Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107057939/sf3060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107057939/sf3060Isup2.hkl |
CCDC reference: 672567
For related literature, see: Cochran et al. (2000); Dunitz (2004); Dunitz & Taylor (1997); Fauré et al. (1999); Gade & Mountford (2001); Gordon et al. (2002); Howard et al. (1996); Janiak (2000); Schrock et al. (1998); Schrodi et al. (2001); Ward et al. (2002).
The title compound was obtained as a side product from an alkylation reaction of HN(CH2CH2NHC6F5)2 with benzyl chloride in the presence of K2CO3, according to the general method described by Cochran et al. (2000). [Recrystallization from which solvent?]
H atoms were located in a difference Fourier map and refined freely. [Please check added text]
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).
C24H17F10N3O2 | F(000) = 2304 |
Mr = 569.41 | Dx = 1.624 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8495 reflections |
a = 7.6382 (7) Å | θ = 2.5–29.8° |
b = 14.9272 (15) Å | µ = 0.16 mm−1 |
c = 40.857 (4) Å | T = 120 K |
V = 4658.4 (8) Å3 | Block, colourless |
Z = 8 | 0.30 × 0.20 × 0.20 mm |
Bruker SMART 1K diffractometer | 5603 independent reflections |
Radiation source: fine-focus sealed tube | 4174 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −9→10 |
Tmin = 0.925, Tmax = 1.000 | k = −19→9 |
25323 measured reflections | l = −53→48 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0347P)2 + 2.4908P] where P = (Fo2 + 2Fc2)/3 |
5603 reflections | (Δ/σ)max < 0.001 |
420 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C24H17F10N3O2 | V = 4658.4 (8) Å3 |
Mr = 569.41 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.6382 (7) Å | µ = 0.16 mm−1 |
b = 14.9272 (15) Å | T = 120 K |
c = 40.857 (4) Å | 0.30 × 0.20 × 0.20 mm |
Bruker SMART 1K diffractometer | 5603 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 4174 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 1.000 | Rint = 0.048 |
25323 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.102 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.25 e Å−3 |
5603 reflections | Δρmin = −0.27 e Å−3 |
420 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | −0.22240 (19) | 0.16839 (10) | 0.14863 (4) | 0.0215 (3) | |
N2 | −0.4225 (2) | 0.06994 (11) | 0.20308 (4) | 0.0284 (4) | |
N3 | −0.0730 (2) | 0.28221 (11) | 0.09205 (4) | 0.0240 (3) | |
O1 | −0.32683 (17) | 0.02918 (9) | 0.13640 (3) | 0.0284 (3) | |
O2 | −0.06745 (16) | 0.07645 (8) | 0.11586 (3) | 0.0237 (3) | |
C11 | −0.2138 (2) | 0.08699 (12) | 0.13402 (4) | 0.0221 (4) | |
C12 | −0.0422 (3) | −0.01483 (13) | 0.10390 (5) | 0.0292 (4) | |
C13 | 0.1128 (2) | −0.01703 (11) | 0.08137 (5) | 0.0241 (4) | |
C14 | 0.0908 (3) | −0.04241 (12) | 0.04890 (5) | 0.0289 (4) | |
C15 | 0.2351 (3) | −0.05220 (13) | 0.02839 (5) | 0.0318 (5) | |
C16 | 0.4013 (3) | −0.03634 (13) | 0.04027 (5) | 0.0308 (4) | |
C17 | 0.4241 (3) | −0.00885 (13) | 0.07244 (5) | 0.0286 (4) | |
C18 | 0.2811 (3) | 0.00029 (12) | 0.09300 (5) | 0.0254 (4) | |
C21 | −0.3887 (2) | 0.19409 (13) | 0.16399 (5) | 0.0256 (4) | |
C22 | −0.4053 (3) | 0.16794 (13) | 0.19981 (5) | 0.0271 (4) | |
C23 | −0.3807 (2) | 0.02600 (12) | 0.23162 (5) | 0.0245 (4) | |
C24 | −0.3146 (3) | −0.06146 (13) | 0.23106 (5) | 0.0296 (4) | |
C25 | −0.2777 (3) | −0.10982 (13) | 0.25884 (5) | 0.0350 (5) | |
C26 | −0.3033 (3) | −0.07221 (14) | 0.28932 (5) | 0.0367 (5) | |
C27 | −0.3676 (3) | 0.01344 (14) | 0.29108 (5) | 0.0338 (5) | |
C28 | −0.4070 (3) | 0.06099 (12) | 0.26309 (5) | 0.0285 (4) | |
C31 | −0.0755 (2) | 0.23139 (11) | 0.15058 (5) | 0.0214 (4) | |
C32 | −0.0895 (3) | 0.30861 (12) | 0.12617 (5) | 0.0245 (4) | |
C33 | 0.0787 (2) | 0.25282 (11) | 0.07725 (4) | 0.0191 (4) | |
C34 | 0.0692 (2) | 0.21446 (12) | 0.04612 (4) | 0.0228 (4) | |
C35 | 0.2125 (2) | 0.18822 (11) | 0.02825 (4) | 0.0240 (4) | |
C36 | 0.3783 (2) | 0.19818 (12) | 0.04110 (4) | 0.0237 (4) | |
C37 | 0.3928 (2) | 0.23370 (12) | 0.07200 (5) | 0.0226 (4) | |
C38 | 0.2484 (2) | 0.26037 (11) | 0.08975 (4) | 0.0206 (4) | |
F24 | −0.28452 (19) | −0.09986 (8) | 0.20144 (3) | 0.0436 (3) | |
F25 | −0.2119 (2) | −0.19330 (8) | 0.25656 (3) | 0.0569 (4) | |
F26 | −0.2651 (2) | −0.11886 (9) | 0.31666 (3) | 0.0586 (4) | |
F27 | −0.3941 (2) | 0.05121 (9) | 0.32056 (3) | 0.0527 (4) | |
F28 | −0.47823 (18) | 0.14354 (8) | 0.26672 (3) | 0.0420 (3) | |
F34 | −0.09213 (14) | 0.20300 (8) | 0.03285 (3) | 0.0330 (3) | |
F35 | 0.19206 (16) | 0.15264 (8) | −0.00181 (3) | 0.0338 (3) | |
F36 | 0.52101 (14) | 0.17269 (8) | 0.02426 (3) | 0.0336 (3) | |
F37 | 0.55281 (13) | 0.24290 (9) | 0.08591 (3) | 0.0351 (3) | |
