Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041955/bi2229sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041955/bi2229Isup2.hkl |
CCDC reference: 663554
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.060
- wR factor = 0.133
- Data-to-parameter ratio = 13.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for O11 - C1 .. 10.23 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O11 - C12 .. 18.62 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O12 - C2 .. 12.90 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O16 - C10 .. 8.96 su PLAT230_ALERT_2_B Hirshfeld Test Diff for O16 - C11 .. 11.56 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C9 - C10 .. 8.48 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C11 - C12 .. 11.94 su PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for O16
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - C26 .. 5.55 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for O11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for O15 PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C9 - C10 ... 1.42 Ang. PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C11 - C12 ... 1.36 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 H2 O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 H2 O
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (3) 3.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 26
0 ALERT level A = In general: serious problem 9 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 15 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the crystal structure of [Fe(HChel)Cl(H2O)2], see: Laine et al. (1995). For other literature related to the use of chelidamic acid as a ligand, see: Cline et al. (1979); Hall et al. (2000); Ng (1998, 1999); Riegel (1926); Thich et al. (1976); Yang et al. (2002).
A mixture of FeCl3.6H2O (0.068 g, 0.25 mmol), 18-crown-6 (0.066 g, 0.25 mmol) and H3Chel (50 mg, 0.25 mmol) was dissolved in 20 ml of a mixed ethanol:water (1:1) solvent. After dropping 1–2 drops KOH (1M) into the solution and stirring for about 4 h, the solution was filtered and the filtrate was allowed to stand at room temperature. Yellow–brown crystals of the title compound were obtained after 4–5 days (yield: 63%).
H atoms bonded to C atoms and the H atom of the hydroxyl group were placed at calculated positions and allowed to ride during subsequent refinement with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). The H atoms of the water molecules were located in difference Fourier maps and refined with O—H distances restrained to a target value of 0.96 (1) Å, and with Uiso(H) = 1.5Ueq(O). The anisotropic displacement parameters of C1, C2 and C12 were restrained to approximate isotropic behaviour.
Since the first report of chelidamic acid (4-hydroxypyridine-2,6-dicarboxylic acid) in 1926 (Riegel, 1926), its coordination chemistry has been extensively investigated. Much of this work focuses on the design and synthesis of polymers in which chelidamic acid acts as a ligand (Ng, 1998, 1999; Riegel, 1926; Hall et al., 2000; Cline et al., 1979; Yang et al., 2002; Thich et al., 1976, Laine et al., 1995). Herein, we report the synthesis and crystal structure of the title compound, which is an FeIII complex in which chelidamic acid acts as a tridentate chelating ligand.
The asymmetric unit (Fig. 1) consists of one FeIII atom coordinated by one chelidamic acid ligand, one Cl atom and two coordinated water molecules, as well as one 18-crown-6 molecule and two lattice water molecules. The coordination environment of FeIII comprises two carboxylic O atoms (Fe1—O2 = 2.0248 (17), Fe1—O4 = 2.0507 (16) Å) and one N atom (Fe1—N1 = 2.055 (2) Å) from the tridentate chelated chelidamic acid ligand, one Cl atom (Fe1—Cl1 = 2.2522 (9) Å) lying in the equatorial plane, and two water molecules (Fe1—O1W = 2.0531 (19), Fe1—O2W = 2.0613 (18) Å) in the axial positions, forming a distorted octahedral geometry. Due to the monodentate coordination mode of both carboxylate groups of the chelidamic acid ligand, the C—O bond distances of the coordinated O atoms (C26—O2 = 1.293 (3) and C27—O4 = 1.280 (3) Å) are slightly longer than the C—O bond distances of the uncoordinated O atoms (C26—O1 = 1.218 (3) and C27—O3 = 1.233 (3) Å).
The coordinated water molecules, O1W and O2W, act as hydrogen bond donors to form O—H···O hydrogen bonds with six O atoms from 18-crown-6 molecules (Table 1). These hydrogen bonds link alternate FeIII complexes and 18-crown-6 molecules into chains running along the a direction (Fig. 2). The lattice water molecules, O3W and O4W, lie between chains, accepting an O—H···O hydrogen bond from the hydroxyl group of the chelidamic acid ligand, and forming O—H···O hydrogen bonds to the non-coordinated O atoms of the carboxyl groups (Table 1).
