organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

4,6-Di-tert-butyl-2,3-di­hy­droxy­benzalde­hyde

aLaboratory of Free Radical Polymerization, G.A. Razuvaev Institute of ­Organometallic Chemistry of the Russian Academy of Science, Tropinina str, 49, Nizhny Novgorod, 603950, Russian Federation, bGroup of X-Ray Diffraction Investigations, G.A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Science, Tropinina str, 49, Nizhny Novgorod, 603950, Russian Federation, and cLaboratory of the Chemistry of Organometallic Compounds, G.A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Science, Tropinina str, 49, Nizhny Novgorod, 603950, Russian Federation
*Correspondence e-mail: mars@iomc.ras.ru

(Received 23 August 2013; accepted 13 September 2013; online 18 September 2013)

The title compound, C15H22O3, crystallizes with two independent mol­ecules in the asymmetric unit. In each mol­ecule, one hy­droxy group (at position 2) is involved in an intra­molecular O—H⋯O hydrogen bond, and another one (at position 3) exhibits bifurcated hydrogen-bonding being involved in intra- and inter­molecular O—H⋯O inter­actions. In the crystal, O—H⋯O hydrogen bonds link alternating independent mol­ecules into chains running along [010].

Related literature

For the crystal structure of 2,3-di­hydroxy­benzaldehyde, see: Ng (2005[Ng, S. W. (2005). Acta Cryst. E61, o2301-o2302.]). For applications of Shiff base ligands based on 2,3-di­hydroxy­benzaldehyde, see: Albrecht et al. (2004[Albrecht, M., Janser, I., Kamptmann, S., Weis, P., Wibbeling, B. & Froehlich, R. (2004). Dalton Trans. pp. 37-43.]); Furutachi et al. (2010[Furutachi, M., Chen, Z., Matsunaga, S. & Shibasaki, M. (2010). Molecules, 15, 532-544.]); Belmonte et al. (2012[Belmonte, M. M., Escudero-Adan, E. C., Martin, E. & Kleij, A. W. (2012). Dalton Trans. 41, 5193-5200.]).

[Scheme 1]

Experimental

Crystal data
  • C15H22O3

  • Mr = 250.33

  • Triclinic, [P \overline 1]

  • a = 9.3113 (9) Å

  • b = 10.6511 (10) Å

  • c = 15.3962 (15) Å

  • α = 95.242 (2)°

  • β = 103.085 (2)°

  • γ = 95.492 (2)°

  • V = 1470.4 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 K

  • 0.70 × 0.16 × 0.16 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) Tmin = 0.948, Tmax = 0.988

  • 8903 measured reflections

  • 5740 independent reflections

  • 4411 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.130

  • S = 1.06

  • 5740 reflections

  • 361 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1A—H1A⋯O2A 0.885 (15) 2.169 (15) 2.6360 (10) 112.4 (11)
O2A—H2A⋯O3A 1.154 (14) 1.484 (14) 2.5013 (10) 142.7 (12)
O1B—H1B⋯O2B 0.883 (17) 2.212 (16) 2.6443 (10) 109.7 (12)
O2B—H2B⋯O3B 0.974 (17) 1.608 (16) 2.5046 (10) 150.9 (16)
O1B—H1B⋯O3A 0.883 (17) 1.916 (17) 2.7485 (11) 156.4 (15)
O1A—H1A⋯O3Bi 0.885 (15) 1.912 (15) 2.7289 (11) 152.9 (13)
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Bruker, 2008[Bruker (2008). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

2,3-Dihydroxybenzaldehyde is well known building-block for preparing Schiff-base ligands containining catechol fragment. These ligands are used for the synthesis of polynuclear metal complexes (Belmonte et al., 2012), supramolecular compounds (Albrecht et al., 2004) and catalysts (Furutachi et al., 2010). Here we report the crystal structure of the title compound (I).

The asymmetric unit of (I) contains two independent molecules (Fig. 1) with non-typical arrangement of tert-butyl groups (orto- and para- despite meta-position relative to CHO-group). All bond lengths and angles in (I) are normal and correspond to those observed in the related 2,3-dihydroxybenzaldehyde (Ng, 2005). The structure shows two types of O—H···O hydrogen bonds (Table 1) - intra- and intermolecular ones.

In the crystal, intermolecular O—H···O hydrogen bonds link alternating independent molecules into chains running in [010] (Fig. 1).

Related literature top

For the crystal structure of 2,3-dihydroxybenzaldehyde, see: Ng (2005). For applications of Shiff base ligands based on 2,3-dihydroxybenzaldehyde, see: Albrecht et al. (2004); Furutachi et al. (2010); Belmonte et al. (2012).

Experimental top

4,6-Di-tert-butyl-2,3-dihydroxybenzaldehyde was synthesized by following scheme (Fig. 2).

1,2-Bis(benzyloxy)-3,5-di-tert-butylbenzene (1). Mixture of 3,5-di-tert-butyl-catechol (22.2 g, 0.1 mol), benzyl chloride (23.0 ml, 0.2 mol) and K2CO3 (27.6 g, 0.2 mol) in DMF (100 ml) was heated at 90°C for 24 h under argon atmosphere. After cooling, water (300 ml) was added to reaction mixture and the product was extracted by hexane (3*200 ml). Extract was dried by Na2SO4. The solvent was evaporated and the product was dried under vacuum. The yield was 39.4 g (98%). m.p.=86-87°C dH (200 MHz CDCl3) 7.48-7.28 (m, 10H, 2Ph), 7.02 (d, 1H, Car-H, JHH=2.2 Hz), 6.95 (d, 1H, Car-H, JHH=2.2 Hz), 5.16 (s, 2H, CH2Ph), 5.11 (s, 2H, CH2Ph), 1.43 and 1.32 (s, both 9H, t-Bu). dC (50 MHz CDCl3) 151.85, 145.71, 145.46, 142.73, 138.57, 137.33, 128.45, 128.22, 127.83, 127.79, 127.58, 127.33, 116.55, 110.78, 73.50, 71.44, 35.48, 34.80, 31.56, 30.87.

2,3-bis(benzyloxy)-4,6-di-tert-butylbenzaldehyde (2). The compound 1 (20.1 g, 0.05 mol) was dissolved in THF (200 ml), and the solution was cooled to -78°C. TMEDA (7.5 ml, 0.05 mol) and BuLi in hexane (160 ml 0.6 M, 0.1 mol) were added to the mixture. It was stirred for 3 h and DMF (7.7 ml, 0.1 mol) was added. Mixture was stirred at -78°C for 3 h and then was warmed to room temperature, and stirring was continued overnight. The resulting mixture was diluted by water (300 ml) and neutralized by conc. HCl. The mixture of 1 and 2 was extracted by hexane (3*200 ml). The solvent was evaporated and the crude product was purified by column chromatography on silica gel (eluent hexane:ethyl acetate 40:1, second fraction). The yield was 15.3 g (71%). m.p.=84-85°C. dH (200 MHz CDCl3) 10.53 (s, 1H, CHO), 7.51-7.31 (m, 11H, 2Ph and Car-H), 5.21 (s, 2H, CH2Ph), 4.98 (s, 2H, CH2Ph), 1.45 and 1.36 (s, both 9H, t-Bu). dC (50 MHz CDCl3) 196.65, 151.76, 149.07, 146.09, 144.31, 137.89, 136.49, 132.26, 128.88, 128.41, 128.36,128.22, 127.56, 127.16, 120.83, 75.85, 73.69, 36.13, 35.86, 32.02, 30.53.

4,6-Di-tert-butyl-2,3-dihydroxybenzaldehyde (3). 0.1 M solution of BCl3 in CH2Cl2 (60 ml) was added with cooling (0°C) to 2 (12.9 g, 0.03 mol) in CH2Cl2 (30 ml). Reaction mixture was stirred for 24 h. Water (50 ml) was added to the mixture, and stirring was continued for 24 h. Product was extracted by CH2Cl2 and washed by water (4*50 ml). Extract was dried by Na2SO4 and the solvent was evaporated. 3 was recrystallized from methanol (50 ml). Yellow crystalline (6.4 g, 85%). m.p.=115-116°C. nmax (nujol) 3620.86 (nar.), 3529-3240 (br.), 1624 (C=O)cm-1. dH (200 MHz CDCl3) 12.92 (s, 1H, OH), 10.71 (s, 1H, CHO), 6.88 (s, 1H, Car-H), 5.99 (s, 1H, OH), 1.42 and 1.49 (s, both 9H, t-Bu). dC (50 MHz CDCl3) 196.58, 151.93, 143.24, 141.77, 141.73, 115.99 (C-H), 115.19, 35.75, 35.72, 33.76, 29.00. Anal. Calcd for C15H22O3: C 71.97, H 8.86. Found: C 71.89, H 8.90.

Refinement top

C-bound H atoms, excluding H7A and H7B, were placed in calculated positions and were refined in the riding model. The rest H atoms were located on a difference map and were refined isotropically.

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Two independent molecules of the title compound showing the atomic numering and 30% probability displacement ellipsoids. Dashed lines denote hydrogen bonds. C-bound H atoms omitted for clarity.
[Figure 2] Fig. 2. Synthesis of sterically hindered salicylic aldehyde 3. Reagents and conditions: a) benzyl chloride (BnCl), K2CO3, DMF (98%); b) butyllithium (BuLi) in hexane, tetramethylethylenediamine (TMEDA); DMF; H2O (71%); c) BCl3 in CH2Cl2; H2O (85%).
(I) top
Crystal data top
C15H22O3Z = 4
Mr = 250.33F(000) = 544
Triclinic, P1Dx = 1.131 Mg m3
Hall symbol: -P 1Melting point: 115 K
a = 9.3113 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.6511 (10) ÅCell parameters from 900 reflections
c = 15.3962 (15) Åθ = 2–30°
α = 95.242 (2)°µ = 0.08 mm1
β = 103.085 (2)°T = 100 K
γ = 95.492 (2)°Prism, yellow
V = 1470.4 (2) Å30.70 × 0.16 × 0.16 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5740 independent reflections
Radiation source: fine-focus sealed tube4411 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
h = 1111
Tmin = 0.948, Tmax = 0.988k = 1113
8903 measured reflectionsl = 1818
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.046 w = 1/[σ2(Fo2) + (0.0779P)2 + 0.0742P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.130(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.25 e Å3
5740 reflectionsΔρmin = 0.21 e Å3
361 parameters
Crystal data top
C15H22O3γ = 95.492 (2)°
Mr = 250.33V = 1470.4 (2) Å3
Triclinic, P1Z = 4
a = 9.3113 (9) ÅMo Kα radiation
b = 10.6511 (10) ŵ = 0.08 mm1
c = 15.3962 (15) ÅT = 100 K
α = 95.242 (2)°0.70 × 0.16 × 0.16 mm
β = 103.085 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5740 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)
4411 reflections with I > 2σ(I)
Tmin = 0.948, Tmax = 0.988Rint = 0.018
8903 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.25 e Å3
5740 reflectionsΔρmin = 0.21 e Å3
361 parameters
Special details top

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
xyzUiso*/Ueq
O1A0.13058 (9)0.38259 (6)0.24551 (5)0.0316 (2)
H1A0.1319 (16)0.3993 (13)0.1884 (10)0.054 (4)*
O2A0.14084 (8)0.22900 (6)0.12158 (5)0.02752 (18)
H2A0.1392 (16)0.1505 (13)0.0745 (10)0.057 (4)*
O3A0.15955 (9)0.01066 (7)0.07434 (5)0.02887 (19)
C1A0.15563 (11)0.25515 (9)0.27164 (7)0.0226 (2)
C2A0.16112 (11)0.17213 (9)0.20646 (7)0.0216 (2)
C3A0.18605 (10)0.03905 (9)0.22842 (7)0.0214 (2)
C4A0.21238 (11)0.01227 (9)0.32024 (7)0.0223 (2)
C5A0.20502 (11)0.07376 (9)0.38215 (7)0.0229 (2)
H5AA0.22180.04070.44350.027*
C6A0.17450 (11)0.20648 (9)0.36057 (7)0.0232 (2)
C7A0.18009 (12)0.03568 (9)0.15347 (7)0.0253 (2)
H7A0.1889 (13)0.1306 (11)0.1631 (8)0.031 (3)*
C8A0.24859 (12)0.15602 (9)0.35317 (7)0.0261 (3)
C9A0.28235 (14)0.18201 (10)0.45588 (8)0.0352 (3)
H9AA0.19520.15070.47680.053*
H9AB0.30660.27360.47410.053*
H9AC0.36680.13830.48230.053*
C10A0.11678 (13)0.22788 (10)0.31648 (8)0.0337 (3)
H10A0.02990.19420.33680.051*
H10B0.09400.21690.25070.051*
H10C0.14230.31840.33850.051*
C11A0.38925 (13)0.21161 (10)0.32590 (8)0.0331 (3)
H11A0.37040.20480.26030.050*
H11B0.47190.16410.34930.050*
H11C0.41460.30110.35080.050*
C12A0.15986 (13)0.29441 (10)0.43265 (7)0.0295 (3)
C13A0.17984 (15)0.22047 (11)0.52559 (8)0.0369 (3)
H13A0.10430.16200.52330.055*
H13B0.27890.17210.54370.055*
H13C0.16910.28010.56920.055*
C14A0.00288 (14)0.36849 (11)0.40655 (8)0.0382 (3)
H14A0.01110.42010.34850.057*
H14B0.07130.30860.40200.057*
H14C0.00880.42400.45250.057*
C15A0.27806 (14)0.38673 (11)0.43956 (8)0.0387 (3)
H15A0.26600.43690.38120.058*
H15B0.26640.44370.48460.058*
H15C0.37720.33850.45730.058*
O1B0.19869 (9)0.08055 (6)0.08108 (5)0.02929 (19)
H1B0.1807 (18)0.0734 (14)0.0277 (11)0.067 (5)*
O2B0.14124 (8)0.25992 (6)0.03230 (5)0.02881 (18)
H2B0.1334 (19)0.3373 (15)0.0690 (11)0.075 (5)*
O3B0.14462 (10)0.48947 (7)0.08636 (5)0.0382 (2)
C1B0.22899 (11)0.20423 (9)0.09443 (7)0.0229 (2)
C2B0.19582 (11)0.30029 (9)0.03624 (7)0.0227 (2)
C3B0.22243 (11)0.42972 (9)0.04678 (7)0.0242 (2)
C4B0.28051 (11)0.46447 (9)0.12054 (7)0.0241 (2)
C5B0.31494 (11)0.36661 (9)0.17478 (7)0.0247 (2)
H5BA0.35570.38850.22340.030*
C6B0.29418 (11)0.23659 (9)0.16335 (7)0.0230 (2)
C7B0.19374 (14)0.51970 (10)0.02154 (8)0.0338 (3)
H7B0.2122 (16)0.6105 (13)0.0160 (10)0.055 (4)*
C8B0.30439 (12)0.60314 (10)0.14183 (8)0.0302 (3)
C9B0.43000 (15)0.68113 (11)0.06932 (10)0.0469 (4)
H9BA0.44260.76870.08370.070*
H9BB0.52260.64360.06710.070*
H9BC0.40490.68090.01080.070*
C10B0.16044 (14)0.66445 (11)0.15304 (9)0.0418 (3)
H10D0.17630.74940.17140.063*
H10E0.13050.67120.09590.063*
H10F0.08210.61210.19910.063*
C11B0.34989 (16)0.60891 (11)0.23132 (9)0.0459 (4)
H11D0.36060.69740.24410.069*
H11E0.27340.55870.27960.069*
H11F0.44470.57430.22740.069*
C12B0.34396 (12)0.13435 (10)0.22352 (7)0.0279 (3)
C13B0.42121 (14)0.19175 (11)0.29129 (8)0.0379 (3)
H13D0.35190.23740.33090.057*
H13E0.45300.12370.32720.057*
H13F0.50810.25080.25910.057*
C14B0.20742 (14)0.04340 (11)0.27618 (8)0.0378 (3)
H14D0.13820.09110.31410.057*
H14E0.15810.00360.23400.057*
H14F0.23900.02250.31400.057*
C15B0.45488 (13)0.06066 (11)0.16510 (8)0.0358 (3)
H15D0.54140.11940.13190.054*
H15E0.48690.00420.20350.054*
H15F0.40720.01980.12260.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0487 (5)0.0195 (3)0.0268 (4)0.0008 (3)0.0121 (4)0.0013 (3)
O2A0.0381 (4)0.0244 (3)0.0206 (4)0.0004 (3)0.0105 (3)0.0001 (3)
O3A0.0371 (4)0.0276 (3)0.0233 (4)0.0024 (3)0.0099 (3)0.0047 (3)
C1A0.0237 (5)0.0197 (4)0.0254 (5)0.0007 (4)0.0085 (4)0.0027 (4)
C2A0.0216 (5)0.0247 (5)0.0187 (5)0.0008 (4)0.0069 (4)0.0005 (4)
C3A0.0190 (5)0.0214 (4)0.0257 (5)0.0020 (4)0.0087 (4)0.0043 (4)
C4A0.0184 (5)0.0233 (5)0.0257 (5)0.0028 (4)0.0065 (4)0.0019 (4)
C5A0.0233 (5)0.0252 (5)0.0205 (5)0.0017 (4)0.0072 (4)0.0006 (4)
C6A0.0209 (5)0.0254 (5)0.0240 (5)0.0018 (4)0.0063 (4)0.0043 (4)
C7A0.0260 (5)0.0254 (5)0.0259 (5)0.0023 (4)0.0090 (4)0.0037 (4)
C8A0.0289 (5)0.0225 (5)0.0268 (5)0.0012 (4)0.0099 (4)0.0006 (4)
C9A0.0444 (7)0.0274 (5)0.0314 (6)0.0031 (5)0.0101 (5)0.0043 (4)
C10A0.0368 (6)0.0237 (5)0.0414 (7)0.0052 (4)0.0120 (5)0.0000 (4)
C11A0.0320 (6)0.0298 (5)0.0362 (6)0.0049 (4)0.0105 (5)0.0007 (4)
C12A0.0351 (6)0.0289 (5)0.0250 (6)0.0017 (4)0.0075 (5)0.0077 (4)
C13A0.0491 (7)0.0382 (6)0.0252 (6)0.0048 (5)0.0107 (5)0.0093 (5)
C14A0.0422 (7)0.0395 (6)0.0353 (6)0.0043 (5)0.0141 (5)0.0136 (5)
C15A0.0484 (7)0.0333 (6)0.0345 (6)0.0091 (5)0.0054 (6)0.0118 (5)
O1B0.0419 (4)0.0208 (3)0.0293 (4)0.0014 (3)0.0179 (3)0.0031 (3)
O2B0.0417 (4)0.0246 (3)0.0253 (4)0.0046 (3)0.0177 (3)0.0045 (3)
O3B0.0614 (5)0.0276 (4)0.0314 (4)0.0090 (3)0.0219 (4)0.0026 (3)
C1B0.0244 (5)0.0206 (4)0.0237 (5)0.0012 (4)0.0058 (4)0.0041 (4)
C2B0.0243 (5)0.0258 (5)0.0190 (5)0.0016 (4)0.0071 (4)0.0051 (4)
C3B0.0247 (5)0.0235 (5)0.0245 (5)0.0042 (4)0.0045 (4)0.0054 (4)
C4B0.0201 (5)0.0261 (5)0.0254 (5)0.0001 (4)0.0036 (4)0.0072 (4)
C5B0.0208 (5)0.0309 (5)0.0235 (5)0.0007 (4)0.0067 (4)0.0078 (4)
C6B0.0195 (5)0.0286 (5)0.0202 (5)0.0014 (4)0.0046 (4)0.0012 (4)
C7B0.0471 (7)0.0253 (5)0.0318 (6)0.0068 (5)0.0135 (5)0.0054 (4)
C8B0.0290 (5)0.0257 (5)0.0361 (6)0.0009 (4)0.0069 (5)0.0114 (4)
C9B0.0423 (7)0.0293 (6)0.0591 (9)0.0062 (5)0.0059 (7)0.0095 (6)
C10B0.0364 (6)0.0305 (5)0.0613 (8)0.0034 (5)0.0112 (6)0.0217 (5)
C11B0.0562 (8)0.0345 (6)0.0534 (8)0.0021 (5)0.0235 (6)0.0196 (5)
C12B0.0287 (5)0.0322 (5)0.0250 (5)0.0032 (4)0.0122 (4)0.0003 (4)
C13B0.0427 (6)0.0439 (6)0.0335 (6)0.0085 (5)0.0210 (5)0.0043 (5)
C14B0.0378 (6)0.0408 (6)0.0322 (6)0.0012 (5)0.0112 (5)0.0107 (5)
C15B0.0373 (6)0.0364 (6)0.0377 (6)0.0109 (5)0.0159 (5)0.0013 (5)
Geometric parameters (Å, º) top
O1A—C1A1.3623 (11)O1B—C1B1.3645 (12)
O1A—H1A0.885 (15)O1B—H1B0.883 (17)
O2A—C2A1.3535 (12)O2B—C2B1.3567 (13)
O2A—H2A1.154 (14)O2B—H2B0.974 (17)
O3A—C7A1.2373 (13)O3B—C7B1.2436 (15)
C1A—C6A1.3849 (15)C1B—C6B1.3899 (15)
C1A—C2A1.4030 (14)C1B—C2B1.4011 (15)
C2A—C3A1.4112 (13)C2B—C3B1.4078 (14)
C3A—C4A1.4260 (14)C3B—C4B1.4269 (15)
C3A—C7A1.4545 (15)C3B—C7B1.4450 (16)
C4A—C5A1.3893 (14)C4B—C5B1.3830 (15)
C4A—C8A1.5483 (13)C4B—C8B1.5482 (14)
C5A—C6A1.4086 (13)C5B—C6B1.4124 (14)
C5A—H5AA0.9500C5B—H5BA0.9500
C6A—C12A1.5366 (15)C6B—C12B1.5380 (15)
C7A—H7A1.001 (11)C7B—H7B0.981 (14)
C8A—C9A1.5345 (16)C8B—C10B1.5284 (17)
C8A—C10A1.5349 (16)C8B—C11B1.5350 (19)
C8A—C11A1.5454 (16)C8B—C9B1.5355 (16)
C9A—H9AA0.9800C9B—H9BA0.9800
C9A—H9AB0.9800C9B—H9BB0.9800
C9A—H9AC0.9800C9B—H9BC0.9800
C10A—H10A0.9800C10B—H10D0.9800
C10A—H10B0.9800C10B—H10E0.9800
C10A—H10C0.9800C10B—H10F0.9800
C11A—H11A0.9800C11B—H11D0.9800
C11A—H11B0.9800C11B—H11E0.9800
C11A—H11C0.9800C11B—H11F0.9800
C12A—C13A1.5323 (16)C12B—C13B1.5335 (17)
C12A—C15A1.5372 (17)C12B—C15B1.5347 (16)
C12A—C14A1.5414 (16)C12B—C14B1.5382 (15)
C13A—H13A0.9800C13B—H13D0.9800
C13A—H13B0.9800C13B—H13E0.9800
C13A—H13C0.9800C13B—H13F0.9800
C14A—H14A0.9800C14B—H14D0.9800
C14A—H14B0.9800C14B—H14E0.9800
C14A—H14C0.9800C14B—H14F0.9800
C15A—H15A0.9800C15B—H15D0.9800
C15A—H15B0.9800C15B—H15E0.9800
C15A—H15C0.9800C15B—H15F0.9800
C1A—O1A—H1A110.9 (9)C1B—O1B—H1B112.1 (10)
C2A—O2A—H2A107.9 (7)C2B—O2B—H2B105.0 (10)
O1A—C1A—C6A121.43 (9)O1B—C1B—C6B121.39 (9)
O1A—C1A—C2A118.85 (9)O1B—C1B—C2B119.02 (10)
C6A—C1A—C2A119.71 (9)C6B—C1B—C2B119.58 (9)
O2A—C2A—C1A115.16 (8)O2B—C2B—C1B115.32 (9)
O2A—C2A—C3A122.78 (9)O2B—C2B—C3B122.63 (9)
C1A—C2A—C3A122.06 (9)C1B—C2B—C3B122.02 (10)
C2A—C3A—C4A118.86 (9)C2B—C3B—C4B119.22 (9)
C2A—C3A—C7A116.16 (9)C2B—C3B—C7B116.57 (10)
C4A—C3A—C7A124.98 (9)C4B—C3B—C7B124.17 (9)
C5A—C4A—C3A116.85 (9)C5B—C4B—C3B116.59 (9)
C5A—C4A—C8A119.49 (9)C5B—C4B—C8B119.99 (10)
C3A—C4A—C8A123.65 (9)C3B—C4B—C8B123.41 (9)
C4A—C5A—C6A124.74 (9)C4B—C5B—C6B124.97 (10)
C4A—C5A—H5AA117.6C4B—C5B—H5BA117.5
C6A—C5A—H5AA117.6C6B—C5B—H5BA117.5
C1A—C6A—C5A117.68 (9)C1B—C6B—C5B117.45 (9)
C1A—C6A—C12A120.97 (9)C1B—C6B—C12B120.95 (9)
C5A—C6A—C12A121.34 (9)C5B—C6B—C12B121.59 (10)
O3A—C7A—C3A124.01 (9)O3B—C7B—C3B124.19 (10)
O3A—C7A—H7A115.1 (7)O3B—C7B—H7B117.6 (9)
C3A—C7A—H7A120.8 (7)C3B—C7B—H7B118.2 (9)
C9A—C8A—C10A106.64 (9)C10B—C8B—C11B105.50 (10)
C9A—C8A—C11A106.03 (9)C10B—C8B—C9B111.32 (10)
C10A—C8A—C11A110.55 (9)C11B—C8B—C9B106.67 (10)
C9A—C8A—C4A111.89 (9)C10B—C8B—C4B111.07 (9)
C10A—C8A—C4A111.07 (8)C11B—C8B—C4B111.32 (9)
C11A—C8A—C4A110.48 (9)C9B—C8B—C4B110.77 (9)
C8A—C9A—H9AA109.5C8B—C9B—H9BA109.5
C8A—C9A—H9AB109.5C8B—C9B—H9BB109.5
H9AA—C9A—H9AB109.5H9BA—C9B—H9BB109.5
C8A—C9A—H9AC109.5C8B—C9B—H9BC109.5
H9AA—C9A—H9AC109.5H9BA—C9B—H9BC109.5
H9AB—C9A—H9AC109.5H9BB—C9B—H9BC109.5
C8A—C10A—H10A109.5C8B—C10B—H10D109.5
C8A—C10A—H10B109.5C8B—C10B—H10E109.5
H10A—C10A—H10B109.5H10D—C10B—H10E109.5
C8A—C10A—H10C109.5C8B—C10B—H10F109.5
H10A—C10A—H10C109.5H10D—C10B—H10F109.5
H10B—C10A—H10C109.5H10E—C10B—H10F109.5
C8A—C11A—H11A109.5C8B—C11B—H11D109.5
C8A—C11A—H11B109.5C8B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C8A—C11A—H11C109.5C8B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
C13A—C12A—C6A112.27 (9)C13B—C12B—C15B107.54 (10)
C13A—C12A—C15A107.87 (9)C13B—C12B—C6B112.18 (9)
C6A—C12A—C15A110.06 (10)C15B—C12B—C6B109.49 (9)
C13A—C12A—C14A107.79 (10)C13B—C12B—C14B108.16 (9)
C6A—C12A—C14A108.50 (9)C15B—C12B—C14B110.12 (9)
C15A—C12A—C14A110.33 (9)C6B—C12B—C14B109.32 (9)
C12A—C13A—H13A109.5C12B—C13B—H13D109.5
C12A—C13A—H13B109.5C12B—C13B—H13E109.5
H13A—C13A—H13B109.5H13D—C13B—H13E109.5
C12A—C13A—H13C109.5C12B—C13B—H13F109.5
H13A—C13A—H13C109.5H13D—C13B—H13F109.5
H13B—C13A—H13C109.5H13E—C13B—H13F109.5
C12A—C14A—H14A109.5C12B—C14B—H14D109.5
C12A—C14A—H14B109.5C12B—C14B—H14E109.5
H14A—C14A—H14B109.5H14D—C14B—H14E109.5
C12A—C14A—H14C109.5C12B—C14B—H14F109.5
H14A—C14A—H14C109.5H14D—C14B—H14F109.5
H14B—C14A—H14C109.5H14E—C14B—H14F109.5
C12A—C15A—H15A109.5C12B—C15B—H15D109.5
C12A—C15A—H15B109.5C12B—C15B—H15E109.5
H15A—C15A—H15B109.5H15D—C15B—H15E109.5
C12A—C15A—H15C109.5C12B—C15B—H15F109.5
H15A—C15A—H15C109.5H15D—C15B—H15F109.5
H15B—C15A—H15C109.5H15E—C15B—H15F109.5
O1A—C1A—C2A—O2A0.23 (14)O1B—C1B—C2B—O2B2.92 (13)
C6A—C1A—C2A—O2A179.75 (9)C6B—C1B—C2B—O2B175.97 (8)
O1A—C1A—C2A—C3A179.77 (9)O1B—C1B—C2B—C3B179.19 (9)
C6A—C1A—C2A—C3A0.25 (16)C6B—C1B—C2B—C3B1.93 (15)
O2A—C2A—C3A—C4A177.43 (9)O2B—C2B—C3B—C4B179.78 (9)
C1A—C2A—C3A—C4A2.57 (15)C1B—C2B—C3B—C4B2.04 (15)
O2A—C2A—C3A—C7A3.57 (14)O2B—C2B—C3B—C7B2.22 (14)
C1A—C2A—C3A—C7A176.43 (9)C1B—C2B—C3B—C7B175.52 (10)
C2A—C3A—C4A—C5A2.79 (14)C2B—C3B—C4B—C5B3.52 (14)
C7A—C3A—C4A—C5A176.12 (10)C7B—C3B—C4B—C5B173.84 (10)
C2A—C3A—C4A—C8A176.94 (9)C2B—C3B—C4B—C8B175.97 (9)
C7A—C3A—C4A—C8A4.15 (16)C7B—C3B—C4B—C8B6.67 (16)
C3A—C4A—C5A—C6A0.36 (15)C3B—C4B—C5B—C6B1.28 (15)
C8A—C4A—C5A—C6A179.38 (9)C8B—C4B—C5B—C6B178.23 (9)
O1A—C1A—C6A—C5A177.85 (9)O1B—C1B—C6B—C5B177.04 (9)
C2A—C1A—C6A—C5A2.65 (15)C2B—C1B—C6B—C5B4.10 (14)
O1A—C1A—C6A—C12A3.19 (15)O1B—C1B—C6B—C12B4.00 (14)
C2A—C1A—C6A—C12A176.32 (9)C2B—C1B—C6B—C12B174.86 (9)
C4A—C5A—C6A—C1A2.40 (16)C4B—C5B—C6B—C1B2.58 (15)
C4A—C5A—C6A—C12A176.56 (10)C4B—C5B—C6B—C12B176.38 (9)
C2A—C3A—C7A—O3A2.33 (16)C2B—C3B—C7B—O3B1.77 (17)
C4A—C3A—C7A—O3A178.74 (10)C4B—C3B—C7B—O3B179.20 (10)
C5A—C4A—C8A—C9A3.81 (14)C5B—C4B—C8B—C10B123.69 (11)
C3A—C4A—C8A—C9A175.91 (10)C3B—C4B—C8B—C10B55.79 (13)
C5A—C4A—C8A—C10A115.24 (11)C5B—C4B—C8B—C11B6.45 (14)
C3A—C4A—C8A—C10A65.03 (13)C3B—C4B—C8B—C11B173.02 (10)
C5A—C4A—C8A—C11A121.69 (11)C5B—C4B—C8B—C9B112.06 (12)
C3A—C4A—C8A—C11A58.03 (13)C3B—C4B—C8B—C9B68.47 (14)
C1A—C6A—C12A—C13A178.10 (10)C1B—C6B—C12B—C13B176.58 (9)
C5A—C6A—C12A—C13A0.83 (15)C5B—C6B—C12B—C13B2.35 (13)
C1A—C6A—C12A—C15A61.73 (12)C1B—C6B—C12B—C15B57.26 (12)
C5A—C6A—C12A—C15A119.34 (11)C5B—C6B—C12B—C15B121.66 (10)
C1A—C6A—C12A—C14A59.08 (14)C1B—C6B—C12B—C14B63.45 (12)
C5A—C6A—C12A—C14A119.85 (11)C5B—C6B—C12B—C14B117.63 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O2A0.885 (15)2.169 (15)2.6360 (10)112.4 (11)
O2A—H2A···O3A1.154 (14)1.484 (14)2.5013 (10)142.7 (12)
O1B—H1B···O2B0.883 (17)2.212 (16)2.6443 (10)109.7 (12)
O2B—H2B···O3B0.974 (17)1.608 (16)2.5046 (10)150.9 (16)
O1B—H1B···O3A0.883 (17)1.916 (17)2.7485 (11)156.4 (15)
O1A—H1A···O3Bi0.885 (15)1.912 (15)2.7289 (11)152.9 (13)
Symmetry code: (i) x, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O2A0.885 (15)2.169 (15)2.6360 (10)112.4 (11)
O2A—H2A···O3A1.154 (14)1.484 (14)2.5013 (10)142.7 (12)
O1B—H1B···O2B0.883 (17)2.212 (16)2.6443 (10)109.7 (12)
O2B—H2B···O3B0.974 (17)1.608 (16)2.5046 (10)150.9 (16)
O1B—H1B···O3A0.883 (17)1.916 (17)2.7485 (11)156.4 (15)
O1A—H1A···O3Bi0.885 (15)1.912 (15)2.7289 (11)152.9 (13)
Symmetry code: (i) x, y1, z.
 

Acknowledgements

This work was carried out in the framework of the Federal Target Program Scientific and Pedagogical Specialists of Inno­vative Russia for 2009–2013 (Contract GK_8460 from 31/08/2012 and Target aspirant agreement N14.132.21.1462 from 01/10/2012), and was supported financially by a Russian Presi­dent Grant supporting scientific schools (NSh-1113/2012/3).

References

First citationAlbrecht, M., Janser, I., Kamptmann, S., Weis, P., Wibbeling, B. & Froehlich, R. (2004). Dalton Trans. pp. 37–43.  Web of Science CSD CrossRef
First citationBelmonte, M. M., Escudero-Adan, E. C., Martin, E. & Kleij, A. W. (2012). Dalton Trans. 41, 5193–5200.  PubMed
First citationBruker (2008). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFurutachi, M., Chen, Z., Matsunaga, S. & Shibasaki, M. (2010). Molecules, 15, 532–544.  Web of Science CrossRef CAS PubMed
First citationNg, S. W. (2005). Acta Cryst. E61, o2301–o2302.  Web of Science CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds