catena-Poly[[[(dimethyl­malonato-κ2O:O′)(perchlorato-κO)copper(II)]-μ-bis­(3-pyridylmeth­yl)piperazinediium-κ2N1′:N4′] perchlorate dihydrate]

Farnum, G.A.; LaDuca, R.L.

doi:10.1107/S1600536808036490

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1524

doi:10.1107/S1600536808036490

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catena-Poly[[[(dimethylmalonato-κ²O:O′)(perchlorato-κO)copper(II)]-μ-bis(3-pyridylmethyl)piperazinediium-κ²N^1′:N^4′] perchlorate dihydrate]

Gregory A. Farnum ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825 USA
^*Correspondence e-mail: laduca@msu.edu

(Received 1 November 2008; accepted 6 November 2008; online 13 November 2008)

In the title compound, {[Cu(C₅H₆O₄)(ClO₄)(C₁₆H₂₂N₄)]ClO₄·2H₂O}_n, square-pyramidally coordinated Cu atoms with perchlorate and dimethylmalonate ligands are connected into cationic sinusoidal coordination polymer chains by doubly protonated bis(3-pyridylmethyl)piperazine (3-bpmp) ligands. The chains aggregate into pseudo-layers parallel to the (101) crystal planes by N—H⋯O hydrogen bonding. Unligated perchlorate anions and water molecules of crystallization provide additional hydrogen bonding between pseudo-layers.

Related literature

For copper carboxylate coordination polymers containing 3-bpmp, see: Johnston et al. (2008 ). For the synthesis of 3-bpmp, see: Pocic et al. (2005 ).

Experimental

Crystal data

[Cu(C₅H₆O₄)(ClO₄)(C₁₆H₂₂N₄)]ClO₄·2H₂O
M_r = 698.95
Triclinic, $[P \overline 1]$
a = 9.6284 (15) Å
b = 10.5140 (16) Å
c = 14.061 (2) Å
α = 86.950 (2)°
β = 82.634 (2)°
γ = 84.638 (2)°
V = 1404.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 173 (2) K
0.40 × 0.30 × 0.15 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.680, T_max = 0.859
14378 measured reflections
6309 independent reflections
4904 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.099
S = 1.05
6309 reflections
397 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O12	0.894 (18)	1.98 (2)	2.838 (4)	160 (4)
O1W—H1WB⋯O8ⁱ	0.875 (18)	2.35 (3)	3.053 (4)	137 (3)
O1W—H1WB⋯O2ⁱⁱ	0.875 (18)	2.46 (3)	3.120 (3)	133 (3)
O2W—H2WA⋯O7	0.929 (19)	2.14 (2)	3.044 (4)	164 (4)
O2W—H2WB⋯O1Wⁱⁱⁱ	0.941 (19)	1.95 (3)	2.807 (5)	150 (5)
N2—H2N⋯O2^iv	0.887 (17)	1.804 (18)	2.673 (3)	166 (3)
N4—H4N⋯O4^v	0.923 (17)	1.727 (17)	2.647 (3)	175 (3)
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z+1; (iii) x+1, y, z-1; (iv) -x+2, -y+1, -z; (v) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036490/lh2730sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036490/lh2730Isup2.hkl

checkCIF report

Comment top

In comparison to coordination polymers based on the rigid rod tether 4,4'- bipyridine, extended phases based on the flexible and hydrogen-bonding capable bis(3-pyridylmethyl)piperazine (3-bpmp) ligand are much less common (Johnston et al., 2008).

The asymmetric unit of the title compound contains a divalent copper atom, two halves of two 3-bpmp molecules protonated at their piperazinyl nitrogen atoms, one dimethylmalonate dianion, one bound and one unbound perchlorate ion and two water molecules of crystallization (Figure 1). The Cu atoms are square pyramidally coordinated in a {CuN₂O₃} arrangement, with the basal plane occupied by two cis N atom donors from two crystallographically distinct 3-bpmp ligands and two cis O atom donors from a dimethylmalonate ligand in a 1,3-chelating binding mode. The apical position is filled by a ligated perchlorate anion.

The 3-bpmp ligands link the Cu atoms into sinusoidal cationic coordination polymer chains with formulation [Cu(3-bpmpH₂)(dimethylmalonate)(ClO₄)]_nⁿ⁺ (Figure 2), in which the through ligand Cu···Cu contact distance is 15.441 Å. The "wavelength" of this chain, defined by unbridged Cu···Cu contacts, is 15.991 Å. The chains are aligned parallel to the [1 0 1] crystal direction.

Neighboring chains interdigitate and aggregate into a pseudolayer (Figure 3) parallel to the (1 0 1) crystal plane by N—H···O hydrogen bonding between protonated piperazinyl N atoms and unligated dimethylmalonate O atoms. These stack into three dimensions (Figure 4) through additional hydrogen bonding patterns involving unligated perchlorate anions and water molecule dimers, and dimethylmalonate O atoms within the coordination polymer chains.

Related literature top

For copper carboxylate coordination polymers containing 3-bpmp, see: Johnston et al. (2008). For the synthesis of 3-bpmp, see: Pocic et al. (2005).

Experimental top

All chemicals were obtained commercially, except for 3-bpmp which was synthesized by a literature method (Pocic et al., 2005). Copper perchlorate hexahydrate (19 mg, 0.051 mmol) and dimethylmalonic acid (7 mg, 0.05 mmol) were dissolved in 3 ml water in a glass vial. A 1 ml aliquot of a 1:1 water:ethanol solution was carefully layered onto the aqueous solution, followed by 3 ml of an ethanolic solution of 3-bpmp (27 mg, 0.10 mmol). Blue blocks of the title compound formed after 1 week.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination environment of the title compound, showing 50% probability ellipsoids and atom numbering scheme. Hydrogen atoms are not shown. Color codes: dark blue Cu, light blue N, red O, black C, green Cl and orange O atoms of water molecules.
	Fig. 2. A single cationic [Cu(dimethylmalonate)(ClO₄)(3-bpmpH₂)]_n chain in the title compound.
	Fig. 3. A supramolecular [Cu(dimethylmalonate)(ClO₄)(3-bpmpH₂)]_n layer in the title compound. Hydrogen bonding between protonated piperazinyl N atoms and unligated dimethylmalonate carboxylate O atoms is shown as dashed lines.
	Fig. 4. Packing diagram illustrating the interaction of pseudolayers via hydrogen bonding involving the dimethylmalonate carboxylate O atoms, co-crystallized water molecules, and unligated perchlorate anions.

catena-Poly[[[(dimethylmalonato-κ²O:O')(perchlorato- κO)copper(II)]-µ-bis(3-pyridylmethyl)piperazinediium- κ²N^1':N^4'] perchlorate dihydrate] top

Crystal data top

[Cu(C₅H₆O₄)(ClO₄)(C₁₆H₂₂N₄)]ClO₄·2H₂O	Z = 2
M_r = 698.95	F(000) = 722
Triclinic, P1	D_x = 1.653 Mg m⁻³
a = 9.6284 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5140 (16) Å	Cell parameters from 14378 reflections
c = 14.061 (2) Å	θ = 1.5–28.3°
α = 86.950 (2)°	µ = 1.04 mm⁻¹
β = 82.634 (2)°	T = 173 K
γ = 84.638 (2)°	Block, blue
V = 1404.3 (4) Å³	0.40 × 0.30 × 0.15 mm

Data collection top

Bruker SMART 1K diffractometer	6309 independent reflections
Radiation source: fine-focus sealed tube	4904 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.680, T_max = 0.859	k = −13→13
14378 measured reflections	l = −18→18

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0402P)² + 1.0163P] where P = (F_o² + 2F_c²)/3
6309 reflections	(Δ/σ)_max < 0.001
397 parameters	Δρ_max = 0.57 e Å⁻³
8 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cu(C₅H₆O₄)(ClO₄)(C₁₆H₂₂N₄)]ClO₄·2H₂O	γ = 84.638 (2)°
M_r = 698.95	V = 1404.3 (4) Å³
Triclinic, P1	Z = 2
a = 9.6284 (15) Å	Mo Kα radiation
b = 10.5140 (16) Å	µ = 1.04 mm⁻¹
c = 14.061 (2) Å	T = 173 K
α = 86.950 (2)°	0.40 × 0.30 × 0.15 mm
β = 82.634 (2)°

