Bis(2,6-di-methyl-anilinium) di-aqua-bis-(di-hydrogen diphosphato-κ(2) O,O')cobaltate(II).

In the title compound, (C8H12N)2[Co(H2P2O7)2(H2O)2], the Co(2+) ion lies on a crystallographic inversion centre and adopts a slightly distorted octa-hedral CoO6 coordination geometry arising from two chelating diphosphate [H2P2O7](2-) ligands and two trans water mol-ecules. In the crystal, the components are linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds and weak aromatic π-π stacking [shortest centroid-centroid separation = 3.778 (2) Å] inter-actions. (001) layers of alternating organic cations and complex inorganic anions are apparent.

Related literature

For related structures, see: Ahmed et al. (2006 ▶); Selmi et al. (2006 ▶, 2009 ▶); Gharbi et al. (1994 ▶); Gharbi & Jouini (2004 ▶); Elboulali et al. (2013a ▶,b ▶); Essehli et al. (2006 ▶).

Experimental

Crystal data

(C8H12N)2[Co(H2P2O7)2(H2O)2]

M = 691.25

Triclinic,

a = 7.320 (3) Å

b = 7.584 (4) Å

c = 13.413 (2) Å

α = 85.35 (3)°

β = 75.56 (2)°

γ = 74.42 (5)°

V = 694.5 (5) Å3

Z = 1

Ag Kα radiation

λ = 0.56087 Å

μ = 0.48 mm−1

T = 293 K

0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.799, T max = 0.982

9085 measured reflections

6683 independent reflections

5514 reflections with I > 2σ(I)

R int = 0.080

2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.168

S = 1.04

6683 reflections

189 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.57 e Å−3

Δρmin = −0.82 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/S1600536814002530/hb7194sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002530/hb7194Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C8H12N)2[Co(H2P2O7)2(H2O)2]	Z = 1
Mr = 691.25	F(000) = 357
Triclinic, P1	Dx = 1.653 Mg m−3
a = 7.320 (3) Å	Ag Kα radiation, λ = 0.56087 Å
b = 7.584 (4) Å	Cell parameters from 25 reflections
c = 13.413 (2) Å	θ = 9–11°
α = 85.35 (3)°	µ = 0.48 mm−1
β = 75.56 (2)°	T = 293 K
γ = 74.42 (5)°	Prism, pink
V = 694.5 (5) Å3	0.40 × 0.30 × 0.20 mm

Enraf–Nonius CAD-4 diffractometer	5514 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.080
Graphite monochromator	θmax = 28.0°, θmin = 2.2°
non–profiled ω scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.799, Tmax = 0.982	l = −5→22
9085 measured reflections	2 standard reflections every 120 min
6683 independent reflections	intensity decay: 5%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0826P)2 + 0.9452P] where P = (Fo2 + 2Fc2)/3
6683 reflections	(Δ/σ)max = 0.005
189 parameters	Δρmax = 1.57 e Å−3
3 restraints	Δρmin = −0.82 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
Co1	0.5000	0.5000	0.5000	0.01796 (9)
P1	0.69129 (7)	0.72084 (7)	0.63065 (4)	0.01948 (10)
P2	0.80524 (7)	0.75466 (7)	0.40670 (4)	0.01867 (10)
O1	0.5727 (2)	0.5931 (2)	0.62242 (13)	0.0242 (3)
O2	0.8322 (3)	0.6463 (2)	0.70245 (15)	0.0287 (3)
H2	0.8794	0.5361	0.6937	0.043*
O3	0.5808 (3)	0.9121 (2)	0.66208 (16)	0.0306 (4)
O4	0.8430 (2)	0.7284 (3)	0.52092 (14)	0.0274 (3)
O5	0.6535 (2)	0.6611 (2)	0.40048 (13)	0.0245 (3)
O6	1.0029 (2)	0.6880 (2)	0.33643 (15)	0.0281 (3)
O7	0.7321 (3)	0.9654 (2)	0.39394 (17)	0.0308 (4)
H7	0.6270	0.9903	0.3778	0.046*
O1W	0.7487 (2)	0.2730 (2)	0.49181 (18)	0.0327 (4)
H1W1	0.748 (6)	0.178 (4)	0.462 (3)	0.049*
H2W1	0.865 (4)	0.291 (5)	0.477 (3)	0.049*
N1	0.3681 (3)	0.7717 (3)	0.26576 (15)	0.0258 (3)
H1A	0.3675	0.8804	0.2865	0.039*
H1B	0.4577	0.6849	0.2885	0.039*
H1C	0.2511	0.7508	0.2908	0.039*
C1	0.4143 (4)	0.7700 (4)	0.15241 (18)	0.0291 (4)
C2	0.2798 (5)	0.8852 (4)	0.1038 (2)	0.0367 (5)
C3	0.3238 (7)	0.8820 (6)	−0.0032 (3)	0.0530 (9)
H3	0.2364	0.9570	−0.0382	0.064*
C4	0.4949 (8)	0.7695 (7)	−0.0583 (2)	0.0616 (12)
H4	0.5210	0.7680	−0.1298	0.074*
C5	0.6260 (6)	0.6602 (6)	−0.0078 (2)	0.0540 (10)
H5	0.7416	0.5865	−0.0457	0.065*
C6	0.5902 (5)	0.6569 (4)	0.0994 (2)	0.0378 (6)
C7	0.0963 (5)	1.0126 (5)	0.1621 (3)	0.0477 (7)
H7A	0.0077	0.9431	0.1985	0.072*
H7B	0.0364	1.0961	0.1147	0.072*
H7C	0.1273	1.0802	0.2102	0.072*
C8	0.7374 (5)	0.5355 (6)	0.1532 (3)	0.0556 (9)
H8A	0.8042	0.6090	0.1783	0.083*
H8B	0.8302	0.4477	0.1057	0.083*
H8C	0.6715	0.4726	0.2100	0.083*

