Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009163/cf6079sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009163/cf6079Isup2.hkl |
CCDC reference: 170790
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å Some non-H atoms missing
- R factor = 0.060
- wR factor = 0.141
- Data-to-parameter ratio = 18.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
PLAT_601 Alert A Structure Contains Solvent Accessible VOIDS of 494.00 A 3
Author response: Structure contains highly disordered toluene solvent molecules. These were treated by the SQUEEZE procedure of PLATON. |
General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C32.5 H46 N2 Atom count from the _atom_site data: C29 H42 N2 CELLZ_01 From the CIF: _cell_formula_units_Z 8 From the CIF: _chemical_formula_sum C32.5 H46 N2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 260.00 232.00 28.00 H 368.00 336.00 32.00 N 16.00 16.00 0.00 Difference between formula and atom_site contents detected. ALERT: Large difference may be due to a symmetry error - see SYMMG tests CHEMW_03 From the CIF: _cell_formula_units_Z 8 From the CIF: _chemical_formula_weight 464.71 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 29.00 348.32 H 1.01 42.00 42.34 N 14.01 2.00 28.01 Calculated formula weight 418.67 ALERT: The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.90 <> 1.10
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
Compound (I) was synthesized by acid-catalysed condensation of 2,4-pentanedione and 2,6-diisopropylaniline in ethanol (Parks & Holm, 1968). Crystals were obtained from a saturated solution in toluene at 243 K.
The toluene solvent molecule, located over a centre of inversion, was too highly disordered for individual atoms to be resolved; this was treated with the SQUEEZE procedure of PLATON (Spek, 1990). H atoms attached to C atoms were placed in calculated positions and subsequently allowed to ride on their parent atoms with Uiso(H) = 1.2Ueq(C). Methyl groups were treated as rotating rigid groups with Uiso(H) = 1.5Ueq(C). H atoms attached to N atoms were located in a difference synthesis and were freely refined, each with 50% occupancy.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A view of (I) with the atom-numbering scheme. Displacement ellipsoids are at the 30% probability level. |
C29H42N2·0.5C7H8 | F(000) = 2040 |
Mr = 464.71 | Dx = 1.020 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 26.655 (5) Å | Cell parameters from 10829 reflections |
b = 18.004 (3) Å | θ = 2.2–26.4° |
c = 12.623 (2) Å | µ = 0.06 mm−1 |
β = 91.972 (3)° | T = 150 K |
V = 6054.0 (19) Å3 | Block, colourless |
Z = 8 | 0.19 × 0.16 × 0.07 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5322 independent reflections |
Radiation source: fine-focus sealed tube | 4677 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −31→31 |
Tmin = 0.989, Tmax = 0.996 | k = −21→21 |
21824 measured reflections | l = −14→14 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0507P)2 + 4.1159P] where P = (Fo2 + 2Fc2)/3 |
5322 reflections | (Δ/σ)max < 0.001 |
296 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C29H42N2·0.5C7H8 | V = 6054.0 (19) Å3 |
Mr = 464.71 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.655 (5) Å | µ = 0.06 mm−1 |
b = 18.004 (3) Å | T = 150 K |
c = 12.623 (2) Å | 0.19 × 0.16 × 0.07 mm |
β = 91.972 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 5322 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 4677 reflections with I > 2σ(I) |
Tmin = 0.989, Tmax = 0.996 | Rint = 0.025 |
21824 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.141 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.19 e Å−3 |
5322 reflections | Δρmin = −0.17 e Å−3 |
296 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 | Occ. (<1) | |
C1 | 0.45282 (6) | 0.19078 (11) | 0.45141 (14) | 0.0431 (4) | |
H1A | 0.4479 | 0.1407 | 0.4797 | 0.065* | |
H1B | 0.4432 | 0.2276 | 0.5042 | 0.065* | |
H1C | 0.4882 | 0.1976 | 0.4351 | 0.065* | |
C2 | 0.42081 (6) | 0.20054 (8) | 0.35211 (12) | 0.0294 (4) | |
C3 | 0.36959 (6) | 0.21714 (9) | 0.35133 (12) | 0.0315 (4) | |
H3 | 0.3554 | 0.2320 | 0.2846 | 0.038* | |
C4 | 0.33599 (6) | 0.21517 (9) | 0.43424 (12) | 0.0301 (4) | |
C5 | 0.34609 (7) | 0.17537 (11) | 0.53763 (14) | 0.0470 (5) | |
H5A | 0.3672 | 0.2066 | 0.5845 | 0.070* | |
H5B | 0.3634 | 0.1284 | 0.5243 | 0.070* | |
H5C | 0.3142 | 0.1652 | 0.5713 | 0.070* | |
N1 | 0.44584 (5) | 0.19537 (8) | 0.26339 (11) | 0.0333 (3) | |
H1N | 0.4794 (12) | 0.1932 (18) | 0.259 (3) | 0.040* | 0.50 |
C6 | 0.42228 (6) | 0.19119 (10) | 0.16055 (13) | 0.0370 (4) | |
C7 | 0.41329 (7) | 0.12038 (12) | 0.11755 (15) | 0.0488 (5) | |
C8 | 0.39627 (8) | 0.11616 (15) | 0.01214 (18) | 0.0647 (7) | |
H8 | 0.3897 | 0.0689 | −0.0187 | 0.078* | |
C9 | 0.38884 (8) | 0.17889 (17) | −0.04818 (17) | 0.0686 (7) | |
H9 | 0.3781 | 0.1747 | −0.1205 | 0.082* | |
C10 | 0.39694 (7) | 0.24739 (15) | −0.00415 (16) | 0.0596 (6) | |
H10 | 0.3911 | 0.2904 | −0.0464 | 0.071* | |
C11 | 0.41347 (6) | 0.25570 (11) | 0.10105 (14) | 0.0430 (4) | |
C12 | 0.42287 (7) | 0.33206 (11) | 0.14694 (16) | 0.0492 (5) | |
H12 | 0.4262 | 0.3265 | 0.2257 | 0.059* | |
C13 | 0.37920 (9) | 0.38491 (14) | 0.1235 (2) | 0.0780 (7) | |
H13A | 0.3852 | 0.4319 | 0.1611 | 0.117* | |
H13B | 0.3480 | 0.3625 | 0.1473 | 0.117* | |
H13C | 0.3763 | 0.3944 | 0.0471 | 0.117* | |
C14 | 0.47210 (9) | 0.36467 (14) | 0.1094 (2) | 0.0723 (7) | |
H14A | 0.4777 | 0.4134 | 0.1424 | 0.108* | |
H14B | 0.4703 | 0.3702 | 0.0321 | 0.108* | |
H14C | 0.4999 | 0.3314 | 0.1297 | 0.108* | |
C15 | 0.42146 (9) | 0.05100 (12) | 0.1828 (2) | 0.0661 (6) | |
H15 | 0.4404 | 0.0655 | 0.2493 | 0.079* | |
C16 | 0.45263 (12) | −0.00658 (16) | 0.1264 (3) | 0.0980 (10) | |
H16A | 0.4580 | −0.0498 | 0.1727 | 0.147* | |
H16B | 0.4851 | 0.0150 | 0.1093 | 0.147* | |
H16C | 0.4348 | −0.0221 | 0.0608 | 0.147* | |
C17 | 0.37154 (12) | 0.01708 (17) | 0.2146 (3) | 0.1102 (11) | |
H17A | 0.3780 | −0.0285 | 0.2552 | 0.165* | |
H17B | 0.3511 | 0.0054 | 0.1508 | 0.165* | |
H17C | 0.3536 | 0.0526 | 0.2583 | 0.165* | |
N2 | 0.29097 (5) | 0.24651 (8) | 0.42564 (10) | 0.0319 (3) | |
H2N | 0.2670 (13) | 0.243 (2) | 0.473 (3) | 0.038* | 0.50 |
C18 | 0.27649 (6) | 0.29483 (9) | 0.34030 (12) | 0.0323 (4) | |
C19 | 0.25237 (6) | 0.26592 (10) | 0.24923 (13) | 0.0376 (4) | |
C20 | 0.23346 (6) | 0.31551 (12) | 0.17346 (14) | 0.0461 (5) | |
H20 | 0.2169 | 0.2969 | 0.1111 | 0.055* | |
C21 | 0.23820 (7) | 0.39072 (12) | 0.18709 (15) | 0.0508 (5) | |
H21 | 0.2244 | 0.4238 | 0.1352 | 0.061* | |
C22 | 0.26304 (7) | 0.41825 (11) | 0.27607 (16) | 0.0487 (5) | |
H22 | 0.2666 | 0.4704 | 0.2844 | 0.058* | |
C23 | 0.28308 (6) | 0.37118 (10) | 0.35411 (14) | 0.0400 (4) | |
C24 | 0.31120 (8) | 0.40243 (11) | 0.45052 (17) | 0.0558 (5) | |
H24 | 0.3187 | 0.3599 | 0.4995 | 0.067* | |
C25 | 0.36144 (11) | 0.4357 (2) | 0.4207 (3) | 0.1203 (14) | |
H25A | 0.3803 | 0.4506 | 0.4852 | 0.180* | |
H25B | 0.3555 | 0.4792 | 0.3754 | 0.180* | |
H25C | 0.3807 | 0.3986 | 0.3824 | 0.180* | |
C26 | 0.28106 (10) | 0.45799 (14) | 0.51090 (19) | 0.0734 (7) | |
H26A | 0.2999 | 0.4728 | 0.5755 | 0.110* | |
H26B | 0.2491 | 0.4355 | 0.5300 | 0.110* | |
H26C | 0.2745 | 0.5018 | 0.4665 | 0.110* | |
C27 | 0.24576 (7) | 0.18283 (11) | 0.23286 (14) | 0.0454 (5) | |
H27 | 0.2665 | 0.1569 | 0.2891 | 0.054* | |
C28 | 0.26451 (10) | 0.15802 (14) | 0.12547 (19) | 0.0735 (7) | |
H28A | 0.2422 | 0.1775 | 0.0688 | 0.110* | |
H28B | 0.2648 | 0.1036 | 0.1222 | 0.110* | |
H28C | 0.2986 | 0.1770 | 0.1165 | 0.110* | |
C29 | 0.19131 (8) | 0.16009 (13) | 0.24554 (17) | 0.0601 (6) | |
H29A | 0.1883 | 0.1060 | 0.2388 | 0.090* | |
H29B | 0.1702 | 0.1841 | 0.1904 | 0.090* | |
H29C | 0.1804 | 0.1755 | 0.3155 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0313 (9) | 0.0593 (12) | 0.0388 (10) | 0.0017 (8) | 0.0046 (7) | 0.0116 (8) |
C2 | 0.0290 (8) | 0.0274 (8) | 0.0323 (9) | −0.0009 (6) | 0.0066 (6) | 0.0018 (6) |
C3 | 0.0308 (8) | 0.0363 (9) | 0.0275 (8) | 0.0015 (7) | 0.0024 (6) | 0.0034 (7) |
C4 | 0.0282 (8) | 0.0320 (8) | 0.0304 (8) | −0.0002 (6) | 0.0038 (6) | −0.0001 (7) |
C5 | 0.0359 (9) | 0.0662 (13) | 0.0394 (10) | 0.0058 (9) | 0.0097 (8) | 0.0168 (9) |
N1 | 0.0239 (7) | 0.0404 (8) | 0.0360 (8) | 0.0019 (6) | 0.0055 (6) | −0.0031 (6) |
C6 | 0.0217 (8) | 0.0538 (11) | 0.0358 (9) | −0.0009 (7) | 0.0078 (6) | −0.0063 (8) |
C7 | 0.0353 (9) | 0.0620 (13) | 0.0497 (12) | −0.0061 (9) | 0.0087 (8) | −0.0183 (10) |
