Synthesis and crystal structure of bis­(tert-butyl isocyanide-κC)[5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinato-κ⁴N]iron(II)

Mol­ecules of the title complex are centrosymmetric and the Fe—N bond lengths to the N atoms of the porphyrin ring indicate that the Fe^II atom is in the low-spin state.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 115 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.083
• Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.612 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Fe       --C23      .       10.1 s.u.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H25C     ..CL1      .       2.86 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H27B     ..CL1      .       2.86 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H7       ..CL1      .       2.94 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H13      ..N2       .       2.86 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Fe        (III)     .       3.43 Info
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         11 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         15 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Bis(tert-butyl isocyanide-κC)[5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato-κ⁴N]iron(II)

Crystal data

[Fe(C44H24Cl4N4)(C5H9N)2]	F(000) = 1004
Mr = 972.58	Dx = 1.427 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.9679 (5) Å	Cell parameters from 9956 reflections
b = 16.9240 (7) Å	θ = 2.4–27.2°
c = 13.3536 (5) Å	µ = 0.62 mm^−1
β = 114.015 (1)°	T = 115 K
V = 2264.15 (16) Å^3	Prism, dark violet
Z = 2	0.28 × 0.21 × 0.18 mm

Data collection

Nonius Kappa APEXII diffractometer	5201 independent reflections
Radiation source: X-ray tube	4077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 512 x 512 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
φ and ω scans	h = −14→14
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −22→21
Tmin = 0.903, Tmax = 0.982	l = −17→15
44887 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 1.8163P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
5201 reflections	Δρmax = 0.43 e Å^−3
295 parameters	Δρmin = −0.35 e Å^−3

Special details

Experimental. SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0545 before and 0.0502 after correction. The Ratio of minimum to maximum transmission is 0.9200. The λ/2 correction factor is 0.0015.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe	1.0000	0.0000	0.5000	0.01108 (9)
C23	1.02702 (17)	0.01547 (10)	0.36771 (14)	0.0145 (4)
N3	1.05491 (15)	0.03942 (9)	0.29849 (12)	0.0170 (3)
C24	1.10111 (19)	0.08937 (11)	0.23145 (15)	0.0198 (4)
C25	1.0239 (2)	0.16655 (11)	0.21248 (19)	0.0276 (5)
H25A	1.0520	0.2019	0.1677	0.041*
H25B	1.0418	0.1917	0.2832	0.041*
H25C	0.9281	0.1558	0.1744	0.041*
C26	1.2495 (2)	0.10337 (15)	0.29680 (19)	0.0349 (5)
H26A	1.2841	0.1367	0.2543	0.052*
H26B	1.2966	0.0526	0.3123	0.052*
H26C	1.2636	0.1298	0.3660	0.052*
C27	1.0745 (2)	0.04753 (13)	0.12358 (17)	0.0312 (5)
H27A	1.1054	0.0808	0.0785	0.047*
H27B	0.9786	0.0378	0.0845	0.047*
H27C	1.1226	−0.0029	0.1384	0.047*
N1	0.82346 (14)	0.05565 (8)	0.43209 (11)	0.0123 (3)
N2	1.09274 (14)	0.10501 (8)	0.53887 (11)	0.0123 (3)
C1	0.69880 (17)	0.02084 (10)	0.38631 (14)	0.0137 (3)
C2	0.59681 (18)	0.08046 (10)	0.34686 (14)	0.0164 (4)
H2	0.5034	0.0716	0.3103	0.020*
C3	0.65836 (18)	0.15122 (11)	0.37137 (15)	0.0175 (4)
H3	0.6166	0.2016	0.3566	0.021*
C4	0.79981 (17)	0.13574 (10)	0.42436 (14)	0.0137 (3)
C5	0.89792 (17)	0.19464 (10)	0.46487 (14)	0.0138 (3)
C6	1.03494 (17)	0.17860 (10)	0.51399 (14)	0.0138 (3)
C7	1.13680 (18)	0.23832 (10)	0.53796 (15)	0.0176 (4)
H7	1.1230	0.2937	0.5281	0.021*
C8	1.25547 (18)	0.20053 (10)	0.57700 (15)	0.0177 (4)
H8	1.3410	0.2243	0.5995	0.021*
C9	1.22812 (17)	0.11779 (10)	0.57818 (14)	0.0142 (3)
C10	0.67285 (17)	−0.05975 (10)	0.38344 (14)	0.0137 (3)
C11	0.85653 (17)	0.27954 (10)	0.45362 (14)	0.0152 (4)
C12	0.78007 (18)	0.31308 (10)	0.35164 (15)	0.0172 (4)
H12	0.7471	0.2803	0.2884	0.021*
C13	0.75130 (18)	0.39353 (11)	0.34085 (15)	0.0188 (4)
H13	0.6975	0.4156	0.2714	0.023*
C14	0.80245 (18)	0.44073 (10)	0.43308 (16)	0.0190 (4)
C15	0.87414 (19)	0.40905 (11)	0.53618 (16)	0.0217 (4)
H15	0.9057	0.4420	0.5992	0.026*
C16	0.89919 (19)	0.32841 (11)	0.54595 (15)	0.0196 (4)
H16	0.9461	0.3060	0.6166	0.024*
C17	0.52953 (17)	−0.08653 (10)	0.33800 (14)	0.0148 (4)
C18	0.46030 (18)	−0.10376 (12)	0.22725 (15)	0.0219 (4)
H18	0.5034	−0.0973	0.1788	0.026*
C19	0.32887 (19)	−0.13036 (12)	0.18617 (16)	0.0236 (4)
H19	0.2825	−0.1420	0.1104	0.028*
C20	0.26692 (18)	−0.13963 (11)	0.25659 (17)	0.0209 (4)
C21	0.3315 (2)	−0.12213 (14)	0.36586 (17)	0.0299 (5)
H21	0.2873	−0.1280	0.4136	0.036*
C22	0.4631 (2)	−0.09559 (13)	0.40590 (16)	0.0270 (5)
