Ethyl 2-(2,6-difluoro­benz­yloxy)-4-(4,6-dimethoxy­pyrimidin-2-yl)quinoline-3-carboxyl­ate

Li, Y.

doi:10.1107/S1600536809030499

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2101

doi:10.1107/S1600536809030499

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Ethyl 2-(2,6-difluorobenzyloxy)-4-(4,6-dimethoxypyrimidin-2-yl)quinoline-3-carboxylate

Yuan-xiang Li ^a ^*

^aKey Laboratory of Hunan Province for the Study and Utilization, of Ethnic Medicinal Plant Resources, Huaihua University, Huaihua 418008, People's Republic of China
^*Correspondence e-mail: hhhhxylyx@yahoo.com.cn

(Received 20 July 2009; accepted 31 July 2009; online 8 August 2009)

In the title compound, C₂₅H₂₁F₂N₃O₅, the pyrimidine and difluorobenzyloxy rings are twisted away from the central quinoline ring system, making dihedral angles of 54.6 (1) and 74.1 (1)°, respectively. A weak C—H⋯O interaction links symmetry-related molecules, forming a pseudo-dimer. π–π interactions between the quinoline rings of symmetry-related molecules [centroid–centroid distance = 3.5479 (10) Å] link these dimers into chains parallel to [101]. Weak C—H⋯π interactions join adjacent chains, forming a two-dimensional layer parallel to (101).

Related literature

Pyrimidinylbenzoates are highly effective herbicides with acetohydroxy acid synthase (AHAS) as target, see: Duggleby & Pang (2000 ). For related structures, see: Li & Huang (2007 ); Li & Wang (2007 ); Li et al. (2006 ).

Experimental

Crystal data

C₂₅H₂₁F₂N₃O₅
M_r = 481.45
Triclinic, $[P \overline 1]$
a = 9.6623 (6) Å
b = 10.7044 (6) Å
c = 11.3856 (7) Å
α = 84.466 (1)°
β = 82.251 (2)°
γ = 81.394 (1)°
V = 1150.21 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 297 K
0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.959, T_max = 0.989
12431 measured reflections
4954 independent reflections
3541 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.170
S = 1.06
4954 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯O3ⁱ	0.93	2.60	3.476 (2)	158
C18—H18B⋯Cg3ⁱⁱ	0.96	2.91	3.612 (2)	131
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x, y-1, z.

Table 2
Table 2. π-π stacking in the title compound (Å, °)

CgI–CgJ	Cg–Cg	α	(Cg–Cg)_Perp	(CgJ–CgI)_Perp	Slippage
Cg1–Cg2ⁱⁱⁱ	3.5479 (10)	3.27	3.482	3.483	0.676
Cg1 and Cg2 are the centroids of the N1,C1,C6–C9 and C1–C6 rings, respectively, and α is the angle between the corresponding planes. Symmetry code: (iii) -x, 2-y, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030499/dn2477sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030499/dn2477Isup2.hkl

checkCIF report

Comment top

Pyrimidine derivatives have broad biological properties: in particular pyrimidinylbenzoates is a highly effective herbicide with acetohydroxyacid synthase (AHAS) as target (Duggleby & Pang, 2000;). We herein report the crystal structure of one such pyrimidine derivative, the title compound, (I).

In the title compound (Fig.1), the pyrimidine (N2/N3/C10–C13) and difluorobenzyloxy (C20—C25) rings are twisted away from the mid quinoline ring (N1/C1—C9) with the dihedral angles of 54.6 (1)° and 74.1 (1)°, respectively. No other abnormal bond lengths and bond angles were observed in (I) in contrast with its some analogs (Li et al., 2006; Li & Huang, 2007; Li & Wang, 2007).

A weak C—H···O interactions links symmetry related molecules to form a pseudo dimer (Fig.2 and Table 1). Then π-π interactions between the quinoline rings of symmetry related molecules link these dimers into a one-dimensional chain running parallel to the [1 0 1] direction (Table 2). Furthermore, weak C—H···π interactions (Table 1) join these adjacent [101] chains to form a two-dimensional layer running parallel to the (101) plane.

Related literature top

Pyrimidinylbenzoates are highly effective herbicides with acetohydroxy acid synthase (AHAS) as target, see: Duggleby & Pang (2000). For related structures, see: Li & Huang (2007); Li & Wang (2007); Li et al. (2006).

Experimental top

A sulution of ethyl 4-(4,6-dimethoxypyrimidin-2-yl)-2-oxo-1,2-dihydroquinoline -3-carboxylate (0.35 g, 1 mmol) and NaH (60%, dispersion in mineral oil) (0.05 g, 1.2 mmol) in 10 ml N,N-dimethylformamide(DMF) was stirred at 273k for 0.5 h, and 2-(bromomethyl)-1,3-difluorobenzene (0.23 g, 1.1 mmol) was then added for 10 h.The reaction 200 ml of water, extracted with ethyl acetate (50 ml × 3), dried with anhydrous magnesium sulfate, and filtered off by suction, and the solvent was evaporated to give the crude product, which was purified by chromatography on silica using petroleum ether/acetone (8:1 v/v) as eluant to obtain the title compound as a white solid (yield 0.19 g, 47%). The product was recrystallized from an ethanol at room temperature to give crystals suitable for single-crystal X-ray diffraction.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of the pseudo dimer through C-H···O hydrogen bonds. Hydrogen atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) -x+1, -y+2, -z+1]

Ethyl 2-(2,6-difluorobenzyloxy)-4-(4,6-dimethoxypyrimidin-2-yl)quinoline-3- carboxylate top

Crystal data top

C₂₅H₂₁F₂N₃O₅	Z = 2
M_r = 481.45	F(000) = 500
Triclinic, P1	D_x = 1.390 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6623 (6) Å	Cell parameters from 4454 reflections
b = 10.7044 (6) Å	θ = 2.5–27.9°
c = 11.3856 (7) Å	µ = 0.11 mm⁻¹
α = 84.466 (1)°	T = 297 K
β = 82.251 (2)°	Block, colourless
γ = 81.394 (1)°	0.20 × 0.20 × 0.10 mm
V = 1150.21 (12) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4954 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	3541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
0.3° wide ω exposures scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→12
T_min = 0.959, T_max = 0.989	k = −13→13
12431 measured reflections	l = −14→14

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1077P)² + 0.004P] where P = (F_o² + 2F_c²)/3
4954 reflections	(Δ/σ)_max < 0.001
319 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₅H₂₁F₂N₃O₅	γ = 81.394 (1)°
M_r = 481.45	V = 1150.21 (12) Å³
Triclinic, P1	Z = 2
a = 9.6623 (6) Å	Mo Kα radiation
b = 10.7044 (6) Å	µ = 0.11 mm⁻¹
c = 11.3856 (7) Å	T = 297 K
α = 84.466 (1)°	0.20 × 0.20 × 0.10 mm
β = 82.251 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4954 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	3541 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.989	R_int = 0.035
12431 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.06	Δρ_max = 0.30 e Å⁻³
4954 reflections	Δρ_min = −0.23 e Å⁻³
319 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
C1	−0.11250 (16)	1.02922 (15)	0.13717 (14)	0.0399 (4)
C2	−0.20285 (19)	1.12507 (18)	0.08156 (17)	0.0518 (4)
H2	−0.1963	1.2096	0.0892	0.062*
C3	−0.3002 (2)	1.09504 (19)	0.01640 (17)	0.0559 (5)
H3	−0.3596	1.1593	−0.0200	0.067*
C4	−0.31136 (19)	0.96834 (19)	0.00409 (17)	0.0535 (5)
H4	−0.3772	0.9490	−0.0414	0.064*
C5	−0.22682 (18)	0.87332 (17)	0.05793 (15)	0.0467 (4)
H5	−0.2358	0.7894	0.0496	0.056*
C6	−0.12486 (16)	0.90099 (15)	0.12685 (13)	0.0382 (4)
C7	−0.02903 (16)	0.80657 (15)	0.18258 (14)	0.0379 (4)
C8	0.07269 (16)	0.84312 (14)	0.23904 (14)	0.0378 (4)
C9	0.07460 (16)	0.97547 (15)	0.24412 (14)	0.0397 (4)
C10	−0.03328 (16)	0.66870 (15)	0.17606 (13)	0.0378 (4)
C11	−0.15329 (17)	0.50141 (15)	0.20841 (15)	0.0439 (4)
C12	−0.03457 (18)	0.42061 (16)	0.17093 (16)	0.0474 (4)
H12	−0.0349	0.3339	0.1700	0.057*
C13	0.08520 (18)	0.47704 (15)	0.13469 (15)	0.0428 (4)
C14	−0.3984 (2)	0.5352 (2)	0.2799 (2)	0.0682 (6)
H14A	−0.3829	0.5797	0.3452	0.102*
H14B	−0.4753	0.4874	0.3041	0.102*
H14C	−0.4207	0.5951	0.2145	0.102*
C15	0.3280 (2)	0.4621 (2)	0.0603 (2)	0.0650 (5)
H15A	0.3116	0.5246	−0.0044	0.097*
H15B	0.4055	0.3993	0.0354	0.097*
H15C	0.3501	0.5021	0.1261	0.097*
C16	0.17828 (19)	0.75111 (15)	0.29953 (15)	0.0439 (4)
C17	0.1993 (3)	0.5997 (2)	0.4653 (2)	0.0774 (7)
H17A	0.1614	0.6036	0.5484	0.093*
H17B	0.2941	0.6220	0.4559	0.093*
C18	0.2047 (3)	0.4705 (2)	0.4309 (2)	0.0838 (7)
H18A	0.1105	0.4507	0.4343	0.126*
H18B	0.2555	0.4119	0.4845	0.126*
H18C	0.2516	0.4643	0.3514	0.126*
C19	0.17799 (19)	1.13573 (16)	0.31615 (18)	0.0514 (5)
H19A	0.0887	1.1728	0.3567	0.062*
H19B	0.1933	1.1807	0.2384	0.062*
C20	0.29534 (18)	1.14504 (15)	0.38676 (16)	0.0445 (4)
C21	0.2822 (2)	1.12069 (18)	0.50781 (18)	0.0598 (5)
C22	0.3845 (3)	1.1322 (2)	0.5770 (2)	0.0815 (8)
H22	0.3701	1.1150	0.6590	0.098*
C23	0.5084 (3)	1.1696 (2)	0.5223 (3)	0.0841 (8)
H23	0.5792	1.1781	0.5676	0.101*
C24	0.5287 (2)	1.1944 (2)	0.4020 (3)	0.0767 (7)
H24	0.6129	1.2195	0.3648	0.092*
C25	0.4223 (2)	1.18172 (18)	0.33639 (19)	0.0555 (5)
F1	0.16058 (16)	1.08091 (16)	0.55995 (13)	0.0978 (5)
F2	0.44154 (15)	1.20738 (14)	0.21759 (13)	0.0900 (5)
N1	−0.01274 (14)	1.06487 (12)	0.19857 (12)	0.0431 (3)
N2	0.08787 (14)	0.60077 (13)	0.13662 (12)	0.0415 (3)
N3	−0.15616 (14)	0.62592 (13)	0.21236 (12)	0.0435 (3)
O1	−0.27320 (13)	0.45076 (12)	0.24386 (13)	0.0572 (4)
O2	0.20379 (13)	0.40262 (12)	0.09621 (12)	0.0580 (4)
O3	0.30275 (14)	0.73618 (13)	0.27045 (13)	0.0606 (4)
O4	0.11257 (15)	0.68999 (12)	0.39364 (12)	0.0596 (4)
O5	0.17624 (12)	1.00344 (10)	0.30413 (11)	0.0485 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0371 (8)	0.0391 (9)	0.0455 (9)	−0.0126 (7)	−0.0069 (7)	0.0001 (7)
C2	0.0490 (10)	0.0417 (9)	0.0676 (12)	−0.0110 (8)	−0.0175 (9)	0.0032 (8)
C3	0.0509 (11)	0.0558 (11)	0.0623 (11)	−0.0051 (9)	−0.0198 (9)	0.0044 (9)
C4	0.0453 (10)	0.0634 (12)	0.0571 (11)	−0.0112 (9)	−0.0203 (8)	−0.0056 (9)
C5	0.0449 (9)	0.0472 (10)	0.0533 (10)	−0.0138 (7)	−0.0150 (7)	−0.0063 (7)
C6	0.0352 (8)	0.0413 (9)	0.0410 (8)	−0.0122 (7)	−0.0073 (6)	−0.0027 (6)
C7	0.0390 (8)	0.0360 (8)	0.0419 (8)	−0.0137 (6)	−0.0069 (6)	−0.0029 (6)
C8	0.0378 (8)	0.0329 (8)	0.0464 (9)	−0.0124 (6)	−0.0108 (7)	−0.0022 (6)
C9	0.0385 (8)	0.0357 (8)	0.0495 (9)	−0.0154 (7)	−0.0119 (7)	−0.0020 (7)
C10	0.0402 (8)	0.0360 (8)	0.0422 (8)	−0.0126 (6)	−0.0144 (6)	−0.0041 (6)
C11	0.0468 (10)	0.0412 (9)	0.0512 (9)	−0.0201 (7)	−0.0213 (7)	0.0019 (7)
C12	0.0550 (10)	0.0336 (8)	0.0616 (11)	−0.0168 (8)	−0.0227 (8)	−0.0049 (7)
C13	0.0476 (9)	0.0376 (9)	0.0492 (9)	−0.0106 (7)	−0.0182 (7)	−0.0085 (7)
C14	0.0474 (11)	0.0685 (14)	0.0941 (16)	−0.0252 (10)	−0.0097 (10)	−0.0055 (11)
C15	0.0515 (11)	0.0654 (13)	0.0776 (14)	−0.0086 (10)	−0.0020 (10)	−0.0108 (11)
C16	0.0513 (10)	0.0331 (8)	0.0542 (10)	−0.0139 (7)	−0.0213 (8)	−0.0048 (7)
C17	0.1054 (18)	0.0602 (13)	0.0727 (14)	−0.0146 (12)	−0.0449 (13)	0.0172 (11)
C18	0.1047 (19)	0.0519 (13)	0.1008 (18)	−0.0081 (12)	−0.0420 (15)	0.0019 (12)
C19	0.0514 (10)	0.0326 (9)	0.0774 (12)	−0.0126 (7)	−0.0247 (9)	−0.0068 (8)
C20	0.0461 (9)	0.0311 (8)	0.0616 (11)	−0.0103 (7)	−0.0155 (8)	−0.0101 (7)
C21	0.0686 (13)	0.0479 (11)	0.0653 (12)	−0.0085 (9)	−0.0097 (10)	−0.0141 (9)
C22	0.120 (2)	0.0638 (14)	0.0692 (14)	−0.0051 (14)	−0.0414 (14)	−0.0200 (11)
C23	0.1000 (19)	0.0523 (13)	0.119 (2)	−0.0128 (13)	−0.0703 (17)	−0.0179 (13)
C24	0.0579 (13)	0.0531 (12)	0.131 (2)	−0.0246 (10)	−0.0378 (13)	−0.0045 (13)
C25	0.0548 (11)	0.0440 (10)	0.0733 (13)	−0.0174 (8)	−0.0191 (9)	−0.0007 (9)
F1	0.0910 (10)	0.1135 (12)	0.0842 (10)	−0.0252 (9)	0.0183 (8)	−0.0065 (8)
F2	0.0820 (9)	0.1069 (12)	0.0810 (9)	−0.0321 (8)	−0.0064 (7)	0.0174 (8)
N1	0.0414 (7)	0.0344 (7)	0.0575 (9)	−0.0139 (6)	−0.0137 (6)	0.0002 (6)
N2	0.0443 (8)	0.0374 (7)	0.0475 (8)	−0.0127 (6)	−0.0122 (6)	−0.0066 (6)
N3	0.0433 (8)	0.0389 (8)	0.0539 (8)	−0.0171 (6)	−0.0131 (6)	−0.0040 (6)
O1	0.0496 (7)	0.0471 (7)	0.0822 (9)	−0.0258 (6)	−0.0164 (6)	−0.0001 (6)
O2	0.0518 (8)	0.0441 (7)	0.0809 (9)	−0.0077 (6)	−0.0085 (6)	−0.0169 (6)
O3	0.0431 (7)	0.0551 (8)	0.0882 (10)	−0.0084 (6)	−0.0251 (6)	−0.0016 (7)
O4	0.0696 (9)	0.0501 (8)	0.0614 (8)	−0.0137 (6)	−0.0221 (7)	0.0121 (6)
O5	0.0503 (7)	0.0322 (6)	0.0715 (8)	−0.0135 (5)	−0.0286 (6)	−0.0050 (5)

Geometric parameters (Å, º) top

C1—N1	1.381 (2)	C14—H14C	0.9600
C1—C2	1.404 (2)	C15—O2	1.435 (2)
C1—C6	1.413 (2)	C15—H15A	0.9600
C2—C3	1.365 (2)	C15—H15B	0.9600
C2—H2	0.9300	C15—H15C	0.9600
C3—C4	1.398 (3)	C16—O3	1.194 (2)
C3—H3	0.9300	C16—O4	1.336 (2)
C4—C5	1.358 (3)	C17—O4	1.446 (2)
C4—H4	0.9300	C17—C18	1.465 (3)
C5—C6	1.419 (2)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C6—C7	1.427 (2)	C18—H18A	0.9600
C7—C8	1.366 (2)	C18—H18B	0.9600
C7—C10	1.492 (2)	C18—H18C	0.9600
C8—C9	1.426 (2)	C19—O5	1.4386 (18)
C8—C16	1.498 (2)	C19—C20	1.496 (2)
C9—N1	1.295 (2)	C19—H19A	0.9700
C9—O5	1.3525 (18)	C19—H19B	0.9700
C10—N2	1.329 (2)	C20—C21	1.370 (3)
C10—N3	1.336 (2)	C20—C25	1.378 (3)
C11—N3	1.334 (2)	C21—F1	1.352 (2)
C11—O1	1.3487 (19)	C21—C22	1.370 (3)
C11—C12	1.374 (2)	C22—C23	1.370 (4)
C12—C13	1.381 (2)	C22—H22	0.9300
C12—H12	0.9300	C23—C24	1.363 (4)
C13—N2	1.331 (2)	C23—H23	0.9300
C13—O2	1.341 (2)	C24—C25	1.380 (3)
C14—O1	1.435 (2)	C24—H24	0.9300
C14—H14A	0.9600	C25—F2	1.347 (2)
C14—H14B	0.9600

N1—C1—C2	118.10 (14)	H15A—C15—H15C	109.5
N1—C1—C6	122.54 (14)	H15B—C15—H15C	109.5
C2—C1—C6	119.36 (14)	O3—C16—O4	124.76 (16)
C3—C2—C1	120.49 (17)	O3—C16—C8	125.61 (16)
C3—C2—H2	119.8	O4—C16—C8	109.61 (15)
C1—C2—H2	119.8	O4—C17—C18	111.28 (18)
C2—C3—C4	120.44 (17)	O4—C17—H17A	109.4
C2—C3—H3	119.8	C18—C17—H17A	109.4
C4—C3—H3	119.8	O4—C17—H17B	109.4
C5—C4—C3	120.58 (16)	C18—C17—H17B	109.4
C5—C4—H4	119.7	H17A—C17—H17B	108.0
C3—C4—H4	119.7	C17—C18—H18A	109.5
C4—C5—C6	120.53 (16)	C17—C18—H18B	109.5
C4—C5—H5	119.7	H18A—C18—H18B	109.5
C6—C5—H5	119.7	C17—C18—H18C	109.5
C1—C6—C5	118.59 (14)	H18A—C18—H18C	109.5
C1—C6—C7	117.55 (13)	H18B—C18—H18C	109.5
C5—C6—C7	123.81 (14)	O5—C19—C20	107.44 (13)
C8—C7—C6	119.30 (14)	O5—C19—H19A	110.2
C8—C7—C10	119.15 (14)	C20—C19—H19A	110.2
C6—C7—C10	121.50 (13)	O5—C19—H19B	110.2
C7—C8—C9	118.12 (14)	C20—C19—H19B	110.2
C7—C8—C16	123.18 (14)	H19A—C19—H19B	108.5
C9—C8—C16	118.67 (13)	C21—C20—C25	115.06 (17)
N1—C9—O5	120.62 (13)	C21—C20—C19	121.87 (17)
N1—C9—C8	125.03 (14)	C25—C20—C19	123.05 (17)
O5—C9—C8	114.34 (13)	F1—C21—C20	116.70 (18)
N2—C10—N3	126.87 (14)	F1—C21—C22	119.1 (2)
N2—C10—C7	115.84 (14)	C20—C21—C22	124.1 (2)
N3—C10—C7	117.27 (14)	C23—C22—C21	118.3 (2)
N3—C11—O1	118.56 (15)	C23—C22—H22	120.8
N3—C11—C12	123.87 (15)	C21—C22—H22	120.8
O1—C11—C12	117.57 (15)	C24—C23—C22	120.5 (2)
C11—C12—C13	115.41 (15)	C24—C23—H23	119.8
C11—C12—H12	122.3	C22—C23—H23	119.8
C13—C12—H12	122.3	C23—C24—C25	118.9 (2)
N2—C13—O2	119.06 (15)	C23—C24—H24	120.5
N2—C13—C12	123.08 (16)	C25—C24—H24	120.5
O2—C13—C12	117.86 (15)	F2—C25—C20	117.91 (16)
O1—C14—H14A	109.5	F2—C25—C24	119.04 (19)
O1—C14—H14B	109.5	C20—C25—C24	123.0 (2)
H14A—C14—H14B	109.5	C9—N1—C1	117.38 (13)
O1—C14—H14C	109.5	C10—N2—C13	115.82 (14)
H14A—C14—H14C	109.5	C11—N3—C10	114.94 (14)
H14B—C14—H14C	109.5	C11—O1—C14	117.78 (14)
O2—C15—H15A	109.5	C13—O2—C15	117.34 (14)
O2—C15—H15B	109.5	C16—O4—C17	117.21 (17)
H15A—C15—H15B	109.5	C9—O5—C19	116.23 (12)
O2—C15—H15C	109.5

