10-(3,5-Dinitro-phen-yl)-5,5-difluoro-1,3,7,9-tetra-methyl-5H-dipyrrolo-[1,2-c:2',1'-f][1,3,2]diaza-borinin-4-ium-5-uide.

In an effort to discover new potential boron-dipyrromethene (BODIPY) dyes, the title compound, C19H17BF2N4O4, was prepared from 2,4-dimethyl-pyrrole, 3,5-dinitro-benzaldehyde and boron trifluoride in a one-pot reaction. The BODIPY fragment is nearly planar, with a maximum deviation from the least-squares plane of 0.251 (2) Å, and the benzene ring is inclined at a dihedral angle of 86.8 (6)° to the BODIPY mean plane. In the crystal, pairs of C-H⋯F hydrogen bonds connect neighbouring mol-ecules into inversion dimers, which are linked by further strong C-H⋯F inter-actions, forming a supra-molecular layered array parallel to the bc plane.

Related literature

For the use of related compounds for fluorescence analysis, see: Weiner et al. (2001 ▶); Gabe et al. (2004 ▶). For the structural characterization of related compounds, see: Euler et al. (2002a ▶,b ▶); Cui et al. (2006 ▶). For the synthetic procedure, see: Kollmannsberger et al. (1998 ▶).

Experimental

Crystal data

C19H17BF2N4O4

M = 414.18

Monoclinic,

a = 29.016 (3) Å

b = 9.1763 (9) Å

c = 16.8294 (16) Å

β = 121.086 (2)°

V = 3837.4 (7) Å3

Z = 8

Mo Kα radiation

μ = 0.11 mm−1

T = 295 K

0.21 × 0.21 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.973, T max = 0.985

11322 measured reflections

3767 independent reflections

2276 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.114

S = 1.04

3767 reflections

275 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813008027/zl2539sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008027/zl2539Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008027/zl2539Isup3.cml

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

C19H17BF2N4O4	F(000) = 1712
Mr = 414.18	Dx = 1.434 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2164 reflections
a = 29.016 (3) Å	θ = 2.4–24.3°
b = 9.1763 (9) Å	µ = 0.11 mm−1
c = 16.8294 (16) Å	T = 295 K
β = 121.086 (2)°	Block, purple
V = 3837.4 (7) Å3	0.21 × 0.21 × 0.16 mm
Z = 8

Bruker APEXII CCD diffractometer	3767 independent reflections
Radiation source: fine-focus sealed tube	2276 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −34→35
Tmin = 0.973, Tmax = 0.985	k = −9→11
11322 measured reflections	l = −20→18

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0507P)2] where P = (Fo2 + 2Fc2)/3
3767 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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 > 2sigma(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
B1	0.21971 (10)	0.3620 (3)	0.35983 (14)	0.0507 (6)
N1	0.02477 (8)	0.7770 (2)	0.44115 (15)	0.0721 (5)
N2	0.10066 (8)	0.3996 (2)	0.68190 (12)	0.0618 (5)
N3	0.16759 (6)	0.29249 (18)	0.34430 (10)	0.0501 (4)
N4	0.24400 (6)	0.45079 (17)	0.45002 (10)	0.0481 (4)
O1	−0.00805 (8)	0.8018 (2)	0.46364 (14)	0.1030 (6)
O2	0.02809 (8)	0.8443 (2)	0.38261 (15)	0.1074 (7)
O3	0.07160 (8)	0.44618 (19)	0.70880 (11)	0.0898 (6)
O4	0.12896 (7)	0.2925 (2)	0.71305 (11)	0.0828 (5)
C1	0.06408 (8)	0.5895 (2)	0.56281 (13)	0.0539 (5)
H1	0.0419	0.6201	0.5843	0.065*
C2	0.06252 (8)	0.6547 (2)	0.48802 (13)	0.0519 (5)
C3	0.09496 (8)	0.6107 (2)	0.45427 (13)	0.0513 (5)
H3A	0.0926	0.6562	0.4029	0.062*
C4	0.13103 (7)	0.4974 (2)	0.49844 (11)	0.0445 (5)
C5	0.13404 (8)	0.4307 (2)	0.57523 (12)	0.0468 (5)
H5	0.1586	0.3562	0.6064	0.056*
C6	0.09981 (8)	0.4773 (2)	0.60432 (12)	0.0474 (5)
C7	0.16365 (7)	0.4434 (2)	0.45850 (11)	0.0451 (5)
C8	0.13997 (8)	0.3386 (2)	0.38813 (12)	0.0493 (5)
C9	0.21486 (8)	0.4977 (2)	0.49101 (12)	0.0450 (5)
C10	0.24901 (8)	0.5908 (2)	0.56652 (12)	0.0478 (5)
C11	0.29708 (8)	0.5971 (2)	0.56926 (13)	0.0544 (5)
H11	0.3273	0.6492	0.6121	0.065*
C12	0.29309 (8)	0.5123 (2)	0.49699 (13)	0.0524 (5)
C13	0.23721 (9)	0.6657 (2)	0.63311 (13)	0.0596 (6)
H13A	0.2356	0.5949	0.6735	0.089*
H13B	0.2033	0.7155	0.5992	0.089*
H13C	0.2652	0.7349	0.6693	0.089*
C14	0.04881 (9)	0.2612 (3)	0.37558 (16)	0.0758 (7)
H14A	0.0298	0.3520	0.3555	0.114*
H14B	0.0651	0.2521	0.4416	0.114*
H14C	0.0241	0.1821	0.3454	0.114*
C15	0.09174 (8)	0.2570 (2)	0.35092 (13)	0.0563 (5)
C16	0.09160 (9)	0.1637 (3)	0.28651 (13)	0.0636 (6)
H16	0.0650	0.0956	0.2515	0.076*
C17	0.13746 (9)	0.1876 (2)	0.28228 (13)	0.0572 (5)
C18	0.15291 (10)	0.1167 (3)	0.21963 (14)	0.0707 (7)
H18A	0.1544	0.1887	0.1797	0.106*
H18B	0.1267	0.0440	0.1827	0.106*
H18C	0.1876	0.0716	0.2561	0.106*
C19	0.33455 (9)	0.4896 (3)	0.47106 (15)	0.0665 (6)
H19A	0.3463	0.3900	0.4824	0.100*
H19B	0.3647	0.5527	0.5076	0.100*
H19C	0.3193	0.5116	0.4065	0.100*
F1	0.20797 (5)	0.45458 (14)	0.28592 (7)	0.0708 (4)
F2	0.25531 (5)	0.25610 (13)	0.36548 (8)	0.0695 (4)

	U11	U22	U33	U12	U13	U23
B1	0.0537 (15)	0.0672 (15)	0.0426 (12)	0.0197 (12)	0.0330 (11)	0.0136 (11)
N1	0.0556 (12)	0.0716 (13)	0.0916 (15)	0.0124 (10)	0.0396 (11)	0.0006 (11)
N2	0.0609 (13)	0.0867 (14)	0.0507 (10)	−0.0185 (11)	0.0379 (10)	−0.0127 (10)
N3	0.0512 (10)	0.0681 (11)	0.0365 (8)	0.0141 (9)	0.0266 (8)	0.0045 (8)
N4	0.0472 (10)	0.0679 (11)	0.0399 (8)	0.0095 (8)	0.0302 (8)	0.0095 (8)
O1	0.0840 (13)	0.1048 (15)	0.1403 (16)	0.0355 (11)	0.0721 (13)	0.0046 (12)
O2	0.0984 (15)	0.1041 (15)	0.1317 (16)	0.0395 (12)	0.0679 (13)	0.0494 (14)
O3	0.1098 (15)	0.1162 (14)	0.0872 (12)	−0.0138 (11)	0.0820 (11)	−0.0146 (10)
O4	0.0828 (12)	0.1060 (14)	0.0694 (10)	0.0068 (11)	0.0462 (9)	0.0238 (10)
C1	0.0446 (12)	0.0673 (14)	0.0607 (12)	−0.0095 (10)	0.0349 (10)	−0.0200 (11)
C2	0.0401 (11)	0.0577 (12)	0.0586 (12)	0.0029 (10)	0.0259 (10)	−0.0053 (10)
C3	0.0438 (12)	0.0643 (13)	0.0493 (11)	0.0043 (10)	0.0265 (10)	0.0031 (10)
C4	0.0372 (11)	0.0629 (12)	0.0381 (10)	0.0010 (9)	0.0227 (9)	−0.0028 (9)
C5	0.0422 (11)	0.0621 (12)	0.0385 (10)	0.0014 (9)	0.0226 (9)	−0.0045 (9)
C6	0.0443 (12)	0.0645 (13)	0.0398 (10)	−0.0092 (10)	0.0263 (9)	−0.0097 (10)
C7	0.0426 (11)	0.0635 (12)	0.0334 (10)	0.0109 (10)	0.0227 (9)	0.0072 (9)
C8	0.0438 (12)	0.0721 (13)	0.0368 (10)	0.0096 (10)	0.0242 (9)	0.0019 (10)
C9	0.0465 (12)	0.0617 (12)	0.0359 (9)	0.0090 (10)	0.0278 (9)	0.0091 (9)
C10	0.0517 (12)	0.0574 (12)	0.0416 (10)	0.0060 (10)	0.0293 (9)	0.0102 (9)
C11	0.0486 (13)	0.0685 (14)	0.0502 (11)	−0.0013 (10)	0.0285 (10)	0.0064 (10)
C12	0.0475 (13)	0.0694 (14)	0.0489 (11)	0.0071 (10)	0.0310 (10)	0.0171 (11)
C13	0.0604 (14)	0.0709 (14)	0.0540 (12)	−0.0030 (11)	0.0342 (11)	−0.0046 (11)
C14	0.0470 (13)	0.1140 (19)	0.0679 (14)	−0.0121 (13)	0.0308 (11)	−0.0276 (14)
C15	0.0429 (12)	0.0824 (15)	0.0398 (10)	0.0061 (11)	0.0186 (9)	−0.0057 (10)
C16	0.0509 (14)	0.0831 (16)	0.0476 (12)	0.0036 (12)	0.0189 (10)	−0.0102 (11)
C17	0.0602 (14)	0.0725 (14)	0.0369 (10)	0.0164 (12)	0.0235 (10)	0.0029 (11)
C18	0.0807 (17)	0.0867 (16)	0.0507 (12)	0.0180 (14)	0.0381 (12)	−0.0042 (12)
C19	0.0601 (14)	0.0842 (16)	0.0769 (14)	0.0077 (12)	0.0508 (12)	0.0157 (13)
F1	0.0903 (10)	0.0893 (9)	0.0471 (6)	0.0167 (7)	0.0457 (6)	0.0206 (6)
F2	0.0640 (8)	0.0823 (8)	0.0780 (8)	0.0215 (7)	0.0478 (7)	0.0026 (6)

B1—F2	1.385 (2)	C7—C8	1.400 (3)
B1—F1	1.396 (2)	C8—C15	1.416 (3)
B1—N3	1.534 (3)	C9—C10	1.423 (3)
B1—N4	1.536 (3)	C10—C11	1.373 (3)
N1—O2	1.208 (2)	C10—C13	1.497 (2)
N1—O1	1.214 (2)	C11—C12	1.397 (3)
N1—C2	1.480 (3)	C11—H11	0.9300
N2—O4	1.213 (2)	C12—C19	1.491 (3)
N2—O3	1.222 (2)	C13—H13A	0.9600
N2—C6	1.477 (2)	C13—H13B	0.9600
N3—C17	1.356 (3)	C13—H13C	0.9600
N3—C8	1.405 (2)	C14—C15	1.503 (3)
N4—C12	1.345 (2)	C14—H14A	0.9600
N4—C9	1.407 (2)	C14—H14B	0.9600
C1—C6	1.369 (3)	C14—H14C	0.9600
C1—C2	1.373 (3)	C15—C16	1.380 (3)
C1—H1	0.9300	C16—C17	1.386 (3)
C2—C3	1.387 (2)	C16—H16	0.9300
C3—C4	1.387 (3)	C17—C18	1.492 (3)
C3—H3A	0.9300	C18—H18A	0.9600
C4—C5	1.392 (2)	C18—H18B	0.9600
C4—C7	1.500 (2)	C18—H18C	0.9600
C5—C6	1.383 (2)	C19—H19A	0.9600
C5—H5	0.9300	C19—H19B	0.9600
C7—C9	1.385 (3)	C19—H19C	0.9600
F2—B1—F1	108.56 (15)	N4—C9—C10	107.70 (17)
F2—B1—N3	110.77 (18)	C11—C10—C9	106.38 (16)
F1—B1—N3	109.62 (16)	C11—C10—C13	125.20 (19)
F2—B1—N4	111.02 (16)	C9—C10—C13	128.40 (18)
F1—B1—N4	109.52 (18)	C10—C11—C12	108.75 (18)
N3—B1—N4	107.34 (14)	C10—C11—H11	125.6
O2—N1—O1	124.3 (2)	C12—C11—H11	125.6
O2—N1—C2	118.27 (19)	N4—C12—C11	109.37 (17)
O1—N1—C2	117.4 (2)	N4—C12—C19	122.61 (19)
O4—N2—O3	124.47 (19)	C11—C12—C19	128.0 (2)
O4—N2—C6	118.18 (17)	C10—C13—H13A	109.5
O3—N2—C6	117.3 (2)	C10—C13—H13B	109.5
C17—N3—C8	107.57 (17)	H13A—C13—H13B	109.5
C17—N3—B1	127.84 (16)	C10—C13—H13C	109.5
C8—N3—B1	124.36 (17)	H13A—C13—H13C	109.5
C12—N4—C9	107.79 (16)	H13B—C13—H13C	109.5
C12—N4—B1	127.57 (16)	C15—C14—H14A	109.5
C9—N4—B1	124.17 (16)	C15—C14—H14B	109.5
C6—C1—C2	116.96 (17)	H14A—C14—H14B	109.5
C6—C1—H1	121.5	C15—C14—H14C	109.5
C2—C1—H1	121.5	H14A—C14—H14C	109.5
C1—C2—C3	122.70 (19)	H14B—C14—H14C	109.5
C1—C2—N1	118.96 (18)	C16—C15—C8	106.07 (18)
C3—C2—N1	118.34 (18)	C16—C15—C14	124.5 (2)
C2—C3—C4	118.85 (18)	C8—C15—C14	129.41 (18)
C2—C3—H3A	120.6	C15—C16—C17	109.2 (2)
C4—C3—H3A	120.6	C15—C16—H16	125.4
C3—C4—C5	119.71 (16)	C17—C16—H16	125.4
C3—C4—C7	118.93 (15)	N3—C17—C16	109.11 (17)
C5—C4—C7	121.26 (17)	N3—C17—C18	123.0 (2)
C6—C5—C4	118.72 (18)	C16—C17—C18	127.9 (2)
C6—C5—H5	120.6	C17—C18—H18A	109.5
C4—C5—H5	120.6	C17—C18—H18B	109.5
C1—C6—C5	123.04 (18)	H18A—C18—H18B	109.5
C1—C6—N2	118.49 (17)	C17—C18—H18C	109.5
C5—C6—N2	118.45 (19)	H18A—C18—H18C	109.5
C9—C7—C8	122.66 (16)	H18B—C18—H18C	109.5
C9—C7—C4	120.02 (17)	C12—C19—H19A	109.5
C8—C7—C4	117.32 (16)	C12—C19—H19B	109.5
C7—C8—N3	119.15 (17)	H19A—C19—H19B	109.5
C7—C8—C15	132.72 (17)	C12—C19—H19C	109.5
N3—C8—C15	108.06 (17)	H19A—C19—H19C	109.5
C7—C9—N4	119.35 (17)	H19B—C19—H19C	109.5
C7—C9—C10	132.80 (16)
F2—B1—N3—C17	−47.3 (2)	C9—C7—C8—C15	172.3 (2)
F1—B1—N3—C17	72.5 (2)	C4—C7—C8—C15	−8.1 (3)
N4—B1—N3—C17	−168.62 (16)	C17—N3—C8—C7	177.55 (16)
F2—B1—N3—C8	138.92 (17)	B1—N3—C8—C7	−7.6 (3)
F1—B1—N3—C8	−101.31 (19)	C17—N3—C8—C15	0.4 (2)
N4—B1—N3—C8	17.6 (2)	B1—N3—C8—C15	175.24 (16)
F2—B1—N4—C12	48.5 (3)	C8—C7—C9—N4	2.4 (3)
F1—B1—N4—C12	−71.4 (2)	C4—C7—C9—N4	−177.16 (15)
N3—B1—N4—C12	169.67 (17)	C8—C7—C9—C10	−172.43 (19)
F2—B1—N4—C9	−140.44 (17)	C4—C7—C9—C10	8.0 (3)
F1—B1—N4—C9	99.7 (2)	C12—N4—C9—C7	−176.52 (16)
N3—B1—N4—C9	−19.2 (2)	B1—N4—C9—C7	10.9 (3)
C6—C1—C2—C3	0.4 (3)	C12—N4—C9—C10	−0.5 (2)
C6—C1—C2—N1	−179.64 (17)	B1—N4—C9—C10	−173.08 (16)
O2—N1—C2—C1	171.6 (2)	C7—C9—C10—C11	175.1 (2)
O1—N1—C2—C1	−9.3 (3)	N4—C9—C10—C11	−0.2 (2)
O2—N1—C2—C3	−8.4 (3)	C7—C9—C10—C13	−3.3 (3)
O1—N1—C2—C3	170.7 (2)	N4—C9—C10—C13	−178.58 (18)
C1—C2—C3—C4	−0.9 (3)	C9—C10—C11—C12	0.8 (2)
N1—C2—C3—C4	179.11 (17)	C13—C10—C11—C12	179.24 (18)
C2—C3—C4—C5	0.0 (3)	C9—N4—C12—C11	1.0 (2)
C2—C3—C4—C7	176.17 (17)	B1—N4—C12—C11	173.25 (17)
C3—C4—C5—C6	1.5 (3)	C9—N4—C12—C19	−178.41 (17)
C7—C4—C5—C6	−174.66 (17)	B1—N4—C12—C19	−6.1 (3)
C2—C1—C6—C5	1.1 (3)	C10—C11—C12—N4	−1.1 (2)
C2—C1—C6—N2	−176.91 (16)	C10—C11—C12—C19	178.22 (19)
C4—C5—C6—C1	−2.1 (3)	C7—C8—C15—C16	−176.2 (2)
C4—C5—C6—N2	175.98 (16)	N3—C8—C15—C16	0.4 (2)
O4—N2—C6—C1	173.66 (18)	C7—C8—C15—C14	1.6 (4)
O3—N2—C6—C1	−4.6 (3)	N3—C8—C15—C14	178.3 (2)
O4—N2—C6—C5	−4.5 (3)	C8—C15—C16—C17	−1.0 (2)
O3—N2—C6—C5	177.23 (17)	C14—C15—C16—C17	−179.0 (2)
C3—C4—C7—C9	94.5 (2)	C8—N3—C17—C16	−1.0 (2)
C5—C4—C7—C9	−89.4 (2)	B1—N3—C17—C16	−175.65 (17)
C3—C4—C7—C8	−85.2 (2)	C8—N3—C17—C18	177.46 (18)
C5—C4—C7—C8	91.0 (2)	B1—N3—C17—C18	2.8 (3)
C9—C7—C8—N3	−4.0 (3)	C15—C16—C17—N3	1.3 (2)
C4—C7—C8—N3	175.56 (16)	C15—C16—C17—C18	−177.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F2i	0.93	2.51	3.307 (2)	144
C13—H13A···F1ii	0.96	2.45	3.287 (2)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F2i	0.93	2.51	3.307 (2)	144
C13—H13A⋯F1ii	0.96	2.45	3.287 (2)	146

Symmetry codes: (i) ; (ii) .