Two new [Ni(tren)₂]²⁺ complexes: [Ni(tren)₂]Cl₂ and [Ni(tren)₂]WS₄

Both title compounds, bis­[tris(2-amino­ethyl)­amine]­nickel(II) dichloride, [Ni(tren)₂]Cl₂, (I), and bis­[tris(2-amino­ethyl)­amine]­nickel(II) tetra­thio­tungstate, [Ni(tren)₂]WS₄, (II), contain the [Ni(tren)₂]²⁺ cation [tren is tris(2-amino­ethyl)­amine, C₆H₁₈N₄]. The tren mol­ecule acts as a tridentate ligand around the central Ni atom, with the remaining primary amine group not bound to the central atom. In (I), Ni²⁺ is located on a centre of inversion surrounded by one crystallographically independent tren mol­ecule. In the [Ni(tren)₂]²⁺ cation of (II), the Ni atom is bound to two crystallographically independent tren mol­ecules. The Ni atoms in the [Ni(tren)₂]²⁺ complexes are in a distorted octahedral environment consisting of six N atoms from the chelating tren mol­ecules. The counter-ions are chloride anions in (I) and the tetrahedral [WS₄]^2- anion in (II). Hydro­gen bonding is observed in both compounds.

S1. Comment

It is well documented that the tren molecule can act as a tri- or tetradentate ligand and several transition metal complexes have been prepared (Gaudin et al., 1986). Many transition metal ions prefer the octahedral geometry with tren as a tetradentate ligand, leaving two cis positions available for bonding to other ligands. Examples are [Ni(tren)(H₂O)Cl]Cl·H₂O (Marzotto et al., 1993) and [Ni(tren){N(CN)₂}₂] (Březina et al., 1999). If the two cis positions are used by another multidentate ligand, such as the oxalate anion. dimeric complexes were obtained, with the two Ni(tren) units bridged by the other multidentate ligand, as in [Ni₂(tren)₂(C₂O₄)](ClO₄)₂ (Castro et al., 1997; Březina et al., 1997) and [Ni₂(tren)₂(C₆O₄Cl₂)](BPh₄)₂ (Pierpont et al., 1977). Another binding mode of the tren ligand yields cationic chains. These chains are found in the two compounds {[Ni₂(tren)₃](ClO₄)₄·H₂O}_n (Masters et al., 1999) and {[Ni₂(tren)₃][Mo₂O₂S₆]₂·2.75H₂O}_n (Ellermeier & Bensch, 2001). In the polymeric chains, one Ni atom is coordinated by two tren molecules which act as tridentate ligands. The other Ni atom is coordinated by all four N atoms of one tren molecule and by the two remaining N atoms of the two tren ligands which are tridentate bound to the neighboured Ni atoms. The coordination behavior of the tren molecules leads to the formation of zigzag [Ni₂(tren)₃]_n chains. The two new [Ni(tren)₂]²⁺ complexes presented here contain isolated cations with the tren molecules acting as a tridentate ligand. This coordination mode was first reported by Colpas et al. (1990) for [Ni(tren)₂](BF₄)₂.

Violet crystals of [Ni(tren)₂]Cl₂, (I), were obtained by attempts to synthesize compounds which could be used as precursors for the syntheses of new thioantimonates with complex transition metal cations (Stähler & Bensch, 2001). Due to the abovementioned variety in the bonding modes of the multidentate tren molecule, a single-crystal diffraction study was performed. In contrast, [Ni(tren)₂]WS₄, (II), was obtained as part of a project on the synthesis of new thiotungstates with transition metals under solvothermal conditions. Both compounds contain the [Ni(tren)₂]²⁺ complex cation, and the counter-ions are Cl^- in (I) and the tetrahedral [WS₄]^2- anion in (II). Each Ni²⁺ cation in [Ni(tren)₂]²⁺ in (I) and (II) is sixfold coordinated by the N atoms of two tren molecules acting as tridentate ligands. Therefore, each tren ligand has one primary amine group which is not connected to the transition metal atom. The structures of the cations in (I) and (II) are illustrated in Figs. 1 and 2, and selected bond lengths and angles are given in Tables 1 and 3, respectively. In (I), the Ni atom is on a centre of inversion, surrounded by one crystallographically independent tren molecule. The environment is completed by a tren molecule generated by symmetry. In (II), the Ni atom is bound to two crystallographically independent tren molecules. The Ni—N bond lengths in (I) are between 2.105 (3) and 2.176 (3) Å. The N—Ni—N angles range from 80.56 (11) to 99.44 (11)°, reflecting the distortion of the octahedral geometry. The chloride anions in (I) are involved in a complicated hydrogen-bond network (Table 2) that may significantly contribute to the stability of the compound. There are five short intermolecular contacts between the Cl^- anions and the H atoms of the tren ligand ranging from 2.40 (4) (H3N···Clⁱⁱ) to 2.61 (4) Å [H2N···Clⁱⁱ; symmetry code: (ii) -x, -y, -z]. A short contact is also observed between an H atom and an N atom of neighbouring tren molecules [H4N···N4ⁱⁱⁱ; symmetry code: (iii) -x + 1/2, y + 1/2, -z + 3/2].

The WS₄ tetrahedron in compound (II) is only slightly distorted (Fig. 2), with S—W—S angles between 108.39 (4) and 110.78 (4)° (Table 3). The W—S bond lengths range from 2.1580 (10) to 2.2122 (9) Å. The W—S3 distance of 2.2122 (9) Å is significantly longer than the average W—S bond length in [WS₄]^2- anions of 2.177 Å (Müller et al., 1981). One reason may be that S3 is involved in three short contacts to H atoms of the tren ligands (Table 4). The other S atoms have only one relatively short contact to H atoms. The geometrical parameters for the [Ni(tren)₂]²⁺ cation in (II) are in good agreement with that found in the cation of (I) and with the [Ni(tren)₂]²⁺ cation described by Colpas et al. (1990). The Ni—N bond lengths vary from 2.130 (3) to 2.152 (2) Å and the corresponding cis-N—Ni—N angles range from 80.95 (10) to 100.13 (10)° (Table 3). The [WS₄]^2- anions and [Ni(tren)₂]²⁺ cations in (II) each form rods along the a and c axes and the rods alterante along the b axis (Fig. 3).

S2. Experimental

[Ni(tren)₂]Cl₂, (I), was prepared in a 100 ml glass flask at room temperature (293 K). NiCl₂·6H₂O (237.7 mg, 1 mmol) was dissolved in ethanol (99%, 10 ml) and tren (95%, 10 ml) was added to the mixture. Violet crystals were received after 48 h. The phase-pure product was washed with ethanol and dried under vacuum. [Ni(tren)₂]WS₄, (II), was prepared under solvothermal conditions. NiCl₂·6H₂O, Na₂WO₄·2H₂O and sulfur (0.50 mmol, molar ratio 1:2:8) were reacted in tris(2-aminoethyl)amine (95%, 3 ml) in a Teflon-lined steel autoclave at 393 K for 5 d. The product was filtered off and washed with water. The yield of the phase-pure product is about 60%. The yellow–brown crystals obtained are stable on air.

S3. Refinement

The H atoms were positioned with idealized geometry and refined isotropically.

Computing details

For both compounds, data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 1999); software used to prepare material for publication: CIFTAB in SHELXL97.

Figures

	Fig. 1. A view of the [Ni(tren)2]^2+ cation in (I) with the atom-labelling scheme and displacement ellipsoids drawn at the 50% propability level [symmetry code: (i) -x, 1 - y, 1 - z].
	Fig. 2. The crystal structure of the anion and cation in [Ni(tren)2]WS4, (II), showing the atom-labelling scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 3. The packing diagram for (II), viewed along the c axis. H atoms have been omitted for clarity.

(I) 'bis[tris(2-aminoethyl)amine]nickel(II) dichoride'

Crystal data

[Ni(C6H18N4)2]Cl2	F(000) = 452
Mr = 422.10	Dx = 1.439 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0336 (18) Å	Cell parameters from 37 reflections
b = 10.630 (2) Å	θ = 9–16°
c = 10.717 (2) Å	µ = 1.28 mm^−1
β = 108.78 (3)°	T = 293 K
V = 974.3 (3) Å^3	Needle, violet
Z = 2	0.5 × 0.1 × 0.1 mm

Data collection

STOE AED-II four-circle diffractometer	1131 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω–θ scans	h = 0→10
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)	k = −12→1
Tmin = 0.810, Tmax = 0.840	l = −12→12
2042 measured reflections	4 standard reflections every 120 min
1715 independent reflections	intensity decay: none

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	Only H-atom coordinates refined
S = 1.01	Calculated w = 1/[σ^2(Fo^2) + (0.0306P)^2] where P = (Fo^2 + 2Fc^2)/3
1715 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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
Ni	0.0000	0.5000	0.5000	0.02336 (16)
Cl	0.60984 (11)	0.22982 (9)	0.43273 (9)	0.0475 (3)
N1	0.0988 (3)	0.5908 (3)	0.3655 (3)	0.0313 (7)
H1N	0.024 (4)	0.621 (3)	0.293 (3)	0.038*
H2N	0.155 (4)	0.651 (3)	0.403 (3)	0.038*
N2	0.1686 (3)	0.3570 (3)	0.4910 (2)	0.0268 (6)
N3	0.1847 (3)	0.5603 (3)	0.6654 (3)	0.0291 (6)
H3N	0.236 (4)	0.623 (3)	0.642 (3)	0.035*
H4N	0.158 (4)	0.587 (3)	0.731 (3)	0.035*
N4	0.3488 (3)	0.0913 (3)	0.5586 (3)	0.0361 (7)
H5N	0.360 (4)	0.011 (4)	0.553 (4)	0.054*
H6N	0.412 (4)	0.135 (4)	0.523 (4)	0.054*
C1	0.1978 (4)	0.5019 (5)	0.3199 (3)	0.0384 (8)
H1C	0.310 (4)	0.530 (3)	0.357 (3)	0.046*
H2C	0.173 (4)	0.505 (4)	0.223 (3)	0.046*
C2	0.1795 (4)	0.3672 (4)	0.3563 (3)	0.0344 (8)
H3C	0.088 (4)	0.326 (3)	0.299 (3)	0.041*
H4C	0.268 (4)	0.319 (3)	0.344 (3)	0.041*
C3	0.2947 (4)	0.4550 (3)	0.7090 (3)	0.0336 (8)
H5C	0.249 (4)	0.393 (3)	0.756 (3)	0.040*
H6C	0.395 (4)	0.487 (3)	0.766 (3)	0.040*
C4	0.3208 (3)	0.3922 (4)	0.5921 (3)	0.0336 (8)
H7C	0.373 (4)	0.463 (3)	0.553 (3)	0.040*
H8C	0.392 (4)	0.325 (3)	0.612 (3)	0.040*
C5	0.1124 (4)	0.2306 (3)	0.5155 (3)	0.0321 (8)
H9C	−0.005 (4)	0.228 (3)	0.465 (3)	0.039*
H10C	0.119 (3)	0.228 (3)	0.606 (3)	0.039*
C6	0.1857 (4)	0.1147 (4)	0.4772 (4)	0.0375 (9)
H11C	0.130 (4)	0.042 (3)	0.493 (3)	0.045*
H12C	0.176 (4)	0.119 (3)	0.381 (3)	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0198 (3)	0.0282 (3)	0.0206 (2)	0.0007 (3)	0.00450 (19)	0.0012 (3)
Cl	0.0483 (5)	0.0425 (6)	0.0569 (6)	−0.0148 (5)	0.0242 (5)	−0.0105 (5)
N1	0.0301 (16)	0.0325 (17)	0.0305 (15)	−0.0024 (13)	0.0085 (12)	0.0052 (13)
N2	0.0218 (13)	0.0330 (15)	0.0229 (13)	0.0002 (12)	0.0033 (10)	−0.0022 (12)
N3	0.0292 (16)	0.0332 (16)	0.0234 (13)	−0.0009 (13)	0.0065 (12)	−0.0018 (13)
N4	0.0340 (16)	0.0361 (18)	0.0402 (16)	0.0052 (14)	0.0146 (13)	0.0037 (15)
C1	0.0339 (17)	0.052 (2)	0.0339 (16)	0.004 (2)	0.0164 (13)	0.005 (2)
C2	0.0315 (19)	0.045 (2)	0.0283 (18)	0.0036 (18)	0.0124 (15)	−0.0039 (17)
C3	0.0252 (18)	0.037 (2)	0.0301 (16)	0.0020 (15)	−0.0026 (14)	0.0017 (15)
C4	0.0172 (16)	0.044 (2)	0.0357 (18)	0.0043 (16)	0.0028 (14)	−0.0041 (17)
C5	0.0268 (17)	0.033 (2)	0.0345 (18)	0.0020 (15)	0.0067 (15)	0.0027 (16)
C6	0.041 (2)	0.034 (2)	0.0369 (19)	0.0016 (17)	0.0112 (16)	−0.0033 (17)