N1—C1—C2—C3	177.81 (17)	C25—C20—C21—F1	−178.15 (16)
C6—C1—C2—C3	−1.1 (3)	C19—C20—C21—F1	3.6 (3)
C1—C2—C3—C4	0.0 (3)	C25—C20—C21—C22	0.7 (3)
C2—C3—C4—C5	0.8 (3)	C19—C20—C21—C22	−177.59 (18)
C3—C4—C5—C6	−0.5 (3)	F1—C21—C22—C23	178.40 (19)
N1—C1—C6—C5	−177.47 (15)	C20—C21—C22—C23	−0.4 (3)
C2—C1—C6—C5	1.4 (2)	C21—C22—C23—C24	−0.1 (3)
N1—C1—C6—C7	−0.2 (2)	C22—C23—C24—C25	0.2 (4)
C2—C1—C6—C7	178.70 (15)	C21—C20—C25—F2	−179.82 (17)
C4—C5—C6—C1	−0.6 (3)	C19—C20—C25—F2	−1.5 (3)
C4—C5—C6—C7	−177.72 (16)	C21—C20—C25—C24	−0.5 (3)
C1—C6—C7—C8	−2.4 (2)	C19—C20—C25—C24	177.74 (17)
C5—C6—C7—C8	174.76 (15)	C23—C24—C25—F2	179.4 (2)
C1—C6—C7—C10	−179.66 (14)	C23—C24—C25—C20	0.1 (3)
C5—C6—C7—C10	−2.5 (2)	O5—C9—N1—C1	179.15 (14)
C6—C7—C8—C9	2.7 (2)	C8—C9—N1—C1	−2.2 (2)
C10—C7—C8—C9	180.00 (14)	C2—C1—N1—C9	−176.48 (15)
C6—C7—C8—C16	−179.72 (15)	C6—C1—N1—C9	2.4 (2)
C10—C7—C8—C16	−2.4 (2)	N3—C10—N2—C13	−0.7 (2)
C7—C8—C9—N1	−0.4 (2)	C7—C10—N2—C13	177.77 (13)
C16—C8—C9—N1	−178.08 (16)	O2—C13—N2—C10	−179.84 (14)
C7—C8—C9—O5	178.39 (14)	C12—C13—N2—C10	0.0 (2)
C16—C8—C9—O5	0.7 (2)	O1—C11—N3—C10	179.87 (14)
C8—C7—C10—N2	−50.7 (2)	C12—C11—N3—C10	0.3 (2)
C6—C7—C10—N2	126.58 (16)	N2—C10—N3—C11	0.5 (2)
C8—C7—C10—N3	127.95 (16)	C7—C10—N3—C11	−177.91 (13)
C6—C7—C10—N3	−54.8 (2)	N3—C11—O1—C14	2.2 (2)
N3—C11—C12—C13	−0.9 (2)	C12—C11—O1—C14	−178.28 (16)
O1—C11—C12—C13	179.53 (14)	N2—C13—O2—C15	0.7 (2)
C11—C12—C13—N2	0.8 (2)	C12—C13—O2—C15	−179.17 (16)
C11—C12—C13—O2	−179.41 (15)	O3—C16—O4—C17	0.2 (3)
C7—C8—C16—O3	115.1 (2)	C8—C16—O4—C17	−178.10 (15)
C9—C8—C16—O3	−67.3 (2)	C18—C17—O4—C16	−96.3 (2)
C7—C8—C16—O4	−66.5 (2)	N1—C9—O5—C19	1.6 (2)
C9—C8—C16—O4	111.05 (16)	C8—C9—O5—C19	−177.26 (14)
O5—C19—C20—C21	−77.8 (2)	C20—C19—O5—C9	178.85 (14)
O5—C19—C20—C25	104.00 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N3	0.93	2.54	3.075 (2)	117
C23—H23···O3ⁱ	0.93	2.60	3.476 (2)	158
C18—H18B···Cg3ⁱⁱ	0.96	2.91	3.612 (2)	131

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₁F₂N₃O₅
M_r	481.45
Crystal system, space group	Triclinic, P1
Temperature (K)	297
a, b, c (Å)	9.6623 (6), 10.7044 (6), 11.3856 (7)
α, β, γ (°)	84.466 (1), 82.251 (2), 81.394 (1)
V (Å³)	1150.21 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.959, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	12431, 4954, 3541
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.170, 1.06
No. of reflections	4954
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···O3ⁱ	0.93	2.60	3.476 (2)	157.7
C18—H18B···Cg3ⁱⁱ	0.96	2.91	3.612 (2)	131.

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

Table 2. π-π stacking in the title compound (Å, °) top

Cg(I)–Cg(J)	Cg–Cg	α	(CgI–CgJ)_Perp	(CgJ–CgI)_Perp	Slippage
Cg1–Cg2ⁱⁱⁱ	3.5479 (10)	3.27	3.482	3.483	0.676

Cg1 and Cg2 are the centroids of the N1,C1,C6–C9 and C1–C6 rings, respectively, and α is the angle between the corresponding planes. Symmetry code: (iii) -x, 2-y, -z.

Acknowledgements

The author acknowledges financial support by the Key Laboratory of Hunan Province for the Study and Utilization of Ethnic Medicinal Plant Resources, Huaihua University (No. SYSXM200911), the Project Planning of Science and Technology Department of Huaihua City (2009) and the Scientific Research Foundation of Huaihua University.

References

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