1,4-Diazo­niabicyclo­[2.2.2]octane hexa­aqua­magnesium bis­(sulfate)

Zheng, W.-N.

doi:10.1107/S1600536811005368

metal-organic compounds

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Volume 67| Part 3| March 2011| Page m344

doi:10.1107/S1600536811005368

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1,4-Diazoniabicyclo[2.2.2]octane hexaaquamagnesium bis(sulfate)

Wen-Ni Zheng ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 29 January 2011; accepted 14 February 2011; online 19 February 2011)

In the title compound, (C₆H₁₄N₂)[Mg(H₂O)₆](SO₄)₂, the Mg^II ion, lying on an inversion center, is coordinated by six water molecules in a slightly distorted octahedral geometry. The 1,4-diazoniabicyclo[2.2.2]octane cation is located about a twofold rotation axis. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the cations and the anions into a three-dimensional network.

Related literature

For the properties and applications of amide salt compounds, see: Fu et al. (2007 , 2008 , 2009 ); Fu & Xiong (2008 ).

Experimental

Crystal data

(C₆H₁₄N₂)[Mg(H₂O)₆](SO₄)₂
M_r = 438.74
Monoclinic, C 2/c
a = 14.968 (3) Å
b = 9.1860 (18) Å
c = 14.334 (3) Å
β = 117.12 (3)°
V = 1754.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.89, T_max = 0.95
8747 measured reflections
2014 independent reflections
1839 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.169
S = 1.26
2014 reflections
116 parameters
H-atom parameters constrained
Δρ_max = 1.30 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.91	1.87	2.734 (3)	157
O1W—H1WA⋯O3ⁱ	0.85	1.90	2.751 (3)	179
O1W—H1WB⋯O1ⁱⁱ	0.85	2.01	2.835 (3)	165
O2W—H2WA⋯O2	0.85	2.00	2.809 (3)	158
O2W—H2WB⋯O2ⁱⁱⁱ	0.85	1.83	2.674 (3)	173
O3W—H3WA⋯O4^iv	0.85	1.85	2.694 (3)	170
O3W—H3WB⋯O1ⁱⁱⁱ	0.85	1.92	2.769 (3)	177
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005368/hy2403sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005368/hy2403Isup2.hkl

checkCIF report

Comment top

Salts of amide have attracted more attention as phase transition dielectric materials for their applications in micro-electronics and memory storage (Fu et al., 2007, 2008, 2009; Fu & Xiong, 2008). With the purpose of obtaining phase transition crystals, the interactions of 1,4-diazabicyclo[2.2.2]octane with various metal ions have been studied and we have elaborated a serie of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound.

The asymmetric unit is composed of an SO₄^2- anion, half 1,4-diazoniabicyclo[2.2.2]octane cation and half [Mg(H₂O)₆]²⁺ cation. (Fig. 1). The Mg^II ion, lying on an inversion center, is in a slightly distorted octahedral geometry formed by six O atoms from the water molecules. The [Mg(H₂O)₆]²⁺ cation possesses typical Mg—O bond lengths [2.035 (2)–2.086 (2) Å], while the O—Mg—O bond angles [88.90 (8)–91.86 (9)°] indicating some distortion from a regular octahedron.

In the crystal, the interionic hydrogen bonds are formed by all H atoms of the water molecules and the amine groups with all O atoms of the SO₄^2- anion and its symmetric equivalents (Table 1). The complex cations [Mg(H₂O)₆]²⁺ and SO₄^2- anions are linked through O—H···O hydrogen bonds into a three-dimensional network, indicating that SO₄^2- anion is a good hydrogen-bonding acceptor. In addition, the amino cations are hydrogen bonded to the SO₄^2- anions through N—H···O hydrogen bonds, which play an important role in stabilizing the crystal structure (Fig. 2).

Related literature top

For the properties and applications of amide salt compounds, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008).

Experimental top

Commercial 1,4-diazabicyclo[2.2.2]octane (3 mmol), H₂SO₄ (3 mmol) and MgSO₄ (3 mmol) were dissolved in water. The solvent was slowly evaporated in air, affording colorless block-shaped crystals of the title compound suitable for X-ray analysis.

The permittivity measurement shows that there is no phase transition within the temperature range from 100 to 400 K, while the permittivity is 10.2 at 1 MHz at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A) -x, y, 0.5-z; (B) 0.5-x, 0.5-y, -z.]
	Fig. 2. The crystal packing of the title compound, showing the three-dimensional hydrogen-bonded network. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

1,4-Diazoniabicyclo[2.2.2]octane hexaaquamagnesium bis(sulfate) top

Crystal data top

(C₆H₁₄N₂)[Mg(H₂O)₆](SO₄)₂	F(000) = 928
M_r = 438.74	D_x = 1.661 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2014 reflections
a = 14.968 (3) Å	θ = 3.1–27.5°
b = 9.1860 (18) Å	µ = 0.41 mm⁻¹
c = 14.334 (3) Å	T = 298 K
β = 117.12 (3)°	Block, colorless
V = 1754.2 (8) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini CCD diffractometer	2014 independent reflections
Radiation source: fine-focus sealed tube	1839 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −19→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.89, T_max = 0.95	l = −18→18
8747 measured reflections

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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.169	w = 1/[σ²(F_o²) + (0.0899P)² + 2.4679P] where P = (F_o² + 2F_c²)/3
S = 1.26	(Δ/σ)_max < 0.001
2014 reflections	Δρ_max = 1.30 e Å⁻³
116 parameters	Δρ_min = −1.08 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.045 (4)

Crystal data top

(C₆H₁₄N₂)[Mg(H₂O)₆](SO₄)₂	V = 1754.2 (8) Å³
M_r = 438.74	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.968 (3) Å	µ = 0.41 mm⁻¹
b = 9.1860 (18) Å	T = 298 K
c = 14.334 (3) Å	0.40 × 0.30 × 0.20 mm
β = 117.12 (3)°

Data collection top

Rigaku SCXmini CCD diffractometer	2014 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1839 reflections with I > 2σ(I)
T_min = 0.89, T_max = 0.95	R_int = 0.022
8747 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.26	Δρ_max = 1.30 e Å⁻³
2014 reflections	Δρ_min = −1.08 e Å⁻³
116 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.61852 (4)	0.24340 (6)	0.11814 (4)	0.0233 (3)
O1W	0.17086 (15)	0.3991 (2)	0.04379 (17)	0.0371 (5)
H1WA	0.1091	0.3776	0.0197	0.056*
H1WB	0.1876	0.4636	0.0913	0.056*
Mg1	0.2500	0.2500	0.0000	0.0216 (3)
O2W	0.37984 (14)	0.3255 (2)	0.11889 (15)	0.0352 (5)
H2WA	0.4372	0.3244	0.1203	0.053*
H2WB	0.3855	0.3321	0.1805	0.053*
O1	0.68789 (16)	0.1296 (2)	0.18242 (15)	0.0383 (5)
O3W	0.23727 (17)	0.1023 (2)	0.10262 (15)	0.0397 (5)
H3WA	0.2082	0.0203	0.0839	0.059*
H3WB	0.2606	0.1142	0.1684	0.059*
O2	0.58702 (19)	0.3346 (3)	0.18142 (17)	0.0490 (7)
N1	−0.02189 (19)	0.2779 (3)	0.15657 (17)	0.0352 (6)
H1	−0.0387	0.2783	0.0870	0.042*
O3	0.52895 (16)	0.1720 (3)	0.03471 (16)	0.0450 (6)
O4	0.66399 (19)	0.3290 (2)	0.06522 (19)	0.0472 (6)
C1	0.0764 (3)	0.2074 (5)	0.2138 (3)	0.0538 (9)
H1B	0.1276	0.2641	0.2066	0.065*
H1C	0.0748	0.1110	0.1855	0.065*
C2	−0.1004 (3)	0.1967 (5)	0.1718 (3)	0.0569 (10)
H2A	−0.1012	0.0955	0.1522	0.068*
H2B	−0.1660	0.2382	0.1283	0.068*
C3	−0.0189 (4)	0.4288 (4)	0.1915 (3)	0.0575 (10)
H3A	−0.0855	0.4713	0.1572	0.069*
H3B	0.0254	0.4863	0.1734	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0256 (4)	0.0261 (4)	0.0189 (4)	−0.0006 (2)	0.0108 (3)	−0.00084 (19)
O1W	0.0286 (10)	0.0394 (11)	0.0437 (11)	−0.0001 (8)	0.0166 (9)	−0.0157 (9)
Mg1	0.0226 (6)	0.0232 (6)	0.0179 (6)	0.0001 (4)	0.0085 (5)	−0.0008 (4)
O2W	0.0254 (9)	0.0532 (13)	0.0245 (9)	−0.0056 (8)	0.0091 (8)	−0.0064 (8)
O1	0.0425 (11)	0.0411 (11)	0.0247 (9)	0.0132 (9)	0.0095 (8)	0.0013 (8)
O3W	0.0609 (14)	0.0335 (11)	0.0253 (10)	−0.0144 (9)	0.0203 (10)	−0.0001 (8)
O2	0.0632 (15)	0.0555 (15)	0.0317 (11)	0.0207 (12)	0.0247 (11)	−0.0024 (10)
N1	0.0370 (13)	0.0521 (15)	0.0166 (10)	0.0083 (11)	0.0122 (10)	0.0022 (9)
O3	0.0314 (11)	0.0643 (16)	0.0304 (11)	−0.0149 (10)	0.0064 (9)	−0.0022 (10)
O4	0.0637 (15)	0.0410 (13)	0.0503 (13)	−0.0170 (11)	0.0378 (13)	−0.0022 (10)
C1	0.052 (2)	0.073 (2)	0.0464 (19)	0.0296 (18)	0.0312 (17)	0.0097 (18)
C2	0.0463 (19)	0.078 (3)	0.0433 (19)	−0.0272 (19)	0.0174 (15)	−0.0236 (18)
C3	0.080 (3)	0.0389 (18)	0.064 (2)	0.0159 (17)	0.042 (2)	0.0226 (16)

Geometric parameters (Å, º) top

S1—O4	1.458 (2)	O3W—H3WB	0.8502
S1—O2	1.462 (2)	N1—C3	1.467 (5)
S1—O1	1.466 (2)	N1—C1	1.469 (4)
S1—O3	1.482 (2)	N1—C2	1.490 (5)
O1W—Mg1	2.0856 (19)	N1—H1	0.9100
O1W—H1WA	0.8502	C1—C2ⁱⁱ	1.513 (5)
O1W—H1WB	0.8500	C1—H1B	0.9700
Mg1—O2W	2.035 (2)	C1—H1C	0.9700
Mg1—O2Wⁱ	2.035 (2)	C2—C1ⁱⁱ	1.513 (5)
Mg1—O3Wⁱ	2.0728 (19)	C2—H2A	0.9700
Mg1—O3W	2.0728 (19)	C2—H2B	0.9700
Mg1—O1Wⁱ	2.0856 (19)	C3—C3ⁱⁱ	1.506 (8)
O2W—H2WA	0.8499	C3—H3A	0.9700
O2W—H2WB	0.8502	C3—H3B	0.9700
O3W—H3WA	0.8499

