Bis(2-meth-oxy-benzyl-ammonium) di-aqua-bis-(di-hydrogen diphosphato-κ(2) O,O')manganate(II) dihydrate.

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-meth-oxy-benyl-ammonium cation and a solvent water mol-ecule. The Mn(II) complex anion lies across an inversion center, and has a slightly distorted octa-hedral coordination environment for the Mn(II) ion, formed by two bidentate dihydrogendiphosphate ligands and two water mol-ecules. In the crystal, the components are linked by O-H⋯O and N-H⋯O hydrogen bonds, forming layers parallel to (100). An intra-molecular N-H⋯O hydrogen bond is also observed.

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 = 755.29

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.112

S = 0.98

7513 reflections

212 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.98 e Å−3

Δρmin = −0.45 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C8H12NO)2[Mn(H2P2O7)2(H2O)2]·2H2O	F(000) = 782
Mr = 755.29	Dx = 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

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

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(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3
7513 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.98 e Å−3
6 restraints	Δρmin = −0.45 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O3iv	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···O7iv	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

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⋯O6iv	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) ; (ii) ; (iii) ; (iv) .