2-(Pyridin-4-yl)-2,3-di­hydro-1H-naphtho­[1,8-de][1,3,2]di­aza­borinine

Yamamoto, R.; Hashimoto, S.; Okuno, T.

doi:10.1107/S2414314624006151

2-(Pyridin-4-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine

The title compound, C₁₅H₁₂BN₃, is a type of diazaborinane featuring substitution at 1, 2, and 3 positions in the nitrogen–boron six-membered heterocycle. It is comprised of two almost planar units, the pyridyl ring and the Bdan (dan = 1,8-diaminonaphtho) group, which subtend a dihedral angle of 24.57 (5)°. In the crystal, the molecules are linked into R₄⁴(28) hydrogen-bonding networks around the fourfold inversion axis, giving cyclic tetramers. The molecules form columnar stacks along the c axis.

Keywords: crystal structure; pyridine derivative; tetrameric structure; dan.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2414314624006151/bx4031sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2414314624006151/bx4031Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2414314624006151/bx4031Isup3.cml Supplementary material

CCDC reference: 2364937

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.031
wR factor = 0.083
Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Bond Without Acceptor  N3       --H3       .     Please Check

Alert level G
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High .      0.300 Report
PLAT795_ALERT_4_G C-Atom in CIF Coordinate List Out-of-Sequence ..         C1 Note
PLAT797_ALERT_4_G N-Atom in CIF Coordinate List Out-of-Sequence ..         N2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         37 Note
PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ...........      2.177 Note
              Predicted wR2: Based on SigI   2  3.79 or SHELX Weight  7.82       
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          4 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

\ 2-(Pyridin-4-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]\ diazaborinine top

Crystal data top

C₁₅H₁₂BN₃	D_x = 1.376 Mg m⁻³
M_r = 245.09	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, I4	Cell parameters from 5132 reflections
a = 21.5659 (3) Å	θ = 2.9–75.0°
c = 5.0863 (1) Å	µ = 0.65 mm⁻¹
V = 2365.58 (8) Å³	T = 100 K
Z = 8	Block, clear colourless
F(000) = 1024	0.2 × 0.05 × 0.05 mm

Data collection top

XtaLAB Synergy R, DW system, HyPix diffractometer	2268 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	2125 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.036
Detector resolution: 10.0000 pixels mm^-1	θ_max = 75.0°, θ_min = 2.9°
ω scans	h = −25→26
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024)	k = −26→27
T_min = 0.807, T_max = 1.000	l = −5→6
7772 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0502P)² + 0.1789P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.083	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.15 e Å⁻³
2268 reflections	Δρ_min = −0.15 e Å⁻³
180 parameters	Absolute structure: Flack x determined using 840 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.2 (3)
Primary atom site location: structure-invariant direct methods

Special details top

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. The positions of the N-bound H atoms were obtained from difference Fourier maps and were refined isotropically. The C-bound H atoms were placed at ideal positions and were refined as riding on their parent C atoms. U_iso(H) values of the H atoms were set at 1.2U_eq(parent atom for Csp²).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N3	0.20041 (7)	0.03150 (8)	−0.0041 (4)	0.0233 (4)
C7	0.28868 (9)	0.15497 (9)	0.5132 (4)	0.0252 (4)
H7	0.3324	0.1604	0.5071	0.030*
C1	0.39265 (9)	−0.01777 (9)	−0.5063 (4)	0.0270 (4)
H1	0.4315	−0.0032	−0.5689	0.032*
N2	0.29394 (8)	0.07934 (7)	0.1587 (3)	0.0217 (3)
C13	0.10022 (9)	0.05895 (9)	0.1820 (4)	0.0267 (4)
H13	0.0797	0.0324	0.0611	0.032*
C10	0.15895 (9)	0.14042 (9)	0.5376 (4)	0.0255 (4)
C15	0.19455 (9)	0.10642 (8)	0.3491 (4)	0.0219 (4)
C5	0.31573 (9)	−0.08947 (9)	−0.5129 (4)	0.0273 (4)
H5	0.2989	−0.1270	−0.5796	0.033*
C6	0.26012 (9)	0.11421 (8)	0.3414 (4)	0.0218 (4)
C14	0.16387 (9)	0.06513 (9)	0.1728 (4)	0.0231 (4)
C11	0.09363 (10)	0.13134 (9)	0.5452 (4)	0.0288 (5)
H11	0.0693	0.1527	0.6721	0.035*
B1	0.26579 (10)	0.03753 (10)	−0.0181 (4)	0.0220 (4)
C3	0.30411 (9)	−0.00146 (9)	−0.2242 (4)	0.0220 (4)
C4	0.28147 (9)	−0.05701 (9)	−0.3271 (4)	0.0262 (4)
H4	0.2426	−0.0727	−0.2700	0.031*
C12	0.06564 (9)	0.09191 (9)	0.3700 (4)	0.0286 (5)
H12	0.0219	0.0868	0.3758	0.034*
N1	0.37087 (8)	−0.07118 (8)	−0.6036 (3)	0.0268 (4)
C2	0.36184 (9)	0.01756 (9)	−0.3191 (4)	0.0246 (4)
H2A	0.3801	0.0547	−0.2555	0.030*
C9	0.19006 (10)	0.18127 (9)	0.7109 (4)	0.0277 (5)
H9	0.1670	0.2039	0.8380	0.033*
C8	0.25310 (10)	0.18841 (9)	0.6969 (4)	0.0279 (4)
H8	0.2732	0.2164	0.8132	0.033*
H3	0.1804 (12)	0.0058 (12)	−0.125 (6)	0.042 (7)*
H2	0.3364 (11)	0.0870 (10)	0.167 (5)	0.028 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0236 (8)	0.0238 (8)	0.0225 (8)	0.0017 (6)	−0.0004 (7)	−0.0003 (7)
C7	0.0272 (9)	0.0252 (9)	0.0233 (10)	0.0016 (8)	−0.0001 (8)	0.0025 (8)
C1	0.0229 (9)	0.0263 (9)	0.0317 (10)	0.0004 (8)	0.0016 (9)	0.0004 (9)
N2	0.0203 (8)	0.0225 (7)	0.0223 (8)	0.0012 (6)	0.0012 (7)	0.0008 (7)
C13	0.0254 (10)	0.0260 (9)	0.0287 (10)	−0.0001 (8)	0.0002 (9)	0.0042 (9)
C10	0.0313 (10)	0.0235 (9)	0.0216 (10)	0.0058 (8)	0.0042 (8)	0.0068 (8)
C15	0.0262 (9)	0.0202 (8)	0.0193 (9)	0.0045 (7)	0.0022 (8)	0.0053 (7)
C5	0.0272 (10)	0.0245 (9)	0.0301 (10)	−0.0008 (8)	−0.0020 (9)	−0.0043 (8)
C6	0.0270 (9)	0.0200 (8)	0.0183 (9)	0.0027 (7)	0.0016 (8)	0.0050 (8)
C14	0.0271 (9)	0.0209 (9)	0.0214 (9)	0.0025 (7)	0.0018 (8)	0.0057 (8)
C11	0.0301 (10)	0.0283 (10)	0.0278 (11)	0.0088 (8)	0.0094 (9)	0.0068 (8)
B1	0.0254 (10)	0.0194 (9)	0.0212 (10)	0.0027 (8)	0.0001 (9)	0.0041 (9)
C3	0.0227 (9)	0.0228 (9)	0.0204 (9)	0.0030 (7)	−0.0033 (7)	0.0017 (7)
C4	0.0223 (9)	0.0274 (9)	0.0290 (10)	−0.0008 (8)	−0.0003 (8)	0.0000 (9)
C12	0.0248 (9)	0.0290 (10)	0.0319 (11)	0.0044 (8)	0.0051 (9)	0.0092 (9)
N1	0.0272 (9)	0.0263 (8)	0.0270 (9)	0.0038 (7)	−0.0015 (7)	−0.0034 (7)
C2	0.0253 (9)	0.0210 (9)	0.0276 (10)	−0.0009 (8)	−0.0009 (8)	−0.0012 (8)
C9	0.0383 (11)	0.0243 (10)	0.0205 (10)	0.0092 (8)	0.0042 (9)	0.0014 (8)
C8	0.0387 (11)	0.0223 (9)	0.0226 (10)	0.0035 (8)	−0.0019 (9)	0.0010 (8)

Geometric parameters (Å, º) top

N3—C14	1.399 (3)	C10—C9	1.416 (3)
N3—B1	1.418 (3)	C15—C6	1.425 (3)
N3—H3	0.93 (3)	C15—C14	1.426 (3)
C7—H7	0.9500	C5—H5	0.9500
C7—C6	1.384 (3)	C5—C4	1.389 (3)
C7—C8	1.408 (3)	C5—N1	1.335 (3)
C1—H1	0.9500	C11—H11	0.9500
C1—N1	1.339 (3)	C11—C12	1.372 (3)
C1—C2	1.389 (3)	B1—C3	1.578 (3)
N2—C6	1.401 (2)	C3—C4	1.396 (3)
N2—B1	1.411 (3)	C3—C2	1.397 (3)
N2—H2	0.93 (2)	C4—H4	0.9500
C13—H13	0.9500	C12—H12	0.9500
C13—C14	1.380 (3)	C2—H2A	0.9500
C13—C12	1.405 (3)	C9—H9	0.9500
C10—C15	1.431 (3)	C9—C8	1.370 (3)
C10—C11	1.423 (3)	C8—H8	0.9500

C14—N3—B1	123.02 (17)	C13—C14—N3	122.15 (18)
C14—N3—H3	118.1 (17)	C13—C14—C15	120.03 (18)
B1—N3—H3	118.8 (17)	C10—C11—H11	119.9
C6—C7—H7	119.9	C12—C11—C10	120.23 (18)
C6—C7—C8	120.13 (18)	C12—C11—H11	119.9
C8—C7—H7	119.9	N3—B1—C3	120.36 (18)
N1—C1—H1	118.0	N2—B1—N3	117.04 (18)
N1—C1—C2	123.90 (18)	N2—B1—C3	122.60 (17)
C2—C1—H1	118.0	C4—C3—B1	121.57 (17)
C6—N2—B1	122.82 (16)	C4—C3—C2	115.74 (18)
C6—N2—H2	112.8 (15)	C2—C3—B1	122.68 (17)
B1—N2—H2	124.4 (15)	C5—C4—C3	120.12 (18)
C14—C13—H13	119.9	C5—C4—H4	119.9
C14—C13—C12	120.1 (2)	C3—C4—H4	119.9
C12—C13—H13	119.9	C13—C12—H12	119.3
C11—C10—C15	118.62 (19)	C11—C12—C13	121.46 (18)
C9—C10—C15	118.83 (18)	C11—C12—H12	119.3
C9—C10—C11	122.54 (18)	C5—N1—C1	116.03 (17)
C6—C15—C10	119.37 (18)	C1—C2—C3	120.15 (17)
C6—C15—C14	121.14 (17)	C1—C2—H2A	119.9
C14—C15—C10	119.49 (17)	C3—C2—H2A	119.9
C4—C5—H5	118.0	C10—C9—H9	119.7
N1—C5—H5	118.0	C8—C9—C10	120.51 (19)
N1—C5—C4	124.06 (18)	C8—C9—H9	119.7
C7—C6—N2	121.89 (17)	C7—C8—H8	119.4
C7—C6—C15	119.97 (17)	C9—C8—C7	121.19 (19)
N2—C6—C15	118.14 (16)	C9—C8—H8	119.4
N3—C14—C15	117.81 (16)

N3—B1—C3—C4	−23.9 (3)	C11—C10—C15—C6	−179.01 (17)
N3—B1—C3—C2	154.92 (19)	C11—C10—C15—C14	0.7 (3)
N2—B1—C3—C4	156.09 (19)	C11—C10—C9—C8	179.81 (19)
N2—B1—C3—C2	−25.1 (3)	B1—N3—C14—C13	179.50 (19)
C10—C15—C6—C7	−0.8 (3)	B1—N3—C14—C15	−1.1 (3)
C10—C15—C6—N2	178.65 (16)	B1—N2—C6—C7	179.99 (18)
C10—C15—C14—N3	−178.38 (17)	B1—N2—C6—C15	0.5 (3)
C10—C15—C14—C13	1.0 (3)	B1—C3—C4—C5	178.49 (18)
C10—C11—C12—C13	0.9 (3)	B1—C3—C2—C1	−178.13 (18)
C10—C9—C8—C7	−0.8 (3)	C4—C5—N1—C1	−0.6 (3)
C15—C10—C11—C12	−1.7 (3)	C4—C3—C2—C1	0.7 (3)
C15—C10—C9—C8	0.5 (3)	C12—C13—C14—N3	177.53 (17)
C6—C7—C8—C9	0.3 (3)	C12—C13—C14—C15	−1.8 (3)
C6—N2—B1—N3	−0.3 (3)	N1—C1—C2—C3	−1.1 (3)
C6—N2—B1—C3	179.77 (16)	N1—C5—C4—C3	0.3 (3)
C6—C15—C14—N3	1.4 (3)	C2—C1—N1—C5	0.9 (3)
C6—C15—C14—C13	−179.24 (18)	C2—C3—C4—C5	−0.4 (3)
C14—N3—B1—N2	0.6 (3)	C9—C10—C15—C6	0.3 (3)
C14—N3—B1—C3	−179.47 (17)	C9—C10—C15—C14	−179.93 (16)
C14—C13—C12—C11	0.9 (3)	C9—C10—C11—C12	179.00 (18)
C14—C15—C6—C7	179.45 (17)	C8—C7—C6—N2	−178.96 (17)
C14—C15—C6—N2	−1.1 (3)	C8—C7—C6—C15	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.93 (2)	2.21 (2)	3.113 (2)	162 (2)

Symmetry code: (i) y+1/2, −x+1/2, −z−1/2.

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

2-(Pyridin-4-yl)-2,3-di­hydro-1H-naphtho­[1,8-de][1,3,2]di­aza­borinine

Supporting information

Key indicators

checkCIF/PLATON results

2-(Pyridin-4-yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine