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In the title compounds, C7H8NO2+·NO3, (I), C7H8NO2+·ClO4·H2O, (II), and 2C7H8NO2+·SO42−, (III), the carboxyl planes of the 4-carboxy­phenyl­ammonium cations are twisted from the aromatic plane. A homonuclear C(8) hydrogen-bonding motif of 4-carboxy­phenyl­ammonium cations is observed in both (I) and (II), leading to `head-to-tail' layers. The cations in (III) form carboxyl group dimers, making a graph-set motif of R22(8). In all the structures, anions connect the cationic layers and an infinite chain running along the c axis is observed, having the C22(6) graph-set motif. Inter­estingly, in (II), the anions are connected through weak hydrogen bonds involving the water mol­ecules, leading to a graph-set motif of R44(12). Alternate hydro­phobic and hydro­philic layers are observed in all three compounds as a result of the column-like arrangement of the aromatic rings of the cations and the anions. Furthermore, in (I), head-to-tail N—H...O inter­actions and inter­actions linking the cations and anions form an R64(16) hydrogen-bonding motif, resulting in a pseudo-inversion centre at (1\over2, 1\over2, 0).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106033506/av3034sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106033506/av3034Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106033506/av3034IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106033506/av3034IIIsup4.hkl
Contains datablock III

CCDC references: 625694; 625695; 625696

Comment top

p-Aminobenzoic acid (PABA) is an essential biological molecule, acting as a bacterial cofactor involved in the synthesis of folic acid. PABA is also a starting material in the manufacture of target esters, salts, folic acid, azo dyes and some other organic compounds. It is used in medicine for preparing local anesthetics and ointments. PABA has proved to be a versatile reagent for structure extension by linear hydrogen-bonding associations, through both the carboxylic acid and the amine functional groups. Considering these facts and to study the hydrogen-bonding association by different graph-set motifs, PABA was treated with three different inorganic acids, viz. nitric acid, perchloric acid and sulfuric acid, and crystals were obtained. As expected, PABA forms pronotated units with the transfer of an H atom from the inorganic acid; correspondingly, the crystal is stabilized by an extensive intermolecular hydrogen-bonding network. Crystallographic studies of PABA compounds were initiated by Pant (1965), who studied the crystal structure of 3,5-dibromo-p-aminobenzoic acid. Later, Lai & Marsh (1967) extensively studied the structure of this vitamin. The structures of 4-carboxyanilinium dihydrogenmonoarsenate monohydrate (Tordjman et al., 1988), 2,4,6-trinitrobenzoic acid 4-aminobenzoic acid monohydrate (Lynch et al., 1992), bis(p-aminobenzoic acid-N)dichlorocadmium(II) (Le Fur & Masse, 1996), 4-carboxyanilinium (2R,3R)-hydrogen tartrate monohydrate (Ziqiang et al., 2002) and bis(4-aminobenzoic acid-N)silver(I) nitrate (Wang et al., 2004) have been reported previously.

The asymmetric part of (I) contains two planar moieties, namely, a p-carboxyphenylammonium cation and a nitrate anion, nearly perpendicular to one another, with a dihedral angle of 85.89° (Fig. 1). p-Carboxyphenylammonium cations are stacked almost parallel to the (001) plane, the small angular deviation of this plane being only 3.89 (2)°. In (II), the asymmetric part of the unit cell contains a p-caboxyphenylammonium cation, a perchlorate anion and a solvent water molecule (Fig. 2). Two crystallographically independent p-carboxyphenylammonium cations and a sulfate anion constitute the asymmetric part of (III) (Fig. 3). In all three compounds, the transfer of proton(s) from the inorganic acid lead(s) to a protonation on the NH2 site of the bacterial vitamin p-aminobenzoic acid and forms p-carboxyphenylammonium (or p-carboxyanilinium) cation. The protonation on the cation (NH3+) is well confirmed by the comparison of the C—N bond distance (Tables 1, 3 and 5) with the literature value of 1.38 Å for the unprotonated NH2 group (Lai & Marsh, 1967).

In compounds (I) and (II), the head (NH3+) and tail (COOH) of the cations are connected through glide-related hydrogen bonds, N4—H4A···O1A(−x + 2, y + 1/2, −z + 3/2) and N4—H4A···O1A(x − 1, −y + 1/2, z − 1/2), respectively, leading to a C(8) hydrogen-bonding graph-set motif. In (I), these motifs form a layered structure stacked parallel to the ab plane with an inter-layer distance of 6.695 Å. In (II), aggregation of these C(8) motifs leads to a sheet-like structure on the (102) parallel planes of the unit cell leading to strong X-ray reflections for the corresponding planes. These sheets are stacked with an inter-layer distance of 7.009 Å. From the Cambridge Structural Database, it is observed that a head-to-tail hydrogen-bonding association and carboxylic group dimerization are characterestic features found in most PABA complexes (Allen, 2002). The former feature is observed in (I) and (II) and the later in (III). In (III), the carboxyl groups of the cations are dimerized through O1B—H1B···O2A and O2B···H2B···O1A hydrogen bonds, leading to a graph-set motif of R22(8). Schematic diagrams of different hydrogen-bond motifs are shown in Fig. 4.

In all three structures, twisting of the carboxyl plane from the aromatic ring is observed. The angle of twisting is 9.55 (9)° in (I), 6.25 (3)° in (II), and 5.95 (3) and 3.41 (2)° for the cations in (III). In structure (II), atom O1A deviates by 0.151 (4) Å, which is more than the deviation of O1B (the hydroxy atom), whereas in structure (I) and both the residues of structure (III), atom O1B deviates [0.277 (7) Å in (I), and 0.215 (7) and 0.121 (6) Å in (III)] more than O1A. This twisting of the carboxylic acid group is due to the hydrogen-bonding association and the packing specificity of the crystal. In all three structures, the cations are linked by the anions through N—H···O bonds to form an infinite chain running along the c axis with the linear C22(6) graph-set motif [N4—H4C···O1/N4—H4B···O2 (x, y, z + 1) in (I), N4—H4B···O2(x − 1, −y + 1/2, z+1/2)/N4—H4C···O3(x − 1, −y + 1/2, z − 1/2) in (II), and N14—H14B···O2(x, y, z − 1)/N14—H14C···O1 and N24—H24A···O4(1 + x, y, 1 + z)/N24—H24C···O3(1 + x, y, z) in both the cations of (III).

The packing diagram of (I) in Fig. 5 shows hydrophobic layers formed by the stacking of aromatic rings at x = 0. Also in (I), a hydrogen-bonding graph-set motif of R64(16) exists as a result of glide-related direct interactions and interactions tinvolving the anions and the amine and carboxylic groups. These closed rings of size 2.850 × 8.681 Å (including contact radii) extend along the c axis. This closed-ring R64(16) structure results in a pseudo-inversion centre at (1/2, 1/2, 0), which is extended as a pseudo-inversion axis through (1/2, 1/2, 1/2) (Fig. 6). Such pseudo-symmetries are also observed in the structure of PABA (Lai & Marsh, 1967). Fig. 7 represents the structural overlay of the cation in structure (I) (minor occupancy of OH group is omitted) with both the residues of structure (III) by fitting together the atoms of the aromatic ring. Slight deviation of the amino and carboxyl groups of the cations in (I) is observed.

In (II), perchlorate anions are sandwiched between hydrophobic layers of cations at y = 1/4 and 3/4, thus forming alternating hydrophilic and hydrophobic columns in the bc plane of the unit cell (Fig. 8). Primary C22(6) graph-set motifs connect two adjacent sheets of the p-carboxyphenylammonium ion formed by the above-mentioned C(8) primary graph-set motif. Combination of these two primary motifs leads to a new secondary graph-set motif R66(28) (Fig. 9). The water molecules interact with the anions through weak hydrogen bonds, connecting two inversely related perchlorate anions to form a closed hydrogen-bonding dimer or ring, leading to a graph-set motif of R44(12) (Fig. 10). These motifs are connected linearly along the c axis by another weak interaction O1W···O4(−x + 1, −y + 1, −z + 1) [3.162 (4) Å]. Three-centered hydrogen bonds, formed by the amino group with the anion, relate two inversely related cations through weak hydrogen bonds [N4—H4C···O1(x − 1, −y + 1/2, z + 1/2) and N4—H4C···O3(1 − x, 1/2 + y, 3/2 − z)] making a graph-set motif of R24(10).

In (III), the sulfate anions are stacked nearly at x = 0 forming hydrophilic columns. Alternatively, hydrophobic layers are observed nearly at x = 1/2 and 3/4 owing to the stacking of aromatic rings (Fig. 11). The anions are connected to the cationic dimers through extensive hydrogen bonding between the O atoms of the anion and the amino group. The cationic dimers connected by the above-mentioned C22(6) hydrogen-bond motifs form a sheet-like structure parallel to the ac plane (Fig. 12). The planes of the cationic dimers make a dihedral angle of 20.87° with the ac plane of the unit cell.

Experimental top

The title compounds, (I), (II) and (III), were crystallized from aqueous solutions containing p-aminobenzoic acid with nitric acid, perchloric acid and sulfuric acid in the stochiometric ratios 1:1, 1:1 and 1:2, respectively, at room temperature, by the technique of slow evaporation.

Refinement top

The water H atoms in (II) were located and refined isotropically. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å, O—H = 0.82 Å and N—H = 0.89 Å and Uiso(H) = 1.2–1.5Ueq(parent atom). In structure (I), the hydroxy group O1B is disordered over two positions with major and minor site occupancies of 0.75 and 1/4, respectively.

Computing details top

For all compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC. Molecular graphics: SHELXTL/PC and PLATON (Spek, 2003) for (I); SHELXTL/PC, Mercury (Version 1.4.1, Macrae et al., 2006) and PLATON (Spek, 2003) for (II), (III). For all compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids. The major (75%) and minor (25%) occupancies of the hydroxy group are shown.
[Figure 2] Fig. 2. The molecular structure of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids.
[Figure 3] Fig. 3. The molecular structure of (III), with the atom-numbering scheme and 50% probability displacement ellipsoids.
[Figure 4] Fig. 4. Schemes showing the different hydrogen-bonding motifs.
[Figure 5] Fig. 5. The packing of (I), viewed down the c axis. Hydrogen bonds are drawn as dashed lines and H atoms not invovled in these interactions have been omitted.
[Figure 6] Fig. 6. Head-to-tail C(8) and linear C22(6) hydrogen-bonding motifs, resulting in a secondary structure of an R33(28) motif in (II). Hydrogen bonds are drawn as dashed lines.
[Figure 7] Fig. 7. Structural overlay diagram of p-carboxyphenylammonium cations in (I) and (III) [the minor occupancy component of the OH group in (I) has been omitted].
[Figure 8] Fig. 8. The packing of (II), viewed down the a axis. Hydrogen bonds are drawn as dashed lines and H atoms not invovled in these interactions have been omitted.
[Figure 9] Fig. 9. The pseudo-inversion centre and the cavity formed by anions and cations in the R64(16) hydrogen-bonded motif in (I). Hydrogen bonds are drawn as dashed lines and C-bound H atoms have been omitted.
[Figure 10] Fig. 10. The R22(12) hydrogen-bonding motif formed by the interaction between perchlorate and water molecules in (II). Hydrogen bonds are drawn as dashed lines.
[Figure 11] Fig. 11. The packing of (III), viewed down the c axis. Hydrogen bonds are drawn as dashed lines and H atoms not invovled in these interactions have been omitted.
[Figure 12] Fig. 12. Molecular aggregation of cationic dimers [R22(6) motif] and the C22(6) graph-set motif running along the c axis, forming a sheet-like structure in (III). Hydrogen bonds are drawn as dashed lines and C-bound H atoms have been omitted.
(I) top
Crystal data top
C7H8NO2+·NO3F(000) = 416
Mr = 200.15Dx = 1.497 Mg m3
Dm = 1.49 Mg m3
Dm measured by flotation using a liquid mixture of xylene and bromoform
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.8154 (9) Åθ = 9.9–14.4°
b = 15.0516 (3) ŵ = 0.13 mm1
c = 6.6950 (6) ÅT = 293 K
β = 90.933 (12)°Block, light pink
V = 888.14 (14) Å30.22 × 0.19 × 0.17 mm
Z = 4
Data collection top
Nonius MACH3 sealed tube
diffractometer
Rint = 0.016
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.3°
Graphite monochromatorh = 1010
ω–2θ scansk = 117
1832 measured reflectionsl = 07
1549 independent reflections3 standard reflections every 60 min
1264 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0712P)2 + 0.3551P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1549 reflectionsΔρmax = 0.29 e Å3
139 parametersΔρmin = 0.21 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.047 (6)
Crystal data top
C7H8NO2+·NO3V = 888.14 (14) Å3
Mr = 200.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.8154 (9) ŵ = 0.13 mm1
b = 15.0516 (3) ÅT = 293 K
c = 6.6950 (6) Å0.22 × 0.19 × 0.17 mm
β = 90.933 (12)°
Data collection top
Nonius MACH3 sealed tube
diffractometer
Rint = 0.016
1832 measured reflections3 standard reflections every 60 min
1549 independent reflections intensity decay: none
1264 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.08Δρmax = 0.29 e Å3
1549 reflectionsΔρmin = 0.21 e Å3
139 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C11.0614 (2)0.26541 (13)0.7285 (3)0.0402 (5)
C20.9128 (2)0.23648 (13)0.7434 (3)0.0415 (5)
H20.89160.17600.74830.050*
C30.7965 (2)0.29739 (14)0.7508 (3)0.0430 (5)
H30.69630.27850.75890.052*
C40.8308 (2)0.38687 (12)0.7461 (3)0.0365 (5)
C50.9772 (2)0.41687 (13)0.7335 (3)0.0452 (5)
H50.99800.47740.73180.054*
C61.0933 (2)0.35541 (14)0.7234 (4)0.0480 (6)
H61.19320.37460.71310.058*
C111.1830 (2)0.19752 (15)0.7135 (4)0.0504 (6)
O1A1.16056 (18)0.11868 (10)0.7343 (3)0.0564 (5)
O1B1.3149 (3)0.2309 (2)0.6546 (4)0.0552 (8)0.75
H1B1.37800.19100.64860.083*0.75
O1B'1.3167 (9)0.2319 (6)0.792 (3)0.094 (4)0.25
H1B'1.38320.19390.78840.142*0.25
N40.70517 (18)0.45084 (11)0.7523 (3)0.0415 (5)
H4A0.74190.50580.74570.062*
H4B0.65520.44410.86580.062*
H4C0.64230.44130.64920.062*
N10.59434 (19)0.41968 (12)0.2482 (3)0.0486 (5)
O10.5333 (2)0.39844 (15)0.4074 (3)0.0763 (6)
O20.5345 (2)0.39385 (13)0.0872 (3)0.0662 (6)
O30.7100 (2)0.46391 (14)0.2473 (4)0.0836 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0393 (11)0.0329 (10)0.0483 (12)0.0007 (8)0.0006 (8)0.0009 (9)
C20.0432 (11)0.0277 (10)0.0536 (12)0.0027 (8)0.0023 (9)0.0009 (9)
C30.0344 (10)0.0370 (11)0.0575 (13)0.0058 (8)0.0022 (9)0.0009 (9)
C40.0346 (10)0.0324 (10)0.0427 (10)0.0015 (8)0.0019 (8)0.0001 (8)
C50.0377 (11)0.0285 (10)0.0695 (14)0.0031 (9)0.0019 (9)0.0011 (9)
C60.0321 (10)0.0368 (11)0.0752 (15)0.0037 (8)0.0014 (9)0.0008 (10)
C110.0416 (12)0.0414 (12)0.0683 (15)0.0032 (9)0.0008 (10)0.0001 (10)
O1A0.0524 (9)0.0329 (8)0.0842 (12)0.0071 (7)0.0052 (8)0.0022 (7)
O1B0.0419 (13)0.0481 (15)0.0759 (17)0.0088 (10)0.0132 (13)0.0070 (14)
O1B'0.031 (4)0.036 (4)0.216 (14)0.009 (3)0.006 (7)0.008 (7)
N40.0349 (9)0.0354 (9)0.0543 (10)0.0017 (7)0.0036 (7)0.0001 (7)
N10.0321 (9)0.0389 (10)0.0749 (14)0.0038 (8)0.0010 (9)0.0011 (9)
O10.0634 (12)0.1024 (16)0.0629 (11)0.0225 (10)0.0017 (9)0.0012 (10)
O20.0552 (10)0.0820 (13)0.0615 (11)0.0216 (9)0.0046 (8)0.0048 (9)
O30.0521 (11)0.0696 (13)0.1290 (19)0.0285 (9)0.0008 (11)0.0035 (12)
Geometric parameters (Å, º) top
C1—C61.384 (3)C11—O1A1.211 (3)
C1—C21.386 (3)C11—O1B1.333 (3)
C1—C111.486 (3)C11—O1B'1.383 (10)
C2—C31.377 (3)O1B—H1B0.8200
C2—H20.9300O1B'—H1B'0.8200
C3—C41.381 (3)N4—H4A0.8900
C3—H30.9300N4—H4B0.8900
C4—C51.371 (3)N4—H4C0.8900
C4—N41.468 (2)N1—O31.217 (2)
C5—C61.382 (3)N1—O11.244 (3)
C5—H50.9300N1—O21.254 (3)
C6—H60.9300
C6—C1—C2120.16 (19)O1A—C11—O1B123.3 (2)
C6—C1—C11121.61 (18)O1A—C11—O1B'117.6 (5)
C2—C1—C11118.22 (18)O1B—C11—O1B'39.5 (6)
C3—C2—C1119.91 (18)O1A—C11—C1123.1 (2)
C3—C2—H2120.0O1B—C11—C1113.2 (2)
C1—C2—H2120.0O1B'—C11—C1109.2 (4)
C2—C3—C4119.04 (18)C11—O1B—H1B109.5
C2—C3—H3120.5C11—O1B'—H1B'109.5
C4—C3—H3120.5C4—N4—H4A109.5
C5—C4—C3121.94 (18)C4—N4—H4B109.5
C5—C4—N4119.80 (17)H4A—N4—H4B109.5
C3—C4—N4118.26 (17)C4—N4—H4C109.5
C4—C5—C6118.77 (18)H4A—N4—H4C109.5
C4—C5—H5120.6H4B—N4—H4C109.5
C6—C5—H5120.6O3—N1—O1121.3 (2)
C5—C6—C1120.17 (19)O3—N1—O2120.4 (2)
C5—C6—H6119.9O1—N1—O2118.35 (18)
C1—C6—H6119.9
C6—C1—C2—C30.7 (3)C2—C1—C6—C50.1 (3)
C11—C1—C2—C3177.81 (19)C11—C1—C6—C5178.6 (2)
C1—C2—C3—C40.9 (3)C6—C1—C11—O1A173.6 (2)
C2—C3—C4—C50.2 (3)C2—C1—C11—O1A7.9 (3)
C2—C3—C4—N4179.44 (18)C6—C1—C11—O1B13.0 (3)
C3—C4—C5—C60.6 (3)C2—C1—C11—O1B165.5 (2)
N4—C4—C5—C6178.57 (19)C6—C1—C11—O1B'29.3 (8)
C4—C5—C6—C10.8 (3)C2—C1—C11—O1B'152.2 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···O1i0.822.573.202 (3)135
O1B—H1B···O2i0.822.323.038 (10)146
N4—H4A···O1Aii0.891.912.791 (2)171
N4—H4B···O2iii0.891.992.853 (2)163
N4—H4C···O10.891.982.852 (3)167
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+2, y+1/2, z+3/2; (iii) x, y, z+1.
(II) top
Crystal data top
C7H8NO2+·ClO4·H2OF(000) = 528
Mr = 255.61Dx = 1.622 Mg m3
Dm = 1.61 Mg m3
Dm measured by flotation technique using a liquid mixture of carbon tetrachloride and bromoform
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.5492 (7) Åθ = 11.5–14.3°
b = 19.3871 (5) ŵ = 0.39 mm1
c = 7.2974 (3) ÅT = 293 K
β = 101.524 (5)°Block, colourless
V = 1046.42 (12) Å30.23 × 0.20 × 0.18 mm
Z = 4
Data collection top
Nonius MACH3 sealed tube
diffractometer
1587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 25.0°, θmin = 2.1°
ω–2θ scansh = 88
Absorption correction: ψ scan
(North et al., 1968)
k = 2323
Tmin = 0.911, Tmax = 0.994l = 08
3032 measured reflections3 standard reflections every 60 min
1833 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0592P)2 + 0.8272P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1833 reflectionsΔρmax = 0.52 e Å3
156 parametersΔρmin = 0.33 e Å3
2 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.049 (4)
Crystal data top
C7H8NO2+·ClO4·H2OV = 1046.42 (12) Å3
Mr = 255.61Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5492 (7) ŵ = 0.39 mm1
b = 19.3871 (5) ÅT = 293 K
c = 7.2974 (3) Å0.23 × 0.20 × 0.18 mm
β = 101.524 (5)°
Data collection top
Nonius MACH3 sealed tube
diffractometer
1587 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.029
Tmin = 0.911, Tmax = 0.9943 standard reflections every 60 min
3032 measured reflections intensity decay: none
1833 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0422 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.52 e Å3
1833 reflectionsΔρmin = 0.33 e Å3
156 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3520 (3)0.26926 (11)0.9953 (3)0.0303 (5)
C20.3959 (3)0.19965 (12)1.0169 (3)0.0356 (6)
H20.51200.18651.07500.043*
C30.2671 (3)0.15006 (12)0.9523 (3)0.0363 (6)
H30.29600.10340.96510.044*
C40.0950 (3)0.17067 (11)0.8685 (3)0.0311 (5)
C50.0483 (3)0.23973 (12)0.8465 (3)0.0354 (5)
H50.06840.25280.79010.042*
C60.1785 (3)0.28871 (12)0.9098 (3)0.0347 (5)
H60.14960.33530.89510.042*
N40.0423 (3)0.11817 (10)0.8007 (3)0.0371 (5)
H4A0.14560.13870.74880.056*
H4B0.05960.09220.89610.056*
H4C0.00500.09180.71610.056*
C110.4921 (3)0.32139 (12)1.0682 (3)0.0340 (5)
O1A0.6400 (2)0.30696 (9)1.1586 (3)0.0488 (5)
O1B0.4390 (2)0.38523 (9)1.0268 (3)0.0491 (5)
H1B0.51710.41211.07850.074*
Cl10.80735 (8)0.44858 (3)0.75074 (8)0.0401 (3)
O10.8161 (3)0.51293 (12)0.8533 (4)0.0712 (7)
O20.9551 (4)0.44862 (14)0.6567 (4)0.0793 (8)
O30.8212 (4)0.39423 (12)0.8810 (4)0.0755 (7)
O40.6381 (4)0.44810 (16)0.6250 (4)0.0877 (9)
O1W0.3392 (3)0.52034 (10)0.7949 (3)0.0506 (5)
H1W0.386 (5)0.502 (2)0.719 (4)0.080 (14)*
H2W0.295 (6)0.491 (2)0.850 (6)0.109 (17)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0281 (11)0.0315 (11)0.0306 (11)0.0003 (9)0.0041 (9)0.0004 (9)
C20.0273 (11)0.0353 (12)0.0403 (13)0.0048 (9)0.0026 (9)0.0024 (10)
C30.0356 (12)0.0275 (11)0.0424 (13)0.0039 (9)0.0004 (10)0.0014 (10)
C40.0307 (11)0.0317 (11)0.0291 (11)0.0029 (9)0.0016 (9)0.0007 (9)
C50.0258 (11)0.0357 (12)0.0409 (13)0.0043 (9)0.0023 (9)0.0012 (10)
C60.0316 (12)0.0280 (11)0.0426 (13)0.0037 (9)0.0029 (10)0.0024 (10)
N40.0325 (10)0.0342 (10)0.0407 (11)0.0025 (8)0.0022 (8)0.0012 (9)
C110.0311 (12)0.0333 (12)0.0367 (12)0.0007 (9)0.0046 (9)0.0019 (10)
O1A0.0328 (9)0.0386 (10)0.0669 (13)0.0042 (7)0.0093 (8)0.0064 (9)
O1B0.0392 (10)0.0303 (9)0.0702 (13)0.0012 (7)0.0077 (9)0.0000 (9)
Cl10.0412 (4)0.0394 (4)0.0390 (4)0.0017 (2)0.0067 (3)0.0057 (2)
O10.0846 (17)0.0518 (13)0.0805 (16)0.0033 (11)0.0241 (13)0.0134 (12)
O20.0811 (17)0.102 (2)0.0657 (15)0.0181 (14)0.0399 (13)0.0167 (14)
O30.0924 (18)0.0600 (14)0.0791 (16)0.0131 (12)0.0289 (14)0.0306 (12)
O40.0640 (15)0.107 (2)0.0786 (17)0.0162 (14)0.0181 (13)0.0087 (15)
O1W0.0485 (11)0.0396 (11)0.0606 (13)0.0032 (9)0.0034 (10)0.0022 (10)
Geometric parameters (Å, º) top
C1—C61.386 (3)N4—H4A0.8900
C1—C21.391 (3)N4—H4B0.8900
C1—C111.483 (3)N4—H4C0.8900
C2—C31.381 (3)C11—O1A1.211 (3)
C2—H20.9300C11—O1B1.317 (3)
C3—C41.380 (3)O1B—H1B0.8200
C3—H30.9300Cl1—O31.409 (2)
C4—C51.386 (3)Cl1—O41.416 (2)
C4—N41.466 (3)Cl1—O21.421 (2)
C5—C61.378 (3)Cl1—O11.449 (2)
C5—H50.9300O1W—H1W0.794 (19)
C6—H60.9300O1W—H2W0.81 (2)
C6—C1—C2119.8 (2)C4—N4—H4A109.5
C6—C1—C11121.2 (2)C4—N4—H4B109.5
C2—C1—C11118.9 (2)H4A—N4—H4B109.5
C3—C2—C1120.1 (2)C4—N4—H4C109.5
C3—C2—H2120.0H4A—N4—H4C109.5
C1—C2—H2120.0H4B—N4—H4C109.5
C4—C3—C2119.1 (2)O1A—C11—O1B123.2 (2)
C4—C3—H3120.5O1A—C11—C1123.5 (2)
C2—C3—H3120.5O1B—C11—C1113.30 (19)
C3—C4—C5121.7 (2)C11—O1B—H1B109.5
C3—C4—N4119.2 (2)O3—Cl1—O4111.62 (17)
C5—C4—N4119.06 (19)O3—Cl1—O2111.48 (16)
C6—C5—C4118.6 (2)O4—Cl1—O2112.36 (18)
C6—C5—H5120.7O3—Cl1—O1107.81 (16)
C4—C5—H5120.7O4—Cl1—O1106.41 (17)
C5—C6—C1120.7 (2)O2—Cl1—O1106.80 (15)
C5—C6—H6119.7H1W—O1W—H2W109 (5)
C1—C6—H6119.7
C6—C1—C2—C30.4 (4)C4—C5—C6—C10.6 (4)
C11—C1—C2—C3179.2 (2)C2—C1—C6—C50.3 (4)
C1—C2—C3—C40.7 (4)C11—C1—C6—C5178.5 (2)
C2—C3—C4—C50.4 (4)C6—C1—C11—O1A173.0 (2)
C2—C3—C4—N4179.6 (2)C2—C1—C11—O1A5.8 (4)
C3—C4—C5—C60.2 (4)C6—C1—C11—O1B6.1 (3)
N4—C4—C5—C6179.7 (2)C2—C1—C11—O1B175.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O1Ai0.891.932.818 (3)173
N4—H4B···O2ii0.892.042.906 (3)164
N4—H4C···O1iii0.892.223.018 (3)150
N4—H4C···O3i0.892.553.039 (3)116
O1B—H1B···O1Wiv0.821.832.641 (3)171
O1W—H1W···O40.79 (2)2.39 (3)3.116 (4)152 (4)
O1W—H2W···O1iv0.81 (2)2.47 (4)3.096 (4)135 (4)
Symmetry codes: (i) x1, y+1/2, z1/2; (ii) x1, y+1/2, z+1/2; (iii) x+1, y1/2, z+3/2; (iv) x+1, y+1, z+2.
(III) top
Crystal data top
2C7H8NO2+·SO42F(000) = 776
Mr = 372.35Dx = 1.566 Mg m3
Dm = 1.56 Mg m3
Dm measured by flotation technique using a liquid mixture of carbon xylene and bromoform
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 18.7094 (8) Åθ = 10.2–13.2°
b = 14.0562 (4) ŵ = 0.25 mm1
c = 6.0551 (5) ÅT = 293 K
β = 97.272 (5)°Block, colourless
V = 1579.51 (15) Å30.26 × 0.22 × 0.18 mm
Z = 4
Data collection top
Nonius MACH3 sealed tube
diffractometer
2014 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
Graphite monochromatorθmax = 25.0°, θmin = 2.2°
ω–2θ scansh = 2222
Absorption correction: ψ scan
(North et al., 1968)
k = 116
Tmin = 0.953, Tmax = 0.997l = 07
3323 measured reflections3 standard reflections every 60 min
2763 independent reflections intensity decay: none
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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.1287P)2 + 0.1992P]
where P = (Fo2 + 2Fc2)/3
2763 reflections(Δ/σ)max < 0.001
230 parametersΔρmax = 0.84 e Å3
0 restraintsΔρmin = 0.69 e Å3
Crystal data top
2C7H8NO2+·SO42V = 1579.51 (15) Å3
Mr = 372.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 18.7094 (8) ŵ = 0.25 mm1
b = 14.0562 (4) ÅT = 293 K
c = 6.0551 (5) Å0.26 × 0.22 × 0.18 mm
β = 97.272 (5)°
Data collection top
Nonius MACH3 sealed tube
diffractometer
2014 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.045
Tmin = 0.953, Tmax = 0.9973 standard reflections every 60 min
3323 measured reflections intensity decay: none
2763 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.181H-atom parameters constrained
S = 1.05Δρmax = 0.84 e Å3
2763 reflectionsΔρmin = 0.69 e Å3
230 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C110.39211 (19)0.3808 (2)0.4043 (6)0.0398 (8)
C1110.4695 (2)0.3776 (3)0.4989 (7)0.0482 (10)
O1A0.48737 (16)0.4072 (3)0.6910 (5)0.0739 (10)
O1B0.51279 (16)0.3420 (3)0.3765 (6)0.0762 (11)
H1B0.55270.33630.44860.114*
C120.34168 (19)0.4139 (3)0.5331 (6)0.0424 (9)
H120.35690.43870.67350.051*
C130.26935 (19)0.4107 (3)0.4575 (5)0.0377 (8)
H130.23580.43230.54670.045*
C140.24710 (17)0.3752 (2)0.2474 (5)0.0303 (7)
N140.17053 (14)0.3649 (2)0.1747 (4)0.0324 (6)
H14A0.15810.30400.18240.049*
H14B0.16070.38520.03490.049*
H14C0.14580.39930.26240.049*
C150.29666 (19)0.3446 (3)0.1117 (6)0.0401 (9)
H150.28110.32210.03070.048*
C160.3694 (2)0.3476 (3)0.1891 (6)0.0444 (9)
H160.40310.32760.09840.053*
C210.74070 (19)0.3673 (2)0.8710 (6)0.0364 (8)
C2110.66428 (19)0.3649 (3)0.7710 (6)0.0427 (9)
O2A0.64839 (15)0.3377 (2)0.5768 (5)0.0620 (9)
O2B0.61855 (15)0.3933 (3)0.8960 (5)0.0642 (9)
H2B0.57800.39200.82630.096*
C220.79444 (18)0.3423 (2)0.7468 (5)0.0354 (8)
H220.78200.32110.60150.042*
C230.86627 (18)0.3477 (2)0.8319 (5)0.0339 (8)
H230.90200.33160.74490.041*
C240.88392 (17)0.3777 (2)1.0505 (5)0.0271 (7)
N240.95875 (14)0.38738 (18)1.1427 (4)0.0294 (6)
H24A0.96870.34661.25480.044*
H24B0.96690.44651.19240.044*
H24C0.98670.37501.03770.044*
C250.83084 (18)0.4025 (2)1.1790 (5)0.0345 (8)
H250.84350.42271.32500.041*
C260.75969 (19)0.3976 (3)1.0921 (6)0.0392 (8)
H260.72400.41411.17900.047*
S10.07132 (4)0.36963 (5)0.63025 (11)0.0261 (3)
O10.08188 (12)0.44111 (15)0.4598 (3)0.0323 (6)
O20.14086 (13)0.32125 (17)0.6978 (4)0.0393 (6)
O30.05029 (13)0.41852 (15)0.8284 (3)0.0343 (6)
O40.01590 (13)0.30125 (16)0.5442 (4)0.0377 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0322 (18)0.046 (2)0.041 (2)0.0016 (15)0.0009 (15)0.0001 (16)
C1110.0333 (19)0.059 (2)0.050 (2)0.0007 (17)0.0011 (17)0.0067 (19)
O1A0.0402 (17)0.112 (3)0.064 (2)0.0064 (17)0.0133 (15)0.028 (2)
O1B0.0311 (15)0.115 (3)0.080 (2)0.0097 (17)0.0001 (15)0.029 (2)
C120.038 (2)0.059 (2)0.0288 (18)0.0043 (17)0.0008 (14)0.0056 (16)
C130.0354 (18)0.054 (2)0.0242 (17)0.0026 (15)0.0043 (13)0.0045 (15)
C140.0312 (17)0.0358 (17)0.0240 (16)0.0020 (13)0.0040 (13)0.0046 (13)
N140.0305 (14)0.0446 (15)0.0211 (13)0.0028 (12)0.0010 (11)0.0037 (12)
C150.0377 (19)0.056 (2)0.0265 (17)0.0038 (16)0.0022 (14)0.0087 (15)
C160.0359 (19)0.060 (2)0.038 (2)0.0001 (17)0.0103 (15)0.0073 (17)
C210.0332 (18)0.0396 (18)0.0354 (18)0.0010 (14)0.0001 (14)0.0018 (15)
C2110.0341 (19)0.050 (2)0.043 (2)0.0025 (16)0.0006 (16)0.0002 (17)
O2A0.0365 (15)0.092 (2)0.0535 (18)0.0011 (15)0.0078 (13)0.0198 (17)
O2B0.0304 (14)0.103 (2)0.0576 (19)0.0070 (16)0.0007 (13)0.0120 (18)
C220.0376 (19)0.0458 (19)0.0215 (16)0.0014 (15)0.0011 (13)0.0057 (14)
C230.0340 (18)0.0437 (18)0.0242 (16)0.0001 (14)0.0048 (13)0.0045 (14)
C240.0290 (16)0.0287 (15)0.0236 (15)0.0009 (12)0.0032 (12)0.0022 (12)
N240.0290 (14)0.0361 (14)0.0222 (13)0.0002 (11)0.0001 (10)0.0017 (11)
C250.0400 (19)0.0431 (17)0.0204 (15)0.0020 (15)0.0038 (13)0.0044 (14)
C260.0356 (18)0.049 (2)0.0341 (19)0.0009 (16)0.0084 (15)0.0049 (16)
S10.0291 (4)0.0328 (4)0.0161 (4)0.0006 (3)0.0011 (3)0.0001 (3)
O10.0381 (13)0.0354 (12)0.0237 (12)0.0018 (10)0.0049 (9)0.0029 (9)
O20.0367 (13)0.0502 (13)0.0310 (13)0.0091 (11)0.0047 (10)0.0023 (11)
O30.0448 (14)0.0383 (12)0.0212 (11)0.0039 (10)0.0096 (10)0.0025 (9)
O40.0445 (14)0.0419 (13)0.0254 (12)0.0088 (11)0.0012 (10)0.0032 (10)
Geometric parameters (Å, º) top
C11—C121.378 (5)C21—C2111.481 (5)
C11—C161.399 (5)C211—O2A1.237 (5)
C11—C1111.489 (5)C211—O2B1.276 (5)
C111—O1A1.241 (5)O2B—H2B0.8200
C111—O1B1.268 (5)C22—C231.379 (5)
O1B—H1B0.8200C22—H220.9300
C12—C131.373 (5)C23—C241.389 (4)
C12—H120.9300C23—H230.9300
C13—C141.381 (5)C24—C251.381 (4)
C13—H130.9300C24—N241.447 (4)
C14—C151.383 (5)N24—H24A0.8900
C14—N141.452 (4)N24—H24B0.8900
N14—H14A0.8900N24—H24C0.8900
N14—H14B0.8900C25—C261.370 (5)
N14—H14C0.8900C25—H250.9300
C15—C161.383 (5)C26—H260.9300
C15—H150.9300S1—O41.461 (2)
C16—H160.9300S1—O11.472 (2)
C21—C221.375 (5)S1—O31.478 (2)
C21—C261.407 (5)S1—O21.479 (2)
C12—C11—C16119.4 (3)O2A—C211—O2B124.2 (3)
C12—C11—C111119.7 (3)O2A—C211—C21120.0 (3)
C16—C11—C111120.9 (3)O2B—C211—C21115.8 (3)
O1A—C111—O1B124.4 (4)C211—O2B—H2B109.5
O1A—C111—C11118.9 (4)C21—C22—C23121.8 (3)
O1B—C111—C11116.7 (4)C21—C22—H22119.1
C111—O1B—H1B109.5C23—C22—H22119.1
C13—C12—C11121.1 (3)C22—C23—C24118.4 (3)
C13—C12—H12119.4C22—C23—H23120.8
C11—C12—H12119.4C24—C23—H23120.8
C12—C13—C14119.2 (3)C25—C24—C23120.8 (3)
C12—C13—H13120.4C25—C24—N24119.3 (3)
C14—C13—H13120.4C23—C24—N24119.9 (3)
C13—C14—C15120.9 (3)C24—N24—H24A109.5
C13—C14—N14119.1 (3)C24—N24—H24B109.5
C15—C14—N14119.9 (3)H24A—N24—H24B109.5
C14—N14—H14A109.5C24—N24—H24C109.5
C14—N14—H14B109.5H24A—N24—H24C109.5
H14A—N14—H14B109.5H24B—N24—H24C109.5
C14—N14—H14C109.5C26—C25—C24120.2 (3)
H14A—N14—H14C109.5C26—C25—H25119.9
H14B—N14—H14C109.5C24—C25—H25119.9
C16—C15—C14119.6 (3)C25—C26—C21119.8 (3)
C16—C15—H15120.2C25—C26—H26120.1
C14—C15—H15120.2C21—C26—H26120.1
C15—C16—C11119.7 (3)O4—S1—O1110.57 (12)
C15—C16—H16120.1O4—S1—O3110.22 (14)
C11—C16—H16120.1O1—S1—O3108.97 (13)
C22—C21—C26118.9 (3)O4—S1—O2110.84 (14)
C22—C21—C211120.4 (3)O1—S1—O2108.44 (13)
C26—C21—C211120.7 (3)O3—S1—O2107.73 (13)
C12—C11—C111—O1A1.8 (6)C22—C21—C211—O2A2.1 (6)
C16—C11—C111—O1A179.6 (4)C26—C21—C211—O2A179.6 (4)
C12—C11—C111—O1B176.5 (4)C22—C21—C211—O2B177.1 (4)
C16—C11—C111—O1B1.2 (6)C26—C21—C211—O2B1.2 (5)
C16—C11—C12—C133.0 (6)C26—C21—C22—C231.2 (5)
C111—C11—C12—C13174.8 (4)C211—C21—C22—C23177.1 (3)
C11—C12—C13—C141.0 (6)C21—C22—C23—C241.2 (5)
C12—C13—C14—C151.2 (5)C22—C23—C24—C250.7 (5)
C12—C13—C14—N14175.2 (3)C22—C23—C24—N24177.9 (3)
C13—C14—C15—C161.5 (5)C23—C24—C25—C260.2 (5)
N14—C14—C15—C16174.9 (3)N24—C24—C25—C26177.4 (3)
C14—C15—C16—C110.5 (6)C24—C25—C26—C210.2 (5)
C12—C11—C16—C152.7 (6)C22—C21—C26—C250.7 (5)
C111—C11—C16—C15175.0 (4)C211—C21—C26—C25177.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···O2A0.821.862.670 (4)170
N14—H14A···O2i0.891.792.682 (3)175
N14—H14B···O2ii0.892.222.936 (3)137
N14—H14C···O10.891.892.757 (3)165
O2B—H2B···O1A0.821.802.614 (4)171
N24—H24A···O4iii0.891.972.804 (3)156
N24—H24B···O3iv0.891.932.741 (3)151
N24—H24C···O3v0.891.942.752 (3)150
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z1; (iii) x+1, y, z+1; (iv) x+1, y+1, z+2; (v) x+1, y, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC7H8NO2+·NO3C7H8NO2+·ClO4·H2O2C7H8NO2+·SO42
Mr200.15255.61372.35
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)293293293
a, b, c (Å)8.8154 (9), 15.0516 (3), 6.6950 (6)7.5492 (7), 19.3871 (5), 7.2974 (3)18.7094 (8), 14.0562 (4), 6.0551 (5)
β (°) 90.933 (12) 101.524 (5) 97.272 (5)
V3)888.14 (14)1046.42 (12)1579.51 (15)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.130.390.25
Crystal size (mm)0.22 × 0.19 × 0.170.23 × 0.20 × 0.180.26 × 0.22 × 0.18
Data collection
DiffractometerNonius MACH3 sealed tube
diffractometer
Nonius MACH3 sealed tube
diffractometer
Nonius MACH3 sealed tube
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
Tmin, Tmax0.911, 0.9940.953, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
1832, 1549, 1264 3032, 1833, 1587 3323, 2763, 2014
Rint0.0160.0290.045
(sin θ/λ)max1)0.5950.5950.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.134, 1.08 0.042, 0.120, 1.07 0.060, 0.181, 1.05
No. of reflections154918332763
No. of parameters139156230
No. of restraints020
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.210.52, 0.330.84, 0.69

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXTL/PC (Bruker, 2000), SHELXTL/PC and PLATON (Spek, 2003), SHELXTL/PC, Mercury (Version 1.4.1, Macrae et al., 2006) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) for (I) top
C4—N41.468 (2)C11—O1B1.333 (3)
C11—O1A1.211 (3)
O1A—C11—C1123.1 (2)O1B—C11—C1113.2 (2)
C2—C1—C11—O1A7.9 (3)C6—C1—C11—O1B13.0 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···O1i0.822.573.202 (3)135
O1B'—H1B'···O2i0.822.323.038 (10)146
N4—H4A···O1Aii0.891.912.791 (2)171
N4—H4B···O2iii0.891.992.853 (2)163
N4—H4C···O10.891.982.852 (3)167
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+2, y+1/2, z+3/2; (iii) x, y, z+1.
Selected geometric parameters (Å, º) for (II) top
C4—N41.466 (3)C11—O1B1.317 (3)
C11—O1A1.211 (3)
C2—C1—C11—O1A5.8 (4)C6—C1—C11—O1B6.1 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O1Ai0.891.932.818 (3)173
N4—H4B···O2ii0.892.042.906 (3)164
N4—H4C···O1iii0.892.223.018 (3)150
N4—H4C···O3i0.892.553.039 (3)116
O1B—H1B···O1Wiv0.821.832.641 (3)171
O1W—H1W···O40.794 (19)2.39 (3)3.116 (4)152 (4)
O1W—H2W···O1iv0.81 (2)2.47 (4)3.096 (4)135 (4)
Symmetry codes: (i) x1, y+1/2, z1/2; (ii) x1, y+1/2, z+1/2; (iii) x+1, y1/2, z+3/2; (iv) x+1, y+1, z+2.
Selected geometric parameters (Å, º) for (III) top
C111—O1A1.241 (5)C211—O2A1.237 (5)
C111—O1B1.268 (5)C211—O2B1.276 (5)
C14—N141.452 (4)C24—N241.447 (4)
C12—C11—C111—O1A1.8 (6)C22—C21—C211—O2A2.1 (6)
C16—C11—C111—O1A179.6 (4)C26—C21—C211—O2A179.6 (4)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···O2A0.821.862.670 (4)170
N14—H14A···O2i0.891.792.682 (3)175
N14—H14B···O2ii0.892.222.936 (3)137
N14—H14C···O10.891.892.757 (3)165
O2B—H2B···O1A0.821.802.614 (4)171
N24—H24A···O4iii0.891.972.804 (3)156
N24—H24B···O3iv0.891.932.741 (3)151
N24—H24C···O3v0.891.942.752 (3)150
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z1; (iii) x+1, y, z+1; (iv) x+1, y+1, z+2; (v) x+1, y, z.
 

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