H22	0.5083	−0.0834	0.4816	0.032*
Cl2	0.10157 (5)	−0.17304 (3)	0.20542 (5)	0.03464 (14)
Cl1	0.78308 (5)	0.54293 (3)	0.41772 (5)	0.03197 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.00822 (17)	0.01188 (16)	0.01215 (17)	−0.00047 (13)	0.00312 (13)	0.00022 (13)
C23	0.0088 (8)	0.0138 (8)	0.0178 (9)	−0.0010 (6)	0.0024 (7)	−0.0018 (7)
N3	0.0138 (7)	0.0197 (8)	0.0167 (8)	0.0018 (6)	0.0053 (6)	−0.0003 (6)
C24	0.0179 (9)	0.0241 (9)	0.0198 (9)	0.0024 (8)	0.0102 (8)	0.0065 (8)
C25	0.0253 (11)	0.0195 (9)	0.0401 (12)	0.0018 (8)	0.0154 (10)	0.0045 (9)
C26	0.0185 (11)	0.0500 (14)	0.0349 (12)	−0.0002 (10)	0.0095 (9)	0.0147 (11)
C27	0.0425 (13)	0.0337 (12)	0.0243 (11)	0.0067 (10)	0.0207 (10)	0.0053 (9)
N1	0.0107 (7)	0.0130 (7)	0.0132 (7)	−0.0004 (5)	0.0049 (6)	0.0000 (6)
N2	0.0084 (7)	0.0133 (7)	0.0138 (7)	−0.0003 (5)	0.0031 (6)	0.0001 (6)
C1	0.0104 (8)	0.0171 (8)	0.0136 (8)	0.0003 (7)	0.0049 (7)	−0.0003 (7)
C2	0.0101 (8)	0.0192 (9)	0.0175 (9)	0.0013 (7)	0.0032 (7)	0.0019 (7)
C3	0.0145 (9)	0.0178 (9)	0.0194 (9)	0.0024 (7)	0.0060 (7)	0.0025 (7)
C4	0.0123 (8)	0.0155 (8)	0.0132 (8)	0.0025 (7)	0.0051 (7)	0.0016 (7)
C5	0.0151 (9)	0.0137 (8)	0.0132 (8)	0.0009 (7)	0.0062 (7)	0.0000 (7)
C6	0.0149 (9)	0.0128 (8)	0.0136 (8)	−0.0002 (7)	0.0056 (7)	−0.0009 (7)
C7	0.0163 (9)	0.0136 (8)	0.0214 (9)	−0.0022 (7)	0.0060 (8)	−0.0002 (7)
C8	0.0135 (9)	0.0160 (9)	0.0220 (9)	−0.0043 (7)	0.0054 (8)	−0.0023 (7)
C9	0.0124 (8)	0.0171 (8)	0.0128 (8)	−0.0026 (7)	0.0047 (7)	−0.0017 (7)
C10	0.0105 (8)	0.0177 (8)	0.0118 (8)	−0.0012 (7)	0.0036 (7)	−0.0012 (7)
C11	0.0131 (9)	0.0149 (8)	0.0187 (9)	−0.0001 (7)	0.0078 (7)	0.0002 (7)
C12	0.0162 (9)	0.0167 (8)	0.0181 (9)	−0.0008 (7)	0.0062 (7)	−0.0008 (7)
C13	0.0147 (9)	0.0205 (9)	0.0212 (9)	0.0029 (7)	0.0072 (8)	0.0049 (7)
C14	0.0157 (9)	0.0119 (8)	0.0309 (11)	0.0018 (7)	0.0112 (8)	−0.0006 (7)
C15	0.0194 (10)	0.0205 (9)	0.0226 (10)	0.0020 (8)	0.0061 (8)	−0.0055 (8)
C16	0.0191 (9)	0.0205 (9)	0.0176 (9)	0.0029 (7)	0.0058 (8)	−0.0004 (7)
C17	0.0103 (8)	0.0114 (8)	0.0202 (9)	0.0009 (6)	0.0035 (7)	0.0007 (7)
C18	0.0137 (9)	0.0317 (11)	0.0204 (10)	−0.0021 (8)	0.0071 (8)	−0.0027 (8)
C19	0.0150 (9)	0.0300 (10)	0.0215 (10)	−0.0030 (8)	0.0029 (8)	−0.0071 (8)
C20	0.0088 (8)	0.0187 (9)	0.0312 (10)	−0.0037 (7)	0.0041 (8)	0.0001 (8)
C21	0.0173 (10)	0.0489 (13)	0.0257 (11)	−0.0065 (9)	0.0109 (9)	0.0028 (10)
C22	0.0163 (10)	0.0453 (13)	0.0185 (10)	−0.0059 (9)	0.0061 (8)	−0.0032 (9)
Cl2	0.0135 (2)	0.0395 (3)	0.0448 (3)	−0.0117 (2)	0.0056 (2)	−0.0006 (2)
Cl1	0.0304 (3)	0.0139 (2)	0.0455 (3)	0.00429 (19)	0.0091 (2)	0.0003 (2)

Geometric parameters (Å, º)

Fe—C23	1.9244 (18)	C5—C11	1.496 (2)
Fe—C23^i	1.9244 (18)	C6—C7	1.443 (2)
Fe—N1^i	2.0074 (14)	C7—C8	1.350 (3)
Fe—N1	2.0074 (14)	C7—H7	0.9500
Fe—N2^i	2.0081 (14)	C8—C9	1.434 (2)
Fe—N2	2.0081 (14)	C8—H8	0.9500
C23—N3	1.159 (2)	C9—C10^i	1.398 (2)
N3—C24	1.464 (2)	C10—C9^i	1.398 (2)
C24—C26	1.520 (3)	C10—C17	1.506 (2)
C24—C25	1.521 (3)	C11—C12	1.397 (2)
C24—C27	1.523 (3)	C11—C16	1.398 (2)
C25—H25A	0.9800	C12—C13	1.392 (2)
C25—H25B	0.9800	C12—H12	0.9500
C25—H25C	0.9800	C13—C14	1.381 (3)
C26—H26A	0.9800	C13—H13	0.9500
C26—H26B	0.9800	C14—C15	1.386 (3)
C26—H26C	0.9800	C14—Cl1	1.7446 (18)
C27—H27A	0.9800	C15—C16	1.388 (3)
C27—H27B	0.9800	C15—H15	0.9500
C27—H27C	0.9800	C16—H16	0.9500
N1—C4	1.376 (2)	C17—C22	1.383 (3)
N1—C1	1.382 (2)	C17—C18	1.391 (3)
N2—C6	1.376 (2)	C18—C19	1.392 (3)
N2—C9	1.376 (2)	C18—H18	0.9500
C1—C10	1.391 (2)	C19—C20	1.375 (3)
C1—C2	1.438 (2)	C19—H19	0.9500
C2—C3	1.348 (2)	C20—C21	1.370 (3)
C2—H2	0.9500	C20—Cl2	1.7513 (18)
C3—C4	1.443 (2)	C21—C22	1.394 (3)
C3—H3	0.9500	C21—H21	0.9500
C4—C5	1.404 (2)	C22—H22	0.9500
C5—C6	1.400 (2)
C23—Fe—C23^i	180.0	N1—C4—C3	110.35 (15)
C23—Fe—N1^i	89.88 (6)	C5—C4—C3	124.23 (16)
C23^i—Fe—N1^i	90.12 (6)	C6—C5—C4	123.44 (16)
C23—Fe—N1	90.12 (6)	C6—C5—C11	117.22 (15)
C23^i—Fe—N1	89.88 (6)	C4—C5—C11	119.32 (15)
N1^i—Fe—N1	180.00 (5)	N2—C6—C5	126.17 (15)
C23—Fe—N2^i	97.71 (6)	N2—C6—C7	109.97 (15)
C23^i—Fe—N2^i	82.29 (6)	C5—C6—C7	123.69 (16)
N1^i—Fe—N2^i	89.75 (6)	C8—C7—C6	106.95 (16)
N1—Fe—N2^i	90.25 (6)	C8—C7—H7	126.5
C23—Fe—N2	82.29 (6)	C6—C7—H7	126.5
C23^i—Fe—N2	97.71 (6)	C7—C8—C9	107.09 (16)
N1^i—Fe—N2	90.25 (6)	C7—C8—H8	126.5
N1—Fe—N2	89.75 (6)	C9—C8—H8	126.5
N2^i—Fe—N2	180.00 (4)	N2—C9—C10^i	125.90 (16)
N3—C23—Fe	165.75 (15)	N2—C9—C8	110.34 (15)
C23—N3—C24	163.66 (17)	C10^i—C9—C8	123.75 (16)
N3—C24—C26	107.17 (15)	C1—C10—C9^i	124.00 (16)
N3—C24—C25	106.85 (15)	C1—C10—C17	118.33 (15)
C26—C24—C25	110.81 (17)	C9^i—C10—C17	117.65 (15)
N3—C24—C27	109.23 (16)	C12—C11—C16	118.18 (16)
C26—C24—C27	111.31 (17)	C12—C11—C5	121.71 (16)
C25—C24—C27	111.25 (16)	C16—C11—C5	120.05 (16)
C24—C25—H25A	109.5	C13—C12—C11	121.30 (17)
C24—C25—H25B	109.5	C13—C12—H12	119.4
H25A—C25—H25B	109.5	C11—C12—H12	119.4
C24—C25—H25C	109.5	C14—C13—C12	118.74 (17)
H25A—C25—H25C	109.5	C14—C13—H13	120.6
H25B—C25—H25C	109.5	C12—C13—H13	120.6
C24—C26—H26A	109.5	C13—C14—C15	121.51 (17)
C24—C26—H26B	109.5	C13—C14—Cl1	118.87 (14)
H26A—C26—H26B	109.5	C15—C14—Cl1	119.55 (14)
C24—C26—H26C	109.5	C14—C15—C16	118.98 (17)
H26A—C26—H26C	109.5	C14—C15—H15	120.5
H26B—C26—H26C	109.5	C16—C15—H15	120.5
C24—C27—H27A	109.5	C15—C16—C11	121.10 (17)
C24—C27—H27B	109.5	C15—C16—H16	119.4
H27A—C27—H27B	109.5	C11—C16—H16	119.4
C24—C27—H27C	109.5	C22—C17—C18	117.94 (17)
H27A—C27—H27C	109.5	C22—C17—C10	120.72 (16)
H27B—C27—H27C	109.5	C18—C17—C10	121.34 (16)
C4—N1—C1	105.33 (14)	C17—C18—C19	121.09 (18)
C4—N1—Fe	127.86 (11)	C17—C18—H18	119.5
C1—N1—Fe	126.77 (11)	C19—C18—H18	119.5
C6—N2—C9	105.64 (14)	C20—C19—C18	119.22 (18)
C6—N2—Fe	127.13 (11)	C20—C19—H19	120.4
C9—N2—Fe	126.32 (11)	C18—C19—H19	120.4
N1—C1—C10	125.79 (16)	C21—C20—C19	121.22 (17)
N1—C1—C2	110.18 (15)	C21—C20—Cl2	119.33 (16)
C10—C1—C2	123.93 (16)	C19—C20—Cl2	119.44 (15)
C3—C2—C1	107.24 (16)	C20—C21—C22	118.95 (19)
C3—C2—H2	126.4	C20—C21—H21	120.5
C1—C2—H2	126.4	C22—C21—H21	120.5
C2—C3—C4	106.85 (16)	C17—C22—C21	121.57 (18)
C2—C3—H3	126.6	C17—C22—H22	119.2
C4—C3—H3	126.6	C21—C22—H22	119.2
N1—C4—C5	125.39 (16)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the N1/C1–C4 pyrrole ring.

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25C···Cl1^ii	0.98	2.86	3.738 (2)	149
C27—H27B···Cl1^ii	0.98	2.86	3.733 (2)	149
C7—H7···Cl1^iii	0.95	2.94	3.7953 (18)	151
C13—H13···N2^iv	0.95	2.86	3.685 (2)	146
C21—H21···Cg1^v	0.96	2.69	3.518 (2)	146

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