[μ-N,N,N′,N′-Tetra­kis(2-pyridyl­meth­yl)butane-1,4-diamine]­bis­[diacetato­cadmium(II)] nona­hydrate

Bartholomä, M.; Cheung, H.; Zubieta, J.

doi:10.1107/S1600536810034550

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages m1195-m1196

doi:10.1107/S1600536810034550

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[μ-N,N,N′,N′-Tetrakis(2-pyridylmethyl)butane-1,4-diamine]bis[diacetatocadmium(II)] nonahydrate

Mark Bartholomä,^a ‡ Hoi Cheung ^a and Jon Zubieta ^a ^*

^aDepartment of Chemistry, Syracuse University, Syracuse, New York 13244, USA
^*Correspondence e-mail: jazubiet@syr.edu

(Received 29 July 2010; accepted 26 August 2010; online 4 September 2010)

The title dinuclear complex, [Cd₂(CH₃CO₂)₄(C₂₈H₃₂N₆)]·9H₂O, is located on a crystallographic inversion center. The unique Cd^II ion displays a 5 + 2 coordination. A distorted square-pyramidal geometry is formed by the dipicolylamine unit of the ligand via the N atoms in a meridional fashion and two O atoms of the acetate ligands with short Cd—O distances. The coordination is completed by two loosely bound O atoms of the acetate ligands. The Cd—N distances involving the pyridine N atoms differ slightly from each other and the Cd—N distance involving the tertiary N atom is the longest. In the crystal structure, complex molecules and solvent water molecules are connected into a three-dimensional network via intermolecular O—H⋯O hydrogen bonds. One of the water molecules lies on a twofold rotation axis.

Related literature

For related crystal structures of tetrakis(pyridin-2-yl-methyl)alkyl-diamine compounds, see: Fujihara et al. (2004 ); Mambanda et al. (2007 ). For dinuclear platinum complexes of similar ligands, see: Ertürk et al. (2007 ). For the superoxide dismutase activity of iron complexes, see: Tamura et al. (2000 ). For the use of the dipicolylamine moiety for binding of the M(CO)₃ core (M = Re, ^99mTc), see: Bartholomä et al. (2009 ). For crystal structures closely related to the title compound, see: Bartholomä et al. (2010a ,b ,c ,d ).

Experimental

Crystal data

[Cd₂(C₂H₃O₂)₄(C₂₈H₃₂N₆)]·9H₂O
M_r = 1075.72
Monoclinic, C 2/c
a = 15.9680 (17) Å
b = 11.4320 (12) Å
c = 26.451 (3) Å
β = 100.127 (2)°
V = 4753.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 90 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.760, T_max = 0.910
23441 measured reflections
5847 independent reflections
5621 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.103
S = 1.20
5847 reflections
314 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.55 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O4	2.240 (2)
Cd1—O2	2.251 (3)
Cd1—N3	2.313 (3)
Cd1—N2	2.379 (3)
Cd1—N1	2.405 (3)
Cd1—O1	2.550 (3)
Cd1—O3	2.729 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O3	0.80 (6)	2.06 (6)	2.829 (5)	160 (6)
O6—H6A⋯O4	0.77 (5)	1.98 (5)	2.745 (4)	170 (5)
O9—H9B⋯O5ⁱ	0.79 (5)	2.07 (5)	2.852 (3)	170 (5)
O7—H7C⋯O1ⁱⁱ	0.76 (5)	1.91 (5)	2.673 (4)	177 (5)
O8—H8A⋯O9ⁱⁱⁱ	0.73 (5)	2.04 (5)	2.769 (4)	172 (5)
O6—H6B⋯O8^iv	0.85 (5)	1.97 (5)	2.792 (4)	164 (5)
O5—H5A⋯O7ⁱⁱ	0.76 (4)	1.96 (4)	2.708 (3)	170 (5)
O8—H8B⋯O6^v	0.78 (5)	2.06 (5)	2.825 (4)	166 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) -x, -y+1, -z; (v) x, y-1, z.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034550/lh5104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034550/lh5104Isup2.hkl

checkCIF report

Comment top

The described ligand N¹,N¹,N⁴,N⁴-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine has been used as starting material in the hydrothermal synthesis of metal-organic transition metal/molybdateoxide frameworks in the principal author's laboratory. The dipicolylamine moiety has originally been used in our laboratory as metal chelating entity for binding of the M(CO)₃ core (M = Re,⁹⁹^mTc) for radiopharmaceutical purposes. However, a different coordination mode has been observed for the M(CO)₃ core in which the dipicolylamine metal chelate is bound in a facial manner (Bartholomä, 2009).

Crystal structures of the ligands N¹,N¹,N³,N³-tetrakis(2-pyridiniomethyl)-1,3-diaminopropane and N¹,N¹,N⁴,N⁴-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine have been described recently (Fujihara, 2004; Mambanda, 2007). Superoxide dismutase activity of iron(II) complexes of N¹,N¹,N³,N³-tetrakis(2-pyridiniomethyl)-1,3-diaminopropane and related ligands has been investigated by Tamura et al. (2000). Studies on the thermodynamic and kinetic behaviour of the reaction of platinum(II) complexes of higher ligand homologues with chloride have been performed by Ertürk et al. (2007).

The title complex was prepared as part of a series with different cadmium and copper salts to study the coordination properties of the ligand with these metals without the interaction of metaloxide clusters (Bartholomä, 2010b,c,d). We have reported another crystal structure of a molecular dinuclear cadmium complex using the corresponding nitrate salt as metal source (Bartholomä, 2010a). In the cadmium nitrate structure, the Cd—N distances involving the pyridine N atoms [2.250 (2) Å and 2.251 (2) Å] are slightly shorter whereas the Cd—N distance involving the tertiary nitrogen atom [2.427 (2) Å] is marginally longer when compared to the related distances in the title compound.

Related literature top

For related crystal structures of tetrakis(pyridin-2-yl-methyl)alkyl-diamine compounds, see: Fujihara et al. (2004); Mambanda et al. (2007). For dinuclear platinum complexes of similar ligands, see: Ertürk et al. (2007). For the superoxide dismutase activity of iron complexes, see: Tamura et al. (2000). For the use of the dipicolylamine moiety for binding of the M(CO)₃ core (M = Re, ⁹⁹^mTc) see: Bartholomä et al. (2009). For crystal structures closely related to the title compound, see: Bartholomä et al. (2010a,b,c,d).

Experimental top

N¹,N¹,N⁴,N⁴-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine. An amount of 1.00 g (11.34 mmol) 1,4-diaminobutane was dissolved in 30 ml anhydrous dichloroethane under an inert atmosphere (argon) followed by the addition of 4.55 ml (47.65 mmol) pyridine-2-carboxaldehyde. The mixture was stirred for 15 min at r.t. and then cooled with an ice bath prior to the portionwise addition of 14.43 g (68.06 mmol) sodium triacetoxyborohydride (gas evolution, exothermic reaction). The reaction was stirred overnight allowing the temperature slowly to rise to room temperature. The reaction was quenched by the dropwise addition of saturated sodium bicarbonate solution and stirring was continued until the gas evolution ceased. The mixture was separated and the organic layer was further washed with saturated sodium bicarbonate solution, water and brine. The organic phase was dried with anhydrous sodium sulfate, filtered and the solvent removed under reduced pressure. The crude reaction mixture was then purified by silica gel column chromatography starting with chloroform and increasing gradient to chloroform:methanol 10:1 (v/v). Yield: 4.02 g (78%). ¹H NMR (CDCl₃): δ = 8.40 (m, 4H), 7.51 (m, 4H), 7.39 (d, J = 7.81 Hz, 4H), 7.02 (m, 4H), 3.67 (s, 8H), 2.39 (m, 4H), 1.42 (m, 4H) p.p.m..

Synthesis of metal complex. To 2 ml of an aqueous solution of cadmium acetate, two equivalents (50 mg, 0.11 mmol) of N¹,N¹,N⁴,N⁴-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine in 2 ml methanol were added followed by the addition of 2 ml N,N-dimethylformamide. Single crystals were obtained after a week by slow evaporation of the solvents at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The crystal structure of the title complex. The displacement ellipsoids are drawn at 50% probability level. Water of crystallization and hydrogen atoms are omitted for clarity. Unlabeled atoms are related by the symmetry code (-x, -y+1, -z).

[µ-N,N,N',N'-Tetrakis(2-pyridylmethyl)butane- 1,4-diamine]bis[diacetatocadmium(II)] nonahydrate top

Crystal data top

[Cd₂(C₂H₃O₂)₄(C₂₈H₃₂N₆)]·9H₂O	F(000) = 2208
M_r = 1075.72	D_x = 1.503 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5663 reflections
a = 15.9680 (17) Å	θ = 2.6–28.3°
b = 11.4320 (12) Å	µ = 0.97 mm⁻¹
c = 26.451 (3) Å	T = 90 K
β = 100.127 (2)°	Block, colourless
V = 4753.3 (9) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	5847 independent reflections
Radiation source: fine-focus sealed tube	5621 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 512 pixels mm^-1	θ_max = 28.3°, θ_min = 2.2°
ϕ and ω scans	h = −20→21
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −15→15
T_min = 0.760, T_max = 0.910	l = −35→34
23441 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.0355P)² + 21.0991P] where P = (F_o² + 2F_c²)/3
5847 reflections	(Δ/σ)_max = 0.001
314 parameters	Δρ_max = 1.55 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[Cd₂(C₂H₃O₂)₄(C₂₈H₃₂N₆)]·9H₂O	V = 4753.3 (9) Å³
M_r = 1075.72	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.9680 (17) Å	µ = 0.97 mm⁻¹
b = 11.4320 (12) Å	T = 90 K
c = 26.451 (3) Å	0.30 × 0.20 × 0.10 mm
β = 100.127 (2)°

