Crystal structure of (2-{[3,5-bis­(1,1-di­methyl­eth­yl)-4-hy­droxy­phen­yl](5-methyl-2H-pyrrol-2-yl­idene)meth­yl}-5-methyl-1H-pyrrolido-κ2N,N′)di­fluoridoboron

Morimoto, Y.; Ogawa, K.; Uto, Y.; Nagasawa, H.; Hori, H.

doi:10.1107/S2056989015015789

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 9| September 2015| Pages o694-o695

https://doi.org/10.1107/S2056989015015789

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Crystal structure of (2-{[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl](5-methyl-2H-pyrrol-2-ylidene)methyl}-5-methyl-1H-pyrrolido-κ²N,N′)difluoridoboron

Yukio Morimoto,^a ^* Keizo Ogawa,^b Yoshihiro Uto,^c Hideko Nagasawa ^d and Hitoshi Hori ^e

^aResearch Reactor Institute, Kyoto University, 2-1 Asashiro-Nishi, Kumatori, Osaka 590-0494, Japan, ^bNihon University Junior College, 7-24-1 Narashinodai, Funabashi, Chiba 274-8501, Japan, ^cDepartment of Engineering, The University of Tokushima, Minami-Josanjima, Tokushima 770-8506, Japan, ^dLaboratory of Pharmaceutical & Medicinal Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigakunishi, Gifu, 501-1196, Japan, and ^eNiigata University of Pharmacy and Applied Life Sciences, 265-1 Higashijima, Akiha-ku, Niigata 956-8603, Japan
^*Correspondence e-mail: morimoto@rri.kyoto-u.ac.jp

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 August 2015; accepted 23 August 2015; online 29 August 2015)

The title compound, C₂₅H₃₁BF₂N₂O, is a potential boron tracedrug in boron neutron capture therapy (BNCT), in which the B atom adopts a distorted BN₂F₂ tetrahedral geometry: it is soluble in dimethyl sulfoxide, dimethylformamide and methanol. The pyrrolylidenemethylpyrrole triple fused ring system is almost planar (r.m.s. deviation = 0.031 Å) and subtends a dihedral angle of 47.09 (5)° with the plane of the pendant phenol ring. The phenol –OH group is blocked from forming hydrogen bonds by the adjacent bulky tert-butyl groups. In the crystal, inversion dimers linked by pairs of very weak C—H⋯F interactions generate R₂²(22) loops.

Keywords: crystal structure; boron tracedrug; boron neutron capture therapy (BNCT).

CCDC reference: 1420063

1. Related literature

For background to tracer compounds for BNCT, see: Hori et al. (2010 , 2012 ). For further synthetic details, see: Nakata et al. (2011 ).

2. Experimental

2.1. Crystal data

C₂₅H₃₁BF₂N₂O
M_r = 424.34
Triclinic, $[P \overline 1]$
a = 9.2518 (2) Å
b = 10.0975 (2) Å
c = 12.5142 (3) Å
α = 79.364 (6)°
β = 89.613 (6)°
γ = 83.367 (6)°
V = 1141.18 (5) Å³
Z = 2
Cu Kα radiation
μ = 0.69 mm⁻¹
T = 296 K
0.16 × 0.08 × 0.04 mm

2.2. Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ) T_min = 0.749, T_max = 0.973
13606 measured reflections
4044 independent reflections
3644 reflections with F² > 2.0σ(F²)
R_int = 0.026

2.3. Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.09
4044 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12C⋯F2ⁱ	0.96	2.54	3.4464 (18)	158
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: RAPID-AUTO (Rigaku, 2011 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: Il Milione (Burla et al., 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalStructure (Rigaku, 2011); software used to prepare material for publication: CrystalStructure.

Supporting information

CCDC reference: 1420063

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015015789/hb7487sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015789/hb7487Isup2.hkl

checkCIF report

Chemical context top

For the synthesis of 2-{[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl](5-methyl-2H-pyrrol-2-ylidene)methyl}-5-methyl-1H-pyrrolido-κ²N,N']difluoridoboron see: Nakata, et al. (2011). The compound: CAS Registry Number 1415304-92-5. The ring compound binding BF₂ is a contracted form given in IUPAC.

Structural commentary top

The traceability of boron tracedrugs is based on the neutron capture activity of the stable isotope boron-10 embedded in the drug. Thus, newly designed boron tracedrugs would be novel pharmaceuticals, the structures of which would always include natural boron (B¹¹, 80.4%; B¹⁰, 19.6%), as tracers, embedded deeply in their skeletons or scaffolds. The compound is used at a cancer therapy by an irradiation of neutron, since B¹⁰ atom generates a high energy alpha-line within a cancer cell by fission of the atom. The compound is required to keep a suitable three-dimensional structure until reaching cancer cell via intravenous injection and an irradiation of neutron. Our group has developed boron tracedrugs in use of boron-neutron reaction (Hori, et al. 2010, 2012), in this study a suitable compound has been reported and presents that two bulky rings tilt each other to avoid steric hindrance.

Synthesis and crystallization top

Crystals were obtained from methanol solvent at room temperature by slow evaporation. Crystal structure has no present of solvent molecule. The synthesis of the title compound was decribed by Nakata et al. (2011). The compound: CAS Registry Number 1415304-92-5. The ring compound binding BF₂ is a contracted form given in IUPAC.

Refinement top

All hydrogen atoms were placed in the calculated positions and constrained their parent atoms with a C—H distances of 0.95 Å (aromatic) and 0.99 Å (methylene) and with Uiso(H) = 1.2Ueq(C), and 0.98 Å for CH3 [Uiso(H)= 1.5Ueq(C)].

Related literature top

For background to tracer compounds for BNCT, see: Hori et al. (2010, 2012). For further synthetic details, see: Nakata et al. (2011).

Structure description top

For background to tracer compounds for BNCT, see: Hori et al. (2010, 2012). For further synthetic details, see: Nakata et al. (2011).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2011); cell refinement: RAPID-AUTO (Rigaku, 2011); data reduction: RAPID-AUTO (Rigaku, 2011); program(s) used to solve structure: Il Milione (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2011); software used to prepare material for publication: CrystalStructure (Rigaku, 2011).

Figures top

Fig. 1. Molecular structure of the compound. Displacement ellipsoids are shown at the 50% probability level. H atoms are depicted as small spheres of arbitrary radius.

(2-{[3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl](5-methyl-2H-pyrrol-2-ylidene)methyl}-5-methyl-1H-pyrrolido-κ²N,N')difluoridoboron top

