2,6-Bis(1-isopropyl-5-phenyl-1H-pyrazol-3-yl)pyridine

Liu, P.; Zhou, Y.-B.; Li, M.-G.; An, C.-X.

doi:10.1107/S1600536807065191

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o226

https://doi.org/10.1107/S1600536807065191

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2,6-Bis(1-isopropyl-5-phenyl-1H-pyrazol-3-yl)pyridine

Ping Liu,^a Yong-Bo Zhou,^b ^* Min-Guo Li ^c and Cai-Xia An ^a

^aSchool of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, Henan 453003, People's Republic of China, ^bDepartment of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, People's Republic of China, and ^cDepartment of Agriculture, Guangshan County, Henan 465400, People's Republic of China
^*Correspondence e-mail: zybdjy@163.com

(Received 20 November 2007; accepted 3 December 2007; online 6 December 2007)

In the title compound, C₂₉H₂₉N₅, the central pyridine ring and the two pyrazole rings are approximately coplanar, the dihedral angles between the pyridine and pyrazole rings being 3.94 (12) and 14.84 (12)°. The pyrazole and phenyl rings on each side of the molecule are twisted with dihedral angles of 46.72 (8) and 73.39 (8)°. One phenyl ring interacts with a pyrazole ring of a neighbouring molecule via a weak intermolecular C—H⋯π interaction, which stabilizes the molecular packing.

Related literature

For general background, see: Dias & Gamage (2007 ); Zhou & Chen (2007 ).

Experimental

Crystal data

C₂₉H₂₉N₅
M_r = 447.57
Triclinic, $[P \overline 1]$
a = 9.973 (3) Å
b = 10.172 (3) Å
c = 14.014 (4) Å
α = 110.940 (4)°
β = 106.494 (4)°
γ = 94.583 (4)°
V = 1246.8 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 (2) K
0.53 × 0.43 × 0.39 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.963, T_max = 0.972
6572 measured reflections
4332 independent reflections
2417 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.123
S = 1.05
4332 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20⋯Cg1ⁱ	0.93	2.86	3.710 (3)	153
Symmetry code: (i) -x+1, -y, -z. Cg1 is the centroid of the C6-C8/N2/N3 pyrazole ring.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807065191/is2264sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065191/is2264Isup2.hkl

checkCIF report

Comment top

Pyrazolyl ligands are a kind of mutifuntional organic ligands often displaying exo-bidentate coordination mode (Dias & Gamage, 2007). The title compound, 2,6-bis(5-phenyl-1-isopropyl-1H-pyrazol-3-yl)pyridine (hereinafter abbreviated to bpipp), is a potentially tridentate pincer ligand by N-alkylation of a bispyrazolyl ligand.

The asymmetric unit of the title compound contains only one bpipp molecule (Fig. 1). The pyrazole and pyridine rings are near-coplanar [inter-ring dihedral angles 3.94 (12) and 14.84 (12)°], whereas the pyrazole rings are twisted from the phenyl rings with the two dihedral angles 46.72 (8) and 73.39 (8)°. The phenyl ring interacts with the pyrazole ring of the neighbouring molecule to afford a weak intermolecular C—H··· π interaction (Table 1; Cg1 is the centroid of the C6—C8/N2/N3 pyrazole ring) which stabilizes the molecular packing. The centroid to centroid distance between stacked pyridine rings is ca 4.88 Å, which is very long and prevents π-π stacking (Fig. 2). All bond lengths and angles are normal.

Related literature top

For general background, see: Dias & Gamage (2007); Zhou & Chen (2007). Cg1 is the centroid of the C6—C8/N2/N3 pyrazole ring.

Experimental top

All chemicals were of reagent grade quality obtained from commercial sources and used as received, unless stated otherwise. 2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine (bppp) was prepared by the general procedure of Zhou and Chen (2007). A mixture of bppp (0.72 g, 2 mmol) and 60% NaH (0.32 g, 8 mmol) in dry DMF (15 ml) was stirred for 2 h at room temperature. To the solution was added 2-bromopropane (0.98 g, 8 mmol). After stirring at 333 K for two days, the resulting solution was concentrated to 4 ml. Addition of H₂O (15 ml) precipitated a pale yellow powder. Column chromatography involved elution with ethyl acetate/ petroleum ether (1:4) separated the compound as a white powder (0.56 g). Yield: 62%. Anal. Calcd for C₂₉H₂₉N₅: C 77.82, H 6.53, N 15.65; Found: C 77.60, H 6.62, N 15.57. MS (m/z): 447 (M⁺, 100), 432, 405, 390, 363, 334, 304, 195, 168, 115, 77. ¹H NMR (DMSO-d₆): 7.90 (br, 3H), 7.56–7.48 (m, 10H), 6.99 (s, 2H), 4.58(m, 2H), 1.47(s, 6H), 1.45 (s, 6H). ¹³C NMR (100 MHz, DMSO-d₆): δ 151.8, 150.5, 144.5, 130.6, 129.3, 129.2, 129.0, 125.14, 118.1, 104.8, 50.3, 23.2, 23.1. Colorless single crystals were grown from slow evaporation of a saturated MeOH solution of the compound.

Structure description top

For general background, see: Dias & Gamage (2007); Zhou & Chen (2007). Cg1 is the centroid of the C6—C8/N2/N3 pyrazole ring.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and publCIF (Westrip, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing view of the title compound along the b axis. H atoms have been omitted for clarity.

2,6-Bis(1-isopropyl-5-phenyl-1H-pyrazol-3-yl)pyridine top

Crystal data top

C₂₉H₂₉N₅	Z = 2
M_r = 447.57	F(000) = 476
Triclinic, P1	D_x = 1.192 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.973 (3) Å	Cell parameters from 1546 reflections
b = 10.172 (3) Å	θ = 2.8–21.8°
c = 14.014 (4) Å	µ = 0.07 mm⁻¹
α = 110.940 (4)°	T = 298 K
β = 106.494 (4)°	Prism, colorless
γ = 94.583 (4)°	0.53 × 0.43 × 0.39 mm
V = 1246.8 (6) Å³

Data collection top

SMART 1K CCD area-detector diffractometer	4332 independent reflections
Radiation source: fine-focus sealed tube	2417 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −11→7
T_min = 0.963, T_max = 0.972	k = −10→12
6572 measured reflections	l = −15→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0483P)² + 0.0355P] where P = (F_o² + 2F_c²)/3
4332 reflections	(Δ/σ)_max < 0.001
307 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₉H₂₉N₅	γ = 94.583 (4)°
M_r = 447.57	V = 1246.8 (6) Å³
Triclinic, P1	Z = 2
a = 9.973 (3) Å	Mo Kα radiation
b = 10.172 (3) Å	µ = 0.07 mm⁻¹
c = 14.014 (4) Å	T = 298 K
α = 110.940 (4)°	0.53 × 0.43 × 0.39 mm
β = 106.494 (4)°

Data collection top

SMART 1K CCD area-detector diffractometer	4332 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	2417 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.972	R_int = 0.023
6572 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	Δρ_max = 0.14 e Å⁻³
4332 reflections	Δρ_min = −0.18 e Å⁻³
307 parameters

Special details top

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

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.49140 (17)	0.25670 (17)	0.32171 (13)	0.0437 (5)
N2	0.75204 (19)	0.58665 (18)	0.45974 (14)	0.0507 (5)
N3	0.77219 (19)	0.67986 (18)	0.41370 (14)	0.0510 (5)
N4	0.28141 (19)	−0.09220 (18)	0.24676 (14)	0.0522 (5)
N5	0.19993 (19)	−0.17780 (17)	0.14410 (14)	0.0519 (5)
C1	0.4400 (2)	0.1424 (2)	0.33672 (17)	0.0419 (5)
C2	0.4774 (2)	0.1347 (2)	0.43729 (17)	0.0494 (6)
H2	0.4400	0.0539	0.4450	0.059*
C3	0.5705 (2)	0.2481 (2)	0.52506 (18)	0.0520 (6)
H3	0.5976	0.2451	0.5933	0.062*
C4	0.6235 (2)	0.3662 (2)	0.51153 (17)	0.0491 (6)
H4	0.6857	0.4449	0.5705	0.059*
C5	0.5832 (2)	0.3665 (2)	0.40889 (17)	0.0412 (5)
C6	0.6374 (2)	0.4876 (2)	0.38672 (17)	0.0437 (5)
C7	0.5864 (2)	0.5158 (2)	0.29458 (17)	0.0473 (6)
H7	0.5088	0.4614	0.2327	0.057*
C8	0.6735 (2)	0.6402 (2)	0.31321 (18)	0.0468 (6)
C9	0.6679 (2)	0.7231 (2)	0.24527 (19)	0.0492 (6)
C10	0.6480 (3)	0.6519 (3)	0.1365 (2)	0.0699 (8)
H10	0.6402	0.5528	0.1073	0.084*
C11	0.6396 (3)	0.7265 (4)	0.0706 (2)	0.0927 (10)
H11	0.6257	0.6775	−0.0027	0.111*
C12	0.6517 (3)	0.8726 (4)	0.1130 (3)	0.0894 (9)
H12	0.6478	0.9227	0.0687	0.107*
C13	0.6693 (3)	0.9441 (3)	0.2190 (3)	0.0743 (8)
H13	0.6771	1.0433	0.2475	0.089*
C14	0.6757 (3)	0.8699 (3)	0.2845 (2)	0.0623 (7)
H14	0.6856	0.9196	0.3569	0.075*
C15	0.3432 (2)	0.0234 (2)	0.23969 (17)	0.0436 (5)
C16	0.3022 (2)	0.0097 (2)	0.13208 (17)	0.0489 (6)
H16	0.3311	0.0759	0.1065	0.059*
C17	0.2110 (2)	−0.1202 (2)	0.07220 (16)	0.0454 (6)
C18	0.1321 (3)	−0.1941 (2)	−0.04508 (17)	0.0469 (6)
C19	0.2024 (3)	−0.2537 (3)	−0.1166 (2)	0.0655 (7)
H19	0.3005	−0.2471	−0.0907	0.079*
C20	0.1282 (3)	−0.3234 (3)	−0.2265 (2)	0.0724 (8)
H20	0.1766	−0.3643	−0.2740	0.087*
C21	−0.0148 (3)	−0.3324 (2)	−0.2656 (2)	0.0632 (7)
H21	−0.0641	−0.3793	−0.3397	0.076*
C22	−0.0861 (3)	−0.2729 (3)	−0.1964 (2)	0.0647 (7)
H22	−0.1841	−0.2792	−0.2230	0.078*
C23	−0.0128 (3)	−0.2035 (2)	−0.08679 (19)	0.0603 (7)
H23	−0.0620	−0.1621	−0.0401	0.072*
C24	0.9034 (2)	0.7923 (2)	0.46856 (19)	0.0549 (6)
H24	0.9062	0.8436	0.4216	0.066*
C25	1.0336 (3)	0.7258 (3)	0.4818 (2)	0.0694 (7)
H25A	1.0305	0.6584	0.4122	0.104*
H25B	1.0354	0.6768	0.5292	0.104*
H25C	1.1180	0.7998	0.5123	0.104*
C26	0.8991 (3)	0.8999 (2)	0.5743 (2)	0.0707 (8)
H26A	0.8147	0.9392	0.5609	0.106*
H26B	0.9820	0.9759	0.6067	0.106*
H26C	0.8978	0.8530	0.6227	0.106*
C27	0.1273 (3)	−0.3221 (2)	0.12085 (19)	0.0606 (7)
H27	0.0613	−0.3627	0.0459	0.073*
C28	0.0417 (3)	−0.3145 (3)	0.1945 (3)	0.1074 (11)
H28A	−0.0257	−0.2539	0.1854	0.161*
H28B	0.1046	−0.2755	0.2684	0.161*
H28C	−0.0085	−0.4093	0.1766	0.161*
C29	0.2353 (3)	−0.4163 (3)	0.1301 (2)	0.0955 (10)
H29A	0.2869	−0.4181	0.0815	0.143*
H29B	0.1870	−0.5121	0.1116	0.143*
H29C	0.3007	−0.3787	0.2032	0.143*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0443 (11)	0.0382 (10)	0.0421 (11)	−0.0014 (9)	0.0103 (9)	0.0141 (9)
N2	0.0509 (12)	0.0475 (11)	0.0481 (11)	−0.0066 (9)	0.0097 (10)	0.0214 (9)
N3	0.0506 (12)	0.0459 (11)	0.0497 (12)	−0.0065 (9)	0.0095 (10)	0.0205 (9)
N4	0.0565 (12)	0.0441 (11)	0.0403 (11)	−0.0105 (9)	0.0036 (9)	0.0132 (9)
N5	0.0594 (13)	0.0424 (11)	0.0393 (11)	−0.0091 (9)	0.0037 (10)	0.0137 (9)
C1	0.0401 (13)	0.0374 (12)	0.0413 (13)	0.0013 (10)	0.0089 (10)	0.0131 (10)
C2	0.0519 (14)	0.0473 (13)	0.0439 (14)	−0.0016 (11)	0.0075 (12)	0.0214 (11)
C3	0.0570 (15)	0.0535 (14)	0.0390 (13)	−0.0010 (12)	0.0081 (12)	0.0197 (11)
C4	0.0458 (14)	0.0482 (14)	0.0410 (14)	−0.0025 (11)	0.0067 (11)	0.0124 (11)
C5	0.0390 (12)	0.0383 (12)	0.0410 (13)	0.0022 (10)	0.0116 (10)	0.0124 (10)
C6	0.0414 (13)	0.0403 (12)	0.0429 (14)	0.0002 (10)	0.0125 (11)	0.0123 (10)
C7	0.0460 (14)	0.0445 (13)	0.0404 (13)	−0.0023 (11)	0.0077 (11)	0.0121 (11)
C8	0.0447 (14)	0.0465 (13)	0.0443 (14)	0.0037 (11)	0.0114 (11)	0.0166 (11)
C9	0.0435 (14)	0.0525 (14)	0.0516 (15)	0.0037 (11)	0.0138 (11)	0.0239 (12)
C10	0.091 (2)	0.0616 (16)	0.0548 (17)	0.0085 (15)	0.0238 (15)	0.0228 (14)
C11	0.132 (3)	0.098 (2)	0.0558 (19)	0.021 (2)	0.0343 (18)	0.0376 (18)
C12	0.120 (3)	0.090 (2)	0.084 (2)	0.027 (2)	0.042 (2)	0.057 (2)
C13	0.090 (2)	0.0635 (17)	0.088 (2)	0.0216 (15)	0.0353 (18)	0.0445 (17)
C14	0.0726 (18)	0.0569 (16)	0.0619 (17)	0.0134 (13)	0.0242 (14)	0.0274 (14)
C15	0.0450 (13)	0.0386 (12)	0.0415 (13)	−0.0004 (10)	0.0093 (11)	0.0154 (10)
C16	0.0562 (15)	0.0434 (13)	0.0432 (14)	−0.0009 (11)	0.0111 (11)	0.0195 (11)
C17	0.0489 (14)	0.0437 (13)	0.0372 (13)	0.0027 (11)	0.0072 (11)	0.0157 (11)
C18	0.0556 (15)	0.0380 (12)	0.0382 (13)	0.0017 (11)	0.0077 (12)	0.0131 (10)
C19	0.0613 (17)	0.0722 (17)	0.0494 (17)	0.0066 (14)	0.0105 (14)	0.0167 (14)
C20	0.079 (2)	0.0789 (19)	0.0476 (17)	0.0149 (16)	0.0219 (15)	0.0116 (14)
C21	0.082 (2)	0.0518 (15)	0.0399 (15)	0.0044 (14)	0.0058 (15)	0.0136 (12)
C22	0.0591 (17)	0.0623 (16)	0.0521 (17)	0.0051 (13)	−0.0022 (14)	0.0172 (13)
C23	0.0582 (17)	0.0623 (16)	0.0450 (15)	0.0106 (13)	0.0088 (13)	0.0110 (12)
C24	0.0507 (15)	0.0502 (14)	0.0573 (16)	−0.0097 (12)	0.0108 (12)	0.0239 (12)
C25	0.0542 (17)	0.0721 (17)	0.0763 (19)	0.0010 (14)	0.0205 (14)	0.0266 (14)
C26	0.0722 (18)	0.0486 (15)	0.0715 (18)	−0.0080 (13)	0.0199 (15)	0.0092 (13)
C27	0.0692 (17)	0.0422 (14)	0.0496 (15)	−0.0176 (13)	−0.0001 (13)	0.0164 (12)
C28	0.107 (3)	0.091 (2)	0.120 (3)	−0.0275 (19)	0.048 (2)	0.038 (2)
C29	0.106 (2)	0.0529 (17)	0.105 (3)	0.0048 (17)	0.016 (2)	0.0243 (16)

Geometric parameters (Å, º) top

N1—C1	1.341 (2)	C15—C16	1.397 (3)
N1—C5	1.343 (2)	C16—C17	1.364 (3)
N2—C6	1.335 (2)	C16—H16	0.9300
N2—N3	1.355 (2)	C17—C18	1.474 (3)
N3—C8	1.363 (2)	C18—C19	1.377 (3)
N3—C24	1.474 (2)	C18—C23	1.378 (3)
N4—C15	1.332 (2)	C19—C20	1.383 (3)
N4—N5	1.348 (2)	C19—H19	0.9300
N5—C17	1.358 (3)	C20—C21	1.357 (3)
N5—C27	1.463 (2)	C20—H20	0.9300
C1—C2	1.385 (3)	C21—C22	1.362 (3)
C1—C15	1.462 (3)	C21—H21	0.9300
C2—C3	1.368 (3)	C22—C23	1.377 (3)
C2—H2	0.9300	C22—H22	0.9300
C3—C4	1.370 (3)	C23—H23	0.9300
C3—H3	0.9300	C24—C25	1.507 (3)
C4—C5	1.380 (3)	C24—C26	1.510 (3)
C4—H4	0.9300	C24—H24	0.9800
C5—C6	1.473 (3)	C25—H25A	0.9600
C6—C7	1.387 (3)	C25—H25B	0.9600
C7—C8	1.373 (3)	C25—H25C	0.9600
C7—H7	0.9300	C26—H26A	0.9600
C8—C9	1.474 (3)	C26—H26B	0.9600
C9—C10	1.380 (3)	C26—H26C	0.9600
C9—C14	1.381 (3)	C27—C28	1.501 (4)
C10—C11	1.378 (3)	C27—C29	1.506 (3)
C10—H10	0.9300	C27—H27	0.9800
C11—C12	1.369 (4)	C28—H28A	0.9600
C11—H11	0.9300	C28—H28B	0.9600
C12—C13	1.351 (4)	C28—H28C	0.9600
C12—H12	0.9300	C29—H29A	0.9600
C13—C14	1.374 (3)	C29—H29B	0.9600
C13—H13	0.9300	C29—H29C	0.9600
C14—H14	0.9300

C1—N1—C5	117.55 (18)	N5—C17—C16	105.95 (18)
C6—N2—N3	104.67 (17)	N5—C17—C18	122.37 (18)
N2—N3—C8	112.07 (16)	C16—C17—C18	131.7 (2)
N2—N3—C24	117.84 (17)	C19—C18—C23	118.0 (2)
C8—N3—C24	129.40 (18)	C19—C18—C17	120.6 (2)
C15—N4—N5	104.86 (17)	C23—C18—C17	121.5 (2)
N4—N5—C17	112.34 (16)	C18—C19—C20	120.6 (2)
N4—N5—C27	119.23 (17)	C18—C19—H19	119.7
C17—N5—C27	127.95 (18)	C20—C19—H19	119.7
N1—C1—C2	122.68 (18)	C21—C20—C19	120.4 (3)
N1—C1—C15	116.11 (18)	C21—C20—H20	119.8
C2—C1—C15	121.20 (18)	C19—C20—H20	119.8
C3—C2—C1	118.8 (2)	C20—C21—C22	120.0 (2)
C3—C2—H2	120.6	C20—C21—H21	120.0
C1—C2—H2	120.6	C22—C21—H21	120.0
C2—C3—C4	119.5 (2)	C21—C22—C23	119.9 (2)
C2—C3—H3	120.3	C21—C22—H22	120.1
C4—C3—H3	120.3	C23—C22—H22	120.1
C3—C4—C5	118.91 (19)	C22—C23—C18	121.2 (3)
C3—C4—H4	120.5	C22—C23—H23	119.4
C5—C4—H4	120.5	C18—C23—H23	119.4
N1—C5—C4	122.63 (18)	N3—C24—C25	110.52 (18)
N1—C5—C6	114.89 (18)	N3—C24—C26	110.4 (2)
C4—C5—C6	122.47 (18)	C25—C24—C26	113.2 (2)
N2—C6—C7	111.30 (18)	N3—C24—H24	107.5
N2—C6—C5	120.23 (19)	C25—C24—H24	107.5
C7—C6—C5	128.46 (19)	C26—C24—H24	107.5
C8—C7—C6	106.11 (18)	C24—C25—H25A	109.5
C8—C7—H7	126.9	C24—C25—H25B	109.5
C6—C7—H7	126.9	H25A—C25—H25B	109.5
N3—C8—C7	105.83 (18)	C24—C25—H25C	109.5
N3—C8—C9	123.87 (18)	H25A—C25—H25C	109.5
C7—C8—C9	130.3 (2)	H25B—C25—H25C	109.5
C10—C9—C14	117.7 (2)	C24—C26—H26A	109.5
C10—C9—C8	119.4 (2)	C24—C26—H26B	109.5
C14—C9—C8	122.9 (2)	H26A—C26—H26B	109.5
C11—C10—C9	120.6 (3)	C24—C26—H26C	109.5
C11—C10—H10	119.7	H26A—C26—H26C	109.5
C9—C10—H10	119.7	H26B—C26—H26C	109.5
C12—C11—C10	120.1 (3)	N5—C27—C28	110.2 (2)
C12—C11—H11	120.0	N5—C27—C29	109.6 (2)
C10—C11—H11	120.0	C28—C27—C29	112.5 (2)
C13—C12—C11	120.3 (3)	N5—C27—H27	108.2
C13—C12—H12	119.8	C28—C27—H27	108.2
C11—C12—H12	119.8	C29—C27—H27	108.2
C12—C13—C14	119.7 (3)	C27—C28—H28A	109.5
C12—C13—H13	120.1	C27—C28—H28B	109.5
C14—C13—H13	120.1	H28A—C28—H28B	109.5
C13—C14—C9	121.5 (2)	C27—C28—H28C	109.5
C13—C14—H14	119.2	H28A—C28—H28C	109.5
C9—C14—H14	119.2	H28B—C28—H28C	109.5
N4—C15—C16	110.78 (18)	C27—C29—H29A	109.5
N4—C15—C1	120.71 (19)	C27—C29—H29B	109.5
C16—C15—C1	128.51 (19)	H29A—C29—H29B	109.5
C17—C16—C15	106.06 (18)	C27—C29—H29C	109.5
C17—C16—H16	127.0	H29A—C29—H29C	109.5
C15—C16—H16	127.0	H29B—C29—H29C	109.5

C6—N2—N3—C8	−0.6 (2)	C12—C13—C14—C9	1.5 (4)
C6—N2—N3—C24	−171.95 (18)	C10—C9—C14—C13	−2.3 (4)
C15—N4—N5—C17	1.2 (2)	C8—C9—C14—C13	−179.6 (2)
C15—N4—N5—C27	173.9 (2)	N5—N4—C15—C16	−0.8 (2)
C5—N1—C1—C2	0.3 (3)	N5—N4—C15—C1	179.42 (19)
C5—N1—C1—C15	−178.48 (18)	N1—C1—C15—N4	−176.9 (2)
N1—C1—C2—C3	0.0 (3)	C2—C1—C15—N4	4.3 (3)
C15—C1—C2—C3	178.8 (2)	N1—C1—C15—C16	3.4 (3)
C1—C2—C3—C4	0.3 (3)	C2—C1—C15—C16	−175.4 (2)
C2—C3—C4—C5	−1.1 (3)	N4—C15—C16—C17	0.2 (3)
C1—N1—C5—C4	−1.1 (3)	C1—C15—C16—C17	179.9 (2)
C1—N1—C5—C6	179.08 (18)	N4—N5—C17—C16	−1.1 (3)
C3—C4—C5—N1	1.5 (3)	C27—N5—C17—C16	−173.0 (2)
C3—C4—C5—C6	−178.7 (2)	N4—N5—C17—C18	179.9 (2)
N3—N2—C6—C7	0.9 (2)	C27—N5—C17—C18	8.0 (4)
N3—N2—C6—C5	179.74 (19)	C15—C16—C17—N5	0.5 (2)
N1—C5—C6—N2	−164.57 (19)	C15—C16—C17—C18	179.4 (2)
C4—C5—C6—N2	15.6 (3)	N5—C17—C18—C19	−107.9 (3)
N1—C5—C6—C7	14.0 (3)	C16—C17—C18—C19	73.4 (3)
C4—C5—C6—C7	−165.8 (2)	N5—C17—C18—C23	73.3 (3)
N2—C6—C7—C8	−0.9 (3)	C16—C17—C18—C23	−105.4 (3)
C5—C6—C7—C8	−179.6 (2)	C23—C18—C19—C20	−1.4 (4)
N2—N3—C8—C7	0.0 (2)	C17—C18—C19—C20	179.8 (2)
C24—N3—C8—C7	170.1 (2)	C18—C19—C20—C21	0.8 (4)
N2—N3—C8—C9	178.7 (2)	C19—C20—C21—C22	−0.1 (4)
C24—N3—C8—C9	−11.2 (4)	C20—C21—C22—C23	0.1 (4)
C6—C7—C8—N3	0.5 (2)	C21—C22—C23—C18	−0.7 (4)
C6—C7—C8—C9	−178.1 (2)	C19—C18—C23—C22	1.4 (3)
N3—C8—C9—C10	135.3 (2)	C17—C18—C23—C22	−179.8 (2)
C7—C8—C9—C10	−46.4 (4)	N2—N3—C24—C25	57.3 (3)
N3—C8—C9—C14	−47.5 (3)	C8—N3—C24—C25	−112.3 (3)
C7—C8—C9—C14	130.9 (3)	N2—N3—C24—C26	−68.7 (3)
C14—C9—C10—C11	1.4 (4)	C8—N3—C24—C26	121.7 (2)
C8—C9—C10—C11	178.8 (2)	N4—N5—C27—C28	52.8 (3)
C9—C10—C11—C12	0.3 (5)	C17—N5—C27—C28	−135.8 (3)
C10—C11—C12—C13	−1.2 (5)	N4—N5—C27—C29	−71.5 (3)
C11—C12—C13—C14	0.3 (5)	C17—N5—C27—C29	99.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···Cg1ⁱ	0.93	2.86	3.710 (3)	153

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₉H₂₉N₅
M_r	447.57
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.973 (3), 10.172 (3), 14.014 (4)
α, β, γ (°)	110.940 (4), 106.494 (4), 94.583 (4)
V (Å³)	1246.8 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.53 × 0.43 × 0.39

Data collection
Diffractometer	SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.963, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	6572, 4332, 2417
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.123, 1.05
No. of reflections	4332
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001) and publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···Cg1ⁱ	0.93	2.86	3.710 (3)	153

Symmetry code: (i) −x+1, −y, −z.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dias, H. V. R. & Gamage, C. S. P. (2007). Angew. Chem. Int. Ed. 46, 2192–2194. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2001). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2002). SADABS. Version 2.03. University of Göttingen, Germany. Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
Zhou, Y. B. & Chen, W. Z. (2007). Dalton Trans. pp. 5123–5125. Web of Science CSD CrossRef Google Scholar

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