Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106037310/bg3019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037310/bg3019Isup2.hkl |
CCDC reference: 628494
[Fe(III)(bpca−)2]ClO4·2CH3CN was obtained as orange crystals by slow evaporation of an acetonitrile solution containing Fe(ClO4)2·6H2O (0.1 mmol), di(2-picolyl)amine (0.2 mmol) and Et3N (0.2 mmol). The resulting crystals three hours were collected by filtration, washed with diethyl ether and dried in a vacuum two hours (yield 23%). Elemental analysis calculated for C28H22ClFeN8O8: C 48.75, H 3.21, N 16.24%; found: C 49.17, H 3.93, N 16.53%. Spectroscopic details are given in the CIF.
H atoms were introduced in calulated positions and treated as riding on their carrier atoms, with C—H = 0.95 Å for the aromatic H atoms and 0.98 Å for the acetonitril methyl H atoms. The methyl groups were allowed to rotate around the C—C bond during refinement. Uiso(H) values were set at 1.5Ueq(methyl C) or 1.2Ueq(aromatic C).
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
[Fe(C12H8N3O2)2]ClO4·2C2H3N | F(000) = 1412 |
Mr = 689.84 | Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set. |
Monoclinic, P21/c | Dx = 1.580 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.800 (2) Å | Cell parameters from 385 reflections |
b = 16.565 (3) Å | θ = 2.0–25.0° |
c = 14.895 (2) Å | µ = 0.68 mm−1 |
β = 113.356 (16)° | T = 150 K |
V = 2899.4 (9) Å3 | Plate, orange |
Z = 4 | 0.40 × 0.18 × 0.02 mm |
Nonius KappaCCD area-detector diffractometer | 6607 independent reflections |
Radiation source: Rotating Anode | 4867 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
Detector resolution: 18.4 pixels mm-1 | θmax = 27.4°, θmin = 1.7° |
ϕ scans, and ω scans with κ offset | h = −16→16 |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | k = −21→21 |
Tmin = 0.875, Tmax = 0.989 | l = −19→19 |
70020 measured reflections |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0423P)2 + 1.4P] where P = (Fo2 + 2Fc2)/3 |
6607 reflections | (Δ/σ)max = 0.001 |
417 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Fe(C12H8N3O2)2]ClO4·2C2H3N | V = 2899.4 (9) Å3 |
Mr = 689.84 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.800 (2) Å | µ = 0.68 mm−1 |
b = 16.565 (3) Å | T = 150 K |
c = 14.895 (2) Å | 0.40 × 0.18 × 0.02 mm |
β = 113.356 (16)° |
Nonius KappaCCD area-detector diffractometer | 6607 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2003) | 4867 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 0.989 | Rint = 0.080 |
70020 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.38 e Å−3 |
6607 reflections | Δρmin = −0.36 e Å−3 |
417 parameters |
Experimental. IR (ν / cm−1): 3112 (w), 1718 (s), 1661 (m), 1604 (s), 1568 (m), 1471 (m), 1446 (m), 1321 (s), 1289 (s), 1257 (m), 1188 (m), 1160 (w), 1076 (s), 1051 (s), 820 (w), 763 (m), 700 (m), 657 (m), 620 (s), 552 (w), 493 (m). |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | 0.39115 (2) | 0.18358 (2) | 0.15722 (2) | 0.0194 (1) | |
O1 | 0.55942 (13) | 0.23478 (10) | −0.01336 (11) | 0.0336 (5) | |
O2 | 0.42000 (14) | 0.09579 (10) | −0.08348 (11) | 0.0370 (6) | |
O3 | 0.38064 (13) | 0.13124 (10) | 0.41801 (10) | 0.0337 (5) | |
O4 | 0.23611 (14) | 0.26513 (10) | 0.32723 (11) | 0.0366 (5) | |
N1 | 0.50297 (14) | 0.27235 (10) | 0.19678 (11) | 0.0207 (5) | |
N2 | 0.43868 (14) | 0.17615 (10) | 0.05075 (12) | 0.0214 (5) | |
N3 | 0.28887 (14) | 0.09604 (10) | 0.08530 (11) | 0.0206 (5) | |
N4 | 0.50032 (14) | 0.10390 (10) | 0.24337 (12) | 0.0224 (5) | |
N5 | 0.34806 (14) | 0.19036 (10) | 0.26705 (11) | 0.0207 (5) | |
N6 | 0.26854 (14) | 0.26320 (10) | 0.10334 (11) | 0.0201 (5) | |
C11 | 0.53042 (18) | 0.32040 (13) | 0.27554 (14) | 0.0244 (6) | |
C12 | 0.60896 (19) | 0.38178 (14) | 0.29375 (16) | 0.0312 (7) | |
C13 | 0.6619 (2) | 0.39479 (14) | 0.23047 (17) | 0.0339 (8) | |
C14 | 0.63332 (19) | 0.34589 (14) | 0.14854 (16) | 0.0293 (7) | |
C15 | 0.55422 (17) | 0.28575 (13) | 0.13389 (14) | 0.0224 (6) | |
C16 | 0.51961 (18) | 0.22969 (13) | 0.04778 (14) | 0.0245 (6) | |
C21 | 0.21011 (17) | 0.05945 (13) | 0.10936 (15) | 0.0239 (6) | |
C22 | 0.14372 (18) | −0.00270 (13) | 0.05341 (16) | 0.0281 (7) | |
C23 | 0.1567 (2) | −0.02672 (14) | −0.02989 (17) | 0.0332 (7) | |
C24 | 0.23756 (19) | 0.01129 (14) | −0.05538 (16) | 0.0314 (7) | |
C25 | 0.30241 (18) | 0.07125 (13) | 0.00381 (14) | 0.0244 (6) | |
C26 | 0.39354 (18) | 0.11513 (13) | −0.01681 (15) | 0.0249 (6) | |
C31 | 0.57910 (19) | 0.06174 (13) | 0.22485 (16) | 0.0295 (7) | |
C32 | 0.6529 (2) | 0.00938 (15) | 0.29271 (18) | 0.0400 (8) | |
C33 | 0.6463 (2) | −0.00041 (15) | 0.38219 (18) | 0.0408 (8) | |
C34 | 0.5638 (2) | 0.04149 (14) | 0.40117 (16) | 0.0331 (8) | |
C35 | 0.49250 (18) | 0.09244 (13) | 0.33070 (15) | 0.0244 (6) | |
C36 | 0.40100 (18) | 0.13984 (12) | 0.34600 (14) | 0.0240 (6) | |
C41 | 0.22901 (18) | 0.29518 (13) | 0.01330 (14) | 0.0241 (6) | |
C42 | 0.14386 (19) | 0.35272 (13) | −0.01541 (15) | 0.0289 (7) | |
C43 | 0.09887 (19) | 0.37937 (13) | 0.04925 (16) | 0.0285 (7) | |
C44 | 0.13928 (18) | 0.34625 (13) | 0.14253 (15) | 0.0262 (7) | |
C45 | 0.22258 (17) | 0.28818 (12) | 0.16652 (14) | 0.0215 (6) | |
C46 | 0.26814 (18) | 0.24731 (13) | 0.26379 (14) | 0.0239 (6) | |
N7 | 0.7673 (2) | 0.16218 (18) | 0.1904 (2) | 0.0717 (11) | |
C51 | 0.9636 (2) | 0.2277 (2) | 0.2382 (2) | 0.0573 (11) | |
C52 | 0.8541 (2) | 0.19042 (16) | 0.2124 (2) | 0.0439 (9) | |
N8 | 0.9587 (3) | 0.30670 (18) | 0.4872 (3) | 0.0813 (15) | |
C61 | 0.7905 (3) | 0.2065 (2) | 0.4429 (3) | 0.0723 (14) | |
C62 | 0.8847 (3) | 0.2630 (2) | 0.4671 (2) | 0.0581 (12) | |
Cl1 | 0.93200 (5) | 0.01938 (3) | 0.69799 (4) | 0.0354 (2) | |
O5 | 0.8610 (2) | 0.05876 (17) | 0.61221 (16) | 0.0861 (10) | |
O6 | 0.8735 (2) | −0.04449 (13) | 0.72108 (16) | 0.0712 (9) | |
O7 | 1.02648 (17) | −0.01286 (12) | 0.68245 (17) | 0.0638 (8) | |
O8 | 0.9694 (2) | 0.07583 (13) | 0.77667 (16) | 0.0736 (9) | |
H11 | 0.49480 | 0.31180 | 0.31980 | 0.0290* | |
H12 | 0.62660 | 0.41500 | 0.34980 | 0.0370* | |
H13 | 0.71690 | 0.43640 | 0.24270 | 0.0410* | |
H14 | 0.66780 | 0.35380 | 0.10330 | 0.0350* | |
H21 | 0.19970 | 0.07660 | 0.16610 | 0.0290* | |
H22 | 0.08950 | −0.02860 | 0.07250 | 0.0340* | |
H23 | 0.11090 | −0.06880 | −0.06950 | 0.0400* | |
H24 | 0.24770 | −0.00400 | −0.11280 | 0.0380* | |
H31 | 0.58430 | 0.06810 | 0.16340 | 0.0350* | |
H32 | 0.70790 | −0.01970 | 0.27780 | 0.0480* | |
H33 | 0.69750 | −0.03540 | 0.43000 | 0.0490* | |
H34 | 0.55650 | 0.03510 | 0.46180 | 0.0400* | |
H41 | 0.26020 | 0.27790 | −0.03170 | 0.0290* | |
H42 | 0.11630 | 0.37390 | −0.07990 | 0.0350* | |
H43 | 0.04130 | 0.41960 | 0.03050 | 0.0340* | |
H44 | 0.10990 | 0.36340 | 0.18880 | 0.0310* | |
H51A | 1.01770 | 0.18790 | 0.23330 | 0.0860* | |
H51B | 0.99070 | 0.24810 | 0.30540 | 0.0860* | |
H51C | 0.95710 | 0.27260 | 0.19340 | 0.0860* | |
H61A | 0.81700 | 0.15700 | 0.48150 | 0.1080* | |
H61B | 0.76170 | 0.19330 | 0.37310 | 0.1080* | |
H61C | 0.72960 | 0.23090 | 0.45780 | 0.1080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0246 (2) | 0.0222 (2) | 0.0160 (1) | −0.0002 (1) | 0.0130 (1) | −0.0005 (1) |
O1 | 0.0408 (9) | 0.0436 (10) | 0.0279 (8) | −0.0130 (8) | 0.0260 (7) | −0.0094 (7) |
O2 | 0.0528 (10) | 0.0396 (10) | 0.0326 (9) | −0.0140 (8) | 0.0319 (8) | −0.0145 (7) |
O3 | 0.0425 (9) | 0.0441 (10) | 0.0231 (8) | 0.0066 (8) | 0.0221 (7) | 0.0080 (7) |
O4 | 0.0467 (10) | 0.0488 (10) | 0.0243 (8) | 0.0171 (8) | 0.0247 (7) | 0.0063 (7) |
N1 | 0.0240 (9) | 0.0234 (9) | 0.0178 (8) | 0.0007 (7) | 0.0116 (7) | 0.0009 (7) |
N2 | 0.0264 (9) | 0.0246 (9) | 0.0193 (8) | −0.0025 (7) | 0.0155 (7) | −0.0029 (7) |
