organic papers
o1896
Helen L. Aberdeenet al. C20H12F12N2 DOI: 10.1107/S160053680302508X Acta Cryst.(2003). E59, o1896±o1897Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
[3,5-Bis(trifluoromethyl)phenyl]{(
E
)-2-[(
E
)-3,5-bis(trifluoromethyl)phenylimino]-1-methylpropylidene}amine
Helen L. Aberdeen,aRobert E.
Allanband Jonathan D. Cranea*
aDepartment of Chemistry, University of Hull,
Cottingham Road, Kingston-upon-Hull HU6 7RX, England, andbBP Chemicals Ltd, Hull
Research and Technology Centre, Saltend, Kingston-upon-Hull HU12 8DS, England
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 150 K
Mean(C±C) = 0.002 AÊ Disorder in main residue
Rfactor = 0.059
wRfactor = 0.192
Data-to-parameter ratio = 21.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
At 150 K, the two imine groups of the title compound, C20H12F12N2, are mutually trans. The molecule has
crystal-lographic inversion symmetry.
Comment
The title compound, (I), is of interest as a bidentate ligand for catalytically active platinum(II) compounds (Johanssonet al., 1999), in which the imine groups are mutuallycis.
The molecule of (I) is centrosymmetric in the crystal structure. Thus the central diimine group istransand planar. The dihedral angle between the least-squares planes of this group and the benzene ring is 77.25 (12). Atom C3 lies 0.0291 (16) AÊ out of the least-squares plane of the diimine group and N1 lies 0.1344 (13) AÊ out of the plane of the benzene ring. Thus, there is a slight pyramidalization ofipso-C atom C3, which lies 0.0471 (14) AÊ above the plane of its bonded neighbouring atoms (N1, C4 and C8).
Experimental
The title compound was prepared by the method of Johanssonet al.
(1999). Suitable crystals were grown from chloroform by slow evaporation.
Received 17 October 2003 Accepted 30 October 2003 Online 8 November 2003
Figure 1
Crystal data
C20H12F12N2 Mr= 508.32
Triclinic,P1
a= 8.1406 (12) AÊ
b= 8.2225 (12) AÊ
c= 8.7087 (13) AÊ
= 82.044 (12)
= 71.590 (11)
= 68.264 (11) V= 513.62 (13) AÊ3
Z= 1
Dx= 1.643 Mg mÿ3
MoKradiation Cell parameters from 8717
re¯ections
= 2.5±32.3
= 0.17 mmÿ1 T= 150 (2) K Lath, colourless 0.600.300.10 mm
Data collection
Stoe IPDS-II diffractometer
!scans
Absorption correction: none 10945 measured re¯ections 3638 independent re¯ections 2477 re¯ections withI> 2(I)
Rint= 0.036
max= 32.3 h=ÿ12!12
k=ÿ12!12
l=ÿ13!13
Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.059 wR(F2) = 0.192 S= 1.15 3638 re¯ections 166 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.1038P)2
+ 0.0549P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.62 e AÊÿ3 min=ÿ0.45 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.065 (17)
Table 1
Selected geometric parameters (AÊ,).
N1ÐC1 1.2731 (19)
N1ÐC3 1.4079 (18) C1ÐC2C1ÐC1i 1.497 (2)1.505 (3)
C1ÐN1ÐC3 121.92 (13) N1ÐC1ÐC2 126.47 (13) N1ÐC1ÐC1i 115.74 (16)
C2ÐC1ÐC1i 117.77 (15)
C8ÐC3ÐN1 119.56 (13) C4ÐC3ÐN1 120.81 (13) C3ÐN1ÐC1ÐC2 2.5 (2)
C3ÐN1ÐC1ÐC1i ÿ179.06 (14) C1ÐN1ÐC3ÐC8C1ÐN1ÐC3ÐC4 ÿ107.89 (17)78.82 (19)
Symmetry code: (i)ÿx;2ÿy;1ÿz.
All H atoms were initially located in a difference Fourier map. The methyl H atoms were constrained to an ideal geometry, with CÐH distances of 0.98 AÊ, but each group was allowed to rotate freely about its XÐC bond. All other H atoms were placed in geometrically idealized positions, with CÐH distances of 0.95 AÊ.Uiso(H) values
were set at 1.2Ueq(C) for all H atoms. The C10 CF3 group was
disordered over two sites with relative occupancies of 0.887 (2):0.113 (2).
Data collection: X-AREA (Stoe & Cie, 2001); cell re®nement:
X-AREA; data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: X-STEP32 (Stoe & Cie, 2001) and
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
WinGX(Farrugia, 1999) andSHELXL97 (Sheldrick, 1997); molec-ular graphics:ORTEP-3for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX.