C8 | 0.0459 (12) | 0.0916 (18) | 0.0571 (14) | −0.0110 (11) | 0.0085 (10) | −0.0325 (13) |
C9 | 0.0418 (11) | 0.127 (2) | 0.0368 (12) | 0.0003 (13) | 0.0000 (9) | −0.0178 (14) |
C10 | 0.0416 (11) | 0.0994 (18) | 0.0379 (11) | 0.0080 (11) | 0.0044 (8) | 0.0063 (11) |
C11 | 0.0275 (9) | 0.0650 (13) | 0.0368 (10) | 0.0045 (8) | 0.0068 (7) | 0.0022 (9) |
C12 | 0.0494 (11) | 0.0523 (12) | 0.0462 (11) | 0.0082 (9) | 0.0084 (9) | 0.0124 (9) |
C13 | 0.0699 (15) | 0.0734 (17) | 0.0914 (19) | 0.0241 (13) | 0.0118 (14) | 0.0160 (14) |
C14 | 0.0615 (14) | 0.0651 (15) | 0.0912 (18) | −0.0046 (12) | 0.0146 (13) | 0.0000 (13) |
C15 | 0.0779 (16) | 0.0460 (12) | 0.0748 (15) | −0.0053 (11) | 0.0088 (12) | −0.0183 (11) |
C16 | 0.105 (2) | 0.0704 (18) | 0.119 (2) | 0.0113 (16) | 0.0185 (19) | −0.0276 (17) |
C17 | 0.112 (2) | 0.0726 (19) | 0.149 (3) | −0.0101 (17) | 0.052 (2) | 0.0129 (19) |
N2 | 0.0293 (7) | 0.0395 (8) | 0.0274 (7) | 0.0017 (6) | 0.0088 (5) | 0.0014 (6) |
C18 | 0.0268 (8) | 0.0430 (10) | 0.0278 (8) | 0.0027 (7) | 0.0094 (6) | 0.0025 (7) |
C19 | 0.0283 (8) | 0.0517 (11) | 0.0331 (9) | 0.0006 (7) | 0.0075 (7) | 0.0021 (8) |
C20 | 0.0349 (9) | 0.0684 (14) | 0.0350 (10) | 0.0016 (9) | 0.0006 (7) | 0.0059 (9) |
C21 | 0.0421 (10) | 0.0652 (14) | 0.0452 (11) | 0.0100 (9) | 0.0049 (9) | 0.0202 (10) |
C22 | 0.0474 (11) | 0.0426 (11) | 0.0566 (12) | 0.0070 (9) | 0.0087 (9) | 0.0094 (9) |
C23 | 0.0369 (9) | 0.0425 (10) | 0.0411 (10) | 0.0042 (8) | 0.0079 (7) | 0.0011 (8) |
C24 | 0.0741 (14) | 0.0396 (11) | 0.0529 (12) | 0.0029 (10) | −0.0070 (10) | −0.0074 (9) |
C25 | 0.0680 (18) | 0.169 (3) | 0.123 (3) | −0.0252 (19) | 0.0005 (17) | −0.086 (3) |
C26 | 0.0954 (18) | 0.0671 (15) | 0.0580 (14) | 0.0098 (13) | 0.0073 (13) | −0.0158 (12) |
C27 | 0.0462 (10) | 0.0546 (12) | 0.0350 (10) | −0.0058 (9) | −0.0028 (8) | −0.0057 (8) |
C28 | 0.0825 (17) | 0.0737 (16) | 0.0654 (15) | −0.0171 (13) | 0.0195 (13) | −0.0257 (12) |
C29 | 0.0561 (12) | 0.0678 (14) | 0.0562 (13) | −0.0150 (11) | −0.0001 (10) | 0.0076 (11) |
C1—C2 | 1.502 (2) | C16—H16A | 0.980 |
C1—H1A | 0.980 | C16—H16B | 0.980 |
C1—H1B | 0.980 | C16—H16C | 0.980 |
C1—H1C | 0.980 | C17—H17A | 0.980 |
C2—N1 | 1.326 (2) | C17—H17B | 0.980 |
C2—C3 | 1.398 (2) | C17—H17C | 0.980 |
C3—C4 | 1.401 (2) | N2—C18 | 1.428 (2) |
C3—H3 | 0.950 | N2—H2N | 0.89 (3) |
C4—N2 | 1.327 (2) | C18—C23 | 1.396 (2) |
C4—C5 | 1.505 (2) | C18—C19 | 1.398 (2) |
C5—H5A | 0.980 | C19—C20 | 1.390 (3) |
C5—H5B | 0.980 | C19—C27 | 1.520 (3) |
C5—H5C | 0.980 | C20—C21 | 1.370 (3) |
N1—C6 | 1.424 (2) | C20—H20 | 0.950 |
N1—H1N | 0.90 (3) | C21—C22 | 1.377 (3) |
C6—C11 | 1.399 (3) | C21—H21 | 0.950 |
C6—C7 | 1.403 (3) | C22—C23 | 1.392 (3) |
C7—C8 | 1.393 (3) | C22—H22 | 0.950 |
C7—C15 | 1.508 (3) | C23—C24 | 1.515 (3) |
C8—C9 | 1.373 (4) | C24—C26 | 1.506 (3) |