Geometric parameters (Å, º)

Ni—N1	2.152 (3)	N4—H6N	0.90 (4)
Ni—N2	2.176 (3)	C1—C2	1.507 (6)
Ni—N3	2.105 (3)	C1—H1C	1.01 (3)
Ni—N3^i	2.105 (3)	C1—H2C	0.99 (3)
Ni—N1^i	2.152 (3)	C2—H3C	0.96 (3)
Ni—N2^i	2.176 (3)	C2—H4C	0.99 (3)
N1—C1	1.487 (5)	C3—C4	1.504 (5)
N1—H1N	0.91 (3)	C3—H5C	0.99 (3)
N1—H2N	0.84 (4)	C3—H6C	0.98 (3)
N2—C2	1.482 (4)	C4—H7C	1.04 (3)
N2—C5	1.490 (4)	C4—H8C	0.94 (4)
N2—C4	1.498 (4)	C5—C6	1.516 (5)
N3—C3	1.469 (4)	C5—H9C	1.02 (3)
N3—H3N	0.89 (3)	C5—H10C	0.96 (3)
N3—H4N	0.86 (3)	C6—H11C	0.97 (3)
N4—C6	1.471 (4)	C6—H12C	1.00 (3)
N4—H5N	0.87 (4)
N1—Ni—N2	80.56 (11)	N1—C1—C2	113.0 (3)
N1^i—Ni—N2	99.44 (11)	N1—C1—H1C	109 (2)
N3^i—Ni—N1	87.71 (11)	C2—C1—H1C	111 (2)
N3—Ni—N1	92.29 (11)	N1—C1—H2C	111 (2)
N3—Ni—N2	82.72 (10)	C2—C1—H2C	107 (2)
N3—Ni—N2^i	97.28 (10)	H1C—C1—H2C	106 (3)
N3—Ni—N3^i	180.0	N2—C2—C1	111.6 (3)
N3—Ni—N1^i	87.71 (11)	N2—C2—H3C	106 (2)
N3^i—Ni—N1^i	92.29 (11)	C1—C2—H3C	114 (2)
N1^i—Ni—N1	180.0	N2—C2—H4C	113.8 (19)
N3^i—Ni—N2^i	82.72 (10)	C1—C2—H4C	107 (2)
N1^i—Ni—N2^i	80.56 (11)	H3C—C2—H4C	104 (3)
N1—Ni—N2^i	99.44 (10)	N3—C3—C4	110.1 (3)
N3^i—Ni—N2	97.28 (10)	N3—C3—H5C	109 (2)
N2^i—Ni—N2	180.0	C4—C3—H5C	109 (2)
C1—N1—Ni	111.0 (2)	N3—C3—H6C	110 (2)
C1—N1—H1N	108 (2)	C4—C3—H6C	108.2 (18)
Ni—N1—H1N	112 (2)	H5C—C3—H6C	111 (3)
C1—N1—H2N	108 (2)	N2—C4—C3	111.1 (3)
Ni—N1—H2N	110 (2)	N2—C4—H7C	108.4 (18)
H1N—N1—H2N	108 (3)	C3—C4—H7C	103.2 (18)
C2—N2—C5	111.8 (3)	N2—C4—H8C	112 (2)
C2—N2—C4	110.7 (3)	C3—C4—H8C	116 (2)
C5—N2—C4	112.5 (3)	H7C—C4—H8C	106 (3)
C2—N2—Ni	105.0 (2)	N2—C5—C6	118.8 (3)
C5—N2—Ni	109.81 (18)	N2—C5—H9C	106.5 (18)
C4—N2—Ni	106.6 (2)	C6—C5—H9C	107.5 (18)
C3—N3—Ni	107.9 (2)	N2—C5—H10C	107 (2)
C3—N3—H3N	107 (2)	C6—C5—H10C	111 (2)
Ni—N3—H3N	109 (2)	H9C—C5—H10C	105 (2)
C3—N3—H4N	110 (2)	N4—C6—C5	114.7 (3)
Ni—N3—H4N	116 (2)	N4—C6—H11C	104 (2)
H3N—N3—H4N	107 (3)	C5—C6—H11C	108 (2)
C6—N4—H5N	104 (3)	N4—C6—H12C	110.6 (19)
C6—N4—H6N	108 (2)	C5—C6—H12C	110 (2)
H5N—N4—H6N	112 (4)	H11C—C6—H12C	110 (3)
N3—Ni—N1—C1	93.6 (2)	N3^i—Ni—N3—C3	121 (100)
N3^i—Ni—N1—C1	−86.4 (2)	N1^i—Ni—N3—C3	80.4 (2)
N1^i—Ni—N1—C1	48 (100)	N1—Ni—N3—C3	−99.6 (2)
N2^i—Ni—N1—C1	−168.7 (2)	N2^i—Ni—N3—C3	160.6 (2)
N2—Ni—N1—C1	11.3 (2)	N2—Ni—N3—C3	−19.4 (2)
N3—Ni—N2—C2	−124.8 (2)	Ni—N1—C1—C2	11.3 (3)
N3^i—Ni—N2—C2	55.2 (2)	C5—N2—C2—C1	166.1 (3)
N1^i—Ni—N2—C2	148.7 (2)	C4—N2—C2—C1	−67.6 (4)
N1—Ni—N2—C2	−31.3 (2)	Ni—N2—C2—C1	47.1 (3)
N2^i—Ni—N2—C2	169 (100)	N1—C1—C2—N2	−40.2 (4)
N3—Ni—N2—C5	114.8 (2)	Ni—N3—C3—C4	43.5 (3)
N3^i—Ni—N2—C5	−65.2 (2)	C2—N2—C4—C3	146.7 (3)
N1^i—Ni—N2—C5	28.4 (2)	C5—N2—C4—C3	−87.4 (3)
N1—Ni—N2—C5	−151.6 (2)	Ni—N2—C4—C3	33.0 (3)
N2^i—Ni—N2—C5	49 (100)	N3—C3—C4—N2	−52.6 (4)
N3—Ni—N2—C4	−7.4 (2)	C2—N2—C5—C6	47.0 (4)
N3^i—Ni—N2—C4	172.6 (2)	C4—N2—C5—C6	−78.3 (4)
N1^i—Ni—N2—C4	−93.8 (2)	Ni—N2—C5—C6	163.1 (2)
N1—Ni—N2—C4	86.2 (2)	N2—C5—C6—N4	69.7 (4)
N2^i—Ni—N2—C4	−73 (100)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl^ii	0.91 (3)	2.60 (3)	3.475 (3)	162 (3)
N1—H2N···Cl^iii	0.84 (4)	2.61 (4)	3.402 (3)	159 (3)
N3—H3N···Cl^iii	0.89 (4)	2.40 (4)	3.284 (3)	172 (3)
N3—H4N···N4^iv	0.86 (3)	2.28 (3)	3.087 (4)	156 (3)
N4—H5N···Cl^v	0.87 (4)	2.57 (4)	3.432 (3)	172 (4)
N4—H6N···Cl	0.90 (4)	2.51 (4)	3.406 (3)	172 (3)

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y, −z+1.

(II) bis[tris(2-aminoethyl)amine]nickel(II) tetrathiotungstate

Crystal data

[Ni(C6H18N4)2]WS4	F(000) = 1320
Mr = 663.29	Dx = 1.978 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.147 (2) Å	Cell parameters from 128 reflections
b = 11.852 (2) Å	θ = 4–20°
c = 19.122 (4) Å	µ = 6.40 mm^−1
β = 104.44 (3)°	T = 293 K
V = 2227.1 (8) Å^3	Polyhedron, yellow-orange
Z = 4	0.2 × 0.08 × 0.04 mm

Data collection

Philips PW 1100 4-circle- diffractometer	4522 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 28.0°, θmin = 2.7°
ω–θ scans	h = 0→13
Absorption correction: ψ scan X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)	k = −15→2
Tmin = 0.358, Tmax = 0.463	l = −25→24
6750 measured reflections	4 standard reflections every 120 min
5386 independent reflections	intensity decay: none

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.053	Only H-atom coordinates refined
S = 1.03	Calculated w = 1/[σ^2(Fo^2) + (0.0246P)^2 + 1.1404P] where P = (Fo^2 + 2Fc^2)/3
5386 reflections	(Δ/σ)max = 0.002
343 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

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
W	0.208831 (12)	0.263872 (10)	0.639058 (6)	0.02600 (4)
Ni	0.69114 (3)	0.25185 (3)	0.381889 (18)	0.02017 (7)
S1	0.01227 (10)	0.18292 (9)	0.61700 (5)	0.0498 (2)
S2	0.22893 (10)	0.37285 (8)	0.73337 (5)	0.0411 (2)
S3	0.37402 (9)	0.13706 (7)	0.66069 (5)	0.0444 (2)
S4	0.21983 (10)	0.36718 (7)	0.54555 (5)	0.0417 (2)
N1	0.7978 (3)	0.1048 (2)	0.42911 (15)	0.0299 (5)
H1N	0.793 (3)	0.092 (3)	0.474 (2)	0.036*
H2N	0.765 (4)	0.048 (3)	0.4057 (19)	0.036*
N2	0.8559 (2)	0.2631 (2)	0.33040 (13)	0.0243 (5)
N3	0.5992 (3)	0.1667 (2)	0.28322 (14)	0.0287 (5)
H3N	0.595 (3)	0.093 (3)	0.2907 (18)	0.034*
H4N	0.521 (4)	0.190 (3)	0.2664 (19)	0.034*
N4	1.1187 (3)	0.5000 (3)	0.3448 (2)	0.0507 (8)
H5N	1.148 (4)	0.491 (4)	0.392 (2)	0.061*
H6N	1.062 (4)	0.553 (4)	0.346 (2)	0.061*
N5	0.5928 (3)	0.4036 (2)	0.33604 (14)	0.0287 (5)
H7N	0.647 (3)	0.464 (3)	0.3365 (18)	0.034*
H8N	0.558 (4)	0.392 (3)	0.291 (2)	0.034*
N6	0.5187 (2)	0.2402 (2)	0.42811 (13)	0.0248 (5)
N7	0.7791 (3)	0.3383 (2)	0.48101 (14)	0.0284 (5)
H9N	0.850 (4)	0.305 (3)	0.5061 (19)	0.034*
H10N	0.799 (3)	0.403 (3)	0.4761 (19)	0.034*
N8	0.2772 (4)	−0.0069 (3)	0.4206 (2)	0.0484 (8)
H11N	0.297 (4)	−0.029 (4)	0.379 (2)	0.058*
H12N	0.197 (4)	−0.009 (4)	0.400 (2)	0.058*
C1	0.9396 (3)	0.1191 (3)	0.42383 (19)	0.0349 (7)
H1C	0.996 (4)	0.048 (3)	0.4361 (19)	0.042*
H2C	0.984 (4)	0.175 (3)	0.4580 (19)	0.042*
C2	0.9370 (3)	0.1575 (3)	0.34778 (19)	0.0331 (7)
H3C	1.023 (4)	0.176 (3)	0.3394 (19)	0.040*
H4C	0.894 (3)	0.099 (3)	0.3124 (19)	0.040*
C3	0.6805 (3)	0.1805 (3)	0.22942 (18)	0.0361 (7)
H5C	0.623 (4)	0.205 (3)	0.187 (2)	0.043*
H6C	0.721 (4)	0.114 (3)	0.2233 (19)	0.043*
C4	0.7894 (3)	0.2705 (3)	0.25226 (16)	0.0322 (6)
H7C	0.852 (4)	0.265 (3)	0.223 (2)	0.039*
H8C	0.751 (4)	0.342 (3)	0.2403 (19)	0.039*
C5	0.9393 (3)	0.3646 (3)	0.35566 (17)	0.0282 (6)
H9C	0.995 (3)	0.352 (3)	0.4084 (19)	0.034*
H10C	0.879 (3)	0.427 (3)	0.3526 (18)	0.034*
C6	1.0417 (4)	0.4006 (3)	0.3134 (2)	0.0392 (8)
H11C	1.107 (4)	0.345 (3)	0.308 (2)	0.047*
H12C	0.997 (4)	0.423 (3)	0.265 (2)	0.047*
C7	0.4840 (4)	0.4312 (3)	0.3716 (2)	0.0369 (7)
H13C	0.411 (4)	0.467 (3)	0.342 (2)	0.044*
H14C	0.525 (4)	0.480 (3)	0.413 (2)	0.044*
C8	0.4189 (3)	0.3245 (3)	0.39028 (19)	0.0327 (7)
H15C	0.352 (4)	0.343 (3)	0.4167 (19)	0.039*
H16C	0.369 (4)	0.287 (3)	0.345 (2)	0.039*
C9	0.6793 (4)	0.3488 (4)	0.5246 (2)	0.0480 (9)
H17C	0.611 (4)	0.417 (4)	0.508 (2)	0.058*
H18C	0.729 (4)	0.337 (4)	0.574 (2)	0.058*
C10	0.5700 (4)	0.2620 (3)	0.50690 (18)	0.0401 (8)
H19C	0.495 (4)	0.272 (3)	0.531 (2)	0.048*
H20C	0.625 (4)	0.187 (3)	0.529 (2)	0.048*
C11	0.4579 (3)	0.1257 (3)	0.41681 (19)	0.0315 (6)
H21C	0.528 (3)	0.068 (3)	0.4366 (18)	0.038*
H22C	0.438 (3)	0.108 (3)	0.3657 (19)	0.038*
C12	0.3276 (4)	0.1064 (3)	0.4406 (2)	0.0428 (8)
H23C	0.349 (4)	0.111 (3)	0.491 (2)	0.051*
H24C	0.261 (4)	0.166 (4)	0.420 (2)	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W	0.03021 (7)	0.02242 (6)	0.02403 (6)	−0.00081 (5)	0.00424 (4)	0.00048 (4)
Ni	0.02156 (16)	0.01876 (17)	0.02060 (16)	0.00015 (12)	0.00602 (13)	−0.00127 (12)
S1	0.0450 (5)	0.0585 (6)	0.0450 (5)	−0.0151 (4)	0.0097 (4)	−0.0015 (4)
S2	0.0533 (5)	0.0360 (4)	0.0313 (4)	0.0021 (4)	0.0058 (4)	−0.0045 (3)
S3	0.0456 (5)	0.0314 (4)	0.0478 (5)	0.0097 (4)	−0.0042 (4)	−0.0051 (4)
S4	0.0613 (6)	0.0329 (4)	0.0341 (4)	−0.0009 (4)	0.0179 (4)	0.0061 (3)
N1	0.0369 (14)	0.0209 (12)	0.0324 (14)	0.0017 (10)	0.0097 (12)	0.0020 (10)
N2	0.0253 (11)	0.0243 (12)	0.0246 (11)	−0.0023 (9)	0.0085 (9)	−0.0027 (9)
N3	0.0259 (12)	0.0313 (14)	0.0284 (13)	−0.0047 (11)	0.0061 (10)	−0.0049 (10)
N4	0.0438 (19)	0.0419 (19)	0.071 (2)	−0.0165 (14)	0.0227 (18)	−0.0084 (17)
N5	0.0320 (13)	0.0245 (13)	0.0307 (13)	0.0010 (10)	0.0097 (11)	0.0048 (10)
N6	0.0252 (11)	0.0261 (12)	0.0240 (11)	−0.0004 (9)	0.0079 (9)	0.0008 (9)
N7	0.0302 (13)	0.0280 (13)	0.0265 (12)	−0.0035 (11)	0.0061 (10)	−0.0029 (10)
N8	0.0417 (17)	0.0440 (18)	0.060 (2)	−0.0126 (15)	0.0135 (16)	0.0036 (15)
C1	0.0335 (17)	0.0298 (16)	0.0389 (17)	0.0066 (13)	0.0043 (14)	0.0030 (13)
C2	0.0307 (16)	0.0270 (15)	0.0447 (18)	0.0036 (12)	0.0151 (14)	−0.0035 (13)
C3	0.0323 (17)	0.048 (2)	0.0289 (15)	−0.0036 (14)	0.0099 (13)	−0.0125 (14)
C4	0.0317 (15)	0.0420 (18)	0.0248 (14)	−0.0061 (14)	0.0106 (12)	−0.0034 (13)
C5	0.0255 (14)	0.0276 (15)	0.0316 (15)	−0.0049 (12)	0.0076 (12)	−0.0032 (12)
C6	0.0324 (17)	0.043 (2)	0.046 (2)	−0.0110 (15)	0.0169 (15)	−0.0059 (16)
C7	0.0351 (17)	0.0291 (16)	0.049 (2)	0.0092 (13)	0.0148 (15)	0.0055 (14)
C8	0.0252 (15)	0.0334 (17)	0.0417 (18)	0.0057 (12)	0.0124 (14)	0.0052 (14)
C9	0.047 (2)	0.065 (3)	0.0340 (18)	−0.0135 (19)	0.0145 (16)	−0.0162 (18)
C10	0.0391 (17)	0.058 (2)	0.0263 (15)	−0.0104 (16)	0.0144 (13)	−0.0049 (15)
C11	0.0303 (16)	0.0277 (15)	0.0384 (17)	−0.0015 (12)	0.0123 (13)	0.0025 (13)
C12	0.0405 (19)	0.0385 (19)	0.054 (2)	−0.0077 (15)	0.0212 (17)	0.0025 (17)

Geometric parameters (Å, º)

W—S1	2.1580 (10)	N8—H11N	0.91 (4)
W—S2	2.1860 (9)	N8—H12N	0.81 (4)
W—S3	2.2122 (9)	C1—C2	1.518 (5)
W—S4	2.1929 (9)	C1—H1C	1.01 (4)
Ni—N1	2.130 (3)	C1—H2C	0.96 (4)
Ni—N2	2.146 (2)	C2—H3C	0.95 (4)
Ni—N3	2.138 (3)	C2—H4C	0.99 (4)
Ni—N5	2.136 (3)	C3—C4	1.519 (5)
Ni—N6	2.152 (2)	C3—H5C	0.93 (4)
Ni—N7	2.143 (3)	C3—H6C	0.91 (4)
N1—C1	1.477 (4)	C4—H7C	0.95 (4)
N1—H1N	0.87 (4)	C4—H8C	0.94 (4)
N1—H2N	0.83 (4)	C5—C6	1.528 (4)
N2—C5	1.480 (4)	C5—H9C	1.04 (3)
N2—C4	1.481 (4)	C5—H10C	0.95 (3)
N2—C2	1.489 (4)	C6—H11C	0.96 (4)
N3—C3	1.480 (4)	C6—H12C	0.97 (4)
N3—H3N	0.89 (4)	C7—C8	1.510 (5)
N3—H4N	0.83 (4)	C7—H13C	0.91 (4)
N4—C6	1.457 (5)	C7—H14C	0.98 (4)
N4—H5N	0.88 (4)	C8—H15C	0.97 (4)
N4—H6N	0.86 (4)	C8—H16C	0.99 (4)
N5—C7	1.471 (4)	C9—C10	1.488 (5)
N5—H7N	0.90 (4)	C9—H17C	1.06 (4)
N5—H8N	0.86 (4)	C9—H18C	0.96 (4)
N6—C8	1.477 (4)	C10—H19C	0.99 (4)
N6—C11	1.485 (4)	C10—H20C	1.08 (4)
N6—C10	1.489 (4)	C11—C12	1.519 (4)
N7—C9	1.468 (4)	C11—H21C	0.99 (4)
N7—H9N	0.86 (4)	C11—H22C	0.97 (3)
N7—H10N	0.80 (4)	C12—H23C	0.94 (4)
N8—C12	1.454 (5)	C12—H24C	0.99 (4)
S1—W—S2	108.39 (4)	H1C—C1—H2C	106 (3)
S1—W—S3	110.78 (4)	N2—C2—C1	110.0 (2)
S1—W—S4	108.75 (5)	N2—C2—H3C	104 (2)
S2—W—S3	109.68 (4)	C1—C2—H3C	116 (2)
S2—W—S4	109.24 (4)	N2—C2—H4C	108 (2)
S4—W—S3	109.97 (4)	C1—C2—H4C	110 (2)
N1—Ni—N2	82.75 (10)	H3C—C2—H4C	108 (3)
N1—Ni—N3	92.96 (11)	N3—C3—C4	111.7 (3)
N1—Ni—N5	177.34 (11)	N3—C3—H5C	108 (2)
N1—Ni—N6	98.77 (10)	C4—C3—H5C	106 (2)
N1—Ni—N7	87.74 (11)	N3—C3—H6C	110 (2)
N3—Ni—N2	80.95 (10)	C4—C3—H6C	109 (2)
N5—Ni—N2	95.56 (10)	H5C—C3—H6C	112 (3)
N2—Ni—N6	177.05 (9)	N2—C4—C3	111.4 (3)
N7—Ni—N2	100.13 (10)	N2—C4—H7C	113 (2)
N5—Ni—N3	88.79 (11)	C3—C4—H7C	109 (2)
N3—Ni—N6	96.42 (10)	N2—C4—H8C	111 (2)
N3—Ni—N7	178.78 (10)	C3—C4—H8C	110 (2)
N5—Ni—N6	83.01 (9)	H7C—C4—H8C	102 (3)
N5—Ni—N7	90.54 (11)	N2—C5—C6	117.6 (3)
N7—Ni—N6	82.49 (10)	N2—C5—H9C	109.0 (19)
C1—N1—Ni	106.11 (19)	C6—C5—H9C	106.3 (19)
C1—N1—H1N	112 (2)	N2—C5—H10C	108 (2)
Ni—N1—H1N	114 (2)	C6—C5—H10C	105 (2)
C1—N1—H2N	109 (2)	H9C—C5—H10C	111 (3)
Ni—N1—H2N	110 (3)	N4—C6—C5	111.9 (3)
H1N—N1—H2N	106 (3)	N4—C6—H11C	107 (2)
C5—N2—C4	111.2 (2)	C5—C6—H11C	116 (2)
C5—N2—C2	111.8 (2)	N4—C6—H12C	104 (2)
C4—N2—C2	111.2 (2)	C5—C6—H12C	112 (2)
C5—N2—Ni	110.36 (17)	H11C—C6—H12C	104 (3)
C4—N2—Ni	104.81 (17)	N5—C7—C8	110.2 (3)
C2—N2—Ni	107.19 (18)	N5—C7—H13C	113 (2)
C3—N3—Ni	111.42 (19)	C8—C7—H13C	102 (2)
C3—N3—H3N	106 (2)	N5—C7—H14C	107 (2)
Ni—N3—H3N	110 (2)	C8—C7—H14C	115 (2)
C3—N3—H4N	110 (2)	H13C—C7—H14C	110 (3)
Ni—N3—H4N	111 (3)	N6—C8—C7	113.3 (3)
H3N—N3—H4N	108 (3)	N6—C8—H15C	113 (2)
C6—N4—H5N	110 (3)	C7—C8—H15C	110 (2)
C6—N4—H6N	108 (3)	N6—C8—H16C	105 (2)
H5N—N4—H6N	96 (4)	C7—C8—H16C	109 (2)
C7—N5—Ni	108.98 (19)	H15C—C8—H16C	106 (3)
C7—N5—H7N	111 (2)	N7—C9—C10	113.1 (3)
Ni—N5—H7N	116 (2)	N7—C9—H17C	113 (2)
C7—N5—H8N	109 (2)	C10—C9—H17C	94 (2)
Ni—N5—H8N	108 (2)	N7—C9—H18C	106 (2)
H7N—N5—H8N	104 (3)	C10—C9—H18C	108 (3)
C8—N6—C11	109.8 (2)	H17C—C9—H18C	123 (3)
C8—N6—C10	113.7 (3)	C9—C10—N6	113.7 (3)
