C15—C16—H16	120.3	C54—C53—C52	119.07 (17)
C11—C16—H16	120.3	C54—C53—H53	120.5
C3—C31—C32	109.56 (16)	C52—C53—H53	120.5
C3—C31—C33	110.60 (16)	C53—C54—C55	121.83 (18)
C32—C31—C33	109.72 (16)	C53—C54—Cl54	118.88 (15)
C3—C31—C34	109.37 (15)	C55—C54—Cl54	119.28 (15)
C32—C31—C34	109.00 (17)	C54—C55—C56	118.25 (17)
C33—C31—C34	108.57 (16)	C54—C55—H55	120.9
C31—C32—H32A	109.5	C56—C55—H55	120.9
C31—C32—H32B	109.5	C55—C56—C51	121.60 (18)
H32A—C32—H32B	109.5	C55—C56—H56	119.2
C31—C32—H32C	109.5	C51—C56—H56	119.2
C5—N1—N2—C3	1.21 (19)	N1—C11—C16—C15	−179.77 (16)
C11—N1—N2—C3	175.93 (15)	N2—C3—C31—C32	153.33 (17)
N1—N2—C3—C4	−1.0 (2)	C4—C3—C31—C32	−29.2 (3)
N1—N2—C3—C31	176.89 (15)	N2—C3—C31—C33	32.3 (2)
N2—C3—C4—C5	0.4 (2)	C4—C3—C31—C33	−150.29 (19)
C31—C3—C4—C5	−177.26 (17)	N2—C3—C31—C34	−87.3 (2)
N2—N1—C5—C4	−1.0 (2)	C4—C3—C31—C34	90.2 (2)
C11—N1—C5—C4	−175.15 (17)	N1—C5—N51—C57	−163.66 (16)
N2—N1—C5—N51	178.72 (16)	C4—C5—N51—C57	16.0 (3)
C11—N1—C5—N51	4.6 (3)	C5—N51—C57—C51	−89.3 (2)
C3—C4—C5—N1	0.4 (2)	N51—C57—C51—C52	−0.6 (2)
C3—C4—C5—N51	−179.31 (19)	N51—C57—C51—C56	−179.02 (16)
C5—N1—C11—C16	133.66 (19)	C56—C51—C52—C53	−1.0 (3)
N2—N1—C11—C16	−40.1 (2)	C57—C51—C52—C53	−179.49 (17)
C5—N1—C11—C12	−46.8 (3)	C51—C52—C53—C54	0.8 (3)
N2—N1—C11—C12	139.50 (17)	C52—C53—C54—C55	0.1 (3)
C16—C11—C12—C13	−1.1 (3)	C52—C53—C54—Cl54	−179.08 (14)
N1—C11—C12—C13	179.38 (16)	C53—C54—C55—C56	−0.8 (3)
C11—C12—C13—C14	0.6 (3)	Cl54—C54—C55—C56	178.40 (14)
C12—C13—C14—C15	0.2 (3)	C54—C55—C56—C51	0.6 (3)
C13—C14—C15—C16	−0.6 (3)	C52—C51—C56—C55	0.3 (3)
C14—C15—C16—C11	0.2 (3)	C57—C51—C56—C55	178.86 (17)
C12—C11—C16—C15	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51···Cl54^i	0.88	2.83	3.486 (2)	133
C55—H55···N2^ii	0.95	2.49	3.410 (3)	163
C57—H572···Cg3^iii	0.99	2.88	3.557 (2)	126

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

(V) 5-(4-bromobenzyl)-3-tert-butyl-1-phenyl-1H-pyrazole

Crystal data

C20H22BrN3	F(000) = 1584
Mr = 384.32	Dx = 1.430 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4071 reflections
a = 20.1981 (6) Å	θ = 2.9–27.5°
b = 7.3960 (9) Å	µ = 2.31 mm^−1
c = 24.171 (4) Å	T = 120 K
β = 98.634 (7)°	Needle, colourless
V = 3569.9 (7) Å^3	0.44 × 0.13 × 0.11 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	4071 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2871 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −25→26
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.499, Tmax = 0.785	l = −31→31
28981 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 13.3406P] where P = (Fo^2 + 2Fc^2)/3
4071 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.80342 (13)	0.5250 (4)	0.26616 (11)	0.0161 (5)
N2	0.84310 (13)	0.4995 (4)	0.31685 (10)	0.0173 (5)
C3	0.80086 (16)	0.4875 (4)	0.35294 (13)	0.0177 (6)
C4	0.73400 (16)	0.5064 (4)	0.32722 (13)	0.0176 (6)
H4	0.6948	0.5015	0.3446	0.021*
C5	0.73765 (15)	0.5331 (4)	0.27197 (13)	0.0153 (6)
C11	0.83441 (16)	0.5489 (4)	0.21827 (13)	0.0169 (6)
C12	0.80415 (16)	0.4858 (4)	0.16672 (13)	0.0185 (6)
H12	0.7625	0.4241	0.1632	0.022*
C13	0.83556 (17)	0.5141 (5)	0.12051 (14)	0.0224 (7)
H13	0.8148	0.4741	0.0848	0.027*
C14	0.89664 (18)	0.5996 (5)	0.12568 (15)	0.0261 (8)
H14	0.9177	0.6196	0.0936	0.031*
C15	0.92702 (18)	0.6559 (5)	0.17759 (16)	0.0279 (8)
H15	0.9696	0.7127	0.1814	0.033*
C16	0.89611 (17)	0.6304 (5)	0.22403 (14)	0.0224 (7)
H16	0.9173	0.6690	0.2598	0.027*
C31	0.82519 (17)	0.4664 (4)	0.41454 (13)	0.0196 (7)
C32	0.90061 (17)	0.4395 (5)	0.42545 (15)	0.0264 (8)
H32A	0.9120	0.3255	0.4085	0.040*
H32B	0.9158	0.4356	0.4659	0.040*
H32C	0.9226	0.5400	0.4090	0.040*
C33	0.8068 (2)	0.6369 (5)	0.44358 (15)	0.0307 (8)
H33A	0.8271	0.7418	0.4279	0.046*
H33B	0.8235	0.6283	0.4837	0.046*
H33C	0.7580	0.6507	0.4379	0.046*
C34	0.79148 (19)	0.3058 (5)	0.43727 (15)	0.0293 (8)
H34A	0.7428	0.3215	0.4297	0.044*
H34B	0.8059	0.2967	0.4777	0.044*
H34C	0.8039	0.1951	0.4190	0.044*
N51	0.68844 (13)	0.5587 (4)	0.22681 (11)	0.0188 (6)
H51	0.7007	0.6478	0.2064	0.023*
C51	0.57057 (15)	0.5712 (5)	0.18715 (13)	0.0166 (6)
C52	0.51577 (17)	0.6843 (5)	0.17890 (14)	0.0235 (7)
H52	0.5119	0.7781	0.2051	0.028*
C53	0.46654 (17)	0.6638 (5)	0.13350 (15)	0.0266 (8)
H53	0.4282	0.7397	0.1289	0.032*
C44	0.47381 (17)	0.5321 (5)	0.09504 (14)	0.0220 (7)
Br54	0.40667 (2)	0.50388 (6)	0.033022 (16)	0.03814 (16)
C55	0.52881 (16)	0.4213 (5)	0.10105 (14)	0.0208 (7)
H55	0.5337	0.3327	0.0735	0.025*
C56	0.57672 (16)	0.4397 (4)	0.14735 (14)	0.0182 (7)
H56	0.6145	0.3616	0.1522	0.022*
C57	0.62110 (15)	0.5897 (5)	0.23852 (13)	0.0189 (7)
H571	0.6182	0.7127	0.2542	0.023*
H572	0.6109	0.5018	0.2670	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0164 (13)	0.0165 (14)	0.0153 (12)	−0.0001 (10)	0.0019 (10)	0.0033 (10)
N2	0.0196 (13)	0.0166 (13)	0.0148 (12)	−0.0005 (11)	−0.0002 (10)	0.0003 (11)
C3	0.0219 (15)	0.0116 (15)	0.0192 (15)	−0.0036 (13)	0.0022 (12)	−0.0006 (13)
C4	0.0183 (15)	0.0173 (15)	0.0178 (14)	−0.0027 (13)	0.0046 (11)	−0.0017 (13)
C5	0.0173 (15)	0.0104 (16)	0.0184 (15)	−0.0001 (11)	0.0039 (11)	0.0004 (11)
C11	0.0218 (16)	0.0115 (15)	0.0183 (15)	0.0056 (12)	0.0057 (12)	0.0044 (12)
C12	0.0198 (15)	0.0156 (16)	0.0201 (15)	0.0040 (13)	0.0032 (12)	0.0023 (13)
C13	0.0298 (18)	0.0195 (17)	0.0183 (15)	0.0087 (14)	0.0052 (13)	0.0021 (14)
C14	0.0298 (19)	0.0242 (19)	0.0272 (19)	0.0075 (15)	0.0141 (15)	0.0076 (15)
C15	0.0223 (18)	0.027 (2)	0.036 (2)	−0.0004 (15)	0.0089 (15)	0.0049 (16)
C16	0.0225 (17)	0.0195 (17)	0.0251 (18)	0.0014 (13)	0.0032 (13)	0.0031 (14)
C31	0.0255 (17)	0.0170 (17)	0.0156 (15)	−0.0033 (13)	0.0011 (12)	0.0014 (12)
C32	0.0254 (18)	0.033 (2)	0.0193 (17)	−0.0048 (15)	−0.0006 (13)	0.0021 (15)
C33	0.042 (2)	0.031 (2)	0.0189 (18)	0.0020 (17)	0.0040 (15)	−0.0061 (15)
C34	0.033 (2)	0.032 (2)	0.0218 (18)	−0.0112 (16)	0.0007 (14)	0.0086 (16)
N51	0.0161 (13)	0.0216 (14)	0.0193 (14)	0.0009 (11)	0.0042 (10)	0.0032 (11)
C51	0.0141 (15)	0.0169 (15)	0.0202 (16)	0.0012 (12)	0.0070 (12)	0.0029 (13)
C52	0.0254 (18)	0.0202 (18)	0.0267 (18)	0.0060 (14)	0.0093 (14)	−0.0016 (14)
C53	0.0186 (17)	0.0251 (19)	0.037 (2)	0.0087 (14)	0.0061 (14)	0.0069 (16)
C44	0.0178 (16)	0.0241 (19)	0.0227 (16)	−0.0037 (13)	−0.0009 (12)	0.0078 (14)
Br54	0.0331 (2)	0.0449 (3)	0.0316 (2)	−0.00233 (18)	−0.01112 (15)	0.00885 (19)
C55	0.0216 (17)	0.0190 (17)	0.0217 (17)	0.0001 (14)	0.0035 (13)	−0.0005 (14)
C56	0.0164 (15)	0.0148 (15)	0.0241 (17)	0.0033 (12)	0.0052 (12)	0.0033 (13)
C57	0.0181 (16)	0.0190 (17)	0.0203 (16)	−0.0001 (13)	0.0053 (12)	−0.0004 (13)

Geometric parameters (Å, º)

N1—C5	1.358 (4)	C32—H32B	0.9800
N1—N2	1.373 (4)	C32—H32C	0.9800
N1—C11	1.408 (4)	C33—H33A	0.9800
N2—C3	1.312 (4)	C33—H33B	0.9800
C3—C4	1.406 (4)	C33—H33C	0.9800
C3—C31	1.504 (4)	C34—H34A	0.9800
C4—C5	1.363 (4)	C34—H34B	0.9800
C4—H4	0.9500	C34—H34C	0.9800
C5—N51	1.375 (4)	N51—C57	1.449 (4)
C11—C16	1.372 (5)	N51—H51	0.8797
C11—C12	1.384 (5)	C57—C51	1.490 (4)
C12—C13	1.381 (4)	C57—H571	0.9900
C12—H12	0.9500	C57—H572	0.9900
C13—C14	1.375 (5)	C51—C52	1.378 (5)
C13—H13	0.9500	C51—C56	1.386 (5)
C14—C15	1.376 (5)	C52—C53	1.374 (5)
C14—H14	0.9500	C52—H52	0.9500
C15—C16	1.377 (5)	C53—C44	1.370 (5)
C15—H15	0.9500	C53—H53	0.9500
C16—H16	0.9500	C44—C55	1.370 (5)
C31—C34	1.513 (5)	C44—Br54	1.876 (3)
C31—C33	1.516 (5)	C55—C56	1.372 (5)
C31—C32	1.519 (5)	C55—H55	0.9500
C32—H32A	0.9800	C56—H56	0.9500
C5—N1—N2	111.3 (2)	H32A—C32—H32C	109.5
C5—N1—C11	130.0 (3)	H32B—C32—H32C	109.5
N2—N1—C11	118.6 (3)	C31—C33—H33A	109.5
C3—N2—N1	104.6 (3)	C31—C33—H33B	109.5
N2—C3—C4	112.1 (3)	H33A—C33—H33B	109.5
N2—C3—C31	121.1 (3)	C31—C33—H33C	109.5
C4—C3—C31	126.7 (3)	H33A—C33—H33C	109.5
C5—C4—C3	105.0 (3)	H33B—C33—H33C	109.5
C5—C4—H4	127.5	C31—C34—H34A	109.5
C3—C4—H4	127.5	C31—C34—H34B	109.5
N1—C5—C4	107.0 (3)	H34A—C34—H34B	109.5
N1—C5—N51	121.7 (3)	C31—C34—H34C	109.5
C4—C5—N51	131.2 (3)	H34A—C34—H34C	109.5
C16—C11—C12	120.7 (3)	H34B—C34—H34C	109.5
C16—C11—N1	118.7 (3)	C5—N51—C57	117.1 (3)
C12—C11—N1	120.5 (3)	C5—N51—H51	108.5
C13—C12—C11	118.9 (3)	C57—N51—H51	110.0
C13—C12—H12	120.6	N51—C57—C51	111.6 (3)
C11—C12—H12	120.6	N51—C57—H571	109.3
C14—C13—C12	120.7 (3)	C51—C57—H571	109.3
C14—C13—H13	119.6	N51—C57—H572	109.3
C12—C13—H13	119.6	C51—C57—H572	109.3
C13—C14—C15	119.6 (3)	H571—C57—H572	108.0
C13—C14—H14	120.2	C52—C51—C56	118.6 (3)
C15—C14—H14	120.2	C52—C51—C57	120.0 (3)
C14—C15—C16	120.5 (3)	C56—C51—C57	121.4 (3)
C14—C15—H15	119.8	C53—C52—C51	121.2 (3)
C16—C15—H15	119.8	C53—C52—H52	119.4
C11—C16—C15	119.6 (3)	C51—C52—H52	119.4
C11—C16—H16	120.2	C44—C53—C52	118.8 (3)
C15—C16—H16	120.2	C44—C53—H53	120.6
C3—C31—C34	110.0 (3)	C52—C53—H53	120.6
C3—C31—C33	107.8 (3)	C53—C44—C55	121.4 (3)
C34—C31—C33	109.3 (3)	C53—C44—Br54	118.9 (3)
C3—C31—C32	110.8 (3)	C55—C44—Br54	119.7 (3)
C34—C31—C32	109.2 (3)	C44—C55—C56	119.2 (3)
C33—C31—C32	109.7 (3)	C44—C55—H55	120.4
C31—C32—H32A	109.5	C56—C55—H55	120.4
C31—C32—H32B	109.5	C55—C56—C51	120.7 (3)
H32A—C32—H32B	109.5	C55—C56—H56	119.7
C31—C32—H32C	109.5	C51—C56—H56	119.7
C5—N1—N2—C3	1.6 (3)	C14—C15—C16—C11	−0.3 (5)
C11—N1—N2—C3	178.0 (3)	N2—C3—C31—C34	−127.6 (3)
N1—N2—C3—C4	−0.6 (3)	C4—C3—C31—C34	56.0 (4)
N1—N2—C3—C31	−177.5 (3)	N2—C3—C31—C33	113.3 (3)
N2—C3—C4—C5	−0.6 (4)	C4—C3—C31—C33	−63.0 (4)
C31—C3—C4—C5	176.0 (3)	N2—C3—C31—C32	−6.8 (4)
N2—N1—C5—C4	−2.1 (3)	C4—C3—C31—C32	176.9 (3)
C11—N1—C5—C4	−177.9 (3)	N1—C5—N51—C57	−171.9 (3)
N2—N1—C5—N51	179.7 (3)	C4—C5—N51—C57	10.4 (5)
C11—N1—C5—N51	3.9 (5)	C5—N51—C57—C51	−166.3 (3)
C3—C4—C5—N1	1.6 (3)	N51—C57—C51—C52	−142.8 (3)
C3—C4—C5—N51	179.6 (3)	N51—C57—C51—C56	38.3 (4)
C5—N1—C11—C16	144.7 (3)	C56—C51—C52—C53	2.6 (5)
N2—N1—C11—C16	−30.9 (4)	C57—C51—C52—C53	−176.4 (3)
C5—N1—C11—C12	−37.4 (5)	C51—C52—C53—C44	−2.3 (5)
N2—N1—C11—C12	147.0 (3)	C52—C53—C44—C55	0.1 (5)
C16—C11—C12—C13	−3.1 (5)	C52—C53—C44—Br54	180.0 (3)
N1—C11—C12—C13	179.1 (3)	C53—C44—C55—C56	1.7 (5)
C11—C12—C13—C14	1.5 (5)	Br54—C44—C55—C56	−178.2 (2)
C12—C13—C14—C15	0.6 (5)	C44—C55—C56—C51	−1.4 (5)
C13—C14—C15—C16	−1.3 (5)	C52—C51—C56—C55	−0.8 (5)
C12—C11—C16—C15	2.5 (5)	C57—C51—C56—C55	178.2 (3)
N1—C11—C16—C15	−179.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.51	2.980 (4)	111
N51—H51···Cg1^i	0.88	2.72	3.504 (3)	148
C15—H15···Cg3^ii	0.95	2.95	3.687 (4)	135

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

(VI) 3-tert-butyl-5-(4-nitrobenzylamino)-1-phenyl-1H-pyrazole

Crystal data

C20H22N4O2	F(000) = 744
Mr = 350.42	Dx = 1.271 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4192 reflections
a = 9.6594 (11) Å	θ = 2.9–27.5°
b = 12.3991 (11) Å	µ = 0.09 mm^−1
c = 15.4338 (15) Å	T = 120 K
β = 97.744 (8)°	Block, colourless
V = 1831.6 (3) Å^3	0.29 × 0.27 × 0.24 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	4192 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2657 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→15
Tmin = 0.959, Tmax = 0.980	l = −20→20
29100 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.169	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 1.4326P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4192 reflections	Δρmax = 0.66 e Å^−3
239 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

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

	x	y	z	Uiso*/Ueq
N1	0.54515 (19)	0.29546 (15)	0.37184 (12)	0.0206 (4)
N2	0.5523 (2)	0.40273 (15)	0.34981 (13)	0.0229 (5)
C3	0.6634 (2)	0.43900 (19)	0.40051 (15)	0.0232 (5)
C4	0.7276 (3)	0.35830 (19)	0.45548 (16)	0.0242 (5)
H4	0.8088	0.3650	0.4973	0.029*
C5	0.6483 (2)	0.26791 (19)	0.43621 (15)	0.0218 (5)
C11	0.4367 (2)	0.23064 (19)	0.32945 (14)	0.0216 (5)
C12	0.4654 (3)	0.1275 (2)	0.30360 (16)	0.0267 (6)
H12	0.5581	0.1003	0.3142	0.032*
C13	0.3596 (3)	0.0642 (2)	0.26241 (17)	0.0321 (6)
H13	0.3790	−0.0075	0.2460	0.038*
C14	0.2261 (3)	0.1039 (2)	0.24483 (17)	0.0316 (6)
H14	0.1534	0.0600	0.2161	0.038*
C15	0.1980 (3)	0.2078 (2)	0.26904 (16)	0.0288 (6)
H15	0.1061	0.2360	0.2559	0.035*
C16	0.3028 (2)	0.2712 (2)	0.31232 (15)	0.0250 (5)
H16	0.2829	0.3422	0.3302	0.030*
C31	0.7023 (3)	0.55641 (19)	0.39837 (16)	0.0273 (6)
C32	0.8514 (3)	0.5736 (3)	0.4381 (3)	0.0600 (11)
H32A	0.8633	0.5501	0.4993	0.090*
H32B	0.8748	0.6503	0.4353	0.090*
H32C	0.9133	0.5316	0.4057	0.090*
C33	0.6033 (4)	0.6183 (2)	0.4499 (2)	0.0473 (8)
H33A	0.5070	0.6097	0.4214	0.071*
H33B	0.6282	0.6950	0.4518	0.071*
H33C	0.6113	0.5899	0.5096	0.071*
C34	0.6827 (3)	0.5997 (2)	0.30547 (19)	0.0416 (7)
H34A	0.7484	0.5638	0.2718	0.062*
H34B	0.7003	0.6776	0.3065	0.062*
H34C	0.5868	0.5857	0.2782	0.062*
N51	0.6612 (2)	0.16617 (16)	0.47086 (13)	0.0234 (5)
H51	0.5823	0.1299	0.4673	0.028*
C51	0.8964 (2)	0.14249 (17)	0.55521 (15)	0.0206 (5)
C52	0.9570 (2)	0.14165 (18)	0.47924 (15)	0.0216 (5)
H52	0.9004	0.1517	0.4245	0.026*
C53	1.0986 (3)	0.12631 (18)	0.48192 (16)	0.0235 (5)
H53	1.1403	0.1241	0.4296	0.028*
C54	1.1782 (2)	0.11428 (18)	0.56191 (16)	0.0236 (5)
C55	1.1214 (3)	0.11572 (19)	0.63885 (16)	0.0247 (5)
H55	1.1786	0.1079	0.6936	0.030*
C56	0.9799 (3)	0.12875 (19)	0.63437 (15)	0.0243 (5)
H56	0.9383	0.1283	0.6867	0.029*
C57	0.7421 (2)	0.1560 (2)	0.55646 (15)	0.0237 (5)
H571	0.7071	0.0931	0.5865	0.028*
H572	0.7266	0.2211	0.5911	0.028*
N54	1.3281 (2)	0.09935 (16)	0.56544 (16)	0.0304 (5)
O41	1.37432 (19)	0.08451 (15)	0.49616 (14)	0.0381 (5)
O42	1.40060 (19)	0.10297 (16)	0.63617 (14)	0.0408 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0202 (10)	0.0182 (10)	0.0225 (10)	−0.0006 (8)	−0.0003 (8)	0.0001 (8)
N2	0.0243 (10)	0.0201 (10)	0.0241 (10)	−0.0017 (8)	0.0019 (8)	0.0009 (8)
C3	0.0207 (12)	0.0237 (13)	0.0255 (12)	−0.0010 (10)	0.0044 (10)	−0.0032 (10)
C4	0.0198 (12)	0.0252 (13)	0.0264 (12)	−0.0006 (9)	−0.0007 (10)	−0.0029 (10)
C5	0.0182 (11)	0.0229 (12)	0.0242 (12)	0.0015 (9)	0.0025 (9)	0.0001 (10)
C11	0.0214 (12)	0.0248 (12)	0.0181 (11)	−0.0024 (9)	0.0007 (9)	0.0021 (9)
C12	0.0259 (13)	0.0274 (13)	0.0260 (13)	−0.0004 (10)	0.0006 (10)	−0.0006 (10)
C13	0.0347 (15)	0.0262 (14)	0.0333 (14)	−0.0052 (11)	−0.0027 (12)	−0.0049 (11)
C14	0.0300 (14)	0.0317 (15)	0.0305 (14)	−0.0097 (11)	−0.0046 (11)	−0.0018 (11)
C15	0.0216 (12)	0.0357 (15)	0.0271 (13)	−0.0032 (11)	−0.0037 (10)	0.0059 (11)
C16	0.0243 (13)	0.0248 (13)	0.0250 (12)	−0.0004 (10)	0.0006 (10)	0.0027 (10)
C31	0.0275 (13)	0.0212 (12)	0.0326 (13)	−0.0040 (10)	0.0021 (11)	−0.0029 (10)
C32	0.0401 (18)	0.0311 (17)	0.100 (3)	−0.0104 (14)	−0.0210 (19)	0.0092 (17)
C33	0.064 (2)	0.0319 (16)	0.0496 (19)	−0.0035 (14)	0.0189 (16)	−0.0051 (13)
C34	0.0476 (18)	0.0308 (15)	0.0468 (18)	−0.0077 (13)	0.0078 (14)	0.0051 (13)
N51	0.0185 (10)	0.0236 (10)	0.0266 (10)	−0.0019 (8)	−0.0021 (8)	0.0028 (8)
C51	0.0225 (12)	0.0153 (11)	0.0231 (12)	−0.0004 (9)	0.0000 (10)	0.0002 (9)
C52	0.0238 (12)	0.0198 (12)	0.0205 (11)	−0.0007 (9)	0.0004 (9)	0.0031 (9)
C53	0.0264 (13)	0.0183 (12)	0.0270 (12)	−0.0011 (9)	0.0080 (10)	0.0021 (9)
C54	0.0197 (12)	0.0159 (11)	0.0349 (14)	0.0005 (9)	0.0023 (10)	0.0007 (10)
C55	0.0248 (13)	0.0236 (12)	0.0237 (12)	0.0013 (10)	−0.0038 (10)	0.0001 (10)
C56	0.0267 (13)	0.0240 (12)	0.0220 (12)	0.0003 (10)	0.0027 (10)	−0.0011 (10)
C57	0.0215 (12)	0.0276 (13)	0.0220 (12)	0.0002 (10)	0.0030 (10)	0.0010 (10)
N54	0.0224 (11)	0.0207 (11)	0.0478 (14)	−0.0008 (8)	0.0040 (11)	0.0033 (10)
O41	0.0270 (10)	0.0330 (11)	0.0575 (13)	−0.0012 (8)	0.0170 (9)	−0.0008 (9)
O42	0.0248 (10)	0.0425 (12)	0.0514 (13)	0.0026 (8)	−0.0079 (9)	0.0065 (9)

