trans-Bis­[N-(2-hydroxy­ethyl)­ethyl­ene­di­amine-κ²N,N′]­bis­(iso­thio­cyanato-κN)­nickel(II)

The crystal structure of the title compound, [Ni(NCS)₂(C₄H₁₂N₂O)₂], has two crystallographically independent half-mol­ecules in the asymmetric unit, with each Ni atom residing on a centre of symmetry. The two mol­ecules exhibit similar coordination geometry but display differences with regard to other structural features. Each Ni^II centre is octahedrally coordinated by two mutually trans chelating hydroxy­ethyl­ethyl­ene­di­amine ligands and two mutually trans iso­thio­cyanate ions. The two independent mol­ecules form chains through different types of non-covalent interactions. In the case of one of the mol­ecules, only NCS and free OH groups participate in hydrogen bonding, while in the chain based on the second mol­ecule, the NCS, NH, NH₂ and free OH groups are involved in intermolecular hydrogen bonding. The two chains interact with one another through hydrogen bonding, forming planar sheets. The third packing direction is mediated only by van der Waals interactions.

S1. Comment

Studies on the synthesis, structures and properties of metal complexes containing ambidentate ligands are of interest for a number of reasons, some of which involve controlling the reactivities of the coordination sites in the metal complexes. Many transition metal complexes of this type have been synthesized and their structures and physical properties, as well as the linkage isomerization reactions of the ambidentate units, have been investigated (Kabesova et al., 1995; Buckingham, 1994; Burmeister, 1990). The coordination mode of an ambidentate ligand depends strongly on the nature of the central metal and the adjacent ligands. In this context, we have undertaken a study of the effect of N-(2-hydroxethyl)-ethylendiamine (hydet-en) on the coordination behaviour of thiocyonate ions in nickel complexes. Hydet-en, with three donor sites, has been the subject of few studies (Yilmaz et al., 2002; Karadag et al., 2004)), and its coordination behaviour is, therefore, not well characterized. This study reports the synthesis and crystal structure determination of [Ni(NCS)₂(C₄H₁₂N₂O)₂], (I).

An ORTEPIII (Burnett & Johnson, 1996) view of the molecular structure of (I) is shown in Fig.1. The structure has two crystallographically independent molecules, which exhibit similar coordination geometry about the metal centre but which have differences in other structural features.

Each Ni^II centre lies on a centre of symmetry and is octahedrally coordinated by two mutually trans hydet-en ligands and two mutually trans isothiocyanate ions. The hydet-en ligand chelates through its two amine N atoms, while the ethanol groups of this ligand are uncoordinated, as was observed in the copper and cadmium saccharin complexes with the hydet-en ligand (Yilmaz et al., 2002) and the cyano-bridged Zn^II/Ni^II complex (Karadag et al., 2004). The isothiocynate ions in each molecule act as N-donor ligands, as reported for other similar structures (Xu et al., 2003; Yilmaz et al., 2000). In each molecule, the coordinated amine N atoms of two hydet-en ligands form the equatorial planes (N1/N2/N1ⁱⁱ/N2ⁱⁱ and N4/N5/N4ⁱ/N5ⁱ), while the N atoms of the isothiocynate ions are located in the axial positions (symmetry codes as in the caption to Fig. 1). The dihedral angle between the equatorial planes of the two molecules is 27.6 (1)°.

The ring puckering of the five-membered chelate rings is similar in the two molecules. While both rings can best be characterized as being twisted about the C–C bond (as analyzed by PLATON; Spek, 2003), the situation for molecule A (the molecule containing Ni1) is not so clear, since the displacement ellipsoids of atoms C3 and C4 are elongated perpendicular to the plane of the other three atoms, raising the possibility of slight conformational disorder.

Small but statistically significant differences between the geometrical parameters involving the Ni atoms of the two independent molecules reflect their different packing environments (Table 1). The Ni—N_amine bond distances for molecule A are slightly longer than the corresponding bond lengths in molecule B (containing Ni2), while the Ni—N_NCS bond for molecule A is slightly shorter than that for molecule B. The five-membered chelate ring gives rise to the usual considerable distortion from ideal octahedral geometry, with bite angles of 82.59 (7) and 83.29 (7)° for molecules A and B, respectively. The observed geometries are, however, generally consistent with those observed in related di- and triethonalamine complexes of Ni^II (Hursthouse et al., 1990; Icbudak et al., 1995). The NCS groups are almost linear [178.7 (2)° for molecule A and 178.5 (2)° for molecule B]. Nevertheless, pronounced bending at the N atom is observed in molecule B [Ni2—N6—C10 = 150.51 (18)°], while the Ni1—N3—C5 angle in molecule A is 174.75 (19)°, similar to those observed in the mixed-ligand diethanolamine Ni^II complex of isothiocyanate (Yilmaz et al., 2000).

The hydrogen-bonding schemes (Table 2) are different for the two molecules. Only the NCS and free OH groups participate in hydrogen bonding in molecule A, whereas the NCS, NH, NH₂ and free OH groups in molecule B are all involved in intermolecular hydrogen bonding. The two molecules form two parallel chains, which are connected to each other via hydrogen bonding, as shown in Fig. 2. Hydrogen bonding between the H atoms of the NH₂ and OH groups connects successive molecules of B into one chain. The other chain, formed by molecule A, is linked by one fork of a bifurcated hydrogen bond in which an H atom of an OH group of A serves as a donor both to an S atom of the next molecule A in the chain and to an S atom of molecule B in a neighbouring chain. Other hydrogen bonds link the chains to one another. These involve the H atoms of NH₂ groups in molecule B acting as donors to S atoms in molecule A; in addition, the H atoms of the NH and OH groups in molecule B donate to an OH group in A. The chains are thus linked to form sheets, which in turn are stacked with only van der Waals interactions between them.

S2. Experimental

Solid KSCN (10 mmol, 097 g) was added slowly with continuous stirring to a solution of NiCl₂·6H₂O (5 mmol, 1.19 g). This solution was then mixed with a solution of N-(2-hydroxethyl)-ethylenediamine (10 mmol, 1.04 g) in distilled water and the reaction mixture was stirred for about 2 h. Violet crystals suitable for X-ray analysis were obtained by slow evaporation of the resulting solution at room temperature.

S3. Refinement

H atoms of the hydroxy, NH and NH₂ groups were found in a difference map and their parameters were refined freely. The bond distances and U_iso(H) values were in the range 0.79 (3)–0.82 (3) Å and 0.079 (11)–0.087 (13) Ų for the OH groups, 0.83 (3)–0.86 (2) Å and 0.044 (7)–0.047 (7) Ų for the NH groups, and 0.85 (3)–0.93 (3) Å and 0.056 (8)–0.073 (10) Ų for the NH₂ groups. Other H atoms were introduced at idealized positions and were allowed to ride on their parent atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEPIII (Burnett & Johnson, 1996) view of (I), with the atom-numbering scheme. Displacement elipsoids are sh own at the 50% probability level. All H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, −y, −z; (ii) 1 − x, 1 − y,-z.]
	Fig. 2. Hydrogen bonding involving molecules A (containing Ni1) and B (containing Ni2), viewed along the b axis. Dashed lines illustrate the hydrogen bonds. Methylene H atoms have been omitted for clarity.

(I)

Crystal data

[Ni(NCS)2(C4H12N2O)2]	F(000) = 808
Mr = 383.18	Dx = 1.504 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16351 reflections
a = 8.3891 (7) Å	θ = 2.0–29.3°
b = 13.8940 (8) Å	µ = 1.41 mm^−1
c = 14.5530 (12) Å	T = 293 K
β = 94.025 (7)°	Prism, violet
V = 1692.1 (2) Å^3	0.31 × 0.25 × 0.21 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	4605 independent reflections
Radiation source: fine-focus sealed tube	2777 reflections with I > 2 σ(I)
Plane graphite monochromator	Rint = 0.050
Detector resolution: 6.67 pixels mm^-1	θmax = 29.3°, θmin = 2.0°
rotation method scans	h = −11→11
Absorption correction: integration X-RED32 (Stoe & Cie, 2002)	k = −19→17
Tmin = 0.698, Tmax = 0.770	l = −20→19
32390 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0414P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
4605 reflections	Δρmax = 0.57 e Å^−3
226 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (6)

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	0.9350 (3)	0.58119 (19)	0.18460 (17)	0.0524 (6)
H1A	1.0168	0.5430	0.1579	0.063*
H1B	0.9774	0.6454	0.1960	0.063*
C2	0.7895 (3)	0.58681 (17)	0.11781 (16)	0.0467 (5)
H2A	0.7129	0.6299	0.1433	0.056*
H2B	0.8209	0.6155	0.0611	0.056*
C3	0.8129 (3)	0.42155 (18)	0.05768 (16)	0.0444 (5)
H3A	0.8957	0.4030	0.1042	0.053*
H3B	0.8638	0.4473	0.0051	0.053*
C4	0.7133 (3)	0.33578 (17)	0.02894 (17)	0.0488 (6)
H4A	0.7797	0.2871	0.0029	0.059*
H4B	0.6664	0.3083	0.0821	0.059*
C5	0.2953 (2)	0.40325 (16)	0.15549 (14)	0.0357 (4)
C6	0.0658 (3)	0.1835 (2)	0.02274 (18)	0.0555 (7)
H6A	0.1097	0.2335	0.0635	0.067*
H6B	0.0058	0.2146	−0.0284	0.067*
C7	0.1994 (3)	0.1286 (2)	−0.01342 (16)	0.0501 (6)
H7A	0.1540	0.0793	−0.0546	0.060*
H7B	0.2591	0.1722	−0.0502	0.060*
C8	0.3932 (3)	0.14756 (18)	0.12160 (16)	0.0469 (6)
H8A	0.3157	0.1741	0.1611	0.056*
H8B	0.4410	0.2004	0.0897	0.056*
C9	0.5205 (3)	0.09389 (18)	0.17894 (15)	0.0463 (5)
H9A	0.5780	0.1381	0.2209	0.056*
H9B	0.4715	0.0449	0.2152	0.056*
C10	0.6518 (2)	0.14976 (15)	−0.13194 (14)	0.0341 (4)
N1	0.7086 (2)	0.49508 (14)	0.09506 (12)	0.0354 (4)
N2	0.5858 (2)	0.36560 (15)	−0.04007 (14)	0.0404 (4)
N3	0.3692 (2)	0.43336 (15)	0.09809 (13)	0.0454 (5)
N4	0.3134 (2)	0.08171 (14)	0.05449 (12)	0.0363 (4)
N5	0.6324 (2)	0.04859 (16)	0.11841 (13)	0.0383 (4)
N6	0.5754 (2)	0.11812 (14)	−0.07656 (13)	0.0416 (4)
O1	0.8962 (2)	0.53893 (17)	0.26958 (12)	0.0576 (5)
O2	−0.03955 (19)	0.12680 (16)	0.07092 (13)	0.0579 (5)
S1	0.18727 (8)	0.36054 (5)	0.23510 (4)	0.04958 (16)
S2	0.76429 (9)	0.19463 (6)	−0.20855 (5)	0.05864 (19)
Ni1	0.5000	0.5000	0.0000	0.03151 (10)
Ni2	0.5000	0.0000	0.0000	0.03016 (10)
H1N	0.675 (3)	0.4721 (18)	0.1448 (17)	0.044 (7)*
H1O	0.907 (4)	0.481 (2)	0.271 (2)	0.087 (13)*
H2N1	0.511 (4)	0.324 (2)	−0.047 (2)	0.073 (10)*
H2N2	0.628 (3)	0.371 (2)	−0.091 (2)	0.062 (9)*
H2N	0.267 (3)	0.041 (2)	0.0851 (16)	0.047 (7)*
H2O	−0.002 (4)	0.103 (2)	0.117 (2)	0.079 (11)*
H5A	0.685 (3)	−0.0025 (19)	0.1491 (18)	0.056 (8)*
H5B	0.710 (3)	0.085 (2)	0.1037 (18)	0.061 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0466 (13)	0.0500 (15)	0.0596 (15)	−0.0088 (12)	−0.0027 (11)	−0.0102 (12)
C2	0.0507 (13)	0.0386 (12)	0.0500 (13)	−0.0058 (11)	−0.0015 (10)	−0.0023 (11)
C3	0.0350 (11)	0.0501 (14)	0.0476 (12)	0.0065 (10)	0.0001 (9)	−0.0077 (11)
C4	0.0488 (13)	0.0395 (13)	0.0566 (14)	0.0138 (10)	−0.0078 (11)	−0.0092 (11)
C5	0.0367 (11)	0.0359 (11)	0.0339 (10)	0.0008 (9)	−0.0011 (8)	−0.0044 (9)
C6	0.0448 (13)	0.0671 (18)	0.0547 (14)	0.0141 (13)	0.0043 (11)	0.0084 (13)
C7	0.0445 (12)	0.0635 (16)	0.0433 (12)	0.0167 (12)	0.0090 (10)	0.0115 (12)
C8	0.0516 (13)	0.0392 (13)	0.0511 (13)	0.0066 (11)	0.0119 (11)	−0.0063 (11)
C9	0.0523 (13)	0.0507 (14)	0.0360 (11)	−0.0037 (11)	0.0038 (10)	−0.0086 (10)
C10	0.0347 (10)	0.0311 (11)	0.0363 (10)	0.0032 (9)	−0.0002 (8)	−0.0022 (9)
N1	0.0355 (8)	0.0364 (9)	0.0344 (8)	−0.0023 (8)	0.0024 (7)	−0.0025 (8)
N2	0.0414 (10)	0.0355 (10)	0.0440 (11)	0.0036 (9)	0.0004 (8)	−0.0082 (9)
N3	0.0444 (10)	0.0515 (12)	0.0412 (10)	−0.0028 (9)	0.0099 (8)	0.0066 (9)
N4	0.0331 (9)	0.0384 (10)	0.0384 (9)	0.0081 (8)	0.0095 (7)	0.0050 (8)
N5	0.0336 (9)	0.0423 (11)	0.0385 (9)	−0.0019 (9)	0.0000 (8)	0.0003 (9)
N6	0.0422 (10)	0.0382 (11)	0.0449 (10)	−0.0041 (8)	0.0084 (8)	0.0049 (8)
O1	0.0687 (12)	0.0566 (12)	0.0460 (10)	0.0056 (11)	−0.0060 (8)	−0.0113 (9)
O2	0.0334 (8)	0.0856 (15)	0.0551 (11)	0.0064 (9)	0.0054 (8)	0.0165 (10)
S1	0.0582 (4)	0.0519 (4)	0.0407 (3)	−0.0063 (3)	0.0182 (3)	0.0001 (3)
S2	0.0630 (4)	0.0640 (5)	0.0515 (4)	−0.0066 (3)	0.0218 (3)	0.0086 (3)
Ni1	0.03200 (18)	0.03189 (19)	0.03099 (17)	0.00063 (17)	0.00472 (13)	−0.00040 (16)
Ni2	0.02514 (17)	0.03322 (19)	0.03247 (18)	0.00140 (16)	0.00442 (13)	0.00134 (16)

Geometric parameters (Å, º)

C1—O1	1.427 (3)	C8—N4	1.465 (3)
C1—C2	1.508 (3)	C8—C9	1.506 (3)
C1—H1A	0.9700	C8—H8A	0.9700
C1—H1B	0.9700	C8—H8B	0.9700
C2—N1	1.471 (3)	C9—N5	1.473 (3)
C2—H2A	0.9700	C9—H9A	0.9700
C2—H2B	0.9700	C9—H9B	0.9700
C3—N1	1.474 (3)	C10—N6	1.152 (3)
C3—C4	1.498 (3)	C10—S2	1.634 (2)
C3—H3A	0.9700	N1—Ni1	2.1542 (17)
C3—H3B	0.9700	N1—H1N	0.86 (2)
C4—N2	1.474 (3)	N2—Ni1	2.0986 (19)
C4—H4A	0.9700	N2—H2N1	0.85 (3)
C4—H4B	0.9700	N2—H2N2	0.85 (3)
C5—N3	1.153 (3)	N3—Ni1	2.0782 (18)
C5—S1	1.632 (2)	N4—Ni2	2.1316 (17)
C6—O2	1.407 (3)	N4—H2N	0.83 (3)
C6—C7	1.482 (3)	N5—Ni2	2.0952 (18)
C6—H6A	0.9700	N5—H5A	0.93 (3)
C6—H6B	0.9700	N5—H5B	0.86 (3)
C7—N4	1.478 (3)	N6—Ni2	2.1057 (18)
C7—H7A	0.9700	O1—H1O	0.82 (3)
C7—H7B	0.9700	O2—H2O	0.79 (3)
O1—C1—C2	110.9 (2)	C8—C9—H9A	109.7
O1—C1—H1A	109.5	N5—C9—H9B	109.7
C2—C1—H1A	109.5	C8—C9—H9B	109.7
O1—C1—H1B	109.5	H9A—C9—H9B	108.2
C2—C1—H1B	109.5	N6—C10—S2	178.50 (19)
H1A—C1—H1B	108.1	C2—N1—C3	114.04 (18)
N1—C2—C1	116.1 (2)	C2—N1—Ni1	117.27 (14)
N1—C2—H2A	108.3	C3—N1—Ni1	105.16 (12)
C1—C2—H2A	108.3	C2—N1—H1N	107.8 (17)
N1—C2—H2B	108.3	C3—N1—H1N	107.0 (17)
C1—C2—H2B	108.3	Ni1—N1—H1N	104.7 (16)
H2A—C2—H2B	107.4	C4—N2—Ni1	107.90 (14)
N1—C3—C4	108.69 (18)	C4—N2—H2N1	113 (2)
N1—C3—H3A	110.0	Ni1—N2—H2N1	112 (2)
C4—C3—H3A	110.0	C4—N2—H2N2	107.2 (19)
N1—C3—H3B	110.0	Ni1—N2—H2N2	109 (2)
C4—C3—H3B	110.0	H2N1—N2—H2N2	108 (3)
H3A—C3—H3B	108.3	C5—N3—Ni1	174.75 (19)
N2—C4—C3	109.3 (2)	C8—N4—C7	114.47 (19)
N2—C4—H4A	109.8	C8—N4—Ni2	105.50 (13)
C3—C4—H4A	109.8	C7—N4—Ni2	116.36 (13)
N2—C4—H4B	109.8	C8—N4—H2N	106.1 (17)
C3—C4—H4B	109.8	C7—N4—H2N	110.6 (17)
H4A—C4—H4B	108.3	Ni2—N4—H2N	102.7 (18)
N3—C5—S1	178.7 (2)	C9—N5—Ni2	107.84 (13)
O2—C6—C7	114.0 (2)	C9—N5—H5A	109.7 (16)
O2—C6—H6A	108.8	Ni2—N5—H5A	110.7 (16)
C7—C6—H6A	108.8	C9—N5—H5B	114.6 (18)
O2—C6—H6B	108.8	Ni2—N5—H5B	110.5 (17)
C7—C6—H6B	108.8	H5A—N5—H5B	103 (2)
H6A—C6—H6B	107.7	C10—N6—Ni2	150.51 (18)
N4—C7—C6	117.34 (19)	C1—O1—H1O	113 (2)
N4—C7—H7A	108.0	C6—O2—H2O	115 (2)
C6—C7—H7A	108.0	N3—Ni1—N2	90.14 (9)
N4—C7—H7B	108.0	N3—Ni1—N1	89.37 (7)
C6—C7—H7B	108.0	N2—Ni1—N1	82.59 (7)
H7A—C7—H7B	107.2	N2^i—Ni1—N1	97.41 (7)
N4—C8—C9	109.47 (19)	N3—Ni1—N1^i	90.63 (7)
N4—C8—H8A	109.8	N3^i—Ni1—N2	89.86 (9)
C9—C8—H8A	109.8	N5—Ni2—N6	91.29 (8)
N4—C8—H8B	109.8	N5—Ni2—N4	83.29 (7)
C9—C8—H8B	109.8	N6—Ni2—N4	92.15 (7)
H8A—C8—H8B	108.2	N5—Ni2—N6^ii	88.71 (8)
N5—C9—C8	109.70 (18)	N5^ii—Ni2—N4	96.71 (7)
N5—C9—H9A	109.7	N6—Ni2—N4^ii	87.85 (7)
O1—C1—C2—N1	−57.7 (3)	C4—N2—Ni1—N3	−77.78 (17)
N1—C3—C4—N2	58.3 (3)	C4—N2—Ni1—N1	11.57 (17)
O2—C6—C7—N4	−63.1 (3)	C2—N1—Ni1—N3	−123.76 (16)
N4—C8—C9—N5	55.9 (3)	C3—N1—Ni1—N3	108.32 (15)
C1—C2—N1—C3	−56.6 (3)	C2—N1—Ni1—N2	146.02 (17)
C1—C2—N1—Ni1	179.93 (16)	C3—N1—Ni1—N2	18.10 (15)
C4—C3—N1—C2	−174.54 (19)	C9—N5—Ni2—N6	102.39 (16)
C4—C3—N1—Ni1	−44.7 (2)	C9—N5—Ni2—N4	10.38 (16)
C3—C4—N2—Ni1	−39.7 (2)	C10—N6—Ni2—N5	107.0 (3)
C9—C8—N4—C7	−172.86 (18)	C10—N6—Ni2—N4	−169.6 (3)
C9—C8—N4—Ni2	−43.6 (2)	C8—N4—Ni2—N5	18.21 (15)
C6—C7—N4—C8	−58.2 (3)	C7—N4—Ni2—N5	146.31 (18)
C6—C7—N4—Ni2	178.23 (19)	C8—N4—Ni2—N6	−72.83 (15)
C8—C9—N5—Ni2	−37.2 (2)	C7—N4—Ni2—N6	55.27 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···O2^iii	0.86 (3)	2.26 (3)	3.082 (3)	158 (3)
N5—H5A···S1^iv	0.93 (3)	2.71 (3)	3.634 (2)	170 (2)
N4—H2N···O1^iv	0.83 (3)	2.60 (2)	3.261 (3)	137 (2)
O1—H1O···S1^iii	0.82 (3)	2.96 (3)	3.539 (2)	130 (3)
O1—H1O···S2^v	0.82 (3)	2.74 (3)	3.450 (2)	147 (3)
O2—H2O···O1^iv	0.79 (3)	2.03 (3)	2.817 (3)	177 (3)

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