Tri­phenyl­boroxin complex with N-cyclo­hexyl­hydroxy­lamine and its isobutyr­aldehyde nitro­ne

Kliegel, W.; Lubkowitz, G.; Patrick, B.O.; Rettig, S.J.; Trotter, J.

doi:10.1107/S1600536802015052

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Triphenylboroxin complex with N-cyclohexylhydroxylamine and its isobutyraldehyde nitrone

W. Kliegel, G. Lubkowitz, B. O. Patrick, S. J. Rettig and J. Trotter

N-Cyclohexylhydroxylamine(O–B)triphenylboroxin N-cyclohexyl-C-(2-propyl)nitrone hemibenzene hemisolvate, C₂₄H₂₈B₃NO₄.C₁₀H₁₉NO·0.5C₆H₆, contains one molecule of N-cyclohexylhydroxylamine in its N-oxide form added to a boroxin heterocycle, with one molecule of N-cyclohexyl-C-(2-propyl)nitrone linked by an O

H—N hydrogen bond to the protonated hydroxylamine moiety, and a molecule of benzene which is located on a centre of inversion.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015052/om6103sup1.cif Contains datablocks global, III
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015052/om6103IIIsup2.hkl Contains datablock III

CCDC reference: 197485

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.007 Å
R factor = 0.047
wR factor = 0.057
Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           77.50
         From the CIF: _reflns_number_total               7215
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         7847
         Completeness (_total/calc)             91.95%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Triphenylboroxin and N-cyclohexyl-C-(2-propyl)nitrone form the 1:1 B–O–N adduct (I). B,N-Betainic complexes of this type, which are readily obtained as crystalline compounds from boroxins and nitrones [a series of various nitrone–triphenylboroxin 1:1 complexes has been synthesized (Lubkowitz, 1992)], correspond with other nitrone adducts of arylboronates (Paetzold et al., 1976; Kliegel, Preu et al., 1985) and diarylborinates (Kliegel, Lauterbach et al., 1987; Kliegel, Metge et al., 1997, 1998a,b; Kliegel et al., 2000, 2001). Addition of an equimolar amount of N-cyclohexylhydroxylamine to (I) was expected to give the complex (II), a double addition product of the nitrone as well as the hydroxylamine, the latter presumably in its N-oxide form, as recently was established for the B–O–N complex from triphenylboroxin and N,N-diethylhydoxylamine (Kliegel et al., 2002). An N—B coordination between the hydroxylamine and the boron compound could not be entirely excluded at this point, however. The crystalline reaction product (method A), which could also be obtained in a three component one-pot reaction from 3 mole quivalents (m.e.) of phenylboronic acid, 2 m.e. of N-cyclohexylhydroxylamine and 1 m.e. of isobutyraldehyde (method B), shows indeed the elemental analysis of (II). Some spectroscopic data, however, might call the adduct structure (II) into question. Comparing the IR spectra of (I) and of the adduct, the nitrone-C═N vibration is shifted from 1660 in (I) to about 1600 cm⁻¹ in the adduct, and in the ¹H NMR spectra, the signal of the N═CH methine H atom is displaced from δ = 6.97 in (I) to 6.73 p.p.m. in the adduct. Both the IR and the ¹H NMR data of the nitrone portion of the adduct coincide roughly with those of free N-cyclohexylisobutyraldonitrone. The X-ray analysis establishes the molecular structure (III) for the adduct, representing a triphenylboroxin complex with N-cyclohexylhydroxylamine in its N-oxide form, and the N-cyclohexylisobutyraldonitrone linked by an O···H—N⁺ hydrogen bond to the hydoxylamine moiety [the crystals contain additionally (solvate) benzene from the solvent mixture used for obtaining single crystals].

Obviously the N-alkylhydroxylamine (N-oxide form) is the stronger nucleophile and substitutes for the azomethine N-oxide (nitrone). It seems that, in this case, a mono-coordination with the boroxin ring system is preferred over a bifold coordination as depicted in (II). This is in line with the findings about the complex formation between triphenylboroxin, N,N-diethylhydroxylamine, and N,N-dimethylformamide (Kliegel et al., 2002). Multiple coordination had been suggested previously for a nitrone adduct of triphenyboroxin (Paetzold et al., 1975).

The crystal structure of (III) contains three separate fragments: an N-cyclohexylhydroxylamine–triphenylboroxin complex, an N-cyclohexyl-C-(2-propyl)nitrone (Fig. 1), and a benzene molecule which lies on a centre of inversion. The six-membered boroxin ring has an approximate envelope conformation, the O1—B2—O2—B3—O3 ring portion forming a rather distorted plane, with B1 on the `flap' [a closer description is perhaps a boat conformation, with B1 and to a lesser extent O2 displaced from the plane of the other four atoms]. The ring dimensions are very similar to those in related boroxin ring systems containing one tetrahedral sp³ B atom (Kliegel, Motzkus et al., 1985; Kliegel et al., 2002); in particular, two of the O—B bonds are short [O1—B2 = 1.345 (4) Å and O3—B3 = 1.347 (4) Å], with a high amount of double-bond charcter by (pp)π back donation. The longest O—B distance [O4—B1 = 1.530 (4)%A] is found in the exocyclic donor–acceptor bond between the N-oxide form of N-cyclohexylhydroxylamine and the boroxin moiety, very much like in the N,N-diethylhydroxylamine adduct reported (Kliegel et al., 2002). The geometry of the nitrone molecule, which shows a Z configuration with near planarity around the C═N double bond [C31—N2 = 1.304 (5) Å] is typical for aldonitrones (Bedford et al., 1991, and references therein; Kliegel, Preu et al., 1985; Kliegel et al., 1998a,b; Olszewski & Stadnicka, 1995; Greci & Sgarabotto, 1984; Christensen et al., 1990).

The hydroxylamine–boroxin complex and the nitrone are linked by an N1—H1···O5 hydrogen bond: N···O = 2.751 (3), N—H = 0.98 (calculated H-atom site, assuming tetrahedral angles at N1), H···O = 1.80 Å and N—H···O = 163°. There is also an intra-boroxine contact which might represent a bifurcation of this hydrogen-bond system [N1—H1···O3: N···O = 2.904 (3), H···O = 2.45 Å and N—H···O = 108°]; this arrangement results in fairly short O5···B3 [2.860 (5) Å] and O5···O3 [2.991 (3) Å] distances. Finally, there is an inter-boroxin hydrogen bond [N1—H2···O4: N···O = 2.852 (3), N—H = 0.98, H···O = 2.03 Å and N—H···O = 141°].

The thermal motion is rather high, as evidenced by the ellipsoids in Fig. 1.

Experimental top

N-Cyclohexyl-C-(2-propyl)nitrone(O—B)triphenylboroxin, (I): triphenylboroxin (2.50 g, 8 mmol) and N-cyclohexyl-C-(2-propyl)nitrone (1.35 g, 8 mmol) [N-(2-methylpropylidene)cyclohexanamine N-oxide; prepared according to the literature (Coates & Cummings, 1986)] were dissolved in 50 ml of ethanol and refluxed for 30 min. The solvent was distilled off in vacuo and the remaining oil mixed with a small amount of toluene. A crystalline substance was obtained after addition of petroleum ether and cooling. Yield: 3.66 g (95%) of colorless crystals; m.p. 413–415 K (from toluene/petroleum ether). IR (KBr): 1660 (C═N), 1600 cm^-l (phenyl-C═C). ¹H NMR (90 MHz, DMSO-d₆/TMS), δ (p.p.m.): 1.00 [d, J = 7 Hz, (CH₃)₂C], 1.06–1.90 [m, (CH₂)₅], 3.02 (m, J = 7 Hz, N═C—CH), 3.77 (m, N—CH), 6.97 (d, J = 7 Hz, N═CH), 7.15–7.43 (m, 9 aromatic H), 7.68–7.96 (m, 6 aromatic H). Analysis calculated for C₂₈H₃₄B₃NO₄: C 69.92, H 7.12, B 6.74, N 2.91%; found: C 69.92, H 7.13, B 6.95, N 3.04%.

N-Cyclohexylhydroxylamine(O—B)triphenylboroxin N-cyclohexyl-C-(2- propyl)nitrone, (III) [2-(cyclohexylammonio-oxy)-2,4,6-triphenyl-1,3,5-trioxa-4,6-dibora-2- boratacyclohexane N-(2-methylpropylidene)cyclohexanamine N-oxide]: method A: (I) (1.44 g, 3 mmol) and N-cyclohexylhydroxylamine (0.35 g, 3 mmol) were suspended in 30 ml of ethanol and refluxed for 30 min. The solution was evaporated to half of the volume and mixed with 200 ml of petroleum ether. Upon cooling, 1.69 g (90%) of colorless crystals were obtained; m.p. 379–380 K (from ethanol/petroleum ether). IR (KBr): 2710, 2560 (N—H), 1600 cm^-l (C═N/C═C). ¹H NMR (90 MHz, DMSO-d₆-TMS), δ (p.p.m.): 1.00 [d, J = 7 Hz, (CH₃)₂], 1.11–2.24 [m, 2 (CH₂)₅], 2.89 (m, J = 7 Hz, N═C—CH), 3.17–3.83 (m and m, 2 N—CH), 6.73 (d, J = 7 Hz, N═CH), 7.03–7.49 (m, 9 aromatic H), 7.68–7.81 (m, 6 aromatic H), 7.91 (s, exchangeable, NH), 9.50 (s, very broad, exchangeable, NH). Analysis calculated for C₃₄H₄₇B₃N₂O₅: C 68.50, H 7.95, B 5.44, N 4.70%; found: C 68.22, H 7.97, B 5.34, N 4.80%.

Method B: phenylboronic acid (1.83 g, 15 mmol) and N-cyclohexylhydroxylamine (1.15 g, 10 mmol) were dissolved in 40 ml of ethanol and mixed with 2-methylpropionaldehyde (isobutyraldehyde) (0.36 g, 5 mmol). After 1 h of refluxing, the solution is evaporated to a small volume. Addition of petroleum ether and cooling yields 2.69 g (90%) of colorless crystals, identical with the product from method A.

Single crystals suitable for X-ray analysis were obtained by slow crystallization from a solvent mixture of ethanol, petroleum ether, and a small amount of benzene.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: MITHRIL (Gilmore, 1984); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures top

Fig. 1. Views of the hydroxylamineboroxin complex and the nitrone components of the structure (ellipsoids at the 33% probability level).

(III) top

Crystal data top

C₂₄H₂₈B₃NO₄·C₁₀H₁₉NO·0.5C₆H₆	F(000) = 1364
M_r = 635.24	D_x = 1.145 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 13.660 (1) Å	Cell parameters from 25 reflections
b = 19.504 (3) Å	θ = 46.5–73.8°
c = 14.433 (2) Å	µ = 0.58 mm⁻¹
β = 106.626 (8)°	T = 294 K
V = 3684.6 (8) Å³	Prism, colorless
Z = 4	0.35 × 0.30 × 0.25 mm

Data collection top

Rigaku AFC-6S diffractometer	3098 reflections with I > 3σ(I)
Radiation source: X-ray tube	R_int = 0.038
Graphite monochromator	θ_max = 77.5°, θ_min = 1.7°
ω–2θ scans	h = 0→17
Absorption correction: ψ scan AFC6 (Molecular Structure Corporation, 1989)	k = 0→24
T_min = 0.84, T_max = 0.87	l = −18→17
7579 measured reflections	3 standard reflections every 250 reflections
7215 independent reflections	intensity decay: 2.2%

Refinement top

Refinement on F	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	Weighting scheme based on measured s.u.'s w = 1/[σ²(F_o) + 0.0004F_o²]
wR(F²) = 0.057	(Δ/σ)_max = 0.001
S = 1.89	Δρ_max = 0.22 e Å⁻³
7215 reflections	Δρ_min = −0.14 e Å⁻³
425 parameters	Extinction correction: MSC (1989), equ(3) Acta Cryst.(1968) A24, 213
0 restraints	Extinction coefficient: 1.69E-6 (3)

Crystal data top

C₂₄H₂₈B₃NO₄·C₁₀H₁₉NO·0.5C₆H₆	V = 3684.6 (8) Å³
M_r = 635.24	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 13.660 (1) Å	µ = 0.58 mm⁻¹
b = 19.504 (3) Å	T = 294 K
c = 14.433 (2) Å	0.35 × 0.30 × 0.25 mm
β = 106.626 (8)°

Data collection top

Rigaku AFC-6S diffractometer	3098 reflections with I > 3σ(I)
Absorption correction: ψ scan AFC6 (Molecular Structure Corporation, 1989)	R_int = 0.038
T_min = 0.84, T_max = 0.87	3 standard reflections every 250 reflections
7579 measured reflections	intensity decay: 2.2%
7215 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.057	H-atom parameters constrained
S = 1.89	Δρ_max = 0.22 e Å⁻³
7215 reflections	Δρ_min = −0.14 e Å⁻³
425 parameters

Special details top

Experimental. The scan width was (1.10 + 0.20tanθ)° with an ω scan speed of 32° per minute (up to 10 scans to achieve I/σ(I) > 40). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. Three standard reflections decreased gradually in intensity by 2.2%; a linear decay correction was applied to the data.

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

	x	y	z	U_iso*/U_eq
O1	0.5734 (1)	0.14938 (9)	0.6865 (1)	0.0584 (11)
O2	0.6121 (2)	0.2567 (1)	0.6286 (1)	0.0619 (11)
O3	0.6264 (1)	0.1559 (1)	0.5411 (1)	0.0608 (13)
O4	0.5511 (1)	0.05186 (9)	0.5795 (1)	0.0579 (10)
O5	0.4106 (2)	0.2064 (1)	0.4821 (2)	0.075 (1)
N1	0.4491 (2)	0.0704 (1)	0.5290 (2)	0.054 (1)
N2	0.3544 (2)	0.2485 (1)	0.4183 (2)	0.065 (1)
C1	0.3753 (2)	0.0605 (1)	0.5866 (2)	0.061 (1)
C2	0.2689 (3)	0.0698 (2)	0.5196 (2)	0.075 (2)
C3	0.1907 (3)	0.0592 (3)	0.5743 (3)	0.106 (2)
C4	0.2030 (4)	−0.0098 (3)	0.6244 (4)	0.120 (4)
C5	0.3095 (4)	−0.0196 (2)	0.6877 (3)	0.111 (4)
C6	0.3881 (3)	−0.0094 (2)	0.6335 (3)	0.086 (2)
C7	0.7280 (3)	0.0789 (1)	0.6770 (2)	0.066 (1)
C8	0.8140 (3)	0.0885 (2)	0.6462 (3)	0.095 (2)
C9	0.9081 (4)	0.0606 (3)	0.6951 (5)	0.136 (4)
C10	0.9174 (5)	0.0231 (3)	0.7756 (6)	0.151 (4)
C11	0.8366 (5)	0.0122 (2)	0.8081 (4)	0.139 (4)
C12	0.7409 (3)	0.0404 (2)	0.7595 (3)	0.099 (2)
C13	0.5354 (2)	0.2568 (2)	0.7678 (2)	0.061 (1)
C14	0.5469 (3)	0.3273 (2)	0.7816 (2)	0.073 (2)
C15	0.5142 (3)	0.3613 (2)	0.8500 (3)	0.095 (2)
C16	0.4679 (3)	0.3264 (3)	0.9074 (3)	0.105 (2)
C17	0.4545 (3)	0.2567 (3)	0.8971 (3)	0.106 (2)
C18	0.4881 (3)	0.2230 (2)	0.8269 (3)	0.084 (2)
C19	0.6494 (2)	0.2709 (2)	0.4690 (2)	0.068 (2)
C20	0.6768 (3)	0.2436 (2)	0.3924 (3)	0.099 (2)
C21	0.6977 (4)	0.2857 (4)	0.3215 (3)	0.129 (4)
C22	0.6906 (4)	0.3549 (4)	0.3297 (4)	0.143 (5)
C23	0.6661 (4)	0.3829 (3)	0.4047 (4)	0.123 (4)
C24	0.6442 (3)	0.3416 (2)	0.4737 (3)	0.092 (2)
C25	0.3001 (3)	0.3015 (2)	0.4577 (2)	0.070 (2)
C26	0.2426 (3)	0.2706 (2)	0.5202 (3)	0.105 (2)
C27	0.1875 (4)	0.3241 (3)	0.5607 (4)	0.141 (4)
C28	0.2612 (6)	0.3775 (4)	0.6155 (4)	0.187 (6)
C29	0.3238 (4)	0.4075 (3)	0.5553 (5)	0.155 (5)
C30	0.3771 (3)	0.3541 (2)	0.5133 (3)	0.109 (2)
C31	0.3497 (3)	0.2467 (2)	0.3268 (3)	0.077 (2)
C32	0.4041 (3)	0.1965 (2)	0.2844 (3)	0.096 (2)
C33	0.4274 (3)	0.2264 (3)	0.1937 (3)	0.130 (4)
C34	0.3415 (3)	0.1320 (2)	0.2594 (3)	0.115 (2)
C35	1.0162 (6)	0.4747 (5)	0.4188 (4)	0.142 (5)
C36	0.9448 (5)	0.4472 (3)	0.4547 (6)	0.139 (5)
C37	0.9279 (4)	0.4712 (4)	0.5359 (6)	0.128 (4)
B1	0.6203 (3)	0.1126 (2)	0.6218 (3)	0.058 (2)
B2	0.5745 (3)	0.2183 (2)	0.6908 (3)	0.057 (2)
B3	0.6272 (3)	0.2248 (2)	0.5481 (3)	0.060 (2)
H1	0.4483	0.1189	0.5108	0.065*
H2	0.4269	0.0423	0.4704	0.065*
H3	0.3878	0.0956	0.6372	0.072*
H4	0.2620	0.1162	0.4926	0.090*
H5	0.2572	0.0363	0.4669	0.090*
H6	0.1989	0.0954	0.6230	0.128*
H7	0.1222	0.0620	0.5287	0.128*
H8	0.1556	−0.0126	0.6640	0.144*
H9	0.1870	−0.0461	0.5754	0.144*
H10	0.3225	0.0136	0.7408	0.133*
H11	0.3161	−0.0662	0.7141	0.133*
H12	0.3792	−0.0448	0.5835	0.104*
H13	0.4568	−0.0131	0.6788	0.104*
H14	0.8083	0.1158	0.5880	0.114*
H15	0.9675	0.0682	0.6712	0.163*
H16	0.9839	0.0037	0.8104	0.180*
H17	0.8439	−0.0156	0.8662	0.167*
H18	0.6825	0.0326	0.7849	0.119*
H19	0.5798	0.3535	0.7408	0.089*
H20	0.5241	0.4110	0.8576	0.114*
H21	0.4441	0.3510	0.9561	0.126*
H22	0.4217	0.2312	0.9385	0.128*
H23	0.4777	0.1734	0.8193	0.101*
H24	0.6819	0.1937	0.3870	0.118*
H25	0.7170	0.2657	0.2670	0.155*
H26	0.7036	0.3847	0.2798	0.171*
H27	0.6637	0.4329	0.4106	0.147*
H28	0.6244	0.3629	0.5272	0.111*
H29	0.2515	0.3247	0.4035	0.084*
H30	0.1926	0.2381	0.4819	0.125*
H31	0.2905	0.2464	0.5738	0.125*
H32	0.1360	0.3462	0.5076	0.168*
H33	0.1539	0.3021	0.6046	0.168*
H34	0.2225	0.4144	0.6350	0.225*
H35	0.3072	0.3563	0.6733	0.225*
H36	0.2785	0.4338	0.5022	0.186*
H37	0.3752	0.4382	0.5960	0.186*
H38	0.4285	0.3311	0.5656	0.132*
H39	0.4107	0.3759	0.4694	0.132*
H40	0.3074	0.2810	0.2839	0.094*
H41	0.4689	0.1853	0.3324	0.115*
H42	0.4694	0.2677	0.2115	0.157*
H43	0.4644	0.1923	0.1669	0.157*
H44	0.3632	0.2381	0.1452	0.157*
H45	0.2761	0.1426	0.2119	0.138*
H46	0.3787	0.0983	0.2320	0.138*
H47	0.3291	0.1132	0.3179	0.138*
H48	1.0278	0.4559	0.3599	0.171*
H49	0.9040	0.4085	0.4209	0.166*
H50	0.8762	0.4502	0.5619	0.155*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.072 (1)	0.042 (1)	0.063 (1)	0.002 (1)	0.021 (1)	−0.003 (1)
O2	0.072 (1)	0.046 (1)	0.065 (1)	−0.005 (1)	0.016 (1)	−0.006 (1)
O3	0.065 (1)	0.050 (1)	0.065 (1)	0.003 (1)	0.017 (1)	−0.002 (1)
O4	0.053 (1)	0.044 (1)	0.070 (1)	0.005 (1)	0.007 (1)	−0.004 (1)
O5	0.083 (2)	0.048 (1)	0.080 (1)	0.016 (1)	0.004 (1)	0.012 (1)
N1	0.056 (2)	0.043 (1)	0.062 (2)	0.004 (1)	0.010 (1)	−0.003 (1)
N2	0.060 (2)	0.047 (1)	0.075 (2)	0.003 (1)	0.004 (1)	−0.002 (1)
C1	0.066 (2)	0.055 (2)	0.063 (2)	−0.000 (2)	0.024 (2)	−0.006 (2)
C2	0.061 (2)	0.077 (2)	0.086 (2)	−0.002 (2)	0.018 (2)	0.004 (2)
C3	0.069 (3)	0.148 (4)	0.107 (3)	−0.007 (3)	0.032 (2)	−0.003 (3)
C4	0.120 (4)	0.146 (4)	0.113 (4)	−0.051 (3)	0.064 (3)	−0.009 (3)
C5	0.132 (4)	0.111 (3)	0.108 (3)	−0.006 (3)	0.062 (3)	0.019 (3)
C6	0.102 (3)	0.076 (2)	0.089 (3)	0.006 (2)	0.040 (2)	0.019 (2)
C7	0.070 (2)	0.040 (2)	0.075 (2)	0.001 (2)	0.003 (2)	−0.015 (2)
C8	0.065 (3)	0.098 (3)	0.114 (3)	0.010 (2)	0.012 (2)	−0.014 (2)
C9	0.063 (3)	0.128 (4)	0.197 (6)	0.020 (3)	0.004 (4)	−0.026 (4)
C10	0.092 (4)	0.095 (4)	0.205 (7)	0.025 (4)	−0.052 (5)	−0.033 (4)
C11	0.135 (5)	0.084 (3)	0.147 (5)	0.018 (4)	−0.043 (4)	0.020 (3)
C12	0.095 (3)	0.073 (2)	0.105 (3)	0.008 (2)	−0.008 (3)	0.017 (2)
C13	0.056 (2)	0.055 (2)	0.064 (2)	0.002 (2)	0.007 (2)	−0.005 (2)
C14	0.086 (3)	0.059 (2)	0.073 (2)	0.010 (2)	0.016 (2)	−0.009 (2)
C15	0.114 (3)	0.073 (3)	0.094 (3)	0.013 (2)	0.024 (3)	−0.021 (2)
C16	0.109 (3)	0.107 (4)	0.103 (3)	0.020 (3)	0.039 (3)	−0.031 (3)
C17	0.108 (3)	0.121 (4)	0.104 (3)	−0.003 (3)	0.055 (3)	−0.016 (3)
C18	0.094 (3)	0.072 (2)	0.090 (3)	−0.007 (2)	0.032 (2)	−0.013 (2)
C19	0.054 (2)	0.068 (2)	0.068 (2)	−0.008 (2)	0.008 (2)	0.005 (2)
C20	0.093 (3)	0.113 (3)	0.091 (3)	−0.020 (2)	0.028 (3)	0.001 (3)
C21	0.119 (4)	0.186 (6)	0.090 (4)	−0.040 (4)	0.044 (3)	0.005 (4)
C22	0.127 (5)	0.179 (7)	0.111 (4)	−0.047 (5)	0.015 (4)	0.057 (5)
C23	0.125 (4)	0.104 (4)	0.127 (4)	−0.018 (3)	0.016 (3)	0.043 (4)
C24	0.094 (3)	0.073 (2)	0.106 (3)	−0.007 (2)	0.020 (2)	0.026 (2)
C25	0.070 (2)	0.061 (2)	0.073 (2)	0.016 (2)	0.008 (2)	0.004 (2)
C26	0.098 (3)	0.109 (3)	0.111 (3)	0.033 (3)	0.036 (3)	0.014 (3)
C27	0.140 (5)	0.179 (5)	0.111 (4)	0.050 (4)	0.050 (3)	−0.001 (4)
C28	0.178 (7)	0.242 (8)	0.118 (5)	0.113 (6)	0.000 (4)	−0.075 (5)
C29	0.123 (5)	0.116 (4)	0.195 (6)	0.032 (3)	−0.006 (4)	−0.087 (4)
C30	0.097 (3)	0.070 (2)	0.135 (4)	0.012 (2)	−0.009 (3)	−0.029 (2)
C31	0.073 (2)	0.081 (2)	0.067 (2)	0.015 (2)	0.001 (2)	−0.003 (2)
C32	0.076 (3)	0.107 (3)	0.094 (3)	0.018 (2)	0.008 (2)	−0.016 (3)
C33	0.103 (3)	0.201 (5)	0.099 (3)	0.006 (3)	0.045 (3)	0.007 (3)
C34	0.112 (3)	0.084 (3)	0.135 (4)	0.009 (3)	0.010 (3)	−0.022 (3)
C35	0.123 (5)	0.176 (6)	0.126 (5)	0.002 (4)	0.034 (4)	−0.014 (5)
C36	0.113 (5)	0.131 (5)	0.171 (7)	−0.004 (4)	0.040 (4)	−0.023 (4)
C37	0.117 (5)	0.129 (5)	0.145 (5)	0.005 (4)	0.048 (4)	0.027 (4)
B1	0.064 (2)	0.043 (2)	0.063 (2)	−0.001 (2)	0.011 (2)	−0.005 (2)
B2	0.054 (2)	0.052 (2)	0.057 (2)	0.001 (2)	0.005 (2)	−0.004 (2)
B3	0.048 (2)	0.059 (2)	0.067 (2)	−0.003 (2)	0.007 (2)	0.000 (2)

Geometric parameters (Å, º) top

O1—B1	1.463 (5)	C16—H21	0.98
O1—B2	1.345 (4)	C17—C18	1.391 (7)
O2—B2	1.376 (5)	C17—H22	0.98
O2—B3	1.384 (5)	C18—H23	0.98
O3—B1	1.460 (5)	C19—C20	1.372 (6)
O3—B3	1.347 (4)	C19—C24	1.383 (5)
O4—N1	1.422 (3)	C19—B3	1.550 (6)
O4—B1	1.530 (4)	C20—C21	1.404 (8)
O5—N2	1.306 (3)	C20—H24	0.98
N1—C1	1.491 (4)	C21—C22	1.36 (1)
N1—H1	0.98	C21—H25	0.98
N1—H2	0.98	C22—C23	1.338 (9)
N2—C25	1.478 (5)	C22—H26	0.98
N2—C31	1.304 (5)	C23—C24	1.379 (8)
C1—C2	1.509 (4)	C23—H27	0.98
C1—C6	1.510 (4)	C24—H28	0.98
C1—H3	0.98	C25—C26	1.483 (6)
C2—C3	1.513 (6)	C25—C30	1.523 (5)
C2—H4	0.98	C25—H29	0.98
C2—H5	0.98	C26—C27	1.500 (7)
C3—C4	1.514 (8)	C26—H30	0.98
C3—H6	0.98	C26—H31	0.98
C3—H7	0.98	C27—C28	1.506 (9)
C4—C5	1.492 (7)	C27—H32	0.98
C4—H8	0.98	C27—H33	0.98
C4—H9	0.98	C28—C29	1.50 (1)
C5—C6	1.512 (7)	C28—H34	0.98
C5—H10	0.98	C28—H35	0.98
C5—H11	0.98	C29—C30	1.495 (8)
C6—H12	0.98	C29—H36	0.98
C6—H13	0.98	C29—H37	0.98
C7—C8	1.383 (6)	C30—H38	0.98
C7—C12	1.376 (5)	C30—H39	0.98
C7—B1	1.600 (5)	C31—C32	1.465 (6)
C8—C9	1.388 (6)	C31—H40	0.98
C8—H14	0.98	C32—C33	1.547 (7)
C9—C10	1.35 (1)	C32—C34	1.506 (5)
C9—H15	0.98	C32—H41	0.98
C10—C11	1.33 (1)	C33—H42	0.98
C10—H16	0.98	C33—H43	0.98
C11—C12	1.407 (7)	C33—H44	0.98
C11—H17	0.98	C34—H45	0.98
C12—H18	0.98	C34—H46	0.98
C13—C14	1.392 (5)	C34—H47	0.98
C13—C18	1.377 (6)	C35—C36	1.34 (1)
C13—B2	1.557 (6)	C35—C37ⁱ	1.36 (1)
C14—C15	1.366 (6)	C35—H48	0.98
C14—H19	0.98	C36—C37	1.34 (1)
C15—C16	1.360 (7)	C36—H49	0.98
C15—H20	0.98	C37—H50	0.98
C16—C17	1.374 (8)

O1···O5	3.336 (3)	O5···B2	3.206 (4)
O2···O5	3.111 (3)	O5···C1	3.320 (3)
O3···O5	2.991 (3)	O5···C2	3.426 (5)
O4···N1ⁱⁱ	2.852 (3)	O5···B1	3.509 (4)
O4···O4ⁱⁱ	3.078 (3)	O5···C19	3.551 (4)
O4···C6ⁱⁱ	3.505 (5)	N1···N1ⁱⁱ	3.293 (5)
O4···C1ⁱⁱ	3.597 (3)	C12···C34ⁱⁱ	3.532 (5)
O5···N1	2.751 (3)	C17···C21ⁱⁱⁱ	3.463 (7)
O5···B3	2.860 (5)

B1—O1—B2	121.2 (3)	C20—C21—C22	118.8 (5)
B2—O2—B3	118.4 (3)	C20—C21—H25	120.7
B1—O3—B3	121.2 (3)	C22—C21—H25	120.5
N1—O4—B1	114.2 (2)	C21—C22—C23	121.1 (6)
O4—N1—C1	113.6 (2)	C21—C22—H26	119.5
O4—N1—H1	108.5	C23—C22—H26	119.5
O4—N1—H2	108.4	C22—C23—C24	120.2 (6)
C1—N1—H1	108.5	C22—C23—H27	119.9
C1—N1—H2	108.5	C24—C23—H27	119.9
H1—N1—H2	109.3	C19—C24—C23	121.5 (4)
O5—N2—C25	115.3 (3)	C19—C24—H28	119.4
O5—N2—C31	123.1 (3)	C23—C24—H28	119.1
C25—N2—C31	121.6 (3)	N2—C25—C26	111.2 (3)
N1—C1—C2	107.9 (2)	N2—C25—C30	109.1 (3)
N1—C1—C6	110.9 (3)	N2—C25—H29	108.4
N1—C1—H3	108.9	C26—C25—C30	111.1 (3)
C2—C1—C6	111.3 (3)	C26—C25—H29	108.5
C2—C1—H3	108.9	C30—C25—H29	108.5
C6—C1—H3	108.9	C25—C26—C27	111.5 (4)
C1—C2—C3	110.1 (3)	C25—C26—H30	109.0
C1—C2—H4	109.4	C25—C26—H31	109.0
C1—C2—H5	109.3	C27—C26—H30	108.9
C3—C2—H4	109.4	C27—C26—H31	108.9
C3—C2—H5	109.3	H30—C26—H31	109.5
H4—C2—H5	109.4	C26—C27—C28	110.6 (5)
C2—C3—C4	111.8 (4)	C26—C27—H32	109.2
C2—C3—H6	108.8	C26—C27—H33	109.1
C2—C3—H7	108.9	C28—C27—H32	109.2
C4—C3—H6	108.9	C28—C27—H33	109.2
C4—C3—H7	108.9	H32—C27—H33	109.5
H6—C3—H7	109.5	C27—C28—C29	111.8 (5)
C3—C4—C5	111.2 (4)	C27—C28—H34	108.9
C3—C4—H8	109.1	C27—C28—H35	108.9
C3—C4—H9	109.0	C29—C28—H34	108.9
C5—C4—H8	109.1	C29—C28—H35	108.9
C5—C4—H9	109.0	H34—C28—H35	109.4
H8—C4—H9	109.4	C28—C29—C30	112.8 (5)
C4—C5—C6	112.3 (4)	C28—C29—H36	108.6
C4—C5—H10	108.7	C28—C29—H37	108.7
C4—C5—H11	108.8	C30—C29—H36	108.6
C6—C5—H10	108.7	C30—C29—H37	108.7
C6—C5—H11	108.9	H36—C29—H37	109.4
H10—C5—H11	109.4	C25—C30—C29	109.9 (4)
C1—C6—C5	110.0 (3)	C25—C30—H38	109.4
C1—C6—H12	109.4	C25—C30—H39	109.4
C1—C6—H13	109.3	C29—C30—H38	109.3
C5—C6—H12	109.3	C29—C30—H39	109.4
C5—C6—H13	109.3	H38—C30—H39	109.4
H12—C6—H13	109.4	N2—C31—C32	123.9 (3)
C8—C7—C12	116.2 (3)	N2—C31—H40	118.1
C8—C7—B1	121.9 (3)	C32—C31—H40	118.1
C12—C7—B1	121.8 (4)	C31—C32—C33	110.7 (4)
C7—C8—C9	122.1 (4)	C31—C32—C34	109.7 (4)
C7—C8—H14	118.9	C31—C32—H41	108.5
C9—C8—H14	119.0	C33—C32—C34	110.6 (4)
C8—C9—C10	119.7 (6)	C33—C32—H41	108.6
C8—C9—H15	120.1	C34—C32—H41	108.6
C10—C9—H15	120.2	C32—C33—H42	109.6
C9—C10—C11	120.4 (6)	C32—C33—H43	109.4
C9—C10—H16	119.8	C32—C33—H44	109.5
C11—C10—H16	119.8	H42—C33—H43	109.4
C10—C11—C12	120.4 (5)	H42—C33—H44	109.5
C10—C11—H17	119.8	H43—C33—H44	109.5
C12—C11—H17	119.7	C32—C34—H45	109.4
C7—C12—C11	121.0 (5)	C32—C34—H46	109.4
C7—C12—H18	119.5	C32—C34—H47	109.4
C11—C12—H18	119.5	H45—C34—H46	109.5
C14—C13—C18	116.0 (3)	H45—C34—H47	109.5
C14—C13—B2	122.1 (3)	H46—C34—H47	109.5
C18—C13—B2	121.9 (4)	C36—C35—C37ⁱ	119.8 (7)
C13—C14—C15	122.4 (4)	C36—C35—H48	120.1
C13—C14—H19	118.8	C37ⁱ—C35—H48	120.1
C15—C14—H19	118.8	C35—C36—C37	121.6 (6)
C14—C15—C16	120.2 (4)	C35—C36—H49	119.2
C14—C15—H20	119.8	C37—C36—H49	119.2
C16—C15—H20	120.0	C35ⁱ—C37—C36	118.6 (7)
C15—C16—C17	120.0 (5)	C35ⁱ—C37—H50	120.6
C15—C16—H21	120.0	C36—C37—H50	120.8
C17—C16—H21	120.0	O1—B1—O3	111.2 (3)
C16—C17—C18	119.0 (4)	O1—B1—O4	107.5 (3)
C16—C17—H22	120.4	O1—B1—C7	113.1 (3)
C18—C17—H22	120.6	O3—B1—O4	107.4 (3)
C13—C18—C17	122.4 (4)	O3—B1—C7	112.4 (3)
C13—C18—H23	118.8	O4—B1—C7	104.8 (2)
C17—C18—H23	118.7	O1—B2—O2	121.0 (4)
C20—C19—C24	117.1 (4)	O1—B2—C13	120.9 (4)
C20—C19—B3	121.6 (4)	O2—B2—C13	118.1 (3)
C24—C19—B3	121.2 (3)	O2—B3—O3	120.7 (3)
C19—C20—C21	121.3 (4)	O2—B3—C19	117.7 (3)
C19—C20—H24	119.4	O3—B3—C19	121.5 (4)
C21—C20—H24	119.3

O1—B1—O3—B3	24.1 (4)	C3—C2—C1—C6	57.3 (4)
O1—B1—O4—N1	57.7 (3)	C3—C4—C5—C6	−54.4 (5)
O1—B1—C7—C8	−129.7 (3)	C7—C8—C9—C10	−0.3 (8)
O1—B1—C7—C12	48.3 (4)	C7—C12—C11—C10	0.9 (7)
O1—B2—O2—B3	14.4 (4)	C7—B1—O1—B2	103.8 (3)
O1—B2—C13—C14	172.1 (3)	C7—B1—O3—B3	−103.8 (3)
O1—B2—C13—C18	−7.3 (4)	C8—C7—C12—C11	−0.7 (5)
O2—B2—O1—B1	5.6 (4)	C8—C9—C10—C11	0.5 (9)
O2—B2—C13—C14	−6.6 (4)	C9—C8—C7—C12	0.4 (6)
O2—B2—C13—C18	173.9 (3)	C9—C8—C7—B1	178.6 (4)
O2—B3—O3—B1	−6.4 (4)	C9—C10—C11—C12	−0.8 (9)
O2—B3—C19—C20	172.4 (3)	C11—C12—C7—B1	−178.8 (3)
O2—B3—C19—C24	−6.4 (4)	C13—C14—C15—C16	−0.4 (5)
O3—B1—O1—B2	−23.7 (4)	C13—C18—C17—C16	0.7 (5)
O3—B1—O4—N1	−62.1 (3)	C13—B2—O1—B1	−173.1 (3)
O3—B1—C7—C8	−2.9 (4)	C13—B2—O2—B3	−166.9 (3)
O3—B1—C7—C12	175.1 (3)	C14—C13—C18—C17	−0.7 (5)
O3—B3—O2—B2	−14.0 (5)	C14—C15—C16—C17	0.4 (5)
O3—B3—C19—C20	−5.1 (5)	C15—C14—C13—C18	0.5 (5)
O3—B3—C19—C24	176.1 (3)	C15—C14—C13—B2	−179.0 (3)
O4—N1—C1—C2	−170.1 (2)	C15—C16—C17—C18	−0.6 (5)
O4—N1—C1—C6	−48.0 (3)	C17—C18—C13—B2	178.8 (3)
O4—B1—O1—B2	−141.0 (2)	C19—C20—C21—C22	0.1 (6)
O4—B1—O3—B3	141.4 (3)	C19—C24—C23—C22	1.7 (7)
O4—B1—C7—C8	113.4 (3)	C19—B3—O2—B2	168.5 (3)
O4—B1—C7—C12	−68.5 (4)	C19—B3—O3—B1	171.0 (3)
O5—N2—C25—C26	−50.9 (3)	C20—C19—C24—C23	−0.3 (5)
O5—N2—C25—C30	71.9 (4)	C20—C21—C22—C23	1.3 (7)
O5—N2—C31—C32	1.8 (5)	C21—C20—C19—C24	−0.6 (5)
N1—O4—B1—C7	178.2 (3)	C21—C20—C19—B3	−179.4 (3)
N1—C1—C2—C3	179.2 (3)	C21—C22—C23—C24	−2.2 (7)
N1—C1—C6—C5	−177.4 (3)	C23—C24—C19—B3	178.5 (4)
N2—C25—C26—C27	179.8 (3)	C25—N2—C31—C32	178.3 (3)
N2—C25—C30—C29	−179.0 (4)	C25—C26—C27—C28	−56.5 (5)
N2—C31—C32—C33	−152.2 (4)	C25—C30—C29—C28	53.9 (5)
N2—C31—C32—C34	85.4 (4)	C26—C25—N2—C31	132.3 (3)
C1—N1—O4—B1	−100.5 (3)	C26—C25—C30—C29	−56.1 (5)
C1—C2—C3—C4	−55.3 (4)	C26—C27—C28—C29	53.5 (7)
C1—C6—C5—C4	55.9 (4)	C27—C26—C25—C30	58.2 (4)
C2—C1—C6—C5	−57.3 (4)	C27—C28—C29—C30	−53.5 (7)
C2—C3—C4—C5	54.1 (5)	C30—C25—N2—C31	−104.9 (3)

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₈B₃NO₄·C₁₀H₁₉NO·0.5C₆H₆
M_r	635.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	13.660 (1), 19.504 (3), 14.433 (2)
β (°)	106.626 (8)
V (Å³)	3684.6 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Rigaku AFC-6S diffractometer
Absorption correction	ψ scan AFC6 (Molecular Structure Corporation, 1989)
T_min, T_max	0.84, 0.87
No. of measured, independent and observed [I > 3σ(I)] reflections	7579, 7215, 3098
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.057, 1.89
No. of reflections	7215
No. of parameters	425
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.14

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1989), MITHRIL (Gilmore, 1984), TEXSAN.

Selected geometric parameters (Å, º) top

O1—B1	1.463 (5)	C13—C18	1.377 (6)
O1—B2	1.345 (4)	C13—B2	1.557 (6)
O2—B2	1.376 (5)	C14—C15	1.366 (6)
O2—B3	1.384 (5)	C15—C16	1.360 (7)
O3—B1	1.460 (5)	C16—C17	1.374 (8)
O3—B3	1.347 (4)	C17—C18	1.391 (7)
O4—N1	1.422 (3)	C19—C20	1.372 (6)
O4—B1	1.530 (4)	C19—C24	1.383 (5)
O5—N2	1.306 (3)	C19—B3	1.550 (6)
N1—C1	1.491 (4)	C20—C21	1.404 (8)
N2—C25	1.478 (5)	C21—C22	1.36 (1)
N2—C31	1.304 (5)	C22—C23	1.338 (9)
C1—C2	1.509 (4)	C23—C24	1.379 (8)
C1—C6	1.510 (4)	C25—C26	1.483 (6)
C2—C3	1.513 (6)	C25—C30	1.523 (5)
C3—C4	1.514 (8)	C26—C27	1.500 (7)
C4—C5	1.492 (7)	C27—C28	1.506 (9)
C5—C6	1.512 (7)	C28—C29	1.50 (1)
C7—C8	1.383 (6)	C29—C30	1.495 (8)
C7—C12	1.376 (5)	C31—C32	1.465 (6)
C7—B1	1.600 (5)	C32—C33	1.547 (7)
C8—C9	1.388 (6)	C32—C34	1.506 (5)
C9—C10	1.35 (1)	C35—C36	1.34 (1)
C10—C11	1.33 (1)	C35—C37ⁱ	1.36 (1)
C11—C12	1.407 (7)	C36—C37	1.34 (1)
C13—C14	1.392 (5)

B1—O1—B2	121.2 (3)	C24—C19—B3	121.2 (3)
B2—O2—B3	118.4 (3)	C19—C20—C21	121.3 (4)
B1—O3—B3	121.2 (3)	C20—C21—C22	118.8 (5)
N1—O4—B1	114.2 (2)	C21—C22—C23	121.1 (6)
O4—N1—C1	113.6 (2)	C22—C23—C24	120.2 (6)
O5—N2—C25	115.3 (3)	C19—C24—C23	121.5 (4)
O5—N2—C31	123.1 (3)	N2—C25—C26	111.2 (3)
C25—N2—C31	121.6 (3)	N2—C25—C30	109.1 (3)
N1—C1—C2	107.9 (2)	C26—C25—C30	111.1 (3)
N1—C1—C6	110.9 (3)	C25—C26—C27	111.5 (4)
C2—C1—C6	111.3 (3)	C26—C27—C28	110.6 (5)
C1—C2—C3	110.1 (3)	C27—C28—C29	111.8 (5)
C2—C3—C4	111.8 (4)	C28—C29—C30	112.8 (5)
C3—C4—C5	111.2 (4)	C25—C30—C29	109.9 (4)
C4—C5—C6	112.3 (4)	N2—C31—C32	123.9 (3)
C1—C6—C5	110.0 (3)	C31—C32—C33	110.7 (4)
C8—C7—C12	116.2 (3)	C31—C32—C34	109.7 (4)
C8—C7—B1	121.9 (3)	C33—C32—C34	110.6 (4)
C12—C7—B1	121.8 (4)	C36—C35—C37ⁱ	119.8 (7)
C7—C8—C9	122.1 (4)	C35—C36—C37	121.6 (6)
C8—C9—C10	119.7 (6)	C35ⁱ—C37—C36	118.6 (7)
C9—C10—C11	120.4 (6)	O1—B1—O3	111.2 (3)
C10—C11—C12	120.4 (5)	O1—B1—O4	107.5 (3)
C7—C12—C11	121.0 (5)	O1—B1—C7	113.1 (3)
C14—C13—C18	116.0 (3)	O3—B1—O4	107.4 (3)
C14—C13—B2	122.1 (3)	O3—B1—C7	112.4 (3)
C18—C13—B2	121.9 (4)	O4—B1—C7	104.8 (2)
C13—C14—C15	122.4 (4)	O1—B2—O2	121.0 (4)
C14—C15—C16	120.2 (4)	O1—B2—C13	120.9 (4)
C15—C16—C17	120.0 (5)	O2—B2—C13	118.1 (3)
C16—C17—C18	119.0 (4)	O2—B3—O3	120.7 (3)
C13—C18—C17	122.4 (4)	O2—B3—C19	117.7 (3)
C20—C19—C24	117.1 (4)	O3—B3—C19	121.5 (4)
C20—C19—B3	121.6 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

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