Two new transition metal inorganic–organic hybrid borates: [tris­(2-amino­eth­oxy)trihy­droxy­hexa­borato]­cobalt(II) and its nickel(II) analogue

The two isomorphous title compounds, [1,5,9-tris­(2-aminoeth­oxy)-3,7,11-trihy­droxy-3,7,11-tribora-1,5,9-triborata-2,4,6,8,10,12-hexa­oxa-13-oxoniatricyclo­[7.3.1.0^5,13]trideca­ne]­co­balt(II), [Co(C₆H₂₁B₆N₃O₁₃)] or Co{B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}, and the Ni^II analogue, [Ni(C₆H₂₁B₆N₃O₁₃)], each consist of an M^II cation and an inorganic–organic hybrid {B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}²⁻ anion. The M^II cation lies on a crystallographic threefold axis (as does one O atom) and is octa­hedrally coordinated by three N atoms from the organic component. Three O atoms covalently link the B–O cluster and the organic component. Mol­ecules are connected to one another through N—H...O and O—H...O hydrogen bonds, forming a three-dimensional supra­molecular network.

S1. Comment

[AUTHOR: Extensive changes to text below - please check.] In recent decades, borate materials have been extensively studied because of their rich structural chemistry and potential applications, especially in mineralogy, nonlinear optics and photoluminescence (Christ & Clark, 1977; Heller, 1986; Becker, 1998; Burns, 1995; Grice et al., 1999; Chen et al., 1995; Sasaki et al., 2000; Lin et al., 2007). The synthesis of new inorganic–organic hybrid compounds is a relatively new research area, which has been growing rapidly in recent years. In the search for useful inorganic–organic borate materials, the synthesis and structure of the metallo-organically templated borates have been investigated: examples include [Cu(en)₂][B₇O₁₃H₃]_n (en is ethylenediamine; Sung et al., 2000), [Mn(C₁₀H₁₈N₆)][B₅O₆(OH)₄]₂ (Zhang et al., 2004), [Ni(C₄H₁₀N₂)(C₂H₈N₂)₂][B₅O₆(OH)₄]₂ (Liu et al., 2006), [Zn(dien)₂][B₅O₆(OH)₄]₂ and [B₅O₇(OH)₃Zn(tren)] [dien is diethylenetriamine and tren is tris(2-aminoethyl)amine; Wang et al., 2005], [Ag(py)₂]₂[B₁₀O₁₄(OH)₄] (py is pyridine; Wang et al., 2008), [Zn(C₂H₃O₂)(C₆H₁₈N₄)][B₅O₆(OH)₄] (Wu et al., 2009) and [Cd(TETA)(C₂H₃O₂)][B₅O₆(OH)₄] (TETA is triethylenetetramine; Yang et al., 2011). These compounds usually contain isolated or layered boron polyanion hosts and interstitial transition metal complex cations. We describe herein the synthesis and crystal structures of two novel inorganic–organic hybrid borates, M{B₆O₇(OH)₃[O(CH₂)₂NH₂]₃} [M = Co^II, (I), or Ni^II, (II)].

Compounds (I) and (II) (see Scheme) were obtained under mild solvothermal conditions. Both compounds crystallize in the cubic system (space group Pa3) and they are isomorphous (Figs. 1a and 1b). Each compound consists of an inorganic–organic hybrid anion {B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}^2- and an M^II cation residing on a crystallographic threefold axis. The M^II cation is octahedrally coordinated by three N atoms from the organic component, and three O atoms covalently linking the B—O cluster and organic component (Figs. 1a and 1b). The three M—N bond lengths [2.1309 (15) Å for (I) and 2.080 (3) Å for (II)] are equivalent by symmetry. The N—M—N angles are 100.11 (6)° for (I) and 98.7 (13)° for (II). The three M—O bond lengths are equivalent by symmetry, viz. 2.1359 (12) Å for (I) and 2.102 (3) Å for (II). These structural differences between (I) and (II) may be attributed to the different ionic radii of the Co^II and Ni^II cations. [##AUTHOR: Please specify these ionic radii and provide a reference for them]

The hexaborate anion (see Scheme), B₆O₇(OH)₆^2-, found in aksaite, mcallisterite and rivadavite (Hanic et al., 1971; Dal Negro et al., 1969, 1971;Dal Negro & Ungaretti, 1973), is a common fundamental building block in borates. The {B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}^2- anion in (I) can be regarded as resulting from the dehydration reaction of three 2-aminoethanol molecules with the three hydroxy groups attached to the four-coordinate B atoms in B₆O₇(OH)₆^2-, to form an isolated cage-like structure. The B—O cluster moiety in {B₆O₇(OH)₃[O(CH₂)₂NH₂]₃}^2- is composed of three trigonal BO₃ units and three BO₄ tetrahedra linked to each other. This B—O cluster is characterized by three [B₃O₃] rings linked by three shared BO₄ tetrahedra and a central common O atom (O5) which lies on a crystallographic threefold axis. Each ring is produced by two shared BO₄ tetrahedra and one trigonal BO₃ unit. The trigonally coordinated B atoms have B—O distances in the range 1.355 (2)–1.379 (2) Å, similar to those observed in the hexaborate anion B₆O₇(OH)₆^2- [B—O = 1.343 (6)–1.398 (1) Å; Genkina et al., 1976; Dal Negro et al., 1971]. The tetrahedral B atoms have longer B—O distances [1.436 (5)–1.5179 (16) Å], lengths that are also comparable with those reported for B₆O₇(OH)₆^2- [B—O = 1.445 (5)–1.517 (2) Å; Genkina et al., 1976; Dal Negro et al., 1971]. The O—B—O angles of the trigonal BO₃ units lie in the range 115.86 (15)–122.47 (15)° and those of the BO₄ tetrahedra are in the range 105.35 (3)–113.0 (3)° (see Tables 1 and 3). The esterification of B₆O₇(OH)₆^2- with 2-aminoethanol shows no substantial influence on the structure of the B—O cluster moiety. It is interesting to compare compound (I) with a 2-aminoethanol borate, i.e. [HOCH₂CH₂NH₃][B₅O₆(OH)₄].H₂O, obtained from a 2-aminoethanol–boric acid solution containing a significant excess of boric acid (Schubert et al., 2008). In this example, 2-aminoethanol is protonated. However, under the present reaction conditions with a large excess of 2-aminoethanol, the free base 2-aminoethanol can react with the B—O cluster anion to form a borate ester analogue.

Molecules are connected via N—H···O and O—H···O hydrogen bonds in both (I) and (II) (Fig. 2), forming three-dimensional supramolecular networks. Hydrogen-bonding parameters for (I) and (II) are listed in Tables 2 and 4, respectively.

Related literature

For related literature, see: Becker (1998); Burns (1995); Chen et al. (1995); Christ & Clark (1977); Dal Negro & Ungaretti (1973); Dal Negro, Sabelli & Ungaretti (1969); Dal Negro, Ungaretti & Sabelli (1971); Genkina et al. (1976); Grice et al. (1999); Hanic et al. (1971); Heller (1986); Lin et al. (2007); Liu et al. (2006); Sasaki et al. (2000); Schubert et al. (2008); Sung et al. (2000); Wang et al. (2005, 2008); Wu et al. (2009); Yang et al. (2011); Zhang et al. (2004).

S2. Experimental

Compounds (I) and (II) were prepared under mild solvothermal conditions. For the synthesis of (I), typically Co(CH₃COO)₂.4H₂O (1 mmol, 248 mg), H₃BO₃ (6 mmol, 368 mg) and H₂O (0.6 ml) were placed in a Teflon-lined autoclave and stirred at room temperature, then 2-aminoethanol (3 ml) was added and thorough mixing was carried out. The mixture was heated to 453 K for 3 d, and then cooled to room temperature at a rate of 5 K h^-1. Pale-pink crystals of (I) were obtained. For the synthesis of (II), the same procedure was used, but using Ni(CH₃COO)₂.4H₂O (1 mmol, 248 mg) in place of Co(CH₃COO)₂.4H₂O to yield blue block-shaped crystals of (II).

S3. Refinement

All C- and N-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and N—H = 0.90 Å and with U_iso(H) = 1.2U_eq(C or N). H atoms attached to O atoms were located in a difference Fourier map and refined using a riding model, with U_iso(H) = 1.2U_eq(O)

Computing details

For both compounds, data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structures of (a) (I) and (b) (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 45% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) y, z, x; (ii) z, x, y.]
	Fig. 2. A view of the packing structure of (I) down the a axis. Dashed lines indicate hydrogen bonds.

(I) [1,5,9-tris(2-aminoethoxy)-3,7,11-trihydroxy- 3,7,11-tribora-1,5,9-triborata-2,4,6,8,10,12-hexaoxa-13- oxoniatricyclo[7.3.1.0^5,13]tridecane]cobalt(II)

Crystal data

[Co(C6H21B6N3O13)]	Dx = 1.739 Mg m^−3
Mr = 467.05	Mo Kα radiation, λ = 0.71073 Å
Cubic, Pa3	Cell parameters from 25748 reflections
Hall symbol: -P 2ac 2ab 3	θ = 3.3–25.0°
a = 15.2796 (18) Å	µ = 1.04 mm^−1
V = 3567.3 (7) Å^3	T = 293 K
Z = 8	Block, pale pink
F(000) = 1912	0.34 × 0.32 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	1057 independent reflections
Radiation source: fine-focus sealed tube	1025 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 0 pixels mm^-1	θmax = 25.0°, θmin = 3.3°
ω scans	h = −18→17
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	k = −18→18
Tmin = 0.710, Tmax = 0.756	l = −18→18
25748 measured reflections

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 1.702P] where P = (Fo^2 + 2Fc^2)/3
1057 reflections	(Δ/σ)max < 0.001
91 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Co1	0.131061 (13)	0.131061 (13)	0.131061 (13)	0.02009 (15)
O1	0.32642 (7)	0.12440 (6)	0.30563 (7)	0.0201 (2)
O2	0.26659 (7)	0.11257 (7)	0.15998 (7)	0.0213 (2)
O3	0.38769 (6)	0.21073 (7)	0.19145 (7)	0.0217 (3)
O4	0.31865 (8)	0.10226 (8)	0.45622 (7)	0.0269 (3)
O5	0.24263 (6)	0.24263 (6)	0.24263 (6)	0.0153 (3)
B1	0.30894 (10)	0.17090 (10)	0.22458 (10)	0.0172 (3)
B2	0.28342 (12)	0.14069 (10)	0.38326 (11)	0.0191 (3)
N1	0.17831 (10)	0.09872 (10)	0.00375 (9)	0.0318 (3)
C1	0.31151 (11)	0.07367 (11)	0.08804 (10)	0.0290 (4)
C2	0.27420 (12)	0.10950 (13)	0.00365 (11)	0.0342 (4)
H1C	0.3044	0.0106	0.0897	0.035*
H1D	0.3735	0.0869	0.0916	0.035*
H2A	0.2889	0.1710	−0.0019	0.041*
H2B	0.2993	0.0785	−0.0458	0.041*
H4	0.3038 (15)	0.1223 (14)	0.4991 (15)	0.041*
H1A	0.1642	0.0431	−0.0095	0.038*
H1B	0.1539	0.1342	−0.0365	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02009 (15)	0.02009 (15)	0.02009 (15)	−0.00191 (7)	−0.00191 (7)	−0.00191 (7)
O1	0.0227 (5)	0.0206 (5)	0.0169 (5)	0.0053 (4)	−0.0001 (4)	0.0018 (4)
O2	0.0222 (5)	0.0241 (5)	0.0177 (5)	0.0025 (4)	0.0008 (4)	−0.0053 (4)
O3	0.0161 (5)	0.0232 (5)	0.0258 (6)	0.0024 (4)	0.0022 (4)	0.0040 (4)
O4	0.0341 (6)	0.0315 (6)	0.0151 (5)	0.0096 (5)	−0.0006 (5)	0.0022 (5)
O5	0.0153 (3)	0.0153 (3)	0.0153 (3)	0.0012 (4)	0.0012 (4)	0.0012 (4)
B1	0.0165 (8)	0.0174 (8)	0.0176 (8)	0.0029 (6)	−0.0001 (6)	0.0005 (6)
B2	0.0226 (8)	0.0169 (8)	0.0177 (8)	−0.0019 (6)	−0.0008 (7)	−0.0004 (6)
N1	0.0392 (8)	0.0343 (8)	0.0220 (7)	0.0054 (6)	−0.0066 (6)	−0.0048 (6)
C1	0.0302 (8)	0.0319 (9)	0.0250 (8)	0.0087 (7)	0.0017 (7)	−0.0099 (7)
C2	0.0409 (10)	0.0406 (10)	0.0211 (8)	0.0025 (8)	0.0071 (7)	−0.0034 (7)

Geometric parameters (Å, º)

Co1—N1	2.1330 (14)	O4—H4	0.76 (2)
Co1—O2	2.1363 (11)	N1—C2	1.474 (2)
O1—B1	1.4525 (18)	N1—H1A	0.9000
O1—B2	1.379 (2)	N1—H1B	0.9000
O2—B1	1.4790 (19)	C1—C2	1.512 (2)
O3—B1	1.4403 (18)	C1—H1C	0.9700
O3—B2^i	1.356 (2)	C1—H1D	0.9700
O4—B2	1.370 (2)	C2—H2A	0.9700
O5—B1	1.5179 (15)	C2—H2B	0.9700
O2—C1	1.4256 (18)
N1^i—Co1—N1	100.13 (5)	O4—B2—O1	115.81 (14)
N1—Co1—O2	80.20 (5)	C2—N1—Co1	108.15 (10)
N1^ii—Co1—O2	91.95 (5)	C2—N1—H1A	110.1
N1^ii—Co1—O2^i	167.63 (5)	Co1—N1—H1A	110.1
O2^ii—Co1—O2	87.43 (4)	C2—N1—H1B	110.1
B1^i—O5—B1	118.17 (4)	Co1—N1—H1B	110.1
B2—O1—B1	123.89 (12)	H6—N1—H1B	108.4
B2^i—O3—B1	120.35 (12)	O2—C1—C2	108.97 (13)
C1—O2—B1	123.72 (11)	O2—C1—H1C	109.9
C1—O2—Co1	111.24 (9)	C2—C1—H1C	109.9
B1—O2—Co1	118.85 (8)	O2—C1—H1D	109.9
B2—O4—H4	114.3 (17)	C2—C1—H1D	109.9
O1—B1—O2	110.78 (12)	H1—C1—H1D	108.3
O1—B1—O5	108.72 (11)	N1—C2—C1	109.46 (14)
O2—B1—O5	105.33 (12)	N1—C2—H2A	109.8
O3—B1—O1	110.66 (12)	C1—C2—H2A	109.8
O3—B1—O2	112.68 (12)	N1—C2—H2B	109.8
O3—B1—O5	108.44 (11)	C1—C2—H2B	109.8
O3^ii—B2—O1	122.45 (14)	H3—C2—H2B	108.2
O3^ii—B2—O4	121.74 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1^iii	0.76 (2)	2.07 (2)	2.7982 (15)	162 (2)
N1—H1B···O1^iv	0.90	2.33	3.1869 (17)	159
N1—H1A···O4^v	0.90	2.30	3.1559 (19)	160

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

(II) [1,5,9-tris(2-aminoethoxy)-3,7,11-trihydroxy- 3,7,11-tribora-1,5,9-triborata-2,4,6,8,10,12-hexaoxa-13- oxoniatricyclo[7.3.1.0^5,13]tridecane]nickel(II)

Crystal data

[Ni(C6H21B6N3O13)]	Dx = 1.758 Mg m^−3
Mr = 466.83	Mo Kα radiation, λ = 0.71073 Å
Cubic, Pa3	Cell parameters from 25821 reflections
Hall symbol: -P 2ac 2ab 3	θ = 3.0–25.0°
a = 15.2217 (18) Å	µ = 1.17 mm^−1
V = 3526.9 (7) Å^3	T = 293 K
Z = 8	Block, blue
F(000) = 1920	0.14 × 0.14 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	1042 independent reflections
Radiation source: fine-focus sealed tube	885 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 0 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −18→18
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	k = −18→18
Tmin = 0.849, Tmax = 0.849	l = −18→17
25821 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0353P)^2 + 9.9478P] where P = (Fo^2 + 2Fc^2)/3
1042 reflections	(Δ/σ)max < 0.001
91 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.13077 (3)	0.13077 (3)	0.13077 (3)	0.0231 (3)
O1	0.32601 (16)	0.12309 (15)	0.30443 (15)	0.0239 (6)
O2	0.26448 (16)	0.11086 (16)	0.15913 (15)	0.0238 (6)
O3	0.38667 (15)	0.20905 (16)	0.18920 (16)	0.0245 (6)
O4	0.31826 (18)	0.10076 (18)	0.45563 (17)	0.0303 (6)
O5	0.24183 (14)	0.24183 (14)	0.24183 (14)	0.0182 (9)
B1	0.3080 (3)	0.1696 (3)	0.2231 (3)	0.0216 (9)
B2	0.2828 (3)	0.1388 (3)	0.3823 (3)	0.0218 (8)
N1	0.1734 (2)	0.1002 (2)	0.0045 (2)	0.0341 (8)
C1	0.3090 (3)	0.0726 (3)	0.0856 (2)	0.0313 (9)
C2	0.2702 (3)	0.1099 (3)	0.0021 (3)	0.0359 (10)
H1C	0.3019	0.0093	0.0865	0.038*
H1D	0.3712	0.0859	0.0885	0.038*
H2A	0.2856	0.1715	−0.0033	0.043*
H2B	0.2937	0.0790	−0.0484	0.043*
H4	0.302 (3)	0.119 (3)	0.502 (3)	0.043*
H1A	0.1582	0.0448	−0.0091	0.041*
H1B	0.1484	0.1367	−0.0347	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0231 (3)	0.0231 (3)	0.0231 (3)	−0.00170 (18)	−0.00170 (18)	−0.00170 (18)
O1	0.0275 (13)	0.0247 (13)	0.0194 (12)	0.0053 (10)	−0.0015 (10)	0.0034 (10)
O2	0.0256 (13)	0.0267 (13)	0.0189 (12)	0.0017 (10)	−0.0004 (10)	−0.0048 (10)
O3	0.0188 (12)	0.0249 (13)	0.0298 (14)	0.0004 (10)	0.0039 (10)	0.0046 (11)
O4	0.0355 (15)	0.0372 (15)	0.0181 (13)	0.0094 (12)	−0.0013 (12)	0.0031 (12)
O5	0.0182 (9)	0.0182 (9)	0.0182 (9)	0.0011 (10)	0.0011 (10)	0.0011 (10)
B1	0.0188 (19)	0.022 (2)	0.024 (2)	0.0030 (16)	−0.0022 (16)	−0.0028 (16)
B2	0.0214 (19)	0.025 (2)	0.019 (2)	−0.0014 (16)	0.0009 (16)	−0.0032 (16)
N1	0.040 (2)	0.0354 (19)	0.0267 (17)	0.0030 (15)	−0.0058 (15)	0.0002 (14)
C1	0.030 (2)	0.036 (2)	0.028 (2)	0.0088 (17)	0.0017 (16)	−0.0098 (17)
C2	0.037 (2)	0.040 (2)	0.030 (2)	−0.0005 (19)	0.0052 (18)	−0.0021 (18)

Geometric parameters (Å, º)

Ni1—N1	2.081 (3)	O4—H4	0.79 (5)
Ni1—O2	2.102 (2)	N1—C2	1.481 (5)
O1—B1	1.453 (4)	N1—H1A	0.9000
O1—B2	1.377 (5)	N1—H1B	0.9000
O2—B1	1.479 (4)	C1—C2	1.513 (6)
O3—B1	1.435 (5)	C1—H1C	0.9700
O3—B2^i	1.361 (5)	C1—H1D	0.9700
O4—B2	1.369 (5)	C2—H2A	0.9700
O5—B1	1.518 (4)	C2—H2B	0.9700
O2—C1	1.432 (4)
N1—Ni1—N1^i	98.72 (12)	O4—B2—O1	116.1 (3)
N1^ii—Ni1—O2	91.09 (11)	C2—N1—Ni1	108.2 (2)
N1^i—Ni1—O2^i	81.68 (11)	C2—N1—H1A	110.1
N1^ii—Ni1—O2^i	169.98 (12)	Ni1—N1—H1A	110.1
O2^ii—Ni1—O2	88.30 (9)	C2—N1—H1B	110.1
B1—O1—B2	124.0 (3)	Ni1—N1—H1B	110.1
B1^i—O5—B1	117.98 (10)	H6—N1—H1B	108.4
B2^i—O3—B1	120.4 (3)	O2—C1—C2	108.7 (3)
C1—O2—B1	123.3 (3)	O2—C1—H1C	110.0
C1—O2—Ni1	110.9 (2)	C2—C1—H1C	110.0
B1—O2—Ni1	118.8 (2)	O2—C1—H1D	110.0
B2—O4—H4	117 (3)	C2—C1—H1D	110.0
O1—B1—O2	110.5 (3)	H1—C1—H2D	108.3
O1—B1—O5	108.5 (3)	N1—C2—C1	109.2 (3)
O2—B1—O5	105.3 (3)	N1—C2—H2A	109.8
O3—B1—O1	110.7 (3)	C1—C2—H2A	109.8
O3—B1—O2	113.0 (3)	N1—C2—H2B	109.8
O3—B1—O5	108.6 (3)	C1—C2—H2B	109.8
O3^ii—B2—O1	122.3 (3)	H3—C2—H2B	108.3
O3^ii—B2—O4	121.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1^iii	0.79 (5)	2.03 (5)	2.790 (3)	161 (5)
N1—H1B···O1^iv	0.90	2.33	3.175 (4)	156
N1—H1A···O4^v	0.90	2.31	3.151 (4)	156

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