catena-Poly[[diaqua­cadmium(II)]bis­(μ-2,2-dimethyl­butane­dioato-κ4O,O′:O′′,O′′′)[diaqua­cadmium(II)]-μ-1,4-bis­(3-pyridylmeth­yl)piperazine-κ2N3:N3′]

Pochodylo, A.L.; LaDuca, R.L.

doi:10.1107/S1600536810018799

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m708

https://doi.org/10.1107/S1600536810018799

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catena-Poly[[diaquacadmium(II)]bis(μ-2,2-dimethylbutanedioato-κ⁴O,O′:O′′,O′′′)[diaquacadmium(II)]-μ-1,4-bis(3-pyridylmethyl)piperazine-κ²N³:N^3′]

Amy L. Pochodylo ^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 14 May 2010; accepted 19 May 2010; online 26 May 2010)

In the title compound, [Cd₂(C₆H₈O₄)₂(C₁₆H₂₀N₄)(H₂O)₄]_n, pentagonal-bipyramidally coordinated Cd^II ions are connected into {Cd₂(2,2-dimethylsuccinate)₂(H₂O)₄} centrosymmetric dimeric clusters. In turn, these clusters are linked by tethering 1,4-bis(3-pyridylmethyl)piperazine (3-bpmp) ligands into [Cd₂(2,2-dimethylsuccinate)₂(3-bpmp)(H₂O)₄]_n coordination polymer chains. The chain motifs are oriented parallel to [1 $[\overline{1}]$ 0]. Individual chains are connected into supramolecular layers via O—H⋯N and O—H⋯O hydrogen-bonding mechanisms.

Related literature

For other dicarboxylate coordination polymers containing 3-bpmp ligands, see: Johnston et al. (2008 ). For the preparation of 3-bpmp, see: Niu et al. (2001 ).

Experimental

Crystal data

[Cd₂(C₆H₈O₄)₂(C₁₆H₂₀N₄)(H₂O)₄]
M_r = 426.74
Triclinic, $[P \overline 1]$
a = 9.275 (3) Å
b = 10.378 (3) Å
c = 10.625 (5) Å
α = 114.461 (3)°
β = 101.274 (3)°
γ = 106.687 (2)°
V = 831.6 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 173 K
0.26 × 0.18 × 0.13 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.723, T_max = 0.840
12027 measured reflections
3047 independent reflections
2909 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.099
S = 1.16
3047 reflections
222 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −1.07 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5C⋯O4	0.84 (4)	1.93 (2)	2.705 (3)	154 (4)
O5—H5D⋯O1ⁱ	0.83 (2)	1.99 (2)	2.744 (3)	152 (3)
O6—H6C⋯O3ⁱⁱ	0.85 (2)	1.84 (2)	2.679 (3)	171 (4)
O6—H6D⋯N2ⁱⁱⁱ	0.83 (2)	2.03 (2)	2.851 (4)	173 (4)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z; (iii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810018799/lh5049sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018799/lh5049Isup2.hkl

checkCIF report

Comment top

Recently we have been investigating bis(3-pyridylmethyl)piperazine (3-bpmp) as a neutral dipodal tethering ligand for the construction of divalent metal coordination polymers in tandem with aromatic dicarboxylate ligands (Johnston et al., 2008). This chemistry has been extended into an aliphatic dicarboxylate system with the synthesis of the title compound.

The asymmetric unit of the title compound contains a Cd^II ion, one 2,2-dimethylsuccinate ligand, two aqua ligands, and one-half of a 3-bpmp ligand whose central piperazinyl ring is situated over a crystallographic inversion centre. The Cd^II ion is pentagonal bipyramidally coordinated in a {CdO₆N} environment, with its apical positions occupied by aqua ligands. Its basal plane consists of two chelating carboxylate groups from two 2,2-dimethylsuccinate ligands and one pyridyl N donor atom from a 3-bpmp ligand. A pair of Cd^II ions is aggregated into a centrosymmetric {Cd₂(H₂O)₄(2,2-dimethylsuccinate)₂} dinuclear cluster (Fig. 1) by two bis(chelating) 2,2-dimethylsuccinate ligands, which adopt a gauche conformation.

