catena-Poly[[[bis­(O,O′-diisobutyl dithio­phosphato-κ2S,S′)nickel(II)]-μ-1,2-bis­(4-pyridylmethyl­ene)hydrazine-κ2N:N′] toluene disolvate]

Berdugo, E.; Tiekink, E.R.T.

doi:10.1107/S1600536808017121

catena-Poly[[[bis(O,O′-diisobutyl dithiophosphato-κ²S,S′)nickel(II)]-μ-1,2-bis(4-pyridylmethylene)hydrazine-κ²N:N′] toluene disolvate]

The polymeric title compound, {[Ni(C₈H₁₈O₂PS₂)₂(C₁₂H₁₀N₄)]·2C₇H₇}_n, has a linear topology and features octahedrally coordinated Ni atoms with a trans-N₂S₄ donor set. The toluene solvent molecules occupy channels defined by the three-dimensional stacking of the polymeric chains. The Ni atom is located at a centre of inversion and the bridging 1,2-bis(4-pyridylmethylene)hydrazine4-pyridine molecule is also disposed about a centre of inversion. One isobutoxy group is disordered equally over two positions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808017121/ng2459sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808017121/ng2459Isup2.hkl Contains datablock I

CCDC reference: 696423

checkCIF report

Key indicators

Single-crystal X-ray study
T = 98 K
Mean (C-C) = 0.005 Å
Disorder in main residue
R factor = 0.055
wR factor = 0.142
Data-to-parameter ratio = 19.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O2     --  C5      ..       8.22 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O32    --  C5      ..       8.22 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C5     --  C35     ..       7.81 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C6     --  C36     ..      11.78 su

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.64 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.27 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C37
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C36
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.24
PLAT301_ALERT_3_C Main Residue  Disorder .........................      16.00 Perc.
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........         O2
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........        O32
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.93
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            S1  -NI  -S1  -P1     11.00  0.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            S2  -NI  -S2  -P1      2.00  0.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         23
            N1  -NI  -N1  -C13     8.00  0.00   2.666   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         28
            N1  -NI  -N1  -C9     10.00  0.00   2.666   1.555   1.555   1.555
PLAT779_ALERT_4_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              O32  -P1   -O2      1.555   1.555   1.555

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.934
            Tmax scaled      0.934 Tmin scaled      0.742

   0 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  12 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Interest in examining structures related to the title compound (I), Fig. 1, relates in the main to attempts to control polymer formation and when formed topology (Lai et al., 2004; Chen et al. 2006; Tiekink, 2006; Benson et al., 2007 & Berdugo et al., 2007). A linear polymer is found in (I), Fig. 2, in which the Ni atom is located on a centre of inversion and the bridging 4-pyridinealdazine ligand is disposed about another centre of inversion. The Ni atom exists in a trans-N₂S₄ octahedral coordination geommetry. The polymers are aligned along the c-direction and form layers in the ac-plane that are stabilized by C—H···S contacts, Table 1. Layers stack along the b axis and define approximate squares with Ni···Ni edges 12.1 and 12.3 Å. Despite the fact that the isobutyl residues protrude into the resulting channels, the toluene molecules are accommodated in these as seen in Fig. 3.

Related literature top

For a related structure, see: Berdugo et al. (2007). For related literature, see: Lai et al. (2004); Chen et al. (2006); Tiekink (2006); Benson et al. (2007).

Experimental top

The title compound was prepared by refluxing equimolar amounts of the parent nickel dithiophosphate with 4-pyridinealdazine (Sigma-Aldrich) in toluene (30 ml) for 30 min following a literature procedure (Berdugo et al., 2007). Brown crystals of (I) were isolated by the slow evaporation (3 days) of this toluene solution. The crystals lost crystallinity with standing in air after a few minutes. IR (cm^-1): v(C—O) 1126, v(P—O) 951, v(P—S)_asymm 672, v(P—S)_sym 593.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHEXLS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination geometry of the Ni atom in (I) showing the crystallographic numbering scheme. Displacement ellipsoids are shown at the 70% probability level. Symmetry operation i: 1 - x, 1 - y, 1 - z & ii: 2 - x, 1 - y, 2 - z. Only one orientation of the disordered O2—C5—C8 butyl group is shown for clarity.
	Fig. 2. Polymer topology in (I). Colour code: Ni (orange), S (yellow), P (pink), O (red), N (blue), C (grey) & H (green).
	Fig. 3. A view of the crystal packing in (I) highlighting the channels occupied by the solvent toluene molecules (four shown in space filling mode). Colour code as for Fig. 2.

catena-Poly[[[bis(O,O'-diisobutyl dithiophosphato-κ²S,S')nickel(II)]-µ-1,2- bis(4-pyridylmethylene)hydrazine-κ²N:N'] toluene disolvate] top

Crystal data top

[Ni(C₈H₁₈O₂PS₂)₂(C₁₂H₁₀N₄)]·2C₇H₇	Z = 1
M_r = 935.85	F(000) = 496
Triclinic, P1	D_x = 1.294 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.7132 (15) Å	Cell parameters from 4131 reflections
b = 12.089 (2) Å	θ = 2.3–40.7°
c = 12.293 (2) Å	µ = 0.69 mm⁻¹
α = 82.662 (10)°	T = 98 K
β = 86.528 (10)°	Prism, brown-orange
γ = 69.321 (6)°	0.30 × 0.20 × 0.10 mm
V = 1201.4 (4) Å³

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5457 independent reflections
Radiation source: fine-focus sealed tube	4980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.795, T_max = 1	k = −13→15
8239 measured reflections	l = −15→15

Refinement top

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.064P)² + 1.4047P] where P = (F_o² + 2F_c²)/3
5457 reflections	(Δ/σ)_max < 0.001
279 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Ni(C₈H₁₈O₂PS₂)₂(C₁₂H₁₀N₄)]·2C₇H₇	γ = 69.321 (6)°
M_r = 935.85	V = 1201.4 (4) Å³
Triclinic, P1	Z = 1
a = 8.7132 (15) Å	Mo Kα radiation
b = 12.089 (2) Å	µ = 0.69 mm⁻¹
c = 12.293 (2) Å	T = 98 K
α = 82.662 (10)°	0.30 × 0.20 × 0.10 mm
β = 86.528 (10)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	5457 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4980 reflections with I > 2σ(I)
T_min = 0.795, T_max = 1	R_int = 0.033
8239 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.08	Δρ_max = 0.64 e Å⁻³
5457 reflections	Δρ_min = −0.78 e Å⁻³
279 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni	0.5000	0.5000	0.5000	0.02039 (14)
S1	0.38649 (8)	0.38353 (7)	0.64197 (5)	0.02552 (17)
S2	0.67986 (8)	0.29788 (6)	0.46088 (5)	0.02452 (16)
P1	0.55031 (9)	0.24313 (7)	0.58030 (6)	0.02530 (17)
O1	0.6644 (3)	0.15123 (18)	0.67162 (16)	0.0295 (4)
N1	0.6658 (3)	0.5003 (2)	0.61646 (17)	0.0205 (4)
N2	0.9368 (3)	0.5058 (2)	0.96412 (18)	0.0256 (5)
C1	0.7711 (4)	0.1916 (3)	0.7302 (2)	0.0309 (6)
H1A	0.7063	0.2423	0.7859	0.037*
H1B	0.8205	0.2396	0.6782	0.037*
C2	0.9051 (4)	0.0857 (3)	0.7856 (2)	0.0303 (6)
H2	0.9674	0.0343	0.7286	0.036*
C3	1.0219 (4)	0.1321 (3)	0.8386 (3)	0.0420 (8)
H3A	1.1097	0.0648	0.8754	0.063*
H3B	0.9610	0.1855	0.8923	0.063*
H3C	1.0695	0.1755	0.7818	0.063*
C4	0.8358 (5)	0.0118 (3)	0.8709 (3)	0.0399 (8)
H4A	0.9260	−0.0558	0.9049	0.060*
H4B	0.7624	−0.0175	0.8352	0.060*
H4C	0.7744	0.0613	0.9273	0.060*
