Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112030168/bm3120sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030168/bm3120Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030168/bm3120IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030168/bm3120IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112030168/bm3120IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112030168/bm3120Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112030168/bm3120IIsup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112030168/bm3120IIIsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112030168/bm3120IVsup9.cml |
CCDC references: 908125; 908126; 908127; 908128
The title compounds were synthesized by heating together under reflux for 15 min quantities (1 mmol) of cis-cyclohexane-1,2-dicarboxylic anhydride and o-anisidine [for (I)], p-anisidine [for (II)], m-aminobenzoic acid [for (III)] and p-aminobenzoic acid [for (IV)] in ethanol–water (50 ml, 1:1 v/v). After volume reduction to 30 ml, the hot-filtered solutions were allowed to evaporate to incipient dryness at room temperature over a period of several weeks, giving either colourless plates [of (I)–(III)] or fine needles [of (IV)] from which specimens were cleaved for structural analyses.
H atoms potentially involved in hydrogen-bonding interactions in (I), (III) and (IV) were located by difference methods but their positional parameters were allowed to ride in the refinement with the isotropic displacement parameters Uiso(H) = 1.2Ueq(O). Other H atoms in all structures were included in the respective refinements at calculated positions (C—H = 0.93–0.97 Å), with Uiso(H) = 1.2Ueq(C), using a riding-model approximation. The water molecule of solvation in (IV) was found to be disordered over two adjacent sites [O···O = 1.503 (12) Å], with occupancy factors determined as 0.81 (1) (O1W) and 0.19 (1) (O2W). The occupancies were subsequently fixed and the minor component was refined isotropically. With chiral (III), in the absence of a suitable heavy atom, Friedel pairs (1062) were merged, the configuration of the chiral centres (C8S and C9R) being arbitrarily assigned.
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010). Program(s) used to solve structure: SIR92 (Altomare et al., 1993) for (I), (III), (IV); SHELXS97 (Sheldrick, 2008) for (II). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
C15H19NO4 | Z = 2 |
Mr = 277.31 | F(000) = 296 |
Triclinic, P1 | Dx = 1.362 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3557 (4) Å | Cell parameters from 4313 reflections |
b = 8.3630 (4) Å | θ = 3.3–28.8° |
c = 11.7128 (6) Å | µ = 0.10 mm−1 |
α = 100.453 (4)° | T = 200 K |
β = 97.232 (4)° | Flat prism, colourless |
γ = 104.042 (4)° | 0.45 × 0.30 × 0.18 mm |
V = 676.40 (6) Å3 |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2640 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2082 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.3° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −10→10 |
Tmin = 0.975, Tmax = 0.980 | l = −14→14 |
8079 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0513P)2] where P = (Fo2 + 2Fc2)/3 |
2640 reflections | (Δ/σ)max < 0.001 |
189 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C15H19NO4 | γ = 104.042 (4)° |
Mr = 277.31 | V = 676.40 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3557 (4) Å | Mo Kα radiation |
b = 8.3630 (4) Å | µ = 0.10 mm−1 |
c = 11.7128 (6) Å | T = 200 K |
α = 100.453 (4)° | 0.45 × 0.30 × 0.18 mm |
β = 97.232 (4)° |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2640 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2082 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.980 | Rint = 0.024 |
8079 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.18 e Å−3 |
2640 reflections | Δρmin = −0.20 e Å−3 |
189 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O12 | −0.14926 (13) | 0.07111 (14) | 0.19578 (9) | 0.0449 (4) | |
O21 | 0.08493 (13) | 0.41630 (11) | 0.38713 (8) | 0.0321 (3) | |
O22 | 0.01483 (14) | 0.29940 (13) | 0.53760 (8) | 0.0375 (4) | |
O211 | 0.19154 (12) | 0.36885 (11) | −0.06244 (8) | 0.0318 (3) | |
N11 | 0.04741 (16) | 0.20455 (13) | 0.08805 (9) | 0.0258 (3) | |
C1 | 0.18449 (16) | 0.13300 (15) | 0.26727 (10) | 0.0213 (4) | |
C2 | 0.13519 (16) | 0.14141 (14) | 0.39152 (10) | 0.0211 (4) | |
C3 | 0.30154 (18) | 0.12408 (16) | 0.47820 (11) | 0.0267 (4) | |
C4 | 0.48581 (17) | 0.25512 (16) | 0.47911 (11) | 0.0282 (4) | |
C5 | 0.53572 (17) | 0.24351 (17) | 0.35632 (12) | 0.0316 (4) | |
C6 | 0.37447 (17) | 0.25898 (16) | 0.26619 (11) | 0.0259 (4) | |
C11 | −0.08286 (17) | 0.22259 (15) | −0.00513 (10) | 0.0235 (4) | |
C12 | 0.01120 (17) | 0.13474 (15) | 0.18109 (11) | 0.0236 (4) | |
C21 | −0.00335 (18) | 0.31266 (15) | −0.08506 (11) | 0.0248 (4) | |
C22 | 0.07697 (16) | 0.29933 (15) | 0.43665 (10) | 0.0219 (4) | |
C31 | −0.12003 (19) | 0.34059 (16) | −0.17739 (11) | 0.0301 (4) | |
C41 | −0.3160 (2) | 0.27757 (17) | −0.19104 (12) | 0.0322 (4) | |
C51 | −0.39563 (19) | 0.18700 (16) | −0.11428 (12) | 0.0314 (4) | |
C61 | −0.27918 (18) | 0.15905 (16) | −0.02087 (11) | 0.0284 (4) | |
C211 | 0.2820 (2) | 0.44485 (18) | −0.14755 (13) | 0.0378 (5) | |
H1 | 0.20390 | 0.02080 | 0.24310 | 0.0260* | |
H2 | 0.02610 | 0.04440 | 0.38650 | 0.0250* | |
H3A | 0.27110 | 0.13760 | 0.55700 | 0.0320* | |
H3B | 0.31850 | 0.01190 | 0.45580 | 0.0320* | |
H4A | 0.58840 | 0.23800 | 0.53200 | 0.0340* | |
H4B | 0.47270 | 0.36720 | 0.50840 | 0.0340* | |
H5A | 0.56310 | 0.13610 | 0.33090 | 0.0380* | |
H5B | 0.64970 | 0.33270 | 0.35930 | 0.0380* | |
H6A | 0.40640 | 0.23830 | 0.18800 | 0.0310* | |
H6B | 0.36120 | 0.37300 | 0.28410 | 0.0310* | |
H11 | 0.164 (2) | 0.2508 (18) | 0.0824 (13) | 0.045 (4)* | |
H21A | 0.41750 | 0.47850 | −0.12170 | 0.0450* | |
H21B | 0.23900 | 0.54230 | −0.15640 | 0.0450* | |
H21C | 0.25030 | 0.36500 | −0.22190 | 0.0450* | |
H22 | −0.015 (3) | 0.402 (3) | 0.5587 (17) | 0.082 (6)* | |
H31 | −0.06730 | 0.40120 | −0.23000 | 0.0360* | |
H41 | −0.39450 | 0.29680 | −0.25280 | 0.0390* | |
H51 | −0.52710 | 0.14440 | −0.12470 | 0.0380* | |
H61 | −0.33300 | 0.09770 | 0.03110 | 0.0340* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O12 | 0.0229 (5) | 0.0766 (8) | 0.0336 (6) | 0.0013 (5) | 0.0032 (4) | 0.0261 (5) |
O21 | 0.0487 (6) | 0.0297 (5) | 0.0297 (5) | 0.0212 (4) | 0.0179 (4) | 0.0142 (4) |
O22 | 0.0604 (7) | 0.0392 (6) | 0.0276 (6) | 0.0274 (5) | 0.0234 (5) | 0.0153 (4) |
O211 | 0.0295 (5) | 0.0369 (5) | 0.0288 (5) | 0.0041 (4) | 0.0088 (4) | 0.0113 (4) |
N11 | 0.0217 (6) | 0.0309 (6) | 0.0247 (6) | 0.0042 (5) | 0.0033 (5) | 0.0102 (5) |
C1 | 0.0237 (6) | 0.0200 (6) | 0.0205 (7) | 0.0071 (5) | 0.0046 (5) | 0.0031 (5) |
C2 | 0.0231 (6) | 0.0189 (6) | 0.0214 (7) | 0.0040 (5) | 0.0043 (5) | 0.0069 (5) |
C3 | 0.0336 (7) | 0.0246 (7) | 0.0248 (7) | 0.0118 (6) | 0.0040 (5) | 0.0084 (5) |
C4 | 0.0280 (7) | 0.0273 (7) | 0.0285 (8) | 0.0097 (6) | −0.0027 (5) | 0.0068 (5) |
C5 | 0.0220 (7) | 0.0364 (8) | 0.0349 (8) | 0.0062 (6) | 0.0019 (6) | 0.0084 (6) |
C6 | 0.0237 (6) | 0.0308 (7) | 0.0236 (7) | 0.0064 (5) | 0.0058 (5) | 0.0073 (5) |
C11 | 0.0272 (7) | 0.0222 (6) | 0.0202 (7) | 0.0085 (5) | 0.0013 (5) | 0.0018 (5) |
C12 | 0.0236 (6) | 0.0245 (7) | 0.0204 (7) | 0.0046 (5) | 0.0043 (5) | 0.0015 (5) |
C21 | 0.0294 (7) | 0.0217 (6) | 0.0223 (7) | 0.0074 (5) | 0.0057 (5) | 0.0010 (5) |
C22 | 0.0197 (6) | 0.0288 (7) | 0.0172 (6) | 0.0065 (5) | 0.0025 (5) | 0.0058 (5) |
C31 | 0.0430 (8) | 0.0297 (7) | 0.0216 (7) | 0.0143 (6) | 0.0089 (6) | 0.0073 (5) |
C41 | 0.0392 (8) | 0.0347 (8) | 0.0241 (7) | 0.0174 (6) | −0.0023 (6) | 0.0055 (6) |
C51 | 0.0275 (7) | 0.0331 (8) | 0.0313 (8) | 0.0095 (6) | −0.0005 (6) | 0.0037 (6) |
C61 | 0.0287 (7) | 0.0282 (7) | 0.0278 (8) | 0.0060 (6) | 0.0040 (6) | 0.0083 (6) |
C211 | 0.0412 (8) | 0.0416 (9) | 0.0365 (9) | 0.0113 (7) | 0.0199 (7) | 0.0147 (7) |
O12—C12 | 1.2188 (17) | C31—C41 | 1.387 (2) |
O21—C22 | 1.2180 (15) | C41—C51 | 1.375 (2) |
O22—C22 | 1.3202 (15) | C51—C61 | 1.3926 (19) |
O22—H22 | 0.94 (2) | C1—H1 | 0.9800 |
O211—C211 | 1.4255 (18) | C2—H2 | 0.9800 |
O211—C21 | 1.3705 (16) | C3—H3A | 0.9700 |
N11—C11 | 1.4138 (16) | C3—H3B | 0.9700 |
N11—C12 | 1.3520 (16) | C4—H4A | 0.9700 |
N11—H11 | 0.867 (15) | C4—H4B | 0.9700 |
C1—C12 | 1.5278 (17) | C5—H5A | 0.9700 |
C1—C6 | 1.5355 (18) | C5—H5B | 0.9700 |
C1—C2 | 1.5370 (16) | C6—H6A | 0.9700 |
C2—C3 | 1.5413 (18) | C6—H6B | 0.9700 |
C2—C22 | 1.5117 (17) | C31—H31 | 0.9300 |
C3—C4 | 1.5197 (19) | C41—H41 | 0.9300 |
C4—C5 | 1.5206 (18) | C51—H51 | 0.9300 |
C5—C6 | 1.5319 (19) | C61—H61 | 0.9300 |
C11—C61 | 1.3881 (19) | C211—H21A | 0.9600 |
C11—C21 | 1.4021 (17) | C211—H21B | 0.9600 |
C21—C31 | 1.3842 (18) | C211—H21C | 0.9600 |
C22—O22—H22 | 106.5 (13) | C22—C2—H2 | 107.00 |
C21—O211—C211 | 117.55 (10) | C2—C3—H3A | 109.00 |
C11—N11—C12 | 128.84 (12) | C2—C3—H3B | 109.00 |
C12—N11—H11 | 119.8 (10) | C4—C3—H3A | 109.00 |
C11—N11—H11 | 111.3 (10) | C4—C3—H3B | 109.00 |
C2—C1—C6 | 112.86 (10) | H3A—C3—H3B | 108.00 |
C2—C1—C12 | 109.56 (10) | C3—C4—H4A | 109.00 |
C6—C1—C12 | 116.96 (10) | C3—C4—H4B | 109.00 |
C1—C2—C3 | 110.70 (10) | C5—C4—H4A | 109.00 |
C1—C2—C22 | 112.47 (10) | C5—C4—H4B | 109.00 |
C3—C2—C22 | 111.18 (10) | H4A—C4—H4B | 108.00 |
C2—C3—C4 | 111.44 (10) | C4—C5—H5A | 109.00 |
C3—C4—C5 | 111.35 (11) | C4—C5—H5B | 109.00 |
C4—C5—C6 | 112.20 (11) | C6—C5—H5A | 109.00 |
C1—C6—C5 | 111.51 (11) | C6—C5—H5B | 109.00 |
N11—C11—C21 | 116.06 (11) | H5A—C5—H5B | 108.00 |
C21—C11—C61 | 119.37 (11) | C1—C6—H6A | 109.00 |
N11—C11—C61 | 124.56 (11) | C1—C6—H6B | 109.00 |
N11—C12—C1 | 116.37 (11) | C5—C6—H6A | 109.00 |
O12—C12—C1 | 120.40 (11) | C5—C6—H6B | 109.00 |
O12—C12—N11 | 123.19 (12) | H6A—C6—H6B | 108.00 |
O211—C21—C11 | 114.89 (11) | C21—C31—H31 | 120.00 |
O211—C21—C31 | 124.91 (12) | C41—C31—H31 | 120.00 |
C11—C21—C31 | 120.20 (12) | C31—C41—H41 | 120.00 |
O22—C22—C2 | 112.97 (10) | C51—C41—H41 | 120.00 |
O21—C22—O22 | 122.14 (12) | C41—C51—H51 | 120.00 |
O21—C22—C2 | 124.89 (11) | C61—C51—H51 | 120.00 |
C21—C31—C41 | 119.62 (12) | C11—C61—H61 | 120.00 |
C31—C41—C51 | 120.77 (13) | C51—C61—H61 | 120.00 |
C41—C51—C61 | 119.94 (13) | O211—C211—H21A | 110.00 |
C11—C61—C51 | 120.10 (12) | O211—C211—H21B | 109.00 |
C2—C1—H1 | 106.00 | O211—C211—H21C | 109.00 |
C6—C1—H1 | 105.00 | H21A—C211—H21B | 109.00 |
C12—C1—H1 | 105.00 | H21A—C211—H21C | 109.00 |
C1—C2—H2 | 107.00 | H21B—C211—H21C | 109.00 |
C3—C2—H2 | 107.00 | ||
C211—O211—C21—C11 | 173.23 (11) | C1—C2—C22—O21 | −6.84 (17) |
C211—O211—C21—C31 | −7.53 (18) | C1—C2—C22—O22 | 173.17 (10) |
C12—N11—C11—C21 | 175.18 (12) | C3—C2—C22—O21 | 117.95 (13) |
C12—N11—C11—C61 | −4.3 (2) | C3—C2—C22—O22 | −62.04 (14) |
C11—N11—C12—O12 | 1.7 (2) | C2—C3—C4—C5 | −56.81 (14) |
C11—N11—C12—C1 | 179.56 (11) | C3—C4—C5—C6 | 55.64 (15) |
C6—C1—C2—C3 | −52.76 (13) | C4—C5—C6—C1 | −52.67 (14) |
C6—C1—C2—C22 | 72.30 (13) | N11—C11—C21—O211 | 0.97 (16) |
C12—C1—C2—C3 | 175.02 (10) | N11—C11—C21—C31 | −178.31 (11) |
C12—C1—C2—C22 | −59.92 (13) | C61—C11—C21—O211 | −179.48 (11) |
C2—C1—C6—C5 | 51.65 (14) | C61—C11—C21—C31 | 1.24 (19) |
C12—C1—C6—C5 | −179.88 (10) | N11—C11—C61—C51 | 178.56 (12) |
C2—C1—C12—O12 | −31.79 (16) | C21—C11—C61—C51 | −0.95 (19) |
C2—C1—C12—N11 | 150.33 (11) | O211—C21—C31—C41 | −179.81 (12) |
C6—C1—C12—O12 | −161.82 (12) | C11—C21—C31—C41 | −0.61 (19) |
C6—C1—C12—N11 | 20.30 (16) | C21—C31—C41—C51 | −0.3 (2) |
C1—C2—C3—C4 | 55.06 (13) | C31—C41—C51—C61 | 0.6 (2) |
C22—C2—C3—C4 | −70.72 (13) | C41—C51—C61—C11 | 0.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O211 | 0.867 (15) | 2.119 (15) | 2.6003 (14) | 114.4 (12) |
O22—H22···O21i | 0.94 (2) | 1.76 (2) | 2.6866 (14) | 173 (2) |
C3—H3A···O22 | 0.97 | 2.58 | 2.9294 (17) | 101 |
C6—H6B···O21 | 0.97 | 2.56 | 3.1171 (16) | 117 |
C51—H51···O12ii | 0.93 | 2.55 | 3.4232 (18) | 157 |