Data collection top

Bruker SMART 1K diffractometer	6309 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4904 reflections with I > 2σ(I)
T_min = 0.680, T_max = 0.859	R_int = 0.035
14378 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	8 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.57 e Å⁻³
6309 reflections	Δρ_min = −0.44 e Å⁻³
397 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	0.73682 (3)	0.38286 (3)	0.22768 (2)	0.01649 (9)
Cl1	0.52659 (6)	0.15993 (6)	0.15616 (4)	0.01940 (14)
Cl2	0.04531 (7)	0.26708 (7)	0.67794 (5)	0.02767 (17)
O1	0.89350 (18)	0.26684 (16)	0.17600 (12)	0.0185 (4)
O1W	−0.3036 (3)	0.0931 (2)	0.7673 (2)	0.0524 (7)
H1WA	−0.221 (3)	0.124 (3)	0.747 (3)	0.063*
H1WB	−0.284 (4)	0.013 (2)	0.785 (3)	0.063*
O2	1.06366 (18)	0.11347 (16)	0.18831 (12)	0.0196 (4)
O2W	0.6049 (5)	0.2872 (3)	−0.1037 (2)	0.0946 (12)
H2WA	0.573 (6)	0.247 (4)	−0.045 (2)	0.114*
H2WB	0.602 (6)	0.218 (4)	−0.143 (3)	0.114*
O3	0.71336 (18)	0.28139 (17)	0.34603 (13)	0.0211 (4)
O4	0.78008 (19)	0.12856 (17)	0.44779 (13)	0.0211 (4)
O5	0.6183 (2)	0.07458 (18)	0.20754 (14)	0.0282 (5)
O6	0.5848 (2)	0.28179 (18)	0.13822 (15)	0.0287 (5)
O7	0.5127 (2)	0.1087 (2)	0.06554 (15)	0.0362 (5)
O8	0.3908 (2)	0.1798 (2)	0.21162 (16)	0.0370 (5)
O9	0.1580 (3)	0.1796 (2)	0.70439 (19)	0.0536 (7)
O10	0.0031 (3)	0.3535 (2)	0.75267 (17)	0.0514 (7)
O11	0.0911 (3)	0.3375 (3)	0.59195 (18)	0.0571 (7)
O12	−0.0708 (3)	0.2017 (2)	0.6593 (2)	0.0650 (9)
N1	0.7670 (2)	0.50054 (19)	0.11139 (15)	0.0167 (5)
N2	0.8888 (2)	0.91571 (19)	0.00109 (15)	0.0144 (4)
H2N	0.908 (3)	0.893 (2)	−0.0593 (13)	0.017*
N3	0.5816 (2)	0.50287 (19)	0.29083 (15)	0.0182 (5)
N4	0.4942 (2)	0.8624 (2)	0.49802 (15)	0.0156 (4)
H4N	0.3982 (18)	0.863 (3)	0.514 (2)	0.019*
C1	0.9729 (3)	0.1943 (2)	0.22604 (18)	0.0153 (5)
C2	0.9626 (3)	0.2108 (2)	0.33488 (18)	0.0166 (5)
C3	0.8085 (3)	0.2046 (2)	0.37928 (18)	0.0161 (5)
C4	1.0062 (3)	0.3455 (3)	0.3502 (2)	0.0300 (7)
H4A	0.9451	0.4102	0.3190	0.045*
H4B	1.1041	0.3516	0.3223	0.045*
H4C	0.9969	0.3600	0.4191	0.045*
C5	1.0578 (3)	0.1103 (3)	0.3830 (2)	0.0255 (6)
H5A	1.0483	0.1242	0.4520	0.038*
H5B	1.1557	0.1172	0.3553	0.038*
H5C	1.0309	0.0250	0.3728	0.038*
C11	0.7887 (3)	0.4505 (3)	0.02408 (19)	0.0221 (6)
H11	0.7937	0.3602	0.0201	0.027*
C12	0.8040 (3)	0.5242 (3)	−0.0596 (2)	0.0246 (6)
H12	0.8197	0.4854	−0.1200	0.029*
C13	0.7962 (3)	0.6561 (3)	−0.05452 (19)	0.0211 (6)
H13	0.8042	0.7092	−0.1114	0.025*
C14	0.7766 (3)	0.7096 (2)	0.03496 (19)	0.0169 (5)
C15	0.7619 (3)	0.6285 (2)	0.11544 (19)	0.0166 (5)
H15	0.7475	0.6649	0.1767	0.020*
C16	0.7611 (3)	0.8529 (2)	0.0465 (2)	0.0196 (6)
H16A	0.6780	0.8906	0.0169	0.024*
H16B	0.7447	0.8704	0.1157	0.024*
C17	1.0141 (3)	0.8795 (2)	0.05230 (18)	0.0164 (5)
H17A	1.0344	0.7855	0.0539	0.020*
H17B	0.9939	0.9070	0.1193	0.020*
C18	0.8594 (3)	1.0583 (2)	−0.00249 (19)	0.0165 (5)
H18A	0.8365	1.0888	0.0636	0.020*
H18B	0.7774	1.0827	−0.0375	0.020*
C21	0.4487 (3)	0.5093 (3)	0.2703 (2)	0.0247 (6)
H21	0.4271	0.4612	0.2197	0.030*
C22	0.3425 (3)	0.5851 (3)	0.3216 (2)	0.0307 (7)
H22	0.2487	0.5871	0.3069	0.037*
C23	0.3727 (3)	0.6571 (3)	0.3935 (2)	0.0254 (6)
H23	0.3001	0.7085	0.4293	0.031*
C24	0.5109 (3)	0.6542 (2)	0.41357 (18)	0.0187 (5)
C25	0.6108 (3)	0.5742 (2)	0.36102 (18)	0.0176 (5)
H25	0.7050	0.5694	0.3753	0.021*
C26	0.5575 (3)	0.7270 (2)	0.49164 (19)	0.0196 (6)
H26A	0.5329	0.6812	0.5540	0.023*
H26B	0.6611	0.7272	0.4807	0.023*
C27	0.5498 (3)	0.9241 (2)	0.57676 (18)	0.0194 (6)
