Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025081/bh2100sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025081/bh2100Isup2.hkl |
CCDC reference: 635308
A solution of FeCl2 (50 mg, 0.25 mmol) in water (10 ml) was added to 10 ml of an aqueous solution of dmp (105 mg, 0.5 mmol) and pydcH2 (69 mg, 0.5 mmol). Pale yellow crystals of the title compound were obtained after allowing the mixture to stand for a week at room temperature.
C and N-bonded H atoms were positioned geometrically and refined using a riding model (including torsional freedom for methyl groups), with C—H = 0.95–0.98 Å, and with Uiso(H) constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom. H atoms for water molecules were found in a difference map and their parameters constrained to fit an idealized geometry: O—H = 0.95 Å and Uiso(H) = 1.2Uiso(carrier O).
Continuing our research on proton-transfer compounds, we reached a system which is highly soluble in polar solvents. This compound has not been crystallized until now, but its metal-organic derivatives can be obtained as suitable crystals. In this report, the crystal structure of the iron(III) derivative is described.
The FeIII ion is located at the centre of a distorted octahedral arrangement (Fig. 1). The O1—Fe1—O5—C8 [92.4 (3)°], O1—Fe1—O8—C14 [-91.4 (3)°], O8—Fe1—O1—C1 [-96.6 (3)°] and O8—Fe1—O4—C7 [98.1 (3)°] torsion angles, and O1—Fe1—O8 [95.78 (12)°] and O4—Fe1—O5 [94.88 (11)°] bond angles indicate that the dianionic pydc2- units are almost perpendicular to each other. The important characteristic of the crystal structure is the infinite one dimensional chains based on [010] vector. Figure 2 shows the wavy chains of [Fe(pydc)2]- complex anions formed through the C—H···O interactions, in which the R22(10) and C22(16) graph set can be observed. The space between two chains is filled with dmpH+ cations and lattice water molecules. Hydrogen bonds play an important role in stabilizing the crystal structure.
Other intermolecular interactions exist between aromatic cations and the ligands bonded to the metal center. The centroid to centroid separation between the π–systems of the cation, labeled as B, and the anion, A1 and A2, are 3.531 and 3.457 Å, respectively (Fig. 3). The shortest interplanar distances for A1/B (3.355 Å) and A2/B (3.449 Å) and their related interplanar angles, 1.89 and 5.45°, respectively, confirm the effective π–π stacking interactions. Therefore, in the formation of this FeIII complex, ion pairing, metal–ligand coordinations, hydrogen–bonding and π–π stacking as well as van der Waals forces, play important roles in the construction of the observed three–dimensional network.
There are several reports on proton transfer between a carboxylic acid and a heterocyclic amine, and on the ability of the resulting self-associated proton-transfer systems to react with metal ions, affording transition metal complexes (Aghabozorg et al., 2006; Zhao et al., 2005).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
(C14H13N2)[Fe(C7H3NO4)2]·2H2O | F(000) = 1300 |
Mr = 631.35 | Dx = 1.612 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3591 reflections |
a = 8.9535 (14) Å | θ = 2.5–25.3° |
b = 18.607 (3) Å | µ = 0.65 mm−1 |
c = 15.674 (2) Å | T = 150 K |
β = 94.826 (3)° | Plate, pale yellow |
V = 2602.1 (7) Å3 | 0.50 × 0.40 × 0.08 mm |
Z = 4 |
Bruker SMART diffractometer | 5986 independent reflections |
Radiation source: fine-focus sealed tube | 2776 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.127 |
Detector resolution: 100 pixels mm-1 | θmax = 27.7°, θmin = 1.7° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | k = −24→23 |
Tmin = 0.737, Tmax = 0.950 | l = −20→20 |
29654 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0795P)2] where P = (Fo2 + 2Fc2)/3 |
5986 reflections | (Δ/σ)max = 0.001 |
390 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.81 e Å−3 |
(C14H13N2)[Fe(C7H3NO4)2]·2H2O | V = 2602.1 (7) Å3 |
Mr = 631.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.9535 (14) Å | µ = 0.65 mm−1 |
b = 18.607 (3) Å | T = 150 K |
c = 15.674 (2) Å | 0.50 × 0.40 × 0.08 mm |
β = 94.826 (3)° |
Bruker SMART diffractometer | 5986 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 2776 reflections with I > 2σ(I) |
Tmin = 0.737, Tmax = 0.950 | Rint = 0.127 |
29654 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.55 e Å−3 |
5986 reflections | Δρmin = −0.81 e Å−3 |
390 parameters |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.00816 (6) | 0.59166 (3) | 0.79981 (3) | 0.03083 (19) | |
N1 | 0.0103 (3) | 0.59937 (17) | 0.66923 (19) | 0.0271 (7) | |
N2 | 0.0118 (3) | 0.60327 (17) | 0.93011 (19) | 0.0290 (8) | |
N3 | 0.1130 (3) | 0.85237 (17) | 1.1817 (2) | 0.0308 (8) | |
H3A | 0.1723 | 0.8278 | 1.2255 | 0.037* | |
N4 | 0.3022 (3) | 0.74239 (18) | 1.1490 (2) | 0.0337 (8) | |
O1 | 0.1666 (3) | 0.66723 (15) | 0.78243 (16) | 0.0374 (7) | |
O2 | 0.2907 (3) | 0.72973 (16) | 0.68816 (17) | 0.0453 (8) | |
O3 | −0.2573 (3) | 0.46501 (16) | 0.63913 (18) | 0.0467 (8) | |
O4 | −0.1384 (3) | 0.51698 (14) | 0.75482 (16) | 0.0351 (7) | |
O5 | 0.1630 (3) | 0.52142 (15) | 0.84458 (17) | 0.0382 (7) | |
O6 | 0.2980 (3) | 0.47772 (17) | 0.9602 (2) | 0.0555 (9) | |
O7 | −0.2787 (3) | 0.72774 (17) | 0.91050 (18) | 0.0516 (9) | |
O8 | −0.1594 (3) | 0.66250 (15) | 0.81730 (16) | 0.0390 (7) | |
O9 | 0.1840 (3) | 0.43660 (17) | 0.69343 (19) | 0.0573 (9) | |
H9B | 0.1065 | 0.4021 | 0.6964 | 0.069* | |
H9A | 0.1900 | 0.4509 | 0.7518 | 0.069* | |
O10 | 0.4860 (3) | 0.80382 (17) | 0.80094 (18) | 0.0598 (9) | |
H10B | 0.5093 | 0.8536 | 0.8009 | 0.072* | |
H10A | 0.5375 | 0.7847 | 0.8514 | 0.072* | |
C1 | 0.1945 (4) | 0.6862 (2) | 0.7062 (3) | 0.0352 (10) | |
C2 | 0.0991 (4) | 0.6478 (2) | 0.6361 (2) | 0.0295 (9) | |
C3 | 0.0992 (4) | 0.6569 (2) | 0.5490 (2) | 0.0361 (10) | |
H3 | 0.1638 | 0.6907 | 0.5256 | 0.043* | |
C4 | 0.0022 (4) | 0.6152 (2) | 0.4967 (3) | 0.0377 (10) | |
H4 | −0.0015 | 0.6203 | 0.4363 | 0.045* | |
C5 | −0.0902 (4) | 0.5654 (2) | 0.5332 (3) | 0.0349 (10) | |
H5 | −0.1581 | 0.5368 | 0.4979 | 0.042* | |
C6 | −0.0822 (4) | 0.5584 (2) | 0.6199 (2) | 0.0294 (9) | |
C7 | −0.1676 (4) | 0.5071 (2) | 0.6735 (3) | 0.0335 (10) | |
C8 | 0.2013 (4) | 0.5167 (2) | 0.9265 (3) | 0.0356 (10) | |
C9 | 0.1112 (4) | 0.5660 (2) | 0.9794 (3) | 0.0311 (9) | |
C10 | 0.1242 (5) | 0.5746 (2) | 1.0666 (3) | 0.0384 (11) | |
H10 | 0.1962 | 0.5482 | 1.1020 | 0.046* | |
C11 | 0.0282 (5) | 0.6232 (2) | 1.1014 (3) | 0.0416 (11) | |
H11 | 0.0336 | 0.6296 | 1.1617 | 0.050* | |
C12 | −0.0744 (5) | 0.6620 (2) | 1.0500 (2) | 0.0382 (11) | |
H12 | −0.1390 | 0.6956 | 1.0739 | 0.046* | |
C13 | −0.0806 (4) | 0.6508 (2) | 0.9628 (2) | 0.0328 (10) | |
C14 | −0.1835 (4) | 0.6849 (2) | 0.8936 (3) | 0.0357 (10) | |
C15 | 0.0199 (5) | 0.9230 (3) | 1.2958 (3) | 0.0496 (13) | |
H15C | 0.0366 | 0.8793 | 1.3304 | 0.074* | |
H15B | −0.0775 | 0.9438 | 1.3062 | 0.074* | |
H15A | 0.0994 | 0.9578 | 1.3118 | 0.074* | |
C16 | 0.0215 (4) | 0.9047 (2) | 1.2041 (3) | 0.0404 (11) | |
C17 | −0.0667 (5) | 0.9402 (2) | 1.1396 (3) | 0.0454 (12) | |
H17 | −0.1329 | 0.9774 | 1.1539 | 0.054* | |
C18 | −0.0577 (4) | 0.9213 (2) | 1.0562 (3) | 0.0457 (12) | |
H18 | −0.1187 | 0.9456 | 1.0128 | 0.055* | |
C19 | 0.0387 (4) | 0.8672 (2) | 1.0329 (3) | 0.0359 (10) | |
C20 | 0.0586 (5) | 0.8467 (2) | 0.9465 (3) | 0.0442 (11) | |
H20 | 0.0003 | 0.8696 | 0.9009 | 0.053* | |
C21 | 0.1576 (5) | 0.7959 (2) | 0.9285 (3) | 0.0428 (11) | |
H21 | 0.1706 | 0.7845 | 0.8705 | 0.051* | |
C22 | 0.2434 (4) | 0.7591 (2) | 0.9956 (3) | 0.0358 (10) | |
C23 | 0.3494 (5) | 0.7056 (2) | 0.9805 (3) | 0.0397 (11) | |
H23 | 0.3669 | 0.6928 | 0.9235 | 0.048* | |
C24 | 0.4261 (5) | 0.6725 (2) | 1.0473 (3) | 0.0429 (11) | |
H24 | 0.4982 | 0.6367 | 1.0373 | 0.052* | |
C25 | 0.3988 (4) | 0.6913 (2) | 1.1322 (3) | 0.0390 (11) | |
C26 | 0.4740 (5) | 0.6527 (3) | 1.2077 (3) | 0.0553 (13) | |
H26C | 0.4998 | 0.6871 | 1.2539 | 0.083* | |
H26B | 0.5655 | 0.6295 | 1.1911 | 0.083* | |
H26A | 0.4061 | 0.6162 | 1.2275 | 0.083* | |
C27 | 0.2274 (4) | 0.7761 (2) | 1.0811 (2) | 0.0323 (9) | |
C28 | 0.1244 (4) | 0.8313 (2) | 1.0993 (2) | 0.0321 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0346 (3) | 0.0349 (4) | 0.0232 (3) | −0.0007 (3) | 0.0037 (2) | −0.0011 (3) |
N1 | 0.0287 (17) | 0.0283 (19) | 0.0244 (16) | 0.0021 (15) | 0.0027 (13) | −0.0016 (15) |