For the crystal structure of [Fe(HChel)Cl(H2O)2], see: Laine et al. (1995). For other literature related to the use of chelidamic acid as a ligand, see: Cline et al. (1979); Hall et al. (2000); Ng (1998, 1999); Riegel (1926); Thich et al. (1976); Yang et al. (2002).
Data collection: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1994); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Fe(C7H3NO5)Cl(H2O)2]·C12H24O6·2H2O | Z = 2 |
Mr = 608.78 | F(000) = 638 |
Triclinic, P1 | Dx = 1.507 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7355 (9) Å | Cell parameters from 20 reflections |
b = 10.4503 (17) Å | θ = 3.0–25.0° |
c = 17.185 (3) Å | µ = 0.73 mm−1 |
α = 77.971 (12)° | T = 293 K |
β = 89.779 (11)° | Plate, yellow |
γ = 81.075 (11)° | 0.30 × 0.25 × 0.05 mm |
V = 1341.7 (4) Å3 |
Rigaku AFC-7R diffractometer | 2831 reflections with I > 2σ(I) |
Radiation source: rotating-anode generator | Rint = 0.037 |
Graphite monochromator | θmax = 25.0°, θmin = 3.0° |
ω/2θ scans | h = −2→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→12 |
Tmin = 0.851, Tmax = 0.964 | l = −20→20 |
5197 measured reflections | 3 standard reflections every 200 reflections |
4738 independent reflections | intensity decay: 2.4% |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0449P)2] where P = (Fo2 + 2Fc2)/3 |
4738 reflections | (Δ/σ)max = 0.002 |
358 parameters | Δρmax = 0.89 e Å−3 |
26 restraints | Δρmin = −0.45 e Å−3 |
[Fe(C7H3NO5)Cl(H2O)2]·C12H24O6·2H2O | γ = 81.075 (11)° |
Mr = 608.78 | V = 1341.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7355 (9) Å | Mo Kα radiation |
b = 10.4503 (17) Å | µ = 0.73 mm−1 |
c = 17.185 (3) Å | T = 293 K |
α = 77.971 (12)° | 0.30 × 0.25 × 0.05 mm |
β = 89.779 (11)° |
Rigaku AFC-7R diffractometer | 2831 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.037 |
Tmin = 0.851, Tmax = 0.964 | 3 standard reflections every 200 reflections |
5197 measured reflections | intensity decay: 2.4% |
4738 independent reflections |
R[F2 > 2σ(F2)] = 0.060 | 26 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.89 e Å−3 |
4738 reflections | Δρmin = −0.45 e Å−3 |
358 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 | 0.77559 (5) | 0.72036 (4) | 0.69984 (2) | 0.03157 (11) | |
N1 | 0.7714 (3) | 0.78986 (18) | 0.80335 (11) | 0.0299 (6) | |
O1 | 0.6479 (3) | 1.11514 (18) | 0.69990 (12) | 0.0527 (7) | |
O2 | 0.7032 (2) | 0.91875 (16) | 0.66429 (10) | 0.0371 (5) | |
O3 | 0.9002 (3) | 0.47201 (17) | 0.91676 (10) | 0.0454 (6) | |
O4 | 0.8442 (2) | 0.55333 (16) | 0.78711 (9) | 0.0350 (5) | |
O5 | 0.8038 (3) | 0.93481 (19) | 1.00395 (11) | 0.0644 (7) | |
