Di­hydrogen phosphate mediated supra­molecular frameworks in 2- and 4-chloro­anilinium dihydrogen phosphate salts

The title compounds, 2-chloro­anilinium dihydrogen phosphate (2CADHP) and 4-chloro­anilinium di­hydrogen phosphate (4CADHP), both C₆H₇NCl⁺·H₂PO₄⁻, form two-dimensional supra­molecular organic–inorganic hybrid frameworks. In 2CADHP, the dihydrogen phosphate anions form a double-stranded anionic chain generated parallel to the [010] direction through O—H...O hydrogen bonds, whereas in 4CADHP they form a two-dimensional supra­molecular net extending parallel to the crystallographic (001) plane into which the cations are linked through strong N—H...O hydrogen bonds.

S1. Comment

The construction of organic–inorganic hybrid compounds has been of considerable interest and importance in recent years, not only because they are a powerful means of generating interesting supramolecular frameworks but also due to their potential for providing new materials with magnetic, semiconducting, optical and electrolytic properties (Doyle et al., 2002; Zaccaro & Ibanez, 2000; Chisholm & Haile, 2000). The supramolecular frameworks of these organic–inorganic compounds are generated by hydrogen-bond interactions between donor (D) and acceptor (A) moieties. Orthophosphoric acid (H₃PO₄), an inorganic oxy-acid, forms dihydrogen phosphate salts with organic amines, resulting in organic–inorganic hybrid systems with potentially powerful hydrogen-bonded D/A moieties. The dihydrogen phosphate anions (H₂PO₄^-) form substructures in these compounds, generating anionic networks via O—H···O hydrogen bonds which act as a template for the assembly of cations (Shylaja et al., 2008). A considerable number of dihydrogen phosphate salts are recorded in the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002). In the crystal structure of N-benzyl ammonium dihydrogen phosphate monohydrate (Elaoud et al., 1998), the H₂PO₄^- anions form a one-dimensional chain network, while in 3-amino-2-chloropyridinium dihydrogen phosphate (Hamed et al., 2007) they form chains of fused R₂²(8) ring motifs [for graph-set analysis, see Bernstein et al. (1995)]. Two-dimensional nets of anionic substructures were also observed in dimethylammonium dihydrogen phosphate (Pietraszko et al., 1999) and 2-methylpiperazinediium dihydrogen phosphate (Choudhury et al., 2000). Interestingly, in the structure of imidazolinium dihydrogen phosphate (Blessing, 1986), the H₂PO₄^- anions form a three-dimensional cage-type framework inside which the imidazolinium cations are trapped. We have prepared the dihydrogen phosphate salts 2-chloroanilinium dihydrogen phosphate (2CADHP) and 4-chloroanilinium dihydrogen phosphate (4CADHP), and have determined their structures and studied the supramolecular networks in these salts.

The salt 2CADHP crystallizes in the space group P2₁/n, whereas 4CADHP crystallizes in Pbca. The asymmetric units of both 2CADHP and 4CADHP contain a dihydrogen phosphate anion, and a singly protonated 2- or 4-chloroanilinium cation, respectively. In the tetrahedral dihydrogen phosphate group of both 2CADHP and 4CADHP, the protonated P—O bond distances are P1—O1 = 1.570 (1) Å and P1—O2 = 1.553 (1) Å for 2CADHP, and P1—O1 = 1.541 (2) Å and P1—O2 = 1.557 (2) Å for 4CADHP. These values are as expected and are longer than the other two P—O bonds, P1—O3 = 1.504 (1) Å and P1—O4 = 1.503 (1) Å for 2CADHP, and P1—O3 = 1.517 (2) Å and P1—O4 = 1.496 (2) Å for 4CADHP. The identical P1—O3 and P1—O4 bond distances observed in 2CADHP indicate delocalization of negative charge between them (Demir et al., 2006). The geometries of the 2- and 4-chloroanilinium cations show characteristic values compared with other reported structures (Muthamizhchelvan et al., 2005; Glidewell et al., 2005). The C—N distances of the 2- and 4-chloroanilinium cations, C1—N1 = 1.455 (2) and 1.467 (3) Å, respectively, are longer than the normal value and this lengthening is due to the transfer of an H atom to the N atom from the orthophosphoric acid.

The hydrogen-bonded organic–inorganic supramolecular frameworks of 2CADHP and 4CADHP are determined primarily by a combination of O—H···O and N—H···O hydrogen bonds (Tables 1 and 2).

In 2CADHP, the inversion-related H₂PO₄^- anions are linked through an O1—H1D···O3ⁱⁱⁱ hydrogen bond [symmetry code: (iii) -x + 1, -y + 1, -z + 1], forming an O—H···O dimer with a ring motif of R₂²(8) with its centroid occupying the inversion centre. These dimers are interlinked through an O2—H2D···O3ⁱⁱ hydrogen bond [symmetry code: (ii) x, y + 1, z] to form a ring motif of type R₄²(12). The alternately fused R₂²(8) and R₄²(12) supramolecular motifs in turn generate a double-stranded inorganic H₂PO₄^- chain made of P—OH···O═P hydrogen bonds extending infinitely along the [010] direction (Fig. 3). The 2-chloroanilinium cations are linked to the anionic substructure through three N—H···O hydrogen bonds and a Cl···O short contact [Cl···O = 3.170 (1) Å]. The N1—H1A···O4 and N1—H1C···O4ⁱⁱ hydrogen bonds [symmetry code: (ii) x, y + 1, z], with O2—H2D···O3ⁱⁱ, form a chain of edge-fused R₃³(10) ring motifs extending along the [010] direction, as observed in the structure of 3-acetylanilinium dihydrogen phosphate (Cinčić & Kaitner, 2008). The Cl···O1 interaction, which acts as a pseudo hydrogen bond (Bryant et al., 1998; Kubicki & Wagner, 2007), with the Cl atom at (x, y, z) as donor and atom O1 at (-x + 1/2, y + 1/2, -z + 1/2) as acceptor, along with the N—H···O hydrogen bonds, forms a chain of fused R₄²(10) motifs extending along the [010] direction. The 2₁ screw-related chains of R₃³(10) and R₄²(10) motifs along (1/4, y, 1/4) (Fig. 4) link the anionic substructure, resulting in the formation of an organic–inorganic sheet framework parallel to (101) (Fig. 5).

In 4CADHP, the H₂PO₄^- anions form dimers through an O2—H2D···O3^iv hydrogen bond [symmetry code: (iv) -x + 1,-y, -z + 1], with the characteristic ring motif of R₂²(8), in which the centroid of the dimer occupies the crystallographic inversion centre. The O1—H1D···O4ⁱⁱⁱ hydrogen bond [symmetry code: (iii) -x + 3/2, y - 1/2, z] generates a C4 chain which connects the glide-related anionic dimers with the glide plane perpendicular to the [100] direction, the glide component of which is [0, 1/2, 0]. This forms an infinite two-dimensional layer in the form of a net extending parallel to the (001) plane. This inorganic supramolecular net of H₂PO₄^- anions is built from R₂²(8) and R₆⁶(24)-type ring motifs (Fig. 6). The 4-chloroanilinium cations are anchored to the H₂PO₄^- anionic net through N1—H1A···O4ⁱ [symmetry code: -x + 1, -y + 1, -z + 1], N1—H1B···O3 and N1—H1C···O3ⁱⁱ [symmetry code: -x + 3/2, y + 1/2, z] hydrogen bonds, forming fused ring motifs of R₅³(14) and R₅³(12) types with O—H···O hydrogen bonds (Fig. 7). The 4-chloroanilinium cations are pendant on both faces of the anionic net, thus resulting in the formation of two-dimensional sheet of an organic–inorganic supramolecular framework (Fig. 8) extending infinitely parallel to the crystallographic (001) plane.

It is of interest to note that in both the title compounds, although they form different types of anionic substructures, the overall anionic–cationic supramolecular framework results in the formation of infinite two-dimensional sheets. In 2CADHP the formation of an anionic double-stranded substructure and the linking of the cations to it is analogous with other reported structures. In the crystal structures of 2,4-dimethylanilinium dihydrogen phosphate (Fábry et al., 2001), 2-(methoxy carbonyl)anilinium dihydrogen phosphate (Shafiq et al., 2009) and 3,5-dimethoxyanilinium dihydrogen phosphate (Kaabi et al., 2004) (Z' = 2Z), the respective cations bound to the anionic substructures form two-dimensional sheets. In the last compound the substructure was formed with different ring motifs than the other two structures. A three-dimensional hydrogen-bonded framework was observed for 1,3-propanediammonium bis(dihydrogen phosphate) (Marsh, 2004), in which the cation contains an additional three N—H bonds involved in hydrogen bonding. The crystal structure of 4CADHP is isomorphous with 4-bromoanilinium dihydrogen phosphate (CSD refcode UGISEI; Zhang et al., 2001) but no H atoms are reported in CSD. In 4CADHP, the hydrogen-bonded anionic substructure formation and the linking of cation pendants from the supramolecular net are analogous with the structures of 4-methylanilinium dihydrogen phosphate (Smirani et al., 2004) and 4-ethylanilinium dihydrogen phosphate (Kaabi et al., 2003), but has markedly different cell dimensions from 4-bromoanilinium dihydrogen phosphate, even though they belong to the same Pbca space group.

S2. Experimental

Ethanol solutions containing equimolar quantities of 2-chloroaniline and orthophosphoric acid were mixed to produce a white precipitate, which was filtered off, dried for a few hours, dissolved in ethanol and allowed to recrystallize to afford colourless single crystals of 2CADHP after a period of about two weeks.

Colourless crystals of 4CADHP were obtained from a solution of 4-chloroaniline and orthophosphoric acid mixed at a 1:1 stoichiometric ratio in a mixed solvent of ethanol and water in equal proportions (50:50 v/v) upon gentle heating. The solution thus prepared was allowed to crystallize.

S3. Refinement

The positions of the H atoms bound to N and O atoms were identified from difference electron-density maps, but were subsequently geometrically optimized (O—H = 0.82 Å and N—H = 0.89 Å) and allowed to ride at the best staggered positions, with U_iso(H) = 1.5U_eq(O,N), except for O2 of 2CADHP whose O—H vector was allowed to rotate around the P—O bond. H atoms bound to C atoms were treated as riding atoms, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The independent components of 2CADHP, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The independent components of 4CADHP, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Part of the crystal structure of 2CADHP, showing the formation of the double-stranded H2PO4^- anionic chain built from R2^2(8) and R4^2(12) rings through O2—H2D···O3^ii and O1—H1D···O3^iii hydrogen bonds extending infinitely along the [010] direction. [Symmetry codes: (i) x, y + 1, z; (iii) -x + 1, -y + 1, -z + 1.] [Please indicate where axes labels O/a/b/c should be placed]
	Fig. 4. Part of the crystal structure of 2CADHP, showing the 21 screw-related chains of fused R3^3(10) and R4^2(10) rings extending along the [010] direction and linked to the H2PO4^- anions through N1—H1A···O4, N1—H1C···O4^i, N1—H1B···O1^ii and O2—H2D···O3^ii hydrogen bonds. H atoms attached to C atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1/2, y + 1/2, -z + 1/2; (ii) x, y + 1, z.] [Please indicate where axes labels O/a/b/c should be placed]
	Fig. 5. Part of the crystal structure of 2CADHP, showing the formation of the organic–inorganic supramolecular (101) sheet built from R2^2(8), R4^2(12), R3^3(10) and R4^2(10) rings via N—H···O and O—H···O hydrogen bonds and a Cl···O interaction extending along the [010] and [101] directions, respectively. H atoms attached to C atoms have been omitted for clarity. [Please indicate where axes labels O/a/b/c should be placed]
	Fig. 6. Part of the crystal structure of 4CADHP, showing the formation of the two-dimensional (001) net of H2PO4^- anions built from R2^2(8) and R6^6(24) rings through O1—H1D···O4^iii and O2—H2D···O3^iv hydrogen bonds, respectively. [Symmetry codes: (iii) x, y + 1, z; (iv) -x + 1, -y, -z + 1.] [Please indicate where axes labels O/a/b/c should be placed]
	Fig. 7. Part of the crystal structure of 4CADHP, showing the cations linked to the anionic substructure forming R5^3(14) and R5^3(12) fused ring motifs through N1—H1A···O4^i, N1—H1B···O3, N1—H1C···O3^ii, O1—H1D···O4^iii and O2—H2D···O3^iv hydrogen bonds. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 3/2, y + 1/2, z; (iii) -x + 3/2, y - 1/2, z; (iv) -x + 1, -y, -z + 1.] H atoms bonded to C atoms, and the unit-cell outline, have been omitted for clarity.
	Fig. 8. A projection, down [001], of part of the crystal structure of 4CADHP, showing the (001) sheet of the organic–inorganic supramolecular framework built from R2^2(8), R6^6(24), R5^3(14) and R5^3(12) ring motifs extending parallel to the [100] and [010] directions. H atoms bonded to C atoms have been omitted for clarity. [Please indicate where axes labels should be placed]

(2CADHP) 2-chloroanilinium dihydrogen phosphate

Crystal data

C6H7ClN^+·H2PO4^−	F(000) = 464
Mr = 225.56	Dx = 1.681 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2577 reflections
a = 11.3143 (6) Å	θ = 2.6–37.6°
b = 4.7466 (2) Å	µ = 0.59 mm^−1
c = 17.5024 (9) Å	T = 292 K
β = 108.540 (3)°	Prism, colourless
V = 891.17 (8) Å^3	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker Kappa APEX2 CCD area-detector diffractometer	2044 independent reflections
Radiation source: fine-focus sealed tube	1902 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω and ϕ scan	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker 1999)	h = −14→14
Tmin = 0.867, Tmax = 0.917	k = −6→5
9738 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 0.5784P] where P = (Fo^2 + 2Fc^2)/3
2044 reflections	(Δ/σ)max < 0.001
122 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.33498 (4)	0.64044 (10)	0.07416 (3)	0.04460 (14)
N1	0.37364 (12)	1.0574 (3)	0.20551 (8)	0.0286 (3)
H1A	0.3708	0.9044	0.2343	0.045 (6)*
H1B	0.3022	1.0743	0.1654	0.043 (6)*
H1C	0.3852	1.2088	0.2370	0.043 (6)*
C1	0.47615 (13)	1.0322 (3)	0.17262 (9)	0.0251 (3)
C2	0.46861 (14)	0.8402 (3)	0.11197 (9)	0.0296 (3)
C3	0.56680 (17)	0.8111 (4)	0.08157 (11)	0.0398 (4)
H3	0.5621	0.6805	0.0411	0.048*
C4	0.67135 (16)	0.9755 (4)	0.11129 (11)	0.0403 (4)
H4	0.7373	0.9564	0.0907	0.048*
C5	0.67890 (15)	1.1683 (4)	0.17127 (12)	0.0394 (4)
H5	0.7495	1.2806	0.1907	0.047*
C6	0.58152 (15)	1.1959 (4)	0.20286 (10)	0.0339 (3)
H6	0.5872	1.3239	0.2441	0.041*
P1	0.46720 (3)	0.59433 (8)	0.37887 (2)	0.02464 (12)
O1	0.37359 (10)	0.6990 (3)	0.42244 (7)	0.0325 (3)
H1D	0.4056	0.6818	0.4713	0.049*
O2	0.56282 (12)	0.8335 (3)	0.38337 (10)	0.0447 (3)
H2D	0.5365	0.9815	0.3959	0.067*
O3	0.53878 (11)	0.3420 (2)	0.42139 (7)	0.0324 (3)
O4	0.39025 (11)	0.5470 (3)	0.29244 (7)	0.0352 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0364 (2)	0.0442 (3)	0.0524 (3)	−0.01116 (18)	0.01287 (19)	−0.0176 (2)
N1	0.0243 (6)	0.0287 (7)	0.0343 (6)	−0.0005 (5)	0.0115 (5)	−0.0029 (5)
C1	0.0229 (6)	0.0247 (7)	0.0279 (7)	0.0020 (5)	0.0084 (5)	0.0026 (6)
C2	0.0267 (7)	0.0288 (8)	0.0328 (7)	−0.0014 (6)	0.0090 (6)	−0.0013 (6)
C3	0.0393 (9)	0.0438 (10)	0.0411 (9)	0.0008 (8)	0.0197 (7)	−0.0082 (8)
C4	0.0309 (8)	0.0491 (11)	0.0466 (9)	0.0039 (8)	0.0206 (7)	0.0045 (8)
C5	0.0257 (7)	0.0405 (10)	0.0518 (10)	−0.0050 (7)	0.0118 (7)	0.0021 (8)
C6	0.0287 (7)	0.0324 (8)	0.0400 (8)	−0.0030 (6)	0.0101 (6)	−0.0054 (7)
P1	0.02322 (19)	0.0191 (2)	0.0331 (2)	0.00011 (13)	0.01108 (15)	−0.00416 (14)
O1	0.0262 (5)	0.0394 (7)	0.0341 (6)	0.0079 (5)	0.0126 (4)	−0.0008 (5)
O2	0.0368 (6)	0.0235 (6)	0.0835 (10)	−0.0073 (5)	0.0329 (7)	−0.0143 (6)
O3	0.0353 (6)	0.0230 (5)	0.0389 (6)	0.0059 (4)	0.0117 (5)	−0.0023 (5)
O4	0.0398 (6)	0.0322 (6)	0.0325 (6)	0.0011 (5)	0.0101 (5)	−0.0043 (5)

Geometric parameters (Å, º)

Cl1—C2	1.7281 (16)	C4—H4	0.9300
N1—C1	1.4545 (18)	C5—C6	1.387 (2)
N1—H1A	0.8900	C5—H5	0.9300
N1—H1B	0.8900	C6—H6	0.9300
N1—H1C	0.8900	P1—O4	1.5031 (12)
C1—C6	1.380 (2)	P1—O3	1.5036 (12)
C1—C2	1.381 (2)	P1—O2	1.5529 (12)
C2—C3	1.383 (2)	P1—O1	1.5696 (11)
C3—C4	1.374 (3)	O1—H1D	0.8200
C3—H3	0.9300	O2—H2D	0.8200
C4—C5	1.375 (3)
C1—N1—H1A	109.5	C3—C4—H4	119.9
C1—N1—H1B	109.5	C5—C4—H4	119.9
H1A—N1—H1B	109.5	C4—C5—C6	120.20 (16)
C1—N1—H1C	109.5	C4—C5—H5	119.9
H1A—N1—H1C	109.5	C6—C5—H5	119.9
H1B—N1—H1C	109.5	C1—C6—C5	119.52 (16)
C6—C1—C2	120.08 (14)	C1—C6—H6	120.2
C6—C1—N1	120.15 (14)	C5—C6—H6	120.2
C2—C1—N1	119.76 (13)	O4—P1—O3	115.32 (7)
C1—C2—C3	120.05 (15)	O4—P1—O2	109.36 (8)
C1—C2—Cl1	119.28 (12)	O3—P1—O2	107.48 (7)
C3—C2—Cl1	120.67 (13)	O4—P1—O1	105.78 (7)
C4—C3—C2	119.86 (16)	O3—P1—O1	110.63 (7)
C4—C3—H3	120.1	O2—P1—O1	108.10 (7)
C2—C3—H3	120.1	P1—O1—H1D	109.5
C3—C4—C5	120.28 (16)	P1—O2—H2D	109.5
C6—C1—C2—C3	0.2 (2)	C2—C3—C4—C5	0.2 (3)
N1—C1—C2—C3	−178.68 (15)	C3—C4—C5—C6	0.7 (3)
C6—C1—C2—Cl1	−179.20 (13)	C2—C1—C6—C5	0.7 (3)
N1—C1—C2—Cl1	1.9 (2)	N1—C1—C6—C5	179.57 (15)
C1—C2—C3—C4	−0.6 (3)	C4—C5—C6—C1	−1.2 (3)
Cl1—C2—C3—C4	178.74 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.89	1.95	2.8348 (19)	170
N1—H1B···O1^i	0.89	2.17	3.0509 (18)	169
N1—H1C···O4^ii	0.89	1.87	2.7515 (18)	172
O1—H1D···O3^iii	0.82	1.78	2.6017 (17)	174
O2—H2D···O3^ii	0.82	1.77	2.5411 (17)	157

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

(4CADHP) 4-chloroanilinium dihydrogen phosphate

Crystal data

C6H7ClN^+·H2PO4^−	F(000) = 928
Mr = 225.56	Dx = 1.554 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5587 reflections
a = 9.7371 (19) Å	θ = 2.7–32.2°
b = 7.8756 (16) Å	µ = 0.55 mm^−1
c = 25.141 (5) Å	T = 292 K
V = 1927.9 (7) Å^3	Block, colourless
Z = 8	0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEX2 CCD area-detector diffractometer	1687 independent reflections
Radiation source: fine-focus sealed tube	1483 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω and ϕ scan	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker 1999)	h = −11→6
Tmin = 0.876, Tmax = 0.899	k = −8→9
8591 measured reflections	l = −29→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0676P)^2 + 1.7857P] where P = (Fo^2 + 2Fc^2)/3
1687 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.61909 (6)	0.19672 (8)	0.46396 (2)	0.0289 (2)
Cl1	0.61167 (12)	0.36351 (16)	0.80580 (3)	0.0813 (4)
O1	0.7408 (3)	0.1346 (3)	0.43001 (9)	0.0736 (8)
H1D	0.7639	0.0395	0.4398	0.093 (15)*
O2	0.4834 (3)	0.1235 (3)	0.44054 (9)	0.0703 (8)
H2D	0.4699	0.0284	0.4527	0.102 (16)*
O3	0.63585 (16)	0.1436 (2)	0.52159 (7)	0.0308 (4)
O4	0.60899 (17)	0.3847 (2)	0.45644 (8)	0.0387 (5)
N1	0.6296 (2)	0.4693 (3)	0.57205 (8)	0.0312 (5)
H1A	0.5527	0.5201	0.5614	0.041 (7)*
H1B	0.6371	0.3689	0.5561	0.069 (11)*
H1C	0.7014	0.5337	0.5635	0.046 (8)*
C1	0.6256 (2)	0.4451 (3)	0.62989 (9)	0.0293 (5)
C2	0.5171 (3)	0.3573 (4)	0.65153 (10)	0.0398 (6)
H2	0.4475	0.3155	0.6298	0.048*
C3	0.5125 (3)	0.3318 (4)	0.70585 (11)	0.0475 (7)
H3	0.4404	0.2714	0.7210	0.057*
C4	0.6158 (3)	0.3967 (4)	0.73744 (11)	0.0468 (8)
C5	0.7237 (3)	0.4844 (4)	0.71567 (11)	0.0516 (8)
H5	0.7930	0.5271	0.7374	0.062*
C6	0.7288 (3)	0.5091 (4)	0.66095 (10)	0.0430 (7)
H6	0.8014	0.5684	0.6456	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0317 (4)	0.0256 (4)	0.0295 (4)	−0.0008 (2)	−0.0001 (2)	0.0046 (2)
Cl1	0.1035 (8)	0.1110 (9)	0.0294 (4)	0.0185 (6)	0.0018 (4)	0.0117 (4)
O1	0.0992 (19)	0.0690 (16)	0.0525 (12)	0.0503 (15)	0.0374 (13)	0.0272 (12)
O2	0.0885 (17)	0.0660 (16)	0.0564 (13)	−0.0453 (13)	−0.0389 (13)	0.0316 (12)
O3	0.0313 (9)	0.0311 (9)	0.0301 (9)	−0.0035 (7)	−0.0023 (7)	0.0037 (7)
O4	0.0350 (10)	0.0291 (10)	0.0519 (11)	0.0000 (7)	−0.0002 (8)	0.0095 (8)
N1	0.0320 (11)	0.0298 (11)	0.0318 (11)	0.0023 (8)	−0.0008 (8)	0.0026 (9)
C1	0.0309 (12)	0.0277 (13)	0.0294 (12)	0.0051 (9)	0.0000 (9)	0.0026 (10)
C2	0.0332 (13)	0.0479 (16)	0.0384 (14)	−0.0019 (12)	−0.0016 (11)	0.0044 (12)
C3	0.0422 (15)	0.0597 (19)	0.0406 (15)	0.0015 (13)	0.0097 (12)	0.0097 (13)
C4	0.0578 (18)	0.0544 (19)	0.0283 (13)	0.0134 (14)	0.0001 (12)	0.0040 (12)
C5	0.0597 (18)	0.0521 (18)	0.0431 (15)	−0.0044 (15)	−0.0180 (14)	−0.0026 (14)
C6	0.0430 (15)	0.0456 (16)	0.0404 (14)	−0.0092 (13)	−0.0055 (11)	0.0056 (12)

Geometric parameters (Å, º)

P1—O4	1.4957 (19)	C1—C6	1.369 (4)
P1—O3	1.5168 (17)	C1—C2	1.375 (3)
P1—O1	1.541 (2)	C2—C3	1.381 (4)
P1—O2	1.557 (2)	C2—H2	0.9300
Cl1—C4	1.739 (3)	C3—C4	1.379 (4)
O1—H1D	0.8200	C3—H3	0.9300
O2—H2D	0.8200	C4—C5	1.372 (4)
N1—C1	1.467 (3)	C5—C6	1.390 (4)
N1—H1A	0.8900	C5—H5	0.9300
N1—H1B	0.8900	C6—H6	0.9300
N1—H1C	0.8900
O4—P1—O3	113.62 (11)	C2—C1—N1	118.5 (2)
O4—P1—O1	107.15 (12)	C1—C2—C3	119.3 (3)
O3—P1—O1	111.03 (11)	C1—C2—H2	120.4
O4—P1—O2	105.25 (12)	C3—C2—H2	120.4
O3—P1—O2	110.52 (11)	C4—C3—C2	119.5 (3)
O1—P1—O2	109.00 (17)	C4—C3—H3	120.2
P1—O1—H1D	109.5	C2—C3—H3	120.2
P1—O2—H2D	109.5	C5—C4—C3	121.0 (3)
C1—N1—H1A	109.5	C5—C4—Cl1	119.2 (2)
C1—N1—H1B	109.5	C3—C4—Cl1	119.8 (2)
H1A—N1—H1B	109.5	C4—C5—C6	119.5 (3)
C1—N1—H1C	109.5	C4—C5—H5	120.2
H1A—N1—H1C	109.5	C6—C5—H5	120.2
H1B—N1—H1C	109.5	C1—C6—C5	119.1 (3)
C6—C1—C2	121.6 (2)	C1—C6—H6	120.4
C6—C1—N1	119.9 (2)	C5—C6—H6	120.4
C6—C1—C2—C3	−0.6 (4)	C3—C4—C5—C6	0.3 (5)
N1—C1—C2—C3	179.3 (2)	Cl1—C4—C5—C6	179.0 (2)
C1—C2—C3—C4	0.9 (4)	C2—C1—C6—C5	0.1 (4)
C2—C3—C4—C5	−0.7 (5)	N1—C1—C6—C5	−179.8 (2)
C2—C3—C4—Cl1	−179.4 (2)	C4—C5—C6—C1	0.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^i	0.89	1.80	2.689 (3)	176
N1—H1B···O3	0.89	1.97	2.862 (3)	175
N1—H1C···O3^ii	0.89	2.09	2.951 (3)	162
O1—H1D···O4^iii	0.82	1.79	2.540 (3)	152
O2—H2D···O3^iv	0.82	1.82	2.585 (3)	155

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