O2	0.4688 (3)	0.1558 (2)	0.54352 (18)	0.0365 (5)	0.50
C5	0.3314 (8)	0.2219 (5)	0.4584 (5)	0.0237 (12)	0.50
H5A	0.2908	0.3076	0.4683	0.028*	0.50
H5B	0.3821	0.2143	0.3842	0.028*	0.50
C6	0.2185 (9)	0.1915 (8)	0.4606 (6)	0.0447 (17)	0.50
H6A	0.1330	0.2627	0.4881	0.054*	0.50
C7	0.1788 (5)	0.0918 (4)	0.5366 (3)	0.0565 (11)	0.50
H7A	0.0721	0.0903	0.5173	0.085*	0.50
H7B	0.1752	0.1075	0.6131	0.085*	0.50
H7C	0.2640	0.0148	0.5273	0.085*	0.50
C8	0.1386 (4)	0.1940 (3)	0.3445 (3)	0.0392 (7)	0.50
H8A	0.0449	0.1669	0.3574	0.059*	0.50
H8B	0.2210	0.1413	0.2985	0.059*	0.50
H8C	0.1017	0.2754	0.3073	0.059*	0.50
O32	0.4688 (3)	0.1558 (2)	0.54352 (18)	0.0365 (5)	0.50
C35	0.3937 (10)	0.1619 (8)	0.4454 (5)	0.0359 (15)	0.50
H35A	0.3574	0.2468	0.4149	0.043*	0.50
H35B	0.4830	0.1191	0.3961	0.043*	0.50
C36	0.2674 (7)	0.1257 (5)	0.4299 (5)	0.0216 (10)	0.50
H36A	0.3227	0.0475	0.4005	0.026*	0.50
C37	0.1788 (5)	0.0918 (4)	0.5366 (3)	0.0565 (11)	0.50
H37A	0.0915	0.0649	0.5169	0.085*	0.50
H37B	0.1312	0.1616	0.5767	0.085*	0.50
H37C	0.2582	0.0278	0.5830	0.085*	0.50
C38	0.1386 (4)	0.1940 (3)	0.3445 (3)	0.0392 (7)	0.50
H38A	0.0580	0.1546	0.3438	0.059*	0.50
H38B	0.1916	0.1960	0.2720	0.059*	0.50
H38C	0.0833	0.2755	0.3627	0.059*	0.50
C9	0.6097 (3)	0.5338 (2)	0.7157 (2)	0.0226 (5)
H9	0.4946	0.5601	0.7293	0.027*
C10	0.7099 (3)	0.5319 (2)	0.7990 (2)	0.0227 (5)
H10	0.6648	0.5576	0.8676	0.027*
C11	0.8794 (3)	0.4915 (2)	0.7802 (2)	0.0214 (5)
C12	0.9386 (3)	0.4578 (2)	0.6774 (2)	0.0224 (5)
H12	1.0532	0.4305	0.6617	0.027*
C13	0.8285 (3)	0.4644 (2)	0.5982 (2)	0.0225 (5)
H13	0.8699	0.4425	0.5278	0.027*
C14	0.9924 (3)	0.4844 (2)	0.8672 (2)	0.0236 (5)
H14	1.1066	0.4638	0.8516	0.028*
C15	0.5105 (4)	0.7783 (3)	−0.0282 (3)	0.0331 (7)
C16	0.4464 (4)	0.6899 (3)	0.0108 (3)	0.0341 (7)
H16	0.4841	0.6424	0.0782	0.041*
C17	0.3289 (4)	0.6702 (3)	−0.0467 (3)	0.0396 (7)
H17	0.2853	0.6104	−0.0182	0.048*
C18	0.2746 (4)	0.7376 (3)	−0.1460 (3)	0.0412 (8)
H18	0.1939	0.7242	−0.1858	0.049*
C19	0.3388 (5)	0.8241 (3)	−0.1867 (3)	0.0409 (8)
H19	0.3024	0.8700	−0.2550	0.049*
C20	0.4562 (4)	0.8450 (3)	−0.1289 (3)	0.0374 (7)
H20	0.4995	0.9048	−0.1578	0.045*
C21	0.6361 (5)	0.8005 (3)	0.0363 (3)	0.0461 (8)
H21A	0.6290	0.7699	0.1134	0.069*
H21B	0.6150	0.8862	0.0304	0.069*
H21C	0.7460	0.7598	0.0069	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.0115 (2)	0.0342 (3)	0.0152 (2)	−0.00714 (19)	−0.00478 (17)	−0.00191 (18)
S1	0.0150 (3)	0.0399 (4)	0.0199 (3)	−0.0084 (3)	−0.0028 (2)	0.0008 (3)
