Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019761/cv6159sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019761/cv6159Isup2.hkl |
CCDC reference: 202313
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.106
- Data-to-parameter ratio = 13.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Fumaric acid (3.08 g, 27 mmol) and cyclopentadiene (2.3 ml, 2.3 g, 35 mmol) in 50 ml of dry THF were stirred at room temperature for 48 h. The solvent was removed using rotary evaporator and the residue recrystallized from doubly distilled water, yielding 4.41 g (93%) of (I) [m.p. 458–459 K, cf. 460–461 K (Alder & Stein, 1933)].
All H atoms were refined in isotropic approximation; C—H distances were in the range 0.97 (2)–0.99 (2) Å.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
C9H10O4 | Dx = 1.456 Mg m−3 |
Mr = 182.17 | Melting point: 185–185°C K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.698 (1) Å | Cell parameters from 471 reflections |
b = 5.3906 (3) Å | θ = 10.2–20.0° |
c = 12.153 (1) Å | µ = 0.12 mm−1 |
β = 92.56 (1)° | T = 150 K |
V = 831.04 (11) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.22 × 0.16 mm |
F(000) = 384 |
SMART 1K CCD area-detector diffractometer | 1773 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 29.0°, θmin = 1.6° |
Detector resolution: 8 pixels mm-1 | h = −12→17 |
ω scans | k = −7→6 |
6167 measured reflections | l = −16→14 |
2187 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | All H-atom parameters refined |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0291P)2 + 0.6115P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2187 reflections | Δρmax = 0.32 e Å−3 |
159 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.024 (3) |
C9H10O4 | V = 831.04 (11) Å3 |
Mr = 182.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.698 (1) Å | µ = 0.12 mm−1 |
b = 5.3906 (3) Å | T = 150 K |
c = 12.153 (1) Å | 0.40 × 0.22 × 0.16 mm |
β = 92.56 (1)° |
SMART 1K CCD area-detector diffractometer | 1773 reflections with I > 2σ(I) |
6167 measured reflections | Rint = 0.039 |
2187 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.32 e Å−3 |
2187 reflections | Δρmin = −0.22 e Å−3 |
159 parameters |
Experimental. The data collection nominally covered more than a hemisphere of reciprocal space, by a combination of 4 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (10 s exposure) covering 0.3° in ω. Crystal to detector distance 4.52 cm. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 42 duplicate reflections, which showed a 0.5% fall of intensity. " |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.08686 (10) | 0.7105 (2) | 0.43274 (11) | 0.0334 (3) | |
H01 | 0.032 (2) | 0.704 (5) | 0.481 (2) | 0.071 (8)* | |
O2 | 0.05741 (10) | 0.3044 (2) | 0.41813 (11) | 0.0318 (3) | |
O3 | 0.45985 (9) | 0.2297 (2) | 0.41626 (10) | 0.0273 (3) | |
H03 | 0.5147 (19) | 0.301 (4) | 0.4585 (19) | 0.049 (7)* | |
O4 | 0.38292 (9) | 0.5890 (2) | 0.45826 (10) | 0.0283 (3) | |
C1 | 0.29903 (12) | 0.1375 (3) | 0.24774 (12) | 0.0196 (3) | |
H1 | 0.3371 (14) | −0.021 (3) | 0.2579 (14) | 0.021 (4)* | |
C2 | 0.34528 (13) | 0.3228 (3) | 0.16899 (12) | 0.0240 (3) | |
H2 | 0.4209 (16) | 0.331 (4) | 0.1535 (16) | 0.029 (5)* | |
C3 | 0.26965 (14) | 0.4828 (3) | 0.13903 (12) | 0.0256 (4) | |
H3 | 0.2763 (15) | 0.629 (4) | 0.0938 (17) | 0.033 (5)* | |
C4 | 0.17152 (13) | 0.4121 (3) | 0.19849 (12) | 0.0216 (3) | |
H4 | 0.1028 (15) | 0.477 (3) | 0.1713 (15) | 0.023 (5)* | |
C5 | 0.20037 (11) | 0.4853 (3) | 0.32208 (12) | 0.0172 (3) | |
H5 | 0.2327 (14) | 0.648 (4) | 0.3265 (14) | 0.021 (4)* | |
C6 | 0.28176 (11) | 0.2821 (3) | 0.35717 (11) | 0.0169 (3) | |
H6 | 0.2518 (14) | 0.170 (4) | 0.4107 (15) | 0.024 (5)* | |
C7 | 0.18371 (13) | 0.1273 (3) | 0.20292 (13) | 0.0227 (3) | |
H71 | 0.1353 (15) | 0.045 (3) | 0.2529 (15) | 0.023 (5)* | |
H72 | 0.1763 (16) | 0.050 (4) | 0.1295 (17) | 0.031 (5)* | |
C8 | 0.10782 (11) | 0.4889 (3) | 0.39496 (12) | 0.0183 (3) | |
C9 | 0.37962 (11) | 0.3847 (3) | 0.41454 (12) | 0.0191 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0368 (7) | 0.0199 (6) | 0.0452 (8) | 0.0004 (5) | 0.0207 (6) | −0.0036 (5) |
O2 | 0.0309 (6) | 0.0224 (6) | 0.0437 (7) | −0.0059 (5) | 0.0182 (5) | −0.0065 (5) |
O3 | 0.0187 (5) | 0.0309 (6) | 0.0315 (6) | 0.0052 (5) | −0.0065 (5) | −0.0124 (5) |
O4 | 0.0240 (6) | 0.0252 (6) | 0.0350 (6) | 0.0032 (5) | −0.0080 (5) | −0.0106 (5) |
C1 | 0.0215 (7) | 0.0182 (7) | 0.0190 (7) | −0.0009 (6) | 0.0003 (5) | −0.0033 (5) |
C2 | 0.0284 (8) | 0.0259 (8) | 0.0180 (7) | −0.0045 (7) | 0.0056 (6) | −0.0053 (6) |
C3 | 0.0375 (9) | 0.0243 (8) | 0.0153 (7) | −0.0039 (7) | 0.0047 (6) | −0.0001 (6) |
C4 | 0.0237 (7) | 0.0231 (7) | 0.0175 (7) | 0.0005 (6) | −0.0035 (6) | 0.0012 (6) |
C5 | 0.0173 (7) | 0.0167 (7) | 0.0175 (6) | −0.0008 (5) | 0.0000 (5) | 0.0007 (5) |
C6 | 0.0170 (6) | 0.0182 (6) | 0.0156 (6) | −0.0007 (5) | 0.0006 (5) | 0.0008 (5) |
C7 | 0.0249 (8) | 0.0210 (7) | 0.0216 (7) | −0.0023 (6) | −0.0046 (6) | −0.0024 (6) |
C8 | 0.0170 (6) | 0.0192 (7) | 0.0186 (7) | 0.0013 (5) | −0.0020 (5) | 0.0001 (5) |
C9 | 0.0174 (7) | 0.0241 (7) | 0.0159 (6) | 0.0004 (6) | 0.0012 (5) | −0.0015 (6) |
O1—C8 | 1.3111 (19) | C3—C4 | 1.517 (2) |
O1—H01 | 0.94 (3) | C3—H3 | 0.97 (2) |
O2—C8 | 1.2227 (19) | C4—C7 | 1.544 (2) |
O3—C9 | 1.3173 (18) | C4—C5 | 1.580 (2) |
O3—H03 | 0.93 (2) | C4—H4 | 0.985 (19) |
O4—C9 | 1.2227 (19) | C5—C8 | 1.503 (2) |
C1—C2 | 1.520 (2) | C5—C6 | 1.553 (2) |
C1—C7 | 1.540 (2) | C5—H5 | 0.969 (19) |
C1—C6 | 1.565 (2) | C6—C9 | 1.503 (2) |
C1—H1 | 0.984 (18) | C6—H6 | 0.978 (19) |
C2—C3 | 1.330 (2) | C7—H71 | 0.988 (19) |
C2—H2 | 0.99 (2) | C7—H72 | 0.99 (2) |
C8—O1—H01 | 110.7 (18) | C6—C5—C4 | 102.02 (11) |
C9—O3—H03 | 107.9 (15) | C8—C5—H5 | 107.2 (11) |
C2—C1—C7 | 100.88 (12) | C6—C5—H5 | 110.4 (10) |
C2—C1—C6 | 106.29 (12) | C4—C5—H5 | 111.0 (10) |
C7—C1—C6 | 98.70 (12) | C9—C6—C5 | 113.20 (12) |
C2—C1—H1 | 116.5 (10) | C9—C6—C1 | 115.68 (12) |
C7—C1—H1 | 117.8 (10) | C5—C6—C1 | 103.58 (11) |
C6—C1—H1 | 114.3 (10) | C9—C6—H6 | 104.9 (11) |
C3—C2—C1 | 107.72 (14) | C5—C6—H6 | 110.2 (11) |
C3—C2—H2 | 127.9 (12) | C1—C6—H6 | 109.3 (11) |
C1—C2—H2 | 123.9 (12) | C1—C7—C4 | 93.96 (12) |
C2—C3—C4 | 107.76 (14) | C1—C7—H71 | 114.0 (11) |
C2—C3—H3 | 127.1 (12) | C4—C7—H71 | 113.8 (11) |
C4—C3—H3 | 124.8 (12) | C1—C7—H72 | 112.7 (12) |
C3—C4—C7 | 100.57 (13) | C4—C7—H72 | 112.7 (12) |
C3—C4—C5 | 103.27 (12) | H71—C7—H72 | 109.2 (16) |
C7—C4—C5 | 101.33 (12) | O2—C8—O1 | 122.95 (14) |
C3—C4—H4 | 119.0 (11) | O2—C8—C5 | 123.80 (14) |
C7—C4—H4 | 117.0 (11) | O1—C8—C5 | 113.24 (13) |
C5—C4—H4 | 113.2 (11) | O4—C9—O3 | 123.58 (14) |
C8—C5—C6 | 112.08 (12) | O4—C9—C6 | 123.02 (13) |
C8—C5—C4 | 114.16 (12) | O3—C9—C6 | 113.36 (13) |
O2—C8—C5—C6 | −49.76 (19) | C5—C6—C9—O4 | 20.6 (2) |
C8—C5—C6—C9 | −105.37 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01···O2i | 0.94 (3) | 1.70 (3) | 2.6350 (17) | 173 (3) |
O3—H03···O4ii | 0.93 (2) | 1.72 (2) | 2.6446 (16) | 176 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C9H10O4 |
Mr | 182.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 12.698 (1), 5.3906 (3), 12.153 (1) |
β (°) | 92.56 (1) |
V (Å3) | 831.04 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.40 × 0.22 × 0.16 |
Data collection | |
Diffractometer | SMART 1K CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6167, 2187, 1773 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 1.08 |
No. of reflections | 2187 |
No. of parameters | 159 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.22 |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
O1—C8 | 1.3111 (19) | C2—C3 | 1.330 (2) |
O2—C8 | 1.2227 (19) | C3—C4 | 1.517 (2) |
O3—C9 | 1.3173 (18) | C4—C7 | 1.544 (2) |
O4—C9 | 1.2227 (19) | C4—C5 | 1.580 (2) |
C1—C2 | 1.520 (2) | C5—C8 | 1.503 (2) |
C1—C7 | 1.540 (2) | C5—C6 | 1.553 (2) |
C1—C6 | 1.565 (2) | C6—C9 | 1.503 (2) |
C2—C1—C7 | 100.88 (12) | C8—C5—C6 | 112.08 (12) |
C2—C1—C6 | 106.29 (12) | C8—C5—C4 | 114.16 (12) |
C7—C1—C6 | 98.70 (12) | C6—C5—C4 | 102.02 (11) |
C3—C2—C1 | 107.72 (14) | C9—C6—C5 | 113.20 (12) |
C2—C3—C4 | 107.76 (14) | C9—C6—C1 | 115.68 (12) |
C3—C4—C7 | 100.57 (13) | C5—C6—C1 | 103.58 (11) |
C3—C4—C5 | 103.27 (12) | C1—C7—C4 | 93.96 (12) |
C7—C4—C5 | 101.33 (12) | ||
O2—C8—C5—C6 | −49.76 (19) | C5—C6—C9—O4 | 20.6 (2) |
C8—C5—C6—C9 | −105.37 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H01···O2i | 0.94 (3) | 1.70 (3) | 2.6350 (17) | 173 (3) |
O3—H03···O4ii | 0.93 (2) | 1.72 (2) | 2.6446 (16) | 176 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
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The title compound, (I), alternatively called bicyclo[2.2.1]hept-2-ene-trans-5,6-dicarboxylic acid, was studied as part of a series of small-molecule models of organic polymers influencing the crystallization of inorganic salts, particularly CaCO3 (Megson, 1997; Feast et al., 2002).
Compound (I) was prepared by the Diels–Alder addition of cyclopentadiene to fumaric acid (Diels & Alder, 1928; Alder & Stein, 1933). The asymmetric unit of (I) comprises one molecule. Both carboxyl groups form usual pairs of hydrogen bonds with their inversion equivalents (Fig. 1), linking the molecules into an infinite zigzag chain, the general direction of which is parallel to the crystallographic a axis. trans-Substitution results in a slight twisting of the norbornene skeleton, the C2═C3 and C5—C6 bonds forming an angle of 4.6 (2)°. On the other hand, the C5—C6 bond in (I) is slightly shorter than the corresponding bonds in cis-dicarboxylic acid derivatives, e.g. 1.566 (2)–1.574 (2) Å (Bolte et al., 2000, Batsanov & Hesselink, 2002a,b,c), due to lower steric repulsion between the carboxylic acid groups.