Synthesis and structural characterization of donor-stabilized disubstituted diphenyldithiophosphates of nickel(II)

Donor-stabilized addition complexes of nickel(II) with disubstituted diphenyldithiophosphates, [{(ArO)₂PS₂}₂NiL₂] {Ar = 2,4-(CH₃)₂C₆H₃ [(1), (5)], 2,5-(CH₃)₂C₆H₃ [(2), (6)], 3,4-(CH₃)₂C₆H₃ [(3), (7)] and 3,5-(CH₃)₂C₆H₃ [(4), (8)]; L = C₅H₅N [(1)-(4)] and C₇H₉N [(5)-(8)]}, were successfully isolated and characterized by elemental analysis, magnetic moment, IR spectroscopy and single-crystal X-ray analysis. Compound (4) crystallizes in the monoclinic space group P2₁/n whereas compounds (7) and (8) crystallize in the triclinic space group . The single-crystal X-ray diffraction analysis of (4), (7) and (8) reveals a six-coordinated octahedral geometry for the NiS₄N₂ chromophore. Two diphenyldithiophosphate ions act as bidentate ligands with their S atoms coordinated to the Ni centre. Each of them forms a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Ni atom.

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

For all compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1993) for Py_JAMMU_0m; SHELXS97 (Altomare et al., 1993) for 35etpy_0m; Sir-92 (Altomare et al., 1993) for 34ETPY_LT_0m. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures

(Py_JAMMU_0m)

Crystal data

C42H46N2NiO4P2S4	F(000) = 932
Mr = 891.72	Dx = 1.399 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9912 reflections
a = 11.7905 (3) Å	θ = 2.2–33.7°
b = 14.4443 (4) Å	µ = 0.77 mm^−1
c = 12.8825 (3) Å	T = 296 K
β = 105.195 (1)°	Needles, green
V = 2117.26 (9) Å^3	0.13 × 0.11 × 0.08 mm
Z = 2

Data collection

Bruker APEX-II CCD diffractometer	8779 independent reflections
Radiation source: fine-focus sealed tube	6366 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 34.2°, θmin = 2.1°
Absorption correction: multi-scan SADABS2008/1 - Bruker AXS area detector scaling and absorption correction	h = −18→18
Tmin = 0.674, Tmax = 0.747	k = −22→22
33731 measured reflections	l = −14→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 0.3611P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
8779 reflections	Δρmax = 0.43 e Å^−3
250 parameters	Δρmin = −0.26 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.40981 (12)	0.02987 (10)	−0.25281 (10)	0.0288 (3)
C2	−0.52576 (12)	0.02809 (11)	−0.24933 (11)	0.0324 (3)
H2	−0.5465	0.0021	−0.1908	0.039*
C3	−0.61157 (13)	0.06583 (12)	−0.33473 (12)	0.0370 (3)
C4	−0.73997 (15)	0.05947 (17)	−0.33606 (17)	0.0566 (5)
H4A	−0.7792	0.1158	−0.3645	0.085*
H4B	−0.7467	0.0502	−0.2641	0.085*
H4C	−0.7755	0.0084	−0.3804	0.085*
C5	−0.57707 (14)	0.10503 (11)	−0.42000 (12)	0.0403 (3)
H5	−0.6338	0.1316	−0.4763	0.048*
C6	−0.46057 (14)	0.10582 (11)	−0.42381 (11)	0.0371 (3)
C7	−0.42775 (19)	0.14551 (14)	−0.52053 (14)	0.0522 (4)
H7A	−0.4120	0.2105	−0.5097	0.078*
H7B	−0.4915	0.1366	−0.5836	0.078*
H7C	−0.3589	0.1147	−0.5297	0.078*
C8	−0.37564 (13)	0.06751 (11)	−0.33857 (11)	0.0342 (3)
H8	−0.2970	0.0672	−0.3393	0.041*
C9	−0.37217 (11)	0.13128 (10)	0.05952 (11)	0.0294 (3)
C10	−0.27510 (12)	0.14982 (12)	0.14433 (12)	0.0361 (3)
H10	−0.2013	0.1273	0.1440	0.043*
C11	−0.29011 (13)	0.20290 (12)	0.23019 (12)	0.0368 (3)
C12	−0.18648 (16)	0.22457 (16)	0.32391 (15)	0.0567 (5)
H12A	−0.2128	0.2586	0.3773	0.085*
H12B	−0.1305	0.2610	0.2994	0.085*
H12C	−0.1502	0.1679	0.3547	0.085*
C13	−0.40104 (13)	0.23595 (11)	0.22823 (12)	0.0363 (3)
H13	−0.4106	0.2714	0.2856	0.044*
C14	−0.49830 (12)	0.21754 (10)	0.14304 (12)	0.0333 (3)
C15	−0.48285 (11)	0.16430 (10)	0.05772 (11)	0.0308 (3)
H15	−0.5466	0.1510	−0.0002	0.037*
C16	−0.61786 (14)	0.25317 (15)	0.14434 (17)	0.0537 (5)
H16A	−0.6351	0.3081	0.1012	0.081*
H16B	−0.6188	0.2673	0.2169	0.081*
H16C	−0.6760	0.2068	0.1157	0.081*
C17	0.03890 (15)	0.01432 (11)	0.24296 (12)	0.0376 (3)
H17	0.0136	−0.0469	0.2348	0.045*
C18	0.07306 (18)	0.05105 (15)	0.34554 (13)	0.0509 (4)
H18	0.0706	0.0153	0.4049	0.061*
C19	0.11111 (17)	0.14216 (15)	0.35829 (15)	0.0551 (5)
H19	0.1358	0.1684	0.4264	0.066*
C20	0.11171 (17)	0.19256 (14)	0.26904 (16)	0.0523 (4)
H20	0.1357	0.2541	0.2753	0.063*
C21	0.07620 (14)	0.15102 (11)	0.16915 (13)	0.0395 (3)
H21	0.0771	0.1860	0.1088	0.047*
N1	0.04056 (10)	0.06282 (8)	0.15505 (9)	0.0291 (2)
O1	−0.32521 (9)	−0.01500 (7)	−0.17008 (8)	0.0317 (2)
O2	−0.36813 (8)	0.07618 (8)	−0.02823 (8)	0.0383 (2)
P1	−0.25683 (3)	0.03299 (3)	−0.05975 (3)	0.02614 (8)
S1	−0.17964 (3)	−0.06773 (3)	0.03665 (3)	0.03126 (8)
S2	−0.14329 (3)	0.12875 (2)	−0.07671 (3)	0.03202 (8)
Ni1	0.0000	0.0000	0.0000	0.02378 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0293 (6)	0.0316 (6)	0.0220 (5)	0.0012 (5)	0.0004 (5)	−0.0047 (5)
C2	0.0318 (6)	0.0375 (7)	0.0271 (6)	0.0007 (5)	0.0059 (5)	0.0002 (5)
C3	0.0310 (6)	0.0429 (8)	0.0334 (7)	0.0040 (6)	0.0019 (5)	−0.0019 (6)
C4	0.0310 (8)	0.0788 (14)	0.0564 (11)	0.0069 (8)	0.0051 (7)	0.0039 (10)
C5	0.0421 (8)	0.0414 (8)	0.0310 (7)	0.0040 (6)	−0.0017 (6)	0.0021 (6)
C6	0.0486 (8)	0.0358 (7)	0.0254 (6)	−0.0051 (6)	0.0070 (6)	−0.0015 (6)
C7	0.0739 (12)	0.0514 (10)	0.0332 (8)	−0.0092 (9)	0.0174 (8)	0.0026 (7)
C8	0.0339 (7)	0.0406 (8)	0.0279 (6)	−0.0039 (6)	0.0075 (5)	−0.0049 (6)
C9	0.0267 (6)	0.0355 (7)	0.0257 (6)	0.0020 (5)	0.0061 (5)	−0.0047 (5)
C10	0.0264 (6)	0.0499 (9)	0.0298 (7)	0.0042 (6)	0.0036 (5)	−0.0077 (6)
C11	0.0322 (6)	0.0449 (8)	0.0307 (7)	−0.0010 (6)	0.0037 (5)	−0.0082 (6)
C12	0.0411 (9)	0.0785 (14)	0.0429 (9)	0.0054 (9)	−0.0025 (7)	−0.0255 (9)
C13	0.0379 (7)	0.0385 (8)	0.0335 (7)	0.0003 (6)	0.0114 (6)	−0.0094 (6)
C14	0.0295 (6)	0.0341 (7)	0.0369 (7)	0.0024 (5)	0.0097 (5)	−0.0054 (6)
C15	0.0256 (5)	0.0366 (7)	0.0285 (6)	0.0022 (5)	0.0041 (5)	−0.0024 (5)
C16	0.0337 (8)	0.0635 (12)	0.0631 (11)	0.0092 (7)	0.0112 (7)	−0.0248 (10)
C17	0.0438 (8)	0.0390 (8)	0.0281 (7)	0.0035 (6)	0.0060 (6)	0.0034 (6)
C18	0.0593 (11)	0.0638 (12)	0.0260 (7)	0.0109 (9)	0.0046 (7)	0.0034 (7)
C19	0.0528 (10)	0.0687 (13)	0.0349 (8)	0.0101 (9)	−0.0047 (7)	−0.0174 (9)
C20	0.0536 (10)	0.0458 (10)	0.0532 (11)	−0.0080 (8)	0.0063 (8)	−0.0187 (8)
C21	0.0430 (8)	0.0355 (8)	0.0385 (8)	−0.0050 (6)	0.0079 (6)	−0.0029 (6)
N1	0.0276 (5)	0.0310 (6)	0.0270 (5)	0.0014 (4)	0.0039 (4)	0.0000 (4)
O1	0.0303 (5)	0.0363 (5)	0.0243 (4)	0.0056 (4)	0.0000 (4)	−0.0050 (4)
O2	0.0254 (4)	0.0567 (7)	0.0301 (5)	0.0051 (4)	0.0025 (4)	−0.0164 (5)
P1	0.02289 (14)	0.03223 (17)	0.02170 (14)	0.00304 (12)	0.00300 (11)	−0.00184 (12)
S1	0.02839 (15)	0.03534 (18)	0.02821 (16)	−0.00350 (12)	0.00416 (12)	0.00716 (13)
S2	0.03340 (16)	0.02825 (16)	0.03250 (17)	0.00190 (12)	0.00527 (13)	0.00500 (13)
Ni1	0.02310 (10)	0.02506 (11)	0.02187 (11)	0.00003 (8)	0.00358 (8)	0.00204 (8)

Geometric parameters (Å, º)

C1—C2	1.380 (2)	C13—H13	0.9300
C1—C8	1.383 (2)	C14—C15	1.392 (2)
C1—O1	1.4121 (16)	C14—C16	1.505 (2)
C2—C3	1.396 (2)	C15—H15	0.9300
C2—H2	0.9300	C16—H16A	0.9600
C3—C5	1.388 (2)	C16—H16B	0.9600
C3—C4	1.512 (2)	C16—H16C	0.9600
C4—H4A	0.9600	C17—N1	1.3361 (19)
C4—H4B	0.9600	C17—C18	1.382 (2)
C4—H4C	0.9600	C17—H17	0.9300
C5—C6	1.387 (2)	C18—C19	1.386 (3)
C5—H5	0.9300	C18—H18	0.9300
C6—C8	1.392 (2)	C19—C20	1.362 (3)
C6—C7	1.511 (2)	C19—H19	0.9300
C7—H7A	0.9600	C20—C21	1.382 (2)
C7—H7B	0.9600	C20—H20	0.9300
C7—H7C	0.9600	C21—N1	1.339 (2)
C8—H8	0.9300	C21—H21	0.9300
C9—C15	1.3838 (18)	N1—Ni1	2.1310 (11)
C9—C10	1.3855 (19)	O1—P1	1.5968 (10)
C9—O2	1.3935 (16)	O2—P1	1.5987 (10)
C10—C11	1.395 (2)	P1—S1	1.9734 (5)
C10—H10	0.9300	P1—S2	1.9765 (5)
C11—C13	1.386 (2)	S1—Ni1	2.4881 (3)
C11—C12	1.508 (2)	S2—Ni1	2.5326 (3)
C12—H12A	0.9600	Ni1—N1^i	2.1310 (11)
C12—H12B	0.9600	Ni1—S1^i	2.4881 (3)
C12—H12C	0.9600	Ni1—S2^i	2.5326 (3)
C13—C14	1.389 (2)
C2—C1—C8	122.15 (13)	C9—C15—H15	120.2
C2—C1—O1	118.48 (12)	C14—C15—H15	120.2
C8—C1—O1	119.17 (12)	C14—C16—H16A	109.5
C1—C2—C3	119.13 (14)	C14—C16—H16B	109.5
C1—C2—H2	120.4	H16A—C16—H16B	109.5
C3—C2—H2	120.4	C14—C16—H16C	109.5
C5—C3—C2	118.74 (14)	H16A—C16—H16C	109.5
C5—C3—C4	121.06 (14)	H16B—C16—H16C	109.5
C2—C3—C4	120.13 (15)	N1—C17—C18	122.94 (16)
C3—C4—H4A	109.5	N1—C17—H17	118.5
C3—C4—H4B	109.5	C18—C17—H17	118.5
H4A—C4—H4B	109.5	C17—C18—C19	118.80 (17)
C3—C4—H4C	109.5	C17—C18—H18	120.6
H4A—C4—H4C	109.5	C19—C18—H18	120.6
H4B—C4—H4C	109.5	C20—C19—C18	118.72 (16)
C6—C5—C3	121.97 (14)	C20—C19—H19	120.6
C6—C5—H5	119.0	C18—C19—H19	120.6
C3—C5—H5	119.0	C19—C20—C21	119.12 (17)
C5—C6—C8	118.88 (14)	C19—C20—H20	120.4
C5—C6—C7	120.14 (15)	C21—C20—H20	120.4
C8—C6—C7	120.96 (15)	N1—C21—C20	123.18 (16)
C6—C7—H7A	109.5	N1—C21—H21	118.4
C6—C7—H7B	109.5	C20—C21—H21	118.4
H7A—C7—H7B	109.5	C17—N1—C21	117.24 (13)
C6—C7—H7C	109.5	C17—N1—Ni1	121.45 (10)
H7A—C7—H7C	109.5	C21—N1—Ni1	121.18 (10)
H7B—C7—H7C	109.5	C1—O1—P1	124.37 (9)
C1—C8—C6	119.11 (14)	C9—O2—P1	129.34 (9)
C1—C8—H8	120.4	O1—P1—O2	97.99 (5)
C6—C8—H8	120.4	O1—P1—S1	106.38 (4)
C15—C9—C10	121.81 (13)	O2—P1—S1	113.69 (5)
C15—C9—O2	114.57 (11)	O1—P1—S2	113.83 (4)
C10—C9—O2	123.59 (12)	O2—P1—S2	112.32 (5)
C9—C10—C11	118.77 (13)	S1—P1—S2	111.81 (2)
C9—C10—H10	120.6	P1—S1—Ni1	82.288 (15)
C11—C10—H10	120.6	P1—S2—Ni1	81.073 (15)
C13—C11—C10	119.34 (13)	N1^i—Ni1—N1	180.00 (6)
C13—C11—C12	120.37 (14)	N1^i—Ni1—S1	91.00 (3)
C10—C11—C12	120.28 (14)	N1—Ni1—S1	89.00 (3)
C11—C12—H12A	109.5	N1^i—Ni1—S1^i	89.00 (3)
C11—C12—H12B	109.5	N1—Ni1—S1^i	91.00 (3)
H12A—C12—H12B	109.5	S1—Ni1—S1^i	180.0
C11—C12—H12C	109.5	N1^i—Ni1—S2	89.09 (3)
H12A—C12—H12C	109.5	N1—Ni1—S2	90.91 (3)
H12B—C12—H12C	109.5	S1—Ni1—S2	81.303 (12)
C11—C13—C14	121.87 (13)	S1^i—Ni1—S2	98.696 (12)
C11—C13—H13	119.1	N1^i—Ni1—S2^i	90.91 (3)
C14—C13—H13	119.1	N1—Ni1—S2^i	89.09 (3)
C13—C14—C15	118.53 (13)	S1—Ni1—S2^i	98.697 (12)
C13—C14—C16	120.50 (13)	S1^i—Ni1—S2^i	81.304 (12)
C15—C14—C16	120.97 (13)	S2—Ni1—S2^i	180.0
C9—C15—C14	119.68 (12)
C8—C1—C2—C3	−0.3 (2)	C2—C1—O1—P1	−88.69 (15)
O1—C1—C2—C3	−175.07 (13)	C8—C1—O1—P1	96.41 (14)
C1—C2—C3—C5	−0.8 (2)	C15—C9—O2—P1	174.30 (11)
C1—C2—C3—C4	176.24 (16)	C10—C9—O2—P1	−7.8 (2)
C2—C3—C5—C6	1.5 (2)	C1—O1—P1—O2	49.54 (12)
C4—C3—C5—C6	−175.47 (17)	C1—O1—P1—S1	167.19 (10)
C3—C5—C6—C8	−1.1 (2)	C1—O1—P1—S2	−69.22 (11)
C3—C5—C6—C7	177.30 (16)	C9—O2—P1—O1	−177.58 (13)
C2—C1—C8—C6	0.7 (2)	C9—O2—P1—S1	70.54 (14)
O1—C1—C8—C6	175.42 (13)	C9—O2—P1—S2	−57.67 (14)
C5—C6—C8—C1	0.0 (2)	O1—P1—S1—Ni1	108.14 (4)
C7—C6—C8—C1	−178.41 (15)	O2—P1—S1—Ni1	−145.17 (5)
C15—C9—C10—C11	0.3 (2)	S2—P1—S1—Ni1	−16.69 (2)
O2—C9—C10—C11	−177.47 (15)	O1—P1—S2—Ni1	−104.14 (4)
C9—C10—C11—C13	−0.3 (2)	O2—P1—S2—Ni1	145.64 (4)
C9—C10—C11—C12	−179.96 (17)	S1—P1—S2—Ni1	16.44 (2)
C10—C11—C13—C14	0.2 (3)	C17—N1—Ni1—S1	48.95 (11)
C12—C11—C13—C14	179.81 (18)	C21—N1—Ni1—S1	−135.48 (11)
C11—C13—C14—C15	0.0 (2)	C17—N1—Ni1—S1^i	−131.05 (11)
C11—C13—C14—C16	178.98 (17)	C21—N1—Ni1—S1^i	44.52 (11)
C10—C9—C15—C14	−0.1 (2)	C17—N1—Ni1—S2	130.23 (11)
O2—C9—C15—C14	177.84 (14)	C21—N1—Ni1—S2	−54.20 (11)
C13—C14—C15—C9	0.0 (2)	C17—N1—Ni1—S2^i	−49.77 (11)
C16—C14—C15—C9	−179.00 (16)	C21—N1—Ni1—S2^i	125.80 (11)
N1—C17—C18—C19	−0.2 (3)	P1—S1—Ni1—N1^i	−76.77 (3)
C17—C18—C19—C20	1.0 (3)	P1—S1—Ni1—N1	103.23 (3)
C18—C19—C20—C21	−1.0 (3)	P1—S1—Ni1—S2	12.155 (15)
C19—C20—C21—N1	0.1 (3)	P1—S1—Ni1—S2^i	−167.843 (15)
C18—C17—N1—C21	−0.7 (2)	P1—S2—Ni1—N1^i	78.97 (3)
C18—C17—N1—Ni1	175.09 (13)	P1—S2—Ni1—N1	−101.03 (3)
C20—C21—N1—C17	0.7 (2)	P1—S2—Ni1—S1	−12.174 (15)
C20—C21—N1—Ni1	−175.07 (13)	P1—S2—Ni1—S1^i	167.825 (15)

Symmetry code: (i) −x, −y, −z.

(35etpy_0m)

Crystal data

C46H54N2NiO4P2S4	Z = 1
Mr = 947.82	F(000) = 498
Triclinic, P1	Dx = 1.338 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5505 (8) Å	Cell parameters from 9906 reflections
b = 9.8010 (8) Å	θ = 2.4–27.3°
c = 14.2026 (12) Å	µ = 0.70 mm^−1
α = 99.315 (4)°	T = 296 K
β = 98.447 (3)°	Needles, green
γ = 112.821 (3)°	0.15 × 0.11 × 0.09 mm
V = 1176.64 (17) Å^3

