Ethane-1,2-diphosphonic acid as a building block in supramolecular chemistry; a pillared-layer framework and framework-encapsulated cations

Wheatley, P.S.; Lough, A.J.; Ferguson, G.; Burchell, C.J.; Glidewell, C.

doi:10.1107/S0108768100014841

Ethane-1,2-diphosphonic acid as a building block in supramolecular chemistry; a pillared-layer framework and framework-encapsulated cations

P. S. Wheatley, A. J. Lough, G. Ferguson, C. J. Burchell and C. Glidewell

The 1:1 adduct of piperazine and ethane-1,2-diphosphonic acid is a salt [C₄H₁₂N₂]²⁺·[C₂H₆O₆P₂]²⁻, in which both ions lie across centres of inversion in space group P2₁/c. The anions are linked by a single type of O—H

O hydrogen bond [O

O, 2.562 (3) Å; H

O, 1.73 Å, O—H

O, 169°] into (6, 3) nets built from a single type of

ring. The cations lie between these nets, linked to them by two types of N—H

O hydrogen bond [N

O, 2.635 (3) and 2.735 (3) Å; H

O 1.72 and 1.82 Å, N—H

O, 175 and 177°] such that the cations link adjacent sheets, thus forming a pillared-layer framework. The aquated adduct formed between trimethylenedipiperidine and ethane-1,2-diphosphonic acid is also a salt [C₁₃H₂₈N₂]²⁺·[C₂H₆O₆P₂]²⁻·2.8[H₂O], in which there are 12 different types of hydrogen bond, eight O—H

O and four N—H

O. The anions are linked into chains by pairs of O—H

O hydrogen bonds and these chains are linked by the water molecules into a continuous three-dimensional framework. Within the anion/water framework are large voids which contain pairs of cations, linked to the framework by N—H

O hydrogen bonds.

Keywords: supramolecular chemistry; pillared-layer framework; adducts; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100014841/na0111sup1.cif Contains datablocks global, 18, 17
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768100014841/na011118sup2.hkl Contains datablock 18
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768100014841/na011117sup3.hkl Contains datablock 17

CCDC references: 159972; 159973

Comment top

In full text version

Experimental top

In full text version

Computing details top

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

Figures top

In full text version

(18) Piperazine-ethane-1,2-diphosphonic acid (1/1) top

Crystal data top

C₄H₁₂N₂·C₂H₆O₆P₂	F(000) = 292
M_r = 276.16	D_x = 1.488 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.3914 (6) Å	Cell parameters from 3237 reflections
b = 9.3343 (7) Å	θ = 2.9–27.4°
c = 9.3590 (6) Å	µ = 0.37 mm⁻¹
β = 107.291 (4)°	T = 150 K
V = 616.53 (8) Å³	Needle, colourless
Z = 2	0.20 × 0.06 × 0.02 mm

Data collection top

Kappa-CCD diffractometer	1401 independent reflections
Radiation source: fine-focus sealed X-ray tube	947 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ scans and ω scans with κ offsets	θ_max = 27.4°, θ_min = 2.9°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→9
T_min = 0.930, T_max = 0.993	k = 0→12
3237 measured reflections	l = −12→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0312P)² + 0.6688P] where P = (F_o² + 2F_c²)/3
1401 reflections	(Δ/σ)_max < 0.001
74 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₄H₁₂N₂·C₂H₆O₆P₂	V = 616.53 (8) Å³
M_r = 276.16	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3914 (6) Å	µ = 0.37 mm⁻¹
b = 9.3343 (7) Å	T = 150 K
c = 9.3590 (6) Å	0.20 × 0.06 × 0.02 mm
β = 107.291 (4)°

Data collection top

Kappa-CCD diffractometer	1401 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	947 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.993	R_int = 0.057
3237 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.37 e Å⁻³
1401 reflections	Δρ_min = −0.43 e Å⁻³
74 parameters

Special details top

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

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

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

	x	y	z	U_iso*/U_eq
P1	0.94421 (13)	0.41065 (9)	0.20303 (9)	0.0164 (3)
O1	0.7583 (3)	0.3578 (2)	0.2177 (2)	0.0206 (6)
O2	1.0375 (3)	0.5304 (2)	0.3082 (2)	0.0205 (6)
O3	1.0943 (3)	0.2861 (2)	0.2286 (3)	0.0220 (6)
C1	0.9100 (4)	0.4705 (4)	0.0138 (3)	0.0204 (8)
N1	0.6521 (4)	0.4553 (3)	0.4446 (3)	0.0208 (7)
C2	0.5123 (5)	0.3499 (4)	0.4674 (4)	0.0219 (8)
C3	0.5674 (5)	0.5999 (4)	0.4102 (4)	0.0236 (8)
H3	1.0379	0.2069	0.2118	0.033*
H1A	0.8626	0.3892	−0.0551	0.024*
H1B	0.8115	0.5460	−0.0102	0.024*
H1C	0.7540	0.4597	0.5296	0.025*
H1D	0.6954	0.4251	0.3670	0.025*
H2A	0.5746	0.2557	0.4949	0.026*
H2B	0.4081	0.3381	0.3731	0.026*
H3A	0.4652	0.5972	0.3139	0.028*
H3B	0.6653	0.6682	0.4000	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0180 (5)	0.0168 (5)	0.0148 (4)	−0.0004 (4)	0.0053 (3)	−0.0008 (4)
O1	0.0195 (13)	0.0258 (13)	0.0191 (12)	−0.0030 (11)	0.0095 (10)	−0.0028 (10)
O2	0.0240 (14)	0.0151 (12)	0.0191 (11)	−0.0036 (10)	0.0013 (10)	−0.0046 (10)
O3	0.0212 (14)	0.0114 (12)	0.0330 (13)	−0.0015 (10)	0.0074 (11)	−0.0018 (11)
C1	0.0202 (19)	0.025 (2)	0.0157 (16)	−0.0028 (16)	0.0047 (14)	0.0001 (14)
N1	0.0199 (16)	0.0273 (17)	0.0162 (14)	0.0013 (13)	0.0069 (12)	−0.0021 (12)
C2	0.0227 (19)	0.0210 (18)	0.0219 (17)	0.0010 (16)	0.0064 (15)	0.0019 (15)
C3	0.025 (2)	0.026 (2)	0.0214 (17)	−0.0006 (17)	0.0095 (15)	0.0038 (15)

Geometric parameters (Å, º) top

P1—O1	1.504 (2)	N1—C2	1.487 (4)
P1—O2	1.514 (2)	N1—H1C	0.9200
P1—O3	1.575 (2)	N1—H1D	0.9200
P1—C1	1.802 (3)	C2—C3ⁱⁱ	1.510 (5)
O3—H3	0.8400	C2—H2A	0.9900
C1—C1ⁱ	1.531 (6)	C2—H2B	0.9900
C1—H1A	0.9900	C3—C2ⁱⁱ	1.510 (5)
C1—H1B	0.9900	C3—H3A	0.9900
N1—C3	1.482 (4)	C3—H3B	0.9900

O1—P1—O2	115.77 (13)	C3—N1—H1D	109.3
O1—P1—O3	111.42 (13)	C2—N1—H1D	109.3
O2—P1—O3	106.39 (13)	H1C—N1—H1D	108.0
O1—P1—C1	109.04 (13)	N1—C2—C3ⁱⁱ	110.4 (3)
O2—P1—C1	108.31 (14)	N1—C2—H2A	109.6
O3—P1—C1	105.36 (15)	C3ⁱⁱ—C2—H2A	109.6
P1—O3—H3	109.5	N1—C2—H2B	109.6
C1ⁱ—C1—P1	113.7 (3)	C3ⁱⁱ—C2—H2B	109.6
C1ⁱ—C1—H1A	108.8	H2A—C2—H2B	108.1
P1—C1—H1A	108.8	N1—C3—C2ⁱⁱ	110.7 (3)
C1ⁱ—C1—H1B	108.8	N1—C3—H3A	109.5
P1—C1—H1B	108.8	C2ⁱⁱ—C3—H3A	109.5
H1A—C1—H1B	107.7	N1—C3—H3B	109.5
C3—N1—C2	111.5 (3)	C2ⁱⁱ—C3—H3B	109.5
C3—N1—H1C	109.3	H3A—C3—H3B	108.1
C2—N1—H1C	109.3

O1—P1—C1—C1ⁱ	178.9 (3)	C3—N1—C2—C3ⁱⁱ	−56.5 (4)
O2—P1—C1—C1ⁱ	52.1 (4)	C2—N1—C3—C2ⁱⁱ	56.7 (4)
O3—P1—C1—C1ⁱ	−61.4 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱⁱⁱ	0.84	1.73	2.562 (2)	169
N1—H1C···O2^iv	0.92	1.82	2.735 (3)	177
N1—H1D···O1	0.92	1.72	2.635 (3)	175
C2—H2A···O1^v	0.99	2.37	3.166 (4)	136
C2—H2B···O3^vi	0.99	2.36	3.285 (5)	155

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

(17) 4,4'-trimethylenedipiperidine-ethane-1,2-diphosphonic acid-water (1/1/2.8). top

Crystal data top

(C₁₃H₂₈N₂)·(C₂H₆O₆P₂)·2.8(H₂O)	F(000) = 973
M_r = 450.01	D_x = 1.332 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1218 (2) Å	Cell parameters from 13672 reflections
b = 20.6215 (7) Å	θ = 3.0–30.1°
c = 18.1831 (7) Å	µ = 0.24 mm⁻¹
β = 99.942 (2)°	T = 120 K
V = 2260.98 (14) Å³	Block, colourless
Z = 4	0.30 × 0.12 × 0.12 mm

Data collection top

Kappa-CCD diffractometer	6599 independent reflections
Radiation source: fine-focus sealed X-ray tube	4617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ scans and ω scans with κ offsets	θ_max = 30.1°, θ_min = 3.0°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→8
T_min = 0.932, T_max = 0.972	k = −29→0
13672 measured reflections	l = −25→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0333P)² + 1.181P] where P = (F_o² + 2F_c²)/3
6599 reflections	(Δ/σ)_max = 0.001
284 parameters	Δρ_max = 0.40 e Å⁻³
6 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

(C₁₃H₂₈N₂)·(C₂H₆O₆P₂)·2.8(H₂O)	V = 2260.98 (14) Å³
M_r = 450.01	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1218 (2) Å	µ = 0.24 mm⁻¹
b = 20.6215 (7) Å	T = 120 K
c = 18.1831 (7) Å	0.30 × 0.12 × 0.12 mm
β = 99.942 (2)°

Data collection top

Kappa-CCD diffractometer	6599 independent reflections
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	4617 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.972	R_int = 0.033
13672 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	6 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	Δρ_max = 0.40 e Å⁻³
6599 reflections	Δρ_min = −0.39 e Å⁻³
284 parameters

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
N11	0.2398 (2)	0.26517 (8)	0.50540 (9)	0.0190 (3)
C12	0.1348 (3)	0.33055 (10)	0.50280 (12)	0.0246 (4)
C13	0.3078 (3)	0.38363 (9)	0.50220 (12)	0.0231 (4)
C14	0.4954 (3)	0.37781 (9)	0.56953 (11)	0.0197 (4)
C15	0.5957 (3)	0.30998 (9)	0.56861 (11)	0.0198 (4)
C16	0.4226 (3)	0.25759 (10)	0.57085 (11)	0.0218 (4)
C17	0.6671 (3)	0.43166 (9)	0.57012 (11)	0.0227 (4)
C18	0.8409 (3)	0.43454 (9)	0.64141 (11)	0.0231 (4)
C19	0.9987 (3)	0.49186 (9)	0.64262 (11)	0.0225 (4)
N21	1.4015 (2)	0.56843 (7)	0.84112 (9)	0.0196 (3)
C22	1.2669 (3)	0.50973 (9)	0.85170 (11)	0.0213 (4)
C23	1.0895 (3)	0.50044 (10)	0.78325 (11)	0.0219 (4)
C24	1.1834 (3)	0.49508 (9)	0.71087 (11)	0.0198 (4)
C25	1.3363 (3)	0.55287 (9)	0.70467 (11)	0.0218 (4)
C26	1.5105 (3)	0.56218 (10)	0.77452 (11)	0.0227 (4)
P1	0.51784 (7)	0.18672 (2)	0.36067 (3)	0.01750 (11)
P2	0.97414 (7)	0.28310 (2)	0.22866 (3)	0.01652 (11)
O11	0.5704 (2)	0.13972 (7)	0.42480 (8)	0.0251 (3)
O12	0.4089 (2)	0.24934 (6)	0.37945 (7)	0.0201 (3)
O13	0.3689 (2)	0.15207 (6)	0.29305 (8)	0.0231 (3)
O21	0.8935 (2)	0.33129 (6)	0.16740 (7)	0.0220 (3)
O22	1.0973 (2)	0.22498 (6)	0.20657 (7)	0.0194 (3)
O23	1.1228 (2)	0.32169 (6)	0.29441 (8)	0.0221 (3)
C1	0.7729 (3)	0.20749 (9)	0.32879 (10)	0.0197 (4)
C2	0.7328 (3)	0.25730 (9)	0.26563 (11)	0.0189 (4)
O3	0.3198 (2)	0.08832 (8)	0.52162 (8)	0.0274 (3)
O4	−0.0510 (4)	0.16833 (16)	0.52524 (9)	0.0251 (8)	0.866 (11)
O41	−0.122 (3)	0.1948 (8)	0.5260 (6)	0.017 (4)*	0.134 (11)
O5	0.1802 (7)	−0.02668 (15)	0.5826 (3)	0.0366 (14)	0.585 (10)
O51	0.1100 (16)	−0.0376 (4)	0.5439 (7)	0.030 (3)*	0.209 (11)
H11A	0.2956	0.2586	0.4622	0.023*
H11B	0.1336	0.2340	0.5078	0.023*
H12A	0.0615	0.3362	0.5468	0.030*
H12B	0.0201	0.3341	0.4574	0.030*
H13A	0.2360	0.4266	0.5030	0.028*
H13B	0.3703	0.3805	0.4556	0.028*
H14	0.4292	0.3820	0.6159	0.024*
H15A	0.6612	0.3047	0.5228	0.024*
H15B	0.7160	0.3050	0.6122	0.024*
H16A	0.4915	0.2143	0.5695	0.026*
H16B	0.3619	0.2611	0.6178	0.026*
H17A	0.5889	0.4738	0.5635	0.027*
H17B	0.7439	0.4254	0.5270	0.027*
H18A	0.7645	0.4375	0.6850	0.028*
H18B	0.9280	0.3938	0.6461	0.028*
H19A	0.9112	0.5324	0.6402	0.027*
H19B	1.0674	0.4900	0.5972	0.027*
H21A	1.3111	0.6044	0.8358	0.023*
H21B	1.5081	0.5744	0.8829	0.023*
H22A	1.1969	0.5152	0.8965	0.026*
H22B	1.3640	0.4710	0.8592	0.026*
H23A	0.9854	0.5375	0.7792	0.026*
H23B	1.0046	0.4606	0.7897	0.026*
H24	1.2731	0.4544	0.7128	0.024*
H25A	1.4117	0.5463	0.6613	0.026*
H25B	1.2456	0.5928	0.6956	0.026*
H26A	1.6127	0.5246	0.7809	0.027*
H26B	1.5984	0.6017	0.7692	0.027*
H13	0.2829	0.1793	0.2688	0.035*
H23	1.2158	0.2964	0.3187	0.033*
H1A	0.8799	0.2254	0.3710	0.024*
H1B	0.8387	0.1678	0.3110	0.024*
H2A	0.6635	0.2961	0.2840	0.023*
H2B	0.6246	0.2388	0.2242	0.023*
H31	0.197 (2)	0.1081 (10)	0.5193 (14)	0.040*
H32	0.380 (3)	0.1032 (11)	0.4864 (9)	0.040*
H41	−0.173 (3)	0.1595 (14)	0.4967 (13)	0.040*	0.866 (11)
H42	−0.066 (5)	0.1721 (14)	0.5706 (5)	0.040*	0.866 (11)
H51	0.206 (7)	−0.0030 (18)	0.5468 (18)	0.040*	0.585 (10)
H52	0.244 (6)	−0.0617 (11)	0.574 (2)	0.040*	0.585 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0165 (7)	0.0241 (8)	0.0165 (8)	−0.0035 (6)	0.0031 (6)	−0.0025 (6)
C12	0.0163 (8)	0.0299 (11)	0.0262 (11)	0.0021 (8)	−0.0005 (8)	−0.0052 (9)
C13	0.0205 (9)	0.0211 (10)	0.0256 (11)	0.0027 (7)	−0.0021 (8)	−0.0015 (8)
C14	0.0180 (8)	0.0232 (10)	0.0174 (9)	−0.0004 (7)	0.0012 (7)	−0.0031 (8)
C15	0.0162 (8)	0.0220 (10)	0.0199 (9)	−0.0013 (7)	−0.0002 (7)	0.0026 (8)
C16	0.0205 (9)	0.0265 (10)	0.0176 (10)	−0.0035 (8)	0.0012 (7)	0.0037 (8)
C17	0.0246 (9)	0.0191 (9)	0.0224 (10)	0.0012 (8)	−0.0019 (8)	−0.0021 (8)
C18	0.0238 (9)	0.0224 (10)	0.0212 (10)	−0.0014 (8)	−0.0010 (8)	−0.0020 (8)
C19	0.0250 (9)	0.0207 (10)	0.0206 (10)	−0.0024 (8)	0.0007 (8)	−0.0008 (8)
N21	0.0160 (7)	0.0205 (8)	0.0209 (8)	0.0017 (6)	−0.0005 (6)	−0.0012 (7)
C22	0.0210 (9)	0.0227 (10)	0.0198 (10)	−0.0022 (7)	0.0023 (7)	0.0006 (8)
C23	0.0156 (8)	0.0268 (10)	0.0223 (10)	−0.0027 (7)	0.0005 (7)	−0.0003 (8)
C24	0.0184 (8)	0.0190 (9)	0.0213 (10)	0.0002 (7)	0.0014 (7)	−0.0023 (8)
C25	0.0227 (9)	0.0216 (10)	0.0218 (10)	−0.0042 (8)	0.0064 (8)	−0.0034 (8)
C26	0.0173 (8)	0.0238 (10)	0.0277 (11)	−0.0032 (7)	0.0063 (8)	−0.0033 (8)
P1	0.0165 (2)	0.0196 (2)	0.0159 (2)	0.00030 (18)	0.00156 (17)	0.00276 (19)
P2	0.0166 (2)	0.0180 (2)	0.0150 (2)	0.00223 (18)	0.00275 (17)	0.00145 (19)
O11	0.0200 (6)	0.0305 (8)	0.0240 (8)	−0.0005 (6)	0.0012 (6)	0.0115 (6)
O12	0.0204 (6)	0.0237 (7)	0.0162 (7)	0.0024 (5)	0.0031 (5)	−0.0007 (5)
O13	0.0244 (7)	0.0176 (7)	0.0242 (8)	0.0010 (5)	−0.0047 (6)	−0.0003 (6)
O21	0.0240 (6)	0.0241 (7)	0.0185 (7)	0.0069 (5)	0.0059 (5)	0.0053 (5)
O22	0.0201 (6)	0.0208 (7)	0.0171 (7)	0.0040 (5)	0.0030 (5)	−0.0002 (5)
O23	0.0234 (7)	0.0196 (7)	0.0216 (7)	0.0017 (5)	−0.0013 (6)	−0.0003 (6)
C1	0.0186 (8)	0.0231 (10)	0.0174 (9)	0.0023 (7)	0.0025 (7)	0.0023 (8)
C2	0.0159 (8)	0.0224 (10)	0.0179 (9)	0.0014 (7)	0.0018 (7)	0.0025 (8)
O3	0.0221 (7)	0.0372 (9)	0.0227 (8)	0.0027 (6)	0.0033 (6)	0.0068 (7)
O4	0.0207 (11)	0.0370 (17)	0.0174 (9)	−0.0077 (11)	0.0026 (7)	−0.0007 (8)
O5	0.040 (2)	0.0316 (18)	0.043 (3)	0.0086 (13)	0.0215 (19)	0.0061 (15)

Geometric parameters (Å, º) top

N11—C12	1.491 (2)	C23—H23B	0.9900
N11—C16	1.494 (2)	C24—C25	1.532 (3)
N11—H11A	0.9200	C24—H24	1.0000
N11—H11B	0.9200	C25—C26	1.523 (3)
C12—C13	1.524 (3)	C25—H25A	0.9900
C12—H12A	0.9900	C25—H25B	0.9900
C12—H12B	0.9900	C26—H26A	0.9900
C13—C14	1.532 (2)	C26—H26B	0.9900
C13—H13A	0.9900	P1—O11	1.5076 (14)
C13—H13B	0.9900	P1—O12	1.5189 (14)
C14—C17	1.528 (3)	P1—O13	1.5707 (13)
C14—C15	1.529 (3)	P1—C1	1.8086 (19)
C14—H14	1.0000	P2—O22	1.5071 (13)
C15—C16	1.519 (2)	P2—O21	1.5105 (13)
C15—H15A	0.9900	P2—O23	1.5860 (13)
C15—H15B	0.9900	P2—C2	1.8055 (18)
C16—H16A	0.9900	O13—H13	0.8400
C16—H16B	0.9900	O23—H23	0.8400
C17—C18	1.530 (3)	C1—C2	1.529 (3)
C17—H17A	0.9900	C1—H1A	0.9900
C17—H17B	0.9900	C1—H1B	0.9900
C18—C19	1.524 (3)	C2—H2A	0.9900
C18—H18A	0.9900	C2—H2B	0.9900
C18—H18B	0.9900	O3—H31	0.85 (2)
C19—C24	1.529 (2)	O3—H32	0.85 (2)
C19—H19A	0.9900	O4—O41	0.701 (18)
C19—H19B	0.9900	O4—H41	0.850 (3)
N21—C26	1.486 (2)	O4—H42	0.850 (3)
N21—C22	1.495 (2)	O41—H41	0.92 (2)
N21—H21A	0.9200	O41—H42	0.95 (2)
N21—H21B	0.9200	O5—O51	0.791 (10)
C22—C23	1.516 (3)	O5—H51	0.850 (3)
C22—H22A	0.9900	O5—H52	0.850 (3)
C22—H22B	0.9900	O51—H51	0.92 (4)
C23—C24	1.528 (3)	O51—H52	1.03 (3)
C23—H23A	0.9900

C12—N11—C16	112.30 (15)	H22A—C22—H22B	108.3
C12—N11—H11A	109.1	C22—C23—C24	113.18 (15)
C16—N11—H11A	109.1	C22—C23—H23A	108.9
C12—N11—H11B	109.1	C24—C23—H23A	108.9
C16—N11—H11B	109.1	C22—C23—H23B	108.9
H11A—N11—H11B	107.9	C24—C23—H23B	108.9
N11—C12—C13	110.69 (15)	H23A—C23—H23B	107.8
N11—C12—H12A	109.5	C23—C24—C19	111.52 (15)
C13—C12—H12A	109.5	C23—C24—C25	109.42 (15)
N11—C12—H12B	109.5	C19—C24—C25	110.47 (16)
C13—C12—H12B	109.5	C23—C24—H24	108.5
H12A—C12—H12B	108.1	C19—C24—H24	108.5
C12—C13—C14	111.34 (16)	C25—C24—H24	108.5
C12—C13—H13A	109.4	C26—C25—C24	112.68 (16)
C14—C13—H13A	109.4	C26—C25—H25A	109.1
C12—C13—H13B	109.4	C24—C25—H25A	109.1
C14—C13—H13B	109.4	C26—C25—H25B	109.1
H13A—C13—H13B	108.0	C24—C25—H25B	109.1
C17—C14—C15	112.84 (15)	H25A—C25—H25B	107.8
C17—C14—C13	111.63 (16)	N21—C26—C25	110.04 (15)
C15—C14—C13	108.05 (15)	N21—C26—H26A	109.7
C17—C14—H14	108.1	C25—C26—H26A	109.7
C15—C14—H14	108.1	N21—C26—H26B	109.7
C13—C14—H14	108.1	C25—C26—H26B	109.7
C16—C15—C14	111.55 (15)	H26A—C26—H26B	108.2
C16—C15—H15A	109.3	O11—P1—O12	114.59 (8)
C14—C15—H15A	109.3	O11—P1—O13	109.30 (8)
C16—C15—H15B	109.3	O12—P1—O13	110.17 (7)
C14—C15—H15B	109.3	O11—P1—C1	108.62 (8)
H15A—C15—H15B	108.0	O12—P1—C1	107.92 (8)
N11—C16—C15	109.52 (15)	O13—P1—C1	105.87 (8)
N11—C16—H16A	109.8	O22—P2—O21	116.20 (8)
C15—C16—H16A	109.8	O22—P2—O23	110.58 (7)
N11—C16—H16B	109.8	O21—P2—O23	107.33 (8)
C15—C16—H16B	109.8	O22—P2—C2	110.12 (8)
H16A—C16—H16B	108.2	O21—P2—C2	106.51 (8)
C14—C17—C18	114.29 (16)	O23—P2—C2	105.50 (8)
C14—C17—H17A	108.7	P1—O13—H13	109.5
C18—C17—H17A	108.7	P2—O23—H23	109.5
C14—C17—H17B	108.7	C2—C1—P1	111.37 (12)
C18—C17—H17B	108.7	C2—C1—H1A	109.4
H17A—C17—H17B	107.6	P1—C1—H1A	109.4
C19—C18—C17	112.88 (16)	C2—C1—H1B	109.4
C19—C18—H18A	109.0	P1—C1—H1B	109.4
C17—C18—H18A	109.0	H1A—C1—H1B	108.0
C19—C18—H18B	109.0	C1—C2—P2	116.24 (12)
C17—C18—H18B	109.0	C1—C2—H2A	108.2
H18A—C18—H18B	107.8	P2—C2—H2A	108.2
C18—C19—C24	115.05 (16)	C1—C2—H2B	108.2
C18—C19—H19A	108.5	P2—C2—H2B	108.2
C24—C19—H19A	108.5	H2A—C2—H2B	107.4
C18—C19—H19B	108.5	H31—O3—H32	107 (2)
C24—C19—H19B	108.5	O41—O4—H41	72 (2)
H19A—C19—H19B	107.5	O41—O4—H42	75 (2)
C26—N21—C22	111.69 (15)	H41—O4—H42	112 (3)
C26—N21—H21A	109.3	O4—O41—H41	61.3 (16)
C22—N21—H21A	109.3	O4—O41—H42	59.8 (15)
C26—N21—H21B	109.3	H41—O41—H42	98 (3)
C22—N21—H21B	109.3	O51—O5—H51	68 (3)
H21A—N21—H21B	107.9	O51—O5—H52	78 (3)
N21—C22—C23	109.22 (15)	H51—O5—H52	101 (4)
N21—C22—H22A	109.8	O5—O51—H51	58.9 (17)
C23—C22—H22A	109.8	O5—O51—H52	53.8 (16)
N21—C22—H22B	109.8	H51—O51—H52	84 (3)
C23—C22—H22B	109.8

C16—N11—C12—C13	56.4 (2)	C22—C23—C24—C25	−52.4 (2)
N11—C12—C13—C14	−56.2 (2)	C18—C19—C24—C23	−60.2 (2)
C12—C13—C14—C17	−178.88 (16)	C18—C19—C24—C25	177.84 (16)
C12—C13—C14—C15	56.5 (2)	C23—C24—C25—C26	51.4 (2)
C17—C14—C15—C16	177.95 (16)	C19—C24—C25—C26	174.59 (16)
C13—C14—C15—C16	−58.1 (2)	C22—N21—C26—C25	59.5 (2)
C12—N11—C16—C15	−57.2 (2)	C24—C25—C26—N21	−55.5 (2)
C14—C15—C16—N11	58.6 (2)	O11—P1—C1—C2	−177.70 (13)
C15—C14—C17—C18	−66.4 (2)	O12—P1—C1—C2	−52.92 (15)
C13—C14—C17—C18	171.71 (16)	O13—P1—C1—C2	65.02 (15)
C14—C17—C18—C19	−175.63 (16)	P1—C1—C2—P2	179.53 (10)
C17—C18—C19—C24	−176.98 (17)	O22—P2—C2—C1	52.81 (16)
C26—N21—C22—C23	−59.66 (19)	O21—P2—C2—C1	179.60 (14)
N21—C22—C23—C24	56.5 (2)	O23—P2—C2—C1	−66.54 (16)
C22—C23—C24—C19	−174.92 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O22ⁱ	0.84	1.74	2.568 (2)	170
O23—H23···O12ⁱⁱ	0.84	1.76	2.598 (2)	173
O3—H31···O4	0.85 (2)	1.98 (2)	2.816 (3)	168 (2)
O3—H32···O11	0.85 (2)	1.91 (2)	2.740 (2)	167 (2)
O4—H41···O11ⁱ	0.85 (2)	1.91 (2)	2.756 (3)	174 (2)
O4—H42···O21ⁱⁱⁱ	0.85 (2)	1.82 (2)	2.665 (2)	172 (3)
O5—H51···O3	0.85 (4)	2.09 (4)	2.813 (4)	143 (3)
O5—H52···O11^iv	0.85 (3)	1.97 (3)	2.802 (4)	168 (3)
N11—H11A···O12	0.92	1.77	2.691 (2)	177
N11—H11B···O4	0.92	1.83	2.740 (3)	172
N21—H21A···O21^v	0.92	1.82	2.732 (2)	172
N21—H21B···O3^vi	0.92	1.89	2.800 (3)	169

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

Experimental details

	(18)	(17)
Crystal data
Chemical formula	C₄H₁₂N₂·C₂H₆O₆P₂	(C₁₃H₂₈N₂)·(C₂H₆O₆P₂)·2.8(H₂O)
M_r	276.16	450.01
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	150	120
a, b, c (Å)	7.3914 (6), 9.3343 (7), 9.3590 (6)	6.1218 (2), 20.6215 (7), 18.1831 (7)
β (°)	107.291 (4)	99.942 (2)
V (Å³)	616.53 (8)	2260.98 (14)
Z	2	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.37	0.24
Crystal size (mm)	0.20 × 0.06 × 0.02	0.30 × 0.12 × 0.12

Data collection
Diffractometer	Kappa-CCD diffractometer	Kappa-CCD diffractometer
Absorption correction	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	Multi-scan DENZO-SMN (Otwinowski & Minor, 1997)
T_min, T_max	0.930, 0.993	0.932, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	3237, 1401, 947	13672, 6599, 4617
R_int	0.057	0.033
(sin θ/λ)_max (Å⁻¹)	0.647	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.123, 1.04	0.051, 0.114, 1.02
No. of reflections	1401	6599
No. of parameters	74	284
No. of restraints	0	6
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.43	0.40, −0.39

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

Hydrogen-bond geometry (Å, º) for (18) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.84	1.73	2.562 (2)	169
N1—H1C···O2ⁱⁱ	0.92	1.82	2.735 (3)	177
N1—H1D···O1	0.92	1.72	2.635 (3)	175
C2—H2A···O1ⁱⁱⁱ	0.99	2.37	3.166 (4)	136
C2—H2B···O3^iv	0.99	2.36	3.285 (5)	155

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

Hydrogen-bond geometry (Å, º) for (17) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O22ⁱ	0.84	1.74	2.568 (2)	170
O23—H23···O12ⁱⁱ	0.84	1.76	2.598 (2)	173
O3—H31···O4	0.85 (2)	1.98 (2)	2.816 (3)	168 (2)
O3—H32···O11	0.85 (2)	1.91 (2)	2.740 (2)	167 (2)
O4—H41···O11ⁱ	0.85 (2)	1.91 (2)	2.756 (3)	174 (2)
O4—H42···O21ⁱⁱⁱ	0.85 (2)	1.82 (2)	2.665 (2)	172 (3)
O5—H51···O3	0.85 (4)	2.09 (4)	2.813 (4)	143 (3)
O5—H52···O11^iv	0.85 (3)	1.97 (3)	2.802 (4)	168 (3)
N11—H11A···O12	0.92	1.77	2.691 (2)	177
N11—H11B···O4	0.92	1.83	2.740 (3)	172
N21—H21A···O21^v	0.92	1.82	2.732 (2)	172
N21—H21B···O3^vi	0.92	1.89	2.800 (3)	169

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

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