metal-organic compounds
Tris(1,10-phenanthroline-κ2N,N′)iron(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) hemihydrate
aDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955 de Skikda, 21000 Skikda, Algeria, bUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Mentouri Constantine, 25000 Constantine, Algeria, cLaboatoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas de Sétif, 19000 Sétif, Algeria, dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, eChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, fClermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, 63000 Clermont-Ferrand, France, and gCNRS UMR 6296, ICCF, BP 80026, 63171 Aubière, France
*Correspondence e-mail: fat_setifi@yahoo.fr
In the title hydrated molecular salt, [Fe(C12H8N2)3](C9H5N4O)2·0.5H2O, the water molecule site is half-occupied. The Fe—N bond lengths within the octahedral tris-chelate [Fe(phen)3]2+ ion (phen is 1,10-phenantroline) are indicative of a low-spin d6 for the metal ion. The C—N, C—C and C—O bond lengths in the polynitrile anions indicate extensive electronic delocalization. In the crystal, the components are linked through O—H⋯N hydrogen bonds, forming [100] chains, as well as through Coulombic interactions.
Related literature
For background to 1,10-phenanthroline as a chelating ligand, see: Hoshina et al. (2000); Hwang & Ha (2006); Aparici Plaza et al. (2007); Zhou & Guo (2007). For a related structure, see: Cai & Zhan (2012). For further synthetic details, see: Middleton & Engelhardt (1958).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812048611/hb6994sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048611/hb6994Isup2.hkl
Potassium 1,1,3,3-tetracyano-2-ethoxypropenide (Ktcnoet) was prepared by reaction in ethanol of 1,1-diethoxy-2,2-dicyanoethene with malononitrile and potassium t-butoxide as described in Ref (Middleton & Engelhardt, 1958). Under aerobic conditions, an aqueous solution of Fe(BF4)2.6H2O (0.034 g, 5 ml) was slowly added to an ethanolique solution of 1,10-phenanthroline (0.020 g, 5 ml). To the resulting red soluion was added dropwise an aqueous solution of the polynitrile potassium salt Ktcnoet (0.045 g, 10 ml). The final solution was filtered and the filtrate was allowed to evaporate for few days at r.t. offorded red prisms of (I).
Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2 to 1.5 U(C).The water H-atoms were placed in calculated positions on the basis of hydrogen bonding and their temperature factors tied by a factor of 1.5 times. As the oxygen atom displayed extremely large temperature factors, the
of its occupancy was attempted. This refined to nearly 0.5; the occupancy was then set to exactly 0.5.The two ethyl groups are disordered over two positions in a 1:1 ratio. The C—C distance was restrained to 1.54±0.01 Å. For each group, the pair of O—C distances were restrained to within 0.01 Å of each other. The anisotropic temperature factors of the C atoms of the groups as well as those of the water molecule were tightly restrained to be nearly isotropic.
Omitted from the
were several reflections affected by the beamstop: (0 0 2), (0 1 0), (0 - 1 1), (1 - 1 1), (0 1 1), (0 1 2), (-1 1 0), (-1 1 1), (0 2 0), (0 0 1) and (0 0 3).1,10-Phenanthroline (phen) is a widely utilized chelating ligand in coordination chemistry and a lot of complexes with phen as a ligand have been reported (Hoshina et al., 2000; Hwang & Ha, 2006; Zhou & Guo, 2007). Recently, Cai et al. (2012) has reported the structure of a complex with [Fe(phen)3]2+ as cation and 1,1-dicyano-2-ethoxy-2-oxoethanide as counter-ion. We report here the synthesis and
of the title compound, in which a polynitrile anion acts as counter-ion.The structure of (I) is composed of a discrete [Fe(phen)3]2+ cations, uncoordinated tcnoet anions and water molecules of crystallization (Fig. 1).
Six nitrogen atoms from three bidentate phen ligands form a distorted octahedron around the iron atom with a mean Fe1—N bond length of 1.972 (18) Å. The main distortion from the octahedral geometry is observed in the values of the angles subtended by phen at the metal atom (82.36 (7)°, 82.50 (8)° and 83.02 (8)° for N1—Fe1—N2, N4—Fe1—N3 and N6—Fe1—N5, respectively) which deviate significantly from the ideal value of 90°. Each phenanthroline ligand is coplanar to within 0.04 Å. The average value of dihedral angle between pairs of phenanthroline planes is 82,1(3)°. The carbon-carbon and carbon-nitrogen intra-ring bond lengths agree with those observed in other metal complexes with chelating phen (Hoshina et al., 2000; Aparici Plaza et al., 2007; Cai & Zhan, 2012).
Examination of the intermolecular contacts in the
of (I) reveals that the main contacts are associated with O—H···N hydrogen bonds involving the water H atoms and those of the N atoms of the CN groups of the tcnoet anions containing atoms O1 (Table 1). In the crystal, this leads to the formation of an infinite one-dimensional {[(H2O)(tcnoet)2]2-}n anionic chains (Fig. 2), which interact with the cationic entities [Fe(phen)3]2+ and the tcnoet anions involving atoms O2 via coulombic forces.Due to the presence of the supplementary π electron systems of the cyano groups, the tcnoet ligands of (I) present a strong electronic delocalization, as indicated by C—N, C—C and C—O bond lengths.
For background to 1,10-phenanthroline as a chelating ligand, see: Hoshina et al. (2000); Hwang & Ha (2006); Aparici Plaza et al. (2007); Zhou & Guo (2007). For a related structure, see: Cai & Zhan (2012). For further synthetic details, see: Middleton & Engelhardt (1958).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Fe(C12H8N2)3](C9H5N4O)2·0.5H2O | Z = 2 |
Mr = 975.81 | F(000) = 1006 |
Triclinic, P1 | Dx = 1.355 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3497 (3) Å | Cell parameters from 7674 reflections |
b = 14.1736 (4) Å | θ = 2.6–23.7° |
c = 18.6086 (6) Å | µ = 0.38 mm−1 |
α = 94.462 (2)° | T = 293 K |
β = 96.562 (1)° | Prism, red |
γ = 101.129 (1)° | 0.55 × 0.35 × 0.15 mm |
V = 2391.12 (13) Å3 |
Bruker SMART APEX CCD diffractometer | 10845 independent reflections |
Radiation source: fine-focus sealed tube | 6909 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→9 |
Tmin = 0.820, Tmax = 0.946 | k = −18→18 |
38167 measured reflections | l = −23→24 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.6022P] where P = (Fo2 + 2Fc2)/3 |
10845 reflections | (Δ/σ)max = 0.001 |
661 parameters | Δρmax = 0.36 e Å−3 |
40 restraints | Δρmin = −0.43 e Å−3 |
[Fe(C12H8N2)3](C9H5N4O)2·0.5H2O | γ = 101.129 (1)° |
Mr = 975.81 | V = 2391.12 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3497 (3) Å | Mo Kα radiation |
b = 14.1736 (4) Å | µ = 0.38 mm−1 |
c = 18.6086 (6) Å | T = 293 K |
α = 94.462 (2)° | 0.55 × 0.35 × 0.15 mm |
β = 96.562 (1)° |
Bruker SMART APEX CCD diffractometer | 10845 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6909 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.946 | Rint = 0.043 |
38167 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 40 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.36 e Å−3 |
10845 reflections | Δρmin = −0.43 e Å−3 |
661 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.50347 (3) | 0.85774 (2) | 0.224833 (17) | 0.03344 (11) | |
O1 | 0.3012 (2) | 0.22872 (14) | 0.20343 (10) | 0.0616 (5) | |
O2 | 1.14419 (19) | 0.66090 (12) | 0.39687 (10) | 0.0537 (5) | |
O1W | 0.7463 (5) | 0.5451 (3) | 0.1682 (3) | 0.0894 (15) | 0.50 |
H11 | 0.6566 | 0.5202 | 0.1662 | 0.134* | 0.50 |
H12 | 0.7908 | 0.5022 | 0.1546 | 0.134* | 0.50 |
N1 | 0.5443 (2) | 0.76256 (13) | 0.29244 (10) | 0.0361 (4) | |
N2 | 0.39483 (19) | 0.89919 (13) | 0.30300 (10) | 0.0376 (4) | |
N3 | 0.4689 (2) | 0.95925 (14) | 0.16118 (10) | 0.0380 (4) | |
N4 | 0.67007 (19) | 0.95977 (14) | 0.27045 (10) | 0.0368 (4) | |
N5 | 0.6138 (2) | 0.80877 (13) | 0.15141 (10) | 0.0367 (4) | |
N6 | 0.3394 (2) | 0.76187 (13) | 0.17130 (10) | 0.0370 (4) | |
N7 | 0.4217 (3) | 0.4827 (2) | 0.16948 (15) | 0.0812 (8) | |
N8 | −0.0519 (3) | 0.4093 (2) | 0.12339 (18) | 0.0859 (9) | |
N9 | −0.1061 (3) | 0.1837 (2) | 0.02106 (15) | 0.0761 (8) | |
N10 | 0.0661 (3) | 0.0069 (2) | 0.17246 (17) | 0.0878 (9) | |
N11 | 0.9634 (3) | 0.7897 (2) | 0.28465 (15) | 0.0779 (8) | |
N12 | 0.8732 (3) | 0.87480 (19) | 0.49783 (14) | 0.0709 (7) | |
N13 | 0.8445 (4) | 0.6721 (2) | 0.58681 (16) | 0.0889 (9) | |
N14 | 1.2477 (4) | 0.5698 (2) | 0.57159 (18) | 0.0987 (10) | |
C1 | 0.4990 (2) | 0.77928 (17) | 0.35844 (12) | 0.0394 (5) | |
C2 | 0.6104 (3) | 0.68844 (17) | 0.28387 (14) | 0.0456 (6) | |
H2 | 0.6416 | 0.6750 | 0.2392 | 0.055* | |
C3 | 0.6353 (3) | 0.6299 (2) | 0.33882 (16) | 0.0576 (7) | |
H3 | 0.6793 | 0.5774 | 0.3298 | 0.069* | |
C4 | 0.5956 (3) | 0.6491 (2) | 0.40522 (16) | 0.0592 (8) | |
H4 | 0.6148 | 0.6115 | 0.4425 | 0.071* | |
C5 | 0.5254 (3) | 0.72648 (19) | 0.41700 (13) | 0.0495 (6) | |
C6 | 0.4788 (3) | 0.7556 (2) | 0.48418 (15) | 0.0650 (8) | |
H6 | 0.4979 | 0.7226 | 0.5243 | 0.078* | |
C7 | 0.4086 (3) | 0.8287 (2) | 0.49128 (14) | 0.0643 (8) | |
H7 | 0.3815 | 0.8459 | 0.5363 | 0.077* | |
C8 | 0.3742 (3) | 0.88111 (19) | 0.43108 (14) | 0.0499 (6) | |
C9 | 0.2964 (3) | 0.9560 (2) | 0.43273 (16) | 0.0605 (8) | |
H9 | 0.2642 | 0.9766 | 0.4756 | 0.073* | |
C10 | 0.2684 (3) | 0.9981 (2) | 0.37134 (17) | 0.0613 (8) | |
H10 | 0.2157 | 1.0474 | 0.3721 | 0.074* | |
C11 | 0.3178 (3) | 0.96841 (18) | 0.30664 (15) | 0.0489 (6) | |
H11A | 0.2960 | 0.9981 | 0.2651 | 0.059* | |
C12 | 0.4207 (2) | 0.85541 (17) | 0.36471 (12) | 0.0383 (5) | |
C13 | 0.5731 (3) | 1.04231 (17) | 0.17762 (13) | 0.0410 (6) | |
C14 | 0.3676 (3) | 0.9556 (2) | 0.10430 (13) | 0.0486 (6) | |
H14 | 0.2952 | 0.8998 | 0.0924 | 0.058* | |
C15 | 0.3654 (4) | 1.0324 (2) | 0.06164 (16) | 0.0637 (8) | |
H15 | 0.2933 | 1.0268 | 0.0219 | 0.076* | |
C16 | 0.4689 (4) | 1.1150 (2) | 0.07842 (17) | 0.0659 (8) | |
H16 | 0.4680 | 1.1662 | 0.0501 | 0.079* | |
C17 | 0.5771 (3) | 1.1230 (2) | 0.13850 (15) | 0.0546 (7) | |
C18 | 0.6900 (4) | 1.2064 (2) | 0.1631 (2) | 0.0712 (9) | |
H18 | 0.6951 | 1.2606 | 0.1377 | 0.085* | |
C19 | 0.7891 (4) | 1.2086 (2) | 0.2221 (2) | 0.0703 (9) | |
H19 | 0.8596 | 1.2646 | 0.2372 | 0.084* | |
C20 | 0.7877 (3) | 1.12635 (19) | 0.26187 (16) | 0.0524 (7) | |
C21 | 0.8876 (3) | 1.1224 (2) | 0.32361 (17) | 0.0632 (8) | |
H21 | 0.9611 | 1.1758 | 0.3415 | 0.076* | |
C22 | 0.8755 (3) | 1.0399 (2) | 0.35668 (16) | 0.0596 (7) | |
H22 | 0.9398 | 1.0368 | 0.3980 | 0.071* | |
C23 | 0.7672 (3) | 0.96011 (19) | 0.32887 (14) | 0.0464 (6) | |
H23 | 0.7619 | 0.9040 | 0.3521 | 0.056* | |
C24 | 0.6805 (3) | 1.04381 (17) | 0.23827 (13) | 0.0407 (6) | |
C25 | 0.5282 (3) | 0.73853 (16) | 0.10219 (12) | 0.0371 (5) | |
C26 | 0.7553 (3) | 0.83529 (19) | 0.14283 (13) | 0.0456 (6) | |
H26 | 0.8160 | 0.8828 | 0.1760 | 0.055* | |
C27 | 0.8151 (3) | 0.7944 (2) | 0.08606 (15) | 0.0561 (7) | |
H27 | 0.9139 | 0.8154 | 0.0815 | 0.067* | |
C28 | 0.7299 (3) | 0.7238 (2) | 0.03722 (15) | 0.0583 (8) | |
H28 | 0.7702 | 0.6962 | −0.0006 | 0.070* | |
C29 | 0.5804 (3) | 0.69269 (18) | 0.04414 (13) | 0.0463 (6) | |
C30 | 0.4781 (4) | 0.6204 (2) | −0.00332 (15) | 0.0624 (8) | |
H30 | 0.5106 | 0.5886 | −0.0420 | 0.075* | |
C31 | 0.3358 (4) | 0.5970 (2) | 0.00644 (15) | 0.0609 (8) | |
H31 | 0.2720 | 0.5501 | −0.0260 | 0.073* | |
C32 | 0.2801 (3) | 0.64234 (17) | 0.06550 (13) | 0.0464 (6) | |
C33 | 0.1346 (3) | 0.6214 (2) | 0.08017 (16) | 0.0574 (7) | |
H33 | 0.0648 | 0.5752 | 0.0499 | 0.069* | |
C34 | 0.0957 (3) | 0.6688 (2) | 0.13894 (16) | 0.0561 (7) | |
H34 | −0.0005 | 0.6542 | 0.1494 | 0.067* | |
C35 | 0.1998 (3) | 0.73890 (19) | 0.18332 (14) | 0.0478 (6) | |
H35 | 0.1709 | 0.7710 | 0.2229 | 0.057* | |
C36 | 0.3778 (3) | 0.71246 (16) | 0.11279 (12) | 0.0368 (5) | |
C37 | 0.4801 (14) | 0.2478 (16) | 0.3099 (11) | 0.082 (3) | 0.50 |
H37A | 0.5131 | 0.2828 | 0.3570 | 0.123* | 0.50 |
H37B | 0.5590 | 0.2565 | 0.2807 | 0.123* | 0.50 |
H37C | 0.4493 | 0.1803 | 0.3150 | 0.123* | 0.50 |
C38 | 0.3543 (10) | 0.2847 (10) | 0.2741 (5) | 0.072 (2) | 0.50 |
H38A | 0.2758 | 0.2787 | 0.3044 | 0.086* | 0.50 |
H38B | 0.3854 | 0.3525 | 0.2675 | 0.086* | 0.50 |
C37' | 0.4354 (15) | 0.2331 (16) | 0.3176 (11) | 0.082 (3) | 0.50 |
H37D | 0.5006 | 0.2716 | 0.3574 | 0.123* | 0.50 |
H37E | 0.4803 | 0.1826 | 0.2989 | 0.123* | 0.50 |
H37F | 0.3448 | 0.2052 | 0.3343 | 0.123* | 0.50 |
C38' | 0.4052 (10) | 0.2956 (9) | 0.2589 (5) | 0.072 (2) | 0.50 |
H38C | 0.3616 | 0.3481 | 0.2767 | 0.086* | 0.50 |
H38D | 0.4946 | 0.3223 | 0.2395 | 0.086* | 0.50 |
C39 | 0.3170 (3) | 0.4245 (2) | 0.16383 (15) | 0.0592 (7) | |
C40 | 0.1870 (3) | 0.3516 (2) | 0.15409 (14) | 0.0501 (6) | |
C41 | 0.0544 (3) | 0.3820 (2) | 0.13560 (16) | 0.0588 (7) | |
C42 | 0.1886 (3) | 0.2547 (2) | 0.16271 (13) | 0.0504 (7) | |
C43 | 0.0813 (3) | 0.1764 (2) | 0.13052 (14) | 0.0511 (6) | |
C44 | −0.0228 (3) | 0.1823 (2) | 0.07024 (16) | 0.0550 (7) | |
C45 | 0.0744 (3) | 0.0832 (2) | 0.15443 (16) | 0.0607 (8) | |
C46 | 1.2014 (13) | 0.5419 (14) | 0.3149 (9) | 0.095 (3) | 0.50 |
H46A | 1.2218 | 0.4780 | 0.3106 | 0.143* | 0.50 |
H46B | 1.2914 | 0.5886 | 0.3169 | 0.143* | 0.50 |
H46C | 1.1344 | 0.5492 | 0.2737 | 0.143* | 0.50 |
C47 | 1.1335 (19) | 0.5573 (5) | 0.3836 (10) | 0.069 (2) | 0.50 |
H47A | 1.0315 | 0.5236 | 0.3773 | 0.082* | 0.50 |
H47B | 1.1864 | 0.5336 | 0.4240 | 0.082* | 0.50 |
C46' | 1.1337 (13) | 0.5284 (14) | 0.3094 (9) | 0.095 (3) | 0.50 |
H46D | 1.1242 | 0.4595 | 0.3026 | 0.143* | 0.50 |
H46E | 1.2107 | 0.5588 | 0.2838 | 0.143* | 0.50 |
H46F | 1.0426 | 0.5450 | 0.2909 | 0.143* | 0.50 |
C47' | 1.1709 (19) | 0.5630 (5) | 0.3900 (10) | 0.069 (2) | 0.50 |
H47C | 1.1089 | 0.5218 | 0.4182 | 0.082* | 0.50 |
H47D | 1.2730 | 0.5627 | 0.4068 | 0.082* | 0.50 |
C48 | 1.0607 (3) | 0.69078 (17) | 0.44425 (14) | 0.0446 (6) | |
C49 | 0.9870 (3) | 0.76048 (18) | 0.41913 (14) | 0.0452 (6) | |
C50 | 0.9760 (3) | 0.7760 (2) | 0.34445 (17) | 0.0527 (7) | |
C51 | 0.9244 (3) | 0.8222 (2) | 0.46418 (14) | 0.0501 (6) | |
C52 | 1.0539 (3) | 0.65510 (19) | 0.51216 (15) | 0.0523 (7) | |
C53 | 0.9382 (4) | 0.6662 (2) | 0.55343 (16) | 0.0626 (8) | |
C54 | 1.1624 (4) | 0.6080 (2) | 0.54415 (17) | 0.0662 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.03130 (18) | 0.0387 (2) | 0.0314 (2) | 0.00944 (14) | 0.00527 (13) | 0.00311 (14) |
O1 | 0.0539 (11) | 0.0735 (13) | 0.0546 (12) | 0.0231 (10) | −0.0069 (9) | −0.0160 (10) |
O2 | 0.0536 (11) | 0.0461 (11) | 0.0661 (12) | 0.0149 (9) | 0.0178 (9) | 0.0074 (9) |
O1W | 0.056 (2) | 0.070 (3) | 0.133 (4) | −0.001 (2) | 0.027 (3) | −0.035 (3) |
N1 | 0.0345 (10) | 0.0384 (11) | 0.0353 (11) | 0.0076 (8) | 0.0043 (8) | 0.0028 (8) |
N2 | 0.0326 (10) | 0.0412 (11) | 0.0382 (11) | 0.0067 (8) | 0.0059 (8) | 0.0001 (9) |
N3 | 0.0371 (10) | 0.0451 (12) | 0.0351 (11) | 0.0146 (9) | 0.0069 (9) | 0.0054 (9) |
N4 | 0.0328 (10) | 0.0419 (11) | 0.0369 (11) | 0.0109 (8) | 0.0061 (8) | 0.0013 (9) |
N5 | 0.0367 (10) | 0.0427 (11) | 0.0335 (11) | 0.0122 (9) | 0.0070 (9) | 0.0077 (9) |
N6 | 0.0378 (10) | 0.0401 (11) | 0.0335 (11) | 0.0088 (9) | 0.0052 (8) | 0.0040 (9) |
N7 | 0.0645 (18) | 0.086 (2) | 0.083 (2) | −0.0033 (16) | 0.0072 (15) | −0.0035 (16) |
N8 | 0.0693 (18) | 0.0659 (18) | 0.118 (2) | 0.0124 (15) | −0.0099 (17) | 0.0170 (16) |
N9 | 0.0671 (17) | 0.092 (2) | 0.0589 (17) | 0.0024 (15) | −0.0104 (14) | 0.0039 (15) |
N10 | 0.0750 (19) | 0.076 (2) | 0.109 (2) | 0.0100 (16) | −0.0034 (17) | 0.0215 (18) |
N11 | 0.0790 (19) | 0.111 (2) | 0.0620 (18) | 0.0474 (17) | 0.0268 (15) | 0.0255 (16) |
N12 | 0.0793 (18) | 0.0732 (18) | 0.0631 (17) | 0.0322 (15) | 0.0048 (14) | −0.0110 (13) |
N13 | 0.115 (3) | 0.0733 (19) | 0.086 (2) | 0.0148 (17) | 0.054 (2) | 0.0074 (16) |
N14 | 0.090 (2) | 0.100 (2) | 0.106 (2) | 0.0214 (19) | −0.0108 (19) | 0.042 (2) |
C1 | 0.0386 (13) | 0.0425 (14) | 0.0332 (13) | −0.0002 (10) | 0.0031 (10) | 0.0027 (11) |
C2 | 0.0463 (14) | 0.0454 (15) | 0.0472 (15) | 0.0145 (12) | 0.0049 (12) | 0.0066 (12) |
C3 | 0.0578 (17) | 0.0507 (17) | 0.067 (2) | 0.0177 (13) | 0.0038 (15) | 0.0157 (14) |
C4 | 0.0579 (17) | 0.0590 (18) | 0.0603 (19) | 0.0076 (14) | −0.0012 (15) | 0.0277 (15) |
C5 | 0.0507 (15) | 0.0564 (17) | 0.0364 (15) | −0.0006 (13) | 0.0002 (12) | 0.0098 (12) |
C6 | 0.068 (2) | 0.081 (2) | 0.0409 (17) | −0.0001 (17) | 0.0043 (14) | 0.0167 (15) |
C7 | 0.073 (2) | 0.082 (2) | 0.0306 (15) | −0.0034 (17) | 0.0154 (14) | 0.0008 (14) |
C8 | 0.0446 (14) | 0.0558 (17) | 0.0433 (15) | −0.0037 (12) | 0.0127 (12) | −0.0078 (13) |
C9 | 0.0578 (17) | 0.069 (2) | 0.0530 (18) | 0.0037 (15) | 0.0260 (14) | −0.0111 (15) |
C10 | 0.0505 (16) | 0.0605 (18) | 0.076 (2) | 0.0179 (14) | 0.0230 (15) | −0.0115 (16) |
C11 | 0.0425 (14) | 0.0524 (16) | 0.0554 (17) | 0.0181 (12) | 0.0105 (12) | 0.0007 (13) |
C12 | 0.0349 (12) | 0.0448 (14) | 0.0315 (13) | 0.0001 (10) | 0.0070 (10) | −0.0028 (10) |
C13 | 0.0434 (13) | 0.0407 (14) | 0.0436 (14) | 0.0130 (11) | 0.0162 (11) | 0.0074 (11) |
C14 | 0.0487 (15) | 0.0585 (17) | 0.0403 (14) | 0.0169 (13) | 0.0009 (12) | 0.0072 (12) |
C15 | 0.072 (2) | 0.079 (2) | 0.0474 (17) | 0.0319 (18) | 0.0023 (15) | 0.0184 (16) |
C16 | 0.085 (2) | 0.064 (2) | 0.063 (2) | 0.0322 (18) | 0.0232 (17) | 0.0317 (16) |
C17 | 0.0641 (18) | 0.0508 (17) | 0.0581 (18) | 0.0190 (14) | 0.0254 (15) | 0.0180 (14) |
C18 | 0.081 (2) | 0.0509 (19) | 0.089 (3) | 0.0115 (17) | 0.035 (2) | 0.0229 (17) |
C19 | 0.067 (2) | 0.0474 (18) | 0.093 (3) | −0.0028 (15) | 0.0266 (19) | −0.0027 (17) |
C20 | 0.0481 (15) | 0.0428 (16) | 0.0644 (19) | 0.0014 (12) | 0.0178 (14) | −0.0023 (13) |
C21 | 0.0471 (16) | 0.0581 (19) | 0.072 (2) | −0.0079 (14) | 0.0056 (15) | −0.0180 (16) |
C22 | 0.0418 (15) | 0.073 (2) | 0.0561 (18) | 0.0065 (14) | −0.0024 (13) | −0.0122 (16) |
C23 | 0.0372 (13) | 0.0557 (16) | 0.0447 (15) | 0.0100 (12) | 0.0016 (11) | 0.0001 (12) |
C24 | 0.0379 (13) | 0.0397 (14) | 0.0457 (15) | 0.0088 (11) | 0.0118 (11) | 0.0000 (11) |
C25 | 0.0473 (14) | 0.0394 (13) | 0.0286 (12) | 0.0175 (11) | 0.0043 (10) | 0.0068 (10) |
C26 | 0.0384 (13) | 0.0591 (16) | 0.0427 (15) | 0.0139 (12) | 0.0103 (11) | 0.0083 (12) |
C27 | 0.0499 (16) | 0.078 (2) | 0.0499 (17) | 0.0255 (15) | 0.0206 (14) | 0.0153 (16) |
C28 | 0.072 (2) | 0.077 (2) | 0.0416 (16) | 0.0423 (17) | 0.0249 (15) | 0.0109 (15) |
C29 | 0.0640 (17) | 0.0507 (16) | 0.0308 (13) | 0.0268 (13) | 0.0072 (12) | 0.0060 (12) |
C30 | 0.091 (2) | 0.0595 (19) | 0.0419 (16) | 0.0319 (17) | 0.0086 (16) | −0.0019 (14) |
C31 | 0.085 (2) | 0.0477 (17) | 0.0438 (17) | 0.0128 (15) | −0.0054 (15) | −0.0096 (13) |
C32 | 0.0587 (16) | 0.0385 (14) | 0.0396 (15) | 0.0099 (12) | −0.0043 (12) | 0.0050 (12) |
C33 | 0.0582 (18) | 0.0459 (16) | 0.0581 (19) | −0.0028 (13) | −0.0112 (14) | 0.0044 (14) |
C34 | 0.0400 (14) | 0.0572 (18) | 0.0651 (19) | −0.0030 (13) | 0.0010 (13) | 0.0110 (15) |
C35 | 0.0374 (13) | 0.0552 (16) | 0.0497 (16) | 0.0047 (12) | 0.0085 (12) | 0.0064 (13) |
C36 | 0.0452 (13) | 0.0351 (13) | 0.0310 (13) | 0.0117 (11) | 0.0002 (10) | 0.0067 (10) |
C37 | 0.069 (7) | 0.107 (6) | 0.065 (4) | 0.019 (6) | −0.006 (5) | −0.002 (3) |
C38 | 0.085 (6) | 0.089 (4) | 0.046 (4) | 0.040 (4) | −0.001 (3) | −0.012 (3) |
C37' | 0.069 (7) | 0.107 (6) | 0.065 (4) | 0.019 (6) | −0.006 (5) | −0.002 (3) |
C38' | 0.085 (6) | 0.089 (4) | 0.046 (4) | 0.040 (4) | −0.001 (3) | −0.012 (3) |
C39 | 0.0559 (18) | 0.070 (2) | 0.0483 (17) | 0.0075 (16) | 0.0082 (14) | −0.0055 (14) |
C40 | 0.0497 (15) | 0.0563 (17) | 0.0422 (15) | 0.0085 (13) | 0.0055 (12) | −0.0003 (13) |
C41 | 0.0578 (18) | 0.0516 (17) | 0.0642 (19) | 0.0052 (14) | 0.0025 (15) | 0.0112 (14) |
C42 | 0.0437 (14) | 0.0711 (19) | 0.0377 (15) | 0.0164 (14) | 0.0074 (12) | −0.0015 (13) |
C43 | 0.0476 (15) | 0.0593 (18) | 0.0468 (16) | 0.0133 (13) | 0.0048 (12) | 0.0044 (13) |
C44 | 0.0518 (16) | 0.0635 (18) | 0.0467 (17) | 0.0045 (14) | 0.0077 (14) | 0.0029 (14) |
C45 | 0.0505 (17) | 0.072 (2) | 0.0584 (19) | 0.0134 (15) | 0.0040 (14) | 0.0028 (16) |
C46 | 0.132 (9) | 0.079 (5) | 0.080 (3) | 0.027 (7) | 0.032 (7) | −0.003 (3) |
C47 | 0.076 (7) | 0.0497 (19) | 0.088 (4) | 0.022 (3) | 0.029 (4) | 0.0052 (19) |
C46' | 0.132 (9) | 0.079 (5) | 0.080 (3) | 0.027 (7) | 0.032 (7) | −0.003 (3) |
C47' | 0.076 (7) | 0.0497 (19) | 0.088 (4) | 0.022 (3) | 0.029 (4) | 0.0052 (19) |
C48 | 0.0407 (13) | 0.0393 (14) | 0.0518 (16) | 0.0043 (11) | 0.0081 (12) | −0.0003 (12) |
C49 | 0.0419 (14) | 0.0455 (15) | 0.0476 (16) | 0.0081 (11) | 0.0085 (12) | −0.0007 (12) |
C50 | 0.0445 (15) | 0.0611 (18) | 0.0580 (19) | 0.0185 (13) | 0.0149 (13) | 0.0085 (15) |
C51 | 0.0466 (15) | 0.0532 (17) | 0.0488 (16) | 0.0120 (13) | −0.0002 (13) | 0.0002 (13) |
C52 | 0.0560 (16) | 0.0477 (16) | 0.0509 (17) | 0.0064 (13) | 0.0051 (13) | 0.0030 (13) |
C53 | 0.085 (2) | 0.0438 (17) | 0.0564 (19) | 0.0035 (15) | 0.0148 (17) | 0.0034 (14) |
C54 | 0.069 (2) | 0.0602 (19) | 0.066 (2) | 0.0021 (16) | 0.0033 (16) | 0.0191 (16) |
Fe1—N6 | 1.9563 (19) | C19—C20 | 1.426 (4) |
Fe1—N5 | 1.9654 (18) | C19—H19 | 0.9300 |
Fe1—N4 | 1.9686 (19) | C20—C24 | 1.390 (3) |
Fe1—N1 | 1.9752 (18) | C20—C21 | 1.407 (4) |
Fe1—N2 | 1.9819 (18) | C21—C22 | 1.355 (4) |
Fe1—N3 | 1.9836 (18) | C21—H21 | 0.9300 |
O1—C42 | 1.353 (3) | C22—C23 | 1.385 (4) |
O1—C38 | 1.463 (6) | C22—H22 | 0.9300 |
O1—C38' | 1.473 (6) | C23—H23 | 0.9300 |
O2—C48 | 1.339 (3) | C25—C29 | 1.401 (3) |
O2—C47 | 1.452 (6) | C25—C36 | 1.424 (3) |
O2—C47' | 1.455 (6) | C26—C27 | 1.389 (3) |
O1W—H11 | 0.8400 | C26—H26 | 0.9300 |
O1W—H12 | 0.8400 | C27—C28 | 1.359 (4) |
N1—C2 | 1.326 (3) | C27—H27 | 0.9300 |
N1—C1 | 1.362 (3) | C28—C29 | 1.405 (4) |
N2—C11 | 1.326 (3) | C28—H28 | 0.9300 |
N2—C12 | 1.367 (3) | C29—C30 | 1.426 (4) |
N3—C14 | 1.328 (3) | C30—C31 | 1.344 (4) |
N3—C13 | 1.364 (3) | C30—H30 | 0.9300 |
N4—C23 | 1.334 (3) | C31—C32 | 1.429 (4) |
N4—C24 | 1.366 (3) | C31—H31 | 0.9300 |
N5—C26 | 1.336 (3) | C32—C36 | 1.388 (3) |
N5—C25 | 1.361 (3) | C32—C33 | 1.398 (4) |
N6—C35 | 1.332 (3) | C33—C34 | 1.360 (4) |
N6—C36 | 1.368 (3) | C33—H33 | 0.9300 |
N7—C39 | 1.140 (4) | C34—C35 | 1.390 (4) |
N8—C41 | 1.140 (4) | C34—H34 | 0.9300 |
N9—C44 | 1.136 (3) | C35—H35 | 0.9300 |
N10—C45 | 1.149 (4) | C37—C38 | 1.487 (9) |
N11—C50 | 1.141 (3) | C37—H37A | 0.9600 |
N12—C51 | 1.145 (3) | C37—H37B | 0.9600 |
N13—C53 | 1.142 (4) | C37—H37C | 0.9600 |
N14—C54 | 1.143 (4) | C38—H38A | 0.9700 |
C1—C5 | 1.395 (3) | C38—H38B | 0.9700 |
C1—C12 | 1.421 (3) | C37'—C38' | 1.495 (9) |
C2—C3 | 1.393 (3) | C37'—H37D | 0.9600 |
C2—H2 | 0.9300 | C37'—H37E | 0.9600 |
C3—C4 | 1.353 (4) | C37'—H37F | 0.9600 |
C3—H3 | 0.9300 | C38'—H38C | 0.9700 |
C4—C5 | 1.398 (4) | C38'—H38D | 0.9700 |
C4—H4 | 0.9300 | C39—C40 | 1.419 (4) |
C5—C6 | 1.427 (4) | C40—C42 | 1.398 (4) |
C6—C7 | 1.334 (4) | C40—C41 | 1.404 (4) |
C6—H6 | 0.9300 | C42—C43 | 1.388 (4) |
C7—C8 | 1.432 (4) | C43—C44 | 1.417 (4) |
C7—H7 | 0.9300 | C43—C45 | 1.418 (4) |
C8—C9 | 1.398 (4) | C46—C47 | 1.509 (9) |
C8—C12 | 1.400 (3) | C46—H46A | 0.9600 |
C9—C10 | 1.352 (4) | C46—H46B | 0.9600 |
C9—H9 | 0.9300 | C46—H46C | 0.9600 |
C10—C11 | 1.401 (4) | C47—H47A | 0.9700 |
C10—H10 | 0.9300 | C47—H47B | 0.9700 |
C11—H11A | 0.9300 | C46'—C47' | 1.521 (9) |
C13—C17 | 1.399 (3) | C46'—H46D | 0.9600 |
C13—C24 | 1.418 (3) | C46'—H46E | 0.9600 |
C14—C15 | 1.398 (4) | C46'—H46F | 0.9600 |
C14—H14 | 0.9300 | C47'—H47C | 0.9700 |
C15—C16 | 1.357 (4) | C47'—H47D | 0.9700 |
C15—H15 | 0.9300 | C48—C49 | 1.389 (3) |
C16—C17 | 1.401 (4) | C48—C52 | 1.401 (4) |
C16—H16 | 0.9300 | C49—C51 | 1.416 (4) |
C17—C18 | 1.430 (4) | C49—C50 | 1.419 (4) |
C18—C19 | 1.348 (4) | C52—C54 | 1.419 (4) |
C18—H18 | 0.9300 | C52—C53 | 1.422 (4) |
N6—Fe1—N5 | 83.02 (8) | N5—C25—C29 | 123.8 (2) |
N6—Fe1—N4 | 174.79 (7) | N5—C25—C36 | 115.8 (2) |
N5—Fe1—N4 | 94.35 (8) | C29—C25—C36 | 120.3 (2) |
N6—Fe1—N1 | 90.18 (7) | N5—C26—C27 | 122.3 (3) |
N5—Fe1—N1 | 93.45 (7) | N5—C26—H26 | 118.8 |
N4—Fe1—N1 | 94.48 (8) | C27—C26—H26 | 118.8 |
N6—Fe1—N2 | 96.56 (8) | C28—C27—C26 | 120.3 (3) |
N5—Fe1—N2 | 175.80 (7) | C28—C27—H27 | 119.9 |
N4—Fe1—N2 | 86.38 (7) | C26—C27—H27 | 119.9 |
N1—Fe1—N2 | 82.36 (7) | C27—C28—C29 | 119.7 (2) |
N6—Fe1—N3 | 92.90 (8) | C27—C28—H28 | 120.2 |
N5—Fe1—N3 | 88.01 (7) | C29—C28—H28 | 120.2 |
N4—Fe1—N3 | 82.50 (8) | C25—C29—C28 | 116.5 (2) |
N1—Fe1—N3 | 176.74 (8) | C25—C29—C30 | 117.7 (3) |
N2—Fe1—N3 | 96.18 (7) | C28—C29—C30 | 125.7 (2) |
C42—O1—C38 | 116.7 (6) | C31—C30—C29 | 121.6 (3) |
C42—O1—C38' | 123.4 (6) | C31—C30—H30 | 119.2 |
C48—O2—C47 | 116.9 (7) | C29—C30—H30 | 119.2 |
C48—O2—C47' | 123.0 (7) | C30—C31—C32 | 121.6 (3) |
H11—O1W—H12 | 108.7 | C30—C31—H31 | 119.2 |
C2—N1—C1 | 116.7 (2) | C32—C31—H31 | 119.2 |
C2—N1—Fe1 | 130.32 (16) | C36—C32—C33 | 116.9 (2) |
C1—N1—Fe1 | 112.96 (15) | C36—C32—C31 | 117.8 (3) |
C11—N2—C12 | 117.2 (2) | C33—C32—C31 | 125.3 (3) |
C11—N2—Fe1 | 130.11 (17) | C34—C33—C32 | 119.7 (3) |
C12—N2—Fe1 | 112.15 (14) | C34—C33—H33 | 120.2 |
C14—N3—C13 | 117.4 (2) | C32—C33—H33 | 120.2 |
C14—N3—Fe1 | 129.94 (18) | C33—C34—C35 | 120.0 (3) |
C13—N3—Fe1 | 112.52 (15) | C33—C34—H34 | 120.0 |
C23—N4—C24 | 116.6 (2) | C35—C34—H34 | 120.0 |
C23—N4—Fe1 | 129.93 (17) | N6—C35—C34 | 122.5 (2) |
C24—N4—Fe1 | 113.38 (15) | N6—C35—H35 | 118.7 |
C26—N5—C25 | 117.4 (2) | C34—C35—H35 | 118.7 |
C26—N5—Fe1 | 129.83 (17) | N6—C36—C32 | 124.0 (2) |
C25—N5—Fe1 | 112.78 (15) | N6—C36—C25 | 115.2 (2) |
C35—N6—C36 | 116.9 (2) | C32—C36—C25 | 120.8 (2) |
C35—N6—Fe1 | 129.92 (17) | C38—C37—H37A | 109.5 |
C36—N6—Fe1 | 113.17 (15) | C38—C37—H37B | 109.5 |
N1—C1—C5 | 123.7 (2) | H37A—C37—H37B | 109.5 |
N1—C1—C12 | 115.5 (2) | C38—C37—H37C | 109.5 |
C5—C1—C12 | 120.8 (2) | H37A—C37—H37C | 109.5 |
N1—C2—C3 | 122.9 (2) | H37B—C37—H37C | 109.5 |
N1—C2—H2 | 118.5 | O1—C38—C37 | 109.1 (12) |
C3—C2—H2 | 118.5 | O1—C38—H38A | 109.9 |
C4—C3—C2 | 120.2 (3) | C37—C38—H38A | 109.9 |
C4—C3—H3 | 119.9 | O1—C38—H38B | 109.9 |
C2—C3—H3 | 119.9 | C37—C38—H38B | 109.9 |
C3—C4—C5 | 119.1 (2) | H38A—C38—H38B | 108.3 |
C3—C4—H4 | 120.5 | C38'—C37'—H37D | 109.5 |
C5—C4—H4 | 120.5 | C38'—C37'—H37E | 109.5 |
C1—C5—C4 | 117.3 (2) | H37D—C37'—H37E | 109.5 |
C1—C5—C6 | 117.5 (3) | C38'—C37'—H37F | 109.5 |
C4—C5—C6 | 125.2 (3) | H37D—C37'—H37F | 109.5 |
C7—C6—C5 | 122.2 (3) | H37E—C37'—H37F | 109.5 |
C7—C6—H6 | 118.9 | O1—C38'—C37' | 103.5 (12) |
C5—C6—H6 | 118.9 | O1—C38'—H38C | 111.1 |
C6—C7—C8 | 121.4 (3) | C37'—C38'—H38C | 111.1 |
C6—C7—H7 | 119.3 | O1—C38'—H38D | 111.1 |
C8—C7—H7 | 119.3 | C37'—C38'—H38D | 111.1 |
C9—C8—C12 | 116.8 (2) | H38C—C38'—H38D | 109.0 |
C9—C8—C7 | 125.3 (3) | N7—C39—C40 | 178.0 (3) |
C12—C8—C7 | 117.9 (2) | C42—C40—C41 | 121.1 (2) |
C10—C9—C8 | 119.3 (2) | C42—C40—C39 | 122.6 (2) |
C10—C9—H9 | 120.4 | C41—C40—C39 | 116.3 (3) |
C8—C9—H9 | 120.4 | N8—C41—C40 | 177.0 (4) |
C9—C10—C11 | 120.9 (3) | O1—C42—C43 | 113.2 (2) |
C9—C10—H10 | 119.6 | O1—C42—C40 | 121.5 (2) |
C11—C10—H10 | 119.6 | C43—C42—C40 | 125.2 (2) |
N2—C11—C10 | 121.9 (3) | C42—C43—C44 | 123.1 (3) |
N2—C11—H11A | 119.1 | C42—C43—C45 | 121.1 (2) |
C10—C11—H11A | 119.1 | C44—C43—C45 | 115.7 (3) |
N2—C12—C8 | 123.9 (2) | N9—C44—C43 | 177.6 (3) |
N2—C12—C1 | 115.9 (2) | N10—C45—C43 | 178.3 (3) |
C8—C12—C1 | 120.2 (2) | C47—C46—H46A | 109.5 |
N3—C13—C17 | 123.5 (2) | C47—C46—H46B | 109.5 |
N3—C13—C24 | 116.1 (2) | H46A—C46—H46B | 109.5 |
C17—C13—C24 | 120.3 (2) | C47—C46—H46C | 109.5 |
N3—C14—C15 | 122.6 (3) | H46A—C46—H46C | 109.5 |
N3—C14—H14 | 118.7 | H46B—C46—H46C | 109.5 |
C15—C14—H14 | 118.7 | O2—C47—C46 | 106.0 (12) |
C16—C15—C14 | 119.8 (3) | O2—C47—H47A | 110.5 |
C16—C15—H15 | 120.1 | C46—C47—H47A | 110.5 |
C14—C15—H15 | 120.1 | O2—C47—H47B | 110.5 |
C15—C16—C17 | 119.8 (3) | C46—C47—H47B | 110.5 |
C15—C16—H16 | 120.1 | H47A—C47—H47B | 108.7 |
C17—C16—H16 | 120.1 | C47'—C46'—H46D | 109.5 |
C13—C17—C16 | 116.8 (3) | C47'—C46'—H46E | 109.5 |
C13—C17—C18 | 117.6 (3) | H46D—C46'—H46E | 109.5 |
C16—C17—C18 | 125.5 (3) | C47'—C46'—H46F | 109.5 |
C19—C18—C17 | 121.8 (3) | H46D—C46'—H46F | 109.5 |
C19—C18—H18 | 119.1 | H46E—C46'—H46F | 109.5 |
C17—C18—H18 | 119.1 | O2—C47'—C46' | 105.4 (12) |
C18—C19—C20 | 121.1 (3) | O2—C47'—H47C | 110.7 |
C18—C19—H19 | 119.4 | C46'—C47'—H47C | 110.7 |
C20—C19—H19 | 119.4 | O2—C47'—H47D | 110.7 |
C24—C20—C21 | 117.2 (3) | C46'—C47'—H47D | 110.7 |
C24—C20—C19 | 118.1 (3) | H47C—C47'—H47D | 108.8 |
C21—C20—C19 | 124.7 (3) | O2—C48—C49 | 112.9 (2) |
C22—C21—C20 | 119.3 (3) | O2—C48—C52 | 121.9 (2) |
C22—C21—H21 | 120.3 | C49—C48—C52 | 125.2 (2) |
C20—C21—H21 | 120.3 | C48—C49—C51 | 124.2 (2) |
