catena-Poly[[bis-(O,O'-diisopropyl dithio-phosphato-κS,S')nickel(II)]-μ-bis-(4-pyridylmethyl-ene)diazane-κN:N'].

The Ni atom in the title linear supra-molecular polymer, [Ni(C(6)H(14)O(2)PS(2))(2)(C(12)H(10)N(4))](n), exists within a trans-N(2)S(4) octa-hedral donor set defined by two symmetrically coordinating dithio-phosphate ligands and pyridine N atoms derived from two bridging bis-(4-pyridylmethyl-ene)diazane ligands. The Ni atom lies on a centre of inversion and the bis-(4-pyridylmethyl-ene)diazane ligand is also disposed about a centre of inversion. The chains are arranged into layers sustained by C-H⋯S contacts and inter-digitate with neighbouring layers, forming the crystal structure.

Related literature

For background to supra­molecular polymers of metal dithio­phosphates, see: Lai & Tiekink (2004 ▶); Chen et al. (2006 ▶); Aragoni et al. (2007 ▶). For a related iso-butyl structure and the synthesis, see: Berdugo & Tiekink (2008 ▶).

Experimental

Crystal data

[Ni(C6H14O2PS2)2(C12H10N4)]

M = 695.47

Triclinic,

a = 8.661 (2) Å

b = 8.753 (2) Å

c = 11.159 (3) Å

α = 88.110 (8)°

β = 81.502 (7)°

γ = 89.813 (10)°

V = 836.2 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.96 mm−1

T = 98 K

0.50 × 0.08 × 0.05 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.794, T max = 1

7552 measured reflections

3810 independent reflections

3555 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.111

S = 1.09

3810 reflections

178 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.70 e Å−3

Data collection: CrystalClear (Rigaku/MSC 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043505/hb5163sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043505/hb5163Isup2.hkl

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

[Ni(C6H14O2PS2)2(C12H10N4)]	Z = 1
Mr = 695.47	F(000) = 364
Triclinic, P1	Dx = 1.381 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.661 (2) Å	Cell parameters from 2817 reflections
b = 8.753 (2) Å	θ = 3.0–32.3°
c = 11.159 (3) Å	µ = 0.96 mm−1
α = 88.110 (8)°	T = 98 K
β = 81.502 (7)°	Prism, brown-orange
γ = 89.813 (10)°	0.50 × 0.08 × 0.05 mm
V = 836.2 (4) Å3

