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The structures of the 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with 4-nitro­phthalic acid [4-carbamoylpiperidinium 2-carb­oxy-4-nitro­benzoate, C6H13N2O8+·C8H4O6-, (I)], 4,5-dichloro­phthalic acid [4-carbamoylpiperidinium 2-carb­oxy-4,5-dichloro­benzo­ate, C6H13N2O8+·C8H3Cl2O4-, (II)] and 5-nitro­isophthalic acid [4-carbamoylpiperidinium 3-carb­oxy-5-nitro­benzoate, C6H13N2O8+·C8H4O6-, (III)], as well as the 2:1 compound with terephthalic acid [bis­(4-carbamoylpiperidinium) benzene-1,2-dicarboxyl­ate dihydrate, 2C6H13N2O8+·C8H4O42-·2H2O, (IV)], have been determined at 200 K. All salts form hydrogen-bonded structures, viz. one-dimensional in (II) and three-dimensional in (I), (III) and (IV). In (I) and (III), the centrosymmetric R22(8) cyclic amide-amide association is found, while in (IV) several different types of water-bridged cyclic associations are present [graph sets R42(8), R43(10), R44(12), R33(18) and R64(22)]. The one-dimensional structure of (I) features the common `planar' hydrogen 4,5-dichloro­phthalate anion, together with enlarged cyclic R33(13) and R43(17) associations. In the structures of (I) and (III), the presence of head-to-tail hydrogen phthalate chain substructures is found. In (IV), head-to-tail primary cation-anion associations are extended longitudinally into chains through the water-bridged cation associations, and laterally by piperidinium-carboxylate N-H...O and water-carboxylate O-H...O hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of cation-anion association with this cation is also shown in the asymmetric three-centre piperidinium-carboxylate N-H...O,O' inter­action in the first-reported structure of a 2:1 isonipecotamide-carboxyl­ate salt.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111020518/su3064sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IVsup5.hkl
Contains datablock IV

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064Isup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064IIsup7.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064IIIsup8.cml
Supplementary material

CCDC references: 838165; 838166; 838167; 838168

Comment top

Our project of investigating the hydrogen-bonding modes in salts of the Lewis base 4-piperidinecarboxamide (isonipecotamide; INIPA) with carboxylic acids has provided a considerable number of structures, the majority being anhydrous 1:1 salts with aromatic acids (Smith & Wermuth, 2010d,f, 2011a). Solvated examples are the nicotinate (a partial hydrate; Smith & Wermuth, 2011c), the acetate (a monohydrate; Smith & Wermuth, 2010e) and the 6-carboxypyridine-2-carboxylate (a methanol monosolvate; Smith & Wermuth, 2011c), while with o-phthalic acid a 1:1 hydrogen phthalate–phthalic acid salt adduct is found (Smith & Wermuth, 2011b). Anhydrous picrates are also known (Smith & Wermuth, 2010c), together with a 2:1 salt with bipyridine-4,4'-disulfonate (Smith et al., 2010). In the light of the unusual formation of a 1:1:1 cation–anion–phthalic acid adduct from a 1:1 stoichiometric reaction (Smith & Wermuth, 2011b), our further aim was to investigate the nature of the products formed from similar reactions of INIPA with a series of aromatic dicarboxylic acids in various alcoholic and aqueous alcoholic solutions. Examples included 4-nitrophthalic acid (NPHA), 4,5-dichlorophthalic acid (DCPA), 5-nitroisophthalic acid (NIPA) and terephthalic acid (TPA), which provided good crystalline products. The 1:1 anhydrous salts of 4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate, (I), 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate, (II), and 4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, (III), were obtained, and the 2:1 hydrated salt of the terephthalate, bis(4-carbamoylpiperidinium) benzene-1,2-dicarboxylate dihydrate, (IV), was also identified. The structures of (I)–(IV) are described here.

With the 1:1 salts, (I)–(III) (Figs. 1–4), proton transfer has occurred to the hetero N atom of the piperidine ring, while with the terephthalate salt, (IV), it involves a two-proton transfer with the formation of a dianion. The resulting piperidinium group of the anion in each salt, together with the hydrogen donor and acceptor p-related substituent amide group, are subsequently involved in hydrogen-bonding interactions. These result in supramolecular structures, which are three-dimensional in (I), (III) and (IV) and one-dimensional in (II) (Figs. 5–8). A feature of the hydrogen-bonding in (I) and (III) is the presence of the centrosymmetric cyclic homomolecular N—H···O hydrogen-bonded amide–amide motif (Allen et al., 1998), with graph set R22(8) (Etter et al., 1990; Bernstein et al., 1995). This motif has now been found in 11 of the 24 known structures of INIPA proton-transfer salts, including the present examples.

In the structure of the 1:1 INIPA salt with 4-nitrophthalic acid, (I), the 1-carboxy rather than the 2-carboxy group is deprotonated (Fig. 1), giving a primary piperidinium N—H···Ocarboxyl ion-pair interaction. The hydrogen phthalate anions form head-to-tail hydrogen-bonded chain substructures featuring short carboxylic acid O—H···Ocarboxyl hydrogen bonds [graph set C(7); Fig. 5]. These substructures are common among hydrogen phthalate salt structures (Glidewell et al., 2005; Smith & Wermuth, 2010b). The peripherally bound INIPA anions give structure extension across (011) through classic centrosymmetric R22(8) amide–amide N—H···O hydrogen-bonded dimer associations. In addition, amide N—H···Onitro and piperidinium N—H···Ocarboxyl associations (Table 1) result in a three-dimensional structure. In the nitrophthalate anion, the carboxylate group is rotated significantly out of the benzene plane [torsion angle C2—C1—C11—O12 = -76.7 (2)°], while the carboxylic acid and nitro groups are essentially coplanar with the benzene plane [torsion angles C1—C2—C21—O22 = 169.25 (16)° and C3—C4—N4—O42 = -174.03 (18)°, respectively].

In the structure of the 1:1 INIPA salt with 4,5-dichlorophthalic acid, (II) (Fig. 2), one of the two primary piperidinium cation–anion associations also involves a secondary longer three-centre interaction [N1A···O12 = 3.044 (4) Å and N1A—H11A···O12 = 118 (3)° Please check - 3.042 (4) and 117 (3) in CIF data tables], which is probably an artefact of the overall cyclic hydrogen-bonding motif. This association [graph set R43(17)] involves piperidinium N—H···Ocarboxy, amide N—H···Ocarboxy and amide N—H···Oamide hydrogen bonds from two INIPA cations and one DCPA anion, and is closed by the intramolecular carboxylic acid O—H···Ocarboxyl hydrogen bond (Fig. 6). A second cyclic association [graph set R33(13)] involves one piperidinium and two amide–carboxyl hydrogen bonds (Table 2), and the two motifs link the DCPA anions peripherally into head-to-head N—H···O amide-linked cation chain substructures. This results in one-dimensional ribbon structures which extend along the b cell direction. In the crystal structures of DCPA salts with Lewis bases, this low dimensionality in the hydrogen-bonded structures is commonly associated with the `planar' DCPA monoanion, which features the cyclic intramolecular carboxylic acid O—H···Ocarboxyl hydrogen-bonding association [graph set S(7); Smith et al., 2010]. The short hydrogen bond [2.393 (3) Å] in the `planar' DCPA anion in (II) results in a C2—C1—C11—O11 torsion angle of 174.1 (3)°, while another feature of this conformation is elongation of the C1—C11 and C2—C21 bonds [1.522 (4) and 1.534 (4) Å, respectively] and distortion of the external bond angles at C1 and C2 [128.8 (2) and 128.1 (2)°, respectively; Smith et al., 2010].

In the structure of the hydrogen 5-nitroisphthalate salt, (III) (Fig. 3), the primary cation–anion interaction has a second longer N—H···Ocarboxyl contact [N1A···O12 = 3.0366 (17) Å and N1A—H12A···O12 = 118.1 (7)° Please check - 3.0366 (19) and 118.1 (17) in CIF data tables], similar to that in (II). The cation–anion associations are also similar in some respects to those of (I). The hydrogen isophthalate anions give zig-zag head-to-tail hydrogen-bonded chain substructures through carboxylic acid O—H···Ocarboxyl hydrogen bonds (Table 3) but these are classified as graph set C(8), rather than C(7) as in (I). In addition, the centrosymmetric R22(8) hydrogen-bonded INPA amide–amide dimers give peripheral structure extension through piperidinium N—H···Ocarboxyl hydrogen bonds which involve two anions, enclosing cyclic R33(10) rings (Fig. 7). The three-dimensional framework structure is generated through amide N—H···Ocarboxyl hydrogen-bonding associations. The nitro O atoms are unassociated, except for weak intermolecular cation C—H···O associations [C2A···O52ii = 3.308 (2) Å and C2A—H22A···O52ii = 151°] (see Table 3 for symmetry code). The anion in (III) is essentially planar, but with the carboxylate group rotated slightly out of the plane of the benzene ring [torsion angle C2—C1—C11—O11 = -161.47 (16)°, cf. C2—C3—C31—O32 = 172.04 (15)° (the carboxylic acid group) and C4—C5—N51—O52 = 175.06 (17)° (the nitro group)].

With the terephthalate salt, (IV), one of the piperidinium N—H···Ocarboxyl hydrogen bonds seen in Fig. 4 is accompanied by an asymmetric three-centre N–H···O,O'carboxyl interaction [graph set R21(4)] with the centrosymmetric terephthalate dianion (Fig. 8). This second association links two INIPA cations to the terephthalate dianion, which is extended longitudinally in the approximate b cell direction through centrosymmetric cyclic water-bridged amide–amide associations [graph set R44(12)]. The water molecules also act as acceptors in bridging these chains laterally through amide N—H···O hydrogen bonds (Table 4), forming centrosymmetric cyclic R42(8) associations. The lateral piperidinium N—H···Ocarboxyl hydrogen bonds shown in Fig. 4, together with the water O—H···Ocarboxyl associations [graph sets R43(10), R33(18) and R64(22)], complete a three-dimensional framework structure. The centrosymmetric terephthalate dianion deviates slightly from planarity [torsion angle C2—C1—C11—O11 = 169.25 (12)°].

The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of INIPA cation–anion association is also shown in the asymmetric three-centre piperidinium N—H···O,O'carboxyl interaction in the first-reported structure of a 2:1 isonipecotamide carboxylate salt.

Related literature top

For related literature, see: Allen et al. (1998); Bernstein et al. (1995); Etter et al. (1990); Glidewell et al. (2005); Smith & Wermuth (2010b, 2010c, 2010d, 2010e, 2010f, 2011a, 2011b, 2011c); Smith et al. (2010).

Experimental top

The title compounds were synthesized by heating together under reflux for 10 min 4-piperidinecarboxamide (isonipecotamide, 1 mmol) with either 4-nitrophthalic acid (1 mmol) for (I), 4,5-dichlorophthalic acid (1 mmol) for (II), 5-nitroisophthalic acid (1 mmol) for (III) or terephthalic acid (1 mmol) for (IV) in either methanol (50 ml) for (III), methanol–water (80%, 50 ml) for (I) and (IV) or ethanol–water (50%, 50 ml) for (II). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave colourless plates of (I) and (III), blocks of (II) or prisms of (IV).

Refinement top

H atoms involved in hydrogen-bonding interactions were located by difference methods and, with the exception of the carboxylic acid H atoms, which were set invariant in the final cycles of refinement, their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinements at calculated positions [C—H(aliphatic) = 0.97 or 0.98 Å, and C—H(aromatic) = 0.93 Å] using a riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (II), (III); SHELXS97 (Sheldrick, 2008) for (IV). 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).

Figures top
[Figure 1] Fig. 1. The molecular conformation and atom-numbering scheme for the INIPA cation and NPHA monoanion in (I). Displacement ellipsoids are drawn at the 40% probability level and the inter-species hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. The molecular configuration and atom-numbering scheme for the INIPA cation and DCPA monoanion in (II). Displacement ellipsoids are drawn at the 40% probability level and the inter-species hydrogen bond is shown as a dashed line.
[Figure 3] Fig. 3. The molecular conformation and atom-numbering scheme for the INIPA cation and NIPA monoanion in (III). Displacement ellipsoids are drawn at the 40% probability level. The inter-species hydrogen bonds is shown as a dashed line.
[Figure 4] Fig. 4. The molecular conformation and atom-numbering scheme for the INIPA cation, the TPA dianion and the solvent water molecule in the asymmetric unit of (IV). The dianion has inversion symmetry [symmetry code: (i) -x, -y + 1, -z]. Displacement ellipsoids are drawn at the 40% probability level and inter-species hydrogen bonds are shown as dashed lines.
[Figure 5] Fig. 5. The two-dimensional hydrogen-bonded network structure of (I), extending across the bOc plane of the unit cell, showing hydrogen-bonding associations as dashed lines. Graph sets for cyclic hydrogen-bonding associations are also indicated. Non-interactive H atoms have been omitted. (For symmetry codes, see Table 1.)
[Figure 6] Fig. 6. The one-dimensional hydrogen-bonded ribbon structure of (II), extending along the b cell direction, showing hydrogen-bonding associations as dashed lines. Graph sets for cyclic hydrogen-bonding associations are also indicated. Non-interactive H atoms have been omitted. (For symmetry codes, see Table 2.)
[Figure 7] Fig. 7. A perspective view of the three-dimensional hydrogen-bonded framework structure of (III), showing the NIPA chain substructures and amide–amide dimer associations. Hydrogen bonds are shown as dashed lines. Graph sets for cyclic hydrogen-bonding associations are also indicated. Non-interactive H atoms have been omitted. [Symmetry code: (v) -x + 1, y - 1/2, -z + 1/2; for other codes, see Table 3.]
[Figure 8] Fig. 8. The three-dimensional hydrogen-bonded framework structure of (IV), in a perspective view of the unit cell, showing hydrogen-bonding associations as dashed lines. Graph sets for cyclic hydrogen-bonding associations are also indicated. Non-interactive H atoms have been omitted. [For symmetry code (i), see Fig. 1; for other codes, see Table 4.]
(I) 4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate top
Crystal data top
C6H13N2O+·C8H4NO6F(000) = 712
Mr = 339.31Dx = 1.483 Mg m3
Monoclinic, P21/nMelting point: 467 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 5.8637 (5) ÅCell parameters from 4796 reflections
b = 11.2707 (8) Åθ = 3.2–28.8°
c = 23.0268 (19) ŵ = 0.12 mm1
β = 93.082 (8)°T = 200 K
V = 1519.6 (2) Å3Plate, colourless
Z = 40.40 × 0.40 × 0.12 mm
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
2989 independent reflections
Radiation source: Enhance (Mo) X-ray source2375 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 76
Tmin = 0.915, Tmax = 0.980k = 1313
10364 measured reflectionsl = 2826
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0482P)2 + 0.9247P]
where P = (Fo2 + 2Fc2)/3
2989 reflections(Δ/σ)max < 0.001
233 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C6H13N2O+·C8H4NO6V = 1519.6 (2) Å3
Mr = 339.31Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.8637 (5) ŵ = 0.12 mm1
b = 11.2707 (8) ÅT = 200 K
c = 23.0268 (19) Å0.40 × 0.40 × 0.12 mm
β = 93.082 (8)°
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
2989 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2375 reflections with I > 2σ(I)
Tmin = 0.915, Tmax = 0.980Rint = 0.023
10364 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.35 e Å3
2989 reflectionsΔρmin = 0.26 e Å3
233 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O41A0.5071 (3)0.87661 (14)0.55291 (7)0.0470 (6)
N1A0.0153 (3)0.63006 (16)0.65455 (8)0.0299 (6)
N41A0.2315 (4)0.9218 (2)0.48579 (9)0.0430 (7)
C2A0.0994 (5)0.5737 (2)0.60175 (11)0.0455 (8)
C3A0.2620 (4)0.65623 (19)0.57243 (11)0.0436 (8)
C4A0.1494 (4)0.77453 (18)0.55762 (8)0.0304 (6)
C5A0.0609 (4)0.82942 (19)0.61283 (10)0.0348 (7)
C6A0.0971 (4)0.7461 (2)0.64247 (11)0.0424 (8)
C41A0.3124 (4)0.86121 (18)0.53162 (8)0.0298 (6)
O110.6413 (3)0.51227 (13)0.69033 (6)0.0360 (5)
O120.4026 (2)0.46519 (13)0.75858 (6)0.0348 (5)
O210.3549 (3)0.72451 (13)0.73146 (7)0.0406 (5)
O220.3569 (2)0.84857 (12)0.80634 (6)0.0307 (4)
O411.0325 (3)0.85304 (16)0.93918 (7)0.0484 (6)
O421.2952 (3)0.71969 (18)0.93283 (8)0.0547 (6)
N41.1086 (3)0.76236 (17)0.91794 (7)0.0358 (6)
C10.7105 (3)0.58879 (16)0.78603 (8)0.0219 (5)
C20.6377 (3)0.69872 (16)0.80700 (8)0.0205 (5)
C30.7680 (3)0.75455 (17)0.85112 (8)0.0244 (5)
C40.9697 (3)0.70127 (17)0.87223 (8)0.0259 (6)
C51.0447 (3)0.59532 (19)0.85117 (9)0.0309 (6)
C60.9130 (3)0.53851 (18)0.80846 (9)0.0295 (6)
C110.5745 (3)0.51917 (16)0.74006 (9)0.0243 (6)
C210.4318 (3)0.75916 (16)0.77889 (8)0.0219 (5)
H4A0.020000.761100.529700.0370*
H11A0.098 (5)0.578 (2)0.6715 (11)0.050 (7)*
H12A0.138 (5)0.641 (2)0.6813 (11)0.046 (7)*
H21A0.028800.554900.575000.0550*
H22A0.177400.500300.612200.0550*
H31A0.310800.619400.537100.0520*
H32A0.396300.669400.598100.0520*
H42A0.318 (5)0.983 (2)0.4725 (12)0.053 (8)*
H43A0.104 (5)0.902 (3)0.4714 (13)0.059 (9)*
H51A0.189200.849000.639400.0420*
H52A0.019900.902400.602900.0420*
H61A0.141100.781100.678700.0510*
H62A0.234500.734000.617800.0510*
H30.721100.826400.866300.0290*
H51.182000.562500.865500.0370*
H60.960000.465600.794400.0350*
H220.251300.895100.780300.0370*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0394 (10)0.0472 (10)0.0533 (10)0.0162 (8)0.0076 (8)0.0227 (8)
N1A0.0290 (10)0.0349 (10)0.0257 (9)0.0114 (8)0.0004 (8)0.0048 (7)
N41A0.0359 (12)0.0520 (13)0.0407 (12)0.0080 (10)0.0005 (9)0.0226 (10)
C2A0.0645 (17)0.0317 (12)0.0421 (13)0.0095 (12)0.0186 (12)0.0007 (10)
C3A0.0569 (16)0.0316 (12)0.0446 (14)0.0015 (11)0.0232 (12)0.0045 (10)
C4A0.0325 (11)0.0348 (11)0.0234 (10)0.0111 (9)0.0043 (8)0.0043 (8)
C5A0.0317 (12)0.0311 (11)0.0422 (13)0.0008 (9)0.0085 (10)0.0070 (9)
C6A0.0335 (13)0.0444 (13)0.0505 (14)0.0008 (10)0.0134 (11)0.0102 (11)
C41A0.0357 (12)0.0308 (11)0.0230 (10)0.0024 (9)0.0033 (9)0.0016 (8)
O110.0379 (9)0.0366 (8)0.0348 (8)0.0131 (7)0.0137 (7)0.0089 (7)
O120.0297 (8)0.0386 (8)0.0369 (8)0.0172 (7)0.0107 (6)0.0063 (7)
O210.0411 (9)0.0388 (9)0.0396 (9)0.0146 (7)0.0194 (7)0.0125 (7)
O220.0334 (8)0.0281 (7)0.0303 (8)0.0120 (6)0.0015 (6)0.0022 (6)
O410.0539 (11)0.0506 (10)0.0396 (9)0.0067 (9)0.0078 (8)0.0139 (8)
O420.0345 (10)0.0814 (13)0.0458 (10)0.0067 (9)0.0198 (8)0.0017 (9)
N40.0351 (11)0.0448 (11)0.0268 (9)0.0070 (9)0.0033 (8)0.0032 (8)
C10.0190 (9)0.0212 (9)0.0261 (10)0.0015 (7)0.0065 (7)0.0042 (7)
C20.0185 (9)0.0203 (9)0.0228 (9)0.0028 (7)0.0024 (7)0.0026 (7)
C30.0277 (10)0.0217 (9)0.0239 (9)0.0015 (8)0.0023 (8)0.0017 (8)
C40.0234 (10)0.0332 (11)0.0208 (9)0.0075 (8)0.0023 (8)0.0045 (8)
C50.0223 (10)0.0341 (11)0.0363 (11)0.0046 (9)0.0005 (9)0.0075 (9)
C60.0240 (11)0.0244 (10)0.0404 (12)0.0044 (8)0.0052 (9)0.0005 (9)
C110.0234 (10)0.0169 (9)0.0331 (11)0.0015 (8)0.0075 (8)0.0010 (8)
C210.0224 (10)0.0183 (9)0.0250 (9)0.0010 (7)0.0010 (8)0.0008 (7)
Geometric parameters (Å, º) top
O41A—C41A1.230 (3)C2A—H21A0.9700
O11—C111.233 (2)C2A—H22A0.9700
O12—C111.271 (2)C3A—H31A0.9700
O21—C211.223 (2)C3A—H32A0.9700
O22—C211.280 (2)C4A—H4A0.9800
O41—N41.227 (3)C5A—H51A0.9700
O42—N41.227 (3)C5A—H52A0.9700
O22—H220.9900C6A—H62A0.9700
N1A—C2A1.480 (3)C6A—H61A0.9700
N1A—C6A1.484 (3)C1—C21.405 (3)
N41A—C41A1.323 (3)C1—C111.510 (3)
N1A—H12A0.93 (3)C1—C61.390 (3)
N1A—H11A0.98 (3)C2—C31.389 (3)
N41A—H42A0.92 (3)C2—C211.502 (3)
N41A—H43A0.83 (3)C3—C41.391 (3)
N4—C41.467 (3)C4—C51.370 (3)
C2A—C3A1.516 (3)C5—C61.376 (3)
C3A—C4A1.519 (3)C3—H30.9300
C4A—C41A1.513 (3)C5—H50.9300
C4A—C5A1.529 (3)C6—H60.9300
C5A—C6A1.508 (3)
C21—O22—H22110.00C3A—C4A—H4A109.00
C2A—N1A—C6A112.87 (18)C4A—C5A—H52A109.00
C2A—N1A—H12A108.7 (16)C6A—C5A—H51A109.00
C6A—N1A—H11A107.3 (15)C4A—C5A—H51A109.00
C2A—N1A—H11A109.4 (14)C6A—C5A—H52A109.00
H11A—N1A—H12A109 (2)H51A—C5A—H52A108.00
C6A—N1A—H12A109.1 (14)N1A—C6A—H62A109.00
H42A—N41A—H43A125 (3)C5A—C6A—H61A110.00
C41A—N41A—H43A117 (2)C5A—C6A—H62A109.00
C41A—N41A—H42A118.2 (18)N1A—C6A—H61A109.00
O41—N4—O42123.56 (19)H61A—C6A—H62A108.00
O41—N4—C4118.48 (17)C2—C1—C11122.71 (16)
O42—N4—C4117.95 (18)C6—C1—C11117.19 (16)
N1A—C2A—C3A110.35 (18)C2—C1—C6120.09 (17)
C2A—C3A—C4A111.3 (2)C1—C2—C21120.26 (16)
C5A—C4A—C41A108.52 (17)C3—C2—C21120.50 (16)
C3A—C4A—C5A109.35 (17)C1—C2—C3119.07 (16)
C3A—C4A—C41A112.31 (19)C2—C3—C4118.96 (17)
C4A—C5A—C6A111.62 (18)N4—C4—C3118.49 (17)
N1A—C6A—C5A110.86 (18)C3—C4—C5122.39 (17)
O41A—C41A—C4A121.73 (18)N4—C4—C5119.11 (16)
N41A—C41A—C4A116.2 (2)C4—C5—C6118.70 (17)
O41A—C41A—N41A122.0 (2)C1—C6—C5120.76 (18)
H21A—C2A—H22A108.00O11—C11—C1120.12 (17)
N1A—C2A—H22A110.00O12—C11—C1114.33 (17)
N1A—C2A—H21A110.00O11—C11—O12125.39 (18)
C3A—C2A—H22A110.00O21—C21—C2119.29 (17)
C3A—C2A—H21A110.00O22—C21—C2115.69 (16)
C2A—C3A—H31A109.00O21—C21—O22124.94 (17)
C4A—C3A—H31A109.00C2—C3—H3121.00
H31A—C3A—H32A108.00C4—C3—H3121.00
C2A—C3A—H32A109.00C4—C5—H5121.00
C4A—C3A—H32A109.00C6—C5—H5121.00
C41A—C4A—H4A109.00C1—C6—H6120.00
C5A—C4A—H4A109.00C5—C6—H6120.00
C6A—N1A—C2A—C3A56.6 (3)C11—C1—C2—C217.4 (3)
C2A—N1A—C6A—C5A55.9 (3)C2—C1—C6—C50.1 (3)
O41—N4—C4—C36.0 (3)C11—C1—C6—C5178.87 (18)
O41—N4—C4—C5175.20 (18)C2—C1—C11—O11107.7 (2)
O42—N4—C4—C3174.03 (18)C2—C1—C11—O1276.7 (2)
O42—N4—C4—C54.8 (3)C6—C1—C11—O1173.6 (2)
N1A—C2A—C3A—C4A56.8 (3)C6—C1—C11—O12102.0 (2)
C2A—C3A—C4A—C5A56.0 (2)C1—C2—C3—C41.6 (3)
C2A—C3A—C4A—C41A176.54 (18)C21—C2—C3—C4173.75 (17)
C5A—C4A—C41A—O41A75.2 (3)C1—C2—C21—O2114.0 (3)
C5A—C4A—C41A—N41A103.0 (2)C1—C2—C21—O22169.25 (16)
C3A—C4A—C41A—O41A45.8 (3)C3—C2—C21—O21161.27 (18)
C3A—C4A—C5A—C6A55.2 (2)C3—C2—C21—O2215.5 (3)
C41A—C4A—C5A—C6A178.04 (18)C2—C3—C4—N4178.65 (17)
C3A—C4A—C41A—N41A136.0 (2)C2—C3—C4—C50.2 (3)
C4A—C5A—C6A—N1A54.9 (2)N4—C4—C5—C6179.79 (17)
C6—C1—C2—C31.4 (3)C3—C4—C5—C61.4 (3)
C6—C1—C2—C21173.89 (17)C4—C5—C6—C11.5 (3)
C11—C1—C2—C3177.23 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O11i0.98 (3)1.77 (3)2.729 (2)163 (2)
N1A—H12A···O210.93 (3)1.92 (3)2.803 (2)158 (2)
N41A—H42A···O41Aii0.92 (3)1.99 (3)2.907 (3)176 (2)
N41A—H43A···O42iii0.83 (3)2.40 (3)3.200 (3)161 (3)
O22—H22···O12iv0.991.472.4562 (19)179
C4A—H4A···O42iii0.982.543.454 (3)156
C2A—H22A···O22v0.972.553.305 (3)134
Symmetry codes: (i) x1, y, z; (ii) x+1, y+2, z+1; (iii) x3/2, y+3/2, z1/2; (iv) x+1/2, y+1/2, z+3/2; (v) x+1/2, y1/2, z+3/2.
(II) 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate top
Crystal data top
C6H13N2O+·C8H3Cl2O4F(000) = 752
Mr = 363.19Dx = 1.536 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8871 reflections
a = 6.6897 (4) Åθ = 3.1–28.9°
b = 9.7392 (5) ŵ = 0.44 mm1
c = 24.1222 (13) ÅT = 200 K
β = 92.479 (4)°Block, colourless
V = 1570.15 (15) Å30.30 × 0.25 × 0.20 mm
Z = 4
Data collection top
Oxford Gemini S CCD area-detector
diffractometer
3084 independent reflections
Radiation source: Enhance (Mo) X-ray source2777 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 88
Tmin = 0.908, Tmax = 0.980k = 1212
19231 measured reflectionsl = 2929
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.30 w = 1/[σ2(Fo2) + (0.0177P)2 + 2.734P]
where P = (Fo2 + 2Fc2)/3
3084 reflections(Δ/σ)max = 0.001
224 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C6H13N2O+·C8H3Cl2O4V = 1570.15 (15) Å3
Mr = 363.19Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.6897 (4) ŵ = 0.44 mm1
b = 9.7392 (5) ÅT = 200 K
c = 24.1222 (13) Å0.30 × 0.25 × 0.20 mm
β = 92.479 (4)°
Data collection top
Oxford Gemini S CCD area-detector
diffractometer
3084 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2777 reflections with I > 2σ(I)
Tmin = 0.908, Tmax = 0.980Rint = 0.028
19231 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.30Δρmax = 0.37 e Å3
3084 reflectionsΔρmin = 0.29 e Å3
224 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O41A0.7063 (4)0.2890 (2)0.24101 (10)0.0453 (9)
N1A0.8063 (4)0.4798 (3)0.42405 (10)0.0251 (8)
N41A0.7344 (5)0.5032 (4)0.20550 (11)0.0379 (10)
C2A0.9600 (4)0.5342 (3)0.38672 (11)0.0278 (9)
C3A0.9429 (4)0.4642 (3)0.33052 (12)0.0284 (9)
C4A0.7313 (4)0.4792 (3)0.30467 (11)0.0234 (8)
C5A0.5823 (5)0.4163 (3)0.34351 (12)0.0283 (9)
C6A0.5975 (4)0.4870 (3)0.39972 (12)0.0278 (9)
C41A0.7207 (5)0.4135 (3)0.24744 (12)0.0292 (9)
Cl40.70276 (15)1.20000 (9)0.67633 (3)0.0436 (3)
Cl50.73906 (13)0.88021 (9)0.70518 (3)0.0346 (2)
O110.7966 (3)0.6468 (2)0.51891 (8)0.0312 (7)
O120.7517 (4)0.7842 (2)0.44724 (8)0.0365 (7)
O210.7440 (3)1.0235 (2)0.42476 (8)0.0309 (7)
O220.7514 (4)1.2225 (2)0.46816 (9)0.0393 (8)
C10.7580 (4)0.8846 (3)0.53926 (11)0.0194 (7)
C20.7464 (4)1.0267 (3)0.52629 (11)0.0201 (8)
C30.7329 (4)1.1194 (3)0.57002 (12)0.0250 (8)
C40.7292 (4)1.0782 (3)0.62488 (11)0.0245 (8)
C50.7429 (4)0.9395 (3)0.63756 (11)0.0231 (8)
C60.7570 (4)0.8455 (3)0.59506 (11)0.0219 (8)
C110.7709 (4)0.7639 (3)0.49947 (11)0.0237 (8)
C210.7479 (4)1.0964 (3)0.46933 (12)0.0246 (8)
H4A0.701200.577200.300600.0280*
H11A0.818 (5)0.531 (4)0.4561 (15)0.041 (10)*
H12A0.827 (5)0.394 (4)0.4321 (15)0.041 (10)*
H21A1.092500.518700.403500.0330*
H22A0.941700.632400.382000.0330*
H31A0.975100.367500.334800.0340*
H32A1.038100.504600.306100.0340*
H41A0.737 (5)0.467 (4)0.1749 (16)0.038 (10)*
H42A0.759 (6)0.595 (4)0.2140 (15)0.043 (11)*
H51A0.447600.426200.327500.0340*
H52A0.609900.319000.348100.0340*
H61A0.557800.582400.395500.0330*
H62A0.507100.443200.424600.0330*
H30.726101.212700.562000.0300*
H60.766100.752700.603900.0260*
H120.748900.883800.438000.0440*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0668 (18)0.0325 (14)0.0373 (13)0.0036 (12)0.0091 (12)0.0144 (10)
N1A0.0399 (15)0.0181 (13)0.0176 (12)0.0011 (11)0.0035 (10)0.0015 (10)
N41A0.0473 (18)0.0476 (19)0.0188 (13)0.0047 (15)0.0016 (12)0.0000 (13)
C2A0.0276 (16)0.0319 (16)0.0238 (14)0.0008 (13)0.0002 (12)0.0005 (12)
C3A0.0281 (16)0.0329 (17)0.0246 (14)0.0010 (13)0.0052 (12)0.0023 (12)
C4A0.0325 (16)0.0161 (13)0.0218 (13)0.0015 (12)0.0034 (12)0.0005 (11)
C5A0.0291 (16)0.0296 (16)0.0263 (14)0.0068 (13)0.0036 (12)0.0041 (12)
C6A0.0308 (16)0.0283 (16)0.0250 (14)0.0024 (13)0.0085 (12)0.0018 (12)
C41A0.0291 (17)0.0332 (18)0.0256 (14)0.0019 (13)0.0032 (12)0.0046 (13)
Cl40.0669 (6)0.0320 (4)0.0322 (4)0.0029 (4)0.0072 (4)0.0148 (3)
Cl50.0467 (5)0.0405 (4)0.0167 (3)0.0004 (4)0.0042 (3)0.0023 (3)
O110.0497 (14)0.0189 (10)0.0250 (10)0.0022 (10)0.0033 (9)0.0003 (8)
O120.0677 (16)0.0235 (11)0.0182 (10)0.0047 (11)0.0001 (10)0.0018 (8)
O210.0436 (13)0.0308 (12)0.0184 (10)0.0001 (10)0.0018 (9)0.0055 (8)
O220.0601 (16)0.0216 (12)0.0364 (12)0.0040 (11)0.0031 (11)0.0110 (9)
C10.0193 (13)0.0200 (13)0.0190 (12)0.0016 (11)0.0012 (10)0.0004 (10)
C20.0173 (13)0.0215 (14)0.0214 (13)0.0008 (11)0.0004 (10)0.0012 (11)
C30.0281 (15)0.0174 (13)0.0296 (15)0.0021 (12)0.0016 (12)0.0002 (12)
C40.0270 (15)0.0236 (15)0.0230 (14)0.0032 (12)0.0018 (11)0.0071 (11)
C50.0230 (14)0.0292 (15)0.0171 (13)0.0027 (12)0.0012 (11)0.0008 (11)
C60.0248 (14)0.0193 (14)0.0216 (13)0.0006 (11)0.0026 (11)0.0023 (11)
C110.0269 (15)0.0229 (14)0.0214 (13)0.0014 (12)0.0036 (11)0.0009 (11)
C210.0221 (14)0.0245 (15)0.0272 (15)0.0018 (12)0.0026 (11)0.0066 (12)
Geometric parameters (Å, º) top
Cl4—C41.731 (3)C2A—H22A0.9700
Cl5—C51.732 (3)C2A—H21A0.9700
O41A—C41A1.226 (4)C3A—H31A0.9700
O11—C111.242 (3)C3A—H32A0.9700
O12—C111.276 (3)C4A—H4A0.9800
O21—C211.288 (3)C5A—H51A0.9700
O22—C211.229 (4)C5A—H52A0.9700
O12—H121.0000C6A—H62A0.9700
N1A—C2A1.493 (4)C6A—H61A0.9700
N1A—C6A1.493 (4)C1—C21.420 (4)
N41A—C41A1.343 (4)C1—C111.522 (4)
N1A—H12A0.87 (4)C1—C61.399 (4)
N1A—H11A0.92 (4)C2—C211.533 (4)
N41A—H42A0.93 (4)C2—C31.394 (4)
N41A—H41A0.82 (4)C3—C41.384 (4)
C2A—C3A1.517 (4)C4—C51.387 (4)
C3A—C4A1.529 (4)C5—C61.381 (4)
C4A—C41A1.521 (4)C3—H30.9300
C4A—C5A1.526 (4)C6—H60.9300
C5A—C6A1.520 (4)
C11—O12—H12112.00C6A—C5A—H52A110.00
C2A—N1A—C6A113.8 (2)H51A—C5A—H52A108.00
C6A—N1A—H11A110 (2)C4A—C5A—H52A110.00
C2A—N1A—H11A106 (2)C4A—C5A—H51A110.00
C2A—N1A—H12A112 (2)C5A—C6A—H61A109.00
C6A—N1A—H12A106 (2)N1A—C6A—H61A109.00
H11A—N1A—H12A109 (3)N1A—C6A—H62A110.00
H41A—N41A—H42A127 (4)H61A—C6A—H62A108.00
C41A—N41A—H42A118 (2)C5A—C6A—H62A109.00
C41A—N41A—H41A114 (3)C2—C1—C11128.1 (2)
N1A—C2A—C3A110.6 (2)C2—C1—C6118.3 (3)
C2A—C3A—C4A110.7 (2)C6—C1—C11113.5 (2)
C5A—C4A—C41A112.5 (2)C1—C2—C21128.8 (2)
C3A—C4A—C5A109.2 (2)C1—C2—C3118.0 (2)
C3A—C4A—C41A109.6 (2)C3—C2—C21113.2 (3)
C4A—C5A—C6A110.2 (2)C2—C3—C4122.7 (3)
N1A—C6A—C5A110.8 (2)Cl4—C4—C5121.1 (2)
O41A—C41A—N41A123.8 (3)C3—C4—C5119.3 (3)
O41A—C41A—C4A122.1 (3)Cl4—C4—C3119.6 (2)
N41A—C41A—C4A114.1 (3)C4—C5—C6119.2 (2)
N1A—C2A—H22A110.00Cl5—C5—C4121.9 (2)
N1A—C2A—H21A109.00Cl5—C5—C6118.9 (2)
H21A—C2A—H22A108.00C1—C6—C5122.5 (3)
C3A—C2A—H21A110.00O11—C11—C1118.8 (2)
C3A—C2A—H22A109.00O12—C11—C1119.8 (2)
C4A—C3A—H31A109.00O11—C11—O12121.4 (3)
C4A—C3A—H32A110.00O22—C21—C2117.7 (3)
H31A—C3A—H32A108.00O21—C21—O22122.1 (3)
C2A—C3A—H32A110.00O21—C21—C2120.2 (2)
C2A—C3A—H31A109.00C2—C3—H3119.00
C5A—C4A—H4A108.00C4—C3—H3119.00
C3A—C4A—H4A108.00C1—C6—H6119.00
C41A—C4A—H4A109.00C5—C6—H6119.00
C6A—C5A—H51A110.00
C6A—N1A—C2A—C3A53.9 (3)C2—C1—C11—O11174.1 (3)
C2A—N1A—C6A—C5A54.3 (3)C2—C1—C11—O127.1 (4)
N1A—C2A—C3A—C4A55.6 (3)C6—C1—C11—O116.2 (4)
C2A—C3A—C4A—C5A58.7 (3)C6—C1—C11—O12172.6 (3)
C2A—C3A—C4A—C41A177.6 (2)C1—C2—C3—C40.4 (4)
C3A—C4A—C5A—C6A58.8 (3)C21—C2—C3—C4180.0 (2)
C41A—C4A—C5A—C6A179.2 (2)C1—C2—C21—O215.9 (4)
C3A—C4A—C41A—O41A78.8 (4)C1—C2—C21—O22174.7 (3)
C3A—C4A—C41A—N41A99.4 (3)C3—C2—C21—O21174.6 (2)
C5A—C4A—C41A—O41A43.0 (4)C3—C2—C21—O224.9 (4)
C5A—C4A—C41A—N41A138.9 (3)C2—C3—C4—Cl4177.6 (2)
C4A—C5A—C6A—N1A56.3 (3)C2—C3—C4—C51.2 (4)
C6—C1—C2—C30.5 (4)Cl4—C4—C5—Cl51.2 (3)
C6—C1—C2—C21179.0 (3)Cl4—C4—C5—C6177.8 (2)
C11—C1—C2—C3179.1 (3)C3—C4—C5—Cl5180.0 (2)
C11—C1—C2—C211.3 (5)C3—C4—C5—C60.9 (4)
C2—C1—C6—C50.8 (4)Cl5—C5—C6—C1179.0 (2)
C11—C1—C6—C5179.0 (2)C4—C5—C6—C10.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O110.92 (4)1.90 (4)2.810 (3)170 (3)
N1A—H11A···O120.92 (4)2.51 (4)3.042 (4)117 (3)
N1A—H12A···O22i0.87 (4)1.96 (4)2.753 (3)152 (3)
N41A—H41A···O21ii0.82 (4)2.48 (4)3.158 (3)142 (4)
N41A—H42A···O41Aiii0.93 (4)2.19 (4)3.086 (4)163 (3)
O12—H12···O211.001.402.393 (3)180
C3—H3···O220.932.282.662 (4)104
C4A—H4A···O41Aiii0.982.393.245 (4)146
C6—H6···O110.932.312.689 (3)104
C2A—H21A···O11iv0.972.563.259 (3)129
C2A—H22A···O120.972.543.190 (4)124
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2; (iii) x+3/2, y+1/2, z+1/2; (iv) x+2, y+1, z+1.
(III) 4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate top
Crystal data top
C6H13N2O+·C8H4NO6F(000) = 712
Mr = 339.31Dx = 1.500 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4846 reflections
a = 9.4117 (4) Åθ = 3.2–28.7°
b = 14.3552 (5) ŵ = 0.12 mm1
c = 11.4490 (5) ÅT = 200 K
β = 103.787 (4)°Plate, colourless
V = 1502.27 (11) Å30.45 × 0.40 × 0.18 mm
Z = 4
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
2940 independent reflections
Radiation source: fine-focus sealed tube2284 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1111
Tmin = 0.98, Tmax = 0.99k = 1717
9866 measured reflectionsl = 1412
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0694P)2]
where P = (Fo2 + 2Fc2)/3
2940 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C6H13N2O+·C8H4NO6V = 1502.27 (11) Å3
Mr = 339.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.4117 (4) ŵ = 0.12 mm1
b = 14.3552 (5) ÅT = 200 K
c = 11.4490 (5) Å0.45 × 0.40 × 0.18 mm
β = 103.787 (4)°
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer
2940 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2284 reflections with I > 2σ(I)
Tmin = 0.98, Tmax = 0.99Rint = 0.025
9866 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.35 e Å3
2940 reflectionsΔρmin = 0.24 e Å3
237 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O41A0.59457 (16)0.89483 (8)0.55593 (10)0.0441 (4)
N1A0.75063 (17)0.59544 (9)0.44483 (12)0.0274 (4)
N41A0.45092 (16)0.91398 (9)0.37052 (13)0.0276 (4)
C2A0.6261 (2)0.60070 (10)0.50398 (16)0.0329 (5)
C3A0.5943 (2)0.70018 (11)0.53417 (15)0.0308 (5)
C4A0.56894 (18)0.76325 (10)0.42330 (14)0.0259 (5)
C5A0.7036 (2)0.75760 (10)0.37175 (14)0.0297 (5)
C6A0.7315 (2)0.65785 (10)0.33822 (14)0.0335 (6)
C41A0.53807 (19)0.86299 (10)0.45496 (14)0.0263 (5)
O110.72771 (14)0.40335 (7)0.39084 (10)0.0310 (4)
O120.90850 (18)0.42023 (8)0.55448 (11)0.0504 (5)
O311.04577 (13)0.14479 (7)0.82832 (9)0.0309 (4)
O320.96788 (14)0.00396 (7)0.75335 (10)0.0318 (4)
O510.75616 (14)0.03200 (7)0.32869 (10)0.0342 (4)
O520.6672 (2)0.08685 (8)0.22188 (12)0.0623 (5)
N510.73297 (16)0.05155 (9)0.31637 (11)0.0280 (4)
C10.82957 (18)0.26747 (10)0.49770 (13)0.0224 (4)
C20.89685 (18)0.22902 (10)0.60935 (13)0.0232 (4)
C30.90771 (17)0.13329 (10)0.62527 (13)0.0217 (4)
C40.85331 (17)0.07377 (10)0.52947 (13)0.0221 (4)
C50.78839 (17)0.11326 (10)0.41904 (13)0.0216 (4)
C60.77429 (18)0.20842 (10)0.40177 (13)0.0223 (4)
C110.8197 (2)0.37206 (10)0.47962 (13)0.0276 (5)
C310.98111 (18)0.09530 (10)0.74656 (14)0.0239 (5)
H4A0.484300.739900.363100.0310*
H11A0.836 (2)0.6109 (14)0.5012 (19)0.051 (6)*
H12A0.756 (3)0.5313 (15)0.417 (2)0.061 (6)*
H21A0.648800.564000.577200.0390*
H22A0.539500.574200.450900.0390*
H31A0.675900.723900.595300.0370*
H32A0.508100.701200.566700.0370*
H41A0.414 (2)0.8948 (12)0.3024 (17)0.036 (5)*
H42A0.433 (2)0.9761 (13)0.3885 (16)0.036 (5)*
H51A0.689500.796800.300900.0360*
H52A0.788100.780600.430700.0360*
H61A0.649800.636200.275500.0400*
H62A0.818800.655800.307200.0400*
H20.934900.268200.673900.0280*
H40.860200.009500.539000.0260*
H60.728400.232500.326900.0270*
H321.026 (3)0.0185 (15)0.825 (2)0.067 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0673 (10)0.0278 (6)0.0267 (6)0.0133 (6)0.0098 (6)0.0068 (5)
N1A0.0347 (9)0.0150 (6)0.0268 (7)0.0030 (6)0.0038 (7)0.0000 (5)
N41A0.0314 (8)0.0216 (7)0.0259 (7)0.0066 (6)0.0006 (6)0.0016 (6)
C2A0.0344 (10)0.0223 (8)0.0382 (9)0.0032 (7)0.0013 (8)0.0105 (7)
C3A0.0349 (11)0.0273 (8)0.0324 (9)0.0030 (7)0.0122 (8)0.0065 (7)
C4A0.0296 (10)0.0183 (8)0.0247 (8)0.0009 (7)0.0034 (7)0.0012 (6)
C5A0.0500 (12)0.0167 (7)0.0233 (8)0.0047 (7)0.0105 (8)0.0025 (6)
C6A0.0558 (13)0.0198 (8)0.0245 (8)0.0087 (8)0.0088 (8)0.0020 (6)
C41A0.0298 (9)0.0213 (8)0.0266 (8)0.0019 (7)0.0044 (7)0.0006 (6)
O110.0418 (8)0.0170 (5)0.0285 (6)0.0040 (5)0.0028 (5)0.0024 (4)
O120.0814 (11)0.0200 (6)0.0343 (7)0.0081 (6)0.0166 (7)0.0063 (5)
O310.0363 (7)0.0286 (6)0.0227 (6)0.0010 (5)0.0033 (5)0.0027 (4)
O320.0415 (8)0.0226 (6)0.0255 (6)0.0028 (5)0.0033 (6)0.0085 (4)
O510.0482 (8)0.0149 (5)0.0383 (7)0.0017 (5)0.0078 (6)0.0053 (4)
O520.1003 (13)0.0318 (7)0.0324 (7)0.0136 (7)0.0285 (8)0.0090 (5)
N510.0335 (9)0.0211 (7)0.0258 (7)0.0015 (6)0.0001 (6)0.0038 (5)
C10.0267 (9)0.0177 (7)0.0210 (7)0.0002 (6)0.0020 (7)0.0007 (6)
C20.0274 (9)0.0202 (7)0.0201 (7)0.0027 (7)0.0019 (6)0.0021 (5)
C30.0213 (8)0.0213 (7)0.0219 (8)0.0010 (6)0.0040 (6)0.0030 (6)
C40.0238 (8)0.0151 (7)0.0261 (8)0.0013 (6)0.0037 (7)0.0026 (6)
C50.0230 (8)0.0177 (7)0.0227 (7)0.0007 (6)0.0027 (6)0.0026 (6)
C60.0266 (9)0.0182 (7)0.0196 (7)0.0025 (6)0.0005 (6)0.0019 (6)
C110.0393 (10)0.0184 (7)0.0223 (8)0.0007 (7)0.0019 (7)0.0013 (6)
C310.0234 (9)0.0237 (8)0.0231 (8)0.0005 (7)0.0027 (7)0.0042 (6)
Geometric parameters (Å, º) top
O41A—C41A1.2390 (19)C2A—H21A0.9700
O11—C111.251 (2)C2A—H22A0.9700
O12—C111.253 (2)C3A—H31A0.9700
O31—C311.2165 (18)C3A—H32A0.9700
O32—C311.3211 (18)C4A—H4A0.9800
O51—N511.2212 (16)C5A—H51A0.9700
O52—N511.2211 (19)C5A—H52A0.9700
O32—H320.93 (2)C6A—H62A0.9700
N1A—C2A1.489 (2)C6A—H61A0.9700
N1A—C6A1.490 (2)C1—C21.398 (2)
N41A—C41A1.329 (2)C1—C111.515 (2)
N1A—H12A0.98 (2)C1—C61.387 (2)
N1A—H11A0.93 (2)C2—C31.387 (2)
N41A—H41A0.822 (19)C3—C41.388 (2)
N41A—H42A0.940 (19)C3—C311.499 (2)
N51—C51.4650 (19)C4—C51.387 (2)
C2A—C3A1.516 (2)C5—C61.382 (2)
C3A—C4A1.531 (2)C2—H20.9300
C4A—C41A1.522 (2)C4—H40.9300
C4A—C5A1.522 (3)C6—H60.9300
C5A—C6A1.521 (2)
C31—O32—H32110.7 (14)C3A—C4A—H4A109.00
C2A—N1A—C6A112.81 (14)C4A—C5A—H52A109.00
C2A—N1A—H12A107.6 (16)C6A—C5A—H51A109.00
C6A—N1A—H11A109.9 (13)C4A—C5A—H51A109.00
C2A—N1A—H11A108.4 (12)C6A—C5A—H52A109.00
H11A—N1A—H12A110 (2)H51A—C5A—H52A108.00
C6A—N1A—H12A107.7 (13)N1A—C6A—H62A110.00
H41A—N41A—H42A117.9 (17)C5A—C6A—H61A110.00
C41A—N41A—H42A118.4 (11)C5A—C6A—H62A109.00
C41A—N41A—H41A123.6 (13)N1A—C6A—H61A109.00
O51—N51—O52123.29 (13)H61A—C6A—H62A108.00
O51—N51—C5118.79 (12)C2—C1—C11121.05 (13)
O52—N51—C5117.92 (12)C6—C1—C11119.88 (13)
N1A—C2A—C3A111.79 (13)C2—C1—C6119.05 (13)
C2A—C3A—C4A111.61 (14)C1—C2—C3120.97 (13)
C5A—C4A—C41A111.49 (13)C2—C3—C31119.06 (13)
C3A—C4A—C5A108.07 (13)C4—C3—C31120.66 (13)
C3A—C4A—C41A111.09 (13)C2—C3—C4120.28 (13)
C4A—C5A—C6A110.96 (13)C3—C4—C5117.90 (13)
N1A—C6A—C5A110.71 (13)N51—C5—C6118.63 (13)
O41A—C41A—C4A120.36 (14)C4—C5—C6122.73 (14)
N41A—C41A—C4A117.70 (14)N51—C5—C4118.64 (13)
O41A—C41A—N41A121.93 (14)C1—C6—C5119.06 (13)
H21A—C2A—H22A108.00O11—C11—C1118.34 (13)
N1A—C2A—H22A109.00O12—C11—C1116.37 (14)
N1A—C2A—H21A109.00O11—C11—O12125.26 (14)
C3A—C2A—H22A109.00O31—C31—C3122.42 (13)
C3A—C2A—H21A109.00O32—C31—C3112.74 (13)
C2A—C3A—H31A109.00O31—C31—O32124.84 (14)
C4A—C3A—H31A109.00C1—C2—H2120.00
H31A—C3A—H32A108.00C3—C2—H2120.00
C2A—C3A—H32A109.00C3—C4—H4121.00
C4A—C3A—H32A109.00C5—C4—H4121.00
C41A—C4A—H4A109.00C1—C6—H6120.00
C5A—C4A—H4A109.00C5—C6—H6120.00
C6A—N1A—C2A—C3A52.98 (18)C2—C1—C6—C50.5 (3)
C2A—N1A—C6A—C5A54.44 (18)C11—C1—C6—C5177.98 (16)
O51—N51—C5—C45.9 (2)C2—C1—C11—O11161.47 (16)
O51—N51—C5—C6173.90 (16)C2—C1—C11—O1220.3 (3)
O52—N51—C5—C4175.06 (17)C6—C1—C11—O1120.1 (3)
O52—N51—C5—C65.2 (2)C6—C1—C11—O12158.15 (17)
N1A—C2A—C3A—C4A54.6 (2)C1—C2—C3—C40.9 (3)
C2A—C3A—C4A—C5A57.05 (18)C1—C2—C3—C31179.86 (16)
C2A—C3A—C4A—C41A179.65 (15)C2—C3—C4—C50.2 (2)
C5A—C4A—C41A—O41A88.89 (19)C31—C3—C4—C5179.10 (15)
C5A—C4A—C41A—N41A90.25 (19)C2—C3—C31—O318.3 (3)
C3A—C4A—C41A—O41A31.7 (2)C2—C3—C31—O32172.04 (15)
C3A—C4A—C5A—C6A58.75 (16)C4—C3—C31—O31170.71 (16)
C41A—C4A—C5A—C6A178.89 (13)C4—C3—C31—O329.0 (2)
C3A—C4A—C41A—N41A149.14 (16)C3—C4—C5—N51178.81 (15)
C4A—C5A—C6A—N1A58.01 (18)C3—C4—C5—C61.0 (2)
C6—C1—C2—C30.5 (3)N51—C5—C6—C1178.46 (15)
C11—C1—C2—C3179.03 (16)C4—C5—C6—C11.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O31i0.93 (2)2.06 (2)2.9236 (18)153.6 (17)
N1A—H12A···O110.98 (2)1.87 (2)2.8229 (16)164 (2)
N1A—H12A···O120.98 (2)2.45 (2)3.0366 (19)118.1 (17)
N41A—H41A···O11ii0.822 (19)2.298 (19)3.0669 (19)155.9 (17)
N41A—H42A···O41Aiii0.940 (19)1.996 (19)2.9321 (18)174.1 (16)
O32—H32···O12iv0.93 (2)1.63 (2)2.5336 (17)164 (3)
C2A—H22A···O52ii0.972.433.308 (2)151
C5A—H51A···O51v0.972.543.1187 (18)118
C6A—H61A···O41Avi0.972.483.2700 (19)138
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+2, z+1; (iv) x+2, y1/2, z+3/2; (v) x, y+1, z; (vi) x, y+3/2, z1/2.
(IV) bis(4-carbamoylpiperidinium) benzene-1,2-dicarboxylate dihydrate top
Crystal data top
2C6H13N2O8+·C8H4O42·2H2OZ = 1
Mr = 458.51F(000) = 246
Triclinic, P1Dx = 1.367 Mg m3
Hall symbol: -P 1Melting point: 531 K
a = 6.5099 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.7777 (6) ÅCell parameters from 3616 reflections
c = 11.6865 (12) Åθ = 3.4–28.7°
α = 76.429 (8)°µ = 0.11 mm1
β = 76.968 (7)°T = 200 K
γ = 80.885 (7)°Needle, colourless
V = 556.89 (9) Å30.50 × 0.15 × 0.08 mm
Data collection top
Oxford Gemini-S CCD are-detector
diffractometer
2177 independent reflections
Radiation source: Enhance (Mo) X-ray source1746 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 88
Tmin = 0.965, Tmax = 0.990k = 99
6562 measured reflectionsl = 1414
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0583P)2]
where P = (Fo2 + 2Fc2)/3
2177 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
2C6H13N2O8+·C8H4O42·2H2Oγ = 80.885 (7)°
Mr = 458.51V = 556.89 (9) Å3
Triclinic, P1Z = 1
a = 6.5099 (5) ÅMo Kα radiation
b = 7.7777 (6) ŵ = 0.11 mm1
c = 11.6865 (12) ÅT = 200 K
α = 76.429 (8)°0.50 × 0.15 × 0.08 mm
β = 76.968 (7)°
Data collection top
Oxford Gemini-S CCD are-detector
diffractometer
2177 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
1746 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.990Rint = 0.024
6562 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.23 e Å3
2177 reflectionsΔρmin = 0.16 e Å3
169 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O41A0.02732 (15)0.38666 (12)0.39711 (9)0.0283 (3)
N1A0.49004 (18)0.84055 (14)0.16744 (10)0.0228 (3)
N41A0.3297 (2)0.23446 (15)0.44750 (11)0.0301 (4)
C2A0.6401 (2)0.69868 (17)0.22515 (12)0.0230 (4)
C3A0.5391 (2)0.52630 (16)0.27457 (12)0.0208 (4)
C4A0.32588 (19)0.55264 (16)0.36062 (11)0.0184 (4)
C5A0.1803 (2)0.70710 (16)0.30251 (12)0.0220 (4)
C6A0.2890 (2)0.87498 (17)0.25378 (13)0.0270 (4)
C41A0.2150 (2)0.38311 (16)0.40264 (11)0.0200 (4)
O110.37675 (16)0.82742 (12)0.04688 (9)0.0311 (3)
O120.17970 (16)0.92206 (12)0.18601 (9)0.0326 (3)
C10.1102 (2)0.65006 (16)0.04709 (11)0.0183 (4)
C20.0742 (2)0.63855 (16)0.08456 (12)0.0219 (4)
C60.1841 (2)0.50915 (16)0.03731 (11)0.0206 (4)
C110.2303 (2)0.81224 (16)0.09757 (11)0.0208 (4)
O1W0.79377 (16)0.11269 (13)0.41900 (10)0.0298 (3)
H4A0.354400.584000.431600.0220*
H11A0.457 (3)0.811 (2)0.0983 (15)0.042 (5)*
H12A0.554 (3)0.952 (2)0.1349 (16)0.052 (5)*
H21A0.678900.737200.289800.0280*
H22A0.768400.678700.166600.0280*
H31A0.635000.438900.316700.0250*
H32A0.517200.480400.208400.0250*
H41A0.266 (3)0.130 (2)0.4741 (17)0.054 (5)*
H42A0.477 (3)0.233 (2)0.4429 (15)0.046 (5)*
H51A0.136400.673300.237600.0260*
H52A0.054000.730600.361600.0260*
H61A0.195200.967400.213700.0320*
H62A0.319900.916300.319500.0320*
H20.124200.730600.141700.0260*
H60.308500.514400.062200.0250*
H11W0.876 (3)0.189 (2)0.4192 (15)0.044 (5)*
H12W0.810 (3)0.102 (2)0.3396 (17)0.044 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0233 (6)0.0260 (5)0.0360 (6)0.0110 (4)0.0049 (4)0.0025 (4)
N1A0.0258 (6)0.0174 (5)0.0238 (6)0.0098 (5)0.0039 (5)0.0023 (5)
N41A0.0265 (7)0.0181 (6)0.0404 (7)0.0075 (5)0.0037 (6)0.0048 (5)
C2A0.0183 (7)0.0237 (7)0.0260 (7)0.0069 (5)0.0031 (5)0.0011 (5)
C3A0.0180 (7)0.0175 (6)0.0245 (7)0.0032 (5)0.0041 (5)0.0010 (5)
C4A0.0195 (7)0.0175 (6)0.0180 (6)0.0055 (5)0.0034 (5)0.0012 (5)
C5A0.0181 (7)0.0184 (6)0.0266 (7)0.0032 (5)0.0012 (5)0.0012 (5)
C6A0.0262 (8)0.0166 (6)0.0346 (8)0.0017 (5)0.0035 (6)0.0013 (6)
C41A0.0228 (7)0.0185 (6)0.0171 (6)0.0063 (5)0.0006 (5)0.0023 (5)
O110.0333 (6)0.0305 (5)0.0332 (6)0.0195 (4)0.0111 (5)0.0010 (4)
O120.0415 (6)0.0215 (5)0.0345 (6)0.0135 (4)0.0131 (5)0.0067 (4)
C10.0183 (7)0.0163 (6)0.0200 (6)0.0047 (5)0.0003 (5)0.0049 (5)
C20.0238 (7)0.0163 (6)0.0245 (7)0.0040 (5)0.0073 (6)0.0013 (5)
C60.0182 (7)0.0211 (6)0.0242 (7)0.0053 (5)0.0065 (5)0.0038 (5)
C110.0226 (7)0.0176 (6)0.0224 (7)0.0072 (5)0.0006 (5)0.0051 (5)
O1W0.0315 (6)0.0240 (5)0.0336 (6)0.0134 (4)0.0084 (5)0.0036 (4)
Geometric parameters (Å, º) top
O41A—C41A1.2336 (17)C5A—C6A1.5139 (19)
O11—C111.2637 (17)C2A—H22A0.9700
O12—C111.2476 (16)C2A—H21A0.9700
O1W—H12W0.932 (19)C3A—H31A0.9700
O1W—H11W0.861 (18)C3A—H32A0.9700
N1A—C6A1.4909 (18)C4A—H4A0.9800
N1A—C2A1.4943 (18)C5A—H52A0.9700
N41A—C41A1.3370 (18)C5A—H51A0.9700
N1A—H12A0.979 (17)C6A—H61A0.9700
N1A—H11A0.966 (17)C6A—H62A0.9700
N41A—H42A0.95 (2)C1—C61.3947 (18)
N41A—H41A0.927 (17)C1—C111.5184 (18)
C2A—C3A1.5192 (19)C1—C21.3894 (19)
C3A—C4A1.5353 (18)C2—C6i1.3860 (18)
C4A—C5A1.5327 (18)C2—H20.9300
C4A—C41A1.5292 (18)C6—H60.9300
H11W—O1W—H12W106.9 (16)H31A—C3A—H32A108.00
C2A—N1A—C6A111.57 (10)C2A—C3A—H31A109.00
C2A—N1A—H12A111.2 (11)C5A—C4A—H4A108.00
C6A—N1A—H11A109.2 (12)C41A—C4A—H4A108.00
C2A—N1A—H11A111.9 (10)C3A—C4A—H4A108.00
H11A—N1A—H12A103.9 (15)C4A—C5A—H52A109.00
C6A—N1A—H12A108.8 (10)C6A—C5A—H51A109.00
H41A—N41A—H42A120.6 (15)C6A—C5A—H52A109.00
C41A—N41A—H42A120.5 (10)H51A—C5A—H52A108.00
C41A—N41A—H41A118.5 (12)C4A—C5A—H51A109.00
N1A—C2A—C3A110.62 (11)N1A—C6A—H61A110.00
C2A—C3A—C4A112.00 (11)N1A—C6A—H62A110.00
C3A—C4A—C41A112.20 (10)C5A—C6A—H62A110.00
C5A—C4A—C41A110.45 (11)H61A—C6A—H62A108.00
C3A—C4A—C5A110.71 (10)C5A—C6A—H61A110.00
C4A—C5A—C6A111.97 (11)C2—C1—C6118.76 (12)
N1A—C6A—C5A110.47 (11)C2—C1—C11120.76 (11)
O41A—C41A—C4A120.74 (11)C6—C1—C11120.48 (12)
N41A—C41A—C4A116.78 (12)C1—C2—C6i120.46 (12)
O41A—C41A—N41A122.47 (12)C1—C6—C2i120.77 (12)
N1A—C2A—H21A110.00O11—C11—C1117.52 (11)
C3A—C2A—H21A110.00O12—C11—C1118.61 (12)
C3A—C2A—H22A110.00O11—C11—O12123.87 (12)
N1A—C2A—H22A110.00C1—C2—H2120.00
H21A—C2A—H22A108.00C6i—C2—H2120.00
C2A—C3A—H32A109.00C1—C6—H6120.00
C4A—C3A—H31A109.00C2i—C6—H6120.00
C4A—C3A—H32A109.00
C6A—N1A—C2A—C3A58.63 (14)C4A—C5A—C6A—N1A55.90 (14)
C2A—N1A—C6A—C5A59.19 (14)C6—C1—C2—C6i1.03 (19)
N1A—C2A—C3A—C4A54.73 (14)C11—C1—C2—C6i179.41 (12)
C2A—C3A—C4A—C5A51.45 (14)C2—C1—C6—C2i1.03 (19)
C2A—C3A—C4A—C41A175.35 (11)C11—C1—C6—C2i179.41 (12)
C3A—C4A—C5A—C6A52.06 (14)C2—C1—C11—O11169.25 (12)
C41A—C4A—C5A—C6A176.96 (11)C2—C1—C11—O1210.82 (18)
C3A—C4A—C41A—O41A130.14 (13)C6—C1—C11—O1111.19 (18)
C3A—C4A—C41A—N41A51.36 (15)C6—C1—C11—O12168.74 (12)
C5A—C4A—C41A—O41A6.10 (16)C1—C2—C6i—C1i1.05 (19)
C5A—C4A—C41A—N41A175.41 (11)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O110.966 (17)1.856 (18)2.7937 (16)162.9 (14)
N1A—H12A···O11ii0.979 (17)1.847 (17)2.8030 (15)164.7 (17)
N1A—H12A···O12ii0.979 (17)2.367 (19)3.1200 (16)133.3 (14)
N41A—H41A···O1Wiii0.927 (17)2.045 (17)2.9181 (16)156.5 (17)
N41A—H42A···O1W0.95 (2)2.111 (19)2.9870 (17)153.2 (14)
O1W—H11W···O41Aiv0.861 (18)1.892 (18)2.7410 (15)168.7 (17)
O1W—H12W···O12v0.932 (19)1.833 (19)2.7632 (15)175.6 (19)
C6A—H61A···O12vi0.972.523.3773 (18)147
Symmetry codes: (ii) x+1, y+2, z; (iii) x+1, y, z+1; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x, y+2, z.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC6H13N2O+·C8H4NO6C6H13N2O+·C8H3Cl2O4C6H13N2O+·C8H4NO62C6H13N2O8+·C8H4O42·2H2O
Mr339.31363.19339.31458.51
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/nMonoclinic, P21/cTriclinic, P1
Temperature (K)200200200200
a, b, c (Å)5.8637 (5), 11.2707 (8), 23.0268 (19)6.6897 (4), 9.7392 (5), 24.1222 (13)9.4117 (4), 14.3552 (5), 11.4490 (5)6.5099 (5), 7.7777 (6), 11.6865 (12)
α, β, γ (°)90, 93.082 (8), 9090, 92.479 (4), 9090, 103.787 (4), 9076.429 (8), 76.968 (7), 80.885 (7)
V3)1519.6 (2)1570.15 (15)1502.27 (11)556.89 (9)
Z4441
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.120.440.120.11
Crystal size (mm)0.40 × 0.40 × 0.120.30 × 0.25 × 0.200.45 × 0.40 × 0.180.50 × 0.15 × 0.08
Data collection
DiffractometerOxford Gemini-S CCD area-detector
diffractometer
Oxford Gemini S CCD area-detector
diffractometer
Oxford Gemini-S CCD area-detector
diffractometer
Oxford Gemini-S CCD are-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.915, 0.9800.908, 0.9800.98, 0.990.965, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
10364, 2989, 2375 19231, 3084, 2777 9866, 2940, 2284 6562, 2177, 1746
Rint0.0230.0280.0250.024
(sin θ/λ)max1)0.6170.6170.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.114, 1.05 0.046, 0.113, 1.30 0.037, 0.106, 1.01 0.034, 0.093, 1.05
No. of reflections2989308429402177
No. of parameters233224237169
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.260.37, 0.290.35, 0.240.23, 0.16

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O11i0.98 (3)1.77 (3)2.729 (2)163 (2)
N1A—H12A···O210.93 (3)1.92 (3)2.803 (2)158 (2)
N41A—H42A···O41Aii0.92 (3)1.99 (3)2.907 (3)176 (2)
N41A—H43A···O42iii0.83 (3)2.40 (3)3.200 (3)161 (3)
O22—H22···O12iv0.991.472.4562 (19)179
Symmetry codes: (i) x1, y, z; (ii) x+1, y+2, z+1; (iii) x3/2, y+3/2, z1/2; (iv) x+1/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O110.92 (4)1.90 (4)2.810 (3)170 (3)
N1A—H12A···O22i0.87 (4)1.96 (4)2.753 (3)152 (3)
N41A—H41A···O21ii0.82 (4)2.48 (4)3.158 (3)142 (4)
N41A—H42A···O41Aiii0.93 (4)2.19 (4)3.086 (4)163 (3)
O12—H12···O211.001.402.393 (3)180
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2; (iii) x+3/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O31i0.93 (2)2.06 (2)2.9236 (18)153.6 (17)
N1A—H12A···O110.98 (2)1.87 (2)2.8229 (16)164 (2)
N1A—H12A···O120.98 (2)2.45 (2)3.0366 (19)118.1 (17)
N41A—H41A···O11ii0.822 (19)2.298 (19)3.0669 (19)155.9 (17)
N41A—H42A···O41Aiii0.940 (19)1.996 (19)2.9321 (18)174.1 (16)
O32—H32···O12iv0.93 (2)1.63 (2)2.5336 (17)164 (3)
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x+1, y+1/2, z+1/2; (iii) x+1, y+2, z+1; (iv) x+2, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O110.966 (17)1.856 (18)2.7937 (16)162.9 (14)
N1A—H12A···O11i0.979 (17)1.847 (17)2.8030 (15)164.7 (17)
N1A—H12A···O12i0.979 (17)2.367 (19)3.1200 (16)133.3 (14)
N41A—H41A···O1Wii0.927 (17)2.045 (17)2.9181 (16)156.5 (17)
N41A—H42A···O1W0.95 (2)2.111 (19)2.9870 (17)153.2 (14)
O1W—H11W···O41Aiii0.861 (18)1.892 (18)2.7410 (15)168.7 (17)
O1W—H12W···O12iv0.932 (19)1.833 (19)2.7632 (15)175.6 (19)
Symmetry codes: (i) x+1, y+2, z; (ii) x+1, y, z+1; (iii) x+1, y, z; (iv) x+1, y+1, z.
 

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