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Two related proton-transfer compounds, namely piperazine-1,4-diium 4-oxo-4H-pyran-2,6-dicarboxyl­ate monohydrate, C4H12N22+·C7H2O62-·H2O or (pipzH2)(cdo)·H2O, (I), and piperazine-1,4-diium bis­(6-carb­oxy-4-oxo-4H-pyran-2-carbox­yl­ate), C4H12N22+·2C7H3O6- or (pipzH2)(cdoH)2, (II), were obtained by the reaction of 4-oxo-4H-pyran-2,6-dicarb­oxy­lic acid (chelidonic acid, cdoH2) and piperazine (pipz). In (I), both carboxyl H atoms of chelidonic acid have been transferred to piperazine to form the piperazine-1,4-diium ion. The structure is a monohydrate. All potential N-H donors are involved in N-H...O hydrogen bonds. The water mol­ecule spans two anions via the 4-oxo group of the pyranose ring and a carboxyl­ate O atom. The hydrogen-bonding motif is essentially two-dimensional. The structure is a pseudomero­hedral twin. In the asymmetric unit of (II), the anion consists of monodeprotonated chelidonic acid, while the piperazine-1,4-diium cation is located on an inversion centre. The single carboxyl H atom is disordered in two respects. Firstly, the disordered H atom is shared equally by both carb­oxy­lic acid groups. Secondly, the H atom is statistically disordered between two positions on either side of a centre of symmetry and is engaged in a very short hydrogen-bonding inter­action; the relevant O...O distances are 2.4549 (11) and 2.4395 (11) Å, and the O-H...O angles are 177 (6) and 177 (5)°, respectively. Further hydrogen bonding of the type N-H...O places the (pipzH2)2+ cations in pockets formed by the chains of (cdoH)- anions. In contrast with (I), the (pipzH2)2+ cations form hydrogen-bonding arrays that are perpendicular to the anions, yielding a three-dimensional hydrogen-bonding motif. The structures of both (I) and (II) also feature [pi]-[pi] stacking inter­actions between aromatic rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111008110/sk3402sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111008110/sk3402Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111008110/sk3402IIsup3.hkl
Contains datablock II

CCDC references: 824044; 824045

Comment top

4-Oxo-4H-pyran-2,6-dicarboxylic acid, also called chelidonic acid, is a weak acid extracted from the perennial herb celandine (Chelidonium majus) as a white crystalline substance (m.p. 538 K). The structures of several metal complexes containing the 4-oxo-4H-pyran-2,6-dicarboxylate dianion, (cdo)2-, illustrate the versatile ability of this ligand to coordinate in a monodentate, bidentate or bridging fashion. Crystal structures include complexes of Ag+, Be2+, Ca2+, Mn2+, Cu2+, Cd2+, Sn2+, Zn2+ and Tb3+ (Manojlovic-Muir et al., 1999; Ng et al., 2000; Olovsson et al., 2001; Fainerman-Melnikova et al., 2006; Yasodha, Govindarajan, Low & Glidewell, 2007; Chen, 2009; Zhang et al., 2009; Zhou et al. 2009). A salt of [Ni(H2O)6](cdo) (Yasodha, Govindarajan, Manivannan & Büyükgüngör , 2007) has also been reported.

As a continuation of our research on the synthesis of proton-transfer compounds by the use of different dicarboxylic acids and numerous amines [for a similar proton-transfer compound of pyridine-2,6-dicarboxylic acid with piperazine, see Aghabozorg, Ghadermazi et al. (2006) and for a proton-transfer compound of piperazine with oxalate, refer to Aghabozorg, Ghadermazi & Sheshmani (2006)], we report here the synthesis and structure determination of two proton-transfer compounds, (I) and (II), obtained from 4-oxo-4H-pyran-2,6-dicarboxylic acid (cdoH2) and piperazine (pipz).

In (pipzH2)(cdo).H2O, (I) (Fig. 1), both H atoms of cdoH2 are transferred to pipz, and the negative charge of (cdo)2- is balanced by the doubly protonated piperazine-1,4-diium ion. All possible N—H donors are engaged in hydrogen bonds to O atoms (see Table 2). The water molecule spans two different anions via a 4-oxo group of the pyranose ring (O4) and a carboxylate O atom (O2). Atom O2 is also hydrogen-bonded to an N—H donor. These hydrogen-bonding interactions form a motif that is two-dimensional (Fig. 3).

