Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681400292X/hy2642sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053681400292X/hy2642Isup2.hkl |
CCDC reference: 982220
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.043
- wR factor = 0.096
- Data-to-parameter ratio = 17.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... Ni1 Check PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.1 Note PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 2.936 Check PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 5 Why ?
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT128_ALERT_4_G Alternate Setting for Input Space-Group Pnam Pnma Note PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 Check
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Formic acid (0.5 ml) was added to a stirred solution of 2,3-butanedione (0.09 g, 1.00 mmol) and 2,6-diethyl-4-phenylbenzenamine (0.45 g, 2.00 mmol) in ethanol (10 ml). The mixture was refluxed for 24 h, then cooled and the precipitate was separated by filtration. The solid was recrystallized from EtOH/CH2Cl2 (v/v, 10:1), washed and dried under vacuum to give bis[N,N'-(2,6-diethyl-4-(1-phenyl)imino]-1,2-dimethylethane (yield: 0.69 g, 85%). Analysis, calculated for C36H40N2: C 86.35, H 8.05, N 5.59%; found: C 84.96, H 7.21, N 7.82%.
NiBr2(DME) (0.13 g, 1.20 mmol), bis[N,N'-(2,6-diethyl-4-(1-phenyl)imino]-1,2-dimethylethane (0.20 g, 4.00 mmol) and dichloromethane (40 ml) were mixed in a Schlenk flask and stirred at room temperature for 24 h. The resulting suspension was filtered. The solvent was removed under vacuum and the residue was washed with diethyl ether (15 ml) three times, and then dried under vacuum at room temperature to give the title compound (yield: 0.63 g, 82%). Analysis, calculated for C36H40Br2N2Ni: C 60.12, H 5.61, N 3.89%; found: C 59.88, H 5.31, N 3.56%. FT-IR (KBr, cm-1): 1649 (C═N). Crystals suitable for X-ray structure determination were grown from a solution of the title compound in a mixture of cyclohexane/dichloromethane (v/v, 1:4).
H atoms were placed in calculated positions and refined as riding atoms, with C—H = 0.93 (aromatic), 0.97 (CH2) and 0.96 (CH3) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C).
Data collection: CrysAlis PRO (Oxford Diffraction, 2012); cell refinement: CrysAlis PRO (Oxford Diffraction, 2012); data reduction: CrysAlis PRO (Oxford Diffraction, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. Molecular structure of the title compound, showing the 30% probability level ellipsoids. [Symmetry code: (a) x, y, 3/2-z.] |
[NiBr2(C36H40N2)] | Dx = 1.457 Mg m−3 |
Mr = 719.19 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnam | Cell parameters from 2436 reflections |
a = 15.6587 (5) Å | θ = 3.5–26.1° |
b = 6.9359 (3) Å | µ = 3.06 mm−1 |
c = 30.1928 (16) Å | T = 293 K |
V = 3279.2 (2) Å3 | Block, brown |
Z = 4 | 0.42 × 0.38 × 0.35 mm |
F(000) = 1472 |
Oxford Diffraction SuperNova CCD diffractometer | 3415 independent reflections |
Radiation source: fine-focus sealed tube | 2376 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 26.4°, θmin = 3.0° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012) | h = −19→18 |
Tmin = 0.508, Tmax = 1.000 | k = −8→4 |
10334 measured reflections | l = −37→22 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0361P)2 + 2.0948P] where P = (Fo2 + 2Fc2)/3 |
3415 reflections | (Δ/σ)max < 0.001 |
193 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[NiBr2(C36H40N2)] | V = 3279.2 (2) Å3 |
Mr = 719.19 | Z = 4 |
Orthorhombic, Pnam | Mo Kα radiation |
a = 15.6587 (5) Å | µ = 3.06 mm−1 |
b = 6.9359 (3) Å | T = 293 K |
c = 30.1928 (16) Å | 0.42 × 0.38 × 0.35 mm |
Oxford Diffraction SuperNova CCD diffractometer | 3415 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2012) | 2376 reflections with I > 2σ(I) |
Tmin = 0.508, Tmax = 1.000 | Rint = 0.046 |
10334 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.53 e Å−3 |
3415 reflections | Δρmin = −0.53 e Å−3 |
193 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 | ||
Ni1 | 0.34408 (3) | 0.82145 (10) | 0.7500 | 0.03485 (18) | |
Br2 | 0.28258 (4) | 0.51120 (8) | 0.7500 | 0.05577 (19) | |
Br3 | 0.49179 (3) | 0.84183 (12) | 0.7500 | 0.0705 (2) | |
N1 | 0.26850 (15) | 0.9588 (4) | 0.70741 (8) | 0.0293 (6) | |
C1 | 0.28083 (18) | 0.9383 (5) | 0.66015 (10) | 0.0292 (7) | |
C2 | 0.20665 (19) | 1.0521 (5) | 0.72490 (10) | 0.0311 (8) | |
C3 | 0.23084 (19) | 0.8070 (5) | 0.63611 (11) | 0.0330 (8) | |
C4 | 0.3703 (2) | 0.9915 (5) | 0.59746 (11) | 0.0345 (8) | |
H4 | 0.4167 | 1.0528 | 0.5844 | 0.041* | |
C5 | 0.2544 (2) | 0.7728 (5) | 0.59207 (11) | 0.0379 (8) | |
H5 | 0.2217 | 0.6882 | 0.5753 | 0.046* | |
C6 | 0.3243 (2) | 0.8598 (5) | 0.57262 (11) | 0.0347 (8) | |
C7 | 0.34987 (18) | 1.0362 (5) | 0.64119 (10) | 0.0309 (7) | |
C8 | 0.3998 (2) | 1.1906 (5) | 0.66489 (12) | 0.0420 (9) | |
H8A | 0.3808 | 1.1971 | 0.6954 | 0.050* | |
H8B | 0.4598 | 1.1556 | 0.6650 | 0.050* | |
C9 | 0.0769 (2) | 0.7102 (8) | 0.62840 (16) | 0.0748 (15) | |
H9A | 0.0857 | 0.6469 | 0.6005 | 0.112* | |
H9B | 0.0627 | 0.8430 | 0.6234 | 0.112* | |
H9C | 0.0310 | 0.6482 | 0.6440 | 0.112* | |
C10 | 0.1368 (2) | 1.1541 (6) | 0.70058 (12) | 0.0476 (9) | |
H10A | 0.0831 | 1.0933 | 0.7070 | 0.071* | |
H10B | 0.1475 | 1.1479 | 0.6693 | 0.071* | |
H10C | 0.1348 | 1.2865 | 0.7098 | 0.071* | |
C11 | 0.3499 (2) | 0.8120 (5) | 0.52645 (11) | 0.0411 (9) | |
C12 | 0.2902 (3) | 0.8027 (6) | 0.49250 (12) | 0.0540 (11) | |
H12 | 0.2330 | 0.8278 | 0.4984 | 0.065* | |
C13 | 0.1566 (2) | 0.6983 (6) | 0.65535 (12) | 0.0475 (10) | |
H13A | 0.1725 | 0.5639 | 0.6585 | 0.057* | |
H13B | 0.1448 | 0.7483 | 0.6847 | 0.057* | |
C14 | 0.3154 (3) | 0.7564 (7) | 0.44983 (13) | 0.0664 (13) | |
H14 | 0.2752 | 0.7525 | 0.4272 | 0.080* | |
C15 | 0.3988 (4) | 0.7166 (7) | 0.44081 (14) | 0.0742 (15) | |
H15 | 0.4151 | 0.6847 | 0.4121 | 0.089* | |
C16 | 0.4587 (3) | 0.7232 (8) | 0.47362 (15) | 0.0754 (15) | |
H16 | 0.5156 | 0.6956 | 0.4673 | 0.091* | |
C17 | 0.4343 (3) | 0.7713 (7) | 0.51643 (13) | 0.0603 (12) | |
H17 | 0.4753 | 0.7763 | 0.5387 | 0.072* | |
C18 | 0.3901 (3) | 1.3857 (6) | 0.64409 (15) | 0.0692 (13) | |
H18A | 0.4087 | 1.3804 | 0.6138 | 0.104* | |
H18B | 0.4241 | 1.4776 | 0.6600 | 0.104* | |
H18C | 0.3312 | 1.4240 | 0.6451 | 0.104* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0328 (3) | 0.0534 (4) | 0.0183 (3) | 0.0117 (3) | 0.000 | 0.000 |
Br2 | 0.0802 (4) | 0.0450 (3) | 0.0421 (3) | 0.0080 (3) | 0.000 | 0.000 |
Br3 | 0.0341 (3) | 0.1250 (6) | 0.0523 (4) | 0.0136 (3) | 0.000 | 0.000 |
N1 | 0.0306 (13) | 0.0418 (16) | 0.0154 (12) | 0.0013 (12) | 0.0013 (11) | −0.0002 (12) |
C1 | 0.0321 (16) | 0.0389 (19) | 0.0165 (15) | 0.0037 (15) | −0.0012 (13) | 0.0011 (14) |
C2 | 0.0314 (16) | 0.0382 (19) | 0.0236 (17) | −0.0002 (14) | −0.0044 (14) | 0.0020 (15) |
C3 | 0.0342 (16) | 0.041 (2) | 0.0241 (17) | −0.0025 (15) | −0.0030 (14) | 0.0060 (16) |
C4 | 0.0348 (16) | 0.045 (2) | 0.0239 (16) | −0.0035 (16) | 0.0037 (15) | 0.0028 (17) |
C5 | 0.0451 (19) | 0.044 (2) | 0.0244 (17) | −0.0068 (17) | −0.0058 (16) | −0.0037 (17) |
C6 | 0.0417 (18) | 0.041 (2) | 0.0209 (16) | 0.0002 (16) | −0.0033 (15) | −0.0004 (16) |
C7 | 0.0334 (16) | 0.037 (2) | 0.0222 (16) | 0.0030 (15) | −0.0022 (14) | −0.0015 (15) |
C8 | 0.0433 (19) | 0.049 (2) | 0.0339 (19) | −0.0061 (18) | −0.0022 (16) | −0.0062 (19) |
C9 | 0.050 (2) | 0.118 (4) | 0.056 (3) | −0.031 (3) | −0.008 (2) | 0.008 (3) |
C10 | 0.048 (2) | 0.061 (2) | 0.0336 (19) | 0.0162 (19) | −0.0063 (17) | 0.003 (2) |
C11 | 0.060 (2) | 0.042 (2) | 0.0215 (17) | −0.0061 (18) | 0.0019 (17) | −0.0008 (17) |
C12 | 0.068 (2) | 0.066 (3) | 0.028 (2) | −0.016 (2) | −0.0033 (19) | −0.002 (2) |
C13 | 0.049 (2) | 0.060 (3) | 0.034 (2) | −0.014 (2) | 0.0001 (17) | 0.009 (2) |
C14 | 0.102 (4) | 0.076 (3) | 0.022 (2) | −0.026 (3) | −0.013 (2) | −0.003 (2) |
C15 | 0.124 (4) | 0.072 (3) | 0.027 (2) | −0.011 (3) | 0.019 (3) | −0.007 (2) |
C16 | 0.090 (3) | 0.098 (4) | 0.038 (3) | 0.010 (3) | 0.024 (3) | −0.007 (3) |
C17 | 0.063 (3) | 0.090 (3) | 0.028 (2) | 0.009 (2) | 0.0031 (19) | −0.007 (2) |
C18 | 0.104 (3) | 0.053 (3) | 0.050 (3) | −0.022 (3) | 0.011 (3) | −0.009 (2) |
Ni1—N1 | 1.991 (2) | C9—H9A | 0.9600 |
Ni1—Br2 | 2.3575 (9) | C9—H9B | 0.9600 |
Ni1—Br3 | 2.3173 (8) | C9—H9C | 0.9600 |
N1—C2 | 1.279 (4) | C10—H10A | 0.9600 |
N1—C1 | 1.447 (4) | C10—H10B | 0.9600 |
C1—C7 | 1.399 (4) | C10—H10C | 0.9600 |
C1—C3 | 1.403 (4) | C11—C17 | 1.386 (5) |
C2—C10 | 1.496 (4) | C11—C12 | 1.388 (5) |
C2—C2i | 1.516 (6) | C12—C14 | 1.385 (6) |
C3—C5 | 1.400 (5) | C12—H12 | 0.9300 |
C3—C13 | 1.503 (4) | C13—H13A | 0.9700 |
C4—C6 | 1.384 (5) | C13—H13B | 0.9700 |
C4—C7 | 1.393 (4) | C14—C15 | 1.363 (6) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.381 (5) | C15—C16 | 1.365 (7) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C11 | 1.488 (4) | C16—C17 | 1.389 (5) |
C7—C8 | 1.507 (4) | C16—H16 | 0.9300 |
C8—C18 | 1.499 (6) | C17—H17 | 0.9300 |
C8—H8A | 0.9700 | C18—H18A | 0.9600 |
C8—H8B | 0.9700 | C18—H18B | 0.9600 |
C9—C13 | 1.492 (5) | C18—H18C | 0.9600 |
N1i—Ni1—N1 | 80.49 (14) | C13—C9—H9C | 109.5 |
N1i—Ni1—Br3 | 124.35 (7) | H9A—C9—H9C | 109.5 |
N1—Ni1—Br3 | 124.35 (7) | H9B—C9—H9C | 109.5 |
N1i—Ni1—Br2 | 101.19 (8) | C2—C10—H10A | 109.5 |
N1—Ni1—Br2 | 101.19 (8) | C2—C10—H10B | 109.5 |
Br3—Ni1—Br2 | 117.61 (4) | H10A—C10—H10B | 109.5 |
C2—N1—C1 | 123.9 (3) | C2—C10—H10C | 109.5 |
C2—N1—Ni1 | 115.2 (2) | H10A—C10—H10C | 109.5 |
C1—N1—Ni1 | 120.70 (19) | H10B—C10—H10C | 109.5 |
C7—C1—C3 | 122.3 (3) | C17—C11—C12 | 118.1 (3) |
C7—C1—N1 | 117.3 (3) | C17—C11—C6 | 120.4 (3) |
C3—C1—N1 | 120.0 (3) | C12—C11—C6 | 121.4 (3) |
N1—C2—C10 | 126.2 (3) | C14—C12—C11 | 120.4 (4) |
N1—C2—C2i | 114.40 (17) | C14—C12—H12 | 119.8 |
C10—C2—C2i | 119.41 (18) | C11—C12—H12 | 119.8 |
C5—C3—C1 | 117.0 (3) | C9—C13—C3 | 114.1 (3) |
C5—C3—C13 | 119.1 (3) | C9—C13—H13A | 108.7 |
C1—C3—C13 | 123.9 (3) | C3—C13—H13A | 108.7 |
C6—C4—C7 | 122.7 (3) | C9—C13—H13B | 108.7 |
C6—C4—H4 | 118.6 | C3—C13—H13B | 108.7 |
C7—C4—H4 | 118.6 | H13A—C13—H13B | 107.6 |
C6—C5—C3 | 122.6 (3) | C15—C14—C12 | 120.4 (4) |
C6—C5—H5 | 118.7 | C15—C14—H14 | 119.8 |
C3—C5—H5 | 118.7 | C12—C14—H14 | 119.8 |
C5—C6—C4 | 118.1 (3) | C14—C15—C16 | 120.5 (4) |
C5—C6—C11 | 121.0 (3) | C14—C15—H15 | 119.8 |
C4—C6—C11 | 121.0 (3) | C16—C15—H15 | 119.8 |
C4—C7—C1 | 117.2 (3) | C15—C16—C17 | 119.6 (4) |
C4—C7—C8 | 119.3 (3) | C15—C16—H16 | 120.2 |
C1—C7—C8 | 123.5 (3) | C17—C16—H16 | 120.2 |
C18—C8—C7 | 113.0 (3) | C11—C17—C16 | 121.0 (4) |
C18—C8—H8A | 109.0 | C11—C17—H17 | 119.5 |
C7—C8—H8A | 109.0 | C16—C17—H17 | 119.5 |
C18—C8—H8B | 109.0 | C8—C18—H18A | 109.5 |
C7—C8—H8B | 109.0 | C8—C18—H18B | 109.5 |
H8A—C8—H8B | 107.8 | H18A—C18—H18B | 109.5 |
C13—C9—H9A | 109.5 | C8—C18—H18C | 109.5 |
C13—C9—H9B | 109.5 | H18A—C18—H18C | 109.5 |
H9A—C9—H9B | 109.5 | H18B—C18—H18C | 109.5 |
N1i—Ni1—N1—C2 | −5.1 (3) | C7—C4—C6—C11 | −178.2 (3) |
Br3—Ni1—N1—C2 | −130.5 (2) | C6—C4—C7—C1 | 1.4 (5) |
Br2—Ni1—N1—C2 | 94.5 (2) | C6—C4—C7—C8 | −176.1 (3) |
N1i—Ni1—N1—C1 | 179.54 (19) | C3—C1—C7—C4 | −3.0 (5) |
Br3—Ni1—N1—C1 | 54.2 (3) | N1—C1—C7—C4 | 169.6 (3) |
Br2—Ni1—N1—C1 | −80.8 (2) | C3—C1—C7—C8 | 174.4 (3) |
C2—N1—C1—C7 | 110.0 (4) | N1—C1—C7—C8 | −13.0 (5) |
Ni1—N1—C1—C7 | −75.1 (3) | C4—C7—C8—C18 | 63.1 (4) |
C2—N1—C1—C3 | −77.2 (4) | C1—C7—C8—C18 | −114.3 (4) |
Ni1—N1—C1—C3 | 97.7 (3) | C5—C6—C11—C17 | −132.5 (4) |
C1—N1—C2—C10 | 0.4 (5) | C4—C6—C11—C17 | 46.9 (5) |
Ni1—N1—C2—C10 | −174.8 (3) | C5—C6—C11—C12 | 46.1 (5) |
C1—N1—C2—C2i | 179.5 (2) | C4—C6—C11—C12 | −134.4 (4) |
Ni1—N1—C2—C2i | 4.3 (2) | C17—C11—C12—C14 | −0.8 (6) |
C7—C1—C3—C5 | 1.8 (5) | C6—C11—C12—C14 | −179.5 (4) |
N1—C1—C3—C5 | −170.6 (3) | C5—C3—C13—C9 | −52.4 (5) |
C7—C1—C3—C13 | 179.7 (3) | C1—C3—C13—C9 | 129.8 (4) |
N1—C1—C3—C13 | 7.2 (5) | C11—C12—C14—C15 | 1.0 (7) |
C1—C3—C5—C6 | 1.1 (5) | C12—C14—C15—C16 | −0.5 (7) |
C13—C3—C5—C6 | −176.8 (3) | C14—C15—C16—C17 | −0.1 (8) |
C3—C5—C6—C4 | −2.7 (5) | C12—C11—C17—C16 | 0.2 (7) |
C3—C5—C6—C11 | 176.8 (3) | C6—C11—C17—C16 | 178.9 (4) |
C7—C4—C6—C5 | 1.3 (5) | C15—C16—C17—C11 | 0.3 (8) |
Symmetry code: (i) x, y, −z+3/2. |
There is a considerable interest in the development of new late transition metal catalysts for the polymerization of α-olefins since Brookhart et al. discovered highly active α-diimine nickel catalysts (Johnson et al., 1995; Killian et al., 1996). The ligand structure has a dramatic effect on the reactivity of organometallic complexes (Popeney et al., 2011; Popeney & Guan, 2010). Advances in the field of homogeneous catalysis have led to the synthesis of well defined transition metal complexes capable of catalyzing a wide range of organic transformations. It is well known that the Lewis acid catalyzed Friedel-Crafts alkylation of substituted aromatic rings is a highly versatile C—C bond forming method. In this study, we designed and synthesized the title compound, and its molecular structure was characterized by X-ray diffraction. The dihedral angle formed between the benzene ring and phenylethyl ring is 47.1 (1)°.