Poly[(2,2′-bipyridine-κ2N,N′)(μ2-dihydrogen phosphato-κ2O:O′)(μ2-hydrogen phosphato-κ2O:O′)aluminium(III)], Al(2,2′-bipy)(HPO4)(H2PO4), a layered inorganic–organic hybrid material

Chippindale, A.M.

doi:10.1107/S0108270106024309

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 8| August 2006| Pages m372-m374

doi:10.1107/S0108270106024309

Poly[(2,2′-bipyridine-κ²N,N′)(μ₂-dihydrogen phosphato-κ²O:O′)(μ₂-hydrogen phosphato-κ²O:O′)aluminium(III)], Al(2,2′-bipy)(HPO₄)(H₂PO₄), a layered inorganic–organic hybrid material

Ann M. Chippindale ^a ^*

^aSchool of Chemistry, University of Reading, Berks RG6 6AD, England
^*Correspondence e-mail: a.m.chippindale@rdg.ac.uk

(Received 13 June 2006; accepted 23 June 2006; online 29 July 2006)

The title compound, [Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)]_n, consists of AlO₄N₂ octahedra vertex-linked to H₂PO₄ and HPO₄ tetrahedra to form layers based on a (4,12)-net. The layers stack in an AAA fashion, held in place by π–π interactions between 2,2′-bipyridine molecules coordinated to Al atoms in adjacent layers.

Comment

The use of organic amines as structure-directing agents or templates in the solvothermal synthesis of open-framework metal phosphates is well documented (Cheetham et al., 1999 ). In a few metal phosphates, amines also act as ligands and bond via nitrogen to the metal centres to form MO_xN_y units within the framework. For example, in [TH₂]₂[TH]₂[Zn₁₂(PO₄)₁₀(H₂O)₂]·H₂O (T = 1,3-diaminopropane; Vaidhyanathan et al., 1999 ), the diamine is present in two distinct forms, both as a free dication and as a monocation with the –NH₂ group bonded to zinc generating ZnO₃N as well as ZnO₄ tetrahedra within the zinc–phosphate framework. Several such metal phosphates containing MO_xN_y units have been prepared using 2,2′-bipyridine. The majority of these have chain structures in which metal and phosphorus centres are linked through oxygen bridges. Examples include phosphates of Mn (Sarneski et al., 1993 ), Cd (Lin et al., 2003 ) and mixed Zn–V (Finn & Zubieta, 2002 ). In addition, layered phosphates of Ga (Lin et al., 2004 ), V (Lu et al., 2002 ) and mixed Cu–V (Finn & Zubieta, 2000 ) are also known, in which the metals coordinate to 2,2′-bipyridine. In this work, the first aluminium phosphate (AlPO) incorporating 2,2′-bipyridine is described. The structure of the title compound, (I), differs from that of all previously reported AlPOs in that it has direct Al—N bonding, giving rise to unusual AlO₄N₂ units with octahedral coordination.

The Al atom, like all the atoms in the asymmetric unit, lies on a general position with average Al1—N and Al1—O

distances of 2.075 (16) and 1.86 (3) Å, respectively (Table 1

). These average bonding distances are similar to those found in other octahedrally coordinated aluminium compounds in which aluminium is coordinated to 2,2′-bipyridine (Bellavance et al., 1977

) or constitutes part of an AlPO framework (Kniep et al., 1978

), respectively. Atom Al1 is connected via Al—O—P bridges to two crystallographically distinct P atoms, viz. P1 and P2, both of which have two terminal P—O bonds to complete the tetrahedral coordination. The O—P—O angles lie in the range 106.6 (1)–114.1 (1)°. Linkages P1—O2, P1—O3 and P2—O7 constitute POH groups, as confirmed both by the location of H atoms in the difference Fourier maps and by bond-valence calculations (Brese & O'Keeffe, 1991

) (Fig. 1

). The remaining terminal linkage, P2—O6, has some degree of multiple-bond character, although hydrogen-bonding interactions between atom O6 and neighbouring POH groups (see below) leads to a lengthening of this bond compared with a free P=O bond. The Al1O₄N₂, H₂P1O₄ and HP2O₄ units link through their vertices to generate infinite undulating neutral layers of formula [Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)], which lie in the bc plane and stack in an AAA sequence along the a axis. The layers can be described as consisting of four-membered rings of alternating Al1O₄N₂ and H₂P1O₄ units linked together by bridging HP2O₄ units to give 12-membered rings with cross-pore oxygen-to-oxygen distances O1ⁱ⋯O1ⁱⁱ = 8.510 (3) Å, O2ⁱ⋯O2ⁱⁱ = 7.679 (4) Å and O7ⁱ⋯O7ⁱⁱ = 5.172 (3) Å (Fig. 2

