4,4-Difluoro-3-[(4-methoxy­phen­yl)styr­yl]-1,5,7,8-tetra­methyl-4-bora-3a,4a-diaza-s-indacene

In the title compound, C₂₂H₂₃BF₂N₂O, the styrene and boron-dipyrromethene (BODIPY) fused-ring fragments are almost coplanar. Short C-C bond lengths suggest some electronic conjugation between the two systems.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.132
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C3
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C4
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

4,4-Difluoro-3-[(4-methoxyphenyl)styryl]-1,5,7,8-tetramethyl-4-bora-3a,4a- diaza-s-indacene

Crystal data

C22H23BF2N2O	Z = 2
Mr = 380.23	F(000) = 400
Triclinic, P1	Dx = 1.334 Mg m^−3
Hall symbol: -P 1	Melting point: 192(1) K
a = 8.6442 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0246 (3) Å	Cell parameters from 3314 reflections
c = 12.0034 (3) Å	θ = 2.3–32.1°
α = 64.565 (1)°	µ = 0.10 mm^−1
β = 73.311 (2)°	T = 298 K
γ = 68.007 (1)°	Cube, dark-blue
V = 946.90 (4) Å^3	0.60 × 0.60 × 0.60 mm

Data collection

Bruker SMART APEX-II CCD diffractometer	2915 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
Detector resolution: 9.81 pixels mm^-1	h = −10→10
φ and ω scans	k = −13→13
11471 measured reflections	l = −14→14
3314 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0798P)^2 + 0.1878P] where P = (Fo^2 + 2Fc^2)/3
3314 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Experimental. Mp.: 465 K; ¹H NMR (CDCl₃): δ 7.531(d, 2H), 7.512 (d, 2H, J = 16.4 Hz), 7.185 (d, 2H, J = 16.4 Hz), 6.895 (d, 2H), 6.667 (s, 1H), 6.075 (s, 1H), 3.840 (s, 3H), 2.612(s, 3H), 2.558 (s, 3H), 2.473 (s, 3H), 2.434(s, 3H). HRMS(EI): 380.1874, calculated: 380.1872.

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 (Ų)

	x	y	z	Uiso*/Ueq
N2	0.36476 (16)	0.67075 (14)	0.19591 (12)	0.0413 (3)
F2	0.10390 (11)	0.65366 (11)	0.17985 (10)	0.0558 (3)
F1	0.17586 (13)	0.56574 (11)	0.37107 (9)	0.0559 (3)
N1	0.33360 (15)	0.44167 (14)	0.23143 (12)	0.0400 (3)
C22	0.53238 (19)	0.62762 (18)	0.14186 (14)	0.0416 (4)
C21	0.50183 (19)	0.40301 (17)	0.17676 (14)	0.0407 (4)
C20	0.2675 (2)	0.33585 (17)	0.26462 (15)	0.0422 (4)
C19	0.59970 (19)	0.49473 (17)	0.13254 (14)	0.0421 (4)
C18	−0.4596 (2)	0.19315 (17)	0.52047 (15)	0.0445 (4)
C17	−0.1409 (2)	0.22971 (16)	0.40255 (14)	0.0412 (4)
C16	0.5384 (2)	0.26409 (18)	0.17899 (15)	0.0449 (4)
C15	0.6018 (2)	0.73986 (19)	0.10410 (15)	0.0480 (4)
C14	−0.1788 (2)	0.10801 (17)	0.42635 (16)	0.0463 (4)
H14A	−0.0959	0.0372	0.4020	0.056*
C13	0.0945 (2)	0.34170 (17)	0.32130 (15)	0.0454 (4)
H13A	0.0266	0.4196	0.3420	0.054*
C12	−0.3342 (2)	0.08877 (18)	0.48446 (17)	0.0484 (4)
H12A	−0.3550	0.0058	0.4995	0.058*
O	−0.60802 (16)	0.16346 (14)	0.57983 (14)	0.0629 (4)
C11	0.3309 (2)	0.80130 (18)	0.19290 (16)	0.0473 (4)
C10	0.0283 (2)	0.24025 (17)	0.34520 (15)	0.0446 (4)
H10A	0.1009	0.1653	0.3218	0.053*
C9	0.4754 (2)	0.8453 (2)	0.13713 (17)	0.0536 (4)
H9A	0.4850	0.9318	0.1243	0.064*
B	0.2385 (2)	0.58434 (19)	0.24703 (17)	0.0403 (4)
C8	0.3939 (2)	0.22544 (18)	0.23256 (16)	0.0472 (4)
H8A	0.3809	0.1400	0.2458	0.057*
C7	−0.4275 (2)	0.31659 (18)	0.49603 (18)	0.0526 (4)
H7A	−0.5117	0.3878	0.5190	0.063*
C6	−0.2705 (2)	0.33435 (18)	0.43756 (18)	0.0504 (4)
H6A	−0.2508	0.4182	0.4211	0.060*
C5	0.7799 (2)	0.4522 (2)	0.07340 (18)	0.0574 (5)
H5A	0.8079	0.3592	0.0735	0.086*
H5B	0.8527	0.4533	0.1198	0.086*
H5C	0.7942	0.5167	−0.0109	0.086*
C4	0.7756 (2)	0.7516 (2)	0.0404 (2)	0.0656 (5)
H4A	0.7824	0.8416	0.0277	0.098*
H4B	0.7978	0.7416	−0.0388	0.098*
H4C	0.8575	0.6789	0.0915	0.098*
C3	0.1633 (3)	0.8809 (2)	0.2414 (2)	0.0632 (5)
H3A	0.0875	0.8242	0.2747	0.095*
H3B	0.1189	0.9653	0.1748	0.095*
H3C	0.1753	0.9047	0.3060	0.095*
C2	−0.7436 (2)	0.2661 (2)	0.6177 (2)	0.0607 (5)
H2A	−0.8390	0.2303	0.6582	0.091*
H2B	−0.7735	0.3492	0.5458	0.091*
H2C	−0.7103	0.2884	0.6746	0.091*
C1	0.6989 (2)	0.1702 (2)	0.13461 (19)	0.0601 (5)
H1A	0.6812	0.0832	0.1496	0.090*
H1B	0.7863	0.1521	0.1790	0.090*
H1C	0.7318	0.2153	0.0468	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0339 (7)	0.0473 (7)	0.0418 (7)	−0.0128 (6)	−0.0013 (5)	−0.0173 (6)
F2	0.0353 (5)	0.0575 (6)	0.0745 (7)	−0.0075 (4)	−0.0140 (5)	−0.0252 (5)
F1	0.0605 (6)	0.0617 (6)	0.0476 (6)	−0.0276 (5)	0.0139 (5)	−0.0273 (5)
N1	0.0312 (7)	0.0473 (7)	0.0416 (7)	−0.0120 (5)	−0.0014 (5)	−0.0183 (6)
C22	0.0305 (7)	0.0559 (9)	0.0379 (8)	−0.0144 (7)	−0.0027 (6)	−0.0164 (7)
C21	0.0310 (7)	0.0517 (9)	0.0368 (8)	−0.0082 (6)	−0.0033 (6)	−0.0179 (6)
C20	0.0389 (8)	0.0470 (9)	0.0420 (8)	−0.0138 (7)	−0.0045 (6)	−0.0172 (7)
C19	0.0319 (8)	0.0565 (9)	0.0352 (8)	−0.0116 (7)	−0.0034 (6)	−0.0163 (7)
C18	0.0400 (9)	0.0470 (9)	0.0503 (9)	−0.0179 (7)	−0.0023 (7)	−0.0194 (7)
C17	0.0403 (8)	0.0436 (8)	0.0423 (8)	−0.0141 (7)	−0.0048 (6)	−0.0173 (6)
C16	0.0405 (9)	0.0510 (9)	0.0392 (8)	−0.0067 (7)	−0.0047 (6)	−0.0192 (7)
C15	0.0403 (9)	0.0634 (10)	0.0430 (9)	−0.0233 (8)	−0.0045 (7)	−0.0157 (8)
C14	0.0413 (9)	0.0454 (9)	0.0575 (10)	−0.0110 (7)	−0.0037 (7)	−0.0271 (8)
C13	0.0390 (8)	0.0471 (9)	0.0512 (9)	−0.0137 (7)	−0.0017 (7)	−0.0209 (7)
C12	0.0459 (9)	0.0435 (9)	0.0642 (10)	−0.0189 (7)	−0.0048 (8)	−0.0241 (8)
O	0.0441 (7)	0.0599 (8)	0.0889 (10)	−0.0259 (6)	0.0116 (6)	−0.0354 (7)
C11	0.0445 (9)	0.0489 (9)	0.0492 (9)	−0.0164 (7)	−0.0027 (7)	−0.0187 (7)
C10	0.0405 (8)	0.0470 (9)	0.0483 (9)	−0.0130 (7)	−0.0027 (7)	−0.0214 (7)
C9	0.0552 (11)	0.0540 (10)	0.0571 (10)	−0.0261 (8)	−0.0033 (8)	−0.0197 (8)
B	0.0305 (8)	0.0467 (10)	0.0438 (9)	−0.0113 (7)	−0.0003 (7)	−0.0198 (7)
C8	0.0472 (9)	0.0457 (9)	0.0498 (9)	−0.0136 (7)	−0.0043 (7)	−0.0203 (7)
C7	0.0424 (9)	0.0456 (9)	0.0721 (12)	−0.0138 (7)	0.0050 (8)	−0.0312 (8)
C6	0.0471 (9)	0.0411 (8)	0.0672 (11)	−0.0196 (7)	0.0026 (8)	−0.0247 (8)
C5	0.0363 (9)	0.0695 (12)	0.0624 (11)	−0.0153 (8)	0.0063 (8)	−0.0290 (9)
C4	0.0481 (11)	0.0841 (14)	0.0702 (13)	−0.0359 (10)	0.0008 (9)	−0.0251 (11)
C3	0.0569 (11)	0.0519 (10)	0.0771 (13)	−0.0163 (9)	0.0060 (9)	−0.0296 (9)
C2	0.0424 (10)	0.0654 (11)	0.0683 (12)	−0.0171 (8)	0.0054 (8)	−0.0261 (9)
C1	0.0500 (11)	0.0595 (11)	0.0622 (11)	−0.0041 (8)	0.0015 (8)	−0.0305 (9)

Geometric parameters (Å, º)

N2—C11	1.343 (2)	C13—C10	1.330 (2)
N2—C22	1.398 (2)	C13—H13A	0.9300
N2—B	1.538 (2)	C12—H12A	0.9300
F2—B	1.390 (2)	O—C2	1.415 (2)
F1—B	1.382 (2)	C11—C9	1.392 (2)
N1—C20	1.348 (2)	C11—C3	1.486 (3)
N1—C21	1.3982 (19)	C10—H10A	0.9300
N1—B	1.543 (2)	C9—H9A	0.9300
C22—C19	1.401 (2)	C8—H8A	0.9300
C22—C15	1.420 (2)	C7—C6	1.380 (2)
C21—C19	1.393 (2)	C7—H7A	0.9300
C21—C16	1.433 (2)	C6—H6A	0.9300
C20—C8	1.410 (2)	C5—H5A	0.9600
C20—C13	1.444 (2)	C5—H5B	0.9600
C19—C5	1.501 (2)	C5—H5C	0.9600
C18—O	1.360 (2)	C4—H4A	0.9600
C18—C7	1.381 (2)	C4—H4B	0.9600
C18—C12	1.382 (2)	C4—H4C	0.9600
C17—C14	1.391 (2)	C3—H3A	0.9600
C17—C6	1.393 (2)	C3—H3B	0.9600
C17—C10	1.452 (2)	C3—H3C	0.9600
C16—C8	1.363 (2)	C2—H2A	0.9600
C16—C1	1.501 (2)	C2—H2B	0.9600
C15—C9	1.378 (3)	C2—H2C	0.9600
C15—C4	1.503 (2)	C1—H1A	0.9600
C14—C12	1.373 (2)	C1—H1B	0.9600
C14—H14A	0.9300	C1—H1C	0.9600
C11—N2—C22	108.83 (13)	C15—C9—H9A	125.6
C11—N2—B	125.63 (14)	C11—C9—H9A	125.6
C22—N2—B	125.52 (13)	F1—B—F2	108.36 (13)
C20—N1—C21	108.88 (13)	F1—B—N2	110.70 (13)
C20—N1—B	125.84 (13)	F2—B—N2	109.93 (13)
C21—N1—B	125.25 (13)	F1—B—N1	110.72 (13)
N2—C22—C19	120.36 (14)	F2—B—N1	109.94 (13)
N2—C22—C15	107.21 (14)	N2—B—N1	107.20 (12)
C19—C22—C15	132.43 (15)	C16—C8—C20	108.98 (15)
C19—C21—N1	120.69 (15)	C16—C8—H8A	125.5
C19—C21—C16	132.22 (15)	C20—C8—H8A	125.5
N1—C21—C16	107.09 (14)	C6—C7—C18	120.07 (16)
N1—C20—C8	108.32 (14)	C6—C7—H7A	120.0
N1—C20—C13	123.63 (14)	C18—C7—H7A	120.0
C8—C20—C13	128.04 (15)	C7—C6—C17	121.61 (15)
C21—C19—C22	120.95 (14)	C7—C6—H6A	119.2
C21—C19—C5	120.12 (15)	C17—C6—H6A	119.2
C22—C19—C5	118.93 (15)	C19—C5—H5A	109.5
O—C18—C7	124.93 (15)	C19—C5—H5B	109.5
O—C18—C12	115.60 (14)	H5A—C5—H5B	109.5
C7—C18—C12	119.47 (15)	C19—C5—H5C	109.5
C14—C17—C6	116.73 (14)	H5A—C5—H5C	109.5
C14—C17—C10	119.19 (14)	H5B—C5—H5C	109.5
C6—C17—C10	124.07 (14)	C15—C4—H4A	109.5
C8—C16—C21	106.72 (14)	C15—C4—H4B	109.5
C8—C16—C1	122.95 (16)	H4A—C4—H4B	109.5
C21—C16—C1	130.33 (16)	C15—C4—H4C	109.5
C9—C15—C22	106.41 (14)	H4A—C4—H4C	109.5
C9—C15—C4	123.50 (17)	H4B—C4—H4C	109.5
C22—C15—C4	130.09 (17)	C11—C3—H3A	109.5
C12—C14—C17	122.31 (15)	C11—C3—H3B	109.5
C12—C14—H14A	118.8	H3A—C3—H3B	109.5
C17—C14—H14A	118.8	C11—C3—H3C	109.5
C10—C13—C20	122.69 (15)	H3A—C3—H3C	109.5
C10—C13—H13A	118.7	H3B—C3—H3C	109.5
C20—C13—H13A	118.7	O—C2—H2A	109.5
C14—C12—C18	119.78 (15)	O—C2—H2B	109.5
C14—C12—H12A	120.1	H2A—C2—H2B	109.5
C18—C12—H12A	120.1	O—C2—H2C	109.5
C18—O—C2	118.96 (14)	H2A—C2—H2C	109.5
N2—C11—C9	108.68 (15)	H2B—C2—H2C	109.5
N2—C11—C3	123.49 (15)	C16—C1—H1A	109.5
C9—C11—C3	127.83 (16)	C16—C1—H1B	109.5
C13—C10—C17	129.31 (15)	H1A—C1—H1B	109.5
C13—C10—H10A	115.3	C16—C1—H1C	109.5
C17—C10—H10A	115.3	H1A—C1—H1C	109.5
C15—C9—C11	108.87 (16)	H1B—C1—H1C	109.5
C11—N2—C22—C19	−179.57 (14)	C7—C18—O—C2	1.7 (3)
B—N2—C22—C19	−1.2 (2)	C12—C18—O—C2	−178.89 (16)
C11—N2—C22—C15	−0.23 (17)	C22—N2—C11—C9	−0.05 (19)
B—N2—C22—C15	178.19 (14)	B—N2—C11—C9	−178.46 (15)
C20—N1—C21—C19	179.29 (14)	C22—N2—C11—C3	179.31 (17)
B—N1—C21—C19	1.1 (2)	B—N2—C11—C3	0.9 (3)
C20—N1—C21—C16	−0.68 (17)	C20—C13—C10—C17	179.17 (16)
B—N1—C21—C16	−178.90 (13)	C14—C17—C10—C13	−175.48 (17)
C21—N1—C20—C8	0.55 (17)	C6—C17—C10—C13	3.7 (3)
B—N1—C20—C8	178.75 (14)	C22—C15—C9—C11	−0.5 (2)
C21—N1—C20—C13	−178.55 (15)	C4—C15—C9—C11	179.40 (16)
B—N1—C20—C13	−0.3 (2)	N2—C11—C9—C15	0.3 (2)
N1—C21—C19—C22	0.1 (2)	C3—C11—C9—C15	−179.01 (18)
C16—C21—C19—C22	−179.93 (15)	C11—N2—B—F1	−59.0 (2)
N1—C21—C19—C5	−179.66 (15)	C22—N2—B—F1	122.82 (16)
C16—C21—C19—C5	0.3 (3)	C11—N2—B—F2	60.7 (2)
N2—C22—C19—C21	−0.1 (2)	C22—N2—B—F2	−117.49 (16)
C15—C22—C19—C21	−179.22 (16)	C11—N2—B—N1	−179.87 (14)
N2—C22—C19—C5	179.70 (14)	C22—N2—B—N1	2.0 (2)
C15—C22—C19—C5	0.5 (3)	C20—N1—B—F1	59.3 (2)
C19—C21—C16—C8	−179.41 (17)	C21—N1—B—F1	−122.77 (15)
N1—C21—C16—C8	0.55 (17)	C20—N1—B—F2	−60.4 (2)
C19—C21—C16—C1	0.9 (3)	C21—N1—B—F2	117.53 (15)
N1—C21—C16—C1	−179.13 (17)	C20—N1—B—N2	−179.85 (13)
N2—C22—C15—C9	0.42 (18)	C21—N1—B—N2	−1.9 (2)
C19—C22—C15—C9	179.65 (17)	C21—C16—C8—C20	−0.23 (18)
N2—C22—C15—C4	−179.43 (17)	C1—C16—C8—C20	179.48 (16)
C19—C22—C15—C4	−0.2 (3)	N1—C20—C8—C16	−0.19 (19)
C6—C17—C14—C12	−1.7 (3)	C13—C20—C8—C16	178.86 (16)
C10—C17—C14—C12	177.55 (16)	O—C18—C7—C6	178.50 (18)
N1—C20—C13—C10	175.05 (16)	C12—C18—C7—C6	−0.9 (3)
C8—C20—C13—C10	−3.9 (3)	C18—C7—C6—C17	−0.4 (3)
C17—C14—C12—C18	0.5 (3)	C14—C17—C6—C7	1.7 (3)
O—C18—C12—C14	−178.59 (16)	C10—C17—C6—C7	−177.55 (17)
C7—C18—C12—C14	0.8 (3)