Three-dimensional hydrogen-bonded structures in the guanidinium salts of the monocyclic dicarb­oxy­lic acids rac-trans-cyclo­hexane-1,2-dicarb­oxy­lic acid (2:1, anhydrous), isophthalic acid (1:1, monohydrate) and terephthalic acid (2:1, trihydrate)

The structures of bis­(guanidinium) rac-trans-cyclo­hexane-1,2-dicarboxyl­ate, 2CH₆N₃⁺·C₈H₁₀O₄²⁻, (I), guanidinium 3-carb­oxy­benzoate monohydrate, CH₆N₃⁺·C₈H₅O₄⁻·H₂O, (II), and bis­(guanidinium) benzene-1,4-dicarboxyl­ate trihydrate, 2CH₆N₃⁺·C₈H₄O₄²⁻·3H₂O, (III), all reveal three-dimensional hydrogen-bonded framework structures. In anhydrous (I), both guanidinium cations form classic cyclic R₂²(8) N—H...O,O′_carboxylate and asymmetric cyclic R₂¹(6) hydrogen-bonding inter­actions, while one cation forms an unusual enlarged cyclic inter­action with O-atom acceptors of separate ortho-related carboxylate groups [graph set R₂²(11)]. Cations and anions also associate across inversion centres, giving cyclic R₄²(8) motifs. In the 1:1 guanidinium salt, (II), the cation forms two separate cyclic R₂¹(6) inter­actions, one with a carboxyl O-atom acceptor and the other with the solvent water mol­ecule. The structure is unusual in that both carboxyl groups form short inter­anion O...H...O contacts, one across a crystallographic inversion centre [O...O = 2.483 (2) Å] and the other about a twofold axis of rotation [O...O = 2.462 (2) Å], representing shared sites on these elements for the single acid H atom. The water mol­ecule links the cation–anion ribbon structures into a three-dimensional framework. In (III), the repeating mol­ecular unit comprises a benzene-1,4-dicarboxyl­ate dianion which lies across a crystallographic inversion centre, two guanidinium cations and two solvent water mol­ecules (each set related by twofold rotational symmetry), and a single water mol­ecule which lies on a twofold axis. Each guanidinium cation forms three types of cyclic inter­action with the dianions: one R₂¹(6), the others R₃²(8) and R₃³(10) (both of these involving the water mol­ecules), giving a three-dimensional structure through bridges down the b-cell direction. The water mol­ecule at the general site also forms an unusual cyclic R₂²(4) homodimeric association across an inversion centre [O...O = 2.875 (2) Å]. The work described here provides further examples of the common cyclic guanidinium–carboxyl­ate hydrogen-bonding associations, as well as featuring other less common cyclic motifs.

S1. Comment

The structures of the guanidinium salts of aromatic and heteroaromatic polyfunctional carboxylic acids are not numerous in the crystallographic literature, but they are of interest because of the the capacity of the guanidinium cation to generate stable supramolecular framework structures through hydrogen-bonding associations, largely cyclic, such as those found in the structures of guanidinium carbonate (Adams & Small, 1974) and guanidinium bicarbonate (Baldwin et al., 1986). Among the known aromatic and heteroaromatic carboxylate examples are the monoguanidinium salts of the dicarboxylic acids 4-hydroxypyridine-2,6-dicarboxylic acid (an unusual anhydrous compound in which the pyridine N atom and one of the carboxylic acid groups exist as a zwitterion; Moghimi et al., 2005) and 3-nitrophthalic acid (a monohydrate; Smith, Wermuth & Healy, 2007). Other bifunctional acid salts are those with 4-chloro-3-nitrobenzoic acid (a monohydrate; Najafpour et al., 2007), 4-amino-2,4,6-trichloropicolinic acid (Parthasarathi et al., 1984), 4-nitroanthranilic acid (Smith, Wermuth, Healy & White, 2007), 3-nitrobenzoic acid (Smith & Wermuth, 2010), 4-nitrobenzoic acid (Schurmann et al., 1998), 4-aminobenzoic acid (Pereira Silva et al., 2010) and 3,5-dinitrobenzoic acid (Smith, Wermuth & White, 2007) (all anhydrates). The known bis(guanidinium) salts are those with phthalic acid (anhydrous; Krumbe & Haussuhl, 1987) and pyrazine-2,3-dicarboxylic acid (a trihydrate; Smith et al., 2006). Another bis(guanidinium) example but with a tetracarboxylic acid is that with 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid; Sun et al., 2002). However, the most spectacular examples have been found in the supramolecular ribbon structures of the guanidinium bicarbonate tert-butylammonium salts of terephthalic acid (Mak & Xue, 2000). Among these examples, high-dimensional hydrogen-bonded structures are predominant, with the guanidinium cation forming multiple cyclic hydrogen-bonding associations with carboxylate O-acceptors, most commonly those defined by graph sets R₂²(8) and R₂¹(6) and, to a lesser extent, R²₁(4) (Etter et al., 1990). In the hydrated examples, the water molecules are usually incorporated in expanded cyclic associations.

Our 1:1 stoichiometric reactions of a number of monocyclic dicarboxylic acids, including rac-trans-cyclohexane-1,2-dicarboxylic acid, isophthalic acid and terephthalic acid, with guanidinium carbonate in aqueous propan-2-ol gave relatively hard chemically stable crystals of the anhydrous salt bis(guanidinium) rac-trans-cyclohexane-1,2-dicarboxylate, (I), guanidinium 3-carboxybenzoate monohydrate, (II), and bis(guanidinium) benzene-1,4-dicarboxylate trihydrate, (III), respectively. The structures and hydrogen-bonding patterns for (I)–(III) are reported here. The molecular contents of the asymmetric units of these three compounds and their atom-numbering schemes are shown in Figs. 1–3.

In the anhydrous 2:1 guanidinium salt, (I), both cations (A and B) give classic cyclic R₂²(8) N—H···O_carboxyl hydrogen-bonding interactions with, respectively, O21ⁱⁱ/O22ⁱⁱ and O11ⁱⁱⁱ/O12ⁱⁱⁱ (Fig. 4) (for symmetry code, see Table 1). Each cation is also involved in asymmetric cyclic R₂¹(6) interactions with carboxyl O-atom acceptors. Additionally, cation B gives an unusual enlarged cyclic interaction [graph set R₂²(11)] with acceptors O12 and O22 of the two adjacent cis-related carboxyl groups. Further hydrogen-bonding extensions, including a centrosymmetric cyclic bis(cation–anion) association [graph set R₂²(8)] (Fig. 4), give the three-dimensional framework structure. The structure also contains a relatively long intermolecular N2B–H···N3B^v interaction [3.3191 (18) Å; for symmetry code see Table 1], and there is one potential guanidinium donor (H22A) for which there is no reasonable acceptor.

The structure of the hydrated 1:1 guanidinium hydrogen isophthalate salt, (II) (Fig. 2), is unusual in that each of the carboxyl groups gives short interanion O—H—O contacts, one across a crystallographic inversion centre [O12···O12ⁱⁱⁱ = 2.483 (2) Å] and the other about a twofold axis of rotation [O31···O31^vi = 2.462 (2) Å] (Fig. 5) (for symmetry codes, see Table 2). H atoms were located on these symmetry elements and therefore represent half-occupancy delocalized H atoms. These interactions effectively give anion–anion associated ribbon structures, which extend across the approximate ac diagonal in the cell (Fig. 6) and accommodate both the cations and the water molecules. The cation gives two separate cyclic R₂¹(6) interactions, one with a carboxyl O-atom acceptor (involving atoms N1A and N3A) and the other with the solvent water molecule (involving atoms N1A and N2A), and [these?] are interlinked by the water molecules and further expanded down the b axis into a three-dimensional framework structure (Fig. 7).

In guanidinium terephthalate trihydrate, (III), the formula unit comprises a benzene-1,4-dicarboxylate dianion which lies across a crystallographic inversion centre, two guanidinium cations and two solvent water molecules (both pairs related by twofold rotational symmetry), and a third water molecule (O1W) lying on a crystallographic twofold axis (Fig. 3). The guanidinium cations and the dianion give two types of cyclic hydrogen-bonding motifs, one the common guanidinium R₂¹(6) association (with atoms N1A and N3A) and the others incorporating the two water molecules: (a) atom O1W with atoms N1A and N2A [graph set R₃³(10)] and (b) atom O2W with atoms N2A and N3A [graph set R₃²(8)] (Table 3) (Figs. 8, 9), giving the three-dimensional framework structure. Present also in the structure of (III) are unusual inversion-related water–water interactions involving atoms O2W and O2W^vi [2.875 (2) Å; symmetry code: (vi) −x + 2, −y + 2, −z + 1, giving discrete cyclic dimers. Although the O2W–H22W···O2W^vi `bond' angle (113°) is less than would normally be accepted for a conventional hydrogen bond, this unusual R₂²(4) association must be recognized as such in the assembly of the structure of (III).

In the hydrogen isophthalate anion of (II), one of the carboxyl groups is close to coplanar with the benzene ring [torsion angle C2—C1—C11—O11 = −170.30 (19)°], while the other is twisted out of the plane [torsion angle C2—C3—C31—O32 = 159.9 (2)°]. This latter value is comparable with that for the C2—C1—C11—O12 torsion angle in both carboxyl groups in (III) [−159.86 (15)°].

The three-dimensional structures of (I)–(III) reported here show not only classic guanidinium cyclic R₂²(8) N—H···O_carboxyl and R₂¹(6) hydrogen-bonding motifs but, in addition, various expanded cyclic associations involving the solvent water molecules, and in the case of anhydrous (I), an unusual R₂²(11) cyclic guanidinium–carboxylate interaction. In addition, with (II), the 1:1 guanidinium salt appears to be preferred over the 2:1 salt as expected and found in (I) and (III), considering the identical 2:1 stoichiometric reaction conditions employed in all three preparations [1:1 stoichiometry stated above - please clarify].

S2. Experimental

The title compounds, (I)–(III), were synthesized by heating together under reflux for 10 min 1 mmol quantities of, respectively, rac-trans-cyclohexane-1,2-dicarboxylic acid [for (I)], benzene-1,3-dicarboxylic acid (isophthalic acid) [for (II)] and benzene-1,4-dicarboxylic acid (terephthalic acid) [for (III)], with guanidine carbonate [1 mmol?] in 50% aqueous propan-2-ol (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave large colourless plates [(I) and (III)] or small colourless flat prisms [(II)] [Please clarify - block given in CIF tables for (I) and (III), and platelet for (II)] [m.p. 525 K for (I), 474 K for (II) and 505 K for (III)]. For (I) and (III), specimens suitable for X-ray analysis were cleaved from larger crystals.

S3. Refinement

H atoms involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined, with the exception of the water H atoms of (III) which were constrained with U_iso(H) = 1.2U_eq(O). Aromatic H atoms were included in the refinement in calculated positions using a riding-model approximation, with C–H = 0.95 Å and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis CCD (Oxford Diffraction, 2008) for (III). Cell refinement: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis RED (Oxford Diffraction, 2008) for (III). Data reduction: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis RED (Oxford Diffraction, 2008) for (III). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (III); SHELXS97 (Sheldrick, 2008) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (I), (III); SHELXL97 (Sheldrick, 2008) for (II). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the two guanidinium cations (A and B) and the cyclohexane-1,2-dicarboxylate anion in (I). Inter-species hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The molecular configuration and atom-numbering scheme for the guanidinium cation, hydrogen isophthalate anion and solvent water molecule in (II). Inter-species hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 3. The molecular configuration and atom-numbering scheme for the guanidinium cation (A), the benzene-1,4-dicarboxylate dianion and the two solvent water molecules in the asymmetric unit of (III). The dianion lies across an inversion centre [symmetry code: (ii) −x + 3/2, −y + 1/2, −z + 1], while the water molecule O1W lies on the twofold rotation axis at (1/2, y, 3/4). Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 4. The three-dimensional framework structure of (I), viewed down the approximate c-axis direction in the unit cell, showing hydrogen-bonding associations as dashed lines. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. (For symmetry codes, see Table 1.)
	Fig. 5. The head-to-tail hydrogen-bonding extensions of the hydrogen isophthalate anions with the attached guanidinium cation and water species in the structure of (II), showing the delocalized half-occupancy acid H atoms H12 [located on an inversion centre at (3/4, 3/4, 1/2)] and H31 [located on the twofold axis at (1, y, 3/4). (For symmetry codes, see Table 2.)
	Fig. 6. The hydrogen-bonded framework structure of (II), viewed down the b-axis direction of the unit cell, showing hydrogen-bonding associations as dashed lines. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 7. A second view of the hydrogen-bonding in the framework structure of (II), viewed down the approximate a direction of the unit cell, showing extensions down c. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. (For symmetry codes, see Table 2.)
	Fig. 8. The hydogen-bonding in the structure of (III), viewed down the b axis in the unit cell, showing associations as dashed lines. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. [Symmetry code: (vi) −x + 2, −y + 2, −z + 1; for other symmetry codes, see Table 3 and Fig. 3.]
	Fig. 9. The hydrogen-bonded framework structure of (III), viewed perpendicular to b, showing the role of the unusual centrosymmetric associated water dimers in the structure extension. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

(I) bis(guanidinium) rac-trans-cyclohexane-1,2-dicarboxylate

Crystal data

2CH6N3^+·C8H10O4^2^−	F(000) = 624
Mr = 290.34	Dx = 1.325 Mg m^−3
Monoclinic, P21/c	Melting point: 525 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.7425 (10) Å	Cell parameters from 4460 reflections
b = 16.0538 (15) Å	θ = 3.3–27.3°
c = 8.5067 (8) Å	µ = 0.10 mm^−1
β = 97.224 (9)°	T = 200 K
V = 1455.4 (2) Å^3	Block, colourless
Z = 4	0.50 × 0.50 × 0.45 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2858 independent reflections
Radiation source: Enhance (Mo) X-ray source	2222 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 26.0°, θmin = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −13→13
Tmin = 0.956, Tmax = 0.980	k = −19→19
10102 measured reflections	l = −10→10

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0499P)^2] where P = (Fo^2 + 2Fc^2)/3
2858 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 0.21 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
O11	0.28367 (9)	0.65888 (5)	0.22616 (10)	0.0388 (3)
O12	0.38881 (10)	0.54439 (6)	0.18356 (12)	0.0532 (4)
O21	0.13764 (9)	0.46127 (6)	0.22862 (12)	0.0467 (3)
O22	0.23469 (9)	0.34074 (5)	0.28527 (10)	0.0383 (3)
C1	0.30811 (11)	0.55434 (8)	0.43121 (15)	0.0317 (4)
C2	0.31330 (12)	0.45930 (8)	0.43500 (15)	0.0326 (4)
C3	0.29719 (14)	0.42556 (9)	0.59977 (16)	0.0457 (5)
C4	0.17857 (15)	0.45842 (10)	0.65769 (17)	0.0520 (6)
C5	0.17851 (15)	0.55300 (9)	0.66004 (17)	0.0504 (5)
C6	0.19322 (13)	0.58938 (9)	0.49817 (15)	0.0380 (5)
C11	0.32681 (11)	0.58714 (8)	0.26785 (15)	0.0336 (4)
C21	0.21998 (11)	0.41906 (8)	0.30680 (14)	0.0307 (4)
N1A	−0.14413 (12)	0.71415 (8)	0.02360 (15)	0.0404 (4)
N2A	0.03214 (14)	0.72334 (9)	0.20525 (15)	0.0451 (4)
N3A	0.01995 (12)	0.62499 (8)	0.00845 (15)	0.0410 (4)
C1A	−0.03143 (12)	0.68735 (8)	0.07946 (14)	0.0319 (4)
N1B	0.47601 (13)	0.39190 (8)	0.04825 (16)	0.0447 (4)
N2B	0.48434 (14)	0.29413 (8)	0.24571 (15)	0.0443 (4)
N3B	0.63072 (11)	0.29361 (8)	0.07093 (15)	0.0379 (4)
C1B	0.53062 (12)	0.32699 (8)	0.12250 (15)	0.0326 (4)
H1	0.38110	0.57330	0.50300	0.0380*
H2	0.39750	0.44320	0.41330	0.0390*
H31	0.29400	0.36520	0.59590	0.0550*
H32	0.36920	0.44150	0.67410	0.0550*
H41	0.17300	0.43750	0.76350	0.0620*
H42	0.10590	0.43860	0.58850	0.0620*
H51	0.24670	0.57250	0.73680	0.0610*
H52	0.10040	0.57260	0.69310	0.0610*
H61	0.20100	0.64940	0.50710	0.0460*
H62	0.11850	0.57720	0.42530	0.0460*
H11A	−0.1770 (15)	0.7570 (10)	0.0751 (17)	0.057 (5)*
H12A	−0.1796 (15)	0.6929 (9)	−0.0661 (19)	0.049 (4)*
H21A	0.1066 (17)	0.7077 (10)	0.2333 (19)	0.054 (5)*
H22A	−0.0005 (15)	0.7647 (10)	0.2435 (18)	0.056 (5)*
H31A	−0.0265 (14)	0.5966 (10)	−0.0628 (18)	0.047 (4)*
H32A	0.0840 (16)	0.6043 (10)	0.0540 (19)	0.055 (5)*
H11B	0.5152 (14)	0.4140 (10)	−0.0279 (18)	0.051 (4)*
H12B	0.4289 (16)	0.4197 (11)	0.094 (2)	0.062 (5)*
H21B	0.4117 (17)	0.3086 (10)	0.2649 (19)	0.055 (5)*
H22B	0.5235 (15)	0.2521 (10)	0.2943 (18)	0.058 (5)*
H31B	0.6636 (15)	0.2503 (11)	0.1179 (18)	0.054 (5)*
H32B	0.6650 (15)	0.3180 (10)	−0.0156 (18)	0.056 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0442 (6)	0.0319 (5)	0.0428 (5)	0.0016 (4)	0.0148 (4)	0.0009 (4)
O12	0.0660 (7)	0.0424 (6)	0.0594 (7)	0.0126 (5)	0.0396 (6)	0.0056 (5)
O21	0.0394 (6)	0.0456 (6)	0.0507 (6)	0.0093 (5)	−0.0120 (5)	−0.0135 (5)
O22	0.0477 (6)	0.0302 (5)	0.0374 (5)	−0.0040 (4)	0.0075 (4)	0.0013 (4)
C1	0.0250 (7)	0.0364 (8)	0.0338 (7)	−0.0064 (5)	0.0039 (5)	−0.0036 (5)
C2	0.0241 (7)	0.0358 (7)	0.0371 (7)	−0.0028 (5)	0.0004 (5)	0.0019 (5)
C3	0.0522 (9)	0.0464 (9)	0.0347 (8)	−0.0104 (7)	−0.0088 (7)	0.0068 (6)
C4	0.0612 (11)	0.0621 (10)	0.0344 (8)	−0.0208 (8)	0.0123 (7)	0.0056 (7)
C5	0.0546 (10)	0.0605 (10)	0.0395 (8)	−0.0134 (8)	0.0193 (7)	−0.0070 (7)
C6	0.0370 (8)	0.0395 (8)	0.0401 (8)	−0.0054 (6)	0.0147 (6)	−0.0061 (6)
C11	0.0282 (7)	0.0329 (7)	0.0415 (7)	−0.0039 (6)	0.0113 (6)	−0.0023 (6)
C21	0.0285 (7)	0.0338 (7)	0.0311 (7)	−0.0030 (5)	0.0088 (5)	0.0001 (5)
N1A	0.0447 (8)	0.0398 (7)	0.0367 (7)	0.0112 (5)	0.0053 (6)	−0.0060 (5)
N2A	0.0458 (8)	0.0473 (8)	0.0423 (7)	0.0024 (6)	0.0056 (6)	−0.0157 (6)
N3A	0.0318 (7)	0.0473 (8)	0.0428 (7)	0.0072 (6)	0.0006 (6)	−0.0166 (6)
C1A	0.0353 (7)	0.0328 (7)	0.0293 (7)	−0.0020 (6)	0.0103 (6)	−0.0017 (5)
N1B	0.0503 (8)	0.0420 (7)	0.0461 (7)	0.0147 (6)	0.0231 (6)	0.0129 (6)
N2B	0.0479 (8)	0.0439 (8)	0.0436 (7)	0.0120 (6)	0.0152 (6)	0.0145 (6)
N3B	0.0405 (7)	0.0315 (7)	0.0430 (7)	0.0064 (5)	0.0107 (6)	0.0016 (5)
C1B	0.0362 (7)	0.0284 (7)	0.0331 (7)	−0.0004 (5)	0.0041 (6)	−0.0017 (5)

Geometric parameters (Å, º)

O11—C11	1.2750 (15)	N3B—H32B	0.948 (16)
O12—C11	1.2445 (16)	N3B—H31B	0.856 (17)
O21—C21	1.2393 (16)	C1—C6	1.5300 (19)
O22—C21	1.2832 (15)	C1—C2	1.5270 (18)
N1A—C1A	1.3160 (18)	C1—C11	1.5228 (18)
N2A—C1A	1.3272 (18)	C2—C3	1.5326 (19)
N3A—C1A	1.3250 (18)	C2—C21	1.5286 (18)
N1A—H12A	0.878 (16)	C3—C4	1.518 (2)
N1A—H11A	0.910 (16)	C4—C5	1.519 (2)
N2A—H21A	0.844 (18)	C5—C6	1.522 (2)
N2A—H22A	0.836 (16)	C1—H1	0.9800
N3A—H31A	0.865 (15)	C2—H2	0.9800
N3A—H32A	0.817 (17)	C3—H31	0.9700
N1B—C1B	1.3175 (18)	C3—H32	0.9700
N2B—C1B	1.3248 (18)	C4—H42	0.9700
N3B—C1B	1.3246 (18)	C4—H41	0.9700
N1B—H11B	0.890 (15)	C5—H51	0.9700
N1B—H12B	0.810 (17)	C5—H52	0.9700
N2B—H22B	0.871 (16)	C6—H61	0.9700
N2B—H21B	0.850 (18)	C6—H62	0.9700
C1A—N1A—H12A	117.8 (10)	O21—C21—C2	120.77 (11)
H11A—N1A—H12A	124.0 (14)	C11—C1—H1	106.00
C1A—N1A—H11A	117.9 (10)	C2—C1—H1	106.00
C1A—N2A—H21A	118.2 (11)	C6—C1—H1	106.00
C1A—N2A—H22A	117.5 (11)	C21—C2—H2	107.00
H21A—N2A—H22A	123.8 (16)	C3—C2—H2	107.00
C1A—N3A—H31A	118.8 (10)	C1—C2—H2	107.00
C1A—N3A—H32A	117.7 (11)	C2—C3—H32	109.00
H31A—N3A—H32A	119.7 (15)	C4—C3—H31	109.00
C1B—N1B—H12B	118.2 (12)	C4—C3—H32	109.00
H11B—N1B—H12B	120.8 (16)	H31—C3—H32	108.00
C1B—N1B—H11B	116.2 (10)	C2—C3—H31	109.00
C1B—N2B—H22B	118.5 (10)	C3—C4—H42	109.00
H21B—N2B—H22B	121.4 (15)	C3—C4—H41	109.00
C1B—N2B—H21B	119.2 (11)	C5—C4—H42	110.00
H31B—N3B—H32B	121.4 (14)	H41—C4—H42	108.00
C1B—N3B—H32B	120.1 (10)	C5—C4—H41	110.00
C1B—N3B—H31B	118.6 (11)	C6—C5—H52	109.00
C6—C1—C11	114.69 (10)	H51—C5—H52	108.00
C2—C1—C11	110.86 (10)	C6—C5—H51	109.00
C2—C1—C6	112.86 (11)	C4—C5—H51	109.00
C3—C2—C21	111.33 (11)	C4—C5—H52	109.00
C1—C2—C3	111.37 (11)	C1—C6—H61	109.00
C1—C2—C21	112.85 (10)	C5—C6—H61	109.00
C2—C3—C4	111.72 (12)	C5—C6—H62	109.00
C3—C4—C5	110.71 (13)	H61—C6—H62	108.00
C4—C5—C6	111.81 (12)	C1—C6—H62	109.00
C1—C6—C5	112.09 (12)	N2A—C1A—N3A	119.66 (13)
O11—C11—O12	122.68 (12)	N1A—C1A—N2A	120.37 (13)
O12—C11—C1	118.47 (11)	N1A—C1A—N3A	119.96 (12)
O11—C11—C1	118.76 (11)	N2B—C1B—N3B	120.13 (13)
O21—C21—O22	123.47 (11)	N1B—C1B—N2B	120.36 (13)
O22—C21—C2	115.75 (11)	N1B—C1B—N3B	119.49 (13)
C6—C1—C2—C3	−50.89 (14)	C1—C2—C3—C4	54.26 (15)
C6—C1—C2—C21	75.18 (13)	C21—C2—C3—C4	−72.64 (14)
C11—C1—C2—C3	178.88 (11)	C1—C2—C21—O21	−10.73 (17)
C11—C1—C2—C21	−55.05 (13)	C1—C2—C21—O22	168.09 (10)
C2—C1—C6—C5	50.69 (15)	C3—C2—C21—O21	115.36 (13)
C11—C1—C6—C5	178.95 (11)	C3—C2—C21—O22	−65.82 (14)
C2—C1—C11—O11	155.96 (11)	C2—C3—C4—C5	−57.11 (15)
C2—C1—C11—O12	−27.39 (16)	C3—C4—C5—C6	56.55 (16)
C6—C1—C11—O11	26.70 (16)	C4—C5—C6—C1	−53.32 (16)
C6—C1—C11—O12	−156.65 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O22^i	0.910 (16)	1.946 (15)	2.8492 (16)	171.2 (13)
N1A—H12A···O22^ii	0.878 (16)	1.960 (16)	2.8255 (15)	168.6 (14)
N2A—H21A···O11	0.844 (18)	2.065 (18)	2.8780 (18)	161.6 (15)
N3A—H31A···O21^ii	0.865 (15)	1.963 (15)	2.8270 (16)	176.4 (16)
N3A—H32A···O11	0.817 (17)	2.593 (17)	3.2299 (16)	135.9 (14)
N1B—H11B···O12^iii	0.890 (15)	1.899 (15)	2.7863 (17)	175.0 (15)
N1B—H12B···O12	0.810 (17)	2.204 (18)	2.9097 (17)	145.9 (16)
N2B—H21B···O22	0.850 (18)	1.999 (18)	2.8447 (18)	173.8 (16)
N2B—H22B···O11^iv	0.871 (16)	2.579 (16)	3.2913 (17)	139.6 (13)
N2B—H22B···N3B^v	0.871 (16)	2.593 (15)	3.3191 (18)	141.5 (13)
N3B—H31B···O11^iv	0.856 (17)	2.011 (17)	2.8468 (15)	165.1 (15)
N3B—H32B···O11^iii	0.948 (16)	1.975 (15)	2.8981 (15)	164.2 (14)

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

(II) guanidinium 3-carboxybenzoate monohydrate

Crystal data

CH6N3^+·C8H5O4^−·H2O	F(000) = 1024
Mr = 243.22	Dx = 1.413 Mg m^−3
Monoclinic, C2/c	Melting point: 474 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.970 (3) Å	Cell parameters from 1819 reflections
b = 5.1421 (6) Å	θ = 3.8–28.8°
c = 22.241 (2) Å	µ = 0.12 mm^−1
β = 107.577 (14)°	T = 297 K
V = 2286.3 (5) Å^3	Platelet, colourless
Z = 8	0.40 × 0.30 × 0.16 mm

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2239 independent reflections
Radiation source: Enhance (Mo) X-ray source	1694 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ω scans	θmax = 26.0°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −25→24
Tmin = 0.907, Tmax = 0.987	k = −5→6
3906 measured reflections	l = −27→16

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0881P)^2 + 1.4498P] where P = (Fo^2 + 2Fc^2)/3
2239 reflections	(Δ/σ)max = 0.002
181 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.50 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
O11	0.66357 (7)	0.4840 (3)	0.52173 (7)	0.0458 (5)
O12	0.77147 (7)	0.5771 (3)	0.53995 (7)	0.0453 (5)
O31	0.94195 (8)	0.1767 (4)	0.71504 (8)	0.0632 (7)
O32	0.91247 (10)	−0.0160 (4)	0.79184 (8)	0.0717 (7)
C1	0.74351 (9)	0.2626 (4)	0.60568 (8)	0.0309 (6)
C2	0.80914 (9)	0.2562 (4)	0.64532 (9)	0.0320 (6)
C3	0.82785 (10)	0.0833 (4)	0.69596 (9)	0.0346 (6)
C4	0.78025 (11)	−0.0864 (4)	0.70603 (10)	0.0408 (7)
C5	0.71536 (11)	−0.0851 (4)	0.66614 (10)	0.0426 (7)
C6	0.69681 (10)	0.0894 (4)	0.61645 (9)	0.0376 (6)
C11	0.72328 (9)	0.4525 (4)	0.55200 (9)	0.0330 (6)
C31	0.89860 (11)	0.0781 (5)	0.73853 (10)	0.0433 (7)
N1A	0.92726 (17)	0.4335 (6)	0.55135 (12)	0.0725 (10)
N2A	1.01868 (12)	0.5649 (5)	0.63160 (13)	0.0645 (9)
N3A	0.92136 (13)	0.8032 (5)	0.60519 (13)	0.0604 (8)
C1A	0.95621 (11)	0.6008 (5)	0.59668 (10)	0.0419 (7)
O1W	0.55885 (14)	0.6030 (5)	0.57132 (16)	0.1076 (13)
H2	0.84080	0.36830	0.63800	0.0380*
H4	0.79230	−0.20140	0.73990	0.0490*
H5	0.68410	−0.20140	0.67270	0.0510*
H6	0.65290	0.09120	0.59010	0.0450*
H12	0.75000	0.75000	0.50000	0.102 (16)*
H31	1.00000	0.146 (11)	0.75000	0.112 (17)*
H11A	0.882 (2)	0.434 (8)	0.5312 (19)	0.107 (13)*
H12A	0.952 (2)	0.330 (10)	0.539 (2)	0.121 (18)*
H21A	1.0371 (18)	0.437 (7)	0.6227 (17)	0.088 (12)*
H22A	1.0417 (16)	0.679 (7)	0.6666 (16)	0.084 (10)*
H31A	0.877 (3)	0.841 (11)	0.578 (3)	0.16 (2)*
H32A	0.9406 (15)	0.897 (6)	0.6354 (15)	0.059 (9)*
H11W	0.57800	0.56590	0.61220	0.1290*
H12W	0.59240	0.58380	0.54880	0.1290*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0298 (8)	0.0580 (10)	0.0419 (8)	0.0015 (7)	−0.0006 (6)	0.0120 (7)
O12	0.0309 (8)	0.0531 (10)	0.0472 (9)	0.0006 (7)	0.0049 (6)	0.0235 (7)
O31	0.0357 (9)	0.1032 (15)	0.0400 (9)	−0.0126 (9)	−0.0047 (7)	0.0184 (9)
O32	0.0632 (11)	0.1043 (16)	0.0400 (9)	0.0143 (11)	0.0041 (8)	0.0312 (10)
C1	0.0315 (10)	0.0327 (10)	0.0278 (9)	−0.0002 (8)	0.0081 (8)	−0.0007 (8)
C2	0.0311 (10)	0.0347 (10)	0.0302 (9)	−0.0012 (8)	0.0092 (8)	0.0044 (8)
C3	0.0385 (11)	0.0376 (11)	0.0278 (9)	0.0042 (9)	0.0101 (8)	0.0019 (8)
C4	0.0538 (13)	0.0360 (12)	0.0346 (10)	0.0017 (10)	0.0163 (9)	0.0080 (9)
C5	0.0473 (12)	0.0403 (12)	0.0431 (12)	−0.0119 (10)	0.0179 (10)	0.0020 (10)
C6	0.0317 (10)	0.0422 (12)	0.0374 (10)	−0.0053 (9)	0.0080 (8)	−0.0029 (9)
C11	0.0309 (10)	0.0359 (11)	0.0291 (9)	0.0011 (8)	0.0043 (8)	−0.0004 (8)
C31	0.0448 (12)	0.0493 (13)	0.0313 (10)	0.0082 (10)	0.0049 (9)	0.0053 (10)
N1A	0.0739 (18)	0.0752 (19)	0.0587 (15)	−0.0258 (16)	0.0056 (13)	−0.0193 (13)
N2A	0.0437 (12)	0.0649 (16)	0.0723 (16)	0.0022 (12)	−0.0012 (11)	−0.0088 (13)
N3A	0.0558 (14)	0.0620 (15)	0.0601 (14)	0.0054 (12)	0.0124 (11)	−0.0059 (12)
C1A	0.0401 (11)	0.0448 (12)	0.0371 (11)	−0.0091 (10)	0.0061 (9)	−0.0013 (10)
O1W	0.1022 (18)	0.0861 (17)	0.166 (3)	0.0114 (15)	0.0878 (18)	0.0111 (18)

Geometric parameters (Å, º)

