organic compounds
Escitalopram oxalate: co-existence of oxalate dianions and oxalic acid molecules in the same crystal
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, and bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
*Correspondence e-mail: w.harrison@abdn.ac.uk
The title compound {systematic name: (+)-(S)-3-[5-cyano-2-(4-fluorophenyl)-1,3-dihydroisobenzofuran-2yl]propanaminium oxalate oxalic acid 0.325-hydrate}, 2C20H22FN2O+·C2O42−·C2H2O4·0.325H2O, is a molecular salt of the N-protonated escitalopram cation. As well as charge-balancing oxalate dianions, neutral molecules of oxalic acid are present. The component species interact by way of N—H⋯O and short O—H⋯O hydrogen bonds, resulting in supramolecular chains.
Comment
(+)-(S)-1-[3-(Dimethylammonio)propyl]-1-(4-fluorophenyl)-5-phthalan-5-carbonitrile oxalate (C20H21FN2O), common names escitalopram or S-(+)-citalopram, is a widely prescribed drug used to treat depression and related conditions (Burke, 2002). It is conveniently introduced as an oxalate salt, with a nominal formula usually given as C20H21FN2O·C2H2O4, i.e. the presumed proton-transfer reaction is not specified (Sorbera et al., 2001). As part of our ongoing crystallographic studies of pharmaceutical molecules (Harrison et al., 2005), we now report the structure of the title compound, (I), in which two N-protonated escitalopram cations (C20H22FN2O+) and a C2O42− oxalate dianon are accompanied by a neutral molecule of oxalic acid and a partially occupied water molecule (Fig. 1).
The bond lengths and angles in (I) fall within their expected ranges (Cambridge Structural Database, Version 5.27; Allen, 2002). There are two C20H22FN2O+ cations in the atoms C8 and C28 are assumed to possess S configurations, consistent with the known of the biologically active of citalopram (Sanchez et al., 2004). For the C1-containing molecule, the dihedral angle between the mean planes of the C2–C7 and C9–C14 benzene rings is 62.83 (13)°, and the C1/C2/C7/C8/O1 five-membered ring displays an with atom O1 in the flap position [the displacement from the C-atom mean plane is 0.435 (5) Å]. In the C21-containing molecule, the dihedral angle between the C22–C27 and C29–C34 mean planes is 81.99 (13)°, and the for C21/C22/C27/C28/O2 is less pronounced, with atom O2 displaced from the C-atom mean plane by 0.113 (6) Å. The oxalate species are both approximately planar; the dihedral angle between the C41/O3/O4 and C42/O5/O6 groupings is 4.4 (3)°, and the equivalent value for C43/O7/O8 and C44/O9/O10 is 2.8 (6)°.
The component species in (I) interact by way of N—H⋯O and O—H⋯O hydrogen bonds (Table 1), such that both C20H22FN2O+ cations make bifurcated N—H⋯(O,O) hydrogen bonds to the same oxalate dianion. Then, the 2C20H22FN2O+·C2O42− units are linked into [001] chains by way of the oxalic acid molecules, i.e. the oxalate dianions and oxalic acid molecules alternate in the chains (Fig. 2). The short H⋯O separations of the oxalic acid-to-oxalate hydrogen bonds suggests that they are strong interactions.
Although it is not expected from a consideration of the pKa values of oxalic acid (pKa1 = 1.23 and pKa2 = 4.19; Newkome et al., 1985) the co-existence of oxalate dianions and oxalic acid molecules in the same crystal has been observed in a number of compounds, three examples being bis(pyridinium) oxalate oxalic acid (Newkome et al., 1985), barium oxalate oxalic acid dihydrate (Chaix-Pluchery et al., 1989) and 1-(α-pyrrolidiniobenzyl)-2-naphthol oxalate oxalic acid (Periasamy et al., 2004). These three compounds show the same alternating oxalate–oxalic acid hydrogen-bonded chains seen in (I).
Experimental
The title compound was obtained as a gift sample from Jubilant Organosys, Nanjangud, India. The sample of (I) was recrystallized from ethanol (m.p. 420 K).
Crystal data
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Refinement
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was assigned on the basis of the known of escitalopram (Sanchez et al., 2004). The C- and N-bound H atoms were placed in idealized locations (C—H = 0.95–0.99 Å and N—H = 0.93 Å) and refined as riding with Uiso(H) values of 1.2Ueq(carrier) or 1.5Ueq(methyl C). The oxalic acid H atoms were located in a difference map and refined with the restraint O—H = 0.90 (1) Å and the constraint Uiso(H) = 1.2Ueq(O). The H atoms of the partially occupied water molecule could not be located.
effects were negligible and Friedel pairs were merged before The of (I)Data collection: COLLECT (Nonius, 1998); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S010827010605520X/gd3075sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S010827010605520X/gd3075Isup2.hkl
The title compound was obtained as a gift sample from Jubilant Organosys, Nanjangud, India. The sample of (I) was recrystallized from ethanol (m.p. 420 K).
Anomalous dispersion effects were negligible and Friedel pairs were merged before
The of (I) was assigned on the basis of the known of escitalopram (Sanchez et al., 2004). The C– and N-bound H atoms were placed in idealized locations (C—H = 0.95–0.99 Å and N—H = 0.93 Å) and refined as riding with Uiso(H) values of 1.2Ueq(carrier) or 1.5Ueq(methyl C). The oxalic acid H atoms were located in a difference map and refined with the restraint O—H = 0.90 (1) Å and the constraint Uiso(H) = 1.2Ueq(O). The H atoms of the partially occupied water molecule could not be located.Data collection: COLLECT (Nonius, 1998); cell
SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.2C20H22FN2O+·C2O42−·C2H2O4·0.325H2O | F(000) = 879 |
Mr = 834.05 | Dx = 1.324 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4241 reflections |
a = 7.9355 (3) Å | θ = 1.0–27.5° |
b = 24.7376 (9) Å | µ = 0.10 mm−1 |
c = 11.1332 (5) Å | T = 120 K |
β = 106.589 (2)° | Block, colourless |
V = 2094.54 (14) Å3 | 0.32 × 0.24 × 0.18 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 3609 independent reflections |
Radiation source: fine-focus sealed tube | 2652 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and ϕ scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −9→7 |
Tmin = 0.969, Tmax = 0.982 | k = −28→20 |
7581 measured reflections | l = −11→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0473P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.008 |
3609 reflections | Δρmax = 0.17 e Å−3 |
562 parameters | Δρmin = −0.21 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0118 (16) |
2C20H22FN2O+·C2O42−·C2H2O4·0.325H2O | V = 2094.54 (14) Å3 |
Mr = 834.05 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.9355 (3) Å | µ = 0.10 mm−1 |
b = 24.7376 (9) Å | T = 120 K |
c = 11.1332 (5) Å | 0.32 × 0.24 × 0.18 mm |
β = 106.589 (2)° |
Nonius KappaCCD diffractometer | 3609 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2652 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.982 | Rint = 0.037 |
7581 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 3 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.17 e Å−3 |
3609 reflections | Δρmin = −0.21 e Å−3 |
562 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1867 (5) | 0.50590 (17) | 0.2222 (5) | 0.0372 (12) | |
H1A | 0.2960 | 0.5224 | 0.2131 | 0.045* | |
H1B | 0.1401 | 0.5288 | 0.2783 | 0.045* | |
C2 | 0.0547 (5) | 0.49930 (16) | 0.0984 (4) | 0.0293 (11) | |
C3 | 0.0086 (5) | 0.53215 (17) | −0.0070 (5) | 0.0309 (10) | |
H3A | 0.0603 | 0.5668 | −0.0060 | 0.037* | |
C4 | −0.1143 (5) | 0.51331 (16) | −0.1139 (4) | 0.0304 (11) | |
C5 | −0.1927 (5) | 0.46288 (16) | −0.1166 (4) | 0.0292 (10) | |
H5 | −0.2759 | 0.4506 | −0.1910 | 0.035* | |
C6 | −0.1488 (5) | 0.43037 (16) | −0.0094 (4) | 0.0290 (11) | |
H6 | −0.2028 | 0.3961 | −0.0097 | 0.035* | |
C7 | −0.0255 (5) | 0.44895 (15) | 0.0968 (4) | 0.0244 (10) | |
C8 | 0.0571 (4) | 0.42090 (15) | 0.2204 (4) | 0.0258 (10) | |
C9 | −0.0554 (5) | 0.42440 (15) | 0.3107 (4) | 0.0245 (10) | |
C10 | 0.0145 (5) | 0.44332 (16) | 0.4313 (4) | 0.0303 (10) | |
H10 | 0.1341 | 0.4543 | 0.4581 | 0.036* | |
C11 | −0.0863 (5) | 0.44663 (17) | 0.5139 (4) | 0.0367 (11) | |
H11 | −0.0380 | 0.4601 | 0.5966 | 0.044* | |
C12 | −0.2579 (6) | 0.42998 (18) | 0.4731 (5) | 0.0412 (13) | |
C13 | −0.3339 (5) | 0.41126 (17) | 0.3553 (5) | 0.0378 (12) | |
H13 | −0.4538 | 0.4005 | 0.3298 | 0.045* | |
C14 | −0.2312 (5) | 0.40827 (16) | 0.2736 (4) | 0.0315 (11) | |
H14 | −0.2813 | 0.3950 | 0.1911 | 0.038* | |
C15 | 0.1078 (5) | 0.36332 (15) | 0.1956 (4) | 0.0270 (10) | |
H15A | 0.1887 | 0.3656 | 0.1426 | 0.032* | |
H15B | 0.0000 | 0.3448 | 0.1454 | 0.032* | |
C16 | 0.1942 (5) | 0.32708 (15) | 0.3076 (4) | 0.0237 (10) | |
H16A | 0.3000 | 0.3447 | 0.3632 | 0.028* | |
H16B | 0.1111 | 0.3190 | 0.3567 | 0.028* | |
C17 | 0.2436 (5) | 0.27583 (15) | 0.2503 (4) | 0.0254 (10) | |
H17A | 0.1377 | 0.2622 | 0.1868 | 0.030* | |
H17B | 0.3316 | 0.2852 | 0.2061 | 0.030* | |
C18 | 0.1856 (5) | 0.20924 (16) | 0.4014 (4) | 0.0340 (11) | |