	U11	U22	U33	U12	U13	U23
Co1	0.01549 (15)	0.01757 (15)	0.02352 (17)	−0.00720 (11)	−0.00640 (12)	−0.00003 (12)
P1	0.0174 (2)	0.01835 (19)	0.0248 (2)	−0.00437 (15)	−0.00820 (16)	−0.00249 (16)
P2	0.01319 (18)	0.01767 (19)	0.0260 (2)	−0.00567 (14)	−0.00438 (15)	−0.00018 (16)
O1	0.0256 (7)	0.0265 (7)	0.0252 (7)	−0.0133 (5)	−0.0071 (5)	−0.0016 (5)
O2	0.0286 (7)	0.0271 (7)	0.0330 (8)	−0.0007 (6)	−0.0171 (6)	−0.0051 (6)
O3	0.0286 (7)	0.0206 (6)	0.0450 (10)	−0.0003 (6)	−0.0174 (7)	−0.0082 (6)
O4	0.0206 (6)	0.0389 (8)	0.0276 (7)	−0.0137 (6)	−0.0087 (5)	0.0010 (6)
O5	0.0236 (6)	0.0279 (7)	0.0279 (7)	−0.0154 (5)	−0.0083 (5)	0.0032 (5)
O6	0.0176 (6)	0.0248 (7)	0.0369 (9)	−0.0044 (5)	0.0010 (6)	0.0012 (6)
O7	0.0235 (7)	0.0185 (6)	0.0539 (11)	−0.0040 (5)	−0.0166 (7)	−0.0014 (6)
O1W	0.0191 (6)	0.0259 (7)	0.0549 (12)	−0.0031 (6)	−0.0118 (7)	−0.0099 (7)
N1	0.0265 (8)	0.0297 (8)	0.0232 (8)	−0.0104 (7)	−0.0062 (6)	0.0003 (6)
C1	0.0362 (11)	0.0345 (10)	0.0227 (9)	−0.0204 (9)	−0.0061 (8)	0.0002 (8)
C2	0.0475 (14)	0.0433 (13)	0.0310 (11)	−0.0272 (12)	−0.0166 (10)	0.0089 (10)
C3	0.078 (3)	0.068 (2)	0.0340 (14)	−0.045 (2)	−0.0286 (16)	0.0146 (14)
C4	0.099 (3)	0.080 (3)	0.0228 (12)	−0.057 (3)	−0.0082 (16)	0.0011 (14)
C5	0.070 (2)	0.065 (2)	0.0286 (13)	−0.0376 (19)	0.0110 (14)	−0.0132 (13)
C6	0.0413 (13)	0.0433 (13)	0.0295 (11)	−0.0205 (11)	0.0030 (10)	−0.0084 (10)
C7	0.0455 (16)	0.0484 (17)	0.0554 (19)	−0.0149 (13)	−0.0249 (15)	0.0147 (14)
C8	0.0376 (15)	0.061 (2)	0.057 (2)	−0.0017 (15)	0.0009 (14)	−0.0131 (17)