). Within the 12-membered rings, there are strong hydrogen bonds involving the terminal P2—O6 groups and P1—OH and P2—OH groups (Table 2

). The bidentate bipyridine groups bonded to atom Al1 lie perpendicular to the AlPO (4,12)-net (Wells, 1984

) and project into the interlayer space (Fig. 3

). The shortest distance between 2,2′-bipyridine molecules on adjacent layers is 3.386 (4) Å, suggesting some degree of π–π interaction.

[Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)] is isostructural with a reported layered gallium phosphate (Lin et al., 2004). The structure is also closely related to that of [Mn(HPO₄)(H₂PO₄)(C₁₀H₈N₂)] (Sarneski et al., 1993). In the latter, the four-membered rings of Mn₂P₂ units link through further phosphate groups to give a linear polymeric array rather than the layered structure observed here.

The title structure does, however, possess several features that are rare in AlPOs. Firstly, the layers are not charged; all other layered AlPOs have negatively charged metal–phosphate layers with positively charged species, e.g. alkali-metal or amine cations, between the layers. Secondly, the mixed oxygen–nitrogen octahedral coordination of aluminium is unknown in AlPOs, although AlO₄N₂ units have been observed previously in an aluminophosphinate dimer and related polymer (Wang et al., 2000 ). In a typical contrasting example, an AlPO prepared in the presence of 4,4′-bipyridine, viz. (C₁₀H₉N₂)[Al(PO₄)(H₂PO₄)], which has the same Al:P ratio of 1:2 as the title compound, has an AlPO framework consisting of negatively charged chains of linked AlO₄ and PO₄ tetrahedra held together by hydrogen bonding between the framework O atoms and the 4,4′-bipyridine cations (Chippindale & Turner, 1997 ).

Figure 1
The local coordination of atoms in [Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)] (50% probability displacement ellipsoids). [Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

Figure 2
A view along the a axis of one layer of the title compound, showing the (4,12)-network formed from linking octahedral AlO₄N₂ and tetrahedral HPO₄ and H₂PO₄ units. The four- and 12-membered rings (4 and 12 MR) referred to in the Comment are labelled, together with atoms O1, O2 and O7. The C atoms of 2,2′-bipyridine and all H atoms have been omitted. Short O⋯O contacts, indicative of intralayer hydrogen bonds, occur between the terminal O6 group and the O2—H, O3—H and O7—H groups. Key: Al black spheres, P grey spheres, O white spheres and N small grey spheres. [Symmetry codes: (i) $[x, -y+{1\over2}, z+{1\over2}]$ ; (ii) -x+1, $[y+{1\over2}]$ , $[-z+{1\over2}]$ ; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z.]

Figure 3
A view along the c axis showing the stacking of the layers. Key as for Fig. 2

, with small black spheres representing H atoms.

Experimental

Single crystals of [Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)] were prepared under solvothermal conditions. Aluminium isopropoxide (1 g) was dispersed in butan-2-ol (7.86 ml) by stirring, followed by addition of 2,2′-bipyridine (1.835 g) and a small amount of Si(OEt)₄ (0.1 ml), which acts as a mineralizer. Aqueous H₃PO₄ (0.63 ml, 85 wt%) was then added, and the gel was stirred until homogeneous, sealed in a Teflon-lined autoclave and heated at 453 K for 10 d. The solid product was collected by filtration, washed copiously with water and dried in air at 353 K. A clear colourless hexagonal plate was isolated from the bulk sample for analysis. The experimental and simulated powder X-ray diffraction patterns are in good agreement, suggesting that the sample is monophasic. Thermogravimetric analysis showed a smooth weight loss of 46.7% over the range 553–693 K, to give a black X-ray amorphous product. The observed weight loss is in good agreement with the loss of one mole of 2,2′-bipyridine (41.5%) and one mole of water (4.8%).

Crystal data

[Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)]
M_r = 376.14
Monoclinic, P 2₁ /c
a = 10.9253 (2) Å
b = 15.6992 (3) Å
c = 8.3683 (2) Å
β = 109.0658 (11)°
V = 1356.58 (5) Å³
Z = 4
D_x = 1.842 Mg m⁻³
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 150 (2) K
Hexagonal plate, colourless
0.08 × 0.08 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.97, T_max = 1.00
5615 measured reflections
3079 independent reflections
2238 reflections with I > 2σ(I)
R_int = 0.021
θ_max = 27.5°

Refinement

Refinement on F
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.041
S = 1.12
2238 reflections
220 parameters
H atoms treated by a mixture of independent and constrained refinement
Modified Chebychev polynomial (Watkin, 1994 ) with the coefficients 0.747, 0.542 and 0.526
(Δ/σ)_max < 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Al1—O1	1.8899 (17)
Al1—O4ⁱ	1.8319 (17)
Al1—O5	1.8307 (17)
Al1—O8ⁱⁱ	1.8744 (17)
Al1—N1	2.063 (2)
Al1—N2	2.086 (2)
P1—O1	1.5013 (16)
P1—O2	1.5565 (17)
P1—O3	1.5604 (18)
P1—O4	1.5075 (16)
P2—O5	1.5128 (16)
P2—O6	1.5375 (17)
P2—O7	1.5801 (17)
P2—O8	1.5134 (16)

O1—Al1—O4ⁱ	92.40 (7)
O1—Al1—O5	90.10 (8)
O4ⁱ—Al1—O5	100.33 (8)
O1—Al1—O8ⁱⁱ	170.90 (8)
O4ⁱ—Al1—O8ⁱⁱ	92.46 (8)
O5—Al1—O8ⁱⁱ	96.59 (8)
O1—Al1—N1	86.11 (8)
O4ⁱ—Al1—N1	169.43 (8)
O5—Al1—N1	90.15 (8)
O8ⁱⁱ—Al1—N1	87.70 (8)
O1—Al1—N2	87.15 (8)
O4ⁱ—Al1—N2	91.51 (8)
O5—Al1—N2	167.95 (8)
O8ⁱⁱ—Al1—N2	85.04 (8)
N1—Al1—N2	77.97 (8)
Al1—O1—P1	137.6 (1)
Al1ⁱ—O4—P1	154.29 (11)
Al1—O5—P2	147.74 (12)
Al1ⁱⁱⁱ—O8—P2	148.21 (11)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6^iv	0.86 (4)	1.73 (4)	2.581 (2)	169 (4)
O3—H3⋯O6ⁱ	0.84 (4)	1.80 (4)	2.644 (3)	178 (4)
O7—H7⋯O6ⁱⁱⁱ	0.90 (4)	1.76 (4)	2.658 (3)	176 (4)
Symmetry codes: (i) -x+1, -y, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, $[y-{\script{1\over 2}}]$ , $[-z+{\script{1\over 2}}]$ .

H atoms attached to the 2,2′-bipyridine and phosphate units were located in difference Fourier maps. The fractional coordinates and isotropic displacement parameters of the phosphate H atoms were refined. The bipyridine H atoms were, however, positioned geometrically during the final refinement cycles and constrained to ride on their parent C atoms [C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C)].

Data collection: COLLECT (Nonius, 2001 ); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: CAMERON (Watkin et al., 1996 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106024309/bg3011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106024309/bg3011Isup2.hkl

Comment top

The use of organic amines as structure-directing agents or templates in the solvothermal synthesis of open-framework metal phosphates is well documented (Cheetham et al., 1999). In a few metal phosphates, amines also act as ligands and bond via nitrogen to the metal centres to form MO_xN_y units within the framework. For example, in [TH₂]₂[TH]₂[Zn₁₂(OH₂)₂(PO₄)₁₀]·H₂O (T = 1,3-diaminopropane) (Vaidhyanathan et al., 1999), the diamine is present in two distinct forms, both as a free dication and as a monocation with the –NH₂ group bonded to zinc generating ZnO₃N as well as ZnO₄ tetrahedra within the zinc–phosphate framework. Several such metal phosphates containing MO_xN_y units have been prepared using 2,2'-bipyridine. The majority of these have chain structures in which metal and phosphorus centres are linked through oxygen bridges. Examples include phosphates of Mn (Sarneski et al., 1993), Cd (Lin et al., 2003) and mixed Zn–V (Finn & Zubieta, 2002). In addition, layered phosphates of Ga (Lin et al., 2004), V (Lu et al., 2002) and mixed Cu–V (Finn & Zubieta, 2000) are also known, in which the metals coordinate to 2,2'-bipyridine. In this work, the first aluminium phosphate (AlPO) incorporating 2,2'-bipyridine is described. The structure differs from all previously reported AlPOs in that it has direct Al—N bonding giving rise to unusual AlO₄N₂ units with octahedral coordination.

The Al atom, like all the atoms in the asymmetric unit, lies on a general position with Al1—N_av and Al1—O_av distances of 2.075 (16) and 1.86 (3) Å, respectively. Both of these average bonding distances are similar to those found in other octahedrally coordinated aluminium compounds in which the aluminium is coordinated to 2,2'-bipyridine (Bellavance et al., 1977) or constitutes part of an AlPO framework (Kniep et al., 1978), respectively. Atom Al1 is connected via Al—O—P bridges to two crystallographically distinct P atoms, P1 and P2, both of which have two terminal P—O bonds to complete the tetrahedral coordination. The O—P—O angles lie in the range 106.6 (1)–114.1 (1)°. P1—O2, P1—O3 and P2—O7 constitute P—OH groups, as confirmed both by the location of hydrogen atoms in the difference Fourier maps and by bond-valence calculations (Brese & O'Keeffe, 1991) (Fig. 1). The remaining terminal linkage, P2—O6, has some degree of multiple-bond character, although hydrogen-bonding interactions between O6 and neighbouring P—OH groups (see below) leads to a lengthening of this bond compared with a free P═O bond. The Al1O₄N₂, H₂P1O₄ and HP2O₄ units link through their vertices to generate infinite undulating neutral layers of formula Al(C₁₀N₂H₈)(HPO₄)(H₂PO₄), which lie in the bc plane and stack in an AAA sequence along the a axis. The layers can be described as consisting of four-membered rings of alternating Al1O₄N₂ and H₂P1O₄ units linked together by bridging HP2O₄ units to give 12-membered rings with cross-pore oxygen to oxygen distances O1···O1' = 8.510 (3) Å, O2···O2' = 7.679 (4) Å and O7···O7' = 5.172 (3) Å (Fig. 2). Within the 12-membered rings, there are strong hydrogen bonds involving the terminal P2/O6 groups and P1/OH and P2/OH groups [O6···O distances lie in the range 2.581 (2)–2.658 (3) Å]. The bidentate bipyridine groups bonded to atom Al1 lie perpendicular to the AlPO (4,12)-net (Wells, 1984) and project into the interlayer space (Fig. 3). The shortest distance between 2,2'-bipyridine molecules on adjacent layers is 3.386 (4) Å suggesting some degree of π–π interaction.

Al(C₁₀N₂H₈)(HPO₄)(H₂PO₄) is isostructural with a layered gallium phosphate reported recently (Lin et al., 2004). The structure is also closely related to that of Mn(C₁₀N₂H₈)(HPO₄)(H₂PO₄) (Sarneski et al., 1993). In the latter, the four-membered rings of Mn₂P₂ units link through further phosphate groups to give a linear polymeric array rather than the layered structure observed here.

The title structure does, however, possess several features that are rare in AlPOs. Firstly, the layers are not charged; all other layered AlPOs have negatively charged metal-phosphate layers with positively charged species, e.g. alkali-metal or amine cations, between the layers. Secondly, the mixed oxygen–nitrogen octahedral coordination of aluminium is unknown in AlPOs, although AlO₄N₂ units have been observed previously in an aluminophosphinate dimer and related polymer (Wang et al., 2000). In a typical contrasting example, an AlPO prepared in the presence of 4,4'-bipyridine, [C₁₀N₂H₉][Al(PO₄)(H₂PO₄)], which has the same Al:P ratio of 1:2 as the title compound, has an AlPO framework consisting of negatively charged chains of linked AlO₄ and PO₄ tetrahedra held together by hydrogen bonding between the framework O atoms and the 4,4'-bipyridine cations (Chippindale & Turner, 1997).

Experimental top

Single crystals of Al(C₁₀N₂H₈)(HPO₄)(H₂PO₄) were prepared under solvothermal conditions. Aluminium isopropoxide (1 g) was dispersed in butan-2-ol (7.86 ml) by stirring, followed by addition of 2,2'-bipyridine (1.835 g) and a small amount of Si(OEt)₄ (0.1 ml), which acts as a mineralizer. Aqueous H₃PO₄ (0.63 ml, 85 wt%) was then added and the gel was stirred until homogeneous, sealed in a Teflon-lined autoclave, and heated at 453 K for 10 d. The solid product was collected by filtration, washed copiously with water and dried in air at 353 K. A clear colourless hexagonal plate was isolated from the bulk sample for analysis. The experimental and simulated powder X-ray diffraction patterns are in good agreement, suggesting that the sample is monophasic. Thermogravimetric analysis using a Stanton Redcroft STA 1000 Thermal Analyser over the range 295–1073 K, at a heating rate of 10 K min⁻¹ under flowing N₂, showed a smooth weight loss of 46.7% over 553–693 K, to give a black X-ray amorphous product. The observed weight loss is in good agreement with the loss of one mole of 2,2'-bipyridine (41.5%) and one mole of water (4.8%).

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK; data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

Figures top

	Fig. 1. Local coordination of atoms in Al(C₁₀N₂H₈)(HPO₄)(H₂PO₄) (50% probability displacement ellipsoids). [Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) x, −y + 1/2, z + 1/2.]
	Fig. 2. A view along the a axis of one layer of the title compound, showing the (4,12)-network formed from linking octahedral AlO₄N₂ and tetrahedral HPO₄ and H₂PO₄ units. The four- and 12-membered rings (4 and 12 MR) referred to in the text are labelled, together with atoms O1 O2 and O7. The C atoms of the 2,2'-bipyridine and all H atoms have been omitted. Short O···O contacts, indicative of intralayer hydrogen bonds, occur between the terminal O6 group and atoms O2H, O3H and O7H. Key: Al, black spheres; P, grey spheres; O, white spheres; N, small grey spheres.
	Fig. 3. A view along the c axis showing the stacking of the layers. Key as for Fig. 2, with small grey spheres representing hydrogen.

Poly[(2,2'-bipyridine-κ²N,N')(µ₂-hydrogen phosphato)(µ₂-dihydrogen phosphato)aluminium(III)] top

Crystal data top

[Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)]	F(000) = 768.000
M_r = 376.14	D_x = 1.842 Mg m⁻³
Monoclinic, P2₁/c	Melting point: not measured K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.9253 (2) Å	Cell parameters from 3131 reflections
b = 15.6992 (3) Å	θ = 5–27°
c = 8.3683 (2) Å	µ = 0.43 mm⁻¹
β = 109.0658 (11)°	T = 150 K
V = 1356.58 (5) Å³	Hexagonal plate, colourless
Z = 4	0.08 × 0.08 × 0.01 mm

Data collection top

Enraf–Nonius KappaCCD diffractometer	2238 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −14→14
T_min = 0.97, T_max = 1.00	k = −20→18
5615 measured reflections	l = −10→10
3079 independent reflections

Refinement top

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	Modified Chebychev polynomial (Watkin, 1994); W = [weight][1 - (δF/6σF)²]², with coefficients 0.747, 0.542 and 0.526
S = 1.12	(Δ/σ)_max = 0.000137
2238 reflections	Δρ_max = 0.35 e Å⁻³
220 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints

Crystal data top

[Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)]	V = 1356.58 (5) Å³
M_r = 376.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9253 (2) Å	µ = 0.43 mm⁻¹
b = 15.6992 (3) Å	T = 150 K
c = 8.3683 (2) Å	0.08 × 0.08 × 0.01 mm
β = 109.0658 (11)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	3079 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	2238 reflections with I > 2σ(I)
T_min = 0.97, T_max = 1.00	R_int = 0.021
5615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.041	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.35 e Å⁻³
2238 reflections	Δρ_min = −0.48 e Å⁻³
220 parameters

Special details top

Experimental. Thermogravimetric analysis using a Stanton Redcroft STA 1000 Thermal Analyser over the range 295–1073 K, at a heating rate of 10 K min⁻¹ under flowing N₂.

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

	x	y	z	U_iso*/U_eq
Al1	0.33722 (6)	0.11702 (4)	0.45485 (8)	0.0151
P1	0.35434 (5)	−0.07885 (4)	0.37549 (7)	0.0137
P2	0.44344 (5)	0.21582 (4)	0.19047 (7)	0.0151
O1	0.29540 (15)	0.0085 (1)	0.3538 (2)	0.0163
O2	0.29123 (18)	−0.12728 (12)	0.2062 (2)	0.0252
O3	0.31179 (18)	−0.12502 (13)	0.5139 (2)	0.0279
O4	0.49944 (14)	−0.0829 (1)	0.4190 (2)	0.0171
O5	0.36772 (16)	0.15630 (11)	0.2653 (2)	0.0204
O6	0.55159 (16)	0.25843 (11)	0.33436 (19)	0.0199
O7	0.51146 (17)	0.15828 (11)	0.0893 (2)	0.0215
O8	0.35594 (15)	0.2779 (1)	0.0666 (2)	0.0191
N1	0.14300 (19)	0.14493 (13)	0.3472 (3)	0.0200
N2	0.26171 (19)	0.07492 (14)	0.6399 (2)	0.0199
C1	0.0885 (2)	0.17565 (17)	0.1911 (3)	0.0257
C2	−0.0449 (3)	0.18628 (19)	0.1194 (4)	0.0364
C3	−0.1235 (3)	0.16563 (19)	0.2133 (5)	0.0390
C4	−0.0683 (3)	0.13487 (19)	0.3760 (4)	0.0329
C5	0.0655 (2)	0.12496 (15)	0.4400 (3)	0.0210
C6	0.1342 (2)	0.09104 (15)	0.6102 (3)	0.0222
C7	0.0758 (3)	0.0765 (2)	0.7322 (4)	0.0339
C8	0.1503 (3)	0.0440 (2)	0.8874 (4)	0.0373
C9	0.2779 (3)	0.02525 (19)	0.9158 (3)	0.0345
C10	0.3318 (3)	0.04208 (18)	0.7896 (3)	0.0259
H2	0.340 (4)	−0.169 (3)	0.201 (5)	0.038 (9)*
H3	0.356 (4)	−0.168 (3)	0.560 (5)	0.04 (1)*
H7	0.521 (3)	0.187 (3)	0.000 (5)	0.04 (1)*
H11	0.1454	0.1916	0.1235	0.0282*
H21	−0.0830	0.2086	0.0016	0.0391*
H31	−0.2195	0.1728	0.1642	0.0423*
H41	−0.1237	0.1200	0.4464	0.0391*
H71	−0.0181	0.0893	0.7086	0.0451*
H81	0.1110	0.0343	0.9782	0.0503*
H91	0.3318	−0.0002	1.0259	0.0420*
H101	0.4255	0.0293	0.8113	0.0310*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0143 (3)	0.0144 (3)	0.0163 (3)	−0.0000 (2)	0.0047 (2)	−0.0001 (2)
P1	0.0124 (2)	0.0139 (3)	0.0144 (3)	−0.0001 (2)	0.0038 (2)	−0.0001 (2)
P2	0.0171 (3)	0.0132 (3)	0.0164 (3)	0.0009 (2)	0.0076 (2)	0.0017 (2)
O1	0.0153 (7)	0.0138 (8)	0.0186 (8)	0.0015 (6)	0.0037 (6)	−0.0007 (6)
O2	0.0220 (9)	0.0228 (9)	0.0231 (9)	0.0041 (7)	−0.0033 (7)	−0.0098 (7)
O3	0.0240 (9)	0.032 (1)	0.033 (1)	0.0101 (8)	0.0167 (8)	0.0177 (8)
O4	0.0134 (7)	0.0155 (8)	0.0223 (8)	0.0011 (6)	0.0057 (6)	−0.0010 (6)
O5	0.0239 (8)	0.0179 (8)	0.0216 (8)	−0.0024 (7)	0.0105 (7)	0.0029 (6)
O6	0.0224 (8)	0.0214 (9)	0.0154 (7)	−0.0022 (7)	0.0055 (7)	0.0010 (6)
O7	0.0266 (9)	0.0216 (9)	0.0190 (8)	0.0063 (7)	0.0112 (7)	0.0023 (7)
O8	0.0180 (7)	0.0149 (8)	0.0239 (8)	0.0009 (6)	0.0062 (6)	0.0055 (6)
N1	0.0196 (9)	0.0157 (9)	0.023 (1)	−0.0016 (7)	0.0055 (8)	−0.0027 (8)
N2	0.0218 (9)	0.021 (1)	0.0179 (9)	−0.0021 (8)	0.0084 (8)	−0.0021 (8)
C1	0.0234 (12)	0.0218 (12)	0.0253 (12)	−0.001 (1)	−0.001 (1)	−0.000 (1)
C2	0.0315 (14)	0.0255 (14)	0.0409 (15)	0.0017 (12)	−0.0037 (12)	0.0003 (12)
C3	0.0190 (11)	0.0275 (14)	0.0592 (19)	0.0019 (11)	−0.0027 (12)	−0.0090 (13)
C4	0.0204 (12)	0.0282 (14)	0.0492 (17)	−0.001 (1)	0.0102 (11)	−0.0099 (12)
C5	0.0182 (11)	0.015 (1)	0.0304 (12)	−0.0013 (9)	0.0090 (9)	−0.0062 (9)
C6	0.0257 (12)	0.0159 (11)	0.0293 (12)	−0.0024 (9)	0.015 (1)	−0.0063 (9)
C7	0.0364 (14)	0.0350 (15)	0.0413 (15)	−0.0067 (12)	0.0275 (13)	−0.0073 (13)
C8	0.0571 (19)	0.0331 (15)	0.0354 (15)	−0.0151 (14)	0.0339 (14)	−0.0070 (12)
C9	0.0503 (18)	0.0323 (15)	0.0225 (12)	−0.0136 (13)	0.0141 (12)	0.0010 (11)
C10	0.0327 (13)	0.0278 (13)	0.0170 (11)	−0.005 (1)	0.008 (1)	0.0024 (9)

Geometric parameters (Å, º) top

Al1—O1	1.8899 (17)	N2—C6	1.356 (3)
Al1—O4ⁱ	1.8319 (17)	N2—C10	1.339 (3)
Al1—O5	1.8307 (17)	C1—C2	1.392 (4)
Al1—O8ⁱⁱ	1.8744 (17)	C1—H11	1.000
Al1—N1	2.063 (2)	C2—C3	1.379 (5)
Al1—N2	2.086 (2)	C2—H21	1.000
P1—O1	1.5013 (16)	C3—C4	1.384 (5)
P1—O2	1.5565 (17)	C3—H31	1.000
P1—O3	1.5604 (18)	C4—C5	1.392 (4)
P1—O4	1.5075 (16)	C4—H41	1.000
P2—O5	1.5128 (16)	C5—C6	1.476 (4)
P2—O6	1.5375 (17)	C6—C7	1.388 (3)
P2—O7	1.5801 (17)	C7—C8	1.386 (5)
P2—O8	1.5134 (16)	C7—H71	1.000
O2—H2	0.86 (4)	C8—C9	1.367 (5)
O3—H3	0.84 (4)	C8—H81	1.000
O7—H7	0.90 (4)	C9—C10	1.393 (4)
N1—C1	1.336 (3)	C9—H91	1.000
N1—C5	1.360 (3)	C10—H101	1.000

O1—Al1—O4ⁱ	92.40 (7)	Al1—N1—C5	116.45 (16)
O1—Al1—O5	90.10 (8)	C1—N1—C5	118.7 (2)
O4ⁱ—Al1—O5	100.33 (8)	Al1—N2—C6	115.87 (16)
O1—Al1—O8ⁱⁱ	170.90 (8)	Al1—N2—C10	124.91 (17)
O4ⁱ—Al1—O8ⁱⁱ	92.46 (8)	C6—N2—C10	118.8 (2)
O5—Al1—O8ⁱⁱ	96.59 (8)	N1—C1—C2	122.3 (3)
O1—Al1—N1	86.11 (8)	N1—C1—H11	118.847
O4ⁱ—Al1—N1	169.43 (8)	C2—C1—H11	118.847
O5—Al1—N1	90.15 (8)	C1—C2—C3	119.0 (3)
O8ⁱⁱ—Al1—N1	87.70 (8)	C1—C2—H21	120.499
O1—Al1—N2	87.15 (8)	C3—C2—H21	120.499
O4ⁱ—Al1—N2	91.51 (8)	C2—C3—C4	119.4 (3)
O5—Al1—N2	167.95 (8)	C2—C3—H31	120.314
O8ⁱⁱ—Al1—N2	85.04 (8)	C4—C3—H31	120.307
N1—Al1—N2	77.97 (8)	C3—C4—C5	118.9 (3)
O1—P1—O2	106.9 (1)	C3—C4—H41	120.557
O1—P1—O3	107.1 (1)	C5—C4—H41	120.556
O2—P1—O3	107.35 (11)	N1—C5—C4	121.8 (3)
O1—P1—O4	116.31 (9)	N1—C5—C6	114.8 (2)
O2—P1—O4	108.5 (1)	C4—C5—C6	123.5 (2)
O3—P1—O4	110.3 (1)	N2—C6—C5	114.4 (2)
O5—P2—O6	109.19 (9)	N2—C6—C7	121.7 (2)
O5—P2—O7	106.6 (1)	C5—C6—C7	123.9 (2)
O6—P2—O7	107.03 (9)	C6—C7—C8	118.6 (3)
O5—P2—O8	111.9 (1)	C6—C7—H71	120.699
O6—P2—O8	114.1 (1)	C8—C7—H71	120.695
O7—P2—O8	107.7 (1)	C7—C8—C9	119.8 (2)
Al1—O1—P1	137.6 (1)	C7—C8—H81	120.119
P1—O2—H2	109 (2)	C9—C8—H81	120.119
P1—O3—H3	116 (3)	C8—C9—C10	119.1 (3)
Al1ⁱ—O4—P1	154.29 (11)	C8—C9—H91	120.438
Al1—O5—P2	147.74 (12)	C10—C9—H91	120.435
P2—O7—H7	111 (3)	N2—C10—C9	121.9 (3)
Al1ⁱⁱⁱ—O8—P2	148.21 (11)	N2—C10—H101	119.062
Al1—N1—C1	124.75 (17)	C9—C10—H101	119.063

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6^iv	0.86 (4)	1.73 (4)	2.581 (2)	169 (4)
O3—H3···O6ⁱ	0.84 (4)	1.80 (4)	2.644 (3)	178 (4)
O7—H7···O6ⁱⁱⁱ	0.90 (4)	1.76 (4)	2.658 (3)	176 (4)

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

Experimental details

Crystal data
Chemical formula	[Al(HPO₄)(H₂PO₄)(C₁₀H₈N₂)]
M_r	376.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	10.9253 (2), 15.6992 (3), 8.3683 (2)
β (°)	109.0658 (11)
V (Å³)	1356.58 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.08 × 0.08 × 0.01

Data collection
Diffractometer	Enraf–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.97, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	5615, 3079, 2238
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.041, 1.12
No. of reflections	2238
No. of parameters	220
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.48

Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1996), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), CRYSTALS.

Selected geometric parameters (Å, º) top

Al1—O1	1.8899 (17)	P1—O2	1.5565 (17)
Al1—O4ⁱ	1.8319 (17)	P1—O3	1.5604 (18)
Al1—O5	1.8307 (17)	P1—O4	1.5075 (16)
Al1—O8ⁱⁱ	1.8744 (17)	P2—O5	1.5128 (16)
Al1—N1	2.063 (2)	P2—O6	1.5375 (17)
Al1—N2	2.086 (2)	P2—O7	1.5801 (17)
P1—O1	1.5013 (16)	P2—O8	1.5134 (16)

O1—Al1—O4ⁱ	92.40 (7)	O1—Al1—N2	87.15 (8)
O1—Al1—O5	90.10 (8)	O4ⁱ—Al1—N2	91.51 (8)
O4ⁱ—Al1—O5	100.33 (8)	O5—Al1—N2	167.95 (8)
O1—Al1—O8ⁱⁱ	170.90 (8)	O8ⁱⁱ—Al1—N2	85.04 (8)
O4ⁱ—Al1—O8ⁱⁱ	92.46 (8)	N1—Al1—N2	77.97 (8)
O5—Al1—O8ⁱⁱ	96.59 (8)	Al1—O1—P1	137.6 (1)
O1—Al1—N1	86.11 (8)	Al1ⁱ—O4—P1	154.29 (11)
O4ⁱ—Al1—N1	169.43 (8)	Al1—O5—P2	147.74 (12)
O5—Al1—N1	90.15 (8)	Al1ⁱⁱⁱ—O8—P2	148.21 (11)
O8ⁱⁱ—Al1—N1	87.70 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6^iv	0.86 (4)	1.73 (4)	2.581 (2)	169 (4)
O3—H3···O6ⁱ	0.84 (4)	1.80 (4)	2.644 (3)	178 (4)
O7—H7···O6ⁱⁱⁱ	0.90 (4)	1.76 (4)	2.658 (3)	176 (4)

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

Acknowledgements

The author thanks the Leverhulme Trust for a Research Fellowship. Charlie Turner and Dr Andrew Cowley, Chemical Crystallography Laboratory, Oxford, are also thanked for practical assistance.

References

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ISSN: 2053-2296

Volume 62| Part 8| August 2006| Pages m372-m374

doi:10.1107/S0108270106024309

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