(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene)copper(II) bis­[O,O′-bis­(4-methyl­phen­yl)dithio­phosphate]

Zou, L.-K.; Xie, B.; Feng, J.-S.; Lai, C.

doi:10.1107/S1600536810046672

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1592

https://doi.org/10.1107/S1600536810046672

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(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)copper(II) bis[O,O′-bis(4-methylphenyl)dithiophosphate]

Li-Ke Zou,^a ^* Bin Xie,^a Jian-Shen Feng ^a and Chuan Lai ^a

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

(Received 31 October 2010; accepted 11 November 2010; online 17 November 2010)

In the title compound, [Cu(C₂₄H₃₂N₄)](C₁₄H₁₄O₂PS₂)₂, the Cu^II atom lies on an inversion center and is chelated by the macrocyclic ligand in a distorted CuN₄ square-planar geometry. Two O,O′-bis(4-methylphenyl)dithiophosphate anions occupy the axial positions with long Cu⋯S distances of 3.0090 (8) Å. Intermolecular N—H⋯S and C—H⋯S hydrogen bonding is present between the anions and the cation.

Related literature

For bond-length data, see: Allen et al. (1987 ). For complexes of Cu^I and Cu^II with O,O′-dialkyldithiophosphate (DPP) ligands, see: Drew et al. (1987 ); Liaw et al. (2005 ). For the ability of Cu^II to form high nuclearity clusters, see: Liu et al. (1995 ); Li et al. (2008 ). For related structures, see: Feng et al. (2009 ); Xie et al. (2009 ); He et al. (2010 ). For the synthesis, see: Curtis (2001 ).

Experimental

Crystal data

[Cu(C₂₄H₃₂N₄)](C₁₄H₁₄O₂PS₂)₂
M_r = 1058.76
Monoclinic, P 2₁ /n
a = 9.9467 (18) Å
b = 19.829 (3) Å
c = 13.550 (2) Å
β = 107.563 (2)°
V = 2548.0 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 103 K
0.43 × 0.27 × 0.17 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.750, T_max = 0.890
19915 measured reflections
5836 independent reflections
4826 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.093
S = 1.00
5836 reflections
311 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S2ⁱ	0.81 (2)	2.73 (2)	3.4868 (19)	157
C6—H6C⋯S2ⁱⁱ	0.98	2.80	3.755 (2)	164
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXS97 (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: https://doi.org/10.1107/S1600536810046672/xu5079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046672/xu5079Isup2.hkl

checkCIF report

Comment top

The complexes of Cu^I and Cu^II with O,O' -dialkyldithiophosphate ligands (DDP), have been explored extensively in the past decades because of their potential use as anti-oxidants, additives to lubricating oils, flotation reagents, insecticides (Drew et al., 1987; Liaw et al., 2005). A remarkable feature of the Cu^I is its ability to form high nuclearity clusters, in which the DDP ligands possess a variety of bridge bonding characteristics (Liu et al., 1995; Li et al., 2008). However, the reactions between Cu^II and DDP rarely give stable Cu^II complexes because the Cu^II atom is readily reduced by DDP to form Cu^I clusters. When reacting with DDP, the Cu^II can be stabilized by the formation of adducts with tetradentate nitrogen-donor ligands, e.g. macrocyclic tetramine. We have recently reported several structures of such kind of adducts (Feng et al., 2009; He et al., 2010). Herein, we report the structure of [Cu(meso-diphenyl[14]dien)] [S₂P(OC₆H₄Me-4)₂]₂, where meso-diphenyl[14]dien is C-meso-N-meso-5,12-dimethyl-7,14- diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene.

The molecular of the title adduct comprises a complex cation [Cu(meso-diphenyl[14]dien)]²⁺ and two uncoordinated [S₂P(OC₆H₄Me-4)₂]^- anion. Its structure is remarkably similar to the analogues, [Cu(trans-[14]dien)][S₂P(OC₆H₄Me-4)₂]₂ (He et al., 2010) and ([Ni(trans-[14]dien)] [S₂P(OC₆H₄Me-4)₂]₂ (Xie et al., 2009), where trans-[14]dien is meso-5,7,7,12,14,14-hexamethyl-1, 4,8,11-tetraazacyclotetradeca-4,11-diene. The Cu^II atom, lying on an inversion centre, is coordinated by four N atoms from the macrocyclic tetramine meso-diphenyl[14]dien and adopts a relatively undistorted square-planar geometry (Fig.1). The two [S₂P(OC₆H₄Me-4)₂]^- anion, occupying the axial positions to form an octahedral asymmetric unit, only act as counter-ions to balance the charge and interact with the complex cation through N—H···S hydrogen bonds (Table 1). All the bond lengths and angles in the complex are generally within normal ranges (Allen et al., 1987).

Related literature top

For bond-length data, see: Allen et al. (1987). For complexes of Cu^I and Cu^II with O,O'-dialkyldithiophosphate (DPP) ligands, see: Drew et al. (1987); Liaw et al. (2005). For the ability of the Cu^I to form high nuclearity clusters, see: Liu et al. (1995); Li et al. (2008). For related structures, see: Feng et al. (2009); Xie et al. (2009); He et al. (2010). For the synthesis, see: Curtis (2001).

Experimental top

5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (diphenyl[14]dien) was synthesized according to the procedure described by Curtis (2001).

A hot solution of CuCl₂.H₂O (1 mmol, 0.171 g) and diphenyl[14]dien (1 mmol, 0.376 g) in 20 ml ethanol was quickly added to [Et₂NH₂][S₂P(OC₆H₄Me-4)₂] (2 mmol, 0.823 g) dissolved in 20 ml hot ethanol with stirring. The mixture was refluxed for 4 h and refrigerated overnight, the purple product was filtered off, washed successively with water, methanol, ether and then air dried. The crude product was dissolved in hot dimethylformamide and filtered. The filtrate was kept at room temperature and violet block crystals suitable for X-ray diffraction studies were obtained after two months.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen-bonds are shown as dashed lines [symmetry code: (i) -x + 1, -y + 1, -z + 1].

(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11- tetraazacyclotetradeca-4,11-diene)copper(II) bis[O,O'-bis(4-methylphenyl)dithiophosphate] top

Crystal data top

[Cu(C₂₄H₃₂N₄)](C₁₄H₁₄O₂PS₂)₂	F(000) = 1110
M_r = 1058.76	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6736 reflections
a = 9.9467 (18) Å	θ = 3.0–27.5°
b = 19.829 (3) Å	µ = 0.70 mm⁻¹
c = 13.550 (2) Å	T = 103 K
β = 107.563 (2)°	Block, violet
V = 2548.0 (8) Å³	0.43 × 0.27 × 0.17 mm
Z = 2

Data collection top

Rigaku SPIDER diffractometer	5836 independent reflections
Radiation source: Rotating Anode	4826 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.750, T_max = 0.890	k = −18→25
19915 measured reflections	l = −15→17

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0451P)² + 1.360P] where P = (F_o² + 2F_c²)/3
5836 reflections	(Δ/σ)_max = 0.001
311 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu(C₂₄H₃₂N₄)](C₁₄H₁₄O₂PS₂)₂	V = 2548.0 (8) Å³
M_r = 1058.76	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.9467 (18) Å	µ = 0.70 mm⁻¹
b = 19.829 (3) Å	T = 103 K
c = 13.550 (2) Å	0.43 × 0.27 × 0.17 mm
β = 107.563 (2)°

Data collection top

Rigaku SPIDER diffractometer	5836 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4826 reflections with I > 2σ(I)
T_min = 0.750, T_max = 0.890	R_int = 0.037
19915 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.39 e Å⁻³
5836 reflections	Δρ_min = −0.29 e Å⁻³
311 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	0.5000	0.5000	0.01698 (10)
P1	0.73029 (5)	0.58172 (3)	0.33214 (4)	0.01667 (12)
S1	0.53338 (5)	0.59003 (3)	0.33017 (4)	0.02142 (12)
S2	0.87798 (5)	0.61491 (3)	0.45230 (4)	0.02187 (12)
O1	0.73913 (15)	0.61604 (7)	0.22511 (11)	0.0209 (3)
O2	0.77276 (15)	0.50382 (7)	0.31829 (11)	0.0196 (3)
N1	0.34219 (17)	0.44424 (8)	0.40943 (13)	0.0142 (3)
N2	0.35057 (17)	0.56801 (8)	0.49380 (13)	0.0153 (3)
C1	0.2328 (2)	0.49252 (10)	0.35271 (16)	0.0175 (4)
H1A	0.1433	0.4684	0.3200	0.021*
H1B	0.2628	0.5150	0.2976	0.021*
C2	0.2112 (2)	0.54459 (10)	0.42844 (16)	0.0181 (4)
H2A	0.1562	0.5831	0.3903	0.022*
H2B	0.1581	0.5244	0.4723	0.022*
C3	0.3657 (2)	0.62765 (10)	0.53057 (16)	0.0168 (4)
C4	0.5066 (2)	0.65355 (10)	0.59550 (18)	0.0215 (4)
H4A	0.4890	0.6873	0.6440	0.026*
H4B	0.5497	0.6779	0.5489	0.026*
C5	0.6161 (2)	0.60396 (10)	0.65898 (15)	0.0166 (4)
H5	0.5719	0.5778	0.7042	0.020*
C6	0.2489 (2)	0.67873 (10)	0.50813 (17)	0.0212 (4)
H6A	0.2389	0.7000	0.4410	0.025*
H6B	0.2712	0.7133	0.5624	0.025*
H6C	0.1604	0.6563	0.5064	0.025*
C7	0.7405 (2)	0.64289 (10)	0.72869 (15)	0.0172 (4)
C8	0.8229 (2)	0.68434 (10)	0.68628 (16)	0.0196 (4)
H8	0.8024	0.6874	0.6133	0.024*
C9	0.9344 (2)	0.72098 (11)	0.75002 (17)	0.0235 (5)
H9	0.9897	0.7489	0.7205	0.028*
C10	0.9650 (2)	0.71691 (11)	0.85647 (18)	0.0274 (5)
H10	1.0407	0.7423	0.9001	0.033*
C11	0.8852 (2)	0.67582 (12)	0.89898 (17)	0.0276 (5)
H11	0.9065	0.6727	0.9720	0.033*
C12	0.7739 (2)	0.63893 (11)	0.83531 (16)	0.0229 (5)
H12	0.7199	0.6106	0.8654	0.027*
C13	0.8664 (2)	0.61490 (11)	0.20000 (16)	0.0200 (4)
