Tetra­aqua­(7-hydroxy-5-oxidoflavone-6-sulfonato-κ²O⁴,O⁵)nickel(II) dimethyl­formamide solvate monohydrate

In the title compound, [Ni(C₁₅H₈O₇S)(H₂O)₄]·C₃H₇NO·H₂O, the Ni^II cation is chelated by a 7-hydroxy-5-oxidoflavone-6-sulfonate ligand through one oxide and one carbonyl O atom, and the sixfold coordination is completed by four aqua ligands. Individual mol­ecules are linked into hydrogen-bonded dimers by way of five pairs of O—H...O hydrogen bonds. These dimers, in turn, determine a three-dimensional supra­molecular arrangement through a variety of inter­dimeric inter­actions, such as O—H...O, C—H...O and π–π stacking.

S1. Comment

Flavonoids (2-phenylbenzo-γ-pyrones) are a broad class of polyphenolic secondary metabolites abundant in vascular plants and in a variety of edible vegetables, such as apples, soy, onions and tea (Zheng et al., 2003). They possess a number of pharmacological properties, including anti-oxidant, anticancer, antiviral and anti-inflammatory (Bertrand & Oliver, 1999). Chrysin, a naturally occurring and widely distributed flavone, has been reported to have many different biological activities, such as anti-oxidant (Chan et al., 2000), antivirus (Zheng et al., 2003), antidiabetogenic (Sternsdorf et al., 1997) and anti-anxiolytic (Shin et al., 1999). Furthermore, chrysin has demonstrated anticancer activities (Liu et al., 1992; Hebtemariam, 1997). Owing to the particularities of its carbonyl and hydroxyl groups, chrysin or chrysinsulfonate is able to coordinate with some metal ions (Puse & Nikta, 1997, 2000; Puse et al., 2001, 2003; Zhang et al., 2004b). We report here the crystal structure of a nickel(II) complex of chrysin-6-sulfonate, namely tetraaqua(5,7-dihydroxyflavone-6-sulfonate-κ²O,O')nickel(II) dimethylformamide solvate monohydrate, (I).

The compound consists of an Ni^II center sixfold coordinated by a chelating 5-(hydroxy anion)-7-hydroxyflavone-6-sulfonate ligand plus four coordinated water molecules, and is stabilized by a solvent dimethylformamide molecule and a solvent water molecule (Fig. 1). The ligand possesses a flavone skeleton, and the bond lengths and bond angles are in agreement with those reported for flavone (Waller et al., 2003). The benzopyranone system consists of ring A (C1–C6) and ring C (O7/C5–C9), which are planar [the mean deviation from the least-squares planes is 0.050 (2) Å] and subtend a dihedral angle of 5.4 (1)°. The planes of ring B (C10–C15) and ring C, in turn, make an angle of 8.3 (1)°, which shows that the flavone skeleton deviates only slightly from planarity; the overall mean deviation from the least-squares planes is 0.098 (3) Å. The Ni^II cation is coordinated by six O atoms (O1–O6) from the carbonyl and hydroxy groups of the chelating 5-(hydroxy anion)-7-hydroxyflavone-6-sulfonate ligand and from four coordinated water molecules, defining a slightly distorted octahedron. The range of the Ni—O bond lengths is 1.9995 (17)–2.1149 (19) Å (Table 1), and can be considered as normal (Chen & Wen, 2004).

The S—O distances and angles in (I) have similar values, suggesting that the negative charge is delocalized over the three sulfonate O atoms, thus giving some shared double-bond character to the whole group (Zhang et al., 2004a). The S1—O9 bond is slightly longer than the S1—O10 and S1—O11 values, owing to the O8—H8A···O9 intramolecular hydrogen bond between the 7-hydroxy and sulfonate groups in the ligand (first entry in Table 2, and Fig. 1).

There are three hydrogen bonds linking the main molecule and the water and dimethylformamide solvent molecules into a group (entries 2–4 in Table 2, and Fig. 1); these groups, in turn, are connected into well defined hydrogen-bonded dimers by way of five pairs of (O—H)_aqua···O hydrogen bonds (entries 5–9 in Table 2, and Fig. 1).

Finally, a neat three-dimensional supramolecular structure arises from a variety of interdimeric interactions, the most relevant of which are the hydrogen bonds presented in Table 2 as entries 10–13, and a stacking contact between the AC ring system and ring B, with a centroid–centroid distance [Cg_AC···Cg_B(−x + 2, −y + 1, −z + 1); Fig. 2] of 3.708 (2) Å and a mean slippage angle of 15 (2)°.

In the process, some interesting hydrogen-bonded structures build up, such as the R₅⁵(10) synthon (Etter, 1990) determined by atoms O12, O5, O13, O4^iv and O6ⁱⁱⁱ and shown in Fig. 2, and the R₂²(12) motif defined by the 10t h and 11t h hydrogen bonds in Table 2 and shown in Fig. 3.

S2. Experimental

Chrysin (2.0 g) was added with stirring to a concentrated sulfuric acid solution (10 ml) at 353 K for 12 h. After cooling to room temperature, it was poured into an aqueous solution of saturated sodium chloride (100 ml) and a yellow precipitate began to appear. After 2 h, the yellow precipitate was filtered off and washed with a saturated sodium chloride solution until the pH of the filtrate was 7. It was then dissolved in a buffer solution of NH₄Cl–NH₃·H₂O (pH = 10, 100 ml) and mixed with a saturated NiSO₄ solution (10 ml), at which point a green precipitate appeared. This was filtrated and added to boiling water (50 ml) (some of the green precipitate could not be dissolved). The solution was filtrated and recrystallized in a 95% DMF (v/v) solution, from which (I) was obtained (yield 62.8%). Analysis calculated for C₁₈H₂₅NNiO₁₃S: C 38.99, H 4.51, N 2.53%; found: C 38.76, H 4.54, N 2.45%. IR (KBr disk; cm⁻¹): 3365 (br, v), 1638 (s), 1599 (s), 1546 (s), 1450 (s), 1379 (s), 1168 (br, v), 1150 (s), 1029 (s), 926, 774, 590.

S3. Refinement

All H atoms, except methyl H atoms, were found in difference maps. H atoms bonded to C atoms were placed in calculated positions (C—H = 0.93 and 0.96 Å) and refined as riding, allowing for free rotation of the rigid methyl groups; U_iso(H) values were constrained to be 1.2 or 1.5 times U_eq(C). The positions of O-bound H atoms were refined freely (hydroxy group) or with distance restraints (water molecules), with U_iso(H) set at 0.08 Ų. Please check changes to text.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. : Part of the crystal structure of (I), showing the numbering scheme, the hydrogen-bonded dimer and intermolecular iteractions. Displacement ellipsoids are drawn at the 30% probability level. For clarity, some H atoms have been omitted. Thin dashed lines indicate the hydrogen-bonding interactions. [Symmetry code (i), see Table 2.]
	Fig. 2. : A view of the packing of (I), showing some of the hydrogen bonds, the π–π stacking interactions and the R5^5(10) synthon. For clarity, H atoms have been omitted. Thin dashed lines indicate hydrogen-bonding and π–π stacking interactions. CgAC and CgB are the centroids of the C1–C9/O7 ring system and the C10–C15 ring, respectively. [Symmetry codes: (v) −x + 2, −y + 1, −z + 1; for (iii) and (iv), see Table 2.]
	Fig. 3. : A complementary packing view of (I), showing the remaining hydorgen bonds and the resulting supramolecular R2^2(12) synthon. Thin dashed lines indicate the hydrogen bonding. [Symmetry code (ii), see Table 2.]

Tetraaqua(5,7-dihydroxyflavone-6-sulfonate-κ²O⁴,O⁵)nickel(II) dimethylformamide solvate monohydrate

Crystal data

[Ni(C15H8O7S)(H2O)4]·C3H7NO·H2O	F(000) = 1152
Mr = 554.16	Dx = 1.569 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2739 reflections
a = 7.876 (2) Å	θ = 2.6–25.3°
b = 15.594 (4) Å	µ = 0.98 mm^−1
c = 19.136 (5) Å	T = 298 K
β = 93.214 (5)°	Block, green
V = 2346.6 (10) Å^3	0.36 × 0.26 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4182 independent reflections
Radiation source: fine-focus sealed tube	3060 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→8
Tmin = 0.717, Tmax = 0.898	k = −17→18
11820 measured reflections	l = −14→22

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.04P] where P = (Fo^2 + 2Fc^2)/3
4182 reflections	(Δ/σ)max = 0.008
342 parameters	Δρmax = 0.46 e Å^−3
12 restraints	Δρmin = −0.31 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
Ni1	0.84573 (4)	0.890643 (19)	0.435940 (15)	0.03092 (11)
N1	0.3867 (3)	0.67843 (16)	0.32050 (13)	0.0560 (7)
O1	0.8865 (2)	0.76825 (10)	0.41063 (8)	0.0403 (4)
O2	0.9178 (2)	0.86428 (10)	0.53568 (8)	0.0340 (4)
O3	0.7630 (3)	0.92156 (12)	0.33393 (9)	0.0413 (5)
O4	0.8046 (2)	1.01786 (11)	0.45829 (9)	0.0349 (4)
O5	0.5983 (3)	0.86151 (16)	0.45611 (11)	0.0581 (6)
O6	1.0977 (2)	0.92063 (11)	0.41185 (10)	0.0369 (4)
O7	0.7871 (2)	0.56216 (10)	0.53235 (9)	0.0450 (5)
O8	0.8826 (3)	0.70036 (12)	0.74466 (10)	0.0554 (6)
O9	0.9502 (2)	0.85724 (11)	0.76199 (8)	0.0454 (5)
O10	1.1106 (2)	0.91237 (11)	0.66806 (9)	0.0414 (4)
O11	0.8125 (2)	0.94433 (11)	0.67114 (9)	0.0453 (5)
O12	0.3116 (3)	0.80491 (14)	0.36600 (12)	0.0658 (6)
S1	0.94601 (8)	0.88206 (4)	0.68808 (3)	0.03457 (17)
C1	0.8910 (3)	0.79212 (15)	0.56606 (12)	0.0301 (6)
C2	0.8983 (3)	0.78698 (15)	0.64041 (12)	0.0307 (6)
C3	0.8705 (3)	0.70958 (16)	0.67445 (13)	0.0385 (6)
C4	0.8278 (4)	0.63615 (16)	0.63658 (13)	0.0451 (7)
H4	0.8024	0.5855	0.6594	0.054*
C5	0.8237 (3)	0.63962 (16)	0.56502 (13)	0.0374 (6)
C6	0.8563 (3)	0.71392 (15)	0.52708 (12)	0.0319 (6)
C7	0.8609 (3)	0.70703 (16)	0.45245 (13)	0.0357 (6)
C8	0.8342 (3)	0.62331 (16)	0.42304 (13)	0.0420 (7)
H8	0.8453	0.6158	0.3753	0.050*
C9	0.7938 (3)	0.55530 (16)	0.46181 (14)	0.0391 (6)
C10	0.7488 (3)	0.46850 (17)	0.43588 (14)	0.0425 (7)
C11	0.6896 (5)	0.40693 (19)	0.48015 (18)	0.0727 (11)
H11	0.6788	0.4198	0.5271	0.087*
C12	0.6460 (5)	0.3261 (2)	0.4552 (2)	0.0887 (13)
H12	0.6045	0.2854	0.4853	0.106*
C13	0.6635 (5)	0.3060 (2)	0.3871 (2)	0.0760 (11)
H13	0.6372	0.2510	0.3711	0.091*
C14	0.7201 (4)	0.3665 (2)	0.34159 (19)	0.0721 (10)
H14	0.7295	0.3532	0.2946	0.086*
C15	0.7628 (4)	0.44741 (19)	0.36640 (16)	0.0585 (8)
H15	0.8015	0.4883	0.3357	0.070*
C17	0.3538 (5)	0.5866 (2)	0.3149 (2)	0.0934 (14)
H17A	0.2432	0.5743	0.3310	0.140*
H17B	0.4383	0.5559	0.3430	0.140*
H17C	0.3583	0.5692	0.2669	0.140*
C18	0.5328 (4)	0.7139 (3)	0.28944 (19)	0.0864 (12)
H18A	0.5262	0.7753	0.2902	0.130*
H18B	0.5358	0.6944	0.2419	0.130*
H18C	0.6341	0.6955	0.3154	0.130*
C16	0.2868 (4)	0.7282 (2)	0.35455 (17)	0.0595 (9)
H16	0.1894	0.7038	0.3714	0.071*
O13	0.5144 (3)	0.90243 (18)	0.58480 (13)	0.0838 (8)
H4B	0.818 (4)	1.035 (2)	0.4990 (10)	0.080*
H6A	1.152 (4)	0.8775 (15)	0.4018 (17)	0.080*
H3A	0.796 (4)	0.9713 (14)	0.3214 (16)	0.080*
H6B	1.113 (4)	0.9634 (16)	0.3844 (15)	0.080*
H8A	0.914 (4)	0.742 (2)	0.7618 (18)	0.080*
H4A	0.858 (4)	1.0477 (19)	0.4324 (15)	0.080*
H3B	0.801 (4)	0.8835 (17)	0.3079 (15)	0.080*
H5B	0.527 (3)	0.856 (2)	0.4244 (13)	0.080*
H5A	0.568 (4)	0.881 (2)	0.4942 (12)	0.080*
H13B	0.602 (3)	0.9242 (19)	0.6089 (16)	0.080*
H13A	0.442 (3)	0.9443 (16)	0.5947 (12)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0416 (2)	0.02603 (19)	0.02525 (18)	−0.00306 (14)	0.00335 (14)	0.00036 (13)
N1	0.0523 (15)	0.0539 (17)	0.0604 (17)	0.0109 (13)	−0.0090 (13)	−0.0176 (13)
O1	0.0677 (12)	0.0260 (10)	0.0279 (10)	−0.0046 (9)	0.0093 (9)	0.0010 (7)
O2	0.0509 (10)	0.0252 (9)	0.0262 (9)	−0.0059 (8)	0.0033 (8)	0.0026 (7)
O3	0.0592 (12)	0.0328 (11)	0.0317 (11)	−0.0014 (9)	0.0004 (9)	−0.0011 (8)
O4	0.0427 (10)	0.0292 (10)	0.0331 (10)	−0.0021 (8)	0.0057 (9)	0.0001 (8)
O5	0.0477 (13)	0.0813 (16)	0.0457 (13)	−0.0174 (11)	0.0055 (10)	−0.0052 (12)
O6	0.0448 (11)	0.0278 (10)	0.0387 (11)	0.0014 (8)	0.0083 (9)	0.0009 (8)
O7	0.0739 (13)	0.0264 (10)	0.0347 (11)	−0.0096 (9)	0.0024 (10)	−0.0002 (8)
O8	0.1061 (17)	0.0341 (11)	0.0265 (11)	−0.0152 (12)	0.0063 (11)	0.0042 (8)
O9	0.0736 (13)	0.0369 (11)	0.0264 (10)	−0.0108 (9)	0.0082 (9)	0.0005 (8)
O10	0.0504 (11)	0.0404 (11)	0.0336 (10)	−0.0132 (8)	0.0048 (9)	0.0011 (8)
O11	0.0594 (12)	0.0339 (11)	0.0432 (11)	0.0078 (9)	0.0075 (9)	−0.0024 (8)
O12	0.0568 (13)	0.0533 (15)	0.0883 (17)	0.0020 (11)	0.0114 (12)	−0.0212 (12)
S1	0.0505 (4)	0.0281 (4)	0.0255 (3)	−0.0038 (3)	0.0060 (3)	−0.0005 (3)
C1	0.0348 (13)	0.0250 (13)	0.0303 (14)	−0.0007 (11)	0.0019 (11)	0.0024 (10)
C2	0.0420 (15)	0.0236 (13)	0.0272 (14)	−0.0013 (11)	0.0069 (11)	0.0000 (10)
C3	0.0561 (17)	0.0321 (15)	0.0278 (15)	−0.0021 (13)	0.0071 (13)	0.0024 (11)
C4	0.075 (2)	0.0268 (15)	0.0341 (16)	−0.0070 (13)	0.0047 (15)	0.0064 (11)
C5	0.0514 (16)	0.0250 (14)	0.0355 (15)	−0.0032 (12)	0.0009 (13)	−0.0020 (11)
C6	0.0424 (14)	0.0245 (13)	0.0290 (14)	−0.0023 (11)	0.0036 (12)	0.0015 (10)
C7	0.0455 (15)	0.0294 (15)	0.0325 (15)	−0.0015 (12)	0.0048 (12)	−0.0022 (11)
C8	0.0646 (19)	0.0309 (16)	0.0310 (15)	−0.0041 (13)	0.0074 (14)	−0.0046 (11)
C9	0.0487 (16)	0.0325 (15)	0.0360 (15)	0.0009 (12)	0.0003 (13)	−0.0035 (12)
C10	0.0514 (17)	0.0304 (15)	0.0451 (17)	−0.0020 (13)	−0.0030 (14)	−0.0038 (12)
C11	0.125 (3)	0.0394 (19)	0.053 (2)	−0.0240 (19)	−0.001 (2)	−0.0005 (15)
C12	0.149 (4)	0.039 (2)	0.075 (3)	−0.032 (2)	−0.020 (3)	0.0056 (18)
C13	0.101 (3)	0.038 (2)	0.086 (3)	−0.0097 (19)	−0.016 (2)	−0.0207 (19)
C14	0.095 (3)	0.053 (2)	0.068 (2)	−0.0133 (19)	0.006 (2)	−0.0289 (18)
C15	0.075 (2)	0.0447 (19)	0.056 (2)	−0.0066 (16)	0.0093 (17)	−0.0131 (15)
C17	0.104 (3)	0.056 (2)	0.115 (3)	0.014 (2)	−0.041 (3)	−0.027 (2)
C18	0.070 (2)	0.108 (3)	0.083 (3)	0.026 (2)	0.018 (2)	0.004 (2)
C16	0.0463 (18)	0.058 (2)	0.074 (2)	0.0032 (16)	−0.0012 (17)	−0.0095 (18)
O13	0.0574 (15)	0.118 (2)	0.0754 (18)	0.0264 (15)	−0.0005 (13)	−0.0253 (15)

Geometric parameters (Å, º)

Ni1—O1	1.9995 (17)	C2—C3	1.395 (3)
Ni1—O2	2.0031 (16)	C3—C4	1.386 (3)
Ni1—O4	2.0588 (19)	C4—C5	1.369 (3)
Ni1—O5	2.059 (2)	C4—H4	0.9300
Ni1—O3	2.0796 (19)	C5—C6	1.399 (3)
Ni1—O6	2.1149 (19)	C6—C7	1.435 (3)
N1—C16	1.306 (4)	C7—C8	1.433 (3)
N1—C18	1.435 (4)	C8—C9	1.343 (3)
N1—C17	1.458 (4)	C8—H8	0.9300
O1—C7	1.269 (3)	C9—C10	1.478 (3)
O2—C1	1.289 (3)	C10—C11	1.379 (4)
O3—H3A	0.856 (18)	C10—C15	1.380 (4)
O3—H3B	0.842 (18)	C11—C12	1.384 (4)
O4—H4B	0.826 (17)	C11—H11	0.9300
O4—H4A	0.815 (18)	C12—C13	1.355 (5)
O5—H5B	0.806 (17)	C12—H12	0.9300
O5—H5A	0.834 (18)	C13—C14	1.376 (5)
O6—H6A	0.824 (17)	C13—H13	0.9300
O6—H6B	0.862 (18)	C14—C15	1.383 (4)
O7—C9	1.358 (3)	C14—H14	0.9300
O7—C5	1.383 (3)	C15—H15	0.9300
O8—C3	1.349 (3)	C17—H17A	0.9600
O8—H8A	0.77 (3)	C17—H17B	0.9600
O9—S1	1.4649 (17)	C17—H17C	0.9600
O10—S1	1.4516 (18)	C18—H18A	0.9600
O11—S1	1.4541 (18)	C18—H18B	0.9600
O12—C16	1.230 (4)	C18—H18C	0.9600
S1—C2	1.770 (2)	C16—H16	0.9300
C1—C2	1.423 (3)	O13—H13B	0.877 (17)
C1—C6	1.448 (3)	O13—H13A	0.892 (15)
O1—Ni1—O2	89.67 (7)	C3—C4—H4	120.6
O1—Ni1—O4	177.94 (7)	C4—C5—O7	114.2 (2)
O2—Ni1—O4	92.25 (7)	C4—C5—C6	123.9 (2)
O1—Ni1—O5	90.07 (9)	O7—C5—C6	121.9 (2)
O2—Ni1—O5	89.81 (8)	C5—C6—C7	118.1 (2)
O4—Ni1—O5	90.69 (9)	C5—C6—C1	117.7 (2)
O1—Ni1—O3	92.29 (7)	C7—C6—C1	124.2 (2)
O2—Ni1—O3	177.53 (7)	O1—C7—C8	117.6 (2)
O4—Ni1—O3	85.81 (7)	O1—C7—C6	125.8 (2)
O5—Ni1—O3	88.68 (8)	C8—C7—C6	116.6 (2)
O1—Ni1—O6	89.60 (7)	C9—C8—C7	122.5 (2)
O2—Ni1—O6	91.95 (7)	C9—C8—H8	118.8
O4—Ni1—O6	89.58 (7)	C7—C8—H8	118.8
O5—Ni1—O6	178.21 (8)	C8—C9—O7	120.7 (2)
O3—Ni1—O6	89.58 (8)	C8—C9—C10	126.7 (2)
C16—N1—C18	119.9 (3)	O7—C9—C10	112.6 (2)
C16—N1—C17	120.7 (3)	C11—C10—C15	118.3 (3)
C18—N1—C17	119.4 (3)	C11—C10—C9	121.0 (3)
C7—O1—Ni1	122.15 (16)	C15—C10—C9	120.7 (3)
C1—O2—Ni1	124.34 (15)	C10—C11—C12	120.5 (3)
Ni1—O3—H3A	113 (2)	C10—C11—H11	119.7
Ni1—O3—H3B	107 (2)	C12—C11—H11	119.7
H3A—O3—H3B	110 (3)	C13—C12—C11	120.4 (3)
Ni1—O4—H4B	120 (2)	C13—C12—H12	119.8
Ni1—O4—H4A	109 (2)	C11—C12—H12	119.8
H4B—O4—H4A	110 (3)	C12—C13—C14	120.2 (3)
Ni1—O5—H5B	120 (2)	C12—C13—H13	119.9
Ni1—O5—H5A	114 (2)	C14—C13—H13	119.9
H5B—O5—H5A	119 (4)	C13—C14—C15	119.4 (3)
Ni1—O6—H6A	112 (2)	C13—C14—H14	120.3
Ni1—O6—H6B	118 (2)	C15—C14—H14	120.3
H6A—O6—H6B	114 (3)	C10—C15—C14	121.2 (3)
C9—O7—C5	119.95 (19)	C10—C15—H15	119.4
C3—O8—H8A	110 (3)	C14—C15—H15	119.4
O10—S1—O11	111.65 (11)	N1—C17—H17A	109.5
O10—S1—O9	111.63 (11)	N1—C17—H17B	109.5
O11—S1—O9	111.63 (11)	H17A—C17—H17B	109.5
O10—S1—C2	107.68 (11)	N1—C17—H17C	109.5
O11—S1—C2	108.33 (11)	H17A—C17—H17C	109.5
O9—S1—C2	105.60 (11)	H17B—C17—H17C	109.5
O2—C1—C2	120.1 (2)	N1—C18—H18A	109.5
O2—C1—C6	122.3 (2)	N1—C18—H18B	109.5
C2—C1—C6	117.6 (2)	H18A—C18—H18B	109.5
C3—C2—C1	121.1 (2)	N1—C18—H18C	109.5
C3—C2—S1	121.24 (18)	H18A—C18—H18C	109.5
C1—C2—S1	117.62 (17)	H18B—C18—H18C	109.5
O8—C3—C4	115.7 (2)	O12—C16—N1	124.9 (3)
O8—C3—C2	123.6 (2)	O12—C16—H16	117.5
C4—C3—C2	120.7 (2)	N1—C16—H16	117.5
C5—C4—C3	118.8 (2)	H13B—O13—H13A	95.6 (19)
C5—C4—H4	120.6
O2—Ni1—O1—C7	33.53 (19)	C4—C5—C6—C1	−2.0 (4)
O5—Ni1—O1—C7	−56.3 (2)	O7—C5—C6—C1	179.1 (2)
O3—Ni1—O1—C7	−144.96 (19)	O2—C1—C6—C5	−178.0 (2)
O6—Ni1—O1—C7	125.48 (19)	C2—C1—C6—C5	3.2 (3)
O1—Ni1—O2—C1	−33.55 (18)	O2—C1—C6—C7	5.0 (4)
O4—Ni1—O2—C1	147.21 (18)	C2—C1—C6—C7	−173.8 (2)
O5—Ni1—O2—C1	56.52 (19)	Ni1—O1—C7—C8	158.20 (18)
O6—Ni1—O2—C1	−123.13 (18)	Ni1—O1—C7—C6	−21.8 (3)
Ni1—O2—C1—C2	−160.82 (17)	C5—C6—C7—O1	179.0 (2)
Ni1—O2—C1—C6	20.4 (3)	C1—C6—C7—O1	−4.0 (4)
O2—C1—C2—C3	−179.7 (2)	C5—C6—C7—C8	−1.0 (4)
C6—C1—C2—C3	−0.9 (4)	C1—C6—C7—C8	176.0 (2)
O2—C1—C2—S1	−0.4 (3)	O1—C7—C8—C9	−175.0 (2)
C6—C1—C2—S1	178.46 (17)	C6—C7—C8—C9	5.0 (4)
O10—S1—C2—C3	120.5 (2)	C7—C8—C9—O7	−4.2 (4)
O11—S1—C2—C3	−118.6 (2)	C7—C8—C9—C10	174.1 (2)
O9—S1—C2—C3	1.1 (2)	C5—O7—C9—C8	−0.7 (4)
O10—S1—C2—C1	−58.9 (2)	C5—O7—C9—C10	−179.3 (2)
O11—S1—C2—C1	62.0 (2)	C8—C9—C10—C11	−171.9 (3)
O9—S1—C2—C1	−178.25 (18)	O7—C9—C10—C11	6.6 (4)
C1—C2—C3—O8	177.2 (2)	C8—C9—C10—C15	7.1 (5)
S1—C2—C3—O8	−2.1 (4)	O7—C9—C10—C15	−174.4 (3)
C1—C2—C3—C4	−2.8 (4)	C15—C10—C11—C12	0.2 (5)
S1—C2—C3—C4	177.9 (2)	C9—C10—C11—C12	179.3 (3)
O8—C3—C4—C5	−176.0 (2)	C10—C11—C12—C13	1.0 (6)
C2—C3—C4—C5	4.0 (4)	C11—C12—C13—C14	−1.9 (6)
C3—C4—C5—O7	177.3 (2)	C12—C13—C14—C15	1.6 (6)
C3—C4—C5—C6	−1.6 (4)	C11—C10—C15—C14	−0.6 (5)
C9—O7—C5—C4	−174.3 (2)	C9—C10—C15—C14	−179.6 (3)
C9—O7—C5—C6	4.7 (4)	C13—C14—C15—C10	−0.3 (5)
C4—C5—C6—C7	175.2 (3)	C18—N1—C16—O12	−4.0 (5)
O7—C5—C6—C7	−3.7 (4)	C17—N1—C16—O12	174.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O9	0.77 (3)	1.81 (3)	2.522 (2)	153 (4)
O5—H5B···O12	0.81 (2)	2.14 (2)	2.900 (3)	159 (3)
O5—H5A···O13	0.83 (2)	1.84 (2)	2.663 (3)	169 (3)
O13—H13B···O11	0.88 (2)	2.01 (2)	2.870 (3)	166 (3)
O3—H3A···O10^i	0.86 (2)	1.96 (2)	2.775 (3)	158 (3)
O4—H4A···O10^i	0.82 (2)	2.05 (2)	2.767 (2)	147 (3)
O4—H4A···O2^i	0.82 (2)	2.29 (3)	2.854 (2)	127 (3)
O4—H4B···O6^i	0.83 (2)	1.92 (2)	2.734 (3)	167 (3)
O6—H6B···O11^i	0.86 (2)	1.90 (2)	2.754 (3)	170 (3)
O3—H3B···O8^ii	0.84 (2)	1.92 (2)	2.757 (3)	177 (3)
C8—H8···O9^ii	0.93	2.40	3.277 (3)	157
O6—H6A···O12^iii	0.82 (2)	1.85 (2)	2.652 (3)	163 (3)
O13—H13A···O4^iv	0.89 (2)	2.22 (2)	2.882 (3)	130 (2)

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