Crystal data top

C₂₅H₃₁BF₂N₂O	Z = 2
M_r = 424.34	F(000) = 452.00
Triclinic, P1	D_x = 1.235 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54187 Å
a = 9.2518 (2) Å	Cell parameters from 11333 reflections
b = 10.0975 (2) Å	θ = 3.6–68.2°
c = 12.5142 (3) Å	µ = 0.69 mm⁻¹
α = 79.364 (6)°	T = 296 K
β = 89.613 (6)°	Platelet, orange
γ = 83.367 (6)°	0.16 × 0.08 × 0.04 mm
V = 1141.18 (5) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3644 reflections with F² > 2.0σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 67.5°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −10→10
T_min = 0.749, T_max = 0.973	k = −12→12
13606 measured reflections	l = −14→14
4044 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0594P)² + 0.4471P] where P = (F_o² + 2F_c²)/3
4044 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₅H₃₁BF₂N₂O	γ = 83.367 (6)°
M_r = 424.34	V = 1141.18 (5) Å³
Triclinic, P1	Z = 2
a = 9.2518 (2) Å	Cu Kα radiation
b = 10.0975 (2) Å	µ = 0.69 mm⁻¹
c = 12.5142 (3) Å	T = 296 K
α = 79.364 (6)°	0.16 × 0.08 × 0.04 mm
β = 89.613 (6)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	4044 independent reflections
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	3644 reflections with F² > 2.0σ(F²)
T_min = 0.749, T_max = 0.973	R_int = 0.026
13606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
4044 reflections	Δρ_min = −0.20 e Å⁻³
289 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
F1	0.16643 (10)	0.79448 (8)	0.09158 (7)	0.0297 (2)
F2	0.39555 (10)	0.84379 (8)	0.11327 (7)	0.0294 (2)
O1	0.22265 (12)	0.68344 (10)	0.86928 (8)	0.0231 (2)
N1	0.30765 (13)	0.67065 (12)	0.24855 (9)	0.0191 (3)
N2	0.21212 (13)	0.91383 (12)	0.23671 (9)	0.0193 (3)
C1	0.23318 (15)	0.70635 (14)	0.75831 (11)	0.0181 (3)
C2	0.18152 (15)	0.60808 (13)	0.70604 (11)	0.0183 (3)
C3	0.18647 (15)	0.63023 (14)	0.59314 (11)	0.0187 (3)
C4	0.24376 (15)	0.74233 (13)	0.53267 (11)	0.0185 (3)
C5	0.29681 (15)	0.83469 (14)	0.58803 (11)	0.0188 (3)
C6	0.29266 (15)	0.82094 (13)	0.70055 (11)	0.0185 (3)
C7	0.12345 (16)	0.47938 (14)	0.76987 (11)	0.0203 (3)
C8	−0.00798 (17)	0.51496 (15)	0.83913 (12)	0.0263 (3)
C9	0.24586 (17)	0.39358 (14)	0.84310 (12)	0.0252 (3)
C10	0.07400 (18)	0.38987 (15)	0.69353 (12)	0.0257 (3)
C11	0.34936 (16)	0.92882 (14)	0.75712 (11)	0.0207 (3)
C12	0.47337 (17)	0.86627 (15)	0.83888 (12)	0.0264 (3)
C13	0.22373 (18)	1.00162 (15)	0.81377 (13)	0.0267 (3)
C14	0.41194 (18)	1.03996 (15)	0.67502 (12)	0.0274 (3)
C15	0.24904 (15)	0.76195 (14)	0.41279 (11)	0.0189 (3)
C16	0.30154 (15)	0.65409 (14)	0.36187 (11)	0.0189 (3)
C17	0.35863 (16)	0.51942 (14)	0.40509 (12)	0.0219 (3)
C18	0.39704 (17)	0.45610 (15)	0.31931 (12)	0.0241 (3)
C19	0.36563 (16)	0.55126 (14)	0.22312 (12)	0.0213 (3)
C20	0.16017 (16)	1.04503 (14)	0.19924 (12)	0.0218 (3)
C21	0.11602 (16)	1.10733 (15)	0.28709 (12)	0.0235 (3)
C22	0.14065 (16)	1.01132 (14)	0.38080 (12)	0.0218 (3)
C23	0.20257 (15)	0.88981 (14)	0.34988 (11)	0.0192 (3)
C24	0.38939 (18)	0.53166 (16)	0.10909 (12)	0.0259 (3)
C25	0.15235 (18)	1.10739 (15)	0.08147 (12)	0.0264 (3)
B1	0.27066 (19)	0.80652 (16)	0.16769 (13)	0.0209 (3)
H1	0.24213	0.7504	0.8922	0.0277*
H3	0.15046	0.56837	0.55667	0.0224*
H5	0.33661	0.90855	0.5481	0.0225*
H8A	−0.03914	0.43306	0.87955	0.0316*
H8B	−0.08608	0.56366	0.79254	0.0316*
H8C	0.01911	0.5704	0.88858	0.0316*
H9A	0.21123	0.31164	0.88038	0.0302*
H9B	0.2753	0.44429	0.89533	0.0302*
H9C	0.32743	0.37128	0.79929	0.0302*
H10A	−0.002	0.44051	0.64586	0.0308*
H10B	0.03821	0.31134	0.73579	0.0308*
H10C	0.15488	0.36182	0.65121	0.0308*
H12A	0.55293	0.8262	0.80142	0.0317*
H12B	0.43873	0.79781	0.8935	0.0317*
H12C	0.50577	0.93581	0.87267	0.0317*
H13A	0.25886	1.07288	0.84391	0.0320*
H13B	0.18676	0.93777	0.87091	0.0320*
H13C	0.14735	1.03955	0.76174	0.0320*
H14A	0.49141	0.99973	0.63759	0.0329*
H14B	0.44603	1.10512	0.71286	0.0329*
H14C	0.33743	1.08438	0.62338	0.0329*
H17	0.36849	0.48053	0.47844	0.0262*
H18	0.43675	0.36626	0.32406	0.0289*
H21	0.0771	1.1973	0.28295	0.0282*
H22	0.12026	1.02419	0.45129	0.0261*
H24A	0.43805	0.60446	0.07017	0.0311*
H24B	0.29725	0.531	0.0745	0.0311*
H24C	0.44821	0.44688	0.10904	0.0311*
H25A	0.08056	1.06873	0.04575	0.0316*
H25B	0.2455	1.09007	0.04932	0.0316*
H25C	0.12595	1.20352	0.07348	0.0316*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0432 (6)	0.0228 (4)	0.0232 (5)	−0.0056 (4)	−0.0130 (4)	−0.0026 (3)
F2	0.0376 (5)	0.0257 (5)	0.0273 (5)	−0.0101 (4)	0.0142 (4)	−0.0075 (4)
O1	0.0345 (6)	0.0206 (5)	0.0158 (5)	−0.0088 (4)	0.0015 (4)	−0.0040 (4)
N1	0.0194 (6)	0.0217 (6)	0.0168 (6)	−0.0031 (5)	0.0001 (5)	−0.0048 (5)
N2	0.0195 (6)	0.0208 (6)	0.0173 (6)	−0.0034 (5)	0.0001 (5)	−0.0018 (5)
C1	0.0189 (7)	0.0192 (7)	0.0155 (7)	0.0005 (5)	0.0001 (5)	−0.0027 (5)
C2	0.0172 (7)	0.0167 (7)	0.0199 (7)	−0.0008 (5)	0.0001 (5)	−0.0018 (5)
C3	0.0194 (7)	0.0183 (7)	0.0190 (7)	−0.0021 (5)	−0.0009 (5)	−0.0051 (5)
C4	0.0182 (7)	0.0189 (7)	0.0183 (7)	−0.0010 (5)	0.0008 (5)	−0.0037 (5)
C5	0.0185 (7)	0.0181 (7)	0.0191 (7)	−0.0022 (5)	0.0014 (5)	−0.0014 (5)
C6	0.0176 (7)	0.0182 (7)	0.0198 (7)	−0.0009 (5)	−0.0003 (5)	−0.0042 (5)
C7	0.0248 (8)	0.0178 (7)	0.0183 (7)	−0.0047 (6)	−0.0001 (6)	−0.0021 (5)
C8	0.0284 (9)	0.0232 (7)	0.0274 (8)	−0.0073 (6)	0.0057 (6)	−0.0021 (6)
C9	0.0321 (9)	0.0182 (7)	0.0242 (8)	−0.0032 (6)	−0.0039 (6)	−0.0008 (6)
C10	0.0325 (9)	0.0218 (7)	0.0239 (8)	−0.0099 (6)	−0.0005 (6)	−0.0027 (6)
C11	0.0258 (8)	0.0186 (7)	0.0188 (7)	−0.0054 (6)	0.0004 (6)	−0.0045 (6)
C12	0.0302 (9)	0.0247 (8)	0.0259 (8)	−0.0080 (6)	−0.0040 (6)	−0.0058 (6)
C13	0.0348 (9)	0.0199 (7)	0.0274 (8)	−0.0050 (6)	0.0054 (7)	−0.0085 (6)
C14	0.0363 (9)	0.0245 (8)	0.0241 (8)	−0.0133 (7)	0.0010 (7)	−0.0056 (6)
C15	0.0160 (7)	0.0217 (7)	0.0195 (7)	−0.0055 (5)	−0.0001 (5)	−0.0034 (6)
C16	0.0188 (7)	0.0234 (7)	0.0151 (7)	−0.0051 (6)	−0.0002 (5)	−0.0036 (5)
C17	0.0218 (8)	0.0241 (7)	0.0187 (7)	−0.0011 (6)	−0.0014 (6)	−0.0025 (6)
C18	0.0253 (8)	0.0211 (7)	0.0248 (8)	0.0027 (6)	−0.0003 (6)	−0.0048 (6)
C19	0.0194 (8)	0.0239 (7)	0.0212 (7)	−0.0015 (6)	0.0006 (6)	−0.0065 (6)
C20	0.0196 (8)	0.0220 (7)	0.0225 (7)	−0.0029 (6)	−0.0013 (6)	−0.0005 (6)
C21	0.0239 (8)	0.0198 (7)	0.0257 (8)	0.0010 (6)	0.0000 (6)	−0.0034 (6)
C22	0.0219 (8)	0.0245 (7)	0.0193 (7)	−0.0019 (6)	0.0017 (6)	−0.0053 (6)
C23	0.0190 (7)	0.0220 (7)	0.0170 (7)	−0.0044 (6)	0.0007 (5)	−0.0035 (5)
C24	0.0285 (8)	0.0277 (8)	0.0219 (8)	0.0006 (6)	0.0021 (6)	−0.0078 (6)
C25	0.0308 (9)	0.0245 (8)	0.0218 (8)	−0.0009 (6)	−0.0013 (6)	−0.0005 (6)
B1	0.0268 (9)	0.0209 (8)	0.0159 (8)	−0.0063 (7)	0.0005 (6)	−0.0034 (6)

