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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015006891/hb7398sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989015006891/hb7398Isup2.hkl
Contains datablock I

CCDC reference: 1058073

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.003 Å
  • Disorder in main residue
  • R factor = 0.041
  • wR factor = 0.162
  • Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.1 Note PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 7.957 Check PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 6 Report PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers .... 1 Check
Alert level G PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ... 1 Report PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large. 0.11 Report PLAT300_ALERT_4_G Atom Site Occupancy of >O3A is Constrained at 0.630 Check PLAT300_ALERT_4_G Atom Site Occupancy of <O3B is Constrained at 0.370 Check PLAT300_ALERT_4_G Atom Site Occupancy of >O3A_a is Constrained at 0.630 Check PLAT300_ALERT_4_G Atom Site Occupancy of <O3B_a is Constrained at 0.370 Check PLAT301_ALERT_3_G Main Residue Disorder ............ Percentage = 9 Note PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 6 Note PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 38 % PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ... 2 Report PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ....... Please Check
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 12 ALERT level G = General information/check it is not something unexpected 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 7 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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

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.

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 .

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.

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

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).

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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular packing of the title compound when viewed along c axis. Dashed lines indicate intermolecular C—H···O interactions.
[Figure 3] 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
C17H16O6Block
Mr = 316.30Dx = 1.316 Mg m3
Orthorhombic, PbcnMelting point: 465 K
Hall symbol: -P 2n 2abMo Kα radiation, λ = 0.71073 Å
a = 5.4307 (19) ÅCell parameters from 1405 reflections
b = 8.131 (3) Åθ = 3.4–25.0°
c = 36.149 (10) ŵ = 0.10 mm1
V = 1596.3 (9) Å3T = 296 K
Z = 4Block, colourless
F(000) = 6640.18 × 0.16 × 0.14 mm
Data collection top
Bruker APEXII CCD
diffractometer
1405 independent reflections
Radiation source: fine-focus sealed tube1008 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 2.09 pixels mm-1θmax = 25.0°, θmin = 3.4°
phi and ω scansh = 66
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
k = 98
Tmin = 0.982, Tmax = 0.986l = 4242
6486 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.162 w = 1/[σ2(Fo2) + (0.1061P)2 + 0.0364P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.004
1405 reflectionsΔρmax = 0.18 e Å3
121 parametersΔρmin = 0.16 e Å3
6 restraintsExtinction correction: SHELXL2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 constraintsExtinction coefficient: 0.019 (4)
Primary atom site location: structure-invariant direct methods
Crystal data top
C17H16O6V = 1596.3 (9) Å3
Mr = 316.30Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 5.4307 (19) ŵ = 0.10 mm1
b = 8.131 (3) ÅT = 296 K
c = 36.149 (10) Å0.18 × 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)
Tmin = 0.982, Tmax = 0.986Rint = 0.036
6486 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0416 restraints
wR(F2) = 0.162H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.18 e Å3
1405 reflectionsΔρmin = 0.16 e Å3
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
xyzUiso*/UeqOcc. (<1)
O20.0641 (3)0.84493 (15)0.31318 (4)0.0610 (5)
O10.0400 (3)0.60669 (15)0.45593 (4)0.0591 (5)
C80.0313 (6)0.7692 (3)0.28435 (6)0.0854 (9)
C10.2471 (4)0.6502 (3)0.47762 (6)0.0697 (7)
H1B0.39470.61450.46540.105*
H1A0.23530.59830.50140.105*
H1C0.25150.76750.48070.105*
C90.00000.8706 (5)0.25000.0964 (15)
C20.0277 (3)0.66889 (19)0.42034 (5)0.0454 (5)
C50.0275 (3)0.7785 (2)0.34879 (5)0.0468 (5)
C40.1692 (3)0.8324 (2)0.36942 (5)0.0511 (6)
H40.28240.90520.35920.061*
C70.1689 (3)0.6158 (2)0.39913 (6)0.0523 (5)
H70.28290.54300.40910.063*
C60.1967 (3)0.6706 (2)0.36313 (6)0.0525 (6)
H60.32860.63480.34880.063*
C30.1984 (3)0.7778 (2)0.40568 (5)0.0499 (6)
H30.33060.81380.41990.060*
O3B0.051 (3)0.6253 (9)0.2836 (3)0.080 (4)0.37 (3)
O3A0.194 (5)0.661 (2)0.2893 (2)0.152 (6)0.63 (3)
H9A0.139 (6)0.936 (4)0.2521 (11)0.150 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0850 (11)0.0534 (8)0.0445 (10)0.0136 (6)0.0043 (7)0.0011 (6)
O10.0721 (10)0.0615 (9)0.0438 (9)0.0056 (6)0.0010 (6)0.0048 (6)
C80.147 (3)0.0634 (16)0.0460 (15)0.0256 (15)0.0084 (14)0.0017 (11)
C10.0823 (16)0.0756 (14)0.0514 (14)0.0012 (11)0.0106 (12)0.0041 (10)
C90.183 (5)0.062 (2)0.045 (2)0.0000.010 (2)0.000
C20.0547 (12)0.0396 (9)0.0418 (12)0.0040 (7)0.0041 (8)0.0033 (7)
C50.0602 (12)0.0424 (10)0.0380 (11)0.0083 (8)0.0005 (8)0.0023 (7)
C40.0547 (12)0.0448 (10)0.0538 (13)0.0037 (7)0.0023 (9)0.0015 (8)
C70.0523 (12)0.0483 (10)0.0562 (13)0.0066 (8)0.0061 (9)0.0019 (8)
C60.0509 (12)0.0514 (11)0.0553 (13)0.0006 (8)0.0072 (9)0.0071 (9)
C30.0529 (12)0.0471 (10)0.0497 (12)0.0045 (8)0.0054 (8)0.0016 (8)
O3B0.140 (8)0.043 (5)0.057 (4)0.026 (4)0.001 (4)0.006 (2)
O3A0.244 (14)0.158 (7)0.053 (3)0.132 (9)0.017 (5)0.002 (3)
Geometric parameters (Å, º) top
O2—C81.316 (3)C9—H9A0.92 (3)
O2—C51.410 (2)C2—C71.383 (3)
O1—C21.384 (2)C2—C31.387 (3)
O1—C11.416 (3)C5—C61.372 (3)
C8—O3B1.176 (9)C5—C41.375 (3)
C8—O3A1.262 (10)C4—C31.393 (3)
C8—C91.500 (3)C4—H40.9300
C1—H1B0.9600C7—C61.384 (3)
C1—H1A0.9600C7—H70.9300
C1—H1C0.9600C6—H60.9300
C9—C8i1.500 (3)C3—H30.9300
C8—O2—C5119.22 (16)O1—C2—C3123.81 (16)
C2—O1—C1117.48 (15)C7—C2—C3120.20 (18)
O3B—C8—O2121.3 (5)C6—C5—C4121.32 (17)
O3A—C8—O2119.4 (4)C6—C5—O2119.70 (16)
O3B—C8—C9122.6 (6)C4—C5—O2118.82 (16)
O3A—C8—C9125.5 (5)C5—C4—C3119.79 (17)
O2—C8—C9110.7 (2)C5—C4—H4120.1
O1—C1—H1B109.5C3—C4—H4120.1
O1—C1—H1A109.5C2—C7—C6120.35 (17)
H1B—C1—H1A109.5C2—C7—H7119.8
O1—C1—H1C109.5C6—C7—H7119.8
H1B—C1—H1C109.5C5—C6—C7119.19 (17)
H1A—C1—H1C109.5C5—C6—H6120.4
C8—C9—C8i113.4 (3)C7—C6—H6120.4
C8—C9—H9A110 (2)C2—C3—C4119.15 (17)
C8i—C9—H9A107 (2)C2—C3—H3120.4
O1—C2—C7116.00 (16)C4—C3—H3120.4
C5—O2—C8—O3B32.7 (11)C6—C5—C4—C30.3 (3)
C5—O2—C8—O3A14.9 (17)O2—C5—C4—C3175.19 (14)
C5—O2—C8—C9172.58 (17)O1—C2—C7—C6179.78 (15)
O3B—C8—C9—C8i6.5 (10)C3—C2—C7—C60.1 (3)
O3A—C8—C9—C8i56.1 (17)C4—C5—C6—C70.3 (3)
O2—C8—C9—C8i147.9 (3)O2—C5—C6—C7175.16 (15)
C1—O1—C2—C7176.14 (16)C2—C7—C6—C50.2 (3)
C1—O1—C2—C33.8 (3)O1—C2—C3—C4179.77 (16)
C8—O2—C5—C691.6 (2)C7—C2—C3—C40.1 (3)
C8—O2—C5—C492.8 (2)C5—C4—C3—C20.2 (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···AD—HH···AD···AD—H···A
C9—H9A···O3Aii0.92 (3)2.53 (3)3.216 (6)131 (3)
C4—H4···Cg1iii0.932.993.6957134
C7—H7···Cg1iv0.932.993.6980134
Symmetry codes: (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y1/2, z; (iv) x1/2, y3/2, z.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the benzene ring.
D—H···AD—HH···AD···AD—H···A
C9—H9A···O3Ai0.92 (3)2.53 (3)3.216 (6)131 (3)
C4—H4···Cg1ii0.932.993.6957134
C7—H7···Cg1iii0.932.993.6980134
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x+1/2, y1/2, z; (iii) x1/2, y3/2, z.
 

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