(meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) bis-[O,O'-(1,2-phenyl-ene) dithio-phosphate].

In the crystal structure of the title compound, [Ni(C(16)H(36)N(4))](C(6)H(4)O(2)PS(2))(2), the Ni(II) cation is located on a center of inversion and is chelated by the folded tetra-amine macrocycle ligand in a slightly distorted NiN(4) square-planar geometry. Two symmetry-related O,O'-(1,2-phenyl-ene)dithio-phosphate anions are located on either side of the Ni(II) cation, with Ni⋯S of 3.9558 (5) Å, and link to the tetra-amine macrocycle ligand via N-H⋯S hydrogen bonding.

Related literature

For general background to tetra­amine macrocycle compounds, see: Aoki & Kimura (2002 ▶). For the structures of analogous adducts, see: Feng et al. (2010 ▶); Lai et al. (2011 ▶); Zou et al. (2010 ▶). For the synthesis of [Et3NH][(o-C6H4O2)PS2], see: Feng et al. (2010 ▶).

Experimental

Crystal data

[Ni(C16H36N4)](C6H4O2PS2)2

M = 749.56

Monoclinic,

a = 9.0012 (15) Å

b = 20.500 (3) Å

c = 9.6682 (17) Å

β = 101.029 (3)°

V = 1751.1 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.92 mm−1

T = 103 K

0.24 × 0.21 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.809, T max = 0.852

9094 measured reflections

3103 independent reflections

2504 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.087

S = 1.04

3103 reflections

197 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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 datablock(s) I, global. DOI: 10.1107/S1600536811050951/xu5399sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050951/xu5399Isup2.hkl

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

[Ni(C16H36N4)](C6H4O2PS2)2	F(000) = 788
Mr = 749.56	Dx = 1.422 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2892 reflections
a = 9.0012 (15) Å	θ = 2.4–24.5°
b = 20.500 (3) Å	µ = 0.92 mm−1
c = 9.6682 (17) Å	T = 103 K
β = 101.029 (3)°	Block, orange
V = 1751.1 (5) Å3	0.24 × 0.21 × 0.18 mm
Z = 2

Bruker SMART 1000 CCD area-detector diffractometer	3103 independent reflections
Radiation source: fine-focus sealed tube	2504 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.809, Tmax = 0.852	k = −24→21
9094 measured reflections	l = −10→11

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0391P)2 + 0.6628P] where P = (Fo2 + 2Fc2)/3
3103 reflections	(Δ/σ)max < 0.001
197 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.27 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
Ni1	0.5000	0.0000	0.5000	0.03286 (14)
S1	0.84141 (10)	0.04903 (4)	0.31736 (11)	0.0756 (3)
S2	0.57109 (9)	0.16238 (5)	0.21370 (10)	0.0726 (3)
P1	0.78079 (8)	0.13550 (4)	0.24736 (8)	0.0500 (2)
O1	0.8895 (2)	0.18987 (10)	0.34393 (19)	0.0570 (5)
O2	0.8521 (2)	0.14989 (10)	0.10467 (19)	0.0585 (5)
N1	0.3804 (2)	0.03328 (10)	0.3268 (2)	0.0399 (5)
H1	0.4450	0.0565	0.2935	0.060*
N2	0.3989 (2)	0.06439 (9)	0.5965 (2)	0.0382 (5)
H2	0.3256	0.0411	0.6148	0.057*
C1	0.3140 (3)	−0.01378 (13)	0.2112 (3)	0.0480 (7)
C2	0.2676 (3)	0.08059 (14)	0.3600 (3)	0.0586 (8)
H2A	0.2407	0.1116	0.2836	0.070*
H2B	0.1766	0.0580	0.3729	0.070*
C3	0.3369 (4)	0.11486 (13)	0.4913 (3)	0.0557 (8)
H3A	0.2615	0.1409	0.5255	0.067*
H3B	0.4172	0.1435	0.4741	0.067*
C4	0.4665 (3)	0.09635 (12)	0.7326 (3)	0.0446 (6)
H4	0.5371	0.1300	0.7131	0.054*
C5	0.5544 (3)	0.04792 (14)	0.8347 (3)	0.0519 (7)
H5A	0.4844	0.0148	0.8546	0.062*
H5B	0.5927	0.0706	0.9223	0.062*
C6	0.2265 (4)	0.02438 (17)	0.0854 (3)	0.0718 (10)
H6A	0.1377	0.0433	0.1104	0.108*
H6B	0.1972	−0.0046	0.0069	0.108*
H6C	0.2897	0.0583	0.0600	0.108*
C7	0.2087 (3)	−0.06079 (15)	0.2663 (4)	0.0655 (9)
H7A	0.2609	−0.0803	0.3522	0.098*
H7B	0.1769	−0.0942	0.1975	0.098*
H7C	0.1217	−0.0375	0.2841	0.098*
C8	0.3449 (4)	0.12954 (15)	0.7982 (3)	0.0619 (8)
H8A	0.2989	0.1640	0.7376	0.093*
H8B	0.3902	0.1473	0.8883	0.093*
H8C	0.2692	0.0982	0.8102	0.093*
C9	0.9811 (3)	0.18714 (13)	0.1402 (3)	0.0471 (7)
C10	1.0029 (3)	0.20927 (12)	0.2761 (3)	0.0468 (7)
C11	1.1268 (3)	0.24600 (14)	0.3339 (4)	0.0624 (9)
H11	1.1422	0.2608	0.4265	0.075*
C12	1.2278 (4)	0.25961 (15)	0.2455 (5)	0.0791 (12)
H12	1.3141	0.2839	0.2807	0.095*
C13	1.2051 (4)	0.23869 (18)	0.1089 (5)	0.0787 (11)
H13	1.2743	0.2497	0.0527	0.094*
C14	1.0806 (3)	0.20142 (16)	0.0538 (4)	0.0641 (9)
H14	1.0647	0.1865	−0.0387	0.077*

	U11	U22	U33	U12	U13	U23
Ni1	0.0389 (3)	0.0275 (2)	0.0334 (2)	−0.00032 (19)	0.00984 (18)	0.00063 (18)
S1	0.0628 (5)	0.0595 (5)	0.1091 (7)	−0.0099 (4)	0.0279 (5)	0.0137 (5)
S2	0.0503 (5)	0.0852 (7)	0.0857 (6)	−0.0006 (4)	0.0217 (4)	0.0079 (5)
P1	0.0474 (4)	0.0560 (5)	0.0498 (4)	−0.0123 (4)	0.0176 (3)	−0.0053 (3)
O1	0.0628 (12)	0.0608 (13)	0.0503 (11)	−0.0129 (10)	0.0184 (10)	−0.0141 (9)
O2	0.0536 (11)	0.0802 (14)	0.0446 (11)	−0.0208 (11)	0.0167 (9)	−0.0084 (10)
N1	0.0484 (12)	0.0350 (12)	0.0364 (11)	0.0004 (10)	0.0083 (9)	−0.0002 (9)
N2	0.0435 (12)	0.0317 (11)	0.0410 (12)	−0.0022 (9)	0.0126 (9)	−0.0001 (9)
C1	0.0514 (16)	0.0494 (17)	0.0402 (15)	−0.0020 (13)	0.0014 (12)	−0.0059 (12)
C2	0.0638 (19)	0.0555 (18)	0.0521 (17)	0.0238 (15)	−0.0002 (14)	−0.0023 (14)
C3	0.073 (2)	0.0432 (16)	0.0505 (17)	0.0183 (14)	0.0106 (15)	0.0000 (13)
C4	0.0549 (16)	0.0376 (14)	0.0432 (15)	−0.0049 (12)	0.0138 (12)	−0.0072 (12)
C5	0.0651 (18)	0.0538 (17)	0.0369 (15)	−0.0001 (15)	0.0100 (13)	−0.0087 (13)
C6	0.083 (2)	0.079 (2)	0.0445 (18)	0.0131 (19)	−0.0088 (16)	−0.0060 (16)
C7	0.0553 (19)	0.0515 (18)	0.090 (2)	−0.0115 (15)	0.0137 (17)	−0.0112 (17)
C8	0.081 (2)	0.0542 (18)	0.0559 (18)	0.0109 (16)	0.0270 (16)	−0.0090 (14)
C9	0.0394 (15)	0.0453 (16)	0.0571 (17)	0.0003 (12)	0.0103 (13)	0.0099 (13)
C10	0.0436 (15)	0.0351 (14)	0.0619 (18)	0.0019 (12)	0.0109 (13)	0.0032 (13)
C11	0.0501 (17)	0.0376 (16)	0.091 (2)	0.0022 (14)	−0.0069 (17)	−0.0060 (15)
C12	0.0405 (18)	0.0412 (19)	0.152 (4)	−0.0033 (15)	0.010 (2)	0.015 (2)
C13	0.050 (2)	0.069 (2)	0.123 (3)	0.0075 (18)	0.031 (2)	0.040 (2)
C14	0.0521 (19)	0.075 (2)	0.070 (2)	0.0051 (17)	0.0218 (16)	0.0247 (17)

Ni1—N1	1.9332 (19)	C4—C8	1.526 (4)
Ni1—N1i	1.9332 (19)	C4—H4	0.9800
Ni1—N2i	1.9410 (19)	C5—C1i	1.514 (4)
Ni1—N2	1.9410 (19)	C5—H5A	0.9700
S1—P1	1.9383 (12)	C5—H5B	0.9700
S2—P1	1.9332 (12)	C6—H6A	0.9600
P1—O1	1.6497 (19)	C6—H6B	0.9600
P1—O2	1.6554 (19)	C6—H6C	0.9600
O1—C10	1.374 (3)	C7—H7A	0.9600
O2—C9	1.377 (3)	C7—H7B	0.9600
N1—C2	1.483 (3)	C7—H7C	0.9600
N1—C1	1.511 (3)	C8—H8A	0.9600
N1—H1	0.8600	C8—H8B	0.9600
N2—C3	1.483 (3)	C8—H8C	0.9600
N2—C4	1.491 (3)	C9—C10	1.368 (4)
N2—H2	0.8600	C9—C14	1.368 (4)
C1—C5i	1.514 (4)	C10—C11	1.373 (4)
C1—C7	1.518 (4)	C11—C12	1.390 (5)
C1—C6	1.532 (4)	C11—H11	0.9300
C2—C3	1.480 (4)	C12—C13	1.366 (5)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C14	1.377 (5)
C3—H3A	0.9700	C13—H13	0.9300
C3—H3B	0.9700	C14—H14	0.9300
C4—C5	1.512 (4)
N1—Ni1—N1i	180.00 (13)	C5—C4—C8	110.4 (2)
N1—Ni1—N2i	93.33 (8)	N2—C4—H4	108.0
N1i—Ni1—N2i	86.67 (8)	C5—C4—H4	108.0
N1—Ni1—N2	86.67 (8)	C8—C4—H4	108.0
N1i—Ni1—N2	93.33 (8)	C4—C5—C1i	117.0 (2)
N2i—Ni1—N2	180.00 (9)	C4—C5—H5A	108.1
O1—P1—O2	93.95 (10)	C1i—C5—H5A	108.1
O1—P1—S2	110.90 (9)	C4—C5—H5B	108.1
O2—P1—S2	109.30 (9)	C1i—C5—H5B	108.1
O1—P1—S1	108.88 (9)	H5A—C5—H5B	107.3
O2—P1—S1	109.02 (9)	C1—C6—H6A	109.5
S2—P1—S1	121.33 (5)	C1—C6—H6B	109.5
C10—O1—P1	109.87 (17)	H6A—C6—H6B	109.5
C9—O2—P1	109.47 (16)	C1—C6—H6C	109.5
C2—N1—C1	112.8 (2)	H6A—C6—H6C	109.5
C2—N1—Ni1	109.51 (16)	H6B—C6—H6C	109.5
C1—N1—Ni1	119.43 (16)	C1—C7—H7A	109.5
C2—N1—H1	105.0	C1—C7—H7B	109.5
C1—N1—H1	106.1	H7A—C7—H7B	109.5
Ni1—N1—H1	102.4	C1—C7—H7C	109.5
C3—N2—C4	109.58 (19)	H7A—C7—H7C	109.5
C3—N2—Ni1	107.08 (15)	H7B—C7—H7C	109.5
C4—N2—Ni1	124.98 (15)	C4—C8—H8A	109.5
C3—N2—H2	109.1	C4—C8—H8B	109.5
C4—N2—H2	105.2	H8A—C8—H8B	109.5
Ni1—N2—H2	99.7	C4—C8—H8C	109.5
N1—C1—C5i	106.9 (2)	H8A—C8—H8C	109.5
N1—C1—C7	109.4 (2)	H8B—C8—H8C	109.5
C5i—C1—C7	112.7 (2)	C10—C9—C14	121.7 (3)
N1—C1—C6	109.4 (2)	C10—C9—O2	112.5 (2)
C5i—C1—C6	108.4 (2)	C14—C9—O2	125.8 (3)
C7—C1—C6	110.0 (2)	C9—C10—C11	121.9 (3)
C3—C2—N1	107.6 (2)	C9—C10—O1	112.3 (2)
C3—C2—H2A	110.2	C11—C10—O1	125.8 (3)
N1—C2—H2A	110.2	C10—C11—C12	115.8 (3)
C3—C2—H2B	110.2	C10—C11—H11	122.1
N1—C2—H2B	110.2	C12—C11—H11	122.1
H2A—C2—H2B	108.5	C13—C12—C11	122.5 (3)
C2—C3—N2	107.4 (2)	C13—C12—H12	118.8
C2—C3—H3A	110.2	C11—C12—H12	118.8
N2—C3—H3A	110.2	C12—C13—C14	120.6 (3)
C2—C3—H3B	110.2	C12—C13—H13	119.7
N2—C3—H3B	110.2	C14—C13—H13	119.7
H3A—C3—H3B	108.5	C9—C14—C13	117.5 (3)
N2—C4—C5	111.2 (2)	C9—C14—H14	121.3
N2—C4—C8	111.0 (2)	C13—C14—H14	121.3
O2—P1—O1—C10	−12.84 (19)	C4—N2—C3—C2	−178.4 (2)
S2—P1—O1—C10	−125.24 (16)	Ni1—N2—C3—C2	43.3 (3)
S1—P1—O1—C10	98.80 (17)	C3—N2—C4—C5	−170.2 (2)
O1—P1—O2—C9	12.24 (19)	Ni1—N2—C4—C5	−41.2 (3)
S2—P1—O2—C9	126.01 (16)	C3—N2—C4—C8	66.5 (3)
S1—P1—O2—C9	−99.28 (17)	Ni1—N2—C4—C8	−164.52 (18)
N2i—Ni1—N1—C2	172.52 (18)	N2—C4—C5—C1i	60.0 (3)
N2—Ni1—N1—C2	−7.48 (18)	C8—C4—C5—C1i	−176.3 (2)
N2i—Ni1—N1—C1	40.32 (19)	P1—O2—C9—C10	−8.4 (3)
N2—Ni1—N1—C1	−139.68 (19)	P1—O2—C9—C14	171.1 (2)
N1—Ni1—N2—C3	−19.90 (17)	C14—C9—C10—C11	−1.1 (4)
N1i—Ni1—N2—C3	160.10 (17)	O2—C9—C10—C11	178.4 (2)
N1—Ni1—N2—C4	−149.9 (2)	C14—C9—C10—O1	179.5 (2)
N1i—Ni1—N2—C4	30.1 (2)	O2—C9—C10—O1	−1.0 (3)
C2—N1—C1—C5i	167.1 (2)	P1—O1—C10—C9	10.0 (3)
Ni1—N1—C1—C5i	−62.1 (3)	P1—O1—C10—C11	−169.3 (2)
C2—N1—C1—C7	−70.6 (3)	C9—C10—C11—C12	0.4 (4)
Ni1—N1—C1—C7	60.1 (3)	O1—C10—C11—C12	179.7 (3)
C2—N1—C1—C6	49.9 (3)	C10—C11—C12—C13	0.8 (5)
Ni1—N1—C1—C6	−179.32 (19)	C11—C12—C13—C14	−1.5 (5)
C1—N1—C2—C3	169.0 (2)	C10—C9—C14—C13	0.5 (4)
Ni1—N1—C2—C3	33.5 (3)	O2—C9—C14—C13	−179.0 (3)
N1—C2—C3—N2	−50.3 (3)	C12—C13—C14—C9	0.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2	0.86	2.63	3.444 (2)	158
N2—H2···S1i	0.86	2.55	3.386 (2)	166

Table 1

Selected bond lengths (Å)

Ni1—N1	1.9332 (19)
Ni1—N2	1.9410 (19)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2	0.86	2.63	3.444 (2)	158
N2—H2⋯S1i	0.86	2.55	3.386 (2)	166

Symmetry code: (i) .