(meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene)copper(II) bis-[O,O'-bis-(4-methyl-phen-yl) dithio-phosphate].

The title compound, [Cu(C(16)H(32)N(4))](C(14)H(14)O(2)PS(2))(2) or [Cu(trans[14]dien)][S(2)P(OC(6)H(4)Me-4)(2)](2), where trans[14]dien is meso-5,7,7,12,14,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-deca-4,11-diene, was obtained by the reaction of [Cu(trans[14]dien)](ClO(4))(2) and [(C(2)H(5))(2)NH](2) [S(2)P(OC(6)H(4)Me-4)(2)](2). The Cu(II) atom lies on a centre of inversion and possesses a relatively undistorted square-planar coordination arrangement with four N atoms of the macrocyclic tetra-mine trans[14]dien [Cu-N = 1.9716 (19) and 2.0075 (19) Å]. The two uncoordinated [(4-MeC(6)H(4)O)(2)PS(2)](-) groups act as counter-ions to balance the charge and inter-act with the [Cu(trans[14]dien)](2+ )complex cation through N-H⋯S hydrogen bonds.

Related literature

For general background to the potential uses of copper(I) and copper(II) complexes with O,O′-dialkyl­dithio­phosphate ligands, see: Drew et al. (1987 ▶); Liu et al. (1995 ▶); Liaw et al. (2005 ▶). For a related structure, see: Xie et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C16H32N4)](C14H14O2PS2)2

M = 962.68

Triclinic,

a = 8.1043 (9) Å

b = 10.2120 (11) Å

c = 15.8435 (17) Å

α = 82.456 (2)°

β = 79.623 (2)°

γ = 70.797 (2)°

V = 1214.3 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.73 mm−1

T = 273 K

0.18 × 0.13 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.862, T max = 0.924

6424 measured reflections

4266 independent reflections

3527 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.092

S = 1.03

4266 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009815/dn2547sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009815/dn2547Isup2.hkl

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

[Cu(C16H32N4)](C14H14O2PS2)2	Z = 1
Mr = 962.68	F(000) = 507
Triclinic, P1	Dx = 1.316 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1043 (9) Å	Cell parameters from 2875 reflections
b = 10.2120 (11) Å	θ = 2.6–26.6°
c = 15.8435 (17) Å	µ = 0.73 mm−1
α = 82.456 (2)°	T = 273 K
β = 79.623 (2)°	Block, purple
γ = 70.797 (2)°	0.18 × 0.13 × 0.08 mm
V = 1214.3 (2) Å3

Bruker SMART CCD area-detector diffractometer	4266 independent reflections
Radiation source: fine-focus sealed tube	3527 reflections with I > 2σ(I)
graphite	Rint = 0.015
phi and ω scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.862, Tmax = 0.924	k = −12→12
6424 measured reflections	l = −14→18

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.042P)2 + 0.4609P] where P = (Fo2 + 2Fc2)/3
4266 reflections	(Δ/σ)max = 0.002
273 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
Cu1	0.5000	1.0000	0.5000	0.04864 (14)
N1	0.3721 (2)	0.97265 (18)	0.41247 (12)	0.0433 (4)
N2	0.3604 (2)	1.20195 (18)	0.48345 (13)	0.0455 (5)
H1	0.4288	1.2261	0.4408	0.055*
C15	0.2619 (3)	1.1075 (2)	0.37755 (16)	0.0504 (6)
H15A	0.1598	1.0966	0.3589	0.060*
H15B	0.3291	1.1435	0.3285	0.060*
C16	0.2037 (3)	1.2058 (2)	0.44768 (17)	0.0537 (6)
H16A	0.1464	1.2994	0.4246	0.064*
H16B	0.1202	1.1781	0.4924	0.064*
C17	0.3685 (3)	0.8572 (2)	0.39127 (15)	0.0457 (5)
C18	0.2533 (4)	0.8444 (3)	0.3313 (2)	0.0770 (9)
H18A	0.1657	0.9327	0.3219	0.116*
H18B	0.1961	0.7766	0.3559	0.116*
H18C	0.3240	0.8157	0.2774	0.116*
C19	0.4815 (3)	0.7214 (2)	0.42779 (17)	0.0520 (6)
H19A	0.4940	0.6512	0.3893	0.062*
H19B	0.4172	0.6973	0.4822	0.062*
C20	0.6663 (3)	0.7096 (2)	0.44375 (16)	0.0479 (6)
C21	0.7585 (4)	0.5565 (2)	0.4696 (2)	0.0673 (8)
H21A	0.8772	0.5448	0.4778	0.101*
H21B	0.7610	0.5004	0.4250	0.101*
H21C	0.6952	0.5282	0.5222	0.101*
C22	0.7720 (3)	0.7578 (3)	0.36425 (18)	0.0627 (7)
H22A	0.7205	0.8560	0.3518	0.094*
H22B	0.7712	0.7095	0.3163	0.094*
H22C	0.8915	0.7384	0.3741	0.094*
S1	0.49170 (8)	0.58786 (7)	0.69163 (5)	0.05677 (18)
S2	0.20902 (8)	0.88776 (7)	0.62430 (5)	0.05820 (19)
P1	0.26451 (8)	0.73303 (6)	0.71235 (4)	0.04638 (17)
O1	0.2353 (2)	0.78874 (18)	0.80671 (11)	0.0551 (4)
O2	0.0998 (2)	0.67359 (18)	0.72844 (12)	0.0593 (5)
C1	0.3506 (3)	0.8508 (3)	0.82839 (15)	0.0527 (6)
C2	0.3047 (4)	0.9926 (3)	0.82335 (18)	0.0678 (7)
H2	0.1998	1.0474	0.8040	0.081*
C3	0.4174 (6)	1.0532 (4)	0.8476 (2)	0.0854 (10)
H3	0.3861	1.1497	0.8445	0.102*
C4	0.5727 (5)	0.9756 (4)	0.8758 (2)	0.0829 (10)
C5	0.6147 (5)	0.8334 (4)	0.8803 (2)	0.0824 (9)
H5	0.7200	0.7784	0.8991	0.099*
C6	0.5046 (4)	0.7706 (3)	0.85759 (18)	0.0679 (7)
H6	0.5344	0.6741	0.8620	0.082*
C7	0.6929 (7)	1.0447 (5)	0.9027 (3)	0.1315 (18)
H7A	0.6468	1.1437	0.8911	0.197*
H7B	0.8091	1.0110	0.8709	0.197*
H7C	0.6985	1.0232	0.9632	0.197*
C8	0.0709 (3)	0.5670 (2)	0.78801 (16)	0.0500 (6)
C9	−0.0702 (3)	0.5272 (3)	0.78031 (17)	0.0571 (6)
H9	−0.1370	0.5682	0.7363	0.069*
C10	−0.1141 (4)	0.4258 (3)	0.83797 (19)	0.0654 (7)
H10	−0.2101	0.3989	0.8319	0.078*
C11	−0.0189 (4)	0.3637 (3)	0.90417 (19)	0.0637 (7)
C12	0.1238 (4)	0.4049 (3)	0.9097 (2)	0.0735 (8)
H12	0.1912	0.3636	0.9535	0.088*
C13	0.1709 (4)	0.5060 (3)	0.85227 (19)	0.0664 (8)
H13	0.2683	0.5319	0.8573	0.080*
C14	−0.0684 (5)	0.2542 (4)	0.9688 (2)	0.0930 (11)
H14A	−0.0184	0.1649	0.9456	0.140*
H14B	−0.1946	0.2769	0.9803	0.140*
H14C	−0.0234	0.2515	1.0212	0.140*

	U11	U22	U33	U12	U13	U23
Cu1	0.0435 (2)	0.0334 (2)	0.0719 (3)	−0.00251 (17)	−0.0267 (2)	−0.01418 (18)
N1	0.0372 (10)	0.0391 (10)	0.0572 (12)	−0.0120 (8)	−0.0136 (8)	−0.0074 (9)
N2	0.0381 (10)	0.0374 (10)	0.0615 (12)	−0.0095 (8)	−0.0103 (9)	−0.0079 (9)
C15	0.0434 (13)	0.0466 (13)	0.0644 (16)	−0.0120 (11)	−0.0225 (11)	−0.0016 (11)
C16	0.0428 (13)	0.0430 (13)	0.0735 (17)	−0.0054 (11)	−0.0197 (12)	−0.0040 (12)
C17	0.0364 (12)	0.0483 (13)	0.0563 (14)	−0.0154 (10)	−0.0050 (10)	−0.0147 (11)
C18	0.0620 (17)	0.076 (2)	0.104 (2)	−0.0157 (15)	−0.0330 (17)	−0.0351 (18)
C19	0.0513 (14)	0.0393 (13)	0.0718 (16)	−0.0188 (11)	−0.0079 (12)	−0.0164 (11)
C20	0.0424 (12)	0.0353 (12)	0.0661 (15)	−0.0086 (10)	−0.0088 (11)	−0.0127 (11)
C21	0.0658 (17)	0.0361 (13)	0.096 (2)	−0.0034 (12)	−0.0184 (15)	−0.0155 (13)
C22	0.0513 (15)	0.0569 (16)	0.0782 (19)	−0.0167 (13)	0.0024 (13)	−0.0166 (14)
S1	0.0490 (4)	0.0516 (4)	0.0687 (4)	−0.0070 (3)	−0.0151 (3)	−0.0149 (3)
S2	0.0438 (3)	0.0557 (4)	0.0707 (4)	−0.0152 (3)	−0.0071 (3)	0.0078 (3)
P1	0.0383 (3)	0.0466 (3)	0.0570 (4)	−0.0161 (3)	−0.0082 (3)	−0.0049 (3)
O1	0.0499 (10)	0.0603 (10)	0.0573 (10)	−0.0226 (8)	0.0021 (8)	−0.0119 (8)
O2	0.0500 (10)	0.0637 (11)	0.0735 (12)	−0.0307 (9)	−0.0224 (9)	0.0144 (9)
C1	0.0565 (15)	0.0581 (15)	0.0452 (14)	−0.0204 (12)	0.0002 (11)	−0.0142 (11)
C2	0.080 (2)	0.0573 (17)	0.0662 (18)	−0.0202 (15)	−0.0092 (15)	−0.0124 (14)
C3	0.130 (3)	0.066 (2)	0.075 (2)	−0.047 (2)	−0.012 (2)	−0.0162 (16)
C4	0.110 (3)	0.101 (3)	0.0615 (19)	−0.057 (2)	−0.0210 (18)	−0.0138 (17)
C5	0.087 (2)	0.102 (3)	0.069 (2)	−0.031 (2)	−0.0292 (17)	−0.0147 (18)
C6	0.0755 (19)	0.0644 (17)	0.0664 (18)	−0.0162 (15)	−0.0215 (15)	−0.0134 (14)
C7	0.183 (5)	0.171 (4)	0.100 (3)	−0.118 (4)	−0.049 (3)	−0.016 (3)
C8	0.0468 (13)	0.0470 (13)	0.0595 (15)	−0.0190 (11)	−0.0076 (11)	−0.0040 (11)
C9	0.0477 (14)	0.0660 (17)	0.0648 (16)	−0.0268 (13)	−0.0121 (12)	−0.0016 (13)
C10	0.0578 (16)	0.0706 (18)	0.079 (2)	−0.0379 (14)	−0.0041 (14)	−0.0082 (15)
C11	0.0751 (19)	0.0575 (16)	0.0657 (18)	−0.0340 (15)	−0.0027 (15)	−0.0052 (13)
C12	0.088 (2)	0.0710 (19)	0.0742 (19)	−0.0385 (17)	−0.0310 (17)	0.0119 (15)
C13	0.0683 (17)	0.0664 (17)	0.0800 (19)	−0.0395 (15)	−0.0285 (15)	0.0128 (15)
C14	0.122 (3)	0.087 (2)	0.084 (2)	−0.061 (2)	−0.006 (2)	0.0100 (19)

Cu1—N1i	1.9714 (18)	P1—O2	1.6075 (16)
Cu1—N1	1.9714 (18)	P1—O1	1.6193 (18)
Cu1—N2i	2.0079 (18)	O1—C1	1.398 (3)
Cu1—N2	2.0080 (17)	O2—C8	1.396 (3)
N1—C17	1.278 (3)	C1—C2	1.367 (4)
N1—C15	1.473 (3)	C1—C6	1.371 (4)
N2—C16	1.468 (3)	C2—C3	1.388 (4)
N2—C20i	1.499 (3)	C2—H2	0.9300
N2—H1	0.8576	C3—C4	1.366 (5)
C15—C16	1.502 (3)	C3—H3	0.9300
C15—H15A	0.9700	C4—C5	1.373 (5)
C15—H15B	0.9700	C4—C7	1.519 (4)
C16—H16A	0.9700	C5—C6	1.376 (4)
C16—H16B	0.9700	C5—H5	0.9300
C17—C18	1.491 (3)	C6—H6	0.9300
C17—C19	1.497 (3)	C7—H7A	0.9600
C18—H18A	0.9600	C7—H7B	0.9600
C18—H18B	0.9600	C7—H7C	0.9600
C18—H18C	0.9600	C8—C9	1.363 (3)
C19—C20	1.527 (3)	C8—C13	1.371 (4)
C19—H19A	0.9700	C9—C10	1.382 (4)
C19—H19B	0.9700	C9—H9	0.9300
C20—N2i	1.499 (3)	C10—C11	1.376 (4)
C20—C22	1.513 (4)	C10—H10	0.9300
C20—C21	1.531 (3)	C11—C12	1.375 (4)
C21—H21A	0.9600	C11—C14	1.518 (4)
C21—H21B	0.9600	C12—C13	1.389 (4)
C21—H21C	0.9600	C12—H12	0.9300
C22—H22A	0.9600	C13—H13	0.9300
C22—H22B	0.9600	C14—H14A	0.9600
C22—H22C	0.9600	C14—H14B	0.9600
S1—P1	1.9519 (9)	C14—H14C	0.9600
S2—P1	1.9556 (9)
N1i—Cu1—N1	180.000 (1)	H22A—C22—H22C	109.5
N1i—Cu1—N2i	85.26 (7)	H22B—C22—H22C	109.5
N1—Cu1—N2i	94.74 (7)	O2—P1—O1	97.09 (9)
N1i—Cu1—N2	94.74 (7)	O2—P1—S1	112.84 (7)
N1—Cu1—N2	85.26 (7)	O1—P1—S1	110.67 (7)
N2i—Cu1—N2	180.00 (12)	O2—P1—S2	105.49 (7)
C17—N1—C15	121.97 (19)	O1—P1—S2	111.15 (7)
C17—N1—Cu1	127.29 (16)	S1—P1—S2	117.61 (4)
C15—N1—Cu1	110.51 (13)	C1—O1—P1	120.99 (14)
C16—N2—C20i	117.81 (18)	C8—O2—P1	128.25 (15)
C16—N2—Cu1	105.96 (13)	C2—C1—C6	120.3 (3)
C20i—N2—Cu1	117.25 (14)	C2—C1—O1	119.2 (2)
C16—N2—H1	105.2	C6—C1—O1	120.4 (2)
C20i—N2—H1	109.6	C1—C2—C3	118.8 (3)
Cu1—N2—H1	98.8	C1—C2—H2	120.6
N1—C15—C16	107.80 (19)	C3—C2—H2	120.6
N1—C15—H15A	110.1	C4—C3—C2	122.1 (3)
C16—C15—H15A	110.1	C4—C3—H3	119.0
N1—C15—H15B	110.1	C2—C3—H3	119.0
C16—C15—H15B	110.1	C3—C4—C5	117.7 (3)
H15A—C15—H15B	108.5	C3—C4—C7	121.0 (4)
N2—C16—C15	108.29 (19)	C5—C4—C7	121.3 (4)
N2—C16—H16A	110.0	C4—C5—C6	121.5 (3)
C15—C16—H16A	110.0	C4—C5—H5	119.3
N2—C16—H16B	110.0	C6—C5—H5	119.3
C15—C16—H16B	110.0	C1—C6—C5	119.7 (3)
H16A—C16—H16B	108.4	C1—C6—H6	120.2
N1—C17—C18	124.4 (2)	C5—C6—H6	120.2
N1—C17—C19	121.0 (2)	C4—C7—H7A	109.5
C18—C17—C19	114.6 (2)	C4—C7—H7B	109.5
C17—C18—H18A	109.5	H7A—C7—H7B	109.5
C17—C18—H18B	109.5	C4—C7—H7C	109.5
H18A—C18—H18B	109.5	H7A—C7—H7C	109.5
C17—C18—H18C	109.5	H7B—C7—H7C	109.5
H18A—C18—H18C	109.5	C9—C8—C13	120.3 (2)
H18B—C18—H18C	109.5	C9—C8—O2	115.3 (2)
C17—C19—C20	119.01 (19)	C13—C8—O2	124.3 (2)
C17—C19—H19A	107.6	C8—C9—C10	120.0 (3)
C20—C19—H19A	107.6	C8—C9—H9	120.0
C17—C19—H19B	107.6	C10—C9—H9	120.0
C20—C19—H19B	107.6	C11—C10—C9	121.5 (3)
H19A—C19—H19B	107.0	C11—C10—H10	119.3
N2i—C20—C22	111.23 (19)	C9—C10—H10	119.3
N2i—C20—C19	105.85 (18)	C12—C11—C10	117.2 (3)
C22—C20—C19	111.6 (2)	C12—C11—C14	121.0 (3)
N2i—C20—C21	110.8 (2)	C10—C11—C14	121.8 (3)
C22—C20—C21	109.8 (2)	C11—C12—C13	122.3 (3)
C19—C20—C21	107.38 (19)	C11—C12—H12	118.9
C20—C21—H21A	109.5	C13—C12—H12	118.9
C20—C21—H21B	109.5	C8—C13—C12	118.7 (3)
H21A—C21—H21B	109.5	C8—C13—H13	120.6
C20—C21—H21C	109.5	C12—C13—H13	120.6
H21A—C21—H21C	109.5	C11—C14—H14A	109.5
H21B—C21—H21C	109.5	C11—C14—H14B	109.5
C20—C22—H22A	109.5	H14A—C14—H14B	109.5
C20—C22—H22B	109.5	C11—C14—H14C	109.5
H22A—C22—H22B	109.5	H14A—C14—H14C	109.5
C20—C22—H22C	109.5	H14B—C14—H14C	109.5
C17—N1—C15—C16	143.9 (2)	C1—C2—C3—C4	0.3 (5)
C20i—N2—C16—C15	−178.75 (19)	C2—C3—C4—C5	−0.5 (5)
N1—C15—C16—N2	50.8 (3)	C2—C3—C4—C7	−179.5 (3)
C15—N1—C17—C18	−1.0 (4)	C3—C4—C5—C6	−0.2 (5)
C15—N1—C17—C19	−179.9 (2)	C7—C4—C5—C6	178.7 (3)
N1—C17—C19—C20	−36.3 (3)	C2—C1—C6—C5	−1.2 (4)
C18—C17—C19—C20	144.7 (2)	O1—C1—C6—C5	−178.7 (3)
C17—C19—C20—N2i	68.8 (3)	C4—C5—C6—C1	1.1 (5)
C17—C19—C20—C22	−52.3 (3)	P1—O2—C8—C9	−172.40 (19)
C17—C19—C20—C21	−172.8 (2)	P1—O2—C8—C13	9.3 (4)
O2—P1—O1—C1	178.84 (18)	C13—C8—C9—C10	0.6 (4)
S1—P1—O1—C1	61.14 (19)	O2—C8—C9—C10	−177.8 (2)
S2—P1—O1—C1	−71.48 (18)	C8—C9—C10—C11	0.5 (4)
O1—P1—O2—C8	−62.5 (2)	C9—C10—C11—C12	−1.2 (4)
S1—P1—O2—C8	53.5 (2)	C9—C10—C11—C14	178.8 (3)
S2—P1—O2—C8	−176.78 (19)	C10—C11—C12—C13	0.8 (5)
P1—O1—C1—C2	98.2 (2)	C14—C11—C12—C13	−179.2 (3)
P1—O1—C1—C6	−84.4 (3)	C9—C8—C13—C12	−1.0 (4)
C6—C1—C2—C3	0.5 (4)	O2—C8—C13—C12	177.3 (3)
O1—C1—C2—C3	178.0 (2)	C11—C12—C13—C8	0.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···S1i	0.86	2.77	3.559 (2)	153
N2—H1···S2i	0.86	2.83	3.477 (2)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯S1i	0.86	2.77	3.559 (2)	153
N2—H1⋯S2i	0.86	2.83	3.477 (2)	134

Symmetry code: (i) .