Crystal structure of bis­(4-meth­oxy­phenyl) malonate

Devarajegowda, H.C.; Suchetan, P.A.; Sreenivasa, S.; Srinivasa, H.T.; Palakshamurthy, B.S.

doi:10.1107/S2056989015006891

organic compounds

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Volume 71| Part 5| May 2015| Pages o330-o331

https://doi.org/10.1107/S2056989015006891

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Crystal structure of bis(4-methoxyphenyl) malonate

H. C. Devarajegowda,^a P. A. Suchetan,^b S. Sreenivasa,^c H. T. Srinivasa ^d and B. S. Palakshamurthy ^a ^*

^aDepartment of Physics, Yuvaraja's College (Constituent College), University of, Mysore, Mysore, Karnataka 570 005, India, ^bDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka, 572 103, India, ^cDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, and ^dRaman Research Institute, C. V. Raman, Avenue, Sadashivanagar, Bangalore, Karnataka, India
^*Correspondence e-mail: palaksha.bspm@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 6 April 2015; accepted 6 April 2015; online 22 April 2015)

The complete molecule of the title compound, C₁₇H₁₆O₆, is generated by crystallographic twofold symmetry, with the central methylene C atom lying on the rotation axis. The carbonyl O atom is disordered over two adjacent positions in a 0.63 (3):0.37 (3) ratio and the dihedral angle between the benzene rings in the two halves of the molecule is 79.31 (12)°. In the crystal, molecules are connected by C—H⋯O hydrogen bonds, generating (110) sheets. Very weak intrasheet C—H⋯π interactions are also observed.

Keywords: crystal structure; orientational disorder; C—H⋯O interactions; C—H⋯π interactions.

CCDC reference: 1058073

1. Related literature

For the application of the 4-methoxyphenyl group in chemiluminescence, see: Teranishi et al.(1999 ). For its biological activity, see: Prasanna Kumar et al., (2013 ).

2. Experimental

2.1. Crystal data

C₁₇H₁₆O₆
M_r = 316.30
Orthorhombic, P b c n
a = 5.4307 (19) Å
b = 8.131 (3) Å
c = 36.149 (10) Å
V = 1596.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.18 × 0.16 × 0.14 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.982, T_max = 0.986
6486 measured reflections
1405 independent reflections
1008 reflections with I > 2σ(I)
R_int = 0.036

2.3. Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.162
S = 1.03
1405 reflections
121 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O3Aⁱ	0.92 (3)	2.53 (3)	3.216 (6)	131 (3)
C4—H4⋯Cg1ⁱⁱ	0.93	2.99	3.6957	134
C7—H7⋯Cg1ⁱⁱⁱ	0.93	2.99	3.6980	134
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x-{\script{1\over 2}}, y-{\script{3\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Supporting information

CCDC reference: 1058073

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015006891/hb7398sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006891/hb7398Isup2.hkl

checkCIF report

Chemical context top

4-Methoxyphenyl derivatives play significant role in synthesizing chemiluminescence (Teranishi et al., 1999), biologically active materials (Prasanna Kumar et al., 2013) and molecule-based magnetic materials etc., Keeping these things in mind, and our interest towards synthesizing liquid crystals bearing malonate moiety [–C(O)O—CH2—C(O)O-], we report here the crystal structure of the title compound.

Structural commentary top

The molecules of the title compound, C₁₇H₁₆O₆, show two fold rotation symmetry, for which the 2-fold rotation crystallographic axis passes through the C9 atom (with symmetry code -x, y, -z+1/2). The asymmetric unit of the title compound contains half molecule. The carbonyl oxygen atom is disordered over two positions due to crystallographic 2-fold rotation axis (orientational disorder), the occupancy ratio being 0.63 (3) : 0.37 (3). The dihedral angle between the benzene rings in the two halves of the molecule is 79.31 (12)^o. Further, the dihedral angle between the central –CH₂–C(O)–O– segment and the phenyl ring is 86.41 (6)^o. The methoxy group is approximately coplanar with the attached benzene ring, the C1—O1—C2—C3 torsion being 3.76 (1)^o .

Supramolecular features top

In the crystal structure, the molecules are connected via C9—H9···O3 intermolecular interactions running into C(4) chains along crystallographic a and b axis, thus forming sheets in the ab plane. These sheets are further stabilized by C4—H4···pi and C7—H7···pi interactions (where Cg is the centroid of the phenyl ring)along [010], and thus, a two dimensional architecture is observed.

Synthesis and crystallization top

A mixture of malonic acid (1 mmol) and phosphorous oxychloride (POCl₃) was stirred for about an hour at 30°C . To this mixture, 4-methoxyphenol (2 mmol) was added and the reaction mixture was heated to 50°C for 30 minutes. The reaction mixture was poured into crushed ice and the solid obtained was thoroughly washed with water, dilute sodium hydroxide and again with water.

Colourless blocks of the title compound were obtained from slow evaporation technique using methanol as the solvent.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were positioned with idealized geometry using a riding model with C—H = 0.95-0.99 Å. All H-atoms were refined with isotropic displacement parameters (set to 1.2-1.5 times of the U eq of the parent atom). The carbonyl oxygen atom is disordered over two sites and refined with site occupancy factors 0.63 (3) : 0.37 (3).

Related literature top

For the application of the 4-methoxyphenyl group in chemiluminescence, see: Teranishi et al.(1999). For its biological activity, see: Prasanna Kumar et al., (2013).

Structure description top

For the application of the 4-methoxyphenyl group in chemiluminescence, see: Teranishi et al.(1999). For its biological activity, see: Prasanna Kumar et al., (2013).

Synthesis and crystallization top

Colourless blocks of the title compound were obtained from slow evaporation technique using methanol as the solvent.

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The molecular packing of the title compound when viewed along c axis. Dashed lines indicate intermolecular C—H···O interactions.
	Fig. 3. The molecular packing of the title compound when viewed along a axis. Dashed lines indicate intermolecular C—H···π interactions.

Bis(4-methoxyphenyl) malonate top

Crystal data top

C₁₇H₁₆O₆	Block
M_r = 316.30	D_x = 1.316 Mg m⁻³
Orthorhombic, Pbcn	Melting point: 465 K
Hall symbol: -P 2n 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 5.4307 (19) Å	Cell parameters from 1405 reflections
b = 8.131 (3) Å	θ = 3.4–25.0°
c = 36.149 (10) Å	µ = 0.10 mm⁻¹
V = 1596.3 (9) Å³	T = 296 K
Z = 4	Block, colourless
F(000) = 664	0.18 × 0.16 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	1405 independent reflections
Radiation source: fine-focus sealed tube	1008 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 2.09 pixels mm^-1	θ_max = 25.0°, θ_min = 3.4°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −9→8
T_min = 0.982, T_max = 0.986	l = −42→42
6486 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.1061P)² + 0.0364P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.004
1405 reflections	Δρ_max = 0.18 e Å⁻³
121 parameters	Δρ_min = −0.16 e Å⁻³
6 restraints	Extinction correction: SHELXL2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 constraints	Extinction coefficient: 0.019 (4)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₇H₁₆O₆	V = 1596.3 (9) Å³
M_r = 316.30	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 5.4307 (19) Å	µ = 0.10 mm⁻¹
b = 8.131 (3) Å	T = 296 K
c = 36.149 (10) Å	0.18 × 0.16 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	1405 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1008 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.986	R_int = 0.036
6486 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	6 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.18 e Å⁻³
1405 reflections	Δρ_min = −0.16 e Å⁻³
121 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O2	−0.0641 (3)	0.84493 (15)	0.31318 (4)	0.0610 (5)
O1	0.0400 (3)	0.60669 (15)	0.45593 (4)	0.0591 (5)
C8	0.0313 (6)	0.7692 (3)	0.28435 (6)	0.0854 (9)
C1	0.2471 (4)	0.6502 (3)	0.47762 (6)	0.0697 (7)
H1B	0.3947	0.6145	0.4654	0.105*
H1A	0.2353	0.5983	0.5014	0.105*
H1C	0.2515	0.7675	0.4807	0.105*
C9	0.0000	0.8706 (5)	0.2500	0.0964 (15)
C2	0.0277 (3)	0.66889 (19)	0.42034 (5)	0.0454 (5)
C5	−0.0275 (3)	0.7785 (2)	0.34879 (5)	0.0468 (5)
C4	0.1692 (3)	0.8324 (2)	0.36942 (5)	0.0511 (6)
H4	0.2824	0.9052	0.3592	0.061*
C7	−0.1689 (3)	0.6158 (2)	0.39913 (6)	0.0523 (5)
H7	−0.2829	0.5430	0.4091	0.063*
C6	−0.1967 (3)	0.6706 (2)	0.36313 (6)	0.0525 (6)
H6	−0.3286	0.6348	0.3488	0.063*
C3	0.1984 (3)	0.7778 (2)	0.40568 (5)	0.0499 (6)
H3	0.3306	0.8138	0.4199	0.060*
O3B	0.051 (3)	0.6253 (9)	0.2836 (3)	0.080 (4)	0.37 (3)
O3A	0.194 (5)	0.661 (2)	0.2893 (2)	0.152 (6)	0.63 (3)
H9A	−0.139 (6)	0.936 (4)	0.2521 (11)	0.150 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0850 (11)	0.0534 (8)	0.0445 (10)	0.0136 (6)	−0.0043 (7)	0.0011 (6)
O1	0.0721 (10)	0.0615 (9)	0.0438 (9)	−0.0056 (6)	0.0010 (6)	0.0048 (6)
C8	0.147 (3)	0.0634 (16)	0.0460 (15)	0.0256 (15)	0.0084 (14)	−0.0017 (11)
C1	0.0823 (16)	0.0756 (14)	0.0514 (14)	0.0012 (11)	−0.0106 (12)	0.0041 (10)
C9	0.183 (5)	0.062 (2)	0.045 (2)	0.000	−0.010 (2)	0.000
C2	0.0547 (12)	0.0396 (9)	0.0418 (12)	0.0040 (7)	0.0041 (8)	−0.0033 (7)
C5	0.0602 (12)	0.0424 (10)	0.0380 (11)	0.0083 (8)	−0.0005 (8)	−0.0023 (7)
C4	0.0547 (12)	0.0448 (10)	0.0538 (13)	−0.0037 (7)	0.0023 (9)	0.0015 (8)
C7	0.0523 (12)	0.0483 (10)	0.0562 (13)	−0.0066 (8)	0.0061 (9)	−0.0019 (8)
C6	0.0509 (12)	0.0514 (11)	0.0553 (13)	−0.0006 (8)	−0.0072 (9)	−0.0071 (9)
C3	0.0529 (12)	0.0471 (10)	0.0497 (12)	−0.0045 (8)	−0.0054 (8)	−0.0016 (8)
O3B	0.140 (8)	0.043 (5)	0.057 (4)	0.026 (4)	0.001 (4)	−0.006 (2)
O3A	0.244 (14)	0.158 (7)	0.053 (3)	0.132 (9)	0.017 (5)	0.002 (3)

Geometric parameters (Å, º) top

O2—C8	1.316 (3)	C9—H9A	0.92 (3)
O2—C5	1.410 (2)	C2—C7	1.383 (3)
O1—C2	1.384 (2)	C2—C3	1.387 (3)
O1—C1	1.416 (3)	C5—C6	1.372 (3)
C8—O3B	1.176 (9)	C5—C4	1.375 (3)
C8—O3A	1.262 (10)	C4—C3	1.393 (3)
C8—C9	1.500 (3)	C4—H4	0.9300
C1—H1B	0.9600	C7—C6	1.384 (3)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1C	0.9600	C6—H6	0.9300
C9—C8ⁱ	1.500 (3)	C3—H3	0.9300

C8—O2—C5	119.22 (16)	O1—C2—C3	123.81 (16)
C2—O1—C1	117.48 (15)	C7—C2—C3	120.20 (18)
O3B—C8—O2	121.3 (5)	C6—C5—C4	121.32 (17)
O3A—C8—O2	119.4 (4)	C6—C5—O2	119.70 (16)
O3B—C8—C9	122.6 (6)	C4—C5—O2	118.82 (16)
O3A—C8—C9	125.5 (5)	C5—C4—C3	119.79 (17)
O2—C8—C9	110.7 (2)	C5—C4—H4	120.1
O1—C1—H1B	109.5	C3—C4—H4	120.1
O1—C1—H1A	109.5	C2—C7—C6	120.35 (17)
H1B—C1—H1A	109.5	C2—C7—H7	119.8
O1—C1—H1C	109.5	C6—C7—H7	119.8
H1B—C1—H1C	109.5	C5—C6—C7	119.19 (17)
H1A—C1—H1C	109.5	C5—C6—H6	120.4
C8—C9—C8ⁱ	113.4 (3)	C7—C6—H6	120.4
C8—C9—H9A	110 (2)	C2—C3—C4	119.15 (17)
C8ⁱ—C9—H9A	107 (2)	C2—C3—H3	120.4
O1—C2—C7	116.00 (16)	C4—C3—H3	120.4

C5—O2—C8—O3B	32.7 (11)	C6—C5—C4—C3	−0.3 (3)
C5—O2—C8—O3A	−14.9 (17)	O2—C5—C4—C3	175.19 (14)
C5—O2—C8—C9	−172.58 (17)	O1—C2—C7—C6	−179.78 (15)
O3B—C8—C9—C8ⁱ	6.5 (10)	C3—C2—C7—C6	0.1 (3)
O3A—C8—C9—C8ⁱ	56.1 (17)	C4—C5—C6—C7	0.3 (3)
O2—C8—C9—C8ⁱ	−147.9 (3)	O2—C5—C6—C7	−175.16 (15)
C1—O1—C2—C7	176.14 (16)	C2—C7—C6—C5	−0.2 (3)
C1—O1—C2—C3	−3.8 (3)	O1—C2—C3—C4	179.77 (16)
C8—O2—C5—C6	−91.6 (2)	C7—C2—C3—C4	−0.1 (3)
C8—O2—C5—C4	92.8 (2)	C5—C4—C3—C2	0.2 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O3Aⁱⁱ	0.92 (3)	2.53 (3)	3.216 (6)	131 (3)
C4—H4···Cg1ⁱⁱⁱ	0.93	2.99	3.6957	134
C7—H7···Cg1^iv	0.93	2.99	3.6980	134

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O3Aⁱ	0.92 (3)	2.53 (3)	3.216 (6)	131 (3)
C4—H4···Cg1ⁱⁱ	0.93	2.99	3.6957	134
C7—H7···Cg1ⁱⁱⁱ	0.93	2.99	3.6980	134

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

Acknowledgements

BSPM thank Dr Biraj, Sophisticated Analytical Instrumentation Centre (SAIC), Tezpur University, Assam, for his help with the data collection and the UGC, Government of India, for financial support under a Minor Research Project.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o330-o331

https://doi.org/10.1107/S2056989015006891

Open

access