The crystal structure of the title compound, [Et3NH][(Me2bpb)FeCl2] or (C6H16N)[FeCl2(C20H16N4O2)], has been determined. Four N atoms of the Me2bpb [1,2-bis(2-pyridinecarboxamido)-4,5-dimethylbenzene] ligand and two chloro ligands are coordinated to the iron(III) ion. The geometry of the complex anion is distorted octahedral, with a Cl-Fe-Cl angle of 156.59 (3)°. The 4,5-dimethylbenzene ring of the Me2bpb ligand is tilted from the N4 plane by 9.5 (1)°.
Supporting information
CCDC reference: 185745
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.120
- Data-to-parameter ratio = 16.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
For the preparation of the ligand
1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene (H2Me2bpb), a
modification of the method of Patra et al. (2000) was used. To a
stirred solution of picolinic acid (0.246 g, 2 mmol) in pyridine (1 ml), a
solution of 4,5-dimethyl-1,2-diaminobenzene (0.136 g, 1 mmol) in pyridine (1.5 ml) was added dropwise. The solution was stirred for 15 min and triphenyl
phosphite (520 µl, 2 mmol) was added dropwise. The temperature of the
reaction mixture was increased to 393 K, and the mixture was stirred for 4 h.
The volume was then reduced to 2 ml and kept in air. After 24 h, a white
precipitate that resulted was collected by filtration. Recrystallization from
CHCl3 and diethyl ether afforded white needles. For the preparation of (I),
a modification of the method of Yang et al. (1991) was used.
FeCl3.xH2O (0.162 g, 1 mmol) was added to a solution of H2Me2bpb
(0.346 g, 1 mmol) and 300 µl of Et3N in 30 ml of dry acetonitrile under a
nitrogen atmosphere. The solution turned dark-green immediately. The solution
was stirred overnight. A small amount of brown precipitate was removed by
filtration. A mixture of dark-green crystals of [(Et3NH)][(Me2bpb)FeCl2]
and a white powder of Et3NHCl was formed and isolated by filtration.
Dark-green single crystals of [(Et3NH)][(Me2bpb)FeCl2] were grown from
acetonitrile underlayering ether at room temperature.
The H atoms attached to C atoms were placed at calculated positions and treated
as riding with isotropic displacement parameters.
Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Crystal data top
(C6H16N)[FeCl2(C20H16N4O2)] | F(000) = 1196 |
Mr = 573.32 | Dx = 1.390 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 11.0038 (10) Å | θ = 9.6–12.3° |
b = 16.273 (2) Å | µ = 0.78 mm−1 |
c = 15.578 (2) Å | T = 298 K |
β = 100.789 (10)° | Block cut from plate, dark green |
V = 2740.2 (5) Å3 | 0.35 × 0.35 × 0.25 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 MACH3 diffractometer | Rint = 0.029 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.1° |
Graphite monochromator | h = 0→13 |
2θ–ω scans | k = 0→20 |
5637 measured reflections | l = −19→18 |
5352 independent reflections | 3 standard reflections every 60 min |
4515 reflections with I > 2σ(I) | intensity decay: negligible' |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0774P)2 + 1.2196P] where P = (Fo2 + 2Fc2)/3 |
5352 reflections | (Δ/σ)max < 0.001 |
334 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
Crystal data top
(C6H16N)[FeCl2(C20H16N4O2)] | V = 2740.2 (5) Å3 |
Mr = 573.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0038 (10) Å | µ = 0.78 mm−1 |
b = 16.273 (2) Å | T = 298 K |
c = 15.578 (2) Å | 0.35 × 0.35 × 0.25 mm |
β = 100.789 (10)° | |
Data collection top
Enraf-Nonius CAD-4 MACH3 diffractometer | Rint = 0.029 |
5637 measured reflections | 3 standard reflections every 60 min |
5352 independent reflections | intensity decay: negligible' |
4515 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.70 e Å−3 |
5352 reflections | Δρmin = −0.64 e Å−3 |
334 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 | |
Fe1 | 0.43795 (3) | 0.140014 (18) | 0.346984 (19) | 0.02867 (12) | |
Cl1 | 0.25261 (6) | 0.20788 (4) | 0.35577 (4) | 0.04375 (17) | |
Cl2 | 0.60189 (6) | 0.04664 (4) | 0.38843 (4) | 0.04393 (17) | |
N1 | 0.50532 (18) | 0.19638 (12) | 0.47187 (12) | 0.0343 (4) | |
N2 | 0.53808 (17) | 0.23778 (11) | 0.31418 (12) | 0.0314 (4) | |
N3 | 0.41062 (17) | 0.12999 (11) | 0.21417 (12) | 0.0303 (4) | |
N4 | 0.32519 (18) | 0.03203 (11) | 0.32242 (13) | 0.0334 (4) | |
O1 | 0.6361 (2) | 0.35770 (12) | 0.36829 (14) | 0.0600 (6) | |
O2 | 0.33026 (18) | 0.04615 (10) | 0.09685 (11) | 0.0432 (4) | |
C1 | 0.4890 (3) | 0.17013 (17) | 0.54974 (16) | 0.0444 (6) | |
H1 | 0.4453 | 0.1217 | 0.5532 | 0.053* | |
C2 | 0.5350 (3) | 0.21276 (19) | 0.62588 (17) | 0.0516 (7) | |
H2 | 0.5228 | 0.1932 | 0.6797 | 0.062* | |
C3 | 0.5990 (3) | 0.28441 (19) | 0.62023 (18) | 0.0526 (7) | |
H3 | 0.6313 | 0.3140 | 0.6704 | 0.063* | |
C4 | 0.6148 (2) | 0.31184 (17) | 0.54018 (18) | 0.0462 (6) | |
H4 | 0.6568 | 0.3607 | 0.5352 | 0.055* | |
C5 | 0.5674 (2) | 0.26586 (14) | 0.46606 (15) | 0.0346 (5) | |
C6 | 0.5834 (2) | 0.29131 (14) | 0.37623 (16) | 0.0356 (5) | |
C7 | 0.5344 (2) | 0.24981 (13) | 0.22441 (15) | 0.0318 (5) | |
C8 | 0.5906 (2) | 0.31226 (15) | 0.18567 (17) | 0.0398 (5) | |
H8 | 0.6444 | 0.3477 | 0.2210 | 0.048* | |
C9 | 0.5691 (2) | 0.32363 (15) | 0.09573 (17) | 0.0421 (6) | |
C10 | 0.4875 (2) | 0.27111 (15) | 0.04238 (16) | 0.0407 (5) | |
C11 | 0.4381 (2) | 0.20528 (15) | 0.07972 (15) | 0.0364 (5) | |
H11 | 0.3884 | 0.1681 | 0.0437 | 0.044* | |
C12 | 0.4604 (2) | 0.19263 (13) | 0.16977 (15) | 0.0306 (4) | |
C13 | 0.3509 (2) | 0.06451 (13) | 0.17511 (14) | 0.0309 (5) | |
C14 | 0.3035 (2) | 0.00933 (13) | 0.23826 (15) | 0.0329 (5) | |
C15 | 0.2418 (2) | −0.06262 (16) | 0.21124 (18) | 0.0445 (6) | |
H15 | 0.2286 | −0.0783 | 0.1528 | 0.053* | |
C16 | 0.2001 (3) | −0.11083 (17) | 0.2723 (2) | 0.0525 (7) | |
H16 | 0.1594 | −0.1600 | 0.2557 | 0.063* | |
C17 | 0.2190 (3) | −0.08586 (17) | 0.3579 (2) | 0.0502 (7) | |
H17 | 0.1892 | −0.1169 | 0.3996 | 0.060* | |
C18 | 0.2830 (2) | −0.01405 (15) | 0.38112 (17) | 0.0422 (6) | |
H18 | 0.2971 | 0.0027 | 0.4392 | 0.051* | |
C19 | 0.6313 (4) | 0.3939 (2) | 0.0574 (2) | 0.0712 (10) | |
H19A | 0.5699 | 0.4328 | 0.0312 | 0.085* | |
H19B | 0.6744 | 0.3731 | 0.0138 | 0.085* | |
H19C | 0.6890 | 0.4203 | 0.1028 | 0.085* | |
C20 | 0.4506 (3) | 0.2849 (2) | −0.05528 (19) | 0.0610 (8) | |
H20A | 0.3943 | 0.2425 | −0.0803 | 0.073* | |
H20B | 0.5230 | 0.2834 | −0.0814 | 0.073* | |
H20C | 0.4111 | 0.3375 | −0.0660 | 0.073* | |
N5 | 0.2692 (2) | 0.48698 (13) | 0.63768 (14) | 0.0410 (5) | |
H5 | 0.307 (3) | 0.536 (2) | 0.641 (2) | 0.058 (9)* | |
C21 | 0.3037 (3) | 0.4488 (2) | 0.7269 (2) | 0.0610 (8) | |
H21A | 0.2637 | 0.4791 | 0.7676 | 0.073* | |
H21B | 0.2730 | 0.3928 | 0.7245 | 0.073* | |
C22 | 0.4402 (4) | 0.4481 (3) | 0.7602 (2) | 0.0831 (11) | |
H22A | 0.4779 | 0.4069 | 0.7296 | 0.100* | |
H22B | 0.4563 | 0.4360 | 0.8216 | 0.100* | |
H22C | 0.4740 | 0.5010 | 0.7507 | 0.100* | |
C31 | 0.3178 (3) | 0.44050 (18) | 0.56786 (18) | 0.0508 (7) | |
H31A | 0.3011 | 0.4722 | 0.5142 | 0.061* | |
H31B | 0.4069 | 0.4354 | 0.5851 | 0.061* | |
C32 | 0.2638 (4) | 0.3568 (2) | 0.5501 (3) | 0.0835 (12) | |
H32A | 0.2802 | 0.3247 | 0.6027 | 0.100* | |
H32B | 0.3004 | 0.3305 | 0.5059 | 0.100* | |
H32C | 0.1761 | 0.3612 | 0.5302 | 0.100* | |
C41 | 0.1330 (3) | 0.5029 (2) | 0.6117 (2) | 0.0557 (7) | |
H41A | 0.1145 | 0.5189 | 0.5506 | 0.067* | |
H41B | 0.0884 | 0.4525 | 0.6178 | 0.067* | |
C42 | 0.0888 (3) | 0.5684 (2) | 0.6652 (3) | 0.0675 (9) | |
H42A | 0.0917 | 0.5486 | 0.7236 | 0.081* | |
H42B | 0.0052 | 0.5830 | 0.6398 | 0.081* | |
H42C | 0.1409 | 0.6159 | 0.6668 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.03711 (19) | 0.02292 (18) | 0.02493 (18) | −0.00332 (12) | 0.00314 (13) | 0.00038 (11) |
Cl1 | 0.0438 (3) | 0.0447 (3) | 0.0420 (3) | 0.0082 (3) | 0.0061 (3) | −0.0007 (3) |
Cl2 | 0.0496 (4) | 0.0413 (3) | 0.0396 (3) | 0.0121 (3) | 0.0051 (3) | 0.0039 (2) |
N1 | 0.0397 (10) | 0.0309 (10) | 0.0299 (10) | 0.0000 (8) | 0.0003 (8) | −0.0011 (8) |
N2 | 0.0363 (10) | 0.0254 (9) | 0.0315 (10) | −0.0042 (7) | 0.0036 (8) | −0.0009 (7) |
N3 | 0.0365 (9) | 0.0267 (9) | 0.0273 (9) | −0.0040 (7) | 0.0047 (7) | 0.0003 (7) |
N4 | 0.0380 (10) | 0.0270 (9) | 0.0346 (10) | −0.0039 (8) | 0.0055 (8) | 0.0023 (8) |
O1 | 0.0842 (15) | 0.0442 (11) | 0.0512 (12) | −0.0344 (10) | 0.0120 (11) | −0.0081 (9) |
O2 | 0.0599 (11) | 0.0368 (9) | 0.0298 (9) | −0.0094 (8) | 0.0000 (8) | −0.0035 (7) |
C1 | 0.0555 (15) | 0.0424 (14) | 0.0338 (13) | −0.0005 (12) | 0.0048 (11) | 0.0017 (11) |
C2 | 0.0631 (17) | 0.0597 (18) | 0.0292 (12) | 0.0050 (14) | 0.0015 (12) | −0.0006 (12) |
C3 | 0.0569 (16) | 0.0617 (18) | 0.0335 (13) | 0.0025 (14) | −0.0061 (12) | −0.0131 (12) |
C4 | 0.0440 (14) | 0.0481 (14) | 0.0424 (14) | −0.0081 (11) | −0.0022 (11) | −0.0116 (12) |
C5 | 0.0327 (11) | 0.0339 (12) | 0.0343 (12) | −0.0001 (9) | −0.0012 (9) | −0.0047 (9) |
C6 | 0.0369 (12) | 0.0302 (11) | 0.0383 (12) | −0.0049 (9) | 0.0035 (10) | −0.0031 (9) |
C7 | 0.0334 (11) | 0.0281 (11) | 0.0344 (11) | 0.0008 (9) | 0.0079 (9) | 0.0005 (9) |
C8 | 0.0468 (13) | 0.0323 (12) | 0.0424 (14) | −0.0069 (10) | 0.0138 (11) | −0.0027 (10) |
C9 | 0.0537 (15) | 0.0324 (12) | 0.0445 (14) | −0.0019 (11) | 0.0206 (12) | 0.0044 (11) |
C10 | 0.0534 (14) | 0.0363 (12) | 0.0355 (13) | 0.0028 (11) | 0.0160 (11) | 0.0054 (10) |
C11 | 0.0434 (13) | 0.0346 (12) | 0.0312 (12) | −0.0003 (10) | 0.0073 (10) | 0.0010 (9) |
C12 | 0.0349 (11) | 0.0257 (10) | 0.0318 (11) | 0.0018 (9) | 0.0079 (9) | 0.0021 (8) |
C13 | 0.0331 (11) | 0.0279 (10) | 0.0301 (11) | 0.0003 (9) | 0.0016 (9) | −0.0007 (9) |
C14 | 0.0343 (11) | 0.0269 (11) | 0.0360 (12) | −0.0020 (9) | 0.0030 (9) | −0.0003 (9) |
C15 | 0.0469 (14) | 0.0371 (13) | 0.0484 (15) | −0.0118 (11) | 0.0061 (11) | −0.0069 (11) |
C16 | 0.0523 (15) | 0.0366 (13) | 0.0689 (19) | −0.0176 (12) | 0.0120 (14) | −0.0023 (13) |
C17 | 0.0525 (15) | 0.0414 (14) | 0.0590 (17) | −0.0083 (12) | 0.0166 (13) | 0.0122 (13) |
C18 | 0.0492 (14) | 0.0380 (13) | 0.0398 (13) | −0.0048 (11) | 0.0093 (11) | 0.0046 (10) |
C19 | 0.108 (3) | 0.0558 (18) | 0.0591 (19) | −0.0292 (19) | 0.0399 (19) | 0.0026 (16) |
C20 | 0.090 (2) | 0.0582 (18) | 0.0379 (15) | −0.0071 (16) | 0.0185 (15) | 0.0107 (13) |
N5 | 0.0475 (12) | 0.0360 (11) | 0.0385 (11) | −0.0099 (9) | 0.0055 (9) | 0.0018 (9) |
C21 | 0.083 (2) | 0.0595 (18) | 0.0397 (15) | −0.0070 (16) | 0.0100 (15) | 0.0094 (13) |
C22 | 0.096 (3) | 0.088 (3) | 0.056 (2) | 0.014 (2) | −0.0101 (19) | 0.0157 (19) |
C31 | 0.0605 (17) | 0.0508 (16) | 0.0399 (14) | 0.0035 (13) | 0.0064 (12) | 0.0022 (12) |
C32 | 0.087 (3) | 0.065 (2) | 0.098 (3) | −0.0068 (19) | 0.014 (2) | −0.035 (2) |
C41 | 0.0415 (14) | 0.0635 (18) | 0.0604 (18) | −0.0098 (13) | 0.0053 (13) | −0.0025 (15) |
C42 | 0.0630 (19) | 0.0525 (19) | 0.090 (3) | −0.0024 (15) | 0.0229 (18) | 0.0054 (17) |
Geometric parameters (Å, º) top
Fe1—N3 | 2.0408 (19) | C14—C15 | 1.379 (3) |
Fe1—N2 | 2.0535 (18) | C15—C16 | 1.376 (4) |
Fe1—N4 | 2.1438 (19) | C15—H15 | 0.93 |
Fe1—N1 | 2.1531 (19) | C16—C17 | 1.373 (4) |
Fe1—Cl1 | 2.3457 (7) | C16—H16 | 0.93 |
Fe1—Cl2 | 2.3546 (7) | C17—C18 | 1.377 (4) |
N1—C1 | 1.330 (3) | C17—H17 | 0.93 |
N1—C5 | 1.333 (3) | C18—H18 | 0.93 |
N2—C6 | 1.327 (3) | C19—H19A | 0.96 |
N2—C7 | 1.405 (3) | C19—H19B | 0.96 |
N3—C13 | 1.337 (3) | C19—H19C | 0.96 |
N3—C12 | 1.400 (3) | C20—H20A | 0.96 |
N4—C18 | 1.332 (3) | C20—H20B | 0.96 |
N4—C14 | 1.340 (3) | C20—H20C | 0.96 |
O1—C6 | 1.243 (3) | N5—C41 | 1.500 (4) |
O1—N5i | 2.742 (3) | N5—C31 | 1.503 (4) |
O2—C13 | 1.234 (3) | N5—C21 | 1.505 (4) |
C1—C2 | 1.386 (4) | N5—H5 | 0.89 (3) |
C1—H1 | 0.93 | C21—C22 | 1.495 (5) |
C2—C3 | 1.373 (4) | C21—H21A | 0.97 |
C2—H2 | 0.93 | C21—H21B | 0.97 |
C3—C4 | 1.366 (4) | C22—H22A | 0.96 |
C3—H3 | 0.93 | C22—H22B | 0.96 |
C4—C5 | 1.393 (3) | C22—H22C | 0.96 |
C4—H4 | 0.93 | C31—C32 | 1.492 (4) |
C5—C6 | 1.501 (3) | C31—H31A | 0.97 |
C7—C8 | 1.385 (3) | C31—H31B | 0.97 |
C7—C12 | 1.412 (3) | C32—H32A | 0.96 |
C8—C9 | 1.389 (4) | C32—H32B | 0.96 |
C8—H8 | 0.93 | C32—H32C | 0.96 |
C9—C10 | 1.396 (4) | C41—C42 | 1.491 (5) |
C9—C19 | 1.511 (4) | C41—H41A | 0.97 |
C10—C11 | 1.379 (3) | C41—H41B | 0.97 |
C10—C20 | 1.516 (4) | C42—H42A | 0.96 |
C11—C12 | 1.393 (3) | C42—H42B | 0.96 |
C11—H11 | 0.93 | C42—H42C | 0.96 |
C13—C14 | 1.496 (3) | | |
| | | |
N3—Fe1—N2 | 78.10 (7) | N4—C14—C13 | 117.26 (19) |
N3—Fe1—N4 | 77.47 (7) | C15—C14—C13 | 121.4 (2) |
N2—Fe1—N4 | 155.53 (8) | C16—C15—C14 | 118.8 (3) |
N3—Fe1—N1 | 155.59 (7) | C16—C15—H15 | 120.6 |
N2—Fe1—N1 | 77.58 (7) | C14—C15—H15 | 120.6 |
N4—Fe1—N1 | 126.89 (7) | C17—C16—C15 | 119.6 (2) |
N3—Fe1—Cl1 | 97.59 (6) | C17—C16—H16 | 120.2 |
N2—Fe1—Cl1 | 99.36 (6) | C15—C16—H16 | 120.2 |
N4—Fe1—Cl1 | 85.17 (6) | C16—C17—C18 | 118.9 (2) |
N1—Fe1—Cl1 | 84.42 (6) | C16—C17—H17 | 120.6 |
N3—Fe1—Cl2 | 100.74 (6) | C18—C17—H17 | 120.6 |
N2—Fe1—Cl2 | 98.57 (6) | N4—C18—C17 | 121.6 (2) |
N4—Fe1—Cl2 | 84.73 (6) | N4—C18—H18 | 119.2 |
N1—Fe1—Cl2 | 84.87 (5) | C17—C18—H18 | 119.2 |
Cl1—Fe1—Cl2 | 156.59 (3) | C9—C19—H19A | 109.5 |
C1—N1—C5 | 119.5 (2) | C9—C19—H19B | 109.5 |
C1—N1—Fe1 | 127.23 (17) | H19A—C19—H19B | 109.5 |
C5—N1—Fe1 | 113.22 (15) | C9—C19—H19C | 109.5 |
C6—N2—C7 | 124.77 (19) | H19A—C19—H19C | 109.5 |
C6—N2—Fe1 | 118.25 (15) | H19B—C19—H19C | 109.5 |
C7—N2—Fe1 | 116.02 (14) | C10—C20—H20A | 109.5 |
C13—N3—C12 | 124.05 (19) | C10—C20—H20B | 109.5 |
C13—N3—Fe1 | 119.44 (15) | H20A—C20—H20B | 109.5 |
C12—N3—Fe1 | 116.47 (14) | C10—C20—H20C | 109.5 |
C18—N4—C14 | 119.7 (2) | H20A—C20—H20C | 109.5 |
C18—N4—Fe1 | 127.12 (17) | H20B—C20—H20C | 109.5 |
C14—N4—Fe1 | 113.06 (14) | C41—N5—C31 | 111.4 (2) |
C6—O1—N5i | 172.6 (2) | C41—N5—C21 | 112.8 (2) |
N1—C1—C2 | 122.0 (3) | C31—N5—C21 | 113.5 (2) |
N1—C1—H1 | 119.0 | C41—N5—H5 | 107 (2) |
C2—C1—H1 | 119.0 | C31—N5—H5 | 105 (2) |
C3—C2—C1 | 118.7 (3) | C21—N5—H5 | 106 (2) |
C3—C2—H2 | 120.7 | C22—C21—N5 | 112.7 (3) |
C1—C2—H2 | 120.7 | C22—C21—H21A | 109.1 |
C4—C3—C2 | 119.4 (3) | N5—C21—H21A | 109.1 |
C4—C3—H3 | 120.3 | C22—C21—H21B | 109.1 |
C2—C3—H3 | 120.3 | N5—C21—H21B | 109.1 |
C3—C4—C5 | 119.3 (3) | H21A—C21—H21B | 107.8 |
C3—C4—H4 | 120.4 | C21—C22—H22A | 109.5 |
C5—C4—H4 | 120.4 | C21—C22—H22B | 109.5 |
N1—C5—C4 | 121.1 (2) | H22A—C22—H22B | 109.5 |
N1—C5—C6 | 116.6 (2) | C21—C22—H22C | 109.5 |
C4—C5—C6 | 122.2 (2) | H22A—C22—H22C | 109.5 |
O1—C6—N2 | 128.1 (2) | H22B—C22—H22C | 109.5 |
O1—C6—C5 | 118.1 (2) | C32—C31—N5 | 114.2 (3) |
N2—C6—C5 | 113.83 (19) | C32—C31—H31A | 108.7 |
C8—C7—N2 | 127.1 (2) | N5—C31—H31A | 108.7 |
C8—C7—C12 | 118.4 (2) | C32—C31—H31B | 108.7 |
N2—C7—C12 | 114.47 (19) | N5—C31—H31B | 108.7 |
C7—C8—C9 | 122.1 (2) | H31A—C31—H31B | 107.6 |
C7—C8—H8 | 118.9 | C31—C32—H32A | 109.5 |
C9—C8—H8 | 118.9 | C31—C32—H32B | 109.5 |
C8—C9—C10 | 119.2 (2) | H32A—C32—H32B | 109.5 |
C8—C9—C19 | 119.7 (3) | C31—C32—H32C | 109.5 |
C10—C9—C19 | 121.1 (2) | H32A—C32—H32C | 109.5 |
C11—C10—C9 | 119.0 (2) | H32B—C32—H32C | 109.5 |
C11—C10—C20 | 119.0 (2) | C42—C41—N5 | 112.7 (2) |
C9—C10—C20 | 121.9 (2) | C42—C41—H41A | 109.0 |
C10—C11—C12 | 122.1 (2) | N5—C41—H41A | 109.0 |
C10—C11—H11 | 119.0 | C42—C41—H41B | 109.0 |
C12—C11—H11 | 119.0 | N5—C41—H41B | 109.0 |
C11—C12—N3 | 126.4 (2) | H41A—C41—H41B | 107.8 |
C11—C12—C7 | 118.8 (2) | C41—C42—H42A | 109.5 |
N3—C12—C7 | 114.6 (2) | C41—C42—H42B | 109.5 |
O2—C13—N3 | 128.8 (2) | H42A—C42—H42B | 109.5 |
O2—C13—C14 | 118.8 (2) | C41—C42—H42C | 109.5 |
N3—C13—C14 | 112.41 (19) | H42A—C42—H42C | 109.5 |
N4—C14—C15 | 121.3 (2) | H42B—C42—H42C | 109.5 |
| | | |
N3—Fe1—N1—C1 | 178.0 (2) | Fe1—N2—C6—C5 | 7.3 (3) |
N2—Fe1—N1—C1 | −177.2 (2) | N1—C5—C6—O1 | 176.8 (2) |
N4—Fe1—N1—C1 | 2.3 (2) | C4—C5—C6—O1 | −3.4 (4) |
Cl1—Fe1—N1—C1 | 82.0 (2) | N1—C5—C6—N2 | −3.3 (3) |
Cl2—Fe1—N1—C1 | −77.2 (2) | C4—C5—C6—N2 | 176.5 (2) |
N3—Fe1—N1—C5 | −0.5 (3) | C6—N2—C7—C8 | 9.4 (4) |
N2—Fe1—N1—C5 | 4.29 (15) | Fe1—N2—C7—C8 | 177.97 (19) |
N4—Fe1—N1—C5 | −176.27 (14) | C6—N2—C7—C12 | −167.9 (2) |
Cl1—Fe1—N1—C5 | −96.59 (16) | Fe1—N2—C7—C12 | 0.6 (2) |
Cl2—Fe1—N1—C5 | 104.25 (16) | N2—C7—C8—C9 | −172.5 (2) |
N3—Fe1—N2—C6 | 171.47 (18) | C12—C7—C8—C9 | 4.8 (4) |
N4—Fe1—N2—C6 | 174.60 (18) | C7—C8—C9—C10 | 0.6 (4) |
N1—Fe1—N2—C6 | −6.50 (17) | C7—C8—C9—C19 | 178.8 (3) |
Cl1—Fe1—N2—C6 | 75.62 (17) | C8—C9—C10—C11 | −5.2 (4) |
Cl2—Fe1—N2—C6 | −89.27 (17) | C19—C9—C10—C11 | 176.6 (3) |
N3—Fe1—N2—C7 | 2.14 (15) | C8—C9—C10—C20 | 174.1 (3) |
N4—Fe1—N2—C7 | 5.3 (3) | C19—C9—C10—C20 | −4.1 (4) |
N1—Fe1—N2—C7 | −175.83 (16) | C9—C10—C11—C12 | 4.4 (4) |
Cl1—Fe1—N2—C7 | −93.71 (15) | C20—C10—C11—C12 | −174.9 (2) |
Cl2—Fe1—N2—C7 | 101.40 (15) | C10—C11—C12—N3 | 177.1 (2) |
N2—Fe1—N3—C13 | 173.44 (18) | C10—C11—C12—C7 | 1.0 (3) |
N4—Fe1—N3—C13 | −5.24 (16) | C13—N3—C12—C11 | 12.1 (4) |
N1—Fe1—N3—C13 | 178.24 (17) | Fe1—N3—C12—C11 | −169.83 (18) |
Cl1—Fe1—N3—C13 | −88.54 (16) | C13—N3—C12—C7 | −171.5 (2) |
Cl2—Fe1—N3—C13 | 76.83 (17) | Fe1—N3—C12—C7 | 6.5 (2) |
N2—Fe1—N3—C12 | −4.68 (15) | C8—C7—C12—C11 | −5.5 (3) |
N4—Fe1—N3—C12 | 176.64 (17) | N2—C7—C12—C11 | 172.1 (2) |
N1—Fe1—N3—C12 | 0.1 (3) | C8—C7—C12—N3 | 177.9 (2) |
Cl1—Fe1—N3—C12 | 93.34 (15) | N2—C7—C12—N3 | −4.5 (3) |
Cl2—Fe1—N3—C12 | −101.28 (15) | C12—N3—C13—O2 | 1.3 (4) |
N3—Fe1—N4—C18 | −178.5 (2) | Fe1—N3—C13—O2 | −176.70 (19) |
N2—Fe1—N4—C18 | 178.34 (19) | C12—N3—C13—C14 | −177.75 (19) |
N1—Fe1—N4—C18 | −0.3 (2) | Fe1—N3—C13—C14 | 4.3 (2) |
Cl1—Fe1—N4—C18 | −79.6 (2) | C18—N4—C14—C15 | −2.3 (4) |
Cl2—Fe1—N4—C18 | 79.2 (2) | Fe1—N4—C14—C15 | 174.34 (19) |
N3—Fe1—N4—C14 | 5.15 (16) | C18—N4—C14—C13 | 178.7 (2) |
N2—Fe1—N4—C14 | 2.0 (3) | Fe1—N4—C14—C13 | −4.7 (2) |
N1—Fe1—N4—C14 | −176.65 (14) | O2—C13—C14—N4 | −178.6 (2) |
Cl1—Fe1—N4—C14 | 104.04 (16) | N3—C13—C14—N4 | 0.6 (3) |
Cl2—Fe1—N4—C14 | −97.10 (16) | O2—C13—C14—C15 | 2.4 (3) |
C5—N1—C1—C2 | −0.2 (4) | N3—C13—C14—C15 | −178.4 (2) |
Fe1—N1—C1—C2 | −178.7 (2) | N4—C14—C15—C16 | 1.2 (4) |
N1—C1—C2—C3 | 0.3 (4) | C13—C14—C15—C16 | −179.9 (2) |
C1—C2—C3—C4 | 0.4 (4) | C14—C15—C16—C17 | 1.0 (4) |
C2—C3—C4—C5 | −1.0 (4) | C15—C16—C17—C18 | −2.0 (4) |
C1—N1—C5—C4 | −0.4 (4) | C14—N4—C18—C17 | 1.2 (4) |
Fe1—N1—C5—C4 | 178.26 (19) | Fe1—N4—C18—C17 | −174.9 (2) |
C1—N1—C5—C6 | 179.4 (2) | C16—C17—C18—N4 | 0.9 (4) |
Fe1—N1—C5—C6 | −1.9 (3) | C41—N5—C21—C22 | −168.7 (3) |
C3—C4—C5—N1 | 1.0 (4) | C31—N5—C21—C22 | 63.5 (4) |
C3—C4—C5—C6 | −178.7 (2) | C41—N5—C31—C32 | −63.0 (3) |
C7—N2—C6—O1 | −4.5 (4) | C21—N5—C31—C32 | 65.5 (4) |
Fe1—N2—C6—O1 | −172.8 (2) | C31—N5—C41—C42 | −163.1 (3) |
C7—N2—C6—C5 | 175.64 (19) | C21—N5—C41—C42 | 68.0 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | (C6H16N)[FeCl2(C20H16N4O2)] |
Mr | 573.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 11.0038 (10), 16.273 (2), 15.578 (2) |
β (°) | 100.789 (10) |
V (Å3) | 2740.2 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.35 × 0.35 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 MACH3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5637, 5352, 4515 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.120, 1.04 |
No. of reflections | 5352 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −0.64 |
Selected geometric parameters (Å, º) topFe1—N3 | 2.0408 (19) | Fe1—Cl2 | 2.3546 (7) |
Fe1—N2 | 2.0535 (18) | O1—C6 | 1.243 (3) |
Fe1—N4 | 2.1438 (19) | O1—N5i | 2.742 (3) |
Fe1—N1 | 2.1531 (19) | O2—C13 | 1.234 (3) |
Fe1—Cl1 | 2.3457 (7) | | |
| | | |
N3—Fe1—N2 | 78.10 (7) | N4—Fe1—Cl1 | 85.17 (6) |
N3—Fe1—N4 | 77.47 (7) | N1—Fe1—Cl1 | 84.42 (6) |
N2—Fe1—N4 | 155.53 (8) | N3—Fe1—Cl2 | 100.74 (6) |
N3—Fe1—N1 | 155.59 (7) | N2—Fe1—Cl2 | 98.57 (6) |
N2—Fe1—N1 | 77.58 (7) | N4—Fe1—Cl2 | 84.73 (6) |
N4—Fe1—N1 | 126.89 (7) | N1—Fe1—Cl2 | 84.87 (5) |
N3—Fe1—Cl1 | 97.59 (6) | Cl1—Fe1—Cl2 | 156.59 (3) |
N2—Fe1—Cl1 | 99.36 (6) | | |
| | | |
C6—N2—C7—C8 | 9.4 (4) | C13—N3—C12—C11 | 12.1 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
The discovery that mononuclear nonheme iron proteins, such as lipoxygenase, isopenicillin N synthase and phenylalanine hydroxylase, can oxidize inert substrates selectively has stimulated chemists to investigate the biomimetic reactions of nonheme iron complexes with various oxidants, H2O2, iodosylbenzene (PhIO), m-chloroperbenzoic acid (MCPBA), and etc. (Que & Ho, 1996). However, few examples have shown the biomimetic reactivity in a nonheme ligand environment (Chen & Que, 2001; Kim et al., 1997; Leung et al., 1991; Mekmouche et al., 2001). Yang et al. have first reported the crystal structure of the complex, [(Et3NH)Fe(bpb)X2] [H2bpb is 1,2-bis(2-pyridinecarboxamido)benzene; X = Cl- and OTf-], with a tetradentate pyridine/amide ligand, and have found that it can catalyze the epoxidation of olefins by iodosylbenzene (Yang et al., 1991). In order to further develop functional models for mononuclear nonheme iron oxygenases, therefore, we have studied on a family of the nonheme iron catalyst, represented by [(bpb)FeCl2]. First of all, to examine the electronic effect of the ligand on the reactivity of the complex [(bpb)FeCl2], we have synthesized the title complex, with two methyl groups on the phenyl ring of the bpb ligand, H2Me2bpb [1,2-bis(2-pyridinecarboxamido)-4,5-dimethylbenzene] and obtained the crystal of its iron(III) complex. We now report the structure of an electron-rich iron complex [Et3NH][(Me2bpb)FeCl2], (I).
The asymmetric unit contains an [(Me2bpb)FeCl2]- anion and a triethylammonium cation [Et3NH]+ in P21/n with Z = 4. Four N atoms of the Me2bpb2- ligand are coordinated to the iron(III) ion. The Fe—N distances range from 2.041 (2) to 2.153 (2) Å. Two chloro ligands are also coordinted to the iron(III) ion, with Fe—Cl distances of 2.3457 (7) and 2.3546 (7) Å. The geometry of the anion complex is distorted octahedral, with a Cl—Fe—Cl angle of 156.59 (3)°. The N1—Fe1—N3 and N2—Fe1—N4 angles are 155.59 (7) and 155.53 (8)°, respectively. The 4,5-dimethylbenzene ring of the Me2bpb2- ligand is tilted from the N1/N2/N3/N4 plane, with torsion angles of 9.4 (4) and 12.1 (4)° for C6—N2—C7—C8 and C13—N3—C12—C11, respectively. The C—O bond distances of the Me2bpb2- ligand are 1.243 (3) and 1.234 (3) Å. There is an intermolecular interaction between the N atom of a triethylammonium cation and the carbonyl O atom of next anion complex, with an N5···O1 distance of 2.73 (1) Å.