[5,10,15,20-meso-Tetrakis(2-thienyl)­porphyrinato-κ⁴N]copper(II)

The title compound, [Cu(C₃₆H₂₀N₄S₄)], was synthesized and its molecular structure was precisely characterized by low-temperature single-crystal analysis. The mol­ecules are located on crystallographic centers of inversion.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.046
• wR factor = 0.130
• Data-to-parameter ratio = 11.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



SHFSU_01  Alert B The absolute value of parameter shift to su ratio > 0.10
          Absolute value of the parameter shift to su ratio given   0.118
          Additional refinement cycles may be required.

Author response: The disorder of one of the thiophene rings does not allow a better convergence.

 Alert Level C:



PLAT_213  Alert C Atom  C17    has ADP max/min Ratio ...........       3.90

PLAT_301  Alert C Main Residue Disorder ........................       8.00 Perc.


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

The title compound, (I), was synthesized as a potential building block for the supramolecular synthesis of multiporphyrin arrays. The S-atom sites of the thiophene rings are potential ligating sites for coordination of Cu^I and Ag^I ions, and may thus facilitate formulations of coordination polymers through external metal ion auxiliaries.

The porphyrin core is nearly planar with only a slight roughening, the deviations of the individual atoms from its mean plane not exceeding 0.01 Å. One of the thiophene rings (C18 through S22) exhibits a twofold disorder, with equally populated orientations. The latter are characterized by 50% occupancy of positions 19 and 22 by either C or S atoms, with the appropriate adjustment of the corresponding bond lengths that involve these atoms. Assumption of a single orientation (with only S19 and C22, or alternatively with only C19 and S22) raises the R factor for the observed reflections above 0.098 (as opposed to 0.046 for the disordered model), with a deep trough near the chosen C-atom site and a high peak near the chosen S-atom site. The dihedral angles between the ordered thiophene ring C13—C17 and the C18—S22 thiophene ring in its two equally populated orientations are 7.2 (1) and 4.6 (1)°. As opposed to related tetraaryl metalloporphyrins, which tend to crystallize as clathrates, the present compound crystallized as a pure homogeneous solid. The disorder of the C18—S22 ring is probably affected by the tendency to optimize intermolecular S···S cohesive interactions. In the observed structure, S14···S19(1 - x, 0.5 + y, 0.5 - z) is 3.748 (2) Å, and S14···S22(x, 1 + y, z) is 3.796 (2) Å. A similar disorder of the C13—C17 thiophene ring does not occur, as the distance between position 17 and sites S19 or S22 of neighboring species is larger than 4.8 Å.

S2. Experimental

Pyrrole and all common solvents were obtained from Aldrich. The thiophene-2-carbaldehyde component was prepared by mixing thiophene (21 g, 250 mmol), dimethylformamide (DMF; 23 g, 314 mmol) and dichloroethane (100 g, 1010 mmol) at 273 K. To this solution, phosphorous oxychloride (48 g, 313 mmol) was added drowise with vigorous stirring. The resulting mixture was heated in an oil bath, neutralized with sodium acetate trihydrate (200 g), and the product was extracted with diethyl ether. The ether layer was washed several times with sodium bicarbonate and then with brine, and finally dried over anhydrous sodium sulfate. The solvents were distilled off and the crude thiophene-2-carbaldehyde was purified by reduced-pressure distillation to yield pale-yellow viscous oil (18 g, 64%). ¹H NMR (CDCl₃): δ 7.23 (m, 2H), 7.79 (m, 3H, Ar—H), 9.95 (s, 1H, CHO). A mixture of pyrrole (2.71 g, 40.0 mmol) and the thiophene-2-carbaldehyde (4.48 g, 40 mmol) were added dropwise to 150 ml of boiling propionic acid. The mixture was refluxed with stirring for 1 h, cooled to room temperature and allowed to stand overnight. The resulting dark-coloured mixture was filtered, washed with methanol and then with hot water, and purified by column chromatography (silica, 63–200, 60 Å), using a mixture of petrol ether and chloroform as eluent. This procedure yielded 2.0 g (31%) of tetra(2-thiophene)porphyrin. The latter was then dissolved in DMF heated to boiling, and treated with excess of copper(II) acetate. The resulting product was purified by column chromatography (silica, 63–200, 60 Å) using a mixture of chloroform and ethyl acetate as eluent to yield (I) in high yield (90%). The product was characterized by ¹H NMR and MS analyses. ¹H NMR (CDCl₃): δ 7.53 (m, 1H, Ar—H), 7.7 (m, 1H, Ar—H), 7.87 (m, 1H, Ar—H), 9.04 (s, 1H, CHO).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski, 1985); data reduction: DENZO; program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I). The shown ellipsoids represent the displacement parameters at the 50% probability level at 110 K. Only one orientation of the twofold disordered C18—S22 thiophene ring is shown. The N1—Cu23 and N2—Cu23 bond lengths are 1.999 (4) and 2.012 (4) Å, respectively.
	Fig. 2. Crystal packing viewed down the short a axis of the crystal (b is horizontal and c is vertical; contents of two unit cells are shown). The mean interplanar distance between neighboring molecules displaced along the a axis is 3.6 Å. Atoms are shown as arbitrarily sized spheres; the Cu, N, and S atoms are denoted by crossed circles.

[5,10,15,20-meso-Tetrakis(2-thienyl)porphyrinato-κ⁴N]copper(II)

Crystal data

[Cu(C36H20N4S4)]	F(000) = 714
Mr = 700.34	Dx = 1.583 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
a = 6.5550 (2) Å	Cell parameters from 2307 reflections
b = 10.9180 (3) Å	θ = 2.7–25.4°
c = 20.5590 (6) Å	µ = 1.06 mm^−1
β = 93.2030 (15)°	T = 110 K
V = 1469.06 (7) Å^3	Prism, dark-blue
Z = 2	0.35 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	2587 independent reflections
Radiation source: fine-focus sealed tube	2307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 56 microns pixels mm^-1	θmax = 25.4°, θmin = 2.7°
1.0° ϕ and ω scans	h = 0→7
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = 0→13
Tmin = 0.707, Tmax = 0.857	l = −24→24
4433 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycle	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0554P)^2 + 6.3287P] where P = (Fo^2 + 2Fc^2)/3
2587 reflections	(Δ/σ)max = 0.118
223 parameters	Δρmax = 0.88 e Å^−3
1 restraint	Δρmin = −0.78 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.

One of the thiophene rings suffers a twofold disorder.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.6931 (4)	−0.0297 (3)	0.42979 (14)	0.0167 (6)
N2	0.6580 (4)	0.1511 (3)	0.52748 (14)	0.0170 (6)
C3	0.8155 (5)	0.2042 (3)	0.49591 (17)	0.0180 (7)
C4	0.9098 (5)	0.1549 (3)	0.44295 (17)	0.0179 (7)
C5	0.8570 (5)	0.0422 (3)	0.41479 (16)	0.0181 (7)
C6	0.9683 (6)	−0.0154 (3)	0.36476 (18)	0.0220 (8)
H6	1.0887	0.0148	0.3466	0.026*
C7	0.8695 (6)	−0.1203 (3)	0.34843 (17)	0.0212 (8)
H7	0.9071	−0.1779	0.3166	0.025*
C8	0.6969 (5)	−0.1287 (3)	0.38822 (16)	0.0173 (7)
C9	0.5508 (5)	−0.2220 (3)	0.38367 (16)	0.0171 (7)
C10	0.3882 (5)	−0.2323 (3)	0.42396 (16)	0.0179 (7)
C11	0.2551 (6)	−0.3367 (3)	0.42475 (18)	0.0220 (8)
H11	0.2538	−0.4043	0.3956	0.026*
C12	0.1320 (6)	−0.3210 (3)	0.47459 (18)	0.0229 (8)
H12	0.0303	−0.3763	0.4878	0.028*
C13	1.0738 (6)	0.2265 (3)	0.41429 (17)	0.0200 (7)
S14	1.05374 (18)	0.27758 (11)	0.33550 (5)	0.0311 (3)
C15	1.2805 (7)	0.3491 (4)	0.3413 (2)	0.0368 (11)
H15	1.3348	0.3942	0.3067	0.044*
C16	1.3760 (6)	0.3356 (4)	0.3997 (2)	0.0335 (10)
H16	1.5060	0.3709	0.4103	0.040*
C17	1.2701 (5)	0.2647 (3)	0.44526 (14)	0.0084 (6)
H17	1.3187	0.2455	0.4884	0.010*
C18	0.5728 (5)	−0.3171 (3)	0.33281 (17)	0.0179 (7)
S19	0.4076 (3)	−0.32363 (17)	0.26643 (8)	0.0225 (4)	0.50
C20	0.5331 (6)	−0.4338 (4)	0.23345 (18)	0.0287 (9)
H20	0.4951	−0.4630	0.1910	0.034*
C21	0.6918 (7)	−0.4816 (4)	0.26840 (19)	0.0287 (9)
H21	0.7710	−0.5492	0.2553	0.034*
C22	0.729 (3)	−0.4090 (18)	0.3352 (10)	0.124 (8)	0.50
H22	0.8316	−0.4233	0.3689	0.145*	0.5
C19	0.435 (2)	−0.3220 (9)	0.2723 (4)	0.024 (3)	0.50
H19	0.3207	−0.2723	0.2600	0.030*	0.5
S22	0.7498 (3)	−0.42670 (18)	0.33832 (10)	0.0284 (5)	0.50
Cu23	0.5000	0.0000	0.5000	0.01424 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0205 (15)	0.0140 (14)	0.0158 (14)	−0.0017 (11)	0.0029 (12)	−0.0010 (11)
N2	0.0181 (15)	0.0162 (15)	0.0169 (14)	−0.0004 (11)	0.0021 (12)	−0.0025 (11)
C3	0.0170 (17)	0.0174 (18)	0.0195 (17)	−0.0017 (13)	0.0004 (14)	0.0008 (14)
C4	0.0185 (17)	0.0174 (17)	0.0180 (17)	0.0002 (13)	0.0027 (14)	0.0012 (13)
C5	0.0204 (18)	0.0173 (18)	0.0167 (16)	0.0000 (14)	0.0025 (14)	0.0013 (14)
C6	0.0232 (19)	0.0225 (19)	0.0213 (18)	−0.0015 (15)	0.0099 (15)	−0.0012 (14)
C7	0.0269 (19)	0.0192 (18)	0.0183 (17)	0.0005 (14)	0.0083 (15)	−0.0038 (14)
C8	0.0212 (18)	0.0158 (17)	0.0149 (16)	0.0025 (13)	0.0012 (14)	−0.0008 (13)
C9	0.0218 (18)	0.0150 (17)	0.0144 (16)	0.0019 (14)	0.0012 (14)	−0.0008 (13)
C10	0.0187 (17)	0.0184 (18)	0.0166 (16)	0.0002 (13)	0.0012 (14)	−0.0035 (13)
C11	0.0234 (19)	0.0170 (18)	0.0259 (19)	−0.0024 (14)	0.0035 (16)	−0.0070 (14)
C12	0.0235 (19)	0.0183 (18)	0.0274 (19)	−0.0060 (14)	0.0053 (16)	−0.0045 (15)
C13	0.0234 (18)	0.0172 (17)	0.0199 (17)	−0.0013 (14)	0.0062 (15)	−0.0020 (14)
S14	0.0309 (6)	0.0315 (6)	0.0306 (6)	−0.0069 (5)	0.0025 (5)	0.0047 (4)
C15	0.053 (3)	0.022 (2)	0.038 (2)	−0.0013 (19)	0.026 (2)	0.0044 (18)
C16	0.023 (2)	0.025 (2)	0.054 (3)	−0.0041 (16)	0.010 (2)	−0.0013 (19)
C17	0.0094 (14)	0.0086 (14)	0.0077 (13)	−0.0036 (11)	0.0036 (12)	0.0043 (11)
C18	0.0213 (18)	0.0160 (17)	0.0167 (16)	−0.0005 (14)	0.0041 (14)	−0.0038 (13)
S19	0.0333 (10)	0.0200 (9)	0.0139 (8)	−0.0001 (7)	−0.0010 (7)	−0.0057 (7)
C20	0.038 (2)	0.030 (2)	0.0183 (18)	−0.0086 (18)	0.0049 (17)	−0.0060 (16)
C21	0.034 (2)	0.027 (2)	0.027 (2)	0.0033 (17)	0.0160 (18)	0.0004 (16)
C22	0.129 (18)	0.14 (2)	0.103 (15)	−0.040 (15)	0.034 (14)	−0.039 (14)
C19	0.020 (9)	0.027 (5)	0.023 (4)	−0.009 (5)	0.009 (5)	−0.005 (4)
S22	0.0302 (10)	0.0258 (10)	0.0303 (10)	−0.0057 (8)	0.0119 (8)	−0.0152 (8)
Cu23	0.0162 (3)	0.0130 (3)	0.0138 (3)	−0.0009 (2)	0.0030 (2)	−0.0018 (2)

Geometric parameters (Å, º)

N1—C5	1.379 (6)	C13—C17	1.464 (6)
N1—C8	1.380 (6)	C13—S14	1.711 (5)
N1—Cu23	1.999 (4)	S14—C15	1.677 (6)
N2—C3	1.377 (6)	C15—C16	1.331 (9)
N2—C10^i	1.382 (6)	C15—H15	0.9500
N2—Cu23	2.012 (4)	C16—C17	1.425 (7)
C3—C4	1.390 (7)	C16—H16	0.9500
C3—C12^i	1.446 (6)	C17—H17	0.9500
C4—C5	1.396 (7)	C18—C19	1.496 (13)
C4—C13	1.478 (6)	C18—C22	1.433 (16)
C5—C6	1.438 (7)	C18—S22	1.666 (4)
C6—C7	1.350 (7)	C18—S19	1.696 (5)
C6—H6	0.9500	S19—C20	1.626 (6)
C7—C8	1.435 (7)	C20—C21	1.337 (8)
C7—H7	0.9500	C20—C19	1.610 (13)
C8—C9	1.398 (6)	C20—H20	0.9500
C9—C10	1.391 (7)	C21—S22	1.584 (5)
C9—C18	1.486 (6)	C21—C22	1.59 (2)
C10—N2^i	1.382 (6)	C21—H21	0.9500
C10—C11	1.436 (6)	C22—H22	0.9500
C11—C12	1.350 (7)	C19—H19	0.9500
C11—H11	0.9500	Cu23—N1^i	1.999 (4)
C12—C3^i	1.446 (6)	Cu23—N2^i	2.012 (4)
C12—H12	0.9500
C5—N1—C8	105.4 (4)	C15—S14—C13	93.6 (3)
C5—N1—Cu23	127.0 (3)	C16—C15—S14	112.5 (4)
C8—N1—Cu23	127.5 (3)	C16—C15—H15	123.7
C3—N2—C10^i	105.7 (4)	S14—C15—H15	123.7
C3—N2—Cu23	126.9 (3)	C15—C16—C17	115.6 (5)
C10^i—N2—Cu23	126.8 (3)	C15—C16—H16	122.2
N2—C3—C4	125.7 (4)	C17—C16—H16	122.2
N2—C3—C12^i	109.9 (4)	C16—C17—C13	108.5 (4)
C4—C3—C12^i	124.3 (4)	C16—C17—H17	125.7
C3—C4—C5	123.7 (4)	C13—C17—H17	125.7
C3—C4—C13	118.2 (4)	C19—C18—C22	113.6 (8)
C5—C4—C13	118.0 (4)	C19—C18—C9	122.2 (5)
N1—C5—C4	126.0 (4)	C22—C18—C9	124.2 (9)
N1—C5—C6	110.1 (4)	C19—C18—S22	114.5 (5)
C4—C5—C6	123.9 (4)	C9—C18—S22	123.3 (3)
C7—C6—C5	107.0 (4)	C22—C18—S19	114.9 (8)
C7—C6—H6	126.5	C9—C18—S19	120.9 (3)
C5—C6—H6	126.5	S22—C18—S19	115.8 (3)
C6—C7—C8	107.2 (4)	C20—S19—C18	92.9 (3)
C6—C7—H7	126.4	C21—C20—S19	117.5 (4)
C8—C7—H7	126.4	C21—C20—C19	110.4 (5)
N1—C8—C9	125.2 (4)	C21—C20—H20	121.3
N1—C8—C7	110.2 (4)	S19—C20—H20	121.3
C9—C8—C7	124.6 (4)	C19—C20—H20	128.3
C10—C9—C8	124.3 (4)	C20—C21—S22	118.7 (4)
C10—C9—C18	118.1 (4)	C20—C21—C22	110.3 (7)
C8—C9—C18	117.6 (4)	C20—C21—H21	124.9
N2^i—C10—C9	125.8 (4)	S22—C21—H21	116.4
N2^i—C10—C11	110.1 (4)	C22—C21—H21	124.9
C9—C10—C11	123.9 (4)	C18—C22—C21	104.1 (12)
C12—C11—C10	107.3 (4)	C18—C19—C20	101.6 (8)
C12—C11—H11	126.4	C21—S22—C18	94.6 (2)
C10—C11—H11	126.4	N1—Cu23—N1^i	179.998 (1)
C11—C12—C3^i	107.0 (4)	N1—Cu23—N2^i	90.08 (15)
C11—C12—H12	126.5	N1^i—Cu23—N2^i	89.92 (15)
C3^i—C12—H12	126.5	N1—Cu23—N2	89.92 (15)
C17—C13—C4	128.2 (4)	N1^i—Cu23—N2	90.08 (15)
C17—C13—S14	109.8 (3)	N2^i—Cu23—N2	180.0
C4—C13—S14	122.0 (3)

Symmetry code: (i) −x+1, −y, −z+1.