Di-tert-butyl N-{[1-(pyridin-4-yl)-1H-1,2,3-triazol-4-yl]methyl}iminodiacetate

François, A.; Marty, L.; Picard, C.; Mallet-Ladeira, S.; Benoist, E.

doi:10.1107/S1600536812042596

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3162

doi:10.1107/S1600536812042596

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Di-tert-butyl N-{[1-(pyridin-4-yl)-1H-1,2,3-triazol-4-yl]methyl}iminodiacetate

Alison François,^a Louise Marty,^a Claude Picard,^a Sonia Mallet-Ladeira ^b and Eric Benoist ^a ^*

^aLSPCMIB, UMR-CNRS 5068, Université de Toulouse, 118 route de Narbonne, F-31062 Toulouse cedex 9, and ^bUniversité de Toulouse, UPS and CNRS, Institut de Chimie de Toulouse, FR2599, 118 route de Narbonne, F-31062 Toulouse cedex 9, France
^*Correspondence e-mail: benoist@chimie.ups-tlse.fr

(Received 5 October 2012; accepted 11 October 2012; online 20 October 2012)

In the title compound, C₂₀H₂₉N₅O₄, the pyridine ring makes a dihedral angle of 10.41 (16)° with the triazole ring, which exhibits an azo-like character. In the crystal, molecules are linked by C—H⋯O and C—H⋯N hydrogen bonds, and C—H⋯π interactions involving a methyl group and the pyridine ring of a neighbouring molecule, leading to the formation of a three-dimensional network.

Related literature

For 4-pyridyl-1,2,3-triazoles as building blocks in the synthesis of chelating agents for biomedical applications, see: Bonnet et al. (2012 ); Pellegatti et al. (2008 ). For the crystal structures of structural isomers such as 2-pyridyl-1,2,3-triazoles, see: Obata et al. (2008 ); Schweinfurth et al. (2008 ); Boulay et al. (2010 ); Seridi et al. (2011 ); Crowley et al. (2010 ); Kilpin et al. (2011 ).

Experimental

Crystal data

C₂₀H₂₉N₅O₄
M_r = 403.48
Monoclinic, P 2₁
a = 9.1568 (8) Å
b = 11.4452 (10) Å
c = 11.4928 (11) Å
β = 110.840 (4)°
V = 1125.66 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 193 K
0.2 × 0.1 × 0.04 mm

Data collection

Bruker Kappa APEXII Quazar diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.989, T_max = 0.997
11329 measured reflections
3530 independent reflections
1947 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.122
S = 1.00
3530 reflections
268 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.54	3.443 (4)	160
C6—H6⋯N1ⁱⁱ	0.95	2.31	3.252 (4)	173
C9—H9B⋯N3ⁱⁱⁱ	0.99	2.50	3.449 (4)	160
C18—H18A⋯Cg1^iv	0.98	2.91	3.864 (4)	166
Symmetry codes: (i) x, y+1, z; (ii) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (iv) x, y-1, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042596/su2510sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042596/su2510Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042596/su2510Isup3.cml

checkCIF report

Comment top

If 1,2,3-Triazoles are well known for their biological properties, particular attention has been recently devoted to the development of 2-pyridyl-1,2,3-triazole derivatives (or pyta) as alternative ligands to 2,2'-bipyridines. This interest is explained by the easy preparation of such ligands using a click chemistry strategy (Obata et al., 2008; Schweinfurth et al., 2008), and the use of pyta derivatives as efficient chelator systems for Tc(CO)₃⁺ or Re(CO)₃⁺ organometallic cores (Boulay et al., 2010; Seridi et al., 2011). Recently, structural pyta isomers like 4-pyridyl-1,2,3-triazole have been described as building blocks in the synthesis of chelating agents for biomedical applications (Bonnet et al., 2012; Pellegatti et al., 2008). In this paper, we report on the first X-ray structure analysis of a 4-pyridyl-1,2,3-triazole derivative.

