Hydrated salts of 3,5-dihydroxybenzoic acid with organic diamines: hydrogen-bonded supramolecular structures in two and three dimensions

Burchell, C.J.; Ferguson, G.; Lough, A.J.; Gregson, R.M.; Glidewell, C.

doi:10.1107/S0108768100019832

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Hydrated salts of 3,5-dihydroxybenzoic acid with organic diamines: hydrogen-bonded supramolecular structures in two and three dimensions

C. J. Burchell, G. Ferguson, A. J. Lough, R. M. Gregson and C. Glidewell

The trigonally trisubstituted acid 3,5-dihydroxybenzoic acid forms hydrated salt-type adducts with organic diamines. In 1,4-diazabicyclo[2.2.2]octane–3,5-dihydroxybenzoic acid–water (1/1/1) (1), where Z′ = 2 in P2₁/c, the constitution is [HN(CH₂CH₂)₃N]⁺·[(HO)₂C₆H₃COO]⁻·H₂O: the anions and the water molecules are linked by six O—H

O hydrogen bonds to form two-dimensional sheets and each cation is linked to a single sheet by one O—H

N and one N—H

O hydrogen bond. Piperazine–3,5-dihydroxybenzoic acid–water (1/2/4) (2) and 1,2-diaminoethane–3,5-dihydroxybenzoic acid–water (1/2/2) (3) are also both salts with constitutions [H₂N(CH₂CH₂)₂NH₂]²⁺·2[(HO)₂C₆H₃COO]⁻·4H₂O and [H₃NCH₂CH₂NH₃]²⁺·2[(HO)₂C₆H₃COO]⁻·2H₂O, respectively. Both (2) and (3) have supramolecular structures which are three-dimensional: in (2) the anions and the water molecules are linked by six O—H

O hydrogen bonds to form a three-dimensional framework enclosing large centrosymmetric voids, which contain the cations that are linked to the framework by two N—H

O hydrogen bonds; in (3) the construction of the three-dimensional framework requires the participation of cations, anions and water molecules, which are linked together by four O—H

O and three N—H

O hydrogen bonds.

Keywords: hydrated salts; hydrogen bonds; supramolecular structures; organic diamines.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100019832/na0115sup1.cif Contains datablocks global, 1, 2, 3
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768100019832/na01151sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768100019832/na01152sup3.hkl Contains datablock 2
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768100019832/na01153sup4.hkl Contains datablock 3

CCDC references: 166502; 166503; 166504

Comment top

In full text version

Experimental top

In full text version

Computing details top

For all compounds, data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b) for (1); NRCVAX96 and SHELXL97 (Sheldrick, 1997b) for (2), (3). Molecular graphics: ORTEP (Johnson, 1976), PLATON (Spek, 2000) for (1); NRCVAX96, ORTEP (Johnson, 1976), PLATON (Spek, 2000) for (2), (3). Software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999) for (1); NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999) for (2), (3).

Figures top

In full text version

(1) 1,4-Diazabicyclo[2.2.2]octane–3,5-dihydroxybenzoic acid–water (1/1/1) top

Crystal data top

C₆H₁₃N₂·C₇H₅O₄·H₂O	F(000) = 1216
M_r = 284.31	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4478 (4) Å	Cell parameters from 15105 reflections
b = 11.7644 (4) Å	θ = 2.8–27.5°
c = 25.9024 (12) Å	µ = 0.10 mm⁻¹
β = 101.969 (2)°	T = 100 K
V = 2816.4 (2) Å³	Plate, colourless
Z = 8	0.30 × 0.25 × 0.13 mm

Data collection top

Kappa-CCD diffractometer	6382 independent reflections
Radiation source: fine-focus sealed X-ray tube	3976 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ scans and ω scans with κ offsets	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→12
T_min = 0.970, T_max = 0.987	k = −15→0
15105 measured reflections	l = −33→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0544P)² + 0.0968P] where P = (F_o² + 2F_c²)/3
6382 reflections	(Δ/σ)_max < 0.001
379 parameters	Δρ_max = 0.28 e Å⁻³
4 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₆H₁₃N₂·C₇H₅O₄·H₂O	V = 2816.4 (2) Å³
M_r = 284.31	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4478 (4) Å	µ = 0.10 mm⁻¹
b = 11.7644 (4) Å	T = 100 K
c = 25.9024 (12) Å	0.30 × 0.25 × 0.13 mm
β = 101.969 (2)°

Data collection top

Kappa-CCD diffractometer	6382 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	3976 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.987	R_int = 0.028
15105 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	4 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.05	Δρ_max = 0.28 e Å⁻³
6382 reflections	Δρ_min = −0.22 e Å⁻³
379 parameters

Special details top

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O11	0.36065 (14)	0.22719 (10)	0.38842 (5)	0.0249 (3)
O13	0.32294 (16)	0.28105 (10)	0.19326 (5)	0.0307 (4)
O12	0.31406 (15)	0.04408 (10)	0.39657 (5)	0.0277 (3)
O15	0.36665 (17)	−0.12219 (10)	0.22238 (5)	0.0307 (4)
C11	0.33986 (19)	0.11054 (15)	0.31178 (7)	0.0188 (4)
C12	0.3335 (2)	0.20387 (15)	0.27838 (7)	0.0206 (4)
C13	0.3337 (2)	0.18777 (15)	0.22520 (7)	0.0223 (4)
C14	0.3426 (2)	0.07860 (15)	0.20554 (7)	0.0217 (4)
C15	0.3521 (2)	−0.01404 (15)	0.23915 (7)	0.0211 (4)
C16	0.3492 (2)	0.00104 (15)	0.29214 (7)	0.0205 (4)
C17	0.3381 (2)	0.12686 (15)	0.36933 (7)	0.0199 (4)
O21	0.16930 (19)	0.94541 (12)	0.55696 (6)	0.0470 (5)
O22	0.17361 (16)	0.77812 (11)	0.59704 (5)	0.0315 (4)
O23	0.20451 (15)	0.83694 (11)	0.36934 (5)	0.0275 (3)
O25	0.13207 (17)	0.48982 (10)	0.45457 (5)	0.0331 (4)
C21	0.1703 (2)	0.77829 (15)	0.50540 (7)	0.0204 (4)
C22	0.1848 (2)	0.83976 (16)	0.46093 (7)	0.0217 (4)
C23	0.1869 (2)	0.78241 (15)	0.41432 (7)	0.0209 (4)
C24	0.1711 (2)	0.66506 (15)	0.41152 (7)	0.0219 (4)
C25	0.1526 (2)	0.60463 (15)	0.45574 (7)	0.0223 (4)
C26	0.1538 (2)	0.66076 (15)	0.50312 (7)	0.0217 (4)
C27	0.1710 (2)	0.84099 (17)	0.55641 (8)	0.0255 (5)
N31	0.34719 (17)	0.22007 (12)	0.49341 (6)	0.0223 (4)
N32	0.33476 (17)	0.25056 (13)	0.58905 (6)	0.0226 (4)
C31	0.1919 (2)	0.22225 (16)	0.49827 (7)	0.0248 (5)
C32	0.1884 (2)	0.2400 (2)	0.55635 (8)	0.0396 (6)
C33	0.4229 (2)	0.12401 (16)	0.52558 (7)	0.0265 (5)
C34	0.4167 (3)	0.14669 (18)	0.58332 (8)	0.0354 (6)
C35	0.4207 (2)	0.32963 (16)	0.51227 (7)	0.0269 (5)
C36	0.4078 (3)	0.34652 (18)	0.56955 (8)	0.0403 (6)
N41	0.14892 (17)	0.88461 (12)	0.68157 (6)	0.0229 (4)
N42	0.13296 (17)	0.97439 (13)	0.76916 (6)	0.0244 (4)
C41	0.2969 (2)	0.91240 (17)	0.71126 (8)	0.0292 (5)
C42	0.2852 (2)	0.95525 (17)	0.76594 (8)	0.0299 (5)
C43	0.0776 (2)	0.80384 (16)	0.71260 (8)	0.0282 (5)
C44	0.0576 (2)	0.86338 (16)	0.76306 (8)	0.0286 (5)
C45	0.0608 (2)	0.99054 (17)	0.67159 (8)	0.0309 (5)
C46	0.0629 (2)	1.04780 (16)	0.72492 (7)	0.0268 (5)
O1	0.40434 (17)	−0.13282 (12)	0.12370 (6)	0.0321 (4)
O2	0.14775 (18)	0.39832 (12)	0.36246 (6)	0.0350 (4)
H13	0.3264	0.2607	0.1625	0.046*
H15	0.3793	−0.1209	0.1912	0.046*
H12	0.3289	0.2785	0.2919	0.025*
H14	0.3421	0.0675	0.1692	0.026*
H16	0.3535	−0.0629	0.3148	0.025*
H23	0.2337	0.9036	0.3768	0.041*
H25	0.1363	0.4648	0.4245	0.050*
H22	0.1932	0.9202	0.4625	0.026*
H24	0.1729	0.6263	0.3795	0.026*
H26	0.1435	0.6193	0.5336	0.026*
H31	0.3515	0.2091	0.4582	0.027*
H31A	0.1442	0.1496	0.4856	0.030*
H31B	0.1401	0.2848	0.4767	0.030*
H32A	0.1326	0.3097	0.5601	0.047*
H32B	0.1385	0.1750	0.5690	0.047*
H33A	0.5247	0.1195	0.5216	0.032*
H33B	0.3746	0.0511	0.5137	0.032*
H34A	0.3707	0.0811	0.5973	0.042*
H34B	0.5164	0.1543	0.6044	0.042*
H35A	0.3740	0.3935	0.4903	0.032*
H35B	0.5238	0.3267	0.5098	0.032*
H36A	0.5057	0.3555	0.5919	0.048*
H36B	0.3529	0.4171	0.5724	0.048*
H41	0.1548	0.8514	0.6495	0.028*
H41A	0.3406	0.9717	0.6924	0.035*
H41B	0.3590	0.8439	0.7146	0.035*
H42A	0.3290	0.8988	0.7929	0.036*
H42B	0.3398	1.0272	0.7736	0.036*
H43A	0.1382	0.7352	0.7216	0.034*
H43B	−0.0176	0.7802	0.6915	0.034*
H44A	−0.0468	0.8752	0.7618	0.034*
H44B	0.0966	0.8147	0.7939	0.034*
H45A	−0.0398	0.9720	0.6540	0.037*
H45B	0.1019	1.0423	0.6484	0.037*
H46A	0.1159	1.1207	0.7266	0.032*
H46B	−0.0375	1.0645	0.7282	0.032*
H1A	0.328 (3)	−0.178 (2)	0.1098 (11)	0.082 (5)*
H1B	0.484 (3)	−0.176 (2)	0.1225 (11)	0.082 (5)*
H2A	0.147 (3)	0.445 (2)	0.3330 (10)	0.082 (5)*
H2B	0.221 (3)	0.349 (2)	0.3646 (11)	0.082 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0363 (9)	0.0214 (7)	0.0181 (7)	−0.0014 (6)	0.0080 (6)	−0.0001 (6)
O13	0.0539 (10)	0.0238 (7)	0.0160 (7)	0.0065 (7)	0.0107 (7)	0.0051 (6)
O12	0.0421 (9)	0.0244 (7)	0.0177 (7)	−0.0053 (6)	0.0086 (6)	0.0031 (6)
O15	0.0496 (10)	0.0217 (7)	0.0230 (8)	−0.0017 (6)	0.0124 (7)	−0.0040 (6)
C11	0.0172 (11)	0.0243 (10)	0.0144 (9)	0.0003 (8)	0.0024 (8)	−0.0003 (8)
C12	0.0238 (11)	0.0213 (10)	0.0164 (9)	0.0026 (8)	0.0036 (8)	0.0003 (8)
C13	0.0245 (11)	0.0230 (10)	0.0191 (10)	0.0008 (8)	0.0037 (8)	0.0032 (9)
C14	0.0248 (11)	0.0262 (10)	0.0144 (9)	0.0009 (8)	0.0050 (8)	−0.0003 (8)
C15	0.0217 (11)	0.0202 (10)	0.0215 (10)	−0.0037 (8)	0.0048 (8)	−0.0053 (8)
C16	0.0224 (11)	0.0217 (10)	0.0176 (10)	−0.0008 (8)	0.0045 (8)	0.0021 (8)
C17	0.0190 (11)	0.0229 (10)	0.0172 (10)	0.0015 (8)	0.0024 (8)	−0.0012 (9)
O21	0.0904 (14)	0.0241 (8)	0.0314 (9)	−0.0077 (8)	0.0241 (9)	−0.0053 (7)
O22	0.0454 (10)	0.0315 (8)	0.0198 (7)	0.0027 (7)	0.0117 (7)	−0.0001 (6)
O23	0.0413 (9)	0.0243 (7)	0.0182 (7)	−0.0058 (7)	0.0096 (6)	0.0028 (6)
O25	0.0605 (11)	0.0184 (7)	0.0224 (8)	−0.0014 (7)	0.0129 (7)	−0.0007 (6)
C21	0.0192 (11)	0.0226 (10)	0.0197 (10)	−0.0006 (8)	0.0046 (8)	0.0002 (8)
C22	0.0230 (11)	0.0196 (10)	0.0220 (10)	−0.0035 (8)	0.0033 (8)	−0.0029 (8)
C23	0.0215 (11)	0.0235 (10)	0.0179 (10)	−0.0001 (8)	0.0046 (8)	0.0042 (8)
C24	0.0269 (12)	0.0210 (10)	0.0181 (10)	0.0011 (8)	0.0054 (8)	−0.0013 (8)
C25	0.0256 (11)	0.0185 (10)	0.0225 (10)	0.0014 (8)	0.0048 (8)	0.0011 (8)
C26	0.0232 (11)	0.0235 (10)	0.0186 (10)	0.0023 (8)	0.0048 (8)	0.0043 (8)
C27	0.0259 (12)	0.0282 (12)	0.0232 (11)	−0.0026 (9)	0.0068 (9)	−0.0018 (9)
N31	0.0255 (10)	0.0270 (9)	0.0153 (8)	−0.0013 (7)	0.0063 (7)	−0.0032 (7)
N32	0.0262 (10)	0.0230 (8)	0.0185 (8)	0.0007 (7)	0.0044 (7)	−0.0020 (7)
C31	0.0222 (12)	0.0296 (11)	0.0218 (10)	−0.0002 (9)	0.0023 (8)	0.0020 (9)
C32	0.0271 (13)	0.0698 (16)	0.0217 (11)	0.0059 (11)	0.0048 (10)	−0.0026 (11)
C33	0.0259 (12)	0.0260 (11)	0.0274 (11)	0.0070 (8)	0.0053 (9)	−0.0015 (9)
C34	0.0480 (15)	0.0350 (12)	0.0215 (11)	0.0144 (11)	0.0034 (10)	0.0002 (10)
C35	0.0335 (13)	0.0257 (11)	0.0228 (11)	−0.0059 (9)	0.0086 (9)	−0.0008 (9)
C36	0.0631 (17)	0.0343 (12)	0.0273 (12)	−0.0158 (11)	0.0178 (11)	−0.0057 (10)
N41	0.0273 (10)	0.0250 (9)	0.0175 (8)	0.0001 (7)	0.0068 (7)	−0.0030 (7)
N42	0.0239 (10)	0.0262 (9)	0.0228 (9)	−0.0007 (7)	0.0038 (7)	−0.0034 (7)
C41	0.0231 (12)	0.0332 (11)	0.0320 (12)	−0.0022 (9)	0.0070 (9)	−0.0021 (10)
C42	0.0217 (12)	0.0330 (11)	0.0321 (12)	−0.0004 (9)	−0.0012 (9)	−0.0099 (10)
C43	0.0317 (13)	0.0263 (11)	0.0283 (11)	−0.0075 (9)	0.0100 (9)	−0.0025 (9)
C44	0.0346 (13)	0.0305 (11)	0.0211 (11)	−0.0067 (9)	0.0066 (9)	−0.0005 (9)
C45	0.0361 (13)	0.0310 (11)	0.0235 (11)	0.0090 (10)	0.0012 (9)	0.0003 (9)
C46	0.0259 (12)	0.0262 (11)	0.0281 (11)	0.0037 (9)	0.0052 (9)	−0.0027 (9)
O1	0.0370 (10)	0.0317 (8)	0.0274 (8)	0.0038 (7)	0.0059 (7)	−0.0060 (7)
O2	0.0523 (11)	0.0304 (8)	0.0246 (8)	0.0081 (7)	0.0132 (8)	0.0012 (7)

Geometric parameters (Å, º) top

O11—C17	1.280 (2)	C31—H31A	0.99
O13—C13	1.365 (2)	C31—H31B	0.99
O13—H13	0.84	C32—H32A	0.99
O12—C17	1.251 (2)	C32—H32B	0.99
O15—C15	1.361 (2)	C33—C34	1.532 (3)
O15—H15	0.84	C33—H33A	0.99
C11—C12	1.391 (2)	C33—H33B	0.99
C11—C16	1.395 (2)	C34—H34A	0.99
C11—C17	1.507 (3)	C34—H34B	0.99
C12—C13	1.391 (3)	C35—C36	1.527 (3)
C12—H12	0.95	C35—H35A	0.99
C13—C14	1.390 (3)	C35—H35B	0.99
C14—C15	1.386 (3)	C36—H36A	0.99
C14—H14	0.95	C36—H36B	0.99
C15—C16	1.390 (2)	N41—C41	1.486 (2)
C16—H16	0.95	N41—C45	1.491 (2)
O21—C27	1.229 (2)	N41—C43	1.493 (2)
O22—C27	1.282 (2)	N41—H41	0.93
O23—C23	1.370 (2)	N42—C42	1.475 (2)
O23—H23	0.84	N42—C46	1.477 (2)
O25—C25	1.364 (2)	N42—C44	1.480 (2)
O25—H25	0.84	C41—C42	1.529 (3)
C21—C22	1.391 (2)	C41—H41A	0.99
C21—C26	1.391 (2)	C41—H41B	0.99
C21—C27	1.512 (3)	C42—H42A	0.99
C22—C23	1.387 (2)	C42—H42B	0.99
C22—H22	0.95	C43—C44	1.529 (3)
C23—C24	1.389 (2)	C43—H43A	0.99
C24—C25	1.390 (3)	C43—H43B	0.99
C24—H24	0.95	C44—H44A	0.99
C25—C26	1.391 (3)	C44—H44B	0.99
C26—H26	0.95	C45—C46	1.533 (3)
N31—C33	1.495 (2)	C45—H45A	0.99
N31—C35	1.497 (2)	C45—H45B	0.99
N31—C31	1.498 (2)	C46—H46A	0.99
N31—H31	0.93	C46—H46B	0.99
N32—C36	1.466 (3)	O1—H1A	0.91 (2)
N32—C32	1.469 (2)	O1—H1B	0.91 (2)
N32—C34	1.470 (2)	O2—H2A	0.94 (2)
C31—C32	1.526 (3)	O2—H2B	0.90 (2)

C13—O13—H13	109.5	C34—C33—H33A	110.2
C15—O15—H15	109.5	N31—C33—H33B	110.2
C12—C11—C16	120.01 (17)	C34—C33—H33B	110.2
C12—C11—C17	120.45 (16)	H33A—C33—H33B	108.5
C16—C11—C17	119.54 (16)	N32—C34—C33	111.75 (15)
C13—C12—C11	119.97 (17)	N32—C34—H34A	109.3
C13—C12—H12	120.0	C33—C34—H34A	109.3
C11—C12—H12	120.0	N32—C34—H34B	109.3
O13—C13—C14	121.54 (16)	C33—C34—H34B	109.3
O13—C13—C12	118.39 (16)	H34A—C34—H34B	107.9
C14—C13—C12	120.06 (17)	N31—C35—C36	107.71 (15)
C15—C14—C13	119.82 (17)	N31—C35—H35A	110.2
C15—C14—H14	120.1	C36—C35—H35A	110.2
C13—C14—H14	120.1	N31—C35—H35B	110.2
O15—C15—C14	122.18 (17)	C36—C35—H35B	110.2
O15—C15—C16	117.30 (16)	H35A—C35—H35B	108.5
C14—C15—C16	120.52 (17)	N32—C36—C35	111.87 (16)
C15—C16—C11	119.59 (17)	N32—C36—H36A	109.2
C15—C16—H16	120.2	C35—C36—H36A	109.2
C11—C16—H16	120.2	N32—C36—H36B	109.2
O12—C17—O11	122.36 (17)	C35—C36—H36B	109.2
O12—C17—C11	119.97 (16)	H36A—C36—H36B	107.9
O11—C17—C11	117.67 (16)	C41—N41—C45	109.72 (15)
C23—O23—H23	109.5	C41—N41—C43	110.05 (15)
C25—O25—H25	109.5	C45—N41—C43	109.09 (16)
C22—C21—C26	120.72 (17)	C41—N41—H41	109.3
C22—C21—C27	119.13 (16)	C45—N41—H41	109.3
C26—C21—C27	120.14 (17)	C43—N41—H41	109.3
C23—C22—C21	119.32 (17)	C42—N42—C46	109.30 (16)
C23—C22—H22	120.3	C42—N42—C44	108.20 (15)
C21—C22—H22	120.3	C46—N42—C44	107.75 (14)
O23—C23—C22	122.59 (16)	N41—C41—C42	108.13 (16)
O23—C23—C24	116.85 (16)	N41—C41—H41A	110.1
C22—C23—C24	120.56 (17)	C42—C41—H41A	110.1
C23—C24—C25	119.73 (17)	N41—C41—H41B	110.1
C23—C24—H24	120.1	C42—C41—H41B	110.1
C25—C24—H24	120.1	H41A—C41—H41B	108.4
O25—C25—C24	121.99 (16)	N42—C42—C41	111.17 (15)
O25—C25—C26	117.70 (16)	N42—C42—H42A	109.4
C24—C25—C26	120.32 (17)	C41—C42—H42A	109.4
C25—C26—C21	119.31 (17)	N42—C42—H42B	109.4
C25—C26—H26	120.3	C41—C42—H42B	109.4
C21—C26—H26	120.3	H42A—C42—H42B	108.0
O21—C27—O22	124.42 (18)	N41—C43—C44	108.56 (14)
O21—C27—C21	120.01 (18)	N41—C43—H43A	110.0
O22—C27—C21	115.57 (16)	C44—C43—H43A	110.0
C33—N31—C35	109.46 (14)	N41—C43—H43B	110.0
C33—N31—C31	109.24 (15)	C44—C43—H43B	110.0
C35—N31—C31	110.71 (15)	H43A—C43—H43B	108.4
C33—N31—H31	109.1	N42—C44—C43	110.72 (16)
C35—N31—H31	109.1	N42—C44—H44A	109.5
C31—N31—H31	109.1	C43—C44—H44A	109.5
C36—N32—C32	108.69 (16)	N42—C44—H44B	109.5
C36—N32—C34	108.05 (17)	C43—C44—H44B	109.5
C32—N32—C34	108.90 (16)	H44A—C44—H44B	108.1
N31—C31—C32	107.89 (15)	N41—C45—C46	107.98 (15)
N31—C31—H31A	110.1	N41—C45—H45A	110.1
C32—C31—H31A	110.1	C46—C45—H45A	110.1
N31—C31—H31B	110.1	N41—C45—H45B	110.1
C32—C31—H31B	110.1	C46—C45—H45B	110.1
H31A—C31—H31B	108.4	H45A—C45—H45B	108.4
N32—C32—C31	111.67 (17)	N42—C46—C45	111.23 (15)
N32—C32—H32A	109.3	N42—C46—H46A	109.4
C31—C32—H32A	109.3	C45—C46—H46A	109.4
N32—C32—H32B	109.3	N42—C46—H46B	109.4
C31—C32—H32B	109.3	C45—C46—H46B	109.4
H32A—C32—H32B	107.9	H46A—C46—H46B	108.0
N31—C33—C34	107.56 (15)	H1A—O1—H1B	105 (2)
N31—C33—H33A	110.2	H2A—O2—H2B	108 (2)

C16—C11—C12—C13	1.2 (3)	C26—C21—C27—O22	8.2 (3)
C17—C11—C12—C13	−179.36 (17)	C33—N31—C31—C32	60.58 (19)
C11—C12—C13—O13	178.06 (16)	C35—N31—C31—C32	−60.0 (2)
C11—C12—C13—C14	−1.0 (3)	C36—N32—C32—C31	58.5 (2)
O13—C13—C14—C15	−179.45 (18)	C34—N32—C32—C31	−59.0 (2)
C12—C13—C14—C15	−0.4 (3)	N31—C31—C32—N32	0.6 (2)
C13—C14—C15—O15	−177.42 (17)	C35—N31—C33—C34	59.2 (2)
C13—C14—C15—C16	1.7 (3)	C31—N31—C33—C34	−62.15 (19)
O15—C15—C16—C11	177.65 (17)	C36—N32—C34—C33	−60.6 (2)
C14—C15—C16—C11	−1.5 (3)	C32—N32—C34—C33	57.2 (2)
C12—C11—C16—C15	0.1 (3)	N31—C33—C34—N32	2.5 (2)
C17—C11—C16—C15	−179.41 (17)	C33—N31—C35—C36	−62.2 (2)
C12—C11—C17—O12	165.34 (17)	C31—N31—C35—C36	58.3 (2)
C16—C11—C17—O12	−15.2 (3)	C32—N32—C36—C35	−60.3 (2)
C12—C11—C17—O11	−14.1 (3)	C34—N32—C36—C35	57.7 (2)
C16—C11—C17—O11	165.36 (17)	N31—C35—C36—N32	2.4 (3)
C26—C21—C22—C23	−1.8 (3)	C45—N41—C41—C42	65.9 (2)
C27—C21—C22—C23	178.83 (17)	C43—N41—C41—C42	−54.1 (2)
C21—C22—C23—O23	−178.29 (17)	C46—N42—C42—C41	−52.3 (2)
C21—C22—C23—C24	1.6 (3)	C44—N42—C42—C41	64.8 (2)
O23—C23—C24—C25	−179.91 (17)	N41—C41—C42—N42	−9.7 (2)
C22—C23—C24—C25	0.2 (3)	C41—N41—C43—C44	64.5 (2)
C23—C24—C25—O25	177.90 (17)	C45—N41—C43—C44	−55.9 (2)
C23—C24—C25—C26	−1.8 (3)	C42—N42—C44—C43	−53.9 (2)
O25—C25—C26—C21	−178.18 (17)	C46—N42—C44—C43	64.2 (2)
C24—C25—C26—C21	1.5 (3)	N41—C43—C44—N42	−8.2 (2)
C22—C21—C26—C25	0.3 (3)	C41—N41—C45—C46	−55.9 (2)
C27—C21—C26—C25	179.62 (17)	C43—N41—C45—C46	64.7 (2)
C22—C21—C27—O21	7.5 (3)	C42—N42—C46—C45	62.4 (2)
C26—C21—C27—O21	−171.86 (18)	C44—N42—C46—C45	−54.9 (2)
C22—C21—C27—O22	−172.46 (17)	N41—C45—C46—N42	−7.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N32ⁱ	0.84	1.93	2.750 (2)	167
O15—H15···O1	0.84	1.82	2.656 (2)	175
O23—H23···O12ⁱⁱ	0.84	1.85	2.684 (2)	175
O25—H25···O2	0.84	1.81	2.649 (2)	175
N31—H31···O11	0.93	1.84	2.750 (2)	165
N41—H41···O22	0.93	1.65	2.575 (2)	173
O1—H1A···O22ⁱ	0.91	1.85	2.743 (2)	167
O1—H1B···O11ⁱⁱⁱ	0.91	1.92	2.834 (2)	173
O2—H2A···N42^iv	0.94	1.89	2.822 (2)	173
O2—H2B···O11	0.90	1.96	2.827 (2)	163

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

(2) Piperazinee–3,5-dihydroxybenzoic acid–water (1/2/4) top

Crystal data top

C₄H₁₂N₂·2(C₇H₅O₄)·4(H₂O)	Z = 1
M_r = 466.44	F(000) = 248
Triclinic, P1	D_x = 1.426 Mg m⁻³
a = 7.7793 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1656 (3) Å	Cell parameters from 5313 reflections
c = 9.0662 (4) Å	θ = 2.6–27.4°
α = 104.981 (2)°	µ = 0.12 mm⁻¹
β = 97.134 (2)°	T = 100 K
γ = 98.066 (2)°	Block, colourless
V = 543.02 (4) Å³	0.36 × 0.35 × 0.25 mm

Data collection top

Kappa-CCD diffractometer	2430 independent reflections
Radiation source: fine-focus sealed X-ray tube	2133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ scans and ω scans with κ offsets	θ_max = 27.4°, θ_min = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→10
T_min = 0.958, T_max = 0.971	k = −10→10
5313 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0343P)² + 0.2285P] where P = (F_o² + 2F_c²)/3
2430 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.37 e Å⁻³
4 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₁₂N₂·2(C₇H₅O₄)·4(H₂O)	γ = 98.066 (2)°
M_r = 466.44	V = 543.02 (4) Å³
Triclinic, P1	Z = 1
a = 7.7793 (3) Å	Mo Kα radiation
b = 8.1656 (3) Å	µ = 0.12 mm⁻¹
c = 9.0662 (4) Å	T = 100 K
α = 104.981 (2)°	0.36 × 0.35 × 0.25 mm
β = 97.134 (2)°

Data collection top

Kappa-CCD diffractometer	2430 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	2133 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.971	R_int = 0.022
5313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	4 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.06	Δρ_max = 0.37 e Å⁻³
2430 reflections	Δρ_min = −0.24 e Å⁻³
169 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O11	0.31130 (13)	0.03684 (11)	0.19272 (10)	0.0222 (2)
O12	0.22143 (13)	0.07173 (11)	−0.03919 (10)	0.0233 (2)
O13	−0.09415 (12)	−0.53185 (11)	−0.33656 (10)	0.0202 (2)
O15	0.33241 (11)	−0.59393 (11)	0.06812 (10)	0.0188 (2)
C11	0.20747 (16)	−0.21402 (15)	−0.02008 (14)	0.0158 (2)
C12	0.08083 (16)	−0.28557 (15)	−0.15306 (14)	0.0161 (2)
C13	0.03720 (15)	−0.46389 (15)	−0.21061 (13)	0.0155 (2)
C14	0.12236 (16)	−0.57084 (15)	−0.14087 (14)	0.0155 (2)
C15	0.24868 (15)	−0.49737 (15)	−0.00874 (14)	0.0148 (2)
C16	0.29204 (16)	−0.31895 (15)	0.05212 (14)	0.0161 (2)
C17	0.24984 (16)	−0.02119 (15)	0.04836 (14)	0.0173 (3)
N1	0.39363 (13)	0.36987 (13)	0.37028 (11)	0.0162 (2)
C2	0.36286 (17)	0.37976 (16)	0.53142 (14)	0.0199 (3)
C3	0.41841 (16)	0.56356 (16)	0.63309 (14)	0.0196 (3)
O1	0.1731 (4)	−0.1323 (2)	0.40019 (15)	0.0350 (7)	0.823 (6)
O1A	0.2602 (15)	−0.1591 (10)	0.4031 (9)	0.034*	0.177 (6)
O2	0.35406 (16)	0.02471 (16)	−0.31268 (13)	0.0325 (3)	0.912 (2)
O2A	0.1675 (16)	0.0368 (15)	−0.3552 (14)	0.032*	0.088 (2)
H13	−0.1194	−0.6391	−0.3523	0.030*
H15	0.2893	−0.6987	0.0278	0.028*
H12	0.0253	−0.2136	−0.2035	0.019*
H14	0.0943	−0.6925	−0.1832	0.019*
H16	0.3787	−0.2693	0.1423	0.019*
H1C	0.3227	0.4333	0.3285	0.019*
H1D	0.3634	0.2572	0.3104	0.019*
H2C	0.4312	0.3038	0.5737	0.024*
H2D	0.2365	0.3396	0.5304	0.024*
H3A	0.3425	0.6374	0.5962	0.024*
H3B	0.4033	0.5681	0.7408	0.024*
H1A	0.227 (3)	−0.079 (3)	0.4903 (15)	0.050 (3)*	0.823 (6)
H1B	0.216 (3)	−0.088 (3)	0.335 (2)	0.050 (3)*	0.823 (6)
H2A	0.4552 (17)	0.008 (3)	−0.282 (2)	0.050 (3)*	0.912 (2)
H2B	0.293 (3)	0.030 (3)	−0.241 (2)	0.050 (3)*	0.912 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0312 (5)	0.0135 (4)	0.0176 (4)	0.0018 (4)	−0.0012 (4)	0.0008 (3)
O12	0.0350 (5)	0.0127 (4)	0.0214 (5)	0.0037 (4)	0.0007 (4)	0.0055 (4)
O13	0.0214 (5)	0.0164 (4)	0.0183 (5)	0.0016 (3)	−0.0056 (4)	0.0021 (4)
O15	0.0225 (5)	0.0129 (4)	0.0194 (5)	0.0031 (3)	−0.0035 (4)	0.0050 (4)
C11	0.0177 (6)	0.0129 (5)	0.0158 (6)	0.0012 (4)	0.0036 (5)	0.0026 (5)
C12	0.0178 (6)	0.0155 (6)	0.0158 (6)	0.0047 (4)	0.0021 (5)	0.0053 (5)
C13	0.0148 (6)	0.0168 (6)	0.0133 (5)	0.0015 (4)	0.0016 (4)	0.0024 (5)
C14	0.0167 (6)	0.0124 (5)	0.0163 (6)	0.0018 (4)	0.0031 (5)	0.0027 (4)
C15	0.0151 (6)	0.0150 (6)	0.0157 (6)	0.0039 (4)	0.0034 (5)	0.0058 (5)
C16	0.0171 (6)	0.0153 (6)	0.0140 (6)	0.0011 (4)	0.0002 (4)	0.0030 (5)
C17	0.0188 (6)	0.0135 (6)	0.0187 (6)	0.0025 (4)	0.0025 (5)	0.0033 (5)
N1	0.0182 (5)	0.0141 (5)	0.0139 (5)	0.0019 (4)	−0.0017 (4)	0.0025 (4)
C2	0.0218 (6)	0.0214 (6)	0.0147 (6)	−0.0026 (5)	0.0010 (5)	0.0060 (5)
C3	0.0170 (6)	0.0241 (6)	0.0149 (6)	0.0018 (5)	0.0014 (5)	0.0021 (5)
O1	0.0548 (16)	0.0218 (7)	0.0179 (6)	−0.0122 (7)	−0.0007 (6)	0.0006 (5)
O2	0.0316 (7)	0.0419 (7)	0.0205 (6)	0.0028 (5)	−0.0012 (5)	0.0073 (5)

Geometric parameters (Å, º) top

O11—C17	1.2753 (15)	N1—C2	1.4931 (15)
O12—C17	1.2527 (15)	N1—C3ⁱ	1.4937 (15)
O13—C13	1.3709 (14)	N1—H1C	0.92
O13—H13	0.84	N1—H1D	0.92
O15—C15	1.3590 (14)	C2—C3	1.5142 (17)
O15—H15	0.84	C2—H2C	0.99
C11—C16	1.3917 (16)	C2—H2D	0.99
C11—C12	1.3945 (17)	C3—N1ⁱ	1.4937 (15)
C11—C17	1.5071 (16)	C3—H3A	0.99
C12—C13	1.3900 (16)	C3—H3B	0.99
C12—H12	0.95	O1—O1A	0.740 (10)
C13—C14	1.3947 (16)	O1—H1A	0.845 (10)
C14—C15	1.3897 (17)	O1—H1B	0.845 (10)
C14—H14	0.95	O2—O2A	1.478 (12)
C15—C16	1.3932 (16)	O2—H2A	0.845 (10)
C16—H16	0.95	O2—H2B	0.845 (10)

C13—O13—H13	109.5	O11—C17—C11	117.55 (10)
C15—O15—H15	109.5	C2—N1—C3ⁱ	111.57 (9)
C16—C11—C12	120.70 (11)	C2—N1—H1C	109.3
C16—C11—C17	119.67 (11)	C3ⁱ—N1—H1C	109.3
C12—C11—C17	119.61 (11)	C2—N1—H1D	109.3
C13—C12—C11	118.93 (11)	C3ⁱ—N1—H1D	109.3
C13—C12—H12	120.5	H1C—N1—H1D	108.0
C11—C12—H12	120.5	N1—C2—C3	109.99 (10)
O13—C13—C12	118.06 (10)	N1—C2—H2C	109.7
O13—C13—C14	120.86 (10)	C3—C2—H2C	109.7
C12—C13—C14	121.07 (11)	N1—C2—H2D	109.7
C15—C14—C13	119.21 (11)	C3—C2—H2D	109.7
C15—C14—H14	120.4	H2C—C2—H2D	108.2
C13—C14—H14	120.4	N1ⁱ—C3—C2	110.59 (10)
O15—C15—C14	122.32 (10)	N1ⁱ—C3—H3A	109.5
O15—C15—C16	117.16 (10)	C2—C3—H3A	109.5
C14—C15—C16	120.51 (11)	N1ⁱ—C3—H3B	109.5
C11—C16—C15	119.54 (11)	C2—C3—H3B	109.5
C11—C16—H16	120.2	H3A—C3—H3B	108.1
C15—C16—H16	120.2	H1A—O1—H1B	109 (2)
O12—C17—O11	124.18 (11)	H2A—O2—H2B	110 (2)
O12—C17—C11	118.26 (11)

C16—C11—C12—C13	1.48 (17)	C17—C11—C16—C15	178.05 (11)
C17—C11—C12—C13	−176.99 (11)	O15—C15—C16—C11	−178.62 (10)
C11—C12—C13—O13	176.60 (10)	C14—C15—C16—C11	0.19 (18)
C11—C12—C13—C14	−2.34 (18)	C16—C11—C17—O12	156.59 (12)
O13—C13—C14—C15	−176.79 (10)	C12—C11—C17—O12	−24.92 (17)
C12—C13—C14—C15	2.13 (18)	C16—C11—C17—O11	−23.96 (17)
C13—C14—C15—O15	177.71 (11)	C12—C11—C17—O11	154.53 (11)
C13—C14—C15—C16	−1.03 (17)	C3ⁱ—N1—C2—C3	56.90 (14)
C12—C11—C16—C15	−0.42 (18)	N1—C2—C3—N1ⁱ	−56.33 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱⁱ	0.84 (2)	1.85 (2)	2.694 (2)	176 (2)
O1—H1B···O11	0.85 (2)	1.99 (2)	2.834 (2)	175 (2)
O2—H2A···O11ⁱⁱⁱ	0.84 (2)	2.02 (2)	2.856 (2)	175 (2)
O2—H2B···O12	0.85 (2)	1.94 (2)	2.759 (2)	163 (2)
O13—H13···O1^iv	0.84	1.78	2.618 (2)	176
O15—H15···O12^v	0.84	1.79	2.627 (2)	172
N1—H1C···O13^vi	0.92	2.05	2.858 (2)	145
N1—H1D···O11	0.92	1.80	2.718 (2)	178

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

(3) 1,2-Diaminoethane–3,5-dihydroxybenzoic acid–water (1/2/2) top

Crystal data top

C₂H₁₀N₂·2(C₇H₅O₄)·2(H₂O)	F(000) = 428
M_r = 404.37	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.0804 (3) Å	Cell parameters from 2104 reflections
b = 10.6021 (6) Å	θ = 2.7–27.5°
c = 11.3988 (6) Å	µ = 0.12 mm⁻¹
β = 109.243 (3)°	T = 100 K
V = 921.97 (8) Å³	Block, colourless
Z = 2	0.20 × 0.20 × 0.13 mm

Data collection top

Kappa-CCD diffractometer	2104 independent reflections
Radiation source: fine-focus sealed X-ray tube	1756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ scans and ω scans with κ offsets	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→10
T_min = 0.976, T_max = 0.984	k = 0→13
21623 measured reflections	l = −14→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0527P)² + 0.3193P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.015
2104 reflections	Δρ_max = 0.26 e Å⁻³
146 parameters	Δρ_min = −0.25 e Å⁻³
3 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (6)

Crystal data top

C₂H₁₀N₂·2(C₇H₅O₄)·2(H₂O)	V = 921.97 (8) Å³
M_r = 404.37	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0804 (3) Å	µ = 0.12 mm⁻¹
b = 10.6021 (6) Å	T = 100 K
c = 11.3988 (6) Å	0.20 × 0.20 × 0.13 mm
β = 109.243 (3)°

Data collection top

Kappa-CCD diffractometer	2104 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	1756 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.984	R_int = 0.024
21623 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	3 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	Δρ_max = 0.26 e Å⁻³
2104 reflections	Δρ_min = −0.25 e Å⁻³
146 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.54428 (15)	0.61096 (11)	0.63631 (11)	0.0211 (3)
C1	0.44966 (18)	0.51431 (14)	0.54434 (13)	0.0230 (3)
O5	0.18734 (12)	0.56858 (10)	1.25780 (9)	0.0225 (3)
O2	0.35831 (13)	0.62042 (10)	0.79721 (9)	0.0249 (3)
O3	−0.21720 (12)	0.71640 (10)	0.86948 (9)	0.0233 (3)
O1	0.54408 (12)	0.69042 (10)	0.97736 (9)	0.0237 (3)
C11	0.24974 (16)	0.64972 (13)	0.96525 (12)	0.0180 (3)
C12	0.07983 (17)	0.68039 (13)	0.89140 (12)	0.0186 (3)
C13	−0.05313 (17)	0.68038 (13)	0.94391 (12)	0.0179 (3)
C14	−0.01931 (17)	0.64522 (13)	1.06687 (13)	0.0183 (3)
C15	0.15011 (18)	0.61045 (12)	1.13835 (13)	0.0181 (3)
C16	0.28684 (17)	0.61580 (13)	1.08937 (13)	0.0190 (3)
C17	0.39427 (17)	0.65316 (13)	0.90906 (13)	0.0190 (3)
O11	−0.0887 (3)	0.9669 (2)	0.8267 (2)	0.0361 (7)	0.874 (6)
O11A	−0.022 (3)	1.014 (2)	0.866 (2)	0.037*	0.075 (6)
O11B	−0.037 (3)	1.009 (2)	0.934 (2)	0.037*	0.053 (3)
H1A	0.6546	0.5832	0.6780	0.032*
H1B	0.4860	0.6247	0.6912	0.032*
H1C	0.5502	0.6841	0.5962	0.032*
H1D	0.3310	0.5455	0.4968	0.028*
H1E	0.4368	0.4362	0.5882	0.028*
H5	0.0935	0.5572	1.2729	0.034*
H3	−0.2891	0.7053	0.9075	0.035*
H12	0.0549	0.7011	0.8062	0.022*
H14	−0.1109	0.6449	1.1019	0.022*
H16	0.4035	0.5966	1.1398	0.023*
H111	−0.135 (3)	0.9019 (15)	0.843 (2)	0.056*	0.874 (6)
H112	−0.164 (2)	1.0180 (19)	0.785 (2)	0.056*	0.874 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0194 (6)	0.0279 (7)	0.0169 (6)	0.0021 (5)	0.0072 (5)	−0.0001 (5)
C1	0.0214 (7)	0.0299 (8)	0.0186 (7)	−0.0005 (6)	0.0079 (6)	−0.0023 (6)
O5	0.0195 (5)	0.0303 (6)	0.0192 (5)	0.0031 (4)	0.0085 (4)	0.0041 (4)
O2	0.0220 (5)	0.0333 (6)	0.0231 (6)	−0.0017 (4)	0.0124 (4)	−0.0034 (4)
O3	0.0139 (5)	0.0353 (6)	0.0218 (5)	0.0031 (4)	0.0073 (4)	0.0051 (4)
O1	0.0154 (5)	0.0315 (6)	0.0259 (5)	−0.0016 (4)	0.0091 (4)	−0.0039 (4)
C11	0.0158 (6)	0.0186 (7)	0.0215 (7)	−0.0008 (5)	0.0088 (5)	−0.0029 (5)
C12	0.0183 (6)	0.0204 (7)	0.0180 (7)	−0.0008 (5)	0.0071 (5)	0.0005 (5)
C13	0.0142 (6)	0.0183 (7)	0.0209 (7)	0.0007 (5)	0.0052 (5)	−0.0003 (5)
C14	0.0162 (6)	0.0206 (7)	0.0207 (7)	−0.0008 (5)	0.0096 (5)	−0.0013 (5)
C15	0.0199 (6)	0.0173 (7)	0.0177 (7)	−0.0002 (5)	0.0070 (5)	−0.0011 (5)
C16	0.0149 (6)	0.0210 (7)	0.0205 (7)	0.0012 (5)	0.0052 (5)	−0.0010 (5)
C17	0.0178 (6)	0.0192 (7)	0.0221 (7)	0.0021 (5)	0.0094 (5)	0.0011 (5)
O11	0.0305 (10)	0.0369 (11)	0.0503 (11)	0.0144 (9)	0.0260 (9)	0.0189 (9)

Geometric parameters (Å, º) top

N1—C1	1.4850 (18)	C11—C17	1.5061 (18)
N1—H1A	0.9100	C12—C13	1.3916 (18)
N1—H1B	0.9100	C12—H12	0.9500
N1—H1C	0.9100	C13—C14	1.3877 (19)
C1—C1ⁱ	1.523 (3)	C14—C15	1.3923 (19)
C1—H1D	0.9900	C14—H14	0.9500
C1—H1E	0.9900	C15—C16	1.3937 (18)
O5—C15	1.3679 (16)	C16—H16	0.9500
O5—H5	0.8400	O11—O11A	0.76 (3)
O2—C17	1.2595 (17)	O11—O11B	1.23 (3)
O3—C13	1.3718 (15)	O11—H111	0.836 (5)
O3—H3	0.8400	O11—H112	0.836 (5)
O1—C17	1.2674 (17)	O11A—O11B	0.82 (3)
C11—C12	1.3920 (19)	O11A—H112	1.21 (3)
C11—C16	1.3933 (19)	O11B—O11Bⁱⁱ	1.45 (5)

C1—N1—H1A	109.5	C13—C14—H14	120.3
C1—N1—H1B	109.5	C15—C14—H14	120.3
H1A—N1—H1B	109.5	O5—C15—C14	121.31 (12)
C1—N1—H1C	109.5	O5—C15—C16	117.95 (12)
H1A—N1—H1C	109.5	C14—C15—C16	120.74 (13)
H1B—N1—H1C	109.5	C11—C16—C15	118.92 (12)
N1—C1—C1ⁱ	110.05 (14)	C11—C16—H16	120.5
N1—C1—H1D	109.7	C15—C16—H16	120.5
C1ⁱ—C1—H1D	109.7	O2—C17—O1	124.24 (12)
N1—C1—H1E	109.7	O2—C17—C11	118.11 (12)
C1ⁱ—C1—H1E	109.7	O1—C17—C11	117.64 (12)
H1D—C1—H1E	108.2	O11A—O11—O11B	40.3 (18)
C15—O5—H5	109.5	O11A—O11—H111	133 (3)
C13—O3—H3	109.5	O11B—O11—H111	96 (2)
C12—C11—C16	120.91 (12)	O11A—O11—H112	99 (2)
C12—C11—C17	119.06 (12)	O11B—O11—H112	106 (2)
C16—C11—C17	120.04 (12)	H111—O11—H112	111 (3)
C13—C12—C11	119.16 (12)	O11—O11A—O11B	103 (4)
C13—C12—H12	120.4	O11—O11A—H112	42.8 (16)
C11—C12—H12	120.4	O11B—O11A—H112	109 (3)
O3—C13—C14	121.87 (12)	O11A—O11B—O11	37 (3)
O3—C13—C12	117.37 (12)	O11A—O11B—O11Bⁱⁱ	149 (4)
C14—C13—C12	120.76 (12)	O11—O11B—O11Bⁱⁱ	151 (3)
C13—C14—C15	119.38 (12)

C16—C11—C12—C13	1.8 (2)	C17—C11—C16—C15	−178.50 (12)
C17—C11—C12—C13	−178.38 (12)	O5—C15—C16—C11	175.58 (12)
C11—C12—C13—O3	177.25 (12)	C14—C15—C16—C11	−3.6 (2)
C11—C12—C13—C14	−2.7 (2)	C12—C11—C17—O2	−35.31 (19)
O3—C13—C14—C15	−179.51 (12)	C16—C11—C17—O2	144.49 (14)
C12—C13—C14—C15	0.4 (2)	C12—C11—C17—O1	143.87 (14)
C13—C14—C15—O5	−176.39 (12)	C16—C11—C17—O1	−36.34 (19)
C13—C14—C15—C16	2.8 (2)	O11—O11A—O11B—O11Bⁱⁱ	128 (7)
C12—C11—C16—C15	1.3 (2)	O11A—O11—O11B—O11Bⁱⁱ	−123 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱⁱⁱ	0.84	1.78	2.622 (2)	175
O5—H5···O11^iv	0.84	1.79	2.625 (3)	172
O11—H111···O3	0.83	2.13	2.950 (2)	168
O11—H112···O2^v	0.84	1.88	2.713 (2)	171
N1—H1A···O5^vi	0.91	2.03	2.839 (2)	147
N1—H1B···O2	0.91	1.83	2.729 (2)	169
N1—H1C···O1^vii	0.91	1.89	2.778 (2)	166

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

Experimental details

	(1)	(2)	(3)
Crystal data
Chemical formula	C₆H₁₃N₂·C₇H₅O₄·H₂O	C₄H₁₂N₂·2(C₇H₅O₄)·4(H₂O)	C₂H₁₀N₂·2(C₇H₅O₄)·2(H₂O)
M_r	284.31	466.44	404.37
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P1	Monoclinic, P2₁/c
Temperature (K)	100	100	100
a, b, c (Å)	9.4478 (4), 11.7644 (4), 25.9024 (12)	7.7793 (3), 8.1656 (3), 9.0662 (4)	8.0804 (3), 10.6021 (6), 11.3988 (6)
α, β, γ (°)	90, 101.969 (2), 90	104.981 (2), 97.134 (2), 98.066 (2)	90, 109.243 (3), 90
V (Å³)	2816.4 (2)	543.02 (4)	921.97 (8)
Z	8	1	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.10	0.12	0.12
Crystal size (mm)	0.30 × 0.25 × 0.13	0.36 × 0.35 × 0.25	0.20 × 0.20 × 0.13

Data collection
Diffractometer	Kappa-CCD diffractometer	Kappa-CCD diffractometer	Kappa-CCD diffractometer
Absorption correction	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)
T_min, T_max	0.970, 0.987	0.958, 0.971	0.976, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	15105, 6382, 3976	5313, 2430, 2133	21623, 2104, 1756
R_int	0.028	0.022	0.024
(sin θ/λ)_max (Å⁻¹)	0.649	0.648	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.131, 1.05	0.037, 0.096, 1.06	0.041, 0.113, 1.06
No. of reflections	6382	2430	2104
No. of parameters	379	169	146
No. of restraints	4	4	3
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.22	0.37, −0.24	0.26, −0.25

Computer programs: Kappa-CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997a), NRCVAX96 and SHELXL97 (Sheldrick, 1997b), NRCVAX96, ORTEP (Johnson, 1976), PLATON (Spek, 2000), NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N32ⁱ	0.84	1.93	2.750 (2)	167
O15—H15···O1	0.84	1.82	2.656 (2)	175
O23—H23···O12ⁱⁱ	0.84	1.85	2.684 (2)	175
O25—H25···O2	0.84	1.81	2.649 (2)	175
N31—H31···O11	0.93	1.84	2.750 (2)	165
N41—H41···O22	0.93	1.65	2.575 (2)	173
O1—H1A···O22ⁱ	0.91	1.85	2.743 (2)	167
O1—H1B···O11ⁱⁱⁱ	0.91	1.92	2.834 (2)	173
O2—H2A···N42^iv	0.94	1.89	2.822 (2)	173
O2—H2B···O11	0.90	1.96	2.827 (2)	163

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

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.84 (2)	1.85 (2)	2.694 (2)	176 (2)
O1—H1B···O11	0.85 (2)	1.99 (2)	2.834 (2)	175 (2)
O2—H2A···O11ⁱⁱ	0.84 (2)	2.02 (2)	2.856 (2)	175 (2)
O2—H2B···O12	0.85 (2)	1.94 (2)	2.759 (2)	163 (2)
O13—H13···O1ⁱⁱⁱ	0.84	1.78	2.618 (2)	176
O15—H15···O12^iv	0.84	1.79	2.627 (2)	172
N1—H1C···O13^v	0.92	2.05	2.858 (2)	145
N1—H1D···O11	0.92	1.80	2.718 (2)	178

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

Hydrogen-bond geometry (Å, º) for (3) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱ	0.84	1.78	2.622 (2)	175
O5—H5···O11ⁱⁱ	0.84	1.79	2.625 (3)	172
O11—H111···O3	0.83	2.13	2.950 (2)	168
O11—H112···O2ⁱⁱⁱ	0.84	1.88	2.713 (2)	171
N1—H1A···O5^iv	0.91	2.03	2.839 (2)	147
N1—H1B···O2	0.91	1.83	2.729 (2)	169
N1—H1C···O1^v	0.91	1.89	2.778 (2)	166

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

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