C21—C22—C23 | 119.9 (3) | C48—C49—C50 | 120.1 (2) |
C21—C22—H22 | 120.0 | C51—C49—C50 | 115.7 (2) |
C23—C22—H22 | 120.0 | N11—C50—C49 | 177.9 (3) |
N4—C23—C22 | 123.3 (3) | N12—C51—C49 | 176.6 (3) |
N4—C23—H23 | 118.4 | C48—C52—C54 | 122.4 (3) |
C22—C23—H23 | 118.4 | C48—C52—C53 | 121.2 (2) |
N4—C24—C20 | 123.7 (2) | C54—C52—C53 | 116.4 (3) |
N4—C24—C13 | 115.4 (2) | N13—C53—C52 | 177.9 (3) |
C20—C24—C13 | 120.9 (2) | N14—C54—C52 | 178.1 (4) |
N6—Fe1—N1—C2 | 77.2 (2) | N3—C13—C17—C18 | 178.1 (2) |
N5—Fe1—N1—C2 | −5.8 (2) | C24—C13—C17—C18 | −1.6 (4) |
N4—Fe1—N1—C2 | −100.5 (2) | C15—C16—C17—C13 | 1.2 (4) |
N2—Fe1—N1—C2 | 173.8 (2) | C15—C16—C17—C18 | −178.5 (3) |
N6—Fe1—N1—C1 | −104.61 (16) | C13—C17—C18—C19 | −0.5 (4) |
N5—Fe1—N1—C1 | 172.37 (16) | C16—C17—C18—C19 | 179.2 (3) |
N4—Fe1—N1—C1 | 77.72 (16) | C17—C18—C19—C20 | 1.5 (5) |
N2—Fe1—N1—C1 | −8.02 (15) | C18—C19—C20—C24 | −0.3 (4) |
N6—Fe1—N2—C11 | −89.7 (2) | C18—C19—C20—C21 | 179.6 (3) |
N4—Fe1—N2—C11 | 86.0 (2) | C24—C20—C21—C22 | 0.1 (4) |
N1—Fe1—N2—C11 | −179.0 (2) | C19—C20—C21—C22 | −179.8 (3) |
N3—Fe1—N2—C11 | 3.9 (2) | C20—C21—C22—C23 | 1.1 (4) |
N6—Fe1—N2—C12 | 98.77 (15) | C24—N4—C23—C22 | −0.6 (3) |
N4—Fe1—N2—C12 | −85.53 (15) | Fe1—N4—C23—C22 | −176.88 (18) |
N1—Fe1—N2—C12 | 9.48 (15) | C21—C22—C23—N4 | −0.9 (4) |
N3—Fe1—N2—C12 | −167.58 (15) | C23—N4—C24—C20 | 1.9 (3) |
N6—Fe1—N3—C14 | 0.1 (2) | Fe1—N4—C24—C20 | 178.83 (19) |
N5—Fe1—N3—C14 | 83.0 (2) | C23—N4—C24—C13 | −178.1 (2) |
N4—Fe1—N3—C14 | 177.6 (2) | Fe1—N4—C24—C13 | −1.2 (2) |
N2—Fe1—N3—C14 | −96.8 (2) | C21—C20—C24—N4 | −1.7 (4) |
N6—Fe1—N3—C13 | −175.51 (15) | C19—C20—C24—N4 | 178.2 (2) |
N5—Fe1—N3—C13 | −92.61 (15) | C21—C20—C24—C13 | 178.4 (2) |
N4—Fe1—N3—C13 | 2.05 (15) | C19—C20—C24—C13 | −1.7 (4) |
N2—Fe1—N3—C13 | 87.56 (15) | N3—C13—C24—N4 | 3.1 (3) |
N5—Fe1—N4—C23 | −96.6 (2) | C17—C13—C24—N4 | −177.2 (2) |
N1—Fe1—N4—C23 | −2.8 (2) | N3—C13—C24—C20 | −177.0 (2) |
N2—Fe1—N4—C23 | 79.2 (2) | C17—C13—C24—C20 | 2.7 (3) |
N3—Fe1—N4—C23 | 176.0 (2) | C26—N5—C25—C29 | 0.5 (3) |
N5—Fe1—N4—C24 | 86.99 (15) | Fe1—N5—C25—C29 | 179.39 (17) |
N1—Fe1—N4—C24 | −179.20 (15) | C26—N5—C25—C36 | −179.68 (19) |
N2—Fe1—N4—C24 | −97.16 (15) | Fe1—N5—C25—C36 | −0.8 (2) |
N3—Fe1—N4—C24 | −0.43 (15) | C25—N5—C26—C27 | 0.5 (3) |
N6—Fe1—N5—C26 | 179.6 (2) | Fe1—N5—C26—C27 | −178.19 (18) |
N4—Fe1—N5—C26 | 4.2 (2) | N5—C26—C27—C28 | −0.9 (4) |
N1—Fe1—N5—C26 | −90.6 (2) | C26—C27—C28—C29 | 0.4 (4) |
N3—Fe1—N5—C26 | 86.5 (2) | N5—C25—C29—C28 | −1.0 (3) |
N6—Fe1—N5—C25 | 0.94 (14) | C36—C25—C29—C28 | 179.2 (2) |
N4—Fe1—N5—C25 | −174.54 (14) | N5—C25—C29—C30 | −179.9 (2) |
N1—Fe1—N5—C25 | 90.70 (15) | C36—C25—C29—C30 | 0.3 (3) |
N3—Fe1—N5—C25 | −92.22 (15) | C27—C28—C29—C25 | 0.5 (4) |
N5—Fe1—N6—C35 | 179.3 (2) | C27—C28—C29—C30 | 179.3 (2) |
N1—Fe1—N6—C35 | 85.9 (2) | C25—C29—C30—C31 | 0.6 (4) |
N2—Fe1—N6—C35 | 3.5 (2) | C28—C29—C30—C31 | −178.2 (3) |
N5—Fe1—N6—C36 | −0.92 (14) | C29—C30—C31—C32 | −0.9 (4) |
N1—Fe1—N6—C36 | −94.38 (15) | C30—C31—C32—C36 | 0.4 (4) |
N2—Fe1—N6—C36 | −176.71 (14) | C30—C31—C32—C33 | −179.0 (3) |
N3—Fe1—N6—C36 | 86.72 (15) | C36—C32—C33—C34 | −0.4 (4) |
C2—N1—C1—C5 | 3.4 (3) | C31—C32—C33—C34 | 179.0 (2) |
Fe1—N1—C1—C5 | −175.04 (18) | C32—C33—C34—C35 | 1.1 (4) |
C2—N1—C1—C12 | −176.4 (2) | C36—N6—C35—C34 | −0.5 (3) |
Fe1—N1—C1—C12 | 5.2 (3) | Fe1—N6—C35—C34 | 179.29 (18) |
C1—N1—C2—C3 | −0.6 (4) | C33—C34—C35—N6 | −0.7 (4) |
Fe1—N1—C2—C3 | 177.50 (19) | C35—N6—C36—C32 | 1.2 (3) |
N1—C2—C3—C4 | −2.1 (4) | Fe1—N6—C36—C32 | −178.56 (17) |
C2—C3—C4—C5 | 2.0 (4) | C35—N6—C36—C25 | −179.46 (19) |
N1—C1—C5—C4 | −3.4 (4) | Fe1—N6—C36—C25 | 0.7 (2) |
C12—C1—C5—C4 | 176.4 (2) | C33—C32—C36—N6 | −0.8 (3) |
N1—C1—C5—C6 | 176.5 (2) | C31—C32—C36—N6 | 179.7 (2) |
C12—C1—C5—C6 | −3.7 (4) | C33—C32—C36—C25 | 179.9 (2) |
C3—C4—C5—C1 | 0.5 (4) | C31—C32—C36—C25 | 0.5 (3) |
C3—C4—C5—C6 | −179.4 (3) | N5—C25—C36—N6 | 0.0 (3) |
C1—C5—C6—C7 | 1.9 (4) | C29—C25—C36—N6 | 179.86 (19) |
C4—C5—C6—C7 | −178.2 (3) | N5—C25—C36—C32 | 179.37 (19) |
C5—C6—C7—C8 | 1.0 (5) | C29—C25—C36—C32 | −0.8 (3) |
C6—C7—C8—C9 | 177.4 (3) | C42—O1—C38—C37 | −178.4 (7) |
C6—C7—C8—C12 | −2.0 (4) | C42—O1—C38'—C37' | 143.5 (8) |
C12—C8—C9—C10 | 1.0 (4) | C38—O1—C42—C43 | −136.6 (6) |
C7—C8—C9—C10 | −178.5 (3) | C38'—O1—C42—C43 | −162.0 (5) |
C8—C9—C10—C11 | −0.7 (4) | C38—O1—C42—C40 | 44.9 (6) |
C12—N2—C11—C10 | 1.9 (4) | C38'—O1—C42—C40 | 19.5 (6) |
Fe1—N2—C11—C10 | −169.21 (19) | C41—C40—C42—O1 | −156.7 (3) |
C9—C10—C11—N2 | −0.8 (4) | C39—C40—C42—O1 | 22.8 (4) |
C11—N2—C12—C8 | −1.7 (3) | C41—C40—C42—C43 | 24.9 (4) |
Fe1—N2—C12—C8 | 171.01 (19) | C39—C40—C42—C43 | −155.6 (3) |
C11—N2—C12—C1 | 177.9 (2) | O1—C42—C43—C44 | −161.2 (2) |
Fe1—N2—C12—C1 | −9.4 (2) | C40—C42—C43—C44 | 17.4 (4) |
C9—C8—C12—N2 | 0.2 (4) | O1—C42—C43—C45 | 15.6 (3) |
C7—C8—C12—N2 | 179.7 (2) | C40—C42—C43—C45 | −165.9 (3) |
C9—C8—C12—C1 | −179.3 (2) | C48—O2—C47—C46 | 164.3 (7) |
C7—C8—C12—C1 | 0.2 (3) | C47'—O2—C47—C46 | −76 (6) |
N1—C1—C12—N2 | 2.9 (3) | C48—O2—C47'—C46' | 128.5 (8) |
C5—C1—C12—N2 | −176.9 (2) | C47—O2—C48—C49 | −133.8 (8) |
N1—C1—C12—C8 | −177.5 (2) | C47'—O2—C48—C49 | −148.0 (8) |
C5—C1—C12—C8 | 2.7 (3) | C47—O2—C48—C52 | 47.5 (9) |
C14—N3—C13—C17 | 0.8 (3) | C47'—O2—C48—C52 | 33.3 (9) |
Fe1—N3—C13—C17 | 176.96 (18) | O2—C48—C49—C51 | −162.4 (2) |
C14—N3—C13—C24 | −179.5 (2) | C52—C48—C49—C51 | 16.3 (4) |
Fe1—N3—C13—C24 | −3.3 (2) | O2—C48—C49—C50 | 15.0 (3) |
C13—N3—C14—C15 | 0.4 (3) | C52—C48—C49—C50 | −166.3 (2) |
Fe1—N3—C14—C15 | −174.98 (19) | O2—C48—C52—C54 | 18.5 (4) |
N3—C14—C15—C16 | −0.7 (4) | C49—C48—C52—C54 | −160.1 (3) |
C14—C15—C16—C17 | −0.1 (4) | O2—C48—C52—C53 | −162.8 (2) |
N3—C13—C17—C16 | −1.6 (4) | C49—C48—C52—C53 | 18.7 (4) |
C24—C13—C17—C16 | 178.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H11···N7 | 0.84 | 2.17 | 2.996 (5) | 169 |
O1w—H12···N8i | 0.84 | 2.25 | 3.078 (5) | 169 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C12H8N2)3](C9H5N4O)2·0.5H2O |
Mr | 975.81 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.3497 (3), 14.1736 (4), 18.6086 (6) |
α, β, γ (°) | 94.462 (2), 96.562 (1), 101.129 (1) |
V (Å3) | 2391.12 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.55 × 0.35 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.820, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38167, 10845, 6909 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.134, 1.02 |
No. of reflections | 10845 |
No. of parameters | 661 |
No. of restraints | 40 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.43 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
Fe1—N6 | 1.9563 (19) | Fe1—N1 | 1.9752 (18) |
Fe1—N5 | 1.9654 (18) | Fe1—N2 | 1.9819 (18) |
Fe1—N4 | 1.9686 (19) | Fe1—N3 | 1.9836 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H11···N7 | 0.84 | 2.17 | 2.996 (5) | 169 |
O1w—H12···N8i | 0.84 | 2.25 | 3.078 (5) | 169 |
Symmetry code: (i) x+1, y, z. |
Acknowledgements
We are grateful for financial assistance from the DG–RSDT and ANDRU (Diretion Générale de la Recherche Scientifique et du Développement Technologique et l'Agence Nationale pour le Développement de la Recherche Universitaire, Algéria) through the PNR project. We also acknowledge the Ministry of Higher Education of Malaysia (grant No·UM.C/HIR/MOHE/SC/12) for supporting this study.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
1,10-Phenanthroline (phen) is a widely utilized chelating ligand in coordination chemistry and a lot of complexes with phen as a ligand have been reported (Hoshina et al., 2000; Hwang & Ha, 2006; Zhou & Guo, 2007). Recently, Cai et al. (2012) has reported the structure of a complex with [Fe(phen)3]2+ as cation and 1,1-dicyano-2-ethoxy-2-oxoethanide as counter-ion. We report here the synthesis and crystal structure of the title compound, in which a polynitrile anion acts as counter-ion.
The structure of (I) is composed of a discrete [Fe(phen)3]2+ cations, uncoordinated tcnoet anions and water molecules of crystallization (Fig. 1).
Six nitrogen atoms from three bidentate phen ligands form a distorted octahedron around the iron atom with a mean Fe1—N bond length of 1.972 (18) Å. The main distortion from the octahedral geometry is observed in the values of the angles subtended by phen at the metal atom (82.36 (7)°, 82.50 (8)° and 83.02 (8)° for N1—Fe1—N2, N4—Fe1—N3 and N6—Fe1—N5, respectively) which deviate significantly from the ideal value of 90°. Each phenanthroline ligand is coplanar to within 0.04 Å. The average value of dihedral angle between pairs of phenanthroline planes is 82,1(3)°. The carbon-carbon and carbon-nitrogen intra-ring bond lengths agree with those observed in other metal complexes with chelating phen (Hoshina et al., 2000; Aparici Plaza et al., 2007; Cai & Zhan, 2012).
Examination of the intermolecular contacts in the crystal structure of (I) reveals that the main contacts are associated with O—H···N hydrogen bonds involving the water H atoms and those of the N atoms of the CN groups of the tcnoet anions containing atoms O1 (Table 1). In the crystal, this leads to the formation of an infinite one-dimensional {[(H2O)(tcnoet)2]2-}n anionic chains (Fig. 2), which interact with the cationic entities [Fe(phen)3]2+ and the tcnoet anions involving atoms O2 via coulombic forces.
Due to the presence of the supplementary π electron systems of the cyano groups, the tcnoet ligands of (I) present a strong electronic delocalization, as indicated by C—N, C—C and C—O bond lengths.