Bis-{μ-3,3'-(1,3,4-thia-diazole-2,5-diyl-dithio)bis-[penta-ne-dionato(1-)]}bis-[diaqua-nickel(II)] dimethyl-formamide disolvate trihydrate.

The title compound, [Ni(2)(C(12)H(12)N(2)O(4)S(3))(H(2)O)(4)]·2C(3)H(7)NO·3H(2)O, is made up of a centrosymmetric, bimetallic complex containing a 24-membered macrocyclic ring, two dimethyl-formamide and three water solvent mol-ecules. The Ni atom adopts a slightly distorted NiO(6) octahedral geometry arising from two O,O-bidentate ligands and two water molecules. There are inter-molecular O-H⋯O and O-H⋯N inter-actions in the crystal structure. One of the uncoordinated water molecules is diordered over two sets of sites of equal occupancy.

Related literature

For background to metallamacrocycles, see: Gaynor et al. (2002 ▶); Shan et al. (2004 ▶); Weng et al. (2004 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

[Ni2(C12H12N2O4S3)(H2O)4]·2Cn class="Chemical">3H7NO·3H2O

M = 1078.56

Triclinic,

a = 10.582 (2) Å

b = 11.469 (1) Å

c = 12.136 (2) Å

α = 102.30 (3)°

β = 107.21 (1)°

γ = 116.26 (3)°

V = 1155.6 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.16 mm−1

T = 295 (2) K

0.23 × 0.20 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

6130 measured reflections

4039 independent reflections

3498 reflections with I > 2σ(I)

R int = 0.013

3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.095

S = 1.03

4039 reflections

284 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.60 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043699/at2698sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043699/at2698Isup2.hkl

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

[Ni2(C12H12N2O4S3)(H2O)4]·2C3H7NO·3H2O	Z = 1
Mr = 1078.56	F(000) = 562
Triclinic, P1	Dx = 1.550 Mg m−3
Hall symbol: -P 1	Melting point: 554.6 K
a = 10.582 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.469 (1) Å	Cell parameters from 25 reflections
c = 12.136 (2) Å	θ = 4–14°
α = 102.30 (3)°	µ = 1.16 mm−1
β = 107.21 (1)°	T = 295 K
γ = 116.26 (3)°	Block, green
V = 1155.6 (6) Å3	0.23 × 0.20 × 0.16 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.013
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.9°
graphite	h = −11→12
ω scans	k = −13→13
6130 measured reflections	l = −14→10
4039 independent reflections	3 standard reflections every 100 reflections
3498 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0451P)2 + 0.9813P] where P = (Fo2 + 2Fc2)/3
4039 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.60 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	Occ. (<1)
Ni1	0.26742 (4)	0.62302 (4)	0.03339 (3)	0.03044 (12)
S1	0.57596 (10)	0.85228 (10)	0.50283 (7)	0.0503 (2)
S2	0.96862 (10)	0.64320 (10)	0.43743 (7)	0.0517 (2)
S5	0.70843 (10)	0.70555 (9)	0.37703 (7)	0.0483 (2)
O1	0.2162 (2)	0.5835 (2)	0.17277 (17)	0.0363 (4)
O2	0.4302 (3)	0.8227 (2)	0.15619 (19)	0.0444 (5)
O1W	0.1000 (3)	0.6732 (2)	−0.0185 (2)	0.0483 (5)
H1W1	0.0024	0.6117	−0.0648	0.058*
H2W1	0.1129	0.7547	−0.0008	0.058*
O3	0.8900 (2)	0.5791 (2)	0.08790 (18)	0.0372 (4)
O2W	0.4322 (2)	0.5712 (2)	0.08969 (19)	0.0413 (5)
H1W2	0.4835	0.5644	0.1540	0.050*
H2W2	0.4945	0.6091	0.0590	0.050*
O4	0.6766 (2)	0.3368 (2)	0.10243 (18)	0.0401 (5)
N1	0.8243 (3)	0.8407 (3)	0.6137 (2)	0.0542 (7)
N2	0.9174 (3)	0.7907 (3)	0.5975 (2)	0.0529 (7)
C1	0.5014 (4)	0.8636 (3)	0.2726 (3)	0.0396 (7)
C2	0.4545 (3)	0.7796 (3)	0.3404 (3)	0.0375 (6)
C3	0.3124 (3)	0.6462 (3)	0.2874 (3)	0.0359 (6)
C4	0.6446 (5)	1.0111 (4)	0.3393 (4)	0.0639 (10)
H4A	0.6582	1.0525	0.2795	0.096*
H4B	0.7353	1.0081	0.3800	0.096*
H4C	0.6324	1.0672	0.4012	0.096*
C5	0.2640 (4)	0.5707 (4)	0.3676 (3)	0.0580 (9)
H5A	0.1646	0.4824	0.3160	0.087*
H5B	0.2543	0.6286	0.4303	0.087*
H5C	0.3419	0.5524	0.4081	0.087*
C6	0.7117 (4)	0.8037 (3)	0.5087 (3)	0.0412 (7)
C7	0.8711 (4)	0.7194 (3)	0.4804 (3)	0.0410 (7)
C8	0.9326 (3)	0.6343 (3)	0.2039 (3)	0.0370 (6)
C9	0.8698 (3)	0.5594 (3)	0.2722 (3)	0.0376 (6)
C10	0.7436 (3)	0.4150 (3)	0.2166 (3)	0.0364 (6)
C11	1.0570 (4)	0.7901 (3)	0.2674 (3)	0.0622 (10)
H11A	1.0861	0.8227	0.2069	0.093*
H11B	1.1477	0.8063	0.3335	0.093*
H11C	1.0169	0.8410	0.3025	0.093*
C12	0.6796 (5)	0.3461 (4)	0.2957 (3)	0.0558 (9)
H12A	0.5956	0.2490	0.2436	0.084*
H12B	0.6404	0.3956	0.3341	0.084*
H12C	0.7617	0.3495	0.3600	0.084*
O5	0.3257 (3)	0.2918 (3)	−0.0367 (3)	0.0627 (7)
N6	0.2517 (4)	0.1686 (4)	0.0772 (4)	0.0702 (9)
C13	0.2358 (8)	0.2730 (6)	0.1515 (6)	0.110 (2)
H13A	0.2517	0.3453	0.1194	0.165*
H13B	0.3128	0.3150	0.2376	0.165*
H13C	0.1322	0.2280	0.1469	0.165*
C14	0.2237 (8)	0.0463 (5)	0.1088 (6)	0.1039 (18)
H14A	0.2292	−0.0190	0.0491	0.156*
H14B	0.1214	−0.0001	0.1063	0.156*
H14C	0.3023	0.0774	0.1918	0.156*
C15	0.2982 (5)	0.1897 (4)	−0.0082 (4)	0.0663 (11)
H15A	0.2931	0.1006	−0.0592	0.079*
O3W	0.8641 (5)	0.1907 (5)	0.1821 (4)	0.1309 (16)
H1W3	0.9173	0.1787	0.2412	0.157*
H2W3	0.8417	0.2476	0.2148	0.157*
O4W	0.4494 (6)	−0.0168 (7)	−0.0250 (7)	0.089 (2)	0.50
H1W4	0.3783	−0.0739	−0.0101	0.107*	0.50
H2W4	0.4044	−0.0037	−0.0875	0.107*	0.50

	U11	U22	U33	U12	U13	U23
Ni1	0.0302 (2)	0.0303 (2)	0.02522 (19)	0.01252 (15)	0.01182 (15)	0.01108 (14)
S1	0.0508 (5)	0.0655 (5)	0.0274 (4)	0.0360 (4)	0.0116 (3)	0.0044 (4)
S2	0.0520 (5)	0.0692 (6)	0.0281 (4)	0.0411 (5)	0.0063 (3)	0.0073 (4)
S5	0.0499 (5)	0.0640 (5)	0.0237 (4)	0.0367 (4)	0.0069 (3)	0.0057 (3)
O1	0.0323 (10)	0.0410 (11)	0.0295 (10)	0.0144 (9)	0.0148 (8)	0.0145 (9)
O2	0.0502 (13)	0.0328 (11)	0.0331 (11)	0.0141 (10)	0.0126 (10)	0.0118 (9)
O1W	0.0495 (13)	0.0527 (13)	0.0606 (14)	0.0344 (11)	0.0284 (11)	0.0324 (11)
O3	0.0346 (10)	0.0328 (10)	0.0341 (11)	0.0126 (9)	0.0138 (9)	0.0116 (9)
O2W	0.0397 (11)	0.0540 (13)	0.0381 (11)	0.0274 (10)	0.0205 (9)	0.0226 (10)
O4	0.0414 (11)	0.0387 (11)	0.0293 (11)	0.0135 (9)	0.0155 (9)	0.0138 (9)
N1	0.0613 (18)	0.0711 (19)	0.0285 (14)	0.0439 (16)	0.0124 (13)	0.0096 (13)
N2	0.0566 (17)	0.0703 (19)	0.0276 (13)	0.0420 (16)	0.0089 (12)	0.0090 (13)
C1	0.0405 (16)	0.0349 (15)	0.0353 (16)	0.0201 (13)	0.0132 (13)	0.0062 (13)
C2	0.0397 (16)	0.0431 (16)	0.0258 (14)	0.0239 (14)	0.0119 (12)	0.0077 (12)
C3	0.0388 (16)	0.0457 (16)	0.0306 (15)	0.0266 (14)	0.0181 (13)	0.0155 (13)
C4	0.061 (2)	0.0381 (18)	0.053 (2)	0.0113 (17)	0.0108 (18)	0.0078 (16)
C5	0.059 (2)	0.071 (2)	0.0419 (19)	0.0280 (19)	0.0273 (17)	0.0299 (18)
C6	0.0438 (17)	0.0480 (18)	0.0274 (15)	0.0252 (15)	0.0131 (13)	0.0105 (13)
C7	0.0420 (16)	0.0460 (17)	0.0269 (15)	0.0235 (14)	0.0093 (13)	0.0100 (13)
C8	0.0336 (15)	0.0366 (15)	0.0350 (16)	0.0193 (13)	0.0112 (12)	0.0098 (13)
C9	0.0381 (16)	0.0434 (16)	0.0263 (14)	0.0242 (14)	0.0090 (12)	0.0085 (12)
C10	0.0410 (16)	0.0472 (17)	0.0290 (15)	0.0275 (14)	0.0164 (13)	0.0192 (13)
C11	0.061 (2)	0.0355 (18)	0.052 (2)	0.0108 (17)	0.0151 (18)	0.0028 (15)
C12	0.071 (2)	0.062 (2)	0.0417 (18)	0.0329 (19)	0.0325 (18)	0.0279 (17)
O5	0.0641 (16)	0.0535 (15)	0.095 (2)	0.0349 (13)	0.0507 (15)	0.0428 (14)
N6	0.076 (2)	0.062 (2)	0.094 (3)	0.0371 (18)	0.052 (2)	0.0472 (19)
C13	0.160 (6)	0.112 (4)	0.141 (5)	0.095 (4)	0.115 (5)	0.077 (4)
C14	0.151 (5)	0.073 (3)	0.122 (4)	0.061 (3)	0.082 (4)	0.064 (3)
C15	0.071 (3)	0.052 (2)	0.087 (3)	0.033 (2)	0.045 (2)	0.031 (2)
O3W	0.143 (4)	0.201 (5)	0.117 (3)	0.117 (4)	0.066 (3)	0.113 (3)
O4W	0.063 (5)	0.068 (4)	0.109 (6)	0.023 (5)	0.018 (4)	0.046 (4)