C11—N6—C10	109.5 (2)	C9—C10—H19C	116 (2)
C8—N6—Ni	106.48 (18)	N6—C10—H19C	112 (2)
C11—N6—Ni	110.46 (18)	C9—C10—H20C	101 (2)
C10—N6—Ni	106.82 (18)	N6—C10—H20C	106 (2)
C9—N7—Ni	110.4 (2)	H19C—C10—H20C	107 (3)
C9—N7—H9N	109 (2)	N6—C11—C12	117.1 (3)
Ni—N7—H9N	113 (2)	N6—C11—H21C	110 (2)
C9—N7—H10N	102 (3)	C12—C11—H21C	112 (2)
Ni—N7—H10N	114 (3)	N6—C11—H22C	109 (2)
H9N—N7—H10N	108 (3)	C12—C11—H22C	107 (2)
C12—N8—H11N	111 (3)	H21C—C11—H22C	101 (3)
C12—N8—H12N	113 (3)	N8—C12—C11	109.6 (3)
H11N—N8—H12N	89 (4)	N8—C12—H23C	107 (3)
N1—C1—C2	108.4 (3)	C11—C12—H23C	108 (2)
N1—C1—H1C	113 (2)	N8—C12—H24C	113 (2)
C2—C1—H1C	110 (2)	C11—C12—H24C	110 (2)
N1—C1—H2C	110 (2)	H23C—C12—H24C	109 (3)
C2—C1—H2C	110 (2)
N5—Ni—N1—C1	−29 (2)	N2—Ni—N6—C11	70.6 (18)
N3—Ni—N1—C1	101.9 (2)	N1—Ni—N6—C10	68.7 (2)
N7—Ni—N1—C1	−79.1 (2)	N5—Ni—N6—C10	−109.3 (2)
N2—Ni—N1—C1	21.4 (2)	N3—Ni—N6—C10	162.7 (2)
N6—Ni—N1—C1	−161.2 (2)	N7—Ni—N6—C10	−17.9 (2)
N1—Ni—N2—C5	−114.2 (2)	N2—Ni—N6—C10	−170.4 (17)
N5—Ni—N2—C5	63.7 (2)	N1—Ni—N7—C9	−101.8 (3)
N3—Ni—N2—C5	151.6 (2)	N5—Ni—N7—C9	80.2 (3)
N7—Ni—N2—C5	−27.9 (2)	N3—Ni—N7—C9	24 (5)
N6—Ni—N2—C5	124.5 (17)	N2—Ni—N7—C9	176.0 (3)
N1—Ni—N2—C4	126.0 (2)	N6—Ni—N7—C9	−2.7 (3)
N5—Ni—N2—C4	−56.1 (2)	Ni—N1—C1—C2	−46.8 (3)
N3—Ni—N2—C4	31.82 (19)	C5—N2—C2—C1	85.5 (3)
N7—Ni—N2—C4	−147.61 (19)	C4—N2—C2—C1	−149.6 (3)
N6—Ni—N2—C4	4.7 (19)	Ni—N2—C2—C1	−35.5 (3)
N1—Ni—N2—C2	7.7 (2)	N1—C1—C2—N2	56.7 (3)
N5—Ni—N2—C2	−174.35 (19)	Ni—N3—C3—C4	−12.1 (4)
N3—Ni—N2—C2	−86.5 (2)	C5—N2—C4—C3	−167.5 (3)
N7—Ni—N2—C2	94.1 (2)	C2—N2—C4—C3	67.2 (3)
N6—Ni—N2—C2	−113.5 (18)	Ni—N2—C4—C3	−48.3 (3)
N1—Ni—N3—C3	−93.3 (2)	N3—C3—C4—N2	41.3 (4)
N5—Ni—N3—C3	84.7 (2)	C4—N2—C5—C6	−51.2 (4)
N7—Ni—N3—C3	141 (5)	C2—N2—C5—C6	73.8 (4)
N2—Ni—N3—C3	−11.1 (2)	Ni—N2—C5—C6	−167.0 (2)
N6—Ni—N3—C3	167.5 (2)	N2—C5—C6—N4	−178.8 (3)
N1—Ni—N5—C7	−120 (2)	Ni—N5—C7—C8	−34.9 (3)
N3—Ni—N5—C7	109.0 (2)	C11—N6—C8—C7	−155.7 (3)
N7—Ni—N5—C7	−70.0 (2)	C10—N6—C8—C7	81.2 (3)
N2—Ni—N5—C7	−170.3 (2)	Ni—N6—C8—C7	−36.1 (3)
N6—Ni—N5—C7	12.3 (2)	N5—C7—C8—N6	49.2 (4)
N1—Ni—N6—C8	−169.5 (2)	Ni—N7—C9—C10	23.6 (4)
N5—Ni—N6—C8	12.5 (2)	N7—C9—C10—N6	−41.5 (5)
N3—Ni—N6—C8	−75.4 (2)	C8—N6—C10—C9	−80.5 (4)
N7—Ni—N6—C8	104.0 (2)	C11—N6—C10—C9	156.3 (3)
N2—Ni—N6—C8	−48.6 (19)	Ni—N6—C10—C9	36.6 (4)
N1—Ni—N6—C11	−50.3 (2)	C8—N6—C11—C12	−57.7 (4)
N5—Ni—N6—C11	131.7 (2)	C10—N6—C11—C12	67.8 (4)
N3—Ni—N6—C11	43.7 (2)	Ni—N6—C11—C12	−174.8 (3)
N7—Ni—N6—C11	−136.8 (2)	N6—C11—C12—N8	175.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N8^i	0.87 (4)	2.52 (4)	3.358 (4)	161 (3)
N1—H2N···S3^i	0.83 (4)	2.75 (4)	3.565 (3)	171 (3)
N3—H3N···S3^i	0.89 (4)	2.87 (4)	3.747 (3)	169 (3)
N3—H4N···S2^ii	0.83 (4)	2.97 (4)	3.669 (3)	144 (3)
N3—H4N···S3^ii	0.83 (4)	3.00 (4)	3.667 (3)	139 (3)
N5—H7N···S2^iii	0.90 (4)	2.82 (4)	3.640 (3)	152 (3)
N5—H8N···S3^ii	0.86 (4)	2.73 (4)	3.562 (3)	162 (3)
N7—H9N···S1^iv	0.86 (4)	2.75 (4)	3.561 (3)	158 (3)
N7—H10N···S4^iii	0.80 (4)	2.76 (4)	3.528 (3)	162 (3)
N8—H12N···S1^v	0.81 (4)	2.92 (5)	3.528 (3)	133 (4)

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