Co1—O5i	2.0645 (18)	N1—H1B	0.8900
Co1—O5	2.0645 (18)	N1—H1C	0.8900
Co1—O1	2.0744 (17)	C1—C2	1.386 (4)
Co1—O1i	2.0744 (17)	C1—C6	1.396 (4)
Co1—O1Wi	2.130 (2)	C2—C3	1.391 (4)
Co1—O1W	2.130 (2)	C2—C7	1.500 (5)
P1—O1	1.4905 (17)	C3—C4	1.383 (7)
P1—O3	1.495 (2)	C3—H3	0.9300
P1—O2	1.5505 (18)	C4—C5	1.369 (7)
P1—O4	1.6151 (19)	C4—H4	0.9300
P2—O5	1.4910 (17)	C5—C6	1.395 (4)
P2—O6	1.4971 (18)	C5—H5	0.9300
P2—O7	1.5529 (19)	C6—C8	1.509 (6)
P2—O4	1.6110 (19)	C7—H7A	0.9600
O2—H2	0.8200	C7—H7B	0.9600
O7—H7	0.8200	C7—H7C	0.9600
O1W—H1W1	0.856 (18)	C8—H8A	0.9600
O1W—H2W1	0.867 (18)	C8—H8B	0.9600
N1—C1	1.473 (3)	C8—H8C	0.9600
N1—H1A	0.8900
O5i—Co1—O5	180.0	C1—N1—H1B	109.5
O5i—Co1—O1	90.34 (7)	H1A—N1—H1B	109.5
O5—Co1—O1	89.66 (7)	C1—N1—H1C	109.5
O5i—Co1—O1i	89.66 (7)	H1A—N1—H1C	109.5
O5—Co1—O1i	90.34 (7)	H1B—N1—H1C	109.5
O1—Co1—O1i	180.0	C2—C1—C6	123.4 (3)
O5i—Co1—O1Wi	93.83 (8)	C2—C1—N1	117.4 (2)
O5—Co1—O1Wi	86.17 (8)	C6—C1—N1	119.2 (2)
O1—Co1—O1Wi	92.18 (8)	C1—C2—C3	117.1 (3)
O1i—Co1—O1Wi	87.82 (8)	C1—C2—C7	122.5 (3)
O5i—Co1—O1W	86.17 (8)	C3—C2—C7	120.4 (3)
O5—Co1—O1W	93.83 (8)	C4—C3—C2	121.2 (4)
O1—Co1—O1W	87.82 (8)	C4—C3—H3	119.4
O1i—Co1—O1W	92.18 (8)	C2—C3—H3	119.4
O1Wi—Co1—O1W	180.0	C5—C4—C3	120.0 (3)
O1—P1—O3	116.44 (11)	C5—C4—H4	120.0
O1—P1—O2	112.85 (11)	C3—C4—H4	120.0
O3—P1—O2	107.98 (11)	C4—C5—C6	121.5 (4)
O1—P1—O4	108.32 (10)	C4—C5—H5	119.2
O3—P1—O4	108.67 (12)	C6—C5—H5	119.2
O2—P1—O4	101.45 (10)	C5—C6—C1	116.8 (3)
O5—P2—O6	116.77 (11)	C5—C6—C8	120.5 (3)
O5—P2—O7	111.33 (10)	C1—C6—C8	122.8 (3)
O6—P2—O7	109.58 (11)	C2—C7—H7A	109.5
O5—P2—O4	109.55 (9)	C2—C7—H7B	109.5
O6—P2—O4	104.85 (10)	H7A—C7—H7B	109.5
O7—P2—O4	103.77 (11)	C2—C7—H7C	109.5
P1—O1—Co1	133.68 (10)	H7A—C7—H7C	109.5
P1—O2—H2	109.5	H7B—C7—H7C	109.5
P2—O4—P1	129.66 (11)	C6—C8—H8A	109.5
P2—O5—Co1	134.76 (11)	C6—C8—H8B	109.5
P2—O7—H7	109.5	H8A—C8—H8B	109.5
Co1—O1W—H1W1	116 (3)	C6—C8—H8C	109.5
Co1—O1W—H2W1	120 (3)	H8A—C8—H8C	109.5
H1W1—O1W—H2W1	111 (3)	H8B—C8—H8C	109.5
C1—N1—H1A	109.5
O3—P1—O1—Co1	99.39 (16)	O1—Co1—O5—P2	17.64 (15)
O2—P1—O1—Co1	−134.89 (14)	O1i—Co1—O5—P2	−162.36 (15)
O4—P1—O1—Co1	−23.38 (17)	O1Wi—Co1—O5—P2	109.84 (16)
O5i—Co1—O1—P1	178.85 (15)	O1W—Co1—O5—P2	−70.16 (16)
O5—Co1—O1—P1	−1.15 (15)	C6—C1—C2—C3	1.6 (4)
O1i—Co1—O1—P1	10 (100)	N1—C1—C2—C3	−179.6 (2)
O1Wi—Co1—O1—P1	−87.30 (15)	C6—C1—C2—C7	−176.8 (3)
O1W—Co1—O1—P1	92.70 (15)	N1—C1—C2—C7	2.0 (4)
O5—P2—O4—P1	−35.28 (19)	C1—C2—C3—C4	−0.4 (5)
O6—P2—O4—P1	−161.35 (15)	C7—C2—C3—C4	178.1 (3)
O7—P2—O4—P1	83.69 (17)	C2—C3—C4—C5	−0.9 (6)
O1—P1—O4—P2	47.67 (18)	C3—C4—C5—C6	1.0 (6)
O3—P1—O4—P2	−79.70 (17)	C4—C5—C6—C1	0.1 (5)
O2—P1—O4—P2	166.66 (15)	C4—C5—C6—C8	−179.8 (4)
O6—P2—O5—Co1	114.85 (16)	C2—C1—C6—C5	−1.5 (4)
O7—P2—O5—Co1	−118.29 (16)	N1—C1—C6—C5	179.7 (2)
O4—P2—O5—Co1	−4.09 (18)	C2—C1—C6—C8	178.5 (3)
O5i—Co1—O5—P2	−89 (100)	N1—C1—C6—C8	−0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6ii	0.82	1.72	2.532 (3)	174
O7—H7···O3iii	0.82	1.70	2.505 (3)	167
O1W—H2W1···O4ii	0.87 (2)	2.11 (2)	2.947 (3)	161 (4)
O1W—H1W1···O7iv	0.86 (2)	1.96 (2)	2.813 (3)	177 (4)
N1—H1C···O6v	0.89	1.94	2.828 (3)	175
N1—H1A···O3iii	0.89	1.93	2.805 (3)	168
N1—H1B···O5	0.89	2.29	3.005 (3)	138
N1—H1B···O1i	0.89	2.37	3.016 (3)	129
C7—H7C···O2iii	0.96	2.58	3.497 (5)	160
C7—H7A···O6v	0.96	2.57	3.343 (4)	138

Table 1

Selected bond lengths (Å)

Co1—O5	2.0645 (18)
Co1—O1	2.0744 (17)
Co1—O1W	2.130 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O6i	0.82	1.72	2.532 (3)	174
O7—H7⋯O3ii	0.82	1.70	2.505 (3)	167
O1W—H2W1⋯O4i	0.87 (2)	2.11 (2)	2.947 (3)	161 (4)
O1W—H1W1⋯O7iii	0.86 (2)	1.96 (2)	2.813 (3)	177 (4)
N1—H1C⋯O6iv	0.89	1.94	2.828 (3)	175
N1—H1A⋯O3ii	0.89	1.93	2.805 (3)	168
N1—H1B⋯O5	0.89	2.29	3.005 (3)	138
N1—H1B⋯O1v	0.89	2.37	3.016 (3)	129
C7—H7C⋯O2ii	0.96	2.58	3.497 (5)	160
C7—H7A⋯O6iv	0.96	2.57	3.343 (4)	138

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