Crystal structure of trans-aqua­(perchlorato-κO)bis­(propane-1,3-di­amine-κ2N,N′)copper(II) perchlorate

Govindaraj, J.; Rajkumar, K.; Ganeshraja, A.S.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S1600536814023496

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Volume 70| Part 11| November 2014| Pages 438-440

doi:10.1107/S1600536814023496

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Crystal structure of trans-aqua(perchlorato-κO)bis(propane-1,3-diamine-κ²N,N′)copper(II) perchlorate

J. Govindaraj,^a K. Rajkumar,^b A. S. Ganeshraja,^b K. Anbalagan ^b and A. SubbiahPandi ^c,^a ^*

^aDepartment of Physics, Pachaiyappa's College for Men, Kanchipuram 631 501, India, ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, and ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 13 October 2014; accepted 25 October 2014; online 31 October 2014)

In the title compound, [Cu(ClO₄)(C₃H₁₀N₂)₂(H₂O)]ClO₄, the Cu^II atom has a distorted octahedral coordination sphere and is coordinated by the N atoms of two propane-1,3-diamine ligands in the equatorial plane. The axial positions are occupied by a water O atom and an O atom of a disordered perchlorate anion [occupancy ratio 0.631 (9):0.369 (9)]. In the crystal, the various components are linked via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (001).

Keywords: crystal structure; propane-1,3-diamine; copper(II) complex.

CCDC reference: 1031014

1. Chemical context

There have been numerous reports of bis(propane-1,3-diamine)copper(II) complexes, essentially with the copper atom coordinated by the N atoms of the ligands in the equatorial plane of the copper octahedral coordination sphere and with two identical O-containing ligands in the axial positions, for example, trans-diaquabis(propane-1,3-diamine-κ²N,N′)copper(II) dithionate (Kim et al., 2003 ) and bis[aqua(1,3-diaminopropane-κ²N,N′)]copper(II) difluoride (Emsley et al., 1988 ). In order to further develop the coordination chemistry of such copper complexes, we report herein on the synthesis and crystal structure of the title complex, which has two different ligands in the axial positions of the octahedral coordination sphere of the copper atom.

2. Structural commentary

The molecular structure of the title complex is illustrated in Fig. 1. The Cu^II atom has a distorted octahedral coordination sphere, reflecting the characteristic Jahn–Teller distortion. It is coordinated by the N atoms of two propane-1,3-diamine ligands in the equatorial plane with Cu—N bond lengths varying between 2.003 (4)–2.023 (3) Å. The axial positions are occupied by the water O9 atom and by atom O7 of a disordered perchlorate anion [occupancy ratio 0.631 (9):0.369 (9)], with Cu—O bond lengths of 2.585 (6) and 2.680 (10) Å, respectively.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The minor components of the disordered coordinating perchlorate anion have been omitted for clarity.

3. Supramolecular features

In the crystal, the various components are linked via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds forming sheets lying parallel to (001); see Table 1 and Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9B⋯O3ⁱ	0.90 (2)	2.38 (11)	2.917 (9)	118 (9)
N1—H1C⋯O1	0.90	2.22	3.040 (7)	151
N1—H1D⋯O1ⁱⁱ	0.90	2.69	3.511 (8)	151
N1—H1D⋯O9	0.90	2.41	2.927 (8)	117
N2—H2C⋯O5ⁱⁱⁱ	0.90	2.58	3.443 (12)	162
N2—H2C⋯O8ⁱⁱⁱ	0.90	2.42	3.183 (10)	143
N2—H2C⋯O5′ⁱⁱⁱ	0.90	2.39	3.23 (3)	156
N2—H2D⋯O3ⁱⁱⁱ	0.90	2.70	3.449 (11)	141
N3—H3C⋯O6^iv	0.90	2.15	3.014 (9)	160
N3—H3C⋯O7′^iv	0.90	2.36	3.246 (17)	169
N3—H3D⋯O3	0.90	2.28	3.137 (8)	160
N4—H4C⋯O2ⁱⁱⁱ	0.90	2.35	3.127 (6)	144
N4—H4D⋯O4ⁱ	0.90	2.45	3.223 (7)	145
C4—H4A⋯O5′^v	0.97	2.47	3.264 (14)	139
C5—H5B⋯O4ⁱ	0.97	2.63	3.368 (7)	133
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) -x, -y, -z.

