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Acta Cryst. (2009). E65, m1022    [ doi:10.1107/S1600536809030037 ]

(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane)copper(II) bis(O,S-dibenzyl dithiophosphate)

J.-S. Feng, L.-K. Zou, B. Xie and Y. Wu

Abstract top

In the crystal structure of the title compound, [Cu(C16H36N4)](C14H14O2PS2)2, the CuII atom is located on an inversion center and is chelated by four N atoms of the macrocyclic meso-5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane ligand in a square-planar geometry, with Cu-N distances of 2.013 (3) and 2.014 (3) Å. In the crystal structure, one O,S-dibenzyl dithiophosphate counter-anion links with the CuII complex cation through N-H...O and N-H...S hydrogen bonding. During the synthesis, the structure of the anion re-arranged from O,O'-dibenzyl dithiophosphate in the starting material to O,S-dibenzyl dithiophosphate in the title compound.

Comment top

As part of an investigation to the tetramine macrocyclic transition metal complexs and their potential applications as artificial enzyme models, we have reported the structures of [Ni(tet-a)][S2P(OCH2Ph)2]2, where tet-a is a macrocyclic tetramine, meso-5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane (Xie et al., 2008). Here we report the crystal structure of the corresponding title CuII compound, [Cu(tet-a)][OSP(OCH2Ph)(SCH2Ph)]2.

In the title crystal structure, the complex cation [Cu(tet-a)]2+ possesses square-planar geometry about the CuII atom (Fig. 1), which lies across a centre of inversion and is four-coordinated by four N atoms of the tetramine macrocyclic ligand tet-a. All the bond lengths and angles in the adduct are generally within normal ranges (Allen et al., 1987). The two O,S-dibenzyl dithiophosphate anions act as counter-ions to balance the charge of the CuII complex cation, they interact with the complex cation through N—H···O and N—H···S hydrogen bonds (Table 1).

Related literature top

For a related NiII complex, see: Xie et al. (2008). For bond-length data, see Allen et al. (1987).

Experimental top

A solution of meso-5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane dihydrate (0.32 g, 1 mmol) and CuCl2.2H2O (0.17 g, 1 mmol) in 20 ml methanol was added to a solution of diethylammonium O,O'-dibenzyldithiophosphate, [NH2(C2H5)2]+[(PhCH2O)2PS2]- (Fig. 2), (0.77 g, 2 mmol) in 20 ml methanol. The mixture was refluxed for 24 h, then cooled to room temperature, the dark-violet precipitate was collected by filtration, washed with small amounts of methanol. A solution of the title compound in DMSO was kept at room temperature, and dark-violet block crystals suitable for X-ray diffraction studies were obtained in three months.

It should be noted that the title compound contains an unexpected re-arrangement product of the anion; in the starting reagent, [NH2(C2H5)2]+[(PhCH2O)2PS2]-, both of the two benzyl-groups bonded with O atoms, but in the title compound one of them migrated to the neighbouring S atom.

Refinement top

All H atoms attached to C and N atom were fixed geometrically and treated as riding with C—H = 0.98 Å (methine), 0.97 Å (methylene), 0.96 Å (methyl) or 0.93 Å (aromatic) and N—H = 0.91 Å with Uiso(H) = 1.2Ueq(C, N) or Uiso(H) = 1.5Ueq(methyl).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen-bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (i) -x + 1, -y, -z + 1].
[Figure 2] Fig. 2. The starting material [NH2(C2H5)2]+[(PhCH2O)2PS2]-.
(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11- tetraazacyclotetradecane)copper(II) bis(O,S-dibenzyl dithiophosphate) top
Crystal data top
[Cu(C16H36N4)](C14H14O2PS2)2F(000) = 1022
Mr = 966.71Dx = 1.351 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 29 reflections
a = 11.476 (4) Åθ = 4.4–11.5°
b = 17.592 (4) ŵ = 0.75 mm−1
c = 11.945 (4) ÅT = 289 K
β = 99.78 (2)°Block, dark-violet
V = 2376.4 (13) Å30.44 × 0.40 × 0.35 mm
Z = 2
Data collection top
Enraf–Nonius CAD-4
diffractometer		2900 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.006
graphiteθmax = 25.6°, θmin = 1.8°
ω/2θ scansh = −13→13
Absorption correction: ψ scan
(North et al., 1968)		k = 0→21
Tmin = 0.730, Tmax = 0.770l = −4→14
4797 measured reflections3 standard reflections every 300 reflections
4420 independent reflections intensity decay: 6.7%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0968P)2]
where P = (Fo2 + 2Fc2)/3
4420 reflections(Δ/σ)max < 0.001
275 parametersΔρmax = 0.45 e Å−3
0 restraintsΔρmin = −0.69 e Å−3
Crystal data top
[Cu(C16H36N4)](C14H14O2PS2)2V = 2376.4 (13) Å3
Mr = 966.71Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.476 (4) ŵ = 0.75 mm−1
b = 17.592 (4) ÅT = 289 K
c = 11.945 (4) Å0.44 × 0.40 × 0.35 mm
β = 99.78 (2)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		2900 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.006
Tmin = 0.730, Tmax = 0.770θmax = 25.6°
4797 measured reflections3 standard reflections every 300 reflections
4420 independent reflections intensity decay: 6.7%
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.154Δρmax = 0.45 e Å−3
S = 1.04Δρmin = −0.69 e Å−3
4420 reflectionsAbsolute structure: ?
275 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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 (Å2) top
xyzUiso*/Ueq
Cu10.50000.00000.50000.0373 (2)
S10.45680 (10)0.16085 (8)0.65146 (9)0.0633 (3)
S20.60091 (9)0.16270 (6)0.90486 (8)0.0523 (3)
P10.46223 (8)0.11046 (6)0.79879 (8)0.0426 (3)
O10.3474 (2)0.12698 (17)0.8538 (2)0.0550 (7)
O20.4729 (3)0.02701 (17)0.8069 (3)0.0610 (8)
N10.6456 (2)0.06574 (17)0.5164 (2)0.0376 (7)
H10.63230.10220.56690.045*
N20.4441 (2)0.05885 (17)0.3564 (2)0.0369 (7)
H20.46820.03120.30020.044*
C10.6406 (3)0.1077 (2)0.4085 (3)0.0475 (9)
H1A0.67120.07620.35350.057*
H1B0.68860.15330.42110.057*
C20.5149 (3)0.1285 (2)0.3647 (3)0.0431 (9)
H2A0.48670.16420.41590.052*
H2B0.50860.15220.29060.052*
C30.3165 (3)0.0731 (2)0.3165 (3)0.0444 (9)
H30.28940.11010.36790.053*
C40.2455 (3)0.0014 (2)0.3192 (3)0.0480 (9)
H4A0.2786−0.03660.27470.058*
H4B0.16580.01170.28040.058*
C50.2935 (4)0.1062 (3)0.1966 (4)0.0708 (14)
H5A0.33970.15140.19430.106*
H5B0.21110.11830.17570.106*
H5C0.31520.06950.14420.106*
C60.7638 (3)0.0344 (2)0.5661 (3)0.0415 (8)
C70.8558 (4)0.0984 (3)0.5855 (4)0.0667 (13)
H7A0.85870.12370.51490.100*
H7B0.93210.07730.61470.100*
H7C0.83430.13420.63920.100*
C80.8018 (4)−0.0231 (2)0.4853 (4)0.0546 (10)
H8A0.7366−0.05590.45720.082*
H8B0.8662−0.05280.52460.082*
H8C0.82680.00290.42280.082*
C90.3028 (5)0.2003 (3)0.8600 (5)0.0731 (14)
H9A0.28870.22320.78510.088*
H9B0.35970.23140.90920.088*
C100.1885 (3)0.1965 (2)0.9066 (3)0.0476 (9)
C110.1010 (5)0.1453 (3)0.8683 (4)0.0669 (12)
H110.11190.11130.81140.080*
C12−0.0002 (4)0.1428 (3)0.9107 (5)0.0750 (14)
H12−0.05770.10700.88320.090*
C13−0.0188 (4)0.1915 (3)0.9925 (4)0.0703 (14)
H13−0.08940.18951.02080.084*
C140.0652 (5)0.2437 (3)1.0342 (4)0.0700 (14)
H140.05300.27721.09140.084*
C150.1705 (4)0.2460 (2)0.9893 (4)0.0579 (11)
H150.22840.28171.01630.070*
C160.5930 (4)0.1139 (3)1.0376 (3)0.0676 (14)
H16A0.52850.13461.07100.081*
H16B0.57780.06031.02300.081*
C170.7064 (3)0.1235 (3)1.1178 (3)0.0492 (10)
C180.7318 (4)0.1904 (3)1.1759 (4)0.0618 (12)
H180.67780.23031.16550.074*
C190.8376 (6)0.1983 (3)1.2498 (4)0.0812 (17)
H190.85360.24371.28930.097*
C200.9167 (5)0.1428 (4)1.2658 (4)0.0847 (18)
H200.98820.14961.31450.102*
C210.8919 (5)0.0752 (3)1.2098 (5)0.0809 (16)
H210.94560.03521.22220.097*
C220.7873 (4)0.0666 (3)1.1349 (4)0.0663 (12)
H220.77180.02111.09550.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0326 (3)0.0406 (4)0.0394 (3)0.0051 (3)0.0081 (2)0.0141 (3)
S10.0623 (7)0.0895 (9)0.0385 (5)0.0165 (6)0.0100 (5)0.0071 (5)
S20.0512 (6)0.0614 (7)0.0420 (5)−0.0119 (5)0.0015 (4)0.0061 (5)
P10.0407 (5)0.0505 (6)0.0381 (5)0.0035 (4)0.0110 (4)−0.0066 (4)
O10.0499 (16)0.0567 (18)0.0628 (17)0.0093 (14)0.0223 (13)−0.0028 (14)
O20.083 (2)0.0394 (16)0.0649 (18)0.0009 (15)0.0241 (16)−0.0094 (14)
N10.0390 (15)0.0383 (17)0.0360 (15)0.0010 (13)0.0080 (12)0.0041 (13)
N20.0401 (15)0.0398 (17)0.0317 (14)0.0087 (13)0.0085 (12)0.0053 (13)
C10.051 (2)0.049 (2)0.044 (2)−0.0070 (18)0.0104 (17)0.0137 (17)
C20.054 (2)0.034 (2)0.0422 (19)0.0028 (17)0.0115 (16)0.0112 (16)
C30.040 (2)0.045 (2)0.047 (2)0.0107 (17)0.0050 (16)0.0115 (17)
C40.041 (2)0.056 (2)0.045 (2)0.0057 (18)−0.0001 (16)0.0022 (18)
C50.060 (3)0.088 (4)0.059 (3)0.010 (3)−0.003 (2)0.036 (3)
C60.0346 (18)0.043 (2)0.046 (2)−0.0012 (16)0.0029 (15)0.0039 (17)
C70.052 (3)0.067 (3)0.075 (3)−0.019 (2)−0.004 (2)0.010 (2)
C80.053 (2)0.058 (3)0.055 (2)0.011 (2)0.0157 (19)0.006 (2)
C90.077 (3)0.051 (3)0.100 (4)0.000 (2)0.041 (3)0.006 (3)
C100.040 (2)0.050 (2)0.056 (2)0.0059 (18)0.0167 (17)0.0112 (19)
C110.084 (3)0.055 (3)0.064 (3)0.006 (3)0.015 (2)−0.004 (2)
C120.056 (3)0.080 (4)0.087 (4)−0.015 (3)0.007 (3)0.006 (3)
C130.051 (3)0.096 (4)0.068 (3)0.015 (3)0.019 (2)0.028 (3)
C140.081 (3)0.082 (4)0.049 (2)0.035 (3)0.015 (2)0.003 (2)
C150.057 (3)0.050 (3)0.062 (3)0.002 (2)−0.003 (2)0.001 (2)
C160.055 (3)0.102 (4)0.045 (2)−0.023 (3)0.0031 (19)0.018 (2)
C170.046 (2)0.063 (3)0.039 (2)−0.013 (2)0.0062 (16)0.0060 (19)
C180.074 (3)0.066 (3)0.048 (2)−0.006 (2)0.018 (2)0.005 (2)
C190.114 (5)0.084 (4)0.044 (3)−0.044 (4)0.008 (3)−0.004 (3)
C200.070 (3)0.113 (5)0.061 (3)−0.036 (3)−0.016 (3)0.023 (3)
C210.059 (3)0.093 (4)0.085 (4)0.012 (3)−0.004 (3)0.029 (3)
C220.072 (3)0.055 (3)0.070 (3)−0.010 (2)0.008 (2)0.004 (2)
Geometric parameters (Å, °) top
Cu1—N2i2.013 (3)C7—H7B0.9600
Cu1—N22.013 (3)C7—H7C0.9600
Cu1—N1i2.014 (3)C8—H8A0.9600
Cu1—N12.014 (3)C8—H8B0.9600
S1—P11.9619 (15)C8—H8C0.9600
S2—C161.818 (4)C9—C101.510 (6)
S2—P12.0729 (15)C9—H9A0.9700
P1—O21.475 (3)C9—H9B0.9700
P1—O11.596 (3)C10—C151.359 (6)
O1—C91.394 (5)C10—C111.368 (6)
N1—C11.478 (4)C11—C121.344 (7)
N1—C61.491 (4)C11—H110.9300
N1—H10.9100C12—C131.343 (7)
N2—C21.465 (5)C12—H120.9300
N2—C31.482 (4)C13—C141.364 (7)
N2—H20.9100C13—H130.9300
C1—C21.493 (5)C14—C151.404 (7)
C1—H1A0.9700C14—H140.9300
C1—H1B0.9700C15—H150.9300
C2—H2A0.9700C16—C171.489 (5)
C2—H2B0.9700C16—H16A0.9700
C3—C41.506 (5)C16—H16B0.9700
C3—C51.527 (5)C17—C221.356 (6)
C3—H30.9800C17—C181.372 (6)
C4—C6i1.528 (5)C18—C191.382 (7)
C4—H4A0.9700C18—H180.9300
C4—H4B0.9700C19—C201.325 (8)
C5—H5A0.9600C19—H190.9300
C5—H5B0.9600C20—C211.370 (8)
C5—H5C0.9600C20—H200.9300
C6—C81.513 (5)C21—C221.379 (7)
C6—C4i1.528 (5)C21—H210.9300
C6—C71.533 (5)C22—H220.9300
C7—H7A0.9600
N2i—Cu1—N2180.0C4i—C6—C7108.6 (3)
N2i—Cu1—N1i85.80 (11)C6—C7—H7A109.5
N2—Cu1—N1i94.20 (12)C6—C7—H7B109.5
N2i—Cu1—N194.20 (12)H7A—C7—H7B109.5
N2—Cu1—N185.80 (11)C6—C7—H7C109.5
N1i—Cu1—N1180.0H7A—C7—H7C109.5
C16—S2—P1100.18 (15)H7B—C7—H7C109.5
O2—P1—O1102.66 (17)C6—C8—H8A109.5
O2—P1—S1119.89 (13)C6—C8—H8B109.5
O1—P1—S1112.60 (12)H8A—C8—H8B109.5
O2—P1—S2110.77 (14)C6—C8—H8C109.5
O1—P1—S2105.65 (12)H8A—C8—H8C109.5
S1—P1—S2104.60 (7)H8B—C8—H8C109.5
C9—O1—P1121.8 (3)O1—C9—C10109.2 (4)
C1—N1—C6115.4 (3)O1—C9—H9A109.8
C1—N1—Cu1107.0 (2)C10—C9—H9A109.8
C6—N1—Cu1120.7 (2)O1—C9—H9B109.8
C1—N1—H1103.9C10—C9—H9B109.8
C6—N1—H1103.9H9A—C9—H9B108.3
Cu1—N1—H1103.9C15—C10—C11118.1 (4)
C2—N2—C3112.7 (3)C15—C10—C9119.2 (4)
C2—N2—Cu1106.3 (2)C11—C10—C9122.6 (4)
C3—N2—Cu1121.0 (2)C12—C11—C10121.9 (5)
C2—N2—H2105.2C12—C11—H11119.1
C3—N2—H2105.2C10—C11—H11119.1
Cu1—N2—H2105.2C13—C12—C11120.5 (5)
N1—C1—C2108.7 (3)C13—C12—H12119.8
N1—C1—H1A110.0C11—C12—H12119.8
C2—C1—H1A110.0C12—C13—C14120.4 (4)
N1—C1—H1B110.0C12—C13—H13119.8
C2—C1—H1B110.0C14—C13—H13119.8
H1A—C1—H1B108.3C13—C14—C15118.7 (4)
N2—C2—C1108.1 (3)C13—C14—H14120.7
N2—C2—H2A110.1C15—C14—H14120.7
C1—C2—H2A110.1C10—C15—C14120.4 (4)
N2—C2—H2B110.1C10—C15—H15119.8
C1—C2—H2B110.1C14—C15—H15119.8
H2A—C2—H2B108.4C17—C16—S2109.9 (3)
N2—C3—C4111.1 (3)C17—C16—H16A109.7
N2—C3—C5111.7 (3)S2—C16—H16A109.7
C4—C3—C5109.3 (3)C17—C16—H16B109.7
N2—C3—H3108.2S2—C16—H16B109.7
C4—C3—H3108.2H16A—C16—H16B108.2
C5—C3—H3108.2C22—C17—C18118.4 (4)
C3—C4—C6i119.0 (3)C22—C17—C16120.9 (4)
C3—C4—H4A107.6C18—C17—C16120.6 (4)
C6i—C4—H4A107.6C17—C18—C19119.8 (5)
C3—C4—H4B107.6C17—C18—H18120.1
C6i—C4—H4B107.6C19—C18—H18120.1
H4A—C4—H4B107.0C20—C19—C18121.6 (5)
C3—C5—H5A109.5C20—C19—H19119.2
C3—C5—H5B109.5C18—C19—H19119.2
H5A—C5—H5B109.5C19—C20—C21119.3 (5)
C3—C5—H5C109.5C19—C20—H20120.3
H5A—C5—H5C109.5C21—C20—H20120.3
H5B—C5—H5C109.5C20—C21—C22119.8 (5)
N1—C6—C8109.6 (3)C20—C21—H21120.1
N1—C6—C4i108.1 (3)C22—C21—H21120.1
C8—C6—C4i111.6 (3)C17—C22—C21121.0 (5)
N1—C6—C7110.2 (3)C17—C22—H22119.5
C8—C6—C7108.8 (3)C21—C22—H22119.5
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S10.912.613.359 (3)140
N2—H2···O2i0.911.852.762 (4)176
Symmetry codes: (i) −x+1, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S10.912.613.359 (3)140
N2—H2···O2i0.911.852.762 (4)176
Symmetry codes: (i) −x+1, −y, −z+1.
Acknowledgements top

This project was supported by the Education Committee of Sichuan Province of China (project No. 2006 A110, 07ZA161) and the Science and Technology Office of Zigong City of China (Project No. 08X01) and the University Key Laboratory of Corrosion and Protection of Materials of Sichuan Province of China (Project No. 2008 C L04).

references
References top

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