N3 | 0.0248 (9) | 0.0215 (9) | 0.0179 (8) | 0.0008 (7) | 0.0111 (7) | 0.0005 (7) |
N4 | 0.0258 (9) | 0.0244 (9) | 0.0205 (8) | −0.0010 (7) | 0.0128 (7) | 0.0001 (7) |
N5 | 0.0256 (9) | 0.0257 (9) | 0.0162 (8) | 0.0016 (7) | 0.0139 (7) | 0.0014 (7) |
N6 | 0.0235 (9) | 0.0233 (9) | 0.0169 (8) | −0.0025 (7) | 0.0116 (7) | −0.0018 (7) |
C11 | 0.0289 (11) | 0.0294 (11) | 0.0186 (10) | 0.0013 (10) | 0.0133 (9) | −0.0019 (9) |
C12 | 0.0380 (13) | 0.0328 (13) | 0.0260 (11) | −0.0045 (11) | 0.0161 (10) | −0.0095 (10) |
C13 | 0.0354 (13) | 0.0341 (13) | 0.0369 (13) | −0.0109 (11) | 0.0195 (11) | −0.0088 (10) |
C14 | 0.0333 (13) | 0.0342 (12) | 0.0277 (11) | −0.0062 (10) | 0.0199 (10) | −0.0032 (9) |
C15 | 0.0262 (11) | 0.0260 (11) | 0.0191 (10) | 0.0003 (9) | 0.0133 (8) | −0.0001 (8) |
C16 | 0.0273 (11) | 0.0301 (12) | 0.0207 (10) | −0.0004 (9) | 0.0143 (9) | 0.0002 (9) |
C21 | 0.0264 (11) | 0.0283 (12) | 0.0209 (10) | 0.0010 (9) | 0.0136 (9) | 0.0036 (9) |
C22 | 0.0261 (11) | 0.0301 (12) | 0.0302 (11) | −0.0005 (10) | 0.0134 (9) | 0.0049 (9) |
C23 | 0.0351 (13) | 0.0328 (13) | 0.0313 (12) | −0.0109 (10) | 0.0129 (10) | −0.0048 (10) |
C24 | 0.0379 (13) | 0.0346 (13) | 0.0259 (11) | −0.0058 (11) | 0.0171 (10) | −0.0066 (10) |
C25 | 0.0308 (12) | 0.0262 (11) | 0.0206 (10) | 0.0001 (9) | 0.0148 (9) | −0.0005 (8) |
C26 | 0.0321 (12) | 0.0275 (11) | 0.0204 (10) | −0.0004 (9) | 0.0160 (9) | −0.0002 (8) |
C31 | 0.0357 (13) | 0.0297 (12) | 0.0289 (11) | 0.0056 (10) | 0.0190 (10) | 0.0001 (9) |
C32 | 0.0453 (15) | 0.0399 (14) | 0.0412 (14) | 0.0171 (12) | 0.0241 (12) | 0.0072 (11) |
C33 | 0.0442 (14) | 0.0408 (15) | 0.0371 (13) | 0.0176 (12) | 0.0159 (12) | 0.0135 (11) |
C34 | 0.0391 (14) | 0.0353 (13) | 0.0262 (12) | 0.0051 (11) | 0.0142 (10) | 0.0065 (10) |
C35 | 0.0296 (12) | 0.0241 (11) | 0.0220 (10) | −0.0019 (9) | 0.0128 (9) | 0.0003 (8) |
C36 | 0.0297 (12) | 0.0260 (11) | 0.0196 (10) | −0.0033 (9) | 0.0133 (9) | −0.0006 (8) |
C41 | 0.0288 (11) | 0.0293 (11) | 0.0186 (10) | −0.0034 (9) | 0.0141 (9) | −0.0005 (8) |
C42 | 0.0330 (12) | 0.0312 (12) | 0.0219 (11) | −0.0012 (10) | 0.0102 (9) | 0.0050 (9) |
C43 | 0.0281 (12) | 0.0285 (12) | 0.0313 (12) | 0.0019 (10) | 0.0144 (10) | 0.0034 (9) |
C44 | 0.0287 (12) | 0.0268 (11) | 0.0284 (11) | −0.0002 (9) | 0.0171 (10) | −0.0020 (9) |
C45 | 0.0242 (11) | 0.0234 (10) | 0.0210 (10) | −0.0026 (9) | 0.0133 (8) | −0.0013 (8) |
C46 | 0.0268 (11) | 0.0290 (12) | 0.0202 (10) | −0.0022 (9) | 0.0139 (9) | −0.0003 (8) |
N7 | 0.0533 (17) | 0.0665 (18) | 0.102 (2) | −0.0047 (15) | 0.0380 (16) | 0.0003 (16) |
C51 | 0.0514 (18) | 0.065 (2) | 0.0540 (18) | −0.0122 (15) | 0.0193 (15) | 0.0047 (15) |
C52 | 0.0461 (16) | 0.0376 (15) | 0.0518 (16) | 0.0067 (13) | 0.0235 (13) | 0.0039 (12) |
N8 | 0.101 (3) | 0.0474 (18) | 0.109 (3) | 0.0218 (17) | 0.056 (2) | 0.0099 (17) |
C61 | 0.068 (2) | 0.087 (3) | 0.070 (2) | 0.021 (2) | 0.0360 (19) | 0.0186 (19) |
C62 | 0.075 (2) | 0.051 (2) | 0.063 (2) | 0.0309 (18) | 0.0429 (19) | 0.0154 (16) |
Cl1 | 0.0482 (4) | 0.0324 (3) | 0.0334 (3) | −0.0043 (3) | 0.0246 (3) | −0.0017 (2) |
O5 | 0.0915 (18) | 0.106 (2) | 0.0501 (13) | 0.0353 (16) | 0.0167 (13) | 0.0236 (13) |
O6 | 0.1130 (19) | 0.0557 (13) | 0.0851 (16) | −0.0362 (13) | 0.0819 (15) | −0.0200 (11) |
O7 | 0.0595 (13) | 0.0497 (12) | 0.1026 (17) | −0.0045 (10) | 0.0539 (13) | −0.0079 (12) |
O8 | 0.1106 (19) | 0.0544 (13) | 0.0598 (14) | −0.0181 (13) | 0.0382 (13) | −0.0268 (11) |
Fe1—N1 | 1.9722 (18) | C24—C25 | 1.368 (3) |
Fe1—N2 | 1.9145 (18) | C25—C26 | 1.506 (3) |
Fe1—N3 | 1.9627 (17) | C31—C32 | 1.382 (3) |
Fe1—N4 | 1.9798 (18) | C32—C33 | 1.378 (4) |
Fe1—N5 | 1.9257 (17) | C33—C34 | 1.383 (4) |
Fe1—N6 | 1.9617 (18) | C34—C35 | 1.374 (3) |
Cl1—O6 | 1.415 (2) | C35—C36 | 1.501 (3) |
Cl1—O7 | 1.422 (2) | C41—C42 | 1.382 (3) |
Cl1—O8 | 1.426 (2) | C42—C43 | 1.376 (3) |
Cl1—O5 | 1.401 (2) | C43—C44 | 1.389 (3) |
O1—C16 | 1.210 (3) | C44—C45 | 1.374 (3) |
O2—C26 | 1.213 (3) | C45—C46 | 1.493 (3) |
O3—C36 | 1.208 (3) | C11—H11 | 0.9500 |
O4—C46 | 1.206 (3) | C12—H12 | 0.9500 |
N1—C15 | 1.358 (3) | C13—H13 | 0.9500 |
N1—C11 | 1.344 (3) | C14—H14 | 0.9500 |
N2—C26 | 1.381 (3) | C21—H21 | 0.9500 |
N2—C16 | 1.378 (3) | C22—H22 | 0.9500 |
N3—C21 | 1.341 (3) | C23—H23 | 0.9500 |
N3—C25 | 1.356 (3) | C24—H24 | 0.9500 |
N4—C31 | 1.342 (3) | C31—H31 | 0.9500 |
N4—C35 | 1.357 (3) | C32—H32 | 0.9500 |
N5—C46 | 1.378 (3) | C33—H33 | 0.9500 |
N5—C36 | 1.382 (3) | C34—H34 | 0.9500 |
N6—C41 | 1.341 (2) | C41—H41 | 0.9500 |
N6—C45 | 1.357 (3) | C42—H42 | 0.9500 |
N7—C52 | 1.128 (4) | C43—H43 | 0.9500 |
N8—C62 | 1.134 (5) | C44—H44 | 0.9500 |
C11—C12 | 1.379 (3) | C51—C52 | 1.438 (4) |
C12—C13 | 1.379 (4) | C51—H51A | 0.9800 |
C13—C14 | 1.388 (3) | C51—H51B | 0.9800 |
C14—C15 | 1.375 (3) | C51—H51C | 0.9800 |
C15—C16 | 1.501 (3) | C61—C62 | 1.454 (5) |
C21—C22 | 1.384 (3) | C61—H61B | 0.9800 |
C22—C23 | 1.374 (3) | C61—H61C | 0.9800 |
C23—C24 | 1.387 (4) | C61—H61A | 0.9800 |
Cl1···H44i | 3.0400 | C11···O2v | 3.269 (3) |
Cl1···H42ii | 2.9000 | C13···C21x | 3.566 (3) |
O1···C36iii | 3.073 (3) | C14···N7 | 3.427 (4) |
O1···O2 | 2.846 (2) | C15···N7 | 3.243 (4) |
O1···C61iii | 3.413 (5) | C15···O3iii | 3.392 (3) |
O1···C11iii | 3.152 (3) | C16···N7 | 3.237 (4) |
O1···O3iii | 3.058 (2) | C16···C36iii | 3.520 (3) |
O2···O1 | 2.846 (2) | C16···O3iii | 3.079 (3) |
O2···C31iv | 3.356 (3) | C21···O6vii | 3.119 (3) |
O2···C32iv | 3.363 (3) | C21···C13ii | 3.566 (3) |
O2···C11iii | 3.269 (3) | C22···C22xi | 3.382 (3) |
O2···O4iii | 3.184 (3) | C22···N8ii | 3.380 (4) |
O3···O4 | 2.861 (2) | C23···O8xii | 3.385 (3) |
O3···C15v | 3.392 (3) | C23···N8ii | 3.308 (4) |
O3···O1v | 3.058 (2) | C26···C31 | 3.550 (3) |
O3···C41v | 3.074 (3) | C26···O4iii | 3.111 (3) |
O3···C16v | 3.079 (3) | C31···O2iv | 3.356 (3) |
O4···C51vi | 3.262 (3) | C31···N7 | 3.133 (4) |
O4···C41v | 2.981 (3) | C31···C26 | 3.550 (3) |
O4···O3 | 2.861 (2) | C32···O2iv | 3.363 (3) |
O4···C26v | 3.111 (3) | C33···C42ii | 3.584 (3) |
O4···O2v | 3.184 (3) | C36···C16v | 3.520 (3) |
O5···C61 | 3.370 (5) | C36···O1v | 3.073 (3) |
O6···C21vii | 3.119 (3) | C41···O4iii | 2.981 (3) |
O7···C44i | 3.277 (3) | C41···O3iii | 3.074 (3) |
O7···C42ii | 3.406 (3) | C42···O7x | 3.406 (3) |
O7···C43i | 3.338 (3) | C42···C33x | 3.584 (3) |
O7···C52viii | 3.397 (3) | C43···C62xiii | 3.452 (4) |
O8···C23ix | 3.385 (3) | C43···O7xiii | 3.338 (3) |
O8···C51v | 3.300 (4) | C44···O7xiii | 3.277 (3) |
O1···H11iii | 2.4100 | C46···C11 | 3.507 (3) |
O1···H61Ciii | 2.4500 | C51···O8iii | 3.300 (4) |
O1···H14 | 2.6300 | C51···O4xiv | 3.262 (3) |
O2···H11iii | 2.5400 | C52···O7viii | 3.397 (3) |
O2···H24 | 2.6500 | C61···O5 | 3.370 (5) |
O3···H41v | 2.4700 | C61···O1v | 3.413 (5) |
O3···H34 | 2.6200 | C62···C43i | 3.452 (4) |
O4···H41v | 2.1200 | C21···H12ii | 3.0800 |
O4···H44 | 2.6200 | C21···H13ii | 2.8700 |
O4···H51Avi | 2.8800 | C22···H13ii | 3.0200 |
O5···H14v | 2.8200 | C22···H22xi | 2.8700 |
O5···H61A | 2.4300 | C22···H12ii | 3.0400 |
O6···H51Aviii | 2.7000 | C23···H22xi | 3.1000 |
O6···H13v | 2.8000 | C26···H31 | 2.9300 |
O6···H21vii | 2.2900 | C36···H21 | 3.0700 |
O6···H42ii | 2.5500 | C41···H33x | 2.9700 |
O7···H42ii | 2.6400 | C42···H51Bxiii | 3.1000 |
O7···H44i | 2.6800 | C42···H33x | 2.6700 |
O7···H43i | 2.8100 | C43···H33x | 2.8700 |
O8···H22vii | 2.7500 | C44···H51Cvi | 2.9800 |
O8···H44i | 2.8000 | C44···H32x | 2.8900 |
O8···H51Cv | 2.7800 | C46···H11 | 2.8900 |
N1···N2 | 2.555 (2) | C52···H61B | 3.0600 |
N1···N4 | 2.879 (2) | C52···H23iv | 3.0900 |
N1···N5 | 2.919 (3) | H11···O2v | 2.5400 |
N1···N6 | 2.766 (3) | H11···C46 | 2.8900 |
N1···C45 | 3.445 (3) | H11···O1v | 2.4100 |
N1···C16 | 2.418 (3) | H11···N5 | 2.6500 |
N2···C25 | 2.363 (3) | H12···C21x | 3.0800 |
N2···C15 | 2.359 (3) | H12···C22x | 3.0400 |
N2···N1 | 2.555 (2) | H13···O6iii | 2.8000 |
N2···N3 | 2.547 (3) | H13···C21x | 2.8700 |
N2···N4 | 2.914 (2) | H13···C22x | 3.0200 |
N2···N6 | 2.965 (3) | H14···O5iii | 2.8200 |
N2···C31 | 3.139 (3) | H14···O1 | 2.6300 |
N2···C41 | 3.196 (3) | H21···N5 | 2.6700 |
N3···N5 | 2.953 (2) | H21···C36 | 3.0700 |
N3···C26 | 2.413 (3) | H21···O6vii | 2.2900 |
N3···N2 | 2.547 (3) | H22···C22xi | 2.8700 |
N3···N4 | 2.799 (2) | H22···O8vii | 2.7500 |
N3···N6 | 2.804 (2) | H22···C23xi | 3.1000 |
N4···N1 | 2.879 (2) | H22···N8ii | 2.8600 |
N4···C36 | 2.418 (3) | H23···N8ii | 2.7200 |
N4···N5 | 2.553 (3) | H23···C52iv | 3.0900 |
N4···N3 | 2.799 (2) | H24···N7iv | 2.8400 |
N4···N2 | 2.914 (2) | H24···O2 | 2.6500 |
N5···N3 | 2.953 (2) | H31···N7 | 2.7100 |
N5···C11 | 3.142 (3) | H31···C26 | 2.9300 |
N5···C21 | 3.170 (3) | H31···N2 | 2.6500 |
N5···N1 | 2.919 (3) | H32···C44ii | 2.8900 |
N5···N4 | 2.553 (3) | H33···C41ii | 2.9700 |
N5···N6 | 2.544 (2) | H33···C42ii | 2.6700 |
N5···C45 | 2.354 (3) | H33···C43ii | 2.8700 |
N5···C35 | 2.358 (3) | H34···H34vii | 2.4600 |
N6···N2 | 2.965 (3) | H34···O3 | 2.6200 |
N6···C46 | 2.406 (3) | H41···O4iii | 2.1200 |
N6···N1 | 2.766 (3) | H41···N2 | 2.7100 |
N6···N5 | 2.544 (2) | H41···O3iii | 2.4700 |
N6···C11 | 3.449 (3) | H42···O7x | 2.6400 |
N6···N3 | 2.804 (2) | H42···Cl1x | 2.9000 |
N7···C31 | 3.133 (4) | H42···O6x | 2.5500 |
N7···C14 | 3.427 (4) | H43···O7xiii | 2.8100 |
N7···C16 | 3.237 (4) | H44···Cl1xiii | 3.0400 |
N7···C15 | 3.243 (4) | H44···H51Cvi | 2.4900 |
N8···C23x | 3.308 (4) | H44···O8xiii | 2.8000 |
N8···C22x | 3.380 (4) | H44···O4 | 2.6200 |
N2···H41 | 2.7100 | H44···O7xiii | 2.6800 |
N2···H31 | 2.6500 | H51A···O6viii | 2.7000 |
N5···H11 | 2.6500 | H51A···O4xiv | 2.8800 |
N5···H21 | 2.6700 | H51B···C42i | 3.1000 |
N7···H24iv | 2.8400 | H51C···H44xiv | 2.4900 |
N7···H61B | 2.8000 | H51C···O8iii | 2.7800 |
N7···H31 | 2.7100 | H51C···C44xiv | 2.9800 |
N8···H22x | 2.8600 | H61A···O5 | 2.4300 |
N8···H23x | 2.7200 | H61B···N7 | 2.8000 |
C11···C46 | 3.507 (3) | H61B···C52 | 3.0600 |
C11···O1v | 3.152 (3) | H61C···O1v | 2.4500 |
N1—Fe1—N2 | 82.19 (7) | C34—C35—C36 | 121.8 (2) |
N1—Fe1—N3 | 164.15 (7) | N4—C35—C34 | 122.6 (2) |
N1—Fe1—N4 | 93.51 (7) | N4—C35—C36 | 115.53 (18) |
N1—Fe1—N5 | 96.95 (7) | O3—C36—C35 | 121.94 (19) |
N1—Fe1—N6 | 89.37 (7) | O3—C36—N5 | 128.4 (2) |
N2—Fe1—N3 | 82.10 (7) | N5—C36—C35 | 109.66 (18) |
N2—Fe1—N4 | 96.87 (8) | N6—C41—C42 | 121.4 (2) |
N2—Fe1—N5 | 178.24 (8) | C41—C42—C43 | 120.2 (2) |
N2—Fe1—N6 | 99.77 (7) | C42—C43—C44 | 118.7 (2) |
N3—Fe1—N4 | 90.45 (7) | C43—C44—C45 | 118.7 (2) |
N3—Fe1—N5 | 98.81 (7) | N6—C45—C46 | 115.14 (18) |
N3—Fe1—N6 | 91.21 (7) | N6—C45—C44 | 122.56 (18) |
N4—Fe1—N5 | 81.64 (7) | C44—C45—C46 | 122.3 (2) |
N4—Fe1—N6 | 163.35 (7) | N5—C46—C45 | 110.10 (18) |
N5—Fe1—N6 | 81.73 (7) | O4—C46—N5 | 128.16 (19) |
O7—Cl1—O8 | 110.49 (15) | O4—C46—C45 | 121.7 (2) |
O5—Cl1—O7 | 108.20 (15) | C12—C11—H11 | 119.00 |
O5—Cl1—O8 | 109.23 (15) | N1—C11—H11 | 119.00 |
O5—Cl1—O6 | 110.81 (15) | C11—C12—H12 | 120.00 |
O6—Cl1—O8 | 109.16 (14) | C13—C12—H12 | 120.00 |
O6—Cl1—O7 | 108.95 (14) | C14—C13—H13 | 121.00 |
C11—N1—C15 | 118.34 (19) | C12—C13—H13 | 121.00 |
Fe1—N1—C15 | 114.06 (13) | C15—C14—H14 | 121.00 |
Fe1—N1—C11 | 127.59 (15) | C13—C14—H14 | 121.00 |
C16—N2—C26 | 123.40 (18) | N3—C21—H21 | 119.00 |
Fe1—N2—C16 | 118.37 (13) | C22—C21—H21 | 119.00 |
Fe1—N2—C26 | 118.17 (15) | C21—C22—H22 | 120.00 |
C21—N3—C25 | 118.60 (18) | C23—C22—H22 | 120.00 |
Fe1—N3—C21 | 126.69 (14) | C24—C23—H23 | 120.00 |
Fe1—N3—C25 | 114.71 (15) | C22—C23—H23 | 120.00 |
Fe1—N4—C31 | 127.48 (14) | C23—C24—H24 | 121.00 |
Fe1—N4—C35 | 114.41 (15) | C25—C24—H24 | 121.00 |
C31—N4—C35 | 118.11 (18) | N4—C31—H31 | 119.00 |
Fe1—N5—C36 | 118.59 (15) | C32—C31—H31 | 119.00 |
C36—N5—C46 | 123.44 (18) | C33—C32—H32 | 120.00 |
Fe1—N5—C46 | 117.94 (13) | C31—C32—H32 | 120.00 |
C41—N6—C45 | 118.54 (18) | C32—C33—H33 | 121.00 |
Fe1—N6—C41 | 126.76 (15) | C34—C33—H33 | 121.00 |
Fe1—N6—C45 | 114.69 (13) | C35—C34—H34 | 121.00 |
N1—C11—C12 | 121.8 (2) | C33—C34—H34 | 121.00 |
C11—C12—C13 | 119.9 (2) | N6—C41—H41 | 119.00 |
C12—C13—C14 | 118.7 (2) | C42—C41—H41 | 119.00 |
C13—C14—C15 | 118.9 (2) | C41—C42—H42 | 120.00 |
C14—C15—C16 | 122.2 (2) | C43—C42—H42 | 120.00 |
N1—C15—C14 | 122.39 (19) | C44—C43—H43 | 121.00 |
N1—C15—C16 | 115.38 (19) | C42—C43—H43 | 121.00 |
O1—C16—N2 | 127.98 (19) | C43—C44—H44 | 121.00 |
N2—C16—C15 | 109.99 (18) | C45—C44—H44 | 121.00 |
O1—C16—C15 | 122.0 (2) | N7—C52—C51 | 178.5 (3) |
N3—C21—C22 | 121.5 (2) | H51B—C51—H51C | 109.00 |
C21—C22—C23 | 119.6 (2) | H51A—C51—H51C | 109.00 |
C22—C23—C24 | 119.1 (2) | C52—C51—H51A | 110.00 |
C23—C24—C25 | 118.8 (2) | C52—C51—H51B | 110.00 |
N3—C25—C26 | 114.88 (18) | C52—C51—H51C | 109.00 |
N3—C25—C24 | 122.4 (2) | H51A—C51—H51B | 109.00 |
C24—C25—C26 | 122.7 (2) | N8—C62—C61 | 179.1 (4) |
O2—C26—C25 | 122.0 (2) | H61B—C61—H61C | 110.00 |
O2—C26—N2 | 128.2 (2) | C62—C61—H61A | 109.00 |
N2—C26—C25 | 109.81 (18) | C62—C61—H61B | 109.00 |
N4—C31—C32 | 121.9 (2) | C62—C61—H61C | 110.00 |
C31—C32—C33 | 119.7 (2) | H61A—C61—H61B | 109.00 |
C32—C33—C34 | 118.9 (2) | H61A—C61—H61C | 109.00 |
C33—C34—C35 | 118.8 (2) | ||
N2—Fe1—N1—C11 | 179.45 (19) | Fe1—N3—C21—C22 | −179.06 (16) |
N2—Fe1—N1—C15 | 1.18 (15) | C25—N3—C21—C22 | 0.4 (3) |
N4—Fe1—N1—C11 | −84.09 (18) | Fe1—N3—C25—C24 | −179.46 (18) |
N4—Fe1—N1—C15 | 97.64 (15) | Fe1—N3—C25—C26 | 0.1 (2) |
N5—Fe1—N1—C11 | −2.10 (19) | C21—N3—C25—C24 | 1.1 (3) |
N5—Fe1—N1—C15 | 179.64 (15) | C21—N3—C25—C26 | −179.37 (19) |
N6—Fe1—N1—C11 | 79.49 (18) | Fe1—N4—C31—C32 | 178.03 (18) |
N6—Fe1—N1—C15 | −98.77 (15) | C35—N4—C31—C32 | −1.6 (3) |
N1—Fe1—N2—C16 | −0.44 (16) | Fe1—N4—C35—C34 | −177.79 (18) |
N1—Fe1—N2—C26 | 176.84 (17) | Fe1—N4—C35—C36 | 1.7 (2) |
N3—Fe1—N2—C16 | 177.44 (17) | C31—N4—C35—C34 | 1.9 (3) |
N3—Fe1—N2—C26 | −5.29 (16) | C31—N4—C35—C36 | −178.61 (19) |
N4—Fe1—N2—C16 | −93.06 (16) | Fe1—N5—C36—O3 | −174.57 (18) |
N4—Fe1—N2—C26 | 84.21 (16) | Fe1—N5—C36—C35 | 4.6 (2) |
N6—Fe1—N2—C16 | 87.57 (16) | C46—N5—C36—O3 | 7.5 (4) |
N6—Fe1—N2—C26 | −95.16 (16) | C46—N5—C36—C35 | −173.35 (19) |
N2—Fe1—N3—C21 | −177.92 (18) | Fe1—N5—C46—O4 | −174.1 (2) |
N2—Fe1—N3—C25 | 2.64 (15) | Fe1—N5—C46—C45 | 5.4 (2) |
N4—Fe1—N3—C21 | 85.21 (18) | C36—N5—C46—O4 | 3.9 (4) |
N4—Fe1—N3—C25 | −94.24 (15) | C36—N5—C46—C45 | −176.57 (19) |
N5—Fe1—N3—C21 | 3.60 (19) | Fe1—N6—C41—C42 | −178.21 (17) |
N5—Fe1—N3—C25 | −175.85 (15) | C45—N6—C41—C42 | 0.4 (3) |
N6—Fe1—N3—C21 | −78.22 (18) | Fe1—N6—C45—C44 | 177.14 (17) |
N6—Fe1—N3—C25 | 102.33 (15) | Fe1—N6—C45—C46 | −3.5 (2) |
N1—Fe1—N4—C31 | −82.51 (19) | C41—N6—C45—C44 | −1.6 (3) |
N1—Fe1—N4—C35 | 97.16 (16) | C41—N6—C45—C46 | 177.71 (19) |
N2—Fe1—N4—C31 | 0.05 (19) | N1—C11—C12—C13 | −0.3 (4) |
N2—Fe1—N4—C35 | 179.70 (15) | C11—C12—C13—C14 | 0.8 (4) |
N3—Fe1—N4—C31 | 82.14 (19) | C12—C13—C14—C15 | −0.7 (4) |
N3—Fe1—N4—C35 | −98.20 (16) | C13—C14—C15—N1 | −0.1 (4) |
N5—Fe1—N4—C31 | −179.03 (19) | C13—C14—C15—C16 | −179.3 (2) |
N5—Fe1—N4—C35 | 0.63 (15) | N1—C15—C16—O1 | −179.5 (2) |
N1—Fe1—N5—C36 | −95.69 (16) | N1—C15—C16—N2 | 1.3 (3) |
N1—Fe1—N5—C46 | 82.40 (16) | C14—C15—C16—O1 | −0.2 (3) |
N3—Fe1—N5—C36 | 86.02 (16) | C14—C15—C16—N2 | −179.4 (2) |
N3—Fe1—N5—C46 | −95.89 (16) | N3—C21—C22—C23 | −1.3 (3) |
N4—Fe1—N5—C36 | −3.14 (15) | C21—C22—C23—C24 | 0.9 (3) |
N4—Fe1—N5—C46 | 174.95 (17) | C22—C23—C24—C25 | 0.4 (4) |
N6—Fe1—N5—C36 | 175.97 (16) | C23—C24—C25—N3 | −1.4 (3) |
N6—Fe1—N5—C46 | −5.94 (16) | C23—C24—C25—C26 | 179.0 (2) |
N1—Fe1—N6—C41 | 86.58 (18) | N3—C25—C26—O2 | 175.1 (2) |
N1—Fe1—N6—C45 | −92.07 (15) | N3—C25—C26—N2 | −4.1 (3) |
N2—Fe1—N6—C41 | 4.62 (19) | C24—C25—C26—O2 | −5.3 (3) |
N2—Fe1—N6—C45 | −174.03 (15) | C24—C25—C26—N2 | 175.5 (2) |
N3—Fe1—N6—C41 | −77.58 (18) | N4—C31—C32—C33 | 0.0 (4) |
N3—Fe1—N6—C45 | 103.77 (15) | C31—C32—C33—C34 | 1.3 (4) |
N5—Fe1—N6—C41 | −176.30 (19) | C32—C33—C34—C35 | −1.1 (4) |
N5—Fe1—N6—C45 | 5.05 (15) | C33—C34—C35—N4 | −0.6 (4) |
Fe1—N1—C11—C12 | −178.61 (17) | C33—C34—C35—C36 | 180.0 (2) |
C15—N1—C11—C12 | −0.4 (3) | N4—C35—C36—O3 | 175.3 (2) |
Fe1—N1—C15—C14 | 179.03 (18) | N4—C35—C36—N5 | −4.0 (3) |
Fe1—N1—C15—C16 | −1.7 (2) | C34—C35—C36—O3 | −5.2 (3) |
C11—N1—C15—C14 | 0.6 (3) | C34—C35—C36—N5 | 175.5 (2) |
C11—N1—C15—C16 | 179.88 (19) | N6—C41—C42—C43 | 1.0 (3) |
Fe1—N2—C16—O1 | −179.43 (19) | C41—C42—C43—C44 | −1.2 (3) |
Fe1—N2—C16—C15 | −0.3 (2) | C42—C43—C44—C45 | 0.0 (3) |
C26—N2—C16—O1 | 3.5 (4) | C43—C44—C45—N6 | 1.4 (3) |
C26—N2—C16—C15 | −177.44 (19) | C43—C44—C45—C46 | −177.9 (2) |
Fe1—N2—C26—O2 | −172.65 (19) | N6—C45—C46—O4 | 178.5 (2) |
Fe1—N2—C26—C25 | 6.4 (2) | N6—C45—C46—N5 | −1.1 (3) |
C16—N2—C26—O2 | 4.5 (4) | C44—C45—C46—O4 | −2.2 (3) |
C16—N2—C26—C25 | −176.43 (19) | C44—C45—C46—N5 | 178.3 (2) |
Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, −y, −z; (v) x, −y+1/2, z+1/2; (vi) x−1, y, z; (vii) −x+1, −y, −z+1; (viii) −x+2, −y, −z+1; (ix) x+1, y, z+1; (x) −x+1, y+1/2, −z+1/2; (xi) −x, −y, −z; (xii) x−1, y, z−1; (xiii) x−1, −y+1/2, z−1/2; (xiv) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1v | 0.95 | 2.41 | 3.152 (3) | 134 |
C11—H11···O2v | 0.95 | 2.54 | 3.269 (3) | 134 |
C21—H21···O6vii | 0.95 | 2.29 | 3.119 (3) | 146 |
C41—H41···O3iii | 0.95 | 2.47 | 3.074 (3) | 121 |
C41—H41···O4iii | 0.95 | 2.12 | 2.981 (3) | 150 |
C42—H42···O6x | 0.95 | 2.55 | 3.434 (3) | 156 |
C61—H61A···O5 | 0.98 | 2.43 | 3.370 (5) | 161 |
C61—H61C···O1v | 0.98 | 2.45 | 3.413 (5) | 168 |
Symmetry codes: (iii) x, −y+1/2, z−1/2; (v) x, −y+1/2, z+1/2; (vii) −x+1, −y, −z+1; (x) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C12H8N3O2)2]ClO4·2C2H3N |
Mr | 689.84 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 12.800 (2), 16.565 (3), 14.895 (2) |
β (°) | 113.356 (16) |
V (Å3) | 2899.4 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.40 × 0.18 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 2003) |
Tmin, Tmax | 0.875, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 70020, 6607, 4867 |
Rint | 0.080 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.095, 1.03 |
No. of reflections | 6607 |
No. of parameters | 417 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.36 |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
Fe1—N1 | 1.9722 (18) | Fe1—N4 | 1.9798 (18) |
Fe1—N2 | 1.9145 (18) | Fe1—N5 | 1.9257 (17) |
Fe1—N3 | 1.9627 (17) | Fe1—N6 | 1.9617 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O1i | 0.95 | 2.41 | 3.152 (3) | 134 |
C11—H11···O2i | 0.95 | 2.54 | 3.269 (3) | 134 |
C21—H21···O6ii | 0.95 | 2.29 | 3.119 (3) | 146 |
C41—H41···O3iii | 0.95 | 2.47 | 3.074 (3) | 121 |
C41—H41···O4iii | 0.95 | 2.12 | 2.981 (3) | 150 |
C42—H42···O6iv | 0.95 | 2.55 | 3.434 (3) | 156 |
C61—H61A···O5 | 0.98 | 2.43 | 3.370 (5) | 161 |
C61—H61C···O1i | 0.98 | 2.45 | 3.413 (5) | 168 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2. |
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During our investigations of iron complexes with di(2-picolyl)amine, we have noticed an unusual reactivity of the –CH2– group attached to the picolyl unit. In the presence of air, this group can be oxidized into a carbonyl group. The storage of a reaction mixture containing Fe(ClO4)2·6H2O, di(2-picolyl)amine and Et3N in the presence of air therefore unintentionally resulted in the formation of the title compound, (I), [Fe(III)(bpca−)2]ClO4·2MeCN, where bpca− is bis(2-pyridylcarbonyl)aminate. We report here the crystal structure of this complex.
The ligand bpca− is present in 68 crystal structures included in the Cambridge Structural Database (Version 5.27 of November 2005, with updates in January, May and August 2006; Allen, 2002), ten of which contain complexes of type M(bpca−)2. Among these are several `pseudopolymorphs', crystal structures containing the same coordination complexes but different counter-ions or solvent molecules. Two main types can be discerned, viz. the neutral complexes with MII and the cationic complexes with MIII as central ion. Neutral complexes have been reported where MII is Cu with water as cocrystallized solvent (Marcos, Martinez-Mañez et al., 1989), Fe with water (Wocadlo et al., 1993), Fe without solvent (Kamiyama et al., 2002), Mn with water (Marcos, Folgado et al., 1990), Rh with water (Paul, Tyagi, Bilakhiya et al., 1999) and Ni without solvent (Kamiyama et al., 2002). In the reported cationic complexes, MIII is Rh with PF6− counter-ions (Paul, Tyagi, Bhadbhade et al., 1997), Fe with NO3− and water (Wocadlo et al., 1993), Co with ClO4− and MeOH (Rowland et al., 2002), and Co with ClO4− and water (Kajiwara et al., 2002). The structure reported here is a pseudopolymorph of the FeIII cationic complex reported by Wocadlo and co-workers, which crystallizes in spacegroup P1.
The iron(III) ion in the structure of (I) has a distorted octahedral coordination, similar to that found in the nitrate/water pseudopolymorph. The two bpca− ligands coordinate the Fe ion in a meridional configuration. The average N,N bite angle in the four five-membered chelate rings is 81.9 (3)°. As a consequence of this small bite angle, the N(pyridine)—Fe—N(pyridine) angles in one ligand [average value 163.8 (6)°] have the largest deviation from the ideal octahedral value of 180°. The Fe—N(pyridine) bonds are, with an average value of 1.969 (8) Å, significantly longer than the Fe—N(amine) bonds, with an average value of 1.920 (8) Å (Table 1 and Fig. 1). This difference in bond lengths is found in all structures containing bpca− ligands coordinating metal ions. The average difference between the M—N(pyridine) and M—N(amine) bonds is 0.07 Å.
The structure of (I) contains a number of short C—H···O contacts (Table 2), with C···O distances as small as 2.981 (3) Å, i.e. 0.24 Å shorter then the sum of their van der Waals radii (Bondi, 1964). Neighbouring molecules are linked by a bifurcated C—H···O,O contact linking a pyridine H atom at an ortho position to the two O atoms of the ligand. Since these contacts occur for both independent ligands, the molecules are linked into an infinite one-dimensional chain, running in the c direction (Fig. 2). Inversion centres are located between C—H···O,O-linked molecules. The ClO4− counter-ion is also involved in this chain through C—H····O contacts and provides an extra link between two neighbouring molecules. In the nitrate/water pseudopolymorph, the same packing motif is found; bifurcated C—H···O,O contacts link the molecules into infinite one-dimensional chains with inversion centres located between the neighbouring molecules. Here also the counter-ion provides an extra link between neighbouring molecules through C—H····O contacts. The other M(bpca−)2 structures of which coordinates are included in the CSD display a great variety in packing, from one-dimensional chains to three-dimensional networks. However, all these structures display the bifurcated pyridine-ortho-H···O,O-urea motif for at least one bpca− ligand, even in the presence of classical hydrogen-bond donors, such as MeOH and water.