Bis(2-meth­oxy­benzyl­ammonium) di­aqua­bis­(di­hydrogen diphosphato-κ2O,O′)manganate(II) dihydrate

Elboulali, A.; Akriche, S.; Rzaigui, M.

doi:10.1107/S1600536813026366

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page m572

doi:10.1107/S1600536813026366

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Bis(2-methoxybenzylammonium) diaquabis(dihydrogen diphosphato-κ²O,O′)manganate(II) dihydrate

Adel Elboulali,^a Samah Akriche ^a and Mohamed Rzaigui ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: mohamedrzaigui@yahoo.fr

(Received 16 September 2013; accepted 24 September 2013; online 2 October 2013)

The asymmetric unit of the title compound, (C₈H₁₂NO)₂[Mn(H₂P₂O₇)₂(H₂O)₂]·2H₂O, consists of half an Mn^II complex anion, a 2-methoxybenylammonium cation and a solvent water molecule. The Mn^II complex anion lies across an inversion center, and has a slightly distorted octahedral coordination environment for the Mn^II ion, formed by two bidentate dihydrogendiphosphate ligands and two water molecules. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds, forming layers parallel to (100). An intramolecular N—H⋯O hydrogen bond is also observed.

CCDC reference: 962829

Related literature

For related structures, see: Alaoui Tahiri et al. (2003 ); Selmi et al. (2006 , 2009 ); Ahmed et al. (2006 ); Gharbi et al. (1994 ); Gharbi & Jouini (2004 ); Elboulali et al. (2013 ). For valence-sum calculations, see: Brown & Altermatt (1985 ).

Experimental

Crystal data

(C₈H₁₂NO)₂[Mn(H₂P₂O₇)₂(H₂O)₂]·2H₂O
M_r = 755.29
Monoclinic, P 2₁ /c
a = 13.971 (2) Å
b = 12.150 (3) Å
c = 9.169 (2) Å
β = 93.80 (4)°
V = 1553.0 (6) Å³
Z = 2
Ag Kα radiation
λ = 0.56087 Å
μ = 0.37 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.920, T_max = 0.933
9935 measured reflections
7513 independent reflections
4417 reflections with I > 2σ(I)
R_int = 0.028
2 standard reflections every 120 min intensity decay: −1%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.112
S = 0.98
7513 reflections
212 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O3ⁱ	0.82	1.77	2.5689 (17)	164
O5—H5O5⋯O7ⁱⁱ	0.82	1.76	2.5711 (18)	169
O1W—H1W1⋯O3ⁱⁱⁱ	0.86 (1)	1.98 (1)	2.8304 (19)	174 (3)
O1W—H2W1⋯O7ⁱⁱ	0.85 (1)	2.04 (1)	2.879 (2)	167 (2)
O2W—H1W2⋯O7ⁱⁱⁱ	0.86 (1)	2.03 (1)	2.886 (2)	175 (3)
O2W—H2W2⋯O3ⁱⁱ	0.85 (1)	2.05 (1)	2.8842 (19)	164 (2)
N1—H1N1⋯O2W	0.89	1.97	2.826 (2)	160
N1—H2N1⋯O6^iv	0.89	2.06	2.826 (2)	144
N1—H3N1⋯O8	0.89	2.45	2.991 (2)	120
N1—H3N1⋯O2	0.89	2.27	2.957 (2)	134
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 962829

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813026366/lh5654sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026366/lh5654Isup2.hkl

checkCIF report

Comment top

As a part of our study of crystal packing in diphosphate materials, a new hybrid compound of mixed organic-metal cations have been synthesized: (C₈H₁₂NO)₂[Mn(H₂P₂O₇)₂(H₂O)₂]·2H₂O (I).

The asymmetric unit of (I) is made up of a half of mononuclear [Mn(H₂P₂O₇)₂(H₂O)₂]^2- moiety, one of organic cation and one water of crystallization. As the Mn^II ion lies on inversion centre, the complete formula unit is generated by this element of symmetry (Fig. 1).

In the crystal packing, each Mn^II ion is coordinated by two bidentate diphosphate ligands and two coordinated O1W water molecules to form a slightly distorted MnO₆ octahedron. The valence bond calculation (Brown & Altermatt, 1985) gives an effective bond valence of 1.9417 consistent with the cationic charge of +2.

The Mn—O bond distances around the Mn^II ion are in the range 2.1389 (12)–2.1987 (14) Å which is close to those reported for Mn metal in K₂Mn(H₂P₂O₇)₂·2(H₂O) framework (mean Mn—O = 2.173 Å) (Alaoui Tahiri et al., 2003), and slightly longer compared to those around Co in related structures (Selmi et al., 2006,2009; Ahmed et al., 2006). The P₂O₇ ligand has a quasi-eclipsed conformation with O—P—P—O torsion angles averaging 19.5 ° and it bridges the Mn^II ion through O2—P1 and O6—P2 linkages thus producing a bent P₂O₇ group, with a P1—O4—P2 angle of 134.68 (9)° as observed in other M(II)–organic diphosphate frameworks (Selmi et al., 2006, 2009; Ahmed et al., 2006; Gharbi et al., 2004;1994). On the other hand the main bond lenghts of organic cations, are comparable to those observed in the 4-methoxybenzylammonium cations in the (C₈H₁₂NO)₂(H₂P₂O₇) structure reported earlier (Elboulali et al., 2013).

The MnO₆ octahedra are arranged into anionic layers spreading along a-axis at x = 1/2 (Fig.2) via O—H···O hydrogen bonding interactions involving the hydroxyl groups of [H₂P₂O₇]^2- and OW1 water molecules. The remaining uncoordinated O2W water molecules and 2-methoxybenzylammonium cations further link these so as to contribute to their cohesion with O···O and N···O separations ranging from 2.826 (2)to 2.991 (2) Å (Table 1) and build a two-dimensionnal network parallel to (100).

Related literature top

For related structures, see: Alaoui Tahiri et al. (2003); Selmi et al. (2006, 2009); Ahmed et al. (2006); Gharbi et al. (1994); Gharbi & Jouini (2004); Elboulali et al. (2013). For valence-bond calculations, see: Brown & Altermatt (1985).

Experimental top

Crystals of the title compound were synthesized by the reaction of diphosphoric acid H₄P₂O₇ (2 mmol), MnCl₂·4H₂O (0.2 g; 1 mmol) and 2-methoxybenzylamine (0.138 g; 1 mmol) carried out in an acidic medium. The diphosphoric acid, H₄P₂O₇, was obtained from Na₄P₂O₇ by using an ion-exchange resin (Amberlite IR 120).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are represented as dotted lines [Symmetry code: (i) 1 - x, 1 - y, 1 - z]. Only the symmetry unique cation and solvent water molecule are shown.
	Fig. 2. Crystal packing of (I) viewed along the b-axis. The H-atoms not involved in H-bonding are omitted.

(I) top

Crystal data top

(C₈H₁₂NO)₂[Mn(H₂P₂O₇)₂(H₂O)₂]·2H₂O	F(000) = 782
M_r = 755.29	D_x = 1.615 Mg m⁻³
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56087 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 13.971 (2) Å	θ = 9–11°
b = 12.150 (3) Å	µ = 0.37 mm⁻¹
c = 9.169 (2) Å	T = 293 K
β = 93.80 (4)°	Prism, colorless
V = 1553.0 (6) Å³	0.3 × 0.2 × 0.1 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	4417 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 28.0°, θ_min = 2.2°
non–profiled ω scans	h = −2→23
Absorption correction: multi-scan (Blessing, 1995)	k = −20→2
T_min = 0.920, T_max = 0.933	l = −15→15
9935 measured reflections	2 standard reflections every 120 min
7513 independent reflections	intensity decay: −1%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.051P)²] where P = (F_o² + 2F_c²)/3
7513 reflections	(Δ/σ)_max = 0.001
212 parameters	Δρ_max = 0.98 e Å⁻³
6 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

(C₈H₁₂NO)₂[Mn(H₂P₂O₇)₂(H₂O)₂]·2H₂O	V = 1553.0 (6) Å³
M_r = 755.29	Z = 2
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56087 Å
a = 13.971 (2) Å	µ = 0.37 mm⁻¹
b = 12.150 (3) Å	T = 293 K
c = 9.169 (2) Å	0.3 × 0.2 × 0.1 mm
β = 93.80 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	4417 reflections with I > 2σ(I)
Absorption correction: multi-scan (Blessing, 1995)	R_int = 0.028
T_min = 0.920, T_max = 0.933	2 standard reflections every 120 min
9935 measured reflections	intensity decay: −1%
7513 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	6 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.98 e Å⁻³
7513 reflections	Δρ_min = −0.45 e Å⁻³
212 parameters

Special details top

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

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

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

	x	y	z	U_iso*/U_eq
Mn1	0.5000	0.5000	0.5000	0.01975 (7)
P1	0.40929 (3)	0.24580 (3)	0.52770 (4)	0.01970 (8)
P2	0.61630 (3)	0.25518 (3)	0.48651 (4)	0.02071 (8)
O1	0.36950 (13)	0.19825 (11)	0.38021 (12)	0.0416 (4)
H1O1	0.3705	0.2459	0.3170	0.062*
O2	0.40268 (9)	0.36785 (9)	0.53325 (13)	0.0254 (2)
O3	0.36529 (9)	0.18355 (9)	0.64756 (11)	0.0265 (2)
O4	0.51947 (10)	0.20876 (11)	0.54427 (18)	0.0434 (4)
O5	0.68873 (10)	0.23523 (12)	0.61998 (13)	0.0372 (3)
H5O5	0.6689	0.2648	0.6925	0.056*
O6	0.60365 (9)	0.37401 (9)	0.45084 (14)	0.0281 (2)
O7	0.64655 (11)	0.18277 (10)	0.36615 (12)	0.0328 (3)
O8	0.15813 (12)	0.37510 (16)	0.4909 (2)	0.0591 (5)
O1W	0.53579 (13)	0.49630 (11)	0.73711 (14)	0.0397 (3)
H1W1	0.5620 (17)	0.5541 (11)	0.775 (3)	0.060*
H2W1	0.5603 (18)	0.4381 (11)	0.776 (3)	0.060*
O2W	0.24876 (11)	0.49273 (11)	1.02182 (16)	0.0372 (3)
H1W2	0.2768 (17)	0.5511 (12)	1.057 (3)	0.056*
H2W2	0.2729 (17)	0.4349 (11)	1.062 (2)	0.056*
N1	0.27883 (11)	0.49595 (12)	0.72005 (17)	0.0308 (3)
H1N1	0.2782	0.4801	0.8148	0.046*
H2N1	0.3274	0.5412	0.7059	0.046*
H3N1	0.2859	0.4342	0.6696	0.046*
C1	0.18760 (15)	0.54946 (17)	0.6701 (3)	0.0406 (5)
H1A	0.1913	0.5724	0.5692	0.049*
H1B	0.1793	0.6150	0.7282	0.049*
C2	0.10154 (15)	0.47695 (17)	0.6805 (2)	0.0378 (4)
C3	0.0334 (2)	0.4970 (2)	0.7795 (3)	0.0602 (7)
H3	0.0429	0.5533	0.8477	0.072*
C4	−0.0495 (2)	0.4331 (4)	0.7777 (4)	0.0810 (11)
H4	−0.0955	0.4468	0.8443	0.097*
C5	−0.0629 (2)	0.3510 (3)	0.6785 (4)	0.0788 (10)
H5	−0.1188	0.3094	0.6769	0.095*
C6	0.00385 (19)	0.3278 (2)	0.5809 (4)	0.0623 (7)
H6	−0.0061	0.2705	0.5144	0.075*
C7	0.08660 (15)	0.39064 (18)	0.5820 (2)	0.0423 (5)
C8	0.1448 (3)	0.2977 (3)	0.3750 (4)	0.0961 (13)
H8A	0.1356	0.2257	0.4147	0.144*
H8B	0.2004	0.2974	0.3188	0.144*
H8C	0.0894	0.3178	0.3132	0.144*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02626 (17)	0.01297 (12)	0.02024 (13)	−0.00102 (13)	0.00333 (11)	−0.00008 (12)
P1	0.02775 (18)	0.01485 (17)	0.01671 (15)	−0.00373 (16)	0.00300 (13)	0.00009 (13)
P2	0.02652 (19)	0.01738 (17)	0.01837 (16)	0.00336 (16)	0.00264 (13)	0.00126 (14)
O1	0.0818 (11)	0.0257 (6)	0.0167 (5)	−0.0164 (7)	−0.0012 (6)	−0.0003 (5)
O2	0.0296 (6)	0.0157 (5)	0.0311 (6)	−0.0023 (4)	0.0044 (5)	−0.0019 (4)
O3	0.0400 (7)	0.0221 (5)	0.0178 (5)	−0.0083 (5)	0.0045 (5)	0.0020 (4)
O4	0.0319 (7)	0.0262 (6)	0.0733 (10)	0.0032 (5)	0.0135 (7)	0.0195 (7)
O5	0.0430 (7)	0.0460 (8)	0.0218 (5)	0.0175 (6)	−0.0033 (5)	−0.0051 (5)
O6	0.0313 (6)	0.0170 (5)	0.0370 (6)	0.0015 (4)	0.0111 (5)	0.0024 (4)
O7	0.0538 (8)	0.0244 (6)	0.0205 (5)	0.0076 (6)	0.0038 (5)	−0.0016 (4)
O8	0.0425 (9)	0.0722 (12)	0.0618 (10)	0.0020 (9)	−0.0021 (8)	−0.0262 (9)
O1W	0.0682 (10)	0.0235 (6)	0.0254 (6)	−0.0043 (7)	−0.0122 (6)	0.0004 (5)
O2W	0.0397 (7)	0.0319 (7)	0.0395 (7)	0.0032 (6)	−0.0020 (6)	0.0002 (6)
N1	0.0305 (7)	0.0275 (7)	0.0346 (7)	−0.0001 (6)	0.0043 (6)	0.0013 (6)
C1	0.0389 (11)	0.0283 (9)	0.0535 (12)	0.0026 (8)	−0.0065 (9)	0.0057 (8)
C2	0.0314 (9)	0.0397 (11)	0.0417 (10)	0.0038 (8)	−0.0019 (8)	0.0058 (8)
C3	0.0462 (13)	0.0774 (19)	0.0575 (14)	0.0148 (14)	0.0077 (11)	0.0006 (13)
C4	0.0421 (15)	0.125 (3)	0.078 (2)	0.0154 (18)	0.0190 (14)	0.037 (2)
C5	0.0373 (14)	0.093 (2)	0.105 (3)	−0.0157 (15)	−0.0083 (15)	0.049 (2)
C6	0.0424 (13)	0.0519 (15)	0.089 (2)	−0.0130 (11)	−0.0224 (13)	0.0182 (14)
C7	0.0328 (10)	0.0407 (11)	0.0515 (12)	−0.0007 (9)	−0.0107 (9)	0.0063 (9)
C8	0.079 (2)	0.114 (3)	0.092 (2)	0.026 (2)	−0.0193 (19)	−0.062 (2)

Geometric parameters (Å, º) top

Mn1—O2ⁱ	2.1389 (12)	O2W—H2W2	0.854 (9)
Mn1—O2	2.1389 (12)	N1—C1	1.476 (3)
Mn1—O6ⁱ	2.1749 (12)	N1—H1N1	0.8900
Mn1—O6	2.1749 (12)	N1—H2N1	0.8900
Mn1—O1Wⁱ	2.1987 (14)	N1—H3N1	0.8900
Mn1—O1W	2.1987 (14)	C1—C2	1.499 (3)
P1—O2	1.4868 (12)	C1—H1A	0.9700
P1—O3	1.4991 (12)	C1—H1B	0.9700
P1—O1	1.5400 (13)	C2—C3	1.380 (4)
P1—O4	1.6013 (15)	C2—C7	1.390 (3)
P2—O6	1.4883 (13)	C3—C4	1.393 (5)
P2—O7	1.4941 (13)	C3—H3	0.9300
P2—O5	1.5545 (14)	C4—C5	1.355 (5)
P2—O4	1.5886 (15)	C4—H4	0.9300
O1—H1O1	0.8200	C5—C6	1.363 (5)
O5—H5O5	0.8200	C5—H5	0.9300
O8—C7	1.357 (3)	C6—C7	1.385 (3)
O8—C8	1.422 (3)	C6—H6	0.9300
O1W—H1W1	0.855 (9)	C8—H8A	0.9600
O1W—H2W1	0.852 (9)	C8—H8B	0.9600
O2W—H1W2	0.861 (9)	C8—H8C	0.9600

O2ⁱ—Mn1—O2	180.0	C1—N1—H1N1	109.5
O2ⁱ—Mn1—O6ⁱ	86.53 (5)	C1—N1—H2N1	109.5
O2—Mn1—O6ⁱ	93.47 (5)	H1N1—N1—H2N1	109.5
O2ⁱ—Mn1—O6	93.47 (5)	C1—N1—H3N1	109.5
O2—Mn1—O6	86.53 (5)	H1N1—N1—H3N1	109.5
O6ⁱ—Mn1—O6	180.00 (7)	H2N1—N1—H3N1	109.5
O2ⁱ—Mn1—O1Wⁱ	87.07 (6)	N1—C1—C2	113.65 (16)
O2—Mn1—O1Wⁱ	92.93 (6)	N1—C1—H1A	108.8
O6ⁱ—Mn1—O1Wⁱ	94.56 (6)	C2—C1—H1A	108.8
O6—Mn1—O1Wⁱ	85.44 (6)	N1—C1—H1B	108.8
O2ⁱ—Mn1—O1W	92.93 (6)	C2—C1—H1B	108.8
O2—Mn1—O1W	87.07 (6)	H1A—C1—H1B	107.7
O6ⁱ—Mn1—O1W	85.44 (6)	C3—C2—C7	118.7 (2)
O6—Mn1—O1W	94.56 (6)	C3—C2—C1	122.0 (2)
O1Wⁱ—Mn1—O1W	180.0	C7—C2—C1	119.3 (2)
O2—P1—O3	116.66 (7)	C2—C3—C4	120.2 (3)
O2—P1—O1	112.62 (7)	C2—C3—H3	119.9
O3—P1—O1	108.22 (7)	C4—C3—H3	119.9
O2—P1—O4	109.79 (7)	C5—C4—C3	119.7 (3)
O3—P1—O4	103.12 (8)	C5—C4—H4	120.1
O1—P1—O4	105.47 (10)	C3—C4—H4	120.1
O6—P2—O7	116.38 (7)	C4—C5—C6	121.5 (3)
O6—P2—O5	112.70 (8)	C4—C5—H5	119.2
O7—P2—O5	106.76 (7)	C6—C5—H5	119.2
O6—P2—O4	109.04 (7)	C5—C6—C7	119.2 (3)
O7—P2—O4	109.02 (9)	C5—C6—H6	120.4
O5—P2—O4	101.92 (9)	C7—C6—H6	120.4
P1—O1—H1O1	109.5	O8—C7—C6	124.5 (2)
P1—O2—Mn1	134.61 (8)	O8—C7—C2	114.79 (19)
P2—O4—P1	134.68 (9)	C6—C7—C2	120.7 (3)
P2—O5—H5O5	109.5	O8—C8—H8A	109.5
P2—O6—Mn1	135.10 (8)	O8—C8—H8B	109.5
C7—O8—C8	119.1 (2)	H8A—C8—H8B	109.5
Mn1—O1W—H1W1	116.6 (16)	O8—C8—H8C	109.5
Mn1—O1W—H2W1	119.0 (16)	H8A—C8—H8C	109.5
H1W1—O1W—H2W1	111.4 (19)	H8B—C8—H8C	109.5
H1W2—O2W—H2W2	111 (2)

O3—P1—O2—Mn1	136.77 (10)	O1Wⁱ—Mn1—O6—P2	−116.08 (12)
O1—P1—O2—Mn1	−97.20 (12)	O1W—Mn1—O6—P2	63.92 (12)
O4—P1—O2—Mn1	19.99 (13)	N1—C1—C2—C3	111.1 (2)
O6ⁱ—Mn1—O2—P1	−178.37 (10)	N1—C1—C2—C7	−72.7 (2)
O6—Mn1—O2—P1	1.63 (10)	C7—C2—C3—C4	−1.5 (4)
O1Wⁱ—Mn1—O2—P1	86.87 (11)	C1—C2—C3—C4	174.7 (2)
O1W—Mn1—O2—P1	−93.13 (11)	C2—C3—C4—C5	0.2 (4)
O6—P2—O4—P1	22.20 (18)	C3—C4—C5—C6	1.0 (5)
O7—P2—O4—P1	−105.83 (15)	C4—C5—C6—C7	−0.8 (4)
O5—P2—O4—P1	141.55 (15)	C8—O8—C7—C6	7.3 (4)
O2—P1—O4—P2	−38.38 (18)	C8—O8—C7—C2	−172.6 (2)
O3—P1—O4—P2	−163.37 (14)	C5—C6—C7—O8	179.7 (2)
O1—P1—O4—P2	83.20 (16)	C5—C6—C7—C2	−0.5 (4)
O7—P2—O6—Mn1	139.06 (11)	C3—C2—C7—O8	−178.5 (2)
O5—P2—O6—Mn1	−97.14 (12)	C1—C2—C7—O8	5.2 (3)
O4—P2—O6—Mn1	15.27 (14)	C3—C2—C7—C6	1.6 (3)
O2ⁱ—Mn1—O6—P2	157.14 (11)	C1—C2—C7—C6	−174.7 (2)
O2—Mn1—O6—P2	−22.86 (11)

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
O1—H1O1···O3ⁱⁱ	0.82	1.77	2.5689 (17)	164
O5—H5O5···O7ⁱⁱⁱ	0.82	1.76	2.5711 (18)	169
O1W—H1W1···O3^iv	0.86 (1)	1.98 (1)	2.8304 (19)	174 (3)
O1W—H2W1···O7ⁱⁱⁱ	0.85 (1)	2.04 (1)	2.879 (2)	167 (2)
O2W—H1W2···O7^iv	0.86 (1)	2.03 (1)	2.886 (2)	175 (3)
O2W—H2W2···O3ⁱⁱⁱ	0.85 (1)	2.05 (1)	2.8842 (19)	164 (2)
N1—H1N1···O2W	0.89	1.97	2.826 (2)	160
N1—H2N1···O6ⁱ	0.89	2.06	2.826 (2)	144
N1—H3N1···O8	0.89	2.45	2.991 (2)	120
N1—H3N1···O2	0.89	2.27	2.957 (2)	134

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O3ⁱ	0.82	1.77	2.5689 (17)	163.7
O5—H5O5···O7ⁱⁱ	0.82	1.76	2.5711 (18)	168.8
O1W—H1W1···O3ⁱⁱⁱ	0.855 (9)	1.979 (10)	2.8304 (19)	174 (3)
O1W—H2W1···O7ⁱⁱ	0.852 (9)	2.041 (11)	2.879 (2)	167 (2)
O2W—H1W2···O7ⁱⁱⁱ	0.861 (9)	2.027 (10)	2.886 (2)	175 (3)
O2W—H2W2···O3ⁱⁱ	0.854 (9)	2.053 (12)	2.8842 (19)	164 (2)
N1—H1N1···O2W	0.89	1.97	2.826 (2)	159.6
N1—H2N1···O6^iv	0.89	2.06	2.826 (2)	143.9
N1—H3N1···O8	0.89	2.45	2.991 (2)	119.6
N1—H3N1···O2	0.89	2.27	2.957 (2)	134.0

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

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