Bis[(1-vinyl-1H-imidazol-2-yl-κN ³)methanamine-κN]copper(II) bis­(hexa­fluoridophosphate)

Abstract

In the title compound, [Cu(C₆H₉N₃)₂](PF₆)₂, the Cu atom is located on a crystallographic center of inversion. The coordination environment of the Cu atom is square-planar with two amino and two imidazole N atoms bonded to the metal in a trans configuration.

Related literature

For the title ligand as a building block for tripodal tetra­amine ligands, see: Blackman (2005 ▶). For catalytic activity of copper(II) complexes with similar mulidendate N-donor ligands, see: Schiller et al. (2005 ▶, 2006 ▶).

Experimental

Crystal data

• [Cu(C₆H₉N₃)₂](PF₆)₂

• M _r = 599.80

• Monoclinic,

• a = 11.543 (2) Å

• b = 12.282 (2) Å

• c = 8.2793 (14) Å

• β = 96.476 (15)°

• V = 1166.3 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 1.18 mm⁻¹

• T = 140 K

• 0.24 × 0.20 × 0.16 mm

Data collection

• Oxford Diffraction KM-4/Sapphire CCD diffractometer

• Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.657, T _max = 1.000

• 6439 measured reflections

• 1955 independent reflections

• 1396 reflections with I > 2σ(I)

• R _int = 0.088

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.123

• S = 0.97

• 1955 reflections

• 151 parameters

• H-atom parameters constrained

• Δρ_max = 0.91 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: ORTEP-3 (Farrugia, 1997 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The described ligand has been used as a building block for the synthesis of the chelate ligand tris[(1-vinylimidazole-2-yl)methyl]amine (L). The complexes [Zn(L)Cl]PF₆ and [Cu(L)Cl]PF₆ were obtained upon reaction with L and immobilized by co-polymerization with ethylene glycol dimethacrylate. The supported complexes were found to be efficient heterogenous catalysts for the hydrolysis of bis(p-nitrophenyl)phosphate (Schiller et al., 2006).

The structure of the title compound feature Cu on an inversion centre (Wyckoff position 2a). Two ligands coordinate to it in a trans fashion (Fig. 1).

Experimental

Synthesis of the metal complex. Anhydrous copper(II) chloride (25.0 mg, 0.186 mmol) was added to a solution of (1-vinyl-1H-imidazol-2-yl)-methylamine (45.8 mg, 0.372 mmol) in ethanol (4 ml). NH₄PF₆ (60.6 mg, 0.372 mmol) was added and pink crystals were formed after 2 h. The product was isolated, washed with ethanol, and dried in a vacuum (yield: 83.7 mg, 75%). IR: ν (cm^-1) = 3368/3314/3205 (w, NH), 1652 (vs, CH=CH₂), 822 (vs, PF₆).

Refinement

Hydrogen atoms have been placed in calculated positions with C–H distances of 0.99Å for the methylene group and 0.95Å for all other hydrogen atoms bonded to carbon and 0.92Å for the amino function. Refinement was performed using a riding model with U_iso(H) = 1.2 U_eq(C).

Figures

Fig. 1.

Molecular structure of the title compound. Second ligand is created by (i): -x, -y, -z. Ellipsoids are depicted on the 50% probability level.

Crystal data

[Cu(C6H9N3)2](PF6)2	F(000) = 598
Mr = 599.80	Dx = 1.708 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3520 reflections
a = 11.543 (2) Å	θ = 2.4–26.6°
b = 12.282 (2) Å	µ = 1.18 mm−1
c = 8.2793 (14) Å	T = 140 K
β = 96.476 (15)°	Prismatic, pink
V = 1166.3 (4) Å3	0.24 × 0.20 × 0.16 mm
Z = 2

Data collection

Oxford Diffraction KM-4/Sapphire CCD diffractometer	1955 independent reflections
Radiation source: fine-focus sealed tube	1396 reflections with I > 2σ(I)
graphite	Rint = 0.088
φ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −13→13
Tmin = 0.657, Tmax = 1.000	k = −14→14
6439 measured reflections	l = −9→9

Refinement

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 0.97	w = 1/[σ2(Fo2) + (0.0677P)2] where P = (Fo2 + 2Fc2)/3
1955 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.91 e Å−3
0 restraints	Δρmin = −0.46 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.0000	0.0000	0.0000	0.0228 (2)
N1	0.1254 (3)	0.1059 (2)	−0.0384 (4)	0.0259 (8)
N2	0.3038 (3)	0.1375 (2)	−0.1192 (4)	0.0274 (8)
N3	0.1108 (3)	−0.1091 (2)	−0.0966 (4)	0.0266 (8)
H3A	0.1138	−0.1725	−0.0370	0.032*
H3B	0.0811	−0.1258	−0.2015	0.032*
C1	0.2219 (3)	0.0595 (3)	−0.0873 (5)	0.0222 (9)
C2	0.2538 (4)	0.2409 (3)	−0.0848 (6)	0.0315 (11)
H2	0.2886	0.3104	−0.0940	0.038*
C3	0.1460 (4)	0.2200 (3)	−0.0360 (5)	0.0296 (10)
H3	0.0933	0.2736	−0.0054	0.036*
C4	0.4149 (4)	0.1189 (3)	−0.1822 (5)	0.0316 (10)
H4	0.4311	0.0471	−0.2160	0.038*
C5	0.4952 (4)	0.1947 (4)	−0.1960 (7)	0.0474 (14)
H5A	0.4821	0.2675	−0.1634	0.057*
H5B	0.5658	0.1763	−0.2383	0.057*
C6	0.2332 (3)	−0.0645 (3)	−0.0967 (5)	0.0227 (9)
H6A	0.2661	−0.0860	−0.1974	0.027*
H6B	0.2847	−0.0924	−0.0021	0.027*
P1	0.19988 (10)	0.57233 (7)	0.90769 (13)	0.0244 (3)
F1	0.0883 (2)	0.51137 (19)	0.8082 (3)	0.0463 (8)
F2	0.2875 (2)	0.50369 (17)	0.8029 (3)	0.0392 (7)
F3	0.1923 (3)	0.66853 (17)	0.7698 (3)	0.0472 (8)
F4	0.3113 (2)	0.6338 (2)	1.0077 (3)	0.0531 (8)
F5	0.1112 (2)	0.64221 (17)	1.0131 (3)	0.0396 (7)
F6	0.2065 (2)	0.47717 (17)	1.0447 (3)	0.0365 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.0264 (4)	0.0165 (3)	0.0261 (5)	0.0009 (3)	0.0056 (3)	0.0002 (3)
N1	0.029 (2)	0.0210 (15)	0.028 (2)	0.0045 (14)	0.0070 (16)	−0.0020 (14)
N2	0.0282 (19)	0.0216 (16)	0.034 (2)	−0.0003 (14)	0.0092 (17)	−0.0042 (14)
N3	0.031 (2)	0.0185 (15)	0.031 (2)	−0.0002 (14)	0.0089 (17)	0.0000 (14)
C1	0.025 (2)	0.0223 (19)	0.020 (2)	−0.0004 (16)	0.0026 (19)	0.0021 (16)
C2	0.037 (3)	0.0180 (19)	0.041 (3)	−0.0049 (17)	0.010 (2)	−0.0024 (18)
C3	0.033 (2)	0.0182 (18)	0.039 (3)	0.0005 (17)	0.010 (2)	−0.0044 (17)
C4	0.029 (2)	0.032 (2)	0.035 (3)	0.0010 (19)	0.009 (2)	−0.0055 (19)
C5	0.031 (3)	0.043 (3)	0.070 (4)	−0.001 (2)	0.016 (3)	−0.008 (3)
C6	0.024 (2)	0.0181 (19)	0.027 (2)	0.0029 (15)	0.0081 (19)	0.0022 (16)
P1	0.0330 (6)	0.0177 (5)	0.0230 (6)	−0.0002 (4)	0.0053 (5)	−0.0003 (4)
F1	0.0429 (17)	0.0558 (17)	0.0388 (18)	−0.0141 (13)	−0.0018 (14)	−0.0081 (13)
F2	0.0548 (18)	0.0329 (13)	0.0336 (16)	0.0120 (12)	0.0212 (14)	−0.0019 (11)
F3	0.084 (2)	0.0240 (12)	0.0376 (17)	0.0114 (13)	0.0255 (15)	0.0086 (11)
F4	0.0495 (17)	0.0613 (17)	0.050 (2)	−0.0274 (14)	0.0112 (15)	−0.0192 (14)
F5	0.0579 (17)	0.0311 (12)	0.0329 (16)	0.0117 (12)	0.0193 (13)	−0.0003 (11)
F6	0.0568 (18)	0.0257 (12)	0.0277 (15)	0.0051 (11)	0.0080 (14)	0.0052 (10)

Geometric parameters (Å, °)

Cu1—N1	1.998 (3)	C2—H2	0.9500
Cu1—N1i	1.998 (3)	C3—H3	0.9500
Cu1—N3	2.074 (3)	C4—C5	1.328 (6)
Cu1—N3i	2.074 (3)	C4—H4	0.9500
N1—C1	1.352 (5)	C5—H5A	0.9500
N1—C3	1.421 (4)	C5—H5B	0.9500
N2—C1	1.392 (5)	C6—H6A	0.9900
N2—C2	1.436 (5)	C6—H6B	0.9900
N2—C4	1.456 (5)	P1—F6	1.625 (2)
N3—C6	1.516 (5)	P1—F1	1.631 (3)
N3—H3A	0.9200	P1—F4	1.634 (3)
N3—H3B	0.9200	P1—F2	1.638 (3)
C1—C6	1.531 (5)	P1—F3	1.638 (3)
C2—C3	1.375 (6)	P1—F5	1.658 (3)
N1—Cu1—N1i	180.00 (13)	C5—C4—N2	124.9 (4)
N1—Cu1—N3	82.53 (13)	C5—C4—H4	117.6
N1i—Cu1—N3	97.47 (13)	N2—C4—H4	117.6
N1—Cu1—N3i	97.47 (13)	C4—C5—H5A	120.0
N1i—Cu1—N3i	82.53 (13)	C4—C5—H5B	120.0
N3—Cu1—N3i	180.0	H5A—C5—H5B	120.0
C1—N1—C3	106.1 (3)	N3—C6—C1	106.0 (3)
C1—N1—Cu1	114.2 (2)	N3—C6—H6A	110.5
C3—N1—Cu1	139.7 (3)	C1—C6—H6A	110.5
C1—N2—C2	105.9 (3)	N3—C6—H6B	110.5
C1—N2—C4	127.2 (3)	C1—C6—H6B	110.5
C2—N2—C4	126.8 (3)	H6A—C6—H6B	108.7
C6—N3—Cu1	112.4 (2)	F6—P1—F1	89.70 (14)
C6—N3—H3A	109.1	F6—P1—F4	90.34 (15)
Cu1—N3—H3A	109.1	F1—P1—F4	179.76 (17)
C6—N3—H3B	109.1	F6—P1—F2	90.94 (13)
Cu1—N3—H3B	109.1	F1—P1—F2	89.76 (15)
H3A—N3—H3B	107.8	F4—P1—F2	90.48 (15)
N1—C1—N2	111.5 (3)	F6—P1—F3	179.61 (16)
N1—C1—C6	120.8 (3)	F1—P1—F3	90.11 (15)
N2—C1—C6	127.7 (3)	F4—P1—F3	89.84 (15)
C3—C2—N2	106.8 (3)	F2—P1—F3	89.41 (13)
C3—C2—H2	126.6	F6—P1—F5	89.31 (13)
N2—C2—H2	126.6	F1—P1—F5	90.23 (15)
C2—C3—N1	109.6 (4)	F4—P1—F5	89.53 (14)
C2—C3—H3	125.2	F2—P1—F5	179.75 (14)
N1—C3—H3	125.2	F3—P1—F5	90.34 (13)
N1i—Cu1—N1—C1	−64.0 (4)	C4—N2—C1—N1	−176.5 (4)
N3—Cu1—N1—C1	−6.8 (3)	C2—N2—C1—C6	−177.1 (4)
N3i—Cu1—N1—C1	173.2 (3)	C4—N2—C1—C6	5.6 (6)
N1i—Cu1—N1—C3	113.2 (6)	C1—N2—C2—C3	−0.4 (4)
N3—Cu1—N1—C3	170.4 (4)	C4—N2—C2—C3	176.9 (4)
N3i—Cu1—N1—C3	−9.6 (4)	N2—C2—C3—N1	−0.1 (5)
N1—Cu1—N3—C6	16.6 (3)	C1—N1—C3—C2	0.6 (5)
N1i—Cu1—N3—C6	−163.4 (3)	Cu1—N1—C3—C2	−176.8 (3)
N3i—Cu1—N3—C6	−41 (3)	C1—N2—C4—C5	−173.1 (4)
C3—N1—C1—N2	−0.9 (4)	C2—N2—C4—C5	10.1 (7)
Cu1—N1—C1—N2	177.2 (2)	Cu1—N3—C6—C1	−21.4 (4)
C3—N1—C1—C6	177.2 (3)	N1—C1—C6—N3	17.6 (5)
Cu1—N1—C1—C6	−4.7 (5)	N2—C1—C6—N3	−164.7 (4)
C2—N2—C1—N1	0.8 (4)

Symmetry codes: (i) −x, −y, −z.