The crystal structures of 1-(4-fluorophenyl)-2-phenyl-4,5,6,7-tetrahydro-1
H-indole, C
20H
18FN, and 1-(4-fluorophenyl)-6,6-dimethyl-2-phenyl-4,5,6,7-tetrahydro-1
H-indole, C
22H
22FN, have been determined in order to study the role of `organic fluorine' in crystal engineering. These molecules pack in the crystal structure
via different types of molecular motifs utilizing weak C—H
F and C—H
π interactions.
Supporting information
CCDC references: 251312; 251313
Compounds (I) and (II) were synthesized according to the procedure reported in the literature (Nagarajan et al., 1985). The compounds were crystallized from a solution in dichloromethane and hexane (1:3) by slow evaporation at 263 K. Colourless crystals of (I) grew as long rods, whereas crystals of (II) grew as pale-yellow prisms.
All H atoms were located from difference Fourier maps and were refined isotropically.
For both compounds, data collection: SMART (Bruker, 2004); cell refinement: SMART; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 for Windows (Farrugia, 1997), POV-RAY (The POV-RAY Team, 2004) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 1990).
(I) 1-(4-fluorophenyl)-2-phenyl-4,5,6,7-tetrahydro-1
H-indole
top
Crystal data top
C20H18FN | F(000) = 616 |
Mr = 291.35 | Dx = 1.272 Mg m−3 |
Monoclinic, P21/c | Melting point = 129–130 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.256 (6) Å | Cell parameters from 758 reflections |
b = 10.939 (7) Å | θ = 2.3–24.5° |
c = 15.169 (9) Å | µ = 0.08 mm−1 |
β = 97.75 (1)° | T = 100 K |
V = 1521.9 (17) Å3 | Rod, colourless |
Z = 4 | 0.60 × 0.20 × 0.20 mm |
Data collection top
Bruker SMART CCD area detector diffractometer | 3073 independent reflections |
Radiation source: fine-focus sealed tube | 2619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.912, Tmax = 0.984 | k = −13→13 |
15212 measured reflections | l = −18→18 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0457P)2 + 0.5815P] where P = (Fo2 + 2Fc2)/3 |
3073 reflections | (Δ/σ)max < 0.001 |
271 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C20H18FN | V = 1521.9 (17) Å3 |
Mr = 291.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.256 (6) Å | µ = 0.08 mm−1 |
b = 10.939 (7) Å | T = 100 K |
c = 15.169 (9) Å | 0.60 × 0.20 × 0.20 mm |
β = 97.75 (1)° | |
Data collection top
Bruker SMART CCD area detector diffractometer | 3073 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2619 reflections with I > 2σ(I) |
Tmin = 0.912, Tmax = 0.984 | Rint = 0.030 |
15212 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.29 e Å−3 |
3073 reflections | Δρmin = −0.20 e Å−3 |
271 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 | Uiso*/Ueq | |
F1 | 0.22476 (9) | −0.49091 (7) | −0.00613 (6) | 0.0334 (2) | |
N1 | 0.26904 (11) | 0.01196 (9) | 0.01684 (7) | 0.0180 (2) | |
C2 | 0.22719 (13) | 0.09328 (11) | −0.05254 (8) | 0.0182 (3) | |
C3 | 0.24698 (13) | 0.20934 (12) | −0.01825 (9) | 0.0201 (3) | |
C4 | 0.33881 (15) | 0.29738 (12) | 0.14326 (9) | 0.0242 (3) | |
C5 | 0.41394 (16) | 0.24149 (13) | 0.23020 (10) | 0.0270 (3) | |
C6 | 0.33994 (17) | 0.12287 (13) | 0.25364 (9) | 0.0278 (3) | |
C7 | 0.35343 (15) | 0.02321 (12) | 0.18405 (9) | 0.0229 (3) | |
C8 | 0.31226 (13) | 0.07806 (11) | 0.09390 (8) | 0.0188 (3) | |
C9 | 0.30096 (13) | 0.19992 (12) | 0.07379 (9) | 0.0200 (3) | |
C10 | 0.25635 (13) | −0.11820 (11) | 0.01305 (8) | 0.0176 (3) | |
C11 | 0.11982 (14) | −0.17268 (12) | −0.00857 (8) | 0.0190 (3) | |
C12 | 0.10853 (14) | −0.29893 (12) | −0.01476 (8) | 0.0211 (3) | |
C13 | 0.23514 (15) | −0.36721 (11) | 0.00112 (9) | 0.0229 (3) | |
C14 | 0.37191 (15) | −0.31565 (12) | 0.02365 (9) | 0.0240 (3) | |
C15 | 0.38205 (14) | −0.18927 (12) | 0.02957 (9) | 0.0208 (3) | |
C16 | 0.16892 (13) | 0.05249 (11) | −0.14285 (8) | 0.0185 (3) | |
