Phosphonoacetic acid as a building block in supramolecular chemistry: salts with organic polyamines

Phosphonoacetic acid, (HO)₂P(O)CH₂COOH, forms adducts with a range of amines. The acid component in these adducts may be the neutral molecule C₂H₅O₅P, the mono-anion (C₂H₄O₅P)^- or the di-anion (C₂H₃O₅P)^2-. The substructure formed by the acid component takes the form of simple chains in compounds (1)-(3), which are the 1:1 adducts formed with 1,4-diazabicyclo[2.2.2]octane, 4,4'-bipyridyl and 1,3-trimethylenedipiperidine, respectively. These adducts contain C₂H₅O₅P, (C₂H₄O₅P)^- and (C₂H₃O₅P)^2-, respectively, although (3) is solvated by a mixture of methanol and water. The (C₂H₄O₅P)^- anion substructure in (4), which is the adduct formed with meso-5,5,7,12,12,14-hexa-C-methyl-1,4,8,11-tetraazacyclotetradecane, is a chain of spiro-fused rings, while the substructure in (5), which is the adduct formed with 2,2'-dipyridylamine, is a chain of edge-fused rings. In (6), the adduct formed with 1,2-bis(4'-pyridyl)ethane, the anion substructure is two-dimensional. The chain substructures are linked by the amine units into two-dimensional structures in (1) and (4) and into three-dimensional frameworks in (2), (3) and (5), while the anion sheets in (6) are likewise linked by the amine units into a three-dimensional framework.

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).

(I) 1,4-Diazabicyclo[2.2.2]octane–phosphonoacetic acid (1/1)

Crystal data

C6H12N2·C2H5O5P	F(000) = 536
Mr = 252.21	Dx = 1.521 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1987 reflections
a = 20.3011 (17) Å	θ = 3.6–25.5°
b = 6.7692 (5) Å	µ = 0.26 mm^−1
c = 8.0158 (6) Å	T = 150 K
V = 1101.55 (15) Å^3	Plate, colourless
Z = 4	0.18 × 0.10 × 0.03 mm

Data collection

Kappa-CCD diffractometer	1462 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.119
Graphite monochromator	θmax = 25.5°, θmin = 3.6°
φ scans, and ω scans with κ offsets	h = −21→24
7195 measured reflections	k = −8→8
1987 independent reflections	l = −9→9

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 0.0408P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.016
1987 reflections	Δρmax = 0.30 e Å^−3
148 parameters	Δρmin = −0.53 e Å^−3
1 restraint	Absolute structure: Flack (1983); 884 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (2)

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

	x	y	z	Uiso*/Ueq
P1	0.68565 (6)	0.48698 (16)	0.53883 (16)	0.0289 (3)
O1	0.54657 (16)	0.2173 (5)	0.5973 (4)	0.0400 (9)
O2	0.52098 (19)	0.4200 (5)	0.3873 (4)	0.0425 (9)
O3	0.72162 (17)	0.6460 (5)	0.6475 (4)	0.0370 (9)
O4	0.70480 (16)	0.2805 (5)	0.5891 (5)	0.0362 (8)
O5	0.69242 (17)	0.5376 (5)	0.3583 (4)	0.0374 (9)
C1	0.5513 (2)	0.3857 (7)	0.5141 (6)	0.0327 (12)
C2	0.5992 (3)	0.5261 (7)	0.5928 (6)	0.0325 (11)
N1	0.43608 (18)	0.0288 (5)	0.5533 (5)	0.0285 (8)
N2	0.32223 (18)	−0.1258 (6)	0.5745 (5)	0.0307 (9)
C11	0.3922 (3)	0.1118 (8)	0.4248 (6)	0.0377 (13)
C12	0.4408 (2)	−0.1871 (6)	0.5285 (7)	0.0342 (11)
C13	0.4072 (2)	0.0661 (8)	0.7185 (6)	0.0349 (12)
C21	0.3229 (2)	0.0148 (8)	0.4322 (7)	0.0350 (12)
C22	0.3726 (2)	−0.2848 (6)	0.5465 (7)	0.0334 (10)
C23	0.3382 (3)	−0.0194 (7)	0.7326 (6)	0.0319 (11)
H1	0.5133	0.1547	0.5641	0.060*
H3	0.7417	0.5900	0.7260	0.056*
H4	0.7423	0.2824	0.6336	0.054*
H2A	0.5946	0.5164	0.7155	0.039*
H2B	0.5868	0.6623	0.5602	0.039*
H11A	0.4117	0.0896	0.3132	0.045*
H11B	0.3879	0.2561	0.4419	0.045*
H12A	0.4714	−0.2439	0.6119	0.041*
H12B	0.4587	−0.2149	0.4160	0.041*
H13A	0.4055	0.2103	0.7386	0.042*
H13B	0.4357	0.0065	0.8053	0.042*
H21A	0.2887	0.1173	0.4481	0.042*
H21B	0.3136	−0.0560	0.3267	0.042*
H22A	0.3618	−0.3599	0.4441	0.040*
H22B	0.3728	−0.3777	0.6419	0.040*
H23A	0.3359	−0.1118	0.8281	0.038*
H23B	0.3060	0.0880	0.7516	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0313 (6)	0.0284 (6)	0.0272 (6)	0.0007 (5)	−0.0005 (6)	−0.0006 (6)
O1	0.0363 (19)	0.042 (2)	0.0412 (18)	−0.0059 (15)	−0.0050 (17)	0.0099 (16)
O2	0.046 (2)	0.047 (2)	0.034 (2)	−0.0038 (19)	−0.0062 (18)	0.0013 (18)
O3	0.039 (2)	0.0304 (19)	0.042 (2)	−0.0003 (16)	−0.0120 (17)	−0.0025 (15)
O4	0.0341 (18)	0.0305 (17)	0.044 (2)	0.0036 (15)	−0.0089 (17)	0.0050 (15)
O5	0.037 (2)	0.050 (2)	0.0250 (17)	−0.0004 (16)	0.0048 (15)	0.0041 (16)
C1	0.035 (3)	0.034 (3)	0.030 (3)	0.000 (2)	0.004 (2)	0.000 (2)
C2	0.040 (3)	0.034 (3)	0.024 (2)	0.001 (2)	0.002 (2)	−0.001 (2)
N1	0.0325 (19)	0.0296 (19)	0.023 (2)	0.0012 (15)	−0.0022 (18)	0.001 (2)
N2	0.037 (2)	0.030 (2)	0.026 (2)	0.0030 (16)	−0.0015 (18)	0.0015 (16)
C11	0.049 (3)	0.032 (3)	0.032 (3)	−0.004 (2)	−0.005 (2)	0.008 (2)
C12	0.041 (3)	0.026 (2)	0.036 (3)	0.000 (2)	0.003 (2)	−0.001 (3)
C13	0.036 (3)	0.038 (3)	0.031 (2)	−0.008 (2)	0.003 (2)	−0.005 (2)
C21	0.039 (3)	0.035 (3)	0.030 (3)	0.000 (2)	0.000 (2)	0.002 (2)
C22	0.038 (3)	0.024 (2)	0.038 (3)	0.0027 (19)	0.001 (2)	0.001 (3)
C23	0.038 (3)	0.028 (3)	0.030 (3)	−0.001 (2)	0.003 (2)	−0.002 (2)

Geometric parameters (Å, º)

P1—O5	1.493 (3)	N2—C22	1.502 (6)
P1—O4	1.506 (3)	C11—C21	1.554 (7)
P1—O3	1.565 (3)	C11—H11A	0.99
P1—C2	1.827 (5)	C11—H11B	0.99
O1—C1	1.324 (6)	C12—C22	1.541 (6)
O1—H1	0.84	C12—H12A	0.99
O2—C1	1.211 (5)	C12—H12B	0.99
O3—H3	0.84	C13—C23	1.520 (7)
O4—H4	0.84	C13—H13A	0.99
C1—C2	1.498 (7)	C13—H13B	0.99
C2—H2A	0.99	C21—H21A	0.99
C2—H2B	0.99	C21—H21B	0.99
N1—C13	1.470 (6)	C22—H22A	0.99
N1—C11	1.473 (6)	C22—H22B	0.99
N1—C12	1.478 (5)	C23—H23A	0.99
N2—C21	1.486 (6)	C23—H23B	0.99
N2—C23	1.493 (6)
O5—P1—O4	116.6 (2)	N1—C12—C22	110.7 (4)
O5—P1—O3	109.8 (2)	N1—C12—H12A	109.5
O4—P1—O3	111.6 (2)	C22—C12—H12A	109.5
O5—P1—C2	106.5 (2)	N1—C12—H12B	109.5
O4—P1—C2	108.6 (2)	C22—C12—H12B	109.5
O3—P1—C2	102.5 (2)	H12A—C12—H12B	108.1
C1—O1—H1	109.5	N1—C13—C23	111.6 (4)
P1—O3—H3	109.5	N1—C13—H13A	109.3
P1—O4—H4	109.5	C23—C13—H13A	109.3
O2—C1—O1	123.4 (5)	N1—C13—H13B	109.3
O2—C1—C2	124.2 (5)	C23—C13—H13B	109.3
O1—C1—C2	112.4 (4)	H13A—C13—H13B	108.0
C1—C2—P1	115.5 (3)	N2—C21—C11	107.9 (4)
C1—C2—H2A	108.4	N2—C21—H21A	110.1
P1—C2—H2A	108.4	C11—C21—H21A	110.1
C1—C2—H2B	108.4	N2—C21—H21B	110.1
P1—C2—H2B	108.4	C11—C21—H21B	110.1
H2A—C2—H2B	107.5	H21A—C21—H21B	108.4
C13—N1—C11	108.9 (4)	N2—C22—C12	108.6 (3)
C13—N1—C12	108.5 (4)	N2—C22—H22A	110.0
C11—N1—C12	108.8 (4)	C12—C22—H22A	110.0
C21—N2—C23	109.9 (4)	N2—C22—H22B	110.0
C21—N2—C22	109.8 (4)	C12—C22—H22B	110.0
C23—N2—C22	109.0 (4)	H22A—C22—H22B	108.4
N1—C11—C21	111.1 (4)	N2—C23—C13	108.7 (4)
N1—C11—H11A	109.4	N2—C23—H23A	109.9
C21—C11—H11A	109.4	C13—C23—H23A	109.9
N1—C11—H11B	109.4	N2—C23—H23B	109.9
C21—C11—H11B	109.4	C13—C23—H23B	109.9
H11A—C11—H11B	108.0	H23A—C23—H23B	108.3
O2—C1—C2—P1	−95.8 (5)	C12—N1—C13—C23	−61.3 (5)
O1—C1—C2—P1	83.1 (5)	C23—N2—C21—C11	58.1 (5)
O5—P1—C2—C1	67.9 (4)	C22—N2—C21—C11	−61.7 (5)
O4—P1—C2—C1	−58.5 (4)	N1—C11—C21—N2	2.8 (6)
O3—P1—C2—C1	−176.8 (3)	C21—N2—C22—C12	58.8 (5)
C13—N1—C11—C21	−60.2 (5)	C23—N2—C22—C12	−61.6 (5)
C12—N1—C11—C21	57.9 (6)	N1—C12—C22—N2	3.1 (6)
C13—N1—C12—C22	57.2 (5)	C21—N2—C23—C13	−62.0 (5)
C11—N1—C12—C22	−61.1 (5)	C22—N2—C23—C13	58.3 (5)
C11—N1—C13—C23	57.0 (5)	N1—C13—C23—N2	3.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.79	2.605 (5)	164
O3—H3···O5^i	0.84	1.74	2.538 (5)	157
O4—H4···N2^ii	0.84	2.00	2.606 (5)	129

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

(II) 4,4'-Bipyridyl–phosphonoacetic acid (1/1)

Crystal data

C10H9N2·C2H4O5P	F(000) = 616
Mr = 296.21	Dx = 1.585 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2390 reflections
a = 4.6225 (2) Å	θ = 2.6–27.5°
b = 17.2421 (6) Å	µ = 0.24 mm^−1
c = 15.6529 (7) Å	T = 150 K
β = 95.7190 (15)°	Block, colourless
V = 1241.35 (9) Å^3	0.34 × 0.20 × 0.15 mm
Z = 4

Data collection

Kappa-CCD diffractometer	2194 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
φ scans, and ω scans with κ offsets	h = 0→6
8078 measured reflections	k = 0→22
2824 independent reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0414P)^2 + 0.5382P] where P = (Fo^2 + 2Fc^2)/3
2824 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.4032 (0.0015) x - 4.8344 (0.0130) y + 8.4445 (0.0079) z = 3.9557 (0.0085)

* -0.0027 (0.0013) N1 * 0.0046 (0.0014) C12 * -0.0031 (0.0015) C13 * 0.0009 (0.0015) C14 * 0.0032 (0.0014) C15 * -0.0019 (0.0013) C16 * -0.0010 (0.0010) C24

Rms deviation of fitted atoms = 0.0028

3.3545 (0.0015) x - 6.3684 (0.0127) y + 7.9092 (0.0087) z = 2.9606 (0.0083)

Angle to previous plane (with approximate e.s.d.) = 5.52 (0.09)

* -0.0153 (0.0013) N2 * -0.0051 (0.0013) C22 * 0.0180 (0.0014) C23 * 0.0104 (0.0015) C24 * 0.0129 (0.0015) C25 * 0.0000 (0.0014) C26 * -0.0209 (0.0010) C14

Rms deviation of fitted atoms = 0.0136

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

	x	y	z	Uiso*/Ueq
P1	0.30053 (10)	0.20506 (3)	0.57660 (3)	0.01651 (14)
O1	0.4716 (3)	0.38663 (7)	0.47806 (8)	0.0241 (3)
O2	0.4454 (3)	0.28344 (7)	0.39146 (8)	0.0280 (3)
O3	0.5681 (3)	0.24250 (7)	0.63093 (8)	0.0236 (3)
O4	0.0690 (3)	0.18501 (7)	0.63398 (8)	0.0230 (3)
O5	0.3931 (3)	0.13936 (7)	0.52205 (8)	0.0212 (3)
C1	0.3706 (4)	0.31774 (10)	0.45331 (11)	0.0192 (4)
C2	0.1562 (4)	0.28474 (10)	0.50903 (11)	0.0192 (4)
N1	1.7828 (3)	0.61103 (9)	0.09945 (10)	0.0218 (4)
C12	1.6889 (4)	0.65358 (11)	0.16250 (13)	0.0269 (4)
C13	1.5059 (4)	0.62223 (11)	0.21742 (12)	0.0250 (4)
C14	1.4191 (4)	0.54498 (10)	0.20862 (11)	0.0166 (4)
C15	1.5231 (4)	0.50222 (11)	0.14253 (11)	0.0215 (4)
C16	1.7036 (4)	0.53702 (11)	0.08908 (12)	0.0234 (4)
N2	0.8371 (3)	0.44314 (9)	0.37416 (10)	0.0209 (3)
C22	0.9231 (4)	0.40412 (11)	0.30759 (12)	0.0233 (4)
C23	1.1147 (4)	0.43451 (11)	0.25371 (11)	0.0231 (4)
C24	1.2218 (4)	0.50913 (10)	0.26739 (11)	0.0167 (4)
C25	1.1336 (4)	0.54944 (11)	0.33755 (12)	0.0241 (4)
C26	0.9440 (4)	0.51459 (11)	0.38833 (12)	0.0258 (4)
H1A	0.5866	0.4025	0.4436	0.036*
H3	0.7190	0.2173	0.6236	0.035*
H2A	−0.0162	0.2662	0.4720	0.023*
H2B	0.0911	0.3265	0.5461	0.023*
H1	1.8980	0.6321	0.0644	0.026*
H12	1.7493	0.7061	0.1695	0.032*
H13	1.4384	0.6533	0.2615	0.030*
H15	1.4696	0.4493	0.1344	0.026*
H16	1.7731	0.5077	0.0440	0.028*
H22	0.8496	0.3532	0.2966	0.028*
H23	1.1726	0.4044	0.2075	0.028*
H25	1.2036	0.6004	0.3502	0.029*
H26	0.8861	0.5428	0.4359	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0153 (2)	0.0158 (2)	0.0191 (2)	0.00144 (18)	0.00533 (18)	0.00088 (18)
O1	0.0275 (7)	0.0205 (7)	0.0263 (7)	−0.0060 (6)	0.0122 (6)	0.0000 (5)
O2	0.0371 (8)	0.0219 (7)	0.0272 (7)	0.0030 (6)	0.0137 (6)	−0.0015 (6)
O3	0.0177 (7)	0.0231 (7)	0.0295 (7)	0.0046 (5)	0.0007 (6)	−0.0066 (6)
O4	0.0191 (7)	0.0249 (7)	0.0264 (7)	0.0028 (5)	0.0093 (5)	0.0072 (5)
O5	0.0248 (7)	0.0161 (6)	0.0241 (7)	0.0010 (5)	0.0087 (5)	−0.0008 (5)
C1	0.0191 (9)	0.0166 (9)	0.0217 (9)	0.0053 (7)	0.0017 (7)	0.0039 (7)
C2	0.0168 (9)	0.0182 (9)	0.0231 (9)	0.0010 (7)	0.0040 (7)	0.0014 (7)
N1	0.0190 (8)	0.0236 (8)	0.0236 (8)	0.0005 (6)	0.0067 (6)	0.0066 (7)
C12	0.0315 (11)	0.0183 (9)	0.0324 (11)	−0.0034 (8)	0.0113 (9)	0.0018 (8)
C13	0.0305 (11)	0.0195 (9)	0.0267 (10)	−0.0010 (8)	0.0115 (8)	−0.0010 (8)
C14	0.0145 (8)	0.0180 (9)	0.0175 (8)	0.0018 (7)	0.0019 (7)	0.0032 (7)
C15	0.0232 (9)	0.0190 (9)	0.0234 (9)	−0.0014 (8)	0.0072 (8)	−0.0021 (7)
C16	0.0224 (9)	0.0271 (10)	0.0218 (9)	0.0020 (8)	0.0072 (8)	−0.0009 (8)
N2	0.0197 (8)	0.0200 (8)	0.0233 (8)	0.0011 (6)	0.0041 (6)	0.0044 (6)
C22	0.0283 (10)	0.0186 (9)	0.0231 (10)	−0.0051 (8)	0.0032 (8)	0.0010 (7)
C23	0.0284 (10)	0.0221 (9)	0.0199 (9)	−0.0024 (8)	0.0077 (8)	−0.0023 (8)
C24	0.0152 (8)	0.0175 (9)	0.0175 (8)	0.0013 (7)	0.0016 (7)	0.0016 (7)
C25	0.0287 (11)	0.0184 (9)	0.0264 (10)	−0.0031 (8)	0.0100 (8)	−0.0014 (8)
C26	0.0336 (11)	0.0200 (9)	0.0261 (10)	0.0004 (8)	0.0146 (8)	−0.0005 (8)

Geometric parameters (Å, º)

P1—O3	1.5684 (13)	C13—H13	0.95
P1—O4	1.5045 (13)	C14—C15	1.394 (2)
P1—O5	1.5061 (12)	C14—C24	1.492 (2)
P1—C2	1.8196 (18)	C15—C16	1.377 (3)
O1—C1	1.320 (2)	C15—H15	0.95
O1—H1A	0.84	C16—H16	0.95
O2—C1	1.214 (2)	N2—C22	1.334 (2)
O3—H3	0.84	N2—C26	1.338 (2)
C1—C2	1.496 (2)	C22—C23	1.385 (3)
C2—H2A	0.99	C22—H22	0.95
C2—H2B	0.99	C23—C24	1.388 (3)
N1—C12	1.336 (2)	C23—H23	0.95
N1—C16	1.333 (2)	C24—C25	1.394 (2)
N1—H1	0.88	C25—C26	1.378 (3)
C12—C13	1.376 (3)	C25—H25	0.95
C12—H12	0.95	C26—H26	0.95
C13—C14	1.394 (2)
O4—P1—O5	115.15 (7)	C13—C14—C15	117.49 (16)
O4—P1—O3	109.90 (8)	C13—C14—C24	121.49 (16)
O5—P1—O3	111.33 (7)	C15—C14—C24	121.02 (16)
O4—P1—C2	106.20 (8)	C16—C15—C14	119.67 (17)
O5—P1—C2	110.29 (8)	C16—C15—H15	120.2
O3—P1—C2	103.18 (8)	C14—C15—H15	120.2
C1—O1—H1A	109.5	N1—C16—C15	121.25 (17)
P1—O3—H3	109.5	N1—C16—H16	119.4
O2—C1—O1	123.50 (17)	C15—C16—H16	119.4
O2—C1—C2	122.52 (17)	C22—N2—C26	117.42 (16)
O1—C1—C2	113.98 (15)	N2—C22—C23	122.89 (17)
C1—C2—P1	113.57 (12)	N2—C22—H22	118.6
C1—C2—H2A	108.9	C23—C22—H22	118.6
P1—C2—H2A	108.9	C22—C23—C24	119.79 (17)
C1—C2—H2B	108.9	C22—C23—H23	120.1
P1—C2—H2B	108.9	C24—C23—H23	120.1
H2A—C2—H2B	107.7	C23—C24—C25	117.11 (16)
C16—N1—C12	120.68 (16)	C23—C24—C14	121.30 (16)
C16—N1—H1	119.7	C25—C24—C14	121.58 (16)
C12—N1—H1	119.7	C26—C25—C24	119.31 (17)
N1—C12—C13	120.73 (17)	C26—C25—H25	120.3
N1—C12—H12	119.6	C24—C25—H25	120.3
C13—C12—H12	119.6	N2—C26—C25	123.46 (18)
C12—C13—C14	120.17 (17)	N2—C26—H26	118.3
C12—C13—H13	119.9	C25—C26—H26	118.3
C14—C13—H13	119.9
O2—C1—C2—P1	72.2 (2)	C26—N2—C22—C23	−0.1 (3)
O1—C1—C2—P1	−107.22 (15)	N2—C22—C23—C24	−1.0 (3)
O4—P1—C2—C1	174.26 (12)	C22—C23—C24—C25	1.6 (3)
O5—P1—C2—C1	−60.34 (15)	C22—C23—C24—C14	−177.50 (17)
O3—P1—C2—C1	58.66 (14)	C13—C14—C24—C23	174.03 (18)
C16—N1—C12—C13	−0.8 (3)	C15—C14—C24—C23	−5.8 (3)
N1—C12—C13—C14	0.9 (3)	C13—C14—C24—C25	−5.0 (3)
C12—C13—C14—C15	−0.4 (3)	C15—C14—C24—C25	175.17 (17)
C12—C13—C14—C24	179.72 (17)	C23—C24—C25—C26	−1.1 (3)
C13—C14—C15—C16	−0.2 (3)	C14—C24—C25—C26	177.99 (17)
C24—C14—C15—C16	179.67 (16)	C22—N2—C26—C25	0.6 (3)
C12—N1—C16—C15	0.2 (3)	C24—C25—C26—N2	0.0 (3)
C14—C15—C16—N1	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2	0.84	1.81	2.645 (2)	176
O3—H3···O4^i	0.84	1.70	2.515 (2)	162
N1—H1···O5^ii	0.88	1.74	2.582 (2)	158
C12—H12···O2^ii	0.95	2.22	2.978 (2)	135
C13—H13···O3^iii	0.95	2.46	3.369 (2)	159
C15—H15···O4^iv	0.95	2.36	3.239 (2)	153
C26—H26···O1^v	0.95	2.54	3.430 (2)	155

Symmetry codes: (i) x+1, y, z; (ii) −x+5/2, y+1/2, −z+1/2; (iii) −x+2, −y+1, −z+1; (iv) x+3/2, −y+1/2, z−1/2; (v) −x+1, −y+1, −z+1.

(III) 1,3-trimethylenedipiperidine–phosphonoacetic acid (1/1) methanol/water solvate

Crystal data

2(C13H28N2)2(C2H3O5P)·1.58(H2O)0.70(CH4O)	Z = 2
Mr = 745.67	F(000) = 805
Triclinic, P1	Dx = 1.288 Mg m^−3
a = 11.7486 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.3913 (4) Å	Cell parameters from 8765 reflections
c = 13.8206 (5) Å	θ = 3.1–27.6°
α = 96.9260 (17)°	µ = 0.18 mm^−1
β = 109.4140 (16)°	T = 150 K
γ = 105.4830 (15)°	Plate, colourless
V = 1923.20 (10) Å^3	0.16 × 0.10 × 0.06 mm

Data collection

Kappa-CCD diffractometer	5307 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.108
Graphite monochromator	θmax = 27.6°, θmin = 3.1°
φ scans, and ω scans with κ offsets	h = −15→15
24179 measured reflections	k = −17→17
8765 independent reflections	l = −17→17

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)] = 0.080	H-atom parameters constrained
wR(F^2) = 0.228	w = 1/[σ^2(Fo^2) + (0.0954P)^2 + 1.4703P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
8765 reflections	Δρmax = 0.68 e Å^−3
466 parameters	Δρmin = −0.43 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: 0.028 (4)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	0.1531 (3)	0.3251 (3)	0.0767 (2)	0.0333 (7)
N21	0.0254 (3)	−0.3591 (3)	−0.4688 (2)	0.0331 (7)
C12	0.1184 (4)	0.2895 (3)	−0.0388 (3)	0.0387 (9)
C13	0.1752 (4)	0.2036 (3)	−0.0620 (3)	0.0348 (9)
C14	0.1365 (4)	0.1096 (3)	−0.0148 (3)	0.0317 (8)
C15	0.1763 (4)	0.1503 (3)	0.1032 (3)	0.0347 (9)
C16	0.1182 (4)	0.2345 (3)	0.1258 (3)	0.0361 (9)
C17	0.1906 (4)	0.0212 (3)	−0.0365 (3)	0.0336 (8)
C18	0.1463 (4)	−0.0309 (3)	−0.1532 (3)	0.0363 (9)
C22	0.1669 (4)	−0.3247 (4)	−0.4098 (3)	0.0383 (9)
C23	0.2016 (4)	−0.2711 (3)	−0.2955 (3)	0.0340 (8)
C24	0.1521 (4)	−0.1776 (3)	−0.2869 (3)	0.0342 (9)
C25	0.0084 (4)	−0.2162 (3)	−0.3499 (3)	0.0352 (9)
C26	−0.0241 (4)	−0.2682 (3)	−0.4650 (3)	0.0380 (9)
C27	0.1899 (4)	−0.1263 (3)	−0.1705 (3)	0.0338 (9)
N31	0.5461 (3)	0.7212 (3)	0.4435 (2)	0.0326 (7)
N41	0.5875 (3)	1.3930 (3)	0.9766 (2)	0.0320 (7)
C32	0.5858 (4)	0.6853 (3)	0.5441 (3)	0.0364 (9)
C33	0.5413 (4)	0.7384 (3)	0.6215 (3)	0.0351 (9)
C34	0.5901 (4)	0.8598 (3)	0.6428 (3)	0.0310 (8)
C35	0.5576 (4)	0.8948 (3)	0.5380 (3)	0.0320 (8)
C36	0.6008 (4)	0.8387 (3)	0.4622 (3)	0.0355 (9)
C37	0.5334 (4)	0.9081 (3)	0.7144 (3)	0.0352 (9)
C38	0.5949 (4)	1.0274 (3)	0.7633 (3)	0.0343 (9)
C42	0.6607 (4)	1.3771 (3)	0.9094 (3)	0.0318 (8)
C43	0.5991 (4)	1.2661 (3)	0.8362 (3)	0.0311 (8)
C44	0.5890 (4)	1.1782 (3)	0.8975 (3)	0.0305 (8)
C45	0.5142 (4)	1.1985 (3)	0.9646 (3)	0.0340 (9)
C46	0.5734 (4)	1.3086 (3)	1.0377 (3)	0.0322 (8)
C47	0.5253 (4)	1.0657 (3)	0.8283 (3)	0.0357 (9)
P1	0.17183 (9)	0.55017 (8)	0.33192 (8)	0.0302 (3)
O11	−0.1422 (2)	0.4767 (2)	0.1523 (2)	0.0369 (6)
O12	−0.0356 (3)	0.3959 (3)	0.0839 (2)	0.0486 (8)
O13	0.2218 (3)	0.4558 (2)	0.3094 (2)	0.0374 (7)
O14	0.0817 (3)	0.5163 (2)	0.3868 (2)	0.0349 (6)
O15	0.2810 (3)	0.6535 (2)	0.3852 (2)	0.0361 (6)
C1	−0.0407 (4)	0.4728 (3)	0.1420 (3)	0.0338 (9)
C2	0.0796 (4)	0.5660 (3)	0.2036 (3)	0.0374 (9)
P2	0.70208 (9)	0.60565 (8)	0.25323 (8)	0.0310 (3)
O21	0.4499 (3)	0.5105 (2)	0.3196 (2)	0.0385 (7)
O22	0.4122 (3)	0.4020 (2)	0.1680 (2)	0.0360 (6)
O23	0.8468 (3)	0.6136 (2)	0.2883 (2)	0.0378 (7)
O24	0.6424 (2)	0.5889 (2)	0.1349 (2)	0.0330 (6)
O25	0.6916 (3)	0.6976 (2)	0.3194 (2)	0.0359 (6)
C3	0.4854 (4)	0.4632 (3)	0.2556 (3)	0.0302 (8)
C4	0.6282 (4)	0.4859 (3)	0.2886 (3)	0.0323 (8)
O71	0.8950 (11)	0.0319 (9)	0.5737 (13)	0.074 (5)	0.297 (9)
O81	0.7744 (5)	0.1610 (4)	0.5900 (5)	0.074 (2)	0.703 (9)
C82	0.8700 (7)	0.1432 (7)	0.6677 (7)	0.074 (3)	0.703 (9)
O91	0.2380 (10)	0.1071 (6)	0.6914 (7)	0.051 (3)	0.434 (15)
O92	0.1436 (6)	0.0750 (5)	0.6188 (6)	0.099 (3)	0.845 (19)
H11A	0.2396	0.3603	0.1088	0.040*
H11B	0.1120	0.3723	0.0880	0.040*
H21A	0.0059	−0.3901	−0.5379	0.040*
H21B	−0.0142	−0.4094	−0.4401	0.040*
H12A	0.1504	0.3511	−0.0667	0.046*
H12B	0.0242	0.2610	−0.0749	0.046*
H13A	0.1462	0.1784	−0.1392	0.042*
H13B	0.2695	0.2347	−0.0329	0.042*
H14	0.0412	0.0785	−0.0465	0.038*
H15A	0.1487	0.0901	0.1344	0.042*
H15B	0.2706	0.1809	0.1366	0.042*
H16A	0.0240	0.2022	0.0979	0.043*
H16B	0.1485	0.2612	0.2029	0.043*
H17A	0.2850	0.0512	−0.0065	0.040*
H17B	0.1657	−0.0344	0.0007	0.040*
H18A	0.0518	−0.0540	−0.1855	0.044*
H18B	0.1800	0.0224	−0.1892	0.044*
H22A	0.2104	−0.2744	−0.4434	0.046*
H22B	0.1962	−0.3874	−0.4124	0.046*
H23A	0.2957	−0.2455	−0.2585	0.041*
H23B	0.1651	−0.3239	−0.2604	0.041*
H24	0.1936	−0.1233	−0.3192	0.041*
H25A	−0.0238	−0.1551	−0.3474	0.042*
H25B	−0.0347	−0.2683	−0.3176	0.042*
H26A	−0.1178	−0.2937	−0.5039	0.046*
H26B	0.0149	−0.2154	−0.4989	0.046*
H27A	0.1529	−0.1805	−0.1368	0.041*
H27B	0.2840	−0.1035	−0.1349	0.041*
H31A	0.5734	0.6890	0.3969	0.039*
H31B	0.4584	0.7008	0.4137	0.039*
H41A	0.5078	1.3922	0.9345	0.038*
H41B	0.6289	1.4586	1.0227	0.038*
H32A	0.6800	0.7042	0.5748	0.044*
H32B	0.5480	0.6070	0.5300	0.044*
H33A	0.5713	0.7165	0.6888	0.042*
H33B	0.4468	0.7133	0.5931	0.042*
H34	0.6852	0.8849	0.6800	0.037*
H35A	0.4641	0.8794	0.5052	0.038*
H35B	0.5992	0.9727	0.5519	0.038*
H36A	0.5736	0.8604	0.3944	0.043*
H36B	0.6952	0.8603	0.4915	0.043*
H37A	0.4416	0.8938	0.6729	0.042*
H37B	0.5389	0.8704	0.7723	0.042*
H38A	0.5924	1.0666	0.7067	0.041*
H38B	0.6855	1.0428	0.8091	0.041*
H42A	0.7497	1.3861	0.9549	0.038*
H42B	0.6632	1.4314	0.8668	0.038*
H43A	0.6504	1.2568	0.7938	0.037*
H43B	0.5126	1.2594	0.7871	0.037*
H44	0.6771	1.1847	0.9455	0.037*
H45A	0.4260	1.1900	0.9176	0.041*
H45B	0.5091	1.1444	1.0073	0.041*
H46A	0.5187	1.3186	1.0768	0.039*
H46B	0.6582	1.3152	1.0897	0.039*
H47A	0.4395	1.0606	0.7791	0.043*
H47B	0.5129	1.0158	0.8741	0.043*
H13	0.2963	0.4802	0.3111	0.056*
H2A	0.0562	0.6312	0.2135	0.045*
H2B	0.1340	0.5762	0.1617	0.045*
H23	0.8580	0.5807	0.2384	0.057*
H4A	0.6439	0.4247	0.2539	0.039*
H4B	0.6675	0.4943	0.3658	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0297 (17)	0.0363 (18)	0.0335 (17)	0.0109 (14)	0.0134 (14)	0.0027 (14)
N21	0.0374 (18)	0.0355 (18)	0.0270 (16)	0.0094 (15)	0.0156 (14)	0.0054 (13)
C12	0.041 (2)	0.046 (2)	0.032 (2)	0.0178 (19)	0.0132 (18)	0.0098 (18)
C13	0.038 (2)	0.041 (2)	0.0295 (19)	0.0146 (18)	0.0160 (17)	0.0090 (17)
C14	0.031 (2)	0.034 (2)	0.0283 (19)	0.0084 (16)	0.0128 (16)	0.0023 (15)
C15	0.038 (2)	0.037 (2)	0.0277 (19)	0.0095 (18)	0.0149 (17)	0.0042 (16)
C16	0.038 (2)	0.038 (2)	0.034 (2)	0.0082 (18)	0.0192 (18)	0.0055 (17)
C17	0.033 (2)	0.037 (2)	0.0303 (19)	0.0093 (17)	0.0131 (16)	0.0042 (16)
C18	0.040 (2)	0.040 (2)	0.0287 (19)	0.0139 (18)	0.0148 (17)	0.0041 (16)
C22	0.036 (2)	0.045 (2)	0.033 (2)	0.0136 (19)	0.0151 (18)	0.0037 (18)
C23	0.034 (2)	0.037 (2)	0.0303 (19)	0.0115 (17)	0.0130 (17)	0.0046 (16)
C24	0.039 (2)	0.039 (2)	0.0283 (19)	0.0142 (18)	0.0161 (17)	0.0067 (16)
C25	0.032 (2)	0.042 (2)	0.0293 (19)	0.0131 (18)	0.0103 (16)	0.0026 (17)
C26	0.040 (2)	0.044 (2)	0.0277 (19)	0.0171 (19)	0.0096 (17)	0.0038 (17)
C27	0.033 (2)	0.040 (2)	0.0286 (19)	0.0136 (17)	0.0119 (16)	0.0029 (16)
N31	0.0345 (18)	0.0376 (18)	0.0255 (16)	0.0128 (15)	0.0110 (14)	0.0057 (13)
N41	0.0292 (17)	0.0346 (18)	0.0300 (16)	0.0123 (14)	0.0094 (13)	0.0013 (13)
C32	0.043 (2)	0.041 (2)	0.0263 (19)	0.0202 (19)	0.0098 (17)	0.0067 (16)
C33	0.044 (2)	0.034 (2)	0.0278 (19)	0.0106 (18)	0.0155 (17)	0.0096 (16)
C34	0.034 (2)	0.035 (2)	0.0251 (18)	0.0138 (17)	0.0101 (16)	0.0069 (15)
C35	0.035 (2)	0.032 (2)	0.0289 (19)	0.0104 (17)	0.0122 (16)	0.0090 (15)
C36	0.042 (2)	0.037 (2)	0.0277 (19)	0.0122 (18)	0.0150 (17)	0.0059 (16)
C37	0.041 (2)	0.035 (2)	0.033 (2)	0.0136 (18)	0.0179 (18)	0.0067 (16)
C38	0.036 (2)	0.039 (2)	0.0296 (19)	0.0136 (18)	0.0146 (17)	0.0040 (16)
C42	0.033 (2)	0.035 (2)	0.0290 (19)	0.0106 (17)	0.0147 (16)	0.0075 (16)
C43	0.032 (2)	0.039 (2)	0.0252 (18)	0.0138 (17)	0.0130 (16)	0.0061 (15)
C44	0.032 (2)	0.038 (2)	0.0285 (18)	0.0170 (17)	0.0151 (16)	0.0087 (16)
C45	0.037 (2)	0.037 (2)	0.0305 (19)	0.0132 (18)	0.0170 (17)	0.0039 (16)
C46	0.031 (2)	0.037 (2)	0.0278 (19)	0.0096 (16)	0.0120 (16)	0.0041 (16)
C47	0.039 (2)	0.038 (2)	0.033 (2)	0.0128 (18)	0.0181 (18)	0.0045 (17)
P1	0.0280 (5)	0.0355 (6)	0.0271 (5)	0.0105 (4)	0.0115 (4)	0.0049 (4)
O11	0.0274 (14)	0.0470 (17)	0.0327 (14)	0.0123 (12)	0.0107 (12)	−0.0014 (12)
O12	0.0374 (17)	0.064 (2)	0.0401 (16)	0.0236 (15)	0.0111 (13)	−0.0073 (15)
O13	0.0289 (14)	0.0384 (16)	0.0423 (16)	0.0125 (12)	0.0124 (13)	0.0000 (12)
O14	0.0355 (15)	0.0407 (16)	0.0296 (14)	0.0081 (12)	0.0176 (12)	0.0066 (11)
O15	0.0304 (14)	0.0381 (16)	0.0363 (15)	0.0092 (12)	0.0118 (12)	0.0028 (12)
C1	0.034 (2)	0.045 (2)	0.0240 (18)	0.0180 (18)	0.0096 (16)	0.0068 (16)
C2	0.035 (2)	0.046 (2)	0.037 (2)	0.0145 (19)	0.0187 (18)	0.0156 (18)
P2	0.0266 (5)	0.0413 (6)	0.0252 (5)	0.0129 (4)	0.0098 (4)	0.0043 (4)
O21	0.0357 (16)	0.0458 (17)	0.0361 (15)	0.0145 (13)	0.0176 (13)	0.0028 (12)
O22	0.0329 (15)	0.0443 (17)	0.0290 (14)	0.0125 (13)	0.0116 (12)	0.0028 (12)
O23	0.0311 (15)	0.0503 (18)	0.0300 (14)	0.0162 (13)	0.0104 (12)	−0.0008 (12)
O24	0.0297 (14)	0.0433 (16)	0.0266 (13)	0.0122 (12)	0.0113 (11)	0.0080 (11)
O25	0.0331 (15)	0.0395 (16)	0.0358 (15)	0.0136 (12)	0.0156 (12)	0.0006 (12)
C3	0.034 (2)	0.033 (2)	0.0289 (19)	0.0147 (16)	0.0141 (16)	0.0115 (16)
C4	0.033 (2)	0.039 (2)	0.0251 (18)	0.0157 (17)	0.0090 (16)	0.0058 (15)
O71	0.046 (7)	0.043 (7)	0.141 (13)	0.002 (5)	0.060 (8)	0.008 (7)
O81	0.058 (3)	0.047 (3)	0.103 (5)	0.021 (3)	0.011 (3)	0.007 (3)
C82	0.025 (4)	0.072 (6)	0.096 (7)	0.002 (3)	−0.006 (4)	0.033 (5)
O91	0.056 (7)	0.048 (5)	0.045 (5)	0.009 (4)	0.021 (5)	0.011 (4)
O92	0.065 (5)	0.117 (5)	0.134 (7)	0.028 (4)	0.044 (5)	0.085 (5)

Geometric parameters (Å, º)

N11—C16	1.489 (5)	C33—C34	1.527 (5)
N11—C12	1.490 (5)	C33—H33A	0.99
N11—H11A	0.92	C33—H33B	0.99
N11—H11B	0.92	C34—C35	1.535 (5)
N21—C26	1.485 (5)	C34—C37	1.535 (5)
N21—C22	1.497 (5)	C34—H34	1.00
N21—H21A	0.92	C35—C36	1.511 (5)
N21—H21B	0.92	C35—H35A	0.99
C12—C13	1.527 (6)	C35—H35B	0.99
C12—H12A	0.99	C36—H36A	0.99
C12—H12B	0.99	C36—H36B	0.99
C13—C14	1.518 (5)	C37—C38	1.526 (6)
C13—H13A	0.99	C37—H37A	0.99
C13—H13B	0.99	C37—H37B	0.99
C14—C15	1.522 (5)	C38—C47	1.529 (5)
C14—C17	1.529 (5)	C38—H38A	0.99
C14—H14	1.00	C38—H38B	0.99
C15—C16	1.518 (6)	C42—C43	1.527 (5)
C15—H15A	0.99	C42—H42A	0.99
C15—H15B	0.99	C42—H42B	0.99
C16—H16A	0.99	C43—C44	1.532 (5)
C16—H16B	0.99	C43—H43A	0.99
C17—C18	1.528 (5)	C43—H43B	0.99
C17—H17A	0.99	C44—C45	1.523 (5)
C17—H17B	0.99	C44—C47	1.523 (5)
C18—C27	1.519 (5)	C44—H44	1.00
C18—H18A	0.99	C45—C46	1.518 (5)
C18—H18B	0.99	C45—H45A	0.99
C22—C23	1.523 (5)	C45—H45B	0.99
C22—H22A	0.99	C46—H46A	0.99
C22—H22B	0.99	C46—H46B	0.99
C23—C24	1.523 (5)	C47—H47A	0.99
C23—H23A	0.99	C47—H47B	0.99
C23—H23B	0.99	P1—O14	1.504 (3)
C24—C25	1.525 (5)	P1—O15	1.510 (3)
C24—C27	1.534 (5)	P1—O13	1.569 (3)
C24—H24	1.00	P1—C2	1.817 (4)
C25—C26	1.533 (5)	O11—C1	1.260 (5)
C25—H25A	0.99	O12—C1	1.255 (5)
C25—H25B	0.99	O13—H13	0.84
C26—H26A	0.99	C1—C2	1.511 (6)
C26—H26B	0.99	C2—H2A	0.99
C27—H27A	0.99	C2—H2B	0.99
C27—H27B	0.99	P2—O25	1.501 (3)
N31—C36	1.486 (5)	P2—O24	1.511 (3)
N31—C32	1.494 (5)	P2—O23	1.575 (3)
N31—H31A	0.92	P2—C4	1.815 (4)
N31—H31B	0.92	O21—C3	1.268 (4)
N41—C42	1.493 (5)	O22—C3	1.253 (5)
N41—C46	1.497 (5)	O23—H23	0.84
N41—H41A	0.92	C3—C4	1.517 (5)
N41—H41B	0.92	C4—H4A	0.99
C32—C33	1.519 (5)	C4—H4B	0.99
C32—H32A	0.99	O81—C82	1.369 (9)
C32—H32B	0.99	O91—O92	1.150 (9)
C16—N11—C12	112.2 (3)	C33—C32—H32B	109.7
C16—N11—H11A	109.2	H32A—C32—H32B	108.2
C12—N11—H11A	109.2	C32—C33—C34	112.9 (3)
C16—N11—H11B	109.2	C32—C33—H33A	109.0
C12—N11—H11B	109.2	C34—C33—H33A	109.0
H11A—N11—H11B	107.9	C32—C33—H33B	109.0
C26—N21—C22	111.8 (3)	C34—C33—H33B	109.0
C26—N21—H21A	109.3	H33A—C33—H33B	107.8
C22—N21—H21A	109.3	C33—C34—C35	109.7 (3)
C26—N21—H21B	109.3	C33—C34—C37	110.3 (3)
C22—N21—H21B	109.3	C35—C34—C37	111.5 (3)
H21A—N21—H21B	107.9	C33—C34—H34	108.4
N11—C12—C13	111.1 (3)	C35—C34—H34	108.4
N11—C12—H12A	109.4	C37—C34—H34	108.4
C13—C12—H12A	109.4	C36—C35—C34	112.0 (3)
N11—C12—H12B	109.4	C36—C35—H35A	109.2
C13—C12—H12B	109.4	C34—C35—H35A	109.2
H12A—C12—H12B	108.0	C36—C35—H35B	109.2
C14—C13—C12	112.0 (3)	C34—C35—H35B	109.2
C14—C13—H13A	109.2	H35A—C35—H35B	107.9
C12—C13—H13A	109.2	N31—C36—C35	111.1 (3)
C14—C13—H13B	109.2	N31—C36—H36A	109.4
C12—C13—H13B	109.2	C35—C36—H36A	109.4
H13A—C13—H13B	107.9	N31—C36—H36B	109.4
C13—C14—C15	108.6 (3)	C35—C36—H36B	109.4
C13—C14—C17	113.9 (3)	H36A—C36—H36B	108.0
C15—C14—C17	110.8 (3)	C38—C37—C34	116.6 (3)
C13—C14—H14	107.8	C38—C37—H37A	108.1
C15—C14—H14	107.8	C34—C37—H37A	108.1
C17—C14—H14	107.8	C38—C37—H37B	108.1
C16—C15—C14	111.4 (3)	C34—C37—H37B	108.1
C16—C15—H15A	109.4	H37A—C37—H37B	107.3
C14—C15—H15A	109.4	C37—C38—C47	111.1 (3)
C16—C15—H15B	109.4	C37—C38—H38A	109.4
C14—C15—H15B	109.4	C47—C38—H38A	109.4
H15A—C15—H15B	108.0	C37—C38—H38B	109.4
N11—C16—C15	111.4 (3)	C47—C38—H38B	109.4
N11—C16—H16A	109.4	H38A—C38—H38B	108.0
C15—C16—H16A	109.4	N41—C42—C43	110.7 (3)
N11—C16—H16B	109.4	N41—C42—H42A	109.5
C15—C16—H16B	109.4	C43—C42—H42A	109.5
H16A—C16—H16B	108.0	N41—C42—H42B	109.5
C18—C17—C14	114.4 (3)	C43—C42—H42B	109.5
C18—C17—H17A	108.7	H42A—C42—H42B	108.1
C14—C17—H17A	108.7	C42—C43—C44	112.0 (3)
C18—C17—H17B	108.7	C42—C43—H43A	109.2
C14—C17—H17B	108.7	C44—C43—H43A	109.2
H17A—C17—H17B	107.6	C42—C43—H43B	109.2
C27—C18—C17	112.6 (3)	C44—C43—H43B	109.2
C27—C18—H18A	109.1	H43A—C43—H43B	107.9
C17—C18—H18A	109.1	C45—C44—C47	109.9 (3)
C27—C18—H18B	109.1	C45—C44—C43	107.2 (3)
C17—C18—H18B	109.1	C47—C44—C43	114.3 (3)
H18A—C18—H18B	107.8	C45—C44—H44	108.4
N21—C22—C23	110.1 (3)	C47—C44—H44	108.4
N21—C22—H22A	109.6	C43—C44—H44	108.4
C23—C22—H22A	109.6	C46—C45—C44	113.1 (3)
N21—C22—H22B	109.6	C46—C45—H45A	109.0
C23—C22—H22B	109.6	C44—C45—H45A	109.0
H22A—C22—H22B	108.1	C46—C45—H45B	109.0
C22—C23—C24	112.0 (3)	C44—C45—H45B	109.0
C22—C23—H23A	109.2	H45A—C45—H45B	107.8
C24—C23—H23A	109.2	N41—C46—C45	110.7 (3)
C22—C23—H23B	109.2	N41—C46—H46A	109.5
C24—C23—H23B	109.2	C45—C46—H46A	109.5
H23A—C23—H23B	107.9	N41—C46—H46B	109.5
C23—C24—C25	108.9 (3)	C45—C46—H46B	109.5
C23—C24—C27	109.9 (3)	H46A—C46—H46B	108.1
C25—C24—C27	113.4 (3)	C44—C47—C38	117.1 (3)
C23—C24—H24	108.2	C44—C47—H47A	108.0
C25—C24—H24	108.2	C38—C47—H47A	108.0
C27—C24—H24	108.2	C44—C47—H47B	108.0
C24—C25—C26	111.3 (3)	C38—C47—H47B	108.0
C24—C25—H25A	109.4	H47A—C47—H47B	107.3
C26—C25—H25A	109.4	O14—P1—O15	117.01 (16)
C24—C25—H25B	109.4	O14—P1—O13	107.97 (16)
C26—C25—H25B	109.4	O15—P1—O13	111.20 (16)
H25A—C25—H25B	108.0	O14—P1—C2	107.75 (17)
N21—C26—C25	109.4 (3)	O15—P1—C2	106.42 (18)
N21—C26—H26A	109.8	O13—P1—C2	105.88 (18)
C25—C26—H26A	109.8	P1—O13—H13	109.5
N21—C26—H26B	109.8	O12—C1—O11	123.2 (4)
C25—C26—H26B	109.8	O12—C1—C2	119.3 (4)
H26A—C26—H26B	108.2	O11—C1—C2	117.5 (3)
C18—C27—C24	114.0 (3)	C1—C2—P1	113.9 (3)
C18—C27—H27A	108.7	C1—C2—H2A	108.8
C24—C27—H27A	108.7	P1—C2—H2A	108.8
C18—C27—H27B	108.7	C1—C2—H2B	108.8
C24—C27—H27B	108.7	P1—C2—H2B	108.8
H27A—C27—H27B	107.6	H2A—C2—H2B	107.7
C36—N31—C32	111.0 (3)	O25—P2—O24	117.53 (16)
C36—N31—H31A	109.4	O25—P2—O23	109.04 (16)
C32—N31—H31A	109.4	O24—P2—O23	110.04 (15)
C36—N31—H31B	109.4	O25—P2—C4	107.10 (17)
C32—N31—H31B	109.4	O24—P2—C4	107.96 (17)
H31A—N31—H31B	108.0	O23—P2—C4	104.31 (17)
C42—N41—C46	111.9 (3)	P2—O23—H23	109.5
C42—N41—H41A	109.2	O22—C3—O21	125.0 (4)
C46—N41—H41A	109.2	O22—C3—C4	118.7 (3)
C42—N41—H41B	109.2	O21—C3—C4	116.3 (3)
C46—N41—H41B	109.2	C3—C4—P2	111.3 (3)
H41A—N41—H41B	107.9	C3—C4—H4A	109.4
N31—C32—C33	109.7 (3)	P2—C4—H4A	109.4
N31—C32—H32A	109.7	C3—C4—H4B	109.4
C33—C32—H32A	109.7	P2—C4—H4B	109.4
N31—C32—H32B	109.7	H4A—C4—H4B	108.0
C16—N11—C12—C13	−53.9 (4)	C37—C34—C35—C36	−173.9 (3)
N11—C12—C13—C14	55.4 (5)	C32—N31—C36—C35	−59.5 (4)
C12—C13—C14—C15	−56.3 (4)	C34—C35—C36—N31	55.8 (4)
C12—C13—C14—C17	179.7 (3)	C33—C34—C37—C38	166.6 (3)
C13—C14—C15—C16	56.9 (4)	C35—C34—C37—C38	−71.3 (4)
C17—C14—C15—C16	−177.3 (3)	C34—C37—C38—C47	177.4 (3)
C12—N11—C16—C15	55.0 (4)	C46—N41—C42—C43	55.5 (4)
C14—C15—C16—N11	−56.9 (4)	N41—C42—C43—C44	−57.5 (4)
C13—C14—C17—C18	−62.1 (5)	C42—C43—C44—C45	56.6 (4)
C15—C14—C17—C18	175.2 (3)	C42—C43—C44—C47	178.6 (3)
C14—C17—C18—C27	−173.5 (3)	C47—C44—C45—C46	178.8 (3)
C26—N21—C22—C23	57.8 (4)	C43—C44—C45—C46	−56.4 (4)
N21—C22—C23—C24	−56.0 (4)	C42—N41—C46—C45	−54.7 (4)
C22—C23—C24—C25	55.3 (4)	C44—C45—C46—N41	56.5 (4)
C22—C23—C24—C27	−179.8 (3)	C45—C44—C47—C38	−174.1 (3)
C23—C24—C25—C26	−56.4 (4)	C43—C44—C47—C38	65.4 (5)
C27—C24—C25—C26	−179.1 (3)	C37—C38—C47—C44	169.5 (3)
C22—N21—C26—C25	−58.8 (4)	O12—C1—C2—P1	−87.9 (4)
C24—C25—C26—N21	58.5 (4)	O11—C1—C2—P1	91.8 (4)
C17—C18—C27—C24	−177.4 (3)	O14—P1—C2—C1	−49.0 (3)
C23—C24—C27—C18	179.3 (3)	O15—P1—C2—C1	−175.2 (3)
C25—C24—C27—C18	−58.6 (5)	O13—P1—C2—C1	66.4 (3)
C36—N31—C32—C33	59.0 (4)	O22—C3—C4—P2	93.7 (4)
N31—C32—C33—C34	−56.3 (4)	O21—C3—C4—P2	−85.0 (4)
C32—C33—C34—C35	52.3 (4)	O25—P2—C4—C3	66.9 (3)
C32—C33—C34—C37	175.5 (3)	O24—P2—C4—C3	−60.5 (3)
C33—C34—C35—C36	−51.5 (4)	O23—P2—C4—C3	−177.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O22	0.92	1.81	2.716 (4)	168
N11—H11B···O12	0.92	1.83	2.659 (4)	149
N21—H21A···O23^i	0.92	2.52	3.228 (4)	134
N21—H21B···O14^ii	0.92	1.81	2.722 (4)	174
N31—H31A···O25	0.92	2.01	2.840 (4)	150
N31—H31A···O21	0.92	2.34	2.832 (4)	113
N31—H31B···O15	0.92	1.90	2.797 (4)	166
N41—H41A···O24^iii	0.92	1.81	2.721 (4)	171
N41—H41B···O24^iv	0.92	2.12	2.976 (4)	154
N41—H41B···O11^v	0.92	2.62	3.091 (4)	113
O13—H13···O21	0.84	1.70	2.533 (4)	171
O23—H23···O11^vi	0.84	1.72	2.524 (4)	160

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

(IV) meso-5,5,7,12,12,14-Hexa-C-methyl-1,4,8,11- tetraazacyclotetradecane–phosphonoacetic acid (1/2)

Crystal data

C16H38N4·2(C2H4O5P)	Z = 1
Mr = 564.55	F(000) = 304
Triclinic, P1	Dx = 1.348 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7219 (2) Å	Cell parameters from 2923 reflections
b = 9.8947 (1) Å	θ = 2.6–27.4°
c = 9.9343 (2) Å	µ = 0.21 mm^−1
α = 62.5110 (9)°	T = 150 K
β = 85.6800 (8)°	Needle, colourless
γ = 67.1910 (9)°	0.40 × 0.24 × 0.20 mm
V = 695.42 (2) Å^3

Data collection

Kappa-CCD diffractometer	2745 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.026
Graphite monochromator	θmax = 27.4°, θmin = 2.6°
φ scans, and ω scans with κ offsets	h = 0→11
9161 measured reflections	k = −11→12
3148 independent reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 0.3032P] where P = (Fo^2 + 2Fc^2)/3
3148 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.27 e Å^−3
2 restraints	Δρmin = −0.41 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.38142 (14)	0.75819 (15)	0.36971 (14)	0.0249 (3)
C2	0.50414 (19)	0.7679 (2)	0.25656 (18)	0.0320 (3)
C3	0.53834 (19)	0.6374 (2)	0.20624 (17)	0.0333 (3)
N4	0.63215 (15)	0.47060 (17)	0.33057 (14)	0.0297 (3)
C5	0.6823 (2)	0.3331 (2)	0.2899 (2)	0.0387 (4)
C51	0.8089 (2)	0.3448 (3)	0.1729 (3)	0.0543 (5)
C52	0.5273 (3)	0.3286 (4)	0.2214 (3)	0.0440 (7)	0.711 (4)
C6	0.7627 (2)	0.1684 (2)	0.4368 (2)	0.0413 (4)
C7	0.6511 (2)	0.1265 (2)	0.5616 (2)	0.0384 (4)
C71	0.7326 (4)	−0.0533 (2)	0.6870 (3)	0.0730 (8)
C72	0.5066 (6)	0.1389 (7)	0.4802 (6)	0.0319 (14)*	0.289 (4)
P1	−0.07373 (4)	0.85424 (5)	0.20055 (4)	0.02476 (12)
O1	0.04282 (14)	0.40071 (13)	0.39647 (12)	0.0301 (2)
O2	0.22829 (14)	0.50639 (14)	0.39544 (13)	0.0354 (3)
O3	−0.20618 (13)	0.98336 (14)	0.05432 (12)	0.0359 (3)
O4	0.07233 (13)	0.90260 (13)	0.19184 (12)	0.0303 (2)
O5	−0.16478 (13)	0.83423 (13)	0.33803 (12)	0.0303 (2)
C11	0.10463 (18)	0.51497 (18)	0.33723 (16)	0.0253 (3)
C12	0.0033 (2)	0.6616 (2)	0.18921 (17)	0.0304 (3)
H1A	0.4193	0.6508	0.4480	0.030*
H1B	0.2811	0.7807	0.3228	0.030*
H2A	0.6104	0.7521	0.3029	0.038*
H2B	0.4595	0.8795	0.1663	0.038*
H3A	0.4307	0.6437	0.1726	0.040*
H3B	0.6033	0.6595	0.1181	0.040*
H4	0.7275	0.4692	0.3660	0.036*
H51A	0.7578	0.4489	0.0779	0.081*
H51B	0.8407	0.2506	0.1518	0.081*
H51C	0.9089	0.3423	0.2145	0.081*
H52A	0.4383	0.3353	0.2874	0.066*	0.711 (4)
H52B	0.5625	0.2246	0.2158	0.066*	0.711 (4)
H52C	0.4853	0.4230	0.1186	0.066*	0.711 (4)
H6A	0.8059	0.0775	0.4088	0.050*
H6B	0.8603	0.1697	0.4802	0.050*
H71A	0.6562	−0.0762	0.7639	0.110*
H71B	0.8374	−0.0712	0.7354	0.110*
H71C	0.7566	−0.1281	0.6421	0.110*
H72A	0.4364	0.2561	0.4133	0.048*	0.289 (4)
H72B	0.4402	0.0875	0.5550	0.048*	0.289 (4)
H72C	0.5476	0.0812	0.4186	0.048*	0.289 (4)
H1	0.0942	0.3285	0.4841	0.045*
H3	−0.1563	1.0155	−0.0225	0.054*
H12A	−0.0930	0.6435	0.1651	0.036*
H12B	0.0739	0.6702	0.1053	0.036*
H5	0.5862	0.3303	0.2474	0.050*	0.29
H7	0.5552	0.1346	0.5080	0.050*	0.71

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0199 (6)	0.0202 (6)	0.0308 (6)	−0.0062 (5)	−0.0019 (5)	−0.0098 (5)
C2	0.0252 (7)	0.0323 (8)	0.0290 (7)	−0.0137 (6)	0.0001 (6)	−0.0048 (6)
C3	0.0249 (7)	0.0426 (9)	0.0238 (7)	−0.0098 (7)	0.0020 (6)	−0.0117 (7)
N4	0.0217 (6)	0.0363 (7)	0.0264 (6)	−0.0035 (5)	0.0004 (5)	−0.0172 (6)
C5	0.0271 (8)	0.0536 (10)	0.0396 (9)	−0.0056 (7)	0.0034 (7)	−0.0336 (9)
C51	0.0387 (10)	0.0883 (16)	0.0603 (12)	−0.0219 (10)	0.0188 (9)	−0.0584 (13)
C52	0.0332 (13)	0.0618 (17)	0.0536 (16)	−0.0168 (12)	0.0013 (11)	−0.0411 (14)
C6	0.0306 (8)	0.0410 (9)	0.0560 (11)	0.0013 (7)	−0.0029 (8)	−0.0372 (9)
C7	0.0388 (9)	0.0266 (8)	0.0524 (10)	−0.0096 (7)	−0.0084 (8)	−0.0212 (8)
C71	0.102 (2)	0.0228 (9)	0.0812 (17)	−0.0100 (11)	−0.0250 (15)	−0.0212 (10)
P1	0.0222 (2)	0.02398 (19)	0.02130 (19)	−0.01077 (15)	0.00025 (14)	−0.00380 (15)
O1	0.0358 (6)	0.0300 (6)	0.0262 (5)	−0.0177 (5)	0.0040 (4)	−0.0109 (4)
O2	0.0271 (6)	0.0327 (6)	0.0413 (6)	−0.0126 (5)	0.0013 (5)	−0.0127 (5)
O3	0.0252 (6)	0.0385 (6)	0.0270 (6)	−0.0148 (5)	−0.0037 (4)	0.0004 (5)
O4	0.0272 (5)	0.0276 (5)	0.0270 (5)	−0.0146 (4)	−0.0033 (4)	−0.0020 (4)
O5	0.0296 (6)	0.0274 (5)	0.0275 (5)	−0.0104 (5)	0.0057 (4)	−0.0092 (4)
C11	0.0252 (7)	0.0268 (7)	0.0269 (7)	−0.0100 (6)	0.0095 (6)	−0.0161 (6)
C12	0.0367 (8)	0.0341 (8)	0.0216 (7)	−0.0166 (7)	0.0052 (6)	−0.0123 (6)

Geometric parameters (Å, º)

N1—C2	1.4890 (19)	C6—H6A	0.99
N1—C7^i	1.5119 (19)	C6—H6B	0.99
N1—H1A	0.92	C7—C72	1.484 (5)
N1—H1B	0.92	C7—N1^i	1.5119 (19)
C2—C3	1.511 (2)	C7—C71	1.526 (3)
C2—H2A	0.99	C7—H7	0.98
C2—H2B	0.99	C71—H71A	0.98
C3—N4	1.464 (2)	C71—H71B	0.98
C3—H3A	0.99	C71—H71C	0.98
C3—H3B	0.99	C72—H72A	0.98
N4—C5	1.492 (2)	C72—H72B	0.98
N4—H4	0.92	C72—H72C	0.98
C5—C6	1.533 (3)	P1—O5	1.4980 (11)
C5—C51	1.538 (2)	P1—O4	1.5090 (10)
C5—C52	1.583 (3)	P1—O3	1.5724 (11)
C5—H5	0.98	P1—C12	1.8146 (16)
C51—H51A	0.98	O1—C11	1.3137 (17)
C51—H51B	0.98	O1—H1	0.84
C51—H51C	0.98	O2—C11	1.2176 (18)
C52—H52A	0.98	O3—H3	0.84
C52—H52B	0.98	C11—C12	1.510 (2)
C52—H52C	0.98	C12—H12A	0.99
C6—C7	1.521 (3)	C12—H12B	0.99
C2—N1—C7^i	115.82 (12)	C7—C6—H6A	108.1
C2—N1—H1A	108.3	C5—C6—H6A	108.1
C7^i—N1—H1A	108.3	C7—C6—H6B	108.1
C2—N1—H1B	108.3	C5—C6—H6B	108.1
C7^i—N1—H1B	108.3	H6A—C6—H6B	107.3
H1A—N1—H1B	107.4	C72—C7—N1^i	118.2 (2)
N1—C2—C3	111.22 (12)	C72—C7—C6	102.7 (2)
N1—C2—H2A	109.4	N1^i—C7—C6	108.02 (13)
C3—C2—H2A	109.4	C72—C7—C71	106.5 (3)
N1—C2—H2B	109.4	N1^i—C7—C71	109.42 (15)
C3—C2—H2B	109.4	C6—C7—C71	111.90 (17)
H2A—C2—H2B	108.0	N1^i—C7—H7	118.1
N4—C3—C2	111.18 (12)	C6—C7—H7	102.9
N4—C3—H3A	109.4	C71—C7—H7	106.5
C2—C3—H3A	109.4	C7—C71—H71A	109.5
N4—C3—H3B	109.4	C7—C71—H71B	109.5
C2—C3—H3B	109.4	H71A—C71—H71B	109.5
H3A—C3—H3B	108.0	C7—C71—H71C	109.5
C3—N4—C5	115.51 (12)	H71A—C71—H71C	109.5
C3—N4—H4	108.4	H71B—C71—H71C	109.5
C5—N4—H4	108.4	C7—C72—H72A	109.5
N4—C5—C6	107.89 (12)	C7—C72—H72B	109.5
N4—C5—C51	112.25 (16)	H72A—C72—H72B	109.5
C6—C5—C51	108.92 (15)	C7—C72—H72C	109.5
N4—C5—C52	112.53 (15)	H72A—C72—H72C	109.5
C6—C5—C52	107.47 (18)	H72B—C72—H72C	109.5
C51—C5—C52	107.63 (16)	H72A—C72—H7	109.6
N4—C5—H5	112.5	H72B—C72—H7	109.1
C6—C5—H5	107.5	H72C—C72—H7	109.7
C51—C5—H5	107.6	O5—P1—O4	116.93 (6)
C5—C51—H51A	109.5	O5—P1—O3	107.75 (6)
C5—C51—H51B	109.5	O4—P1—O3	110.26 (6)
H51A—C51—H51B	109.5	O5—P1—C12	109.11 (6)
C5—C51—H51C	109.5	O4—P1—C12	107.60 (7)
H51A—C51—H51C	109.5	O3—P1—C12	104.47 (7)
H51B—C51—H51C	109.5	C11—O1—H1	109.5
C5—C52—H52A	109.5	P1—O3—H3	109.5
C5—C52—H52B	109.5	O2—C11—O1	124.27 (14)
H52A—C52—H52B	109.5	O2—C11—C12	123.12 (13)
C5—C52—H52C	109.5	O1—C11—C12	112.60 (13)
H52A—C52—H52C	109.5	C11—C12—P1	111.65 (10)
H52B—C52—H52C	109.5	C11—C12—H12A	109.3
H52A—C52—H5	109.5	P1—C12—H12A	109.3
H52B—C52—H5	109.5	C11—C12—H12B	109.3
H52C—C52—H5	109.5	P1—C12—H12B	109.3
C7—C6—C5	116.82 (13)	H12A—C12—H12B	108.0
C7^i—N1—C2—C3	174.97 (12)	C5—C6—C7—C72	54.5 (3)
N1—C2—C3—N4	−69.30 (16)	C5—C6—C7—N1^i	−71.09 (17)
C2—C3—N4—C5	−176.17 (12)	C6—C7—N1^i—C2^i	173.6 (2)
C3—N4—C5—C6	−174.41 (13)	C5—C6—C7—C71	168.41 (15)
C3—N4—C5—C51	65.58 (18)	O2—C11—C12—P1	−57.35 (17)
C3—N4—C5—C52	−56.0 (2)	O1—C11—C12—P1	121.49 (11)
N4—C5—C6—C7	63.29 (18)	O5—P1—C12—C11	−52.86 (12)
C51—C5—C6—C7	−174.62 (14)	O4—P1—C12—C11	74.93 (11)
C52—C5—C6—C7	−58.29 (19)	O3—P1—C12—C11	−167.87 (10)

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
N1—H1A···N4^i	0.92	2.08	2.817 (2)	137
N1—H1B···O4	0.92	1.92	2.799 (2)	160
N4—H4···O2^i	0.92	2.56	3.198 (2)	127
N4—H4···O1^ii	0.92	2.57	3.428 (2)	155
O1—H1···O5^iii	0.84	1.69	2.517 (2)	167
O3—H3···O4^iv	0.84	1.74	2.581 (2)	174
C2—H2A···O5^ii	0.99	2.50	3.426 (2)	156

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

(V) 2,2'-Dipyridylamine–phosphonoacetic acid (1/1)

Crystal data

C10H10N3·C2H4O5P	Z = 2
Mr = 311.23	F(000) = 324
Triclinic, P1	Dx = 1.538 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0706 (2) Å	Cell parameters from 3079 reflections
b = 10.6500 (3) Å	θ = 3.1–27.6°
c = 10.7020 (4) Å	µ = 0.23 mm^−1
α = 115.8690 (13)°	T = 150 K
β = 98.8120 (15)°	Plate, colourless
γ = 104.0040 (13)°	0.34 × 0.16 × 0.16 mm
V = 671.96 (4) Å^3

Data collection

Kappa-CCD diffractometer	2471 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.056
Graphite monochromator	θmax = 27.6°, θmin = 3.1°
φ scans, and ω scans with κ offsets	h = −9→9
9556 measured reflections	k = −13→13
3079 independent reflections	l = −13→13

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.2307P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3079 reflections	Δρmax = 0.31 e Å^−3
198 parameters	Δρmin = −0.36 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: 0.015 (4)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.51314 (7)	0.30480 (5)	0.32094 (5)	0.02138 (15)
O1	−0.0328 (2)	0.16780 (14)	0.20237 (16)	0.0322 (3)
O2	0.1096 (2)	0.39365 (17)	0.2324 (2)	0.0515 (5)
O3	0.6160 (2)	0.46751 (13)	0.35201 (15)	0.0273 (3)
O4	0.43906 (19)	0.30642 (13)	0.44647 (13)	0.0244 (3)
O5	0.6523 (2)	0.21936 (15)	0.27471 (17)	0.0335 (3)
C1	0.1144 (3)	0.2717 (2)	0.2029 (2)	0.0258 (4)
C2	0.2899 (3)	0.2223 (2)	0.1648 (2)	0.0285 (4)
N1	0.3613 (2)	0.10773 (16)	0.54655 (17)	0.0208 (4)	0.916 (4)
C11	0.2153 (3)	−0.02955 (19)	0.4590 (2)	0.0236 (4)
N12	0.1871 (2)	−0.13001 (16)	0.50572 (17)	0.0245 (3)
C13	0.0426 (3)	−0.26680 (19)	0.4236 (2)	0.0259 (4)
C14	−0.0787 (3)	−0.3089 (2)	0.2904 (2)	0.0270 (4)
C15	−0.0514 (3)	−0.2081 (2)	0.2383 (2)	0.0263 (4)
C16	0.0947 (3)	−0.06801 (19)	0.3228 (2)	0.0248 (4)
C21	0.4754 (3)	0.1724 (2)	0.68984 (19)	0.0232 (4)
N22	0.4571 (2)	0.08625 (16)	0.75188 (17)	0.0258 (3)
C23	0.5620 (3)	0.1469 (2)	0.8920 (2)	0.0271 (4)
C24	0.6889 (3)	0.2936 (2)	0.9749 (2)	0.0281 (4)
C25	0.7092 (3)	0.3813 (2)	0.9084 (2)	0.0275 (4)
C26	0.6026 (3)	0.32177 (19)	0.7648 (2)	0.0247 (4)
N1A	0.334 (3)	−0.0296 (18)	0.6520 (18)	0.021 (5)*	0.084 (4)
H1A	−0.1259	0.2007	0.2259	0.048*
H3	0.5910	0.5274	0.4246	0.041*
H2A	0.3277	0.2492	0.0921	0.034*
H2B	0.2452	0.1127	0.1197	0.034*
H1	0.3867	0.1634	0.5057	0.025*	0.916 (4)
H12	0.2642	−0.1058	0.5912	0.029*
H13	0.0255	−0.3348	0.4596	0.031*
H14	−0.1802	−0.4052	0.2337	0.032*
H15	−0.1334	−0.2361	0.1449	0.032*
H16	0.1131	0.0015	0.2887	0.030*
H23	0.5483	0.0860	0.9362	0.033*
H24	0.7603	0.3338	1.0743	0.034*
H25	0.7969	0.4824	0.9624	0.033*
H26	0.6151	0.3802	0.7182	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0193 (2)	0.0215 (2)	0.0315 (3)	0.00863 (18)	0.01155 (19)	0.0178 (2)
O1	0.0264 (7)	0.0284 (7)	0.0517 (9)	0.0127 (6)	0.0208 (7)	0.0232 (7)
O2	0.0273 (8)	0.0383 (9)	0.1032 (15)	0.0137 (7)	0.0182 (9)	0.0459 (9)
O3	0.0303 (7)	0.0225 (6)	0.0354 (8)	0.0073 (5)	0.0158 (6)	0.0185 (6)
O4	0.0277 (7)	0.0224 (6)	0.0292 (7)	0.0071 (5)	0.0114 (5)	0.0177 (5)
O5	0.0292 (7)	0.0341 (7)	0.0571 (9)	0.0194 (6)	0.0242 (7)	0.0310 (7)
C1	0.0219 (9)	0.0293 (9)	0.0273 (10)	0.0068 (7)	0.0042 (7)	0.0170 (8)
C2	0.0242 (9)	0.0337 (10)	0.0267 (10)	0.0087 (8)	0.0116 (8)	0.0137 (8)
N1	0.0242 (9)	0.0181 (8)	0.0249 (9)	0.0062 (6)	0.0091 (7)	0.0145 (7)
C11	0.0215 (9)	0.0212 (8)	0.0286 (9)	0.0096 (7)	0.0134 (7)	0.0096 (7)
N12	0.0237 (8)	0.0261 (8)	0.0248 (8)	0.0082 (6)	0.0086 (6)	0.0132 (6)
C13	0.0265 (9)	0.0221 (8)	0.0322 (10)	0.0073 (7)	0.0135 (8)	0.0148 (8)
C14	0.0250 (9)	0.0217 (8)	0.0303 (10)	0.0054 (7)	0.0111 (8)	0.0098 (8)
C15	0.0251 (9)	0.0267 (9)	0.0283 (10)	0.0105 (7)	0.0103 (8)	0.0130 (8)
C16	0.0262 (9)	0.0233 (9)	0.0306 (10)	0.0113 (7)	0.0134 (8)	0.0151 (8)
C21	0.0208 (8)	0.0271 (9)	0.0246 (9)	0.0119 (7)	0.0108 (7)	0.0120 (7)
N22	0.0277 (8)	0.0238 (8)	0.0293 (8)	0.0100 (6)	0.0126 (7)	0.0142 (7)
C23	0.0328 (10)	0.0276 (9)	0.0282 (10)	0.0137 (8)	0.0130 (8)	0.0168 (8)
C24	0.0302 (10)	0.0285 (9)	0.0251 (9)	0.0116 (8)	0.0079 (8)	0.0122 (8)
C25	0.0257 (9)	0.0247 (9)	0.0299 (10)	0.0082 (7)	0.0075 (8)	0.0123 (8)
C26	0.0244 (9)	0.0254 (9)	0.0306 (10)	0.0108 (7)	0.0113 (8)	0.0169 (8)

Geometric parameters (Å, º)

P1—O5	1.4937 (13)	C13—C14	1.360 (3)
P1—O4	1.5097 (13)	C13—H13	0.95
P1—O3	1.5670 (12)	C14—C15	1.399 (3)
P1—C2	1.815 (2)	C14—H14	0.95
O1—C1	1.320 (2)	C15—C16	1.379 (3)
O1—H1A	0.84	C15—H15	0.95
O2—C1	1.206 (2)	C16—H16	0.95
O3—H3	0.84	C21—N22	1.342 (2)
C1—C2	1.505 (2)	C21—C26	1.399 (2)
C2—H2A	0.99	N22—C23	1.341 (2)
C2—H2B	0.99	C23—C24	1.379 (3)
N1—C11	1.364 (2)	C23—H23	0.95
N1—C21	1.381 (2)	C24—C25	1.394 (3)
N1—H1	0.88	C24—H24	0.95
C11—N12	1.352 (2)	C25—C26	1.377 (3)
C11—C16	1.396 (3)	C25—H25	0.95
N12—C13	1.351 (2)	C26—H26	0.95
N12—H12	0.88
O5—P1—O4	116.90 (8)	N12—C13—H13	119.4
O5—P1—O3	109.12 (7)	C14—C13—H13	119.4
O4—P1—O3	110.52 (7)	C13—C14—C15	118.89 (17)
O5—P1—C2	106.88 (9)	C13—C14—H14	120.6
O4—P1—C2	107.39 (8)	C15—C14—H14	120.6
O3—P1—C2	105.33 (9)	C16—C15—C14	119.84 (18)
C1—O1—H1A	109.5	C16—C15—H15	120.1
P1—O3—H3	109.5	C14—C15—H15	120.1
O2—C1—O1	123.54 (18)	C15—C16—C11	119.25 (17)
O2—C1—C2	123.69 (17)	C15—C16—H16	120.4
O1—C1—C2	112.77 (16)	C11—C16—H16	120.4
C1—C2—P1	113.16 (13)	N22—C21—N1	117.14 (16)
C1—C2—H2A	108.9	N22—C21—C26	122.53 (17)
P1—C2—H2A	108.9	N1—C21—C26	120.33 (17)
C1—C2—H2B	108.9	C21—N22—C23	118.56 (16)
P1—C2—H2B	108.9	N22—C23—C24	122.89 (18)
H2A—C2—H2B	107.8	N22—C23—H23	118.6
C11—N1—C21	129.65 (16)	C24—C23—H23	118.6
C11—N1—H1	115.2	C23—C24—C25	117.97 (18)
C21—N1—H1	115.2	C23—C24—H24	121.0
N12—C11—N1	119.05 (17)	C25—C24—H24	121.0
N12—C11—C16	119.56 (16)	C26—C25—C24	120.24 (17)
N1—C11—C16	121.38 (17)	C26—C25—H25	119.9
C13—N12—C11	121.23 (17)	C24—C25—H25	119.9
C13—N12—H12	119.4	C25—C26—C21	117.80 (17)
C11—N12—H12	119.4	C25—C26—H26	121.1
N12—C13—C14	121.22 (17)	C21—C26—H26	121.1
O2—C1—C2—P1	73.8 (2)	N12—C11—C16—C15	0.0 (3)
O1—C1—C2—P1	−105.37 (16)	N1—C11—C16—C15	−179.82 (16)
O5—P1—C2—C1	166.44 (13)	C11—N1—C21—N22	6.7 (3)
O4—P1—C2—C1	40.25 (16)	C11—N1—C21—C26	−173.01 (17)
O3—P1—C2—C1	−77.57 (14)	N1—C21—N22—C23	−178.36 (15)
C21—N1—C11—N12	−9.3 (3)	C26—C21—N22—C23	1.3 (3)
C21—N1—C11—C16	170.54 (17)	C21—N22—C23—C24	−0.4 (3)
N1—C11—N12—C13	179.19 (15)	N22—C23—C24—C25	−0.6 (3)
C16—C11—N12—C13	−0.7 (3)	C23—C24—C25—C26	0.8 (3)
C11—N12—C13—C14	0.5 (3)	C24—C25—C26—C21	0.0 (3)
N12—C13—C14—C15	0.3 (3)	N22—C21—C26—C25	−1.1 (3)
C13—C14—C15—C16	−0.9 (3)	N1—C21—C26—C25	178.56 (16)
C14—C15—C16—C11	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5^i	0.84	1.76	2.570 (2)	163
O3—H3···O4^ii	0.84	1.80	2.604 (2)	161
N1—H1···O4	0.88	1.87	2.743 (2)	171
N12—H12···N22	0.88	1.97	2.632 (2)	131
N12—H12···O5^iii	0.88	2.34	3.062 (2)	140
C24—H24···O2^iv	0.95	2.53	3.312 (3)	140
C26—H26···O2^ii	0.95	2.48	3.201 (3)	132

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

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

Crystal data

C12H14N2·2(C2H4O5P)	F(000) = 484
Mr = 464.30	Dx = 1.556 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5037 reflections
a = 8.8501 (3) Å	θ = 2.7–27.5°
b = 15.1862 (6) Å	µ = 0.28 mm^−1
c = 7.3741 (3) Å	T = 150 K
β = 90.761 (2)°	Plate, colourless
V = 990.99 (7) Å^3	0.28 × 0.12 × 0.08 mm
Z = 2

Data collection

Kappa-CCD diffractometer	1883 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.035
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
φ scans, and ω scans with κ offsets	h = −11→11
6047 measured reflections	k = −19→19
2263 independent reflections	l = −9→9

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 0.3391P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2263 reflections	Δρmax = 0.31 e Å^−3
139 parameters	Δρmin = −0.44 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: 0.011 (3)

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

	x	y	z	Uiso*/Ueq
N11	0.34697 (17)	0.22012 (10)	0.4545 (2)	0.0243 (3)
C12	0.3901 (2)	0.13831 (12)	0.4128 (3)	0.0250 (4)
C13	0.2983 (2)	0.06793 (12)	0.4530 (2)	0.0226 (4)
C14	0.16064 (19)	0.08219 (11)	0.5379 (2)	0.0200 (4)
C15	0.1202 (2)	0.16862 (12)	0.5789 (3)	0.0248 (4)
C16	0.2152 (2)	0.23682 (12)	0.5355 (3)	0.0263 (4)
C17	0.05716 (19)	0.00666 (11)	0.5789 (2)	0.0201 (4)
P1	0.68900 (5)	0.32839 (3)	0.36203 (6)	0.01589 (16)
O1	0.61750 (14)	0.49497 (8)	0.64863 (17)	0.0228 (3)
O2	0.79401 (15)	0.54881 (8)	0.46390 (19)	0.0293 (3)
O3	0.75737 (14)	0.35912 (8)	0.17802 (16)	0.0216 (3)
O4	0.52239 (13)	0.35167 (8)	0.36887 (18)	0.0222 (3)
O5	0.72120 (14)	0.23257 (8)	0.39571 (16)	0.0213 (3)
C1	0.73635 (19)	0.48752 (11)	0.5417 (2)	0.0190 (4)
C2	0.79104 (19)	0.39360 (11)	0.5294 (2)	0.0195 (4)
H11	0.4069	0.2644	0.4280	0.029*
H12	0.4841	0.1287	0.3555	0.030*
H13	0.3287	0.0098	0.4229	0.027*
H15	0.0270	0.1803	0.6368	0.030*
H16	0.1875	0.2957	0.5628	0.032*
H17A	0.0022	0.0188	0.6923	0.024*
H17B	0.1172	−0.0477	0.5968	0.024*
H1	0.5843	0.5467	0.6436	0.034*
H3	0.7424	0.3202	0.0989	0.032*
H2A	0.7811	0.3653	0.6496	0.023*
H2B	0.8996	0.3939	0.4988	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0241 (8)	0.0232 (8)	0.0256 (8)	−0.0095 (6)	−0.0007 (6)	0.0029 (6)
C12	0.0214 (8)	0.0280 (10)	0.0257 (10)	−0.0044 (7)	0.0014 (7)	−0.0008 (8)
C13	0.0229 (9)	0.0218 (9)	0.0230 (9)	−0.0015 (7)	0.0011 (7)	−0.0027 (7)
C14	0.0200 (8)	0.0228 (9)	0.0172 (8)	−0.0046 (7)	−0.0039 (6)	0.0012 (7)
C15	0.0207 (9)	0.0236 (9)	0.0302 (10)	−0.0026 (7)	0.0025 (7)	−0.0006 (7)
C16	0.0254 (9)	0.0220 (9)	0.0313 (11)	−0.0029 (7)	−0.0009 (8)	0.0004 (8)
C17	0.0207 (8)	0.0200 (9)	0.0197 (9)	−0.0035 (7)	−0.0003 (7)	0.0015 (7)
P1	0.0174 (2)	0.0147 (2)	0.0156 (2)	−0.00116 (15)	0.00267 (16)	−0.00017 (15)
O1	0.0257 (7)	0.0204 (6)	0.0226 (7)	0.0024 (5)	0.0033 (5)	−0.0009 (5)
O2	0.0343 (7)	0.0211 (7)	0.0325 (8)	−0.0038 (6)	0.0052 (6)	0.0013 (6)
O3	0.0286 (7)	0.0202 (6)	0.0162 (6)	−0.0067 (5)	0.0050 (5)	−0.0010 (5)
O4	0.0181 (6)	0.0186 (6)	0.0299 (7)	−0.0010 (5)	0.0027 (5)	−0.0020 (5)
O5	0.0299 (7)	0.0163 (6)	0.0180 (6)	0.0002 (5)	0.0021 (5)	−0.0006 (5)
C1	0.0202 (8)	0.0205 (8)	0.0162 (8)	−0.0015 (7)	−0.0039 (6)	−0.0011 (7)
C2	0.0214 (8)	0.0190 (8)	0.0179 (8)	0.0005 (6)	−0.0003 (6)	−0.0004 (7)

Geometric parameters (Å, º)

N11—C12	1.337 (2)	C17—H17A	0.99
N11—C16	1.342 (2)	C17—H17B	0.99
N11—H11	0.88	P1—O5	1.5029 (12)
C12—C13	1.377 (2)	P1—O4	1.5178 (12)
C12—H12	0.95	P1—O3	1.5643 (12)
C13—C14	1.394 (2)	P1—C2	1.8136 (18)
C13—H13	0.95	O1—C1	1.328 (2)
C14—C15	1.395 (2)	O1—H1	0.84
C14—C17	1.501 (2)	O2—C1	1.210 (2)
C15—C16	1.374 (2)	O3—H3	0.84
C15—H15	0.95	C1—C2	1.509 (2)
C16—H16	0.95	C2—H2A	0.99
C17—C17^i	1.545 (3)	C2—H2B	0.99
C12—N11—C16	122.05 (15)	C14—C17—H17B	109.6
C12—N11—H11	119.0	C17^i—C17—H17B	109.6
C16—N11—H11	119.0	H17A—C17—H17B	108.2
N11—C12—C13	120.07 (16)	O5—P1—O4	113.71 (7)
N11—C12—H12	120.0	O5—P1—O3	110.95 (7)
C13—C12—H12	120.0	O4—P1—O3	110.27 (7)
C12—C13—C14	119.83 (17)	O5—P1—C2	108.95 (8)
C12—C13—H13	120.1	O4—P1—C2	108.99 (7)
C14—C13—H13	120.1	O3—P1—C2	103.44 (7)
C13—C14—C15	118.16 (16)	C1—O1—H1	109.5
C13—C14—C17	120.73 (16)	P1—O3—H3	109.5
C15—C14—C17	121.09 (16)	O2—C1—O1	123.95 (16)
C16—C15—C14	119.94 (17)	O2—C1—C2	124.11 (16)
C16—C15—H15	120.0	O1—C1—C2	111.94 (14)
C14—C15—H15	120.0	C1—C2—P1	113.57 (12)
N11—C16—C15	119.95 (17)	C1—C2—H2A	108.9
N11—C16—H16	120.0	P1—C2—H2A	108.9
C15—C16—H16	120.0	C1—C2—H2B	108.9
C14—C17—C17^i	110.08 (18)	P1—C2—H2B	108.9
C14—C17—H17A	109.6	H2A—C2—H2B	107.7
C17^i—C17—H17A	109.6
C16—N11—C12—C13	0.0 (3)	C13—C14—C17—C17^i	−92.4 (2)
N11—C12—C13—C14	−0.3 (3)	C15—C14—C17—C17^i	85.9 (2)
C12—C13—C14—C15	0.3 (3)	O2—C1—C2—P1	−96.25 (18)
C12—C13—C14—C17	178.54 (16)	O1—C1—C2—P1	83.93 (15)
C13—C14—C15—C16	0.0 (3)	O5—P1—C2—C1	−164.52 (12)
C17—C14—C15—C16	−178.25 (17)	O4—P1—C2—C1	−39.92 (14)
C12—N11—C16—C15	0.3 (3)	O3—P1—C2—C1	77.40 (13)
C14—C15—C16—N11	−0.3 (3)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O4	0.88	1.73	2.613 (2)	178
O1—H1···O4^ii	0.84	1.81	2.640 (2)	169
O3—H3···O5^iii	0.84	1.71	2.521 (2)	163
C13—H13···O3^iv	0.95	2.52	3.349 (2)	146
C15—H15···O3^v	0.95	2.48	3.329 (2)	148
C16—H16···O2^ii	0.95	2.38	3.256 (2)	154

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