O11—C11	1.240 (2)	N3A—H31A	0.96 (6)
O12—C11	1.291 (3)	N3A—H32A	0.83 (3)
O31—C31	1.282 (3)	C1—C2	1.393 (3)
O32—C31	1.231 (3)	C1—C11	1.501 (3)
O12—H12	1.2400	C1—C6	1.397 (3)
O31—H31	1.241 (6)	C2—C3	1.395 (3)
O1W—H12W	0.9800	C3—C4	1.394 (3)
O1W—H11W	0.9000	C3—C31	1.500 (3)
N1A—C1A	1.325 (4)	C4—C5	1.382 (3)
N2A—C1A	1.319 (4)	C5—C6	1.385 (3)
N3A—C1A	1.318 (4)	C2—H2	0.9300
N1A—H12A	0.85 (5)	C4—H4	0.9300
N1A—H11A	0.92 (4)	C5—H5	0.9300
N2A—H22A	0.98 (4)	C6—H6	0.9300
N2A—H21A	0.82 (4)
C11—O12—H12	112.00	C4—C5—C6	120.0 (2)
C31—O31—H31	112.1 (12)	C1—C6—C5	120.49 (19)
H11W—O1W—H12W	109.00	O12—C11—C1	115.91 (17)
H11A—N1A—H12A	119 (4)	O11—C11—O12	123.21 (19)
C1A—N1A—H12A	118 (3)	O11—C11—C1	120.88 (18)
C1A—N1A—H11A	123 (3)	O31—C31—O32	123.9 (2)
H21A—N2A—H22A	121 (3)	O31—C31—C3	115.07 (19)
C1A—N2A—H21A	115 (3)	O32—C31—C3	121.1 (2)
C1A—N2A—H22A	123 (2)	C1—C2—H2	120.00
H31A—N3A—H32A	122 (4)	C3—C2—H2	120.00
C1A—N3A—H31A	123 (4)	C3—C4—H4	120.00
C1A—N3A—H32A	115 (2)	C5—C4—H4	120.00
C2—C1—C11	120.45 (18)	C6—C5—H5	120.00
C6—C1—C11	120.45 (17)	C4—C5—H5	120.00
C2—C1—C6	119.10 (18)	C5—C6—H6	120.00
C1—C2—C3	120.62 (19)	C1—C6—H6	120.00
C2—C3—C4	119.23 (19)	N1A—C1A—N2A	120.2 (3)
C4—C3—C31	120.48 (19)	N1A—C1A—N3A	118.4 (3)
C2—C3—C31	120.29 (19)	N2A—C1A—N3A	121.4 (2)
C3—C4—C5	120.52 (19)
C6—C1—C2—C3	−1.4 (3)	C1—C2—C3—C31	−179.85 (19)
C11—C1—C2—C3	178.81 (18)	C2—C3—C4—C5	0.5 (3)
C2—C1—C6—C5	0.5 (3)	C31—C3—C4—C5	−178.8 (2)
C11—C1—C6—C5	−179.71 (19)	C2—C3—C31—O31	−20.3 (3)
C2—C1—C11—O11	−170.30 (19)	C2—C3—C31—O32	159.9 (2)
C2—C1—C11—O12	9.8 (3)	C4—C3—C31—O31	159.0 (2)
C6—C1—C11—O11	9.9 (3)	C4—C3—C31—O32	−20.9 (3)
C6—C1—C11—O12	−170.02 (18)	C3—C4—C5—C6	−1.4 (3)
C1—C2—C3—C4	0.9 (3)	C4—C5—C6—C1	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O12	0.92 (4)	2.50 (4)	3.284 (4)	144 (3)
N1A—H12A···O1W^i	0.85 (5)	2.44 (5)	3.156 (5)	144 (4)
N2A—H21A···O1W^i	0.82 (4)	2.19 (4)	2.972 (4)	161 (4)
N2A—H22A···O32^ii	0.98 (4)	1.92 (4)	2.854 (3)	158 (3)
N3A—H31A···O12	0.96 (6)	2.52 (6)	3.253 (3)	133 (4)
N3A—H31A···O11^iii	0.96 (6)	2.31 (6)	3.050 (3)	134 (5)
N3A—H32A···O31^iv	0.83 (3)	2.28 (3)	3.034 (3)	153 (3)
O1W—H11W···O32^v	0.90	2.12	2.982 (4)	160
O1W—H12W···O11	0.98	1.84	2.806 (4)	166
O12—H12···O12^iii	1.24	1.24	2.483 (2)	180
O31—H31···O31^vi	1.241 (6)	1.241 (6)	2.462 (2)	165 (5)

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

(III) bis(guanidinium) benzene-1,4-dicarboxylate trihydrate

Crystal data

2CH6N3^+·C8H4O4^2^−·3H2O	F(000) = 720
Mr = 338.34	Dx = 1.423 Mg m^−3
Monoclinic, C2/c	Melting point: 505 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 18.0402 (7) Å	Cell parameters from 1952 reflections
b = 5.1420 (2) Å	θ = 3.0–28.6°
c = 18.1496 (7) Å	µ = 0.12 mm^−1
β = 110.297 (4)°	T = 297 K
V = 1579.07 (11) Å^3	Block, colourless
Z = 4	0.25 × 0.25 × 0.25 mm

Data collection

Oxford Gemini-S Ultra CCD area-detector diffractometer	1546 independent reflections
Radiation source: Enhance (Mo) X-ray source	1177 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 16.0774 pixels mm^-1	θmax = 26.0°, θmin = 3.9°
ω scans	h = −21→22
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −6→6
Tmin = 0.98, Tmax = 0.99	l = −22→11
3988 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0724P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
1546 reflections	Δρmax = 0.23 e Å^−3
130 parameters	Δρmin = −0.48 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