Ni1—O4i	1.9851 (19)	C4—H4C	0.9600
Ni1—O2	1.992 (2)	C5—H5A	0.9600
Ni1—O3i	1.998 (2)	C5—H5B	0.9600
Ni1—O1	2.0029 (19)	C5—H5C	0.9600
Ni1—O2W	2.060 (2)	C8—C9	1.411 (4)
Ni1—O1W	2.065 (2)	C8—C11	1.500 (4)
S1—C6	1.745 (3)	C9—C10	1.419 (4)
S1—C2	1.756 (3)	C10—C12	1.496 (4)
S2—C7	1.739 (3)	C11—H11A	0.9600
S2—C9	1.757 (3)	C11—H11B	0.9600
S5—C7	1.720 (3)	C11—H11C	0.9600
S5—C6	1.728 (3)	C12—H12A	0.9600
O1—C3	1.256 (3)	C12—H12B	0.9600
O2—C1	1.248 (4)	C12—H12C	0.9600
O1W—H1W1	0.8500	O5—C15	1.228 (4)
O1W—H2W1	0.8500	N6—C15	1.295 (5)
O3—C8	1.256 (3)	N6—C13	1.443 (6)
O3—Ni1i	1.998 (2)	N6—C14	1.460 (5)
O2W—H1W2	0.8500	C13—H13A	0.9600
O2W—H2W2	0.8501	C13—H13B	0.9600
O4—C10	1.247 (3)	C13—H13C	0.9600
O4—Ni1i	1.9851 (19)	C14—H14A	0.9600
N1—C6	1.284 (4)	C14—H14B	0.9600
N1—N2	1.381 (4)	C14—H14C	0.9600
N2—C7	1.290 (4)	C15—H15A	1.0463
C1—C2	1.418 (4)	O3W—H1W3	0.8498
C1—C4	1.495 (5)	O3W—H2W3	0.8500
C2—C3	1.410 (4)	O4W—O4Wii	0.901 (10)
C3—C5	1.490 (4)	O4W—H1W4	0.8500
C4—H4A	0.9600	O4W—H2W4	0.8500
C4—H4B	0.9600
O4i—Ni1—O2	91.40 (9)	H5B—C5—H5C	109.5
O4i—Ni1—O3i	88.63 (9)	N1—C6—S5	114.8 (2)
O2—Ni1—O3i	177.92 (9)	N1—C6—S1	121.4 (2)
O4i—Ni1—O1	178.59 (8)	S5—C6—S1	123.82 (17)
O2—Ni1—O1	87.98 (9)	N2—C7—S5	114.7 (2)
O3i—Ni1—O1	91.95 (9)	N2—C7—S2	120.5 (2)
O4i—Ni1—O2W	91.54 (9)	S5—C7—S2	124.88 (17)
O2—Ni1—O2W	88.80 (9)	O3—C8—C9	124.0 (3)
O3i—Ni1—O2W	89.12 (9)	O3—C8—C11	114.9 (3)
O1—Ni1—O2W	87.18 (8)	C9—C8—C11	121.0 (3)
O4i—Ni1—O1W	90.39 (9)	C8—C9—C10	124.1 (3)
O2—Ni1—O1W	91.24 (10)	C8—C9—S2	117.8 (2)
O3i—Ni1—O1W	90.85 (10)	C10—C9—S2	117.7 (2)
O1—Ni1—O1W	90.90 (9)	O4—C10—C9	124.8 (3)
O2W—Ni1—O1W	178.07 (8)	O4—C10—C12	114.8 (3)
C6—S1—C2	102.53 (14)	C9—C10—C12	120.4 (3)
C7—S2—C9	105.44 (14)	C8—C11—H11A	109.5
C7—S5—C6	86.11 (15)	C8—C11—H11B	109.5
C3—O1—Ni1	124.99 (18)	H11A—C11—H11B	109.5
C1—O2—Ni1	126.2 (2)	C8—C11—H11C	109.5
Ni1—O1W—H1W1	123.7	H11A—C11—H11C	109.5
Ni1—O1W—H2W1	128.6	H11B—C11—H11C	109.5
H1W1—O1W—H2W1	107.7	C10—C12—H12A	109.5
C8—O3—Ni1i	128.97 (19)	C10—C12—H12B	109.5
Ni1—O2W—H1W2	139.2	H12A—C12—H12B	109.5
Ni1—O2W—H2W2	104.0	C10—C12—H12C	109.5
H1W2—O2W—H2W2	107.7	H12A—C12—H12C	109.5
C10—O4—Ni1i	128.75 (19)	H12B—C12—H12C	109.5
C6—N1—N2	112.1 (3)	C15—N6—C13	120.0 (4)
C7—N2—N1	112.3 (3)	C15—N6—C14	122.7 (4)
O2—C1—C2	124.1 (3)	C13—N6—C14	117.2 (4)
O2—C1—C4	115.3 (3)	N6—C13—H13A	109.5
C2—C1—C4	120.6 (3)	N6—C13—H13B	109.5
C3—C2—C1	124.2 (3)	H13A—C13—H13B	109.5
C3—C2—S1	118.3 (2)	N6—C13—H13C	109.5
C1—C2—S1	117.4 (2)	H13A—C13—H13C	109.5
O1—C3—C2	124.1 (3)	H13B—C13—H13C	109.5
O1—C3—C5	114.9 (3)	N6—C14—H14A	109.5
C2—C3—C5	120.9 (3)	N6—C14—H14B	109.5
C1—C4—H4A	109.5	H14A—C14—H14B	109.5
C1—C4—H4B	109.5	N6—C14—H14C	109.5
H4A—C4—H4B	109.5	H14A—C14—H14C	109.5
C1—C4—H4C	109.5	H14B—C14—H14C	109.5
H4A—C4—H4C	109.5	O5—C15—N6	125.1 (4)
H4B—C4—H4C	109.5	O5—C15—H15A	123.6
C3—C5—H5A	109.5	N6—C15—H15A	110.6
C3—C5—H5B	109.5	H1W3—O3W—H2W3	107.7
H5A—C5—H5B	109.5	O4Wii—O4W—H1W4	118.3
C3—C5—H5C	109.5	O4Wii—O4W—H2W4	134.0
H5A—C5—H5C	109.5	H1W4—O4W—H2W4	107.7
O2—Ni1—O1—C3	−29.7 (2)	C7—S5—C6—S1	−179.8 (2)
O3i—Ni1—O1—C3	148.2 (2)	C2—S1—C6—N1	178.6 (3)
O2W—Ni1—O1—C3	59.2 (2)	C2—S1—C6—S5	−0.7 (3)
O1W—Ni1—O1—C3	−121.0 (2)	N1—N2—C7—S5	0.0 (4)
O4i—Ni1—O2—C1	−151.7 (3)	N1—N2—C7—S2	−178.8 (2)
O1—Ni1—O2—C1	27.1 (3)	C6—S5—C7—N2	−0.4 (3)
O2W—Ni1—O2—C1	−60.1 (3)	C6—S5—C7—S2	178.3 (2)
O1W—Ni1—O2—C1	117.9 (3)	C9—S2—C7—N2	−179.4 (3)
C6—N1—N2—C7	0.7 (4)	C9—S2—C7—S5	1.9 (3)
Ni1—O2—C1—C2	−14.5 (4)	Ni1i—O3—C8—C9	−1.8 (4)
Ni1—O2—C1—C4	165.2 (2)	Ni1i—O3—C8—C11	178.8 (2)
O2—C1—C2—C3	−7.7 (5)	O3—C8—C9—C10	−4.6 (5)
C4—C1—C2—C3	172.7 (3)	C11—C8—C9—C10	174.8 (3)
O2—C1—C2—S1	176.6 (2)	O3—C8—C9—S2	167.6 (2)
C4—C1—C2—S1	−3.0 (4)	C11—C8—C9—S2	−13.0 (4)
C6—S1—C2—C3	96.7 (2)	C7—S2—C9—C8	96.1 (3)
C6—S1—C2—C1	−87.3 (3)	C7—S2—C9—C10	−91.2 (3)
Ni1—O1—C3—C2	20.1 (4)	Ni1i—O4—C10—C9	6.6 (4)
Ni1—O1—C3—C5	−161.4 (2)	Ni1i—O4—C10—C12	−174.2 (2)
C1—C2—C3—O1	4.4 (5)	C8—C9—C10—O4	2.1 (5)
S1—C2—C3—O1	−179.9 (2)	S2—C9—C10—O4	−170.1 (2)
C1—C2—C3—C5	−173.9 (3)	C8—C9—C10—C12	−177.1 (3)
S1—C2—C3—C5	1.7 (4)	S2—C9—C10—C12	10.7 (4)
N2—N1—C6—S5	−1.1 (4)	C13—N6—C15—O5	−3.0 (7)
N2—N1—C6—S1	179.6 (2)	C14—N6—C15—O5	−178.7 (5)
C7—S5—C6—N1	0.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3iii	0.85	2.48	2.817 (5)	104
O1W—H1W1···O1iv	0.85	2.11	2.932 (2)	162
O3W—H1W3···N2v	0.85	2.04	2.865 (6)	164
O2W—H2W2···O5i	0.85	1.87	2.700 (4)	164

Table 1

Selected bond lengths (Å)

Ni1—O4i	1.9851 (19)
Ni1—O2	1.992 (2)
Ni1—O3i	1.998 (2)
Ni1—O1	2.0029 (19)
Ni1—O2W	2.060 (2)
Ni1—O1W	2.065 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O3ii	0.85	2.48	2.817 (5)	104
O1W—H1W1⋯O1iii	0.85	2.11	2.932 (2)	162
O3W—H1W3⋯N2iv	0.85	2.04	2.865 (6)	164
O2W—H2W2⋯O5i	0.85	1.87	2.700 (4)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .