(NH₄)₃[VO₂(SO₄)₂(H₂O)₂]·1.5H₂O

The title compound, tri­ammonium cis-di­aqua-cis-dioxo-trans-disulfatovanadate 1.5-hydrate, was obtained by oxidizing V^IV to V^V in a 2 M sulfuric acid solution of vanadyl­ sulfate and adding ammonium sulfate. Here, the V atom is sandwiched by two sulfate groups by corner-sharing to form a discrete [VO₂(SO₄)₂(OH₂)₂]^3- anion. The water mol­ecules occupy cis positions in the equatorial plane of the vanadium octahedron.

S1. Comment

Vanadate solutions in concentrated sulfuric acid (2 ~6 M) are commercially used as an electrolyte for redox-flow batteries (Kazacos et al., 1990; Kumamoto et al., 1999). However, the chemistry of vanadate in such concentrated and highly acidic solutions is still sketchy and the exact composition and structure of the species in solution is not yet known. During the study of such a solution we have isolated the title compound, (I). \sch

The present compound (Fig. 1) consists of a discrete disulfatodiaquadioxovanadate anion, ammonium cations and water of crystallization. The anion shows the trans arrangement of the sulfate ligand about the vanadium atom. A similar connection mode has been observed for V(O₃SCF₃)₂(C₅NH₅)₄ (Ghosh et al., 1995) and K[VO₂(SO₄)(OH₂)₂] (Richter & Mattes, 1991). Four additional oxygen atoms bind to the metal centre to complete a distorted octahedral coordination. Those four oxygen atoms lie in a plane that contains the vanadium atom [+0.0161 (7) to −0.0141 (6) Å]. The V1—O distances for two of these O atoms are relatively long [V1—OW1 2.232 (1), V1—OW2 2.259 (1) Å] and indicate that these two oxygen atoms are those of coordinated water molecules. The distances for the other two [V1—O1 1.634 (1), V1—O2 1.620 (1) Å] are normal for terminal oxo ligands. Both terminal oxo ligands and water molecules assume a cis arrangement. In other words, the coordination site trans to an oxo ligand is occupied by a water molecule. The coordination around the vanadium atom is highly distorted and all the O—V1—O angles deviate significantly from the ideal values of 90 and 180°. In addition, the vanadium atom is displaced from the center of the octahedron towards two terminal oxo ligands. This kind of cis dioxo octahedral unit is commonly found in polymolybdates and polytungstates (Pope, 1983). However, the current compound is the first such example for discrete inorganic vanadates to the best of our knowledge. The sulfate tetrahedra, on the other hand, are quite normal. The bond lengths of S—O(—V1) [1.512 (1) Å for S1—O11 and 1.506 (1) Å for S2—O21] are longer than those of other S—O [1.460 (2) to 1.468 (1) Å] due to the coordination to the V atom. The angle S1—V1—S2 is 162.60 (1)° and thus the feature of the anion is slightly bent. Hydrogen bonds formed in the crystal are listed in Table 2. The water of crystallization (OW3 and OW4) and ammonium cations (N1, N2 and N3) form a hydrogen-bond network through the crystal with each other and the disulfatovanado anion. The slightly longer distance of V1—O1 than V1—O2 is probably caused by the rather short contact of OW3 to O1 [2.803 (2) Å].

S2. Experimental

An appropriate amount of vanadyl sulfate, VOSO₄, was dissolved in sulfuric acid, and water was added to achieve the concentration of 2 M for both VOSO₄ and H₂SO₄. Then V^IV was electrolytically oxidized to V^V. To a 4 ml portion of this solution, (NH₄)₂SO₄ (3.3 g, 25 mmol) was added and the mixture was heated to 323 K to dissolve the ammonium sulfate. The resulting solution was kept at 301 K for 3 d to obtain the orange tabular crystals.

S3. Refinement

All H atoms were fixed at the positions obtained from differential Fourier maps.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software); data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The structure of [VO2(SO4)2(OH2)2]^3−. Displacement ellipsoids are plotted at the 30% probability level. H atoms are omitted for omitted for clarity.