We acknowledge the University of Hull and BP Chemicals for support.
References
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.
Johansson, L., Ryan, O. B. & Tilset, M. (1999).J. Am. Chem. Soc.121, 1974± 1975.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Stoe & Cie (2001).X-AREA, X-STEP32 andX-RED. Stoe & Cie GmbH, Darmstadt, Germany.
Figure 2
supporting information
sup-1 Acta Cryst. (2003). E59, o1896–o1897
supporting information
Acta Cryst. (2003). E59, o1896–o1897 [https://doi.org/10.1107/S160053680302508X]
[3,5-Bis(trifluoromethyl)phenyl]{(
E
)-2-[(
E
)-3,5-bis(trifluoromethyl)phenyl-imino]-1-methylpropylidene}amine
Helen L. Aberdeen, Robert E. Allan and Jonathan D. Crane
[3,5-Bis(trifluoromethyl)phenyl]{(E)-2-[(E)-3,5- bis(trifluoromethyl)phenylimino]-1-methylpropylidene}amine
Crystal data
C20H12F12N2 Mr = 508.32 Triclinic, P1 Hall symbol: -P 1
a = 8.1406 (12) Å
b = 8.2225 (12) Å
c = 8.7087 (13) Å
α = 82.044 (12)°
β = 71.590 (11)°
γ = 68.264 (11)°
V = 513.62 (13) Å3
Z = 1
F(000) = 254
Dx = 1.643 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8717 reflections
θ = 2.5–32.3°
µ = 0.17 mm−1 T = 150 K Lath, colourless 0.60 × 0.30 × 0.10 mm
Data collection
Stoe IPDS-II diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
10945 measured reflections 3638 independent reflections
2477 reflections with I > 2σ(I)
Rint = 0.036
θmax = 32.3°, θmin = 2.5°
h = −12→12
k = −12→12
l = −13→13
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.059 wR(F2) = 0.192 S = 1.15 3638 reflections 166 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.1038P)2 + 0.0549P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.62 e Å−3
Δρmin = −0.45 e Å−3
Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Special details
Experimental. The crystal was mounted under the perfluoro-polyether PFO-XR75 (Lancaster Synthesis). A total of 290 frames (1 minute exposure) were collected (phi/omega: 10/175–180, 55/25–165, 160/25–170, delta-omega = 1 °.)
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.
Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II— A),807).
Plane 1
Atom d s d/s (d/s)**2 C1 * 0.0000 0.0016 0.000 0.000 N1 * 0.0000 0.0015 0.000 0.000 C2 * 0.0000 0.0020 0.000 0.000 C3 0.0527 0.0016 32.357 1047.007 ============ Sum((d/s)**2) for starred atoms 0.000
Plane 2
Atom d s d/s (d/s)**2 C3 * 0.0011 0.0014 0.796 0.634 C4 * 0.0036 0.0015 2.397 5.748 C5 * -0.0033 0.0015 - 2.174 4.725 C6 * -0.0021 0.0014 - 1.427 2.037 C7 * 0.0073 0.0015 4.852 23.542 C8 * -0.0067 0.0015 - 4.460 19.887 N1 - 0.1344 0.0013 - 105.129 11052.209 C9 - 0.0046 0.0020 - 2.304 5.308 C10 - 0.0108 0.0018 - 5.874 34.507
============ Sum((d/s)**2) for starred atoms 56.573
Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 3
Atom d s d/s (d/s)**2 N1 * 0.0000 0.0013 0.000 0.000 C4 * 0.0000 0.0015 0.000 0.000 C8 * 0.0000 0.0015 0.000 0.000 C3 0.0471 0.0014 32.873 1080.603 ============ Sum((d/s)**2) for starred atoms 0.000
Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 77.25 (0.12) 102.75 (0.12)
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)
x y z Uiso*/Ueq Occ. (<1)
F1 0.8750 (2) 0.7737 (2) 0.0966 (2) 0.0691 (4)
F2 0.8530 (2) 0.7511 (3) 0.3476 (2) 0.0840 (6)
F3 1.00766 (17) 0.5284 (2) 0.1932 (2) 0.0699 (5)
F4 0.4303 (3) 0.2896 (2) 0.0917 (3) 0.0693 (6) 0.887 (2)
F5 0.4953 (5) 0.1598 (2) 0.2999 (2) 0.0918 (9) 0.887 (2)
F6 0.7091 (3) 0.1735 (3) 0.0907 (4) 0.0996 (10) 0.887 (2)
F7 0.641 (3) 0.1373 (17) 0.228 (3) 0.0693 (6) 0.113 (2)
F8 0.614 (5) 0.249 (2) 0.0361 (17) 0.0918 (9) 0.113 (2)
F9 0.377 (2) 0.244 (3) 0.239 (3) 0.0996 (10) 0.113 (2)
N1 0.18628 (17) 0.80521 (17) 0.48625 (15) 0.0303 (3)
C1 0.08685 (19) 0.95044 (18) 0.43766 (17) 0.0267 (3)
C2 0.1239 (2) 1.0281 (2) 0.2698 (2) 0.0391 (4)
H2C 0.2426 0.9531 0.2021 0.047*
H2B 0.1282 1.1450 0.2734 0.047*
H2A 0.0253 1.0370 0.2239 0.047*
C3 0.35389 (19) 0.69984 (18) 0.38339 (17) 0.0272 (3)
C4 0.5147 (2) 0.73974 (18) 0.34964 (18) 0.0296 (3)
H4 0.5094 0.8455 0.3866 0.036*
C5 0.6824 (2) 0.6240 (2) 0.26176 (18) 0.0299 (3)
C6 0.6941 (2) 0.46924 (19) 0.20517 (17) 0.0298 (3)
supporting information
sup-3 Acta Cryst. (2003). E59, o1896–o1897
C7 0.5334 (2) 0.43248 (19) 0.23842 (18) 0.0294 (3)
C8 0.3644 (2) 0.54413 (19) 0.32800 (18) 0.0295 (3)
H8 0.2566 0.5146 0.3514 0.035*
C9 0.8534 (2) 0.6686 (3) 0.2271 (2) 0.0417 (4)
C10 0.5418 (3) 0.2648 (2) 0.1809 (2) 0.0386 (4)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
F1 0.0545 (8) 0.0723 (9) 0.0774 (10) −0.0373 (7) −0.0046 (7) 0.0178 (7)
F2 0.0597 (9) 0.1383 (16) 0.0763 (10) −0.0627 (10) 0.0009 (7) −0.0421 (10)
F3 0.0281 (6) 0.0583 (8) 0.1160 (13) −0.0096 (5) −0.0165 (7) −0.0042 (8)
F4 0.1058 (14) 0.0449 (8) 0.0876 (12) −0.0263 (8) −0.0693 (11) 0.0009 (7)
F5 0.205 (3) 0.0450 (9) 0.0498 (9) −0.0684 (14) −0.0447 (13) 0.0113 (7)
F6 0.0545 (11) 0.0784 (13) 0.155 (3) −0.0102 (9) 0.0036 (12) −0.0842 (16)
F7 0.1058 (14) 0.0449 (8) 0.0876 (12) −0.0263 (8) −0.0693 (11) 0.0009 (7)
F8 0.205 (3) 0.0450 (9) 0.0498 (9) −0.0684 (14) −0.0447 (13) 0.0113 (7)
F9 0.0545 (11) 0.0784 (13) 0.155 (3) −0.0102 (9) 0.0036 (12) −0.0842 (16)
N1 0.0252 (6) 0.0275 (6) 0.0303 (6) −0.0022 (4) −0.0053 (4) −0.0024 (4)
C1 0.0229 (6) 0.0248 (6) 0.0299 (6) −0.0055 (5) −0.0066 (5) −0.0032 (5)
C2 0.0319 (8) 0.0354 (8) 0.0321 (7) 0.0013 (6) −0.0022 (6) 0.0021 (6)
C3 0.0252 (6) 0.0241 (6) 0.0266 (6) −0.0031 (5) −0.0067 (5) −0.0001 (5)
C4 0.0293 (7) 0.0246 (6) 0.0319 (7) −0.0064 (5) −0.0079 (5) −0.0017 (5)
C5 0.0253 (6) 0.0306 (6) 0.0304 (6) −0.0078 (5) −0.0066 (5) 0.0016 (5)
C6 0.0249 (6) 0.0282 (6) 0.0286 (6) −0.0025 (5) −0.0046 (5) −0.0026 (5)
C7 0.0302 (7) 0.0257 (6) 0.0292 (6) −0.0050 (5) −0.0092 (5) −0.0024 (5)
C8 0.0264 (6) 0.0278 (6) 0.0322 (7) −0.0065 (5) −0.0085 (5) −0.0019 (5)
C9 0.0290 (8) 0.0429 (9) 0.0498 (10) −0.0129 (7) −0.0048 (7) −0.0043 (7)
C10 0.0427 (9) 0.0310 (7) 0.0409 (8) −0.0074 (6) −0.0142 (7) −0.0078 (6)
Geometric parameters (Å, º)
F1—C9 1.336 (2) C2—H2B 0.9800
F2—C9 1.324 (3) C2—H2A 0.9800
F3—C9 1.335 (2) C3—C8 1.394 (2)
F4—C10 1.316 (2) C3—C4 1.399 (2)
F5—C10 1.307 (3) C4—C5 1.391 (2)
F6—C10 1.329 (2) C4—H4 0.9500
F7—C10 1.176 (13) C5—C6 1.387 (2)
F8—C10 1.214 (16) C5—C9 1.498 (2)
F9—C10 1.345 (16) C6—C7 1.384 (2)
N1—C1 1.2731 (19) C6—H6 0.9500
N1—C3 1.4079 (18) C7—C8 1.389 (2)
C1—C2 1.497 (2) C7—C10 1.502 (2)
C1—C1i 1.505 (3) C8—H8 0.9500
C2—H2C 0.9800
N1—C1—C2 126.47 (13) F2—C9—F1 105.95 (18)
N1—C1—C1i 115.74 (16) F3—C9—F1 104.06 (16)
C2—C1—C1i 117.77 (15) F2—C9—C5 112.63 (15)
C1—C2—H2C 109.5 F3—C9—C5 112.76 (15)
C1—C2—H2B 109.5 F1—C9—C5 112.42 (16)
H2C—C2—H2B 109.5 F7—C10—F8 99.7 (15)
C1—C2—H2A 109.5 F7—C10—F5 53.0 (12)
H2C—C2—H2A 109.5 F8—C10—F5 134.4 (6)
H2B—C2—H2A 109.5 F7—C10—F4 132.4 (6)
C8—C3—C4 119.29 (13) F8—C10—F4 63.8 (15)
C8—C3—N1 119.56 (13) F5—C10—F4 105.4 (2)
C4—C3—N1 120.81 (13) F7—C10—F6 56.5 (12)
C5—C4—C3 119.74 (13) F8—C10—F6 46.2 (13)
C5—C4—H4 120.1 F5—C10—F6 106.3 (2)
C3—C4—H4 120.1 F4—C10—F6 105.8 (2)
C6—C5—C4 121.40 (13) F7—C10—F9 103.2 (15)
C6—C5—C9 119.59 (14) F8—C10—F9 116.5 (16)
C4—C5—C9 119.01 (14) F5—C10—F9 53.4 (12)
C7—C6—C5 118.12 (13) F4—C10—F9 57.0 (12)
C7—C6—H6 120.9 F6—C10—F9 136.7 (5)
C5—C6—H6 120.9 F7—C10—C7 114.4 (6)
C6—C7—C8 121.81 (13) F8—C10—C7 112.0 (6)
C6—C7—C10 119.42 (13) F5—C10—C7 112.76 (15)
C8—C7—C10 118.74 (14) F4—C10—C7 113.08 (15)
C7—C8—C3 119.62 (14) F6—C10—C7 112.89 (16)
C7—C8—H8 120.2 F9—C10—C7 110.4 (5)
C3—C8—H8 120.2
C3—N1—C1—C2 2.5 (2) C4—C5—C9—F2 35.6 (2)
C3—N1—C1—C1i −179.06 (14) C6—C5—C9—F3 −21.7 (2)
C1—N1—C3—C8 −107.89 (17) C4—C5—C9—F3 158.67 (16)
C1—N1—C3—C4 78.82 (19) C6—C5—C9—F1 95.61 (19)
C8—C3—C4—C5 −0.1 (2) C4—C5—C9—F1 −84.1 (2)
N1—C3—C4—C5 173.24 (13) C6—C7—C10—F7 57.6 (14)
C3—C4—C5—C6 0.5 (2) C8—C7—C10—F7 −120.6 (14)
C3—C4—C5—C9 −179.83 (14) C6—C7—C10—F8 −54.9 (16)
C4—C5—C6—C7 0.0 (2) C8—C7—C10—F8 127.0 (16)
C9—C5—C6—C7 −179.61 (15) C6—C7—C10—F5 115.8 (2)
C5—C6—C7—C8 −1.1 (2) C8—C7—C10—F5 −62.4 (3)
C5—C6—C7—C10 −179.14 (14) C6—C7—C10—F4 −124.7 (2)
C6—C7—C8—C3 1.5 (2) C8—C7—C10—F4 57.2 (2)
C10—C7—C8—C3 179.60 (14) C6—C7—C10—F6 −4.7 (3)
C4—C3—C8—C7 −0.9 (2) C8—C7—C10—F6 177.2 (2)
N1—C3—C8—C7 −174.31 (13) C6—C7—C10—F9 173.5 (14)
C6—C5—C9—F2 −144.78 (18) C8—C7—C10—F9 −4.6 (14)
