3-Benzotriazol-1-yl 5-tert-butyl 2,6-dimethyl-4-(3-nitro­phen­yl)-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Liu, B.-S.; Sun, F.-X.; Zhou, L.-N.; Sun, H.; Wang, J.-K.

doi:10.1107/S1600536805040079

3-Benzotriazol-1-yl 5-tert-butyl 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate

B.-S. Liu, F.-X. Sun, L.-N. Zhou, H. Sun and J.-K. Wang

The title compound, C₂₅H₂₅N₅O₆, is an important intermediate in the synthesis of nefidipine-type pharmaceuticals. The crystal packing is stabilized by intermolecular N—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040079/ww6455sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040079/ww6455Isup2.hkl Contains datablock I

CCDC reference: 296705

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.048
wR factor = 0.155
Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.08 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.10 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.83 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C8
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

4-Aryl-1,4-dihydropyridine-3,5-dicarboxylic diesters of the nefidipine type have become almost indispensable for the treatment of cardiovascular diseases since they first appeared on the market in 1975 (Yiu & Knaus, 1999; Goldmann & Stoltefuss, 1991). The title compound, (I), is a key intermediate for preparation of them.

Fig. 1 shows the structure of the title compound. The molecule contains an aromatic ring, a dihydropyridine ring and a benzotriazole ring. The dihedral angles between the aromatic and dihydropyridine rings, the dihydropyridine and benzotriazole rings, and the aromatic and benzotriazole rings are 88.3, 92.3 and 43.4°, respectively. This is compared well with that of nefidipine (Hofmann & Cimiraglia, 1990; Ramusino & Varí, 1999).

An intermolecular hydrogen bond, involving N1—H1D as donor, and O4 as acceptor, respectively, links the molecules into infinite chains.

Experimental top

2,6-Dimethyl-4-(3-nitro-phenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid mono-tert-butyl ester (491 mg, 1 mmol) was dissolved in CH₂Cl₂ (30 ml), dicyclohexylcarbodiimide (206 mg, 1 mmol), and benzotriazol-1-ol (135 mg, 1 mmol) in CH₂Cl₂ (10 ml) was added to the solution at 278 K. The reaction mixture was stirred at 276–279 K for a further 10 h. The solvent CH₂Cl₂ was removed by vacuum evaporation at 293 K. The product was purified by chromatography on a silica gel column (eluted by ethyl acetate and petroleum, 1:5) at room temperature with a yield of 92% (450 mg). Suitable crystals were obtained by slow evaporation of a solution in methanol.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A view of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing of (I).

3-Benzotriazol-1-yl 5-tert-butyl 2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate top

Crystal data top

C₂₅H₂₅N₅O₆	F(000) = 1032
M_r = 491.50	D_x = 1.302 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 458.5 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.332 (2) Å	Cell parameters from 19215 reflections
b = 15.163 (3) Å	θ = 3.3–25.5°
c = 16.010 (3) Å	µ = 0.10 mm⁻¹
β = 90.96 (3)°	T = 293 K
V = 2507.6 (9) Å³	Rod, yellow
Z = 4	0.38 × 0.25 × 0.11 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	4620 independent reflections
Radiation source: rotating anode	3165 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
oscillation scans	θ_max = 25.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.965, T_max = 0.989	k = −18→18
23558 measured reflections	l = −19→19

