Aqua­trichlorido(1-cyano­methyl-4-aza-1-azoniabicyclo­[2.2.2]octane-κN4)copper(II) monohydrate

Zhou, Q.; Zhang, Y.

doi:10.1107/S1600536812017205

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m674

doi:10.1107/S1600536812017205

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Aquatrichlorido(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane-κN⁴)copper(II) monohydrate

Qinqin Zhou ^a and Yi Zhang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhouqinqin623@sina.com

(Received 15 March 2012; accepted 18 April 2012; online 25 April 2012)

The asymmetric unit of the title compound, [CuCl₃(C₈H₁₄N₃)(H₂O)]·H₂O, comprises a neutral complex and a molecule of free water. The complex contains coordinated Cu^II ions, with Cu—Cl distances ranging from 2.3471 (8) to 2.4011 (8) Å, and with Cu—N and Cu—O distances of 2.0775 (19) and 2.0048 (18) Å, respectively. The resulting coordination polyhedron is a trigonal bipyramid with the Cl atoms in the equatorial plane. In the crystal, O—H⋯Cl and O—H⋯O hydrogen bonds link the molecules into a three-dimensional structure.

Related literature

For background to dielectric-ferroelectric materials, see: Fu et al. (2010 ); Zhang et al. (2008 ). The title compound was prepared in an attempt to make analogs of (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂]·H₂O (Wei & Willett, 1996 ) and (dabcoH₂)CuCl₄ and Zn(dabcoH)Cl₃ (Wei & Willett, 2001 ) (dabco is 1,4-diazabicyclo[2.2.2]octan).

Experimental

Crystal data

[CuCl₃(C₈H₁₄N₃)(H₂O)]·H₂O
M_r = 358.14
Monoclinic, C 2/c
a = 24.301 (5) Å
b = 8.2794 (17) Å
c = 14.069 (3) Å
β = 101.69 (3)°
V = 2771.9 (10) Å³
Z = 8
Mo Kα radiation
μ = 2.15 mm⁻¹
T = 298 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.963, T_max = 0.971
13618 measured reflections
3155 independent reflections
2881 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.093
S = 1.10
3155 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H13⋯Cl2ⁱ	0.93 (4)	2.24 (4)	3.128 (2)	159 (3)
O2—H12⋯O1	0.80 (4)	1.92 (4)	2.693 (3)	160 (4)
O1—H11⋯Cl3ⁱⁱ	0.77 (5)	2.72 (5)	3.447 (3)	159 (4)
O1—H10⋯Cl3ⁱ	0.80 (5)	2.54 (6)	3.337 (3)	171 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017205/fj2535sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017205/fj2535Isup2.hkl

checkCIF report

Comment top

The study of ferroelectric materials has received much attention and some materials have predominantly dielectric-ferroelectric performance (Fu et al.(2010); Zhang et al.(2008)). The title compound was prepared in an attempt to make analogs to (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂].H₂O (Wei & Willett, 1996) and to (dabcoH₂)CuCl₄ and Zn(dabcoH)Cl₃(Wei & Willett, 2001).

The asymmetric unit of the title compound, (dabcoCH₂CN)[CuCl₃(H₂O)].H₂O(dabco is 1,4-bicyclo[2.2.2]octane), comprises a (dabcoCH₂CN)[CuCl₃(H₂O)] moleculeand a molecule of free water.The Cu(dabcoCH₂CN)Cl₃(H₂O) molecule coordinated Cu^II ion has Cu—Cl distances ranging from 2.347 (8) to 2.401 (8) Å, a Cu—N distance of 2.078 (19) Å and a Cu—O distance of 2.005 (18) Å.There are hydrogen bonds found which are O(1)—H(10)···Cl(3), O(1)—H(11)···Cl(3), O(2)—H(13)···Cl(2), O(1)—H(12)···O(1).The hydrogen-bonded sheets link the molecules into a three-dimensional structure.

Related literature top

For background to dielectric-ferroelectric materials, see: Fu et al. (2010); Zhang et al. (2008). The title compound was prepared in an attempt to make analogs of (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂].H₂O (Wei & Willett, 1996) and to (dabcoH₂)CuCl₄ and Zn(dabcoH)Cl₃(Wei & Willett, 2001).

Experimental top

(dabcoCH₂CN)Cl(10 mmol,1.68 g) were dissolved in 15 mL water,thenCuCl₂^.H₂O (10 mmol, 1.70 g) in 15 ml water was added into the previous solution and the mixed solution was filtered last. After a few days a great quantity of green microcrystasls were obtained by by slow evaporation at room temperature in air.

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/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

Aquatrichlorido(1-cyanomethyl-4-aza-1-azoniabicyclo[2.2.2]octane- κN⁴)copper(II) monohydrate top

Crystal data top

[CuCl₃(C₈H₁₄N₃)(H₂O)]·H₂O	F(000) = 1464
M_r = 358.14	D_x = 1.716 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 12903 reflections
a = 24.301 (5) Å	θ = 3.1–27.5°
b = 8.2794 (17) Å	µ = 2.15 mm⁻¹
c = 14.069 (3) Å	T = 298 K
β = 101.69 (3)°	Block, green
V = 2771.9 (10) Å³	0.36 × 0.32 × 0.28 mm
Z = 8

Data collection top

Rigaku SCXmini diffractometer	3155 independent reflections
Radiation source: fine-focus sealed tube	2881 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −31→31
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.963, T_max = 0.971	l = −18→18
13618 measured reflections

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.037P)² + 2.7164P] where P = (F_o² + 2F_c²)/3
3155 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[CuCl₃(C₈H₁₄N₃)(H₂O)]·H₂O	V = 2771.9 (10) Å³
M_r = 358.14	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 24.301 (5) Å	µ = 2.15 mm⁻¹
b = 8.2794 (17) Å	T = 298 K
c = 14.069 (3) Å	0.36 × 0.32 × 0.28 mm
β = 101.69 (3)°

Data collection top

Rigaku SCXmini diffractometer	3155 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2881 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.971	R_int = 0.068
13618 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.62 e Å⁻³
3155 reflections	Δρ_min = −0.86 e Å⁻³
170 parameters

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
C1	0.08955 (10)	0.0927 (3)	0.17062 (17)	0.0250 (5)
H1A	0.0550	0.0937	0.1951	0.030*
H1B	0.1083	−0.0094	0.1887	0.030*
C2	0.07568 (10)	0.1079 (3)	0.05965 (17)	0.0246 (5)
H2A	0.0922	0.0182	0.0309	0.030*
H2B	0.0353	0.1042	0.0366	0.030*
C3	0.09449 (10)	0.3817 (3)	0.19080 (16)	0.0215 (5)
H3A	0.1182	0.4723	0.2164	0.026*
H3B	0.0621	0.3820	0.2212	0.026*
C4	0.07485 (10)	0.4018 (3)	0.08053 (16)	0.0232 (5)
H4A	0.0341	0.4002	0.0636	0.028*
H4B	0.0877	0.5047	0.0603	0.028*
C5	0.17741 (9)	0.2318 (3)	0.17037 (17)	0.0215 (5)
H5A	0.1965	0.1285	0.1806	0.026*
H5B	0.2031	0.3142	0.2019	0.026*
C6	0.16180 (10)	0.2671 (3)	0.06133 (18)	0.0261 (5)
H6A	0.1764	0.3718	0.0479	0.031*
H6B	0.1782	0.1859	0.0258	0.031*
C7	0.08423 (11)	0.2867 (3)	−0.07951 (18)	0.0300 (6)
H7A	0.0986	0.3898	−0.0964	0.036*
H7B	0.1023	0.2023	−0.1099	0.036*
C8	0.02328 (12)	0.2805 (3)	−0.11707 (18)	0.0314 (6)
Cl2	0.20113 (3)	0.44899 (7)	0.38684 (4)	0.02851 (16)
Cl3	0.19677 (3)	−0.05276 (7)	0.34199 (4)	0.02920 (16)
Cl4	0.06069 (3)	0.23400 (10)	0.39370 (5)	0.03668 (18)
Cu1	0.151563 (11)	0.19653 (3)	0.364527 (19)	0.01994 (11)
H10	0.217 (2)	0.384 (6)	0.666 (3)	0.091 (19)*
H11	0.187 (2)	0.295 (5)	0.709 (3)	0.074 (17)*
H12	0.1751 (17)	0.215 (5)	0.543 (3)	0.063 (13)*
H13	0.2148 (17)	0.111 (4)	0.521 (3)	0.055 (10)*
N1	0.12648 (8)	0.2280 (2)	0.21552 (13)	0.0166 (4)
N2	0.09851 (8)	0.2654 (2)	0.02936 (14)	0.0197 (4)
N3	−0.02358 (12)	0.2753 (4)	−0.14739 (19)	0.0471 (7)
O1	0.18732 (11)	0.3383 (3)	0.66114 (18)	0.0418 (5)
O2	0.17734 (8)	0.1430 (2)	0.50550 (13)	0.0276 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0211 (12)	0.0239 (12)	0.0279 (12)	−0.0077 (10)	0.0001 (9)	0.0016 (9)
C2	0.0241 (12)	0.0221 (12)	0.0263 (12)	−0.0055 (10)	0.0018 (9)	−0.0047 (9)
C3	0.0207 (11)	0.0226 (12)	0.0208 (11)	0.0067 (9)	0.0030 (9)	0.0008 (8)
C4	0.0241 (12)	0.0215 (12)	0.0228 (12)	0.0048 (9)	0.0019 (9)	−0.0007 (9)
C5	0.0121 (11)	0.0287 (12)	0.0238 (12)	0.0007 (9)	0.0036 (9)	0.0016 (9)
C6	0.0133 (12)	0.0402 (14)	0.0255 (13)	−0.0021 (10)	0.0057 (9)	0.0013 (10)
C7	0.0272 (14)	0.0432 (16)	0.0190 (12)	0.0016 (11)	0.0035 (10)	−0.0018 (10)
C8	0.0329 (16)	0.0393 (15)	0.0204 (12)	0.0038 (12)	0.0013 (11)	−0.0021 (10)
Cl2	0.0248 (3)	0.0267 (3)	0.0309 (3)	−0.0035 (2)	−0.0016 (2)	−0.0039 (2)
Cl3	0.0303 (3)	0.0266 (3)	0.0309 (3)	0.0101 (2)	0.0067 (2)	0.0034 (2)
Cl4	0.0170 (3)	0.0620 (5)	0.0328 (4)	0.0085 (3)	0.0093 (3)	0.0129 (3)
Cu1	0.01484 (17)	0.02434 (18)	0.01982 (17)	0.00123 (10)	0.00157 (11)	0.00118 (10)
N1	0.0110 (9)	0.0189 (9)	0.0196 (9)	−0.0008 (7)	0.0023 (7)	0.0001 (7)
N2	0.0159 (10)	0.0259 (10)	0.0172 (9)	0.0007 (8)	0.0029 (7)	−0.0018 (7)
N3	0.0357 (16)	0.0609 (18)	0.0387 (15)	0.0060 (13)	−0.0065 (11)	−0.0060 (12)
O1	0.0392 (14)	0.0456 (13)	0.0378 (13)	0.0086 (11)	0.0013 (10)	−0.0065 (10)
O2	0.0252 (10)	0.0324 (10)	0.0229 (9)	0.0049 (8)	−0.0007 (7)	0.0000 (7)

Geometric parameters (Å, º) top

C1—N1	1.493 (3)	C6—N2	1.513 (3)
C1—C2	1.534 (3)	C6—H6A	0.9700
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C7—C8	1.469 (4)
C2—N2	1.512 (3)	C7—N2	1.511 (3)
C2—H2A	0.9700	C7—H7A	0.9700
C2—H2B	0.9700	C7—H7B	0.9700
C3—N1	1.495 (3)	C8—N3	1.133 (4)
C3—C4	1.537 (3)	Cl2—Cu1	2.4011 (8)
C3—H3A	0.9700	Cl3—Cu1	2.3893 (7)
C3—H3B	0.9700	Cl4—Cu1	2.3471 (8)
C4—N2	1.514 (3)	Cu1—O2	2.0048 (18)
C4—H4A	0.9700	Cu1—N1	2.0775 (19)
C4—H4B	0.9700	O1—H10	0.80 (5)
C5—N1	1.502 (3)	O1—H11	0.77 (5)
C5—C6	1.532 (3)	O2—H12	0.80 (4)
C5—H5A	0.9700	O2—H13	0.93 (4)
C5—H5B	0.9700

N1—C1—C2	111.02 (18)	H6A—C6—H6B	108.3
N1—C1—H1A	109.4	C8—C7—N2	111.6 (2)
C2—C1—H1A	109.4	C8—C7—H7A	109.3
N1—C1—H1B	109.4	N2—C7—H7A	109.3
C2—C1—H1B	109.4	C8—C7—H7B	109.3
H1A—C1—H1B	108.0	N2—C7—H7B	109.3
N2—C2—C1	109.86 (18)	H7A—C7—H7B	108.0
N2—C2—H2A	109.7	N3—C8—C7	179.0 (3)
C1—C2—H2A	109.7	O2—Cu1—N1	174.24 (8)
N2—C2—H2B	109.7	O2—Cu1—Cl4	88.43 (6)
C1—C2—H2B	109.7	N1—Cu1—Cl4	93.78 (6)
H2A—C2—H2B	108.2	O2—Cu1—Cl3	83.13 (6)
N1—C3—C4	111.57 (18)	N1—Cu1—Cl3	91.32 (5)
N1—C3—H3A	109.3	Cl4—Cu1—Cl3	127.71 (3)
C4—C3—H3A	109.3	O2—Cu1—Cl2	90.87 (6)
N1—C3—H3B	109.3	N1—Cu1—Cl2	93.43 (6)
C4—C3—H3B	109.3	Cl4—Cu1—Cl2	109.08 (3)
H3A—C3—H3B	108.0	Cl3—Cu1—Cl2	122.51 (3)
N2—C4—C3	109.19 (18)	C1—N1—C3	107.48 (17)
N2—C4—H4A	109.8	C1—N1—C5	108.24 (18)
C3—C4—H4A	109.8	C3—N1—C5	108.54 (18)
N2—C4—H4B	109.8	C1—N1—Cu1	111.19 (14)
C3—C4—H4B	109.8	C3—N1—Cu1	111.95 (13)
H4A—C4—H4B	108.3	C5—N1—Cu1	109.34 (14)
N1—C5—C6	111.69 (18)	C7—N2—C2	111.36 (18)
N1—C5—H5A	109.3	C7—N2—C6	108.14 (18)
C6—C5—H5A	109.3	C2—N2—C6	109.45 (19)
N1—C5—H5B	109.3	C7—N2—C4	111.33 (18)
C6—C5—H5B	109.3	C2—N2—C4	108.25 (18)
H5A—C5—H5B	107.9	C6—N2—C4	108.26 (18)
N2—C6—C5	109.06 (18)	H10—O1—H11	109 (5)
N2—C6—H6A	109.9	Cu1—O2—H12	116 (3)
C5—C6—H6A	109.9	Cu1—O2—H13	113 (2)
N2—C6—H6B	109.9	H12—O2—H13	104 (4)
C5—C6—H6B	109.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H13···Cl2ⁱ	0.93 (4)	2.24 (4)	3.128 (2)	159 (3)
O2—H12···O1	0.80 (4)	1.92 (4)	2.693 (3)	160 (4)
O1—H11···Cl3ⁱⁱ	0.77 (5)	2.72 (5)	3.447 (3)	159 (4)
O1—H10···Cl3ⁱ	0.80 (5)	2.54 (6)	3.337 (3)	171 (5)

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

Experimental details

Crystal data
Chemical formula	[CuCl₃(C₈H₁₄N₃)(H₂O)]·H₂O
M_r	358.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	24.301 (5), 8.2794 (17), 14.069 (3)
β (°)	101.69 (3)
V (Å³)	2771.9 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.15
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.963, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	13618, 3155, 2881
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.093, 1.10
No. of reflections	3155
No. of parameters	170
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.86

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H13···Cl2ⁱ	0.93 (4)	2.24 (4)	3.128 (2)	159 (3)
O2—H12···O1	0.80 (4)	1.92 (4)	2.693 (3)	160 (4)
O1—H11···Cl3ⁱⁱ	0.77 (5)	2.72 (5)	3.447 (3)	159 (4)
O1—H10···Cl3ⁱ	0.80 (5)	2.54 (6)	3.337 (3)	171 (5)

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

Acknowledgements

This work was supported by Jiangsu Planned Projects for Postdoctoral Research Funds (1101010B).

References

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