Hydrogen-bonding motifs in 4-carboxy­phenyl­ammonium nitrate and perchlorate monohydrate, and in bis(4-carboxy­phenyl­ammonium) sulfate

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 (, , 0).

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2–1.5U_eq(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

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

	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.
	Fig. 2. The molecular structure of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 3. The molecular structure of (III), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 4. Schemes showing the different hydrogen-bonding motifs.
	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.
	Fig. 6. Head-to-tail C(8) and linear C2^2(6) hydrogen-bonding motifs, resulting in a secondary structure of an R3^3(28) motif in (II). Hydrogen bonds are drawn as dashed lines.
	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].
	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.
	Fig. 9. The pseudo-inversion centre and the cavity formed by anions and cations in the R6^4(16) hydrogen-bonded motif in (I). Hydrogen bonds are drawn as dashed lines and C-bound H atoms have been omitted.
	Fig. 10. The R2^2(12) hydrogen-bonding motif formed by the interaction between perchlorate and water molecules in (II). Hydrogen bonds are drawn as dashed lines.
	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.
	Fig. 12. Molecular aggregation of cationic dimers [R2^2(6) motif] and the C2^2(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)

Crystal data

C7H8NO2^+·NO3^−	F(000) = 416
Mr = 200.15	Dx = 1.497 Mg m^−3 Dm = 1.49 Mg m^−3 Dm measured by flotation using a liquid mixture of xylene and bromoform
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.8154 (9) Å	θ = 9.9–14.4°
b = 15.0516 (3) Å	µ = 0.13 mm^−1
c = 6.6950 (6) Å	T = 293 K
β = 90.933 (12)°	Block, light pink
V = 888.14 (14) Å^3	0.22 × 0.19 × 0.17 mm
Z = 4

Data collection

Nonius MACH3 sealed tube diffractometer	Rint = 0.016
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.3°
Graphite monochromator	h = −10→10
ω–2θ scans	k = −1→17
1832 measured reflections	l = 0→7
1549 independent reflections	3 standard reflections every 60 min
1264 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0712P)^2 + 0.3551P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1549 reflections	Δρmax = 0.29 e Å^−3
139 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (6)

Special details

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	1.0614 (2)	0.26541 (13)	0.7285 (3)	0.0402 (5)
C2	0.9128 (2)	0.23648 (13)	0.7434 (3)	0.0415 (5)
H2	0.8916	0.1760	0.7483	0.050*
C3	0.7965 (2)	0.29739 (14)	0.7508 (3)	0.0430 (5)
H3	0.6963	0.2785	0.7589	0.052*
C4	0.8308 (2)	0.38687 (12)	0.7461 (3)	0.0365 (5)
C5	0.9772 (2)	0.41687 (13)	0.7335 (3)	0.0452 (5)
H5	0.9980	0.4774	0.7318	0.054*
C6	1.0933 (2)	0.35541 (14)	0.7234 (4)	0.0480 (6)
H6	1.1932	0.3746	0.7131	0.058*
C11	1.1830 (2)	0.19752 (15)	0.7135 (4)	0.0504 (6)
O1A	1.16056 (18)	0.11868 (10)	0.7343 (3)	0.0564 (5)
O1B	1.3149 (3)	0.2309 (2)	0.6546 (4)	0.0552 (8)	0.75
H1B	1.3780	0.1910	0.6486	0.083*	0.75
O1B'	1.3167 (9)	0.2319 (6)	0.792 (3)	0.094 (4)	0.25
H1B'	1.3832	0.1939	0.7884	0.142*	0.25
N4	0.70517 (18)	0.45084 (11)	0.7523 (3)	0.0415 (5)
H4A	0.7419	0.5058	0.7457	0.062*
H4B	0.6552	0.4441	0.8658	0.062*
H4C	0.6423	0.4413	0.6492	0.062*
N1	0.59434 (19)	0.41968 (12)	0.2482 (3)	0.0486 (5)
O1	0.5333 (2)	0.39844 (15)	0.4074 (3)	0.0763 (6)
O2	0.5345 (2)	0.39385 (13)	0.0872 (3)	0.0662 (6)
O3	0.7100 (2)	0.46391 (14)	0.2473 (4)	0.0836 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0393 (11)	0.0329 (10)	0.0483 (12)	0.0007 (8)	0.0006 (8)	0.0009 (9)
C2	0.0432 (11)	0.0277 (10)	0.0536 (12)	−0.0027 (8)	0.0023 (9)	0.0009 (9)
C3	0.0344 (10)	0.0370 (11)	0.0575 (13)	−0.0058 (8)	0.0022 (9)	0.0009 (9)
C4	0.0346 (10)	0.0324 (10)	0.0427 (10)	0.0015 (8)	0.0019 (8)	0.0001 (8)
C5	0.0377 (11)	0.0285 (10)	0.0695 (14)	−0.0031 (9)	0.0019 (9)	0.0011 (9)
C6	0.0321 (10)	0.0368 (11)	0.0752 (15)	−0.0037 (8)	0.0014 (9)	0.0008 (10)
C11	0.0416 (12)	0.0414 (12)	0.0683 (15)	0.0032 (9)	0.0008 (10)	−0.0001 (10)
O1A	0.0524 (9)	0.0329 (8)	0.0842 (12)	0.0071 (7)	0.0052 (8)	0.0022 (7)
O1B	0.0419 (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)
N4	0.0349 (9)	0.0354 (9)	0.0543 (10)	0.0017 (7)	0.0036 (7)	0.0001 (7)
N1	0.0321 (9)	0.0389 (10)	0.0749 (14)	0.0038 (8)	0.0010 (9)	−0.0011 (9)
O1	0.0634 (12)	0.1024 (16)	0.0629 (11)	−0.0225 (10)	−0.0017 (9)	0.0012 (10)
O2	0.0552 (10)	0.0820 (13)	0.0615 (11)	−0.0216 (9)	0.0046 (8)	−0.0048 (9)
O3	0.0521 (11)	0.0696 (13)	0.1290 (19)	−0.0285 (9)	0.0008 (11)	−0.0035 (12)

Geometric parameters (Å, º)

C1—C6	1.384 (3)	C11—O1A	1.211 (3)
C1—C2	1.386 (3)	C11—O1B	1.333 (3)
C1—C11	1.486 (3)	C11—O1B'	1.383 (10)
C2—C3	1.377 (3)	O1B—H1B	0.8200
C2—H2	0.9300	O1B'—H1B'	0.8200
C3—C4	1.381 (3)	N4—H4A	0.8900
C3—H3	0.9300	N4—H4B	0.8900
C4—C5	1.371 (3)	N4—H4C	0.8900
C4—N4	1.468 (2)	N1—O3	1.217 (2)
C5—C6	1.382 (3)	N1—O1	1.244 (3)
C5—H5	0.9300	N1—O2	1.254 (3)
C6—H6	0.9300
C6—C1—C2	120.16 (19)	O1A—C11—O1B	123.3 (2)
C6—C1—C11	121.61 (18)	O1A—C11—O1B'	117.6 (5)
C2—C1—C11	118.22 (18)	O1B—C11—O1B'	39.5 (6)
C3—C2—C1	119.91 (18)	O1A—C11—C1	123.1 (2)
C3—C2—H2	120.0	O1B—C11—C1	113.2 (2)
C1—C2—H2	120.0	O1B'—C11—C1	109.2 (4)
C2—C3—C4	119.04 (18)	C11—O1B—H1B	109.5
C2—C3—H3	120.5	C11—O1B'—H1B'	109.5
C4—C3—H3	120.5	C4—N4—H4A	109.5
C5—C4—C3	121.94 (18)	C4—N4—H4B	109.5
C5—C4—N4	119.80 (17)	H4A—N4—H4B	109.5
C3—C4—N4	118.26 (17)	C4—N4—H4C	109.5
C4—C5—C6	118.77 (18)	H4A—N4—H4C	109.5
C4—C5—H5	120.6	H4B—N4—H4C	109.5
C6—C5—H5	120.6	O3—N1—O1	121.3 (2)
C5—C6—C1	120.17 (19)	O3—N1—O2	120.4 (2)
C5—C6—H6	119.9	O1—N1—O2	118.35 (18)
C1—C6—H6	119.9
C6—C1—C2—C3	0.7 (3)	C2—C1—C6—C5	0.1 (3)
C11—C1—C2—C3	−177.81 (19)	C11—C1—C6—C5	178.6 (2)
C1—C2—C3—C4	−0.9 (3)	C6—C1—C11—O1A	173.6 (2)
C2—C3—C4—C5	0.2 (3)	C2—C1—C11—O1A	−7.9 (3)
C2—C3—C4—N4	179.44 (18)	C6—C1—C11—O1B	−13.0 (3)
C3—C4—C5—C6	0.6 (3)	C2—C1—C11—O1B	165.5 (2)
N4—C4—C5—C6	−178.57 (19)	C6—C1—C11—O1B'	29.3 (8)
C4—C5—C6—C1	−0.8 (3)	C2—C1—C11—O1B'	−152.2 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O1^i	0.82	2.57	3.202 (3)	135
O1B′—H1B′···O2^i	0.82	2.32	3.038 (10)	146
N4—H4A···O1A^ii	0.89	1.91	2.791 (2)	171
N4—H4B···O2^iii	0.89	1.99	2.853 (2)	163
N4—H4C···O1	0.89	1.98	2.852 (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)

Crystal data

C7H8NO2^+·ClO4^−·H2O	F(000) = 528
Mr = 255.61	Dx = 1.622 Mg m^−3 Dm = 1.61 Mg m^−3 Dm measured by flotation technique using a liquid mixture of carbon tetrachloride and bromoform
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.5492 (7) Å	θ = 11.5–14.3°
b = 19.3871 (5) Å	µ = 0.39 mm^−1
c = 7.2974 (3) Å	T = 293 K
β = 101.524 (5)°	Block, colourless
V = 1046.42 (12) Å^3	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection

Nonius MACH3 sealed tube diffractometer	1587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω–2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = −23→23
Tmin = 0.911, Tmax = 0.994	l = 0→8
3032 measured reflections	3 standard reflections every 60 min
1833 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0592P)^2 + 0.8272P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1833 reflections	Δρmax = 0.52 e Å^−3
156 parameters	Δρmin = −0.33 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (4)

Special details

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3520 (3)	0.26926 (11)	0.9953 (3)	0.0303 (5)
C2	0.3959 (3)	0.19965 (12)	1.0169 (3)	0.0356 (6)
H2	0.5120	0.1865	1.0750	0.043*
C3	0.2671 (3)	0.15006 (12)	0.9523 (3)	0.0363 (6)
H3	0.2960	0.1034	0.9651	0.044*
C4	0.0950 (3)	0.17067 (11)	0.8685 (3)	0.0311 (5)
C5	0.0483 (3)	0.23973 (12)	0.8465 (3)	0.0354 (5)
H5	−0.0684	0.2528	0.7901	0.042*
C6	0.1785 (3)	0.28871 (12)	0.9098 (3)	0.0347 (5)
H6	0.1496	0.3353	0.8951	0.042*
N4	−0.0423 (3)	0.11817 (10)	0.8007 (3)	0.0371 (5)
H4A	−0.1456	0.1387	0.7488	0.056*
H4B	−0.0596	0.0922	0.8961	0.056*
H4C	−0.0050	0.0918	0.7161	0.056*
C11	0.4921 (3)	0.32139 (12)	1.0682 (3)	0.0340 (5)
O1A	0.6400 (2)	0.30696 (9)	1.1586 (3)	0.0488 (5)
O1B	0.4390 (2)	0.38523 (9)	1.0268 (3)	0.0491 (5)
H1B	0.5171	0.4121	1.0785	0.074*
Cl1	0.80735 (8)	0.44858 (3)	0.75074 (8)	0.0401 (3)
O1	0.8161 (3)	0.51293 (12)	0.8533 (4)	0.0712 (7)
O2	0.9551 (4)	0.44862 (14)	0.6567 (4)	0.0793 (8)
O3	0.8212 (4)	0.39423 (12)	0.8810 (4)	0.0755 (7)
O4	0.6381 (4)	0.44810 (16)	0.6250 (4)	0.0877 (9)
O1W	0.3392 (3)	0.52034 (10)	0.7949 (3)	0.0506 (5)
H1W	0.386 (5)	0.502 (2)	0.719 (4)	0.080 (14)*
H2W	0.295 (6)	0.491 (2)	0.850 (6)	0.109 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0281 (11)	0.0315 (11)	0.0306 (11)	0.0003 (9)	0.0041 (9)	0.0004 (9)
C2	0.0273 (11)	0.0353 (12)	0.0403 (13)	0.0048 (9)	−0.0026 (9)	0.0024 (10)
C3	0.0356 (12)	0.0275 (11)	0.0424 (13)	0.0039 (9)	−0.0004 (10)	0.0014 (10)
C4	0.0307 (11)	0.0317 (11)	0.0291 (11)	−0.0029 (9)	0.0016 (9)	−0.0007 (9)
C5	0.0258 (11)	0.0357 (12)	0.0409 (13)	0.0043 (9)	−0.0023 (9)	0.0012 (10)
C6	0.0316 (12)	0.0280 (11)	0.0426 (13)	0.0037 (9)	0.0029 (10)	0.0024 (10)
N4	0.0325 (10)	0.0342 (10)	0.0407 (11)	−0.0025 (8)	−0.0022 (8)	−0.0012 (9)
C11	0.0311 (12)	0.0333 (12)	0.0367 (12)	−0.0007 (9)	0.0046 (9)	0.0019 (10)
O1A	0.0328 (9)	0.0386 (10)	0.0669 (13)	−0.0042 (7)	−0.0093 (8)	0.0064 (9)
O1B	0.0392 (10)	0.0303 (9)	0.0702 (13)	−0.0012 (7)	−0.0077 (9)	0.0000 (9)
Cl1	0.0412 (4)	0.0394 (4)	0.0390 (4)	−0.0017 (2)	0.0067 (3)	0.0057 (2)
O1	0.0846 (17)	0.0518 (13)	0.0805 (16)	−0.0033 (11)	0.0241 (13)	−0.0134 (12)
O2	0.0811 (17)	0.102 (2)	0.0657 (15)	−0.0181 (14)	0.0399 (13)	−0.0167 (14)
O3	0.0924 (18)	0.0600 (14)	0.0791 (16)	0.0131 (12)	0.0289 (14)	0.0306 (12)
O4	0.0640 (15)	0.107 (2)	0.0786 (17)	−0.0162 (14)	−0.0181 (13)	0.0087 (15)
O1W	0.0485 (11)	0.0396 (11)	0.0606 (13)	−0.0032 (9)	0.0034 (10)	−0.0022 (10)

Geometric parameters (Å, º)

C1—C6	1.386 (3)	N4—H4A	0.8900
C1—C2	1.391 (3)	N4—H4B	0.8900
C1—C11	1.483 (3)	N4—H4C	0.8900
C2—C3	1.381 (3)	C11—O1A	1.211 (3)
C2—H2	0.9300	C11—O1B	1.317 (3)
C3—C4	1.380 (3)	O1B—H1B	0.8200
C3—H3	0.9300	Cl1—O3	1.409 (2)
C4—C5	1.386 (3)	Cl1—O4	1.416 (2)
C4—N4	1.466 (3)	Cl1—O2	1.421 (2)
C5—C6	1.378 (3)	Cl1—O1	1.449 (2)
C5—H5	0.9300	O1W—H1W	0.794 (19)
C6—H6	0.9300	O1W—H2W	0.81 (2)
C6—C1—C2	119.8 (2)	C4—N4—H4A	109.5
C6—C1—C11	121.2 (2)	C4—N4—H4B	109.5
C2—C1—C11	118.9 (2)	H4A—N4—H4B	109.5
C3—C2—C1	120.1 (2)	C4—N4—H4C	109.5
C3—C2—H2	120.0	H4A—N4—H4C	109.5
C1—C2—H2	120.0	H4B—N4—H4C	109.5
C4—C3—C2	119.1 (2)	O1A—C11—O1B	123.2 (2)
C4—C3—H3	120.5	O1A—C11—C1	123.5 (2)
C2—C3—H3	120.5	O1B—C11—C1	113.30 (19)
C3—C4—C5	121.7 (2)	C11—O1B—H1B	109.5
C3—C4—N4	119.2 (2)	O3—Cl1—O4	111.62 (17)
C5—C4—N4	119.06 (19)	O3—Cl1—O2	111.48 (16)
C6—C5—C4	118.6 (2)	O4—Cl1—O2	112.36 (18)
C6—C5—H5	120.7	O3—Cl1—O1	107.81 (16)
C4—C5—H5	120.7	O4—Cl1—O1	106.41 (17)
C5—C6—C1	120.7 (2)	O2—Cl1—O1	106.80 (15)
C5—C6—H6	119.7	H1W—O1W—H2W	109 (5)
C1—C6—H6	119.7
C6—C1—C2—C3	0.4 (4)	C4—C5—C6—C1	−0.6 (4)
C11—C1—C2—C3	179.2 (2)	C2—C1—C6—C5	0.3 (4)
C1—C2—C3—C4	−0.7 (4)	C11—C1—C6—C5	−178.5 (2)
C2—C3—C4—C5	0.4 (4)	C6—C1—C11—O1A	173.0 (2)
C2—C3—C4—N4	−179.6 (2)	C2—C1—C11—O1A	−5.8 (4)
C3—C4—C5—C6	0.2 (4)	C6—C1—C11—O1B	−6.1 (3)
N4—C4—C5—C6	−179.7 (2)	C2—C1—C11—O1B	175.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1A^i	0.89	1.93	2.818 (3)	173
N4—H4B···O2^ii	0.89	2.04	2.906 (3)	164
N4—H4C···O1^iii	0.89	2.22	3.018 (3)	150
N4—H4C···O3^i	0.89	2.55	3.039 (3)	116
O1B—H1B···O1W^iv	0.82	1.83	2.641 (3)	171
O1W—H1W···O4	0.79 (2)	2.39 (3)	3.116 (4)	152 (4)
O1W—H2W···O1^iv	0.81 (2)	2.47 (4)	3.096 (4)	135 (4)

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

(III)

Crystal data

2C7H8NO2^+·SO4^2^−	F(000) = 776
Mr = 372.35	Dx = 1.566 Mg m^−3 Dm = 1.56 Mg m^−3 Dm measured by flotation technique using a liquid mixture of carbon xylene and bromoform
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 18.7094 (8) Å	θ = 10.2–13.2°
b = 14.0562 (4) Å	µ = 0.25 mm^−1
c = 6.0551 (5) Å	T = 293 K
β = 97.272 (5)°	Block, colourless
V = 1579.51 (15) Å^3	0.26 × 0.22 × 0.18 mm
Z = 4

Data collection

Nonius MACH3 sealed tube diffractometer	2014 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω–2θ scans	h = −22→22
Absorption correction: ψ scan (North et al., 1968)	k = −1→16
Tmin = 0.953, Tmax = 0.997	l = 0→7
3323 measured reflections	3 standard reflections every 60 min
2763 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.181	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1287P)^2 + 0.1992P] where P = (Fo^2 + 2Fc^2)/3
2763 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	0.39211 (19)	0.3808 (2)	0.4043 (6)	0.0398 (8)
C111	0.4695 (2)	0.3776 (3)	0.4989 (7)	0.0482 (10)
O1A	0.48737 (16)	0.4072 (3)	0.6910 (5)	0.0739 (10)
O1B	0.51279 (16)	0.3420 (3)	0.3765 (6)	0.0762 (11)
H1B	0.5527	0.3363	0.4486	0.114*
C12	0.34168 (19)	0.4139 (3)	0.5331 (6)	0.0424 (9)
H12	0.3569	0.4387	0.6735	0.051*
C13	0.26935 (19)	0.4107 (3)	0.4575 (5)	0.0377 (8)
H13	0.2358	0.4323	0.5467	0.045*
C14	0.24710 (17)	0.3752 (2)	0.2474 (5)	0.0303 (7)
N14	0.17053 (14)	0.3649 (2)	0.1747 (4)	0.0324 (6)
H14A	0.1581	0.3040	0.1824	0.049*
H14B	0.1607	0.3852	0.0349	0.049*
H14C	0.1458	0.3993	0.2624	0.049*
C15	0.29666 (19)	0.3446 (3)	0.1117 (6)	0.0401 (9)
H15	0.2811	0.3221	−0.0307	0.048*
C16	0.3694 (2)	0.3476 (3)	0.1891 (6)	0.0444 (9)
H16	0.4031	0.3276	0.0984	0.053*
C21	0.74070 (19)	0.3673 (2)	0.8710 (6)	0.0364 (8)
C211	0.66428 (19)	0.3649 (3)	0.7710 (6)	0.0427 (9)
O2A	0.64839 (15)	0.3377 (2)	0.5768 (5)	0.0620 (9)
O2B	0.61855 (15)	0.3933 (3)	0.8960 (5)	0.0642 (9)
H2B	0.5780	0.3920	0.8263	0.096*
C22	0.79444 (18)	0.3423 (2)	0.7468 (5)	0.0354 (8)
H22	0.7820	0.3211	0.6015	0.042*
C23	0.86627 (18)	0.3477 (2)	0.8319 (5)	0.0339 (8)
H23	0.9020	0.3316	0.7449	0.041*
C24	0.88392 (17)	0.3777 (2)	1.0505 (5)	0.0271 (7)
N24	0.95875 (14)	0.38738 (18)	1.1427 (4)	0.0294 (6)
H24A	0.9687	0.3466	1.2548	0.044*
H24B	0.9669	0.4465	1.1924	0.044*
H24C	0.9867	0.3750	1.0377	0.044*
C25	0.83084 (18)	0.4025 (2)	1.1790 (5)	0.0345 (8)
H25	0.8435	0.4227	1.3250	0.041*
C26	0.75969 (19)	0.3976 (3)	1.0921 (6)	0.0392 (8)
H26	0.7240	0.4141	1.1790	0.047*
S1	0.07132 (4)	0.36963 (5)	0.63025 (11)	0.0261 (3)
O1	0.08188 (12)	0.44111 (15)	0.4598 (3)	0.0323 (6)
O2	0.14086 (13)	0.32125 (17)	0.6978 (4)	0.0393 (6)
O3	0.05029 (13)	0.41852 (15)	0.8284 (3)	0.0343 (6)
O4	0.01590 (13)	0.30125 (16)	0.5442 (4)	0.0377 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0322 (18)	0.046 (2)	0.041 (2)	−0.0016 (15)	0.0009 (15)	−0.0001 (16)
C111	0.0333 (19)	0.059 (2)	0.050 (2)	−0.0007 (17)	−0.0011 (17)	−0.0067 (19)
O1A	0.0402 (17)	0.112 (3)	0.064 (2)	0.0064 (17)	−0.0133 (15)	−0.028 (2)
O1B	0.0311 (15)	0.115 (3)	0.080 (2)	0.0097 (17)	0.0001 (15)	−0.029 (2)
C12	0.038 (2)	0.059 (2)	0.0288 (18)	−0.0043 (17)	−0.0008 (14)	−0.0056 (16)
C13	0.0354 (18)	0.054 (2)	0.0242 (17)	−0.0026 (15)	0.0043 (13)	−0.0045 (15)
C14	0.0312 (17)	0.0358 (17)	0.0240 (16)	−0.0020 (13)	0.0040 (13)	0.0046 (13)
N14	0.0305 (14)	0.0446 (15)	0.0211 (13)	−0.0028 (12)	−0.0010 (11)	0.0037 (12)
C15	0.0377 (19)	0.056 (2)	0.0265 (17)	−0.0038 (16)	0.0022 (14)	−0.0087 (15)
C16	0.0359 (19)	0.060 (2)	0.038 (2)	−0.0001 (17)	0.0103 (15)	−0.0073 (17)
C21	0.0332 (18)	0.0396 (18)	0.0354 (18)	−0.0010 (14)	0.0001 (14)	0.0018 (15)
C211	0.0341 (19)	0.050 (2)	0.043 (2)	−0.0025 (16)	0.0006 (16)	−0.0002 (17)
O2A	0.0365 (15)	0.092 (2)	0.0535 (18)	0.0011 (15)	−0.0078 (13)	−0.0198 (17)
O2B	0.0304 (14)	0.103 (2)	0.0576 (19)	0.0070 (16)	0.0007 (13)	−0.0120 (18)
C22	0.0376 (19)	0.0458 (19)	0.0215 (16)	−0.0014 (15)	−0.0011 (13)	−0.0057 (14)
C23	0.0340 (18)	0.0437 (18)	0.0242 (16)	0.0001 (14)	0.0048 (13)	−0.0045 (14)
C24	0.0290 (16)	0.0287 (15)	0.0236 (15)	−0.0009 (12)	0.0032 (12)	0.0022 (12)
N24	0.0290 (14)	0.0361 (14)	0.0222 (13)	0.0002 (11)	−0.0001 (10)	0.0017 (11)
C25	0.0400 (19)	0.0431 (17)	0.0204 (15)	0.0020 (15)	0.0038 (13)	−0.0044 (14)
C26	0.0356 (18)	0.049 (2)	0.0341 (19)	0.0009 (16)	0.0084 (15)	−0.0049 (16)
S1	0.0291 (4)	0.0328 (4)	0.0161 (4)	0.0006 (3)	0.0011 (3)	−0.0001 (3)
O1	0.0381 (13)	0.0354 (12)	0.0237 (12)	−0.0018 (10)	0.0049 (9)	0.0029 (9)
O2	0.0367 (13)	0.0502 (13)	0.0310 (13)	0.0091 (11)	0.0047 (10)	0.0023 (11)
O3	0.0448 (14)	0.0383 (12)	0.0212 (11)	0.0039 (10)	0.0096 (10)	−0.0025 (9)
O4	0.0445 (14)	0.0419 (13)	0.0254 (12)	−0.0088 (11)	−0.0012 (10)	0.0032 (10)

Geometric parameters (Å, º)

C11—C12	1.378 (5)	C21—C211	1.481 (5)
C11—C16	1.399 (5)	C211—O2A	1.237 (5)
C11—C111	1.489 (5)	C211—O2B	1.276 (5)
C111—O1A	1.241 (5)	O2B—H2B	0.8200
C111—O1B	1.268 (5)	C22—C23	1.379 (5)
O1B—H1B	0.8200	C22—H22	0.9300
C12—C13	1.373 (5)	C23—C24	1.389 (4)
C12—H12	0.9300	C23—H23	0.9300
C13—C14	1.381 (5)	C24—C25	1.381 (4)
C13—H13	0.9300	C24—N24	1.447 (4)
C14—C15	1.383 (5)	N24—H24A	0.8900
C14—N14	1.452 (4)	N24—H24B	0.8900
N14—H14A	0.8900	N24—H24C	0.8900
N14—H14B	0.8900	C25—C26	1.370 (5)
N14—H14C	0.8900	C25—H25	0.9300
C15—C16	1.383 (5)	C26—H26	0.9300
C15—H15	0.9300	S1—O4	1.461 (2)
C16—H16	0.9300	S1—O1	1.472 (2)
C21—C22	1.375 (5)	S1—O3	1.478 (2)
C21—C26	1.407 (5)	S1—O2	1.479 (2)
C12—C11—C16	119.4 (3)	O2A—C211—O2B	124.2 (3)
C12—C11—C111	119.7 (3)	O2A—C211—C21	120.0 (3)
C16—C11—C111	120.9 (3)	O2B—C211—C21	115.8 (3)
O1A—C111—O1B	124.4 (4)	C211—O2B—H2B	109.5
O1A—C111—C11	118.9 (4)	C21—C22—C23	121.8 (3)
O1B—C111—C11	116.7 (4)	C21—C22—H22	119.1
C111—O1B—H1B	109.5	C23—C22—H22	119.1
C13—C12—C11	121.1 (3)	C22—C23—C24	118.4 (3)
C13—C12—H12	119.4	C22—C23—H23	120.8
C11—C12—H12	119.4	C24—C23—H23	120.8
C12—C13—C14	119.2 (3)	C25—C24—C23	120.8 (3)
C12—C13—H13	120.4	C25—C24—N24	119.3 (3)
C14—C13—H13	120.4	C23—C24—N24	119.9 (3)
C13—C14—C15	120.9 (3)	C24—N24—H24A	109.5
C13—C14—N14	119.1 (3)	C24—N24—H24B	109.5
C15—C14—N14	119.9 (3)	H24A—N24—H24B	109.5
C14—N14—H14A	109.5	C24—N24—H24C	109.5
C14—N14—H14B	109.5	H24A—N24—H24C	109.5
H14A—N14—H14B	109.5	H24B—N24—H24C	109.5
C14—N14—H14C	109.5	C26—C25—C24	120.2 (3)
H14A—N14—H14C	109.5	C26—C25—H25	119.9
H14B—N14—H14C	109.5	C24—C25—H25	119.9
C16—C15—C14	119.6 (3)	C25—C26—C21	119.8 (3)
C16—C15—H15	120.2	C25—C26—H26	120.1
C14—C15—H15	120.2	C21—C26—H26	120.1
C15—C16—C11	119.7 (3)	O4—S1—O1	110.57 (12)
C15—C16—H16	120.1	O4—S1—O3	110.22 (14)
C11—C16—H16	120.1	O1—S1—O3	108.97 (13)
C22—C21—C26	118.9 (3)	O4—S1—O2	110.84 (14)
C22—C21—C211	120.4 (3)	O1—S1—O2	108.44 (13)
C26—C21—C211	120.7 (3)	O3—S1—O2	107.73 (13)
C12—C11—C111—O1A	−1.8 (6)	C22—C21—C211—O2A	2.1 (6)
C16—C11—C111—O1A	−179.6 (4)	C26—C21—C211—O2A	−179.6 (4)
C12—C11—C111—O1B	176.5 (4)	C22—C21—C211—O2B	−177.1 (4)
C16—C11—C111—O1B	−1.2 (6)	C26—C21—C211—O2B	1.2 (5)
C16—C11—C12—C13	3.0 (6)	C26—C21—C22—C23	−1.2 (5)
C111—C11—C12—C13	−174.8 (4)	C211—C21—C22—C23	177.1 (3)
C11—C12—C13—C14	−1.0 (6)	C21—C22—C23—C24	1.2 (5)
C12—C13—C14—C15	−1.2 (5)	C22—C23—C24—C25	−0.7 (5)
C12—C13—C14—N14	175.2 (3)	C22—C23—C24—N24	−177.9 (3)
C13—C14—C15—C16	1.5 (5)	C23—C24—C25—C26	0.2 (5)
N14—C14—C15—C16	−174.9 (3)	N24—C24—C25—C26	177.4 (3)
C14—C15—C16—C11	0.5 (6)	C24—C25—C26—C21	−0.2 (5)
C12—C11—C16—C15	−2.7 (6)	C22—C21—C26—C25	0.7 (5)
C111—C11—C16—C15	175.0 (4)	C211—C21—C26—C25	−177.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O2A	0.82	1.86	2.670 (4)	170
N14—H14A···O2^i	0.89	1.79	2.682 (3)	175
N14—H14B···O2^ii	0.89	2.22	2.936 (3)	137
N14—H14C···O1	0.89	1.89	2.757 (3)	165
O2B—H2B···O1A	0.82	1.80	2.614 (4)	171
N24—H24A···O4^iii	0.89	1.97	2.804 (3)	156
N24—H24B···O3^iv	0.89	1.93	2.741 (3)	151
N24—H24C···O3^v	0.89	1.94	2.752 (3)	150

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