trans-Dichlorido-tetra-kis-[(di-methyl-phosphor-yl)methanaminium-κO]cobalt(II) tetra-chloridocobaltate(II).

The asymmetric unit of the title structure, [CoCl2(C3H11NOP)4][CoCl4]2, consists of one half of the trans-dichlorido-tetra-kis-[(di-methyl-phosphor-yl)methanaminium]cobalt(II) tetra-cation lying on an inversion center and one tetra-chloridocobaltate(II) dianion on a general position. Four O-coordinated cationic (di-methyl-phosphor-yl)methanaminium (dpmaH(+)) ligands occupy the equatorial coordination sites, whereas the chloride ligands occupy axial positions of the roughly o-cta-hedral coordination polyhedron of the cobalt metal center. Intra-molecular hydrogen bonds between the aminium groups and the O atom of the phosphoryl groups and additional hydrogen bonds between the aminium groups and the chloride ligands are present. Furthermore, four of the six H atoms not involved in intra-molecular bonding of each cobalt(II) tetra-cation form weak hydrogen bonds to four adjacent tetra-chloridocobaltate(II) counter-anions. By these inter-molecular hydrogen bonds, one-dimensional polymeric strands are formed along the b-axis direction. The hydrogen bonding is analyzed using the graph-set method and the structural similarity with dpmaHCl is discussed.

Related literature

For related dpma compounds, see: Dodoff et al. (1990 ▶); Borisov et al. (1994 ▶); Trendafilova et al. (1997 ▶); Kochel (2009 ▶); Reiss & Jörgens (2012 ▶); van Megen et al. (2013 ▶). For a definition of the term tecton, see: Brunet et al. (1997 ▶). For related methyl­phosphinic acids and their 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 cobalt complexes, see: Kubíčk et al. (2003 ▶); Girma et al. (2005 ▶); Guzei et al. (2010 ▶).

Experimental

Crystal data

[CoCl2(C3H11NOP)4][CoCl4]2

M = 963.68

Triclinic,

a = 7.7748 (3) Å

b = 11.1557 (5) Å

c = 12.1205 (5) Å

α = 110.738 (4)°

β = 97.688 (4)°

γ = 104.331 (5)°

V = 923.66 (8) Å3

Z = 1

Mo Kα radiation

μ = 2.25 mm−1

T = 173 K

0.76 × 0.33 × 0.08 mm

Data collection

Oxford Xcalibur diffractometer

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.402, T max = 0.838

15687 measured reflections

4920 independent reflections

4552 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.042

S = 1.09

4920 reflections

197 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.38 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2012 ▶); 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/S1600536813008945/sj5313sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008945/sj5313Isup2.hkl

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

[CoCl2(C3H11NOP)4][CoCl4]2	Z = 1
Mr = 963.68	F(000) = 487
Triclinic, P1	Dx = 1.732 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7748 (3) Å	Cell parameters from 13303 reflections
b = 11.1557 (5) Å	θ = 2.9–32.6°
c = 12.1205 (5) Å	µ = 2.25 mm−1
α = 110.738 (4)°	T = 173 K
β = 97.688 (4)°	Block, blue
γ = 104.331 (5)°	0.76 × 0.33 × 0.08 mm
V = 923.66 (8) Å3

Oxford Xcalibur diffractometer	4920 independent reflections
Graphite monochromator	4552 reflections with I > 2σ(I)
Detector resolution: 16.2711 pixels mm-1	Rint = 0.020
ω scans	θmax = 29.0°, θmin = 2.9°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	h = −10→10
Tmin = 0.402, Tmax = 0.838	k = −15→15
15687 measured reflections	l = −16→16

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)] = 0.018	Hydrogen site location: difference Fourier map
wR(F2) = 0.042	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.012P)2 + 0.5P], where P = (Fo2 + 2Fc2)/3
4920 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark & Reid, 1995).

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.

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.0000	0.5000	0.00707 (5)
Cl1	−0.22848 (4)	0.05961 (3)	0.61151 (3)	0.01037 (6)
P1	0.27356 (4)	−0.01270 (3)	0.73117 (3)	0.00824 (6)
C11	0.48106 (18)	0.09673 (14)	0.84045 (13)	0.0149 (3)
H11A	0.5714	0.1238	0.7997	0.022*
H11B	0.5241	0.0503	0.8858	0.022*
H11C	0.4599	0.1753	0.8949	0.022*
C12	0.31916 (19)	−0.15805 (14)	0.63526 (13)	0.0149 (3)
H12A	0.2069	−0.2229	0.5800	0.022*
H12B	0.3725	−0.1973	0.6841	0.022*
H12C	0.4027	−0.1323	0.5899	0.022*
C13	0.11865 (17)	−0.06627 (14)	0.81714 (12)	0.0117 (2)
H13A	0.1385	−0.1437	0.8293	0.014*
H13B	0.1417	0.0064	0.8963	0.014*
N1	−0.07340 (15)	−0.10285 (12)	0.74832 (11)	0.0112 (2)
H11	−0.093 (2)	−0.0313 (19)	0.7437 (17)	0.022 (5)*
H12	−0.094 (3)	−0.162 (2)	0.6731 (19)	0.026 (5)*
H13	−0.149 (3)	−0.1352 (19)	0.7854 (18)	0.024 (5)*
O1	0.18513 (12)	0.05528 (9)	0.66322 (8)	0.00960 (17)
P2	0.25797 (4)	0.32277 (3)	0.61086 (3)	0.00895 (6)
C21	0.2810 (2)	0.47433 (13)	0.58704 (13)	0.0158 (3)
H21A	0.3016	0.4603	0.5077	0.024*
H21B	0.3827	0.5461	0.6477	0.024*
H21C	0.1710	0.4981	0.5929	0.024*
C22	0.47331 (18)	0.29394 (14)	0.61459 (13)	0.0152 (3)
H22A	0.4593	0.2039	0.6092	0.023*
H22B	0.5591	0.3581	0.6894	0.023*
H22C	0.5177	0.3043	0.5472	0.023*
C23	0.22948 (18)	0.36089 (13)	0.76527 (12)	0.0119 (2)
H23A	0.2637	0.2967	0.7933	0.014*
H23B	0.3122	0.4504	0.8183	0.014*
N2	0.03979 (16)	0.35581 (12)	0.77545 (11)	0.0122 (2)
H21	0.003 (2)	0.4202 (18)	0.7562 (17)	0.019 (4)*
H22	−0.041 (2)	0.2708 (19)	0.7275 (17)	0.018 (4)*
H23	0.035 (3)	0.3711 (19)	0.8492 (19)	0.026 (5)*
O2	0.10036 (12)	0.20618 (9)	0.51575 (8)	0.00961 (17)
Co2	0.17901 (2)	0.34799 (2)	0.10713 (2)	0.01000 (4)
Cl21	0.08194 (5)	0.41433 (3)	0.28405 (3)	0.01496 (7)
Cl22	0.27225 (5)	0.53299 (3)	0.06796 (3)	0.01464 (7)
Cl23	0.38534 (4)	0.24331 (3)	0.14315 (3)	0.01438 (7)
Cl24	−0.04975 (4)	0.19017 (3)	−0.05026 (3)	0.01361 (6)

	U11	U22	U33	U12	U13	U23
Co1	0.00685 (11)	0.00721 (11)	0.00612 (11)	0.00138 (8)	0.00071 (9)	0.00240 (9)
Cl1	0.00962 (13)	0.01193 (13)	0.00975 (14)	0.00396 (11)	0.00322 (11)	0.00394 (11)
P1	0.00786 (14)	0.00935 (14)	0.00738 (15)	0.00274 (11)	0.00126 (11)	0.00342 (12)
C11	0.0116 (6)	0.0186 (7)	0.0110 (6)	0.0019 (5)	−0.0005 (5)	0.0053 (5)
C12	0.0174 (7)	0.0158 (6)	0.0134 (7)	0.0098 (5)	0.0037 (5)	0.0050 (5)
C13	0.0104 (6)	0.0144 (6)	0.0115 (6)	0.0030 (5)	0.0023 (5)	0.0073 (5)
N1	0.0106 (5)	0.0111 (5)	0.0128 (6)	0.0026 (4)	0.0036 (4)	0.0060 (5)
O1	0.0100 (4)	0.0099 (4)	0.0087 (4)	0.0029 (3)	0.0014 (3)	0.0040 (3)
P2	0.00928 (15)	0.00761 (14)	0.00711 (15)	0.00123 (11)	0.00126 (12)	0.00099 (12)
C21	0.0194 (7)	0.0099 (6)	0.0156 (7)	0.0016 (5)	0.0030 (5)	0.0048 (5)
C22	0.0098 (6)	0.0157 (6)	0.0147 (7)	0.0026 (5)	0.0017 (5)	0.0015 (5)
C23	0.0132 (6)	0.0131 (6)	0.0086 (6)	0.0059 (5)	0.0020 (5)	0.0027 (5)
N2	0.0149 (6)	0.0124 (5)	0.0101 (6)	0.0047 (4)	0.0046 (5)	0.0045 (5)
O2	0.0094 (4)	0.0082 (4)	0.0087 (4)	0.0008 (3)	0.0005 (3)	0.0024 (3)
Co2	0.01132 (8)	0.00894 (8)	0.00817 (8)	0.00225 (6)	0.00091 (7)	0.00285 (7)
Cl21	0.02275 (16)	0.01359 (14)	0.01120 (15)	0.00812 (12)	0.00686 (12)	0.00548 (12)
Cl22	0.01898 (16)	0.01075 (14)	0.01158 (15)	0.00080 (12)	0.00219 (12)	0.00476 (12)
Cl23	0.01173 (14)	0.01845 (15)	0.01554 (16)	0.00614 (12)	0.00327 (12)	0.00890 (13)
Cl24	0.01358 (14)	0.01152 (14)	0.01105 (15)	0.00125 (11)	−0.00131 (11)	0.00264 (12)

Co1—O1i	2.0737 (9)	N1—H13	0.87 (2)
Co1—O1	2.0737 (9)	P2—O2	1.5144 (9)
Co1—O2i	2.1671 (9)	P2—C22	1.7791 (14)
Co1—O2	2.1671 (9)	P2—C21	1.7843 (14)
Co1—Cl1i	2.4525 (3)	P2—C23	1.8238 (14)
Co1—Cl1	2.4526 (3)	C21—H21A	0.9600
P1—O1	1.5083 (9)	C21—H21B	0.9600
P1—C11	1.7763 (14)	C21—H21C	0.9600
P1—C12	1.7794 (14)	C22—H22A	0.9600
P1—C13	1.8204 (13)	C22—H22B	0.9600
C11—H11A	0.9600	C22—H22C	0.9600
C11—H11B	0.9600	C23—N2	1.4852 (17)
C11—H11C	0.9600	C23—H23A	0.9700
C12—H12A	0.9600	C23—H23B	0.9700
C12—H12B	0.9600	N2—H21	0.924 (19)
C12—H12C	0.9600	N2—H22	0.920 (19)
C13—N1	1.4886 (17)	N2—H23	0.86 (2)
C13—H13A	0.9700	Co2—Cl22	2.2485 (4)
C13—H13B	0.9700	Co2—Cl24	2.2507 (4)
N1—H11	0.867 (19)	Co2—Cl23	2.2866 (4)
N1—H12	0.88 (2)	Co2—Cl21	2.3024 (4)
O1i—Co1—O1	180.00 (4)	C13—N1—H13	109.9 (13)
O1i—Co1—O2i	88.92 (3)	H11—N1—H13	109.5 (17)
O1—Co1—O2i	91.08 (3)	H12—N1—H13	109.9 (17)
O1i—Co1—O2	91.08 (3)	P1—O1—Co1	138.08 (6)
O1—Co1—O2	88.92 (3)	O2—P2—C22	113.83 (6)
O2i—Co1—O2	180.0	O2—P2—C21	111.21 (6)
O1i—Co1—Cl1i	89.89 (3)	C22—P2—C21	107.23 (7)
O1—Co1—Cl1i	90.11 (3)	O2—P2—C23	112.87 (6)
O2i—Co1—Cl1i	89.54 (3)	C22—P2—C23	104.79 (6)
O2—Co1—Cl1i	90.46 (3)	C21—P2—C23	106.37 (6)
O1i—Co1—Cl1	90.11 (3)	P2—C21—H21A	109.5
O1—Co1—Cl1	89.88 (3)	P2—C21—H21B	109.5
O2i—Co1—Cl1	90.46 (3)	H21A—C21—H21B	109.5
O2—Co1—Cl1	89.54 (3)	P2—C21—H21C	109.5
Cl1i—Co1—Cl1	180.0	H21A—C21—H21C	109.5
O1—P1—C11	113.52 (6)	H21B—C21—H21C	109.5
O1—P1—C12	113.89 (6)	P2—C22—H22A	109.5
C11—P1—C12	107.60 (7)	P2—C22—H22B	109.5
O1—P1—C13	108.03 (6)	H22A—C22—H22B	109.5
C11—P1—C13	105.63 (6)	P2—C22—H22C	109.5
C12—P1—C13	107.70 (7)	H22A—C22—H22C	109.5
P1—C11—H11A	109.5	H22B—C22—H22C	109.5
P1—C11—H11B	109.5	N2—C23—P2	113.44 (9)
H11A—C11—H11B	109.5	N2—C23—H23A	108.9
P1—C11—H11C	109.5	P2—C23—H23A	108.9
H11A—C11—H11C	109.5	N2—C23—H23B	108.9
H11B—C11—H11C	109.5	P2—C23—H23B	108.9
P1—C12—H12A	109.5	H23A—C23—H23B	107.7
P1—C12—H12B	109.5	C23—N2—H21	112.8 (11)
H12A—C12—H12B	109.5	C23—N2—H22	110.3 (11)
P1—C12—H12C	109.5	H21—N2—H22	110.3 (16)
H12A—C12—H12C	109.5	C23—N2—H23	108.5 (13)
H12B—C12—H12C	109.5	H21—N2—H23	107.4 (17)
N1—C13—P1	108.91 (9)	H22—N2—H23	107.3 (17)
N1—C13—H13A	109.9	P2—O2—Co1	128.45 (5)
P1—C13—H13A	109.9	Cl22—Co2—Cl24	108.699 (15)
N1—C13—H13B	109.9	Cl22—Co2—Cl23	119.352 (15)
P1—C13—H13B	109.9	Cl24—Co2—Cl23	106.345 (14)
H13A—C13—H13B	108.3	Cl22—Co2—Cl21	106.654 (14)
C13—N1—H11	109.2 (12)	Cl24—Co2—Cl21	111.513 (15)
C13—N1—H12	111.8 (12)	Cl23—Co2—Cl21	104.233 (14)
H11—N1—H12	106.4 (17)
O1—P1—C13—N1	32.47 (10)	O2—P2—C23—N2	−41.65 (11)
C11—P1—C13—N1	154.27 (9)	C22—P2—C23—N2	−166.05 (9)
C12—P1—C13—N1	−90.96 (10)	C21—P2—C23—N2	80.57 (10)
C11—P1—O1—Co1	158.09 (8)	C22—P2—O2—Co1	60.81 (9)
C12—P1—O1—Co1	34.48 (10)	C21—P2—O2—Co1	−177.94 (7)
C13—P1—O1—Co1	−85.12 (9)	C23—P2—O2—Co1	−58.48 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Cl1	0.867 (19)	2.437 (19)	3.1879 (12)	145.3 (16)
N1—H11···Cl24ii	0.867 (19)	2.730 (19)	3.2573 (13)	120.5 (15)
N1—H12···O2i	0.88 (2)	2.16 (2)	2.9504 (16)	150.3 (17)
N1—H13···Cl23i	0.87 (2)	2.38 (2)	3.2403 (12)	171.3 (17)
N2—H22···Cl1	0.920 (19)	2.250 (19)	3.1697 (13)	177.8 (15)
N2—H21···Cl21iii	0.924 (19)	2.288 (19)	3.2124 (12)	177.8 (16)
N2—H23···Cl22ii	0.86 (2)	2.71 (2)	3.3612 (13)	134.0 (16)
N2—H23···Cl24ii	0.86 (2)	2.70 (2)	3.2989 (12)	128.1 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯Cl1	0.867 (19)	2.437 (19)	3.1879 (12)	145.3 (16)
N1—H11⋯Cl24i	0.867 (19)	2.730 (19)	3.2573 (13)	120.5 (15)
N1—H12⋯O2ii	0.88 (2)	2.16 (2)	2.9504 (16)	150.3 (17)
N1—H13⋯Cl23ii	0.87 (2)	2.38 (2)	3.2403 (12)	171.3 (17)
N2—H22⋯Cl1	0.920 (19)	2.250 (19)	3.1697 (13)	177.8 (15)
N2—H21⋯Cl21iii	0.924 (19)	2.288 (19)	3.2124 (12)	177.8 (16)
N2—H23⋯Cl22i	0.86 (2)	2.71 (2)	3.3612 (13)	134.0 (16)
N2—H23⋯Cl24i	0.86 (2)	2.70 (2)	3.2989 (12)	128.1 (16)

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