3,5-Bis(benz­yloxy)benzoic acid

Moreno-Fuquen, R.; Grande, C.; Advincula, R.C.; Tenorio, J.C.; Ellena, J.

doi:10.1107/S1600536812043796

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages o3247-o3248

doi:10.1107/S1600536812043796

Open

access

3,5-Bis(benzyloxy)benzoic acid

Rodolfo Moreno-Fuquen,^a ^* Carlos Grande,^b Rigoberto C. Advincula,^c Juan C. Tenorio ^d and Javier Ellena ^d

^aDepartamento de Química, Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, ^bPrograma de Ingenieria Agroindustrial, Universidad San Buenaventura, AA 7154, Santiago de Cali, Colombia, ^cCase Western Reserve University, Department of Macromolecular Science and Engineering, 2100 Adelbert Road, Kent Hale Smith Bldg, Cleveland, Ohio 44106, USA, and ^dInstituto de Física de São Carlos, IFSC, Universidade de São Paulo, USP, São Carlos, SP, Brazil
^*Correspondence e-mail: rodimo26@yahoo.es

(Received 2 October 2012; accepted 22 October 2012; online 31 October 2012)

In the title compound, C₂₁H₁₈O₄, the outer benzyl rings are disordered over two resolved positions in a 0.50 ratio. The O—CH₂ groups form dihedral angles of 4.1 (2) and 10.9 (4)° with the central benzene ring, adopting a syn–anti conformation with respect to this ring. In the crystal, the molecules are linked by O—H⋯O hydrogen bonds and weak C—H⋯O interactions, forming chains along [010].

Related literature

For properties of dendrimer chemistry, see: Fréchet (2002 ). For the diverse applications of 3,5-bis(benzyloxy)benzoic acid and its benzoate derivatives, see: Sivakumar et al. (2010 ); Remya et al. (2008 ); Hawker & Fréchet (1992 ). For magnetic and luminiscent properties of lanthanide benzoates, see: Busskamp et al. (2007 ). For the conformation of O—CH₂ groups, see: Xiao et al. (2007 ). For related structures, see: Gainsford et al. (2009 ); Zhu et al. (2009 ). For graph-set motifs, see: Etter (1990 ). For hydrogen bonding, see: Nardelli (1995 ); Desiraju & Steiner (1999 ).

Experimental

Crystal data

C₂₁H₁₈O₄
M_r = 334.37
Triclinic, $[P \overline 1]$
a = 5.2801 (2) Å
b = 11.6830 (5) Å
c = 14.4803 (7) Å
α = 83.303 (2)°
β = 80.775 (2)°
γ = 79.031 (1)°
V = 862.17 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.43 × 0.11 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
5626 measured reflections
3084 independent reflections
1801 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.163
S = 1.03
3084 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.82	2.6333 (18)	175
C20—H20⋯O1ⁱⁱ	0.93	2.66	3.507 (13)	153
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+2, -y, -z+1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812043796/hg5257sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043796/hg5257Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043796/hg5257Isup3.cml

checkCIF report

Comment top

Dendrimer chemistry provides new opportunities of research in design of supramolecular architectures (Fréchet, 2002). 3,5-Bis-benzyloxy-benzoic acid (I) was used for the synthesis of luminescent lanthanide coordination complexes that display unique line-like emission bands (Sivakumar et al., 2010; Remya et al., 2008). Lanthanide benzoates and their derivatives have potential applications in a wide variety of fields because their novel luminescent and magnetic properties (Busskamp et al., 2007). The title compound was also used in the synthesis of monodispersed dendritic polyesters with removable chain ends using a convergent growth process (Hawker & Fréchet, 1992). Other related compounds were crystallized and studied by X-ray diffraction (Gainsford et al., 2009; Zhu et al., 2009) and their parameters can be used to compare with the parameters of the title system. A perspective view of the molecule of (I), showing the atomic numbering scheme, is given in Fig. 1. The title compound crystallizes in the triclinic system with a P-1 space group. The outer benzyl rings are disordered over two resolved positions in a 0.50 ratio. The molecules are bonded by intermolecular O—H···O hydrogen bonds of moderate character (Desiraju & Steiner, 1999). Indeed, carbonylic O2 and O1 are linked with an O···O distance of 2.633 (2) Å. The propagation of these interactions generate centrosymmetric rings with graphs-set notation R₂²(8) (Etter, 1990). Other weak C—H···O intermolecular interactions (Nardelli, 1995) contribute to stabilization of the molecules along b (Fig. 2). Other classical hydrogen bond interactions are not exhibited in the crystal packing. In the title structure, the O—CH₂ groups adopt a syn-anti conformation with respect to the central phenyl ring, similar to the behavior presented in the 1,3-Dibenzyloxy-5-(bromomethyl)-benzene system (Zhu et al., 2009), while in other similar structures, the O—CH₂ groups adopt a syn-syn conformation (Xiao et al., 2007). The O—CH₂ groups, C4—O3—C8—C9 and C6—O4—C15—C16 are essentially planar (r.m.s. deviation of non-hydrogen atoms= 0.0355 Å and 0.0217 Å respectivelly) and form dihedral angles of 4.1 (2)° and 10.9 (4)° with the central phenyl ring.

Related literature top

For properties of dendrimer chemistry, see: Fréchet (2002). For the diverse applications of 3,5-bis(benzyloxy)benzoic acid and its benzoate derivatives, see: Sivakumar et al. (2010); Remya et al. (2008); Hawker & Fréchet (1992). For magnetic and luminiscent properties of lanthanide benzoates, see: Busskamp et al. (2007). For the conformation of O—CH₂ groups, see: Xiao et al. (2007). For related structures, see: Gainsford et al. (2009); Zhu et al. (2009). For graph-set motifs, see: Etter (1990). For hydrogen bonding, see: Nardelli (1995); Desiraju & Steiner (1999).

Experimental top

Methyl 3,5-dihydroxybenzoate (2.0g, 12 mmol) was dissolved in 50 ml of acetonitrile and refluxed with potassium carbonate (8.0 g, 58 mmol) for 30 min. The resulting reaction mixture was refluxed at 68° C for 48 h following the addition of benzyl bromide (4.0 g, 24 mmol). The acetonitrile was evaporated off, and the residual mixture was poured into ice cold water. Methyl 3,5-bis-(benzyloxy)benzoate was obtained as a white precipitate. (2.0 g, 5.74 mmol), were taken from the precipitate, which was dissolved in 50 ml of ethanol. To this solution was added (1 g, 17.77 mmol) of KOH and it was placed under reflux. The reaction was followed by TLC until the presence of KOH was not longer observed. The reaction mixture was poured into ice cold water, acidified with dilute HCl, and the resulting precipitate was filtered, washed, dried, and recrystallized from ethanol. Yield, 1.67 g (89%). 3,5-Bis(benzyloxy)benzoic Acid, ¹H-NMR (500 MHz) δ(p.p.m.), 7.45–7.46(d, 4H, J= 7 Hz), 7.39–7.41 (t, 4H, J=7 Hz), 7.32–7.35 (t, 2H, J= 7 Hz), 7.16(d, 2H, J= 2.5 Hz), 6.92–6.93 (t, 1H, J= 2.5 Hz), 5.15 (s, 4H). ¹³C-NMR: 166.88, 159.35, 136.64, 132.79, 138.45, 127.90, 127.63, 107.96, 106.50, 69.45. F T—IR (KBr): 3033 (Ar—H); 1690, 1159, 733, 698 cm^-1.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP-3 (Farrugia, 1997) plot of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure of (I), showing the formation of chains running along [010]. Symmetry code: (i) -x,-y + 1,-z + 1; (ii) -x + 2,-y,-z + 1

3,5-Bis(benzyloxy)benzoic acid top

Crystal data top

C₂₁H₁₈O₄	Z = 2
M_r = 334.37	F(000) = 352
Triclinic, P1	D_x = 1.288 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2801 (2) Å	Cell parameters from 3147 reflections
b = 11.6830 (5) Å	θ = 2.9–26.4°
c = 14.4803 (7) Å	µ = 0.09 mm⁻¹
α = 83.303 (2)°	T = 295 K
β = 80.775 (2)°	Block, colourless
γ = 79.031 (1)°	0.43 × 0.11 × 0.10 mm
V = 862.17 (6) Å³

Data collection top

Nonius KappaCCD diffractometer	1801 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.2°, θ_min = 3.5°
CCD rotation images, thick slices scans	h = −6→6
5626 measured reflections	k = −14→14
3084 independent reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.094P)² + 0.0032P] where P = (F_o² + 2F_c²)/3
3084 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₂₁H₁₈O₄	γ = 79.031 (1)°
M_r = 334.37	V = 862.17 (6) Å³
Triclinic, P1	Z = 2
a = 5.2801 (2) Å	Mo Kα radiation
b = 11.6830 (5) Å	µ = 0.09 mm⁻¹
c = 14.4803 (7) Å	T = 295 K
α = 83.303 (2)°	0.43 × 0.11 × 0.10 mm
β = 80.775 (2)°

Data collection top

Nonius KappaCCD diffractometer	1801 reflections with I > 2σ(I)
5626 measured reflections	R_int = 0.036
3084 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	Δρ_max = 0.15 e Å⁻³
3084 reflections	Δρ_min = −0.15 e Å⁻³
316 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2556 (3)	0.46372 (17)	0.58387 (13)	0.0623 (5)
C2	0.4505 (3)	0.43437 (15)	0.65014 (12)	0.0597 (5)
C3	0.4690 (3)	0.51344 (17)	0.71085 (12)	0.0644 (5)
H3	0.3589	0.5858	0.7109	0.077*
C4	0.6534 (3)	0.48473 (16)	0.77226 (12)	0.0639 (5)
C5	0.8181 (4)	0.37791 (17)	0.77144 (13)	0.0673 (5)
H5	0.9413	0.3585	0.8125	0.081*
C6	0.7989 (4)	0.29977 (17)	0.70920 (14)	0.0690 (5)
C7	0.6163 (3)	0.32636 (17)	0.64802 (13)	0.0690 (5)
H7	0.6042	0.2734	0.6064	0.083*
C8	0.8524 (4)	0.55033 (19)	0.88979 (15)	0.0773 (6)
H8A	1.0236	0.5321	0.8534	0.093*
H8B	0.8282	0.4854	0.9366	0.093*
C9	0.8300 (5)	0.65976 (19)	0.93627 (17)	0.0705 (6)	0.50
C11	0.592 (6)	0.802 (3)	1.0445 (16)	0.132 (8)	0.50
H11	0.4429	0.8290	1.0849	0.159*	0.50
C10	0.626 (5)	0.699 (2)	0.9975 (15)	0.112 (6)	0.50
H10	0.4933	0.6553	1.0109	0.134*	0.50
C12	0.798 (6)	0.854 (3)	1.0238 (16)	0.128 (9)	0.50
H12	0.7988	0.9192	1.0546	0.153*	0.50
C13	1.003 (4)	0.8186 (14)	0.9621 (15)	0.109 (4)	0.50
H13	1.1409	0.8600	0.9478	0.131*	0.50
C14	1.007 (3)	0.7216 (16)	0.9208 (10)	0.089 (4)	0.50
H14	1.1510	0.6978	0.8771	0.107*	0.50
C15	1.0002 (5)	0.1234 (2)	0.64080 (18)	0.0965 (8)
H15A	1.0431	0.1663	0.5806	0.116*
H15B	0.8372	0.0966	0.6407	0.116*
O1	0.2389 (2)	0.39389 (12)	0.52819 (9)	0.0771 (4)
O2	0.1076 (2)	0.56551 (11)	0.58910 (9)	0.0786 (5)
H2	0.0056	0.5746	0.5506	0.118*
O3	0.6562 (3)	0.56890 (12)	0.82994 (9)	0.0821 (5)
O4	0.9731 (3)	0.19714 (13)	0.71375 (11)	0.0918 (5)
C16	1.2137 (4)	0.01969 (19)	0.65555 (17)	0.0819 (6)	0.50
C17	1.311 (3)	−0.0007 (14)	0.7341 (13)	0.123 (6)	0.50
H17	1.2647	0.0503	0.7812	0.148*	0.50
C18	1.498 (2)	−0.1088 (13)	0.7431 (10)	0.118 (4)	0.50
H18	1.5568	−0.1319	0.8008	0.141*	0.50
C19	1.592 (4)	−0.1779 (19)	0.672 (2)	0.107 (7)	0.50
H19	1.7133	−0.2461	0.6796	0.128*	0.50
C20	1.506 (2)	−0.1445 (10)	0.5925 (11)	0.119 (4)	0.50
H20	1.5708	−0.1903	0.5427	0.143*	0.50
C21	1.3231 (14)	−0.0455 (7)	0.5771 (6)	0.102 (2)	0.50
H21	1.2735	−0.0222	0.5180	0.123*	0.50
C21A	1.388 (3)	0.0108 (12)	0.7188 (12)	0.087 (4)	0.50
H21A	1.3649	0.0714	0.7574	0.105*	0.50
C17A	1.2212 (16)	−0.0818 (6)	0.6129 (5)	0.091 (2)	0.50
H17A	1.0879	−0.0863	0.5792	0.110*	0.50
C18A	1.420 (2)	−0.1752 (10)	0.6191 (9)	0.104 (3)	0.50
H18A	1.4344	−0.2395	0.5851	0.124*	0.50
C19A	1.604 (4)	−0.170 (2)	0.680 (2)	0.116 (9)	0.50
H19A	1.7397	−0.2329	0.6857	0.139*	0.50
C20A	1.588 (3)	−0.0765 (13)	0.7298 (13)	0.109 (4)	0.50
H20A	1.7085	−0.0737	0.7693	0.131*	0.50
C11A	0.945 (5)	0.8536 (15)	0.9366 (15)	0.122 (5)	0.50
H11A	1.0322	0.9136	0.9086	0.146*	0.50
C9A	0.8300 (5)	0.65976 (19)	0.93627 (17)	0.0705 (6)	0.50
C10A	0.986 (4)	0.7480 (16)	0.8932 (12)	0.101 (4)	0.50
H10A	1.1073	0.7352	0.8397	0.121*	0.50
C12A	0.777 (5)	0.870 (2)	1.021 (2)	0.118 (8)	0.50
H12A	0.7512	0.9388	1.0496	0.141*	0.50
C14A	0.663 (4)	0.678 (2)	1.0200 (13)	0.081 (3)	0.50
H14A	0.5643	0.6216	1.0477	0.097*	0.50
C13A	0.645 (4)	0.776 (2)	1.0596 (13)	0.096 (5)	0.50
H13A	0.5398	0.7840	1.1172	0.115*	0.50
C16A	1.2137 (4)	0.01969 (19)	0.65555 (17)	0.0819 (6)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0606 (10)	0.0610 (12)	0.0628 (11)	−0.0002 (9)	−0.0110 (9)	−0.0101 (9)
C2	0.0577 (10)	0.0599 (12)	0.0602 (11)	−0.0032 (8)	−0.0116 (8)	−0.0069 (9)
C3	0.0648 (11)	0.0612 (12)	0.0641 (11)	0.0030 (8)	−0.0142 (9)	−0.0097 (9)
C4	0.0703 (11)	0.0595 (12)	0.0620 (11)	−0.0017 (9)	−0.0167 (9)	−0.0125 (9)
C5	0.0692 (11)	0.0666 (13)	0.0666 (12)	0.0001 (9)	−0.0224 (9)	−0.0100 (10)
C6	0.0713 (11)	0.0596 (12)	0.0744 (12)	0.0063 (9)	−0.0215 (10)	−0.0127 (10)
C7	0.0713 (11)	0.0648 (13)	0.0712 (12)	0.0012 (10)	−0.0203 (9)	−0.0145 (9)
C8	0.0778 (12)	0.0754 (14)	0.0830 (14)	−0.0039 (10)	−0.0320 (11)	−0.0114 (11)
C9	0.0755 (13)	0.0689 (13)	0.0719 (14)	−0.0086 (12)	−0.0259 (12)	−0.0111 (11)
C11	0.158 (16)	0.098 (11)	0.134 (13)	−0.007 (10)	0.007 (10)	−0.043 (10)
C10	0.144 (13)	0.095 (10)	0.103 (12)	−0.048 (9)	−0.001 (8)	−0.017 (8)
C12	0.20 (2)	0.100 (12)	0.089 (10)	−0.025 (10)	−0.011 (10)	−0.054 (8)
C13	0.111 (6)	0.079 (8)	0.146 (14)	−0.022 (6)	−0.025 (7)	−0.022 (7)
C14	0.090 (4)	0.078 (7)	0.096 (10)	−0.009 (4)	−0.006 (6)	−0.018 (6)
C15	0.1051 (16)	0.0757 (16)	0.1102 (18)	0.0201 (12)	−0.0423 (14)	−0.0365 (13)
O1	0.0803 (9)	0.0747 (9)	0.0783 (9)	0.0080 (7)	−0.0301 (7)	−0.0240 (7)
O2	0.0789 (8)	0.0692 (9)	0.0882 (10)	0.0108 (7)	−0.0338 (7)	−0.0184 (7)
O3	0.0962 (10)	0.0701 (9)	0.0839 (9)	0.0106 (7)	−0.0419 (8)	−0.0244 (7)
O4	0.1028 (10)	0.0712 (10)	0.1016 (11)	0.0268 (8)	−0.0480 (8)	−0.0317 (8)
C16	0.0851 (14)	0.0636 (14)	0.0955 (17)	0.0050 (11)	−0.0223 (13)	−0.0177 (12)
C17	0.118 (12)	0.134 (9)	0.086 (5)	0.055 (7)	−0.017 (7)	0.000 (5)
C18	0.134 (10)	0.096 (9)	0.104 (5)	0.034 (7)	−0.035 (7)	0.007 (6)
C19	0.131 (12)	0.051 (9)	0.136 (13)	0.002 (7)	−0.035 (11)	−0.007 (8)
C20	0.116 (7)	0.079 (7)	0.158 (11)	0.010 (5)	−0.011 (6)	−0.051 (6)
C21	0.107 (5)	0.080 (5)	0.120 (6)	0.019 (4)	−0.032 (4)	−0.041 (4)
C21A	0.082 (6)	0.072 (4)	0.107 (9)	0.013 (4)	−0.023 (5)	−0.037 (5)
C17A	0.112 (5)	0.066 (4)	0.096 (5)	−0.002 (3)	−0.026 (4)	−0.011 (3)
C18A	0.137 (9)	0.054 (5)	0.115 (6)	−0.002 (5)	−0.022 (6)	−0.007 (4)
C19A	0.090 (9)	0.087 (15)	0.138 (14)	0.036 (8)	0.012 (11)	0.002 (9)
C20A	0.087 (6)	0.082 (7)	0.158 (9)	−0.002 (5)	−0.038 (6)	−0.007 (6)
C11A	0.173 (15)	0.083 (10)	0.123 (10)	−0.058 (9)	−0.027 (9)	−0.006 (7)
C9A	0.0755 (13)	0.0689 (13)	0.0719 (14)	−0.0086 (12)	−0.0259 (12)	−0.0111 (11)
C10A	0.143 (9)	0.094 (9)	0.076 (7)	−0.058 (6)	−0.004 (5)	−0.011 (6)
C12A	0.127 (10)	0.082 (8)	0.162 (19)	−0.026 (7)	−0.043 (11)	−0.042 (8)
C14A	0.098 (5)	0.088 (9)	0.059 (6)	−0.027 (5)	−0.002 (4)	−0.017 (5)
C13A	0.109 (7)	0.112 (15)	0.069 (4)	−0.025 (8)	0.001 (5)	−0.027 (6)
C16A	0.0851 (14)	0.0636 (14)	0.0955 (17)	0.0050 (11)	−0.0223 (13)	−0.0177 (12)

Geometric parameters (Å, º) top

C1—O1	1.236 (2)	C15—H15B	0.9700
C1—O2	1.296 (2)	O2—H2	0.8200
C1—C2	1.484 (2)	C16—C17	1.302 (18)
C2—C3	1.374 (2)	C16—C21	1.424 (8)
C2—C7	1.393 (2)	C17—C18	1.45 (2)
C3—C4	1.391 (2)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.36 (3)
C4—O3	1.366 (2)	C18—H18	0.9300
C4—C5	1.379 (3)	C19—C20	1.30 (4)
C5—C6	1.383 (3)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.379 (14)
C6—O4	1.367 (2)	C20—H20	0.9300
C6—C7	1.381 (3)	C21—H21	0.9300
C7—H7	0.9300	C21A—C20A	1.33 (2)
C8—O3	1.425 (2)	C21A—H21A	0.9300
C8—C9	1.490 (3)	C17A—C18A	1.369 (14)
C8—H8A	0.9700	C17A—H17A	0.9300
C8—H8B	0.9700	C18A—C19A	1.42 (4)
C9—C14	1.26 (2)	C18A—H18A	0.9300
C9—C10	1.33 (3)	C19A—C20A	1.36 (3)
C11—C12	1.32 (5)	C19A—H19A	0.9300
C11—C10	1.41 (4)	C20A—H20A	0.9300
C11—H11	0.9300	C11A—C12A	1.40 (3)
C10—H10	0.9300	C11A—C10A	1.41 (3)
C12—C13	1.32 (3)	C11A—H11A	0.9300
C12—H12	0.9300	C10A—H10A	0.9300
C13—C14	1.34 (3)	C12A—C13A	1.42 (4)
C13—H13	0.9300	C12A—H12A	0.9300
C14—H14	0.9300	C14A—C13A	1.32 (3)
C15—O4	1.413 (3)	C14A—H14A	0.9300
C15—C16	1.510 (3)	C13A—H13A	0.9300
C15—H15A	0.9700

O1—C1—O2	123.33 (16)	C16—C15—H15A	109.8
O1—C1—C2	121.00 (16)	O4—C15—H15B	109.8
O2—C1—C2	115.67 (16)	C16—C15—H15B	109.8
C3—C2—C7	121.05 (17)	H15A—C15—H15B	108.3
C3—C2—C1	120.35 (16)	C1—O2—H2	109.5
C7—C2—C1	118.59 (16)	C4—O3—C8	118.81 (14)
C2—C3—C4	119.62 (17)	C6—O4—C15	117.70 (15)
C2—C3—H3	120.2	C17—C16—C21	121.6 (8)
C4—C3—H3	120.2	C17—C16—C15	120.5 (8)
O3—C4—C5	124.69 (16)	C21—C16—C15	117.4 (4)
O3—C4—C3	115.23 (16)	C16—C17—C18	115.3 (14)
C5—C4—C3	120.07 (17)	C16—C17—H17	122.4
C4—C5—C6	119.60 (17)	C18—C17—H17	122.4
C4—C5—H5	120.2	C19—C18—C17	123.6 (17)
C6—C5—H5	120.2	C19—C18—H18	118.2
O4—C6—C7	124.09 (17)	C17—C18—H18	118.2
O4—C6—C5	114.69 (16)	C20—C19—C18	117.0 (17)
C7—C6—C5	121.21 (17)	C20—C19—H19	121.5
C6—C7—C2	118.43 (17)	C18—C19—H19	121.5
C6—C7—H7	120.8	C19—C20—C21	124.2 (14)
C2—C7—H7	120.8	C19—C20—H20	117.9
O3—C8—C9	107.77 (15)	C21—C20—H20	117.9
O3—C8—H8A	110.2	C20—C21—C16	117.1 (9)
C9—C8—H8A	110.2	C20—C21—H21	121.4
O3—C8—H8B	110.2	C16—C21—H21	121.4
C9—C8—H8B	110.2	C20A—C21A—H21A	116.9
H8A—C8—H8B	108.5	C18A—C17A—H17A	119.2
C14—C9—C10	114.7 (15)	C17A—C18A—C19A	117.3 (13)
C14—C9—C8	122.2 (8)	C17A—C18A—H18A	121.3
C10—C9—C8	123.1 (13)	C19A—C18A—H18A	121.3
C12—C11—C10	112 (3)	C20A—C19A—C18A	122.3 (15)
C12—C11—H11	124.2	C20A—C19A—H19A	118.8
C10—C11—H11	124.2	C18A—C19A—H19A	118.8
C9—C10—C11	126 (3)	C21A—C20A—C19A	116.2 (16)
C9—C10—H10	116.9	C21A—C20A—H20A	121.9
C11—C10—H10	116.9	C19A—C20A—H20A	121.9
C13—C12—C11	124 (3)	C12A—C11A—C10A	121.5 (19)
C13—C12—H12	117.9	C12A—C11A—H11A	119.3
C11—C12—H12	117.9	C10A—C11A—H11A	119.3
C12—C13—C14	118 (2)	C11A—C10A—H10A	121.4
C12—C13—H13	121.1	C11A—C12A—C13A	117 (2)
C14—C13—H13	121.1	C11A—C12A—H12A	121.6
C9—C14—C13	125.4 (14)	C13A—C12A—H12A	121.6
C9—C14—H14	117.3	C13A—C14A—H14A	120.4
C13—C14—H14	117.3	C14A—C13A—C12A	125 (2)
O4—C15—C16	109.24 (18)	C14A—C13A—H13A	117.6
O4—C15—H15A	109.8	C12A—C13A—H13A	117.6

O1—C1—C2—C3	179.21 (16)	C10—C9—C14—C13	1.5 (18)
O2—C1—C2—C3	−1.0 (2)	C8—C9—C14—C13	−177.8 (11)
O1—C1—C2—C7	0.4 (3)	C12—C13—C14—C9	0 (3)
O2—C1—C2—C7	−179.85 (16)	C5—C4—O3—C8	4.4 (3)
C7—C2—C3—C4	−1.0 (3)	C3—C4—O3—C8	−175.13 (16)
C1—C2—C3—C4	−179.76 (15)	C9—C8—O3—C4	173.58 (17)
C2—C3—C4—O3	−179.84 (15)	C7—C6—O4—C15	12.0 (3)
C2—C3—C4—C5	0.6 (3)	C5—C6—O4—C15	−167.82 (19)
O3—C4—C5—C6	−179.43 (16)	C16—C15—O4—C6	176.14 (18)
C3—C4—C5—C6	0.1 (3)	O4—C15—C16—C17	11.0 (9)
C4—C5—C6—O4	179.37 (17)	O4—C15—C16—C21	−161.8 (4)
C4—C5—C6—C7	−0.4 (3)	C21—C16—C17—C18	−12.9 (17)
O4—C6—C7—C2	−179.70 (18)	C15—C16—C17—C18	174.6 (9)
C5—C6—C7—C2	0.1 (3)	C16—C17—C18—C19	8 (2)
C3—C2—C7—C6	0.6 (3)	C17—C18—C19—C20	−1 (3)
C1—C2—C7—C6	179.44 (16)	C18—C19—C20—C21	−1 (3)
O3—C8—C9—C14	−114.4 (7)	C19—C20—C21—C16	−3.7 (18)
O3—C8—C9—C10	66.4 (9)	C17—C16—C21—C20	11.5 (13)
C14—C9—C10—C11	1 (2)	C15—C16—C21—C20	−175.8 (6)
C8—C9—C10—C11	179.8 (15)	C17A—C18A—C19A—C20A	−1 (3)
C12—C11—C10—C9	−3 (3)	C18A—C19A—C20A—C21A	0 (3)
C10—C11—C12—C13	4 (4)	C10A—C11A—C12A—C13A	−1 (3)
C11—C12—C13—C14	−3 (4)	C11A—C12A—C13A—C14A	−3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.82	2.6333 (18)	175
C20—H20···O1ⁱⁱ	0.93	2.66	3.507 (13)	153

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₈O₄
M_r	334.37
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	5.2801 (2), 11.6830 (5), 14.4803 (7)
α, β, γ (°)	83.303 (2), 80.775 (2), 79.031 (1)
V (Å³)	862.17 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.11 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5626, 3084, 1801
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.163, 1.03
No. of reflections	3084
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.15

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.82	2.6333 (18)	174.5
C20—H20···O1ⁱⁱ	0.93	2.66	3.507 (13)	152.6

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

Acknowledgements

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database. RMF also thanks the Universidad del Valle, Colombia, and CG thanks the Universidad San Buenaventura, Cali, Colombia, for partial financial support.

References

Busskamp, H., Deacon, G. B., Hilder, M., Junk, P. C., Kynast, U. H., Lee, W. W. & Turner, D. R. (2007). CrystEngComm, 9, 394–411. CAS Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, pp. 350–362. New York: Oxford University Press Inc. Google Scholar
Etter, M. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fréchet, J. M. J. (2002). PNAS, 99, 4782-4787. Web of Science PubMed Google Scholar
Gainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2009). Acta Cryst. E65, o3261–o3262. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hawker, C. & Fréchet, J. M. J. (1992). J. Chem. Soc. Perkin Trans. 1, pp. 2459–2469. CrossRef Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Remya, P. N., Biju, S., Reddy, M. L., Cowley, A. H. & Findlater, M. (2008). Inorg. Chem. 47, 7396–7404. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sivakumar, S., Reddy, M. L., Cowley, A. H. & Vasudevan, K. V. (2010). Dalton Trans. 39, 776–786. Web of Science CrossRef CAS PubMed Google Scholar
Xiao, Z.-P., Fang, R.-Q., Shi, L., Ding, H., Xu, C. & Zhu, H.-L. (2007). Can. J. Chem. 85, 951–957. Web of Science CSD CrossRef CAS Google Scholar
Zhu, P., Zhao, Y., Chen, H., Cui, Q. & Wei, Q. (2009). Acta Cryst. E65, o823. Web of Science CSD CrossRef IUCr Journals Google Scholar