Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108013498/sq3144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108013498/sq3144Isup2.hkl |
CCDC reference: 692657
For related literature, see: Gütlich et al. (1994); Goodwin (1976); Jäger et al. (1985); König (1991); Kahn & Martinez (1998); Leibeling (2003); Weber et al. (2008).
The synthesis of (I) was carried out under argon using Schlenk tube techniques. [FeL(MeOH)2] (Jäger et al., 1985) and 30 equivalents of 3-aminopyridine (Fluka) were dissolved in 40 ml of absolute methanol and heated to reflux for 1 h. 24 h later, the product was filtered off and washed two times with ice-cold methanol. Pure crystals of (I) were obtained, with a yield of 70%. Analysis found: C 54.8, H 5.5, N 10.1%; C26H32FeN4O7 requires: C 54.9, H 5.7, N 9.9%. IR (PE): ν% 3344 (w, NH), 1676 (m, COO), 1569 (m, CO) cm-1. MS (DEI+,70 eV): m/z (%) 442 (100) [M+].
With the exception of the methanol hydroxy atom H31, all H atoms were located in difference maps and treated as riding on their parent atoms (N—H = 0.88 Å and C—H = 0.95-0.98 Å). One common Uiso(H) parameter for these H atoms was refined to 0.0649 (15). Atom H31 was refined isotropically.
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Fe(C20H22N2O6)(C5H6N2)(CH4O)] | Z = 2 |
Mr = 568.40 | F(000) = 596 |
Triclinic, P1 | Dx = 1.394 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.234 (4) Å | Cell parameters from 8635 reflections |
b = 11.5760 (11) Å | θ = 3.7–26.2° |
c = 11.834 (3) Å | µ = 0.61 mm−1 |
α = 72.740 (17)° | T = 200 K |
β = 75.67 (3)° | Block, brown |
γ = 68.91 (2)° | 0.32 × 0.12 × 0.08 mm |
V = 1354.0 (6) Å3 |
Oxford XCalibur diffractometer | 2998 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 25.2°, θmin = 3.7° |
ω scans | h = −13→13 |
23067 measured reflections | k = −14→14 |
4708 independent 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.045P)2] where P = (Fo2 + 2Fc2)/3 |
4708 reflections | (Δ/σ)max < 0.001 |
353 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
[Fe(C20H22N2O6)(C5H6N2)(CH4O)] | γ = 68.91 (2)° |
Mr = 568.40 | V = 1354.0 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.234 (4) Å | Mo Kα radiation |
b = 11.5760 (11) Å | µ = 0.61 mm−1 |
c = 11.834 (3) Å | T = 200 K |
α = 72.740 (17)° | 0.32 × 0.12 × 0.08 mm |
β = 75.67 (3)° |
Oxford XCalibur diffractometer | 2998 reflections with I > 2σ(I) |
23067 measured reflections | Rint = 0.037 |
4708 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.34 e Å−3 |
4708 reflections | Δρmin = −0.21 e Å−3 |
353 parameters |
Experimental. Susceptibility measurements were performed using a Quantum Design MPMSR-XL SQUID magnetometer in the temperature range from 295 to 20 K at 500 G. |
