Piperazine-1,4-diium bis­(hexa­hydroxido­hepta­oxidohexa­borato-κ3O,O′,O′′)cobaltate(II) hexa­hydrate

Jamai, N.; Rzaigui, M.; Toumi, S.A.

doi:10.1107/S1600536814007090

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Pages m167-m168

doi:10.1107/S1600536814007090

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Piperazine-1,4-diium bis(hexahydroxidoheptaoxidohexaborato-κ³O,O′,O′′)cobaltate(II) hexahydrate

Nabil Jamai,^a Mohamed Rzaigui ^a and Samah Akriche Toumi ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: samah.akriche@fsb.rnu.tn

(Received 3 March 2014; accepted 30 March 2014; online 5 April 2014)

In the title hydrate, (C₄H₁₂N₂)[Co{B₆O₇(OH)₆}₂]·6H₂O, both the dication and dianion are generated by crystallographic inversion symmetry. The Co²⁺ ion in the dianion adopts a fairly regular CoO₆ octahedral coordination geometry arising from the two O,O′,O′′-tridentate ligands. In the crystal, the dianions and water molecules are linked by O—H⋯O hydrogen bonds, generating a framework with large [100] channels, which are occupied by the organic dications. N—H⋯O and C—H⋯O hydrogen bonds consolidate the structure.

CCDC reference: 994558

Related literature

For related structures, see: Natarajan et al. (2003 ); Negro et al. (1971 ); Zhihong et al. (2005 ); Yue et al. (2003 ).

Experimental

Crystal data

(C₄H₁₂N₂)[Co(H₆B₆O₁₃)₂]·6H₂O
M_r = 813.00
Triclinic, $[P \overline 1]$
a = 8.226 (3) Å
b = 10.157 (2) Å
c = 11.298 (4) Å
α = 65.98 (2)°
β = 74.20 (3)°
γ = 69.03 (5)°
V = 796.2 (4) Å³
Z = 1
Ag Kα radiation
λ = 0.56087 Å
μ = 0.35 mm⁻¹
T = 298 K
0.23 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
9895 measured reflections
7785 independent reflections
6118 reflections with I > 2σ(I)
R_int = 0.014
2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.153
S = 1.06
7785 reflections
259 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.42 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O2	2.0539 (17)
Co1—O1	2.0648 (14)
Co1—O4	2.1926 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2W	0.82 (1)	2.00 (2)	2.7525 (19)	153 (3)
O2—H2⋯O6ⁱ	0.81 (1)	2.11 (1)	2.876 (2)	157 (3)
O3—H3⋯O23ⁱⁱ	0.82	1.93	2.745 (2)	172
O4—H4⋯O2W	0.81 (1)	2.08 (1)	2.864 (2)	164 (3)
O5—H5⋯O45ⁱⁱⁱ	0.82	1.91	2.7159 (18)	169
O6—H6⋯O4ⁱ	0.82	1.95	2.734 (2)	160
O1W—H1W1⋯O5	0.86 (1)	1.96 (2)	2.771 (2)	158 (4)
O1W—H2W1⋯O26^iv	0.86 (1)	2.27 (1)	3.108 (3)	167 (3)
O1W—H2W1⋯O23^iv	0.86 (1)	2.51 (3)	3.158 (3)	133 (3)
O2W—H1W2⋯O3^v	0.85 (1)	2.05 (2)	2.861 (2)	159 (3)
O2W—H2W2⋯O1W^vi	0.85 (1)	2.01 (1)	2.838 (3)	164 (3)
O3W—H2W3⋯O1W^vii	0.85 (1)	2.05 (2)	2.842 (3)	155 (3)
O3W—H1W3⋯O1^viii	0.85 (1)	2.24 (1)	3.088 (3)	179 (1)
N1—H1A⋯O16	0.90	1.78	2.654 (2)	165
N1—H1A⋯O6	0.90	2.46	2.986 (3)	117
N1—H1B⋯O3W	0.90	1.98	2.836 (3)	157
C1—H1C⋯O34^v	0.97	2.56	3.321 (3)	136
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y+1, -z; (iv) -x+2, -y+1, -z; (v) x, y+1, z; (vi) -x+1, -y+2, -z; (vii) -x+2, -y+2, -z; (viii) x+1, y, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 994558