Figure 2
A view along the a axis of the crystal structure of the title compound. O—H⋯O and N—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

for details; the minor components of the disordered coordinating perchlorate anion and the C-bound H atoms have been omitted for clarity)

4. Synthesis and crystallization

The complex was prepared by mixing copper(II) perchlorate hexahydrate with 1,3-diaminopropane in a (1:2) molar ratio. Cu(ClO₄)₂·6H₂O (3.7 g, 1 M) was dissolved in 15 ml of warm water. After an hour, about 10 ml of an ethanol solution of 1,3-diaminopropane (1.48 g, 2M) was added dropwise with continuous stirring. This solution was then filtered to remove any impurities and the solution was kept over P₂O₅ in a desiccator. Finally, violet–purple-coloured crystals suitable for X-ray diffraction analysis were harvested and washed repeatedly with cold water (yield 70%).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms were located in a difference Fourier map and refined with a distance restraint, O—H = 0.90 (2) Å, and with U_iso(H) = 1.5U_eq(O). The N -and C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.90 and C—H = 0.97 Å, and with U_iso(H) = 1.2U_eq(N,C). The disordered coordinating perchlorate anion, involving atom Cl2, was refined with an occupancy ratio of 0.631 (9):0.369 (9).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)(C₃H₁₀N₂)₂(H₂O)]ClO₄
M_r	428.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.8563 (4), 14.2936 (6), 14.8769 (7)
β (°)	100.022 (5)
V (Å³)	1645.11 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.70
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Oxford Diffraction Xcalibur with an Eos detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.607, 0.654
No. of measured, independent and observed [I > 2σ(I)] reflections	7573, 2900, 2353
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.06
No. of reflections	2900
No. of parameters	242
No. of restraints	109
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.42
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1031014

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814023496/su2799sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814023496/su2799Isup2.hkl

checkCIF report

Structural commentary top

There have been numerous reports of bis(propane-1,3-diamine)copper(II) complexes, essentially with the copper atom coordinated by the N atoms of the ligands in the equatorial plane of the copper octahedral coordination sphere and with two identical O-containing ligands in the axial positions, for example, trans-diaquabis(propane-1,3-diamine-κ²N,N')copper(II) dithionate (Kim et al., 2003) and bis[aqua(1,3-diaminopropane-κ²N,N')]copper(II) difluoride (Emsley et al., 1988). In order to further develop the coordination chemistry of such copper complexes, we report herein on the synthesis and crystal structure of the title complex, which has two different ligands in the axial positions of the octahedral coordination sphere of the copper atom.

The molecular structure of the title complex is illustrated in Fig. 1. The Cu^II atom has a distorted octahedral coordination sphere. It is coordinated by the N atoms of two propane-1,3-diamine ligands in the equatorial plane with Cu—N bond lengths varying between 2.003 (4)–2.023 (3) Å. The axial positions are occupied by the water O9 atom and by atom O7 of the disordered perchlorate anion [occupancy ratio 0.631 (9):369 (9)], with Cu—O bond lengths of 2.585 (6) and 2.680 (10) Å, respectively.

Supramolecular features top

In the crystal, the various components are linked via O—H..O, N—H···O and C—H···O hydrogen bonds forming sheets lying parallel to (001); see Table 1 and Fig. 2.

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The water H atoms were refined with a distance restraint, O—H = 0.90 (2) Å, and with U_iso(H) = 1.5U_eq(O). The N -and C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.90 and C—H = 0.97 Å, and with U_iso(H) = 1.2U_eq(N,C). The disordered coordinating perchlorate anion, involving atom Cl2, was refined with an occupancy ratio of 0.631 (9):369 (9).

Related literature top

For related copper(II) bis(propane-1,3-diamine) complexes, see: Kim et al. (2003); Emsley et al. (1988).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The minor components of the coordinated perchlorate anion have been omitted for clarity.

A view along the a axis of the crystal packing of the title compound. O—H···O and N—H···O hydrogen bonds are shown as dashed lines (see Table 1 for details; the minor components of the coordinated perchlorate anion and the C-bound H atoms have been omitted for clarity)

trans-Aqua(perchlorato-κO)bis(propane-1,3-diamine-κ²N,N')copper(II) perchlorate top

Crystal data top

[Cu(ClO₄)(C₃H₁₀N₂)₂(H₂O)]ClO₄	F(000) = 884
M_r = 428.72	D_x = 1.731 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2353 reflections
a = 7.8563 (4) Å	θ = 3.8–25.0°
b = 14.2936 (6) Å	µ = 1.70 mm⁻¹
c = 14.8769 (7) Å	T = 293 K
β = 100.022 (5)°	Block, violet-purple
V = 1645.11 (13) Å³	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection top

Oxford diffraction Xcalibur diffractometer with an Eos detector	2900 independent reflections
Radiation source: fine-focus sealed tube	2353 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scans	θ_max = 25.0°, θ_min = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.607, T_max = 0.654	k = −16→16
7573 measured reflections	l = −17→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0667P)² + 1.2858P] where P = (F_o² + 2F_c²)/3
2900 reflections	(Δ/σ)_max = 0.002
242 parameters	Δρ_max = 0.60 e Å⁻³
109 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu(ClO₄)(C₃H₁₀N₂)₂(H₂O)]ClO₄	V = 1645.11 (13) Å³
M_r = 428.72	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8563 (4) Å	µ = 1.70 mm⁻¹
b = 14.2936 (6) Å	T = 293 K
c = 14.8769 (7) Å	0.30 × 0.30 × 0.25 mm
β = 100.022 (5)°