C61—H61···O12 | 0.93 | 2.29 | 2.8812 (17) | 121 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1, −y, −z. |
C15H17NO3 | F(000) = 552 |
Mr = 259.30 | Dx = 1.352 Mg m−3 |
Monoclinic, P21/n | Melting point: 428 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7119 (5) Å | Cell parameters from 4720 reflections |
b = 6.6705 (3) Å | θ = 3.3–28.7° |
c = 17.2898 (8) Å | µ = 0.09 mm−1 |
β = 109.482 (5)° | T = 200 K |
V = 1273.42 (11) Å3 | Flat prism, purple brown |
Z = 4 | 0.40 × 0.25 × 0.12 mm |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2498 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1959 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 26.0°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −14→14 |
Tmin = 0.929, Tmax = 0.981 | k = −8→8 |
8552 measured reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0496P)2] where P = (Fo2 + 2Fc2)/3 |
2498 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C15H17NO3 | V = 1273.42 (11) Å3 |
Mr = 259.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.7119 (5) Å | µ = 0.09 mm−1 |
b = 6.6705 (3) Å | T = 200 K |
c = 17.2898 (8) Å | 0.40 × 0.25 × 0.12 mm |
β = 109.482 (5)° |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2498 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1959 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.981 | Rint = 0.024 |
8552 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.18 e Å−3 |
2498 reflections | Δρmin = −0.17 e Å−3 |
172 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O1 | 0.60601 (9) | 0.55074 (13) | 0.38265 (6) | 0.0389 (3) | |
O3 | 0.44297 (8) | 0.03988 (12) | 0.20453 (5) | 0.0335 (3) | |
O41 | 0.69783 (9) | 0.65459 (13) | 0.03909 (6) | 0.0371 (3) | |
N2 | 0.54233 (9) | 0.31061 (14) | 0.28078 (6) | 0.0248 (3) | |
C1 | 0.55873 (11) | 0.39094 (19) | 0.35851 (8) | 0.0274 (4) | |
C3 | 0.48336 (11) | 0.12526 (17) | 0.26984 (8) | 0.0243 (4) | |
C4 | 0.38378 (12) | −0.08664 (18) | 0.35410 (8) | 0.0307 (4) | |
C5 | 0.26841 (12) | 0.02011 (19) | 0.35074 (9) | 0.0337 (4) | |
C6 | 0.29309 (12) | 0.18467 (19) | 0.41557 (9) | 0.0343 (5) | |
C7 | 0.37770 (12) | 0.34107 (19) | 0.40050 (8) | 0.0316 (4) | |
C8 | 0.49925 (11) | 0.25028 (18) | 0.40214 (8) | 0.0270 (4) | |
C9 | 0.48592 (12) | 0.05478 (17) | 0.35351 (7) | 0.0263 (4) | |
C11 | 0.58123 (11) | 0.40478 (18) | 0.21881 (7) | 0.0243 (4) | |
C21 | 0.54235 (11) | 0.59554 (18) | 0.19122 (8) | 0.0270 (4) | |
C31 | 0.57910 (11) | 0.68403 (18) | 0.13073 (8) | 0.0283 (4) | |
C41 | 0.65478 (11) | 0.58023 (18) | 0.09807 (8) | 0.0266 (4) | |
C42 | 0.64175 (13) | 0.8314 (2) | −0.00325 (9) | 0.0400 (5) | |
C51 | 0.69393 (12) | 0.38858 (18) | 0.12627 (8) | 0.0293 (4) | |
C61 | 0.65808 (11) | 0.30128 (18) | 0.18673 (8) | 0.0272 (4) | |
H4A | 0.36650 | −0.17640 | 0.30750 | 0.0370* | |
H4B | 0.41090 | −0.16770 | 0.40350 | 0.0370* | |
H5A | 0.21180 | −0.07600 | 0.35960 | 0.0400* | |
H5B | 0.23160 | 0.07860 | 0.29680 | 0.0400* | |
H6A | 0.21740 | 0.24750 | 0.41350 | 0.0410* | |
H6B | 0.32960 | 0.12670 | 0.46970 | 0.0410* | |
H7A | 0.39280 | 0.44440 | 0.44220 | 0.0380* | |
H7B | 0.33870 | 0.40360 | 0.34760 | 0.0380* | |
H8 | 0.55210 | 0.22960 | 0.45890 | 0.0320* | |
H9 | 0.56180 | −0.01950 | 0.37740 | 0.0320* | |
H21 | 0.49140 | 0.66480 | 0.21320 | 0.0320* | |
H31 | 0.55300 | 0.81250 | 0.11220 | 0.0340* | |
H42A | 0.65590 | 0.94100 | 0.03480 | 0.0480* | |
H42B | 0.55620 | 0.80940 | −0.02760 | 0.0480* | |
H42C | 0.67550 | 0.86260 | −0.04540 | 0.0480* | |
H51 | 0.74460 | 0.31890 | 0.10420 | 0.0350* | |
H61 | 0.68520 | 0.17370 | 0.20590 | 0.0330* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0453 (6) | 0.0348 (5) | 0.0367 (6) | −0.0172 (5) | 0.0137 (5) | −0.0077 (4) |
O3 | 0.0460 (6) | 0.0277 (5) | 0.0285 (5) | −0.0054 (4) | 0.0147 (4) | −0.0053 (4) |
O41 | 0.0447 (6) | 0.0356 (5) | 0.0411 (6) | 0.0045 (4) | 0.0279 (5) | 0.0094 (4) |
N2 | 0.0272 (6) | 0.0238 (5) | 0.0252 (6) | −0.0029 (4) | 0.0112 (4) | 0.0004 (4) |
C1 | 0.0250 (7) | 0.0285 (7) | 0.0269 (7) | −0.0027 (5) | 0.0063 (5) | −0.0008 (6) |
C3 | 0.0247 (7) | 0.0206 (6) | 0.0289 (7) | 0.0032 (5) | 0.0105 (5) | 0.0006 (5) |
C4 | 0.0418 (8) | 0.0227 (7) | 0.0291 (7) | −0.0045 (6) | 0.0138 (6) | 0.0022 (6) |
C5 | 0.0316 (7) | 0.0332 (7) | 0.0373 (8) | −0.0089 (6) | 0.0127 (6) | 0.0009 (6) |
C6 | 0.0355 (8) | 0.0366 (8) | 0.0359 (8) | −0.0021 (6) | 0.0187 (6) | 0.0003 (6) |
C7 | 0.0394 (8) | 0.0256 (7) | 0.0329 (7) | −0.0014 (6) | 0.0161 (6) | −0.0032 (6) |
C8 | 0.0307 (7) | 0.0288 (7) | 0.0200 (6) | −0.0048 (5) | 0.0066 (5) | −0.0001 (5) |
C9 | 0.0279 (7) | 0.0238 (6) | 0.0269 (7) | 0.0024 (5) | 0.0089 (5) | 0.0046 (5) |
C11 | 0.0237 (7) | 0.0255 (6) | 0.0246 (6) | −0.0025 (5) | 0.0093 (5) | 0.0004 (5) |
C21 | 0.0253 (7) | 0.0265 (7) | 0.0326 (7) | 0.0026 (5) | 0.0143 (6) | −0.0007 (6) |
C31 | 0.0296 (7) | 0.0234 (6) | 0.0331 (7) | 0.0044 (5) | 0.0122 (6) | 0.0049 (6) |
C41 | 0.0258 (7) | 0.0282 (7) | 0.0276 (7) | −0.0022 (5) | 0.0112 (5) | 0.0010 (5) |
C42 | 0.0452 (9) | 0.0434 (8) | 0.0342 (8) | 0.0015 (7) | 0.0168 (7) | 0.0125 (7) |
C51 | 0.0272 (7) | 0.0283 (7) | 0.0372 (8) | 0.0036 (5) | 0.0171 (6) | −0.0005 (6) |
C61 | 0.0244 (7) | 0.0235 (6) | 0.0339 (7) | 0.0032 (5) | 0.0100 (6) | 0.0038 (5) |
O1—C1 | 1.2095 (16) | C41—C51 | 1.3904 (17) |
O3—C3 | 1.2112 (15) | C51—C61 | 1.3787 (19) |
O41—C41 | 1.3723 (17) | C4—H4A | 0.9700 |
O41—C42 | 1.4274 (17) | C4—H4B | 0.9700 |
N2—C1 | 1.3993 (16) | C5—H5A | 0.9700 |
N2—C3 | 1.3980 (15) | C5—H5B | 0.9700 |
N2—C11 | 1.4408 (16) | C6—H6A | 0.9700 |
C1—C8 | 1.5117 (18) | C6—H6B | 0.9700 |
C3—C9 | 1.5119 (17) | C7—H7A | 0.9700 |
C4—C5 | 1.511 (2) | C7—H7B | 0.9700 |
C4—C9 | 1.5262 (19) | C8—H8 | 0.9800 |
C5—C6 | 1.5260 (19) | C9—H9 | 0.9800 |
C6—C7 | 1.520 (2) | C21—H21 | 0.9300 |
C7—C8 | 1.539 (2) | C31—H31 | 0.9300 |
C8—C9 | 1.5311 (17) | C42—H42A | 0.9600 |
C11—C21 | 1.3817 (17) | C42—H42B | 0.9600 |
C11—C61 | 1.3883 (18) | C42—H42C | 0.9600 |
C21—C31 | 1.3884 (18) | C51—H51 | 0.9300 |
C31—C41 | 1.3848 (19) | C61—H61 | 0.9300 |
C41—O41—C42 | 117.36 (11) | C4—C5—H5A | 109.00 |
C1—N2—C3 | 111.84 (10) | C4—C5—H5B | 109.00 |
C1—N2—C11 | 124.83 (10) | C6—C5—H5A | 109.00 |
C3—N2—C11 | 123.33 (10) | C6—C5—H5B | 109.00 |
O1—C1—N2 | 124.70 (12) | H5A—C5—H5B | 108.00 |
O1—C1—C8 | 127.51 (12) | C5—C6—H6A | 110.00 |
N2—C1—C8 | 107.64 (10) | C5—C6—H6B | 110.00 |
O3—C3—N2 | 124.32 (12) | C7—C6—H6A | 110.00 |
O3—C3—C9 | 128.52 (11) | C7—C6—H6B | 110.00 |
N2—C3—C9 | 107.12 (10) | H6A—C6—H6B | 108.00 |
C5—C4—C9 | 113.66 (10) | C6—C7—H7A | 109.00 |
C4—C5—C6 | 111.27 (12) | C6—C7—H7B | 109.00 |
C5—C6—C7 | 110.02 (12) | C8—C7—H7A | 109.00 |
C6—C7—C8 | 112.26 (11) | C8—C7—H7B | 109.00 |
C1—C8—C7 | 108.91 (10) | H7A—C7—H7B | 108.00 |
C1—C8—C9 | 103.54 (10) | C1—C8—H8 | 110.00 |
C7—C8—C9 | 113.63 (11) | C7—C8—H8 | 110.00 |
C3—C9—C4 | 115.67 (10) | C9—C8—H8 | 110.00 |
C3—C9—C8 | 103.09 (9) | C3—C9—H9 | 107.00 |
C4—C9—C8 | 117.35 (11) | C4—C9—H9 | 107.00 |
N2—C11—C21 | 120.58 (11) | C8—C9—H9 | 107.00 |
N2—C11—C61 | 119.23 (11) | C11—C21—H21 | 120.00 |
C21—C11—C61 | 120.20 (12) | C31—C21—H21 | 120.00 |
C11—C21—C31 | 120.15 (12) | C21—C31—H31 | 120.00 |
C21—C31—C41 | 119.73 (11) | C41—C31—H31 | 120.00 |
O41—C41—C31 | 124.48 (11) | O41—C42—H42A | 109.00 |
O41—C41—C51 | 115.66 (12) | O41—C42—H42B | 109.00 |
C31—C41—C51 | 119.85 (12) | O41—C42—H42C | 109.00 |
C41—C51—C61 | 120.40 (13) | H42A—C42—H42B | 109.00 |
C11—C61—C51 | 119.66 (11) | H42A—C42—H42C | 110.00 |
C5—C4—H4A | 109.00 | H42B—C42—H42C | 110.00 |
C5—C4—H4B | 109.00 | C41—C51—H51 | 120.00 |
C9—C4—H4A | 109.00 | C61—C51—H51 | 120.00 |
C9—C4—H4B | 109.00 | C11—C61—H61 | 120.00 |
H4A—C4—H4B | 108.00 | C51—C61—H61 | 120.00 |
C42—O41—C41—C31 | −13.59 (19) | C5—C4—C9—C8 | 38.31 (15) |
C42—O41—C41—C51 | 167.66 (12) | C5—C4—C9—C3 | −83.79 (14) |
C3—N2—C1—C8 | −3.10 (14) | C9—C4—C5—C6 | −50.57 (15) |
C11—N2—C1—C8 | 177.11 (11) | C4—C5—C6—C7 | 61.34 (14) |
C11—N2—C3—C9 | 166.12 (11) | C5—C6—C7—C8 | −58.69 (15) |
C1—N2—C11—C21 | −56.72 (18) | C6—C7—C8—C1 | 160.25 (11) |
C3—N2—C11—C21 | 123.52 (13) | C6—C7—C8—C9 | 45.42 (15) |
C3—N2—C1—O1 | −179.06 (13) | C7—C8—C9—C3 | 92.97 (13) |
C11—N2—C1—O1 | 1.2 (2) | C7—C8—C9—C4 | −35.41 (15) |
C11—N2—C3—O3 | −11.6 (2) | C1—C8—C9—C3 | −25.01 (13) |
C1—N2—C3—C9 | −13.68 (14) | C1—C8—C9—C4 | −153.39 (11) |
C1—N2—C11—C61 | 123.53 (13) | N2—C11—C61—C51 | 178.75 (12) |
C3—N2—C11—C61 | −56.23 (17) | C21—C11—C61—C51 | −1.00 (19) |
C1—N2—C3—O3 | 168.63 (13) | N2—C11—C21—C31 | −179.18 (12) |
N2—C1—C8—C7 | −103.15 (12) | C61—C11—C21—C31 | 0.57 (19) |
O1—C1—C8—C9 | −166.11 (14) | C11—C21—C31—C41 | 0.08 (19) |
N2—C1—C8—C9 | 18.08 (13) | C21—C31—C41—C51 | −0.3 (2) |
O1—C1—C8—C7 | 72.67 (17) | C21—C31—C41—O41 | −179.00 (12) |
O3—C3—C9—C8 | −158.30 (14) | O41—C41—C51—C61 | 178.67 (12) |
N2—C3—C9—C4 | 153.56 (11) | C31—C41—C51—C61 | −0.1 (2) |
O3—C3—C9—C4 | −28.9 (2) | C41—C51—C61—C11 | 0.8 (2) |
N2—C3—C9—C8 | 24.14 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O3i | 0.93 | 2.56 | 3.2205 (15) | 128 |
C51—H51···O1ii | 0.93 | 2.46 | 3.2914 (17) | 149 |
Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z+1/2. |
C15H15NO4 | F(000) = 576 |
Mr = 273.28 | Dx = 1.383 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2474 reflections |
a = 6.4958 (2) Å | θ = 3.3–28.7° |
b = 12.5236 (4) Å | µ = 0.10 mm−1 |
c = 16.1281 (6) Å | T = 200 K |
V = 1312.03 (8) Å3 | Needles, colourless |
Z = 4 | 0.45 × 0.12 × 0.08 mm |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 1728 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1395 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 16.077 pixels mm-1 | θmax = 28.0°, θmin = 3.3° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −16→12 |
Tmin = 0.980, Tmax = 0.990 | l = −21→9 |
4693 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0446P)2] where P = (Fo2 + 2Fc2)/3 |
1728 reflections | (Δ/σ)max < 0.001 |
185 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C15H15NO4 | V = 1312.03 (8) Å3 |
Mr = 273.28 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.4958 (2) Å | µ = 0.10 mm−1 |
b = 12.5236 (4) Å | T = 200 K |
c = 16.1281 (6) Å | 0.45 × 0.12 × 0.08 mm |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 1728 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1395 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.990 | Rint = 0.024 |
4693 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.18 e Å−3 |
1728 reflections | Δρmin = −0.18 e Å−3 |
185 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O1 | 0.3742 (2) | 0.03578 (12) | 0.64532 (10) | 0.0283 (5) | |
O3 | −0.0620 (3) | 0.20661 (15) | 0.46989 (11) | 0.0471 (7) | |
O31 | 0.3658 (3) | 0.40076 (13) | 0.77921 (11) | 0.0336 (6) | |
O32 | 0.1156 (3) | 0.41628 (12) | 0.87409 (10) | 0.0306 (5) | |
N2 | 0.1305 (3) | 0.12973 (13) | 0.57271 (11) | 0.0190 (5) | |
C1 | 0.2977 (3) | 0.06243 (16) | 0.57948 (15) | 0.0203 (7) | |
C3 | 0.0710 (4) | 0.14497 (18) | 0.49016 (15) | 0.0267 (7) | |
C4 | 0.0431 (4) | −0.0268 (2) | 0.41929 (17) | 0.0337 (8) | |
C5 | 0.1575 (4) | −0.1282 (2) | 0.39722 (17) | 0.0394 (9) | |
C6 | 0.3037 (4) | −0.15842 (19) | 0.46748 (18) | 0.0407 (9) | |
C7 | 0.4642 (4) | −0.07326 (19) | 0.47977 (17) | 0.0352 (8) | |
C8 | 0.3732 (4) | 0.03688 (18) | 0.49230 (15) | 0.0273 (7) | |
C9 | 0.1892 (4) | 0.06670 (18) | 0.43767 (15) | 0.0281 (8) | |
C11 | 0.0356 (3) | 0.18358 (16) | 0.64192 (14) | 0.0176 (6) | |
C21 | 0.1500 (3) | 0.25567 (16) | 0.68784 (13) | 0.0190 (6) | |
C31 | 0.0592 (3) | 0.30532 (17) | 0.75634 (13) | 0.0201 (6) | |
C41 | −0.1440 (3) | 0.28329 (18) | 0.77614 (15) | 0.0248 (7) | |
C51 | −0.2570 (3) | 0.21244 (19) | 0.72850 (15) | 0.0280 (7) | |
C61 | −0.1674 (3) | 0.16229 (17) | 0.66081 (15) | 0.0235 (7) | |
C311 | 0.1794 (3) | 0.37990 (17) | 0.80984 (15) | 0.0216 (7) | |
H4A | −0.04230 | −0.03990 | 0.46760 | 0.0400* | |
H4B | −0.04680 | −0.00740 | 0.37370 | 0.0400* | |
H5A | 0.23510 | −0.11750 | 0.34650 | 0.0470* | |
H5B | 0.06000 | −0.18560 | 0.38800 | 0.0470* | |
H6A | 0.22610 | −0.16770 | 0.51830 | 0.0490* | |
H6B | 0.37050 | −0.22570 | 0.45450 | 0.0490* | |
H7A | 0.55400 | −0.07180 | 0.43170 | 0.0420* | |
H7B | 0.54740 | −0.09140 | 0.52770 | 0.0420* | |
H8 | 0.48270 | 0.08820 | 0.47970 | 0.0330* | |
H9 | 0.23550 | 0.10040 | 0.38610 | 0.0340* | |
H21 | 0.28550 | 0.27090 | 0.67330 | 0.0230* | |
H31 | 0.427 (4) | 0.444 (2) | 0.8157 (19) | 0.049 (9)* | |
H41 | −0.20480 | 0.31630 | 0.82170 | 0.0300* | |
H51 | −0.39360 | 0.19840 | 0.74190 | 0.0340* | |
H61 | −0.24330 | 0.11490 | 0.62860 | 0.0280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0247 (9) | 0.0310 (8) | 0.0292 (9) | 0.0063 (8) | −0.0091 (8) | 0.0012 (7) |
O3 | 0.0641 (13) | 0.0478 (11) | 0.0293 (10) | 0.0328 (11) | −0.0152 (10) | −0.0065 (9) |
O31 | 0.0260 (9) | 0.0416 (10) | 0.0332 (10) | −0.0113 (9) | 0.0027 (8) | −0.0162 (8) |
O32 | 0.0373 (10) | 0.0321 (8) | 0.0225 (9) | −0.0037 (8) | 0.0027 (8) | −0.0083 (8) |
N2 | 0.0194 (9) | 0.0179 (8) | 0.0197 (10) | 0.0011 (8) | −0.0033 (8) | −0.0012 (7) |
C1 | 0.0166 (11) | 0.0141 (10) | 0.0303 (13) | −0.0029 (9) | −0.0039 (10) | −0.0014 (10) |
C3 | 0.0352 (14) | 0.0235 (11) | 0.0215 (12) | 0.0037 (11) | −0.0058 (11) | −0.0011 (10) |
C4 | 0.0342 (14) | 0.0375 (14) | 0.0294 (14) | 0.0048 (13) | −0.0093 (13) | −0.0062 (12) |
C5 | 0.0484 (17) | 0.0354 (13) | 0.0344 (15) | 0.0015 (14) | −0.0098 (14) | −0.0127 (12) |
C6 | 0.0509 (18) | 0.0283 (13) | 0.0429 (17) | 0.0087 (13) | −0.0094 (15) | −0.0073 (12) |
C7 | 0.0299 (14) | 0.0391 (14) | 0.0367 (15) | 0.0108 (13) | −0.0038 (12) | −0.0102 (12) |
C8 | 0.0242 (12) | 0.0299 (12) | 0.0279 (13) | −0.0015 (11) | 0.0001 (12) | −0.0064 (10) |
C9 | 0.0358 (14) | 0.0271 (12) | 0.0215 (13) | 0.0061 (11) | 0.0007 (11) | −0.0008 (10) |
C11 | 0.0181 (11) | 0.0158 (10) | 0.0188 (11) | 0.0030 (9) | −0.0038 (10) | 0.0007 (9) |
C21 | 0.0169 (11) | 0.0203 (10) | 0.0198 (11) | −0.0011 (10) | −0.0014 (10) | 0.0013 (9) |
C31 | 0.0216 (11) | 0.0198 (10) | 0.0188 (11) | 0.0009 (10) | −0.0023 (10) | 0.0024 (9) |
C41 | 0.0229 (12) | 0.0293 (11) | 0.0223 (11) | 0.0034 (11) | 0.0035 (11) | −0.0024 (10) |
C51 | 0.0169 (11) | 0.0346 (13) | 0.0326 (14) | −0.0040 (11) | 0.0019 (11) | 0.0029 (12) |
C61 | 0.0194 (12) | 0.0218 (11) | 0.0292 (13) | −0.0035 (10) | −0.0051 (10) | −0.0010 (10) |
C311 | 0.0223 (12) | 0.0202 (11) | 0.0223 (12) | 0.0026 (10) | −0.0018 (10) | 0.0016 (9) |
O1—C1 | 1.219 (3) | C31—C41 | 1.386 (3) |
O3—C3 | 1.204 (3) | C31—C311 | 1.492 (3) |
O31—C311 | 1.334 (3) | C41—C51 | 1.384 (3) |
O32—C311 | 1.206 (3) | C51—C61 | 1.388 (3) |
O31—H31 | 0.89 (3) | C4—H4A | 0.9700 |
N2—C3 | 1.399 (3) | C4—H4B | 0.9700 |
N2—C11 | 1.443 (3) | C5—H5A | 0.9700 |
N2—C1 | 1.379 (3) | C5—H5B | 0.9700 |
C1—C8 | 1.523 (3) | C6—H6A | 0.9700 |
C3—C9 | 1.506 (3) | C6—H6B | 0.9700 |
C4—C9 | 1.536 (4) | C7—H7A | 0.9700 |
C4—C5 | 1.514 (4) | C7—H7B | 0.9700 |
C5—C6 | 1.526 (4) | C8—H8 | 0.9800 |
C6—C7 | 1.505 (4) | C9—H9 | 0.9800 |
C7—C8 | 1.514 (3) | C21—H21 | 0.9300 |
C8—C9 | 1.531 (4) | C41—H41 | 0.9300 |
C11—C61 | 1.379 (3) | C51—H51 | 0.9300 |
C11—C21 | 1.384 (3) | C61—H61 | 0.9300 |
C21—C31 | 1.398 (3) | ||
C311—O31—H31 | 106.2 (18) | C9—C4—H4A | 109.00 |
C1—N2—C3 | 112.10 (19) | C4—C5—H5A | 110.00 |
C3—N2—C11 | 123.67 (18) | C4—C5—H5B | 110.00 |
C1—N2—C11 | 124.13 (18) | C6—C5—H5A | 110.00 |
O1—C1—C8 | 127.98 (19) | C6—C5—H5B | 110.00 |
N2—C1—C8 | 107.99 (19) | H5A—C5—H5B | 108.00 |
O1—C1—N2 | 123.9 (2) | C7—C6—H6A | 110.00 |
O3—C3—N2 | 123.0 (2) | C7—C6—H6B | 110.00 |
N2—C3—C9 | 107.78 (19) | C5—C6—H6B | 109.00 |
O3—C3—C9 | 129.1 (2) | C5—C6—H6A | 110.00 |
C5—C4—C9 | 112.4 (2) | H6A—C6—H6B | 108.00 |
C4—C5—C6 | 109.8 (2) | H7A—C7—H7B | 108.00 |
C5—C6—C7 | 110.7 (2) | C6—C7—H7B | 109.00 |
C6—C7—C8 | 113.1 (2) | C8—C7—H7B | 109.00 |
C1—C8—C7 | 116.1 (2) | C6—C7—H7A | 109.00 |
C7—C8—C9 | 116.8 (2) | C8—C7—H7A | 109.00 |
C1—C8—C9 | 103.22 (19) | C1—C8—H8 | 107.00 |
C3—C9—C4 | 106.8 (2) | C7—C8—H8 | 107.00 |
C4—C9—C8 | 114.04 (19) | C9—C8—H8 | 107.00 |
C3—C9—C8 | 103.49 (19) | C3—C9—H9 | 111.00 |
N2—C11—C61 | 119.28 (19) | C8—C9—H9 | 111.00 |
C21—C11—C61 | 121.4 (2) | C4—C9—H9 | 111.00 |
N2—C11—C21 | 119.31 (18) | C11—C21—H21 | 120.00 |
C11—C21—C31 | 119.10 (18) | C31—C21—H21 | 120.00 |
C21—C31—C41 | 119.69 (19) | C51—C41—H41 | 120.00 |
C21—C31—C311 | 120.97 (18) | C31—C41—H41 | 120.00 |
C41—C31—C311 | 119.33 (19) | C41—C51—H51 | 120.00 |
C31—C41—C51 | 120.3 (2) | C61—C51—H51 | 120.00 |
C41—C51—C61 | 120.29 (19) | C11—C61—H61 | 120.00 |
C11—C61—C51 | 119.2 (2) | C51—C61—H61 | 120.00 |
H4A—C4—H4B | 108.00 | O31—C311—C31 | 112.55 (19) |
C5—C4—H4B | 109.00 | O32—C311—C31 | 123.63 (19) |
C9—C4—H4B | 109.00 | O31—C311—O32 | 123.8 (2) |
C5—C4—H4A | 109.00 | ||
C3—N2—C1—O1 | −178.5 (2) | C4—C5—C6—C7 | −62.6 (3) |
C3—N2—C1—C8 | 5.7 (2) | C5—C6—C7—C8 | 53.8 (3) |
C11—N2—C1—O1 | 5.1 (3) | C6—C7—C8—C1 | 81.3 (3) |
C11—N2—C1—C8 | −170.65 (18) | C6—C7—C8—C9 | −40.9 (3) |
C1—N2—C3—O3 | −174.6 (2) | C1—C8—C9—C3 | 22.7 (2) |
C1—N2—C3—C9 | 9.7 (3) | C1—C8—C9—C4 | −93.0 (2) |
C11—N2—C3—O3 | 1.8 (4) | C7—C8—C9—C3 | 151.4 (2) |
C11—N2—C3—C9 | −173.96 (19) | C7—C8—C9—C4 | 35.7 (3) |
C1—N2—C11—C21 | 61.8 (3) | N2—C11—C21—C31 | −178.14 (18) |
C1—N2—C11—C61 | −118.4 (2) | C61—C11—C21—C31 | 2.0 (3) |
C3—N2—C11—C21 | −114.2 (2) | N2—C11—C61—C51 | 178.6 (2) |
C3—N2—C11—C61 | 65.7 (3) | C21—C11—C61—C51 | −1.5 (3) |
O1—C1—C8—C7 | 37.3 (3) | C11—C21—C31—C41 | −1.2 (3) |
O1—C1—C8—C9 | 166.3 (2) | C11—C21—C31—C311 | 177.28 (19) |
N2—C1—C8—C7 | −147.2 (2) | C21—C31—C41—C51 | 0.1 (3) |
N2—C1—C8—C9 | −18.1 (2) | C311—C31—C41—C51 | −178.5 (2) |
O3—C3—C9—C4 | −75.2 (3) | C21—C31—C311—O31 | 7.1 (3) |
O3—C3—C9—C8 | 164.1 (3) | C21—C31—C311—O32 | −172.2 (2) |
N2—C3—C9—C4 | 100.2 (2) | C41—C31—C311—O31 | −174.4 (2) |
N2—C3—C9—C8 | −20.5 (2) | C41—C31—C311—O32 | 6.3 (3) |
C9—C4—C5—C6 | 57.4 (3) | C31—C41—C51—C61 | 0.4 (3) |
C5—C4—C9—C3 | −157.6 (2) | C41—C51—C61—C11 | 0.3 (3) |
C5—C4—C9—C8 | −43.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O1i | 0.89 (3) | 1.84 (3) | 2.682 (2) | 156 (3) |
C21—H21···O3ii | 0.93 | 2.53 | 3.193 (3) | 129 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1/2, −y+1/2, −z+1. |
C15H15NO4·H2O | F(000) = 616 |
Mr = 291.30 | Dx = 1.363 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2417 reflections |
a = 13.077 (2) Å | θ = 3.1–28.7° |
b = 6.6713 (7) Å | µ = 0.10 mm−1 |
c = 16.432 (2) Å | T = 200 K |
β = 97.982 (13)° | Prism, colourless |
V = 1419.6 (3) Å3 | 0.30 × 0.10 × 0.08 mm |
Z = 4 |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2790 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1374 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −16→13 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −8→8 |
Tmin = 0.813, Tmax = 0.980 | l = −14→20 |
9649 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0704P)2] where P = (Fo2 + 2Fc2)/3 |
2790 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C15H15NO4·H2O | V = 1419.6 (3) Å3 |
Mr = 291.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.077 (2) Å | µ = 0.10 mm−1 |
b = 6.6713 (7) Å | T = 200 K |
c = 16.432 (2) Å | 0.30 × 0.10 × 0.08 mm |
β = 97.982 (13)° |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 2790 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1374 reflections with I > 2σ(I) |
Tmin = 0.813, Tmax = 0.980 | Rint = 0.055 |
9649 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.34 e Å−3 |
2790 reflections | Δρmin = −0.20 e Å−3 |
194 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
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 > 2sigma(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) | |
O1 | 0.80344 (15) | 0.0890 (3) | 0.54274 (11) | 0.0502 (7) | |
O3 | 0.58298 (15) | 0.6120 (2) | 0.56137 (11) | 0.0480 (7) | |
O41 | 0.50408 (17) | −0.2147 (3) | 0.82985 (12) | 0.0632 (9) | |
O42 | 0.53908 (18) | 0.0528 (3) | 0.90848 (13) | 0.0732 (10) | |
N2 | 0.68963 (16) | 0.3350 (3) | 0.57093 (12) | 0.0333 (7) | |
C1 | 0.7620 (2) | 0.2489 (4) | 0.52623 (16) | 0.0370 (9) | |
C3 | 0.6525 (2) | 0.5193 (3) | 0.53794 (15) | 0.0371 (10) | |
C4 | 0.6735 (3) | 0.7105 (4) | 0.40365 (19) | 0.0664 (14) | |
C5 | 0.6294 (3) | 0.5965 (5) | 0.3295 (2) | 0.0707 (14) | |
C6 | 0.7017 (3) | 0.4390 (4) | 0.30655 (18) | 0.0656 (13) | |
C7 | 0.7239 (3) | 0.2867 (4) | 0.37592 (16) | 0.0580 (13) | |
C8 | 0.7723 (2) | 0.3861 (4) | 0.45460 (15) | 0.0422 (10) | |
C9 | 0.7219 (2) | 0.5812 (4) | 0.47533 (17) | 0.0490 (10) | |
C11 | 0.65230 (19) | 0.2395 (3) | 0.64028 (14) | 0.0312 (8) | |
C21 | 0.6115 (2) | 0.0499 (3) | 0.63172 (15) | 0.0361 (9) | |
C31 | 0.5750 (2) | −0.0399 (4) | 0.69778 (15) | 0.0376 (9) | |
C41 | 0.57975 (19) | 0.0608 (4) | 0.77213 (15) | 0.0341 (9) | |
C51 | 0.6220 (2) | 0.2516 (4) | 0.78004 (16) | 0.0397 (9) | |
C61 | 0.6595 (2) | 0.3428 (4) | 0.71395 (15) | 0.0370 (9) | |
C411 | 0.5398 (2) | −0.0315 (4) | 0.84418 (18) | 0.0461 (11) | |
O1W | 0.9383 (2) | −0.1718 (3) | 0.46543 (15) | 0.0644 (10) | 0.810 |
O2W | 0.9381 (10) | 0.0061 (18) | 0.4139 (7) | 0.079 (3)* | 0.190 |
H4A | 0.61920 | 0.79100 | 0.42180 | 0.0800* | |
H4B | 0.72560 | 0.80150 | 0.38870 | 0.0800* | |
H5A | 0.61330 | 0.68870 | 0.28380 | 0.0850* | |
H5B | 0.56550 | 0.53340 | 0.33950 | 0.0850* | |
H6A | 0.76580 | 0.50090 | 0.29610 | 0.0790* | |
H6B | 0.67120 | 0.37170 | 0.25670 | 0.0790* | |
H7A | 0.66000 | 0.22200 | 0.38490 | 0.0690* | |
H7B | 0.77020 | 0.18440 | 0.36030 | 0.0690* | |
H8 | 0.84560 | 0.41010 | 0.45180 | 0.0510* | |
H9 | 0.77710 | 0.66240 | 0.50550 | 0.0590* | |
H21 | 0.60850 | −0.01750 | 0.58190 | 0.0430* | |
H31 | 0.54720 | −0.16830 | 0.69240 | 0.0450* | |
H41 | 0.48190 | −0.25400 | 0.87690 | 0.0950* | |
H51 | 0.62530 | 0.31920 | 0.82980 | 0.0480* | |
H61 | 0.68860 | 0.47010 | 0.71910 | 0.0440* | |
H11W | 0.89650 | −0.09080 | 0.47990 | 0.0970* | 0.810 |
H12W | 0.94650 | −0.26180 | 0.49990 | 0.0970* | 0.810 |
H21W | 0.89720 | 0.02910 | 0.45270 | 0.1180* | 0.190 |
H22W | 0.96620 | 0.12910 | 0.41170 | 0.1180* | 0.190 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0626 (14) | 0.0463 (11) | 0.0474 (12) | 0.0216 (10) | 0.0273 (10) | 0.0153 (9) |
O3 | 0.0564 (14) | 0.0348 (10) | 0.0570 (13) | 0.0078 (9) | 0.0228 (11) | −0.0050 (9) |
O41 | 0.0800 (17) | 0.0664 (14) | 0.0488 (13) | −0.0164 (11) | 0.0285 (12) | 0.0104 (10) |
O42 | 0.0885 (19) | 0.1014 (17) | 0.0363 (13) | −0.0290 (13) | 0.0319 (12) | −0.0105 (12) |
N2 | 0.0435 (15) | 0.0305 (11) | 0.0289 (12) | 0.0023 (9) | 0.0157 (11) | −0.0005 (9) |
C1 | 0.0432 (18) | 0.0394 (15) | 0.0311 (15) | 0.0026 (13) | 0.0148 (13) | 0.0002 (12) |
C3 | 0.0484 (19) | 0.0287 (14) | 0.0355 (16) | −0.0019 (12) | 0.0102 (14) | −0.0047 (11) |
C4 | 0.091 (3) | 0.0535 (19) | 0.059 (2) | 0.0228 (17) | 0.026 (2) | 0.0202 (16) |
C5 | 0.070 (3) | 0.071 (2) | 0.065 (2) | 0.0037 (18) | −0.012 (2) | 0.0190 (18) |
C6 | 0.093 (3) | 0.063 (2) | 0.0380 (18) | 0.0043 (18) | −0.0004 (18) | 0.0000 (15) |
C7 | 0.090 (3) | 0.0442 (17) | 0.0397 (18) | −0.0029 (15) | 0.0088 (18) | −0.0030 (13) |
C8 | 0.054 (2) | 0.0395 (15) | 0.0356 (16) | 0.0060 (12) | 0.0150 (14) | 0.0066 (12) |
C9 | 0.066 (2) | 0.0412 (16) | 0.0426 (17) | 0.0025 (14) | 0.0178 (15) | 0.0070 (13) |
C11 | 0.0349 (16) | 0.0317 (13) | 0.0291 (14) | 0.0027 (11) | 0.0120 (12) | −0.0015 (11) |
C21 | 0.0458 (18) | 0.0348 (15) | 0.0299 (15) | 0.0016 (12) | 0.0133 (13) | −0.0035 (11) |
C31 | 0.0413 (18) | 0.0350 (14) | 0.0378 (16) | −0.0031 (11) | 0.0102 (13) | −0.0014 (12) |
C41 | 0.0306 (16) | 0.0423 (15) | 0.0312 (15) | 0.0007 (11) | 0.0107 (12) | 0.0009 (12) |
C51 | 0.0389 (17) | 0.0520 (16) | 0.0298 (15) | −0.0018 (13) | 0.0104 (13) | −0.0099 (12) |
C61 | 0.0335 (16) | 0.0390 (14) | 0.0402 (16) | −0.0046 (11) | 0.0113 (13) | −0.0078 (13) |
C411 | 0.0396 (18) | 0.061 (2) | 0.0399 (18) | −0.0030 (14) | 0.0136 (14) | 0.0037 (15) |
O1W | 0.078 (2) | 0.0581 (14) | 0.0693 (18) | 0.0183 (13) | 0.0533 (15) | 0.0055 (13) |
O1—C1 | 1.210 (3) | C11—C61 | 1.385 (3) |
O3—C3 | 1.206 (3) | C21—C31 | 1.382 (3) |
O41—C411 | 1.318 (3) | C31—C41 | 1.388 (4) |
O42—C411 | 1.198 (4) | C41—C411 | 1.492 (4) |
O41—H41 | 0.9000 | C41—C51 | 1.387 (4) |
O1W—H12W | 0.8200 | C51—C61 | 1.392 (4) |
O1W—H11W | 0.8300 | C4—H4B | 0.9700 |
O2W—H22W | 0.9000 | C4—H4A | 0.9700 |
O2W—H21W | 0.9000 | C5—H5B | 0.9700 |
N2—C1 | 1.399 (3) | C5—H5A | 0.9700 |
N2—C3 | 1.403 (3) | C6—H6B | 0.9700 |
N2—C11 | 1.448 (3) | C6—H6A | 0.9700 |
C1—C8 | 1.512 (4) | C7—H7A | 0.9700 |
C3—C9 | 1.521 (4) | C7—H7B | 0.9700 |
C4—C5 | 1.483 (5) | C8—H8 | 0.9800 |
C4—C9 | 1.525 (4) | C9—H9 | 0.9800 |
C5—C6 | 1.496 (5) | C21—H21 | 0.9300 |
C6—C7 | 1.525 (4) | C31—H31 | 0.9300 |
C7—C8 | 1.512 (4) | C51—H51 | 0.9300 |
C8—C9 | 1.519 (4) | C61—H61 | 0.9300 |
C11—C21 | 1.372 (3) | ||
C411—O41—H41 | 105.00 | C9—C4—H4A | 109.00 |
H11W—O1W—H12W | 108.00 | C9—C4—H4B | 109.00 |
H21W—O2W—H22W | 99.00 | C4—C5—H5B | 109.00 |
C1—N2—C3 | 112.3 (2) | C6—C5—H5A | 109.00 |
C1—N2—C11 | 124.0 (2) | H5A—C5—H5B | 108.00 |
C3—N2—C11 | 123.6 (2) | C4—C5—H5A | 109.00 |
N2—C1—C8 | 107.5 (2) | C6—C5—H5B | 109.00 |
O1—C1—C8 | 128.5 (2) | C5—C6—H6B | 110.00 |
O1—C1—N2 | 124.0 (2) | C7—C6—H6A | 110.00 |
N2—C3—C9 | 107.0 (2) | H6A—C6—H6B | 108.00 |
O3—C3—N2 | 124.2 (2) | C7—C6—H6B | 110.00 |
O3—C3—C9 | 128.6 (2) | C5—C6—H6A | 110.00 |
C5—C4—C9 | 114.6 (2) | C8—C7—H7B | 109.00 |
C4—C5—C6 | 112.3 (3) | C6—C7—H7A | 109.00 |
C5—C6—C7 | 109.9 (3) | C6—C7—H7B | 109.00 |
C6—C7—C8 | 111.2 (2) | C8—C7—H7A | 109.00 |
C1—C8—C7 | 109.2 (2) | H7A—C7—H7B | 108.00 |
C7—C8—C9 | 115.1 (2) | C7—C8—H8 | 109.00 |
C1—C8—C9 | 104.8 (2) | C9—C8—H8 | 109.00 |
C3—C9—C4 | 117.0 (2) | C1—C8—H8 | 109.00 |
C4—C9—C8 | 117.3 (2) | C8—C9—H9 | 106.00 |
C3—C9—C8 | 103.7 (2) | C3—C9—H9 | 106.00 |
N2—C11—C61 | 118.7 (2) | C4—C9—H9 | 106.00 |
C21—C11—C61 | 121.8 (2) | C11—C21—H21 | 120.00 |
N2—C11—C21 | 119.6 (2) | C31—C21—H21 | 120.00 |
C11—C21—C31 | 119.4 (2) | C21—C31—H31 | 120.00 |
C21—C31—C41 | 120.2 (2) | C41—C31—H31 | 120.00 |
C31—C41—C51 | 119.7 (2) | C41—C51—H51 | 120.00 |
C51—C41—C411 | 118.9 (2) | C61—C51—H51 | 120.00 |
C31—C41—C411 | 121.4 (2) | C11—C61—H61 | 121.00 |
C41—C51—C61 | 120.5 (2) | C51—C61—H61 | 121.00 |
C11—C61—C51 | 118.4 (2) | O42—C411—C41 | 123.6 (2) |
H4A—C4—H4B | 108.00 | O41—C411—O42 | 123.2 (3) |
C5—C4—H4A | 109.00 | O41—C411—C41 | 113.3 (2) |
C5—C4—H4B | 109.00 | ||
C3—N2—C1—O1 | −179.1 (2) | C4—C5—C6—C7 | 61.6 (4) |
C3—N2—C1—C8 | −1.8 (3) | C5—C6—C7—C8 | −59.7 (4) |
C11—N2—C1—O1 | −2.7 (4) | C6—C7—C8—C1 | 162.2 (3) |
C11—N2—C1—C8 | 174.6 (2) | C6—C7—C8—C9 | 44.7 (4) |
C1—N2—C3—O3 | 172.9 (2) | C1—C8—C9—C3 | −20.8 (3) |
C1—N2—C3—C9 | −11.9 (3) | C1—C8—C9—C4 | −151.4 (2) |
C11—N2—C3—O3 | −3.5 (4) | C7—C8—C9—C3 | 99.2 (3) |
C11—N2—C3—C9 | 171.7 (2) | C7—C8—C9—C4 | −31.4 (4) |
C1—N2—C11—C21 | −53.8 (3) | N2—C11—C21—C31 | −179.3 (2) |
C1—N2—C11—C61 | 125.9 (3) | C61—C11—C21—C31 | 1.0 (4) |
C3—N2—C11—C21 | 122.2 (3) | N2—C11—C61—C51 | 179.0 (2) |
C3—N2—C11—C61 | −58.2 (3) | C21—C11—C61—C51 | −1.4 (4) |
O1—C1—C8—C7 | 67.9 (4) | C11—C21—C31—C41 | −0.1 (4) |
O1—C1—C8—C9 | −168.3 (3) | C21—C31—C41—C51 | −0.5 (4) |
N2—C1—C8—C7 | −109.3 (3) | C21—C31—C41—C411 | 179.3 (2) |
N2—C1—C8—C9 | 14.6 (3) | C31—C41—C51—C61 | 0.1 (4) |
O3—C3—C9—C4 | −34.1 (4) | C411—C41—C51—C61 | −179.6 (2) |
O3—C3—C9—C8 | −164.9 (3) | C31—C41—C411—O41 | 2.0 (4) |
N2—C3—C9—C4 | 151.1 (2) | C31—C41—C411—O42 | −177.3 (3) |
N2—C3—C9—C8 | 20.3 (3) | C51—C41—C411—O41 | −178.3 (2) |
C9—C4—C5—C6 | −47.3 (4) | C51—C41—C411—O42 | 2.4 (4) |
C5—C4—C9—C3 | −91.9 (3) | C41—C51—C61—C11 | 0.8 (4) |
C5—C4—C9—C8 | 32.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O1Wi | 0.90 | 1.71 | 2.609 (3) | 179 |
O1W—H11W···O1 | 0.83 | 2.08 | 2.894 (3) | 167 |
O1W—H12W···O42ii | 0.82 | 1.94 | 2.754 (3) | 172 |
O2W—H21W···O1 | 0.90 | 2.10 | 2.991 (12) | 179 |
O2W—H22W···O42iii | 0.90 | 2.33 | 3.233 (12) | 178 |
C9—H9···O1Wiv | 0.98 | 2.55 | 3.298 (4) | 133 |
C21—H21···O3v | 0.93 | 2.51 | 3.145 (3) | 126 |
C31—H31···O41 | 0.93 | 2.42 | 2.737 (3) | 100 |
Symmetry codes: (i) x−1/2, −y−1/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x, y+1, z; (v) x, y−1, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C15H19NO4 | C15H17NO3 | C15H15NO4 | C15H15NO4·H2O |
Mr | 277.31 | 259.30 | 273.28 | 291.30 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n | Orthorhombic, P212121 | Monoclinic, P21/n |
Temperature (K) | 200 | 200 | 200 | 200 |
a, b, c (Å) | 7.3557 (4), 8.3630 (4), 11.7128 (6) | 11.7119 (5), 6.6705 (3), 17.2898 (8) | 6.4958 (2), 12.5236 (4), 16.1281 (6) | 13.077 (2), 6.6713 (7), 16.432 (2) |
α, β, γ (°) | 100.453 (4), 97.232 (4), 104.042 (4) | 90, 109.482 (5), 90 | 90, 90, 90 | 90, 97.982 (13), 90 |
V (Å3) | 676.40 (6) | 1273.42 (11) | 1312.03 (8) | 1419.6 (3) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.09 | 0.10 | 0.10 |
Crystal size (mm) | 0.45 × 0.30 × 0.18 | 0.40 × 0.25 × 0.12 | 0.45 × 0.12 × 0.08 | 0.30 × 0.10 × 0.08 |
Data collection | ||||
Diffractometer | Oxford Diffraction Gemini-S CCD-detector diffractometer | Oxford Diffraction Gemini-S CCD-detector diffractometer | Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | Oxford Diffraction Gemini-S CCD-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.975, 0.980 | 0.929, 0.981 | 0.980, 0.990 | 0.813, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8079, 2640, 2082 | 8552, 2498, 1959 | 4693, 1728, 1395 | 9649, 2790, 1374 |
Rint | 0.024 | 0.024 | 0.024 | 0.055 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.660 | 0.617 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.087, 1.03 | 0.035, 0.088, 1.09 | 0.038, 0.086, 1.10 | 0.052, 0.132, 0.85 |
No. of reflections | 2640 | 2498 | 1728 | 2790 |
No. of parameters | 189 | 172 | 185 | 194 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 | 0.18, −0.17 | 0.18, −0.18 | 0.34, −0.20 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1993), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O22—H22···O21i | 0.94 (2) | 1.76 (2) | 2.6866 (14) | 173 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O3i | 0.93 | 2.56 | 3.2205 (15) | 128 |
C51—H51···O1ii | 0.93 | 2.46 | 3.2914 (17) | 149 |
Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O1i | 0.89 (3) | 1.84 (3) | 2.682 (2) | 156 (3) |
Symmetry code: (i) −x+1, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O1Wi | 0.90 | 1.71 | 2.609 (3) | 179 |
O1W—H11W···O1 | 0.83 | 2.08 | 2.894 (3) | 167 |
O1W—H12W···O42ii | 0.82 | 1.94 | 2.754 (3) | 172 |
O2W—H21W···O1 | 0.90 | 2.10 | 2.991 (12) | 179 |
O2W—H22W···O42iii | 0.90 | 2.33 | 3.233 (12) | 178 |
Symmetry codes: (i) x−1/2, −y−1/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x+1/2, −y+1/2, z−1/2. |
The 1:1 stoichiometric reaction of cis-cyclohexane-1,2-dicarboxylic anhydride (cis-CHDC anhydride) with substituted anilines has been found to give both open-chain amide carboxylic acids or more commonly cyclic imides under mild reaction conditions (Smith & Wermuth, 2012a). These products are analogous to the phthalanilic acids and phthalimides formed in the reactions of phthalic anhydride with anilines (Perry & Parveen, 2001). We previously reported the structure of the amide acid from the reaction of cis-CHDC anhydride with 3-fluoroaniline and the isomeric cyclic imides from the parallel reactions with the 2- and 4-fluoroanilines (Smith & Wermuth, 2012a), which are among only the very few crystallographically characterized examples of these compounds.
The parallel reaction of 2-methoxyaniline (o-anisidine), 4-methoxyaniline (p-anisidine), 3-carboxyaniline (m-aminobenzoic acid) and 4-carboxyaniline (p-aminobenzoic acid) with cis-CHDC anhydride under common mild reaction conditions in 50% ethanol–water solution yielded, respectively, the open-chain amide carboxylic acid racemic cis-2-[(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, (I), and the cyclic imides racemic 2-(4-methoxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, (II), chiral 2-(3-carboxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, (III), and racemic 2-(4-carboxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione monohydrate, (IV) (Figs. 1–4), and the structures are reported here.
With the racemic amide acid (I) (Fig. 1), the phenylcarbamoyl group is essentially planar [C21—C11—N11—C12 torsion angle = 175.18 (12)°], with a maximum deviation from the least-squares plane of 0.060 (1) Å for the carbonyl O atom. The conformation is stabilized by intramolecular N11—H···O211(methoxy) and aromatic C61—H···O12(carbonyl) interactions [2.6003 (14) and 2.8812 (17) Å, respectively]. The carboxylic acid group on the cyclohexane ring is almost parallel to the C1—C3 bond [C1—C2—C22—O22 torsion angle = 173.17 (10)°] and the methoxy group is close to coplanar with the benzene ring [C11—C21—O211—C211 torsion angle = 173.23 (11)°]. The molecules form discrete centrosymmetric dimers through classical intermolecular cyclic carboxyl–carboxyl O—H···O hydrogen-bonding interactions (Table 1) [graph-set notation R22(8); Etter et al., 1990] (Fig. 5). The amide group is not involved in intermolecular interactions, which is unlike the p-chloro-substituted analogue in which the amide group links hydrogen-bonded carboxylic acid chains into a two-dimensional sheet structure (Smith & Wermuth, 2012b).
The cyclic imides (II) and (IV) (Figs. 2 and 4) are racemic while compound (III) is chiral. However, the absolute configurations for the two chiral centres in (II) were not determined, being arbitrarily assigned (C8S,C9R). Conformationally, compounds (II)–(IV) are similar, with comparable ring rotations about the imide N—Car bond [minimum torsion angles C1/C3—N2—C11—C21 = -56.72 (18)° for (II), 61.8 (2)° for (III) and -53.8 (2)° for (IV)]. These correspond to dihedral angles of 51.55 (7), 59.22 (12) and 51.99 (14)°, respectively, between the benzene ring and the plane of the isoindole ring, in which distortion results in either atom C8 or C9 showing a maximum deviation of 0.157 (1) Å in (II), 0.139 (2) Å in (III) and 0.131 (3) Å in (IV). These values compare closely to those of 0.152 and 0.149 Å for the 2- and 4-fluoro analogues, respectively (Smith & Wermuth, 2012a), and 0.153 and 0.138 Å for the 4-bromo- and 3-carboxy-4-hydroxy-substituted analogues, respectively (Smith & Wermuth, 2012b). In (III) and (IV), the carboxylic acid substituent groups are close to being coplanar with the benzene rings [C21—C31—C311—O32 = -172.2 (2)° in (III) and C31—C41—C411—O42 = -177.3 (3)° in (IV)].
Unlike the structure of (II), in which there is only weak aromatic C—H···Oimide hydrogen-bonding interactions (Table 2), the crystal packing of both imides (III) and (IV) show strong intermolecular O—H···O hydrogen-bonding interactions involving carboxylic acid groups. In (III), these are with imide O-atom acceptors (Table 3), giving one-dimensional (C9) zigzag chains which extend along (010) (Fig. 6). With the monohydrate (IV), the para-related carboxylic acid substituent group forms a hydrogen bond with the partially disordered water molecule [O1W, occupancy factor = 0.81 (1); O2W, occupancy factor = 0.19 (1)], both components of which also act as donors to both imide and carboxyl O-atom acceptors (Table 4). These interactions give an R44(12) ring motif and extend the structure into a two-dimensional sheet (Fig. 7).
The structures reported here expand the structural database for compounds of this series, formed in the facile reaction of cis-CHDC anhydride with substituted anilines, among which there is a much larger incidence of cyclic imides compared to amide carboxylic acids [currently 8:3, among known examples, which, apart from our previously reported structures, include the imide from the reaction with 5-benzyloxy-2,4-dichloroaniline (Wang et al., 2005) and those from the reactions with 4-bromoaniline and 5-aminosalicylic acid (Smith & Wermuth, 2012b)]. However, there are no apparent structural features which might allow a definitive prediction of the preferred reaction product.