Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022325/pv2010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022325/pv2010Isup2.hkl |
CCDC reference: 651432
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.085
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Adams (1977); Blessing (1986); Desiraju (1989, 1995); Nelmes & Choudhary (1978); Spek (2003).
For related literature, see: Hebert (1978); Masse & Durif (1990).
Single crystals of C5H6N2ClH2PO4 were prepared by adding drop by drop 0.25 mmol of orthophosphoric acid in 50 ml of water, to a solution of 3-amino-2chloro pyridine (m = 0.5 g, 3.88 mmol) in ethanol. The solution thus obtained was slowly evaporated at room temperature, until the formation of crystals of (I) of good quality.
Chemistry of organic-inorganic hybrid materials continue to be a focus area in material science. In the last few years, a considerable stategy employed in crystal engineering, is to take advantage of hydrogen bond interactions. Indeed, hydrogen bonds are of value not only because they are recognized as the most powerful force to generate interesting supramolecular networks (Desiraju, 1989; Desiraju, 1995)) but also because of their widespread biological occurrence (Adams, (1977); Nelmes & Choudhary (1978); Blessing, (1986)). As part of our continuing interest in this field, we have synthesized a new compound, 3-amino-2-chloropiridinium dihydrogenmonophosphate (I),
The Crystal structure of (I), consists of dihydrogenmonophosphate anions, and 3-amino-2-chloropiridinium cations. The asymmetric unit contains one crystallographically independent cation and an anion (Fig. 1). The H2PO4- anion shows its normal tetrahedral geometry with the protonated P1—O1 and P1—O2 vertices showing their expected lengthening relative to the unprotonated P—O bonds (Table 1). The 3-amino-2-cloropyridinium cation shows no unusual geometrical features. The anions are linked into polymeric chains of single tetrahedra propagating along [001] by way of the O1—H1···O4 and O2—H2···O3 hydrogen bonds. Similar chains have been seen in amphetamine dihydrogenmonophosphate (Hebert,1978) and in L,b-methyl alaninium dihydrogenmonophosphate (Masse & Durif, 1990). These polymeric chains are interconnected by means of N—H···O hydrogen bonds originating from the NH2 groups of organic cation, to form infinite layers parallel to the ac plane and centred at y = 0 and y =1/2, as shown in Fig. 2. Charge compensation of these layers is achieved by the incorporation of the protonated pyridinium cation in the inetrlayer spaces. The cationic units interact with the anionic framework through different interactions (electrostatic, H-bonds and Van Der Waals) to make up into three dimensional infinite network. The organic and the inorganic species interact by way of three types of hydrogen bonds. The first one O—H···.O, involving short contacts H···.O of lengths 1.81 Å and 1.83 Å, connects the H2PO4- anions to develop the corrugated chains along the c direction. The second type N—H···.O, with N···O distances ranging from 2.577 (3) Å to 3.052 (3) Å, interconnects two successive chains, while the pertinent angles fall in the interval 149° to 173°. A PLATON (Spek, 2003) analysis of (I) indicated the presence of a third type of weak C—H···O contacts that ensure the cohesion of the ionic groups, giving rise to three-dimensional complex network of hydrogen bonds. It is worth noticing, the presence of a weak intramolecular bonding identified by PLATON (Spek, 2003) analysis (N2—H21···Cl = 2.66 (3) Å), occurring between NH2 group adjacent to Cl group to reinforce the pyridinium cation.
For related literature, see: Adams (1977); Blessing (1986); Desiraju (1989, 1995); Nelmes & Choudhary (1978); Spek (2003).
