Structural explanation of the spectral features of the nonsymmetrical complex {2,3,7,8,12,13,17,18-octa­ethyl-5-[(methyl­imino)­meth­yl]porphyrinato-κ⁴N²¹,N²²,N²³,N²⁴}palladium(II)

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.

Computing details

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)

Crystal data

[Pd(C38H47N5)]	F(000) = 1424
Mr = 680.20	Dx = 1.357 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54186 Å
a = 29.525 (2) Å	Cell parameters from 1454 reflections
b = 4.9400 (8) Å	θ = 4–64°
c = 25.6630 (11) Å	µ = 4.75 mm^−1
β = 117.225 (1)°	T = 295 K
V = 3328.4 (6) Å^3	Prism, red
Z = 4	0.21 × 0.10 × 0.10 mm

Data collection

Stoe diffractometer	3245 independent reflections
Radiation source: Cu GeniX 3D	2366 reflections with I > 2σ(I)
None monochromator	Rint = 0.063
Detector resolution: 5.81 pixels mm^-1	θmax = 73.0°, θmin = 3.4°
rotation method scans	h = −36→24
Absorption correction: multi-scan (Blessing, 1995)	k = −6→5
Tmin = 0.481, Tmax = 0.630	l = −30→31
12253 measured reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.183	w = 1/[σ^2(Fo^2) + (0.075P)^2 + 16.3947P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
3245 reflections	Δρmax = 0.69 e Å^−3
221 parameters	Δρmin = −0.74 e Å^−3

Special details

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	Occ. (<1)
Pd1	0.2500	0.2500	0.0000	0.0552 (2)
N1	0.26383 (19)	−0.0387 (11)	0.0617 (2)	0.0551 (12)
N2	0.32481 (19)	0.2307 (12)	0.0185 (2)	0.0597 (12)
C2	0.2286 (3)	−0.1465 (15)	0.0760 (3)	0.0593 (15)
C3	0.2513 (3)	−0.3474 (15)	0.1216 (3)	0.0634 (16)
C4	0.3019 (3)	−0.3576 (16)	0.1347 (3)	0.0656 (17)
C5	0.3097 (3)	−0.1655 (13)	0.0968 (3)	0.0573 (15)
C7	0.3614 (2)	0.0656 (15)	0.0576 (3)	0.0615 (16)
C8	0.4087 (2)	0.1068 (17)	0.0532 (3)	0.0684 (18)
C9	0.3985 (3)	0.3034 (16)	0.0119 (3)	0.071 (2)
C10	0.3464 (2)	0.3815 (16)	−0.0087 (3)	0.0612 (16)
C11	0.1778 (2)	−0.0736 (14)	0.0509 (3)	0.0611 (15)
H11	0.1577	−0.1660	0.0642	0.073*
C12	0.4324 (3)	0.407 (2)	−0.0127 (4)	0.087 (2)
H12A	0.4675	0.3725	0.0155	0.104*
H12B	0.4281	0.6014	−0.0175	0.104*
C13	0.4228 (4)	0.283 (2)	−0.0709 (5)	0.115 (4)
H13A	0.4259	0.0896	−0.0669	0.172*
H13B	0.4473	0.3515	−0.0824	0.172*
H13C	0.3891	0.3289	−0.1000	0.172*
C14	0.4594 (3)	−0.028 (2)	0.0882 (5)	0.101 (3)
H14A	0.4762	−0.0511	0.0637	0.121*
H14B	0.4540	−0.2064	0.1003	0.121*
C15	0.4940 (4)	0.138 (3)	0.1428 (6)	0.162 (7)
H15A	0.4994	0.3141	0.1311	0.243*
H15B	0.5262	0.0470	0.1636	0.243*
H15C	0.4781	0.1548	0.1680	0.243*
C18	0.3415 (3)	−0.5306 (19)	0.1813 (4)	0.087 (2)
H18A	0.3674	−0.5757	0.1695	0.105*
H18B	0.3257	−0.6984	0.1841	0.105*
C19	0.3667 (4)	−0.400 (3)	0.2407 (4)	0.130 (4)
H19A	0.3830	−0.2358	0.2386	0.195*
H19B	0.3916	−0.5217	0.2681	0.195*
H19C	0.3415	−0.3603	0.2534	0.195*
C20	0.2235 (3)	−0.5050 (17)	0.1470 (3)	0.0741 (19)
H20A	0.2439	−0.6597	0.1678	0.089*
H20B	0.1920	−0.5727	0.1154	0.089*
C21	0.2109 (4)	−0.3387 (19)	0.1888 (4)	0.092 (3)
H21A	0.2415	−0.2564	0.2180	0.138*
H21B	0.1967	−0.4549	0.2075	0.138*
H21C	0.1868	−0.2004	0.1673	0.138*
C6	0.3545 (3)	−0.1175 (15)	0.0951 (3)	0.0642 (16)
H6	0.3829	−0.2144	0.1211	0.077*	0.5
C16	0.4009 (6)	−0.272 (3)	0.1390 (6)	0.072 (4)	0.5
H16	0.4070	−0.4473	0.1303	0.087*	0.5
N3	0.4312 (5)	−0.165 (3)	0.1871 (6)	0.081 (4)	0.5
C17	0.4744 (8)	−0.347 (5)	0.2266 (9)	0.121 (8)	0.5
H17A	0.4681	−0.5281	0.2113	0.182*	0.5
H17B	0.4769	−0.3463	0.2652	0.182*	0.5
H17C	0.5058	−0.2824	0.2283	0.182*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0576 (4)	0.0599 (4)	0.0509 (3)	−0.0035 (3)	0.0273 (3)	−0.0071 (3)
N1	0.060 (3)	0.053 (3)	0.055 (3)	−0.002 (2)	0.028 (2)	−0.011 (2)
N2	0.059 (3)	0.070 (3)	0.055 (3)	−0.005 (3)	0.030 (2)	−0.003 (3)
C2	0.070 (4)	0.060 (3)	0.053 (3)	−0.005 (3)	0.033 (3)	−0.008 (3)
C3	0.079 (4)	0.058 (4)	0.056 (4)	−0.002 (3)	0.033 (3)	−0.002 (3)
C4	0.077 (4)	0.059 (4)	0.060 (4)	−0.001 (4)	0.031 (3)	−0.007 (3)
C5	0.071 (4)	0.054 (3)	0.053 (3)	0.002 (3)	0.033 (3)	−0.007 (3)
C7	0.055 (3)	0.068 (4)	0.062 (4)	0.005 (3)	0.027 (3)	−0.004 (3)
C8	0.060 (4)	0.073 (5)	0.069 (4)	0.002 (4)	0.028 (3)	−0.002 (4)
C9	0.064 (4)	0.075 (5)	0.076 (4)	−0.011 (3)	0.034 (3)	−0.008 (4)
C10	0.054 (3)	0.071 (4)	0.062 (4)	−0.009 (3)	0.029 (3)	−0.009 (3)
C11	0.067 (4)	0.058 (4)	0.066 (4)	−0.005 (3)	0.037 (3)	−0.006 (3)
C12	0.063 (4)	0.103 (7)	0.099 (6)	−0.006 (5)	0.042 (4)	0.013 (5)
C13	0.100 (6)	0.146 (10)	0.134 (9)	−0.003 (7)	0.084 (7)	0.007 (7)
C14	0.066 (5)	0.097 (7)	0.129 (8)	0.002 (5)	0.036 (5)	0.018 (6)
C15	0.096 (7)	0.113 (9)	0.168 (12)	−0.015 (7)	−0.034 (8)	0.017 (9)
C18	0.098 (6)	0.077 (5)	0.085 (5)	0.019 (5)	0.041 (5)	0.015 (4)
C19	0.124 (8)	0.146 (10)	0.078 (6)	0.036 (8)	0.010 (6)	−0.003 (7)
C20	0.085 (5)	0.074 (5)	0.067 (4)	−0.007 (4)	0.037 (4)	0.007 (4)
C21	0.119 (7)	0.081 (6)	0.096 (6)	−0.005 (5)	0.067 (6)	0.007 (5)
C6	0.071 (4)	0.065 (4)	0.058 (4)	0.003 (4)	0.031 (3)	−0.009 (3)
C16	0.078 (9)	0.069 (9)	0.072 (8)	0.008 (8)	0.035 (7)	−0.004 (8)
N3	0.075 (8)	0.086 (9)	0.068 (7)	0.017 (7)	0.019 (6)	0.002 (7)
C17	0.100 (14)	0.140 (19)	0.093 (13)	0.038 (14)	0.018 (10)	0.020 (13)

Geometric parameters (Å, º)

