Tris(5-methyl-3-phenyl-1H-pyrazol-1-yl)methane

Harding, D.J.; Harding, P.; Plant, S.E.

doi:10.1107/S1600536808010866

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o896

doi:10.1107/S1600536808010866

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Tris(5-methyl-3-phenyl-1H-pyrazol-1-yl)methane

David J. Harding,^a ^* Phimphaka Harding ^a and Sarah E. Plant ^b

^aMolecular Technology Unit Cell, Department of Chemistry, Walailak University, Thasala, Nakorn Si Thammarat 80161, Thailand, and ^bDepartment of Chemistry, Faculty of Science, University of Sheffield, Brook Hill, Sheffield S3 7HF, England
^*Correspondence e-mail: hdavid@wu.ac.th

(Received 10 April 2008; accepted 18 April 2008; online 23 April 2008)

The first crystal structure of a second-generation tris(pyrazolyl)methane, namely the title compound, C₃₁H₂₈N₆, is reported. The molecule exhibits a helical conformation with an average twist of 35.1°. In addition, there are C—H⋯π interactions of 3.202 (2) Å between the pyrazole C—H group and neighbouring phenyl groups.

Related literature

For related literature, see: Astley et al. (1993 ); Fujisawa et al. (2004 ); Goodman & Bateman (2001 ); Ochando et al. (1997 ); Pettinari & Pettinari (2005 ); Reger et al. (2000 , 2002 ); Riche & Pascard-Billy (1974 ); Declercq & Van Meerssche (1984 ).

Experimental

Crystal data

C₃₁H₂₈N₆
M_r = 484.59
Monoclinic, C c
a = 6.678 (3) Å
b = 21.730 (9) Å
c = 17.831 (7) Å
β = 94.922 (7)°
V = 2578.2 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 (2) K
0.38 × 0.34 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.972, T_max = 0.984
9586 measured reflections
2932 independent reflections
2129 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.071
S = 0.98
2932 reflections
337 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010866/rk2085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010866/rk2085Isup2.hkl

checkCIF report

Comment top

Tris–(pyrazolyl)methanes (tpzm^R,R'), neutral analogues of the more widely studied tris–(pyrazolyl)borates (tp^R,R'), are an increasing important class of ligands with a wide variety of coordination and organometallic complexes now reported (Pettinari & Pettinari, 2005). In most of these studies only the simplest members of the series tpzm and tpzm^Me,Me which generally form inert sandwich complexes with first row transition metals are utilized (Astley et al., 1993; Reger et al., 2002). In contrast, second generation tris–(pyrazolyl)methane ligands (tpzm^Ph, tpzm^i–Pr and tpzm^t–Bu) remain poorly represented owing to their time consuming synthesis and low yields. However, Reger (Reger et al., 2000) recently reported an improved procedure for these ligands, while Fujisawa and co–workers (Fujisawa et al., 2004) have shown that even tzpm^{i–Pr,i–Pr} may be prepared. Structural studies of tris–(pyrazolyl)methanes are even rarer and to date only tpzm^Me,Me has been reported (Declercq & Van Meerssche, 1984; Ochando et al., 1997). Herein, we report the synthesis and the first structural characterization of a second generation tris–(pyrazolyl)methane ligand namely, tpzm^Ph,Me (I).

Colourless block shaped crystals of I were grown from CH₂Cl₂/n–hexane, the compound crystallizing in a monoclinic Cc space group. The structure of the molecule I is shown on Fig. 1. The pyrazoles are bonded to the central CH–group in a tetrahedral fashion with N—C1—N angles [112.8 (2)°, 110.4 (2)° and 111.1 (2)°] close to the ideal tetrahedral value of 109.5° and similar to those found in tpzm^Me,Me [110°, 111°, 111° (Declercq & Van Meerssche, 1984)]. In addition, the structure shows that the methyl groups are in the 5–position of the pyrazole rings with the phenyl rings in the 3–position thereby minimizing steric congestion around the central CH–group and confirming the presence of a single regioisomer.

The propeller–like conformation of the molecule can be defined by the angle between the plane formed by H1A, C1 and the first pyrazole N atom and the mean plane of the pyrazole ring. The values for I are 50.4 (2)°, 18.7 (3)° and 36.3 (2)° and are comparable to those observed in the structures of tpzm^Me,Me [the values of each ring averaged over four molecules are 29 (3)°, 23 (2)° and 62 (1)° (Declercq & Van Meerssche, 1984)] and triphenylmethane [30°, 34° and 53°, and 21°, 38° and 47° for each one of the two molecules in the asymmetric unit (Riche & Pascard-Billy, 1974)]. A further method for describing this helical twist is through H1A–C1–N–N torsion angles (Ochando et al., 1997). The torsion angles for I are 133.7 (3)°, -18.3 (4)° and 148.9 (3)° for H1A–C1–N1–N2, H1A–C1–N3–N4 and H1A–C1–N5–N6, respectively. These are in good agreement with the values observed in tpzm^Me,Me [121 (1)°, -21 (1)° and 147 (1)° (Declercq & Van Meerssche, 1984)]. Assuming an α–conformation when the torsion angle is negative and β– when positive, it follows that the conformation in the case of I is β–α–β–, identical to the most stable conformer of tpzm^Me,Me (Declercq & Van Meerssche, 1984).

The pyrazole bond lengths in I vary between 1.328 (3)Å and 1.414 (3)Å and are very similar to those found in tpzm^Me,Me [1.33–1.40Å (Declercq & Van Meerssche, 1984)]. The phenyl rings are essentially co-planar with the pyrazole rings (dihedral angles: 3.4 (1)° and 2.8 (1)°) except in the case of the C20—N5 pyrazole ring in which the dihedral angles between the two planes is 15.7 (2)°.

A further point of interest is the packing within the structure of I which reveals C—H···π interactions between the pyrazole C3—H3 and the centroid of the ring C14/C15/C16/C17/C18/C19 (Cg), the phenyl group attached to the α–pyrazole (Fig. 2). All these interactions occur within a single layer of molecules with adjacent layers, which are related by inversion, exhibiting interactions in the opposite direction. Thus, the interactions H3 (x+1/2, y-1/2, z)···Cg (x, y, z) and H3 (x-1/2, -y+3/2, z-1/2)···Cgⁱⁱ (x-1, -y+1, z-1/2) are both 3.202 (2)Å.

Related literature top

For related literature, see: Astley et al. (1993); Fujisawa et al. (2004); Goodman & Bateman (2001); Ochando et al. (1997); Pettinari & Pettinari (2005); Reger et al. (2000, 2002); Riche & Pascard-Billy (1974); Declercq & Van Meerssche (1984).

Experimental top

Distilled water (20 ml) was added to a 250 ml flask containing a mixture of Hpz^Ph,Me (6.33 g, 40 mmol) and NBu₄Br (0.68 g, 2 mmol). With vigorous stirring Na₂CO₃ (8.5 g, 80 mmol) was added to the reaction mixture. After cooling CHCl₃ (75 ml) was added and the mixture refluxed for four days yielding a dark yellow–orange emulsion. The mixture was allowed to cool to room temperature and filtered through a Buchner funnel. The organic layer was separated from the aqueous layer, washed with water (3 × 30 ml) and dried over sodium sulfate. The solution was filtered to remove the drying agent and the solvent removed on a rotary evapourator to give a yellow solid. The solid was redissolved in toluene (70 ml) and a catalytic amount of p–toluenesulfonic acid (0.1 g, 0.53 mmol) was added. The solution was refluxed for a day giving a yellow solution. The solution was then cooled to room temperature, neutralized with a 5% aqueous Na₂CO₃ solution and washed with distilled water (3 × 15 ml). The solution was then dried over sodium sulfate, filtered and the solvent removed on a rotary evapourator resulting in a light brown solid. The solid was dissolved in CH₂Cl₂ (20 ml) and chromatographed on a silica gel column that was packed with a CH₂Cl₂:toluene (1:1) solution. The fractions containing the desired product were combined and the solvent removed by rotary evapouration to give an off–white solid (1.83 g, 29%). Analysis calculated for C₃₁H₂₈N₆: C 76.8, H 5.8, N 17.3%; found: C 76.7, H 5.8, N 17.0%. ESI⁺ MS: (m/z) Anal. Calc. 484.60; found: [MH]⁺485.65. ¹H–NMR (CDCl₃) δ 8.42 (s, 1H, CH), 7.77–7.72 [m, 6H, o–H (Ph)], 7.38–7.33 [m, 6H, m–H (Ph)], 7.30–7.28 [m, 3H, p–H, (Ph)], 6.47 [s, 3H, 4–H (pz)] and 2.22 (s, 9H, CH₃). It should be noted that I (see Fig. 3) was previously reported as a by–product in the synthesis of more complex tris–(pyrazolyl)methanes (Goodman & Bateman, 2001). However, it was not isolated and the above represents the first designed synthesis of I.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom–labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a spheres of arbitrary radius.
	Fig. 2. The molecular packing showing the C—H···π interactions in two adjacent chains. Only selected H atoms are shown and labelled for clarity. Symmetry codes: (i) x+1/2, y-1/2, z; (ii) x-1, -y+1, z-1/2; (iii) x-1/2, -y+3/2, z-1/2.
	Fig. 3. A schematic diagram of formation title compound.

Tris(5-methyl-3-phenyl-1H-pyrazol-1-yl)methane top

Crystal data top

C₃₁H₂₈N₆	F(000) = 1024
M_r = 484.59	D_x = 1.249 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 879 reflections
a = 6.678 (3) Å	θ = 4.6–46.9°
b = 21.730 (9) Å	µ = 0.08 mm⁻¹
c = 17.831 (7) Å	T = 150 K
β = 94.922 (7)°	Block, colourless
V = 2578.2 (19) Å³	0.38 × 0.34 × 0.21 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2932 independent reflections
Radiation source: Fine-focus sealed tube	2129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 100 pixels mm^-1	θ_max = 27.6°, θ_min = 1.9°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −27→25
T_min = 0.972, T_max = 0.984	l = −19→22
9586 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0288P)²] where P = (F_o² + 2F_c²)/3
2932 reflections	(Δ/σ)_max < 0.001
337 parameters	Δρ_max = 0.12 e Å⁻³
2 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₃₁H₂₈N₆	V = 2578.2 (19) Å³
M_r = 484.59	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 6.678 (3) Å	µ = 0.08 mm⁻¹
b = 21.730 (9) Å	T = 150 K
c = 17.831 (7) Å	0.38 × 0.34 × 0.21 mm
β = 94.922 (7)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2932 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2129 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.984	R_int = 0.039
9586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	2 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 0.98	Δρ_max = 0.12 e Å⁻³
2932 reflections	Δρ_min = −0.14 e Å⁻³
337 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F², conventional R–factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F² are statistically about twice as large as those based on F, and R–factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.8396 (3)	0.83570 (9)	0.68651 (11)	0.0408 (5)
N2	0.6619 (3)	0.85821 (9)	0.65488 (11)	0.0414 (5)
N3	0.8952 (3)	0.73399 (9)	0.73501 (11)	0.0401 (5)
N4	1.0565 (3)	0.69625 (9)	0.75166 (11)	0.0399 (5)
N5	0.7907 (3)	0.74998 (8)	0.60399 (11)	0.0396 (5)
N6	0.6231 (3)	0.71502 (9)	0.61064 (11)	0.0398 (5)
C1	0.9043 (4)	0.77355 (10)	0.67027 (14)	0.0420 (6)
H1A	1.0482	0.7759	0.6589	0.050*
C2	0.9315 (4)	0.87441 (12)	0.73918 (14)	0.0460 (6)
C3	0.8081 (4)	0.92398 (12)	0.74119 (15)	0.0493 (7)
H3A	0.8289	0.9592	0.7724	0.059*
C4	0.6429 (4)	0.91297 (11)	0.68788 (15)	0.0410 (6)
C5	0.4662 (4)	0.95123 (10)	0.66896 (14)	0.0424 (6)
C6	0.3172 (4)	0.93283 (12)	0.61469 (16)	0.0551 (7)
H6A	0.3321	0.8955	0.5880	0.066*
C7	0.1474 (5)	0.96829 (13)	0.59919 (17)	0.0646 (8)