The title molecule, Fig. 1, can be considered as a ditopic ligand with two distinct transition metal complexing sites, the iminodiacetate (IDA) pincer and the 4-pyridine moiety. Bond lengths and angles are within normal ranges, and comparable with values found for structural isomers, such as 2-pyridyl-1,2,3-triazole derivatives (Obata et al. 2008; Schweinfurth et al., 2008; Seridi et al., 2011; Boulay et al., 2010). As is often observed in these ligand systems, the pyridyl and triazole units are coplanar (Crowley et al., 2010; Kilpin et al., 2011). Unarguably, the structure exhibits a practically planar geometry with slight deviation of the pyridyl moiety, which makes a dihedral angle of 10.41 (16)° with the mean plane of the triazole ring. As expected, the N3–N4 distance of the 1,2,3-triazole at 1.308 (4) Å is shorter than the N4–C7 and N2–N3 bonds, 1.358 (4) and 1.356 (3) Å respectively, confirming the azo character of the triazolyl entity.

In the crystal, molecules are linked by C–H···O and C–H···N hydrogen bonds (Table 1 and Fig. 2). It is noteworthy that a C–H···π interaction between of the hydrogen H18A of one methyl group and the π cloud of the pyridine ring was also observed, this interaction participates in the cohesion of the crystal.

Related literature top

For 4-pyridyl-1,2,3-triazoles as building blocks in the synthesis of chelating agents for biomedical applications, see: Bonnet et al. (2012); Pellegatti et al. (2008). For the crystal structures of structural isomers such as 2-pyridyl-1,2,3-triazoles, see: Obata et al. (2008); Schweinfurth et al. (2008); Boulay et al. (2010); Seridi et al. (2011); Crowley et al. (2010); Kilpin et al. (2011).

Experimental top

Freshly prepared 4-azidopyridine (0.4 g, 3.3 mmol), 3-[bis(tert-butoxycarbonylmeth-yl) amino]-prop-1-yne (0.94 g, 3.3 mmol), copper(II) acetate monohydrate (130 mg, 0.66 mmol) and sodium ascorbate (260 mg, 1.32 mmol) were mixed in acetonitrile (5 ml) and stirred overnight at 303 K. The resulting brown solution was cooled then diluted with chloroform (10 ml) and washed twice with saturated Na₂edta solution (2x15 ml). The aqueous solutions were extracted with chloroform (3x7 ml). The organic extracts were combined, dried over Na₂SO₄ and the solvent was taken off under reduce pressure. The crude product was purified by column chromatography on neutral alumina (eluent: CH₂Cl₂) to give 1.03 g of the title compound [Yield: 77%]. Analysis calculated for C₂₀H₂₉N₅O₄: C 59.54, H 7.24, N 17.36%; found: C 59.24, H 7.32, N 17.44%. Plate-like colourless crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of a methanol-dichloromethane (1:1 / v:v) solution. Further spectroscopic data for the title compound are available in the archived CIF.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the crystal packing of the title compound, showing the C-H···O and C-H···N hydrogen bonds and the C—H··· π interactions (dashed lines). H atoms not involved in these interactions have been omitted for clarity.

Di-tert-butyl N-{[1-(pyridin-4-yl)-1H-1,2,3-triazol-4-yl]methyl}iminodiacetate top

Crystal data top

C₂₀H₂₉N₅O₄	F(000) = 432
M_r = 403.48	D_x = 1.19 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1261 reflections
a = 9.1568 (8) Å	θ = 2.4–21.3°
b = 11.4452 (10) Å	µ = 0.09 mm⁻¹
c = 11.4928 (11) Å	T = 193 K
β = 110.840 (4)°	Plate, colourless
V = 1125.66 (18) Å³	0.2 × 0.1 × 0.04 mm
Z = 2

Data collection top

Bruker Kappa APEXII Quazar diffractometer	3530 independent reflections
Radiation source: microfocus sealed tube	1947 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.077
phi and ω scans	θ_max = 30.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→11
T_min = 0.989, T_max = 0.997	k = −14→16
11329 measured reflections	l = −16→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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0464P)²] where P = (F_o² + 2F_c²)/3
3530 reflections	(Δ/σ)_max = 0.001
268 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₂₉N₅O₄	V = 1125.66 (18) Å³
M_r = 403.48	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.1568 (8) Å	µ = 0.09 mm⁻¹
b = 11.4452 (10) Å	T = 193 K
c = 11.4928 (11) Å	0.2 × 0.1 × 0.04 mm
β = 110.840 (4)°

