Pyridinium diaqua-bis-(methyl-enediphospho-nato-κO,O')chromate(III) tetra-hydrate.

In the title complex, (C(5)H(6)N)[Cr(CH(4)O(6)P(2))(2)(H(2)O)(2)]·4H(2)O, the Cr(III) atom, lying on an inversion centre, is coordinated by two bidentate methyl-ene diphospho-nate ligands and two water molecules in a distorted octa-hedral coordination geometry. The pyridinium cation is located on an inversion centre, with an N atom and a C atom sharing a position each at a half occupancy. A three-dimensional network is constructed by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds between the pyridin-ium cation, complex anion and uncoordinated water mol-ecules.

Related literature

For general background to metal-organic frameworks with diphospho­nic acids, see: Barthelet et al. (2002 ▶). For related structures, see: Byun et al. (2006 ▶); Suh et al. (1997 ▶); Van der Merwe et al. (2009 ▶); Visser et al. (2010 ▶).

Experimental

Crystal data

(C5H6N)[Cr(CH4O6P2)2(H2O)2]·4H2O

M = 588.17

Triclinic,

a = 7.206 (5) Å

b = 7.485 (5) Å

c = 10.984 (5) Å

α = 107.085 (5)°

β = 106.128 (5)°

γ = 94.496 (5)°

V = 535.7 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.92 mm−1

T = 100 K

0.22 × 0.16 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; (Bruker, 2001 ▶) T min = 0.843, T max = 0.931

8784 measured reflections

2632 independent reflections

2483 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.070

S = 1.05

2632 reflections

179 parameters

16 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.62 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810028990/hy2333sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028990/hy2333Isup2.hkl

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

(C5H6N)[Cr(CH4O6P2)2(H2O)2]·4H2O	Z = 1
Mr = 588.17	F(000) = 303
Triclinic, P1	Dx = 1.823 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.206 (5) Å	Cell parameters from 6300 reflections
b = 7.485 (5) Å	θ = 0.8–0.9°
c = 10.984 (5) Å	µ = 0.92 mm−1
α = 107.085 (5)°	T = 100 K
β = 106.128 (5)°	Cuboid, green
γ = 94.496 (5)°	0.22 × 0.16 × 0.08 mm
V = 535.7 (6) Å3

Bruker APEXII CCD diffractometer	2483 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.020
Absorption correction: multi-scan (SADABS; (Bruker, 2001)	θmax = 28.3°, θmin = 4.1°
Tmin = 0.843, Tmax = 0.931	h = −9→9
8784 measured reflections	k = −9→6
2632 independent reflections	l = −14→14

Refinement on F2	16 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.0342P)2 + 0.4874P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.070	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.47 e Å−3
2632 reflections	Δρmin = −0.62 e Å−3
179 parameters

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cr1	0.5000	0.5000	0.5000	0.0082 (3)
P2	0.2173 (2)	0.79359 (19)	0.41325 (14)	0.0086 (4)
P1	0.29362 (19)	0.7622 (2)	0.69142 (14)	0.0085 (4)
O2	0.4491 (6)	0.6457 (6)	0.6635 (4)	0.0110 (8)
O5	−0.0069 (6)	0.7069 (6)	0.3539 (4)	0.0128 (8)
O3	0.3700 (6)	0.8943 (6)	0.8418 (4)	0.0134 (8)
H3	0.4774	0.9569	0.8570	0.020*
O7	0.3373 (6)	0.6353 (6)	0.3947 (4)	0.0113 (8)
O9	−0.0373 (8)	0.7358 (7)	0.8942 (5)	0.0235 (10)
O1	0.7325 (6)	0.6953 (6)	0.5401 (4)	0.0121 (8)
C1	0.2683 (8)	0.9145 (8)	0.5903 (6)	0.0108 (10)
H4	0.3885	1.0063	0.6226	0.013*
H5	0.1633	0.9841	0.6027	0.013*
O4	0.0957 (6)	0.6494 (6)	0.6673 (4)	0.0118 (8)
O8	0.2601 (7)	0.9720 (7)	1.1133 (5)	0.0198 (10)
N1	0.381 (7)	0.479 (8)	0.070 (5)	0.028 (12)	0.50
H1	0.3025	0.4691	0.1145	0.034*	0.50
C4	0.381 (8)	0.466 (10)	0.078 (5)	0.024 (10)	0.50
H4A	0.3051	0.4405	0.1294	0.029*	0.50
C3	0.5612 (13)	0.5896 (11)	0.1367 (8)	0.0312 (17)
H3A	0.6025	0.6454	0.2295	0.037*
C2	0.3206 (12)	0.3837 (11)	−0.0627 (8)	0.0322 (17)
H2	0.2008	0.3014	−0.1034	0.039*
O6	0.2543 (6)	0.9385 (6)	0.3492 (4)	0.0133 (8)
H8	0.193 (16)	0.882 (13)	1.042 (9)	0.06 (3)*
H7	0.262 (14)	0.950 (13)	1.184 (7)	0.03 (2)*
H1B	0.844 (10)	0.677 (12)	0.577 (8)	0.03 (2)*
H1A	0.731 (13)	0.806 (9)	0.573 (8)	0.025*
H6	−0.032 (11)	0.597 (8)	0.352 (9)	0.03 (3)*
H9A	0.002 (13)	0.710 (13)	0.828 (8)	0.03 (2)*
H10	−0.110 (17)	0.817 (16)	0.888 (14)	0.07 (4)*

	U11	U22	U33	U12	U13	U23
Cr1	0.0067 (6)	0.0081 (6)	0.0107 (6)	0.0020 (4)	0.0035 (4)	0.0035 (5)
P2	0.0072 (6)	0.0076 (7)	0.0120 (7)	0.0015 (5)	0.0031 (5)	0.0042 (5)
P1	0.0068 (6)	0.0084 (7)	0.0103 (7)	0.0011 (5)	0.0032 (5)	0.0025 (5)
O2	0.0103 (18)	0.0121 (19)	0.0119 (19)	0.0050 (15)	0.0043 (15)	0.0042 (15)
O5	0.0077 (18)	0.011 (2)	0.019 (2)	0.0004 (15)	0.0019 (15)	0.0053 (16)
O3	0.0110 (18)	0.013 (2)	0.0126 (19)	−0.0004 (15)	0.0036 (15)	0.0006 (16)
O7	0.0103 (18)	0.0116 (19)	0.0136 (19)	0.0046 (15)	0.0047 (15)	0.0048 (15)
O9	0.029 (3)	0.024 (3)	0.021 (2)	0.004 (2)	0.014 (2)	0.007 (2)
O1	0.0082 (18)	0.0088 (19)	0.019 (2)	0.0013 (15)	0.0034 (16)	0.0043 (16)
C1	0.010 (2)	0.008 (2)	0.013 (3)	0.0014 (19)	0.003 (2)	0.003 (2)
O4	0.0085 (18)	0.0114 (19)	0.0153 (19)	0.0000 (14)	0.0039 (15)	0.0043 (15)
O8	0.018 (2)	0.026 (2)	0.013 (2)	−0.0028 (18)	0.0032 (17)	0.0052 (19)
N1	0.04 (2)	0.028 (18)	0.033 (19)	0.019 (13)	0.019 (16)	0.023 (13)
C4	0.026 (18)	0.019 (15)	0.018 (15)	−0.001 (12)	−0.008 (12)	0.008 (13)
C3	0.042 (5)	0.020 (3)	0.021 (3)	0.007 (3)	−0.004 (3)	0.006 (3)
C2	0.033 (4)	0.023 (4)	0.029 (4)	0.000 (3)	−0.008 (3)	0.009 (3)
O6	0.0148 (19)	0.0108 (19)	0.016 (2)	0.0016 (15)	0.0053 (16)	0.0073 (16)

Cr1—O1	1.991 (4)	O1—H1B	0.83 (6)
Cr1—O2	1.956 (4)	O1—H1A	0.80 (6)
Cr1—O7	1.964 (4)	C1—H4	0.9700
P2—O6	1.499 (4)	C1—H5	0.9700
P2—O7	1.519 (4)	O8—H8	0.85 (7)
P2—O5	1.568 (4)	O8—H7	0.83 (6)
P2—C1	1.804 (6)	N1—C2	1.34 (5)
P1—O4	1.512 (4)	N1—C3	1.36 (4)
P1—O4	1.512 (4)	N1—H1	0.8600
P1—O2	1.515 (4)	C4—C3	1.40 (5)
P1—O3	1.568 (4)	C4—C2	1.41 (5)
P1—C1	1.797 (6)	C4—H4A	0.9300
O5—H6	0.83 (5)	C3—C2i	1.371 (13)
O3—H3	0.8200	C3—H3A	0.9300
O9—H9A	0.83 (6)	C2—C3i	1.371 (13)
O9—H10	0.84 (7)	C2—H2	0.9300
O2ii—Cr1—O2	180.00 (15)	P2—O5—H6	114 (5)
O2ii—Cr1—O7	88.35 (17)	P1—O3—H3	109.5
O2—Cr1—O7	91.65 (17)	P2—O7—Cr1	140.0 (3)
O2ii—Cr1—O7ii	91.65 (17)	H9A—O9—H10	108 (10)
O2—Cr1—O7ii	88.35 (17)	Cr1—O1—H1B	119 (6)
O7—Cr1—O7ii	180.0 (2)	Cr1—O1—H1A	120 (6)
O2ii—Cr1—O1ii	90.51 (17)	H1B—O1—H1A	107 (9)
O2—Cr1—O1ii	89.49 (17)	P1—C1—P2	114.8 (3)
O7—Cr1—O1ii	90.81 (18)	P1—C1—H4	108.6
O7ii—Cr1—O1ii	89.19 (18)	P2—C1—H4	108.6
O2ii—Cr1—O1	89.49 (17)	P1—C1—H5	108.6
O2—Cr1—O1	90.51 (17)	P2—C1—H5	108.6
O7—Cr1—O1	89.19 (18)	H4—C1—H5	107.5
O7ii—Cr1—O1	90.81 (18)	H8—O8—H7	114 (10)
O1ii—Cr1—O1	180.0 (3)	C2—N1—C3	123 (4)
O6—P2—O7	114.8 (2)	C2—N1—H1	118.3
O6—P2—O5	107.8 (2)	C3—N1—H1	118.3
O7—P2—O5	109.7 (2)	C3—C4—C2	116 (5)
O6—P2—C1	108.2 (3)	C3—C4—H4A	122.1
O7—P2—C1	109.0 (2)	C2—C4—H4A	122.1
O5—P2—C1	107.1 (2)	N1—C3—C2i	118 (2)
O4—P1—O2	115.5 (2)	C2i—C3—C4	122 (3)
O4—P1—O2	115.5 (2)	N1—C3—H3A	121.1
O4—P1—O3	107.9 (2)	C2i—C3—H3A	121.1
O4—P1—O3	107.9 (2)	C4—C3—H3A	116.7
O2—P1—O3	108.6 (2)	N1—C2—C3i	119 (2)
O4—P1—C1	110.1 (2)	C3i—C2—C4	122 (2)
O4—P1—C1	110.1 (2)	N1—C2—H2	120.7
O2—P1—C1	107.6 (2)	C3i—C2—H2	120.7
O3—P1—C1	106.9 (3)	C4—C2—H2	117.1
P1—O2—Cr1	134.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H4···O6iii	0.97	2.49	3.346 (7)	147
C4—H4A···O9iv	0.93	2.16	2.93 (7)	140
N1—H1···O9iv	0.86	2.32	3.03 (5)	141
O1—H1A···O6iii	0.80 (6)	1.83 (6)	2.634 (6)	176 (9)
O1—H1B···O4v	0.83 (6)	1.87 (6)	2.704 (6)	177 (9)
O3—H3···O8vi	0.82	1.83	2.629 (6)	163
O5—H6···O4iv	0.83 (5)	1.80 (5)	2.619 (6)	175 (10)
O8—H7···O6vii	0.83 (6)	1.86 (6)	2.687 (6)	171 (9)
O8—H8···O9	0.85 (7)	1.94 (8)	2.748 (7)	158 (11)
O9—H9A···O4	0.83 (6)	2.00 (6)	2.833 (6)	179 (10)
O9—H10···O8viii	0.84 (7)	1.99 (7)	2.820 (7)	174 (13)

Table 1

Selected bond lengths (Å)

Cr1—O1	1.991 (4)
Cr1—O2	1.956 (4)
Cr1—O7	1.964 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H4⋯O6i	0.97	2.49	3.346 (7)	147
C4—H4A⋯O9ii	0.93	2.16	2.93 (7)	140
N1—H1⋯O9ii	0.86	2.32	3.03 (5)	141
O1—H1A⋯O6i	0.80 (6)	1.83 (6)	2.634 (6)	176 (9)
O1—H1B⋯O4iii	0.83 (6)	1.87 (6)	2.704 (6)	177 (9)
O3—H3⋯O8iv	0.82	1.83	2.629 (6)	163
O5—H6⋯O4ii	0.83 (5)	1.80 (5)	2.619 (6)	175 (10)
O8—H7⋯O6v	0.83 (6)	1.86 (6)	2.687 (6)	171 (9)
O8—H8⋯O9	0.85 (7)	1.94 (8)	2.748 (7)	158 (11)
O9—H9A⋯O4	0.83 (6)	2.00 (6)	2.833 (6)	179 (10)
O9—H10⋯O8vi	0.84 (7)	1.99 (7)	2.820 (7)	174 (13)

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