Retracted: Ethyl­enediammonium perchlorate

The the crystal structure of the title compound, C₂H₉N₂⁺·ClO₄⁻, C—H...O, N—H...O and N—H...Cl hydrogen bonds result in the formation of a supra­molecular network structure.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.048
• wR factor = 0.143
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O2      ..       2.59 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2E    ..  CL1     ..       2.89 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen -bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring Dy metal chains by reaction of the dysprosium (III) ion with ethylene diamine and p-acetaminobenzoic acid ligands. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one C₂N₂H₉⁺ cation and one ClO₄^- anion.

In the crystal structure, C—H···O, N—H···O and N—H···Cl hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.

Related literature

For related literature, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). For bond-length data, see: Allen et al. (1987)

S2. Experimental

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Dysprosium (III) perchlorate hexahydrate (558.8 mg, 1 mmol), ethylene diamine (120.2 mg, 2 mmol), p-acetaminobenzoic acid (179.1 mg, 1 mmol) and distilled water (8 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

S3. Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH₂), 0.89 Å (for NH₃) and C—H = 0.97 Å for methylene H atoms, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,N), where x = 1.5 for NH₃ H, and x = 1.2 for all other H atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Ethylenediammonium perchlorate

Crystal data

C2H9N2^+·ClO4^−	F(000) = 336
Mr = 160.56	Dx = 1.587 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2295 reflections
a = 7.417 (2) Å	θ = 2.5–27.9°
b = 11.9078 (13) Å	µ = 0.52 mm^−1
c = 8.1023 (16) Å	T = 273 K
β = 110.105 (4)°	Prism, colorless
V = 672.0 (2) Å^3	0.22 × 0.17 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1334 independent reflections
Radiation source: fine-focus sealed tube	1078 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 26.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.892, Tmax = 0.924	k = −14→14
4245 measured reflections	l = −9→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0847P)^2 + 1.0354P] where P = (Fo^2 + 2Fc^2)/3
1334 reflections	(Δ/σ)max < 0.001
83 parameters	Δρmax = 0.87 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.58506 (9)	0.36384 (5)	0.24194 (8)	0.0190 (3)
O1	0.6650 (3)	0.25634 (16)	0.3425 (2)	0.0239 (5)
O2	0.6771 (3)	0.38079 (17)	0.0940 (3)	0.0246 (5)
O3	0.6418 (3)	0.46860 (16)	0.3568 (2)	0.0209 (4)
O4	0.3699 (3)	0.35523 (16)	0.1531 (2)	0.0209 (5)
N1	−0.2506 (3)	0.65783 (19)	0.2210 (3)	0.0183 (5)
H1D	−0.3092	0.6061	0.1483	0.022*
H1C	−0.3155	0.7088	0.2511	0.022*
N2	0.2444 (3)	0.55704 (19)	0.2860 (3)	0.0179 (5)
H2D	0.2905	0.6200	0.2566	0.027*
H2C	0.2847	0.4985	0.2399	0.027*
H2E	0.2858	0.5505	0.4025	0.027*
C1	−0.0398 (4)	0.6591 (2)	0.2940 (4)	0.0217 (6)
H1A	0.0033	0.6534	0.4211	0.026*
H1B	0.0087	0.7288	0.2634	0.026*
C2	0.0337 (4)	0.5605 (3)	0.2183 (4)	0.0269 (7)
H2A	−0.0164	0.4914	0.2487	0.032*
H2B	−0.0114	0.5665	0.0912	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0188 (4)	0.0196 (4)	0.0189 (4)	−0.0006 (2)	0.0071 (3)	0.0003 (2)
O1	0.0284 (10)	0.0206 (10)	0.0236 (10)	0.0083 (8)	0.0101 (8)	0.0064 (7)
O2	0.0288 (11)	0.0267 (10)	0.0249 (11)	−0.0074 (8)	0.0178 (9)	−0.0032 (8)
O3	0.0265 (10)	0.0185 (10)	0.0187 (9)	−0.0040 (8)	0.0090 (7)	−0.0032 (7)
O4	0.0142 (10)	0.0251 (11)	0.0219 (10)	−0.0017 (7)	0.0042 (8)	0.0013 (7)
N1	0.0099 (10)	0.0227 (11)	0.0217 (11)	0.0030 (8)	0.0045 (8)	−0.0039 (8)
N2	0.0130 (11)	0.0210 (11)	0.0195 (11)	0.0020 (8)	0.0052 (8)	−0.0011 (8)
C1	0.0122 (13)	0.0252 (14)	0.0262 (14)	−0.0003 (10)	0.0048 (10)	−0.0076 (11)
C2	0.0138 (13)	0.0295 (15)	0.0344 (16)	−0.0002 (11)	0.0043 (11)	−0.0143 (12)

Geometric parameters (Å, º)

Cl1—O4	1.512 (2)	N2—H2D	0.8900
Cl1—O1	1.5236 (19)	N2—H2C	0.8900
Cl1—O3	1.5266 (19)	N2—H2E	0.8900
Cl1—O2	1.583 (2)	C1—C2	1.511 (4)
N1—C1	1.469 (3)	C1—H1A	0.9700
N1—H1D	0.8600	C1—H1B	0.9700
N1—H1C	0.8600	C2—H2A	0.9700
N2—C2	1.468 (3)	C2—H2B	0.9700
O4—Cl1—O1	110.52 (11)	H2C—N2—H2E	109.5
O4—Cl1—O3	111.74 (11)	N1—C1—C2	108.1 (2)
O1—Cl1—O3	112.68 (11)	N1—C1—H1A	110.1
O4—Cl1—O2	107.91 (11)	C2—C1—H1A	110.1
O1—Cl1—O2	108.79 (11)	N1—C1—H1B	110.1
O3—Cl1—O2	104.91 (10)	C2—C1—H1B	110.1
C1—N1—H1D	120.0	H1A—C1—H1B	108.4
C1—N1—H1C	120.0	N2—C2—C1	110.9 (2)
H1D—N1—H1C	120.0	N2—C2—H2A	109.5
C2—N2—H2D	109.5	C1—C2—H2A	109.5
C2—N2—H2C	109.5	N2—C2—H2B	109.5
H2D—N2—H2C	109.5	C1—C2—H2B	109.5
C2—N2—H2E	109.5	H2A—C2—H2B	108.0
H2D—N2—H2E	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O4	0.89	2.03	2.914 (3)	174
N2—H2C···Cl1	0.89	2.74	3.525 (2)	148
N2—H2C···O3	0.89	2.51	2.994 (3)	115
N2—H2E···Cl1^i	0.89	2.89	3.714 (2)	154
N2—H2E···O3^i	0.89	1.85	2.739 (3)	176
N2—H2D···O1^ii	0.89	1.89	2.765 (3)	168
N1—H1C···Cl1^iii	0.86	2.74	3.574 (2)	165
N1—H1C···O1^iii	0.86	2.50	3.162 (3)	134
N1—H1C···O4^iii	0.86	2.01	2.823 (3)	158
N1—H1D···O4^iv	0.86	2.37	2.855 (3)	116
C2—H2A···O2^v	0.97	2.55	3.280 (4)	132

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