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
O11	0.91167 (6)	0.6439 (2)	0.62864 (7)	0.0362 (4)
O12	0.80638 (7)	0.7267 (2)	0.66117 (7)	0.0379 (4)
C1	0.79313 (9)	0.4245 (3)	0.55846 (9)	0.0267 (5)
C2	0.83110 (10)	0.2372 (3)	0.52989 (10)	0.0320 (5)
C6	0.71103 (9)	0.4345 (3)	0.52779 (10)	0.0318 (5)
C11	0.84013 (9)	0.6122 (3)	0.62100 (9)	0.0280 (5)
N1A	0.67652 (9)	0.6121 (3)	0.71264 (10)	0.0414 (6)
N2A	0.55815 (9)	0.8196 (4)	0.68312 (11)	0.0446 (5)
N3A	0.65240 (11)	0.9751 (3)	0.63647 (10)	0.0411 (5)
C1A	0.62841 (9)	0.8024 (3)	0.67693 (9)	0.0303 (5)
O1W	0.50000	0.4250 (3)	0.75000	0.0414 (6)
O2W	1.00186 (8)	0.7514 (3)	0.53680 (9)	0.0513 (5)
H2	0.88600	0.22690	0.54990	0.0380*
H6	0.68430	0.55830	0.54640	0.0380*
H11A	0.7265 (13)	0.600 (4)	0.7065 (13)	0.051 (6)*
H12A	0.6644 (12)	0.506 (5)	0.7446 (14)	0.052 (6)*
H21A	0.5402 (13)	0.686 (5)	0.7100 (15)	0.064 (7)*
H22A	0.5261 (14)	0.955 (5)	0.6619 (15)	0.075 (8)*
H31A	0.6211 (15)	1.082 (4)	0.6093 (15)	0.058 (7)*
H32A	0.7004 (12)	0.959 (4)	0.6331 (12)	0.042 (5)*
H11W	0.46660	0.32690	0.70930	0.0500*
H21W	0.96610	0.73390	0.55720	0.0620*
H22W	0.97120	0.81500	0.48360	0.0620*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0248 (6)	0.0458 (7)	0.0392 (7)	−0.0037 (5)	0.0125 (5)	−0.0077 (6)
O12	0.0333 (7)	0.0453 (8)	0.0389 (7)	−0.0039 (5)	0.0175 (5)	−0.0146 (6)
C1	0.0264 (8)	0.0295 (9)	0.0256 (7)	−0.0003 (6)	0.0109 (6)	0.0018 (6)
C2	0.0218 (7)	0.0377 (9)	0.0362 (9)	0.0024 (7)	0.0098 (7)	−0.0016 (8)
C6	0.0282 (8)	0.0326 (9)	0.0356 (9)	0.0042 (7)	0.0124 (7)	−0.0053 (7)
C11	0.0269 (8)	0.0311 (9)	0.0259 (8)	0.0023 (7)	0.0092 (6)	0.0029 (7)
N1A	0.0352 (9)	0.0433 (10)	0.0500 (10)	0.0094 (7)	0.0202 (7)	0.0155 (8)
N2A	0.0350 (8)	0.0476 (10)	0.0560 (10)	0.0109 (8)	0.0217 (7)	0.0100 (9)
N3A	0.0391 (9)	0.0392 (9)	0.0457 (9)	0.0046 (8)	0.0157 (8)	0.0105 (8)
C1A	0.0300 (9)	0.0305 (9)	0.0304 (8)	0.0007 (7)	0.0104 (7)	−0.0010 (7)
O1W	0.0388 (10)	0.0383 (10)	0.0396 (10)	0.0000	0.0041 (8)	0.0000
O2W	0.0493 (8)	0.0595 (10)	0.0532 (8)	0.0110 (7)	0.0282 (7)	0.0136 (7)

Geometric parameters (Å, º)

O11—C11	1.260 (2)	N2A—H22A	0.90 (3)
O12—C11	1.248 (2)	N2A—H21A	0.96 (3)
O1W—H11W	0.9200	N3A—H32A	0.89 (2)
O1W—H11W^i	0.9200	N3A—H31A	0.82 (2)
O2W—H21W	0.8500	C1—C2	1.383 (2)
O2W—H22W	0.9900	C1—C11	1.507 (2)
N1A—C1A	1.319 (2)	C1—C6	1.391 (2)
N2A—C1A	1.314 (2)	C2—C6^ii	1.379 (2)
N3A—C1A	1.317 (2)	C2—H2	0.9300
N1A—H12A	0.88 (2)	C6—H6	0.9300
N1A—H11A	0.95 (2)
H11W—O1W—H11W^i	114.00	C2—C1—C11	120.40 (15)
H21W—O2W—H22W	102.00	C1—C2—C6^ii	121.09 (17)
C1A—N1A—H12A	120.9 (16)	C1—C6—C2^ii	120.68 (16)
C1A—N1A—H11A	118.8 (13)	O11—C11—O12	124.30 (15)
H11A—N1A—H12A	120 (2)	O11—C11—C1	116.94 (14)
C1A—N2A—H22A	120.7 (17)	O12—C11—C1	118.76 (15)
H21A—N2A—H22A	119 (2)	C6^ii—C2—H2	119.00
C1A—N2A—H21A	120.0 (15)	C1—C2—H2	119.00
H31A—N3A—H32A	120 (2)	C2^ii—C6—H6	120.00
C1A—N3A—H31A	120 (2)	C1—C6—H6	120.00
C1A—N3A—H32A	119.3 (13)	N1A—C1A—N3A	119.11 (17)
C6—C1—C11	121.37 (14)	N2A—C1A—N3A	121.03 (17)
C2—C1—C6	118.23 (15)	N1A—C1A—N2A	119.85 (17)
C6—C1—C2—C6^ii	0.4 (2)	C2—C1—C11—O12	−159.86 (15)
C11—C1—C2—C6^ii	−179.45 (15)	C6—C1—C11—O11	−159.19 (15)
C2—C1—C6—C2^ii	−0.4 (2)	C6—C1—C11—O12	20.3 (2)
C11—C1—C6—C2^ii	179.45 (15)	C1—C2—C6^ii—C1^ii	−0.4 (3)
C2—C1—C11—O11	20.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O12	0.95 (2)	2.00 (2)	2.868 (2)	151.3 (19)
N1A—H12A···O12^iii	0.88 (2)	2.15 (2)	2.963 (2)	153 (2)
N2A—H21A···O1W	0.96 (3)	1.79 (3)	2.752 (2)	174 (2)
N2A—H22A···O11^iv	0.90 (3)	2.17 (3)	2.988 (2)	151 (2)
N3A—H31A···O2W^iv	0.82 (2)	2.27 (3)	3.043 (2)	157 (2)
N3A—H32A···O12	0.89 (2)	2.16 (2)	2.947 (2)	146.6 (18)
O1W—H11W···O11^v	0.92	1.73	2.6542 (14)	174
O2W—H21W···O11	0.85	1.93	2.7591 (19)	162
O2W—H22W···O2W^vi	0.99	2.34	2.875 (2)	113

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