Bis(2-meth-oxy-benzyl-ammonium) di-aqua-bis-(di-hydrogen diphosphato-κ(2) O,O')cobaltate(II) dihydrate.

The title compound, (C8H12NO)2[Co(H2P2O7)2(H2O)2]·2H2O, crystallizes isotypically with its Mn(II) analogue. It consists of alternating layers of organic cations and inorganic complex anions, extending parallel to (100). The complex cobaltate(II) anion exhibits -1 symmetry. Its Co(2+) atom has an octa-hedral coordination sphere, defined by two water mol-ecules in apical positions and two H2P2O7 (2-) ligands in equatorial positions. The cohesion between inorganic and organic layers is accomplished by a set of O-H⋯O and N-H⋯O hydrogen bonds involving the organic cation, the inorganic anion and the remaining lattice water mol-ecules.

Related literature

For the isotypic MnII structure, see: Elboulali et al. (2013b ▶). For related structures with diphosphate units, see: Alaoui Tahiri et al. (2003 ▶); Essehli et al. (2005 ▶); Selmi et al. (2006 ▶, 2009 ▶); Ahmed et al. (2006 ▶); Gharbi et al. (1994 ▶); Gharbi & Jouini (2004 ▶); Elboulali et al. (2013a ▶). For distortion index calculations, see: Kobashi et al. (1997 ▶).

Experimental

Crystal data

(C8H12NO)2[Co(H2P2O7)2(H2O)2]·2H2O

M = 759.28

Monoclinic,

a = 14.050 (5) Å

b = 11.971 (5) Å

c = 9.161 (5) Å

β = 93.718 (5)°

V = 1537.6 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.85 mm−1

T = 293 K

0.25 × 0.19 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer

33422 measured reflections

4645 independent reflections

3135 reflections with I > 2σ(I)

R int = 0.081

Refinement

R[F 2 > 2σ(F 2)] = 0.096

wR(F 2) = 0.266

S = 1.08

4645 reflections

212 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.59 e Å−3

Δρmin = −1.26 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); 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/S1600536814006102/wm5011sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006102/wm5011Isup2.hkl

CCDC reference: 992564

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

(C8H12NO)2[Co(H2P2O7)2(H2O)2]·2H2O	F(000) = 786
Mr = 759.28	Dx = 1.640 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 33422 reflections
a = 14.050 (5) Å	θ = 2.2–30.9°
b = 11.971 (5) Å	µ = 0.85 mm−1
c = 9.161 (5) Å	T = 293 K
β = 93.718 (5)°	Prism, pink
V = 1537.6 (12) Å3	0.25 × 0.19 × 0.13 mm
Z = 2

Nonius KappaCCD diffractometer	3135 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.081
Horizonally mounted graphite crystal monochromator	θmax = 30.9°, θmin = 2.2°
Detector resolution: 9 pixels mm-1	h = −20→18
ω and φ CCD rotation images, thick slices scans	k = −17→17
33422 measured reflections	l = −10→13
4645 independent reflections

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)] = 0.096	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.266	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0687P)2 + 17.5972P] where P = (Fo2 + 2Fc2)/3
4645 reflections	(Δ/σ)max = 0.003
212 parameters	Δρmax = 2.59 e Å−3
7 restraints	Δρmin = −1.26 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	0.0248 (3)
P1	0.58873 (11)	0.24678 (12)	0.46988 (14)	0.0240 (3)
P2	0.38517 (11)	0.25622 (12)	0.51633 (14)	0.0249 (3)
O1	0.5946 (3)	0.3708 (3)	0.4662 (4)	0.0278 (8)
O2	0.6336 (3)	0.1843 (3)	0.3488 (4)	0.0302 (9)
O3	0.6288 (4)	0.1972 (4)	0.6168 (5)	0.0471 (13)
H3	0.6494	0.2477	0.6704	0.071*
O4	0.4796 (4)	0.2083 (4)	0.4534 (6)	0.0446 (12)
O5	0.3993 (3)	0.3764 (4)	0.5528 (5)	0.0309 (9)
O6	0.3105 (4)	0.2386 (5)	0.3853 (5)	0.0434 (12)
H6	0.3333	0.2586	0.3094	0.065*
O7	0.3549 (4)	0.1825 (4)	0.6378 (4)	0.0349 (10)
O1W	0.4616 (4)	0.4955 (4)	0.2753 (5)	0.0402 (11)
H1W1	0.441 (6)	0.558 (3)	0.240 (8)	0.060*
H2W1	0.435 (5)	0.438 (3)	0.233 (8)	0.060*
O8	0.8402 (5)	0.3749 (6)	0.5079 (7)	0.0663 (18)
N1	0.7205 (4)	0.4951 (5)	0.2793 (6)	0.0369 (12)
H1A	0.7210	0.4784	0.1847	0.055*
H1B	0.6716	0.5403	0.2934	0.055*
H1C	0.7145	0.4327	0.3307	0.055*
C1	0.8971 (5)	0.4798 (7)	0.3192 (8)	0.0454 (17)
C2	0.9128 (6)	0.3901 (7)	0.4183 (9)	0.0514 (19)
C3	0.9953 (7)	0.3286 (9)	0.4206 (12)	0.068 (3)
H3A	1.0057	0.2708	0.4875	0.082*
C4	1.0628 (8)	0.3536 (11)	0.3228 (15)	0.085 (4)
H4	1.1191	0.3126	0.3253	0.101*
C5	1.0490 (8)	0.4362 (13)	0.2235 (14)	0.087 (4)
H5	1.0952	0.4509	0.1578	0.105*
C6	0.9657 (7)	0.4997 (10)	0.2192 (11)	0.071 (3)
H6A	0.9559	0.5555	0.1493	0.085*
C7	0.8106 (5)	0.5514 (7)	0.3277 (9)	0.0474 (17)
H7A	0.8066	0.5760	0.4280	0.057*
H7B	0.8179	0.6173	0.2679	0.057*
C8	0.8535 (9)	0.2951 (13)	0.6208 (15)	0.103 (5)
H8A	0.8584	0.2220	0.5788	0.154*
H8B	0.8003	0.2973	0.6812	0.154*
H8C	0.9110	0.3118	0.6791	0.154*
O2W	0.7511 (4)	0.4927 (5)	−0.0240 (6)	0.0487 (13)
H1W2	0.732 (6)	0.435 (4)	−0.071 (9)	0.073*
H2W2	0.732 (7)	0.555 (3)	−0.061 (9)	0.073*

	U11	U22	U33	U12	U13	U23
Co1	0.0412 (6)	0.0166 (5)	0.0165 (4)	0.0007 (4)	0.0011 (4)	0.0000 (4)
P1	0.0361 (8)	0.0222 (7)	0.0139 (5)	0.0062 (5)	0.0016 (5)	0.0004 (5)
P2	0.0336 (7)	0.0266 (7)	0.0144 (6)	−0.0044 (6)	0.0011 (5)	−0.0018 (5)
O1	0.031 (2)	0.0224 (19)	0.030 (2)	0.0035 (15)	0.0028 (16)	0.0026 (15)
O2	0.047 (3)	0.029 (2)	0.0150 (16)	0.0088 (17)	0.0041 (16)	−0.0026 (14)
O3	0.089 (4)	0.034 (3)	0.0170 (19)	0.015 (3)	−0.004 (2)	0.0004 (17)
O4	0.050 (3)	0.026 (2)	0.059 (3)	−0.002 (2)	0.009 (2)	−0.018 (2)
O5	0.032 (2)	0.028 (2)	0.034 (2)	0.0022 (16)	0.0104 (17)	−0.0002 (16)
O6	0.047 (3)	0.066 (3)	0.0172 (18)	−0.019 (2)	−0.0035 (18)	0.005 (2)
O7	0.057 (3)	0.029 (2)	0.0189 (18)	−0.0036 (19)	0.0000 (18)	0.0025 (15)
O1W	0.072 (3)	0.026 (2)	0.0205 (19)	0.002 (2)	−0.014 (2)	−0.0017 (16)
O8	0.058 (4)	0.087 (5)	0.052 (3)	−0.003 (3)	−0.001 (3)	0.022 (3)
N1	0.039 (3)	0.040 (3)	0.032 (3)	−0.001 (2)	0.006 (2)	−0.003 (2)
C1	0.035 (4)	0.059 (5)	0.041 (4)	−0.004 (3)	−0.006 (3)	−0.004 (3)
C2	0.039 (4)	0.058 (5)	0.054 (5)	−0.003 (3)	−0.012 (3)	−0.005 (4)
C3	0.051 (5)	0.073 (7)	0.078 (7)	0.003 (4)	−0.021 (5)	−0.013 (5)
C4	0.053 (6)	0.099 (9)	0.100 (9)	0.018 (6)	−0.006 (6)	−0.037 (8)
C5	0.062 (7)	0.130 (11)	0.072 (7)	−0.013 (7)	0.022 (5)	−0.036 (7)
C6	0.055 (6)	0.102 (8)	0.055 (5)	−0.016 (5)	0.007 (4)	−0.002 (5)
C7	0.047 (4)	0.046 (4)	0.048 (4)	0.002 (3)	−0.007 (3)	−0.002 (3)
C8	0.069 (7)	0.140 (12)	0.096 (9)	−0.025 (7)	−0.019 (6)	0.058 (9)
O2W	0.056 (3)	0.051 (3)	0.038 (3)	−0.005 (3)	−0.003 (2)	0.001 (2)

Co1—O1i	2.075 (4)	N1—H1A	0.8900
Co1—O1	2.075 (4)	N1—H1B	0.8900
Co1—O1Wi	2.095 (4)	N1—H1C	0.8900
Co1—O1W	2.095 (4)	C1—C6	1.393 (12)
Co1—O5	2.124 (4)	C1—C2	1.414 (12)
Co1—O5i	2.124 (4)	C1—C7	1.494 (11)
P1—O1	1.488 (4)	C2—C3	1.373 (12)
P1—O2	1.509 (4)	C3—C4	1.379 (17)
P1—O3	1.543 (4)	C3—H3A	0.9300
P1—O4	1.598 (5)	C4—C5	1.349 (18)
P2—O5	1.488 (5)	C4—H4	0.9300
P2—O7	1.503 (4)	C5—C6	1.393 (16)
P2—O6	1.556 (4)	C5—H5	0.9300
P2—O4	1.588 (5)	C6—H6A	0.9300
O3—H3	0.8200	C7—H7A	0.9700
O6—H6	0.8200	C7—H7B	0.9700
O1W—H1W1	0.86 (2)	C8—H8A	0.9600
O1W—H2W1	0.86 (2)	C8—H8B	0.9600
O8—C2	1.362 (11)	C8—H8C	0.9600
O8—C8	1.411 (12)	O2W—H1W2	0.85 (2)
N1—C7	1.477 (9)	O2W—H2W2	0.85 (2)
O1i—Co1—O1	180.0 (2)	C7—N1—H1B	109.5
O1i—Co1—O1Wi	87.73 (18)	H1A—N1—H1B	109.5
O1—Co1—O1Wi	92.27 (18)	C7—N1—H1C	109.5
O1i—Co1—O1W	92.27 (18)	H1A—N1—H1C	109.5
O1—Co1—O1W	87.73 (18)	H1B—N1—H1C	109.5
O1Wi—Co1—O1W	180.000 (1)	C6—C1—C2	117.8 (8)
O1i—Co1—O5	92.42 (16)	C6—C1—C7	122.5 (8)
O1—Co1—O5	87.58 (16)	C2—C1—C7	119.7 (7)
O1Wi—Co1—O5	85.82 (19)	O8—C2—C3	125.7 (9)
O1W—Co1—O5	94.18 (19)	O8—C2—C1	113.4 (7)
O1i—Co1—O5i	87.58 (16)	C3—C2—C1	120.9 (9)
O1—Co1—O5i	92.42 (16)	C2—C3—C4	119.3 (11)
O1Wi—Co1—O5i	94.18 (19)	C2—C3—H3A	120.4
O1W—Co1—O5i	85.82 (19)	C4—C3—H3A	120.4
O5—Co1—O5i	180.00 (16)	C5—C4—C3	121.5 (11)
O1—P1—O2	116.8 (2)	C5—C4—H4	119.2
O1—P1—O3	112.7 (3)	C3—C4—H4	119.2
O2—P1—O3	107.7 (3)	C4—C5—C6	120.1 (11)
O1—P1—O4	109.8 (2)	C4—C5—H5	119.9
O2—P1—O4	103.4 (3)	C6—C5—H5	119.9
O3—P1—O4	105.4 (3)	C1—C6—C5	120.3 (11)
O5—P2—O7	116.2 (2)	C1—C6—H6A	119.9
O5—P2—O6	112.2 (3)	C5—C6—H6A	119.9
O7—P2—O6	106.4 (3)	N1—C7—C1	114.0 (6)
O5—P2—O4	109.2 (2)	N1—C7—H7A	108.7
O7—P2—O4	109.9 (3)	C1—C7—H7A	108.7
O6—P2—O4	102.0 (3)	N1—C7—H7B	108.7
P1—O1—Co1	134.7 (3)	C1—C7—H7B	108.7
P1—O3—H3	109.5	H7A—C7—H7B	107.6
P2—O4—P1	132.9 (3)	O8—C8—H8A	109.5
P2—O5—Co1	134.7 (2)	O8—C8—H8B	109.5
P2—O6—H6	109.5	H8A—C8—H8B	109.5
Co1—O1W—H1W1	114 (5)	O8—C8—H8C	109.5
Co1—O1W—H2W1	123 (5)	H8A—C8—H8C	109.5
H1W1—O1W—H2W1	114 (3)	H8B—C8—H8C	109.5
C2—O8—C8	117.6 (8)	H1W2—O2W—H2W2	116 (3)
C7—N1—H1A	109.5
O2—P1—O1—Co1	136.9 (3)	O1Wi—Co1—O5—P2	−116.7 (4)
O3—P1—O1—Co1	−97.5 (4)	O1W—Co1—O5—P2	63.3 (4)
O4—P1—O1—Co1	19.7 (4)	O5i—Co1—O5—P2	−67 (100)
O1i—Co1—O1—P1	−141 (100)	C8—O8—C2—C3	5.4 (14)
O1Wi—Co1—O1—P1	88.9 (4)	C8—O8—C2—C1	−173.5 (9)
O1W—Co1—O1—P1	−91.1 (4)	C6—C1—C2—O8	−177.8 (8)
O5—Co1—O1—P1	3.2 (4)	C7—C1—C2—O8	4.2 (10)
O5i—Co1—O1—P1	−176.8 (4)	C6—C1—C2—C3	3.3 (12)
O5—P2—O4—P1	23.1 (6)	C7—C1—C2—C3	−174.7 (8)
O7—P2—O4—P1	−105.4 (5)	O8—C2—C3—C4	179.9 (9)
O6—P2—O4—P1	142.0 (5)	C1—C2—C3—C4	−1.3 (14)
O1—P1—O4—P2	−39.1 (6)	C2—C3—C4—C5	−0.8 (16)
O2—P1—O4—P2	−164.5 (5)	C3—C4—C5—C6	0.8 (18)
O3—P1—O4—P2	82.6 (5)	C2—C1—C6—C5	−3.3 (14)
O7—P2—O5—Co1	140.4 (4)	C7—C1—C6—C5	174.7 (9)
O6—P2—O5—Co1	−96.9 (4)	C4—C5—C6—C1	1.3 (17)
O4—P2—O5—Co1	15.5 (5)	C6—C1—C7—N1	111.2 (9)
O1i—Co1—O5—P2	155.7 (4)	C2—C1—C7—N1	−70.9 (9)
O1—Co1—O5—P2	−24.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ii	0.82	1.85	2.553 (6)	143
O6—H6···O7iii	0.82	1.77	2.571 (6)	166
O1W—H1W1···O2iv	0.86 (2)	1.98 (3)	2.827 (6)	168 (7)
O1W—H2W1···O7iii	0.86 (2)	2.00 (2)	2.851 (6)	171 (8)
N1—H1A···O2W	0.89	1.99	2.840 (8)	159
N1—H1A···O3iii	0.89	2.53	2.988 (7)	113
N1—H1B···O5i	0.89	2.04	2.810 (7)	145
N1—H1C···O1	0.89	2.28	2.944 (7)	131
N1—H1C···O8	0.89	2.42	2.972 (9)	120
O2W—H1W2···O2iii	0.85 (2)	2.08 (4)	2.885 (7)	157 (9)
O2W—H2W2···O7iv	0.85 (2)	2.06 (4)	2.876 (7)	161 (9)

Table 1

Selected bond lengths (Å)

Co1—O1	2.075 (4)
Co1—O1W	2.095 (4)
Co1—O5	2.124 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2i	0.82	1.85	2.553 (6)	143
O6—H6⋯O7ii	0.82	1.77	2.571 (6)	166
O1W—H1W1⋯O2iii	0.86 (2)	1.98 (3)	2.827 (6)	168 (7)
O1W—H2W1⋯O7ii	0.86 (2)	2.00 (2)	2.851 (6)	171 (8)
N1—H1A⋯O2W	0.89	1.99	2.840 (8)	159
N1—H1A⋯O3ii	0.89	2.53	2.988 (7)	113
N1—H1B⋯O5iv	0.89	2.04	2.810 (7)	145
N1—H1C⋯O1	0.89	2.28	2.944 (7)	131
N1—H1C⋯O8	0.89	2.42	2.972 (9)	120
O2W—H1W2⋯O2ii	0.85 (2)	2.08 (4)	2.885 (7)	157 (9)
O2W—H2W2⋯O7iii	0.85 (2)	2.06 (4)	2.876 (7)	161 (9)

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