Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029776/hb6268sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029776/hb6268Isup2.hkl |
CCDC reference: 287568
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.047
- wR factor = 0.126
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.59 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N7 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N8 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C32
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion
The ligand (2.15 g, 11.0 mmol) (Tam & Li, 2002) was dissolved in a NaHCO3/Na2CO3 buffer solution (100 ml, pH 9.7), and FeCl3·6H2O (0.988 g, 3.67 mmol) was added. The mixture was stirred at room temperature for a few days. The resulting red solid was collected by filtration, and was recrystallized from a mixture of CH2Cl2 and ethyl acetate. Suitable crystals of (I) for X-ray structure determination were obtained by recrystallization from wet DMF and diethyl ether.
All H atoms were placed in calculated positions, with C—H distances ranging from 0.95 to 0.98 Å and N—H = 0.88 Å. They were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(carrier) or Uiso(H) = 1.5Ueq(methyl carrier).
Data collection: Collect (Nonius, 2003); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fe(C9H11N2O3)3·2C3H7NO | Z = 2 |
Mr = 787.64 | F(000) = 830 |
Triclinic, P1 | Dx = 1.435 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.1137 (2) Å | Cell parameters from 24188 reflections |
b = 13.0414 (3) Å | θ = 2.9–27.5° |
c = 13.8382 (3) Å | µ = 0.48 mm−1 |
α = 79.1515 (10)° | T = 150 K |
β = 68.8106 (10)° | Needle, red |
γ = 79.7017 (9)° | 0.10 × 0.06 × 0.04 mm |
V = 1823.18 (7) Å3 |
Bruker–Nonius KappaCCD diffractometer | 8323 independent reflections |
Radiation source: fine-focus sealed tube | 6063 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ scans and ω scans with κ offsets | h = −14→14 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −16→16 |
Tmin = 0.910, Tmax = 0.982 | l = −17→17 |
24188 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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0484P)2 + 0.7105P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
8323 reflections | Δρmax = 0.55 e Å−3 |
492 parameters | Δρmin = −0.49 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0071 (13) |
Fe(C9H11N2O3)3·2C3H7NO | γ = 79.7017 (9)° |
Mr = 787.64 | V = 1823.18 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.1137 (2) Å | Mo Kα radiation |
b = 13.0414 (3) Å | µ = 0.48 mm−1 |
c = 13.8382 (3) Å | T = 150 K |
α = 79.1515 (10)° | 0.10 × 0.06 × 0.04 mm |
β = 68.8106 (10)° |
Bruker–Nonius KappaCCD diffractometer | 8323 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 6063 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.982 | Rint = 0.062 |
24188 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.55 e Å−3 |
8323 reflections | Δρmin = −0.49 e Å−3 |
492 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.28889 (3) | 0.78711 (3) | 0.31899 (3) | 0.02347 (11) | |
O1 | 0.13327 (15) | 0.86403 (13) | 0.42099 (12) | 0.0277 (4) | |
O2 | 0.15914 (15) | 0.78742 (12) | 0.25152 (12) | 0.0249 (3) | |
O3 | −0.0445 (2) | 0.88024 (15) | 0.09043 (14) | 0.0442 (5) | |
O4 | 0.39554 (15) | 0.78024 (12) | 0.41420 (12) | 0.0273 (4) | |
O5 | 0.26770 (16) | 0.64055 (12) | 0.39429 (12) | 0.0272 (4) | |
O6 | 0.12059 (19) | 0.42974 (16) | 0.64768 (15) | 0.0457 (5) | |
O7 | 0.44153 (15) | 0.74585 (12) | 0.19147 (13) | 0.0282 (4) | |
O8 | 0.34766 (15) | 0.92895 (12) | 0.25283 (13) | 0.0277 (4) | |
O9 | 0.5792 (2) | 1.15986 (18) | 0.1839 (2) | 0.0608 (6) | |
N1 | −0.18036 (19) | 0.89789 (16) | 0.32609 (16) | 0.0293 (4) | |
N2 | −0.0428 (2) | 0.71133 (16) | 0.16850 (16) | 0.0329 (5) | |
H2A | −0.0475 | 0.6693 | 0.2272 | 0.040* | |
N3 | 0.34979 (18) | 0.51250 (15) | 0.62407 (15) | 0.0276 (4) | |
N4 | 0.18348 (19) | 0.43692 (16) | 0.47298 (16) | 0.0306 (4) | |
H4A | 0.2386 | 0.4583 | 0.4114 | 0.037* | |
N5 | 0.64957 (19) | 0.99485 (17) | 0.04944 (16) | 0.0322 (5) | |
N6 | 0.3728 (2) | 1.12730 (18) | 0.2389 (2) | 0.0465 (6) | |
H6A | 0.3171 | 1.0888 | 0.2359 | 0.056* | |
C1 | 0.0307 (2) | 0.87723 (17) | 0.39419 (17) | 0.0240 (5) | |
C2 | 0.0437 (2) | 0.83489 (17) | 0.30184 (17) | 0.0228 (5) | |
C3 | −0.0623 (2) | 0.84712 (18) | 0.26940 (18) | 0.0261 (5) | |
C4 | −0.1943 (2) | 0.93950 (19) | 0.4134 (2) | 0.0314 (5) | |
C5 | −0.0893 (2) | 0.92964 (19) | 0.4468 (2) | 0.0296 (5) | |
H5A | −0.0993 | 0.9594 | 0.5073 | 0.036* | |
C6 | −0.0494 (2) | 0.81407 (19) | 0.16729 (19) | 0.0292 (5) | |
C7 | −0.0279 (3) | 0.6658 (2) | 0.0762 (2) | 0.0475 (7) | |
H7A | −0.0269 | 0.5893 | 0.0938 | 0.071* | |
H7B | 0.0539 | 0.6822 | 0.0211 | 0.071* | |
H7C | −0.1008 | 0.6952 | 0.0514 | 0.071* | |
C8 | −0.2936 (2) | 0.9061 (2) | 0.2919 (2) | 0.0412 (7) | |
H8A | −0.3672 | 0.8802 | 0.3509 | 0.062* | |
H8B | −0.2715 | 0.8637 | 0.2350 | 0.062* | |
H8C | −0.3173 | 0.9798 | 0.2672 | 0.062* | |
C9 | −0.3236 (3) | 0.9950 (2) | 0.4713 (2) | 0.0443 (7) | |
H9A | −0.3149 | 1.0291 | 0.5254 | 0.066* | |
H9B | −0.3865 | 0.9440 | 0.5041 | 0.066* | |
H9C | −0.3540 | 1.0483 | 0.4223 | 0.066* | |
C10 | 0.3841 (2) | 0.69697 (18) | 0.48249 (18) | 0.0248 (5) | |
C11 | 0.3128 (2) | 0.61858 (18) | 0.47260 (17) | 0.0245 (5) | |
C12 | 0.2925 (2) | 0.53021 (19) | 0.54708 (18) | 0.0260 (5) | |
C13 | 0.4169 (2) | 0.5842 (2) | 0.63377 (19) | 0.0317 (5) | |
C14 | 0.4330 (2) | 0.6767 (2) | 0.56441 (19) | 0.0309 (5) | |
H14A | 0.4785 | 0.7275 | 0.5731 | 0.037* | |
C15 | 0.1930 (2) | 0.46036 (18) | 0.55926 (19) | 0.0288 (5) | |
C16 | 0.0819 (3) | 0.3759 (2) | 0.4802 (2) | 0.0383 (6) | |
H16A | 0.0584 | 0.3953 | 0.4168 | 0.058* | |
H16B | 0.0053 | 0.3906 | 0.5414 | 0.058* | |
H16C | 0.1139 | 0.3007 | 0.4872 | 0.058* | |
C17 | 0.3462 (3) | 0.4106 (2) | 0.6930 (2) | 0.0364 (6) | |
H17A | 0.4291 | 0.3907 | 0.7057 | 0.055* | |
H17B | 0.3319 | 0.3565 | 0.6592 | 0.055* | |
H17C | 0.2753 | 0.4172 | 0.7597 | 0.055* | |
C18 | 0.4712 (3) | 0.5635 (3) | 0.7213 (2) | 0.0446 (7) | |
H18A | 0.4024 | 0.5448 | 0.7876 | 0.067* | |
H18B | 0.5047 | 0.6268 | 0.7248 | 0.067* | |
H18C | 0.5418 | 0.5053 | 0.7087 | 0.067* | |
C19 | 0.5094 (2) | 0.82285 (19) | 0.14194 (18) | 0.0272 (5) | |
C20 | 0.4609 (2) | 0.92401 (18) | 0.17708 (18) | 0.0255 (5) | |
C21 | 0.5344 (2) | 1.00793 (19) | 0.13354 (19) | 0.0283 (5) | |
C22 | 0.6930 (2) | 0.9018 (2) | 0.01139 (19) | 0.0327 (6) | |
C23 | 0.6256 (2) | 0.8157 (2) | 0.05765 (19) | 0.0324 (5) | |
H23A | 0.6592 | 0.7503 | 0.0314 | 0.039* | |
C24 | 0.4979 (3) | 1.1057 (2) | 0.1849 (2) | 0.0366 (6) | |
C25 | 0.3250 (3) | 1.2117 (3) | 0.3024 (3) | 0.0590 (9) | |
H25A | 0.2370 | 1.2022 | 0.3510 | 0.088* | |
H25B | 0.3230 | 1.2792 | 0.2573 | 0.088* | |
H25C | 0.3824 | 1.2112 | 0.3421 | 0.088* | |
C26 | 0.7246 (3) | 1.0846 (2) | −0.0055 (2) | 0.0514 (8) | |
H26A | 0.7450 | 1.0885 | −0.0811 | 0.077* | |
H26B | 0.8054 | 1.0745 | 0.0102 | 0.077* | |
H26C | 0.6728 | 1.1501 | 0.0181 | 0.077* | |
C27 | 0.8154 (3) | 0.8938 (3) | −0.0817 (2) | 0.0426 (7) | |
H27A | 0.8872 | 0.9118 | −0.0655 | 0.064* | |
H27B | 0.8031 | 0.9426 | −0.1415 | 0.064* | |
H27C | 0.8357 | 0.8218 | −0.0990 | 0.064* | |
N7 | 0.0956 (2) | 0.73488 (19) | 0.75274 (17) | 0.0398 (5) | |
O10 | 0.1436 (2) | 0.58480 (17) | 0.85225 (16) | 0.0527 (5) | |
C28 | 0.0412 (4) | 0.7850 (3) | 0.6726 (3) | 0.0683 (10) | |
H28A | −0.0033 | 0.7348 | 0.6574 | 0.102* | |
H28B | 0.1111 | 0.8083 | 0.6089 | 0.102* | |
H28C | −0.0211 | 0.8459 | 0.6972 | 0.102* | |
C29 | 0.1687 (3) | 0.7974 (3) | 0.7827 (3) | 0.0538 (8) | |
H29A | 0.1925 | 0.7583 | 0.8423 | 0.081* | |
H29B | 0.1152 | 0.8635 | 0.8024 | 0.081* | |
H29C | 0.2477 | 0.8125 | 0.7236 | 0.081* | |
C30 | 0.0919 (3) | 0.6329 (2) | 0.7895 (2) | 0.0436 (7) | |
H30A | 0.0456 | 0.5947 | 0.7654 | 0.052* | |
O11 | 0.2237 (3) | 0.4605 (2) | 0.24787 (19) | 0.0664 (7) | |
N8 | 0.2922 (3) | 0.54095 (19) | 0.0819 (2) | 0.0525 (7) | |
C31 | 0.3368 (5) | 0.6347 (3) | 0.0119 (3) | 0.0888 (15) | |
H31A | 0.3473 | 0.6850 | 0.0519 | 0.133* | |
H31B | 0.2729 | 0.6667 | −0.0220 | 0.133* | |
H31C | 0.4205 | 0.6158 | −0.0414 | 0.133* | |
C32 | 0.2877 (4) | 0.4527 (3) | 0.0343 (3) | 0.0704 (11) | |
H32A | 0.2566 | 0.3943 | 0.0890 | 0.106* | |
H32B | 0.3750 | 0.4304 | −0.0124 | 0.106* | |
H32C | 0.2285 | 0.4735 | −0.0059 | 0.106* | |
C33 | 0.2574 (3) | 0.5368 (2) | 0.1850 (3) | 0.0527 (8) | |
H33A | 0.2592 | 0.5986 | 0.2112 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.02321 (18) | 0.02204 (18) | 0.02636 (19) | −0.00289 (12) | −0.01067 (13) | −0.00142 (12) |
O1 | 0.0258 (8) | 0.0318 (9) | 0.0298 (9) | −0.0028 (7) | −0.0132 (7) | −0.0077 (7) |
O2 | 0.0245 (8) | 0.0249 (8) | 0.0268 (8) | −0.0007 (6) | −0.0108 (7) | −0.0046 (6) |
O3 | 0.0644 (13) | 0.0429 (11) | 0.0341 (10) | −0.0199 (10) | −0.0288 (10) | 0.0109 (8) |
O4 | 0.0276 (8) | 0.0250 (8) | 0.0319 (9) | −0.0048 (7) | −0.0139 (7) | −0.0008 (7) |
O5 | 0.0328 (9) | 0.0248 (8) | 0.0278 (9) | −0.0064 (7) | −0.0156 (7) | 0.0007 (6) |
O6 | 0.0476 (11) | 0.0570 (13) | 0.0323 (10) | −0.0245 (10) | −0.0125 (9) | 0.0099 (9) |
O7 | 0.0278 (8) | 0.0256 (8) | 0.0311 (9) | −0.0036 (7) | −0.0101 (7) | −0.0035 (7) |
O8 | 0.0252 (8) | 0.0233 (8) | 0.0322 (9) | −0.0023 (6) | −0.0081 (7) | −0.0023 (7) |
O9 | 0.0505 (13) | 0.0507 (13) | 0.0900 (18) | −0.0192 (11) | −0.0243 (13) | −0.0172 (12) |
N1 | 0.0247 (10) | 0.0305 (11) | 0.0362 (11) | −0.0022 (8) | −0.0168 (9) | −0.0012 (9) |
N2 | 0.0435 (12) | 0.0329 (12) | 0.0247 (10) | −0.0087 (10) | −0.0133 (9) | −0.0018 (8) |
N3 | 0.0252 (10) | 0.0290 (11) | 0.0259 (10) | 0.0014 (8) | −0.0101 (8) | 0.0012 (8) |
N4 | 0.0314 (11) | 0.0299 (11) | 0.0309 (11) | −0.0050 (9) | −0.0106 (9) | −0.0040 (8) |
N5 | 0.0270 (10) | 0.0390 (12) | 0.0314 (11) | −0.0098 (9) | −0.0126 (9) | 0.0042 (9) |
N6 | 0.0402 (13) | 0.0332 (13) | 0.0691 (17) | −0.0049 (10) | −0.0159 (12) | −0.0187 (12) |
C1 | 0.0257 (11) | 0.0213 (11) | 0.0259 (12) | −0.0051 (9) | −0.0104 (9) | 0.0003 (9) |
C2 | 0.0245 (11) | 0.0190 (11) | 0.0252 (11) | −0.0034 (9) | −0.0103 (9) | 0.0011 (8) |
C3 | 0.0289 (12) | 0.0238 (12) | 0.0280 (12) | −0.0052 (9) | −0.0138 (10) | 0.0014 (9) |
C4 | 0.0264 (12) | 0.0287 (13) | 0.0381 (14) | −0.0001 (10) | −0.0105 (11) | −0.0061 (10) |
C5 | 0.0268 (12) | 0.0303 (13) | 0.0342 (13) | −0.0027 (10) | −0.0107 (10) | −0.0098 (10) |
C6 | 0.0273 (12) | 0.0357 (14) | 0.0289 (13) | −0.0098 (10) | −0.0148 (10) | 0.0019 (10) |
C7 | 0.064 (2) | 0.0491 (18) | 0.0336 (15) | −0.0096 (15) | −0.0181 (14) | −0.0107 (13) |
C8 | 0.0309 (13) | 0.0507 (17) | 0.0517 (17) | −0.0011 (12) | −0.0265 (13) | −0.0088 (13) |
C9 | 0.0275 (13) | 0.0487 (17) | 0.0561 (18) | 0.0044 (12) | −0.0136 (13) | −0.0157 (14) |
C10 | 0.0204 (10) | 0.0260 (12) | 0.0273 (12) | 0.0004 (9) | −0.0080 (9) | −0.0051 (9) |
C11 | 0.0228 (11) | 0.0256 (12) | 0.0253 (12) | 0.0004 (9) | −0.0098 (9) | −0.0035 (9) |
C12 | 0.0244 (11) | 0.0302 (12) | 0.0237 (12) | −0.0023 (9) | −0.0095 (9) | −0.0027 (9) |
C13 | 0.0237 (12) | 0.0434 (15) | 0.0273 (13) | −0.0010 (10) | −0.0107 (10) | −0.0023 (10) |
C14 | 0.0282 (12) | 0.0381 (14) | 0.0311 (13) | −0.0059 (10) | −0.0150 (10) | −0.0039 (10) |
C15 | 0.0331 (13) | 0.0230 (12) | 0.0296 (13) | −0.0037 (10) | −0.0125 (10) | 0.0024 (9) |
C16 | 0.0456 (15) | 0.0301 (14) | 0.0440 (16) | −0.0123 (12) | −0.0168 (13) | −0.0054 (11) |
C17 | 0.0372 (14) | 0.0360 (14) | 0.0312 (13) | 0.0015 (11) | −0.0138 (11) | 0.0058 (11) |
C18 | 0.0429 (15) | 0.0623 (19) | 0.0343 (15) | −0.0128 (14) | −0.0221 (13) | 0.0039 (13) |
C19 | 0.0248 (11) | 0.0318 (13) | 0.0285 (12) | −0.0008 (10) | −0.0149 (10) | −0.0027 (10) |
C20 | 0.0246 (11) | 0.0281 (12) | 0.0268 (12) | −0.0035 (9) | −0.0141 (10) | 0.0001 (9) |
C21 | 0.0276 (12) | 0.0300 (13) | 0.0304 (13) | −0.0050 (10) | −0.0154 (10) | 0.0012 (10) |
C22 | 0.0282 (12) | 0.0442 (15) | 0.0268 (13) | −0.0047 (11) | −0.0125 (10) | −0.0005 (11) |
C23 | 0.0294 (12) | 0.0357 (14) | 0.0332 (13) | −0.0003 (10) | −0.0120 (11) | −0.0082 (11) |
C24 | 0.0380 (14) | 0.0314 (14) | 0.0457 (16) | −0.0107 (11) | −0.0205 (13) | 0.0011 (11) |
C25 | 0.0552 (19) | 0.0407 (17) | 0.081 (2) | −0.0076 (15) | −0.0140 (18) | −0.0240 (16) |
C26 | 0.0516 (18) | 0.0476 (18) | 0.0467 (18) | −0.0241 (15) | −0.0050 (14) | 0.0070 (14) |
C27 | 0.0329 (14) | 0.0627 (19) | 0.0280 (14) | −0.0047 (13) | −0.0079 (11) | −0.0018 (13) |
N7 | 0.0429 (13) | 0.0457 (14) | 0.0328 (12) | −0.0045 (11) | −0.0142 (10) | −0.0079 (10) |
O10 | 0.0632 (14) | 0.0483 (13) | 0.0406 (12) | 0.0009 (11) | −0.0138 (10) | −0.0060 (9) |
C28 | 0.095 (3) | 0.067 (2) | 0.053 (2) | 0.008 (2) | −0.043 (2) | −0.0124 (17) |
C29 | 0.0523 (18) | 0.058 (2) | 0.0531 (19) | −0.0166 (16) | −0.0153 (15) | −0.0070 (15) |
C30 | 0.0431 (16) | 0.0496 (18) | 0.0372 (15) | −0.0060 (13) | −0.0064 (13) | −0.0176 (13) |
O11 | 0.0832 (18) | 0.0606 (16) | 0.0525 (14) | −0.0037 (13) | −0.0231 (13) | −0.0055 (12) |
N8 | 0.085 (2) | 0.0335 (13) | 0.0498 (15) | −0.0063 (13) | −0.0375 (15) | −0.0041 (11) |
C31 | 0.162 (5) | 0.055 (2) | 0.075 (3) | −0.043 (3) | −0.070 (3) | 0.017 (2) |
C32 | 0.119 (3) | 0.0432 (19) | 0.061 (2) | −0.010 (2) | −0.042 (2) | −0.0128 (16) |
C33 | 0.077 (2) | 0.0359 (16) | 0.057 (2) | 0.0051 (15) | −0.0400 (18) | −0.0095 (14) |
Fe1—O2 | 1.9801 (15) | C12—C15 | 1.499 (3) |
Fe1—O5 | 2.0071 (16) | C13—C14 | 1.388 (4) |
Fe1—O8 | 2.0121 (16) | C13—C18 | 1.500 (3) |
Fe1—O1 | 2.0342 (16) | C14—H14A | 0.9500 |
Fe1—O7 | 2.0367 (16) | C16—H16A | 0.9800 |
Fe1—O4 | 2.0483 (16) | C16—H16B | 0.9800 |
C1—O1 | 1.295 (3) | C16—H16C | 0.9800 |
C2—O2 | 1.321 (3) | C17—H17A | 0.9800 |
O3—C6 | 1.228 (3) | C17—H17B | 0.9800 |
C10—O4 | 1.290 (3) | C17—H17C | 0.9800 |
C11—O5 | 1.316 (3) | C18—H18A | 0.9800 |
O6—C15 | 1.234 (3) | C18—H18B | 0.9800 |
C19—O7 | 1.298 (3) | C18—H18C | 0.9800 |
C20—O8 | 1.315 (3) | C19—C23 | 1.395 (3) |
O9—C24 | 1.237 (3) | C19—C20 | 1.437 (3) |
N1—C4 | 1.363 (3) | C20—C21 | 1.394 (3) |
N1—C3 | 1.384 (3) | C21—C24 | 1.498 (4) |
N1—C8 | 1.477 (3) | C22—C23 | 1.384 (3) |
N2—C6 | 1.326 (3) | C22—C27 | 1.502 (3) |
N2—C7 | 1.453 (3) | C23—H23A | 0.9500 |
N2—H2A | 0.8800 | C25—H25A | 0.9800 |
N3—C13 | 1.348 (3) | C25—H25B | 0.9800 |
N3—C12 | 1.392 (3) | C25—H25C | 0.9800 |
N3—C17 | 1.481 (3) | C26—H26A | 0.9800 |
N4—C15 | 1.331 (3) | C26—H26B | 0.9800 |
N4—C16 | 1.459 (3) | C26—H26C | 0.9800 |
N4—H4A | 0.8800 | C27—H27A | 0.9800 |
N5—C22 | 1.352 (3) | C27—H27B | 0.9800 |
N5—C21 | 1.394 (3) | C27—H27C | 0.9800 |
N5—C26 | 1.483 (3) | N7—C30 | 1.334 (4) |
N6—C24 | 1.327 (4) | N7—C28 | 1.447 (4) |
N6—C25 | 1.444 (4) | N7—C29 | 1.450 (4) |
N6—H6A | 0.8800 | O10—C30 | 1.226 (4) |
C1—C5 | 1.392 (3) | C28—H28A | 0.9800 |
C1—C2 | 1.436 (3) | C28—H28B | 0.9800 |
C2—C3 | 1.380 (3) | C28—H28C | 0.9800 |
C3—C6 | 1.505 (3) | C29—H29A | 0.9800 |
C4—C5 | 1.381 (3) | C29—H29B | 0.9800 |
C4—C9 | 1.499 (3) | C29—H29C | 0.9800 |
C5—H5A | 0.9500 | C30—H30A | 0.9500 |
C7—H7A | 0.9800 | O11—C33 | 1.208 (4) |
C7—H7B | 0.9800 | N8—C33 | 1.329 (4) |
C7—H7C | 0.9800 | N8—C32 | 1.446 (4) |
C8—H8A | 0.9800 | N8—C31 | 1.450 (4) |
C8—H8B | 0.9800 | C31—H31A | 0.9800 |
C8—H8C | 0.9800 | C31—H31B | 0.9800 |
C9—H9A | 0.9800 | C31—H31C | 0.9800 |
C9—H9B | 0.9800 | C32—H32A | 0.9800 |
C9—H9C | 0.9800 | C32—H32B | 0.9800 |
C10—C14 | 1.390 (3) | C32—H32C | 0.9800 |
C10—C11 | 1.453 (3) | C33—H33A | 0.9500 |
C11—C12 | 1.385 (3) | ||
O2—Fe1—O5 | 93.98 (6) | N4—C15—C12 | 118.0 (2) |
O2—Fe1—O8 | 99.02 (7) | N4—C16—H16A | 109.5 |
O5—Fe1—O8 | 166.59 (7) | N4—C16—H16B | 109.5 |
O2—Fe1—O1 | 81.53 (6) | H16A—C16—H16B | 109.5 |
O5—Fe1—O1 | 98.07 (7) | N4—C16—H16C | 109.5 |
O8—Fe1—O1 | 87.16 (6) | H16A—C16—H16C | 109.5 |
O2—Fe1—O7 | 93.14 (6) | H16B—C16—H16C | 109.5 |
O5—Fe1—O7 | 96.30 (7) | N3—C17—H17A | 109.5 |
O8—Fe1—O7 | 79.79 (6) | N3—C17—H17B | 109.5 |
O1—Fe1—O7 | 164.98 (7) | H17A—C17—H17B | 109.5 |
O2—Fe1—O4 | 169.33 (6) | N3—C17—H17C | 109.5 |
O5—Fe1—O4 | 80.10 (6) | H17A—C17—H17C | 109.5 |
O8—Fe1—O4 | 87.55 (6) | H17B—C17—H17C | 109.5 |
O1—Fe1—O4 | 90.46 (6) | C13—C18—H18A | 109.5 |
O7—Fe1—O4 | 96.32 (7) | C13—C18—H18B | 109.5 |
C1—O1—Fe1 | 112.04 (14) | H18A—C18—H18B | 109.5 |
C2—O2—Fe1 | 112.54 (13) | C13—C18—H18C | 109.5 |
C10—O4—Fe1 | 112.76 (14) | H18A—C18—H18C | 109.5 |
C11—O5—Fe1 | 113.43 (13) | H18B—C18—H18C | 109.5 |
C19—O7—Fe1 | 112.58 (15) | O7—C19—C23 | 125.5 (2) |
C20—O8—Fe1 | 113.46 (14) | O7—C19—C20 | 117.3 (2) |
C4—N1—C3 | 121.22 (19) | C23—C19—C20 | 117.2 (2) |
C4—N1—C8 | 119.4 (2) | O8—C20—C21 | 124.3 (2) |
C3—N1—C8 | 119.3 (2) | O8—C20—C19 | 115.4 (2) |
C6—N2—C7 | 122.2 (2) | C21—C20—C19 | 120.3 (2) |
C6—N2—H2A | 118.9 | N5—C21—C20 | 119.0 (2) |
C7—N2—H2A | 118.9 | N5—C21—C24 | 120.6 (2) |
C13—N3—C12 | 121.4 (2) | C20—C21—C24 | 120.0 (2) |
C13—N3—C17 | 118.1 (2) | N5—C22—C23 | 120.5 (2) |
C12—N3—C17 | 120.4 (2) | N5—C22—C27 | 118.8 (2) |
C15—N4—C16 | 120.2 (2) | C23—C22—C27 | 120.7 (2) |
C15—N4—H4A | 119.9 | C22—C23—C19 | 121.4 (2) |
C16—N4—H4A | 119.9 | C22—C23—H23A | 119.3 |
C22—N5—C21 | 121.4 (2) | C19—C23—H23A | 119.3 |
C22—N5—C26 | 117.6 (2) | O9—C24—N6 | 121.1 (3) |
C21—N5—C26 | 120.9 (2) | O9—C24—C21 | 122.8 (3) |
C24—N6—C25 | 122.2 (2) | N6—C24—C21 | 115.9 (2) |
C24—N6—H6A | 118.9 | N6—C25—H25A | 109.5 |
C25—N6—H6A | 118.9 | N6—C25—H25B | 109.5 |
O1—C1—C5 | 125.4 (2) | H25A—C25—H25B | 109.5 |
O1—C1—C2 | 116.7 (2) | N6—C25—H25C | 109.5 |
C5—C1—C2 | 118.0 (2) | H25A—C25—H25C | 109.5 |
O2—C2—C3 | 123.7 (2) | H25B—C25—H25C | 109.5 |
O2—C2—C1 | 117.19 (19) | N5—C26—H26A | 109.5 |
C3—C2—C1 | 119.1 (2) | N5—C26—H26B | 109.5 |
C2—C3—N1 | 120.5 (2) | H26A—C26—H26B | 109.5 |
C2—C3—C6 | 120.9 (2) | N5—C26—H26C | 109.5 |
N1—C3—C6 | 118.44 (19) | H26A—C26—H26C | 109.5 |
N1—C4—C5 | 119.5 (2) | H26B—C26—H26C | 109.5 |
N1—C4—C9 | 119.3 (2) | C22—C27—H27A | 109.5 |
C5—C4—C9 | 121.2 (2) | C22—C27—H27B | 109.5 |
C4—C5—C1 | 121.7 (2) | H27A—C27—H27B | 109.5 |
C4—C5—H5A | 119.2 | C22—C27—H27C | 109.5 |
C1—C5—H5A | 119.2 | H27A—C27—H27C | 109.5 |
O3—C6—N2 | 124.8 (2) | H27B—C27—H27C | 109.5 |
O3—C6—C3 | 120.2 (2) | C30—N7—C28 | 122.1 (3) |
N2—C6—C3 | 115.0 (2) | C30—N7—C29 | 120.7 (3) |
N2—C7—H7A | 109.5 | C28—N7—C29 | 116.8 (3) |
N2—C7—H7B | 109.5 | N7—C28—H28A | 109.5 |
H7A—C7—H7B | 109.5 | N7—C28—H28B | 109.5 |
N2—C7—H7C | 109.5 | H28A—C28—H28B | 109.5 |
H7A—C7—H7C | 109.5 | N7—C28—H28C | 109.5 |
H7B—C7—H7C | 109.5 | H28A—C28—H28C | 109.5 |
N1—C8—H8A | 109.5 | H28B—C28—H28C | 109.5 |
N1—C8—H8B | 109.5 | N7—C29—H29A | 109.5 |
H8A—C8—H8B | 109.5 | N7—C29—H29B | 109.5 |
N1—C8—H8C | 109.5 | H29A—C29—H29B | 109.5 |
H8A—C8—H8C | 109.5 | N7—C29—H29C | 109.5 |
H8B—C8—H8C | 109.5 | H29A—C29—H29C | 109.5 |
C4—C9—H9A | 109.5 | H29B—C29—H29C | 109.5 |
C4—C9—H9B | 109.5 | O10—C30—N7 | 124.9 (3) |
H9A—C9—H9B | 109.5 | O10—C30—H30A | 117.5 |
C4—C9—H9C | 109.5 | N7—C30—H30A | 117.5 |
H9A—C9—H9C | 109.5 | C33—N8—C32 | 121.9 (3) |
H9B—C9—H9C | 109.5 | C33—N8—C31 | 121.2 (3) |
O4—C10—C14 | 125.6 (2) | C32—N8—C31 | 116.9 (3) |
O4—C10—C11 | 116.6 (2) | N8—C31—H31A | 109.5 |
C14—C10—C11 | 117.8 (2) | N8—C31—H31B | 109.5 |
O5—C11—C12 | 125.2 (2) | H31A—C31—H31B | 109.5 |
O5—C11—C10 | 116.04 (19) | N8—C31—H31C | 109.5 |
C12—C11—C10 | 118.7 (2) | H31A—C31—H31C | 109.5 |
C11—C12—N3 | 120.3 (2) | H31B—C31—H31C | 109.5 |
C11—C12—C15 | 121.9 (2) | N8—C32—H32A | 109.5 |
N3—C12—C15 | 117.03 (19) | N8—C32—H32B | 109.5 |
N3—C13—C14 | 120.0 (2) | H32A—C32—H32B | 109.5 |
N3—C13—C18 | 119.2 (2) | N8—C32—H32C | 109.5 |
C14—C13—C18 | 120.8 (2) | H32A—C32—H32C | 109.5 |
C13—C14—C10 | 121.6 (2) | H32B—C32—H32C | 109.5 |
C13—C14—H14A | 119.2 | O11—C33—N8 | 125.0 (3) |
C10—C14—H14A | 119.2 | O11—C33—H33A | 117.5 |
O6—C15—N4 | 122.5 (2) | N8—C33—H33A | 117.5 |
O6—C15—C12 | 119.4 (2) | ||
C2—C3—C6—O3 | −102.5 (3) | C20—C21—C24—O9 | 146.6 (3) |
C11—C12—C15—O6 | −135.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O6i | 0.88 | 1.96 | 2.797 (3) | 158 |
N4—H4A···O11 | 0.88 | 2.32 | 2.946 (3) | 128 |
N4—H4A···O5 | 0.88 | 2.41 | 2.860 (3) | 112 |
N6—H6A···O8 | 0.88 | 2.03 | 2.615 (3) | 123 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | Fe(C9H11N2O3)3·2C3H7NO |
Mr | 787.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 11.1137 (2), 13.0414 (3), 13.8382 (3) |
α, β, γ (°) | 79.1515 (10), 68.8106 (10), 79.7017 (9) |
V (Å3) | 1823.18 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.10 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.910, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24188, 8323, 6063 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.126, 1.01 |
No. of reflections | 8323 |
No. of parameters | 492 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.49 |
Computer programs: Collect (Nonius, 2003), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick, 2001), SHELXTL.
Fe1—O2 | 1.9801 (15) | C1—O1 | 1.295 (3) |
Fe1—O5 | 2.0071 (16) | C2—O2 | 1.321 (3) |
Fe1—O8 | 2.0121 (16) | C10—O4 | 1.290 (3) |
Fe1—O1 | 2.0342 (16) | C11—O5 | 1.316 (3) |
Fe1—O7 | 2.0367 (16) | C19—O7 | 1.298 (3) |
Fe1—O4 | 2.0483 (16) | C20—O8 | 1.315 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O6i | 0.88 | 1.96 | 2.797 (3) | 158 |
N4—H4A···O11 | 0.88 | 2.32 | 2.946 (3) | 128 |
N4—H4A···O5 | 0.88 | 2.41 | 2.860 (3) | 112 |
N6—H6A···O8 | 0.88 | 2.03 | 2.615 (3) | 123 |
Symmetry code: (i) −x, −y+1, −z+1. |
Iron chelation therapy is now a mainstay for the treatment of human conditions of iron overload, e.g. transfusion-dependent β-thalassaemia (Cohen et al., 2004). At present, the bidentate 1,2-dimethyl-3-hydroxy-4-pyridinone ligand (L1; also known as CP20, deferiprone or Ferriprox) is the only oral iron chelator drug approved (in 48 countries) for β-thalassaemic patients (Tam et al., 2003). However, L1 undergoes extensive metabolism in the liver, and more than 85% of the administered drug is recovered in the urine as the inactive 3-O-glucuronide. Hence, information on the structure of the ligand (L), as well as of the FeL3 chelate, is important for the design of new bidentate FeIII-sequestering agents with better pharmacokinetic profiles. The single-crystal X-ray structures of Fe(L1)3 (Charalambous et al., 1988; Clarke et al., 1992) and M(L1)3 (M = Al and Ga; Nelson et al., 1988) have been reported previously. We report here the structure of the title compound, (I), an iron(III) complex of a related ligand, 2-N-methylaminocarbonyl-3-hydroxy-1,6-dimethyl-1,4-dihydro-4-pyridinone (L2).
The structure of (I) is shown in Fig. 1, and selected geometrical data are given in Table 1. The FeIII ion is six-coordinate, with a distorted octahedral configuration consisting of six donor O atoms from three bidentate ligands. There is a difference in the Fe—O bond lengths (Table 1), with three (Fe—O2,O5,O8) being significantly shorter than the other three (Fe—O1,O3,O7). In addition, the short and long bond distances (Table 1) for the chelating C—O groups indicate that some ketonic character has been retained in the complex.
The amide groups of all three ligands are rotated out of the planes of the respective pyridinone rings to which they are bonded, giving dihedral angles of −102.5 (3), −135.3 (3) and 146.6 (3)° for C2—C3—C6—O3, C11—C12—C15—O6 and C20—C21—C24—O9, respectively. The largest out of plane rotation for the amide group containing N2 facilitates the formation of an intermolecular N—H···O hydrogen bond linking molecules into centrosymmetric dimers (Fig. 2), creating R22(24) rings (Bernstein et al., 1995), while the NH groups of the other two amide moieties are involved in intramolecular N—H···O hydrogen bonds, one of which is also involved in the formation of an N—H···O hydrogen bond to one dimethylformamide solvent molecule (see Table 2 for hydrogen-bond geometries). There are also numerous weak C—H···O interactions present in the crystal structure of (I), with H···O distances ranging from 2.17 to 2.59 Å, but these are not discussed in detail here.