Methyl 2-(5,5-dimethyl-1,3,2-dioxa-borinan-2-yl)-4-nitro-benzoate.

The six-membered boronate ester ring of the title compound, C(13)H(16)BNO(6), adopts an envelope conformation with the C atom bearing the dimethyl substituents at the flap. The O-B-C-C torsion angles between the boronate group and the benzene ring are 72.5 (2) and 81.0 (2)°. The 4-nitro-benzoate unit adopts a slightly twisted conformation, with dihedral angles between the benzene ring and the nitrate and methyl ester groups of 17.5 (2) and 14.4 (3)°, respectively. In the crystal, inversion-related pairs of mol-ecules show weak π-π stacking inter-actions [centroid-centroid distance = 4.0585 (9) Å and inter-planar spacing = 3.6254 (7) Å].

Related literature

For use of boronic acids as synthetic inter­mediates, see: Hall (2005 ▶); for their use as sensors in the alcoholic beverage industry, see: Wiskur & Anslyn (2001 ▶) and as saccharide sensors, see: Baxter et al. (1990 ▶); Fedorak et al. (1989 ▶); Yamamoto et al. (1990 ▶); Yasuda et al. (1990 ▶). For a review on borolectins, see: Yang et al. (2002 ▶, 2004 ▶). For the utilization of boronic acids as enzyme inhibitors, see: Adams et al. (1998 ▶); Fevig et al. (1996 ▶); Johnson & Houston (2002 ▶); Kettner et al. (1990 ▶); Prusoff et al. (1993 ▶). For the synthesis of aromatic ortho-substituted boronate esters, see: Baudoin et al. (2000 ▶); Fang et al. (2005 ▶); Ishiyama et al. (2010 ▶); Wang et al. (2006 ▶).

Experimental

Crystal data

C13H16BNO6

M = 293.08

Monoclinic,

a = 12.1774 (3) Å

b = 9.7928 (3) Å

c = 13.4921 (4) Å

β = 115.4764 (12)°

V = 1452.49 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 150 K

0.25 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.92, T max = 0.98

16148 measured reflections

3286 independent reflections

2229 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.114

S = 0.92

3286 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.39 e Å−3

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029650/pk2392sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029650/pk2392Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812029650/pk2392Isup3.cml

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

C13H16BNO6	F(000) = 616
Mr = 293.08	Dx = 1.340 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3373 reflections
a = 12.1774 (3) Å	θ = 5–27°
b = 9.7928 (3) Å	µ = 0.11 mm−1
c = 13.4921 (4) Å	T = 150 K
β = 115.4764 (12)°	Plate, colourless
V = 1452.49 (7) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Nonius KappaCCD diffractometer	2229 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −15→15
Tmin = 0.92, Tmax = 0.98	k = −12→12
16148 measured reflections	l = −17→17
3286 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.114	Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.05P)2 + 0.66P] , where P = (max(Fo2,0) + 2Fc2)/3
S = 0.92	(Δ/σ)max = 0.000214
3286 reflections	Δρmax = 0.36 e Å−3
190 parameters	Δρmin = −0.39 e Å−3
0 restraints

	x	y	z	Uiso*/Ueq
O1	0.12715 (11)	0.67634 (11)	0.37794 (9)	0.0363
C2	0.13726 (17)	0.77688 (17)	0.30436 (13)	0.0384
C3	0.14982 (15)	0.91980 (17)	0.35044 (13)	0.0325
C4	0.17357 (18)	1.01872 (19)	0.27425 (15)	0.0443
C5	0.0341 (2)	0.9608 (2)	0.3611 (2)	0.0649
C6	0.25847 (18)	0.91925 (19)	0.46109 (14)	0.0457
O7	0.25147 (12)	0.81218 (13)	0.53161 (9)	0.0474
B8	0.18826 (16)	0.69741 (19)	0.48684 (14)	0.0305
C9	0.17022 (14)	0.59224 (16)	0.56803 (12)	0.0295
C10	0.23148 (13)	0.46714 (17)	0.59640 (12)	0.0301
C11	0.31710 (14)	0.43635 (17)	0.54680 (13)	0.0329
O12	0.35352 (10)	0.30678 (12)	0.55875 (10)	0.0380
C13	0.43385 (17)	0.2710 (2)	0.50882 (15)	0.0444
O14	0.34969 (12)	0.52155 (13)	0.50062 (11)	0.0502
C15	0.21684 (14)	0.37785 (18)	0.67027 (13)	0.0344
C16	0.14051 (14)	0.41192 (18)	0.71801 (13)	0.0345
C17	0.07746 (14)	0.53350 (17)	0.68739 (12)	0.0312
C18	0.09013 (14)	0.62350 (17)	0.61390 (13)	0.0325
N19	−0.00773 (13)	0.56838 (15)	0.73455 (12)	0.0385
O20	0.00100 (11)	0.50649 (14)	0.81687 (10)	0.0451
O21	−0.08423 (13)	0.65719 (14)	0.68873 (13)	0.0569
H22	0.2125	0.7563	0.2935	0.0495*
H21	0.0629	0.7702	0.2345	0.0499*
H42	0.1825	1.1106	0.3051	0.0710*
H41	0.2498	0.9921	0.2680	0.0704*
H43	0.1034	1.0155	0.2010	0.0710*
H52	0.0436	1.0553	0.3874	0.1049*
H53	0.0229	0.8990	0.4128	0.1046*
H51	−0.0345	0.9535	0.2899	0.1051*
H62	0.2630	1.0067	0.4988	0.0527*
H61	0.3341	0.9062	0.4495	0.0531*
H132	0.4574	0.1757	0.5267	0.0723*
H131	0.5044	0.3321	0.5356	0.0723*
H133	0.3879	0.2814	0.4298	0.0724*
H151	0.2617	0.2923	0.6890	0.0415*
H161	0.1301	0.3524	0.7695	0.0400*
H181	0.0457	0.7074	0.5971	0.0378*

	U11	U22	U33	U12	U13	U23
O1	0.0496 (7)	0.0290 (6)	0.0286 (6)	−0.0096 (5)	0.0151 (5)	0.0004 (5)
C2	0.0548 (10)	0.0329 (9)	0.0298 (8)	−0.0059 (8)	0.0204 (8)	0.0027 (7)
C3	0.0400 (9)	0.0271 (8)	0.0358 (8)	0.0050 (7)	0.0212 (7)	0.0057 (7)
C4	0.0591 (11)	0.0335 (10)	0.0478 (10)	0.0048 (9)	0.0300 (9)	0.0102 (8)
C5	0.0695 (14)	0.0599 (14)	0.0888 (16)	0.0288 (12)	0.0564 (13)	0.0306 (12)
C6	0.0613 (12)	0.0318 (10)	0.0396 (10)	−0.0140 (9)	0.0175 (9)	0.0046 (8)
O7	0.0626 (8)	0.0362 (7)	0.0305 (6)	−0.0196 (6)	0.0078 (6)	0.0041 (5)
B8	0.0313 (9)	0.0274 (10)	0.0290 (9)	−0.0022 (7)	0.0093 (7)	0.0010 (7)
C9	0.0295 (8)	0.0292 (9)	0.0251 (7)	−0.0046 (7)	0.0072 (6)	0.0005 (6)
C10	0.0266 (7)	0.0323 (9)	0.0272 (8)	−0.0035 (7)	0.0077 (6)	0.0025 (7)
C11	0.0292 (8)	0.0347 (10)	0.0317 (8)	−0.0009 (7)	0.0103 (7)	0.0068 (7)
O12	0.0403 (6)	0.0366 (7)	0.0451 (7)	0.0044 (5)	0.0260 (5)	0.0098 (5)
C13	0.0498 (10)	0.0436 (11)	0.0531 (11)	0.0030 (9)	0.0348 (9)	0.0049 (9)
O14	0.0525 (8)	0.0402 (8)	0.0727 (9)	0.0043 (6)	0.0408 (7)	0.0197 (7)
C15	0.0308 (8)	0.0362 (10)	0.0345 (9)	0.0029 (7)	0.0124 (7)	0.0107 (7)
C16	0.0341 (8)	0.0385 (10)	0.0293 (8)	−0.0012 (7)	0.0120 (7)	0.0070 (7)
C17	0.0310 (8)	0.0345 (9)	0.0262 (8)	−0.0051 (7)	0.0104 (6)	−0.0046 (7)
C18	0.0345 (8)	0.0268 (9)	0.0308 (8)	−0.0030 (7)	0.0091 (7)	−0.0018 (7)
N19	0.0441 (8)	0.0347 (8)	0.0399 (8)	−0.0064 (7)	0.0211 (7)	−0.0089 (7)
O20	0.0517 (7)	0.0552 (8)	0.0336 (6)	−0.0089 (6)	0.0233 (6)	−0.0066 (6)
O21	0.0658 (9)	0.0415 (8)	0.0790 (10)	0.0151 (7)	0.0459 (8)	0.0069 (7)

O1—C2	1.4406 (18)	C9—C10	1.399 (2)
O1—B8	1.347 (2)	C9—C18	1.395 (2)
C2—C3	1.512 (2)	C10—C11	1.492 (2)
C2—H22	1.009	C10—C15	1.394 (2)
C2—H21	0.989	C11—O12	1.331 (2)
C3—C4	1.528 (2)	C11—O14	1.2061 (19)
C3—C5	1.531 (2)	O12—C13	1.4492 (19)
C3—C6	1.510 (2)	C13—H132	0.976
C4—H42	0.977	C13—H131	0.979
C4—H41	1.002	C13—H133	0.974
C4—H43	0.990	C15—C16	1.380 (2)
C5—H52	0.980	C15—H151	0.972
C5—H53	0.977	C16—C17	1.380 (2)
C5—H51	0.967	C16—H161	0.956
C6—O7	1.443 (2)	C17—C18	1.384 (2)
C6—H62	0.986	C17—N19	1.471 (2)
C6—H61	1.006	C18—H181	0.955
O7—B8	1.349 (2)	N19—O20	1.2291 (18)
B8—C9	1.586 (2)	N19—O21	1.2292 (19)
C2—O1—B8	118.43 (13)	O7—B8—C9	116.97 (14)
O1—C2—C3	111.88 (13)	O1—B8—C9	118.56 (14)
O1—C2—H22	108.4	B8—C9—C10	122.79 (14)
C3—C2—H22	107.9	B8—C9—C18	119.65 (14)
O1—C2—H21	107.3	C10—C9—C18	117.56 (14)
C3—C2—H21	110.0	C9—C10—C11	116.57 (14)
H22—C2—H21	111.4	C9—C10—C15	121.85 (15)
C2—C3—C4	108.97 (13)	C11—C10—C15	121.53 (15)
C2—C3—C5	110.29 (16)	C10—C11—O12	113.52 (13)
C4—C3—C5	110.20 (15)	C10—C11—O14	122.73 (16)
C2—C3—C6	107.08 (14)	O12—C11—O14	123.75 (15)
C4—C3—C6	109.18 (14)	C11—O12—C13	115.50 (13)
C5—C3—C6	111.04 (16)	O12—C13—H132	107.6
C3—C4—H42	108.4	O12—C13—H131	110.0
C3—C4—H41	110.0	H132—C13—H131	112.0
H42—C4—H41	109.7	O12—C13—H133	107.4
C3—C4—H43	108.6	H132—C13—H133	109.9
H42—C4—H43	110.1	H131—C13—H133	109.8
H41—C4—H43	110.0	C10—C15—C16	120.07 (15)
C3—C5—H52	108.1	C10—C15—H151	119.8
C3—C5—H53	108.7	C16—C15—H151	120.2
H52—C5—H53	110.9	C15—C16—C17	117.93 (15)
C3—C5—H51	108.9	C15—C16—H161	121.2
H52—C5—H51	110.2	C17—C16—H161	120.9
H53—C5—H51	109.8	C16—C17—C18	123.00 (15)
C3—C6—O7	112.30 (14)	C16—C17—N19	118.41 (14)
C3—C6—H62	109.8	C18—C17—N19	118.59 (15)
O7—C6—H62	107.3	C9—C18—C17	119.52 (15)
C3—C6—H61	108.5	C9—C18—H181	121.0
O7—C6—H61	109.1	C17—C18—H181	119.4
H62—C6—H61	109.8	C17—N19—O20	118.24 (14)
C6—O7—B8	119.62 (13)	C17—N19—O21	118.01 (14)
O7—B8—O1	123.85 (15)	O20—N19—O21	123.75 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H42···O21i	0.98	2.59	3.460 (3)	149
C13—H132···O20ii	0.98	2.56	3.356 (3)	139
C13—H131···O14iii	0.98	2.49	3.373 (3)	150
C16—H161···O7ii	0.96	2.47	3.205 (3)	134