2-Amino-5-chloro-pyridinium cis-diaqua-dioxalatochromate(III) sesquihydrate.

In the crystal structure of the title compound, (C(5)H(6)ClN(2))[Cr(C(2)O(4))(2)(H(2)O)(2)]·1.5H(2)O, the Cr(III) atom adopts a distorted octa-hedral geometry being coordinated by two O atoms of two cis water mol-ecules and four O atoms from two chelating oxalate dianions. The cis-diaqua-dioxalatochromate(III) anions, 2-amino-5-chloro-pyridinium cations and uncoordinated water mol-ecules are linked into a three-dimensional supra-molecular array by O-H⋯O and N-H⋯O hydrogen-bonding inter-actions. One of the two independent lattice water molecules is situated on a twofold rotation axis.

Related literature

For structural characterization of salts containing the [Cr(C2O4)2(H2O)2]− anion with various cations see: Bélombé et al. (2009 ▶); Nenwa et al. (2010 ▶); Chérif et al. (2011 ▶). For the building of hybrid supra­molecular networks, see: Zhang et al. (2000 ▶); Paraschiv et al. (2007 ▶). For discussion of hydrogen bonding, see: Blessing (1986 ▶); Brown (1976 ▶).

Experimental

Crystal data

(C5H6ClN2)[Cr(C2O4)2(H2O)2]·1.5H2O

M = 420.66

Orthorhombic,

a = 11.376 (2) Å

b = 53.041 (3) Å

c = 10.413 (2) Å

V = 6283.1 (17) Å3

Z = 16

Mo Kα radiation

μ = 0.96 mm−1

T = 298 K

0.42 × 0.32 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.792, T max = 0.882

3854 measured reflections

3414 independent reflections

3180 reflections with I > 2σ(I)

R int = 0.022

2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.074

S = 1.07

3414 reflections

243 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.31 e Å−3

Absolute structure: Flack (1983 ▶), 1608 Friedel pairs

Flack parameter: 0.000 (18)

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023392/kp2416sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023392/kp2416Isup2.hkl

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

(C5H6ClN2)[Cr(C2O4)2(H2O)2]·1.5H2O	F(000) = 3424
Mr = 420.66	Dx = 1.779 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 25 reflections
a = 11.376 (2) Å	θ = 10–15°
b = 53.041 (3) Å	µ = 0.96 mm−1
c = 10.413 (2) Å	T = 298 K
V = 6283.1 (17) Å3	Prism, violet
Z = 16	0.42 × 0.32 × 0.13 mm

Enraf–Nonius CAD-4 diffractometer	3180 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 27.0°, θmin = 2.7°
ω/2θ scans	h = −14→1
Absorption correction: ψ scan (North et al., 1968)	k = −1→67
Tmin = 0.792, Tmax = 0.882	l = −13→13
3854 measured reflections	2 standard reflections every 120 min
3414 independent reflections	intensity decay: 5%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0316P)2 + 13.7688P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3414 reflections	Δρmax = 0.30 e Å−3
243 parameters	Δρmin = −0.31 e Å−3
8 restraints	Absolute structure: Flack (1983), 1608 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.000 (18)

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
Cr	0.28854 (3)	0.029597 (7)	0.12687 (3)	0.01808 (9)
O1	0.45606 (16)	0.02882 (3)	0.17139 (17)	0.0219 (4)
O2	0.27072 (17)	0.03331 (4)	0.31611 (17)	0.0238 (4)
O3	0.57607 (15)	0.02584 (3)	0.34029 (18)	0.0245 (4)
O4	0.37907 (17)	0.03041 (4)	0.49507 (17)	0.0295 (4)
O5	0.29574 (17)	0.06593 (3)	0.09653 (16)	0.0286 (4)
O6	0.32410 (18)	0.02782 (3)	−0.05749 (16)	0.0228 (4)
O7	0.3518 (3)	0.05318 (4)	−0.2259 (2)	0.0467 (6)
O8	0.3288 (3)	0.09378 (4)	−0.0606 (2)	0.0471 (6)
O1W	0.28282 (17)	−0.00790 (3)	0.1438 (2)	0.0289 (4)
H11W	0.228 (2)	−0.0153 (6)	0.103 (3)	0.043*
H12W	0.313 (3)	−0.0148 (6)	0.210 (3)	0.043*
O2W	0.11515 (17)	0.03017 (4)	0.10241 (18)	0.0297 (5)
H21W	0.086 (3)	0.0282 (7)	0.023 (2)	0.045*
H22W	0.075 (3)	0.0209 (6)	0.158 (3)	0.045*
O3W	0.5956 (2)	0.05669 (5)	−0.0077 (3)	0.0541 (7)
H31W	0.646 (3)	0.0476 (8)	−0.052 (4)	0.081*
H32W	0.572 (4)	0.0474 (8)	0.058 (3)	0.081*
O4W	0.5000	0.0000	−0.2206 (3)	0.0366 (7)
H4W	0.448 (3)	0.0093 (7)	−0.177 (3)	0.055*
C1	0.4779 (2)	0.02831 (4)	0.2921 (2)	0.0186 (5)
C2	0.3677 (2)	0.03087 (4)	0.3782 (2)	0.0204 (5)
C3	0.3332 (2)	0.04963 (5)	−0.1130 (3)	0.0264 (5)
C4	0.3183 (3)	0.07223 (5)	−0.0199 (3)	0.0290 (6)
C5	0.1933 (3)	0.15991 (6)	0.3233 (3)	0.0418 (8)
H5	0.1933	0.1774	0.3230	0.050*
C6	0.2315 (3)	0.14673 (6)	0.2190 (3)	0.0423 (7)
C7	0.2297 (3)	0.12042 (6)	0.2198 (3)	0.0438 (8)
H7	0.2549	0.1114	0.1482	0.053*
C8	0.1909 (3)	0.10801 (6)	0.3254 (3)	0.0422 (8)
H8	0.1899	0.0905	0.3262	0.051*
C9	0.1518 (3)	0.12160 (6)	0.4344 (3)	0.0379 (7)
N1	0.1138 (3)	0.11041 (6)	0.5402 (3)	0.0565 (9)
H1A	0.0913	0.1193	0.6047	0.068*
H1B	0.1115	0.0942	0.5445	0.068*
N2	0.1552 (3)	0.14686 (5)	0.4280 (2)	0.0394 (6)
H2	0.1319	0.1553	0.4938	0.047*
Cl	0.27889 (13)	0.162724 (19)	0.08436 (9)	0.0737 (4)

	U11	U22	U33	U12	U13	U23
Cr	0.02037 (17)	0.02121 (17)	0.01267 (16)	−0.00028 (16)	−0.00167 (15)	0.00091 (14)
O1	0.0205 (9)	0.0299 (10)	0.0153 (8)	−0.0020 (7)	−0.0002 (7)	−0.0005 (7)
O2	0.0199 (9)	0.0364 (10)	0.0152 (8)	0.0007 (7)	0.0009 (7)	−0.0006 (7)
O3	0.0202 (9)	0.0318 (10)	0.0217 (9)	0.0023 (7)	−0.0022 (7)	−0.0021 (7)
O4	0.0292 (10)	0.0449 (12)	0.0144 (9)	−0.0055 (8)	−0.0002 (8)	−0.0022 (7)
O5	0.0426 (11)	0.0237 (9)	0.0195 (10)	0.0004 (8)	0.0002 (8)	−0.0017 (7)
O6	0.0323 (10)	0.0215 (9)	0.0147 (9)	−0.0017 (7)	0.0003 (8)	−0.0004 (6)
O7	0.0840 (19)	0.0369 (12)	0.0193 (10)	−0.0082 (12)	0.0086 (11)	0.0046 (9)
O8	0.0819 (18)	0.0244 (11)	0.0352 (12)	−0.0008 (11)	0.0065 (12)	0.0055 (9)
O1W	0.0335 (10)	0.0240 (9)	0.0290 (11)	−0.0057 (8)	−0.0117 (8)	0.0064 (8)
O2W	0.0230 (10)	0.0415 (12)	0.0247 (12)	−0.0020 (8)	−0.0070 (8)	0.0010 (8)
O3W	0.0566 (16)	0.0432 (14)	0.0626 (17)	0.0086 (12)	0.0283 (14)	0.0134 (12)
O4W	0.0340 (16)	0.0394 (18)	0.0365 (16)	0.0055 (13)	0.000	0.000
C1	0.0209 (12)	0.0191 (11)	0.0160 (11)	−0.0019 (9)	0.0000 (10)	−0.0007 (9)
C2	0.0211 (11)	0.0225 (11)	0.0177 (11)	−0.0028 (9)	0.0009 (10)	0.0008 (10)
C3	0.0349 (13)	0.0254 (12)	0.0189 (12)	−0.0019 (10)	−0.0013 (11)	0.0022 (10)
C4	0.0372 (14)	0.0234 (13)	0.0263 (13)	−0.0009 (11)	0.0028 (11)	0.0011 (11)
C5	0.063 (2)	0.0263 (15)	0.0361 (16)	0.0034 (14)	0.0054 (16)	−0.0047 (12)
C6	0.062 (2)	0.0331 (16)	0.0318 (15)	0.0050 (15)	0.0083 (16)	−0.0007 (13)
C7	0.069 (2)	0.0321 (15)	0.0305 (15)	0.0067 (15)	0.0075 (16)	−0.0089 (13)
C8	0.064 (2)	0.0254 (14)	0.0373 (16)	0.0024 (15)	0.0092 (16)	−0.0069 (12)
C9	0.0452 (19)	0.0375 (16)	0.0311 (15)	−0.0007 (14)	0.0043 (13)	−0.0044 (13)
N1	0.092 (3)	0.0399 (16)	0.0380 (16)	−0.0064 (16)	0.0192 (17)	−0.0017 (13)
N2	0.0595 (18)	0.0302 (13)	0.0284 (12)	0.0027 (12)	0.0068 (12)	−0.0092 (11)
Cl	0.1375 (11)	0.0385 (5)	0.0451 (5)	0.0074 (6)	0.0346 (7)	0.0065 (4)

Cr—O1	1.9618 (19)	O3W—H32W	0.883 (19)
Cr—O2	1.9907 (19)	O4W—H4W	0.897 (18)
Cr—O5	1.9547 (19)	C1—C2	1.547 (3)
Cr—O6	1.9642 (18)	C3—C4	1.551 (4)
Cr—O1W	1.9978 (18)	C5—N2	1.363 (4)
Cr—O2W	1.9891 (19)	C5—C6	1.363 (4)
O1—C1	1.282 (3)	C5—H5	0.9300
O2—C2	1.286 (3)	C6—C7	1.396 (4)
O3—C1	1.231 (3)	C6—Cl	1.725 (3)
O4—C2	1.224 (3)	C7—C8	1.355 (5)
O5—C4	1.284 (3)	C7—H7	0.9300
O6—C3	1.297 (3)	C8—C9	1.417 (4)
O7—C3	1.209 (3)	C8—H8	0.9300
O8—C4	1.225 (3)	C9—N1	1.324 (4)
O1W—H11W	0.850 (18)	C9—N2	1.342 (4)
O1W—H12W	0.850 (18)	N1—H1A	0.8600
O2W—H21W	0.896 (18)	N1—H1B	0.8600
O2W—H22W	0.885 (18)	N2—H2	0.8600
O3W—H31W	0.880 (19)
O5—Cr—O1	91.04 (8)	O4—C2—C1	119.3 (2)
O5—Cr—O6	83.15 (7)	O2—C2—C1	114.4 (2)
O1—Cr—O6	91.71 (8)	O7—C3—O6	125.9 (3)
O5—Cr—O2W	90.33 (9)	O7—C3—C4	120.4 (2)
O1—Cr—O2W	173.68 (8)	O6—C3—C4	113.7 (2)
O6—Cr—O2W	94.58 (8)	O8—C4—O5	126.1 (3)
O5—Cr—O2	93.82 (8)	O8—C4—C3	119.7 (2)
O1—Cr—O2	82.36 (7)	O5—C4—C3	114.3 (2)
O6—Cr—O2	173.31 (9)	N2—C5—C6	118.6 (3)
O2W—Cr—O2	91.39 (8)	N2—C5—H5	120.7
O5—Cr—O1W	175.72 (9)	C6—C5—H5	120.7
O1—Cr—O1W	89.42 (8)	C5—C6—C7	120.2 (3)
O6—Cr—O1W	92.58 (8)	C5—C6—Cl	119.7 (3)
O2W—Cr—O1W	89.67 (9)	C7—C6—Cl	120.1 (3)
O2—Cr—O1W	90.46 (8)	C8—C7—C6	119.7 (3)
C1—O1—Cr	114.86 (16)	C8—C7—H7	120.2
C2—O2—Cr	113.60 (17)	C6—C7—H7	120.2
C4—O5—Cr	114.69 (16)	C7—C8—C9	120.3 (3)
C3—O6—Cr	114.13 (16)	C7—C8—H8	119.8
Cr—O1W—H11W	116 (2)	C9—C8—H8	119.8
Cr—O1W—H12W	119 (3)	N1—C9—N2	119.9 (3)
H11W—O1W—H12W	120 (3)	N1—C9—C8	122.8 (3)
Cr—O2W—H21W	119 (2)	N2—C9—C8	117.3 (3)
Cr—O2W—H22W	115 (2)	C9—N1—H1A	120.0
H21W—O2W—H22W	110 (3)	C9—N1—H1B	120.0
H31W—O3W—H32W	107 (5)	H1A—N1—H1B	120.0
O3—C1—O1	125.3 (2)	C9—N2—C5	123.8 (3)
O3—C1—C2	120.5 (2)	C9—N2—H2	118.1
O1—C1—C2	114.2 (2)	C5—N2—H2	118.1
O4—C2—O2	126.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O4i	0.85 (2)	1.84 (3)	2.686 (3)	172 (3)
O1W—H12W···O3ii	0.85 (2)	1.94 (3)	2.769 (3)	163 (3)
O2W—H21W···O3iii	0.90 (2)	1.91 (2)	2.775 (3)	161 (3)
O2W—H21W···O4iii	0.90 (2)	2.37 (3)	2.909 (3)	118 (2)
O2W—H22W···O4Wiv	0.89 (2)	1.89 (3)	2.770 (3)	176 (3)
O3W—H31W···O2v	0.88 (2)	2.12 (4)	2.979 (3)	167 (4)
O3W—H32W···O1	0.88 (2)	2.03 (4)	2.861 (3)	157 (4)
O4W—H4W···O6	0.90 (2)	2.12 (3)	3.011 (3)	173 (3)
N1—H1A···O8vi	0.86	2.15	2.911 (4)	147
N1—H1B···O3Wiv	0.86	2.07	2.900 (4)	161
N2—H2···O8vi	0.86	2.13	2.900 (4)	150
N2—H2···O7vi	0.86	2.25	2.897 (4)	132

Table 1

Selected bond lengths (Å)

Cr—O1	1.9618 (19)
Cr—O2	1.9907 (19)
Cr—O5	1.9547 (19)
Cr—O6	1.9642 (18)
Cr—O1W	1.9978 (18)
Cr—O2W	1.9891 (19)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O4i	0.85 (2)	1.84 (3)	2.686 (3)	172 (3)
O1W—H12W⋯O3ii	0.85 (2)	1.94 (3)	2.769 (3)	163 (3)
O2W—H21W⋯O3iii	0.90 (2)	1.91 (2)	2.775 (3)	161 (3)
O2W—H21W⋯O4iii	0.90 (2)	2.37 (3)	2.909 (3)	118 (2)
O2W—H22W⋯O4Wiv	0.89 (2)	1.89 (3)	2.770 (3)	176 (3)
O3W—H31W⋯O2v	0.88 (2)	2.12 (4)	2.979 (3)	167 (4)
O3W—H32W⋯O1	0.88 (2)	2.03 (4)	2.861 (3)	157 (4)
O4W—H4W⋯O6	0.90 (2)	2.12 (3)	3.011 (3)	173 (3)
N1—H1A⋯O8vi	0.86	2.15	2.911 (4)	147
N1—H1B⋯O3Wiv	0.86	2.07	2.900 (4)	161
N2—H2⋯O8vi	0.86	2.13	2.900 (4)	150
N2—H2⋯O7vi	0.86	2.25	2.897 (4)	132

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