C8—H8 | 0.950 | C24—C25 | 1.526 (4) |
C9—C10 | 1.367 (3) | C24—H24 | 1.0000 |
C9—H9 | 0.950 | C25—H25A | 0.980 |
C10—C11 | 1.393 (3) | C25—H25B | 0.980 |
C10—H10 | 0.950 | C25—H25C | 0.980 |
C11—C12 | 1.509 (3) | C26—H26A | 0.980 |
C12—C13 | 1.524 (3) | C26—H26B | 0.980 |
C12—C14 | 1.528 (3) | C26—H26C | 0.980 |
C12—H12 | 1.000 | C27—C29 | 1.522 (3) |
C13—H13A | 0.980 | C27—C28 | 1.528 (3) |
C13—H13B | 0.980 | C27—H27 | 1.000 |
C13—H13C | 0.980 | C28—H28A | 0.980 |
C14—H14A | 0.980 | C28—H28B | 0.980 |
C14—H14B | 0.980 | C28—H28C | 0.980 |
C14—H14C | 0.980 | C29—H29A | 0.980 |
C15—C16 | 1.520 (3) | C29—H29B | 0.980 |
C15—C17 | 1.530 (4) | C29—H29C | 0.980 |
C15—H15 | 1.000 | ||
C2—C1—H1A | 109.5 | H16A—C16—H16B | 109.5 |
C2—C1—H1B | 109.5 | C15—C16—H16C | 109.5 |
H1A—C1—H1B | 109.5 | H16A—C16—H16C | 109.5 |
C2—C1—H1C | 109.5 | H16B—C16—H16C | 109.5 |
H1A—C1—H1C | 109.5 | C15—C17—H17A | 109.5 |
H1B—C1—H1C | 109.5 | C15—C17—H17B | 109.5 |
N1—C2—C3 | 121.92 (15) | H17A—C17—H17B | 109.5 |
N1—C2—C1 | 114.12 (14) | C15—C17—H17C | 109.5 |
C3—C2—C1 | 123.89 (14) | H17A—C17—H17C | 109.5 |
C2—C3—C4 | 129.70 (15) | H17B—C17—H17C | 109.5 |
C2—C3—H3 | 115.1 | C4—N2—C18 | 122.77 (13) |
C4—C3—H3 | 115.1 | C4—N2—H2N | 126 (2) |
N2—C4—C3 | 121.84 (14) | C18—N2—H2N | 112 (2) |
N2—C4—C5 | 114.06 (13) | C23—C18—C19 | 121.44 (15) |
C3—C4—C5 | 124.05 (14) | C23—C18—N2 | 118.45 (15) |
C4—C5—H5A | 109.5 | C19—C18—N2 | 119.89 (15) |
C4—C5—H5B | 109.5 | C20—C19—C18 | 118.17 (17) |
H5A—C5—H5B | 109.5 | C20—C19—C27 | 120.07 (16) |
C4—C5—H5C | 109.5 | C18—C19—C27 | 121.75 (15) |
H5A—C5—H5C | 109.5 | C21—C20—C19 | 121.24 (18) |
H5B—C5—H5C | 109.5 | C21—C20—H20 | 119.4 |
C2—N1—C6 | 123.66 (13) | C19—C20—H20 | 119.4 |
C2—N1—H1N | 126 (2) | C20—C21—C22 | 119.86 (18) |
C6—N1—H1N | 110 (2) | C20—C21—H21 | 120.1 |
C11—C6—C7 | 121.57 (17) | C22—C21—H21 | 120.1 |
C11—C6—N1 | 120.41 (16) | C21—C22—C23 | 121.35 (19) |
C7—C6—N1 | 117.69 (16) | C21—C22—H22 | 119.3 |
C8—C7—C6 | 117.7 (2) | C23—C22—H22 | 119.3 |
C8—C7—C15 | 120.8 (2) | C22—C23—C18 | 117.88 (17) |
C6—C7—C15 | 121.47 (18) | C22—C23—C24 | 120.62 (17) |
C9—C8—C7 | 121.4 (2) | C18—C23—C24 | 121.50 (16) |
C9—C8—H8 | 119.3 | C26—C24—C23 | 113.27 (18) |
C7—C8—H8 | 119.3 | C26—C24—C25 | 110.6 (2) |
C10—C9—C8 | 119.9 (2) | C23—C24—C25 | 111.22 (19) |
C10—C9—H9 | 120.0 | C26—C24—H24 | 107.1 |
C8—C9—H9 | 120.0 | C23—C24—H24 | 107.1 |
C9—C10—C11 | 121.7 (2) | C25—C24—H24 | 107.1 |
C9—C10—H10 | 119.2 | C24—C25—H25A | 109.5 |
C11—C10—H10 | 119.2 | C24—C25—H25B | 109.5 |
C10—C11—C6 | 117.68 (19) | H25A—C25—H25B | 109.5 |
C10—C11—C12 | 120.44 (19) | C24—C25—H25C | 109.5 |
C6—C11—C12 | 121.85 (16) | H25A—C25—H25C | 109.5 |
C11—C12—C13 | 112.25 (18) | H25B—C25—H25C | 109.5 |
C11—C12—C14 | 111.35 (17) | C24—C26—H26A | 109.5 |
C13—C12—C14 | 110.99 (18) | C24—C26—H26B | 109.5 |
