Phosphonopropionic acid as a building block in supramolecular chemistry: salts with organic diamines

The structures of seven salts formed by phosphonopropionic acid with organic diamines are reported; in these salts, the hydrogen-bonded substructures formed by the anions can be zero-, one- or two-dimensional, while the overall hydrogen-bonded supramolecular structures are three-dimensional. The 1:1 adduct, compound (1), formed between 1,2-bis(4′-pyri­dyl)ethene and phosphonopropionic acid is a salt, [{(C₁₂H₁₀N₂)H₂}²⁺]·[(C₁₂H₁₀N₂)]·[(C₃H₆O₅P)⁻]₂, in which both diamine components lie across centres of inversion in space group P2₁/c. The anions form hydrogen-bonded head-to-head dimers, and these are linked by the two diamine units into sheets, which are themselves linked by C—H...O hydrogen bonds. With 2,2′-dipyridylamine the acid forms the hydrated salt [{(C₁₀H₉N₃)H}⁺]·[(C₃H₆O₅P)⁻]·H₂O (2), in which all components are disordered with occupancy 0.5 in space group Fmm2. The anions form head-to-tail dimers, which are linked into sheets by the cations, and the sheets are linked into a three-dimensional framework by the water molecules. The piperazine salt [{(C₄H₁₀N₂)H₂}²⁺]·[(C₃H₅O₅P)²⁻] (3) contains simple anion chains linked into a three-dimensional framework by the two independent cations, both of which are centrosymmetric. In the hydrated salt formed by N,N′-dimethylpiperazine, [{(MeNC₄H₈NMe)H₂}²⁺]·[(C₃H₆O₅P)⁻]₂·(H₂O)₂ (4), head-to-tail anion chains combine with the water molecules to form a three-dimensional framework, which encloses voids that contain the cations. In the 4,4′-bipyridyl adduct [{(C₁₀H₈N₂)H_0.72}^0.72+]·[{(H_0.5O)₃PCH₂CH₂COOH_0.78}^0.72−] (5), there is extensive disorder of the H atoms that are bonded to N and O atoms, and the anion chains are linked by the cations into sheets, which are themselves linked by C—H...O hydrogen bonds. In the 1:2 adduct formed with 1,2-bis(4′-pyridyl)ethane, [{(C₁₂H₁₂N₂)H₂}²⁺]·[(C₃H₆O₅P)⁻]₂ (6), where the cation lies across an inversion centre, the anions form molecular ladders. These ladders are linked into sheets by the cations, which are themselves linked by C—H...O hydrogen bonds. In the methanol-solvated salt formed with 2,6-dimethylpiperazine, [{(C₆H₁₄N₂)H₂}²⁺]·[(C₃H₆O₅P)⁻]₂· (CH₄O)_0.34 (7), the anions form sheets that are linked into a three-dimensional framework by the cations. The supramolecular structures are compared with those of analogous salts formed by phosphonoacetic acid.

S1. Comment

In full text version

S2. Experimental

In full text version

S3. Refinement

In full text version

Computing details

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, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a) and PRPKAPPA (Ferguson, 1999).

Figures

In full text version

(I) 1,2-Bis(4'-pyridyl)ethene–phosphonopropionic acid (1/1)

Crystal data

C12H12N2^2+·C12H10N2·2(C3H6O5P)^−	F(000) = 704
Mr = 672.55	Dx = 1.461 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3496 reflections
a = 10.1600 (3) Å	θ = 2.8–27.5°
b = 10.4061 (3) Å	µ = 0.21 mm^−1
c = 14.5441 (5) Å	T = 150 K
β = 96.2880 (12)°	Block, colourless
V = 1528.44 (8) Å^3	0.22 × 0.16 × 0.14 mm
Z = 2

Data collection

Kappa-CCD diffractometer	2880 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.042
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ϕ scans, and ω scans with κ offsets	h = −13→13
13452 measured reflections	k = −13→13
3496 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0404P)^2 + 0.6401P] where P = (Fo^2 + 2Fc^2)/3
3496 reflections	(Δ/σ)max = 0.001
210 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N11	−0.12432 (12)	0.46207 (14)	0.21704 (9)	0.0255 (3)
C12	−0.18883 (15)	0.36667 (16)	0.16967 (11)	0.0250 (3)
C13	−0.29918 (15)	0.38614 (16)	0.10699 (11)	0.0231 (3)
C14	−0.34753 (14)	0.51103 (15)	0.09126 (10)	0.0212 (3)
C15	−0.27925 (16)	0.60983 (16)	0.14024 (12)	0.0274 (4)
C16	−0.16981 (16)	0.58185 (17)	0.20161 (12)	0.0288 (4)
C17	−0.46417 (14)	0.54284 (15)	0.02611 (11)	0.0221 (3)
N21	0.62522 (12)	0.59514 (13)	0.79666 (9)	0.0216 (3)
C22	0.70080 (14)	0.68140 (16)	0.84635 (11)	0.0236 (3)
C23	0.81286 (15)	0.64407 (15)	0.90215 (11)	0.0238 (3)
C24	0.84758 (14)	0.51395 (15)	0.90851 (10)	0.0197 (3)
C25	0.76696 (15)	0.42735 (15)	0.85448 (11)	0.0222 (3)
C26	0.65671 (15)	0.47024 (15)	0.79968 (11)	0.0231 (3)
C27	0.96084 (14)	0.46486 (15)	0.97001 (11)	0.0220 (3)
P1	0.40649 (3)	0.59435 (4)	0.59827 (3)	0.01825 (12)
O1	0.07888 (11)	0.42023 (12)	0.34015 (9)	0.0319 (3)
O2	0.02148 (11)	0.60505 (11)	0.40398 (9)	0.0290 (3)
O3	0.45265 (10)	0.45215 (10)	0.61687 (8)	0.0222 (2)
O4	0.41924 (10)	0.66590 (11)	0.68904 (7)	0.0239 (3)
O5	0.48314 (10)	0.65546 (10)	0.52532 (8)	0.0224 (2)
C1	0.09583 (14)	0.51387 (16)	0.40157 (11)	0.0219 (3)
C2	0.22088 (15)	0.49638 (17)	0.46571 (12)	0.0266 (4)
C3	0.23605 (14)	0.58554 (16)	0.54947 (11)	0.0234 (3)
H12	−0.1571	0.2814	0.1797	0.030*
H13	−0.3419	0.3155	0.0749	0.028*
H15	−0.3080	0.6963	0.1314	0.033*
H16	−0.1246	0.6506	0.2344	0.035*
H17	−0.4903	0.6304	0.0209	0.026*
H21	0.5540	0.6209	0.7616	0.026*
H22	0.6768	0.7697	0.8431	0.028*
H23	0.8663	0.7065	0.9362	0.029*
H25	0.7885	0.3385	0.8556	0.027*
H26	0.6024	0.4105	0.7636	0.028*
H27	0.9798	0.3757	0.9667	0.026*
H1	0.0138	0.4373	0.3013	0.048*
H3	0.4723	0.4191	0.5675	0.033*
H2A	0.2974	0.5097	0.4301	0.032*
H2B	0.2245	0.4064	0.4880	0.032*
H3A	0.1812	0.5533	0.5968	0.028*
H3B	0.2042	0.6725	0.5306	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0214 (6)	0.0348 (8)	0.0191 (7)	0.0030 (6)	−0.0034 (5)	−0.0041 (6)
C12	0.0239 (7)	0.0282 (8)	0.0218 (8)	0.0040 (6)	−0.0016 (6)	−0.0003 (7)
C13	0.0224 (7)	0.0255 (8)	0.0204 (8)	−0.0001 (6)	−0.0022 (6)	−0.0031 (6)
C14	0.0188 (7)	0.0274 (8)	0.0171 (7)	0.0015 (6)	−0.0004 (6)	−0.0021 (6)
C15	0.0279 (8)	0.0262 (8)	0.0266 (9)	0.0038 (7)	−0.0037 (7)	−0.0046 (7)
C16	0.0271 (8)	0.0316 (9)	0.0259 (9)	0.0002 (7)	−0.0059 (7)	−0.0088 (7)
C17	0.0221 (7)	0.0225 (7)	0.0210 (8)	0.0042 (6)	−0.0006 (6)	−0.0010 (6)
N21	0.0179 (6)	0.0267 (7)	0.0188 (7)	0.0017 (5)	−0.0042 (5)	0.0022 (5)
C22	0.0240 (7)	0.0224 (8)	0.0233 (8)	0.0018 (6)	−0.0023 (6)	0.0016 (6)
C23	0.0228 (7)	0.0215 (8)	0.0256 (8)	−0.0015 (6)	−0.0042 (6)	−0.0012 (6)
C24	0.0178 (7)	0.0230 (8)	0.0177 (7)	−0.0003 (6)	−0.0004 (6)	0.0022 (6)
C25	0.0231 (7)	0.0208 (7)	0.0217 (8)	0.0000 (6)	−0.0019 (6)	0.0008 (6)
C26	0.0216 (7)	0.0247 (8)	0.0217 (8)	−0.0025 (6)	−0.0033 (6)	−0.0004 (6)
C27	0.0193 (7)	0.0221 (8)	0.0237 (8)	0.0013 (6)	−0.0023 (6)	0.0031 (6)
P1	0.01556 (19)	0.0199 (2)	0.0182 (2)	0.00056 (14)	−0.00320 (14)	−0.00039 (15)
O1	0.0255 (6)	0.0379 (7)	0.0290 (7)	0.0072 (5)	−0.0121 (5)	−0.0113 (5)
O2	0.0243 (6)	0.0278 (6)	0.0325 (7)	0.0043 (5)	−0.0074 (5)	−0.0016 (5)
O3	0.0259 (5)	0.0200 (5)	0.0200 (6)	0.0015 (4)	−0.0009 (4)	0.0010 (4)
O4	0.0213 (5)	0.0279 (6)	0.0208 (6)	0.0043 (4)	−0.0056 (4)	−0.0048 (5)
O5	0.0221 (5)	0.0191 (5)	0.0260 (6)	−0.0009 (4)	0.0020 (4)	0.0007 (4)
C1	0.0178 (7)	0.0260 (8)	0.0214 (8)	−0.0026 (6)	−0.0011 (6)	0.0018 (6)
C2	0.0197 (7)	0.0308 (9)	0.0272 (9)	0.0026 (6)	−0.0069 (6)	−0.0054 (7)
C3	0.0167 (7)	0.0306 (8)	0.0219 (8)	0.0012 (6)	−0.0026 (6)	−0.0028 (7)

Geometric parameters (Å, º)

N11—C12	1.338 (2)	C24—C27	1.470 (2)
N11—C16	1.340 (2)	C25—C26	1.376 (2)
C12—C13	1.380 (2)	C25—H25	0.95
C12—H12	0.95	C26—H26	0.95
C13—C14	1.399 (2)	C27—C27^ii	1.333 (3)
C13—H13	0.95	C27—H27	0.95
C14—C15	1.392 (2)	P1—O4	1.5088 (11)
C14—C17	1.472 (2)	P1—O5	1.5223 (11)
C15—C16	1.379 (2)	P1—O3	1.5668 (11)
C15—H15	0.95	P1—C3	1.8005 (15)
C16—H16	0.95	O1—C1	1.320 (2)
C17—C17^i	1.335 (3)	O1—H1	0.84
C17—H17	0.95	O2—C1	1.2157 (19)
N21—C26	1.338 (2)	O3—H3	0.84
N21—C22	1.340 (2)	C1—C2	1.503 (2)
N21—H21	0.88	C2—C3	1.526 (2)
C22—C23	1.380 (2)	C2—H2A	0.99
C22—H22	0.95	C2—H2B	0.99
C23—C24	1.400 (2)	C3—H3A	0.99
C23—H23	0.95	C3—H3B	0.99
C24—C25	1.400 (2)
C12—N11—C16	117.61 (14)	C26—C25—H25	119.8
N11—C12—C13	123.21 (15)	C24—C25—H25	119.8
N11—C12—H12	118.4	N21—C26—C25	120.70 (14)
C13—C12—H12	118.4	N21—C26—H26	119.7
C12—C13—C14	119.31 (15)	C25—C26—H26	119.7
C12—C13—H13	120.3	C27^ii—C27—C24	125.38 (19)
C14—C13—H13	120.3	C27^ii—C27—H27	117.3
C15—C14—C13	117.13 (14)	C24—C27—H27	117.3
C15—C14—C17	118.97 (14)	O4—P1—O5	113.72 (7)
C13—C14—C17	123.90 (14)	O4—P1—O3	108.64 (6)
C16—C15—C14	119.79 (15)	O5—P1—O3	110.40 (6)
C16—C15—H15	120.1	O4—P1—C3	110.89 (7)
C14—C15—H15	120.1	O5—P1—C3	106.85 (7)
N11—C16—C15	122.95 (15)	O3—P1—C3	106.07 (7)
N11—C16—H16	118.5	C1—O1—H1	109.5
C15—C16—H16	118.5	P1—O3—H3	109.5
C17^i—C17—C14	124.53 (19)	O2—C1—O1	124.06 (14)
C17^i—C17—H17	117.7	O2—C1—C2	124.23 (15)
C14—C17—H17	117.7	O1—C1—C2	111.67 (13)
C26—N21—C22	120.80 (13)	C1—C2—C3	115.26 (13)
C26—N21—H21	119.6	C1—C2—H2A	108.5
C22—N21—H21	119.6	C3—C2—H2A	108.5
N21—C22—C23	121.05 (15)	C1—C2—H2B	108.5
N21—C22—H22	119.5	C3—C2—H2B	108.5
C23—C22—H22	119.5	H2A—C2—H2B	107.5
C22—C23—C24	119.81 (14)	C2—C3—P1	110.76 (10)
C22—C23—H23	120.1	C2—C3—H3A	109.5
C24—C23—H23	120.1	P1—C3—H3A	109.5
C23—C24—C25	117.25 (13)	C2—C3—H3B	109.5
C23—C24—C27	123.46 (14)	P1—C3—H3B	109.5
C25—C24—C27	119.27 (14)	H3A—C3—H3B	108.1
C26—C25—C24	120.37 (14)
C16—N11—C12—C13	−0.5 (2)	C22—C23—C24—C27	−176.52 (15)
N11—C12—C13—C14	0.0 (2)	C23—C24—C25—C26	−1.6 (2)
C12—C13—C14—C15	0.5 (2)	C27—C24—C25—C26	176.90 (14)
C12—C13—C14—C17	179.99 (15)	C22—N21—C26—C25	0.5 (2)
C13—C14—C15—C16	−0.6 (2)	C24—C25—C26—N21	0.4 (2)
C17—C14—C15—C16	179.96 (15)	C23—C24—C27—C27^ii	3.8 (3)
C12—N11—C16—C15	0.4 (3)	C25—C24—C27—C27^ii	−174.64 (19)
C14—C15—C16—N11	0.1 (3)	O2—C1—C2—C3	12.9 (2)
C15—C14—C17—C17^i	178.49 (19)	O1—C1—C2—C3	−169.25 (14)
C13—C14—C17—C17^i	−1.0 (3)	C1—C2—C3—P1	−160.80 (12)
C26—N21—C22—C23	−0.2 (2)	O4—P1—C3—C2	−171.44 (11)
N21—C22—C23—C24	−1.1 (2)	O5—P1—C3—C2	64.13 (13)
C22—C23—C24—C25	1.9 (2)	O3—P1—C3—C2	−53.67 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O4	0.88	1.70	2.580 (2)	177
O1—H1···N11	0.84	1.78	2.617 (2)	176
O3—H3···O5^iii	0.84	1.66	2.501 (2)	176
C13—H13···O5^iv	0.95	2.55	3.489 (2)	170
C17—H17···O5^v	0.95	2.25	3.185 (2)	169
C22—H22···O3^vi	0.95	2.41	3.292 (2)	153
C23—H23···O2^vii	0.95	2.59	3.361 (2)	138

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

(II) 2,2'-Dipyridylamine–phosphonopropionic acid–water (1/1/1)

Crystal data

C10H10N3^+·C3H6O5P^−·H2O	F(000) = 1440
Mr = 343.27	Dx = 1.514 Mg m^−3
Orthorhombic, Fmm2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2	Cell parameters from 1703 reflections
a = 18.7267 (11) Å	θ = 3.2–27.5°
b = 22.6805 (11) Å	µ = 0.22 mm^−1
c = 7.0893 (4) Å	T = 150 K
V = 3011.0 (3) Å^3	Needle, colourless
Z = 8	0.34 × 0.08 × 0.08 mm

Data collection

Kappa-CCD diffractometer	1445 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.085
Graphite monochromator	θmax = 27.5°, θmin = 3.2°
ϕ scans, and ω scans with κ offsets	h = −21→24
8696 measured reflections	k = −29→28
1703 independent reflections	l = −9→9

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0134P)^2 + 1.5818P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.111	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.19 e Å^−3
1703 reflections	Δρmin = −0.26 e Å^−3
216 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
33 restraints	Extinction coefficient: 0.0030 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 708 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.2 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.14853 (14)	0.03268 (12)	0.4885 (5)	0.0219 (5)	0.50
O3	0.10568 (17)	0.04733 (14)	0.3037 (5)	0.0286 (8)	0.50
O4	0.22710 (13)	0.04602 (11)	0.4613 (5)	0.0254 (7)	0.50
O5	0.11160 (18)	0.06517 (13)	0.6473 (5)	0.0268 (7)	0.50
C1	0.0499 (2)	−0.1289 (2)	0.5803 (12)	0.0291 (11)	0.50
C2	0.0608 (2)	−0.06304 (17)	0.5606 (7)	0.0251 (9)	0.50
C3	0.1389 (5)	−0.0460 (4)	0.5290 (17)	0.024 (3)	0.50
O1	−0.01644 (14)	−0.14672 (14)	0.6123 (6)	0.0285 (11)	0.50
O2	0.09813 (15)	−0.16460 (12)	0.5694 (6)	0.0388 (9)	0.50
O6	0.17568 (16)	0.04406 (13)	−0.0095 (5)	0.0347 (7)	0.50
N1	0.28612 (17)	0.15719 (17)	0.4770 (7)	0.0267 (8)	0.50
C11	0.35778 (17)	0.15477 (10)	0.5228 (6)	0.0252 (10)	0.50
N12	0.39386 (14)	0.20516 (12)	0.5483 (6)	0.0265 (8)	0.50
C13	0.46353 (15)	0.20518 (11)	0.5914 (7)	0.0313 (10)	0.50
C14	0.5000	0.15219 (10)	0.6111 (6)	0.0327 (10)
C15	0.46341 (16)	0.09946 (12)	0.5854 (7)	0.0305 (10)	0.50
C16	0.39126 (16)	0.10035 (13)	0.5398 (6)	0.0274 (10)	0.50
C21	0.2448 (2)	0.20801 (16)	0.4420 (11)	0.0264 (16)	0.50
N22	0.27667 (19)	0.26023 (13)	0.4679 (6)	0.0272 (9)	0.50
C23	0.2386 (2)	0.3095 (2)	0.4402 (12)	0.0271 (17)	0.50
C24	0.1683 (2)	0.30746 (15)	0.3777 (7)	0.0302 (10)	0.50
C25	0.13592 (19)	0.25274 (13)	0.3568 (8)	0.0290 (10)	0.50
C26	0.1737 (2)	0.20111 (15)	0.3906 (7)	0.0277 (9)	0.50
H3	0.1314	0.0405	0.2091	0.043*	0.50
H2A	0.0432	−0.0433	0.6762	0.030*	0.50
H2B	0.0320	−0.0485	0.4532	0.030*	0.50
H3A	0.1578	−0.0678	0.4187	0.028*	0.50
H3B	0.1674	−0.0574	0.6408	0.028*	0.50
H11	−0.0449	−0.1188	0.5912	0.043*	0.50
H1	0.2637	0.1232	0.4688	0.032*	0.50
H12	0.3713	0.2390	0.5364	0.032*	0.50
H13	0.4880	0.2415	0.6084	0.038*	0.50
H14	0.5494	0.1520	0.6418	0.039*	0.50
H15	0.4877	0.0629	0.5989	0.037*	0.50
H16	0.3655	0.0647	0.5208	0.033*	0.50
H23	0.2602	0.3467	0.4638	0.032*	0.50
H24	0.1430	0.3427	0.3499	0.036*	0.50
H25	0.0873	0.2506	0.3190	0.035*	0.50
H26	0.1522	0.1633	0.3792	0.033*	0.50
H61	0.1550	0.0500	−0.113	0.030*	0.50
H62	0.2085	0.0189	−0.016	0.030*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0195 (7)	0.0179 (10)	0.0283 (13)	−0.0001 (7)	−0.0018 (8)	−0.0010 (9)
O3	0.0238 (17)	0.0311 (16)	0.0308 (18)	0.0021 (14)	−0.0015 (14)	0.0032 (14)
O4	0.0172 (14)	0.0210 (13)	0.038 (2)	−0.0004 (10)	0.0005 (13)	0.0014 (14)
O5	0.0258 (17)	0.0237 (16)	0.0308 (19)	0.0038 (14)	−0.0002 (16)	−0.0041 (14)
C1	0.021 (3)	0.028 (3)	0.037 (3)	0.0017 (19)	0.002 (2)	0.001 (3)
C2	0.0185 (19)	0.022 (2)	0.035 (2)	0.0046 (16)	−0.0011 (18)	0.0007 (19)
C3	0.025 (4)	0.016 (5)	0.030 (6)	0.005 (3)	−0.006 (4)	−0.003 (3)
O1	0.017 (3)	0.0200 (13)	0.0486 (19)	−0.0034 (12)	0.0014 (14)	0.0028 (13)
O2	0.0267 (16)	0.0198 (14)	0.070 (3)	0.0047 (12)	0.0039 (17)	0.0011 (17)
O6	0.0368 (17)	0.0387 (16)	0.0286 (15)	0.0160 (13)	−0.0006 (19)	0.0014 (19)
N1	0.0194 (15)	0.0230 (16)	0.038 (2)	−0.0038 (13)	−0.0022 (19)	0.002 (2)
C11	0.0212 (18)	0.0257 (18)	0.029 (3)	−0.0020 (16)	−0.0003 (17)	0.0024 (17)
N12	0.0226 (18)	0.0224 (15)	0.035 (2)	0.0016 (13)	−0.0038 (14)	0.0011 (15)
C13	0.022 (2)	0.031 (2)	0.041 (3)	−0.0012 (17)	−0.006 (2)	0.006 (2)
C14	0.0255 (19)	0.031 (2)	0.042 (2)	−0.013 (11)	−0.001 (16)	0.0030 (19)
C15	0.024 (2)	0.031 (2)	0.037 (3)	0.0014 (17)	−0.004 (2)	0.003 (2)
C16	0.024 (2)	0.0259 (19)	0.032 (3)	−0.0009 (17)	0.0011 (16)	0.0024 (18)
C21	0.029 (3)	0.016 (4)	0.034 (3)	0.001 (3)	−0.010 (3)	0.010 (3)
N22	0.0309 (19)	0.0149 (17)	0.036 (2)	−0.0032 (15)	−0.0025 (19)	−0.001 (2)
C23	0.028 (3)	0.016 (3)	0.037 (3)	0.000 (3)	0.003 (3)	−0.008 (3)
C24	0.032 (2)	0.026 (2)	0.033 (3)	0.0019 (19)	−0.003 (2)	0.0031 (19)
C25	0.025 (2)	0.028 (2)	0.033 (3)	−0.0004 (19)	−0.008 (2)	−0.0006 (19)
C26	0.025 (2)	0.026 (2)	0.033 (2)	−0.0056 (17)	−0.0036 (19)	0.0030 (19)

Geometric parameters (Å, º)

P1—O5	1.513 (3)	C11—C16	1.3898 (11)
P1—O4	1.514 (4)	N12—C13	1.3401 (11)
P1—O3	1.572 (5)	N12—H12	0.88
P1—C3	1.815 (6)	C13—C14	1.3894 (11)
O3—H3	0.84	C13—H13	0.95
C1—O2	1.216 (5)	C14—C15	1.3902 (11)
C1—O1	1.326 (5)	C14—H14	0.95
C1—C2	1.513 (5)	C15—C16	1.3894 (11)
C2—C3	1.530 (8)	C15—H15	0.95
C2—H2A	0.99	C16—H16	0.95
C2—H2B	0.99	C21—N22	1.3387 (11)
C3—H3A	0.99	C21—C26	1.3892 (11)
C3—H3B	0.99	N22—C23	1.3400 (11)
O1—H11	0.84	C23—C24	1.3895 (11)
O6—H61	0.84	C23—H23	0.95
O6—H62	0.84	C24—C25	1.3895 (11)
N1—C11	1.382 (4)	C24—H24	0.95
N1—C21	1.410 (4)	C25—C26	1.3891 (11)
N1—H1	0.88	C25—H25	0.95
C11—N12	1.3397 (11)	C26—H26	0.95
O5—P1—O4	116.2 (3)	C13—N12—H12	119.3
O5—P1—O3	106.5 (2)	N12—C13—C14	120.1 (3)
O4—P1—O3	110.3 (3)	N12—C13—H13	120.0
O5—P1—C3	108.4 (5)	C14—C13—H13	120.0
O4—P1—C3	108.2 (4)	C13—C14—C15	119.3 (2)
O3—P1—C3	106.8 (5)	C13—C14—H14	120.4
O2—C1—O1	120.2 (4)	C15—C14—H14	120.4
O2—C1—C2	123.4 (4)	C16—C15—C14	119.8 (3)
O1—C1—C2	116.3 (4)	C16—C15—H15	120.1
C1—C2—C3	113.1 (4)	C14—C15—H15	120.1
C1—C2—H2A	109.0	C15—C16—C11	118.1 (3)
C3—C2—H2A	109.0	C15—C16—H16	120.9
C1—C2—H2B	109.0	C11—C16—H16	120.9
C3—C2—H2B	109.0	N22—C21—C26	124.2 (4)
H2A—C2—H2B	107.8	N22—C21—N1	117.0 (4)
C2—C3—P1	111.5 (6)	C26—C21—N1	118.7 (3)
C2—C3—H3A	109.3	C21—N22—C23	118.7 (4)
P1—C3—H3A	109.3	N22—C23—C24	121.5 (4)
C2—C3—H3B	109.3	N22—C23—H23	119.2
P1—C3—H3B	109.3	C24—C23—H23	119.2
H3A—C3—H3B	108.0	C23—C24—C25	118.5 (4)
H61—O6—H62	114	C23—C24—H24	120.7
C11—N1—C21	127.3 (3)	C25—C24—H24	120.7
C11—N1—H1	116.3	C26—C25—C24	120.8 (3)
C21—N1—H1	116.3	C26—C25—H25	119.6
N12—C11—N1	119.2 (3)	C24—C25—H25	119.6
N12—C11—C16	121.2 (3)	C25—C26—C21	116.0 (4)
N1—C11—C16	119.6 (3)	C25—C26—H26	122.0
C11—N12—C13	121.5 (3)	C21—C26—H26	122.0
C11—N12—H12	119.3
O2—C1—C2—C3	−0.9 (11)	C14—C15—C16—C11	−0.5 (7)
O1—C1—C2—C3	178.5 (7)	N12—C11—C16—C15	0.4 (7)
C1—C2—C3—P1	175.7 (6)	N1—C11—C16—C15	179.8 (4)
O5—P1—C3—C2	52.4 (9)	C11—N1—C21—N22	−4.9 (9)
O4—P1—C3—C2	179.2 (5)	C11—N1—C21—C26	177.5 (5)
O3—P1—C3—C2	−62.0 (8)	C26—C21—N22—C23	−1.1 (8)
C21—N1—C11—N12	3.9 (7)	N1—C21—N22—C23	−178.5 (8)
C21—N1—C11—C16	−175.5 (6)	C21—N22—C23—C24	−2.8 (9)
N1—C11—N12—C13	−179.5 (4)	N22—C23—C24—C25	4.6 (11)
C16—C11—N12—C13	−0.1 (7)	C23—C24—C25—C26	−2.5 (8)
C11—N12—C13—C14	−0.1 (7)	C24—C25—C26—C21	−1.1 (8)
N12—C13—C14—C15	0.1 (7)	N22—C21—C26—C25	3.0 (9)
C13—C14—C15—C16	0.2 (7)	N1—C21—C26—C25	−179.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6	0.84	1.76	2.579 (5)	165
O3—H3···O6^i	0.84	2.60	3.308 (5)	143
O1—H11···O5^ii	0.84	1.79	2.580 (4)	156
N1—H1···O4	0.88	1.88	2.755 (4)	173
N12—H12···N22	0.88	1.90	2.589 (5)	134
N12—H12···O2^iii	0.88	2.27	2.961 (4)	135
O6—H61···O5^iv	0.84	1.92	2.755 (6)	177
O6—H62···O4^v	0.84	1.91	2.744 (4)	172

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

(III) Piperazine–phosphonopropionic acid (1/1)

Crystal data

C4H12N2^2+·C3H5O5P^2^−	F(000) = 512
Mr = 240.20	Dx = 1.477 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2230 reflections
a = 10.6065 (3) Å	θ = 3.0–27.5°
b = 7.9214 (2) Å	µ = 0.26 mm^−1
c = 12.8892 (4) Å	T = 150 K
β = 94.0540 (12)°	Plate, colourless
V = 1080.22 (5) Å^3	0.30 × 0.28 × 0.15 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2447 independent reflections
Radiation source: fine-focus sealed X-ray tube	2048 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −13→13
Tmin = 0.904, Tmax = 0.971	k = −10→9
6785 measured reflections	l = −16→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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0261P)^2 + 0.5908P] where P = (Fo^2 + 2Fc^2)/3
2447 reflections	(Δ/σ)max = 0.001
137 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	−0.14995 (3)	0.38468 (5)	0.30764 (3)	0.01246 (12)
O1	0.31411 (11)	0.55269 (17)	0.28397 (9)	0.0255 (3)
O2	0.18824 (11)	0.58144 (17)	0.13997 (9)	0.0252 (3)
O3	−0.28138 (10)	0.41331 (14)	0.24556 (9)	0.0194 (3)
O4	−0.11942 (10)	0.19878 (13)	0.29566 (9)	0.0174 (2)
O5	−0.15216 (10)	0.44479 (15)	0.41824 (8)	0.0182 (3)
C1	0.20731 (15)	0.5426 (2)	0.23447 (12)	0.0177 (3)
C2	0.09908 (14)	0.4697 (2)	0.29166 (12)	0.0180 (3)
C3	−0.03428 (14)	0.5046 (2)	0.24297 (12)	0.0160 (3)
N11	0.36504 (12)	0.51669 (18)	0.48988 (10)	0.0201 (3)
C12	0.44696 (16)	0.6649 (2)	0.51645 (13)	0.0223 (4)
C13	0.57438 (16)	0.6432 (2)	0.47229 (13)	0.0217 (4)
N21	0.42462 (12)	0.57172 (16)	0.07702 (10)	0.0148 (3)
C22	0.43507 (15)	0.6577 (2)	−0.02486 (12)	0.0179 (3)
C23	0.55922 (16)	0.6144 (2)	−0.06889 (12)	0.0183 (3)
H3	−0.2977	0.5171	0.2430	0.029*
H2A	0.1051	0.5152	0.3634	0.022*
H2B	0.1107	0.3459	0.2968	0.022*
H3A	−0.0388	0.4741	0.1683	0.019*
H3B	−0.0532	0.6265	0.2484	0.019*
H11A	0.3489	0.5112	0.4189	0.024*
H11B	0.2891	0.5297	0.5193	0.024*
H12A	0.4585	0.6771	0.5930	0.027*
H12B	0.4059	0.7687	0.4878	0.027*
H13A	0.5636	0.6417	0.3954	0.026*
H13B	0.6296	0.7398	0.4935	0.026*
H21A	0.4853	0.6140	0.1246	0.018*
H21B	0.3467	0.5946	0.1009	0.018*
H22A	0.4292	0.7814	−0.0154	0.021*
H22B	0.3643	0.6218	−0.0742	0.021*
H23A	0.5622	0.6659	−0.1387	0.022*
H23B	0.6296	0.6620	−0.0235	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0113 (2)	0.0122 (2)	0.0136 (2)	−0.00021 (14)	−0.00108 (14)	0.00052 (14)
O1	0.0169 (6)	0.0408 (8)	0.0187 (6)	−0.0066 (5)	0.0008 (5)	0.0033 (5)
O2	0.0181 (6)	0.0404 (8)	0.0173 (6)	0.0000 (5)	0.0033 (5)	0.0089 (5)
O3	0.0149 (5)	0.0152 (5)	0.0266 (6)	0.0012 (4)	−0.0079 (5)	−0.0002 (5)
O4	0.0153 (5)	0.0137 (5)	0.0225 (6)	0.0005 (4)	−0.0035 (4)	−0.0002 (4)
O5	0.0155 (5)	0.0240 (6)	0.0152 (6)	−0.0009 (5)	0.0013 (4)	−0.0026 (4)
C1	0.0178 (8)	0.0180 (8)	0.0176 (8)	0.0003 (6)	0.0032 (6)	0.0002 (6)
C2	0.0152 (7)	0.0213 (8)	0.0177 (8)	−0.0007 (6)	0.0020 (6)	0.0044 (6)
C3	0.0164 (7)	0.0167 (8)	0.0148 (7)	−0.0009 (6)	0.0000 (6)	0.0024 (6)
N11	0.0137 (6)	0.0317 (8)	0.0151 (7)	−0.0014 (6)	0.0022 (5)	−0.0025 (6)
C12	0.0214 (8)	0.0245 (9)	0.0213 (8)	0.0000 (7)	0.0028 (6)	−0.0052 (7)
C13	0.0211 (8)	0.0249 (9)	0.0193 (8)	−0.0050 (7)	0.0026 (6)	−0.0017 (7)
N21	0.0141 (6)	0.0165 (6)	0.0139 (6)	−0.0004 (5)	0.0013 (5)	−0.0014 (5)
C22	0.0223 (8)	0.0171 (7)	0.0141 (7)	0.0023 (6)	0.0004 (6)	0.0017 (6)
C23	0.0230 (8)	0.0152 (8)	0.0173 (8)	−0.0026 (6)	0.0056 (6)	0.0009 (6)

Geometric parameters (Å, º)

P1—O5	1.5047 (11)	C12—C13	1.513 (2)
P1—O4	1.5179 (11)	C12—H12A	0.99
P1—O3	1.5739 (11)	C12—H12B	0.99
P1—C3	1.8019 (15)	C13—N11^i	1.487 (2)
O1—C1	1.2628 (19)	C13—H13A	0.99
O2—C1	1.2587 (19)	C13—H13B	0.99
O3—H3	0.84	N21—C23^ii	1.489 (2)
C1—C2	1.521 (2)	N21—C22	1.4901 (19)
C2—C3	1.532 (2)	N21—H21A	0.92
C2—H2A	0.99	N21—H21B	0.92
C2—H2B	0.99	C22—C23	1.510 (2)
C3—H3A	0.99	C22—H22A	0.99
C3—H3B	0.99	C22—H22B	0.99
N11—C12	1.486 (2)	C23—N21^ii	1.489 (2)
N11—C13^i	1.487 (2)	C23—H23A	0.99
N11—H11A	0.92	C23—H23B	0.99
N11—H11B	0.92
O5—P1—O4	114.90 (7)	N11—C12—H12A	109.6
O5—P1—O3	111.31 (6)	C13—C12—H12A	109.6
O4—P1—O3	106.01 (6)	N11—C12—H12B	109.6
O5—P1—C3	109.15 (7)	C13—C12—H12B	109.6
O4—P1—C3	107.90 (7)	H12A—C12—H12B	108.1
O3—P1—C3	107.24 (7)	N11^i—C13—C12	110.49 (14)
P1—O3—H3	109.5	N11^i—C13—H13A	109.6
O2—C1—O1	123.41 (15)	C12—C13—H13A	109.6
O2—C1—C2	119.11 (14)	N11^i—C13—H13B	109.6
O1—C1—C2	117.38 (14)	C12—C13—H13B	109.6
C1—C2—C3	116.08 (13)	H13A—C13—H13B	108.1
C1—C2—H2A	108.3	C23^ii—N21—C22	111.98 (12)
C3—C2—H2A	108.3	C23^ii—N21—H21A	109.2
C1—C2—H2B	108.3	C22—N21—H21A	109.2
C3—C2—H2B	108.3	C23^ii—N21—H21B	109.2
H2A—C2—H2B	107.4	C22—N21—H21B	109.2
C2—C3—P1	110.77 (10)	H21A—N21—H21B	107.9
C2—C3—H3A	109.5	N21—C22—C23	110.41 (12)
P1—C3—H3A	109.5	N21—C22—H22A	109.6
C2—C3—H3B	109.5	C23—C22—H22A	109.6
P1—C3—H3B	109.5	N21—C22—H22B	109.6
H3A—C3—H3B	108.1	C23—C22—H22B	109.6
C12—N11—C13^i	111.44 (13)	H22A—C22—H22B	108.1
C12—N11—H11A	109.3	N21^ii—C23—C22	111.03 (13)
C13^i—N11—H11A	109.3	N21^ii—C23—H23A	109.4
C12—N11—H11B	109.3	C22—C23—H23A	109.4
C13^i—N11—H11B	109.3	N21^ii—C23—H23B	109.4
H11A—N11—H11B	108.0	C22—C23—H23B	109.4
N11—C12—C13	110.29 (14)	H23A—C23—H23B	108.0
O2—C1—C2—C3	−20.5 (2)	O3—P1—C3—C2	−174.17 (10)
O1—C1—C2—C3	163.06 (15)	C13^i—N11—C12—C13	56.89 (19)
C1—C2—C3—P1	171.29 (11)	N11—C12—C13—N11^i	−56.34 (18)
O5—P1—C3—C2	65.12 (12)	C23^ii—N21—C22—C23	−55.72 (18)
O4—P1—C3—C2	−60.36 (12)	N21—C22—C23—N21^ii	55.18 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^iii	0.84	1.74	2.535 (2)	157
N11—H11A···O1	0.92	1.78	2.686 (2)	167
N11—H11B···O5^iv	0.92	1.72	2.640 (2)	176
N21—H21A···O4^v	0.92	1.82	2.738 (2)	172
N21—H21B···O1	0.92	2.43	2.992 (2)	119
N21—H21B···O2	0.92	1.79	2.690 (2)	165
C13—H13B···O2^vi	0.99	2.41	3.243 (2)	142
C22—H22A···O5^vii	0.99	2.47	3.349 (2)	148
C22—H22B···O3^viii	0.99	2.34	3.227 (2)	149

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

(IV) N,N'-Dimethylpiperazine–phosphonopropionic acid–water (1/2/2)

Crystal data

C6H16N2^2+·2(C3H6O5P^−)·2(H2O)	F(000) = 488
Mr = 458.34	Dx = 1.430 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2415 reflections
a = 6.9270 (2) Å	θ = 2.9–27.5°
b = 20.6027 (5) Å	µ = 0.26 mm^−1
c = 8.0115 (2) Å	T = 150 K
β = 111.4092 (10)°	Block, colourless
V = 1064.47 (5) Å^3	0.32 × 0.22 × 0.16 mm
Z = 2

Data collection

Kappa-CCD diffractometer	1990 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.035
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
ϕ scans, and ω scans with κ offsets	h = −8→8
6838 measured reflections	k = −26→26
2415 independent 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 0.3605P] where P = (Fo^2 + 2Fc^2)/3
2415 reflections	(Δ/σ)max = 0.001
135 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.29332 (6)	0.382569 (18)	0.06467 (5)	0.01690 (13)
O1	−0.2948 (2)	0.22877 (6)	−0.2716 (2)	0.0426 (4)
O2	−0.03885 (19)	0.18412 (6)	−0.04435 (18)	0.0369 (3)
O3	0.21194 (18)	0.42239 (5)	−0.11368 (14)	0.0244 (3)
O4	0.19661 (16)	0.40809 (5)	0.19357 (14)	0.0216 (3)
O5	0.52786 (16)	0.38202 (5)	0.14543 (16)	0.0247 (3)
C1	−0.1178 (2)	0.23078 (8)	−0.1329 (2)	0.0247 (4)
C2	−0.0318 (3)	0.29874 (8)	−0.1004 (2)	0.0280 (4)
C3	0.2023 (2)	0.30174 (7)	−0.0040 (2)	0.0228 (3)
N11	0.45581 (19)	0.43241 (6)	0.51960 (16)	0.0189 (3)
C12	0.6670 (2)	0.45397 (8)	0.5346 (2)	0.0210 (3)
C13	0.6520 (2)	0.51458 (8)	0.4228 (2)	0.0218 (3)
C14	0.4643 (3)	0.37154 (8)	0.6226 (2)	0.0270 (4)
O6	0.1965 (2)	0.54462 (7)	−0.0611 (3)	0.0298 (6)	0.928 (6)
O61	0.154 (3)	0.5377 (9)	−0.161 (4)	0.025*	0.072 (6)
H1	−0.3442	0.1911	−0.2824	0.064*
H3	0.2154	0.4622	−0.0898	0.037*
H2A	−0.0985	0.3225	−0.0284	0.034*
H2B	−0.0689	0.3212	−0.2171	0.034*
H3A	0.2702	0.2849	−0.0846	0.027*
H3B	0.2426	0.2733	0.1029	0.027*
H11	0.3803	0.4238	0.3994	0.023*
H12A	0.7359	0.4189	0.4925	0.025*
H12B	0.7517	0.4632	0.6616	0.025*
H13A	0.7930	0.5291	0.4358	0.026*
H13B	0.5750	0.5045	0.2948	0.026*
H14A	0.3232	0.3581	0.6075	0.040*
H14B	0.5443	0.3792	0.7499	0.040*
H14C	0.5310	0.3373	0.5780	0.040*
H61	0.0767	0.5599	−0.1065	0.065*
H62	0.2756	0.5670	−0.0951	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0139 (2)	0.0155 (2)	0.0197 (2)	0.00018 (14)	0.00415 (15)	0.00017 (15)
O1	0.0290 (7)	0.0225 (7)	0.0541 (8)	−0.0081 (5)	−0.0114 (6)	0.0042 (6)
O2	0.0297 (7)	0.0246 (7)	0.0443 (8)	−0.0030 (5)	−0.0008 (6)	0.0058 (6)
O3	0.0310 (6)	0.0210 (6)	0.0209 (6)	0.0010 (5)	0.0092 (5)	0.0017 (5)
O4	0.0179 (5)	0.0264 (6)	0.0190 (5)	0.0007 (5)	0.0049 (4)	−0.0025 (5)
O5	0.0141 (6)	0.0189 (6)	0.0376 (7)	0.0002 (4)	0.0053 (5)	0.0007 (5)
C1	0.0191 (8)	0.0214 (8)	0.0300 (8)	−0.0015 (7)	0.0046 (7)	−0.0001 (7)
C2	0.0204 (8)	0.0198 (8)	0.0357 (9)	−0.0021 (6)	0.0007 (7)	0.0000 (7)
C3	0.0194 (8)	0.0180 (8)	0.0287 (8)	−0.0004 (6)	0.0059 (7)	−0.0008 (7)
N11	0.0193 (6)	0.0185 (6)	0.0168 (6)	−0.0007 (5)	0.0043 (5)	−0.0008 (5)
C12	0.0166 (7)	0.0212 (8)	0.0237 (8)	0.0001 (6)	0.0054 (6)	−0.0022 (6)
C13	0.0204 (8)	0.0219 (8)	0.0238 (8)	−0.0006 (6)	0.0088 (6)	−0.0021 (6)
C14	0.0287 (9)	0.0206 (8)	0.0283 (9)	−0.0017 (7)	0.0064 (7)	0.0045 (7)
O6	0.0210 (7)	0.0211 (7)	0.0492 (16)	0.0033 (5)	0.0152 (8)	0.0065 (7)

Geometric parameters (Å, º)

P1—O5	1.5136 (11)	N11—C12	1.4911 (19)
P1—O4	1.5154 (11)	N11—H11	0.93
P1—O3	1.5635 (11)	C12—C13	1.518 (2)
P1—C3	1.7945 (16)	C12—H12A	0.99
O1—C1	1.3212 (19)	C12—H12B	0.99
O1—H1	0.84	C13—N11^i	1.488 (2)
O2—C1	1.201 (2)	C13—H13A	0.99
O3—H3	0.84	C13—H13B	0.99
C1—C2	1.507 (2)	C14—H14A	0.98
C2—C3	1.521 (2)	C14—H14B	0.98
C2—H2A	0.99	C14—H14C	0.98
C2—H2B	0.99	O6—O61	0.76 (3)
C3—H3A	0.99	O6—H61	0.84
C3—H3B	0.99	O6—H62	0.84
N11—C13^i	1.488 (2)	O61—H61	0.92
N11—C14	1.490 (2)	O61—H62	1.02
O5—P1—O4	112.57 (6)	C14—N11—H11	107.8
O5—P1—O3	111.54 (7)	C12—N11—H11	107.8
O4—P1—O3	109.82 (6)	N11—C12—C13	110.10 (12)
O5—P1—C3	109.05 (7)	N11—C12—H12A	109.6
O4—P1—C3	109.73 (7)	C13—C12—H12A	109.6
O3—P1—C3	103.74 (7)	N11—C12—H12B	109.6
C1—O1—H1	109.5	C13—C12—H12B	109.6
P1—O3—H3	109.5	H12A—C12—H12B	108.2
O2—C1—O1	123.67 (15)	N11^i—C13—C12	110.76 (12)
O2—C1—C2	125.13 (15)	N11^i—C13—H13A	109.5
O1—C1—C2	111.20 (14)	C12—C13—H13A	109.5
C1—C2—C3	113.98 (14)	N11^i—C13—H13B	109.5
C1—C2—H2A	108.8	C12—C13—H13B	109.5
C3—C2—H2A	108.8	H13A—C13—H13B	108.1
C1—C2—H2B	108.8	N11—C14—H14A	109.5
C3—C2—H2B	108.8	N11—C14—H14B	109.5
H2A—C2—H2B	107.7	H14A—C14—H14B	109.5
C2—C3—P1	112.55 (11)	N11—C14—H14C	109.5
C2—C3—H3A	109.1	H14A—C14—H14C	109.5
P1—C3—H3A	109.1	H14B—C14—H14C	109.5
C2—C3—H3B	109.1	O61—O6—H61	70.6
P1—C3—H3B	109.1	O61—O6—H62	79.1
H3A—C3—H3B	107.8	H61—O6—H62	108.5
C13^i—N11—C14	111.63 (12)	O6—O61—H61	58.7
C13^i—N11—C12	110.18 (12)	O6—O61—H62	53.8
C14—N11—C12	111.51 (12)	H61—O61—H62	88.6
C13^i—N11—H11	107.8
O3—P1—C3—C2	−56.5 (2)	P1—C3—C2—C1	−170.4 (2)
O4—P1—C3—C2	60.8 (2)	C3—C2—C1—O1	−154.9 (2)
O5—P1—C3—C2	−175.5 (2)	C3—C2—C1—O2	25.9 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5^ii	0.84	1.74	2.562 (2)	167
O3—H3···O6	0.84	1.73	2.562 (2)	174
N11—H11···O4	0.93	1.71	2.622 (2)	168
O6—H61···O4^iii	0.84	1.88	2.717 (2)	176
O6—H62···O5^iv	0.83	1.88	2.707 (2)	174

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

(V) 4,4'-Bipyridyl–phosphonopropionic acid (1/1)

Crystal data

C10H8.82N20.72+·C3H6O5.28P0.72=	F(000) = 648
Mr = 1240.98	Dx = 1.537 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3059 reflections
a = 11.3482 (5) Å	θ = 3.3–27.5°
b = 6.7178 (3) Å	µ = 0.23 mm^−1
c = 17.7354 (7) Å	T = 150 K
β = 97.4980 (18)°	Plate, colourless
V = 1340.50 (10) Å^3	0.22 × 0.20 × 0.08 mm
Z = 1

Data collection

Kappa-CCD diffractometer	2113 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.060
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
ϕ scans, and ω scans with κ offsets	h = −14→14
13381 measured reflections	k = −8→8
3059 independent reflections	l = −22→23

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 0.2557P] where P = (Fo^2 + 2Fc^2)/3
3059 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	−0.25452 (14)	0.2979 (2)	0.32676 (9)	0.0255 (4)
C12	−0.33789 (17)	0.2537 (3)	0.37035 (10)	0.0233 (4)
C13	−0.45783 (16)	0.2444 (3)	0.34295 (10)	0.0221 (4)
C14	−0.49461 (16)	0.2853 (3)	0.26663 (10)	0.0195 (4)
C15	−0.40681 (17)	0.3329 (3)	0.22137 (11)	0.0294 (5)
C16	−0.28898 (18)	0.3364 (3)	0.25306 (11)	0.0320 (5)
N21	−0.86140 (13)	0.2691 (2)	0.17454 (9)	0.0236 (4)
C22	−0.77653 (17)	0.2587 (3)	0.12837 (11)	0.0234 (4)
C23	−0.65690 (16)	0.2626 (3)	0.15610 (10)	0.0220 (4)
C24	−0.62221 (16)	0.2792 (3)	0.23439 (10)	0.0195 (4)
C25	−0.71148 (16)	0.2900 (3)	0.28117 (10)	0.0219 (4)
C26	−0.82974 (16)	0.2843 (3)	0.24981 (11)	0.0231 (4)
P1	0.36541 (4)	0.25021 (7)	0.53910 (3)	0.01867 (15)
O1	−0.02847 (12)	0.2992 (3)	0.37185 (8)	0.0377 (4)
O2	−0.05061 (12)	0.2529 (2)	0.49404 (8)	0.0311 (4)
O3	0.39660 (11)	0.4400 (2)	0.49837 (8)	0.0275 (3)
O4	0.41748 (12)	0.24594 (19)	0.62307 (7)	0.0262 (3)
O5	0.39726 (11)	0.0642 (2)	0.49603 (7)	0.0266 (3)
C1	0.01158 (16)	0.2721 (3)	0.44412 (10)	0.0223 (4)
C2	0.14589 (15)	0.2672 (3)	0.45486 (10)	0.0220 (4)
C3	0.20659 (15)	0.2485 (3)	0.53604 (10)	0.0201 (4)
H11	−0.1790	0.3017	0.3458	0.031*	0.22 (4)
H12	−0.3140	0.2273	0.4227	0.028*
H13	−0.5143	0.2106	0.3759	0.027*
H15	−0.4280	0.3627	0.1690	0.035*
H16	−0.2301	0.3674	0.2214	0.038*
H21	−0.9370	0.2659	0.1555	0.028*	0.50
H22	−0.7995	0.2483	0.0751	0.028*
H23	−0.5988	0.2542	0.1222	0.026*
H25	−0.6912	0.3014	0.3347	0.026*
H26	−0.8898	0.2914	0.2824	0.028*
H1	−0.1031	0.2950	0.3658	0.057*	0.78 (4)
H3	0.4705	0.4573	0.5054	0.041*	0.50
H4	0.4919	0.2375	0.6267	0.039*	0.50
H5	0.5000	0.0000	0.5000	0.040*
H2A	0.1747	0.3906	0.4328	0.026*
H2B	0.1716	0.1540	0.4252	0.026*
H3A	0.1815	0.1230	0.5585	0.024*
H3B	0.1820	0.3605	0.5667	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0174 (8)	0.0324 (9)	0.0257 (8)	0.0002 (6)	−0.0010 (6)	0.0015 (7)
C12	0.0220 (9)	0.0275 (10)	0.0194 (9)	0.0007 (7)	−0.0009 (7)	−0.0002 (7)
C13	0.0198 (9)	0.0280 (10)	0.0185 (9)	−0.0006 (7)	0.0025 (7)	0.0013 (7)
C14	0.0168 (9)	0.0215 (9)	0.0200 (9)	−0.0004 (7)	0.0013 (7)	0.0003 (7)
C15	0.0210 (10)	0.0455 (12)	0.0212 (10)	−0.0002 (9)	0.0013 (8)	0.0047 (9)
C16	0.0211 (10)	0.0471 (13)	0.0281 (11)	−0.0030 (9)	0.0051 (8)	0.0062 (9)
N21	0.0182 (8)	0.0283 (9)	0.0231 (8)	0.0006 (6)	−0.0015 (6)	0.0010 (6)
C22	0.0232 (10)	0.0262 (10)	0.0195 (9)	0.0000 (7)	−0.0019 (7)	0.0007 (7)
C23	0.0206 (9)	0.0264 (10)	0.0188 (9)	−0.0005 (7)	0.0022 (7)	−0.0004 (7)
C24	0.0188 (9)	0.0201 (9)	0.0193 (9)	0.0010 (7)	0.0010 (7)	−0.0003 (7)
C25	0.0208 (9)	0.0266 (10)	0.0177 (9)	0.0000 (7)	0.0008 (7)	−0.0007 (7)
C26	0.0197 (9)	0.0266 (10)	0.0233 (9)	0.0007 (7)	0.0043 (7)	−0.0013 (7)
P1	0.0126 (2)	0.0240 (3)	0.0191 (3)	0.00014 (17)	0.00073 (17)	0.00022 (18)
O1	0.0143 (7)	0.0745 (11)	0.0234 (7)	0.0006 (7)	−0.0010 (5)	0.0026 (7)
O2	0.0186 (7)	0.0502 (9)	0.0253 (7)	−0.0003 (6)	0.0059 (6)	0.0023 (6)
O3	0.0191 (7)	0.0301 (8)	0.0324 (8)	−0.0034 (5)	0.0004 (6)	0.0069 (6)
O4	0.0184 (7)	0.0377 (8)	0.0211 (7)	0.0002 (6)	−0.0025 (5)	0.0008 (6)
O5	0.0214 (7)	0.0302 (8)	0.0279 (8)	0.0047 (5)	0.0018 (6)	−0.0056 (5)
C1	0.0170 (9)	0.0281 (10)	0.0214 (9)	0.0004 (7)	0.0010 (7)	−0.0021 (7)
C2	0.0132 (8)	0.0320 (10)	0.0207 (9)	−0.0002 (7)	0.0019 (7)	0.0002 (8)
C3	0.0143 (8)	0.0269 (9)	0.0189 (9)	0.0000 (7)	0.0016 (7)	−0.0005 (7)

Geometric parameters (Å, º)

N11—C12	1.331 (2)	C25—C26	1.385 (3)
N11—C16	1.340 (2)	C25—H25	0.95
N11—H11	0.88	C26—H26	0.95
C12—C13	1.386 (3)	P1—O4	1.5292 (13)
C12—H12	0.95	P1—O3	1.5293 (13)
C13—C14	1.391 (2)	P1—O5	1.5320 (13)
C13—H13	0.95	P1—C3	1.7961 (18)
C14—C15	1.396 (3)	O1—C1	1.315 (2)
C14—C24	1.486 (3)	O1—H1	0.84
C15—C16	1.381 (3)	O2—C1	1.209 (2)
C15—H15	0.95	O3—H3	0.84
C16—H16	0.95	O4—H4	0.84
N21—C26	1.340 (2)	O5—H5	1.2366
N21—C22	1.345 (2)	C1—C2	1.511 (2)
N21—H21	0.88	C2—C3	1.518 (2)
C22—C23	1.382 (3)	C2—H2A	0.99
C22—H22	0.95	C2—H2B	0.99
C23—C24	1.397 (2)	C3—H3A	0.99
C23—H23	0.95	C3—H3B	0.99
C24—C25	1.393 (3)
C12—N11—C16	118.07 (17)	C26—C25—H25	119.9
C12—N11—H11	121.0	C24—C25—H25	119.9
C16—N11—H11	121.0	N21—C26—C25	121.47 (17)
N11—C12—C13	123.12 (17)	N21—C26—H26	119.3
N11—C12—H12	118.4	C25—C26—H26	119.3
C13—C12—H12	118.4	O4—P1—O3	113.07 (8)
C12—C13—C14	119.26 (17)	O4—P1—O5	112.58 (7)
C12—C13—H13	120.4	O3—P1—O5	111.11 (8)
C14—C13—H13	120.4	O4—P1—C3	106.74 (8)
C13—C14—C15	117.31 (17)	O3—P1—C3	106.50 (8)
C13—C14—C24	121.50 (16)	O5—P1—C3	106.31 (8)
C15—C14—C24	121.19 (17)	C1—O1—H1	109.5
C16—C15—C14	119.72 (18)	P1—O3—H3	109.5
C16—C15—H15	120.1	P1—O4—H4	109.5
C14—C15—H15	120.1	P1—O5—H5	122.6
N11—C16—C15	122.51 (18)	O2—C1—O1	124.59 (17)
N11—C16—H16	118.7	O2—C1—C2	125.51 (17)
C15—C16—H16	118.7	O1—C1—C2	109.90 (15)
C26—N21—C22	119.36 (16)	C1—C2—C3	116.53 (15)
C26—N21—H21	120.3	C1—C2—H2A	108.2
C22—N21—H21	120.3	C3—C2—H2A	108.2
N21—C22—C23	122.03 (17)	C1—C2—H2B	108.2
N21—C22—H22	119.0	C3—C2—H2B	108.2
C23—C22—H22	119.0	H2A—C2—H2B	107.3
C22—C23—C24	119.42 (17)	C2—C3—P1	110.95 (12)
C22—C23—H23	120.3	C2—C3—H3A	109.4
C24—C23—H23	120.3	P1—C3—H3A	109.4
C25—C24—C23	117.62 (16)	C2—C3—H3B	109.4
C25—C24—C14	121.15 (16)	P1—C3—H3B	109.4
C23—C24—C14	121.23 (16)	H3A—C3—H3B	108.0
C26—C25—C24	120.10 (17)
C16—N11—C12—C13	0.5 (3)	C15—C14—C24—C25	−160.98 (19)
N11—C12—C13—C14	−0.8 (3)	C13—C14—C24—C23	−161.26 (17)
C12—C13—C14—C15	0.4 (3)	C15—C14—C24—C23	18.9 (3)
C12—C13—C14—C24	−179.47 (16)	C23—C24—C25—C26	0.0 (3)
C13—C14—C15—C16	0.4 (3)	C14—C24—C25—C26	179.91 (16)
C24—C14—C15—C16	−179.74 (19)	C22—N21—C26—C25	0.1 (3)
C12—N11—C16—C15	0.4 (3)	C24—C25—C26—N21	−0.2 (3)
C14—C15—C16—N11	−0.8 (3)	O2—C1—C2—C3	−3.8 (3)
C26—N21—C22—C23	0.2 (3)	O1—C1—C2—C3	176.69 (16)
N21—C22—C23—C24	−0.4 (3)	C1—C2—C3—P1	−178.76 (12)
C22—C23—C24—C25	0.3 (3)	O4—P1—C3—C2	176.01 (12)
C22—C23—C24—C14	−179.61 (16)	O3—P1—C3—C2	54.96 (14)
C13—C14—C24—C25	18.8 (3)	O5—P1—C3—C2	−63.60 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N11	0.84	1.77	2.585 (2)	164
O3—H3···O3^i	0.84	1.67	2.475 (2)	160
O4—H4···N21^ii	0.84	1.77	2.558 (2)	156
O5—H5···O5^iii	1.24	1.24	2.473 (2)	180
N11—H11···O1	0.88	1.71	2.585 (2)	173
N21—H21···O4^iv	0.88	1.68	2.558 (2)	177

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

(VI) 1,2-Bis(4'-pyridyl)ethane–phosphonopropionic acid (1/2)

Crystal data

C12H14N2^2+·2(C3H6O5P^−)	Z = 1
Mr = 492.35	F(000) = 258
Triclinic, P1	Dx = 1.520 Mg m^−3
Hall symbol: -P -1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5651 (3) Å	Cell parameters from 5037 reflections
b = 8.6472 (3) Å	θ = 2.8–27.6°
c = 9.0077 (4) Å	µ = 0.26 mm^−1
α = 72.6340 (14)°	T = 150 K
β = 73.1760 (15)°	Plate, colourless
γ = 87.386 (2)°	0.30 × 0.14 × 0.12 mm
V = 537.79 (4) Å^3

Data collection

Kappa-CCD diffractometer	2457 independent reflections
Radiation source: fine-focus sealed X-ray tube	2163 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ scans, and ω scans with κ offsets	θmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.930, Tmax = 0.973	k = −11→11
6047 measured reflections	l = −11→11

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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0237P)^2 + 0.2452P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2457 reflections	Δρmax = 0.32 e Å^−3
148 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (7)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N11	0.37635 (17)	0.04194 (14)	0.85339 (16)	0.0206 (3)
C12	0.2617 (2)	−0.04464 (17)	0.99512 (19)	0.0213 (3)
C13	0.2703 (2)	−0.21093 (17)	1.04550 (18)	0.0203 (3)
C14	0.39673 (19)	−0.28923 (16)	0.94808 (18)	0.0173 (3)
C15	0.5144 (2)	−0.19391 (17)	0.80193 (19)	0.0215 (3)
C16	0.5006 (2)	−0.02859 (18)	0.75733 (19)	0.0233 (3)
C17	0.40381 (19)	−0.47121 (16)	0.9967 (2)	0.0210 (3)
P1	0.22718 (5)	0.39160 (4)	0.61755 (5)	0.01547 (13)
O1	0.18632 (15)	0.99449 (12)	0.57217 (14)	0.0262 (3)
O2	−0.02062 (17)	0.83045 (13)	0.78710 (15)	0.0325 (3)
O3	0.30644 (14)	0.45771 (12)	0.42584 (13)	0.0193 (2)
O4	0.38859 (13)	0.35962 (11)	0.69065 (13)	0.0189 (2)
O5	0.09918 (14)	0.24752 (11)	0.66071 (14)	0.0215 (2)
C1	0.1045 (2)	0.85194 (16)	0.66337 (19)	0.0189 (3)
C2	0.1917 (2)	0.71868 (16)	0.59294 (19)	0.0198 (3)
C3	0.09578 (19)	0.55173 (15)	0.68156 (18)	0.0173 (3)
H11	0.3700	0.1481	0.8224	0.025*
H12	0.1746	0.0084	1.0608	0.026*
H13	0.1902	−0.2726	1.1467	0.024*
H15	0.6035	−0.2431	0.7337	0.026*
H16	0.5799	0.0365	0.6574	0.028*
H17A	0.3668	−0.5119	0.9178	0.025*
H17B	0.3140	−0.5176	1.1048	0.025*
H1	0.1425	1.0658	0.6170	0.039*
H3	0.3995	0.5199	0.4009	0.029*
H2A	0.3221	0.7122	0.5947	0.024*
H2B	0.1918	0.7484	0.4779	0.024*
H3A	−0.0265	0.5517	0.6620	0.021*
H3B	0.0748	0.5298	0.7998	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0242 (6)	0.0130 (5)	0.0258 (7)	0.0038 (5)	−0.0090 (5)	−0.0065 (5)
C12	0.0184 (7)	0.0204 (7)	0.0263 (8)	0.0053 (5)	−0.0047 (6)	−0.0112 (6)
C13	0.0178 (7)	0.0201 (7)	0.0198 (7)	0.0007 (5)	−0.0009 (6)	−0.0058 (6)
C14	0.0165 (7)	0.0151 (6)	0.0205 (7)	0.0015 (5)	−0.0058 (6)	−0.0051 (5)
C15	0.0233 (7)	0.0168 (7)	0.0209 (8)	0.0036 (5)	−0.0007 (6)	−0.0065 (6)
C16	0.0248 (8)	0.0193 (7)	0.0208 (8)	0.0004 (6)	−0.0010 (6)	−0.0039 (6)
C17	0.0190 (7)	0.0144 (7)	0.0272 (8)	0.0010 (5)	−0.0041 (6)	−0.0051 (6)
P1	0.0148 (2)	0.01102 (18)	0.0200 (2)	0.00057 (12)	−0.00161 (14)	−0.00699 (14)
O1	0.0290 (6)	0.0130 (5)	0.0321 (7)	−0.0007 (4)	0.0031 (5)	−0.0118 (4)
O2	0.0374 (7)	0.0198 (5)	0.0320 (7)	0.0004 (5)	0.0079 (5)	−0.0128 (5)
O3	0.0179 (5)	0.0194 (5)	0.0207 (6)	−0.0019 (4)	−0.0024 (4)	−0.0089 (4)
O4	0.0173 (5)	0.0149 (5)	0.0228 (6)	0.0018 (4)	−0.0042 (4)	−0.0049 (4)
O5	0.0186 (5)	0.0134 (5)	0.0311 (6)	−0.0011 (4)	−0.0002 (4)	−0.0112 (4)
C1	0.0190 (7)	0.0142 (6)	0.0243 (8)	0.0018 (5)	−0.0042 (6)	−0.0090 (6)
C2	0.0195 (7)	0.0139 (6)	0.0250 (8)	0.0011 (5)	−0.0013 (6)	−0.0094 (6)
C3	0.0162 (7)	0.0133 (6)	0.0218 (7)	0.0010 (5)	−0.0019 (5)	−0.0079 (5)

Geometric parameters (Å, º)

N11—C12	1.338 (2)	P1—O5	1.4980 (10)
N11—C16	1.340 (2)	P1—O4	1.5254 (11)
N11—H11	0.88	P1—O3	1.5846 (11)
C12—C13	1.377 (2)	P1—C3	1.8048 (14)
C12—H12	0.95	O1—C1	1.3222 (17)
C13—C14	1.397 (2)	O1—H1	0.84
C13—H13	0.95	O2—C1	1.2059 (19)
C14—C15	1.395 (2)	O3—H3	0.84
C14—C17	1.5052 (18)	C1—C2	1.5134 (19)
C15—C16	1.373 (2)	C2—C3	1.5234 (18)
C15—H15	0.95	C2—H2A	0.99
C16—H16	0.95	C2—H2B	0.99
C17—C17^i	1.528 (3)	C3—H3A	0.99
C17—H17A	0.99	C3—H3B	0.99
C17—H17B	0.99
C12—N11—C16	121.84 (13)	O5—P1—O4	114.93 (6)
C12—N11—H11	119.1	O5—P1—O3	108.77 (6)
C16—N11—H11	119.1	O4—P1—O3	108.82 (6)
N11—C12—C13	119.76 (13)	O5—P1—C3	108.77 (6)
N11—C12—H12	120.1	O4—P1—C3	108.83 (6)
C13—C12—H12	120.1	O3—P1—C3	106.38 (6)
C12—C13—C14	120.16 (14)	C1—O1—H1	109.5
C12—C13—H13	119.9	P1—O3—H3	109.5
C14—C13—H13	119.9	O2—C1—O1	124.74 (13)
C15—C14—C13	118.05 (13)	O2—C1—C2	124.54 (13)
C15—C14—C17	120.61 (13)	O1—C1—C2	110.71 (12)
C13—C14—C17	121.32 (13)	C1—C2—C3	114.53 (12)
C16—C15—C14	119.54 (14)	C1—C2—H2A	108.6
C16—C15—H15	120.2	C3—C2—H2A	108.6
C14—C15—H15	120.2	C1—C2—H2B	108.6
N11—C16—C15	120.64 (14)	C3—C2—H2B	108.6
N11—C16—H16	119.7	H2A—C2—H2B	107.6
C15—C16—H16	119.7	C2—C3—P1	112.83 (10)
C14—C17—C17^i	112.33 (14)	C2—C3—H3A	109.0
C14—C17—H17A	109.1	P1—C3—H3A	109.0
C17^i—C17—H17A	109.1	C2—C3—H3B	109.0
C14—C17—H17B	109.1	P1—C3—H3B	109.0
C17^i—C17—H17B	109.1	H3A—C3—H3B	107.8
H17A—C17—H17B	107.9
C16—N11—C12—C13	0.2 (2)	C15—C14—C17—C17^i	57.0 (2)
N11—C12—C13—C14	−0.8 (2)	C13—C14—C17—C17^i	−124.38 (18)
C12—C13—C14—C15	1.3 (2)	O2—C1—C2—C3	6.2 (2)
C12—C13—C14—C17	−177.40 (13)	O1—C1—C2—C3	−174.92 (13)
C13—C14—C15—C16	−1.1 (2)	C1—C2—C3—P1	−169.43 (10)
C17—C14—C15—C16	177.54 (14)	O5—P1—C3—C2	−159.26 (10)
C12—N11—C16—C15	−0.1 (2)	O4—P1—C3—C2	74.85 (12)
C14—C15—C16—N11	0.5 (2)	O3—P1—C3—C2	−42.25 (12)

Symmetry code: (i) −x+1, −y−1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O4	0.88	1.84	2.692 (2)	161
O1—H1···O5^ii	0.84	1.73	2.542 (2)	163
O3—H3···O4^iii	0.84	1.79	2.619 (2)	168
C12—H12···O2^iv	0.95	2.29	3.224 (2)	167
C13—H13···O5^v	0.95	2.41	3.196 (2)	139

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

(VII) 2,6-Dimethylpiperazine–phosphonopropionic acid–methanol (1/2/0.34)

Crystal data

C6H16N2^2+·2(C3H6O5P^−)·0.3(CH4O)	F(000) = 910
Mr = 429.31	Dx = 1.377 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 4652 reflections
a = 20.2229 (17) Å	θ = 3.8–27.5°
b = 8.6162 (6) Å	µ = 0.26 mm^−1
c = 11.8812 (9) Å	T = 150 K
V = 2070.2 (3) Å^3	Plate, colourless
Z = 4	0.24 × 0.10 × 0.04 mm

Data collection

Kappa-CCD diffractometer	3521 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.125
Graphite monochromator	θmax = 27.5°, θmin = 3.8°
ϕ scans, and ω scans with κ offsets	h = −26→25
15150 measured reflections	k = −11→11
4652 independent reflections	l = −15→15

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.064	w = 1/[σ^2(Fo^2) + (0.0488P)^2 + 2.3804P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.168	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.56 e Å^−3
4652 reflections	Δρmin = −0.30 e Å^−3
250 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.019 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2161 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.07 (15)

Special details

Experimental. ?e' command in the SHELXL97 input file.

Geometry. Mean-plane data from the final SHELXL97 refinement run:-

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.41188 (19)	0.4517 (4)	0.2262 (3)	0.0389 (9)
N4	0.4030 (2)	0.5321 (5)	0.4606 (4)	0.0441 (10)
C2	0.3906 (3)	0.3365 (5)	0.3133 (4)	0.0403 (11)
C3	0.4224 (3)	0.3749 (6)	0.4246 (5)	0.0453 (12)
C5	0.4215 (3)	0.6522 (6)	0.3742 (5)	0.0437 (11)
C6	0.3931 (3)	0.6175 (5)	0.2601 (5)	0.0413 (10)
C7	0.4077 (3)	0.1733 (6)	0.2744 (6)	0.0537 (15)
C8	0.4172 (3)	0.7278 (6)	0.1727 (5)	0.0541 (14)
P1	0.10255 (6)	0.52993 (13)	0.24994 (11)	0.0361 (3)
O11	0.0993 (2)	1.1155 (4)	0.2527 (7)	0.107 (2)
O12	0.20082 (18)	1.0163 (4)	0.2506 (4)	0.0519 (9)
O13	0.07487 (17)	0.5181 (4)	0.3735 (3)	0.0429 (8)
O14	0.04324 (17)	0.5500 (4)	0.1730 (3)	0.0417 (8)
O15	0.14568 (17)	0.3921 (4)	0.2219 (3)	0.0451 (9)
C11	0.1420 (3)	0.9984 (5)	0.2567 (6)	0.0501 (12)
C12	0.1083 (3)	0.8438 (5)	0.2678 (7)	0.0577 (16)
C13	0.1512 (2)	0.7024 (5)	0.2433 (5)	0.0426 (11)
P2	0.22451 (6)	0.38493 (12)	0.53461 (11)	0.0353 (3)
O21	0.21387 (17)	−0.2113 (4)	0.5093 (3)	0.0451 (9)
O22	0.31199 (18)	−0.1005 (4)	0.4738 (3)	0.0505 (9)
O23	0.23345 (16)	0.3816 (4)	0.6663 (3)	0.0393 (8)
O24	0.15009 (15)	0.3965 (4)	0.5195 (3)	0.0393 (7)
O25	0.26564 (16)	0.5123 (3)	0.4808 (3)	0.0383 (8)
C21	0.2535 (3)	−0.0882 (5)	0.4985 (4)	0.0398 (10)
C22	0.2190 (2)	0.0597 (5)	0.5268 (5)	0.0416 (10)
C23	0.2546 (3)	0.2034 (5)	0.4835 (4)	0.0409 (11)
O1	0.0298 (6)	0.2034 (13)	0.5328 (12)	0.058 (4)*	0.337 (13)
C1	0.0061 (10)	0.043 (2)	0.5029 (16)	0.058 (4)*	0.337 (13)
H1A	0.3922	0.4278	0.1585	0.047*
H1B	0.4570	0.4456	0.2167	0.047*
H4A	0.4234	0.5552	0.5277	0.053*
H4B	0.3580	0.5348	0.4721	0.053*
H2	0.3416	0.3439	0.3222	0.048*
H3A	0.4084	0.2983	0.4820	0.054*
H3B	0.4711	0.3692	0.4173	0.054*
H5A	0.4055	0.7551	0.3995	0.052*
H5B	0.4703	0.6574	0.3683	0.052*
H6	0.3438	0.6250	0.2645	0.050*
H7A	0.3889	0.1553	0.1996	0.081*
H7B	0.3895	0.0977	0.3276	0.081*
H7C	0.4559	0.1617	0.2711	0.081*
H8A	0.4014	0.8326	0.1901	0.081*
H8B	0.4005	0.6961	0.0988	0.081*
H8C	0.4657	0.7273	0.1717	0.081*
H11	0.1195	1.1981	0.2377	0.160*
H13	0.1052	0.4892	0.4170	0.064*
H12A	0.0700	0.8419	0.2159	0.069*
H12B	0.0909	0.8344	0.3453	0.069*
H13A	0.1875	0.6965	0.2991	0.051*
H13B	0.1712	0.7123	0.1676	0.051*
H21	0.2369	−0.2921	0.5152	0.068*
H23	0.2704	0.4198	0.6833	0.059*
H22A	0.2145	0.0674	0.6096	0.050*
H22B	0.1739	0.0571	0.4944	0.050*
H23A	0.2517	0.2041	0.4004	0.049*
H23B	0.3019	0.1946	0.5037	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.033 (2)	0.041 (2)	0.043 (3)	−0.0025 (16)	−0.0003 (17)	−0.0034 (17)
N4	0.040 (2)	0.049 (2)	0.043 (2)	0.0000 (19)	0.0051 (18)	−0.0033 (19)
C2	0.036 (2)	0.036 (2)	0.049 (3)	−0.009 (2)	0.000 (2)	0.002 (2)
C3	0.035 (2)	0.049 (3)	0.052 (3)	−0.002 (2)	−0.002 (2)	0.003 (2)
C5	0.039 (3)	0.038 (2)	0.055 (3)	0.005 (2)	0.001 (2)	−0.006 (2)
C6	0.039 (2)	0.038 (2)	0.046 (3)	0.001 (2)	−0.002 (2)	−0.001 (2)
C7	0.046 (3)	0.041 (3)	0.074 (4)	−0.003 (2)	−0.001 (3)	0.008 (3)
C8	0.057 (3)	0.041 (3)	0.064 (4)	−0.001 (2)	−0.003 (3)	0.005 (3)
P1	0.0335 (6)	0.0304 (5)	0.0443 (6)	−0.0002 (5)	0.0020 (6)	−0.0001 (6)
O11	0.051 (3)	0.0317 (19)	0.237 (8)	0.0030 (18)	0.018 (4)	0.021 (4)
O12	0.049 (2)	0.0370 (17)	0.070 (2)	−0.0045 (15)	0.006 (2)	−0.002 (2)
O13	0.0378 (18)	0.050 (2)	0.0407 (18)	0.0076 (16)	0.0029 (15)	0.0097 (16)
O14	0.0342 (17)	0.0475 (18)	0.0433 (19)	0.0004 (14)	0.0023 (14)	−0.0046 (15)
O15	0.0403 (18)	0.0296 (15)	0.065 (2)	0.0002 (13)	0.0091 (17)	−0.0100 (15)
C11	0.048 (3)	0.028 (2)	0.075 (4)	−0.0027 (18)	−0.001 (3)	0.000 (3)
C12	0.051 (3)	0.0210 (18)	0.101 (5)	−0.001 (2)	0.010 (3)	−0.002 (3)
C13	0.040 (2)	0.032 (2)	0.055 (3)	0.0001 (18)	0.003 (2)	−0.002 (2)
P2	0.0343 (6)	0.0277 (5)	0.0439 (6)	0.0005 (4)	0.0003 (6)	0.0002 (6)
O21	0.0430 (19)	0.0264 (15)	0.066 (3)	0.0020 (13)	0.0047 (17)	0.0020 (16)
O22	0.0395 (19)	0.0381 (18)	0.074 (3)	0.0063 (15)	0.0078 (18)	−0.0033 (18)
O23	0.0357 (18)	0.0374 (17)	0.0449 (18)	−0.0023 (14)	−0.0029 (14)	−0.0013 (15)
O24	0.0295 (15)	0.0428 (16)	0.045 (2)	0.0025 (13)	0.0002 (14)	0.0045 (16)
O25	0.0394 (19)	0.0268 (14)	0.0488 (19)	−0.0017 (13)	0.0041 (15)	0.0015 (13)
C21	0.040 (2)	0.034 (2)	0.046 (3)	−0.007 (2)	0.004 (2)	−0.005 (2)
C22	0.036 (2)	0.032 (2)	0.057 (3)	−0.0024 (18)	0.007 (2)	−0.001 (3)
C23	0.043 (3)	0.030 (2)	0.049 (3)	0.001 (2)	0.008 (2)	0.002 (2)

Geometric parameters (Å, º)

N1—C2	1.497 (6)	P1—C13	1.785 (5)
N1—C6	1.532 (6)	O11—C11	1.329 (6)
N1—H1A	0.92	O11—H11	0.84
N1—H1B	0.92	O12—C11	1.201 (6)
N4—C3	1.474 (7)	O13—H13	0.84
N4—C5	1.505 (7)	C11—C12	1.503 (6)
N4—H4A	0.92	C12—C13	1.524 (7)
N4—H4B	0.92	C12—H12A	0.99
C2—C3	1.507 (7)	C12—H12B	0.99
C2—C7	1.520 (7)	C13—H13A	0.99
C2—H2	1.00	C13—H13B	0.99
C3—H3A	0.99	P2—O25	1.518 (3)
C3—H3B	0.99	P2—O24	1.519 (3)
C5—C6	1.503 (7)	P2—O23	1.575 (3)
C5—H5A	0.99	P2—C23	1.785 (5)
C5—H5B	0.99	O21—C21	1.335 (5)
C6—C8	1.490 (8)	O21—H21	0.84
C6—H6	1.00	O22—C21	1.224 (6)
C7—H7A	0.98	O23—H23	0.84
C7—H7B	0.98	C21—C22	1.492 (6)
C7—H7C	0.98	C22—C23	1.522 (6)
C8—H8A	0.98	C22—H22A	0.99
C8—H8B	0.98	C22—H22B	0.99
C8—H8C	0.98	C23—H23A	0.99
P1—O15	1.511 (3)	C23—H23B	0.99
P1—O14	1.518 (4)	O1—C1	1.50 (2)
P1—O13	1.575 (4)
C2—N1—C6	111.4 (4)	H8B—C8—H8C	109.5
C2—N1—H1A	109.3	O15—P1—O14	114.4 (2)
C6—N1—H1A	109.3	O15—P1—O13	111.1 (2)
C2—N1—H1B	109.3	O14—P1—O13	106.8 (2)
C6—N1—H1B	109.3	O15—P1—C13	109.1 (2)
H1A—N1—H1B	108.0	O14—P1—C13	108.3 (2)
C3—N4—C5	111.6 (4)	O13—P1—C13	106.9 (2)
C3—N4—H4A	109.3	C11—O11—H11	109.5
C5—N4—H4A	109.3	P1—O13—H13	109.5
C3—N4—H4B	109.3	O12—C11—O11	123.0 (4)
C5—N4—H4B	109.3	O12—C11—C12	124.7 (5)
H4A—N4—H4B	108.0	O11—C11—C12	112.4 (5)
N1—C2—C3	109.8 (4)	C11—C12—C13	115.6 (5)
N1—C2—C7	109.8 (4)	C11—C12—H12A	108.4
C3—C2—C7	111.9 (4)	C13—C12—H12A	108.4
N1—C2—H2	108.4	C11—C12—H12B	108.4
C3—C2—H2	108.4	C13—C12—H12B	108.4
C7—C2—H2	108.4	H12A—C12—H12B	107.4
N4—C3—C2	110.0 (4)	C12—C13—P1	110.0 (4)
N4—C3—H3A	109.7	C12—C13—H13A	109.7
C2—C3—H3A	109.7	P1—C13—H13A	109.7
N4—C3—H3B	109.7	C12—C13—H13B	109.7
C2—C3—H3B	109.7	P1—C13—H13B	109.7
H3A—C3—H3B	108.2	H13A—C13—H13B	108.2
C6—C5—N4	112.5 (4)	O25—P2—O24	116.47 (19)
C6—C5—H5A	109.1	O25—P2—O23	111.6 (2)
N4—C5—H5A	109.1	O24—P2—O23	103.4 (2)
C6—C5—H5B	109.1	O25—P2—C23	107.7 (2)
N4—C5—H5B	109.1	O24—P2—C23	110.8 (2)
H5A—C5—H5B	107.8	O23—P2—C23	106.4 (2)
C8—C6—C5	112.1 (4)	C21—O21—H21	109.5
C8—C6—N1	109.3 (4)	P2—O23—H23	109.5
C5—C6—N1	109.1 (4)	O22—C21—O21	122.3 (4)
C8—C6—H6	108.8	O22—C21—C22	125.5 (4)
C5—C6—H6	108.8	O21—C21—C22	112.1 (4)
N1—C6—H6	108.8	C21—C22—C23	113.4 (4)
C2—C7—H7A	109.5	C21—C22—H22A	108.9
C2—C7—H7B	109.5	C23—C22—H22A	108.9
H7A—C7—H7B	109.5	C21—C22—H22B	108.9
C2—C7—H7C	109.5	C23—C22—H22B	108.9
H7A—C7—H7C	109.5	H22A—C22—H22B	107.7
H7B—C7—H7C	109.5	C22—C23—P2	115.9 (3)
C6—C8—H8A	109.5	C22—C23—H23A	108.3
C6—C8—H8B	109.5	P2—C23—H23A	108.3
H8A—C8—H8B	109.5	C22—C23—H23B	108.3
C6—C8—H8C	109.5	P2—C23—H23B	108.3
H8A—C8—H8C	109.5	H23A—C23—H23B	107.4
C6—N1—C2—C3	−58.9 (5)	O11—C11—C12—C13	165.1 (7)
C6—N1—C2—C7	177.8 (4)	C11—C12—C13—P1	−175.7 (5)
C5—N4—C3—C2	−57.7 (5)	O15—P1—C13—C12	178.2 (4)
N1—C2—C3—N4	59.5 (5)	O14—P1—C13—C12	53.2 (5)
C7—C2—C3—N4	−178.3 (4)	O13—P1—C13—C12	−61.6 (5)
C3—N4—C5—C6	55.8 (5)	O22—C21—C22—C23	20.7 (8)
N4—C5—C6—C8	−174.2 (4)	O21—C21—C22—C23	−163.0 (4)
N4—C5—C6—N1	−53.0 (5)	C21—C22—C23—P2	−169.4 (4)
C2—N1—C6—C8	178.1 (4)	O25—P2—C23—C22	−179.3 (4)
C2—N1—C6—C5	55.2 (5)	O24—P2—C23—C22	−50.8 (5)
O12—C11—C12—C13	−14.0 (11)	O23—P2—C23—C22	60.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O24^i	0.92	1.88	2.798 (5)	175
N1—H1A···O23^i	0.92	2.58	3.084 (5)	116
N1—H1B···O14^ii	0.92	1.82	2.731 (5)	170
N4—H4A···O14^iii	0.92	1.85	2.752 (6)	165
N4—H4B···O25	0.92	1.88	2.792 (5)	171
O11—H11···O15^iv	0.84	1.76	2.587 (5)	166
O13—H13···O24	0.84	1.72	2.534 (5)	164
O21—H21···O25^v	0.84	1.83	2.624 (4)	157
O23—H23···O15^iii	0.84	1.77	2.533 (5)	149

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