Hexa­aqua­manganese(II) bis­[hydrogen (4-amino­phen­yl)arsonate] tetra­hydrate

In the structure of the complex salt formed from the reaction of manganese(II) acetate with (4-amino­phen­yl)arsonic acid (p-arsanilic acid), [Mn(H₂O)₆](C₆H₇AsNO₃)₂·4H₂O, the centrosymmetric Mn(H₂O)₆ coordination polyhedron has slightly distorted octa­hedral stereochemistry, with the two hydrogen (4-amino­phen­yl)arsonate anions and the four water mol­ecules of solvation related by inversion. Extensive O—H...O, O—H...N and N—H...O hydrogen bonds link all species, giving an overall three-dimensional supra­molecular structure, which also has weak π–π ring inter­actions [minimum ring-centroid separation = 3.7304 (15) Å]. The structure is isotypic with that of the Mg salt.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.068
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         20 Note
PLAT005_ALERT_5_G No Embedded Refinement Details found  in the CIF     Please Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         13 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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).

Hexaaquamanganese(II) bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate

Crystal data

[Mn(H2O)6](C6H7AsNO3)2·4H2O	F(000) = 678
Mr = 667.19	Dx = 1.739 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1801 reflections
a = 15.2040 (9) Å	θ = 3.9–29.2°
b = 6.7388 (3) Å	µ = 3.17 mm^−1
c = 13.0699 (8) Å	T = 200 K
β = 107.951 (7)°	Block, colourless
V = 1273.91 (13) Å^3	0.35 × 0.26 × 0.18 mm
Z = 2

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2496 independent reflections
Radiation source: Enhance (Mo) X-ray source	2128 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −18→11
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −8→8
Tmin = 0.662, Tmax = 0.980	l = −12→16
5155 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0288P)^2 + 0.7443P] where P = (Fo^2 + 2Fc^2)/3
2496 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.32 e Å^−3
13 restraints	Δρmin = −0.46 e Å^−3

Special details

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 esds 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 > 2sigma(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
As1	0.22953 (2)	0.74539 (4)	0.59945 (2)	0.0134 (1)
O11	0.29612 (12)	0.8896 (3)	0.69561 (14)	0.0193 (6)
O12	0.26527 (12)	0.5118 (3)	0.60584 (15)	0.0193 (5)
O13	0.23649 (13)	0.8281 (3)	0.47601 (15)	0.0200 (6)
N4	−0.17885 (16)	0.7872 (3)	0.5635 (2)	0.0196 (7)
C1	0.10328 (18)	0.7644 (3)	0.5914 (2)	0.0157 (8)
C2	0.07608 (19)	0.7936 (4)	0.6825 (2)	0.0228 (8)
C3	−0.01696 (19)	0.7990 (4)	0.6739 (2)	0.0229 (9)
C4	−0.08400 (18)	0.7749 (4)	0.5742 (2)	0.0170 (8)
C5	−0.05619 (19)	0.7490 (4)	0.4827 (2)	0.0184 (8)
C6	0.03656 (18)	0.7431 (3)	0.4914 (2)	0.0167 (8)
Mn1	0.50000	0.50000	0.50000	0.0164 (2)
O1W	0.44009 (13)	0.4411 (3)	0.62823 (15)	0.0203 (6)
O2W	0.38051 (15)	0.6723 (3)	0.40765 (16)	0.0293 (7)
O3W	0.43599 (15)	0.2291 (3)	0.42193 (18)	0.0281 (7)
O4W	0.26434 (15)	0.2457 (3)	0.26621 (17)	0.0244 (7)
O5W	0.54204 (13)	0.5174 (3)	0.83471 (16)	0.0228 (6)
H2	0.12130	0.80990	0.75080	0.0270*
H3	−0.03530	0.81930	0.73630	0.0280*
H5	−0.10130	0.73540	0.41410	0.0220*
H6	0.05500	0.72450	0.42890	0.0200*
H13	0.223 (2)	0.948 (3)	0.465 (3)	0.0300*
H41	−0.190 (2)	0.764 (4)	0.6237 (18)	0.0230*
H42	−0.2109 (19)	0.704 (4)	0.516 (2)	0.0230*
H11W	0.470 (2)	0.474 (5)	0.6899 (16)	0.0300*
H12W	0.3851 (13)	0.467 (4)	0.624 (3)	0.0300*
H21W	0.340 (2)	0.724 (5)	0.429 (3)	0.0440*
H22W	0.359 (2)	0.674 (5)	0.3397 (15)	0.0440*
H31W	0.469 (2)	0.147 (4)	0.402 (3)	0.0420*
H32W	0.3817 (16)	0.226 (5)	0.375 (2)	0.0420*
H41W	0.266 (2)	0.164 (4)	0.218 (2)	0.0370*
H42W	0.263 (2)	0.359 (3)	0.238 (2)	0.0370*
H51W	0.5943 (15)	0.473 (4)	0.833 (3)	0.0340*
H52W	0.546 (2)	0.636 (3)	0.858 (3)	0.0340*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.0117 (2)	0.0153 (2)	0.0139 (2)	0.0010 (1)	0.0052 (1)	0.0003 (1)
O11	0.0173 (10)	0.0222 (10)	0.0176 (9)	−0.0039 (8)	0.0041 (8)	−0.0026 (8)
O12	0.0162 (9)	0.0169 (9)	0.0253 (10)	0.0029 (7)	0.0073 (8)	0.0013 (8)
O13	0.0234 (10)	0.0224 (10)	0.0179 (10)	0.0081 (8)	0.0117 (8)	0.0048 (9)
N4	0.0141 (12)	0.0240 (12)	0.0221 (13)	−0.0006 (9)	0.0077 (10)	−0.0002 (11)
C1	0.0134 (13)	0.0163 (13)	0.0185 (14)	0.0010 (10)	0.0064 (11)	0.0004 (11)
C2	0.0191 (14)	0.0349 (16)	0.0136 (13)	0.0012 (12)	0.0041 (11)	−0.0003 (12)
C3	0.0209 (15)	0.0351 (16)	0.0148 (14)	0.0037 (12)	0.0085 (12)	0.0026 (12)
C4	0.0153 (13)	0.0149 (13)	0.0230 (14)	0.0012 (10)	0.0091 (11)	0.0019 (11)
C5	0.0172 (14)	0.0201 (14)	0.0163 (13)	0.0005 (10)	0.0028 (11)	0.0003 (11)
C6	0.0174 (13)	0.0196 (14)	0.0159 (13)	0.0013 (10)	0.0091 (11)	−0.0014 (11)
Mn1	0.0156 (3)	0.0203 (3)	0.0145 (3)	0.0014 (2)	0.0065 (2)	−0.0006 (2)
O1W	0.0139 (10)	0.0322 (11)	0.0164 (9)	0.0032 (8)	0.0070 (8)	−0.0001 (9)
O2W	0.0256 (12)	0.0448 (13)	0.0170 (10)	0.0168 (10)	0.0057 (9)	−0.0006 (10)
O3W	0.0240 (12)	0.0276 (12)	0.0313 (12)	0.0008 (9)	0.0064 (10)	−0.0085 (10)
O4W	0.0312 (12)	0.0238 (11)	0.0212 (11)	−0.0031 (9)	0.0126 (9)	−0.0018 (9)
O5W	0.0203 (10)	0.0216 (10)	0.0269 (11)	0.0001 (9)	0.0079 (9)	−0.0045 (9)

Geometric parameters (Å, º)

Mn1—O1W	2.177 (2)	O4W—H41W	0.84 (3)
Mn1—O1W^i	2.177 (2)	O4W—H42W	0.85 (2)
Mn1—O2W	2.180 (2)	O5W—H51W	0.86 (3)
Mn1—O2W^i	2.180 (2)	O5W—H52W	0.85 (2)
Mn1—O3W	2.170 (2)	N4—C4	1.408 (4)
Mn1—O3W^i	2.170 (2)	N4—H41	0.87 (2)
As1—O11	1.6627 (19)	N4—H42	0.87 (3)
As1—O12	1.659 (2)	C1—C6	1.393 (4)
As1—O13	1.7407 (19)	C1—C2	1.390 (4)
As1—C1	1.894 (3)	C2—C3	1.385 (4)
O13—H13	0.84 (2)	C3—C4	1.395 (4)
O1W—H12W	0.84 (2)	C4—C5	1.397 (4)
O1W—H11W	0.82 (2)	C5—C6	1.380 (4)
O2W—H21W	0.83 (3)	C2—H2	0.9500
O2W—H22W	0.847 (19)	C3—H3	0.9500
O3W—H32W	0.86 (3)	C5—H5	0.9500
O3W—H31W	0.84 (3)	C6—H6	0.9500
O11—As1—O12	113.76 (10)	H21W—O2W—H22W	105 (3)
O11—As1—O13	108.46 (9)	Mn1—O3W—H32W	123 (2)
O11—As1—C1	111.90 (10)	H31W—O3W—H32W	107 (3)
O12—As1—O13	103.77 (9)	Mn1—O3W—H31W	118 (2)
O12—As1—C1	112.19 (9)	H41W—O4W—H42W	105 (2)
O13—As1—C1	106.08 (10)	H51W—O5W—H52W	112 (3)
O1W^i—Mn1—O3W	91.42 (8)	C4—N4—H41	112 (2)
O2W^i—Mn1—O3W	89.35 (8)	H41—N4—H42	108 (3)
O3W—Mn1—O3W^i	180.00	C4—N4—H42	112 (2)
O1W^i—Mn1—O2W^i	92.77 (8)	C2—C1—C6	119.7 (3)
O1W^i—Mn1—O3W^i	88.58 (8)	As1—C1—C6	118.5 (2)
O2W^i—Mn1—O3W^i	90.65 (8)	As1—C1—C2	121.7 (2)
O1W^i—Mn1—O2W	87.23 (8)	C1—C2—C3	120.0 (2)
O1W—Mn1—O2W	92.77 (8)	C2—C3—C4	120.5 (2)
O1W—Mn1—O3W	88.58 (8)	N4—C4—C3	121.2 (2)
O1W—Mn1—O1W^i	180.00	C3—C4—C5	119.2 (3)
O1W—Mn1—O2W^i	87.23 (8)	N4—C4—C5	119.6 (2)
O1W—Mn1—O3W^i	91.42 (8)	C4—C5—C6	120.3 (2)
O2W—Mn1—O3W	90.65 (8)	C1—C6—C5	120.3 (2)
O2W—Mn1—O2W^i	180.00	C3—C2—H2	120.00
O2W—Mn1—O3W^i	89.35 (8)	C1—C2—H2	120.00
As1—O13—H13	113 (3)	C2—C3—H3	120.00
Mn1—O1W—H11W	118 (2)	C4—C3—H3	120.00
H11W—O1W—H12W	104 (3)	C6—C5—H5	120.00
Mn1—O1W—H12W	124 (2)	C4—C5—H5	120.00
Mn1—O2W—H21W	128 (3)	C1—C6—H6	120.00
Mn1—O2W—H22W	125 (2)	C5—C6—H6	120.00
O11—As1—C1—C2	−34.0 (2)	As1—C1—C6—C5	177.71 (18)
O11—As1—C1—C6	147.69 (16)	C2—C1—C6—C5	−0.6 (3)
O12—As1—C1—C2	95.2 (2)	C1—C2—C3—C4	0.1 (4)
O12—As1—C1—C6	−83.06 (18)	C2—C3—C4—N4	−177.7 (2)
O13—As1—C1—C2	−152.12 (19)	C2—C3—C4—C5	−1.2 (4)
O13—As1—C1—C6	29.59 (19)	N4—C4—C5—C6	177.9 (2)
As1—C1—C2—C3	−177.48 (19)	C3—C4—C5—C6	1.4 (4)
C6—C1—C2—C3	0.8 (4)	C4—C5—C6—C1	−0.5 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···N4^ii	0.84 (2)	1.90 (2)	2.734 (3)	174 (4)
N4—H41···O4W^iii	0.87 (2)	2.09 (3)	2.911 (3)	158 (3)
N4—H42···O12^iii	0.87 (3)	2.13 (3)	2.982 (3)	169 (3)
O1W—H11W···O5W	0.82 (2)	1.90 (2)	2.715 (3)	173 (3)
O1W—H12W···O12	0.84 (2)	1.79 (2)	2.626 (3)	176 (4)
O2W—H21W···O13	0.83 (3)	1.99 (3)	2.811 (3)	175 (4)
O2W—H22W···O11^iv	0.85 (2)	1.88 (2)	2.704 (3)	164 (3)
O3W—H31W···O5W^v	0.84 (3)	1.96 (3)	2.791 (3)	171 (3)
O3W—H32W···O4W	0.86 (3)	1.91 (3)	2.773 (3)	174 (3)
O4W—H41W···O12^v	0.84 (3)	1.88 (3)	2.725 (3)	177 (3)
O4W—H42W···O11^iv	0.85 (2)	1.90 (2)	2.720 (3)	164 (3)
O5W—H51W···O11^vi	0.86 (3)	1.90 (3)	2.749 (3)	170 (4)
O5W—H52W···O1W^vii	0.85 (2)	2.07 (2)	2.895 (3)	164 (3)

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