High-spin [Fe(TTP)(THF)₂]

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-tetratolylporphyrin), is a six-coordinate high-spin iron(II) tetra­tolyl­porphyrin with two tetra­hydro­furan mol­ecules as axial ligands. The Fe^II atom is at an inversion center. The average Fe-N distance is 2.067 (7) Å and the Fe-O distance is 2.3208 (8) Å.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.102
• Data-to-parameter ratio = 25.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.72 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Fe1    -   N1      ..       6.12 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker Nonius, 2004); cell refinement: APEX2 and SAINT (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.

Difuran(5,10,15,20-tetra-p-tolylporphyrinato)iron(II)

Crystal data

[Fe(C48H36N4)(C4H8O)2]	F(000) = 916
Mr = 868.87	Dx = 1.312 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7064 reflections
a = 13.6820 (2) Å	θ = 2.5–31.5°
b = 9.7320 (1) Å	µ = 0.39 mm^−1
c = 17.1014 (2) Å	T = 100 K
β = 104.964 (1)°	Needle, red
V = 2199.89 (5) Å^3	0.49 × 0.15 × 0.09 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	7311 independent reflections
Radiation source: fine-focus sealed tube	6283 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 8.33 pixels mm^-1	θmax = 31.5°, θmin = 2.2°
φ and ω scans	h = −20→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −11→14
Tmin = 0.83, Tmax = 0.97	l = −22→25
31446 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0487P)^2 + 1.0408P] where P = (Fo^2 + 2Fc^2)/3
7311 reflections	(Δ/σ)max = 0.001
288 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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. 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 (Ų)

	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*
C20	−0.49222 (9)	0.71245 (14)	0.02066 (8)	0.0237 (2)
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01120 (10)	0.01111 (11)	0.01589 (10)	0.00294 (7)	0.00608 (8)	0.00126 (7)
O1	0.0178 (4)	0.0176 (4)	0.0210 (4)	−0.0006 (3)	0.0021 (3)	−0.0006 (3)
N1	0.0124 (4)	0.0131 (4)	0.0155 (4)	0.0021 (3)	0.0057 (3)	0.0010 (3)
N2	0.0122 (4)	0.0128 (4)	0.0172 (4)	0.0026 (3)	0.0060 (3)	0.0012 (3)
C1	0.0127 (4)	0.0132 (5)	0.0156 (4)	0.0032 (4)	0.0048 (3)	0.0002 (3)
C2	0.0156 (5)	0.0164 (5)	0.0201 (5)	0.0062 (4)	0.0070 (4)	0.0026 (4)
C3	0.0170 (5)	0.0151 (5)	0.0194 (5)	0.0053 (4)	0.0067 (4)	0.0041 (4)
C4	0.0138 (5)	0.0120 (4)	0.0154 (4)	0.0024 (4)	0.0045 (4)	0.0009 (3)
C5	0.0142 (5)	0.0123 (5)	0.0155 (4)	0.0014 (4)	0.0050 (4)	0.0010 (3)
C6	0.0127 (5)	0.0136 (5)	0.0175 (4)	0.0011 (4)	0.0062 (4)	0.0018 (4)
C7	0.0151 (5)	0.0179 (5)	0.0253 (5)	0.0028 (4)	0.0103 (4)	0.0057 (4)
C8	0.0146 (5)	0.0183 (5)	0.0245 (5)	0.0035 (4)	0.0103 (4)	0.0048 (4)
C9	0.0119 (4)	0.0141 (5)	0.0173 (4)	0.0018 (4)	0.0060 (4)	0.0006 (4)
C10	0.0120 (4)	0.0140 (5)	0.0156 (4)	0.0027 (4)	0.0049 (4)	−0.0001 (3)
C11	0.0125 (4)	0.0135 (5)	0.0166 (4)	0.0018 (4)	0.0049 (4)	0.0021 (4)
C12	0.0176 (5)	0.0149 (5)	0.0155 (4)	0.0010 (4)	0.0046 (4)	−0.0001 (4)
C13	0.0175 (5)	0.0135 (5)	0.0214 (5)	0.0003 (4)	0.0052 (4)	0.0004 (4)
C14	0.0161 (5)	0.0174 (5)	0.0214 (5)	0.0008 (4)	0.0057 (4)	0.0048 (4)
C15	0.0167 (5)	0.0213 (5)	0.0160 (4)	0.0019 (4)	0.0067 (4)	0.0023 (4)
C16	0.0144 (5)	0.0156 (5)	0.0178 (4)	0.0016 (4)	0.0061 (4)	−0.0004 (4)
C17	0.0410 (8)	0.0203 (6)	0.0318 (6)	0.0016 (6)	0.0163 (6)	0.0098 (5)
C18	0.0131 (5)	0.0149 (5)	0.0174 (4)	0.0035 (4)	0.0067 (4)	0.0024 (4)
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—N1^i	2.0619 (9)	C13—H13	0.9500
Fe1—N1	2.0619 (9)	C14—C15	1.3955 (17)
Fe1—N2^i	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—O1^i	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—C10^i	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—C1^i	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
C13—C14	1.3958 (16)	C28—H28B	0.9900
N1^i—Fe1—N1	180.0	C15—C14—C13	118.04 (10)
N1^i—Fe1—N2^i	89.57 (4)	C15—C14—C17	121.86 (11)
N1—Fe1—N2^i	90.43 (4)	C13—C14—C17	120.11 (11)
N1^i—Fe1—N2	90.43 (4)	C16—C15—C14	121.07 (10)
N1—Fe1—N2	89.57 (4)	C16—C15—H15	119.5
N2^i—Fe1—N2	180.0	C14—C15—H15	119.5
N1^i—Fe1—O1	90.66 (3)	C15—C16—C11	120.99 (10)
N1—Fe1—O1	89.34 (3)	C15—C16—H16	119.5
N2^i—Fe1—O1	91.04 (3)	C11—C16—H16	119.5
N2—Fe1—O1	88.96 (3)	C14—C17—H17A	109.5
N1^i—Fe1—O1^i	89.34 (3)	C14—C17—H17B	109.5
N1—Fe1—O1^i	90.66 (3)	H17A—C17—H17B	109.5
N2^i—Fe1—O1^i	88.96 (3)	C14—C17—H17C	109.5
N2—Fe1—O1^i	91.04 (3)	H17A—C17—H17C	109.5
O1—Fe1—O1^i	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—C10^i	126.02 (10)	C20—C21—C22	117.82 (11)
N1—C1—C2	109.48 (9)	C20—C21—C24	121.69 (12)
C10^i—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
C9—C8—H8	126.4	C27—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—C1^i	126.00 (10)	C28—C27—C26	102.95 (11)
C9—C10—C18	118.44 (9)	C28—C27—H27A	111.2
C1^i—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

Symmetry code: (i) −x, −y+1, −z.