metal-organic compounds
Bis[N-(2-pyridylcarbonyl)pyridine-2-carboximidato]iron(III) perchlorate methanol solvate
aAnhui Key Laboratory of Functional Coordination Compounds, School of Chemistry and Chemical Engineering, Anqing Teachers College, Anqing, 246011 Anhui, People's Republic of China
*Correspondence e-mail: wudayu_nju@yahoo.com.cn
In the title complex, [Fe(C12H8N3O2)2]ClO4·CH3OH, the iron(III) ion is surrounded by two tridentate N-(2-pyridylcarbonyl)pyridine-2-carboximidate (bpca) ligands and exhibits a distorted octahedral coordination by six bpca N atoms. A classical O—H⋯O hydrogen bond exists between the methanol solvent molecule and the perchlorate anion. measurements indicated the complex to be in the low-spin state in the temperature range 5–400 K.
Related literature
For the structure and magnetic properties of methanol-free [Fe(bpca)2]ClO4 and related compounds, see: Wocadlo et al. (1993).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536809040549/si2207sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040549/si2207Isup2.hkl
A methanolic solution (25 ml) containing the bpca ligand (0.2 mmol, 0.046 g) was added dropwise to Fe(ClO4)2.6 H2O (0.1 mmol, 0.036 g). After stirring for 15 minutes, the dark solution was filtered. Red block-shaped crystals suitable for single-crystal X-ray diffraction were obtained by evaporating the resulting filtration in air for several days (yield: 56.2%). Anal calc (%). for C25 H20 Cl Fe N6 O9: H 3.15 C 46.95 N 13.15. Found: H 3.12, C 46.87, N 13.54.
C-bound H atoms were placed geometrically and allowed to ride during
with C—H = 0.93–0.96 Å with Uiso(H) = 1.2 Ueq(C). The hydroxy H atom of the methanol solvent molecule was located in a difference Fourier map and refined as riding with the parent atom with Uiso(H) = 1.5Ueq(O).Our recent work indicated the N-donor tridentate ligand is suitable for the synthesis of spin-crossover materials. The N-2-pyridinylcarbonyl-2-pyridinecarboximidate (bpca) ligand has a typical rigid tridentate donor and was well studied to construct transition metal complexes inculding Fe(II), Fe(III), Co(II), Ni(II) and Cu(II) (Wocadlo et al. 1993 and references cited therein).. One of the examples is reported by Wocadlo and coworkers, which interestingly showed the spin state can be tuned by the different counterion and solvent. It was claimed that Fe(III) complex [Fe(bpca)Cl2(H2O)] (CH3)2CO and [Fe(bpca)2](NO3) 1.67 H2O adopt high spin state and the low-spin one in all the range of measured temperatures, respectively, while the [Fe(bpca)2](C1O4) evidence the spin-crossover behaviour. Here, we reported the crystal stucture of complex [Fe(bpca)6](C1O4) CH3OH.(Fig. 1). The coordination environments of Fe(III) ions are completed by two bpca ligands with average Fe—N bond length of being 1.954 Å (Table 1). A classical hyrogen bond O—H···O exists between methanol and chlorate anion with D···A distance being 2.916 (3)Å (Table 2). The temperature-dependent
was measured down to 5 K. The data in the form of molar multiply temperature is nearly constant and equal to about 0.45 emu K mol-1, consistent with low spin state of Fe(III) (s = 1/2).For the structure and magnetic properties of methanol-free [Fe(bpca)2]ClO4 and related compounds, see: Wocadlo et al. (1993).
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, the thermal ellipsoids were drawn at 50% probability level. |
[Fe(C12H8N3O2)2]ClO4·CH4O | Z = 2 |
Mr = 639.77 | F(000) = 654 |
Triclinic, P1 | Dx = 1.645 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 8.799 (3) Å | Cell parameters from 5465 reflections |
b = 11.603 (4) Å | θ = 3.0–27.8° |
c = 14.356 (6) Å | µ = 0.76 mm−1 |
α = 109.507 (4)° | T = 143 K |
β = 103.394 (3)° | Block, red |
γ = 100.091 (3)° | 0.32 × 0.26 × 0.23 mm |
V = 1292.0 (8) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 4421 independent reflections |
Radiation source: fine-focus sealed tube | 4177 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008) | h = −8→10 |
Tmin = 0.790, Tmax = 0.840 | k = −13→13 |
8499 measured reflections | l = −17→16 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0537P)2 + 1.8601P] where P = (Fo2 + 2Fc2)/3 |
4421 reflections | (Δ/σ)max < 0.001 |
379 parameters | Δρmax = 1.48 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Fe(C12H8N3O2)2]ClO4·CH4O | γ = 100.091 (3)° |
Mr = 639.77 | V = 1292.0 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.799 (3) Å | Mo Kα radiation |
b = 11.603 (4) Å | µ = 0.76 mm−1 |
c = 14.356 (6) Å | T = 143 K |
α = 109.507 (4)° | 0.32 × 0.26 × 0.23 mm |
β = 103.394 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 4421 independent reflections |
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008) | 4177 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.840 | Rint = 0.040 |
8499 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.48 e Å−3 |
4421 reflections | Δρmin = −0.48 e Å−3 |
379 parameters |
Experimental. The magnetic measurements were performed on Quantum Design SQUID, MPMS-5S magnetometer. |
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 | 0.58016 (4) | 0.81056 (3) | 0.23045 (2) | 0.01007 (12) | |
O1 | 0.2790 (2) | 0.51858 (16) | −0.02782 (13) | 0.0148 (4) | |
N2 | 0.5013 (2) | 0.68770 (19) | 0.09138 (15) | 0.0112 (4) | |
O2 | 0.5569 (2) | 0.63892 (17) | −0.06690 (13) | 0.0168 (4) | |
N1 | 0.3602 (2) | 0.73605 (19) | 0.23053 (15) | 0.0121 (4) | |
N6 | 0.6689 (2) | 0.70815 (19) | 0.30342 (16) | 0.0129 (4) | |
N3 | 0.7802 (2) | 0.84703 (19) | 0.19255 (16) | 0.0127 (4) | |
N5 | 0.6579 (2) | 0.93790 (19) | 0.36992 (15) | 0.0136 (4) | |
N4 | 0.5149 (2) | 0.95113 (19) | 0.19857 (15) | 0.0124 (4) | |
C5 | 0.2725 (3) | 0.6311 (2) | 0.14314 (18) | 0.0118 (5) | |
O4 | 0.7774 (3) | 0.97129 (19) | 0.54311 (14) | 0.0338 (5) | |
O3 | 0.6870 (3) | 1.15149 (18) | 0.46500 (15) | 0.0326 (5) | |
C7 | 0.5952 (3) | 0.6937 (2) | 0.02702 (18) | 0.0121 (5) | |
C6 | 0.3479 (3) | 0.6029 (2) | 0.05672 (18) | 0.0119 (5) | |
