organic compounds
Dimethyl 4,5-dichlorophthalate
aDepartment of Chemistry, Pomona College, 645 N. College Ave., Claremont, CA 91711, USA, bDepartment of Chemistry and Biochemistry, W.M. Keck Foundation Center for Molecular Structure, California State University San Marcos, 333. S. Twin Oaks Valley Road, San Marcos, CA 92096, USA, and cDepartment of Chemistry, Harvey Mudd College, 301 Platt Blvd., Claremont, CA 91711, USA
*Correspondence e-mail: Daniel_OLeary@pomona.edu
While endeavoring to synthesize new chlorinated ligands for ruthenium-based metathesis catalysts, the title compound dimethyl 4,5-dichlorophthalate, C10H8Cl2O4, was prepared from commercially available 4,5-dichlorophthalic acid in ∼77% yield. The title molecule, which also finds utility as a precursor molecule for the synthesis of drugs used in the treatment of Alzheimer's disease, shows one carbonyl-containing methyl ester moiety lying nearly co-planar with the chlorine-derivatized aromatic ring while the second methyl ester shows a significant deviation of 101.05 (12)° from the least-squares plane of the aromatic ring. Within the crystal, structural integrity is maintained by the concerted effects of electrostatic interactions involving the electron-deficient carbonyl carbon atom and the electron-rich aromatic ring along the a-axis direction and C—H⋯O hydrogen bonds between neighboring molecules parallel to b.
Keywords: crystal structure; carbonyl; ester; metathesis; catalyst.
CCDC reference: 720360
Structure description
While endeavoring to synthesize new chlorinated ligands for ruthenium-based metathesis catalysts (Anderson et al., 2006), the title compound, 1, was prepared from commercially available 4,5-dichlorophthalic acid in ∼77% yield. The title molecule also finds utility as a precursor molecule for the synthesis of drugs used in the treatment of Alzheimer's disease (Hennessy & Buchwald, 2005).
Compound 1 crystallizes in the centrosymmetric triclinic P with a full molecule of the title compound as the contents of (Fig. 1, Table 1). Within the structure of 1, one of the carbonyl-containing ester groups is nearly co-planar with the aromatic ring demonstrating a deviation of 3.41 (12)° from the least-squares plane of the chlorine-derivatized aromatic ring. The second ester group reveals a much larger deviation from planarity as the dihedral angle involving the second carbonyl group is 101.05 (12)°.
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Looking down the a-axis, and involving a second molecule of 1 related by inversion, the centroid of the electron-rich, chlorine-derivatized aromatic ring of the first molecule lies above the electron-deficient carbonyl carbon atom of the second at a distance of 3.4600 (12) Å, suggesting the presence of electrostatic interactions (Fig. 2). In addition to the electrostatic interactions, when looking into the bc-plane, between H5 on the aromatic ring and O1 from the carbonyl that is nearly co-planar with the aromatic ring, a C—H⋯O [d(C5⋯O1) = 3.23 Å; Θ(C5—H5—O1) = 159°] hydrogen bond was observed (Fig. 3, Table 2). A one-dimensional array of symmetry-equivalent molecules of 1 linked by C—H⋯O hydrogen bonds results along the b-axis direction when looking into the bc-plane (Fig. 3). While there are no additional interactions between neighboring, co-planar one-dimensional arrays parallel to one another along c, weak C—H⋯O [d(C10⋯O3) = 3.54 Å; Θ(C10—H10B—O3) = 147°] interactions with a neighboring layer having the symmetry code (1 − x, −y, −z) yielded a centrosymmetric dimer (Fig. 4, Table 2) having the R22(10) graph-set notation (Bernstein et al., 1995).
Synthesis and crystallization
Compound 1 was synthesized by adding 4,5-dichlorophthalic acid (23.68 mmol, 5.566 g) to 70 ml of CH3OH in a 200 ml flask. While stirring, 1.0 ml H2SO4 (98%) was added dropwise and the mixture was allowed to reflux at 70°C overnight. The product was extracted with ethyl acetate, and washed with water, concentrated NaHCO3, 10% NaHCO3, and then a of NaCl. After filtering through Na2SO4 to remove trace moisture, the solvent was removed in vacuo to yield a clear oil, which later crystallized into small rods. Recrystallization from the mixed solvents of isopropyl alcohol and dichloromethane produced X-ray quality crystals of 1 up to 2 mm.
Refinement
Crystal data, data collection and structure 1 are summarized in Table 2. The choice of the P for 1 was unambiguously verified by PLATON (Spek, 2003; Spek, 2020).
details forStructural data
CCDC reference: 720360
https://doi.org/10.1107/S2414314621010439/bv4041sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621010439/bv4041Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314621010439/bv4041Isup3.cml
Data collection: APEX2 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C10H8Cl2O4 | Z = 2 |
Mr = 263.06 | F(000) = 268 |
Triclinic, P1 | Dx = 1.628 Mg m−3 |
a = 7.0204 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.7661 (6) Å | Cell parameters from 548 reflections |
c = 10.5392 (8) Å | θ = 2.4–27.7° |
α = 97.733 (1)° | µ = 0.60 mm−1 |
β = 109.293 (1)° | T = 173 K |
γ = 90.217 (1)° | Irregular, colorless |
V = 536.69 (7) Å3 | 0.35 × 0.29 × 0.28 mm |
Bruker APEX CCD area detector diffractometer | 2582 independent reflections |
Radiation source: Fine-focus sealed tube | 2417 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
phi and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −9→9 |
Tmin = 0.838, Tmax = 0.927 | k = −10→10 |
5934 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.1955P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2582 reflections | Δρmax = 0.45 e Å−3 |
147 parameters | Δρmin = −0.21 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. All non-hydrogen atoms were refined anisotropically. H atoms bound to C atoms were constrained to ride on the atoms onto which they are bonded, where C—H = 0.95 (aromatic) or 0.98 Å (methyl) with Uiso(H) = 1.2Ueq(C). |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.81953 (5) | 0.48342 (4) | 0.83259 (3) | 0.02349 (9) | |
Cl2 | 0.74478 (5) | 0.08068 (4) | 0.71750 (3) | 0.02487 (9) | |
O1 | 0.76916 (17) | 0.76700 (12) | 0.40055 (10) | 0.0310 (2) | |
O2 | 0.69277 (14) | 0.55617 (11) | 0.22210 (9) | 0.02121 (18) | |
O3 | 0.50933 (14) | 0.17388 (12) | 0.16137 (9) | 0.02470 (19) | |
O4 | 0.84744 (13) | 0.20884 (11) | 0.21752 (8) | 0.02113 (18) | |
C1 | 0.73795 (16) | 0.47447 (14) | 0.43804 (11) | 0.0158 (2) | |
C2 | 0.77075 (17) | 0.53010 (15) | 0.57530 (12) | 0.0170 (2) | |
H2 | 0.7904 | 0.6508 | 0.6094 | 0.020* | |
C3 | 0.77483 (17) | 0.41014 (15) | 0.66231 (11) | 0.0172 (2) | |
C4 | 0.74445 (17) | 0.23318 (15) | 0.61230 (12) | 0.0181 (2) | |
C5 | 0.71216 (18) | 0.17662 (15) | 0.47593 (12) | 0.0185 (2) | |
H5 | 0.6921 | 0.0558 | 0.4423 | 0.022* | |
C6 | 0.70903 (17) | 0.29623 (14) | 0.38820 (11) | 0.0159 (2) | |
C7 | 0.73570 (17) | 0.61539 (15) | 0.35369 (12) | 0.0179 (2) | |
C8 | 0.6829 (2) | 0.68909 (17) | 0.13612 (13) | 0.0247 (3) | |
H8A | 0.6390 | 0.6352 | 0.0408 | 0.037* | |
H8B | 0.8168 | 0.7473 | 0.1603 | 0.037* | |
H8C | 0.5863 | 0.7746 | 0.1491 | 0.037* | |
C9 | 0.67274 (18) | 0.22206 (14) | 0.24202 (12) | 0.0175 (2) | |
C10 | 0.8297 (2) | 0.14662 (17) | 0.07783 (12) | 0.0249 (3) | |
H10A | 0.7640 | 0.2330 | 0.0200 | 0.037* | |
H10B | 0.7485 | 0.0365 | 0.0474 | 0.037* | |
H10C | 0.9646 | 0.1283 | 0.0717 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02835 (16) | 0.02741 (16) | 0.01490 (15) | −0.00009 (11) | 0.00920 (12) | −0.00131 (11) |
Cl2 | 0.03392 (18) | 0.02289 (16) | 0.01804 (15) | −0.00098 (12) | 0.00730 (12) | 0.00740 (11) |
O1 | 0.0505 (6) | 0.0152 (4) | 0.0266 (5) | 0.0004 (4) | 0.0124 (4) | 0.0022 (3) |
O2 | 0.0281 (4) | 0.0181 (4) | 0.0175 (4) | −0.0002 (3) | 0.0066 (3) | 0.0052 (3) |
O3 | 0.0253 (5) | 0.0269 (4) | 0.0174 (4) | −0.0058 (3) | 0.0021 (3) | 0.0010 (3) |
O4 | 0.0235 (4) | 0.0248 (4) | 0.0136 (4) | 0.0029 (3) | 0.0056 (3) | −0.0005 (3) |
C1 | 0.0142 (5) | 0.0158 (5) | 0.0169 (5) | 0.0010 (4) | 0.0045 (4) | 0.0026 (4) |
C2 | 0.0152 (5) | 0.0161 (5) | 0.0188 (5) | 0.0008 (4) | 0.0056 (4) | −0.0004 (4) |
C3 | 0.0156 (5) | 0.0217 (5) | 0.0139 (5) | 0.0011 (4) | 0.0052 (4) | 0.0000 (4) |
C4 | 0.0183 (5) | 0.0196 (5) | 0.0164 (5) | 0.0003 (4) | 0.0049 (4) | 0.0050 (4) |
C5 | 0.0216 (5) | 0.0155 (5) | 0.0171 (5) | −0.0003 (4) | 0.0048 (4) | 0.0019 (4) |
C6 | 0.0155 (5) | 0.0165 (5) | 0.0143 (5) | 0.0002 (4) | 0.0034 (4) | 0.0011 (4) |
C7 | 0.0168 (5) | 0.0167 (5) | 0.0204 (5) | 0.0019 (4) | 0.0059 (4) | 0.0036 (4) |
C8 | 0.0292 (6) | 0.0237 (6) | 0.0243 (6) | 0.0038 (5) | 0.0098 (5) | 0.0115 (5) |
C9 | 0.0242 (6) | 0.0125 (5) | 0.0150 (5) | 0.0009 (4) | 0.0049 (4) | 0.0030 (4) |
C10 | 0.0342 (7) | 0.0261 (6) | 0.0147 (5) | 0.0029 (5) | 0.0097 (5) | −0.0001 (4) |
Cl1—C3 | 1.7305 (12) | C2—C3 | 1.3865 (16) |
Cl2—C4 | 1.7272 (12) | C3—C4 | 1.3931 (16) |
O1—C7 | 1.2042 (15) | C4—C5 | 1.3871 (16) |
O2—C7 | 1.3330 (15) | C5—H5 | 0.9500 |
O2—C8 | 1.4500 (14) | C5—C6 | 1.3915 (15) |
O3—C9 | 1.2022 (15) | C6—C9 | 1.5069 (16) |
O4—C9 | 1.3359 (15) | C8—H8A | 0.9800 |
O4—C10 | 1.4503 (14) | C8—H8B | 0.9800 |
C1—C2 | 1.3940 (16) | C8—H8C | 0.9800 |
C1—C6 | 1.4018 (15) | C10—H10A | 0.9800 |
C1—C7 | 1.4969 (15) | C10—H10B | 0.9800 |
C2—H2 | 0.9500 | C10—H10C | 0.9800 |
C7—O2—C8 | 115.05 (9) | C5—C6—C9 | 116.26 (10) |
C9—O4—C10 | 115.31 (10) | O1—C7—O2 | 123.60 (11) |
C2—C1—C6 | 119.63 (10) | O1—C7—C1 | 123.11 (11) |
C2—C1—C7 | 115.67 (10) | O2—C7—C1 | 113.29 (9) |
C6—C1—C7 | 124.70 (10) | O2—C8—H8A | 109.5 |
C1—C2—H2 | 119.8 | O2—C8—H8B | 109.5 |
C3—C2—C1 | 120.33 (10) | O2—C8—H8C | 109.5 |
C3—C2—H2 | 119.8 | H8A—C8—H8B | 109.5 |
C2—C3—Cl1 | 119.14 (9) | H8A—C8—H8C | 109.5 |
C2—C3—C4 | 119.92 (10) | H8B—C8—H8C | 109.5 |
C4—C3—Cl1 | 120.94 (9) | O3—C9—O4 | 125.21 (11) |
C3—C4—Cl2 | 121.06 (9) | O3—C9—C6 | 124.09 (11) |
C5—C4—Cl2 | 118.80 (9) | O4—C9—C6 | 110.60 (10) |
C5—C4—C3 | 120.14 (10) | O4—C10—H10A | 109.5 |
C4—C5—H5 | 119.9 | O4—C10—H10B | 109.5 |
C4—C5—C6 | 120.23 (10) | O4—C10—H10C | 109.5 |
C6—C5—H5 | 119.9 | H10A—C10—H10B | 109.5 |
C1—C6—C9 | 124.00 (10) | H10A—C10—H10C | 109.5 |
C5—C6—C1 | 119.74 (10) | H10B—C10—H10C | 109.5 |
Cl1—C3—C4—Cl2 | 1.42 (14) | C4—C5—C6—C1 | −0.23 (17) |
Cl1—C3—C4—C5 | −178.93 (9) | C4—C5—C6—C9 | −179.96 (10) |
Cl2—C4—C5—C6 | 179.38 (9) | C5—C6—C9—O3 | 78.67 (15) |
C1—C2—C3—Cl1 | 179.08 (9) | C5—C6—C9—O4 | −97.92 (12) |
C1—C2—C3—C4 | −0.50 (17) | C6—C1—C2—C3 | 0.00 (17) |
C1—C6—C9—O3 | −101.05 (14) | C6—C1—C7—O1 | −176.90 (12) |
C1—C6—C9—O4 | 82.36 (13) | C6—C1—C7—O2 | 3.20 (16) |
C2—C1—C6—C5 | 0.37 (17) | C7—C1—C2—C3 | 179.72 (10) |
C2—C1—C6—C9 | −179.92 (10) | C7—C1—C6—C5 | −179.33 (10) |
C2—C1—C7—O1 | 3.39 (17) | C7—C1—C6—C9 | 0.38 (18) |
C2—C1—C7—O2 | −176.51 (10) | C8—O2—C7—O1 | −1.71 (17) |
C2—C3—C4—Cl2 | −179.00 (8) | C8—O2—C7—C1 | 178.18 (9) |
C2—C3—C4—C5 | 0.65 (17) | C10—O4—C9—O3 | 6.33 (17) |
C3—C4—C5—C6 | −0.28 (18) | C10—O4—C9—C6 | −177.12 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.95 | 2.33 | 3.2327 (15) | 159 |
C10—H10B···O3ii | 0.98 | 2.68 | 3.5380 (16) | 147 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z. |
Funding information
Funding for this research was provided by: Pomona College; Harvey Mudd College.
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