Download citation
Download citation
link to html
The title complex, [Fe(C32H36N4)(C4H8O)2]ClO4, shows an S4-ruffled porphyrin ring, where the maximum deviation of the meso-carbon from the least-squares plane of the [Fe(C20N4)] core is as high as 0.675 (9) Å. This is the highest class of deviation among S4-ruffled iron(III) porphyrin complexes. The average Fe—Np bond distance is 1.967 (12) Å (Np denotes an N atom of the equatorial ligand).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015833/oa1111sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015833/oa1111Isup2.hkl
Contains datablock I

CCDC reference: 162538

Comment top

Metalloporphyrins with nonplanar structures are of essential interest in understanding the role and functions of haemoproteins with a deformed porphyrin ring (Finzel et al., 1984; Hobbs & Shelnutt, 1995; Ikeue et al., 2000). In this paper, we describe the molecular structure of the title complex, (I), which shows the presence of a highly deformed porphyrin ring. \sch

The molecular structure of (I) with the atom-numbering scheme is shown in Fig. 1. The porphyrin ring exhibits the S4-ruffled structure, where the shifts of the meso C atoms C5, C10, C15 and C20 from the least-squares plane of the [Fe(C20N4)] porphyrinato core are -0.675 (9), 0.623 (8), -0.579 (8) and 0.640 (8) Å, respectively. The ruffling dihedral angles of the two pairs of diagonal pyrroles, 37.4 (7) and 38.3 (7)°, are much larger than those in [Fe(TEtP)(thf)2]ClO4 [22.3 (1) and 21.2 (1)°; Ohgo et al., 1999; TEtP is the dianion of meso-tetraethylporphyrin and thf is tetrahydrofuran].

Both thf rings in (I) are parallel to the Cmeso—Fe—Cmeso axis and are perpendicular to each other [C5···Fe1—O1—C33 1.4 (4), C10···Fe1—O2—C40 8.5 (4), C40—O2—O1—C33 96.5 (7) and C37—O2—O1—C36 79.5 (7)°]. One of the two coordinated thf molecules shows a bent form, which is well illustrated by the Fe1—O2—C40—C39 and Fe1—O2—C37—C38 dihedral angles of 124.4 (6) and -124.1 (7)°, respectively. In contrast, the other thf molecule shows a planar form: the Fe1—O1—C33—C34 and Fe1—O1–36-C35A dihedral angles are -173.6 (4) and -163.7 (15)°, respectively. This difference in coordination structure of the thf molecules is ascribed to the crystal packing in the direction normal to the porphyrin ring.

The Fe—Np bond distances of (I) [average 1.967 (12) Å] are significantly shorter than those of other bis(thf) complexes, such as [Fe(TEtP)(thf)2]ClO4 [average 2.006 (3) Å; Ohgo et al., 1999], [Fe(TPP)(thf)2]ClO4 [average 2.016 (3) Å; Chen et al., 1998; TPP is the dianion of meso-tetraphenylporphyrin] and [Fe(OEP)(thf)2]ClO4 [1.994 Å; Masuda et al., 1982; OEP is the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin]. The average deviation of meso C atoms from the least-squares plane of porphyrin ring is well known as an index of the degree of deformation. In the case of (I), it is 0.68 Å, which is much larger than the corresponding values in [Fe(TPP)(thf)2]ClO4 (0.01 Å) and [Fe(OEP)(THF)2]ClO4 (0.03 Å). In addition, there is a tendency that higher deformed complexes have shorter Fe—Np bonds, as in (I). These results suggest that (I) is one of the most highly deformed (porphyrinato)iron(III) complexes known to date.

Related literature top

For related literature, see: Chen et al. (1998); Ema et al. (1994); Finzel et al. (1984); Hobbs & Shelnutt (1995); Ikeue et al. (2000); Masuda et al. (1982); Ohgo et al. (1999).

Experimental top

meso-Tetraisopropylporphyrin was prepared according to the procedure of Ema et al. (1994). Insertion of iron was carried out by refluxing meso-tetraisopropylporphyrin with FeCl2·4H2O in methanol-chloroform (1:3). The resulting chloro-iron(III) complex was converted into the title complex, (I), by treatment with AgClO4 in tetrahydrofuran solution. The solid thus obtained was recrystallized from tetrahydrofuran-heptane (3:1).

Refinement top

There is disorder in one of the two coordinated thf molecules, with site occupancy factors for the disordered atoms, C35A and C35B, of 0.43 and 0.57. H atoms were refined using a riding model, with C—H distances of 0.96 Å for primary H, 0.97 Å for secondary and 0.93 Å for aromatic. H atom U values were constrained to 1.2 times the equivalent isotropic U of the atoms to which they were attached (1.5 for methyl groups).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992b); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SV (Nemoto & Ohashi, 1993); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure (ORTEP; Johnson, 1965) of (I) with the atomic numbering. Displacement ellipsoids are shown at the 30% probability level and H atoms have been omitted for clarity.
[Bis(tetrahydrofuran-κO)(meso-5,10,15,20-tetraisopropylporphyrinato-κ4N) iron(III)] perchlorate top
Crystal data top
[Fe(C32H36N4)(C4H8O)2]·ClO4F(000) = 1644
Mr = 776.16Dx = 1.274 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 10.56 (10) ÅCell parameters from 25 reflections
b = 32.98 (15) Åθ = 14.4–15.6°
c = 11.64 (8) ŵ = 0.49 mm1
β = 92.8 (7)°T = 298 K
V = 4048 (51) Å3Prismatic, brown
Z = 40.5 × 0.4 × 0.2 mm
Data collection top
Rigaku AFC-5
diffractometer
4237 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
Graphite monochromatorθmax = 27.5°, θmin = 2.0°
ω scansh = 1313
Absorption correction: ψ-scan
(North et al., 1968)
k = 042
Tmin = 0.819, Tmax = 0.907l = 015
9566 measured reflections3 standard reflections every 100 reflections
9128 independent reflections intensity decay: 0.7%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.215H-atom parameters constrained
S = 0.91Calculated w = 1/[σ2(Fo2) + (0.1329P)2]
where P = (Fo2 + 2Fc2)/3
9128 reflections(Δ/σ)max < 0.001
495 parametersΔρmax = 0.68 e Å3
6 restraintsΔρmin = 0.41 e Å3
Crystal data top
[Fe(C32H36N4)(C4H8O)2]·ClO4V = 4048 (51) Å3
Mr = 776.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.56 (10) ŵ = 0.49 mm1
b = 32.98 (15) ÅT = 298 K
c = 11.64 (8) Å0.5 × 0.4 × 0.2 mm
β = 92.8 (7)°
Data collection top
Rigaku AFC-5
diffractometer
4237 reflections with I > 2σ(I)
Absorption correction: ψ-scan
(North et al., 1968)
Rint = 0.037
Tmin = 0.819, Tmax = 0.9073 standard reflections every 100 reflections
9566 measured reflections intensity decay: 0.7%
9128 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0636 restraints
wR(F2) = 0.215H-atom parameters constrained
S = 0.91Δρmax = 0.68 e Å3
9128 reflectionsΔρmin = 0.41 e Å3
495 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.25256 (5)0.122097 (15)0.63416 (5)0.04879 (18)
Cl10.21760 (18)0.14060 (5)0.19720 (16)0.1082 (5)
O10.4307 (3)0.10868 (9)0.7364 (2)0.0656 (7)
O20.0801 (3)0.13103 (9)0.5259 (3)0.0705 (8)
O30.2323 (7)0.17856 (15)0.2445 (5)0.188 (3)
O40.0944 (7)0.1341 (2)0.1771 (8)0.232 (4)
O50.2488 (5)0.10967 (16)0.2813 (6)0.158 (2)
O60.2833 (15)0.1382 (3)0.1071 (9)0.344 (8)
N10.3525 (3)0.14029 (10)0.5079 (3)0.0562 (8)
N20.2545 (3)0.06553 (9)0.5753 (3)0.0497 (7)
N30.1525 (3)0.10439 (10)0.7613 (3)0.0521 (7)
N40.2513 (3)0.17846 (10)0.6933 (3)0.0568 (8)
C10.4277 (4)0.17498 (13)0.5060 (4)0.0647 (11)
C20.4947 (4)0.17452 (17)0.4013 (5)0.0819 (14)
H20.55440.19340.37950.098*
C30.4554 (5)0.14196 (16)0.3409 (4)0.0763 (13)
H30.47990.13530.26750.092*
C40.3698 (4)0.11889 (14)0.4067 (3)0.0616 (10)
C50.3237 (4)0.07968 (14)0.3796 (3)0.0606 (10)
C60.2782 (4)0.05373 (12)0.4647 (3)0.0543 (9)
C70.2653 (5)0.00991 (14)0.4567 (4)0.0727 (12)
H70.27450.00550.39080.087*
C80.2379 (4)0.00453 (13)0.5604 (4)0.0681 (12)
H80.22780.03160.58010.082*
C90.2272 (3)0.02995 (11)0.6354 (3)0.0515 (9)
C100.1805 (4)0.02860 (12)0.7450 (3)0.0550 (9)
C110.1364 (4)0.06421 (12)0.7985 (3)0.0556 (9)
C120.0571 (4)0.06471 (15)0.8936 (4)0.0716 (12)
H120.03310.04230.93590.086*
C130.0222 (4)0.10415 (16)0.9116 (4)0.0729 (12)
H130.03220.11310.96680.087*
C140.0834 (4)0.12910 (13)0.8315 (3)0.0611 (10)
C150.0829 (4)0.17203 (14)0.8308 (4)0.0674 (11)
C160.1681 (4)0.19452 (13)0.7699 (4)0.0663 (11)
C170.1971 (6)0.23750 (14)0.7855 (5)0.0891 (16)
H170.15260.25570.82930.107*
C180.2987 (6)0.24612 (14)0.7257 (5)0.0866 (16)
H180.33960.27110.72360.104*
C190.3337 (5)0.20982 (12)0.6650 (4)0.0680 (12)
C200.4258 (4)0.20738 (13)0.5853 (4)0.0705 (13)
C210.3302 (5)0.06221 (16)0.2581 (4)0.0776 (13)
H210.27250.03890.25600.093*
C220.2748 (6)0.0917 (2)0.1650 (4)0.112 (2)
H22A0.19590.10250.18900.168*
H22B0.26070.07740.09370.168*
H22C0.33350.11350.15470.168*
C230.4593 (5)0.04476 (18)0.2321 (5)0.1011 (18)
H23A0.51870.06650.22370.152*
H23B0.45210.02940.16200.152*
H23C0.48860.02740.29410.152*
C240.1655 (4)0.01377 (13)0.7989 (4)0.0645 (11)
H240.21500.03240.75320.077*
C250.0280 (5)0.02952 (14)0.7894 (5)0.0856 (15)
H25A0.02360.01360.83780.128*
H25B0.02620.05740.81330.128*
H25C0.00420.02740.71100.128*
C260.2231 (5)0.01635 (16)0.9228 (4)0.0860 (15)
H26A0.17680.00110.97180.129*
H26B0.31020.00800.92410.129*
H26C0.21810.04380.94980.129*
C270.0055 (5)0.19439 (17)0.9093 (4)0.0931 (16)
H270.05660.17160.93450.112*
C280.1074 (7)0.2197 (3)0.8510 (6)0.198 (5)
H28A0.09320.24780.86980.297*
H28B0.18850.21150.87670.297*
H28C0.10580.21620.76920.297*
C290.0546 (6)0.20754 (17)1.0239 (4)0.0984 (18)
H29A0.12220.22621.01130.148*
H29B0.08760.18421.06470.148*
H29C0.00800.22051.06830.148*
C300.5187 (5)0.24315 (17)0.5793 (6)0.110 (2)
H300.49020.25710.64780.132*
C310.4923 (6)0.27670 (15)0.5000 (5)0.1002 (18)
H31A0.55220.29810.51570.150*
H31B0.40800.28660.50970.150*
H31C0.49930.26740.42230.150*
C320.6479 (5)0.2327 (2)0.6294 (9)0.187 (5)
H32A0.69920.22270.56970.280*
H32B0.64070.21230.68740.280*
H32C0.68660.25650.66320.280*
C330.5372 (5)0.0885 (2)0.6924 (5)0.112 (2)
H33A0.57550.10510.63470.134*
H33B0.51170.06290.65760.134*
C340.6295 (6)0.0816 (3)0.7935 (6)0.131 (3)
H34A0.61760.05510.82750.157*
H34B0.71640.08410.77130.157*
C35A0.5957 (10)0.1147 (9)0.874 (3)0.228 (19)0.43 (2)
H35A0.63730.13990.85520.274*0.43 (2)
H35B0.61880.10750.95310.274*0.43 (2)
C35B0.5496 (13)0.0868 (5)0.8959 (8)0.113 (7)0.57 (2)
H35C0.50820.06160.91520.136*0.57 (2)
H35D0.60000.09630.96250.136*0.57 (2)
C360.4548 (6)0.1181 (2)0.8550 (5)0.117 (2)
H36A0.41180.09910.90340.140*
H36B0.42640.14540.87180.140*
C370.0397 (5)0.16935 (15)0.4739 (5)0.0883 (16)
H37A0.03840.16750.39060.106*
H37B0.09670.19100.49870.106*
C380.0883 (7)0.1769 (2)0.5129 (7)0.121 (2)
H38A0.14280.18800.45120.145*
H38B0.08590.19560.57730.145*
C390.1345 (7)0.1351 (3)0.5490 (7)0.138 (3)
H39A0.15150.13500.63010.166*
H39B0.21180.12800.50530.166*
C400.0308 (5)0.10559 (16)0.5253 (5)0.0892 (16)
H40A0.02280.08500.58480.107*
H40B0.04600.09250.45130.107*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0517 (3)0.0435 (3)0.0510 (3)0.0051 (2)0.0009 (2)0.0021 (2)
Cl10.1148 (13)0.0931 (11)0.1175 (13)0.0000 (9)0.0170 (10)0.0177 (10)
O10.0624 (18)0.0771 (19)0.0567 (17)0.0065 (15)0.0022 (14)0.0015 (14)
O20.0634 (18)0.0611 (18)0.085 (2)0.0129 (14)0.0176 (16)0.0168 (15)
O30.299 (8)0.081 (3)0.185 (5)0.025 (4)0.068 (5)0.014 (4)
O40.190 (7)0.211 (7)0.304 (10)0.058 (5)0.161 (7)0.080 (6)
O50.143 (4)0.109 (4)0.230 (6)0.007 (3)0.068 (4)0.034 (4)
O60.52 (2)0.256 (10)0.235 (10)0.015 (11)0.234 (12)0.040 (7)
N10.0534 (19)0.0572 (19)0.058 (2)0.0115 (16)0.0019 (15)0.0124 (16)
N20.0531 (18)0.0468 (17)0.0496 (18)0.0040 (14)0.0070 (14)0.0003 (14)
N30.0536 (18)0.0530 (18)0.0491 (17)0.0022 (15)0.0072 (14)0.0005 (14)
N40.062 (2)0.0462 (17)0.061 (2)0.0052 (16)0.0088 (16)0.0014 (15)
C10.057 (2)0.063 (3)0.072 (3)0.015 (2)0.008 (2)0.020 (2)
C20.063 (3)0.088 (4)0.096 (4)0.019 (3)0.013 (3)0.033 (3)
C30.071 (3)0.090 (4)0.070 (3)0.018 (3)0.015 (2)0.022 (3)
C40.058 (2)0.077 (3)0.051 (2)0.010 (2)0.0042 (18)0.013 (2)
C50.056 (2)0.077 (3)0.049 (2)0.007 (2)0.0065 (18)0.007 (2)
C60.056 (2)0.059 (2)0.050 (2)0.0075 (18)0.0120 (17)0.0068 (18)
C70.090 (3)0.064 (3)0.068 (3)0.007 (2)0.022 (2)0.017 (2)
C80.089 (3)0.050 (2)0.067 (3)0.008 (2)0.024 (2)0.003 (2)
C90.051 (2)0.047 (2)0.057 (2)0.0061 (16)0.0040 (18)0.0016 (17)
C100.054 (2)0.055 (2)0.056 (2)0.0014 (18)0.0057 (18)0.0065 (18)
C110.055 (2)0.057 (2)0.057 (2)0.0026 (18)0.0110 (18)0.0070 (18)
C120.077 (3)0.072 (3)0.065 (3)0.005 (2)0.022 (2)0.005 (2)
C130.065 (3)0.090 (3)0.066 (3)0.006 (2)0.017 (2)0.007 (2)
C140.060 (2)0.070 (3)0.054 (2)0.007 (2)0.0005 (19)0.009 (2)
C150.068 (3)0.067 (3)0.068 (3)0.006 (2)0.004 (2)0.017 (2)
C160.080 (3)0.051 (2)0.063 (3)0.009 (2)0.016 (2)0.008 (2)
C170.132 (5)0.050 (3)0.082 (3)0.013 (3)0.015 (3)0.009 (2)
C180.127 (5)0.043 (2)0.086 (3)0.007 (3)0.023 (3)0.001 (2)
C190.082 (3)0.050 (2)0.069 (3)0.011 (2)0.028 (2)0.011 (2)
C200.069 (3)0.058 (3)0.081 (3)0.019 (2)0.024 (2)0.023 (2)
C210.079 (3)0.095 (4)0.057 (3)0.017 (3)0.014 (2)0.005 (2)
C220.120 (5)0.164 (7)0.053 (3)0.020 (4)0.001 (3)0.011 (3)
C230.103 (4)0.106 (4)0.098 (4)0.016 (3)0.046 (3)0.018 (3)
C240.070 (3)0.059 (3)0.067 (3)0.003 (2)0.017 (2)0.010 (2)
C250.085 (3)0.069 (3)0.104 (4)0.020 (3)0.016 (3)0.015 (3)
C260.092 (4)0.087 (3)0.081 (3)0.011 (3)0.008 (3)0.030 (3)
C270.096 (4)0.099 (4)0.084 (4)0.030 (3)0.004 (3)0.029 (3)
C280.140 (7)0.314 (14)0.145 (7)0.125 (8)0.038 (6)0.099 (8)
C290.131 (5)0.084 (4)0.081 (4)0.004 (3)0.013 (3)0.025 (3)
C300.097 (4)0.092 (4)0.133 (5)0.048 (3)0.041 (4)0.044 (4)
C310.123 (5)0.067 (3)0.111 (4)0.030 (3)0.013 (3)0.031 (3)
C320.081 (4)0.127 (6)0.351 (14)0.041 (4)0.072 (6)0.078 (8)
C330.070 (3)0.172 (7)0.093 (4)0.037 (4)0.004 (3)0.001 (4)
C340.090 (4)0.170 (7)0.132 (6)0.036 (4)0.033 (4)0.006 (5)
C35A0.23 (3)0.13 (2)0.30 (3)0.074 (18)0.20 (3)0.12 (2)
C35B0.117 (10)0.150 (13)0.068 (7)0.061 (10)0.037 (6)0.025 (7)
C360.125 (5)0.127 (5)0.087 (4)0.024 (4)0.037 (4)0.029 (4)
C370.087 (4)0.075 (3)0.100 (4)0.002 (3)0.025 (3)0.024 (3)
C380.109 (5)0.104 (5)0.146 (6)0.025 (4)0.002 (4)0.000 (5)
C390.080 (4)0.189 (8)0.150 (7)0.003 (5)0.026 (4)0.010 (6)
C400.069 (3)0.083 (3)0.114 (4)0.024 (3)0.021 (3)0.013 (3)
Geometric parameters (Å, º) top
Fe1—N11.946 (14)C22—H22B0.9600
Fe1—N31.950 (14)C22—H22C0.9600
Fe1—N41.982 (9)C23—H23A0.9600
Fe1—N21.988 (9)C23—H23B0.9600
Fe1—O22.183 (19)C23—H23C0.9600
Fe1—O12.221 (19)C24—C261.540 (13)
Cl1—O61.231 (12)C24—C251.541 (14)
Cl1—O41.351 (14)C24—H240.9800
Cl1—O31.379 (7)C25—H25A0.9600
Cl1—O51.462 (8)C25—H25B0.9600
O1—C331.423 (12)C25—H25C0.9600
O1—C361.426 (11)C26—H26A0.9600
O2—C401.441 (11)C26—H26B0.9600
O2—C371.456 (8)C26—H26C0.9600
N1—C11.393 (8)C27—C281.499 (10)
N1—C41.393 (9)C27—C291.511 (13)
N2—C61.380 (10)C27—H270.9800
N2—C91.403 (7)C28—H28A0.9600
N3—C141.387 (9)C28—H28B0.9600
N3—C111.407 (8)C28—H28C0.9600
N4—C161.387 (11)C29—H29A0.9600
N4—C191.402 (9)C29—H29B0.9600
C1—C201.413 (9)C29—H29C0.9600
C1—C21.439 (13)C30—C311.459 (9)
C2—C31.338 (9)C30—C321.497 (13)
C2—H20.9300C30—H300.9800
C3—C41.432 (10)C31—H31A0.9600
C3—H30.9300C31—H31B0.9600
C4—C51.412 (8)C31—H31C0.9600
C5—C61.410 (9)C32—H32A0.9600
C5—C211.532 (11)C32—H32B0.9600
C6—C71.454 (9)C32—H32C0.9600
C7—C81.342 (10)C33—C341.508 (14)
C7—H70.9300C33—H33A0.9700
C8—C91.441 (8)C33—H33B0.9700
C8—H80.9300C34—C35A1.493 (8)
C9—C101.391 (11)C34—C35B1.504 (12)
C10—C111.419 (8)C34—H34A0.9700
C10—C241.543 (8)C34—H34B0.9700
C11—C121.420 (12)C35A—C361.498 (15)
C12—C131.371 (9)C35A—H35A0.9700
C12—H120.9300C35A—H35B0.9700
C13—C141.422 (10)C35B—C361.501 (9)
C13—H130.9300C35B—H35C0.9700
C14—C151.416 (9)C35B—H35D0.9700
C15—C161.388 (11)C36—H36A0.9700
C15—C271.527 (11)C36—H36B0.9700
C16—C171.459 (9)C37—C381.468 (15)
C17—C181.337 (13)C37—H37A0.9700
C17—H170.9300C37—H37B0.9700
C18—C191.447 (9)C38—C391.526 (11)
C18—H180.9300C38—H38A0.9700
C19—C201.379 (13)C38—H38B0.9700
C20—C301.538 (9)C39—C401.501 (12)
C21—C231.524 (14)C39—H39A0.9700
C21—C221.549 (11)C39—H39B0.9700
C21—H210.9800C40—H40A0.9700
C22—H22A0.9600C40—H40B0.9700
N1—Fe1—N3179.45 (14)C26—C24—C25112.1 (7)
N1—Fe1—N489.2 (3)C26—C24—C10112.8 (4)
N3—Fe1—N490.2 (3)C25—C24—C10113.0 (5)
N1—Fe1—N290.8 (3)C26—C24—H24106.1
N3—Fe1—N289.7 (3)C25—C24—H24106.1
N4—Fe1—N2179.75 (14)C10—C24—H24106.1
N1—Fe1—O289.5 (7)C24—C25—H25A109.5
N3—Fe1—O290.6 (7)C24—C25—H25B109.5
N4—Fe1—O293.1 (3)H25A—C25—H25B109.5
N2—Fe1—O287.1 (3)C24—C25—H25C109.5
N1—Fe1—O189.4 (7)H25A—C25—H25C109.5
N3—Fe1—O190.6 (7)H25B—C25—H25C109.5
N4—Fe1—O191.2 (3)C24—C26—H26A109.5
N2—Fe1—O188.6 (3)C24—C26—H26B109.5
O2—Fe1—O1175.53 (12)H26A—C26—H26B109.5
O6—Cl1—O4110.5 (10)C24—C26—H26C109.5
O6—Cl1—O3109.1 (6)H26A—C26—H26C109.5
O4—Cl1—O3110.0 (6)H26B—C26—H26C109.5
O6—Cl1—O5112.9 (8)C28—C27—C29120.0 (7)
O4—Cl1—O5104.8 (6)C28—C27—C15116.4 (7)
O3—Cl1—O5109.4 (6)C29—C27—C15115.1 (7)
C33—O1—C36110.2 (7)C28—C27—H2799.8
C33—O1—Fe1124.3 (6)C29—C27—H2799.8
C36—O1—Fe1125.5 (6)C15—C27—H2799.8
C40—O2—C37106.3 (6)C27—C28—H28A109.5
C40—O2—Fe1125.4 (5)C27—C28—H28B109.5
C37—O2—Fe1125.2 (3)H28A—C28—H28B109.5
C1—N1—C4107.7 (6)C27—C28—H28C109.5
C1—N1—Fe1126.6 (4)H28A—C28—H28C109.5
C4—N1—Fe1125.5 (5)H28B—C28—H28C109.5
C6—N2—C9106.3 (5)C27—C29—H29A109.5
C6—N2—Fe1126.3 (2)C27—C29—H29B109.5
C9—N2—Fe1127.4 (4)H29A—C29—H29B109.5
C14—N3—C11107.3 (5)C27—C29—H29C109.5
C14—N3—Fe1126.3 (5)H29A—C29—H29C109.5
C11—N3—Fe1126.5 (3)H29B—C29—H29C109.5
C16—N4—C19106.8 (6)C31—C30—C32124.2 (6)
C16—N4—Fe1126.6 (3)C31—C30—C20120.5 (6)
C19—N4—Fe1126.6 (5)C32—C30—C20112.2 (6)
N1—C1—C20125.7 (6)C31—C30—H3095.8
N1—C1—C2108.0 (5)C32—C30—H3095.8
C20—C1—C2125.8 (5)C20—C30—H3095.8
C3—C2—C1107.5 (5)C30—C31—H31A109.5
C3—C2—H2126.3C30—C31—H31B109.5
C1—C2—H2126.3H31A—C31—H31B109.5
C2—C3—C4109.5 (6)C30—C31—H31C109.5
C2—C3—H3125.3H31A—C31—H31C109.5
C4—C3—H3125.3H31B—C31—H31C109.5
N1—C4—C5126.5 (5)C30—C32—H32A109.5
N1—C4—C3107.2 (6)C30—C32—H32B109.5
C5—C4—C3126.0 (5)H32A—C32—H32B109.5
C6—C5—C4121.7 (5)C30—C32—H32C109.5
C6—C5—C21116.9 (6)H32A—C32—H32C109.5
C4—C5—C21121.3 (4)H32B—C32—H32C109.5
N2—C6—C5124.6 (5)O1—C33—C34106.3 (7)
N2—C6—C7108.6 (4)O1—C33—H33A110.5
C5—C6—C7126.3 (4)C34—C33—H33A110.5
C8—C7—C6108.6 (4)O1—C33—H33B110.5
C8—C7—H7125.7C34—C33—H33B110.5
C6—C7—H7125.7H33A—C33—H33B108.7
C7—C8—C9106.9 (5)C35A—C34—C35B42.2 (12)
C7—C8—H8126.5C35A—C34—C33102.3 (12)
C9—C8—H8126.5C35B—C34—C33103.6 (9)
C10—C9—N2125.1 (4)C35A—C34—H34A111.3
C10—C9—C8124.9 (4)C35B—C34—H34A72.0
N2—C9—C8109.5 (6)C33—C34—H34A111.3
C9—C10—C11121.0 (4)C35A—C34—H34B111.3
C9—C10—C24116.8 (4)C35B—C34—H34B141.0
C11—C10—C24121.9 (5)C33—C34—H34B111.3
N3—C11—C10126.7 (5)H34A—C34—H34B109.2
N3—C11—C12108.3 (4)C34—C35A—C36103.2 (8)
C10—C11—C12124.8 (4)C34—C35A—H35A111.1
C13—C12—C11107.7 (4)C36—C35A—H35A111.1
C13—C12—H12126.2C34—C35A—H35B111.1
C11—C12—H12126.2C36—C35A—H35B111.1
C12—C13—C14108.3 (6)H35A—C35A—H35B109.1
C12—C13—H13125.9C36—C35B—C34102.6 (8)
C14—C13—H13125.9C36—C35B—H35C111.2
N3—C14—C15125.9 (5)C34—C35B—H35C111.2
N3—C14—C13108.4 (6)C36—C35B—H35D111.2
C15—C14—C13125.5 (5)C34—C35B—H35D111.2
C16—C15—C14122.3 (5)H35C—C35B—H35D109.2
C16—C15—C27118.6 (6)O1—C36—C35A104.8 (12)
C14—C15—C27118.8 (5)O1—C36—C35B103.9 (7)
N4—C16—C15124.9 (6)C35A—C36—C35B42.2 (12)
N4—C16—C17108.4 (5)O1—C36—H36A110.8
C15—C16—C17126.3 (5)C35A—C36—H36A110.8
C18—C17—C16108.1 (5)C35B—C36—H36A72.2
C18—C17—H17126.0O1—C36—H36B110.8
C16—C17—H17126.0C35A—C36—H36B110.8
C17—C18—C19108.0 (6)C35B—C36—H36B141.5
C17—C18—H18126.0H36A—C36—H36B108.9
C19—C18—H18126.0O2—C37—C38105.9 (6)
C20—C19—N4125.6 (5)O2—C37—H37A110.6
C20—C19—C18125.6 (5)C38—C37—H37A110.6
N4—C19—C18108.6 (7)O2—C37—H37B110.6
C19—C20—C1121.1 (5)C38—C37—H37B110.6
C19—C20—C30117.3 (6)H37A—C37—H37B108.7
C1—C20—C30121.4 (7)C37—C38—C39104.1 (6)
C23—C21—C5114.0 (7)C37—C38—H38A110.9
C23—C21—C22114.1 (6)C39—C38—H38A110.9
C5—C21—C22112.1 (6)C37—C38—H38B110.9
C23—C21—H21105.1C39—C38—H38B110.9
C5—C21—H21105.1H38A—C38—H38B108.9
C22—C21—H21105.1C40—C39—C38106.8 (7)
C21—C22—H22A109.5C40—C39—H39A110.4
C21—C22—H22B109.5C38—C39—H39A110.4
H22A—C22—H22B109.5C40—C39—H39B110.4
C21—C22—H22C109.5C38—C39—H39B110.4
H22A—C22—H22C109.5H39A—C39—H39B108.6
H22B—C22—H22C109.5O2—C40—C39102.8 (7)
C21—C23—H23A109.5O2—C40—H40A111.2
C21—C23—H23B109.5C39—C40—H40A111.2
H23A—C23—H23B109.5O2—C40—H40B111.2
C21—C23—H23C109.5C39—C40—H40B111.2
H23A—C23—H23C109.5H40A—C40—H40B109.1
H23B—C23—H23C109.5
N1—Fe1—O1—C3344.5 (6)N2—C9—C10—C1110.5 (6)
N3—Fe1—O1—C33136.0 (6)C8—C9—C10—C11160.2 (5)
N4—Fe1—O1—C33133.7 (5)N2—C9—C10—C24176.0 (3)
N2—Fe1—O1—C3346.3 (5)C8—C9—C10—C2413.2 (6)
O2—Fe1—O1—C3330.4 (16)C14—N3—C11—C10173.8 (4)
N1—Fe1—O1—C36136.7 (6)Fe1—N3—C11—C105.8 (6)
N3—Fe1—O1—C3642.7 (6)C14—N3—C11—C120.6 (4)
N4—Fe1—O1—C3647.5 (5)Fe1—N3—C11—C12179.8 (3)
N2—Fe1—O1—C36132.4 (5)C9—C10—C11—N311.5 (6)
O2—Fe1—O1—C36148.3 (14)C24—C10—C11—N3175.4 (4)
N1—Fe1—O2—C40143.2 (4)C9—C10—C11—C12162.1 (4)
N3—Fe1—O2—C4037.3 (4)C24—C10—C11—C1211.1 (6)
N4—Fe1—O2—C40127.6 (5)N3—C11—C12—C131.9 (5)
N2—Fe1—O2—C4052.4 (5)C10—C11—C12—C13172.6 (4)
O1—Fe1—O2—C4068.3 (16)C11—C12—C13—C142.5 (5)
N1—Fe1—O2—C3759.3 (4)C11—N3—C14—C15173.7 (4)
N3—Fe1—O2—C37120.1 (4)Fe1—N3—C14—C156.7 (6)
N4—Fe1—O2—C3729.9 (5)C11—N3—C14—C130.9 (4)
N2—Fe1—O2—C37150.2 (5)Fe1—N3—C14—C13178.7 (3)
O1—Fe1—O2—C37134.2 (14)C12—C13—C14—N32.1 (5)
N3—Fe1—N1—C116 (14)C12—C13—C14—C15172.5 (4)
N4—Fe1—N1—C122.3 (4)N3—C14—C15—C1610.0 (7)
N2—Fe1—N1—C1157.4 (4)C13—C14—C15—C16163.8 (5)
O2—Fe1—N1—C1115.4 (5)N3—C14—C15—C27176.3 (4)
O1—Fe1—N1—C168.9 (5)C13—C14—C15—C279.9 (7)
N3—Fe1—N1—C4170 (23)C19—N4—C16—C15170.6 (4)
N4—Fe1—N1—C4163.4 (4)Fe1—N4—C16—C159.8 (6)
N2—Fe1—N1—C416.9 (4)C19—N4—C16—C172.4 (4)
O2—Fe1—N1—C470.3 (5)Fe1—N4—C16—C17177.2 (3)
O1—Fe1—N1—C4105.4 (5)C14—C15—C16—N48.2 (7)
N1—Fe1—N2—C620.3 (4)C27—C15—C16—N4178.1 (4)
N3—Fe1—N2—C6159.8 (4)C14—C15—C16—C17163.6 (5)
N4—Fe1—N2—C6114 (26)C27—C15—C16—C1710.1 (7)
O2—Fe1—N2—C669.1 (7)N4—C16—C17—C183.6 (6)
O1—Fe1—N2—C6109.6 (7)C15—C16—C17—C18169.3 (5)
N1—Fe1—N2—C9162.6 (4)C16—C17—C18—C193.2 (6)
N3—Fe1—N2—C917.3 (4)C16—N4—C19—C20175.5 (4)
N4—Fe1—N2—C968 (26)Fe1—N4—C19—C204.1 (6)
O2—Fe1—N2—C9108.0 (7)C16—N4—C19—C180.5 (4)
O1—Fe1—N2—C973.3 (7)Fe1—N4—C19—C18179.1 (3)
N1—Fe1—N3—C1423 (14)C17—C18—C19—C20173.2 (4)
N4—Fe1—N3—C1417.1 (4)C17—C18—C19—N41.8 (5)
N2—Fe1—N3—C14163.2 (4)N4—C19—C20—C113.8 (7)
O2—Fe1—N3—C1476.0 (4)C18—C19—C20—C1160.4 (4)
O1—Fe1—N3—C14108.3 (4)N4—C19—C20—C30171.5 (4)
N1—Fe1—N3—C11157 (13)C18—C19—C20—C3014.3 (6)
N4—Fe1—N3—C11163.4 (4)N1—C1—C20—C199.2 (7)
N2—Fe1—N3—C1116.4 (4)C2—C1—C20—C19162.0 (4)
O2—Fe1—N3—C11103.5 (4)N1—C1—C20—C30176.3 (4)
O1—Fe1—N3—C1172.2 (4)C2—C1—C20—C3012.5 (7)
N1—Fe1—N4—C16161.3 (4)C6—C5—C21—C2394.6 (6)
N3—Fe1—N4—C1618.8 (4)C4—C5—C21—C2380.9 (7)
N2—Fe1—N4—C16105 (26)C6—C5—C21—C22133.8 (6)
O2—Fe1—N4—C1671.9 (7)C4—C5—C21—C2250.8 (8)
O1—Fe1—N4—C16109.4 (7)C9—C10—C24—C26131.4 (6)
N1—Fe1—N4—C1918.2 (4)C11—C10—C24—C2655.2 (7)
N3—Fe1—N4—C19161.7 (4)C9—C10—C24—C25100.1 (7)
N2—Fe1—N4—C1976 (26)C11—C10—C24—C2573.3 (8)
O2—Fe1—N4—C19107.6 (7)C16—C15—C27—C2869.7 (9)
O1—Fe1—N4—C1971.1 (7)C14—C15—C27—C28116.3 (8)
C4—N1—C1—C20171.6 (4)C16—C15—C27—C2978.4 (7)
Fe1—N1—C1—C2013.3 (6)C14—C15—C27—C2995.5 (7)
C4—N1—C1—C21.0 (5)C19—C20—C30—C3192.2 (9)
Fe1—N1—C1—C2174.1 (3)C1—C20—C30—C3182.5 (9)
N1—C1—C2—C33.2 (5)C19—C20—C30—C32106.8 (9)
C20—C1—C2—C3169.4 (4)C1—C20—C30—C3278.5 (9)
C1—C2—C3—C44.1 (6)C36—O1—C33—C345.3 (8)
C1—N1—C4—C5171.9 (4)Fe1—O1—C33—C34173.6 (4)
Fe1—N1—C4—C53.3 (6)O1—C33—C34—C35A25.6 (16)
C1—N1—C4—C31.4 (5)O1—C33—C34—C35B17.7 (10)
Fe1—N1—C4—C3176.6 (3)C35B—C34—C35A—C3661.3 (11)
C2—C3—C4—N13.5 (5)C33—C34—C35A—C3635 (2)
C2—C3—C4—C5169.8 (5)C35A—C34—C35B—C3660.8 (10)
N1—C4—C5—C614.9 (7)C33—C34—C35B—C3632.7 (13)
C3—C4—C5—C6157.2 (5)C33—O1—C36—C35A17.3 (16)
N1—C4—C5—C21169.8 (4)Fe1—O1—C36—C35A163.7 (15)
C3—C4—C5—C2118.1 (7)C33—O1—C36—C35B26.2 (9)
C9—N2—C6—C5172.4 (4)Fe1—O1—C36—C35B152.7 (8)
Fe1—N2—C6—C510.0 (6)C34—C35A—C36—O133 (3)
C9—N2—C6—C70.1 (4)C34—C35A—C36—C35B61.5 (11)
Fe1—N2—C6—C7177.7 (3)C34—C35B—C36—O136.2 (13)
C4—C5—C6—N211.1 (7)C34—C35B—C36—C35A60.6 (11)
C21—C5—C6—N2173.4 (4)C40—O2—C37—C3836.9 (7)
C4—C5—C6—C7159.8 (5)Fe1—O2—C37—C38124.1 (7)
C21—C5—C6—C715.6 (7)O2—C37—C38—C3920.6 (7)
N2—C6—C7—C81.6 (5)C37—C38—C39—C401.6 (8)
C5—C6—C7—C8170.5 (4)C37—O2—C40—C3936.6 (7)
C6—C7—C8—C92.5 (5)Fe1—O2—C40—C39124.4 (6)
C6—N2—C9—C10170.4 (4)C38—C39—C40—O223.1 (8)
Fe1—N2—C9—C107.2 (5)C6—C5—C21—H2120.0
C6—N2—C9—C81.6 (4)C4—C5—C21—H21164.5
Fe1—N2—C9—C8179.2 (3)C11—C10—C24—H24170.9
C7—C8—C9—C10169.4 (4)C16—C15—C27—H27175.9
C7—C8—C9—N22.6 (5)C1—C20—C30—H30177.2

Experimental details

Crystal data
Chemical formula[Fe(C32H36N4)(C4H8O)2]·ClO4
Mr776.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)10.56 (10), 32.98 (15), 11.64 (8)
β (°) 92.8 (7)
V3)4048 (51)
Z4
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.5 × 0.4 × 0.2
Data collection
DiffractometerRigaku AFC-5
diffractometer
Absorption correctionψ-scan
(North et al., 1968)
Tmin, Tmax0.819, 0.907
No. of measured, independent and
observed [I > 2σ(I)] reflections
9566, 9128, 4237
Rint0.037
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.215, 0.91
No. of reflections9128
No. of parameters495
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.68, 0.41

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992b), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SV (Nemoto & Ohashi, 1993), SHELXL97.

Selected geometric parameters (Å, º) top
Fe1—N11.946 (14)Fe1—N21.988 (9)
Fe1—N31.950 (14)Fe1—O22.183 (19)
Fe1—N41.982 (9)Fe1—O12.221 (19)
N1—Fe1—N3179.45 (14)N4—Fe1—N2179.75 (14)
Fe1—O1—C36—C35A163.7 (15)C11—C10—C24—H24170.9
Fe1—O1—C36—C35B152.7 (8)C16—C15—C27—H27175.9
Fe1—O2—C37—C38124.1 (7)C1—C20—C30—H30177.2
C4—C5—C21—H21164.5
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds