Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011266/cv6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011266/cv6032Isup2.hkl |
CCDC reference: 170925
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.002 Å
- R factor = 0.029
- wR factor = 0.076
- Data-to-parameter ratio = 25.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.61 From the CIF: _reflns_number_total 4871 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 5405 Completeness (_total/calc) 90.12% Alert C: < 95% complete WEIGH_01 Alert C Extra text has been found in the _refine_ls_weighting_scheme field. This should be in the _refine_ls_weighting_details field. Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.0376P)^2^] wher Weighting scheme identified as calc General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.885 Tmax scaled 0.430 Tmin scaled 0.131 ABSTY_01 Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Data were collected at 183 K using a Siemens SMART CCD diffractometer equipped witha Siemens LT-2 A low temperature device. Slightly more than a hemisphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). Exposure time was 4.5 s per frame. The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 7513 reflections with I > 10σ(I) after integration of all the frames data using SAINT (Siemens, 1995). The data were empirically corrected for absorption and other effects Using SADABS (Sheldrick, 1996) based on the method of Blessing (1995). H atoms (with the exception of those of the water molecule) were refined freely in an isotropic approximation and were constrained to ideal geometry using an appropriate riding model. For hydroxyl groups, the O—H distances (0.84 Å) and C—O—H angles (109.5°) were fixed, the torsion angle was chosen to maximize the electron density.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL.
C12H16NO5+·Br−·H2O | Z = 2 |
Mr = 352.18 | F(000) = 360 |
Triclinic, P1 | Dx = 1.587 Mg m−3 |
a = 8.7253 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9271 (1) Å | Cell parameters from 7513 reflections |
c = 11.5975 (2) Å | θ = 1.9–32.6° |
α = 72.68 (1)° | µ = 2.81 mm−1 |
β = 71.25 (1)° | T = 183 K |
γ = 61.01 (1)° | Block, colourless |
V = 737.12 (2) Å3 | 1.00 × 0.40 × 0.30 mm |
Siemens SMART CCD diffractometer | 4871 independent reflections |
Radiation source: fine-focus sealed tube | 4148 reflections with F2 > 2σ(F2) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 32.6°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; sheldrick, 1996) ? | h = −12→13 |