H18A | 0.1483 | 0.2381 | 0.4485 | 0.051* | |
H18B | 0.2394 | 0.1799 | 0.4586 | 0.051* | |
H18C | 0.0832 | 0.1954 | 0.3369 | 0.051* | |
C19 | 0.3830 (5) | 0.18763 (16) | 0.2745 (4) | 0.0302 (11) | |
H19A | 0.4372 | 0.1592 | 0.3344 | 0.045* | |
H19B | 0.4707 | 0.2026 | 0.2370 | 0.045* | |
H19C | 0.2851 | 0.1723 | 0.2085 | 0.045* | |
C20 | −0.1608 (6) | 0.54493 (18) | −0.2272 (5) | 0.0361 (12) | |
N1 | 0.3165 (4) | 0.23120 (12) | 0.3405 (3) | 0.0221 (8) | |
H1 | 0.4111 | 0.2449 | 0.4030 | 0.026* | |
N2 | −0.1973 (5) | 0.56893 (16) | −0.3191 (5) | 0.0496 (12) | |
O1 | 0.2185 (3) | 0.45139 (11) | 0.2705 (3) | 0.0313 (7) | |
F1 | −0.3583 (3) | 0.43279 (11) | 0.5554 (3) | 0.0620 (9) | |
C21 | 1.2617 (5) | 0.08104 (16) | 0.6468 (4) | 0.0304 (11) | |
H21A | 1.1715 | 0.0967 | 0.5747 | 0.037* | |
H21B | 1.2602 | 0.0412 | 0.6379 | 0.037* | |
C22 | 1.4402 (4) | 0.10331 (15) | 0.6546 (4) | 0.0244 (10) | |
C23 | 1.5332 (4) | 0.10253 (16) | 0.5663 (4) | 0.0268 (10) | |
H23 | 1.4855 | 0.0860 | 0.4868 | 0.032* | |
C24 | 1.6998 (5) | 0.12684 (15) | 0.5982 (5) | 0.0299 (11) | |
C25 | 1.7717 (5) | 0.14936 (17) | 0.7160 (5) | 0.0372 (13) | |
H25 | 1.8850 | 0.1655 | 0.7362 | 0.045* | |
C26 | 1.6790 (5) | 0.14833 (16) | 0.8037 (5) | 0.0349 (12) | |
H26 | 1.7291 | 0.1626 | 0.8854 | 0.042* | |
C27 | 1.5114 (5) | 0.12614 (15) | 0.7704 (4) | 0.0258 (10) | |
C28 | 1.3852 (5) | 0.12033 (16) | 0.8490 (4) | 0.0283 (10) | |
C29 | 1.4661 (5) | 0.08086 (17) | 0.9568 (5) | 0.0323 (11) | |
C30 | 1.4517 (5) | 0.02579 (18) | 0.9328 (5) | 0.0423 (13) | |
H30 | 1.3806 | 0.0133 | 0.8539 | 0.051* | |
C31 | 1.5397 (6) | −0.01152 (19) | 1.0225 (6) | 0.0459 (14) | |
H31 | 1.5306 | −0.0492 | 1.0050 | 0.055* | |
C32 | 1.6387 (7) | 0.0069 (2) | 1.1354 (6) | 0.0527 (16) | |
C33 | 1.6570 (7) | 0.0606 (2) | 1.1644 (5) | 0.0631 (16) | |
H33 | 1.7267 | 0.0725 | 1.2442 | 0.076* | |
C34 | 1.5691 (6) | 0.0975 (2) | 1.0718 (5) | 0.0516 (14) | |
H34 | 1.5813 | 0.1351 | 1.0893 | 0.062* | |
C35 | 1.3299 (5) | 0.17483 (15) | 0.8933 (4) | 0.0316 (11) | |
H35A | 1.2347 | 0.1681 | 0.9326 | 0.038* | |
H35B | 1.4313 | 0.1899 | 0.9585 | 0.038* | |
C36 | 1.2669 (5) | 0.21680 (15) | 0.7906 (4) | 0.0276 (10) | |
H36A | 1.1649 | 0.2027 | 0.7244 | 0.033* | |
H36B | 1.3620 | 0.2254 | 0.7523 | 0.033* | |
C37 | 1.2147 (5) | 0.26719 (15) | 0.8497 (4) | 0.0248 (10) | |
H37A | 1.1214 | 0.2574 | 0.8887 | 0.030* | |
H37B | 1.3177 | 0.2798 | 0.9173 | 0.030* | |
C38 | 1.2811 (5) | 0.33380 (17) | 0.7003 (4) | 0.0311 (11) | |
H38A | 1.3148 | 0.3048 | 0.6519 | 0.047* | |
H38B | 1.3852 | 0.3464 | 0.7651 | 0.047* | |
H38C | 1.2303 | 0.3638 | 0.6443 | 0.047* | |
C39 | 1.0881 (5) | 0.35777 (16) | 0.8273 (4) | 0.0336 (11) | |
H39A | 0.9993 | 0.3438 | 0.8649 | 0.050* | |
H39B | 1.0366 | 0.3866 | 0.7678 | 0.050* | |
H39C | 1.1879 | 0.3722 | 0.8932 | 0.050* | |
C40 | 1.7918 (5) | 0.12983 (17) | 0.5048 (5) | 0.0392 (12) | |
N3 | 1.1498 (4) | 0.31321 (12) | 0.7601 (3) | 0.0238 (8) | |
H2 | 1.0535 | 0.3009 | 0.6969 | 0.029* | |
N4 | 1.8635 (5) | 0.13274 (15) | 0.4290 (5) | 0.0543 (12) | |
O2 | 1.2306 (3) | 0.09660 (11) | 0.7634 (3) | 0.0319 (7) | |
F2 | 1.7240 (4) | −0.02926 (13) | 1.2247 (3) | 0.0738 (10) | |
C41 | 0.7749 (5) | 0.27769 (15) | 0.4960 (4) | 0.0222 (9) | |
C42 | 0.6823 (5) | 0.27435 (15) | 0.6015 (4) | 0.0229 (10) | |
O3 | 0.9337 (3) | 0.28748 (11) | 0.5248 (3) | 0.0305 (7) | |
O4 | 0.6729 (3) | 0.26948 (11) | 0.3869 (3) | 0.0295 (7) | |
O5 | 0.7829 (3) | 0.28588 (12) | 0.7101 (3) | 0.0317 (7) | |
O6 | 0.5271 (3) | 0.26119 (10) | 0.5749 (3) | 0.0287 (7) | |
C43 | 0.7576 (5) | 0.27084 (16) | 0.9901 (4) | 0.0241 (10) | |
C44 | 0.6897 (4) | 0.28035 (17) | 1.1045 (4) | 0.0255 (10) | |
O7 | 0.6595 (3) | 0.29301 (13) | 0.8892 (3) | 0.0365 (8) | |
H3 | 0.702 (5) | 0.2899 (17) | 0.822 (2) | 0.044* | |
O8 | 0.8913 (3) | 0.24532 (12) | 0.9986 (3) | 0.0345 (8) | |
O9 | 0.7910 (3) | 0.26052 (13) | 1.2057 (3) | 0.0354 (8) | |
H4 | 0.756 (5) | 0.2628 (17) | 1.276 (2) | 0.042* | |
O10 | 0.5536 (3) | 0.30523 (13) | 1.0950 (3) | 0.0425 (8) | |
O11 | 0.9399 (12) | 0.1504 (4) | 1.1364 (11) | 0.055 (5) | 0.325 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.041 (2) | 0.031 (3) | 0.040 (4) | −0.008 (2) | 0.012 (3) | 0.001 (2) |
C2 | 0.029 (2) | 0.027 (2) | 0.034 (3) | −0.0025 (17) | 0.013 (2) | −0.001 (2) |
C3 | 0.035 (2) | 0.025 (2) | 0.036 (3) | −0.0013 (18) | 0.014 (2) | 0.003 (2) |
C4 | 0.033 (2) | 0.031 (3) | 0.030 (3) | 0.0106 (19) | 0.014 (2) | 0.011 (2) |
C5 | 0.0242 (19) | 0.033 (3) | 0.029 (3) | 0.0060 (17) | 0.005 (2) | 0.000 (2) |
C6 | 0.028 (2) | 0.027 (2) | 0.032 (3) | 0.0050 (17) | 0.009 (2) | −0.002 (2) |
C7 | 0.0234 (19) | 0.022 (2) | 0.029 (3) | 0.0049 (17) | 0.010 (2) | 0.001 (2) |
C8 | 0.0256 (19) | 0.024 (2) | 0.027 (3) | −0.0051 (17) | 0.007 (2) | 0.0001 (19) |
C9 | 0.0270 (19) | 0.019 (2) | 0.027 (3) | −0.0024 (16) | 0.008 (2) | 0.0023 (19) |
C10 | 0.029 (2) | 0.033 (2) | 0.027 (3) | 0.0023 (18) | 0.005 (2) | 0.003 (2) |
C11 | 0.043 (2) | 0.038 (3) | 0.029 (3) | 0.003 (2) | 0.011 (2) | −0.001 (2) |
C12 | 0.046 (3) | 0.046 (3) | 0.042 (4) | 0.010 (2) | 0.029 (3) | 0.015 (3) |
C13 | 0.031 (2) | 0.042 (3) | 0.042 (4) | −0.005 (2) | 0.013 (3) | 0.005 (2) |
C14 | 0.033 (2) | 0.035 (3) | 0.028 (3) | −0.0047 (18) | 0.011 (2) | 0.000 (2) |
C15 | 0.030 (2) | 0.026 (2) | 0.026 (3) | −0.0022 (17) | 0.009 (2) | −0.004 (2) |
C16 | 0.0260 (19) | 0.029 (2) | 0.016 (3) | −0.0016 (16) | 0.005 (2) | 0.0033 (18) |
C17 | 0.0234 (17) | 0.028 (2) | 0.026 (3) | 0.0011 (16) | 0.009 (2) | 0.006 (2) |
C18 | 0.035 (2) | 0.037 (3) | 0.038 (3) | −0.0017 (18) | 0.025 (2) | 0.008 (2) |
C19 | 0.031 (2) | 0.029 (2) | 0.034 (3) | 0.0042 (17) | 0.015 (2) | −0.001 (2) |
C20 | 0.040 (2) | 0.033 (3) | 0.039 (4) | 0.008 (2) | 0.017 (3) | 0.008 (2) |
N1 | 0.0194 (14) | 0.0285 (19) | 0.018 (2) | −0.0005 (13) | 0.0044 (16) | −0.0004 (16) |
N2 | 0.054 (2) | 0.043 (3) | 0.053 (4) | 0.0105 (19) | 0.018 (3) | 0.014 (2) |
O1 | 0.0239 (13) | 0.0326 (18) | 0.034 (2) | −0.0073 (12) | 0.0031 (15) | 0.0009 (14) |
F1 | 0.0614 (17) | 0.087 (2) | 0.052 (2) | 0.0086 (15) | 0.0385 (18) | 0.0066 (17) |
C21 | 0.030 (2) | 0.032 (2) | 0.030 (3) | −0.0037 (17) | 0.010 (2) | −0.004 (2) |
C22 | 0.0222 (18) | 0.023 (2) | 0.024 (3) | 0.0042 (17) | 0.0006 (19) | 0.003 (2) |
C23 | 0.0278 (19) | 0.023 (2) | 0.027 (3) | 0.0034 (17) | 0.004 (2) | 0.0028 (19) |
C24 | 0.026 (2) | 0.024 (2) | 0.042 (4) | 0.0043 (18) | 0.015 (2) | 0.008 (2) |
C25 | 0.025 (2) | 0.025 (2) | 0.062 (4) | 0.0002 (18) | 0.013 (3) | 0.000 (2) |
C26 | 0.035 (2) | 0.027 (2) | 0.041 (4) | 0.0013 (19) | 0.007 (3) | −0.006 (2) |
C27 | 0.0273 (19) | 0.020 (2) | 0.029 (3) | 0.0053 (17) | 0.006 (2) | 0.003 (2) |
C28 | 0.0233 (19) | 0.035 (2) | 0.020 (3) | −0.0007 (17) | −0.003 (2) | −0.002 (2) |
C29 | 0.032 (2) | 0.036 (3) | 0.032 (3) | 0.0093 (19) | 0.013 (2) | 0.004 (2) |
C30 | 0.032 (2) | 0.039 (3) | 0.057 (4) | −0.001 (2) | 0.015 (3) | 0.010 (2) |
C31 | 0.035 (2) | 0.038 (3) | 0.066 (5) | 0.004 (2) | 0.017 (3) | 0.018 (3) |
C32 | 0.054 (3) | 0.055 (4) | 0.056 (5) | 0.031 (3) | 0.027 (3) | 0.027 (3) |
C33 | 0.087 (4) | 0.072 (4) | 0.026 (4) | 0.044 (3) | 0.010 (3) | 0.007 (3) |
C34 | 0.071 (3) | 0.051 (3) | 0.026 (4) | 0.031 (3) | 0.002 (3) | −0.004 (3) |
C35 | 0.032 (2) | 0.033 (3) | 0.029 (3) | 0.0055 (18) | 0.007 (2) | −0.004 (2) |
C36 | 0.0257 (19) | 0.032 (3) | 0.026 (3) | 0.0021 (17) | 0.010 (2) | −0.002 (2) |
C37 | 0.0219 (17) | 0.032 (2) | 0.019 (3) | 0.0036 (16) | 0.0027 (19) | −0.0006 (19) |
C38 | 0.033 (2) | 0.035 (3) | 0.030 (3) | −0.0013 (18) | 0.016 (2) | 0.002 (2) |
C39 | 0.037 (2) | 0.032 (2) | 0.035 (3) | 0.0044 (18) | 0.015 (2) | −0.004 (2) |
C40 | 0.028 (2) | 0.034 (3) | 0.058 (4) | 0.0022 (19) | 0.015 (3) | 0.004 (2) |
N3 | 0.0192 (14) | 0.0313 (19) | 0.022 (2) | 0.0003 (13) | 0.0066 (16) | −0.0049 (16) |
N4 | 0.042 (2) | 0.057 (3) | 0.071 (4) | −0.0001 (19) | 0.028 (3) | 0.005 (2) |
O2 | 0.0291 (14) | 0.0355 (17) | 0.032 (2) | −0.0022 (12) | 0.0106 (15) | −0.0015 (14) |
F2 | 0.078 (2) | 0.077 (2) | 0.070 (3) | 0.0371 (17) | 0.026 (2) | 0.043 (2) |
C41 | 0.0251 (18) | 0.025 (2) | 0.018 (3) | 0.0038 (17) | 0.008 (2) | 0.001 (2) |
C42 | 0.0237 (18) | 0.025 (2) | 0.020 (3) | 0.0038 (17) | 0.007 (2) | 0.002 (2) |
O3 | 0.0183 (12) | 0.0506 (18) | 0.023 (2) | −0.0027 (12) | 0.0056 (13) | −0.0012 (14) |
O4 | 0.0245 (13) | 0.051 (2) | 0.0131 (19) | −0.0077 (13) | 0.0056 (14) | −0.0013 (14) |
O5 | 0.0272 (13) | 0.0516 (19) | 0.017 (2) | −0.0091 (13) | 0.0078 (15) | −0.0059 (15) |
O6 | 0.0218 (13) | 0.0460 (19) | 0.020 (2) | −0.0028 (12) | 0.0082 (14) | 0.0008 (14) |
C43 | 0.0219 (17) | 0.033 (3) | 0.016 (3) | −0.0099 (17) | 0.004 (2) | −0.003 (2) |
C44 | 0.0182 (17) | 0.039 (2) | 0.018 (3) | −0.0083 (18) | 0.002 (2) | −0.002 (2) |
O7 | 0.0342 (16) | 0.060 (2) | 0.020 (2) | 0.0028 (14) | 0.0147 (16) | 0.0021 (16) |
O8 | 0.0313 (14) | 0.0528 (19) | 0.019 (2) | 0.0030 (14) | 0.0066 (15) | −0.0032 (15) |
O9 | 0.0330 (15) | 0.059 (2) | 0.018 (2) | 0.0056 (14) | 0.0131 (16) | 0.0045 (15) |
O10 | 0.0263 (14) | 0.078 (2) | 0.024 (2) | 0.0048 (15) | 0.0083 (15) | −0.0047 (16) |
O11 | 0.060 (7) | 0.048 (7) | 0.045 (9) | 0.009 (5) | −0.004 (6) | 0.000 (5) |
C1—O1 | 1.447 (5) | C23—C24 | 1.403 (5) |
C1—C2 | 1.483 (6) | C23—H23 | 0.9500 |
C1—H1A | 0.9900 | C24—C25 | 1.389 (6) |
C1—H1B | 0.9900 | C24—C40 | 1.433 (6) |
C2—C3 | 1.388 (6) | C25—C26 | 1.380 (6) |
C2—C7 | 1.396 (5) | C25—H25 | 0.9500 |
C3—C4 | 1.386 (6) | C26—C27 | 1.388 (5) |
C3—H3A | 0.9500 | C26—H26 | 0.9500 |
C4—C5 | 1.391 (6) | C27—C28 | 1.513 (5) |
C4—C20 | 1.440 (6) | C28—O2 | 1.446 (5) |
C5—C6 | 1.398 (5) | C28—C29 | 1.538 (6) |
C5—H5 | 0.9500 | C28—C35 | 1.542 (6) |
C6—C7 | 1.381 (5) | C29—C34 | 1.370 (6) |
C6—H6 | 0.9500 | C29—C30 | 1.386 (6) |
C7—C8 | 1.513 (6) | C30—C31 | 1.392 (6) |
C8—O1 | 1.453 (4) | C30—H30 | 0.9500 |
C8—C15 | 1.526 (5) | C31—C32 | 1.356 (7) |
C8—C9 | 1.526 (5) | C31—H31 | 0.9500 |
C9—C10 | 1.380 (6) | C32—F2 | 1.364 (6) |
C9—C14 | 1.395 (5) | C32—C33 | 1.365 (7) |
C10—C11 | 1.383 (5) | C33—C34 | 1.405 (7) |
C10—H10 | 0.9500 | C33—H33 | 0.9500 |
C11—C12 | 1.370 (6) | C34—H34 | 0.9500 |
C11—H11 | 0.9500 | C35—C36 | 1.519 (6) |
C12—C13 | 1.358 (6) | C35—H35A | 0.9900 |
C12—F1 | 1.377 (5) | C35—H35B | 0.9900 |
C13—C14 | 1.386 (5) | C36—C37 | 1.521 (5) |
C13—H13 | 0.9500 | C36—H36A | 0.9900 |
C14—H14 | 0.9500 | C36—H36B | 0.9900 |
C15—C16 | 1.530 (5) | C37—N3 | 1.504 (5) |
C15—H15A | 0.9900 | C37—H37A | 0.9900 |
C15—H15B | 0.9900 | C37—H37B | 0.9900 |
C16—C17 | 1.520 (5) | C38—N3 | 1.478 (4) |
C16—H16A | 0.9900 | C38—H38A | 0.9800 |
C16—H16B | 0.9900 | C38—H38B | 0.9800 |
C17—N1 | 1.493 (5) | C38—H38C | 0.9800 |
C17—H17A | 0.9900 | C39—N3 | 1.491 (5) |
C17—H17B | 0.9900 | C39—H39A | 0.9800 |
C18—N1 | 1.496 (4) | C39—H39B | 0.9800 |
C18—H18A | 0.9800 | C39—H39C | 0.9800 |
C18—H18B | 0.9800 | C40—N4 | 1.147 (6) |
C18—H18C | 0.9800 | N3—H2 | 0.9300 |
C19—N1 | 1.484 (5) | C41—O3 | 1.233 (4) |
C19—H19A | 0.9800 | C41—O4 | 1.269 (5) |
C19—H19B | 0.9800 | C41—C42 | 1.555 (5) |
C19—H19C | 0.9800 | C42—O6 | 1.225 (4) |
C20—N2 | 1.146 (6) | C42—O5 | 1.277 (5) |
N1—H1 | 0.9300 | C43—O8 | 1.215 (4) |
C21—O2 | 1.441 (5) | C43—O7 | 1.292 (5) |
C21—C22 | 1.499 (5) | C43—C44 | 1.536 (5) |
C21—H21A | 0.9900 | C44—O10 | 1.221 (4) |
C21—H21B | 0.9900 | C44—O9 | 1.280 (5) |
C22—C27 | 1.373 (6) | O7—H3 | 0.91 (3) |
C22—C23 | 1.387 (5) | O9—H4 | 0.91 (3) |
O1—C1—C2 | 104.2 (3) | C27—C22—C21 | 109.5 (3) |
O1—C1—H1A | 110.9 | C23—C22—C21 | 129.7 (4) |
C2—C1—H1A | 110.9 | C22—C23—C24 | 117.9 (4) |
O1—C1—H1B | 110.9 | C22—C23—H23 | 121.0 |
C2—C1—H1B | 110.9 | C24—C23—H23 | 121.0 |
H1A—C1—H1B | 108.9 | C25—C24—C23 | 121.0 (4) |
C3—C2—C7 | 120.2 (4) | C25—C24—C40 | 120.5 (4) |
C3—C2—C1 | 131.8 (4) | C23—C24—C40 | 118.5 (4) |
C7—C2—C1 | 108.0 (4) | C26—C25—C24 | 120.1 (4) |
C2—C3—C4 | 118.7 (4) | C26—C25—H25 | 119.9 |
C2—C3—H3A | 120.7 | C24—C25—H25 | 119.9 |
C4—C3—H3A | 120.7 | C25—C26—C27 | 118.8 (4) |
C3—C4—C5 | 121.4 (4) | C25—C26—H26 | 120.6 |
C3—C4—C20 | 120.7 (4) | C27—C26—H26 | 120.6 |
C5—C4—C20 | 117.9 (4) | C22—C27—C26 | 121.3 (4) |
C4—C5—C6 | 119.8 (4) | C22—C27—C28 | 109.9 (3) |
C4—C5—H5 | 120.1 | C26—C27—C28 | 128.7 (4) |
C6—C5—H5 | 120.1 | O2—C28—C27 | 103.6 (3) |
C7—C6—C5 | 118.8 (4) | O2—C28—C29 | 110.1 (3) |
C7—C6—H6 | 120.6 | C27—C28—C29 | 108.3 (3) |
C5—C6—H6 | 120.6 | O2—C28—C35 | 107.5 (3) |
C6—C7—C2 | 121.1 (4) | C27—C28—C35 | 113.4 (3) |
C6—C7—C8 | 130.0 (4) | C29—C28—C35 | 113.5 (4) |
C2—C7—C8 | 108.7 (4) | C34—C29—C30 | 118.0 (4) |
O1—C8—C7 | 102.5 (3) | C34—C29—C28 | 122.9 (4) |
O1—C8—C15 | 107.8 (3) | C30—C29—C28 | 118.7 (4) |
C7—C8—C15 | 109.4 (3) | C29—C30—C31 | 121.1 (5) |
O1—C8—C9 | 109.5 (3) | C29—C30—H30 | 119.5 |
C7—C8—C9 | 112.9 (3) | C31—C30—H30 | 119.5 |
C15—C8—C9 | 114.0 (3) | C32—C31—C30 | 118.8 (5) |
C10—C9—C14 | 118.3 (4) | C32—C31—H31 | 120.6 |
C10—C9—C8 | 120.8 (3) | C30—C31—H31 | 120.6 |
C14—C9—C8 | 120.9 (4) | C31—C32—F2 | 119.4 (5) |
C9—C10—C11 | 121.3 (4) | C31—C32—C33 | 122.7 (5) |
C9—C10—H10 | 119.4 | F2—C32—C33 | 117.9 (6) |
C11—C10—H10 | 119.4 | C32—C33—C34 | 117.5 (6) |
C12—C11—C10 | 118.0 (4) | C32—C33—H33 | 121.2 |
C12—C11—H11 | 121.0 | C34—C33—H33 | 121.2 |
C10—C11—H11 | 121.0 | C29—C34—C33 | 121.9 (5) |
C13—C12—C11 | 123.2 (4) | C29—C34—H34 | 119.0 |
C13—C12—F1 | 118.5 (4) | C33—C34—H34 | 119.0 |
C11—C12—F1 | 118.2 (5) | C36—C35—C28 | 114.8 (4) |
C12—C13—C14 | 118.0 (4) | C36—C35—H35A | 108.6 |
C12—C13—H13 | 121.0 | C28—C35—H35A | 108.6 |
C14—C13—H13 | 121.0 | C36—C35—H35B | 108.6 |
C13—C14—C9 | 121.1 (4) | C28—C35—H35B | 108.6 |
C13—C14—H14 | 119.5 | H35A—C35—H35B | 107.5 |
C9—C14—H14 | 119.5 | C35—C36—C37 | 107.9 (3) |
C8—C15—C16 | 118.7 (3) | C35—C36—H36A | 110.1 |
C8—C15—H15A | 107.7 | C37—C36—H36A | 110.1 |
C16—C15—H15A | 107.7 | C35—C36—H36B | 110.1 |
C8—C15—H15B | 107.7 | C37—C36—H36B | 110.1 |
C16—C15—H15B | 107.7 | H36A—C36—H36B | 108.4 |
H15A—C15—H15B | 107.1 | N3—C37—C36 | 114.7 (3) |
C17—C16—C15 | 104.9 (3) | N3—C37—H37A | 108.6 |
C17—C16—H16A | 110.8 | C36—C37—H37A | 108.6 |
C15—C16—H16A | 110.8 | N3—C37—H37B | 108.6 |
C17—C16—H16B | 110.8 | C36—C37—H37B | 108.6 |
C15—C16—H16B | 110.8 | H37A—C37—H37B | 107.6 |
H16A—C16—H16B | 108.9 | N3—C38—H38A | 109.5 |
N1—C17—C16 | 115.6 (3) | N3—C38—H38B | 109.5 |
N1—C17—H17A | 108.4 | H38A—C38—H38B | 109.5 |
C16—C17—H17A | 108.4 | N3—C38—H38C | 109.5 |
N1—C17—H17B | 108.4 | H38A—C38—H38C | 109.5 |
C16—C17—H17B | 108.4 | H38B—C38—H38C | 109.5 |
H17A—C17—H17B | 107.4 | N3—C39—H39A | 109.5 |
N1—C18—H18A | 109.5 | N3—C39—H39B | 109.5 |
N1—C18—H18B | 109.5 | H39A—C39—H39B | 109.5 |
H18A—C18—H18B | 109.5 | N3—C39—H39C | 109.5 |
N1—C18—H18C | 109.5 | H39A—C39—H39C | 109.5 |
H18A—C18—H18C | 109.5 | H39B—C39—H39C | 109.5 |
H18B—C18—H18C | 109.5 | N4—C40—C24 | 178.9 (5) |
N1—C19—H19A | 109.5 | C38—N3—C39 | 110.2 (3) |
N1—C19—H19B | 109.5 | C38—N3—C37 | 114.0 (3) |
H19A—C19—H19B | 109.5 | C39—N3—C37 | 109.0 (3) |
N1—C19—H19C | 109.5 | C38—N3—H2 | 107.8 |
H19A—C19—H19C | 109.5 | C39—N3—H2 | 107.8 |
H19B—C19—H19C | 109.5 | C37—N3—H2 | 107.8 |
N2—C20—C4 | 178.3 (5) | C21—O2—C28 | 111.8 (3) |
C19—N1—C17 | 109.2 (3) | O3—C41—O4 | 127.3 (3) |
C19—N1—C18 | 110.6 (3) | O3—C41—C42 | 118.8 (4) |
C17—N1—C18 | 112.8 (3) | O4—C41—C42 | 113.9 (3) |
C19—N1—H1 | 108.0 | O6—C42—O5 | 127.0 (3) |
C17—N1—H1 | 108.0 | O6—C42—C41 | 119.4 (4) |
C18—N1—H1 | 108.0 | O5—C42—C41 | 113.6 (3) |
C1—O1—C8 | 107.5 (3) | O8—C43—O7 | 125.8 (4) |
O2—C21—C22 | 104.6 (3) | O8—C43—C44 | 121.4 (4) |
O2—C21—H21A | 110.8 | O7—C43—C44 | 112.9 (3) |
C22—C21—H21A | 110.8 | O10—C44—O9 | 125.9 (4) |
O2—C21—H21B | 110.8 | O10—C44—C43 | 121.1 (4) |
C22—C21—H21B | 110.8 | O9—C44—C43 | 112.9 (3) |
H21A—C21—H21B | 108.9 | C43—O7—H3 | 114 (3) |
C27—C22—C23 | 120.8 (3) | C44—O9—H4 | 118 (3) |
O1—C1—C2—C3 | −158.6 (4) | C22—C23—C24—C25 | 2.1 (6) |
O1—C1—C2—C7 | 19.1 (4) | C22—C23—C24—C40 | −175.5 (4) |
C7—C2—C3—C4 | −1.6 (5) | C23—C24—C25—C26 | −0.3 (6) |
C1—C2—C3—C4 | 175.8 (4) | C40—C24—C25—C26 | 177.3 (4) |
C2—C3—C4—C5 | 0.7 (5) | C24—C25—C26—C27 | −2.2 (6) |
C2—C3—C4—C20 | −177.4 (3) | C23—C22—C27—C26 | −1.0 (6) |
C3—C4—C5—C6 | 0.6 (5) | C21—C22—C27—C26 | 178.0 (4) |
C20—C4—C5—C6 | 178.7 (3) | C23—C22—C27—C28 | −178.6 (3) |
C4—C5—C6—C7 | −1.0 (5) | C21—C22—C27—C28 | 0.4 (4) |
C5—C6—C7—C2 | 0.1 (5) | C25—C26—C27—C22 | 2.8 (6) |
C5—C6—C7—C8 | −174.3 (3) | C25—C26—C27—C28 | 179.9 (4) |
C3—C2—C7—C6 | 1.2 (5) | C22—C27—C28—O2 | −4.9 (4) |
C1—C2—C7—C6 | −176.8 (3) | C26—C27—C28—O2 | 177.7 (4) |
C3—C2—C7—C8 | 176.7 (3) | C22—C27—C28—C29 | 111.9 (4) |
C1—C2—C7—C8 | −1.3 (4) | C26—C27—C28—C29 | −65.4 (5) |
C6—C7—C8—O1 | 158.1 (3) | C22—C27—C28—C35 | −121.1 (4) |
C2—C7—C8—O1 | −16.8 (4) | C26—C27—C28—C35 | 61.5 (5) |
C6—C7—C8—C15 | 43.9 (5) | O2—C28—C29—C34 | −155.7 (4) |
C2—C7—C8—C15 | −131.0 (3) | C27—C28—C29—C34 | 91.8 (5) |
C6—C7—C8—C9 | −84.1 (5) | C35—C28—C29—C34 | −35.1 (5) |
C2—C7—C8—C9 | 101.0 (3) | O2—C28—C29—C30 | 32.0 (5) |
O1—C8—C9—C10 | −13.7 (5) | C27—C28—C29—C30 | −80.6 (4) |
C7—C8—C9—C10 | −127.3 (4) | C35—C28—C29—C30 | 152.5 (3) |
C15—C8—C9—C10 | 107.1 (4) | C34—C29—C30—C31 | −0.3 (6) |
O1—C8—C9—C14 | 166.7 (3) | C28—C29—C30—C31 | 172.4 (3) |
C7—C8—C9—C14 | 53.1 (5) | C29—C30—C31—C32 | 0.9 (6) |
C15—C8—C9—C14 | −72.5 (5) | C30—C31—C32—F2 | 179.2 (4) |
C14—C9—C10—C11 | −0.3 (6) | C30—C31—C32—C33 | −0.6 (7) |
C8—C9—C10—C11 | −180.0 (3) | C31—C32—C33—C34 | −0.3 (7) |
C9—C10—C11—C12 | 0.7 (6) | F2—C32—C33—C34 | 179.9 (4) |
C10—C11—C12—C13 | −1.0 (7) | C30—C29—C34—C33 | −0.7 (7) |
C10—C11—C12—F1 | 179.4 (4) | C28—C29—C34—C33 | −173.0 (4) |
C11—C12—C13—C14 | 0.9 (7) | C32—C33—C34—C29 | 1.0 (7) |
F1—C12—C13—C14 | −179.5 (4) | O2—C28—C35—C36 | −64.0 (4) |
C12—C13—C14—C9 | −0.5 (6) | C27—C28—C35—C36 | 49.9 (5) |
C10—C9—C14—C13 | 0.2 (6) | C29—C28—C35—C36 | 174.0 (3) |
C8—C9—C14—C13 | 179.9 (4) | C28—C35—C36—C37 | 178.9 (3) |
O1—C8—C15—C16 | 69.2 (4) | C35—C36—C37—N3 | 179.6 (3) |
C7—C8—C15—C16 | 180.0 (3) | C36—C37—N3—C38 | −61.5 (4) |
C9—C8—C15—C16 | −52.5 (4) | C36—C37—N3—C39 | 174.9 (3) |
C8—C15—C16—C17 | −174.3 (3) | C22—C21—O2—C28 | −7.7 (4) |
C15—C16—C17—N1 | −174.6 (3) | C27—C28—O2—C21 | 7.9 (4) |
C16—C17—N1—C19 | −171.5 (3) | C29—C28—O2—C21 | −107.7 (4) |
C16—C17—N1—C18 | 65.1 (4) | C35—C28—O2—C21 | 128.2 (3) |
C2—C1—O1—C8 | −30.3 (4) | O3—C41—C42—O6 | −175.3 (4) |
C7—C8—O1—C1 | 29.0 (4) | O4—C41—C42—O6 | 4.5 (5) |
C15—C8—O1—C1 | 144.3 (3) | O3—C41—C42—O5 | 4.2 (5) |
C9—C8—O1—C1 | −91.2 (4) | O4—C41—C42—O5 | −175.9 (3) |
O2—C21—C22—C27 | 4.3 (4) | O8—C43—C44—O10 | −178.7 (4) |
O2—C21—C22—C23 | −176.8 (4) | O7—C43—C44—O10 | 2.0 (5) |
C27—C22—C23—C24 | −1.5 (6) | O8—C43—C44—O9 | 2.3 (5) |
C21—C22—C23—C24 | 179.8 (4) | O7—C43—C44—O9 | −177.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6 | 0.93 | 1.91 | 2.768 (4) | 152 |
N1—H1···O4 | 0.93 | 2.22 | 2.886 (4) | 128 |
N3—H2···O3 | 0.93 | 1.91 | 2.764 (4) | 152 |
N3—H2···O5 | 0.93 | 2.22 | 2.884 (4) | 127 |
O7—H3···O5 | 0.91 (3) | 1.56 (3) | 2.466 (4) | 177 (4) |
O9—H4···O4i | 0.91 (3) | 1.57 (3) | 2.465 (4) | 173 (4) |
Symmetry code: (i) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | 2C20H22FN2O+·C2O42−·C2H2O4·0.325H2O |
Mr | 834.05 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 120 |
a, b, c (Å) | 7.9355 (3), 24.7376 (9), 11.1332 (5) |
β (°) | 106.589 (2) |
V (Å3) | 2094.54 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.32 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.969, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7581, 3609, 2652 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.095, 1.02 |
No. of reflections | 3609 |
No. of parameters | 562 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.21 |
Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6 | 0.93 | 1.91 | 2.768 (4) | 152 |
N1—H1···O4 | 0.93 | 2.22 | 2.886 (4) | 128 |
N3—H2···O3 | 0.93 | 1.91 | 2.764 (4) | 152 |
N3—H2···O5 | 0.93 | 2.22 | 2.884 (4) | 127 |
O7—H3···O5 | 0.91 (3) | 1.56 (3) | 2.466 (4) | 177 (4) |
O9—H4···O4i | 0.91 (3) | 1.57 (3) | 2.465 (4) | 173 (4) |
Symmetry code: (i) x, y, z+1. |
Acknowledgements
We thank the EPSRC National Crystallography Service (University of Southampton) for data collection.
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burke, W. J. (2002). Expert Opin. Invest. Drugs, 11, 1477–1486. Web of Science CrossRef CAS Google Scholar
Chaix-Pluchery, O., Mutin, J. C., Bouillot, J. & Niepce, J. C. (1989). Acta Cryst. C45, 1699–1705. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harrison, W. T. A., Yathirajan, H. S., Anilkumar, H. G., Sarojini, B. K., Narayana, B. & Lobo, K. G. (2005). Acta Cryst. E61, o3810–o3812. Web of Science CSD CrossRef IUCr Journals Google Scholar
Newkome, G. R., Theriot, K. J. & Fronczek, F. R. (1985). Acta Cryst. C41, 1642–1644. CSD CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). 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
Periasamy, M., Reddy, M. N. & Anwar, S. (2004). Tetrahedron Asymmetry, 15, 1809–1812. Web of Science CSD CrossRef CAS Google Scholar
Sanchez, C., Bogeso, K. P., Ebert, B., Reines, E. H. & Braestrup, C. (2004). Psychopharmacology, 174, 163–176. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sorbera, L. A., Revel, L., Martin, L. & Castaner, J. (2001). Drugs Future, 26, 115–120. Web of Science CrossRef CAS Google Scholar
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(S)-(+)-1-[3-(dimethylamino)propyl]-1-(4-fluorophenyl)- 5-phthalan-5-carbonitrileoxalate (C20H21FON2), common names escitalopram or S-(+)-citalopram, is a widely prescribed drug used to treat depression and related conditions (Burke, 2002). It is conveniently introduced as an oxalate salt, with a nominal formula usually given as C20H21FON2·C2H2O4, i.e. the presumed proton-transfer reaction is not specified (Sorbera et al., 2001). As part of our ongoing crystallographic studies of pharmaceutical molecules (Harrison et al., 2005), we now report the structure of the title compound, (I), in which two N-protonated escitalopram cations (C20H22FON2+), and a C2O42- oxalate dianon are accompanied by a neutral molecule of oxalic acid and a partially occupied water molecule (Fig. 1).
The bond lengths and angles in (I) fall within their expected ranges (Cambridge Structural Database, Version 5.27; Allen, 2002). There are two C20H22FON2+ cations in the asymmetric unit; atoms C8 and C28 are assumed to possess S configurations, consistent with the known absolute structure of the biologically active enantiomer of citalopram (Sanchez et al., 2004). For the C1-containing molecule, the dihedral angle between the mean planes of the C2–C7 and C9–C14 benzene rings is 62.83 (13)° and the C1/C2/C7/C8/O1 five-membered ring displays an envelope conformation with atom O1 in the flap position [the displacement from the C-atom mean plane is 0.435 (5) Å]. In the C21-containing molecule, the dihedral angle between the C22–C27 and C29–C34 mean planes is 81.99 (13)° and the envelope conformation for C21/C22/C27/C28/O2 is less pronounced, with atom O2 displaced from the C-atom mean plane by 0.113 (6) Å. The oxalate species are both approximately planar; the dihedral angle between the C41/O3/O4 and C42/O5/O6 groupings is 4.4 (3)° and the equivalent value for C43/O7/O8 and C44/O9/O10 is 2.8 (6)°.
The component species in (I) interact by way of N—H···O and O—H···O hydrogen bonds (Table 1), such that both C20H22FON2+ cations make bifurcated N—H···(O,O) hydrogen bonds to the same oxalate dianion. Then, the (C20H22FON2+)2·C2O42- units are linked into [001] chains by way of the oxalic acid molecules, i.e. the oxalate dianions and oxalic acid molecules alternate in the chains. The short H···O seprations of the oxalic acid-to-oxalate hydrogen bonds suggests that they are strong interactions.
Although it is not expected from a consideration of the pKa values of oxalic acid (pKa1 = 1.23, pKa2 = 4.19; Newkome et al., 1985) the co-existence of oxalate dianions and oxalic acid molecues in the same crystal has been observed in a number of compounds, with three examples being bis(pyridinium) oxalate oxalic acid (Newkome et al., 1985), barium oxalate oxalic acid dihydrate (Chaix-Pluchery et al., 1989), and 1-(α-pyrrolidiniobenzyl)-2-naphthol oxalate oxalic acid (Periasamy et al., 2004). These three compounds show the same altertnating oxalate–oxalic acid hydrogen-bonded chains seen in (I).