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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 63| Part 1| January 2007| Pages o21-o25
doi:10.1107/S0108270106050360

Three substituted 4-pyrazolylbenzoates: hydrogen-bonded supra­mol­ecular structures in one, two and three dimensions

CROSSMARK_Color_square_no_text.svg
Jaime Portilla,a Ernesto G. Mata,b Manuel Nogueras,c Justo Cobo,c John N. Lowd and Christopher Glidewelle*

aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, bCONICET–Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Rosario, Suipacha 531, S2002LRK, Argentina, cDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and eSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 15 November 2006; accepted 22 November 2006; online 12 December 2006)

The mol­ecules of ethyl 4-(5-amino-3-methyl-1H-pyrazol-1-yl)­benzoate, C13H15N3O2, are linked by two independent N—H⋯O hydrogen bonds into a chain of edge-fused and alternating R42(8) and R22(20) rings. A combination of N—H⋯N and N—H⋯O hydrogen bonds links the mol­ecules of methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoate, C15H19N3O2, into sheets of alternating R22(20) and R66(32) rings. In 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate, C11H11N3O2·H2O, the mol­ecular components are linked into a three-dimensional framework structure by a combination of five independent hydrogen bonds, two of O—H⋯N type and one each of O—H⋯O, N—H⋯O and N—H⋯N types.

Comment

As precursors for the synthesis of pyrazolo[1,5-a][1,3,5]­benzo­triazepines, which are useful as drugs, agrochemicals and dye inter­mediates (Tachibana & Kaneko, 1989[Tachibana, K. & Kaneko, Y. (1989). Jpn Kokai Tokkyo Koho, JP 01003187, A2; Application: JP 87-159281, 1987; Chem. Abstr. (1989), 111, 97297.]), we have synthesized several 4-(5-amino­pyrazol-1-yl)benzoates by construction of the pyrazole ring from 4-hydrazinobenzoic acid and 3-amino­crotononitrile, and report here the structures of three substituted 4-pyrazolylbenzoic acid derivatives, namely ethyl 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoate, (I)[link], methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoate, (II)[link], and 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate, (III)[link] (Figs. 1[link]–3[link][link]).

The intra­molecular geometries of compounds (I)–(III)[link] present no unexpected features; the pyrazole rings all exhibit marked bond fixation, and the dihedral angles between the two rings in (I)–(III)[link] are 30.1 (2), 34.2 (2) and 46.5 (2)°, respectively. The principal points of inter­est in the structures of compounds (I)–(III)[link] are the different modes of supra­molecular aggregation, leading to hydrogen-bonded structures in one, two and three dimensions, respectively.

[Scheme 1]

The supra­molecular structure of compound (I)[link] is simple. Amino atom N45 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H45A and H45B, to the O11 atoms in the mol­ecules at (−x, 1 − y, 1 − z) and (x, y, 1 + z), respectively (Table 1[link]). Propagation by translation and inversion of these two hydrogen bonds then generates a chain of edge-fused centrosymmetric rings running parallel to the [001] direction, with R22(20) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) rings centred at (0, [1\over 2], n + [1\over 2]) (where n represents zero or an integer), and R42(8) rings centred at (0, [1\over 2], n) (n = zero or integer) (Fig. 4[link]). There are no direction-specific inter­actions between adjacent chains; in particular C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking inter­actions are both absent.

The mol­ecules of compound (II)[link] are linked by a combination of N—H⋯O and N—H⋯N hydrogen bonds (Table 2[link]); this may be contrasted with compound (I)[link], where N—H⋯N hydrogen bonds were absent. The mol­ecules are linked into sheets, and the formation of the sheet is readily analysed in terms of a dimeric building block. Amino atom N45 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H45A, to atom O11 in the mol­ecule at (1 − x, 1 − y, 1 − z), so generating by inversion a dimeric unit characterized by an R22(20) motif. In addition, the N45 atoms in the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which are components of the R22(20) dimer centred at ([1\over 2], [1\over 2], [1\over 2]), act as hydrogen-bond donors, via H45B, to the ring atoms N42 of the mol­ecules at (1 − x, [{1\over 2}] + y, [{1\over 2}] − z) and (x, [{1\over 2}] − y, [{1\over 2}] + z), respectively, which are themselves components of the dimers centred at ([1\over 2], 1, 0) and ([1\over 2], 0, 1). In a similar way, atoms N42 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms N45 in the mol­ecules at (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z) and (x, [3\over 2] − y, [{1\over 2}] + z), which are components of the dimers centred at ([1\over 2], 0, 0) and ([1\over 2], 1, 1) respectively. Thus, each dimer is directly linked, via N—H⋯N hydrogen bonds, to four adjacent dimers, and propagation of this inter­action by the space group leads to the formation of a sheet parallel to (100) built from alternating R22(20) and R66(32) rings, where both ring types are centrosymmetric (Fig. 5[link]). There are no direction-specific inter­actions between adjacent sheets, nor is there any inter­weaving of adjacent sheets, despite the occurrence of the large R66(32) rings; inter­weaving is prevented by the effective masking of the large rings by pairs of tert-butyl groups (Fig. 5[link]).

Compound (III)[link] is a stoichiometric monohydrate, and in the selected asymmetric unit (Fig. 3[link]), the components are linked by a rather short and almost linear O—H⋯O hydrogen bond (Table 3[link]). Four further hydrogen bonds link the mol­ecular components into a single three-dimensional framework structure, whose formation is readily analysed in terms of three independent one-dimensional substructures, only one of which involves the water mol­ecule. In the first substructure, which runs parallel to the [100] direction, water atom O1 at (x, y, z) acts as a hydrogen-bond donor, via H1A and H1B, respectively, to atom N42 at (−x, 1 − y, 1 − z) and N45 at (1 − x, 1 − y, 1 − z). Propagation by inversion of these two hydrogen bonds then generates a chain of edge-fused centrosymmetric rings with R44(22) rings centred at (n, [1\over2], [1\over2]) (n = zero or integer) and R44(24) rings centred at (n + [1\over2], [1\over2], [1\over2]) (n = zero or integer) (Fig. 6[link]).

The second substructure runs parallel to the [010] direction and consists of simple chains built from the organic component only; amino atom N45 at (x, y, z) acts as a hydrogen-bond donor, via H45A, to ring atom N42 at ([{1\over 2}] − x, [{1\over 2}] + y, [{1\over 2}] − z), so forming a C(5) chain generated by the 21 screw axis along ([1\over4], y, [1\over4]) (Fig. 7[link]). The third substructure is also built from only the organic components, and runs along the [10[\overline{1}]] direction; amino atom N45 at (x, y, z) acts as a hydrogen-bond donor, this time via H45B, to atom O11 at ([{1\over 2}] + x, [{3\over 2}] − y, −[{1\over 2}] + z), so forming a C(10) chain generated by the n-glide plane at y = [3\over4] (Fig. 8[link]). The combination of the chains along [100], [010] and [10[\overline{1}]] suffices to link all the mol­ecules into a single three-dimensional framework structure.

Thus, rather modest changes in the peripheral substituents in compounds (I)–(III)[link] are associated with substantial changes both in the patterns of the hydrogen bonds deployed and in the dimensionality of the resulting supra­molecular structures.

[Figure 1]
Figure 1
A mol­ecule of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
A mol­ecule of (II)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
The independent mol­ecular components of (III)[link], showing the atom-labelling scheme and the O—H⋯O hydrogen bond within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I)[link], showing the formation of a chain of alternating R22(20) and R42(8) rings along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (II)[link], showing the formation of a sheet of R22(20) and R66(32) rings parallel to (100). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 6]
Figure 6
A stereoview of part of the crystal structure of (III)[link], showing the formation of a chain of alternating R44(22) and R44(24) rings along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 7]
Figure 7
Part of the crystal structure of (III)[link], showing the formation of a C(5) chain along [010]. For the sake of clarity, water mol­ecules and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] − x, [{1\over 2}] + y, [{1\over 2}] − z) and ([{1\over 2}] − x, −[{1\over 2}] + y, [{1\over 2}] − z), respectively.
[Figure 8]
Figure 8
Part of the crystal structure of (III)[link], showing the formation of a C(10) chain along [10[\overline{1}]]. For the sake of clarity, the water mol­ecule and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] + x, [{3\over 2}] − y, −[{1\over 2}] + z) and (−[{1\over 2}] + x, [{3\over 2}] − y, [{1\over 2}] + z), respectively.

Experimental

For the synthesis of compounds (I)[link] and (III)[link], 3-amino­crotononitrile (3.3 mmol) was added at ambient temperature to a stirred solution of 4-hydrazinobenzoic acid (3.3 mmol) in ethanol (6 ml). The resulting suspension was stirred for 20 min and then 5 M HCl solution (15 ml) was added. The mixture was stirred for 40 min at 368 K and, after cooling (< 263 K), the solution was made either basic or neutral, in separate experiments, using aqueous ammonia solution. From the basic solution, compound (I)[link] was precipitated upon removal of the solvent; compound (I) was collected by filtration and recrystallized from dimethyl sulfoxide to give yellow crystals suitable for single-crystal X-ray diffraction (yield 13%, m.p. 430–431 K). MS (70 eV) m/z (%): 245 (100, M+), 217 (21), 200 (39), 134 (11), 122 (26). From the neutral solution, compound (III)[link] was precipitated upon removal of the solvent; the compound was collected by filtration and recrystallized from ethanol to give yellow crystals suitable for single-crystal X-ray diffraction (yield 72%, m.p. 503–504 K). MS (70 eV) m/z (%): 217 (100, M+), 200 (28). For the synthesis of compound (II)[link], 4,4-dimethyl-3-oxo­pentane­nitrile (3.3 mmol) was added at ambient temperature to a stirred solution of 4-hydrazinobenzoic acid (3.3 mmol) in methanol (6 ml). The resulting suspension was stirred for 20 min and then 5 M HCl solution (15 ml) was added. The mixture was stirred for 40 min at 368 K and, after cooling (< 263 K), the mixture was neutralized using aqueous ammonia solution. The inter­mediate 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoic acid was precipitated as a yellow solid (yield 80%, m.p. 468–469 K). A suspension of the entire batch of this inter­mediate in methanol (6 ml) was treated with diazo­methane (3.3 mmol) at 273–283 K. Compound (II)[link] was formed as a yellow solid, which was collected by filtration and then recrystallized from methanol to afford yellow crystals suitable for single-crystal X-ray diffraction (overall yield 76%, m.p. 468–469 K). MS (70 eV) m/z (%): 273 (53, M+), 258 (100), 231 (83).

Compound (I)[link]

Crystal data

  • C13H15N3O2

  • Mr = 245.28

  • Triclinic, [P \overline 1]

  • a = 7.2228 (4) Å

  • b = 8.4433 (3) Å

  • c = 10.5938 (5) Å

  • α = 98.234 (3)°

  • β = 107.609 (2)°

  • γ = 97.907 (3)°

  • V = 598.12 (5) Å3

  • Z = 2

  • Dx = 1.362 Mg m−3

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.28 × 0.14 × 0.06 mm
Data collection

  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.979, Tmax = 0.994

  • 12140 measured reflections

  • 2748 independent reflections

  • 1904 reflections with I > 2σ(I)

  • Rint = 0.052

  • θmax = 27.6°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.049

  • wR(F2) = 0.136

  • S = 1.08

  • 2748 reflections

  • 165 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0676P)2 + 0.0939P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N45—H45A⋯O11i 0.94 2.30 3.1190 (19) 146
N45—H45B⋯O11ii 0.94 2.11 3.0252 (18) 165
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y, z+1.

Compound (II)[link]

Crystal data

  • C15H19N3O2

  • Mr = 273.33

  • Monoclinic, P 21 /c

  • a = 6.1272 (2) Å

  • b = 11.6374 (3) Å

  • c = 20.3182 (7) Å

  • β = 98.629 (2)°

  • V = 1432.38 (8) Å3

  • Z = 4

  • Dx = 1.267 Mg m−3

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 120 (2) K

  • Lath, yellow

  • 0.48 × 0.22 × 0.12 mm
Data collection

  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.971, Tmax = 0.990

  • 24177 measured reflections

  • 3269 independent reflections

  • 2353 reflections with I > 2σ(I)

  • Rint = 0.050

  • θmax = 27.5°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.112

  • S = 1.03

  • 3269 reflections

  • 185 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0591P)2 + 0.2591P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.34 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N45—H45A⋯O11i 0.93 2.22 3.1388 (16) 172
N45—H45B⋯N42ii 0.92 2.34 3.2386 (17) 166
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Compound (III)[link]

Crystal data

  • C11H11N3O2·H2O

  • Mr = 235.24

  • Monoclinic, P 21 /n

  • a = 8.0166 (2) Å

  • b = 7.5082 (2) Å

  • c = 18.5507 (5) Å

  • β = 91.8140 (16)°

  • V = 1116.01 (5) Å3

  • Z = 4

  • Dx = 1.400 Mg m−3

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 120 (2) K

  • Block, yellow

  • 0.54 × 0.36 × 0.18 mm
Data collection

  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.961, Tmax = 0.982

  • 11603 measured reflections

  • 2551 independent reflections

  • 2037 reflections with I > 2σ(I)

  • Rint = 0.031

  • θmax = 27.5°
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.121

  • S = 1.10

  • 2551 reflections

  • 155 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0673P)2 + 0.2827P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.28 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O12—H12⋯O1 0.95 1.66 2.6005 (13) 172
O1—H1A⋯N42i 0.90 1.90 2.8002 (16) 176
O1—H1B⋯N45ii 0.90 2.06 2.9556 (15) 180
N45—H45A⋯N42iii 0.91 2.31 3.1446 (17) 152
N45—H45B⋯O11iv 0.91 2.01 2.9020 (15) 168
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) [-x+{\script{1\over 2}}], [y+{\script{1\over 2}}], [-z+{\script{1\over 2}}]; (iv) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

For compounds (II)[link] and (III)[link], the space groups P21/c and P21/n, respectively, were uniquely assigned from the systematic absences. Crystals of compound (I)[link] are triclinic; space group P[\overline{1}] was selected and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned standard C—H distances [0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), with Uiso(H) = kUeq(C), where k = 1.5 for methyl groups and 1.2 for other H atoms bonded to C atoms]. The H atoms bonded to N or O atoms were permitted to ride at the distances found from difference maps [N—H = 0.91–0.94 Å and O—H = 0.90 Å, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O).]

For all compounds, data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (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.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S0108270106050360/gg3055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106050360/gg3055Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270106050360/gg3055IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270106050360/gg3055IIIsup4.hkl


Comment top

As precursors for the synthesis of pyrazolo[1,5-a][1,3,5]benzotriazepines, which are useful as drugs, agrochemicals or dye intermediates (Tachibana & Kaneko, 1989), we have synthesized several 4-(5-aminopyrazol-1-yl)benzoates by construction of the pyrazole ring from 4-hydrazinobenzoic acid and 3-aminocrotononitrile, and report the structures of three substituted 4-pyrazolylbenzoic acid derivatives, ethyl 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoate, (I), methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoate, (II), and 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate, (III) (Figs. 1–3).

The intramolecular geometries of compounds (I)–(III) present no unexpected features; the pyrazole rings all exhibit marked bond fixation and the dihedral angles between the two rings in (I)–(III) are 30.1 (2), 34.2 (2) and 46.5 (2)°, respectively. The principal points of interest in the structures of compounds (I)–(III) are the different modes of supramolecular aggregation leading to hydrogen-bonded structures in one, two and three dimensions, respectively.

The supramolecular structure of compound (I) is simple. Amino atom N45 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H45A and H45B, to atoms O11 in the molecules at (−x, 1 − y, 1 − z) and (x, y, 1 + z), respectively (Table 1). Propagation by translation and inversion of these two hydrogen bonds then generates a chain of edge-fused centrosymmetric rings running parallel to the [001] direction, with R22(20) (Bernstein et al., 1995) rings centred at (0, 1/2, n + 1/2) (where n represents zero or an integer), and R24(8) rings centred at (0, 1/2, n) (n = zero or integer) (Fig. 4). There are no direction-specific interactions between adjacent chains; in particular C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are both absent.

The molecules of compound (II) are linked by a combination of N—H···O and N—H···N hydrogen bonds (Table 2); this may be contrasted with compound (I), where N—H···N hydrogen bonds were absent. The molecules are linked into sheets, and the formation of the sheet is readily analysed in terms of a dimeric building block. Amino atom N45 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H45A, to atom O11 in the molecule at (1 − x, 1 − y, 1 − z), so generating by inversion a dimeric unit characterized by an R22(20) motif. In addition, atoms N45 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which are components of the R22(20) dimer centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors, via H45B, to the ring atoms N42 of the molecules at (1 − x, 1/2 + y, 1/2 − z) and (x, 1/2 − y, 1/2 + z), respectively, which are themselves components of the dimers centred at (1/2, 1, 0) and (1/2, 0, 1). In a similar way, atoms N42 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms N45 in the molecules at (1 − x, −1/2 + y, 1/2 − z) and (x, 1.5 − y, 1/2 + z), which are components of the dimers centred at (1/2, 0, 0) an (1/2, 1, 1) respectively. Thus each dimer is directly linked, via N—H···N hydrogen bonds, to four adjacent dimers, and propagation of this interaction by the space group leads to the formation of a sheet parallel to (100) built form alternating R22(20) and R66(32) rings, where both ring types are centrosymmetric (Fig. 5). There are no direction-specific interactions between adjacent sheets, nor is there any interweaving of adjacent sheets, despite the occurrence of the large R66(32) rings; interweaving is prevented by the effective masking of the large rings by pairs of tert-butyl groups (Fig. 5).

Compound (III) is a stoichiometric monohydrate, and in the selected asymmetric unit (Fig.3), the components are linked by a rather short and almost linear O—H···O hydrogen bond (Table 3). Four further hydrogen bonds link the molecular components into a single three-dimensional framework structure, whose formation is readily analysed in terms of three independent one-dimensional substructures, only one of which involves the water molecule. In the first substructure, which runs parallel to the [100] direction, water atom O1 at (x, y, z) acts as a hydrogen-bond donor, via H1A and H1B, respectively, to atoms N42 at (−x, 1 − y, 1 − z) and N45 at (1 − x, 1 − y, 1 − z). Propagation by inversion of these two hydrogen bonds then generates a chain of edge-fused centrosymmetric rings with R44(22) rings centred at (n, 1/2, 1/2) (n = zero or integer) and R44(24) rings centred at (n + 1/2, 1/2, 1/2) (n = zero or integer) (Fig. 6).

The second substructure runs parallel to the [010] direction and consists of simple chains built from the organic component only; amino atom N45 at (x, y, z) acts as a hydrogen-bond donor, via H45A, to ring atom N42 at (1/2 − x, 1/2 + y, 1/2 − z), so forming a C(5) chain generated by the 21 screw axis along (1/4, y, 1/4) (Fig. 7). The third substructure is also built from only the organic components, and runs along the [101] direction; amino atom N45 at (x, y, z) acts as a hydrogen-bond donor, this time via H45B, to atom O11 at (1/2 + x, 3/2 − y, −1/2 + z), so forming a C(10) chain generated by the n-glide plane at y = 3/4 (Fig. 8). The combination of the chains along [100], [010] and [101] suffices to link all the molecules into a single three-dimensional framework structure.

Thus, rather modest changes in the peripheral substituents in compounds (I)–(III) are associated with substantial changes both in the patterns of the hydrogen bonds deployed and in the dimensionality of the resulting supramolecular structures.

Experimental top

For the synthesis of compounds (I) and (III), 3-aminocrotononitrile (3.3 mmol) was added at ambient temperature to a stirred solution of 4-hydrazinobenzoic acid (3.3 mmol) in ethanol (6 ml). The resulting suspension was stirred for 20 min and then 5 M HCl solution (15 ml) was added. The mixture was stirred for 40 min at 368 K, and after cooling (< 263 K) the solution was made either basic or neutral, in separate experiments, using aqueous ammonia solution. From the basic solution, compound (I) was precipitated upon removal of the solvent; the compound was collected by filtration and recrystallized from DMSO to give yellow crystals suitable for single-crystal X-ray diffraction (yield 13%, m.p. 430–431 K). MS (70 eV) m/z (%) 245 (100, M+), 217?(21), 200?(39), 134?(11), 122?(26). From the neutral solution, compound (III) was precipitated upon removal of the solvent; the compound was collected by filtration and recrystallized from ethanol to give yellow crystals suitable for single-crystal X-ray diffraction (yield 72%, m.p. 503–504 K). MS (70 eV) m/z (%) = 217 (100, M+), 200 ?(28). For the synthesis of compound (II) 4,4-dimethyl-3-oxopentanenitrile (3.3 mmol) was added at ambient temperature to a stirred solution of 4-hydrazinobenzoic acid (3.3 mmol) in methanol (6 ml). The resulting suspension was stirred for 20 min and then 5M HCl solution (15 ml) was added. The mixture was stirred for 40 min at 368 K, and after cooling (< 263 K) the mixture was neutralized using aqueous ammonia solution. The intermediate 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoic acid was precipitated as a yellow solid (yield 80%, m.p. 468–469 K). A suspension of the entire batch of this intermediate in methanol (6 ml) was treated with diazomethane (3.3 mmol) at 273–283 K. Compound (II) was formed as a yellow solid, which was collected by filtration and then recrystallized from methanol to afford yellow crystals suitable for single-crystal X-ray diffraction (overall yield 76%, m.p. 468–469 K). MS (70 eV) m/z (%) = 273 (53, M+), 258?(100), 231?(83).

Refinement top

For compounds (II) and (III), the space groups P21/c and P21/n, respectively, were uniquely assigned from the systematic absences. Crystals of compound (I) are triclinic; space group P1 was selected, and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned standard C—H distances [0.95 Å (aromatic), 0.98 Å (CH3) or 0.99 Å (CH2), with Uiso(H) = kUeq(C), where k = 1.5 for methyl groups and 1.2 for other H atoms]. The H atoms bonded to N or O atoms were permitted to ride at the distances found from difference maps [N—H = 0.91–0.94 Å and O—H = 0.90 Å, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O).]

Computing details top

For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A molecule of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The independent molecular components of (III), showing the atom-labelling scheme and the O—H···O hydrogen bond within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a chain of alternating R22(20) and R24(8) rings along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a sheet of R22(20) and R66(32) rings parallel to (100). For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (III), showing the formation of a chain of alternating R44(22) and R44(24) rings along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 7] Fig. 7. Part of the crystal structure of (III), showing the formation of a C(5) chain along [010]. For the sake of clarity, water molecules and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 − x, 1/2 + y, 1/2 − z) and (1/2 − x, −1/2 + y, 1/2 − z), respectively.
[Figure 8] Fig. 8. Part of the crystal structure of (III), showing the formation of a C(10) chain along [101]. For the sake of clarity, the water molecule and H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 3/2 − y, −1/2 + z) and (−1/2 + x, 3/2 − y, 1/2 + z), respectively.
(I) Ethyl 4-(5-amino-3-methyl-1H-pyrazol-1-yl)benzoate top
Crystal data top
C13H15N3O2Z = 2
Mr = 245.28F(000) = 260
Triclinic, P1Dx = 1.362 Mg m−3
Hall symbol: -P 1Melting point: 430 K
a = 7.2228 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.4433 (3) ÅCell parameters from 2748 reflections
c = 10.5938 (5) Åθ = 2.1–27.6°
α = 98.234 (3)°µ = 0.10 mm−1
β = 107.609 (2)°T = 120 K
γ = 97.907 (3)°Plate, colourless
V = 598.12 (5) Å30.28 × 0.14 × 0.06 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer		2748 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1904 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 2.1°
ϕ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −10→10
Tmin = 0.979, Tmax = 0.994l = −13→13
12140 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0676P)2 + 0.0939P]
where P = (Fo2 + 2Fc2)/3
2748 reflections(Δ/σ)max = 0.001
165 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.32 e Å−3
Crystal data top
C13H15N3O2γ = 97.907 (3)°
Mr = 245.28V = 598.12 (5) Å3
Triclinic, P1Z = 2
a = 7.2228 (4) ÅMo Kα radiation
b = 8.4433 (3) ŵ = 0.10 mm−1
c = 10.5938 (5) ÅT = 120 K
α = 98.234 (3)°0.28 × 0.14 × 0.06 mm
β = 107.609 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer		2748 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1904 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.994Rint = 0.052
12140 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.08Δρmax = 0.23 e Å−3
2748 reflectionsΔρmin = −0.32 e Å−3
165 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2358 (2)0.48950 (19)0.47329 (16)0.0203 (4)
C20.3291 (2)0.5776 (2)0.60484 (16)0.0223 (4)
C110.2299 (2)0.56079 (19)0.35266 (17)0.0211 (4)
O110.15727 (17)0.48372 (14)0.23714 (11)0.0273 (3)
O120.30959 (18)0.71974 (14)0.38273 (11)0.0249 (3)
C120.3015 (3)0.7981 (2)0.26690 (17)0.0265 (4)
C1210.3781 (3)0.9772 (2)0.3201 (2)0.0393 (5)
C30.3304 (2)0.50584 (19)0.71474 (17)0.0218 (4)
C40.2337 (2)0.34459 (19)0.69318 (16)0.0202 (4)
C50.1408 (3)0.2555 (2)0.56222 (17)0.0235 (4)
C60.1434 (2)0.3274 (2)0.45321 (17)0.0229 (4)
N410.2326 (2)0.26682 (16)0.80299 (13)0.0211 (3)
N420.2263 (2)0.09975 (16)0.78477 (14)0.0238 (3)
C430.2324 (2)0.0635 (2)0.90363 (17)0.0230 (4)
C4310.2345 (3)−0.1079 (2)0.92392 (19)0.0286 (4)
C440.2385 (2)0.20233 (19)0.99792 (17)0.0226 (4)
C450.2370 (2)0.32944 (19)0.93107 (16)0.0211 (4)
N450.2409 (2)0.49295 (16)0.97490 (14)0.0248 (4)
H20.39260.68800.61920.027*
H12A0.16360.77890.20480.032*
H12B0.38390.75260.21670.032*
H12C0.29451.02110.36860.059*
H12D0.37561.03280.24470.059*
H12E0.51430.99470.38180.059*
H30.39660.56590.80400.026*
H50.07560.14560.54780.028*
H60.08190.26580.36400.028*
H43A0.2237−0.17800.83890.043*
H43B0.1225−0.14640.95290.043*
H43C0.3586−0.11180.99330.043*
H440.24280.20651.08890.027*
H45A0.15720.53880.90940.030*
H45B0.20590.50691.05380.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0213 (9)0.0239 (8)0.0187 (9)0.0078 (7)0.0083 (7)0.0061 (7)
C20.0246 (9)0.0215 (8)0.0217 (9)0.0035 (7)0.0091 (7)0.0046 (7)
C110.0218 (9)0.0230 (9)0.0209 (9)0.0061 (7)0.0094 (7)0.0049 (7)
O110.0326 (7)0.0313 (7)0.0181 (7)0.0054 (5)0.0087 (5)0.0049 (5)
