Dipyridine­(2,3,12,13-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin)iron(II) pyridine solvate

The complex mol­ecule of the title compound, [Fe(C₄₄H₂₄Br₄N₄)(C₅H₅N)₂]·C₅H₅N, is located on a twofold axis that passes through the Fe atom and the pyridine ligands. Only slight asymmetry, viz. 0.010 Å elongation due to the Br substituents, is seen in the Fe-N_porph distances. The pyridine ligands are twisted by 19.18 (13)° from each other. The uncoordinated pyridine molecule is disordered over an inversion center.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
Some non-H atoms missing
• R factor = 0.036
• wR factor = 0.108
• Data-to-parameter ratio = 19.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C59 H39 Br4 Fe1 N7
            Atom count from the _atom_site data:  C60 H38.98 Br4 Fe1 N6
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C59 H39 Br4 Fe N7
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        236.00    240.00   -4.00
           H        156.00    155.92    0.08
           Br        16.00     16.00    0.00
           Fe         4.00      4.00    0.00
           N         28.00     24.00    4.00

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Sheldrick, 2003); program(s) used to solve structure: XS (Sheldrick, 2001); program(s) used to refine structure: XL (Sheldrick, 2001); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XL and enCIFer (Allen et al., 2004).

(2,3,12,13-Tetrabromo-5,10,15,20-tetraphenylporphyrin)dipyridineiron(II) pyridine solvate

Crystal data

[Fe(C44H24Br4N4)(C5H5N)2]·C5H5N	F(000) = 2432
Mr = 1221.46	Dx = 1.674 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8017 reflections
a = 18.4633 (5) Å	θ = 2.6–28.5°
b = 19.9786 (6) Å	µ = 3.66 mm^−1
c = 14.4636 (4) Å	T = 100 K
β = 114.688 (1)°	Block, dark red
V = 4847.5 (2) Å^3	0.15 × 0.11 × 0.11 mm
Z = 4

Data collection

Bruker X8 APEXII CCD area-detector diffractometer	6171 independent reflections
Radiation source: fine-focus sealed tube	4952 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.33 pixels mm^-1	θmax = 28.6°, θmin = 1.6°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −26→26
Tmin = 0.60, Tmax = 0.67	l = −19→19
51139 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 9.6451P] where P = (Fo^2 + 2Fc^2)/3
6171 reflections	(Δ/σ)max = 0.001
323 parameters	Δρmax = 1.03 e Å^−3
0 restraints	Δρmin = −1.02 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. 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	Occ. (<1)
Fe1	0.0000	0.16037 (3)	0.7500	0.01889 (12)
Br1	−0.152432 (18)	0.208496 (16)	1.03201 (2)	0.03224 (10)
Br2	0.046996 (19)	0.243510 (17)	1.16001 (2)	0.03563 (10)
N1	−0.01550 (14)	0.16358 (12)	0.87741 (16)	0.0218 (4)
N2	0.11625 (13)	0.15616 (11)	0.83063 (15)	0.0206 (4)
N3	0.0000	0.06024 (16)	0.7500	0.0191 (6)
N4	0.0000	0.26247 (16)	0.7500	0.0227 (6)
C1	−0.08765 (16)	0.16263 (13)	0.88463 (18)	0.0220 (5)
C2	−0.07585 (17)	0.18629 (14)	0.98439 (19)	0.0244 (5)
C3	0.00266 (18)	0.19773 (14)	1.03676 (19)	0.0248 (6)
C4	0.04198 (17)	0.17870 (14)	0.97290 (19)	0.0236 (5)
C5	0.12352 (16)	0.16730 (14)	1.00398 (18)	0.0223 (5)
C6	0.15619 (16)	0.15272 (13)	0.93491 (19)	0.0220 (5)
C7	0.23674 (17)	0.13016 (14)	0.9633 (2)	0.0253 (6)
H7	0.2763	0.1241	1.0307	0.030*
C8	0.24558 (17)	0.11916 (15)	0.8766 (2)	0.0257 (6)
H8	0.2920	0.1029	0.8711	0.031*
C9	0.17087 (16)	0.13694 (14)	0.79376 (19)	0.0218 (5)
C10	0.15866 (17)	0.14042 (14)	0.69204 (19)	0.0230 (5)
C11	0.17614 (17)	0.15965 (14)	1.11460 (19)	0.0246 (6)
C12	0.15875 (18)	0.10998 (16)	1.1698 (2)	0.0290 (6)
H12	0.1136	0.0820	1.1369	0.035*
C13	0.2068 (2)	0.10101 (18)	1.2722 (2)	0.0375 (7)
H13	0.1942	0.0671	1.3092	0.045*
C14	0.2727 (2)	0.14089 (18)	1.3209 (2)	0.0412 (8)
H14	0.3050	0.1352	1.3915	0.049*
C15	0.2915 (2)	0.18914 (18)	1.2664 (2)	0.0412 (8)
H15	0.3377	0.2161	1.2993	0.049*
C16	0.24327 (19)	0.19863 (15)	1.1633 (2)	0.0315 (7)
H16	0.2566	0.2321	1.1264	0.038*
C17	0.22321 (18)	0.11589 (15)	0.6642 (2)	0.0262 (6)
C18	0.2087 (2)	0.05898 (17)	0.6034 (2)	0.0376 (7)
H18	0.1589	0.0367	0.5819	0.045*
C19	0.2659 (3)	0.0347 (2)	0.5741 (3)	0.0510 (10)
H19	0.2552	−0.0039	0.5321	0.061*
C20	0.3376 (2)	0.0660 (2)	0.6053 (3)	0.0461 (9)
H20	0.3770	0.0487	0.5857	0.055*
C21	0.3535 (2)	0.1226 (2)	0.6652 (3)	0.0439 (8)
H21	0.4034	0.1446	0.6859	0.053*
C22	0.2962 (2)	0.14738 (18)	0.6951 (3)	0.0359 (7)
H22	0.3073	0.1861	0.7370	0.043*
C23	0.03318 (15)	0.02527 (14)	0.83711 (19)	0.0224 (5)
H23	0.0566	0.0491	0.8995	0.027*
C24	0.03473 (18)	−0.04322 (15)	0.8397 (2)	0.0303 (6)
H24	0.0595	−0.0662	0.9028	0.036*
C25	0.0000	−0.0784 (2)	0.7500	0.0362 (10)
H25	0.0000	−0.1260	0.7500	0.043*
C26	0.05111 (19)	0.29773 (16)	0.8292 (2)	0.0328 (7)
H26	0.0884	0.2740	0.8860	0.039*
C27	0.0524 (2)	0.36633 (17)	0.8324 (2)	0.0384 (7)
H27	0.0890	0.3891	0.8909	0.046*
C28	0.0000	0.4021 (2)	0.7500	0.0347 (10)
H28	0.0000	0.4497	0.7500	0.042*
C1S	0.5312 (3)	0.0622 (3)	1.0251 (4)	0.0702 (14)
H1S	0.5531	0.1058	1.0432	0.084*	0.83
C2S	0.5665 (3)	0.0094 (3)	1.0852 (3)	0.0717 (15)
H2S	0.6138	0.0158	1.1454	0.086*	0.83
C3S	0.5351 (3)	−0.0527 (3)	1.0604 (4)	0.0725 (15)
H3S	0.5600	−0.0895	1.1035	0.087*	0.83

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0246 (3)	0.0221 (3)	0.0098 (2)	0.000	0.00714 (19)	0.000
Br1	0.03756 (17)	0.04201 (19)	0.02213 (14)	0.00590 (13)	0.01739 (12)	−0.00305 (11)
Br2	0.03913 (18)	0.0466 (2)	0.01864 (14)	0.00632 (14)	0.00957 (12)	−0.00854 (12)
N1	0.0269 (11)	0.0266 (12)	0.0118 (9)	0.0017 (9)	0.0081 (8)	0.0002 (8)
N2	0.0260 (11)	0.0242 (11)	0.0117 (9)	−0.0019 (9)	0.0079 (8)	−0.0006 (8)
N3	0.0211 (14)	0.0244 (16)	0.0153 (13)	0.000	0.0110 (11)	0.000
N4	0.0297 (16)	0.0233 (16)	0.0160 (14)	0.000	0.0105 (13)	0.000
C1	0.0305 (13)	0.0235 (13)	0.0136 (11)	0.0064 (11)	0.0106 (10)	0.0029 (9)
C2	0.0345 (14)	0.0252 (13)	0.0165 (11)	0.0065 (11)	0.0137 (11)	0.0018 (10)
C3	0.0360 (14)	0.0272 (14)	0.0123 (10)	0.0028 (11)	0.0111 (10)	−0.0036 (10)
C4	0.0328 (14)	0.0254 (14)	0.0131 (11)	0.0044 (11)	0.0099 (10)	−0.0003 (10)
C5	0.0291 (13)	0.0253 (14)	0.0119 (10)	0.0007 (10)	0.0079 (10)	−0.0005 (9)
C6	0.0284 (13)	0.0231 (13)	0.0136 (11)	−0.0008 (10)	0.0079 (10)	−0.0008 (9)
C7	0.0296 (13)	0.0276 (14)	0.0159 (11)	0.0009 (11)	0.0067 (10)	0.0010 (10)
C8	0.0270 (13)	0.0319 (15)	0.0180 (12)	0.0014 (11)	0.0092 (10)	0.0005 (10)
C9	0.0255 (13)	0.0241 (13)	0.0160 (11)	−0.0034 (10)	0.0086 (10)	−0.0019 (10)
C10	0.0301 (13)	0.0237 (13)	0.0171 (11)	−0.0044 (11)	0.0118 (10)	−0.0031 (10)
C11	0.0305 (13)	0.0292 (14)	0.0130 (11)	0.0058 (11)	0.0081 (10)	−0.0022 (10)
C12	0.0335 (14)	0.0361 (16)	0.0195 (12)	0.0068 (12)	0.0133 (11)	0.0046 (11)
C13	0.0493 (19)	0.0451 (19)	0.0219 (14)	0.0170 (15)	0.0185 (13)	0.0129 (13)
C14	0.055 (2)	0.0446 (19)	0.0137 (12)	0.0164 (16)	0.0039 (13)	0.0006 (12)
C15	0.052 (2)	0.0342 (17)	0.0203 (14)	0.0018 (15)	−0.0017 (13)	−0.0043 (12)
C16	0.0409 (17)	0.0278 (15)	0.0185 (13)	0.0016 (12)	0.0053 (12)	−0.0018 (11)
C17	0.0343 (14)	0.0302 (15)	0.0168 (11)	0.0033 (12)	0.0133 (11)	0.0022 (10)
C18	0.0511 (19)	0.0324 (17)	0.0312 (15)	0.0012 (14)	0.0191 (14)	−0.0032 (13)
C19	0.075 (3)	0.039 (2)	0.047 (2)	0.0106 (19)	0.033 (2)	−0.0075 (16)
C20	0.059 (2)	0.051 (2)	0.0375 (18)	0.0199 (18)	0.0292 (17)	0.0012 (16)
C21	0.0389 (18)	0.060 (2)	0.0410 (18)	0.0022 (16)	0.0248 (15)	−0.0010 (17)
C22	0.0399 (17)	0.0400 (18)	0.0361 (16)	−0.0025 (14)	0.0242 (14)	−0.0057 (14)
C23	0.0230 (12)	0.0291 (14)	0.0172 (11)	−0.0001 (10)	0.0105 (10)	0.0015 (10)
C24	0.0339 (15)	0.0292 (15)	0.0273 (14)	0.0025 (12)	0.0124 (12)	0.0066 (11)
C25	0.046 (3)	0.025 (2)	0.037 (2)	0.000	0.016 (2)	0.000
C26	0.0340 (15)	0.0328 (16)	0.0239 (14)	0.0038 (13)	0.0044 (12)	−0.0026 (12)
C27	0.0395 (17)	0.0343 (17)	0.0315 (16)	0.0016 (14)	0.0050 (13)	−0.0071 (13)
C28	0.035 (2)	0.025 (2)	0.037 (2)	0.000	0.0084 (18)	0.000
C1S	0.045 (2)	0.108 (4)	0.061 (3)	0.000 (3)	0.026 (2)	−0.014 (3)
C2S	0.036 (2)	0.136 (5)	0.043 (2)	0.004 (3)	0.0164 (17)	−0.016 (3)
C3S	0.046 (2)	0.116 (5)	0.058 (3)	0.007 (3)	0.025 (2)	−0.006 (3)

Geometric parameters (Å, º)

Fe1—N2^i	1.971 (2)	C13—H13	0.9500
Fe1—N2	1.971 (2)	C14—C15	1.378 (5)
Fe1—N1^i	1.980 (2)	C14—H14	0.9500
Fe1—N1	1.981 (2)	C15—C16	1.393 (4)
Fe1—N3	2.001 (3)	C15—H15	0.9500
Fe1—N4	2.040 (3)	C16—H16	0.9500
Br1—C2	1.866 (3)	C17—C22	1.382 (4)
Br2—C3	1.862 (3)	C17—C18	1.393 (4)
N1—C4	1.379 (3)	C18—C19	1.381 (5)
N1—C1	1.379 (4)	C18—H18	0.9500
N2—C6	1.376 (3)	C19—C20	1.358 (6)
N2—C9	1.378 (4)	C19—H19	0.9500
N3—C23^i	1.344 (3)	C20—C21	1.381 (5)
N3—C23	1.344 (3)	C20—H20	0.9500
N4—C26	1.340 (3)	C21—C22	1.390 (5)
N4—C26^i	1.340 (3)	C21—H21	0.9500
C1—C10^i	1.390 (4)	C22—H22	0.9500
C1—C2	1.446 (3)	C23—C24	1.369 (4)
C2—C3	1.345 (4)	C23—H23	0.9500
C3—C4	1.444 (4)	C24—C25	1.377 (4)
C4—C5	1.398 (4)	C24—H24	0.9500
C5—C6	1.396 (4)	C25—C24^i	1.377 (4)
C5—C11	1.493 (3)	C25—H25	0.9500
C6—C7	1.440 (4)	C26—C27	1.371 (5)
C7—C8	1.349 (4)	C26—H26	0.9500
C7—H7	0.9500	C27—C28	1.380 (4)
C8—C9	1.444 (4)	C27—H27	0.9500
C8—H8	0.9500	C28—C27^i	1.380 (4)
C9—C10	1.394 (3)	C28—H28	0.9500
C10—C1^i	1.389 (4)	C1S—C3S^ii	1.341 (7)
C10—C17	1.491 (4)	C1S—C2S	1.349 (8)
C11—C16	1.382 (4)	C1S—H1S	0.9500
C11—C12	1.392 (4)	C2S—C3S	1.352 (8)
C12—C13	1.385 (4)	C2S—H2S	0.9500
C12—H12	0.9500	C3S—C1S^ii	1.341 (7)
C13—C14	1.377 (5)	C3S—H3S	0.9500
N2^i—Fe1—N2	175.11 (13)	C13—C12—C11	120.5 (3)
N2^i—Fe1—N1^i	89.76 (9)	C13—C12—H12	119.8
N2—Fe1—N1^i	90.40 (9)	C11—C12—H12	119.8
N2^i—Fe1—N1	90.40 (9)	C14—C13—C12	120.4 (3)
N2—Fe1—N1	89.75 (9)	C14—C13—H13	119.8
N1^i—Fe1—N1	176.29 (14)	C12—C13—H13	119.8
N2^i—Fe1—N3	87.55 (7)	C13—C14—C15	119.5 (3)
N2—Fe1—N3	87.55 (7)	C13—C14—H14	120.2
N1^i—Fe1—N3	91.85 (7)	C15—C14—H14	120.2
N1—Fe1—N3	91.85 (7)	C14—C15—C16	120.4 (3)
N2^i—Fe1—N4	92.45 (7)	C14—C15—H15	119.8
N2—Fe1—N4	92.45 (7)	C16—C15—H15	119.8
N1^i—Fe1—N4	88.15 (7)	C11—C16—C15	120.4 (3)
N1—Fe1—N4	88.15 (7)	C11—C16—H16	119.8
N3—Fe1—N4	180.000 (1)	C15—C16—H16	119.8
C4—N1—C1	106.9 (2)	C22—C17—C18	118.7 (3)
C4—N1—Fe1	126.12 (19)	C22—C17—C10	123.0 (3)
C1—N1—Fe1	126.12 (17)	C18—C17—C10	118.3 (3)
C6—N2—C9	105.5 (2)	C19—C18—C17	120.7 (3)
C6—N2—Fe1	127.10 (18)	C19—C18—H18	119.7
C9—N2—Fe1	125.12 (17)	C17—C18—H18	119.7
C23^i—N3—C23	117.3 (3)	C20—C19—C18	120.0 (3)
C23^i—N3—Fe1	121.33 (17)	C20—C19—H19	120.0
C23—N3—Fe1	121.33 (17)	C18—C19—H19	120.0
C26—N4—C26^i	116.6 (4)	C19—C20—C21	120.5 (3)
C26—N4—Fe1	121.71 (18)	C19—C20—H20	119.7
C26^i—N4—Fe1	121.71 (18)	C21—C20—H20	119.7
N1—C1—C10^i	124.3 (2)	C20—C21—C22	119.8 (4)
N1—C1—C2	108.9 (2)	C20—C21—H21	120.1
C10^i—C1—C2	126.8 (3)	C22—C21—H21	120.1
C3—C2—C1	107.2 (2)	C17—C22—C21	120.2 (3)
C3—C2—Br1	123.8 (2)	C17—C22—H22	119.9
C1—C2—Br1	128.6 (2)	C21—C22—H22	119.9
C2—C3—C4	107.9 (2)	N3—C23—C24	122.8 (3)
C2—C3—Br2	124.2 (2)	N3—C23—H23	118.6
C4—C3—Br2	127.2 (2)	C24—C23—H23	118.6
N1—C4—C5	124.1 (2)	C23—C24—C25	119.2 (3)
N1—C4—C3	108.4 (2)	C23—C24—H24	120.4
C5—C4—C3	126.8 (2)	C25—C24—H24	120.4
C6—C5—C4	122.2 (2)	C24—C25—C24^i	118.6 (4)
C6—C5—C11	117.6 (2)	C24—C25—H25	120.7
C4—C5—C11	119.5 (2)	C24^i—C25—H25	120.7
N2—C6—C5	125.4 (2)	N4—C26—C27	123.4 (3)
N2—C6—C7	110.2 (2)	N4—C26—H26	118.3
C5—C6—C7	124.4 (2)	C27—C26—H26	118.3
C8—C7—C6	107.3 (2)	C26—C27—C28	119.5 (3)
C8—C7—H7	126.4	C26—C27—H27	120.2
C6—C7—H7	126.4	C28—C27—H27	120.2
C7—C8—C9	106.7 (3)	C27^i—C28—C27	117.6 (4)
C7—C8—H8	126.7	C27^i—C28—H28	121.2
C9—C8—H8	126.7	C27—C28—H28	121.2
N2—C9—C10	124.9 (2)	C3S^ii—C1S—C2S	119.5 (6)
N2—C9—C8	110.3 (2)	C3S^ii—C1S—H1S	120.2
C10—C9—C8	124.4 (3)	C2S—C1S—H1S	120.2
C1^i—C10—C9	122.8 (3)	C1S—C2S—C3S	120.5 (5)
C1^i—C10—C17	118.9 (2)	C1S—C2S—H2S	119.7
C9—C10—C17	118.3 (2)	C3S—C2S—H2S	119.7
C16—C11—C12	118.8 (3)	C1S^ii—C3S—C2S	120.0 (6)
C16—C11—C5	122.2 (3)	C1S^ii—C3S—H3S	120.0
C12—C11—C5	119.0 (3)	C2S—C3S—H3S	120.0

Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1, −y, −z+2.