{Cd₂(H₂O)₄(2,2-dimethylsuccinate)₂} dinuclear clusters are connected by tethering 3-bpmp ligands into one-dimensional [Cd₂(2,2-dimethylsuccinate)₂(H₂O)₄(3-bpmp)]_n coordination polymer chains, which are oriented parallel to the (1 1 0) crystal direction (Fig. 2). The through-ligand Cd···Cd contact distance is 13.381 (6) Å. Individual chains are connected into supramolecular pseudo layers (Fig. 3) via O—H···N and O—H···O interactions (Table 1). Within the pseudo layers, aqua ligands (O6) donate hydrogen bonds to piperazinyl N atoms of 3-bpmp ligands and ligated 2,2-dimethylsuccinate carboxylate O atoms in neighboring chains. Neighboring pseudo layers stack into the three-dimensional crystal structure (Fig. 4) of the title compound by crystal packing forces.

Related literature top

For other dicarboxylate coordination polymers containing 3-bpmp ligands, see: Johnston et al. (2008). For the preparation of 3-bpmp, see: Niu et al. (2001).

Experimental top

All starting materials were obtained commercially, except for 3-bpmp, which was prepared by a published procedure (Niu et al., 2001). A mixture of cadmium nitrate tetrahydrate (114 mg, 0.37 mmol), 2,2-dimethylsuccinic acid (54 mg, 0.37 mmol), 3-bpmp (199 mg, 0.742 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 393 K for 72 h. Colourless blocks of the title compound (57 mg, 26% yield) were isolated after washing with distilled water and acetone, and drying in air.

Structure description top

For other dicarboxylate coordination polymers containing 3-bpmp ligands, see: Johnston et al. (2008). For the preparation of 3-bpmp, see: Niu et al. (2001).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environment and dinuclear cluster of the title compound, showing 50% probability ellipsoids and partial atom numbering scheme. Hydrogen atom positions are shown as grey sticks. Color codes: violet Cd, red O, light blue N, black C. Symmetry code: (i) -x, -y + 1, -z + 1.
	Fig. 2. A single [Cd₂(2,2-dimethylsuccinate)₂(H₂O)₄ (3-bpmp)]_n coordination polymer chain
	Fig. 3. Supramolecular layer of [Cd₂(2,2-dimethylsuccinate)₂(H₂O)₄ (3-bpmp)]_n chains. Although the H atoms have been omitted the O—H···N and O—H···O hydrogen bonds are shown as dashed lines between the donor and acceptor atoms.
	Fig. 4. Stacking of supramolecular layers in the title compound.

catena-Poly[[diaquacadmium(II)]bis(µ-2,2-dimethylbutanedioato- κ⁴O,O':O'',O''')[diaquacadmium(II)]-µ- 1,4-bis(3-pyridylmethyl)piperazine-κ²N³:N^3'] top

Crystal data top

[Cd₂(C₆H₈O₄)₂(C₁₆H₂₀N₄)(H₂O)₄]	Z = 2
M_r = 426.74	F(000) = 432
Triclinic, P1	D_x = 1.704 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.275 (3) Å	Cell parameters from 12027 reflections
b = 10.378 (3) Å	θ = 2.3–25.4°
c = 10.625 (5) Å	µ = 1.34 mm⁻¹
α = 114.461 (3)°	T = 173 K
β = 101.274 (3)°	Block, colourless
γ = 106.687 (2)°	0.26 × 0.18 × 0.13 mm
V = 831.6 (5) Å³

Data collection top

Bruker APEXII diffractometer	3047 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ω–φ scans	θ_max = 25.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.723, T_max = 0.840	k = −12→12
12027 measured reflections	l = −12→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0539P)² + 0.0373P] where P = (F_o² + 2F_c²)/3
3047 reflections	(Δ/σ)_max < 0.001
222 parameters	Δρ_max = 0.65 e Å⁻³
6 restraints	Δρ_min = −1.07 e Å⁻³

Crystal data top

[Cd₂(C₆H₈O₄)₂(C₁₆H₂₀N₄)(H₂O)₄]	γ = 106.687 (2)°
M_r = 426.74	V = 831.6 (5) Å³
Triclinic, P1	Z = 2
a = 9.275 (3) Å	Mo Kα radiation
b = 10.378 (3) Å	µ = 1.34 mm⁻¹
c = 10.625 (5) Å	T = 173 K
α = 114.461 (3)°	0.26 × 0.18 × 0.13 mm
β = 101.274 (3)°

Data collection top

Bruker APEXII diffractometer	3047 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2909 reflections with I > 2σ(I)
T_min = 0.723, T_max = 0.840	R_int = 0.058
12027 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	6 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 0.65 e Å⁻³
3047 reflections	Δρ_min = −1.07 e Å⁻³
222 parameters

Special details top

Experimental. The largest peak of 0.645 e^- Å³ was located 0.90 Å from Cd1. The largest hole of -1.065 e^- Å³ was located 0.94 Å from Cd1.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cd1	0.18482 (2)	0.45331 (2)	0.36199 (2)	0.03562 (13)
O1	0.0456 (2)	0.6107 (3)	0.3511 (2)	0.0425 (5)
O2	−0.0444 (3)	0.3806 (3)	0.1510 (3)	0.0436 (5)
O3	−0.3418 (3)	0.5696 (3)	0.4297 (3)	0.0452 (5)
O4	−0.2497 (3)	0.3895 (3)	0.3798 (3)	0.0423 (5)
O5	−0.0262 (3)	0.2695 (3)	0.3722 (3)	0.0413 (5)
H5C	−0.098 (4)	0.297 (5)	0.346 (4)	0.050*
H5D	−0.007 (4)	0.295 (4)	0.461 (2)	0.050*
O6	0.4016 (3)	0.6335 (3)	0.3687 (3)	0.0389 (5)
H6C	0.483 (3)	0.611 (4)	0.379 (4)	0.047*
H6D	0.430 (4)	0.720 (3)	0.441 (3)	0.047*
N1	0.2421 (3)	0.2552 (3)	0.2065 (3)	0.0369 (5)
N2	0.5008 (3)	0.0578 (3)	0.3970 (3)	0.0367 (5)
C1	0.1678 (4)	0.1796 (4)	0.0587 (4)	0.0418 (7)
H1	0.0989	0.2150	0.0165	0.050*
C2	0.1890 (4)	0.0519 (4)	−0.0333 (4)	0.0460 (8)
H2	0.1354	0.0005	−0.1376	0.055*
C3	0.2875 (4)	−0.0005 (4)	0.0262 (4)	0.0435 (7)
H3	0.2997	−0.0904	−0.0364	0.052*
C4	0.3700 (4)	0.0788 (4)	0.1793 (4)	0.0375 (6)
C5	0.3413 (4)	0.2057 (4)	0.2633 (4)	0.0392 (7)
H5	0.3956	0.2609	0.3677	0.047*
C6	0.4891 (4)	0.0317 (4)	0.2474 (4)	0.0405 (7)
H6A	0.4588	−0.0801	0.1810	0.049*
H6B	0.5971	0.0900	0.2520	0.049*
C7	0.3498 (4)	−0.0430 (4)	0.3945 (4)	0.0402 (7)
H7A	0.3231	−0.1530	0.3243	0.048*
H7B	0.2605	−0.0176	0.3595	0.048*
C8	0.6337 (4)	0.0216 (4)	0.4535 (4)	0.0400 (7)
H8A	0.7361	0.0906	0.4580	0.048*
H8B	0.6126	−0.0871	0.3846	0.048*
C9	−0.0570 (4)	0.5055 (4)	0.2235 (3)	0.0373 (7)
C10	−0.2056 (4)	0.5280 (4)	0.1593 (4)	0.0390 (7)
C11	−0.3507 (4)	0.4289 (4)	0.1793 (3)	0.0400 (7)
H11A	−0.4454	0.4496	0.1483	0.048*
H11B	−0.3787	0.3173	0.1142	0.048*
C12	−0.3141 (3)	0.4641 (4)	0.3390 (3)	0.0377 (7)
C13	−0.2436 (4)	0.4650 (4)	−0.0073 (4)	0.0471 (8)
H13A	−0.3426	0.4721	−0.0503	0.071*
H13B	−0.2585	0.3561	−0.0552	0.071*
H13C	−0.1540	0.5264	−0.0228	0.071*
C14	−0.1754 (4)	0.6995 (4)	0.2367 (4)	0.0478 (8)
H14A	−0.0781	0.7601	0.2292	0.072*
H14B	−0.1607	0.7363	0.3414	0.072*
H14C	−0.2681	0.7121	0.1892	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03706 (18)	0.03714 (18)	0.03548 (19)	0.01797 (13)	0.01430 (13)	0.01828 (14)
O1	0.0399 (12)	0.0476 (12)	0.0378 (12)	0.0189 (10)	0.0107 (10)	0.0205 (10)
O2	0.0480 (13)	0.0440 (12)	0.0446 (12)	0.0250 (10)	0.0183 (10)	0.0223 (11)
O3	0.0475 (13)	0.0516 (14)	0.0391 (12)	0.0263 (11)	0.0185 (10)	0.0197 (11)
O4	0.0431 (12)	0.0469 (12)	0.0427 (12)	0.0227 (10)	0.0174 (10)	0.0239 (11)
O5	0.0441 (13)	0.0429 (13)	0.0388 (13)	0.0205 (11)	0.0149 (11)	0.0205 (11)
O6	0.0414 (12)	0.0383 (12)	0.0373 (13)	0.0188 (10)	0.0139 (10)	0.0177 (11)
N1	0.0372 (13)	0.0380 (13)	0.0382 (14)	0.0173 (11)	0.0150 (11)	0.0194 (12)
N2	0.0397 (13)	0.0369 (13)	0.0395 (14)	0.0181 (11)	0.0170 (11)	0.0215 (12)
C1	0.0429 (17)	0.0438 (17)	0.0412 (17)	0.0193 (14)	0.0141 (14)	0.0230 (15)
C2	0.0541 (19)	0.0447 (18)	0.0343 (17)	0.0216 (15)	0.0125 (15)	0.0161 (15)
C3	0.0505 (18)	0.0384 (16)	0.0423 (18)	0.0214 (14)	0.0194 (15)	0.0175 (15)
C4	0.0427 (16)	0.0366 (15)	0.0379 (16)	0.0167 (13)	0.0190 (14)	0.0204 (13)
C5	0.0393 (16)	0.0405 (16)	0.0379 (16)	0.0172 (13)	0.0135 (13)	0.0193 (14)
C6	0.0492 (18)	0.0394 (16)	0.0417 (17)	0.0224 (14)	0.0221 (14)	0.0226 (15)
C7	0.0386 (15)	0.0405 (16)	0.0454 (17)	0.0177 (13)	0.0165 (13)	0.0234 (15)
C8	0.0404 (16)	0.0403 (16)	0.0456 (17)	0.0197 (13)	0.0181 (13)	0.0236 (14)
C9	0.0398 (16)	0.0461 (17)	0.0380 (16)	0.0211 (14)	0.0201 (14)	0.0264 (15)
C10	0.0426 (17)	0.0429 (17)	0.0370 (17)	0.0206 (14)	0.0142 (14)	0.0227 (15)
C11	0.0368 (16)	0.0447 (17)	0.0396 (17)	0.0207 (14)	0.0114 (13)	0.0205 (15)
C12	0.0316 (16)	0.0445 (18)	0.0385 (16)	0.0153 (14)	0.0144 (13)	0.0217 (15)
C13	0.053 (2)	0.058 (2)	0.0372 (17)	0.0269 (17)	0.0162 (15)	0.0268 (16)
C14	0.058 (2)	0.0441 (18)	0.052 (2)	0.0275 (16)	0.0221 (17)	0.0280 (16)

Geometric parameters (Å, º) top

Cd1—O6	2.284 (2)	C3—H3	0.9500
Cd1—N1	2.323 (3)	C4—C5	1.386 (4)
Cd1—O5	2.364 (2)	C4—C6	1.507 (5)
Cd1—O4ⁱ	2.374 (3)	C5—H5	0.9500
Cd1—O1	2.378 (2)	C6—H6A	0.9900
Cd1—O2	2.435 (2)	C6—H6B	0.9900
Cd1—O3ⁱ	2.540 (2)	C7—C8ⁱⁱ	1.506 (4)
O1—C9	1.268 (4)	C7—H7A	0.9900
O2—C9	1.258 (4)	C7—H7B	0.9900
O3—C12	1.256 (4)	C8—C7ⁱⁱ	1.506 (4)
O4—C12	1.259 (4)	C8—H8A	0.9900
O5—H5C	0.84 (4)	C8—H8B	0.9900
O5—H5D	0.830 (18)	C9—C10	1.539 (4)
O6—H6C	0.851 (18)	C10—C14	1.528 (4)
O6—H6D	0.825 (18)	C10—C13	1.532 (4)
N1—C5	1.336 (4)	C10—C11	1.553 (5)
N1—C1	1.342 (4)	C11—C12	1.523 (4)
N2—C6	1.474 (4)	C11—H11A	0.9900
N2—C7	1.475 (4)	C11—H11B	0.9900
N2—C8	1.478 (4)	C13—H13A	0.9800
C1—C2	1.379 (5)	C13—H13B	0.9800
C1—H1	0.9500	C13—H13C	0.9800
C2—C3	1.369 (5)	C14—H14A	0.9800
C2—H2	0.9500	C14—H14B	0.9800
C3—C4	1.397 (5)	C14—H14C	0.9800

H14B—C14—H14C	109.5	C5—C4—C6	122.3 (3)
O6—Cd1—N1	90.10 (9)	C3—C4—C6	121.2 (3)
O6—Cd1—O5	175.51 (7)	N1—C5—C4	124.1 (3)
N1—Cd1—O5	90.19 (9)	N1—C5—H5	118.0
O6—Cd1—O4ⁱ	90.71 (8)	C4—C5—H5	118.0
N1—Cd1—O4ⁱ	138.03 (8)	N2—C6—C4	115.3 (3)
O5—Cd1—O4ⁱ	86.08 (8)	N2—C6—H6A	108.5
O6—Cd1—O1	86.80 (8)	C4—C6—H6A	108.5
N1—Cd1—O1	140.28 (8)	N2—C6—H6B	108.5
O5—Cd1—O1	95.83 (8)	C4—C6—H6B	108.5
O4ⁱ—Cd1—O1	81.63 (8)	H6A—C6—H6B	107.5
O6—Cd1—O2	106.73 (8)	N2—C7—C8ⁱⁱ	110.9 (3)
N1—Cd1—O2	88.92 (8)	N2—C7—H7A	109.5
O5—Cd1—O2	77.76 (8)	C8ⁱⁱ—C7—H7A	109.5
O4ⁱ—Cd1—O2	130.56 (8)	N2—C7—H7B	109.5
O1—Cd1—O2	54.59 (7)	C8ⁱⁱ—C7—H7B	109.5
O6—Cd1—O3ⁱ	95.93 (8)	H7A—C7—H7B	108.1
N1—Cd1—O3ⁱ	85.50 (8)	N2—C8—C7ⁱⁱ	111.1 (2)
O5—Cd1—O3ⁱ	79.62 (8)	N2—C8—H8A	109.4
O4ⁱ—Cd1—O3ⁱ	52.70 (8)	C7ⁱⁱ—C8—H8A	109.4
O1—Cd1—O3ⁱ	134.21 (7)	N2—C8—H8B	109.4
O2—Cd1—O3ⁱ	156.67 (9)	C7ⁱⁱ—C8—H8B	109.4
O6—Cd1—C9	98.97 (9)	H8A—C8—H8B	108.0
N1—Cd1—C9	115.36 (9)	O2—C9—O1	121.9 (3)
O5—Cd1—C9	84.95 (9)	O2—C9—C10	119.1 (3)
O4ⁱ—Cd1—C9	105.92 (9)	O1—C9—C10	118.9 (3)
O1—Cd1—C9	27.43 (8)	O2—C9—Cd1	62.34 (16)
O2—Cd1—C9	27.24 (8)	O1—C9—Cd1	59.80 (16)
O3ⁱ—Cd1—C9	154.14 (8)	C10—C9—Cd1	171.7 (2)
C9—O1—Cd1	92.76 (18)	C14—C10—C13	110.1 (3)
C9—O2—Cd1	90.42 (18)	C14—C10—C9	110.8 (3)
C12—O3—Cd1ⁱ	89.11 (19)	C13—C10—C9	109.0 (3)
C12—O4—Cd1ⁱ	96.79 (19)	C14—C10—C11	111.3 (3)
Cd1—O5—H5C	96 (3)	C13—C10—C11	107.9 (3)
Cd1—O5—H5D	107 (3)	C9—C10—C11	107.5 (3)
H5C—O5—H5D	108 (3)	C12—C11—C10	112.2 (3)
Cd1—O6—H6C	111 (3)	C12—C11—H11A	109.2
Cd1—O6—H6D	110 (3)	C10—C11—H11A	109.2
H6C—O6—H6D	106 (3)	C12—C11—H11B	109.2
C5—N1—C1	118.2 (3)	C10—C11—H11B	109.2
C5—N1—Cd1	120.3 (2)	H11A—C11—H11B	107.9
C1—N1—Cd1	121.3 (2)	O3—C12—O4	120.7 (3)
C6—N2—C7	111.3 (3)	O3—C12—C11	120.6 (3)
C6—N2—C8	108.4 (2)	O4—C12—C11	118.6 (3)
C7—N2—C8	108.8 (2)	C10—C13—H13A	109.5
N1—C1—C2	121.6 (3)	C10—C13—H13B	109.5
N1—C1—H1	119.2	H13A—C13—H13B	109.5
C2—C1—H1	119.2	C10—C13—H13C	109.5
C3—C2—C1	119.8 (3)	H13A—C13—H13C	109.5
C3—C2—H2	120.1	H13B—C13—H13C	109.5
C1—C2—H2	120.1	C10—C14—H14A	109.5
C2—C3—C4	119.8 (3)	C10—C14—H14B	109.5
C2—C3—H3	120.1	H14A—C14—H14B	109.5
C4—C3—H3	120.1	C10—C14—H14C	109.5
C5—C4—C3	116.5 (3)	H14A—C14—H14C	109.5

O6—Cd1—O1—C9	116.54 (18)	C5—C4—C6—N2	34.4 (4)
N1—Cd1—O1—C9	30.2 (2)	C3—C4—C6—N2	−148.3 (3)
O5—Cd1—O1—C9	−67.12 (18)	C6—N2—C7—C8ⁱⁱ	176.9 (2)
O4ⁱ—Cd1—O1—C9	−152.27 (18)	C8—N2—C7—C8ⁱⁱ	57.5 (3)
O2—Cd1—O1—C9	3.36 (16)	C6—N2—C8—C7ⁱⁱ	−178.9 (2)
O3ⁱ—Cd1—O1—C9	−148.30 (17)	C7—N2—C8—C7ⁱⁱ	−57.7 (4)
O6—Cd1—O2—C9	−76.80 (18)	Cd1—O2—C9—O1	6.1 (3)
N1—Cd1—O2—C9	−166.58 (17)	Cd1—O2—C9—C10	−170.7 (2)
O5—Cd1—O2—C9	102.99 (18)	Cd1—O1—C9—O2	−6.2 (3)
O4ⁱ—Cd1—O2—C9	29.1 (2)	Cd1—O1—C9—C10	170.6 (2)
O1—Cd1—O2—C9	−3.38 (16)	O6—Cd1—C9—O2	109.28 (17)
O3ⁱ—Cd1—O2—C9	117.4 (2)	N1—Cd1—C9—O2	14.88 (19)
O6—Cd1—N1—C5	89.2 (2)	O5—Cd1—C9—O2	−72.93 (17)
O5—Cd1—N1—C5	−86.3 (2)	O4ⁱ—Cd1—C9—O2	−157.39 (16)
O4ⁱ—Cd1—N1—C5	−1.9 (3)	O1—Cd1—C9—O2	174.0 (3)
O1—Cd1—N1—C5	174.34 (19)	O3ⁱ—Cd1—C9—O2	−126.3 (2)
O2—Cd1—N1—C5	−164.0 (2)	O6—Cd1—C9—O1	−64.73 (18)
O3ⁱ—Cd1—N1—C5	−6.7 (2)	N1—Cd1—C9—O1	−159.13 (16)
C9—Cd1—N1—C5	−170.8 (2)	O5—Cd1—C9—O1	113.06 (18)
O6—Cd1—N1—C1	−96.0 (2)	O4ⁱ—Cd1—C9—O1	28.61 (18)
O5—Cd1—N1—C1	88.5 (2)	O2—Cd1—C9—O1	−174.0 (3)
O4ⁱ—Cd1—N1—C1	172.8 (2)	O3ⁱ—Cd1—C9—O1	59.7 (3)
O1—Cd1—N1—C1	−10.9 (3)	O2—C9—C10—C14	−162.7 (3)
O2—Cd1—N1—C1	10.7 (2)	O1—C9—C10—C14	20.4 (4)
O3ⁱ—Cd1—N1—C1	168.1 (2)	O2—C9—C10—C13	−41.4 (4)
C9—Cd1—N1—C1	4.0 (3)	O1—C9—C10—C13	141.7 (3)
C5—N1—C1—C2	1.5 (5)	O2—C9—C10—C11	75.4 (3)
Cd1—N1—C1—C2	−173.4 (2)	O1—C9—C10—C11	−101.5 (3)
N1—C1—C2—C3	0.2 (5)	C14—C10—C11—C12	−68.5 (3)
C1—C2—C3—C4	−2.1 (5)	C13—C10—C11—C12	170.5 (3)
C2—C3—C4—C5	2.1 (5)	C9—C10—C11—C12	53.1 (3)
C2—C3—C4—C6	−175.2 (3)	Cd1ⁱ—O3—C12—O4	8.2 (3)
C1—N1—C5—C4	−1.4 (5)	Cd1ⁱ—O3—C12—C11	−169.0 (2)
Cd1—N1—C5—C4	173.5 (2)	Cd1ⁱ—O4—C12—O3	−8.9 (3)
C3—C4—C5—N1	−0.4 (5)	Cd1ⁱ—O4—C12—C11	168.4 (2)
C6—C4—C5—N1	176.9 (3)	C10—C11—C12—O3	89.1 (3)
C7—N2—C6—C4	66.3 (3)	C10—C11—C12—O4	−88.2 (3)
C8—N2—C6—C4	−174.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O4	0.84 (4)	1.93 (2)	2.705 (3)	154 (4)
O5—H5D···O1ⁱ	0.83 (2)	1.99 (2)	2.744 (3)	152 (3)
O6—H6C···O3ⁱⁱⁱ	0.85 (2)	1.84 (2)	2.679 (3)	171 (4)
O6—H6D···N2^iv	0.83 (2)	2.03 (2)	2.851 (4)	173 (4)

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

Experimental details

Crystal data
Chemical formula	[Cd₂(C₆H₈O₄)₂(C₁₆H₂₀N₄)(H₂O)₄]
M_r	426.74
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.275 (3), 10.378 (3), 10.625 (5)
α, β, γ (°)	114.461 (3), 101.274 (3), 106.687 (2)
V (Å³)	831.6 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.26 × 0.18 × 0.13

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.723, 0.840
No. of measured, independent and observed [I > 2σ(I)] reflections	12027, 3047, 2909
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.16
No. of reflections	3047
No. of parameters	222
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −1.07

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O4	0.84 (4)	1.93 (2)	2.705 (3)	154 (4)
O5—H5D···O1ⁱ	0.830 (18)	1.99 (2)	2.744 (3)	152 (3)
O6—H6C···O3ⁱⁱ	0.851 (18)	1.836 (19)	2.679 (3)	171 (4)
O6—H6D···N2ⁱⁱⁱ	0.825 (18)	2.031 (19)	2.851 (4)	173 (4)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work. We also thank Anthony H. LaDuca for experimental assistance.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Johnston, L. L., Martin, D. P., Supkowski, R. M. & LaDuca, R. L. (2008). Inorg. Chim. Acta, 361, 2887–2894. Web of Science CSD CrossRef CAS Google Scholar
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Palmer, D. (2007). CrystalMaker. CrystalMaker Software, Bicester, England. 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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