Dimethyl­ammonium bis­(3-oxidonaphthalene-2-carboxyl­ato)borate hemihydrate

Tombul, M.; Güven, K.; Svoboda, I.

doi:10.1107/S1600536807066810

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages o309-o310

https://doi.org/10.1107/S1600536807066810

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Dimethylammonium bis(3-oxidonaphthalene-2-carboxylato)borate hemihydrate

Mustafa Tombul,^a ^* Kutalmış Güven ^b and Ingrid Svoboda ^c

^aDepartment of Chemistry, Faculty of Arts and Sciences, University of Kırıkkale, Campus, Yahşihan, 71450 Kırıkkale, Turkey, ^bDepartment of Physics, Faculty of Arts and Sciences, University of Kırıkkale, Campus, Yahşihan, 71450 Kırıkkale, Turkey, and ^cStructural Research, Material Science, Darmstadt University of Technology, Petersen Strasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: mustafatombul38@gmail.com

(Received 28 November 2007; accepted 13 December 2007; online 18 December 2007)

The title compound, C₂H₈N⁺·C₂₂H₁₂BO₆⁻·0.5H₂O, was synthesized under atmospheric conditions in the presence of dimethylformamide acting as a template. The structure is composed of [NH₂(CH₃)₂]⁺ cations, bis(3-oxidonaphthalene-2-carboxylato)borate anions and water molecules. The water molecule lies on a twofold rotation axis. The stabilization of the crystal structure comes from electrostatic interactions and is assisted by intermolecular O—H⋯O and N—H⋯O hydrogen bonds between the layers.

Related literature

For related literature, see: Carr et al. (2005 ); Downard et al. (2002 ); Errington et al. (1999 ); Green et al. (2000 ); Grice et al. (1999 ); Li & Liu (2006 ); Schubert et al. (2000 ); Tombul et al. (2003 ); Tombul, Guven, Büyükgüngör et al. (2007 ); Touboul et al. (2003 ); Zhang & Liu (2006 ); Zhang et al. (2005 ).

Experimental

Crystal data

C₂H₈N⁺·C₂₂H₁₂BO₆⁻·0.5H₂O
M_r = 438.24
Monoclinic, C 2/c
a = 32.011 (3) Å
b = 9.774 (1) Å
c = 14.742 (1) Å
β = 112.628 (7)°
V = 4257.2 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 303 (2) K
0.48 × 0.08 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: numerical [using a multifaceted crystal model based on expressions derived (Clark & Reid, 1995 )] T_min = 0.981, T_max = 0.994
16173 measured reflections
4321 independent reflections
1708 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.093
wR(F²) = 0.152
S = 1.12
4321 reflections
299 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—B1	1.427 (5)
O2—B1	1.496 (5)
O4—B1	1.426 (5)
O5—B1	1.502 (5)

O4—B1—O1	110.7 (4)
O4—B1—O2	107.7 (3)
O1—B1—O2	112.4 (3)
O4—B1—O5	112.0 (3)
O1—B1—O5	107.9 (3)
O2—B1—O5	106.1 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H25A⋯O3ⁱ	1.00	1.88	2.849 (4)	162
N5—H25B⋯O6ⁱⁱ	0.95	2.12	2.839 (4)	131
N5—H25B⋯O3ⁱⁱⁱ	0.95	2.33	2.871 (4)	116
O7—H27⋯O5	0.85 (3)	2.18 (4)	3.010 (3)	163.3 (12)
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.31.4. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.31.4. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066810/at2517sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066810/at2517Isup2.hkl

checkCIF report

Comment top

Owing to their rich structural chemistry and potential applications in mineralogy (Grice et al., 1999) and nonlinear optical materials (Touboul et al., 2003), borates have provided an abounding area of research for over half a century. Boron can form a large variety of compounds due to the complexity of the structures involved. Boron atom coordinate with oxygen not only in fourfold coordination (tetrahedral, BO₄) but also in threefold coordination (triangular, BO₃). These BO₃ and BO₄ groups favour polymerization via common corners into large polynuclear anion units including isolated or finite clusters, chains, sheets, and networks (Grice et al., 1999). Most borates synthesized and studied to date have been prepared under the templating effect of inorganic cations, such as alkali-metal, alkaline-earth, rare-earth or transition cations. Accordingly, many borate systems taking into account alkali metal, alkaline earth metal, rare-earth, and transition metals have been explored in recent years (Schubert et al., 2000). Currently, studies conducted in this area are primarily focused on improving existing materials utilized and search for new materials. In comparison to inorganic borates, synthesis, crystal structure and application of organic borates seem to be insufficient (Li & Liu, 2006; Zhang & Liu, 2006; Carr et al., 2005; Zhang et al., 2005; Downard et al., 2002; Green et al., 2000). As part of our ongoing study of the synthesis and structure of organoborate complexes (Errington et al., 1999; Tombul et al., 2003; Tombul, Guven, Büyükgüngör et al., 2007), we have prepared a new organically templated borate, (I), using dimethylformamide as the structure-directing agent.

The asymmetric unit of (I) (Fig.1) consists of [BO₄(C₁₁H₆O)₂]^- anions, [NH₂(CH₃)₂]⁺ cations and water molecule. The [BO₄(C₁₁H₆O)₂]^- anion consists of one set of distorted [BO₄] tetrahedra and two sets of slightly deformed [C₁₁H₆O] planes with oxygen atoms as sharing vertexes. The boron atom is bonded to four oxygen atoms to form a highly tetrahedral environment (mean OBO bond angle of 109.46 (3)°). The B—O bond lengths are typical for such tetrahedral borates, with B—O_carboxyl bond lengths (mean 1.499 (5) Å) being slightly longer than B—O_hyroxyl bond lengths (mean 1.427 (5) Å). Each [C₁₁H₆O] unit is almost planar, and both [C₁₁H₆O] units in BO₄(C₁₁H₆O)₂]^- are nearly perpendicular to each other. The borate rings highly coplanar with the corresponding aryl rings [with 0.0779 Å r.m.s. deviation for Plane A (C1—C11/O1—O3) and 0.0648 Å r.m.s. deviation for Plane B (C12—C22/,O4—O6)]. The coordination planes (Planes C (O2, B1, O1) and D (O5, B1, O4) intersects at an angle of 89.73 (26) °. Dimethylammonium cation is distorted tetrahedral environment with CNC bond angle of 113.5 (4) ° and located with a large distance from the anion (B—N distance 6.108 (15) Å).

In the crystal structure [BO₄(C₁₁H₆O)₂]^- anions and [NH₂(CH₃)₂]⁺ cations are discrete units and they interact both electrostatically and via N—H···O hydrogen bonds with N···O distances in the range 2.839 (4) Å – 2.872 (4) Å (Fig.2). The water molecule is also involved in normal, slightly bent, hydrogen bond with the borate anion at a distance of 3.012 (3) Å. The acceptors are all carboxylate O atoms of the aromatic ring (Table 2). For the synthesis of (I), dimethylformamide acts not only as the solvent, but also as the reactant and it decomposes under experimental conditions forming [NH₂(CH₃)₂]⁺ cations.

Related literature top

For related literature, see: Carr et al. (2005); Downard et al. (2002); Errington et al. (1999); Green et al. (2000); Grice et al. (1999); Li & Liu (2006); Schubert et al. (2000); Tombul et al. (2003); Tombul, Guven, Büyükgüngör et al. (2007); Touboul et al. (2003); Zhang & Liu (2006); Zhang et al. (2005).

Experimental top

For the preparation of title compound, (I), B(OH)₃(133 mg, 2.16 mmol,) was carefully added to a stirred DMF (10.0 ml) solution of 3-hydroxynaphthalene-2-carboxylic acid (875 mg, 4.65 mmol) at ambient temperature. The reaction mixture initially gave a brown solution which was stirred at 398 K for 2.5 h until all became a gel-like material. This product was then redissolved in the mixture of MeOH/CH₂Cl₂ (10 ml; 1:1) and allowed to stand at room temperature for a couple of hours, whereupon transparent and fine crystals were harvested. Yield, 79% (based on B(OH)₃); Elemental analysis: (Found): C 65.48, H 5.18, N 3.19%. Calculated for C₂₄H₂₂O₇NB: C 64.45, H 4.96, N 3.13%. ¹H NMR (d⁶-DMSO-CDCl₃, 298 K, TMS): δ (p.p.m.): All aromatic signals are observed between the region at 7.12 and 8.43. ¹³C NMR (d⁶-DMSO-CDCl₃, 298 K, TMS): δ (p.p.m.): δ 119.7, 122.5, 128.1, 132.2, 142.4, 160.0, 161.6, 169.7, 177.0.

Structure description top

For related literature, see: Carr et al. (2005); Downard et al. (2002); Errington et al. (1999); Green et al. (2000); Grice et al. (1999); Li & Liu (2006); Schubert et al. (2000); Tombul et al. (2003); Tombul, Guven, Büyükgüngör et al. (2007); Touboul et al. (2003); Zhang & Liu (2006); Zhang et al. (2005).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006).; software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Showing the atom-labelling scheme of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Hydrogen bond labelling scheme for (I). Dashed lines indicate hydrogen bonds. Some hydrogen atoms were omited for clarity). [Symmetry codes: (i): x, -y + 1, z - 1/2, (ii): x, y + 1, z, (iii):-x, -y + 1, -z + 1].

Dimethylammonium bis(3-oxidonaphthalene-2-carboxylato)borate hemihydrate top

Crystal data top

C₂H₈N⁺·C₂₂H₁₂BO₆⁻·0.5H₂O	F(000) = 1832
M_r = 438.24	D_x = 1.367 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2075 reflections
a = 32.011 (3) Å	θ = 2.5–21.1°
b = 9.774 (1) Å	µ = 0.10 mm⁻¹
c = 14.742 (1) Å	T = 303 K
β = 112.628 (7)°	Rod shape, light yellow
V = 4257.2 (7) Å³	0.48 × 0.08 × 0.08 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	4321 independent reflections
Radiation source: fine-focus sealed tube	1708 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 8.4012 pixels mm^-1	θ_max = 26.4°, θ_min = 2.5°
Rotation method data acquisition using ω and φ scans	h = −40→40
Absorption correction: numerical [absorption correction using a multifaceted crystal model based on expressions derived (Clark & Reid, 1995)]	k = −9→12
T_min = 0.981, T_max = 0.994	l = −18→18
16173 measured reflections

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)] = 0.093	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0247P)² + 7.7951P] where P = (F_o² + 2F_c²)/3
4321 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.21 e Å⁻³
3 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂H₈N⁺·C₂₂H₁₂BO₆⁻·0.5H₂O	V = 4257.2 (7) Å³
M_r = 438.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 32.011 (3) Å	µ = 0.10 mm⁻¹
b = 9.774 (1) Å	T = 303 K
c = 14.742 (1) Å	0.48 × 0.08 × 0.08 mm
β = 112.628 (7)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	4321 independent reflections
Absorption correction: numerical [absorption correction using a multifaceted crystal model based on expressions derived (Clark & Reid, 1995)]	1708 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.994	R_int = 0.079
16173 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.093	3 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.21 e Å⁻³
4321 reflections	Δρ_min = −0.23 e Å⁻³
299 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
O1	−0.01987 (8)	0.4067 (3)	0.37753 (18)	0.0487 (8)
O2	−0.03911 (9)	0.2873 (3)	0.5007 (2)	0.0520 (8)
O3	0.01354 (9)	0.2159 (3)	0.6392 (2)	0.0643 (9)
O4	−0.09425 (8)	0.4084 (3)	0.37123 (19)	0.0474 (7)
O5	−0.06167 (9)	0.2000 (3)	0.33692 (19)	0.0498 (8)
O6	−0.10420 (9)	0.0190 (3)	0.2734 (2)	0.0608 (9)
C1	0.02357 (13)	0.3624 (4)	0.4222 (3)	0.0421 (11)
C2	0.05411 (13)	0.3882 (4)	0.3807 (3)	0.0443 (11)
H2	0.0451	0.4358	0.3216	0.053*
C3	0.09922 (13)	0.3435 (4)	0.4264 (3)	0.0423 (11)
C4	0.13136 (14)	0.3649 (5)	0.3838 (3)	0.0564 (13)
H4	0.1230	0.4126	0.3249	0.068*
C5	0.17420 (16)	0.3169 (5)	0.4274 (4)	0.0693 (15)
H5	0.1947	0.3314	0.3976	0.083*
C6	0.18799 (15)	0.2461 (5)	0.5163 (4)	0.0712 (15)
H6	0.2175	0.2135	0.5452	0.085*
C7	0.15843 (14)	0.2246 (5)	0.5608 (3)	0.0615 (13)
H7	0.1679	0.1784	0.6205	0.074*
C8	0.11340 (13)	0.2721 (4)	0.5170 (3)	0.0443 (11)
C9	0.08061 (13)	0.2483 (4)	0.5579 (3)	0.0457 (11)
H9	0.0890	0.2026	0.6176	0.055*
C10	0.03693 (13)	0.2910 (4)	0.5115 (3)	0.0398 (10)
C11	0.00351 (14)	0.2617 (4)	0.5560 (4)	0.0482 (12)
C12	−0.13259 (13)	0.3378 (4)	0.3605 (3)	0.0406 (10)
C13	−0.16686 (12)	0.4009 (4)	0.3771 (3)	0.0462 (11)
H13	−0.1638	0.4923	0.3962	0.055*
C14	−0.20682 (13)	0.3303 (5)	0.3661 (3)	0.0470 (12)
C15	−0.24235 (14)	0.3923 (5)	0.3855 (3)	0.0686 (15)
H15	−0.2397	0.4828	0.4065	0.082*
C16	−0.28029 (16)	0.3202 (6)	0.3738 (4)	0.0833 (17)
H16	−0.3035	0.3628	0.3863	0.100*
C17	−0.28545 (16)	0.1834 (6)	0.3434 (4)	0.0858 (17)
H17	−0.3117	0.1356	0.3362	0.103*
C18	−0.25178 (14)	0.1214 (5)	0.3245 (3)	0.0694 (14)
H18	−0.2551	0.0304	0.3046	0.083*
C19	−0.21161 (13)	0.1922 (5)	0.3345 (3)	0.0457 (11)
C20	−0.17613 (13)	0.1312 (4)	0.3159 (3)	0.0463 (11)
H20	−0.1792	0.0412	0.2937	0.056*
C21	−0.13709 (12)	0.2008 (4)	0.3295 (3)	0.0379 (10)
C22	−0.10027 (14)	0.1318 (5)	0.3107 (3)	0.0466 (11)
B1	−0.05381 (15)	0.3300 (5)	0.3956 (4)	0.0444 (13)
N5	−0.06832 (10)	0.8557 (4)	0.1613 (2)	0.0518 (9)
H25A	−0.0368	0.8299	0.1688	0.062*
H25B	−0.0619	0.9008	0.2225	0.062*
C23	−0.09329 (15)	0.7284 (5)	0.1570 (4)	0.0791 (16)
H23A	−0.0763	0.6713	0.2117	0.095*
H23B	−0.0979	0.6813	0.0967	0.095*
H23C	−0.1221	0.7494	0.1596	0.095*
C24	−0.09181 (16)	0.9503 (5)	0.0806 (3)	0.0898 (18)
H24A	−0.0997	0.9036	0.0190	0.108*
H24B	−0.0723	1.0261	0.0831	0.108*
H24C	−0.1188	0.9833	0.0869	0.108*
O7	0.0000	0.0715 (4)	0.2500	0.0849 (15)
H27	−0.0156 (12)	0.1236 (14)	0.271 (3)	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0322 (16)	0.061 (2)	0.0533 (19)	−0.0011 (15)	0.0168 (15)	0.0074 (15)
O2	0.0364 (16)	0.071 (2)	0.053 (2)	−0.0023 (16)	0.0217 (15)	0.0056 (17)
O3	0.0504 (18)	0.088 (3)	0.058 (2)	−0.0010 (17)	0.0247 (17)	0.0188 (19)
O4	0.0370 (16)	0.0427 (19)	0.0651 (19)	−0.0031 (14)	0.0226 (15)	−0.0049 (15)
O5	0.0442 (17)	0.047 (2)	0.063 (2)	0.0006 (15)	0.0262 (16)	−0.0089 (16)
O6	0.0632 (19)	0.051 (2)	0.078 (2)	0.0015 (17)	0.0375 (17)	−0.0150 (18)
C1	0.037 (3)	0.042 (3)	0.048 (3)	−0.006 (2)	0.017 (2)	0.000 (2)
C2	0.040 (3)	0.050 (3)	0.045 (3)	−0.008 (2)	0.020 (2)	0.000 (2)
C3	0.038 (3)	0.043 (3)	0.049 (3)	−0.010 (2)	0.019 (2)	−0.012 (2)
C4	0.046 (3)	0.067 (3)	0.067 (3)	−0.013 (3)	0.033 (3)	−0.011 (3)
C5	0.052 (3)	0.084 (4)	0.088 (4)	−0.009 (3)	0.045 (3)	−0.012 (3)
C6	0.040 (3)	0.076 (4)	0.103 (4)	0.001 (3)	0.033 (3)	0.001 (3)
C7	0.043 (3)	0.060 (3)	0.079 (3)	0.003 (2)	0.020 (3)	0.007 (3)
C8	0.038 (3)	0.042 (3)	0.049 (3)	−0.004 (2)	0.012 (2)	−0.003 (2)
C9	0.046 (3)	0.045 (3)	0.049 (3)	−0.003 (2)	0.021 (2)	0.000 (2)
C10	0.035 (2)	0.040 (3)	0.048 (3)	−0.005 (2)	0.021 (2)	0.001 (2)
C11	0.046 (3)	0.047 (3)	0.056 (3)	−0.004 (2)	0.024 (3)	−0.002 (3)
C12	0.038 (2)	0.038 (3)	0.047 (3)	−0.001 (2)	0.017 (2)	−0.002 (2)
C13	0.040 (2)	0.041 (3)	0.060 (3)	0.001 (2)	0.021 (2)	−0.008 (2)
C14	0.034 (2)	0.054 (3)	0.056 (3)	0.005 (2)	0.020 (2)	−0.003 (2)
C15	0.047 (3)	0.069 (4)	0.100 (4)	0.002 (3)	0.039 (3)	−0.007 (3)
C16	0.054 (3)	0.085 (5)	0.123 (5)	0.004 (3)	0.048 (3)	−0.006 (4)
C17	0.049 (3)	0.086 (5)	0.133 (5)	−0.015 (3)	0.046 (3)	−0.006 (4)
C18	0.053 (3)	0.070 (4)	0.089 (4)	−0.011 (3)	0.031 (3)	−0.004 (3)
C19	0.035 (2)	0.053 (3)	0.050 (3)	−0.003 (2)	0.018 (2)	0.001 (2)
C20	0.048 (3)	0.045 (3)	0.047 (3)	−0.002 (2)	0.019 (2)	−0.005 (2)
C21	0.033 (2)	0.041 (3)	0.040 (3)	0.004 (2)	0.014 (2)	0.001 (2)
C22	0.049 (3)	0.045 (3)	0.048 (3)	0.001 (3)	0.021 (2)	−0.002 (2)
B1	0.027 (3)	0.057 (4)	0.050 (3)	−0.002 (3)	0.017 (3)	0.001 (3)
N5	0.048 (2)	0.056 (2)	0.052 (2)	0.006 (2)	0.0200 (19)	−0.003 (2)
C23	0.069 (3)	0.074 (4)	0.097 (4)	−0.020 (3)	0.035 (3)	−0.026 (3)
C24	0.106 (4)	0.096 (5)	0.065 (4)	0.040 (4)	0.029 (3)	0.013 (3)
O7	0.086 (4)	0.060 (3)	0.135 (4)	0.000	0.071 (3)	0.000

Geometric parameters (Å, º) top

O1—C1	1.360 (4)	C12—C21	1.405 (5)
O1—B1	1.427 (5)	C13—C14	1.406 (5)
O2—C11	1.316 (4)	C13—H13	0.9300
O2—B1	1.496 (5)	C14—C15	1.412 (5)
O3—C11	1.227 (4)	C14—C19	1.417 (5)
O4—C12	1.363 (4)	C15—C16	1.356 (6)
O4—B1	1.426 (5)	C15—H15	0.9300
O5—C22	1.324 (4)	C16—C17	1.399 (6)
O5—B1	1.502 (5)	C16—H16	0.9300
O6—C22	1.216 (4)	C17—C18	1.355 (6)
C1—C2	1.362 (5)	C17—H17	0.9300
C1—C10	1.404 (5)	C18—C19	1.417 (5)
C2—C3	1.408 (5)	C18—H18	0.9300
C2—H2	0.9300	C19—C20	1.400 (5)
C3—C4	1.412 (5)	C20—C21	1.368 (5)
C3—C8	1.417 (5)	C20—H20	0.9300
C4—C5	1.355 (6)	C21—C22	1.473 (5)
C4—H4	0.9300	N5—C24	1.466 (5)
C5—C6	1.395 (6)	N5—C23	1.467 (5)
C5—H5	0.9300	N5—H25A	1.0035
C6—C7	1.360 (5)	N5—H25B	0.9530
C6—H6	0.9300	C23—H23A	0.9600
C7—C8	1.412 (5)	C23—H23B	0.9600
C7—H7	0.9300	C23—H23C	0.9600
C8—C9	1.416 (5)	C24—H24A	0.9600
C9—C10	1.364 (5)	C24—H24B	0.9600
C9—H9	0.9300	C24—H24C	0.9600
C10—C11	1.482 (5)	O7—H27	0.85 (3)
C12—C13	1.361 (5)

C1—O1—B1	116.9 (3)	C16—C15—H15	119.9
C11—O2—B1	122.2 (3)	C14—C15—H15	119.9
C12—O4—B1	116.5 (3)	C15—C16—C17	121.8 (5)
C22—O5—B1	121.6 (3)	C15—C16—H16	119.1
O1—C1—C2	120.0 (4)	C17—C16—H16	119.1
O1—C1—C10	119.9 (4)	C18—C17—C16	119.2 (5)
C2—C1—C10	120.1 (4)	C18—C17—H17	120.4
C1—C2—C3	120.5 (4)	C16—C17—H17	120.4
C1—C2—H2	119.7	C17—C18—C19	121.4 (5)
C3—C2—H2	119.7	C17—C18—H18	119.3
C2—C3—C4	121.9 (4)	C19—C18—H18	119.3
C2—C3—C8	120.2 (4)	C20—C19—C18	122.9 (4)
C4—C3—C8	117.9 (4)	C20—C19—C14	118.5 (4)
C5—C4—C3	121.0 (5)	C18—C19—C14	118.6 (4)
C5—C4—H4	119.5	C21—C20—C19	121.6 (4)
C3—C4—H4	119.5	C21—C20—H20	119.2
C4—C5—C6	120.9 (4)	C19—C20—H20	119.2
C4—C5—H5	119.5	C20—C21—C12	119.7 (4)
C6—C5—H5	119.5	C20—C21—C22	119.8 (4)
C7—C6—C5	120.2 (4)	C12—C21—C22	120.5 (4)
C7—C6—H6	119.9	O6—C22—O5	120.7 (4)
C5—C6—H6	119.9	O6—C22—C21	123.3 (4)
C6—C7—C8	120.4 (5)	O5—C22—C21	116.0 (4)
C6—C7—H7	119.8	O4—B1—O1	110.7 (4)
C8—C7—H7	119.8	O4—B1—O2	107.7 (3)
C7—C8—C9	123.0 (4)	O1—B1—O2	112.4 (3)
C7—C8—C3	119.6 (4)	O4—B1—O5	112.0 (3)
C9—C8—C3	117.4 (4)	O1—B1—O5	107.9 (3)
C10—C9—C8	121.4 (4)	O2—B1—O5	106.1 (4)
C10—C9—H9	119.3	C24—N5—C23	113.5 (4)
C8—C9—H9	119.3	C24—N5—H25A	115.4
C9—C10—C1	120.4 (4)	C23—N5—H25A	107.4
C9—C10—C11	119.6 (4)	C24—N5—H25B	109.4
C1—C10—C11	120.0 (4)	C23—N5—H25B	110.4
O3—C11—O2	119.9 (4)	H25A—N5—H25B	99.9
O3—C11—C10	123.9 (4)	N5—C23—H23A	109.5
O2—C11—C10	116.2 (4)	N5—C23—H23B	109.5
C13—C12—O4	120.1 (4)	H23A—C23—H23B	109.5
C13—C12—C21	120.1 (4)	N5—C23—H23C	109.5
O4—C12—C21	119.7 (4)	H23A—C23—H23C	109.5
C12—C13—C14	121.2 (4)	H23B—C23—H23C	109.5
C12—C13—H13	119.4	N5—C24—H24A	109.5
C14—C13—H13	119.4	N5—C24—H24B	109.5
C13—C14—C15	122.3 (4)	H24A—C24—H24B	109.5
C13—C14—C19	118.9 (4)	N5—C24—H24C	109.5
C15—C14—C19	118.8 (4)	H24A—C24—H24C	109.5
C16—C15—C14	120.2 (5)	H24B—C24—H24C	109.5

B1—O1—C1—C2	152.4 (4)	C13—C14—C15—C16	180.0 (4)
B1—O1—C1—C10	−28.0 (5)	C19—C14—C15—C16	−0.2 (7)
O1—C1—C2—C3	179.7 (4)	C14—C15—C16—C17	0.6 (8)
C10—C1—C2—C3	0.1 (6)	C15—C16—C17—C18	−0.4 (9)
C1—C2—C3—C4	178.0 (4)	C16—C17—C18—C19	−0.3 (8)
C1—C2—C3—C8	−0.6 (6)	C17—C18—C19—C20	179.8 (5)
C2—C3—C4—C5	−177.7 (4)	C17—C18—C19—C14	0.8 (7)
C8—C3—C4—C5	1.0 (6)	C13—C14—C19—C20	0.2 (6)
C3—C4—C5—C6	−0.7 (7)	C15—C14—C19—C20	−179.6 (4)
C4—C5—C6—C7	−0.2 (8)	C13—C14—C19—C18	179.3 (4)
C5—C6—C7—C8	0.8 (7)	C15—C14—C19—C18	−0.5 (6)
C6—C7—C8—C9	177.5 (4)	C18—C19—C20—C21	−177.6 (4)
C6—C7—C8—C3	−0.5 (6)	C14—C19—C20—C21	1.4 (6)
C2—C3—C8—C7	178.3 (4)	C19—C20—C21—C12	−1.7 (6)
C4—C3—C8—C7	−0.4 (6)	C19—C20—C21—C22	178.9 (4)
C2—C3—C8—C9	0.2 (6)	C13—C12—C21—C20	0.2 (6)
C4—C3—C8—C9	−178.5 (4)	O4—C12—C21—C20	−178.1 (3)
C7—C8—C9—C10	−177.3 (4)	C13—C12—C21—C22	179.6 (4)
C3—C8—C9—C10	0.7 (6)	O4—C12—C21—C22	1.4 (5)
C8—C9—C10—C1	−1.2 (6)	B1—O5—C22—O6	−171.3 (4)
C8—C9—C10—C11	178.9 (4)	B1—O5—C22—C21	8.7 (5)
O1—C1—C10—C9	−178.8 (4)	C20—C21—C22—O6	8.0 (6)
C2—C1—C10—C9	0.8 (6)	C12—C21—C22—O6	−171.4 (4)
O1—C1—C10—C11	1.1 (6)	C20—C21—C22—O5	−172.0 (4)
C2—C1—C10—C11	−179.3 (4)	C12—C21—C22—O5	8.5 (5)
B1—O2—C11—O3	−173.9 (4)	C12—O4—B1—O1	163.5 (3)
B1—O2—C11—C10	6.0 (6)	C12—O4—B1—O2	−73.2 (4)
C9—C10—C11—O3	9.7 (6)	C12—O4—B1—O5	43.1 (5)
C1—C10—C11—O3	−170.2 (4)	C1—O1—B1—O4	161.8 (3)
C9—C10—C11—O2	−170.2 (4)	C1—O1—B1—O2	41.4 (5)
C1—C10—C11—O2	9.9 (6)	C1—O1—B1—O5	−75.3 (4)
B1—O4—C12—C13	153.2 (4)	C11—O2—B1—O4	−153.3 (4)
B1—O4—C12—C21	−28.6 (5)	C11—O2—B1—O1	−31.1 (6)
O4—C12—C13—C14	179.7 (4)	C11—O2—B1—O5	86.6 (4)
C21—C12—C13—C14	1.5 (6)	C22—O5—B1—O4	−34.1 (5)
C12—C13—C14—C15	178.2 (4)	C22—O5—B1—O1	−156.1 (3)
C12—C13—C14—C19	−1.7 (6)	C22—O5—B1—O2	83.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H25A···O3ⁱ	1.00	1.88	2.849 (4)	162
N5—H25B···O6ⁱⁱ	0.95	2.12	2.839 (4)	131
N5—H25B···O3ⁱⁱⁱ	0.95	2.33	2.871 (4)	116
O7—H27···O5	0.85 (3)	2.18 (4)	3.010 (3)	163 (1)

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

Experimental details

Crystal data
Chemical formula	C₂H₈N⁺·C₂₂H₁₂BO₆⁻·0.5H₂O
M_r	438.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	303
a, b, c (Å)	32.011 (3), 9.774 (1), 14.742 (1)
β (°)	112.628 (7)
V (Å³)	4257.2 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.48 × 0.08 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Numerical [absorption correction using a multifaceted crystal model based on expressions derived (Clark & Reid, 1995)]
T_min, T_max	0.981, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	16173, 4321, 1708
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.093, 0.152, 1.12
No. of reflections	4321
No. of parameters	299
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Mercury (Macrae et al., 2006)., publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

O1—B1	1.427 (5)	O4—B1	1.426 (5)
O2—B1	1.496 (5)	O5—B1	1.502 (5)

O4—B1—O1	110.7 (4)	O4—B1—O5	112.0 (3)
O4—B1—O2	107.7 (3)	O1—B1—O5	107.9 (3)
O1—B1—O2	112.4 (3)	O2—B1—O5	106.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H25A···O3ⁱ	1.00	1.88	2.849 (4)	161.8
N5—H25B···O6ⁱⁱ	0.95	2.12	2.839 (4)	130.7
N5—H25B···O3ⁱⁱⁱ	0.95	2.33	2.871 (4)	115.5
O7—H27···O5	0.85 (3)	2.18 (4)	3.010 (3)	163.3 (12)

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

Acknowledgements

The authors gratefully acknowledge Kırıkkale University Scientific Research Centre for financial support of this work (grant No. 2007/49) and Professor Dr Hartmut Fuess, Institute of Materials Science, Darmstadt University of Technology, Germany, for use of the diffractometer.

References

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