Tetra­kis(1H-imidazole-κN3)(perchlorato-κO)copper(II) perchlorate dimethyl­amine disolvate

Zhou, Y.-X.; Cheng, G.-X.; Wu, B.-L.; Zhang, H.-Y.

doi:10.1107/S1600536807037440

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Tetrakis(1H-imidazole-κN³)(perchlorato-κO)copper(II) perchlorate dimethylamine disolvate

Y.-X. Zhou, G.-X. Cheng, B.-L. Wu and H.-Y. Zhang

The asymmetric unit of the title compound, [Cu(ClO₄)(C₃H₄N₂)₄]ClO₄·2C₂H₇N₂, consists of a cationic tetrakis(1H-imidazole)perchloratocopper(II) complex, two dimethylamine solvent molecules and one perchlorate counter-anion. The coordination geometry of the metal atom is tetragonal-pyramidal, with four imidazole molecules in the basal plane and a perchlorate anion at the apex. The complex cations act as multiple connectors and self-assemble into a one-dimensional hydrogen-bonded ribbon, which is further hydrogen bonded with the perchlorate anion and solvent dimethylamine to form a two-dimensional framework.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037440/at2354sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037440/at2354Isup2.hkl Contains datablock I

CCDC reference: 660063

checkCIF report

Key indicators

Single-crystal X-ray study
T = 273 K
Mean (C-C) = 0.004 Å
R factor = 0.039
wR factor = 0.119
Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT165_ALERT_3_C Nr. of Status R Flagged Non-Hydrogen Atoms .....          2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N9
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        N10
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2
PLAT751_ALERT_4_C Bond    Calc     1.47252, Rep    1.472(4) ......  Senseless su
              N10  -C16     1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     1.47931, Rep    1.480(4) ......  Senseless su
              N10  -C15     1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     1.45362, Rep    1.454(4) ......  Senseless su
              N9   -C13     1.555   1.555
PLAT751_ALERT_4_C Bond    Calc     1.47444, Rep    1.475(4) ......  Senseless su
              N9   -C14     1.555   1.555
PLAT752_ALERT_4_C Angle   Calc      113.44, Rep    113.4(2) ......  Senseless su
              C16  -N10  -C15     1.555   1.555   1.555
PLAT752_ALERT_4_C Angle   Calc      113.75, Rep    113.7(3) ......  Senseless su
              C13  -N9   -C14     1.555   1.555   1.555
PLAT757_ALERT_4_C D...A   Calc     2.69290, Rep    2.693(3) ......  Senseless su
              N9   -O5      1.555   1.545
PLAT757_ALERT_4_C D...A   Calc     2.71724, Rep    2.717(3) ......  Senseless su
              N9   -O6      1.555   3.566
PLAT757_ALERT_4_C D...A   Calc     2.74923, Rep    2.749(2) ......  Senseless su
              N10  -O3      1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C2 H7 N

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.13

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

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

Comment top

In decades, hydrogen bonding with directionality and strength has been widely exploited by crystal engineers to control and tune structure topologies. For example, the carboxylic acid moiety as a graceful supramolecular synthon can be hydrogen bonded into not only discrete aggregates and one-dimensional polymers but also two-dimensional and three-dimensional networks; and calix-C-methylresorcin-[4]arenes self-assembled with water molecules held together by hydrogen bonds into a spheroid with a very large enclosed cavity of 1375 Å³ (Moulton & Zaworotko, 2001). Of currently attractive are coordination complexes encoding multiple hydrogen-bonding acceptors and donors embedded in ligands because these supramolecular synthons incorporating stereostructure and H-bond sites can further construct higher-ordered aggregates through H-bond recognitions (Lavalette et al., 2003; Głowiak & Wnęk, 1985). We communicate herein the synthesis and hydrogen-bonded two-dimensional planar sheet constructed by novel one-dimensional hydrogen-bonded ribbons of the title compound, [Cu(C₃H₄N₂)₄(ClO₄)]⁺.(ClO₄)^-.2(C₂H₇N), (I).

In (I), the coordination enviroment of Cu(II) ion is axially elongated tetragonal-pyramidal (Fig. 1 and Table 1). The Cu(II) atom is Penta-coordinated by N₄O with four terminal imidazole molecules arranged almost perpendicular to the Cu—N₄ plane in base [Cu—N, from 2.0104 (19) to 2.0347 (19) Å] and a terminal perchlorate anion at apex [Cu—O, 2.2796 (19) Å]. As clearly shown in Fig. 2, the cation complex is an excellent supramolecular synthon. The four terminal imidazole ligands acting as hydrogen-bonding donors bind two lattice perchlorates and two coordination perchlorates, respectively, while, with the free coordination oxygen O4 as hydrogen-bonding acceptors, the coordination perchlorate anion also connect with two imidazole ligands from different complex ions (Table 2). Thus, the cation complex is a notable six-connector, and self-assembles into a novel one-dimensional hydrogen-bonded ribbon by paired N—H···O hydrogen bonds. With lattice perchlorate being captured at one corner by other paired N—H···O hydrogen bonds, the novel one-dimensional hydrogen-bonded ribbons finally extend into a hydrogen-bonded two-dimensional planar sheet in the direction parallel to the (1 0 1) plane (Fig. 3), and pack up in crystals (Fig. 4). Remarkably, through H-bond interactions, dimethylamine molecules which have been determined by single-crystal and elemental analysis inhabit in cavities of the one-dimensional hydrogen-bonded ribbons or ride at the lattice perchlorate. Perhaps, the dimethylamine derived from the decomposition of N,N-dimethylformamide in the reaction system (Xu et al., 2004).

Related literature top

For related literature, see: Głowiak & Wnęk (1985); Lavalette et al. (2003); Moulton & Zaworotko (2001); Sengupta et al. (2001); Xu et al. (2004).

Experimental top

A solution of imidazole (0.0272 g, 0.4 mmol) and N,N-dimethylformamide (5 ml) was mixed with a solution of Cu(ClO₄)₂.6H₂O (0.0371 g, 0.1 mmol) in methanol (15 ml) with sharp stir. Then the mixture was heated for half an hour in water bath at 333 K, which led to a green solution. With the solution slowly evaporating in room temperature for three week, green block crystal appeared. Filtrated, washed with a few drops of methanol and dried naturally, pure title compound of 0.047 g was obtained (yield 75%); Analysis calculated for C₁₆H₃₀Cl₂CuN₁₀O₈: C 30.75, H 4.84, N 22.41%. Found: C 30.82, H 4.79, N 22.45%.

Structure description top

For related literature, see: Głowiak & Wnęk (1985); Lavalette et al. (2003); Moulton & Zaworotko (2001); Sengupta et al. (2001); Xu et al. (2004).

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. An ORTEP representation of the asymmetry unit in the title compound (I), showing tetragonal-pyramidal coordination geometry around metal center Cu(II). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. View of the self-assembly of complex (I) into a novel one-dimensional hydrogen-bonded ribbon by paired N—H···O hydrogen bonds.
	Fig. 3. View of a hydrogen-bonded two-dimensional planar sheet extending in the direction parallel to the (1 0 1) plane.
	Fig. 4. Packing diagram of the title compound (I), showing guest dimethylamine molecules inhabited in the cavities (partial hydrogen atoms have been omitted for clarity).

Tetrakis(1H-imidazole-κN³)(perchlorato-κO)copper(II) perchlorate dimethylamine disolvate top

Crystal data top

[Cu(ClO₄)(C₃H₄N₂)₄]ClO₄·2C₂H₇N₂	F(000) = 1292
M_r = 624.94	D_x = 1.606 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6261 reflections
a = 16.5302 (17) Å	θ = 2.5–27.9°
b = 9.2777 (10) Å	µ = 1.11 mm⁻¹
c = 20.7248 (15) Å	T = 273 K
β = 125.580 (5)°	Block, green
V = 2585.0 (5) Å³	0.32 × 0.29 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	6240 independent reflections
Radiation source: fine-focus sealed tube	4989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→21
T_min = 0.712, T_max = 0.765	k = −12→12
21182 measured reflections	l = −27→26

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0615P)² + 1.869P] where P = (F_o² + 2F_c²)/3
6240 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[Cu(ClO₄)(C₃H₄N₂)₄]ClO₄·2C₂H₇N₂	V = 2585.0 (5) Å³
M_r = 624.94	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.5302 (17) Å	µ = 1.11 mm⁻¹
b = 9.2777 (10) Å	T = 273 K
c = 20.7248 (15) Å	0.32 × 0.29 × 0.25 mm
β = 125.580 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6240 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4989 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.765	R_int = 0.030
21182 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	Δρ_max = 0.66 e Å⁻³
6240 reflections	Δρ_min = −0.87 e Å⁻³
328 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
Cu1	0.28355 (2)	0.24588 (3)	0.777041 (17)	0.02098 (10)
Cl1	0.52647 (4)	0.21986 (6)	0.92904 (3)	0.02249 (13)
O1	0.45053 (13)	0.28852 (19)	0.85304 (10)	0.0293 (4)
N1	0.25032 (16)	0.0965 (2)	0.82932 (12)	0.0243 (4)
C1	0.1562 (2)	0.0424 (3)	0.79480 (16)	0.0311 (5)
H1A	0.0997	0.0647	0.7429	0.037*
Cl2	0.04412 (4)	0.77614 (6)	0.43718 (3)	0.02472 (14)
O2	0.51351 (15)	0.2707 (2)	0.99015 (11)	0.0388 (5)
N2	0.25177 (17)	−0.0490 (2)	0.91358 (13)	0.0311 (5)
H2B	0.2736	−0.0988	0.9570	0.037*
C2	0.1568 (2)	−0.0483 (3)	0.84686 (16)	0.0318 (6)
H2C	0.1019	−0.1006	0.8382	0.038*
O3	0.51743 (15)	0.06216 (19)	0.92169 (12)	0.0402 (5)
N3	0.25347 (16)	0.3963 (2)	0.83014 (12)	0.0244 (4)
C3	0.30678 (19)	0.0401 (3)	0.90176 (15)	0.0269 (5)
H3B	0.3756	0.0595	0.9396	0.032*
O4	0.62696 (14)	0.26129 (18)	0.95327 (11)	0.0283 (4)
N4	0.26774 (17)	0.5529 (2)	0.91551 (13)	0.0311 (5)
H4B	0.2947	0.6063	0.9584	0.037*
C4	0.3164 (2)	0.4596 (3)	0.89952 (15)	0.0273 (5)
H4C	0.3859	0.4417	0.9332	0.033*
O5	0.01465 (19)	0.9259 (2)	0.43397 (19)	0.0682 (8)
N5	0.27036 (15)	0.3940 (2)	0.70031 (11)	0.0225 (4)
C5	0.1696 (2)	0.5503 (3)	0.85361 (16)	0.0343 (6)
H5B	0.1176	0.6056	0.8482	0.041*
O6	0.01920 (16)	0.6908 (3)	0.48374 (13)	0.0492 (6)
N6	0.2068 (2)	0.5493 (2)	0.60361 (13)	0.0435 (6)
H6B	0.1627	0.6045	0.5638	0.052*
C6	0.1612 (2)	0.4522 (3)	0.80090 (16)	0.0321 (6)
H6C	0.1010	0.4266	0.7518	0.039*
O7	−0.00792 (18)	0.7188 (3)	0.35769 (13)	0.0571 (7)
N7	0.29348 (15)	0.0923 (2)	0.71186 (12)	0.0235 (4)
C7	0.1884 (2)	0.4609 (3)	0.64449 (15)	0.0326 (6)
H7B	0.1251	0.4481	0.6347	0.039*
O8	0.15263 (14)	0.7693 (2)	0.47831 (12)	0.0352 (4)
N8	0.25757 (17)	−0.0565 (2)	0.61590 (12)	0.0316 (5)
H8B	0.2230	−0.1104	0.5731	0.038*
C8	0.3048 (3)	0.5398 (3)	0.63370 (17)	0.0425 (7)
H8C	0.3388	0.5906	0.6164	0.051*
C9	0.3441 (2)	0.4422 (3)	0.69392 (16)	0.0309 (5)
H9A	0.4117	0.4123	0.7263	0.037*
C10	0.38020 (19)	0.0519 (3)	0.72164 (15)	0.0282 (5)
H10A	0.4451	0.0835	0.7631	0.034*
C11	0.3582 (2)	−0.0407 (3)	0.66236 (16)	0.0311 (5)
H11A	0.4040	−0.0853	0.6550	0.037*
C12	0.21965 (11)	0.02468 (15)	0.64659 (9)	0.0289 (5)
H12A	0.1510	0.0325	0.6251	0.035*
N10	0.42910 (11)	−0.20296 (15)	0.86560 (9)	0.0321 (5)
H10B	0.4422	−0.1364	0.9021	0.038*
N9	0.06492 (11)	0.20562 (15)	0.44547 (9)	0.0434 (6)
H9B	0.0467	0.1522	0.4701	0.052*
C13	0.1675 (3)	0.2473 (4)	0.4811 (3)	0.0596 (10)
H13A	0.2102	0.2075	0.5348	0.089*
H13B	0.1727	0.3526	0.4835	0.089*
H13C	0.1886	0.2098	0.4488	0.089*
C14	−0.0058 (4)	0.2612 (4)	0.3643 (3)	0.0669 (11)
H14A	−0.0733	0.2299	0.3441	0.100*
H14B	0.0120	0.2239	0.3298	0.100*
H14C	−0.0031	0.3668	0.3650	0.100*
C15	0.3270 (3)	−0.2450 (3)	0.79940 (18)	0.0380 (7)
H15A	0.2788	−0.1894	0.8023	0.057*
H15B	0.3174	−0.3481	0.8032	0.057*
H15C	0.3171	−0.2255	0.7488	0.057*
C16	0.5070 (3)	−0.2820 (4)	0.8665 (2)	0.0578 (9)
H16A	0.5726	−0.2499	0.9117	0.087*
H16B	0.5004	−0.2632	0.8171	0.087*
H16C	0.4997	−0.3856	0.8712	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03030 (18)	0.01577 (14)	0.02325 (16)	0.00019 (11)	0.01922 (14)	0.00038 (10)
Cl1	0.0205 (3)	0.0258 (3)	0.0189 (3)	−0.0009 (2)	0.0102 (2)	0.0005 (2)
O1	0.0261 (10)	0.0329 (9)	0.0209 (8)	0.0013 (7)	0.0091 (8)	0.0040 (7)
N1	0.0319 (11)	0.0206 (9)	0.0251 (10)	−0.0007 (8)	0.0191 (9)	0.0013 (8)
C1	0.0279 (14)	0.0321 (13)	0.0299 (13)	0.0001 (10)	0.0148 (11)	0.0064 (11)
Cl2	0.0223 (3)	0.0272 (3)	0.0228 (3)	−0.0005 (2)	0.0120 (2)	0.0007 (2)
O2	0.0337 (11)	0.0634 (14)	0.0236 (9)	0.0114 (9)	0.0192 (9)	0.0030 (8)
N2	0.0388 (13)	0.0302 (11)	0.0302 (11)	0.0049 (9)	0.0234 (10)	0.0096 (9)
C2	0.0299 (14)	0.0314 (13)	0.0374 (14)	−0.0029 (11)	0.0216 (12)	0.0051 (11)
O3	0.0384 (12)	0.0222 (9)	0.0433 (11)	−0.0062 (8)	0.0143 (10)	0.0013 (8)
N3	0.0310 (11)	0.0200 (9)	0.0267 (10)	−0.0010 (8)	0.0194 (9)	−0.0029 (8)
C3	0.0291 (13)	0.0264 (12)	0.0272 (12)	−0.0006 (10)	0.0176 (11)	0.0005 (10)
O4	0.0224 (9)	0.0373 (10)	0.0257 (9)	−0.0079 (7)	0.0143 (8)	−0.0061 (7)
N4	0.0393 (13)	0.0277 (11)	0.0267 (10)	−0.0026 (9)	0.0193 (10)	−0.0092 (9)
C4	0.0301 (13)	0.0245 (11)	0.0268 (12)	−0.0008 (10)	0.0162 (11)	−0.0017 (9)
O5	0.0570 (16)	0.0278 (11)	0.129 (2)	0.0085 (10)	0.0591 (18)	0.0038 (13)
N5	0.0247 (11)	0.0199 (9)	0.0231 (9)	0.0013 (8)	0.0140 (9)	0.0025 (7)
C5	0.0332 (15)	0.0359 (14)	0.0361 (14)	0.0015 (11)	0.0215 (13)	−0.0085 (12)
O6	0.0421 (13)	0.0645 (14)	0.0445 (12)	−0.0002 (11)	0.0272 (11)	0.0217 (11)
N6	0.0555 (17)	0.0292 (12)	0.0263 (11)	0.0066 (11)	0.0126 (12)	0.0112 (9)
C6	0.0294 (14)	0.0361 (14)	0.0311 (13)	−0.0024 (11)	0.0178 (12)	−0.0101 (11)
O7	0.0407 (14)	0.0908 (19)	0.0264 (11)	−0.0196 (12)	0.0119 (10)	−0.0220 (11)
N7	0.0296 (11)	0.0200 (9)	0.0246 (10)	0.0004 (8)	0.0178 (9)	−0.0011 (8)
C7	0.0286 (14)	0.0286 (12)	0.0291 (13)	0.0034 (10)	0.0102 (11)	0.0003 (10)
O8	0.0199 (10)	0.0517 (12)	0.0274 (9)	0.0010 (8)	0.0099 (8)	0.0011 (8)
N8	0.0403 (13)	0.0263 (11)	0.0245 (10)	−0.0054 (9)	0.0168 (10)	−0.0074 (8)
C8	0.064 (2)	0.0360 (15)	0.0364 (15)	−0.0126 (14)	0.0343 (16)	0.0014 (12)
C9	0.0320 (14)	0.0340 (13)	0.0323 (13)	−0.0027 (11)	0.0219 (12)	0.0036 (11)
C10	0.0285 (13)	0.0300 (12)	0.0281 (12)	−0.0045 (10)	0.0177 (11)	−0.0077 (10)
C11	0.0334 (14)	0.0318 (13)	0.0319 (13)	0.0001 (11)	0.0212 (12)	−0.0067 (11)
C12	0.0304 (14)	0.0259 (12)	0.0280 (12)	−0.0013 (10)	0.0157 (11)	−0.0009 (10)
N10	0.0443 (14)	0.0265 (10)	0.0293 (11)	−0.0029 (10)	0.0237 (11)	−0.0048 (9)
N9	0.0523 (17)	0.0352 (12)	0.0491 (15)	−0.0021 (12)	0.0331 (14)	0.0038 (11)
C13	0.064 (3)	0.054 (2)	0.064 (3)	−0.0127 (17)	0.040 (2)	−0.0039 (17)
C14	0.073 (3)	0.071 (3)	0.057 (2)	0.008 (2)	0.037 (2)	0.0065 (18)
C15	0.0472 (19)	0.0309 (14)	0.0317 (14)	−0.0038 (12)	0.0206 (14)	−0.0025 (11)
C16	0.061 (2)	0.064 (2)	0.064 (2)	0.0081 (18)	0.045 (2)	−0.0023 (18)

Geometric parameters (Å, º) top

Cu1—N3	2.0104 (19)	N6—H6B	0.8800
Cu1—N5	2.0151 (19)	C6—H6C	0.9500
Cu1—N1	2.0223 (19)	N7—C12	1.339 (2)
Cu1—N7	2.0347 (19)	N7—C10	1.378 (3)
Cu1—O1	2.2796 (19)	C7—H7B	0.9500
Cl1—O3	1.4695 (19)	N8—C12	1.352 (3)
Cl1—O1	1.4702 (18)	N8—C11	1.361 (4)
Cl1—O2	1.4794 (19)	N8—H8B	0.8800
Cl1—O4	1.4794 (18)	C8—C9	1.362 (4)
N1—C3	1.330 (3)	C8—H8C	0.9500
N1—C1	1.375 (3)	C9—H9A	0.9500
C1—C2	1.363 (3)	C10—C11	1.363 (3)
C1—H1A	0.9500	C10—H10A	0.9500
Cl2—O7	1.445 (2)	C11—H11A	0.9500
Cl2—O5	1.461 (2)	C12—H12A	0.9500
Cl2—O8	1.473 (2)	N10—C16	1.472 (4)
Cl2—O6	1.480 (2)	N10—C15	1.480 (4)
N2—C3	1.352 (3)	N10—H10B	0.9000
N2—C2	1.360 (4)	N9—C13	1.454 (4)
N2—H2B	0.8800	N9—C14	1.475 (4)
C2—H2C	0.9500	N9—H9B	0.8800
N3—C4	1.324 (3)	C13—H13A	0.9800
N3—C6	1.374 (3)	C13—H13B	0.9800
C3—H3B	0.9500	C13—H13C	0.9800
N4—C4	1.348 (3)	C14—H14A	0.9800
N4—C5	1.362 (4)	C14—H14B	0.9800
N4—H4B	0.8800	C14—H14C	0.9800
C4—H4C	0.9500	C15—H15A	0.9800
N5—C7	1.317 (3)	C15—H15B	0.9800
N5—C9	1.375 (3)	C15—H15C	0.9800
C5—C6	1.365 (3)	C16—H16A	0.9800
C5—H5B	0.9500	C16—H16B	0.9800
N6—C7	1.335 (4)	C16—H16C	0.9800
N6—C8	1.359 (4)

N3—Cu1—N5	90.64 (8)	C5—C6—H6C	125.4
N3—Cu1—N1	87.23 (8)	N3—C6—H6C	125.4
N5—Cu1—N1	162.13 (9)	C12—N7—C10	106.26 (17)
N3—Cu1—N7	172.14 (8)	C12—N7—Cu1	128.37 (14)
N5—Cu1—N7	88.11 (8)	C10—N7—Cu1	124.88 (16)
N1—Cu1—N7	91.59 (8)	N5—C7—N6	110.4 (2)
N3—Cu1—O1	94.99 (8)	N5—C7—H7B	124.8
N5—Cu1—O1	87.62 (7)	N6—C7—H7B	124.8
N1—Cu1—O1	110.24 (8)	C12—N8—C11	108.51 (19)
N7—Cu1—O1	92.71 (7)	C12—N8—H8B	125.7
O3—Cl1—O1	110.39 (11)	C11—N8—H8B	125.7
O3—Cl1—O2	110.46 (12)	N6—C8—C9	105.6 (2)
O1—Cl1—O2	108.68 (11)	N6—C8—H8C	127.2
O3—Cl1—O4	108.68 (11)	C9—C8—H8C	127.2
O1—Cl1—O4	109.96 (11)	C8—C9—N5	109.1 (3)
O2—Cl1—O4	108.65 (11)	C8—C9—H9A	125.4
Cl1—O1—Cu1	126.93 (11)	N5—C9—H9A	125.4
C3—N1—C1	106.4 (2)	C11—C10—N7	109.2 (2)
C3—N1—Cu1	130.05 (18)	C11—C10—H10A	125.4
C1—N1—Cu1	123.33 (16)	N7—C10—H10A	125.4
C2—C1—N1	109.2 (2)	N8—C11—C10	106.3 (2)
C2—C1—H1A	125.4	N8—C11—H11A	126.8
N1—C1—H1A	125.4	C10—C11—H11A	126.8
O7—Cl2—O5	109.68 (17)	N7—C12—N8	109.67 (16)
O7—Cl2—O8	111.14 (13)	N7—C12—H12A	125.2
O5—Cl2—O8	109.20 (13)	N8—C12—H12A	125.2
O7—Cl2—O6	109.84 (15)	C16—N10—C15	113.4 (2)
O5—Cl2—O6	109.05 (15)	C16—N10—H10B	123.4
O8—Cl2—O6	107.88 (12)	C15—N10—H10B	123.2
C3—N2—C2	108.2 (2)	C13—N9—C14	113.7 (3)
C3—N2—H2B	125.9	C13—N9—H9B	123.1
C2—N2—H2B	125.9	C14—N9—H9B	123.1
N2—C2—C1	106.3 (2)	N9—C13—H13A	109.5
N2—C2—H2C	126.9	N9—C13—H13B	109.5
C1—C2—H2C	126.9	H13A—C13—H13B	109.5
C4—N3—C6	106.3 (2)	N9—C13—H13C	109.5
C4—N3—Cu1	127.88 (17)	H13A—C13—H13C	109.5
C6—N3—Cu1	125.83 (17)	H13B—C13—H13C	109.5
N1—C3—N2	109.9 (2)	N9—C14—H14A	109.5
N1—C3—H3B	125.0	N9—C14—H14B	109.5
N2—C3—H3B	125.0	H14A—C14—H14B	109.5
C4—N4—C5	108.1 (2)	N9—C14—H14C	109.5
C4—N4—H4B	125.9	H14A—C14—H14C	109.5
C5—N4—H4B	125.9	H14B—C14—H14C	109.5
N3—C4—N4	110.4 (2)	N10—C15—H15A	109.5
N3—C4—H4C	124.8	N10—C15—H15B	109.5
N4—C4—H4C	124.8	H15A—C15—H15B	109.5
C7—N5—C9	106.2 (2)	N10—C15—H15C	109.5
C7—N5—Cu1	126.73 (18)	H15A—C15—H15C	109.5
C9—N5—Cu1	127.08 (17)	H15B—C15—H15C	109.5
N4—C5—C6	106.1 (2)	N10—C16—H16A	109.5
N4—C5—H5B	127.0	N10—C16—H16B	109.5
C6—C5—H5B	127.0	H16A—C16—H16B	109.5
C7—N6—C8	108.7 (2)	N10—C16—H16C	109.5
C7—N6—H6B	125.7	H16A—C16—H16C	109.5
C8—N6—H6B	125.7	H16B—C16—H16C	109.5
C5—C6—N3	109.2 (2)

O3—Cl1—O1—Cu1	51.84 (16)	N1—Cu1—N5—C7	15.6 (4)
O2—Cl1—O1—Cu1	−69.45 (16)	N7—Cu1—N5—C7	104.9 (2)
O4—Cl1—O1—Cu1	171.74 (11)	O1—Cu1—N5—C7	−162.3 (2)
N3—Cu1—O1—Cl1	89.35 (14)	N3—Cu1—N5—C9	114.8 (2)
N5—Cu1—O1—Cl1	179.78 (14)	N1—Cu1—N5—C9	−162.2 (2)
N1—Cu1—O1—Cl1	0.47 (16)	N7—Cu1—N5—C9	−72.9 (2)
N7—Cu1—O1—Cl1	−92.23 (14)	O1—Cu1—N5—C9	19.9 (2)
N3—Cu1—N1—C3	−84.1 (2)	C4—N4—C5—C6	0.5 (3)
N5—Cu1—N1—C3	−167.5 (2)	N4—C5—C6—N3	−0.5 (3)
N7—Cu1—N1—C3	103.7 (2)	C4—N3—C6—C5	0.2 (3)
O1—Cu1—N1—C3	10.3 (2)	Cu1—N3—C6—C5	179.30 (18)
N3—Cu1—N1—C1	89.9 (2)	N5—Cu1—N7—C12	−84.60 (17)
N5—Cu1—N1—C1	6.5 (4)	N1—Cu1—N7—C12	77.53 (18)
N7—Cu1—N1—C1	−82.3 (2)	O1—Cu1—N7—C12	−172.12 (17)
O1—Cu1—N1—C1	−175.75 (18)	N5—Cu1—N7—C10	86.23 (19)
C3—N1—C1—C2	−0.7 (3)	N1—Cu1—N7—C10	−111.65 (19)
Cu1—N1—C1—C2	−175.89 (17)	O1—Cu1—N7—C10	−1.30 (19)
C3—N2—C2—C1	0.2 (3)	C9—N5—C7—N6	−0.3 (3)
N1—C1—C2—N2	0.3 (3)	Cu1—N5—C7—N6	−178.51 (17)
N5—Cu1—N3—C4	−105.0 (2)	C8—N6—C7—N5	0.1 (3)
N1—Cu1—N3—C4	92.8 (2)	C7—N6—C8—C9	0.1 (3)
O1—Cu1—N3—C4	−17.3 (2)	N6—C8—C9—N5	−0.3 (3)
N5—Cu1—N3—C6	76.1 (2)	C7—N5—C9—C8	0.4 (3)
N1—Cu1—N3—C6	−86.1 (2)	Cu1—N5—C9—C8	178.57 (18)
O1—Cu1—N3—C6	163.8 (2)	C12—N7—C10—C11	−0.3 (3)
C1—N1—C3—N2	0.8 (3)	Cu1—N7—C10—C11	−172.86 (17)
Cu1—N1—C3—N2	175.60 (16)	C12—N8—C11—C10	−0.1 (3)
C2—N2—C3—N1	−0.7 (3)	N7—C10—C11—N8	0.3 (3)
C6—N3—C4—N4	0.1 (3)	C10—N7—C12—N8	0.3 (2)
Cu1—N3—C4—N4	−178.94 (16)	Cu1—N7—C12—N8	172.43 (15)
C5—N4—C4—N3	−0.4 (3)	C11—N8—C12—N7	−0.1 (2)
N3—Cu1—N5—C7	−67.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4ⁱ	0.88	2.21	3.013 (3)	152
N4—H4B···O4ⁱⁱ	0.88	1.94	2.808 (3)	167
N8—H8B···O8ⁱⁱⁱ	0.88	1.95	2.828 (3)	177
N9—H9B···O5ⁱⁱⁱ	0.88	2.19	2.693 (3)	116
N9—H9B···O6^iv	0.88	2.33	2.717 (3)	107
N6—H6B···O6	0.88	2.11	2.924 (3)	154
N6—H6B···O8	0.88	2.27	3.001 (3)	140
N10—H10B···O3	0.90	2.13	2.749 (2)	126

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

Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)(C₃H₄N₂)₄]ClO₄·2C₂H₇N₂
M_r	624.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	16.5302 (17), 9.2777 (10), 20.7248 (15)
β (°)	125.580 (5)
V (Å³)	2585.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.32 × 0.29 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.712, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	21182, 6240, 4989
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.119, 1.07
No. of reflections	6240
No. of parameters	328
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.87

Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1994), SHELXTL (Sheldrick, 1997b), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL.

Selected geometric parameters (Å, º) top

Cu1—N3	2.0104 (19)	Cu1—N7	2.0347 (19)
Cu1—N5	2.0151 (19)	Cu1—O1	2.2796 (19)
Cu1—N1	2.0223 (19)

N3—Cu1—N5	90.64 (8)	N1—Cu1—N7	91.59 (8)
N3—Cu1—N1	87.23 (8)	N3—Cu1—O1	94.99 (8)
N5—Cu1—N1	162.13 (9)	N5—Cu1—O1	87.62 (7)
N3—Cu1—N7	172.14 (8)	N1—Cu1—O1	110.24 (8)
N5—Cu1—N7	88.11 (8)	N7—Cu1—O1	92.71 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O4ⁱ	0.88	2.21	3.013 (3)	151.8
N4—H4B···O4ⁱⁱ	0.88	1.94	2.808 (3)	167.3
N8—H8B···O8ⁱⁱⁱ	0.88	1.95	2.828 (3)	177.0
N9—H9B···O5ⁱⁱⁱ	0.88	2.19	2.693 (3)	116.0
N9—H9B···O6^iv	0.88	2.33	2.717 (3)	106.6
N6—H6B···O6	0.88	2.11	2.924 (3)	153.8
N6—H6B···O8	0.88	2.27	3.001 (3)	140.2
N10—H10B···O3	0.90	2.13	2.749 (2)	125.7

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

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