H27A	0.6525	0.9282	0.5606	0.023*
H27B	0.5336	0.8714	0.6369	0.023*
C28	0.5198 (3)	0.9422 (2)	0.40762 (18)	0.0174 (5)
H28A	0.4809	0.9038	0.3551	0.021*
H28B	0.6222	0.9457	0.3891	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01812 (17)	0.01517 (16)	0.01464 (17)	0.00267 (12)	0.00069 (12)	−0.00020 (12)
Cl1	0.0194 (3)	0.0213 (3)	0.0175 (3)	−0.0024 (2)	−0.0016 (2)	−0.0016 (2)
Cl2	0.0217 (3)	0.0271 (4)	0.0340 (4)	−0.0028 (3)	−0.0008 (3)	−0.0043 (3)
O1	0.0208 (9)	0.0205 (9)	0.0129 (9)	0.0050 (7)	−0.0027 (7)	−0.0007 (7)
O1W	0.0443 (15)	0.0369 (14)	0.074 (2)	−0.0042 (12)	−0.0019 (14)	0.0062 (14)
O2	0.0199 (9)	0.0211 (9)	0.0160 (9)	0.0040 (8)	0.0009 (7)	−0.0013 (7)
O2W	0.160 (4)	0.070 (2)	0.050 (2)	−0.014 (2)	0.005 (2)	0.0045 (17)
O3	0.0181 (9)	0.0240 (10)	0.0182 (10)	0.0053 (8)	0.0020 (7)	0.0040 (8)
O4	0.0197 (9)	0.0232 (10)	0.0179 (10)	0.0010 (8)	0.0024 (7)	0.0048 (8)
O5	0.0284 (11)	0.0276 (11)	0.0268 (11)	0.0047 (9)	−0.0029 (9)	0.0028 (9)
O6	0.0333 (11)	0.0223 (10)	0.0330 (12)	−0.0087 (9)	−0.0098 (9)	0.0009 (9)
O7	0.0451 (13)	0.0387 (13)	0.0287 (12)	−0.0031 (10)	−0.0144 (10)	−0.0129 (10)
O8	0.0193 (10)	0.0534 (14)	0.0336 (12)	0.0031 (10)	0.0056 (9)	0.0099 (11)
O9	0.0453 (15)	0.0555 (16)	0.0568 (17)	0.0255 (12)	−0.0116 (13)	−0.0118 (13)
O10	0.0655 (17)	0.0493 (15)	0.0382 (14)	0.0187 (13)	−0.0128 (13)	−0.0165 (12)
O11	0.0573 (17)	0.079 (2)	0.0366 (15)	−0.0206 (15)	−0.0037 (12)	0.0089 (14)
O12	0.0332 (14)	0.0416 (15)	0.123 (3)	−0.0146 (11)	−0.0043 (15)	−0.0191 (16)
N1	0.0172 (11)	0.0154 (10)	0.0169 (11)	−0.0011 (8)	0.0000 (9)	−0.0012 (9)
N2	0.0158 (10)	0.0127 (10)	0.0138 (11)	−0.0002 (8)	0.0014 (8)	−0.0008 (8)
N3	0.0207 (11)	0.0150 (10)	0.0175 (12)	0.0014 (9)	0.0005 (9)	0.0010 (9)
N4	0.0148 (10)	0.0183 (11)	0.0130 (11)	−0.0004 (9)	0.0012 (8)	−0.0016 (8)
C1	0.0150 (12)	0.0135 (12)	0.0169 (13)	−0.0041 (10)	0.0018 (10)	0.0004 (10)
C2	0.0165 (13)	0.0186 (13)	0.0148 (13)	−0.0019 (10)	−0.0015 (10)	−0.0015 (10)
C3	0.0177 (13)	0.0142 (12)	0.0158 (13)	0.0000 (10)	0.0013 (10)	−0.0052 (10)
C4	0.0348 (17)	0.0286 (16)	0.0288 (17)	−0.0155 (13)	−0.0019 (13)	−0.0060 (13)
C5	0.0197 (14)	0.0377 (17)	0.0172 (14)	0.0049 (12)	−0.0015 (11)	0.0023 (12)
C11	0.0282 (15)	0.0166 (13)	0.0208 (14)	0.0000 (11)	−0.0007 (11)	−0.0025 (11)
C12	0.0336 (16)	0.0228 (14)	0.0167 (14)	−0.0034 (12)	0.0009 (12)	−0.0040 (11)
C13	0.0248 (14)	0.0204 (13)	0.0175 (14)	−0.0060 (11)	0.0005 (11)	0.0030 (11)
C14	0.0139 (12)	0.0141 (12)	0.0224 (14)	−0.0037 (10)	0.0003 (10)	0.0005 (10)
C15	0.0174 (13)	0.0161 (12)	0.0164 (13)	−0.0031 (10)	−0.0006 (10)	−0.0028 (10)
C16	0.0171 (13)	0.0155 (12)	0.0250 (15)	−0.0033 (10)	0.0037 (11)	0.0000 (11)
C17	0.0189 (13)	0.0128 (12)	0.0170 (13)	0.0008 (10)	−0.0031 (10)	0.0029 (10)
C18	0.0165 (12)	0.0117 (11)	0.0203 (14)	0.0010 (10)	−0.0009 (10)	0.0003 (10)
C21	0.0272 (15)	0.0213 (14)	0.0261 (15)	0.0033 (12)	−0.0073 (12)	−0.0052 (12)
C22	0.0218 (15)	0.0313 (16)	0.0394 (19)	0.0047 (12)	−0.0073 (13)	−0.0101 (14)
C23	0.0203 (14)	0.0266 (15)	0.0283 (16)	0.0031 (12)	0.0004 (12)	−0.0088 (12)
C24	0.0209 (13)	0.0172 (13)	0.0172 (13)	−0.0013 (10)	0.0000 (11)	0.0011 (10)
C25	0.0177 (13)	0.0171 (12)	0.0175 (13)	−0.0008 (10)	−0.0007 (10)	0.0004 (10)
C26	0.0198 (13)	0.0186 (13)	0.0190 (14)	0.0035 (11)	−0.0010 (11)	−0.0020 (11)
C27	0.0244 (14)	0.0211 (13)	0.0133 (13)	−0.0012 (11)	−0.0041 (11)	−0.0018 (10)
C28	0.0212 (13)	0.0197 (13)	0.0107 (12)	−0.0030 (10)	0.0016 (10)	−0.0018 (10)

