Crystal structure of 3-(4,4-di­fluoro-5,7-dimethyl-4-bora-3a,4a-di­aza-s-indacen-3-yl)propanoic acid

Kato, T.; Doi, M.

doi:10.1107/S2056989017016942

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Volume 73| Part 12| December 2017| Pages 1974-1976

https://doi.org/10.1107/S2056989017016942

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Crystal structure of 3-(4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacen-3-yl)propanoic acid

Takuma Kato ^a ^* and Mitsunobu Doi ^a

^aOsaka University of Pharmaceutical Sciences, Nasahara, Osaka 569-1094, Japan
^*Correspondence e-mail: t.kato@gly.oups.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 10 November 2017; accepted 24 November 2017; online 30 November 2017)

The crystal structure of the title compound, C₁₄H₁₅BF₂N₂O₂, which comprises a boron–dipyrromethene (BODIPY) backbone and a propionic acid group, has been determined at 100 K. The BODIPY fused-ring system is nearly planar, with a maximum deviation from the mean plane of 0.032 (2) Å. In the crystal, pairs of O—H⋯O hydrogen bonds connect the molecules, forming inversion dimers. The dimers are linked via C—H⋯O hydrogen bonds, forming a tape along the a axis. The tapes are stacked along the c axis through C—H⋯F hydrogen bonds and π–π interactions.

Keywords: crystal structure; fluorescence; BODIPY.

CCDC reference: 1587383

1. Chemical context

Boron–dipyrromethene (BODIPY) dyes have promising applications in material sciences for labeling biomolecules such as peptides, proteins, lipids and nucleic acids. BODIPY dyes have many advantages over other dyes, such as robustness against light and chemicals, high absorption coefficients and fluorescence quantum yields, narrow emission bandwidths, and so on (Boens et al., 2012 ). Moreover, their spectroscopic and photophysical properties are easy to tune by attachment of some residues at the appropriate positions of the difluoroboron dipyrromethene moiety (Loudet & Burgess, 2007 ; Ulrich et al., 2008 ). Herein we report the crystal structure of the title compound (Fig. 1) having the BODIPY fragment.

Figure 1
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

2. Structural commentary

The title compound is composed of a boron–dipyrromethene (BODIPY) backbone and a propionic acid group. The BODIPY fused-ring system is nearly planar, with a maximum deviation from the mean plane of 0.032 (2) Å for atom N4. The bond lengths in the BODIPY framework indicate the strongly delocalized π-system nature [C—C = 1.374 (2)–1.425 (2) Å and C—N = 1.346 (2)–1.401 (2) Å; Fig. 1]. There are weak intramolecular C—H⋯F hydrogen bonds present (C11—H11A⋯F1 and C13—H13B⋯F1; Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N5/C5–C7/C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯F1	0.96	2.52	3.146 (2)	123
C13—H13B⋯F1	0.97	2.49	3.096 (2)	120
C11—H11B⋯F2ⁱ	0.96	2.42	3.311 (2)	154
C6—H6⋯Cg2ⁱ	0.93	2.82	3.664 (1)	152
O16—H16⋯O15ⁱⁱ	0.91 (2)	1.75 (2)	2.648 (2)	175 (2)
C2—H2⋯O16ⁱⁱⁱ	0.93	2.57	3.479 (2)	168
C14—H14A⋯F1^iv	0.97	2.43	3.125 (2)	128
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+3; (iii) -x, -y+1, -z+3; (iv) x, y, z+1.

3. Supramolecular features

Packing diagrams of the title compound are shown in Figs. 2–4 . A pair of O—H⋯O hydrogen bonds between the carboxylic acid groups of opposite-facing molecules connect the two molecules (O16—H16⋯O15ⁱⁱ; symmetry code as in Table 1), forming inversion dimers (Fig. 2), and these dimers are linked into a tape structure along the a-axis direction via C—H⋯O hydrogen bonds (C2—H2⋯O16ⁱⁱⁱ; symmetry code as in Table 1). Furthermore, extended stacking of the tapes along the c-axis direction forms a layer parallel to the ac plane (Fig. 3) via C—H⋯F hydrogen bonds (C14—H14A⋯F1^iv; symmetry code as in Table 1) and π–π interactions [Cg1⋯Cg2^iv = 3.7802 (8) Å; symmetry code: (iv) x, y, z + 1; Cg1 and Cg 2 are the centroids of the N4/C1–C3/C9 and N5/C5–C7/C10 five-membered rings, respectively]. Between the layers, intermolecular C—H⋯F and C—H⋯π interactions (C11—H11B⋯F2ⁱ and C6—H6⋯Cg2ⁱ; symmetry code as in Table 1) are observed (Fig. 4).

Figure 2
A packing diagram of the title compound, showing the O16—H16⋯O15ⁱⁱ and C2—H2⋯O16ⁱⁱⁱ interactions (dashed blue lines). [Symmetry codes: (ii) −x + 1, −y + 1, −z + 3; (iii) −x, −y + 1, −z + 3.]

Figure 3
A packing diagram of the title compound, showing the C14—H14A⋯F1^iv and π–π (Cg1⋯Cg2^iv and Cg2⋯Cg1^v) interactions (dashed blue lines). [Symmetry codes: (iv) x, y, z + 1; (v) x, y, z − 1.]

Figure 4
A packing diagram of the title compound, showing the C11—H11B⋯F2ⁱ and C6—H6⋯Cg2ⁱ interactions (dashed blue lines). [Symmetry code: (i) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .]

4. Database survey

A search of the Cambridge Structural Database (CSD Version 5.38; Groom et al., 2016 ) for BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes) derivatives yielded 806 hits. Until 2001, there were only five reports [CSD refcode OCEBIL10 (Bonfiglio et al., 1983 ), JEHFUX (Picou et al., 1990 ), RETLUX (Kollmannsberger et al., 1997 ), QAQTOR (Chen et al., 1999 ) and XEJQAE (Burghart et al., 1999 )], but as the utility of BODIPY dyes was recognized, structural reports increased significantly. In all cases, the nearly planar BODIPY skeleton is modified with various functional groups, but no compound having a carboxylic acid directly attached to the BODIPY skeleton has been reported.

5. Synthesis and crystallization

The title compound was synthesized according to a previously described method (Giessler et al., 2010 ; Bihovsky & Pendrak, 1996 ). The compound was purified by column chromatography. Single crystals were obtained by slow evaporation from a mixed solution of cyclohexane/dichloromethane (1:1 vv) at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atom of the carboxyl group was refined freely, while the other H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and treated as riding on their parent atoms, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for methylene and aromatic H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₅BF₂N₂O₂
M_r	292.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.9474 (3), 27.3202 (9), 6.3886 (2)
β (°)	103.903 (3)
V (Å³)	1346.48 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.97
Crystal size (mm)	0.35 × 0.17 × 0.13

Data collection
Diffractometer	Rigaku Oxford Diffraction XtaLAB Pro: Kappa single and P200K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Yarnton, England.]$ )
T_min, T_max	0.739, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	7185, 2650, 2441
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.06
No. of reflections	2650
No. of parameters	196
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1587383

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016942/is5481sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016942/is5481Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017016942/is5481Isup3.cdx

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

3-(4,4-Difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacen-3-yl)propanoic acid top

Crystal data top

C₁₄H₁₅BF₂N₂O₂	F(000) = 608
M_r = 292.09	D_x = 1.441 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.9474 (3) Å	Cell parameters from 4875 reflections
b = 27.3202 (9) Å	θ = 6.6–73.9°
c = 6.3886 (2) Å	µ = 0.97 mm⁻¹
β = 103.903 (3)°	T = 100 K
V = 1346.48 (8) Å³	Plate, red
Z = 4	0.35 × 0.17 × 0.13 mm

Data collection top

Rigaku Oxford Diffraction XtaLAB Pro: Kappa single and P200K diffractometer	2650 independent reflections
Radiation source: rotated anode	2441 reflections with I > 2σ(I)
Detector resolution: 8.336 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 74.1°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −9→9
T_min = 0.739, T_max = 0.878	k = −33→33
7185 measured reflections	l = −7→7

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0442P)² + 0.5604P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2650 reflections	Δρ_max = 0.20 e Å⁻³
196 parameters	Δρ_min = −0.19 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
F1	0.13158 (9)	0.60985 (3)	0.65315 (12)	0.0255 (2)
F2	0.08937 (9)	0.67726 (3)	0.84017 (12)	0.02436 (19)
B4	0.00668 (17)	0.64191 (5)	0.6943 (2)	0.0198 (3)
N4	−0.12985 (13)	0.61414 (4)	0.78542 (17)	0.0199 (2)
N5	−0.09242 (13)	0.66655 (4)	0.48014 (16)	0.0191 (2)
O15	0.39633 (12)	0.54006 (4)	1.32206 (16)	0.0290 (2)
O16	0.28087 (13)	0.49056 (4)	1.52940 (16)	0.0290 (2)
H16	0.395 (3)	0.4817 (8)	1.583 (4)	0.060 (6)*
C1	−0.38942 (17)	0.58795 (5)	0.8312 (2)	0.0247 (3)
H1	−0.507975	0.582922	0.811031	0.030*
C2	−0.26001 (17)	0.56942 (5)	0.9971 (2)	0.0251 (3)
H2	−0.275726	0.549606	1.109267	0.030*
C3	−0.10063 (17)	0.58593 (5)	0.9655 (2)	0.0218 (3)
C5	−0.02424 (16)	0.69272 (5)	0.3422 (2)	0.0207 (3)
C6	−0.15801 (17)	0.70826 (5)	0.1669 (2)	0.0224 (3)
H6	−0.143874	0.726714	0.049951	0.027*
C7	−0.31272 (17)	0.69140 (5)	0.1990 (2)	0.0221 (3)
C8	−0.37630 (16)	0.64040 (5)	0.5064 (2)	0.0217 (3)
H8	−0.495594	0.640225	0.449840	0.026*
C9	−0.30802 (16)	0.61578 (5)	0.6990 (2)	0.0212 (3)
C10	−0.27228 (16)	0.66503 (5)	0.3973 (2)	0.0204 (3)
C11	0.16412 (16)	0.70348 (5)	0.3788 (2)	0.0240 (3)
H11A	0.225357	0.688706	0.511699	0.036*
H11B	0.181863	0.738252	0.386612	0.036*
H11C	0.206667	0.690412	0.261876	0.036*
C12	−0.48969 (17)	0.69906 (6)	0.0566 (2)	0.0284 (3)
H12A	−0.547730	0.724511	0.115597	0.043*
H12B	−0.554999	0.669256	0.047816	0.043*
H12C	−0.479989	0.708339	−0.084927	0.043*
C13	0.07910 (17)	0.57591 (5)	1.0954 (2)	0.0251 (3)
H13A	0.128247	0.606001	1.164537	0.030*
H13B	0.149880	0.565559	0.999090	0.030*
C14	0.08684 (17)	0.53691 (5)	1.2669 (2)	0.0230 (3)
H14A	0.029454	0.548953	1.374614	0.028*
H14B	0.025020	0.508035	1.201109	0.028*
C15	0.26966 (17)	0.52318 (5)	1.3743 (2)	0.0235 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0230 (4)	0.0268 (4)	0.0273 (4)	0.0073 (3)	0.0073 (3)	0.0027 (3)
F2	0.0249 (4)	0.0249 (4)	0.0224 (4)	−0.0054 (3)	0.0041 (3)	−0.0017 (3)
B4	0.0182 (6)	0.0208 (7)	0.0202 (7)	0.0013 (5)	0.0043 (5)	0.0005 (5)
N4	0.0197 (5)	0.0185 (5)	0.0210 (5)	0.0004 (4)	0.0040 (4)	0.0006 (4)
N5	0.0181 (5)	0.0197 (5)	0.0201 (5)	0.0009 (4)	0.0057 (4)	0.0000 (4)
O15	0.0257 (5)	0.0280 (5)	0.0309 (5)	−0.0027 (4)	0.0021 (4)	0.0099 (4)
O16	0.0272 (5)	0.0309 (5)	0.0283 (5)	0.0031 (4)	0.0058 (4)	0.0120 (4)
C1	0.0222 (6)	0.0252 (7)	0.0279 (7)	−0.0020 (5)	0.0081 (5)	0.0016 (5)
C2	0.0281 (7)	0.0235 (6)	0.0246 (7)	−0.0020 (5)	0.0079 (5)	0.0036 (5)
C3	0.0257 (6)	0.0181 (6)	0.0214 (6)	−0.0003 (5)	0.0054 (5)	0.0002 (5)
C5	0.0219 (6)	0.0194 (6)	0.0222 (6)	0.0016 (5)	0.0078 (5)	−0.0005 (5)
C6	0.0245 (6)	0.0228 (6)	0.0210 (6)	0.0029 (5)	0.0077 (5)	0.0031 (5)
C7	0.0225 (6)	0.0223 (6)	0.0213 (6)	0.0035 (5)	0.0053 (5)	−0.0005 (5)
C8	0.0179 (6)	0.0224 (6)	0.0244 (6)	0.0009 (5)	0.0045 (5)	−0.0012 (5)
C9	0.0187 (6)	0.0212 (6)	0.0239 (6)	0.0001 (5)	0.0054 (5)	−0.0005 (5)
C10	0.0182 (6)	0.0215 (6)	0.0215 (6)	0.0025 (5)	0.0045 (5)	−0.0006 (5)
C11	0.0208 (6)	0.0251 (7)	0.0274 (7)	−0.0006 (5)	0.0081 (5)	0.0014 (5)
C12	0.0224 (6)	0.0363 (8)	0.0258 (7)	0.0057 (6)	0.0044 (5)	0.0046 (6)
C13	0.0246 (6)	0.0223 (6)	0.0262 (7)	−0.0015 (5)	0.0016 (5)	0.0041 (5)
C14	0.0258 (6)	0.0207 (6)	0.0215 (6)	−0.0002 (5)	0.0035 (5)	0.0000 (5)
C15	0.0290 (7)	0.0193 (6)	0.0209 (6)	−0.0012 (5)	0.0034 (5)	0.0008 (5)

Geometric parameters (Å, º) top

F1—B4	1.3953 (15)	C6—C7	1.3738 (18)
F2—B4	1.3926 (16)	C6—H6	0.9300
B4—N4	1.5479 (17)	C7—C10	1.4253 (18)
B4—N5	1.5579 (17)	C7—C12	1.4948 (18)
N4—C3	1.3575 (16)	C8—C10	1.3781 (18)
N4—C9	1.3915 (16)	C8—C9	1.3926 (18)
N5—C5	1.3458 (16)	C8—H8	0.9300
N5—C10	1.4006 (16)	C11—H11A	0.9600
O15—C15	1.2243 (16)	C11—H11B	0.9600
O16—C15	1.3197 (16)	C11—H11C	0.9600
O16—H16	0.92 (2)	C12—H12A	0.9600
C1—C2	1.3833 (19)	C12—H12B	0.9600
C1—C9	1.4047 (18)	C12—H12C	0.9600
C1—H1	0.9300	C13—C14	1.5189 (18)
C2—C3	1.4042 (18)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C13	1.4948 (18)	C14—C15	1.4978 (18)
C5—C6	1.4117 (18)	C14—H14A	0.9700
C5—C11	1.4878 (17)	C14—H14B	0.9700

F2—B4—F1	108.59 (10)	N4—C9—C8	120.64 (11)
F2—B4—N4	110.42 (10)	N4—C9—C1	108.39 (11)
F1—B4—N4	110.96 (10)	C8—C9—C1	130.90 (12)
F2—B4—N5	110.23 (10)	C8—C10—N5	120.33 (11)
F1—B4—N5	109.78 (10)	C8—C10—C7	131.45 (12)
N4—B4—N5	106.86 (10)	N5—C10—C7	108.22 (11)
C3—N4—C9	107.77 (11)	C5—C11—H11A	109.5
C3—N4—B4	127.19 (11)	C5—C11—H11B	109.5
C9—N4—B4	124.98 (10)	H11A—C11—H11B	109.5
C5—N5—C10	107.65 (10)	C5—C11—H11C	109.5
C5—N5—B4	127.34 (10)	H11A—C11—H11C	109.5
C10—N5—B4	125.02 (10)	H11B—C11—H11C	109.5
C15—O16—H16	109.7 (14)	C7—C12—H12A	109.5
C2—C1—C9	107.09 (12)	C7—C12—H12B	109.5
C2—C1—H1	126.5	H12A—C12—H12B	109.5
C9—C1—H1	126.5	C7—C12—H12C	109.5
C1—C2—C3	107.61 (11)	H12A—C12—H12C	109.5
C1—C2—H2	126.2	H12B—C12—H12C	109.5
C3—C2—H2	126.2	C3—C13—C14	113.36 (11)
N4—C3—C2	109.13 (11)	C3—C13—H13A	108.9
N4—C3—C13	121.36 (11)	C14—C13—H13A	108.9
C2—C3—C13	129.50 (12)	C3—C13—H13B	108.9
N5—C5—C6	109.54 (11)	C14—C13—H13B	108.9
N5—C5—C11	123.37 (12)	H13A—C13—H13B	107.7
C6—C5—C11	127.08 (12)	C15—C14—C13	111.89 (11)
C7—C6—C5	108.12 (11)	C15—C14—H14A	109.2
C7—C6—H6	125.9	C13—C14—H14A	109.2
C5—C6—H6	125.9	C15—C14—H14B	109.2
C6—C7—C10	106.47 (11)	C13—C14—H14B	109.2
C6—C7—C12	127.39 (12)	H14A—C14—H14B	107.9
C10—C7—C12	126.14 (12)	O15—C15—O16	123.19 (12)
C10—C8—C9	121.93 (12)	O15—C15—C14	123.47 (12)
C10—C8—H8	119.0	O16—C15—C14	113.34 (11)
C9—C8—H8	119.0

F2—B4—N4—C3	−62.77 (16)	C5—C6—C7—C10	−0.11 (15)
F1—B4—N4—C3	57.69 (16)	C5—C6—C7—C12	179.56 (13)
N5—B4—N4—C3	177.34 (11)	C3—N4—C9—C8	−176.99 (11)
F2—B4—N4—C9	114.21 (13)	B4—N4—C9—C8	5.53 (19)
F1—B4—N4—C9	−125.33 (12)	C3—N4—C9—C1	0.32 (14)
N5—B4—N4—C9	−5.68 (16)	B4—N4—C9—C1	−177.16 (11)
F2—B4—N5—C5	62.94 (16)	C10—C8—C9—N4	−1.75 (19)
F1—B4—N5—C5	−56.64 (16)	C10—C8—C9—C1	−178.37 (13)
N4—B4—N5—C5	−177.05 (11)	C2—C1—C9—N4	−0.17 (15)
F2—B4—N5—C10	−117.07 (12)	C2—C1—C9—C8	176.77 (13)
F1—B4—N5—C10	123.35 (12)	C9—C8—C10—N5	−0.94 (19)
N4—B4—N5—C10	2.94 (16)	C9—C8—C10—C7	178.50 (13)
C9—C1—C2—C3	−0.03 (15)	C5—N5—C10—C8	179.99 (11)
C9—N4—C3—C2	−0.34 (14)	B4—N5—C10—C8	0.00 (18)
B4—N4—C3—C2	177.06 (12)	C5—N5—C10—C7	0.43 (14)
C9—N4—C3—C13	178.81 (11)	B4—N5—C10—C7	−179.55 (11)
B4—N4—C3—C13	−3.79 (19)	C6—C7—C10—C8	−179.68 (13)
C1—C2—C3—N4	0.23 (15)	C12—C7—C10—C8	0.6 (2)
C1—C2—C3—C13	−178.83 (13)	C6—C7—C10—N5	−0.19 (14)
C10—N5—C5—C6	−0.51 (14)	C12—C7—C10—N5	−179.87 (12)
B4—N5—C5—C6	179.48 (11)	N4—C3—C13—C14	−170.06 (11)
C10—N5—C5—C11	178.33 (11)	C2—C3—C13—C14	8.9 (2)
B4—N5—C5—C11	−1.69 (19)	C3—C13—C14—C15	172.63 (11)
N5—C5—C6—C7	0.39 (15)	C13—C14—C15—O15	−3.02 (18)
C11—C5—C6—C7	−178.39 (12)	C13—C14—C15—O16	177.79 (11)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the N5/C5–C7/C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···F1	0.96	2.52	3.146 (2)	123
C13—H13B···F1	0.97	2.49	3.096 (2)	120
C11—H11B···F2ⁱ	0.96	2.42	3.311 (2)	154
C6—H6···Cg2ⁱ	0.93	2.82	3.664 (1)	152
O16—H16···O15ⁱⁱ	0.91 (2)	1.75 (2)	2.648 (2)	175 (2)
C2—H2···O16ⁱⁱⁱ	0.93	2.57	3.479 (2)	168
C14—H14A···F1^iv	0.97	2.43	3.125 (2)	128

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+3; (iii) −x, −y+1, −z+3; (iv) x, y, z+1.

Funding information

This work was performed in part under the Cooperative Research Program of the Institute for Protein Research, Osaka University (CR-16–05).

References

Bihovsky, R. & Pendrak, I. (1996). Bioorg. Med. Chem. Lett. 6, 1541–1542. CrossRef CAS
Boens, N., Leen, V. & Dehaen, W. (2012). Chem. Soc. Rev. 41, 1130–1172. Web of Science CrossRef CAS PubMed
Bonfiglio, J. V., Bonnett, R., Buckley, D. G., Hamzetash, D., Hursthouse, M. B., Malik, K. M. A., McDonagh, A. F. & Trotter, J. (1983). Tetrahedron, 39, 1865–1874. CrossRef CAS
Burghart, A., Kim, H., Welch, M. B., Thoresen, L. H., Reibenspies, J., Burgess, K., Bergström, F. & Johansson, L. B. A. (1999). J. Org. Chem. 64, 7813–7819. CrossRef CAS
Chen, J., Reibenspies, J., Derecskei-Kovacs, A. & Burgess, K. (1999). Chem. Commun. pp. 2501–2502. CrossRef
Giessler, K., Griesser, H., Göhringer, D., Sabirov, T. & Richert, C. (2010). Eur. J. Org. Chem. pp. 3611–3620.
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Kollmannsberger, M., Gareis, T., Heinl, S., Daub, J. & Breu, J. (1997). Angew. Chem. Int. Ed. Engl. 36, 1333–1335. CrossRef CAS
Loudet, A. & Burgess, K. (2007). Chem. Rev. 107, 4891–4932. Web of Science CrossRef PubMed CAS
Picou, C. L., Stevens, E. D., Shah, M. & Boyer, J. H. (1990). Acta Cryst. C46, 1148–1150. CSD CrossRef CAS Web of Science IUCr Journals
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Corporation, Yarnton, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals
Ulrich, G., Ziessel, R. & Harriman, A. (2008). Angew. Chem. Int. Ed. 47, 1184–1201. Web of Science CrossRef CAS
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals

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