F38 | 0.27832 (13) | 0.29414 (7) | 0.12014 (2) | 0.0276 (2) | |
H2 | −0.396 (3) | 0.0424 (15) | 0.1852 (6) | 0.034 (6)* | |
H3 | −0.166 (3) | 0.2639 (15) | 0.0824 (6) | 0.037 (6)* | |
H14 | −0.029 (3) | −0.0537 (14) | 0.0414 (5) | 0.032 (6)* | |
H15 | 0.216 (3) | −0.0712 (15) | 0.0075 (6) | 0.040 (6)* | |
H16 | 0.495 (3) | −0.0441 (15) | 0.0263 (6) | 0.040 (6)* | |
H17 | 0.538 (3) | 0.0026 (14) | 0.0802 (5) | 0.036 (6)* | |
H18 | 0.301 (3) | 0.0165 (14) | 0.1155 (6) | 0.033 (6)* | |
H121 | −0.151 (3) | −0.0349 (15) | 0.0926 (5) | 0.038 (6)* | |
H122 | −0.017 (3) | −0.0534 (14) | 0.1239 (5) | 0.032 (6)* | |
H211 | −0.398 (2) | 0.2601 (13) | 0.1628 (5) | 0.024 (5)* | |
H212 | −0.482 (3) | 0.1711 (13) | 0.1514 (5) | 0.027 (5)* | |
H221 | −0.510 (3) | 0.1978 (13) | 0.2086 (5) | 0.026 (5)* | |
H222 | −0.297 (3) | 0.1902 (13) | 0.2127 (5) | 0.022 (5)* | |
H311 | 0.031 (3) | 0.1985 (12) | 0.1472 (5) | 0.020 (5)* | |
H312 | −0.070 (2) | 0.2555 (13) | 0.1736 (5) | 0.022 (5)* | |
H322 | −0.205 (3) | 0.3387 (13) | 0.1280 (5) | 0.026 (5)* | |
H321 | −0.002 (3) | 0.3544 (14) | 0.1317 (5) | 0.029 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0217 (7) | 0.0205 (7) | 0.0224 (8) | −0.0012 (6) | 0.0030 (6) | 0.0010 (6) |
N2 | 0.0374 (10) | 0.0270 (8) | 0.0208 (9) | −0.0053 (7) | 0.0051 (7) | −0.0006 (7) |
N3 | 0.0183 (7) | 0.0299 (8) | 0.0239 (8) | 0.0007 (6) | −0.0001 (6) | 0.0047 (7) |
O1 | 0.0313 (7) | 0.0307 (7) | 0.0230 (7) | −0.0096 (6) | 0.0031 (6) | −0.0035 (6) |
O2 | 0.0279 (7) | 0.0180 (6) | 0.0252 (7) | −0.0016 (5) | 0.0042 (5) | −0.0029 (5) |
C11 | 0.0253 (9) | 0.0245 (9) | 0.0165 (9) | −0.0011 (7) | −0.0016 (7) | 0.0011 (7) |
C12 | 0.0337 (11) | 0.0207 (9) | 0.0332 (11) | −0.0025 (8) | 0.0038 (9) | −0.0053 (8) |
C13 | 0.0315 (10) | 0.0154 (8) | 0.0254 (10) | 0.0002 (7) | −0.0012 (8) | −0.0024 (7) |
C14 | 0.0339 (11) | 0.0247 (9) | 0.0281 (11) | 0.0003 (8) | −0.0059 (9) | −0.0040 (8) |
C15 | 0.0508 (13) | 0.0255 (9) | 0.0189 (10) | 0.0032 (9) | −0.0029 (9) | −0.0032 (8) |
C16 | 0.0398 (12) | 0.0244 (10) | 0.0284 (11) | 0.0061 (9) | 0.0085 (10) | 0.0019 (8) |
C17 | 0.0303 (10) | 0.0268 (10) | 0.0287 (11) | 0.0025 (8) | −0.0024 (9) | 0.0002 (8) |
C18 | 0.0375 (11) | 0.0194 (8) | 0.0192 (10) | 0.0006 (8) | −0.0034 (8) | −0.0024 (7) |
C21 | 0.0237 (9) | 0.0273 (10) | 0.0259 (10) | 0.0033 (8) | 0.0027 (8) | 0.0014 (8) |
C22 | 0.0304 (10) | 0.0262 (9) | 0.0245 (10) | 0.0003 (8) | 0.0073 (8) | 0.0002 (8) |
C23 | 0.0246 (9) | 0.0254 (9) | 0.0235 (10) | −0.0060 (8) | 0.0058 (8) | −0.0018 (7) |
C24 | 0.0400 (11) | 0.0266 (9) | 0.0221 (10) | −0.0037 (8) | 0.0037 (9) | −0.0065 (8) |
C25 | 0.0476 (13) | 0.0232 (10) | 0.0341 (12) | 0.0038 (9) | 0.0027 (10) | −0.0028 (8) |
C26 | 0.0527 (14) | 0.0337 (11) | 0.0236 (11) | 0.0020 (10) | 0.0021 (10) | 0.0034 (8) |
C27 | 0.0476 (12) | 0.0335 (11) | 0.0203 (10) | −0.0022 (9) | 0.0099 (9) | −0.0061 (8) |
C28 | 0.0331 (10) | 0.0236 (9) | 0.0289 (10) | 0.0001 (8) | 0.0106 (9) | −0.0012 (8) |
C31 | 0.0244 (9) | 0.0186 (8) | 0.0212 (10) | 0.0000 (7) | 0.0013 (7) | −0.0018 (7) |
C32 | 0.0248 (9) | 0.0188 (8) | 0.0299 (10) | 0.0030 (8) | 0.0056 (8) | 0.0023 (7) |
C33 | 0.0203 (8) | 0.0182 (8) | 0.0187 (9) | −0.0015 (7) | −0.0004 (7) | 0.0049 (7) |
C34 | 0.0219 (9) | 0.0234 (9) | 0.0230 (9) | −0.0044 (7) | −0.0070 (7) | 0.0034 (7) |
C35 | 0.0332 (10) | 0.0197 (8) | 0.0192 (9) | −0.0022 (7) | −0.0016 (8) | −0.0004 (7) |
C36 | 0.0238 (9) | 0.0222 (9) | 0.0250 (10) | 0.0014 (7) | 0.0049 (7) | 0.0003 (7) |
C37 | 0.0177 (8) | 0.0256 (9) | 0.0246 (10) | −0.0012 (7) | −0.0039 (7) | 0.0021 (7) |
C38 | 0.0244 (8) | 0.0207 (8) | 0.0167 (9) | −0.0022 (7) | −0.0032 (7) | −0.0004 (7) |
F24 | 0.0747 (9) | 0.0309 (6) | 0.0250 (6) | 0.0028 (6) | 0.0042 (6) | −0.0099 (5) |
F25 | 0.0976 (12) | 0.0318 (7) | 0.0415 (8) | 0.0218 (7) | 0.0030 (8) | −0.0024 (6) |
F26 | 0.1011 (12) | 0.0473 (8) | 0.0272 (7) | 0.0189 (8) | −0.0017 (8) | 0.0077 (6) |
F27 | 0.0932 (11) | 0.0439 (7) | 0.0210 (6) | 0.0125 (7) | 0.0138 (7) | −0.0041 (5) |
F28 | 0.0636 (9) | 0.0300 (6) | 0.0323 (7) | 0.0119 (6) | 0.0184 (6) | −0.0010 (5) |
F34 | 0.0254 (6) | 0.0437 (7) | 0.0298 (6) | −0.0073 (5) | −0.0110 (5) | 0.0007 (5) |
F35 | 0.0452 (7) | 0.0344 (6) | 0.0219 (6) | −0.0053 (5) | −0.0039 (5) | −0.0070 (5) |
F36 | 0.0303 (6) | 0.0393 (6) | 0.0311 (6) | 0.0062 (5) | 0.0104 (5) | −0.0031 (5) |
F37 | 0.0174 (5) | 0.0574 (8) | 0.0307 (6) | −0.0008 (5) | −0.0033 (5) | −0.0023 (6) |
F38 | 0.0258 (5) | 0.0372 (6) | 0.0198 (6) | −0.0033 (5) | −0.0025 (4) | −0.0051 (4) |
N1—C11 | 1.355 (2) | C22—H221 | 0.98 (2) |
N1—C31 | 1.466 (2) | C22—H222 | 1.03 (2) |
N1—C21 | 1.468 (2) | C23—C24 | 1.400 (3) |
