Bis(μ₂-dihydrogen phosphato-κ²O:O′)(μ₂-hydrogen phosphato-κ²O:O′)bis­[(1,10-phenanthroline-κ²N,N′)manganese(II)]

In the title manganese phosphate, [Mn₂(C₁₂H₈N₂)₂(H_1.5PO₄)₂(H₂PO₄)], a crystallographic twofold rotation axis passes through the bridging H atom and the P atom carrying two OH groups. The structure consists of distorted trigonal–bipyramidal MnO₃N₂ and tetra­hedral PO₄ units linked through their vertices, giving rise to a discrete dinuclear molecular structure. The crystal structure is stabilized by inter­molecular hydrogen bonds and strong π–π stacking inter­actions (the distance between adjacent phenanthroline rings is 3.24 Å).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.021
• wR factor = 0.050
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.25 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   N2      ..       5.14 su
PLAT432_ALERT_2_C Short Inter X...Y Contact  C3     ..  C10     ..       3.11 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.47
           From the CIF: _reflns_number_total               2965
           Count of symmetry unique reflns         1576
           Completeness (_total/calc)            188.13%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1389
           Fraction of Friedel pairs measured     0.881
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The molecular structure of the title compound, (I), which is isostructural with the previously reported zinc analogue (Ganesan et al., 2003) is illustrated in Fig 1. It consists of distorted trigonal-bipyramidal MnO₃N₂ and tetrahedral PO₄ units. The Mn(II) cation is five coordinated by three oxygen and two nitrogen atoms, with Mn–O distances in of 2.039 (2)—2.088 (1) Å and Mn–N distances in the range 2.250 (2)–2.281 (2) Å. While all the O atoms bonded to Mn are connected to P atoms, only two oxygen atoms attached to P atoms are engaged in P–O–Mn bonds and the other two are terminal ones. The P–O distances range from 1.500 (1)–1.572 (1) Å and O–P–O bond angles fall in the range of 104.71 (8)–116.5 (1)°. It is noteworthy that the hydrogen atom attached to the O(4) atom is shared by two symmetry related H_1.5P(1)O₄ groups. Such O–H–O linkages have been found in zinc carbonate (Zheng et al., 1995) and also described in zinc phosphate (Lin et al., 2003) and gallophosphate (Chen et al., 2000).

The zero-dimensional molecular manganese phosphate is stably stacked into three-dimensional supramolecular arrays via strong H-bonding and π–π stacking interactions. The extensive multi-point hydrogen bonds involving the phosphate groups, forming a sheet-like structure parallel to the bc plane. Neighboring phen ligands from two adjacent layers exhibit a parallel stacking mode and are separated by 3.24 Å indicating significant attractive intermolecular aromatic interaction (Fig. 2).

Related literature

The title complex is isostructural with the previously reported zinc analogue (Ganesan et al., 2003;Lin et al., 2003).

For related literature, see: Chen et al. (2000); Zheng & Adam (1995).

S2. Experimental

Compound (I) was prepared hydrothermally from a mixture of MnCO₃ (0.2294 g), H₃PO₄ (0.4 ml 85wt%), H₃BO₃ (0.7287 g), phen (0.3980 g) and H₂O(18 ml) in the molar ratio of 1:3:6:1:500, which was stirred for 30 min and heated at 443 K for 5 days in a Teflon-lined stainless steel autoclave (27 ml) under autogenous pressure. After cooling to room temperature, orange block-shaped crystals of (I) were obtained and washed with distilled water and dried in air. The product cannot be obtained without H₃BO₃ in the reaction system, although H₃BO₃ is absent in it.

S3. Refinement

All H atoms bound to C were generated geometrically and refined as riding, with C–H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The H atom attached to O4 was located from the difference Fourier map and refined with U_iso(H) = 1.5U_eq(O). All other hydrogen atoms attached to O were located from the difference Fourier map and refined freely.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson,1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The complex molecule [(C12H8N2Mn)2(H1.5PO4)2(H2PO4)] with displacement ellipsoids drawn at the 45% probability level.
	Fig. 2. View of the π–π stacking interactions between neighboring chains.