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. C-bonded H: H-atom parameters constrained, N-bonded H: H-atom parameters constrained, anisotrop refinement of all none-hydrogen atoms. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.26975 (3) | 0.13889 (3) | 0.24612 (3) | 0.03288 (13) | |
O1 | 0.23706 (14) | 0.24756 (14) | 0.36599 (13) | 0.0376 (4) | |
O2 | 0.34759 (14) | −0.04822 (14) | 0.32078 (13) | 0.0353 (4) | |
O3 | 0.47277 (17) | 0.1377 (2) | 0.21418 (17) | 0.0525 (5) | |
O4 | 0.16546 (15) | 0.66097 (14) | 0.12468 (14) | 0.0439 (4) | |
O5 | 0.12752 (18) | 0.64697 (16) | 0.32171 (16) | 0.0582 (5) | |
O6 | 0.49180 (16) | −0.37323 (15) | 0.19183 (14) | 0.0502 (5) | |
O7 | 0.45911 (15) | −0.26432 (14) | 0.00782 (14) | 0.0438 (4) | |
N1 | 0.21335 (16) | 0.31245 (16) | 0.12293 (15) | 0.0297 (4) | |
N2 | 0.29832 (17) | 0.07854 (17) | 0.08867 (16) | 0.0300 (4) | |
N3 | 0.07251 (17) | 0.12383 (17) | 0.30644 (15) | 0.0320 (5) | |
N4 | −0.09005 (18) | −0.11921 (18) | 0.38595 (16) | 0.0440 (5) | |
H4A | −0.1655 | −0.1300 | 0.4201 | 0.0649 (15)* | |
H4B | −0.0272 | −0.1811 | 0.3589 | 0.0649 (15)* | |
C1 | 0.2158 (2) | 0.3659 (2) | 0.3551 (2) | 0.0352 (6) | |
C2 | 0.1918 (2) | 0.4573 (2) | 0.24656 (19) | 0.0326 (6) | |
C3 | 0.1927 (2) | 0.4259 (2) | 0.1386 (2) | 0.0328 (6) | |
H3 | 0.1766 | 0.4947 | 0.0706 | 0.0649 (15)* | |
C4 | 0.2048 (2) | 0.3014 (2) | 0.00887 (18) | 0.0283 (5) | |
C5 | 0.1529 (2) | 0.4018 (2) | −0.0823 (2) | 0.0367 (6) | |
H5 | 0.1208 | 0.4860 | −0.0703 | 0.0649 (15)* | |
C6 | 0.1470 (2) | 0.3818 (2) | −0.1900 (2) | 0.0389 (6) | |
H6 | 0.1125 | 0.4517 | −0.2518 | 0.0649 (15)* | |
C7 | 0.1918 (2) | 0.2591 (2) | −0.2071 (2) | 0.0394 (6) | |
H7 | 0.1879 | 0.2444 | −0.2808 | 0.0649 (15)* | |
C8 | 0.2415 (2) | 0.1592 (2) | −0.1179 (2) | 0.0367 (6) | |
H8 | 0.2707 | 0.0754 | −0.1302 | 0.0649 (15)* | |
C9 | 0.2506 (2) | 0.1769 (2) | −0.00948 (18) | 0.0273 (5) | |
C10 | 0.3581 (2) | −0.0371 (2) | 0.0728 (2) | 0.0314 (6) | |
H10 | 0.3704 | −0.0472 | −0.0065 | 0.0649 (15)* | |
C11 | 0.4067 (2) | −0.1494 (2) | 0.16015 (19) | 0.0305 (6) | |
C12 | 0.4023 (2) | −0.1482 (2) | 0.2806 (2) | 0.0324 (6) | |
C13 | 0.2200 (3) | 0.4007 (2) | 0.4664 (2) | 0.0532 (7) | |
H13A | 0.1323 | 0.4271 | 0.5104 | 0.0649 (15)* | |
H13B | 0.2568 | 0.4709 | 0.4441 | 0.0649 (15)* | |
H13C | 0.2738 | 0.3269 | 0.5172 | 0.0649 (15)* | |
C14 | 0.1603 (2) | 0.5939 (2) | 0.2401 (2) | 0.0360 (6) | |
C15 | 0.1199 (2) | 0.7980 (2) | 0.1010 (2) | 0.0423 (6) | |
H15A | 0.1766 | 0.8299 | 0.1276 | 0.0649 (15)* | |
H15B | 0.0309 | 0.8279 | 0.1438 | 0.0649 (15)* | |
C16 | 0.1227 (3) | 0.8440 (2) | −0.0316 (2) | 0.0603 (8) | |
H16A | 0.2097 | 0.8076 | −0.0727 | 0.0649 (15)* | |
H16B | 0.0994 | 0.9370 | −0.0533 | 0.0649 (15)* | |
H16C | 0.0608 | 0.8176 | −0.0556 | 0.0649 (15)* | |
C17 | 0.4627 (2) | −0.2647 (2) | 0.3719 (2) | 0.0486 (7) | |
H17A | 0.4620 | −0.2395 | 0.4443 | 0.0649 (15)* | |
H17B | 0.5520 | −0.3055 | 0.3383 | 0.0649 (15)* | |
H17C | 0.4133 | −0.3247 | 0.3924 | 0.0649 (15)* | |
C18 | 0.4546 (2) | −0.2631 (2) | 0.1122 (2) | 0.0354 (6) | |
C19 | 0.5383 (3) | −0.4887 (2) | 0.1480 (2) | 0.0542 (7) | |
H19A | 0.6054 | −0.4819 | 0.0763 | 0.0649 (15)* | |
H19B | 0.4664 | −0.5035 | 0.1259 | 0.0649 (15)* | |
C20 | 0.5923 (3) | −0.5928 (3) | 0.2445 (3) | 0.0927 (11) | |
H20A | 0.6610 | −0.5753 | 0.2676 | 0.0649 (15)* | |
H20B | 0.6281 | −0.6723 | 0.2171 | 0.0649 (15)* | |
H20C | 0.5242 | −0.6008 | 0.3137 | 0.0649 (15)* | |
C21 | −0.0230 (2) | 0.2191 (2) | 0.3454 (2) | 0.0396 (6) | |
H21 | −0.0079 | 0.2977 | 0.3344 | 0.0649 (15)* | |
C22 | −0.1425 (2) | 0.2073 (2) | 0.4010 (2) | 0.0438 (6) | |
H22 | −0.2080 | 0.2765 | 0.4287 | 0.0649 (15)* | |
C23 | −0.1667 (2) | 0.0945 (2) | 0.4163 (2) | 0.0378 (6) | |
H23 | −0.2487 | 0.0853 | 0.4550 | 0.0649 (15)* | |
C24 | −0.0702 (2) | −0.0052 (2) | 0.37487 (19) | 0.0329 (6) | |
C25 | 0.0479 (2) | 0.0151 (2) | 0.32063 (18) | 0.0327 (6) | |
H25 | 0.1151 | −0.0524 | 0.2919 | 0.0649 (15)* | |
C26 | 0.5549 (2) | 0.0917 (2) | 0.3009 (2) | 0.0527 (7) | |
H26A | 0.5189 | 0.1415 | 0.3623 | 0.0649 (15)* | |
H26B | 0.6405 | 0.0993 | 0.2626 | 0.0649 (15)* | |
H26C | 0.5624 | 0.0021 | 0.3381 | 0.0649 (15)* | |
H31 | 0.493 (3) | 0.182 (3) | 0.155 (3) | 0.070 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0385 (2) | 0.0325 (2) | 0.0263 (2) | −0.01143 (16) | −0.00592 (16) | −0.00364 (16) |
O1 | 0.0485 (11) | 0.0363 (10) | 0.0286 (9) | −0.0144 (8) | −0.0084 (8) | −0.0048 (8) |
O2 | 0.0389 (10) | 0.0342 (10) | 0.0287 (9) | −0.0090 (8) | −0.0065 (8) | −0.0033 (8) |
O3 | 0.0451 (12) | 0.0788 (15) | 0.0318 (11) | −0.0307 (11) | −0.0119 (10) | 0.0088 (11) |
O4 | 0.0639 (12) | 0.0289 (10) | 0.0365 (11) | −0.0142 (8) | −0.0047 (9) | −0.0069 (8) |
O5 | 0.0903 (15) | 0.0422 (11) | 0.0403 (11) | −0.0089 (10) | −0.0151 (10) | −0.0175 (10) |
O6 | 0.0732 (13) | 0.0309 (10) | 0.0360 (10) | −0.0040 (9) | −0.0144 (9) | −0.0026 (9) |
O7 | 0.0583 (12) | 0.0381 (10) | 0.0296 (10) | −0.0116 (8) | −0.0034 (9) | −0.0069 (8) |
N1 | 0.0329 (11) | 0.0318 (12) | 0.0253 (11) | −0.0106 (9) | −0.0066 (9) | −0.0058 (9) |
N2 | 0.0302 (11) | 0.0312 (12) | 0.0282 (11) | −0.0109 (9) | −0.0063 (9) | −0.0033 (9) |
N3 | 0.0360 (12) | 0.0305 (11) | 0.0286 (11) | −0.0078 (10) | −0.0068 (9) | −0.0069 (9) |
N4 | 0.0453 (13) | 0.0529 (14) | 0.0445 (13) | −0.0261 (11) | 0.0005 (10) | −0.0193 (11) |
C1 | 0.0360 (15) | 0.0419 (16) | 0.0303 (15) | −0.0153 (12) | −0.0015 (11) | −0.0112 (13) |