Data collection top

Bruker SMART APEX diffractometer	5847 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	5621 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.910	R_int = 0.022
23441 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.0355P)² + 21.0991P] where P = (F_o² + 2F_c²)/3
5847 reflections	Δρ_max = 1.55 e Å⁻³
314 parameters	Δρ_min = −0.57 e Å⁻³

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
Cd1	0.165978 (14)	0.604997 (19)	0.132379 (8)	0.02575 (8)
O1	0.2134 (2)	0.4939 (3)	0.21610 (10)	0.0556 (9)
O2	0.2542 (2)	0.6682 (3)	0.20295 (11)	0.0560 (8)
O3	0.2906 (2)	0.7203 (3)	0.09388 (13)	0.0616 (9)
O4	0.15464 (17)	0.7426 (2)	0.07125 (11)	0.0423 (6)
O5	0.0000	0.2308 (3)	0.2500	0.0322 (7)
O6	0.00239 (19)	0.8361 (3)	0.02426 (12)	0.0402 (6)
O7	0.85601 (17)	0.3567 (3)	0.22061 (12)	0.0377 (6)
O8	0.0253 (2)	0.0574 (3)	0.07224 (12)	0.0418 (6)
O9	0.4442 (2)	0.6321 (3)	0.15079 (13)	0.0437 (7)
N1	0.05268 (16)	0.4637 (2)	0.12010 (9)	0.0228 (5)
N2	0.04401 (19)	0.6870 (3)	0.15915 (10)	0.0300 (6)
N3	0.21759 (17)	0.4384 (2)	0.09883 (10)	0.0259 (5)
C1	0.0067 (2)	0.4816 (3)	0.16377 (12)	0.0276 (6)
H1A	0.0419	0.4517	0.1957	0.033*
H1B	−0.0471	0.4366	0.1575	0.033*
C2	−0.0127 (2)	0.6095 (3)	0.17043 (11)	0.0273 (6)
C3	−0.0848 (2)	0.6442 (3)	0.18900 (13)	0.0349 (7)
H3	−0.1241	0.5878	0.1971	0.042*
C4	−0.0988 (3)	0.7620 (4)	0.19562 (14)	0.0407 (8)
H4	−0.1474	0.7876	0.2088	0.049*
C5	−0.0413 (3)	0.8423 (3)	0.18282 (13)	0.0396 (8)
H5	−0.0500	0.9239	0.1864	0.047*
C6	0.0289 (3)	0.8011 (3)	0.16482 (13)	0.0361 (8)
H6	0.0686	0.8561	0.1560	0.043*
C7	0.0917 (2)	0.3463 (3)	0.12297 (12)	0.0270 (6)
H7A	0.0498	0.2899	0.1049	0.032*
H7B	0.1056	0.3222	0.1594	0.032*
C8	0.17205 (19)	0.3403 (3)	0.09967 (11)	0.0246 (6)
C9	0.1976 (2)	0.2339 (3)	0.08241 (12)	0.0299 (7)
H9	0.1638	0.1658	0.0832	0.036*
C10	0.2736 (2)	0.2291 (3)	0.06395 (13)	0.0339 (7)
H10	0.2928	0.1572	0.0521	0.041*
C11	0.3211 (2)	0.3300 (3)	0.06300 (13)	0.0332 (7)
H11	0.3733	0.3284	0.0505	0.040*
C12	0.2915 (2)	0.4325 (3)	0.08031 (12)	0.0301 (7)
H12	0.3240	0.5018	0.0793	0.036*
C13	−0.00785 (19)	0.4817 (3)	0.07122 (11)	0.0264 (6)
H13A	−0.0380	0.5567	0.0733	0.032*
H13B	−0.0509	0.4185	0.0675	0.032*
C14	0.03306 (18)	0.4836 (3)	0.02357 (11)	0.0246 (6)
H14A	0.0571	0.4057	0.0184	0.029*
H14B	0.0801	0.5413	0.0281	0.029*
C15	0.2586 (2)	0.5762 (3)	0.23017 (13)	0.0387 (8)
C16	0.3163 (3)	0.5767 (5)	0.28214 (16)	0.0603 (14)
H16A	0.2953	0.5199	0.3047	0.090*
H16B	0.3166	0.6550	0.2973	0.090*
H16C	0.3742	0.5555	0.2780	0.090*
C17	0.2281 (3)	0.7765 (4)	0.07178 (16)	0.0440 (9)
C18	0.2414 (3)	0.8863 (4)	0.0423 (2)	0.0635 (14)
H18A	0.2959	0.8813	0.0302	0.095*
H18B	0.2419	0.9545	0.0648	0.095*
H18C	0.1951	0.8944	0.0128	0.095*
H8B	0.017 (3)	−0.008 (4)	0.0639 (16)	0.033 (11)*