Geometric parameters (Å, º) top

Cu1—O3	1.9283 (18)	C4—H4C	0.9800
Cu1—O1	1.9394 (17)	C5—H5A	0.9800
Cu1—N1	2.005 (2)	C5—H5B	0.9800
Cu1—N3	2.010 (2)	C5—H5C	0.9800
Cu1—O6	2.400 (2)	C11—C12	1.374 (4)
Cl1—O5	1.433 (2)	C11—H11	0.9500
Cl1—O7	1.436 (2)	C12—C13	1.387 (4)
Cl1—O8	1.438 (2)	C12—H12	0.9500
Cl1—O6	1.443 (2)	C13—C14	1.389 (4)
Cl2—O10	1.420 (2)	C13—H13	0.9500
Cl2—O12	1.425 (3)	C14—C15	1.381 (3)
Cl2—O11	1.426 (3)	C14—C16	1.516 (3)
Cl2—O9	1.429 (2)	C15—H15	0.9500
O1—C1	1.278 (3)	C16—H16A	0.9900
O1W—H1WA	0.894 (18)	C16—H16B	0.9900
O1W—H1WB	0.875 (18)	C17—C18ⁱ	1.511 (3)
O2—C1	1.248 (3)	C17—H17A	0.9900
O2W—H2WA	0.929 (19)	C17—H17B	0.9900
O2W—H2WB	0.941 (19)	C18—C17ⁱ	1.511 (3)
O3—C3	1.281 (3)	C18—H18A	0.9900
O4—C3	1.239 (3)	C18—H18B	0.9900
N1—C11	1.345 (3)	C21—C22	1.386 (4)
N1—C15	1.346 (3)	C21—H21	0.9500
N2—C17	1.492 (3)	C22—C23	1.370 (4)
N2—C18	1.499 (3)	C22—H22	0.9500
N2—C16	1.503 (3)	C23—C24	1.392 (4)
N2—H2N	0.887 (17)	C23—H23	0.9500
N3—C21	1.342 (4)	C24—C25	1.383 (3)
N3—C25	1.343 (3)	C24—C26	1.507 (4)
N4—C28	1.492 (3)	C25—H25	0.9500
N4—C27	1.493 (3)	C26—H26A	0.9900
N4—C26	1.498 (3)	C26—H26B	0.9900
N4—H4N	0.923 (17)	C27—C28ⁱⁱ	1.514 (3)
C1—C2	1.539 (4)	C27—H27A	0.9900
C2—C5	1.522 (3)	C27—H27B	0.9900
C2—C3	1.540 (3)	C28—C27ⁱⁱ	1.514 (3)
C2—C4	1.548 (4)	C28—H28A	0.9900
C4—H4A	0.9800	C28—H28B	0.9900
C4—H4B	0.9800

O3—Cu1—O1	91.49 (7)	H5B—C5—H5C	109.5
O3—Cu1—N1	174.84 (8)	N1—C11—C12	122.9 (2)
O1—Cu1—N1	90.38 (8)	N1—C11—H11	118.6
O3—Cu1—N3	85.44 (8)	C12—C11—H11	118.6
O1—Cu1—N3	175.47 (8)	C11—C12—C13	118.9 (3)
N1—Cu1—N3	92.41 (8)	C11—C12—H12	120.5
O3—Cu1—O6	99.44 (7)	C13—C12—H12	120.5
O1—Cu1—O6	89.56 (7)	C12—C13—C14	119.1 (2)
N1—Cu1—O6	85.38 (8)	C12—C13—H13	120.5
N3—Cu1—O6	94.23 (8)	C14—C13—H13	120.5
O5—Cl1—O7	110.03 (13)	C15—C14—C13	118.2 (2)
O5—Cl1—O8	110.26 (12)	C15—C14—C16	119.5 (2)
O7—Cl1—O8	109.95 (14)	C13—C14—C16	122.2 (2)
O5—Cl1—O6	109.60 (12)	N1—C15—C14	123.3 (2)
O7—Cl1—O6	108.42 (13)	N1—C15—H15	118.4
O8—Cl1—O6	108.54 (13)	C14—C15—H15	118.4
O10—Cl2—O12	110.28 (17)	N2—C16—C14	112.3 (2)
O10—Cl2—O11	109.08 (17)	N2—C16—H16A	109.1
O12—Cl2—O11	107.14 (19)	C14—C16—H16A	109.1
O10—Cl2—O9	109.14 (15)	N2—C16—H16B	109.1
O12—Cl2—O9	111.41 (17)	C14—C16—H16B	109.1
O11—Cl2—O9	109.75 (16)	H16A—C16—H16B	107.9
C1—O1—Cu1	125.13 (16)	N2—C17—C18ⁱ	110.5 (2)
H1WA—O1W—H1WB	106 (3)	N2—C17—H17A	109.5
H2WA—O2W—H2WB	98 (3)	C18ⁱ—C17—H17A	109.5
C3—O3—Cu1	125.71 (16)	N2—C17—H17B	109.5
Cl1—O6—Cu1	129.66 (12)	C18ⁱ—C17—H17B	109.5
C11—N1—C15	117.6 (2)	H17A—C17—H17B	108.1
C11—N1—Cu1	118.88 (17)	N2—C18—C17ⁱ	110.23 (19)
C15—N1—Cu1	123.45 (17)	N2—C18—H18A	109.6
C17—N2—C18	109.43 (19)	C17ⁱ—C18—H18A	109.6
C17—N2—C16	112.43 (19)	N2—C18—H18B	109.6
C18—N2—C16	110.56 (18)	C17ⁱ—C18—H18B	109.6
C17—N2—H2N	109.4 (18)	H18A—C18—H18B	108.1
C18—N2—H2N	106.6 (17)	N3—C21—C22	121.2 (3)
C16—N2—H2N	108.2 (18)	N3—C21—H21	119.4
C21—N3—C25	118.6 (2)	C22—C21—H21	119.4
C21—N3—Cu1	123.14 (19)	C23—C22—C21	120.0 (3)
C25—N3—Cu1	118.18 (17)	C23—C22—H22	120.0
C28—N4—C27	108.84 (19)	C21—C22—H22	120.0
C28—N4—C26	114.45 (19)	C22—C23—C24	119.3 (3)
C27—N4—C26	109.3 (2)	C22—C23—H23	120.3
C28—N4—H4N	107.8 (17)	C24—C23—H23	120.3
C27—N4—H4N	107.2 (18)	C25—C24—C23	117.4 (2)
C26—N4—H4N	109.1 (17)	C25—C24—C26	117.9 (2)
O2—C1—O1	121.6 (2)	C23—C24—C26	124.5 (2)
O2—C1—C2	118.6 (2)	N3—C25—C24	123.4 (2)
O1—C1—C2	119.7 (2)	N3—C25—H25	118.3
C5—C2—C1	112.0 (2)	C24—C25—H25	118.3
C5—C2—C3	110.5 (2)	N4—C26—C24	114.5 (2)
C1—C2—C3	108.9 (2)	N4—C26—H26A	108.6
C5—C2—C4	109.5 (2)	C24—C26—H26A	108.6
C1—C2—C4	107.7 (2)	N4—C26—H26B	108.6
C3—C2—C4	108.1 (2)	C24—C26—H26B	108.6
O4—C3—O3	121.7 (2)	H26A—C26—H26B	107.6
O4—C3—C2	119.4 (2)	N4—C27—C28ⁱⁱ	111.7 (2)
O3—C3—C2	118.9 (2)	N4—C27—H27A	109.3
C2—C4—H4A	109.5	C28ⁱⁱ—C27—H27A	109.3
C2—C4—H4B	109.5	N4—C27—H27B	109.3
H4A—C4—H4B	109.5	C28ⁱⁱ—C27—H27B	109.3
C2—C4—H4C	109.5	H27A—C27—H27B	107.9
H4A—C4—H4C	109.5	N4—C28—C27ⁱⁱ	109.3 (2)
H4B—C4—H4C	109.5	N4—C28—H28A	109.8
C2—C5—H5A	109.5	C27ⁱⁱ—C28—H28A	109.8
C2—C5—H5B	109.5	N4—C28—H28B	109.8
H5A—C5—H5B	109.5	C27ⁱⁱ—C28—H28B	109.8
C2—C5—H5C	109.5	H28A—C28—H28B	108.3
H5A—C5—H5C	109.5

O3—Cu1—O1—C1	−25.1 (2)	C1—C2—C3—O3	−55.3 (3)
N1—Cu1—O1—C1	150.0 (2)	C4—C2—C3—O3	61.4 (3)
O6—Cu1—O1—C1	−124.6 (2)	C15—N1—C11—C12	−0.7 (4)
O1—Cu1—O3—C3	23.3 (2)	Cu1—N1—C11—C12	177.0 (2)
N3—Cu1—O3—C3	−153.4 (2)	N1—C11—C12—C13	−0.3 (4)
O6—Cu1—O3—C3	113.1 (2)	C11—C12—C13—C14	1.5 (4)
O5—Cl1—O6—Cu1	−27.77 (19)	C12—C13—C14—C15	−1.7 (4)
O7—Cl1—O6—Cu1	−147.89 (15)	C12—C13—C14—C16	−177.5 (2)
O8—Cl1—O6—Cu1	92.71 (17)	C11—N1—C15—C14	0.5 (4)
O3—Cu1—O6—Cl1	−15.88 (17)	Cu1—N1—C15—C14	−177.01 (19)
O1—Cu1—O6—Cl1	75.56 (16)	C13—C14—C15—N1	0.7 (4)
N1—Cu1—O6—Cl1	165.97 (17)	C16—C14—C15—N1	176.6 (2)
N3—Cu1—O6—Cl1	−101.95 (16)	C17—N2—C16—C14	−68.1 (3)
O1—Cu1—N1—C11	45.5 (2)	C18—N2—C16—C14	169.3 (2)
N3—Cu1—N1—C11	−138.1 (2)	C15—C14—C16—N2	123.4 (3)
O6—Cu1—N1—C11	−44.05 (19)	C13—C14—C16—N2	−60.9 (3)
O1—Cu1—N1—C15	−137.0 (2)	C18—N2—C17—C18ⁱ	−58.4 (3)
N3—Cu1—N1—C15	39.4 (2)	C16—N2—C17—C18ⁱ	178.3 (2)
O6—Cu1—N1—C15	133.5 (2)	C17—N2—C18—C17ⁱ	58.2 (3)
O3—Cu1—N3—C21	−103.2 (2)	C16—N2—C18—C17ⁱ	−177.4 (2)
N1—Cu1—N3—C21	81.5 (2)	C25—N3—C21—C22	−1.7 (4)
O6—Cu1—N3—C21	−4.0 (2)	Cu1—N3—C21—C22	174.1 (2)
O3—Cu1—N3—C25	72.62 (18)	N3—C21—C22—C23	1.3 (4)
N1—Cu1—N3—C25	−102.68 (19)	C21—C22—C23—C24	0.6 (4)
O6—Cu1—N3—C25	171.78 (18)	C22—C23—C24—C25	−2.1 (4)
Cu1—O1—C1—O2	173.27 (17)	C22—C23—C24—C26	−178.9 (3)
Cu1—O1—C1—C2	−9.9 (3)	C21—N3—C25—C24	0.0 (4)
O2—C1—C2—C5	−7.0 (3)	Cu1—N3—C25—C24	−175.96 (19)
O1—C1—C2—C5	176.1 (2)	C23—C24—C25—N3	1.9 (4)
O2—C1—C2—C3	−129.6 (2)	C26—C24—C25—N3	178.8 (2)
O1—C1—C2—C3	53.5 (3)	C28—N4—C26—C24	−56.9 (3)
O2—C1—C2—C4	113.4 (3)	C27—N4—C26—C24	−179.2 (2)
O1—C1—C2—C4	−63.5 (3)	C25—C24—C26—N4	139.4 (2)
Cu1—O3—C3—O4	−168.75 (18)	C23—C24—C26—N4	−43.9 (4)
Cu1—O3—C3—C2	13.4 (3)	C28—N4—C27—C28ⁱⁱ	59.3 (3)
C5—C2—C3—O4	3.3 (3)	C26—N4—C27—C28ⁱⁱ	−175.1 (2)
C1—C2—C3—O4	126.8 (2)	C27—N4—C28—C27ⁱⁱ	−57.8 (3)
C4—C2—C3—O4	−116.5 (3)	C26—N4—C28—C27ⁱⁱ	179.7 (2)
C5—C2—C3—O3	−178.8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O12	0.89 (2)	1.98 (2)	2.838 (4)	160 (4)
O1W—H1WB···O8ⁱⁱⁱ	0.88 (2)	2.35 (3)	3.053 (4)	137 (3)
O1W—H1WB···O2^iv	0.88 (2)	2.46 (3)	3.120 (3)	133 (3)
O2W—H2WA···O7	0.93 (2)	2.14 (2)	3.044 (4)	164 (4)
O2W—H2WB···O1W^v	0.94 (2)	1.95 (3)	2.807 (5)	150 (5)
N2—H2N···O2^vi	0.89 (2)	1.80 (2)	2.673 (3)	166 (3)
N4—H4N···O4^vii	0.92 (2)	1.73 (2)	2.647 (3)	175 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₅H₆O₄)(ClO₄)(C₁₆H₂₂N₄)]ClO₄·2H₂O
M_r	698.95
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.6284 (15), 10.5140 (16), 14.061 (2)
α, β, γ (°)	86.950 (2), 82.634 (2), 84.638 (2)
V (Å³)	1404.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.40 × 0.30 × 0.15

Data collection
Diffractometer	Bruker SMART 1K diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.680, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	14378, 6309, 4904
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.05
No. of reflections	6309
No. of parameters	397
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.44

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Crystal Maker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O12	0.894 (18)	1.98 (2)	2.838 (4)	160 (4)
O1W—H1WB···O8ⁱ	0.875 (18)	2.35 (3)	3.053 (4)	137 (3)
O1W—H1WB···O2ⁱⁱ	0.875 (18)	2.46 (3)	3.120 (3)	133 (3)
O2W—H2WA···O7	0.929 (19)	2.14 (2)	3.044 (4)	164 (4)
O2W—H2WB···O1Wⁱⁱⁱ	0.941 (19)	1.95 (3)	2.807 (5)	150 (5)
N2—H2N···O2^iv	0.887 (17)	1.804 (18)	2.673 (3)	166 (3)
N4—H4N···O4^v	0.923 (17)	1.727 (17)	2.647 (3)	175 (3)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund and Michigan State University for funding this work.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Johnston, L. L., Martin, D. P. & LaDuca, R. L. (2008). Inorg. Chim. Acta, 361, 2887–2894. Web of Science CSD CrossRef CAS Google Scholar
Palmer, D. (2007). Crystal Maker. Crystal Maker, Bicester, Oxfordshire, England. Google Scholar
Pocic, D., Planeix, J.-M., Kyritsakas, N., Jouaiti, A., Abdelaziz, H. & Wais, M. (2005). CrystEngComm, 7, 624–628. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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