4,4-Difluoro-8-(4-iodo­phen­yl)-1,3,5,7-tetra­methyl-3a-aza-4a-azonia-4-borata-s-indacene

Sun, Y.

doi:10.1107/S1600536812004072

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1302

doi:10.1107/S1600536812004072

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4,4-Difluoro-8-(4-iodophenyl)-1,3,5,7-tetramethyl-3a-aza-4a-azonia-4-borata-s-indacene

Yongling Sun ^a ^*

^aDepartment of Biology, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: sylswx@163.com

(Received 20 January 2012; accepted 31 January 2012; online 4 April 2012)

In the title compound, C₁₉H₁₈BF₂IN₂, which is a boron–dipyrromethene (BODIPY) derivative, the BODIPY mean plane forms dihedral angles of 88.95 (4) and 78.21 (3)° with the F/B/F and 4-iodophenyl planes, respectively.

Related literature

For the crystal structures of related boron–dipyrromethene derivatives, see: Zhou (2010 ); Chen & Jiang (2011 ); Hinkle et al. (2011 ); Cui et al. (2012 ).

Experimental

Crystal data

C₁₉H₁₈BF₂IN₂
M_r = 450.06
Monoclinic, P 2₁ /c
a = 12.1004 (3) Å
b = 8.1992 (2) Å
c = 18.0607 (4) Å
β = 90.577 (3)°
V = 1791.77 (8) Å³
Z = 4
Cu Kα radiation
μ = 14.24 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.102, T_max = 0.110
6829 measured reflections
3348 independent reflections
2770 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.166
S = 1.05
3348 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −1.36 e Å⁻³

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004072/cv5238sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004072/cv5238Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004072/cv5238Isup3.cml

checkCIF report

Comment top

In our search for new potential boron-dipyrromethene (BODIPY) fluorescent dyes (Chen & Jiang, 2011), we have obtained the title compound (I). Herewith we report its crystal structure.

In (I) (Fig. 1), all bond lengths and angles are normal in relation to to those observed in the related boron-dipyrromethene derivatives (Zhou, 2010; Hinkle et al., 2011; Cui et al., 2012). The C—C and C—N bond lengths within BODIPY fragment are in the range of 1.371–1.422 and 1.337–1.402 Å, respectively, without any clear distinction between single and double bonds, indicating strongly delocalized π-system. The C₉BN₂ fragment is essentially flat, with the maximum deviation from the least-squares mean plane of 0.065 (3) Å. The dihedral angle between the F—B—F plane and the BODIPY mean plane is 88.95 (4)°. Due to the presence of two methyl groups attached to C1 and C7 atoms in BODIPY fragment, the dihedral angles between the BODIPY mean plane and 4-iodophenyl fragment is 78.21 (3)°.

Related literature top

For the crystal structures of related boron–dipyrromethene derivatives, see: Zhou (2010); Chen & Jiang (2011); Hinkle et al. (2011); Cui et al. (2012).

Experimental top

To the mixture of p-iodobenzyldehyde (231 mg, 1 mmol) and 2,4-dimethylpyrrole (190 mg, 2.00 mmol) dissolved in CH₂Cl₂ (150 ml), one drop of TFA was added. After the resulting mixture was stirred for five hours at room temperature under N₂ atmosphere, a solution of DDQ (227 mg, 1 mmol) in CH₂Cl₂ (60 ml) was added and the reaction mixture was further stirred for another 10 min. After the addition of N, N-diisopropylethylamine (DIEA) (2 ml) into the mixture for 15 min, the BF₃—OEt₂ (2.0 ml) was added into the reaction mixture and stirring was continued for another 30 min. The resulting mixture was evaporated, and the residue was chromatographed on a silica gel column using CH₂Cl₂ as eluent. Repeated chromatography followed by recrystallization from CH₂Cl₂ and MeOH gave the target compound as red crystals. Yield: 130 mg, 28.9%. Anal. for C₁₉H₁₈BF₂IN₂: Calc. C, 50.70; H, 4.03; N, 6.22; Found: C, 50.42; H, 4.17; N, 6.31%. The No. of CCDC: 863227.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

2,2-difluoro-8-(4-iodophenyl)-4,6,10,12-tetramethyl-1λ⁵,3-diaza-2λ⁴- boratricyclo[7.3.0.0^{{3,7}]dodeca-1(12),4,6,8,10-pentaen-1-ylium top}

Crystal data top

C₁₉H₁₈BF₂IN₂	F(000) = 888
M_r = 450.06	D_x = 1.668 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.1004 (3) Å	Cell parameters from 3440 reflections
b = 8.1992 (2) Å	µ = 14.24 mm⁻¹
c = 18.0607 (4) Å	T = 293 K
β = 90.577 (3)°	Block, red
V = 1791.77 (8) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3348 independent reflections
Radiation source: fine-focus sealed tube	2770 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
phi and ω scans	θ_max = 70.8°, θ_min = 4.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→14
T_min = 0.102, T_max = 0.110	k = −10→8
6829 measured reflections	l = −21→21

Refinement top

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0917P)² + 0.3111P] where P = (F_o² + 2F_c²)/3
3348 reflections	(Δ/σ)_max = 0.001
230 parameters	Δρ_max = 1.33 e Å⁻³
0 restraints	Δρ_min = −1.36 e Å⁻³

Crystal data top

C₁₉H₁₈BF₂IN₂	V = 1791.77 (8) Å³
M_r = 450.06	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.1004 (3) Å	µ = 14.24 mm⁻¹
b = 8.1992 (2) Å	T = 293 K
c = 18.0607 (4) Å	0.20 × 0.18 × 0.16 mm
β = 90.577 (3)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3348 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2770 reflections with I > 2σ(I)
T_min = 0.102, T_max = 0.110	R_int = 0.044
6829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.05	Δρ_max = 1.33 e Å⁻³
3348 reflections	Δρ_min = −1.36 e Å⁻³
230 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
I	0.46758 (4)	−0.22865 (6)	0.54374 (2)	0.0515 (2)
F1	1.0026 (3)	0.3904 (5)	0.8798 (2)	0.0540 (10)
N2	0.8395 (4)	0.2246 (6)	0.8934 (3)	0.0334 (11)
F2	0.8499 (4)	0.5070 (5)	0.9279 (2)	0.0569 (11)
N1	0.8479 (3)	0.4411 (6)	0.7983 (2)	0.0305 (10)
C15	0.7292 (4)	0.0148 (7)	0.6658 (3)	0.0345 (13)
H6	0.8056	0.0233	0.6619	0.041*
C2	0.8031 (5)	−0.0117 (8)	0.9496 (3)	0.0401 (14)
H7	0.8028	−0.0933	0.9853	0.048*
C9	0.7415 (4)	0.1937 (7)	0.7768 (3)	0.0278 (11)
C1	0.7510 (4)	−0.0199 (7)	0.8812 (3)	0.0332 (12)
C14	0.6760 (4)	0.0933 (7)	0.7238 (3)	0.0280 (11)
C10	0.7747 (4)	0.1305 (7)	0.8456 (3)	0.0272 (11)
C8	0.7754 (4)	0.3485 (7)	0.7541 (3)	0.0273 (11)
C7	0.7538 (4)	0.4399 (7)	0.6886 (3)	0.0325 (12)
C13	0.9491 (6)	0.7053 (9)	0.7908 (4)	0.0510 (17)
H15B	1.0239	0.6742	0.7807	0.077*
H15C	0.9397	0.7166	0.8432	0.077*
H15A	0.9331	0.8074	0.7669	0.077*
C6	0.8157 (5)	0.5794 (8)	0.6943 (3)	0.0390 (13)
H16	0.8192	0.6614	0.6588	0.047*
C4	0.9226 (6)	0.2003 (10)	1.0198 (4)	0.0522 (18)
H17C	0.8915	0.3008	1.0371	0.078*
H17A	0.9972	0.2187	1.0043	0.078*
H17B	0.9223	0.1214	1.0591	0.078*
C17	0.5569 (5)	−0.0896 (7)	0.6206 (3)	0.0357 (13)
C5	0.8727 (5)	0.5783 (8)	0.7620 (3)	0.0354 (13)
C18	0.5021 (5)	−0.0124 (8)	0.6784 (3)	0.0370 (13)
H20	0.4259	−0.0218	0.6826	0.044*
C16	0.6705 (5)	−0.0756 (8)	0.6139 (3)	0.0389 (14)
H21	0.7069	−0.1262	0.5750	0.047*
C19	0.5624 (5)	0.0783 (8)	0.7293 (3)	0.0362 (13)
H22	0.5260	0.1299	0.7679	0.043*
C3	0.8559 (5)	0.1382 (8)	0.9563 (3)	0.0384 (14)
B	0.8873 (5)	0.3956 (9)	0.8772 (4)	0.0346 (14)
C12	0.6745 (5)	0.4019 (9)	0.6266 (3)	0.0465 (16)
H25A	0.6999	0.3077	0.6002	0.070*
H25C	0.6703	0.4933	0.5935	0.070*
H25B	0.6027	0.3804	0.6465	0.070*
C11A	0.6824 (5)	−0.1606 (8)	0.8552 (4)	0.0419 (14)
H1AB	0.6056	−0.1314	0.8567	0.063*
H1AC	0.6955	−0.2529	0.8868	0.063*
H1AA	0.7020	−0.1878	0.8053	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I	0.0601 (4)	0.0609 (4)	0.0331 (3)	−0.0223 (2)	−0.0201 (2)	−0.00197 (17)
F1	0.0302 (17)	0.081 (3)	0.050 (2)	−0.0144 (19)	−0.0154 (16)	0.009 (2)
N2	0.031 (2)	0.048 (3)	0.021 (2)	0.001 (2)	−0.0043 (19)	−0.003 (2)
F2	0.082 (3)	0.057 (2)	0.0314 (18)	−0.001 (2)	−0.0013 (19)	−0.0118 (17)
N1	0.025 (2)	0.039 (3)	0.027 (2)	−0.001 (2)	−0.0030 (17)	−0.006 (2)
C15	0.023 (2)	0.047 (3)	0.034 (3)	0.000 (2)	−0.006 (2)	−0.009 (3)
C2	0.043 (3)	0.048 (4)	0.029 (3)	0.003 (3)	−0.009 (2)	0.008 (3)
C9	0.021 (2)	0.037 (3)	0.026 (3)	0.002 (2)	−0.002 (2)	−0.006 (2)
C1	0.028 (3)	0.042 (3)	0.030 (3)	0.004 (3)	0.000 (2)	−0.001 (2)
C14	0.027 (2)	0.040 (3)	0.017 (2)	−0.003 (2)	−0.0031 (19)	0.001 (2)
C10	0.020 (2)	0.035 (3)	0.027 (2)	0.001 (2)	−0.0028 (19)	−0.005 (2)
C8	0.021 (2)	0.033 (3)	0.028 (2)	0.000 (2)	−0.0051 (19)	−0.007 (2)
C7	0.029 (3)	0.043 (3)	0.026 (2)	0.002 (3)	−0.003 (2)	−0.003 (2)
C13	0.047 (4)	0.051 (4)	0.055 (5)	−0.007 (3)	−0.001 (3)	−0.005 (3)
C6	0.046 (3)	0.042 (3)	0.029 (3)	−0.002 (3)	0.000 (2)	0.001 (2)
C4	0.053 (4)	0.075 (5)	0.029 (3)	−0.011 (4)	−0.016 (3)	0.001 (3)
C17	0.044 (3)	0.037 (3)	0.026 (3)	−0.012 (3)	−0.017 (2)	−0.002 (2)
C5	0.034 (3)	0.039 (3)	0.033 (3)	−0.001 (3)	−0.002 (2)	−0.003 (2)
C18	0.027 (3)	0.048 (4)	0.036 (3)	−0.009 (3)	−0.004 (2)	0.004 (3)
C16	0.034 (3)	0.054 (4)	0.028 (3)	0.001 (3)	0.002 (2)	−0.008 (3)
C19	0.035 (3)	0.049 (3)	0.025 (3)	−0.004 (3)	−0.004 (2)	−0.002 (2)
C3	0.038 (3)	0.055 (4)	0.023 (3)	−0.001 (3)	−0.008 (2)	0.002 (3)
B	0.028 (3)	0.047 (4)	0.028 (3)	−0.006 (3)	−0.002 (2)	−0.007 (3)
C12	0.047 (3)	0.061 (4)	0.032 (3)	−0.007 (3)	−0.015 (3)	0.012 (3)
C11A	0.038 (3)	0.044 (4)	0.044 (3)	0.000 (3)	−0.001 (3)	0.003 (3)

