Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011308/cv6036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011308/cv6036Isup2.hkl |
CCDC reference: 170866
Key indicators
- Single-crystal X-ray study
- T = 110 K
- Mean (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
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).
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.
[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) Å3 | Prism, dark-blue |
Z = 2 | 0.35 × 0.20 × 0.15 mm |
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 on F2 | 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[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0554P)2 + 6.3287P] where P = (Fo2 + 2Fc2)/3 |
2587 reflections | (Δ/σ)max = 0.118 |
223 parameters | Δρmax = 0.88 e Å−3 |
1 restraint | Δρmin = −0.78 e Å−3 |
[Cu(C36H20N4S4)] | V = 1469.06 (7) Å3 |
Mr = 700.34 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.5550 (2) Å | µ = 1.06 mm−1 |
b = 10.9180 (3) Å | T = 110 K |
c = 20.5590 (6) Å | 0.35 × 0.20 × 0.15 mm |
β = 93.2030 (15)° |
Nonius KappaCCD diffractometer | 2587 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2307 reflections with I > 2σ(I) |
Tmin = 0.707, Tmax = 0.857 | Rint = 0.038 |
4433 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.98 | (Δ/σ)max = 0.118 |
2587 reflections | Δρmax = 0.88 e Å−3 |
223 parameters | Δρmin = −0.78 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—C10i | 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—C12i | 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—N2i | 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—N1i | 1.999 (4) |
C12—C3i | 1.446 (6) | Cu23—N2i | 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—C10i | 105.7 (4) | S14—C15—H15 | 123.7 |
C3—N2—Cu23 | 126.9 (3) | C15—C16—C17 | 115.6 (5) |
C10i—N2—Cu23 | 126.8 (3) | C15—C16—H16 | 122.2 |
N2—C3—C4 | 125.7 (4) | C17—C16—H16 | 122.2 |
N2—C3—C12i | 109.9 (4) | C16—C17—C13 | 108.5 (4) |
C4—C3—C12i | 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 |
N2i—C10—C9 | 125.8 (4) | S22—C21—H21 | 116.4 |
N2i—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—N1i | 179.998 (1) |
C11—C12—C3i | 107.0 (4) | N1—Cu23—N2i | 90.08 (15) |
C11—C12—H12 | 126.5 | N1i—Cu23—N2i | 89.92 (15) |
C3i—C12—H12 | 126.5 | N1—Cu23—N2 | 89.92 (15) |
C17—C13—C4 | 128.2 (4) | N1i—Cu23—N2 | 90.08 (15) |
C17—C13—S14 | 109.8 (3) | N2i—Cu23—N2 | 180.0 |
C4—C13—S14 | 122.0 (3) |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C36H20N4S4)] |
Mr | 700.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 110 |
a, b, c (Å) | 6.5550 (2), 10.9180 (3), 20.5590 (6) |
β (°) | 93.2030 (15) |
V (Å3) | 1469.06 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.707, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4433, 2587, 2307 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.130, 0.98 |
No. of reflections | 2587 |
No. of parameters | 223 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
(Δ/σ)max | 0.118 |
Δρmax, Δρmin (e Å−3) | 0.88, −0.78 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski, 1985), DENZO, DIRDIF96 (Beurskens et al., 1996), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
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 CuI and AgI 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.