Data collection top

Oxford diffraction Xcalibur diffractometer with an Eos detector	2900 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2353 reflections with I > 2σ(I)
T_min = 0.607, T_max = 0.654	R_int = 0.032
7573 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	109 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.60 e Å⁻³
2900 reflections	Δρ_min = −0.42 e Å⁻³
242 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	Occ. (<1)
C1	0.2060 (10)	0.0648 (5)	0.4655 (4)	0.0879 (19)
H1A	0.2841	0.0599	0.5234	0.105*
H1B	0.1231	0.0142	0.4630	0.105*
C2	0.1130 (10)	0.1523 (5)	0.4648 (4)	0.099 (2)
H2A	0.0517	0.1508	0.5160	0.119*
H2B	0.1985	0.2017	0.4771	0.119*
C3	−0.0098 (8)	0.1800 (5)	0.3854 (4)	0.0846 (17)
H3A	−0.0506	0.2423	0.3965	0.101*
H3B	−0.1084	0.1383	0.3802	0.101*
C4	0.1631 (8)	0.0875 (3)	0.0573 (3)	0.0667 (14)
H4A	0.1641	0.1259	0.0037	0.080*
H4B	0.0489	0.0602	0.0524	0.080*
C5	0.2934 (7)	0.0105 (3)	0.0589 (3)	0.0659 (13)
H5A	0.2758	−0.0197	−0.0004	0.079*
H5B	0.4083	0.0376	0.0693	0.079*
C6	0.2841 (8)	−0.0610 (3)	0.1296 (3)	0.0700 (14)
H6A	0.1671	−0.0851	0.1218	0.084*
H6B	0.3597	−0.1126	0.1208	0.084*
N1	0.3041 (7)	0.0504 (4)	0.3943 (3)	0.0860 (15)
H1C	0.3285	−0.0111	0.3940	0.103*
H1D	0.4054	0.0803	0.4113	0.103*
N2	0.0484 (6)	0.1812 (3)	0.2978 (3)	0.0705 (12)
H2C	0.0951	0.2380	0.2925	0.085*
H2D	−0.0471	0.1780	0.2546	0.085*
N3	0.3333 (6)	−0.0259 (3)	0.2235 (3)	0.0678 (11)
H3C	0.4473	−0.0136	0.2325	0.081*
H3D	0.3180	−0.0730	0.2614	0.081*
N4	0.1967 (6)	0.1474 (2)	0.1393 (2)	0.0573 (10)
H4C	0.1117	0.1902	0.1342	0.069*
H4D	0.2958	0.1786	0.1382	0.069*
O1	0.3452 (8)	−0.1512 (3)	0.4593 (5)	0.149 (2)
O2	0.1810 (6)	−0.2818 (4)	0.4266 (4)	0.1161 (16)
O3	0.3230 (12)	−0.2194 (6)	0.3219 (5)	0.185 (3)
O4	0.4749 (7)	−0.2926 (4)	0.4506 (5)	0.156 (3)
Cl1	0.33528 (15)	−0.23745 (7)	0.41570 (8)	0.0557 (3)
Cl2	−0.18163 (15)	−0.06425 (9)	0.24310 (7)	0.0576 (3)
Cu1	0.21563 (6)	0.08711 (3)	0.26368 (3)	0.0411 (2)
O5	−0.2890 (12)	−0.1162 (7)	0.1754 (6)	0.102 (3)	0.631 (9)
O6	−0.2845 (9)	−0.0126 (8)	0.2958 (6)	0.109 (3)	0.631 (9)
O7	−0.0828 (12)	−0.0013 (7)	0.2023 (6)	0.133 (4)	0.631 (9)
O8	−0.0665 (16)	−0.1226 (7)	0.3013 (6)	0.142 (4)	0.631 (9)
O5'	−0.188 (3)	−0.1082 (17)	0.1585 (9)	0.156 (9)	0.369 (9)
O6'	−0.0084 (12)	−0.0497 (11)	0.2830 (12)	0.117 (5)	0.369 (9)
O7'	−0.2628 (19)	0.0227 (8)	0.2243 (14)	0.131 (6)	0.369 (9)
O8'	−0.258 (2)	−0.1212 (13)	0.2983 (10)	0.138 (6)	0.369 (9)
O9	0.4814 (7)	0.1951 (5)	0.3062 (4)	0.133 (2)
H9B	0.557 (10)	0.173 (8)	0.272 (6)	0.200*
H9A	0.536 (11)	0.222 (7)	0.357 (4)	0.200*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.121 (5)	0.097 (4)	0.048 (3)	0.019 (4)	0.022 (3)	0.011 (3)
C2	0.141 (6)	0.105 (5)	0.058 (3)	0.035 (5)	0.032 (4)	−0.006 (3)
C3	0.081 (4)	0.101 (4)	0.076 (4)	0.024 (3)	0.026 (3)	−0.019 (3)
C4	0.092 (4)	0.062 (3)	0.045 (2)	0.005 (3)	0.009 (3)	0.003 (2)
C5	0.073 (3)	0.067 (3)	0.064 (3)	−0.004 (3)	0.028 (3)	−0.013 (2)
C6	0.081 (4)	0.054 (3)	0.076 (3)	0.015 (3)	0.017 (3)	−0.014 (2)
N1	0.115 (4)	0.086 (3)	0.056 (2)	0.043 (3)	0.013 (3)	0.019 (2)
N2	0.088 (3)	0.066 (3)	0.063 (2)	0.036 (2)	0.028 (2)	0.0098 (19)
N3	0.078 (3)	0.060 (2)	0.064 (2)	0.031 (2)	0.010 (2)	0.0014 (19)
N4	0.080 (3)	0.045 (2)	0.049 (2)	0.0049 (19)	0.0173 (19)	0.0063 (15)
O1	0.138 (5)	0.072 (3)	0.221 (6)	0.001 (3)	−0.014 (4)	−0.046 (4)
O2	0.078 (3)	0.114 (3)	0.163 (5)	−0.024 (3)	0.039 (3)	0.001 (3)
O3	0.245 (9)	0.197 (7)	0.139 (5)	0.046 (6)	0.107 (6)	0.062 (5)
O4	0.080 (3)	0.107 (4)	0.276 (8)	0.042 (3)	0.021 (4)	0.059 (5)
Cl1	0.0524 (6)	0.0451 (6)	0.0733 (7)	0.0054 (5)	0.0212 (6)	0.0074 (5)
Cl2	0.0526 (6)	0.0603 (7)	0.0599 (7)	−0.0013 (5)	0.0092 (5)	−0.0059 (5)
Cu1	0.0435 (3)	0.0393 (3)	0.0415 (3)	0.0075 (2)	0.0096 (2)	0.00435 (19)
O5	0.104 (6)	0.099 (5)	0.097 (6)	−0.017 (5)	0.002 (5)	−0.030 (5)
O6	0.069 (4)	0.162 (9)	0.098 (5)	0.007 (5)	0.019 (4)	−0.049 (6)
O7	0.109 (7)	0.167 (8)	0.127 (7)	−0.064 (6)	0.037 (6)	0.023 (6)
O8	0.185 (10)	0.101 (6)	0.117 (6)	0.043 (7)	−0.040 (7)	0.016 (5)
O5'	0.23 (2)	0.172 (15)	0.059 (8)	0.010 (18)	0.020 (12)	−0.023 (9)
O6'	0.045 (6)	0.115 (11)	0.184 (14)	−0.002 (7)	−0.002 (7)	0.008 (10)
O7'	0.108 (11)	0.064 (7)	0.203 (16)	0.002 (7)	−0.022 (12)	−0.012 (9)
O8'	0.128 (12)	0.182 (15)	0.109 (10)	−0.019 (12)	0.036 (9)	0.044 (10)
O9	0.118 (4)	0.150 (5)	0.133 (5)	−0.054 (4)	0.024 (4)	−0.030 (4)

Geometric parameters (Å, º) top

C1—N1	1.429 (7)	N2—H2C	0.9000
C1—C2	1.447 (8)	N2—H2D	0.9000
C1—H1A	0.9700	N3—Cu1	2.003 (4)
C1—H1B	0.9700	N3—H3C	0.9000
C2—C3	1.445 (9)	N3—H3D	0.9000
C2—H2A	0.9700	N4—Cu1	2.023 (3)
C2—H2B	0.9700	N4—H4C	0.9000
C3—N2	1.454 (6)	N4—H4D	0.9000
C3—H3A	0.9700	O1—Cl1	1.388 (5)
C3—H3B	0.9700	O2—Cl1	1.402 (4)
C4—N4	1.476 (6)	O3—Cl1	1.406 (6)
C4—C5	1.500 (7)	O4—Cl1	1.377 (5)
C4—H4A	0.9700	Cl2—O8'	1.368 (11)
C4—H4B	0.9700	Cl2—O7	1.395 (7)
C5—C6	1.478 (7)	Cl2—O5'	1.399 (12)
C5—H5A	0.9700	Cl2—O6'	1.402 (9)
C5—H5B	0.9700	Cl2—O7'	1.403 (10)
C6—N3	1.471 (6)	Cl2—O5	1.408 (7)
C6—H6A	0.9700	Cl2—O8	1.411 (7)
C6—H6B	0.9700	Cl2—O6	1.425 (6)
N1—Cu1	2.015 (4)	O9—H9B	0.90 (2)
N1—H1C	0.9000	O9—H9A	0.89 (2)
N1—H1D	0.9000	Cu1—09	2.585 (6)
N2—Cu1	2.006 (4)	Cu1—O7	2.680 (1)

N1—C1—C2	117.2 (5)	C6—N3—H3D	107.3
N1—C1—H1A	108.0	Cu1—N3—H3D	107.3
C2—C1—H1A	108.0	H3C—N3—H3D	106.9
N1—C1—H1B	108.0	C4—N4—Cu1	118.9 (3)
C2—C1—H1B	108.0	C4—N4—H4C	107.6
H1A—C1—H1B	107.3	Cu1—N4—H4C	107.6
C3—C2—C1	120.5 (5)	C4—N4—H4D	107.6
C3—C2—H2A	107.2	Cu1—N4—H4D	107.6
C1—C2—H2A	107.2	H4C—N4—H4D	107.0
C3—C2—H2B	107.2	O4—Cl1—O1	110.8 (4)
C1—C2—H2B	107.2	O4—Cl1—O2	110.2 (3)
H2A—C2—H2B	106.8	O1—Cl1—O2	109.1 (4)
C2—C3—N2	117.8 (5)	O4—Cl1—O3	113.1 (5)
C2—C3—H3A	107.9	O1—Cl1—O3	106.8 (5)
N2—C3—H3A	107.9	O2—Cl1—O3	106.6 (5)
C2—C3—H3B	107.9	O8'—Cl2—O7	169.0 (9)
N2—C3—H3B	107.9	O8'—Cl2—O5'	108.7 (11)
H3A—C3—H3B	107.2	O7—Cl2—O5'	80.5 (10)
N4—C4—C5	112.9 (4)	O8'—Cl2—O6'	109.2 (10)
N4—C4—H4A	109.0	O7—Cl2—O6'	61.0 (7)
C5—C4—H4A	109.0	O5'—Cl2—O6'	109.2 (10)
N4—C4—H4B	109.0	O8'—Cl2—O7'	114.5 (10)
C5—C4—H4B	109.0	O7—Cl2—O7'	67.0 (8)
H4A—C4—H4B	107.8	O5'—Cl2—O7'	105.9 (13)
C6—C5—C4	113.7 (4)	O6'—Cl2—O7'	109.1 (8)
C6—C5—H5A	108.8	O8'—Cl2—O5	81.0 (9)
C4—C5—H5A	108.8	O7—Cl2—O5	109.8 (6)
C6—C5—H5B	108.8	O5'—Cl2—O5	36.4 (9)
C4—C5—H5B	108.8	O6'—Cl2—O5	142.9 (7)
H5A—C5—H5B	107.7	O7'—Cl2—O5	97.5 (8)
N3—C6—C5	113.7 (4)	O8'—Cl2—O8	65.3 (8)
N3—C6—H6A	108.8	O7—Cl2—O8	107.6 (6)
C5—C6—H6A	108.8	O5'—Cl2—O8	101.9 (11)
N3—C6—H6B	108.8	O6'—Cl2—O8	50.0 (7)
C5—C6—H6B	108.8	O7'—Cl2—O8	150.1 (8)
H6A—C6—H6B	107.7	O5—Cl2—O8	111.6 (6)
C1—N1—Cu1	122.5 (4)	O8'—Cl2—O6	68.1 (8)
C1—N1—H1C	106.7	O7—Cl2—O6	108.5 (6)
Cu1—N1—H1C	106.7	O5'—Cl2—O6	142.2 (11)
C1—N1—H1D	106.7	O6'—Cl2—O6	106.9 (7)
Cu1—N1—H1D	106.7	O7'—Cl2—O6	50.9 (8)
H1C—N1—H1D	106.6	O5—Cl2—O6	109.9 (5)
C3—N2—Cu1	122.8 (3)	O8—Cl2—O6	109.5 (6)
C3—N2—H2C	106.6	N3—Cu1—N2	166.5 (2)
Cu1—N2—H2C	106.6	N3—Cu1—N1	88.76 (17)
C3—N2—H2D	106.6	N2—Cu1—N1	93.53 (17)
Cu1—N2—H2D	106.6	N3—Cu1—N4	91.99 (15)
H2C—N2—H2D	106.6	N2—Cu1—N4	89.94 (15)
C6—N3—Cu1	120.0 (3)	N1—Cu1—N4	161.9 (2)
C6—N3—H3C	107.3	H9B—O9—H9A	111 (3)
Cu1—N3—H3C	107.3

N1—C1—C2—C3	56.0 (10)	C6—N3—Cu1—N4	−35.4 (4)
C1—C2—C3—N2	−53.1 (10)	C3—N2—Cu1—N3	79.8 (9)
N4—C4—C5—C6	67.7 (6)	C3—N2—Cu1—N1	−19.6 (5)
C4—C5—C6—N3	−66.7 (6)	C3—N2—Cu1—N4	178.1 (5)
C2—C1—N1—Cu1	−41.1 (9)	C1—N1—Cu1—N3	−144.4 (5)
C2—C3—N2—Cu1	35.8 (8)	C1—N1—Cu1—N2	22.4 (5)
C5—C6—N3—Cu1	54.2 (6)	C1—N1—Cu1—N4	123.0 (6)
C5—C4—N4—Cu1	−55.5 (5)	C4—N4—Cu1—N3	36.2 (4)
C6—N3—Cu1—N2	62.7 (8)	C4—N4—Cu1—N2	−130.4 (4)
C6—N3—Cu1—N1	162.7 (4)	C4—N4—Cu1—N1	128.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O3ⁱ	0.90 (2)	2.38 (11)	2.917 (9)	118 (9)
N1—H1C···O1	0.90	2.22	3.040 (7)	151
N1—H1D···O1ⁱⁱ	0.90	2.69	3.511 (8)	151
N1—H1D···O9	0.90	2.41	2.927 (8)	117
N2—H2C···O5ⁱⁱⁱ	0.90	2.58	3.443 (12)	162
N2—H2C···O8ⁱⁱⁱ	0.90	2.42	3.183 (10)	143
N2—H2C···O5′ⁱⁱⁱ	0.90	2.39	3.23 (3)	156
N2—H2D···O3ⁱⁱⁱ	0.90	2.70	3.449 (11)	141
N3—H3C···O6^iv	0.90	2.15	3.014 (9)	160
N3—H3C···O7′^iv	0.90	2.36	3.246 (17)	169
N3—H3D···O3	0.90	2.28	3.137 (8)	160
N4—H4C···O2ⁱⁱⁱ	0.90	2.35	3.127 (6)	144
N4—H4D···O4ⁱ	0.90	2.45	3.223 (7)	145
C4—H4A···O5′^v	0.97	2.47	3.264 (14)	139
C5—H5B···O4ⁱ	0.97	2.63	3.368 (7)	133

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O3ⁱ	0.90 (2)	2.38 (11)	2.917 (9)	118 (9)
N1—H1C···O1	0.90	2.22	3.040 (7)	151
N1—H1D···O1ⁱⁱ	0.90	2.69	3.511 (8)	151
N1—H1D···O9	0.90	2.41	2.927 (8)	117
N2—H2C···O5ⁱⁱⁱ	0.90	2.58	3.443 (12)	162
N2—H2C···O8ⁱⁱⁱ	0.90	2.42	3.183 (10)	143
N2—H2C···O5'ⁱⁱⁱ	0.90	2.39	3.23 (3)	156
N2—H2D···O3ⁱⁱⁱ	0.90	2.70	3.449 (11)	141
N3—H3C···O6^iv	0.90	2.15	3.014 (9)	160
N3—H3C···O7'^iv	0.90	2.36	3.246 (17)	169
N3—H3D···O3	0.90	2.28	3.137 (8)	160
N4—H4C···O2ⁱⁱⁱ	0.90	2.35	3.127 (6)	144
N4—H4D···O4ⁱ	0.90	2.45	3.223 (7)	145
C4—H4A···O5'^v	0.97	2.47	3.264 (14)	139
C5—H5B···O4ⁱ	0.97	2.63	3.368 (7)	133

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

Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)(C₃H₁₀N₂)₂(H₂O)]ClO₄
M_r	428.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.8563 (4), 14.2936 (6), 14.8769 (7)
β (°)	100.022 (5)
V (Å³)	1645.11 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.70
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Oxford diffraction Xcalibur diffractometer with an Eos detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.607, 0.654
No. of measured, independent and observed [I > 2σ(I)] reflections	7573, 2900, 2353
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.06
No. of reflections	2900
No. of parameters	242
No. of restraints	109
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.42

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

JG and ASP are grateful to the CSIR, New Delhi [Lr: No. 01 (2570)/12/EMR-II/3.4.2012] for financial support through a major research project. The authors thank the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

References

Emsley, J., Arif, M., Bates, P. A. & Hursthouse, M. B. (1988). Inorg. Chim. Acta, 154, 17–20. CSD CrossRef CAS Web of Science Google Scholar
Kim, Y., Skelton, B. W. & White, A. H. (2003). Acta Cryst. C59, m546–m548. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 70| Part 11| November 2014| Pages 438-440

doi:10.1107/S1600536814023496

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