4-Bromo­phenyl­boronic acid ethanol 0.04-solvate

The title compound, C₆H₆BBrO₂·0.04C₂H₆O, is known to show very high antibacterial activity in the family of aryl-substituted boronic acids. Individual molecules are interconnected by hydrogen bonding, resulting in an extended chain. These chains are held parallel by weak van der Waals forces.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.049
• wR factor = 0.149
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      58.93 Deg.

Author Response: We have used a combination of CuK\a radiation along with multiwire proportional counter. Thus the instrumental geometry restricts the maximum theta angle to theta = 60 degrees.

PLAT312_ALERT_2_A Strange C-O-H Geometry (C-O .LT. 1.25 Ang) .....        O20

Author Response: 1. The occupancy of the ethanol molecule is too low to refine the position very accurately.

Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5556
PLAT023_ALERT_3_B Resolution (too) Low [sin(th)/Lambda < 0.6].....      58.93 Deg.
PLAT417_ALERT_2_B Short Inter D-H..H-D       H1     ..  H4      ..       1.52 Ang.
PLAT417_ALERT_2_B Short Inter D-H..H-D       H2A    ..  H2A     ..       2.00 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT213_ALERT_2_C Atom O20     has ADP max/min Ratio .............       3.90 prolat
PLAT213_ALERT_2_C Atom C21     has ADP max/min Ratio .............       3.90 prolat
PLAT213_ALERT_2_C Atom C22     has ADP max/min Ratio .............       3.90 prolat
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT301_ALERT_3_C Main Residue  Disorder .........................       1.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  Br2     ..       3.55 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.27 Ratio

   2 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: FRAMBO (Bruker–Nonius, 2003); cell refinement: CELL-NOW (Sheldrick, 2003) and SAINT (Bruker–Nonius, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2001); program(s) used to refine structure: SHELXL97 (Sheldrick, 2001); molecular graphics: X-SEED (Barbour, 1999) and Diamond (Brandenbourg, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and PLATON (Spek, 2004) as incorporated in WinGX (Farrugia, 1999).

4-bromophenylboronic acid'

Crystal data

C6H6BBrO2·0.04C2H6O	F(000) = 1585
Mr = 202.67	Dx = 1.595 Mg m^−3
Monoclinic, C2/m	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2y	Cell parameters from 5323 reflections
a = 29.1857 (11) Å	θ = 3.1–58.5°
b = 9.8249 (4) Å	µ = 6.17 mm^−1
c = 12.0285 (5) Å	T = 110 K
β = 101.902 (2)°	Block, colorless
V = 3375.0 (2) Å^3	0.08 × 0.06 × 0.04 mm
Z = 16

Data collection

BRUKER GADDS D8 Discover diffractometer	2529 independent reflections
Radiation source: fine-focus sealed tube	1953 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 58.9°, θmin = 6.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −32→32
Tmin = 0.638, Tmax = 0.791	k = −10→10
15334 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0951P)^2 + 7.7358P] where P = (Fo^2 + 2Fc^2)/3
2529 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 1.11 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

Special details

Experimental. For data collection a BRUKER GADDS D8 Discover instrument equipped with a combination of monochromated (with graphite) CuKa radiation, to provide higher intensity, and a HI-STAR multi-wire proportional counter area detector was used.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.10930 (3)	0.0000	1.15897 (6)	0.0553 (3)
Br2	0.18168 (3)	0.0000	0.43533 (7)	0.0561 (3)
Br3	0.26821 (3)	0.0000	0.74754 (10)	0.0767 (4)
Br4	0.24421 (4)	0.0000	1.11904 (9)	0.1026 (5)
B1	0.3895 (3)	0.0000	0.3777 (7)	0.0364 (18)
B2	0.4722 (3)	0.0000	0.6587 (6)	0.0332 (18)
B3	−0.0174 (3)	0.0000	0.6723 (6)	0.0327 (17)
B4	0.1077 (3)	0.0000	0.6452 (6)	0.0316 (17)
C1	0.3372 (2)	0.0000	0.3902 (5)	0.0319 (15)
C2	0.31330 (17)	0.1214 (5)	0.3959 (4)	0.0417 (12)
H2	0.3289	0.2054	0.3913	0.050*
C3	0.26742 (17)	0.1220 (6)	0.4080 (4)	0.0432 (13)
H3	0.2515	0.2057	0.4114	0.052*
C4	0.2448 (2)	0.0000	0.4151 (6)	0.0413 (17)
C5	0.4204 (2)	0.0000	0.6800 (5)	0.0325 (15)
C6	0.39688 (18)	0.1209 (5)	0.6913 (5)	0.0476 (13)
H6	0.4121	0.2050	0.6841	0.057*
C7	0.35231 (19)	0.1223 (6)	0.7125 (5)	0.0554 (15)
H7	0.3372	0.2062	0.7214	0.066*
C8	0.3297 (3)	0.0000	0.7209 (7)	0.050 (2)
C9	0.0142 (2)	0.0000	0.7927 (5)	0.0309 (15)
C10	0.0292 (2)	0.1183 (6)	0.8500 (5)	0.0595 (17)
H10	0.0203	0.2027	0.8134	0.071*
C11	0.0569 (3)	0.1196 (6)	0.9599 (5)	0.0683 (19)
H11	0.0661	0.2033	0.9974	0.082*
C12	0.0705 (3)	0.0000	1.0117 (6)	0.0451 (18)
C13	0.1415 (2)	0.0000	0.7645 (6)	0.0329 (15)
C14	0.15724 (19)	0.1206 (6)	0.8203 (4)	0.0486 (14)
H14	0.1473	0.2050	0.7848	0.058*
C15	0.1872 (2)	0.1208 (7)	0.9267 (5)	0.0608 (17)
H15	0.1973	0.2043	0.9637	0.073*
C16	0.2020 (3)	0.0000	0.9772 (6)	0.057 (2)
O1	−0.03255 (12)	−0.1186 (3)	0.6166 (3)	0.0396 (8)
H1	−0.0431	−0.1020	0.5476	0.059*
O2	0.49501 (12)	0.1180 (3)	0.6497 (3)	0.0419 (8)
H2A	0.4984	0.1279	0.5824	0.063*
O3	0.41357 (12)	0.1171 (3)	0.3713 (3)	0.0470 (9)
H3A	0.4238	0.1176	0.3109	0.071*
O4	0.09238 (12)	0.1174 (3)	0.5902 (3)	0.0415 (8)
H4	0.0930	0.1097	0.5210	0.062*
O20	0.0713 (9)	0.5000	1.0222 (18)	0.022 (4)	0.16
H20A	0.0420	0.5000	0.9954	0.033*	0.16
C21	0.1441 (13)	0.5000	0.941 (3)	0.022 (4)	0.16
H21A	0.1480	0.5000	0.8641	0.033*	0.16
H21B	0.1586	0.5798	0.9794	0.033*	0.16
C22	0.0908 (14)	0.5000	0.944 (3)	0.022 (4)	0.16
H22A	0.0787	0.5778	0.8993	0.026*	0.16

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0429 (5)	0.0807 (7)	0.0380 (5)	0.000	−0.0016 (4)	0.000
Br2	0.0305 (5)	0.0858 (7)	0.0529 (5)	0.000	0.0109 (4)	0.000
Br3	0.0407 (6)	0.0923 (8)	0.1066 (8)	0.000	0.0370 (6)	0.000
Br4	0.0763 (8)	0.1737 (14)	0.0440 (6)	0.000	−0.0193 (5)	0.000
B1	0.040 (5)	0.032 (5)	0.036 (4)	0.000	0.004 (4)	0.000
B2	0.038 (5)	0.029 (5)	0.032 (4)	0.000	0.005 (3)	0.000
B3	0.033 (4)	0.030 (5)	0.037 (4)	0.000	0.011 (3)	0.000
B4	0.025 (4)	0.030 (4)	0.041 (4)	0.000	0.011 (3)	0.000
C1	0.033 (4)	0.029 (4)	0.034 (3)	0.000	0.006 (3)	0.000
C2	0.041 (3)	0.035 (3)	0.049 (3)	−0.003 (2)	0.009 (2)	−0.002 (2)
C3	0.035 (3)	0.042 (3)	0.053 (3)	0.006 (2)	0.010 (2)	−0.006 (2)
C4	0.031 (4)	0.059 (5)	0.034 (4)	0.000	0.007 (3)	0.000
C5	0.033 (4)	0.030 (4)	0.034 (3)	0.000	0.006 (3)	0.000
C6	0.040 (3)	0.032 (3)	0.074 (4)	0.003 (2)	0.022 (3)	0.006 (3)
C7	0.045 (3)	0.045 (3)	0.082 (4)	0.011 (3)	0.026 (3)	0.004 (3)
C8	0.036 (4)	0.054 (5)	0.062 (5)	0.000	0.018 (4)	0.000
C9	0.028 (4)	0.028 (4)	0.036 (4)	0.000	0.006 (3)	0.000
C10	0.079 (4)	0.033 (3)	0.052 (3)	−0.007 (3)	−0.019 (3)	0.006 (2)
C11	0.101 (5)	0.038 (3)	0.051 (3)	−0.016 (3)	−0.019 (3)	−0.005 (3)
C12	0.032 (4)	0.066 (6)	0.036 (4)	0.000	0.003 (3)	0.000
C13	0.034 (4)	0.033 (4)	0.036 (3)	0.000	0.016 (3)	0.000
C14	0.048 (3)	0.055 (4)	0.040 (3)	−0.006 (3)	0.003 (3)	−0.006 (2)
C15	0.060 (4)	0.071 (5)	0.048 (3)	−0.011 (3)	0.003 (3)	−0.017 (3)
C16	0.040 (5)	0.093 (7)	0.036 (4)	0.000	0.006 (4)	0.000
O1	0.043 (2)	0.0304 (18)	0.0410 (18)	0.0009 (15)	−0.0001 (16)	−0.0060 (14)
O2	0.0363 (19)	0.0299 (19)	0.059 (2)	−0.0029 (15)	0.0089 (17)	0.0078 (16)
O3	0.039 (2)	0.037 (2)	0.069 (2)	−0.0090 (16)	0.0181 (18)	−0.0064 (17)
O4	0.041 (2)	0.0378 (19)	0.0436 (19)	0.0097 (15)	0.0031 (17)	0.0067 (15)
O20	0.046 (12)	0.003 (8)	0.016 (8)	0.000	0.005 (8)	0.000
C21	0.046 (12)	0.003 (8)	0.016 (8)	0.000	0.005 (8)	0.000
C22	0.046 (12)	0.003 (8)	0.016 (8)	0.000	0.005 (8)	0.000

Geometric parameters (Å, º)

Br1—C12	1.896 (7)	C7—C8	1.384 (7)
Br2—C4	1.908 (7)	C7—H7	0.9500
Br3—C8	1.888 (7)	C8—C7^i	1.384 (7)
Br4—C16	1.887 (8)	C9—C10	1.375 (7)
B1—O3^i	1.359 (6)	C9—C10^i	1.375 (7)
B1—O3	1.359 (6)	C10—C11	1.401 (8)
B1—C1	1.565 (10)	C10—H10	0.9500
B2—O2	1.353 (5)	C11—C12	1.350 (7)
B2—O2^i	1.353 (5)	C11—H11	0.9500
B2—C5	1.585 (10)	C12—C11^i	1.350 (7)
B3—O1	1.371 (5)	C13—C14	1.392 (7)
B3—O1^i	1.371 (5)	C13—C14^i	1.392 (7)
B3—C9	1.549 (10)	C14—C15	1.395 (8)
B4—O4^i	1.358 (5)	C14—H14	0.9500
B4—O4	1.358 (5)	C15—C16	1.361 (8)
B4—C13	1.565 (10)	C15—H15	0.9500
C1—C2^i	1.390 (6)	C16—C15^i	1.361 (8)
C1—C2	1.390 (6)	O1—H1	0.8400
C2—C3	1.377 (7)	O2—H2A	0.8400
C2—H2	0.9500	O3—H3A	0.8400
C3—C4	1.379 (6)	O4—H4	0.8400
C3—H3	0.9500	O20—C22	1.20 (4)
C4—C3^i	1.379 (6)	O20—H20A	0.8499
C5—C6^i	1.392 (6)	C21—C22	1.56 (5)
C5—C6	1.392 (6)	C21—H21A	0.9600
C6—C7	1.376 (7)	C21—H21B	0.9600
C6—H6	0.9500	C22—H22A	0.9600
O3^i—B1—O3	115.7 (7)	C10—C9—C10^i	115.4 (7)
O3^i—B1—C1	122.1 (3)	C10—C9—B3	122.3 (3)
O3—B1—C1	122.1 (3)	C10^i—C9—B3	122.3 (3)
O2—B2—O2^i	118.0 (6)	C9—C10—C11	122.8 (5)
O2—B2—C5	121.0 (3)	C9—C10—H10	118.6
O2^i—B2—C5	121.0 (3)	C11—C10—H10	118.6
O1—B3—O1^i	116.4 (6)	C12—C11—C10	119.0 (6)
O1—B3—C9	121.8 (3)	C12—C11—H11	120.5
O1^i—B3—C9	121.8 (3)	C10—C11—H11	120.5
O4^i—B4—O4	116.3 (6)	C11^i—C12—C11	120.9 (7)
O4^i—B4—C13	121.9 (3)	C11^i—C12—Br1	119.5 (4)
O4—B4—C13	121.9 (3)	C11—C12—Br1	119.5 (4)
C2^i—C1—C2	118.2 (6)	C14—C13—C14^i	116.7 (7)
C2^i—C1—B1	120.9 (3)	C14—C13—B4	121.7 (3)
C2—C1—B1	120.9 (3)	C14^i—C13—B4	121.7 (3)
C3—C2—C1	121.1 (5)	C13—C14—C15	121.7 (6)
C3—C2—H2	119.4	C13—C14—H14	119.1
C1—C2—H2	119.4	C15—C14—H14	119.1
C2—C3—C4	119.4 (5)	C16—C15—C14	119.3 (6)
C2—C3—H3	120.3	C16—C15—H15	120.4
C4—C3—H3	120.3	C14—C15—H15	120.4
C3—C4—C3^i	120.7 (6)	C15^i—C16—C15	121.3 (8)
C3—C4—Br2	119.7 (3)	C15^i—C16—Br4	119.4 (4)
C3^i—C4—Br2	119.7 (3)	C15—C16—Br4	119.4 (4)
C6^i—C5—C6	117.1 (6)	B3—O1—H1	109.5
C6^i—C5—B2	121.4 (3)	B2—O2—H2A	109.5
C6—C5—B2	121.4 (3)	B1—O3—H3A	109.5
C7—C6—C5	122.0 (5)	B4—O4—H4	109.5
C7—C6—H6	119.0	C22—O20—H20A	108.0
C5—C6—H6	119.0	C22—C21—H21A	109.7
C6—C7—C8	119.1 (5)	C22—C21—H21B	109.3
C6—C7—H7	120.4	H21A—C21—H21B	109.5
C8—C7—H7	120.4	O20—C22—C21	131 (3)
C7—C8—C7^i	120.5 (7)	O20—C22—H22A	105.0
C7—C8—Br3	119.7 (3)	C21—C22—H22A	104.1
C7^i—C8—Br3	119.7 (3)
O3^i—B1—C1—C2^i	0.3 (10)	O1—B3—C9—C10	−179.2 (6)
O3—B1—C1—C2^i	179.7 (6)	O1^i—B3—C9—C10	−0.5 (10)
O3^i—B1—C1—C2	−179.7 (6)	O1—B3—C9—C10^i	0.5 (10)
O3—B1—C1—C2	−0.3 (10)	O1^i—B3—C9—C10^i	179.2 (6)
C2^i—C1—C2—C3	0.7 (10)	C10^i—C9—C10—C11	−1.1 (12)
B1—C1—C2—C3	−179.4 (5)	B3—C9—C10—C11	178.6 (6)
C1—C2—C3—C4	0.3 (8)	C9—C10—C11—C12	1.2 (11)
C2—C3—C4—C3^i	−1.2 (10)	C10—C11—C12—C11^i	−1.2 (13)
C2—C3—C4—Br2	178.6 (4)	C10—C11—C12—Br1	178.5 (5)
O2—B2—C5—C6^i	−178.9 (6)	O4^i—B4—C13—C14	179.7 (5)
O2^i—B2—C5—C6^i	0.7 (10)	O4—B4—C13—C14	0.4 (9)
O2—B2—C5—C6	−0.7 (10)	O4^i—B4—C13—C14^i	−0.4 (9)
O2^i—B2—C5—C6	178.9 (6)	O4—B4—C13—C14^i	−179.7 (5)
C6^i—C5—C6—C7	−0.1 (11)	C14^i—C13—C14—C15	−0.2 (10)
B2—C5—C6—C7	−178.4 (6)	B4—C13—C14—C15	179.8 (5)
C5—C6—C7—C8	−1.2 (10)	C13—C14—C15—C16	0.7 (9)
C6—C7—C8—C7^i	2.6 (12)	C14—C15—C16—C15^i	−1.3 (12)
C6—C7—C8—Br3	−179.0 (5)	C14—C15—C16—Br4	177.9 (4)

Symmetry code: (i) x, −y, z.