Geometric parameters (Å, º)

N1—C5	1.353 (3)	C32—H32C	0.9800
N1—N2	1.377 (3)	C33—H33A	0.9800
N1—C11	1.409 (3)	C33—H33B	0.9800
N2—C3	1.319 (3)	C33—H33C	0.9800
C3—C4	1.401 (3)	C34—H34A	0.9800
C3—C31	1.505 (3)	C34—H34B	0.9800
C4—C5	1.367 (3)	C34—H34C	0.9800
C4—H4	0.9500	N51—C57	1.447 (3)
C5—N51	1.369 (3)	N51—H51	0.8801
C11—C12	1.379 (3)	C57—C51	1.503 (3)
C11—C16	1.380 (3)	C57—H571	0.9900
C12—C13	1.375 (3)	C57—H572	0.9900
C12—H12	0.9500	C51—C52	1.379 (3)
C13—C14	1.372 (4)	C51—C56	1.381 (3)
C13—H13	0.9500	C52—C53	1.376 (3)
C14—C15	1.379 (4)	C52—H52	0.9500
C14—H14	0.9500	C53—C54	1.372 (3)
C15—C16	1.380 (3)	C53—H53	0.9500
C15—H15	0.9500	C54—C55	1.374 (3)
C16—H16	0.9500	C54—N54	1.453 (3)
C31—C32	1.503 (4)	C55—C56	1.369 (3)
C31—C34	1.519 (4)	C55—H55	0.9500
C31—C33	1.530 (4)	C56—H56	0.9500
C32—H32A	0.9800	N54—O42	1.216 (3)
C32—H32B	0.9800	N54—O41	1.227 (3)
C5—N1—N2	111.64 (18)	C31—C33—H33A	109.5
C5—N1—C11	128.7 (2)	C31—C33—H33B	109.5
N2—N1—C11	119.68 (18)	H33A—C33—H33B	109.5
C3—N2—N1	104.28 (18)	C31—C33—H33C	109.5
N2—C3—C4	111.9 (2)	H33A—C33—H33C	109.5
N2—C3—C31	120.1 (2)	H33B—C33—H33C	109.5
C4—C3—C31	127.8 (2)	C31—C34—H34A	109.5
C5—C4—C3	105.4 (2)	C31—C34—H34B	109.5
C5—C4—H4	127.3	H34A—C34—H34B	109.5
C3—C4—H4	127.3	C31—C34—H34C	109.5
N1—C5—C4	106.7 (2)	H34A—C34—H34C	109.5
N1—C5—N51	122.6 (2)	H34B—C34—H34C	109.5
C4—C5—N51	130.7 (2)	C5—N51—C57	116.49 (19)
C12—C11—C16	120.2 (2)	C5—N51—H51	114.5
C12—C11—N1	119.8 (2)	C57—N51—H51	111.6
C16—C11—N1	120.0 (2)	N51—C57—C51	114.4 (2)
C13—C12—C11	119.8 (2)	N51—C57—H571	108.7
C13—C12—H12	120.1	C51—C57—H571	108.7
C11—C12—H12	120.1	N51—C57—H572	108.7
C14—C13—C12	120.4 (2)	C51—C57—H572	108.7
C14—C13—H13	119.8	H571—C57—H572	107.6
C12—C13—H13	119.8	C52—C51—C56	119.2 (2)
C13—C14—C15	119.7 (2)	C52—C51—C57	123.1 (2)
C13—C14—H14	120.1	C56—C51—C57	117.7 (2)
C15—C14—H14	120.1	C53—C52—C51	120.6 (2)
C14—C15—C16	120.3 (2)	C53—C52—H52	119.7
C14—C15—H15	119.8	C51—C52—H52	119.7
C16—C15—H15	119.8	C54—C53—C52	118.5 (2)
C11—C16—C15	119.5 (2)	C54—C53—H53	120.8
C11—C16—H16	120.2	C52—C53—H53	120.8
C15—C16—H16	120.2	C53—C54—C55	122.4 (2)
C32—C31—C3	110.9 (2)	C53—C54—N54	118.8 (2)
C32—C31—C34	109.0 (2)	C55—C54—N54	118.8 (2)
C3—C31—C34	111.3 (2)	C56—C55—C54	118.1 (2)
C32—C31—C33	110.4 (3)	C56—C55—H55	121.0
C3—C31—C33	107.4 (2)	C54—C55—H55	121.0
C34—C31—C33	107.9 (2)	C55—C56—C51	121.3 (2)
C31—C32—H32A	109.5	C55—C56—H56	119.4
C31—C32—H32B	109.5	C51—C56—H56	119.4
H32A—C32—H32B	109.5	O42—N54—O41	123.7 (2)
C31—C32—H32C	109.5	O42—N54—C54	118.6 (2)
H32A—C32—H32C	109.5	O41—N54—C54	117.7 (2)
H32B—C32—H32C	109.5
C5—N1—N2—C3	1.4 (2)	C4—C3—C31—C32	21.8 (4)
C11—N1—N2—C3	−180.0 (2)	N2—C3—C31—C34	−40.9 (3)
N1—N2—C3—C4	−0.7 (3)	C4—C3—C31—C34	143.3 (3)
N1—N2—C3—C31	−177.1 (2)	N2—C3—C31—C33	77.0 (3)
N2—C3—C4—C5	−0.3 (3)	C4—C3—C31—C33	−98.9 (3)
C31—C3—C4—C5	175.8 (2)	N1—C5—N51—C57	−159.4 (2)
N2—N1—C5—C4	−1.6 (3)	C4—C5—N51—C57	20.5 (4)
C11—N1—C5—C4	179.9 (2)	C5—N51—C57—C51	−86.6 (3)
N2—N1—C5—N51	178.4 (2)	N51—C57—C51—C52	1.1 (3)
C11—N1—C5—N51	−0.1 (4)	N51—C57—C51—C56	−177.9 (2)
C3—C4—C5—N1	1.1 (3)	C56—C51—C52—C53	0.6 (3)
C3—C4—C5—N51	−178.8 (2)	C57—C51—C52—C53	−178.4 (2)
C5—N1—C11—C12	−43.7 (3)	C51—C52—C53—C54	−1.4 (3)
N2—N1—C11—C12	137.9 (2)	C52—C53—C54—C55	0.8 (3)
C5—N1—C11—C16	137.6 (2)	C52—C53—C54—N54	−179.3 (2)
N2—N1—C11—C16	−40.8 (3)	C53—C54—C55—C56	0.6 (3)
C16—C11—C12—C13	−1.5 (4)	N54—C54—C55—C56	−179.3 (2)
N1—C11—C12—C13	179.9 (2)	C54—C55—C56—C51	−1.4 (3)
C11—C12—C13—C14	1.7 (4)	C52—C51—C56—C55	0.8 (3)
C12—C13—C14—C15	−0.3 (4)	C57—C51—C56—C55	179.9 (2)
C13—C14—C15—C16	−1.3 (4)	C53—C54—N54—O42	170.4 (2)
C12—C11—C16—C15	−0.1 (3)	C55—C54—N54—O42	−9.6 (3)
N1—C11—C16—C15	178.6 (2)	C53—C54—N54—O41	−9.1 (3)
C14—C15—C16—C11	1.5 (4)	C55—C54—N54—O41	170.9 (2)
N2—C3—C31—C32	−162.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N51	0.95	2.62	3.026 (3)	106
N51—H51···O41^i	0.88	2.19	3.025 (3)	158

Symmetry code: (i) x−1, y, z.

(VII) 3-tert-butyl-5-(3,4,5-trimethoxybenzylamino)-1-phenyl-1H-pyrazole

Crystal data

C23H29N3O3	Z = 4
Mr = 395.49	F(000) = 848
Triclinic, P1	Dx = 1.251 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.1533 (11) Å	Cell parameters from 9621 reflections
b = 11.1645 (10) Å	θ = 2.8–27.5°
c = 20.927 (2) Å	µ = 0.08 mm^−1
α = 84.820 (8)°	T = 120 K
β = 82.988 (8)°	Block, colourless
γ = 63.153 (7)°	0.48 × 0.35 × 0.25 mm
V = 2099.0 (4) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	9621 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	5050 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.961, Tmax = 0.986	l = −27→27
50489 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.174	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 1.2088P] where P = (Fo^2 + 2Fc^2)/3
9621 reflections	(Δ/σ)max = 0.001
535 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.4845 (2)	0.5027 (2)	0.37462 (9)	0.0215 (5)
N12	0.4429 (2)	0.6033 (2)	0.32691 (10)	0.0237 (5)
C13	0.3008 (3)	0.6418 (3)	0.32406 (12)	0.0233 (6)
C14	0.2485 (3)	0.5671 (3)	0.36792 (12)	0.0247 (6)
H14	0.1501	0.5766	0.3748	0.030*
C15	0.3685 (3)	0.4777 (3)	0.39877 (12)	0.0230 (6)
C111	0.6336 (3)	0.4403 (2)	0.38909 (12)	0.0231 (6)
C112	0.6730 (3)	0.3844 (3)	0.44909 (13)	0.0263 (6)
H112	0.5990	0.3879	0.4824	0.032*
C113	0.8195 (3)	0.3234 (3)	0.46074 (14)	0.0335 (7)
H113	0.8470	0.2841	0.5022	0.040*
C114	0.9268 (3)	0.3189 (3)	0.41289 (15)	0.0368 (7)
H114	1.0282	0.2756	0.4211	0.044*
C115	0.8871 (3)	0.3771 (3)	0.35320 (15)	0.0349 (7)
H115	0.9610	0.3756	0.3203	0.042*
C116	0.7411 (3)	0.4372 (3)	0.34092 (13)	0.0272 (6)
H116	0.7138	0.4766	0.2995	0.033*
C131	0.2167 (3)	0.7451 (3)	0.27459 (12)	0.0259 (6)
C132	0.2825 (3)	0.8429 (3)	0.25543 (13)	0.0332 (7)
H12A	0.2759	0.8921	0.2931	0.050*
H12B	0.2273	0.9065	0.2218	0.050*
H12C	0.3867	0.7931	0.2390	0.050*
C133	0.2247 (3)	0.6728 (3)	0.21475 (13)	0.0325 (7)
H13A	0.3284	0.6231	0.1978	0.049*
H13B	0.1691	0.7388	0.1819	0.049*
H13C	0.1815	0.6101	0.2261	0.049*
C134	0.0560 (3)	0.8233 (3)	0.30055 (14)	0.0374 (7)
H14A	0.0105	0.7620	0.3098	0.056*
H14B	0.0024	0.8925	0.2684	0.056*
H14C	0.0513	0.8661	0.3402	0.056*
N151	0.3801 (2)	0.3805 (2)	0.44557 (10)	0.0249 (5)
H151	0.4609	0.3038	0.4421	0.030*
C157	0.2476 (3)	0.3603 (3)	0.45965 (13)	0.0301 (6)
H57A	0.2133	0.3512	0.4189	0.036*
H57B	0.1678	0.4395	0.4813	0.036*
C151	0.2780 (3)	0.2370 (3)	0.50204 (12)	0.0252 (6)
C152	0.2948 (3)	0.1215 (3)	0.47569 (12)	0.0245 (6)
H152	0.2845	0.1212	0.4312	0.029*
C153	0.3266 (3)	0.0065 (3)	0.51401 (12)	0.0235 (6)
C154	0.3460 (3)	0.0051 (2)	0.57797 (12)	0.0224 (6)
C155	0.3286 (3)	0.1213 (3)	0.60472 (12)	0.0236 (6)
C156	0.2927 (3)	0.2376 (3)	0.56680 (12)	0.0265 (6)
H156	0.2781	0.3179	0.5852	0.032*
O13	0.3456 (2)	−0.11283 (18)	0.49307 (8)	0.0303 (4)
C136	0.3171 (3)	−0.1144 (3)	0.42827 (13)	0.0360 (7)
H16A	0.2134	−0.0521	0.4226	0.054*
H16B	0.3360	−0.2054	0.4187	0.054*
H16C	0.3822	−0.0867	0.3989	0.054*
O14	0.38984 (19)	−0.11335 (17)	0.61413 (8)	0.0255 (4)
C137	0.2707 (3)	−0.1236 (3)	0.65358 (13)	0.0303 (6)
H17A	0.2278	−0.0515	0.6844	0.045*
H17B	0.3077	−0.2109	0.6771	0.045*
H17C	0.1947	−0.1155	0.6265	0.045*
O15	0.3523 (2)	0.10801 (18)	0.66821 (8)	0.0294 (4)
C138	0.3325 (3)	0.2260 (3)	0.69753 (13)	0.0317 (7)
H18A	0.3981	0.2611	0.6740	0.048*
H18B	0.3567	0.2041	0.7424	0.048*
H18C	0.2292	0.2940	0.6964	0.048*
N21	0.9342 (2)	0.5185 (2)	0.87675 (10)	0.0233 (5)
N22	0.8767 (2)	0.6204 (2)	0.83089 (10)	0.0248 (5)
C23	0.7324 (3)	0.6593 (3)	0.83826 (12)	0.0252 (6)
C24	0.6943 (3)	0.5851 (3)	0.88833 (12)	0.0246 (6)
H24	0.5975	0.5964	0.9036	0.029*
C25	0.8253 (3)	0.4930 (3)	0.91064 (11)	0.0226 (6)
C211	1.0891 (3)	0.4567 (2)	0.88130 (12)	0.0220 (6)
C212	1.1495 (3)	0.3944 (3)	0.93789 (12)	0.0264 (6)
H212	1.0872	0.3919	0.9752	0.032*
C213	1.3012 (3)	0.3358 (3)	0.93968 (13)	0.0292 (6)
H213	1.3433	0.2913	0.9783	0.035*
C214	1.3919 (3)	0.3411 (3)	0.88638 (13)	0.0306 (6)
H214	1.4964	0.3003	0.8880	0.037*
C215	1.3306 (3)	0.4057 (3)	0.83074 (13)	0.0287 (6)
H215	1.3928	0.4111	0.7940	0.034*
C216	1.1799 (3)	0.4625 (3)	0.82787 (12)	0.0252 (6)
H216	1.1383	0.5059	0.7890	0.030*
C231	0.6306 (3)	0.7693 (3)	0.79524 (13)	0.0280 (6)
C232	0.7078 (4)	0.7734 (4)	0.72993 (16)	0.0725 (13)
H22A	0.7425	0.6870	0.7099	0.109*
H22B	0.7928	0.7906	0.7342	0.109*
H22C	0.6388	0.8452	0.7030	0.109*
C233	0.4964 (4)	0.7500 (4)	0.7893 (2)	0.0805 (15)
H23A	0.4439	0.7523	0.8321	0.121*
H23B	0.5265	0.6630	0.7707	0.121*
H23C	0.4307	0.8220	0.7614	0.121*
C234	0.5794 (5)	0.9038 (3)	0.82534 (19)	0.0680 (12)
H24A	0.6652	0.9205	0.8284	0.102*
H24B	0.5303	0.9024	0.8685	0.102*
H24C	0.5096	0.9754	0.7985	0.102*
N251	0.8534 (2)	0.3909 (2)	0.95660 (10)	0.0238 (5)
H251	0.9324	0.3143	0.9494	0.029*
C257	0.7249 (3)	0.3702 (3)	0.98259 (12)	0.0258 (6)
H271	0.6702	0.3688	0.9468	0.031*
H272	0.6573	0.4453	1.0103	0.031*
C251	0.7731 (3)	0.2405 (3)	1.02110 (12)	0.0248 (6)
C252	0.7750 (3)	0.1311 (3)	0.99469 (12)	0.0265 (6)
H252	0.7399	0.1400	0.9536	0.032*
C253	0.8280 (3)	0.0082 (3)	1.02820 (12)	0.0241 (6)
C254	0.8802 (3)	−0.0053 (2)	1.08764 (12)	0.0234 (6)
C255	0.8760 (3)	0.1064 (3)	1.11431 (12)	0.0242 (6)
C256	0.8224 (3)	0.2290 (3)	1.08126 (12)	0.0260 (6)
H256	0.8192	0.3051	1.0996	0.031*
