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In the title compound, C13H16N22+·2C2H4O5P-, the cation lies across a twofold rotation axis in space group Fdd2. The anions are linked into molecular ladders by two O-H...O hydrogen bonds [H...O = 1.73 and 1.77 Å, O...O = 2.538 (2) and 2.598 (3) Å, and O-H...O = 160 and 170°], these ladders are linked into sheets by a single type of N-H...O hydrogen bond [H...O = 1.75 Å, N...O = 2.624 (3) Å and N-H...O = 171°] and the sheets are linked into a three-dimensional framework by a single type of C-H...O hydrogen bond [H...O = 2.48 Å, C...O = 3.419 (4) Å and C-H...O = 167°].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011818/sk1644sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011818/sk1644Isup2.hkl
Contains datablock I

CCDC reference: 219582

Comment top

We have recently described the supramolecular structures of the adducts formed by carboxymethylphosphonic acid [phosphonoacetic acid, HOOCCH2P(O)(OH)2] with 4,4'-bipyridyl (NC5H4—C5H4N), where a 1:1 adduct is formed, and 1,2-bis(4-pyridyl)ethane (NC5H4—CH2CH2—C5H4N), where a 1:2 adduct is formed (Bowes et al. 2003). These two adducts are both salts, with constitutions C10H9N2+·C2H4O5P and C12H14N22+·2C2H4O5P, respectively. In the 4,4'-bipyridyl adduct, the anions form simple C(4) chains, which are linked by the cations into sheets of R66(38) rings, which in turn are linked by multiple C—H···O hydrogen bonds. In the 1,2-bis(4-pyridyl) adduct, on the other hand, the anions alone form sheets of alternating R22(12) and R66(28) rings, which are linked by the cations into a three-dimensional framework. In continuation of this study, we have now prepared and structurally characterized the title compound, (I), the adduct formed between 4,4'-trimethylenedipyridine and carboxymethylphosphonic acid.

Compound (I) (Fig. 1) is a salt, [HNC5H4(CH2)3C5H4NH]2+·2[HOOCCH2P(O)2(OH)], in which complete transfer of H atoms, to the N atome from one of the phosphonate O atoms, has occurred. The cation lies across a twofold rotation axis in space group Fdd2, and for the reference cation this axis was selected as that along (1/2, 1/2, z). The anion lies in a general position. In the anion, the P—O and C—O distances (Table 1) are fully consistent with the H-atom locations deduced from difference maps. In the cation, the central C14—C17—C18—C17i—C14i fragment [symmetry code: (i) 1 − x, 1 − y, z] is effectively planar, with an all-trans conformation (Table 1), but the pyridinium ring is rotated out of this plane. All other bond lengths and angles have unexceptional values.

The ions are linked by a small number of hydrogen bonds (Table 2) into a single three-dimensional framework, within which it is possible to identify substructures in one and two dimensions. The anions alone form a one-dimensional substructure in the form of a molecular ladder, or chain of edge-fused rings. The anions and cations are linked into sheets by a combination of all of the hard (Desiraju & Steiner, 1999) hydrogen bonds, all of which have D···A distances that are short for their types, and the sheets are themselves linked into a continuous framework by a single soft C—H···O hydrogen bond.

Phosphonic acid atom O3 in the anion at (x, y, z) acts as a hydrogen-bond donor to phosphonate atom O4 in the anion at (x, y, 1 + z), so generating by translation a C(4) chain running parallel to the [001] direction. In addition, carboxyl atom O1 at (x, y, z) acts as a hydrogen-bond donor to phosphonate atom O5 at (1 − x, 0.5 − y, −0.5 + z), so producing a C(6) chain parallel to [001] and generated by the 21 screw axis along (1/2, 1/4, z). The combination of the C(4) and C(6) motifs generates a molecular ladder along [001] (Fig. 2), which can alternatively be regarded as a chain of edge-fused R33(16) rings. The anion substructure thus contains two of the three hydrogen-bonded motifs most characteristic of phosphonic acids and phosphonate anions, but the third such motif, R22(8) rings, is absent.

There are eight [001] ladders running through each unit cell, viz. two each generated by screw axes at x = 0, 1/4, 0.5 and 0.75. For each of these values of x, the anion ladders are linked by cations, via N—H···O hydrogen bonds, into (100) sheets. The N atoms at (x, y, z) and (1 − x, 1 − y, z) are both components of the cation lying across the twofold rotation axis along (1/2, 1/2, z). These atoms act as hydrogen-bond donors to phosphonate atoms O5 in the anions at (x, y, z) and (1 − x, 1 − y, z), respectively, which lie in the anion ladders along (1/2, 1/4, z) and ().5, 3/4, z), respectively. Propagation of these hydrogen bonds thus links all of the cations lying across rotation axes having x = 1/2, and all of the anion ladders generated by 21 axes having x = 1/2, into a (100) sheet built from R66(40) rings (Fig. 3).

Four (100) sheets pass through each unit cell, and these sheets are linked by a single C—H···O hydrogen bond (Table 2) into a single three-dimensional framework. Atoms C13 at (x, y, z) and (1 − x, 1 − y, z), which are components of the cation lying across the twofold rotation axis along (1/2, 1/2, z), act as hydrogen-bond donors, respectively, to phosphonate atoms O4 in the anions at (0.25 + x, 0.75 − y, −0.25 + z) and (0.75 − x, 0.25 + y, −0.25 + z). These two anions lie, respectively, in the (100) sheets generated by the axes at x = 0.75 and 1/4, and propagation by the space group of this single soft hydrogen bond links all of the (100) sheets into a single framework.

Thus, a single type of hydrogen bond, namely O—H···O, gives rise to a one-dimensional substructure, the combination of two types of hydrogen bond, namely O—H···O and N—H···O, gives rise to a two-dimensional sub-structure, and the combination of three types of hydrogen bond, namely O—H···O, N—H···O and C—H···O, generates the entire three-dimensional structure. The anion substructure, in particular, differs from those found in the corresponding salts formed from 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane.

In contrast to (I), the simple salt 4,4'-trimethylenedipyridinium dinitrate, (II) (Lee et al., 2003), whose constitution precludes the formation of O—H···O hydrogen bonds, contains just three-component aggregates containing a pair of N—H···O hydrogen bonds, but with no significant C—H···O hydrogen bonds between these aggregates. On the other hand, there are strong electrostatic interactions between adjacent pyridinium rings and nitrate ions, whose planes are nearly parallel to one another. Note also the contrast between (II) and the hydrated nitrate, (III), formed by 1,2-bis(4-pyridyl)ethane, which contains a monoprotonated diamine (Almeida Paz et al., 2003). In (III), the cations are linked into chains by N—H···N hydrogen bonds, and the nitrate ions and water molecules form hydrogen-bonded layers, but there are no hard hydrogen bonds between cations and anions.

Experimental top

Stoichiometric quantities of 4,4'-trimethylenedipyridine and carboxymethylphosphonic acid (both purchased from Aldrich) were dissolved separately in methanol. The solutions were mixed and the mixture was set aside to crystallize, providing analytically pure (I). Analysis found: C 42.8, H 5.2, N 5.8%; C17H24N2O10P2 requires: C 42.7, H 5.1, N 5.9%. Crystals suitable for single-crystal X-ray diffraction were selected directly from the analytical sample.

Refinement top

Crystals of (I) are orthorhombic and the space group Fdd2 was assigned uniquely from the systematic absences. All H atoms were located from difference maps and were subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.99 Å (CH2), N—-H distances of 0.88 Å, and O—H 0.84 Å. The correct orientation of the structure with respect to the polar axis was established using the Flack (1983) parameter.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The independent components of (I), showing the atom-labelling scheme. Displacement ellipsoids have been drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a chain of edge-fused R33(16) rings containing anions only. For clarity, H atoms bonded to C atoms, and the unit-cell box, have been omitted. Atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (x, y, 1 + z), (x, y, −1 + z), (1 − x, 0.5 − y, −0.5 + z) and (1 − x, 0.5 − y, 0.5 + z), respectively.
[Figure 3] Fig. 3. Stereoview of part of the crystal structure of (I), showing the formation via the hard hydrogen bonds of the (100) sheet at x = 0.5.
[Figure 4] Fig. 4. Stereoview of part of the crystal structure of (I), showing the linking of the (100) sheets into a single framework by a single C—H···O hydrogen bond.
4,4'-Trimethylenedipyridinium bis[carboxymethylphosphonate(1-)] top
Crystal data top
C13H16N22+·2C2H4O5PF(000) = 2000
Mr = 478.32Dx = 1.470 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 2418 reflections
a = 27.366 (2) Åθ = 2.9–27.5°
b = 32.347 (2) ŵ = 0.26 mm1
c = 4.8818 (3) ÅT = 150 K
V = 4321.4 (5) Å3Needle, colourless
Z = 80.16 × 0.06 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
2418 independent reflections
Radiation source: fine-focus sealed X-ray tube1864 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.084
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan
(DENZO–SMN; Otwinowski & Minor, 1997)
h = 3534
Tmin = 0.886, Tmax = 0.990k = 3742
7640 measured reflectionsl = 66
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044 w = 1/[σ2(Fo2) + (0.0427P)2 + 0.6064P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.103(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.30 e Å3
2418 reflectionsΔρmin = 0.24 e Å3
144 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.00136 (19)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1029 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.06 (13)
Crystal data top
C13H16N22+·2C2H4O5PV = 4321.4 (5) Å3
Mr = 478.32Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 27.366 (2) ŵ = 0.26 mm1
b = 32.347 (2) ÅT = 150 K
c = 4.8818 (3) Å0.16 × 0.06 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
2418 independent reflections
Absorption correction: multi-scan
(DENZO–SMN; Otwinowski & Minor, 1997)
1864 reflections with I > 2σ(I)
Tmin = 0.886, Tmax = 0.990Rint = 0.084
7640 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.30 e Å3
S = 1.05Δρmin = 0.24 e Å3
2418 reflectionsAbsolute structure: Flack (1983), 1029 Friedel pairs
144 parametersAbsolute structure parameter: 0.06 (13)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
P10.39420 (3)0.27700 (2)0.87865 (14)0.0252 (2)
O10.49101 (8)0.21961 (7)0.7812 (5)0.0347 (5)
O20.43769 (8)0.18466 (7)0.5217 (5)0.0380 (6)
O30.35287 (7)0.28358 (7)1.0967 (4)0.0308 (5)
O40.37252 (7)0.28622 (7)0.6044 (4)0.0328 (5)
O50.43899 (7)0.30201 (6)0.9515 (4)0.0293 (5)
C10.44687 (11)0.20679 (9)0.7158 (6)0.0285 (7)
C20.40885 (11)0.22249 (9)0.9112 (7)0.0289 (7)
N10.46225 (10)0.35877 (7)0.5904 (6)0.0348 (6)
C120.50721 (11)0.37515 (9)0.5786 (7)0.0326 (7)
C130.51670 (11)0.40816 (9)0.4078 (6)0.0301 (7)
C140.47936 (10)0.42485 (9)0.2468 (6)0.0261 (7)
C150.43317 (11)0.40659 (9)0.2642 (7)0.0318 (7)
C160.42598 (11)0.37327 (10)0.4362 (6)0.0368 (8)
C170.48856 (11)0.46211 (8)0.0728 (6)0.0278 (7)
C180.50000.50000.2493 (9)0.0280 (9)
H10.51120.21080.66550.052*
H30.36460.28071.25460.046*
H2A0.42030.21731.10050.035*
H2B0.37850.20630.88390.035*
H1A0.45660.33800.70240.042*
H120.53260.36400.68840.039*
H130.54870.41960.39960.036*
H150.40680.41710.15810.038*
H160.39470.36050.44470.044*
H17A0.45940.46780.04110.033*
H17B0.51640.45660.05160.033*
H18A0.47160.50610.36860.034*0.50
H18B0.52840.49390.36860.034*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0222 (4)0.0300 (4)0.0234 (4)0.0018 (3)0.0007 (3)0.0006 (3)
O10.0281 (12)0.0411 (13)0.0350 (13)0.0010 (10)0.0050 (10)0.0066 (10)
O20.0375 (13)0.0375 (12)0.0389 (13)0.0023 (10)0.0009 (11)0.0095 (11)
O30.0250 (10)0.0444 (12)0.0229 (11)0.0042 (10)0.0005 (9)0.0015 (10)
O40.0300 (11)0.0446 (12)0.0237 (11)0.0066 (9)0.0014 (10)0.0031 (10)
O50.0239 (10)0.0276 (11)0.0365 (13)0.0014 (9)0.0023 (9)0.0016 (9)
C10.0283 (16)0.0267 (15)0.0306 (17)0.0012 (13)0.0009 (13)0.0041 (13)
C20.0320 (15)0.0254 (14)0.0293 (17)0.0035 (13)0.0080 (14)0.0012 (12)
N10.0449 (16)0.0236 (13)0.0360 (15)0.0021 (12)0.0051 (14)0.0022 (12)
C120.0358 (17)0.0260 (15)0.0361 (18)0.0028 (13)0.0002 (14)0.0025 (14)
C130.0285 (14)0.0256 (15)0.0363 (18)0.0011 (12)0.0008 (15)0.0005 (13)
C140.0312 (16)0.0191 (15)0.0281 (16)0.0012 (12)0.0001 (13)0.0036 (12)
C150.0280 (15)0.0306 (16)0.0369 (17)0.0013 (14)0.0014 (14)0.0014 (14)
C160.0320 (18)0.0321 (17)0.046 (2)0.0069 (14)0.0079 (16)0.0017 (14)
C170.0268 (16)0.0228 (15)0.0338 (18)0.0043 (12)0.0017 (13)0.0022 (12)
C180.031 (2)0.022 (2)0.031 (2)0.0005 (18)0.0000.000
Geometric parameters (Å, º) top
P1—O31.568 (2)C12—H120.95
P1—O41.495 (2)C13—C141.398 (4)
P1—O51.511 (2)C13—H130.95
P1—C21.815 (3)C14—C151.398 (4)
C1—O11.317 (4)C14—C171.496 (4)
O1—H10.84C15—C161.380 (4)
C1—O21.214 (4)C15—H150.95
O3—H30.84C16—H160.95
C1—C21.500 (4)C17—C181.531 (4)
C2—H2A0.99C17—H17A0.99
C2—H2B0.99C17—H17B0.99
N1—C161.331 (4)C18—C17i1.531 (4)
N1—C121.341 (4)C18—H18A0.99
N1—H1A0.88C18—H18B0.99
C12—C131.379 (4)
O4—P1—O5115.20 (12)C12—C13—H13120.0
O4—P1—O3107.15 (12)C14—C13—H13120.0
O5—P1—O3110.65 (11)C13—C14—C15117.6 (3)
O4—P1—C2111.10 (14)C13—C14—C17120.5 (3)
O5—P1—C2108.68 (13)C15—C14—C17121.8 (3)
O3—P1—C2103.41 (13)C16—C15—C14119.7 (3)
C1—O1—H1109.5C16—C15—H15120.1
P1—O3—H3109.5C14—C15—H15120.1
O2—C1—O1124.4 (3)N1—C16—C15120.8 (3)
O2—C1—C2123.6 (3)N1—C16—H16119.6
O1—C1—C2112.1 (3)C15—C16—H16119.6
C1—C2—P1115.3 (2)C14—C17—C18111.1 (2)
C1—C2—H2A108.5C14—C17—H17A109.4
P1—C2—H2A108.5C18—C17—H17A109.4
C1—C2—H2B108.5C14—C17—H17B109.4
P1—C2—H2B108.5C18—C17—H17B109.4
H2A—C2—H2B107.5H17A—C17—H17B108.0
C16—N1—C12121.4 (3)C17i—C18—C17111.5 (3)
C16—N1—H1A119.3C17i—C18—H18A109.3
C12—N1—H1A119.3C17—C18—H18A109.3
N1—C12—C13120.3 (3)C17i—C18—H18B109.3
N1—C12—H12119.9C17—C18—H18B109.3
C13—C12—H12119.8H18A—C18—H18B108.0
C12—C13—C14120.1 (3)
C13—C14—C17—C1865.0 (3)C14—C17—C18—C17i177.8 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O5ii0.841.772.598 (3)170
O3—H3···O4iii0.841.732.537 (3)160
N1—H1A···O50.881.752.624 (3)171
C13—H13···O4iv0.952.483.419 (4)167
Symmetry codes: (ii) x+1, y+1/2, z1/2; (iii) x, y, z+1; (iv) x+1/4, y+3/4, z1/4.

Experimental details

Crystal data
Chemical formulaC13H16N22+·2C2H4O5P
Mr478.32
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)150
a, b, c (Å)27.366 (2), 32.347 (2), 4.8818 (3)
V3)4321.4 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.16 × 0.06 × 0.06
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO–SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.886, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
7640, 2418, 1864
Rint0.084
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.103, 1.05
No. of reflections2418
No. of parameters144
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.24
Absolute structureFlack (1983), 1029 Friedel pairs
Absolute structure parameter0.06 (13)

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
P1—O31.568 (2)C1—O11.317 (4)
P1—O41.495 (2)C1—O21.214 (4)
P1—O51.511 (2)
C13—C14—C17—C1865.0 (3)C14—C17—C18—C17i177.8 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O5ii0.841.772.598 (3)170
O3—H3···O4iii0.841.732.537 (3)160
N1—H1A···O50.881.752.624 (3)171
C13—H13···O4iv0.952.483.419 (4)167
Symmetry codes: (ii) x+1, y+1/2, z1/2; (iii) x, y, z+1; (iv) x+1/4, y+3/4, z1/4.
 

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