Bis[3-(dihydroxy-boryl)anilinium] sulfate.

In the title compound, 2C(6)H(9)BNO(2) (+)·SO(4) (2-), the dihydroxy-boryl group of one of the two independent boronic acid mol-ecules participates in (B)O-H⋯O(B) and N-H⋯O(B) hydrogen bonds, while the second is involved mainly in the formation of the charge-assisted heterodimeric synthon -B(OH)(2)⋯(-)O(2)SO(2) (-). These aggregates are further connected through N-H⋯O(sulfate) inter-actions, forming a complex three-dimensional hydrogen-bonded network.

Related literature

For related salts, see: Braga et al. (2003 ▶); Kara et al. (2006 ▶); Rogowska et al. (2006 ▶); Melendez et al. (1996 ▶); Plaut et al. (2000 ▶); SeethaLekshmi et al. (2006 ▶). For the use of boronic acids in crystal engineering, see: Aakeröy et al. (2005 ▶); Filthaus et al. (2008 ▶); Fournier et al. (2003 ▶); Pedireddi et al. (2004 ▶); Rodríguez-Cuamatzi et al. (2004a ▶,b ▶, 2005 ▶, 2009 ▶); Shimpi et al. (2007 ▶); Zhang et al. (2007 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

2C6H9BNO2 +·SO4 2−

M = 371.96

Monoclinic,

a = 5.3589 (9) Å

b = 15.695 (3) Å

c = 20.489 (3) Å

β = 101.423 (3)°

V = 1689.1 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 173 K

0.41 × 0.18 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.83, T max = 1.00

18634 measured reflections

3675 independent reflections

2642 reflections with I > 2σ(I)

R int = 0.096

Refinement

R[F 2 > 2σ(F 2)] = 0.078

wR(F 2) = 0.145

S = 1.12

3675 reflections

256 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus NT (Bruker, 2001 ▶); data reduction: SAINT-Plus NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810012092/tk2649sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012092/tk2649Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C6H9BNO2+·SO42−	F(000) = 776
Mr = 371.96	Dx = 1.463 Mg m−3
Monoclinic, P21/c	Melting point > 573 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.3589 (9) Å	Cell parameters from 1721 reflections
b = 15.695 (3) Å	θ = 2.6–20.0°
c = 20.489 (3) Å	µ = 0.24 mm−1
β = 101.423 (3)°	T = 173 K
V = 1689.1 (5) Å3	Rectangular prism, colourless
Z = 4	0.41 × 0.18 × 0.09 mm

Bruker SMART APEX CCD area-detector diffractometer	3675 independent reflections
Radiation source: fine-focus sealed tube	2642 reflections with I > 2σ(I)
graphite	Rint = 0.096
Detector resolution: 8.3 pixels mm-1	θmax = 27.0°, θmin = 1.7°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −19→20
Tmin = 0.83, Tmax = 1.00	l = −26→26
18634 measured reflections

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0357P)2 + 2.0612P] where P = (Fo2 + 2Fc2)/3
3675 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.36 e Å−3
10 restraints	Δρmin = −0.37 e Å−3

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 > 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.

	x	y	z	Uiso*/Ueq
B1	0.5330 (8)	0.8900 (3)	0.3774 (2)	0.0287 (10)
N1	0.3567 (8)	0.6073 (2)	0.47243 (17)	0.0409 (9)
H1A	0.475 (6)	0.594 (3)	0.451 (2)	0.061*
H1B	0.230 (6)	0.578 (3)	0.451 (2)	0.061*
H1C	0.381 (9)	0.588 (3)	0.5125 (8)	0.061*
O1	0.5531 (6)	0.97477 (16)	0.38584 (13)	0.0415 (8)
H1'	0.602 (9)	1.000 (3)	0.3546 (16)	0.062*
O2	0.6184 (5)	0.85326 (15)	0.32467 (12)	0.0271 (6)
H2'	0.586 (7)	0.8010 (6)	0.320 (2)	0.041*
C1	0.4023 (7)	0.8355 (2)	0.42509 (17)	0.0277 (9)
C2	0.4458 (7)	0.7479 (2)	0.43246 (17)	0.0259 (8)
H2	0.5704	0.7219	0.4119	0.031*
C3	0.3110 (7)	0.6988 (2)	0.46910 (18)	0.0274 (9)
C4	0.1327 (7)	0.7344 (3)	0.50092 (19)	0.0350 (10)
H4	0.0392	0.7000	0.5258	0.042*
C5	0.0930 (8)	0.8213 (3)	0.4958 (2)	0.0433 (11)
H5	−0.0273	0.8470	0.5181	0.052*
C6	0.2248 (8)	0.8711 (3)	0.45906 (19)	0.0379 (10)
H6	0.1951	0.9308	0.4566	0.045*
B31	1.3528 (8)	0.6344 (3)	0.2462 (2)	0.0234 (9)
N31	0.7762 (6)	0.88966 (19)	0.20148 (15)	0.0218 (6)
H31A	0.664 (5)	0.910 (2)	0.1691 (12)	0.033*
H31B	0.911 (4)	0.920 (2)	0.2040 (19)	0.033*
H31C	0.714 (6)	0.894 (2)	0.2370 (10)	0.033*
O31	1.3885 (5)	0.55072 (15)	0.23406 (12)	0.0259 (6)
H31'	1.522 (4)	0.530 (2)	0.2572 (17)	0.039*
O32	1.5200 (5)	0.68048 (15)	0.29159 (12)	0.0272 (6)
H32'	1.633 (5)	0.649 (2)	0.3138 (17)	0.041*
C31	1.1043 (7)	0.6786 (2)	0.20739 (16)	0.0221 (8)
C32	1.0514 (6)	0.7641 (2)	0.21890 (17)	0.0220 (8)
H32	1.1704	0.7966	0.2495	0.026*
C33	0.8294 (6)	0.8014 (2)	0.18643 (16)	0.0201 (7)
C34	0.6537 (7)	0.7561 (2)	0.14105 (17)	0.0254 (8)
H34	0.5010	0.7825	0.1188	0.030*
C35	0.7032 (7)	0.6721 (2)	0.12854 (18)	0.0285 (9)
H35	0.5845	0.6405	0.0971	0.034*
C36	0.9239 (7)	0.6335 (2)	0.16143 (17)	0.0251 (8)
H36	0.9541	0.5753	0.1527	0.030*
S51	0.18611 (16)	0.99469 (6)	0.11838 (4)	0.0218 (2)
O51	−0.0477 (5)	0.95998 (18)	0.08028 (13)	0.0375 (7)
O52	0.4070 (5)	0.9546 (2)	0.09827 (13)	0.0452 (8)
O53	0.2071 (5)	0.97849 (15)	0.19058 (11)	0.0274 (6)
O54	0.1982 (6)	1.08633 (17)	0.10711 (14)	0.0470 (8)

	U11	U22	U33	U12	U13	U23
B1	0.032 (2)	0.033 (3)	0.020 (2)	0.007 (2)	0.0024 (18)	0.0038 (18)
N1	0.066 (3)	0.033 (2)	0.0265 (19)	−0.0244 (19)	0.0168 (19)	−0.0051 (16)
O1	0.077 (2)	0.0217 (15)	0.0305 (16)	0.0007 (14)	0.0210 (15)	0.0008 (12)
O2	0.0406 (16)	0.0190 (13)	0.0232 (13)	−0.0056 (12)	0.0098 (12)	0.0010 (11)
C1	0.031 (2)	0.035 (2)	0.0169 (18)	0.0012 (17)	0.0029 (16)	0.0030 (15)
C2	0.028 (2)	0.032 (2)	0.0184 (18)	−0.0022 (16)	0.0060 (15)	−0.0012 (15)
C3	0.028 (2)	0.033 (2)	0.0207 (19)	−0.0066 (17)	0.0039 (16)	−0.0012 (16)
C4	0.023 (2)	0.057 (3)	0.026 (2)	−0.0051 (19)	0.0057 (17)	0.0067 (19)
C5	0.033 (2)	0.065 (3)	0.034 (2)	0.019 (2)	0.0135 (19)	0.007 (2)
C6	0.041 (2)	0.046 (3)	0.026 (2)	0.014 (2)	0.0045 (18)	0.0082 (19)
B31	0.031 (2)	0.022 (2)	0.020 (2)	0.0009 (18)	0.0101 (18)	0.0015 (17)
N31	0.0212 (16)	0.0228 (16)	0.0224 (16)	0.0006 (13)	0.0065 (13)	0.0024 (13)
O31	0.0284 (15)	0.0223 (14)	0.0254 (14)	0.0043 (11)	0.0013 (11)	−0.0028 (11)
O32	0.0331 (15)	0.0181 (13)	0.0270 (14)	0.0037 (11)	−0.0022 (12)	−0.0040 (11)
C31	0.0243 (19)	0.0234 (19)	0.0192 (17)	−0.0002 (15)	0.0059 (15)	0.0007 (15)
C32	0.0206 (19)	0.026 (2)	0.0186 (18)	−0.0023 (15)	0.0019 (14)	−0.0002 (14)
C33	0.0231 (19)	0.0196 (18)	0.0195 (17)	−0.0019 (14)	0.0091 (15)	0.0025 (14)
C34	0.025 (2)	0.028 (2)	0.0224 (19)	−0.0011 (16)	0.0021 (15)	0.0038 (15)
C35	0.031 (2)	0.027 (2)	0.026 (2)	−0.0054 (17)	0.0014 (17)	0.0007 (16)
C36	0.034 (2)	0.0183 (19)	0.0233 (19)	−0.0013 (16)	0.0067 (16)	−0.0033 (14)
S51	0.0197 (4)	0.0264 (5)	0.0190 (4)	0.0009 (4)	0.0035 (3)	0.0033 (4)
O51	0.0253 (15)	0.0582 (19)	0.0267 (15)	−0.0102 (13)	−0.0002 (12)	0.0024 (13)
O52	0.0317 (16)	0.079 (2)	0.0254 (15)	0.0252 (15)	0.0063 (12)	−0.0004 (14)
O53	0.0279 (14)	0.0339 (15)	0.0205 (13)	−0.0081 (11)	0.0049 (11)	0.0021 (11)
O54	0.071 (2)	0.0271 (16)	0.0368 (17)	−0.0020 (15)	−0.0049 (15)	0.0082 (13)

B1—O1	1.344 (5)	B31—C31	1.571 (5)
B1—O2	1.380 (5)	N31—C33	1.460 (4)
B1—C1	1.565 (6)	N31—H31A	0.86 (3)
N1—C3	1.456 (5)	N31—H31B	0.86 (3)
N1—H1A	0.87 (4)	N31—H31C	0.86 (2)
N1—H1B	0.86 (4)	O31—H31'	0.84 (3)
N1—H1C	0.86 (2)	O32—H32'	0.84 (3)
O1—H1'	0.84 (4)	C31—C32	1.400 (5)
O2—H2'	0.840 (12)	C31—C36	1.401 (5)
C1—C2	1.397 (5)	C32—C33	1.374 (5)
C1—C6	1.401 (5)	C32—H32	0.9500
C2—C3	1.376 (5)	C33—C34	1.381 (5)
C2—H2	0.9500	C34—C35	1.380 (5)
C3—C4	1.378 (5)	C34—H34	0.9500
C4—C5	1.381 (6)	C35—C36	1.380 (5)
C4—H4	0.9500	C35—H35	0.9500
C5—C6	1.374 (6)	C36—H36	0.9500
C5—H5	0.9500	S51—O51	1.445 (3)
C6—H6	0.9500	S51—O54	1.460 (3)
B31—O31	1.358 (5)	S51—O52	1.470 (3)
B31—O32	1.364 (5)	S51—O53	1.483 (2)
O1—B1—O2	119.0 (4)	C33—N31—H31A	108 (3)
O1—B1—C1	119.7 (4)	C33—N31—H31B	110 (3)
O2—B1—C1	121.3 (4)	H31A—N31—H31B	107 (3)
C3—N1—H1A	110 (3)	C33—N31—H31C	112 (3)
C3—N1—H1B	113 (3)	H31A—N31—H31C	107 (4)
H1A—N1—H1B	102 (4)	H31B—N31—H31C	111 (4)
C3—N1—H1C	113 (3)	B31—O31—H31'	114 (3)
H1A—N1—H1C	114 (5)	B31—O32—H32'	111 (3)
H1B—N1—H1C	104 (4)	C32—C31—C36	117.5 (3)
B1—O1—H1'	114 (3)	C32—C31—B31	121.2 (3)
B1—O2—H2'	114 (3)	C36—C31—B31	121.3 (3)
C2—C1—C6	117.0 (4)	C33—C32—C31	120.8 (3)
C2—C1—B1	121.3 (3)	C33—C32—H32	119.6
C6—C1—B1	121.6 (4)	C31—C32—H32	119.6
C3—C2—C1	121.0 (4)	C32—C33—C34	121.1 (3)
C3—C2—H2	119.5	C32—C33—N31	119.3 (3)
C1—C2—H2	119.5	C34—C33—N31	119.6 (3)
C2—C3—C4	121.3 (4)	C35—C34—C33	119.1 (3)
C2—C3—N1	118.5 (3)	C35—C34—H34	120.4
C4—C3—N1	120.2 (3)	C33—C34—H34	120.4
C3—C4—C5	118.4 (4)	C36—C35—C34	120.4 (3)
C3—C4—H4	120.8	C36—C35—H35	119.8
C5—C4—H4	120.8	C34—C35—H35	119.8
C6—C5—C4	121.0 (4)	C35—C36—C31	121.1 (3)
C6—C5—H5	119.5	C35—C36—H36	119.4
C4—C5—H5	119.5	C31—C36—H36	119.4
C5—C6—C1	121.3 (4)	O51—S51—O54	110.29 (17)
C5—C6—H6	119.4	O51—S51—O52	110.33 (17)
C1—C6—H6	119.4	O54—S51—O52	108.31 (19)
O31—B31—O32	122.7 (3)	O51—S51—O53	111.12 (15)
O31—B31—C31	118.1 (3)	O54—S51—O53	109.24 (16)
O32—B31—C31	119.2 (3)	O52—S51—O53	107.46 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31'···O53i	0.84 (3)	1.81 (3)	2.653 (4)	175 (3)
O32—H32'···O54i	0.84 (3)	1.96 (3)	2.744 (4)	155 (3)
N1—H1A···O54ii	0.87 (4)	2.31 (4)	3.161 (5)	169 (4)
N1—H1C···O52iii	0.86 (2)	1.86 (2)	2.718 (4)	176 (5)
O1—H1'···O31iv	0.84 (4)	1.99 (4)	2.803 (4)	163 (4)
N31—H31A···O52	0.86 (3)	1.92 (3)	2.787 (4)	179 (3)
N31—H31C···O2	0.86 (2)	2.07 (2)	2.874 (4)	156 (3)
O2—H2'···O32v	0.84 (1)	1.99 (2)	2.820 (3)	169 (4)
N1—H1B···O51vi	0.86 (4)	2.13 (4)	2.923 (5)	152 (4)
N1—H1B···O54vi	0.86 (4)	2.37 (4)	3.112 (5)	144 (4)
N31—H31B···O53vii	0.86 (3)	1.90 (3)	2.744 (4)	168 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O31—H31′⋯O53i	0.84 (3)	1.81 (3)	2.653 (4)	175 (3)
O32—H32′⋯O54i	0.84 (3)	1.96 (3)	2.744 (4)	155 (3)
N1—H1A⋯O54ii	0.87 (4)	2.31 (4)	3.161 (5)	169 (4)
N1—H1C⋯O52iii	0.86 (2)	1.86 (2)	2.718 (4)	176 (5)
O1—H1′⋯O31iv	0.84 (4)	1.99 (4)	2.803 (4)	163 (4)
N31—H31A⋯O52	0.86 (3)	1.92 (3)	2.787 (4)	179 (3)
N31—H31C⋯O2	0.86 (2)	2.07 (2)	2.874 (4)	156 (3)
O2—H2′⋯O32v	0.84 (1)	1.99 (2)	2.820 (3)	169 (4)
N1—H1B⋯O51vi	0.86 (4)	2.13 (4)	2.923 (5)	152 (4)
N1—H1B⋯O54vi	0.86 (4)	2.37 (4)	3.112 (5)	144 (4)
N31—H31B⋯O53vii	0.86 (3)	1.90 (3)	2.744 (4)	168 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .