8-[3,4-Bis(ethoxy­carbonyl­meth­oxy)­phen­yl]-4,4-difluoro-1,3,5,7-tetra­methyl-4-bora-3a,4a-diaza-s-indacene

Wang, D.-C.; Hu, Z.-Z.; Chi, H.-J.; Zhang, Z.-Q.; Peng, X.-J.

doi:10.1107/S1600536807026979

8-[3,4-Bis(ethoxycarbonylmethoxy)phenyl]-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene

D.-C. Wang, Z.-Z. Hu, H.-J. Chi, Z.-Q. Zhang and X.-J. Peng

In the title compound, C₂₇H₃₁BF₂N₂O₆, the benzene ring is almost perpendicular to the fused-ring system [the dihedral angle is 82.3 (1)°]. The B-N distances in the central ring are almost identical, indicating delocalization of the formal positive charge over the two N atoms.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026979/hb2443sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026979/hb2443Isup2.hkl Contains datablock I

CCDC reference: 654580

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.005 Å
R factor = 0.056
wR factor = 0.152
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         49 Perc.
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.62 mm
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C3
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C9
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C10

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

   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Boron-dipyrromethene (BODIPY) dyes are well known as fluorescence labels and biomolecule sensors (Wu et al., 2005; Trieflinger et al., 2005; Dost et al., 2006). So As part of our ongoing studies of BOPIPY species (Qin et al., 2005; Yu et al., 2007) the structure of the title compound, (I), (Fig. 1) is now reported.

The BODIPY skeleton formed by the three conjugated heterocyclic rings is almost coplanar, with an r.m.s. deviation of 0.061 (3) Å; the maximum deviations from the mean plane are 0.113 (3) Å for B and 0.094 (3) Å for C4. Perhaps due to the presence of the C3 and C10 methyl groups, the benzene ring is almost perpendicular to the BODIPY mean plane, with the dihedral angle is 82.3 (1)°. The B—N distances in the central ring are almost identical, indicating delocaization of the formal positive charge on one of the N atoms (Table 1).

Related literature top

For background, see: Wu et al. (2005); Trieflinger et al. (2005); Dost et al. (2006); Qin et al. (2005); Yu et al. (2007).

Experimental top

8 mmol (0.8 ml) of 2,4-dimethyl-pyrrole and 4 mmol (1240 mg) (2-ethoxycarbonylmethoxy-4-formyl-phenoxy)-acetic acid ethyl ester were dissolved in 350 ml absolute DCM and 0.15 ml trifluoroacetic acid was added immediately under an nitrogen atmosphere. After being stirred at room temperature for 8 h, 320 ml DCM was evaporated, a solution of 2,3-dichloro-5,6-dicyano-benzoquinone (4 mmol) in DCM (30 ml) was added and stirred for half an hour, followed by injecting 74 mmol triethylamine (8 ml) into the dark residue. Then 75 mmol (12 ml) boron trifluoride ethyl ether complex was injected slowly. After stirring for 3 h, the solution was washed with an aqueous solution of NaHCO₃, the organic layer was dried over Na₂SO₄, and the solvent was evaporated by reduced pressure.

Chromatography on a silica column was carried out and eluted with ethyl acetate/petroleum ether (1:4 v/v) mitxture. The collected red fraction was subsequently recrystallized from chloroform/hexane (1:4 v/v) to acquire 507 mg (yield 24%) of the title compound.

Red slabs of (I) were acquired after 7 weeks by slow evaporation of a DCM/hexane (1:2 v/v) solution.

Structure description top

For background, see: Wu et al. (2005); Trieflinger et al. (2005); Dost et al. (2006); Qin et al. (2005); Yu et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); 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.

Figures top

Fig. 1.

8-[3,4-Bis(ethoxycarbonylmethoxy)phenyl]- 4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene top

Crystal data top

C₂₇H₃₁BF₂N₂O₆	F(000) = 1112
M_r = 528.35	D_x = 1.315 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 392K K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.6068 (6) Å	Cell parameters from 6052 reflections
b = 7.5418 (6) Å	θ = 2.2–27.5°
c = 36.896 (2) Å	µ = 0.10 mm⁻¹
β = 93.231 (5)°	T = 298 K
V = 2669.0 (3) Å³	Slab, red
Z = 4	0.62 × 0.21 × 0.08 mm

Data collection top

Bruker SMART APEX II CCD diffractometer	4681 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 3.53 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −8→8
T_min = 0.940, T_max = 0.992	l = −43→43
12387 measured reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0659P)²] where P = (F_o² + 2F_c²)/3
4681 reflections	(Δ/σ)_max < 0.001
343 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₇H₃₁BF₂N₂O₆	V = 2669.0 (3) Å³
M_r = 528.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6068 (6) Å	µ = 0.10 mm⁻¹
b = 7.5418 (6) Å	T = 298 K
c = 36.896 (2) Å	0.62 × 0.21 × 0.08 mm
β = 93.231 (5)°

Data collection top

Bruker SMART APEX II CCD diffractometer	4681 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2283 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.992	R_int = 0.079
12387 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 0.93	Δρ_max = 0.25 e Å⁻³
4681 reflections	Δρ_min = −0.20 e Å⁻³
343 parameters

Special details top

Experimental. Mp.: 392–393 K(uncorrected);

¹H NMR (CDCl₃, 400 MHz): δ 6.961 (d, 1H, Ar—H, J = 8.4 Hz), 6.840 (dd, 1H, Ar—H, J = 8.0 Hz), 6.746 (d, 1H, Ar—H, J = 1.2 Hz), 5.962 (s, 2H, pyrrole-H), 4.763 (s, 2H, methoxy-H), 4.698 (s, 2H, methoxy-H), 4.287–4.234 (m, 2H, ethoxy-H), 4.222–4.169 (m, 2H, ethoxy-H), 2.530 (s, 6H, pyrrole-CH₃), 1.430 (s, 6H, pyrrole-CH₃), 1.278 (t, 3H, ethyl ester-CH₃), 1.242 (t, 3H, ethyl ester-CH₃);

¹³C NMR (CDCl₃, 400 MHz): δ 168.667, 168.464, 155.704, 148.751, 148.432, 143.270, 140.728, 131.649, 128.818, 121.834, 121.341, 115.443, 114.494, 66.679, 66.292, 61.616, 61.555, 14.720, 14.500, 14.280, 14.211;

HRMS(TOF MS EI⁺): Found: 528.2246, calculated: 528.2243.

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
O6	−0.1822 (2)	0.8666 (3)	0.06347 (5)	0.0579 (6)
O5	−0.00951 (19)	1.0920 (3)	0.04268 (5)	0.0507 (6)
O4	0.2203 (2)	0.9416 (3)	0.02309 (5)	0.0577 (6)
F2	0.5394 (2)	1.1742 (3)	0.24401 (5)	0.0815 (7)
C27	0.1234 (3)	1.0922 (4)	0.10128 (8)	0.0458 (8)
H27A	0.1871	1.1750	0.0936	0.055*
O3	0.3274 (2)	1.1992 (4)	0.01361 (6)	0.0743 (8)
C26	0.0153 (3)	1.0365 (4)	0.07791 (7)	0.0424 (8)
N2	0.3670 (3)	1.2976 (4)	0.20215 (7)	0.0535 (7)
C25	−0.0805 (3)	0.9139 (4)	0.08945 (8)	0.0467 (8)
N1	0.4885 (3)	1.0196 (4)	0.18797 (6)	0.0534 (7)
F1	0.61150 (19)	1.2953 (3)	0.19255 (6)	0.0860 (7)
O2	−0.3397 (2)	0.4649 (3)	0.08974 (7)	0.0765 (8)
C24	0.1374 (3)	1.0247 (4)	0.13646 (8)	0.0452 (8)
O1	−0.1254 (2)	0.5049 (4)	0.07078 (7)	0.0823 (8)
C23	0.2524 (3)	1.2409 (5)	0.17989 (8)	0.0482 (8)
C22	−0.0683 (3)	0.8504 (5)	0.12437 (8)	0.0547 (9)
H22A	−0.1333	0.7701	0.1324	0.066*
C21	0.2249 (3)	1.1173 (5)	0.02085 (8)	0.0536 (9)
C20	−0.2360 (4)	0.5594 (5)	0.07760 (9)	0.0566 (9)
C19	0.2586 (3)	1.0815 (4)	0.16097 (7)	0.0443 (8)
C18	−0.2858 (3)	0.7483 (5)	0.07327 (9)	0.0569 (9)
H18A	−0.3620	0.7518	0.0549	0.068*
H18B	−0.3217	0.7874	0.0960	0.068*
C17	0.0898 (3)	1.2038 (5)	0.02750 (8)	0.0539 (9)
H17A	0.1075	1.3036	0.0437	0.065*
H17B	0.0502	1.2501	0.0047	0.065*
C16	0.3740 (3)	0.9695 (5)	0.16491 (7)	0.0488 (8)
C15	0.0413 (3)	0.9063 (5)	0.14764 (8)	0.0543 (9)
H15A	0.0494	0.8625	0.1712	0.065*
C14	0.4054 (3)	0.8035 (5)	0.14945 (8)	0.0544 (9)
C13	0.1425 (3)	1.3670 (5)	0.18329 (9)	0.0575 (9)
C12	0.5842 (3)	0.8895 (6)	0.18741 (9)	0.0629 (10)
C11	0.5356 (4)	0.7565 (5)	0.16382 (10)	0.0667 (11)
H11A	0.5832	0.6530	0.1586	0.080*
C10	0.3210 (4)	0.6941 (5)	0.12208 (9)	0.0720 (11)
H10A	0.3709	0.5874	0.1170	0.108*
H10B	0.3050	0.7609	0.1001	0.108*
H10C	0.2331	0.6641	0.1317	0.108*
C9	0.4263 (4)	1.5517 (6)	0.24383 (9)	0.0861 (13)
H9A	0.5151	1.4933	0.2464	0.129*
H9B	0.3863	1.5578	0.2671	0.129*
H9C	0.4384	1.6695	0.2347	0.129*
C8	0.7207 (3)	0.8948 (6)	0.20889 (11)	0.0952 (15)
H8A	0.7273	1.0029	0.2227	0.143*
H8B	0.7954	0.8897	0.1927	0.143*
H8C	0.7270	0.7953	0.2251	0.143*
C7	0.3452 (4)	0.8467 (6)	0.01443 (12)	0.0840 (13)
H7A	0.4207	0.8733	0.0321	0.101*
H7B	0.3735	0.8809	−0.0094	0.101*
C6	−0.4550 (4)	0.1959 (6)	0.09749 (12)	0.0955 (14)
H6A	−0.4454	0.0703	0.1011	0.143*
H6B	−0.5098	0.2180	0.0754	0.143*
H6C	−0.5004	0.2470	0.1175	0.143*
C5	0.3318 (4)	1.4503 (5)	0.21813 (9)	0.0628 (10)
C4	0.1942 (4)	1.4927 (5)	0.20706 (9)	0.0663 (10)
H4A	0.1455	1.5912	0.2147	0.080*
B	0.5065 (4)	1.1986 (6)	0.20735 (10)	0.0595 (11)
C3	−0.0018 (4)	1.3661 (5)	0.16650 (10)	0.0809 (12)
H3A	−0.0504	1.4699	0.1740	0.121*
H3B	−0.0498	1.2621	0.1741	0.121*
H3C	0.0015	1.3657	0.1405	0.121*
C2	−0.3184 (4)	0.2748 (5)	0.09514 (12)	0.0856 (13)
H2A	−0.2714	0.2244	0.0749	0.103*
H2B	−0.2618	0.2531	0.1173	0.103*
C1	0.3110 (5)	0.6528 (6)	0.01509 (13)	0.1050 (15)
H1A	0.3918	0.5853	0.0095	0.158*
H1B	0.2364	0.6281	−0.0026	0.158*
H1C	0.2829	0.6207	0.0388	0.158*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O6	0.0483 (12)	0.0693 (17)	0.0549 (13)	−0.0203 (12)	−0.0077 (11)	0.0065 (12)
O5	0.0440 (11)	0.0644 (17)	0.0433 (12)	−0.0055 (11)	−0.0022 (9)	0.0107 (11)
O4	0.0510 (13)	0.0592 (19)	0.0629 (14)	0.0028 (13)	0.0033 (11)	0.0007 (12)
F2	0.0780 (13)	0.1115 (19)	0.0524 (12)	−0.0054 (13)	−0.0198 (10)	−0.0045 (11)
C27	0.0427 (16)	0.048 (2)	0.0469 (18)	−0.0087 (16)	0.0020 (14)	0.0028 (16)
O3	0.0523 (14)	0.085 (2)	0.0860 (17)	−0.0195 (14)	0.0077 (12)	0.0007 (15)
C26	0.0389 (15)	0.045 (2)	0.0430 (18)	0.0013 (16)	−0.0003 (14)	0.0030 (16)
N2	0.0592 (17)	0.055 (2)	0.0455 (15)	−0.0085 (15)	−0.0056 (13)	−0.0067 (14)
C25	0.0404 (16)	0.051 (2)	0.0485 (19)	−0.0083 (16)	−0.0019 (15)	0.0019 (16)
N1	0.0473 (15)	0.063 (2)	0.0497 (15)	0.0006 (15)	−0.0027 (13)	0.0047 (15)
F1	0.0632 (12)	0.0949 (18)	0.1007 (16)	−0.0268 (13)	0.0126 (11)	−0.0043 (13)
O2	0.0625 (15)	0.0504 (18)	0.119 (2)	−0.0049 (13)	0.0233 (14)	0.0027 (15)
C24	0.0443 (17)	0.049 (2)	0.0424 (18)	0.0000 (17)	0.0010 (14)	−0.0006 (16)
O1	0.0527 (14)	0.078 (2)	0.117 (2)	0.0019 (14)	0.0122 (14)	−0.0158 (16)
C23	0.0500 (18)	0.053 (2)	0.0415 (18)	−0.0021 (18)	−0.0016 (15)	0.0006 (17)
C22	0.0516 (18)	0.063 (3)	0.049 (2)	−0.0173 (18)	0.0011 (16)	0.0040 (18)
C21	0.051 (2)	0.059 (3)	0.051 (2)	−0.006 (2)	−0.0065 (16)	0.0029 (19)
C20	0.0440 (19)	0.062 (3)	0.063 (2)	−0.004 (2)	−0.0056 (17)	−0.0109 (19)
C19	0.0437 (17)	0.051 (2)	0.0376 (17)	−0.0056 (16)	−0.0003 (14)	0.0027 (16)
C18	0.0426 (17)	0.066 (3)	0.062 (2)	−0.0160 (19)	−0.0021 (16)	0.0035 (19)
C17	0.0470 (18)	0.058 (2)	0.056 (2)	−0.0039 (18)	0.0019 (16)	0.0113 (18)
C16	0.0457 (17)	0.059 (3)	0.0411 (17)	−0.0051 (18)	−0.0008 (14)	0.0038 (17)
C15	0.0577 (19)	0.064 (3)	0.0411 (18)	−0.0140 (19)	0.0001 (16)	0.0066 (16)
C14	0.057 (2)	0.056 (3)	0.051 (2)	0.0013 (19)	0.0070 (16)	0.0000 (18)
C13	0.059 (2)	0.060 (3)	0.054 (2)	0.000 (2)	0.0037 (17)	0.0042 (19)
C12	0.056 (2)	0.076 (3)	0.056 (2)	0.008 (2)	0.0037 (18)	0.012 (2)
C11	0.066 (2)	0.067 (3)	0.067 (2)	0.015 (2)	0.0134 (19)	0.008 (2)
C10	0.086 (3)	0.064 (3)	0.065 (2)	−0.002 (2)	0.007 (2)	−0.011 (2)
C9	0.113 (3)	0.091 (3)	0.054 (2)	−0.027 (3)	−0.007 (2)	−0.019 (2)
C8	0.057 (2)	0.134 (4)	0.093 (3)	0.017 (3)	−0.017 (2)	0.006 (3)
C7	0.059 (2)	0.089 (4)	0.103 (3)	0.014 (2)	0.003 (2)	−0.015 (3)
C6	0.103 (3)	0.067 (3)	0.117 (4)	−0.027 (3)	0.017 (3)	0.001 (3)
C5	0.079 (3)	0.064 (3)	0.0453 (19)	−0.010 (2)	0.0061 (18)	−0.0028 (19)
C4	0.087 (3)	0.055 (3)	0.058 (2)	0.010 (2)	0.010 (2)	−0.006 (2)
B	0.050 (2)	0.079 (4)	0.050 (2)	−0.010 (2)	0.0032 (19)	−0.003 (2)
C3	0.069 (2)	0.082 (3)	0.090 (3)	0.017 (2)	−0.005 (2)	0.002 (2)
C2	0.082 (3)	0.048 (3)	0.126 (4)	−0.002 (2)	−0.003 (2)	−0.002 (2)
C1	0.122 (4)	0.069 (4)	0.123 (4)	0.022 (3)	0.002 (3)	−0.018 (3)

Geometric parameters (Å, º) top

B—N1	1.533 (5)	C16—C14	1.415 (5)
B—N2	1.537 (5)	C15—H15A	0.9300
B—F1	1.382 (4)	C14—C11	1.377 (4)
B—F2	1.384 (4)	C14—C10	1.506 (4)
O6—C25	1.377 (3)	C13—C4	1.366 (5)
O6—C18	1.399 (3)	C13—C3	1.486 (4)
O5—C26	1.373 (3)	C12—C11	1.392 (5)
O5—C17	1.413 (3)	C12—C8	1.494 (4)
O4—C21	1.328 (4)	C11—H11A	0.9300
O4—C7	1.448 (4)	C10—H10A	0.9600
C27—C26	1.377 (4)	C10—H10B	0.9600
C27—C24	1.394 (4)	C10—H10C	0.9600
C27—H27A	0.9300	C9—C5	1.487 (5)
O3—C21	1.206 (4)	C9—H9A	0.9600
C26—C25	1.389 (4)	C9—H9B	0.9600
N2—C5	1.346 (4)	C9—H9C	0.9600
N2—C23	1.402 (4)	C8—H8A	0.9600
C25—C22	1.373 (4)	C8—H8B	0.9600
N1—C12	1.345 (4)	C8—H8C	0.9600
N1—C16	1.404 (4)	C7—C1	1.499 (5)
O2—C20	1.323 (4)	C7—H7A	0.9700
O2—C2	1.461 (4)	C7—H7B	0.9700
C24—C15	1.365 (4)	C6—C2	1.448 (5)
C24—C19	1.496 (4)	C6—H6A	0.9600
O1—C20	1.180 (4)	C6—H6B	0.9600
C23—C19	1.393 (4)	C6—H6C	0.9600
C23—C13	1.432 (4)	C5—C4	1.398 (5)
C22—C15	1.386 (4)	C4—H4A	0.9300
C22—H22A	0.9300	C3—H3A	0.9600
C21—C17	1.485 (4)	C3—H3B	0.9600
C20—C18	1.508 (5)	C3—H3C	0.9600
C19—C16	1.395 (4)	C2—H2A	0.9700
C18—H18A	0.9700	C2—H2B	0.9700
C18—H18B	0.9700	C1—H1A	0.9600
C17—H17A	0.9700	C1—H1B	0.9600
C17—H17B	0.9700	C1—H1C	0.9600