N2—C23 | 1.375 (2) | C23—C28 | 1.402 (3) |
N2—C22 | 1.475 (2) | C24—F24 | 1.359 (2) |
N2—H2 | 0.86 (2) | C24—C25 | 1.374 (3) |
N3—C33 | 1.379 (2) | C25—F25 | 1.347 (2) |
N3—C32 | 1.454 (2) | C25—C26 | 1.380 (3) |
N3—H3 | 0.86 (2) | C26—F26 | 1.348 (2) |
O1—C11 | 1.224 (2) | C26—C27 | 1.372 (3) |
O2—C11 | 1.351 (2) | C27—F27 | 1.345 (2) |
O2—C12 | 1.460 (2) | C27—C28 | 1.379 (3) |
C12—C13 | 1.500 (3) | C28—F28 | 1.355 (2) |
C12—H121 | 0.99 (2) | C31—C32 | 1.528 (2) |
C12—H122 | 1.02 (2) | C31—H311 | 0.960 (19) |
C13—C14 | 1.390 (3) | C31—H312 | 1.01 (2) |
C13—C18 | 1.395 (3) | C32—H322 | 0.99 (2) |
C14—C15 | 1.392 (3) | C32—H321 | 0.98 (2) |
C14—H14 | 0.98 (2) | C33—C34 | 1.397 (2) |
C15—C16 | 1.380 (3) | C33—C38 | 1.398 (2) |
C15—H15 | 0.91 (2) | C34—F34 | 1.3572 (19) |
C16—C17 | 1.388 (3) | C34—C35 | 1.373 (3) |
C16—H16 | 0.92 (2) | C35—F35 | 1.347 (2) |
C17—C18 | 1.384 (3) | C35—C36 | 1.378 (3) |
C17—H17 | 0.94 (2) | C36—F36 | 1.344 (2) |
C18—H18 | 0.96 (2) | C36—C37 | 1.374 (3) |
C21—C22 | 1.520 (3) | C37—F37 | 1.355 (2) |
C21—H211 | 0.99 (2) | C37—C38 | 1.378 (2) |
C21—H212 | 0.94 (2) | C38—F38 | 1.3592 (19) |
C11—N1—C31 | 124.19 (15) | N2—C23—C24 | 120.96 (17) |
C11—N1—C21 | 117.67 (15) | N2—C23—C28 | 124.50 (17) |
C31—N1—C21 | 118.13 (14) | C24—C23—C28 | 114.46 (17) |
C23—N2—C22 | 121.97 (16) | F24—C24—C25 | 118.65 (17) |
C23—N2—H2 | 115.9 (15) | F24—C24—C23 | 117.97 (17) |
C22—N2—H2 | 112.1 (15) | C25—C24—C23 | 123.38 (18) |
C33—N3—C32 | 125.41 (16) | F25—C25—C24 | 120.35 (18) |
C33—N3—H3 | 113.3 (15) | F25—C25—C26 | 119.46 (19) |
C32—N3—H3 | 116.9 (15) | C24—C25—C26 | 120.17 (18) |
C11—O2—C12 | 113.69 (14) | F26—C26—C27 | 121.03 (19) |
O1—C11—O2 | 123.02 (16) | F26—C26—C25 | 120.45 (19) |
O1—C11—N1 | 124.25 (17) | C27—C26—C25 | 118.52 (19) |
O2—C11—N1 | 112.72 (15) | F27—C27—C26 | 119.45 (19) |
O2—C12—C13 | 109.27 (15) | F27—C27—C28 | 119.59 (18) |
O2—C12—H121 | 109.0 (13) | C26—C27—C28 | 120.95 (18) |
C13—C12—H121 | 111.6 (13) | F28—C28—C27 | 117.70 (17) |
O2—C12—H122 | 106.6 (12) | F28—C28—C23 | 119.78 (17) |
C13—C12—H122 | 109.3 (12) | C27—C28—C23 | 122.50 (18) |
H121—C12—H122 | 111.0 (17) | N1—C31—C32 | 113.25 (15) |
C14—C13—C18 | 119.15 (18) | N1—C31—H311 | 108.2 (11) |
C14—C13—C12 | 119.77 (18) | C32—C31—H311 | 110.6 (11) |
C18—C13—C12 | 120.94 (17) | N1—C31—H312 | 108.2 (11) |
C13—C14—C15 | 120.52 (19) | C32—C31—H312 | 110.1 (11) |
C13—C14—H14 | 117.2 (12) | H311—C31—H312 | 106.3 (15) |
C15—C14—H14 | 122.3 (12) | N3—C32—C31 | 114.53 (15) |
C16—C15—C14 | 119.91 (19) | N3—C32—H322 | 105.7 (11) |
C16—C15—H15 | 121.9 (15) | C31—C32—H322 | 110.8 (12) |
C14—C15—H15 | 118.2 (15) | N3—C32—H321 | 110.4 (12) |
C15—C16—C17 | 119.9 (2) | C31—C32—H321 | 109.1 (12) |
C15—C16—H16 | 118.2 (14) | H322—C32—H321 | 105.9 (16) |
C17—C16—H16 | 121.8 (14) | N3—C33—C34 | 119.09 (16) |
C18—C17—C16 | 120.34 (19) | N3—C33—C38 | 126.41 (16) |
C18—C17—H17 | 120.5 (14) | C34—C33—C38 | 114.45 (16) |
C16—C17—H17 | 119.1 (14) | F34—C34—C35 | 118.39 (16) |
C17—C18—C13 | 120.12 (18) | F34—C34—C33 | 117.56 (16) |
C17—C18—H18 | 118.6 (13) | C35—C34—C33 | 124.04 (16) |
C13—C18—H18 | 121.3 (13) | F35—C35—C34 | 120.31 (16) |
N1—C21—C22 | 114.62 (16) | F35—C35—C36 | 119.76 (16) |
N1—C21—H211 | 107.6 (11) | C34—C35—C36 | 119.93 (16) |
C22—C21—H211 | 107.3 (11) | F36—C36—C37 | 120.96 (16) |
N1—C21—H212 | 108.9 (12) | F36—C36—C35 | 121.29 (16) |
C22—C21—H212 | 111.7 (12) | C37—C36—C35 | 117.75 (16) |
H211—C21—H212 | 106.3 (16) | F37—C37—C36 | 119.81 (16) |
N2—C22—C21 | 110.46 (16) | F37—C37—C38 | 118.15 (16) |
N2—C22—H221 | 110.2 (11) | C36—C37—C38 | 122.04 (16) |
C21—C22—H221 | 107.7 (12) | F38—C38—C37 | 116.95 (15) |
N2—C22—H222 | 110.1 (11) | F38—C38—C33 | 121.29 (15) |
C21—C22—H222 | 110.0 (11) | C37—C38—C33 | 121.75 (16) |
H221—C22—H222 | 108.2 (15) | ||
C12—O2—C11—O1 | −9.7 (2) | F27—C27—C28—F28 | −2.6 (3) |
C12—O2—C11—N1 | 171.34 (16) | C26—C27—C28—F28 | 176.77 (19) |
C31—N1—C11—O1 | 168.92 (17) | F27—C27—C28—C23 | 179.29 (19) |
C21—N1—C11—O1 | −9.9 (3) | C26—C27—C28—C23 | −1.3 (3) |
C31—N1—C11—O2 | −12.2 (2) | N2—C23—C28—F28 | 0.1 (3) |
C21—N1—C11—O2 | 169.04 (15) | C24—C23—C28—F28 | −176.93 (17) |
C11—O2—C12—C13 | 174.26 (15) | N2—C23—C28—C27 | 178.14 (19) |
O2—C12—C13—C14 | −118.74 (19) | C24—C23—C28—C27 | 1.2 (3) |
O2—C12—C13—C18 | 65.6 (2) | C11—N1—C31—C32 | 102.95 (19) |
C18—C13—C14—C15 | 1.3 (3) | C21—N1—C31—C32 | −78.3 (2) |
C12—C13—C14—C15 | −174.49 (17) | C33—N3—C32—C31 | −70.0 (2) |
C13—C14—C15—C16 | −0.2 (3) | N1—C31—C32—N3 | −67.2 (2) |
C14—C15—C16—C17 | −1.3 (3) | C32—N3—C33—C34 | 168.50 (16) |
C15—C16—C17—C18 | 1.9 (3) | C32—N3—C33—C38 | −14.2 (3) |
C16—C17—C18—C13 | −0.8 (3) | N3—C33—C34—F34 | −4.1 (2) |
C14—C13—C18—C17 | −0.7 (3) | C38—C33—C34—F34 | 178.36 (15) |
C12—C13—C18—C17 | 174.97 (17) | N3—C33—C34—C35 | 175.66 (17) |
C11—N1—C21—C22 | 90.3 (2) | C38—C33—C34—C35 | −1.9 (3) |
C31—N1—C21—C22 | −88.6 (2) | F34—C34—C35—F35 | 0.5 (2) |
C23—N2—C22—C21 | 157.51 (17) | C33—C34—C35—F35 | −179.24 (16) |
N1—C21—C22—N2 | −70.2 (2) | F34—C34—C35—C36 | −179.45 (16) |
C22—N2—C23—C24 | −148.31 (19) | C33—C34—C35—C36 | 0.8 (3) |
C22—N2—C23—C28 | 34.9 (3) | F35—C35—C36—F36 | −0.3 (3) |
N2—C23—C24—F24 | 3.3 (3) | C34—C35—C36—F36 | 179.65 (16) |
C28—C23—C24—F24 | −179.60 (17) | F35—C35—C36—C37 | −179.18 (16) |
N2—C23—C24—C25 | −177.17 (19) | C34—C35—C36—C37 | 0.7 (3) |
C28—C23—C24—C25 | −0.1 (3) | F36—C36—C37—F37 | −0.3 (3) |
F24—C24—C25—F25 | 0.5 (3) | C35—C36—C37—F37 | 178.56 (16) |
C23—C24—C25—F25 | −179.08 (19) | F36—C36—C37—C38 | 179.97 (16) |
F24—C24—C25—C26 | 178.7 (2) | C35—C36—C37—C38 | −1.1 (3) |
C23—C24—C25—C26 | −0.9 (3) | F37—C37—C38—F38 | 0.0 (2) |
F25—C25—C26—F26 | −0.9 (3) | C36—C37—C38—F38 | 179.67 (16) |
C24—C25—C26—F26 | −179.1 (2) | F37—C37—C38—C33 | −179.75 (16) |
F25—C25—C26—C27 | 178.9 (2) | C36—C37—C38—C33 | −0.1 (3) |
C24—C25—C26—C27 | 0.7 (3) | N3—C33—C38—F38 | 4.4 (3) |
F26—C26—C27—F27 | −0.5 (3) | C34—C33—C38—F38 | −178.20 (15) |
C25—C26—C27—F27 | 179.7 (2) | N3—C33—C38—C37 | −175.86 (17) |
F26—C26—C27—C28 | −179.8 (2) | C34—C33—C38—C37 | 1.5 (2) |
C25—C26—C27—C28 | 0.4 (3) | C24—C23—N2—H2 | −5.6 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 (2) | 2.07 (2) | 2.886 (2) | 157 (2) |
N3—H3···F37i | 0.86 (2) | 2.17 (2) | 2.9282 (19) | 147 (2) |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C24H17F10N3O2 |
Mr | 569.41 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 7.6382 (7), 14.9272 (15), 40.857 (4) |
V (Å3) | 4658.4 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.16 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1K diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.925, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25323, 5603, 4174 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.102, 1.04 |
No. of reflections | 5603 |
No. of parameters | 420 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.25, −0.27 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Bruker, 2003).
N1—C11 | 1.355 (2) | O1—C11 | 1.224 (2) |
N2—C23 | 1.375 (2) | O2—C11 | 1.351 (2) |
N3—C33 | 1.379 (2) | ||
C11—N1—C31 | 124.19 (15) | C11—O2—C12 | 113.69 (14) |
C11—N1—C21 | 117.67 (15) | O1—C11—O2 | 123.02 (16) |
C31—N1—C21 | 118.13 (14) | O1—C11—N1 | 124.25 (17) |
C23—N2—C22 | 121.97 (16) | O2—C11—N1 | 112.72 (15) |
C33—N3—C32 | 125.41 (16) | ||
C24—C23—N2—H2 | −5.6 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 (2) | 2.07 (2) | 2.886 (2) | 157 (2) |
N3—H3···F37i | 0.86 (2) | 2.17 (2) | 2.9282 (19) | 147 (2) |
Symmetry code: (i) x−1, y, z. |
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Interest in tris-amine derivatives, RN(CH2CH2NHR')2, has grown steadily over the past two decades. These ligands are widely used to stabilize unusual metal oxidation states and coordination geometry around various metal centres (Fauré et al., 1999; Ward et al., 2002; Gade & Mountford, 2001). Their complexes were applied in several catalytic processes (Gade & Mountford, 2001; Schrodi et al., 2001). Particular attention has been paid to the complexes of fluorinated tris-amine ligands, due to the electron-withdrawal properties of the C6F5-group and additional secondary Ar—F···M interactions (Schrock et al., 1998; Cochran et al., 2000). Here, we report the structure of the title mixed aryl/pentafluoroaryl substituted bis(aminoethyl)carbamate, (I).
As expected for carbamate derivatives, the C11—N1 and C11—O2 bond lengths of (I) are almost equal [1.356 (2) and 1.351 (2) Å, respectively], due to strong conjugation effects (Fig. 1). This causes the central carbamate moiety (N1/O1/O2/C11), together with the adjacent α-carbon atoms (C12/C21/C31), to be planar within 0.110 (1) Å. Compound (I) contains three outward aryl substituents. One of them, the fluorinated ring C23–C28, is linked to the carbamate fragment by a C6F5N—H···O hydrogen bond [2.07 (2) Å]. To the best of our knowledge, similar hydrogen bonding has been observed only once before, in the structure of 2-(pentafluorophenylamino)-pent-2-en-4-one, C6F5NHC(Me)═CHCOMe (Gordon et al., 2002). The rotation of the C23–C28 aryl ring around the N2—C23 bond seems to be restricted, due to noticeable conjugation with the neighbouring amine atom N2. This is confirmed by the C24—C23—N2—H2 torsion angle [-5.6 (17)°] and by sufficient shortening of N2—C23 bond distance [1.375 (2) Å]. The other two aryl groups, C13–C18 and C33–C38, are nearly parallel [dihedral angle 11.56 (6)°] and are bonded by the well known Ar···ArF face-to-face interaction (Dunitz, 2004), with a centroid-to-centroid separation of 3.749 Å and a displacement angle (Janiak, 2000) of 15.0°. Thus, the conformation of the molecule of (I) is completely predetermined by the aforementioned intramolecular interactions.
In the crystal structure of (I), translationally related molecules are linked together by C6F5N—H···F—C hydrogen bonds [2.17 (2) Å], forming chains parallel to the a axis (Fig. 2). The low propensity of organic fluorine to participate in hydrogen bonding has been the subject of several reports (Howard et al., 1996; Dunitz & Taylor, 1997). However, in this case, this unusual hydrogen bonding may result from the high acidity of atom H3, caused by the neighbouring highly electron-withdrawing C6F5 group. Adjacent symmetry-related chains are combined in double zipper-like ribbons by parallel ArF···ArF offset π-stacking interactions (Fig. 3). The interplanar ArF···ArF distance is 3.8191 (4) Å, the centroid-to-centroid separation is 3.902 Å and the displacement angle is 25.0°. Finally, these chains are linked by intermolecular Ar···ArF interactions, forming a complex three-dimensional network.
In conclusion, the molecular geometry and crystal packing of (I) are determined by the different types of secondary bonding formed by the C6F5NH– groups.