Bis(µ₂-dihydrogen phosphato-κ²O:O')(µ₂-hydrogen phosphate-κ²O:O')bis[(1,10-phenanthroline-κ²N,N')manganese(II)]

Crystal data

[Mn2(C12H8N2)2(H1.5PO4)2(H2PO4)]	F(000) = 3072
Mr = 760.24	Dx = 1.903 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F2-2d	Cell parameters from 12033 reflections
a = 40.837 (8) Å	θ = 3.0–27.5°
b = 7.457 (2) Å	µ = 1.21 mm^−1
c = 17.424 (4) Å	T = 298 K
V = 5306 (2) Å^3	Block, orange
Z = 8	0.24 × 0.21 × 0.20 mm

Data collection

Rigaku R AXIS RAPID IP diffractometer	2965 independent reflections
Radiation source: fine-focus sealed tube	2889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −52→52
Tmin = 0.781, Tmax = 0.785	k = −8→9
11691 measured reflections	l = −22→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.0237P)^2 + 5.2948P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.002
2965 reflections	Δρmax = 0.34 e Å^−3
212 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (11)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Mn1	0.044642 (7)	0.13553 (4)	0.281370 (17)	0.00725 (7)
N1	0.09857 (4)	0.0839 (2)	0.26712 (9)	0.0089 (3)
N2	0.07098 (4)	0.3889 (2)	0.32082 (10)	0.0098 (3)
C1	0.05716 (5)	0.5367 (3)	0.34805 (12)	0.0118 (4)
H3A	0.0344	0.5442	0.3482	0.014*
C2	0.07522 (5)	0.6825 (3)	0.37674 (12)	0.0128 (4)
H5A	0.0646	0.7832	0.3960	0.015*
C3	0.10869 (5)	0.6737 (3)	0.37589 (12)	0.0111 (4)
H9A	0.1210	0.7688	0.3947	0.013*
C4	0.12447 (5)	0.5194 (2)	0.34630 (12)	0.0091 (4)
C5	0.15935 (5)	0.5011 (3)	0.34250 (12)	0.0119 (4)
H2A	0.1726	0.5952	0.3586	0.014*
C6	0.17320 (5)	0.3490 (3)	0.31582 (12)	0.0114 (4)
H10A	0.1959	0.3393	0.3142	0.014*
C7	0.15337 (5)	0.2018 (2)	0.28990 (12)	0.0097 (4)
C8	0.16672 (5)	0.0404 (3)	0.25998 (12)	0.0123 (4)
H8A	0.1893	0.0234	0.2584	0.015*
C9	0.14595 (5)	−0.0896 (3)	0.23344 (13)	0.0128 (4)
H11A	0.1543	−0.1949	0.2126	0.015*
C10	0.11195 (5)	−0.0634 (3)	0.23779 (11)	0.0100 (4)
H7A	0.0982	−0.1529	0.2194	0.012*
C11	0.11897 (4)	0.2161 (2)	0.29182 (11)	0.0089 (4)
C12	0.10420 (5)	0.3798 (3)	0.32039 (11)	0.0087 (4)
O1	−0.03585 (3)	0.10010 (17)	0.22335 (9)	0.0121 (3)
O2	0.01414 (3)	0.29950 (17)	0.21556 (8)	0.0109 (3)
O3	−0.03932 (3)	0.40311 (19)	0.16080 (9)	0.0115 (3)
H3	−0.0326 (7)	0.495 (4)	0.1817 (19)	0.039 (9)*
O4	−0.00937 (3)	0.15818 (18)	0.09524 (8)	0.0100 (3)
H1	0.0000	0.0000	0.0959	0.015*
P1	−0.017240 (11)	0.23433 (6)	0.17636 (3)	0.00712 (10)
O5	0.02678 (3)	0.08838 (19)	0.38875 (9)	0.0141 (3)
O6	0.01809 (4)	−0.1380 (2)	0.48733 (9)	0.0156 (3)
H2	0.0070 (8)	−0.188 (4)	0.5200 (18)	0.035 (9)*
P2	0.0000	0.0000	0.43408 (4)	0.00887 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.00656 (12)	0.00744 (12)	0.00776 (14)	−0.00075 (10)	−0.00106 (11)	0.00038 (10)
N1	0.0104 (7)	0.0097 (7)	0.0067 (9)	0.0004 (6)	−0.0003 (6)	0.0022 (6)
N2	0.0103 (8)	0.0101 (8)	0.0089 (9)	0.0003 (6)	−0.0010 (6)	0.0014 (6)
C1	0.0107 (9)	0.0132 (9)	0.0114 (10)	0.0015 (7)	0.0000 (7)	0.0010 (8)
C2	0.0172 (10)	0.0107 (9)	0.0104 (10)	0.0023 (7)	−0.0002 (8)	−0.0001 (7)
C3	0.0149 (9)	0.0093 (9)	0.0090 (10)	−0.0021 (7)	−0.0009 (8)	0.0003 (7)
C4	0.0115 (9)	0.0111 (9)	0.0048 (9)	−0.0022 (7)	−0.0017 (7)	0.0027 (7)
C5	0.0097 (9)	0.0136 (10)	0.0125 (10)	−0.0044 (7)	−0.0022 (7)	0.0021 (8)
C6	0.0070 (8)	0.0174 (9)	0.0100 (10)	−0.0011 (7)	−0.0002 (7)	0.0031 (8)
C7	0.0105 (8)	0.0126 (9)	0.0061 (9)	0.0000 (7)	0.0001 (7)	0.0032 (7)
C8	0.0089 (9)	0.0173 (10)	0.0108 (10)	0.0029 (7)	0.0017 (7)	0.0035 (8)
C9	0.0168 (10)	0.0099 (10)	0.0118 (10)	0.0040 (7)	0.0023 (8)	0.0016 (8)
C10	0.0132 (9)	0.0102 (9)	0.0066 (10)	−0.0026 (7)	−0.0006 (8)	0.0020 (7)
C11	0.0103 (9)	0.0099 (8)	0.0065 (9)	−0.0001 (6)	−0.0010 (7)	0.0021 (7)
C12	0.0090 (8)	0.0109 (9)	0.0062 (9)	−0.0011 (7)	−0.0002 (7)	0.0021 (7)
O1	0.0140 (7)	0.0090 (6)	0.0134 (8)	−0.0016 (5)	0.0023 (6)	0.0016 (6)
O2	0.0113 (7)	0.0082 (6)	0.0132 (7)	−0.0007 (5)	−0.0041 (5)	0.0020 (5)
O3	0.0106 (6)	0.0069 (6)	0.0169 (8)	0.0012 (5)	−0.0048 (5)	−0.0015 (5)
O4	0.0119 (7)	0.0100 (6)	0.0082 (7)	−0.0001 (5)	0.0009 (5)	0.0008 (5)
P1	0.0068 (2)	0.0062 (2)	0.0084 (2)	−0.00046 (16)	−0.00107 (17)	0.00098 (18)
O5	0.0138 (7)	0.0174 (7)	0.0111 (7)	−0.0058 (5)	0.0005 (6)	0.0019 (6)
O6	0.0122 (7)	0.0199 (8)	0.0147 (9)	0.0044 (5)	0.0032 (6)	0.0077 (6)
P2	0.0089 (3)	0.0111 (3)	0.0066 (3)	−0.0004 (2)	0.000	0.000

Geometric parameters (Å, º)