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
4620 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₅H₂₅N₅O₆	V = 2507.6 (9) Å³
M_r = 491.50	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.332 (2) Å	µ = 0.10 mm⁻¹
b = 15.163 (3) Å	T = 293 K
c = 16.010 (3) Å	0.38 × 0.25 × 0.11 mm
β = 90.96 (3)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	4620 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3165 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.989	R_int = 0.050
23558 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.01	Δρ_max = 0.34 e Å⁻³
4620 reflections	Δρ_min = −0.23 e Å⁻³
325 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 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
O1	0.21060 (13)	0.82239 (9)	0.03233 (10)	0.0531 (4)
O2	0.01379 (15)	0.88373 (12)	0.01864 (15)	0.0859 (7)
O3	0.59163 (18)	0.73312 (19)	0.32341 (14)	0.1087 (8)
O4	0.60069 (18)	0.6879 (3)	0.19826 (16)	0.1405 (13)
O5	0.13680 (15)	0.42128 (10)	0.10564 (12)	0.0677 (5)
O6	0.28262 (12)	0.52457 (9)	0.06732 (9)	0.0454 (4)
C1	0.2502 (3)	0.9710 (2)	0.0842 (3)	0.1049 (12)
H1A	0.1616	0.9891	0.0775	0.157*
H1B	0.3057	1.0215	0.0792	0.157*
H1C	0.2628	0.9447	0.1382	0.157*
C2	0.4217 (2)	0.87458 (18)	0.0260 (3)	0.0965 (11)
H2A	0.4397	0.8327	−0.0173	0.145*
H2B	0.4353	0.8473	0.0796	0.145*
H2C	0.4785	0.9244	0.0210	0.145*
C3	0.2523 (3)	0.9399 (2)	−0.0684 (2)	0.1041 (12)
H3A	0.2747	0.8963	−0.1092	0.156*
H3B	0.3015	0.9926	−0.0777	0.156*
H3C	0.1616	0.9530	−0.0732	0.156*
C4	0.2824 (2)	0.90503 (15)	0.01778 (18)	0.0629 (7)
C5	0.08078 (19)	0.82103 (14)	0.03572 (14)	0.0483 (5)
C6	0.03497 (17)	0.73447 (12)	0.06462 (11)	0.0370 (4)
C7	−0.09284 (17)	0.71889 (13)	0.07393 (12)	0.0384 (4)
C8	−0.20410 (18)	0.77928 (15)	0.05539 (14)	0.0490 (5)
H8A	−0.1720	0.8346	0.0351	0.073*
H8B	−0.2520	0.7890	0.1054	0.073*
H8C	−0.2597	0.7530	0.0137	0.073*
C9	−0.05415 (17)	0.56482 (13)	0.10834 (12)	0.0398 (4)
C10	−0.1234 (2)	0.48118 (15)	0.12917 (16)	0.0559 (6)
H10A	−0.2140	0.4931	0.1352	0.084*
H10B	−0.0888	0.4577	0.1806	0.084*
H10C	−0.1117	0.4391	0.0851	0.084*
C11	0.07512 (16)	0.57427 (12)	0.09479 (11)	0.0358 (4)
C12	0.13589 (16)	0.66574 (11)	0.08816 (11)	0.0340 (4)
H12A	0.2005	0.6641	0.0441	0.041*
C13	0.20542 (16)	0.68733 (12)	0.17079 (11)	0.0346 (4)
C14	0.13566 (18)	0.69983 (15)	0.24284 (13)	0.0490 (5)
H14A	0.0458	0.6966	0.2403	0.059*
C15	0.1969 (2)	0.71708 (18)	0.31872 (15)	0.0634 (7)
H15A	0.1479	0.7255	0.3662	0.076*
C16	0.3304 (2)	0.72190 (16)	0.32439 (14)	0.0557 (6)
H16A	0.3725	0.7340	0.3749	0.067*
C17	0.39835 (18)	0.70814 (14)	0.25279 (13)	0.0474 (5)
C18	0.33990 (17)	0.69122 (13)	0.17594 (12)	0.0425 (5)
H18A	0.3896	0.6826	0.1287	0.051*
C19	0.15671 (18)	0.49738 (13)	0.09263 (13)	0.0417 (5)
C20	0.45053 (17)	0.43242 (13)	0.12995 (12)	0.0418 (5)
C21	0.4629 (2)	0.45512 (16)	0.21367 (15)	0.0568 (6)
H21A	0.4104	0.4973	0.2382	0.068*
C22	0.5578 (2)	0.41114 (19)	0.25773 (16)	0.0678 (7)
H22A	0.5696	0.4235	0.3142	0.081*
C23	0.6377 (2)	0.34806 (17)	0.22041 (17)	0.0613 (6)
H23A	0.7013	0.3204	0.2528	0.074*
C24	0.62516 (18)	0.32625 (15)	0.13851 (15)	0.0528 (6)
H24A	0.6786	0.2844	0.1144	0.063*
C25	0.52793 (17)	0.36951 (13)	0.09160 (14)	0.0444 (5)
N1	−0.13211 (14)	0.63705 (11)	0.10347 (11)	0.0440 (4)
H1D	−0.2107	0.6318	0.1197	0.053*
N2	0.54023 (19)	0.71073 (17)	0.25835 (15)	0.0733 (6)
N3	0.37061 (14)	0.45709 (10)	0.06648 (10)	0.0423 (4)
N4	0.39499 (15)	0.41572 (11)	−0.00536 (11)	0.0459 (4)
N5	0.49052 (15)	0.36102 (12)	0.00933 (11)	0.0480 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0388 (8)	0.0356 (8)	0.0851 (11)	−0.0055 (6)	0.0024 (7)	0.0130 (7)
O2	0.0505 (9)	0.0552 (11)	0.152 (2)	0.0086 (8)	0.0013 (10)	0.0404 (11)
O3	0.0581 (11)	0.168 (2)	0.0986 (17)	−0.0299 (13)	−0.0348 (11)	−0.0083 (15)
O4	0.0381 (10)	0.292 (4)	0.0915 (17)	−0.0161 (16)	0.0041 (10)	−0.016 (2)
O5	0.0508 (9)	0.0358 (9)	0.1166 (15)	−0.0012 (7)	0.0058 (9)	0.0122 (9)
O6	0.0330 (7)	0.0363 (7)	0.0669 (9)	0.0047 (6)	0.0030 (6)	0.0048 (6)
C1	0.099 (2)	0.067 (2)	0.149 (3)	−0.0329 (17)	0.023 (2)	−0.022 (2)
C2	0.0506 (14)	0.0576 (17)	0.181 (4)	−0.0180 (13)	0.0095 (17)	0.0200 (19)
C3	0.103 (2)	0.089 (2)	0.121 (3)	−0.0276 (18)	0.010 (2)	0.049 (2)
C4	0.0540 (13)	0.0375 (12)	0.0972 (19)	−0.0120 (10)	0.0062 (12)	0.0094 (12)
C5	0.0381 (10)	0.0425 (12)	0.0642 (14)	0.0010 (9)	−0.0026 (9)	0.0087 (10)
C6	0.0320 (9)	0.0373 (10)	0.0415 (10)	−0.0013 (8)	−0.0034 (7)	0.0026 (8)
C7	0.0350 (9)	0.0414 (11)	0.0387 (10)	0.0013 (8)	−0.0033 (7)	−0.0035 (8)
C8	0.0356 (10)	0.0550 (13)	0.0561 (13)	0.0067 (9)	−0.0040 (8)	0.0020 (10)
C9	0.0347 (9)	0.0423 (11)	0.0423 (11)	−0.0056 (8)	−0.0027 (8)	0.0018 (8)
C10	0.0411 (11)	0.0531 (13)	0.0734 (16)	−0.0129 (10)	0.0003 (10)	0.0096 (11)
C11	0.0328 (9)	0.0340 (10)	0.0405 (10)	−0.0046 (8)	−0.0013 (7)	0.0008 (8)
C12	0.0283 (8)	0.0332 (10)	0.0404 (10)	−0.0035 (7)	0.0008 (7)	0.0017 (7)
C13	0.0307 (9)	0.0298 (9)	0.0431 (10)	0.0000 (7)	−0.0038 (7)	0.0001 (7)
C14	0.0318 (10)	0.0623 (14)	0.0529 (13)	0.0106 (9)	−0.0014 (8)	−0.0074 (10)
C15	0.0507 (13)	0.0889 (19)	0.0505 (13)	0.0164 (12)	0.0008 (10)	−0.0161 (12)
C16	0.0528 (12)	0.0631 (15)	0.0508 (13)	0.0024 (11)	−0.0128 (10)	−0.0114 (11)
C17	0.0353 (10)	0.0465 (12)	0.0601 (13)	−0.0076 (9)	−0.0104 (9)	0.0022 (10)
C18	0.0337 (9)	0.0476 (12)	0.0461 (11)	−0.0072 (8)	0.0010 (8)	0.0021 (9)
C19	0.0358 (10)	0.0383 (11)	0.0509 (12)	−0.0047 (8)	−0.0022 (8)	0.0015 (9)
C20	0.0351 (9)	0.0401 (11)	0.0501 (12)	−0.0018 (8)	0.0007 (8)	0.0047 (9)
C21	0.0597 (13)	0.0576 (14)	0.0529 (14)	0.0019 (11)	0.0005 (10)	−0.0031 (10)
C22	0.0708 (16)	0.0807 (18)	0.0515 (14)	−0.0060 (14)	−0.0099 (11)	0.0094 (12)
C23	0.0464 (12)	0.0698 (16)	0.0673 (16)	−0.0005 (11)	−0.0094 (10)	0.0217 (13)
C24	0.0321 (10)	0.0506 (13)	0.0756 (17)	0.0013 (9)	0.0006 (9)	0.0147 (11)
C25	0.0303 (9)	0.0436 (11)	0.0596 (13)	−0.0028 (8)	0.0037 (8)	0.0047 (9)
N1	0.0274 (8)	0.0485 (10)	0.0561 (11)	−0.0025 (7)	0.0033 (7)	0.0049 (8)
N2	0.0398 (10)	0.1108 (19)	0.0690 (14)	−0.0249 (11)	−0.0098 (10)	0.0076 (12)
N3	0.0355 (8)	0.0399 (9)	0.0515 (10)	0.0079 (7)	−0.0014 (7)	−0.0002 (7)
N4	0.0379 (8)	0.0463 (10)	0.0536 (10)	0.0023 (8)	−0.0016 (7)	−0.0025 (8)
N5	0.0370 (9)	0.0487 (11)	0.0582 (11)	0.0045 (8)	0.0005 (7)	−0.0037 (8)

Geometric parameters (Å, º) top

O1—C5	1.343 (2)	C10—H10B	0.9600
O1—C4	1.477 (2)	C10—H10C	0.9600
O2—C5	1.205 (2)	C11—C19	1.439 (3)
O3—N2	1.210 (3)	C11—C12	1.527 (2)
O4—N2	1.207 (3)	C12—C13	1.530 (3)
O5—C19	1.191 (2)	C12—H12A	0.9800
O6—N3	1.3689 (19)	C13—C14	1.383 (3)
O6—C19	1.430 (2)	C13—C18	1.392 (2)
C1—C4	1.501 (4)	C14—C15	1.385 (3)
C1—H1A	0.9600	C14—H14A	0.9300
C1—H1B	0.9600	C15—C16	1.383 (3)
C1—H1C	0.9600	C15—H15A	0.9300
C2—C4	1.516 (4)	C16—C17	1.370 (3)
C2—H2A	0.9600	C16—H16A	0.9300
C2—H2B	0.9600	C17—C18	1.385 (3)
C2—H2C	0.9600	C17—N2	1.468 (3)
C3—C4	1.505 (4)	C18—H18A	0.9300
C3—H3A	0.9600	C20—N3	1.351 (2)
C3—H3B	0.9600	C20—C21	1.388 (3)
C3—H3C	0.9600	C20—C25	1.394 (3)
C5—C6	1.472 (3)	C21—C22	1.371 (3)
C6—C7	1.352 (3)	C21—H21A	0.9300
C6—C12	1.517 (2)	C22—C23	1.404 (4)
C7—N1	1.391 (3)	C22—H22A	0.9300
C7—C8	1.495 (3)	C23—C24	1.356 (4)
C8—H8A	0.9600	C23—H23A	0.9300
C8—H8B	0.9600	C24—C25	1.406 (3)
C8—H8C	0.9600	C24—H24A	0.9300
C9—N1	1.361 (2)	C25—N5	1.372 (3)
C9—C11	1.364 (3)	N1—H1D	0.8600
C9—C10	1.496 (3)	N3—N4	1.338 (2)
C10—H10A	0.9600	N4—N5	1.308 (2)

C5—O1—C4	121.59 (16)	C11—C12—C13	108.77 (14)
N3—O6—C19	113.25 (14)	C6—C12—H12A	108.2
C4—C1—H1A	109.5	C11—C12—H12A	108.2
C4—C1—H1B	109.5	C13—C12—H12A	108.2
H1A—C1—H1B	109.5	C14—C13—C18	118.58 (18)
C4—C1—H1C	109.5	C14—C13—C12	120.44 (16)
H1A—C1—H1C	109.5	C18—C13—C12	120.93 (16)
H1B—C1—H1C	109.5	C15—C14—C13	121.35 (19)
C4—C2—H2A	109.5	C15—C14—H14A	119.3
C4—C2—H2B	109.5	C13—C14—H14A	119.3
H2A—C2—H2B	109.5	C14—C15—C16	120.5 (2)
C4—C2—H2C	109.5	C14—C15—H15A	119.7
H2A—C2—H2C	109.5	C16—C15—H15A	119.7
H2B—C2—H2C	109.5	C17—C16—C15	117.5 (2)
C4—C3—H3A	109.5	C17—C16—H16A	121.3
C4—C3—H3B	109.5	C15—C16—H16A	121.3
H3A—C3—H3B	109.5	C16—C17—C18	123.34 (19)
C4—C3—H3C	109.5	C16—C17—N2	118.0 (2)
H3A—C3—H3C	109.5	C18—C17—N2	118.6 (2)
H3B—C3—H3C	109.5	C17—C18—C13	118.70 (18)
O1—C4—C3	110.3 (2)	C17—C18—H18A	120.6
O1—C4—C1	109.7 (2)	C13—C18—H18A	120.6
C3—C4—C1	111.7 (3)	O5—C19—O6	119.31 (17)
O1—C4—C2	101.93 (18)	O5—C19—C11	132.66 (18)
C3—C4—C2	111.6 (3)	O6—C19—C11	108.01 (15)
C1—C4—C2	111.3 (3)	N3—C20—C21	134.65 (19)
O2—C5—O1	123.30 (19)	N3—C20—C25	101.89 (17)
O2—C5—C6	126.03 (18)	C21—C20—C25	123.44 (19)
O1—C5—C6	110.66 (16)	C22—C21—C20	115.4 (2)
C7—C6—C5	120.67 (17)	C22—C21—H21A	122.3
C7—C6—C12	121.39 (16)	C20—C21—H21A	122.3
C5—C6—C12	117.85 (15)	C21—C22—C23	122.2 (2)
C6—C7—N1	118.97 (16)	C21—C22—H22A	118.9
C6—C7—C8	128.31 (18)	C23—C22—H22A	118.9
N1—C7—C8	112.72 (16)	C24—C23—C22	122.0 (2)
C7—C8—H8A	109.5	C24—C23—H23A	119.0
C7—C8—H8B	109.5	C22—C23—H23A	119.0
H8A—C8—H8B	109.5	C23—C24—C25	117.3 (2)
C7—C8—H8C	109.5	C23—C24—H24A	121.4
H8A—C8—H8C	109.5	C25—C24—H24A	121.4
H8B—C8—H8C	109.5	N5—C25—C20	109.42 (17)
N1—C9—C11	119.11 (17)	N5—C25—C24	131.0 (2)
N1—C9—C10	114.22 (16)	C20—C25—C24	119.6 (2)
C11—C9—C10	126.67 (18)	C9—N1—C7	124.18 (15)
C9—C10—H10A	109.5	C9—N1—H1D	117.9
C9—C10—H10B	109.5	C7—N1—H1D	117.9
H10A—C10—H10B	109.5	O3—N2—O4	122.8 (2)
C9—C10—H10C	109.5	O3—N2—C17	118.9 (2)
H10A—C10—H10C	109.5	O4—N2—C17	118.3 (2)
H10B—C10—H10C	109.5	N4—N3—C20	113.28 (16)
C9—C11—C19	119.61 (16)	N4—N3—O6	119.58 (15)
C9—C11—C12	120.75 (16)	C20—N3—O6	126.66 (16)
C19—C11—C12	119.50 (14)	N5—N4—N3	107.17 (16)
C6—C12—C11	111.07 (14)	N4—N5—C25	108.22 (16)
C6—C12—C13	112.24 (15)

C5—O1—C4—C3	−65.6 (3)	C12—C13—C18—C17	−177.89 (17)
C5—O1—C4—C1	57.8 (3)	N3—O6—C19—O5	−4.2 (3)
C5—O1—C4—C2	175.8 (2)	N3—O6—C19—C11	177.35 (14)
C4—O1—C5—O2	8.1 (4)	C9—C11—C19—O5	−5.3 (4)
C4—O1—C5—C6	−170.52 (18)	C12—C11—C19—O5	170.3 (2)
O2—C5—C6—C7	0.4 (4)	C9—C11—C19—O6	172.87 (17)
O1—C5—C6—C7	178.97 (18)	C12—C11—C19—O6	−11.5 (2)
O2—C5—C6—C12	−176.2 (2)	N3—C20—C21—C22	178.2 (2)
O1—C5—C6—C12	2.4 (3)	C25—C20—C21—C22	0.0 (3)
C5—C6—C7—N1	−178.32 (17)	C20—C21—C22—C23	0.6 (4)
C12—C6—C7—N1	−1.9 (3)	C21—C22—C23—C24	−0.6 (4)
C5—C6—C7—C8	2.4 (3)	C22—C23—C24—C25	0.0 (3)
C12—C6—C7—C8	178.88 (19)	N3—C20—C25—N5	0.2 (2)
N1—C9—C11—C19	−174.67 (17)	C21—C20—C25—N5	178.96 (19)
C10—C9—C11—C19	5.7 (3)	N3—C20—C25—C24	−179.29 (17)
N1—C9—C11—C12	9.8 (3)	C21—C20—C25—C24	−0.6 (3)
C10—C9—C11—C12	−169.92 (19)	C23—C24—C25—N5	−178.8 (2)
C7—C6—C12—C11	18.1 (2)	C23—C24—C25—C20	0.6 (3)
C5—C6—C12—C11	−165.37 (16)	C11—C9—N1—C7	9.5 (3)
C7—C6—C12—C13	−103.9 (2)	C10—C9—N1—C7	−170.77 (18)
C5—C6—C12—C13	72.6 (2)	C6—C7—N1—C9	−13.7 (3)
C9—C11—C12—C6	−22.2 (2)	C8—C7—N1—C9	165.66 (18)
C19—C11—C12—C6	162.27 (17)	C16—C17—N2—O3	−7.0 (4)
C9—C11—C12—C13	101.9 (2)	C18—C17—N2—O3	173.5 (2)
C19—C11—C12—C13	−73.7 (2)	C16—C17—N2—O4	170.8 (3)
C6—C12—C13—C14	56.2 (2)	C18—C17—N2—O4	−8.6 (4)
C11—C12—C13—C14	−67.1 (2)	C21—C20—N3—N4	−179.4 (2)
C6—C12—C13—C18	−126.50 (18)	C25—C20—N3—N4	−0.9 (2)
C11—C12—C13—C18	110.19 (19)	C21—C20—N3—O6	8.7 (4)
C18—C13—C14—C15	0.8 (3)	C25—C20—N3—O6	−172.81 (16)
C12—C13—C14—C15	178.2 (2)	C19—O6—N3—N4	97.11 (19)
C13—C14—C15—C16	−0.3 (4)	C19—O6—N3—C20	−91.5 (2)
C14—C15—C16—C17	−0.7 (4)	C20—N3—N4—N5	1.3 (2)
C15—C16—C17—C18	1.0 (4)	O6—N3—N4—N5	173.79 (15)
C15—C16—C17—N2	−178.4 (2)	N3—N4—N5—C25	−1.0 (2)
C16—C17—C18—C13	−0.4 (3)	C20—C25—N5—N4	0.5 (2)
N2—C17—C18—C13	179.0 (2)	C24—C25—N5—N4	180.0 (2)
C14—C13—C18—C17	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O4ⁱ	0.86	2.49	3.265 (3)	151

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₅N₅O₆
M_r	491.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.332 (2), 15.163 (3), 16.010 (3)
β (°)	90.96 (3)
V (Å³)	2507.6 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.25 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.965, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	23558, 4620, 3165
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.155, 1.01
No. of reflections	4620
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.23

Computer programs: RAPID-AUTO (Rigaku, 2004), RAPID-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.