For related literature, see: Hebert (1978); Masse & Durif (1990).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. ORTEP-3 (Farrugia,1999) view of (I) with atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level | |
Fig. 2. Projection of (I) along c axis. |
C5H6ClN2+·H2PO4− | F(000) = 464 |
Mr = 226.55 | Dx = 1.687 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.391 (2) Å | θ = 8–10° |
b = 16.230 (3) Å | µ = 0.59 mm−1 |
c = 7.504 (4) Å | T = 293 K |
β = 97.73 (3)° | Prism, colorless |
V = 891.9 (6) Å3 | 0.21 × 0.19 × 0.17 mm |
Z = 4 |
Enraf–Nonius Turbo-CAD-4 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 25°, θmin = 2° |
Graphite monochromator | h = −8→8 |
non–profiled ω scans | k = 0→19 |
3120 measured reflections | l = −8→8 |
1568 independent reflections | 2 standard reflections every 120 min |
1467 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.5528P] where P = (Fo2 + 2Fc2)/3 |
1568 reflections | (Δ/σ)max = 0.0001 |
126 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C5H6ClN2+·H2PO4− | V = 891.9 (6) Å3 |
Mr = 226.55 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.391 (2) Å | µ = 0.59 mm−1 |
b = 16.230 (3) Å | T = 293 K |
c = 7.504 (4) Å | 0.21 × 0.19 × 0.17 mm |
β = 97.73 (3)° |
Enraf–Nonius Turbo-CAD-4 diffractometer | Rint = 0.022 |
3120 measured reflections | 2 standard reflections every 120 min |
1568 independent reflections | intensity decay: 1% |
1467 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.32 e Å−3 |
1568 reflections | Δρmin = −0.39 e Å−3 |
126 parameters |
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. H atoms bonded to N2 were allowed to refine while the rest of the H-atoms were treated as riding, with C—H = 0.93 A °, N—H =0.86 A ° and O—H = 0.82 A °, and with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(O). |
x | y | z | Uiso*/Ueq | ||
P | 0.40091 (7) | 0.51420 (3) | 0.23747 (7) | 0.03013 (17) | |
Cl | 0.32834 (7) | 0.72253 (4) | 0.51245 (8) | 0.04714 (19) | |
O1 | 0.5783 (2) | 0.55975 (10) | 0.3199 (2) | 0.0455 (4) | |
H1 | 0.6305 | 0.5327 | 0.4038 | 0.068* | |
O2 | 0.4582 (2) | 0.42619 (8) | 0.1812 (2) | 0.0424 (4) | |
H2 | 0.5285 | 0.4302 | 0.1059 | 0.064* | |
O3 | 0.3260 (2) | 0.56276 (9) | 0.0720 (2) | 0.0439 (4) | |
O4 | 0.27281 (19) | 0.50273 (9) | 0.3745 (2) | 0.0374 (3) | |
N1 | 0.0778 (2) | 0.82641 (10) | 0.5819 (2) | 0.0357 (4) | |
H11 | 0.1582 | 0.8624 | 0.5625 | 0.043* | |
N2 | 0.0393 (3) | 0.60423 (12) | 0.5991 (3) | 0.0482 (5) | |
H22 | −0.050 (4) | 0.5675 (16) | 0.606 (3) | 0.046 (7)* | |
H21 | 0.138 (4) | 0.5870 (17) | 0.561 (4) | 0.056 (8)* | |
C1 | 0.1183 (3) | 0.74668 (12) | 0.5701 (3) | 0.0322 (4) | |
C2 | −0.0037 (3) | 0.68483 (12) | 0.6048 (3) | 0.0325 (4) | |
C3 | −0.1721 (3) | 0.71241 (12) | 0.6491 (3) | 0.0370 (5) | |
H3 | −0.2588 | 0.6740 | 0.6737 | 0.044* | |
C4 | −0.2113 (3) | 0.79467 (13) | 0.6568 (3) | 0.0418 (5) | |
H4 | −0.3243 | 0.8118 | 0.6847 | 0.050* | |
C5 | −0.0826 (3) | 0.85219 (13) | 0.6228 (3) | 0.0415 (5) | |
H5 | −0.1077 | 0.9082 | 0.6284 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.0342 (3) | 0.0262 (3) | 0.0324 (3) | 0.00296 (18) | 0.0132 (2) | 0.00355 (18) |
Cl | 0.0324 (3) | 0.0520 (3) | 0.0595 (4) | −0.0018 (2) | 0.0151 (2) | −0.0031 (3) |
O1 | 0.0473 (9) | 0.0466 (9) | 0.0440 (9) | −0.0149 (7) | 0.0113 (7) | 0.0093 (7) |
O2 | 0.0565 (9) | 0.0285 (7) | 0.0471 (9) | 0.0075 (6) | 0.0247 (7) | 0.0042 (6) |
O3 | 0.0531 (9) | 0.0438 (8) | 0.0375 (8) | 0.0213 (7) | 0.0161 (7) | 0.0093 (6) |
O4 | 0.0366 (7) | 0.0408 (8) | 0.0383 (8) | −0.0012 (6) | 0.0174 (6) | 0.0004 (6) |
N1 | 0.0394 (9) | 0.0308 (9) | 0.0369 (9) | −0.0086 (7) | 0.0050 (7) | −0.0011 (7) |
N2 | 0.0422 (11) | 0.0303 (9) | 0.0761 (15) | 0.0001 (8) | 0.0229 (10) | −0.0013 (9) |
C1 | 0.0307 (9) | 0.0344 (10) | 0.0318 (10) | −0.0019 (8) | 0.0051 (7) | −0.0018 (8) |
C2 | 0.0329 (10) | 0.0320 (10) | 0.0330 (10) | −0.0021 (8) | 0.0058 (8) | −0.0013 (8) |
C3 | 0.0345 (10) | 0.0362 (11) | 0.0418 (11) | −0.0050 (8) | 0.0110 (9) | −0.0043 (9) |
C4 | 0.0347 (11) | 0.0404 (11) | 0.0519 (13) | 0.0007 (9) | 0.0116 (9) | −0.0089 (10) |
C5 | 0.0433 (12) | 0.0321 (10) | 0.0496 (12) | 0.0008 (9) | 0.0079 (9) | −0.0061 (9) |
P—O4 | 1.5001 (15) | C1—C2 | 1.397 (3) |
P—O3 | 1.5116 (16) | C2—C3 | 1.404 (3) |
P—O1 | 1.5591 (16) | C3—C4 | 1.369 (3) |
P—O2 | 1.5641 (14) | C4—C5 | 1.381 (3) |
O1—H1 | 0.8200 | N2—H22 | 0.90 (3) |
O2—H2 | 0.8200 | N2—H21 | 0.87 (3) |
Cl—C1 | 1.712 (2) | C3—H3 | 0.9300 |
N1—H11 | 0.8600 | C4—C5 | 1.381 (3) |
N1—C5 | 1.332 (3) | C4—H4 | 0.9300 |
N1—C1 | 1.334 (3) | C5—H5 | 0.9300 |
N2—C2 | 1.348 (3) | ||
O4—P—O3 | 115.62 (9) | N1—C5—C4 | 119.14 (19) |
O4—P—O1 | 111.20 (9) | P—O1—H1 | 109.5 |
O3—P—O1 | 105.94 (9) | P—O2—H2 | 109.5 |
O4—P—O2 | 106.88 (8) | C5—N1—H11 | 118.8 |
O3—P—O2 | 109.68 (9) | C1—N1—H11 | 118.8 |
O1—P—O2 | 107.25 (9) | C2—N2—H22 | 117.7 (16) |
C5—N1—C1 | 122.31 (17) | C2—N2—H21 | 122.5 (18) |
N1—C1—C2 | 121.94 (18) | H22—N2—H21 | 118 (2) |
N1—C1—Cl | 117.24 (15) | C4—C3—H3 | 119.3 |
C2—C1—Cl | 120.82 (15) | C2—C3—H3 | 119.3 |
N2—C2—C1 | 122.07 (19) | C3—C4—H4 | 120.1 |
N2—C2—C3 | 122.47 (19) | C5—C4—H4 | 120.1 |
C1—C2—C3 | 115.45 (18) | N1—C5—H5 | 120.4 |
C4—C3—C2 | 121.34 (19) | C4—C5—H5 | 120.4 |
C3—C4—C5 | 119.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.81 | 2.611 (3) | 164 |
O2—H2···O3ii | 0.82 | 1.83 | 2.646 (3) | 177 |
N1—H11···O3iii | 0.86 | 1.73 | 2.577 (3) | 168 |
N2—H21···Cl | 0.87 (3) | 2.66 (3) | 3.008 (3) | 105 (2) |
N2—H21···O4 | 0.87 (3) | 2.28 (3) | 3.052 (3) | 149 (3) |
N2—H22···O4iv | 0.90 (3) | 2.02 (3) | 2.915 (3) | 173 (3) |
C3—H3···O2iv | 0.93 | 2.54 | 3.446 (3) | 166 |
C4—H4···O1v | 0.93 | 2.47 | 3.164 (3) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x, −y+3/2, z+1/2; (iv) −x, −y+1, −z+1; (v) x−1, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C5H6ClN2+·H2PO4− |
Mr | 226.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.391 (2), 16.230 (3), 7.504 (4) |
β (°) | 97.73 (3) |
V (Å3) | 891.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.21 × 0.19 × 0.17 |
Data collection | |
Diffractometer | Enraf–Nonius Turbo-CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3120, 1568, 1467 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.085, 1.08 |
No. of reflections | 1568 |
No. of parameters | 126 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.39 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.81 | 2.611 (3) | 164 |
O2—H2···O3ii | 0.82 | 1.83 | 2.646 (3) | 177 |
N1—H11···O3iii | 0.86 | 1.73 | 2.577 (3) | 168 |
N2—H21···Cl | 0.87 (3) | 2.66 (3) | 3.008 (3) | 105 (2) |
N2—H21···O4 | 0.87 (3) | 2.28 (3) | 3.052 (3) | 149 (3) |
N2—H22···O4iv | 0.90 (3) | 2.02 (3) | 2.915 (3) | 173 (3) |
C3—H3···O2iv | 0.93 | 2.54 | 3.446 (3) | 166 |
C4—H4···O1v | 0.93 | 2.47 | 3.164 (3) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x, −y+3/2, z+1/2; (iv) −x, −y+1, −z+1; (v) x−1, −y+3/2, z+1/2. |
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Chemistry of organic-inorganic hybrid materials continue to be a focus area in material science. In the last few years, a considerable stategy employed in crystal engineering, is to take advantage of hydrogen bond interactions. Indeed, hydrogen bonds are of value not only because they are recognized as the most powerful force to generate interesting supramolecular networks (Desiraju, 1989; Desiraju, 1995)) but also because of their widespread biological occurrence (Adams, (1977); Nelmes & Choudhary (1978); Blessing, (1986)). As part of our continuing interest in this field, we have synthesized a new compound, 3-amino-2-chloropiridinium dihydrogenmonophosphate (I),
The Crystal structure of (I), consists of dihydrogenmonophosphate anions, and 3-amino-2-chloropiridinium cations. The asymmetric unit contains one crystallographically independent cation and an anion (Fig. 1). The H2PO4- anion shows its normal tetrahedral geometry with the protonated P1—O1 and P1—O2 vertices showing their expected lengthening relative to the unprotonated P—O bonds (Table 1). The 3-amino-2-cloropyridinium cation shows no unusual geometrical features. The anions are linked into polymeric chains of single tetrahedra propagating along [001] by way of the O1—H1···O4 and O2—H2···O3 hydrogen bonds. Similar chains have been seen in amphetamine dihydrogenmonophosphate (Hebert,1978) and in L,b-methyl alaninium dihydrogenmonophosphate (Masse & Durif, 1990). These polymeric chains are interconnected by means of N—H···O hydrogen bonds originating from the NH2 groups of organic cation, to form infinite layers parallel to the ac plane and centred at y = 0 and y =1/2, as shown in Fig. 2. Charge compensation of these layers is achieved by the incorporation of the protonated pyridinium cation in the inetrlayer spaces. The cationic units interact with the anionic framework through different interactions (electrostatic, H-bonds and Van Der Waals) to make up into three dimensional infinite network. The organic and the inorganic species interact by way of three types of hydrogen bonds. The first one O—H···.O, involving short contacts H···.O of lengths 1.81 Å and 1.83 Å, connects the H2PO4- anions to develop the corrugated chains along the c direction. The second type N—H···.O, with N···O distances ranging from 2.577 (3) Å to 3.052 (3) Å, interconnects two successive chains, while the pertinent angles fall in the interval 149° to 173°. A PLATON (Spek, 2003) analysis of (I) indicated the presence of a third type of weak C—H···O contacts that ensure the cohesion of the ionic groups, giving rise to three-dimensional complex network of hydrogen bonds. It is worth noticing, the presence of a weak intramolecular bonding identified by PLATON (Spek, 2003) analysis (N2—H21···Cl = 2.66 (3) Å), occurring between NH2 group adjacent to Cl group to reinforce the pyridinium cation.