Rigaku AFC12K/SATURN724 diffractometer	3810 independent reflections
Radiation source: fine-focus sealed tube	3555 reflections with I > 2σ(I)
graphite	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→11
Tmin = 0.794, Tmax = 1	k = −11→11
7552 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0532P)2 + 0.6278P] where P = (Fo2 + 2Fc2)/3
3810 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.70 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
Ni	0.5000	0.5000	0.5000	0.01506 (12)
S1	0.73976 (6)	0.43573 (6)	0.58844 (5)	0.01900 (14)
S2	0.46123 (7)	0.68201 (6)	0.66788 (5)	0.01887 (14)
P1	0.64607 (7)	0.57524 (7)	0.71650 (5)	0.01822 (15)
O1	0.5953 (2)	0.48949 (19)	0.84272 (15)	0.0223 (4)
O2	0.7711 (2)	0.6930 (2)	0.75100 (15)	0.0241 (4)
N1	0.3710 (2)	0.3357 (2)	0.61516 (17)	0.0177 (4)
N2	0.0259 (2)	0.0611 (2)	0.95949 (18)	0.0230 (4)
C1	0.6944 (3)	0.3733 (3)	0.8926 (2)	0.0261 (5)
H1	0.7730	0.3345	0.8257	0.031*
C2	0.5865 (3)	0.2446 (3)	0.9442 (2)	0.0315 (6)
H2A	0.5378	0.2009	0.8792	0.047*
H2B	0.5053	0.2840	1.0061	0.047*
H2C	0.6464	0.1653	0.9810	0.047*
C3	0.7778 (3)	0.4463 (3)	0.9858 (2)	0.0305 (6)
H3A	0.8473	0.5272	0.9464	0.046*
H3B	0.8393	0.3688	1.0230	0.046*
H3C	0.7009	0.4903	1.0486	0.046*
C4	0.8388 (3)	0.8094 (3)	0.6614 (2)	0.0266 (5)
H4	0.7952	0.7981	0.5840	0.032*
C5	1.0132 (3)	0.7830 (3)	0.6398 (3)	0.0384 (7)
H5A	1.0350	0.6822	0.6055	0.058*
H5B	1.0544	0.7876	0.7168	0.058*
H5C	1.0634	0.8621	0.5831	0.058*
C6	0.7934 (3)	0.9641 (3)	0.7138 (3)	0.0380 (7)
H6A	0.6795	0.9747	0.7249	0.057*
H6B	0.8410	1.0454	0.6581	0.057*
H6C	0.8303	0.9718	0.7923	0.057*
C7	0.4224 (3)	0.1924 (3)	0.6265 (2)	0.0198 (4)
H7	0.5144	0.1624	0.5755	0.024*
C8	0.3473 (3)	0.0860 (3)	0.7094 (2)	0.0210 (5)
H8	0.3865	−0.0153	0.7138	0.025*
C9	0.2132 (3)	0.1289 (3)	0.7867 (2)	0.0194 (4)
C10	0.1577 (3)	0.2772 (3)	0.7726 (2)	0.0212 (5)
H10	0.0653	0.3102	0.8217	0.025*
C11	0.2384 (3)	0.3754 (3)	0.6868 (2)	0.0208 (5)
H11	0.1990	0.4758	0.6775	0.025*
C12	0.1396 (3)	0.0206 (3)	0.8798 (2)	0.0225 (5)
H12	0.1765	−0.0817	0.8815	0.027*

	U11	U22	U33	U12	U13	U23
Ni	0.0173 (2)	0.0127 (2)	0.0143 (2)	0.00009 (15)	0.00006 (15)	0.00119 (14)
S1	0.0197 (3)	0.0198 (3)	0.0170 (3)	0.0034 (2)	−0.0009 (2)	−0.0008 (2)
S2	0.0208 (3)	0.0174 (3)	0.0183 (3)	0.0039 (2)	−0.0023 (2)	−0.0019 (2)
P1	0.0192 (3)	0.0193 (3)	0.0158 (3)	0.0020 (2)	−0.0015 (2)	−0.0011 (2)
O1	0.0243 (8)	0.0249 (8)	0.0174 (8)	0.0055 (7)	−0.0025 (6)	0.0016 (6)
O2	0.0240 (9)	0.0279 (9)	0.0209 (9)	−0.0010 (7)	−0.0045 (7)	−0.0036 (7)
N1	0.0182 (9)	0.0170 (9)	0.0165 (9)	−0.0004 (7)	0.0013 (7)	0.0017 (7)
N2	0.0238 (10)	0.0212 (10)	0.0223 (11)	−0.0065 (8)	0.0006 (8)	0.0090 (8)
C1	0.0270 (12)	0.0323 (13)	0.0186 (12)	0.0112 (10)	−0.0032 (10)	0.0033 (9)
C2	0.0412 (15)	0.0265 (13)	0.0280 (14)	0.0055 (11)	−0.0096 (11)	0.0026 (10)
C3	0.0256 (13)	0.0412 (15)	0.0250 (13)	0.0024 (11)	−0.0059 (10)	0.0051 (11)
C4	0.0274 (12)	0.0259 (12)	0.0266 (13)	−0.0038 (10)	−0.0034 (10)	−0.0033 (10)
C5	0.0279 (14)	0.0344 (15)	0.0503 (19)	−0.0032 (12)	0.0044 (12)	−0.0087 (13)
C6	0.0298 (14)	0.0289 (14)	0.056 (2)	0.0019 (11)	−0.0081 (13)	−0.0088 (13)
C7	0.0222 (11)	0.0181 (10)	0.0184 (11)	0.0002 (9)	−0.0008 (9)	0.0019 (8)
C8	0.0240 (11)	0.0155 (10)	0.0233 (12)	0.0003 (9)	−0.0028 (9)	0.0013 (8)
C9	0.0193 (11)	0.0199 (11)	0.0191 (11)	−0.0027 (8)	−0.0040 (8)	0.0028 (8)
C10	0.0198 (11)	0.0209 (11)	0.0210 (12)	−0.0004 (9)	0.0023 (9)	0.0019 (9)
C11	0.0209 (11)	0.0184 (10)	0.0213 (12)	0.0023 (9)	0.0020 (9)	0.0049 (8)
C12	0.0229 (11)	0.0224 (11)	0.0228 (12)	−0.0046 (9)	−0.0062 (9)	0.0056 (9)

Ni—S1	2.4827 (7)	C3—H3A	0.9800
Ni—S2	2.4835 (7)	C3—H3B	0.9800
Ni—N1	2.1051 (19)	C3—H3C	0.9800
Ni—N1i	2.1051 (19)	C4—C5	1.513 (4)
Ni—S1i	2.4827 (7)	C4—C6	1.520 (4)
Ni—S2i	2.4835 (7)	C4—H4	1.0000
S1—P1	1.9895 (9)	C5—H5A	0.9800
S2—P1	1.9859 (9)	C5—H5B	0.9800
P1—O1	1.5779 (17)	C5—H5C	0.9800
P1—O2	1.5934 (18)	C6—H6A	0.9800
O1—C1	1.476 (3)	C6—H6B	0.9800
O2—C4	1.464 (3)	C6—H6C	0.9800
N1—C7	1.338 (3)	C7—C8	1.384 (3)
N1—C11	1.350 (3)	C7—H7	0.9500
N2—C12	1.283 (3)	C8—C9	1.399 (3)
N2—N2ii	1.408 (4)	C8—H8	0.9500
C1—C2	1.510 (4)	C9—C10	1.395 (3)
C1—C3	1.511 (4)	C9—C12	1.459 (3)
C1—H1	1.0000	C10—C11	1.377 (3)
C2—H2A	0.9800	C10—H10	0.9500
C2—H2B	0.9800	C11—H11	0.9500
C2—H2C	0.9800	C12—H12	0.9500
N1—Ni—S1i	89.02 (6)	C1—C3—H3B	109.5
N1i—Ni—S1i	90.98 (6)	H3A—C3—H3B	109.5
N1—Ni—S1	90.98 (6)	C1—C3—H3C	109.5
N1i—Ni—S1	89.02 (6)	H3A—C3—H3C	109.5
N1—Ni—S2i	91.02 (6)	H3B—C3—H3C	109.5
N1i—Ni—S2i	88.98 (6)	O2—C4—C5	107.1 (2)
S1i—Ni—S2i	82.46 (2)	O2—C4—C6	107.0 (2)
S1—Ni—S2i	97.54 (2)	C5—C4—C6	113.4 (2)
N1—Ni—S2	88.98 (6)	O2—C4—H4	109.8
N1i—Ni—S2	91.02 (6)	C5—C4—H4	109.8
S1i—Ni—S2	97.54 (2)	C6—C4—H4	109.8
S1—Ni—S2	82.46 (2)	C4—C5—H5A	109.5
S1i—Ni—S1	180.0	C4—C5—H5B	109.5
S2i—Ni—S2	180.0	H5A—C5—H5B	109.5
N1i—Ni—N1	180.0	C4—C5—H5C	109.5
P1—S1—Ni	82.80 (3)	H5A—C5—H5C	109.5
P1—S2—Ni	82.85 (3)	H5B—C5—H5C	109.5
O1—P1—O2	100.84 (10)	C4—C6—H6A	109.5
O1—P1—S2	108.61 (7)	C4—C6—H6B	109.5
O2—P1—S2	111.61 (7)	H6A—C6—H6B	109.5
O1—P1—S1	112.72 (7)	C4—C6—H6C	109.5
O2—P1—S1	111.82 (7)	H6A—C6—H6C	109.5
S2—P1—S1	110.84 (4)	H6B—C6—H6C	109.5
C1—O1—P1	122.47 (15)	N1—C7—C8	122.9 (2)
C4—O2—P1	119.75 (15)	N1—C7—H7	118.6
C7—N1—C11	117.73 (19)	C8—C7—H7	118.6
C7—N1—Ni	121.63 (15)	C7—C8—C9	119.4 (2)
C11—N1—Ni	120.48 (15)	C7—C8—H8	120.3
C12—N2—N2ii	111.3 (2)	C9—C8—H8	120.3
O1—C1—C2	106.2 (2)	C10—C9—C8	117.6 (2)
O1—C1—C3	108.7 (2)	C10—C9—C12	122.7 (2)
C2—C1—C3	113.5 (2)	C8—C9—C12	119.7 (2)
O1—C1—H1	109.5	C11—C10—C9	119.2 (2)
C2—C1—H1	109.5	C11—C10—H10	120.4
C3—C1—H1	109.5	C9—C10—H10	120.4
C1—C2—H2A	109.5	N1—C11—C10	123.1 (2)
C1—C2—H2B	109.5	N1—C11—H11	118.4
H2A—C2—H2B	109.5	C10—C11—H11	118.4
C1—C2—H2C	109.5	N2—C12—C9	121.1 (2)
H2A—C2—H2C	109.5	N2—C12—H12	119.4
H2B—C2—H2C	109.5	C9—C12—H12	119.4
C1—C3—H3A	109.5
N1—Ni—S1—P1	−82.10 (6)	S2—Ni—N1—C7	−131.96 (18)
N1i—Ni—S1—P1	97.90 (6)	S1i—Ni—N1—C11	−54.34 (18)
S2i—Ni—S1—P1	−173.26 (3)	S1—Ni—N1—C11	125.66 (18)
S2—Ni—S1—P1	6.74 (3)	S2i—Ni—N1—C11	−136.78 (18)
N1—Ni—S2—P1	84.37 (6)	S2—Ni—N1—C11	43.22 (18)
N1i—Ni—S2—P1	−95.63 (6)	P1—O1—C1—C2	−137.26 (18)
S1i—Ni—S2—P1	173.24 (3)	P1—O1—C1—C3	100.3 (2)
S1—Ni—S2—P1	−6.76 (3)	P1—O2—C4—C5	−119.8 (2)
Ni—S2—P1—O1	−115.40 (7)	P1—O2—C4—C6	118.37 (19)
Ni—S2—P1—O2	134.30 (7)	C11—N1—C7—C8	−1.3 (3)
Ni—S2—P1—S1	8.96 (3)	Ni—N1—C7—C8	174.02 (18)
Ni—S1—P1—O1	113.02 (8)	N1—C7—C8—C9	−1.1 (4)
Ni—S1—P1—O2	−134.19 (7)	C7—C8—C9—C10	2.6 (3)
Ni—S1—P1—S2	−8.96 (3)	C7—C8—C9—C12	−175.8 (2)
O2—P1—O1—C1	−75.87 (19)	C8—C9—C10—C11	−1.8 (3)
S2—P1—O1—C1	166.73 (16)	C12—C9—C10—C11	176.6 (2)
S1—P1—O1—C1	43.51 (19)	C7—N1—C11—C10	2.1 (4)
O1—P1—O2—C4	−173.76 (16)	Ni—N1—C11—C10	−173.22 (18)
S2—P1—O2—C4	−58.58 (17)	C9—C10—C11—N1	−0.6 (4)
S1—P1—O2—C4	66.22 (17)	N2ii—N2—C12—C9	−179.5 (2)
S1i—Ni—N1—C7	130.48 (18)	C10—C9—C12—N2	−5.2 (4)
S1—Ni—N1—C7	−49.52 (18)	C8—C9—C12—N2	173.1 (2)
S2i—Ni—N1—C7	48.04 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···S2iii	0.95	2.77	3.694 (3)	164

Ni—S1	2.4827 (7)
Ni—S2	2.4835 (7)
Ni—N1	2.1051 (19)

S1—Ni—S2

82.46 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯S2i	0.95	2.77	3.694 (3)	164

Symmetry code: (i) .