C11—C12—H12 | 107.3 | H26A—C26—H26B | 109.5 |
C13—C12—H12 | 107.3 | C24—C26—H26C | 109.5 |
C14—C12—H12 | 107.3 | H26A—C26—H26C | 109.5 |
C12—C13—H13A | 109.5 | H26B—C26—H26C | 109.5 |
C12—C13—H13B | 109.5 | C19—C27—C29 | 110.92 (16) |
H13A—C13—H13B | 109.5 | C19—C27—C28 | 111.62 (16) |
C12—C13—H13C | 109.5 | C29—C27—C28 | 110.92 (17) |
H13A—C13—H13C | 109.5 | C19—C27—H27 | 107.7 |
H13B—C13—H13C | 109.5 | C29—C27—H27 | 107.7 |
C12—C14—H14A | 109.5 | C28—C27—H27 | 107.7 |
C12—C14—H14B | 109.5 | C27—C28—H28A | 109.5 |
H14A—C14—H14B | 109.5 | C27—C28—H28B | 109.5 |
C12—C14—H14C | 109.5 | H28A—C28—H28B | 109.5 |
H14A—C14—H14C | 109.5 | C27—C28—H28C | 109.5 |
H14B—C14—H14C | 109.5 | H28A—C28—H28C | 109.5 |
C7—C15—C16 | 112.4 (2) | H28B—C28—H28C | 109.5 |
C7—C15—C17 | 111.3 (2) | C27—C29—H29A | 109.5 |
C16—C15—C17 | 110.2 (2) | C27—C29—H29B | 109.5 |
C7—C15—H15 | 107.6 | H29A—C29—H29B | 109.5 |
C16—C15—H15 | 107.6 | C27—C29—H29C | 109.5 |
C17—C15—H15 | 107.6 | H29A—C29—H29C | 109.5 |
C15—C16—H16A | 109.5 | H29B—C29—H29C | 109.5 |
C15—C16—H16B | 109.5 | ||
N1—C2—C3—C4 | 170.52 (16) | C8—C7—C15—C17 | −74.4 (3) |
C1—C2—C3—C4 | −12.6 (3) | C6—C7—C15—C17 | 105.3 (2) |
C2—C3—C4—N2 | 166.31 (16) | C3—C4—N2—C18 | −10.9 (2) |
C2—C3—C4—C5 | −16.5 (3) | C5—C4—N2—C18 | 171.59 (15) |
C3—C2—N1—C6 | −13.0 (2) | C4—N2—C18—C23 | −93.19 (19) |
C1—C2—N1—C6 | 169.83 (15) | C4—N2—C18—C19 | 92.21 (19) |
C2—N1—C6—C11 | 92.75 (19) | C23—C18—C19—C20 | −2.1 (2) |
C2—N1—C6—C7 | −93.79 (19) | N2—C18—C19—C20 | 172.37 (14) |
C11—C6—C7—C8 | 1.4 (2) | C23—C18—C19—C27 | 179.06 (15) |
N1—C6—C7—C8 | −171.93 (15) | N2—C18—C19—C27 | −6.5 (2) |
C11—C6—C7—C15 | −178.29 (17) | C18—C19—C20—C21 | 0.0 (3) |
N1—C6—C7—C15 | 8.3 (2) | C27—C19—C20—C21 | 178.93 (16) |
C6—C7—C8—C9 | 0.5 (3) | C19—C20—C21—C22 | 1.5 (3) |
C15—C7—C8—C9 | −179.78 (19) | C20—C21—C22—C23 | −0.9 (3) |
C7—C8—C9—C10 | −1.7 (3) | C21—C22—C23—C18 | −1.0 (3) |
C8—C9—C10—C11 | 1.0 (3) | C21—C22—C23—C24 | 178.80 (17) |
C9—C10—C11—C6 | 0.8 (3) | C19—C18—C23—C22 | 2.5 (2) |
C9—C10—C11—C12 | 179.03 (18) | N2—C18—C23—C22 | −171.96 (15) |
C7—C6—C11—C10 | −2.1 (2) | C19—C18—C23—C24 | −177.29 (16) |
N1—C6—C11—C10 | 171.11 (15) | N2—C18—C23—C24 | 8.2 (2) |
C7—C6—C11—C12 | 179.76 (16) | C22—C23—C24—C26 | 55.7 (3) |
N1—C6—C11—C12 | −7.0 (2) | C18—C23—C24—C26 | −124.5 (2) |
C10—C11—C12—C13 | 48.9 (2) | C22—C23—C24—C25 | −69.6 (3) |
C6—C11—C12—C13 | −132.95 (18) | C18—C23—C24—C25 | 110.2 (2) |
C10—C11—C12—C14 | −76.2 (2) | C20—C19—C27—C29 | −71.4 (2) |
C6—C11—C12—C14 | 101.9 (2) | C18—C19—C27—C29 | 107.52 (18) |
C8—C7—C15—C16 | 49.7 (3) | C20—C19—C27—C28 | 52.9 (2) |
C6—C7—C15—C16 | −130.6 (2) | C18—C19—C27—C28 | −128.24 (19) |
Experimental details
Crystal data | |
Chemical formula | C29H42N2·0.5C7H8 |
Mr | 464.71 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 26.655 (5), 18.004 (3), 12.623 (2) |
β (°) | 91.972 (3) |
V (Å3) | 6054.0 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.06 |
Crystal size (mm) | 0.19 × 0.16 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.989, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21824, 5322, 4677 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.141, 1.14 |
No. of reflections | 5322 |
No. of parameters | 296 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.
C1—C2 | 1.502 (2) | C4—N2 | 1.327 (2) |
C2—N1 | 1.326 (2) | C4—C5 | 1.505 (2) |
C2—C3 | 1.398 (2) | N1—C6 | 1.424 (2) |
C3—C4 | 1.401 (2) | N2—C18 | 1.428 (2) |
N1—C2—C3 | 121.92 (15) | N2—C4—C5 | 114.06 (13) |
N1—C2—C1 | 114.12 (14) | C3—C4—C5 | 124.05 (14) |
C3—C2—C1 | 123.89 (14) | C2—N1—C6 | 123.66 (13) |
C2—C3—C4 | 129.70 (15) | C4—N2—C18 | 122.77 (13) |
N2—C4—C3 | 121.84 (14) |
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β-Diketimine ligands such as the title compound, (I), are proving to be versatile ligands in the monoanionic form for early transition metals in olefin polymerization (Budzelaar et al., 1998). Recently, we have been interested in the application of (I) for olefin polymerization by nitrogen-ligated organomagnesium species (Bailey et al., 2000). However, whilst there are now many examples of this ligand in the deprotonated monoanionc form as chelates, there are no examples to date of the free protonated parent ligand (I) itself. We report here the crystal structure of (I), which was synthesized via a standard procedure of acid-catalysed condensation of 2,4-pentanedione and 2,6-diisopropylaniline (Parks & Holm, 1968).
The crystal structure is composed of discrete molecules of (I) (Fig. 1) exhibiting no significant intermolecular contacts. The N—C [N1—C2 1.326 (2) and N2—C4 1.327 (2) Å] and C—C [C2—C3 1.398 (2) and C3—C4 1.401 (2) Å] bond lengths of the N—C—C—C—N backbone are in the range associated with aromatic N—C and C—C bonds (Allen et al., 1992). Variation between the N—C (N1—C2 and N2—C4) and C—C (C2—C3 and C3—C4) bonds are statistically insignificant. Compound (I) thus crystallizes as a mixture of the two possible imine–enamine tautomers (see Scheme); inspection of the difference map around C3 gives no evidence to suggest the presence of the third tautomer. As a consequence, the amine proton is disordered in 50:50% occupancy over both N1 and N2 with bond lengths of 0.90 (3) and 0.89 (3) Å, respectively.
The two backbone methyl groups (C1 and C5) adopt a syn orientation; this is surprising as an anti conformation would lead to a less congested conformer. It is likely that small steric, electronic and entropic factors, or crystal-packing forces, are responsible for this. The two phenyl rings adopt a synperiplanar arrangement in order to minimize steric crowding.