Mn1—O5	2.0386 (16)	C7—C11	1.409 (3)
Mn1—O1^i	2.0587 (14)	C7—C8	1.420 (3)
Mn1—O2	2.0884 (14)	C8—C9	1.369 (3)
Mn1—N1	2.2495 (17)	C8—H8A	0.9300
Mn1—N2	2.2805 (16)	C9—C10	1.404 (3)
N1—C10	1.329 (2)	C9—H11A	0.9300
N1—C11	1.360 (2)	C10—H7A	0.9300
N2—C1	1.326 (2)	C11—C12	1.450 (3)
N2—C12	1.358 (2)	O1—P1	1.4998 (14)
C1—C2	1.406 (3)	O1—Mn1^i	2.0587 (14)
C1—H3A	0.9300	O2—P1	1.5313 (13)
C2—C3	1.369 (3)	O3—P1	1.5718 (14)
C2—H5A	0.9300	O3—H3	0.82 (3)
C3—C4	1.416 (3)	O4—P1	1.5568 (15)
C3—H9A	0.9300	O4—H1	1.2402
C4—C12	1.404 (3)	O5—P2	1.5015 (14)
C4—C5	1.433 (3)	O6—P2	1.5704 (15)
C5—C6	1.350 (3)	O6—H2	0.82 (3)
C5—H2A	0.9300	P2—O5^i	1.5015 (14)
C6—C7	1.437 (3)	P2—O6^i	1.5704 (15)
C6—H10A	0.9300
O5—Mn1—O1^i	103.95 (6)	C11—C7—C6	119.76 (17)
O5—Mn1—O2	113.05 (6)	C8—C7—C6	123.10 (17)
O1^i—Mn1—O2	97.24 (6)	C9—C8—C7	119.11 (18)
O5—Mn1—N1	114.96 (6)	C9—C8—H8A	120.4
O1^i—Mn1—N1	88.32 (6)	C7—C8—H8A	120.4
O2—Mn1—N1	128.57 (6)	C8—C9—C10	119.70 (18)
O5—Mn1—N2	92.01 (6)	C8—C9—H11A	120.1
O1^i—Mn1—N2	159.64 (6)	C10—C9—H11A	120.1
O2—Mn1—N2	87.80 (6)	N1—C10—C9	122.85 (18)
N1—Mn1—N2	73.33 (6)	N1—C10—H7A	118.6
C10—N1—C11	117.97 (16)	C9—C10—H7A	118.6
C10—N1—Mn1	125.88 (13)	N1—C11—C7	123.22 (17)
C11—N1—Mn1	116.15 (12)	N1—C11—C12	117.64 (16)
C1—N2—C12	117.95 (17)	C7—C11—C12	119.14 (17)
C1—N2—Mn1	126.56 (13)	N2—C12—C4	123.35 (18)
C12—N2—Mn1	115.34 (13)	N2—C12—C11	117.36 (17)
N2—C1—C2	123.14 (18)	C4—C12—C11	119.29 (17)
N2—C1—H3A	118.4	P1—O1—Mn1^i	157.83 (9)
C2—C1—H3A	118.4	P1—O2—Mn1	123.93 (8)
C3—C2—C1	118.89 (18)	P1—O3—H3	113 (2)
C3—C2—H5A	120.6	P1—O4—H1	113.7
C1—C2—H5A	120.6	O1—P1—O2	113.10 (8)
C2—C3—C4	119.83 (18)	O1—P1—O4	110.90 (8)
C2—C3—H9A	120.1	O2—P1—O4	110.36 (8)
C4—C3—H9A	120.1	O1—P1—O3	109.76 (8)
C12—C4—C3	116.82 (17)	O2—P1—O3	107.63 (8)
C12—C4—C5	120.03 (17)	O4—P1—O3	104.71 (8)
C3—C4—C5	123.15 (18)	P2—O5—Mn1	144.99 (10)
C6—C5—C4	120.84 (18)	P2—O6—H2	117 (2)
C6—C5—H2A	119.6	O5^i—P2—O5	116.52 (13)
C4—C5—H2A	119.6	O5^i—P2—O6	111.46 (8)
C5—C6—C7	120.93 (17)	O5—P2—O6	104.82 (8)
C5—C6—H10A	119.5	O5^i—P2—O6^i	104.82 (8)
C7—C6—H10A	119.5	O5—P2—O6^i	111.46 (8)
C11—C7—C8	117.12 (17)	O6—P2—O6^i	107.57 (12)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^ii	0.82 (3)	1.81 (3)	2.624 (2)	172 (3)
O4—H1···O4^i	1.24	1.24	2.480 (2)	179
O6—H2···O4^iii	0.82 (3)	1.87 (3)	2.665 (2)	166 (3)

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