Triammonium cis-diaqua-cis-dioxo-trans-disulfatovanadate hemitrihydrate

Crystal data

(NH4)3·[VO2(SO4)2(OH2)2]·1.5H2O	Z = 2
Mr = 392.24	F(000) = 406
Triclinic, P1	Dx = 1.903 Mg m^−3
a = 7.748 (2) Å	Mo Kα radiation, λ = 0.71069 Å
b = 14.164 (3) Å	Cell parameters from 25 reflections
c = 6.268 (2) Å	θ = 17.4–17.5°
α = 91.54 (2)°	µ = 1.10 mm^−1
β = 95.30 (2)°	T = 293 K
γ = 88.25 (2)°	Plate, orange
V = 684.4 (3) Å^3	0.60 × 0.50 × 0.20 mm

Data collection

RIGAKU AFC-5R automated four-circle diffractometer	7201 independent reflections
Radiation source: normal focus rotating anode	6049 reflections with F^2 > 2.0σ(F^2)
Graphite monochromator	Rint = 0.000
Detector resolution: 3 pixels mm^-1	θmax = 37.5°, θmin = 2.6°
ω–2θ scans	h = −13→13
Absorption correction: ψ scan TEXSAN (Molecular Structure Corporation, 1995)	k = −23→23
Tmin = 0.576, Tmax = 0.802	l = −10→0
7201 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters not refined
wR(F^2) = 0.100	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 0.245P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
7201 reflections	Δρmax = 0.90 e Å^−3
179 parameters	Δρmin = −0.81 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (17)

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	Occ. (<1)
V1	0.41406 (2)	0.232330 (13)	0.46950 (3)	0.01946 (5)
S1	0.14518 (4)	0.37785 (2)	0.23438 (6)	0.02690 (7)
S2	0.74810 (3)	0.098593 (18)	0.58459 (4)	0.01907 (5)
O1	0.55752 (13)	0.31019 (7)	0.42587 (18)	0.02993 (18)
O2	0.38995 (14)	0.17176 (8)	0.24622 (17)	0.0329 (2)
OW1	0.22757 (12)	0.14909 (7)	0.63305 (19)	0.02893 (18)
OW2	0.41290 (14)	0.30238 (7)	0.79675 (17)	0.03127 (19)
O11	0.19843 (12)	0.31434 (7)	0.42029 (17)	0.02863 (18)
O12	0.13178 (16)	0.31852 (9)	0.0373 (2)	0.0379 (2)
O13	−0.02344 (14)	0.42014 (9)	0.2745 (2)	0.0403 (3)
O14	0.27415 (17)	0.45012 (9)	0.2239 (3)	0.0499 (4)
O21	0.57481 (11)	0.14075 (7)	0.63211 (15)	0.02478 (16)
O22	0.72938 (15)	0.04146 (7)	0.38645 (17)	0.03152 (19)
O23	0.86817 (12)	0.17500 (7)	0.5614 (2)	0.0338 (2)
O24	0.80695 (13)	0.04067 (7)	0.76919 (17)	0.03013 (19)
N1	0.00854 (17)	0.13172 (9)	0.1252 (2)	0.0333 (2)
N2	0.8812 (2)	0.36879 (10)	0.6918 (2)	0.0385 (3)
N3	0.6224 (2)	0.49888 (12)	0.2242 (4)	0.0543 (5)
OW3	0.72234 (18)	0.26757 (14)	0.0540 (2)	0.0547 (4)
OW4	0.5000	0.0000	0.0000	0.0435 (4)
H11	0.2449	0.0954	0.6185	0.060*
H12	0.1249	0.1579	0.6088	0.060*
H21	0.3351	0.2968	0.8714	0.060*
H22	0.5017	0.2938	0.8831	0.060*
H31	0.6830	0.2731	0.1738	0.110*
H32	0.8044	0.3106	0.1203	0.110*
H41	0.5735	0.0210	0.1079	0.090*	0.50
H42	0.6051	0.0109	−0.0352	0.090*	0.50
H51	−0.0432	0.1140	0.0217	0.070*
H52	0.0649	0.1761	0.1060	0.070*
H53	0.0814	0.0903	0.1694	0.070*
H54	−0.0488	0.1498	0.2257	0.070*
H61	0.8299	0.4166	0.7110	0.080*
H62	0.9573	0.3607	0.7914	0.080*
H63	0.8445	0.3244	0.6534	0.080*
H64	0.9354	0.3894	0.5880	0.080*
H71	0.7177	0.4646	0.2001	0.110*
H72	0.5388	0.4600	0.2383	0.110*
H73	0.6402	0.5061	0.3490	0.110*
H74	0.5985	0.5524	0.1314	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.01595 (7)	0.01890 (8)	0.02329 (8)	0.00197 (5)	0.00110 (5)	0.00121 (6)
S1	0.02039 (12)	0.02187 (12)	0.03869 (16)	0.00533 (9)	0.00381 (10)	0.00802 (11)
S2	0.01539 (9)	0.01541 (10)	0.02601 (12)	0.00138 (7)	0.00016 (8)	0.00099 (8)
O1	0.0242 (4)	0.0284 (4)	0.0379 (5)	−0.0037 (3)	0.0038 (3)	0.0060 (4)
O2	0.0321 (5)	0.0344 (5)	0.0303 (4)	0.0061 (4)	−0.0021 (4)	−0.0074 (4)
OW1	0.0198 (3)	0.0206 (3)	0.0466 (5)	−0.0001 (3)	0.0037 (3)	0.0031 (3)
OW2	0.0309 (4)	0.0310 (4)	0.0323 (5)	−0.0010 (4)	0.0064 (4)	−0.0055 (4)
O11	0.0231 (4)	0.0274 (4)	0.0356 (5)	0.0081 (3)	0.0040 (3)	0.0080 (3)
O12	0.0362 (5)	0.0422 (6)	0.0354 (5)	0.0077 (4)	0.0046 (4)	0.0058 (4)
O13	0.0273 (5)	0.0412 (6)	0.0524 (7)	0.0178 (4)	0.0074 (4)	0.0105 (5)
O14	0.0351 (6)	0.0270 (5)	0.0892 (11)	−0.0024 (4)	0.0081 (6)	0.0184 (6)
O21	0.0168 (3)	0.0267 (4)	0.0309 (4)	0.0058 (3)	0.0033 (3)	0.0064 (3)
O22	0.0388 (5)	0.0252 (4)	0.0295 (4)	0.0045 (4)	0.0004 (4)	−0.0051 (3)
O23	0.0198 (4)	0.0224 (4)	0.0601 (7)	−0.0041 (3)	0.0065 (4)	0.0013 (4)
O24	0.0301 (4)	0.0270 (4)	0.0316 (4)	0.0078 (3)	−0.0053 (3)	0.0059 (3)
N1	0.0305 (5)	0.0304 (5)	0.0377 (6)	0.0001 (4)	−0.0033 (4)	0.0020 (4)
N2	0.0452 (7)	0.0302 (6)	0.0387 (6)	−0.0011 (5)	−0.0027 (5)	−0.0047 (5)
N3	0.0362 (7)	0.0389 (7)	0.0888 (14)	−0.0022 (6)	0.0059 (8)	0.0203 (8)
OW3	0.0319 (6)	0.0885 (12)	0.0441 (7)	0.0032 (6)	0.0045 (5)	0.0101 (7)
OW4	0.0360 (8)	0.0578 (11)	0.0363 (8)	−0.0043 (7)	0.0024 (6)	−0.0054 (7)

Geometric parameters (Å, º)

V1—O2	1.6206 (11)	O22—OW4	2.9263 (14)
V1—O1	1.6352 (10)	O22—N1^viii	3.151 (2)
V1—O21	2.0026 (10)	O23—OW1^viii	2.7939 (15)
V1—O11	2.0103 (10)	O23—N2	2.8450 (18)
V1—OW1	2.2296 (11)	O23—N1^viii	3.074 (2)
V1—OW2	2.2551 (12)	O24—N1^i	2.8536 (17)
S1—O14	1.4591 (13)	O24—N1^ix	2.8994 (18)
S1—O13	1.4608 (11)	O24—OW4^iii	2.9740 (14)
S1—O12	1.4725 (14)	N1—O24^i	2.8536 (17)
S1—O11	1.5107 (11)	N1—O24^vi	2.8994 (18)
S2—O22	1.4622 (11)	N1—OW3^ii	2.902 (2)
S2—O24	1.4665 (11)	N1—O23^ii	3.074 (2)
S2—O23	1.4672 (10)	N1—O22^ii	3.151 (2)
S2—O21	1.5045 (9)	N1—H51	0.7706
O1—OW2	2.6785 (17)	N1—H52	0.7942
O1—OW3	2.803 (2)	N1—H53	0.8362
O1—N2	3.006 (2)	N1—H54	0.8342
O1—N3	3.062 (2)	N2—O14^iv	2.857 (2)
O2—OW1	2.8627 (18)	N2—O12^ix	2.862 (2)
O2—OW4	2.9904 (12)	N2—O13^viii	2.899 (2)
O2—N1	3.0488 (19)	N2—OW3^iii	3.087 (2)
OW1—O21	2.6899 (14)	N2—O11^viii	3.181 (2)
OW1—O22^i	2.7103 (15)	N2—H61	0.7869
OW1—O11	2.7180 (15)	N2—H62	0.8260
OW1—OW2	2.7617 (16)	N2—H63	0.7241
OW1—O23^ii	2.7939 (15)	N2—H64	0.8674
OW1—H11	0.7727	N3—OW2^iv	2.825 (2)
OW1—H12	0.8025	N3—O13^viii	2.923 (2)
OW2—O12^iii	2.7620 (17)	N3—O14^vii	3.101 (3)
OW2—O11	2.7637 (17)	N3—H71	0.8939
OW2—O21	2.7957 (15)	N3—H72	0.8747
OW2—OW3^iii	2.8015 (19)	N3—H73	0.786
OW2—N3^iv	2.825 (2)	N3—H74	0.9709
OW2—H21	0.8035	OW3—OW2^v	2.8015 (19)
OW2—H22	0.8430	OW3—N1^viii	2.902 (2)
O11—N2^ii	3.181 (2)	OW3—N2^v	3.087 (2)
O12—OW2^v	2.7620 (17)	OW3—O13^viii	3.171 (2)
O12—N2^vi	2.862 (2)	OW3—H31	0.8368
O12—N1	2.923 (2)	OW3—H32	0.9536
O13—N2^ii	2.899 (2)	OW4—O22^x	2.9263 (14)
O13—N3^ii	2.923 (2)	OW4—O24^i	2.9740 (13)
O13—OW3^ii	3.171 (2)	OW4—O24^v	2.9740 (13)
O13—N2^iv	3.212 (2)	OW4—O2^x	2.9904 (12)
O14—N3	2.805 (2)	OW4—O21^i	3.1926 (12)
O14—N2^iv	2.857 (2)	OW4—O21^v	3.1926 (12)
O14—N3^vii	3.101 (3)	OW4—H41	0.8936
O21—OW4^iii	3.1926 (12)	OW4—H42	0.8822
O22—OW1^i	2.7103 (15)
O2—V1—O1	103.80 (6)	O2—N1—O23^ii	99.08 (5)
O2—V1—O21	97.41 (5)	O24^i—N1—O22^ii	81.91 (5)
O1—V1—O21	97.72 (5)	O24^vi—N1—O22^ii	81.89 (5)
O2—V1—O11	97.06 (5)	OW3^ii—N1—O22^ii	79.21 (5)
O1—V1—O11	98.77 (5)	O12—N1—O22^ii	138.99 (6)
O21—V1—O11	154.76 (4)	O2—N1—O22^ii	131.15 (6)
O2—V1—OW1	94.74 (6)	O23^ii—N1—O22^ii	45.21 (4)
O1—V1—OW1	161.43 (5)	O24^i—N1—H51	97.81
O21—V1—OW1	78.73 (4)	O24^vi—N1—H51	8.23
O11—V1—OW1	79.56 (4)	OW3^ii—N1—H51	75.24
O2—V1—OW2	170.71 (5)	O12—N1—H51	106.77
O1—V1—OW2	85.45 (5)	O2—N1—H51	133.88
O21—V1—OW2	81.85 (5)	O23^ii—N1—H51	126.99
O11—V1—OW2	80.55 (5)	O22^ii—N1—H51	88.17
OW1—V1—OW2	76.02 (4)	O24^i—N1—H52	116.89
O14—S1—O13	111.13 (8)	O24^vi—N1—H52	120.40
O14—S1—O12	110.89 (9)	OW3^ii—N1—H52	82.90
O13—S1—O12	110.92 (8)	O12—N1—H52	14.22
O14—S1—O11	109.56 (8)	O2—N1—H52	48.29
O13—S1—O11	106.40 (7)	O23^ii—N1—H52	104.17
O12—S1—O11	107.78 (7)	O22^ii—N1—H52	148.13
O22—S2—O24	111.37 (6)	H51—N1—H52	112.48
O22—S2—O23	109.61 (7)	O24^i—N1—H53	14.25
O24—S2—O23	110.98 (7)	O24^vi—N1—H53	104.50
O22—S2—O21	109.98 (6)	OW3^ii—N1—H53	167.89
O24—S2—O21	105.69 (6)	O12—N1—H53	118.37
O23—S2—O21	109.13 (6)	O2—N1—H53	56.82
V1—O1—OW2	57.06 (4)	O23^ii—N1—H53	95.85
V1—O1—OW3	112.45 (7)	O22^ii—N1—H53	89.90
OW2—O1—OW3	164.99 (6)	H51—N1—H53	109.98
V1—O1—N2	130.75 (6)	H52—N1—H53	104.30
OW2—O1—N2	86.28 (5)	O24^i—N1—H54	110.11
OW3—O1—N2	95.27 (6)	O24^vi—N1—H54	114.43
V1—O1—N3	146.17 (6)	OW3^ii—N1—H54	59.34
OW2—O1—N3	121.62 (6)	O12—N1—H54	95.68
OW3—O1—N3	73.25 (6)	O2—N1—H54	109.04
N2—O1—N3	79.27 (6)	O23^ii—N1—H54	13.68
V1—O2—OW1	50.91 (4)	O22^ii—N1—H54	44.68
V1—O2—OW4	146.38 (6)	H51—N1—H54	116.73
OW1—O2—OW4	119.18 (5)	H52—N1—H54	103.45
V1—O2—N1	110.71 (6)	H53—N1—H54	109.04
OW1—O2—N1	71.87 (5)	O23—N2—O14^iv	153.08 (7)
OW4—O2—N1	91.25 (4)	O23—N2—O12^ix	89.03 (6)
V1—OW1—O21	46.90 (3)	O14^iv—N2—O12^ix	110.28 (7)
V1—OW1—O22^i	116.59 (5)	O23—N2—O13^viii	91.00 (6)
O21—OW1—O22^i	81.93 (5)	O14^iv—N2—O13^viii	93.68 (6)
V1—OW1—O11	46.67 (3)	O12^ix—N2—O13^viii	122.79 (7)
O21—OW1—O11	92.79 (4)	O23—N2—O1	63.91 (4)
O22^i—OW1—O11	147.86 (6)	O14^iv—N2—O1	90.61 (6)
V1—OW1—OW2	52.41 (3)	O12^ix—N2—O1	145.21 (7)
O21—OW1—OW2	61.69 (4)	O13^viii—N2—O1	81.36 (5)
O22^i—OW1—OW2	137.70 (5)	O23—N2—OW3^iii	74.30 (6)
O11—OW1—OW2	60.57 (4)	O14^iv—N2—OW3^iii	95.61 (7)
V1—OW1—O23^ii	123.01 (5)	O12^ix—N2—OW3^iii	66.95 (5)
O21—OW1—O23^ii	169.25 (6)	O13^viii—N2—OW3^iii	162.78 (7)
O22^i—OW1—O23^ii	102.82 (5)	O1—N2—OW3^iii	84.08 (6)
