Compounds (Ia), (Ib) (II) and (III) were obtained according to
previously described procedures (Sołoducho et al., 1997).
Crystals of
(Ia) and (Ib) were grown in one vessel upon recrystallization
from aqueous solution by slow evaporation at room temperature. Crystals of
(II) were obtained in a similar way. To obtain crystals of (III), the solid
crude product formed upon standing of the reaction mixture was dissolved in
water and the solution was allowed to evaporate slowly. The X-ray data for
(Ia) were collected at room temperature (294 K), owing to twinning of
the crystal seen in the diffraction pattern at low temperature (100 K).
Spectroscopic analysis for (I) (D2O, pH = 5.50): 1H NMR (reference TMS, δ,
p.p.m.): H1 3.86 (3JPH = 19.6 Hz), H21 8.00, H41 7.71, H51 7.57,
H61 7.81; 13C NMR (reference TMS, δ, p.p.m.): C1 51.16 (1JPC =
129.9 Hz), C2 124.83, C3 146.80 (3JPC = 4.2 Hz), C4 127.90, C5
126.76, C6 128.20; 31P NMR (reference 85% H3PO4, p.p.m.): δp 14.54.
Spectroscopic analysis for (II) (D2O, pH = 1.88): 1H NMR (reference TMS,
δ, p.p.m.): H1 3.97 (3JPH = 20.1 Hz), H41 7.40, H51 7.31, H61
7.62; 13C NMR (reference TMS, δ, p.p.m.): C1 50.57 (1JPC = 133.6 Hz), C2 133.51, C3 141.30 (3JPC = 4.50 Hz), C4 122.19, C5 124.59,
C6 133.76; 31P NMR (reference 85% H3PO4, p.p.m.): δp 14.38.
Spectroscopic analysis for (III) (D2O, pH = 1.92): 1H NMR (reference TMS,
δ, p.p.m.): H1 3.90 (3JPH = 19.7 Hz), H21 7.84, H41 7.36, H51
7.46; 13C NMR (reference TMS, δ, p.p.m.): C1 50.83 (1JPC = 134.6 Hz), C2 128.87, C3 144.71 (3JPC = 4.50 Hz), C4 126.31, C5 128.13,
C6 132.67; 31P NMR (reference 85% H3PO4, p.p.m.): δp 14.61.
The 6-chloropyridin-3-aminium cation in (III) is disordered over two positions
[site-occupation factors 0.57 (1) and 0.43 (1)], corresponding to its two
different orientations (Fig. 2). In the final model, the equivalent bond
lengths and angles of the two positions were restrained to be equal using the
SAME instruction [SHELXL97 (Sheldrick, 2008)]. The positions of
the Cl
atoms (Cl2 and Cl20) were refined with the same fractional coordinates and
anisotropic displacement parameters (constraints were applied with the EXYZ
and EADP instructions in SHELXL97).
Non-H atoms were refined anisotropically, except for the C and N atoms of both
positions of the disordered 6-chloropyridin-3-aminium cation in (III). All H
atoms were found in difference Fourier maps. Atom H5 in (III) is located on a
twofold axis between two anions, 1.20 (1) Å from each O5 atom, and was
refined isotropically. Atom H2W bound to O1W in (Ia) was
refined with a site-occupation factor of 0.5, which results in two alternative
positions for this atom, related by the action of a twofold axis (Fig. 1). In
the final refinement cycles, all water H atoms in (Ia) were refined
with O—H and H···H distances restrained to 0.84 and 1.36 Å, respectively,
and with Uiso(H) = 1.5Ueq(O). All remaining H atoms were
treated as riding atoms in geometrically optimized positions, with C—H =
0.93–1.00 Å, N—H = 0.86–0.91 Å and O—H = 0.82–0.84 Å, and with
Uiso(H) = 1.2Ueq(C,N) for CH and NH, or 1.5Ueq(N,O)
for NH3 and OH. Atom H2N in (III) was refined with a site-occupation factor
of 0.5.
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(Ia) hydrogen {phosphono[(pyridin-1-ium-3-yl)amino]methyl}phosphonate
monohydrate
top
Crystal data top
C6H10N2O6P2·H2O | F(000) = 592 |
Mr = 286.12 | Dx = 1.779 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 4599 reflections |
a = 9.068 (3) Å | θ = 3.0–36.6° |
b = 7.513 (2) Å | µ = 0.44 mm−1 |
c = 16.126 (4) Å | T = 294 K |
β = 103.55 (3)° | Plate, colourless |
V = 1068.1 (5) Å3 | 0.38 × 0.30 × 0.15 mm |
Z = 4 | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 2907 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2229 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 30.0°, θmin = 3.0° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −11→12 |
Tmin = 0.880, Tmax = 1.000 | k = −9→10 |
9984 measured reflections | l = −22→17 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0497P)2 + 1.2174P] where P = (Fo2 + 2Fc2)/3 |
2907 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.52 e Å−3 |
4 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C6H10N2O6P2·H2O | V = 1068.1 (5) Å3 |
Mr = 286.12 | Z = 4 |
Monoclinic, P2/n | Mo Kα radiation |
a = 9.068 (3) Å | µ = 0.44 mm−1 |
b = 7.513 (2) Å | T = 294 K |
c = 16.126 (4) Å | 0.38 × 0.30 × 0.15 mm |
β = 103.55 (3)° | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 2907 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | 2229 reflections with I > 2σ(I) |
Tmin = 0.880, Tmax = 1.000 | Rint = 0.034 |
9984 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 4 restraints |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.52 e Å−3 |
2907 reflections | Δρmin = −0.27 e Å−3 |
164 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
P1 | 0.56863 (8) | 0.48611 (10) | 0.64225 (4) | 0.03476 (19) | |
P2 | 0.54692 (8) | 0.89445 (10) | 0.65678 (5) | 0.0400 (2) | |
O1 | 0.4872 (2) | 0.3430 (3) | 0.58346 (12) | 0.0459 (5) | |
O2 | 0.7311 (2) | 0.5206 (3) | 0.63803 (12) | 0.0414 (5) | |
O3 | 0.5568 (2) | 0.4433 (3) | 0.73439 (12) | 0.0413 (5) | |
H3 | 0.6325 | 0.4807 | 0.7683 | 0.062* | |
O4 | 0.5588 (2) | 0.8874 (3) | 0.75121 (14) | 0.0498 (5) | |
O5 | 0.4358 (3) | 1.0345 (3) | 0.6104 (2) | 0.0681 (8) | |
H5 | 0.4797 | 1.1301 | 0.6113 | 0.102* | |
O6 | 0.7007 (2) | 0.9224 (3) | 0.63428 (13) | 0.0467 (5) | |
H6 | 0.7692 | 0.9042 | 0.6766 | 0.070* | |
N1 | 0.3097 (3) | 0.6715 (3) | 0.62392 (15) | 0.0405 (6) | |
H1N | 0.3028 | 0.6332 | 0.6731 | 0.049* | |
N2 | −0.0895 (3) | 0.7016 (4) | 0.5358 (2) | 0.0556 (7) | |
H2N | −0.1711 | 0.6745 | 0.5514 | 0.067* | |
C1 | 0.4619 (3) | 0.6894 (4) | 0.60906 (17) | 0.0341 (5) | |
H1 | 0.4503 | 0.7005 | 0.5473 | 0.041* | |
C2 | 0.0424 (3) | 0.6713 (4) | 0.5892 (2) | 0.0447 (7) | |
H21 | 0.0448 | 0.6233 | 0.6426 | 0.054* | |
C3 | 0.1779 (3) | 0.7103 (4) | 0.56656 (17) | 0.0346 (6) | |
C4 | 0.1690 (3) | 0.7876 (4) | 0.48699 (19) | 0.0419 (7) | |
H41 | 0.2570 | 0.8191 | 0.4704 | 0.050* | |
C5 | 0.0292 (4) | 0.8170 (5) | 0.4330 (2) | 0.0526 (8) | |
H51 | 0.0228 | 0.8667 | 0.3795 | 0.063* | |
C6 | −0.1016 (4) | 0.7728 (5) | 0.4583 (3) | 0.0604 (10) | |
H61 | −0.1964 | 0.7921 | 0.4222 | 0.072* | |
O1W | 0.2500 | 0.4159 (6) | 0.7500 | 0.0778 (12) | |
O2W | 0.2500 | 0.0580 (6) | 0.7500 | 0.1015 (16) | |
H1W | 0.2500 | 0.3039 (10) | 0.7500 | 0.152* | |
H2W | 0.338 (4) | 0.4501 (19) | 0.750 (9) | 0.152* | 0.50 |
H3W | 0.317 (4) | −0.0072 (16) | 0.737 (4) | 0.152* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0338 (4) | 0.0351 (4) | 0.0333 (3) | 0.0017 (3) | 0.0036 (3) | 0.0037 (3) |
P2 | 0.0305 (4) | 0.0360 (4) | 0.0494 (4) | 0.0000 (3) | 0.0008 (3) | 0.0060 (3) |
O1 | 0.0539 (13) | 0.0392 (11) | 0.0390 (11) | −0.0043 (10) | −0.0003 (9) | −0.0002 (9) |
O2 | 0.0338 (10) | 0.0509 (12) | 0.0399 (10) | 0.0038 (9) | 0.0097 (8) | 0.0072 (9) |
O3 | 0.0352 (10) | 0.0516 (12) | 0.0359 (10) | 0.0005 (9) | 0.0059 (8) | 0.0091 (9) |
O4 | 0.0380 (11) | 0.0612 (14) | 0.0507 (12) | −0.0046 (10) | 0.0115 (9) | −0.0104 (11) |
O5 | 0.0400 (13) | 0.0420 (13) | 0.108 (2) | 0.0007 (10) | −0.0106 (13) | 0.0166 (14) |
O6 | 0.0354 (11) | 0.0561 (13) | 0.0455 (11) | −0.0093 (10) | 0.0034 (9) | 0.0118 (10) |
N1 | 0.0304 (12) | 0.0504 (14) | 0.0401 (12) | 0.0005 (11) | 0.0069 (10) | 0.0119 (11) |
N2 | 0.0327 (14) | 0.0644 (19) | 0.0705 (19) | −0.0053 (13) | 0.0135 (13) | −0.0158 (15) |
C1 | 0.0270 (13) | 0.0389 (14) | 0.0352 (13) | 0.0009 (11) | 0.0045 (10) | 0.0071 (11) |
C2 | 0.0363 (15) | 0.0466 (17) | 0.0517 (17) | −0.0049 (13) | 0.0117 (13) | −0.0060 (14) |
C3 | 0.0276 (13) | 0.0339 (14) | 0.0410 (14) | −0.0018 (10) | 0.0056 (11) | −0.0028 (11) |
C4 | 0.0356 (15) | 0.0460 (17) | 0.0425 (15) | −0.0011 (12) | 0.0059 (12) | 0.0002 (13) |
C5 | 0.0514 (19) | 0.058 (2) | 0.0414 (16) | 0.0082 (16) | −0.0037 (14) | −0.0029 (15) |
C6 | 0.0318 (17) | 0.063 (2) | 0.075 (2) | 0.0075 (15) | −0.0113 (16) | −0.0161 (19) |
O1W | 0.113 (4) | 0.068 (2) | 0.069 (2) | 0.000 | 0.054 (3) | 0.000 |
O2W | 0.133 (5) | 0.071 (3) | 0.123 (4) | 0.000 | 0.076 (4) | 0.000 |
Geometric parameters (Å, º) top
P1—O1 | 1.507 (2) | N2—C6 | 1.339 (5) |
P1—O2 | 1.513 (2) | N2—H2N | 0.86 |
P1—O3 | 1.548 (2) | C1—H1 | 0.98 |
P1—C1 | 1.820 (3) | C2—C3 | 1.393 (4) |
P2—O4 | 1.502 (2) | C2—H21 | 0.93 |
P2—O5 | 1.526 (2) | C3—C4 | 1.393 (4) |
P2—O6 | 1.536 (2) | C4—C5 | 1.377 (4) |
P2—C1 | 1.811 (3) | C4—H41 | 0.93 |
O3—H3 | 0.82 | C5—C6 | 1.382 (5) |
O5—H5 | 0.82 | C5—H51 | 0.93 |
O6—H6 | 0.82 | C6—H61 | 0.93 |
N1—C1 | 1.462 (3) | O1W—H1W | 0.84 |
N1—C3 | 1.360 (4) | O1W—H2W | 0.84 |
N1—H1N | 0.86 | O2W—H3W | 0.84 |
N2—C2 | 1.319 (4) | | |
| | | |
O1—P1—O2 | 115.63 (13) | P1—C1—N1 | 109.38 (18) |
O1—P1—O3 | 108.77 (12) | P2—C1—N1 | 109.44 (19) |
O2—P1—O3 | 111.45 (11) | N1—C1—H1 | 107.1 |
O1—P1—C1 | 105.38 (13) | P2—C1—H1 | 107.1 |
O2—P1—C1 | 107.42 (12) | P1—C1—H1 | 107.1 |
O3—P1—C1 | 107.75 (12) | N2—C2—C3 | 120.9 (3) |
O4—P2—O5 | 113.77 (16) | N2—C2—H21 | 119.6 |
O4—P2—O6 | 113.01 (12) | C3—C2—H21 | 119.6 |
O5—P2—O6 | 108.81 (14) | N1—C3—C2 | 117.7 (3) |
O4—P2—C1 | 108.85 (13) | N1—C3—C4 | 124.6 (3) |
O5—P2—C1 | 102.22 (14) | C2—C3—C4 | 117.7 (3) |
O6—P2—C1 | 109.60 (13) | C5—C4—C3 | 119.7 (3) |
P1—O3—H3 | 109.5 | C5—C4—H41 | 120.2 |
P2—O5—H5 | 109.5 | C3—C4—H41 | 120.2 |
P2—O6—H6 | 109.5 | C4—C5—C6 | 120.1 (3) |
C1—N1—C3 | 125.6 (2) | C4—C5—H51 | 119.9 |
C3—N1—H1N | 117.2 | C6—C5—H51 | 119.9 |
C1—N1—H1N | 117.2 | N2—C6—C5 | 118.8 (3) |
C2—N2—C6 | 122.8 (3) | N2—C6—H61 | 120.6 |
C2—N2—H2N | 118.6 | C5—C6—H61 | 120.6 |
C6—N2—H2N | 118.6 | H1W—O1W—H2W | 107.8 (11) |
P1—C1—P2 | 116.41 (14) | | |
| | | |
O1—P1—C1—P2 | −170.95 (14) | C3—N1—C1—P1 | −131.5 (3) |
O2—P1—C1—P2 | −47.14 (18) | C3—N1—C1—P2 | 99.9 (3) |
O3—P1—C1—P2 | 73.05 (17) | C6—N2—C2—C3 | −1.0 (5) |
O4—P2—C1—P1 | −63.49 (18) | C1—N1—C3—C2 | 174.8 (3) |
O5—P2—C1—P1 | 175.87 (17) | C1—N1—C3—C4 | −5.7 (5) |
O6—P2—C1—P1 | 60.57 (18) | N2—C2—C3—N1 | −178.4 (3) |
O1—P1—C1—N1 | 64.4 (2) | N2—C2—C3—C4 | 2.1 (4) |
O2—P1—C1—N1 | −171.79 (18) | N1—C3—C4—C5 | 178.4 (3) |
O3—P1—C1—N1 | −51.6 (2) | C2—C3—C4—C5 | −2.1 (4) |
O4—P2—C1—N1 | 61.1 (2) | C3—C4—C5—C6 | 1.1 (5) |
O5—P2—C1—N1 | −59.5 (2) | C2—N2—C6—C5 | −0.1 (5) |
O6—P2—C1—N1 | −174.80 (17) | C4—C5—C6—N2 | 0.1 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.82 | 1.74 | 2.532 (3) | 162 |
O5—H5···O1ii | 0.82 | 1.67 | 2.424 (3) | 152 |
O6—H6···O4i | 0.82 | 1.72 | 2.519 (3) | 165 |
N1—H1N···O1W | 0.86 | 2.17 | 2.938 (4) | 148 |
N2—H2N···O2iii | 0.86 | 2.16 | 2.911 (4) | 146 |
O1W—H1W···O2W | 0.84 | 1.85 | 2.689 (6) | 180 |
O1W—H2W···O3 | 0.84 | 2.06 | 2.859 (2) | 160 |
O2W—H3W···O4iv | 0.84 | 2.30 | 3.076 (3) | 155 |
O2W—H3W···O5iv | 0.84 | 2.55 | 3.116 (3) | 126 |
C1—H1···O1v | 0.98 | 2.33 | 3.253 (4) | 156 |
C6—H61···O5vi | 0.93 | 2.48 | 3.306 (4) | 148 |
Symmetry codes: (i) −x+3/2, y, −z+3/2; (ii) x, y+1, z; (iii) x−1, y, z; (iv) x, y−1, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y+2, −z+1. |
(Ib) hydrogen {phosphono[(pyridin-1-ium-3-yl)amino]methyl}phosphonate
top
Crystal data top
C6H10N2O6P2 | F(000) = 552 |
Mr = 268.10 | Dx = 1.784 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4018 reflections |
a = 9.172 (3) Å | θ = 4.2–41.9° |
b = 14.802 (4) Å | µ = 0.45 mm−1 |
c = 7.589 (2) Å | T = 120 K |
β = 104.35 (3)° | Needle, colourless |
V = 998.2 (5) Å3 | 0.20 × 0.02 × 0.01 mm |
Z = 4 | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with Onyx CCD camera | 2925 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.168 |
ω and ϕ scans | θmax = 30.1°, θmin = 4.2° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009) | h = −12→12 |
Tmin = 0.954, Tmax = 0.994 | k = −20→20 |
17046 measured reflections | l = −7→10 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 0.82 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
2925 reflections | (Δ/σ)max < 0.001 |
148 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
C6H10N2O6P2 | V = 998.2 (5) Å3 |
Mr = 268.10 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.172 (3) Å | µ = 0.45 mm−1 |
b = 14.802 (4) Å | T = 120 K |
c = 7.589 (2) Å | 0.20 × 0.02 × 0.01 mm |
β = 104.35 (3)° | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with Onyx CCD camera | 2925 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009) | 1307 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.994 | Rint = 0.168 |
17046 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.46 e Å−3 |
2925 reflections | Δρmin = −0.51 e Å−3 |
148 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.78368 (9) | 0.40568 (6) | 0.18642 (9) | 0.01320 (18) | |
P2 | 0.77861 (9) | 0.41123 (6) | 0.59656 (9) | 0.01261 (18) | |
O1 | 0.8594 (2) | 0.49621 (13) | 0.1933 (2) | 0.0144 (5) | |
O2 | 0.6726 (2) | 0.38128 (13) | 0.0103 (2) | 0.0183 (5) | |
O3 | 0.9101 (2) | 0.33353 (12) | 0.2426 (2) | 0.0177 (5) | |
H3 | 0.8758 | 0.2825 | 0.2053 | 0.027* | |
O4 | 0.8730 (2) | 0.33133 (12) | 0.6649 (2) | 0.0174 (5) | |
O5 | 0.6506 (2) | 0.42804 (14) | 0.6912 (2) | 0.0189 (5) | |
H5 | 0.6787 | 0.4121 | 0.8006 | 0.028* | |
O6 | 0.8690 (2) | 0.49965 (13) | 0.6029 (2) | 0.0169 (5) | |
H6 | 0.9546 | 0.4932 | 0.6739 | 0.025* | |
N1 | 0.5901 (3) | 0.31537 (14) | 0.3420 (3) | 0.0131 (5) | |
H1N | 0.6333 | 0.2686 | 0.4056 | 0.016* | |
N2 | 0.2264 (3) | 0.36111 (15) | 0.0378 (3) | 0.0155 (6) | |
H2N | 0.1774 | 0.4073 | −0.0223 | 0.019* | |
C1 | 0.6751 (3) | 0.39968 (18) | 0.3591 (3) | 0.0096 (6) | |
H1 | 0.5999 | 0.4499 | 0.3329 | 0.012* | |
C2 | 0.3675 (3) | 0.37509 (19) | 0.1351 (3) | 0.0129 (7) | |
H21 | 0.4124 | 0.4330 | 0.1366 | 0.016* | |
C3 | 0.4481 (3) | 0.30430 (18) | 0.2340 (3) | 0.0113 (6) | |
C4 | 0.3766 (3) | 0.21973 (19) | 0.2166 (3) | 0.0135 (7) | |
H41 | 0.4296 | 0.1688 | 0.2766 | 0.016* | |
C5 | 0.2307 (4) | 0.20937 (18) | 0.1141 (3) | 0.0157 (6) | |
H51 | 0.1832 | 0.1519 | 0.1050 | 0.019* | |
C6 | 0.1550 (3) | 0.2824 (2) | 0.0256 (3) | 0.0162 (7) | |
H61 | 0.0536 | 0.2770 | −0.0431 | 0.019* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0123 (5) | 0.0153 (4) | 0.0113 (3) | −0.0018 (4) | 0.0017 (3) | 0.0000 (4) |
P2 | 0.0127 (5) | 0.0140 (4) | 0.0102 (3) | −0.0007 (4) | 0.0011 (3) | 0.0002 (4) |
O1 | 0.0169 (13) | 0.0118 (11) | 0.0144 (10) | −0.0037 (9) | 0.0040 (9) | 0.0016 (8) |
O2 | 0.0167 (12) | 0.0284 (13) | 0.0085 (9) | −0.0068 (9) | 0.0005 (8) | −0.0019 (8) |
O3 | 0.0155 (12) | 0.0136 (11) | 0.0235 (11) | −0.0009 (9) | 0.0040 (9) | −0.0032 (9) |
O4 | 0.0199 (13) | 0.0126 (12) | 0.0162 (9) | 0.0012 (9) | −0.0021 (9) | 0.0044 (8) |
O5 | 0.0144 (12) | 0.0327 (14) | 0.0093 (8) | 0.0008 (10) | 0.0023 (8) | 0.0041 (9) |
O6 | 0.0138 (13) | 0.0152 (11) | 0.0175 (11) | −0.0042 (9) | −0.0038 (9) | 0.0027 (9) |
N1 | 0.0122 (14) | 0.0103 (14) | 0.0145 (11) | −0.0007 (10) | −0.0012 (11) | 0.0056 (10) |
N2 | 0.0160 (15) | 0.0123 (14) | 0.0177 (12) | 0.0041 (11) | 0.0034 (11) | 0.0030 (10) |
C1 | 0.0078 (15) | 0.0074 (15) | 0.0114 (12) | −0.0013 (13) | −0.0019 (11) | 0.0026 (12) |
C2 | 0.0101 (17) | 0.0144 (17) | 0.0127 (13) | −0.0038 (13) | −0.0002 (12) | −0.0028 (11) |
C3 | 0.0100 (17) | 0.0140 (17) | 0.0103 (12) | −0.0002 (13) | 0.0036 (12) | 0.0019 (11) |
C4 | 0.0132 (18) | 0.0131 (17) | 0.0155 (14) | −0.0005 (13) | 0.0059 (13) | −0.0009 (13) |
C5 | 0.0181 (18) | 0.0116 (16) | 0.0171 (13) | −0.0060 (15) | 0.0037 (13) | −0.0041 (14) |
C6 | 0.0115 (17) | 0.0242 (19) | 0.0133 (14) | −0.0050 (14) | 0.0038 (13) | −0.0041 (14) |
Geometric parameters (Å, º) top
P1—O1 | 1.504 (2) | N1—H1N | 0.88 |
P1—O2 | 1.5100 (18) | N2—C2 | 1.338 (3) |
P1—O3 | 1.556 (2) | N2—C6 | 1.328 (3) |
P1—C1 | 1.834 (2) | N2—H2N | 0.88 |
P2—O4 | 1.4812 (19) | C1—H1 | 1.00 |
P2—O5 | 1.5405 (19) | C2—C3 | 1.390 (3) |
P2—O6 | 1.544 (2) | C2—H21 | 0.95 |
P2—C1 | 1.825 (2) | C3—C4 | 1.404 (4) |
O3—H3 | 0.84 | C4—C5 | 1.380 (4) |
O5—H5 | 0.84 | C4—H41 | 0.95 |
O6—H6 | 0.84 | C5—C6 | 1.368 (4) |
N1—C1 | 1.460 (3) | C5—H51 | 0.95 |
N1—C3 | 1.366 (3) | C6—H61 | 0.95 |
| | | |
O1—P1—O2 | 116.63 (10) | P1—C1—P2 | 117.34 (14) |
O1—P1—O3 | 107.19 (12) | P1—C1—N1 | 110.51 (17) |
O2—P1—O3 | 111.83 (11) | P2—C1—N1 | 107.66 (16) |
O1—P1—C1 | 110.27 (12) | N1—C1—H1 | 106.9 |
O2—P1—C1 | 104.72 (11) | P2—C1—H1 | 106.9 |
O3—P1—C1 | 105.70 (12) | P1—C1—H1 | 106.9 |
O4—P2—O5 | 114.35 (11) | N2—C2—C3 | 119.6 (3) |
O4—P2—O6 | 113.78 (12) | N2—C2—H21 | 120.2 |
O5—P2—O6 | 108.31 (12) | C3—C2—H21 | 120.2 |
O4—P2—C1 | 112.75 (12) | N1—C3—C2 | 122.3 (3) |
O5—P2—C1 | 101.85 (11) | N1—C3—C4 | 121.1 (2) |
O6—P2—C1 | 104.73 (11) | C2—C3—C4 | 116.6 (3) |
P1—O3—H3 | 109.5 | C5—C4—C3 | 121.1 (3) |
P2—O5—H5 | 109.5 | C5—C4—H41 | 119.4 |
P2—O6—H6 | 109.5 | C3—C4—H41 | 119.4 |
C1—N1—C3 | 124.4 (2) | C6—C5—C4 | 119.5 (3) |
C3—N1—H1N | 117.8 | C6—C5—H51 | 120.2 |
C1—N1—H1N | 117.8 | C4—C5—H51 | 120.2 |
C6—N2—C2 | 124.5 (2) | N2—C6—C5 | 118.5 (3) |
C6—N2—H2N | 117.7 | N2—C6—H61 | 120.7 |
C2—N2—H2N | 117.7 | C5—C6—H61 | 120.7 |
| | | |
O1—P1—C1—P2 | −61.36 (18) | C3—N1—C1—P1 | −88.9 (3) |
O2—P1—C1—P2 | 172.42 (14) | C3—N1—C1—P2 | 141.8 (2) |
O3—P1—C1—P2 | 54.18 (18) | C6—N2—C2—C3 | −0.9 (4) |
O4—P2—C1—P1 | −71.32 (19) | C1—N1—C3—C2 | −3.1 (4) |
O5—P2—C1—P1 | 165.67 (15) | C1—N1—C3—C4 | 176.4 (2) |
O6—P2—C1—P1 | 52.90 (18) | N2—C2—C3—N1 | −177.1 (2) |
O1—P1—C1—N1 | 174.72 (16) | N2—C2—C3—C4 | 3.4 (3) |
O2—P1—C1—N1 | 48.5 (2) | N1—C3—C4—C5 | 177.0 (2) |
O3—P1—C1—N1 | −69.75 (19) | C2—C3—C4—C5 | −3.4 (4) |
O4—P2—C1—N1 | 54.0 (2) | C3—C4—C5—C6 | 0.9 (4) |
O5—P2—C1—N1 | −69.0 (2) | C2—N2—C6—C5 | −1.7 (4) |
O6—P2—C1—N1 | 178.25 (18) | C4—C5—C6—N2 | 1.7 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.84 | 1.71 | 2.514 (2) | 159 |
O5—H5···O2ii | 0.84 | 1.67 | 2.479 (2) | 161 |
O6—H6···O1iii | 0.84 | 1.76 | 2.586 (3) | 167 |
N1—H1N···O2iv | 0.88 | 2.35 | 3.193 (3) | 160 |
N2—H2N···O1v | 0.88 | 1.90 | 2.733 (3) | 157 |
C2—H21···O5vi | 0.95 | 2.58 | 3.220 (3) | 125 |
C4—H41···O2iv | 0.95 | 2.59 | 3.402 (3) | 144 |
C6—H61···O3vii | 0.95 | 2.45 | 3.196 (3) | 136 |
C6—H61···O4viii | 0.95 | 2.55 | 3.346 (4) | 142 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1; (iii) −x+2, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+1, −y+1, −z; (vi) −x+1, −y+1, −z+1; (vii) x−1, −y+1/2, z−1/2; (viii) x−1, y, z−1. |
(II) hydrogen {phosphono[(2-chloropyridin-1-ium-3-yl)amino]methyl}phosphonate
top
Crystal data top
C6H9ClN2O6P2 | Z = 2 |
Mr = 302.54 | F(000) = 308 |
Triclinic, P1 | Dx = 1.874 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.667 (2) Å | Cell parameters from 5273 reflections |
b = 8.364 (2) Å | θ = 3.1–37.5° |
c = 9.283 (3) Å | µ = 0.67 mm−1 |
α = 109.41 (3)° | T = 100 K |
β = 105.31 (3)° | Plate, colourless |
γ = 92.39 (3)° | 0.47 × 0.18 × 0.06 mm |
V = 536.0 (3) Å3 | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 2735 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2503 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 30.0°, θmin = 3.1° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −9→10 |
Tmin = 0.920, Tmax = 1.000 | k = −10→11 |
6017 measured reflections | l = −13→12 |
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)] = 0.027 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0406P)2 + 0.3896P] where P = (Fo2 + 2Fc2)/3 |
2735 reflections | (Δ/σ)max = 0.001 |
157 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
Crystal data top
C6H9ClN2O6P2 | γ = 92.39 (3)° |
Mr = 302.54 | V = 536.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.667 (2) Å | Mo Kα radiation |
b = 8.364 (2) Å | µ = 0.67 mm−1 |
c = 9.283 (3) Å | T = 100 K |
α = 109.41 (3)° | 0.47 × 0.18 × 0.06 mm |
β = 105.31 (3)° | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 2735 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | 2503 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 1.000 | Rint = 0.016 |
6017 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.44 e Å−3 |
2735 reflections | Δρmin = −0.64 e Å−3 |
157 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.56754 (5) | 0.28625 (4) | 0.82457 (4) | 0.01229 (9) | |
P1 | 0.72114 (5) | 0.80652 (5) | 0.63614 (4) | 0.00849 (9) | |
P2 | 0.32414 (5) | 0.79224 (5) | 0.65783 (4) | 0.00872 (9) | |
O1 | 0.68469 (16) | 0.95967 (14) | 0.58852 (13) | 0.0132 (2) | |
O2 | 0.70541 (15) | 0.63999 (13) | 0.50066 (13) | 0.0130 (2) | |
O3 | 0.90617 (15) | 0.84636 (15) | 0.77120 (13) | 0.0149 (2) | |
H3 | 0.9875 | 0.8034 | 0.7315 | 0.022* | |
O4 | 0.22189 (15) | 0.76694 (14) | 0.76917 (13) | 0.0131 (2) | |
O5 | 0.30562 (15) | 0.96590 (13) | 0.64055 (13) | 0.0111 (2) | |
H5 | 0.3192 | 0.9618 | 0.5526 | 0.017* | |
O6 | 0.26506 (15) | 0.64908 (14) | 0.49138 (13) | 0.0136 (2) | |
H6 | 0.2760 | 0.5537 | 0.5018 | 0.020* | |
N1 | 0.58316 (17) | 0.62995 (15) | 0.78885 (15) | 0.0098 (2) | |
H1N | 0.5154 | 0.5339 | 0.7196 | 0.012* | |
N2 | 0.79389 (17) | 0.46916 (16) | 1.10065 (15) | 0.0113 (2) | |
H2N | 0.7830 | 0.3733 | 1.1193 | 0.014* | |
C1 | 0.56473 (19) | 0.78524 (17) | 0.74967 (17) | 0.0083 (3) | |
H1 | 0.6051 | 0.8843 | 0.8534 | 0.010* | |
C2 | 0.69655 (19) | 0.47309 (18) | 0.95934 (17) | 0.0097 (3) | |
C3 | 0.69965 (19) | 0.62560 (18) | 0.92683 (17) | 0.0089 (3) | |
C4 | 0.8222 (2) | 0.76671 (19) | 1.04469 (18) | 0.0118 (3) | |
H41 | 0.8342 | 0.8713 | 1.0264 | 0.014* | |
C5 | 0.9256 (2) | 0.7555 (2) | 1.18721 (18) | 0.0135 (3) | |
H51 | 1.0089 | 0.8514 | 1.2652 | 0.016* | |
C6 | 0.9073 (2) | 0.6049 (2) | 1.21529 (18) | 0.0140 (3) | |
H61 | 0.9739 | 0.5971 | 1.3142 | 0.017* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.01508 (18) | 0.00852 (16) | 0.01122 (17) | −0.00042 (12) | 0.00157 (13) | 0.00295 (13) |
P1 | 0.00845 (18) | 0.00895 (17) | 0.00909 (18) | 0.00152 (12) | 0.00279 (13) | 0.00431 (14) |
P2 | 0.00772 (18) | 0.01010 (17) | 0.00947 (18) | 0.00151 (12) | 0.00236 (13) | 0.00503 (14) |
O1 | 0.0180 (6) | 0.0114 (5) | 0.0141 (5) | 0.0034 (4) | 0.0070 (4) | 0.0076 (4) |
O2 | 0.0181 (6) | 0.0105 (5) | 0.0110 (5) | 0.0031 (4) | 0.0058 (4) | 0.0030 (4) |
O3 | 0.0076 (5) | 0.0230 (6) | 0.0126 (5) | 0.0033 (4) | 0.0026 (4) | 0.0046 (4) |
O4 | 0.0107 (5) | 0.0178 (5) | 0.0172 (5) | 0.0042 (4) | 0.0064 (4) | 0.0124 (4) |
O5 | 0.0139 (5) | 0.0111 (5) | 0.0111 (5) | 0.0035 (4) | 0.0051 (4) | 0.0060 (4) |
O6 | 0.0142 (5) | 0.0108 (5) | 0.0121 (5) | 0.0010 (4) | −0.0006 (4) | 0.0031 (4) |
N1 | 0.0112 (6) | 0.0080 (5) | 0.0089 (5) | −0.0005 (4) | −0.0002 (4) | 0.0039 (4) |
N2 | 0.0112 (6) | 0.0121 (6) | 0.0121 (6) | 0.0018 (4) | 0.0026 (5) | 0.0069 (5) |
C1 | 0.0090 (6) | 0.0082 (6) | 0.0087 (6) | 0.0010 (5) | 0.0023 (5) | 0.0044 (5) |
C2 | 0.0095 (7) | 0.0097 (6) | 0.0095 (6) | 0.0007 (5) | 0.0021 (5) | 0.0035 (5) |
C3 | 0.0088 (6) | 0.0103 (6) | 0.0089 (6) | 0.0021 (5) | 0.0033 (5) | 0.0045 (5) |
C4 | 0.0117 (7) | 0.0114 (7) | 0.0121 (7) | 0.0005 (5) | 0.0028 (5) | 0.0048 (5) |
C5 | 0.0138 (7) | 0.0140 (7) | 0.0104 (7) | −0.0015 (5) | 0.0011 (6) | 0.0039 (5) |
C6 | 0.0124 (7) | 0.0167 (7) | 0.0112 (7) | −0.0003 (5) | −0.0006 (6) | 0.0062 (6) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.7040 (17) | N1—C3 | 1.3671 (18) |
P1—O1 | 1.5018 (11) | N1—H1N | 0.88 |
P1—O2 | 1.5092 (13) | N2—C2 | 1.3388 (19) |
P1—O3 | 1.5617 (13) | N2—C6 | 1.343 (2) |
P1—C1 | 1.8315 (15) | N2—H2N | 0.88 |
P2—O4 | 1.5124 (12) | C1—H1 | 1.00 |
P2—O5 | 1.5217 (11) | C2—C3 | 1.4057 (18) |
P2—O6 | 1.5434 (14) | C3—C4 | 1.407 (2) |
P2—C1 | 1.8288 (16) | C4—C5 | 1.387 (2) |
O3—H3 | 0.84 | C4—H41 | 0.95 |
O5—H5 | 0.84 | C5—C6 | 1.378 (2) |
O6—H6 | 0.84 | C5—H51 | 0.95 |
N1—C1 | 1.4634 (17) | C6—H61 | 0.95 |
| | | |
O1—P1—O2 | 115.63 (7) | P1—C1—P2 | 115.93 (7) |
O1—P1—O3 | 110.53 (7) | P1—C1—N1 | 110.38 (10) |
O2—P1—O3 | 112.38 (7) | P2—C1—N1 | 109.95 (10) |
O1—P1—C1 | 107.64 (7) | N1—C1—H1 | 106.7 |
O2—P1—C1 | 110.20 (7) | P2—C1—H1 | 106.7 |
O3—P1—C1 | 99.10 (7) | P1—C1—H1 | 106.7 |
O4—P2—O5 | 110.88 (7) | N2—C2—C3 | 120.95 (14) |
O4—P2—O6 | 113.35 (7) | N2—C2—Cl1 | 116.67 (11) |
O5—P2—O6 | 109.96 (7) | C3—C2—Cl1 | 122.37 (11) |
O4—P2—C1 | 106.49 (7) | N1—C3—C2 | 119.38 (13) |
O5—P2—C1 | 108.88 (7) | N1—C3—C4 | 124.52 (13) |
O6—P2—C1 | 107.06 (7) | C2—C3—C4 | 116.07 (13) |
P1—O3—H3 | 109.5 | C5—C4—C3 | 121.00 (13) |
P2—O5—H5 | 109.5 | C5—C4—H41 | 119.5 |
P2—O6—H6 | 109.5 | C3—C4—H41 | 119.5 |
C1—N1—C3 | 123.75 (12) | C6—C5—C4 | 119.78 (14) |
C3—N1—H1N | 118.1 | C6—C5—H51 | 120.1 |
C1—N1—H1N | 118.1 | C4—C5—H51 | 120.1 |
C2—N2—C6 | 123.01 (13) | N2—C6—C5 | 118.96 (14) |
C2—N2—H2N | 118.5 | N2—C6—H61 | 120.5 |
C6—N2—H2N | 118.5 | C5—C6—H61 | 120.5 |
| | | |
O1—P1—C1—P2 | 49.65 (10) | C6—N2—C2—C3 | −4.0 (2) |
O2—P1—C1—P2 | −77.27 (10) | C6—N2—C2—Cl1 | 177.08 (12) |
O3—P1—C1—P2 | 164.71 (8) | C1—N1—C3—C2 | 174.83 (13) |
O4—P2—C1—P1 | 178.28 (7) | C1—N1—C3—C4 | −3.1 (2) |
O5—P2—C1—P1 | −62.11 (10) | N2—C2—C3—N1 | −172.61 (14) |
O6—P2—C1—P1 | 56.73 (9) | Cl1—C2—C3—N1 | 6.2 (2) |
O1—P1—C1—N1 | 175.48 (9) | N2—C2—C3—C4 | 5.5 (2) |
O2—P1—C1—N1 | 48.56 (11) | Cl1—C2—C3—C4 | −175.66 (11) |
O3—P1—C1—N1 | −69.46 (11) | N1—C3—C4—C5 | 174.85 (15) |
O4—P2—C1—N1 | 52.23 (11) | C2—C3—C4—C5 | −3.2 (2) |
O5—P2—C1—N1 | 171.84 (9) | C3—C4—C5—C6 | −0.7 (2) |
O6—P2—C1—N1 | −69.32 (11) | C2—N2—C6—C5 | −0.2 (2) |
C3—N1—C1—P1 | 91.50 (15) | C4—C5—C6—N2 | 2.5 (2) |
C3—N1—C1—P2 | −139.37 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.84 | 1.80 | 2.540 (2) | 146 |
O5—H5···O1ii | 0.84 | 1.64 | 2.424 (2) | 153 |
O6—H6···O2iii | 0.84 | 1.63 | 2.461 (2) | 173 |
N1—H1N···Cl1 | 0.88 | 2.57 | 3.002 (2) | 111 |
N1—H1N···O2iii | 0.88 | 2.27 | 3.103 (2) | 158 |
N2—H2N···O4iv | 0.88 | 1.81 | 2.649 (2) | 159 |
C4—H41···O3 | 0.95 | 2.52 | 3.042 (2) | 115 |
C5—H51···O1v | 0.95 | 2.54 | 3.429 (3) | 156 |
C6—H61···O6vi | 0.95 | 2.32 | 3.131 (2) | 143 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x+2, −y+2, −z+2; (vi) x+1, y, z+1. |
(III) bis(6-chloropyridin-3-aminium)
[hydrogen bis({[2-chloropyridin-1-ium-3-yl(0.5+)]amino}methylenediphosphonate)]
top
Crystal data top
2C5H6ClN2+·C12H16Cl2N4O12P42− | F(000) = 880 |
Mr = 862.20 | Dx = 1.802 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 6035 reflections |
a = 8.555 (2) Å | θ = 2.8–36.6° |
b = 7.585 (2) Å | µ = 0.65 mm−1 |
c = 24.560 (5) Å | T = 100 K |
β = 94.32 (3)° | Plate, colourless |
V = 1589.2 (6) Å3 | 0.25 × 0.11 × 0.03 mm |
Z = 2 | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 4513 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 30.0°, θmin = 2.8° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009) | h = −10→11 |
Tmin = 0.895, Tmax = 0.976 | k = −9→10 |
16241 measured reflections | l = −34→31 |
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)] = 0.041 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3 |
4513 reflections | (Δ/σ)max = 0.001 |
226 parameters | Δρmax = 0.46 e Å−3 |
18 restraints | Δρmin = −0.59 e Å−3 |
Crystal data top
2C5H6ClN2+·C12H16Cl2N4O12P42− | V = 1589.2 (6) Å3 |
Mr = 862.20 | Z = 2 |
Monoclinic, P2/c | Mo Kα radiation |
a = 8.555 (2) Å | µ = 0.65 mm−1 |
b = 7.585 (2) Å | T = 100 K |
c = 24.560 (5) Å | 0.25 × 0.11 × 0.03 mm |
β = 94.32 (3)° | |
Data collection top
Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | 4513 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009) | 3162 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.976 | Rint = 0.056 |
16241 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 18 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.46 e Å−3 |
4513 reflections | Δρmin = −0.59 e Å−3 |
226 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl1 | 0.18450 (7) | 0.09767 (8) | 0.51266 (2) | 0.02041 (13) | |
P1 | 0.78559 (6) | 0.06159 (7) | 0.29686 (2) | 0.01046 (12) | |
P2 | 0.78166 (6) | 0.46470 (7) | 0.29984 (2) | 0.01042 (12) | |
O1 | 0.79129 (17) | 0.07478 (19) | 0.23581 (6) | 0.0133 (3) | |
O2 | 0.68939 (17) | −0.08897 (18) | 0.31686 (6) | 0.0146 (3) | |
O3 | 0.95636 (17) | 0.04581 (19) | 0.32526 (6) | 0.0145 (3) | |
H3 | 1.0220 | 0.0656 | 0.3022 | 0.022* | |
O4 | 0.68529 (17) | 0.51126 (19) | 0.24821 (6) | 0.0138 (3) | |
O5 | 0.95569 (17) | 0.4367 (2) | 0.29528 (6) | 0.0151 (3) | |
H5 | 1.0000 | 0.428 (6) | 0.2500 | 0.068 (16)* | |
O6 | 0.76163 (19) | 0.59904 (19) | 0.34715 (6) | 0.0158 (3) | |
H6 | 0.7398 | 0.6989 | 0.3339 | 0.024* | |
N1 | 0.5366 (2) | 0.2680 (2) | 0.32477 (7) | 0.0124 (4) | |
H1N | 0.4857 | 0.3007 | 0.2939 | 0.015* | |
N2 | 0.4302 (2) | 0.0944 (2) | 0.45584 (7) | 0.0133 (4) | |
H2N | 0.4736 | 0.0355 | 0.4839 | 0.016* | 0.50 |
C1 | 0.7072 (2) | 0.2613 (3) | 0.32700 (8) | 0.0099 (4) | |
H1 | 0.7441 | 0.2589 | 0.3666 | 0.012* | |
C2 | 0.5139 (3) | 0.1309 (3) | 0.41291 (9) | 0.0135 (4) | |
H21 | 0.6191 | 0.0904 | 0.4133 | 0.016* | |
C3 | 0.4509 (2) | 0.2266 (3) | 0.36778 (9) | 0.0116 (4) | |
C4 | 0.2926 (3) | 0.2763 (3) | 0.36784 (9) | 0.0137 (4) | |
H41 | 0.2434 | 0.3373 | 0.3374 | 0.016* | |
C5 | 0.2085 (3) | 0.2368 (3) | 0.41201 (9) | 0.0145 (4) | |
H51 | 0.1017 | 0.2706 | 0.4124 | 0.017* | |
C6 | 0.2822 (3) | 0.1473 (3) | 0.45572 (9) | 0.0151 (5) | |
Cl2 | 0.80512 (7) | 0.57726 (8) | −0.02849 (2) | 0.02266 (14) | 0.574 (11) |
N11 | 0.6187 (14) | 0.7999 (15) | 0.1867 (2) | 0.011 (3)* | 0.574 (11) |
H11A | 0.6755 | 0.8973 | 0.1970 | 0.017* | 0.574 (11) |
H11B | 0.6408 | 0.7116 | 0.2111 | 0.017* | 0.574 (11) |
H11C | 0.5147 | 0.8258 | 0.1855 | 0.017* | 0.574 (11) |
N12 | 0.6030 (6) | 0.6492 (8) | 0.0428 (2) | 0.0142 (18)* | 0.574 (11) |
C12 | 0.5619 (7) | 0.6971 (10) | 0.0912 (3) | 0.015 (2)* | 0.574 (11) |
H12 | 0.4531 | 0.6980 | 0.0967 | 0.018* | 0.574 (11) |
C13 | 0.6592 (9) | 0.7437 (11) | 0.13265 (17) | 0.0127 (17)* | 0.574 (11) |
C14 | 0.8273 (6) | 0.7331 (8) | 0.1267 (2) | 0.0136 (15)* | 0.574 (11) |
H14 | 0.9017 | 0.7600 | 0.1562 | 0.016* | 0.574 (11) |
C15 | 0.8740 (7) | 0.6816 (9) | 0.0758 (2) | 0.0158 (17)* | 0.574 (11) |
H15 | 0.9819 | 0.6715 | 0.0695 | 0.019* | 0.574 (11) |
C16 | 0.7638 (7) | 0.6476 (9) | 0.03680 (15) | 0.0138 (14)* | 0.574 (11) |
Cl20 | 0.80512 (7) | 0.57726 (8) | −0.02849 (2) | 0.02266 (14) | 0.426 (11) |
N110 | 0.6287 (17) | 0.797 (2) | 0.1877 (3) | 0.014 (5)* | 0.426 (11) |
H11D | 0.6948 | 0.8811 | 0.2026 | 0.021* | 0.426 (11) |
H11E | 0.6309 | 0.7013 | 0.2102 | 0.021* | 0.426 (11) |
H11F | 0.5295 | 0.8408 | 0.1837 | 0.021* | 0.426 (11) |
N120 | 0.8616 (7) | 0.7014 (11) | 0.0700 (2) | 0.021 (2)* | 0.426 (11) |
C120 | 0.8213 (8) | 0.7499 (12) | 0.1184 (3) | 0.020 (2)* | 0.426 (11) |
H120 | 0.9022 | 0.7916 | 0.1438 | 0.025* | 0.426 (11) |
C130 | 0.6785 (9) | 0.7453 (13) | 0.1345 (2) | 0.006 (2)* | 0.426 (11) |
C140 | 0.5507 (8) | 0.6859 (14) | 0.0962 (3) | 0.016 (3)* | 0.426 (11) |
H140 | 0.4451 | 0.6855 | 0.1057 | 0.020* | 0.426 (11) |
C150 | 0.5906 (8) | 0.6296 (13) | 0.0449 (3) | 0.019 (3)* | 0.426 (11) |
H150 | 0.5135 | 0.5848 | 0.0187 | 0.022* | 0.426 (11) |
C160 | 0.7389 (8) | 0.6408 (10) | 0.03422 (17) | 0.0093 (19)* | 0.426 (11) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0184 (3) | 0.0271 (3) | 0.0165 (3) | −0.0009 (2) | 0.0067 (2) | 0.0038 (2) |
P1 | 0.0106 (3) | 0.0088 (2) | 0.0119 (3) | 0.0007 (2) | −0.0001 (2) | 0.00034 (19) |
P2 | 0.0120 (3) | 0.0092 (2) | 0.0102 (3) | −0.0001 (2) | 0.0017 (2) | 0.00038 (19) |
O1 | 0.0140 (8) | 0.0137 (7) | 0.0123 (7) | −0.0001 (6) | 0.0013 (6) | −0.0005 (6) |
O2 | 0.0145 (8) | 0.0101 (7) | 0.0192 (8) | 0.0003 (6) | 0.0018 (6) | 0.0011 (6) |
O3 | 0.0126 (8) | 0.0160 (8) | 0.0152 (8) | 0.0022 (6) | 0.0022 (6) | 0.0010 (6) |
O4 | 0.0161 (8) | 0.0111 (7) | 0.0140 (8) | 0.0010 (6) | −0.0003 (6) | 0.0020 (6) |
O5 | 0.0113 (8) | 0.0190 (8) | 0.0153 (8) | −0.0008 (6) | 0.0021 (6) | 0.0010 (6) |
O6 | 0.0251 (9) | 0.0095 (7) | 0.0130 (8) | 0.0033 (6) | 0.0033 (7) | 0.0002 (6) |
N1 | 0.0105 (9) | 0.0162 (9) | 0.0104 (8) | 0.0008 (7) | −0.0005 (7) | 0.0037 (7) |
N2 | 0.0136 (9) | 0.0133 (8) | 0.0135 (9) | −0.0024 (7) | 0.0039 (7) | 0.0000 (7) |
C1 | 0.0104 (10) | 0.0086 (9) | 0.0107 (9) | −0.0001 (8) | 0.0014 (8) | −0.0006 (8) |
C2 | 0.0134 (11) | 0.0144 (10) | 0.0129 (11) | −0.0026 (8) | 0.0011 (9) | −0.0009 (8) |
C3 | 0.0135 (11) | 0.0085 (9) | 0.0127 (10) | −0.0017 (8) | −0.0003 (8) | −0.0022 (8) |
C4 | 0.0161 (11) | 0.0131 (10) | 0.0114 (10) | −0.0004 (8) | −0.0012 (8) | −0.0015 (8) |
C5 | 0.0133 (11) | 0.0146 (10) | 0.0158 (10) | −0.0006 (8) | 0.0021 (8) | −0.0026 (8) |
C6 | 0.0180 (12) | 0.0141 (10) | 0.0137 (11) | −0.0042 (9) | 0.0050 (9) | −0.0014 (8) |
Cl2 | 0.0304 (3) | 0.0236 (3) | 0.0144 (3) | 0.0056 (2) | 0.0048 (2) | −0.0014 (2) |
Cl20 | 0.0304 (3) | 0.0236 (3) | 0.0144 (3) | 0.0056 (2) | 0.0048 (2) | −0.0014 (2) |
Geometric parameters (Å, º) top
Cl1—C6 | 1.724 (2) | N11—C13 | 1.459 (3) |
P1—O1 | 1.5070 (16) | N11—H11A | 0.91 |
P1—O2 | 1.5112 (15) | N11—H11B | 0.91 |
P1—O3 | 1.5754 (16) | N11—H11C | 0.91 |
P1—C1 | 1.835 (2) | N12—C12 | 1.317 (7) |
P2—O4 | 1.5016 (16) | N12—C16 | 1.395 (8) |
P2—O5 | 1.5164 (16) | C12—C13 | 1.313 (8) |
P2—O6 | 1.5644 (15) | C12—H12 | 0.95 |
P2—C1 | 1.815 (2) | C13—C14 | 1.459 (9) |
O3—H3 | 0.84 | C14—C15 | 1.397 (8) |
O5—H5 | 1.204 (3) | C14—H14 | 0.95 |
O6—H6 | 0.84 | C15—C16 | 1.319 (8) |
N1—C1 | 1.458 (3) | C15—H15 | 0.95 |
N1—C3 | 1.367 (3) | N110—C130 | 1.459 (3) |
N1—H1N | 0.88 | N110—H11D | 0.91 |
N2—C2 | 1.347 (3) | N110—H11E | 0.91 |
N2—C6 | 1.329 (3) | N110—H11F | 0.91 |
N2—H2N | 0.88 | N120—C120 | 1.317 (7) |
C1—H1 | 1.00 | N120—C160 | 1.395 (8) |
C2—C3 | 1.399 (3) | C120—C130 | 1.312 (8) |
C2—H21 | 0.95 | C120—H120 | 0.95 |
C3—C4 | 1.406 (3) | C130—C140 | 1.460 (9) |
C4—C5 | 1.379 (3) | C140—C150 | 1.396 (8) |
C4—H41 | 0.95 | C140—H140 | 0.95 |
C5—C6 | 1.382 (3) | C150—C160 | 1.317 (8) |
C5—H51 | 0.95 | C150—H150 | 0.95 |
Cl2—C16 | 1.751 (2) | | |
| | | |
O1—P1—O2 | 115.64 (9) | N2—C6—C5 | 121.9 (2) |
O1—P1—O3 | 110.31 (9) | N2—C6—Cl1 | 116.92 (17) |
O2—P1—O3 | 107.95 (8) | C5—C6—Cl1 | 121.15 (17) |
O1—P1—C1 | 112.76 (9) | C12—N12—C16 | 115.5 (4) |
O2—P1—C1 | 105.56 (9) | C13—C12—N12 | 125.2 (6) |
O3—P1—C1 | 103.82 (9) | C13—C12—H12 | 117.4 |
O4—P2—O5 | 116.75 (9) | N12—C12—H12 | 117.4 |
O4—P2—O6 | 112.96 (9) | C12—C13—C14 | 118.7 (3) |
O5—P2—O6 | 108.01 (9) | C12—C13—N11 | 127.1 (8) |
O4—P2—C1 | 108.95 (9) | C14—C13—N11 | 114.2 (7) |
O5—P2—C1 | 106.37 (9) | C15—C14—C13 | 117.1 (5) |
O6—P2—C1 | 102.69 (9) | C15—C14—H14 | 121.5 |
P1—O3—H3 | 109.5 | C13—C14—H14 | 121.5 |
P2—O5—H5 | 117.1 (3) | C16—C15—C14 | 117.9 (5) |
P2—O6—H6 | 109.5 | C16—C15—H15 | 121.0 |
C1—N1—C3 | 123.81 (18) | C14—C15—H15 | 121.0 |
C3—N1—H1N | 118.1 | C15—C16—N12 | 125.3 (2) |
C1—N1—H1N | 118.1 | C15—C16—Cl2 | 122.9 (4) |
C6—N2—C2 | 119.94 (19) | N12—C16—Cl2 | 111.6 (4) |
C6—N2—H2N | 120.0 | C130—N110—H11D | 109.5 |
C2—N2—H2N | 120.0 | C130—N110—H11E | 109.5 |
P1—C1—P2 | 113.86 (11) | H11D—N110—H11E | 109.5 |
P1—C1—N1 | 114.15 (14) | C130—N110—H11F | 109.5 |
P2—C1—N1 | 109.54 (13) | H11D—N110—H11F | 109.5 |
N1—C1—H1 | 106.2 | H11E—N110—H11F | 109.5 |
P2—C1—H1 | 106.2 | C120—N120—C160 | 115.2 (5) |
P1—C1—H1 | 106.2 | C130—C120—N120 | 125.3 (6) |
N2—C2—C3 | 122.1 (2) | C130—C120—H120 | 117.4 |
N2—C2—H21 | 119.0 | N120—C120—H120 | 117.4 |
C3—C2—H21 | 119.0 | C120—C130—N110 | 127.1 (8) |
N1—C3—C2 | 122.3 (2) | C120—C130—C140 | 118.9 (3) |
N1—C3—C4 | 120.77 (19) | N110—C130—C140 | 114.0 (7) |
C2—C3—C4 | 116.9 (2) | C150—C140—C130 | 117.0 (5) |
C5—C4—C3 | 120.1 (2) | C150—C140—H140 | 121.5 |
C5—C4—H41 | 119.9 | C130—C140—H140 | 121.5 |
C3—C4—H41 | 119.9 | C160—C150—C140 | 117.7 (5) |
C4—C5—C6 | 119.0 (2) | C160—C150—H150 | 121.2 |
C4—C5—H51 | 120.5 | C140—C150—H150 | 121.2 |
C6—C5—H51 | 120.5 | C150—C160—N120 | 125.9 (3) |
| | | |
O1—P1—C1—P2 | −42.98 (14) | C2—N2—C6—C5 | 1.3 (3) |
O2—P1—C1—P2 | −170.13 (10) | C2—N2—C6—Cl1 | −179.12 (15) |
O3—P1—C1—P2 | 76.41 (12) | C4—C5—C6—N2 | −1.7 (3) |
O4—P2—C1—P1 | 84.43 (12) | C4—C5—C6—Cl1 | 178.77 (16) |
O5—P2—C1—P1 | −42.21 (14) | C16—N12—C12—C13 | 0.7 (12) |
O6—P2—C1—P1 | −155.56 (11) | N12—C12—C13—C14 | −3.8 (13) |
O1—P1—C1—N1 | 83.82 (16) | N12—C12—C13—N11 | 179.1 (9) |
O2—P1—C1—N1 | −43.33 (16) | C12—C13—C14—C15 | 3.1 (11) |
O3—P1—C1—N1 | −156.79 (14) | N11—C13—C14—C15 | −179.4 (7) |
O4—P2—C1—N1 | −44.73 (16) | C13—C14—C15—C16 | 0.5 (9) |
O5—P2—C1—N1 | −171.38 (13) | C14—C15—C16—N12 | −3.8 (11) |
O6—P2—C1—N1 | 75.27 (15) | C14—C15—C16—Cl2 | −178.6 (5) |
C3—N1—C1—P1 | 99.7 (2) | C12—N12—C16—C15 | 3.3 (11) |
C3—N1—C1—P2 | −131.28 (17) | C12—N12—C16—Cl2 | 178.6 (6) |
C6—N2—C2—C3 | 1.1 (3) | C160—N120—C120—C130 | −0.1 (14) |
C1—N1—C3—C2 | −17.2 (3) | N120—C120—C130—N110 | 179.8 (12) |
C1—N1—C3—C4 | 164.16 (18) | N120—C120—C130—C140 | −1.4 (16) |
N2—C2—C3—N1 | 178.25 (19) | C120—C130—C140—C150 | 2.8 (15) |
N2—C2—C3—C4 | −3.0 (3) | N110—C130—C140—C150 | −178.2 (11) |
N1—C3—C4—C5 | −178.67 (19) | C130—C140—C150—C160 | −2.6 (15) |
C2—C3—C4—C5 | 2.6 (3) | C140—C150—C160—N120 | 1.2 (16) |
C3—C4—C5—C6 | −0.4 (3) | C120—N120—C160—C150 | 0.3 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.84 | 1.91 | 2.729 (2) | 164 |
O5—H5···O5i | 1.20 (1) | 1.20 (1) | 2.403 (3) | 173 (5) |
O6—H6···O2ii | 0.84 | 1.71 | 2.543 (2) | 171 |
N1—H1N···O4iii | 0.88 | 2.35 | 3.115 (2) | 145 |
N2—H2N···N2iv | 0.88 | 1.91 | 2.791 (4) | 179 |
N11—H11A···O1ii | 0.91 | 1.89 | 2.778 (12) | 166 |
N11—H11B···O4 | 0.91 | 1.80 | 2.697 (11) | 169 |
N11—H11C···O2v | 0.91 | 1.86 | 2.763 (11) | 172 |
N110—H11D···O1ii | 0.91 | 1.84 | 2.742 (15) | 168 |
N110—H11E···O4 | 0.91 | 1.76 | 2.651 (16) | 165 |
N110—H11F···O2v | 0.91 | 1.95 | 2.850 (14) | 172 |
C2—H21···Cl1iv | 0.95 | 2.78 | 3.506 (2) | 134 |
C4—H41···O4iii | 0.95 | 2.59 | 3.379 (3) | 140 |
C12—H12···O6iii | 0.95 | 2.49 | 3.337 (7) | 148 |
C14—H14···O3vi | 0.95 | 2.51 | 3.180 (6) | 128 |
C120—H120···O3vi | 0.95 | 2.37 | 3.189 (8) | 144 |
C140—H140···O6iii | 0.95 | 2.28 | 3.174 (7) | 156 |
C150—H150···N12vii | 0.95 | 2.49 | 3.365 (6) | 153 |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) x, y+1, z; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x+1, y+1, −z+1/2; (vi) −x+2, y+1, −z+1/2; (vii) −x+1, −y+1, −z. |
Experimental details
| (Ia) | (Ib) | (II) | (III) |
Crystal data |
Chemical formula | C6H10N2O6P2·H2O | C6H10N2O6P2 | C6H9ClN2O6P2 | 2C5H6ClN2+·C12H16Cl2N4O12P42− |
Mr | 286.12 | 268.10 | 302.54 | 862.20 |
Crystal system, space group | Monoclinic, P2/n | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P2/c |
Temperature (K) | 294 | 120 | 100 | 100 |
a, b, c (Å) | 9.068 (3), 7.513 (2), 16.126 (4) | 9.172 (3), 14.802 (4), 7.589 (2) | 7.667 (2), 8.364 (2), 9.283 (3) | 8.555 (2), 7.585 (2), 24.560 (5) |
α, β, γ (°) | 90, 103.55 (3), 90 | 90, 104.35 (3), 90 | 109.41 (3), 105.31 (3), 92.39 (3) | 90, 94.32 (3), 90 |
V (Å3) | 1068.1 (5) | 998.2 (5) | 536.0 (3) | 1589.2 (6) |
Z | 4 | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.45 | 0.67 | 0.65 |
Crystal size (mm) | 0.38 × 0.30 × 0.15 | 0.20 × 0.02 × 0.01 | 0.47 × 0.18 × 0.06 | 0.25 × 0.11 × 0.03 |
|
Data collection |
Diffractometer | Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | Oxford Xcalibur PX κ-geometry diffractometer with Onyx CCD camera | Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera | Kuma KM-4-CCD κ-geometry diffractometer with Sapphire CCD camera |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | Analytical (CrysAlis RED; Oxford Diffraction, 2009) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | Analytical (CrysAlis RED; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.880, 1.000 | 0.954, 0.994 | 0.920, 1.000 | 0.895, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9984, 2907, 2229 | 17046, 2925, 1307 | 6017, 2735, 2503 | 16241, 4513, 3162 |
Rint | 0.034 | 0.168 | 0.016 | 0.056 |
(sin θ/λ)max (Å−1) | 0.703 | 0.705 | 0.703 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.134, 1.06 | 0.048, 0.056, 0.82 | 0.027, 0.075, 1.06 | 0.041, 0.090, 1.02 |
No. of reflections | 2907 | 2925 | 2735 | 4513 |
No. of parameters | 164 | 148 | 157 | 226 |
No. of restraints | 4 | 0 | 0 | 18 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.27 | 0.46, −0.51 | 0.44, −0.64 | 0.46, −0.59 |
Selected geometric parameters (Å, º) for (Ia) topP1—O1 | 1.507 (2) | P2—O5 | 1.526 (2) |
P1—O2 | 1.513 (2) | P2—O6 | 1.536 (2) |
P1—O3 | 1.548 (2) | P2—C1 | 1.811 (3) |
P1—C1 | 1.820 (3) | N1—C1 | 1.462 (3) |
P2—O4 | 1.502 (2) | N1—C3 | 1.360 (4) |
| | | |
O1—P1—O2 | 115.63 (13) | O5—P2—O6 | 108.81 (14) |
O1—P1—O3 | 108.77 (12) | O4—P2—C1 | 108.85 (13) |
O2—P1—O3 | 111.45 (11) | O5—P2—C1 | 102.22 (14) |
O1—P1—C1 | 105.38 (13) | O6—P2—C1 | 109.60 (13) |
O2—P1—C1 | 107.42 (12) | C1—N1—C3 | 125.6 (2) |
O3—P1—C1 | 107.75 (12) | P1—C1—P2 | 116.41 (14) |
O4—P2—O5 | 113.77 (16) | P1—C1—N1 | 109.38 (18) |
O4—P2—O6 | 113.01 (12) | P2—C1—N1 | 109.44 (19) |
| | | |
O1—P1—C1—P2 | −170.95 (14) | C3—N1—C1—P2 | 99.9 (3) |
O5—P2—C1—P1 | 175.87 (17) | C1—N1—C3—C2 | 174.8 (3) |
C3—N1—C1—P1 | −131.5 (3) | | |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.82 | 1.74 | 2.532 (3) | 162 |
O5—H5···O1ii | 0.82 | 1.67 | 2.424 (3) | 152 |
O6—H6···O4i | 0.82 | 1.72 | 2.519 (3) | 165 |
N1—H1N···O1W | 0.86 | 2.17 | 2.938 (4) | 148 |
N2—H2N···O2iii | 0.86 | 2.16 | 2.911 (4) | 146 |
O1W—H1W···O2W | 0.84 | 1.85 | 2.689 (6) | 180 |
O1W—H2W···O3 | 0.84 | 2.06 | 2.859 (2) | 160 |
O2W—H3W···O4iv | 0.84 | 2.30 | 3.076 (3) | 155 |
O2W—H3W···O5iv | 0.84 | 2.55 | 3.116 (3) | 126 |
C1—H1···O1v | 0.98 | 2.33 | 3.253 (4) | 156 |
C6—H61···O5vi | 0.93 | 2.48 | 3.306 (4) | 148 |
Symmetry codes: (i) −x+3/2, y, −z+3/2; (ii) x, y+1, z; (iii) x−1, y, z; (iv) x, y−1, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y+2, −z+1. |
Selected geometric parameters (Å, º) for (Ib) topP1—O1 | 1.504 (2) | P2—O5 | 1.5405 (19) |
P1—O2 | 1.5100 (18) | P2—O6 | 1.544 (2) |
P1—O3 | 1.556 (2) | P2—C1 | 1.825 (2) |
P1—C1 | 1.834 (2) | N1—C1 | 1.460 (3) |
P2—O4 | 1.4812 (19) | N1—C3 | 1.366 (3) |
| | | |
O1—P1—O2 | 116.63 (10) | O5—P2—O6 | 108.31 (12) |
O1—P1—O3 | 107.19 (12) | O4—P2—C1 | 112.75 (12) |
O2—P1—O3 | 111.83 (11) | O5—P2—C1 | 101.85 (11) |
O1—P1—C1 | 110.27 (12) | O6—P2—C1 | 104.73 (11) |
O2—P1—C1 | 104.72 (11) | C1—N1—C3 | 124.4 (2) |
O3—P1—C1 | 105.70 (12) | P1—C1—P2 | 117.34 (14) |
O4—P2—O5 | 114.35 (11) | P1—C1—N1 | 110.51 (17) |
O4—P2—O6 | 113.78 (12) | P2—C1—N1 | 107.66 (16) |
| | | |
O2—P1—C1—P2 | 172.42 (14) | C3—N1—C1—P2 | 141.8 (2) |
O5—P2—C1—P1 | 165.67 (15) | C1—N1—C3—C2 | −3.1 (4) |
C3—N1—C1—P1 | −88.9 (3) | | |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.84 | 1.71 | 2.514 (2) | 159 |
O5—H5···O2ii | 0.84 | 1.67 | 2.479 (2) | 161 |
O6—H6···O1iii | 0.84 | 1.76 | 2.586 (3) | 167 |
N1—H1N···O2iv | 0.88 | 2.35 | 3.193 (3) | 160 |
N2—H2N···O1v | 0.88 | 1.90 | 2.733 (3) | 157 |
C2—H21···O5vi | 0.95 | 2.58 | 3.220 (3) | 125 |
C4—H41···O2iv | 0.95 | 2.59 | 3.402 (3) | 144 |
C6—H61···O3vii | 0.95 | 2.45 | 3.196 (3) | 136 |
C6—H61···O4viii | 0.95 | 2.55 | 3.346 (4) | 142 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1; (iii) −x+2, −y+1, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+1, −y+1, −z; (vi) −x+1, −y+1, −z+1; (vii) x−1, −y+1/2, z−1/2; (viii) x−1, y, z−1. |
Selected geometric parameters (Å, º) for (II) topP1—O1 | 1.5018 (11) | P2—O5 | 1.5217 (11) |
P1—O2 | 1.5092 (13) | P2—O6 | 1.5434 (14) |
P1—O3 | 1.5617 (13) | P2—C1 | 1.8288 (16) |
P1—C1 | 1.8315 (15) | N1—C1 | 1.4634 (17) |
P2—O4 | 1.5124 (12) | N1—C3 | 1.3671 (18) |
| | | |
O1—P1—O2 | 115.63 (7) | O5—P2—O6 | 109.96 (7) |
O1—P1—O3 | 110.53 (7) | O4—P2—C1 | 106.49 (7) |
O2—P1—O3 | 112.38 (7) | O5—P2—C1 | 108.88 (7) |
O1—P1—C1 | 107.64 (7) | O6—P2—C1 | 107.06 (7) |
O2—P1—C1 | 110.20 (7) | C1—N1—C3 | 123.75 (12) |
O3—P1—C1 | 99.10 (7) | P1—C1—P2 | 115.93 (7) |
O4—P2—O5 | 110.88 (7) | P1—C1—N1 | 110.38 (10) |
O4—P2—O6 | 113.35 (7) | P2—C1—N1 | 109.95 (10) |
| | | |
O3—P1—C1—P2 | 164.71 (8) | C3—N1—C1—P2 | −139.37 (13) |
O4—P2—C1—P1 | 178.28 (7) | C1—N1—C3—C2 | 174.83 (13) |
C3—N1—C1—P1 | 91.50 (15) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.84 | 1.80 | 2.540 (2) | 146 |
O5—H5···O1ii | 0.84 | 1.64 | 2.424 (2) | 153 |
O6—H6···O2iii | 0.84 | 1.63 | 2.461 (2) | 173 |
N1—H1N···Cl1 | 0.88 | 2.57 | 3.002 (2) | 111 |
N1—H1N···O2iii | 0.88 | 2.27 | 3.103 (2) | 158 |
N2—H2N···O4iv | 0.88 | 1.81 | 2.649 (2) | 159 |
C4—H41···O3 | 0.95 | 2.52 | 3.042 (2) | 115 |
C5—H51···O1v | 0.95 | 2.54 | 3.429 (3) | 156 |
C6—H61···O6vi | 0.95 | 2.32 | 3.131 (2) | 143 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z+2; (v) −x+2, −y+2, −z+2; (vi) x+1, y, z+1. |
Selected geometric parameters (Å, º) for (III) topP1—O1 | 1.5070 (16) | P2—O5 | 1.5164 (16) |
P1—O2 | 1.5112 (15) | P2—O6 | 1.5644 (15) |
P1—O3 | 1.5754 (16) | P2—C1 | 1.815 (2) |
P1—C1 | 1.835 (2) | N1—C1 | 1.458 (3) |
P2—O4 | 1.5016 (16) | N1—C3 | 1.367 (3) |
| | | |
O1—P1—O2 | 115.64 (9) | O5—P2—O6 | 108.01 (9) |
O1—P1—O3 | 110.31 (9) | O4—P2—C1 | 108.95 (9) |
O2—P1—O3 | 107.95 (8) | O5—P2—C1 | 106.37 (9) |
O1—P1—C1 | 112.76 (9) | O6—P2—C1 | 102.69 (9) |
O2—P1—C1 | 105.56 (9) | C1—N1—C3 | 123.81 (18) |
O3—P1—C1 | 103.82 (9) | P1—C1—P2 | 113.86 (11) |
O4—P2—O5 | 116.75 (9) | P1—C1—N1 | 114.15 (14) |
O4—P2—O6 | 112.96 (9) | P2—C1—N1 | 109.54 (13) |
| | | |
O2—P1—C1—P2 | −170.13 (10) | C3—N1—C1—P2 | −131.28 (17) |
O6—P2—C1—P1 | −155.56 (11) | C1—N1—C3—C2 | −17.2 (3) |
C3—N1—C1—P1 | 99.7 (2) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1i | 0.84 | 1.91 | 2.729 (2) | 164 |
O5—H5···O5i | 1.204 (3) | 1.204 (3) | 2.403 (3) | 173 (5) |
O6—H6···O2ii | 0.84 | 1.71 | 2.543 (2) | 171 |
N1—H1N···O4iii | 0.88 | 2.35 | 3.115 (2) | 145 |
N2—H2N···N2iv | 0.88 | 1.91 | 2.791 (4) | 179 |
N11—H11A···O1ii | 0.91 | 1.89 | 2.778 (12) | 166 |
N11—H11B···O4 | 0.91 | 1.80 | 2.697 (11) | 169 |
N11—H11C···O2v | 0.91 | 1.86 | 2.763 (11) | 172 |
N110—H11D···O1ii | 0.91 | 1.84 | 2.742 (15) | 168 |
N110—H11E···O4 | 0.91 | 1.76 | 2.651 (16) | 165 |
N110—H11F···O2v | 0.91 | 1.95 | 2.850 (14) | 172 |
C2—H21···Cl1iv | 0.95 | 2.78 | 3.506 (2) | 134 |
C4—H41···O4iii | 0.95 | 2.59 | 3.379 (3) | 140 |
C12—H12···O6iii | 0.95 | 2.49 | 3.337 (7) | 148 |
C14—H14···O3vi | 0.95 | 2.51 | 3.180 (6) | 128 |
C120—H120···O3vi | 0.95 | 2.37 | 3.189 (8) | 144 |
C140—H140···O6iii | 0.95 | 2.28 | 3.174 (7) | 156 |
C150—H150···N12vii | 0.95 | 2.49 | 3.365 (6) | 153 |
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) x, y+1, z; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x+1, y+1, −z+1/2; (vi) −x+2, y+1, −z+1/2; (vii) −x+1, −y+1, −z. |
Pyridine-based bis-phosphonates display a broad spectrum of biological activities, which rely predominantly on their inhibitory potency with respect to FPP synthase, a key enzyme in the mevalonate pathway common in human, parasite and plant cells (De Schutter et al., 2010; Sanders et al., 2003; Szabo et al., 2002; Cao et al., 2008). In recent years, we have investigated the crystal structures of a series of [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids (Matczak-Jon et al., 2001, 2006a,b, 2009; Matczak-Jon, Ślepokura et al., 2010), which are a subclass of pyridine-based acids with a direct C—Namino bond. Their exceptional feature compared with other members of this family is a partially double C2—Namino bond, which leads to two preferred Z and E conformers [Z/E assignment consistent with Matczak-Jon et al. (2001)]. During the course of our studies, it has become apparent that the configurational preferences of [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids are primarily determined by the topology and chemical nature of the substituents attached to the pyridine ring. We have demonstrated that compounds substituted in the 4- or 5-position of the pyridine ring exist in solution as a mixture of almost equally populated Z and E conformers. As long as the pyridine N atom remains protonated, the Z conformer crystallizes preferentially (Sanders et al., 2003; Matczak-Jon et al., 2001, 2006a,b, 2009). The removal of the proton from the pyridinium N atom enables Z/E interconversion and as a result the E form is able to crystallize from a solution (Sanders et al., 2003; Matczak-Jon et al., 2009). A key role for the Z stabilization, in both the solid state and solution, is the symmetrical dimer generated through intermolecular bifurcated N—H···O hydrogen bonds involving both exocyclic and pyridine N atoms as proton donors and an O atom of one of the phosphono/phosphonate group as acceptor. This is a common phenomenon in the crystal structures of all the Z zwitterions of [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids studied to date.
In contrast, acids substituted in the 3-position of the pyridine ring adopt the E conformation, stabilized through an intramolecular hydrogen bond involving the exocyclic N atom as a proton donor and the sterically accessible substituent as a proton acceptor (Szabo et al., 2002; Matczak-Jon et al., 2001), even in the presence of other substituents attached to the pyridine ring (Matczak-Jon, Ślepokura et al., 2010). This generalization fails only for the zwitterion of [(pyridin-2-yl)amino]methane-1,1-diphosphonic acid which, despite almost equal populations of the E and Z conformers in solution, crystallizes as the E conformer (Matczak-Jon et al., 2006a).
Structural data have not as yet been reported for [(pyridinyl)amino]methane-1,1-diphosphonic acids with the aminomethane-1,1-diphosphonate portion attached to the 3-position of the pyridine ring. These compounds display marked differences in their abilities to bind metal ions in solution (Kowalik-Jankowska et al., 2011) compared with 3-, 4-, 5- and 6-ring-substituted [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids (Matczak-Jon, Kowalik-Jankowska et al., 2010; Matczak-Jon et al., 2002). It is, therefore, highly desirable to look for factors which may be responsible for these differences in their behaviour. We present here the crystal structures of the two conformers of hydrogen {phosphono[(pyridin-1-ium-3-yl)amino]methyl}phosphonate as the monohydrate, (Ia), and the unsolvated form, (Ib), the related hydrogen {phosphono[(2-chloropyridin-1-ium-3-yl)amino]methyl}phosphonate, (II), and the salt bis(6-chloropyridin-3-aminium) [hydrogen bis({phosphono[(2-chloropyridin-1-ium-3-yl)amino]methyl}phosphonate)], (III). Principal geometric data are reported in Tables 1, 3, 5 and 7. The asymmetric unit of (Ia) comprises a zwitterion, formed due to proton transfer from one of the phosphono groups to pyridine atom N2 and one water molecule (O1W and O2W, both located on a twofold axis). Compounds (Ib) and (II) crystallize as zwitterions with the same protonation scheme as in (Ia). Compound (III) is a salt, in which atoms H2N and H5 of the anion both have half-occupancy, and the cation is disordered over two orientations with site occupancies of 0.574 (12) and 0.426 (12) (Figs. 1 and 2).
Due to the partial double-bond character of the C3—N1 bond, all four compounds may adopt two different conformations with respect to this bond, labelled pro-E and pro-Z (McNaught & Wilkinson, 1997). We were successful in obtaining crystals of the pro-E and pro-Z conformers of (I). On the other hand, the zwitterion of (II) is the pro-E conformer, while the bis-phosphonate counterpart in (III) adopts the opposite pro-Z conformation. This is reflected in the values of the C1—N1—C3—C2 torsion angle of 174.8 (3)° for (Ia), -3.1 (4)° for (Ib), 174.8 (2)° for (II) and -17.2 (3)° for (III). In (II), the pro-E conformation is additionally stabilized through an intramolecular N1—H1N···Cl1 hydrogen bond. It is also noteworthy that the C3—N1 bonds in (II) and (III) are slightly longer than those found in most of the zwitterions of [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids studied to date (mean value 1.35 Å; Matczak-Jon et al., 2001, 2006a,b, 2009; Matczak-Jon, Ślepokura et al., 2010).
As a consequence of the formal sp2 hybridization of atom N1, atoms N1 and C1 of all four compounds are coplanar with the pyridinium ring. However, as seen from the C1—N1—C3—C2 torsion angles (Tables 1, 3, 5 and 7), in (III) atom C1 deviates from the pyridinium ring plane more than in (Ia), (Ib) and (II).
Similar to [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids, a common feature of all four compounds is the planar W conformation of the HO—P—C—P—O sequence, which enables the formation of O—H···O hydrogen-bonded chains. As a result, each P atom is antiperiplanar (ap) to one of the O atoms from the adjacent phosphonate groups and synclinal (sc) to the remaining atoms of this group. In both conformers of (I) and in (II), the O—P—C—P—OH arrangement is nearly planar, which is reflected in the values of the relevant torsion angles: O1/O2—P1—C1—P2, O5—P2—C1—P1 for (Ia) and (Ib), and O3—P1—C1—P2 and O4—P2—C1—P1 for (II) (Tables 1, 3 and 5). The values of the relevant angles for (III), i.e. O2—P1—C1—P2 and O6—P2—C1—P1 (Table 7), indicate that atom O6 is the most displaced from the P1—C1—P2 plane compared with the O atoms of (Ia), (Ib) and (II).
The orientation of the phosphonate groups relative to the pyridinium ring is defined by the C3—N1—C1—P1 and C3—N1—C1—P2 torsion angles, which reveal that in all four compounds atoms P1 and P2 have an anticlinal orientation with respect to C3.
Consistent with previous observations, the geometry of both the phosphono (–PO3H2) and the phosphonate (–PO3H-) groups deviates significantly from an ideal tetrahedron (Tables 1, 3, 5 and 7). This is mainly reflected in high values of the O1—P1—O2 angle, in which the unprotonated O atoms are involved [average 115.88 (10)°]. On the other hand, the (H)O—P—C1 angles, in which protonated atoms O3, O5 or O6 are involved, have the smallest value in all four compounds [average 101.46 (11)°].
In agreement with the crystal structures of [(pyridin-2-yl)amino]methane-1,1-diphosphonates reported to date, the supramolecular assembly of the zwitterions of (Ia), (Ib) and (II) and the monoanions in (III) is determined by chain–chain interactions involving phosphono (–PO3H2) and phosphonate (–PO3H-) groups (see Figs. 3 and 4, and Tables 2, 4, 6 and 8).
In (Ia) and (III), (—P—C—P—O—H···O)n chains are generated by direct b-axis translation through O5—H5···O1ii and O6—H6···O2iii interactions, respectively (symmetry codes in Tables 2 and 8, respectively [Please confirm added text]). As shown in Fig. 3, in both (Ia) and (III), two bis-phosphonate ions from adjacent chains, related to each other by the action of a twofold axis, are joined by other O—H···O hydrogen bonds to form ribbons along the b axis. The overall architecture of the ribbons is similar and resembles that observed for related derivatives with 1,3-thiazol-2-yl and 1,3-benzothiazol-2-yl rings (Matczak-Jon, Kowalik-Jankowska et al., 2010). The main difference lies in the number of hydrogen bonds per bis-phosphonate pair, which is four in (Ia) and three in (III). However, while the geometry of both unique chain-linking hydrogen bonds in (Ia) (O3—H3···O2i and O6—H6···O4i; Table 2) is actually the same, the O3—H3···O1i and O5···H5···O5i hydrogen bonds joining related chains in (III) (Table 8) are of significantly different geometry, resulting from the different strength/energy of the two interactions. Notable is the short D···A distance [2.424 (3) Å] in the O5···H5···O5i bond, with the H5 atom on a twofold axis.
Ribbon–ribbon interactions in (Ia) and (III) are provided mainly by direct hydrogen bonds [N—H···O in both (Ia) and (III), and additionally N2—H2N···N2 in (III)] and water- [(Ia)] or cation- [(III)] mediated contacts. In the crystal structure of (Ia), water molecules are located on the twofold axis between the ribbons and interact with two zwitterions from two adjacent ribbons each, as well as with each other. Atom O1W is in hydrogen-bonding contact with two zwitterions (related by the action of a twofold axis) through N1—H1N···O1W and O1W—H2W···O3 bonds, and with the other water molecule via O1W—H1W···O2W, as shown in Fig. 1. On the other hand, aatom O2W interacts with two further zwitterions from the same adjacent ribbons through O2W—H3W···O4iv and O2W—H3W···O5iv hydrogen bonds (Table 2). In this way, two hydrogen-bonded water molecules provide interribbon connections by forming hydrogen bonds with four zwitterions from two adjacent ribbons.
An important role is also played by π–π interactions between aromatic rings of adjacent zwitterions in (Ia), and of the cations and anions in (III). In (Ia), the parallel pyridinium rings in the molecules at (x, y, z) and (-x, -y + 1, -z + 1) have an interplanar spacing of 3.418 (2) Å and a centroid-to-centroid distance of 3.725 (2) Å. In (III), the pyridinium ring of the anion forms stacking interactions with the cations at (-x + 1, y - 1, -z + 1/2) and (-x + 1, y, -z + 1/2), with centroid-to-centroid separations of 3.80 (1) and 3.90 (1) Å, respectively.
In contrast with (Ia) and (III), the crystal structures of (Ib) and (II) have a layered architecture (Fig. 4, and Tables 4 and 6). Here, each (—P—C—P—O—H···O)n chain, generated by a direct c- or a-axis translation through O5—H5···O2ii or O3—H3···O4i interactions, respectively (symmetry codes in Tables 4 and 6, respectively [Please confirm added text]), is joined to two adjacent chains of the same type through two significantly different types of interactions. On the one hand, these are centrosymmetric O6—H6···O1iii [in (Ib), Table 4] and O5—H5···O1ii [in (II), Table 6] hydrogen bonds, resulting in R22(12) and R44(16) rings (Fig. 4) [see Bernstein et al. (1995) for hydrogen-bond notation], and this type of interchain connection is the same in (Ib) and (II). On the other hand, a set of O—H···O and N1—H1N···O hydrogen bonds provides another type of interchain connection which is different in (Ib) and (II) and, therefore, results in different architectures of the layers formed in this way, as shown in Fig. 4. However, the highly corrugated monolayers perpendicular to [100] in (Ib), and the flat plane bilayers parallel to (001) in (II) have a common feature. This is an arrangement of the individual zwitterions within the layer, locating the aromatic rings at the interlayer exterior. This determines the interactions between adjacent layers. In both (Ib) and (II), the interlayer contacts are realised mainly through the N2—H2N···O hydrogen bonds and also by weaker C—H···O interactions involving aromatic C atoms (Tables 4 and 6).
In conclusion, chain–chain interactions involving phosphono (–PO3H2) and phosphonate (–PO3H-) groups are dominant in determining the crystal packing in all four title compounds. In (Ia) and (III), O—H···O interactions connect adjacent chains into similar ribbons, which are held together by N—H···O hydrogen bonds [accompanied by N2—H2N···N2 interactions in (III)], water- or cation-mediated contacts and π–π interactions between aromatic rings. In (Ib) and (II), the combination of O—H···O and N1—H1N···O intermolecular interactions results in highly corrugated monolayers or flat bilayers, respectively, joined through N2—H2N···O hydrogen bonds and weak C—H···O contacts. In contrast with previously studied [(pyridin-2-yl)amino]methane-1,1-diphosphonic acids, neither conformational stabilization is provided through inter- or intramolecular hydrogen bonds [except for the intramolecular N1—H1N···OCl1 interaction in (II)]. This leads us to speculate that the barrier for Z/E interconversion in solution for all four compounds is markedly lower than that for aminobis-phosphonates with pyridin-2-yl side chains.