Bis[(m-phenyl­enedimethyl­ene)­diammonium] tetra­deca­borate

Jiang, X.; Wu, S.-L.; Shao, Z.-D.; Liang, Y.-X.

doi:10.1107/S1600536808033333

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2129

doi:10.1107/S1600536808033333

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Bis[(m-phenylenedimethylene)diammonium] tetradecaborate

Xiao Jiang,^a Shu-Li Wu,^a Zhi-Dong Shao ^a and Yun-Xiao Liang ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: liangyunxiao@nbu.edu.cn

(Received 29 September 2008; accepted 14 October 2008; online 18 October 2008)

The title compound 2C₈H₁₄N₂²⁺·[B₁₄O₂₀(OH)₆]⁴⁻, contains diprotonated C₈H₁₄N₂²⁺ cations and centrosymmetric tetradecaborate anions. The crystal structure is stabilized by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For background on the importance of borate compounds, see: Chen et al. (1995 ); Grice et al. (1999 ). For previous work on boron oxoanions, see: Liu et al. (2006 ); Pan et al. (2007 ); Grice et al. (1999); Schubert et al. (2000 ); Touboul et al. (2003 ); Burns (1995 ).

Experimental

Crystal data

2C₈H₁₄N₂²⁺·B₁₄H₆O₂₆⁴⁻
M_r = 849.81
Triclinic, $[P \overline 1]$
a = 9.1025 (18) Å
b = 10.293 (2) Å
c = 10.942 (2) Å
α = 109.68 (3)°
β = 108.24 (3)°
γ = 102.19 (3)°
V = 857.4 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 295 (2) K
0.34 × 0.26 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.964, T_max = 0.973
6803 measured reflections
3009 independent reflections
2002 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.128
S = 1.24
3009 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10A⋯O2ⁱ	0.82	1.98	2.784 (2)	168
O11—H11A⋯O3ⁱⁱ	0.82	1.84	2.659 (2)	179
O13—H13A⋯O11ⁱⁱⁱ	0.82	2.00	2.815 (2)	173
N1—H1A⋯O7	0.89	2.08	2.863 (2)	146
N1—H1B⋯O13^iv	0.89	1.98	2.850 (2)	166
N1—H1C⋯O6^v	0.89	2.20	2.916 (2)	137
N1—H1C⋯O1^v	0.89	2.54	3.394 (2)	161
N2—H2A⋯O4^vi	0.89	1.97	2.822 (2)	159
N2—H2B⋯O1^v	0.89	1.99	2.877 (2)	173
N2—H2B⋯O9^v	0.89	2.55	3.052 (2)	116
N2—H2C⋯O12^vii	0.89	2.19	3.067 (2)	168
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+2; (iii) -x+2, -y+1, -z+2; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1; (vi) x-1, y, z-1; (vii) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033333/bt2801sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033333/bt2801Isup2.hkl

checkCIF report

Comment top

Borate compounds have considerable mineralogical and industrial importance (Chen et al., 1995; Grice et al., 1999). Boron atoms form strong bonds with oxygen atoms not only in trigonal planar BO₃, but also in tetrahedral BO₄ groups. These BO₃ and BO₄ groups may be linked together by sharing common oxygen to form isolated rings and cages or extended chains, sheets, and networks. So far, a number of isolated boron oxoanions have been found in mineral and synthetic borates, such as [B(OH)₄]^-, [B₂O(OH)₆]^2-, [B₃O₃(OH)₄]^-, [B₄O₅(OH)₄]^2-, [B₅O₆(OH)₄]^-, [B₆O₇(OH)₆]^2- (Grice et al., 1999; Touboul et al., 2003), [B₇O₉(OH)₅]^2- (Liu et al., 2006; Pan et al., 2007), [B₉O₁₂(OH)₆]^3- (Schubert et al., 2000), and [B₁₄O₂₀(OH)₆]^4- (Liu et al., 2006; Pan et al., 2007). Compared with metal borates, the synthesis of organically modified nonmetal borates was less well explored in the past decades. Herein, we describe the synthesis and crystal structure of a new nonmetal borate with [B₁₄O₂₀(OH)₆]^4- as polyanions.

As shown in Fig. 1, the title compound consists of isolated [B₁₄O₂₀(OH)₆]^4- polyborate anions and [C₈H₁₄N₂]²⁺ cations. The [B₁₄O₂₀(OH)₆]^4- borate anion is composed of four BO₄, four BO₃, and six BO₂(OH) groups (Burns, 1995). It can also be seen as two [B₇O₉(OH)₅]^2- clusters combined with each other through the dehydration of four hydroxyl groups. Each [B₇O₉(OH)₅]^2- group contains three B₃O₃ cycles held together via two common BO₄ tetrahedra. The B—O bond lengths and O—B—O bond angles are in the range of 1.332 (4)–1.509 (4) Å and 105.9 (3)–124.5 (3)° (Table 1), which are in good agreement with other borates reported previously (Liu et al., 2006; Pan et al., 2007).

In the present instance, the isolated tetradecaborates anions are linked together through hydrogen bonds: O10—H10A···O2, O11—H11A···O3 (Fig. 2), forming a two-dimensional sheetlike structure. The adjacent borate sheets are further linked together by strong H-bonding interactions [O13—H13A···O11] to form a three-dimensional network (Fig. 3). The hydrogen bonds are listed in Table 2.

Related literature top

For background on the importance of borate compounds, see: Chen et al. (1995); Grice et al. (1999). For previous work on boron oxoanions, see: Liu et al. (2006); Pan et al. (2007); Grice et al. (1999); Schubert et al. (2000); Touboul et al. (2003); Burns (1995). [Please check added text]

Experimental top

The title compound was obtained by the reaction of H₃BO₃ and 1,3-Bis(aminomethyl)benzene under mild solvothermal conditions. Typically, a mixture of H₃BO₃ (0.9882 g), 1,3-Bis(aminomethyl)benzene (3 ml) was stirred at room temperature. The final mixture was sealed in a Teflon-lined autoclave, heated to 443 K at a rate of 10 K/h, kept at 443 K for 4 days and then cooled to room temperature at a rate of 5 K/h. Colorless transparent block-like crystals were collected and dried in air.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: Crystal Structure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The crystal structure of [(C₈H₁₄N₂)]₂[B₁₄O₂₀(OH)₆]: (a) [B₁₄O₂₀(OH)₆]^4-; (b) [(C₈H₁₄N₂)]²⁺, drawn at the 50% probability level. [Symmetry codes: (i) -x+1, -y+1, -z+1.]
	Fig. 2. Formation of the two-dimensional sheet from the [B₁₄O₂₀(OH)₆]^4- polyanions. Hydrogen bonds are indicated by dashed lines.
	Fig. 3. View of the diprotonated of organic amines in the inorganic borate network along a axis.

Bis[(m-phenylenedimethylene)diammonium] tetradecaborate top

Crystal data top

2C₈H₁₄N₂²⁺·B₁₄H₆O₂₆⁴⁻	Z = 1
M_r = 849.81	F(000) = 436
Triclinic, P1	D_x = 1.646 Mg m⁻³
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1025 (18) Å	Cell parameters from 4940 reflections
b = 10.293 (2) Å	θ = 6.7–54.9°
c = 10.942 (2) Å	µ = 0.14 mm⁻¹
α = 109.68 (3)°	T = 295 K
β = 108.24 (3)°	Block, colourless
γ = 102.19 (3)°	0.34 × 0.26 × 0.18 mm
V = 857.4 (5) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3009 independent reflections
Radiation source: fine-focus sealed tube	2002 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 25.0°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.964, T_max = 0.973	k = −12→12
6803 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0299P)² + 1.2547P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
3009 reflections	Δρ_max = 0.42 e Å⁻³
272 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (2)

Crystal data top

2C₈H₁₄N₂²⁺·B₁₄H₆O₂₆⁴⁻	γ = 102.19 (3)°
M_r = 849.81	V = 857.4 (5) Å³
Triclinic, P1	Z = 1
a = 9.1025 (18) Å	Mo Kα radiation
b = 10.293 (2) Å	µ = 0.14 mm⁻¹
c = 10.942 (2) Å	T = 295 K
α = 109.68 (3)°	0.34 × 0.26 × 0.18 mm
β = 108.24 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3009 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2002 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.973	R_int = 0.023
6803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.24	Δρ_max = 0.42 e Å⁻³
3009 reflections	Δρ_min = −0.46 e Å⁻³
272 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
B1	0.6460 (5)	0.4668 (4)	0.7888 (4)	0.0240 (8)
B2	0.7413 (4)	0.3345 (4)	0.6060 (4)	0.0222 (8)
B3	0.5338 (4)	0.1936 (4)	0.6602 (4)	0.0247 (8)
B4	0.6535 (4)	0.6248 (4)	1.0187 (4)	0.0209 (7)
B5	0.4617 (5)	0.6104 (4)	0.8040 (4)	0.0233 (8)
B6	0.7437 (4)	0.3478 (4)	0.3829 (4)	0.0225 (8)
B7	0.9709 (5)	0.3173 (4)	0.5343 (4)	0.0252 (8)
O1	0.7649 (3)	0.4597 (2)	0.7304 (2)	0.0238 (5)
O2	0.6220 (3)	0.1961 (2)	0.5811 (2)	0.0279 (5)
O3	0.5410 (3)	0.3195 (2)	0.7601 (2)	0.0266 (5)
O4	0.7324 (3)	0.5555 (2)	0.9474 (2)	0.0231 (5)
O5	0.5160 (3)	0.6519 (2)	0.9489 (2)	0.0259 (5)
O6	0.5330 (3)	0.5377 (2)	0.7283 (2)	0.0248 (5)
O7	0.6718 (3)	0.3576 (2)	0.4736 (2)	0.0263 (5)
O8	0.8946 (3)	0.3301 (3)	0.4095 (2)	0.0297 (6)
O9	0.9009 (3)	0.3166 (2)	0.6244 (2)	0.0260 (5)
O10	0.4275 (3)	0.0652 (3)	0.6413 (3)	0.0447 (7)
H10A	0.4225	−0.0042	0.5733	0.067*
O11	0.7074 (3)	0.6690 (2)	1.1630 (2)	0.0269 (5)
H11A	0.6297	0.6722	1.1852	0.040*
O12	0.3292 (3)	0.6490 (3)	0.7475 (2)	0.0284 (5)
O13	1.1239 (3)	0.3064 (3)	0.5617 (2)	0.0374 (6)
H13A	1.1659	0.3147	0.6433	0.056*
N1	0.3291 (3)	0.3057 (3)	0.4112 (3)	0.0329 (7)
H1A	0.4353	0.3287	0.4654	0.049*
H1B	0.2747	0.3228	0.4662	0.049*
H1C	0.3203	0.3605	0.3633	0.049*
N2	−0.1153 (3)	0.4082 (3)	0.0950 (3)	0.0320 (7)
H2A	−0.1372	0.4667	0.0531	0.048*
H2B	−0.0078	0.4427	0.1513	0.048*
H2C	−0.1730	0.4060	0.1471	0.048*
C1	0.0788 (4)	0.1079 (4)	0.2176 (4)	0.0316 (8)
C2	0.0378 (4)	0.1765 (4)	0.1291 (4)	0.0313 (8)
H2D	0.1214	0.2350	0.1185	0.038*
C3	−0.1245 (4)	0.1600 (4)	0.0564 (4)	0.0310 (8)
C4	−0.2492 (4)	0.0650 (4)	0.0667 (4)	0.0380 (9)
H4A	−0.3593	0.0505	0.0165	0.046*
C5	−0.2107 (5)	−0.0074 (4)	0.1508 (4)	0.0452 (10)
H5A	−0.2949	−0.0713	0.1563	0.054*
C6	−0.0475 (5)	0.0143 (4)	0.2272 (4)	0.0387 (9)
H6A	−0.0220	−0.0337	0.2850	0.046*
C7	0.2573 (5)	0.1467 (4)	0.3083 (4)	0.0413 (9)
H7A	0.2681	0.0865	0.3600	0.050*
H7B	0.3166	0.1274	0.2483	0.050*
C8	−0.1624 (5)	0.2555 (4)	−0.0168 (4)	0.0373 (9)
H8A	−0.2794	0.2172	−0.0789	0.045*
H8B	−0.1006	0.2570	−0.0744	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
B1	0.0293 (19)	0.027 (2)	0.0191 (19)	0.0131 (16)	0.0134 (16)	0.0092 (16)
B2	0.0212 (18)	0.025 (2)	0.0231 (19)	0.0095 (15)	0.0124 (16)	0.0104 (16)
B3	0.0267 (19)	0.024 (2)	0.024 (2)	0.0084 (16)	0.0132 (16)	0.0098 (17)
B4	0.0219 (18)	0.0198 (18)	0.0207 (19)	0.0057 (14)	0.0104 (15)	0.0081 (15)
B5	0.0287 (19)	0.0248 (19)	0.0197 (19)	0.0128 (16)	0.0115 (16)	0.0101 (16)
B6	0.0245 (19)	0.0242 (19)	0.0179 (18)	0.0128 (15)	0.0081 (15)	0.0060 (15)
B7	0.0265 (19)	0.032 (2)	0.0162 (18)	0.0142 (17)	0.0085 (16)	0.0072 (16)
O1	0.0236 (11)	0.0247 (12)	0.0230 (12)	0.0071 (9)	0.0145 (10)	0.0067 (10)
O2	0.0325 (12)	0.0254 (12)	0.0273 (13)	0.0089 (10)	0.0197 (11)	0.0073 (10)
O3	0.0327 (13)	0.0219 (12)	0.0295 (13)	0.0083 (10)	0.0211 (11)	0.0095 (10)
O4	0.0253 (11)	0.0272 (12)	0.0160 (11)	0.0119 (9)	0.0086 (9)	0.0071 (10)
O5	0.0291 (12)	0.0354 (13)	0.0188 (12)	0.0186 (10)	0.0117 (10)	0.0119 (10)
O6	0.0292 (12)	0.0320 (13)	0.0190 (11)	0.0182 (10)	0.0119 (10)	0.0113 (10)
O7	0.0251 (12)	0.0394 (14)	0.0243 (12)	0.0182 (10)	0.0145 (10)	0.0168 (11)
O8	0.0280 (12)	0.0458 (15)	0.0253 (13)	0.0196 (11)	0.0161 (10)	0.0183 (11)
O9	0.0248 (12)	0.0392 (14)	0.0237 (12)	0.0175 (10)	0.0153 (10)	0.0157 (11)
O10	0.0624 (17)	0.0251 (14)	0.0473 (16)	0.0051 (12)	0.0399 (15)	0.0069 (12)
O11	0.0280 (12)	0.0377 (14)	0.0196 (12)	0.0158 (10)	0.0130 (10)	0.0123 (10)
O12	0.0315 (13)	0.0418 (14)	0.0240 (12)	0.0234 (11)	0.0155 (10)	0.0178 (11)
O13	0.0271 (13)	0.0688 (18)	0.0272 (13)	0.0275 (13)	0.0146 (11)	0.0238 (13)
N1	0.0276 (15)	0.0430 (18)	0.0291 (16)	0.0123 (13)	0.0137 (13)	0.0152 (14)
N2	0.0338 (16)	0.0351 (17)	0.0316 (16)	0.0160 (13)	0.0139 (13)	0.0170 (14)
C1	0.0338 (19)	0.0238 (18)	0.0276 (19)	0.0091 (15)	0.0082 (15)	0.0054 (15)
C2	0.0323 (19)	0.0286 (19)	0.0274 (19)	0.0091 (15)	0.0107 (16)	0.0085 (15)
C3	0.0325 (19)	0.0279 (19)	0.0270 (19)	0.0117 (15)	0.0102 (16)	0.0072 (15)
C4	0.0290 (19)	0.029 (2)	0.045 (2)	0.0075 (16)	0.0120 (17)	0.0087 (18)
C5	0.044 (2)	0.033 (2)	0.054 (3)	0.0065 (18)	0.024 (2)	0.014 (2)
C6	0.050 (2)	0.028 (2)	0.043 (2)	0.0132 (17)	0.0213 (19)	0.0194 (18)
C7	0.041 (2)	0.037 (2)	0.038 (2)	0.0188 (18)	0.0109 (18)	0.0096 (18)
C8	0.041 (2)	0.038 (2)	0.0250 (19)	0.0164 (17)	0.0063 (16)	0.0113 (17)

Geometric parameters (Å, º) top

B1—O1	1.421 (4)	O13—H13A	0.8200
B1—O3	1.480 (4)	N1—C7	1.489 (5)
B1—O4	1.496 (4)	N1—H1A	0.8900
B1—O6	1.499 (4)	N1—H1B	0.8900
B2—O1	1.442 (4)	N1—H1C	0.8900
B2—O9	1.463 (4)	N2—C8	1.497 (4)
B2—O2	1.477 (4)	N2—H2A	0.8900
B2—O7	1.509 (4)	N2—H2B	0.8900
B3—O2	1.354 (4)	N2—H2C	0.8900
B3—O3	1.358 (4)	C1—C2	1.385 (5)
B3—O10	1.370 (4)	C1—C6	1.391 (5)
B4—O4	1.351 (4)	C1—C7	1.495 (5)
B4—O11	1.370 (4)	C2—C3	1.383 (5)
B4—O5	1.386 (4)	C2—H2D	0.9300
B5—O6	1.338 (4)	C3—C4	1.394 (5)
B5—O12	1.377 (4)	C3—C8	1.492 (5)
B5—O5	1.380 (4)	C4—C5	1.377 (6)
B6—O7	1.338 (4)	C4—H4A	0.9300
B6—O8	1.377 (4)	C5—C6	1.383 (5)
B6—O12ⁱ	1.388 (4)	C5—H5A	0.9300
B7—O9	1.332 (4)	C6—H6A	0.9300
B7—O13	1.368 (4)	C7—H7A	0.9700
B7—O8	1.388 (4)	C7—H7B	0.9700
O10—H10A	0.8200	C8—H8A	0.9700
O11—H11A	0.8200	C8—H8B	0.9700
O12—B6ⁱ	1.388 (4)

O1—B1—O3	112.6 (3)	C7—N1—H1B	109.5
O1—B1—O4	109.6 (3)	H1A—N1—H1B	109.5
O3—B1—O4	107.5 (2)	C7—N1—H1C	109.5
O1—B1—O6	111.1 (3)	H1A—N1—H1C	109.5
O3—B1—O6	107.2 (3)	H1B—N1—H1C	109.5
O4—B1—O6	108.6 (2)	C8—N2—H2A	109.5
O1—B2—O9	108.6 (3)	C8—N2—H2B	109.5
O1—B2—O2	112.9 (2)	H2A—N2—H2B	109.5
O9—B2—O2	109.0 (3)	C8—N2—H2C	109.5
O1—B2—O7	110.2 (3)	H2A—N2—H2C	109.5
O9—B2—O7	110.1 (2)	H2B—N2—H2C	109.5
O2—B2—O7	105.9 (3)	C2—C1—C6	118.9 (3)
O2—B3—O3	121.8 (3)	C2—C1—C7	118.6 (3)
O2—B3—O10	122.5 (3)	C6—C1—C7	122.2 (3)
O3—B3—O10	115.7 (3)	C3—C2—C1	121.5 (3)
O4—B4—O11	120.4 (3)	C3—C2—H2D	119.2
O4—B4—O5	121.5 (3)	C1—C2—H2D	119.2
O11—B4—O5	118.1 (3)	C2—C3—C4	118.6 (3)
O6—B5—O12	124.5 (3)	C2—C3—C8	120.2 (3)
O6—B5—O5	121.6 (3)	C4—C3—C8	120.9 (3)
O12—B5—O5	113.8 (3)	C5—C4—C3	120.5 (3)
O7—B6—O8	122.9 (3)	C5—C4—H4A	119.8
O7—B6—O12ⁱ	122.9 (3)	C3—C4—H4A	119.8
O8—B6—O12ⁱ	114.2 (3)	C4—C5—C6	120.3 (4)
O9—B7—O13	120.9 (3)	C4—C5—H5A	119.8
O9—B7—O8	122.5 (3)	C6—C5—H5A	119.8
O13—B7—O8	116.6 (3)	C5—C6—C1	120.1 (3)
B1—O1—B2	123.5 (3)	C5—C6—H6A	120.0
B3—O2—B2	122.1 (3)	C1—C6—H6A	120.0
B3—O3—B1	121.8 (2)	N1—C7—C1	109.5 (3)
B4—O4—B1	119.7 (3)	N1—C7—H7A	109.8
B5—O5—B4	118.9 (2)	C1—C7—H7A	109.8
B5—O6—B1	120.7 (2)	N1—C7—H7B	109.8
B6—O7—B2	122.4 (2)	C1—C7—H7B	109.8
B6—O8—B7	117.6 (3)	H7A—C7—H7B	108.2
B7—O9—B2	124.2 (3)	C3—C8—N2	108.3 (3)
B3—O10—H10A	109.5	C3—C8—H8A	110.0
B4—O11—H11A	109.5	N2—C8—H8A	110.0
B5—O12—B6ⁱ	132.5 (3)	C3—C8—H8B	110.0
B7—O13—H13A	109.5	N2—C8—H8B	110.0
C7—N1—H1A	109.5	H8A—C8—H8B	108.4

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O2ⁱⁱ	0.82	1.98	2.784 (2)	168
O11—H11A···O3ⁱⁱⁱ	0.82	1.84	2.659 (2)	179
O13—H13A···O11^iv	0.82	2.00	2.815 (2)	173
N1—H1A···O7	0.89	2.08	2.863 (2)	146
N1—H1B···O13^v	0.89	1.98	2.850 (2)	166
N1—H1C···O6ⁱ	0.89	2.20	2.916 (2)	137
N1—H1C···O1ⁱ	0.89	2.54	3.394 (2)	161
N2—H2A···O4^vi	0.89	1.97	2.822 (2)	159
N2—H2B···O1ⁱ	0.89	1.99	2.877 (2)	173
N2—H2B···O9ⁱ	0.89	2.55	3.052 (2)	116
N2—H2C···O12^vii	0.89	2.19	3.067 (2)	168

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

Experimental details

Crystal data
Chemical formula	2C₈H₁₄N₂²⁺·B₁₄H₆O₂₆⁴⁻
M_r	849.81
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.1025 (18), 10.293 (2), 10.942 (2)
α, β, γ (°)	109.68 (3), 108.24 (3), 102.19 (3)
V (Å³)	857.4 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.34 × 0.26 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.964, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	6803, 3009, 2002
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.128, 1.24
No. of reflections	3009
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.46

Computer programs: RAPID-AUTO (Rigaku, 1998), Crystal Structure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O2ⁱ	0.82	1.98	2.784 (2)	168
O11—H11A···O3ⁱⁱ	0.82	1.84	2.659 (2)	179
O13—H13A···O11ⁱⁱⁱ	0.82	2.00	2.815 (2)	173
N1—H1A···O7	0.89	2.08	2.863 (2)	146
N1—H1B···O13^iv	0.89	1.98	2.850 (2)	166
N1—H1C···O6^v	0.89	2.20	2.916 (2)	137
N1—H1C···O1^v	0.89	2.54	3.394 (2)	161
N2—H2A···O4^vi	0.89	1.97	2.822 (2)	159
N2—H2B···O1^v	0.89	1.99	2.877 (2)	173
N2—H2B···O9^v	0.89	2.55	3.052 (2)	116
N2—H2C···O12^vii	0.89	2.19	3.067 (2)	168

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

Acknowledgements

This work was supported by the Ningbo Natural Science Foundation (grant No. 2007A610022) and the K. C. Wong Magna Fund of Ningbo University.

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