Bis(2-methyl-anilinium) diaqua-bis[dihydrogendiphosphato(2-)]cobaltate(II).

In the title cobalt(II) complex with 2-methyl-anilinium and diphosphate, (C(7)H(10)N)(2)[Co(H(2)P(2)O(7))(2)(H(2)O)(2)], a three-dimensional network is built up from anionic layers of [Co(H(2)P(2)O(7))(2)(H(2)O)(2)](2-) units and 2-methyl-anilinium cations located between these layers. The dihydrogendiphosphate groups present a bent eclipsed conformation, while the Co(2+) ions lie on inversion centers. An intricate network of O-H⋯O and N-H⋯O hydrogen bonds is established between the different components, assuring the cohesion of the network with other inter-actions, being of electrostatic and van der Waals nature.

Related literature

For organic-inorganic transition metal frameworks, see: Cheetham et al. (1999 ▶); Clearfield (1998 ▶). For the role played by diphosphates in inter­actions between metal centers, see: Xu et al. (2008 ▶). For related structures, see: Essehli et al. (2006 ▶); Gharbi et al. (1994 ▶); Gharbi & Jouini (2004 ▶).

Experimental

Crystal data

(C7H10N)2[Co(H2P2O7)2(H2O)2]

M = 663.19

Triclinic,

a = 7.440 (4) Å

b = 7.455 (2) Å

c = 11.747 (3) Å

α = 91.92 (3)°

β = 94.09 (5)°

γ = 104.67 (2)°

V = 627.8 (4) Å3

Z = 1

Ag Kα radiation

μ = 0.53 mm−1

T = 298 K

0.33 × 0.26 × 0.23 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

4678 measured reflections

4486 independent reflections

3911 reflections with I > 2σ(I)

R int = 0.008

2 standard reflections frequency: 120 min intensity decay: 7%

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.078

S = 1.08

4486 reflections

181 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.29 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: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809044079/fl2278sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044079/fl2278Isup2.hkl

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

(C7H10N)2[Co(H2P2O7)2(H2O)2]	Z = 1
Mr = 663.19	F(000) = 341
Triclinic, P1	Dx = 1.754 Mg m−3
a = 7.440 (4) Å	Ag Kα radiation, λ = 0.56085 Å
b = 7.455 (2) Å	Cell parameters from 25 reflections
c = 11.747 (3) Å	θ = 9–11°
α = 91.92 (3)°	µ = 0.53 mm−1
β = 94.09 (5)°	T = 298 K
γ = 104.67 (2)°	Prism, pink
V = 627.8 (4) Å3	0.33 × 0.26 × 0.23 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.008
Radiation source: Enraf Nonius FR590	θmax = 25.0°, θmin = 2.2°
graphite	h = −11→11
Non–profiled ω scans	k = −11→11
4678 measured reflections	l = 0→17
4486 independent reflections	2 standard reflections every 120 min
3911 reflections with I > 2σ(I)	intensity decay: 7%

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0409P)2 + 0.209P] where P = (Fo2 + 2Fc2)/3
4486 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.43 e Å−3
3 restraints	Δρmin = −0.29 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	0.01548 (6)
P1	0.21765 (4)	0.73669 (4)	0.39318 (3)	0.01617 (7)
P2	0.27309 (4)	0.74457 (4)	0.64170 (3)	0.01643 (7)
O1	0.37007 (14)	0.64107 (14)	0.38682 (8)	0.02204 (18)
O2	0.29044 (15)	0.94783 (14)	0.37491 (11)	0.0272 (2)
H2	0.4017	0.9718	0.3647	0.041*
O3	0.04241 (14)	0.65899 (15)	0.31845 (9)	0.0253 (2)
O4	0.15097 (14)	0.73056 (16)	0.52080 (9)	0.02389 (19)
O5	0.39173 (14)	0.61111 (14)	0.63563 (8)	0.02138 (18)
O6	0.11785 (15)	0.68728 (15)	0.72493 (9)	0.0258 (2)
H6	0.0630	0.5776	0.7116	0.039*
O7	0.37403 (15)	0.94287 (14)	0.67018 (10)	0.0275 (2)
O8	0.25633 (15)	0.27064 (15)	0.49415 (11)	0.0291 (2)
N1	0.29299 (18)	0.25923 (18)	0.76160 (10)	0.0234 (2)
H1A	0.3161	0.1554	0.7340	0.035*
H1B	0.3821	0.3566	0.7445	0.035*
H1C	0.1832	0.2687	0.7308	0.035*
C1	0.2890 (2)	0.2541 (2)	0.88612 (12)	0.0242 (3)
C2	0.4492 (2)	0.2523 (2)	0.95316 (14)	0.0313 (3)
C3	0.4354 (3)	0.2471 (3)	1.07075 (16)	0.0469 (5)
H3	0.5407	0.2471	1.1184	0.056*
C4	0.2716 (4)	0.2419 (4)	1.11818 (16)	0.0550 (6)
H4	0.2668	0.2390	1.1970	0.066*
C5	0.1146 (3)	0.2411 (4)	1.04945 (18)	0.0579 (6)
H5	0.0026	0.2356	1.0815	0.069*
C6	0.1229 (3)	0.2486 (3)	0.93204 (15)	0.0439 (5)
H6A	0.0173	0.2499	0.8849	0.053*
C7	0.6297 (3)	0.2562 (4)	0.90335 (19)	0.0530 (6)
H7A	0.6174	0.1429	0.8587	0.079*
H7B	0.7264	0.2685	0.9639	0.079*
H7C	0.6609	0.3596	0.8555	0.079*
H2W	0.266 (3)	0.174 (2)	0.458 (2)	0.052 (7)*
H1W	0.149 (2)	0.287 (4)	0.481 (2)	0.070 (9)*

	U11	U22	U33	U12	U13	U23
Co1	0.01533 (10)	0.01613 (11)	0.01672 (11)	0.00681 (8)	0.00249 (8)	0.00182 (8)
P1	0.01346 (13)	0.01654 (13)	0.01897 (14)	0.00477 (10)	0.00046 (10)	0.00225 (10)
P2	0.01503 (13)	0.01627 (13)	0.01831 (14)	0.00417 (10)	0.00368 (10)	−0.00060 (10)
O1	0.0232 (4)	0.0268 (5)	0.0211 (4)	0.0146 (4)	0.0039 (3)	0.0048 (3)
O2	0.0226 (5)	0.0166 (4)	0.0435 (6)	0.0046 (3)	0.0094 (4)	0.0045 (4)
O3	0.0192 (4)	0.0266 (5)	0.0276 (5)	0.0033 (4)	−0.0058 (4)	0.0029 (4)
O4	0.0175 (4)	0.0356 (5)	0.0208 (4)	0.0104 (4)	0.0031 (3)	0.0036 (4)
O5	0.0249 (4)	0.0240 (4)	0.0188 (4)	0.0124 (4)	0.0029 (3)	0.0005 (3)
O6	0.0244 (5)	0.0267 (5)	0.0252 (5)	0.0023 (4)	0.0113 (4)	−0.0023 (4)
O7	0.0236 (5)	0.0172 (4)	0.0402 (6)	0.0018 (4)	0.0081 (4)	−0.0043 (4)
O8	0.0194 (5)	0.0226 (5)	0.0449 (6)	0.0051 (4)	0.0037 (4)	−0.0048 (4)
N1	0.0260 (5)	0.0274 (6)	0.0187 (5)	0.0100 (4)	0.0022 (4)	0.0020 (4)
C1	0.0268 (6)	0.0295 (7)	0.0181 (5)	0.0105 (5)	0.0013 (5)	0.0029 (5)
C2	0.0302 (7)	0.0405 (8)	0.0249 (7)	0.0136 (6)	−0.0025 (5)	0.0005 (6)
C3	0.0520 (11)	0.0671 (14)	0.0254 (8)	0.0252 (10)	−0.0082 (7)	0.0032 (8)
C4	0.0703 (15)	0.0815 (17)	0.0207 (7)	0.0315 (13)	0.0095 (8)	0.0077 (9)
C5	0.0507 (12)	0.101 (2)	0.0299 (9)	0.0290 (13)	0.0178 (8)	0.0089 (11)
C6	0.0314 (8)	0.0799 (15)	0.0262 (7)	0.0233 (9)	0.0067 (6)	0.0074 (8)
C7	0.0297 (9)	0.0902 (18)	0.0426 (10)	0.0239 (10)	−0.0023 (8)	−0.0015 (11)

Co1—O1	2.0574 (12)	N1—C1	1.4667 (18)
Co1—O1i	2.0574 (12)	N1—H1A	0.8900
Co1—O5	2.0752 (12)	N1—H1B	0.8900
Co1—O5i	2.0752 (12)	N1—H1C	0.8900
Co1—O8	2.1491 (14)	C1—C6	1.375 (2)
Co1—O8i	2.1491 (14)	C1—C2	1.384 (2)
P1—O1	1.4892 (11)	C2—C3	1.394 (2)
P1—O3	1.4919 (14)	C2—C7	1.496 (3)
P1—O2	1.5570 (11)	C3—C4	1.368 (3)
P1—O4	1.6108 (12)	C3—H3	0.9300
P2—O5	1.4909 (11)	C4—C5	1.371 (3)
P2—O7	1.4933 (12)	C4—H4	0.9300
P2—O6	1.5529 (13)	C5—C6	1.387 (3)
P2—O4	1.6160 (13)	C5—H5	0.9300
O2—H2	0.8200	C6—H6A	0.9300
O6—H6	0.8200	C7—H7A	0.9600
O8—H2W	0.842 (9)	C7—H7B	0.9600
O8—H1W	0.842 (9)	C7—H7C	0.9600
O1—Co1—O1i	180.00 (4)	Co1—O8—H1W	121 (2)
O1—Co1—O5	90.50 (5)	H2W—O8—H1W	111 (2)
O1i—Co1—O5	89.50 (5)	C1—N1—H1A	109.5
O1—Co1—O5i	89.50 (5)	C1—N1—H1B	109.5
O1i—Co1—O5i	90.50 (5)	H1A—N1—H1B	109.5
O5—Co1—O5i	180.00 (3)	C1—N1—H1C	109.5
O1—Co1—O8	91.82 (6)	H1A—N1—H1C	109.5
O1i—Co1—O8	88.18 (6)	H1B—N1—H1C	109.5
O5—Co1—O8	86.64 (6)	C6—C1—C2	122.21 (15)
O5i—Co1—O8	93.36 (6)	C6—C1—N1	118.02 (14)
O1—Co1—O8i	88.18 (6)	C2—C1—N1	119.77 (14)
O1i—Co1—O8i	91.82 (6)	C1—C2—C3	116.73 (17)
O5—Co1—O8i	93.36 (6)	C1—C2—C7	122.34 (15)
O5i—Co1—O8i	86.64 (6)	C3—C2—C7	120.94 (17)
O8—Co1—O8i	180.0	C4—C3—C2	122.00 (18)
O1—P1—O3	117.53 (7)	C4—C3—H3	119.0
O1—P1—O2	110.90 (7)	C2—C3—H3	119.0
O3—P1—O2	109.47 (7)	C3—C4—C5	119.95 (18)
O1—P1—O4	109.65 (7)	C3—C4—H4	120.0
O3—P1—O4	104.33 (7)	C5—C4—H4	120.0
O2—P1—O4	103.91 (7)	C4—C5—C6	119.9 (2)
O5—P2—O7	115.99 (7)	C4—C5—H5	120.1
O5—P2—O6	112.76 (7)	C6—C5—H5	120.1
O7—P2—O6	108.25 (7)	C1—C6—C5	119.22 (18)
O5—P2—O4	108.51 (6)	C1—C6—H6A	120.4
O7—P2—O4	108.93 (7)	C5—C6—H6A	120.4
O6—P2—O4	101.36 (7)	C2—C7—H7A	109.5
P1—O1—Co1	134.55 (7)	C2—C7—H7B	109.5
P1—O2—H2	109.5	H7A—C7—H7B	109.5
P1—O4—P2	129.26 (7)	C2—C7—H7C	109.5
P2—O5—Co1	132.40 (6)	H7A—C7—H7C	109.5
P2—O6—H6	109.5	H7B—C7—H7C	109.5
Co1—O8—H2W	114.2 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O3ii	0.82	1.75	2.5712 (17)	177
O2—H2···O7iii	0.82	1.71	2.522 (2)	169
O8—H2W···O2iv	0.84 (1)	1.98 (1)	2.8199 (18)	179 (3)
O8—H1W···O4ii	0.84 (1)	2.20 (1)	3.020 (2)	164 (3)
N1—H1A···O7iv	0.89	1.89	2.7788 (18)	177
N1—H1B···O5	0.89	2.31	3.0083 (19)	135
N1—H1B···O1i	0.89	2.48	3.105 (2)	127
N1—H1C···O3ii	0.89	1.94	2.821 (2)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O3i	0.82	1.75	2.5712 (17)	177
O2—H2⋯O7ii	0.82	1.71	2.522 (2)	169
O8—H2W⋯O2iii	0.842 (9)	1.978 (10)	2.8199 (18)	179 (3)
O8—H1W⋯O4i	0.842 (9)	2.202 (13)	3.020 (2)	164 (3)
N1—H1A⋯O7iii	0.89	1.89	2.7788 (18)	177
N1—H1B⋯O5	0.89	2.31	3.0083 (19)	135
N1—H1B⋯O1iv	0.89	2.48	3.105 (2)	127
N1—H1C⋯O3i	0.89	1.94	2.821 (2)	168

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