O11—OW1—O23^ii	78.04 (4)	O23—N2—O11^viii	70.08 (5)
OW2—OW1—O23^ii	116.91 (5)	O14^iv—N2—O11^viii	129.63 (6)
V1—OW1—O2	34.35 (3)	O12^ix—N2—O11^viii	81.40 (5)
O21—OW1—O2	58.89 (4)	O13^viii—N2—O11^viii	45.79 (4)
O22^i—OW1—O2	92.49 (5)	O1—N2—O11^viii	106.90 (6)
O11—OW1—O2	58.57 (4)	OW3^iii—N2—O11^viii	132.16 (6)
OW2—OW1—O2	86.75 (5)	O23—N2—H61	147.63
O23^ii—OW1—O2	110.90 (5)	O14^iv—N2—H61	5.47
V1—OW1—H11	111.48	O12^ix—N2—H61	114.21
O21—OW1—H11	78.59	O13^viii—N2—H61	94.26
O22^i—OW1—H11	5.37	O1—N2—H61	85.33
O11—OW1—H11	143.16	OW3^iii—N2—H61	93.65
OW2—OW1—H11	136.61	O11^viii—N2—H61	132.82
O23^ii—OW1—H11	105.36	O23—N2—H62	95.14
O2—OW1—H11	87.15	O14^iv—N2—H62	105.33
V1—OW1—H12	120.81	O12^ix—N2—H62	6.68
O21—OW1—H12	167.06	O13^viii—N2—H62	119.84
O22^i—OW1—H12	104.14	O1—N2—H62	151.67
O11—OW1—H12	75.95	OW3^iii—N2—H62	71.38
OW2—OW1—H12	116.06	O11^viii—N2—H62	81.02
O23^ii—OW1—H12	2.22	H61—N2—H62	109.57
O2—OW1—H12	108.95	O23—N2—H63	21.12
H11—OW1—H12	106.53	O14^iv—N2—H63	131.97
V1—OW2—O1	37.48 (3)	O12^ix—N2—H63	104.66
V1—OW2—O12^iii	125.70 (5)	O13^viii—N2—H63	94.13
O1—OW2—O12^iii	152.04 (6)	O1—N2—H63	44.27
V1—OW2—OW1	51.58 (4)	OW3^iii—N2—H63	68.93
O1—OW2—OW1	89.05 (5)	O11^viii—N2—H63	86.76
O12^iii—OW2—OW1	80.14 (5)	H61—N2—H63	126.5
V1—OW2—O11	45.85 (3)	H62—N2—H63	111.25
O1—OW2—O11	61.37 (4)	O23—N2—H64	98.49
O12^iii—OW2—O11	91.19 (5)	O14^iv—N2—H64	93.01
OW1—OW2—O11	58.93 (4)	O12^ix—N2—H64	108.57
V1—OW2—O21	45.16 (3)	O13^viii—N2—H64	15.96
O1—OW2—O21	60.27 (4)	O1—N2—H64	97.30
O12^iii—OW2—O21	129.72 (5)	OW3^iii—N2—H64	171.25
OW1—OW2—O21	57.89 (4)	O11^viii—N2—H64	39.19
O11—OW2—O21	89.56 (5)	H61—N2—H64	95.07
V1—OW2—OW3^iii	112.34 (6)	H62—N2—H64	104.90
O1—OW2—OW3^iii	96.22 (5)	H63—N2—H64	106.09
O12^iii—OW2—OW3^iii	111.64 (6)	O14—N3—OW2^iv	100.67 (7)
OW1—OW2—OW3^iii	118.09 (6)	O14—N3—O13^viii	142.61 (7)
O11—OW2—OW3^iii	156.57 (6)	OW2^iv—N3—O13^viii	116.39 (7)
O21—OW2—OW3^iii	72.06 (5)	O14—N3—O1	63.98 (5)
V1—OW2—N3^iv	112.29 (7)	OW2^iv—N3—O1	152.21 (9)
O1—OW2—N3^iv	85.93 (6)	O13^viii—N3—O1	80.04 (6)
O12^iii—OW2—N3^iv	84.49 (6)	O14—N3—O14^vii	113.62 (8)
OW1—OW2—N3^iv	136.54 (6)	OW2^iv—N3—O14^vii	74.10 (6)
O11—OW2—N3^iv	81.19 (6)	O13^viii—N3—O14^vii	82.77 (6)
O21—OW2—N3^iv	144.94 (6)	O1—N3—O14^vii	132.47 (8)
OW3^iii—OW2—N3^iv	105.37 (7)	O14—N3—H71	131.86
V1—OW2—H21	122.56	OW2^iv—N3—H71	125.49
O1—OW2—H21	155.66	O13^viii—N3—H71	18.95
O12^iii—OW2—H21	10.78	O1—N3—H71	77.45
OW1—OW2—H21	73.49	O14^vii—N3—H71	72.37
O11—OW2—H21	94.69	O14—N3—H72	25.78
O21—OW2—H21	119.44	OW2^iv—N3—H72	125.93
OW3^iii—OW2—H21	106.86	O13^viii—N3—H72	116.86
N3^iv—OW2—H21	95.09	O1—N3—H72	39.23
V1—OW2—H22	117.12	O14^vii—N3—H72	121.33
O1—OW2—H22	100.72	H71—N3—H72	108.12
O12^iii—OW2—H22	107.05	O14—N3—H73	96.43
OW1—OW2—H22	119.73	OW2^iv—N3—H73	86.87
O11—OW2—H22	161.42	O13^viii—N3—H73	81.59
O21—OW2—H22	76.19	O1—N3—H73	72.95
OW3^iii—OW2—H22	4.89	O14^vii—N3—H73	146.66
N3^iv—OW2—H22	103.61	H71—N3—H73	98.71
H21—OW2—H22	102.64	H72—N3—H73	92.0
S1—O11—V1	128.38 (6)	O14—N3—H74	95.02
S1—O11—OW1	155.87 (7)	OW2^iv—N3—H74	34.21
V1—O11—OW1	53.78 (3)	O13^viii—N3—H74	118.11
S1—O11—OW2	142.98 (7)	O1—N3—H74	157.09
V1—O11—OW2	53.60 (4)	O14^vii—N3—H74	45.46
OW1—O11—OW2	60.50 (4)	H71—N3—H74	114.8
S1—O11—N2^ii	96.80 (5)	H72—N3—H74	118.46
V1—O11—N2^ii	134.69 (5)	H73—N3—H74	121.1
OW1—O11—N2^ii	87.10 (5)	OW2^v—OW3—O1	91.03 (6)
OW2—O11—N2^ii	89.44 (5)	OW2^v—OW3—N1^viii	142.74 (8)
S1—O12—OW2^v	118.90 (7)	O1—OW3—N1^viii	112.78 (6)
S1—O12—N2^vi	119.24 (7)	OW2^v—OW3—N2^v	82.67 (6)
OW2^v—O12—N2^vi	96.41 (6)	O1—OW3—N2^v	139.92 (8)
S1—O12—N1	110.34 (7)	N1^viii—OW3—N2^v	94.72 (6)
OW2^v—O12—N1	110.46 (6)	OW2^v—OW3—O13^viii	126.94 (7)
N2^vi—O12—N1	99.25 (6)	O1—OW3—O13^viii	80.00 (6)
S1—O13—N2^ii	110.71 (7)	N1^viii—OW3—O13^viii	86.65 (5)
S1—O13—N3^ii	163.89 (9)	N2^v—OW3—O13^viii	72.84 (5)
N2^ii—O13—N3^ii	83.33 (6)	OW2^v—OW3—H31	98.27
S1—O13—OW3^ii	101.17 (7)	O1—OW3—H31	9.27
N2^ii—O13—OW3^ii	89.93 (6)	N1^viii—OW3—H31	103.62
N3^ii—O13—OW3^ii	70.07 (6)	N2^v—OW3—H31	146.41
S1—O13—N2^iv	93.44 (7)	O13^viii—OW3—H31	80.31
N2^ii—O13—N2^iv	108.69 (6)	OW2^v—OW3—H32	130.11
N3^ii—O13—N2^iv	89.18 (6)	O1—OW3—H32	81.84
OW3^ii—O13—N2^iv	150.57 (6)	N1^viii—OW3—H32	83.17
S1—O14—N3	149.47 (8)	N2^v—OW3—H32	72.78
S1—O14—N2^iv	109.07 (8)	O13^viii—OW3—H32	3.51
N3—O14—N2^iv	100.29 (7)	H31—OW3—H32	81.64
S1—O14—N3^vii	117.86 (10)	O22^x—OW4—O22	180.0
N3—O14—N3^vii	66.38 (8)	O22^x—OW4—O24^i	84.56 (4)
N2^iv—O14—N3^vii	94.72 (6)	O22—OW4—O24^i	95.44 (4)
S2—O21—V1	131.12 (6)	O22^x—OW4—O24^v	95.44 (4)
S2—O21—OW1	156.26 (6)	O22—OW4—O24^v	84.56 (4)
V1—O21—OW1	54.38 (3)	O24^i—OW4—O24^v	180.0
S2—O21—OW2	143.24 (6)	O22^x—OW4—O2	113.74 (3)
V1—O21—OW2	52.99 (4)	O22—OW4—O2	66.26 (3)
OW1—O21—OW2	60.42 (4)	O24^i—OW4—O2	69.74 (4)
S2—O21—OW4^iii	97.50 (4)	O24^v—OW4—O2	110.26 (4)
V1—O21—OW4^iii	129.72 (4)	O22^x—OW4—O2^x	66.26 (3)
OW1—O21—OW4^iii	76.08 (4)	O22—OW4—O2^x	113.74 (3)
OW2—O21—OW4^iii	97.63 (4)	O24^i—OW4—O2^x	110.26 (4)
S2—O22—OW1^i	124.33 (7)	O24^v—OW4—O2^x	69.74 (4)
S2—O22—OW4	144.40 (6)	O2—OW4—O2^x	180.0
OW1^i—O22—OW4	80.52 (4)	O22^x—OW4—O21^i	109.45 (4)
S2—O22—N1^viii	100.75 (6)	O22—OW4—O21^i	70.55 (4)
OW1^i—O22—N1^viii	108.67 (5)	O24^i—OW4—O21^i	44.99 (3)
OW4—O22—N1^viii	92.88 (4)	O24^v—OW4—O21^i	135.01 (3)
S2—O23—OW1^viii	122.36 (6)	O2—OW4—O21^i	93.56 (4)
S2—O23—N2	134.88 (7)	O2^x—OW4—O21^i	86.44 (4)
OW1^viii—O23—N2	92.63 (5)	O22^x—OW4—O21^v	70.55 (4)
S2—O23—N1^viii	104.00 (7)	O22—OW4—O21^v	109.45 (4)
OW1^viii—O23—N1^viii	72.39 (5)	O24^i—OW4—O21^v	135.01 (3)
N2—O23—N1^viii	114.01 (6)	O24^v—OW4—O21^v	44.99 (3)
S2—O24—N1^i	141.20 (7)	O2—OW4—O21^v	86.44 (4)
S2—O24—N1^ix	117.49 (6)	O2^x—OW4—O21^v	93.56 (4)
N1^i—O24—N1^ix	88.38 (5)	O21^i—OW4—O21^v	180.0
S2—O24—OW4^iii	108.12 (5)	O22^x—OW4—H41	171.02
N1^i—O24—OW4^iii	95.57 (5)	O22—OW4—H41	8.98
N1^ix—O24—OW4^iii	97.23 (5)	O24^i—OW4—H41	101.01
O24^i—N1—O24^vi	91.62 (5)	O24^v—OW4—H41	78.99
O24^i—N1—OW3^ii	160.04 (7)	O2—OW4—H41	62.55
O24^vi—N1—OW3^ii	79.38 (5)	O2^x—OW4—H41	117.45
O24^i—N1—O12	131.11 (6)	O21^i—OW4—H41	79.31
O24^vi—N1—O12	115.00 (6)	O21^v—OW4—H41	100.69
OW3^ii—N1—O12	68.69 (5)	O22^x—OW4—H42	109.79
O24^i—N1—O2	70.49 (5)	O22—OW4—H42	70.21
O24^vi—N1—O2	136.43 (6)	O24^i—OW4—H42	165.224
OW3^ii—N1—O2	127.78 (6)	O24^v—OW4—H42	14.776
O12—N1—O2	61.90 (4)	O2—OW4—H42	106.02
O24^i—N1—O23^ii	98.26 (5)	O2^x—OW4—H42	73.98
O24^vi—N1—O23^ii	123.17 (6)	O21^i—OW4—H42	123.33
OW3^ii—N1—O23^ii	72.74 (5)	O21^v—OW4—H42	56.67
O12—N1—O23^ii	99.44 (5)	H41—OW4—H42	65.24

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) x+1, y, z+1; (x) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H11···O22^i	0.7727 (9)	1.9424 (11)	2.7103 (15)	172.49 (9)
OW1—H12···O23^ii	0.8025 (9)	1.9922 (11)	2.7939 (15)	176.88 (8)
OW2—H21···O12^iii	0.8035 (11)	1.9784 (13)	2.7620 (17)	164.87 (9)
OW2—H21···OW1	0.8035 (11)	2.6479 (12)	2.7617 (16)	89.60 (8)
OW2—H22···OW3^iii	0.8430 (11)	1.9628 (15)	2.8015 (19)	173.01 (8)
OW3—H31···O1	0.8368 (15)	1.9813 (12)	2.803 (2)	166.83 (12)
OW3—H32···O13^viii	0.9536 (17)	2.2200 (15)	3.171 (2)	174.98 (10)
OW4—H41···O22	0.8936 (2)	2.0483 (12)	2.9263 (14)	167.11 (3)
OW4—H42···O24^v	0.8822 (2)	2.1329 (13)	2.9740 (13)	159.17 (3)
OW4—H42···O21^v	0.8822 (2)	2.8064 (12)	3.1926 (12)	108.10 (3)
N1—H53···O24^i	0.8362 (13)	2.0534 (10)	2.8536 (17)	159.99 (9)
N1—H51···O24^vi	0.7706 (13)	2.1396 (12)	2.8994 (18)	168.82 (10)
N1—H54···OW3^ii	0.8342 (14)	2.5784 (17)	2.902 (2)	104.51 (10)
N1—H52···O12	0.7942 (13)	2.1621 (14)	2.923 (2)	160.61 (10)
N1—H52···O2	0.7942 (13)	2.5891 (13)	3.0488 (19)	118.48 (10)
N1—H54···O23^ii	0.8342 (14)	2.2724 (14)	3.074 (2)	161.35 (9)
N1—H54···O22^ii	0.8342 (14)	2.6245 (13)	3.151 (2)	122.40 (9)
N2—H63···O23	0.7241 (14)	2.1851 (11)	2.8450 (18)	152.03 (13)
N2—H61···O14^iv	0.7869 (15)	2.0752 (14)	2.857 (2)	172.46 (12)
N2—H62···O12^ix	0.8260 (15)	2.0435 (13)	2.862 (2)	170.62 (11)
N2—H64···O13^viii	0.8674 (16)	2.0791 (15)	2.899 (2)	157.46 (10)
N2—H63···O1	0.7241 (14)	2.5386 (12)	3.006 (2)	124.25 (12)
N2—H63···OW3^iii	0.7241 (14)	2.9058 (17)	3.087 (2)	97.63 (13)
N2—H64···O11^viii	0.8674 (16)	2.5675 (11)	3.181 (2)	128.49 (10)
N3—H72···O14	0.8747 (16)	2.0530 (14)	2.805 (2)	143.54 (11)
N3—H74···OW2^iv	0.9709 (17)	2.0948 (11)	2.825 (2)	130.69 (14)
N3—H71···O13^viii	0.8939 (18)	2.0982 (12)	2.923 (2)	153.10 (15)
N3—H72···O1	0.8747 (16)	2.4473 (11)	3.062 (2)	127.71 (12)
N3—H74···O14^vii	0.9709 (17)	2.5170 (19)	3.101 (3)	118.58 (13)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x, y, z−1; (vi) x−1, y, z−1; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) x+1, y, z+1.