Tmin = 0.148, Tmax = 0.486 | k = −13→13 |
9194 measured reflections | l = −16→17 |
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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | Calculated w = 1/[σ2(Fo2) + (0.0376P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
4871 reflections | Δρmax = 0.69 e Å−3 |
190 parameters | Δρmin = −0.66 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (15) |
C12H16NO5+·Br−·H2O | γ = 61.01 (1)° |
Mr = 352.18 | V = 737.12 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7253 (1) Å | Mo Kα radiation |
b = 8.9271 (1) Å | µ = 2.81 mm−1 |
c = 11.5975 (2) Å | T = 183 K |
α = 72.68 (1)° | 1.00 × 0.40 × 0.30 mm |
β = 71.25 (1)° |
Siemens SMART CCD diffractometer | 4871 independent reflections |
Absorption correction: multi-scan (SADABS; sheldrick, 1996) ? | 4148 reflections with F2 > 2σ(F2) |
Tmin = 0.148, Tmax = 0.486 | Rint = 0.030 |
9194 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.69 e Å−3 |
4871 reflections | Δρmin = −0.66 e Å−3 |
190 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 | ||
Br1 | 0.38680 (2) | 0.17130 (2) | 0.13559 (1) | 0.02615 (6) | |
C1 | 0.54347 (17) | −0.33364 (16) | 0.29389 (12) | 0.0150 (2) | |
H1 | 0.4623 | −0.2627 | 0.3603 | 0.018* | |
C2 | 0.59940 (18) | −0.52570 (18) | 0.35313 (13) | 0.0190 (3) | |
C3 | 0.4992 (2) | −0.58978 (19) | 0.31465 (15) | 0.0241 (3) | |
H3 | 0.5047 | −0.7034 | 0.3417 | 0.029* | |
C4 | 0.3996 (2) | −0.46512 (19) | 0.23639 (15) | 0.0230 (3) | |
H4 | 0.3190 | −0.4770 | 0.2047 | 0.028* | |
C5 | 0.42961 (17) | −0.30275 (17) | 0.20399 (13) | 0.0160 (2) | |
H5 | 0.5016 | −0.2951 | 0.1175 | 0.019* | |
N6 | 0.25759 (15) | −0.13718 (15) | 0.21388 (11) | 0.0172 (2) | |
H6 | 0.2907 | −0.0474 | 0.1988 | 0.021* | |
C7 | 0.1500 (2) | −0.0925 (2) | 0.11873 (16) | 0.0276 (3) | |
H7A | 0.1583 | −0.1993 | 0.1025 | 0.033* | |
H7B | 0.1945 | −0.0292 | 0.0401 | 0.033* | |
C8 | −0.0432 (2) | 0.0222 (2) | 0.17515 (17) | 0.0285 (3) | |
H8A | −0.1238 | −0.0293 | 0.1804 | 0.034* | |
H8B | −0.0847 | 0.1396 | 0.1242 | 0.034* | |
C9 | −0.0423 (2) | 0.0323 (2) | 0.30498 (17) | 0.0284 (3) | |
H9A | −0.0377 | 0.1411 | 0.3046 | 0.034* | |
H9B | −0.1506 | 0.0274 | 0.3652 | 0.034* | |
C10 | 0.12680 (19) | −0.1262 (2) | 0.33681 (14) | 0.0217 (3) | |
H10A | 0.1695 | −0.1085 | 0.3989 | 0.026* | |
H10B | 0.1061 | −0.2323 | 0.3684 | 0.026* | |
C11 | 0.70240 (17) | −0.28489 (17) | 0.23756 (13) | 0.0159 (2) | |
H11 | 0.6532 | −0.1594 | 0.1987 | 0.019* | |
C12 | 0.79378 (19) | −0.30490 (19) | 0.33757 (14) | 0.0196 (3) | |
O13 | 0.68059 (16) | −0.20669 (17) | 0.42144 (11) | 0.0293 (3) | |
H13 | 0.7337 | −0.2215 | 0.4756 | 0.035* | |
O14 | 0.95280 (15) | −0.39638 (16) | 0.33676 (12) | 0.0278 (2) | |
C15 | 0.83878 (18) | −0.38806 (18) | 0.13678 (13) | 0.0172 (2) | |
O16 | 0.95163 (15) | −0.32168 (15) | 0.06895 (11) | 0.0250 (2) | |
H16 | 1.0213 | −0.3808 | 0.0132 | 0.030* | |
O17 | 0.83796 (14) | −0.51700 (13) | 0.12038 (10) | 0.0214 (2) | |
O18 | 0.70492 (15) | −0.60505 (14) | 0.42194 (11) | 0.0258 (2) | |
O1W | 0.84082 (18) | −0.23914 (18) | 0.58545 (12) | 0.0303 (3) | |
H1W | 0.782 (3) | −0.233 (3) | 0.656 (2) | 0.036* | |
H2W | 0.909 (3) | −0.342 (3) | 0.600 (2) | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.03659 (10) | 0.02440 (8) | 0.02059 (9) | −0.01819 (7) | −0.00057 (6) | −0.00507 (5) |
C1 | 0.0148 (5) | 0.0181 (5) | 0.0133 (6) | −0.0087 (4) | −0.0007 (4) | −0.0039 (4) |
C2 | 0.0180 (6) | 0.0195 (6) | 0.0150 (6) | −0.0082 (5) | 0.0028 (5) | −0.0035 (5) |
C3 | 0.0240 (7) | 0.0203 (6) | 0.0288 (8) | −0.0131 (5) | −0.0001 (6) | −0.0049 (5) |
C4 | 0.0232 (7) | 0.0238 (6) | 0.0284 (8) | −0.0133 (5) | −0.0028 (6) | −0.0103 (6) |
C5 | 0.0169 (6) | 0.0193 (5) | 0.0141 (6) | −0.0095 (5) | −0.0014 (5) | −0.0048 (5) |
N6 | 0.0183 (5) | 0.0200 (5) | 0.0171 (6) | −0.0103 (4) | −0.0052 (4) | −0.0027 (4) |
C7 | 0.0276 (8) | 0.0352 (8) | 0.0243 (8) | −0.0125 (6) | −0.0135 (6) | −0.0040 (6) |
C8 | 0.0252 (7) | 0.0304 (7) | 0.0308 (9) | −0.0134 (6) | −0.0133 (6) | 0.0044 (6) |
C9 | 0.0193 (7) | 0.0268 (7) | 0.0378 (10) | −0.0048 (6) | −0.0084 (6) | −0.0101 (7) |
C10 | 0.0174 (6) | 0.0267 (6) | 0.0187 (7) | −0.0067 (5) | −0.0026 (5) | −0.0068 (5) |
C11 | 0.0157 (6) | 0.0194 (6) | 0.0145 (6) | −0.0091 (5) | −0.0015 (5) | −0.0047 (5) |
C12 | 0.0212 (6) | 0.0258 (6) | 0.0168 (7) | −0.0141 (5) | −0.0023 (5) | −0.0051 (5) |
O13 | 0.0260 (6) | 0.0451 (7) | 0.0225 (6) | −0.0141 (5) | −0.0027 (4) | −0.0181 (5) |
O14 | 0.0210 (5) | 0.0369 (6) | 0.0282 (6) | −0.0113 (5) | −0.0076 (4) | −0.0085 (5) |
C15 | 0.0172 (6) | 0.0213 (6) | 0.0144 (6) | −0.0106 (5) | −0.0011 (5) | −0.0034 (5) |
O16 | 0.0272 (5) | 0.0322 (5) | 0.0219 (6) | −0.0218 (5) | 0.0092 (4) | −0.0128 (4) |
O17 | 0.0230 (5) | 0.0240 (5) | 0.0201 (5) | −0.0145 (4) | 0.0037 (4) | −0.0087 (4) |
O18 | 0.0239 (5) | 0.0251 (5) | 0.0201 (6) | −0.0059 (4) | −0.0053 (4) | −0.0003 (4) |
O1W | 0.0341 (6) | 0.0395 (7) | 0.0202 (6) | −0.0158 (5) | −0.0054 (5) | −0.0094 (5) |
C1—C2 | 1.5339 (19) | C8—H8A | 0.9900 |
C1—C11 | 1.5403 (18) | C8—H8B | 0.9900 |
C1—C5 | 1.543 (2) | C9—C10 | 1.527 (2) |
C1—H1 | 1.0000 | C9—H9A | 0.9900 |
C2—O18 | 1.2205 (19) | C9—H9B | 0.9900 |
C2—C3 | 1.476 (2) | C10—H10A | 0.9900 |
C3—C4 | 1.336 (2) | C10—H10B | 0.9900 |
C3—H3 | 0.9500 | C11—C15 | 1.5213 (19) |
C4—C5 | 1.5138 (19) | C11—C12 | 1.532 (2) |
C4—H4 | 0.9500 | C11—H11 | 1.0000 |
C5—N6 | 1.5134 (17) | C12—O14 | 1.2206 (18) |
C5—H5 | 1.0000 | C12—O13 | 1.3195 (18) |
N6—C10 | 1.5077 (19) | O13—H13 | 0.8400 |
N6—C7 | 1.516 (2) | C15—O17 | 1.2250 (17) |
N6—H6 | 0.9300 | C15—O16 | 1.3151 (16) |
C7—C8 | 1.528 (2) | O16—H16 | 0.8400 |
C7—H7A | 0.9900 | O1W—H1W | 0.82 (3) |
C7—H7B | 0.9900 | O1W—H2W | 0.82 (2) |
C8—C9 | 1.538 (3) | ||
C2—C1—C11 | 113.48 (11) | C7—C8—C9 | 106.25 (13) |
C2—C1—C5 | 104.13 (11) | C7—C8—H8A | 110.5 |
C11—C1—C5 | 116.11 (11) | C9—C8—H8A | 110.5 |
C2—C1—H1 | 107.6 | C7—C8—H8B | 110.5 |
C11—C1—H1 | 107.6 | C9—C8—H8B | 110.5 |
C5—C1—H1 | 107.6 | H8A—C8—H8B | 108.7 |
O18—C2—C3 | 128.00 (13) | C10—C9—C8 | 104.55 (13) |
O18—C2—C1 | 124.33 (13) | C10—C9—H9A | 110.8 |
C3—C2—C1 | 107.65 (12) | C8—C9—H9A | 110.8 |
C4—C3—C2 | 110.30 (13) | C10—C9—H9B | 110.8 |
C4—C3—H3 | 124.8 | C8—C9—H9B | 110.8 |
C2—C3—H3 | 124.9 | H9A—C9—H9B | 108.9 |
C3—C4—C5 | 112.36 (13) | N6—C10—C9 | 102.35 (13) |
C3—C4—H4 | 123.8 | N6—C10—H10A | 111.3 |
C5—C4—H4 | 123.8 | C9—C10—H10A | 111.3 |
N6—C5—C4 | 113.52 (11) | N6—C10—H10B | 111.3 |
N6—C5—C1 | 112.25 (11) | C9—C10—H10B | 111.3 |
C4—C5—C1 | 104.39 (11) | H10A—C10—H10B | 109.2 |
N6—C5—H5 | 108.8 | C15—C11—C12 | 110.42 (11) |
C4—C5—H5 | 108.8 | C15—C11—C1 | 112.63 (11) |
C1—C5—H5 | 108.8 | C12—C11—C1 | 111.20 (11) |
C10—N6—C5 | 116.92 (11) | C15—C11—H11 | 107.4 |
C10—N6—C7 | 105.64 (11) | C12—C11—H11 | 107.4 |
C5—N6—C7 | 114.04 (11) | C1—C11—H11 | 107.4 |
C10—N6—H6 | 106.5 | O14—C12—O13 | 124.70 (14) |
C5—N6—H6 | 106.5 | O14—C12—C11 | 123.76 (13) |
C7—N6—H6 | 106.5 | O13—C12—C11 | 111.50 (12) |
N6—C7—C8 | 105.48 (13) | C12—O13—H13 | 109.5 |
N6—C7—H7A | 110.6 | O17—C15—O16 | 124.54 (13) |
C8—C7—H7A | 110.6 | O17—C15—C11 | 122.31 (12) |
N6—C7—H7B | 110.6 | O16—C15—C11 | 113.14 (11) |
C8—C7—H7B | 110.6 | C15—O16—H16 | 109.5 |
H7A—C7—H7B | 108.8 | H1W—O1W—H2W | 95 (2) |
C11—C1—C2—O18 | 45.89 (18) | C5—N6—C7—C8 | 156.04 (12) |
C5—C1—C2—O18 | 173.05 (13) | N6—C7—C8—C9 | −2.87 (17) |
C11—C1—C2—C3 | −135.86 (12) | C7—C8—C9—C10 | −21.07 (17) |
C5—C1—C2—C3 | −8.69 (13) | C5—N6—C10—C9 | −167.28 (12) |
O18—C2—C3—C4 | −178.70 (15) | C7—N6—C10—C9 | −39.21 (15) |
C1—C2—C3—C4 | 3.13 (16) | C8—C9—C10—N6 | 36.80 (16) |
C2—C3—C4—C5 | 4.17 (18) | C2—C1—C11—C15 | 59.74 (16) |
C3—C4—C5—N6 | −132.14 (14) | C5—C1—C11—C15 | −60.88 (15) |
C3—C4—C5—C1 | −9.59 (16) | C2—C1—C11—C12 | −64.80 (14) |
C2—C1—C5—N6 | 133.95 (11) | C5—C1—C11—C12 | 174.58 (11) |
C11—C1—C5—N6 | −100.53 (13) | C15—C11—C12—O14 | −2.35 (19) |
C2—C1—C5—C4 | 10.57 (13) | C1—C11—C12—O14 | 123.43 (15) |
C11—C1—C5—C4 | 136.09 (11) | C15—C11—C12—O13 | 175.49 (12) |
C4—C5—N6—C10 | 56.41 (16) | C1—C11—C12—O13 | −58.73 (15) |
C1—C5—N6—C10 | −61.68 (15) | C12—C11—C15—O17 | 111.88 (15) |
C4—C5—N6—C7 | −67.48 (16) | C1—C11—C15—O17 | −13.09 (19) |
C1—C5—N6—C7 | 174.42 (12) | C12—C11—C15—O16 | −69.82 (16) |
C10—N6—C7—C8 | 26.26 (16) | C1—C11—C15—O16 | 165.21 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O13 | 1.00 | 2.53 | 2.8905 (18) | 101 |
C5—H5···O17 | 1.00 | 2.63 | 3.0936 (17) | 108 |
N6—H6···Br1 | 0.93 | 2.32 | 3.2468 (12) | 173 |
C11—H11···Br1 | 1.00 | 2.79 | 3.7311 (14) | 156 |
O13—H13···O1W | 0.84 | 1.74 | 2.5779 (18) | 177 |
O16—H16···O17i | 0.84 | 1.81 | 2.6446 (15) | 173 |
O1W—H1W···Br1ii | 0.82 (3) | 2.45 (3) | 3.2630 (14) | 170 (2) |
O1W—H2W···O14iii | 0.82 (2) | 2.06 (2) | 2.8741 (19) | 171 (2) |
C10—H10B···O14iv | 0.99 | 2.57 | 3.417 (2) | 144 |
C8—H8B···O16v | 0.99 | 2.64 | 3.451 (2) | 139 |
C5—H5···Br1v | 1.00 | 2.84 | 3.8034 (14) | 162 |
Symmetry codes: (i) −x+2, −y−1, −z; (ii) −x+1, −y, −z+1; (iii) −x+2, −y−1, −z+1; (iv) x−1, y, z; (v) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H16NO5+·Br−·H2O |
Mr | 352.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 8.7253 (1), 8.9271 (1), 11.5975 (2) |
α, β, γ (°) | 72.68 (1), 71.25 (1), 61.01 (1) |
V (Å3) | 737.12 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.81 |
Crystal size (mm) | 1.00 × 0.40 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.148, 0.486 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 9194, 4871, 4148 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.758 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.076, 0.97 |
No. of reflections | 4871 |
No. of parameters | 190 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.69, −0.66 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 1996), SHELXTL (Bruker, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXTL.
C1—C2 | 1.5339 (19) | C7—C8 | 1.528 (2) |
C1—C11 | 1.5403 (18) | C8—C9 | 1.538 (3) |
C1—C5 | 1.543 (2) | C9—C10 | 1.527 (2) |
C2—O18 | 1.2205 (19) | C11—C15 | 1.5213 (19) |
C2—C3 | 1.476 (2) | C11—C12 | 1.532 (2) |
C3—C4 | 1.336 (2) | C12—O14 | 1.2206 (18) |
C4—C5 | 1.5138 (19) | C12—O13 | 1.3195 (18) |
C5—N6 | 1.5134 (17) | C15—O17 | 1.2250 (17) |
N6—C10 | 1.5077 (19) | C15—O16 | 1.3151 (16) |
N6—C7 | 1.516 (2) | ||
C2—C1—C5 | 104.13 (11) | C12—C11—C1 | 111.20 (11) |
C15—C11—C12 | 110.42 (11) | O14—C12—O13 | 124.70 (14) |
C15—C11—C1 | 112.63 (11) | O17—C15—O16 | 124.54 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O13 | 1.00 | 2.53 | 2.8905 (18) | 101.1 |
C5—H5···O17 | 1.00 | 2.63 | 3.0936 (17) | 108.2 |
N6—H6···Br1 | 0.93 | 2.32 | 3.2468 (12) | 172.8 |
C11—H11···Br1 | 1.00 | 2.79 | 3.7311 (14) | 156.2 |
O13—H13···O1W | 0.84 | 1.74 | 2.5779 (18) | 176.6 |
O16—H16···O17i | 0.84 | 1.81 | 2.6446 (15) | 172.9 |
O1W—H1W···Br1ii | 0.82 (3) | 2.45 (3) | 3.2630 (14) | 170 (2) |
O1W—H2W···O14iii | 0.82 (2) | 2.06 (2) | 2.8741 (19) | 171 (2) |
C10—H10B···O14iv | 0.99 | 2.57 | 3.417 (2) | 143.5 |
C8—H8B···O16v | 0.99 | 2.64 | 3.451 (2) | 138.7 |
C5—H5···Br1v | 1.00 | 2.84 | 3.8034 (14) | 162.1 |
Symmetry codes: (i) −x+2, −y−1, −z; (ii) −x+1, −y, −z+1; (iii) −x+2, −y−1, −z+1; (iv) x−1, y, z; (v) −x+1, −y, −z. |
In a continuation of our studies on the synthesis of substituted cyclopentene obtained from activated 2-substituted furan derivatives, we have reported the synthesis of (5-aminosubstituted-cyclopenten-3-en-1-yl)-4H-1,3-dioxin-4-ones (Šafář et al., 2000). It has been found, that the results of the reaction of 6-hydroxy-2,2-dimethyl-5-[2-oxo-5-(pyrrolidin-1-yl)cyclopent-3-en-1-yl]- 4H-1,3-dioxin-4-one, (I), with hydrobromic acid are strongly dependent on the nature of the solvent. While reaction of (I) with hydrobromic acid in methanol resulted in the formation of cyclopentenone hydrobromide (II), treatment of (I) with 10% hydrobromic acid afforded substituted malonic acid hydrobromide (III), having the molecular formula C12H16BrNO5 and a molecular ion (M+. - 80) having m/z = 253 in the mass spectrum.
Spectral data (1H and 13C NMR) were not sufficient to determine the position of pyrrolidine ring and malonic acid on the cyclopentene ring, so an X-ray diffraction study of (III) was undertaken.
The crystal structure of (III) consists of a 2-[2-oxo-5-(pyrrolidin-1-yl)cyclopent-3-en-1-yl]malonic acid cation and a Br- anion, and is stabilized by the presence of a water molecule (Fig. 1). The positions of the bulky substituents are trans and the cation consists of a cyclopentene ring substituted in the 5-position by a pyrrolidine ring and in the 1-position by a malonic acid moiety. The pyrrolidine ring adopts a half-chair conformation, and the cyclopentene ring is nearly planar (χ2 = 5.99 at the 95% probability level) with the main displacement for C1 and C5 atoms of 0.056 (1) and -0.062 (2) Å, respectively. The distance C3—C4 of 1.336 (2) Å clearly indicates double-bond character, while all other C—C and C—N bonds are single. There is also apparent difference for C═O bonds for C2—O18, C12—O14 and C15—O17 of 1.221 (2), 1.221 (2) and 1.225 (2) Å, respectively, and C—O bonds C12—O13 and C15—O16 of 1.320 (2) and 1.315 (2) Å, respectively. The system of hydrogen bonds (see Fig. 2 and Table 2) between the cation, the Br- anion and the water molecule form a three-dimmensional framework and stabilize the crystal structure.