O23	0.8383 (2)	−0.10741 (18)	1.00659 (9)	0.0322 (5)
C236	0.7802 (3)	−0.0986 (3)	0.94749 (13)	0.0366 (7)
H26A	0.8308	−0.0641	0.9134	0.055*
H26B	0.6739	−0.0377	0.9512	0.055*
H26C	0.7957	−0.1880	0.9368	0.055*
O24	0.94095 (19)	−0.12907 (17)	1.11896 (8)	0.0253 (4)
C237	0.8378 (3)	−0.1487 (3)	1.16599 (12)	0.0287 (6)
H27A	0.7564	−0.1475	1.1446	0.043*
H27B	0.7981	−0.0767	1.1967	0.043*
H27C	0.8879	−0.2356	1.1890	0.043*
O25	0.9283 (2)	0.08157 (18)	1.17327 (8)	0.0307 (5)
C238	0.9182 (3)	0.1937 (3)	1.20450 (13)	0.0333 (7)
H28A	0.8147	0.2619	1.2091	0.050*
H28B	0.9786	0.2318	1.1788	0.050*
H28C	0.9545	0.1646	1.2472	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0227 (11)	0.0187 (11)	0.0246 (11)	−0.0102 (9)	−0.0044 (9)	0.0009 (9)
N12	0.0262 (12)	0.0191 (11)	0.0255 (11)	−0.0093 (9)	−0.0056 (9)	0.0005 (9)
C13	0.0238 (14)	0.0208 (14)	0.0252 (13)	−0.0086 (11)	−0.0035 (11)	−0.0062 (11)
C14	0.0220 (13)	0.0241 (14)	0.0291 (14)	−0.0110 (11)	−0.0046 (11)	0.0007 (11)
C15	0.0270 (14)	0.0216 (14)	0.0229 (13)	−0.0128 (11)	−0.0032 (11)	−0.0016 (11)
C111	0.0215 (13)	0.0136 (13)	0.0333 (15)	−0.0056 (11)	−0.0054 (11)	−0.0050 (11)
C112	0.0272 (14)	0.0199 (14)	0.0334 (15)	−0.0109 (11)	−0.0060 (11)	−0.0027 (11)
C113	0.0357 (16)	0.0262 (15)	0.0393 (16)	−0.0115 (13)	−0.0176 (13)	0.0015 (13)
C114	0.0240 (15)	0.0279 (16)	0.059 (2)	−0.0102 (12)	−0.0122 (14)	0.0001 (14)
C115	0.0273 (15)	0.0284 (16)	0.0514 (19)	−0.0151 (13)	−0.0020 (13)	0.0002 (14)
C116	0.0288 (15)	0.0202 (14)	0.0338 (15)	−0.0118 (12)	−0.0032 (12)	−0.0017 (12)
C131	0.0264 (14)	0.0210 (14)	0.0297 (14)	−0.0093 (11)	−0.0057 (11)	−0.0018 (11)
C132	0.0396 (17)	0.0260 (15)	0.0350 (16)	−0.0144 (13)	−0.0110 (13)	0.0038 (12)
C133	0.0333 (16)	0.0302 (16)	0.0339 (15)	−0.0124 (13)	−0.0099 (12)	−0.0017 (12)
C134	0.0322 (16)	0.0321 (17)	0.0368 (16)	−0.0041 (13)	−0.0086 (13)	0.0032 (13)
N151	0.0205 (11)	0.0208 (12)	0.0310 (12)	−0.0075 (9)	−0.0033 (9)	0.0017 (10)
C157	0.0278 (15)	0.0286 (15)	0.0360 (16)	−0.0146 (12)	−0.0070 (12)	0.0062 (12)
C151	0.0183 (13)	0.0245 (14)	0.0333 (15)	−0.0103 (11)	−0.0046 (11)	0.0033 (12)
C152	0.0197 (13)	0.0277 (15)	0.0259 (13)	−0.0102 (11)	−0.0044 (10)	−0.0003 (12)
C153	0.0217 (13)	0.0204 (14)	0.0309 (14)	−0.0111 (11)	−0.0016 (11)	−0.0045 (11)
C154	0.0196 (13)	0.0182 (13)	0.0283 (14)	−0.0079 (11)	−0.0012 (10)	0.0002 (11)
C155	0.0251 (14)	0.0250 (15)	0.0243 (14)	−0.0140 (12)	−0.0042 (11)	0.0003 (11)
C156	0.0271 (14)	0.0212 (14)	0.0326 (15)	−0.0112 (12)	−0.0035 (11)	−0.0037 (12)
O13	0.0399 (11)	0.0249 (10)	0.0276 (10)	−0.0144 (9)	−0.0053 (8)	−0.0055 (8)
C136	0.0424 (17)	0.0371 (17)	0.0311 (15)	−0.0179 (14)	−0.0065 (13)	−0.0087 (13)
O14	0.0280 (10)	0.0192 (10)	0.0281 (10)	−0.0097 (8)	−0.0017 (8)	−0.0002 (8)
C137	0.0380 (16)	0.0270 (15)	0.0298 (15)	−0.0190 (13)	0.0039 (12)	−0.0044 (12)
O15	0.0436 (11)	0.0232 (10)	0.0262 (10)	−0.0183 (9)	−0.0058 (8)	−0.0020 (8)
C138	0.0421 (17)	0.0271 (15)	0.0334 (15)	−0.0211 (13)	−0.0020 (13)	−0.0081 (12)
N21	0.0245 (11)	0.0199 (11)	0.0251 (11)	−0.0092 (9)	−0.0051 (9)	0.0017 (9)
N22	0.0266 (12)	0.0198 (11)	0.0277 (12)	−0.0098 (10)	−0.0052 (9)	0.0018 (9)
C23	0.0288 (15)	0.0213 (14)	0.0255 (14)	−0.0103 (12)	−0.0034 (11)	−0.0044 (11)
C24	0.0236 (14)	0.0247 (14)	0.0260 (14)	−0.0111 (11)	−0.0013 (11)	−0.0037 (11)
C25	0.0277 (14)	0.0202 (14)	0.0221 (13)	−0.0120 (11)	−0.0023 (11)	−0.0040 (11)
C211	0.0242 (14)	0.0158 (13)	0.0274 (14)	−0.0093 (11)	−0.0020 (11)	−0.0057 (11)
C212	0.0283 (15)	0.0231 (14)	0.0278 (14)	−0.0110 (12)	−0.0015 (11)	−0.0039 (11)
C213	0.0306 (15)	0.0245 (15)	0.0325 (15)	−0.0108 (12)	−0.0074 (12)	−0.0033 (12)
C214	0.0236 (14)	0.0290 (16)	0.0394 (16)	−0.0110 (12)	−0.0039 (12)	−0.0045 (13)
C215	0.0290 (15)	0.0261 (15)	0.0321 (15)	−0.0136 (12)	−0.0004 (12)	−0.0030 (12)
C216	0.0285 (15)	0.0215 (14)	0.0263 (14)	−0.0114 (12)	−0.0039 (11)	−0.0008 (11)
C231	0.0274 (14)	0.0245 (15)	0.0312 (15)	−0.0104 (12)	−0.0076 (11)	0.0035 (12)
C232	0.049 (2)	0.082 (3)	0.043 (2)	0.005 (2)	−0.0047 (17)	0.023 (2)
C233	0.057 (2)	0.078 (3)	0.120 (4)	−0.041 (2)	−0.057 (2)	0.057 (3)
C234	0.085 (3)	0.0309 (19)	0.070 (3)	−0.0029 (19)	−0.039 (2)	0.0020 (18)
N251	0.0236 (11)	0.0179 (11)	0.0281 (12)	−0.0081 (9)	−0.0025 (9)	0.0009 (9)
C257	0.0251 (14)	0.0249 (15)	0.0283 (14)	−0.0126 (12)	−0.0016 (11)	0.0023 (11)
C251	0.0222 (13)	0.0214 (14)	0.0299 (14)	−0.0097 (11)	−0.0007 (11)	0.0007 (11)
C252	0.0267 (14)	0.0274 (15)	0.0278 (14)	−0.0138 (12)	−0.0043 (11)	−0.0001 (12)
C253	0.0239 (14)	0.0215 (14)	0.0282 (14)	−0.0115 (11)	0.0007 (11)	−0.0036 (11)
C254	0.0229 (13)	0.0191 (14)	0.0262 (14)	−0.0087 (11)	−0.0007 (11)	0.0024 (11)
C255	0.0240 (13)	0.0256 (15)	0.0235 (13)	−0.0120 (11)	−0.0016 (11)	0.0000 (11)
C256	0.0286 (14)	0.0210 (14)	0.0310 (15)	−0.0131 (12)	−0.0027 (11)	−0.0023 (12)
O23	0.0442 (12)	0.0241 (10)	0.0324 (10)	−0.0171 (9)	−0.0083 (9)	−0.0038 (8)
C236	0.0456 (18)	0.0352 (17)	0.0330 (16)	−0.0193 (15)	−0.0093 (13)	−0.0061 (13)
O24	0.0291 (10)	0.0185 (9)	0.0277 (10)	−0.0108 (8)	−0.0011 (8)	0.0002 (8)
C237	0.0352 (16)	0.0246 (15)	0.0302 (15)	−0.0168 (12)	−0.0022 (12)	−0.0020 (12)
O25	0.0444 (12)	0.0238 (10)	0.0293 (10)	−0.0188 (9)	−0.0097 (8)	0.0006 (8)
C238	0.0452 (18)	0.0309 (16)	0.0305 (15)	−0.0218 (14)	−0.0059 (13)	−0.0034 (12)

