



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015006891/hb7398sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989015006891/hb7398Isup2.hkl |
CCDC reference: 1058073
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(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
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.
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.
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).
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).
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.
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).
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).
C17H16O6 | Block |
Mr = 316.30 | Dx = 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 |
Bruker APEXII CCD diffractometer | 1405 independent reflections |
Radiation source: fine-focus sealed tube | 1008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 2.09 pixels mm-1 | θmax = 25.0°, θmin = 3.4° |
phi and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −9→8 |
Tmin = 0.982, Tmax = 0.986 | l = −42→42 |
6486 measured reflections |
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(Fo2) + (0.1061P)2 + 0.0364P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.004 |
1405 reflections | Δρmax = 0.18 e Å−3 |
121 parameters | Δρmin = −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 |
C17H16O6 | V = 1596.3 (9) Å3 |
Mr = 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 |
Bruker APEXII CCD diffractometer | 1405 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 1008 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.986 | Rint = 0.036 |
6486 measured reflections |
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 | Δρmax = 0.18 e Å−3 |
1405 reflections | Δρmin = −0.16 e Å−3 |
121 parameters |
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. |
x | y | z | Uiso*/Ueq | 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)* |
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) |
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. |
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···Cg1iv | 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. |
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. |