N2 | 0.0318 (18) | 0.032 (2) | 0.0233 (17) | −0.0043 (15) | 0.0002 (14) | −0.0010 (15) |
N3 | 0.0239 (17) | 0.036 (2) | 0.0317 (19) | −0.0033 (15) | −0.0006 (14) | 0.0042 (16) |
N4 | 0.0345 (19) | 0.034 (2) | 0.0315 (19) | −0.0059 (16) | −0.0070 (15) | −0.0004 (16) |
O1 | 0.0468 (17) | 0.0402 (18) | 0.0247 (15) | −0.0065 (14) | −0.0004 (12) | −0.0026 (13) |
O2 | 0.0473 (18) | 0.046 (2) | 0.0425 (18) | −0.0196 (16) | 0.0046 (14) | 0.0031 (15) |
O3 | 0.0488 (19) | 0.044 (2) | 0.0463 (19) | −0.0172 (16) | −0.0025 (15) | −0.0075 (16) |
O4 | 0.0382 (16) | 0.0403 (18) | 0.0271 (15) | −0.0050 (13) | 0.0042 (12) | 0.0022 (13) |
O5 | 0.0404 (17) | 0.0379 (18) | 0.0368 (17) | 0.0023 (14) | 0.0058 (13) | −0.0042 (14) |
O6 | 0.053 (2) | 0.052 (2) | 0.059 (2) | 0.0143 (17) | −0.0112 (16) | 0.0048 (17) |
O7 | 0.0519 (19) | 0.054 (2) | 0.049 (2) | 0.0192 (17) | 0.0067 (15) | −0.0050 (17) |
O8 | 0.0437 (17) | 0.0455 (19) | 0.0271 (16) | 0.0076 (14) | −0.0010 (13) | −0.0008 (14) |
O9 | 0.069 (2) | 0.054 (2) | 0.050 (2) | −0.0097 (18) | 0.0111 (17) | −0.0099 (17) |
O10 | 0.084 (3) | 0.042 (2) | 0.050 (2) | 0.0052 (18) | −0.0086 (18) | −0.0004 (17) |
C1 | 0.035 (2) | 0.031 (3) | 0.039 (3) | 0.004 (2) | 0.0014 (19) | 0.003 (2) |
C2 | 0.029 (2) | 0.029 (2) | 0.031 (2) | 0.0010 (18) | 0.0052 (17) | 0.0006 (19) |
C3 | 0.040 (2) | 0.036 (3) | 0.034 (2) | 0.002 (2) | 0.0096 (19) | 0.008 (2) |
C4 | 0.047 (3) | 0.040 (3) | 0.026 (2) | 0.010 (2) | 0.0002 (19) | 0.000 (2) |
C5 | 0.038 (2) | 0.031 (2) | 0.035 (2) | 0.0081 (19) | −0.0026 (19) | −0.005 (2) |
C6 | 0.028 (2) | 0.028 (2) | 0.032 (2) | 0.0048 (18) | 0.0011 (17) | −0.0052 (19) |
C7 | 0.034 (2) | 0.034 (3) | 0.033 (2) | 0.005 (2) | 0.0022 (18) | 0.000 (2) |
C8 | 0.031 (2) | 0.035 (3) | 0.040 (3) | −0.008 (2) | 0.0027 (19) | 0.000 (2) |
C9 | 0.034 (2) | 0.029 (2) | 0.031 (2) | −0.0057 (18) | 0.0021 (18) | 0.0056 (19) |
C10 | 0.043 (3) | 0.041 (3) | 0.030 (2) | −0.015 (2) | −0.0042 (19) | 0.006 (2) |
C11 | 0.056 (3) | 0.047 (3) | 0.021 (2) | −0.021 (2) | 0.002 (2) | −0.003 (2) |
C12 | 0.044 (3) | 0.040 (3) | 0.032 (2) | −0.008 (2) | 0.007 (2) | −0.010 (2) |
C13 | 0.034 (2) | 0.033 (3) | 0.032 (2) | −0.0094 (19) | 0.0051 (18) | −0.001 (2) |
C14 | 0.037 (2) | 0.034 (3) | 0.036 (3) | 0.002 (2) | 0.0032 (19) | −0.001 (2) |
C15 | 0.041 (3) | 0.060 (3) | 0.049 (3) | 0.003 (2) | 0.015 (2) | −0.011 (3) |
C16 | 0.027 (2) | 0.045 (3) | 0.050 (3) | −0.006 (2) | 0.008 (2) | −0.003 (2) |
C17 | 0.029 (2) | 0.044 (3) | 0.063 (3) | 0.002 (2) | 0.005 (2) | 0.000 (3) |
C18 | 0.030 (2) | 0.044 (3) | 0.062 (3) | 0.000 (2) | −0.004 (2) | 0.012 (3) |
C19 | 0.028 (2) | 0.036 (3) | 0.043 (3) | −0.0035 (19) | −0.0033 (18) | 0.006 (2) |
C20 | 0.053 (3) | 0.045 (3) | 0.032 (3) | −0.001 (2) | −0.013 (2) | 0.007 (2) |
C21 | 0.058 (3) | 0.041 (3) | 0.029 (2) | −0.007 (2) | −0.002 (2) | 0.002 (2) |
C22 | 0.040 (2) | 0.034 (3) | 0.034 (2) | −0.010 (2) | 0.0036 (19) | −0.003 (2) |
C23 | 0.046 (3) | 0.039 (3) | 0.035 (3) | −0.010 (2) | 0.009 (2) | −0.004 (2) |
C24 | 0.044 (3) | 0.034 (3) | 0.051 (3) | −0.002 (2) | 0.008 (2) | −0.004 (2) |
C25 | 0.036 (2) | 0.035 (3) | 0.044 (3) | −0.005 (2) | −0.006 (2) | 0.001 (2) |
C26 | 0.062 (3) | 0.045 (3) | 0.057 (3) | 0.009 (3) | −0.007 (2) | 0.004 (3) |
C27 | 0.030 (2) | 0.031 (2) | 0.035 (2) | −0.0062 (19) | 0.0004 (17) | −0.001 (2) |
C28 | 0.030 (2) | 0.034 (3) | 0.032 (2) | −0.0071 (19) | 0.0009 (17) | 0.0021 (19) |
Fe1—O5 | 1.990 (3) | C8—C9 | 1.514 (5) |
Fe1—O4 | 1.999 (3) | C9—C10 | 1.371 (5) |
Fe1—O1 | 2.032 (3) | C10—C11 | 1.390 (6) |
Fe1—O8 | 2.033 (3) | C10—H10 | 0.9500 |
Fe1—N2 | 2.051 (3) | C11—C12 | 1.375 (5) |
Fe1—N1 | 2.054 (3) | C11—H11 | 0.9500 |
N1—C6 | 1.325 (5) | C12—C13 | 1.379 (5) |
N1—C2 | 1.335 (4) | C12—H12 | 0.9500 |
N2—C9 | 1.325 (5) | C13—C14 | 1.503 (5) |
N2—C13 | 1.342 (5) | C15—C16 | 1.479 (5) |
N3—C16 | 1.338 (5) | C15—H15C | 0.9800 |
N3—C28 | 1.362 (5) | C15—H15B | 0.9800 |
N3—H3A | 0.9501 | C15—H15A | 0.9800 |
N4—C25 | 1.326 (5) | C16—C17 | 1.395 (6) |
N4—C27 | 1.362 (5) | C17—C18 | 1.363 (6) |
O1—C1 | 1.290 (4) | C17—H17 | 0.9500 |
O2—C1 | 1.232 (5) | C18—C19 | 1.395 (6) |
O3—C7 | 1.216 (4) | C18—H18 | 0.9500 |
O4—C7 | 1.292 (4) | C19—C28 | 1.408 (5) |
O5—C8 | 1.303 (4) | C19—C20 | 1.432 (5) |
O6—C8 | 1.215 (5) | C20—C21 | 1.341 (6) |
O7—C14 | 1.213 (4) | C20—H20 | 0.9500 |
O8—C14 | 1.301 (4) | C21—C22 | 1.424 (6) |
O9—H9B | 0.9499 | C21—H21 | 0.9500 |
O9—H9A | 0.9497 | C22—C27 | 1.396 (5) |
O10—H10B | 0.9500 | C22—C23 | 1.409 (5) |
O10—H10A | 0.9502 | C23—C24 | 1.351 (6) |
C1—C2 | 1.514 (5) | C23—H23 | 0.9500 |
C2—C3 | 1.375 (5) | C24—C25 | 1.418 (6) |
C3—C4 | 1.381 (5) | C24—H24 | 0.9500 |
C3—H3 | 0.9500 | C25—C26 | 1.494 (6) |
C4—C5 | 1.396 (5) | C26—H26C | 0.9800 |
C4—H4 | 0.9500 | C26—H26B | 0.9800 |
C5—C6 | 1.361 (5) | C26—H26A | 0.9800 |
C5—H5 | 0.9500 | C27—C28 | 1.426 (5) |
C6—C7 | 1.520 (5) | ||
O5—Fe1—O4 | 94.88 (11) | C12—C11—C10 | 121.1 (4) |
O5—Fe1—O1 | 91.61 (11) | C12—C11—H11 | 119.4 |
O4—Fe1—O1 | 151.51 (10) | C10—C11—H11 | 119.4 |
O5—Fe1—O8 | 151.48 (11) | C11—C12—C13 | 118.0 (4) |
O4—Fe1—O8 | 91.63 (11) | C11—C12—H12 | 121.0 |
O1—Fe1—O8 | 95.78 (12) | C13—C12—H12 | 121.0 |
O5—Fe1—N2 | 76.47 (12) | N2—C13—C12 | 120.2 (4) |
O4—Fe1—N2 | 112.29 (11) | N2—C13—C14 | 111.3 (3) |
O1—Fe1—N2 | 96.20 (11) | C12—C13—C14 | 128.5 (4) |
O8—Fe1—N2 | 75.37 (12) | O7—C14—O8 | 125.8 (4) |
O5—Fe1—N1 | 109.44 (11) | O7—C14—C13 | 121.3 (4) |
O4—Fe1—N1 | 75.98 (11) | O8—C14—C13 | 112.9 (3) |
O1—Fe1—N1 | 75.70 (11) | C16—C15—H15C | 109.5 |
O8—Fe1—N1 | 99.08 (11) | C16—C15—H15B | 109.5 |
N2—Fe1—N1 | 169.85 (12) | H15C—C15—H15B | 109.5 |
C6—N1—C2 | 121.6 (3) | C16—C15—H15A | 109.5 |
C6—N1—Fe1 | 118.9 (3) | H15C—C15—H15A | 109.5 |
C2—N1—Fe1 | 119.4 (3) | H15B—C15—H15A | 109.5 |
C9—N2—C13 | 121.9 (3) | N3—C16—C17 | 118.5 (4) |
C9—N2—Fe1 | 118.6 (3) | N3—C16—C15 | 118.6 (4) |
C13—N2—Fe1 | 119.4 (3) | C17—C16—C15 | 123.0 (4) |
C16—N3—C28 | 123.7 (4) | C18—C17—C16 | 119.8 (4) |
C16—N3—H3A | 118.6 | C18—C17—H17 | 120.1 |
C28—N3—H3A | 117.7 | C16—C17—H17 | 120.1 |
C25—N4—C27 | 117.5 (3) | C17—C18—C19 | 121.7 (4) |
C1—O1—Fe1 | 120.4 (3) | C17—C18—H18 | 119.1 |
C7—O4—Fe1 | 121.3 (3) | C19—C18—H18 | 119.1 |
C8—O5—Fe1 | 120.6 (3) | C18—C19—C28 | 117.3 (4) |
C14—O8—Fe1 | 120.9 (3) | C18—C19—C20 | 124.7 (4) |
H9B—O9—H9A | 97.1 | C28—C19—C20 | 118.0 (4) |
H10B—O10—H10A | 105.9 | C21—C20—C19 | 121.6 (4) |
O2—C1—O1 | 125.9 (4) | C21—C20—H20 | 119.2 |
O2—C1—C2 | 120.4 (4) | C19—C20—H20 | 119.2 |
O1—C1—C2 | 113.7 (3) | C20—C21—C22 | 120.5 (4) |
N1—C2—C3 | 121.3 (4) | C20—C21—H21 | 119.7 |
N1—C2—C1 | 110.7 (3) | C22—C21—H21 | 119.7 |
C3—C2—C1 | 127.9 (4) | C27—C22—C23 | 116.5 (4) |
C2—C3—C4 | 117.8 (4) | C27—C22—C21 | 120.5 (4) |
C2—C3—H3 | 121.1 | C23—C22—C21 | 123.0 (4) |
C4—C3—H3 | 121.1 | C24—C23—C22 | 119.8 (4) |
C3—C4—C5 | 119.6 (4) | C24—C23—H23 | 120.1 |
C3—C4—H4 | 120.2 | C22—C23—H23 | 120.1 |
C5—C4—H4 | 120.2 | C23—C24—C25 | 119.9 (4) |
C6—C5—C4 | 119.3 (4) | C23—C24—H24 | 120.0 |
C6—C5—H5 | 120.4 | C25—C24—H24 | 120.0 |
C4—C5—H5 | 120.4 | N4—C25—C24 | 122.0 (4) |
N1—C6—C5 | 120.4 (4) | N4—C25—C26 | 116.5 (4) |
N1—C6—C7 | 110.9 (3) | C24—C25—C26 | 121.5 (4) |
C5—C6—C7 | 128.7 (4) | C25—C26—H26C | 109.5 |
O3—C7—O4 | 126.9 (4) | C25—C26—H26B | 109.5 |
O3—C7—C6 | 120.2 (4) | H26C—C26—H26B | 109.5 |
O4—C7—C6 | 112.8 (4) | C25—C26—H26A | 109.5 |
O6—C8—O5 | 126.0 (4) | H26C—C26—H26A | 109.5 |
O6—C8—C9 | 121.0 (4) | H26B—C26—H26A | 109.5 |
O5—C8—C9 | 113.0 (4) | N4—C27—C22 | 124.3 (4) |
N2—C9—C10 | 121.1 (4) | N4—C27—C28 | 117.3 (4) |
N2—C9—C8 | 111.1 (3) | C22—C27—C28 | 118.4 (4) |
C10—C9—C8 | 127.8 (4) | N3—C28—C19 | 119.0 (4) |
C9—C10—C11 | 117.6 (4) | N3—C28—C27 | 119.9 (4) |
C9—C10—H10 | 121.2 | C19—C28—C27 | 121.0 (4) |
C11—C10—H10 | 121.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9B···O10i | 0.95 | 2.01 | 2.907 (5) | 157 |
O9—H9A···O5 | 0.95 | 1.99 | 2.866 (4) | 153 |
O10—H10B···O9ii | 0.95 | 2.33 | 2.907 (4) | 119 |
O10—H10A···O7iii | 0.95 | 2.11 | 2.964 (4) | 150 |
N3—H3A···O8iv | 0.95 | 2.00 | 2.832 (4) | 145 |
C3—H3···O7v | 0.95 | 2.45 | 3.304 (5) | 150 |
C12—H12···O2vi | 0.95 | 2.39 | 3.263 (5) | 152 |
C17—H17···O9vi | 0.95 | 2.41 | 3.357 (5) | 175 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1, y, z; (iv) x+1/2, −y+3/2, z+1/2; (v) x+1/2, −y+3/2, z−1/2; (vi) x−1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C14H13N2)[Fe(C7H3NO4)2]·2H2O |
Mr | 631.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 8.9535 (14), 18.607 (3), 15.674 (2) |
β (°) | 94.826 (3) |
V (Å3) | 2602.1 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.50 × 0.40 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.737, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29654, 5986, 2776 |
Rint | 0.127 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.165, 0.89 |
No. of reflections | 5986 |
No. of parameters | 390 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.81 |
Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9B···O10i | 0.95 | 2.01 | 2.907 (5) | 157.1 |
O9—H9A···O5 | 0.95 | 1.99 | 2.866 (4) | 152.7 |
O10—H10A···O7ii | 0.95 | 2.11 | 2.964 (4) | 149.5 |
C3—H3···O7iii | 0.95 | 2.45 | 3.304 (5) | 150 |
C12—H12···O2iv | 0.95 | 2.39 | 3.263 (5) | 152 |
C17—H17···O9iv | 0.95 | 2.41 | 3.357 (5) | 175 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x+1, y, z; (iii) x+1/2, −y+3/2, z−1/2; (iv) x−1/2, −y+3/2, z+1/2. |
Continuing our research on proton-transfer compounds, we reached a system which is highly soluble in polar solvents. This compound has not been crystallized until now, but its metal-organic derivatives can be obtained as suitable crystals. In this report, the crystal structure of the iron(III) derivative is described.
The FeIII ion is located at the centre of a distorted octahedral arrangement (Fig. 1). The O1—Fe1—O5—C8 [92.4 (3)°], O1—Fe1—O8—C14 [-91.4 (3)°], O8—Fe1—O1—C1 [-96.6 (3)°] and O8—Fe1—O4—C7 [98.1 (3)°] torsion angles, and O1—Fe1—O8 [95.78 (12)°] and O4—Fe1—O5 [94.88 (11)°] bond angles indicate that the dianionic pydc2- units are almost perpendicular to each other. The important characteristic of the crystal structure is the infinite one dimensional chains based on [010] vector. Figure 2 shows the wavy chains of [Fe(pydc)2]- complex anions formed through the C—H···O interactions, in which the R22(10) and C22(16) graph set can be observed. The space between two chains is filled with dmpH+ cations and lattice water molecules. Hydrogen bonds play an important role in stabilizing the crystal structure.
Other intermolecular interactions exist between aromatic cations and the ligands bonded to the metal center. The centroid to centroid separation between the π–systems of the cation, labeled as B, and the anion, A1 and A2, are 3.531 and 3.457 Å, respectively (Fig. 3). The shortest interplanar distances for A1/B (3.355 Å) and A2/B (3.449 Å) and their related interplanar angles, 1.89 and 5.45°, respectively, confirm the effective π–π stacking interactions. Therefore, in the formation of this FeIII complex, ion pairing, metal–ligand coordinations, hydrogen–bonding and π–π stacking as well as van der Waals forces, play important roles in the construction of the observed three–dimensional network.