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Acta Cryst. (2010). E66, o2512-o2513    [ doi:10.1107/S1600536810034926 ]

1-{1-[2,8-Bis(trifluoromethyl)-4-quinolyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone

H. C. Devarajegowda, S. Jeyaseelan, V. Sumangala, Bojapoojary and S. P. Nayak

Abstract top

There are two independent molecules in the asymmetric unit of the title compound, C16H10F6N4O. The triazole ring is not coplanar with the quinoline ring system; the dihedral angle between the two planes being 74.47 (12) and 63.97 (13)° in the two molecules. The crystal structure is characterized by intermolecular C-H...F, C-H...N and C-H...O hydrogen bonding. Weak intramolecular C-H...F interactions are observed. Disorder is observed in two F atoms of one of the trifluoromethyl groups of one independent molecule [occupancy ratios 0.77 (3):0.23 (3) and 0.77 (4):0.23 (4)] and in all three F atoms of one of the trifluoromethyl groups of the second independent molecule [occupancy ratios 0.520 (14):0.480 (14), 0.615 (17):0.385 (17) and 0.783 (11):0.217 (11)]. The O atom is also disordered over two positions with occupancies of 0.60 (13) and 0.40 (13) in the first molecule.

Comment top

1,2,3-Triazoles and their benzoderivatives have attracted considerable attention because of their theoretical interest and synthetic value. They also find numerous applications in industry and agriculture due to their extensive biological activitiesand successful application as fluorescent whiteners, light stabilizers and optical brightening agents (Sanghvi et al., 1990).Functionalized 1, 2,3-triazoles constitute one of the common fragments present in biologically active compounds (Bohm et al.,1981).This has resulted in a wealth of synthetic methodology for their preparation and incorporation in more complex structures.The accentuated interest in these compounds continues to be expressed in the pharmaceutical community and biological properties of these agents have been the subject of ongoing investigations (Holla et al., 2005). The triazole scaffold has a wide range of therapeutic uses as it is ubiquitously found in drugs. The derivatives of 1, 2, 3-triazoles constitute an important family of heterocyclic compounds due to their chemotherapeutical values (Sanghvi et al., 1990). Some 1,2,3-triazoles are used as DNA cleaving agents and potassium channels activators (Biagi et al., 2004). Since many of them have remarkable antimicrobial(Karimkulov et al., 1991; Sherement et al., 2004), analgesic & anti-inflammatory (Savini et al. ,1994), local anesthetic (Banu et al. , 1999), antimalarial (Julino et al. , 1998), antiviral (Diana et al. ,1993), anti-proliferatine (Manfredini et al. ,2000), anticonvulsant (Rene et al. ,1986), antineoplastic(Passannanti et al. , 1998) and anticancer activity (Deng et al. ,2008), their synthesis and transformations have been received particular interest for a long time.

Fluorine incorporated compounds exhibit dramatically improved potency compared to their non-fluorinated analogues (Sector et al. ,1971) since its incorporation alters the electronic, lipophilic and steric parameters and can critically increase the intrinsic activity,chemical and metabolic stability.In particular, introduction of CF3 group in organic molecules immensely increased the pharmacological activity as well as lipophilicity (Barnard et al. ,1993).

The structure of 1-{1-[2,8-bis(trifluoromethyl) quinolin-4-yl]-5- methyl-1H-1,2,3-triazol-4-yl}ethanone contains two independent molecules in the asymmetric unit. The triazole ring is not coplanar with the quinoline ring system; the dihedral angle between the two planes is 74.21 (08)°. The structure of the molecules is stabilized by intermolecular C5–H5···F12 & C9–H9···N7, C16–H16A···O2 & C32–H32B···F5A and weak intramolecular C3–H3···F3 & C25–H25···F12 hydrogen bonding (Table 1) and shows two fluorine atoms disordered in one of the trifluoromethyl group and oxygen atom.

Related literature top

For general background to triazoles and their benzo derivatives, see: Sanghvi et al. (1990); Bohm et al. (1981); Holla et al. (2005); Biagi et al. (2004); Karimkulov et al. (1991); Sherement et al. (2004); Savini et al. (1994); Banu et al. (1999); Julino & Stevens (1998); Diana et al. (1993); Manfredini et al. (2000); Rene et al. (1986); Passannanti et al. (1998); Deng et al. (2008); Sector et al. (1971); Barnard et al. (1993). For a related structure, see: Al-eryani et al. (2010).

Experimental top

A solution of 4-Azido-2,8 bis trifluoro methyl quinoline (2.5 g,0.08 mol) in 25 mL me thanol was treated with acetyl acetone (0.9 g, 0.008 mol) and the mixture was cooled to 0°C. Sodium methoxide (0.008 mol) was added in lots under nitrogen over a period of 30 minutes. It was then stirred for 30 minutes. The progress of the reaction was monitored by TLC using ethyl acetate: hexane (1: 4, v/v) as mobile phase. The reaction mass is quenched to ice water. The title compound is isolated by filtration as a yellow solid. The recrystallization of the compound in methanol gave 76% of pure compound. Melting point: 427 K. Mol.Wt: 388.27 IR (KBr, γ/cm-1): 3025 (Ar—H), 1715 (C=O), 1005(C—F). 1H NMR (300 MHz, CDCl3): δ, 2.52(s, CH3, 3H), 2.83(s, 3H, COCH3), 7.26(s, Ar—H,1H), 7.65–7.68(d, 1H, Ar—H, J =8.4 Hz),8.32–8.34 (d, 1H, Ar—H, J =7.2 Hz), 7.83–7. 86 (t, IH, Ar—H, J =7.8 Hz). MS (m/z, %):388 (M+). Anal. calcd for C16 H10F6N4O (in %): C-49.47, H-2.61, N-14.44. Found C-49.49, H-2.60, N-14.43.

Refinement top

All H atoms were positioned at calculated positions with C—H = 0.93Å for aromatic H and 0.96Å for methyl H and refined using a riding model with Uiso(H) =1.5Ueq(C)for methyl H and 1.2U eq(C) for other and also refined two fluorine atoms of the trifluoromethyl group is disordered with two orientations.

variation in Ueq for C1, C11, C17 and C24 as compared to Neighbors

C1, C11, C17 and C24 are free terminal trifluoromethyl carbon attached to benzene ring of quinoline part of the structure. The high electron dense fluorine atoms, freely movable in this case, increase the thermal factor of the C1, C11, C17 and C24. Thus giving variation in Ueq as Compared to Neighbors

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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius and showing intramolecular hydrogen bonds as dashed lines.
[Figure 2] Fig. 2. Packing of the molecules showing hydrogen bonds as dashed lines.
1-{1-[2,8-Bis(trifluoromethyl)-4-quinolyl]-5-methyl-1H-1,2,3-triazol- 4-yl}ethanone top
Crystal data top
C16H10F6N4OF(000) = 1568
Mr = 388.28Dx = 1.534 Mg m−3
Monoclinic, P21/nMelting point: 427 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 14.064 (2) ÅCell parameters from 5923 reflections
b = 8.7275 (13) Åθ = 1.5–25.0°
c = 27.468 (4) ŵ = 0.14 mm−1
β = 94.172 (2)°T = 293 K
V = 3362.6 (9) Å3Plate, colourless
Z = 80.20 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		5923 independent reflections
Radiation source: fine-focus sealed tube4754 reflections with I > 2σ(I)
graphiteRint = 0.028
ω and φ scansθmax = 25.0°, θmin = 1.5°
Absorption correction: ψ scan
(SADABS; Bruker, 2001)		h = −16→16
Tmin = 0.972, Tmax = 0.979k = −10→10
23473 measured reflectionsl = −32→30
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.069P)2 + 1.1626P]
where P = (Fo2 + 2Fc2)/3
5923 reflections(Δ/σ)max < 0.001
547 parametersΔρmax = 0.26 e Å−3
63 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C16H10F6N4OV = 3362.6 (9) Å3
Mr = 388.28Z = 8
Monoclinic, P21/nMo Kα radiation
a = 14.064 (2) ŵ = 0.14 mm−1
b = 8.7275 (13) ÅT = 293 K
c = 27.468 (4) Å0.20 × 0.20 × 0.15 mm
β = 94.172 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		5923 independent reflections
Absorption correction: ψ scan
(SADABS; Bruker, 2001)		4754 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.979Rint = 0.028
23473 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.139Δρmax = 0.26 e Å−3
S = 1.05Δρmin = −0.23 e Å−3
5923 reflectionsAbsolute structure: ?
547 parametersFlack parameter: ?
63 restraintsRogers parameter: ?
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 > 2σ(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
xyzUiso*/UeqOcc. (<1)
F10.62603 (13)−0.2838 (2)0.18151 (6)0.0844 (5)
F20.75645 (12)−0.3765 (2)0.16020 (6)0.0801 (5)
F30.62542 (16)−0.4783 (2)0.13491 (7)0.1023 (7)
F4B0.8238 (11)0.0406 (9)0.23119 (18)0.128 (3)0.77 (3)
F4A0.7910 (14)0.083 (3)0.2312 (5)0.078 (5)0.23 (3)
F5B0.9284 (8)0.158 (3)0.1861 (9)0.094 (6)0.23 (4)
F5A0.9304 (3)0.101 (2)0.1948 (5)0.135 (3)0.77 (4)
F60.82879 (16)0.2748 (2)0.20693 (7)0.0989 (6)
F7B0.2388 (9)0.1504 (13)0.27486 (16)0.134 (5)0.520 (14)
F7A0.1679 (8)0.0748 (7)0.2564 (4)0.121 (4)0.480 (14)
F8B0.2743 (9)0.2284 (13)0.2066 (6)0.135 (6)0.385 (17)
F8A0.2871 (4)0.2331 (8)0.2421 (6)0.150 (4)0.615 (17)
F9B0.1555 (9)0.0653 (10)0.2269 (7)0.096 (6)0.217 (11)
F9A0.1964 (4)0.1177 (6)0.19132 (18)0.128 (2)0.783 (11)
F100.06252 (14)0.3249 (2)0.37351 (6)0.0909 (6)
F110.17217 (12)0.4920 (3)0.37357 (6)0.0939 (6)
F120.04672 (15)0.5362 (3)0.41025 (6)0.1034 (7)
O1B0.8131 (8)0.499 (5)−0.0850 (17)0.094 (6)0.40 (13)
O1A0.8059 (15)0.466 (5)−0.0966 (16)0.088 (6)0.60 (13)
O2−0.05430 (19)0.9546 (3)0.05710 (9)0.0934 (7)
N10.75116 (13)−0.0489 (2)0.14556 (6)0.0459 (4)
N20.70539 (13)0.2637 (2)0.02946 (7)0.0448 (4)
N30.61525 (14)0.3219 (2)0.02063 (8)0.0568 (5)
N40.61674 (15)0.4042 (2)−0.01854 (8)0.0576 (5)
N50.11417 (13)0.3718 (2)0.27600 (7)0.0504 (5)
N6−0.00853 (13)0.5686 (2)0.14652 (6)0.0466 (4)
N7−0.06553 (16)0.4771 (2)0.11648 (7)0.0602 (6)
N8−0.09389 (16)0.5602 (3)0.07907 (8)0.0648 (6)
C10.6679 (2)−0.3437 (3)0.14425 (10)0.0590 (7)
C20.66029 (16)−0.2409 (3)0.10050 (8)0.0456 (5)
C30.61058 (17)−0.2867 (3)0.05863 (9)0.0518 (6)
H30.5842−0.38440.05680.062*
C40.59872 (17)−0.1888 (3)0.01827 (8)0.0527 (6)
H40.5662−0.2234−0.01030.063*
C50.63381 (16)−0.0448 (3)0.02028 (8)0.0469 (5)
H50.62430.0197−0.00660.056*
C60.68504 (14)0.0080 (2)0.06324 (7)0.0405 (5)
C70.70045 (14)−0.0920 (2)0.10371 (7)0.0401 (5)
C80.72286 (15)0.1571 (2)0.06873 (8)0.0422 (5)
C90.77317 (16)0.1999 (3)0.11060 (8)0.0493 (5)
H90.79880.29780.11440.059*
C100.78488 (16)0.0901 (3)0.14781 (8)0.0480 (5)
C110.8398 (2)0.1312 (3)0.19515 (10)0.0672 (8)
C120.76358 (16)0.3096 (3)−0.00439 (8)0.0488 (5)
C130.70503 (18)0.4002 (3)−0.03525 (9)0.0523 (6)
C140.7286 (3)0.4792 (3)−0.07976 (10)0.0699 (8)
C150.6496 (3)0.5594 (5)−0.10873 (13)0.1034 (12)
H15A0.67400.6064−0.13690.155*
H15B0.62300.6367−0.08890.155*
H15C0.60100.4867−0.11910.155*
C160.86421 (19)0.2661 (4)−0.00449 (11)0.0729 (8)
H16A0.88090.20090.02300.109*
H16B0.90310.3566−0.00230.109*
H16C0.87450.2124−0.03410.109*
C170.2014 (2)0.1926 (3)0.23226 (11)0.0745 (8)
C180.13305 (17)0.3238 (3)0.23277 (9)0.0523 (6)
C190.09522 (17)0.3874 (3)0.18863 (9)0.0514 (6)
H190.11230.34980.15880.062*
C200.03335 (15)0.5047 (2)0.19089 (8)0.0431 (5)
C210.00741 (15)0.5608 (3)0.23647 (8)0.0443 (5)
C220.05239 (15)0.4897 (3)0.27825 (8)0.0442 (5)
C230.03100 (17)0.5448 (3)0.32524 (8)0.0526 (6)
C240.0786 (2)0.4748 (4)0.36993 (10)0.0670 (7)
C25−0.03136 (19)0.6618 (3)0.32868 (10)0.0636 (7)
H25−0.04400.69830.35930.076*
C26−0.07694 (19)0.7285 (3)0.28722 (10)0.0645 (7)
H26−0.12010.80780.29060.077*
C27−0.05890 (17)0.6790 (3)0.24192 (9)0.0537 (6)
H27−0.09040.72330.21450.064*
C28−0.00056 (16)0.7101 (3)0.12737 (8)0.0483 (5)
C29−0.05686 (17)0.7031 (3)0.08470 (8)0.0521 (6)
C30−0.07782 (19)0.8242 (4)0.04788 (10)0.0658 (7)
C31−0.1272 (2)0.7785 (5)0.00060 (11)0.0913 (11)
H31A−0.13670.8671−0.01990.137*
H31B−0.18790.73400.00620.137*
H31C−0.08910.7049−0.01520.137*
C320.0637 (2)0.8291 (3)0.14926 (11)0.0700 (8)
H32A0.09170.79370.18010.105*
H32B0.02800.92100.15400.105*
H32C0.11310.85000.12790.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0980 (12)0.1025 (13)0.0544 (10)0.0095 (10)0.0171 (9)0.0280 (9)
F20.0782 (11)0.0789 (11)0.0806 (11)0.0107 (8)−0.0127 (9)0.0266 (9)
F30.1420 (17)0.0650 (11)0.0946 (13)−0.0417 (11)−0.0284 (12)0.0313 (10)
F4B0.233 (7)0.082 (3)0.058 (2)−0.045 (4)−0.070 (3)0.0165 (17)
F4A0.094 (8)0.112 (9)0.028 (5)−0.024 (6)0.007 (5)0.003 (5)
F5B0.073 (8)0.099 (9)0.101 (8)−0.024 (8)−0.042 (6)0.003 (7)
