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The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with picric acid and 3,5-dinitro­salicylic acid, namely 4-carbamoylpiperidinium 2,4,6-trinitro­phenolate, C6H13N2O+·C6H2N3O7, (I), and 4-carbamoylpiperidinium 2-carb­oxy-4,6-dinitro­phenolate [two forms of which were found, the monoclinic α-polymorph, (II), and the triclinic β-polymorph, (III)], C6H13N2O+·C7H3N2O7, have been determined at 200 K. All three compounds form hydrogen-bonded structures, viz. one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). In (I), the cations form centrosymmetric cyclic head-to-tail hydrogen-bonded homodimers [graph set R22(14)] through lateral duplex piperidinium–amide N—H...O inter­actions. These dimers are extended into a two-dimensional network structure through further inter­actions with phenolate and nitro O-atom acceptors, including a direct symmetric piperidinium–phenol/nitro N—H...O,O cation–anion association [graph set R12(6)]. The monoclinic polymorph, (II), has a similar R12(6) cation–anion hydrogen-bonding inter­action to (I) but with an additional conjoint symmetrical R12(4) inter­action as well as head-to-tail piperidinium–amide N—H...O,O hydrogen bonds and amide–carboxyl N—H...O hydrogen bonds, giving a network structure which includes large R43(20) rings. The hydrogen bonding in the triclinic polymorph, (III), is markedly different from that of monoclinic (II). The asymmetric unit contains two independent cation–anion pairs which associate through cyclic piperidinium–carboxyl­ N—H...O,O′ inter­actions [graph set R12(4)]. The cations also show the zigzag head-to-tail piperidinium–amide N—H...O hydrogen-bonded chain sub­structures found in (II), but in addition feature amide–nitro and amide–phenolate N—H...O associations. As well, there is a centrosymmetric double-amide N—H...Ocarboxyl bridged bis­(cation–anion) ring system [graph set R42(8)] in the three-dimensional framework. The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitro­salicylic acid salts show an unusual dis­similarity in hydrogen-bonding characteristics, considering that both were obtained from identical solvent systems.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011004672X/fg3206sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206IIIsup4.hkl
Contains datablock III

CCDC references: 810025; 810026; 810027

Comment top

The structures of 4-piperidinecarboxylic acid (isonipecotic acid) (O'Neil, 2001) and its derivatives are uncommon in the crystallographic literature. Both anhydrous isonipecotic acid (Mora et al., 2005) and its monohydrate (Delgado et al., 2001) show the presence of piperidinium–carboxylate zwitterions while the structure of the hydrochloride is also known (Ma & Li, 2006; Adams et al., 2006; Szafran et al., 2007). However, neither the structures of its amide (isonipecotamide, INIPA) nor any of its derivatives have been reported, although the structures of the acetate (Smith & Wermuth, 2010) and the bipyridine-4,4'-disulfonate (Smith et al., 2010) are now known. Picric acid has been used to produce stable crystalline Lewis base salts suitable for X-ray analysis and the number of picrate structures in the literature reflects this. Similarly, 3,5-dinitrosalicylic acid (DNSA) has proved to be a versatile synthon for crystal engineering usage (Kumar et al., 1999) and a large number of structures of proton-transfer compounds with this acid have also been reported (Smith et al., 2002, 2003, 2007). With these, the majority (circa 70%) are phenolates rather than carboxylates, the H atom being anti-located on the carboxyl O within an intramolecular hydrogen bond.

We therefore carried out 1:1 stoichiometric reactions of isonipecotamide with a number of aromatic acids including picric acid and 3,5-dinitrosalicylic acid in 50% aqueous ethanol, with a view to obtaining crystals suitable for X-ray analysis, hence allowing description of the hydrogen-bonding present in these compounds. We obtained good crystals of the anhydrous picrate salt 4-carbamoylpiperidinium picrate, C6H13N2O+ C6H2N3O7-, (I), as well as two anhydrous polymorphic salts with DNSA, 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O+ C7H3N2O7-: the monoclinic (α) polymorph, (II), and the triclinic (β) polymorph, (III). The crystals of (II) were obtained after partial room-temperature evaporation of solvent whereas with the identical parallel reaction in which the solution was taken to dryness, the second anhydrous triclinic polymorph, (III), was obtained. The structures of (I)–(III) are described here, representing the first reported aromatic organic acid salts of the Lewis base isonipecotamide [excluding the biphenyl-4,4'-disulfonate salt (Smith & Wermuth, 2010)]. It was of particular interest to determine what differences, if any, might be found in the hydrogen bonding in the two polymorphic salts, (II) and (III).

With salts (I)–(III) (Figs. 1–3), proton transfer occurs to the hetero-N of the piperidine ring and in each the resulting group, along with the amine substituent group, are subsequently involved in hydrogen-bonding interactions (Tables 1–3). All three salts are phenolates and form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). A feature of hydrogen-bonding motifs in (II) and (III) is the presence of homomolecular head-to-tail piperidinium N—H···Oamide interactions giving infinite zigzag chain structures.

In (I), the two piperidinium H donors give three hydrogen-bonding interactions. One of the H atoms gives a symmetric cyclic R12(6) association (Etter et al., 1990) with phenolate O and nitro O-acceptors of the anion (Fig. 1). The second proton forms a hydrogen bond with an amide O-acceptor giving a centrosymmetric cyclic head-to-tail homodimer [graph set R22(14)] (Table 1 and Fig. 4). This ring is conjoint with a piperidine–amide N—H···O cyclic R42(8) association and the previously mentioned R12(6) association. These rings are linked by other amide–nitro N—H···O interactions into a two-dimensional network structure which lies in the (O11) plane with the picrate ring systems layering down the b axis of the unit cell. The ortho-related nitro-substituent groups of the picrate anion are significantly rotated out of the benzene plane [torsion angles: C1—C2—N2—O22 = 134.13 (16)° and C5—C6—N6—O62 = -157.57 (16)°], compared with 176.78 (14)° for C3—C4—N4—O42 for the para-nitro group.

In the monoclinic α-polymorph of the 3,5-dinitrosalicylic acid salt, (II), a cyclic R12(6) proximal piperidinium–phenol/nitro N—H···O,O cation–anion association similar to that in (I) is present (Fig. 2). This is also similar to the association found in a number of DNSA proton-transfer compounds (Smith et al., 2007) but in (II), with an additional conjoint symmetrical R12(4) piperidinium N—H···O,O' interaction (Fig. 2). Head-to-tail piperidinium–amide N—H···O hydrogen bonds (Table 2) give ribbon structures which extend along the b cell direction and enclose R43(20) ring systems (Fig. 5). The short intramolecular hydrogen bond which is characteristic of the DNSA anion is found in (II) as well as in the triclinic polymorph, (III). In both structures the anti-related proton is located on the carboxyl group rather than on the phenolic O, but this is the majority case with the DNSA anions in the known structures of the proton-transfer salts of this acid (Smith et al., 2002, 2003, 2007).

The triclinic modification (the β-polymorph) of the isonipecotamide-DNSA compound, (III), has two INPA cations (A and B) as well as two anions (C and D) in the asymmetric unit (Fig. 3). Although there is not any major difference in the amide side-chain conformations of the two independent cations in (III) [as indicated by the torsion angle C3—C4—C41—N41 of 93.6 (2)° for cation A cf. 86.5 (2)° for cation B], these differ significantly from that found in (II) [122.29 (16)°]. With the DNSA anions the differences are less obvious. As expected, because of the presence of the intramolecular hydrogen bond, the carboxylic acid group is essentially coplanar with the benzene ring in all three anions [torsion angle C2—C1—C11—O11 = -179.15 (16)° for (II), -178.18 (18)° for (IIIC) and -179.09 (16)° for (IIID)]. Both nitro groups in the two polymorphs are slightly rotated out of the plane [torsion angles: C2—C3—N3—O32 = 165.64 (17)° for (II) -170.75 (16)° for (IIIC), -177.65 (15)° for (IIID); C4—C5—N5—O52 = -166.78 (16)° for (II), -175.98 (17)° for (IIIC) and -170.94 (18)° for (IIID)]. However, the hydrogen-bonding differences between (II) and (III) are very significant (Table 3). There is an absence of the proximal piperidinium–phenolate/nitro N—H···O,O interaction with either of the DNSA anions. Instead, one of the cations (B) gives an N—H···O,O''carboxylate interaction with a D anion [graph set R12(4)], the other (A) acting as a bridge between cation B amide O and anion nitro O-atom acceptors. The anions also form the zigzag head-to-tail piperidinium–amide N—H···O bridged chain hydrogen-bonded chain substructures also found in (II) (Fig. 6). In addition, the hydrogen bonding in the overall three-dimensional framework structure features a centrosymmetric duplex amide H—N—H-bridged bis(cation–anion) R42(8) ring system (Fig. 6).

The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts (II) and (III) show unusually diverse hydrogen-bonding characteristics with only slight molecular conformational differences. In the absence of any additive induced effects during crystallization, the observed polymorphism can be seen as an artefact of solvent gradient effects, considering that the parallel crystallizations occurred from identical ethanol–water solvent mixtures.

Related literature top

For related literature, see: Delgado et al. (2001); Etter et al. (1990); Kumar et al. (1999); Ma & Li (2006); Mora et al. (2005); O'Neil (2001); Smith & Wermuth (2010); Smith et al. (2002, 2003, 2007); Smith, Wermuth & Young (2010); Szafran et al. (2007).

Experimental top

The title compounds were synthesized by heating together for 10 min under reflux, 1 mmol quantities of piperidine-4-carboxamide (isonipecotamide) and 2,4,6-trinitrophenol (picric acid) [for (I)] or 3,5-dinitrosalicylic acid [for (II) and (III)] in 50 ml of 50% ethanol–water. After concentration to circa 30 ml, partial room-temperature evaporation [(I) and (III)] or evaporation to dryness [(II)] of the hot-filtered solutions gave yellow prisms of (I) (m.p. 452 K) or yellow plates of (II) and (III) (m.p. 475 K).

Refinement top

H atoms involved in hydrogen-bonding interactions were located by difference methods and with the exception of the carboxylic H in both (II) and (III) which were allowed to ride, their positional and isotropic displacement parameters were refined. The other H atoms were included in the refinements at calculated positions [C–H(aliphatic) = 0.99, 1.00 Å and C–H(aromatic) = 0.95 Å] while 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? for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR92 (Altomare et al., 1994) for (II), (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (II), (III). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-naming scheme for the isonipecotamide cation and the picrate anion in (I). Displacement ellipsoids are drawn at the 50% probability level. Intermolecular hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The molecular configuration and atom-naming scheme for the isonipecotamide cation and the DNSA anion in (II). Displacement ellipsoids are drawn at the 50% probability level. Inter- and intramolecular hydrogen bonds and short molecular contacts are shown as dashed lines.
[Figure 3] Fig. 3. The molecular configuration and atom-naming scheme for the two isonipecotamide cations (A and B) and the two DNSA anions (C and D) in the asymmetric unit of (III). Displacement ellipsoids are drawn at the 50% probability level. Inter-species hydrogen bonds are shown as dashed lines.
[Figure 4] Fig. 4. The two-dimensional hydrogen-bonded network structure of (I) extending across the (010) plane of the unit cell, showing hydrogen-bonding associations as dashed lines. Non-associative H atoms have been omitted. For symmetry codes, see Table 1.
[Figure 5] Fig. 5. The one-dimensional hydrogen-bonded ribbon structure of (II) extending along the b cell direction, showing hydrogen-bonding associations and short inter-ion associations as dashed lines. Non-associative H atoms have been omitted. For symmetry codes, see Table 2.
[Figure 6] Fig. 6. The three-dimensional hydrogen-bonded framework structure of (III) in a perspective view of the unit cell, showing hydrogen-bonding associations as dashed lines. Non-associative H atoms have been omitted. For symmetry codes, see Table 3.
(I) 4-carbamoylpiperidinium 2,4,6-trinitrophenolate top
Crystal data top
C6H13N2O+·C6H2N3O7F(000) = 744
Mr = 357.29Dx = 1.562 Mg m3
Monoclinic, P21/cMelting point: 452 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.4426 (11) ÅCell parameters from 3090 reflections
b = 13.7495 (13) Åθ = 2.9–28.8°
c = 8.3662 (15) ŵ = 0.13 mm1
β = 100.752 (13)°T = 200 K
V = 1519.2 (3) Å3Prism, yellow
Z = 40.25 × 0.20 × 0.15 mm
Data collection top
Oxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
2994 independent reflections
Radiation source: Enhance (Mo) X-ray source2279 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 16.0774 pixels mm-1θmax = 26.0°, θmin = 2.9°
ω scansh = 1216
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 1516
Tmin = 0.950, Tmax = 0.981l = 1010
10181 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 0.93 w = 1/[σ2(Fo2) + (0.0765P)2]
where P = (Fo2 + 2Fc2)/3
3422 reflections(Δ/σ)max = 0.001
238 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C6H13N2O+·C6H2N3O7V = 1519.2 (3) Å3
Mr = 357.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.4426 (11) ŵ = 0.13 mm1
b = 13.7495 (13) ÅT = 200 K
c = 8.3662 (15) Å0.25 × 0.20 × 0.15 mm
β = 100.752 (13)°
Data collection top
Oxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
2994 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2279 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.981Rint = 0.034
10181 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.26 e Å3
3422 reflectionsΔρmin = 0.28 e Å3
238 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
O41A0.06810 (9)0.34764 (8)0.56686 (13)0.0274 (3)
N1A0.18005 (10)0.49429 (10)0.32222 (18)0.0260 (4)
N41A0.10370 (12)0.23181 (10)0.37156 (19)0.0301 (4)
C2A0.21777 (12)0.41247 (12)0.4365 (2)0.0274 (5)
C3A0.13100 (11)0.36829 (12)0.50578 (19)0.0254 (5)
C4A0.04262 (11)0.33613 (11)0.37166 (18)0.0216 (5)
C5A0.00917 (11)0.42038 (12)0.2511 (2)0.0261 (5)
C6A0.09878 (12)0.46169 (12)0.1850 (2)0.0290 (5)
C41A0.04822 (11)0.30525 (11)0.44474 (18)0.0220 (4)
O10.28293 (8)0.59470 (8)0.11898 (15)0.0331 (4)
O210.25094 (10)0.55147 (11)0.21660 (18)0.0546 (5)
O220.31332 (10)0.68092 (12)0.30871 (19)0.0561 (5)
O410.68551 (10)0.66623 (11)0.13490 (17)0.0497 (5)
O420.74513 (9)0.66687 (9)0.12388 (16)0.0405 (4)
O610.52197 (10)0.64070 (10)0.49982 (15)0.0439 (5)
O620.38267 (11)0.56120 (12)0.43166 (17)0.0579 (5)
N20.31372 (11)0.61673 (11)0.20480 (18)0.0339 (5)
N40.67462 (11)0.65838 (10)0.00737 (18)0.0294 (4)
N60.45444 (11)0.60545 (10)0.39560 (17)0.0307 (5)
C10.37218 (11)0.60584 (10)0.0979 (2)0.0235 (5)
C20.39689 (12)0.61842 (11)0.0630 (2)0.0248 (5)
C30.49200 (12)0.63475 (11)0.0946 (2)0.0247 (5)
C40.57333 (12)0.63959 (10)0.0369 (2)0.0235 (5)
C50.55838 (12)0.63183 (11)0.19544 (19)0.0238 (5)
C60.46230 (12)0.61382 (11)0.22471 (19)0.0248 (5)
H4A0.065000.280000.311200.0260*
H11A0.2335 (13)0.5220 (13)0.281 (2)0.0310*
H12A0.1553 (14)0.5433 (13)0.377 (2)0.0310*
H21A0.270200.437200.526400.0330*
H22A0.249000.361800.377800.0330*
H31A0.106100.416700.576600.0300*
H32A0.156400.311400.573800.0300*
H43A0.0917 (14)0.2098 (14)0.280 (2)0.0360*
H44A0.1644 (14)0.2184 (13)0.400 (2)0.0360*
H51A0.042600.396400.159600.0310*
H52A0.021900.472600.307000.0310*
H61A0.126100.411300.120400.0350*
H62A0.076000.517500.112500.0350*
H30.502500.642600.203100.0300*
H50.613800.638800.283600.0290*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0285 (6)0.0316 (6)0.0246 (6)0.0003 (5)0.0118 (5)0.0026 (5)
N1A0.0228 (7)0.0261 (7)0.0316 (8)0.0025 (6)0.0117 (6)0.0006 (6)
N41A0.0291 (7)0.0333 (8)0.0313 (8)0.0088 (6)0.0141 (7)0.0070 (6)
C2A0.0209 (8)0.0319 (9)0.0293 (9)0.0012 (7)0.0045 (7)0.0022 (7)
C3A0.0223 (8)0.0308 (9)0.0233 (8)0.0000 (6)0.0047 (7)0.0024 (7)
C4A0.0222 (8)0.0234 (8)0.0207 (8)0.0003 (6)0.0082 (6)0.0014 (6)
C5A0.0232 (8)0.0316 (9)0.0229 (8)0.0034 (7)0.0031 (7)0.0034 (7)
C6A0.0284 (9)0.0348 (9)0.0238 (8)0.0043 (7)0.0048 (7)0.0053 (7)
C41A0.0224 (8)0.0225 (7)0.0219 (8)0.0022 (6)0.0061 (6)0.0033 (6)
O10.0234 (6)0.0373 (7)0.0415 (7)0.0023 (5)0.0133 (5)0.0051 (5)
O210.0421 (8)0.0604 (10)0.0551 (10)0.0176 (7)0.0073 (7)0.0047 (7)
O220.0400 (8)0.0741 (10)0.0504 (9)0.0066 (7)0.0010 (7)0.0275 (8)
O410.0316 (7)0.0863 (11)0.0356 (8)0.0006 (7)0.0177 (6)0.0039 (7)
O420.0243 (6)0.0549 (8)0.0410 (8)0.0084 (5)0.0028 (6)0.0005 (6)
O610.0457 (8)0.0594 (9)0.0269 (7)0.0170 (6)0.0072 (6)0.0069 (6)
O620.0535 (9)0.0866 (11)0.0366 (8)0.0385 (8)0.0163 (7)0.0014 (8)
N20.0250 (8)0.0412 (9)0.0347 (9)0.0031 (7)0.0033 (6)0.0010 (7)
N40.0244 (7)0.0333 (8)0.0324 (8)0.0003 (6)0.0106 (6)0.0009 (6)
N60.0354 (8)0.0317 (8)0.0265 (8)0.0055 (6)0.0099 (7)0.0013 (6)
C10.0249 (8)0.0173 (7)0.0303 (9)0.0009 (6)0.0105 (7)0.0002 (6)
C20.0234 (8)0.0228 (8)0.0276 (9)0.0007 (6)0.0031 (7)0.0011 (6)
C30.0278 (8)0.0232 (8)0.0246 (8)0.0016 (6)0.0087 (7)0.0006 (6)
C40.0210 (8)0.0230 (7)0.0278 (9)0.0006 (6)0.0079 (7)0.0003 (6)
C50.0238 (8)0.0217 (8)0.0255 (9)0.0010 (6)0.0038 (7)0.0005 (6)
C60.0302 (8)0.0213 (8)0.0246 (8)0.0021 (6)0.0094 (7)0.0006 (6)
Geometric parameters (Å, º) top
O41A—C41A1.2477 (19)C4A—C5A1.547 (2)
O1—C11.2542 (19)C4A—C41A1.524 (2)
O21—N21.223 (2)C5A—C6A1.526 (2)
O22—N21.238 (2)C2A—H21A0.9900
O41—N41.231 (2)C2A—H22A0.9900
O42—N41.232 (2)C3A—H32A0.9900
O61—N61.235 (2)C3A—H31A0.9900
O62—N61.225 (2)C4A—H4A1.0000
N1A—C2A1.502 (2)C5A—H51A0.9900
N1A—C6A1.498 (2)C5A—H52A0.9900
N41A—C41A1.334 (2)C6A—H61A0.9900
N1A—H12A0.912 (18)C6A—H62A0.9900
N1A—H11A0.934 (18)C1—C21.456 (2)
N41A—H43A0.866 (17)C1—C61.458 (2)
N41A—H44A0.910 (19)C2—C31.372 (2)
N2—C21.471 (2)C3—C41.401 (2)
N4—C41.452 (2)C4—C51.382 (2)
N6—C61.458 (2)C5—C61.381 (2)
C2A—C3A1.522 (2)C3—H30.9500
C3A—C4A1.539 (2)C5—H50.9500
C2A—N1A—C6A112.03 (13)C2A—C3A—H32A109.00
H11A—N1A—H12A105.2 (16)H31A—C3A—H32A108.00
C2A—N1A—H12A110.2 (11)C4A—C3A—H32A109.00
C6A—N1A—H11A109.9 (10)C3A—C4A—H4A109.00
C2A—N1A—H11A110.4 (11)C5A—C4A—H4A109.00
C6A—N1A—H12A108.9 (11)C41A—C4A—H4A109.00
C41A—N41A—H44A119.0 (11)C4A—C5A—H51A109.00
H43A—N41A—H44A119.0 (16)C4A—C5A—H52A109.00
C41A—N41A—H43A119.3 (13)H51A—C5A—H52A108.00
O22—N2—C2117.27 (14)C6A—C5A—H52A109.00
O21—N2—O22123.62 (16)C6A—C5A—H51A109.00
O21—N2—C2119.07 (14)N1A—C6A—H62A110.00
O41—N4—C4117.70 (14)N1A—C6A—H61A110.00
O42—N4—C4119.33 (14)H61A—C6A—H62A108.00
O41—N4—O42122.97 (15)C5A—C6A—H61A110.00
O62—N6—C6119.03 (14)C5A—C6A—H62A110.00
O61—N6—C6118.91 (14)O1—C1—C2122.27 (15)
O61—N6—O62122.02 (15)O1—C1—C6126.42 (15)
N1A—C2A—C3A110.46 (13)C2—C1—C6111.22 (13)
C2A—C3A—C4A112.28 (13)N2—C2—C1118.28 (14)
C3A—C4A—C41A110.78 (12)N2—C2—C3116.28 (14)
C5A—C4A—C41A108.24 (12)C1—C2—C3125.41 (15)
C3A—C4A—C5A110.56 (13)C2—C3—C4118.40 (15)
C4A—C5A—C6A111.23 (13)N4—C4—C3119.63 (15)
N1A—C6A—C5A110.23 (13)N4—C4—C5119.08 (15)
O41A—C41A—N41A122.85 (15)C3—C4—C5121.21 (15)
O41A—C41A—C4A120.55 (14)C4—C5—C6119.48 (15)
N41A—C41A—C4A116.60 (14)N6—C6—C1120.35 (14)
C3A—C2A—H21A110.00N6—C6—C5115.43 (14)
C3A—C2A—H22A110.00C1—C6—C5124.20 (14)
H21A—C2A—H22A108.00C2—C3—H3121.00
N1A—C2A—H22A110.00C4—C3—H3121.00
N1A—C2A—H21A110.00C4—C5—H5120.00
C4A—C3A—H31A109.00C6—C5—H5120.00
C2A—C3A—H31A109.00
C6A—N1A—C2A—C3A58.04 (17)C3A—C4A—C5A—C6A53.09 (17)
C2A—N1A—C6A—C5A59.34 (17)C3A—C4A—C41A—O41A35.27 (19)
O21—N2—C2—C147.9 (2)C3A—C4A—C41A—N41A144.72 (14)
O21—N2—C2—C3133.90 (16)C4A—C5A—C6A—N1A56.52 (17)
O22—N2—C2—C1134.13 (16)O1—C1—C2—N20.7 (2)
O22—N2—C2—C344.1 (2)O1—C1—C2—C3177.28 (15)
O42—N4—C4—C3176.78 (14)C6—C1—C2—N2177.39 (13)
O42—N4—C4—C50.1 (2)C6—C1—C2—C30.6 (2)
O41—N4—C4—C5179.05 (15)O1—C1—C6—N62.3 (2)
O41—N4—C4—C32.4 (2)O1—C1—C6—C5175.98 (15)
O61—N6—C6—C520.3 (2)C2—C1—C6—N6178.77 (13)
O62—N6—C6—C124.0 (2)C2—C1—C6—C50.5 (2)
O61—N6—C6—C1158.11 (14)N2—C2—C3—C4178.33 (13)
O62—N6—C6—C5157.57 (16)C1—C2—C3—C40.3 (2)
N1A—C2A—C3A—C4A54.42 (17)C2—C3—C4—N4178.99 (14)
C2A—C3A—C4A—C5A52.28 (17)C2—C3—C4—C52.4 (2)
C2A—C3A—C4A—C41A172.27 (13)N4—C4—C5—C6179.91 (14)
C5A—C4A—C41A—N41A93.90 (16)C3—C4—C5—C63.5 (2)
C41A—C4A—C5A—C6A174.60 (13)C4—C5—C6—N6179.13 (13)
C5A—C4A—C41A—O41A86.10 (17)C4—C5—C6—C12.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O10.934 (18)1.901 (17)2.7545 (19)150.8 (15)
N1A—H11A···O620.934 (18)2.227 (17)2.859 (2)124.3 (13)
N1A—H12A···O41Ai0.912 (18)2.012 (18)2.8932 (19)162.0 (16)
N41A—H43A···O41Aii0.866 (17)2.029 (17)2.894 (2)177 (2)
N41A—H44A···O1iii0.910 (19)2.316 (19)3.072 (2)140.3 (15)
N41A—H44A···O22iv0.910 (19)2.437 (19)3.017 (2)121.8 (14)
C3—H3···O61v0.952.553.492 (2)172
C2A—H21A···O620.992.503.022 (2)112
C2A—H22A···O41vi0.992.393.233 (2)142
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x, y+1, z; (v) x, y, z1; (vi) x+1, y+1, z.
(II) 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate top
Crystal data top
C6H13N2O+·C7H3N2O7F(000) = 744
Mr = 356.30Dx = 1.530 Mg m3
Monoclinic, P21/nMelting point: 475 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 11.7131 (12) ÅCell parameters from 5903 reflections
b = 12.6450 (11) Åθ = 3.1–28.9°
c = 11.8521 (14) ŵ = 0.13 mm1
β = 118.196 (14)°T = 200 K
V = 1547.1 (3) Å3Plate, yellow
Z = 40.40 × 0.40 × 0.20 mm
Data collection top
Oxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
3048 independent reflections
Radiation source: Enhance (Mo) X-ray source2456 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1414
Tmin = 0.93, Tmax = 0.98k = 1515
19733 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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0505P)2 + 0.3254P]
where P = (Fo2 + 2Fc2)/3
3048 reflections(Δ/σ)max < 0.001
242 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C6H13N2O+·C7H3N2O7V = 1547.1 (3) Å3
Mr = 356.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.7131 (12) ŵ = 0.13 mm1
b = 12.6450 (11) ÅT = 200 K
c = 11.8521 (14) Å0.40 × 0.40 × 0.20 mm
β = 118.196 (14)°
Data collection top
Oxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
3048 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2456 reflections with I > 2σ(I)
Tmin = 0.93, Tmax = 0.98Rint = 0.033
19733 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.31 e Å3
3048 reflectionsΔρmin = 0.24 e Å3
242 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
O41A0.91435 (11)0.16355 (8)0.34281 (12)0.0376 (4)
N1A0.64157 (13)0.46323 (12)0.24420 (14)0.0302 (4)
N41A1.07432 (14)0.25715 (14)0.33428 (14)0.0326 (5)
C2A0.66526 (17)0.43037 (14)0.13574 (16)0.0389 (6)
C3A0.74700 (16)0.33094 (13)0.16879 (16)0.0356 (5)
C4A0.87494 (14)0.34730 (11)0.29070 (15)0.0251 (5)
C5A0.84626 (16)0.37753 (14)0.40008 (16)0.0344 (5)
C6A0.76398 (16)0.47717 (14)0.36640 (16)0.0350 (5)
C41A0.95693 (14)0.24793 (12)0.32469 (14)0.0257 (5)
O20.47303 (10)0.29794 (9)0.22748 (12)0.0371 (4)
O110.37954 (11)0.01363 (9)0.21453 (13)0.0417 (4)
O120.53269 (11)0.10794 (10)0.26508 (12)0.0405 (4)
O310.37968 (13)0.49662 (10)0.18436 (18)0.0641 (6)
O320.18116 (14)0.51899 (10)0.04687 (15)0.0565 (5)
O510.13172 (11)0.24904 (11)0.05034 (14)0.0496 (4)
O520.07272 (12)0.09399 (11)0.03421 (15)0.0569 (5)
N30.27091 (14)0.46176 (11)0.11677 (15)0.0344 (5)
N50.04816 (12)0.18363 (11)0.01234 (14)0.0342 (5)
C10.31189 (14)0.16553 (11)0.17075 (14)0.0240 (5)
C20.35196 (14)0.27440 (12)0.17692 (14)0.0252 (5)
C30.24707 (15)0.34884 (11)0.12059 (15)0.0256 (5)
C40.11787 (14)0.31943 (12)0.06519 (15)0.0265 (5)
C50.08755 (14)0.21438 (12)0.06551 (15)0.0259 (4)
C60.18314 (14)0.13709 (12)0.11806 (14)0.0251 (5)
C110.41058 (15)0.07888 (12)0.21983 (15)0.0283 (5)
H4A0.923500.406400.276600.0300*
H11A0.591 (2)0.4179 (17)0.2527 (19)0.049 (6)*
H12A0.5991 (18)0.5283 (15)0.2205 (17)0.040 (5)*
H21A0.710100.488100.116000.0470*
H22A0.581300.417500.058600.0470*
H31A0.764500.312500.097200.0430*
H32A0.699000.271500.181200.0430*
H41A1.1000 (17)0.3199 (16)0.3247 (17)0.035 (5)*
H42A1.120 (2)0.2035 (18)0.3522 (19)0.048 (6)*
H51A0.799900.318800.416100.0410*
H52A0.928700.389600.479300.0410*
H61A0.743100.493800.436200.0420*
H62A0.813600.537300.357900.0420*
H40.051300.371000.027600.0320*
H60.159800.065100.117600.0300*
H120.531600.188600.26020.0490*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0362 (7)0.0224 (6)0.0581 (8)0.0004 (5)0.0254 (6)0.0015 (5)
N1A0.0211 (7)0.0230 (7)0.0474 (9)0.0011 (6)0.0170 (6)0.0042 (6)
N41A0.0254 (7)0.0316 (8)0.0422 (9)0.0052 (7)0.0172 (6)0.0031 (7)
C2A0.0396 (10)0.0368 (10)0.0302 (9)0.0097 (8)0.0082 (8)0.0017 (8)
C3A0.0368 (9)0.0349 (9)0.0274 (9)0.0075 (7)0.0089 (7)0.0053 (7)
C4A0.0227 (7)0.0212 (8)0.0336 (9)0.0009 (6)0.0151 (7)0.0002 (6)
C5A0.0333 (9)0.0375 (10)0.0278 (9)0.0101 (7)0.0106 (7)0.0024 (7)
C6A0.0349 (9)0.0343 (9)0.0355 (9)0.0060 (7)0.0165 (8)0.0060 (7)
C41A0.0241 (8)0.0254 (8)0.0271 (8)0.0008 (6)0.0117 (6)0.0036 (6)
O20.0219 (6)0.0299 (6)0.0541 (8)0.0046 (5)0.0136 (5)0.0031 (5)
O110.0366 (7)0.0244 (7)0.0637 (9)0.0042 (5)0.0234 (6)0.0040 (6)
O120.0244 (6)0.0329 (7)0.0585 (8)0.0043 (5)0.0149 (6)0.0053 (6)
O310.0362 (8)0.0295 (7)0.1270 (14)0.0099 (6)0.0388 (9)0.0149 (8)
O320.0602 (9)0.0290 (7)0.0753 (10)0.0087 (6)0.0278 (8)0.0154 (7)
O510.0225 (6)0.0539 (8)0.0652 (9)0.0069 (6)0.0148 (6)0.0013 (7)
O520.0348 (7)0.0396 (8)0.0948 (12)0.0138 (6)0.0293 (8)0.0057 (7)
N30.0359 (8)0.0252 (7)0.0537 (9)0.0016 (6)0.0306 (7)0.0009 (7)
N50.0229 (7)0.0359 (8)0.0448 (9)0.0032 (6)0.0169 (6)0.0085 (7)
C10.0244 (8)0.0236 (8)0.0271 (8)0.0003 (6)0.0147 (6)0.0006 (6)
C20.0236 (8)0.0267 (8)0.0269 (8)0.0038 (6)0.0133 (6)0.0006 (6)
C30.0298 (8)0.0208 (8)0.0308 (9)0.0016 (6)0.0180 (7)0.0002 (6)
C40.0251 (8)0.0273 (8)0.0299 (8)0.0040 (6)0.0152 (7)0.0016 (6)
C50.0218 (7)0.0299 (8)0.0286 (8)0.0029 (6)0.0140 (6)0.0039 (7)
C60.0269 (8)0.0231 (8)0.0295 (8)0.0036 (6)0.0168 (7)0.0039 (6)
C110.0277 (8)0.0264 (8)0.0318 (9)0.0022 (7)0.0149 (7)0.0005 (7)
Geometric parameters (Å, º) top
O41A—C41A1.239 (2)C4A—C41A1.516 (2)
O2—C21.287 (2)C5A—C6A1.521 (3)
O11—C111.218 (2)C2A—H22A0.9900
O12—C111.320 (2)C2A—H21A0.9900
O31—N31.223 (2)C3A—H32A0.9900
O32—N31.222 (2)C3A—H31A0.9900
O51—N51.228 (2)C4A—H4A1.0000
O52—N51.227 (2)C5A—H51A0.9900
O12—H121.01C5A—H52A0.9900
N1A—C6A1.491 (2)C6A—H61A0.9900
N1A—C2A1.496 (2)C6A—H62A0.9900
N41A—C41A1.330 (3)C1—C61.380 (2)
N1A—H12A0.93 (2)C1—C111.497 (2)
N1A—H11A0.86 (2)C1—C21.445 (2)
N41A—H42A0.83 (2)C2—C31.437 (2)
N41A—H41A0.88 (2)C3—C41.386 (3)
N3—C31.460 (2)C4—C51.376 (2)
N5—C51.459 (2)C5—C61.392 (2)
C2A—C3A1.515 (3)C4—H40.9500
C3A—C4A1.527 (2)C6—H60.9500
C4A—C5A1.533 (2)
C11—O12—H12106.00C4A—C3A—H32A110.00
C2A—N1A—C6A112.57 (15)C41A—C4A—H4A109.00
H11A—N1A—H12A109 (2)C3A—C4A—H4A109.00
C6A—N1A—H11A111.3 (14)C5A—C4A—H4A109.00
C2A—N1A—H11A109.4 (14)C4A—C5A—H52A110.00
C2A—N1A—H12A106.0 (12)C4A—C5A—H51A110.00
C6A—N1A—H12A108.6 (12)C6A—C5A—H51A110.00
H41A—N41A—H42A124 (2)C6A—C5A—H52A110.00
C41A—N41A—H41A118.3 (14)H51A—C5A—H52A108.00
C41A—N41A—H42A117.9 (17)H61A—C6A—H62A108.00
O32—N3—C3118.99 (16)N1A—C6A—H62A109.00
O31—N3—C3119.19 (15)C5A—C6A—H61A109.00
O31—N3—O32121.82 (15)N1A—C6A—H61A109.00
O51—N5—C5118.44 (14)C5A—C6A—H62A109.00
O52—N5—C5118.12 (15)C2—C1—C6122.05 (15)
O51—N5—O52123.43 (17)C2—C1—C11120.33 (15)
N1A—C2A—C3A111.06 (14)C6—C1—C11117.61 (13)
C2A—C3A—C4A110.49 (13)O2—C2—C3125.23 (14)
C5A—C4A—C41A110.26 (13)C1—C2—C3114.49 (15)
C3A—C4A—C5A108.95 (15)O2—C2—C1120.27 (15)
C3A—C4A—C41A110.77 (12)N3—C3—C2121.40 (16)
C4A—C5A—C6A110.46 (14)C2—C3—C4123.14 (14)
N1A—C6A—C5A110.88 (14)N3—C3—C4115.46 (15)
O41A—C41A—C4A120.24 (16)C3—C4—C5118.91 (15)
N41A—C41A—C4A116.72 (15)N5—C5—C6119.21 (14)
O41A—C41A—N41A123.04 (16)C4—C5—C6121.68 (16)
C3A—C2A—H22A109.00N5—C5—C4119.09 (15)
N1A—C2A—H22A109.00C1—C6—C5119.71 (14)
C3A—C2A—H21A109.00O11—C11—C1121.76 (17)
H21A—C2A—H22A108.00O12—C11—C1116.34 (14)
N1A—C2A—H21A109.00O11—C11—O12121.87 (16)
C4A—C3A—H31A110.00C3—C4—H4121.00
C2A—C3A—H32A110.00C5—C4—H4121.00
H31A—C3A—H32A108.00C1—C6—H6120.00
C2A—C3A—H31A110.00C5—C6—H6120.00
C6A—N1A—C2A—C3A55.3 (2)C6—C1—C2—O2179.58 (15)
C2A—N1A—C6A—C5A55.14 (19)C6—C1—C2—C31.8 (2)
O31—N3—C3—C215.0 (3)C11—C1—C2—O21.7 (2)
O31—N3—C3—C4165.79 (17)C11—C1—C2—C3176.98 (14)
O32—N3—C3—C2165.64 (17)C2—C1—C6—C51.9 (2)
O32—N3—C3—C413.5 (2)C11—C1—C6—C5176.90 (14)
O52—N5—C5—C4166.78 (16)C2—C1—C11—O11179.15 (16)
O52—N5—C5—C611.7 (2)C2—C1—C11—O121.4 (2)
O51—N5—C5—C6169.32 (15)C6—C1—C11—O110.4 (2)
O51—N5—C5—C412.2 (2)C6—C1—C11—O12177.40 (14)
N1A—C2A—C3A—C4A56.8 (2)O2—C2—C3—N30.3 (3)
C2A—C3A—C4A—C5A58.26 (18)O2—C2—C3—C4178.83 (16)
C2A—C3A—C4A—C41A179.72 (15)C1—C2—C3—N3178.86 (15)
C41A—C4A—C5A—C6A179.97 (15)C1—C2—C3—C40.3 (2)
C3A—C4A—C41A—O41A58.1 (2)N3—C3—C4—C5179.72 (15)
C3A—C4A—C41A—N41A122.29 (16)C2—C3—C4—C51.1 (3)
C5A—C4A—C41A—O41A62.58 (19)C3—C4—C5—N5177.34 (15)
C5A—C4A—C41A—N41A117.03 (16)C3—C4—C5—C61.1 (2)
C3A—C4A—C5A—C6A58.22 (18)N5—C5—C6—C1178.80 (14)
C4A—C5A—C6A—N1A56.7 (2)C4—C5—C6—C10.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O20.86 (2)1.98 (2)2.817 (2)164 (2)
N1A—H11A···O310.86 (2)2.43 (2)2.835 (3)109.7 (17)
N1A—H12A···O310.93 (2)2.43 (2)2.835 (3)106.1 (15)
N1A—H12A···O41Ai0.93 (2)1.844 (19)2.6964 (19)151 (2)
N41A—H41A···O11i0.88 (2)2.19 (2)3.053 (2)168 (2)
O12—H12···O21.011.522.4829 (17)157
C4A—H4A···O11i1.002.483.396 (2)153
C6—H6···O52ii0.952.573.356 (2)141
C6A—H61A···O52iii0.992.523.329 (3)138
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x, y, z; (iii) x+1/2, y+1/2, z+1/2.
(III) 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate top
Crystal data top
C6H13N2O+·C7H3N2O7Z = 4
Mr = 356.30F(000) = 744
Triclinic, P1Dx = 1.559 Mg m3
Hall symbol: -P 1Melting point: 475 K
a = 6.4628 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.2375 (5) ÅCell parameters from 6525 reflections
c = 23.8964 (12) Åθ = 3.2–26.3°
α = 98.644 (4)°µ = 0.13 mm1
β = 96.905 (5)°T = 200 K
γ = 100.753 (5)°Plate, yellow
V = 1517.65 (15) Å30.40 × 0.30 × 0.18 mm
Data collection top
Oxford Diffraction Gemini S Ultra CCD-detector
diffractometer
5940 independent reflections
Radiation source: Enhance (Mo) X-ray source4477 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 16.0774 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = 77
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
k = 1212
Tmin = 0.96, Tmax = 0.98l = 2929
19052 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 0.82 w = 1/[σ2(Fo2) + (0.0513P)2 + 0.942P]
where P = (Fo2 + 2Fc2)/3
5940 reflections(Δ/σ)max = 0.001
475 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C6H13N2O+·C7H3N2O7γ = 100.753 (5)°
Mr = 356.30V = 1517.65 (15) Å3
Triclinic, P1Z = 4
a = 6.4628 (4) ÅMo Kα radiation
b = 10.2375 (5) ŵ = 0.13 mm1
c = 23.8964 (12) ÅT = 200 K
α = 98.644 (4)°0.40 × 0.30 × 0.18 mm
β = 96.905 (5)°
Data collection top
Oxford Diffraction Gemini S Ultra CCD-detector
diffractometer
5940 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
4477 reflections with I > 2σ(I)
Tmin = 0.96, Tmax = 0.98Rint = 0.026
19052 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 0.82Δρmax = 0.23 e Å3
5940 reflectionsΔρmin = 0.23 e Å3
475 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
O41A0.4007 (2)0.55488 (13)0.15540 (6)0.0393 (5)
N1A0.3377 (3)0.28117 (17)0.30206 (6)0.0303 (5)
N41A0.3364 (3)0.36629 (19)0.08796 (7)0.0326 (5)
C2A0.4617 (3)0.22154 (19)0.25964 (7)0.0313 (6)
C3A0.5066 (3)0.31061 (18)0.21499 (7)0.0271 (5)
C4A0.3010 (3)0.34102 (16)0.18570 (7)0.0224 (5)
C5A0.1867 (3)0.40601 (19)0.23145 (7)0.0309 (6)
C6A0.1381 (3)0.3132 (2)0.27419 (8)0.0336 (6)
C41A0.3492 (3)0.43050 (17)0.14166 (7)0.0249 (5)
O41B0.2595 (2)0.04969 (13)0.34894 (6)0.0386 (4)
N1B0.2843 (3)0.21807 (18)0.19773 (7)0.0383 (5)
N41B0.0602 (3)0.02188 (17)0.41370 (7)0.0318 (5)
C2B0.3944 (3)0.1694 (2)0.24597 (8)0.0343 (6)
C3B0.2408 (3)0.06578 (17)0.29159 (7)0.0281 (5)
C4B0.0528 (3)0.12542 (16)0.31373 (7)0.0224 (5)
C5B0.0566 (3)0.17283 (19)0.26336 (8)0.0313 (6)
C6B0.0969 (3)0.2745 (2)0.21742 (8)0.0387 (6)
C41B0.1025 (3)0.02486 (17)0.36037 (7)0.0258 (5)
O2C0.7910 (2)0.36537 (14)0.64334 (5)0.0357 (4)
O11C0.3216 (2)0.12946 (16)0.52181 (6)0.0499 (5)
O12C0.4301 (2)0.22647 (16)0.61149 (6)0.0452 (5)
O31C1.1939 (2)0.47632 (15)0.67064 (6)0.0505 (5)
O32C1.3761 (2)0.52172 (14)0.60282 (7)0.0487 (5)
O51C1.1336 (3)0.31938 (16)0.40967 (6)0.0515 (5)
O52C0.8068 (3)0.21578 (15)0.38024 (5)0.0466 (5)
N3C1.2125 (3)0.46726 (15)0.61903 (7)0.0334 (5)
N5C0.9529 (3)0.27440 (15)0.41862 (6)0.0343 (5)
C1C0.6723 (3)0.26236 (17)0.54569 (7)0.0242 (5)
C2C0.8319 (3)0.34157 (16)0.59197 (7)0.0232 (5)
C3C1.0354 (3)0.38988 (16)0.57617 (7)0.0236 (5)
C4C1.0726 (3)0.36687 (16)0.52000 (7)0.0248 (5)
C5C0.9110 (3)0.29343 (17)0.47753 (7)0.0255 (5)
C6C0.7112 (3)0.23996 (16)0.48980 (7)0.0259 (5)
C11C0.4610 (3)0.19998 (18)0.55862 (8)0.0272 (5)
O2D0.25480 (19)0.09966 (12)0.01267 (5)0.0320 (4)
O11D0.1786 (2)0.05121 (15)0.15760 (5)0.0407 (5)
O12D0.2154 (2)0.12496 (14)0.08783 (6)0.0392 (5)
O31D0.3012 (3)0.04976 (14)0.11857 (6)0.0465 (5)
O32D0.2836 (3)0.15379 (15)0.13274 (5)0.0476 (5)
O51D0.2266 (3)0.52462 (14)0.01892 (6)0.0520 (5)
O52D0.1368 (3)0.50050 (15)0.10611 (6)0.0520 (5)
N3D0.2812 (2)0.07086 (15)0.10056 (6)0.0271 (5)
N5D0.1895 (2)0.45422 (16)0.05479 (6)0.0330 (5)
C1D0.2129 (2)0.09091 (17)0.06083 (7)0.0236 (5)
C2D0.2419 (2)0.02863 (17)0.00131 (7)0.0229 (5)
C3D0.2541 (2)0.11969 (17)0.03879 (7)0.0225 (5)
C4D0.2388 (3)0.25717 (17)0.02187 (7)0.0244 (5)
C5D0.2093 (3)0.31009 (17)0.03614 (7)0.0246 (5)
C6D0.1967 (2)0.22769 (18)0.07723 (7)0.0255 (5)
C11D0.2005 (3)0.0049 (2)0.10630 (8)0.0300 (6)
H4A0.206400.253700.165600.0270*
H11A0.423 (3)0.355 (2)0.3248 (8)0.034 (5)*
H12A0.308 (3)0.217 (2)0.3255 (9)0.040 (6)*
H21A0.380300.131000.240200.0380*
H22A0.598300.210400.280000.0380*
H31A0.577800.264600.185800.0320*
H32A0.604600.396500.233700.0320*
H41A0.295 (3)0.280 (2)0.0779 (9)0.043 (6)*
H42A0.356 (3)0.416 (2)0.0597 (10)0.050 (6)*
H51A0.277600.493100.251700.0370*
H52A0.052200.424500.213000.0370*
H61A0.066500.357300.303800.0400*
H62A0.039900.228500.254300.0400*
H4B0.110200.206100.330500.0270*
H11B0.383 (4)0.284 (2)0.1729 (10)0.056 (7)*
H12B0.244 (4)0.140 (3)0.1801 (10)0.063 (7)*
H21B0.456500.247000.263200.0410*
H22B0.512200.128600.231000.0410*
H31B0.315800.038000.323700.0340*
H32B0.187600.015300.275300.0340*
H41B0.057 (4)0.073 (2)0.4221 (9)0.048 (6)*
H42B0.148 (3)0.035 (2)0.4421 (9)0.036 (5)*
H51B0.117400.093900.246800.0380*
H52B0.175200.214100.277400.0380*
H61B0.023200.298600.184600.0460*
H62B0.146000.357700.232700.0460*
H4C1.208700.401500.510700.0300*
H6C0.602600.188600.460100.0310*
H12C0.5840.2920.6350.061*
H4D0.248300.314200.049600.0290*
H6D0.176900.266000.116700.0310*
H12D0.2290.1310.04100.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O41A0.0525 (9)0.0241 (7)0.0370 (8)0.0035 (6)0.0072 (6)0.0057 (6)
N1A0.0369 (9)0.0298 (9)0.0194 (8)0.0044 (7)0.0028 (6)0.0048 (7)
N41A0.0425 (10)0.0328 (10)0.0202 (8)0.0018 (8)0.0045 (7)0.0056 (7)
C2A0.0342 (10)0.0344 (10)0.0258 (9)0.0074 (8)0.0031 (8)0.0074 (8)
C3A0.0247 (9)0.0328 (10)0.0221 (9)0.0023 (7)0.0034 (7)0.0046 (7)
C4A0.0257 (9)0.0206 (8)0.0177 (8)0.0002 (7)0.0022 (6)0.0006 (7)
C5A0.0363 (10)0.0311 (10)0.0263 (9)0.0091 (8)0.0081 (8)0.0034 (8)
C6A0.0337 (10)0.0413 (11)0.0257 (9)0.0052 (8)0.0103 (8)0.0046 (8)
C41A0.0243 (9)0.0247 (9)0.0237 (9)0.0022 (7)0.0010 (7)0.0036 (7)
O41B0.0317 (7)0.0352 (7)0.0434 (8)0.0082 (6)0.0022 (6)0.0111 (6)
N1B0.0475 (10)0.0366 (10)0.0215 (8)0.0117 (8)0.0017 (7)0.0075 (7)
N41B0.0339 (9)0.0302 (9)0.0253 (8)0.0020 (7)0.0024 (7)0.0029 (7)
C2B0.0301 (10)0.0386 (11)0.0306 (10)0.0001 (8)0.0015 (8)0.0085 (8)
C3B0.0293 (9)0.0266 (9)0.0272 (9)0.0038 (7)0.0014 (7)0.0059 (7)
C4B0.0251 (9)0.0198 (8)0.0218 (8)0.0013 (7)0.0039 (7)0.0058 (7)
C5B0.0324 (10)0.0329 (10)0.0299 (10)0.0053 (8)0.0110 (8)0.0068 (8)
C6B0.0526 (13)0.0319 (10)0.0303 (10)0.0032 (9)0.0170 (9)0.0004 (8)
C41B0.0259 (9)0.0214 (8)0.0302 (10)0.0043 (7)0.0007 (7)0.0085 (7)
O2C0.0387 (7)0.0458 (8)0.0198 (6)0.0046 (6)0.0062 (5)0.0005 (6)
O11C0.0328 (8)0.0577 (10)0.0478 (9)0.0064 (7)0.0050 (7)0.0024 (7)
O12C0.0376 (8)0.0566 (10)0.0425 (9)0.0027 (7)0.0149 (7)0.0143 (7)
O31C0.0596 (10)0.0517 (9)0.0265 (8)0.0039 (7)0.0128 (7)0.0009 (7)
O32C0.0325 (8)0.0397 (8)0.0647 (10)0.0095 (6)0.0050 (7)0.0033 (7)
O51C0.0669 (11)0.0529 (9)0.0361 (8)0.0041 (8)0.0292 (8)0.0061 (7)
O52C0.0700 (10)0.0488 (9)0.0191 (7)0.0191 (8)0.0010 (7)0.0022 (6)
N3C0.0358 (9)0.0238 (8)0.0366 (9)0.0044 (7)0.0036 (7)0.0019 (7)
N5C0.0581 (11)0.0267 (8)0.0219 (8)0.0150 (8)0.0114 (8)0.0044 (7)
C1C0.0270 (9)0.0236 (9)0.0228 (9)0.0079 (7)0.0012 (7)0.0053 (7)
C2C0.0307 (9)0.0213 (8)0.0182 (8)0.0080 (7)0.0017 (7)0.0038 (7)
C3C0.0268 (9)0.0193 (8)0.0229 (9)0.0041 (7)0.0006 (7)0.0024 (7)
C4C0.0289 (9)0.0200 (8)0.0272 (9)0.0061 (7)0.0074 (7)0.0055 (7)
C5C0.0387 (10)0.0219 (9)0.0180 (8)0.0099 (7)0.0062 (7)0.0044 (7)
C6C0.0338 (10)0.0207 (8)0.0211 (9)0.0070 (7)0.0030 (7)0.0015 (7)
C11C0.0243 (9)0.0268 (9)0.0300 (10)0.0054 (7)0.0007 (7)0.0064 (8)
O2D0.0330 (7)0.0273 (7)0.0343 (7)0.0052 (5)0.0024 (5)0.0050 (6)
O11D0.0439 (8)0.0552 (9)0.0261 (7)0.0087 (7)0.0068 (6)0.0175 (6)
O12D0.0438 (8)0.0368 (8)0.0389 (8)0.0057 (6)0.0036 (6)0.0185 (6)
O31D0.0706 (10)0.0332 (8)0.0304 (7)0.0092 (7)0.0054 (7)0.0068 (6)
O32D0.0774 (11)0.0471 (9)0.0194 (7)0.0168 (8)0.0021 (7)0.0088 (6)
O51D0.0891 (12)0.0310 (8)0.0356 (8)0.0160 (8)0.0002 (8)0.0078 (7)
O52D0.0804 (11)0.0389 (8)0.0272 (8)0.0085 (8)0.0055 (7)0.0084 (6)
N3D0.0248 (8)0.0335 (9)0.0204 (7)0.0052 (6)0.0011 (6)0.0000 (7)
N5D0.0385 (9)0.0301 (8)0.0271 (8)0.0041 (7)0.0024 (7)0.0004 (7)
C1D0.0154 (8)0.0323 (10)0.0229 (9)0.0024 (7)0.0030 (6)0.0075 (7)
C2D0.0141 (8)0.0277 (9)0.0263 (9)0.0026 (7)0.0030 (6)0.0048 (7)
C3D0.0187 (8)0.0293 (9)0.0181 (8)0.0037 (7)0.0019 (6)0.0020 (7)
C4D0.0230 (9)0.0301 (9)0.0202 (8)0.0038 (7)0.0031 (7)0.0074 (7)
C5D0.0234 (8)0.0256 (9)0.0221 (9)0.0020 (7)0.0021 (7)0.0007 (7)
C6D0.0196 (8)0.0386 (10)0.0168 (8)0.0036 (7)0.0025 (6)0.0039 (7)
C11D0.0198 (9)0.0431 (11)0.0299 (10)0.0048 (8)0.0055 (7)0.0161 (9)
Geometric parameters (Å, º) top
O41A—C41A1.237 (2)C2A—H22A0.9900
O41B—C41B1.236 (2)C2A—H21A0.9900
O2C—C2C1.284 (2)C3A—H31A0.9900
O11C—C11C1.218 (2)C3A—H32A0.9900
O12C—C11C1.299 (2)C4A—H4A1.0000
O31C—N3C1.245 (2)C5A—H52A0.9900
O32C—N3C1.234 (2)C5A—H51A0.9900
O51C—N5C1.229 (3)C6A—H61A0.9900
O52C—N5C1.228 (2)C6A—H62A0.9900
O12C—H12C1.12C2B—C3B1.516 (3)
O2D—C2D1.290 (2)C3B—C4B1.532 (3)
O11D—C11D1.227 (2)C4B—C5B1.530 (3)
O12D—C11D1.318 (2)C4B—C41B1.520 (2)
O31D—N3D1.222 (2)C5B—C6B1.511 (3)
O32D—N3D1.229 (2)C2B—H21B0.9900
O51D—N5D1.230 (2)C2B—H22B0.9900
O52D—N5D1.229 (2)C3B—H32B0.9900
O12D—H12D1.10C3B—H31B0.9900
N1A—C6A1.494 (3)C4B—H4B1.0000
N1A—C2A1.495 (3)C5B—H51B0.9900
N41A—C41A1.337 (2)C5B—H52B0.9900
N1A—H12A0.93 (2)C6B—H62B0.9900
N1A—H11A0.91 (2)C6B—H61B0.9900
N41A—H41A0.86 (2)C1C—C6C1.382 (2)
N41A—H42A0.91 (2)C1C—C11C1.484 (3)
N1B—C6B1.493 (3)C1C—C2C1.445 (2)
N1B—C2B1.497 (3)C2C—C3C1.432 (3)
N41B—C41B1.332 (2)C3C—C4C1.385 (2)
N1B—H11B0.92 (2)C4C—C5C1.382 (2)
N1B—H12B0.97 (3)C5C—C6C1.389 (3)
N41B—H41B0.90 (2)C4C—H4C0.9500
N41B—H42B0.89 (2)C6C—H6C0.9500
N3C—C3C1.457 (2)C1D—C11D1.502 (3)
N5C—C5C1.457 (2)C1D—C2D1.443 (2)
N3D—C3D1.464 (2)C1D—C6D1.377 (2)
N5D—C5D1.453 (2)C2D—C3D1.439 (2)
C2A—C3A1.524 (3)C3D—C4D1.386 (2)
C3A—C4A1.533 (3)C4D—C5D1.387 (2)
C4A—C41A1.519 (2)C5D—C6D1.392 (2)
C4A—C5A1.531 (3)C4D—H4D0.9500
C5A—C6A1.517 (3)C6D—H6D0.9500
C11C—O12C—H12C105C4B—C5B—C6B111.68 (16)
C11D—O12D—H12D103N1B—C6B—C5B110.62 (16)
C2A—N1A—C6A112.62 (13)O41B—C41B—C4B121.21 (15)
H11A—N1A—H12A106.4 (18)N41B—C41B—C4B116.54 (16)
C2A—N1A—H12A105.4 (13)O41B—C41B—N41B122.25 (17)
C2A—N1A—H11A109.0 (12)C3B—C2B—H21B109.00
C6A—N1A—H11A111.7 (13)N1B—C2B—H22B109.00
C6A—N1A—H12A111.4 (12)N1B—C2B—H21B109.00
H41A—N41A—H42A118 (2)C3B—C2B—H22B109.00
C41A—N41A—H41A123.0 (14)H21B—C2B—H22B108.00
C41A—N41A—H42A118.9 (14)C2B—C3B—H31B110.00
C2B—N1B—C6B112.62 (15)C4B—C3B—H31B110.00
C6B—N1B—H12B112.1 (16)C4B—C3B—H32B110.00
C2B—N1B—H11B106.8 (16)H31B—C3B—H32B108.00
H11B—N1B—H12B111 (2)C2B—C3B—H32B110.00
C6B—N1B—H11B109.6 (15)C5B—C4B—H4B108.00
C2B—N1B—H12B104.8 (15)C3B—C4B—H4B108.00
C41B—N41B—H42B119.1 (13)C41B—C4B—H4B108.00
H41B—N41B—H42B118.2 (19)H51B—C5B—H52B108.00
C41B—N41B—H41B122.7 (13)C4B—C5B—H51B109.00
O32C—N3C—C3C118.70 (16)C6B—C5B—H51B109.00
O31C—N3C—O32C122.24 (17)C4B—C5B—H52B109.00
O31C—N3C—C3C119.06 (17)C6B—C5B—H52B109.00
O51C—N5C—O52C123.02 (16)N1B—C6B—H62B110.00
