(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-azacyclo-tetra-deca-ne)nickel(II) bis-(O,O'-dibenzyl dithio-phosphate).

In the title salt-type 1:2 adduct, [Ni(C(16)H(36)N(4))](C(14)H(14)O(2)PS(2))(2) or [Ni(tet-a)][S(2)P(OCH(2)Ph)(2)](2), where tet-a is meso-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane, the [Ni(tet-a)](2+) complex cation exhibits a relatively undistorted square-planar geometry about the Ni atom, which lies on an inversion centre and is coordinated by four macrocyclic N atoms. The two O,O'-bis-(2-phenyl-meth-yl) dithio-phosphate anions act as counter-ions to balance the charge and they inter-act with the complex through N-H⋯S hydrogen bonds. Important geometric data include Ni-N distances of 1.958 (3) and 1.963 (3) Å.

Related literature

For related literature, see: Burchell et al. (2000 ▶); Ali et al. (2004 ▶); Allen (2002 ▶); Li et al. (2006 ▶); Liu et al. (1997 ▶).

Experimental

Crystal data

[Ni(C16H36N4)](C14H14O2PS2)2

M = 961.88

Monoclinic,

a = 16.371 (5) Å

b = 14.917 (5) Å

c = 9.964 (4) Å

β = 103.11 (3)°

V = 2369.9 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.70 mm−1

T = 290 (2) K

0.40 × 0.38 × 0.36 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.768, T max = 0.787

5571 measured reflections

4393 independent reflections

2880 reflections with I > 2σ(I)

R int = 0.021

3 standard reflections every 300 reflections intensity decay: 1.1%

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.127

S = 1.01

4393 reflections

275 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.34 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008398/dn2324sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008398/dn2324Isup2.hkl

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

[Ni(C16H36N4)](C14H14O2PS2)2	F000 = 1020
Mr = 961.88	Dx = 1.348 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19 reflections
a = 16.371 (5) Å	θ = 4.4–5.5º
b = 14.917 (5) Å	µ = 0.70 mm−1
c = 9.964 (4) Å	T = 290 (2) K
β = 103.11 (3)º	Block, red
V = 2369.9 (15) Å3	0.40 × 0.38 × 0.36 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	Rint = 0.021
Radiation source: fine-focus sealed tube	θmax = 25.5º
Monochromator: graphite	θmin = 1.3º
T = 290(2) K	h = −7→19
ω/2θ scans	k = −18→0
Absorption correction: ψ scan(North et al., 1968)	l = −12→11
Tmin = 0.768, Tmax = 0.787	3 standard reflections
5571 measured reflections	every 300 reflections
4393 independent reflections	intensity decay: 1.1%
2880 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.0689P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
4393 reflections	Δρmax = 0.52 e Å−3
275 parameters	Δρmin = −0.34 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Ni1	0.5000	0.5000	0.0000	0.02975 (18)
S1	0.39590 (6)	0.45749 (7)	0.26928 (12)	0.0569 (3)
S2	0.28652 (6)	0.64383 (7)	0.13356 (11)	0.0498 (3)
P1	0.29136 (6)	0.52753 (7)	0.22790 (10)	0.0406 (3)
O1	0.26427 (15)	0.53665 (18)	0.3726 (3)	0.0509 (7)
O2	0.21601 (15)	0.47114 (17)	0.1325 (3)	0.0521 (7)
N1	0.57052 (16)	0.53521 (17)	0.1790 (3)	0.0341 (7)
H1	0.5357	0.5294	0.2379	0.041*
N2	0.55476 (16)	0.38269 (17)	0.0308 (3)	0.0332 (6)
H2	0.5975	0.3845	−0.0138	0.040*
C1	0.6346 (2)	0.4648 (2)	0.2251 (4)	0.0543 (12)
H1A	0.6539	0.4663	0.3245	0.065*
H1B	0.6824	0.4747	0.1844	0.065*
C2	0.5955 (2)	0.3765 (2)	0.1806 (4)	0.0478 (10)
H2A	0.5540	0.3619	0.2330	0.057*
H2B	0.6378	0.3298	0.1960	0.057*
C3	0.5074 (2)	0.2981 (2)	−0.0165 (3)	0.0353 (8)
H3	0.4636	0.2913	0.0354	0.042*
C4	0.4652 (2)	0.3050 (2)	−0.1675 (4)	0.0397 (9)
H4A	0.4439	0.2462	−0.1989	0.048*
H4B	0.5077	0.3204	−0.2174	0.048*
C5	0.5636 (2)	0.2146 (2)	0.0096 (4)	0.0452 (9)
H5A	0.6067	0.2194	−0.0413	0.068*
H5B	0.5304	0.1621	−0.0197	0.068*
H5C	0.5889	0.2101	0.1062	0.068*
C6	0.6063 (2)	0.6282 (2)	0.2081 (4)	0.0359 (8)
C7	0.6734 (2)	0.6441 (3)	0.1263 (4)	0.0542 (11)
H7A	0.6523	0.6262	0.0323	0.081*
H7B	0.7225	0.6096	0.1658	0.081*
H7C	0.6877	0.7066	0.1293	0.081*
C8	0.6443 (2)	0.6385 (3)	0.3636 (4)	0.0543 (11)
H8A	0.6602	0.6998	0.3838	0.081*
H8B	0.6928	0.6008	0.3896	0.081*
H8C	0.6035	0.6212	0.4144	0.081*
C9	0.1889 (3)	0.5872 (3)	0.3782 (4)	0.0624 (12)
H9A	0.1446	0.5736	0.2982	0.075*
H9B	0.2003	0.6510	0.3783	0.075*
C10	0.1620 (2)	0.5621 (3)	0.5064 (4)	0.0511 (10)
C11	0.1766 (3)	0.6179 (3)	0.6203 (5)	0.0639 (12)
H11	0.2020	0.6734	0.6175	0.077*
C12	0.1527 (3)	0.5897 (5)	0.7399 (5)	0.0884 (18)
H12	0.1623	0.6266	0.8171	0.106*
C13	0.1153 (4)	0.5082 (6)	0.7433 (7)	0.103 (2)
H13	0.0995	0.4899	0.8230	0.123*
C14	0.1010 (4)	0.4537 (5)	0.6318 (8)	0.108 (2)
H14	0.0759	0.3980	0.6349	0.130*
C15	0.1237 (3)	0.4810 (4)	0.5149 (6)	0.0822 (15)
H15	0.1130	0.4435	0.4383	0.099*
C16	0.2008 (2)	0.3800 (3)	0.1649 (5)	0.0604 (12)
H16A	0.1953	0.3756	0.2596	0.072*
H16B	0.2473	0.3425	0.1542	0.072*
C17	0.1214 (2)	0.3495 (2)	0.0688 (4)	0.0472 (10)
C18	0.0461 (3)	0.3895 (3)	0.0682 (5)	0.0681 (13)
H18	0.0439	0.4365	0.1287	0.082*
C19	−0.0272 (3)	0.3613 (4)	−0.0213 (5)	0.0795 (16)
H19	−0.0781	0.3884	−0.0193	0.095*
C20	−0.0245 (3)	0.2952 (4)	−0.1100 (6)	0.0853 (18)
H20	−0.0738	0.2751	−0.1682	0.102*
C21	0.0503 (4)	0.2567 (4)	−0.1159 (6)	0.108 (2)
H21	0.0522	0.2126	−0.1811	0.130*
C22	0.1229 (3)	0.2831 (3)	−0.0256 (6)	0.0808 (16)
H22	0.1734	0.2557	−0.0286	0.097*

	U11	U22	U33	U12	U13	U23
Ni1	0.0297 (3)	0.0263 (3)	0.0308 (3)	0.0014 (2)	0.0017 (2)	0.0013 (3)
S1	0.0404 (5)	0.0557 (6)	0.0758 (8)	0.0085 (5)	0.0157 (5)	0.0121 (6)
S2	0.0506 (6)	0.0459 (6)	0.0535 (6)	−0.0007 (4)	0.0129 (5)	0.0074 (5)
P1	0.0349 (5)	0.0421 (5)	0.0440 (6)	−0.0003 (4)	0.0070 (4)	0.0019 (4)
O1	0.0459 (14)	0.0648 (17)	0.0443 (16)	0.0157 (13)	0.0152 (12)	0.0131 (13)
O2	0.0455 (14)	0.0413 (14)	0.0633 (18)	−0.0079 (11)	−0.0011 (13)	0.0018 (13)
N1	0.0367 (14)	0.0292 (14)	0.0336 (16)	0.0000 (12)	0.0023 (12)	0.0011 (12)
N2	0.0332 (14)	0.0297 (15)	0.0358 (16)	0.0036 (11)	0.0059 (12)	0.0022 (12)
C1	0.052 (2)	0.037 (2)	0.059 (3)	0.0101 (17)	−0.019 (2)	−0.0037 (19)
C2	0.058 (2)	0.035 (2)	0.039 (2)	0.0084 (17)	−0.0113 (18)	0.0016 (17)
C3	0.0396 (18)	0.0274 (16)	0.038 (2)	−0.0049 (14)	0.0082 (15)	−0.0018 (15)
C4	0.0458 (19)	0.0307 (18)	0.041 (2)	−0.0024 (15)	0.0071 (16)	−0.0022 (16)
C5	0.060 (2)	0.0301 (19)	0.044 (2)	0.0053 (16)	0.0098 (18)	0.0000 (17)
C6	0.0390 (18)	0.0301 (18)	0.037 (2)	−0.0041 (14)	0.0046 (15)	−0.0051 (15)
C7	0.041 (2)	0.056 (2)	0.065 (3)	−0.0041 (18)	0.0109 (19)	0.006 (2)
C8	0.058 (2)	0.050 (2)	0.045 (2)	0.0027 (19)	−0.0075 (19)	−0.0090 (19)
C9	0.060 (2)	0.075 (3)	0.056 (3)	0.025 (2)	0.020 (2)	0.014 (2)
C10	0.044 (2)	0.061 (3)	0.050 (3)	0.019 (2)	0.0147 (18)	0.011 (2)
C11	0.058 (3)	0.073 (3)	0.060 (3)	0.019 (2)	0.012 (2)	−0.001 (2)
C12	0.083 (4)	0.128 (5)	0.055 (3)	0.050 (4)	0.018 (3)	−0.003 (3)
C13	0.097 (4)	0.138 (6)	0.091 (5)	0.063 (4)	0.061 (4)	0.053 (5)
C14	0.114 (5)	0.089 (5)	0.146 (6)	0.021 (4)	0.080 (5)	0.043 (5)
C15	0.095 (4)	0.077 (4)	0.086 (4)	−0.002 (3)	0.043 (3)	0.001 (3)
C16	0.055 (2)	0.039 (2)	0.081 (3)	−0.0046 (18)	0.004 (2)	0.005 (2)
C17	0.043 (2)	0.038 (2)	0.059 (3)	−0.0055 (17)	0.0095 (18)	0.0008 (19)
C18	0.060 (3)	0.079 (3)	0.064 (3)	0.020 (2)	0.010 (2)	−0.016 (3)
C19	0.043 (2)	0.118 (5)	0.076 (4)	0.011 (3)	0.009 (2)	0.010 (3)
C20	0.066 (3)	0.060 (3)	0.114 (5)	−0.018 (3)	−0.014 (3)	0.002 (3)
C21	0.113 (5)	0.062 (3)	0.126 (5)	0.007 (3)	−0.023 (4)	−0.044 (4)
C22	0.064 (3)	0.062 (3)	0.109 (4)	0.012 (2)	0.006 (3)	−0.021 (3)

Ni1—N2	1.958 (3)	C7—H7C	0.9600
Ni1—N1	1.963 (3)	C8—H8A	0.9600
S1—P1	1.9674 (14)	C8—H8B	0.9600
S2—P1	1.9661 (15)	C8—H8C	0.9600
P1—O1	1.608 (3)	C9—C10	1.490 (6)
P1—O2	1.613 (3)	C9—H9A	0.9700
O1—C9	1.459 (4)	C9—H9B	0.9700
O2—C16	1.432 (4)	C10—C15	1.374 (7)
N1—C1	1.482 (4)	C10—C11	1.385 (6)
N1—C6	1.509 (4)	C11—C12	1.400 (7)
N1—H1	0.9100	C11—H11	0.9300
N2—C2	1.493 (4)	C12—C13	1.366 (9)
N2—C3	1.501 (4)	C12—H12	0.9300
N2—H2	0.9100	C13—C14	1.354 (9)
C1—C2	1.488 (5)	C13—H13	0.9300
C1—H1A	0.9700	C14—C15	1.363 (8)
C1—H1B	0.9700	C14—H14	0.9300
C2—H2A	0.9700	C15—H15	0.9300
C2—H2B	0.9700	C16—C17	1.500 (5)
C3—C4	1.510 (4)	C16—H16A	0.9700
C3—C5	1.535 (4)	C16—H16B	0.9700
C3—H3	0.9800	C17—C18	1.369 (5)
C4—C6i	1.520 (4)	C17—C22	1.370 (6)
C4—H4A	0.9700	C18—C19	1.388 (6)
C4—H4B	0.9700	C18—H18	0.9300
C5—H5A	0.9600	C19—C20	1.332 (7)
C5—H5B	0.9600	C19—H19	0.9300
C5—H5C	0.9600	C20—C21	1.366 (7)
C6—C4i	1.520 (4)	C20—H20	0.9300
C6—C7	1.528 (5)	C21—C22	1.376 (6)
C6—C8	1.541 (5)	C21—H21	0.9300
C7—H7A	0.9600	C22—H22	0.9300
C7—H7B	0.9600
N2—Ni1—N1	86.71 (11)	C6—C7—H7B	109.5
N2i—Ni1—N1	93.29 (11)	H7A—C7—H7B	109.5
O1—P1—O2	104.07 (15)	C6—C7—H7C	109.5
O1—P1—S2	111.40 (12)	H7A—C7—H7C	109.5
O2—P1—S2	103.65 (11)	H7B—C7—H7C	109.5
O1—P1—S1	105.11 (11)	C6—C8—H8A	109.5
O2—P1—S1	111.05 (11)	C6—C8—H8B	109.5
S2—P1—S1	120.50 (7)	H8A—C8—H8B	109.5
C9—O1—P1	119.1 (2)	C6—C8—H8C	109.5
C16—O2—P1	120.7 (2)	H8A—C8—H8C	109.5
C1—N1—C6	112.0 (2)	H8B—C8—H8C	109.5
C1—N1—Ni1	108.7 (2)	O1—C9—C10	108.6 (3)
C6—N1—Ni1	122.9 (2)	O1—C9—H9A	110.0
C1—N1—H1	103.6	C10—C9—H9A	110.0
C6—N1—H1	103.6	O1—C9—H9B	110.0
Ni1—N1—H1	103.6	C10—C9—H9B	110.0
C2—N2—C3	110.1 (2)	H9A—C9—H9B	108.3
C2—N2—Ni1	107.3 (2)	C15—C10—C11	118.4 (4)
C3—N2—Ni1	121.11 (19)	C15—C10—C9	120.1 (4)
C2—N2—H2	105.8	C11—C10—C9	121.5 (4)
C3—N2—H2	105.8	C10—C11—C12	119.2 (5)
Ni1—N2—H2	105.8	C10—C11—H11	120.4
N1—C1—C2	108.0 (3)	C12—C11—H11	120.4
N1—C1—H1A	110.1	C13—C12—C11	120.1 (6)
C2—C1—H1A	110.1	C13—C12—H12	119.9
N1—C1—H1B	110.1	C11—C12—H12	119.9
C2—C1—H1B	110.1	C14—C13—C12	120.6 (6)
H1A—C1—H1B	108.4	C14—C13—H13	119.7
C1—C2—N2	107.9 (3)	C12—C13—H13	119.7
C1—C2—H2A	110.1	C13—C14—C15	119.5 (6)
N2—C2—H2A	110.1	C13—C14—H14	120.2
C1—C2—H2B	110.1	C15—C14—H14	120.2
N2—C2—H2B	110.1	C14—C15—C10	122.2 (6)
H2A—C2—H2B	108.4	C14—C15—H15	118.9
N2—C3—C4	110.0 (3)	C10—C15—H15	118.9
N2—C3—C5	112.4 (2)	O2—C16—C17	108.3 (3)
C4—C3—C5	110.3 (3)	O2—C16—H16A	110.0
N2—C3—H3	108.0	C17—C16—H16A	110.0
C4—C3—H3	108.0	O2—C16—H16B	110.0
C5—C3—H3	108.0	C17—C16—H16B	110.0
C3—C4—C6i	117.4 (3)	H16A—C16—H16B	108.4
C3—C4—H4A	107.9	C18—C17—C22	118.0 (4)
C6i—C4—H4A	107.9	C18—C17—C16	121.3 (4)
C3—C4—H4B	107.9	C22—C17—C16	120.6 (4)
C6i—C4—H4B	107.9	C17—C18—C19	121.1 (4)
H4A—C4—H4B	107.2	C17—C18—H18	119.4
C3—C5—H5A	109.5	C19—C18—H18	119.4
C3—C5—H5B	109.5	C20—C19—C18	119.8 (5)
H5A—C5—H5B	109.5	C20—C19—H19	120.1
C3—C5—H5C	109.5	C18—C19—H19	120.1
H5A—C5—H5C	109.5	C19—C20—C21	120.3 (5)
H5B—C5—H5C	109.5	C19—C20—H20	119.8
N1—C6—C4i	108.0 (2)	C21—C20—H20	119.8
N1—C6—C7	109.6 (3)	C20—C21—C22	120.1 (5)
C4i—C6—C7	111.1 (3)	C20—C21—H21	120.0
N1—C6—C8	109.6 (3)	C22—C21—H21	120.0
C4i—C6—C8	108.3 (3)	C17—C22—C21	120.6 (5)
C7—C6—C8	110.3 (3)	C17—C22—H22	119.7
C6—C7—H7A	109.5	C21—C22—H22	119.7

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1	0.91	2.61	3.390 (3)	144
N2—H2···S2i	0.91	2.50	3.394 (3)	169

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	3.390 (3)	144
N2—H2⋯S2i	0.91	2.50	3.394 (3)	169

Symmetry code: (i) .