An inter-molecular dative B←N bond in 5-(4,4,5,5-tetra-methyl-1,3,2-dioxa-borolan-2-yl)-1,3-thia-zole.

The title compound, C(9)H(14)BNO(2)S, is in an unusual bend conformation and the B atom of one mol-ecule within the crystal forms an inter-molecular dative bond with the N atom of a neighbouring mol-ecule, an infrequent phenomenon in boronic derivative crystals.

Related literature

For related natural compounds, see: Dondoni & Merino (1996 ▶); Faulkner (1998 ▶); Hutchinson et al. (2000 ▶); Kalgutkar et al. (1996 ▶); Ogino et al. (1996 ▶); Williams & Jacobs (1993 ▶). For boronic esters, see: Allen (2002 ▶); Höpfl (1999 ▶); Hall (2005 ▶); Rettig & Trotter (1975 ▶); Sopková-de Oliveira Santos et al. (2003a ▶,b ▶). For details of the synthesis, see: Primas et al. (2008 ▶, 2009 ▶).

Experimental

Crystal data

C9H14BNO2S

M = 211.08

Monoclinic,

a = 12.6169 (3) Å

b = 7.9845 (2) Å

c = 12.6679 (3) Å

β = 119.064 (1)°

V = 1115.46 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.53 × 0.36 × 0.32 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

42058 measured reflections

5399 independent reflections

3895 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.159

S = 1.04

5399 reflections

139 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.87 e Å−3

Δρmin = −0.68 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052775/dn2507sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052775/dn2507Isup2.hkl

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

C9H14BNO2S	F(000) = 448
Mr = 211.08	Dx = 1.257 Mg m−3
Monoclinic, P21/c	Melting point: 371 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.6169 (3) Å	Cell parameters from 9543 reflections
b = 7.9845 (2) Å	θ = 3.2–35.8°
c = 12.6679 (3) Å	µ = 0.26 mm−1
β = 119.064 (1)°	T = 296 K
V = 1115.46 (5) Å3	Plate, colourless
Z = 4	0.53 × 0.36 × 0.32 mm

Bruker APEXII CCD area-detector diffractometer	3895 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
graphite	θmax = 36.4°, θmin = 1.9°
φ and ω scans	h = −21→21
42058 measured reflections	k = −10→13
5399 independent reflections	l = −21→21

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0814P)2 + 0.2917P] where P = (Fo2 + 2Fc2)/3
5399 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.87 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.16573 (3)	0.62779 (5)	0.44438 (3)	0.04720 (12)
C2	0.06243 (12)	0.77776 (17)	0.42356 (10)	0.0386 (3)
H2	0.0698 (18)	0.848 (3)	0.4859 (19)	0.057 (5)*
N3	−0.02480 (8)	0.78577 (10)	0.31137 (8)	0.02725 (16)
C4	−0.00940 (10)	0.67047 (14)	0.23876 (10)	0.0305 (2)
H4	−0.0704 (14)	0.667 (2)	0.1570 (15)	0.040 (4)*
C5	0.08968 (9)	0.57082 (12)	0.29535 (9)	0.02743 (18)
B1	0.13725 (10)	0.41927 (13)	0.24402 (10)	0.02591 (19)
O2	0.24223 (7)	0.34057 (10)	0.33978 (7)	0.02967 (16)
O1	0.16342 (7)	0.46160 (10)	0.14816 (7)	0.03061 (16)
C6	0.29217 (10)	0.43640 (17)	0.19662 (10)	0.0343 (2)
C8	0.31785 (16)	0.3921 (3)	0.09484 (14)	0.0580 (4)
H8A	0.4032	0.3733	0.1271	0.087*
H8B	0.2925	0.4827	0.0378	0.087*
H8C	0.2741	0.2924	0.0551	0.087*
C9	0.35543 (14)	0.6010 (2)	0.25586 (15)	0.0492 (3)
H9A	0.3213	0.6906	0.1985	0.074*
H9B	0.4405	0.5919	0.2821	0.074*
H9C	0.3441	0.6238	0.3241	0.074*
C7	0.31999 (10)	0.29495 (15)	0.29088 (10)	0.0332 (2)
C10	0.44987 (12)	0.2890 (2)	0.39326 (14)	0.0501 (3)
H10A	0.4674	0.3891	0.4408	0.075*
H10B	0.5041	0.2807	0.3605	0.075*
H10C	0.4602	0.1933	0.4433	0.075*
C11	0.28385 (15)	0.12147 (19)	0.23354 (16)	0.0519 (4)
H11A	0.2824	0.0443	0.2909	0.078*
H11B	0.3416	0.0842	0.2099	0.078*
H11C	0.2048	0.1269	0.1638	0.078*

	U11	U22	U33	U12	U13	U23
S1	0.04648 (19)	0.0520 (2)	0.02922 (15)	0.02133 (14)	0.00746 (12)	−0.00218 (12)
C2	0.0423 (6)	0.0395 (6)	0.0296 (5)	0.0097 (5)	0.0139 (4)	−0.0041 (4)
N3	0.0284 (4)	0.0240 (3)	0.0294 (4)	0.0009 (3)	0.0141 (3)	−0.0013 (3)
C4	0.0298 (4)	0.0294 (4)	0.0292 (4)	0.0042 (3)	0.0119 (4)	−0.0028 (3)
C5	0.0281 (4)	0.0246 (4)	0.0301 (4)	0.0011 (3)	0.0146 (3)	0.0003 (3)
B1	0.0258 (4)	0.0243 (4)	0.0283 (4)	0.0008 (3)	0.0136 (4)	0.0013 (3)
O2	0.0293 (3)	0.0315 (3)	0.0278 (3)	0.0057 (3)	0.0136 (3)	0.0029 (3)
O1	0.0275 (3)	0.0366 (4)	0.0288 (3)	−0.0002 (3)	0.0145 (3)	0.0041 (3)
C6	0.0288 (4)	0.0471 (6)	0.0304 (4)	−0.0017 (4)	0.0171 (4)	−0.0033 (4)
C8	0.0505 (8)	0.0937 (13)	0.0402 (7)	0.0083 (8)	0.0303 (6)	−0.0025 (7)
C9	0.0424 (7)	0.0543 (8)	0.0497 (7)	−0.0174 (6)	0.0214 (6)	−0.0024 (6)
C7	0.0279 (4)	0.0376 (5)	0.0312 (5)	0.0053 (4)	0.0120 (4)	−0.0054 (4)
C10	0.0312 (5)	0.0667 (9)	0.0426 (6)	0.0123 (6)	0.0103 (5)	−0.0041 (6)
C11	0.0541 (8)	0.0399 (6)	0.0550 (8)	0.0094 (6)	0.0212 (7)	−0.0123 (6)

S1—C2	1.6936 (12)	C6—C7	1.5548 (17)
S1—C5	1.7122 (11)	C8—H8A	0.9600
C2—N3	1.3097 (15)	C8—H8B	0.9600
C2—H2	0.94 (2)	C8—H8C	0.9600
N3—C4	1.3803 (13)	C9—H9A	0.9600
N3—B1i	1.6354 (14)	C9—H9B	0.9600
C4—C5	1.3561 (14)	C9—H9C	0.9600
C4—H4	0.945 (16)	C7—C10	1.5182 (17)
C5—B1	1.6207 (15)	C7—C11	1.5273 (18)
B1—O2	1.4351 (13)	C10—H10A	0.9600
B1—O1	1.4447 (13)	C10—H10B	0.9600
B1—N3ii	1.6354 (14)	C10—H10C	0.9600
O2—C7	1.4386 (13)	C11—H11A	0.9600
O1—C6	1.4448 (13)	C11—H11B	0.9600
C6—C8	1.5159 (17)	C11—H11C	0.9600
C6—C9	1.5318 (19)
C2—S1—C5	92.26 (5)	H8A—C8—H8B	109.5
N3—C2—S1	112.39 (8)	C6—C8—H8C	109.5
N3—C2—H2	125.0 (13)	H8A—C8—H8C	109.5
S1—C2—H2	122.6 (13)	H8B—C8—H8C	109.5
C2—N3—C4	111.99 (9)	C6—C9—H9A	109.5
C2—N3—B1i	126.44 (9)	C6—C9—H9B	109.5
C4—N3—B1i	121.50 (8)	H9A—C9—H9B	109.5
C5—C4—N3	115.54 (10)	C6—C9—H9C	109.5
C5—C4—H4	127.7 (11)	H9A—C9—H9C	109.5
N3—C4—H4	116.7 (11)	H9B—C9—H9C	109.5
C4—C5—B1	130.68 (9)	O2—C7—C10	108.61 (10)
C4—C5—S1	107.81 (8)	O2—C7—C11	109.02 (11)
B1—C5—S1	121.49 (7)	C10—C7—C11	109.07 (12)
O2—B1—O1	108.61 (8)	O2—C7—C6	101.54 (8)
O2—B1—C5	110.94 (8)	C10—C7—C6	115.23 (12)
O1—B1—C5	116.29 (8)	C11—C7—C6	112.94 (11)
O2—B1—N3ii	109.23 (8)	C7—C10—H10A	109.5
O1—B1—N3ii	107.26 (8)	C7—C10—H10B	109.5
C5—B1—N3ii	104.22 (8)	H10A—C10—H10B	109.5
B1—O2—C7	106.82 (8)	C7—C10—H10C	109.5
B1—O1—C6	106.21 (8)	H10A—C10—H10C	109.5
O1—C6—C8	109.38 (10)	H10B—C10—H10C	109.5
O1—C6—C9	107.41 (11)	C7—C11—H11A	109.5
C8—C6—C9	109.94 (12)	C7—C11—H11B	109.5
O1—C6—C7	102.43 (8)	H11A—C11—H11B	109.5
C8—C6—C7	114.97 (12)	C7—C11—H11C	109.5
C9—C6—C7	112.19 (10)	H11A—C11—H11C	109.5
C6—C8—H8A	109.5	H11B—C11—H11C	109.5
C6—C8—H8B	109.5
O1—C6—C7—O2	−37.74 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1iii	0.94 (2)	2.36 (2)	3.2446 (14)	157.5 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.94 (2)	2.36 (2)	3.2446 (14)	157.5 (17)

Symmetry code: (i) .