Literature DB >> 21753977

Chlorido{5,10,15,20-tetra-kis-[2-(2,2-dimethyl-propanamido)-phen-yl]porphyrinato-κN,N',N'',N'''}iron(III) chloro-benzene hemisolvate monohydrate.

Mondher Dhifet, Mohamed Salah Belkhiria, Jean-Claude Daran, Habib Nasri.

Abstract

In the title complex, [Fe(C(64)H(64)N(8)O(4))Cl]·0.5C(6)H(5)Cl·H(2)O, the equatorial iron-pyrrole N atom distance (Fe-N(p)) is 2.065 (2) Å and the axial Fe-Cl distance is 2.207 (2) Å. The iron cation is displaced by 0.420 (4) Å from the 24-atom mean plane of the porphyrin core. The asymmetric unit contains a quarter of an [Fe(III)(C(64)H(64)N(8)O(4))Cl] complex mol-ecule, with a fourfold rotation axis passing through the central metal cation and the Cl ligand, along with disordered mol-ecules of chloro-benzene and water of solvation; the solvent mol-ecules were excluded from the refinement.

Entities: Chemical Disease Gene Species

Year: 2011 PMID： 21753977 PMCID： PMC3099838 DOI： 10.1107/S1600536811009299

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For a review of porphyrin complexes, see: Scheidt (2000 ▶). For synthetic procedures, see: Gismelseed et al. (1990 ▶). For structural features of porphyrins, see: Schappacher et al. (1983 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Fe(C64H64N8O4)Cl]·0.5C6H5Cl·H2O M = 1206.84 Tetragonal, a = 18.069 (3) Å c = 18.919 (4) Å V = 6177 (2) Å3 Z = 4 Mo Kα radiation μ = 0.34 mm−1 T = 180 K 0.22 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.842, T max = 0.937 43373 measured reflections 3021 independent reflections 2089 reflections with I > 2σ(I) R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.060 wR(F 2) = 0.180 S = 1.07 3021 reflections 178 parameters H-atom parameters constrained Δρmax = 0.81 e Å−3 Δρmin = −1.34 e Å−3 Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009299/pv2389sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009299/pv2389Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe(C₆₄H₆₄N₈O₄)Cl]·0.5C₆H₅Cl·H₂O	D_x = 1.298 Mg m⁻³
M_r = 1206.84	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/ncc	Cell parameters from 43373 reflections
Hall symbol: -P 4a 2ac	θ = 2.7–26.0°
a = 18.069 (3) Å	µ = 0.34 mm⁻¹
c = 18.919 (4) Å	T = 180 K
V = 6177 (2) Å³	Prism, dark purple
Z = 4	0.22 × 0.18 × 0.16 mm
F(000) = 2536

Bruker APEXII CCD area-detector diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	2089 reflections with I > 2σ(I)
graphite	R_int = 0.064
φ and ω scans	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −22→22
T_min = 0.842, T_max = 0.937	k = −20→22
43373 measured reflections	l = −23→23

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.115P)² + 0.6251P] where P = (F_o² + 2F_c²)/3
3021 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −1.34 e Å⁻³

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	U_iso*/U_eq
Fe	0.2500	0.2500	0.12373 (4)	0.0222 (3)
Cl	0.2500	0.2500	0.24040 (7)	0.0335 (4)
O1	0.56932 (17)	0.3807 (2)	−0.12040 (12)	0.0677 (10)
N1	0.35198 (11)	0.20458 (11)	0.10034 (11)	0.0163 (5)
N2	0.49310 (14)	0.35229 (16)	−0.03138 (13)	0.0371 (7)
HN2	0.4488	0.3373	−0.0231	0.045*
C1	0.36920 (14)	0.13070 (14)	0.09954 (14)	0.0187 (6)
C2	0.44818 (15)	0.12135 (16)	0.09858 (15)	0.0250 (6)
H2	0.4735	0.0766	0.0981	0.030*
C3	0.47859 (15)	0.18914 (15)	0.09854 (15)	0.0249 (6)
H3	0.5289	0.2001	0.0980	0.030*
C4	0.41823 (14)	0.24197 (14)	0.09945 (14)	0.0190 (6)
C5	0.42756 (14)	0.31872 (14)	0.09900 (13)	0.0183 (6)
C6	0.50541 (14)	0.34772 (14)	0.09465 (14)	0.0200 (6)
C7	0.54726 (15)	0.35788 (16)	0.15514 (15)	0.0262 (7)
H7	0.5264	0.3482	0.1991	0.031*
C8	0.61929 (17)	0.38216 (18)	0.15117 (16)	0.0333 (7)
H8	0.6466	0.3890	0.1923	0.040*
C9	0.65061 (18)	0.3961 (2)	0.08699 (18)	0.0433 (9)
H9	0.6995	0.4120	0.0845	0.052*
C10	0.61015 (18)	0.3869 (2)	0.02555 (17)	0.0412 (9)
H10	0.6316	0.3969	−0.0181	0.049*
C11	0.53757 (16)	0.36263 (17)	0.02937 (15)	0.0286 (7)
C12	0.50947 (19)	0.36235 (17)	−0.10004 (16)	0.0327 (7)
C13	0.44577 (19)	0.34785 (17)	−0.15323 (16)	0.0342 (8)
C14	0.4681 (2)	0.2800 (2)	−0.19598 (18)	0.0431 (8)
H14A	0.5152	0.2886	−0.2179	0.065*
H14B	0.4316	0.2707	−0.2317	0.065*
H14C	0.4715	0.2379	−0.1652	0.065*
C15	0.3714 (2)	0.3359 (3)	−0.11812 (18)	0.0494 (10)
H15A	0.3582	0.3791	−0.0915	0.074*
H15B	0.3742	0.2940	−0.0870	0.074*
H15C	0.3345	0.3268	−0.1536	0.074*
C16	0.4413 (3)	0.4155 (2)	−0.2017 (2)	0.0747 (15)
H16A	0.4271	0.4581	−0.1745	0.112*
H16B	0.4052	0.4068	−0.2380	0.112*
H16C	0.4887	0.4242	−0.2229	0.112*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.0228 (3)	0.0228 (3)	0.0211 (4)	0.000	0.000	0.000
Cl	0.0409 (6)	0.0409 (6)	0.0188 (7)	0.000	0.000	0.000
O1	0.0669 (19)	0.111 (3)	0.0255 (13)	−0.0554 (19)	0.0096 (12)	−0.0067 (13)
N1	0.0157 (11)	0.0160 (11)	0.0171 (10)	0.0016 (9)	0.0025 (9)	−0.0008 (9)
N2	0.0264 (14)	0.0630 (19)	0.0220 (13)	−0.0182 (13)	−0.0021 (11)	0.0079 (12)
C1	0.0199 (14)	0.0203 (14)	0.0158 (12)	0.0021 (10)	0.0008 (10)	−0.0001 (10)
C2	0.0189 (14)	0.0226 (15)	0.0336 (15)	0.0052 (11)	0.0024 (12)	0.0002 (12)
C3	0.0167 (14)	0.0257 (15)	0.0323 (15)	0.0024 (11)	0.0038 (12)	−0.0042 (12)
C4	0.0172 (13)	0.0239 (15)	0.0158 (12)	0.0012 (10)	0.0018 (10)	−0.0014 (10)
C5	0.0184 (13)	0.0210 (14)	0.0155 (12)	−0.0026 (10)	0.0028 (10)	0.0009 (11)
C6	0.0166 (14)	0.0202 (14)	0.0232 (14)	−0.0010 (10)	0.0007 (11)	0.0002 (11)
C7	0.0244 (16)	0.0324 (17)	0.0219 (14)	−0.0009 (12)	0.0017 (12)	−0.0027 (12)
C8	0.0258 (16)	0.047 (2)	0.0271 (15)	−0.0057 (14)	−0.0049 (13)	−0.0102 (14)
C9	0.0231 (17)	0.063 (2)	0.0435 (19)	−0.0194 (16)	0.0014 (14)	−0.0035 (18)
C10	0.0304 (18)	0.067 (2)	0.0265 (16)	−0.0233 (16)	0.0047 (13)	0.0042 (15)
C11	0.0267 (16)	0.0364 (17)	0.0226 (15)	−0.0084 (12)	−0.0010 (12)	0.0025 (12)
C12	0.047 (2)	0.0288 (16)	0.0224 (15)	−0.0122 (14)	0.0016 (14)	0.0017 (13)
C13	0.052 (2)	0.0302 (17)	0.0209 (15)	−0.0009 (14)	−0.0103 (14)	0.0017 (12)
C14	0.047 (2)	0.048 (2)	0.0350 (18)	0.0001 (16)	−0.0096 (16)	−0.0104 (16)
C15	0.039 (2)	0.071 (3)	0.0376 (19)	0.0059 (18)	−0.0167 (16)	−0.0144 (18)
C16	0.132 (4)	0.046 (2)	0.046 (2)	0.013 (3)	−0.022 (3)	0.015 (2)

Fe—N1ⁱ	2.065 (2)	C7—C8	1.376 (4)
Fe—N1ⁱⁱ	2.065 (2)	C7—H7	0.9300
Fe—N1	2.065 (2)	C8—C9	1.363 (5)
Fe—N1ⁱⁱⁱ	2.065 (2)	C8—H8	0.9300
Fe—Cl	2.2073 (16)	C9—C10	1.383 (4)
O1—C12	1.195 (4)	C9—H9	0.9300
N1—C1	1.371 (3)	C10—C11	1.385 (4)
N1—C4	1.375 (3)	C10—H10	0.9300
N2—C12	1.345 (4)	C12—C13	1.551 (4)
N2—C11	1.415 (4)	C13—C15	1.515 (5)
N2—HN2	0.8600	C13—C14	1.523 (5)
C1—C5ⁱⁱ	1.393 (4)	C13—C16	1.530 (5)
C1—C2	1.437 (4)	C14—H14A	0.9600
C2—C3	1.343 (4)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.449 (4)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.397 (4)	C15—H15C	0.9600
C5—C1ⁱ	1.393 (4)	C16—H16A	0.9600
C5—C6	1.503 (4)	C16—H16B	0.9600
C6—C7	1.384 (4)	C16—H16C	0.9600
C6—C11	1.391 (4)

N1ⁱ—Fe—N1ⁱⁱ	155.25 (12)	C9—C8—H8	120.0
N1ⁱ—Fe—N1	87.37 (3)	C7—C8—H8	120.0
N1ⁱⁱ—Fe—N1	87.37 (3)	C8—C9—C10	120.4 (3)
N1ⁱ—Fe—N1ⁱⁱⁱ	87.37 (3)	C8—C9—H9	119.8
N1ⁱⁱ—Fe—N1ⁱⁱⁱ	87.37 (3)	C10—C9—H9	119.8
N1—Fe—N1ⁱⁱⁱ	155.25 (12)	C9—C10—C11	119.7 (3)
N1ⁱ—Fe—Cl	102.38 (6)	C9—C10—H10	120.2
N1ⁱⁱ—Fe—Cl	102.38 (6)	C11—C10—H10	120.2
N1—Fe—Cl	102.38 (6)	C10—C11—C6	120.2 (3)
N1ⁱⁱⁱ—Fe—Cl	102.38 (6)	C10—C11—N2	122.5 (3)
C1—N1—C4	106.3 (2)	C6—C11—N2	117.3 (2)
C1—N1—Fe	126.29 (17)	O1—C12—N2	123.2 (3)
C4—N1—Fe	125.75 (17)	O1—C12—C13	120.6 (3)
C12—N2—C11	130.0 (3)	N2—C12—C13	116.2 (3)
C12—N2—HN2	115.0	C15—C13—C14	110.6 (3)
C11—N2—HN2	115.0	C15—C13—C16	109.3 (3)
N1—C1—C5ⁱⁱ	126.0 (2)	C14—C13—C16	109.8 (3)
N1—C1—C2	109.9 (2)	C15—C13—C12	113.5 (3)
C5ⁱⁱ—C1—C2	124.1 (2)	C14—C13—C12	106.5 (3)
C3—C2—C1	107.4 (2)	C16—C13—C12	107.0 (3)
C3—C2—H2	126.3	C13—C14—H14A	109.5
C1—C2—H2	126.3	C13—C14—H14B	109.5
C2—C3—C4	107.0 (2)	H14A—C14—H14B	109.5
C2—C3—H3	126.5	C13—C14—H14C	109.5
C4—C3—H3	126.5	H14A—C14—H14C	109.5
N1—C4—C5	126.4 (2)	H14B—C14—H14C	109.5
N1—C4—C3	109.4 (2)	C13—C15—H15A	109.5
C5—C4—C3	124.2 (2)	C13—C15—H15B	109.5
C1ⁱ—C5—C4	124.0 (2)	H15A—C15—H15B	109.5
C1ⁱ—C5—C6	118.6 (2)	C13—C15—H15C	109.5
C4—C5—C6	117.3 (2)	H15A—C15—H15C	109.5
C7—C6—C11	118.7 (2)	H15B—C15—H15C	109.5
C7—C6—C5	120.8 (2)	C13—C16—H16A	109.5
C11—C6—C5	120.5 (2)	C13—C16—H16B	109.5
C8—C7—C6	120.9 (3)	H16A—C16—H16B	109.5
C8—C7—H7	119.5	C13—C16—H16C	109.5
C6—C7—H7	119.5	H16A—C16—H16C	109.5
C9—C8—C7	120.0 (3)	H16B—C16—H16C	109.5

3 in total

1 in total

1. Crystal structure of chlorido-{5,10,15,20-tetra-kis-[2-(2,2-di-methyl-propanamido)-phen-yl]porphyrinato-κ(4) N}iron(III).

Authors: Dennis Awasabisah; Douglas R Powell; George B Richter-Addo
Journal: Acta Crystallogr E Crystallogr Commun Date: 2015-01-31