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lh5143 scheme

Acta Cryst. (2010). E66, o2797-o2798    [ doi:10.1107/S1600536810040055 ]

3,5-Bis(3-butylimidazolium-1-ylmethyl)toluene bis(hexafluorophosphate)

R. A. Haque, A. Washeel, S. G. Teoh, C. K. Quah and H.-K. Fun

Abstract top

In the title compound [systematic name: 3,3'-Dibutyl-1,1'-(5-methyl-m-phenylenedimethylene)diimidazol-1-ium bis(hexafluoridophosphate)], C23H34N42+·2PF6-, the imidazole rings are inclined at angles of 68.06 (7) and 75.05 (8)° with respect to the central benzene ring. In the crystal, molecules are linked into one-dimensional columns along [010] via weak intermolecular C-H...F hydrogen bonds. The crystal structure is further consolidated by weak C-H...[pi](arene) interactions. One of the n-butyl groups is disordered over two sites with refined occupancies of 0.694 (5) and 0.306 (5). In addition, four of the F atoms of one of the PF6- cations are disordered over two sites with occupancies of 0.64 (3) and 0.36 (3).

Comment top

Since the discovery of stable imidazoline-2-ylidenes, which were isolated and structurally characterized by Arduengo et al. (1991), the organometallic and coordination chemistry of N-heterocyclic carbene (NHC) ligands have been receiving great attention in recent years and much interest has been generated in the chemistry of the metal complexes of these ligands (Chen et al., 2002; Zhou et al., 2008). NHC carbene, a strong σ-donor and a weak π-acceptor, strongly interacts with different transitions metals in various oxidation states (Hahn & Jahnke, 2008; Danopoulos et al., 2007). Heterocyclic carbenes derived from imidazolium ions form complexes with many transition metals; heterocyclic carbene complexes of Pd, Ni, Pt, Rh, Ru, Ag and Au have been reported (Bourissou et al., 2000; McGuinness & Cavell, 2000; Garrison et al., 2001). Extensive catalytic studies on the application to organic synthesis have also been reported (Cavell & McGuinness, 2004; Liu et al., 2007).

The title molecule (Fig. 1) consists of a 3,5-bis(3-butylimidazolium-1- ylmethyl)toluene cation and two hexafluorophosphate anions. Bond lengths (Allen et al., 1987) and angles are within normal ranges.The phenyl ring (C1-C6) is inclined at angles of 68.06 (7) and 75.05 (8) ° with respect to the N1/N2/C8/C9/C10 and N3/N4/C16/C17/C18 imidazole rings. The butyl group (C19-C22) of the cation and four fluorine atoms (F7-F10) of the hexafluorophosphate anion are disordered over two positions with refined site-occupancies of 0.694 (5) : 0.306 (5) and 0.64 (3) : 0.36 (3), respectively.

In the crystal structure, (Fig. 2), the molecules are linked into one-dimensional columns along [010] via intermolecular C–H···F hydrogen bonds (Table 1). The crystal structure is further consolidated by C–H···Cg1 (Table 1) interactions, Cg1 is the centroid of C1-C6 phenyl ring.

Related literature top

For general background to imidazoline-2-ylidenes, see: Arduengo et al. (1991). For the organometallic and coordination chemistry of N-heterocyclic carbene ligands, see: Chen et al. (2002); Zhou et al. (2008); Hahn & Jahnke (2008); Danopoulos et al. (2007); Bourissou et al. (2000); McGuinness & Cavell (2000); Garrison et al. (2001). For catalytic studies related to organic synthesis, see: Cavell & McGuinness (2004); Liu et al. (2007). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For standard bond-length data, see: Allen et al. (1987).

For related literature, see: Bourissou et al. (2000).

Experimental top

N-butylimidazole (0.9 g, 7.2 mmol) was added to a stirred solution of 3,5-bis(bromomethyl)toluene (1.0 g, 3.6 mmol) in 20 ml of 1,4-dioxane. The mixture was refluxed at 373 K for 24 h. The sticky product was isolated by decantation and washed with fresh 1,4-dioxane (2 x 5 ml) and diethyl ether (2 x 3 ml). The resulting bromide salt was converted directly to its hexafluorophosphate salt by metathesis reaction using KPF6 (1.3 g, 7.2 mmol) in 20 ml of methanol. The colourless precipitate formed was collected and washed with distilled water (2 x 5 ml), and then recrystallized from acetonitrile to give colourless crystals. Yield: 1.9 g (79%), m. p.: 369-371 K. Crystals suitable for X-ray diffraction studies were obtained by slow evaporation of the salt solution in acetonitrile at 281 K.