S2	0.0158 (3)	0.0365 (4)	0.0203 (3)	−0.0070 (3)	−0.0042 (2)	−0.0037 (3)
P1	0.0194 (3)	0.0345 (4)	0.0219 (3)	−0.0092 (3)	−0.0064 (3)	−0.0007 (3)
O1	0.0293 (11)	0.0306 (10)	0.0278 (10)	−0.0096 (9)	−0.0100 (9)	0.0017 (8)
N1	0.0135 (10)	0.0313 (11)	0.0171 (10)	−0.0078 (9)	−0.0058 (8)	−0.0010 (8)
N2	0.0194 (11)	0.0366 (12)	0.0227 (11)	−0.0107 (10)	−0.0096 (9)	−0.0029 (9)
C1	0.0312 (15)	0.0320 (14)	0.0269 (14)	−0.0061 (12)	−0.0147 (12)	−0.0020 (11)
C2	0.0295 (15)	0.0310 (14)	0.0238 (13)	−0.0015 (12)	−0.0073 (12)	−0.0019 (11)
C3	0.0416 (19)	0.0414 (17)	0.0380 (17)	−0.0051 (15)	−0.0229 (15)	−0.0037 (14)
C4	0.0437 (19)	0.0377 (16)	0.0264 (15)	−0.0022 (14)	−0.0030 (14)	0.0049 (13)
O2	0.0376 (12)	0.0486 (13)	0.0326 (11)	−0.0256 (11)	−0.0088 (10)	−0.0040 (10)
C5	0.020 (3)	0.016 (2)	0.031 (3)	−0.001 (2)	−0.017 (2)	0.003 (2)
C6	0.032 (4)	0.058 (5)	0.043 (4)	−0.019 (4)	−0.015 (3)	0.015 (4)
C7	0.045 (2)	0.084 (3)	0.049 (2)	−0.042 (2)	−0.0094 (18)	0.022 (2)
C8	0.0304 (16)	0.0492 (18)	0.0411 (18)	−0.0182 (15)	−0.0093 (14)	0.0007 (15)
O32	0.0376 (12)	0.0486 (13)	0.0326 (11)	−0.0256 (11)	−0.0088 (10)	−0.0040 (10)
C35	0.037 (4)	0.053 (5)	0.027 (3)	−0.028 (4)	−0.006 (3)	0.001 (3)
C36	0.024 (3)	0.016 (2)	0.027 (3)	−0.007 (2)	−0.001 (2)	−0.008 (2)
C37	0.045 (2)	0.084 (3)	0.049 (2)	−0.042 (2)	−0.0094 (18)	0.022 (2)
C38	0.0304 (16)	0.0492 (18)	0.0411 (18)	−0.0182 (15)	−0.0093 (14)	0.0007 (15)
C9	0.0167 (12)	0.0315 (13)	0.0190 (12)	−0.0071 (10)	−0.0057 (10)	−0.0022 (10)
C10	0.0190 (12)	0.0303 (13)	0.0192 (12)	−0.0082 (10)	−0.0061 (10)	−0.0024 (10)
C11	0.0174 (12)	0.0281 (12)	0.0204 (12)	−0.0098 (10)	−0.0075 (10)	0.0000 (10)
C12	0.0135 (11)	0.0305 (13)	0.0231 (12)	−0.0080 (10)	−0.0041 (10)	0.0001 (10)
C13	0.0145 (12)	0.0324 (13)	0.0207 (12)	−0.0080 (10)	−0.0035 (10)	−0.0019 (10)
C14	0.0188 (12)	0.0301 (13)	0.0239 (12)	−0.0102 (10)	−0.0075 (10)	−0.0020 (10)
C15	0.0297 (15)	0.0316 (14)	0.0328 (16)	−0.0039 (12)	0.0015 (13)	−0.0061 (12)
C16	0.0316 (16)	0.0323 (14)	0.0305 (15)	−0.0035 (12)	0.0062 (13)	−0.0006 (12)
C17	0.0360 (17)	0.0420 (17)	0.0404 (18)	−0.0140 (14)	0.0092 (14)	−0.0067 (14)
C18	0.0318 (17)	0.0471 (18)	0.0415 (18)	−0.0079 (15)	0.0004 (14)	−0.0119 (15)
C19	0.0439 (19)	0.0386 (16)	0.0303 (16)	−0.0030 (15)	−0.0023 (14)	−0.0010 (13)
C20	0.0431 (18)	0.0309 (15)	0.0340 (16)	−0.0091 (14)	0.0030 (14)	−0.0010 (13)
C21	0.046 (2)	0.0434 (18)	0.050 (2)	−0.0162 (16)	−0.0097 (17)	−0.0032 (16)

Geometric parameters (Å, º) top

Ni—N1	2.096 (2)	C8—H8C	0.9800
Ni—N1ⁱ	2.096 (2)	O32—C35	1.388 (7)
Ni—S1ⁱ	2.4806 (8)	C35—C36	1.352 (8)
Ni—S1	2.4806 (8)	C35—H35A	0.9900
Ni—S2	2.4823 (8)	C35—H35B	0.9900
Ni—S2ⁱ	2.4823 (8)	C36—C38	1.519 (6)
S1—P1	1.9949 (11)	C36—C37	1.564 (7)
S2—P1	1.9864 (10)	C36—H36A	1.0000
P1—O32	1.585 (2)	C37—H37A	0.9800
P1—O2	1.585 (2)	C37—H37B	0.9800
P1—O1	1.587 (2)	C37—H37C	0.9800
O1—C1	1.453 (3)	C38—H38A	0.9800
N1—C13	1.342 (3)	C38—H38B	0.9800
N1—C9	1.344 (3)	C38—H38C	0.9800
N2—C14	1.281 (4)	C9—C10	1.379 (3)
N2—N2ⁱⁱ	1.410 (4)	C9—H9	0.9500
C1—C2	1.511 (4)	C10—C11	1.396 (4)
C1—H1A	0.9900	C10—H10	0.9500
C1—H1B	0.9900	C11—C12	1.391 (4)
C2—C4	1.525 (4)	C11—C14	1.472 (3)
C2—C3	1.533 (4)	C12—C13	1.384 (3)
C2—H2	1.0000	C12—H12	0.9500
C3—H3A	0.9800	C13—H13	0.9500
C3—H3B	0.9800	C14—H14	0.9500
C3—H3C	0.9800	C15—C16	1.393 (4)
C4—H4A	0.9800	C15—C20	1.398 (4)
C4—H4B	0.9800	C15—C21	1.505 (5)
C4—H4C	0.9800	C16—C17	1.381 (5)
O2—C5	1.558 (6)	C16—H16	0.9500
C5—C6	1.164 (9)	C17—C18	1.387 (5)
C5—H5A	0.9900	C17—H17	0.9500
C5—H5B	0.9900	C18—C19	1.380 (5)
C6—C7	1.553 (8)	C18—H18	0.9500
C6—C8	1.617 (8)	C19—C20	1.389 (5)
C6—H6A	1.0000	C19—H19	0.9500
C7—H7A	0.9800	C20—H20	0.9500
C7—H7B	0.9800	C21—H21A	0.9800
C7—H7C	0.9800	C21—H21B	0.9800
C8—H8A	0.9800	C21—H21C	0.9800
C8—H8B	0.9800

N1—Ni—N1ⁱ	180.0	H7B—C7—H7C	109.5
N1—Ni—S1ⁱ	91.71 (6)	C6—C8—H8A	109.5
N1ⁱ—Ni—S1ⁱ	88.29 (6)	C6—C8—H8B	109.5
N1—Ni—S1	88.29 (6)	H8A—C8—H8B	109.5
N1ⁱ—Ni—S1	91.71 (6)	C6—C8—H8C	109.5
S1ⁱ—Ni—S1	180.00 (3)	H8A—C8—H8C	109.5
N1—Ni—S2	90.35 (6)	H8B—C8—H8C	109.5
N1ⁱ—Ni—S2	89.65 (6)	C35—O32—P1	129.0 (3)
S1ⁱ—Ni—S2	98.04 (3)	C36—C35—O32	127.6 (6)
S1—Ni—S2	81.96 (3)	C36—C35—H35A	105.4
N1—Ni—S2ⁱ	89.65 (6)	O32—C35—H35A	105.4
N1ⁱ—Ni—S2ⁱ	90.35 (6)	C36—C35—H35B	105.4
S1ⁱ—Ni—S2ⁱ	81.96 (3)	O32—C35—H35B	105.4
S1—Ni—S2ⁱ	98.04 (3)	H35A—C35—H35B	106.0
S2—Ni—S2ⁱ	180.0	C35—C36—C38	120.7 (5)
P1—S1—Ni	84.11 (3)	C35—C36—C37	115.7 (5)
P1—S2—Ni	84.24 (3)	C38—C36—C37	108.6 (4)
O32—P1—O2	0.00 (17)	C35—C36—H36A	103.1
O32—P1—O1	96.75 (12)	C38—C36—H36A	103.1
O2—P1—O1	96.75 (12)	C37—C36—H36A	103.1
O32—P1—S2	113.02 (9)	C36—C37—H37A	109.5
O2—P1—S2	113.02 (9)	C36—C37—H37B	109.5
O1—P1—S2	111.99 (9)	H37A—C37—H37B	109.5
O32—P1—S1	112.44 (10)	C36—C37—H37C	109.5
O2—P1—S1	112.44 (10)	H37A—C37—H37C	109.5
O1—P1—S1	112.53 (9)	H37B—C37—H37C	109.5
S2—P1—S1	109.66 (5)	C36—C38—H38A	109.5
C1—O1—P1	117.69 (18)	C36—C38—H38B	109.5
C13—N1—C9	117.5 (2)	H38A—C38—H38B	109.5
C13—N1—Ni	122.93 (18)	C36—C38—H38C	109.5
C9—N1—Ni	119.51 (17)	H38A—C38—H38C	109.5
C14—N2—N2ⁱⁱ	111.6 (3)	H38B—C38—H38C	109.5
O1—C1—C2	109.9 (2)	N1—C9—C10	123.6 (2)
O1—C1—H1A	109.7	N1—C9—H9	118.2
C2—C1—H1A	109.7	C10—C9—H9	118.2
O1—C1—H1B	109.7	C9—C10—C11	118.5 (2)
C2—C1—H1B	109.7	C9—C10—H10	120.8
H1A—C1—H1B	108.2	C11—C10—H10	120.8
C1—C2—C4	111.8 (3)	C12—C11—C10	118.4 (2)
C1—C2—C3	108.0 (3)	C12—C11—C14	120.9 (2)
C4—C2—C3	110.8 (3)	C10—C11—C14	120.8 (2)
C1—C2—H2	108.7	C13—C12—C11	119.1 (2)
C4—C2—H2	108.7	C13—C12—H12	120.4
C3—C2—H2	108.7	C11—C12—H12	120.4
C2—C3—H3A	109.5	N1—C13—C12	122.9 (2)
C2—C3—H3B	109.5	N1—C13—H13	118.6
H3A—C3—H3B	109.5	C12—C13—H13	118.6
C2—C3—H3C	109.5	N2—C14—C11	119.9 (2)
H3A—C3—H3C	109.5	N2—C14—H14	120.0
H3B—C3—H3C	109.5	C11—C14—H14	120.0
C2—C4—H4A	109.5	C16—C15—C20	118.4 (3)
C2—C4—H4B	109.5	C16—C15—C21	120.7 (3)
H4A—C4—H4B	109.5	C20—C15—C21	120.9 (3)
C2—C4—H4C	109.5	C17—C16—C15	121.2 (3)
H4A—C4—H4C	109.5	C17—C16—H16	119.4
H4B—C4—H4C	109.5	C15—C16—H16	119.4
C5—O2—P1	111.3 (3)	C16—C17—C18	120.0 (3)
C6—C5—O2	117.8 (6)	C16—C17—H17	120.0
C6—C5—H5A	107.9	C18—C17—H17	120.0
O2—C5—H5A	107.9	C19—C18—C17	119.5 (3)
C6—C5—H5B	107.9	C19—C18—H18	120.2
O2—C5—H5B	107.9	C17—C18—H18	120.2
H5A—C5—H5B	107.2	C18—C19—C20	120.8 (3)
C5—C6—C7	130.3 (6)	C18—C19—H19	119.6
C5—C6—C8	117.4 (6)	C20—C19—H19	119.6
C7—C6—C8	104.4 (5)	C19—C20—C15	120.1 (3)
C5—C6—H6A	99.3	C19—C20—H20	120.0
C7—C6—H6A	99.3	C15—C20—H20	120.0
C8—C6—H6A	99.3	C15—C21—H21A	109.5
C6—C7—H7A	109.5	C15—C21—H21B	109.5
C6—C7—H7B	109.5	H21A—C21—H21B	109.5
H7A—C7—H7B	109.5	C15—C21—H21C	109.5
C6—C7—H7C	109.5	H21A—C21—H21C	109.5
H7A—C7—H7C	109.5	H21B—C21—H21C	109.5

N1—Ni—S1—P1	−91.85 (7)	O32—P1—O2—C5	0 (43)
N1ⁱ—Ni—S1—P1	88.15 (7)	O1—P1—O2—C5	174.5 (3)
S1ⁱ—Ni—S1—P1	114 (100)	S2—P1—O2—C5	−68.1 (3)
S2—Ni—S1—P1	−1.26 (3)	S1—P1—O2—C5	56.7 (3)
S2ⁱ—Ni—S1—P1	178.74 (3)	P1—O2—C5—C6	−146.3 (7)
N1—Ni—S2—P1	89.49 (7)	O2—C5—C6—C7	−0.2 (15)
N1ⁱ—Ni—S2—P1	−90.51 (7)	O2—C5—C6—C8	−143.8 (5)
S1ⁱ—Ni—S2—P1	−178.74 (3)	O2—P1—O32—C35	0 (59)
S1—Ni—S2—P1	1.26 (3)	O1—P1—O32—C35	−158.0 (5)
S2ⁱ—Ni—S2—P1	16 (100)	S2—P1—O32—C35	−40.6 (5)
Ni—S2—P1—O32	124.67 (10)	S1—P1—O32—C35	84.2 (5)
Ni—S2—P1—O2	124.67 (10)	P1—O32—C35—C36	−147.9 (7)
Ni—S2—P1—O1	−127.32 (9)	O32—C35—C36—C38	144.5 (7)
Ni—S2—P1—S1	−1.65 (4)	O32—C35—C36—C37	10.4 (12)
Ni—S1—P1—O32	−124.99 (10)	C13—N1—C9—C10	−0.6 (4)
Ni—S1—P1—O2	−124.99 (10)	Ni—N1—C9—C10	177.1 (2)
Ni—S1—P1—O1	127.01 (9)	N1—C9—C10—C11	−1.0 (4)
Ni—S1—P1—S2	1.65 (4)	C9—C10—C11—C12	1.5 (4)
O32—P1—O1—C1	178.8 (2)	C9—C10—C11—C14	−178.2 (2)
O2—P1—O1—C1	178.8 (2)	C10—C11—C12—C13	−0.5 (4)
S2—P1—O1—C1	60.6 (2)	C14—C11—C12—C13	179.2 (2)
S1—P1—O1—C1	−63.5 (2)	C9—N1—C13—C12	1.7 (4)
N1ⁱ—Ni—N1—C13	83 (100)	Ni—N1—C13—C12	−175.9 (2)
S1ⁱ—Ni—N1—C13	−52.9 (2)	C11—C12—C13—N1	−1.1 (4)
S1—Ni—N1—C13	127.1 (2)	N2ⁱⁱ—N2—C14—C11	179.8 (3)
S2—Ni—N1—C13	45.1 (2)	C12—C11—C14—N2	−173.9 (3)
S2ⁱ—Ni—N1—C13	−134.9 (2)	C10—C11—C14—N2	5.8 (4)
N1ⁱ—Ni—N1—C9	−95 (100)	C20—C15—C16—C17	−1.6 (5)
S1ⁱ—Ni—N1—C9	129.46 (19)	C21—C15—C16—C17	178.8 (3)
S1—Ni—N1—C9	−50.54 (19)	C15—C16—C17—C18	1.0 (5)
S2—Ni—N1—C9	−132.48 (19)	C16—C17—C18—C19	0.0 (5)
S2ⁱ—Ni—N1—C9	47.52 (19)	C17—C18—C19—C20	−0.5 (5)
P1—O1—C1—C2	−162.1 (2)	C18—C19—C20—C15	−0.1 (5)
O1—C1—C2—C4	−62.2 (3)	C16—C15—C20—C19	1.1 (5)
O1—C1—C2—C3	175.6 (3)	C21—C15—C20—C19	−179.3 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···S1ⁱⁱⁱ	0.95	2.76	3.694 (3)	169

Symmetry code: (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₈H₁₈O₂PS₂)₂(C₁₂H₁₀N₄)]·2C₇H₇
M_r	935.85
Crystal system, space group	Triclinic, P1
Temperature (K)	98
a, b, c (Å)	8.7132 (15), 12.089 (2), 12.293 (2)
α, β, γ (°)	82.662 (10), 86.528 (10), 69.321 (6)
V (Å³)	1201.4 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.795, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	8239, 5457, 4980
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.142, 1.08
No. of reflections	5457
No. of parameters	279
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.78

Computer programs: CrystalClear (Rigaku, 2005), SHEXLS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006).