Geometric parameters (Å, º) top

I—C17	2.089 (5)	C7—C12	1.500 (7)
F1—B	1.397 (7)	C13—C5	1.483 (9)
N2—C3	1.352 (8)	C13—H15B	0.9600
N2—C10	1.393 (7)	C13—H15C	0.9600
N2—B	1.546 (9)	C13—H15A	0.9600
F2—B	1.373 (8)	C6—C5	1.399 (8)
N1—C5	1.337 (8)	C6—H16	0.9300
N1—C8	1.403 (6)	C4—C3	1.486 (8)
N1—B	1.544 (8)	C4—H17C	0.9600
C15—C16	1.387 (8)	C4—H17A	0.9600
C15—C14	1.392 (7)	C4—H17B	0.9600
C15—H6	0.9300	C17—C16	1.386 (8)
C2—C1	1.382 (8)	C17—C18	1.394 (8)
C2—C3	1.390 (9)	C18—C19	1.386 (8)
C2—H7	0.9300	C18—H20	0.9300
C9—C8	1.396 (8)	C16—H21	0.9300
C9—C10	1.402 (7)	C19—H22	0.9300
C9—C14	1.485 (7)	C12—H25A	0.9600
C1—C10	1.422 (8)	C12—H25C	0.9600
C1—C11A	1.494 (8)	C12—H25B	0.9600
C14—C19	1.385 (8)	C11A—H1AB	0.9600
C8—C7	1.422 (8)	C11A—H1AC	0.9600
C7—C6	1.370 (9)	C11A—H1AA	0.9600

C3—N2—C10	107.9 (5)	H17C—C4—H17A	109.5
C3—N2—B	125.6 (5)	C3—C4—H17B	109.5
C10—N2—B	126.4 (5)	H17C—C4—H17B	109.5
C5—N1—C8	108.6 (4)	H17A—C4—H17B	109.5
C5—N1—B	125.9 (5)	C16—C17—C18	120.5 (5)
C8—N1—B	125.4 (5)	C16—C17—I	119.6 (4)
C16—C15—C14	121.2 (5)	C18—C17—I	119.9 (4)
C16—C15—H6	119.4	N1—C5—C6	108.8 (5)
C14—C15—H6	119.4	N1—C5—C13	124.2 (5)
C1—C2—C3	109.1 (5)	C6—C5—C13	127.0 (6)
C1—C2—H7	125.5	C19—C18—C17	119.4 (5)
C3—C2—H7	125.5	C19—C18—H20	120.3
C8—C9—C10	120.9 (5)	C17—C18—H20	120.3
C8—C9—C14	118.1 (5)	C17—C16—C15	119.2 (5)
C10—C9—C14	120.8 (5)	C17—C16—H21	120.4
C2—C1—C10	105.7 (5)	C15—C16—H21	120.4
C2—C1—C11A	124.5 (6)	C14—C19—C18	121.0 (5)
C10—C1—C11A	129.9 (5)	C14—C19—H22	119.5
C19—C14—C15	118.7 (5)	C18—C19—H22	119.5
C19—C14—C9	121.7 (5)	N2—C3—C2	109.0 (5)
C15—C14—C9	119.6 (4)	N2—C3—C4	122.9 (6)
N2—C10—C9	120.0 (5)	C2—C3—C4	128.0 (6)
N2—C10—C1	108.3 (5)	F2—B—F1	109.5 (5)
C9—C10—C1	131.7 (5)	F2—B—N1	110.8 (5)
C9—C8—N1	120.6 (5)	F1—B—N1	109.7 (5)
C9—C8—C7	132.1 (5)	F2—B—N2	110.6 (5)
N1—C8—C7	107.2 (5)	F1—B—N2	109.9 (5)
C6—C7—C8	106.4 (5)	N1—B—N2	106.4 (5)
C6—C7—C12	125.0 (6)	C7—C12—H25A	109.5
C8—C7—C12	128.5 (5)	C7—C12—H25C	109.5
C5—C13—H15B	109.5	H25A—C12—H25C	109.5
C5—C13—H15C	109.5	C7—C12—H25B	109.5
H15B—C13—H15C	109.5	H25A—C12—H25B	109.5
C5—C13—H15A	109.5	H25C—C12—H25B	109.5
H15B—C13—H15A	109.5	C1—C11A—H1AB	109.5
H15C—C13—H15A	109.5	C1—C11A—H1AC	109.5
C7—C6—C5	108.9 (5)	H1AB—C11A—H1AC	109.5
C7—C6—H16	125.5	C1—C11A—H1AA	109.5
C5—C6—H16	125.5	H1AB—C11A—H1AA	109.5
C3—C4—H17C	109.5	H1AC—C11A—H1AA	109.5
C3—C4—H17A	109.5

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈BF₂IN₂
M_r	450.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.1004 (3), 8.1992 (2), 18.0607 (4)
β (°)	90.577 (3)
V (Å³)	1791.77 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	14.24
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.102, 0.110
No. of measured, independent and observed [I > 2σ(I)] reflections	6829, 3348, 2770
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.612

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.166, 1.05
No. of reflections	3348
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.33, −1.36

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Y. & Jiang, J. (2011). Acta Cryst. E67, o908. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cui, A.-J., An, J., Sun, F.-A., Hu, M. & Qin, J. (2012). Acta Cryst. E68, o63. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hinkle, L. M., Chitta, R. & Mann, K. R. (2011). Acta Cryst. E67, o2265–o2266. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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