O52C—N5C—C5C118.91 (18)C5B—C6B—H61B109.00
O51C—N5C—C5C118.07 (15)N1B—C6B—H61B110.00
O31D—N3D—O32D122.13 (15)C5B—C6B—H62B110.00
O31D—N3D—C3D119.63 (14)H61B—C6B—H62B108.00
O32D—N3D—C3D118.24 (14)C2C—C1C—C11C119.10 (15)
O51D—N5D—O52D122.75 (16)C6C—C1C—C11C118.67 (16)
O51D—N5D—C5D119.05 (14)C2C—C1C—C6C122.21 (17)
O52D—N5D—C5D118.20 (15)O2C—C2C—C3C123.32 (16)
N1A—C2A—C3A111.46 (15)C1C—C2C—C3C115.22 (15)
C2A—C3A—C4A111.45 (16)O2C—C2C—C1C121.46 (17)
C3A—C4A—C41A110.65 (16)N3C—C3C—C4C117.13 (17)
C3A—C4A—C5A108.97 (14)N3C—C3C—C2C120.84 (15)
C5A—C4A—C41A111.81 (14)C2C—C3C—C4C122.03 (16)
C4A—C5A—C6A110.43 (15)C3C—C4C—C5C119.74 (17)
N1A—C6A—C5A110.89 (16)N5C—C5C—C6C119.97 (16)
O41A—C41A—N41A122.69 (17)C4C—C5C—C6C121.54 (16)
N41A—C41A—C4A115.86 (16)N5C—C5C—C4C118.49 (17)
O41A—C41A—C4A121.44 (15)C1C—C6C—C5C119.20 (16)
H21A—C2A—H22A108.00O11C—C11C—O12C121.22 (18)
C3A—C2A—H22A109.00O11C—C11C—C1C122.32 (17)
C3A—C2A—H21A109.00O12C—C11C—C1C116.44 (16)
N1A—C2A—H22A109.00C5C—C4C—H4C120.00
N1A—C2A—H21A109.00C3C—C4C—H4C120.00
C4A—C3A—H31A109.00C5C—C6C—H6C120.00
C2A—C3A—H31A109.00C1C—C6C—H6C120.00
H31A—C3A—H32A108.00C2D—C1D—C11D119.46 (15)
C2A—C3A—H32A109.00C2D—C1D—C6D121.72 (15)
C4A—C3A—H32A109.00C6D—C1D—C11D118.82 (15)
C3A—C4A—H4A108.00C1D—C2D—C3D115.03 (15)
C5A—C4A—H4A108.00O2D—C2D—C3D124.73 (15)
C41A—C4A—H4A109.00O2D—C2D—C1D120.24 (15)
C6A—C5A—H51A110.00N3D—C3D—C2D121.03 (15)
C6A—C5A—H52A110.00N3D—C3D—C4D116.14 (15)
H51A—C5A—H52A108.00C2D—C3D—C4D122.83 (15)
C4A—C5A—H52A110.00C3D—C4D—C5D118.93 (16)
C4A—C5A—H51A110.00C4D—C5D—C6D121.24 (16)
C5A—C6A—H61A109.00N5D—C5D—C4D119.79 (15)
C5A—C6A—H62A109.00N5D—C5D—C6D118.98 (15)
N1A—C6A—H62A109.00C1D—C6D—C5D120.26 (15)
H61A—C6A—H62A108.00O12D—C11D—C1D115.85 (16)
N1A—C6A—H61A110.00O11D—C11D—O12D121.42 (18)
N1B—C2B—C3B111.12 (16)O11D—C11D—C1D122.73 (18)
C2B—C3B—C4B110.17 (15)C3D—C4D—H4D120.00
C3B—C4B—C5B109.12 (14)C5D—C4D—H4D121.00
C3B—C4B—C41B111.55 (14)C1D—C6D—H6D120.00
C5B—C4B—C41B111.66 (16)C5D—C6D—H6D120.00
C6A—N1A—C2A—C3A53.7 (2)C6C—C1C—C2C—O2C177.56 (17)
C2A—N1A—C6A—C5A55.8 (2)C6C—C1C—C2C—C3C2.7 (3)
C6B—N1B—C2B—C3B56.1 (2)C11C—C1C—C2C—C3C175.82 (16)
C2B—N1B—C6B—C5B54.9 (2)C2C—C1C—C6C—C5C1.0 (3)
O32C—N3C—C3C—C2C170.75 (16)C11C—C1C—C2C—O2C4.0 (3)
O31C—N3C—C3C—C2C9.2 (3)C11C—C1C—C6C—C5C177.53 (16)
O31C—N3C—C3C—C4C171.43 (16)C2C—C1C—C11C—O11C178.18 (18)
O32C—N3C—C3C—C4C8.6 (2)C2C—C1C—C11C—O12C3.0 (3)
O52C—N5C—C5C—C4C175.98 (17)C6C—C1C—C11C—O11C0.4 (3)
O52C—N5C—C5C—C6C3.1 (3)C6C—C1C—C11C—O12C178.44 (17)
O51C—N5C—C5C—C6C177.67 (17)O2C—C2C—C3C—N3C1.8 (3)
O51C—N5C—C5C—C4C3.3 (3)O2C—C2C—C3C—C4C177.54 (17)
O32D—N3D—C3D—C2D177.65 (15)C1C—C2C—C3C—C4C2.7 (2)
O32D—N3D—C3D—C4D1.6 (2)C1C—C2C—C3C—N3C177.99 (15)
O31D—N3D—C3D—C4D178.16 (17)C2C—C3C—C4C—C5C1.0 (3)
O31D—N3D—C3D—C2D2.6 (2)N3C—C3C—C4C—C5C179.62 (16)
O52D—N5D—C5D—C6D8.6 (3)C3C—C4C—C5C—N5C178.15 (16)
O51D—N5D—C5D—C6D171.10 (17)C3C—C4C—C5C—C6C0.9 (3)
O51D—N5D—C5D—C4D9.3 (3)N5C—C5C—C6C—C1C178.11 (16)
O52D—N5D—C5D—C4D170.94 (18)C4C—C5C—C6C—C1C0.9 (3)
N1A—C2A—C3A—C4A54.19 (19)C6D—C1D—C2D—O2D179.44 (13)
C2A—C3A—C4A—C41A179.66 (14)C6D—C1D—C2D—C3D0.50 (19)
C2A—C3A—C4A—C5A56.34 (18)C11D—C1D—C2D—O2D0.7 (2)
C5A—C4A—C41A—O41A36.6 (2)C11D—C1D—C2D—C3D179.33 (14)
C3A—C4A—C41A—O41A85.1 (2)C2D—C1D—C6D—C5D0.4 (2)
C3A—C4A—C5A—C6A58.21 (19)C11D—C1D—C6D—C5D179.48 (16)
C3A—C4A—C41A—N41A93.6 (2)C2D—C1D—C11D—O11D179.09 (16)
C5A—C4A—C41A—N41A144.70 (18)C2D—C1D—C11D—O12D0.7 (2)
C41A—C4A—C5A—C6A179.16 (15)C6D—C1D—C11D—O11D0.8 (3)
C4A—C5A—C6A—N1A58.2 (2)C6D—C1D—C11D—O12D179.49 (15)
N1B—C2B—C3B—C4B57.0 (2)O2D—C2D—C3D—N3D0.6 (2)
C2B—C3B—C4B—C5B57.19 (19)O2D—C2D—C3D—C4D179.80 (15)
C2B—C3B—C4B—C41B178.97 (15)C1D—C2D—C3D—N3D179.38 (12)
C41B—C4B—C5B—C6B179.07 (15)C1D—C2D—C3D—C4D0.1 (2)
C3B—C4B—C5B—C6B57.15 (19)N3D—C3D—C4D—C5D178.91 (16)
C5B—C4B—C41B—N41B151.11 (17)C2D—C3D—C4D—C5D0.4 (3)
C3B—C4B—C41B—O41B93.6 (2)C3D—C4D—C5D—N5D179.03 (16)
C3B—C4B—C41B—N41B86.5 (2)C3D—C4D—C5D—C6D0.5 (3)
C5B—C4B—C41B—O41B28.8 (2)N5D—C5D—C6D—C1D179.39 (14)
C4B—C5B—C6B—N1B55.7 (2)C4D—C5D—C6D—C1D0.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O32Ci0.91 (2)2.113 (19)2.980 (2)160.1 (17)
N1A—H12A···O41B0.93 (2)1.86 (2)2.759 (2)159.7 (19)
N1B—H11B···O41Aii0.92 (2)1.91 (2)2.757 (2)153 (2)
N1B—H12B···O11D0.97 (3)2.09 (3)3.039 (2)167 (2)
N1B—H12B···O12D0.97 (3)2.26 (2)2.980 (2)131 (2)
N41A—H41A···O2Diii0.86 (2)2.18 (2)2.954 (2)148.8 (19)
N41A—H42A···O51Div0.91 (2)2.18 (2)2.999 (2)149.0 (18)
N41B—H41B···O11Cv0.90 (2)2.34 (2)3.176 (2)154.9 (18)
N41B—H41B···O12Cv0.90 (2)2.58 (2)3.388 (2)149.5 (18)
N41B—H42B···O11C0.89 (2)2.09 (2)2.950 (2)164.3 (19)
O12C—H12C···O2C1.121.382.460 (2)157
O12D—H12D···O2D1.101.372.4422 (18)163
C4A—H4A···O31Diii1.002.443.167 (2)129
C2B—H22B···O32Dvi0.992.503.252 (2)132
C3A—H32A···O31Ci0.992.523.367 (2)143
C6B—H61B···O52Dvii0.992.503.197 (2)128
Symmetry codes: (i) x+2, y+1, z+1; (ii) x1, y1, z; (iii) x, y, z; (iv) x, y+1, z; (v) x, y, z+1; (vi) x1, y, z; (vii) x, y1, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC6H13N2O+·C6H2N3O7C6H13N2O+·C7H3N2O7C6H13N2O+·C7H3N2O7
Mr357.29356.30356.30
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/nTriclinic, P1
Temperature (K)200200200
a, b, c (Å)13.4426 (11), 13.7495 (13), 8.3662 (15)11.7131 (12), 12.6450 (11), 11.8521 (14)6.4628 (4), 10.2375 (5), 23.8964 (12)
α, β, γ (°)90, 100.752 (13), 9090, 118.196 (14), 9098.644 (4), 96.905 (5), 100.753 (5)
V3)1519.2 (3)1547.1 (3)1517.65 (15)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.130.130.13
Crystal size (mm)0.25 × 0.20 × 0.150.40 × 0.40 × 0.200.40 × 0.30 × 0.18
Data collection
DiffractometerOxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
Oxford Diffraction Gemini-S Ultra CCD-detector
diffractometer
Oxford Diffraction Gemini S Ultra CCD-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.950, 0.9810.93, 0.980.96, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
10181, 2994, 2279 19733, 3048, 2456 19052, 5940, 4477
Rint0.0340.0330.026
(sin θ/λ)max1)0.6170.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.107, 0.93 0.039, 0.098, 1.06 0.039, 0.095, 0.82
No. of reflections342230485940
No. of parameters238242475
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 refinement
Δρmax, Δρmin (e Å3)0.26, 0.280.31, 0.240.23, 0.23

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), CrysAlis PRO?, SHELXS97 (Sheldrick, 2008), SIR92 (Altomare et al., 1994), 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···O10.934 (18)1.901 (17)2.7545 (19)150.8 (15)
N1A—H11A···O620.934 (18)2.227 (17)2.859 (2)124.3 (13)
N1A—H12A···O41Ai0.912 (18)2.012 (18)2.8932 (19)162.0 (16)
N41A—H43A···O41Aii0.866 (17)2.029 (17)2.894 (2)177 (2)
N41A—H44A···O1iii0.910 (19)2.316 (19)3.072 (2)140.3 (15)
N41A—H44A···O22iv0.910 (19)2.437 (19)3.017 (2)121.8 (14)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1A—H11A···O20.86 (2)1.98 (2)2.817 (2)164 (2)
N1A—H11A···O310.86 (2)2.43 (2)2.835 (3)109.7 (17)
N1A—H12A···O310.93 (2)2.43 (2)2.835 (3)106.1 (15)
N1A—H12A···O41Ai0.93 (2)1.844 (19)2.6964 (19)151 (2)
N41A—H41A···O11i0.88 (2)2.19 (2)3.053 (2)168 (2)
O12—H12···O21.011.522.4829 (17)157
Symmetry code: (i) 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···O32Ci0.91 (2)2.113 (19)2.980 (2)160.1 (17)
N1A—H12A···O41B0.93 (2)1.86 (2)2.759 (2)159.7 (19)
N1B—H11B···O41Aii0.92 (2)1.91 (2)2.757 (2)153 (2)
N1B—H12B···O11D0.97 (3)2.09 (3)3.039 (2)167 (2)
N1B—H12B···O12D0.97 (3)2.26 (2)2.980 (2)131 (2)
N41A—H41A···O2Diii0.86 (2)2.18 (2)2.954 (2)148.8 (19)
N41A—H42A···O51Div0.91 (2)2.18 (2)2.999 (2)149.0 (18)
N41B—H41B···O11Cv0.90 (2)2.34 (2)3.176 (2)154.9 (18)
N41B—H41B···O12Cv0.90 (2)2.58 (2)3.388 (2)149.5 (18)
N41B—H42B···O11C0.89 (2)2.09 (2)2.950 (2)164.3 (19)
O12C—H12C···O2C1.121.382.460 (2)157
O12D—H12D···O2D1.101.372.4422 (18)163
Symmetry codes: (i) x+2, y+1, z+1; (ii) x1, y1, z; (iii) x, y, z; (iv) x, y+1, z; (v) x, y, z+1.
 

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