Synthon preference in the cocrystal of 3,4,5-tri­fluoro­phenyl­boronic acid with urea

The comprehensive description of the crystal structure of a novel 1:1 cocrystal of 3,4,5-trifluoro­phenyl­boronic acid with urea, C₆H₄BF₃O₂·CH₄N₂O, is presented. Both components are good candidates for crystal engineering as they can create a variety of supra­molecular synthons. The preference for the formation of different hetrosynthons is verified based on theoretical calculations. The syn–anti conformation of boronic acid has been found to be the most favourable in the formation of inter­molecular inter­actions with urea. Moreover, the distortions present in the boron coordination sphere have been described qu­anti­tatively based on experimental data according to bond-valence vector model calculations. The results revealed that the deformation of the sphere is typical for a syn–anti conformation of boronic acids. The supra­molecular structure of the cocrystal is composed of large synthons in the form of layers made up of O—H...O and N—H...O hydrogen bonds. The layers are joined via N—H...F hydrogen bonds which are unusual for urea cocrystal structures.

Computing details

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2014); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2014); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Crystal Impact, 2004), CrystalExplorer (Wolff et al., 2012), GaussView (Dennington et al., 2009), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

3,4,5-Triflurophenylboronic acid–carbonic diamide (1/1)

Crystal data

C6H4BF3O2·CH4N2O	F(000) = 480
Mr = 235.96	Dx = 1.621 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.5305 (6) Å	Cell parameters from 3180 reflections
b = 8.2823 (4) Å	θ = 6.9–66.6°
c = 11.5020 (6) Å	µ = 1.42 mm^−1
β = 118.304 (7)°	T = 298 K
V = 967.11 (10) Å^3	Block, colourless
Z = 4	0.20 × 0.08 × 0.08 mm

Data collection

Rigaku Xcalibur Atlas Gemini ultra diffractometer	1720 independent reflections
Radiation source: sealed X-ray tube, Enhance Ultra (Cu) X-ray Source	1404 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.035
Detector resolution: 10.3347 pixels mm^-1	θmax = 67.2°, θmin = 4.4°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2014)	k = −9→9
Tmin = 0.896, Tmax = 1.000	l = −13→13
8913 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0433P)^2 + 0.2553P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1720 reflections	Δρmax = 0.16 e Å^−3
163 parameters	Δρmin = −0.18 e Å^−3
6 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F1	−0.05714 (11)	0.39207 (17)	0.22443 (11)	0.0654 (4)
F2	−0.03799 (11)	0.24804 (17)	0.44331 (12)	0.0645 (4)
F3	0.17696 (13)	0.29250 (16)	0.67705 (11)	0.0663 (4)
O1	0.36346 (12)	0.70035 (16)	0.35408 (11)	0.0433 (3)
H1	0.4267 (17)	0.755 (3)	0.361 (2)	0.065*
O2	0.49688 (11)	0.67205 (16)	0.58143 (11)	0.0402 (3)
H2	0.507 (2)	0.641 (3)	0.6532 (14)	0.060*
C1	0.26752 (15)	0.53300 (19)	0.46804 (16)	0.0334 (4)
C2	0.15370 (16)	0.5095 (2)	0.34767 (17)	0.0389 (4)
H2A	0.1462	0.5582	0.2716	0.047*
C3	0.05331 (16)	0.4154 (2)	0.34085 (18)	0.0421 (4)
C4	0.06096 (17)	0.3416 (2)	0.45099 (18)	0.0422 (4)
C5	0.17188 (18)	0.3651 (2)	0.56966 (17)	0.0410 (4)
C6	0.27463 (16)	0.4587 (2)	0.58017 (16)	0.0382 (4)
H6	0.3488	0.4726	0.6618	0.046*
B1	0.38275 (18)	0.6392 (2)	0.47131 (18)	0.0341 (4)
O3	0.54328 (11)	0.89213 (16)	0.33380 (11)	0.0421 (3)
N1	0.67293 (16)	0.9144 (2)	0.55285 (14)	0.0480 (4)
H1A	0.6231 (19)	0.845 (2)	0.565 (2)	0.058*
H1B	0.7403 (15)	0.956 (3)	0.6186 (16)	0.058*
N2	0.72171 (16)	1.0540 (2)	0.41034 (16)	0.0498 (4)
H2B	0.694 (2)	1.084 (3)	0.3292 (12)	0.060*
H2C	0.7894 (16)	1.095 (3)	0.4762 (17)	0.060*
C7	0.64197 (16)	0.9517 (2)	0.42884 (16)	0.0348 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0400 (6)	0.0860 (9)	0.0469 (7)	−0.0132 (6)	0.0017 (5)	−0.0025 (6)
F2	0.0539 (7)	0.0780 (8)	0.0681 (8)	−0.0311 (6)	0.0342 (6)	−0.0143 (6)
F3	0.0800 (8)	0.0823 (9)	0.0417 (6)	−0.0305 (7)	0.0330 (6)	−0.0004 (6)
O1	0.0441 (7)	0.0513 (8)	0.0314 (6)	−0.0103 (6)	0.0152 (5)	0.0007 (5)
O2	0.0365 (6)	0.0535 (7)	0.0293 (6)	−0.0081 (5)	0.0146 (5)	0.0014 (5)
C1	0.0336 (8)	0.0349 (8)	0.0326 (8)	0.0029 (7)	0.0164 (7)	−0.0019 (7)
C2	0.0379 (9)	0.0424 (10)	0.0340 (9)	0.0027 (8)	0.0152 (7)	0.0025 (7)
C3	0.0301 (8)	0.0503 (10)	0.0377 (9)	−0.0007 (7)	0.0094 (7)	−0.0055 (8)
C4	0.0372 (9)	0.0457 (10)	0.0479 (10)	−0.0091 (8)	0.0235 (8)	−0.0106 (8)
C5	0.0480 (10)	0.0463 (10)	0.0342 (9)	−0.0073 (8)	0.0241 (8)	−0.0039 (7)
C6	0.0382 (9)	0.0449 (10)	0.0298 (8)	−0.0050 (7)	0.0146 (7)	−0.0058 (7)
B1	0.0366 (10)	0.0356 (10)	0.0317 (9)	0.0016 (8)	0.0176 (8)	−0.0025 (7)
O3	0.0393 (6)	0.0568 (8)	0.0272 (6)	−0.0066 (6)	0.0131 (5)	0.0001 (5)
N1	0.0483 (9)	0.0609 (11)	0.0275 (8)	−0.0163 (8)	0.0120 (7)	−0.0006 (7)
N2	0.0443 (9)	0.0646 (11)	0.0377 (8)	−0.0133 (8)	0.0172 (7)	0.0042 (8)
C7	0.0346 (8)	0.0400 (9)	0.0298 (8)	0.0024 (7)	0.0152 (7)	−0.0004 (7)

Geometric parameters (Å, º)

O2—B1	1.353 (2)	C3—C4	1.371 (3)
O1—B1	1.356 (2)	C4—C5	1.372 (3)
C1—B1	1.579 (3)	C5—C6	1.372 (2)
C1—C2	1.398 (2)	C6—H6	0.9300
C1—C6	1.396 (2)	O3—C7	1.246 (2)
F1—C3	1.355 (2)	N1—H1A	0.868 (10)
F2—C4	1.347 (2)	N1—H1B	0.860 (10)
F3—C5	1.350 (2)	N1—C7	1.332 (2)
O1—H1	0.827 (10)	N2—H2B	0.867 (10)
O2—H2	0.820 (10)	N2—H2C	0.860 (10)
C2—H2A	0.9300	N2—C7	1.339 (2)
C2—C3	1.367 (3)
O2—B1—O1	118.93 (15)	C3—C4—C5	118.52 (16)
O1—B1—C1	116.42 (15)	F3—C5—C4	117.58 (15)
O2—B1—C1	124.65 (15)	F3—C5—C6	120.66 (15)
B1—O1—H1	112.5 (16)	C4—C5—C6	121.77 (16)
B1—O2—H2	119.3 (17)	C1—C6—H6	120.1
C6—C1—C2	118.02 (15)	C5—C6—C1	119.84 (15)
C2—C1—B1	119.05 (15)	C5—C6—H6	120.1
C6—C1—B1	122.92 (14)	H1A—N1—H1B	121 (2)
C1—C2—H2A	119.7	C7—N1—H1A	117.6 (15)
C3—C2—C1	120.55 (16)	C7—N1—H1B	121.3 (16)
C3—C2—H2A	119.7	H2B—N2—H2C	123 (2)
F1—C3—C2	120.78 (17)	C7—N2—H2B	115.0 (16)
F1—C3—C4	117.93 (16)	C7—N2—H2C	121.1 (16)
C2—C3—C4	121.29 (16)	O3—C7—N1	121.14 (15)
F2—C4—C3	120.95 (16)	O3—C7—N2	121.40 (15)
F2—C4—C5	120.53 (17)	N1—C7—N2	117.45 (16)
F1—C3—C4—F2	0.5 (3)	C2—C3—C4—F2	−179.49 (17)
F1—C3—C4—C5	−179.57 (16)	C2—C3—C4—C5	0.5 (3)
F2—C4—C5—F3	−0.6 (3)	C3—C4—C5—F3	179.46 (17)
F2—C4—C5—C6	179.45 (17)	C3—C4—C5—C6	−0.5 (3)
F3—C5—C6—C1	−179.91 (16)	C4—C5—C6—C1	0.1 (3)
C1—C2—C3—F1	−179.94 (16)	C6—C1—C2—C3	−0.4 (2)
C1—C2—C3—C4	0.0 (3)	C6—C1—B1—O1	178.30 (16)
C2—C1—C6—C5	0.4 (2)	C6—C1—B1—O2	−1.7 (3)
C2—C1—B1—O1	−0.7 (2)	B1—C1—C2—C3	178.57 (15)
C2—C1—B1—O2	179.33 (16)	B1—C1—C6—C5	−178.57 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.83 (1)	1.90 (1)	2.7084 (17)	166 (2)
O2—H2···O3^i	0.82 (1)	1.93 (1)	2.7427 (16)	169 (2)
N1—H1A···O2	0.87 (1)	2.12 (1)	2.982 (2)	176 (2)
N2—H2B···O1^ii	0.87 (1)	2.12 (1)	2.975 (2)	169 (2)
N1—H1B···F1^iii	0.86 (2)	2.41 (2)	3.214 (2)	155 (2)
N2—H2C···F1^iii	0.86 (2)	2.55 (2)	3.319 (2)	150 (2)

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, −y+3/2, z+1/2.