C17 | 0.04968 (14) | 0.11477 (13) | −0.18938 (9) | 0.0225 (3) | |
C18 | −0.01169 (15) | 0.07642 (14) | −0.27338 (9) | 0.0259 (3) | |
C19 | 0.04425 (15) | −0.02418 (13) | −0.31266 (9) | 0.0255 (3) | |
C20 | 0.16461 (15) | −0.08536 (12) | −0.26833 (9) | 0.0235 (3) | |
C21 | 0.22644 (14) | −0.04735 (12) | −0.18428 (9) | 0.0211 (3) | |
H3 | 0.2292 (16) | 0.2842 (15) | −0.0534 (10) | 0.028 (4)* | |
H4A | 0.4044 (17) | 0.3616 (14) | 0.1198 (10) | 0.026 (4)* | |
H4B | 0.2492 (17) | 0.3410 (14) | 0.1554 (10) | 0.028 (4)* | |
H5A | 0.5192 (18) | 0.2231 (14) | 0.2235 (10) | 0.032 (4)* | |
H5B | 0.4159 (17) | 0.3019 (15) | 0.2786 (11) | 0.032 (4)* | |
H6A | 0.3822 (17) | 0.0921 (14) | 0.3132 (11) | 0.028 (4)* | |
H6B | 0.2308 (18) | 0.1394 (15) | 0.2557 (10) | 0.032 (4)* | |
H7A | 0.4555 (17) | −0.0098 (14) | 0.1906 (10) | 0.028 (4)* | |
H7B | 0.2909 (17) | −0.0475 (14) | 0.1931 (10) | 0.025 (4)* | |
H11 | 0.0339 (16) | −0.1221 (13) | −0.0206 (9) | 0.021 (4)* | |
H12 | 0.0154 (17) | −0.3377 (14) | −0.0301 (10) | 0.027 (4)* | |
H14 | 0.4570 (17) | −0.3668 (15) | 0.0329 (10) | 0.029 (4)* | |
H15 | 0.4775 (17) | −0.1489 (14) | 0.0434 (10) | 0.026 (4)* | |
H17 | 0.0101 (16) | 0.1855 (13) | −0.1622 (10) | 0.021 (4)* | |
H18 | −0.0925 (19) | 0.1214 (15) | −0.3040 (11) | 0.034 (4)* | |
H19 | 0.0026 (17) | −0.0505 (14) | −0.3710 (11) | 0.029 (4)* | |
H20 | 0.2057 (16) | −0.1567 (14) | −0.2954 (10) | 0.026 (4)* | |
H21 | 0.3107 (16) | −0.0917 (13) | −0.1536 (9) | 0.021 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0455 (5) | 0.0142 (4) | 0.0383 (5) | 0.0002 (3) | −0.0028 (4) | −0.0012 (3) |
N1 | 0.0169 (5) | 0.0160 (5) | 0.0210 (5) | 0.0005 (4) | 0.0015 (4) | −0.0014 (4) |
C2 | 0.0140 (6) | 0.0174 (6) | 0.0238 (7) | 0.0014 (5) | 0.0041 (5) | 0.0012 (5) |
C3 | 0.0164 (6) | 0.0174 (6) | 0.0265 (7) | 0.0014 (5) | 0.0031 (5) | 0.0005 (5) |
C5 | 0.0268 (7) | 0.0233 (7) | 0.0298 (8) | −0.0015 (6) | −0.0002 (6) | −0.0092 (6) |
C4 | 0.0234 (7) | 0.0185 (6) | 0.0303 (7) | 0.0006 (5) | 0.0029 (6) | −0.0058 (6) |
C6 | 0.0337 (8) | 0.0266 (7) | 0.0223 (7) | −0.0015 (6) | 0.0011 (6) | −0.0034 (6) |
C7 | 0.0234 (7) | 0.0204 (7) | 0.0241 (7) | −0.0016 (5) | 0.0001 (5) | −0.0018 (5) |
C8 | 0.0142 (6) | 0.0186 (6) | 0.0237 (7) | −0.0001 (5) | 0.0028 (5) | −0.0038 (5) |
C9 | 0.0152 (6) | 0.0182 (6) | 0.0267 (7) | 0.0003 (5) | 0.0034 (5) | −0.0027 (5) |
C10 | 0.0205 (6) | 0.0157 (6) | 0.0166 (6) | −0.0002 (5) | 0.0029 (5) | −0.0010 (5) |
C11 | 0.0184 (6) | 0.0204 (6) | 0.0184 (6) | 0.0012 (5) | 0.0033 (5) | −0.0004 (5) |
C12 | 0.0236 (7) | 0.0216 (7) | 0.0181 (6) | −0.0050 (5) | 0.0030 (5) | −0.0016 (5) |
C13 | 0.0352 (7) | 0.0132 (6) | 0.0199 (6) | −0.0011 (5) | 0.0018 (5) | −0.0007 (5) |
C14 | 0.0255 (7) | 0.0214 (7) | 0.0242 (7) | 0.0062 (5) | −0.0004 (5) | −0.0005 (5) |
C15 | 0.0186 (6) | 0.0206 (7) | 0.0225 (6) | 0.0003 (5) | 0.0004 (5) | −0.0018 (5) |
C16 | 0.0172 (6) | 0.0172 (6) | 0.0214 (6) | −0.0029 (5) | 0.0040 (5) | 0.0018 (5) |
C17 | 0.0214 (7) | 0.0230 (7) | 0.0237 (7) | 0.0021 (5) | 0.0052 (5) | 0.0015 (5) |
C18 | 0.0204 (7) | 0.0343 (8) | 0.0225 (7) | 0.0019 (6) | 0.0015 (5) | 0.0057 (6) |
C19 | 0.0262 (7) | 0.0305 (8) | 0.0198 (7) | −0.0073 (6) | 0.0027 (5) | 0.0006 (6) |
C20 | 0.0283 (7) | 0.0195 (7) | 0.0236 (7) | −0.0033 (5) | 0.0070 (5) | −0.0012 (5) |
C21 | 0.0197 (6) | 0.0193 (6) | 0.0246 (7) | −0.0007 (5) | 0.0040 (5) | 0.0023 (5) |
Geometric parameters (Å, º) top
F1—C13 | 1.3601 (17) | C10—C15 | 1.3937 (18) |
N1—C8 | 1.3869 (17) | C10—C11 | 1.3957 (19) |
N1—C2 | 1.3924 (17) | C11—C12 | 1.387 (2) |
N1—C10 | 1.4292 (18) | C11—H11 | 0.965 (15) |
C2—C3 | 1.3750 (19) | C12—C13 | 1.383 (2) |
C2—C16 | 1.4722 (19) | C12—H12 | 0.961 (16) |
C3—C9 | 1.422 (2) | C13—C14 | 1.386 (2) |
C3—H3 | 0.979 (16) | C14—C15 | 1.388 (2) |
C5—C6 | 1.531 (2) | C14—H14 | 0.960 (16) |
C5—C4 | 1.533 (2) | C15—H15 | 0.984 (16) |
C5—H5A | 1.013 (17) | C16—C21 | 1.4005 (19) |
C5—H5B | 0.987 (17) | C16—C17 | 1.4037 (19) |
C4—C9 | 1.5067 (19) | C17—C18 | 1.388 (2) |
C4—H4A | 1.024 (16) | C17—H17 | 0.971 (15) |
C4—H4B | 0.995 (16) | C18—C19 | 1.385 (2) |
C6—C7 | 1.534 (2) | C18—H18 | 0.961 (17) |
C6—H6A | 0.994 (16) | C19—C20 | 1.393 (2) |
C6—H6B | 1.031 (16) | C19—H19 | 0.960 (16) |
C7—C8 | 1.495 (2) | C20—C21 | 1.389 (2) |
C7—H7A | 1.004 (16) | C20—H20 | 0.982 (15) |
C7—H7B | 0.987 (15) | C21—H21 | 0.981 (15) |
C8—C9 | 1.368 (2) | | |
| | | |
C8—N1—C2 | 108.86 (11) | C3—C9—C4 | 130.79 (12) |
C8—N1—C10 | 124.48 (11) | C15—C10—C11 | 120.76 (13) |
C2—N1—C10 | 126.38 (11) | C15—C10—N1 | 119.11 (11) |
C3—C2—N1 | 107.14 (12) | C11—C10—N1 | 120.12 (11) |
C3—C2—C16 | 130.19 (12) | C12—C11—C10 | 119.90 (12) |
N1—C2—C16 | 122.64 (11) | C12—C11—H11 | 120.3 (9) |
C2—C3—C9 | 108.41 (12) | C10—C11—H11 | 119.8 (9) |
C2—C3—H3 | 124.2 (9) | C13—C12—C11 | 118.14 (12) |
C9—C3—H3 | 127.3 (9) | C13—C12—H12 | 121.0 (9) |
C6—C5—C4 | 111.87 (12) | C11—C12—H12 | 120.9 (9) |
C6—C5—H5A | 108.7 (9) | F1—C13—C12 | 118.31 (12) |
C4—C5—H5A | 108.9 (9) | F1—C13—C14 | 118.49 (12) |
C6—C5—H5B | 111.0 (9) | C12—C13—C14 | 123.19 (13) |
C4—C5—H5B | 109.5 (9) | C13—C14—C15 | 118.22 (12) |
H5A—C5—H5B | 106.6 (13) | C13—C14—H14 | 120.2 (9) |
C9—C4—C5 | 110.81 (12) | C15—C14—H14 | 121.6 (9) |
C9—C4—H4A | 109.6 (8) | C14—C15—C10 | 119.77 (12) |
C5—C4—H4A | 110.5 (8) | C14—C15—H15 | 120.7 (9) |
C9—C4—H4B | 110.4 (9) | C10—C15—H15 | 119.4 (9) |
C5—C4—H4B | 108.9 (9) | C21—C16—C17 | 118.27 (12) |
H4A—C4—H4B | 106.4 (12) | C21—C16—C2 | 122.69 (11) |
C5—C6—C7 | 111.21 (12) | C17—C16—C2 | 119.03 (12) |
C5—C6—H6A | 111.4 (9) | C18—C17—C16 | 120.76 (13) |
C7—C6—H6A | 109.1 (9) | C18—C17—H17 | 120.0 (9) |
C5—C6—H6B | 109.2 (9) | C16—C17—H17 | 119.2 (9) |
C7—C6—H6B | 108.5 (9) | C19—C18—C17 | 120.31 (13) |
H6A—C6—H6B | 107.4 (12) | C19—C18—H18 | 120.8 (10) |
C8—C7—C6 | 108.05 (12) | C17—C18—H18 | 118.9 (10) |
C8—C7—H7A | 110.8 (9) | C18—C19—C20 | 119.69 (13) |
C6—C7—H7A | 110.6 (9) | C18—C19—H19 | 120.5 (9) |
C8—C7—H7B | 111.1 (9) | C20—C19—H19 | 119.7 (9) |
C6—C7—H7B | 110.9 (9) | C21—C20—C19 | 120.21 (13) |
H7A—C7—H7B | 105.4 (12) | C21—C20—H20 | 119.2 (9) |
C9—C8—N1 | 108.38 (12) | C19—C20—H20 | 120.6 (9) |
C9—C8—C7 | 126.68 (12) | C20—C21—C16 | 120.72 (12) |
N1—C8—C7 | 124.80 (12) | C20—C21—H21 | 119.3 (8) |
C8—C9—C3 | 107.20 (11) | C16—C21—H21 | 120.0 (8) |
C8—C9—C4 | 122.00 (12) | | |
| | | |
C8—N1—C2—C3 | 0.93 (13) | C8—N1—C10—C11 | 113.62 (13) |
C10—N1—C2—C3 | 174.98 (11) | C2—N1—C10—C11 | −59.54 (17) |
C8—N1—C2—C16 | −177.14 (11) | C15—C10—C11—C12 | −0.73 (19) |
C10—N1—C2—C16 | −3.09 (18) | N1—C10—C11—C12 | 178.09 (11) |
N1—C2—C3—C9 | −0.37 (13) | C10—C11—C12—C13 | 0.09 (18) |
C16—C2—C3—C9 | 177.50 (12) | C11—C12—C13—F1 | −179.07 (11) |
C6—C5—C4—C9 | −42.60 (16) | C11—C12—C13—C14 | 0.6 (2) |
C4—C5—C6—C7 | 64.40 (16) | F1—C13—C14—C15 | 179.00 (12) |
C5—C6—C7—C8 | −47.59 (16) | C12—C13—C14—C15 | −0.7 (2) |
C2—N1—C8—C9 | −1.15 (13) | C13—C14—C15—C10 | 0.0 (2) |
C10—N1—C8—C9 | −175.33 (11) | C11—C10—C15—C14 | 0.66 (19) |
C2—N1—C8—C7 | 174.87 (11) | N1—C10—C15—C14 | −178.17 (12) |
C10—N1—C8—C7 | 0.68 (18) | C3—C2—C16—C21 | 141.34 (14) |
C6—C7—C8—C9 | 15.50 (18) | N1—C2—C16—C21 | −41.08 (17) |
C6—C7—C8—N1 | −159.78 (12) | C3—C2—C16—C17 | −39.48 (19) |
N1—C8—C9—C3 | 0.90 (14) | N1—C2—C16—C17 | 138.10 (12) |
C7—C8—C9—C3 | −175.02 (12) | C21—C16—C17—C18 | 1.54 (19) |
N1—C8—C9—C4 | 179.55 (11) | C2—C16—C17—C18 | −177.68 (12) |
C7—C8—C9—C4 | 3.6 (2) | C16—C17—C18—C19 | −0.1 (2) |
C2—C3—C9—C8 | −0.32 (14) | C17—C18—C19—C20 | −1.4 (2) |
C2—C3—C9—C4 | −178.81 (12) | C18—C19—C20—C21 | 1.4 (2) |
C5—C4—C9—C8 | 9.98 (17) | C19—C20—C21—C16 | 0.12 (19) |
C5—C4—C9—C3 | −171.72 (13) | C17—C16—C21—C20 | −1.55 (18) |
C8—N1—C10—C15 | −67.54 (16) | C2—C16—C21—C20 | 177.64 (11) |
C2—N1—C10—C15 | 119.29 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···F1i | 0.98 (2) | 2.56 (2) | 3.292 (2) | 131 (1) |
C15—H15···Cg1ii | 0.98 (2) | 2.68 (2) | 3.495 (3) | 141 (1) |
C11—H11···Cg1iii | 0.97 (2) | 2.82 (2) | 3.646 (3) | 144 (1) |
C4—H4B···Cg2iv | 1.00 (2) | 2.82 (2) | 3.708 (3) | 149 (1) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) x, −y+1/2, z+1/2. |
(II) 1-(4-fluorophenyl)-6,6-dimethyl-2-phenyl-4,5,6,7-tetrahydro-1
H-indole
top
Crystal data top
C22H22FN | Z = 2 |
Mr = 319.41 | F(000) = 340 |
Triclinic, P1 | Dx = 1.235 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.273 (2) Å | Cell parameters from 945 reflections |
b = 10.786 (2) Å | θ = 2.4–24.4° |
c = 10.936 (2) Å | µ = 0.08 mm−1 |
α = 61.647 (3)° | T = 100 K |
β = 65.525 (3)° | Prism, pale yellow |
γ = 69.210 (3)° | 0.55 × 0.50 × 0.40 mm |
V = 858.9 (3) Å3 | |
Data collection top
Bruker SMART CCD area detector diffractometer | 3474 independent reflections |
Radiation source: fine-focus sealed tube | 3193 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.938, Tmax = 0.969 | k = −13→13 |
6945 measured reflections | l = −13→13 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0503P)2 + 0.2958P] where P = (Fo2 + 2Fc2)/3 |
3474 reflections | (Δ/σ)max = 0.001 |
305 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C22H22FN | γ = 69.210 (3)° |
Mr = 319.41 | V = 858.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.273 (2) Å | Mo Kα radiation |
b = 10.786 (2) Å | µ = 0.08 mm−1 |
c = 10.936 (2) Å | T = 100 K |
α = 61.647 (3)° | 0.55 × 0.50 × 0.40 mm |
β = 65.525 (3)° | |
Data collection top
Bruker SMART CCD area detector diffractometer | 3474 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3193 reflections with I > 2σ(I) |
Tmin = 0.938, Tmax = 0.969 | Rint = 0.011 |
6945 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.30 e Å−3 |
3474 reflections | Δρmin = −0.26 e Å−3 |
305 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 | Uiso*/Ueq | |
F1 | 0.05379 (8) | 0.27107 (8) | 1.09367 (8) | 0.02903 (19) | |
N1 | 0.52616 (10) | 0.26153 (10) | 0.58141 (9) | 0.0159 (2) | |
C2 | 0.69352 (12) | 0.22494 (11) | 0.55271 (11) | 0.0158 (2) | |
C3 | 0.75945 (13) | 0.22901 (11) | 0.41254 (12) | 0.0169 (2) | |
C4 | 0.63309 (14) | 0.28979 (13) | 0.20741 (12) | 0.0210 (2) | |
C5 | 0.46415 (14) | 0.36120 (13) | 0.18770 (12) | 0.0206 (2) | |
C6 | 0.32642 (13) | 0.29664 (12) | 0.32177 (12) | 0.0195 (2) | |
C7 | 0.32203 (13) | 0.32121 (12) | 0.45158 (12) | 0.0186 (2) | |
C8 | 0.48947 (13) | 0.28668 (11) | 0.46001 (11) | 0.0169 (2) | |
C9 | 0.63108 (13) | 0.26859 (11) | 0.35434 (11) | 0.0174 (2) | |
C10 | 0.40660 (12) | 0.26320 (12) | 0.71529 (11) | 0.0162 (2) | |
C11 | 0.39443 (13) | 0.13754 (12) | 0.83999 (12) | 0.0178 (2) | |
C12 | 0.27696 (13) | 0.13993 (12) | 0.96953 (12) | 0.0199 (2) | |
C13 | 0.17318 (13) | 0.26877 (13) | 0.96883 (12) | 0.0201 (2) | |
C14 | 0.18285 (14) | 0.39517 (13) | 0.84746 (13) | 0.0217 (2) | |
C15 | 0.30232 (13) | 0.39180 (12) | 0.71896 (12) | 0.0195 (2) | |
C16 | 0.77715 (13) | 0.19596 (11) | 0.65491 (11) | 0.0166 (2) | |
C17 | 0.92614 (13) | 0.09977 (12) | 0.65109 (12) | 0.0199 (2) | |
C18 | 1.01508 (14) | 0.07499 (13) | 0.73892 (13) | 0.0234 (3) | |
C19 | 0.95596 (15) | 0.14383 (13) | 0.83469 (13) | 0.0243 (3) | |
C20 | 0.80713 (15) | 0.23747 (13) | 0.84182 (13) | 0.0232 (2) | |
C21 | 0.71887 (14) | 0.26442 (12) | 0.75242 (12) | 0.0196 (2) | |
C22 | 0.16442 (15) | 0.37317 (14) | 0.28941 (14) | 0.0255 (3) | |
C23 | 0.35162 (16) | 0.13617 (13) | 0.35860 (14) | 0.0255 (3) | |
H2 | 0.8750 (18) | 0.2132 (15) | 0.3617 (16) | 0.027 (4)* | |
H4A | 0.6708 (17) | 0.1948 (15) | 0.1977 (15) | 0.023 (3)* | |
H4B | 0.7141 (17) | 0.3491 (15) | 0.1277 (15) | 0.022 (3)* | |
H5A | 0.4604 (17) | 0.3548 (15) | 0.1005 (15) | 0.025 (3)* | |
H5B | 0.4456 (16) | 0.4660 (15) | 0.1659 (15) | 0.022 (3)* | |
H6A | 0.2698 (14) | 0.4270 (13) | 0.4381 (13) | 0.012 (3)* | |
H6B | 0.2498 (16) | 0.2624 (14) | 0.5445 (15) | 0.020 (3)* | |
H11 | 0.4663 (16) | 0.0496 (15) | 0.8355 (15) | 0.021 (3)* | |
H12 | 0.2667 (17) | 0.0523 (16) | 1.0580 (16) | 0.028 (4)* | |
H14 | 0.1085 (18) | 0.4819 (16) | 0.8535 (15) | 0.026 (3)* | |
H15 | 0.3152 (17) | 0.4796 (16) | 0.6308 (16) | 0.025 (3)* | |
H17 | 0.9685 (17) | 0.0496 (15) | 0.5849 (15) | 0.024 (3)* | |
H18 | 1.1176 (19) | 0.0077 (16) | 0.7324 (16) | 0.030 (4)* | |
H19 | 1.0159 (17) | 0.1267 (15) | 0.8974 (15) | 0.026 (3)* | |
H20 | 0.7633 (17) | 0.2857 (16) | 0.9100 (16) | 0.028 (4)* | |
H21 | 0.6151 (17) | 0.3352 (15) | 0.7572 (15) | 0.025 (3)* | |
H22A | 0.1626 (19) | 0.3574 (17) | 0.2078 (18) | 0.038 (4)* | |
H22B | 0.1441 (18) | 0.4789 (17) | 0.2625 (16) | 0.031 (4)* | |
H22C | 0.073 (2) | 0.3364 (17) | 0.3770 (18) | 0.035 (4)* | |
H23A | 0.262 (2) | 0.0942 (17) | 0.4444 (18) | 0.036 (4)* | |
H23B | 0.4538 (19) | 0.0808 (17) | 0.3848 (16) | 0.031 (4)* | |
H23C | 0.3563 (18) | 0.1229 (17) | 0.2735 (17) | 0.035 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0225 (4) | 0.0422 (4) | 0.0224 (4) | −0.0096 (3) | 0.0046 (3) | −0.0196 (3) |
N1 | 0.0148 (4) | 0.0181 (4) | 0.0141 (4) | −0.0031 (3) | −0.0035 (3) | −0.0065 (4) |
C2 | 0.0149 (5) | 0.0139 (5) | 0.0169 (5) | −0.0030 (4) | −0.0037 (4) | −0.0054 (4) |
C3 | 0.0164 (5) | 0.0167 (5) | 0.0163 (5) | −0.0038 (4) | −0.0027 (4) | −0.0067 (4) |
C4 | 0.0208 (5) | 0.0262 (6) | 0.0161 (5) | −0.0050 (5) | −0.0039 (4) | −0.0092 (5) |
C5 | 0.0243 (6) | 0.0221 (6) | 0.0156 (5) | −0.0055 (4) | −0.0073 (4) | −0.0056 (4) |
C6 | 0.0203 (5) | 0.0206 (5) | 0.0194 (5) | −0.0046 (4) | −0.0077 (4) | −0.0071 (4) |
C7 | 0.0170 (5) | 0.0214 (6) | 0.0172 (5) | −0.0044 (4) | −0.0047 (4) | −0.0071 (4) |
C8 | 0.0190 (5) | 0.0169 (5) | 0.0151 (5) | −0.0044 (4) | −0.0053 (4) | −0.0055 (4) |
C9 | 0.0183 (5) | 0.0173 (5) | 0.0159 (5) | −0.0045 (4) | −0.0041 (4) | −0.0060 (4) |
C10 | 0.0143 (5) | 0.0201 (5) | 0.0155 (5) | −0.0043 (4) | −0.0029 (4) | −0.0086 (4) |
C11 | 0.0168 (5) | 0.0179 (5) | 0.0190 (5) | −0.0027 (4) | −0.0053 (4) | −0.0078 (4) |
C12 | 0.0202 (5) | 0.0236 (6) | 0.0162 (5) | −0.0089 (4) | −0.0040 (4) | −0.0059 (5) |
C13 | 0.0153 (5) | 0.0315 (6) | 0.0174 (5) | −0.0076 (4) | 0.0002 (4) | −0.0146 (5) |
C14 | 0.0180 (5) | 0.0240 (6) | 0.0252 (6) | 0.0002 (4) | −0.0057 (5) | −0.0148 (5) |
C15 | 0.0204 (5) | 0.0194 (5) | 0.0183 (5) | −0.0033 (4) | −0.0060 (4) | −0.0073 (5) |
C16 | 0.0170 (5) | 0.0162 (5) | 0.0150 (5) | −0.0065 (4) | −0.0038 (4) | −0.0034 (4) |
C17 | 0.0188 (5) | 0.0201 (5) | 0.0188 (5) | −0.0039 (4) | −0.0043 (4) | −0.0071 (4) |
C18 | 0.0191 (5) | 0.0233 (6) | 0.0244 (6) | −0.0048 (5) | −0.0086 (5) | −0.0043 (5) |
C19 | 0.0281 (6) | 0.0255 (6) | 0.0219 (6) | −0.0116 (5) | −0.0125 (5) | −0.0025 (5) |
C20 | 0.0298 (6) | 0.0240 (6) | 0.0202 (5) | −0.0099 (5) | −0.0079 (5) | −0.0082 (5) |
C21 | 0.0207 (5) | 0.0186 (5) | 0.0195 (5) | −0.0050 (4) | −0.0056 (4) | −0.0069 (4) |
C22 | 0.0238 (6) | 0.0286 (6) | 0.0280 (6) | −0.0048 (5) | −0.0127 (5) | −0.0099 (5) |
C23 | 0.0295 (6) | 0.0222 (6) | 0.0268 (6) | −0.0075 (5) | −0.0084 (5) | −0.0093 (5) |
Geometric parameters (Å, º) top
F1—C13 | 1.3603 (12) | C11—H11 | 0.956 (14) |
N1—C8 | 1.3851 (13) | C12—C13 | 1.3799 (17) |
N1—C2 | 1.3935 (14) | C12—H12 | 0.979 (15) |
N1—C10 | 1.4280 (13) | C13—C14 | 1.3777 (17) |
C2—C3 | 1.3799 (15) | C14—C15 | 1.3906 (16) |
C2—C16 | 1.4706 (14) | C14—H14 | 0.959 (15) |
C3—C9 | 1.4189 (15) | C15—H15 | 0.979 (15) |
C3—H2 | 0.976 (15) | C16—C21 | 1.4007 (16) |
C4—C9 | 1.5046 (15) | C16—C17 | 1.4010 (15) |
C4—C5 | 1.5360 (16) | C17—C18 | 1.3894 (16) |
C4—H4A | 1.000 (14) | C17—H17 | 0.978 (14) |
C4—H4B | 1.001 (14) | C18—C19 | 1.3867 (18) |
C5—C6 | 1.5414 (16) | C18—H18 | 0.969 (15) |
C5—H5A | 1.004 (14) | C19—C20 | 1.3882 (17) |
C5—H5B | 1.002 (14) | C19—H19 | 0.968 (14) |
C6—C23 | 1.5301 (16) | C20—C21 | 1.3908 (16) |
C6—C22 | 1.5317 (16) | C20—H20 | 0.980 (15) |
C6—C7 | 1.5457 (15) | C21—H21 | 0.993 (14) |
C7—C8 | 1.4944 (15) | C22—H22A | 0.992 (17) |
C7—H6A | 1.032 (12) | C22—H22B | 0.998 (16) |
C7—H6B | 1.005 (14) | C22—H22C | 1.000 (17) |
C8—C9 | 1.3685 (15) | C23—H23A | 0.999 (16) |
C10—C15 | 1.3890 (15) | C23—H23B | 0.998 (16) |
C10—C11 | 1.3911 (15) | C23—H23C | 0.988 (16) |
C11—C12 | 1.3894 (15) | | |
| | | |
C8—N1—C2 | 108.80 (9) | C10—C11—H11 | 119.6 (8) |
C8—N1—C10 | 123.45 (9) | C13—C12—C11 | 118.02 (10) |
C2—N1—C10 | 127.58 (9) | C13—C12—H12 | 121.1 (9) |
C3—C2—N1 | 107.14 (9) | C11—C12—H12 | 120.9 (9) |
C3—C2—C16 | 128.65 (10) | F1—C13—C14 | 118.17 (10) |
N1—C2—C16 | 124.14 (9) | F1—C13—C12 | 118.48 (10) |
C2—C3—C9 | 108.20 (10) | C14—C13—C12 | 123.35 (10) |
C2—C3—H2 | 124.9 (8) | C13—C14—C15 | 118.08 (10) |
C9—C3—H2 | 126.8 (8) | C13—C14—H14 | 119.8 (9) |
C9—C4—C5 | 110.28 (9) | C15—C14—H14 | 122.1 (9) |
C9—C4—H4A | 109.4 (8) | C10—C15—C14 | 119.98 (10) |
C5—C4—H4A | 110.8 (8) | C10—C15—H15 | 119.2 (8) |
C9—C4—H4B | 110.8 (8) | C14—C15—H15 | 120.8 (8) |
C5—C4—H4B | 110.2 (8) | C21—C16—C17 | 117.85 (10) |
H4A—C4—H4B | 105.2 (11) | C21—C16—C2 | 123.32 (10) |
C4—C5—C6 | 113.82 (9) | C17—C16—C2 | 118.78 (10) |
C4—C5—H5A | 109.5 (8) | C18—C17—C16 | 121.23 (11) |
C6—C5—H5A | 109.5 (8) | C18—C17—H17 | 119.5 (8) |
C4—C5—H5B | 108.3 (8) | C16—C17—H17 | 119.3 (8) |
C6—C5—H5B | 108.9 (8) | C19—C18—C17 | 120.24 (11) |
H5A—C5—H5B | 106.6 (11) | C19—C18—H18 | 121.4 (9) |
C23—C6—C22 | 109.11 (10) | C17—C18—H18 | 118.3 (9) |
C23—C6—C5 | 110.21 (10) | C18—C19—C20 | 119.27 (10) |
C22—C6—C5 | 109.50 (9) | C18—C19—H19 | 121.2 (9) |
C23—C6—C7 | 110.68 (9) | C20—C19—H19 | 119.6 (9) |
C22—C6—C7 | 108.25 (9) | C19—C20—C21 | 120.69 (11) |
C5—C6—C7 | 109.06 (9) | C19—C20—H20 | 120.1 (9) |
C8—C7—C6 | 110.07 (9) | C21—C20—H20 | 119.2 (9) |
C8—C7—H6A | 110.3 (7) | C20—C21—C16 | 120.69 (11) |
C6—C7—H6A | 109.0 (7) | C20—C21—H21 | 118.7 (8) |
C8—C7—H6B | 111.5 (8) | C16—C21—H21 | 120.6 (8) |
C6—C7—H6B | 110.2 (8) | C6—C22—H22A | 110.1 (9) |
H6A—C7—H6B | 105.7 (10) | C6—C22—H22B | 111.9 (9) |
C9—C8—N1 | 108.44 (9) | H22A—C22—H22B | 108.3 (13) |
C9—C8—C7 | 126.84 (10) | C6—C22—H22C | 110.8 (9) |
N1—C8—C7 | 124.67 (9) | H22A—C22—H22C | 108.9 (13) |
C8—C9—C3 | 107.41 (9) | H22B—C22—H22C | 106.8 (12) |
C8—C9—C4 | 121.72 (10) | C6—C23—H23A | 110.5 (9) |
C3—C9—C4 | 130.87 (10) | C6—C23—H23B | 112.1 (9) |
C15—C10—C11 | 120.56 (10) | H23A—C23—H23B | 106.6 (12) |
C15—C10—N1 | 119.07 (9) | C6—C23—H23C | 109.3 (9) |
C11—C10—N1 | 120.37 (9) | H23A—C23—H23C | 109.8 (13) |
C12—C11—C10 | 119.99 (10) | H23B—C23—H23C | 108.5 (12) |
C12—C11—H11 | 120.4 (8) | | |
| | | |
C8—N1—C2—C3 | 0.52 (12) | C8—N1—C10—C15 | −66.33 (14) |
C10—N1—C2—C3 | 175.81 (9) | C2—N1—C10—C15 | 119.02 (12) |
C8—N1—C2—C16 | 177.66 (9) | C8—N1—C10—C11 | 113.35 (12) |
C10—N1—C2—C16 | −7.05 (16) | C2—N1—C10—C11 | −61.30 (14) |
N1—C2—C3—C9 | 0.01 (12) | C15—C10—C11—C12 | 0.16 (16) |
C16—C2—C3—C9 | −176.96 (10) | N1—C10—C11—C12 | −179.52 (9) |
C9—C4—C5—C6 | −44.48 (13) | C10—C11—C12—C13 | 1.13 (16) |
C4—C5—C6—C23 | −58.79 (12) | C11—C12—C13—F1 | 177.49 (9) |
C4—C5—C6—C22 | −178.82 (9) | C11—C12—C13—C14 | −1.63 (17) |
C4—C5—C6—C7 | 62.90 (12) | F1—C13—C14—C15 | −178.34 (9) |
C23—C6—C7—C8 | 76.83 (11) | C12—C13—C14—C15 | 0.78 (17) |
C22—C6—C7—C8 | −163.64 (9) | C11—C10—C15—C14 | −1.03 (16) |
C5—C6—C7—C8 | −44.57 (12) | N1—C10—C15—C14 | 178.65 (9) |
C2—N1—C8—C9 | −0.86 (12) | C13—C14—C15—C10 | 0.58 (16) |
C10—N1—C8—C9 | −176.39 (9) | C3—C2—C16—C21 | 143.96 (12) |
C2—N1—C8—C7 | 176.69 (10) | N1—C2—C16—C21 | −32.54 (16) |
C10—N1—C8—C7 | 1.16 (16) | C3—C2—C16—C17 | −33.21 (16) |
C6—C7—C8—C9 | 14.42 (15) | N1—C2—C16—C17 | 150.29 (10) |
C6—C7—C8—N1 | −162.68 (10) | C21—C16—C17—C18 | −1.26 (16) |
N1—C8—C9—C3 | 0.85 (12) | C2—C16—C17—C18 | 176.06 (10) |
C7—C8—C9—C3 | −176.64 (10) | C16—C17—C18—C19 | 1.15 (17) |
N1—C8—C9—C4 | −179.35 (10) | C17—C18—C19—C20 | 0.06 (17) |
C7—C8—C9—C4 | 3.16 (17) | C18—C19—C20—C21 | −1.12 (17) |
C2—C3—C9—C8 | −0.53 (12) | C19—C20—C21—C16 | 0.99 (17) |
C2—C3—C9—C4 | 179.69 (11) | C17—C16—C21—C20 | 0.20 (16) |
C5—C4—C9—C8 | 11.45 (15) | C2—C16—C21—C20 | −176.99 (10) |
C5—C4—C9—C3 | −168.80 (11) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22A···F1i | 0.99 (2) | 2.50 (2) | 3.422 (2) | 154 (1) |
C15—H15···Cg1ii | 0.98 (2) | 2.73 (2) | 3.549 (2) | 141 (1) |
C12—H12···Cg2iii | 0.98 (2) | 2.62 (2) | 3.659 (2) | 154 (1) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C20H18FN | C22H22FN |
Mr | 291.35 | 319.41 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 9.256 (6), 10.939 (7), 15.169 (9) | 9.273 (2), 10.786 (2), 10.936 (2) |
α, β, γ (°) | 90, 97.75 (1), 90 | 61.647 (3), 65.525 (3), 69.210 (3) |
V (Å3) | 1521.9 (17) | 858.9 (3) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.60 × 0.20 × 0.20 | 0.55 × 0.50 × 0.40 |
|
Data collection |
Diffractometer | Bruker SMART CCD area detector diffractometer | Bruker SMART CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.912, 0.984 | 0.938, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15212, 3073, 2619 | 6945, 3474, 3193 |
Rint | 0.030 | 0.011 |
(sin θ/λ)max (Å−1) | 0.625 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.097, 1.03 | 0.038, 0.097, 1.05 |
No. of reflections | 3073 | 3474 |
No. of parameters | 271 | 305 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.29, −0.20 | 0.30, −0.26 |
Selected torsion angles (º) for (I) topC10—N1—C2—C16 | −3.09 (18) | C6—C7—C8—C9 | 15.50 (18) |
C6—C5—C4—C9 | −42.60 (16) | C7—C8—C9—C4 | 3.6 (2) |
C4—C5—C6—C7 | 64.40 (16) | C5—C4—C9—C8 | 9.98 (17) |
C5—C6—C7—C8 | −47.59 (16) | C8—N1—C10—C11 | 113.62 (13) |
C10—N1—C8—C9 | −175.33 (11) | N1—C2—C16—C17 | 138.10 (12) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···F1i | 0.98 (2) | 2.56 (2) | 3.292 (2) | 131 (1) |
C15—H15···Cg1ii | 0.98 (2) | 2.68 (2) | 3.495 (3) | 141 (1) |
C11—H11···Cg1iii | 0.97 (2) | 2.82 (2) | 3.646 (3) | 144 (1) |
C4—H4B···Cg2iv | 1.00 (2) | 2.82 (2) | 3.708 (3) | 149 (1) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) x, −y+1/2, z+1/2. |
Selected torsion angles (º) for (II) topC10—N1—C2—C16 | −7.05 (16) | C6—C7—C8—C9 | 14.42 (15) |
C9—C4—C5—C6 | −44.48 (13) | C7—C8—C9—C4 | 3.16 (17) |
C4—C5—C6—C7 | 62.90 (12) | C8—N1—C10—C11 | 113.35 (12) |
C5—C6—C7—C8 | −44.57 (12) | N1—C2—C16—C17 | 150.29 (10) |
C10—N1—C8—C9 | −176.39 (9) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22A···F1i | 0.99 (2) | 2.50 (2) | 3.422 (2) | 154 (1) |
C15—H15···Cg1ii | 0.98 (2) | 2.73 (2) | 3.549 (2) | 141 (1) |
C12—H12···Cg2iii | 0.98 (2) | 2.62 (2) | 3.659 (2) | 154 (1) |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2. |
Crystal engineering via manipulation of hydrogen bonding has attracted a lot of interest recently (Aaker\"oy, 1997; Guru Row, 1999; Desiraju, 2000, 2002; Hunter et al., 2001). Weak C—H···π (Nishio et al., 1995; Umezawa et al., 1999; Takahashi et al., 2000), π stacking (Hunter, 1993 & 1994) and C—H···O (Desiraju & Steiner, 1999; Steiner, 2002) interactions have been found to generate different crystal engineering motifs. Organohalo compounds also have been found to generate motifs via C—H···X, X···X and C—X···π interactions (Thalladi et al., 1998). It has been shown that fluorine does not readily accept hydrogen bonds and hence behaves differently from Cl and Br (Shimoni & Glusker, 1994; Howard et al., 1996; Dunitz & Taylor, 1997; Desiraju et al., 1989). We have shown that a significant number of compounds pack via weak interactions involving organic fluorine only (Prasanna et al., 2000a, 2000b, 2000c, 2001; Choudhury et al., 2002, 2004a) and generate different packing motifs via F···F, C—H···F and C—F···π interactions.
A structural study of 1-(4-fluorophenyl)-2-phenyl- 4,5,6,7-tetrahydro-1H-indole, (I), and 1-(4-fluorophenyl)-6,6-dimethyl-2 -phenyl-4,5,6,7-tetrahydro-1H-indole, (II), was undertaken because in these compounds the interactions predominatly involve `organic fluorine' and there are no other strong directional interactions involving H atoms.
A view of the (I), with the atom-labelling scheme, is shown in Fig. 1. In the tetrahydroindole ring, atoms C5 and C6 deviate from the C4/C9/C8/C7 plane by 0.310 (2) and −0.456 (2) Å, respectively. The two phenyl rings (C10–C15 and C16–C21) subtend an angle of 126.41 (4)° between their planes. Selected torsion angles are given in Table 1. The molecules pack via a C—H···F interaction, along with three independent C—H···π interactions (Table 2; Cg1 and Cg2 are the centers of gravity of N1/C2/C3/C9/C8 and C16–C21 rings, respectively). Two independent C—H···π interactions via atoms H11 and H15 form a chain of molecular dimers in the crystallographic a direction (Fig. 2). These dimers are connected to similar neighboring chains of molecular dimers via one C—H···F interaction through atom H3, generating a sheet of molecules, as shown in Fig. 2, by a combination of inversion and translation operations A further C—H···π interaction generates a chain of molecules via a glide operation along the c axis (Fig. 3); this interaction links the sheets and gives rise to a three-dimensional network.
Fig. 4 depicts (II), with the atom-labelling scheme. In the tetrahydroindole ring, atoms C5 and C6 deviate from the C4/C9/C8/C7 plane by 0.340 (2) and −0.420 (2) Å, respectively. The two phenyl rings (C10–C15 and C16–C21) subtend an angle of 115.38 (4)° between their planes. Selected torsion angles are given in Table 3. The molecules pack via C—H···F interactions, along with two independent C—H···π interactions (Table 4). These C—H···π interactions connected through atoms H11 and H15 form a sheet motif in the bc plane, resulting in molecular dimers (Fig. 5; Cg1 and Cg2 are the centers of gravity N1/C2/C3/C9/C8 and C16–C21 rings, respectively). These dimers are linked via a unique C—H···F interaction through methyl atom H22A (Fig. 5), generating a sheet structure; there are only van der Waals interactions between the sheets.
In our earlier study (Choudhury et al., 2004b), we showed that, in the presence of a strong acceptor such as C═O, the C—H···O interaction takes priority over C—H···F and C—H···π interactions. Although C—H···F interactions are weaker than C—H···O interactions, the former? appear to play a significant role in the crystal packing of the molecules in the crystal structure by a subtle change in the C—H···F and C—H···π interactions in the two structures described here. Our current results suggest that, while interactions involving `organic fluorine' have a significant influence in generating supramolecular assemblies in organic solids, their general use to predict, a priori, packing motifs is yet to be harnessed.