O120.0320 (7)0.0252 (6)0.0195 (6)0.0043 (5)0.0097 (5)0.0091 (5)
C120.0324 (10)0.0302 (9)0.0193 (9)0.0060 (7)0.0094 (8)0.0104 (7)
C1210.0644 (15)0.0283 (10)0.0283 (11)0.0103 (9)0.0169 (10)0.0108 (8)
C30.0259 (9)0.0223 (8)0.0173 (8)0.0049 (7)0.0074 (7)0.0028 (6)
C40.0238 (9)0.0219 (8)0.0191 (9)0.0086 (7)0.0098 (7)0.0074 (7)
C50.0288 (10)0.0203 (8)0.0215 (9)0.0040 (7)0.0088 (7)0.0039 (7)
C60.0268 (9)0.0244 (9)0.0175 (8)0.0058 (7)0.0077 (7)0.0020 (7)
N410.0281 (8)0.0191 (7)0.0180 (7)0.0054 (6)0.0092 (6)0.0052 (5)
N420.0294 (8)0.0194 (7)0.0239 (8)0.0055 (6)0.0094 (6)0.0059 (6)
C430.0210 (9)0.0256 (9)0.0221 (9)0.0038 (7)0.0058 (7)0.0072 (7)
C4310.0313 (10)0.0251 (9)0.0303 (10)0.0042 (7)0.0100 (8)0.0096 (7)
C440.0238 (9)0.0259 (9)0.0179 (9)0.0039 (7)0.0060 (7)0.0066 (7)
C450.0222 (9)0.0245 (8)0.0168 (8)0.0051 (7)0.0062 (7)0.0049 (6)
N450.0336 (9)0.0248 (7)0.0186 (8)0.0080 (6)0.0110 (6)0.0043 (6)
Geometric parameters (Å, º) top
C1—C61.394 (2)C4—N411.417 (2)
C1—C21.395 (2)C5—C61.383 (2)
C1—C111.480 (2)C5—H50.95
C2—C31.385 (2)C6—H60.95
C2—H20.95N41—C451.373 (2)
C11—O111.2190 (19)N41—N421.3887 (18)
C11—O121.3371 (19)N42—C431.327 (2)
O12—C121.465 (2)C43—C441.413 (2)
C12—C1211.499 (2)C43—C4311.495 (2)
C12—H12A0.99C431—H43A0.98
C12—H12B0.99C431—H43B0.98
C121—H12C0.98C431—H43C0.98
C121—H12D0.98C44—C451.367 (2)
C121—H12E0.98C44—H440.95
C3—C41.395 (2)C45—N451.386 (2)
C3—H30.95N45—H45A0.94
C4—C51.393 (2)N45—H45B0.94
C6—C1—C2119.19 (15)C6—C5—C4119.93 (15)
C6—C1—C11118.02 (15)C6—C5—H5120.0
C2—C1—C11122.79 (15)C4—C5—H5120.0
C3—C2—C1120.77 (15)C5—C6—C1120.48 (15)
C3—C2—H2119.6C5—C6—H6119.8
C1—C2—H2119.6C1—C6—H6119.8
O11—C11—O12123.03 (15)C45—N41—N42111.23 (13)
O11—C11—C1123.72 (15)C45—N41—C4130.60 (13)
O12—C11—C1113.24 (14)N42—N41—C4118.17 (13)
C11—O12—C12115.61 (13)C43—N42—N41104.42 (13)
O12—C12—C121107.65 (14)N42—C43—C44111.84 (14)
O12—C12—H12A110.2N42—C43—C431119.79 (15)
C121—C12—H12A110.2C44—C43—C431128.37 (15)
O12—C12—H12B110.2C43—C431—H43A109.5
C121—C12—H12B110.2C43—C431—H43B109.5
H12A—C12—H12B108.5H43A—C431—H43B109.5
C12—C121—H12C109.5C43—C431—H43C109.5
C12—C121—H12D109.5H43A—C431—H43C109.5
H12C—C121—H12D109.5H43B—C431—H43C109.5
C12—C121—H12E109.5C45—C44—C43105.73 (15)
H12C—C121—H12E109.5C45—C44—H44127.1
H12D—C121—H12E109.5C43—C44—H44127.1
C2—C3—C4119.43 (15)C44—C45—N41106.75 (14)
C2—C3—H3120.3C44—C45—N45130.35 (15)
C4—C3—H3120.3N41—C45—N45122.89 (14)
C5—C4—C3120.17 (15)C45—N45—H45A113.1
C5—C4—N41118.75 (14)C45—N45—H45B110.1
C3—C4—N41121.06 (14)H45A—N45—H45B109.4
C6—C1—C2—C3−0.1 (2)C5—C4—N41—C45−150.74 (17)
C11—C1—C2—C3179.84 (14)C3—C4—N41—C4531.1 (3)
C6—C1—C11—O11−3.6 (2)C5—C4—N41—N4229.3 (2)
C2—C1—C11—O11176.42 (16)C3—C4—N41—N42−148.87 (15)
C6—C1—C11—O12175.30 (14)C45—N41—N42—C43−1.64 (17)
C2—C1—C11—O12−4.7 (2)C4—N41—N42—C43178.34 (14)
O11—C11—O12—C121.0 (2)N41—N42—C43—C441.16 (18)
C1—C11—O12—C12−177.91 (13)N41—N42—C43—C431−178.13 (15)
C11—O12—C12—C121174.31 (15)N42—C43—C44—C45−0.30 (19)
C1—C2—C3—C4−1.3 (2)C431—C43—C44—C45178.91 (17)
C2—C3—C4—C51.5 (2)C43—C44—C45—N41−0.71 (18)
C2—C3—C4—N41179.67 (14)C43—C44—C45—N45179.94 (16)
C3—C4—C5—C6−0.4 (2)N42—N41—C45—C441.49 (18)
N41—C4—C5—C6−178.55 (15)C4—N41—C45—C44−178.49 (16)
C4—C5—C6—C1−1.1 (3)N42—N41—C45—N45−179.10 (14)
C2—C1—C6—C51.3 (2)C4—N41—C45—N450.9 (3)
C11—C1—C6—C5−178.66 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N45—H45A···O11i0.942.303.1190 (19)146
N45—H45B···O11ii0.942.113.0252 (18)165
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1.
(II) Methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl)benzoate top
Crystal data top
C15H19N3O2F(000) = 584
Mr = 273.33Dx = 1.267 Mg m−3
Monoclinic, P21/cMelting point: 503 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.1272 (2) ÅCell parameters from 3269 reflections
b = 11.6374 (3) Åθ = 2.7–27.5°
c = 20.3182 (7) ŵ = 0.09 mm−1
β = 98.629 (2)°T = 120 K
V = 1432.38 (8) Å3Lath, yellow
Z = 40.48 × 0.22 × 0.12 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer		3269 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.7°
ϕ and ω scansh = −7→7
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −15→15
Tmin = 0.971, Tmax = 0.990l = −26→26
24177 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0591P)2 + 0.2591P]
where P = (Fo2 + 2Fc2)/3
3269 reflections(Δ/σ)max < 0.001
185 parametersΔρmax = 0.17 e Å−3
0 restraintsΔρmin = −0.34 e Å−3
Crystal data top
C15H19N3O2V = 1432.38 (8) Å3
Mr = 273.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.1272 (2) ŵ = 0.09 mm−1
b = 11.6374 (3) ÅT = 120 K
c = 20.3182 (7) Å0.48 × 0.22 × 0.12 mm
β = 98.629 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer		3269 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2353 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 0.990Rint = 0.050
24177 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.03Δρmax = 0.17 e Å−3
3269 reflectionsΔρmin = −0.34 e Å−3
185 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3898 (2)0.38814 (11)0.45106 (7)0.0207 (3)
C110.3351 (2)0.31923 (12)0.50789 (7)0.0216 (3)
O110.46286 (16)0.25592 (8)0.54173 (5)0.0277 (3)
O120.12389 (15)0.33286 (8)0.51719 (5)0.0263 (2)
C120.0550 (2)0.26119 (14)0.56860 (8)0.0312 (4)
C20.2466 (2)0.47029 (11)0.41881 (7)0.0220 (3)
C30.3021 (2)0.53156 (11)0.36537 (7)0.0228 (3)
C40.5056 (2)0.51185 (11)0.34451 (7)0.0202 (3)
N410.56941 (18)0.57232 (9)0.28996 (6)0.0216 (3)
N420.70612 (19)0.51678 (10)0.25157 (6)0.0227 (3)
C430.7550 (2)0.59636 (12)0.20927 (7)0.0216 (3)
C4310.8967 (2)0.56660 (12)0.15658 (7)0.0238 (3)
C4321.0568 (2)0.46868 (13)0.18120 (8)0.0284 (3)
C4330.7460 (3)0.53063 (14)0.09264 (8)0.0330 (4)
C4341.0317 (2)0.67230 (13)0.14224 (8)0.0330 (4)
C440.6570 (2)0.70301 (12)0.22032 (7)0.0245 (3)
C450.5411 (2)0.68602 (11)0.27208 (7)0.0221 (3)
N450.40923 (19)0.75908 (10)0.30303 (6)0.0263 (3)
C50.6491 (2)0.42901 (12)0.37607 (7)0.0215 (3)
C60.5913 (2)0.36799 (12)0.42921 (7)0.0221 (3)
H12A0.09610.18120.56160.047*
H12B−0.10550.26660.56670.047*
H12C0.12770.28730.61230.047*
H20.10930.48440.43370.026*
H30.20260.58650.34310.027*
H43A1.14560.49080.22350.043*
H43B1.15430.45370.14810.043*
H43C0.97250.39910.18770.043*
H43D0.66300.46170.10130.050*
H43E0.83590.51410.05780.050*
H43F0.64280.59310.07800.050*
H43G0.93130.73440.12480.049*
H43H1.12710.65240.10930.049*
H43I1.12270.69770.18350.049*
H440.66900.77250.19660.029*
H45A0.43550.75880.34920.032*
H45B0.40130.83250.28560.032*
H50.78610.41460.36110.026*
H60.68950.31200.45100.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0216 (7)0.0207 (7)0.0195 (7)−0.0020 (5)0.0019 (6)−0.0032 (5)
C110.0224 (7)0.0226 (7)0.0196 (7)−0.0007 (5)0.0027 (6)−0.0037 (6)
O110.0274 (5)0.0319 (6)0.0239 (6)0.0041 (4)0.0042 (4)0.0055 (4)
O120.0234 (5)0.0302 (6)0.0267 (6)0.0017 (4)0.0080 (4)0.0066 (4)
C120.0286 (8)0.0379 (9)0.0289 (9)−0.0007 (6)0.0101 (7)0.0095 (7)
C20.0196 (6)0.0223 (7)0.0246 (8)−0.0005 (5)0.0048 (6)−0.0019 (6)
C30.0239 (7)0.0202 (7)0.0240 (8)0.0030 (5)0.0031 (6)0.0004 (6)
C40.0230 (7)0.0186 (7)0.0193 (7)−0.0026 (5)0.0039 (5)−0.0015 (5)
N410.0236 (6)0.0183 (6)0.0241 (7)0.0016 (5)0.0077 (5)−0.0006 (5)
N420.0244 (6)0.0212 (6)0.0239 (6)0.0017 (5)0.0077 (5)−0.0003 (5)
C430.0211 (6)0.0218 (7)0.0214 (7)−0.0017 (5)0.0014 (6)0.0013 (6)
C4310.0258 (7)0.0238 (7)0.0226 (8)−0.0005 (6)0.0066 (6)0.0009 (6)
C4320.0304 (8)0.0292 (8)0.0273 (8)0.0030 (6)0.0095 (6)−0.0018 (6)
C4330.0369 (8)0.0372 (9)0.0252 (8)−0.0017 (7)0.0055 (7)−0.0013 (7)
C4340.0322 (8)0.0314 (8)0.0381 (10)−0.0017 (7)0.0141 (7)0.0044 (7)
C440.0268 (7)0.0218 (7)0.0248 (8)0.0009 (6)0.0035 (6)0.0039 (6)
C450.0229 (7)0.0194 (7)0.0236 (7)0.0011 (5)0.0019 (6)0.0010 (6)
N450.0333 (7)0.0202 (6)0.0264 (7)0.0064 (5)0.0082 (5)0.0028 (5)
C50.0197 (6)0.0223 (7)0.0229 (8)0.0002 (5)0.0043 (6)−0.0029 (6)
C60.0232 (7)0.0206 (7)0.0218 (7)0.0026 (5)0.0008 (6)−0.0010 (6)
Geometric parameters (Å, º) top
C1—C21.3930 (19)C431—C4341.534 (2)
C1—C61.3931 (18)C431—C4331.535 (2)
C1—C111.4849 (19)C431—C4321.537 (2)
C11—O111.2112 (16)C432—H43A0.98
C11—O121.3448 (15)C432—H43B0.98
O12—C121.4483 (16)C432—H43C0.98
C12—H12A0.98C433—H43D0.98
C12—H12B0.98C433—H43E0.98
C12—H12C0.98C433—H43F0.98
C2—C31.3834 (19)C434—H43G0.98
C2—H20.95C434—H43H0.98
C3—C41.3947 (18)C434—H43I0.98
C3—H30.95C44—C451.369 (2)
C4—C51.3945 (19)C44—H440.95
C4—N411.4166 (17)C45—N451.3867 (17)
N41—C451.3762 (17)N45—H45A0.93
N41—N421.3871 (15)N45—H45B0.92
N42—C431.3279 (17)C5—C61.3820 (19)
C43—C441.4114 (19)C5—H50.95
C43—C4311.5162 (19)C6—H60.95
C2—C1—C6119.43 (13)C433—C431—C432110.29 (12)
C2—C1—C11122.46 (12)C431—C432—H43A109.5
C6—C1—C11118.11 (12)C431—C432—H43B109.5
O11—C11—O12123.07 (12)H43A—C432—H43B109.5
O11—C11—C1124.60 (12)C431—C432—H43C109.5
O12—C11—C1112.32 (11)H43A—C432—H43C109.5
C11—O12—C12115.10 (11)H43B—C432—H43C109.5
O12—C12—H12A109.5C431—C433—H43D109.5
O12—C12—H12B109.5C431—C433—H43E109.5
H12A—C12—H12B109.5H43D—C433—H43E109.5
O12—C12—H12C109.5C431—C433—H43F109.5
H12A—C12—H12C109.5H43D—C433—H43F109.5
H12B—C12—H12C109.5H43E—C433—H43F109.5
C3—C2—C1120.75 (12)C431—C434—H43G109.5
C3—C2—H2119.6C431—C434—H43H109.5
C1—C2—H2119.6H43G—C434—H43H109.5
C2—C3—C4119.34 (13)C431—C434—H43I109.5
C2—C3—H3120.3H43G—C434—H43I109.5
C4—C3—H3120.3H43H—C434—H43I109.5
C5—C4—C3120.30 (12)C45—C44—C43106.11 (12)
C5—C4—N41118.31 (11)C45—C44—H44126.9
C3—C4—N41121.37 (12)C43—C44—H44126.9
C45—N41—N42111.25 (10)C44—C45—N41106.39 (12)
C45—N41—C4130.19 (11)C44—C45—N45131.64 (13)
N42—N41—C4118.00 (10)N41—C45—N45121.92 (12)
C43—N42—N41104.66 (10)C45—N45—H45A115.6
N42—C43—C44111.56 (12)C45—N45—H45B113.2
N42—C43—C431120.43 (12)H45A—N45—H45B112.5
C44—C43—C431128.00 (12)C6—C5—C4119.79 (12)
C43—C431—C434109.44 (12)C6—C5—H5120.1
C43—C431—C433108.92 (11)C4—C5—H5120.1
C434—C431—C433109.32 (12)C5—C6—C1120.37 (13)
C43—C431—C432110.15 (11)C5—C6—H6119.8
C434—C431—C432108.70 (11)C1—C6—H6119.8
C2—C1—C11—O11−171.87 (13)N42—C43—C431—C434−148.58 (13)
C6—C1—C11—O118.9 (2)C44—C43—C431—C43432.7 (2)
C2—C1—C11—O129.41 (19)N42—C43—C431—C43391.96 (15)
C6—C1—C11—O12−169.80 (12)C44—C43—C431—C433−86.79 (17)
O11—C11—O12—C12−3.30 (19)N42—C43—C431—C432−29.13 (18)
C1—C11—O12—C12175.44 (11)C44—C43—C431—C432152.12 (14)
C6—C1—C2—C30.2 (2)N42—C43—C44—C45−0.43 (17)
C11—C1—C2—C3−179.00 (13)C431—C43—C44—C45178.41 (13)
C1—C2—C3—C4−1.1 (2)C43—C44—C45—N41−0.64 (15)
C2—C3—C4—C51.7 (2)C43—C44—C45—N45−178.23 (15)
C2—C3—C4—N41179.87 (12)N42—N41—C45—C441.49 (16)
C5—C4—N41—C45−141.44 (14)C4—N41—C45—C44172.65 (13)
C3—C4—N41—C4540.4 (2)N42—N41—C45—N45179.37 (12)
C5—C4—N41—N4229.23 (18)C4—N41—C45—N45−9.5 (2)
C3—C4—N41—N42−148.96 (13)C3—C4—C5—C6−1.4 (2)
C45—N41—N42—C43−1.72 (15)N41—C4—C5—C6−179.64 (12)
C4—N41—N42—C43−174.08 (12)C4—C5—C6—C10.5 (2)
N41—N42—C43—C441.29 (15)C2—C1—C6—C50.1 (2)
N41—N42—C43—C431−177.65 (12)C11—C1—C6—C5179.34 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N45—H45A···O11i0.932.223.1388 (16)172
N45—H45B···N42ii0.922.343.2386 (17)166
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2.
(III) 4-(5-Amino-3-methyl-1H-pyrazol-1-yl)benzoic acid monohydrate top
Crystal data top
C11H11N3O2·H2OF(000) = 496
Mr = 235.24Dx = 1.400 Mg m−3
Monoclinic, P21/nMelting point: 468 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.0166 (2) ÅCell parameters from 2551 reflections
b = 7.5082 (2) Åθ = 2.2–27.5°
c = 18.5507 (5) ŵ = 0.10 mm−1
β = 91.8140 (16)°T = 120 K
V = 1116.01 (5) Å3Block, yellow
Z = 40.54 × 0.36 × 0.18 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer		2551 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2037 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.2°
ϕ and ω scansh = −7→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −9→9
Tmin = 0.961, Tmax = 0.982l = −24→24
11603 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0673P)2 + 0.2827P]
where P = (Fo2 + 2Fc2)/3
2551 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.32 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C11H11N3O2·H2OV = 1116.01 (5) Å3
Mr = 235.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.0166 (2) ŵ = 0.10 mm−1
b = 7.5082 (2) ÅT = 120 K
c = 18.5507 (5) Å0.54 × 0.36 × 0.18 mm
β = 91.8140 (16)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer		2551 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2037 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.982Rint = 0.031
11603 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.10Δρmax = 0.32 e Å−3
2551 reflectionsΔρmin = −0.28 e Å−3
155 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.17150 (16)0.63530 (18)0.46782 (7)0.0171 (3)
C110.17354 (17)0.66367 (18)0.54763 (7)0.0180 (3)
O110.06887 (13)0.75336 (14)0.57694 (5)0.0255 (3)
O120.29894 (12)0.58321 (15)0.58222 (5)0.0246 (3)
C20.29764 (17)0.54166 (19)0.43474 (7)0.0184 (3)
C30.29292 (17)0.51800 (19)0.36044 (7)0.0187 (3)
C40.16013 (17)0.58775 (18)0.31982 (7)0.0171 (3)
C50.03112 (17)0.67883 (19)0.35215 (7)0.0191 (3)
C60.03817 (17)0.70322 (18)0.42628 (7)0.0188 (3)
N410.15166 (14)0.56078 (15)0.24359 (6)0.0179 (3)
N420.00292 (15)0.50508 (16)0.21120 (6)0.0213 (3)
C130.03479 (18)0.49248 (18)0.14122 (7)0.0204 (3)
C431−0.0995 (2)0.4290 (2)0.08958 (8)0.0293 (4)
C440.19977 (17)0.54112 (19)0.12778 (7)0.0200 (3)
C450.27172 (17)0.58320 (17)0.19403 (7)0.0169 (3)
N450.43384 (14)0.63540 (16)0.21309 (6)0.0202 (3)
O10.29447 (13)0.58432 (14)0.72233 (5)0.0243 (3)
H120.29170.59300.63310.037*
H20.38750.49360.46310.022*
H30.37950.45490.33770.022*
H5−0.06040.72360.32390.023*
H6−0.04840.76660.44890.023*
H43A−0.07100.31010.07200.044*
H43B−0.10960.51160.04880.044*
H43C−0.20580.42370.11420.044*
H440.25130.54440.08240.024*
H45A0.43990.71970.24830.024*
H45B0.48880.67630.17420.024*
H1A0.19850.55090.74230.036*
H1B0.37720.51740.74190.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0163 (7)0.0208 (7)0.0141 (6)−0.0033 (5)0.0011 (5)0.0002 (5)
C110.0155 (6)0.0235 (7)0.0151 (6)−0.0031 (5)0.0009 (5)0.0001 (5)
O110.0249 (6)0.0345 (6)0.0173 (5)0.0049 (5)0.0032 (4)−0.0051 (4)
O120.0204 (5)0.0404 (6)0.0128 (5)0.0045 (4)−0.0003 (4)−0.0007 (4)
C20.0147 (7)0.0257 (7)0.0146 (6)−0.0004 (5)−0.0008 (5)0.0014 (5)
C30.0154 (7)0.0251 (7)0.0156 (6)0.0005 (5)0.0024 (5)−0.0010 (5)
C40.0186 (7)0.0199 (7)0.0128 (6)−0.0039 (5)0.0010 (5)0.0004 (5)
C50.0170 (6)0.0238 (7)0.0165 (6)0.0001 (5)−0.0018 (5)0.0017 (5)
C60.0166 (7)0.0225 (7)0.0175 (6)0.0005 (5)0.0029 (5)−0.0003 (5)
N410.0157 (6)0.0253 (6)0.0125 (5)−0.0019 (5)−0.0005 (4)0.0002 (4)
N420.0178 (6)0.0305 (7)0.0154 (5)−0.0018 (5)−0.0027 (4)−0.0002 (5)
C130.0228 (7)0.0222 (7)0.0160 (6)0.0022 (6)−0.0019 (5)0.0006 (5)
C4310.0246 (8)0.0437 (10)0.0191 (7)−0.0016 (7)−0.0046 (6)−0.0032 (6)
C440.0221 (7)0.0250 (7)0.0131 (6)0.0024 (6)0.0015 (5)0.0004 (5)
C450.0181 (7)0.0175 (6)0.0151 (6)0.0007 (5)0.0016 (5)0.0021 (5)
N450.0187 (6)0.0267 (6)0.0152 (5)−0.0046 (5)0.0024 (4)0.0006 (4)
O10.0181 (5)0.0392 (6)0.0157 (5)−0.0017 (4)0.0004 (4)0.0020 (4)
Geometric parameters (Å, º) top
C1—C21.3902 (19)N41—C451.3623 (17)
C1—C61.3943 (19)N41—N421.3828 (16)
C1—C111.4953 (17)N42—C131.3343 (17)
C11—O111.2174 (17)C13—C441.402 (2)
C11—O121.3215 (16)C13—C4311.4961 (19)
O12—H120.95C431—H43A0.98
C2—C31.3891 (18)C431—H43B0.98
C2—H20.95C431—H43C0.98
C3—C41.3873 (19)C44—C451.3778 (18)
C3—H30.95C44—H440.95
C4—C51.3915 (19)C45—N451.3924 (17)
C4—N411.4281 (16)N45—H45A0.91
C5—C61.3867 (18)N45—H45B0.91
C5—H50.95O1—H1A0.90
C6—H60.95O1—H1B0.90
C2—C1—C6119.78 (12)C45—N41—C4129.66 (11)
C2—C1—C11121.58 (12)N42—N41—C4119.11 (11)
C6—C1—C11118.63 (12)C13—N42—N41104.78 (11)
O11—C11—O12124.09 (11)N42—C13—C44111.43 (12)
O11—C11—C1122.34 (12)N42—C13—C431119.31 (13)
O12—C11—C1113.58 (11)C44—C13—C431129.25 (12)
C11—O12—H12112.2C13—C431—H43A109.5
C3—C2—C1120.35 (12)C13—C431—H43B109.5
C3—C2—H2119.8H43A—C431—H43B109.5
C1—C2—H2119.8C13—C431—H43C109.5
C4—C3—C2119.14 (12)H43A—C431—H43C109.5
C4—C3—H3120.4H43B—C431—H43C109.5
C2—C3—H3120.4C45—C44—C13105.76 (12)
C3—C4—C5121.30 (11)C45—C44—H44127.1
C3—C4—N41119.73 (12)C13—C44—H44127.1
C5—C4—N41118.93 (12)N41—C45—C44106.79 (12)
C6—C5—C4119.00 (12)N41—C45—N45122.49 (11)
C6—C5—H5120.5C44—C45—N45130.70 (12)
C4—C5—H5120.5C45—N45—H45A114.0
C5—C6—C1120.41 (12)C45—N45—H45B111.4
C5—C6—H6119.8H45A—N45—H45B108.6
C1—C6—H6119.8H1A—O1—H1B107.8
C45—N41—N42111.23 (10)
C2—C1—C11—O11175.98 (13)C5—C4—N41—C45134.47 (15)
C6—C1—C11—O11−4.8 (2)C3—C4—N41—N42132.94 (14)
C2—C1—C11—O12−3.78 (19)C5—C4—N41—N42−44.87 (17)
C6—C1—C11—O12175.45 (12)C45—N41—N42—C130.52 (15)
C6—C1—C2—C31.1 (2)C4—N41—N42—C13179.98 (12)
C11—C1—C2—C3−179.71 (13)N41—N42—C13—C44−0.82 (16)
C1—C2—C3—C4−0.5 (2)N41—N42—C13—C431178.10 (12)
C2—C3—C4—C5−0.8 (2)N42—C13—C44—C450.83 (16)
C2—C3—C4—N41−178.52 (12)C431—C13—C44—C45−177.96 (14)
C3—C4—C5—C61.4 (2)N42—N41—C45—C44−0.02 (15)
N41—C4—C5—C6179.22 (12)C4—N41—C45—C44−179.41 (13)
C4—C5—C6—C1−0.9 (2)N42—N41—C45—N45−178.72 (12)
C2—C1—C6—C5−0.4 (2)C4—N41—C45—N451.9 (2)
C11—C1—C6—C5−179.61 (13)C13—C44—C45—N41−0.46 (15)
C3—C4—N41—C45−47.7 (2)C13—C44—C45—N45178.09 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O10.951.662.6005 (13)172
O1—H1A···N42i0.901.902.8002 (16)176
O1—H1B···N45ii0.902.062.9556 (15)180
N45—H45A···N42iii0.912.313.1446 (17)152
N45—H45B···O11iv0.912.012.9020 (15)168
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, −y+3/2, z−1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC13H15N3O2C15H19N3O2C11H11N3O2·H2O
Mr245.28273.33235.24
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/n
Temperature (K)120120120
a, b, c (Å)7.2228 (4), 8.4433 (3), 10.5938 (5)6.1272 (2), 11.6374 (3), 20.3182 (7)8.0166 (2), 7.5082 (2), 18.5507 (5)
α, β, γ (°)98.234 (3), 107.609 (2), 97.907 (3)90, 98.629 (2), 9090, 91.8140 (16), 90
V (Å3)598.12 (5)1432.38 (8)1116.01 (5)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.100.090.10
Crystal size (mm)0.28 × 0.14 × 0.060.48 × 0.22 × 0.120.54 × 0.36 × 0.18
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer		Bruker–Nonius KappaCCD
diffractometer		Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.979, 0.9940.971, 0.9900.961, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections		12140, 2748, 1904 24177, 3269, 2353 11603, 2551, 2037
Rint0.0520.0500.031
(sin θ/λ)max (Å−1)0.6520.6510.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.136, 1.08 0.042, 0.112, 1.03 0.040, 0.121, 1.10
No. of reflections274832692551
No. of parameters165185155
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.320.17, −0.340.32, −0.28

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N45—H45A···O11i0.942.303.1190 (19)146
N45—H45B···O11ii0.942.113.0252 (18)165
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N45—H45A···O11i0.932.223.1388 (16)172
N45—H45B···N42ii0.922.343.2386 (17)166
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O10.951.662.6005 (13)172
O1—H1A···N42i0.901.902.8002 (16)176
O1—H1B···N45ii0.902.062.9556 (15)180
N45—H45A···N42iii0.912.313.1446 (17)152
N45—H45B···O11iv0.912.012.9020 (15)168
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x+1/2, −y+3/2, z−1/2.
 

Acknowledgements

X-ray data were collected at the EPSRC National Crystallography Service, University of Southampton, England. The authors thank the staff for all their help and advice. MN and JC thank the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JP thanks COLCIENCIAS and UNIVALLE (Universidad del Valle, Columbia) for financial support that has also supported a short stay at Instituto de Química Orgánica de Síntesis, Universidad Nacional de Rosario. EGM thanks CONICET and Universidad Nacional de Rosario for financial support.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationHooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
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 First citationOtwinowski, 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.  Google Scholar
 First citationSheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 63| Part 1| January 2007| Pages o21-o25
doi:10.1107/S0108270106050360
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