C25—O6—C18	118.2 (2)	C14—C11—C12	108.7 (3)
C26—O5—C17	118.1 (2)	C14—C11—H11A	125.7
C21—O4—C7	116.6 (3)	C12—C11—H11A	125.7
C26—C27—C24	120.1 (3)	C14—C10—H10A	109.5
C26—C27—H27A	119.9	C14—C10—H10B	109.5
C24—C27—H27A	119.9	H10A—C10—H10B	109.5
O5—C26—C27	125.8 (3)	C14—C10—H10C	109.5
O5—C26—C25	114.2 (2)	H10A—C10—H10C	109.5
C27—C26—C25	120.0 (3)	H10B—C10—H10C	109.5
C5—N2—C23	108.0 (3)	C5—C9—H9A	109.5
C5—N2—B	126.9 (3)	C5—C9—H9B	109.5
C23—N2—B	125.1 (3)	H9A—C9—H9B	109.5
C22—C25—O6	125.6 (3)	C5—C9—H9C	109.5
C22—C25—C26	119.8 (3)	H9A—C9—H9C	109.5
O6—C25—C26	114.6 (3)	H9B—C9—H9C	109.5
C12—N1—C16	107.9 (3)	C12—C8—H8A	109.5
C12—N1—B	126.2 (3)	C12—C8—H8B	109.5
C16—N1—B	125.7 (3)	H8A—C8—H8B	109.5
C20—O2—C2	118.2 (3)	C12—C8—H8C	109.5
C15—C24—C27	119.2 (3)	H8A—C8—H8C	109.5
C15—C24—C19	121.4 (3)	H8B—C8—H8C	109.5
C27—C24—C19	119.3 (3)	O4—C7—C1	107.1 (3)
C19—C23—N2	120.1 (3)	O4—C7—H7A	110.3
C19—C23—C13	132.0 (3)	C1—C7—H7A	110.3
N2—C23—C13	107.8 (3)	O4—C7—H7B	110.3
C25—C22—C15	119.8 (3)	C1—C7—H7B	110.3
C25—C22—H22A	120.1	H7A—C7—H7B	108.6
C15—C22—H22A	120.1	C2—C6—H6A	109.5
O3—C21—O4	123.7 (3)	C2—C6—H6B	109.5
O3—C21—C17	123.0 (4)	H6A—C6—H6B	109.5
O4—C21—C17	113.3 (3)	C2—C6—H6C	109.5
O1—C20—O2	126.1 (4)	H6A—C6—H6C	109.5
O1—C20—C18	126.2 (3)	H6B—C6—H6C	109.5
O2—C20—C18	107.7 (3)	N2—C5—C4	108.9 (3)
C23—C19—C16	121.8 (3)	N2—C5—C9	124.1 (3)
C23—C19—C24	119.7 (3)	C4—C5—C9	127.0 (4)
C16—C19—C24	118.5 (3)	C13—C4—C5	109.4 (3)
O6—C18—C20	113.8 (3)	C13—C4—H4A	125.3
O6—C18—H18A	108.8	C5—C4—H4A	125.3
C20—C18—H18A	108.8	F1—B—F2	108.9 (3)
O6—C18—H18B	108.8	F1—B—N1	110.3 (3)
C20—C18—H18B	108.8	F2—B—N1	110.7 (3)
H18A—C18—H18B	107.7	F1—B—N2	110.2 (3)
O5—C17—C21	114.8 (3)	F2—B—N2	109.6 (3)
O5—C17—H17A	108.6	N1—B—N2	107.2 (3)
C21—C17—H17A	108.6	C13—C3—H3A	109.5
O5—C17—H17B	108.6	C13—C3—H3B	109.5
C21—C17—H17B	108.6	H3A—C3—H3B	109.5
H17A—C17—H17B	107.5	C13—C3—H3C	109.5
C19—C16—N1	119.4 (3)	H3A—C3—H3C	109.5
C19—C16—C14	132.9 (3)	H3B—C3—H3C	109.5
N1—C16—C14	107.7 (3)	C6—C2—O2	106.9 (3)
C24—C15—C22	121.0 (3)	C6—C2—H2A	110.3
C24—C15—H15A	119.5	O2—C2—H2A	110.3
C22—C15—H15A	119.5	C6—C2—H2B	110.3
C11—C14—C16	106.4 (3)	O2—C2—H2B	110.3
C11—C14—C10	124.1 (4)	H2A—C2—H2B	108.6
C16—C14—C10	129.5 (3)	C7—C1—H1A	109.5
C4—C13—C23	105.9 (3)	C7—C1—H1B	109.5
C4—C13—C3	124.6 (3)	H1A—C1—H1B	109.5
C23—C13—C3	129.5 (3)	C7—C1—H1C	109.5
N1—C12—C11	109.3 (3)	H1A—C1—H1C	109.5
N1—C12—C8	123.5 (4)	H1B—C1—H1C	109.5
C11—C12—C8	127.2 (4)

C17—O5—C26—C27	6.0 (4)	B—N1—C16—C14	173.3 (3)
C17—O5—C26—C25	−174.1 (3)	C27—C24—C15—C22	1.1 (5)
C24—C27—C26—O5	−179.7 (3)	C19—C24—C15—C22	−178.0 (3)
C24—C27—C26—C25	0.5 (5)	C25—C22—C15—C24	0.3 (5)
C18—O6—C25—C22	2.3 (5)	C19—C16—C14—C11	−179.7 (3)
C18—O6—C25—C26	−177.8 (3)	N1—C16—C14—C11	0.9 (3)
O5—C26—C25—C22	−178.9 (3)	C19—C16—C14—C10	1.6 (6)
C27—C26—C25—C22	0.9 (5)	N1—C16—C14—C10	−177.7 (3)
O5—C26—C25—O6	1.1 (4)	C19—C23—C13—C4	176.6 (3)
C27—C26—C25—O6	−179.0 (3)	N2—C23—C13—C4	0.0 (4)
C26—C27—C24—C15	−1.5 (5)	C19—C23—C13—C3	−1.2 (6)
C26—C27—C24—C19	177.6 (3)	N2—C23—C13—C3	−177.7 (3)
C5—N2—C23—C19	−177.7 (3)	C16—N1—C12—C11	1.2 (4)
B—N2—C23—C19	1.5 (5)	B—N1—C12—C11	−173.4 (3)
C5—N2—C23—C13	−0.7 (4)	C16—N1—C12—C8	−179.6 (3)
B—N2—C23—C13	178.5 (3)	B—N1—C12—C8	5.7 (5)
O6—C25—C22—C15	178.6 (3)	C16—C14—C11—C12	−0.2 (4)
C26—C25—C22—C15	−1.3 (5)	C10—C14—C11—C12	178.5 (3)
C7—O4—C21—O3	−3.2 (5)	N1—C12—C11—C14	−0.6 (4)
C7—O4—C21—C17	175.8 (3)	C8—C12—C11—C14	−179.7 (3)
C2—O2—C20—O1	−0.6 (5)	C21—O4—C7—C1	−174.3 (3)
C2—O2—C20—C18	178.2 (3)	C23—N2—C5—C4	1.1 (4)
N2—C23—C19—C16	3.5 (5)	B—N2—C5—C4	−178.1 (3)
C13—C23—C19—C16	−172.7 (3)	C23—N2—C5—C9	180.0 (3)
N2—C23—C19—C24	−178.3 (3)	B—N2—C5—C9	0.8 (5)
C13—C23—C19—C24	5.5 (5)	C23—C13—C4—C5	0.6 (4)
C15—C24—C19—C23	−98.2 (4)	C3—C13—C4—C5	178.5 (3)
C27—C24—C19—C23	82.7 (4)	N2—C5—C4—C13	−1.1 (4)
C15—C24—C19—C16	80.1 (4)	C9—C5—C4—C13	−180.0 (3)
C27—C24—C19—C16	−99.0 (3)	C12—N1—B—F1	63.3 (4)
C25—O6—C18—C20	−73.6 (4)	C16—N1—B—F1	−110.3 (3)
O1—C20—C18—O6	−6.4 (5)	C12—N1—B—F2	−57.2 (4)
O2—C20—C18—O6	174.9 (3)	C16—N1—B—F2	129.1 (3)
C26—O5—C17—C21	69.4 (4)	C12—N1—B—N2	−176.7 (3)
O3—C21—C17—O5	−167.7 (3)	C16—N1—B—N2	9.6 (4)
O4—C21—C17—O5	13.3 (4)	C5—N2—B—F1	−68.2 (4)
C23—C19—C16—N1	−1.3 (4)	C23—N2—B—F1	112.8 (4)
C24—C19—C16—N1	−179.5 (3)	C5—N2—B—F2	51.7 (5)
C23—C19—C16—C14	179.4 (3)	C23—N2—B—F2	−127.4 (3)
C24—C19—C16—C14	1.2 (5)	C5—N2—B—N1	171.8 (3)
C12—N1—C16—C19	179.2 (3)	C23—N2—B—N1	−7.2 (4)
B—N1—C16—C19	−6.1 (5)	C20—O2—C2—C6	−162.9 (3)
C12—N1—C16—C14	−1.3 (3)

Experimental details

Crystal data
Chemical formula	C₂₇H₃₁BF₂N₂O₆
M_r	528.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.6068 (6), 7.5418 (6), 36.896 (2)
β (°)	93.231 (5)
V (Å³)	2669.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.62 × 0.21 × 0.08

Data collection
Diffractometer	Bruker SMART APEX II CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.940, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	12387, 4681, 2283
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.152, 0.93
No. of reflections	4681
No. of parameters	343
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected bond lengths (Å) top

B—N1

1.533 (5)

B—N2

1.537 (5)

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8-[3,4-Bis(ethoxy­carbonyl­meth­oxy)­phen­yl]-4,4-difluoro-1,3,5,7-tetra­methyl-4-bora-3a,4a-diaza-s-indacene

Supporting information

Key indicators

checkCIF/PLATON results

8-[3,4-Bis(ethoxycarbonylmethoxy)phenyl]-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene