Pseudosymmetric fac-di­aqua­trichlorido[(di­methyl­phosphor­yl)methanaminium-κO]manganese(II)

In the title compound, [Mn(C₃H₁₁NOP)Cl₃(H₂O)₂], the Mn^II metal center has a distorted o­cta­hedral geometry, coordinated by the three chloride ligands showing a facial arrangement. Two water mol­ecules and the O-coordinated dpmaH cation [dpmaH = (di­methyl­phosphor­yl)methanaminium] complete the coordination sphere. Each complex mol­ecule is connected to its neighbours by O—H...Cl and N—H...Cl hydrogen bonds. Two of the chloride ligands and the two water ligands form a hydrogen-bonded polymeric sheet in the ab plane. Furthermore, these planes are connected to adjacent planes by hydrogen bonds from the aminium function of cationic dpmaH ligand. A pseudo-mirror plane perpendicular to the b axis in the chiral space group P2₁ is observed together with inversion twinning [ratio = 0.864 (5):0.136 (5)].

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](N-C) = 0.001 Å
• R factor = 0.014
• wR factor = 0.038
• Data-to-parameter ratio = 30.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry .....         91 PerFi

Alert level G
CHEMS02_ALERT_1_G  Please check that you have entered the correct
            _publ_requested_category classification of your compound;
            FI or CI or EI for inorganic; FM or CM or EM for metal-organic;
            FO or CO or EO for organic.
            From the CIF: _publ_requested_category   FI
            From the CIF: _chemical_formula_sum:C3 H15 Cl3 Mn1 N1 O3 P1
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT033_ALERT_4_G Flack x Value Deviates .gt. 2*sigma from Zero ..      0.136
PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem...          m
PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space-group.      P21/m
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  Cl3     ..       11.5 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Mn1    --  O2W     ..        6.7 su
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Manganese complexes are of general interest as these metal centers play important roles in biological systems such as metalloproteins (Wieghardt, 1989). More than one hundred manganese complexes built by aqua, chlorido and any organic donor ligands at the same time are structurally characterized and deposited in the Cambridge Structural Database. If we limit the search on compounds with at least one aqua, one chloride and a ligand with a O-coordinated phosphoryl group the number is reduced to only two examples (Głowiak & Sawka-Dobrowolska, 1977; Kubíček et al., 2003) which are comparable with the title complex. Furthermore, alkyldiphosphinates are known to be efficient tectons (for the term tecton, see: Brunet et al., 1997) to construct hydrogen bonded frameworks (Glidewell et al., 2000). Especially it has also been shown that amino phosphinic anions are able to form hydrogen bonded one-dimensional, two-dimensional and three-dimensional supramolecular architectures (Chen et al., 2010). For the neutral dmpa there are some examples that show its ability to coordinate transition metals (Borisov et al. 1994; Kochel, 2009) and also a salt containing the protonated dpmaH cation has been structurally characterized (Reiss & Jörgens, 2012). The structure determination on fac-diaquatrichlorido((dimethylphosphoryl)methanaminium)manganese(II) is part of our continuing interest in the hydrogen bonding of methylphosphinic acids and its derivatives (Reiss & Engel, 2008) and the field of application as a tectons for the construction of new hydrogen bonded networks (e.g. Meyer et al., 2010).

The title structure crystallizes in the monoclinic, chiral space group P2₁. The asymmetric unit consists of one formula unit of the fac-diaquatrichlorido((dimethylphosphoryl)methanaminium)manganese(II) complex. The three chlorido ligands show a facial arrangement with Mn—Cl distances between 2.5137 (3) and 2.5717 (3) Å which is in excellent agreement with other Mn(II) complexes (Głowiak & Sawka-Dobrowolska, 1977; Kubíček et al., 2003; Karthikeyan et al., 2011). The Cl—Mn—Cl angles of 92.163 (8)° to 93.346 (8)° are in the typical range of hexacoordinate aqua-chlorido manganese(II) complexes (e.g. Feist et al. 1997). The distorted octahedral coordination at the Mn(II) metal center is completed by two water molecules and a O-coordinated dpmaH cation. All Mn—O bond length as well as the geometrical parameters of the dpmaH cation are in the expected ranges. Each manganese complex is connected to adjacent complexes by O–H···Cl and N—H···Cl hydrogen bonds. Two of the chlorido ligands and the two water ligands form a hydrogen bonded two-dimensional polymer in the ab plane (Fig. 1). Adjacent layers are connected to each other by the cationic dpmaH ligand which is located between them. In detail the dpmaH ligand coordinates the manganese of one layer by its oxygen atom and forms a hydrogen bond to the next layer by its aminium group. The hydrogen bonding scheme of the formal two-dimensional polymer in the ab plane is characterized by three different types of annealed rings (Fig. 2; A, B and C-ring). All rings are classified to belong to the R²₂(8) graph-set descriptor (Etter et al., 1990, Bernstein et al., 1995), but they are different in detail. Ring A and B show a pseudo-inversion symmetry (for a more general introduction into pseudo-symmetry, see: Ruck, 2000) whereas ring C seems to have a mirror symmetry. The pseudo-symmetry features of the hydrogen bonding motifs are related to a pseudo-mirror plane present perpendicular to the b axis. According to the checkcif algorithm more than 90% of the atom positions of the title structure fulfill this additional symmetry element. Figure 1 visualizes this pseudosymmetry situation and it is abundantly clear that the aminium group significantly breaks this additional symmetry element. Especially in pseudosymmetric cases where no additional (super-structure) reflections are present a close look on the plausibility of structural model (Reiss, 2002a; Reiss, 2002b; Reiss & Konietzny, 2002;) and on the difference density maps are needed (Jones et al., 1988). In the latter stages of the refinement the presence of inversion twinning (ratio: 0.864 (5) / 0.136 (5)) was detected. The general hydrogen bonding scheme within the ab plane can be abstracted by a so-called constructor graph (Fig. 3; Grell et al., 2002). Especially in the constructor graph of the title structure the pseudosymmetry can be clearly seen. The infrared and Raman spectra of the title compound are shown in Fig. 4. Both spectra show bands similar to those reported for dpmaHCl (Reiss & Jörgens, 2012). A further assignment, especially for the far-infrared region of the Raman spectrum, is difficult as several lines are observed which may belong to modes of the dpma ligand or may result from stretch modes of Mn–O and Mn–Cl bonds.

Related literature

For related dpma compounds, see: Borisov et al. (1994); Kochel (2009); Reiss & Jörgens (2012). For a definition of the term tecton, see: Brunet et al. (1997). For the use of anionic phosphinic acid derivatives as supramolecular tectons, see: Glidewell et al. (2000); Chen et al. (2010). For related methylphosphinic acids and derivatives, see: Reiss & Engel (2008); Meyer et al. (2010). For graph-set theory and its applications, see: Etter et al. (1990); Bernstein et al. (1995); Grell et al. (2002). For related manganese complexes, see: Głowiak & Sawka-Dobrowolska (1977); Feist et al. (1997); Kubíček et al. (2003); Karthikeyan et al. (2011). For manganese complexes as model system for metalloproteins, see: Wieghardt (1989). For examples of pseudo-symmetry, see: Jones et al. (1988); Reiss (2002a,b); Reiss & Konietzny (2002); Ruck (2000).

For related literature, see: .

S2. Experimental

For the synthesis of the title compound (I) equimolar amounts of dpma and manganese(II)chloride tetrahydrate were dissolved in concentrated HCl. Slow evaporation of this solution at room temperature yielded crystals suitable for a crystallographic structure determination.

S3. Refinement

Methyl H-atoms were identified in difference syntheses, idealized and refined using rigid groups allowed to rotate about the P—C bond (AFIX 137 option of the SHELXL97 program). The coordinates of all other H-atoms were refined freely with individual U_isovalues.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. View against the a axis on the hydrogen bonding scheme of the title structure (I). The atoms of the asymmetric unit is labelled and drawn as 45% ellipsoids.
	Fig. 2. View along [001] on a two-dimensional segment of the title structure.Three different hydrogen bonded ring motifs (A, B, C) are shown which are all belonging to the R^22(8) graph-set type.
	Fig. 3. Left part: Wireframe Model of the title structure with the hydrogen bonds shown as arrows. Right part: Constructor-graph (Grell et al., 2002) for the same part of the title structure (large black dots represent the Mn complexes; colour-codes arrows indicate the crystallographically independent hydrogen bonds).
	Fig. 4. Showing the Raman- and the infrared spectra of the title compound.

fac-diaquatrichlorido[(dimethylphosphoryl)methanaminium-κO]manganese(II)

Crystal data

[Mn(C3H11NOP)Cl3(H2O)2]	F(000) = 310
Mr = 305.42	Dx = 1.762 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9869 reflections
a = 6.3535 (3) Å	θ = 3.1–33.6°
b = 10.7304 (6) Å	µ = 1.95 mm^−1
c = 8.5629 (4) Å	T = 290 K
β = 99.490 (2)°	Block, colourless
V = 575.79 (5) Å^3	0.41 × 0.30 × 0.26 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer	4538 independent reflections
Radiation source: fine-focus sealed tube	4518 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 33.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.723, Tmax = 0.980	k = −16→16
29900 measured reflections	l = −13→13