In (pipzH2)(cdoH)2, (II) (Fig. 2), the H atom of the (cdoH)- moiety is disordered with respect to exchange between the two carboxylic acid centres, as well as with respect to a centre of inversion. As shown in Fig. 4, the H-atom position is disordered between opposite sides of the centre of inversion with occupancies of 0.5. Thus, there are two assymmetric hydrogen bonds, O2—H2···O2' and O6—H6···O6'' (see Fig. 4 for symmetry codes). The O···O distances and linear geometry correspond to very short hydrogen bonds (Table 4). On average, each (cdoH)- anion acts as an acceptor, using either O2 or O6, and as a donor, using either H2 or H6. A similar but apparently symmetrically hydrogen-bonded species was reported in the structure of [Zn(phen)3]4[H(hpydc)2](NO3)7.26H2O (phen is 1,10-phenanthroline and Hpydc is 5-carboxypyridine-3-carboxylic acid [OK?]; Moghimi et al., 2005). In this case, the unique H atom resides on a centre of symmetry, bridging two carboxylates, and leads to the formation of a discrete anion with an O···O distance of 2.493 (3) Å. In (II), each of the N—H donor groups is hydrogen-bonded to a different CO group of the anion (see Table 4 for details). The N—N vector of the (pipzH2)2+ cation is perpendicular to the chain of anions, yielding a three-dimensional hydrogen-bonding motif, different from the orientation in (I) where the N—N vector is in the plane of the anions.

There are several other notable differences between the two structures. Although both (I) and (II) feature alternating inversion-related ππ stacking interactions, these differ in their details, as viewed from top to bottom in Fig. 6. If the stacking planes are represented by the six-membered C1–C5/O1 ring, in (I), the perpendicular distances between stacking planes alternate between 3.2856 (5) and 3.4334 (5) Å, with slippage distances of 2.46 and 2.18 Å and centroid-to-centroid distances between 4.1071 (7) and 4.0644 (7) Å, respectively. In (II), the corresponding values are 3.2771 (3) and 3.3451 (3) Å for perpendicular distances, 1.35 and 2.04 Å for slippage distances and 3.5449 (4) and 3.9201 (4) Å for centroid-to-centroid distances.

The carbonyl bond lengths support the existence of deprotonated acid molecules. In particular, the C—O distances indicate full delocalization in (I) and are equal within the s.u. values. In (II), the C—O bond bearing the H atoms is ca 0.05 Å longer than the CO bond (see Tables 1 and 3).

The 4-oxo group of the furan ring is expected to be a strong hydrogen-bond acceptor, but is only engaged in a classical hydrogen bond to water in the structure of (I). In the structure of (II), there are no remaining donors for this purpose and it remains only weakly involved in C—H interactions.

Related literature top

For related literature, see: Aghabozorg, Ghadermazi & Sheshmani (2006); Aghabozorg, Ghadermazi, Manteghi & Nakhjavan (2006); Bruker (2010); Chen (2009); Fainerman-Melnikova, Clegg & Codd (2006); Manojlovic-Muir, Muir, Campbell, McKendrick & Robins (1999); Moghimi et al. (2005); Ng et al. (2000); Olovsson et al. (2001); Sheldrick (2006); Yasodha, Govindarajan, Low & Glidewell (2007); Yasodha, Govindarajan, Manivannan & Büyükgüngör (2007); Zhang et al. (2009); Zhou et al. (2009).

Experimental top

For the preparation of compound (I), 4-oxo-4H-pyran-2,6-dicarboxylic acid (2.02 g, 10 mmol, Acros, chelidonic acid) was dissolved in methanol (200 ml) by heating. To this solution was added a solution of piperazine (0.86 ml, 10 mmol) in methanol (10 ml). After cooling, a light-yellow precipitate was collected. The precipitate was redissolved in water and allowed to evaporate slowly, producing crystals suitable for X-ray diffraction [m.p. 467 K (decomposition)]. Elemental analysis, calculated for C18H18N2O12: C 47.54, H3.96, N 6.16%; found: C 47.09, H 3.91, N 6.08%. Spectroscopic analysis: IR (KBr, ν, cm-1): 1339 (s), 1397 (s), 1644 (s), 2446 (br), 2999 (br), 3075 (w), 3236 (s), 3424 (s), 3620 (s); 1H NMR (D2O, δ, p.p.m.): 3.439 (3H, pipH2), 6.939 (2H, cdo); 13C NMR (D2O, δ, p.p.m.): 184.5, 159.1, 115.8, 40.2; UV: 223 nm.

Compound (II) was obtained when we attempted to obtain a nickel(II) complex with (cdo)2-. To a solution of (I) (1 mmol, 0.27 g) in water was added a solution of Ni(NO3)2.6H2O (0.14 g, 0.5 mmol) (molar ratio of 2:1) in water (25 ml). After one week, a light-yellow precipitate was collected. This was redissolved in water and allowed to evaporate slowly, yielding the crystals used for data collection [m.p. 489 K (decomposition)]. Spectroscopic analysis: IR (KBr, ν, cm-1): 1338 (br), 1383 (s), 1459 (w), 1642 (br), 2489 (br), 3075 (w), 3238 (w), 3622 (br).

Refinement top

For (I), the crystal was a three-component rotational twin. Twin integration was carried out using SAINT (Bruker, 2010) and the absorption correction applied using TWINABS (Sheldrick, 2006). The final reflection file used all components and composites. The excess 447 reflections were discounted in the least-squares instruction in order not to underestimate the s.u. values. In addition, 33 reflections were specifically omitted that were likely affected by overlap of twin domains. The twin laws were as follows: Transforms h1.1(1)->h1.2(2) (-0.99994 0.00089 0.00046/ -0.00252 -1.00000 -0.00009/ 0.24863 -0.00003 0.99994); Transforms h1.1(1)->h1.3(3) (-1.00020 -0.00071 -0.04193/ 0.00208 -1.00000 -0.00066/ 0.00948 -0.00126 1.00020); Transforms h1.2(2)->h1.3(3) (0.98972 0.00160 -0.04239/ -0.00474 0.99999 -0.00057/ 0.23919 0.00144 1.00015). Refined twin parameters for the three components are: 0.6036 (10)/0.2707 (10)/0.1257 (11).

For both (I) and (II), H atoms bonded to C and N atoms were refined as riding, with C—H = 0.95–0.99 Å and N—H = 0.92 Å, and Uiso(H) = 1.2Ueq(C,N). For (I), the H atoms of the hydrate molecule were located in a difference map and subsequently refined with restraints of O—H = 0.84 (2) Å and H···H = 1.34 (4) Å, and with Uiso(H) = 1.5Ueq(O). In the structure of (II), there are two short hydrogen bonds between the protonated carboxyl groups and the unprotonated carboxylate groups of an inversion-related molecule of (cdoH)-. Electron-density maps show that these are assymmetric hydrogen bonds and the H atom does not reside on the centre of symmetry. Each of these H atoms (H2 and H6) is at half-occupancy for charge balance and in order to model the disorder. These two H atoms were freely refined.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of (II), with displacement ellipsoids drawn at the 50% probability level. Atoms H2 and H6 are at half-occupancy. [Symmetry code: (i) -x + 2, -y + 2, -z - 1.]
[Figure 3] Fig. 3. A view, approximately down the a axis, of the packing of (I). Hydrogen-bonding interactions are shown with dashed lines.
[Figure 4] Fig. 4. A portion of the structure of (II), depicting the short hydrogen bonds between carboxyl groups of the (cdoH)- group. Atoms H2 and H6 are at half-occupancy and are disordered with respect to centres of symmetry. [Symmetry codes: (') -x + 2, -y + 2, -z; ('') -x + 1, -y + 1, -z + 1.]
[Figure 5] Fig. 5. A view, approximately down the a axis, of the packing of (II). N—H···O hydrogen-bonding interactions are shown as dashed lines.
[Figure 6] Fig. 6. Stacking of the aromatic anions, showing the alternation of inversion-related ππ interactions. [Symmetry codes, for (I): (') -x, -y + 1, -z; ('') -x + 1, -y + 1, -z; for (II): (') -x + 1, -y + 1, -z; ('') -x + 2, -y + 1, -z.]
(I) piperazine-1,4-diium 4-oxo-4H-pyran-2,6-dicarboxylate monohydrate top
Crystal data top
C4H12N22+·C7H2O62·H2OF(000) = 608
Mr = 288.26Dx = 1.531 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9971 reflections
a = 6.8003 (3) Åθ = 2.2–31.5°
b = 11.3961 (5) ŵ = 0.13 mm1
c = 16.1548 (7) ÅT = 87 K
β = 92.968 (2)°Needle, colourless
V = 1250.27 (9) Å30.42 × 0.14 × 0.06 mm
Z = 4
Data collection top
Bruker SMART APEX DUO
diffractometer
4609 independent reflections
Radiation source: fine-focus sealed tube4303 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 8.3 pixels mm-1θmax = 31.5°, θmin = 2.2°
ω scansh = 109
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2006)
k = 1616
Tmin = 0.948, Tmax = 0.993l = 2323
59584 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.052P)2 + 0.3187P]
where P = (Fo2 + 2Fc2)/3
4609 reflections(Δ/σ)max < 0.001
189 parametersΔρmax = 0.52 e Å3
3 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H12N22+·C7H2O62·H2OV = 1250.27 (9) Å3
Mr = 288.26Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.8003 (3) ŵ = 0.13 mm1
b = 11.3961 (5) ÅT = 87 K
c = 16.1548 (7) Å0.42 × 0.14 × 0.06 mm
β = 92.968 (2)°
Data collection top
Bruker SMART APEX DUO
diffractometer
4609 independent reflections
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2006)
4303 reflections with I > 2σ(I)
Tmin = 0.948, Tmax = 0.993Rint = 0.046
59584 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0353 restraints
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.52 e Å3
4609 reflectionsΔρmin = 0.24 e Å3
189 parameters
Special details top

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.

H atoms bonded to C and N were refined as riding on their bonded atoms with U(iso)= 1.2U(eq) of the bonded atom and C—H in the range 0.95 to 0.99 Å, N—H = 0.92 Å. H atoms of the hydrate molecule were located in a difference map and subsequently refined with restraints of O—H = 0.84 (2); H···H = 1.34 (4) Å and U(iso)= 1.5U(eq) of the bonded O atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.22695 (13)0.40793 (6)0.04088 (5)0.00950 (16)
O20.14864 (15)0.20189 (7)0.10764 (5)0.01377 (17)
O30.20665 (15)0.10755 (7)0.01012 (5)0.01377 (17)
O40.27759 (15)0.44996 (7)0.20777 (5)0.01450 (17)
O50.23249 (15)0.71644 (7)0.03859 (5)0.01442 (17)
O60.22009 (15)0.58961 (7)0.14485 (5)0.01470 (18)
O70.22073 (18)0.29837 (9)0.34369 (7)0.0244 (2)
H7A0.249 (4)0.3417 (18)0.3004 (11)0.037*
H7B0.320 (3)0.3116 (19)0.3761 (12)0.037*
C10.22805 (17)0.31350 (9)0.01049 (7)0.00905 (19)
C20.24851 (18)0.32309 (9)0.09277 (7)0.0101 (2)
H20.25120.25410.12570.012*
C30.26651 (18)0.43672 (9)0.13186 (7)0.00998 (19)
C40.26509 (19)0.53455 (9)0.07451 (7)0.0107 (2)
H40.27920.61220.09470.013*
C50.24398 (17)0.51683 (9)0.00712 (7)0.00900 (19)
C60.23172 (18)0.61606 (9)0.07004 (7)0.01027 (19)
C70.19263 (18)0.19811 (9)0.03303 (7)0.0100 (2)
C80.08090 (18)0.44868 (10)0.35334 (7)0.0120 (2)
H8A0.06610.52980.33200.014*
H8B0.01620.43680.39620.014*
C90.04210 (19)0.36210 (10)0.28322 (7)0.0121 (2)
H9A0.04500.28120.30560.015*
H9B0.09040.37640.25690.015*
C100.39414 (19)0.35568 (10)0.25834 (7)0.0117 (2)
H10A0.49270.36490.21580.014*
H10B0.40580.27520.28120.014*
C110.43271 (18)0.44460 (10)0.32688 (7)0.0113 (2)
H11A0.56630.43250.35280.014*
H11B0.42620.52490.30350.014*
N10.28378 (16)0.43184 (8)0.39064 (6)0.01027 (17)
H1A0.30790.48640.43190.012*
H1B0.29410.35840.41410.012*
N20.19266 (16)0.37408 (8)0.22020 (6)0.01145 (18)
H2A0.18440.44770.19690.014*
H2B0.16840.31990.17870.014*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0140 (4)0.0052 (3)0.0094 (3)0.0004 (3)0.0017 (3)0.0002 (2)
O20.0229 (5)0.0094 (3)0.0092 (4)0.0020 (3)0.0028 (3)0.0003 (3)
O30.0233 (5)0.0073 (3)0.0108 (4)0.0001 (3)0.0017 (3)0.0005 (3)
O40.0205 (5)0.0133 (4)0.0098 (4)0.0012 (3)0.0030 (3)0.0016 (3)
O50.0219 (5)0.0067 (3)0.0149 (4)0.0001 (3)0.0035 (3)0.0002 (3)
O60.0230 (5)0.0101 (3)0.0110 (4)0.0001 (3)0.0010 (3)0.0010 (3)
O70.0283 (6)0.0199 (4)0.0258 (5)0.0050 (4)0.0100 (4)0.0078 (4)
C10.0107 (5)0.0061 (4)0.0104 (4)0.0002 (4)0.0013 (4)0.0006 (3)
C20.0122 (5)0.0081 (4)0.0102 (4)0.0000 (4)0.0015 (4)0.0001 (3)
C30.0103 (5)0.0094 (4)0.0103 (5)0.0004 (4)0.0016 (4)0.0006 (3)
C40.0130 (5)0.0076 (4)0.0115 (5)0.0002 (4)0.0009 (4)0.0008 (3)
C50.0095 (5)0.0054 (4)0.0120 (4)0.0006 (4)0.0005 (4)0.0003 (3)
C60.0094 (5)0.0088 (4)0.0126 (5)0.0002 (4)0.0008 (4)0.0018 (3)
C70.0124 (5)0.0082 (4)0.0095 (4)0.0007 (4)0.0003 (4)0.0007 (3)
C80.0129 (5)0.0109 (5)0.0123 (5)0.0015 (4)0.0019 (4)0.0012 (4)
C90.0120 (5)0.0126 (5)0.0117 (5)0.0013 (4)0.0006 (4)0.0003 (4)
C100.0138 (5)0.0099 (4)0.0118 (5)0.0002 (4)0.0032 (4)0.0015 (4)
C110.0126 (5)0.0098 (4)0.0116 (5)0.0007 (4)0.0016 (4)0.0008 (4)
N10.0150 (5)0.0074 (3)0.0084 (4)0.0003 (3)0.0010 (3)0.0001 (3)
N20.0168 (5)0.0091 (4)0.0084 (4)0.0012 (4)0.0003 (3)0.0003 (3)
Geometric parameters (Å, º) top
O1—C11.3592 (12)C8—C91.5150 (16)
O1—C51.3630 (12)C8—H8A0.9900
O2—C71.2575 (13)C8—H8B0.9900
O3—C71.2518 (13)C9—N21.4871 (16)
O4—C31.2417 (14)C9—H9A0.9900
O5—C61.2518 (13)C9—H9B0.9900
O6—C61.2520 (14)C10—N21.4878 (17)
O7—H7A0.870 (15)C10—C111.5137 (16)
O7—H7B0.891 (16)C10—H10A0.9900
C1—C21.3480 (15)C10—H10B0.9900
C1—C71.5163 (15)C11—N11.4886 (15)
C2—C31.4486 (15)C11—H11A0.9900
C2—H20.9500C11—H11B0.9900
C3—C41.4500 (15)N1—H1A0.9200
C4—C51.3490 (15)N1—H1B0.9200
C4—H40.9500N2—H2A0.9200
C5—C61.5257 (15)N2—H2B0.9200
C8—N11.4891 (16)
C1—O1—C5118.25 (8)N2—C9—H9A109.5
H7A—O7—H7B103.6 (19)C8—C9—H9A109.5
C2—C1—O1122.82 (9)N2—C9—H9B109.5
C2—C1—C7123.67 (9)C8—C9—H9B109.5
O1—C1—C7113.42 (9)H9A—C9—H9B108.1
C1—C2—C3121.17 (10)N2—C10—C11109.24 (10)
C1—C2—H2119.4N2—C10—H10A109.8
C3—C2—H2119.4C11—C10—H10A109.8
O4—C3—C2123.36 (10)N2—C10—H10B109.8
O4—C3—C4122.71 (10)C11—C10—H10B109.8
C2—C3—C4113.91 (9)H10A—C10—H10B108.3
C5—C4—C3120.94 (9)N1—C11—C10110.03 (10)
C5—C4—H4119.5N1—C11—H11A109.7
C3—C4—H4119.5C10—C11—H11A109.7
C4—C5—O1122.89 (9)N1—C11—H11B109.7
C4—C5—C6123.55 (9)C10—C11—H11B109.7
O1—C5—C6113.55 (9)H11A—C11—H11B108.2
O5—C6—O6127.85 (10)C11—N1—C8110.90 (9)
O5—C6—C5113.91 (10)C11—N1—H1A109.5
O6—C6—C5118.23 (9)C8—N1—H1A109.5
O3—C7—O2126.21 (10)C11—N1—H1B109.5
O3—C7—C1115.99 (9)C8—N1—H1B109.5
O2—C7—C1117.78 (9)H1A—N1—H1B108.0
N1—C8—C9109.90 (9)C9—N2—C10110.82 (9)
N1—C8—H8A109.7C9—N2—H2A109.5
C9—C8—H8A109.7C10—N2—H2A109.5
N1—C8—H8B109.7C9—N2—H2B109.5
C9—C8—H8B109.7C10—N2—H2B109.5
H8A—C8—H8B108.2H2A—N2—H2B108.1
N2—C9—C8110.65 (10)
C5—O1—C1—C21.14 (17)O1—C5—C6—O5174.96 (10)
C5—O1—C1—C7175.61 (10)C4—C5—C6—O6177.18 (12)
O1—C1—C2—C31.36 (19)O1—C5—C6—O64.27 (15)
C7—C1—C2—C3175.05 (11)C2—C1—C7—O38.39 (18)
C1—C2—C3—O4176.98 (12)O1—C1—C7—O3174.90 (10)
C1—C2—C3—C41.43 (17)C2—C1—C7—O2170.26 (12)
O4—C3—C4—C5177.00 (12)O1—C1—C7—O26.45 (16)
C2—C3—C4—C51.42 (17)N1—C8—C9—N256.35 (12)
C3—C4—C5—O11.36 (18)N2—C10—C11—N158.96 (12)
C3—C4—C5—C6177.06 (11)C10—C11—N1—C858.88 (12)
C1—O1—C5—C41.14 (17)C9—C8—N1—C1157.12 (12)
C1—O1—C5—C6177.42 (10)C8—C9—N2—C1057.94 (12)
C4—C5—C6—O53.59 (17)C11—C10—N2—C958.80 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7A···O40.87 (2)1.94 (2)2.8049 (14)172 (2)
O7—H7B···O2i0.89 (2)2.27 (2)3.0533 (16)147 (2)
N1—H1A···O3ii0.921.882.7796 (12)166
N1—H1B···O5iii0.921.802.7126 (12)170
N2—H2B···O20.921.772.6815 (12)171
N2—H2A···O60.921.842.7519 (13)168
N1—H1A···O2ii0.922.563.1115 (13)119
N2—H2B···O10.922.492.9436 (12)110
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y1/2, z+1/2.
(II) piperazine-1,4-diium bis(6-carboxy-4-oxo-4H-pyran-2-carboxylate) top
Crystal data top
C4H12N22+·2C7H3O6Z = 1
Mr = 454.34F(000) = 236
Triclinic, P1Dx = 1.667 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7880 (3) ÅCell parameters from 5711 reflections
b = 8.0650 (4) Åθ = 2.6–31.5°
c = 8.5675 (4) ŵ = 0.14 mm1
α = 90.377 (2)°T = 87 K
β = 94.110 (2)°Block, colourless
γ = 104.538 (3)°0.36 × 0.34 × 0.22 mm
V = 452.70 (4) Å3
Data collection top
Bruker SMART APEXII
diffractometer
2971 independent reflections
Radiation source: fine-focus sealed tube2806 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.011
Detector resolution: 8.3 pixels mm-1θmax = 31.5°, θmin = 2.4°
ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1111
Tmin = 0.956, Tmax = 0.976l = 1212
7496 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0569P)2 + 0.1111P]
where P = (Fo2 + 2Fc2)/3
2971 reflections(Δ/σ)max = 0.001
153 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H12N22+·2C7H3O6γ = 104.538 (3)°
Mr = 454.34V = 452.70 (4) Å3
Triclinic, P1Z = 1
a = 6.7880 (3) ÅMo Kα radiation
b = 8.0650 (4) ŵ = 0.14 mm1
c = 8.5675 (4) ÅT = 87 K
α = 90.377 (2)°0.36 × 0.34 × 0.22 mm
β = 94.110 (2)°
Data collection top
Bruker SMART APEXII
diffractometer
2971 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2806 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.976Rint = 0.011
7496 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.53 e Å3
2971 reflectionsΔρmin = 0.24 e Å3
153 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.74410 (8)0.54080 (6)0.11379 (6)0.01081 (11)
O20.91492 (9)0.85356 (7)0.03521 (6)0.01557 (12)
H20.977 (8)0.964 (6)0.006 (7)0.056 (11)*0.50
O30.86543 (9)0.78085 (7)0.22173 (6)0.01539 (12)
O40.62761 (9)0.13354 (7)0.19429 (7)0.01478 (12)
O50.58838 (9)0.23123 (7)0.39606 (6)0.01451 (12)
O60.60388 (9)0.51366 (7)0.38810 (7)0.01521 (12)
H60.523 (7)0.502 (6)0.469 (5)0.046 (9)*0.50
C10.77985 (10)0.56304 (9)0.03965 (8)0.01025 (13)
C20.74579 (11)0.43258 (9)0.14573 (8)0.01153 (13)
H2A0.77440.45610.25140.014*
C30.66578 (10)0.25639 (9)0.10008 (8)0.01113 (13)
C40.63217 (11)0.23805 (9)0.06593 (8)0.01156 (13)
H40.58360.12730.10680.014*
C50.66982 (10)0.37790 (9)0.16164 (8)0.01017 (13)
C60.61799 (10)0.36981 (9)0.33080 (8)0.01090 (13)
C70.85932 (10)0.74826 (9)0.08149 (8)0.01129 (13)
N10.81573 (9)1.02489 (8)0.44256 (7)0.01217 (12)
H1A0.79980.95210.35960.015*
H1B0.70911.07660.44810.015*
C80.80952 (11)0.92372 (9)0.59066 (8)0.01256 (13)
H8A0.81681.00020.68110.015*
H8B0.67930.83410.60420.015*
C91.01302 (11)1.15908 (9)0.41500 (8)0.01219 (13)
H9A1.01441.22160.31490.015*
H9B1.02641.24260.50020.015*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0142 (2)0.0079 (2)0.0094 (2)0.00030 (17)0.00286 (17)0.00102 (17)
O20.0219 (3)0.0097 (2)0.0120 (2)0.00178 (19)0.00101 (19)0.00019 (19)
O30.0214 (3)0.0126 (2)0.0111 (2)0.0018 (2)0.00261 (19)0.00244 (18)
O40.0184 (3)0.0117 (2)0.0131 (2)0.00134 (19)0.00252 (19)0.00338 (19)
O50.0189 (3)0.0120 (2)0.0132 (2)0.00420 (19)0.00339 (19)0.00338 (19)
O60.0221 (3)0.0102 (2)0.0131 (2)0.00213 (19)0.00652 (19)0.00104 (18)
C10.0109 (3)0.0097 (3)0.0096 (3)0.0012 (2)0.0017 (2)0.0013 (2)
C20.0129 (3)0.0109 (3)0.0103 (3)0.0017 (2)0.0017 (2)0.0000 (2)
C30.0115 (3)0.0102 (3)0.0113 (3)0.0018 (2)0.0016 (2)0.0005 (2)
C40.0136 (3)0.0091 (3)0.0114 (3)0.0015 (2)0.0023 (2)0.0001 (2)
C50.0114 (3)0.0086 (3)0.0102 (3)0.0013 (2)0.0021 (2)0.0012 (2)
C60.0112 (3)0.0107 (3)0.0100 (3)0.0013 (2)0.0013 (2)0.0002 (2)
C70.0110 (3)0.0099 (3)0.0123 (3)0.0011 (2)0.0016 (2)0.0010 (2)
N10.0123 (3)0.0111 (3)0.0128 (3)0.0020 (2)0.0027 (2)0.0003 (2)
C80.0128 (3)0.0122 (3)0.0118 (3)0.0016 (2)0.0001 (2)0.0012 (2)
C90.0131 (3)0.0097 (3)0.0128 (3)0.0011 (2)0.0014 (2)0.0012 (2)
Geometric parameters (Å, º) top
O1—C11.3588 (8)C4—C51.3502 (9)
O1—C51.3610 (8)C4—H40.9500
O2—C71.2794 (9)C5—C61.5137 (10)
O2—H20.93 (4)N1—C81.4962 (9)
O3—C71.2330 (9)N1—C91.4981 (9)
O4—C31.2373 (8)N1—H1A0.9200
O5—C61.2303 (9)N1—H1B0.9200
O6—C61.2850 (9)C8—C9i1.5151 (10)
O6—H60.91 (4)C8—H8A0.9900
C1—C21.3496 (9)C8—H8B0.9900
C1—C71.5104 (10)C9—C8i1.5151 (10)
C2—C31.4551 (10)C9—H9A0.9900
C2—H2A0.9500C9—H9B0.9900
C3—C41.4592 (10)
C1—O1—C5117.73 (5)O3—C7—O2127.56 (7)
C7—O2—H2113 (3)O3—C7—C1117.31 (6)
C6—O6—H6113 (3)O2—C7—C1115.13 (6)
C2—C1—O1123.44 (6)C8—N1—C9111.47 (5)
C2—C1—C7122.85 (6)C8—N1—H1A109.3
O1—C1—C7113.71 (6)C9—N1—H1A109.3
C1—C2—C3120.76 (6)C8—N1—H1B109.3
C1—C2—H2A119.6C9—N1—H1B109.3
C3—C2—H2A119.6H1A—N1—H1B108.0
O4—C3—C2122.84 (6)N1—C8—C9i110.03 (6)
O4—C3—C4123.14 (6)N1—C8—H8A109.7
C2—C3—C4114.02 (6)C9i—C8—H8A109.7
C5—C4—C3120.26 (6)N1—C8—H8B109.7
C5—C4—H4119.9C9i—C8—H8B109.7
C3—C4—H4119.9H8A—C8—H8B108.2
C4—C5—O1123.76 (6)N1—C9—C8i109.96 (6)
C4—C5—C6122.98 (6)N1—C9—H9A109.7
O1—C5—C6113.10 (6)C8i—C9—H9A109.7
O5—C6—O6127.44 (7)N1—C9—H9B109.7
O5—C6—C5118.82 (6)C8i—C9—H9B109.7
O6—C6—C5113.70 (6)H9A—C9—H9B108.2
C5—O1—C1—C20.09 (10)C1—O1—C5—C6174.80 (6)
C5—O1—C1—C7179.24 (6)C4—C5—C6—O518.57 (11)
O1—C1—C2—C30.31 (11)O1—C5—C6—O5165.82 (6)
C7—C1—C2—C3178.95 (6)C4—C5—C6—O6159.28 (7)
C1—C2—C3—O4178.15 (7)O1—C5—C6—O616.33 (9)
C1—C2—C3—C41.06 (10)C2—C1—C7—O310.25 (11)
O4—C3—C4—C5177.53 (7)O1—C1—C7—O3169.08 (6)
C2—C3—C4—C51.68 (10)C2—C1—C7—O2169.06 (7)
C3—C4—C5—O11.62 (11)O1—C1—C7—O211.62 (9)
C3—C4—C5—C6173.51 (6)C9—N1—C8—C9i57.73 (8)
C1—O1—C5—C40.77 (10)C8—N1—C9—C8i57.69 (8)
Symmetry code: (i) x+2, y+2, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O2ii0.93 (4)1.52 (4)2.4549 (11)177 (6)
O6—H6···O6iii0.91 (4)1.53 (4)2.4395 (11)177 (5)
N1—H1A···O30.921.942.8032 (8)156
N1—H1B···O5iv0.922.092.8419 (8)138
Symmetry codes: (ii) x+2, y+2, z; (iii) x+1, y+1, z+1; (iv) x, y+1, z1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC4H12N22+·C7H2O62·H2OC4H12N22+·2C7H3O6
Mr288.26454.34
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)8787
a, b, c (Å)6.8003 (3), 11.3961 (5), 16.1548 (7)6.7880 (3), 8.0650 (4), 8.5675 (4)
α, β, γ (°)90, 92.968 (2), 9090.377 (2), 94.110 (2), 104.538 (3)
V3)1250.27 (9)452.70 (4)
Z41
Radiation typeMo KαMo Kα
µ (mm1)0.130.14
Crystal size (mm)0.42 × 0.14 × 0.060.36 × 0.34 × 0.22
Data collection
DiffractometerBruker SMART APEX DUO
diffractometer
Bruker SMART APEXII
diffractometer
Absorption correctionMulti-scan
(TWINABS; Sheldrick, 2006)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.948, 0.9930.956, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
59584, 4609, 4303 7496, 2971, 2806
Rint0.0460.011
(sin θ/λ)max1)0.7360.736
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.099, 1.12 0.031, 0.092, 1.06
No. of reflections46092971
No. of parameters189153
No. of restraints30
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.240.53, 0.24

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) for (I) top
O2—C71.2575 (13)O5—C61.2518 (13)
O3—C71.2518 (13)O6—C61.2520 (14)
O4—C31.2417 (14)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O7—H7A···O40.870 (15)1.941 (16)2.8049 (14)172 (2)
O7—H7B···O2i0.891 (16)2.266 (19)3.0533 (16)147.2 (19)
N1—H1A···O3ii0.921.882.7796 (12)166
N1—H1B···O5iii0.921.802.7126 (12)170
N2—H2B···O20.921.772.6815 (12)171
N2—H2A···O60.921.842.7519 (13)168
N1—H1A···O2ii0.922.563.1115 (13)119
N2—H2B···O10.922.492.9436 (12)110
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y1/2, z+1/2.
Selected bond lengths (Å) for (II) top
O2—C71.2794 (9)O5—C61.2303 (9)
O3—C71.2330 (9)O6—C61.2850 (9)
O4—C31.2373 (8)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O2i0.93 (4)1.52 (4)2.4549 (11)177 (6)
O6—H6···O6ii0.91 (4)1.53 (4)2.4395 (11)177 (5)
N1—H1A···O30.921.942.8032 (8)156
N1—H1B···O5iii0.922.092.8419 (8)138
Symmetry codes: (i) x+2, y+2, z; (ii) x+1, y+1, z+1; (iii) x, y+1, z1.
 

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