Geometric parameters (Å, º)

N11—C15	1.359 (3)	N21—C25	1.365 (3)
N11—N12	1.382 (3)	N21—N22	1.377 (3)
N11—C111	1.411 (3)	N21—C211	1.415 (3)
N12—C13	1.314 (3)	N22—C23	1.319 (3)
C13—C14	1.400 (4)	C23—C24	1.403 (4)
C13—C131	1.497 (3)	C23—C231	1.506 (4)
C14—C15	1.369 (3)	C24—C25	1.370 (3)
C14—H14	0.9500	C24—H24	0.9500
C15—N151	1.368 (3)	C25—N251	1.371 (3)
C111—C112	1.372 (4)	C211—C216	1.376 (4)
C111—C116	1.382 (4)	C211—C212	1.380 (4)
C112—C113	1.371 (4)	C212—C213	1.379 (4)
C112—H112	0.9500	C212—H212	0.9500
C113—C114	1.373 (4)	C213—C214	1.372 (4)
C113—H113	0.9500	C213—H213	0.9500
C114—C115	1.373 (4)	C214—C215	1.372 (4)
C114—H114	0.9500	C214—H214	0.9500
C115—C116	1.370 (4)	C215—C216	1.373 (4)
C115—H115	0.9500	C215—H215	0.9500
C116—H116	0.9500	C216—H216	0.9500
C131—C134	1.518 (4)	C231—C233	1.494 (4)
C131—C132	1.521 (4)	C231—C232	1.498 (4)
C131—C133	1.525 (4)	C231—C234	1.519 (4)
C132—H12A	0.9800	C232—H22A	0.9800
C132—H12B	0.9800	C232—H22B	0.9800
C132—H12C	0.9800	C232—H22C	0.9800
C133—H13A	0.9800	C233—H23A	0.9800
C133—H13B	0.9800	C233—H23B	0.9800
C133—H13C	0.9800	C233—H23C	0.9800
C134—H14A	0.9800	C234—H24A	0.9800
C134—H14B	0.9800	C234—H24B	0.9800
C134—H14C	0.9800	C234—H24C	0.9800
N151—C157	1.453 (3)	N251—C257	1.459 (3)
N151—H151	0.8797	N251—H251	0.8785
C157—C151	1.496 (4)	C257—C251	1.494 (3)
C157—H57A	0.9900	C257—H271	0.9900
C157—H57B	0.9900	C257—H272	0.9900
C151—C152	1.380 (4)	C251—C252	1.377 (4)
C151—C156	1.382 (4)	C251—C256	1.385 (4)
C152—C153	1.378 (4)	C252—C253	1.384 (4)
C152—H152	0.9500	C252—H252	0.9500
C153—O13	1.362 (3)	C253—O23	1.361 (3)
C153—C154	1.374 (4)	C253—C254	1.380 (4)
C154—O14	1.375 (3)	C254—O24	1.373 (3)
C154—C155	1.388 (4)	C254—C255	1.393 (4)
C155—O15	1.362 (3)	C255—O25	1.359 (3)
C155—C156	1.380 (4)	C255—C256	1.377 (4)
C156—H156	0.9500	C256—H256	0.9500
O13—C136	1.424 (3)	O23—C236	1.411 (3)
C136—H16A	0.9800	C236—H26A	0.9800
C136—H16B	0.9800	C236—H26B	0.9800
C136—H16C	0.9800	C236—H26C	0.9800
O14—C137	1.422 (3)	O24—C237	1.425 (3)
C137—H17A	0.9800	C237—H27A	0.9800
C137—H17B	0.9800	C237—H27B	0.9800
C137—H17C	0.9800	C237—H27C	0.9800
O15—C138	1.424 (3)	O25—C238	1.421 (3)
C138—H18A	0.9800	C238—H28A	0.9800
C138—H18B	0.9800	C238—H28B	0.9800
C138—H18C	0.9800	C238—H28C	0.9800
C15—N11—N12	110.92 (19)	C25—N21—N22	111.1 (2)
C15—N11—C111	130.5 (2)	C25—N21—C211	130.6 (2)
N12—N11—C111	118.5 (2)	N22—N21—C211	118.4 (2)
C13—N12—N11	105.1 (2)	C23—N22—N21	105.1 (2)
N12—C13—C14	111.6 (2)	N22—C23—C24	111.4 (2)
N12—C13—C131	121.0 (2)	N22—C23—C231	120.7 (2)
C14—C13—C131	127.2 (2)	C24—C23—C231	127.8 (2)
C15—C14—C13	105.8 (2)	C25—C24—C23	105.8 (2)
C15—C14—H14	127.1	C25—C24—H24	127.1
C13—C14—H14	127.1	C23—C24—H24	127.1
N11—C15—N151	123.0 (2)	N21—C25—C24	106.5 (2)
N11—C15—C14	106.6 (2)	N21—C25—N251	123.1 (2)
N151—C15—C14	130.3 (2)	C24—C25—N251	130.4 (2)
C112—C111—C116	120.1 (2)	C216—C211—C212	120.0 (2)
C112—C111—N11	121.7 (2)	C216—C211—N21	118.3 (2)
C116—C111—N11	118.1 (2)	C212—C211—N21	121.7 (2)
C113—C112—C111	119.7 (3)	C213—C212—C211	119.3 (2)
C113—C112—H112	120.1	C213—C212—H212	120.3
C111—C112—H112	120.1	C211—C212—H212	120.3
C112—C113—C114	120.4 (3)	C214—C213—C212	120.8 (3)
C112—C113—H113	119.8	C214—C213—H213	119.6
C114—C113—H113	119.8	C212—C213—H213	119.6
C113—C114—C115	119.8 (3)	C215—C214—C213	119.4 (3)
C113—C114—H114	120.1	C215—C214—H214	120.3
C115—C114—H114	120.1	C213—C214—H214	120.3
C116—C115—C114	120.2 (3)	C214—C215—C216	120.5 (3)
C116—C115—H115	119.9	C214—C215—H215	119.8
C114—C115—H115	119.9	C216—C215—H215	119.8
C115—C116—C111	119.7 (3)	C215—C216—C211	120.0 (2)
C115—C116—H116	120.1	C215—C216—H216	120.0
C111—C116—H116	120.1	C211—C216—H216	120.0
C13—C131—C134	110.0 (2)	C233—C231—C232	110.2 (3)
C13—C131—C132	111.8 (2)	C233—C231—C23	109.9 (2)
C134—C131—C132	108.9 (2)	C232—C231—C23	111.3 (2)
C13—C131—C133	108.3 (2)	C233—C231—C234	107.7 (3)
C134—C131—C133	109.5 (2)	C232—C231—C234	108.3 (3)
C132—C131—C133	108.3 (2)	C23—C231—C234	109.2 (2)
C131—C132—H12A	109.5	C231—C232—H22A	109.5
C131—C132—H12B	109.5	C231—C232—H22B	109.5
H12A—C132—H12B	109.5	H22A—C232—H22B	109.5
C131—C132—H12C	109.5	C231—C232—H22C	109.5
H12A—C132—H12C	109.5	H22A—C232—H22C	109.5
H12B—C132—H12C	109.5	H22B—C232—H22C	109.5
C131—C133—H13A	109.5	C231—C233—H23A	109.5
C131—C133—H13B	109.5	C231—C233—H23B	109.5
H13A—C133—H13B	109.5	H23A—C233—H23B	109.5
C131—C133—H13C	109.5	C231—C233—H23C	109.5
H13A—C133—H13C	109.5	H23A—C233—H23C	109.5
H13B—C133—H13C	109.5	H23B—C233—H23C	109.5
C131—C134—H14A	109.5	C231—C234—H24A	109.5
C131—C134—H14B	109.5	C231—C234—H24B	109.5
H14A—C134—H14B	109.5	H24A—C234—H24B	109.5
C131—C134—H14C	109.5	C231—C234—H24C	109.5
H14A—C134—H14C	109.5	H24A—C234—H24C	109.5
H14B—C134—H14C	109.5	H24B—C234—H24C	109.5
C15—N151—C157	114.3 (2)	C25—N251—C257	115.0 (2)
C15—N151—H151	116.4	C25—N251—H251	118.0
C157—N151—H151	111.8	C257—N251—H251	111.6
N151—C157—C151	110.8 (2)	N251—C257—C251	110.2 (2)
N151—C157—H57A	109.5	N251—C257—H271	109.6
C151—C157—H57A	109.5	C251—C257—H271	109.6
N151—C157—H57B	109.5	N251—C257—H272	109.6
C151—C157—H57B	109.5	C251—C257—H272	109.6
H57A—C157—H57B	108.1	H271—C257—H272	108.1
C152—C151—C156	120.1 (2)	C252—C251—C256	120.5 (2)
C152—C151—C157	119.5 (2)	C252—C251—C257	119.2 (2)
C156—C151—C157	120.4 (3)	C256—C251—C257	120.2 (2)
C153—C152—C151	119.9 (2)	C251—C252—C253	119.8 (2)
C153—C152—H152	120.0	C251—C252—H252	120.1
C151—C152—H152	120.0	C253—C252—H252	120.1
O13—C153—C154	114.9 (2)	O23—C253—C254	114.6 (2)
O13—C153—C152	124.8 (2)	O23—C253—C252	125.1 (2)
C154—C153—C152	120.3 (2)	C254—C253—C252	120.3 (2)
C153—C154—O14	119.5 (2)	O24—C254—C253	120.1 (2)
C153—C154—C155	120.0 (2)	O24—C254—C255	120.4 (2)
O14—C154—C155	120.5 (2)	C253—C254—C255	119.5 (2)
O15—C155—C156	125.2 (2)	O25—C255—C256	125.3 (2)
O15—C155—C154	115.0 (2)	O25—C255—C254	114.3 (2)
C156—C155—C154	119.8 (2)	C256—C255—C254	120.3 (2)
C155—C156—C151	119.9 (2)	C255—C256—C251	119.6 (2)
C155—C156—H156	120.0	C255—C256—H256	120.2
C151—C156—H156	120.0	C251—C256—H256	120.2
C153—O13—C136	117.0 (2)	C253—O23—C236	117.2 (2)
O13—C136—H16A	109.5	O23—C236—H26A	109.5
O13—C136—H16B	109.5	O23—C236—H26B	109.5
H16A—C136—H16B	109.5	H26A—C236—H26B	109.5
O13—C136—H16C	109.5	O23—C236—H26C	109.5
H16A—C136—H16C	109.5	H26A—C236—H26C	109.5
H16B—C136—H16C	109.5	H26B—C236—H26C	109.5
C154—O14—C137	113.01 (19)	C254—O24—C237	112.51 (19)
O14—C137—H17A	109.5	O24—C237—H27A	109.5
O14—C137—H17B	109.5	O24—C237—H27B	109.5
H17A—C137—H17B	109.5	H27A—C237—H27B	109.5
O14—C137—H17C	109.5	O24—C237—H27C	109.5
H17A—C137—H17C	109.5	H27A—C237—H27C	109.5
H17B—C137—H17C	109.5	H27B—C237—H27C	109.5
C155—O15—C138	116.4 (2)	C255—O25—C238	116.7 (2)
O15—C138—H18A	109.5	O25—C238—H28A	109.5
O15—C138—H18B	109.5	O25—C238—H28B	109.5
H18A—C138—H18B	109.5	H28A—C238—H28B	109.5
O15—C138—H18C	109.5	O25—C238—H28C	109.5
H18A—C138—H18C	109.5	H28A—C238—H28C	109.5
H18B—C138—H18C	109.5	H28B—C238—H28C	109.5
C15—N11—N12—C13	2.1 (3)	C25—N21—N22—C23	1.7 (3)
C111—N11—N12—C13	179.9 (2)	C211—N21—N22—C23	−179.2 (2)
N11—N12—C13—C14	−1.1 (3)	N21—N22—C23—C24	0.3 (3)
N11—N12—C13—C131	−176.3 (2)	N21—N22—C23—C231	−179.0 (2)
N12—C13—C14—C15	−0.3 (3)	N22—C23—C24—C25	−2.2 (3)
C131—C13—C14—C15	174.5 (2)	C231—C23—C24—C25	177.0 (3)
N12—N11—C15—N151	178.4 (2)	N22—N21—C25—C24	−3.1 (3)
C111—N11—C15—N151	1.0 (4)	C211—N21—C25—C24	178.0 (2)
N12—N11—C15—C14	−2.3 (3)	N22—N21—C25—N251	176.0 (2)
C111—N11—C15—C14	−179.8 (2)	C211—N21—C25—N251	−2.9 (4)
C13—C14—C15—N11	1.5 (3)	C23—C24—C25—N21	3.1 (3)
C13—C14—C15—N151	−179.3 (3)	C23—C24—C25—N251	−175.9 (3)
C15—N11—C111—C112	−30.3 (4)	C25—N21—C211—C216	155.0 (3)
N12—N11—C111—C112	152.5 (2)	N22—N21—C211—C216	−23.8 (3)
C15—N11—C111—C116	150.1 (3)	C25—N21—C211—C212	−26.4 (4)
N12—N11—C111—C116	−27.2 (3)	N22—N21—C211—C212	154.8 (2)
C116—C111—C112—C113	−1.1 (4)	C216—C211—C212—C213	−1.5 (4)
N11—C111—C112—C113	179.3 (2)	N21—C211—C212—C213	−180.0 (2)
C111—C112—C113—C114	0.4 (4)	C211—C212—C213—C214	1.2 (4)
C112—C113—C114—C115	0.8 (4)	C212—C213—C214—C215	0.1 (4)
C113—C114—C115—C116	−1.3 (4)	C213—C214—C215—C216	−1.2 (4)
C114—C115—C116—C111	0.7 (4)	C214—C215—C216—C211	1.0 (4)
C112—C111—C116—C115	0.5 (4)	C212—C211—C216—C215	0.4 (4)
N11—C111—C116—C115	−179.8 (2)	N21—C211—C216—C215	178.9 (2)
N12—C13—C131—C134	−150.1 (2)	N22—C23—C231—C233	151.9 (3)
C14—C13—C131—C134	35.5 (4)	C24—C23—C231—C233	−27.2 (4)
N12—C13—C131—C132	−29.0 (3)	N22—C23—C231—C232	29.5 (4)
C14—C13—C131—C132	156.6 (3)	C24—C23—C231—C232	−149.7 (3)
N12—C13—C131—C133	90.2 (3)	N22—C23—C231—C234	−90.1 (3)
C14—C13—C131—C133	−84.1 (3)	C24—C23—C231—C234	90.8 (4)
N11—C15—N151—C157	−173.7 (2)	N21—C25—N251—C257	−173.6 (2)
C14—C15—N151—C157	7.3 (4)	C24—C25—N251—C257	5.3 (4)
C15—N151—C157—C151	169.7 (2)	C25—N251—C257—C251	168.0 (2)
N151—C157—C151—C152	−103.8 (3)	N251—C257—C251—C252	−103.3 (3)
N151—C157—C151—C156	74.7 (3)	N251—C257—C251—C256	73.5 (3)
C156—C151—C152—C153	−0.1 (4)	C256—C251—C252—C253	−0.7 (4)
C157—C151—C152—C153	178.3 (2)	C257—C251—C252—C253	176.0 (2)
C151—C152—C153—O13	−179.9 (2)	C251—C252—C253—O23	−178.5 (2)
C151—C152—C153—C154	−2.0 (4)	C251—C252—C253—C254	−0.5 (4)
O13—C153—C154—O14	3.6 (3)	O23—C253—C254—O24	2.1 (3)
C152—C153—C154—O14	−174.6 (2)	C252—C253—C254—O24	−176.1 (2)
O13—C153—C154—C155	−179.6 (2)	O23—C253—C254—C255	179.6 (2)
C152—C153—C154—C155	2.2 (4)	C252—C253—C254—C255	1.4 (4)
C153—C154—C155—O15	−179.2 (2)	O24—C254—C255—O25	−3.4 (3)
O14—C154—C155—O15	−2.5 (3)	C253—C254—C255—O25	179.2 (2)
C153—C154—C155—C156	−0.4 (4)	O24—C254—C255—C256	176.5 (2)
O14—C154—C155—C156	176.4 (2)	C253—C254—C255—C256	−1.0 (4)
O15—C155—C156—C151	177.0 (2)	O25—C255—C256—C251	179.6 (2)
C154—C155—C156—C151	−1.7 (4)	C254—C255—C256—C251	−0.3 (4)
C152—C151—C156—C155	1.9 (4)	C252—C251—C256—C255	1.1 (4)
C157—C151—C156—C155	−176.5 (2)	C257—C251—C256—C255	−175.6 (2)
C154—C153—O13—C136	175.9 (2)	C254—C253—O23—C236	177.0 (2)
C152—C153—O13—C136	−6.0 (4)	C252—C253—O23—C236	−4.9 (4)
C153—C154—O14—C137	−101.0 (3)	C253—C254—O24—C237	−97.7 (3)
C155—C154—O14—C137	82.3 (3)	C255—C254—O24—C237	84.9 (3)
C156—C155—O15—C138	2.4 (4)	C256—C255—O25—C238	3.9 (4)
C154—C155—O15—C138	−178.8 (2)	C254—C255—O25—C238	−176.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C112—H112···N151	0.95	2.48	3.004 (4)	115
C212—H212···N251	0.95	2.46	3.002 (4)	116
N151—H151···O13^i	0.88	2.57	3.316 (3)	144
N151—H151···O14^i	0.88	2.30	3.095 (3)	150
N251—H251···O24^ii	0.88	2.38	3.150 (3)	147

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