F5A0.086 (3)0.183 (8)0.127 (5)0.044 (3)−0.058 (2)−0.064 (5)
F60.1453 (18)0.0743 (12)0.0709 (11)−0.0031 (11)−0.0348 (11)−0.0232 (9)
F7B0.169 (8)0.152 (7)0.076 (3)0.113 (7)−0.026 (4)0.003 (3)
F7A0.180 (8)0.074 (4)0.110 (6)0.047 (4)0.015 (6)0.025 (4)
F8B0.132 (8)0.138 (7)0.144 (9)0.073 (6)0.068 (6)0.044 (6)
F8A0.083 (3)0.130 (4)0.227 (9)0.047 (3)−0.063 (4)−0.063 (5)
F9B0.115 (8)0.050 (5)0.117 (11)0.010 (5)−0.042 (7)−0.037 (6)
F9A0.142 (4)0.115 (3)0.121 (3)0.067 (3)−0.026 (3)−0.054 (3)
F100.1089 (14)0.0942 (13)0.0684 (11)−0.0121 (11)−0.0012 (10)0.0312 (10)
F110.0689 (11)0.1451 (17)0.0648 (11)−0.0185 (11)−0.0156 (8)0.0198 (11)
F120.1265 (16)0.1486 (18)0.0351 (9)0.0113 (13)0.0062 (9)−0.0014 (10)
O1B0.129 (13)0.106 (10)0.047 (10)−0.015 (10)0.021 (5)0.023 (7)
O1A0.094 (6)0.114 (9)0.059 (9)0.024 (4)0.031 (4)0.029 (7)
O20.1241 (19)0.0700 (14)0.0847 (15)0.0196 (13)−0.0017 (13)0.0242 (12)
N10.0517 (11)0.0504 (11)0.0349 (10)−0.0014 (9)−0.0021 (8)0.0016 (8)
N20.0466 (10)0.0431 (10)0.0442 (10)−0.0013 (8)0.0004 (8)0.0059 (8)
N30.0491 (11)0.0599 (12)0.0609 (13)0.0026 (9)0.0012 (9)0.0120 (10)
N40.0615 (13)0.0535 (12)0.0567 (13)0.0052 (10)−0.0027 (10)0.0111 (10)
N50.0528 (11)0.0510 (11)0.0465 (11)−0.0011 (9)−0.0011 (9)0.0046 (9)
N60.0521 (11)0.0486 (11)0.0383 (10)−0.0030 (8)−0.0022 (8)−0.0018 (8)
N70.0709 (14)0.0609 (13)0.0465 (12)−0.0131 (10)−0.0121 (10)0.0015 (10)
N80.0671 (14)0.0775 (16)0.0476 (12)−0.0073 (12)−0.0113 (10)0.0034 (11)
C10.0687 (17)0.0540 (15)0.0529 (15)−0.0091 (12)−0.0049 (13)0.0107 (12)
C20.0496 (12)0.0448 (12)0.0420 (12)−0.0032 (10)0.0009 (10)0.0040 (9)
C30.0579 (14)0.0452 (13)0.0515 (14)−0.0080 (11)−0.0014 (11)−0.0018 (11)
C40.0576 (14)0.0581 (14)0.0411 (13)−0.0067 (11)−0.0049 (10)−0.0056 (11)
C50.0536 (13)0.0528 (13)0.0336 (11)−0.0031 (11)−0.0013 (9)0.0021 (10)
C60.0409 (11)0.0458 (12)0.0348 (11)−0.0006 (9)0.0035 (9)0.0015 (9)
C70.0426 (11)0.0447 (12)0.0328 (11)−0.0013 (9)0.0008 (9)−0.0003 (9)
C80.0421 (11)0.0460 (12)0.0386 (12)−0.0017 (9)0.0034 (9)0.0040 (9)
C90.0533 (13)0.0459 (12)0.0480 (13)−0.0092 (10)−0.0018 (10)−0.0011 (10)
C100.0498 (13)0.0514 (13)0.0418 (12)−0.0037 (10)−0.0035 (10)−0.0032 (10)
C110.084 (2)0.0591 (17)0.0552 (17)−0.0057 (15)−0.0206 (15)−0.0056 (13)
C120.0575 (13)0.0462 (12)0.0434 (12)0.0015 (10)0.0076 (10)0.0065 (10)
C130.0639 (15)0.0460 (13)0.0470 (13)0.0038 (11)0.0038 (11)0.0051 (10)
C140.093 (2)0.0618 (17)0.0549 (17)0.0063 (16)0.0078 (16)0.0152 (13)
C150.127 (3)0.106 (3)0.077 (2)0.024 (2)0.003 (2)0.044 (2)
C160.0649 (16)0.084 (2)0.0722 (19)0.0182 (15)0.0223 (14)0.0243 (15)
C170.088 (2)0.0654 (19)0.070 (2)0.0224 (17)−0.0001 (18)0.0005 (16)
C180.0547 (13)0.0499 (13)0.0519 (15)0.0016 (11)0.0009 (11)0.0016 (11)
C190.0601 (14)0.0510 (13)0.0430 (13)0.0010 (11)0.0031 (11)−0.0045 (10)
C200.0472 (12)0.0442 (12)0.0372 (12)−0.0039 (9)−0.0008 (9)0.0015 (9)
C210.0423 (11)0.0468 (12)0.0435 (12)−0.0046 (9)0.0014 (9)−0.0021 (10)
C220.0438 (12)0.0480 (13)0.0404 (12)−0.0067 (10)−0.0003 (9)0.0018 (9)
C230.0535 (13)0.0636 (15)0.0406 (13)−0.0104 (12)0.0033 (10)−0.0008 (11)
C240.0702 (18)0.086 (2)0.0445 (15)−0.0115 (15)0.0008 (12)0.0076 (13)
C250.0677 (16)0.0779 (18)0.0465 (14)−0.0004 (14)0.0120 (12)−0.0108 (13)
C260.0644 (16)0.0702 (17)0.0599 (17)0.0123 (13)0.0110 (13)−0.0067 (13)
C270.0518 (13)0.0611 (15)0.0476 (14)0.0039 (11)−0.0004 (11)0.0021 (11)
C280.0529 (13)0.0479 (13)0.0441 (13)0.0045 (10)0.0033 (10)0.0014 (10)
C290.0505 (13)0.0604 (15)0.0455 (13)0.0068 (11)0.0031 (10)0.0055 (11)
C300.0598 (15)0.081 (2)0.0567 (16)0.0181 (14)0.0061 (12)0.0182 (15)
C310.086 (2)0.122 (3)0.0627 (19)0.021 (2)−0.0116 (16)0.0249 (19)
C320.087 (2)0.0544 (15)0.0669 (18)−0.0120 (14)−0.0050 (15)0.0025 (13)
Geometric parameters (Å, °) top
F1—C11.325 (3)C5—H50.9300
F2—C11.321 (3)C6—C81.410 (3)
F3—C11.334 (3)C6—C71.418 (3)
F4B—C111.300 (4)C8—C91.358 (3)
F4A—C111.313 (7)C9—C101.402 (3)
F5B—C111.309 (8)C9—H90.9300
F5A—C111.301 (5)C10—C111.507 (3)
F6—C111.306 (3)C12—C131.386 (3)
F7B—C171.301 (5)C12—C161.465 (3)
F7A—C171.328 (5)C13—C141.462 (4)
F8B—C171.324 (6)C14—C151.493 (4)
F8A—C171.267 (5)C15—H15A0.9600
F9B—C171.288 (7)C15—H15B0.9600
F9A—C171.298 (4)C15—H15C0.9600
F10—C241.333 (3)C16—H16A0.9600
F11—C241.321 (3)C16—H16B0.9600
F12—C241.337 (3)C16—H16C0.9600
O1B—C141.220 (9)C17—C181.496 (4)
O1A—C141.217 (7)C18—C191.402 (3)
O2—C301.207 (4)C19—C201.348 (3)
N1—C101.303 (3)C19—H190.9300
N1—C71.361 (3)C20—C211.417 (3)
N2—C121.344 (3)C21—C271.406 (3)
N2—N31.371 (3)C21—C221.413 (3)
N2—C81.432 (3)C22—C231.429 (3)
N3—N41.295 (3)C23—C251.354 (4)
N4—C131.355 (3)C23—C241.486 (4)
N5—C181.304 (3)C25—C261.393 (4)
N5—C221.352 (3)C25—H250.9300
N6—C281.350 (3)C26—C271.358 (3)
N6—N71.366 (3)C26—H260.9300
N6—C201.428 (3)C27—H270.9300
N7—N81.297 (3)C28—C291.367 (3)
N8—C291.356 (3)C28—C321.475 (4)
C1—C21.497 (3)C29—C301.478 (4)
C2—C31.362 (3)C30—C311.482 (4)
C2—C71.417 (3)C31—H31A0.9600
C3—C41.400 (3)C31—H31B0.9600
C3—H30.9300C31—H31C0.9600
C4—C51.350 (3)C32—H32A0.9600
C4—H40.9300C32—H32B0.9600
C5—C61.414 (3)C32—H32C0.9600
C10—N1—C7117.63 (19)H16A—C16—H16B109.5
C12—N2—N3111.66 (18)C12—C16—H16C109.5
C12—N2—C8129.43 (18)H16A—C16—H16C109.5
N3—N2—C8118.67 (17)H16B—C16—H16C109.5
N4—N3—N2106.37 (18)F8A—C17—F9B136.6 (7)
N3—N4—C13109.73 (19)F8A—C17—F9A108.5 (6)
C18—N5—C22117.40 (19)F9B—C17—F9A58.2 (8)
C28—N6—N7111.18 (18)F8A—C17—F7B64.5 (8)
C28—N6—C20130.48 (19)F9B—C17—F7B91.4 (8)
N7—N6—C20118.33 (18)F9A—C17—F7B129.0 (4)
N8—N7—N6106.56 (19)F8A—C17—F8B44.4 (5)
N7—N8—C29109.3 (2)F9B—C17—F8B123.0 (11)
F2—C1—F1106.9 (2)F9A—C17—F8B69.7 (9)
F2—C1—F3105.7 (2)F7B—C17—F8B105.5 (9)
F1—C1—F3106.1 (2)F8A—C17—F7A118.4 (8)
F2—C1—C2114.0 (2)F9B—C17—F7A36.5 (8)
F1—C1—C2111.9 (2)F9A—C17—F7A92.6 (6)
F3—C1—C2111.6 (2)F7B—C17—F7A57.8 (5)
C3—C2—C7120.0 (2)F8B—C17—F7A139.9 (5)
C3—C2—C1120.3 (2)F8A—C17—C18112.7 (3)
C7—C2—C1119.6 (2)F9B—C17—C18110.2 (6)
C2—C3—C4120.9 (2)F9A—C17—C18113.5 (3)
C2—C3—H3119.6F7B—C17—C18115.2 (3)
C4—C3—H3119.6F8B—C17—C18110.4 (4)
C5—C4—C3120.9 (2)F7A—C17—C18109.7 (4)
C5—C4—H4119.5N5—C18—C19124.8 (2)
C3—C4—H4119.5N5—C18—C17115.3 (2)
C4—C5—C6120.0 (2)C19—C18—C17119.9 (2)
C4—C5—H5120.0C20—C19—C18117.8 (2)
C6—C5—H5120.0C20—C19—H19121.1
C8—C6—C5123.73 (19)C18—C19—H19121.1
C8—C6—C7116.70 (18)C19—C20—C21120.8 (2)
C5—C6—C7119.57 (19)C19—C20—N6119.0 (2)
N1—C7—C2119.19 (19)C21—C20—N6120.17 (19)
N1—C7—C6122.24 (19)C27—C21—C22119.8 (2)
C2—C7—C6118.56 (19)C27—C21—C20124.3 (2)
C9—C8—C6120.9 (2)C22—C21—C20115.9 (2)
C9—C8—N2120.6 (2)N5—C22—C21123.3 (2)
C6—C8—N2118.44 (18)N5—C22—C23118.4 (2)
C8—C9—C10117.1 (2)C21—C22—C23118.3 (2)
C8—C9—H9121.4C25—C23—C22119.8 (2)
C10—C9—H9121.4C25—C23—C24120.5 (2)
N1—C10—C9125.4 (2)C22—C23—C24119.7 (2)
N1—C10—C11115.1 (2)F11—C24—F10106.2 (3)
C9—C10—C11119.5 (2)F11—C24—F12106.5 (2)
F4B—C11—F5A96.2 (11)F10—C24—F12105.3 (2)
F4B—C11—F6111.4 (5)F11—C24—C23113.7 (2)
F5A—C11—F6109.1 (8)F10—C24—C23113.3 (2)
F4B—C11—F5B118.2 (13)F12—C24—C23111.2 (3)
F5A—C11—F5B24.2 (9)C23—C25—C26121.3 (2)
F6—C11—F5B90.5 (12)C23—C25—H25119.3
F4B—C11—F4A26.3 (8)C26—C25—H25119.3
F5A—C11—F4A120.5 (13)C27—C26—C25120.7 (2)
F6—C11—F4A92.3 (11)C27—C26—H26119.7
F5B—C11—F4A139.1 (14)C25—C26—H26119.7
F4B—C11—C10114.0 (4)C26—C27—C21120.0 (2)
F5A—C11—C10112.7 (4)C26—C27—H27120.0
F6—C11—C10112.3 (2)C21—C27—H27120.0
F5B—C11—C10108.3 (11)N6—C28—C29103.5 (2)
F4A—C11—C10108.2 (8)N6—C28—C32123.4 (2)
N2—C12—C13103.2 (2)C29—C28—C32132.8 (2)
N2—C12—C16124.1 (2)N8—C29—C28109.4 (2)
C13—C12—C16132.7 (2)N8—C29—C30121.6 (2)
N4—C13—C12109.0 (2)C28—C29—C30129.0 (3)
N4—C13—C14122.7 (2)O2—C30—C29119.5 (3)
C12—C13—C14128.3 (2)O2—C30—C31122.8 (3)
O1A—C14—O1B20.3 (18)C29—C30—C31117.7 (3)
O1A—C14—C13122.5 (9)C30—C31—H31A109.5
O1B—C14—C13116.5 (15)C30—C31—H31B109.5
O1A—C14—C15119.4 (12)H31A—C31—H31B109.5
O1B—C14—C15124.5 (13)C30—C31—H31C109.5
C13—C14—C15117.5 (3)H31A—C31—H31C109.5
C14—C15—H15A109.5H31B—C31—H31C109.5
C14—C15—H15B109.5C28—C32—H32A109.5
H15A—C15—H15B109.5C28—C32—H32B109.5
C14—C15—H15C109.5H32A—C32—H32B109.5
H15A—C15—H15C109.5C28—C32—H32C109.5
H15B—C15—H15C109.5H32A—C32—H32C109.5
C12—C16—H16A109.5H32B—C32—H32C109.5
C12—C16—H16B109.5
C12—N2—N3—N4−0.1 (3)C12—C13—C14—O1B−19 (3)
C8—N2—N3—N4−174.99 (19)N4—C13—C14—C15−3.4 (4)
N2—N3—N4—C130.2 (3)C12—C13—C14—C15175.0 (3)
C28—N6—N7—N8−0.6 (3)C22—N5—C18—C191.1 (4)
C20—N6—N7—N8−179.6 (2)C22—N5—C18—C17−179.7 (2)
N6—N7—N8—C29−0.5 (3)F8A—C17—C18—N5−76.4 (9)
F2—C1—C2—C3122.6 (3)F9B—C17—C18—N596.7 (10)
F1—C1—C2—C3−115.9 (3)F9A—C17—C18—N5159.8 (4)
F3—C1—C2—C32.9 (4)F7B—C17—C18—N5−4.9 (9)
F2—C1—C2—C7−61.0 (3)F8B—C17—C18—N5−124.3 (10)
F1—C1—C2—C760.5 (3)F7A—C17—C18—N557.8 (7)
F3—C1—C2—C7179.3 (2)F8A—C17—C18—C19102.8 (8)
C7—C2—C3—C40.3 (4)F9B—C17—C18—C19−84.1 (10)
C1—C2—C3—C4176.7 (2)F9A—C17—C18—C19−21.0 (5)
C2—C3—C4—C5−2.0 (4)F7B—C17—C18—C19174.3 (8)
C3—C4—C5—C61.3 (4)F8B—C17—C18—C1955.0 (11)
C4—C5—C6—C8−179.0 (2)F7A—C17—C18—C19−123.0 (7)
C4—C5—C6—C71.0 (3)N5—C18—C19—C20−1.4 (4)
C10—N1—C7—C2−178.2 (2)C17—C18—C19—C20179.5 (2)
C10—N1—C7—C60.9 (3)C18—C19—C20—C21−0.3 (3)
C3—C2—C7—N1−179.0 (2)C18—C19—C20—N6−178.1 (2)
C1—C2—C7—N14.6 (3)C28—N6—C20—C19−115.8 (3)
C3—C2—C7—C61.9 (3)N7—N6—C20—C1963.0 (3)
C1—C2—C7—C6−174.5 (2)C28—N6—C20—C2166.3 (3)
C8—C6—C7—N1−1.6 (3)N7—N6—C20—C21−114.9 (2)
C5—C6—C7—N1178.4 (2)C19—C20—C21—C27−177.8 (2)
C8—C6—C7—C2177.44 (19)N6—C20—C21—C270.0 (3)
C5—C6—C7—C2−2.6 (3)C19—C20—C21—C221.9 (3)
C5—C6—C8—C9−178.6 (2)N6—C20—C21—C22179.73 (18)
C7—C6—C8—C91.4 (3)C18—N5—C22—C210.7 (3)
C5—C6—C8—N22.6 (3)C18—N5—C22—C23−179.7 (2)
C7—C6—C8—N2−177.39 (18)C27—C21—C22—N5177.5 (2)
C12—N2—C8—C979.1 (3)C20—C21—C22—N5−2.2 (3)
N3—N2—C8—C9−107.1 (2)C27—C21—C22—C23−2.1 (3)
C12—N2—C8—C6−102.1 (3)C20—C21—C22—C23178.20 (19)
N3—N2—C8—C671.7 (3)N5—C22—C23—C25−179.3 (2)
C6—C8—C9—C10−0.5 (3)C21—C22—C23—C250.3 (3)
N2—C8—C9—C10178.3 (2)N5—C22—C23—C241.7 (3)
C7—N1—C10—C90.1 (3)C21—C22—C23—C24−178.7 (2)
C7—N1—C10—C11179.6 (2)C25—C23—C24—F11−116.5 (3)
C8—C9—C10—N1−0.3 (4)C22—C23—C24—F1162.5 (3)
C8—C9—C10—C11−179.8 (2)C25—C23—C24—F10122.1 (3)
N1—C10—C11—F4B−18.2 (8)C22—C23—C24—F10−59.0 (3)
C9—C10—C11—F4B161.4 (8)C25—C23—C24—F123.8 (4)
N1—C10—C11—F5A90.1 (11)C22—C23—C24—F12−177.3 (2)
C9—C10—C11—F5A−90.3 (11)C22—C23—C25—C261.2 (4)
N1—C10—C11—F6−146.1 (2)C24—C23—C25—C26−179.8 (3)
C9—C10—C11—F633.5 (3)C23—C25—C26—C27−0.9 (4)
N1—C10—C11—F5B115.6 (12)C25—C26—C27—C21−1.0 (4)
C9—C10—C11—F5B−64.9 (12)C22—C21—C27—C262.4 (4)
N1—C10—C11—F4A−45.7 (13)C20—C21—C27—C26−177.9 (2)
C9—C10—C11—F4A133.9 (13)N7—N6—C28—C291.3 (3)
N3—N2—C12—C130.0 (3)C20—N6—C28—C29−179.8 (2)
C8—N2—C12—C13174.1 (2)N7—N6—C28—C32−173.9 (2)
N3—N2—C12—C16179.8 (2)C20—N6—C28—C324.9 (4)
C8—N2—C12—C16−6.0 (4)N7—N8—C29—C281.3 (3)
N3—N4—C13—C12−0.3 (3)N7—N8—C29—C30−179.3 (2)
N3—N4—C13—C14178.4 (2)N6—C28—C29—N8−1.6 (3)
N2—C12—C13—N40.2 (3)C32—C28—C29—N8173.0 (3)
C16—C12—C13—N4−179.7 (3)N6—C28—C29—C30179.1 (2)
N2—C12—C13—C14−178.4 (3)C32—C28—C29—C30−6.3 (5)
C16—C12—C13—C141.8 (5)N8—C29—C30—O2170.1 (3)
N4—C13—C14—O1A−175 (3)C28—C29—C30—O2−10.6 (4)
C12—C13—C14—O1A4(3)N8—C29—C30—C31−10.1 (4)
N4—C13—C14—O1B163 (3)C28—C29—C30—C31169.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···F30.932.332.677 (3)102
C5—H5···F12i0.932.513.178 (3)129
C9—H9···N7ii0.932.473.312 (4)151
C16—H16A···O2iii0.962.493.359 (4)150
C25—H25···F120.932.312.659 (3)102
C32—H32B···F5Aiv0.962.413.324 (14)158
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) x+1, y−1, z; (iv) x−1, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···F30.932.332.677 (3)102
C5—H5···F12i0.932.513.178 (3)129
C9—H9···N7ii0.932.473.312 (4)151
C16—H16A···O2iii0.962.493.359 (4)150
C25—H25···F120.932.312.659 (3)102
C32—H32B···F5Aiv0.962.413.324 (14)158
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) x+1, y−1, z; (iv) x−1, y+1, z.
Acknowledgements top

The authors thank Professor T. N. Guru Row and Mr Ravish Sankolli, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, for their help with the data collection.

references
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