Proton-transfer compounds of isonipecotamide with the aromatic dicarb­oxy­lic acids 4-nitro­phthalic, 4,5-dichloro­phthalic, 5-nitro­iso­phthalic and terephthalic acid

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⁺·C₈H₄O₄^2-·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.

S1. Comment

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···O_carboxyl ion-pair interaction. The hydrogen phthalate anions form head-to-tail hydrogen-bonded chain substructures featuring short carboxylic acid O—H···O_carboxyl 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···O_nitro and piperidinium N—H···O_carboxyl 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···O_carboxy, amide N—H···O_carboxy and amide N—H···O_amide hydrogen bonds from two INIPA cations and one DCPA anion, and is closed by the intramolecular carboxylic acid O—H···O_carboxyl 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···O<sub>carboxyl</sub> 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···O_carboxyl 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···O_carboxyl 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···O_carboxyl hydrogen bonds which involve two anions, enclosing cyclic R₃³(10) rings (Fig. 7). The three-dimensional framework structure is generated through amide N—H···O_carboxyl 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···O_carboxyl 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···O_carboxyl hydrogen bonds shown in Fig. 4, together with the water O—H···O_carboxyl 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

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2U_eq(C).

Computing details

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

	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.
	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.
	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.
	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.
	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.)
	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.)
	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.]
	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

Crystal data

C6H13N2O^+·C8H4NO6^−	F(000) = 712
Mr = 339.31	Dx = 1.483 Mg m^−3
Monoclinic, P21/n	Melting point: 467 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.8637 (5) Å	Cell parameters from 4796 reflections
b = 11.2707 (8) Å	θ = 3.2–28.8°
c = 23.0268 (19) Å	µ = 0.12 mm^−1
β = 93.082 (8)°	T = 200 K
V = 1519.6 (2) Å^3	Plate, colourless
Z = 4	0.40 × 0.40 × 0.12 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2989 independent reflections
Radiation source: Enhance (Mo) X-ray source	2375 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −7→6
Tmin = 0.915, Tmax = 0.980	k = −13→13
10364 measured reflections	l = −28→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.9247P] where P = (Fo^2 + 2Fc^2)/3
2989 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O41A	0.5071 (3)	0.87661 (14)	0.55291 (7)	0.0470 (6)
N1A	0.0153 (3)	0.63006 (16)	0.65455 (8)	0.0299 (6)
N41A	0.2315 (4)	0.9218 (2)	0.48579 (9)	0.0430 (7)
C2A	0.0994 (5)	0.5737 (2)	0.60175 (11)	0.0455 (8)
C3A	0.2620 (4)	0.65623 (19)	0.57243 (11)	0.0436 (8)
C4A	0.1494 (4)	0.77453 (18)	0.55762 (8)	0.0304 (6)
C5A	0.0609 (4)	0.82942 (19)	0.61283 (10)	0.0348 (7)
C6A	−0.0971 (4)	0.7461 (2)	0.64247 (11)	0.0424 (8)
C41A	0.3124 (4)	0.86121 (18)	0.53162 (8)	0.0298 (6)
O11	0.6413 (3)	0.51227 (13)	0.69033 (6)	0.0360 (5)
O12	0.4026 (2)	0.46519 (13)	0.75858 (6)	0.0348 (5)
O21	0.3549 (3)	0.72451 (13)	0.73146 (7)	0.0406 (5)
O22	0.3569 (2)	0.84857 (12)	0.80634 (6)	0.0307 (4)
O41	1.0325 (3)	0.85304 (16)	0.93918 (7)	0.0484 (6)
O42	1.2952 (3)	0.71969 (18)	0.93283 (8)	0.0547 (6)
N4	1.1086 (3)	0.76236 (17)	0.91794 (7)	0.0358 (6)
C1	0.7105 (3)	0.58879 (16)	0.78603 (8)	0.0219 (5)
C2	0.6377 (3)	0.69872 (16)	0.80700 (8)	0.0205 (5)
C3	0.7680 (3)	0.75455 (17)	0.85112 (8)	0.0244 (5)
C4	0.9697 (3)	0.70127 (17)	0.87223 (8)	0.0259 (6)
C5	1.0447 (3)	0.59532 (19)	0.85117 (9)	0.0309 (6)
C6	0.9130 (3)	0.53851 (18)	0.80846 (9)	0.0295 (6)
C11	0.5745 (3)	0.51917 (16)	0.74006 (9)	0.0243 (6)
C21	0.4318 (3)	0.75916 (16)	0.77889 (8)	0.0219 (5)
H4A	0.02000	0.76110	0.52970	0.0370*
H11A	−0.098 (5)	0.578 (2)	0.6715 (11)	0.050 (7)*
H12A	0.138 (5)	0.641 (2)	0.6813 (11)	0.046 (7)*
H21A	−0.02880	0.55490	0.57500	0.0550*
H22A	0.17740	0.50030	0.61220	0.0550*
H31A	0.31080	0.61940	0.53710	0.0520*
H32A	0.39630	0.66940	0.59810	0.0520*
H42A	0.318 (5)	0.983 (2)	0.4725 (12)	0.053 (8)*
H43A	0.104 (5)	0.902 (3)	0.4714 (13)	0.059 (9)*
H51A	0.18920	0.84900	0.63940	0.0420*
H52A	−0.01990	0.90240	0.60290	0.0420*
H61A	−0.14110	0.78110	0.67870	0.0510*
H62A	−0.23450	0.73400	0.61780	0.0510*
H3	0.72110	0.82640	0.86630	0.0290*
H5	1.18200	0.56250	0.86550	0.0370*
H6	0.96000	0.46560	0.79440	0.0350*
H22	0.25130	0.89510	0.78030	0.0370*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0394 (10)	0.0472 (10)	0.0533 (10)	−0.0162 (8)	−0.0076 (8)	0.0227 (8)
N1A	0.0290 (10)	0.0349 (10)	0.0257 (9)	−0.0114 (8)	0.0004 (8)	0.0048 (7)
N41A	0.0359 (12)	0.0520 (13)	0.0407 (12)	−0.0080 (10)	−0.0005 (9)	0.0226 (10)
C2A	0.0645 (17)	0.0317 (12)	0.0421 (13)	−0.0095 (12)	0.0186 (12)	0.0007 (10)
C3A	0.0569 (16)	0.0316 (12)	0.0446 (14)	−0.0015 (11)	0.0232 (12)	0.0045 (10)
C4A	0.0325 (11)	0.0348 (11)	0.0234 (10)	−0.0111 (9)	−0.0043 (8)	0.0043 (8)
C5A	0.0317 (12)	0.0311 (11)	0.0422 (13)	0.0008 (9)	0.0085 (10)	0.0070 (9)
C6A	0.0335 (13)	0.0444 (13)	0.0505 (14)	−0.0008 (10)	0.0134 (11)	0.0102 (11)
C41A	0.0357 (12)	0.0308 (11)	0.0230 (10)	−0.0024 (9)	0.0033 (9)	0.0016 (8)
O11	0.0379 (9)	0.0366 (8)	0.0348 (8)	−0.0131 (7)	0.0137 (7)	−0.0089 (7)
O12	0.0297 (8)	0.0386 (8)	0.0369 (8)	−0.0172 (7)	0.0107 (6)	−0.0063 (7)
O21	0.0411 (9)	0.0388 (9)	0.0396 (9)	0.0146 (7)	−0.0194 (7)	−0.0125 (7)
O22	0.0334 (8)	0.0281 (7)	0.0303 (8)	0.0120 (6)	−0.0015 (6)	−0.0022 (6)
O41	0.0539 (11)	0.0506 (10)	0.0396 (9)	−0.0067 (9)	−0.0078 (8)	−0.0139 (8)
O42	0.0345 (10)	0.0814 (13)	0.0458 (10)	0.0067 (9)	−0.0198 (8)	−0.0017 (9)
N4	0.0351 (11)	0.0448 (11)	0.0268 (9)	−0.0070 (9)	−0.0033 (8)	0.0032 (8)
C1	0.0190 (9)	0.0212 (9)	0.0261 (10)	−0.0015 (7)	0.0065 (7)	0.0042 (7)
C2	0.0185 (9)	0.0203 (9)	0.0228 (9)	−0.0028 (7)	0.0024 (7)	0.0026 (7)
C3	0.0277 (10)	0.0217 (9)	0.0239 (9)	−0.0015 (8)	0.0023 (8)	0.0017 (8)
C4	0.0234 (10)	0.0332 (11)	0.0208 (9)	−0.0075 (8)	−0.0023 (8)	0.0045 (8)
C5	0.0223 (10)	0.0341 (11)	0.0363 (11)	0.0046 (9)	0.0005 (9)	0.0075 (9)
C6	0.0240 (11)	0.0244 (10)	0.0404 (12)	0.0044 (8)	0.0052 (9)	0.0005 (9)
C11	0.0234 (10)	0.0169 (9)	0.0331 (11)	0.0015 (8)	0.0075 (8)	−0.0010 (8)
C21	0.0224 (10)	0.0183 (9)	0.0250 (9)	−0.0010 (7)	0.0010 (8)	0.0008 (7)

Geometric parameters (Å, º)

O41A—C41A	1.230 (3)	C2A—H21A	0.9700
O11—C11	1.233 (2)	C2A—H22A	0.9700
O12—C11	1.271 (2)	C3A—H31A	0.9700
O21—C21	1.223 (2)	C3A—H32A	0.9700
O22—C21	1.280 (2)	C4A—H4A	0.9800
O41—N4	1.227 (3)	C5A—H51A	0.9700
O42—N4	1.227 (3)	C5A—H52A	0.9700
O22—H22	0.9900	C6A—H62A	0.9700
N1A—C2A	1.480 (3)	C6A—H61A	0.9700
N1A—C6A	1.484 (3)	C1—C2	1.405 (3)
N41A—C41A	1.323 (3)	C1—C11	1.510 (3)
N1A—H12A	0.93 (3)	C1—C6	1.390 (3)
N1A—H11A	0.98 (3)	C2—C3	1.389 (3)
N41A—H42A	0.92 (3)	C2—C21	1.502 (3)
N41A—H43A	0.83 (3)	C3—C4	1.391 (3)
N4—C4	1.467 (3)	C4—C5	1.370 (3)
C2A—C3A	1.516 (3)	C5—C6	1.376 (3)
C3A—C4A	1.519 (3)	C3—H3	0.9300
C4A—C41A	1.513 (3)	C5—H5	0.9300
C4A—C5A	1.529 (3)	C6—H6	0.9300
C5A—C6A	1.508 (3)
C21—O22—H22	110.00	C3A—C4A—H4A	109.00
C2A—N1A—C6A	112.87 (18)	C4A—C5A—H52A	109.00
C2A—N1A—H12A	108.7 (16)	C6A—C5A—H51A	109.00
C6A—N1A—H11A	107.3 (15)	C4A—C5A—H51A	109.00
C2A—N1A—H11A	109.4 (14)	C6A—C5A—H52A	109.00
H11A—N1A—H12A	109 (2)	H51A—C5A—H52A	108.00
C6A—N1A—H12A	109.1 (14)	N1A—C6A—H62A	109.00
H42A—N41A—H43A	125 (3)	C5A—C6A—H61A	110.00
C41A—N41A—H43A	117 (2)	C5A—C6A—H62A	109.00
C41A—N41A—H42A	118.2 (18)	N1A—C6A—H61A	109.00
O41—N4—O42	123.56 (19)	H61A—C6A—H62A	108.00
O41—N4—C4	118.48 (17)	C2—C1—C11	122.71 (16)
O42—N4—C4	117.95 (18)	C6—C1—C11	117.19 (16)
N1A—C2A—C3A	110.35 (18)	C2—C1—C6	120.09 (17)
C2A—C3A—C4A	111.3 (2)	C1—C2—C21	120.26 (16)
C5A—C4A—C41A	108.52 (17)	C3—C2—C21	120.50 (16)
C3A—C4A—C5A	109.35 (17)	C1—C2—C3	119.07 (16)
C3A—C4A—C41A	112.31 (19)	C2—C3—C4	118.96 (17)
C4A—C5A—C6A	111.62 (18)	N4—C4—C3	118.49 (17)
N1A—C6A—C5A	110.86 (18)	C3—C4—C5	122.39 (17)
O41A—C41A—C4A	121.73 (18)	N4—C4—C5	119.11 (16)
N41A—C41A—C4A	116.2 (2)	C4—C5—C6	118.70 (17)
O41A—C41A—N41A	122.0 (2)	C1—C6—C5	120.76 (18)
H21A—C2A—H22A	108.00	O11—C11—C1	120.12 (17)
N1A—C2A—H22A	110.00	O12—C11—C1	114.33 (17)
N1A—C2A—H21A	110.00	O11—C11—O12	125.39 (18)
C3A—C2A—H22A	110.00	O21—C21—C2	119.29 (17)
C3A—C2A—H21A	110.00	O22—C21—C2	115.69 (16)
C2A—C3A—H31A	109.00	O21—C21—O22	124.94 (17)
C4A—C3A—H31A	109.00	C2—C3—H3	121.00
H31A—C3A—H32A	108.00	C4—C3—H3	121.00
C2A—C3A—H32A	109.00	C4—C5—H5	121.00
C4A—C3A—H32A	109.00	C6—C5—H5	121.00
C41A—C4A—H4A	109.00	C1—C6—H6	120.00
C5A—C4A—H4A	109.00	C5—C6—H6	120.00
C6A—N1A—C2A—C3A	56.6 (3)	C11—C1—C2—C21	−7.4 (3)
C2A—N1A—C6A—C5A	−55.9 (3)	C2—C1—C6—C5	−0.1 (3)
O41—N4—C4—C3	6.0 (3)	C11—C1—C6—C5	−178.87 (18)
O41—N4—C4—C5	−175.20 (18)	C2—C1—C11—O11	107.7 (2)
O42—N4—C4—C3	−174.03 (18)	C2—C1—C11—O12	−76.7 (2)
O42—N4—C4—C5	4.8 (3)	C6—C1—C11—O11	−73.6 (2)
N1A—C2A—C3A—C4A	−56.8 (3)	C6—C1—C11—O12	102.0 (2)
C2A—C3A—C4A—C5A	56.0 (2)	C1—C2—C3—C4	1.6 (3)
C2A—C3A—C4A—C41A	176.54 (18)	C21—C2—C3—C4	−173.75 (17)
C5A—C4A—C41A—O41A	75.2 (3)	C1—C2—C21—O21	−14.0 (3)
C5A—C4A—C41A—N41A	−103.0 (2)	C1—C2—C21—O22	169.25 (16)
C3A—C4A—C41A—O41A	−45.8 (3)	C3—C2—C21—O21	161.27 (18)
C3A—C4A—C5A—C6A	−55.2 (2)	C3—C2—C21—O22	−15.5 (3)
C41A—C4A—C5A—C6A	−178.04 (18)	C2—C3—C4—N4	178.65 (17)
C3A—C4A—C41A—N41A	136.0 (2)	C2—C3—C4—C5	−0.2 (3)
C4A—C5A—C6A—N1A	54.9 (2)	N4—C4—C5—C6	179.79 (17)
C6—C1—C2—C3	−1.4 (3)	C3—C4—C5—C6	−1.4 (3)
C6—C1—C2—C21	173.89 (17)	C4—C5—C6—C1	1.5 (3)
C11—C1—C2—C3	177.23 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11^i	0.98 (3)	1.77 (3)	2.729 (2)	163 (2)
N1A—H12A···O21	0.93 (3)	1.92 (3)	2.803 (2)	158 (2)
N41A—H42A···O41A^ii	0.92 (3)	1.99 (3)	2.907 (3)	176 (2)
N41A—H43A···O42^iii	0.83 (3)	2.40 (3)	3.200 (3)	161 (3)
O22—H22···O12^iv	0.99	1.47	2.4562 (19)	179
C4A—H4A···O42^iii	0.98	2.54	3.454 (3)	156
C2A—H22A···O22^v	0.97	2.55	3.305 (3)	134

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) x−3/2, −y+3/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1/2, y−1/2, −z+3/2.

(II) 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C6H13N2O^+·C8H3Cl2O4^−	F(000) = 752
Mr = 363.19	Dx = 1.536 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8871 reflections
a = 6.6897 (4) Å	θ = 3.1–28.9°
b = 9.7392 (5) Å	µ = 0.44 mm^−1
c = 24.1222 (13) Å	T = 200 K
β = 92.479 (4)°	Block, colourless
V = 1570.15 (15) Å^3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Oxford Gemini S CCD area-detector diffractometer	3084 independent reflections
Radiation source: Enhance (Mo) X-ray source	2777 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −8→8
Tmin = 0.908, Tmax = 0.980	k = −12→12
19231 measured reflections	l = −29→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	w = 1/[σ^2(Fo^2) + (0.0177P)^2 + 2.734P] where P = (Fo^2 + 2Fc^2)/3
3084 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O41A	0.7063 (4)	0.2890 (2)	0.24101 (10)	0.0453 (9)
N1A	0.8063 (4)	0.4798 (3)	0.42405 (10)	0.0251 (8)
N41A	0.7344 (5)	0.5032 (4)	0.20550 (11)	0.0379 (10)
C2A	0.9600 (4)	0.5342 (3)	0.38672 (11)	0.0278 (9)
C3A	0.9429 (4)	0.4642 (3)	0.33052 (12)	0.0284 (9)
C4A	0.7313 (4)	0.4792 (3)	0.30467 (11)	0.0234 (8)
C5A	0.5823 (5)	0.4163 (3)	0.34351 (12)	0.0283 (9)
C6A	0.5975 (4)	0.4870 (3)	0.39972 (12)	0.0278 (9)
C41A	0.7207 (5)	0.4135 (3)	0.24744 (12)	0.0292 (9)
Cl4	0.70276 (15)	1.20000 (9)	0.67633 (3)	0.0436 (3)
Cl5	0.73906 (13)	0.88021 (9)	0.70518 (3)	0.0346 (2)
O11	0.7966 (3)	0.6468 (2)	0.51891 (8)	0.0312 (7)
O12	0.7517 (4)	0.7842 (2)	0.44724 (8)	0.0365 (7)
O21	0.7440 (3)	1.0235 (2)	0.42476 (8)	0.0309 (7)
O22	0.7514 (4)	1.2225 (2)	0.46816 (9)	0.0393 (8)
C1	0.7580 (4)	0.8846 (3)	0.53926 (11)	0.0194 (7)
C2	0.7464 (4)	1.0267 (3)	0.52629 (11)	0.0201 (8)
C3	0.7329 (4)	1.1194 (3)	0.57002 (12)	0.0250 (8)
C4	0.7292 (4)	1.0782 (3)	0.62488 (11)	0.0245 (8)
C5	0.7429 (4)	0.9395 (3)	0.63756 (11)	0.0231 (8)
C6	0.7570 (4)	0.8455 (3)	0.59506 (11)	0.0219 (8)
C11	0.7709 (4)	0.7639 (3)	0.49947 (11)	0.0237 (8)
C21	0.7479 (4)	1.0964 (3)	0.46933 (12)	0.0246 (8)
H4A	0.70120	0.57720	0.30060	0.0280*
H11A	0.818 (5)	0.531 (4)	0.4561 (15)	0.041 (10)*
H12A	0.827 (5)	0.394 (4)	0.4321 (15)	0.041 (10)*
H21A	1.09250	0.51870	0.40350	0.0330*
H22A	0.94170	0.63240	0.38200	0.0330*
H31A	0.97510	0.36750	0.33480	0.0340*
H32A	1.03810	0.50460	0.30610	0.0340*
H41A	0.737 (5)	0.467 (4)	0.1749 (16)	0.038 (10)*
H42A	0.759 (6)	0.595 (4)	0.2140 (15)	0.043 (11)*
H51A	0.44760	0.42620	0.32750	0.0340*
H52A	0.60990	0.31900	0.34810	0.0340*
H61A	0.55780	0.58240	0.39550	0.0330*
H62A	0.50710	0.44320	0.42460	0.0330*
H3	0.72610	1.21270	0.56200	0.0300*
H6	0.76610	0.75270	0.60390	0.0260*
H12	0.74890	0.88380	0.43800	0.0440*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0668 (18)	0.0325 (14)	0.0373 (13)	−0.0036 (12)	0.0091 (12)	−0.0144 (10)
N1A	0.0399 (15)	0.0181 (13)	0.0176 (12)	0.0011 (11)	0.0035 (10)	0.0015 (10)
N41A	0.0473 (18)	0.0476 (19)	0.0188 (13)	0.0047 (15)	0.0016 (12)	0.0000 (13)
C2A	0.0276 (16)	0.0319 (16)	0.0238 (14)	−0.0008 (13)	0.0002 (12)	0.0005 (12)
C3A	0.0281 (16)	0.0329 (17)	0.0246 (14)	0.0010 (13)	0.0052 (12)	−0.0023 (12)
C4A	0.0325 (16)	0.0161 (13)	0.0218 (13)	0.0015 (12)	0.0034 (12)	0.0005 (11)
C5A	0.0291 (16)	0.0296 (16)	0.0263 (14)	−0.0068 (13)	0.0036 (12)	−0.0041 (12)
C6A	0.0308 (16)	0.0283 (16)	0.0250 (14)	−0.0024 (13)	0.0085 (12)	−0.0018 (12)
C41A	0.0291 (17)	0.0332 (18)	0.0256 (14)	0.0019 (13)	0.0032 (12)	−0.0046 (13)
Cl4	0.0669 (6)	0.0320 (4)	0.0322 (4)	−0.0029 (4)	0.0072 (4)	−0.0148 (3)
Cl5	0.0467 (5)	0.0405 (4)	0.0167 (3)	−0.0004 (4)	0.0042 (3)	0.0023 (3)
O11	0.0497 (14)	0.0189 (10)	0.0250 (10)	0.0022 (10)	0.0033 (9)	−0.0003 (8)
O12	0.0677 (16)	0.0235 (11)	0.0182 (10)	0.0047 (11)	0.0001 (10)	−0.0018 (8)
O21	0.0436 (13)	0.0308 (12)	0.0184 (10)	−0.0001 (10)	0.0018 (9)	0.0055 (8)
O22	0.0601 (16)	0.0216 (12)	0.0364 (12)	−0.0040 (11)	0.0031 (11)	0.0110 (9)
C1	0.0193 (13)	0.0200 (13)	0.0190 (12)	−0.0016 (11)	0.0012 (10)	−0.0004 (10)
C2	0.0173 (13)	0.0215 (14)	0.0214 (13)	−0.0008 (11)	0.0004 (10)	0.0012 (11)
C3	0.0281 (15)	0.0174 (13)	0.0296 (15)	−0.0021 (12)	0.0016 (12)	0.0002 (12)
C4	0.0270 (15)	0.0236 (15)	0.0230 (14)	−0.0032 (12)	0.0018 (11)	−0.0071 (11)
C5	0.0230 (14)	0.0292 (15)	0.0171 (13)	−0.0027 (12)	0.0012 (11)	0.0008 (11)
C6	0.0248 (14)	0.0193 (14)	0.0216 (13)	−0.0006 (11)	0.0026 (11)	0.0023 (11)
C11	0.0269 (15)	0.0229 (14)	0.0214 (13)	−0.0014 (12)	0.0036 (11)	−0.0009 (11)
C21	0.0221 (14)	0.0245 (15)	0.0272 (15)	−0.0018 (12)	0.0026 (11)	0.0066 (12)

Geometric parameters (Å, º)

Cl4—C4	1.731 (3)	C2A—H22A	0.9700
Cl5—C5	1.732 (3)	C2A—H21A	0.9700
O41A—C41A	1.226 (4)	C3A—H31A	0.9700
O11—C11	1.242 (3)	C3A—H32A	0.9700
O12—C11	1.276 (3)	C4A—H4A	0.9800
O21—C21	1.288 (3)	C5A—H51A	0.9700
O22—C21	1.229 (4)	C5A—H52A	0.9700
O12—H12	1.0000	C6A—H62A	0.9700
N1A—C2A	1.493 (4)	C6A—H61A	0.9700
N1A—C6A	1.493 (4)	C1—C2	1.420 (4)
N41A—C41A	1.343 (4)	C1—C11	1.522 (4)
N1A—H12A	0.87 (4)	C1—C6	1.399 (4)
N1A—H11A	0.92 (4)	C2—C21	1.533 (4)
N41A—H42A	0.93 (4)	C2—C3	1.394 (4)
N41A—H41A	0.82 (4)	C3—C4	1.384 (4)
C2A—C3A	1.517 (4)	C4—C5	1.387 (4)
C3A—C4A	1.529 (4)	C5—C6	1.381 (4)
C4A—C41A	1.521 (4)	C3—H3	0.9300
C4A—C5A	1.526 (4)	C6—H6	0.9300
C5A—C6A	1.520 (4)
C11—O12—H12	112.00	C6A—C5A—H52A	110.00
C2A—N1A—C6A	113.8 (2)	H51A—C5A—H52A	108.00
C6A—N1A—H11A	110 (2)	C4A—C5A—H52A	110.00
C2A—N1A—H11A	106 (2)	C4A—C5A—H51A	110.00
C2A—N1A—H12A	112 (2)	C5A—C6A—H61A	109.00
C6A—N1A—H12A	106 (2)	N1A—C6A—H61A	109.00
H11A—N1A—H12A	109 (3)	N1A—C6A—H62A	110.00
H41A—N41A—H42A	127 (4)	H61A—C6A—H62A	108.00
C41A—N41A—H42A	118 (2)	C5A—C6A—H62A	109.00
C41A—N41A—H41A	114 (3)	C2—C1—C11	128.1 (2)
N1A—C2A—C3A	110.6 (2)	C2—C1—C6	118.3 (3)
C2A—C3A—C4A	110.7 (2)	C6—C1—C11	113.5 (2)
C5A—C4A—C41A	112.5 (2)	C1—C2—C21	128.8 (2)
C3A—C4A—C5A	109.2 (2)	C1—C2—C3	118.0 (2)
C3A—C4A—C41A	109.6 (2)	C3—C2—C21	113.2 (3)
C4A—C5A—C6A	110.2 (2)	C2—C3—C4	122.7 (3)
N1A—C6A—C5A	110.8 (2)	Cl4—C4—C5	121.1 (2)
O41A—C41A—N41A	123.8 (3)	C3—C4—C5	119.3 (3)
O41A—C41A—C4A	122.1 (3)	Cl4—C4—C3	119.6 (2)
N41A—C41A—C4A	114.1 (3)	C4—C5—C6	119.2 (2)
N1A—C2A—H22A	110.00	Cl5—C5—C4	121.9 (2)
N1A—C2A—H21A	109.00	Cl5—C5—C6	118.9 (2)
H21A—C2A—H22A	108.00	C1—C6—C5	122.5 (3)
C3A—C2A—H21A	110.00	O11—C11—C1	118.8 (2)
C3A—C2A—H22A	109.00	O12—C11—C1	119.8 (2)
C4A—C3A—H31A	109.00	O11—C11—O12	121.4 (3)
C4A—C3A—H32A	110.00	O22—C21—C2	117.7 (3)
H31A—C3A—H32A	108.00	O21—C21—O22	122.1 (3)
C2A—C3A—H32A	110.00	O21—C21—C2	120.2 (2)
C2A—C3A—H31A	109.00	C2—C3—H3	119.00
C5A—C4A—H4A	108.00	C4—C3—H3	119.00
C3A—C4A—H4A	108.00	C1—C6—H6	119.00
C41A—C4A—H4A	109.00	C5—C6—H6	119.00
C6A—C5A—H51A	110.00
C6A—N1A—C2A—C3A	−53.9 (3)	C2—C1—C11—O11	174.1 (3)
C2A—N1A—C6A—C5A	54.3 (3)	C2—C1—C11—O12	−7.1 (4)
N1A—C2A—C3A—C4A	55.6 (3)	C6—C1—C11—O11	−6.2 (4)
C2A—C3A—C4A—C5A	−58.7 (3)	C6—C1—C11—O12	172.6 (3)
C2A—C3A—C4A—C41A	177.6 (2)	C1—C2—C3—C4	−0.4 (4)
C3A—C4A—C5A—C6A	58.8 (3)	C21—C2—C3—C4	180.0 (2)
C41A—C4A—C5A—C6A	−179.2 (2)	C1—C2—C21—O21	5.9 (4)
C3A—C4A—C41A—O41A	78.8 (4)	C1—C2—C21—O22	−174.7 (3)
C3A—C4A—C41A—N41A	−99.4 (3)	C3—C2—C21—O21	−174.6 (2)
C5A—C4A—C41A—O41A	−43.0 (4)	C3—C2—C21—O22	4.9 (4)
C5A—C4A—C41A—N41A	138.9 (3)	C2—C3—C4—Cl4	−177.6 (2)
C4A—C5A—C6A—N1A	−56.3 (3)	C2—C3—C4—C5	1.2 (4)
C6—C1—C2—C3	−0.5 (4)	Cl4—C4—C5—Cl5	−1.2 (3)
C6—C1—C2—C21	179.0 (3)	Cl4—C4—C5—C6	177.8 (2)
C11—C1—C2—C3	179.1 (3)	C3—C4—C5—Cl5	−180.0 (2)
C11—C1—C2—C21	−1.3 (5)	C3—C4—C5—C6	−0.9 (4)
C2—C1—C6—C5	0.8 (4)	Cl5—C5—C6—C1	179.0 (2)
C11—C1—C6—C5	−179.0 (2)	C4—C5—C6—C1	0.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11	0.92 (4)	1.90 (4)	2.810 (3)	170 (3)
N1A—H11A···O12	0.92 (4)	2.51 (4)	3.042 (4)	117 (3)
N1A—H12A···O22^i	0.87 (4)	1.96 (4)	2.753 (3)	152 (3)
N41A—H41A···O21^ii	0.82 (4)	2.48 (4)	3.158 (3)	142 (4)
N41A—H42A···O41A^iii	0.93 (4)	2.19 (4)	3.086 (4)	163 (3)
O12—H12···O21	1.00	1.40	2.393 (3)	180
C3—H3···O22	0.93	2.28	2.662 (4)	104
C4A—H4A···O41A^iii	0.98	2.39	3.245 (4)	146
C6—H6···O11	0.93	2.31	2.689 (3)	104
C2A—H21A···O11^iv	0.97	2.56	3.259 (3)	129
C2A—H22A···O12	0.97	2.54	3.190 (4)	124

Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −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

Crystal data

C6H13N2O^+·C8H4NO6^−	F(000) = 712
Mr = 339.31	Dx = 1.500 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4846 reflections
a = 9.4117 (4) Å	θ = 3.2–28.7°
b = 14.3552 (5) Å	µ = 0.12 mm^−1
c = 11.4490 (5) Å	T = 200 K
β = 103.787 (4)°	Plate, colourless
V = 1502.27 (11) Å^3	0.45 × 0.40 × 0.18 mm
Z = 4

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2940 independent reflections
Radiation source: fine-focus sealed tube	2284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −11→11
Tmin = 0.98, Tmax = 0.99	k = −17→17
9866 measured reflections	l = −14→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0694P)^2] where P = (Fo^2 + 2Fc^2)/3
2940 reflections	(Δ/σ)max = 0.001
237 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O41A	0.59457 (16)	0.89483 (8)	0.55593 (10)	0.0441 (4)
N1A	0.75063 (17)	0.59544 (9)	0.44483 (12)	0.0274 (4)
N41A	0.45092 (16)	0.91398 (9)	0.37052 (13)	0.0276 (4)
C2A	0.6261 (2)	0.60070 (10)	0.50398 (16)	0.0329 (5)
C3A	0.5943 (2)	0.70018 (11)	0.53417 (15)	0.0308 (5)
C4A	0.56894 (18)	0.76325 (10)	0.42330 (14)	0.0259 (5)
C5A	0.7036 (2)	0.75760 (10)	0.37175 (14)	0.0297 (5)
C6A	0.7315 (2)	0.65785 (10)	0.33822 (14)	0.0335 (6)
C41A	0.53807 (19)	0.86299 (10)	0.45496 (14)	0.0263 (5)
O11	0.72771 (14)	0.40335 (7)	0.39084 (10)	0.0310 (4)
O12	0.90850 (18)	0.42023 (8)	0.55448 (11)	0.0504 (5)
O31	1.04577 (13)	0.14479 (7)	0.82832 (9)	0.0309 (4)
O32	0.96788 (14)	0.00396 (7)	0.75335 (10)	0.0318 (4)
O51	0.75616 (14)	−0.03200 (7)	0.32869 (10)	0.0342 (4)
O52	0.6672 (2)	0.08685 (8)	0.22188 (12)	0.0623 (5)
N51	0.73297 (16)	0.05155 (9)	0.31637 (11)	0.0280 (4)
C1	0.82957 (18)	0.26747 (10)	0.49770 (13)	0.0224 (4)
C2	0.89685 (18)	0.22902 (10)	0.60935 (13)	0.0232 (4)
C3	0.90771 (17)	0.13329 (10)	0.62527 (13)	0.0217 (4)
C4	0.85331 (17)	0.07377 (10)	0.52947 (13)	0.0221 (4)
C5	0.78839 (17)	0.11326 (10)	0.41904 (13)	0.0216 (4)
C6	0.77429 (18)	0.20842 (10)	0.40177 (13)	0.0223 (4)
C11	0.8197 (2)	0.37206 (10)	0.47962 (13)	0.0276 (5)
C31	0.98111 (18)	0.09530 (10)	0.74656 (14)	0.0239 (5)
H4A	0.48430	0.73990	0.36310	0.0310*
H11A	0.836 (2)	0.6109 (14)	0.5012 (19)	0.051 (6)*
H12A	0.756 (3)	0.5313 (15)	0.417 (2)	0.061 (6)*
H21A	0.64880	0.56400	0.57720	0.0390*
H22A	0.53950	0.57420	0.45090	0.0390*
H31A	0.67590	0.72390	0.59530	0.0370*
H32A	0.50810	0.70120	0.56670	0.0370*
H41A	0.414 (2)	0.8948 (12)	0.3024 (17)	0.036 (5)*
H42A	0.433 (2)	0.9761 (13)	0.3885 (16)	0.036 (5)*
H51A	0.68950	0.79680	0.30090	0.0360*
H52A	0.78810	0.78060	0.43070	0.0360*
H61A	0.64980	0.63620	0.27550	0.0400*
H62A	0.81880	0.65580	0.30720	0.0400*
H2	0.93490	0.26820	0.67390	0.0280*
H4	0.86020	0.00950	0.53900	0.0260*
H6	0.72840	0.23250	0.32690	0.0270*
H32	1.026 (3)	−0.0185 (15)	0.825 (2)	0.067 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0673 (10)	0.0278 (6)	0.0267 (6)	0.0133 (6)	−0.0098 (6)	−0.0068 (5)
N1A	0.0347 (9)	0.0150 (6)	0.0268 (7)	0.0030 (6)	−0.0038 (7)	0.0000 (5)
N41A	0.0314 (8)	0.0216 (7)	0.0259 (7)	0.0066 (6)	−0.0006 (6)	−0.0016 (6)
C2A	0.0344 (10)	0.0223 (8)	0.0382 (9)	−0.0032 (7)	0.0013 (8)	0.0105 (7)
C3A	0.0349 (11)	0.0273 (8)	0.0324 (9)	0.0030 (7)	0.0122 (8)	0.0065 (7)
C4A	0.0296 (10)	0.0183 (8)	0.0247 (8)	0.0009 (7)	−0.0034 (7)	−0.0012 (6)
C5A	0.0500 (12)	0.0167 (7)	0.0233 (8)	0.0047 (7)	0.0105 (8)	0.0025 (6)
C6A	0.0558 (13)	0.0198 (8)	0.0245 (8)	0.0087 (8)	0.0088 (8)	0.0020 (6)
C41A	0.0298 (9)	0.0213 (8)	0.0266 (8)	0.0019 (7)	0.0044 (7)	−0.0006 (6)
O11	0.0418 (8)	0.0170 (5)	0.0285 (6)	0.0040 (5)	−0.0028 (5)	0.0024 (4)
O12	0.0814 (11)	0.0200 (6)	0.0343 (7)	−0.0081 (6)	−0.0166 (7)	−0.0063 (5)
O31	0.0363 (7)	0.0286 (6)	0.0227 (6)	−0.0010 (5)	−0.0033 (5)	0.0027 (4)
O32	0.0415 (8)	0.0226 (6)	0.0255 (6)	−0.0028 (5)	−0.0033 (6)	0.0085 (4)
O51	0.0482 (8)	0.0149 (5)	0.0383 (7)	−0.0017 (5)	0.0078 (6)	−0.0053 (4)
O52	0.1003 (13)	0.0318 (7)	0.0324 (7)	0.0136 (7)	−0.0285 (8)	−0.0090 (5)
N51	0.0335 (9)	0.0211 (7)	0.0258 (7)	0.0015 (6)	0.0001 (6)	−0.0038 (5)
C1	0.0267 (9)	0.0177 (7)	0.0210 (7)	−0.0002 (6)	0.0020 (7)	−0.0007 (6)
C2	0.0274 (9)	0.0202 (7)	0.0201 (7)	−0.0027 (7)	0.0019 (6)	−0.0021 (5)
C3	0.0213 (8)	0.0213 (7)	0.0219 (8)	−0.0010 (6)	0.0040 (6)	0.0030 (6)
C4	0.0238 (8)	0.0151 (7)	0.0261 (8)	0.0013 (6)	0.0037 (7)	0.0026 (6)
C5	0.0230 (8)	0.0177 (7)	0.0227 (7)	0.0007 (6)	0.0027 (6)	−0.0026 (6)
C6	0.0266 (9)	0.0182 (7)	0.0196 (7)	0.0025 (6)	0.0005 (6)	0.0019 (6)
C11	0.0393 (10)	0.0184 (7)	0.0223 (8)	0.0007 (7)	0.0019 (7)	−0.0013 (6)
C31	0.0234 (9)	0.0237 (8)	0.0231 (8)	−0.0005 (7)	0.0027 (7)	0.0042 (6)

Geometric parameters (Å, º)

O41A—C41A	1.2390 (19)	C2A—H21A	0.9700
O11—C11	1.251 (2)	C2A—H22A	0.9700
O12—C11	1.253 (2)	C3A—H31A	0.9700
O31—C31	1.2165 (18)	C3A—H32A	0.9700
O32—C31	1.3211 (18)	C4A—H4A	0.9800
O51—N51	1.2212 (16)	C5A—H51A	0.9700
O52—N51	1.2211 (19)	C5A—H52A	0.9700
O32—H32	0.93 (2)	C6A—H62A	0.9700
N1A—C2A	1.489 (2)	C6A—H61A	0.9700
N1A—C6A	1.490 (2)	C1—C2	1.398 (2)
N41A—C41A	1.329 (2)	C1—C11	1.515 (2)
N1A—H12A	0.98 (2)	C1—C6	1.387 (2)
N1A—H11A	0.93 (2)	C2—C3	1.387 (2)
N41A—H41A	0.822 (19)	C3—C4	1.388 (2)
N41A—H42A	0.940 (19)	C3—C31	1.499 (2)
N51—C5	1.4650 (19)	C4—C5	1.387 (2)
C2A—C3A	1.516 (2)	C5—C6	1.382 (2)
C3A—C4A	1.531 (2)	C2—H2	0.9300
C4A—C41A	1.522 (2)	C4—H4	0.9300
C4A—C5A	1.522 (3)	C6—H6	0.9300
C5A—C6A	1.521 (2)
C31—O32—H32	110.7 (14)	C3A—C4A—H4A	109.00
C2A—N1A—C6A	112.81 (14)	C4A—C5A—H52A	109.00
C2A—N1A—H12A	107.6 (16)	C6A—C5A—H51A	109.00
C6A—N1A—H11A	109.9 (13)	C4A—C5A—H51A	109.00
C2A—N1A—H11A	108.4 (12)	C6A—C5A—H52A	109.00
H11A—N1A—H12A	110 (2)	H51A—C5A—H52A	108.00
C6A—N1A—H12A	107.7 (13)	N1A—C6A—H62A	110.00
H41A—N41A—H42A	117.9 (17)	C5A—C6A—H61A	110.00
C41A—N41A—H42A	118.4 (11)	C5A—C6A—H62A	109.00
C41A—N41A—H41A	123.6 (13)	N1A—C6A—H61A	109.00
O51—N51—O52	123.29 (13)	H61A—C6A—H62A	108.00
O51—N51—C5	118.79 (12)	C2—C1—C11	121.05 (13)
O52—N51—C5	117.92 (12)	C6—C1—C11	119.88 (13)
N1A—C2A—C3A	111.79 (13)	C2—C1—C6	119.05 (13)
C2A—C3A—C4A	111.61 (14)	C1—C2—C3	120.97 (13)
C5A—C4A—C41A	111.49 (13)	C2—C3—C31	119.06 (13)
C3A—C4A—C5A	108.07 (13)	C4—C3—C31	120.66 (13)
C3A—C4A—C41A	111.09 (13)	C2—C3—C4	120.28 (13)
C4A—C5A—C6A	110.96 (13)	C3—C4—C5	117.90 (13)
N1A—C6A—C5A	110.71 (13)	N51—C5—C6	118.63 (13)
O41A—C41A—C4A	120.36 (14)	C4—C5—C6	122.73 (14)
N41A—C41A—C4A	117.70 (14)	N51—C5—C4	118.64 (13)
O41A—C41A—N41A	121.93 (14)	C1—C6—C5	119.06 (13)
H21A—C2A—H22A	108.00	O11—C11—C1	118.34 (13)
N1A—C2A—H22A	109.00	O12—C11—C1	116.37 (14)
N1A—C2A—H21A	109.00	O11—C11—O12	125.26 (14)
C3A—C2A—H22A	109.00	O31—C31—C3	122.42 (13)
C3A—C2A—H21A	109.00	O32—C31—C3	112.74 (13)
C2A—C3A—H31A	109.00	O31—C31—O32	124.84 (14)
C4A—C3A—H31A	109.00	C1—C2—H2	120.00
H31A—C3A—H32A	108.00	C3—C2—H2	120.00
C2A—C3A—H32A	109.00	C3—C4—H4	121.00
C4A—C3A—H32A	109.00	C5—C4—H4	121.00
C41A—C4A—H4A	109.00	C1—C6—H6	120.00
C5A—C4A—H4A	109.00	C5—C6—H6	120.00
C6A—N1A—C2A—C3A	−52.98 (18)	C2—C1—C6—C5	−0.5 (3)
C2A—N1A—C6A—C5A	54.44 (18)	C11—C1—C6—C5	177.98 (16)
O51—N51—C5—C4	−5.9 (2)	C2—C1—C11—O11	−161.47 (16)
O51—N51—C5—C6	173.90 (16)	C2—C1—C11—O12	20.3 (3)
O52—N51—C5—C4	175.06 (17)	C6—C1—C11—O11	20.1 (3)
O52—N51—C5—C6	−5.2 (2)	C6—C1—C11—O12	−158.15 (17)
N1A—C2A—C3A—C4A	54.6 (2)	C1—C2—C3—C4	0.9 (3)
C2A—C3A—C4A—C5A	−57.05 (18)	C1—C2—C3—C31	179.86 (16)
C2A—C3A—C4A—C41A	−179.65 (15)	C2—C3—C4—C5	−0.2 (2)
C5A—C4A—C41A—O41A	−88.89 (19)	C31—C3—C4—C5	−179.10 (15)
C5A—C4A—C41A—N41A	90.25 (19)	C2—C3—C31—O31	−8.3 (3)
C3A—C4A—C41A—O41A	31.7 (2)	C2—C3—C31—O32	172.04 (15)
C3A—C4A—C5A—C6A	58.75 (16)	C4—C3—C31—O31	170.71 (16)
C41A—C4A—C5A—C6A	−178.89 (13)	C4—C3—C31—O32	−9.0 (2)
C3A—C4A—C41A—N41A	−149.14 (16)	C3—C4—C5—N51	178.81 (15)
C4A—C5A—C6A—N1A	−58.01 (18)	C3—C4—C5—C6	−1.0 (2)
C6—C1—C2—C3	−0.5 (3)	N51—C5—C6—C1	−178.46 (15)
C11—C1—C2—C3	−179.03 (16)	C4—C5—C6—C1	1.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O31^i	0.93 (2)	2.06 (2)	2.9236 (18)	153.6 (17)
N1A—H12A···O11	0.98 (2)	1.87 (2)	2.8229 (16)	164 (2)
N1A—H12A···O12	0.98 (2)	2.45 (2)	3.0366 (19)	118.1 (17)
N41A—H41A···O11^ii	0.822 (19)	2.298 (19)	3.0669 (19)	155.9 (17)
N41A—H42A···O41A^iii	0.940 (19)	1.996 (19)	2.9321 (18)	174.1 (16)
O32—H32···O12^iv	0.93 (2)	1.63 (2)	2.5336 (17)	164 (3)
C2A—H22A···O52^ii	0.97	2.43	3.308 (2)	151
C5A—H51A···O51^v	0.97	2.54	3.1187 (18)	118
C6A—H61A···O41A^vi	0.97	2.48	3.2700 (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, y−1/2, −z+3/2; (v) x, y+1, z; (vi) x, −y+3/2, z−1/2.

(IV) bis(4-carbamoylpiperidinium) benzene-1,2-dicarboxylate dihydrate

Crystal data

2C6H13N2O8^+·C8H4O4^2^−·2H2O	Z = 1
Mr = 458.51	F(000) = 246
Triclinic, P1	Dx = 1.367 Mg m^−3
Hall symbol: -P 1	Melting point: 531 K
a = 6.5099 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7777 (6) Å	Cell parameters from 3616 reflections
c = 11.6865 (12) Å	θ = 3.4–28.7°
α = 76.429 (8)°	µ = 0.11 mm^−1
β = 76.968 (7)°	T = 200 K
γ = 80.885 (7)°	Needle, colourless
V = 556.89 (9) Å^3	0.50 × 0.15 × 0.08 mm

Data collection

Oxford Gemini-S CCD are-detector diffractometer	2177 independent reflections
Radiation source: Enhance (Mo) X-ray source	1746 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −8→8
Tmin = 0.965, Tmax = 0.990	k = −9→9
6562 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0583P)^2] where P = (Fo^2 + 2Fc^2)/3
2177 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O41A	0.02732 (15)	0.38666 (12)	0.39711 (9)	0.0283 (3)
N1A	0.49004 (18)	0.84055 (14)	0.16744 (10)	0.0228 (3)
N41A	0.3297 (2)	0.23446 (15)	0.44750 (11)	0.0301 (4)
C2A	0.6401 (2)	0.69868 (17)	0.22515 (12)	0.0230 (4)
C3A	0.5391 (2)	0.52630 (16)	0.27457 (12)	0.0208 (4)
C4A	0.32588 (19)	0.55264 (16)	0.36062 (11)	0.0184 (4)
C5A	0.1803 (2)	0.70710 (16)	0.30251 (12)	0.0220 (4)
C6A	0.2890 (2)	0.87498 (17)	0.25378 (13)	0.0270 (4)
C41A	0.2150 (2)	0.38311 (16)	0.40264 (11)	0.0200 (4)
O11	0.37675 (16)	0.82742 (12)	−0.04688 (9)	0.0311 (3)
O12	0.17970 (16)	0.92206 (12)	−0.18601 (9)	0.0326 (3)
C1	0.1102 (2)	0.65006 (16)	−0.04709 (11)	0.0183 (4)
C2	−0.0742 (2)	0.63855 (16)	−0.08456 (12)	0.0219 (4)
C6	0.1841 (2)	0.50915 (16)	0.03731 (11)	0.0206 (4)
C11	0.2303 (2)	0.81224 (16)	−0.09757 (11)	0.0208 (4)
O1W	0.79377 (16)	0.11269 (13)	0.41900 (10)	0.0298 (3)
H4A	0.35440	0.58400	0.43160	0.0220*
H11A	0.457 (3)	0.811 (2)	0.0983 (15)	0.042 (5)*
H12A	0.554 (3)	0.952 (2)	0.1349 (16)	0.052 (5)*
H21A	0.67890	0.73720	0.28980	0.0280*
H22A	0.76840	0.67870	0.16660	0.0280*
H31A	0.63500	0.43890	0.31670	0.0250*
H32A	0.51720	0.48040	0.20840	0.0250*
H41A	0.266 (3)	0.130 (2)	0.4741 (17)	0.054 (5)*
H42A	0.477 (3)	0.233 (2)	0.4429 (15)	0.046 (5)*
H51A	0.13640	0.67330	0.23760	0.0260*
H52A	0.05400	0.73060	0.36160	0.0260*
H61A	0.19520	0.96740	0.21370	0.0320*
H62A	0.31990	0.91630	0.31950	0.0320*
H2	−0.12420	0.73060	−0.14170	0.0260*
H6	0.30850	0.51440	0.06220	0.0250*
H11W	0.876 (3)	0.189 (2)	0.4192 (15)	0.044 (5)*
H12W	0.810 (3)	0.102 (2)	0.3396 (17)	0.044 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O41A	0.0233 (6)	0.0260 (5)	0.0360 (6)	−0.0110 (4)	−0.0049 (4)	−0.0025 (4)
N1A	0.0258 (6)	0.0174 (5)	0.0238 (6)	−0.0098 (5)	−0.0039 (5)	0.0023 (5)
N41A	0.0265 (7)	0.0181 (6)	0.0404 (7)	−0.0075 (5)	−0.0037 (6)	0.0048 (5)
C2A	0.0183 (7)	0.0237 (7)	0.0260 (7)	−0.0069 (5)	−0.0031 (5)	−0.0011 (5)
C3A	0.0180 (7)	0.0175 (6)	0.0245 (7)	−0.0032 (5)	−0.0041 (5)	0.0010 (5)
C4A	0.0195 (7)	0.0175 (6)	0.0180 (6)	−0.0055 (5)	−0.0034 (5)	−0.0012 (5)
C5A	0.0181 (7)	0.0184 (6)	0.0266 (7)	−0.0032 (5)	−0.0012 (5)	−0.0012 (5)
C6A	0.0262 (8)	0.0166 (6)	0.0346 (8)	−0.0017 (5)	−0.0035 (6)	−0.0013 (6)
C41A	0.0228 (7)	0.0185 (6)	0.0171 (6)	−0.0063 (5)	0.0006 (5)	−0.0023 (5)
O11	0.0333 (6)	0.0305 (5)	0.0332 (6)	−0.0195 (4)	−0.0111 (5)	0.0010 (4)
O12	0.0415 (6)	0.0215 (5)	0.0345 (6)	−0.0135 (4)	−0.0131 (5)	0.0067 (4)
C1	0.0183 (7)	0.0163 (6)	0.0200 (6)	−0.0047 (5)	−0.0003 (5)	−0.0049 (5)
C2	0.0238 (7)	0.0163 (6)	0.0245 (7)	−0.0040 (5)	−0.0073 (6)	0.0013 (5)
C6	0.0182 (7)	0.0211 (6)	0.0242 (7)	−0.0053 (5)	−0.0065 (5)	−0.0038 (5)
C11	0.0226 (7)	0.0176 (6)	0.0224 (7)	−0.0072 (5)	−0.0006 (5)	−0.0051 (5)
O1W	0.0315 (6)	0.0240 (5)	0.0336 (6)	−0.0134 (4)	−0.0084 (5)	0.0036 (4)

Geometric parameters (Å, º)

O41A—C41A	1.2336 (17)	C5A—C6A	1.5139 (19)
O11—C11	1.2637 (17)	C2A—H22A	0.9700
O12—C11	1.2476 (16)	C2A—H21A	0.9700
O1W—H12W	0.932 (19)	C3A—H31A	0.9700
O1W—H11W	0.861 (18)	C3A—H32A	0.9700
N1A—C6A	1.4909 (18)	C4A—H4A	0.9800
N1A—C2A	1.4943 (18)	C5A—H52A	0.9700
N41A—C41A	1.3370 (18)	C5A—H51A	0.9700
N1A—H12A	0.979 (17)	C6A—H61A	0.9700
N1A—H11A	0.966 (17)	C6A—H62A	0.9700
N41A—H42A	0.95 (2)	C1—C6	1.3947 (18)
N41A—H41A	0.927 (17)	C1—C11	1.5184 (18)
C2A—C3A	1.5192 (19)	C1—C2	1.3894 (19)
C3A—C4A	1.5353 (18)	C2—C6^i	1.3860 (18)
C4A—C5A	1.5327 (18)	C2—H2	0.9300
C4A—C41A	1.5292 (18)	C6—H6	0.9300
H11W—O1W—H12W	106.9 (16)	H31A—C3A—H32A	108.00
C2A—N1A—C6A	111.57 (10)	C2A—C3A—H31A	109.00
C2A—N1A—H12A	111.2 (11)	C5A—C4A—H4A	108.00
C6A—N1A—H11A	109.2 (12)	C41A—C4A—H4A	108.00
C2A—N1A—H11A	111.9 (10)	C3A—C4A—H4A	108.00
H11A—N1A—H12A	103.9 (15)	C4A—C5A—H52A	109.00
C6A—N1A—H12A	108.8 (10)	C6A—C5A—H51A	109.00
H41A—N41A—H42A	120.6 (15)	C6A—C5A—H52A	109.00
C41A—N41A—H42A	120.5 (10)	H51A—C5A—H52A	108.00
C41A—N41A—H41A	118.5 (12)	C4A—C5A—H51A	109.00
N1A—C2A—C3A	110.62 (11)	N1A—C6A—H61A	110.00
C2A—C3A—C4A	112.00 (11)	N1A—C6A—H62A	110.00
C3A—C4A—C41A	112.20 (10)	C5A—C6A—H62A	110.00
C5A—C4A—C41A	110.45 (11)	H61A—C6A—H62A	108.00
C3A—C4A—C5A	110.71 (10)	C5A—C6A—H61A	110.00
C4A—C5A—C6A	111.97 (11)	C2—C1—C6	118.76 (12)
N1A—C6A—C5A	110.47 (11)	C2—C1—C11	120.76 (11)
O41A—C41A—C4A	120.74 (11)	C6—C1—C11	120.48 (12)
N41A—C41A—C4A	116.78 (12)	C1—C2—C6^i	120.46 (12)
O41A—C41A—N41A	122.47 (12)	C1—C6—C2^i	120.77 (12)
N1A—C2A—H21A	110.00	O11—C11—C1	117.52 (11)
C3A—C2A—H21A	110.00	O12—C11—C1	118.61 (12)
C3A—C2A—H22A	110.00	O11—C11—O12	123.87 (12)
N1A—C2A—H22A	110.00	C1—C2—H2	120.00
H21A—C2A—H22A	108.00	C6^i—C2—H2	120.00
C2A—C3A—H32A	109.00	C1—C6—H6	120.00
C4A—C3A—H31A	109.00	C2^i—C6—H6	120.00
C4A—C3A—H32A	109.00
C6A—N1A—C2A—C3A	58.63 (14)	C4A—C5A—C6A—N1A	55.90 (14)
C2A—N1A—C6A—C5A	−59.19 (14)	C6—C1—C2—C6^i	1.03 (19)
N1A—C2A—C3A—C4A	−54.73 (14)	C11—C1—C2—C6^i	−179.41 (12)
C2A—C3A—C4A—C5A	51.45 (14)	C2—C1—C6—C2^i	−1.03 (19)
C2A—C3A—C4A—C41A	175.35 (11)	C11—C1—C6—C2^i	179.41 (12)
C3A—C4A—C5A—C6A	−52.06 (14)	C2—C1—C11—O11	169.25 (12)
C41A—C4A—C5A—C6A	−176.96 (11)	C2—C1—C11—O12	−10.82 (18)
C3A—C4A—C41A—O41A	−130.14 (13)	C6—C1—C11—O11	−11.19 (18)
C3A—C4A—C41A—N41A	51.36 (15)	C6—C1—C11—O12	168.74 (12)
C5A—C4A—C41A—O41A	−6.10 (16)	C1—C2—C6^i—C1^i	−1.05 (19)
C5A—C4A—C41A—N41A	175.41 (11)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O11	0.966 (17)	1.856 (18)	2.7937 (16)	162.9 (14)
N1A—H12A···O11^ii	0.979 (17)	1.847 (17)	2.8030 (15)	164.7 (17)
N1A—H12A···O12^ii	0.979 (17)	2.367 (19)	3.1200 (16)	133.3 (14)
N41A—H41A···O1W^iii	0.927 (17)	2.045 (17)	2.9181 (16)	156.5 (17)
N41A—H42A···O1W	0.95 (2)	2.111 (19)	2.9870 (17)	153.2 (14)
O1W—H11W···O41A^iv	0.861 (18)	1.892 (18)	2.7410 (15)	168.7 (17)
O1W—H12W···O12^v	0.932 (19)	1.833 (19)	2.7632 (15)	175.6 (19)
C6A—H61A···O12^vi	0.97	2.52	3.3773 (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.