(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)copper(II) bis-[O,O'-(o-phenyl-ene)dithio-phosphate].

In the title compound, [Cu(C(16)H(36)N(4))](C(6)H(4)O(2)PS(2))(2), the Cu(II) cation lies on an inversion center and is chelated by the macrocyclic tetra-amine ligand in a slightly distorted CuN(4) square-planar geometry. The axial positions are occupied by two O,O'-(o-phenyl-ene)dithio-phosphate anions with long Cu⋯S distances of 3.0940 (7) Å. Inter-molecular N-H⋯S and C-H⋯O hydrogen bonding is present between the anions and the cation and helps to stabilize the crystal structure.

Related literature

For applications of macrocyclic tetra­amine compounds, see: Groeta et al. (2000 ▶); Aoki & Kimura (2002 ▶). For related structures, see: Feng et al. (2009 ▶); He et al. (2010 ▶); Xie et al. (2009 ▶).

Experimental

Crystal data

[Cu(C16H36N4)](C6H4O2PS2)2

M = 754.39

Monoclinic,

a = 12.3107 (4) Å

b = 12.1612 (3) Å

c = 12.3703 (4) Å

β = 107.136 (3)°

V = 1769.78 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.98 mm−1

T = 294 K

0.38 × 0.34 × 0.28 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009 ▶) T min = 0.697, T max = 0.761

7203 measured reflections

3621 independent reflections

2662 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.072

S = 1.02

3621 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046684/xu5086sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046684/xu5086Isup2.hkl

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

[Cu(C16H36N4)](C6H4O2PS2)2	F(000) = 790
Mr = 754.39	Dx = 1.416 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 4041 reflections
a = 12.3107 (4) Å	θ = 3.2–29.2°
b = 12.1612 (3) Å	µ = 0.98 mm−1
c = 12.3703 (4) Å	T = 294 K
β = 107.136 (3)°	Block, dark-violet
V = 1769.78 (9) Å3	0.38 × 0.34 × 0.28 mm
Z = 2

Oxford Diffraction Xcalibur Eos diffractometer	3621 independent reflections
Radiation source: fine-focus sealed tube	2662 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.3°
ω scans	h = −14→15
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	k = −15→14
Tmin = 0.697, Tmax = 0.761	l = −15→8
7203 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0358P)2] where P = (Fo2 + 2Fc2)/3
3621 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.60607 (18)	0.32263 (15)	0.63651 (17)	0.0421 (5)
H1A	0.6460	0.2530	0.6438	0.050*
H1B	0.5573	0.3210	0.6854	0.050*
C6	0.5147 (2)	0.85983 (17)	0.5043 (2)	0.0750 (9)
H6B	0.4588	0.8709	0.5434	0.113*
H6A	0.4810	0.8734	0.4250	0.113*
H6C	0.5770	0.9096	0.5336	0.113*
C3	0.69922 (17)	0.62275 (15)	0.67689 (17)	0.0385 (5)
C4	0.62020 (18)	0.72195 (15)	0.64523 (18)	0.0448 (5)
H4A	0.5636	0.7154	0.6853	0.054*
H4B	0.6647	0.7872	0.6739	0.054*
C2	0.69001 (16)	0.41537 (15)	0.67066 (18)	0.0417 (5)
H2B	0.7315	0.4094	0.7503	0.050*
H2A	0.7441	0.4122	0.6275	0.050*
C5	0.55801 (18)	0.74158 (14)	0.52163 (18)	0.0412 (5)
H5	0.6116	0.7305	0.4777	0.049*
C8	0.7587 (2)	0.62675 (19)	0.80430 (19)	0.0669 (7)
H8A	0.7031	0.6214	0.8445	0.100*
H8C	0.7993	0.6949	0.8231	0.100*
H8B	0.8111	0.5665	0.8253	0.100*
C7	0.78770 (19)	0.62258 (17)	0.6133 (2)	0.0589 (7)
H7B	0.8442	0.5677	0.6449	0.088*
H7C	0.8232	0.6936	0.6198	0.088*
H7A	0.7516	0.6063	0.5349	0.088*
P1	0.76165 (4)	0.41284 (4)	0.34491 (4)	0.03621 (14)
S1	0.62560 (5)	0.50447 (5)	0.31713 (5)	0.05140 (17)
S2	0.77079 (5)	0.27519 (4)	0.42553 (5)	0.04891 (16)
O1	0.79072 (12)	0.39508 (11)	0.22398 (12)	0.0475 (4)
O2	0.87362 (11)	0.49007 (10)	0.40083 (12)	0.0452 (4)
C9	0.91021 (16)	0.53308 (17)	0.31328 (19)	0.0411 (5)
N1	0.53721 (13)	0.33932 (11)	0.51843 (12)	0.0309 (4)
H1	0.5849	0.3263	0.4759	0.037*
C10	0.98455 (17)	0.61848 (17)	0.3208 (2)	0.0554 (6)
H10	1.0162	0.6554	0.3886	0.067*
C13	0.8889 (2)	0.50583 (19)	0.1159 (2)	0.0611 (7)
H13	0.8572	0.4685	0.0483	0.073*
C14	0.86346 (18)	0.47825 (17)	0.21245 (19)	0.0438 (5)
Cu1	0.5000	0.5000	0.5000	0.03160 (11)
N2	0.62678 (12)	0.52077 (11)	0.64861 (13)	0.0315 (4)
H2	0.5886	0.5211	0.7014	0.038*
C11	1.0108 (2)	0.6478 (2)	0.2226 (3)	0.0656 (8)
H11	1.0605	0.7058	0.2246	0.079*
C12	0.9647 (2)	0.5925 (2)	0.1231 (3)	0.0713 (8)
H12	0.9844	0.6133	0.0590	0.086*

	U11	U22	U33	U12	U13	U23
C1	0.0483 (13)	0.0289 (10)	0.0428 (12)	0.0079 (9)	0.0039 (10)	0.0100 (9)
C6	0.095 (2)	0.0260 (11)	0.086 (2)	−0.0022 (12)	−0.0002 (17)	0.0049 (12)
C3	0.0387 (11)	0.0351 (11)	0.0366 (12)	−0.0048 (9)	0.0034 (9)	−0.0070 (9)
C4	0.0538 (14)	0.0319 (11)	0.0451 (13)	−0.0057 (10)	0.0093 (11)	−0.0101 (10)
C2	0.0377 (11)	0.0350 (11)	0.0446 (13)	0.0084 (10)	−0.0001 (10)	0.0061 (9)
C5	0.0477 (13)	0.0242 (10)	0.0493 (14)	−0.0043 (9)	0.0107 (11)	0.0009 (9)
C8	0.0761 (18)	0.0619 (15)	0.0461 (15)	−0.0064 (14)	−0.0075 (13)	−0.0119 (12)
C7	0.0427 (13)	0.0543 (14)	0.0793 (19)	−0.0091 (11)	0.0173 (13)	−0.0009 (13)
P1	0.0333 (3)	0.0453 (3)	0.0317 (3)	−0.0046 (2)	0.0121 (2)	−0.0077 (2)
S1	0.0385 (3)	0.0599 (4)	0.0593 (4)	0.0075 (3)	0.0198 (3)	0.0164 (3)
S2	0.0556 (4)	0.0443 (3)	0.0498 (4)	0.0056 (3)	0.0203 (3)	−0.0009 (3)
O1	0.0522 (9)	0.0577 (9)	0.0393 (9)	−0.0202 (8)	0.0239 (7)	−0.0174 (7)
O2	0.0381 (8)	0.0580 (9)	0.0381 (8)	−0.0114 (7)	0.0092 (7)	−0.0122 (7)
C9	0.0276 (11)	0.0434 (12)	0.0522 (14)	−0.0006 (9)	0.0116 (10)	0.0005 (10)
N1	0.0352 (8)	0.0224 (8)	0.0354 (9)	0.0057 (7)	0.0107 (7)	0.0047 (7)
C10	0.0321 (12)	0.0496 (13)	0.0775 (19)	−0.0012 (10)	0.0050 (12)	0.0001 (13)
C13	0.0662 (16)	0.0712 (17)	0.0568 (16)	−0.0033 (14)	0.0352 (14)	−0.0009 (13)
C14	0.0371 (12)	0.0526 (14)	0.0468 (14)	−0.0015 (10)	0.0201 (10)	−0.0047 (10)
Cu1	0.03122 (18)	0.02070 (16)	0.0368 (2)	0.00205 (14)	0.00057 (14)	0.00432 (14)
N2	0.0308 (9)	0.0325 (9)	0.0305 (9)	0.0028 (7)	0.0080 (7)	0.0025 (7)
C11	0.0361 (13)	0.0555 (15)	0.109 (2)	0.0023 (12)	0.0270 (15)	0.0229 (16)
C12	0.0622 (17)	0.0794 (19)	0.087 (2)	0.0072 (15)	0.0440 (17)	0.0226 (16)

C1—H1A	0.9700	C7—H7A	0.9600
C1—H1B	0.9700	P1—S1	1.9560 (7)
C1—C2	1.504 (3)	P1—S2	1.9348 (8)
C1—N1	1.471 (2)	P1—O1	1.6517 (14)
C6—H6B	0.9600	P1—O2	1.6429 (14)
C6—H6A	0.9600	O1—C14	1.386 (2)
C6—H6C	0.9600	O2—C9	1.392 (2)
C6—C5	1.527 (3)	C9—C10	1.369 (3)
C3—C4	1.527 (3)	C9—C14	1.382 (3)
C3—C8	1.531 (3)	N1—C5i	1.499 (2)
C3—C7	1.520 (3)	N1—H1	0.9100
C3—N2	1.507 (2)	N1—Cu1	2.0047 (13)
C4—H4A	0.9700	C10—H10	0.9300
C4—H4B	0.9700	C10—C11	1.391 (3)
C4—C5	1.514 (3)	C13—H13	0.9300
C2—H2B	0.9700	C13—C14	1.363 (3)
C2—H2A	0.9700	C13—C12	1.393 (3)
C2—N2	1.483 (2)	Cu1—N1i	2.0047 (13)
C5—H5	0.9800	Cu1—N2	2.0466 (15)
C5—N1i	1.498 (2)	Cu1—N2i	2.0466 (15)
C8—H8A	0.9600	N2—H2	0.9100
C8—H8C	0.9600	C11—H11	0.9300
C8—H8B	0.9600	C11—C12	1.370 (4)
C7—H7B	0.9600	C12—H12	0.9300
C7—H7C	0.9600
C1—C2—H2B	110.0	S2—P1—S1	120.01 (4)
C1—C2—H2A	110.0	O1—P1—S1	108.55 (6)
C1—N1—C5i	113.81 (14)	O1—P1—S2	111.01 (6)
C1—N1—H1	105.6	O2—P1—S1	108.48 (5)
C1—N1—Cu1	107.04 (11)	O2—P1—S2	111.31 (6)
H1A—C1—H1B	108.3	O2—P1—O1	94.43 (7)
C6—C5—H5	108.4	C9—O2—P1	108.12 (12)
H6B—C6—H6A	109.5	C9—C10—H10	121.4
H6B—C6—H6C	109.5	C9—C10—C11	117.2 (2)
H6A—C6—H6C	109.5	C9—C14—O1	111.67 (19)
C3—C4—H4A	107.7	N1—C1—H1A	109.9
C3—C4—H4B	107.7	N1—C1—H1B	109.9
C3—C8—H8A	109.5	N1—C1—C2	108.83 (15)
C3—C8—H8C	109.5	N1i—C5—C6	111.41 (17)
C3—C8—H8B	109.5	N1i—C5—C4	110.13 (15)
C3—C7—H7B	109.5	N1i—C5—H5	108.4
C3—C7—H7C	109.5	N1—Cu1—N1i	180.0
C3—C7—H7A	109.5	N1i—Cu1—N2i	85.98 (6)
C3—N2—Cu1	123.54 (11)	N1—Cu1—N2i	94.02 (6)
C3—N2—H2	103.1	N1—Cu1—N2	85.98 (6)
C4—C3—C8	108.33 (17)	N1i—Cu1—N2	94.02 (6)
C4—C5—C6	110.00 (17)	C10—C9—O2	126.6 (2)
C4—C5—H5	108.4	C10—C9—C14	121.3 (2)
H4A—C4—H4B	107.1	C10—C11—H11	119.4
C2—C1—H1A	109.9	C13—C14—O1	126.3 (2)
C2—C1—H1B	109.9	C13—C14—C9	122.0 (2)
C2—N2—C3	115.21 (15)	C13—C12—H12	119.3
C2—N2—Cu1	106.18 (11)	C14—O1—P1	108.47 (12)
C2—N2—H2	103.1	C14—C9—O2	112.15 (18)
H2B—C2—H2A	108.4	C14—C13—H13	121.5
C5—C6—H6B	109.5	C14—C13—C12	116.9 (2)
C5—C6—H6A	109.5	Cu1—N1—H1	105.6
C5—C6—H6C	109.5	Cu1—N2—H2	103.1
C5—C4—C3	118.56 (17)	N2—C3—C4	107.57 (15)
C5—C4—H4A	107.7	N2—C3—C8	109.63 (16)
C5—C4—H4B	107.7	N2—C3—C7	110.12 (16)
C5i—N1—H1	105.6	N2—C2—C1	108.46 (15)
C5i—N1—Cu1	118.17 (12)	N2—C2—H2B	110.0
H8A—C8—H8C	109.5	N2—C2—H2A	110.0
H8A—C8—H8B	109.5	N2—Cu1—N2i	180.0
H8C—C8—H8B	109.5	C11—C10—H10	121.4
C7—C3—C4	111.59 (18)	C11—C12—C13	121.4 (3)
C7—C3—C8	109.55 (19)	C11—C12—H12	119.3
H7B—C7—H7C	109.5	C12—C13—H13	121.5
H7B—C7—H7A	109.5	C12—C11—C10	121.1 (2)
H7C—C7—H7A	109.5	C12—C11—H11	119.4
C1—C2—N2—C3	−179.14 (16)	S1—P1—O2—C9	−90.46 (12)
C1—C2—N2—Cu1	−38.57 (18)	S2—P1—O1—C14	−135.33 (12)
C1—N1—Cu1—N2	15.68 (13)	S2—P1—O2—C9	135.39 (11)
C1—N1—Cu1—N2i	−164.32 (13)	O1—P1—O2—C9	20.78 (13)
C3—C4—C5—C6	−162.4 (2)	O2—P1—O1—C14	−20.48 (14)
C3—C4—C5—N1i	74.4 (2)	O2—C9—C10—C11	179.29 (18)
C4—C3—N2—C2	178.22 (16)	O2—C9—C14—O1	0.8 (3)
C4—C3—N2—Cu1	45.3 (2)	O2—C9—C14—C13	−179.1 (2)
C2—C1—N1—C5i	−173.86 (16)	C9—C10—C11—C12	−0.6 (3)
C2—C1—N1—Cu1	−41.42 (18)	N1—C1—C2—N2	54.5 (2)
C5i—N1—Cu1—N2	145.70 (14)	N1—Cu1—N2—C3	149.25 (14)
C5i—N1—Cu1—N2i	−34.30 (14)	N1i—Cu1—N2—C3	−30.75 (14)
C8—C3—C4—C5	175.34 (19)	N1i—Cu1—N2—C2	−167.17 (12)
C8—C3—N2—C2	−64.2 (2)	N1—Cu1—N2—C2	12.83 (12)
C8—C3—N2—Cu1	162.85 (14)	C10—C9—C14—O1	−179.94 (17)
C7—C3—C4—C5	54.7 (2)	C10—C9—C14—C13	0.2 (3)
C7—C3—N2—C2	56.4 (2)	C10—C11—C12—C13	0.7 (4)
C7—C3—N2—Cu1	−76.55 (19)	C14—C9—C10—C11	0.1 (3)
P1—O1—C14—C9	14.3 (2)	C14—C13—C12—C11	−0.4 (4)
P1—O1—C14—C13	−165.8 (2)	N2—C3—C4—C5	−66.2 (2)
P1—O2—C9—C10	165.19 (17)	C12—C13—C14—O1	−179.9 (2)
P1—O2—C9—C14	−15.6 (2)	C12—C13—C14—C9	−0.1 (3)
S1—P1—O1—C14	90.71 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2	0.91	2.62	3.4849 (16)	160
N2—H2···S1i	0.91	2.60	3.2715 (16)	132
C1—H1A···O1ii	0.97	2.52	3.449 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2	0.91	2.62	3.4849 (16)	160
N2—H2⋯S1i	0.91	2.60	3.2715 (16)	132
C1—H1A⋯O1ii	0.97	2.52	3.449 (2)	160

Symmetry codes: (i) ; (ii) .