Geometric parameters (Å, º) top

F1—B1	1.391 (2)	C22—C23	1.412 (2)
F2—B1	1.391 (2)	O1—H1	0.820
O1—C1	1.3698 (17)	C3—H3	0.930
N1—C16	1.3985 (18)	C5—H5	0.930
N1—C19	1.3536 (19)	C8—H8A	0.960
N1—B1	1.5515 (18)	C8—H8B	0.960
N2—C20	1.3537 (17)	C8—H8C	0.960
N2—C23	1.3960 (18)	C9—H9A	0.960
N2—B1	1.555 (2)	C9—H9B	0.960
C1—C2	1.412 (2)	C9—H9C	0.960
C1—C6	1.4132 (19)	C10—H10A	0.960
C2—C3	1.3904 (19)	C10—H10B	0.960
C2—C7	1.5453 (19)	C10—H10C	0.960
C3—C4	1.3971 (19)	C12—H12A	0.960
C4—C5	1.393 (2)	C12—H12B	0.960
C4—C15	1.4778 (19)	C12—H12C	0.960
C5—C6	1.3899 (19)	C13—H13A	0.960
C6—C11	1.544 (2)	C13—H13B	0.960
C7—C8	1.536 (2)	C13—H13C	0.960
C7—C9	1.5386 (19)	C14—H14A	0.960
C7—C10	1.536 (2)	C14—H14B	0.960
C11—C12	1.540 (2)	C14—H14C	0.960
C11—C13	1.542 (2)	C17—H17	0.930
C11—C14	1.538 (2)	C18—H18	0.930
C15—C16	1.399 (2)	C21—H21	0.930
C15—C23	1.4045 (18)	C22—H22	0.930
C16—C17	1.4096 (18)	C24—H24A	0.960
C17—C18	1.372 (2)	C24—H24B	0.960
C18—C19	1.4036 (19)	C24—H24C	0.960
C19—C24	1.488 (2)	C25—H25A	0.960
C20—C21	1.400 (2)	C25—H25B	0.960
C20—C25	1.491 (2)	C25—H25C	0.960
C21—C22	1.3784 (19)

C16—N1—C19	107.94 (11)	C4—C3—H3	118.911
C16—N1—B1	125.50 (12)	C4—C5—H5	118.675
C19—N1—B1	126.23 (12)	C6—C5—H5	118.675
C20—N2—C23	107.87 (12)	C7—C8—H8A	109.472
C20—N2—B1	126.91 (11)	C7—C8—H8B	109.471
C23—N2—B1	125.21 (11)	C7—C8—H8C	109.472
O1—C1—C2	115.70 (12)	H8A—C8—H8B	109.462
O1—C1—C6	121.79 (13)	H8A—C8—H8C	109.480
C2—C1—C6	122.51 (13)	H8B—C8—H8C	109.471
C1—C2—C3	117.24 (12)	C7—C9—H9A	109.472
C1—C2—C7	122.35 (12)	C7—C9—H9B	109.469
C3—C2—C7	120.40 (13)	C7—C9—H9C	109.475
C2—C3—C4	122.18 (14)	H9A—C9—H9B	109.473
C3—C4—C5	118.46 (13)	H9A—C9—H9C	109.469
C3—C4—C15	120.80 (13)	H9B—C9—H9C	109.470
C5—C4—C15	120.73 (12)	C7—C10—H10A	109.472
C4—C5—C6	122.65 (13)	C7—C10—H10B	109.473
C1—C6—C5	116.91 (13)	C7—C10—H10C	109.472
C1—C6—C11	122.82 (12)	H10A—C10—H10B	109.472
C5—C6—C11	120.27 (12)	H10A—C10—H10C	109.464
C2—C7—C8	111.62 (11)	H10B—C10—H10C	109.474
C2—C7—C9	109.37 (12)	C11—C12—H12A	109.467
C2—C7—C10	111.74 (11)	C11—C12—H12B	109.473
C8—C7—C9	109.89 (11)	C11—C12—H12C	109.474
C8—C7—C10	107.04 (13)	H12A—C12—H12B	109.472
C9—C7—C10	107.06 (12)	H12A—C12—H12C	109.466
C6—C11—C12	111.63 (11)	H12B—C12—H12C	109.475
C6—C11—C13	110.32 (12)	C11—C13—H13A	109.473
C6—C11—C14	111.71 (12)	C11—C13—H13B	109.475
C12—C11—C13	110.63 (12)	C11—C13—H13C	109.468
C12—C11—C14	106.21 (12)	H13A—C13—H13B	109.476
C13—C11—C14	106.14 (11)	H13A—C13—H13C	109.463
C4—C15—C16	120.26 (11)	H13B—C13—H13C	109.472
C4—C15—C23	119.79 (13)	C11—C14—H14A	109.471
C16—C15—C23	119.95 (12)	C11—C14—H14B	109.473
N1—C16—C15	121.13 (11)	C11—C14—H14C	109.466
N1—C16—C17	107.58 (13)	H14A—C14—H14B	109.468
C15—C16—C17	131.26 (13)	H14A—C14—H14C	109.475
C16—C17—C18	107.60 (12)	H14B—C14—H14C	109.473
C17—C18—C19	107.72 (13)	C16—C17—H17	126.206
N1—C19—C18	109.16 (13)	C18—C17—H17	126.198
N1—C19—C24	122.81 (12)	C17—C18—H18	126.137
C18—C19—C24	128.03 (13)	C19—C18—H18	126.139
N2—C20—C21	109.37 (12)	C20—C21—H21	126.155
N2—C20—C25	123.17 (14)	C22—C21—H21	126.156
C21—C20—C25	127.45 (12)	C21—C22—H22	126.369
C20—C21—C22	107.69 (13)	C23—C22—H22	126.370
C21—C22—C23	107.26 (13)	C19—C24—H24A	109.466
N2—C23—C15	121.42 (13)	C19—C24—H24B	109.471
N2—C23—C22	107.79 (11)	C19—C24—H24C	109.467
C15—C23—C22	130.78 (13)	H24A—C24—H24B	109.474
F1—B1—F2	108.79 (12)	H24A—C24—H24C	109.473
F1—B1—N1	110.89 (13)	H24B—C24—H24C	109.476
F1—B1—N2	110.50 (12)	C20—C25—H25A	109.472
F2—B1—N1	109.74 (12)	C20—C25—H25B	109.473
F2—B1—N2	110.35 (13)	C20—C25—H25C	109.478
N1—B1—N2	106.56 (11)	H25A—C25—H25B	109.464
C1—O1—H1	109.476	H25A—C25—H25C	109.468
C2—C3—H3	118.907	H25B—C25—H25C	109.473

C16—N1—C19—C18	0.27 (15)	C1—C2—C7—C10	179.90 (11)
C16—N1—C19—C24	−179.62 (12)	C3—C2—C7—C8	−120.82 (13)
C19—N1—C16—C15	178.62 (12)	C3—C2—C7—C9	117.35 (13)
C19—N1—C16—C17	0.15 (15)	C3—C2—C7—C10	−1.00 (17)
C16—N1—B1—F1	−125.79 (14)	C7—C2—C3—C4	−177.28 (10)
C16—N1—B1—F2	113.99 (15)	C2—C3—C4—C5	−0.29 (19)
C16—N1—B1—N2	−5.49 (19)	C2—C3—C4—C15	179.24 (11)
B1—N1—C16—C15	4.9 (2)	C3—C4—C5—C6	−1.14 (19)
B1—N1—C16—C17	−173.54 (12)	C3—C4—C15—C16	−47.14 (18)
C19—N1—B1—F1	61.66 (19)	C3—C4—C15—C23	133.53 (13)
C19—N1—B1—F2	−58.56 (19)	C5—C4—C15—C16	132.38 (13)
C19—N1—B1—N2	−178.04 (12)	C5—C4—C15—C23	−46.95 (18)
B1—N1—C19—C18	173.90 (12)	C15—C4—C5—C6	179.33 (11)
B1—N1—C19—C24	−6.0 (2)	C4—C5—C6—C1	0.86 (19)
C20—N2—C23—C15	−179.76 (12)	C4—C5—C6—C11	−178.32 (11)
C20—N2—C23—C22	0.77 (15)	C1—C6—C11—C12	59.64 (16)
C23—N2—C20—C21	−0.21 (16)	C1—C6—C11—C13	−63.79 (15)
C23—N2—C20—C25	−179.57 (12)	C1—C6—C11—C14	178.40 (11)
C20—N2—B1—F1	−56.02 (19)	C5—C6—C11—C12	−121.24 (12)
C20—N2—B1—F2	64.34 (18)	C5—C6—C11—C13	115.33 (12)
C20—N2—B1—N1	−176.57 (13)	C5—C6—C11—C14	−2.48 (17)
B1—N2—C20—C21	179.05 (12)	C4—C15—C16—N1	−179.89 (11)
B1—N2—C20—C25	−0.3 (2)	C4—C15—C16—C17	−1.8 (2)
C23—N2—B1—F1	123.11 (13)	C4—C15—C23—N2	177.05 (11)
C23—N2—B1—F2	−116.52 (14)	C4—C15—C23—C22	−3.6 (2)
C23—N2—B1—N1	2.57 (19)	C16—C15—C23—N2	−2.3 (2)
B1—N2—C23—C15	1.0 (2)	C16—C15—C23—C22	177.06 (13)
B1—N2—C23—C22	−178.50 (12)	C23—C15—C16—N1	−0.6 (2)
O1—C1—C2—C3	178.10 (10)	C23—C15—C16—C17	177.49 (13)
O1—C1—C2—C7	−2.77 (17)	N1—C16—C17—C18	−0.52 (16)
O1—C1—C6—C5	−179.44 (10)	C15—C16—C17—C18	−178.77 (14)
O1—C1—C6—C11	−0.28 (19)	C16—C17—C18—C19	0.67 (17)
C2—C1—C6—C5	0.85 (18)	C17—C18—C19—N1	−0.59 (17)
C2—C1—C6—C11	180.00 (11)	C17—C18—C19—C24	179.29 (13)
C6—C1—C2—C3	−2.16 (19)	N2—C20—C21—C22	−0.45 (17)
C6—C1—C2—C7	176.96 (11)	C25—C20—C21—C22	178.88 (14)
C1—C2—C3—C4	1.87 (19)	C20—C21—C22—C23	0.91 (16)
C1—C2—C7—C8	60.08 (16)	C21—C22—C23—N2	−1.04 (16)
C1—C2—C7—C9	−61.75 (16)	C21—C22—C23—C15	179.55 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···F2ⁱ	0.96	2.54	3.4464 (18)	158

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···F2ⁱ	0.96	2.54	3.4464 (18)	158

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

The authors thank Dr Akihito Yamano (Rigaku Co. Ltd) for his kind technical support of data collection, and YM is grateful to the Grant-in-Aid for the project of a molecular mechanism of emotional control (Customer Care Plan 2014, 2015).

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hori, H., Uto, Y. & Nakata, E. (2010). Anticancer Res. 30, 3233–3242. CAS PubMed Google Scholar
Hori, H., Uto, Y. & Nakata, E. (2012). Anticancer Res. 32, 2235–2239. CAS PubMed Google Scholar
Nakata, E., Koizumi, M., Yamashita, Y., Onaka, K., Sakurai, Y., Kondo, N., Ono, K., Uto, Y. & Hori, H. (2011). Anticancer Res. 31, 2477–2481. CAS PubMed Google Scholar
Rigaku (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). RAPID-AUTO and CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 9| September 2015| Pages o694-o695

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