Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301345X/ac6045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680301345X/ac6045Isup2.hkl |
CCDC reference: 217385
Key indicators
- Single-crystal X-ray study
- T = 91 K
- Mean (C-C) = 0.002 Å
- R factor = 0.029
- wR factor = 0.075
- Data-to-parameter ratio = 26.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.48 From the CIF: _reflns_number_total 9258 Count of symmetry unique reflns 5409 Completeness (_total/calc) 171.16% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3849 Fraction of Friedel pairs measured 0.712 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
All chemicals were purchased from Acros and used without further purification. Acetonitrile was dried using appropriate procedures, and the recrystallization was performed using standard Schlenk techniques. The synthesis of ligand N-(2,6-diisopropylphenyl)-2-[(di-2-pyridylmethyl)amino]ethanamide will be described in a subsequent publication (Troeltzsch et al., 2003). The ligand (1.02 g, 2.37 mmol) was dissolved in 25 ml of THF, and then 0.472 g (2.38 mmol) of FeCl2·4H2O was added. The solution was stirred and then concentrated to dryness. The solid was dissolved in boiling, dry acetonitrile, and upon cooling amber needles formed suitable for X-ray analysis [m.p. 446 K (decomposition)]. Elemental composition, calculated: C 58.21, H 6.23, N 11.70%; found: C 57.09, H 6.14, N 11.69%. IR (Thin film, NaCl plates) ν (cm-1): 3410 (broad), 1607 (s), 1563 (m).
H atoms were placed in idealized positions and refined using a model whereby the H atom was riding on the bonded carbon with an Uiso value equal to 1.2 (1.5 for methyl H) times the Ueq value of the bonded carbon.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. View of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
[FeCl2(C27H34N4O)]·CH3CN | Dx = 1.346 Mg m−3 |
Mr = 598.39 | Melting point: 446 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7272 reflections |
a = 13.1579 (4) Å | θ = 2.5–31.4° |
b = 14.2791 (5) Å | µ = 0.72 mm−1 |
c = 15.7210 (5) Å | T = 91 K |
V = 2953.71 (17) Å3 | Needle, brown |
Z = 4 | 0.27 × 0.27 × 0.22 mm |
F(000) = 1256 |
Bruker SMART 1000 diffractometer | 9258 independent reflections |
Radiation source: normal-focus sealed tube | 8527 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 8.2 pixels mm-1 | θmax = 31.5°, θmin = 1.9° |
ω scans | h = −19→19 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −20→20 |
Tmin = 0.829, Tmax = 0.857 | l = −22→22 |
27291 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0464P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
9258 reflections | Δρmax = 0.53 e Å−3 |
348 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Absolute structure: 3928 Friedel pairs were measured for determination of the Flack parameter Flack (1983). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.015 (8) |
[FeCl2(C27H34N4O)]·CH3CN | V = 2953.71 (17) Å3 |
Mr = 598.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.1579 (4) Å | µ = 0.72 mm−1 |
b = 14.2791 (5) Å | T = 91 K |
c = 15.7210 (5) Å | 0.27 × 0.27 × 0.22 mm |
Bruker SMART 1000 diffractometer | 9258 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 8527 reflections with I > 2σ(I) |
Tmin = 0.829, Tmax = 0.857 | Rint = 0.023 |
27291 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 0.53 e Å−3 |
S = 1.07 | Δρmin = −0.22 e Å−3 |
9258 reflections | Absolute structure: 3928 Friedel pairs were measured for determination of the Flack parameter Flack (1983). |
348 parameters | Absolute structure parameter: −0.015 (8) |
0 restraints |
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 | ||
Fe1 | 0.713985 (15) | 0.972432 (13) | 0.944912 (12) | 0.01420 (5) | |
Cl1 | 0.75938 (3) | 0.85357 (2) | 1.03967 (2) | 0.01847 (7) | |
Cl2 | 0.58245 (3) | 1.05705 (2) | 1.03564 (2) | 0.01755 (7) | |
O1 | 0.80662 (8) | 0.90524 (8) | 0.84702 (7) | 0.0181 (2) | |
N1 | 0.82842 (10) | 1.07675 (9) | 0.97473 (9) | 0.0192 (3) | |
N2 | 0.58382 (11) | 0.92640 (9) | 0.87390 (8) | 0.0197 (3) | |
N3 | 0.69149 (10) | 1.08964 (9) | 0.84539 (9) | 0.0184 (2) | |
N4 | 0.86896 (10) | 0.85919 (9) | 0.71966 (8) | 0.0161 (2) | |
H4A | 0.8824 | 0.8773 | 0.6673 | 0.019* | |
C1 | 0.91379 (13) | 1.05968 (11) | 1.01947 (11) | 0.0227 (3) | |
H1 | 0.9211 | 1.0005 | 1.0465 | 0.027* | |
C2 | 0.99117 (14) | 1.12454 (13) | 1.02774 (12) | 0.0281 (4) | |
H2 | 1.0505 | 1.1102 | 1.0596 | 0.034* | |
C3 | 0.98032 (15) | 1.21080 (14) | 0.98872 (13) | 0.0320 (4) | |
H3 | 1.0329 | 1.2562 | 0.9924 | 0.038* | |
C4 | 0.89223 (13) | 1.23014 (11) | 0.94435 (12) | 0.0268 (3) | |
H4 | 0.8829 | 1.2894 | 0.9180 | 0.032* | |
C5 | 0.81731 (12) | 1.16169 (10) | 0.93884 (11) | 0.0211 (3) | |
C6 | 0.71766 (13) | 1.17651 (10) | 0.89280 (10) | 0.0213 (3) | |
H6A | 0.6633 | 1.1913 | 0.9343 | 0.026* | |
H6B | 0.7238 | 1.2297 | 0.8528 | 0.026* | |
C7 | 0.58364 (13) | 1.08689 (12) | 0.82105 (11) | 0.0228 (3) | |
H7A | 0.5757 | 1.1153 | 0.7640 | 0.027* | |
H7B | 0.5438 | 1.1249 | 0.8619 | 0.027* | |
C8 | 0.54166 (12) | 0.98849 (11) | 0.81940 (10) | 0.0200 (3) | |
C9 | 0.45969 (13) | 0.96431 (13) | 0.76778 (11) | 0.0264 (3) | |
H9 | 0.4335 | 1.0075 | 0.7274 | 0.032* | |
C10 | 0.41723 (14) | 0.87638 (14) | 0.77653 (12) | 0.0303 (4) | |
H10 | 0.3607 | 0.8588 | 0.7426 | 0.036* | |
C11 | 0.45758 (14) | 0.81370 (13) | 0.83526 (12) | 0.0291 (4) | |
H11 | 0.4278 | 0.7538 | 0.8436 | 0.035* | |
C12 | 0.54264 (13) | 0.84118 (12) | 0.88140 (11) | 0.0240 (3) | |
H12 | 0.5726 | 0.7978 | 0.9197 | 0.029* | |
C13 | 0.76084 (13) | 1.08697 (11) | 0.77053 (10) | 0.0203 (3) | |
H13A | 0.8308 | 1.1005 | 0.7902 | 0.024* | |
H13B | 0.7409 | 1.1376 | 0.7309 | 0.024* | |
C14 | 0.76199 (12) | 0.99529 (11) | 0.72210 (10) | 0.0201 (3) | |
H14A | 0.6911 | 0.9760 | 0.7103 | 0.024* | |
H14B | 0.7963 | 1.0051 | 0.6668 | 0.024* | |
C15 | 0.81530 (11) | 0.91727 (10) | 0.76933 (9) | 0.0161 (3) | |
C16 | 0.90592 (11) | 0.76933 (10) | 0.74647 (9) | 0.0151 (3) | |
C17 | 0.98788 (11) | 0.76245 (10) | 0.80272 (10) | 0.0167 (3) | |
C18 | 1.02026 (12) | 0.67263 (11) | 0.82660 (10) | 0.0191 (3) | |
H18 | 1.0750 | 0.6661 | 0.8655 | 0.023* | |
C19 | 0.97355 (13) | 0.59347 (11) | 0.79423 (11) | 0.0212 (3) | |
H19 | 0.9963 | 0.5331 | 0.8112 | 0.025* | |
C20 | 0.89360 (12) | 0.60174 (11) | 0.73706 (10) | 0.0209 (3) | |
H20 | 0.8631 | 0.5469 | 0.7143 | 0.025* | |
C21 | 0.85729 (12) | 0.68977 (10) | 0.71252 (10) | 0.0176 (3) | |
C22 | 1.04354 (12) | 0.84742 (10) | 0.83756 (10) | 0.0189 (3) | |
H22 | 1.0095 | 0.9050 | 0.8151 | 0.023* | |
C23 | 1.03971 (14) | 0.85060 (12) | 0.93484 (11) | 0.0265 (3) | |
H23A | 0.9689 | 0.8467 | 0.9538 | 0.040* | |
H23B | 1.0696 | 0.9094 | 0.9549 | 0.040* | |
H23C | 1.0782 | 0.7977 | 0.9581 | 0.040* | |
C24 | 1.15450 (12) | 0.84763 (12) | 0.80676 (11) | 0.0229 (3) | |
H24A | 1.1877 | 0.7892 | 0.8242 | 0.034* | |
H24B | 1.1905 | 0.9010 | 0.8319 | 0.034* | |
H24C | 1.1560 | 0.8528 | 0.7446 | 0.034* | |
C25 | 0.76486 (12) | 0.70013 (11) | 0.65500 (10) | 0.0213 (3) | |
H25 | 0.7777 | 0.7538 | 0.6156 | 0.026* | |
C26 | 0.74310 (16) | 0.61331 (13) | 0.60082 (12) | 0.0307 (4) | |
H26A | 0.8039 | 0.5970 | 0.5680 | 0.046* | |
H26B | 0.6868 | 0.6265 | 0.5618 | 0.046* | |
H26C | 0.7247 | 0.5609 | 0.6380 | 0.046* | |
C27 | 0.67034 (13) | 0.72393 (13) | 0.70881 (13) | 0.0278 (4) | |
H27A | 0.6543 | 0.6711 | 0.7463 | 0.042* | |
H27B | 0.6125 | 0.7361 | 0.6711 | 0.042* | |
H27C | 0.6841 | 0.7797 | 0.7432 | 0.042* | |
N5 | 0.71807 (16) | 0.47898 (16) | 0.88458 (12) | 0.0502 (5) | |
C28 | 0.76392 (16) | 0.53398 (17) | 0.92082 (12) | 0.0382 (5) | |
C29 | 0.82307 (18) | 0.60265 (18) | 0.96872 (16) | 0.0486 (6) | |
H29A | 0.7916 | 0.6126 | 1.0245 | 0.073* | |
H29B | 0.8248 | 0.6620 | 0.9374 | 0.073* | |
H29C | 0.8925 | 0.5794 | 0.9764 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01621 (9) | 0.01389 (8) | 0.01250 (9) | 0.00141 (7) | 0.00049 (7) | 0.00111 (7) |
Cl1 | 0.02268 (16) | 0.01662 (13) | 0.01612 (15) | 0.00270 (12) | 0.00246 (12) | 0.00357 (12) |
Cl2 | 0.01952 (16) | 0.01894 (14) | 0.01420 (15) | 0.00279 (12) | 0.00081 (12) | −0.00129 (11) |
O1 | 0.0206 (5) | 0.0199 (5) | 0.0138 (5) | 0.0044 (4) | 0.0023 (4) | 0.0022 (4) |
N1 | 0.0192 (6) | 0.0167 (6) | 0.0219 (6) | −0.0001 (5) | 0.0024 (5) | −0.0004 (5) |
N2 | 0.0197 (6) | 0.0218 (6) | 0.0176 (6) | 0.0014 (5) | 0.0015 (5) | −0.0031 (5) |
N3 | 0.0198 (6) | 0.0179 (5) | 0.0174 (6) | 0.0038 (5) | 0.0024 (5) | 0.0012 (5) |
N4 | 0.0202 (6) | 0.0153 (5) | 0.0126 (5) | 0.0035 (5) | 0.0012 (4) | 0.0024 (4) |
C1 | 0.0217 (7) | 0.0224 (7) | 0.0242 (7) | −0.0003 (6) | 0.0013 (6) | −0.0028 (6) |
C2 | 0.0237 (8) | 0.0321 (9) | 0.0285 (9) | −0.0045 (6) | −0.0031 (6) | −0.0041 (7) |
C3 | 0.0332 (10) | 0.0311 (9) | 0.0318 (9) | −0.0123 (8) | −0.0009 (8) | −0.0019 (7) |
C4 | 0.0336 (9) | 0.0188 (7) | 0.0279 (8) | −0.0055 (6) | 0.0024 (7) | 0.0014 (7) |
C5 | 0.0228 (7) | 0.0180 (6) | 0.0226 (7) | 0.0000 (5) | 0.0043 (6) | −0.0011 (6) |
C6 | 0.0224 (7) | 0.0162 (6) | 0.0251 (7) | 0.0009 (6) | 0.0029 (6) | 0.0028 (5) |
C7 | 0.0236 (8) | 0.0225 (7) | 0.0223 (8) | 0.0058 (6) | −0.0045 (6) | 0.0003 (6) |
C8 | 0.0166 (6) | 0.0245 (7) | 0.0190 (7) | 0.0026 (6) | −0.0007 (5) | −0.0020 (6) |
C9 | 0.0207 (7) | 0.0347 (9) | 0.0238 (8) | 0.0050 (7) | −0.0045 (6) | −0.0052 (7) |
C10 | 0.0186 (7) | 0.0406 (10) | 0.0317 (9) | −0.0007 (7) | −0.0028 (7) | −0.0106 (7) |
C11 | 0.0271 (8) | 0.0292 (8) | 0.0309 (9) | −0.0078 (7) | 0.0046 (7) | −0.0084 (7) |
C12 | 0.0233 (8) | 0.0271 (8) | 0.0214 (8) | −0.0019 (6) | 0.0016 (6) | −0.0039 (6) |
C13 | 0.0238 (8) | 0.0179 (6) | 0.0192 (7) | 0.0007 (5) | 0.0033 (6) | 0.0025 (5) |
C14 | 0.0234 (8) | 0.0202 (6) | 0.0166 (6) | 0.0054 (5) | 0.0016 (5) | 0.0024 (5) |
C15 | 0.0158 (6) | 0.0146 (6) | 0.0179 (7) | 0.0009 (5) | 0.0014 (5) | 0.0013 (5) |
C16 | 0.0156 (6) | 0.0144 (6) | 0.0153 (6) | 0.0035 (5) | 0.0024 (5) | 0.0015 (5) |
C17 | 0.0159 (7) | 0.0159 (6) | 0.0181 (7) | 0.0013 (5) | 0.0016 (5) | 0.0007 (5) |
C18 | 0.0177 (7) | 0.0190 (7) | 0.0207 (7) | 0.0016 (5) | −0.0012 (6) | 0.0021 (5) |
C19 | 0.0243 (8) | 0.0140 (6) | 0.0253 (8) | 0.0018 (6) | 0.0005 (6) | 0.0019 (5) |
C20 | 0.0227 (7) | 0.0156 (7) | 0.0244 (8) | −0.0006 (6) | −0.0009 (6) | 0.0004 (6) |
C21 | 0.0182 (7) | 0.0175 (6) | 0.0170 (7) | 0.0007 (5) | 0.0006 (5) | −0.0001 (5) |
C22 | 0.0173 (6) | 0.0156 (6) | 0.0238 (7) | 0.0009 (5) | −0.0016 (5) | −0.0001 (5) |
C23 | 0.0280 (8) | 0.0273 (8) | 0.0241 (8) | 0.0008 (6) | 0.0000 (6) | −0.0068 (7) |
C24 | 0.0194 (7) | 0.0207 (7) | 0.0286 (8) | −0.0015 (6) | 0.0005 (6) | 0.0013 (6) |
C25 | 0.0227 (8) | 0.0199 (7) | 0.0211 (7) | 0.0006 (6) | −0.0036 (6) | −0.0012 (5) |
C26 | 0.0344 (9) | 0.0288 (8) | 0.0290 (9) | 0.0006 (7) | −0.0091 (7) | −0.0071 (7) |
C27 | 0.0199 (8) | 0.0280 (8) | 0.0353 (10) | −0.0004 (6) | −0.0031 (7) | −0.0046 (7) |
N5 | 0.0455 (11) | 0.0742 (14) | 0.0308 (8) | −0.0239 (11) | −0.0039 (8) | 0.0035 (9) |
C28 | 0.0319 (10) | 0.0568 (13) | 0.0258 (8) | −0.0118 (9) | 0.0038 (7) | 0.0025 (8) |
C29 | 0.0427 (12) | 0.0600 (14) | 0.0431 (13) | −0.0189 (11) | 0.0141 (10) | −0.0188 (11) |
Fe1—N2 | 2.1475 (14) | C13—H13A | 0.9900 |
Fe1—N1 | 2.1693 (13) | C13—H13B | 0.9900 |
Fe1—O1 | 2.1850 (11) | C14—C15 | 1.512 (2) |
Fe1—N3 | 2.3101 (13) | C14—H14A | 0.9900 |
Fe1—Cl1 | 2.3360 (4) | C14—H14B | 0.9900 |
Fe1—Cl2 | 2.5474 (4) | C16—C17 | 1.398 (2) |
O1—C15 | 1.2387 (18) | C16—C21 | 1.409 (2) |
N1—C5 | 1.3455 (19) | C17—C18 | 1.403 (2) |
N1—C1 | 1.347 (2) | C17—C22 | 1.519 (2) |
N2—C12 | 1.337 (2) | C18—C19 | 1.384 (2) |
N2—C8 | 1.352 (2) | C18—H18 | 0.9500 |
N3—C7 | 1.470 (2) | C19—C20 | 1.389 (2) |
N3—C6 | 1.487 (2) | C19—H19 | 0.9500 |
N3—C13 | 1.490 (2) | C20—C21 | 1.399 (2) |
N4—C15 | 1.3403 (18) | C20—H20 | 0.9500 |
N4—C16 | 1.4354 (18) | C21—C25 | 1.523 (2) |
N4—H4A | 0.8800 | C22—C23 | 1.531 (2) |
C1—C2 | 1.383 (2) | C22—C24 | 1.538 (2) |
C1—H1 | 0.9500 | C22—H22 | 1.0000 |
C2—C3 | 1.383 (3) | C23—H23A | 0.9800 |
C2—H2 | 0.9500 | C23—H23B | 0.9800 |
C3—C4 | 1.381 (3) | C23—H23C | 0.9800 |
C3—H3 | 0.9500 | C24—H24A | 0.9800 |
C4—C5 | 1.391 (2) | C24—H24B | 0.9800 |
C4—H4 | 0.9500 | C24—H24C | 0.9800 |
C5—C6 | 1.513 (2) | C25—C26 | 1.531 (2) |
C6—H6A | 0.9900 | C25—C27 | 1.542 (2) |
C6—H6B | 0.9900 | C25—H25 | 1.0000 |
C7—C8 | 1.510 (2) | C26—H26A | 0.9800 |
C7—H7A | 0.9900 | C26—H26B | 0.9800 |
C7—H7B | 0.9900 | C26—H26C | 0.9800 |
C8—C9 | 1.393 (2) | C27—H27A | 0.9800 |
C9—C10 | 1.381 (3) | C27—H27B | 0.9800 |
C9—H9 | 0.9500 | C27—H27C | 0.9800 |
C10—C11 | 1.391 (3) | N5—C28 | 1.142 (3) |
C10—H10 | 0.9500 | C28—C29 | 1.461 (3) |
C11—C12 | 1.390 (2) | C29—H29A | 0.9800 |
C11—H11 | 0.9500 | C29—H29B | 0.9800 |
C12—H12 | 0.9500 | C29—H29C | 0.9800 |
C13—C14 | 1.514 (2) | ||
N2—Fe1—N1 | 151.17 (5) | C14—C13—H13A | 108.5 |
N2—Fe1—O1 | 86.81 (5) | N3—C13—H13B | 108.5 |
N1—Fe1—O1 | 93.81 (5) | C14—C13—H13B | 108.5 |
N2—Fe1—N3 | 76.56 (5) | H13A—C13—H13B | 107.5 |
N1—Fe1—N3 | 74.80 (5) | C15—C14—C13 | 113.25 (13) |
O1—Fe1—N3 | 84.99 (4) | C15—C14—H14A | 108.9 |
N2—Fe1—Cl1 | 108.24 (4) | C13—C14—H14A | 108.9 |
N1—Fe1—Cl1 | 100.58 (4) | C15—C14—H14B | 108.9 |
O1—Fe1—Cl1 | 89.28 (3) | C13—C14—H14B | 108.9 |
N3—Fe1—Cl1 | 172.34 (3) | H14A—C14—H14B | 107.7 |
N2—Fe1—Cl2 | 83.94 (4) | O1—C15—N4 | 122.50 (13) |
N1—Fe1—Cl2 | 91.43 (4) | O1—C15—C14 | 122.95 (13) |
O1—Fe1—Cl2 | 168.98 (3) | N4—C15—C14 | 114.48 (13) |
N3—Fe1—Cl2 | 87.05 (3) | C17—C16—C21 | 122.23 (13) |
Cl1—Fe1—Cl2 | 99.280 (13) | C17—C16—N4 | 120.66 (13) |
C15—O1—Fe1 | 133.24 (10) | C21—C16—N4 | 117.10 (13) |
C5—N1—C1 | 118.20 (14) | C16—C17—C18 | 117.90 (14) |
C5—N1—Fe1 | 116.93 (11) | C16—C17—C22 | 122.93 (13) |
C1—N1—Fe1 | 124.55 (10) | C18—C17—C22 | 119.16 (13) |
C12—N2—C8 | 119.10 (14) | C19—C18—C17 | 120.91 (14) |
C12—N2—Fe1 | 123.77 (11) | C19—C18—H18 | 119.5 |
C8—N2—Fe1 | 117.13 (11) | C17—C18—H18 | 119.5 |
C7—N3—C6 | 112.09 (12) | C18—C19—C20 | 120.33 (14) |
C7—N3—C13 | 112.63 (13) | C18—C19—H19 | 119.8 |
C6—N3—C13 | 105.99 (12) | C20—C19—H19 | 119.8 |
C7—N3—Fe1 | 106.29 (10) | C19—C20—C21 | 120.91 (14) |
C6—N3—Fe1 | 103.60 (9) | C19—C20—H20 | 119.5 |
C13—N3—Fe1 | 115.98 (9) | C21—C20—H20 | 119.5 |
C15—N4—C16 | 124.09 (12) | C20—C21—C16 | 117.70 (14) |
C15—N4—H4A | 118.0 | C20—C21—C25 | 121.60 (14) |
C16—N4—H4A | 118.0 | C16—C21—C25 | 120.62 (13) |
N1—C1—C2 | 122.81 (16) | C17—C22—C23 | 111.59 (13) |
N1—C1—H1 | 118.6 | C17—C22—C24 | 110.22 (13) |
C2—C1—H1 | 118.6 | C23—C22—C24 | 110.22 (14) |
C1—C2—C3 | 118.60 (17) | C17—C22—H22 | 108.2 |
C1—C2—H2 | 120.7 | C23—C22—H22 | 108.2 |
C3—C2—H2 | 120.7 | C24—C22—H22 | 108.2 |
C4—C3—C2 | 119.25 (17) | C22—C23—H23A | 109.5 |
C4—C3—H3 | 120.4 | C22—C23—H23B | 109.5 |
C2—C3—H3 | 120.4 | H23A—C23—H23B | 109.5 |
C3—C4—C5 | 119.07 (16) | C22—C23—H23C | 109.5 |
C3—C4—H4 | 120.5 | H23A—C23—H23C | 109.5 |
C5—C4—H4 | 120.5 | H23B—C23—H23C | 109.5 |
N1—C5—C4 | 122.02 (16) | C22—C24—H24A | 109.5 |
N1—C5—C6 | 114.89 (13) | C22—C24—H24B | 109.5 |
C4—C5—C6 | 123.08 (14) | H24A—C24—H24B | 109.5 |
N3—C6—C5 | 108.89 (12) | C22—C24—H24C | 109.5 |
N3—C6—H6A | 109.9 | H24A—C24—H24C | 109.5 |
C5—C6—H6A | 109.9 | H24B—C24—H24C | 109.5 |
N3—C6—H6B | 109.9 | C21—C25—C26 | 113.64 (14) |
C5—C6—H6B | 109.9 | C21—C25—C27 | 109.87 (13) |
H6A—C6—H6B | 108.3 | C26—C25—C27 | 109.44 (14) |
N3—C7—C8 | 112.48 (13) | C21—C25—H25 | 107.9 |
N3—C7—H7A | 109.1 | C26—C25—H25 | 107.9 |
C8—C7—H7A | 109.1 | C27—C25—H25 | 107.9 |
N3—C7—H7B | 109.1 | C25—C26—H26A | 109.5 |
C8—C7—H7B | 109.1 | C25—C26—H26B | 109.5 |
H7A—C7—H7B | 107.8 | H26A—C26—H26B | 109.5 |
N2—C8—C9 | 121.62 (15) | C25—C26—H26C | 109.5 |
N2—C8—C7 | 116.69 (13) | H26A—C26—H26C | 109.5 |
C9—C8—C7 | 121.59 (15) | H26B—C26—H26C | 109.5 |
C10—C9—C8 | 118.71 (17) | C25—C27—H27A | 109.5 |
C10—C9—H9 | 120.6 | C25—C27—H27B | 109.5 |
C8—C9—H9 | 120.6 | H27A—C27—H27B | 109.5 |
C9—C10—C11 | 119.78 (16) | C25—C27—H27C | 109.5 |
C9—C10—H10 | 120.1 | H27A—C27—H27C | 109.5 |
C11—C10—H10 | 120.1 | H27B—C27—H27C | 109.5 |
C12—C11—C10 | 118.16 (17) | N5—C28—C29 | 178.6 (3) |
C12—C11—H11 | 120.9 | C28—C29—H29A | 109.5 |
