2-(4-Chloro-phen-yl)naphtho-[1,8-de][1,3,2]diaza-borinane.

The title compound, C(16)H(12)BClN(2), is one in a series of diaza-borinanes, derived from 1,8-diaminona-phthalene, featuring substitution at the 1, 2 and 3 positions in the nitro-gen-boron heterocycle. The structure deviates from planarity, the torsion angle subtended by the p-chloro-phenyl ring relative to the nitro-gen-boron heterocycle being -44-.3(3)°. The mol-ecules form infinite chains with strong inter-actions between the vacant pz orbital of the B atom and the π-system of an adjacent mol-ecule. The distance between the B atom and the 10-atom centroid of an adjacent naphthalene ring is 3.381 (4) Å. One N-H H atom is weakly hydrogen bonded to the Cl atom of an adjacent mol-ecule. This combination of inter-molecular inter-actions leads to the formation of an infinite two-dimensional network perpendic-ular to the c axis.

Related literature

For the synthesis of related compounds, see: Letsinger & Hamilton (1958 ▶); Pailer & Fenzl (1961 ▶); Kaupp et al. (2003 ▶); Slabber 2011 ▶. For single-crystal X-ray structures and lumin­escence studies of related compounds, see: Weber, et al. (2009 ▶).

Experimental

Crystal data

C16H12BClN2

M = 278.54

Monoclinic,

a = 4.7165 (2) Å

b = 10.2815 (4) Å

c = 13.5711 (6) Å

β = 96.555 (4)°

V = 653.79 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.28 mm−1

T = 296 K

0.50 × 0.15 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur 2 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.896, T max = 0.981

4902 measured reflections

2286 independent reflections

2011 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.098

S = 1.00

2286 reflections

189 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▶), 924 Friedel pairs

Flack parameter: 0.05 (7)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811025487/om2441sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025487/om2441Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811025487/om2441Isup3.cml

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

C16H12BClN2	F(000) = 288
Mr = 278.54	Dx = 1.415 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2982 reflections
a = 4.7165 (2) Å	θ = 3.6–32.0°
b = 10.2815 (4) Å	µ = 0.28 mm−1
c = 13.5711 (6) Å	T = 296 K
β = 96.555 (4)°	Plate, colourless
V = 653.79 (5) Å3	0.50 × 0.15 × 0.07 mm
Z = 2

Oxford Diffraction Xcalibur 2 CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	2011 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 8.4190 pixels mm-1	θmax = 26.1°, θmin = 3.6°
ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→11
Tmin = 0.896, Tmax = 0.981	l = −16→16
4902 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0669P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2286 reflections	Δρmax = 0.15 e Å−3
189 parameters	Δρmin = −0.25 e Å−3
1 restraint	Absolute structure: Flack (1983), 924 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (7)

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 > 2σ(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
Cl	−1.03675 (12)	0.41269 (9)	0.42497 (4)	0.0546 (2)
N1	−0.1813 (4)	0.7869 (2)	0.15026 (15)	0.0391 (4)
H1	−0.257 (5)	0.732 (3)	0.1114 (18)	0.048 (8)*
N2	−0.1196 (4)	0.9013 (2)	0.30427 (13)	0.0398 (4)
H2	−0.134 (5)	0.911 (3)	0.3607 (17)	0.047 (7)*
C1	0.0738 (5)	0.9863 (2)	0.26954 (16)	0.0362 (5)
C2	0.2031 (5)	1.0847 (2)	0.32771 (18)	0.0462 (6)
H2A	0.1624	1.0952	0.3927	0.055*
C3	0.3950 (6)	1.1682 (2)	0.28863 (19)	0.0498 (6)
H3	0.4782	1.2354	0.3278	0.060*
C4	0.4629 (5)	1.1536 (2)	0.19447 (19)	0.0479 (6)
H4	0.5938	1.2097	0.1706	0.057*
C5	0.3366 (5)	1.0540 (2)	0.13264 (16)	0.0387 (5)
C6	0.4036 (5)	1.0340 (2)	0.03481 (17)	0.0447 (5)
H6	0.5346	1.0879	0.0087	0.054*
C7	0.2761 (5)	0.9356 (3)	−0.02132 (16)	0.0489 (6)
H7	0.3219	0.9238	−0.0856	0.059*
C8	0.0804 (5)	0.8527 (2)	0.01465 (17)	0.0463 (6)
H8	−0.0039	0.7867	−0.0254	0.056*
C9	0.0105 (4)	0.8681 (2)	0.11029 (16)	0.0359 (5)
C10	0.1391 (4)	0.9690 (2)	0.17085 (16)	0.0350 (5)
C11	−0.4634 (5)	0.7024 (2)	0.29241 (16)	0.0358 (5)
C12	−0.6037 (5)	0.6040 (2)	0.23650 (17)	0.0440 (6)
H11	−0.5771	0.5972	0.1698	0.053*
C13	−0.7810 (5)	0.5156 (2)	0.27541 (17)	0.0455 (6)
H12	−0.8725	0.4510	0.2357	0.055*
C14	−0.8199 (4)	0.5247 (2)	0.37392 (17)	0.0389 (5)
C15	−0.6900 (5)	0.6218 (3)	0.43220 (17)	0.0471 (6)
H14	−0.7205	0.6287	0.4985	0.057*
C16	−0.5137 (5)	0.7092 (3)	0.39146 (17)	0.0485 (6)
H15	−0.4260	0.7746	0.4314	0.058*
B	−0.2545 (5)	0.7993 (3)	0.24819 (18)	0.0346 (5)

	U11	U22	U33	U12	U13	U23
Cl	0.0573 (3)	0.0516 (3)	0.0563 (3)	−0.0125 (3)	0.0131 (2)	0.0070 (3)
N1	0.0428 (10)	0.0405 (11)	0.0344 (10)	−0.0057 (9)	0.0062 (8)	−0.0030 (9)
N2	0.0443 (9)	0.0446 (11)	0.0319 (9)	−0.0039 (9)	0.0107 (7)	−0.0019 (11)
C1	0.0350 (10)	0.0339 (12)	0.0398 (11)	0.0027 (9)	0.0046 (9)	0.0023 (9)
C2	0.0519 (14)	0.0451 (14)	0.0420 (13)	−0.0015 (11)	0.0071 (11)	−0.0053 (11)
C3	0.0554 (15)	0.0415 (15)	0.0511 (16)	−0.0086 (11)	0.0005 (12)	−0.0048 (11)
C4	0.0506 (14)	0.0385 (14)	0.0547 (15)	−0.0025 (11)	0.0065 (11)	0.0089 (11)
C5	0.0360 (11)	0.0359 (12)	0.0437 (12)	0.0038 (9)	0.0019 (9)	0.0091 (10)
C6	0.0490 (13)	0.0469 (13)	0.0395 (13)	0.0008 (11)	0.0109 (10)	0.0118 (11)
C7	0.0551 (13)	0.0576 (18)	0.0356 (11)	0.0042 (11)	0.0123 (10)	0.0064 (11)
C8	0.0534 (14)	0.0521 (14)	0.0342 (12)	−0.0029 (11)	0.0087 (10)	−0.0059 (11)
C9	0.0336 (10)	0.0392 (12)	0.0353 (11)	0.0029 (8)	0.0053 (8)	0.0033 (9)
C10	0.0343 (10)	0.0342 (11)	0.0361 (11)	0.0072 (9)	0.0020 (9)	0.0033 (9)
C11	0.0354 (11)	0.0367 (12)	0.0354 (11)	0.0040 (9)	0.0051 (8)	0.0037 (9)
C12	0.0521 (14)	0.0473 (15)	0.0337 (12)	−0.0039 (11)	0.0094 (11)	−0.0010 (10)
C13	0.0524 (13)	0.0437 (14)	0.0397 (13)	−0.0071 (11)	0.0023 (10)	−0.0035 (10)
C14	0.0354 (11)	0.0378 (12)	0.0435 (13)	0.0018 (9)	0.0047 (9)	0.0058 (10)
C15	0.0564 (14)	0.0538 (15)	0.0325 (12)	−0.0100 (12)	0.0108 (10)	−0.0030 (11)
C16	0.0550 (15)	0.0512 (15)	0.0399 (13)	−0.0140 (12)	0.0074 (11)	−0.0092 (12)
B	0.0319 (11)	0.0361 (13)	0.0358 (12)	0.0030 (10)	0.0037 (9)	0.0049 (10)

Cl—C14	1.736 (2)	C6—H6	0.9300
N1—C9	1.386 (3)	C7—C8	1.386 (3)
N1—B	1.416 (3)	C7—H7	0.9300
N1—H1	0.82 (3)	C8—C9	1.384 (3)
N2—C1	1.384 (3)	C8—H8	0.9300
N2—B	1.405 (3)	C9—C10	1.416 (3)
N2—H2	0.78 (2)	C11—C12	1.387 (3)
C1—C2	1.382 (3)	C11—C16	1.393 (3)
C1—C10	1.419 (3)	C11—B	1.568 (3)
C2—C3	1.396 (3)	C12—C13	1.380 (3)
C2—H2A	0.9300	C12—H11	0.9300
C3—C4	1.361 (3)	C13—C14	1.373 (3)
C3—H3	0.9300	C13—H12	0.9300
C4—C5	1.411 (3)	C14—C15	1.373 (3)
C4—H4	0.9300	C15—C16	1.382 (3)
C5—C6	1.414 (3)	C15—H14	0.9300
C5—C10	1.418 (3)	C16—H15	0.9300
C6—C7	1.364 (3)
C9—N1—B	123.6 (2)	C7—C8—H8	120.0
C9—N1—H1	114.6 (17)	C8—C9—N1	122.3 (2)
B—N1—H1	121.7 (17)	C8—C9—C10	119.74 (19)
C1—N2—B	124.20 (18)	N1—C9—C10	117.99 (18)
C1—N2—H2	113 (2)	C9—C10—C5	119.67 (19)
B—N2—H2	123 (2)	C9—C10—C1	120.99 (19)
C2—C1—N2	122.2 (2)	C5—C10—C1	119.3 (2)
C2—C1—C10	120.1 (2)	C12—C11—C16	116.2 (2)
N2—C1—C10	117.69 (19)	C12—C11—B	122.39 (18)
C1—C2—C3	119.8 (2)	C16—C11—B	121.4 (2)
C1—C2—H2A	120.1	C13—C12—C11	122.9 (2)
C3—C2—H2A	120.1	C13—C12—H11	118.5
C4—C3—C2	121.4 (2)	C11—C12—H11	118.5
C4—C3—H3	119.3	C14—C13—C12	118.8 (2)
C2—C3—H3	119.3	C14—C13—H12	120.6
C3—C4—C5	120.7 (2)	C12—C13—H12	120.6
C3—C4—H4	119.7	C13—C14—C15	120.7 (2)
C5—C4—H4	119.7	C13—C14—Cl	119.54 (18)
C4—C5—C6	122.6 (2)	C15—C14—Cl	119.78 (18)
C4—C5—C10	118.7 (2)	C14—C15—C16	119.4 (2)
C6—C5—C10	118.7 (2)	C14—C15—H14	120.3
C7—C6—C5	120.1 (2)	C16—C15—H14	120.3
C7—C6—H6	120.0	C15—C16—C11	122.0 (2)
C5—C6—H6	120.0	C15—C16—H15	119.0
C6—C7—C8	121.9 (2)	C11—C16—H15	119.0
C6—C7—H7	119.1	N2—B—N1	115.57 (19)
C8—C7—H7	119.1	N2—B—C11	122.17 (18)
C9—C8—C7	120.0 (2)	N1—B—C11	122.22 (19)
C9—C8—H8	120.0
B—N2—C1—C2	−179.4 (2)	C6—C5—C10—C1	178.8 (2)
B—N2—C1—C10	0.1 (3)	C2—C1—C10—C9	179.5 (2)
N2—C1—C2—C3	−179.5 (2)	N2—C1—C10—C9	−0.1 (3)
C10—C1—C2—C3	1.0 (3)	C2—C1—C10—C5	−0.4 (3)
C1—C2—C3—C4	−1.3 (4)	N2—C1—C10—C5	−179.92 (19)
C2—C3—C4—C5	1.1 (4)	C16—C11—C12—C13	−0.9 (4)
C3—C4—C5—C6	−179.1 (2)	B—C11—C12—C13	177.9 (2)
C3—C4—C5—C10	−0.5 (3)	C11—C12—C13—C14	−0.3 (4)
C4—C5—C6—C7	179.6 (2)	C12—C13—C14—C15	1.5 (4)
C10—C5—C6—C7	0.9 (3)	C12—C13—C14—Cl	−178.80 (19)
C5—C6—C7—C8	−0.2 (4)	C13—C14—C15—C16	−1.4 (4)
C6—C7—C8—C9	−0.4 (4)	Cl—C14—C15—C16	178.9 (2)
C7—C8—C9—N1	−179.2 (2)	C14—C15—C16—C11	0.2 (4)
C7—C8—C9—C10	0.2 (3)	C12—C11—C16—C15	0.9 (4)
B—N1—C9—C8	179.2 (2)	B—C11—C16—C15	−177.8 (2)
B—N1—C9—C10	−0.2 (3)	C1—N2—B—N1	−0.2 (3)
C8—C9—C10—C5	0.5 (3)	C1—N2—B—C11	177.6 (2)
N1—C9—C10—C5	179.96 (18)	C9—N1—B—N2	0.2 (3)
C8—C9—C10—C1	−179.3 (2)	C9—N1—B—C11	−177.60 (19)
N1—C9—C10—C1	0.1 (3)	C12—C11—B—N2	178.0 (2)
C4—C5—C10—C9	−179.77 (19)	C16—C11—B—N2	−3.3 (3)
C6—C5—C10—C9	−1.1 (3)	C12—C11—B—N1	−4.3 (3)
C4—C5—C10—C1	0.1 (3)	C16—C11—B—N1	174.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cli	0.78 (2)	2.93 (2)	3.666 (2)	158 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cli	0.78 (2)	2.93 (2)	3.666 (2)	158 (2)

Symmetry code: (i) .