Poly[dimethyl-ammonium [aquadi-μ(2)-oxalato-dysprosate(III)] trihydrate].

The title compound, {(C(2)H(8)N)[Dy(C(2)O(4))(2)(H(2)O)]·3H(2)O}(n), was obtained as an unexpected product under hydro-thermal conditions. The Dy(III) atom is chelated by four oxalate anions, two of which are situated on two different centres of inversion. The distorted tricapped trigonal-prismatic coordination sphere of the Dy(III) atom is completed by a water mol-ecule. The bridging mode of the anions results in the formation of a three-dimensional network with cavities where the ammonium cations and the uncoordinated water mol-ecules reside. The structure is stabilized by numerous N-H⋯O and O-H⋯O hydrogen-bonding inter-actions.

Related literature

For decomposition mechanisms of organic ligands resulting in the formation of oxalates, see: Ghosh et al. (2004 ▶); Zhong et al., (2008 ▶). For other DyIII oxalate compounds, see: Hansson (1973 ▶); Kahwa et al. (1984 ▶); Ollendorff et al. (1969 ▶). The structure of the isotypic EuIII compound was reported by Yang et al. (2005 ▶).

Experimental

Crystal data

(C2H8N)[Dy(C2O4)2(H2O)]·3H2O

M = 456.70

Monoclinic,

a = 9.6239 (2) Å

b = 11.6030 (2) Å

c = 14.3050 (2) Å

β = 122.463 (1)°

V = 1347.77 (4) Å3

Z = 4

Mo Kα radiation

μ = 5.61 mm−1

T = 296 K

0.19 × 0.15 × 0.04 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.374, T max = 0.790

20173 measured reflections

3108 independent reflections

2810 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.047

S = 1.06

3108 reflections

211 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.84 e Å−3

Δρmin = −0.91 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Crystal Impact, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026140/wm2367sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026140/wm2367Isup2.hkl

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

(C2H8N)[Dy(C2O4)2(H2O)]·3H2O	F(000) = 884
Mr = 456.70	Dx = 2.251 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9337 reflections
a = 9.6239 (2) Å	θ = 2.4–27.6°
b = 11.6030 (2) Å	µ = 5.61 mm−1
c = 14.3050 (2) Å	T = 296 K
β = 122.463 (1)°	Block, colourless
V = 1347.77 (4) Å3	0.19 × 0.15 × 0.04 mm
Z = 4

Bruker APEXII area-detector diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	2810 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω scans	θmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→12
Tmin = 0.374, Tmax = 0.790	k = −15→14
20173 measured reflections	l = −18→18

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0236P)2 + 1.0326P] where P = (Fo2 + 2Fc2)/3
3108 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.84 e Å−3
12 restraints	Δρmin = −0.91 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
Dy1	0.117659 (15)	−0.013113 (10)	−0.167676 (10)	0.01672 (5)
N1	0.4246 (4)	−0.1300 (3)	−0.3049 (3)	0.0407 (7)
H1A	0.393 (5)	−0.098 (3)	−0.263 (3)	0.049*
H1B	0.378 (5)	−0.095 (3)	−0.368 (3)	0.049*
O1	0.2048 (2)	−0.21224 (15)	−0.15624 (17)	0.0250 (4)
O1W	0.1053 (3)	−0.02065 (19)	−0.34320 (18)	0.0317 (5)
H1WA	0.036 (4)	−0.061 (2)	−0.396 (2)	0.038*
H1WB	0.106 (4)	0.0401 (18)	−0.375 (2)	0.038*
O2	−0.1030 (2)	−0.13712 (15)	−0.29291 (17)	0.0232 (4)
O2W	0.5505 (4)	−0.2809 (3)	−0.0349 (3)	0.0669 (9)
H2WA	0.489 (5)	−0.291 (5)	−0.009 (3)	0.080*
H2WB	0.624 (4)	−0.238 (4)	0.016 (3)	0.080*
O3	−0.1939 (2)	−0.31830 (15)	−0.32907 (16)	0.0219 (4)
O3W	−0.1188 (4)	−0.1547 (2)	−0.5332 (3)	0.0576 (8)
H3WA	−0.090 (5)	−0.222 (2)	−0.529 (4)	0.069*
H3WB	−0.209 (3)	−0.155 (3)	−0.543 (4)	0.069*
O4	0.1169 (2)	−0.39375 (16)	−0.20338 (18)	0.0278 (5)
O4W	0.6648 (5)	−0.5050 (3)	−0.0068 (3)	0.0701 (11)
H4WA	0.694 (6)	−0.530 (4)	0.056 (3)	0.084*
H4WB	0.596 (5)	−0.456 (4)	−0.020 (4)	0.084*
O5	0.3400 (3)	−0.01122 (16)	0.02214 (18)	0.0263 (5)
O6	0.0192 (3)	−0.11779 (16)	−0.06741 (17)	0.0276 (4)
O7	0.0381 (3)	0.11134 (17)	−0.06433 (18)	0.0300 (5)
O8	0.3894 (3)	−0.01101 (15)	−0.14319 (17)	0.0226 (4)
C1	0.0965 (3)	−0.2872 (2)	−0.2069 (2)	0.0197 (5)
C2	−0.0829 (3)	−0.2435 (2)	−0.2832 (2)	0.0180 (5)
C3	0.4856 (4)	−0.0001 (2)	0.0483 (2)	0.0198 (6)
C4	−0.0055 (3)	−0.0664 (2)	−0.0010 (2)	0.0220 (6)
C5	0.3567 (6)	−0.2468 (4)	−0.3333 (4)	0.0761 (15)
H5A	0.2387	−0.2431	−0.3721	0.091*
H5B	0.3984	−0.2910	−0.2667	0.091*
H5C	0.3882	−0.2827	−0.3796	0.091*
C6	0.6030 (5)	−0.1251 (5)	−0.2451 (4)	0.0710 (14)
H6A	0.6384	−0.0464	−0.2279	0.085*
H6B	0.6396	−0.1572	−0.2901	0.085*
H6C	0.6490	−0.1686	−0.1777	0.085*

	U11	U22	U33	U12	U13	U23
Dy1	0.01578 (8)	0.01427 (7)	0.01843 (8)	−0.00014 (4)	0.00807 (6)	−0.00013 (4)
N1	0.0347 (18)	0.0526 (18)	0.0363 (17)	0.0048 (14)	0.0200 (15)	−0.0078 (14)
O1	0.0179 (11)	0.0192 (9)	0.0295 (11)	−0.0011 (8)	0.0073 (9)	−0.0039 (8)
O1W	0.0342 (14)	0.0367 (12)	0.0218 (11)	−0.0059 (10)	0.0133 (11)	−0.0019 (9)
O2	0.0213 (11)	0.0158 (9)	0.0259 (10)	0.0016 (7)	0.0082 (9)	0.0007 (8)
O2W	0.053 (2)	0.0513 (18)	0.066 (2)	0.0025 (14)	0.0119 (17)	−0.0131 (15)
O3	0.0172 (10)	0.0179 (9)	0.0272 (11)	−0.0014 (7)	0.0096 (9)	−0.0029 (7)
O3W	0.066 (2)	0.0331 (13)	0.0650 (19)	0.0039 (13)	0.0292 (19)	0.0093 (13)
O4	0.0228 (11)	0.0161 (9)	0.0319 (11)	0.0016 (8)	0.0063 (9)	−0.0012 (8)
O4W	0.074 (3)	0.068 (2)	0.0376 (18)	0.0164 (15)	0.0098 (18)	−0.0028 (14)
O5	0.0184 (11)	0.0392 (11)	0.0218 (11)	−0.0021 (8)	0.0111 (9)	−0.0007 (8)
O6	0.0340 (12)	0.0239 (10)	0.0308 (12)	−0.0039 (8)	0.0213 (10)	−0.0040 (8)
O7	0.0389 (13)	0.0241 (10)	0.0397 (13)	0.0032 (9)	0.0294 (11)	0.0059 (9)
O8	0.0177 (11)	0.0297 (10)	0.0187 (10)	−0.0005 (7)	0.0085 (9)	−0.0015 (7)
C1	0.0209 (15)	0.0194 (12)	0.0179 (13)	0.0005 (10)	0.0098 (12)	0.0006 (10)
C2	0.0197 (15)	0.0195 (12)	0.0165 (13)	−0.0014 (10)	0.0108 (12)	−0.0012 (10)
C3	0.0205 (15)	0.0161 (11)	0.0200 (14)	0.0015 (10)	0.0090 (12)	0.0005 (9)
C4	0.0157 (14)	0.0231 (14)	0.0252 (15)	−0.0009 (10)	0.0098 (12)	0.0000 (10)
C5	0.096 (4)	0.059 (3)	0.082 (4)	−0.017 (3)	0.054 (3)	−0.020 (2)
C6	0.035 (2)	0.121 (4)	0.052 (3)	0.007 (2)	0.020 (2)	−0.019 (3)

Dy1—O3i	2.3846 (17)	O3W—H3WA	0.83 (3)
Dy1—O2	2.3883 (19)	O3W—H3WB	0.80 (4)
Dy1—O5	2.390 (2)	O4—C1	1.249 (3)
Dy1—O6	2.427 (2)	O4—Dy1ii	2.4386 (19)
Dy1—O1	2.4335 (18)	O4W—H4WA	0.84 (3)
Dy1—O4i	2.4386 (19)	O4W—H4WB	0.82 (4)
Dy1—O8	2.445 (2)	O5—C3	1.248 (4)
Dy1—O1W	2.451 (2)	O6—C4	1.248 (3)
Dy1—O7	2.464 (2)	O7—C4iii	1.248 (3)
N1—C6	1.451 (5)	O8—C3iv	1.246 (4)
N1—C5	1.463 (6)	C1—C2	1.551 (4)
N1—H1A	0.89 (4)	C3—O8iv	1.246 (4)
N1—H1B	0.87 (4)	C3—C3iv	1.549 (6)
O1—C1	1.248 (3)	C4—O7iii	1.248 (3)
O1W—H1WA	0.84 (4)	C4—C4iii	1.544 (5)
O1W—H1WB	0.84 (4)	C5—H5A	0.9600
O2—C2	1.245 (3)	C5—H5B	0.9600
O2W—H2WA	0.86 (5)	C5—H5C	0.9600
O2W—H2WB	0.85 (4)	C6—H6A	0.9600
O3—C2	1.254 (3)	C6—H6B	0.9600
O3—Dy1ii	2.3846 (17)	C6—H6C	0.9600
O3i—Dy1—O2	135.67 (6)	C5—N1—H1B	104 (3)
O3i—Dy1—O5	85.20 (6)	H1A—N1—H1B	110 (4)
O2—Dy1—O5	138.66 (7)	C1—O1—Dy1	118.16 (17)
O3i—Dy1—O6	135.05 (6)	Dy1—O1W—H1WA	121 (2)
O2—Dy1—O6	70.73 (7)	Dy1—O1W—H1WB	121 (2)
O5—Dy1—O6	74.25 (7)	H1WA—O1W—H1WB	103 (2)
O3i—Dy1—O1	143.39 (7)	C2—O2—Dy1	119.42 (17)
O2—Dy1—O1	67.30 (6)	H2WA—O2W—H2WB	99 (2)
O5—Dy1—O1	82.32 (7)	C2—O3—Dy1ii	118.80 (17)
O6—Dy1—O1	73.44 (7)	H3WA—O3W—H3WB	107 (3)
O3i—Dy1—O4i	67.45 (6)	C1—O4—Dy1ii	118.02 (17)
O2—Dy1—O4i	71.67 (6)	H4WA—O4W—H4WB	105 (3)
O5—Dy1—O4i	139.00 (7)	C3—O5—Dy1	121.19 (19)
O6—Dy1—O4i	103.57 (7)	C4—O6—Dy1	120.35 (17)
O1—Dy1—O4i	137.38 (6)	C4iii—O7—Dy1	119.20 (17)
O3i—Dy1—O8	71.14 (6)	C3iv—O8—Dy1	119.36 (19)
O2—Dy1—O8	124.42 (7)	O1—C1—O4	127.0 (3)
O5—Dy1—O8	66.48 (7)	O1—C1—C2	116.6 (2)
O6—Dy1—O8	130.33 (7)	O4—C1—C2	116.4 (2)
O1—Dy1—O8	72.31 (6)	O2—C2—O3	126.2 (3)
O4i—Dy1—O8	125.97 (7)	O2—C2—C1	116.7 (2)
O3i—Dy1—O1W	81.96 (7)	O3—C2—C1	117.1 (2)
O2—Dy1—O1W	71.05 (7)	O8iv—C3—O5	127.6 (3)
O5—Dy1—O1W	133.30 (8)	O8iv—C3—C3iv	116.1 (3)
O6—Dy1—O1W	140.18 (7)	O5—C3—C3iv	116.3 (3)
O1—Dy1—O1W	81.98 (7)	O7iii—C4—O6	126.7 (3)
O4i—Dy1—O1W	74.28 (8)	O7iii—C4—C4iii	116.5 (3)
O8—Dy1—O1W	66.87 (7)	O6—C4—C4iii	116.8 (3)
O3i—Dy1—O7	69.77 (6)	N1—C5—H5A	109.5
O2—Dy1—O7	111.44 (7)	N1—C5—H5B	109.5
O5—Dy1—O7	71.94 (7)	H5A—C5—H5B	109.5
O6—Dy1—O7	65.99 (7)	N1—C5—H5C	109.5
O1—Dy1—O7	136.30 (7)	H5A—C5—H5C	109.5
O4i—Dy1—O7	70.20 (7)	H5B—C5—H5C	109.5
O8—Dy1—O7	124.13 (7)	N1—C6—H6A	109.5
O1W—Dy1—O7	140.87 (7)	N1—C6—H6B	109.5
C6—N1—C5	114.3 (4)	H6A—C6—H6B	109.5
C6—N1—H1A	108 (2)	N1—C6—H6C	109.5
C5—N1—H1A	108 (2)	H6A—C6—H6C	109.5
C6—N1—H1B	112 (3)	H6B—C6—H6C	109.5
O3i—Dy1—O1—C1	−146.82 (18)	O3i—Dy1—O7—C4iii	−163.0 (2)
O2—Dy1—O1—C1	−9.33 (19)	O2—Dy1—O7—C4iii	64.6 (2)
O5—Dy1—O1—C1	142.0 (2)	O5—Dy1—O7—C4iii	−71.4 (2)
O6—Dy1—O1—C1	66.3 (2)	O6—Dy1—O7—C4iii	8.9 (2)
O4i—Dy1—O1—C1	−25.9 (2)	O1—Dy1—O7—C4iii	−14.4 (3)
O8—Dy1—O1—C1	−150.3 (2)	O4i—Dy1—O7—C4iii	124.6 (2)
O1W—Dy1—O1—C1	−82.1 (2)	O8—Dy1—O7—C4iii	−114.7 (2)
O7—Dy1—O1—C1	88.5 (2)	O1W—Dy1—O7—C4iii	150.63 (19)
O3i—Dy1—O2—C2	156.75 (18)	O3i—Dy1—O8—C3iv	86.85 (17)
O5—Dy1—O2—C2	−34.0 (2)	O2—Dy1—O8—C3iv	−140.12 (16)
O6—Dy1—O2—C2	−67.6 (2)	O5—Dy1—O8—C3iv	−6.14 (16)
O1—Dy1—O2—C2	11.96 (19)	O6—Dy1—O8—C3iv	−46.9 (2)
O4i—Dy1—O2—C2	−179.8 (2)	O1—Dy1—O8—C3iv	−95.32 (18)
O8—Dy1—O2—C2	58.7 (2)	O4i—Dy1—O8—C3iv	128.38 (17)
O1W—Dy1—O2—C2	101.0 (2)	O1W—Dy1—O8—C3iv	176.00 (19)
O7—Dy1—O2—C2	−120.7 (2)	O7—Dy1—O8—C3iv	39.15 (19)
O3i—Dy1—O5—C3	−65.25 (18)	Dy1—O1—C1—O4	−173.8 (2)
O2—Dy1—O5—C3	122.27 (18)	Dy1—O1—C1—C2	6.6 (3)
O6—Dy1—O5—C3	155.14 (19)	Dy1ii—O4—C1—O1	−171.9 (2)
O1—Dy1—O5—C3	80.26 (19)	Dy1ii—O4—C1—C2	7.7 (3)
O4i—Dy1—O5—C3	−112.15 (19)	Dy1—O2—C2—O3	166.6 (2)
O8—Dy1—O5—C3	6.26 (17)	Dy1—O2—C2—C1	−13.2 (3)
O1W—Dy1—O5—C3	9.0 (2)	Dy1ii—O3—C2—O2	165.2 (2)
O7—Dy1—O5—C3	−135.52 (19)	Dy1ii—O3—C2—C1	−15.0 (3)
O3i—Dy1—O6—C4	1.9 (3)	O1—C1—C2—O2	4.2 (4)
O2—Dy1—O6—C4	−134.4 (2)	O4—C1—C2—O2	−175.4 (2)
O5—Dy1—O6—C4	68.0 (2)	O1—C1—C2—O3	−175.6 (2)
O1—Dy1—O6—C4	154.5 (2)	O4—C1—C2—O3	4.7 (4)
O4i—Dy1—O6—C4	−69.7 (2)	Dy1—O5—C3—O8iv	174.11 (19)
O8—Dy1—O6—C4	106.4 (2)	Dy1—O5—C3—C3iv	−5.9 (3)
O1W—Dy1—O6—C4	−151.28 (19)	Dy1—O6—C4—O7iii	−171.5 (2)
O7—Dy1—O6—C4	−8.9 (2)	Dy1—O6—C4—C4iii	8.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O8	0.89 (4)	2.00 (4)	2.866 (4)	163 (4)
N1—H1A···O1W	0.89 (4)	2.52 (4)	3.090 (4)	122 (3)
O1W—H1WA···O3W	0.84 (4)	2.03 (2)	2.857 (4)	173 (3)
O4W—H4WB···O2W	0.82 (4)	2.06 (3)	2.767 (4)	144 (5)
N1—H1B···O4Wv	0.87 (4)	1.91 (4)	2.759 (5)	165 (4)
O1W—H1WB···O3Wvi	0.84 (4)	1.92 (2)	2.744 (3)	167 (3)
O2W—H2WB···O3vii	0.85 (4)	2.06 (2)	2.876 (4)	161 (5)
O3W—H3WA···O7ii	0.85 (4)	2.24 (3)	2.959 (3)	145 (4)
O3W—H3WA···O6viii	0.83 (4)	2.34 (2)	3.110 (3)	156 (4)
O3W—H3WB···O4Wix	0.80 (5)	2.42 (3)	2.959 (5)	125 (4)
O3W—H3WB···O2Wix	0.80 (5)	2.49 (2)	3.256 (5)	160 (4)
O4W—H4WA···O4x	0.84 (4)	2.10 (3)	2.837 (4)	147 (5)

Table 1

Selected bond lengths (Å)

Dy1—O3i	2.3846 (17)
Dy1—O2	2.3883 (19)
Dy1—O5	2.390 (2)
Dy1—O6	2.427 (2)
Dy1—O1	2.4335 (18)
Dy1—O4i	2.4386 (19)
Dy1—O8	2.445 (2)
Dy1—O1W	2.451 (2)
Dy1—O7	2.464 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O8	0.89 (4)	2.00 (4)	2.866 (4)	163 (4)
N1—H1A⋯O1W	0.89 (4)	2.52 (4)	3.090 (4)	122 (3)
O1W—H1WA⋯O3W	0.84 (4)	2.03 (2)	2.857 (4)	173 (3)
O4W—H4WB⋯O2W	0.82 (4)	2.06 (3)	2.767 (4)	144 (5)
N1—H1B⋯O4Wii	0.87 (4)	1.91 (4)	2.759 (5)	165 (4)
O1W—H1WB⋯O3Wiii	0.84 (4)	1.92 (2)	2.744 (3)	167 (3)
O2W—H2WB⋯O3iv	0.85 (4)	2.06 (2)	2.876 (4)	161 (5)
O3W—H3WA⋯O7v	0.85 (4)	2.24 (3)	2.959 (3)	145 (4)
O3W—H3WA⋯O6vi	0.83 (4)	2.34 (2)	3.110 (3)	156 (4)
O3W—H3WB⋯O4Wvii	0.80 (5)	2.42 (3)	2.959 (5)	125 (4)
O3W—H3WB⋯O2Wvii	0.80 (5)	2.49 (2)	3.256 (5)	160 (4)
O4W—H4WA⋯O4viii	0.84 (4)	2.10 (3)	2.837 (4)	147 (5)

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