Pd1—N1	2.029 (5)	C13—H13B	0.9600
Pd1—N1^i	2.029 (5)	C13—H13C	0.9600
Pd1—N2^i	2.038 (5)	C14—C15	1.539 (15)
Pd1—N2	2.038 (5)	C14—H14A	0.9700
N1—C2	1.359 (8)	C14—H14B	0.9700
N1—C5	1.387 (8)	C15—H15A	0.9600
N2—C7	1.359 (8)	C15—H15B	0.9600
N2—C10	1.364 (8)	C15—H15C	0.9600
C2—C11	1.381 (9)	C18—C19	1.502 (13)
C2—C3	1.445 (10)	C18—H18A	0.9700
C3—C4	1.374 (10)	C18—H18B	0.9700
C3—C20	1.482 (10)	C19—H19A	0.9600
C4—C5	1.452 (10)	C19—H19B	0.9600
C4—C18	1.499 (11)	C19—H19C	0.9600
C5—C6	1.362 (10)	C20—C21	1.526 (12)
C7—C6	1.403 (10)	C20—H20A	0.9700
C7—C8	1.464 (9)	C20—H20B	0.9700
C8—C9	1.366 (11)	C21—H21A	0.9600
C8—C14	1.504 (10)	C21—H21B	0.9600
C9—C10	1.430 (10)	C21—H21C	0.9600
C9—C12	1.498 (10)	C6—C16	1.523 (17)
C10—C11^i	1.370 (10)	C6—H6	0.9300
C11—C10^i	1.370 (10)	C16—N3	1.26 (2)
C11—H11	0.9300	C16—H16	0.9300
C12—C13	1.516 (13)	N3—C17	1.51 (2)
C12—H12A	0.9700	C17—H17A	0.9600
C12—H12B	0.9700	C17—H17B	0.9600
C13—H13A	0.9600	C17—H17C	0.9600
N1—Pd1—N1^i	180.0	C8—C14—H14A	109.2
N1—Pd1—N2^i	91.4 (2)	C15—C14—H14A	109.2
N1^i—Pd1—N2^i	88.6 (2)	C8—C14—H14B	109.2
N1—Pd1—N2	88.6 (2)	C15—C14—H14B	109.2
N1^i—Pd1—N2	91.4 (2)	H14A—C14—H14B	107.9
N2^i—Pd1—N2	180.00 (7)	C14—C15—H15A	109.5
C2—N1—C5	106.8 (6)	C14—C15—H15B	109.5
C2—N1—Pd1	125.4 (4)	H15A—C15—H15B	109.5
C5—N1—Pd1	127.7 (4)	C14—C15—H15C	109.5
C7—N2—C10	107.7 (5)	H15A—C15—H15C	109.5
C7—N2—Pd1	127.8 (4)	H15B—C15—H15C	109.5
C10—N2—Pd1	124.5 (5)	C4—C18—C19	114.1 (8)
N1—C2—C11	125.0 (6)	C4—C18—H18A	108.7
N1—C2—C3	111.0 (6)	C19—C18—H18A	108.7
C11—C2—C3	124.0 (6)	C4—C18—H18B	108.7
C4—C3—C2	105.9 (6)	C19—C18—H18B	108.7
C4—C3—C20	129.2 (7)	H18A—C18—H18B	107.6
C2—C3—C20	124.9 (7)	C18—C19—H19A	109.5
C3—C4—C5	107.5 (6)	C18—C19—H19B	109.5
C3—C4—C18	125.5 (7)	H19A—C19—H19B	109.5
C5—C4—C18	127.0 (7)	C18—C19—H19C	109.5
C6—C5—N1	125.1 (6)	H19A—C19—H19C	109.5
C6—C5—C4	126.1 (7)	H19B—C19—H19C	109.5
N1—C5—C4	108.8 (6)	C3—C20—C21	112.9 (7)
N2—C7—C6	125.2 (6)	C3—C20—H20A	109.0
N2—C7—C8	109.0 (6)	C21—C20—H20A	109.0
C6—C7—C8	125.8 (6)	C3—C20—H20B	109.0
C9—C8—C7	106.1 (6)	C21—C20—H20B	109.0
C9—C8—C14	125.8 (7)	H20A—C20—H20B	107.8
C7—C8—C14	128.1 (7)	C20—C21—H21A	109.5
C8—C9—C10	107.3 (6)	C20—C21—H21B	109.5
C8—C9—C12	128.1 (7)	H21A—C21—H21B	109.5
C10—C9—C12	124.4 (7)	C20—C21—H21C	109.5
N2—C10—C11^i	125.8 (6)	H21A—C21—H21C	109.5
N2—C10—C9	109.8 (6)	H21B—C21—H21C	109.5
C11^i—C10—C9	124.4 (6)	C5—C6—C7	125.6 (7)
C10^i—C11—C2	127.8 (6)	C5—C6—C16	116.5 (8)
C10^i—C11—H11	116.1	C7—C6—C16	117.8 (8)
C2—C11—H11	116.1	C5—C6—H6	117.2
C9—C12—C13	114.7 (7)	C7—C6—H6	117.2
C9—C12—H12A	108.6	C16—C6—H6	1.5
C13—C12—H12A	108.6	N3—C16—C6	120.5 (13)
C9—C12—H12B	108.6	N3—C16—H16	119.8
C13—C12—H12B	108.6	C6—C16—H16	119.8
H12A—C12—H12B	107.6	C16—N3—C17	114.2 (16)
C12—C13—H13A	109.5	N3—C17—H17A	109.5
C12—C13—H13B	109.5	N3—C17—H17B	109.5
H13A—C13—H13B	109.5	H17A—C17—H17B	109.5
C12—C13—H13C	109.5	N3—C17—H17C	109.5
H13A—C13—H13C	109.5	H17A—C17—H17C	109.5
H13B—C13—H13C	109.5	H17B—C17—H17C	109.5
C8—C14—C15	111.9 (9)
C5—N1—C2—C11	179.8 (6)	C14—C8—C9—C12	7.3 (14)
Pd1—N1—C2—C11	−0.6 (9)	C7—N2—C10—C11^i	−179.6 (7)
C5—N1—C2—C3	0.3 (7)	Pd1—N2—C10—C11^i	2.3 (10)
Pd1—N1—C2—C3	179.9 (4)	C7—N2—C10—C9	2.3 (8)
N1—C2—C3—C4	0.2 (8)	Pd1—N2—C10—C9	−175.8 (5)
C11—C2—C3—C4	−179.3 (6)	C8—C9—C10—N2	−1.4 (8)
N1—C2—C3—C20	−179.5 (6)	C12—C9—C10—N2	173.7 (7)
C11—C2—C3—C20	1.0 (11)	C8—C9—C10—C11^i	−179.5 (7)
C2—C3—C4—C5	−0.6 (7)	C12—C9—C10—C11^i	−4.5 (12)
C20—C3—C4—C5	179.1 (7)	N1—C2—C11—C10^i	−1.2 (11)
C2—C3—C4—C18	177.6 (7)	C3—C2—C11—C10^i	178.2 (7)
C20—C3—C4—C18	−2.7 (13)	C8—C9—C12—C13	97.7 (11)
C2—N1—C5—C6	178.7 (6)	C10—C9—C12—C13	−76.4 (11)
Pd1—N1—C5—C6	−0.8 (9)	C9—C8—C14—C15	84.7 (12)
C2—N1—C5—C4	−0.7 (7)	C7—C8—C14—C15	−92.7 (12)
Pd1—N1—C5—C4	179.8 (4)	C3—C4—C18—C19	−88.0 (11)
C3—C4—C5—C6	−178.6 (6)	C5—C4—C18—C19	89.9 (11)
C18—C4—C5—C6	3.2 (12)	C4—C3—C20—C21	105.2 (9)
C3—C4—C5—N1	0.8 (7)	C2—C3—C20—C21	−75.1 (9)
C18—C4—C5—N1	−177.4 (7)	N1—C5—C6—C7	−0.4 (11)
C10—N2—C7—C6	178.7 (6)	C4—C5—C6—C7	178.9 (7)
Pd1—N2—C7—C6	−3.3 (10)	N1—C5—C6—C16	178.0 (8)
C10—N2—C7—C8	−2.2 (8)	C4—C5—C6—C16	−2.6 (12)
Pd1—N2—C7—C8	175.8 (4)	N2—C7—C6—C5	2.6 (11)
N2—C7—C8—C9	1.4 (8)	C8—C7—C6—C5	−176.3 (7)
C6—C7—C8—C9	−179.6 (7)	N2—C7—C6—C16	−175.9 (9)
N2—C7—C8—C14	179.1 (8)	C8—C7—C6—C16	5.2 (12)
C6—C7—C8—C14	−1.8 (13)	C5—C6—C16—N3	−95.9 (16)
C7—C8—C9—C10	0.0 (8)	C7—C6—C16—N3	82.7 (16)
C14—C8—C9—C10	−177.8 (8)	C6—C16—N3—C17	178.2 (15)
C7—C8—C9—C12	−174.8 (8)

Symmetry code: (i) −x+1/2, −y+1/2, −z.