C9 | 0.8828 (3) | 0.7988 (2) | 0.0474 (2) | 0.0175 (5) | |
H9A | 0.8652 | 0.7542 | −0.0230 | 0.021* | |
C4 | 0.1249 (3) | 0.5577 (2) | 0.13335 (19) | 0.0165 (5) | |
H4A | 0.0705 | 0.4844 | 0.0739 | 0.020* | |
C15 | 0.4363 (3) | 1.1664 (3) | 0.1802 (2) | 0.0202 (6) | |
H15A | 0.4089 | 1.2379 | 0.1738 | 0.024* | |
C13 | 0.4368 (3) | 0.9487 (2) | 0.10510 (19) | 0.0141 (5) | |
H13A | 0.4096 | 0.8740 | 0.0464 | 0.017* | |
C8 | 0.7602 (3) | 0.7837 (2) | 0.09035 (19) | 0.0133 (5) | |
C11 | 1.0553 (3) | 0.9449 (3) | 0.2156 (2) | 0.0211 (6) | |
H11A | 1.1562 | 0.9995 | 0.2597 | 0.025* | |
C10 | 1.0327 (3) | 0.8812 (3) | 0.1110 (2) | 0.0226 (6) | |
H10A | 1.1174 | 0.8938 | 0.0838 | 0.027* | |
C24 | 0.6699 (3) | 0.5865 (2) | 0.2595 (2) | 0.0145 (5) | |
H24A | 0.6253 | 0.5434 | 0.1878 | 0.017* | |
C14 | 0.3960 (3) | 1.0545 (3) | 0.0939 (2) | 0.0178 (5) | |
H14A | 0.3417 | 1.0501 | 0.0285 | 0.021* | |
C22 | 0.8026 (4) | 0.5867 (3) | 0.4249 (2) | 0.0273 (6) | |
H22A | 0.8482 | 0.5458 | 0.4653 | 0.033* | |
C17 | 0.5555 (3) | 1.0616 (2) | 0.28249 (19) | 0.0160 (5) | |
C18 | 0.6414 (3) | 1.0583 (2) | 0.3844 (2) | 0.0182 (5) | |
C3 | 0.0577 (3) | 0.5945 (3) | 0.2137 (2) | 0.0189 (5) | |
H3A | −0.0422 | 0.5463 | 0.2089 | 0.023* | |
C20 | 0.7334 (3) | 0.7695 (2) | 0.40816 (19) | 0.0177 (5) | |
C21 | 0.8008 (4) | 0.7121 (3) | 0.4710 (2) | 0.0257 (6) | |
H21A | 0.8441 | 0.7564 | 0.5427 | 0.031* | |
C1 | 0.2943 (3) | 0.7719 (2) | 0.30753 (19) | 0.0157 (5) | |
H1A | 0.3519 | 0.8443 | 0.3672 | 0.019* | |
C12 | 0.9269 (3) | 0.9267 (2) | 0.25399 (19) | 0.0156 (5) | |
H12A | 0.9423 | 0.9708 | 0.3242 | 0.019* | |
C23 | 0.7360 (3) | 0.5236 (3) | 0.3187 (2) | 0.0205 (6) | |
H23A | 0.7352 | 0.4393 | 0.2868 | 0.025* | |
C19 | 0.7269 (3) | 0.9048 (2) | 0.4504 (2) | 0.0188 (5) | |
C16 | 0.5182 (3) | 1.1700 (3) | 0.2764 (2) | 0.0208 (6) | |
H16A | 0.5476 | 1.2442 | 0.3358 | 0.025* | |
C2 | 0.1426 (3) | 0.7039 (3) | 0.3005 (2) | 0.0193 (6) | |
H2A | 0.0985 | 0.7320 | 0.3542 | 0.023* | |
Cl1 | 0.91561 (7) | 0.22764 (6) | 0.18640 (5) | 0.02052 (17) | |
O14 | 0.8085 (2) | 0.10315 (19) | 0.15308 (18) | 0.0319 (5) | |
O13 | 1.0750 (2) | 0.2169 (2) | 0.18132 (17) | 0.0346 (5) | |
O12 | 0.9291 (3) | 0.3020 (2) | 0.29168 (18) | 0.0458 (6) | |
O11 | 0.8522 (3) | 0.2870 (2) | 0.1189 (2) | 0.0512 (7) | |
C1W | 0.3474 (5) | 0.5122 (4) | 0.3889 (3) | 0.0481 (9) | |
H1WA | 0.2545 | 0.5255 | 0.4108 | 0.072* | |
H1WB | 0.3419 | 0.5313 | 0.3283 | 0.072* | |
H1WC | 0.4448 | 0.5668 | 0.4438 | 0.072* | |
O1W | 0.3486 (3) | 0.3837 (2) | 0.36481 (19) | 0.0415 (6) | |
H1W | 0.2370 | 0.3263 | 0.3121 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01026 (19) | 0.0101 (2) | 0.0073 (2) | 0.00144 (14) | 0.00143 (14) | 0.00187 (15) |
O1 | 0.0143 (8) | 0.0139 (9) | 0.0091 (9) | 0.0001 (7) | 0.0000 (7) | 0.0002 (8) |
N2 | 0.0109 (10) | 0.0113 (10) | 0.0095 (10) | 0.0014 (8) | 0.0027 (8) | 0.0027 (8) |
O2 | 0.0202 (9) | 0.0179 (9) | 0.0092 (9) | 0.0018 (7) | 0.0047 (7) | 0.0033 (7) |
N1 | 0.0133 (10) | 0.0139 (10) | 0.0091 (10) | 0.0041 (8) | 0.0033 (8) | 0.0045 (9) |
N6 | 0.0126 (10) | 0.0131 (10) | 0.0121 (10) | 0.0022 (8) | 0.0044 (8) | 0.0042 (9) |
N3 | 0.0124 (10) | 0.0123 (10) | 0.0122 (10) | 0.0022 (8) | 0.0014 (8) | 0.0056 (8) |
N5 | 0.0160 (10) | 0.0115 (10) | 0.0091 (10) | 0.0025 (8) | 0.0011 (8) | 0.0015 (8) |
N4 | 0.0097 (9) | 0.0148 (10) | 0.0126 (10) | 0.0012 (8) | 0.0046 (8) | 0.0054 (9) |
C5 | 0.0137 (11) | 0.0116 (11) | 0.0095 (11) | 0.0045 (9) | 0.0029 (9) | 0.0033 (10) |
O4 | 0.0575 (15) | 0.0241 (11) | 0.0087 (10) | 0.0165 (10) | −0.0048 (9) | 0.0003 (9) |
O3 | 0.0580 (14) | 0.0145 (10) | 0.0134 (10) | 0.0100 (9) | −0.0006 (9) | −0.0009 (9) |
C7 | 0.0141 (12) | 0.0115 (12) | 0.0127 (13) | 0.0056 (9) | 0.0053 (10) | 0.0053 (10) |
C6 | 0.0125 (11) | 0.0122 (12) | 0.0113 (12) | 0.0041 (9) | 0.0020 (10) | 0.0057 (11) |
C9 | 0.0177 (12) | 0.0204 (13) | 0.0164 (13) | 0.0053 (10) | 0.0068 (10) | 0.0086 (11) |
C4 | 0.0143 (12) | 0.0179 (13) | 0.0117 (12) | 0.0012 (10) | 0.0010 (10) | 0.0028 (10) |
C15 | 0.0205 (13) | 0.0209 (14) | 0.0277 (15) | 0.0101 (11) | 0.0104 (11) | 0.0157 (12) |
C13 | 0.0098 (11) | 0.0188 (13) | 0.0123 (12) | 0.0019 (9) | 0.0026 (9) | 0.0058 (10) |
C8 | 0.0140 (12) | 0.0139 (12) | 0.0132 (12) | 0.0049 (10) | 0.0035 (10) | 0.0067 (10) |
C11 | 0.0116 (12) | 0.0226 (14) | 0.0256 (15) | 0.0007 (10) | 0.0006 (11) | 0.0108 (12) |
C10 | 0.0143 (12) | 0.0304 (15) | 0.0271 (15) | 0.0053 (11) | 0.0080 (11) | 0.0156 (13) |
C24 | 0.0145 (11) | 0.0134 (12) | 0.0163 (12) | 0.0045 (9) | 0.0079 (10) | 0.0043 (10) |
C14 | 0.0136 (12) | 0.0257 (14) | 0.0194 (13) | 0.0061 (10) | 0.0066 (10) | 0.0140 (12) |
C22 | 0.0356 (16) | 0.0287 (16) | 0.0272 (16) | 0.0166 (13) | 0.0088 (13) | 0.0192 (13) |
C17 | 0.0147 (12) | 0.0156 (12) | 0.0147 (13) | 0.0010 (10) | 0.0031 (10) | 0.0048 (11) |
C18 | 0.0219 (13) | 0.0141 (13) | 0.0150 (13) | 0.0038 (10) | 0.0032 (10) | 0.0036 (11) |
C3 | 0.0127 (12) | 0.0250 (14) | 0.0169 (13) | 0.0005 (10) | 0.0048 (10) | 0.0079 (11) |
C20 | 0.0204 (13) | 0.0175 (13) | 0.0132 (13) | 0.0045 (10) | 0.0032 (10) | 0.0054 (11) |
C21 | 0.0362 (16) | 0.0251 (15) | 0.0149 (13) | 0.0113 (12) | 0.0030 (12) | 0.0087 (12) |
C1 | 0.0178 (12) | 0.0176 (13) | 0.0112 (12) | 0.0057 (10) | 0.0048 (10) | 0.0045 (10) |
C12 | 0.0152 (12) | 0.0156 (12) | 0.0131 (12) | 0.0023 (10) | 0.0002 (10) | 0.0060 (10) |
C23 | 0.0229 (13) | 0.0172 (13) | 0.0268 (15) | 0.0077 (11) | 0.0144 (12) | 0.0098 (12) |
C19 | 0.0218 (13) | 0.0180 (13) | 0.0120 (13) | 0.0058 (11) | 0.0004 (10) | 0.0036 (11) |
C16 | 0.0260 (14) | 0.0148 (13) | 0.0210 (14) | 0.0067 (11) | 0.0078 (11) | 0.0055 (11) |
C2 | 0.0194 (13) | 0.0269 (15) | 0.0153 (13) | 0.0084 (11) | 0.0093 (11) | 0.0091 (12) |
Cl1 | 0.0209 (3) | 0.0169 (3) | 0.0216 (3) | 0.0046 (3) | 0.0049 (3) | 0.0063 (3) |
O14 | 0.0243 (10) | 0.0215 (11) | 0.0485 (13) | 0.0023 (8) | 0.0087 (10) | 0.0160 (10) |
O13 | 0.0217 (10) | 0.0423 (13) | 0.0359 (12) | 0.0036 (9) | 0.0139 (9) | 0.0097 (11) |
O12 | 0.0401 (13) | 0.0555 (16) | 0.0267 (12) | 0.0222 (12) | 0.0075 (10) | −0.0049 (11) |
O11 | 0.0555 (16) | 0.0345 (13) | 0.0552 (16) | 0.0034 (12) | −0.0092 (13) | 0.0299 (12) |
C1W | 0.049 (2) | 0.049 (2) | 0.055 (2) | 0.0203 (18) | 0.0172 (18) | 0.0263 (19) |
O1W | 0.0393 (13) | 0.0343 (13) | 0.0425 (14) | 0.0149 (10) | 0.0025 (11) | 0.0092 (11) |
Fe1—N2 | 1.900 (2) | C13—H13A | 0.9300 |
Fe1—N5 | 1.922 (2) | C11—C10 | 1.381 (4) |
Fe1—N6 | 1.974 (2) | C11—C12 | 1.381 (4) |
Fe1—N4 | 1.976 (2) | C11—H11A | 0.9300 |
Fe1—N1 | 1.977 (2) | C10—H10A | 0.9300 |
Fe1—N3 | 1.977 (2) | C24—C23 | 1.388 (4) |
O1—C6 | 1.206 (3) | C24—H24A | 0.9300 |
N2—C7 | 1.384 (3) | C14—H14A | 0.9300 |
N2—C6 | 1.391 (3) | C22—C23 | 1.377 (4) |
O2—C7 | 1.216 (3) | C22—C21 | 1.387 (4) |
N1—C1 | 1.344 (3) | C22—H22A | 0.9300 |
N1—C5 | 1.362 (3) | C17—C16 | 1.379 (4) |
N6—C24 | 1.343 (3) | C17—C18 | 1.500 (4) |
N6—C20 | 1.356 (3) | C3—C2 | 1.380 (4) |
N3—C12 | 1.345 (3) | C3—H3A | 0.9300 |
N3—C8 | 1.356 (3) | C20—C21 | 1.379 (4) |
N5—C19 | 1.379 (3) | C20—C19 | 1.500 (4) |
N5—C18 | 1.381 (3) | C21—H21A | 0.9300 |
N4—C13 | 1.347 (3) | C1—C2 | 1.390 (4) |
N4—C17 | 1.353 (3) | C1—H1A | 0.9300 |
C5—C4 | 1.371 (3) | C12—H12A | 0.9300 |
C5—C6 | 1.507 (3) | C23—H23A | 0.9300 |
O4—C19 | 1.219 (3) | C16—H16A | 0.9300 |
O3—C18 | 1.211 (3) | C2—H2A | 0.9300 |
C7—C8 | 1.499 (3) | Cl1—O12 | 1.433 (2) |
C9—C8 | 1.374 (4) | Cl1—O14 | 1.434 (2) |
C9—C10 | 1.380 (4) | Cl1—O11 | 1.434 (2) |
C9—H9A | 0.9300 | Cl1—O13 | 1.446 (2) |
C4—C3 | 1.392 (4) | C1W—O1W | 1.416 (4) |
C4—H4A | 0.9300 | C1W—H1WA | 0.9600 |
C15—C14 | 1.381 (4) | C1W—H1WB | 0.9600 |
C15—C16 | 1.384 (4) | C1W—H1WC | 0.9600 |
C15—H15A | 0.9300 | O1W—H1W | 1.0342 |
C13—C14 | 1.385 (4) | ||
N2—Fe1—N5 | 178.55 (8) | C12—C11—H11A | 120.3 |
N2—Fe1—N6 | 100.02 (9) | C9—C10—C11 | 119.2 (2) |
N5—Fe1—N6 | 81.43 (9) | C9—C10—H10A | 120.4 |
N2—Fe1—N4 | 96.55 (9) | C11—C10—H10A | 120.4 |
N5—Fe1—N4 | 82.01 (9) | N6—C24—C23 | 121.5 (2) |
N6—Fe1—N4 | 163.43 (9) | N6—C24—H24A | 119.2 |
N2—Fe1—N1 | 82.14 (8) | C23—C24—H24A | 119.2 |
N5—Fe1—N1 | 97.85 (9) | C15—C14—C13 | 119.8 (2) |
N6—Fe1—N1 | 89.91 (8) | C15—C14—H14A | 120.1 |
N4—Fe1—N1 | 92.51 (8) | C13—C14—H14A | 120.1 |
N2—Fe1—N3 | 82.31 (8) | C23—C22—C21 | 119.2 (3) |
N5—Fe1—N3 | 97.73 (9) | C23—C22—H22A | 120.4 |
N6—Fe1—N3 | 91.22 (8) | C21—C22—H22A | 120.4 |
N4—Fe1—N3 | 90.84 (8) | N4—C17—C16 | 122.9 (2) |
N1—Fe1—N3 | 164.37 (9) | N4—C17—C18 | 115.5 (2) |
C7—N2—C6 | 123.1 (2) | C16—C17—C18 | 121.6 (2) |
C7—N2—Fe1 | 117.82 (16) | O3—C18—N5 | 127.9 (2) |
C6—N2—Fe1 | 118.93 (16) | O3—C18—C17 | 122.0 (2) |
C1—N1—C5 | 118.1 (2) | N5—C18—C17 | 110.1 (2) |
C1—N1—Fe1 | 127.89 (17) | C2—C3—C4 | 118.6 (2) |
C5—N1—Fe1 | 113.91 (16) | C2—C3—H3A | 120.7 |
C24—N6—C20 | 118.5 (2) | C4—C3—H3A | 120.7 |
C24—N6—Fe1 | 126.44 (17) | N6—C20—C21 | 122.6 (2) |
C20—N6—Fe1 | 115.01 (17) | N6—C20—C19 | 114.9 (2) |
C12—N3—C8 | 118.2 (2) | C21—C20—C19 | 122.6 (2) |
C12—N3—Fe1 | 128.32 (17) | C20—C21—C22 | 118.5 (3) |
C8—N3—Fe1 | 113.43 (16) | C20—C21—H21A | 120.7 |
C19—N5—C18 | 123.3 (2) | C22—C21—H21A | 120.7 |
C19—N5—Fe1 | 118.66 (17) | N1—C1—C2 | 121.8 (2) |
C18—N5—Fe1 | 118.07 (16) | N1—C1—H1A | 119.1 |
C13—N4—C17 | 117.9 (2) | C2—C1—H1A | 119.1 |
C13—N4—Fe1 | 127.82 (17) | N3—C12—C11 | 121.8 (2) |
C17—N4—Fe1 | 114.28 (16) | N3—C12—H12A | 119.1 |
N1—C5—C4 | 122.6 (2) | C11—C12—H12A | 119.1 |
N1—C5—C6 | 115.1 (2) | C22—C23—C24 | 119.7 (3) |
C4—C5—C6 | 122.3 (2) | C22—C23—H23A | 120.2 |
O2—C7—N2 | 128.2 (2) | C24—C23—H23A | 120.2 |
O2—C7—C8 | 122.1 (2) | O4—C19—N5 | 127.6 (2) |
N2—C7—C8 | 109.7 (2) | O4—C19—C20 | 122.4 (2) |
O1—C6—N2 | 128.2 (2) | N5—C19—C20 | 110.0 (2) |
O1—C6—C5 | 122.5 (2) | C17—C16—C15 | 118.8 (2) |
N2—C6—C5 | 109.3 (2) | C17—C16—H16A | 120.6 |
C8—C9—C10 | 118.7 (2) | C15—C16—H16A | 120.6 |
C8—C9—H9A | 120.6 | C3—C2—C1 | 119.7 (2) |
C10—C9—H9A | 120.6 | C3—C2—H2A | 120.2 |
C5—C4—C3 | 119.1 (2) | C1—C2—H2A | 120.2 |
C5—C4—H4A | 120.5 | O12—Cl1—O14 | 109.89 (15) |
C3—C4—H4A | 120.5 | O12—Cl1—O11 | 110.31 (17) |
C14—C15—C16 | 118.6 (2) | O14—Cl1—O11 | 108.86 (14) |
C14—C15—H15A | 120.7 | O12—Cl1—O13 | 108.75 (13) |
C16—C15—H15A | 120.7 | O14—Cl1—O13 | 109.36 (13) |
N4—C13—C14 | 121.8 (2) | O11—Cl1—O13 | 109.66 (16) |
N4—C13—H13A | 119.1 | O1W—C1W—H1WA | 109.5 |
C14—C13—H13A | 119.1 | O1W—C1W—H1WB | 109.5 |
N3—C8—C9 | 122.6 (2) | H1WA—C1W—H1WB | 109.5 |
N3—C8—C7 | 115.4 (2) | O1W—C1W—H1WC | 109.5 |
C9—C8—C7 | 121.9 (2) | H1WA—C1W—H1WC | 109.5 |
C10—C11—C12 | 119.5 (2) | H1WB—C1W—H1WC | 109.5 |
C10—C11—H11A | 120.3 | C1W—O1W—H1W | 108.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O13i | 1.03 | 1.92 | 2.916 (3) | 160 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C12H8N3O2)2]ClO4·CH4O |
Mr | 639.77 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 143 |
a, b, c (Å) | 8.799 (3), 11.603 (4), 14.356 (6) |
α, β, γ (°) | 109.507 (4), 103.394 (3), 100.091 (3) |
V (Å3) | 1292.0 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.32 × 0.26 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SHELXTL; Sheldrick, 2008) |
Tmin, Tmax | 0.790, 0.840 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8499, 4421, 4177 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.107, 1.03 |
No. of reflections | 4421 |
No. of parameters | 379 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.48, −0.48 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Fe1—N2 | 1.900 (2) | Fe1—N4 | 1.976 (2) |
Fe1—N5 | 1.922 (2) | Fe1—N1 | 1.977 (2) |
Fe1—N6 | 1.974 (2) | Fe1—N3 | 1.977 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O13i | 1.03 | 1.92 | 2.916 (3) | 159.6 |
Symmetry code: (i) x−1, y, z. |
References
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wocadlo, S., Massa, W. & Folgado, J.-V. (1993). Inorg. Chim. Acta, 207, 199–206. CSD CrossRef CAS Web of Science Google Scholar
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Our recent work indicated the N-donor tridentate ligand is suitable for the synthesis of spin-crossover materials. The N-2-pyridinylcarbonyl-2-pyridinecarboximidate (bpca) ligand has a typical rigid tridentate donor and was well studied to construct transition metal complexes inculding Fe(II), Fe(III), Co(II), Ni(II) and Cu(II) (Wocadlo et al. 1993 and references cited therein).. One of the examples is reported by Wocadlo and coworkers, which interestingly showed the spin state can be tuned by the different counterion and solvent. It was claimed that Fe(III) complex [Fe(bpca)Cl2(H2O)] (CH3)2CO and [Fe(bpca)2](NO3) 1.67 H2O adopt high spin state and the low-spin one in all the range of measured temperatures, respectively, while the [Fe(bpca)2](C1O4) evidence the spin-crossover behaviour. Here, we reported the crystal stucture of complex [Fe(bpca)6](C1O4) CH3OH.(Fig. 1). The coordination environments of Fe(III) ions are completed by two bpca ligands with average Fe—N bond length of being 1.954 Å (Table 1). A classical hyrogen bond O—H···O exists between methanol and chlorate anion with D···A distance being 2.916 (3)Å (Table 2). The temperature-dependent magnetic susceptibility was measured down to 5 K. The data in the form of molar magnetic moment multiply temperature is nearly constant and equal to about 0.45 emu K mol-1, consistent with low spin state of Fe(III) (s = 1/2).