H7A	0.0455	0.9546	0.5625	0.077*
C8	0.1229 (5)	1.02323 (13)	0.63600 (19)	0.0625 (8)
H8A	0.0065	1.0477	0.6244	0.075*
C9	0.2681 (5)	1.04169 (12)	0.68914 (18)	0.0609 (8)
H9A	0.2528	1.0794	0.7149	0.073*
C10	0.4385 (4)	1.00619 (12)	0.70633 (16)	0.0548 (7)
H10A	0.5375	1.0197	0.7442	0.066*
C11	0.7515 (3)	0.72783 (11)	0.78425 (14)	0.0399 (6)
C12	0.8255 (3)	0.68485 (11)	0.83497 (14)	0.0407 (6)
H12A	0.7622	0.6704	0.8773	0.049*
C13	1.0131 (3)	0.66587 (11)	0.81285 (13)	0.0372 (6)
C14	1.1513 (4)	0.61970 (11)	0.84821 (14)	0.0396 (6)
C15	1.0996 (4)	0.58720 (12)	0.91093 (15)	0.0502 (7)
H15A	0.9766	0.5960	0.9318	0.060*
C16	1.2253 (5)	0.54219 (12)	0.94321 (17)	0.0597 (8)
H16A	1.1882	0.5204	0.9861	0.072*
C17	1.4041 (5)	0.52873 (12)	0.91364 (17)	0.0582 (8)
H17A	1.4890	0.4972	0.9353	0.070*
C18	1.4588 (4)	0.56126 (12)	0.85242 (16)	0.0520 (7)
H18A	1.5836	0.5528	0.8327	0.062*
C19	1.3338 (4)	0.60609 (11)	0.81947 (15)	0.0443 (6)
H19A	1.3726	0.6278	0.7768	0.053*
C20	0.8150 (4)	0.76617 (11)	0.53141 (14)	0.0404 (6)
C21	0.6590 (4)	0.73918 (10)	0.48918 (14)	0.0412 (6)
H21A	0.6326	0.7412	0.4360	0.049*
C22	0.5452 (4)	0.70774 (10)	0.53982 (13)	0.0377 (6)
C23	0.3596 (4)	0.67181 (10)	0.52414 (14)	0.0394 (6)
C24	0.2386 (4)	0.65752 (11)	0.58115 (15)	0.0471 (7)
H24A	0.2784	0.6699	0.6313	0.057*
C25	0.0610 (4)	0.62552 (12)	0.56614 (18)	0.0548 (7)
H25A	−0.0209	0.6165	0.6058	0.066*
C26	0.0024 (4)	0.60663 (12)	0.49386 (19)	0.0565 (8)
H26A	−0.1195	0.5844	0.4837	0.068*
C27	0.1197 (4)	0.61980 (12)	0.43680 (18)	0.0589 (8)
H27A	0.0792	0.6067	0.3870	0.071*
C28	0.2975 (4)	0.65226 (12)	0.45144 (16)	0.0521 (7)
H28A	0.3780	0.6613	0.4114	0.063*
C29	1.1317 (4)	0.86029 (13)	0.77999 (16)	0.0595 (8)
H29A	1.2324	0.8556	0.7435	0.089*
H29B	1.1226	0.8220	0.8085	0.089*
H29C	1.1711	0.8940	0.8146	0.089*
C30	0.5591 (3)	0.76287 (12)	0.78100 (15)	0.0480 (7)
H30A	0.4767	0.7475	0.8199	0.072*
H30B	0.4864	0.7575	0.7313	0.072*
H30C	0.5879	0.8066	0.7897	0.072*
C31	0.9840 (4)	0.80561 (11)	0.51083 (16)	0.0507 (7)
H31A	1.1115	0.7841	0.5231	0.076*
H31B	0.9839	0.8443	0.5391	0.076*
H31C	0.9678	0.8144	0.4567	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0423 (12)	0.0441 (11)	0.0359 (12)	0.0008 (10)	0.0025 (9)	−0.0004 (10)
N2	0.0439 (12)	0.0417 (11)	0.0386 (13)	0.0028 (10)	0.0028 (10)	−0.0013 (9)
N3	0.0347 (11)	0.0516 (12)	0.0345 (12)	0.0015 (10)	0.0054 (10)	0.0045 (10)
N4	0.0364 (12)	0.0466 (12)	0.0365 (13)	0.0008 (10)	0.0019 (9)	0.0010 (10)
N5	0.0442 (12)	0.0422 (11)	0.0328 (12)	0.0058 (10)	0.0060 (9)	0.0017 (10)
N6	0.0423 (12)	0.0414 (11)	0.0369 (13)	0.0030 (10)	0.0107 (10)	0.0002 (9)
C1	0.0382 (14)	0.0485 (14)	0.0396 (15)	0.0011 (12)	0.0062 (11)	0.0061 (12)
C2	0.0451 (15)	0.0576 (17)	0.0359 (15)	−0.0132 (13)	0.0060 (12)	−0.0006 (12)
C3	0.0578 (17)	0.0462 (15)	0.0442 (17)	−0.0088 (14)	0.0069 (14)	−0.0074 (12)
C4	0.0465 (16)	0.0419 (14)	0.0361 (15)	−0.0053 (12)	0.0126 (12)	−0.0019 (12)
C5	0.0493 (15)	0.0375 (13)	0.0416 (16)	−0.0019 (12)	0.0107 (13)	0.0032 (12)
C6	0.0687 (19)	0.0474 (15)	0.0473 (18)	0.0085 (15)	−0.0057 (15)	−0.0020 (13)
C7	0.068 (2)	0.0641 (19)	0.060 (2)	0.0108 (17)	−0.0085 (16)	0.0016 (16)
C8	0.0616 (19)	0.0496 (17)	0.078 (2)	0.0107 (15)	0.0150 (17)	0.0142 (16)
C9	0.0630 (19)	0.0450 (16)	0.078 (2)	−0.0001 (15)	0.0269 (17)	−0.0077 (15)
C10	0.0533 (18)	0.0496 (16)	0.063 (2)	−0.0092 (14)	0.0164 (15)	−0.0113 (14)
C11	0.0350 (14)	0.0517 (15)	0.0334 (14)	−0.0044 (12)	0.0053 (11)	−0.0031 (12)
C12	0.0401 (15)	0.0504 (15)	0.0322 (15)	−0.0063 (12)	0.0075 (12)	0.0014 (12)
C13	0.0401 (15)	0.0416 (13)	0.0294 (14)	−0.0063 (11)	−0.0001 (11)	−0.0031 (11)
C14	0.0452 (16)	0.0396 (13)	0.0332 (15)	−0.0083 (11)	−0.0006 (12)	−0.0033 (11)
C15	0.0564 (16)	0.0508 (16)	0.0432 (17)	−0.0055 (14)	0.0030 (14)	0.0046 (14)
C16	0.077 (2)	0.0524 (17)	0.0489 (19)	−0.0083 (16)	−0.0014 (17)	0.0121 (14)
C17	0.076 (2)	0.0380 (15)	0.058 (2)	0.0083 (15)	−0.0095 (17)	−0.0016 (14)
C18	0.0573 (17)	0.0461 (15)	0.0511 (18)	0.0056 (14)	−0.0031 (14)	−0.0081 (14)
C19	0.0487 (15)	0.0450 (14)	0.0385 (15)	−0.0038 (12)	0.0000 (12)	−0.0035 (12)
C20	0.0498 (15)	0.0391 (13)	0.0336 (15)	0.0142 (12)	0.0100 (12)	0.0057 (11)
C21	0.0550 (16)	0.0388 (13)	0.0300 (14)	0.0104 (12)	0.0052 (12)	0.0031 (11)
C22	0.0464 (15)	0.0364 (13)	0.0306 (15)	0.0123 (11)	0.0058 (12)	0.0000 (11)
C23	0.0469 (15)	0.0329 (12)	0.0392 (15)	0.0096 (11)	0.0071 (12)	0.0007 (11)
C24	0.0551 (18)	0.0460 (15)	0.0415 (17)	0.0071 (13)	0.0109 (13)	−0.0008 (13)
C25	0.0552 (18)	0.0478 (15)	0.063 (2)	0.0039 (14)	0.0157 (16)	0.0076 (15)
C26	0.0553 (17)	0.0434 (15)	0.071 (2)	−0.0035 (13)	0.0063 (17)	0.0008 (15)
C27	0.067 (2)	0.0563 (17)	0.052 (2)	−0.0106 (16)	−0.0026 (16)	−0.0054 (14)
C28	0.0645 (19)	0.0527 (16)	0.0399 (16)	−0.0016 (14)	0.0089 (13)	−0.0022 (13)
C29	0.0482 (17)	0.0744 (19)	0.0541 (19)	−0.0096 (15)	−0.0048 (14)	0.0007 (15)
C30	0.0402 (15)	0.0602 (17)	0.0444 (16)	0.0039 (13)	0.0087 (12)	−0.0032 (13)
C31	0.0552 (17)	0.0533 (16)	0.0447 (17)	0.0041 (14)	0.0098 (13)	0.0089 (13)

Geometric parameters (Å, º) top

N1—N2	1.360 (3)	C14—C19	1.394 (4)
N1—C2	1.367 (3)	C15—C16	1.382 (4)
N1—C1	1.455 (3)	C15—H15A	0.9500
N2—C4	1.338 (3)	C16—C17	1.378 (4)
N3—C11	1.361 (3)	C16—H16A	0.9500
N3—N4	1.366 (3)	C17—C18	1.376 (4)
N3—C1	1.445 (3)	C17—H17A	0.9500
N4—C13	1.328 (3)	C18—C19	1.381 (3)
N5—C20	1.364 (3)	C18—H18A	0.9500
N5—N6	1.366 (3)	C19—H19A	0.9500
N5—C1	1.443 (3)	C20—C21	1.364 (3)
N6—C22	1.334 (3)	C20—C31	1.488 (3)
C1—H1A	1.0000	C21—C22	1.406 (3)
C2—C3	1.358 (4)	C21—H21A	0.9500
C2—C29	1.498 (4)	C22—C23	1.471 (3)
C3—C4	1.414 (3)	C23—C24	1.387 (3)
C3—H3A	0.9500	C23—C28	1.393 (4)
C4—C5	1.459 (3)	C24—C25	1.381 (4)
C5—C6	1.386 (3)	C24—H24A	0.9500
C5—C10	1.388 (3)	C25—C26	1.377 (4)
C6—C7	1.379 (4)	C25—H25A	0.9500
C6—H6A	0.9500	C26—C27	1.366 (4)
C7—C8	1.379 (4)	C26—H26A	0.9500
C7—H7A	0.9500	C27—C28	1.387 (4)
C8—C9	1.357 (4)	C27—H27A	0.9500
C8—H8A	0.9500	C28—H28A	0.9500
C9—C10	1.387 (4)	C29—H29A	0.9800
C9—H9A	0.9500	C29—H29B	0.9800
C10—H10A	0.9500	C29—H29C	0.9800
C11—C12	1.363 (3)	C30—H30A	0.9800
C11—C30	1.490 (3)	C30—H30B	0.9800
C12—C13	1.407 (3)	C30—H30C	0.9800
C12—H12A	0.9500	C31—H31A	0.9800
C13—C14	1.468 (3)	C31—H31B	0.9800
C14—C15	1.391 (3)	C31—H31C	0.9800

N2—N1—C2	112.83 (19)	C14—C15—H15A	119.6
N2—N1—C1	120.99 (19)	C17—C16—C15	120.4 (3)
C2—N1—C1	125.8 (2)	C17—C16—H16A	119.8
C4—N2—N1	104.46 (19)	C15—C16—H16A	119.8
C11—N3—N4	112.77 (19)	C18—C17—C16	119.5 (3)
C11—N3—C1	130.86 (19)	C18—C17—H17A	120.2
N4—N3—C1	116.37 (19)	C16—C17—H17A	120.2
C13—N4—N3	104.67 (19)	C17—C18—C19	120.5 (3)
C20—N5—N6	113.01 (19)	C17—C18—H18A	119.7
C20—N5—C1	126.1 (2)	C19—C18—H18A	119.7
N6—N5—C1	120.23 (19)	C18—C19—C14	120.6 (3)
C22—N6—N5	103.87 (19)	C18—C19—H19A	119.7
N5—C1—N3	112.83 (19)	C14—C19—H19A	119.7
N5—C1—N1	110.38 (18)	N5—C20—C21	105.4 (2)
N3—C1—N1	111.1 (2)	N5—C20—C31	122.5 (2)
N5—C1—H1A	107.4	C21—C20—C31	132.1 (2)
N3—C1—H1A	107.4	C20—C21—C22	106.5 (2)
N1—C1—H1A	107.4	C20—C21—H21A	126.8
C3—C2—N1	105.6 (2)	C22—C21—H21A	126.8
C3—C2—C29	131.9 (3)	N6—C22—C21	111.2 (2)
N1—C2—C29	122.5 (3)	N6—C22—C23	119.8 (2)
C2—C3—C4	106.8 (2)	C21—C22—C23	129.0 (2)
C2—C3—H3A	126.6	C24—C23—C28	117.9 (2)
C4—C3—H3A	126.6	C24—C23—C22	120.9 (2)
N2—C4—C3	110.4 (2)	C28—C23—C22	121.1 (2)
N2—C4—C5	120.7 (2)	C25—C24—C23	121.0 (3)
C3—C4—C5	128.9 (2)	C25—C24—H24A	119.5
C6—C5—C10	117.8 (3)	C23—C24—H24A	119.5
C6—C5—C4	121.0 (2)	C26—C25—C24	120.1 (3)
C10—C5—C4	121.2 (2)	C26—C25—H25A	119.9
C7—C6—C5	120.5 (3)	C24—C25—H25A	119.9
C7—C6—H6A	119.7	C27—C26—C25	120.0 (3)
C5—C6—H6A	119.7	C27—C26—H26A	120.0
C6—C7—C8	121.1 (3)	C25—C26—H26A	120.0
C6—C7—H7A	119.4	C26—C27—C28	120.2 (3)
C8—C7—H7A	119.4	C26—C27—H27A	119.9
C9—C8—C7	118.8 (3)	C28—C27—H27A	119.9
C9—C8—H8A	120.6	C27—C28—C23	120.8 (3)
C7—C8—H8A	120.6	C27—C28—H28A	119.6
C8—C9—C10	120.9 (3)	C23—C28—H28A	119.6
C8—C9—H9A	119.6	C2—C29—H29A	109.5
C10—C9—H9A	119.6	C2—C29—H29B	109.5
C9—C10—C5	120.9 (3)	H29A—C29—H29B	109.5
C9—C10—H10A	119.6	C2—C29—H29C	109.5
C5—C10—H10A	119.6	H29A—C29—H29C	109.5
N3—C11—C12	105.1 (2)	H29B—C29—H29C	109.5
N3—C11—C30	125.3 (2)	C11—C30—H30A	109.5
C12—C11—C30	129.6 (2)	C11—C30—H30B	109.5
C11—C12—C13	107.2 (2)	H30A—C30—H30B	109.5
C11—C12—H12A	126.4	C11—C30—H30C	109.5
C13—C12—H12A	126.4	H30A—C30—H30C	109.5
N4—C13—C12	110.3 (2)	H30B—C30—H30C	109.5
N4—C13—C14	121.3 (2)	C20—C31—H31A	109.5
C12—C13—C14	128.4 (2)	C20—C31—H31B	109.5
C15—C14—C19	118.2 (2)	H31A—C31—H31B	109.5
C15—C14—C13	120.2 (2)	C20—C31—H31C	109.5
C19—C14—C13	121.6 (2)	H31A—C31—H31C	109.5
C16—C15—C14	120.7 (3)	H31B—C31—H31C	109.5
C16—C15—H15A	119.6

Experimental details

Crystal data
Chemical formula	C₃₁H₂₈N₆
M_r	484.59
Crystal system, space group	Monoclinic, Cc
Temperature (K)	150
a, b, c (Å)	6.678 (3), 21.730 (9), 17.831 (7)
β (°)	94.922 (7)
V (Å³)	2578.2 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.38 × 0.34 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.972, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	9586, 2932, 2129
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.071, 0.98
No. of reflections	2932
No. of parameters	337
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors gratefully acknowledge the Institute for Research and Development, Walailak University for supporting this work (grant No. 5/2550).

References

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