Data collection top

Bruker Kappa APEXII Quazar diffractometer	3530 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1947 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.997	R_int = 0.077
11329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	1 restraint
wR(F²) = 0.122	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
3530 reflections	Δρ_min = −0.18 e Å⁻³
268 parameters

Special details top

Experimental. Spectroscopic data for the title compound: ¹H NMR (300 MHz, CDCl₃): δ/p.p.m. = 1.45 (s, 18H, CH₃); 3.49 (s, 4H, CH₂); 4.12 (s, 2H, CH₂); 7.72 (m, 2H, CH_Ar); 8.24 (s, 1H, CH_ta); 8.75 (m, 2H, CH_Ar); ¹³C NMR (75 MHz, CDCl₃): δ/p.p.m. = 28.1 (9CH₃); 49.0 (CH₂); 55.5 (2CH₂); 81.3 (2C_IV); 113.6, 151.6 (4CH_Ar); 120.7 (CH_ta); 143.1, 147.5 (2C_IV); 170.3 (2CO); IR (KBr): ν_C=O = 1735 cm^-1; MS (DCI/NH₃): m/z 404, [M⁺]; 426, [M+Na⁺]; 443, [M+K⁺].

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 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
O2	0.8574 (2)	0.02696 (19)	0.4779 (2)	0.0380 (5)
N1	1.0194 (3)	0.7418 (2)	0.9730 (2)	0.0392 (7)
O3	0.6055 (3)	0.0266 (2)	0.8927 (2)	0.0521 (7)
O4	0.5024 (3)	−0.13966 (19)	0.7905 (2)	0.0378 (6)
N5	0.6572 (3)	0.1115 (2)	0.6817 (2)	0.0276 (6)
N3	0.5993 (3)	0.5068 (2)	0.6577 (2)	0.0407 (7)
N4	0.5251 (3)	0.4092 (3)	0.6151 (2)	0.0393 (7)
C4	0.9274 (3)	0.5441 (3)	0.9510 (3)	0.0342 (8)
H4	0.9346	0.4682	0.9859	0.041*
C17	0.4539 (4)	−0.1904 (3)	0.8901 (3)	0.0442 (9)
C6	0.7207 (4)	0.3635 (3)	0.7862 (3)	0.0293 (7)
H6	0.7926	0.3216	0.8537	0.035*
C7	0.5962 (3)	0.3197 (3)	0.6918 (3)	0.0278 (7)
C10	0.8501 (4)	0.0438 (3)	0.5901 (3)	0.0323 (7)
C9	0.7146 (3)	0.1245 (3)	0.5787 (3)	0.0290 (7)
H9A	0.7481	0.2064	0.576	0.035*
H9B	0.6281	0.1081	0.4993	0.035*
N2	0.7201 (3)	0.4797 (2)	0.7634 (2)	0.0277 (6)
C5	0.8218 (3)	0.5684 (3)	0.8340 (3)	0.0279 (7)
C8	0.5345 (3)	0.1981 (3)	0.6690 (3)	0.0335 (8)
H8A	0.4823	0.1794	0.7288	0.04*
H8B	0.4551	0.1931	0.584	0.04*
O1	0.9358 (3)	0.0025 (2)	0.6860 (2)	0.0511 (7)
C16	0.5703 (4)	−0.0346 (3)	0.8019 (3)	0.0339 (7)
C15	0.5930 (4)	−0.0054 (3)	0.6821 (3)	0.0299 (7)
H15A	0.6644	−0.0636	0.6672	0.036*
H15B	0.4912	−0.0113	0.6128	0.036*
C2	0.9161 (4)	0.7613 (3)	0.8589 (3)	0.0408 (8)
H2	0.9119	0.8378	0.8258	0.049*
C3	1.0224 (4)	0.6337 (3)	1.0161 (3)	0.0393 (8)
H3	1.0948	0.6169	1.097	0.047*
C11	0.9656 (4)	−0.0587 (3)	0.4568 (3)	0.0440 (9)
C14	0.9375 (5)	−0.1775 (3)	0.5026 (5)	0.0735 (14)
H14A	0.9729	−0.177	0.5937	0.11*
H14B	0.9957	−0.2369	0.4755	0.11*
H14C	0.8256	−0.1957	0.4682	0.11*
C19	0.3794 (6)	−0.3030 (4)	0.8319 (4)	0.0722 (13)
H19A	0.2924	−0.2864	0.7542	0.108*
H19B	0.34	−0.3444	0.8893	0.108*
H19C	0.4569	−0.3516	0.814	0.108*
C1	0.8158 (4)	0.6794 (3)	0.7858 (3)	0.0380 (8)
H1	0.7448	0.6984	0.705	0.046*
C12	1.1312 (4)	−0.0187 (4)	0.5169 (4)	0.0566 (11)
H12A	1.1436	0.0581	0.484	0.085*
H12B	1.2012	−0.0749	0.499	0.085*
H12C	1.1573	−0.0133	0.6072	0.085*
C18	0.5965 (5)	−0.2123 (4)	1.0045 (4)	0.0658 (12)
H18A	0.6712	−0.2602	0.9821	0.099*
H18B	0.5658	−0.2534	1.067	0.099*
H18C	0.6451	−0.1375	1.0386	0.099*
C20	0.3373 (5)	−0.1108 (4)	0.9149 (4)	0.0656 (12)
H20A	0.3908	−0.0407	0.9584	0.098*
H20B	0.2886	−0.1516	0.9667	0.098*
H20C	0.2567	−0.0884	0.8357	0.098*
C13	0.9166 (5)	−0.0569 (4)	0.3165 (4)	0.0776 (15)
H13A	0.8057	−0.0775	0.279	0.116*
H13B	0.9791	−0.1135	0.2904	0.116*
H13C	0.933	0.0215	0.2892	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0374 (12)	0.0399 (14)	0.0433 (13)	0.0053 (11)	0.0224 (10)	0.0003 (11)
N1	0.0382 (15)	0.0331 (17)	0.0403 (16)	−0.0034 (14)	0.0067 (12)	−0.0002 (13)
O3	0.0732 (17)	0.0544 (16)	0.0345 (13)	−0.0248 (14)	0.0262 (12)	−0.0158 (12)
O4	0.0505 (13)	0.0322 (13)	0.0355 (12)	−0.0114 (11)	0.0213 (10)	0.0007 (10)
N5	0.0300 (13)	0.0248 (14)	0.0315 (13)	−0.0036 (12)	0.0151 (11)	−0.0047 (10)
N3	0.0432 (15)	0.0378 (17)	0.0291 (14)	0.0000 (14)	−0.0020 (12)	0.0014 (12)
N4	0.0437 (16)	0.0287 (16)	0.0354 (15)	−0.0019 (14)	0.0015 (13)	0.0022 (12)
C4	0.0378 (18)	0.0237 (17)	0.0341 (17)	0.0005 (15)	0.0044 (14)	0.0039 (14)
C17	0.058 (2)	0.043 (2)	0.043 (2)	−0.012 (2)	0.0311 (18)	0.0024 (16)
C6	0.0325 (16)	0.0212 (16)	0.0337 (17)	0.0046 (14)	0.0112 (13)	0.0041 (13)
C7	0.0296 (16)	0.0232 (17)	0.0307 (16)	0.0021 (14)	0.0107 (13)	−0.0003 (13)
C10	0.0341 (16)	0.0273 (18)	0.0374 (18)	−0.0035 (15)	0.0150 (14)	0.0013 (14)
C9	0.0305 (15)	0.0227 (17)	0.0354 (17)	−0.0017 (14)	0.0136 (13)	0.0010 (13)
N2	0.0302 (12)	0.0239 (15)	0.0259 (13)	0.0025 (12)	0.0061 (10)	0.0020 (11)
C5	0.0308 (15)	0.0259 (17)	0.0280 (15)	−0.0020 (14)	0.0118 (13)	−0.0014 (13)
C8	0.0284 (15)	0.034 (2)	0.0391 (18)	−0.0007 (15)	0.0129 (14)	−0.0032 (14)
O1	0.0452 (13)	0.0633 (18)	0.0441 (14)	0.0205 (14)	0.0151 (11)	0.0161 (13)
C16	0.0348 (17)	0.0346 (19)	0.0352 (18)	−0.0056 (15)	0.0160 (14)	−0.0026 (14)
C15	0.0347 (16)	0.0261 (17)	0.0297 (15)	−0.0065 (15)	0.0124 (13)	−0.0057 (13)
C2	0.051 (2)	0.0250 (18)	0.0391 (19)	−0.0054 (17)	0.0077 (16)	0.0046 (15)
C3	0.0398 (18)	0.033 (2)	0.0362 (19)	−0.0009 (16)	0.0027 (15)	0.0052 (15)
C11	0.041 (2)	0.037 (2)	0.063 (2)	0.0023 (17)	0.0302 (18)	−0.0075 (17)
C14	0.075 (3)	0.035 (2)	0.129 (4)	0.000 (2)	0.060 (3)	−0.011 (3)
C19	0.098 (3)	0.058 (3)	0.074 (3)	−0.034 (3)	0.047 (3)	0.001 (2)
C1	0.0471 (18)	0.0270 (19)	0.0316 (17)	−0.0006 (17)	0.0039 (14)	0.0083 (14)
C12	0.039 (2)	0.054 (3)	0.087 (3)	0.006 (2)	0.035 (2)	−0.001 (2)
C18	0.079 (3)	0.077 (3)	0.046 (2)	0.002 (3)	0.029 (2)	0.019 (2)
C20	0.067 (3)	0.082 (3)	0.067 (3)	−0.006 (3)	0.048 (2)	0.005 (2)
C13	0.074 (3)	0.106 (4)	0.065 (3)	0.016 (3)	0.041 (2)	−0.023 (3)

Geometric parameters (Å, º) top

O2—C10	1.328 (4)	C8—H8B	0.99
O2—C11	1.474 (4)	C16—C15	1.501 (4)
N1—C3	1.329 (4)	C15—H15A	0.99
N1—C2	1.335 (4)	C15—H15B	0.99
O3—C16	1.202 (4)	C2—C1	1.371 (4)
O4—C16	1.339 (4)	C2—H2	0.95
O4—C17	1.486 (4)	C3—H3	0.95
N5—C15	1.461 (4)	C11—C12	1.497 (5)
N5—C9	1.464 (4)	C11—C13	1.512 (5)
N5—C8	1.466 (4)	C11—C14	1.513 (5)
N3—N4	1.308 (4)	C14—H14A	0.98
N3—N2	1.356 (3)	C14—H14B	0.98
N4—C7	1.358 (4)	C14—H14C	0.98
C4—C5	1.377 (4)	C19—H19A	0.98
C4—C3	1.379 (4)	C19—H19B	0.98
C4—H4	0.95	C19—H19C	0.98
C17—C19	1.499 (5)	C1—H1	0.95
C17—C20	1.506 (5)	C12—H12A	0.98
C17—C18	1.508 (5)	C12—H12B	0.98
C6—N2	1.355 (4)	C12—H12C	0.98
C6—C7	1.359 (4)	C18—H18A	0.98
C6—H6	0.95	C18—H18B	0.98
C7—C8	1.489 (4)	C18—H18C	0.98
C10—O1	1.200 (4)	C20—H20A	0.98
C10—C9	1.514 (4)	C20—H20B	0.98
C9—H9A	0.99	C20—H20C	0.98
C9—H9B	0.99	C13—H13A	0.98
N2—C5	1.421 (4)	C13—H13B	0.98
C5—C1	1.380 (4)	C13—H13C	0.98
C8—H8A	0.99

C10—O2—C11	121.7 (2)	H15A—C15—H15B	107.8
C3—N1—C2	115.8 (3)	N1—C2—C1	125.0 (3)
C16—O4—C17	122.2 (2)	N1—C2—H2	117.5
C15—N5—C9	110.9 (2)	C1—C2—H2	117.5
C15—N5—C8	109.0 (2)	N1—C3—C4	124.4 (3)
C9—N5—C8	109.5 (2)	N1—C3—H3	117.8
N4—N3—N2	106.8 (2)	C4—C3—H3	117.8
N3—N4—C7	109.6 (2)	O2—C11—C12	110.5 (3)
C5—C4—C3	117.9 (3)	O2—C11—C13	101.8 (3)
C5—C4—H4	121	C12—C11—C13	110.8 (3)
C3—C4—H4	121	O2—C11—C14	109.4 (3)
O4—C17—C19	101.9 (3)	C12—C11—C14	112.6 (3)
O4—C17—C20	109.6 (3)	C13—C11—C14	111.1 (4)
C19—C17—C20	111.3 (3)	C11—C14—H14A	109.5
O4—C17—C18	109.4 (3)	C11—C14—H14B	109.5
C19—C17—C18	111.2 (3)	H14A—C14—H14B	109.5
C20—C17—C18	112.8 (3)	C11—C14—H14C	109.5
N2—C6—C7	105.3 (3)	H14A—C14—H14C	109.5
N2—C6—H6	127.4	H14B—C14—H14C	109.5
C7—C6—H6	127.4	C17—C19—H19A	109.5
N4—C7—C6	108.2 (3)	C17—C19—H19B	109.5
N4—C7—C8	121.8 (3)	H19A—C19—H19B	109.5
C6—C7—C8	130.0 (3)	C17—C19—H19C	109.5
O1—C10—O2	126.3 (3)	H19A—C19—H19C	109.5
O1—C10—C9	124.6 (3)	H19B—C19—H19C	109.5
O2—C10—C9	109.1 (2)	C2—C1—C5	117.5 (3)
N5—C9—C10	112.8 (2)	C2—C1—H1	121.2
N5—C9—H9A	109	C5—C1—H1	121.2
C10—C9—H9A	109	C11—C12—H12A	109.5
N5—C9—H9B	109	C11—C12—H12B	109.5
C10—C9—H9B	109	H12A—C12—H12B	109.5
H9A—C9—H9B	107.8	C11—C12—H12C	109.5
C6—N2—N3	110.1 (3)	H12A—C12—H12C	109.5
C6—N2—C5	129.3 (2)	H12B—C12—H12C	109.5
N3—N2—C5	120.5 (2)	C17—C18—H18A	109.5
C4—C5—C1	119.4 (3)	C17—C18—H18B	109.5
C4—C5—N2	120.3 (3)	H18A—C18—H18B	109.5
C1—C5—N2	120.3 (3)	C17—C18—H18C	109.5
N5—C8—C7	112.6 (2)	H18A—C18—H18C	109.5
N5—C8—H8A	109.1	H18B—C18—H18C	109.5
C7—C8—H8A	109.1	C17—C20—H20A	109.5
N5—C8—H8B	109.1	C17—C20—H20B	109.5
C7—C8—H8B	109.1	H20A—C20—H20B	109.5
H8A—C8—H8B	107.8	C17—C20—H20C	109.5
O3—C16—O4	125.4 (3)	H20A—C20—H20C	109.5
O3—C16—C15	125.8 (3)	H20B—C20—H20C	109.5
O4—C16—C15	108.8 (2)	C11—C13—H13A	109.5
N5—C15—C16	113.2 (2)	C11—C13—H13B	109.5
N5—C15—H15A	108.9	H13A—C13—H13B	109.5
C16—C15—H15A	108.9	C11—C13—H13C	109.5
N5—C15—H15B	108.9	H13A—C13—H13C	109.5
C16—C15—H15B	108.9	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.54	3.443 (4)	160
C6—H6···N1ⁱⁱ	0.95	2.31	3.252 (4)	173
C9—H9B···N3ⁱⁱⁱ	0.99	2.50	3.449 (4)	160
C18—H18A···Cg1^iv	0.98	2.91	3.864 (4)	166

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₉N₅O₄
M_r	403.48
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	9.1568 (8), 11.4452 (10), 11.4928 (11)
β (°)	110.840 (4)
V (Å³)	1125.66 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.2 × 0.1 × 0.04

Data collection
Diffractometer	Bruker Kappa APEXII Quazar diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.989, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	11329, 3530, 1947
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.122, 1.00
No. of reflections	3530
No. of parameters	268
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: APEX2 (Bruker, 2008), APEX2 and SAINT (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX publication routines (Farrugia, 2012) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.54	3.443 (4)	160
C6—H6···N1ⁱⁱ	0.95	2.31	3.252 (4)	173
C9—H9B···N3ⁱⁱⁱ	0.99	2.50	3.449 (4)	160
C18—H18A···Cg1^iv	0.98	2.91	3.864 (4)	166

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

Acknowledgements

We gratefully acknowledge the French Ministère de l'Education Nationale, de la Recherche et de la Technologie for financial support.

References

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Volume 68| Part 11| November 2012| Page o3162

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