metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2053-2296

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

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 ππ 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[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268-3292.]). In a few metal phosphates, amines also act as ligands and bond via nitro­gen to the metal centres to form MOxNy 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[Vaidhyanathan, R., Natarajan, S. & Rao, C. N. R. (1999). J. Mater. Chem. 9, 2789-2793.]), 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 MOxNy 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[Sarneski, J. E., Brzezinski, L. J., Anderson, B., Didiuk, M., Manchanda, R., Crabtree, R. H., Brudvig, G. W. & Schulte, G. K. (1993). Inorg. Chem. 32, 3265-3269.]), Cd (Lin et al., 2003[Lin, Z. E., Sun, Y. Q., Zhang, J. & Yang, G. Y. (2003). J. Mater. Chem. 13, 447-449.]) and mixed Zn–V (Finn & Zubieta, 2002[Finn, R. C. & Zubieta, J. (2002). J. Chem. Soc. Dalton Trans. pp. 856-861.]). In addition, layered phosphates of Ga (Lin et al., 2004[Lin, Z. E., Zhang, J., Sun, Y. Q. & Yang, G. Y. (2004). Inorg. Chem. 43, 797-801.]), V (Lu et al., 2002[Lu, Y., Wang, E., Yuan, M., Luan, G., Li, Y., Zhang, H., Hu, C., Yao, Y., Qin, Y. & Chen, Y. (2002). J. Chem. Soc. Dalton Trans. pp. 3029-3031.]) and mixed Cu–V (Finn & Zubieta, 2000[Finn, R. C. & Zubieta, J. (2000). J. Chem. Soc. Dalton Trans. pp. 1321-1322.]) 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)[link], 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

[Scheme 1]
distances of 2.075 (16) and 1.86 (3) Å, respectively (Table 1[link]). 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[Bellavance, P., Corey, E. R., Corey, J. Y. & Hey, G. W. (1977). Inorg. Chem. 16, 462-467.]) or constitutes part of an AlPO framework (Kniep et al., 1978[Kniep, D., Mootz, D. & Wilms, A. (1978). Z. Naturforsch. Teil B, 33, 1047-1048.]), 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[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]) (Fig. 1[link]). 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[link]). 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[link]). The bidentate bipyridine groups bonded to atom Al1 lie perpendicular to the AlPO (4,12)-net (Wells, 1984[Wells, A. F. (1984). Structural Inorganic Chemistry, 5th ed., pp. 63-140. Oxford University Press.]) and project into the inter­layer space (Fig. 3[link]). The shortest distance between 2,2′-bipyridine mol­ecules on adjacent layers is 3.386 (4) Å, suggesting some degree of ππ inter­action.

[Al(HPO4)(H2PO4)(C10H8N2)] is isostructural with a reported layered gallium phosphate (Lin et al., 2004[Lin, Z. E., Zhang, J., Sun, Y. Q. & Yang, G. Y. (2004). Inorg. Chem. 43, 797-801.]). The structure is also closely related to that of [Mn(HPO4)(H2PO4)(C10H8N2)] (Sarneski et al., 1993[Sarneski, J. E., Brzezinski, L. J., Anderson, B., Didiuk, M., Manchanda, R., Crabtree, R. H., Brudvig, G. W. & Schulte, G. K. (1993). Inorg. Chem. 32, 3265-3269.]). 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[Wang, Y., Parkin, S. & Atwood, D. (2000). Chem. Commun. pp. 1799-1800.]). 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[Chippindale, A. M. & Turner, C. (1997). J. Solid State Chem. 128, 318-322.]).

[Figure 1]
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]
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]
Figure 3
A view along the c axis showing the stacking of the layers. Key as for Fig. 2[link], 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)]

  • Mr = 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

  • Dx = 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[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) Tmin = 0.97, Tmax = 1.00

  • 5615 measured reflections

  • 3079 independent reflections

  • 2238 reflections with I > 2σ(I)

  • Rint = 0.021

  • θmax = 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[Watkin, D. (1994). Acta Cryst. A50, 411-437.]) with the coefficients 0.747, 0.542 and 0.526

  • (Δ/σ)max < 0.001

  • Δρmax = 0.35 e Å−3

  • Δρmin = −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 DA D—H⋯A
O2—H2⋯O6iv 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 Uiso(H) = 1.2Ueq(C)].

Data collection: COLLECT (Nonius, 2001[Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Supporting information


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 MOxNy 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 MOxNy 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—Nav and Al1—Oav 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 PO 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 ππ 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%).

Refinement top

The 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 carbon atoms [C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C)].

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
[Figure 1] 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.]
[Figure 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.
[Figure 3] 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
Mr = 376.14Dx = 1.842 Mg m3
Monoclinic, P21/cMelting point: not measured K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.9253 (2) ÅCell parameters from 3131 reflections
b = 15.6992 (3) Åθ = 5–27°
c = 8.3683 (2) ŵ = 0.43 mm1
β = 109.0658 (11)°T = 150 K
V = 1356.58 (5) Å3Hexagonal plate, colourless
Z = 40.08 × 0.08 × 0.01 mm
Data collection top
Enraf–Nonius KappaCCD
diffractometer
2238 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 27.5°, θmin = 5.2°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 1414
Tmin = 0.97, Tmax = 1.00k = 2018
5615 measured reflectionsl = 1010
3079 independent reflections
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H 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 reflectionsΔρmax = 0.35 e Å3
220 parametersΔρmin = 0.48 e Å3
0 restraints
Crystal data top
[Al(HPO4)(H2PO4)(C10H8N2)]V = 1356.58 (5) Å3
Mr = 376.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.9253 (2) ŵ = 0.43 mm1
b = 15.6992 (3) ÅT = 150 K
c = 8.3683 (2) Å0.08 × 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)
Tmin = 0.97, Tmax = 1.00Rint = 0.021
5615 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.041H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.35 e Å3
2238 reflectionsΔρmin = 0.48 e Å3
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
xyzUiso*/Ueq
Al10.33722 (6)0.11702 (4)0.45485 (8)0.0151
P10.35434 (5)0.07885 (4)0.37549 (7)0.0137
P20.44344 (5)0.21582 (4)0.19047 (7)0.0151
O10.29540 (15)0.0085 (1)0.3538 (2)0.0163
O20.29123 (18)0.12728 (12)0.2062 (2)0.0252
O30.31179 (18)0.12502 (13)0.5139 (2)0.0279
O40.49944 (14)0.0829 (1)0.4190 (2)0.0171
O50.36772 (16)0.15630 (11)0.2653 (2)0.0204
O60.55159 (16)0.25843 (11)0.33436 (19)0.0199
O70.51146 (17)0.15828 (11)0.0893 (2)0.0215
O80.35594 (15)0.2779 (1)0.0666 (2)0.0191
N10.14300 (19)0.14493 (13)0.3472 (3)0.0200
N20.26171 (19)0.07492 (14)0.6399 (2)0.0199
C10.0885 (2)0.17565 (17)0.1911 (3)0.0257
C20.0449 (3)0.18628 (19)0.1194 (4)0.0364
C30.1235 (3)0.16563 (19)0.2133 (5)0.0390
C40.0683 (3)0.13487 (19)0.3760 (4)0.0329
C50.0655 (2)0.12496 (15)0.4400 (3)0.0210
C60.1342 (2)0.09104 (15)0.6102 (3)0.0222
C70.0758 (3)0.0765 (2)0.7322 (4)0.0339
C80.1503 (3)0.0440 (2)0.8874 (4)0.0373
C90.2779 (3)0.02525 (19)0.9158 (3)0.0345
C100.3318 (3)0.04208 (18)0.7896 (3)0.0259
H20.340 (4)0.169 (3)0.201 (5)0.038 (9)*
H30.356 (4)0.168 (3)0.560 (5)0.04 (1)*
H70.521 (3)0.187 (3)0.000 (5)0.04 (1)*
H110.14540.19160.12350.0282*
H210.08300.20860.00160.0391*
H310.21950.17280.16420.0423*
H410.12370.12000.44640.0391*
H710.01810.08930.70860.0451*
H810.11100.03430.97820.0503*
H910.33180.00021.02590.0420*
H1010.42550.02930.81130.0310*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0143 (3)0.0144 (3)0.0163 (3)0.0000 (2)0.0047 (2)0.0001 (2)
P10.0124 (2)0.0139 (3)0.0144 (3)0.0001 (2)0.0038 (2)0.0001 (2)
P20.0171 (3)0.0132 (3)0.0164 (3)0.0009 (2)0.0076 (2)0.0017 (2)
O10.0153 (7)0.0138 (8)0.0186 (8)0.0015 (6)0.0037 (6)0.0007 (6)
O20.0220 (9)0.0228 (9)0.0231 (9)0.0041 (7)0.0033 (7)0.0098 (7)
O30.0240 (9)0.032 (1)0.033 (1)0.0101 (8)0.0167 (8)0.0177 (8)
O40.0134 (7)0.0155 (8)0.0223 (8)0.0011 (6)0.0057 (6)0.0010 (6)
O50.0239 (8)0.0179 (8)0.0216 (8)0.0024 (7)0.0105 (7)0.0029 (6)
O60.0224 (8)0.0214 (9)0.0154 (7)0.0022 (7)0.0055 (7)0.0010 (6)
O70.0266 (9)0.0216 (9)0.0190 (8)0.0063 (7)0.0112 (7)0.0023 (7)
O80.0180 (7)0.0149 (8)0.0239 (8)0.0009 (6)0.0062 (6)0.0055 (6)
N10.0196 (9)0.0157 (9)0.023 (1)0.0016 (7)0.0055 (8)0.0027 (8)
N20.0218 (9)0.021 (1)0.0179 (9)0.0021 (8)0.0084 (8)0.0021 (8)
C10.0234 (12)0.0218 (12)0.0253 (12)0.001 (1)0.001 (1)0.000 (1)
C20.0315 (14)0.0255 (14)0.0409 (15)0.0017 (12)0.0037 (12)0.0003 (12)
C30.0190 (11)0.0275 (14)0.0592 (19)0.0019 (11)0.0027 (12)0.0090 (13)
C40.0204 (12)0.0282 (14)0.0492 (17)0.001 (1)0.0102 (11)0.0099 (12)
C50.0182 (11)0.015 (1)0.0304 (12)0.0013 (9)0.0090 (9)0.0062 (9)
C60.0257 (12)0.0159 (11)0.0293 (12)0.0024 (9)0.015 (1)0.0063 (9)
C70.0364 (14)0.0350 (15)0.0413 (15)0.0067 (12)0.0275 (13)0.0073 (13)
C80.0571 (19)0.0331 (15)0.0354 (15)0.0151 (14)0.0339 (14)0.0070 (12)
C90.0503 (18)0.0323 (15)0.0225 (12)0.0136 (13)0.0141 (12)0.0010 (11)
C100.0327 (13)0.0278 (13)0.0170 (11)0.005 (1)0.008 (1)0.0024 (9)
Geometric parameters (Å, º) top
Al1—O11.8899 (17)N2—C61.356 (3)
Al1—O4i1.8319 (17)N2—C101.339 (3)
Al1—O51.8307 (17)C1—C21.392 (4)
Al1—O8ii1.8744 (17)C1—H111.000
Al1—N12.063 (2)C2—C31.379 (5)
Al1—N22.086 (2)C2—H211.000
P1—O11.5013 (16)C3—C41.384 (5)
P1—O21.5565 (17)C3—H311.000
P1—O31.5604 (18)C4—C51.392 (4)
P1—O41.5075 (16)C4—H411.000
P2—O51.5128 (16)C5—C61.476 (4)
P2—O61.5375 (17)C6—C71.388 (3)
P2—O71.5801 (17)C7—C81.386 (5)
P2—O81.5134 (16)C7—H711.000
O2—H20.86 (4)C8—C91.367 (5)
O3—H30.84 (4)C8—H811.000
O7—H70.90 (4)C9—C101.393 (4)
N1—C11.336 (3)C9—H911.000
N1—C51.360 (3)C10—H1011.000
O1—Al1—O4i92.40 (7)Al1—N1—C5116.45 (16)
O1—Al1—O590.10 (8)C1—N1—C5118.7 (2)
O4i—Al1—O5100.33 (8)Al1—N2—C6115.87 (16)
O1—Al1—O8ii170.90 (8)Al1—N2—C10124.91 (17)
O4i—Al1—O8ii92.46 (8)C6—N2—C10118.8 (2)
O5—Al1—O8ii96.59 (8)N1—C1—C2122.3 (3)
O1—Al1—N186.11 (8)N1—C1—H11118.847
O4i—Al1—N1169.43 (8)C2—C1—H11118.847
O5—Al1—N190.15 (8)C1—C2—C3119.0 (3)
O8ii—Al1—N187.70 (8)C1—C2—H21120.499
O1—Al1—N287.15 (8)C3—C2—H21120.499
O4i—Al1—N291.51 (8)C2—C3—C4119.4 (3)
O5—Al1—N2167.95 (8)C2—C3—H31120.314
O8ii—Al1—N285.04 (8)C4—C3—H31120.307
N1—Al1—N277.97 (8)C3—C4—C5118.9 (3)
O1—P1—O2106.9 (1)C3—C4—H41120.557
O1—P1—O3107.1 (1)C5—C4—H41120.556
O2—P1—O3107.35 (11)N1—C5—C4121.8 (3)
O1—P1—O4116.31 (9)N1—C5—C6114.8 (2)
O2—P1—O4108.5 (1)C4—C5—C6123.5 (2)
O3—P1—O4110.3 (1)N2—C6—C5114.4 (2)
O5—P2—O6109.19 (9)N2—C6—C7121.7 (2)
O5—P2—O7106.6 (1)C5—C6—C7123.9 (2)
O6—P2—O7107.03 (9)C6—C7—C8118.6 (3)
O5—P2—O8111.9 (1)C6—C7—H71120.699
O6—P2—O8114.1 (1)C8—C7—H71120.695
O7—P2—O8107.7 (1)C7—C8—C9119.8 (2)
Al1—O1—P1137.6 (1)C7—C8—H81120.119
P1—O2—H2109 (2)C9—C8—H81120.119
P1—O3—H3116 (3)C8—C9—C10119.1 (3)
Al1i—O4—P1154.29 (11)C8—C9—H91120.438
Al1—O5—P2147.74 (12)C10—C9—H91120.435
P2—O7—H7111 (3)N2—C10—C9121.9 (3)
Al1iii—O8—P2148.21 (11)N2—C10—H101119.062
Al1—N1—C1124.75 (17)C9—C10—H101119.063
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O6iv0.86 (4)1.73 (4)2.581 (2)169 (4)
O3—H3···O6i0.84 (4)1.80 (4)2.644 (3)178 (4)
O7—H7···O6iii0.90 (4)1.76 (4)2.658 (3)176 (4)
Symmetry codes: (i) x+1, y, z+1; (iii) x, y+1/2, z1/2; (iv) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Al(HPO4)(H2PO4)(C10H8N2)]
Mr376.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)10.9253 (2), 15.6992 (3), 8.3683 (2)
β (°) 109.0658 (11)
V3)1356.58 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.08 × 0.08 × 0.01
Data collection
DiffractometerEnraf–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.97, 1.00
No. of measured, independent and
observed [I > 2σ(I)] reflections
5615, 3079, 2238
Rint0.021
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.041, 1.12
No. of reflections2238
No. of parameters220
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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—O11.8899 (17)P1—O21.5565 (17)
Al1—O4i1.8319 (17)P1—O31.5604 (18)
Al1—O51.8307 (17)P1—O41.5075 (16)
Al1—O8ii1.8744 (17)P2—O51.5128 (16)
Al1—N12.063 (2)P2—O61.5375 (17)
Al1—N22.086 (2)P2—O71.5801 (17)
P1—O11.5013 (16)P2—O81.5134 (16)
O1—Al1—O4i92.40 (7)O1—Al1—N287.15 (8)
O1—Al1—O590.10 (8)O4i—Al1—N291.51 (8)
O4i—Al1—O5100.33 (8)O5—Al1—N2167.95 (8)
O1—Al1—O8ii170.90 (8)O8ii—Al1—N285.04 (8)
O4i—Al1—O8ii92.46 (8)N1—Al1—N277.97 (8)
O5—Al1—O8ii96.59 (8)Al1—O1—P1137.6 (1)
O1—Al1—N186.11 (8)Al1i—O4—P1154.29 (11)
O4i—Al1—N1169.43 (8)Al1—O5—P2147.74 (12)
O5—Al1—N190.15 (8)Al1iii—O8—P2148.21 (11)
O8ii—Al1—N187.70 (8)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O6iv0.86 (4)1.73 (4)2.581 (2)169 (4)
O3—H3···O6i0.84 (4)1.80 (4)2.644 (3)178 (4)
O7—H7···O6iii0.90 (4)1.76 (4)2.658 (3)176 (4)
Symmetry codes: (i) x+1, y, z+1; (iii) x, y+1/2, z1/2; (iv) x+1, y1/2, 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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