C10—C11—H11 | 120.9 | C28—C29—H29B | 109.5 |
N2—C12—C11 | 122.48 (17) | H29A—C29—H29B | 109.5 |
N2—C12—H12 | 118.8 | C28—C29—H29C | 109.5 |
C11—C12—H12 | 118.8 | H29A—C29—H29C | 109.5 |
N3—C13—C14 | 115.18 (13) | H29B—C29—H29C | 109.5 |
N3—C13—H13A | 108.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···Cl2i | 0.88 | 2.32 | 3.1951 (13) | 173 |
Symmetry code: (i) −x+3/2, −y+2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [FeCl2(C27H34N4O)]·CH3CN |
Mr | 598.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 91 |
a, b, c (Å) | 13.1579 (4), 14.2791 (5), 15.7210 (5) |
V (Å3) | 2953.71 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.27 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.829, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27291, 9258, 8527 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.735 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.075, 1.07 |
No. of reflections | 9258 |
No. of parameters | 348 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.22 |
Absolute structure | 3928 Friedel pairs were measured for determination of the Flack parameter Flack (1983). |
Absolute structure parameter | −0.015 (8) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1994), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···Cl2i | 0.88 | 2.32 | 3.1951 (13) | 173 |
Symmetry code: (i) −x+3/2, −y+2, z−1/2. |
Iron coordination complexes have been studied as small molecule analogs of metalloproteins (Marlin et al., 2002; Rowland et al., 2001; Sams et al., 2001) and recently have gained considerable interest as catalysts for atom transfer reactions and controlled `living' radical polymerizations (Kamigaito et al., 2001; Matyjaszewski & Xia, 2001; Patten & Matyjaszewski, 1999). During the course of our studies on using monoanionic tetradentate ligands to prepare copper(I)–based atom transfer radical polymerization catalysts, we investigated the complexation of a bis(picolyl)amine-based ligand to iron(II) (Kobayashi et al., 1998; Niklas et al., 2000, 2001). The addition of FeCl2·4H2O to a THF solution of N-(2,6-diisopropylphenyl)-2-[(di-2-pyridylmethyl)amino]ethanamide formed the complex. An IR spectrum showed bands corresponding to the presence of the amide N—H group (3410 cm−1) and the amide carbonyl group (1607 cm−1).
The structure of the complex is monomeric with one molecule of cocrystallized acetonitrile, and the iron(II) center is in near octahedral geometry, taking into account the constraints of the tethers between the nitrogen atoms. The amide group is hydrogen bonded to a chlorine atom of the neighboring complex to form chains of complexes throughout the crystal.