O4—S1—O2	111.89 (16)	Mg1—O3W—H3WA	123.8
O4—S1—O1	110.28 (14)	Mg1—O3W—H3WB	125.4
O2—S1—O1	110.80 (12)	H3WA—O3W—H3WB	110.9
O4—S1—O3	106.49 (14)	C3—N1—C1	111.0 (3)
O2—S1—O3	109.00 (14)	C3—N1—C2	109.1 (3)
O1—S1—O3	108.21 (14)	C1—N1—C2	110.7 (3)
Mg1—O1W—H1WA	112.8	C3—N1—H1	108.7
Mg1—O1W—H1WB	134.3	C1—N1—H1	108.7
H1WA—O1W—H1WB	110.8	C2—N1—H1	108.7
O2W—Mg1—O2Wⁱ	180.00 (17)	N1—C1—C2ⁱⁱ	108.5 (3)
O2W—Mg1—O3Wⁱ	90.55 (9)	N1—C1—H1B	110.0
O2Wⁱ—Mg1—O3Wⁱ	89.45 (9)	C2ⁱⁱ—C1—H1B	110.0
O2W—Mg1—O3W	89.45 (9)	N1—C1—H1C	110.0
O2Wⁱ—Mg1—O3W	90.55 (9)	C2ⁱⁱ—C1—H1C	110.0
O3Wⁱ—Mg1—O3W	180.00 (13)	H1B—C1—H1C	108.4
O2W—Mg1—O1Wⁱ	91.10 (8)	N1—C2—C1ⁱⁱ	108.2 (3)
O2Wⁱ—Mg1—O1Wⁱ	88.90 (8)	N1—C2—H2A	110.1
O3Wⁱ—Mg1—O1Wⁱ	88.14 (9)	C1ⁱⁱ—C2—H2A	110.1
O3W—Mg1—O1Wⁱ	91.86 (9)	N1—C2—H2B	110.1
O2W—Mg1—O1W	88.90 (8)	C1ⁱⁱ—C2—H2B	110.1
O2Wⁱ—Mg1—O1W	91.10 (8)	H2A—C2—H2B	108.4
O3Wⁱ—Mg1—O1W	91.86 (9)	N1—C3—C3ⁱⁱ	108.51 (18)
O3W—Mg1—O1W	88.14 (9)	N1—C3—H3A	110.0
O1Wⁱ—Mg1—O1W	180.00 (10)	C3ⁱⁱ—C3—H3A	110.0
Mg1—O2W—H2WA	125.8	N1—C3—H3B	110.0
Mg1—O2W—H2WB	119.9	C3ⁱⁱ—C3—H3B	110.0
H2WA—O2W—H2WB	110.8	H3A—C3—H3B	108.4

C3—N1—C1—C2ⁱⁱ	64.8 (4)	C1—N1—C2—C1ⁱⁱ	65.4 (4)
C2—N1—C1—C2ⁱⁱ	−56.5 (4)	C1—N1—C3—C3ⁱⁱ	−55.0 (5)
C3—N1—C2—C1ⁱⁱ	−57.0 (5)	C2—N1—C3—C3ⁱⁱ	67.3 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.91	1.87	2.734 (3)	157
O1W—H1WA···O3ⁱ	0.85	1.90	2.751 (3)	179
O1W—H1WB···O1ⁱⁱⁱ	0.85	2.01	2.835 (3)	165
O2W—H2WA···O2	0.85	2.00	2.809 (3)	158
O2W—H2WB···O2^iv	0.85	1.83	2.674 (3)	173
O3W—H3WA···O4^v	0.85	1.85	2.694 (3)	170
O3W—H3WB···O1^iv	0.85	1.92	2.769 (3)	177

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

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)[Mg(H₂O)₆](SO₄)₂
M_r	438.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.968 (3), 9.1860 (18), 14.334 (3)
β (°)	117.12 (3)
V (Å³)	1754.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.89, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	8747, 2014, 1839
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.169, 1.26
No. of reflections	2014
No. of parameters	116
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.30, −1.08

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.91	1.87	2.734 (3)	157
O1W—H1WA···O3ⁱ	0.85	1.90	2.751 (3)	179
O1W—H1WB···O1ⁱⁱ	0.85	2.01	2.835 (3)	165
O2W—H2WA···O2	0.85	2.00	2.809 (3)	158
O2W—H2WB···O2ⁱⁱⁱ	0.85	1.83	2.674 (3)	173
O3W—H3WA···O4^iv	0.85	1.85	2.694 (3)	170
O3W—H3WB···O1ⁱⁱⁱ	0.85	1.92	2.769 (3)	177

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

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

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