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814007090/hb7207sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007090/hb7207Isup2.hkl

checkCIF report

Comment top

The mode of condensation of trigonal planar B(OH)₃ and tetrahedral [B(OH)₄]^- primary structural units, leads to a variety of hydrated polyborate structures such as rings, cages, chains, sheets or extended networks. In particular, the polymerization of three tetrahedral BO₃(OH) (3Δ) and three trigonal BO2(OH)(3 T) moieties form tricyclic [B₆O₇(OH)₆]^2- anions featuring an unusual three-coordinate oxygen atom (µ₃–O). To date, various hydrated hexaborate structures including inorganic metals have been extensively studied. In contrast, those with organic and inorganic cations are less explored. On the best of our knowledge only one hydrated hexaborate with transition metal and organic cations, is earlier cited; [(Me)₂NH(CH₂)₂NH(Me)₂]{Zn[B₆O₇(OH)₆]2}·2H₂O (with Me = methyl)(Natarajan et al., 2003). In this work, we report the synthesis and structure of a new organic-inorganic hydrated hexaborate, [C₄N₂H₁₂]{Co[B₆O₇(OH)₆]₂}·6H₂O (I).

The asymmetric unit of the title complex consists of a half [C₄H₁₂N₂]²⁺ diprotonated cation, a half of {Co[B₆O₇(OH)₆]₂}^2- complex hexaborate anions and three lattice water molecules as shown in Figure 1. As the Co²⁺ ion is located on centre of inversion so is bonded to six O atoms of two chelating [B₆O₇(OH)₆]^2- anions forming thus a distorted octahedron. The Co—O distances range from 2.0539 (17) to 2.1926 (12) Å and the O—Co—O angles are between 87.03 (5)–180.00 (7)° (Table 1). The [B₆O₇(OH)₆]^2- unit is formed by three tetrahedral B and three trigonal B atoms (3Δ + 3 T), linked through six double bridged (µ₂–O) and one triple bridged (µ₃–O) oxygen atoms in which each B atom possesses one terminal OH group, resulting in the formation of a tricyclic honeycomb-like structure anion (Fig. 2). Similar hexaborate anions have been encountered in the mineral aksaite (Negro et al., 1971).

The B—O and O—B—O bond lengths range from 1.434 (2) to 1.5123 (18) Å and from 105.58 (12) to 112.53 (12) ° respectively for the tetrahedral B atoms and those for trigonal ones are in the range 1.355 (2)–1.371 (2) Å and from 114.61 (14) to 122.88 (14) °. The longer B—O distances are observed for the tetrahedral B atoms associated with the µ₃ oxygen atom. These structural parameters are in good agreement with those observed for other hydrated hexaborate associated with some alkali and transition metals, such as K₂Mg[B₆O₇(OH)₆]₂·4H₂O (Zhihong et al., 2005) and Rb₂Co[B₆O₇(OH)₆]₂·4H₂O (Yue et al., 2003).

The [B₆O₇(OH)₆]^2- anions are further interconnected through O—H···O hydrogen-bonding interactions of the hydroxyl groups (Table 2) yelding to a three-dimensional framework with channels along the a axis. The negative excess charges of the anionic framework is compensated by [C₄H₁₂N₂]²⁺ cations, which occupy the voids along with water molecules (Fig. 3). It'to be noted that the diprotonated piperazine ring adopts a chair conformation, with puckering parameters Q = 1.7803 Å, θ = 171.58° and ϕ = 90°.

Related literature top

For related structures, see: Natarajan et al. (2003); Negro et al. (1971); Zhihong et al. (2005); Yue et al. (2003).

Experimental top

Piperazine (0.086 g), CoCl₂·6H₂O (0.8 g) and H₃BO₃ (2 g) in a molar ratio: piperazine/Co/ B = 1/4/32 were dissolved in a mixture of 30 ml of distilled water and 20 ml of ethanol and then stirred for 1 h. The pH was adjusted to 9 by addition of 5 ml of pyridine. Within two weeks, pink prisms of the title compound were obtained. The existence of hexaborate anion in the prepared compound is evidenced by characteristic IR absorption band at 685 cm^-1. IR (KBr, cm^-1): 1358 ν_as(BO₃), 908–850 ν_s(BO₃), 1028ν_as(BO₄),807 ν_s(BO₄),1095 ν(BOH) and 685δ(BO₃)+δ(BO₄).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of (I) with displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are represented as dashed lines. [Symmetry code: (i) 1 - x, 1 - y, 1 - z]
	Fig. 2. Crystal structure of I viewed along a axis showing a three-dimensional-supramolecular structure featuring the voids represented as large yellow ball. The H-atoms not included in H-bond scheme are omitted.

Piperazine-1,4-diium bis(hexahydroxidoheptaoxidohexaborato-κ³O,O',O'')cobaltate(II) hexahydrate top

Crystal data top

(C₄H₁₂N₂)[Co(H₆B₆O₁₃)₂]·6H₂O	Z = 1
M_r = 813.00	F(000) = 417
Triclinic, P1	D_x = 1.696 Mg m⁻³
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56087 Å
a = 8.226 (3) Å	Cell parameters from 25 reflections
b = 10.157 (2) Å	θ = 9–11°
c = 11.298 (4) Å	µ = 0.35 mm⁻¹
α = 65.98 (2)°	T = 298 K
β = 74.20 (3)°	Prism, pink
γ = 69.03 (5)°	0.23 × 0.15 × 0.11 mm
V = 796.2 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.014
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.1°
Graphite monochromator	h = −13→13
non–profiled ω scans	k = −16→16
9895 measured reflections	l = −3→18
7785 independent reflections	2 standard reflections every 120 min
6118 reflections with I > 2σ(I)	intensity decay: 2%