Refinement top

All H atoms were positioned geometrically and refined using a riding model with C–H = 0.93-0.97 Å and Uiso(H) = 1.2 or 1.5 Ueq(C). A rotating-group model was applied for the methyl groups. Butyl group (C19-C22) of cation and four fluorine atoms (F7-F10) of the hexafluorophosphate anion are disordered over two positions with refined site-occupancies of 0.694 (5) : 0.306 (5) and 0.64 (3) : 0.36 (3), respectively.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme. Both disorder components are shown.
[Figure 2] Fig. 2. Part of the crystal structure of the title compound, viewed along the b axis. Only the major disorder component is shown. Intermolecular hydrogen bonds are shown in dashed lines.
3,3'-Dibutyl-1,1'-(5-methyl-m-phenylenedimethylene)diimidazol-1-ium bis(hexafluoridophosphate) top
Crystal data top
C23H34N42+·2PF6−F(000) = 1352
Mr = 656.48Dx = 1.486 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9893 reflections
a = 9.6207 (1) Åθ = 2.2–32.2°
b = 11.1801 (1) ŵ = 0.25 mm−1
c = 27.9277 (3) ÅT = 100 K
β = 102.416 (1)°Block, colourless
V = 2933.66 (5) Å30.49 × 0.20 × 0.14 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		10399 independent reflections
Radiation source: fine-focus sealed tube7294 reflections with I > 2σ(I)
graphiteRint = 0.040
φ and ω scansθmax = 32.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		h = −14→14
Tmin = 0.890, Tmax = 0.967k = −15→16
45569 measured reflectionsl = −41→41
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0569P)2 + 0.5709P]
where P = (Fo2 + 2Fc2)/3
10399 reflections(Δ/σ)max = 0.001
448 parametersΔρmax = 0.39 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C23H34N42+·2PF6−V = 2933.66 (5) Å3
Mr = 656.48Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.6207 (1) ŵ = 0.25 mm−1
b = 11.1801 (1) ÅT = 100 K
c = 27.9277 (3) Å0.49 × 0.20 × 0.14 mm
β = 102.416 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		10399 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		7294 reflections with I > 2σ(I)
Tmin = 0.890, Tmax = 0.967Rint = 0.040
45569 measured reflectionsθmax = 32.3°
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.122Δρmax = 0.39 e Å−3
S = 1.03Δρmin = −0.26 e Å−3
10399 reflectionsAbsolute structure: ?
448 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
N10.04726 (12)0.72856 (9)0.87680 (4)0.0197 (2)
N20.25427 (13)0.70746 (10)0.85917 (4)0.0242 (2)
N30.01110 (12)1.25423 (9)0.87615 (4)0.0192 (2)
N40.22616 (13)1.27303 (12)0.86629 (5)0.0289 (3)
C1−0.12271 (14)0.98508 (11)0.87153 (5)0.0201 (3)
H1A−0.10790.98560.83970.024*
C2−0.14332 (14)1.09268 (11)0.89438 (5)0.0203 (2)
C3−0.16796 (15)1.09046 (12)0.94182 (5)0.0241 (3)
H3A−0.18241.16200.95700.029*
C4−0.17140 (17)0.98323 (12)0.96688 (6)0.0262 (3)
C5−0.14902 (16)0.87688 (12)0.94368 (5)0.0257 (3)
H5A−0.15060.80470.96010.031*
C6−0.12428 (14)0.87685 (11)0.89618 (5)0.0209 (3)
C7−0.10445 (14)0.75962 (12)0.87112 (5)0.0230 (3)
H7A−0.15240.69630.88500.028*
H7B−0.14800.76570.83650.028*
C80.12152 (15)0.74404 (12)0.84230 (5)0.0219 (3)
H8A0.08610.77550.81120.026*
C90.13609 (16)0.67800 (12)0.91727 (5)0.0258 (3)
H9A0.11150.65710.94660.031*
C100.26525 (16)0.66465 (13)0.90628 (5)0.0272 (3)
H10A0.34620.63270.92650.033*
C110.36527 (17)0.70733 (14)0.83004 (6)0.0322 (3)
H11A0.45180.74180.84950.039*
H11B0.33450.75730.80130.039*
C120.39714 (16)0.58281 (14)0.81384 (6)0.0296 (3)
H12A0.30860.54320.79910.035*
H12B0.44300.53660.84230.035*
C130.4934 (2)0.58630 (18)0.77702 (8)0.0466 (5)
H13A0.45060.63730.74970.056*
H13B0.58430.62100.79260.056*
C140.5180 (2)0.4634 (2)0.75778 (8)0.0551 (5)
H14A0.57790.47000.73450.083*
H14B0.42830.42890.74210.083*
H14C0.56330.41330.78450.083*
C15−0.13694 (14)1.21063 (12)0.86830 (5)0.0223 (3)
H15A−0.17521.20040.83350.027*
H15B−0.19491.26930.88050.027*
C160.09876 (15)1.22892 (12)0.84694 (5)0.0222 (3)
H16A0.07471.18690.81760.027*
C170.08522 (17)1.31852 (12)0.91586 (5)0.0270 (3)
H17A0.04931.34820.94190.032*
C180.21968 (18)1.32975 (14)0.90954 (6)0.0323 (3)
H18A0.29421.36860.93050.039*
C19A0.3539 (4)1.2443 (3)0.84464 (16)0.0311 (7)0.694 (5)
H19A0.40581.31750.84180.047*0.694 (5)
H19B0.32141.21170.81200.047*0.694 (5)
C20A0.4534 (3)1.1550 (2)0.87594 (12)0.0333 (7)0.694 (5)
H20A0.48751.18940.90820.040*0.694 (5)
H20B0.53521.14280.86140.040*0.694 (5)
C21A0.3866 (2)1.0333 (2)0.88191 (8)0.0271 (6)0.694 (5)
H21A0.30071.04510.89420.041*0.694 (5)
H21B0.36000.99500.85010.041*0.694 (5)
C22A0.4863 (3)0.9528 (3)0.91641 (12)0.0333 (6)0.694 (5)
H22A0.43740.88060.92150.040*0.694 (5)
H22B0.51850.99280.94720.040*0.694 (5)
H22C0.56660.93350.90250.040*0.694 (5)
C19B0.3518 (10)1.2886 (6)0.8487 (4)0.0292 (15)0.306 (5)
H19C0.41961.33840.87070.044*0.306 (5)
H19D0.33161.32430.81630.044*0.306 (5)
C20B0.4073 (6)1.1615 (5)0.8473 (2)0.0280 (13)0.306 (5)
H20C0.49351.16320.83460.034*0.306 (5)
H20D0.33721.11450.82490.034*0.306 (5)
C21B0.4395 (6)1.1003 (5)0.8976 (2)0.0306 (14)0.306 (5)
H21C0.52221.13730.91830.046*0.306 (5)
H21D0.35941.11080.91310.046*0.306 (5)
C22B0.4668 (8)0.9706 (7)0.8925 (4)0.049 (2)0.306 (5)
H22D0.47430.93200.92370.058*0.306 (5)
H22E0.55410.96020.88160.058*0.306 (5)
H22F0.38980.93590.86910.058*0.306 (5)
C23−0.2051 (2)0.98208 (14)1.01718 (6)0.0348 (4)
H23A−0.25081.05571.02250.052*
H23B−0.11850.97351.04150.052*
H23C−0.26730.91621.01960.052*
P10.03700 (4)0.98649 (3)0.736481 (13)0.02052 (8)
F10.14427 (10)1.08561 (8)0.72469 (3)0.0333 (2)
F20.13549 (10)0.88117 (8)0.72386 (3)0.0322 (2)
F3−0.06262 (9)1.09104 (7)0.75081 (3)0.02749 (18)
F40.12345 (10)0.98346 (7)0.79273 (3)0.0288 (2)
F5−0.07193 (9)0.88809 (8)0.74956 (3)0.02905 (19)
F6−0.05042 (10)0.98987 (7)0.68110 (3)0.02762 (19)
P20.70821 (4)0.49928 (3)0.947765 (13)0.02189 (8)
F7A0.5758 (12)0.4191 (10)0.9282 (3)0.078 (2)0.64 (3)
F8A0.6652 (12)0.5050 (9)0.9993 (4)0.0473 (18)0.64 (3)
F9A0.8492 (8)0.5779 (7)0.9694 (3)0.0372 (10)0.64 (3)
F10A0.7584 (13)0.4898 (3)0.8965 (2)0.0429 (14)0.64 (3)
F7B0.5535 (12)0.4370 (13)0.9296 (4)0.052 (2)0.36 (3)
F8B0.689 (2)0.5172 (17)1.0023 (7)0.050 (3)0.36 (3)
F9B0.8528 (13)0.5644 (17)0.9618 (8)0.053 (3)0.36 (3)
F10B0.7239 (19)0.4851 (9)0.8938 (4)0.056 (3)0.36 (3)
F110.62602 (11)0.62115 (9)0.93069 (4)0.0452 (3)
F120.79372 (13)0.37811 (8)0.96468 (4)0.0462 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0263 (6)0.0145 (5)0.0190 (5)0.0008 (4)0.0065 (4)−0.0006 (4)
N20.0266 (6)0.0214 (5)0.0256 (6)0.0007 (5)0.0077 (5)0.0003 (5)
N30.0255 (6)0.0136 (5)0.0181 (5)−0.0010 (4)0.0040 (4)0.0006 (4)
N40.0256 (6)0.0331 (7)0.0261 (6)−0.0044 (5)0.0013 (5)0.0069 (5)
C10.0220 (6)0.0206 (6)0.0192 (6)−0.0008 (5)0.0080 (5)−0.0014 (5)
C20.0231 (6)0.0169 (5)0.0221 (6)0.0001 (5)0.0075 (5)0.0001 (5)
C30.0312 (7)0.0176 (6)0.0268 (7)0.0000 (5)0.0133 (6)−0.0024 (5)
C40.0362 (8)0.0212 (6)0.0252 (7)−0.0007 (5)0.0159 (6)−0.0009 (5)
C50.0352 (8)0.0182 (6)0.0269 (7)−0.0015 (5)0.0137 (6)0.0022 (5)
C60.0235 (6)0.0171 (6)0.0238 (7)−0.0005 (5)0.0091 (5)−0.0021 (5)
C70.0249 (7)0.0180 (6)0.0278 (7)−0.0005 (5)0.0097 (6)−0.0027 (5)
C80.0287 (7)0.0177 (6)0.0196 (6)0.0003 (5)0.0060 (5)0.0002 (5)
C90.0381 (8)0.0210 (6)0.0180 (6)0.0027 (6)0.0055 (6)0.0025 (5)
C100.0322 (8)0.0238 (7)0.0238 (7)0.0037 (6)0.0025 (6)0.0020 (5)
C110.0287 (8)0.0318 (8)0.0400 (9)−0.0006 (6)0.0160 (7)0.0007 (7)
C120.0237 (7)0.0362 (8)0.0298 (8)0.0016 (6)0.0078 (6)−0.0029 (6)
C130.0449 (10)0.0491 (11)0.0542 (12)0.0066 (9)0.0292 (9)0.0007 (9)
C140.0530 (12)0.0621 (13)0.0593 (14)0.0055 (10)0.0320 (11)−0.0127 (11)
C150.0240 (6)0.0191 (6)0.0244 (7)0.0023 (5)0.0065 (5)0.0038 (5)
C160.0265 (7)0.0204 (6)0.0192 (6)0.0005 (5)0.0038 (5)0.0005 (5)
C170.0444 (9)0.0164 (6)0.0182 (6)−0.0023 (6)0.0022 (6)−0.0024 (5)
C180.0410 (9)0.0254 (7)0.0254 (7)−0.0105 (6)−0.0039 (6)0.0028 (6)
C19A0.0258 (13)0.0306 (18)0.0399 (16)−0.0018 (16)0.0136 (11)0.0025 (16)
C20A0.0234 (12)0.0317 (13)0.0454 (19)−0.0030 (9)0.0088 (12)−0.0032 (12)
C21A0.0245 (11)0.0269 (12)0.0288 (11)−0.0001 (9)0.0034 (9)−0.0041 (9)
C22A0.0267 (13)0.0304 (13)0.0396 (16)0.0037 (10)0.0005 (13)−0.0037 (13)
C19B0.027 (3)0.025 (3)0.034 (3)−0.002 (3)0.003 (2)0.001 (3)
C20B0.019 (2)0.041 (3)0.022 (3)−0.007 (2)0.002 (2)−0.002 (2)
C21B0.023 (2)0.028 (3)0.043 (3)0.004 (2)0.014 (2)0.010 (2)
C22B0.031 (4)0.038 (4)0.072 (6)0.004 (3)0.000 (4)0.015 (4)
C230.0534 (10)0.0283 (7)0.0287 (8)0.0001 (7)0.0223 (7)0.0005 (6)
P10.02485 (18)0.01586 (15)0.01977 (17)−0.00042 (12)0.00237 (13)−0.00059 (12)
F10.0344 (5)0.0262 (4)0.0401 (5)−0.0078 (4)0.0098 (4)0.0037 (4)
F20.0330 (5)0.0254 (4)0.0368 (5)0.0078 (4)0.0042 (4)−0.0055 (4)
F30.0323 (4)0.0242 (4)0.0245 (4)0.0060 (3)0.0028 (3)−0.0049 (3)
F40.0343 (5)0.0232 (4)0.0236 (4)−0.0004 (3)−0.0055 (4)−0.0011 (3)
F50.0328 (5)0.0250 (4)0.0279 (4)−0.0080 (3)0.0032 (4)0.0026 (3)
F60.0398 (5)0.0230 (4)0.0182 (4)0.0021 (3)0.0021 (4)−0.0010 (3)
P20.02675 (18)0.01888 (16)0.01996 (17)−0.00170 (13)0.00483 (14)−0.00076 (13)
F7A0.074 (4)0.063 (3)0.079 (3)−0.047 (3)−0.024 (2)0.005 (2)
F8A0.057 (3)0.057 (2)0.037 (4)0.0006 (17)0.031 (3)0.003 (2)
F9A0.039 (2)0.0269 (14)0.0385 (18)−0.0080 (11)−0.0080 (11)−0.0024 (12)
F10A0.084 (4)0.0229 (17)0.0288 (16)0.0030 (13)0.0279 (19)0.0019 (9)
F7B0.027 (3)0.067 (4)0.058 (4)−0.022 (3)0.001 (2)0.029 (3)
F8B0.068 (7)0.060 (5)0.022 (3)0.024 (5)0.008 (3)−0.013 (3)
F9B0.015 (3)0.049 (6)0.088 (8)−0.007 (3)−0.005 (4)0.023 (5)
F10B0.057 (5)0.095 (7)0.021 (2)0.026 (3)0.015 (2)0.011 (3)
F110.0385 (6)0.0373 (5)0.0541 (7)0.0151 (4)−0.0025 (5)0.0061 (5)
F120.0840 (8)0.0214 (4)0.0350 (5)0.0163 (5)0.0168 (5)0.0048 (4)
Geometric parameters (Å, °) top
N1—C81.3285 (17)C17—C181.349 (2)
N1—C91.3828 (18)C17—H17A0.9300
N1—C71.4753 (17)C18—H18A0.9300
N2—C81.3272 (18)C19A—C20A1.522 (5)
N2—C101.3825 (18)C19A—H19A0.9700
N2—C111.4751 (19)C19A—H19B0.9700
N3—C161.3238 (17)C20A—C21A1.528 (3)
N3—C171.3837 (17)C20A—H20A0.9700
N3—C151.4764 (18)C20A—H20B0.9700
N4—C161.3238 (18)C21A—C22A1.504 (4)
N4—C181.378 (2)C21A—H21A0.9700
N4—C19B1.410 (10)C21A—H21B0.9700
N4—C19A1.516 (4)C22A—H22A0.9600
C1—C61.3938 (18)C22A—H22B0.9600
C1—C21.3959 (17)C22A—H22C0.9600
C1—H1A0.9300C19B—C20B1.521 (9)
C2—C31.3954 (18)C19B—H19C0.9700
C2—C151.5141 (18)C19B—H19D0.9700
C3—C41.3921 (19)C20B—C21B1.532 (8)
C3—H3A0.9300C20B—H20C0.9700
C4—C51.3927 (19)C20B—H20D0.9700
C4—C231.508 (2)C21B—C22B1.485 (9)
C5—C61.3972 (19)C21B—H21C0.9700
C5—H5A0.9300C21B—H21D0.9700
C6—C71.5170 (18)C22B—H22D0.9600
C7—H7A0.9700C22B—H22E0.9600
C7—H7B0.9700C22B—H22F0.9600
C8—H8A0.9300C23—H23A0.9600
C9—C101.351 (2)C23—H23B0.9600
C9—H9A0.9300C23—H23C0.9600
C10—H10A0.9300P1—F61.5941 (9)
C11—C121.515 (2)P1—F11.5960 (9)
C11—H11A0.9700P1—F21.5976 (9)
C11—H11B0.9700P1—F41.6120 (9)
C12—C131.525 (2)P1—F51.6145 (9)
C12—H12A0.9700P1—F31.6154 (9)
C12—H12B0.9700P2—F9B1.544 (13)
C13—C141.512 (3)P2—F10B1.556 (11)
C13—H13A0.9700P2—F7A1.557 (6)
C13—H13B0.9700P2—F8A1.583 (9)
C14—H14A0.9600P2—F8B1.584 (16)
C14—H14B0.9600P2—F111.5959 (10)
C14—H14C0.9600P2—F121.6024 (10)
C15—H15A0.9700P2—F10A1.610 (6)
C15—H15B0.9700P2—F9A1.620 (7)
C16—H16A0.9300P2—F7B1.622 (10)
C8—N1—C9108.18 (12)H20A—C20A—H20B107.5
C8—N1—C7124.42 (12)C22A—C21A—C20A112.2 (2)
C9—N1—C7127.40 (12)C22A—C21A—H21A109.2
C8—N2—C10108.38 (12)C20A—C21A—H21A109.2
C8—N2—C11124.06 (13)C22A—C21A—H21B109.2
C10—N2—C11127.46 (13)C20A—C21A—H21B109.2
C16—N3—C17108.54 (12)H21A—C21A—H21B107.9
C16—N3—C15124.05 (11)N4—C19B—C20B103.1 (5)
C17—N3—C15127.23 (12)N4—C19B—H19C111.2
C16—N4—C18108.47 (13)C20B—C19B—H19C111.2
C16—N4—C19B133.8 (4)N4—C19B—H19D111.2
C18—N4—C19B116.9 (4)C20B—C19B—H19D111.2
C16—N4—C19A121.1 (2)H19C—C19B—H19D109.1
C18—N4—C19A129.8 (2)C19B—C20B—C21B113.3 (6)
C19B—N4—C19A19.6 (3)C19B—C20B—H20C108.9
C6—C1—C2120.31 (12)C21B—C20B—H20C108.9
C6—C1—H1A119.8C19B—C20B—H20D108.9
C2—C1—H1A119.8C21B—C20B—H20D108.9
C3—C2—C1119.25 (12)H20C—C20B—H20D107.7
C3—C2—C15120.34 (12)C22B—C21B—C20B110.8 (7)
C1—C2—C15120.41 (12)C22B—C21B—H21C109.5
C4—C3—C2121.32 (12)C20B—C21B—H21C109.5
C4—C3—H3A119.3C22B—C21B—H21D109.5
C2—C3—H3A119.3C20B—C21B—H21D109.5
C3—C4—C5118.60 (13)H21C—C21B—H21D108.1
C3—C4—C23120.58 (13)C21B—C22B—H22D109.5
C5—C4—C23120.77 (13)C21B—C22B—H22E109.5
C4—C5—C6121.11 (13)H22D—C22B—H22E109.5
C4—C5—H5A119.4C21B—C22B—H22F109.5
C6—C5—H5A119.4H22D—C22B—H22F109.5
C1—C6—C5119.40 (12)H22E—C22B—H22F109.5
C1—C6—C7120.42 (12)C4—C23—H23A109.5
C5—C6—C7120.14 (12)C4—C23—H23B109.5
N1—C7—C6111.93 (11)H23A—C23—H23B109.5
N1—C7—H7A109.2C4—C23—H23C109.5
C6—C7—H7A109.2H23A—C23—H23C109.5
N1—C7—H7B109.2H23B—C23—H23C109.5
C6—C7—H7B109.2F6—P1—F190.75 (5)
H7A—C7—H7B107.9F6—P1—F291.01 (5)
N2—C8—N1109.20 (12)F1—P1—F291.48 (5)
N2—C8—H8A125.4F6—P1—F4179.23 (6)
N1—C8—H8A125.4F1—P1—F489.69 (5)
C10—C9—N1107.24 (12)F2—P1—F489.61 (5)
C10—C9—H9A126.4F6—P1—F590.17 (5)
N1—C9—H9A126.4F1—P1—F5178.60 (5)
C9—C10—N2107.00 (13)F2—P1—F589.56 (5)
C9—C10—H10A126.5F4—P1—F589.38 (5)
N2—C10—H10A126.5F6—P1—F390.33 (5)
N2—C11—C12112.49 (13)F1—P1—F389.61 (5)
N2—C11—H11A109.1F2—P1—F3178.26 (5)
C12—C11—H11A109.1F4—P1—F389.04 (5)
N2—C11—H11B109.1F5—P1—F389.34 (5)
C12—C11—H11B109.1F9B—P2—F10B91.4 (7)
H11A—C11—H11B107.8F9B—P2—F7A170.0 (7)
C11—C12—C13111.65 (14)F10B—P2—F7A81.0 (6)
C11—C12—H12A109.3F9B—P2—F8A98.5 (9)
C13—C12—H12A109.3F10B—P2—F8A170.0 (7)
C11—C12—H12B109.3F7A—P2—F8A89.3 (5)
C13—C12—H12B109.3F9B—P2—F8B88.8 (9)
H12A—C12—H12B108.0F10B—P2—F8B178.3 (8)
C14—C13—C12112.36 (16)F7A—P2—F8B99.0 (8)
C14—C13—H13A109.1F8A—P2—F8B9.7 (11)
C12—C13—H13A109.1F9B—P2—F1192.0 (7)
C14—C13—H13B109.1F10B—P2—F1186.7 (4)
C12—C13—H13B109.1F7A—P2—F1194.1 (5)
H13A—C13—H13B107.9F8A—P2—F1191.6 (4)
C13—C14—H14A109.5F8B—P2—F1191.6 (7)
C13—C14—H14B109.5F9B—P2—F1286.9 (7)
H14A—C14—H14B109.5F10B—P2—F1292.8 (4)
C13—C14—H14C109.5F7A—P2—F1286.9 (5)
H14A—C14—H14C109.5F8A—P2—F1289.1 (4)
H14B—C14—H14C109.5F8B—P2—F1288.9 (7)
N3—C15—C2110.71 (11)F11—P2—F12178.80 (7)
N3—C15—H15A109.5F9B—P2—F10A80.3 (7)
C2—C15—H15A109.5F10B—P2—F10A11.7 (7)
N3—C15—H15B109.5F7A—P2—F10A91.7 (4)
C2—C15—H15B109.5F8A—P2—F10A177.3 (5)
H15A—C15—H15B108.1F8B—P2—F10A168.9 (8)
N3—C16—N4109.00 (12)F11—P2—F10A90.8 (2)
N3—C16—H16A125.5F12—P2—F10A88.5 (2)
N4—C16—H16A125.5F9B—P2—F9A9.4 (10)
C18—C17—N3106.69 (13)F10B—P2—F9A99.8 (7)
C18—C17—H17A126.7F7A—P2—F9A177.6 (5)
N3—C17—H17A126.7F8A—P2—F9A90.0 (5)
C17—C18—N4107.30 (13)F8B—P2—F9A80.3 (9)
C17—C18—H18A126.4F11—P2—F9A88.3 (3)
N4—C18—H18A126.4F12—P2—F9A90.8 (3)
N4—C19A—C20A111.9 (3)F10A—P2—F9A88.9 (4)
N4—C19A—H19A109.2F9B—P2—F7B175.9 (8)
C20A—C19A—H19A109.2F10B—P2—F7B85.8 (7)
N4—C19A—H19B109.2F7A—P2—F7B10.6 (9)
C20A—C19A—H19B109.2F8A—P2—F7B84.3 (6)
H19A—C19A—H19B107.9F8B—P2—F7B93.9 (9)
C19A—C20A—C21A114.8 (3)F11—P2—F7B84.9 (5)
C19A—C20A—H20A108.6F12—P2—F7B96.2 (5)
C21A—C20A—H20A108.6F10A—P2—F7B97.1 (5)
C19A—C20A—H20B108.6F9A—P2—F7B170.9 (6)
C21A—C20A—H20B108.6
C6—C1—C2—C3−1.1 (2)N2—C11—C12—C13170.61 (14)
C6—C1—C2—C15178.02 (13)C11—C12—C13—C14−176.02 (17)
C1—C2—C3—C40.4 (2)C16—N3—C15—C290.70 (15)
C15—C2—C3—C4−178.69 (14)C17—N3—C15—C2−83.84 (16)
C2—C3—C4—C50.3 (2)C3—C2—C15—N392.95 (15)
C2—C3—C4—C23−177.08 (15)C1—C2—C15—N3−86.17 (15)
C3—C4—C5—C6−0.3 (2)C17—N3—C16—N40.59 (15)
C23—C4—C5—C6177.02 (15)C15—N3—C16—N4−174.83 (11)
C2—C1—C6—C51.1 (2)C18—N4—C16—N3−0.45 (16)
C2—C1—C6—C7178.94 (12)C19B—N4—C16—N3−169.1 (5)
C4—C5—C6—C1−0.3 (2)C19A—N4—C16—N3171.83 (19)
C4—C5—C6—C7−178.22 (14)C16—N3—C17—C18−0.49 (15)
C8—N1—C7—C6−101.42 (15)C15—N3—C17—C18174.74 (12)
C9—N1—C7—C679.54 (16)N3—C17—C18—N40.22 (16)
C1—C6—C7—N186.62 (16)C16—N4—C18—C170.13 (17)
C5—C6—C7—N1−95.51 (15)C19B—N4—C18—C17171.0 (4)
C10—N2—C8—N11.08 (16)C19A—N4—C18—C17−171.3 (2)
C11—N2—C8—N1177.63 (12)C16—N4—C19A—C20A−105.3 (3)
C9—N1—C8—N2−0.99 (15)C18—N4—C19A—C20A65.2 (3)
C7—N1—C8—N2179.81 (11)C19B—N4—C19A—C20A119.3 (17)
C8—N1—C9—C100.52 (16)N4—C19A—C20A—C21A61.1 (4)
C7—N1—C9—C10179.69 (12)C19A—C20A—C21A—C22A−175.4 (3)
N1—C9—C10—N20.13 (16)C16—N4—C19B—C20B−72.2 (7)
C8—N2—C10—C9−0.73 (16)C18—N4—C19B—C20B119.9 (5)
C11—N2—C10—C9−177.13 (14)C19A—N4—C19B—C20B−15.9 (11)
C8—N2—C11—C12−105.44 (16)N4—C19B—C20B—C21B−60.3 (7)
C10—N2—C11—C1270.44 (19)C19B—C20B—C21B—C22B169.3 (6)
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C1–C6 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C8—H8A···F40.932.423.0154 (16)121
C8—H8A···F50.932.393.2700 (16)157
C16—H16A···F30.932.313.1941 (16)160
C16—H16A···F40.932.453.1677 (16)134
C21A—H21B···F40.972.493.196 (2)130
C3—H3A···F12i0.932.443.3147 (16)157
C5—H5A···F9Aii0.932.553.420 (8)156
C7—H7A···F10Aii0.972.513.427 (6)158
C9—H9A···F12iii0.932.483.2805 (17)144
C12—H12A···F3iv0.972.533.3358 (18)140
C18—H18A···F8Av0.932.383.148 (11)140
C22A—H22C···Cg1vi0.962.763.535 (3)138
C23—H23B···Cg1vii0.962.593.487 (2)155
C22B—H22E···Cg1vi0.962.863.637 (8)139
Symmetry codes: (i) x−1, y+1, z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+2; (iv) −x, y−1/2, −z+3/2; (v) −x+1, −y+2, −z+2; (vi) x+1, y, z; (vii) −x, −y+2, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg1 is the centroid of the C1–C6 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C8—H8A···F40.932.423.0154 (16)121
C8—H8A···F50.932.393.2700 (16)157
C16—H16A···F30.932.313.1941 (16)160
C16—H16A···F40.932.453.1677 (16)134
C21A—H21B···F40.972.493.196 (2)130
C3—H3A···F12i0.932.443.3147 (16)157
C5—H5A···F9Aii0.932.553.420 (8)156
C7—H7A···F10Aii0.972.513.427 (6)158
C9—H9A···F12iii0.932.483.2805 (17)144
C12—H12A···F3iv0.972.533.3358 (18)140
C18—H18A···F8Av0.932.383.148 (11)140
C22A—H22C···Cg1vi0.962.763.535 (3)138
C23—H23B···Cg1vii0.962.593.487 (2)155
C22B—H22E···Cg1vi0.962.863.637 (8)139
Symmetry codes: (i) x−1, y+1, z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+2; (iv) −x, y−1/2, −z+3/2; (v) −x+1, −y+2, −z+2; (vi) x+1, y, z; (vii) −x, −y+2, −z+2.
Acknowledgements top

RAH, AW and SGT thank Universiti Sains Malaysia (USM) for the FRGS fund (203/PKIMIA/671115), the short term grant (304/PKIMIA/639001) and the Research University Grant (1001/PKIMIA/813023). HKF and CKQ thank USM for the Research University Grant (1001/PFIZIK/811160) and CKQ also thanks USM for a research fellowship.

references
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