metal-organic compounds
Bis[2,3,4-trimethyl-5-[(3,4,5-trimethyl-2H-pyrrol-2-ylidene-κN)methyl]-1H-pyrrolato-κN]copper(II)†
aDepartment of Chemistry, Louisiana State University, Baton Rouge LA 70803-1804 USA
*Correspondence e-mail: ffroncz@lsu.edu
In the title complex, [Cu(C15H19N2)2] or [Cu(L2)] (HL is 3,3′,4,4′,5,5′-hexamethylpyrromethene), the CuII atom is coordinated by four N atoms [Cu—N 1.939 (2)–1.976 (2) Å] from two L ligands in a distorted tetrahedral geometry. The mean planes of the CuN2C3 metallocyclic rings form a dihedral angle of 72.73 (6)°. In the L ligands, the pyrrole rings are inclined to each other at dihedral angles of 3.03 (7) and 9.83 (7)°. The crystal packing exhibits weak intermolecular C—H⋯π interactions, which form chains in [100].
Related literature
For the structure of the neutral ligand, see: Mroginski et al. (2005). For the structures of related organometallic complexes, see: Elder & Penfold (1969); Cotton et al. (1970); Fergusson et al. (1971). For a description of the Cambridge Structural Database, see: Allen (2002). For transition metal complexes of see: Bruckner et al. (1997); Zhang et al. (1998). For the chemistry and applications of pyrrole derivatives, see: Dolphin (1979); Falk (1989). For the synthesis of the title compound, see: Murakami & Sakata (1968). For IDEAL software, see: Gould et al. (1988).
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Nonius, 2000); cell DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Supporting information
10.1107/S1600536812040998/cv5335sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812040998/cv5335Isup2.hkl
The title compound was synthesized by heating a suspension of dipyrromethene hydrochloride, copper acetate monohydrate and sodium acetate in ethanol-water (Murakami & Sakata, 1968).
H atoms were placed in calculated positions, guided by difference maps, with C—H bond distances 0.95–0.98 Å, Uiso = 1.2Ueq of the attached carbon atom (1.5 for methyl), and thereafter treated as riding. A torsional parameter was refined for each methyl group.
Data collection: COLLECT (Nonius, 2000); cell
DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).[Cu(C15H19N2)2] | Z = 2 |
Mr = 518.18 | F(000) = 550 |
Triclinic, P1 | Dx = 1.331 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9737 (1) Å | Cell parameters from 6313 reflections |
b = 12.0896 (3) Å | θ = 2.5–30° |
c = 13.9411 (4) Å | µ = 0.87 mm−1 |
α = 92.8065 (8)° | T = 120 K |
β = 105.4205 (8)° | Lath fragment, metallic green |
γ = 91.9772 (18)° | 0.18 × 0.10 × 0.02 mm |
V = 1292.39 (5) Å3 |
Nonius KappaCCD diffractometer | 7342 independent reflections |
Radiation source: sealed tube | 5581 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.052 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 2.6° |
ϕ and ω scans | h = −11→10 |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | k = −17→16 |
Tmin = 0.859, Tmax = 0.983 | l = 0→19 |
20968 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0459P)2 + 1.301P] where P = (Fo2 + 2Fc2)/3 |
7342 reflections | (Δ/σ)max = 0.001 |
328 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
0 constraints |
[Cu(C15H19N2)2] | γ = 91.9772 (18)° |
Mr = 518.18 | V = 1292.39 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9737 (1) Å | Mo Kα radiation |
b = 12.0896 (3) Å | µ = 0.87 mm−1 |
c = 13.9411 (4) Å | T = 120 K |
α = 92.8065 (8)° | 0.18 × 0.10 × 0.02 mm |
β = 105.4205 (8)° |
Nonius KappaCCD diffractometer | 7342 independent reflections |
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) | 5581 reflections with I > 2σ(I) |
Tmin = 0.859, Tmax = 0.983 | Rint = 0.052 |
20968 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.49 e Å−3 |
7342 reflections | Δρmin = −0.48 e Å−3 |
328 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0551 (3) | 0.30099 (19) | 0.06874 (18) | 0.0170 (4) | |
C2 | 0.1508 (3) | 0.3865 (2) | 0.03636 (18) | 0.0182 (5) | |
C3 | 0.2301 (3) | 0.45455 (19) | 0.11937 (18) | 0.0177 (5) | |
C4 | 0.1808 (3) | 0.41018 (18) | 0.20159 (18) | 0.0163 (4) | |
C5 | 0.2270 (3) | 0.45235 (19) | 0.30043 (18) | 0.0166 (4) | |
H5 | 0.293 | 0.521 | 0.313 | 0.02* | |
C6 | 0.1901 (3) | 0.40808 (18) | 0.38310 (18) | 0.0161 (4) | |
C7 | 0.2300 (3) | 0.45367 (19) | 0.48376 (18) | 0.0182 (5) | |
C8 | 0.1726 (3) | 0.3752 (2) | 0.53829 (18) | 0.0180 (5) | |
C9 | 0.0982 (3) | 0.28389 (19) | 0.47050 (18) | 0.0167 (4) | |
C10 | −0.0506 (3) | 0.2066 (2) | 0.00526 (19) | 0.0228 (5) | |
H10A | −0.0581 | 0.1444 | 0.0467 | 0.034* | |
H10B | 0.005 | 0.1832 | −0.0467 | 0.034* | |
H10C | −0.168 | 0.2302 | −0.0259 | 0.034* | |
C11 | 0.1629 (3) | 0.3977 (2) | −0.06840 (19) | 0.0246 (5) | |
H11A | 0.1608 | 0.4762 | −0.0831 | 0.037* | |
H11B | 0.064 | 0.3566 | −0.115 | 0.037* | |
H11C | 0.2719 | 0.3677 | −0.0755 | 0.037* | |
C12 | 0.3503 (4) | 0.5533 (2) | 0.1225 (2) | 0.0278 (6) | |
H12A | 0.4591 | 0.5289 | 0.1102 | 0.042* | |
H12B | 0.3756 | 0.5928 | 0.1882 | 0.042* | |
H12C | 0.295 | 0.603 | 0.0711 | 0.042* | |
C13 | 0.3121 (3) | 0.5663 (2) | 0.5217 (2) | 0.0239 (5) | |
H13A | 0.221 | 0.6179 | 0.5241 | 0.036* | |
H13B | 0.3791 | 0.5927 | 0.477 | 0.036* | |
H13C | 0.39 | 0.5619 | 0.5887 | 0.036* | |
C14 | 0.1815 (3) | 0.3850 (2) | 0.64745 (19) | 0.0273 (6) | |
H14A | 0.2834 | 0.4324 | 0.683 | 0.041* | |
H14B | 0.1911 | 0.3113 | 0.674 | 0.041* | |
H14C | 0.0756 | 0.4179 | 0.6565 | 0.041* | |
C15 | 0.0127 (3) | 0.1785 (2) | 0.49176 (19) | 0.0206 (5) | |
H15A | −0.1134 | 0.1864 | 0.4772 | 0.031* | |
H15B | 0.0591 | 0.1637 | 0.5621 | 0.031* | |
H15C | 0.0365 | 0.1169 | 0.4498 | 0.031* | |
C16 | 0.3462 (3) | 0.07330 (19) | 0.34173 (17) | 0.0149 (4) | |
C17 | 0.4012 (3) | −0.03756 (19) | 0.35150 (16) | 0.0155 (4) | |
C18 | 0.2537 (3) | −0.10652 (19) | 0.31410 (17) | 0.0152 (4) | |
C19 | 0.1112 (3) | −0.03552 (18) | 0.28089 (16) | 0.0133 (4) | |
C20 | −0.0604 (3) | −0.06651 (18) | 0.23318 (16) | 0.0146 (4) | |
H20 | −0.0881 | −0.1441 | 0.225 | 0.018* | |
C21 | −0.1988 (3) | 0.00086 (18) | 0.19539 (17) | 0.0150 (4) | |
C22 | −0.3776 (3) | −0.03267 (19) | 0.15404 (17) | 0.0161 (4) | |
C23 | −0.4672 (3) | 0.0633 (2) | 0.13321 (17) | 0.0169 (4) | |
C24 | −0.3418 (3) | 0.15334 (19) | 0.16063 (17) | 0.0169 (4) | |
C25 | 0.4632 (3) | 0.1757 (2) | 0.37120 (19) | 0.0205 (5) | |
H25A | 0.4076 | 0.2376 | 0.3343 | 0.031* | |
H25B | 0.5741 | 0.1632 | 0.3557 | 0.031* | |
H25C | 0.4844 | 0.1934 | 0.4429 | 0.031* | |
C26 | 0.5858 (3) | −0.0683 (2) | 0.39435 (18) | 0.0202 (5) | |
H26A | 0.5903 | −0.1491 | 0.3948 | 0.03* | |
H26B | 0.6288 | −0.0357 | 0.4627 | 0.03* | |
H26C | 0.6588 | −0.04 | 0.3536 | 0.03* | |
C27 | 0.2415 (3) | −0.23026 (19) | 0.3073 (2) | 0.0211 (5) | |
H27A | 0.3589 | −0.2584 | 0.3252 | 0.032* | |
H27B | 0.1806 | −0.257 | 0.239 | 0.032* | |
H27C | 0.1769 | −0.2566 | 0.3532 | 0.032* | |
C28 | −0.4551 (3) | −0.1488 (2) | 0.13782 (19) | 0.0221 (5) | |
H28A | −0.5556 | −0.1535 | 0.1656 | 0.033* | |
H28B | −0.3677 | −0.1995 | 0.171 | 0.033* | |
H28C | −0.4927 | −0.1695 | 0.0662 | 0.033* | |
C29 | −0.6605 (3) | 0.0712 (2) | 0.09145 (19) | 0.0234 (5) | |
H29A | −0.6925 | 0.0522 | 0.0195 | 0.035* | |
H29B | −0.693 | 0.147 | 0.1037 | 0.035* | |
H29C | −0.7221 | 0.0196 | 0.1239 | 0.035* | |
C30 | −0.3737 (3) | 0.2739 (2) | 0.1535 (2) | 0.0235 (5) | |
H30A | −0.3121 | 0.314 | 0.2165 | 0.035* | |
H30B | −0.4989 | 0.2846 | 0.1402 | 0.035* | |
H30C | −0.331 | 0.3023 | 0.0993 | 0.035* | |
N1 | 0.0723 (2) | 0.31450 (16) | 0.16751 (15) | 0.0158 (4) | |
N2 | 0.1078 (2) | 0.30305 (15) | 0.37825 (14) | 0.0150 (4) | |
N3 | 0.1743 (2) | 0.07482 (15) | 0.30066 (14) | 0.0141 (4) | |
N4 | −0.1810 (2) | 0.11631 (16) | 0.19835 (15) | 0.0154 (4) | |
Cu1 | 0.03402 (3) | 0.20344 (2) | 0.25992 (2) | 0.01496 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0148 (10) | 0.0179 (11) | 0.0179 (11) | 0.0046 (8) | 0.0028 (8) | 0.0022 (9) |
C2 | 0.0173 (11) | 0.0181 (11) | 0.0208 (12) | 0.0059 (8) | 0.0071 (9) | 0.0030 (9) |
C3 | 0.0178 (11) | 0.0155 (11) | 0.0209 (12) | 0.0026 (8) | 0.0063 (9) | 0.0036 (9) |
C4 | 0.0165 (11) | 0.0118 (10) | 0.0217 (12) | 0.0026 (8) | 0.0064 (8) | 0.0034 (9) |
C5 | 0.0148 (10) | 0.0116 (10) | 0.0223 (12) | 0.0016 (8) | 0.0028 (8) | 0.0012 (9) |
C6 | 0.0146 (10) | 0.0118 (10) | 0.0202 (12) | 0.0015 (8) | 0.0019 (8) | 0.0008 (9) |
C7 | 0.0151 (11) | 0.0169 (11) | 0.0208 (12) | 0.0030 (8) | 0.0018 (8) | −0.0012 (9) |
C8 | 0.0159 (11) | 0.0203 (12) | 0.0166 (11) | 0.0027 (8) | 0.0026 (8) | −0.0009 (9) |
C9 | 0.0126 (10) | 0.0179 (11) | 0.0193 (12) | 0.0041 (8) | 0.0027 (8) | 0.0033 (9) |
C10 | 0.0208 (12) | 0.0254 (13) | 0.0203 (13) | −0.0014 (9) | 0.0030 (9) | −0.0015 (10) |
C11 | 0.0264 (13) | 0.0280 (14) | 0.0229 (13) | 0.0025 (10) | 0.0117 (10) | 0.0067 (11) |
C12 | 0.0325 (14) | 0.0204 (13) | 0.0333 (15) | −0.0065 (10) | 0.0147 (11) | 0.0030 (11) |
C13 | 0.0266 (13) | 0.0182 (12) | 0.0233 (13) | −0.0004 (9) | 0.0016 (10) | −0.0059 (10) |
C14 | 0.0287 (14) | 0.0321 (15) | 0.0194 (13) | −0.0012 (11) | 0.0044 (10) | −0.0015 (11) |
C15 | 0.0218 (12) | 0.0202 (12) | 0.0211 (12) | 0.0001 (9) | 0.0080 (9) | 0.0025 (10) |
C16 | 0.0157 (10) | 0.0170 (11) | 0.0126 (10) | 0.0000 (8) | 0.0053 (8) | −0.0003 (8) |
C17 | 0.0187 (11) | 0.0186 (11) | 0.0104 (10) | 0.0029 (8) | 0.0057 (8) | 0.0017 (8) |
C18 | 0.0193 (11) | 0.0141 (10) | 0.0132 (11) | 0.0019 (8) | 0.0058 (8) | 0.0016 (8) |
C19 | 0.0150 (10) | 0.0126 (10) | 0.0126 (10) | 0.0011 (8) | 0.0042 (8) | 0.0015 (8) |
C20 | 0.0193 (11) | 0.0133 (10) | 0.0131 (10) | −0.0014 (8) | 0.0080 (8) | 0.0003 (8) |
C21 | 0.0173 (11) | 0.0150 (11) | 0.0128 (11) | −0.0013 (8) | 0.0044 (8) | 0.0005 (8) |
C22 | 0.0165 (11) | 0.0197 (11) | 0.0126 (11) | −0.0027 (8) | 0.0057 (8) | −0.0017 (9) |
C23 | 0.0139 (11) | 0.0246 (12) | 0.0120 (11) | 0.0003 (8) | 0.0034 (8) | −0.0001 (9) |
C24 | 0.0172 (11) | 0.0191 (11) | 0.0146 (11) | 0.0030 (8) | 0.0042 (8) | 0.0014 (9) |
C25 | 0.0164 (11) | 0.0206 (12) | 0.0235 (13) | −0.0031 (9) | 0.0048 (9) | −0.0015 (10) |
C26 | 0.0183 (11) | 0.0258 (13) | 0.0166 (12) | 0.0058 (9) | 0.0039 (9) | 0.0028 (10) |
C27 | 0.0240 (12) | 0.0149 (11) | 0.0262 (13) | 0.0051 (9) | 0.0091 (10) | 0.0028 (10) |
C28 | 0.0174 (11) | 0.0235 (13) | 0.0235 (13) | −0.0063 (9) | 0.0037 (9) | −0.0030 (10) |
C29 | 0.0168 (12) | 0.0332 (14) | 0.0200 (12) | 0.0023 (10) | 0.0046 (9) | 0.0010 (11) |
C30 | 0.0227 (12) | 0.0205 (12) | 0.0270 (14) | 0.0047 (9) | 0.0054 (10) | 0.0030 (10) |
N1 | 0.0166 (9) | 0.0128 (9) | 0.0174 (10) | 0.0012 (7) | 0.0032 (7) | 0.0025 (7) |
N2 | 0.0142 (9) | 0.0142 (9) | 0.0155 (10) | 0.0008 (7) | 0.0024 (7) | 0.0001 (7) |
N3 | 0.0151 (9) | 0.0130 (9) | 0.0145 (9) | 0.0002 (7) | 0.0045 (7) | 0.0005 (7) |
N4 | 0.0144 (9) | 0.0139 (9) | 0.0175 (10) | 0.0009 (7) | 0.0035 (7) | 0.0018 (7) |
Cu1 | 0.01634 (14) | 0.01081 (13) | 0.01597 (15) | −0.00039 (9) | 0.00133 (10) | 0.00120 (10) |
C1—N1 | 1.348 (3) | C16—C25 | 1.496 (3) |
C1—C2 | 1.425 (3) | C17—C18 | 1.384 (3) |
C1—C10 | 1.495 (3) | C17—C26 | 1.501 (3) |
C2—C3 | 1.378 (3) | C18—C19 | 1.438 (3) |
C2—C11 | 1.501 (4) | C18—C27 | 1.493 (3) |
C3—C4 | 1.429 (3) | C19—C20 | 1.383 (3) |
C3—C12 | 1.497 (3) | C19—N3 | 1.397 (3) |
C4—C5 | 1.394 (3) | C20—C21 | 1.397 (3) |
C4—N1 | 1.404 (3) | C20—H20 | 0.95 |
C5—C6 | 1.390 (3) | C21—N4 | 1.395 (3) |
C5—H5 | 0.95 | C21—C22 | 1.425 (3) |
C6—N2 | 1.399 (3) | C22—C23 | 1.386 (3) |
C6—C7 | 1.431 (3) | C22—C28 | 1.496 (3) |
C7—C8 | 1.384 (3) | C23—C24 | 1.418 (3) |
C7—C13 | 1.499 (3) | C23—C29 | 1.504 (3) |
C8—C9 | 1.420 (3) | C24—N4 | 1.351 (3) |
C8—C14 | 1.503 (4) | C24—C30 | 1.492 (3) |
C9—N2 | 1.339 (3) | C25—H25A | 0.98 |
C9—C15 | 1.503 (3) | C25—H25B | 0.98 |
C10—H10A | 0.98 | C25—H25C | 0.98 |
C10—H10B | 0.98 | C26—H26A | 0.98 |
C10—H10C | 0.98 | C26—H26B | 0.98 |
C11—H11A | 0.98 | C26—H26C | 0.98 |
C11—H11B | 0.98 | C27—H27A | 0.98 |
C11—H11C | 0.98 | C27—H27B | 0.98 |
C12—H12A | 0.98 | C27—H27C | 0.98 |
C12—H12B | 0.98 | C28—H28A | 0.98 |
C12—H12C | 0.98 | C28—H28B | 0.98 |
C13—H13A | 0.98 | C28—H28C | 0.98 |
C13—H13B | 0.98 | C29—H29A | 0.98 |
C13—H13C | 0.98 | C29—H29B | 0.98 |
C14—H14A | 0.98 | C29—H29C | 0.98 |
C14—H14B | 0.98 | C30—H30A | 0.98 |
C14—H14C | 0.98 | C30—H30B | 0.98 |
C15—H15A | 0.98 | C30—H30C | 0.98 |
C15—H15B | 0.98 | N1—Cu1 | 1.9762 (19) |
C15—H15C | 0.98 | N2—Cu1 | 1.9385 (19) |
C16—N3 | 1.339 (3) | N3—Cu1 | 1.9650 (19) |
C16—C17 | 1.426 (3) | N4—Cu1 | 1.9471 (19) |
N1—C1—C2 | 110.9 (2) | C20—C19—N3 | 123.4 (2) |
N1—C1—C10 | 122.6 (2) | C20—C19—C18 | 127.7 (2) |
C2—C1—C10 | 126.5 (2) | N3—C19—C18 | 108.78 (18) |
C3—C2—C1 | 106.8 (2) | C19—C20—C21 | 128.7 (2) |
C3—C2—C11 | 127.4 (2) | C19—C20—H20 | 115.6 |
C1—C2—C11 | 125.8 (2) | C21—C20—H20 | 115.6 |
C2—C3—C4 | 106.9 (2) | N4—C21—C20 | 123.4 (2) |
C2—C3—C12 | 126.1 (2) | N4—C21—C22 | 108.86 (19) |
C4—C3—C12 | 127.0 (2) | C20—C21—C22 | 127.6 (2) |
C5—C4—N1 | 123.5 (2) | C23—C22—C21 | 106.8 (2) |
C5—C4—C3 | 127.6 (2) | C23—C22—C28 | 126.4 (2) |
N1—C4—C3 | 108.9 (2) | C21—C22—C28 | 126.8 (2) |
C6—C5—C4 | 129.1 (2) | C22—C23—C24 | 106.8 (2) |
C6—C5—H5 | 115.5 | C22—C23—C29 | 126.8 (2) |
C4—C5—H5 | 115.5 | C24—C23—C29 | 126.4 (2) |
C5—C6—N2 | 122.2 (2) | N4—C24—C23 | 110.6 (2) |
C5—C6—C7 | 129.2 (2) | N4—C24—C30 | 122.1 (2) |
N2—C6—C7 | 108.6 (2) | C23—C24—C30 | 127.3 (2) |
C8—C7—C6 | 106.7 (2) | C16—C25—H25A | 109.5 |
C8—C7—C13 | 126.8 (2) | C16—C25—H25B | 109.5 |
C6—C7—C13 | 126.5 (2) | H25A—C25—H25B | 109.5 |
C7—C8—C9 | 106.7 (2) | C16—C25—H25C | 109.5 |
C7—C8—C14 | 127.0 (2) | H25A—C25—H25C | 109.5 |
C9—C8—C14 | 126.2 (2) | H25B—C25—H25C | 109.5 |
N2—C9—C8 | 110.9 (2) | C17—C26—H26A | 109.5 |
N2—C9—C15 | 121.2 (2) | C17—C26—H26B | 109.5 |
C8—C9—C15 | 127.9 (2) | H26A—C26—H26B | 109.5 |
C1—C10—H10A | 109.5 | C17—C26—H26C | 109.5 |
C1—C10—H10B | 109.5 | H26A—C26—H26C | 109.5 |
H10A—C10—H10B | 109.5 | H26B—C26—H26C | 109.5 |
C1—C10—H10C | 109.5 | C18—C27—H27A | 109.5 |
H10A—C10—H10C | 109.5 | C18—C27—H27B | 109.5 |
H10B—C10—H10C | 109.5 | H27A—C27—H27B | 109.5 |
C2—C11—H11A | 109.5 | C18—C27—H27C | 109.5 |
C2—C11—H11B | 109.5 | H27A—C27—H27C | 109.5 |
H11A—C11—H11B | 109.5 | H27B—C27—H27C | 109.5 |
C2—C11—H11C | 109.5 | C22—C28—H28A | 109.5 |
H11A—C11—H11C | 109.5 | C22—C28—H28B | 109.5 |
H11B—C11—H11C | 109.5 | H28A—C28—H28B | 109.5 |
C3—C12—H12A | 109.5 | C22—C28—H28C | 109.5 |
C3—C12—H12B | 109.5 | H28A—C28—H28C | 109.5 |
H12A—C12—H12B | 109.5 | H28B—C28—H28C | 109.5 |
C3—C12—H12C | 109.5 | C23—C29—H29A | 109.5 |
H12A—C12—H12C | 109.5 | C23—C29—H29B | 109.5 |
H12B—C12—H12C | 109.5 | H29A—C29—H29B | 109.5 |
C7—C13—H13A | 109.5 | C23—C29—H29C | 109.5 |
C7—C13—H13B | 109.5 | H29A—C29—H29C | 109.5 |
H13A—C13—H13B | 109.5 | H29B—C29—H29C | 109.5 |
C7—C13—H13C | 109.5 | C24—C30—H30A | 109.5 |
H13A—C13—H13C | 109.5 | C24—C30—H30B | 109.5 |
H13B—C13—H13C | 109.5 | H30A—C30—H30B | 109.5 |
C8—C14—H14A | 109.5 | C24—C30—H30C | 109.5 |
C8—C14—H14B | 109.5 | H30A—C30—H30C | 109.5 |
H14A—C14—H14B | 109.5 | H30B—C30—H30C | 109.5 |
C8—C14—H14C | 109.5 | C1—N1—C4 | 106.43 (19) |
H14A—C14—H14C | 109.5 | C1—N1—Cu1 | 128.71 (16) |
H14B—C14—H14C | 109.5 | C4—N1—Cu1 | 121.56 (15) |
C9—C15—H15A | 109.5 | C9—N2—C6 | 107.10 (19) |
C9—C15—H15B | 109.5 | C9—N2—Cu1 | 127.50 (16) |
H15A—C15—H15B | 109.5 | C6—N2—Cu1 | 125.33 (16) |
C9—C15—H15C | 109.5 | C16—N3—C19 | 106.97 (18) |
H15A—C15—H15C | 109.5 | C16—N3—Cu1 | 128.25 (15) |
H15B—C15—H15C | 109.5 | C19—N3—Cu1 | 124.45 (14) |
N3—C16—C17 | 111.2 (2) | C24—N4—C21 | 106.98 (18) |
N3—C16—C25 | 123.5 (2) | C24—N4—Cu1 | 127.95 (16) |
C17—C16—C25 | 125.3 (2) | C21—N4—Cu1 | 124.74 (15) |
C18—C17—C16 | 106.57 (19) | N2—Cu1—N4 | 133.10 (8) |
C18—C17—C26 | 128.8 (2) | N2—Cu1—N3 | 101.81 (8) |
C16—C17—C26 | 124.7 (2) | N4—Cu1—N3 | 95.11 (8) |
C17—C18—C19 | 106.50 (19) | N2—Cu1—N1 | 95.00 (8) |
C17—C18—C27 | 127.7 (2) | N4—Cu1—N1 | 109.25 (8) |
C19—C18—C27 | 125.8 (2) | N3—Cu1—N1 | 126.54 (8) |
N1—C1—C2—C3 | 0.3 (3) | C2—C1—N1—C4 | 0.0 (2) |
C10—C1—C2—C3 | −179.1 (2) | C10—C1—N1—C4 | 179.4 (2) |
N1—C1—C2—C11 | 179.5 (2) | C2—C1—N1—Cu1 | −159.31 (16) |
C10—C1—C2—C11 | 0.2 (4) | C10—C1—N1—Cu1 | 20.1 (3) |
C1—C2—C3—C4 | −0.4 (2) | C5—C4—N1—C1 | 179.0 (2) |
C11—C2—C3—C4 | −179.7 (2) | C3—C4—N1—C1 | −0.3 (2) |
C1—C2—C3—C12 | 177.4 (2) | C5—C4—N1—Cu1 | −19.9 (3) |
C11—C2—C3—C12 | −1.8 (4) | C3—C4—N1—Cu1 | 160.86 (15) |
C2—C3—C4—C5 | −178.8 (2) | C8—C9—N2—C6 | 0.2 (2) |
C12—C3—C4—C5 | 3.4 (4) | C15—C9—N2—C6 | 178.6 (2) |
C2—C3—C4—N1 | 0.4 (3) | C8—C9—N2—Cu1 | 177.39 (15) |
C12—C3—C4—N1 | −177.4 (2) | C15—C9—N2—Cu1 | −4.3 (3) |
N1—C4—C5—C6 | 5.1 (4) | C5—C6—N2—C9 | 177.6 (2) |
C3—C4—C5—C6 | −175.8 (2) | C7—C6—N2—C9 | −0.5 (2) |
C4—C5—C6—N2 | 5.8 (4) | C5—C6—N2—Cu1 | 0.3 (3) |
C4—C5—C6—C7 | −176.6 (2) | C7—C6—N2—Cu1 | −177.68 (14) |
C5—C6—C7—C8 | −177.3 (2) | C17—C16—N3—C19 | −0.8 (3) |
N2—C6—C7—C8 | 0.5 (2) | C25—C16—N3—C19 | 178.2 (2) |
C5—C6—C7—C13 | 4.7 (4) | C17—C16—N3—Cu1 | −174.31 (15) |
N2—C6—C7—C13 | −177.5 (2) | C25—C16—N3—Cu1 | 4.6 (3) |
C6—C7—C8—C9 | −0.3 (2) | C20—C19—N3—C16 | −176.4 (2) |
C13—C7—C8—C9 | 177.6 (2) | C18—C19—N3—C16 | 1.2 (2) |
C6—C7—C8—C14 | −178.6 (2) | C20—C19—N3—Cu1 | −2.5 (3) |
C13—C7—C8—C14 | −0.6 (4) | C18—C19—N3—Cu1 | 175.09 (15) |
C7—C8—C9—N2 | 0.1 (3) | C23—C24—N4—C21 | 0.5 (3) |
C14—C8—C9—N2 | 178.3 (2) | C30—C24—N4—C21 | 179.0 (2) |
C7—C8—C9—C15 | −178.1 (2) | C23—C24—N4—Cu1 | −173.08 (16) |
C14—C8—C9—C15 | 0.2 (4) | C30—C24—N4—Cu1 | 5.5 (3) |
N3—C16—C17—C18 | 0.0 (3) | C20—C21—N4—C24 | −176.6 (2) |
C25—C16—C17—C18 | −178.9 (2) | C22—C21—N4—C24 | 0.1 (3) |
N3—C16—C17—C26 | 179.8 (2) | C20—C21—N4—Cu1 | −2.8 (3) |
C25—C16—C17—C26 | 0.8 (4) | C22—C21—N4—Cu1 | 173.90 (15) |
C16—C17—C18—C19 | 0.8 (2) | C9—N2—Cu1—N4 | 50.3 (2) |
C26—C17—C18—C19 | −179.0 (2) | C6—N2—Cu1—N4 | −133.06 (17) |
C16—C17—C18—C27 | 179.9 (2) | C9—N2—Cu1—N3 | −58.40 (19) |
C26—C17—C18—C27 | 0.2 (4) | C6—N2—Cu1—N3 | 118.25 (18) |
C17—C18—C19—C20 | 176.2 (2) | C9—N2—Cu1—N1 | 172.63 (18) |
C27—C18—C19—C20 | −3.0 (4) | C6—N2—Cu1—N1 | −10.71 (18) |
C17—C18—C19—N3 | −1.2 (3) | C24—N4—Cu1—N2 | 62.3 (2) |
C27—C18—C19—N3 | 179.6 (2) | C21—N4—Cu1—N2 | −110.21 (19) |
N3—C19—C20—C21 | 1.0 (4) | C24—N4—Cu1—N3 | 173.7 (2) |
C18—C19—C20—C21 | −176.1 (2) | C21—N4—Cu1—N3 | 1.21 (19) |
C19—C20—C21—N4 | 1.9 (4) | C24—N4—Cu1—N1 | −54.6 (2) |
C19—C20—C21—C22 | −174.2 (2) | C21—N4—Cu1—N1 | 132.85 (18) |
N4—C21—C22—C23 | −0.6 (3) | C16—N3—Cu1—N2 | −50.2 (2) |
C20—C21—C22—C23 | 175.9 (2) | C19—N3—Cu1—N2 | 137.32 (18) |
N4—C21—C22—C28 | −179.6 (2) | C16—N3—Cu1—N4 | 173.8 (2) |
C20—C21—C22—C28 | −3.0 (4) | C19—N3—Cu1—N4 | 1.31 (19) |
C21—C22—C23—C24 | 0.9 (3) | C16—N3—Cu1—N1 | 55.3 (2) |
C28—C22—C23—C24 | 179.8 (2) | C19—N3—Cu1—N1 | −117.27 (18) |
C21—C22—C23—C29 | −178.0 (2) | C1—N1—Cu1—N2 | 176.26 (19) |
C28—C22—C23—C29 | 0.9 (4) | C4—N1—Cu1—N2 | 19.68 (18) |
C22—C23—C24—N4 | −0.9 (3) | C1—N1—Cu1—N4 | −44.5 (2) |
C29—C23—C24—N4 | 178.1 (2) | C4—N1—Cu1—N4 | 158.88 (16) |
C22—C23—C24—C30 | −179.3 (2) | C1—N1—Cu1—N3 | 67.6 (2) |
C29—C23—C24—C30 | −0.4 (4) | C4—N1—Cu1—N3 | −89.01 (19) |
Cg is the centroid of the N3/C16–C19 pyrrole ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C29—H29C···Cgi | 0.98 | 2.78 | 3.551 (3) | 136 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C15H19N2)2] |
Mr | 518.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 7.9737 (1), 12.0896 (3), 13.9411 (4) |
α, β, γ (°) | 92.8065 (8), 105.4205 (8), 91.9772 (18) |
V (Å3) | 1292.39 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.18 × 0.10 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.859, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20968, 7342, 5581 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.117, 1.02 |
No. of reflections | 7342 |
No. of parameters | 328 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.48 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
Cg is the centroid of the N3/C16–C19 pyrrole ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C29—H29C···Cgi | 0.98 | 2.78 | 3.551 (3) | 136 |
Symmetry code: (i) x−1, y, z. |
Acknowledgements
Purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Dipyrromethenes are fully conjugated anionic ligands which create stable transition metal complexes (Bruckner et al., 1997, Zhang et al., 1998). The high chemical stability of the title compound (I) is associated with its extended aromatic structure. Pyrroles also form crucial building blocks for bile pigments, linear polypyrroles and porphyrins, and have been investigated for treatment of cancer by photodynamic therapy (Dolphin, 1979; Falk, 1989).
The structure of the neutral protonated ligand, C15H20N2, has been determined (Mroginski et al., 2005, CCDC refcode PALFEO, Allen, 2002). Comparison of the ligated anions in I with the neutral species shows excellent structural coincidence for all non-hydrogen atoms, with δr.m.s. = 0.091 Å (IDEAL, Gould et al., 1988).
Intermolecular interactions include weak C—H···π contacts involving methyl group C15 and the pyrrole ring N3/C16-C19 (Table 1), thus forming chains in the [100] direction.