C2 | 0.0385 (15) | 0.0339 (14) | 0.0260 (14) | −0.0105 (11) | −0.0068 (12) | −0.0073 (12) |
C3 | 0.0335 (14) | 0.0345 (15) | 0.0272 (13) | −0.0094 (11) | −0.0065 (11) | −0.0026 (11) |
C4 | 0.0284 (13) | 0.0331 (14) | 0.0214 (13) | −0.0111 (11) | −0.0051 (10) | −0.0008 (11) |
C5 | 0.0432 (15) | 0.0320 (14) | 0.0344 (15) | −0.0103 (12) | −0.0116 (12) | −0.0043 (12) |
C6 | 0.0470 (16) | 0.0399 (16) | 0.0265 (14) | −0.0118 (13) | −0.0154 (12) | 0.0028 (12) |
C7 | 0.0489 (16) | 0.0431 (16) | 0.0286 (14) | −0.0161 (13) | −0.0114 (12) | −0.0049 (13) |
C8 | 0.0456 (16) | 0.0332 (14) | 0.0307 (14) | −0.0115 (12) | −0.0077 (12) | −0.0060 (12) |
C9 | 0.0322 (14) | 0.0312 (14) | 0.0199 (13) | −0.0133 (11) | −0.0065 (11) | −0.0016 (11) |
C10 | 0.0336 (14) | 0.0366 (15) | 0.0263 (13) | −0.0155 (12) | −0.0036 (11) | −0.0055 (12) |
C11 | 0.0310 (14) | 0.0295 (14) | 0.0257 (14) | −0.0071 (11) | −0.0043 (11) | −0.0018 (11) |
C12 | 0.0271 (14) | 0.0349 (15) | 0.0299 (15) | −0.0095 (12) | −0.0021 (11) | −0.0021 (12) |
C13 | 0.079 (2) | 0.0505 (17) | 0.0349 (15) | −0.0196 (15) | −0.0171 (14) | −0.0098 (13) |
C14 | 0.0368 (15) | 0.0366 (15) | 0.0330 (15) | −0.0093 (12) | −0.0063 (12) | −0.0074 (14) |
C15 | 0.0435 (16) | 0.0303 (14) | 0.0509 (17) | −0.0112 (12) | −0.0078 (13) | −0.0059 (13) |
C16 | 0.074 (2) | 0.0382 (16) | 0.0526 (19) | −0.0118 (14) | −0.0043 (16) | 0.0005 (14) |
C17 | 0.0599 (18) | 0.0439 (16) | 0.0290 (15) | −0.0026 (13) | −0.0112 (13) | −0.0027 (13) |
C18 | 0.0307 (14) | 0.0319 (15) | 0.0369 (16) | −0.0085 (11) | −0.0022 (12) | −0.0021 (13) |
C19 | 0.072 (2) | 0.0308 (15) | 0.0528 (18) | −0.0052 (14) | −0.0141 (15) | −0.0101 (14) |
C20 | 0.138 (3) | 0.0406 (19) | 0.084 (3) | −0.0024 (19) | −0.033 (2) | −0.0105 (18) |
C21 | 0.0396 (16) | 0.0336 (15) | 0.0420 (16) | −0.0080 (13) | −0.0071 (13) | −0.0070 (13) |
C22 | 0.0365 (16) | 0.0452 (17) | 0.0450 (16) | −0.0034 (13) | −0.0067 (13) | −0.0149 (13) |
C23 | 0.0314 (15) | 0.0550 (17) | 0.0281 (14) | −0.0131 (13) | −0.0058 (11) | −0.0104 (13) |
C24 | 0.0402 (16) | 0.0416 (15) | 0.0206 (13) | −0.0164 (13) | −0.0083 (12) | −0.0053 (11) |
C25 | 0.0369 (15) | 0.0373 (15) | 0.0232 (13) | −0.0086 (12) | −0.0061 (11) | −0.0082 (11) |
C26 | 0.0496 (17) | 0.0648 (19) | 0.0470 (17) | −0.0185 (14) | −0.0160 (14) | −0.0099 (15) |
Fe1—O2 | 2.0298 (16) | C7—H7 | 0.9500 |
Fe1—O1 | 2.0489 (16) | C8—C9 | 1.390 (3) |
Fe1—N1 | 2.0896 (18) | C8—H8 | 0.9500 |
Fe1—N2 | 2.0924 (18) | C10—C11 | 1.424 (3) |
Fe1—N3 | 2.2071 (19) | C10—H10 | 0.9500 |
Fe1—O3 | 2.2132 (19) | C11—C12 | 1.418 (3) |
O1—C1 | 1.275 (2) | C11—C18 | 1.458 (3) |
O2—C12 | 1.271 (2) | C12—C17 | 1.512 (3) |
O3—C26 | 1.406 (3) | C13—H13A | 0.9800 |
O3—H31 | 0.77 (3) | C13—H13B | 0.9800 |
O4—C14 | 1.355 (3) | C13—H13C | 0.9800 |
O4—C15 | 1.442 (2) | C15—C16 | 1.496 (3) |
O5—C14 | 1.208 (3) | C15—H15A | 0.9900 |
O6—C18 | 1.337 (3) | C15—H15B | 0.9900 |
O6—C19 | 1.451 (3) | C16—H16A | 0.9800 |
O7—C18 | 1.228 (3) | C16—H16B | 0.9800 |
N1—C3 | 1.310 (3) | C16—H16C | 0.9800 |
N1—C4 | 1.422 (3) | C17—H17A | 0.9800 |
N2—C10 | 1.311 (3) | C17—H17B | 0.9800 |
N2—C9 | 1.420 (3) | C17—H17C | 0.9800 |
N3—C21 | 1.336 (3) | C19—C20 | 1.458 (4) |
N3—C25 | 1.338 (3) | C19—H19A | 0.9900 |
N4—C24 | 1.379 (3) | C19—H19B | 0.9900 |
N4—H4A | 0.8800 | C20—H20A | 0.9800 |
N4—H4B | 0.8800 | C20—H20B | 0.9800 |
C1—C2 | 1.415 (3) | C20—H20C | 0.9800 |
C1—C13 | 1.502 (3) | C21—C22 | 1.377 (3) |
C2—C3 | 1.425 (3) | C21—H21 | 0.9500 |
C2—C14 | 1.473 (3) | C22—C23 | 1.379 (3) |
C3—H3 | 0.9500 | C22—H22 | 0.9500 |
C4—C5 | 1.391 (3) | C23—C24 | 1.386 (3) |
C4—C9 | 1.409 (3) | C23—H23 | 0.9500 |
C5—C6 | 1.383 (3) | C24—C25 | 1.393 (3) |
C5—H5 | 0.9500 | C25—H25 | 0.9500 |
C6—C7 | 1.385 (3) | C26—H26A | 0.9800 |
C6—H6 | 0.9500 | C26—H26B | 0.9800 |
C7—C8 | 1.367 (3) | C26—H26C | 0.9800 |
O2—Fe1—O1 | 110.64 (6) | O2—C12—C11 | 122.6 (2) |
O2—Fe1—N1 | 163.09 (6) | O2—C12—C17 | 114.2 (2) |
O1—Fe1—N1 | 85.29 (7) | C11—C12—C17 | 123.3 (2) |
O2—Fe1—N2 | 85.15 (7) | C1—C13—H13A | 109.5 |
O1—Fe1—N2 | 163.46 (6) | C1—C13—H13B | 109.5 |
N1—Fe1—N2 | 78.54 (7) | H13A—C13—H13B | 109.5 |
O2—Fe1—N3 | 91.17 (7) | C1—C13—H13C | 109.5 |
O1—Fe1—N3 | 90.29 (7) | H13A—C13—H13C | 109.5 |
N1—Fe1—N3 | 94.49 (7) | H13B—C13—H13C | 109.5 |
N2—Fe1—N3 | 94.42 (7) | O5—C14—O4 | 120.9 (2) |
O2—Fe1—O3 | 82.78 (7) | O5—C14—C2 | 128.2 (2) |
O1—Fe1—O3 | 85.81 (7) | O4—C14—C2 | 110.7 (2) |
N1—Fe1—O3 | 93.13 (7) | O4—C15—C16 | 106.23 (19) |
N2—Fe1—O3 | 91.54 (7) | O4—C15—H15A | 110.5 |
N3—Fe1—O3 | 171.13 (7) | C16—C15—H15A | 110.5 |
C1—O1—Fe1 | 133.45 (14) | O4—C15—H15B | 110.5 |
C12—O2—Fe1 | 134.73 (14) | C16—C15—H15B | 110.5 |
C26—O3—Fe1 | 126.01 (16) | H15A—C15—H15B | 108.7 |
C26—O3—H31 | 117 (2) | C15—C16—H16A | 109.5 |
Fe1—O3—H31 | 115 (2) | C15—C16—H16B | 109.5 |
C14—O4—C15 | 118.66 (18) | H16A—C16—H16B | 109.5 |
C18—O6—C19 | 117.13 (19) | C15—C16—H16C | 109.5 |
C3—N1—C4 | 118.54 (19) | H16A—C16—H16C | 109.5 |
C3—N1—Fe1 | 126.93 (15) | H16B—C16—H16C | 109.5 |
C4—N1—Fe1 | 114.42 (13) | C12—C17—H17A | 109.5 |
C10—N2—C9 | 119.02 (19) | C12—C17—H17B | 109.5 |
C10—N2—Fe1 | 126.51 (16) | H17A—C17—H17B | 109.5 |
C9—N2—Fe1 | 114.43 (14) | C12—C17—H17C | 109.5 |
C21—N3—C25 | 117.7 (2) | H17A—C17—H17C | 109.5 |
C21—N3—Fe1 | 119.87 (15) | H17B—C17—H17C | 109.5 |
C25—N3—Fe1 | 121.81 (15) | O7—C18—O6 | 119.3 (2) |
C24—N4—H4A | 120.0 | O7—C18—C11 | 125.3 (2) |
C24—N4—H4B | 120.0 | O6—C18—C11 | 115.4 (2) |
H4A—N4—H4B | 120.0 | O6—C19—C20 | 107.0 (2) |
O1—C1—C2 | 122.8 (2) | O6—C19—H19A | 110.3 |
O1—C1—C13 | 114.7 (2) | C20—C19—H19A | 110.3 |
C2—C1—C13 | 122.5 (2) | O6—C19—H19B | 110.3 |
C1—C2—C3 | 123.5 (2) | C20—C19—H19B | 110.3 |
C1—C2—C14 | 120.9 (2) | H19A—C19—H19B | 108.6 |
C3—C2—C14 | 115.6 (2) | C19—C20—H20A | 109.5 |
N1—C3—C2 | 127.1 (2) | C19—C20—H20B | 109.5 |
N1—C3—H3 | 116.5 | H20A—C20—H20B | 109.5 |
C2—C3—H3 | 116.5 | C19—C20—H20C | 109.5 |
C5—C4—C9 | 118.8 (2) | H20A—C20—H20C | 109.5 |
C5—C4—N1 | 125.4 (2) | H20B—C20—H20C | 109.5 |
C9—C4—N1 | 115.80 (18) | N3—C21—C22 | 122.2 (2) |
C6—C5—C4 | 121.4 (2) | N3—C21—H21 | 118.9 |
C6—C5—H5 | 119.3 | C22—C21—H21 | 118.9 |
C4—C5—H5 | 119.3 | C21—C22—C23 | 119.7 (2) |
C5—C6—C7 | 119.5 (2) | C21—C22—H22 | 120.2 |
C5—C6—H6 | 120.3 | C23—C22—H22 | 120.2 |
C7—C6—H6 | 120.3 | C22—C23—C24 | 119.4 (2) |
C8—C7—C6 | 119.8 (2) | C22—C23—H23 | 120.3 |
C8—C7—H7 | 120.1 | C24—C23—H23 | 120.3 |
C6—C7—H7 | 120.1 | N4—C24—C23 | 121.7 (2) |
C7—C8—C9 | 121.9 (2) | N4—C24—C25 | 121.4 (2) |
C7—C8—H8 | 119.1 | C23—C24—C25 | 116.9 (2) |
C9—C8—H8 | 119.1 | N3—C25—C24 | 124.1 (2) |
C8—C9—C4 | 118.7 (2) | N3—C25—H25 | 118.0 |
C8—C9—N2 | 125.5 (2) | C24—C25—H25 | 118.0 |
C4—C9—N2 | 115.83 (18) | O3—C26—H26A | 109.5 |
N2—C10—C11 | 127.8 (2) | O3—C26—H26B | 109.5 |
N2—C10—H10 | 116.1 | H26A—C26—H26B | 109.5 |
C11—C10—H10 | 116.1 | O3—C26—H26C | 109.5 |
C12—C11—C10 | 122.6 (2) | H26A—C26—H26C | 109.5 |
C12—C11—C18 | 125.1 (2) | H26B—C26—H26C | 109.5 |
C10—C11—C18 | 112.2 (2) | ||
O2—Fe1—O1—C1 | 163.20 (18) | Fe1—N1—C4—C5 | 170.70 (16) |
N1—Fe1—O1—C1 | −10.96 (19) | C3—N1—C4—C9 | 168.82 (18) |
N2—Fe1—O1—C1 | 1.3 (3) | Fe1—N1—C4—C9 | −7.7 (2) |
N3—Fe1—O1—C1 | −105.4 (2) | C9—C4—C5—C6 | −0.8 (3) |
O3—Fe1—O1—C1 | 82.5 (2) | N1—C4—C5—C6 | −179.1 (2) |
O1—Fe1—O2—C12 | −166.91 (18) | C4—C5—C6—C7 | 1.0 (3) |
N1—Fe1—O2—C12 | −7.3 (3) | C5—C6—C7—C8 | −0.2 (3) |
N2—Fe1—O2—C12 | 8.01 (19) | C6—C7—C8—C9 | −1.0 (3) |
N3—Fe1—O2—C12 | 102.3 (2) | C7—C8—C9—C4 | 1.2 (3) |
O3—Fe1—O2—C12 | −84.2 (2) | C7—C8—C9—N2 | 178.56 (19) |
O2—Fe1—O3—C26 | −52.5 (2) | C5—C4—C9—C8 | −0.3 (3) |
O1—Fe1—O3—C26 | 58.9 (2) | N1—C4—C9—C8 | 178.15 (18) |
N1—Fe1—O3—C26 | 144.0 (2) | C5—C4—C9—N2 | −177.94 (18) |
N2—Fe1—O3—C26 | −137.4 (2) | N1—C4—C9—N2 | 0.5 (3) |
O2—Fe1—N1—C3 | −152.0 (2) | C10—N2—C9—C8 | 11.6 (3) |
O1—Fe1—N1—C3 | 8.92 (18) | Fe1—N2—C9—C8 | −170.60 (17) |
N2—Fe1—N1—C3 | −167.56 (18) | C10—N2—C9—C4 | −170.96 (18) |
N3—Fe1—N1—C3 | 98.83 (18) | Fe1—N2—C9—C4 | 6.8 (2) |
O3—Fe1—N1—C3 | −76.62 (18) | C9—N2—C10—C11 | −176.44 (19) |
O2—Fe1—N1—C4 | 24.2 (3) | Fe1—N2—C10—C11 | 6.1 (3) |
O1—Fe1—N1—C4 | −174.95 (14) | N2—C10—C11—C12 | −3.8 (3) |
N2—Fe1—N1—C4 | 8.58 (13) | N2—C10—C11—C18 | 173.6 (2) |
N3—Fe1—N1—C4 | −85.03 (14) | Fe1—O2—C12—C11 | −8.4 (3) |
O3—Fe1—N1—C4 | 99.52 (14) | Fe1—O2—C12—C17 | 171.10 (14) |
O2—Fe1—N2—C10 | −6.20 (17) | C10—C11—C12—O2 | 4.4 (3) |
O1—Fe1—N2—C10 | 156.87 (19) | C18—C11—C12—O2 | −172.6 (2) |
N1—Fe1—N2—C10 | 169.30 (18) | C10—C11—C12—C17 | −175.1 (2) |
N3—Fe1—N2—C10 | −97.00 (17) | C18—C11—C12—C17 | 7.9 (3) |
O3—Fe1—N2—C10 | 76.42 (18) | C15—O4—C14—O5 | −5.6 (3) |
O2—Fe1—N2—C9 | 176.20 (14) | C15—O4—C14—C2 | 171.33 (17) |
O1—Fe1—N2—C9 | −20.7 (3) | C1—C2—C14—O5 | −15.0 (4) |
N1—Fe1—N2—C9 | −8.30 (13) | C3—C2—C14—O5 | 163.4 (2) |
N3—Fe1—N2—C9 | 85.40 (14) | C1—C2—C14—O4 | 168.31 (19) |
O3—Fe1—N2—C9 | −101.18 (14) | C3—C2—C14—O4 | −13.3 (3) |
O2—Fe1—N3—C21 | 141.91 (17) | C14—O4—C15—C16 | −173.29 (19) |
O1—Fe1—N3—C21 | 31.27 (17) | C19—O6—C18—O7 | 1.2 (3) |
N1—Fe1—N3—C21 | −54.04 (17) | C19—O6—C18—C11 | 179.14 (19) |
N2—Fe1—N3—C21 | −132.86 (17) | C12—C11—C18—O7 | −179.6 (2) |
O2—Fe1—N3—C25 | −28.95 (16) | C10—C11—C18—O7 | 3.1 (3) |
O1—Fe1—N3—C25 | −139.60 (16) | C12—C11—C18—O6 | 2.6 (3) |
N1—Fe1—N3—C25 | 135.10 (16) | C10—C11—C18—O6 | −174.66 (18) |
N2—Fe1—N3—C25 | 56.28 (16) | C18—O6—C19—C20 | 170.9 (2) |
Fe1—O1—C1—C2 | 9.4 (3) | C25—N3—C21—C22 | 1.5 (3) |
Fe1—O1—C1—C13 | −169.77 (15) | Fe1—N3—C21—C22 | −169.77 (17) |
O1—C1—C2—C3 | −1.9 (4) | N3—C21—C22—C23 | −0.9 (4) |
C13—C1—C2—C3 | 177.3 (2) | C21—C22—C23—C24 | −0.3 (3) |
O1—C1—C2—C14 | 176.42 (19) | C22—C23—C24—N4 | −178.8 (2) |
C13—C1—C2—C14 | −4.4 (3) | C22—C23—C24—C25 | 0.8 (3) |
C4—N1—C3—C2 | 177.4 (2) | C21—N3—C25—C24 | −0.9 (3) |
Fe1—N1—C3—C2 | −6.6 (3) | Fe1—N3—C25—C24 | 170.12 (15) |
C1—C2—C3—N1 | 0.9 (4) | N4—C24—C25—N3 | 179.42 (19) |
C14—C2—C3—N1 | −177.4 (2) | C23—C24—C25—N3 | −0.2 (3) |
C3—N1—C4—C5 | −12.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1i | 0.88 | 2.58 | 3.215 (3) | 130 |
N4—H4B···O5ii | 0.88 | 2.20 | 3.068 (3) | 171 |
O3—H31···O7iii | 0.77 (3) | 1.92 (3) | 2.676 (3) | 167 (4) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y−1, z; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C20H22N2O6)(C5H6N2)(CH4O)] |
Mr | 568.40 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 11.234 (4), 11.5760 (11), 11.834 (3) |
α, β, γ (°) | 72.740 (17), 75.67 (3), 68.91 (2) |
V (Å3) | 1354.0 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.32 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Oxford XCalibur diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23067, 4708, 2998 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.081, 0.94 |
No. of reflections | 4708 |
No. of parameters | 353 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.21 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and SCHAKAL99 (Keller, 1999).
Fe1—O2 | 2.0298 (16) | Fe1—N2 | 2.0924 (18) |
Fe1—O1 | 2.0489 (16) | Fe1—N3 | 2.2071 (19) |
Fe1—N1 | 2.0896 (18) | Fe1—O3 | 2.2132 (19) |
O2—Fe1—O1 | 110.64 (6) | N1—Fe1—N2 | 78.54 (7) |
O2—Fe1—N1 | 163.09 (6) | O2—Fe1—O3 | 82.78 (7) |
O1—Fe1—N2 | 163.46 (6) | N3—Fe1—O3 | 171.13 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1i | 0.88 | 2.58 | 3.215 (3) | 130 |
N4—H4B···O5ii | 0.88 | 2.20 | 3.068 (3) | 171 |
O3—H31···O7iii | 0.77 (3) | 1.92 (3) | 2.676 (3) | 167 (4) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y−1, z; (iii) −x+1, −y, −z. |
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Octahedral iron(II) complexes are an interesting class of complexes because of the possible occurrence of the spin crossover phenomenon. The ability to switch between two or more electronic states on the molecular level under changes in temperature, pressure or light is of potential interest for future applications in molecular switches or memory devices. Although spin crossover could be observed for any octahedral complex with dn (n = 4–7) electronic configuration, the spin transition in octahedral iron(II) complexes with the diamagnetic low-spin (LS) and the paramagnetic high-spin (HS) state are by far the most thoroughly investigated. Of those iron(II) complexes that have been studied, about 90% exhibit N6 coordination, while the others have N4O2, N4C2, N3C2O2 or N4S2 coordination environments (Gütlich et al., 1994; Goodwin, 1976; König, 1991; Kahn & Martinez, 1998). So far, no examples with an N3O3 coordination environment are known.
In this paper we present the strucural and magnetic properties of the octahedral iron(II) complex (3-aminopyridine-κN1){(E,E)-diethyl 2,2'-[1,2-phenylenebis(nitrilomethylidyne)]bis(3-oxobutanate)(2-)-κ2O3,N,N',O3'}(methanol-κO)iron(II), (I), in which the iron ion is centered in an N3O3 coordination environment. The complex was obtained in a one-pot reaction under argon by conversion of [FeL(MeOH)2] and 3-aminopyridine (3-apy) in methanol as solvent and heating to reflux for one hour. A 30 molar excess of 3-apy was used in order to obtain a partial substitution of the axial methanol ligands and therefore an unsymmetric complex with two different axial ligands (Fig. 1).
The coordination around the iron(II) ion is almost ideal octahedral, with a displacement of the Fe2+ ion from the N2O2 coordination plane towards the axial 3-apy ligand of about 0.08 Å. This is surprising, because with methanol as a relatively weak ligand in the axial position one could expect some larger distortion towards the stronger 3-apy. Accordingly, the average bond lengths and angles within the first coordination sphere of the iron centre (Table 1) are within the range reported for similar octahedral iron(II) complexes with N4O2 coordination and the iron centre in the high-spin state (Fe–Neq = 2.09 Å and Fe–Oeq = 2.04 Å; Leibeling, 2003; Weber et al., 2008). The equatorial O2—Fe1—O1 angle is a characteristic tool for the determination of the spin state of this type of iron(II) complex, because the angle changes from about 110° in the HS state to about 90° in the LS state. At 110.64 (6)° in (I), this angle is in the region observed for N4O2-coordinated iron(II) complexes in the HS state (Leibeling, 2003; Weber et al., 2008). The heteroatoms of the axial ligands face one another almost linearly. A possible explanation for the minor distortion is the hydrogen-bond network that the amine group of 3-apy is involved in.
Intermolecular interactions such as hydrogen bonding, π-stacking and van der Waals interactions are thought to play a central role for transmitting cooperative interactions during a spin transition in mononuclear complexes. In complex (I), three different hydrogen bonds (see Table 2) form an infinite two-dimensional network along the (101) plane. The base vectors are [010] and [101]. Amine atom N4 acts as a double hydrogen-bond donor, firstly via atom H4A to carboxylate atom O1i [symmetry code: (i) -x, -y, -z + 1], so that complexes facing each other with the axial methanol ligand are linked, and secondly via atom H4B to carboxylate atom O5ii [symmetry code: (ii) x, y - 1, z], linking the asymmetric units into chains along [010] (Fig. 2). The molecules are further linked along [100] by methanol atom O3, acting as a hydrogen-bond donor via atom H31 to carboxylate atom O7iii [symmetry code: (iii) -x + 1, -y, -z] of the equatorial ligand of the neighboring complex (Fig. 3).
At room temperature, the magnetic moment, expressed as the product χMT, is equal to 3.2 cm3 mol-1 K, which is a typical value for iron(II) in the HS state. The moment remains almost constant down to 25 K (χMT = 3.01 cm3 mol-1 K), indicating that no spin crossover occurs. The decrease of χMT below 25 K is due to zero-field splitting. Obviously, the methanol ligand is too weak to put the overall ligand field in the spin crossover region.