Bis[2,3,4-trimethyl-5-[(3,4,5-trimethyl-2H-pyrrol-2-yl­idene-κN)meth­yl]-1H-pyrrolato-κN]copper(II)

Erdem, S.S.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812040998

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1335-m1336

doi:10.1107/S1600536812040998

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Bis[2,3,4-trimethyl-5-[(3,4,5-trimethyl-2H-pyrrol-2-ylidene-κN)methyl]-1H-pyrrolato-κN]copper(II)†

Sultan S. Erdem,^a ‡ Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge LA 70803-1804 USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 27 August 2012; accepted 28 September 2012; online 6 October 2012)

In the title complex, [Cu(C₁₅H₁₉N₂)₂] or [Cu(L₂)] (HL is 3,3′,4,4′,5,5′-hexamethylpyrromethene), the Cu^II 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 dipyrromethenes, 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

[Cu(C₁₅H₁₉N₂)₂]
M_r = 518.18
Triclinic, $[P \overline 1]$
a = 7.9737 (1) Å
b = 12.0896 (3) Å
c = 13.9411 (4) Å
α = 92.8065 (8)°
β = 105.4205 (8)°
γ = 91.9772 (18)°
V = 1292.39 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 120 K
0.18 × 0.10 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.859, T_max = 0.983
20968 measured reflections
7342 independent reflections
5581 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.117
S = 1.02
7342 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812040998/cv5335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812040998/cv5335Isup2.hkl

checkCIF report

Comment top

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 δ_r.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.

Related literature top

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 dipyrromethenes, 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 top

The title compound was synthesized by heating a suspension of dipyrromethene hydrochloride, copper acetate monohydrate and sodium acetate in ethanol-water (Murakami & Sakata, 1968).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: 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).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids). H atoms are not shown.

Bis[2,3,4-trimethyl-5-[(3,4,5-trimethyl-2H-pyrrol-2-ylidene-κN)methyl]-1H-pyrrolato-κN]copper(II) top

Crystal data top

[Cu(C₁₅H₁₉N₂)₂]	Z = 2
M_r = 518.18	F(000) = 550
Triclinic, P1	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	7342 independent reflections
Radiation source: sealed tube	5581 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.052
Detector resolution: 9 pixels mm^-1	θ_max = 30.0°, θ_min = 2.6°
ϕ and ω scans	h = −11→10
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	k = −17→16
T_min = 0.859, T_max = 0.983	l = 0→19
20968 measured reflections

Refinement top

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(F_o²) + (0.0459P)² + 1.301P] where P = (F_o² + 2F_c²)/3
7342 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³
0 constraints

Crystal data top

[Cu(C₁₅H₁₉N₂)₂]	γ = 91.9772 (18)°
M_r = 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)°

Data collection top

Nonius KappaCCD diffractometer	7342 independent reflections
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	5581 reflections with I > 2σ(I)
T_min = 0.859, T_max = 0.983	R_int = 0.052
20968 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.02	Δρ_max = 0.49 e Å⁻³
7342 reflections	Δρ_min = −0.48 e Å⁻³
328 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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]
M_r	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)
T_min, T_max	0.859, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	20968, 7342, 5581
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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.

Footnotes

†CAS 38504-29-9 and 21710-26-9.

‡Current address: Center for Systems Biology, Massachusetts General Hospital and Harvard Medical School, 185 Cambridge St, Suite 5.210, Boston, MA 02114, USA.

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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Volume 68| Part 11| November 2012| Pages m1335-m1336

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis[2,3,4-tri­methyl-5-[(3,4,5-tri­methyl-2H-pyrrol-2-yl­­idene-κN)meth­yl]-1H-pyrrolato-κN]copper(II)†

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

metal-organic compounds

Bis[2,3,4-trimethyl-5-[(3,4,5-trimethyl-2H-pyrrol-2-ylidene-κN)methyl]-1H-pyrrolato-κN]copper(II)†