1-[2-(Di­carboxy­methyl)-3-oxo­cyclo­pent-4-en-1-yl]­pyrrolidin-1-ium bromide hydrate

Crystallization of 6-hydroxy-2,2-di­methyl-5-[2-oxo-5-(pyrrolidin-1-yl)­cyclo­pent-3-en-1-yl]-4H-1,3-dioxin-4-one from aqueous hydro­bromic acid gave the title compound, C₁₂H₁₆BrNO₅·H₂O. The crystal structure is stabilized by a three-dimensional network of hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 183 K
• Mean [sigma](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

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S1. Comment

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.

S2. Experimental

See above for synthesis details.

S3. Refinement

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.

Computing details

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.

Figures

	Fig. 1. The numbering scheme of (III). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. The system of hydrogen bonds and short contacts in (III). The symmetry code used is the same as in Table 2.

(I)

Crystal data

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) Å^3	1.00 × 0.40 × 0.30 mm

Data collection

Siemens SMART CCD diffractometer	4871 independent reflections
Radiation source: fine-focus sealed tube	4148 reflections with F^2 > 2σ(F^2)
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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	Calculated w = 1/[σ^2(Fo^2) + (0.0376P)^2] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0060 (15)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O17^i	0.84	1.81	2.6446 (15)	173
O1W—H1W···Br1^ii	0.82 (3)	2.45 (3)	3.2630 (14)	170 (2)
O1W—H2W···O14^iii	0.82 (2)	2.06 (2)	2.8741 (19)	171 (2)
C10—H10B···O14^iv	0.99	2.57	3.417 (2)	144
C8—H8B···O16^v	0.99	2.64	3.451 (2)	139
C5—H5···Br1^v	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.