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.014	w = 1/[σ^2(Fo^2) + (0.0222P)^2 + 0.0303P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.038	(Δ/σ)max = 0.001
S = 1.11	Δρmax = 0.49 e Å^−3
4538 reflections	Δρmin = −0.29 e Å^−3
149 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
5 restraints	Extinction coefficient: 0.273 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2165 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.136 (5)

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	0.004766 (16)	0.500568 (11)	−0.133762 (11)	0.01871 (3)
Cl1	0.24906 (3)	0.33264 (2)	−0.20350 (3)	0.02689 (4)
Cl2	−0.18984 (3)	0.51538 (2)	−0.41916 (2)	0.02810 (5)
Cl3	0.27145 (3)	0.673730 (19)	−0.17200 (3)	0.02618 (4)
P1	0.27696 (3)	0.49973 (2)	0.251182 (18)	0.01833 (4)
O1	0.09298 (10)	0.47944 (7)	0.11869 (7)	0.02894 (13)
N1	0.09847 (14)	0.31507 (8)	0.40879 (10)	0.02992 (15)
H11	0.025 (3)	0.3676 (17)	0.467 (2)	0.047 (5)*
H12	0.114 (3)	0.2472 (18)	0.452 (3)	0.054 (5)*
H13	0.017 (3)	0.2997 (16)	0.315 (2)	0.039 (4)*
O1W	−0.21359 (12)	0.65566 (7)	−0.09214 (9)	0.02909 (14)
O2W	−0.24546 (13)	0.36541 (8)	−0.10488 (9)	0.03152 (14)
H1O	−0.3455 (15)	0.645 (2)	−0.121 (2)	0.057 (6)*
H2O	−0.199 (3)	0.6966 (14)	−0.0049 (13)	0.039 (4)*
H3O	−0.3747 (15)	0.365 (2)	−0.135 (2)	0.058 (6)*
H4O	−0.247 (4)	0.325 (2)	−0.0213 (19)	0.079 (7)*
C1	0.30694 (15)	0.36461 (8)	0.38191 (10)	0.02448 (15)
H11A	0.3837	0.2998	0.3358	0.040 (4)*
H12A	0.3909	0.3879	0.4828	0.027 (3)*
C2	0.2410 (2)	0.62945 (10)	0.37378 (13)	0.0359 (2)
H21	0.2240	0.7039	0.3108	0.100 (9)*
H22	0.3636	0.6378	0.4552	0.096 (9)*
H23	0.1161	0.6166	0.4214	0.099 (9)*
C3	0.52844 (13)	0.51400 (13)	0.18863 (10)	0.03147 (18)
H31	0.5500	0.4443	0.1227	0.090 (9)*
H32	0.6393	0.5155	0.2796	0.080 (6)*
H33	0.5322	0.5899	0.1297	0.058 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01908 (5)	0.02042 (5)	0.01630 (5)	−0.00011 (4)	0.00192 (3)	0.00049 (4)
Cl1	0.02524 (9)	0.02786 (9)	0.02755 (8)	0.00643 (7)	0.00433 (6)	0.00031 (7)
Cl2	0.02977 (8)	0.03377 (11)	0.01848 (7)	−0.00040 (7)	−0.00279 (6)	−0.00007 (6)
Cl3	0.02148 (8)	0.02487 (9)	0.03136 (9)	−0.00303 (6)	0.00192 (6)	0.00126 (7)
P1	0.02142 (7)	0.02078 (7)	0.01289 (6)	−0.00034 (7)	0.00309 (5)	0.00136 (7)
O1	0.0264 (3)	0.0411 (4)	0.0174 (2)	−0.0039 (2)	−0.00188 (19)	0.0042 (2)
N1	0.0326 (4)	0.0270 (3)	0.0289 (3)	−0.0090 (3)	0.0016 (3)	0.0044 (3)
O1W	0.0248 (3)	0.0324 (3)	0.0302 (3)	0.0055 (2)	0.0050 (2)	−0.0052 (3)
O2W	0.0267 (3)	0.0393 (4)	0.0281 (3)	−0.0097 (3)	0.0033 (2)	0.0044 (3)
C1	0.0276 (4)	0.0229 (3)	0.0220 (3)	−0.0003 (3)	0.0015 (3)	0.0050 (2)
C2	0.0516 (6)	0.0257 (4)	0.0328 (4)	0.0026 (4)	0.0135 (4)	−0.0048 (3)
C3	0.0238 (3)	0.0482 (6)	0.0234 (3)	−0.0028 (4)	0.0067 (2)	0.0035 (4)

Geometric parameters (Å, º)

Mn1—O1	2.1538 (6)	N1—H13	0.899 (17)
Mn1—O2W	2.1959 (8)	O1W—H1O	0.841 (9)
Mn1—O1W	2.2326 (7)	O1W—H2O	0.858 (9)
Mn1—Cl1	2.5137 (3)	O2W—H3O	0.820 (9)
Mn1—Cl2	2.5554 (2)	O2W—H4O	0.836 (9)
Mn1—Cl3	2.5717 (3)	C1—H11A	0.9700
P1—O1	1.5046 (6)	C1—H12A	0.9700
P1—C3	1.7735 (8)	C2—H21	0.9600
P1—C2	1.7806 (10)	C2—H22	0.9600
P1—C1	1.8225 (8)	C2—H23	0.9600
N1—C1	1.4800 (12)	C3—H31	0.9600
N1—H11	0.928 (19)	C3—H32	0.9600
N1—H12	0.82 (2)	C3—H33	0.9600
O1—Mn1—O2W	83.73 (3)	H11—N1—H13	109.2 (15)
O1—Mn1—O1W	89.08 (3)	H12—N1—H13	104.7 (18)
O2W—Mn1—O1W	89.65 (3)	Mn1—O1W—H1O	118.0 (15)
O1—Mn1—Cl1	95.41 (2)	Mn1—O1W—H2O	122.5 (11)
O2W—Mn1—Cl1	92.30 (2)	H1O—O1W—H2O	106.6 (17)
O1W—Mn1—Cl1	175.27 (2)	Mn1—O2W—H3O	132.3 (15)
O1—Mn1—Cl2	166.216 (19)	Mn1—O2W—H4O	123.2 (17)
O2W—Mn1—Cl2	84.47 (2)	H3O—O2W—H4O	97 (2)
O1W—Mn1—Cl2	83.74 (2)	N1—C1—P1	112.07 (6)
Cl1—Mn1—Cl2	92.163 (8)	N1—C1—H11A	109.2
O1—Mn1—Cl3	97.814 (19)	P1—C1—H11A	109.2
O2W—Mn1—Cl3	174.88 (2)	N1—C1—H12A	109.2
O1W—Mn1—Cl3	85.50 (2)	P1—C1—H12A	109.2
Cl1—Mn1—Cl3	92.413 (8)	H11A—C1—H12A	107.9
Cl2—Mn1—Cl3	93.346 (8)	P1—C2—H21	109.5
O1—P1—C3	114.29 (4)	P1—C2—H22	109.5
O1—P1—C2	113.48 (5)	H21—C2—H22	109.5
C3—P1—C2	108.67 (6)	P1—C2—H23	109.5
O1—P1—C1	109.73 (4)	H21—C2—H23	109.5
C3—P1—C1	104.24 (5)	H22—C2—H23	109.5
C2—P1—C1	105.69 (4)	P1—C3—H31	109.5
P1—O1—Mn1	141.52 (4)	P1—C3—H32	109.5
C1—N1—H11	113.9 (11)	H31—C3—H32	109.5
C1—N1—H12	110.3 (14)	P1—C3—H33	109.5
H11—N1—H12	109.2 (18)	H31—C3—H33	109.5
C1—N1—H13	109.1 (11)	H32—C3—H33	109.5
C3—P1—O1—Mn1	−19.09 (9)	Cl2—Mn1—O1—P1	−168.19 (4)
C2—P1—O1—Mn1	106.29 (8)	Cl3—Mn1—O1—P1	−24.42 (7)
C1—P1—O1—Mn1	−135.75 (7)	O1—P1—C1—N1	−40.28 (7)
O2W—Mn1—O1—P1	160.50 (8)	C3—P1—C1—N1	−163.10 (7)
O1W—Mn1—O1—P1	−109.76 (8)	C2—P1—C1—N1	82.43 (8)
Cl1—Mn1—O1—P1	68.77 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Cl2^i	0.928 (19)	2.402 (19)	3.3220 (10)	171.3 (15)
N1—H12···Cl2^ii	0.82 (2)	2.56 (2)	3.2664 (9)	145.9 (19)
N1—H13···Cl3^ii	0.899 (17)	2.436 (17)	3.2193 (8)	145.8 (14)
O1W—H1O···Cl3^iii	0.84 (1)	2.42 (1)	3.2360 (8)	164 (2)
O1W—H2O···Cl1^iv	0.86 (1)	2.37 (1)	3.2021 (7)	164 (2)
O2W—H3O···Cl1^iii	0.82 (1)	2.39 (1)	3.2026 (8)	171 (2)
O2W—H4O···Cl3^ii	0.84 (1)	2.35 (1)	3.1635 (8)	166 (2)

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