H5C | 0.8646 | 0.8809 | 1.0385 | 0.097* | |
O11 | 0.2884 (3) | 0.6287 (2) | 0.59803 (12) | 0.0710 (8) | |
O12 | 0.1925 (3) | 0.8967 (2) | 0.55633 (13) | 0.0687 (8) | |
O13 | 0.0940 (3) | 0.99078 (18) | 0.69714 (12) | 0.0511 (6) | |
O14 | 0.2819 (3) | 0.8108 (2) | 0.83044 (12) | 0.0670 (8) | |
O15 | 0.4638 (3) | 0.5491 (2) | 0.86997 (12) | 0.0583 (7) | |
O16 | 0.4159 (3) | 0.4420 (2) | 0.73193 (14) | 0.0788 (9) | |
O1W | 1.0349 (2) | 0.74188 (16) | 0.69298 (10) | 0.0385 (5) | |
H1D | 1.0692 (18) | 0.8217 (7) | 0.7014 (11) | 0.058* | |
H1C | 1.0979 (17) | 0.7098 (14) | 0.6512 (6) | 0.058* | |
O2W | 0.5147 (2) | 0.70245 (16) | 0.71188 (10) | 0.0378 (5) | |
H2C | 0.4556 (17) | 0.7136 (19) | 0.7591 (5) | 0.057* | |
H2D | 0.4836 (19) | 0.6244 (7) | 0.6995 (10) | 0.057* | |
O3W | 0.8772 (3) | 1.28637 (19) | 0.72980 (14) | 0.0771 (8) | |
H3D | 0.7804 (10) | 1.2477 (12) | 0.7155 (12) | 0.116* | |
H3C | 0.857 (5) | 1.3798 (7) | 0.7090 (16) | 0.116* | |
O4W | 0.9945 (3) | 0.77074 (19) | 1.11650 (12) | 0.0790 (9) | |
H4D | 1.039 (2) | 0.7788 (19) | 1.1666 (5) | 0.118* | |
H4C | 1.037 (3) | 0.6843 (7) | 1.1074 (11) | 0.118* | |
C1 | 0.3072 (5) | 0.7013 (3) | 0.5185 (2) | 0.0790 (9) | |
H1A | 0.2018 | 0.7063 | 0.4870 | 0.095* | |
H1B | 0.4046 | 0.6560 | 0.4939 | 0.095* | |
C2 | 0.3384 (5) | 0.8350 (3) | 0.5209 (2) | 0.0735 (8) | |
H2A | 0.4444 | 0.8310 | 0.5518 | 0.088* | |
H2B | 0.3515 | 0.8847 | 0.4674 | 0.088* | |
C3 | 0.2084 (5) | 1.0275 (3) | 0.5628 (2) | 0.0815 (14) | |
H3A | 0.1917 | 1.0869 | 0.5109 | 0.098* | |
H3B | 0.3237 | 1.0299 | 0.5839 | 0.098* | |
C4 | 0.0706 (4) | 1.0684 (3) | 0.6177 (2) | 0.0670 (12) | |
H4A | 0.0707 | 1.1607 | 0.6192 | 0.080* | |
H4B | −0.0429 | 1.0613 | 0.5966 | 0.080* | |
C5 | 0.2379 (4) | 1.0168 (3) | 0.7389 (2) | 0.0659 (11) | |
H5A | 0.2292 | 1.1114 | 0.7352 | 0.079* | |
H5B | 0.3461 | 0.9864 | 0.7149 | 0.079* | |
C6 | 0.2406 (5) | 0.9479 (3) | 0.8243 (2) | 0.0684 (11) | |
H6A | 0.3270 | 0.9778 | 0.8541 | 0.082* | |
H6B | 0.1270 | 0.9690 | 0.8466 | 0.082* | |
C7 | 0.3131 (4) | 0.7379 (3) | 0.90998 (17) | 0.0680 (12) | |
H7A | 0.2208 | 0.7679 | 0.9435 | 0.082* | |
H7B | 0.4236 | 0.7524 | 0.9303 | 0.082* | |
C8 | 0.3181 (4) | 0.5953 (4) | 0.9119 (2) | 0.0746 (13) | |
H8A | 0.3266 | 0.5462 | 0.9666 | 0.090* | |
H8B | 0.2112 | 0.5817 | 0.8877 | 0.090* | |
C9 | 0.4847 (5) | 0.4113 (3) | 0.8672 (2) | 0.0883 (15) | |
H9A | 0.6065 | 0.3818 | 0.8575 | 0.106* | |
H9B | 0.4584 | 0.3619 | 0.9190 | 0.106* | |
C10 | 0.3792 (6) | 0.3788 (4) | 0.8087 (3) | 0.0997 (17) | |
H10A | 0.3999 | 0.2837 | 0.8128 | 0.120* | |
H10B | 0.2567 | 0.4049 | 0.8188 | 0.120* | |
C11 | 0.2845 (7) | 0.4236 (4) | 0.6766 (3) | 0.132 (2) | |
H11A | 0.2942 | 0.3301 | 0.6763 | 0.159* | |
H11B | 0.1689 | 0.4524 | 0.6948 | 0.159* | |
C12 | 0.3019 (6) | 0.4921 (4) | 0.6013 (3) | 0.1035 (9) | |
H12A | 0.2119 | 0.4767 | 0.5668 | 0.124* | |
H12B | 0.4148 | 0.4599 | 0.5819 | 0.124* | |
C21 | 0.7340 (3) | 0.9193 (2) | 0.79981 (15) | 0.0332 (8) | |
C22 | 0.7404 (4) | 0.9703 (3) | 0.86702 (16) | 0.0418 (8) | |
H22A | 0.7102 | 1.0608 | 0.8644 | 0.050* | |
C23 | 0.7931 (4) | 0.8834 (3) | 0.93964 (16) | 0.0428 (8) | |
C24 | 0.8338 (3) | 0.7468 (3) | 0.94158 (16) | 0.0379 (8) | |
H24A | 0.8694 | 0.6869 | 0.9889 | 0.046* | |
C25 | 0.8195 (3) | 0.7041 (2) | 0.87178 (14) | 0.0308 (7) | |
C26 | 0.6881 (3) | 0.9950 (3) | 0.71509 (15) | 0.0353 (8) | |
C27 | 0.8577 (3) | 0.5646 (2) | 0.85950 (15) | 0.0335 (8) | |
Cl1 | 0.79064 (11) | 0.62857 (8) | 0.59200 (4) | 0.0548 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0363 (2) | 0.03038 (18) | 0.02747 (18) | −0.00668 (16) | 0.00149 (16) | −0.00377 (14) |
N1 | 0.0304 (12) | 0.0270 (10) | 0.0321 (11) | −0.0072 (10) | 0.0011 (10) | −0.0037 (9) |
O1 | 0.0642 (14) | 0.0284 (10) | 0.0591 (13) | −0.0015 (10) | −0.0062 (11) | 0.0014 (9) |
O2 | 0.0456 (11) | 0.0331 (9) | 0.0285 (9) | −0.0073 (9) | −0.0025 (9) | 0.0039 (8) |
O3 | 0.0599 (13) | 0.0338 (10) | 0.0363 (10) | 0.0012 (10) | −0.0060 (10) | 0.0001 (8) |
O4 | 0.0454 (11) | 0.0307 (9) | 0.0284 (9) | −0.0065 (8) | 0.0017 (9) | −0.0048 (7) |
O5 | 0.0930 (17) | 0.0570 (12) | 0.0437 (11) | 0.0088 (12) | −0.0128 (12) | −0.0262 (9) |
O11 | 0.1046 (19) | 0.0608 (13) | 0.0419 (11) | 0.0133 (14) | −0.0043 (13) | −0.0167 (10) |
O12 | 0.0520 (14) | 0.0733 (15) | 0.0617 (14) | 0.0098 (12) | 0.0219 (11) | 0.0141 (12) |
O13 | 0.0422 (12) | 0.0388 (10) | 0.0701 (13) | −0.0110 (9) | −0.0057 (11) | −0.0027 (10) |
O14 | 0.0798 (16) | 0.0673 (13) | 0.0508 (12) | 0.0121 (13) | −0.0114 (12) | −0.0227 (10) |
O15 | 0.0592 (14) | 0.0603 (13) | 0.0507 (12) | −0.0151 (11) | 0.0034 (11) | 0.0028 (10) |
O16 | 0.118 (2) | 0.0471 (13) | 0.0683 (15) | −0.0159 (14) | −0.0183 (15) | −0.0026 (11) |
O1W | 0.0381 (11) | 0.0419 (10) | 0.0397 (10) | −0.0129 (9) | 0.0096 (9) | −0.0132 (8) |
O2W | 0.0397 (11) | 0.0416 (10) | 0.0363 (10) | −0.0148 (9) | 0.0087 (9) | −0.0117 (8) |
O3W | 0.0901 (18) | 0.0504 (13) | 0.0928 (16) | −0.0068 (13) | −0.0253 (15) | −0.0219 (12) |
O4W | 0.125 (2) | 0.0478 (12) | 0.0605 (13) | 0.0087 (14) | −0.0260 (14) | −0.0191 (10) |
C1 | 0.0788 (13) | 0.0870 (13) | 0.0683 (13) | −0.0001 (10) | 0.0039 (11) | −0.0195 (10) |
C2 | 0.0690 (13) | 0.0797 (13) | 0.0650 (12) | −0.0052 (10) | 0.0064 (10) | −0.0046 (10) |
C3 | 0.066 (2) | 0.071 (2) | 0.089 (3) | −0.0237 (19) | 0.014 (2) | 0.034 (2) |
C4 | 0.050 (2) | 0.0480 (19) | 0.089 (3) | −0.0069 (17) | −0.002 (2) | 0.0174 (18) |
C5 | 0.0447 (19) | 0.0536 (18) | 0.105 (3) | −0.0154 (16) | −0.0110 (19) | −0.0242 (18) |
C6 | 0.053 (2) | 0.073 (2) | 0.087 (2) | 0.0008 (18) | −0.0147 (19) | −0.0429 (17) |
C7 | 0.046 (2) | 0.115 (3) | 0.0381 (16) | 0.010 (2) | 0.0020 (16) | −0.0217 (18) |
C8 | 0.052 (2) | 0.100 (3) | 0.064 (2) | −0.020 (2) | 0.0172 (19) | 0.006 (2) |
C9 | 0.110 (3) | 0.065 (2) | 0.080 (3) | −0.035 (2) | −0.029 (2) | 0.023 (2) |
C10 | 0.103 (3) | 0.061 (2) | 0.125 (4) | −0.027 (2) | −0.016 (3) | 0.014 (2) |
C11 | 0.197 (5) | 0.056 (2) | 0.163 (4) | −0.060 (3) | −0.018 (4) | −0.037 (2) |
C12 | 0.1081 (14) | 0.1023 (14) | 0.1024 (14) | −0.0141 (11) | −0.0015 (11) | −0.0282 (11) |
C21 | 0.0346 (16) | 0.0259 (13) | 0.0377 (14) | −0.0023 (12) | −0.0029 (13) | −0.0050 (11) |
C22 | 0.0426 (17) | 0.0344 (14) | 0.0493 (16) | −0.0021 (13) | −0.0008 (14) | −0.0139 (12) |
C23 | 0.0463 (18) | 0.0487 (15) | 0.0378 (14) | −0.0039 (14) | −0.0020 (14) | −0.0218 (12) |
C24 | 0.0361 (16) | 0.0407 (15) | 0.0355 (14) | −0.0040 (13) | 0.0004 (13) | −0.0060 (12) |
C25 | 0.0307 (15) | 0.0320 (13) | 0.0302 (13) | −0.0081 (12) | 0.0036 (12) | −0.0053 (11) |
C26 | 0.0300 (15) | 0.0384 (14) | 0.0363 (14) | −0.0081 (13) | −0.0052 (13) | −0.0033 (12) |
C27 | 0.0302 (15) | 0.0355 (14) | 0.0338 (14) | −0.0057 (12) | 0.0000 (12) | −0.0044 (12) |
Cl1 | 0.0585 (5) | 0.0694 (5) | 0.0427 (4) | −0.0082 (4) | 0.0020 (4) | −0.0275 (3) |
Fe1—Cl1 | 2.2522 (9) | C1—H1B | 0.970 |
Fe1—N1 | 2.055 (2) | C2—H2A | 0.970 |
Fe1—O2 | 2.0248 (17) | C2—H2B | 0.970 |
Fe1—O4 | 2.0507 (16) | C3—C4 | 1.492 (5) |
Fe1—O1W | 2.0531 (19) | C3—H3A | 0.970 |
Fe1—O2W | 2.0613 (18) | C3—H3B | 0.970 |
N1—C21 | 1.327 (3) | C4—H4A | 0.970 |
N1—C25 | 1.336 (3) | C4—H4B | 0.970 |
O1—C26 | 1.218 (3) | C5—C6 | 1.493 (5) |
O2—C26 | 1.293 (3) | C5—H5A | 0.970 |
O3—C27 | 1.233 (3) | C5—H5B | 0.970 |
O4—C27 | 1.280 (3) | C6—H6A | 0.970 |
O5—C23 | 1.334 (3) | C6—H6B | 0.970 |
O5—H5C | 0.820 | C7—C8 | 1.478 (5) |
O11—C12 | 1.404 (5) | C7—H7A | 0.970 |
O11—C1 | 1.436 (4) | C7—H7B | 0.970 |
O12—C2 | 1.411 (4) | C8—H8A | 0.970 |
O12—C3 | 1.419 (4) | C8—H8B | 0.970 |
O13—C5 | 1.417 (4) | C9—C10 | 1.423 (5) |
O13—C4 | 1.432 (4) | C9—H9A | 0.970 |
O14—C6 | 1.401 (4) | C9—H9B | 0.970 |
O14—C7 | 1.420 (3) | C10—H10A | 0.970 |
O15—C8 | 1.411 (4) | C10—H10B | 0.970 |
O15—C9 | 1.435 (4) | C11—C12 | 1.359 (6) |
O16—C10 | 1.396 (5) | C11—H11A | 0.970 |
O16—C11 | 1.456 (5) | C11—H11B | 0.970 |
O1W—H1D | 0.96 (1) | C12—H12A | 0.970 |
O1W—H1C | 0.96 (1) | C12—H12B | 0.970 |
O2W—H2C | 0.95 (1) | C21—C22 | 1.373 (4) |
O2W—H2D | 0.95 (1) | C21—C26 | 1.519 (3) |
O3W—H3D | 0.96 (1) | C22—C23 | 1.402 (4) |
O3W—H3C | 0.96 (1) | C22—H22A | 0.930 |
O4W—H4D | 0.95 (1) | C23—C24 | 1.406 (4) |
O4W—H4C | 0.96 (1) | C24—C25 | 1.374 (4) |
C1—C2 | 1.463 (5) | C24—H24A | 0.930 |
C1—H1A | 0.970 | C25—C27 | 1.501 (4) |
O2—Fe1—O4 | 151.36 (7) | H5A—C5—H5B | 108.1 |
O2—Fe1—O1W | 90.60 (7) | O14—C6—C5 | 109.6 (3) |
O4—Fe1—O1W | 88.71 (7) | O14—C6—H6A | 109.8 |
O2—Fe1—N1 | 75.58 (7) | C5—C6—H6A | 109.8 |
O4—Fe1—N1 | 75.79 (7) | O14—C6—H6B | 109.8 |
O1W—Fe1—N1 | 87.38 (8) | C5—C6—H6B | 109.8 |
O2—Fe1—O2W | 88.62 (7) | H6A—C6—H6B | 108.2 |
O4—Fe1—O2W | 90.64 (7) | O14—C7—C8 | 109.4 (3) |
O1W—Fe1—O2W | 177.12 (7) | O14—C7—H7A | 109.8 |
N1—Fe1—O2W | 89.73 (8) | C8—C7—H7A | 109.8 |
O2—Fe1—Cl1 | 108.88 (6) | O14—C7—H7B | 109.8 |
O4—Fe1—Cl1 | 99.76 (6) | C8—C7—H7B | 109.8 |
O1W—Fe1—Cl1 | 91.69 (6) | H7A—C7—H7B | 108.2 |
N1—Fe1—Cl1 | 175.46 (6) | O15—C8—C7 | 109.5 (3) |
O2W—Fe1—Cl1 | 91.19 (6) | O15—C8—H8A | 109.8 |
C21—N1—C25 | 121.7 (2) | C7—C8—H8A | 109.8 |
C21—N1—Fe1 | 119.30 (16) | O15—C8—H8B | 109.8 |
C25—N1—Fe1 | 118.83 (17) | C7—C8—H8B | 109.8 |
C26—O2—Fe1 | 121.08 (15) | H8A—C8—H8B | 108.2 |
C27—O4—Fe1 | 119.30 (15) | C10—C9—O15 | 115.6 (3) |
C23—O5—H5C | 109.5 | C10—C9—H9A | 108.4 |
C12—O11—C1 | 111.8 (3) | O15—C9—H9A | 108.4 |
C2—O12—C3 | 112.6 (3) | C10—C9—H9B | 108.4 |
C5—O13—C4 | 113.0 (2) | O15—C9—H9B | 108.4 |
C6—O14—C7 | 113.6 (3) | H9A—C9—H9B | 107.4 |
C8—O15—C9 | 115.4 (3) | O16—C10—C9 | 111.5 (3) |
C10—O16—C11 | 108.7 (3) | O16—C10—H10A | 109.3 |
Fe1—O1W—H1D | 119.4 (9) | C9—C10—H10A | 109.3 |
Fe1—O1W—H1C | 116.3 (9) | O16—C10—H10B | 109.3 |
H1D—O1W—H1C | 112.0 (15) | C9—C10—H10B | 109.3 |
Fe1—O2W—H2C | 121.2 (10) | H10A—C10—H10B | 108.0 |
Fe1—O2W—H2D | 115.1 (9) | C12—C11—O16 | 112.4 (4) |
H2C—O2W—H2D | 105.9 (16) | C12—C11—H11A | 109.1 |
H3D—O3W—H3C | 110 (2) | O16—C11—H11A | 109.1 |
H4D—O4W—H4C | 109.6 (18) | C12—C11—H11B | 109.1 |
O11—C1—C2 | 109.7 (3) | O16—C11—H11B | 109.1 |
O11—C1—H1A | 109.7 | H11A—C11—H11B | 107.9 |
C2—C1—H1A | 109.7 | C11—C12—O11 | 111.7 (4) |
O11—C1—H1B | 109.7 | C11—C12—H12A | 109.3 |
C2—C1—H1B | 109.7 | O11—C12—H12A | 109.3 |
H1A—C1—H1B | 108.2 | C11—C12—H12B | 109.3 |
O12—C2—C1 | 107.3 (3) | O11—C12—H12B | 109.3 |
O12—C2—H2A | 110.2 | H12A—C12—H12B | 107.9 |
C1—C2—H2A | 110.2 | N1—C21—C22 | 121.1 (2) |
O12—C2—H2B | 110.2 | N1—C21—C26 | 111.3 (2) |
C1—C2—H2B | 110.2 | C22—C21—C26 | 127.6 (2) |
H2A—C2—H2B | 108.5 | C21—C22—C23 | 118.7 (2) |
O12—C3—C4 | 107.0 (3) | C21—C22—H22A | 120.6 |
O12—C3—H3A | 110.3 | C23—C22—H22A | 120.6 |
C4—C3—H3A | 110.3 | O5—C23—C22 | 118.1 (2) |
O12—C3—H3B | 110.3 | O5—C23—C24 | 122.9 (2) |
C4—C3—H3B | 110.3 | C22—C23—C24 | 119.0 (3) |
H3A—C3—H3B | 108.6 | C25—C24—C23 | 118.3 (2) |
O13—C4—C3 | 113.5 (2) | C25—C24—H24A | 120.8 |
O13—C4—H4A | 108.9 | C23—C24—H24A | 120.8 |
C3—C4—H4A | 108.9 | N1—C25—C24 | 121.2 (2) |
O13—C4—H4B | 108.9 | N1—C25—C27 | 111.2 (2) |
C3—C4—H4B | 108.9 | C24—C25—C27 | 127.6 (2) |
H4A—C4—H4B | 107.7 | O1—C26—O2 | 126.3 (2) |
O13—C5—C6 | 110.5 (3) | O1—C26—C21 | 121.0 (3) |
O13—C5—H5A | 109.6 | O2—C26—C21 | 112.6 (2) |
C6—C5—H5A | 109.6 | O3—C27—O4 | 125.2 (2) |
O13—C5—H5B | 109.6 | O3—C27—C25 | 120.0 (2) |
C6—C5—H5B | 109.6 | O4—C27—C25 | 114.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1C···O11i | 0.96 (1) | 1.91 (1) | 2.822 (3) | 159 (1) |
O1W—H1C···O12i | 0.96 (1) | 2.47 (1) | 2.937 (3) | 110 (1) |
O1W—H1D···O13i | 0.95 (1) | 1.79 (1) | 2.725 (3) | 166 (1) |
O2W—H2D···O11 | 0.95 (1) | 2.30 (1) | 2.926 (3) | 123 (1) |
O2W—H2C···O14 | 0.95 (1) | 2.10 (1) | 2.996 (3) | 156 (1) |
O2W—H2C···O15 | 0.95 (1) | 2.28 (1) | 2.911 (3) | 124 (1) |
O2W—H2D···O16 | 0.95 (1) | 2.02 (1) | 2.892 (3) | 152 (1) |
O3W—H3D···O1 | 0.96 (1) | 1.91 (1) | 2.826 (3) | 159 (1) |
O4W—H4C···O3ii | 0.96 (1) | 1.76 (1) | 2.717 (3) | 175 (2) |
O5—H5C···O4W | 0.82 | 1.77 | 2.591 (3) | 177 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C7H3NO5)Cl(H2O)2]·C12H24O6·2H2O |
Mr | 608.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.7355 (9), 10.4503 (17), 17.185 (3) |
α, β, γ (°) | 77.971 (12), 89.779 (11), 81.075 (11) |
V (Å3) | 1341.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.30 × 0.25 × 0.05 |
Data collection | |
Diffractometer | Rigaku AFC-7R |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.851, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5197, 4738, 2831 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.133, 1.03 |
No. of reflections | 4738 |
No. of parameters | 358 |
No. of restraints | 26 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.89, −0.45 |
Computer programs: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1994), CrystalStructure (Rigaku/MSC, 2002), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1C···O11i | 0.96 (1) | 1.91 (1) | 2.822 (3) | 158.9 (11) |
O1W—H1C···O12i | 0.96 (1) | 2.47 (1) | 2.937 (3) | 109.8 (11) |
O1W—H1D···O13i | 0.95 (1) | 1.79 (1) | 2.725 (3) | 165.5 (13) |
O2W—H2D···O11 | 0.95 (1) | 2.30 (1) | 2.926 (3) | 122.8 (9) |
O2W—H2C···O14 | 0.95 (1) | 2.10 (1) | 2.996 (3) | 156.2 (14) |
O2W—H2C···O15 | 0.95 (1) | 2.28 (1) | 2.911 (3) | 123.5 (14) |
O2W—H2D···O16 | 0.95 (1) | 2.02 (1) | 2.892 (3) | 151.6 (14) |
O3W—H3D···O1 | 0.96 (1) | 1.91 (1) | 2.826 (3) | 159.4 (11) |
O4W—H4C···O3ii | 0.96 (1) | 1.76 (1) | 2.717 (3) | 175 (2) |
O5—H5C···O4W | 0.82 | 1.77 | 2.591 (3) | 177.0 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+2. |
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Since the first report of chelidamic acid (4-hydroxypyridine-2,6-dicarboxylic acid) in 1926 (Riegel, 1926), its coordination chemistry has been extensively investigated. Much of this work focuses on the design and synthesis of polymers in which chelidamic acid acts as a ligand (Ng, 1998, 1999; Riegel, 1926; Hall et al., 2000; Cline et al., 1979; Yang et al., 2002; Thich et al., 1976, Laine et al., 1995). Herein, we report the synthesis and crystal structure of the title compound, which is an FeIII complex in which chelidamic acid acts as a tridentate chelating ligand.
The asymmetric unit (Fig. 1) consists of one FeIII atom coordinated by one chelidamic acid ligand, one Cl atom and two coordinated water molecules, as well as one 18-crown-6 molecule and two lattice water molecules. The coordination environment of FeIII comprises two carboxylic O atoms (Fe1—O2 = 2.0248 (17), Fe1—O4 = 2.0507 (16) Å) and one N atom (Fe1—N1 = 2.055 (2) Å) from the tridentate chelated chelidamic acid ligand, one Cl atom (Fe1—Cl1 = 2.2522 (9) Å) lying in the equatorial plane, and two water molecules (Fe1—O1W = 2.0531 (19), Fe1—O2W = 2.0613 (18) Å) in the axial positions, forming a distorted octahedral geometry. Due to the monodentate coordination mode of both carboxylate groups of the chelidamic acid ligand, the C—O bond distances of the coordinated O atoms (C26—O2 = 1.293 (3) and C27—O4 = 1.280 (3) Å) are slightly longer than the C—O bond distances of the uncoordinated O atoms (C26—O1 = 1.218 (3) and C27—O3 = 1.233 (3) Å).
The coordinated water molecules, O1W and O2W, act as hydrogen bond donors to form O—H···O hydrogen bonds with six O atoms from 18-crown-6 molecules (Table 1). These hydrogen bonds link alternate FeIII complexes and 18-crown-6 molecules into chains running along the a direction (Fig. 2). The lattice water molecules, O3W and O4W, lie between chains, accepting an O—H···O hydrogen bond from the hydroxyl group of the chelidamic acid ligand, and forming O—H···O hydrogen bonds to the non-coordinated O atoms of the carboxyl groups (Table 1).