metal-organic papers
m830
Huet al. [Fe(C48H36N4)(C4H8O)2] doi:10.1107/S1600536805009633 Acta Cryst.(2005). E61, m830–m831
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
High-spin [Fe(TTP)(THF)
2]
Chuan-Jiang Hu, Bruce C. Noll and W. Robert. Scheidt*
Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, IN 46556-5670, USA
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 100 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.038 wRfactor = 0.102
Data-to-parameter ratio = 25.4
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The title compound, bis(tetrahydrofuran)(5,10,15,20-tetra-p -tolylporphyrinato)iron(II), [Fe(C48H36N4)(C4H8O)2] or
[Fe(TTP)(THF)2] (TTP = dianion of meso
-tetratolylpor-phyrin), is a six-coordinate high-spin iron(II) tetratolyl-porphyrin with two tetrahydrofuran molecules as axial ligands. The FeIIatom is at an inversion center. The average
Fe—N distance is 2.067 (7) A˚ and the Fe—O distance is
2.3208 (8) A˚ .
Comment
Reedet al.(1980) reported the structure of the first six-coor-dinate high-spin iron(II) porphyrinate, [Fe(TPP)(THF)2].
Subsequently, Lecomte et al. (1986) performed an electron-density study of the compound. In this paper, we report the molecular structure of another six-coordinate high-spin
iron(II) porphyrinate, the title compound, (I),
[Fe(TTP)(THF)2].
The molecular structure of (I), with the atom-numbering scheme, is shown in Fig. 1. The FeII atom is located at a crystallographic inversion center. As a result, the FeIIatom is centered in the porphyrin plane. The independent Fe—N bond distances are 2.0619 (9) and 2.0713 (9) A˚ , which are similar to those in [Fe(TPP)(THF)2] (2.054 and 2.060 A˚ ; Reed
et al., 1980). These values are substantially longer than the value of 1.996 (6) A˚ in the low-spin six-coordinate iron(II) porphyrinate [Fe(TPP)(THT)2] (THT is tetrahydrothiophene;
Mashikoet al., 1979).
The axial Fe—O bond distance [2.3208 (8) A˚ ] is similar to the value of 2.351 (3) A˚ in [Fe(TPP)(THF)2] (Reed et al.,
1980). This bond distance indicates that the THF ligand is a weak-field ligand. The Fe—O vector is tipped by 1.3 (1)from
the normal to the mean plane through the plane of the four N
atoms. This is smaller than the 4.3 tip seen in
[Fe(TPP)(THF)2] (Reed et al., 1980). This deviation also
breaks the D4h symmetry of the FeN4O2 coordination. The
THF ligand has an envelope configuration with approximate
Cssymmetry. The O atom is displaced from the mean plane of
the four C atoms by 0.56 (3) A˚ .
Experimental
[image:2.610.315.569.71.229.2]All experimental manipulations were performed under a purified nitrogen atmosphere using standard Schlenk techniques. [Fe(TTP)]2O (35 mg) was reduced in tetrahydrofuran (10 ml) in the
presence of excess EtSH overnight. The solution was transfered into glass tubes and layered with hexane. A week later, high-quality red crystals of (I) formed.
Crystal data
[Fe(C48H36N4)(C4H8O)2] Mr= 868.87
Monoclinic,P21=n a= 13.6820 (2) A˚
b= 9.7320 (1) A˚
c= 17.1014 (2) A˚
= 104.964 (1) V= 2199.89 (5) A˚3
Z= 2
Dx= 1.312 Mg m 3
MoKradiation Cell parameters from 7064
reflections
= 2.5–31.5
= 0.39 mm1
T= 100 (2) K Needle, red
0.490.150.09 mm
Data collection
Bruker SMART APEX2 CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)
Tmin= 0.83,Tmax= 0.97
31 446 measured reflections
7311 independent reflections 6283 reflections withI> 2(I)
Rint= 0.028
max= 31.5 h=20!17
k=11!14
l=22!25
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.038
wR(F2) = 0.102 S= 1.04 7311 reflections 288 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0487P)2
+ 1.0408P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.53 e A˚ 3
min=0.31 e A˚ 3
Table 1
Selected geometric parameters (A˚ ,).
Fe1—N1 2.0619 (9) Fe1—N2 2.0713 (9)
Fe1—O1 2.3208 (8) N1—Fe1—N2 89.57 (4)
N1—Fe1—O1 89.34 (3)
N2—Fe1—O1 88.96 (3)
H atoms were positioned geometrically and treated as riding, with C—H distances in the range 0.95–0.99 A˚ and with Uiso(H) =
1.2Ueq(C).
Data collection:APEX2(Bruker Nonius, 2004); cell refinement:
APEX2andSAINT(Bruker Nonius, 2004); data reduction:SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); software used to prepare material for publication:SHELXL97.
The authors thank the US National Institutes of Health for support of this research under grant No. GM-38401.
References
Bruker Nonius (2004).APEX2andSAINT. Bruker Nonius AXS, Madison, Wisconsin, USA.
Lecomte, C., Blessing, R. H., Coppens, P. & Tabard, A. (1986).J. Am. Chem. Soc.108, 6942–6950.
Mashiko, T., Marchon, J. C., Musser, D. T., Reed, C. A., Kastner, M. E. & Scheidt, W. R. (1979).J. Am. Chem. Soc.101, 3653–3655.
Reed, C. A., Mashiko, T., Scheidt, W. R., Spartalian, K. & Lang, G. (1980).J. Am. Chem. Soc.102, 2302–2306.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Sheldrick, G. M. (2004).SADABS. Version 2.10. University of Go¨ttingen, Germany.
Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.
Figure 1
supporting information
sup-1 Acta Cryst. (2005). E61, m830–m831
supporting information
Acta Cryst. (2005). E61, m830–m831 [https://doi.org/10.1107/S1600536805009633]
High-spin [Fe(TTP)(THF)
2]
Chuan-Jiang Hu, Bruce C. Noll and W. Robert. Scheidt
Difuran(5,10,15,20-tetra-p-tolylporphyrinato)iron(II)
Crystal data
[Fe(C48H36N4)(C4H8O)2] Mr = 868.87
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 13.6820 (2) Å
b = 9.7320 (1) Å
c = 17.1014 (2) Å
β = 104.964 (1)°
V = 2199.89 (5) Å3 Z = 2
F(000) = 916
Dx = 1.312 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 7064 reflections
θ = 2.5–31.5°
µ = 0.39 mm−1 T = 100 K Needle, red
0.49 × 0.15 × 0.09 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 8.33 pixels mm-1 φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)
Tmin = 0.83, Tmax = 0.97
31446 measured reflections 7311 independent reflections 6283 reflections with I > 2σ(I)
Rint = 0.028
θmax = 31.5°, θmin = 2.2°
h = −20→17
k = −11→14
l = −22→25
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.038 wR(F2) = 0.102 S = 1.04 7311 reflections 288 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0487P)2 + 1.0408P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.53 e Å−3
Δρmin = −0.31 e Å−3
Special details
Refinement. The structures were solved by direct methods using SHELXS97 and refined against F2 using SHELXL97;
subsequent difference Fourier syntheses led to the location of most of the remaining non-hydrogen atoms. For the structure refinement all data were used including negative intensities. All nonhydrogen atoms were refined anisotropically. Hydrogen atoms were idealized with the standard SHELXL97 idealization methods. The program
SADABS was applied for the absorption correction.
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Fe1 0.0000 0.5000 0.0000 0.01226 (6)
O1 0.10367 (6) 0.59562 (9) 0.11647 (5) 0.01934 (17) N1 0.07838 (7) 0.31772 (10) 0.02650 (5) 0.01329 (17) N2 −0.09755 (7) 0.43605 (10) 0.06736 (5) 0.01363 (17) C1 0.16784 (8) 0.28681 (11) 0.00780 (6) 0.01362 (19) C2 0.20915 (9) 0.16200 (12) 0.04852 (7) 0.0169 (2)
H2 0.2701 0.1182 0.0456 0.020*
C3 0.14452 (9) 0.11871 (12) 0.09192 (7) 0.0168 (2)
H3 0.1522 0.0394 0.1253 0.020*
C4 0.06174 (8) 0.21634 (11) 0.07763 (6) 0.01360 (19) C5 −0.02064 (8) 0.20994 (11) 0.11343 (6) 0.01378 (19) C6 −0.09502 (8) 0.31293 (11) 0.10728 (6) 0.01419 (19) C7 −0.18128 (9) 0.30474 (12) 0.14189 (7) 0.0185 (2)
H7 −0.1980 0.2300 0.1718 0.022*
C8 −0.23358 (9) 0.42436 (12) 0.12335 (7) 0.0182 (2)
H8 −0.2930 0.4497 0.1388 0.022*
C9 −0.18167 (8) 0.50579 (11) 0.07575 (7) 0.01406 (19) C10 −0.21467 (8) 0.63418 (11) 0.04145 (6) 0.01365 (19) C11 −0.02727 (8) 0.08520 (11) 0.16235 (6) 0.01400 (19) C12 −0.02787 (9) −0.04621 (12) 0.12899 (6) 0.0160 (2)
H12 −0.0258 −0.0557 0.0741 0.019*
C13 −0.03143 (9) −0.16311 (12) 0.17487 (7) 0.0174 (2)
H13 −0.0307 −0.2512 0.1511 0.021*
C14 −0.03608 (9) −0.15334 (12) 0.25526 (7) 0.0181 (2) C15 −0.03564 (9) −0.02251 (12) 0.28876 (7) 0.0175 (2)
H15 −0.0385 −0.0134 0.3434 0.021*
C16 −0.03105 (8) 0.09477 (12) 0.24342 (6) 0.0156 (2)
H16 −0.0305 0.1827 0.2677 0.019*
C17 −0.04172 (12) −0.28142 (14) 0.30315 (9) 0.0298 (3)
H17A 0.0220 −0.2934 0.3448 0.045*
H17B −0.0532 −0.3611 0.2669 0.045*
H17C −0.0976 −0.2732 0.3290 0.045*
C18 −0.30962 (8) 0.69408 (11) 0.05572 (6) 0.01462 (19) C19 −0.40429 (9) 0.64838 (14) 0.01241 (8) 0.0222 (2)
H19 −0.4092 0.5724 −0.0233 0.027*
supporting information
sup-3 Acta Cryst. (2005). E61, m830–m831
H20 −0.5561 0.6795 −0.0097 0.028*
C21 −0.48820 (9) 0.82329 (13) 0.07223 (8) 0.0201 (2) C22 −0.39343 (10) 0.86570 (14) 0.11803 (9) 0.0259 (3)
H22 −0.3888 0.9390 0.1555 0.031*
C23 −0.30539 (9) 0.80243 (14) 0.10973 (8) 0.0232 (2)
H23 −0.2416 0.8336 0.1413 0.028*
C24 −0.58230 (10) 0.89975 (15) 0.07712 (10) 0.0298 (3)
H24A −0.5796 0.9939 0.0574 0.045*
H24B −0.5865 0.9021 0.1335 0.045*
H24C −0.6420 0.8530 0.0437 0.045*
C25 0.17909 (10) 0.69759 (13) 0.11429 (8) 0.0231 (2)
H25A 0.1735 0.7766 0.1494 0.028*
H25B 0.1710 0.7313 0.0584 0.028*
C26 0.28080 (11) 0.62589 (18) 0.14519 (11) 0.0371 (3)
H26A 0.3284 0.6843 0.1849 0.044*
H26B 0.3111 0.6045 0.1000 0.044*
C27 0.25665 (11) 0.49408 (14) 0.18507 (8) 0.0268 (3)
H27A 0.2631 0.4123 0.1523 0.032*
H27B 0.3018 0.4831 0.2402 0.032*
C28 0.14731 (11) 0.51593 (14) 0.18790 (7) 0.0241 (3)
H28A 0.1118 0.4270 0.1865 0.029*
H28B 0.1441 0.5665 0.2374 0.029*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C19 0.0158 (5) 0.0245 (6) 0.0262 (5) 0.0021 (4) 0.0055 (4) −0.0074 (5) C20 0.0128 (5) 0.0282 (6) 0.0299 (6) 0.0026 (4) 0.0051 (4) −0.0028 (5) C21 0.0166 (5) 0.0194 (5) 0.0279 (5) 0.0064 (4) 0.0122 (4) 0.0054 (4) C22 0.0206 (6) 0.0241 (6) 0.0360 (6) 0.0034 (5) 0.0127 (5) −0.0092 (5) C23 0.0157 (5) 0.0246 (6) 0.0299 (6) 0.0018 (4) 0.0071 (4) −0.0088 (5) C24 0.0202 (6) 0.0262 (7) 0.0478 (8) 0.0093 (5) 0.0176 (6) 0.0031 (6) C25 0.0222 (6) 0.0182 (5) 0.0265 (6) −0.0032 (4) 0.0020 (5) −0.0013 (4) C26 0.0213 (7) 0.0346 (8) 0.0556 (9) 0.0023 (6) 0.0106 (6) 0.0068 (7) C27 0.0267 (7) 0.0255 (7) 0.0234 (6) 0.0059 (5) −0.0019 (5) −0.0023 (5) C28 0.0294 (7) 0.0249 (6) 0.0168 (5) −0.0031 (5) 0.0040 (5) 0.0004 (4)
Geometric parameters (Å, º)
Fe1—N1i 2.0619 (9) C13—H13 0.9500
Fe1—N1 2.0619 (9) C14—C15 1.3955 (17)
Fe1—N2i 2.0712 (9) C14—C17 1.5044 (17)
Fe1—N2 2.0713 (9) C15—C16 1.3903 (16)
Fe1—O1 2.3208 (8) C15—H15 0.9500
Fe1—O1i 2.3208 (8) C16—H16 0.9500
O1—C25 1.4391 (15) C17—H17A 0.9800
O1—C28 1.4399 (15) C17—H17B 0.9800
N1—C4 1.3758 (13) C17—H17C 0.9800
N1—C1 1.3758 (13) C18—C19 1.3888 (16)
N2—C6 1.3749 (14) C18—C23 1.3931 (16)
N2—C9 1.3751 (14) C19—C20 1.3942 (17)
C1—C10i 1.4107 (15) C19—H19 0.9500
C1—C2 1.4409 (15) C20—C21 1.3854 (18)
C2—C3 1.3599 (15) C20—H20 0.9500
C2—H2 0.9500 C21—C22 1.3932 (19)
C3—C4 1.4499 (15) C21—C24 1.5079 (17)
C3—H3 0.9500 C22—C23 1.3922 (17)
C4—C5 1.4162 (15) C22—H22 0.9500
C5—C6 1.4128 (15) C23—H23 0.9500
C5—C11 1.4902 (15) C24—H24A 0.9800
C6—C7 1.4527 (15) C24—H24B 0.9800
C7—C8 1.3604 (16) C24—H24C 0.9800
C7—H7 0.9500 C25—C26 1.524 (2)
C8—C9 1.4469 (15) C25—H25A 0.9900
C8—H8 0.9500 C25—H25B 0.9900
C9—C10 1.4045 (15) C26—C27 1.528 (2)
C10—C1i 1.4107 (15) C26—H26A 0.9900
C10—C18 1.5002 (15) C26—H26B 0.9900
C11—C12 1.3995 (15) C27—C28 1.524 (2)
C11—C16 1.4038 (15) C27—H27A 0.9900
C12—C13 1.3899 (16) C27—H27B 0.9900
C12—H12 0.9500 C28—H28A 0.9900
supporting information
sup-5 Acta Cryst. (2005). E61, m830–m831
N1i—Fe1—N1 180.0 C15—C14—C13 118.04 (10)
N1i—Fe1—N2i 89.57 (4) C15—C14—C17 121.86 (11)
N1—Fe1—N2i 90.43 (4) C13—C14—C17 120.11 (11)
N1i—Fe1—N2 90.43 (4) C16—C15—C14 121.07 (10)
N1—Fe1—N2 89.57 (4) C16—C15—H15 119.5
N2i—Fe1—N2 180.0 C14—C15—H15 119.5
N1i—Fe1—O1 90.66 (3) C15—C16—C11 120.99 (10)
N1—Fe1—O1 89.34 (3) C15—C16—H16 119.5
N2i—Fe1—O1 91.04 (3) C11—C16—H16 119.5
N2—Fe1—O1 88.96 (3) C14—C17—H17A 109.5
N1i—Fe1—O1i 89.34 (3) C14—C17—H17B 109.5
N1—Fe1—O1i 90.66 (3) H17A—C17—H17B 109.5
N2i—Fe1—O1i 88.96 (3) C14—C17—H17C 109.5
N2—Fe1—O1i 91.04 (3) H17A—C17—H17C 109.5
O1—Fe1—O1i 180.0 H17B—C17—H17C 109.5
C25—O1—C28 104.50 (9) C19—C18—C23 117.99 (10)
C25—O1—Fe1 122.52 (7) C19—C18—C10 121.09 (10)
C28—O1—Fe1 122.67 (7) C23—C18—C10 120.83 (10)
C4—N1—C1 107.10 (9) C18—C19—C20 120.87 (11)
C4—N1—Fe1 126.48 (7) C18—C19—H19 119.6
C1—N1—Fe1 125.49 (7) C20—C19—H19 119.6
C6—N2—C9 107.03 (9) C21—C20—C19 121.28 (12)
C6—N2—Fe1 126.92 (7) C21—C20—H20 119.4
C9—N2—Fe1 125.91 (7) C19—C20—H20 119.4
N1—C1—C10i 126.02 (10) C20—C21—C22 117.82 (11)
N1—C1—C2 109.48 (9) C20—C21—C24 121.69 (12)
C10i—C1—C2 124.48 (10) C22—C21—C24 120.45 (12)
C3—C2—C1 107.20 (10) C23—C22—C21 121.05 (12)
C3—C2—H2 126.4 C23—C22—H22 119.5
C1—C2—H2 126.4 C21—C22—H22 119.5
C2—C3—C4 107.14 (10) C22—C23—C18 120.89 (12)
C2—C3—H3 126.4 C22—C23—H23 119.6
C4—C3—H3 126.4 C18—C23—H23 119.6
N1—C4—C5 125.96 (10) C21—C24—H24A 109.5
N1—C4—C3 109.07 (9) C21—C24—H24B 109.5
C5—C4—C3 124.93 (10) H24A—C24—H24B 109.5
C6—C5—C4 125.09 (10) C21—C24—H24C 109.5
C6—C5—C11 118.21 (9) H24A—C24—H24C 109.5
C4—C5—C11 116.69 (9) H24B—C24—H24C 109.5
N2—C6—C5 125.49 (9) O1—C25—C26 105.78 (11)
N2—C6—C7 109.33 (9) O1—C25—H25A 110.6
C5—C6—C7 125.17 (10) C26—C25—H25A 110.6
C8—C7—C6 106.97 (10) O1—C25—H25B 110.6
C8—C7—H7 126.5 C26—C25—H25B 110.6
C6—C7—H7 126.5 H25A—C25—H25B 108.7
C7—C8—C9 107.14 (10) C25—C26—C27 104.82 (12)
C7—C8—H8 126.4 C25—C26—H26A 110.8
N2—C9—C10 125.66 (10) C25—C26—H26B 110.8
N2—C9—C8 109.51 (9) C27—C26—H26B 110.8
C10—C9—C8 124.80 (10) H26A—C26—H26B 108.9
C9—C10—C1i 126.00 (10) C28—C27—C26 102.95 (11)
C9—C10—C18 118.44 (9) C28—C27—H27A 111.2
C1i—C10—C18 115.54 (9) C26—C27—H27A 111.2
C12—C11—C16 117.73 (10) C28—C27—H27B 111.2
C12—C11—C5 120.69 (9) C26—C27—H27B 111.2
C16—C11—C5 121.56 (10) H27A—C27—H27B 109.1
C13—C12—C11 121.02 (10) O1—C28—C27 104.10 (10)
C13—C12—H12 119.5 O1—C28—H28A 110.9
C11—C12—H12 119.5 C27—C28—H28A 110.9
C12—C13—C14 121.16 (11) O1—C28—H28B 110.9
C12—C13—H13 119.4 C27—C28—H28B 110.9
C14—C13—H13 119.4 H28A—C28—H28B 109.0