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0924P)² + 0.2147P] where P = (F_o² + 2F_c²)/3
7785 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 2.42 e Å⁻³
12 restraints	Δρ_min = −0.99 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Co(H₆B₆O₁₃)₂]·6H₂O	γ = 69.03 (5)°
M_r = 813.00	V = 796.2 (4) Å³
Triclinic, P1	Z = 1
a = 8.226 (3) Å	Ag Kα radiation, λ = 0.56087 Å
b = 10.157 (2) Å	µ = 0.35 mm⁻¹
c = 11.298 (4) Å	T = 298 K
α = 65.98 (2)°	0.23 × 0.15 × 0.11 mm
β = 74.20 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.014
9895 measured reflections	2 standard reflections every 120 min
7785 independent reflections	intensity decay: 2%
6118 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.049	12 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 2.42 e Å⁻³
7785 reflections	Δρ_min = −0.99 e Å⁻³
259 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.5000	0.5000	0.01614 (7)
B1	0.7384 (2)	0.59885 (17)	0.23924 (15)	0.0163 (2)
B2	0.8734 (2)	0.33738 (17)	0.39832 (16)	0.0167 (2)
B3	0.8346 (2)	0.12594 (18)	0.36263 (17)	0.0200 (3)
B4	0.6375 (2)	0.37212 (16)	0.26842 (15)	0.0161 (2)
B5	0.6174 (2)	0.59847 (19)	0.06603 (16)	0.0210 (3)
B6	1.0368 (2)	0.5217 (2)	0.29973 (17)	0.0203 (3)
O124	0.77220 (13)	0.43050 (11)	0.28482 (10)	0.01562 (17)
O45	0.58438 (15)	0.46319 (12)	0.14086 (11)	0.02026 (19)
O34	0.71305 (15)	0.21657 (12)	0.28139 (12)	0.02037 (19)
O16	0.89561 (14)	0.62883 (13)	0.24323 (12)	0.0225 (2)
O15	0.69605 (17)	0.66434 (13)	0.10864 (11)	0.0232 (2)
O23	0.91602 (16)	0.17965 (12)	0.41590 (12)	0.0229 (2)
O1	0.58976 (15)	0.65398 (12)	0.33104 (12)	0.02076 (19)
H1	0.595 (4)	0.7336 (18)	0.330 (3)	0.031*
O2	0.75590 (15)	0.36962 (14)	0.51227 (11)	0.0222 (2)
H2	0.793 (4)	0.361 (3)	0.5750 (18)	0.033*
O3	0.8757 (2)	−0.02567 (13)	0.38981 (16)	0.0321 (3)
H3	0.9463	−0.0701	0.4421	0.048*
O4	0.51422 (14)	0.61177 (12)	0.62547 (11)	0.01811 (18)
H4	0.528 (4)	0.6931 (17)	0.578 (2)	0.027*
O5	0.5670 (2)	0.67326 (16)	−0.05561 (13)	0.0352 (3)
H5	0.5205	0.6238	−0.0708	0.053*
O6	1.17955 (16)	0.57172 (15)	0.27863 (15)	0.0286 (3)
H6	1.2628	0.5003	0.3070	0.043*
O26	1.03454 (14)	0.37793 (13)	0.37106 (12)	0.0223 (2)
O1W	0.6861 (3)	0.8794 (2)	−0.2835 (2)	0.0489 (4)
H1W1	0.622 (4)	0.833 (4)	−0.216 (3)	0.073*
H2W1	0.773 (3)	0.818 (3)	−0.314 (3)	0.073*
O2W	0.5784 (2)	0.87545 (16)	0.41668 (16)	0.0349 (3)
H1W2	0.676 (2)	0.882 (3)	0.423 (3)	0.052*
H2W2	0.511 (3)	0.959 (2)	0.375 (3)	0.052*
O3W	1.2705 (3)	0.9010 (3)	0.2089 (3)	0.0675 (7)
H2W3	1.253 (5)	0.981 (2)	0.223 (5)	0.101*
H1W3	1.3578	0.8334	0.2430	0.101*
N1	0.9898 (3)	0.8815 (2)	0.1223 (2)	0.0443 (4)
H1A	0.9538	0.8001	0.1763	0.053*
H1B	1.0545	0.8982	0.1646	0.053*
C1	0.8360 (3)	1.0119 (2)	0.0893 (2)	0.0355 (4)
H1C	0.7653	1.0290	0.1686	0.043*
H1D	0.7638	0.9935	0.0458	0.043*
C2	1.1021 (4)	0.8520 (2)	−0.0001 (3)	0.0441 (5)
H2A	1.2028	0.7651	0.0235	0.053*
H2B	1.0339	0.8314	−0.0450	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01484 (11)	0.01703 (12)	0.01733 (12)	−0.00406 (8)	−0.00425 (8)	−0.00587 (9)
B1	0.0158 (5)	0.0161 (5)	0.0180 (6)	−0.0053 (4)	−0.0062 (5)	−0.0038 (5)
B2	0.0157 (5)	0.0159 (5)	0.0194 (6)	−0.0025 (4)	−0.0083 (5)	−0.0050 (5)
B3	0.0214 (6)	0.0157 (6)	0.0240 (7)	−0.0030 (5)	−0.0078 (5)	−0.0070 (5)
B4	0.0168 (5)	0.0154 (5)	0.0179 (6)	−0.0039 (4)	−0.0071 (5)	−0.0053 (5)
B5	0.0255 (7)	0.0211 (6)	0.0173 (6)	−0.0073 (5)	−0.0086 (5)	−0.0034 (5)
B6	0.0160 (6)	0.0245 (7)	0.0241 (7)	−0.0074 (5)	−0.0055 (5)	−0.0090 (6)
O124	0.0151 (4)	0.0150 (4)	0.0180 (4)	−0.0037 (3)	−0.0070 (3)	−0.0046 (3)
O45	0.0244 (5)	0.0208 (4)	0.0182 (4)	−0.0091 (4)	−0.0102 (4)	−0.0025 (4)
O34	0.0233 (5)	0.0158 (4)	0.0252 (5)	−0.0029 (3)	−0.0108 (4)	−0.0078 (4)
O16	0.0176 (4)	0.0203 (4)	0.0316 (6)	−0.0072 (4)	−0.0091 (4)	−0.0058 (4)
O15	0.0321 (6)	0.0206 (5)	0.0194 (5)	−0.0107 (4)	−0.0116 (4)	−0.0014 (4)
O23	0.0262 (5)	0.0148 (4)	0.0294 (5)	−0.0011 (4)	−0.0159 (4)	−0.0058 (4)
O1	0.0199 (4)	0.0178 (4)	0.0254 (5)	−0.0055 (3)	−0.0020 (4)	−0.0088 (4)
O2	0.0187 (4)	0.0287 (5)	0.0192 (5)	−0.0025 (4)	−0.0074 (4)	−0.0091 (4)
O3	0.0400 (7)	0.0156 (5)	0.0460 (8)	−0.0014 (4)	−0.0265 (6)	−0.0085 (5)
O4	0.0174 (4)	0.0182 (4)	0.0203 (4)	−0.0065 (3)	−0.0039 (3)	−0.0061 (3)
O5	0.0583 (9)	0.0321 (6)	0.0227 (6)	−0.0253 (6)	−0.0218 (6)	0.0042 (5)
O6	0.0177 (5)	0.0287 (6)	0.0403 (7)	−0.0093 (4)	−0.0100 (5)	−0.0069 (5)
O26	0.0156 (4)	0.0235 (5)	0.0282 (5)	−0.0055 (4)	−0.0087 (4)	−0.0059 (4)
O1W	0.0409 (9)	0.0369 (8)	0.0484 (10)	−0.0071 (7)	0.0027 (7)	−0.0038 (7)
O2W	0.0407 (7)	0.0262 (6)	0.0426 (8)	−0.0149 (5)	−0.0062 (6)	−0.0116 (6)
O3W	0.0612 (14)	0.0639 (14)	0.0861 (17)	−0.0129 (11)	−0.0395 (13)	−0.0203 (13)
N1	0.0550 (12)	0.0363 (9)	0.0406 (10)	−0.0197 (8)	−0.0131 (9)	−0.0026 (8)
C1	0.0392 (10)	0.0318 (8)	0.0291 (8)	−0.0099 (7)	0.0008 (7)	−0.0081 (7)
C2	0.0509 (13)	0.0232 (8)	0.0485 (12)	−0.0079 (8)	0.0024 (10)	−0.0111 (8)

Geometric parameters (Å, º) top

Co1—O2	2.0539 (17)	B6—O6	1.368 (2)
Co1—O2ⁱ	2.0539 (17)	B6—O16	1.369 (2)
Co1—O1	2.0648 (14)	O1—H1	0.820 (10)
Co1—O1ⁱ	2.0648 (14)	O2—H2	0.811 (10)
Co1—O4ⁱ	2.1926 (12)	O3—H3	0.8200
Co1—O4	2.1926 (12)	O4—B4ⁱ	1.490 (2)
B1—O15	1.434 (2)	O4—H4	0.810 (10)
B1—O16	1.4462 (19)	O5—H5	0.8200
B1—O1	1.475 (2)	O6—H6	0.8200
B1—O124	1.5123 (18)	O1W—H1W1	0.861 (10)
B2—O26	1.4447 (19)	O1W—H2W1	0.856 (10)
B2—O23	1.4510 (19)	O2W—H1W2	0.852 (10)
B2—O2	1.462 (2)	O2W—H2W2	0.854 (10)
B2—O124	1.5041 (19)	O3W—H2W3	0.846 (10)
B3—O34	1.357 (2)	O3W—H1W3	0.847 (2)
B3—O23	1.363 (2)	N1—C1	1.466 (3)
B3—O3	1.371 (2)	N1—C2	1.517 (4)
B4—O34	1.4360 (19)	N1—H1A	0.9000
B4—O45	1.4463 (19)	N1—H1B	0.9000
B4—O4ⁱ	1.490 (2)	C1—C2ⁱⁱ	1.508 (3)
B4—O124	1.5117 (18)	C1—H1C	0.9700
B5—O15	1.356 (2)	C1—H1D	0.9700
B5—O5	1.368 (2)	C2—C1ⁱⁱ	1.508 (3)
B5—O45	1.368 (2)	C2—H2A	0.9700
B6—O26	1.355 (2)	C2—H2B	0.9700

O2—Co1—O2ⁱ	180.0	B2—O124—B4	118.01 (11)
O2—Co1—O1	88.68 (6)	B2—O124—B1	116.87 (11)
O2ⁱ—Co1—O1	91.32 (6)	B4—O124—B1	117.76 (11)
O2—Co1—O1ⁱ	91.32 (6)	B5—O45—B4	124.30 (12)
O2ⁱ—Co1—O1ⁱ	88.68 (6)	B3—O34—B4	120.52 (12)
O1—Co1—O1ⁱ	180.0	B6—O16—B1	124.47 (12)
O2—Co1—O4ⁱ	88.17 (5)	B5—O15—B1	120.85 (12)
O2ⁱ—Co1—O4ⁱ	91.83 (5)	B3—O23—B2	123.44 (12)
O1—Co1—O4ⁱ	87.03 (5)	B1—O1—Co1	118.94 (9)
O1ⁱ—Co1—O4ⁱ	92.97 (5)	B1—O1—H1	109.3 (19)
O2—Co1—O4	91.83 (5)	Co1—O1—H1	121.9 (19)
O2ⁱ—Co1—O4	88.17 (5)	B2—O2—Co1	121.28 (9)
O1—Co1—O4	92.97 (5)	B2—O2—H2	122 (2)
O1ⁱ—Co1—O4	87.03 (5)	Co1—O2—H2	114 (2)
O4ⁱ—Co1—O4	180.0	B3—O3—H3	109.5
O15—B1—O16	110.89 (12)	B4ⁱ—O4—Co1	116.22 (9)
O15—B1—O1	110.91 (13)	B4ⁱ—O4—H4	110.6 (19)
O16—B1—O1	110.56 (12)	Co1—O4—H4	107.3 (19)
O15—B1—O124	109.07 (12)	B5—O5—H5	109.5
O16—B1—O124	108.17 (12)	B6—O6—H6	109.5
O1—B1—O124	107.12 (12)	B6—O26—B2	119.33 (13)
O26—B2—O23	109.16 (13)	H1W1—O1W—H2W1	112 (2)
O26—B2—O2	112.53 (12)	H1W2—O2W—H2W2	113 (2)
O23—B2—O2	110.85 (13)	H2W3—O3W—H1W3	111 (2)
O26—B2—O124	109.35 (12)	C1—N1—C2	110.90 (19)
O23—B2—O124	109.28 (12)	C1—N1—H1A	109.5
O2—B2—O124	105.58 (12)	C2—N1—H1A	109.5
O34—B3—O23	122.88 (14)	C1—N1—H1B	109.5
O34—B3—O3	117.27 (14)	C2—N1—H1B	109.5
O23—B3—O3	119.85 (14)	H1A—N1—H1B	108.0
O34—B4—O45	111.78 (12)	N1—C1—C2ⁱⁱ	109.0 (2)
O34—B4—O4ⁱ	109.79 (12)	N1—C1—H1C	109.9
O45—B4—O4ⁱ	110.85 (12)	C2ⁱⁱ—C1—H1C	109.9
O34—B4—O124	109.48 (12)	N1—C1—H1D	109.9
O45—B4—O124	107.67 (11)	C2ⁱⁱ—C1—H1D	109.9
O4ⁱ—B4—O124	107.13 (11)	H1C—C1—H1D	108.3
O15—B5—O5	117.83 (14)	C1ⁱⁱ—C2—N1	109.18 (18)
O15—B5—O45	122.48 (14)	C1ⁱⁱ—C2—H2A	109.8
O5—B5—O45	119.68 (14)	N1—C2—H2A	109.8
O26—B6—O6	122.85 (15)	C1ⁱⁱ—C2—H2B	109.8
O26—B6—O16	122.54 (14)	N1—C2—H2B	109.8
O6—B6—O16	114.61 (14)	H2A—C2—H2B	108.3

O26—B2—O124—B4	158.42 (12)	O1—B1—O15—B5	−88.84 (17)
O23—B2—O124—B4	38.99 (17)	O124—B1—O15—B5	28.90 (19)
O2—B2—O124—B4	−80.28 (14)	O34—B3—O23—B2	4.1 (3)
O26—B2—O124—B1	−52.13 (16)	O3—B3—O23—B2	−176.41 (15)
O23—B2—O124—B1	−171.56 (11)	O26—B2—O23—B3	−136.34 (15)
O2—B2—O124—B1	69.17 (15)	O2—B2—O23—B3	99.17 (17)
O34—B4—O124—B2	−47.01 (16)	O124—B2—O23—B3	−16.8 (2)
O45—B4—O124—B2	−168.73 (11)	O15—B1—O1—Co1	128.21 (10)
O4ⁱ—B4—O124—B2	71.99 (15)	O16—B1—O1—Co1	−108.36 (12)
O34—B4—O124—B1	163.82 (12)	O124—B1—O1—Co1	9.28 (14)
O45—B4—O124—B1	42.10 (16)	O2—Co1—O1—B1	37.04 (10)
O4ⁱ—B4—O124—B1	−77.18 (14)	O2ⁱ—Co1—O1—B1	−142.96 (10)
O15—B1—O124—B2	160.84 (12)	O1ⁱ—Co1—O1—B1	3 (100)
O16—B1—O124—B2	40.14 (16)	O4ⁱ—Co1—O1—B1	−51.19 (10)
O1—B1—O124—B2	−79.05 (14)	O4—Co1—O1—B1	128.81 (10)
O15—B1—O124—B4	−49.63 (16)	O26—B2—O2—Co1	125.40 (11)
O16—B1—O124—B4	−170.33 (12)	O23—B2—O2—Co1	−112.03 (12)
O1—B1—O124—B4	70.47 (15)	O124—B2—O2—Co1	6.19 (15)
O15—B5—O45—B4	−3.7 (3)	O2ⁱ—Co1—O2—B2	−124 (100)
O5—B5—O45—B4	177.61 (16)	O1—Co1—O2—B2	−47.25 (11)
O34—B4—O45—B5	−135.19 (15)	O1ⁱ—Co1—O2—B2	132.75 (11)
O4ⁱ—B4—O45—B5	101.96 (17)	O4ⁱ—Co1—O2—B2	39.82 (11)
O124—B4—O45—B5	−14.9 (2)	O4—Co1—O2—B2	−140.18 (11)
O23—B3—O34—B4	−12.8 (2)	O2—Co1—O4—B4ⁱ	−134.31 (9)
O3—B3—O34—B4	167.68 (15)	O2ⁱ—Co1—O4—B4ⁱ	45.69 (9)
O45—B4—O34—B3	151.66 (14)	O1—Co1—O4—B4ⁱ	136.92 (10)
O4ⁱ—B4—O34—B3	−84.90 (16)	O1ⁱ—Co1—O4—B4ⁱ	−43.08 (10)
O124—B4—O34—B3	32.44 (19)	O4ⁱ—Co1—O4—B4ⁱ	10 (100)
O26—B6—O16—B1	−7.6 (3)	O6—B6—O26—B2	174.61 (15)
O6—B6—O16—B1	172.53 (15)	O16—B6—O26—B2	−5.2 (2)
O15—B1—O16—B6	−129.57 (16)	O23—B2—O26—B6	152.56 (14)
O1—B1—O16—B6	106.99 (17)	O2—B2—O26—B6	−83.94 (17)
O124—B1—O16—B6	−10.0 (2)	O124—B2—O26—B6	33.05 (19)
O5—B5—O15—B1	174.55 (16)	C2—N1—C1—C2ⁱⁱ	−59.8 (3)
O45—B5—O15—B1	−4.2 (3)	C1—N1—C2—C1ⁱⁱ	59.9 (3)
O16—B1—O15—B5	147.91 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2W	0.82 (1)	2.00 (2)	2.7525 (19)	153 (3)
O2—H2···O6ⁱⁱⁱ	0.81 (1)	2.11 (1)	2.876 (2)	157 (3)
O3—H3···O23^iv	0.82	1.93	2.745 (2)	172
O4—H4···O2W	0.81 (1)	2.08 (1)	2.864 (2)	164 (3)
O5—H5···O45^v	0.82	1.91	2.7159 (18)	169
O6—H6···O4ⁱⁱⁱ	0.82	1.95	2.734 (2)	160
O1W—H1W1···O5	0.86 (1)	1.96 (2)	2.771 (2)	158 (4)
O1W—H2W1···O26^vi	0.86 (1)	2.27 (1)	3.108 (3)	167 (3)
O1W—H2W1···O23^vi	0.86 (1)	2.51 (3)	3.158 (3)	133 (3)
O2W—H1W2···O3^vii	0.85 (1)	2.05 (2)	2.861 (2)	159 (3)
O2W—H2W2···O1W^viii	0.85 (1)	2.01 (1)	2.838 (3)	164 (3)
O3W—H2W3···O1Wⁱⁱ	0.85 (1)	2.05 (2)	2.842 (3)	155 (3)
O3W—H1W3···O1^ix	0.85 (1)	2.24 (1)	3.088 (3)	179 (1)
N1—H1A···O16	0.90	1.78	2.654 (2)	165
N1—H1A···O6	0.90	2.46	2.986 (3)	117
N1—H1B···O3W	0.90	1.98	2.836 (3)	157
C1—H1C···O34^vii	0.97	2.56	3.321 (3)	136

Symmetry codes: (ii) −x+2, −y+2, −z; (iii) −x+2, −y+1, −z+1; (iv) −x+2, −y, −z+1; (v) −x+1, −y+1, −z; (vi) −x+2, −y+1, −z; (vii) x, y+1, z; (viii) −x+1, −y+2, −z; (ix) x+1, y, z.

Selected bond lengths (Å) top

Co1—O2	2.0539 (17)	Co1—O4	2.1926 (12)
Co1—O1	2.0648 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2W	0.820 (10)	1.996 (15)	2.7525 (19)	153 (3)
O2—H2···O6ⁱ	0.811 (10)	2.113 (14)	2.876 (2)	157 (3)
O3—H3···O23ⁱⁱ	0.82	1.93	2.745 (2)	171.8
O4—H4···O2W	0.810 (10)	2.077 (12)	2.864 (2)	164 (3)
O5—H5···O45ⁱⁱⁱ	0.82	1.91	2.7159 (18)	168.6
O6—H6···O4ⁱ	0.82	1.95	2.734 (2)	159.7
O1W—H1W1···O5	0.861 (10)	1.955 (18)	2.771 (2)	158 (4)
O1W—H2W1···O26^iv	0.856 (10)	2.266 (13)	3.108 (3)	167 (3)
O1W—H2W1···O23^iv	0.856 (10)	2.51 (3)	3.158 (3)	133 (3)
O2W—H1W2···O3^v	0.852 (10)	2.050 (15)	2.861 (2)	159 (3)
O2W—H2W2···O1W^vi	0.854 (10)	2.007 (12)	2.838 (3)	164 (3)
O3W—H2W3···O1W^vii	0.846 (10)	2.054 (19)	2.842 (3)	155 (3)
O3W—H1W3···O1^viii	0.847 (2)	2.2407 (19)	3.088 (3)	179.4 (2)
N1—H1A···O16	0.90	1.78	2.654 (2)	165
N1—H1A···O6	0.90	2.46	2.986 (3)	117
N1—H1B···O3W	0.90	1.98	2.836 (3)	157
C1—H1C···O34^v	0.97	2.56	3.321 (3)	136

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+2, −y+1, −z; (v) x, y+1, z; (vi) −x+1, −y+2, −z; (vii) −x+2, −y+2, −z; (viii) x+1, y, z.

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