Data collection

Bruker APEX-II CCD diffractometer	5246 independent reflections
Radiation source: fine-focus sealed tube	4503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ and ω scans	θmax = 27.3°, θmin = 1.5°
Absorption correction: multi-scan SADABS2008/1 - Bruker AXS area detector scaling and absorption correction	h = −12→12
Tmin = 0.645, Tmax = 0.746	k = −12→10
18873 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 0.4175P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
5246 reflections	Δρmax = 0.31 e Å^−3
273 parameters	Δρmin = −0.23 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5327 (2)	0.20782 (19)	0.42517 (14)	0.0427 (4)
H1	0.4292	0.1635	0.4296	0.051*
C2	0.6013 (2)	0.1133 (2)	0.39513 (15)	0.0475 (4)
H2	0.5443	0.0080	0.3798	0.057*
C3	0.7557 (2)	0.1754 (2)	0.38771 (13)	0.0422 (4)
C4	0.83193 (19)	0.3330 (2)	0.41028 (13)	0.0405 (4)
H4	0.9350	0.3802	0.4055	0.049*
C5	0.75535 (18)	0.41989 (19)	0.43978 (12)	0.0364 (3)
H5	0.8093	0.5255	0.4545	0.044*
C6	0.8352 (2)	0.0752 (2)	0.35582 (18)	0.0592 (5)
H6A	0.9446	0.1390	0.3618	0.071*
H6B	0.8293	0.0079	0.3997	0.071*
C7	0.7654 (3)	−0.0195 (3)	0.25259 (18)	0.0709 (6)
H7A	0.6573	−0.0840	0.2461	0.106*
H7B	0.8200	−0.0814	0.2373	0.106*
H7C	0.7744	0.0462	0.2083	0.106*
C8	0.59751 (19)	0.44665 (19)	0.17368 (12)	0.0378 (3)
C9	0.6932 (2)	0.3718 (2)	0.17712 (13)	0.0413 (4)
H9	0.6734	0.2922	0.2084	0.050*
C10	0.8199 (2)	0.4161 (2)	0.13342 (13)	0.0456 (4)
C11	0.8462 (2)	0.5349 (2)	0.08748 (14)	0.0485 (4)
H11	0.9319	0.5662	0.0594	0.058*
C12	0.7482 (2)	0.6085 (2)	0.08213 (13)	0.0463 (4)
C13	0.6222 (2)	0.5631 (2)	0.12594 (13)	0.0446 (4)
H13	0.5550	0.6109	0.1232	0.053*
C14	0.9271 (3)	0.3357 (3)	0.1372 (2)	0.0672 (6)
H14A	0.9671	0.3400	0.2043	0.101*
H14B	1.0122	0.3850	0.1083	0.101*
H14C	0.8698	0.2311	0.1016	0.101*
C15	0.7780 (3)	0.7351 (3)	0.02916 (16)	0.0630 (6)
H15A	0.6994	0.7728	0.0323	0.094*
H15B	0.7747	0.6968	−0.0382	0.094*
H15C	0.8790	0.8164	0.0597	0.094*
C16	0.2901 (2)	0.6754 (2)	0.22377 (13)	0.0412 (4)
C17	0.2095 (2)	0.6937 (2)	0.29398 (15)	0.0517 (5)
H17	0.1899	0.6302	0.3371	0.062*
C18	0.1576 (3)	0.8090 (3)	0.29934 (16)	0.0615 (6)
C19	0.1929 (3)	0.9038 (2)	0.23628 (17)	0.0644 (6)
H19	0.1606	0.9823	0.2410	0.077*
C20	0.2745 (3)	0.8863 (2)	0.16629 (17)	0.0603 (6)
C21	0.3221 (2)	0.7679 (2)	0.15923 (15)	0.0505 (4)
H21	0.3747	0.7518	0.1115	0.061*
C22	0.0592 (4)	0.8241 (4)	0.3709 (2)	0.1077 (12)
H22A	−0.0492	0.7726	0.3379	0.161*
H22B	0.0855	0.9301	0.3964	0.161*
H22C	0.0787	0.7793	0.4238	0.161*
C23	0.3114 (4)	0.9920 (3)	0.0974 (2)	0.0979 (10)
H23A	0.3577	1.0960	0.1347	0.147*
H23B	0.2169	0.9729	0.0522	0.147*
H23C	0.3830	0.9741	0.0617	0.147*
P1	0.41869 (5)	0.49726 (5)	0.28995 (3)	0.03376 (10)
S1	0.27203 (5)	0.36042 (5)	0.35399 (3)	0.03779 (11)
S2	0.59665 (5)	0.66697 (5)	0.38503 (3)	0.03848 (11)
Ni1	0.5000	0.5000	0.5000	0.03037 (8)
N1	0.60740 (15)	0.36043 (15)	0.44840 (10)	0.0343 (3)
O1	0.47024 (14)	0.39259 (13)	0.21748 (9)	0.0414 (3)
O2	0.33424 (15)	0.55433 (14)	0.20882 (9)	0.0439 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0340 (8)	0.0339 (8)	0.0600 (11)	0.0140 (7)	0.0130 (8)	0.0093 (8)
C2	0.0438 (9)	0.0302 (8)	0.0670 (12)	0.0162 (7)	0.0123 (8)	0.0060 (8)
C3	0.0400 (9)	0.0405 (9)	0.0486 (10)	0.0229 (7)	0.0067 (7)	0.0054 (7)
C4	0.0306 (8)	0.0423 (9)	0.0487 (10)	0.0170 (7)	0.0083 (7)	0.0076 (7)
C5	0.0315 (8)	0.0316 (8)	0.0456 (9)	0.0134 (6)	0.0074 (7)	0.0090 (7)
C6	0.0506 (11)	0.0484 (11)	0.0827 (15)	0.0307 (9)	0.0147 (10)	0.0021 (10)
C7	0.0953 (18)	0.0632 (14)	0.0712 (15)	0.0492 (14)	0.0289 (13)	0.0118 (12)
C8	0.0401 (8)	0.0392 (9)	0.0354 (8)	0.0179 (7)	0.0117 (7)	0.0064 (7)
C9	0.0454 (9)	0.0420 (9)	0.0409 (9)	0.0228 (8)	0.0105 (7)	0.0100 (7)
C10	0.0446 (9)	0.0509 (10)	0.0457 (10)	0.0250 (8)	0.0122 (8)	0.0084 (8)
C11	0.0490 (10)	0.0562 (11)	0.0437 (10)	0.0226 (9)	0.0199 (8)	0.0112 (8)
C12	0.0569 (11)	0.0447 (10)	0.0373 (9)	0.0202 (9)	0.0148 (8)	0.0091 (7)
C13	0.0540 (10)	0.0451 (10)	0.0448 (10)	0.0286 (9)	0.0164 (8)	0.0136 (8)
C14	0.0590 (13)	0.0754 (15)	0.0877 (17)	0.0427 (12)	0.0305 (12)	0.0248 (13)
C15	0.0838 (16)	0.0600 (13)	0.0576 (13)	0.0318 (12)	0.0331 (11)	0.0286 (10)
C16	0.0411 (9)	0.0399 (9)	0.0457 (9)	0.0225 (7)	0.0017 (7)	0.0118 (7)
C17	0.0606 (12)	0.0596 (12)	0.0520 (11)	0.0405 (10)	0.0125 (9)	0.0206 (9)
C18	0.0703 (14)	0.0721 (14)	0.0560 (12)	0.0515 (12)	0.0015 (10)	0.0088 (10)
C19	0.0742 (15)	0.0490 (12)	0.0692 (14)	0.0393 (11)	−0.0120 (12)	0.0041 (10)
C20	0.0602 (12)	0.0392 (10)	0.0691 (14)	0.0149 (9)	−0.0092 (10)	0.0178 (9)
C21	0.0477 (10)	0.0463 (10)	0.0530 (11)	0.0160 (8)	0.0039 (8)	0.0168 (9)
C22	0.148 (3)	0.164 (3)	0.086 (2)	0.135 (3)	0.042 (2)	0.039 (2)
C23	0.118 (2)	0.0578 (15)	0.111 (2)	0.0260 (16)	0.0098 (19)	0.0481 (16)
P1	0.0340 (2)	0.0343 (2)	0.0389 (2)	0.01845 (17)	0.01075 (16)	0.01205 (17)
S1	0.03103 (19)	0.0366 (2)	0.0455 (2)	0.01274 (16)	0.01009 (16)	0.01176 (17)
S2	0.0359 (2)	0.0331 (2)	0.0471 (2)	0.01256 (16)	0.01157 (17)	0.01427 (17)
Ni1	0.02844 (14)	0.02798 (15)	0.03867 (16)	0.01456 (11)	0.00938 (11)	0.01019 (11)
N1	0.0318 (6)	0.0314 (7)	0.0419 (7)	0.0157 (5)	0.0087 (5)	0.0087 (6)
O1	0.0442 (6)	0.0370 (6)	0.0505 (7)	0.0209 (5)	0.0202 (5)	0.0122 (5)
O2	0.0520 (7)	0.0494 (7)	0.0416 (6)	0.0318 (6)	0.0105 (5)	0.0139 (5)

Geometric parameters (Å, º)

C1—N1	1.341 (2)	C15—H15A	0.9600
C1—C2	1.376 (2)	C15—H15B	0.9600
C1—H1	0.9300	C15—H15C	0.9600
C2—C3	1.389 (2)	C16—C21	1.375 (3)
C2—H2	0.9300	C16—C17	1.377 (3)
C3—C4	1.384 (2)	C16—O2	1.401 (2)
C3—C6	1.511 (2)	C17—C18	1.395 (3)
C4—C5	1.376 (2)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.376 (3)
C5—N1	1.337 (2)	C18—C22	1.509 (3)
C5—H5	0.9300	C19—C20	1.379 (3)
C6—C7	1.499 (3)	C19—H19	0.9300
C6—H6A	0.9700	C20—C21	1.395 (3)
C6—H6B	0.9700	C20—C23	1.517 (3)
C7—H7A	0.9600	C21—H21	0.9300
C7—H7B	0.9600	C22—H22A	0.9600
C7—H7C	0.9600	C22—H22B	0.9600
C8—C9	1.376 (2)	C22—H22C	0.9600
C8—C13	1.381 (3)	C23—H23A	0.9600
C8—O1	1.405 (2)	C23—H23B	0.9600
C9—C10	1.392 (2)	C23—H23C	0.9600
C9—H9	0.9300	P1—O1	1.5978 (12)
C10—C11	1.383 (3)	P1—O2	1.6051 (12)
C10—C14	1.515 (3)	P1—S2	1.9709 (6)
C11—C12	1.386 (3)	P1—S1	1.9748 (6)
C11—H11	0.9300	S1—Ni1	2.5213 (5)
C12—C13	1.388 (3)	S2—Ni1	2.5164 (4)
C12—C15	1.510 (3)	Ni1—N1	2.1083 (13)
C13—H13	0.9300	Ni1—N1^i	2.1083 (13)
C14—H14A	0.9600	Ni1—S2^i	2.5164 (4)
C14—H14B	0.9600	Ni1—S1^i	2.5213 (5)
C14—H14C	0.9600
N1—C1—C2	123.48 (16)	C21—C16—O2	115.83 (17)
N1—C1—H1	118.3	C17—C16—O2	121.93 (16)
C2—C1—H1	118.3	C16—C17—C18	118.9 (2)
C1—C2—C3	119.82 (16)	C16—C17—H17	120.5
C1—C2—H2	120.1	C18—C17—H17	120.5
C3—C2—H2	120.1	C19—C18—C17	118.9 (2)
C4—C3—C2	116.63 (15)	C19—C18—C22	121.2 (2)
C4—C3—C6	122.09 (16)	C17—C18—C22	119.8 (2)
C2—C3—C6	121.27 (17)	C18—C19—C20	122.21 (19)
C5—C4—C3	120.11 (15)	C18—C19—H19	118.9
C5—C4—H4	119.9	C20—C19—H19	118.9
C3—C4—H4	119.9	C19—C20—C21	118.7 (2)
N1—C5—C4	123.41 (15)	C19—C20—C23	121.2 (2)
N1—C5—H5	118.3	C21—C20—C23	120.2 (2)
C4—C5—H5	118.3	C16—C21—C20	119.2 (2)
C7—C6—C3	113.64 (18)	C16—C21—H21	120.4
C7—C6—H6A	108.8	C20—C21—H21	120.4
C3—C6—H6A	108.8	C18—C22—H22A	109.5
C7—C6—H6B	108.8	C18—C22—H22B	109.5
C3—C6—H6B	108.8	H22A—C22—H22B	109.5
H6A—C6—H6B	107.7	C18—C22—H22C	109.5
C6—C7—H7A	109.5	H22A—C22—H22C	109.5
C6—C7—H7B	109.5	H22B—C22—H22C	109.5
H7A—C7—H7B	109.5	C20—C23—H23A	109.5
C6—C7—H7C	109.5	C20—C23—H23B	109.5
H7A—C7—H7C	109.5	H23A—C23—H23B	109.5
H7B—C7—H7C	109.5	C20—C23—H23C	109.5
C9—C8—C13	121.48 (16)	H23A—C23—H23C	109.5
C9—C8—O1	115.96 (15)	H23B—C23—H23C	109.5
C13—C8—O1	122.50 (15)	O1—P1—O2	97.83 (7)
C8—C9—C10	119.56 (17)	O1—P1—S2	113.19 (5)
C8—C9—H9	120.2	O2—P1—S2	112.47 (5)
C10—C9—H9	120.2	O1—P1—S1	106.59 (5)
C11—C10—C9	118.79 (17)	O2—P1—S1	113.14 (5)
C11—C10—C14	120.98 (18)	S2—P1—S1	112.61 (3)
C9—C10—C14	120.23 (18)	P1—S1—Ni1	81.477 (19)
C10—C11—C12	121.81 (17)	P1—S2—Ni1	81.675 (19)
C10—C11—H11	119.1	N1—Ni1—N1^i	180.00 (5)
C12—C11—H11	119.1	N1—Ni1—S2	90.85 (4)
C11—C12—C13	118.81 (18)	N1^i—Ni1—S2	89.15 (4)
C11—C12—C15	120.43 (18)	N1—Ni1—S2^i	89.15 (4)
C13—C12—C15	120.76 (18)	N1^i—Ni1—S2^i	90.85 (4)
C8—C13—C12	119.53 (17)	S2—Ni1—S2^i	180.0
C8—C13—H13	120.2	N1—Ni1—S1^i	90.04 (4)
C12—C13—H13	120.2	N1^i—Ni1—S1^i	89.96 (4)
C10—C14—H14A	109.5	S2—Ni1—S1^i	98.666 (15)
C10—C14—H14B	109.5	S2^i—Ni1—S1^i	81.334 (15)
H14A—C14—H14B	109.5	N1—Ni1—S1	89.96 (4)
C10—C14—H14C	109.5	N1^i—Ni1—S1	90.04 (4)
H14A—C14—H14C	109.5	S2—Ni1—S1	81.333 (15)
H14B—C14—H14C	109.5	S2^i—Ni1—S1	98.667 (15)
C12—C15—H15A	109.5	S1^i—Ni1—S1	180.0
C12—C15—H15B	109.5	C5—N1—C1	116.54 (14)
H15A—C15—H15B	109.5	C5—N1—Ni1	121.50 (11)
C12—C15—H15C	109.5	C1—N1—Ni1	121.94 (11)
H15A—C15—H15C	109.5	C8—O1—P1	125.11 (11)
H15B—C15—H15C	109.5	C16—O2—P1	127.77 (11)
C21—C16—C17	122.07 (17)
N1—C1—C2—C3	0.0 (3)	S2—P1—S1—Ni1	−15.11 (2)
C1—C2—C3—C4	−1.0 (3)	O1—P1—S2—Ni1	−105.86 (5)
C1—C2—C3—C6	179.47 (19)	O2—P1—S2—Ni1	144.41 (5)
C2—C3—C4—C5	1.0 (3)	S1—P1—S2—Ni1	15.13 (2)
C6—C3—C4—C5	−179.48 (18)	P1—S2—Ni1—N1	78.82 (4)
C3—C4—C5—N1	0.0 (3)	P1—S2—Ni1—N1^i	−101.18 (4)
C4—C3—C6—C7	−115.1 (2)	P1—S2—Ni1—S1^i	168.993 (18)
C2—C3—C6—C7	64.5 (3)	P1—S2—Ni1—S1	−11.006 (18)
C13—C8—C9—C10	1.4 (3)	P1—S1—Ni1—N1	−79.87 (4)
O1—C8—C9—C10	178.54 (15)	P1—S1—Ni1—N1^i	100.13 (4)
C8—C9—C10—C11	0.0 (3)	P1—S1—Ni1—S2	10.991 (18)
C8—C9—C10—C14	179.53 (18)	P1—S1—Ni1—S2^i	−169.009 (18)
C9—C10—C11—C12	−1.4 (3)	C4—C5—N1—C1	−1.0 (2)
C14—C10—C11—C12	179.14 (19)	C4—C5—N1—Ni1	177.26 (13)
C10—C11—C12—C13	1.3 (3)	C2—C1—N1—C5	0.9 (3)
C10—C11—C12—C15	−178.44 (19)	C2—C1—N1—Ni1	−177.25 (15)
C9—C8—C13—C12	−1.4 (3)	S2—Ni1—N1—C5	47.95 (12)
O1—C8—C13—C12	−178.39 (15)	S2^i—Ni1—N1—C5	−132.05 (12)
C11—C12—C13—C8	0.1 (3)	S1^i—Ni1—N1—C5	−50.72 (12)
C15—C12—C13—C8	179.82 (18)	S1—Ni1—N1—C5	129.28 (12)
C21—C16—C17—C18	0.4 (3)	S2—Ni1—N1—C1	−133.94 (13)
O2—C16—C17—C18	−174.57 (18)	S2^i—Ni1—N1—C1	46.06 (13)
C16—C17—C18—C19	−2.0 (3)	S1^i—Ni1—N1—C1	127.40 (13)
C16—C17—C18—C22	175.7 (2)	S1—Ni1—N1—C1	−52.61 (13)
C17—C18—C19—C20	1.7 (3)	C9—C8—O1—P1	133.96 (14)
C22—C18—C19—C20	−176.0 (2)	C13—C8—O1—P1	−48.9 (2)
C18—C19—C20—C21	0.2 (3)	O2—P1—O1—C8	77.40 (14)
C18—C19—C20—C23	179.8 (2)	S2—P1—O1—C8	−41.20 (14)
C17—C16—C21—C20	1.5 (3)	S1—P1—O1—C8	−165.54 (12)
O2—C16—C21—C20	176.76 (16)	C21—C16—O2—P1	136.57 (15)
C19—C20—C21—C16	−1.8 (3)	C17—C16—O2—P1	−48.1 (2)
C23—C20—C21—C16	178.7 (2)	O1—P1—O2—C16	−165.41 (14)
O1—P1—S1—Ni1	109.59 (5)	S2—P1—O2—C16	−46.26 (16)
O2—P1—S1—Ni1	−144.04 (5)	S1—P1—O2—C16	82.74 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

(34ETPY_LT_0m)

Crystal data

C46H54N2NiO4P2S4	Z = 1
Mr = 947.82	F(000) = 498
Triclinic, P1	Dx = 1.383 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9327 (6) Å	Cell parameters from 7562 reflections
b = 11.2267 (10) Å	θ = 2.6–29.0°
c = 15.5768 (14) Å	µ = 0.73 mm^−1
α = 102.744 (3)°	T = 100 K
β = 94.409 (3)°	Needles, green
γ = 103.785 (3)°	0.15 × 0.09 × 0.06 mm
V = 1137.67 (18) Å^3

Data collection

Bruker APEX-II CCD diffractometer	6067 independent reflections
Radiation source: fine-focus sealed tube	4830 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scans	θmax = 29.2°, θmin = 1.9°
Absorption correction: multi-scan SADABS2008/1 - Bruker AXS area detector scaling and absorption correction	h = −8→9
Tmin = 0.691, Tmax = 0.746	k = −15→14
21578 measured reflections	l = −21→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.080P)^2 + 1.7604P] where P = (Fo^2 + 2Fc^2)/3
S = 0.69	(Δ/σ)max = 0.001
6067 reflections	Δρmax = 0.43 e Å^−3
270 parameters	Δρmin = −0.29 e Å^−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0677 (3)	0.28190 (18)	0.58147 (13)	0.0196 (4)
H1	0.2021	0.2777	0.5934	0.024*
C2	0.0261 (3)	0.39810 (18)	0.60615 (13)	0.0204 (4)
H2	0.1308	0.4711	0.6346	0.025*
C3	−0.1682 (3)	0.40885 (18)	0.58952 (13)	0.0185 (4)
C4	−0.3132 (3)	0.29777 (19)	0.54879 (14)	0.0220 (4)
H4	−0.4486	0.2994	0.5360	0.026*
C5	−0.2605 (3)	0.18473 (18)	0.52689 (13)	0.0197 (4)
H5	−0.3633	0.1099	0.4999	0.024*
C6	−0.2117 (3)	0.53688 (19)	0.61347 (15)	0.0254 (4)
H6A	−0.1779	0.5799	0.5654	0.030*
H6B	−0.1220	0.5883	0.6683	0.030*
C7	−0.4272 (3)	0.5349 (2)	0.62813 (16)	0.0306 (5)
H7A	−0.5175	0.4885	0.5732	0.046*
H7B	−0.4398	0.6218	0.6448	0.046*
H7C	−0.4629	0.4930	0.6758	0.046*
C8	0.1830 (3)	−0.16216 (17)	0.77341 (12)	0.0177 (4)
C9	0.3586 (3)	−0.18614 (19)	0.74746 (13)	0.0216 (4)
H9	0.3820	−0.1958	0.6873	0.026*
C10	0.5008 (3)	−0.19576 (19)	0.81221 (14)	0.0236 (4)
H10	0.6232	−0.2115	0.7956	0.028*
C11	0.4683 (3)	−0.18297 (18)	0.90031 (14)	0.0211 (4)
C12	0.2893 (3)	−0.15597 (18)	0.92535 (13)	0.0207 (4)
C13	0.1482 (3)	−0.14537 (18)	0.86079 (13)	0.0195 (4)
H13	0.0275	−0.1265	0.8770	0.023*
C14	0.2461 (3)	−0.1430 (2)	1.01967 (14)	0.0272 (4)
H14A	0.1231	−0.1152	1.0260	0.041*
H14B	0.3582	−0.0804	1.0599	0.041*
H14C	0.2288	−0.2249	1.0346	0.041*
C15	0.6215 (3)	−0.1992 (2)	0.96817 (15)	0.0277 (4)
H15A	0.7320	−0.2224	0.9388	0.042*
H15B	0.5583	−0.2661	0.9960	0.042*
H15C	0.6736	−0.1196	1.0138	0.042*
C16	−0.2481 (3)	0.17716 (19)	0.76843 (13)	0.0202 (4)
H23	−0.3591	0.1086	0.7391	0.024*
C17	−0.0633 (3)	0.15749 (17)	0.78973 (12)	0.0163 (3)
C18	0.1008 (3)	0.25634 (18)	0.83133 (12)	0.0199 (4)
H18	0.2268	0.2403	0.8445	0.024*
C19	0.0807 (3)	0.37952 (19)	0.85387 (13)	0.0239 (4)
C20	0.2612 (4)	0.4870 (2)	0.89871 (18)	0.0368 (5)
H20A	0.2937	0.5450	0.8601	0.055*
H20B	0.3757	0.4529	0.9100	0.055*
H20C	0.2311	0.5327	0.9552	0.055*
C21	−0.1064 (3)	0.40187 (19)	0.83379 (13)	0.0237 (4)
C22	−0.2671 (3)	0.3004 (2)	0.79108 (13)	0.0231 (4)
H22	−0.3935	0.3156	0.7770	0.028*
C23	−0.1330 (4)	0.5345 (2)	0.85876 (17)	0.0358 (5)
H23A	−0.2727	0.5323	0.8407	0.054*
H23B	−0.0445	0.5886	0.8285	0.054*
H23C	−0.0993	0.5686	0.9232	0.054*
N1	−0.0728 (2)	0.17447 (14)	0.54145 (10)	0.0156 (3)
O1	0.02722 (19)	−0.16540 (12)	0.70848 (9)	0.0184 (3)
O2	−0.0423 (2)	0.03328 (12)	0.77571 (8)	0.0178 (3)
P1	−0.00316 (7)	−0.04123 (4)	0.68072 (3)	0.01443 (11)
S1	−0.24247 (6)	−0.09581 (4)	0.59044 (3)	0.01681 (10)
S2	0.23636 (6)	0.05391 (4)	0.64104 (3)	0.01646 (10)
Ni1	0.0000	0.0000	0.5000	0.01306 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0149 (8)	0.0192 (9)	0.0224 (10)	0.0031 (7)	0.0013 (7)	0.0023 (7)
C2	0.0174 (8)	0.0157 (9)	0.0243 (10)	0.0009 (7)	0.0009 (7)	0.0011 (7)
C3	0.0210 (9)	0.0160 (9)	0.0183 (9)	0.0050 (7)	0.0040 (7)	0.0033 (7)
C4	0.0175 (8)	0.0216 (10)	0.0248 (10)	0.0077 (7)	−0.0018 (7)	0.0004 (8)
C5	0.0161 (8)	0.0173 (9)	0.0227 (10)	0.0037 (7)	−0.0011 (7)	0.0006 (7)
C6	0.0267 (10)	0.0166 (10)	0.0319 (11)	0.0077 (8)	0.0028 (8)	0.0023 (8)
C7	0.0312 (11)	0.0262 (11)	0.0351 (12)	0.0159 (9)	0.0046 (9)	−0.0002 (9)
C8	0.0226 (9)	0.0134 (9)	0.0161 (9)	0.0034 (7)	−0.0012 (7)	0.0041 (7)
C9	0.0264 (9)	0.0213 (10)	0.0178 (9)	0.0077 (8)	0.0038 (7)	0.0047 (7)
C10	0.0247 (9)	0.0229 (10)	0.0250 (10)	0.0093 (8)	0.0044 (8)	0.0060 (8)
C11	0.0232 (9)	0.0151 (9)	0.0234 (10)	0.0025 (7)	−0.0012 (7)	0.0053 (7)
C12	0.0278 (10)	0.0158 (9)	0.0167 (9)	0.0016 (7)	0.0025 (7)	0.0053 (7)
C13	0.0227 (9)	0.0162 (9)	0.0187 (9)	0.0028 (7)	0.0034 (7)	0.0047 (7)
C14	0.0363 (11)	0.0257 (11)	0.0181 (10)	0.0046 (9)	0.0032 (8)	0.0060 (8)
C15	0.0283 (10)	0.0246 (11)	0.0276 (11)	0.0043 (8)	−0.0061 (8)	0.0074 (9)
C16	0.0221 (9)	0.0190 (9)	0.0169 (9)	0.0029 (7)	0.0018 (7)	0.0018 (7)
C17	0.0227 (9)	0.0126 (8)	0.0126 (8)	0.0040 (7)	0.0038 (7)	0.0013 (7)
C18	0.0211 (9)	0.0205 (9)	0.0155 (9)	0.0029 (7)	0.0019 (7)	0.0019 (7)
C19	0.0290 (10)	0.0192 (10)	0.0186 (10)	−0.0008 (8)	0.0030 (8)	0.0020 (8)
C20	0.0364 (12)	0.0223 (11)	0.0409 (14)	−0.0045 (9)	−0.0006 (10)	0.0007 (10)
C21	0.0350 (11)	0.0188 (10)	0.0188 (10)	0.0090 (8)	0.0066 (8)	0.0043 (8)
C22	0.0264 (9)	0.0265 (11)	0.0189 (9)	0.0108 (8)	0.0045 (8)	0.0065 (8)
C23	0.0498 (14)	0.0213 (11)	0.0372 (13)	0.0125 (10)	0.0065 (11)	0.0054 (10)
N1	0.0148 (7)	0.0156 (7)	0.0149 (7)	0.0030 (6)	0.0012 (5)	0.0023 (6)
O1	0.0228 (6)	0.0135 (6)	0.0165 (6)	0.0030 (5)	−0.0031 (5)	0.0024 (5)
O2	0.0240 (6)	0.0149 (6)	0.0132 (6)	0.0042 (5)	0.0018 (5)	0.0022 (5)
P1	0.0158 (2)	0.0138 (2)	0.0122 (2)	0.00247 (17)	0.00030 (16)	0.00218 (17)
S1	0.01365 (19)	0.0195 (2)	0.0147 (2)	0.00111 (16)	0.00030 (15)	0.00298 (17)
S2	0.01388 (19)	0.0183 (2)	0.0152 (2)	0.00175 (16)	−0.00042 (15)	0.00349 (17)
Ni1	0.01243 (15)	0.01334 (16)	0.01225 (16)	0.00295 (12)	0.00037 (11)	0.00169 (12)

