2-Amino-5-chloro­pyridinium cis-diaqua­dioxalatochromate(III) sesquihydrate

Chérif, I.; Abdelhak, J.; Zid, M.F.; Driss, A.

doi:10.1107/S1600536812023392

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m824-m825

doi:10.1107/S1600536812023392

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2-Amino-5-chloropyridinium cis-diaquadioxalatochromate(III) sesquihydrate

Ichraf Chérif,^a ^* Jawher Abdelhak,^a Mohamed Faouzi Zid ^a and Ahmed Driss ^a

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia
^*Correspondence e-mail: cherif.ichraf@yahoo.fr

(Received 10 May 2012; accepted 22 May 2012; online 26 May 2012)

In the crystal structure of the title compound, (C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂]·1.5H₂O, the Cr^III atom adopts a distorted octahedral geometry being coordinated by two O atoms of two cis water molecules and four O atoms from two chelating oxalate dianions. The cis-diaquadioxalatochromate(III) anions, 2-amino-5-chloropyridinium cations and uncoordinated water molecules are linked into a three-dimensional supramolecular array by O—H⋯O and N—H⋯O hydrogen-bonding interactions. 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_r = 420.66
Orthorhombic, F d d 2
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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.074
S = 1.07
3414 reflections
243 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 1608 Friedel pairs
Flack parameter: 0.000 (18)

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⋯O4W^iv	0.89 (2)	1.89 (3)	2.770 (3)	176 (3)
O3W—H31W⋯O2^v	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⋯O8^vi	0.86	2.15	2.911 (4)	147
N1—H1B⋯O3W^iv	0.86	2.07	2.900 (4)	161
N2—H2⋯O8^vi	0.86	2.13	2.900 (4)	150
N2—H2⋯O7^vi	0.86	2.25	2.897 (4)	132
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, z; (iii) $[x-{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{3\over 4}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023392/kp2416sup1.cif

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

checkCIF report

Comment top

It is well known that the use of hydrogen-bonding and π-π stacking interactions is a successful way to obtain a large variety of hybrid (organic/inorganic) compounds with extended supramolecular networks through self-assembly (Zhang et al., 2000; Paraschiv et al., 2007). Following this strategy, we recently published the structure of an organic-inorganic hybrid salt: 4-aminopyridinium trans-diaquadioxalatochromate(III) monohydrate (Chérif et al., 2011). In this contribution, we report the crystal structure of an homologous salt with 2-amino-5-chloropyridinium as the organic cation.

The title compound appears to be the first member of salts of general formula (organic cation)[Cr(C₂O₄)₂(H₂O)₂].xH₂O where x = 0 or x = 1 in which the complex anion [Cr(C₂O₄)₂(H₂O)₂]^- adopts the cis geometry. The asymmetric unit is formed by a [Cr(C₂O₄)₂(H₂O)₂]^- anion, a (C₅H₆ClN₂)⁺ cation and 1.5 water molecules [The O4W atom is located on a special position (1/2, 0, z)] (Fig. 1). In the complex anion, each chromium atom is six-coordinated in a distorted octahedral geometry with two O water molecules in cis position and four oxalato-O atoms from two chelating oxalate groups (Table 1). The four Cr—O(ox) distances range from 1.955 (2) to 1.991 (2) Å; three of them in the range 1.955 (2)–1.965 (2) Å are comparable to those reported in similar compounds (Bélombé et al., 2009; Nenwa et al., 2010; Chérif et al., 2011) but the last one, Cr—O2, is slightly longer. The Cr—O(water) distances are shorter than those observed for the quinolinium and 4-dimethylaminopyridinium compounds (Bélombé et al., 2009; Nenwa et al., 2010).

The structure can be described as segregated positive (C₅H₆ClN₂)⁺ and negative [[Cr(C₂O₄)₂(H₂O)₂]^- + H₂O] layers parallel to (010) (Fig. 2) and interconnected via N—H···O and O—H···O hydrogen bonds (Blessing, 1986; Brown, 1976). In fact, an extensive network of hydrogen bonds contributes to the stabilization of the structure. O—H···O hydrogen bonds involving all water molecules and some of the oxalato-O atoms provide the cohesion of the positive layers. The two N atoms of (C₅H₆ClN₂)⁺ are hydrogen bonded to the peripheral O atoms of the oxalate groups (O8 and O7) and to the solvent water molecules (O3W) connecting the positive and negative layers (Fig. 3, Table 2).

Related literature top

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 top

Ethanol solutions of C₅H₅ClN₂ (1 mmol) (10 mL) and H₂C₂O₄.2H₂O (2 mmol) (10 mL) were added to CrCl₃.6H₂O (1 mmol) dissolved in 10 mL of ethanol and stirred for 5 h. The resulting violet solution was left at room temperature and crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); 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).

Figures top

	Fig. 1. The asymmetric unit of (C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂].1.5H₂O with the atom-numbering scheme. Thermal ellipsoids are drawn at the 50% probability level for non-H atoms.
	Fig. 2. Projection of (C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂].1.5H₂O structure along the c axis.
	Fig. 3. N—H···O hydrogen bonds (dashed lines) in (C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂].1.5H₂O showing the connection between positive and negative layers.

2-Amino-5-chloropyridinium cis-diaquadioxalatochromate(III) sesquihydrate top

Crystal data top

(C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂]·1.5H₂O	F(000) = 3424
M_r = 420.66	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0316P)² + 13.7688P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3414 reflections	Δρ_max = 0.30 e Å⁻³
243 parameters	Δρ_min = −0.31 e Å⁻³
8 restraints	Absolute structure: Flack (1983), 1608 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.000 (18)

Crystal data top

(C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂]·1.5H₂O	V = 6283.1 (17) Å³
M_r = 420.66	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 11.376 (2) Å	µ = 0.96 mm⁻¹
b = 53.041 (3) Å	T = 298 K
c = 10.413 (2) Å	0.42 × 0.32 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3180 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.792, T_max = 0.882	2 standard reflections every 120 min
3854 measured reflections	intensity decay: 5%
3414 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0316P)² + 13.7688P] where P = (F_o² + 2F_c²)/3
S = 1.07	Δρ_max = 0.30 e Å⁻³
3414 reflections	Δρ_min = −0.31 e Å⁻³
243 parameters	Absolute structure: Flack (1983), 1608 Friedel pairs
8 restraints	Absolute structure parameter: 0.000 (18)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O4W^iv	0.89 (2)	1.89 (3)	2.770 (3)	176 (3)
O3W—H31W···O2^v	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···O8^vi	0.86	2.15	2.911 (4)	147
N1—H1B···O3W^iv	0.86	2.07	2.900 (4)	161
N2—H2···O8^vi	0.86	2.13	2.900 (4)	150
N2—H2···O7^vi	0.86	2.25	2.897 (4)	132

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1, −y, z; (iii) x−1/2, y, z−1/2; (iv) x−1/2, y, z+1/2; (v) x+1/2, y, z−1/2; (vi) x−1/4, −y+1/4, z+3/4.

Experimental details

Crystal data
Chemical formula	(C₅H₆ClN₂)[Cr(C₂O₄)₂(H₂O)₂]·1.5H₂O
M_r	420.66
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	298
a, b, c (Å)	11.376 (2), 53.041 (3), 10.413 (2)
V (Å³)	6283.1 (17)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.42 × 0.32 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.792, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	3854, 3414, 3180
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.074, 1.07
No. of reflections	3414
No. of parameters	243
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0316P)² + 13.7688P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.31
Absolute structure	Flack (1983), 1608 Friedel pairs
Absolute structure parameter	0.000 (18)

Computer programs: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1998), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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···O4W^iv	0.89 (2)	1.89 (3)	2.770 (3)	176 (3)
O3W—H31W···O2^v	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···O8^vi	0.86	2.15	2.911 (4)	147
N1—H1B···O3W^iv	0.86	2.07	2.900 (4)	161
N2—H2···O8^vi	0.86	2.13	2.900 (4)	150
N2—H2···O7^vi	0.86	2.25	2.897 (4)	132

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1, −y, z; (iii) x−1/2, y, z−1/2; (iv) x−1/2, y, z+1/2; (v) x+1/2, y, z−1/2; (vi) x−1/4, −y+1/4, z+3/4.

References

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Volume 68| Part 6| June 2012| Pages m824-m825

doi:10.1107/S1600536812023392

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