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The features of porphyrins defining their functionality are related to their conformational flexibility. The degree of nonplanarity of metalloporphyrins depends directly on the number of substituents, their size and their location. The introduction of substituents in the meso positions of β-substituted porphyrins increases the steric inter­action and leads to distortions of the porphyrin core. Increasing the distortion of the porphyrin core would augment the batho­chromic (red) shift of the electronic absorption spectra. A new nonsymmetrical 2,3,7,8,12,13,17,18-octa­ethyl-5-[(methyl­imino)­meth­yl]porphyrin complex of palla­dium(II), [Pd(C38H47N5)], was synthesized and characterized by NMR, mass spectrometry and X-ray analysis. The features of the electronic absorption spectrum of the synthesized complex are explained by the planarity of the porphyrin core and the π-system of the imino group orthogonal to it.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616020465/cu3109sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616020465/cu3109Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616020465/cu3109sup4.pdf
Supporting information

CCDC reference: 1524313

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and publCIF (Westrip, 2010).

{2,3,7,8,12,13,17,18-Octaethyl-5-[(methylimino)methyl]porphyrinato-κ4N21,N22,N23,N24}palladium(II) top
Crystal data top
[Pd(C38H47N5)]F(000) = 1424
Mr = 680.20Dx = 1.357 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54186 Å
a = 29.525 (2) ÅCell parameters from 1454 reflections
b = 4.9400 (8) Åθ = 4–64°
c = 25.6630 (11) ŵ = 4.75 mm1
β = 117.225 (1)°T = 295 K
V = 3328.4 (6) Å3Prism, red
Z = 40.21 × 0.10 × 0.10 mm
Data collection top
Stoe
diffractometer
3245 independent reflections
Radiation source: Cu GeniX 3D2366 reflections with I > 2σ(I)
None monochromatorRint = 0.063
Detector resolution: 5.81 pixels mm-1θmax = 73.0°, θmin = 3.4°
rotation method scansh = 3624
Absorption correction: multi-scan
(Blessing, 1995)
k = 65
Tmin = 0.481, Tmax = 0.630l = 3031
12253 measured reflections
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.183 w = 1/[σ2(Fo2) + (0.075P)2 + 16.3947P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
3245 reflectionsΔρmax = 0.69 e Å3
221 parametersΔρmin = 0.74 e Å3
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.25000.25000.00000.0552 (2)
N10.26383 (19)0.0387 (11)0.0617 (2)0.0551 (12)
N20.32481 (19)0.2307 (12)0.0185 (2)0.0597 (12)
C20.2286 (3)0.1465 (15)0.0760 (3)0.0593 (15)
C30.2513 (3)0.3474 (15)0.1216 (3)0.0634 (16)
C40.3019 (3)0.3576 (16)0.1347 (3)0.0656 (17)
C50.3097 (3)0.1655 (13)0.0968 (3)0.0573 (15)
C70.3614 (2)0.0656 (15)0.0576 (3)0.0615 (16)
C80.4087 (2)0.1068 (17)0.0532 (3)0.0684 (18)
C90.3985 (3)0.3034 (16)0.0119 (3)0.071 (2)
C100.3464 (2)0.3815 (16)0.0087 (3)0.0612 (16)
C110.1778 (2)0.0736 (14)0.0509 (3)0.0611 (15)
H110.15770.16600.06420.073*
C120.4324 (3)0.407 (2)0.0127 (4)0.087 (2)
H12A0.46750.37250.01550.104*
H12B0.42810.60140.01750.104*
C130.4228 (4)0.283 (2)0.0709 (5)0.115 (4)
H13A0.42590.08960.06690.172*
H13B0.44730.35150.08240.172*
H13C0.38910.32890.10000.172*
C140.4594 (3)0.028 (2)0.0882 (5)0.101 (3)
H14A0.47620.05110.06370.121*
H14B0.45400.20640.10030.121*
C150.4940 (4)0.138 (3)0.1428 (6)0.162 (7)
H15A0.49940.31410.13110.243*
H15B0.52620.04700.16360.243*
H15C0.47810.15480.16800.243*
C180.3415 (3)0.5306 (19)0.1813 (4)0.087 (2)
H18A0.36740.57570.16950.105*
H18B0.32570.69840.18410.105*
C190.3667 (4)0.400 (3)0.2407 (4)0.130 (4)
H19A0.38300.23580.23860.195*
H19B0.39160.52170.26810.195*
H19C0.34150.36030.25340.195*
C200.2235 (3)0.5050 (17)0.1470 (3)0.0741 (19)
H20A0.24390.65970.16780.089*
H20B0.19200.57270.11540.089*
C210.2109 (4)0.3387 (19)0.1888 (4)0.092 (3)
H21A0.24150.25640.21800.138*
H21B0.19670.45490.20750.138*
H21C0.18680.20040.16730.138*
C60.3545 (3)0.1175 (15)0.0951 (3)0.0642 (16)
H60.38290.21440.12110.077*0.5
C160.4009 (6)0.272 (3)0.1390 (6)0.072 (4)0.5
H160.40700.44730.13030.087*0.5
N30.4312 (5)0.165 (3)0.1871 (6)0.081 (4)0.5
C170.4744 (8)0.347 (5)0.2266 (9)0.121 (8)0.5
H17A0.46810.52810.21130.182*0.5
H17B0.47690.34630.26520.182*0.5
H17C0.50580.28240.22830.182*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0576 (4)0.0599 (4)0.0509 (3)0.0035 (3)0.0273 (3)0.0071 (3)
N10.060 (3)0.053 (3)0.055 (3)0.002 (2)0.028 (2)0.011 (2)
N20.059 (3)0.070 (3)0.055 (3)0.005 (3)0.030 (2)0.003 (3)
C20.070 (4)0.060 (3)0.053 (3)0.005 (3)0.033 (3)0.008 (3)
C30.079 (4)0.058 (4)0.056 (4)0.002 (3)0.033 (3)0.002 (3)
C40.077 (4)0.059 (4)0.060 (4)0.001 (4)0.031 (3)0.007 (3)
C50.071 (4)0.054 (3)0.053 (3)0.002 (3)0.033 (3)0.007 (3)
C70.055 (3)0.068 (4)0.062 (4)0.005 (3)0.027 (3)0.004 (3)
C80.060 (4)0.073 (5)0.069 (4)0.002 (4)0.028 (3)0.002 (4)
C90.064 (4)0.075 (5)0.076 (4)0.011 (3)0.034 (3)0.008 (4)
C100.054 (3)0.071 (4)0.062 (4)0.009 (3)0.029 (3)0.009 (3)
C110.067 (4)0.058 (4)0.066 (4)0.005 (3)0.037 (3)0.006 (3)
C120.063 (4)0.103 (7)0.099 (6)0.006 (5)0.042 (4)0.013 (5)
C130.100 (6)0.146 (10)0.134 (9)0.003 (7)0.084 (7)0.007 (7)
C140.066 (5)0.097 (7)0.129 (8)0.002 (5)0.036 (5)0.018 (6)
C150.096 (7)0.113 (9)0.168 (12)0.015 (7)0.034 (8)0.017 (9)
C180.098 (6)0.077 (5)0.085 (5)0.019 (5)0.041 (5)0.015 (4)
C190.124 (8)0.146 (10)0.078 (6)0.036 (8)0.010 (6)0.003 (7)
C200.085 (5)0.074 (5)0.067 (4)0.007 (4)0.037 (4)0.007 (4)
C210.119 (7)0.081 (6)0.096 (6)0.005 (5)0.067 (6)0.007 (5)
C60.071 (4)0.065 (4)0.058 (4)0.003 (4)0.031 (3)0.009 (3)
C160.078 (9)0.069 (9)0.072 (8)0.008 (8)0.035 (7)0.004 (8)
N30.075 (8)0.086 (9)0.068 (7)0.017 (7)0.019 (6)0.002 (7)
C170.100 (14)0.140 (19)0.093 (13)0.038 (14)0.018 (10)0.020 (13)
Geometric parameters (Å, º) top
Pd1—N12.029 (5)C13—H13B0.9600
Pd1—N1i2.029 (5)C13—H13C0.9600
Pd1—N2i2.038 (5)C14—C151.539 (15)
Pd1—N22.038 (5)C14—H14A0.9700
N1—C21.359 (8)C14—H14B0.9700
N1—C51.387 (8)C15—H15A0.9600
N2—C71.359 (8)C15—H15B0.9600
N2—C101.364 (8)C15—H15C0.9600
C2—C111.381 (9)C18—C191.502 (13)
C2—C31.445 (10)C18—H18A0.9700
C3—C41.374 (10)C18—H18B0.9700
C3—C201.482 (10)C19—H19A0.9600
C4—C51.452 (10)C19—H19B0.9600
C4—C181.499 (11)C19—H19C0.9600
C5—C61.362 (10)C20—C211.526 (12)
C7—C61.403 (10)C20—H20A0.9700
C7—C81.464 (9)C20—H20B0.9700
C8—C91.366 (11)C21—H21A0.9600
C8—C141.504 (10)C21—H21B0.9600
C9—C101.430 (10)C21—H21C0.9600
C9—C121.498 (10)C6—C161.523 (17)
C10—C11i1.370 (10)C6—H60.9300
C11—C10i1.370 (10)C16—N31.26 (2)
C11—H110.9300C16—H160.9300
C12—C131.516 (13)N3—C171.51 (2)
C12—H12A0.9700C17—H17A0.9600
C12—H12B0.9700C17—H17B0.9600
C13—H13A0.9600C17—H17C0.9600
N1—Pd1—N1i180.0C8—C14—H14A109.2
N1—Pd1—N2i91.4 (2)C15—C14—H14A109.2
N1i—Pd1—N2i88.6 (2)C8—C14—H14B109.2
N1—Pd1—N288.6 (2)C15—C14—H14B109.2
N1i—Pd1—N291.4 (2)H14A—C14—H14B107.9
N2i—Pd1—N2180.00 (7)C14—C15—H15A109.5
C2—N1—C5106.8 (6)C14—C15—H15B109.5
C2—N1—Pd1125.4 (4)H15A—C15—H15B109.5
C5—N1—Pd1127.7 (4)C14—C15—H15C109.5
C7—N2—C10107.7 (5)H15A—C15—H15C109.5
C7—N2—Pd1127.8 (4)H15B—C15—H15C109.5
C10—N2—Pd1124.5 (5)C4—C18—C19114.1 (8)
N1—C2—C11125.0 (6)C4—C18—H18A108.7
N1—C2—C3111.0 (6)C19—C18—H18A108.7
C11—C2—C3124.0 (6)C4—C18—H18B108.7
C4—C3—C2105.9 (6)C19—C18—H18B108.7
C4—C3—C20129.2 (7)H18A—C18—H18B107.6
C2—C3—C20124.9 (7)C18—C19—H19A109.5
C3—C4—C5107.5 (6)C18—C19—H19B109.5
C3—C4—C18125.5 (7)H19A—C19—H19B109.5
C5—C4—C18127.0 (7)C18—C19—H19C109.5
C6—C5—N1125.1 (6)H19A—C19—H19C109.5
C6—C5—C4126.1 (7)H19B—C19—H19C109.5
N1—C5—C4108.8 (6)C3—C20—C21112.9 (7)
N2—C7—C6125.2 (6)C3—C20—H20A109.0
N2—C7—C8109.0 (6)C21—C20—H20A109.0
C6—C7—C8125.8 (6)C3—C20—H20B109.0
C9—C8—C7106.1 (6)C21—C20—H20B109.0
C9—C8—C14125.8 (7)H20A—C20—H20B107.8
C7—C8—C14128.1 (7)C20—C21—H21A109.5
C8—C9—C10107.3 (6)C20—C21—H21B109.5
C8—C9—C12128.1 (7)H21A—C21—H21B109.5
C10—C9—C12124.4 (7)C20—C21—H21C109.5
N2—C10—C11i125.8 (6)H21A—C21—H21C109.5
N2—C10—C9109.8 (6)H21B—C21—H21C109.5
C11i—C10—C9124.4 (6)C5—C6—C7125.6 (7)
C10i—C11—C2127.8 (6)C5—C6—C16116.5 (8)
C10i—C11—H11116.1C7—C6—C16117.8 (8)
C2—C11—H11116.1C5—C6—H6117.2
C9—C12—C13114.7 (7)C7—C6—H6117.2
C9—C12—H12A108.6C16—C6—H61.5
C13—C12—H12A108.6N3—C16—C6120.5 (13)
C9—C12—H12B108.6N3—C16—H16119.8
C13—C12—H12B108.6C6—C16—H16119.8
H12A—C12—H12B107.6C16—N3—C17114.2 (16)
C12—C13—H13A109.5N3—C17—H17A109.5
C12—C13—H13B109.5N3—C17—H17B109.5
H13A—C13—H13B109.5H17A—C17—H17B109.5
C12—C13—H13C109.5N3—C17—H17C109.5
H13A—C13—H13C109.5H17A—C17—H17C109.5
H13B—C13—H13C109.5H17B—C17—H17C109.5
C8—C14—C15111.9 (9)
C5—N1—C2—C11179.8 (6)C14—C8—C9—C127.3 (14)
Pd1—N1—C2—C110.6 (9)C7—N2—C10—C11i179.6 (7)
C5—N1—C2—C30.3 (7)Pd1—N2—C10—C11i2.3 (10)
Pd1—N1—C2—C3179.9 (4)C7—N2—C10—C92.3 (8)
N1—C2—C3—C40.2 (8)Pd1—N2—C10—C9175.8 (5)
C11—C2—C3—C4179.3 (6)C8—C9—C10—N21.4 (8)
N1—C2—C3—C20179.5 (6)C12—C9—C10—N2173.7 (7)
C11—C2—C3—C201.0 (11)C8—C9—C10—C11i179.5 (7)
C2—C3—C4—C50.6 (7)C12—C9—C10—C11i4.5 (12)
C20—C3—C4—C5179.1 (7)N1—C2—C11—C10i1.2 (11)
C2—C3—C4—C18177.6 (7)C3—C2—C11—C10i178.2 (7)
C20—C3—C4—C182.7 (13)C8—C9—C12—C1397.7 (11)
C2—N1—C5—C6178.7 (6)C10—C9—C12—C1376.4 (11)
Pd1—N1—C5—C60.8 (9)C9—C8—C14—C1584.7 (12)
C2—N1—C5—C40.7 (7)C7—C8—C14—C1592.7 (12)
Pd1—N1—C5—C4179.8 (4)C3—C4—C18—C1988.0 (11)
C3—C4—C5—C6178.6 (6)C5—C4—C18—C1989.9 (11)
C18—C4—C5—C63.2 (12)C4—C3—C20—C21105.2 (9)
C3—C4—C5—N10.8 (7)C2—C3—C20—C2175.1 (9)
C18—C4—C5—N1177.4 (7)N1—C5—C6—C70.4 (11)
C10—N2—C7—C6178.7 (6)C4—C5—C6—C7178.9 (7)
Pd1—N2—C7—C63.3 (10)N1—C5—C6—C16178.0 (8)
C10—N2—C7—C82.2 (8)C4—C5—C6—C162.6 (12)
Pd1—N2—C7—C8175.8 (4)N2—C7—C6—C52.6 (11)
N2—C7—C8—C91.4 (8)C8—C7—C6—C5176.3 (7)
C6—C7—C8—C9179.6 (7)N2—C7—C6—C16175.9 (9)
N2—C7—C8—C14179.1 (8)C8—C7—C6—C165.2 (12)
C6—C7—C8—C141.8 (13)C5—C6—C16—N395.9 (16)
C7—C8—C9—C100.0 (8)C7—C6—C16—N382.7 (16)
C14—C8—C9—C10177.8 (8)C6—C16—N3—C17178.2 (15)
C7—C8—C9—C12174.8 (8)
Symmetry code: (i) x+1/2, y+1/2, z.
 

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