Pseudosymmetric fac-di-aqua-trichlorido[(di-methyl-phosphor-yl)methanaminium-κO]manganese(II).

In the title compound, [Mn(C3H11NOP)Cl3(H2O)2], the Mn(II) metal center has a distorted o-cta-hedral geometry, coordinated by the three chloride ligands showing a facial arrangement. Two water mol-ecules and the O-coordinated dpmaH cation [dpmaH = (di-methyl-phosphor-yl)methanaminium] complete the coordination sphere. Each complex mol-ecule 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)].

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 ▶).

Experimental

Crystal data

[Mn(C3H11NOP)Cl3(H2O)2]

M = 305.42

Monoclinic,

a = 6.3535 (3) Å

b = 10.7304 (6) Å

c = 8.5629 (4) Å

β = 99.490 (2)°

V = 575.79 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.95 mm−1

T = 290 K

0.41 × 0.30 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.723, T max = 0.980

29900 measured reflections

4538 independent reflections

4518 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.014

wR(F 2) = 0.038

S = 1.11

4538 reflections

149 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 2165 Friedel pairs

Flack parameter: 0.136 (5)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813008751/gg2113sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008751/gg2113Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008751/gg2113Isup3.mol

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

[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) Å3	0.41 × 0.30 × 0.26 mm
Z = 2

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 on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.014	w = 1/[σ2(Fo2) + (0.0222P)2 + 0.0303P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 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+0.001xFc2λ3/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	Flack parameter: 0.136 (5)

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	0.004766 (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)*

	U11	U22	U33	U12	U13	U23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Cl2i	0.928 (19)	2.402 (19)	3.3220 (10)	171.3 (15)
N1—H12···Cl2ii	0.82 (2)	2.56 (2)	3.2664 (9)	145.9 (19)
N1—H13···Cl3ii	0.899 (17)	2.436 (17)	3.2193 (8)	145.8 (14)
O1W—H1O···Cl3iii	0.84 (1)	2.42 (1)	3.2360 (8)	164 (2)
O1W—H2O···Cl1iv	0.86 (1)	2.37 (1)	3.2021 (7)	164 (2)
O2W—H3O···Cl1iii	0.82 (1)	2.39 (1)	3.2026 (8)	171 (2)
O2W—H4O···Cl3ii	0.84 (1)	2.35 (1)	3.1635 (8)	166 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯Cl2i	0.928 (19)	2.402 (19)	3.3220 (10)	171.3 (15)
N1—H12⋯Cl2ii	0.82 (2)	2.56 (2)	3.2664 (9)	145.9 (19)
N1—H13⋯Cl3ii	0.899 (17)	2.436 (17)	3.2193 (8)	145.8 (14)
O1W—H1O⋯Cl3iii	0.84 (1)	2.42 (1)	3.2360 (8)	164 (2)
O1W—H2O⋯Cl1iv	0.86 (1)	2.37 (1)	3.2021 (7)	164 (2)
O2W—H3O⋯Cl1iii	0.82 (1)	2.39 (1)	3.2026 (8)	171 (2)
O2W—H4O⋯Cl3ii	0.84 (1)	2.35 (1)	3.1635 (8)	166 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .