The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-amino­phenyl)arsonic acid

Smith, G.; Wermuth, U.D.

doi:10.1107/S2053229616019434

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 73| Part 1| January 2017| Pages 61-67

https://doi.org/10.1107/S2053229616019434

The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid

Graham Smith ^a ^* and Urs D. Wermuth ^b

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and ^bSchool of Natural Sciences, Griffith University, Nathan, Queensland 4111, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

Edited by A. G. Oliver, University of Notre Dame, USA (Received 26 September 2016; accepted 5 December 2016; online 1 January 2017)

(4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg(H₂O)₆](C₆H₇AsNO₃)·4H₂O, (I), catena-poly[[[diaquacalcium]-bis[μ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O′]-[diaquacalcium]-bis[μ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O]] dihydrate], {[Ca(C₆H₇AsNO₃)₂(H₂O)₂]·2H₂O}_n, (II), catena-poly[[triaquastrontium]-bis[μ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O′]], [Sr(C₆H₇AsNO₃)₂(H₂O)₃]_n, (III), and catena-poly[[triaquabarium]-bis[μ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O′]], [Ba(C₆H₇AsNO₃)₂(H₂O)₃]_n, (IV). In the structure of magnesium salt (I), the centrosymmetric octahedral [Mg(H₂O)₆]²⁺ cation, the two hydrogen p-arsanilate anions and the four water molecules of solvation form a three-dimensional network structure through inter-species O—H and N—H hydrogen-bonding interactions with water and arsonate O-atom and amine N-atom acceptors. In one-dimensional coordination polymer (II), the distorted octahedral CaO₆ coordination polyhedron comprises two trans-related water molecules and four arsonate O-atom donors from bridging hydrogen arsanilate ligands. One bridging extension is four-membered via a single O atom and the other is eight-membered via O:O′-bridging, both across inversion centres, giving a chain coordination polymer extending along the [100] direction. Extensive hydrogen-bonding involving O—H⋯O, O—H⋯N and N—H⋯O interactions gives an overall three-dimensional structure. The structures of the polymeric Sr and Ba complexes (III) and (IV), respectively, are isotypic and are based on irregular MO₇ coordination polyhedra about the M²⁺ centres, which lie on twofold rotation axes along with one of the coordinated water molecules. The coordination centres are linked through inversion-related arsonate O:O′-bridges, giving eight-membered ring motifs and forming coordination polymeric chains extending along the [100] direction. Inter-chain N—H⋯O and O—H⋯O hydrogen-bonding interactions extend the structures into three dimensions and the crystal packing includes π–π ring interactions [minimum ring centroid separations = 3.4666 (17) Å for (III) and 3.4855 (8) Å for (IV)].

Keywords: p-arsanilic acid salts; alkaline earth metals; coordination polymers; hydrogen bonding; crystal structure; one-dimensional coordination polymer; barium; strontium; calcium; magnesium.

CCDC references: 1520680; 1520679; 1520678; 1520677

1. Introduction

The compound (4-aminophenyl)arsonic acid (or p-arsanilic acid) has a continuing usage as an antihelminth in veterinary applications (Steverding, 2010 ) and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl (Ehrlich & Bertheim, 1907 ; O'Neil, 2001 ; Bosch & Rosich, 2008 ). We reported the crystal structure of atoxyl, together with that of the monoammonium salt (Smith & Wermuth, 2014 ) but the number of structures of monometal (as distinct from mixed metal) complexes with p-arsanilic acid are few in the crystallographic literature, examples being with silver(I), zinc, cadmium and lead (Lesikar-Parrish et al., 2013 ) and uranium (as UO₂) (Adelani et al., 2012 ). An example of a mixed-metal compound is the sodium salt of a hybrid organic–inorganic polyoxovanadate cluster formed with p-arsanilate anions (Breen & Schmitt, 2008 ).

Our 2:1 stoichiometric reactions of p-arsanilic acid with magnesium, calcium, strontium and barium carbonates in aqueous ethanol gave the title compounds [Mg(H₂O)₆](C₆H₇AsNO₃)₂. 4H₂O, (I), {[Ca(C₆H₇AsNO₃)₂(H₂O)₂]·2H₂O}_n, (II), [Sr(C₆H₇AsNO₃)₂(H₂O)₃]_n, (III), and [Ba(C₆H₇AsNO₃)₂(H₂O)₃]_n, (IV), respectively. The structures and hydrogen-bonded packing modes for (I)–(IV) are reported herein.

2. Experimental

2.1. Synthesis and crystallization

The title compounds (I)–(IV) were synthesized by heating together under reflux for 5 min, 1.0 mmol (216 mg) of (4-aminophenyl)arsonic acid and 0.5 mmol of the appropriate carbonate, i.e. 42 mg of MgCO₃ for (I), 50 mg of CaCO₃ for (II), 74 mg of SrCO₃ for (III) or 98 mg of BaCO₃ for (IV), in 20 ml of 50% (v/v) ethanol/water. Partial room-temperature evaporation of the solutions gave colourless needles of all compounds from which specimens suitable for the X-ray analyses were cleaved. Crystals were mounted on conventional glass fibres using epoxy resin.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms involved in hydrogen bonds were located by difference Fourier methods and their isotropic displacement parameters were allowed to ride. N—H bond lengths were restrained to 0.88 (2) Å for (I) and (II), and to 0.90 (2) Å for (III) and (IV). O—H bond lengths were restrained to 0.90 (2) Å in all cases. H atoms bonded to C atoms were included in the refinement in calculated positions (C—H = 0.95 Å) and treated as riding, with U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	[Mg(H₂O)₆](C₆H₇AsNO₃)·4H₂O	[Ca(C₆H₇AsNO₃)₂(H₂O)₂]·2H₂O	[Sr(C₆H₇AsNO₃)₂(H₂O)₃]	[Ba(C₆H₇AsNO₃)₂(H₂O)₃]
M_r	636.56	544.24	573.76	623.92
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$	Monoclinic, I2/a	Monoclinic, I2/a
Temperature (K)	200	200	200	200
a, b, c (Å)	15.1693 (6), 6.7367 (2), 12.9532 (4)	9.001 (5), 9.672 (5), 11.756 (5)	9.8935 (3), 7.5844 (3), 23.6669 (9)	9.9997 (8), 7.7305 (6), 23.979 (2)
α, β, γ (°)	90, 108.033 (4), 90	77.096 (5), 74.096 (5), 82.236 (5)	90, 97.866 (3), 90	90, 98.214 (7), 90
V (Å³)	1258.68 (7)	956.4 (8)	1759.17 (11)	1834.7 (3)
Z	2	2	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.75	3.82	6.85	5.79
Crystal size (mm)	0.35 × 0.18 × 0.10	0.35 × 0.11 × 0.10	0.25 × 0.12 × 0.12	0.36 × 0.22 × 0.16

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector	Oxford Diffraction Gemini-S CCD detector	Oxford Diffraction Gemini-S CCD detector	Oxford Diffraction Gemini-S CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.700, 0.980	0.931, 0.980	0.791, 0.980	0.470, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	8901, 2466, 2149	6921, 3744, 3276	3326, 1737, 1606	3485, 1801, 1696
R_int	0.032	0.032	0.020	0.029
(sin θ/λ)_max (Å⁻¹)	0.617	0.617	0.617	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.12	0.031, 0.068, 1.06	0.022, 0.051, 1.09	0.023, 0.055, 1.10
No. of reflections	2466	3744	1737	1801
No. of parameters	190	286	137	137
No. of restraints	13	14	7	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.64	0.55, −0.47	0.47, −0.54	0.85, −0.95
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ) within WinGX (Farrugia, 2012 ), and PLATON (Spek, 2009 ).

3. Results and discussion

In the structure of magnesium compound (I), the cations exist as the commonly found centrosymmetric octahedral [Mg(H₂O)₆]²⁺ species with the hydrogen p-arsanilate acting as counter-anions. The coordinated aqua ligands are related in pairs by (−x + 1, −y + 1, −z + 1), denoted symmetry code (i) (Fig. 1). The Mg—O bond lengths [2.066 (2)–2.0734 (18) Å] are typical of those found in [Mg(H₂O)₆]²⁺ complex cations with analogous phosphonate anions, e.g. with hydrogen diphenylmethylphosphonate (Lee et al., 1988 ), hydrogen (2-aminoethyl)phosphonate (Schier et al., 1990 ) and the carboxylate anion 4-nitrobenzoate (Arlin et al., 2011 ).

Figure 1
The molecular configuration and atom-naming scheme for the hexaaquamagnesium cation, the p-arsanilate anion and the two water molecules of solvation in the the asymmetric unit of (I)

, with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines. [Inversion-related atoms are indicated by the symmetry code (i) −x + 1, −y + 1, −z + 1.]

In the crystal of (I), extensive hydrogen-bonding involving all H-atom donors of the anions and those of both the coordinated and solvent water molecules (O4W and O5W) with arsanilate O- and N-atom acceptors and water O-atom acceptors (Table 2) generate a three-dimensional structure (Figs. 2 and 3). The coordinated water molecules interact with both arsanilate O11^v, O12 and O13ⁱ, and water O4W, O5W and O5W^v atoms. These interactions include an R₃³(10) cyclic motif involving both the Mg and As atoms. The solvent water molecules involve O11, O11^v, O12^vi and O1W^vii acceptors. The arsanilate amine group acts as both a double donor to O12^iv and O4Wⁱⁱⁱ atoms and as an acceptor to the O13 acid H-atom donor of an inversion-related anion, linking these along [010]. Weak π–π associations are also present between inversion-related anions [ring centroid separation Cg⋯Cgⁱⁱ = 3.7187 (14) Å] [symmetry codes: (ii) −x, −y + 2, −z + 1; (iii) x − 1, y, z; (iv) −x, −y + 1, −z + 1; (v) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (vi) −x + 1, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (vii) x, y + 1, z].

Table 2
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13⋯N4ⁱⁱ	0.85 (2)	1.89 (2)	2.746 (3)	177 (3)
N4—H41⋯O4Wⁱⁱⁱ	0.86 (3)	2.07 (3)	2.903 (3)	164 (3)
N4—H42⋯O12^iv	0.86 (2)	2.12 (2)	2.980 (3)	172 (2)
O1W—H11W⋯O12	0.86 (2)	1.78 (2)	2.636 (3)	175 (2)
O1W—H12W⋯O5W^v	0.84 (2)	1.91 (2)	2.745 (2)	172 (3)
O2W—H21W⋯O11^v	0.87 (2)	1.84 (2)	2.707 (2)	174 (2)
O2W—H22W⋯O13ⁱ	0.84 (3)	2.00 (3)	2.832 (3)	177 (3)
O3W—H31W⋯O4W	0.89 (2)	1.90 (2)	2.781 (3)	175 (3)
O3W—H32W⋯O5W	0.87 (2)	1.94 (3)	2.796 (3)	165 (2)
O4W—H41W⋯O11^v	0.85 (2)	1.87 (2)	2.717 (2)	171 (3)
O4W—H42W⋯O12^vi	0.87 (2)	1.86 (2)	2.720 (2)	174 (3)
O5W—H51W⋯O11	0.87 (2)	1.89 (2)	2.754 (3)	170 (2)
O5W—H52W⋯O1W^vii	0.83 (2)	2.14 (2)	2.958 (3)	169 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+2, -z+1; (iii) x-1, y, z; (iv) -x, -y+1, -z+1; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) x, y+1, z.

Figure 2
The hydrogen-bonding extension in the structure of (I)

, showing the symmetry operations (see Table 2

). H atoms not involved in hydrogen bonding have been omitted.

Figure 3
A perspective view of the three-dimensional hydrogen-bonded framework structure of (I)

in the unit cell, showing the hydrogen-bonding associations as dashed lines. H atoms not involved in hydrogen bonding have been omitted. For symmetry codes, see Table 2

In the structure of the coordination polymeric calcium compound (II), the repeat unit is a distorted octahedral CaO₆ complex comprising four O-atom donors (with two bridging) from the two independent hydrogen p-arsanilate anions (A and B), together with two independent monodentate water molecules (O1W and O2W). Present also in the structure are two water molecules of solvation (O3W and O4W) (Fig. 4). The Ca—O bond lengths are in the range 2.306 (2)–2.420 (2) Å (Table 3), typical values for Ca—O bond lengths in the six-coordinate diaquacalcium–carboxylate–L-valine complex (Lamberts & Englert, 2015 ) (2.278–2.372 Å). The bridging carboxylate O atoms in (II) generate a coordination polymer extending along [100] through centrosymmetric cyclic ring systems, i.e. four-membered through O11Bⁱ and eight-membered through O11Aⁱⁱ and O12Aⁱⁱ [symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z + 1] (Fig. 5). The Ca⋯Caⁱ separation in the four-membered ring is 3.801 (2) Å. The crystal structure involves a number of inter-chain N—H⋯O and O—H⋯O hydrogen-bonding interactions to arsonate and water O-atom acceptors, as well as to the amine N-atom acceptors (Table 4 and Fig. 5). These generate an overall three-dimensional framework structure (Fig. 6) in which no π–π ring interactions are present.

Table 3
Selected bond lengths (Å) for (II)

Ca1—O1W	2.392 (3)	Ca1—O11B	2.361 (2)
Ca1—O2W	2.345 (3)	Ca1—O11Bⁱ	2.420 (2)
Ca1—O11A	2.306 (2)	Ca1—O12Aⁱⁱ	2.291 (2)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1.

Table 4
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13A—H13A⋯O12Bⁱⁱ	0.88 (2)	1.67 (2)	2.534 (3)	169 (4)
O13B—H13B⋯O11Aⁱ	0.88 (3)	1.70 (3)	2.578 (3)	170 (3)
N4A—H41A⋯O12Bⁱⁱⁱ	0.88 (2)	2.13 (2)	3.014 (4)	176 (4)
N4B—H42B⋯O4W^iv	0.86 (3)	2.05 (3)	2.901 (5)	172 (4)
O1W—H11W⋯N4B^v	0.90 (4)	2.17 (4)	3.048 (5)	166 (4)
O1W—H12W⋯O3W	0.89 (2)	1.83 (2)	2.712 (4)	171 (3)
O2W—H21W⋯N4A^vi	0.86 (4)	2.04 (4)	2.893 (4)	173 (4)
O2W—H22W⋯O4W^vii	0.88 (3)	1.92 (3)	2.785 (4)	168 (4)
O3W—H31W⋯O13B^viii	0.88 (4)	1.96 (4)	2.827 (4)	169 (4)
O3W—H32W⋯O12B	0.89 (3)	1.92 (3)	2.758 (4)	157 (4)
O4W—H41W⋯O3W^ix	0.87 (4)	2.08 (4)	2.915 (4)	160 (3)
O4W—H42W⋯O13A	0.89 (4)	1.86 (3)	2.748 (4)	176 (2)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z+1; (iv) x, y+1, z-1; (v) x, y, z+1; (vi) x, y, z-1; (vii) -x+1, -y, -z+1; (viii) -x, -y+2, -z+1; (ix) x, y-1, z.

Figure 4
The molecular configuration and atom-naming scheme for the asymmetric unit and the water molecules of solvation (O3W and O4W) in (II)

. Displacement ellipsoids are drawn at the 40% probability level. For symmetry codes, see Table 3

Figure 5
A portion of the one-dimensional coordination polymeric chains in the structure of (II)

extending along a. For symmetry codes, see Table 3

Figure 6
Hydrogen bonding in the three-dimensional structure of (II)

, viewed down b, showing hydrogen bonds as dashed lines. H atoms not involved in hydrogen bonding have been omitted. For symmetry codes, see Table 4

The structures of the polymeric Sr and Ba complexes (III) and (IV), respectively, are isotypic and are based on irregular MO₇ coordination polyhedra about the M²⁺ centres, which lie on twofold rotation axes. The basic SrO₇ or BaO₇ complex repeat units (Figs. 7 and 8) comprise three monodentate water molecules, with one (O2W) lying on a twofold rotation axis and the others (O1W and O1Wⁱ) related by the rotation axis [symmetry code: (i) −x + $[{3\over 2}]$ , y, −z + 1]. The coordination sphere is completed by four O:O′-bridging arsonate O-atom donors, i.e. O11, O11ⁱ, O12ⁱⁱ and O12ⁱⁱⁱ [symmetry codes: (ii) −x + 1, −y, −z + 1; (iii) x + $[{1\over 2}]$ , −y, z]. The M—O bond-length ranges are 2.549 (2)–2.628 (2) (for Sr) and 2.694 (2)–2.779 (2) Å (for Ba) (Tables 5 and 6).

Table 5
Selected bond lengths (Å) for (III)

Sr1—O1W	2.628 (2)	Sr1—O11ⁱ	2.5527 (18)
Sr1—O2W	2.628 (3)	Sr1—O12ⁱⁱ	2.549 (2)
Sr1—O11	2.5527 (18)	Sr1—O12ⁱⁱⁱ	2.549 (2)
Sr1—O1Wⁱ	2.628 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, -z+1]$ ; (ii) -x+1, -y, -z+1; (iii) $[x+{\script{1\over 2}}, -y, z]$ .

Table 6
Selected bond lengths (Å) for (IV)

Ba1—O1W	2.774 (2)	Ba1—O11ⁱ	2.706 (2)
Ba1—O2W	2.779 (4)	Ba1—O12ⁱⁱ	2.694 (2)
Ba1—O11	2.706 (2)	Ba1—O12ⁱⁱⁱ	2.694 (2)
Ba1—O1Wⁱ	2.774 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, -z+1]$ ; (ii) -x+1, -y, -z+1; (iii) $[x+{\script{1\over 2}}, -y, z]$ .

Figure 7
The molecular configuration and atom-naming scheme for the complex unit in (III)

. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry codes: (i) −x + $[3 \over 2]$ , y, −z + 1; (ii) −x + 1, −y, −z + 1; (iii) x + $[1 \over 2]$ , −y, z.]

Figure 8
The molecular configuration and atom-naming scheme for the complex unit in (IV)

. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry codes: (i) −x + $[3 \over 2]$ , y, −z + 1; (ii) −x + 1, −y, −z + 1; (iii) x + $[1 \over 2]$ , −y, z.]

Both O:O′-bridging groups provide eight-membered cyclic extensions of the structure, one of which is centrosymmetric, giving a one-dimensional chain polymer structure extending along [100] (Fig. 9). In the crystal, there are inter-polymer N—H⋯O and O—H⋯O hydrogen-bonding associations to arsonate and water O-atom acceptors (Tables 7 and 8), generating a three-dimensional framework structure (Fig. 10). Present also in the crystal packing of (III) and (IV) are relatively strong π–π aromatic ring interactions with ring centroid separations (Cg⋯Cg^vii) of 3.4666 (17) Å in (III) and 3.4855 (8) Å in (IV) between inversion-related hydrogen arsanilate ligands [symmetry code: (vii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ].

Table 7
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O11^iv	0.88 (2)	1.92 (2)	2.791 (3)	173 (3)
O1W—H12W⋯O13ⁱⁱ	0.88 (3)	2.02 (2)	2.845 (3)	156 (3)
O13—H13⋯O12ⁱⁱⁱ	0.88 (2)	1.73 (2)	2.606 (3)	176 (3)
O2W—H21W⋯O11^iv	0.83 (3)	2.52 (3)	3.267 (2)	149 (3)
N4—H41⋯O1W^v	0.89 (2)	2.24 (3)	3.115 (4)	165 (2)
N4—H42⋯O13^vi	0.89 (3)	2.33 (3)	3.210 (4)	170 (3)
Symmetry codes: (ii) -x+1, -y, -z+1; (iii) $[x+{\script{1\over 2}}, -y, z]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 8
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O11^iv	0.88 (2)	1.87 (2)	2.738 (3)	168 (4)
O1W—H12W⋯O13ⁱⁱ	0.86 (3)	2.13 (3)	2.902 (3)	149 (3)
O13—H13⋯O12ⁱⁱⁱ	0.87 (2)	1.77 (2)	2.626 (3)	167 (3)
O2W—H21W⋯O11^iv	0.87 (4)	2.46 (4)	3.229 (2)	149 (3)
N4—H41⋯O1W^v	0.87 (3)	2.23 (3)	3.092 (4)	171 (3)
N4—H42⋯O13^vi	0.88 (3)	2.37 (3)	3.241 (4)	170 (3)
Symmetry codes: (ii) -x+1, -y, -z+1; (iii) $[x+{\script{1\over 2}}, -y, z]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 9
The one-dimensional coordination polymeric chains in the structure of (III)

, extending along a. The isotypic structure of (IV)

is similar. For symmetry codes, see Tables 7

and 8

Figure 10
The hydrogen bonding in the three-dimensional complex structures of (III)

and (IV)

. Non-associative H atoms have been omitted.

The monoanionic arsonate groups in all four structures are similar in having delocalized As—O11 and As—O12 bonds, which are essentially equal: 1.6617 (15) and 1.6581 (14) Å in (I); 1.673 (2) and 1.645 (2) Å in (IIA), and 1.667 (2) and 1.668 (2) Å in (IIB); 1.6650 (16) and 1.6705 (19) Å in (III); 1.667 (2) and 1.668 (2) Å in (IV). These compare with 1.672 (3) and 1.677 (3), and 1.670 (3) and 1.659 (3) Å in the ammonium and sodium salts, respectively (Smith & Wermuth, 2014), and 1.656 (6) and 1.669 (6) Å in the zwitterionic parent acid (Shimada, 1961 ; Nuttall & Hunter, 1996 ). The As—O13(H) bonds are 1.7412 (16) Å in (I), 1.721 (2) Å in (IIA) and 1.727 (2) Å in (IIB), 1.746 (2) Å in (III) and 1.749 (2) Å in (IV), compared with 1.737 (8) Å in the parent acid.

The work reported here provides a comparison of the coordination chemistry and hydrogen bonding in the three-dimensional structures of the alkaline earth series of complexes with hydrogen (4-aminophenyl)arsonic acid. With the exception of Mg complex (I), all the compounds form basically similar supramolecular structures in which the primary core comprising the polymeric metal complex and water molecules form layers which are linked through the peripheral arsanilate ring systems by hydrogen bonding involving the para-related aniline amino group. This packing feature is also found in the sodium hydrogen p-arsanilate structure (Smith & Wermuth, 2014), although the primary layer differs from the alkaline-earth members (II)–(IV) in that it involves an NaO₅ complex core with one of the three coordinated water molecules bridging.

Supporting information

CCDC references: 1520680; 1520679; 1520678; 1520677

Crystal structure: contains datablocks global, I, II, III, IV. DOI: https://doi.org/10.1107/S2053229616019434/ov3082sup1.cif

Structure factors: contains datablock shelxl. DOI: https://doi.org/10.1107/S2053229616019434/ov3082Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2053229616019434/ov3082IIsup3.hkl

Structure factors: contains datablock shelxl. DOI: https://doi.org/10.1107/S2053229616019434/ov3082IIIsup4.hkl

Structure factors: contains datablock shelxl. DOI: https://doi.org/10.1107/S2053229616019434/ov3082IVsup5.hkl

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015 for (I); CrysAlis PRO (Rigaku OD, 2015) for (II), (III), (IV). For all compounds, cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

(I) Hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate top

Crystal data top

[Mg(H₂O)₆](C₆H₇AsNO₃)·4H₂O	F(000) = 652
M_r = 636.56	D_x = 1.680 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3242 reflections
a = 15.1693 (6) Å	θ = 3.6–29.1°
b = 6.7367 (2) Å	µ = 2.75 mm⁻¹
c = 12.9532 (4) Å	T = 200 K
β = 108.033 (4)°	Prism, colourless
V = 1258.68 (7) Å³	0.35 × 0.18 × 0.10 mm
Z = 2

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2466 independent reflections
Radiation source: Enhance (Mo) X-ray source	2149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −8→8
T_min = 0.700, T_max = 0.980	l = −15→15
8901 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0344P)² + 0.0883P] where P = (F_o² + 2F_c²)/3
2466 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.40 e Å⁻³
13 restraints	Δρ_min = −0.64 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq
As1	0.23165 (2)	0.74327 (3)	0.60063 (2)	0.0166 (1)
O11	0.29867 (12)	0.8873 (2)	0.69756 (12)	0.0246 (5)
O12	0.26694 (12)	0.5094 (2)	0.60663 (12)	0.0236 (5)
O13	0.23879 (12)	0.8264 (2)	0.47619 (12)	0.0244 (5)
N4	−0.17769 (16)	0.7891 (3)	0.56343 (19)	0.0242 (7)
C1	0.10489 (18)	0.7641 (3)	0.59183 (19)	0.0186 (7)
C2	0.07751 (19)	0.7930 (4)	0.6839 (2)	0.0258 (8)
C3	−0.0154 (2)	0.7997 (4)	0.6747 (2)	0.0278 (8)
C4	−0.08290 (19)	0.7765 (3)	0.5742 (2)	0.0206 (7)
C5	−0.0548 (2)	0.7492 (3)	0.4821 (2)	0.0230 (8)
C6	0.0379 (2)	0.7422 (3)	0.4915 (2)	0.0218 (8)
Mg1	0.50000	0.50000	0.50000	0.0192 (3)
O1W	0.44254 (13)	0.4488 (3)	0.62346 (13)	0.0264 (5)
O2W	0.61417 (14)	0.3374 (3)	0.58760 (13)	0.0305 (6)
O3W	0.56172 (16)	0.7579 (2)	0.57476 (16)	0.0308 (7)
O4W	0.73459 (16)	0.7514 (2)	0.73245 (16)	0.0294 (7)
O5W	0.45949 (14)	1.0160 (3)	0.66270 (14)	0.0283 (6)
H2	0.12280	0.80820	0.75290	0.0310*
H3	−0.03370	0.82040	0.73770	0.0330*
H5	−0.10000	0.73540	0.41280	0.0280*
H6	0.05640	0.72220	0.42850	0.0260*
H13	0.2204 (19)	0.945 (3)	0.462 (2)	0.0370*
H41	−0.193 (2)	0.772 (3)	0.6215 (19)	0.0290*
H42	−0.2074 (19)	0.711 (3)	0.5111 (18)	0.0290*
H11W	0.3843 (13)	0.463 (4)	0.615 (2)	0.0400*
H12W	0.4704 (19)	0.481 (4)	0.6882 (15)	0.0400*
H21W	0.641 (2)	0.345 (4)	0.6574 (14)	0.0460*
H22W	0.6573 (19)	0.286 (4)	0.569 (3)	0.0460*
H31W	0.6181 (16)	0.761 (4)	0.623 (2)	0.0460*
H32W	0.5287 (19)	0.852 (3)	0.592 (2)	0.0460*
H41W	0.729 (2)	0.639 (3)	0.760 (2)	0.0440*
H42W	0.738 (2)	0.839 (3)	0.7823 (19)	0.0440*
H51W	0.4052 (14)	0.979 (4)	0.666 (2)	0.0420*
H52W	0.457 (2)	1.135 (3)	0.645 (2)	0.0420*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.0139 (2)	0.0182 (2)	0.0174 (2)	0.0013 (1)	0.0043 (1)	0.0003 (1)
O11	0.0234 (11)	0.0262 (8)	0.0215 (8)	−0.0038 (7)	0.0030 (7)	−0.0036 (7)
O12	0.0209 (10)	0.0188 (8)	0.0305 (9)	0.0025 (7)	0.0069 (7)	0.0011 (7)
O13	0.0278 (11)	0.0250 (8)	0.0232 (9)	0.0068 (8)	0.0122 (8)	0.0044 (7)
N4	0.0171 (13)	0.0292 (10)	0.0275 (12)	−0.0008 (9)	0.0087 (10)	−0.0004 (9)
C1	0.0142 (14)	0.0191 (11)	0.0222 (12)	0.0018 (9)	0.0052 (10)	0.0021 (8)
C2	0.0208 (16)	0.0369 (13)	0.0180 (12)	0.0028 (11)	0.0037 (11)	−0.0006 (10)
C3	0.0264 (17)	0.0387 (13)	0.0203 (12)	0.0041 (12)	0.0103 (12)	0.0017 (11)
C4	0.0192 (15)	0.0168 (10)	0.0261 (13)	0.0017 (10)	0.0074 (11)	0.0024 (9)
C5	0.0189 (16)	0.0275 (13)	0.0204 (12)	0.0003 (10)	0.0031 (11)	−0.0028 (9)
C6	0.0224 (16)	0.0253 (12)	0.0183 (12)	0.0006 (10)	0.0070 (11)	−0.0045 (9)
Mg1	0.0172 (7)	0.0225 (5)	0.0180 (5)	0.0019 (5)	0.0056 (5)	0.0000 (4)
O1W	0.0199 (11)	0.0403 (9)	0.0197 (8)	0.0020 (9)	0.0073 (8)	−0.0018 (8)
O2W	0.0252 (12)	0.0448 (11)	0.0199 (9)	0.0172 (9)	0.0048 (8)	−0.0008 (8)
O3W	0.0246 (13)	0.0304 (10)	0.0352 (11)	0.0010 (8)	0.0060 (9)	−0.0106 (8)
O4W	0.0359 (14)	0.0277 (10)	0.0273 (10)	−0.0049 (8)	0.0136 (10)	−0.0021 (7)
O5W	0.0240 (12)	0.0257 (9)	0.0347 (10)	0.0002 (8)	0.0082 (8)	0.0030 (8)

Geometric parameters (Å, º) top

Mg1—O1W	2.0734 (18)	O4W—H41W	0.85 (2)
Mg1—O2W	2.066 (2)	O4W—H42W	0.86 (2)
Mg1—O3W	2.0668 (16)	O5W—H51W	0.87 (2)
Mg1—O1Wⁱ	2.0734 (18)	O5W—H52W	0.83 (2)
Mg1—O2Wⁱ	2.066 (2)	N4—C4	1.404 (4)
Mg1—O3Wⁱ	2.0668 (16)	N4—H41	0.86 (3)
As1—O11	1.6617 (15)	N4—H42	0.87 (2)
As1—O12	1.6581 (14)	C1—C6	1.388 (4)
As1—O13	1.7412 (15)	C1—C2	1.393 (4)
As1—C1	1.896 (3)	C2—C3	1.378 (4)
O13—H13	0.85 (2)	C3—C4	1.394 (4)
O1W—H12W	0.84 (2)	C4—C5	1.398 (4)
O1W—H11W	0.86 (2)	C5—C6	1.374 (4)
O2W—H21W	0.871 (18)	C2—H2	0.9500
O2W—H22W	0.84 (3)	C3—H3	0.9500
O3W—H32W	0.88 (2)	C5—H5	0.9500
O3W—H31W	0.89 (3)	C6—H6	0.9500

O11—As1—O12	113.97 (8)	H21W—O2W—H22W	100 (3)
O11—As1—O13	108.23 (7)	Mg1—O3W—H32W	121.0 (18)
O11—As1—C1	111.97 (9)	H31W—O3W—H32W	108 (2)
O12—As1—O13	103.73 (7)	Mg1—O3W—H31W	123.1 (17)
O12—As1—C1	112.33 (9)	H41W—O4W—H42W	107 (2)
O13—As1—C1	105.85 (9)	H51W—O5W—H52W	109 (3)
O1Wⁱ—Mg1—O3W	89.08 (8)	C4—N4—H41	117 (2)
O2Wⁱ—Mg1—O3W	89.59 (8)	H41—N4—H42	113 (2)
O3W—Mg1—O3Wⁱ	180.00	C4—N4—H42	108 (2)
O1Wⁱ—Mg1—O2Wⁱ	88.24 (8)	C2—C1—C6	119.4 (3)
O1Wⁱ—Mg1—O3Wⁱ	90.92 (8)	As1—C1—C6	118.9 (2)
O2Wⁱ—Mg1—O3Wⁱ	90.41 (8)	As1—C1—C2	121.65 (19)
O1Wⁱ—Mg1—O2W	91.76 (8)	C1—C2—C3	119.9 (2)
O1W—Mg1—O2W	88.24 (8)	C2—C3—C4	120.9 (2)
O1W—Mg1—O3W	90.92 (8)	N4—C4—C3	121.3 (2)
O1W—Mg1—O1Wⁱ	180.00	C3—C4—C5	118.8 (3)
O1W—Mg1—O2Wⁱ	91.76 (8)	N4—C4—C5	119.8 (2)
O1W—Mg1—O3Wⁱ	89.08 (8)	C4—C5—C6	120.2 (2)
O2W—Mg1—O3W	90.41 (8)	C1—C6—C5	120.8 (2)
O2W—Mg1—O2Wⁱ	180.00	C3—C2—H2	120.00
O2W—Mg1—O3Wⁱ	89.59 (8)	C1—C2—H2	120.00
As1—O13—H13	113.2 (18)	C2—C3—H3	120.00
Mg1—O1W—H11W	122.9 (17)	C4—C3—H3	120.00
H11W—O1W—H12W	106 (3)	C6—C5—H5	120.00
Mg1—O1W—H12W	121.6 (19)	C4—C5—H5	120.00
Mg1—O2W—H21W	125.6 (19)	C1—C6—H6	120.00
Mg1—O2W—H22W	131 (2)	C5—C6—H6	120.00

O11—As1—C1—C2	−34.6 (2)	As1—C1—C6—C5	177.68 (16)
O11—As1—C1—C6	147.97 (16)	C2—C1—C6—C5	0.2 (3)
O12—As1—C1—C2	95.2 (2)	C1—C2—C3—C4	0.5 (4)
O12—As1—C1—C6	−82.29 (18)	C2—C3—C4—N4	−178.0 (2)
O13—As1—C1—C2	−152.29 (18)	C2—C3—C4—C5	−1.0 (4)
O13—As1—C1—C6	30.24 (18)	N4—C4—C5—C6	178.20 (19)
As1—C1—C2—C3	−177.5 (2)	C3—C4—C5—C6	1.1 (3)
C6—C1—C2—C3	0.0 (4)	C4—C5—C6—C1	−0.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N4ⁱⁱ	0.85 (2)	1.90 (2)	2.745 (3)	177 (3)
N4—H41···O4Wⁱⁱⁱ	0.86 (3)	2.07 (3)	2.904 (3)	164 (3)
N4—H42···O12^iv	0.87 (2)	2.12 (2)	2.980 (3)	172 (2)
O1W—H11W···O12	0.86 (2)	1.78 (2)	2.636 (3)	175 (2)
O1W—H12W···O5W^v	0.84 (2)	1.91 (2)	2.745 (2)	172 (3)
O2W—H21W···O11^v	0.87 (2)	1.84 (2)	2.707 (2)	174 (2)
O2W—H22W···O13ⁱ	0.84 (3)	1.99 (3)	2.831 (3)	178 (3)
O3W—H31W···O4W	0.89 (3)	1.89 (3)	2.781 (3)	175 (3)
O3W—H32W···O5W	0.88 (2)	1.94 (3)	2.796 (3)	165 (2)
O4W—H41W···O11^v	0.85 (2)	1.87 (2)	2.716 (2)	172 (3)
O4W—H42W···O12^vi	0.86 (2)	1.86 (2)	2.720 (2)	173 (3)
O5W—H51W···O11	0.87 (2)	1.89 (2)	2.755 (3)	170 (2)
O5W—H52W···O1W^vii	0.83 (2)	2.14 (2)	2.957 (3)	170 (3)

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

(II) catena-Poly[[[diaquacalcium]-bis[µ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O']-[diaquacalcium]-bis[µ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O]] dihydrate] top

Crystal data top

[Ca(C₆H₇AsNO₃)₂(H₂O)₂]·2H₂O	Z = 2
M_r = 544.24	F(000) = 548
Triclinic, P1	D_x = 1.890 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.001 (5) Å	Cell parameters from 2319 reflections
b = 9.672 (5) Å	θ = 3.7–29.1°
c = 11.756 (5) Å	µ = 3.82 mm⁻¹
α = 77.096 (5)°	T = 200 K
β = 74.096 (5)°	Needle, colourless
γ = 82.236 (5)°	0.35 × 0.11 × 0.10 mm
V = 956.4 (8) Å³

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	3744 independent reflections
Radiation source: Enhance (Mo) X-ray source	3276 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −11→11
T_min = 0.931, T_max = 0.980	l = −11→14
6921 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0206P)² + 0.3783P] where P = (F_o² + 2F_c²)/3
3744 reflections	(Δ/σ)_max < 0.001
286 parameters	Δρ_max = 0.55 e Å⁻³
14 restraints	Δρ_min = −0.47 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
As1A	0.46094 (3)	0.29369 (3)	0.70142 (3)	0.0151 (1)
As1B	0.05599 (3)	0.77612 (3)	0.30427 (3)	0.0150 (1)
Ca1	0.21559 (7)	0.47820 (7)	0.49139 (5)	0.0163 (2)
O1W	0.2142 (3)	0.6294 (3)	0.6273 (3)	0.0385 (10)
O2W	0.2504 (3)	0.2937 (3)	0.3844 (2)	0.0337 (9)
O11A	0.3299 (2)	0.3106 (2)	0.62105 (19)	0.0212 (7)
O11B	0.0283 (2)	0.6219 (2)	0.40158 (19)	0.0188 (6)
O12A	0.5836 (2)	0.4184 (2)	0.65510 (19)	0.0237 (7)
O12B	0.1482 (2)	0.8895 (2)	0.3433 (2)	0.0215 (7)
O13A	0.5597 (2)	0.1296 (2)	0.6925 (2)	0.0245 (7)
O13B	−0.1207 (2)	0.8695 (2)	0.3001 (2)	0.0210 (7)
N4A	0.1055 (3)	0.1983 (3)	1.2273 (3)	0.0280 (10)
N4B	0.3873 (3)	0.6567 (4)	−0.1903 (3)	0.0316 (11)
C1A	0.3520 (3)	0.2727 (3)	0.8657 (3)	0.0174 (9)
C1B	0.1555 (3)	0.7413 (3)	0.1487 (3)	0.0175 (9)
C2A	0.2011 (3)	0.3329 (4)	0.8981 (3)	0.0214 (10)
C2B	0.2238 (3)	0.6061 (3)	0.1366 (3)	0.0193 (10)
C3A	0.1191 (3)	0.3081 (4)	1.0179 (3)	0.0219 (10)
C3B	0.3031 (3)	0.5791 (4)	0.0248 (3)	0.0224 (10)
C4A	0.1858 (4)	0.2232 (4)	1.1056 (3)	0.0211 (10)
C4B	0.3143 (4)	0.6866 (4)	−0.0779 (3)	0.0234 (10)
C5A	0.3378 (4)	0.1650 (4)	1.0731 (3)	0.0237 (10)
C5B	0.2442 (4)	0.8224 (4)	−0.0651 (3)	0.0233 (10)
C6A	0.4189 (4)	0.1893 (4)	0.9545 (3)	0.0219 (10)
C6B	0.1668 (3)	0.8504 (4)	0.0465 (3)	0.0220 (10)
O3W	0.1947 (3)	0.9169 (3)	0.5593 (2)	0.0356 (9)
O4W	0.4898 (3)	−0.1005 (3)	0.6212 (3)	0.0354 (9)
H2A	0.15470	0.39070	0.83840	0.0260*
H2B	0.21590	0.53190	0.20580	0.0230*
H3A	0.01610	0.34950	1.04030	0.0260*
H3B	0.35060	0.48650	0.01740	0.0270*
H5A	0.38500	0.10860	1.13290	0.0280*
H5B	0.25020	0.89610	−0.13440	0.0280*
H6A	0.52240	0.14880	0.93250	0.0260*
H6B	0.12120	0.94340	0.05430	0.0260*
H11W	0.273 (4)	0.622 (5)	0.679 (3)	0.0580*
H12W	0.202 (5)	0.723 (2)	0.600 (4)	0.0580*
H13A	0.660 (2)	0.135 (4)	0.680 (3)	0.0370*
H13B	−0.194 (3)	0.810 (3)	0.319 (3)	0.0310*
H21W	0.200 (4)	0.270 (4)	0.340 (3)	0.0510*
H22W	0.325 (3)	0.227 (3)	0.393 (4)	0.0510*
H41A	0.121 (4)	0.109 (2)	1.263 (3)	0.0340*
H41B	0.459 (3)	0.587 (3)	−0.192 (3)	0.0380*
H42A	0.008 (2)	0.230 (4)	1.234 (3)	0.0340*
H42B	0.421 (4)	0.731 (3)	−0.241 (3)	0.0380*
H31W	0.159 (4)	0.984 (4)	0.602 (3)	0.0530*
H32W	0.172 (4)	0.934 (5)	0.488 (2)	0.0530*
H41W	0.415 (4)	−0.087 (5)	0.585 (3)	0.0530*
H42W	0.511 (5)	−0.023 (3)	0.641 (4)	0.0530*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1A	0.0135 (2)	0.0163 (2)	0.0145 (2)	−0.0032 (1)	−0.0032 (1)	−0.0001 (1)
As1B	0.0142 (2)	0.0138 (2)	0.0154 (2)	−0.0020 (1)	−0.0030 (1)	−0.0003 (1)
Ca1	0.0148 (3)	0.0169 (3)	0.0157 (3)	−0.0035 (3)	−0.0033 (3)	0.0008 (3)
O1W	0.0565 (18)	0.0258 (15)	0.0412 (17)	0.0004 (14)	−0.0250 (14)	−0.0096 (14)
O2W	0.0362 (15)	0.0327 (16)	0.0398 (16)	0.0034 (12)	−0.0159 (13)	−0.0184 (13)
O11A	0.0198 (11)	0.0229 (13)	0.0203 (12)	−0.0042 (10)	−0.0078 (9)	0.0016 (10)
O11B	0.0148 (10)	0.0176 (12)	0.0198 (11)	−0.0042 (9)	−0.0027 (9)	0.0043 (10)
O12A	0.0228 (11)	0.0252 (13)	0.0217 (12)	−0.0131 (10)	−0.0002 (10)	−0.0017 (11)
O12B	0.0172 (11)	0.0219 (13)	0.0276 (13)	−0.0032 (9)	−0.0079 (10)	−0.0055 (11)
O13A	0.0179 (11)	0.0204 (13)	0.0345 (14)	0.0014 (10)	−0.0064 (11)	−0.0061 (11)
O13B	0.0162 (11)	0.0176 (12)	0.0281 (13)	−0.0025 (9)	−0.0069 (10)	−0.0001 (10)
N4A	0.0315 (16)	0.0289 (18)	0.0184 (16)	−0.0068 (15)	0.0017 (13)	−0.0011 (14)
N4B	0.0362 (18)	0.032 (2)	0.0212 (17)	−0.0058 (15)	0.0028 (14)	−0.0046 (15)
C1A	0.0182 (15)	0.0179 (17)	0.0147 (16)	−0.0065 (13)	−0.0021 (13)	0.0002 (13)
C1B	0.0159 (15)	0.0203 (17)	0.0160 (16)	−0.0030 (13)	−0.0040 (13)	−0.0018 (14)
C2A	0.0198 (16)	0.0227 (18)	0.0219 (18)	−0.0018 (14)	−0.0082 (14)	−0.0010 (15)
C2B	0.0227 (16)	0.0168 (17)	0.0177 (17)	−0.0054 (14)	−0.0045 (14)	−0.0002 (14)
C3A	0.0128 (15)	0.0235 (19)	0.0276 (19)	−0.0033 (13)	−0.0004 (14)	−0.0061 (16)
C3B	0.0217 (16)	0.0190 (18)	0.0285 (19)	−0.0033 (14)	−0.0084 (15)	−0.0054 (15)
C4A	0.0257 (17)	0.0201 (18)	0.0164 (17)	−0.0094 (14)	0.0005 (14)	−0.0040 (14)
C4B	0.0197 (16)	0.031 (2)	0.0212 (18)	−0.0115 (15)	−0.0040 (14)	−0.0045 (16)
C5A	0.0262 (17)	0.0226 (19)	0.0219 (18)	−0.0019 (15)	−0.0100 (15)	0.0014 (15)
C5B	0.0292 (18)	0.0210 (18)	0.0160 (17)	−0.0047 (15)	−0.0057 (14)	0.0056 (15)
C6A	0.0183 (16)	0.0227 (18)	0.0243 (18)	−0.0020 (14)	−0.0064 (14)	−0.0021 (15)
C6B	0.0226 (16)	0.0167 (17)	0.0250 (18)	−0.0019 (14)	−0.0064 (14)	0.0002 (15)
O3W	0.0452 (16)	0.0310 (16)	0.0298 (16)	0.0053 (13)	−0.0086 (13)	−0.0104 (13)
O4W	0.0402 (15)	0.0256 (15)	0.0433 (17)	−0.0040 (13)	−0.0149 (13)	−0.0067 (13)

Geometric parameters (Å, º) top

Ca1—O1W	2.392 (3)	N4B—C4B	1.380 (5)
Ca1—O2W	2.345 (3)	N4A—H42A	0.88 (2)
Ca1—O11A	2.306 (2)	N4A—H41A	0.88 (2)
Ca1—O11B	2.361 (2)	N4B—H41B	0.87 (3)
Ca1—O11Bⁱ	2.420 (2)	N4B—H42B	0.86 (3)
Ca1—O12Aⁱⁱ	2.291 (2)	C1A—C6A	1.393 (5)
As1A—O11A	1.673 (2)	C1A—C2A	1.390 (4)
As1A—O12A	1.645 (2)	C1B—C6B	1.401 (5)
As1A—O13A	1.721 (2)	C1B—C2B	1.388 (4)
As1A—C1A	1.890 (3)	C2A—C3A	1.383 (5)
As1B—O11B	1.667 (2)	C2B—C3B	1.376 (5)
As1B—O12B	1.668 (2)	C3A—C4A	1.388 (5)
As1B—O13B	1.727 (2)	C3B—C4B	1.396 (5)
As1B—C1B	1.886 (3)	C4A—C5A	1.392 (5)
O1W—H12W	0.89 (2)	C4B—C5B	1.399 (6)
O1W—H11W	0.90 (4)	C5A—C6A	1.369 (5)
O2W—H22W	0.88 (3)	C5B—C6B	1.374 (5)
O2W—H21W	0.86 (4)	C2A—H2A	0.9500
O13A—H13A	0.88 (2)	C2B—H2B	0.9500
O13B—H13B	0.88 (3)	C3A—H3A	0.9500
O3W—H31W	0.88 (4)	C3B—H3B	0.9500
O3W—H32W	0.89 (3)	C5A—H5A	0.9500
O4W—H42W	0.89 (4)	C5B—H5B	0.9500
O4W—H41W	0.87 (4)	C6A—H6A	0.9500
N4A—C4A	1.398 (5)	C6B—H6B	0.9500

O11A—As1A—O12A	114.52 (10)	C4A—N4A—H41A	112 (2)
O11A—As1A—O13A	106.16 (10)	H41A—N4A—H42A	115 (3)
O11A—As1A—C1A	107.43 (11)	C4A—N4A—H42A	109 (2)
O12A—As1A—O13A	109.97 (10)	C4B—N4B—H42B	112 (2)
O12A—As1A—C1A	114.58 (12)	H41B—N4B—H42B	111 (3)
O13A—As1A—C1A	103.28 (12)	C4B—N4B—H41B	116 (2)
O11B—As1B—O12B	114.80 (10)	C2A—C1A—C6A	119.5 (3)
O11B—As1B—O13B	109.59 (10)	As1A—C1A—C2A	120.2 (2)
O11B—As1B—C1B	109.58 (12)	As1A—C1A—C6A	120.2 (2)
O12B—As1B—O13B	102.37 (10)	As1B—C1B—C6B	121.2 (2)
O12B—As1B—C1B	111.56 (12)	C2B—C1B—C6B	119.8 (3)
O13B—As1B—C1B	108.58 (12)	As1B—C1B—C2B	119.0 (2)
O1W—Ca1—O2W	166.97 (10)	C1A—C2A—C3A	119.5 (3)
O1W—Ca1—O11A	83.52 (9)	C1B—C2B—C3B	120.3 (3)
O1W—Ca1—O11B	95.61 (9)	C2A—C3A—C4A	120.6 (3)
O1W—Ca1—O11Bⁱ	97.05 (9)	C2B—C3B—C4B	120.6 (3)
O1W—Ca1—O12Aⁱⁱ	93.82 (9)	N4A—C4A—C3A	121.5 (3)
O2W—Ca1—O11A	83.57 (8)	C3A—C4A—C5A	119.7 (3)
O2W—Ca1—O11B	97.20 (8)	N4A—C4A—C5A	118.8 (3)
O2W—Ca1—O11Bⁱ	84.13 (8)	N4B—C4B—C3B	120.1 (4)
O2W—Ca1—O12Aⁱⁱ	87.99 (8)	C3B—C4B—C5B	118.9 (3)
O11A—Ca1—O11B	162.13 (8)	N4B—C4B—C5B	121.0 (3)
O11A—Ca1—O11Bⁱ	87.66 (7)	C4A—C5A—C6A	119.7 (3)
O11A—Ca1—O12Aⁱⁱ	105.49 (7)	C4B—C5B—C6B	120.8 (3)
O11B—Ca1—O11Bⁱ	74.70 (7)	C1A—C6A—C5A	121.0 (3)
O11B—Ca1—O12Aⁱⁱ	92.38 (7)	C1B—C6B—C5B	119.7 (3)
O11Bⁱ—Ca1—O12Aⁱⁱ	163.83 (8)	C1A—C2A—H2A	120.00
As1A—O11A—Ca1	141.02 (11)	C3A—C2A—H2A	120.00
As1B—O11B—Ca1	126.08 (10)	C1B—C2B—H2B	120.00
As1B—O11B—Ca1ⁱ	127.68 (10)	C3B—C2B—H2B	120.00
Ca1—O11B—Ca1ⁱ	105.30 (8)	C4A—C3A—H3A	120.00
As1A—O12A—Ca1ⁱⁱ	148.32 (12)	C2A—C3A—H3A	120.00
H11W—O1W—H12W	104 (4)	C2B—C3B—H3B	120.00
Ca1—O1W—H11W	130 (3)	C4B—C3B—H3B	120.00
Ca1—O1W—H12W	117 (3)	C4A—C5A—H5A	120.00
Ca1—O2W—H21W	134 (3)	C6A—C5A—H5A	120.00
Ca1—O2W—H22W	118 (2)	C6B—C5B—H5B	120.00
H21W—O2W—H22W	108 (3)	C4B—C5B—H5B	120.00
As1A—O13A—H13A	111 (3)	C1A—C6A—H6A	120.00
As1B—O13B—H13B	110 (2)	C5A—C6A—H6A	119.00
H31W—O3W—H32W	115 (4)	C5B—C6B—H6B	120.00
H41W—O4W—H42W	115 (4)	C1B—C6B—H6B	120.00

O12A—As1A—O11A—Ca1	−20.6 (2)	O12Aⁱⁱ—Ca1—O11B—As1B	−20.34 (14)
O13A—As1A—O11A—Ca1	−142.16 (17)	O12Aⁱⁱ—Ca1—O11B—Ca1ⁱ	170.13 (8)
C1A—As1A—O11A—Ca1	107.86 (19)	O1W—Ca1—O11Bⁱ—As1Bⁱ	−96.79 (15)
O11A—As1A—O12A—Ca1ⁱⁱ	−67.3 (2)	O1W—Ca1—O11Bⁱ—Ca1ⁱ	93.92 (10)
O13A—As1A—O12A—Ca1ⁱⁱ	52.2 (2)	O2W—Ca1—O11Bⁱ—As1Bⁱ	70.16 (14)
C1A—As1A—O12A—Ca1ⁱⁱ	167.9 (2)	O2W—Ca1—O11Bⁱ—Ca1ⁱ	−99.14 (9)
O11A—As1A—C1A—C2A	−28.5 (3)	O11A—Ca1—O11Bⁱ—As1Bⁱ	−13.62 (14)
O11A—As1A—C1A—C6A	147.5 (3)	O11A—Ca1—O11Bⁱ—Ca1ⁱ	177.09 (9)
O12A—As1A—C1A—C2A	100.0 (3)	O11B—Ca1—O11Bⁱ—As1Bⁱ	169.30 (15)
O12A—As1A—C1A—C6A	−84.1 (3)	O11B—Ca1—O11Bⁱ—Ca1ⁱ	0.00 (8)
O13A—As1A—C1A—C2A	−140.4 (3)	O1W—Ca1—O12Aⁱⁱ—As1Aⁱⁱ	−4.1 (2)
O13A—As1A—C1A—C6A	35.5 (3)	O2W—Ca1—O12Aⁱⁱ—As1Aⁱⁱ	−171.2 (2)
O12B—As1B—O11B—Ca1	−46.35 (16)	O11A—Ca1—O12Aⁱⁱ—As1Aⁱⁱ	−88.4 (2)
O12B—As1B—O11B—Ca1ⁱ	120.84 (13)	O11B—Ca1—O12Aⁱⁱ—As1Aⁱⁱ	91.7 (2)
O13B—As1B—O11B—Ca1	−160.87 (12)	As1A—C1A—C2A—C3A	175.4 (3)
O13B—As1B—O11B—Ca1ⁱ	6.33 (16)	C6A—C1A—C2A—C3A	−0.6 (5)
C1B—As1B—O11B—Ca1	80.09 (15)	As1A—C1A—C6A—C5A	−175.5 (3)
C1B—As1B—O11B—Ca1ⁱ	−112.72 (15)	C2A—C1A—C6A—C5A	0.4 (5)
O11B—As1B—C1B—C2B	−14.6 (3)	As1B—C1B—C2B—C3B	−177.1 (2)
O11B—As1B—C1B—C6B	168.0 (2)	C6B—C1B—C2B—C3B	0.3 (4)
O12B—As1B—C1B—C2B	113.7 (2)	As1B—C1B—C6B—C5B	178.0 (3)
O12B—As1B—C1B—C6B	−63.7 (3)	C2B—C1B—C6B—C5B	0.6 (5)
O13B—As1B—C1B—C2B	−134.2 (2)	C1A—C2A—C3A—C4A	−0.4 (5)
O13B—As1B—C1B—C6B	48.3 (3)	C1B—C2B—C3B—C4B	−0.8 (5)
O1W—Ca1—O11A—As1A	−40.53 (19)	C2A—C3A—C4A—N4A	179.2 (3)
O2W—Ca1—O11A—As1A	137.75 (19)	C2A—C3A—C4A—C5A	1.4 (6)
O11Bⁱ—Ca1—O11A—As1A	−137.90 (18)	C2B—C3B—C4B—N4B	−176.7 (3)
O12Aⁱⁱ—Ca1—O11A—As1A	51.65 (19)	C2B—C3B—C4B—C5B	0.3 (5)
O1W—Ca1—O11B—As1B	73.73 (15)	N4A—C4A—C5A—C6A	−179.4 (3)
O1W—Ca1—O11B—Ca1ⁱ	−95.79 (10)	C3A—C4A—C5A—C6A	−1.5 (6)
O2W—Ca1—O11B—As1B	−108.61 (14)	N4B—C4B—C5B—C6B	177.6 (3)
O2W—Ca1—O11B—Ca1ⁱ	81.87 (9)	C3B—C4B—C5B—C6B	0.6 (5)
O11Bⁱ—Ca1—O11B—As1B	169.52 (15)	C4A—C5A—C6A—C1A	0.6 (6)
O11Bⁱ—Ca1—O11B—Ca1ⁱ	0.00 (7)	C4B—C5B—C6B—C1B	−1.1 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13A—H13A···O12Bⁱⁱ	0.88 (2)	1.67 (2)	2.534 (3)	169 (4)
O13B—H13B···O11Aⁱ	0.88 (3)	1.70 (3)	2.578 (3)	170 (3)
N4A—H41A···O12Bⁱⁱⁱ	0.88 (2)	2.13 (2)	3.014 (4)	176 (4)
N4B—H42B···O4W^iv	0.86 (3)	2.05 (3)	2.901 (5)	172 (4)
O1W—H11W···N4B^v	0.90 (4)	2.17 (4)	3.048 (5)	166 (4)
O1W—H12W···O3W	0.89 (2)	1.83 (2)	2.712 (4)	171 (3)
O2W—H21W···N4A^vi	0.86 (4)	2.04 (4)	2.893 (4)	173 (4)
O2W—H22W···O4W^vii	0.88 (3)	1.92 (3)	2.785 (4)	168 (4)
O3W—H31W···O13B^viii	0.88 (4)	1.96 (4)	2.827 (4)	169 (4)
O3W—H32W···O12B	0.89 (3)	1.92 (3)	2.758 (4)	157 (4)
O4W—H41W···O3W^ix	0.87 (4)	2.08 (4)	2.915 (4)	160 (3)
O4W—H42W···O13A	0.89 (4)	1.86 (3)	2.748 (4)	176 (2)

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

(III) catena-Poly[[triaquastrontium]-bis[µ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O']] top

Crystal data top

[Sr(C₆H₇AsNO₃)₂(H₂O)₃]	F(000) = 1128
M_r = 573.76	D_x = 2.166 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 2201 reflections
a = 9.8935 (3) Å	θ = 3.6–29.0°
b = 7.5844 (3) Å	µ = 6.85 mm⁻¹
c = 23.6669 (9) Å	T = 200 K
β = 97.866 (3)°	Block, colourless
V = 1759.17 (11) Å³	0.25 × 0.12 × 0.12 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	1737 independent reflections
Radiation source: Enhance (Mo) X-ray source	1606 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −9→8
T_min = 0.791, T_max = 0.980	l = −29→26
3326 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0188P)² + 2.3681P] where P = (F_o² + 2F_c²)/3
1737 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.47 e Å⁻³
7 restraints	Δρ_min = −0.54 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Sr1	0.75000	0.28095 (5)	0.50000	0.0144 (1)
As1	0.44233 (2)	0.06077 (3)	0.41189 (1)	0.0131 (1)
O1W	0.5937 (2)	0.4181 (3)	0.56983 (10)	0.0265 (7)
O2W	0.75000	0.6274 (4)	0.50000	0.0384 (11)
O11	0.51439 (18)	0.2419 (2)	0.44227 (8)	0.0197 (6)
O12	0.31029 (18)	−0.0183 (3)	0.44109 (8)	0.0198 (6)
O13	0.56339 (18)	−0.1079 (3)	0.42091 (8)	0.0194 (6)
N4	0.3286 (3)	0.0837 (4)	0.15430 (11)	0.0284 (9)
C1	0.3951 (2)	0.0844 (4)	0.33210 (11)	0.0149 (7)
C2	0.2969 (3)	−0.0261 (4)	0.30314 (12)	0.0178 (8)
C3	0.2717 (3)	−0.0238 (4)	0.24435 (12)	0.0198 (8)
C4	0.3452 (3)	0.0894 (4)	0.21317 (12)	0.0189 (8)
C5	0.4396 (3)	0.2040 (4)	0.24267 (12)	0.0209 (9)
C6	0.4645 (3)	0.2017 (4)	0.30139 (12)	0.0188 (8)
H2	0.24690	−0.10380	0.32400	0.0210*
H3	0.20410	−0.09940	0.22490	0.0240*
H5	0.48760	0.28480	0.22210	0.0250*
H6	0.52930	0.28060	0.32090	0.0230*
H11W	0.553 (3)	0.521 (3)	0.5654 (16)	0.0400*
H12W	0.529 (3)	0.344 (3)	0.5764 (14)	0.0400*
H13	0.648 (2)	−0.071 (4)	0.4277 (13)	0.0290*
H21W	0.691 (3)	0.698 (4)	0.5081 (18)	0.0580*
H41	0.254 (2)	0.032 (4)	0.1360 (13)	0.0340*
H42	0.359 (3)	0.177 (3)	0.1374 (14)	0.0340*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sr1	0.0146 (2)	0.0124 (2)	0.0158 (2)	0.0000	0.0004 (1)	0.0000
As1	0.0119 (1)	0.0115 (2)	0.0156 (2)	0.0002 (1)	0.0015 (1)	−0.0001 (1)
O1W	0.0245 (11)	0.0177 (11)	0.0387 (13)	−0.0007 (9)	0.0097 (9)	−0.0027 (10)
O2W	0.051 (2)	0.0175 (17)	0.048 (2)	0.0000	0.0117 (17)	0.0000
O11	0.0218 (10)	0.0129 (9)	0.0224 (10)	−0.0005 (8)	−0.0041 (8)	−0.0018 (9)
O12	0.0153 (9)	0.0228 (10)	0.0220 (11)	0.0016 (8)	0.0052 (7)	0.0053 (9)
O13	0.0130 (9)	0.0144 (9)	0.0304 (11)	0.0012 (8)	0.0011 (8)	−0.0007 (9)
N4	0.0347 (15)	0.0312 (16)	0.0192 (14)	0.0027 (13)	0.0031 (11)	0.0018 (12)
C1	0.0142 (12)	0.0151 (13)	0.0154 (13)	0.0026 (11)	0.0023 (10)	−0.0007 (12)
C2	0.0186 (14)	0.0139 (13)	0.0211 (15)	−0.0026 (11)	0.0036 (11)	−0.0007 (12)
C3	0.0210 (14)	0.0157 (13)	0.0214 (15)	−0.0019 (12)	−0.0012 (11)	−0.0029 (12)
C4	0.0188 (13)	0.0195 (14)	0.0181 (14)	0.0091 (12)	0.0015 (10)	−0.0009 (12)
C5	0.0183 (14)	0.0214 (15)	0.0241 (16)	0.0016 (12)	0.0067 (11)	0.0077 (13)
C6	0.0164 (13)	0.0157 (14)	0.0238 (15)	−0.0018 (11)	0.0010 (11)	0.0005 (12)

Geometric parameters (Å, º) top

Sr1—O1W	2.628 (2)	O13—H13	0.88 (2)
Sr1—O2W	2.628 (3)	N4—C4	1.381 (4)
Sr1—O11	2.5527 (18)	N4—H41	0.89 (2)
Sr1—O1Wⁱ	2.628 (2)	N4—H42	0.89 (3)
Sr1—O11ⁱ	2.5527 (18)	C1—C2	1.391 (4)
Sr1—O12ⁱⁱ	2.549 (2)	C1—C6	1.388 (4)
Sr1—O12ⁱⁱⁱ	2.549 (2)	C2—C3	1.380 (4)
As1—O11	1.6650 (16)	C3—C4	1.399 (4)
As1—O12	1.6705 (19)	C4—C5	1.392 (4)
As1—O13	1.746 (2)	C5—C6	1.378 (4)
As1—C1	1.891 (3)	C2—H2	0.9500
O1W—H11W	0.88 (2)	C3—H3	0.9500
O1W—H12W	0.88 (3)	C5—H5	0.9500
O2W—H21W	0.83 (3)	C6—H6	0.9500
O2W—H21Wⁱ	0.83 (3)

O1W—Sr1—O2W	66.68 (5)	Sr1—O1W—H11W	125 (2)
O1W—Sr1—O11	79.03 (6)	Sr1—O1W—H12W	111.3 (18)
O1W—Sr1—O1Wⁱ	133.36 (7)	H11W—O1W—H12W	105 (3)
O1W—Sr1—O11ⁱ	106.39 (6)	H21W—O2W—H21Wⁱ	100 (3)
O1W—Sr1—O12ⁱⁱ	76.31 (7)	Sr1—O2W—H21Wⁱ	130 (2)
O1W—Sr1—O12ⁱⁱⁱ	148.81 (7)	Sr1—O2W—H21W	130 (2)
O2W—Sr1—O11	96.66 (4)	As1—O13—H13	114.2 (19)
O1Wⁱ—Sr1—O2W	66.68 (5)	C4—N4—H41	118.6 (19)
O2W—Sr1—O11ⁱ	96.66 (4)	H41—N4—H42	116 (3)
O2W—Sr1—O12ⁱⁱ	141.41 (5)	C4—N4—H42	116 (2)
O2W—Sr1—O12ⁱⁱⁱ	141.41 (5)	As1—C1—C6	120.8 (2)
O1Wⁱ—Sr1—O11	106.39 (6)	As1—C1—C2	119.7 (2)
O11—Sr1—O11ⁱ	166.68 (5)	C2—C1—C6	119.4 (2)
O11—Sr1—O12ⁱⁱ	86.40 (6)	C1—C2—C3	120.5 (3)
O11—Sr1—O12ⁱⁱⁱ	83.19 (6)	C2—C3—C4	120.3 (3)
O1Wⁱ—Sr1—O11ⁱ	79.03 (6)	N4—C4—C5	120.3 (3)
O1Wⁱ—Sr1—O12ⁱⁱ	148.81 (7)	N4—C4—C3	121.0 (3)
O1Wⁱ—Sr1—O12ⁱⁱⁱ	76.31 (7)	C3—C4—C5	118.7 (3)
O11ⁱ—Sr1—O12ⁱⁱ	83.19 (6)	C4—C5—C6	120.9 (3)
O11ⁱ—Sr1—O12ⁱⁱⁱ	86.40 (6)	C1—C6—C5	120.2 (3)
O12ⁱⁱ—Sr1—O12ⁱⁱⁱ	77.18 (7)	C1—C2—H2	120.00
O11—As1—O12	115.50 (10)	C3—C2—H2	120.00
O11—As1—O13	107.81 (9)	C2—C3—H3	120.00
O11—As1—C1	112.69 (11)	C4—C3—H3	120.00
O12—As1—O13	104.40 (10)	C4—C5—H5	120.00
O12—As1—C1	110.29 (9)	C6—C5—H5	119.00
O13—As1—C1	105.26 (10)	C1—C6—H6	120.00
Sr1—O11—As1	129.24 (9)	C5—C6—H6	120.00
Sr1ⁱⁱ—O12—As1	139.61 (11)

O1W—Sr1—O11—As1	−127.66 (13)	O12—As1—C1—C6	156.6 (2)
O2W—Sr1—O11—As1	167.73 (11)	O13—As1—C1—C2	83.8 (2)
O1Wⁱ—Sr1—O11—As1	100.13 (13)	O13—As1—C1—C6	−91.3 (2)
O12ⁱⁱ—Sr1—O11—As1	−50.91 (12)	As1—C1—C2—C3	−173.0 (2)
O12ⁱⁱⁱ—Sr1—O11—As1	26.60 (12)	C6—C1—C2—C3	2.2 (4)
O12—As1—O11—Sr1	111.52 (12)	As1—C1—C6—C5	172.8 (2)
O13—As1—O11—Sr1	−4.75 (14)	C2—C1—C6—C5	−2.3 (4)
C1—As1—O11—Sr1	−120.47 (12)	C1—C2—C3—C4	0.3 (5)
O11—As1—O12—Sr1ⁱⁱ	−109.92 (16)	C2—C3—C4—N4	175.0 (3)
O13—As1—O12—Sr1ⁱⁱ	8.26 (18)	C2—C3—C4—C5	−2.6 (4)
C1—As1—O12—Sr1ⁱⁱ	120.88 (16)	N4—C4—C5—C6	−175.1 (3)
O11—As1—C1—C2	−159.0 (2)	C3—C4—C5—C6	2.6 (5)
O11—As1—C1—C6	25.9 (3)	C4—C5—C6—C1	−0.1 (5)
O12—As1—C1—C2	−28.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O11^iv	0.88 (2)	1.92 (2)	2.791 (3)	173 (3)
O1W—H12W···O13ⁱⁱ	0.88 (3)	2.02 (2)	2.845 (3)	156 (3)
O13—H13···O12ⁱⁱⁱ	0.88 (2)	1.73 (2)	2.606 (3)	176 (3)
O2W—H21W···O11^iv	0.83 (3)	2.52 (3)	3.267 (2)	149 (3)
N4—H41···O1W^v	0.89 (2)	2.24 (3)	3.115 (4)	165 (2)
N4—H42···O13^vi	0.89 (3)	2.33 (3)	3.210 (4)	170 (3)

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

(IV) catena-Poly[[triaquabarium]-bis[µ₂-hydrogen (4-aminophenyl)arsonato-κ²O:O']] top

Crystal data top

[Ba(C₆H₇AsNO₃)₂(H₂O)₃]	F(000) = 1200
M_r = 623.92	D_x = 2.257 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 1721 reflections
a = 9.9997 (8) Å	θ = 4.6–29.1°
b = 7.7305 (6) Å	µ = 5.79 mm⁻¹
c = 23.979 (2) Å	T = 200 K
β = 98.214 (7)°	Block, colourless
V = 1834.7 (3) Å³	0.36 × 0.22 × 0.16 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	1801 independent reflections
Radiation source: Enhance (Mo) X-ray source	1696 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.4°
ω scans	h = −12→10
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −9→7
T_min = 0.470, T_max = 0.970	l = −29→28
3485 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0262P)² + 0.1187P] where P = (F_o² + 2F_c²)/3
1801 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.85 e Å⁻³
7 restraints	Δρ_min = −0.95 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Ba1	0.75000	0.28700 (3)	0.50000	0.0145 (1)
As1	0.43401 (3)	0.05954 (4)	0.40830 (1)	0.0122 (1)
O1W	0.5902 (2)	0.4300 (3)	0.57359 (12)	0.0261 (8)
O2W	0.75000	0.6465 (5)	0.50000	0.0350 (11)
O11	0.5036 (2)	0.2376 (3)	0.43911 (10)	0.0208 (7)
O12	0.30116 (19)	−0.0164 (3)	0.43546 (9)	0.0205 (7)
O13	0.55376 (19)	−0.1064 (3)	0.41966 (10)	0.0182 (7)
N4	0.3301 (3)	0.0886 (4)	0.15278 (13)	0.0264 (10)
C1	0.3921 (3)	0.0829 (4)	0.32900 (13)	0.0143 (9)
C2	0.2955 (3)	−0.0255 (4)	0.29931 (14)	0.0174 (9)
C3	0.2734 (3)	−0.0207 (4)	0.24105 (13)	0.0174 (9)
C4	0.3463 (3)	0.0915 (4)	0.21100 (13)	0.0175 (9)
C5	0.4402 (3)	0.2028 (4)	0.24149 (15)	0.0202 (10)
C6	0.4626 (3)	0.1983 (4)	0.30002 (14)	0.0180 (9)
H2	0.24500	−0.10250	0.31910	0.0210*
H3	0.20750	−0.09500	0.22110	0.0210*
H5	0.48910	0.28230	0.22190	0.0240*
H6	0.52650	0.27470	0.32020	0.0220*
H11W	0.555 (3)	0.534 (3)	0.5741 (18)	0.0390*
H12W	0.534 (3)	0.358 (4)	0.5849 (17)	0.0390*
H13	0.636 (2)	−0.071 (4)	0.4302 (14)	0.0270*
H21W	0.688 (4)	0.715 (5)	0.509 (2)	0.0520*
H41	0.259 (3)	0.040 (5)	0.1339 (14)	0.0320*
H42	0.355 (4)	0.180 (4)	0.1350 (15)	0.0320*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0157 (1)	0.0125 (2)	0.0147 (2)	0.0000	0.0004 (1)	0.0000
As1	0.0107 (2)	0.0117 (2)	0.0143 (2)	0.0007 (1)	0.0019 (1)	0.0008 (1)
O1W	0.0243 (12)	0.0181 (13)	0.0382 (16)	−0.0006 (9)	0.0120 (11)	−0.0007 (12)
O2W	0.048 (2)	0.0165 (19)	0.042 (2)	0.0000	0.0120 (19)	0.0000
O11	0.0238 (11)	0.0140 (11)	0.0230 (13)	0.0004 (9)	−0.0026 (10)	−0.0031 (10)
O12	0.0134 (10)	0.0255 (13)	0.0236 (13)	0.0007 (9)	0.0066 (9)	0.0071 (11)
O13	0.0114 (10)	0.0137 (11)	0.0289 (13)	0.0020 (9)	0.0006 (9)	0.0009 (11)
N4	0.0287 (16)	0.0326 (18)	0.0177 (16)	0.0031 (13)	0.0025 (13)	0.0022 (14)
C1	0.0143 (14)	0.0159 (15)	0.0125 (16)	0.0046 (12)	0.0013 (12)	0.0006 (14)
C2	0.0141 (14)	0.0161 (16)	0.0225 (18)	−0.0022 (12)	0.0041 (12)	0.0012 (15)
C3	0.0147 (14)	0.0146 (15)	0.0221 (17)	−0.0014 (12)	−0.0004 (13)	−0.0016 (14)
C4	0.0167 (15)	0.0184 (16)	0.0172 (17)	0.0074 (13)	0.0023 (13)	−0.0002 (15)
C5	0.0187 (16)	0.0210 (18)	0.0221 (19)	0.0022 (13)	0.0067 (14)	0.0083 (15)
C6	0.0141 (14)	0.0168 (16)	0.0229 (18)	−0.0003 (12)	0.0015 (13)	0.0000 (14)

Geometric parameters (Å, º) top

Ba1—O1W	2.774 (2)	O13—H13	0.87 (2)
Ba1—O2W	2.779 (4)	N4—C4	1.382 (4)
Ba1—O11	2.706 (2)	N4—H41	0.87 (3)
Ba1—O1Wⁱ	2.774 (2)	N4—H42	0.88 (3)
Ba1—O11ⁱ	2.706 (2)	C1—C2	1.395 (4)
Ba1—O12ⁱⁱ	2.694 (2)	C1—C6	1.384 (4)
Ba1—O12ⁱⁱⁱ	2.694 (2)	C2—C3	1.383 (5)
As1—O11	1.667 (2)	C3—C4	1.398 (4)
As1—O12	1.668 (2)	C4—C5	1.400 (4)
As1—O13	1.749 (2)	C5—C6	1.390 (5)
As1—C1	1.897 (3)	C2—H2	0.9500
O1W—H11W	0.88 (2)	C3—H3	0.9500
O1W—H12W	0.86 (3)	C5—H5	0.9500
O2W—H21W	0.87 (4)	C6—H6	0.9500
O2W—H21Wⁱ	0.87 (4)

O1W—Ba1—O2W	66.52 (5)	Ba1—O1W—H11W	130 (3)
O1W—Ba1—O11	80.60 (7)	Ba1—O1W—H12W	114 (2)
O1W—Ba1—O1Wⁱ	133.03 (7)	H11W—O1W—H12W	108 (3)
O1W—Ba1—O11ⁱ	106.02 (7)	H21W—O2W—H21Wⁱ	105 (4)
O1W—Ba1—O12ⁱⁱ	76.71 (7)	Ba1—O2W—H21Wⁱ	128 (3)
O1W—Ba1—O12ⁱⁱⁱ	148.07 (6)	Ba1—O2W—H21W	128 (3)
O2W—Ba1—O11	98.11 (5)	As1—O13—H13	114 (2)
O1Wⁱ—Ba1—O2W	66.52 (5)	C4—N4—H41	120 (2)
O2W—Ba1—O11ⁱ	98.11 (5)	H41—N4—H42	111 (3)
O2W—Ba1—O12ⁱⁱ	140.93 (5)	C4—N4—H42	118 (2)
O2W—Ba1—O12ⁱⁱⁱ	140.93 (5)	As1—C1—C6	120.6 (2)
O1Wⁱ—Ba1—O11	106.02 (7)	As1—C1—C2	119.5 (2)
O11—Ba1—O11ⁱ	163.77 (7)	C2—C1—C6	119.8 (3)
O11—Ba1—O12ⁱⁱ	88.13 (7)	C1—C2—C3	119.9 (3)
O11—Ba1—O12ⁱⁱⁱ	79.25 (6)	C2—C3—C4	121.2 (3)
O1Wⁱ—Ba1—O11ⁱ	80.60 (7)	N4—C4—C5	120.7 (3)
O1Wⁱ—Ba1—O12ⁱⁱ	148.07 (6)	N4—C4—C3	121.1 (3)
O1Wⁱ—Ba1—O12ⁱⁱⁱ	76.71 (7)	C3—C4—C5	118.2 (3)
O11ⁱ—Ba1—O12ⁱⁱ	79.25 (6)	C4—C5—C6	120.8 (3)
O11ⁱ—Ba1—O12ⁱⁱⁱ	88.13 (7)	C1—C6—C5	120.2 (3)
O12ⁱⁱ—Ba1—O12ⁱⁱⁱ	78.13 (7)	C1—C2—H2	120.00
O11—As1—O12	115.03 (11)	C3—C2—H2	120.00
O11—As1—O13	107.67 (10)	C2—C3—H3	119.00
O11—As1—C1	112.60 (12)	C4—C3—H3	119.00
O12—As1—O13	104.29 (11)	C4—C5—H5	120.00
O12—As1—C1	110.54 (12)	C6—C5—H5	120.00
O13—As1—C1	105.91 (12)	C1—C6—H6	120.00
Ba1—O11—As1	130.25 (11)	C5—C6—H6	120.00
Ba1ⁱⁱ—O12—As1	136.46 (11)

O1W—Ba1—O11—As1	−129.08 (16)	O12—As1—C1—C6	155.9 (2)
O2W—Ba1—O11—As1	166.49 (14)	O13—As1—C1—C2	84.0 (3)
O1Wⁱ—Ba1—O11—As1	98.70 (15)	O13—As1—C1—C6	−91.7 (3)
O12ⁱⁱ—Ba1—O11—As1	−52.24 (15)	As1—C1—C2—C3	−173.9 (2)
O12ⁱⁱⁱ—Ba1—O11—As1	26.03 (14)	C6—C1—C2—C3	1.9 (5)
O12—As1—O11—Ba1	113.92 (14)	As1—C1—C6—C5	173.8 (2)
O13—As1—O11—Ba1	−1.84 (18)	C2—C1—C6—C5	−1.9 (5)
C1—As1—O11—Ba1	−118.21 (16)	C1—C2—C3—C4	−0.1 (5)
O11—As1—O12—Ba1ⁱⁱ	−106.90 (17)	C2—C3—C4—N4	176.0 (3)
O13—As1—O12—Ba1ⁱⁱ	10.78 (18)	C2—C3—C4—C5	−1.7 (5)
C1—As1—O12—Ba1ⁱⁱ	124.21 (17)	N4—C4—C5—C6	−176.0 (3)
O11—As1—C1—C2	−158.6 (2)	C3—C4—C5—C6	1.7 (5)
O11—As1—C1—C6	25.7 (3)	C4—C5—C6—C1	0.1 (5)
O12—As1—C1—C2	−28.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O11^iv	0.88 (2)	1.87 (2)	2.738 (3)	168 (4)
O1W—H12W···O13ⁱⁱ	0.86 (3)	2.13 (3)	2.902 (3)	149 (3)
O13—H13···O12ⁱⁱⁱ	0.87 (2)	1.77 (2)	2.626 (3)	167 (3)
O2W—H21W···O11^iv	0.87 (4)	2.46 (4)	3.229 (2)	149 (3)
N4—H41···O1W^v	0.87 (3)	2.23 (3)	3.092 (4)	171 (3)
N4—H42···O13^vi	0.88 (3)	2.37 (3)	3.241 (4)	170 (3)

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

Acknowledgements

The authors acknowledge support from the Science and Engineering Faculty, Queensland University of Technology.

References

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STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 73| Part 1| January 2017| Pages 61-67

https://doi.org/10.1107/S2053229616019434

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-amino­phenyl)arsonic acid

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

2.2. Refinement

3. Results and discussion

Supporting information

Acknowledgements

References

research papers

The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid