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

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

doi:10.1107/S1600536809030037

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1022

doi:10.1107/S1600536809030037

Open

access

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

Jian-Shen Feng,^a Li-Ke Zou,^a ^* Bin Xie ^a and Yu Wu ^a

^aCollege of Chemistry & Pharmaceutical Engineering, Sichuan University of Science & Engineering, Zigong 643000, People's Republic of China
^*Correspondence e-mail: zoulike@yahoo.com.cn

(Received 24 July 2009; accepted 29 July 2009; online 8 August 2009)

In the crystal structure of the title compound, [Cu(C₁₆H₃₆N₄)](C₁₄H₁₄O₂PS₂)₂, the Cu^II 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 Cu^II 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.

Related literature

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

Experimental

Crystal data

[Cu(C₁₆H₃₆N₄)](C₁₄H₁₄O₂PS₂)₂
M_r = 966.71
Monoclinic, P 2₁ /c
a = 11.476 (4) Å
b = 17.592 (4) Å
c = 11.945 (4) Å
β = 99.78 (2)°
V = 2376.4 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 289 K
0.44 × 0.40 × 0.35 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.730, T_max = 0.770
4797 measured reflections
4420 independent reflections
2900 reflections with I > 2σ(I)
R_int = 0.006
3 standard reflections every 300 reflections intensity decay: 6.7%

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.154
S = 1.04
4420 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1	0.91	2.61	3.359 (3)	140
N2—H2⋯O2ⁱ	0.91	1.85	2.762 (4)	176
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030037/xu2568sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030037/xu2568Isup2.hkl

checkCIF report

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 Cu^II 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 Cu^II 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 Cu^II 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 Ni^II 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.

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

	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].
	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)₂	F(000) = 1022
M_r = 966.71	D_x = 1.351 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 29 reflections
a = 11.476 (4) Å	θ = 4.4–11.5°
b = 17.592 (4) Å	µ = 0.75 mm⁻¹
c = 11.945 (4) Å	T = 289 K
β = 99.78 (2)°	Block, dark-violet
V = 2376.4 (13) Å³	0.44 × 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 tube	R_int = 0.006
Graphite monochromator	θ_max = 25.6°, θ_min = 1.8°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→21
T_min = 0.730, T_max = 0.770	l = −4→14
4797 measured reflections	3 standard reflections every 300 reflections
4420 independent reflections	intensity decay: 6.7%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0968P)²] where P = (F_o² + 2F_c²)/3
4420 reflections	(Δ/σ)_max < 0.001
275 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Cu(C₁₆H₃₆N₄)](C₁₄H₁₄O₂PS₂)₂	V = 2376.4 (13) Å³
M_r = 966.71	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.476 (4) Å	µ = 0.75 mm⁻¹
b = 17.592 (4) Å	T = 289 K
c = 11.945 (4) Å	0.44 × 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)	R_int = 0.006
T_min = 0.730, T_max = 0.770	3 standard reflections every 300 reflections
4797 measured reflections	intensity decay: 6.7%
4420 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.04	Δρ_max = 0.45 e Å⁻³
4420 reflections	Δρ_min = −0.69 e Å⁻³
275 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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.5000	0.0373 (2)
S1	0.45680 (10)	0.16085 (8)	0.65146 (9)	0.0633 (3)
S2	0.60091 (9)	0.16270 (6)	0.90486 (8)	0.0523 (3)
P1	0.46223 (8)	0.11046 (6)	0.79879 (8)	0.0426 (3)
O1	0.3474 (2)	0.12698 (17)	0.8538 (2)	0.0550 (7)
O2	0.4729 (3)	0.02701 (17)	0.8069 (3)	0.0610 (8)
N1	0.6456 (2)	0.06574 (17)	0.5164 (2)	0.0376 (7)
H1	0.6323	0.1022	0.5669	0.045*
N2	0.4441 (2)	0.05885 (17)	0.3564 (2)	0.0369 (7)
H2	0.4682	0.0312	0.3002	0.044*
C1	0.6406 (3)	0.1077 (2)	0.4085 (3)	0.0475 (9)
H1A	0.6712	0.0762	0.3535	0.057*
H1B	0.6886	0.1533	0.4211	0.057*
C2	0.5149 (3)	0.1285 (2)	0.3647 (3)	0.0431 (9)
H2A	0.4867	0.1642	0.4159	0.052*
H2B	0.5086	0.1522	0.2906	0.052*
C3	0.3165 (3)	0.0731 (2)	0.3165 (3)	0.0444 (9)
H3	0.2894	0.1101	0.3679	0.053*
C4	0.2455 (3)	0.0014 (2)	0.3192 (3)	0.0480 (9)
H4A	0.2786	−0.0366	0.2747	0.058*
H4B	0.1658	0.0117	0.2804	0.058*
C5	0.2935 (4)	0.1062 (3)	0.1966 (4)	0.0708 (14)
H5A	0.3397	0.1514	0.1943	0.106*
H5B	0.2111	0.1183	0.1757	0.106*
H5C	0.3152	0.0695	0.1442	0.106*
C6	0.7638 (3)	0.0344 (2)	0.5661 (3)	0.0415 (8)
C7	0.8558 (4)	0.0984 (3)	0.5855 (4)	0.0667 (13)
H7A	0.8587	0.1237	0.5149	0.100*
H7B	0.9321	0.0773	0.6147	0.100*
H7C	0.8343	0.1342	0.6392	0.100*
C8	0.8018 (4)	−0.0231 (2)	0.4853 (4)	0.0546 (10)
H8A	0.7366	−0.0559	0.4572	0.082*
H8B	0.8662	−0.0528	0.5246	0.082*
H8C	0.8268	0.0029	0.4228	0.082*
C9	0.3028 (5)	0.2003 (3)	0.8600 (5)	0.0731 (14)
H9A	0.2887	0.2232	0.7851	0.088*
H9B	0.3597	0.2314	0.9092	0.088*
C10	0.1885 (3)	0.1965 (2)	0.9066 (3)	0.0476 (9)
C11	0.1010 (5)	0.1453 (3)	0.8683 (4)	0.0669 (12)
H11	0.1119	0.1113	0.8114	0.080*
C12	−0.0002 (4)	0.1428 (3)	0.9107 (5)	0.0750 (14)
H12	−0.0577	0.1070	0.8832	0.090*
C13	−0.0188 (4)	0.1915 (3)	0.9925 (4)	0.0703 (14)
H13	−0.0894	0.1895	1.0208	0.084*
C14	0.0652 (5)	0.2437 (3)	1.0342 (4)	0.0700 (14)
H14	0.0530	0.2772	1.0914	0.084*
C15	0.1705 (4)	0.2460 (2)	0.9893 (4)	0.0579 (11)
H15	0.2284	0.2817	1.0163	0.070*
C16	0.5930 (4)	0.1139 (3)	1.0376 (3)	0.0676 (14)
H16A	0.5285	0.1346	1.0710	0.081*
H16B	0.5778	0.0603	1.0230	0.081*
C17	0.7064 (3)	0.1235 (3)	1.1178 (3)	0.0492 (10)
C18	0.7318 (4)	0.1904 (3)	1.1759 (4)	0.0618 (12)
H18	0.6778	0.2303	1.1655	0.074*
C19	0.8376 (6)	0.1983 (3)	1.2498 (4)	0.0812 (17)
H19	0.8536	0.2437	1.2893	0.097*
C20	0.9167 (5)	0.1428 (4)	1.2658 (4)	0.0847 (18)
H20	0.9882	0.1496	1.3145	0.102*
C21	0.8919 (5)	0.0752 (3)	1.2098 (5)	0.0809 (16)
H21	0.9456	0.0352	1.2222	0.097*
C22	0.7873 (4)	0.0666 (3)	1.1349 (4)	0.0663 (12)
H22	0.7718	0.0211	1.0955	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0326 (3)	0.0406 (4)	0.0394 (3)	0.0051 (3)	0.0081 (2)	0.0141 (3)
S1	0.0623 (7)	0.0895 (9)	0.0385 (5)	0.0165 (6)	0.0100 (5)	0.0071 (5)
S2	0.0512 (6)	0.0614 (7)	0.0420 (5)	−0.0119 (5)	0.0015 (4)	0.0061 (5)
P1	0.0407 (5)	0.0505 (6)	0.0381 (5)	0.0035 (4)	0.0110 (4)	−0.0066 (4)
O1	0.0499 (16)	0.0567 (18)	0.0628 (17)	0.0093 (14)	0.0223 (13)	−0.0028 (14)
O2	0.083 (2)	0.0394 (16)	0.0649 (18)	0.0009 (15)	0.0241 (16)	−0.0094 (14)
N1	0.0390 (15)	0.0383 (17)	0.0360 (15)	0.0010 (13)	0.0080 (12)	0.0041 (13)
N2	0.0401 (15)	0.0398 (17)	0.0317 (14)	0.0087 (13)	0.0085 (12)	0.0053 (13)
C1	0.051 (2)	0.049 (2)	0.044 (2)	−0.0070 (18)	0.0104 (17)	0.0137 (17)
C2	0.054 (2)	0.034 (2)	0.0422 (19)	0.0028 (17)	0.0115 (16)	0.0112 (16)
C3	0.040 (2)	0.045 (2)	0.047 (2)	0.0107 (17)	0.0050 (16)	0.0115 (17)
C4	0.041 (2)	0.056 (2)	0.045 (2)	0.0057 (18)	−0.0001 (16)	0.0022 (18)
C5	0.060 (3)	0.088 (4)	0.059 (3)	0.010 (3)	−0.003 (2)	0.036 (3)
C6	0.0346 (18)	0.043 (2)	0.046 (2)	−0.0012 (16)	0.0029 (15)	0.0039 (17)
C7	0.052 (3)	0.067 (3)	0.075 (3)	−0.019 (2)	−0.004 (2)	0.010 (2)
C8	0.053 (2)	0.058 (3)	0.055 (2)	0.011 (2)	0.0157 (19)	0.006 (2)
C9	0.077 (3)	0.051 (3)	0.100 (4)	0.000 (2)	0.041 (3)	0.006 (3)
C10	0.040 (2)	0.050 (2)	0.056 (2)	0.0059 (18)	0.0167 (17)	0.0112 (19)
C11	0.084 (3)	0.055 (3)	0.064 (3)	0.006 (3)	0.015 (2)	−0.004 (2)
C12	0.056 (3)	0.080 (4)	0.087 (4)	−0.015 (3)	0.007 (3)	0.006 (3)
C13	0.051 (3)	0.096 (4)	0.068 (3)	0.015 (3)	0.019 (2)	0.028 (3)
C14	0.081 (3)	0.082 (4)	0.049 (2)	0.035 (3)	0.015 (2)	0.003 (2)
C15	0.057 (3)	0.050 (3)	0.062 (3)	0.002 (2)	−0.003 (2)	0.001 (2)
C16	0.055 (3)	0.102 (4)	0.045 (2)	−0.023 (3)	0.0031 (19)	0.018 (2)
C17	0.046 (2)	0.063 (3)	0.039 (2)	−0.013 (2)	0.0062 (16)	0.0060 (19)
C18	0.074 (3)	0.066 (3)	0.048 (2)	−0.006 (2)	0.018 (2)	0.005 (2)
C19	0.114 (5)	0.084 (4)	0.044 (3)	−0.044 (4)	0.008 (3)	−0.004 (3)
C20	0.070 (3)	0.113 (5)	0.061 (3)	−0.036 (3)	−0.016 (3)	0.023 (3)
C21	0.059 (3)	0.093 (4)	0.085 (4)	0.012 (3)	−0.004 (3)	0.029 (3)
C22	0.072 (3)	0.055 (3)	0.070 (3)	−0.010 (2)	0.008 (2)	0.004 (2)

Geometric parameters (Å, º) top

Cu1—N2ⁱ	2.013 (3)	C7—H7B	0.9600
Cu1—N2	2.013 (3)	C7—H7C	0.9600
Cu1—N1ⁱ	2.014 (3)	C8—H8A	0.9600
Cu1—N1	2.014 (3)	C8—H8B	0.9600
S1—P1	1.9619 (15)	C8—H8C	0.9600
S2—C16	1.818 (4)	C9—C10	1.510 (6)
S2—P1	2.0729 (15)	C9—H9A	0.9700
P1—O2	1.475 (3)	C9—H9B	0.9700
P1—O1	1.596 (3)	C10—C15	1.359 (6)
O1—C9	1.394 (5)	C10—C11	1.368 (6)
N1—C1	1.478 (4)	C11—C12	1.344 (7)
N1—C6	1.491 (4)	C11—H11	0.9300
N1—H1	0.9100	C12—C13	1.343 (7)
N2—C2	1.465 (5)	C12—H12	0.9300
N2—C3	1.482 (4)	C13—C14	1.364 (7)
N2—H2	0.9100	C13—H13	0.9300
C1—C2	1.493 (5)	C14—C15	1.404 (7)
C1—H1A	0.9700	C14—H14	0.9300
C1—H1B	0.9700	C15—H15	0.9300
C2—H2A	0.9700	C16—C17	1.489 (5)
C2—H2B	0.9700	C16—H16A	0.9700
C3—C4	1.506 (5)	C16—H16B	0.9700
C3—C5	1.527 (5)	C17—C22	1.356 (6)
C3—H3	0.9800	C17—C18	1.372 (6)
C4—C6ⁱ	1.528 (5)	C18—C19	1.382 (7)
C4—H4A	0.9700	C18—H18	0.9300
C4—H4B	0.9700	C19—C20	1.325 (8)
C5—H5A	0.9600	C19—H19	0.9300
C5—H5B	0.9600	C20—C21	1.370 (8)
C5—H5C	0.9600	C20—H20	0.9300
C6—C8	1.513 (5)	C21—C22	1.379 (7)
C6—C4ⁱ	1.528 (5)	C21—H21	0.9300
C6—C7	1.533 (5)	C22—H22	0.9300
C7—H7A	0.9600

N2ⁱ—Cu1—N2	180.0	C4ⁱ—C6—C7	108.6 (3)
N2ⁱ—Cu1—N1ⁱ	85.80 (11)	C6—C7—H7A	109.5
N2—Cu1—N1ⁱ	94.20 (12)	C6—C7—H7B	109.5
N2ⁱ—Cu1—N1	94.20 (12)	H7A—C7—H7B	109.5
N2—Cu1—N1	85.80 (11)	C6—C7—H7C	109.5
N1ⁱ—Cu1—N1	180.0	H7A—C7—H7C	109.5
C16—S2—P1	100.18 (15)	H7B—C7—H7C	109.5
O2—P1—O1	102.66 (17)	C6—C8—H8A	109.5
O2—P1—S1	119.89 (13)	C6—C8—H8B	109.5
O1—P1—S1	112.60 (12)	H8A—C8—H8B	109.5
O2—P1—S2	110.77 (14)	C6—C8—H8C	109.5
O1—P1—S2	105.65 (12)	H8A—C8—H8C	109.5
S1—P1—S2	104.60 (7)	H8B—C8—H8C	109.5
C9—O1—P1	121.8 (3)	O1—C9—C10	109.2 (4)
C1—N1—C6	115.4 (3)	O1—C9—H9A	109.8
C1—N1—Cu1	107.0 (2)	C10—C9—H9A	109.8
C6—N1—Cu1	120.7 (2)	O1—C9—H9B	109.8
C1—N1—H1	103.9	C10—C9—H9B	109.8
C6—N1—H1	103.9	H9A—C9—H9B	108.3
Cu1—N1—H1	103.9	C15—C10—C11	118.1 (4)
C2—N2—C3	112.7 (3)	C15—C10—C9	119.2 (4)
C2—N2—Cu1	106.3 (2)	C11—C10—C9	122.6 (4)
C3—N2—Cu1	121.0 (2)	C12—C11—C10	121.9 (5)
C2—N2—H2	105.2	C12—C11—H11	119.1
C3—N2—H2	105.2	C10—C11—H11	119.1
Cu1—N2—H2	105.2	C13—C12—C11	120.5 (5)
N1—C1—C2	108.7 (3)	C13—C12—H12	119.8
N1—C1—H1A	110.0	C11—C12—H12	119.8
C2—C1—H1A	110.0	C12—C13—C14	120.4 (4)
N1—C1—H1B	110.0	C12—C13—H13	119.8
C2—C1—H1B	110.0	C14—C13—H13	119.8
H1A—C1—H1B	108.3	C13—C14—C15	118.7 (4)
N2—C2—C1	108.1 (3)	C13—C14—H14	120.7
N2—C2—H2A	110.1	C15—C14—H14	120.7
C1—C2—H2A	110.1	C10—C15—C14	120.4 (4)
N2—C2—H2B	110.1	C10—C15—H15	119.8
C1—C2—H2B	110.1	C14—C15—H15	119.8
H2A—C2—H2B	108.4	C17—C16—S2	109.9 (3)
N2—C3—C4	111.1 (3)	C17—C16—H16A	109.7
N2—C3—C5	111.7 (3)	S2—C16—H16A	109.7
C4—C3—C5	109.3 (3)	C17—C16—H16B	109.7
N2—C3—H3	108.2	S2—C16—H16B	109.7
C4—C3—H3	108.2	H16A—C16—H16B	108.2
C5—C3—H3	108.2	C22—C17—C18	118.4 (4)
C3—C4—C6ⁱ	119.0 (3)	C22—C17—C16	120.9 (4)
C3—C4—H4A	107.6	C18—C17—C16	120.6 (4)
C6ⁱ—C4—H4A	107.6	C17—C18—C19	119.8 (5)
C3—C4—H4B	107.6	C17—C18—H18	120.1
C6ⁱ—C4—H4B	107.6	C19—C18—H18	120.1
H4A—C4—H4B	107.0	C20—C19—C18	121.6 (5)
C3—C5—H5A	109.5	C20—C19—H19	119.2
C3—C5—H5B	109.5	C18—C19—H19	119.2
H5A—C5—H5B	109.5	C19—C20—C21	119.3 (5)
C3—C5—H5C	109.5	C19—C20—H20	120.3
H5A—C5—H5C	109.5	C21—C20—H20	120.3
H5B—C5—H5C	109.5	C20—C21—C22	119.8 (5)
N1—C6—C8	109.6 (3)	C20—C21—H21	120.1
N1—C6—C4ⁱ	108.1 (3)	C22—C21—H21	120.1
C8—C6—C4ⁱ	111.6 (3)	C17—C22—C21	121.0 (5)
N1—C6—C7	110.2 (3)	C17—C22—H22	119.5
C8—C6—C7	108.8 (3)	C21—C22—H22	119.5

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.91	2.61	3.359 (3)	140
N2—H2···O2ⁱ	0.91	1.85	2.762 (4)	176

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₆H₃₆N₄)](C₁₄H₁₄O₂PS₂)₂
M_r	966.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	289
a, b, c (Å)	11.476 (4), 17.592 (4), 11.945 (4)
β (°)	99.78 (2)
V (Å³)	2376.4 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.44 × 0.40 × 0.35

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.730, 0.770
No. of measured, independent and observed [I > 2σ(I)] reflections	4797, 4420, 2900
R_int	0.006
(sin θ/λ)_max (Å⁻¹)	0.607

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.154, 1.04
No. of reflections	4420
No. of parameters	275
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.69

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.91	2.61	3.359 (3)	139.5
N2—H2···O2ⁱ	0.91	1.85	2.762 (4)	175.8

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

This project was supported by the Education Committee of Sichuan Province of China (project No. 2006 A110, 07ZA161), 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

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, B., Zou, L.-K., He, Y.-G., Feng, J.-S. & Zhang, X.-L. (2008). Acta Cryst. E64, m622. Web of Science CSD CrossRef IUCr Journals Google Scholar

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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1022

doi:10.1107/S1600536809030037

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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