Geometric parameters (Å, º)

C1—N1	1.344 (2)	C15—H15A	0.9800
C1—C2	1.381 (3)	C15—H15B	0.9800
C1—H1	0.9500	C15—H15C	0.9800
C2—C3	1.390 (2)	C16—C17	1.379 (3)
C2—H2	0.9500	C16—C22	1.391 (3)
C3—C4	1.387 (3)	C16—H23	0.9500
C3—C6	1.511 (3)	C17—C18	1.383 (3)
C4—C5	1.382 (3)	C17—O2	1.408 (2)
C4—H4	0.9500	C18—C19	1.393 (3)
C5—N1	1.340 (2)	C18—H18	0.9500
C5—H5	0.9500	C19—C21	1.403 (3)
C6—C7	1.524 (3)	C19—C20	1.511 (3)
C6—H6A	0.9900	C20—H20A	0.9800
C6—H6B	0.9900	C20—H20B	0.9800
C7—H7A	0.9800	C20—H20C	0.9800
C7—H7B	0.9800	C21—C22	1.389 (3)
C7—H7C	0.9800	C21—C23	1.513 (3)
C8—C9	1.379 (3)	C22—H22	0.9500
C8—C13	1.380 (3)	C23—H23A	0.9800
C8—O1	1.410 (2)	C23—H23B	0.9800
C9—C10	1.395 (3)	C23—H23C	0.9800
C9—H9	0.9500	N1—Ni1	2.1146 (15)
C10—C11	1.390 (3)	O1—P1	1.6020 (13)
C10—H10	0.9500	O2—P1	1.6081 (13)
C11—C12	1.409 (3)	P1—S1	1.9704 (6)
C11—C15	1.511 (3)	P1—S2	1.9708 (7)
C12—C13	1.393 (3)	S1—Ni1	2.4775 (5)
C12—C14	1.505 (3)	S2—Ni1	2.5031 (5)
C13—H13	0.9500	Ni1—N1^i	2.1146 (15)
C14—H14A	0.9800	Ni1—S1^i	2.4775 (5)
C14—H14B	0.9800	Ni1—S2^i	2.5031 (5)
C14—H14C	0.9800
N1—C1—C2	123.15 (17)	C17—C16—H23	121.0
N1—C1—H1	118.4	C22—C16—H23	121.0
C2—C1—H1	118.4	C16—C17—C18	121.83 (17)
C1—C2—C3	120.40 (17)	C16—C17—O2	119.81 (16)
C1—C2—H2	119.8	C18—C17—O2	118.16 (16)
C3—C2—H2	119.8	C17—C18—C19	119.82 (18)
C4—C3—C2	116.37 (17)	C17—C18—H18	120.1
C4—C3—C6	123.37 (17)	C19—C18—H18	120.1
C2—C3—C6	120.24 (17)	C18—C19—C21	119.45 (18)
C5—C4—C3	119.92 (17)	C18—C19—C20	119.43 (19)
C5—C4—H4	120.0	C21—C19—C20	121.1 (2)
C3—C4—H4	120.0	C19—C20—H20A	109.5
N1—C5—C4	123.81 (17)	C19—C20—H20B	109.5
N1—C5—H5	118.1	H20A—C20—H20B	109.5
C4—C5—H5	118.1	C19—C20—H20C	109.5
C3—C6—C7	115.49 (17)	H20A—C20—H20C	109.5
C3—C6—H6A	108.4	H20B—C20—H20C	109.5
C7—C6—H6A	108.4	C22—C21—C19	119.09 (18)
C3—C6—H6B	108.4	C22—C21—C23	120.38 (19)
C7—C6—H6B	108.4	C19—C21—C23	120.5 (2)
H6A—C6—H6B	107.5	C21—C22—C16	121.74 (18)
C6—C7—H7A	109.5	C21—C22—H22	119.1
C6—C7—H7B	109.5	C16—C22—H22	119.1
H7A—C7—H7B	109.5	C21—C23—H23A	109.5
C6—C7—H7C	109.5	C21—C23—H23B	109.5
H7A—C7—H7C	109.5	H23A—C23—H23B	109.5
H7B—C7—H7C	109.5	C21—C23—H23C	109.5
C9—C8—C13	121.77 (17)	H23A—C23—H23C	109.5
C9—C8—O1	119.49 (17)	H23B—C23—H23C	109.5
C13—C8—O1	118.51 (16)	C5—N1—C1	116.34 (16)
C8—C9—C10	117.97 (18)	C5—N1—Ni1	121.84 (12)
C8—C9—H9	121.0	C1—N1—Ni1	121.80 (12)
C10—C9—H9	121.0	C8—O1—P1	122.88 (11)
C11—C10—C9	121.78 (18)	C17—O2—P1	121.25 (11)
C11—C10—H10	119.1	O1—P1—O2	97.93 (7)
C9—C10—H10	119.1	O1—P1—S1	106.94 (5)
C10—C11—C12	119.05 (18)	O2—P1—S1	112.91 (5)
C10—C11—C15	120.55 (18)	O1—P1—S2	113.24 (6)
C12—C11—C15	120.39 (19)	O2—P1—S2	111.66 (6)
C13—C12—C11	119.09 (18)	S1—P1—S2	113.15 (3)
C13—C12—C14	119.86 (18)	P1—S1—Ni1	82.34 (2)
C11—C12—C14	121.02 (18)	P1—S2—Ni1	81.66 (2)
C8—C13—C12	120.30 (18)	N1^i—Ni1—N1	180.00 (7)
C8—C13—H13	119.9	N1^i—Ni1—S1^i	90.12 (4)
C12—C13—H13	119.9	N1—Ni1—S1^i	89.88 (4)
C12—C14—H14A	109.5	N1^i—Ni1—S1	89.88 (4)
C12—C14—H14B	109.5	N1—Ni1—S1	90.12 (4)
H14A—C14—H14B	109.5	S1^i—Ni1—S1	180.0
C12—C14—H14C	109.5	N1^i—Ni1—S2	90.58 (4)
H14A—C14—H14C	109.5	N1—Ni1—S2	89.42 (4)
H14B—C14—H14C	109.5	S1^i—Ni1—S2	97.335 (16)
C11—C15—H15A	109.5	S1—Ni1—S2	82.666 (16)
C11—C15—H15B	109.5	N1^i—Ni1—S2^i	89.42 (4)
H15A—C15—H15B	109.5	N1—Ni1—S2^i	90.58 (4)
C11—C15—H15C	109.5	S1^i—Ni1—S2^i	82.665 (16)
H15A—C15—H15C	109.5	S1—Ni1—S2^i	97.335 (16)
H15B—C15—H15C	109.5	S2—Ni1—S2^i	180.00 (2)
C17—C16—C22	118.06 (18)
N1—C1—C2—C3	−0.4 (3)	C4—C5—N1—Ni1	−176.64 (16)
C1—C2—C3—C4	0.8 (3)	C2—C1—N1—C5	−0.7 (3)
C1—C2—C3—C6	−177.69 (19)	C2—C1—N1—Ni1	177.38 (15)
C2—C3—C4—C5	−0.2 (3)	C9—C8—O1—P1	−95.39 (19)
C6—C3—C4—C5	178.32 (19)	C13—C8—O1—P1	89.96 (19)
C3—C4—C5—N1	−1.0 (3)	C16—C17—O2—P1	85.35 (19)
C4—C3—C6—C7	25.3 (3)	C18—C17—O2—P1	−99.65 (18)
C2—C3—C6—C7	−156.3 (2)	C8—O1—P1—O2	−61.83 (15)
C13—C8—C9—C10	1.3 (3)	C8—O1—P1—S1	−178.78 (13)
O1—C8—C9—C10	−173.18 (17)	C8—O1—P1—S2	55.90 (15)
C8—C9—C10—C11	0.6 (3)	C17—O2—P1—O1	174.94 (13)
C9—C10—C11—C12	−1.8 (3)	C17—O2—P1—S1	−72.83 (13)
C9—C10—C11—C15	177.48 (19)	C17—O2—P1—S2	56.00 (14)
C10—C11—C12—C13	1.3 (3)	O1—P1—S1—Ni1	−121.63 (6)
C15—C11—C12—C13	−178.05 (18)	O2—P1—S1—Ni1	131.80 (6)
C10—C11—C12—C14	179.17 (19)	S2—P1—S1—Ni1	3.74 (3)
C15—C11—C12—C14	−0.2 (3)	O1—P1—S2—Ni1	118.20 (6)
C9—C8—C13—C12	−1.9 (3)	O2—P1—S2—Ni1	−132.42 (6)
O1—C8—C13—C12	172.67 (17)	S1—P1—S2—Ni1	−3.71 (3)
C11—C12—C13—C8	0.5 (3)	C5—N1—Ni1—S1^i	121.70 (15)
C14—C12—C13—C8	−177.40 (18)	C1—N1—Ni1—S1^i	−56.26 (14)
C22—C16—C17—C18	−0.9 (3)	C5—N1—Ni1—S1	−58.30 (15)
C22—C16—C17—O2	173.95 (17)	C1—N1—Ni1—S1	123.74 (14)
C16—C17—C18—C19	0.9 (3)	C5—N1—Ni1—S2	−140.96 (15)
O2—C17—C18—C19	−173.99 (17)	C1—N1—Ni1—S2	41.07 (14)
C17—C18—C19—C21	−0.2 (3)	C5—N1—Ni1—S2^i	39.04 (15)
C17—C18—C19—C20	−179.57 (19)	C1—N1—Ni1—S2^i	−138.93 (14)
C18—C19—C21—C22	−0.6 (3)	P1—S1—Ni1—N1^i	87.87 (4)
C20—C19—C21—C22	178.8 (2)	P1—S1—Ni1—N1	−92.13 (4)
C18—C19—C21—C23	179.1 (2)	P1—S1—Ni1—S2	−2.73 (2)
C20—C19—C21—C23	−1.5 (3)	P1—S1—Ni1—S2^i	177.27 (2)
C19—C21—C22—C16	0.6 (3)	P1—S2—Ni1—N1^i	−87.07 (5)
C23—C21—C22—C16	−179.1 (2)	P1—S2—Ni1—N1	92.93 (5)
C17—C16—C22—C21	0.1 (3)	P1—S2—Ni1—S1^i	−177.27 (2)
C4—C5—N1—C1	1.4 (3)	P1—S2—Ni1—S1	2.73 (2)

Symmetry code: (i) −x, −y, −z+1.