C14	0.8967 (2)	0.56077 (12)	0.14644 (16)	0.0244 (5)
H14	0.8345	0.5233	0.1297	0.029*
C15	1.0187 (2)	0.56155 (13)	0.11728 (17)	0.0275 (5)
H15	1.0403	0.5238	0.0816	0.033*
C16	1.1103 (2)	0.61635 (12)	0.13915 (16)	0.0262 (5)
C17	1.0790 (2)	0.66962 (12)	0.19497 (17)	0.0255 (5)
H17	1.1417	0.7069	0.2127	0.031*
C18	0.9572 (2)	0.66934 (11)	0.22540 (17)	0.0222 (4)
H18	0.9367	0.7062	0.2633	0.027*
C19	1.2364 (3)	0.61845 (15)	0.0991 (2)	0.0380 (6)
H19A	1.2087	0.6383	0.0297	0.046*
H19B	1.2714	0.5725	0.0961	0.046*
H19C	1.3109	0.6459	0.1456	0.046*
C20	0.7003 (2)	0.45865 (10)	0.24260 (16)	0.0190 (4)
C21	0.5841 (2)	0.47540 (11)	0.15902 (16)	0.0211 (4)
H21	0.5468	0.5199	0.1518	0.025*
C22	0.5235 (2)	0.42619 (11)	0.08651 (17)	0.0228 (5)
H22	0.4445	0.4377	0.0293	0.027*
C23	0.5747 (2)	0.36063 (11)	0.09503 (18)	0.0251 (5)
C24	0.6912 (2)	0.34575 (11)	0.17858 (19)	0.0277 (5)
H24	0.7287	0.3013	0.1858	0.033*
C25	0.7547 (2)	0.39399 (11)	0.25185 (18)	0.0233 (5)
H25	0.8350	0.3827	0.3081	0.028*
C26	0.5040 (3)	0.30853 (13)	0.0151 (2)	0.0374 (6)
H26A	0.5641	0.2684	0.0240	0.045*
H26B	0.4892	0.3272	−0.0543	0.045*
H26C	0.4129	0.2961	0.0238	0.045*
H1N	0.313 (2)	0.4242 (11)	0.4505 (17)	0.010 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00918 (16)	0.01796 (18)	0.02017 (18)	0.00287 (13)	−0.00105 (13)	−0.00585 (14)
P1	0.0135 (2)	0.0205 (3)	0.0162 (2)	−0.00016 (19)	0.0050 (2)	0.0009 (2)
S1	0.0133 (2)	0.0297 (3)	0.0214 (3)	0.0016 (2)	0.0055 (2)	0.0021 (2)
S2	0.0159 (2)	0.0296 (3)	0.0201 (3)	−0.0048 (2)	0.0055 (2)	−0.0039 (2)
O1	0.0156 (7)	0.0284 (8)	0.0194 (7)	0.0006 (6)	0.0062 (6)	0.0053 (6)
O2	0.0194 (7)	0.0201 (7)	0.0179 (7)	0.0027 (6)	0.0034 (6)	−0.0002 (6)
N1	0.0111 (8)	0.0157 (9)	0.0154 (8)	0.0015 (6)	0.0033 (7)	0.0002 (7)
N2	0.0107 (8)	0.0172 (8)	0.0166 (8)	0.0004 (6)	0.0023 (6)	−0.0003 (7)
C1	0.0119 (9)	0.0186 (10)	0.0186 (10)	0.0001 (7)	−0.0003 (8)	−0.0010 (8)
C2	0.0095 (9)	0.0168 (10)	0.0256 (11)	0.0004 (7)	0.0018 (8)	−0.0012 (8)
C3	0.0131 (9)	0.0191 (10)	0.0188 (10)	0.0015 (7)	0.0058 (8)	0.0009 (8)
C4	0.0140 (9)	0.0177 (10)	0.0305 (12)	0.0017 (8)	0.0031 (9)	−0.0067 (9)
C5	0.0127 (9)	0.0196 (10)	0.0178 (10)	−0.0006 (7)	0.0050 (8)	−0.0028 (8)
C6	0.0147 (10)	0.0168 (10)	0.0297 (11)	0.0043 (8)	0.0032 (9)	−0.0003 (8)
C7	0.0136 (9)	0.0188 (10)	0.0169 (10)	0.0016 (7)	0.0012 (8)	−0.0044 (8)
C8	0.0181 (10)	0.0223 (11)	0.0176 (10)	0.0001 (8)	0.0039 (8)	−0.0036 (8)
C9	0.0175 (10)	0.0226 (11)	0.0289 (12)	−0.0023 (8)	0.0050 (9)	−0.0048 (9)
C10	0.0191 (11)	0.0296 (12)	0.0270 (12)	−0.0016 (9)	−0.0030 (9)	−0.0123 (10)
C11	0.0260 (12)	0.0355 (13)	0.0166 (10)	0.0042 (10)	−0.0004 (9)	−0.0054 (9)
C12	0.0219 (11)	0.0277 (12)	0.0183 (10)	0.0014 (9)	0.0051 (9)	0.0000 (9)
C13	0.0154 (10)	0.0290 (12)	0.0162 (10)	0.0004 (8)	0.0059 (8)	0.0057 (8)
C14	0.0240 (11)	0.0312 (12)	0.0194 (11)	−0.0051 (9)	0.0085 (9)	−0.0012 (9)
C15	0.0248 (11)	0.0410 (14)	0.0185 (11)	0.0018 (10)	0.0094 (9)	−0.0002 (10)
C16	0.0170 (10)	0.0449 (14)	0.0154 (10)	0.0006 (9)	0.0030 (8)	0.0102 (10)
C17	0.0203 (11)	0.0318 (12)	0.0221 (11)	−0.0050 (9)	0.0031 (9)	0.0102 (9)
C18	0.0223 (11)	0.0228 (11)	0.0210 (11)	0.0010 (8)	0.0058 (9)	0.0053 (8)
C19	0.0198 (11)	0.0663 (19)	0.0288 (13)	−0.0008 (12)	0.0086 (10)	0.0091 (12)
C20	0.0202 (10)	0.0223 (11)	0.0172 (10)	−0.0033 (8)	0.0094 (8)	−0.0001 (8)
C21	0.0237 (11)	0.0220 (11)	0.0184 (10)	−0.0011 (8)	0.0077 (9)	0.0030 (8)
C22	0.0236 (11)	0.0260 (12)	0.0204 (10)	−0.0077 (9)	0.0093 (9)	0.0008 (9)
C23	0.0280 (12)	0.0274 (12)	0.0268 (12)	−0.0104 (9)	0.0184 (10)	−0.0044 (9)
C24	0.0295 (12)	0.0208 (11)	0.0379 (13)	−0.0010 (9)	0.0178 (11)	0.0008 (10)
C25	0.0217 (10)	0.0225 (11)	0.0277 (11)	0.0013 (8)	0.0104 (9)	0.0039 (9)
C26	0.0385 (14)	0.0340 (14)	0.0445 (16)	−0.0150 (11)	0.0198 (13)	−0.0120 (12)

Geometric parameters (Å, º) top

Cu1—N2	1.9899 (16)	C9—C10	1.384 (3)
Cu1—N2ⁱ	1.9900 (16)	C9—H9	0.9500
Cu1—N1ⁱ	2.0074 (16)	C10—C11	1.379 (3)
Cu1—N1	2.0074 (16)	C10—H10	0.9500
Cu1—S1	3.0090 (7)	C11—C12	1.389 (3)
P1—O2	1.6272 (15)	C11—H11	0.9500
P1—O1	1.6283 (15)	C12—H12	0.9500
P1—S2	1.9489 (8)	C13—C14	1.379 (3)
P1—S1	1.9577 (8)	C13—C18	1.383 (3)
O1—C13	1.407 (2)	C14—C15	1.385 (3)
O2—C20	1.388 (2)	C14—H14	0.9500
N1—C5ⁱ	1.475 (2)	C15—C16	1.391 (3)
N1—C1	1.479 (2)	C15—H15	0.9500
N1—H1N	0.81 (2)	C16—C17	1.388 (3)
N2—C3	1.274 (3)	C16—C19	1.510 (3)
N2—C2	1.477 (2)	C17—C18	1.392 (3)
C1—C2	1.516 (3)	C17—H17	0.9500
C1—H1A	0.9900	C18—H18	0.9500
C1—H1B	0.9900	C19—H19A	0.9800
C2—H2A	0.9900	C19—H19B	0.9800
C2—H2B	0.9900	C19—H19C	0.9800
C3—C6	1.502 (3)	C20—C25	1.383 (3)
C3—C4	1.503 (3)	C20—C21	1.393 (3)
C4—C5	1.526 (3)	C21—C22	1.387 (3)
C4—H4A	0.9900	C21—H21	0.9500
C4—H4B	0.9900	C22—C23	1.388 (3)
C5—N1ⁱ	1.475 (2)	C22—H22	0.9500
C5—C7	1.521 (3)	C23—C24	1.386 (3)
C5—H5	1.0000	C23—C26	1.508 (3)
C6—H6A	0.9800	C24—C25	1.386 (3)
C6—H6B	0.9800	C24—H24	0.9500
C6—H6C	0.9800	C25—H25	0.9500
C7—C12	1.383 (3)	C26—H26A	0.9800
C7—C8	1.401 (3)	C26—H26B	0.9800
C8—C9	1.387 (3)	C26—H26C	0.9800
C8—H8	0.9500

N2—Cu1—N2ⁱ	179.999 (1)	C9—C8—C7	120.6 (2)
N2—Cu1—N1ⁱ	95.10 (7)	C9—C8—H8	119.7
N2ⁱ—Cu1—N1ⁱ	84.90 (7)	C7—C8—H8	119.7
N2—Cu1—N1	84.91 (7)	C10—C9—C8	120.1 (2)
N2ⁱ—Cu1—N1	95.10 (7)	C10—C9—H9	120.0
N1ⁱ—Cu1—N1	180.00 (9)	C8—C9—H9	120.0
N2—Cu1—S1	79.57 (5)	C11—C10—C9	119.8 (2)
N2ⁱ—Cu1—S1	100.43 (5)	C11—C10—H10	120.1
N1ⁱ—Cu1—S1	83.94 (5)	C9—C10—H10	120.1
N1—Cu1—S1	96.06 (5)	C10—C11—C12	120.2 (2)
O2—P1—O1	102.03 (8)	C10—C11—H11	119.9
O2—P1—S2	105.09 (6)	C12—C11—H11	119.9
O1—P1—S2	111.92 (6)	C7—C12—C11	120.9 (2)
O2—P1—S1	111.82 (6)	C7—C12—H12	119.5
O1—P1—S1	105.98 (6)	C11—C12—H12	119.5
S2—P1—S1	118.81 (4)	C14—C13—C18	120.6 (2)
P1—S1—Cu1	106.29 (3)	C14—C13—O1	119.69 (19)
C13—O1—P1	120.20 (12)	C18—C13—O1	119.67 (19)
C20—O2—P1	127.06 (13)	C13—C14—C15	119.4 (2)
C5ⁱ—N1—C1	113.27 (16)	C13—C14—H14	120.3
C5ⁱ—N1—Cu1	115.14 (12)	C15—C14—H14	120.3
C1—N1—Cu1	106.15 (12)	C14—C15—C16	121.5 (2)
C5ⁱ—N1—H1N	110.0 (15)	C14—C15—H15	119.3
C1—N1—H1N	108.3 (15)	C16—C15—H15	119.3
Cu1—N1—H1N	103.3 (15)	C17—C16—C15	118.1 (2)
C3—N2—C2	120.32 (16)	C17—C16—C19	121.5 (2)
C3—N2—Cu1	127.88 (14)	C15—C16—C19	120.4 (2)
C2—N2—Cu1	111.48 (12)	C16—C17—C18	121.1 (2)
N1—C1—C2	108.76 (16)	C16—C17—H17	119.5
N1—C1—H1A	109.9	C18—C17—H17	119.5
C2—C1—H1A	109.9	C13—C18—C17	119.4 (2)
N1—C1—H1B	109.9	C13—C18—H18	120.3
C2—C1—H1B	109.9	C17—C18—H18	120.3
H1A—C1—H1B	108.3	C16—C19—H19A	109.5
N2—C2—C1	108.72 (15)	C16—C19—H19B	109.5
N2—C2—H2A	109.9	H19A—C19—H19B	109.5
C1—C2—H2A	109.9	C16—C19—H19C	109.5
N2—C2—H2B	109.9	H19A—C19—H19C	109.5
C1—C2—H2B	109.9	H19B—C19—H19C	109.5
H2A—C2—H2B	108.3	C25—C20—O2	115.45 (19)
N2—C3—C6	123.65 (18)	C25—C20—C21	120.1 (2)
N2—C3—C4	121.68 (18)	O2—C20—C21	124.44 (19)
C6—C3—C4	114.57 (17)	C22—C21—C20	119.0 (2)
C3—C4—C5	119.40 (17)	C22—C21—H21	120.5
C3—C4—H4A	107.5	C20—C21—H21	120.5
C5—C4—H4A	107.5	C21—C22—C23	122.0 (2)
C3—C4—H4B	107.5	C21—C22—H22	119.0
C5—C4—H4B	107.5	C23—C22—H22	119.0
H4A—C4—H4B	107.0	C24—C23—C22	117.6 (2)
N1ⁱ—C5—C7	112.89 (16)	C24—C23—C26	122.3 (2)
N1ⁱ—C5—C4	110.59 (16)	C22—C23—C26	120.1 (2)
C7—C5—C4	109.37 (16)	C25—C24—C23	121.7 (2)
N1ⁱ—C5—H5	107.9	C25—C24—H24	119.1
C7—C5—H5	107.9	C23—C24—H24	119.1
C4—C5—H5	107.9	C20—C25—C24	119.6 (2)
C3—C6—H6A	109.5	C20—C25—H25	120.2
C3—C6—H6B	109.5	C24—C25—H25	120.2
H6A—C6—H6B	109.5	C23—C26—H26A	109.5
C3—C6—H6C	109.5	C23—C26—H26B	109.5
H6A—C6—H6C	109.5	H26A—C26—H26B	109.5
H6B—C6—H6C	109.5	C23—C26—H26C	109.5
C12—C7—C8	118.42 (19)	H26A—C26—H26C	109.5
C12—C7—C5	120.90 (19)	H26B—C26—H26C	109.5
C8—C7—C5	120.67 (18)

O2—P1—S1—Cu1	56.88 (6)	C3—C4—C5—C7	−172.28 (18)
O1—P1—S1—Cu1	167.26 (6)	N1ⁱ—C5—C7—C12	−120.0 (2)
S2—P1—S1—Cu1	−65.82 (4)	C4—C5—C7—C12	116.4 (2)
N2—Cu1—S1—P1	152.82 (5)	N1ⁱ—C5—C7—C8	60.8 (2)
N2ⁱ—Cu1—S1—P1	−27.17 (5)	C4—C5—C7—C8	−62.8 (2)
N1ⁱ—Cu1—S1—P1	56.49 (5)	C12—C7—C8—C9	−0.7 (3)
N1—Cu1—S1—P1	−123.51 (5)	C5—C7—C8—C9	178.54 (18)
O2—P1—O1—C13	−59.27 (16)	C7—C8—C9—C10	−0.1 (3)
S2—P1—O1—C13	52.61 (16)	C8—C9—C10—C11	0.6 (3)
S1—P1—O1—C13	−176.42 (13)	C9—C10—C11—C12	−0.4 (3)
O1—P1—O2—C20	−62.66 (17)	C8—C7—C12—C11	0.8 (3)
S2—P1—O2—C20	−179.58 (14)	C5—C7—C12—C11	−178.35 (19)
S1—P1—O2—C20	50.21 (17)	C10—C11—C12—C7	−0.3 (3)
N2—Cu1—N1—C5ⁱ	152.28 (14)	P1—O1—C13—C14	88.0 (2)
N2ⁱ—Cu1—N1—C5ⁱ	−27.72 (14)	P1—O1—C13—C18	−94.8 (2)
S1—Cu1—N1—C5ⁱ	73.36 (13)	C18—C13—C14—C15	−0.6 (3)
N2—Cu1—N1—C1	26.10 (13)	O1—C13—C14—C15	176.68 (19)
N2ⁱ—Cu1—N1—C1	−153.90 (13)	C13—C14—C15—C16	−1.2 (3)
S1—Cu1—N1—C1	−52.82 (12)	C14—C15—C16—C17	2.5 (3)
N1ⁱ—Cu1—N2—C3	5.34 (18)	C14—C15—C16—C19	−175.1 (2)
N1—Cu1—N2—C3	−174.66 (18)	C15—C16—C17—C18	−2.0 (3)
S1—Cu1—N2—C3	−77.53 (17)	C19—C16—C17—C18	175.5 (2)
N1ⁱ—Cu1—N2—C2	178.79 (13)	C14—C13—C18—C17	1.0 (3)
N1—Cu1—N2—C2	−1.21 (13)	O1—C13—C18—C17	−176.24 (18)
S1—Cu1—N2—C2	95.92 (13)	C16—C17—C18—C13	0.3 (3)
C5ⁱ—N1—C1—C2	−173.11 (16)	P1—O2—C20—C25	−176.35 (14)
Cu1—N1—C1—C2	−45.81 (17)	P1—O2—C20—C21	6.4 (3)
C3—N2—C2—C1	150.36 (18)	C25—C20—C21—C22	0.7 (3)
Cu1—N2—C2—C1	−23.66 (19)	O2—C20—C21—C22	177.87 (18)
N1—C1—C2—N2	46.1 (2)	C20—C21—C22—C23	0.4 (3)
C2—N2—C3—C6	−2.5 (3)	C21—C22—C23—C24	−1.0 (3)
Cu1—N2—C3—C6	170.41 (15)	C21—C22—C23—C26	179.1 (2)
C2—N2—C3—C4	−178.72 (18)	C22—C23—C24—C25	0.5 (3)
Cu1—N2—C3—C4	−5.8 (3)	C26—C23—C24—C25	−179.6 (2)
N2—C3—C4—C5	−27.8 (3)	O2—C20—C25—C24	−178.60 (19)
C6—C3—C4—C5	155.67 (19)	C21—C20—C25—C24	−1.2 (3)
C3—C4—C5—N1ⁱ	62.8 (2)	C23—C24—C25—C20	0.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2ⁱ	0.81 (2)	2.73 (2)	3.4868 (19)	157
C6—H6C···S2ⁱⁱ	0.98	2.80	3.755 (2)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₂₄H₃₂N₄)](C₁₄H₁₄O₂PS₂)₂
M_r	1058.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	103
a, b, c (Å)	9.9467 (18), 19.829 (3), 13.550 (2)
β (°)	107.563 (2)
V (Å³)	2548.0 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.43 × 0.27 × 0.17

Data collection
Diffractometer	Rigaku SPIDER
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.750, 0.890
No. of measured, independent and observed [I > 2σ(I)] reflections	19915, 5836, 4826
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.093, 1.00
No. of reflections	5836
No. of parameters	311
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.29

Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2ⁱ	0.81 (2)	2.73 (2)	3.4868 (19)	157
C6—H6C···S2ⁱⁱ	0.98	2.80	3.755 (2)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

Acknowledgements

This work was supported by the Education Committee of Sichuan Province (No. 09ZA057), the Science and Technology Office of Zigong City (No. 08X01) and the Science and Technology Committee of Sichuan Province, China (No. 2010GZ0130).

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. CSD CrossRef Web of Science Google Scholar
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Volume 66| Part 12| December 2010| Page m1592

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

(C-meso-N-meso-5,12-Di­methyl-7,14-di­phenyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene)copper(II) bis­­[O,O′-bis­­(4-methyl­phen­yl)di­thio­phosphate]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

(C-meso-N-meso-5,12-Dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)copper(II) bis[O,O′-bis(4-methylphenyl)dithiophosphate]