H5A	0.039 (2)	0.271 (4)	0.2553 (17)	0.035 (11)*
H6B	0.001 (3)	0.859 (4)	−0.007 (2)	0.048 (13)*
H8A	0.002 (3)	0.071 (4)	0.093 (2)	0.049 (15)*
H7C	0.835 (3)	0.395 (4)	0.2383 (19)	0.048 (14)*
H9B	0.463 (3)	0.653 (4)	0.1789 (19)	0.043 (13)*
H6A	0.047 (3)	0.812 (4)	0.0345 (19)	0.052 (15)*
H7D	0.824 (3)	0.309 (5)	0.2106 (19)	0.054 (15)*
H9A	0.400 (4)	0.665 (5)	0.141 (2)	0.069 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02604 (13)	0.02573 (12)	0.02352 (12)	−0.00736 (8)	−0.00101 (8)	0.00419 (8)
O1	0.0564 (18)	0.072 (2)	0.0323 (14)	−0.0304 (16)	−0.0097 (12)	0.0150 (14)
O2	0.0591 (19)	0.0571 (19)	0.0434 (16)	−0.0261 (15)	−0.0137 (14)	0.0117 (14)
O3	0.0560 (19)	0.065 (2)	0.0574 (19)	0.0113 (16)	−0.0089 (15)	0.0048 (16)
O4	0.0395 (14)	0.0400 (14)	0.0471 (15)	−0.0045 (11)	0.0070 (12)	0.0182 (12)
O5	0.0285 (18)	0.0317 (18)	0.0355 (18)	0.000	0.0031 (15)	0.000
O6	0.0330 (15)	0.0471 (16)	0.0420 (16)	0.0024 (12)	0.0104 (12)	0.0054 (13)
O7	0.0262 (13)	0.0366 (14)	0.0509 (16)	−0.0037 (11)	0.0086 (12)	−0.0113 (12)
O8	0.0517 (17)	0.0372 (16)	0.0395 (15)	−0.0072 (13)	0.0165 (13)	−0.0059 (12)
O9	0.0422 (16)	0.0450 (16)	0.0430 (17)	0.0027 (13)	0.0049 (13)	−0.0166 (13)
N1	0.0230 (12)	0.0252 (12)	0.0198 (11)	−0.0018 (10)	0.0026 (9)	0.0023 (9)
N2	0.0377 (15)	0.0313 (14)	0.0202 (12)	−0.0047 (12)	0.0033 (11)	0.0014 (10)
N3	0.0250 (13)	0.0292 (13)	0.0209 (12)	−0.0040 (10)	−0.0025 (10)	0.0043 (10)
C1	0.0308 (16)	0.0300 (16)	0.0225 (14)	−0.0035 (13)	0.0062 (12)	0.0055 (12)
C2	0.0330 (16)	0.0311 (16)	0.0172 (13)	−0.0019 (13)	0.0022 (11)	0.0031 (11)
C3	0.0371 (18)	0.0418 (19)	0.0265 (16)	0.0007 (15)	0.0072 (14)	0.0027 (14)
C4	0.045 (2)	0.047 (2)	0.0302 (17)	0.0088 (17)	0.0070 (15)	−0.0028 (15)
C5	0.055 (2)	0.0332 (18)	0.0279 (17)	0.0057 (16)	0.0014 (16)	−0.0036 (14)
C6	0.048 (2)	0.0319 (17)	0.0264 (16)	−0.0060 (15)	0.0022 (14)	−0.0021 (13)
C7	0.0287 (15)	0.0219 (14)	0.0302 (15)	−0.0033 (12)	0.0047 (12)	0.0038 (12)
C8	0.0237 (14)	0.0273 (15)	0.0210 (13)	−0.0030 (12)	−0.0014 (11)	0.0036 (11)
C9	0.0296 (16)	0.0307 (16)	0.0280 (15)	−0.0045 (13)	0.0009 (12)	0.0026 (12)
C10	0.0331 (17)	0.0369 (18)	0.0294 (16)	0.0033 (14)	−0.0007 (13)	−0.0011 (14)
C11	0.0255 (16)	0.0435 (19)	0.0298 (16)	−0.0024 (14)	0.0027 (13)	0.0017 (14)
C12	0.0246 (15)	0.0388 (17)	0.0250 (15)	−0.0062 (13)	−0.0005 (12)	0.0039 (13)
C13	0.0232 (14)	0.0348 (16)	0.0195 (13)	−0.0054 (12)	−0.0009 (11)	0.0000 (12)
C14	0.0211 (14)	0.0299 (15)	0.0211 (14)	−0.0029 (12)	−0.0007 (11)	−0.0003 (11)
C15	0.041 (2)	0.045 (2)	0.0262 (16)	−0.0158 (16)	−0.0051 (14)	0.0073 (14)
C16	0.056 (3)	0.081 (3)	0.035 (2)	−0.033 (2)	−0.0160 (19)	0.016 (2)
C17	0.047 (2)	0.041 (2)	0.041 (2)	−0.0010 (17)	−0.0010 (17)	0.0084 (16)
C18	0.055 (3)	0.053 (3)	0.085 (4)	−0.008 (2)	0.019 (3)	0.030 (3)

Geometric parameters (Å, º) top

Cd1—O4	2.240 (2)	C3—H3	0.9500
Cd1—O4	2.240 (2)	C4—C5	1.382 (6)
Cd1—O2	2.251 (3)	C4—H4	0.9500
Cd1—N3	2.313 (3)	C5—C6	1.376 (6)
Cd1—N2	2.379 (3)	C5—H5	0.9500
Cd1—N1	2.405 (3)	C6—H6	0.9500
Cd1—O1	2.550 (3)	C7—C8	1.519 (4)
Cd1—O3	2.729 (4)	C7—H7A	0.9900
O1—C15	1.205 (5)	C7—H7B	0.9900
O2—C15	1.269 (5)	C8—C9	1.386 (5)
O3—C17	1.242 (5)	C9—C10	1.386 (5)
O4—C17	1.233 (5)	C9—H9	0.9500
O5—H5A	0.76 (4)	C10—C11	1.384 (5)
O6—H6B	0.85 (5)	C10—H10	0.9500
O6—H6A	0.77 (5)	C11—C12	1.371 (5)
O7—H7C	0.76 (5)	C11—H11	0.9500
O7—H7D	0.77 (5)	C12—H12	0.9500
O8—H8B	0.78 (5)	C13—C14	1.518 (4)
O8—H8A	0.73 (5)	C13—H13A	0.9900
O9—H9B	0.79 (5)	C13—H13B	0.9900
O9—H9A	0.80 (6)	C14—C14ⁱ	1.532 (6)
N1—C7	1.475 (4)	C14—H14A	0.9900
N1—C13	1.486 (4)	C14—H14B	0.9900
N1—C1	1.488 (4)	C15—C16	1.514 (5)
N2—C2	1.338 (4)	C16—H16A	0.9800
N2—C6	1.340 (5)	C16—H16B	0.9800
N3—C8	1.339 (4)	C16—H16C	0.9800
N3—C12	1.357 (4)	C17—O4	1.233 (5)
C1—C2	1.512 (5)	C17—O3	1.242 (5)
C1—H1A	0.9900	C17—C18	1.513 (6)
C1—H1B	0.9900	C18—H18A	0.9800
C2—C3	1.387 (5)	C18—H18B	0.9800
C3—C4	1.381 (5)	C18—H18C	0.9800

O4—Cd1—O4	0.0 (2)	C6—C5—C4	118.3 (3)
O4—Cd1—O2	109.44 (11)	C6—C5—H5	120.8
O4—Cd1—O2	109.44 (11)	C4—C5—H5	120.8
O4—Cd1—N3	106.87 (10)	N2—C6—C5	123.1 (4)
O4—Cd1—N3	106.87 (10)	N2—C6—H6	118.5
O2—Cd1—N3	111.66 (11)	C5—C6—H6	118.5
O4—Cd1—N2	88.38 (10)	N1—C7—C8	113.6 (2)
O4—Cd1—N2	88.38 (10)	N1—C7—H7A	108.9
O2—Cd1—N2	93.01 (12)	C8—C7—H7A	108.9
N3—Cd1—N2	143.54 (9)	N1—C7—H7B	108.9
O4—Cd1—N1	114.26 (9)	C8—C7—H7B	108.9
O4—Cd1—N1	114.26 (9)	H7A—C7—H7B	107.7
O2—Cd1—N1	132.37 (10)	N3—C8—C9	122.5 (3)
N3—Cd1—N1	72.86 (9)	N3—C8—C7	117.9 (3)
N2—Cd1—N1	70.68 (9)	C9—C8—C7	119.5 (3)
O4—Cd1—O1	161.92 (10)	C8—C9—C10	118.5 (3)
O4—Cd1—O1	161.92 (10)	C8—C9—H9	120.7
O2—Cd1—O1	52.59 (10)	C10—C9—H9	120.7
N3—Cd1—O1	81.46 (10)	C11—C10—C9	119.3 (3)
N2—Cd1—O1	94.11 (10)	C11—C10—H10	120.3
N1—Cd1—O1	83.35 (9)	C9—C10—H10	120.3
O4—Cd1—O3	50.44 (9)	C12—C11—C10	119.0 (3)
O4—Cd1—O3	50.44 (9)	C12—C11—H11	120.5
O2—Cd1—O3	76.31 (11)	C10—C11—H11	120.5
N3—Cd1—O3	85.54 (10)	N3—C12—C11	122.4 (3)
N2—Cd1—O3	127.56 (10)	N3—C12—H12	118.8
N1—Cd1—O3	148.74 (9)	C11—C12—H12	118.8
O1—Cd1—O3	116.10 (9)	N1—C13—C14	114.5 (2)
C15—O1—Cd1	87.1 (2)	N1—C13—H13A	108.6
C15—O2—Cd1	99.7 (2)	C14—C13—H13A	108.6
C17—O3—Cd1	81.2 (3)	N1—C13—H13B	108.6
C17—O4—Cd1	104.9 (2)	C14—C13—H13B	108.6
H6B—O6—H6A	108 (5)	H13A—C13—H13B	107.6
H7C—O7—H7D	106 (5)	C13—C14—C14ⁱ	110.1 (3)
H8B—O8—H8A	110 (5)	C13—C14—H14A	109.6
H9B—O9—H9A	109 (5)	C14ⁱ—C14—H14A	109.6
C7—N1—C13	112.0 (2)	C13—C14—H14B	109.6
C7—N1—C1	110.3 (2)	C14ⁱ—C14—H14B	109.6
C13—N1—C1	108.8 (2)	H14A—C14—H14B	108.2
C7—N1—Cd1	107.62 (18)	O1—C15—O2	120.1 (3)
C13—N1—Cd1	112.52 (18)	O1—C15—C16	121.2 (3)
C1—N1—Cd1	105.36 (18)	O2—C15—C16	118.5 (3)
C2—N2—C6	118.6 (3)	C15—C16—H16A	109.5
C2—N2—Cd1	115.3 (2)	C15—C16—H16B	109.5
C6—N2—Cd1	126.1 (2)	H16A—C16—H16B	109.5
C8—N3—C12	118.3 (3)	C15—C16—H16C	109.5
C8—N3—Cd1	116.9 (2)	H16A—C16—H16C	109.5
C12—N3—Cd1	124.8 (2)	H16B—C16—H16C	109.5
N1—C1—C2	111.3 (2)	O4—C17—O3	121.8 (4)
N1—C1—H1A	109.4	O4—C17—O3	121.8 (4)
C2—C1—H1A	109.4	O4—C17—O3	121.8 (4)
N1—C1—H1B	109.4	O4—C17—O3	121.8 (4)
C2—C1—H1B	109.4	O4—C17—C18	118.3 (4)
H1A—C1—H1B	108.0	O4—C17—C18	118.3 (4)
N2—C2—C3	121.7 (3)	O3—C17—C18	119.8 (4)
N2—C2—C1	117.0 (3)	O3—C17—C18	119.8 (4)
C3—C2—C1	121.2 (3)	C17—C18—H18A	109.5
C4—C3—C2	119.2 (4)	C17—C18—H18B	109.5
C4—C3—H3	120.4	H18A—C18—H18B	109.5
C2—C3—H3	120.4	C17—C18—H18C	109.5
C3—C4—C5	119.1 (4)	H18A—C18—H18C	109.5
C3—C4—H4	120.4	H18B—C18—H18C	109.5
C5—C4—H4	120.4

O4—Cd1—O1—C15	2.7 (5)	N3—Cd1—N2—C6	−160.9 (2)
O4—Cd1—O1—C15	2.7 (5)	N1—Cd1—N2—C6	−160.6 (3)
O2—Cd1—O1—C15	−4.0 (3)	O1—Cd1—N2—C6	117.9 (3)
N3—Cd1—O1—C15	121.8 (3)	O3—Cd1—N2—C6	−9.8 (3)
N2—Cd1—O1—C15	−94.7 (3)	O4—Cd1—N3—C8	−125.3 (2)
N1—Cd1—O1—C15	−164.7 (3)	O4—Cd1—N3—C8	−125.3 (2)
O3—Cd1—O1—C15	41.0 (3)	O2—Cd1—N3—C8	115.0 (2)
O4—Cd1—O2—C15	−173.9 (3)	N2—Cd1—N3—C8	−14.2 (3)
O4—Cd1—O2—C15	−173.9 (3)	N1—Cd1—N3—C8	−14.5 (2)
N3—Cd1—O2—C15	−55.8 (3)	O1—Cd1—N3—C8	71.1 (2)
N2—Cd1—O2—C15	96.7 (3)	O3—Cd1—N3—C8	−171.6 (2)
N1—Cd1—O2—C15	30.4 (3)	O4—Cd1—N3—C12	57.2 (3)
O1—Cd1—O2—C15	3.9 (3)	O4—Cd1—N3—C12	57.2 (3)
O3—Cd1—O2—C15	−135.3 (3)	O2—Cd1—N3—C12	−62.5 (3)
O4—Cd1—O3—O3	0.00 (18)	N2—Cd1—N3—C12	168.3 (2)
O4—Cd1—O3—O3	0.00 (18)	N1—Cd1—N3—C12	168.0 (3)
O2—Cd1—O3—O3	0.00 (11)	O1—Cd1—N3—C12	−106.4 (2)
N3—Cd1—O3—O3	0.00 (13)	O3—Cd1—N3—C12	10.9 (2)
N2—Cd1—O3—O3	0.00 (13)	C7—N1—C1—C2	164.2 (3)
N1—Cd1—O3—O3	0.00 (6)	C13—N1—C1—C2	−72.5 (3)
O1—Cd1—O3—O3	0.00 (16)	Cd1—N1—C1—C2	48.4 (3)
O4—Cd1—O3—C17	7.3 (2)	C6—N2—C2—C3	−1.8 (5)
O4—Cd1—O3—C17	7.3 (2)	Cd1—N2—C2—C3	176.7 (2)
O2—Cd1—O3—C17	−122.9 (3)	C6—N2—C2—C1	−179.7 (3)
N3—Cd1—O3—C17	123.5 (3)	Cd1—N2—C2—C1	−1.2 (3)
N2—Cd1—O3—C17	−39.8 (3)	N1—C1—C2—N2	−33.5 (4)
N1—Cd1—O3—C17	77.8 (3)	N1—C1—C2—C3	148.6 (3)
O1—Cd1—O3—C17	−158.3 (3)	N2—C2—C3—C4	0.6 (5)
O2—Cd1—O4—O4	0.0 (3)	C1—C2—C3—C4	178.4 (3)
N3—Cd1—O4—O4	0.0 (3)	C2—C3—C4—C5	1.0 (5)
N2—Cd1—O4—O4	0.0 (3)	C3—C4—C5—C6	−1.2 (5)
N1—Cd1—O4—O4	0.0 (2)	C2—N2—C6—C5	1.5 (5)
O1—Cd1—O4—O4	0.0 (4)	Cd1—N2—C6—C5	−176.8 (2)
O3—Cd1—O4—O4	0.0 (2)	C4—C5—C6—N2	0.0 (5)
O4—Cd1—O4—C17	0 (19)	C13—N1—C7—C8	88.0 (3)
O2—Cd1—O4—C17	44.4 (3)	C1—N1—C7—C8	−150.7 (3)
N3—Cd1—O4—C17	−76.6 (3)	Cd1—N1—C7—C8	−36.2 (3)
N2—Cd1—O4—C17	137.0 (3)	C12—N3—C8—C9	0.0 (4)
N1—Cd1—O4—C17	−155.0 (3)	Cd1—N3—C8—C9	−177.7 (2)
O1—Cd1—O4—C17	38.8 (5)	C12—N3—C8—C7	176.9 (3)
O3—Cd1—O4—C17	−7.5 (3)	Cd1—N3—C8—C7	−0.7 (3)
O4—Cd1—N1—C7	127.65 (19)	N1—C7—C8—N3	26.7 (4)
O4—Cd1—N1—C7	127.65 (19)	N1—C7—C8—C9	−156.3 (3)
O2—Cd1—N1—C7	−77.5 (2)	N3—C8—C9—C10	0.5 (5)
N3—Cd1—N1—C7	26.46 (18)	C7—C8—C9—C10	−176.4 (3)
N2—Cd1—N1—C7	−153.4 (2)	C8—C9—C10—C11	−0.4 (5)
O1—Cd1—N1—C7	−56.62 (19)	C9—C10—C11—C12	−0.1 (5)
O3—Cd1—N1—C7	74.8 (3)	C8—N3—C12—C11	−0.5 (4)
O4—Cd1—N1—C13	3.7 (2)	Cd1—N3—C12—C11	176.9 (2)
O4—Cd1—N1—C13	3.7 (2)	C10—C11—C12—N3	0.6 (5)
O2—Cd1—N1—C13	158.6 (2)	C7—N1—C13—C14	−66.3 (3)
N3—Cd1—N1—C13	−97.5 (2)	C1—N1—C13—C14	171.5 (3)
N2—Cd1—N1—C13	82.7 (2)	Cd1—N1—C13—C14	55.2 (3)
O1—Cd1—N1—C13	179.5 (2)	N1—C13—C14—C14ⁱ	−173.6 (3)
O3—Cd1—N1—C13	−49.1 (3)	Cd1—O1—C15—O2	6.6 (4)
O4—Cd1—N1—C1	−114.65 (19)	Cd1—O1—C15—C16	−178.5 (4)
O4—Cd1—N1—C1	−114.65 (19)	Cd1—O2—C15—O1	−7.5 (5)
O2—Cd1—N1—C1	40.2 (2)	Cd1—O2—C15—C16	177.4 (4)
N3—Cd1—N1—C1	144.16 (19)	Cd1—O4—C17—O4	0 (66)
N2—Cd1—N1—C1	−35.66 (18)	O4—O4—C17—O3	0.00 (9)
O1—Cd1—N1—C1	61.08 (19)	Cd1—O4—C17—O3	15.0 (5)
O3—Cd1—N1—C1	−167.51 (19)	O4—O4—C17—O3	0.00 (9)
O4—Cd1—N2—C2	137.5 (2)	Cd1—O4—C17—O3	15.0 (5)
O4—Cd1—N2—C2	137.5 (2)	O4—O4—C17—C18	0.00 (7)
O2—Cd1—N2—C2	−113.1 (2)	Cd1—O4—C17—C18	−168.0 (4)
N3—Cd1—N2—C2	20.7 (3)	O3—O3—C17—O4	0.00 (10)
N1—Cd1—N2—C2	21.0 (2)	Cd1—O3—C17—O4	−12.0 (4)
O1—Cd1—N2—C2	−60.4 (2)	O3—O3—C17—O4	0.00 (10)
O3—Cd1—N2—C2	171.8 (2)	Cd1—O3—C17—O4	−12.0 (4)
O4—Cd1—N2—C6	−44.1 (3)	Cd1—O3—C17—O3	0 (100)
O4—Cd1—N2—C6	−44.1 (3)	O3—O3—C17—C18	0.0 (2)
O2—Cd1—N2—C6	65.3 (3)	Cd1—O3—C17—C18	171.1 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O3	0.80 (6)	2.06 (6)	2.829 (5)	160 (6)
O6—H6A···O4	0.77 (5)	1.98 (5)	2.745 (4)	170 (5)
O9—H9B···O5ⁱⁱ	0.79 (5)	2.07 (5)	2.852 (3)	170 (5)
O7—H7C···O1ⁱⁱⁱ	0.76 (5)	1.91 (5)	2.673 (4)	177 (5)
O8—H8A···O9^iv	0.73 (5)	2.04 (5)	2.769 (4)	172 (5)
O6—H6B···O8ⁱ	0.85 (5)	1.97 (5)	2.792 (4)	164 (5)
O5—H5A···O7ⁱⁱⁱ	0.76 (4)	1.96 (4)	2.708 (3)	170 (5)
O8—H8B···O6^v	0.78 (5)	2.06 (5)	2.825 (4)	166 (4)

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

Experimental details

Crystal data
Chemical formula	[Cd₂(C₂H₃O₂)₄(C₂₈H₃₂N₆)]·9H₂O
M_r	1075.72
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	90
a, b, c (Å)	15.9680 (17), 11.4320 (12), 26.451 (3)
β (°)	100.127 (2)
V (Å³)	4753.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.760, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	23441, 5847, 5621
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.103, 1.20
No. of reflections	5847
No. of parameters	314
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0355P)² + 21.0991P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.55, −0.57

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—O4	2.240 (2)	Cd1—N1	2.405 (3)
Cd1—O2	2.251 (3)	Cd1—O1	2.550 (3)
Cd1—N3	2.313 (3)	Cd1—O3	2.729 (4)
Cd1—N2	2.379 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O3	0.80 (6)	2.06 (6)	2.829 (5)	160 (6)
O6—H6A···O4	0.77 (5)	1.98 (5)	2.745 (4)	170 (5)
O9—H9B···O5ⁱ	0.79 (5)	2.07 (5)	2.852 (3)	170 (5)
O7—H7C···O1ⁱⁱ	0.76 (5)	1.91 (5)	2.673 (4)	177 (5)
O8—H8A···O9ⁱⁱⁱ	0.73 (5)	2.04 (5)	2.769 (4)	172 (5)
O6—H6B···O8^iv	0.85 (5)	1.97 (5)	2.792 (4)	164 (5)
O5—H5A···O7ⁱⁱ	0.76 (4)	1.96 (4)	2.708 (3)	170 (5)
O8—H8B···O6^v	0.78 (5)	2.06 (5)	2.825 (4)	166 (4)

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

Footnotes

‡Current address: Harvard Medical School, Children's Hospital Boston, Department of Radiology, 300 Longwood Ave, Enders 4, Boston, MA 02115, USA.

Acknowledgements

This work was supported by funding from Syracuse University.

References

Bartholomä, M., Cheung, H., Darling, K. & Zubieta, J. (2010d). Acta Cryst. E66, m1201–m1202. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010a). Acta Cryst. E66, m1197. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010b). Acta Cryst. E66, m1198. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010c). Acta Cryst. E66, m1199–m1200. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Valliant, J., Maresca, K. P., Babich, J. & Zubieta, J. (2009). Chem. Commun. 5, 473–604. Google Scholar
Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ertürk, H., Hofmann, A., Puchta, R. & van Eldik, R. (2007). Dalton Trans. pp. 2295–2301. Web of Science PubMed Google Scholar
Fujihara, T., Saito, M. & Nagasawa, A. (2004). Acta Cryst. E60, o1126–o1128. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mambanda, A., Jaganyi, D. & Munro, O. Q. (2007). Acta Cryst. C63, o676–o680. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tamura, M., Urano, Y., Kikuchi, K., Higuchi, T., Hirobe, M. & Nagano, T. (2000). J. Organomet. Chem. 611, 586–592. Web of Science CrossRef CAS Google Scholar

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