Di-μ-nicotinato-κN:O;κO:N-bis-[aqua-(ethyl-enediamine-κN,N')(nicotinato-κN)cadmium(II)] dihydrate.

The dinuclear mol-ecule of the title compound, [Cd(2)(C(6)H(4)NO(2))(4)(C(2)H(8)N(2))(2)(H(2)O)(2)]·2H(2)O, lies on an inversion centre and forms 12-membered (CdNC(3)O)(2) metallacycles with the two Cd(2+) ions bridged by two nicotinate ligands. Both Cd(2+) ions display coordination polyhedra with a distorted octa-hedral geometry that includes two pyridine N atoms from bridging and terminal nicotinate anions, two amine N atoms from chelating ethylene-diamine ligands, carboxylate O atoms from bridging nicotinate anions and water O atoms. Inter-molecular O-H⋯O and N-H⋯O hydrogen bonds result in the formation of a three-dimensional network, and π-π stacking inter-actions are observed between symmetry-related pyridine rings of bridging as well as terminal nicotinate anions (the centroid-centroid distances are 3.59 and 3.69 Å, respectively, and the distances between parallel planes of the stacked pyridine rings are 3.53 and 3.43 Å, respectively). The two methylene groups of the ethylene-diamine ligand are disordered over two positions; the site occupancy factors are ca 0.8 and 0.2.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Chen (2003 ▶); Clegg et al. (1995 ▶); Evans & Lin (2001 ▶); Janiak (2000 ▶); Kang et al. (2007 ▶); Liang & Li (2005 ▶); Lu & Kohler (2002 ▶); Lu et al. (2007 ▶); Luo et al. (2004 ▶); Song et al. (2006 ▶); Xian et al. (2007 ▶); Zhang et al. (1996 ▶); Zhang et al. (2004 ▶). For related structures, see: Ayyappan et al. (2001 ▶); Abu-Youssef (2005 ▶); Chen et al. (2001 ▶, 2008 ▶); Lin et al. (2000 ▶); Liu et al. (2005 ▶); Madalan et al. (2005 ▶); Wang et al. (2002 ▶); Wasson & LaDuca (2007 ▶); Wu et al. (2003 ▶).

Experimental

Crystal data

[Cd2(C6H4NO2)4(C2H8N2)2(H2O)2]·2H2O

M = 905.18

Triclinic,

a = 7.678 (1) Å

b = 10.364 (1) Å

c = 11.984 (2) Å

α = 101.080 (1)°

β = 93.60 (1)°

γ = 109.63 (1)°

V = 873.1 (2) Å3

Z = 1

Mo Kα radiation

μ = 1.29 mm−1

T = 294 (2) K

0.35 × 0.30 × 0.20 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XEMP; Siemens, 1994 ▶) T min = 0.652, T max = 0.776

6118 measured reflections

5071 independent reflections

4491 reflections with I > 2σ(I)

R int = 0.055

3 standard reflections every 97 reflections intensity decay: 2.0%

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.076

S = 1.06

5071 reflections

245 parameters

21 restraints

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.62 e Å−3

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009756/zl2107sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009756/zl2107Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cd2(C6H4NO2)4(C2H8N2)2(H2O)2]·2H2O	Z = 1
Mr = 905.18	F000 = 456
Triclinic, P1	Dx = 1.722 Mg m−3
Hall symbol: -P1	Mo Kα radiation λ = 0.71073 Å
a = 7.6780 (10) Å	Cell parameters from 25 reflections
b = 10.3640 (10) Å	θ = 2.1–8.9º
c = 11.984 (2) Å	µ = 1.29 mm−1
α = 101.080 (10)º	T = 294 (2) K
β = 93.600 (10)º	Prism, colourless
γ = 109.630 (10)º	0.35 × 0.30 × 0.20 mm
V = 873.1 (2) Å3

Siemens P4 diffractometer	Rint = 0.055
Radiation source: fine-focus sealed tube	θmax = 30.0º
Monochromator: graphite	θmin = 1.8º
T = 294(2) K	h = −1→10
2θ/ω scans	k = −14→13
Absorption correction: ψ scan(XEMP; Siemens, 1994)	l = −16→16
Tmin = 0.652, Tmax = 0.776	3 standard reflections
6118 measured reflections	every 97 reflections
5071 independent reflections	intensity decay: 2.0%
4491 reflections with I > 2σ(I)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H-atom parameters constrained
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0307P)2 + 0.1604P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
5071 reflections	Δρmax = 0.57 e Å−3
245 parameters	Δρmin = −0.62 e Å−3
21 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cd1	0.50747 (2)	0.217937 (14)	0.263617 (13)	0.03264 (6)
O1	0.3261 (3)	0.3353 (2)	0.35364 (17)	0.0505 (5)
O1W	0.7358 (3)	0.13999 (17)	0.18352 (18)	0.0457 (4)
H1W	0.7166	0.0558	0.1631	0.069*
H2W	0.8505	0.1895	0.2005	0.069*
O2	0.1020 (3)	0.3222 (2)	0.21860 (16)	0.0471 (4)
O2W	0.1968 (6)	0.0994 (5)	0.4981 (3)	0.1256 (15)
H3W	0.1050	0.0314	0.5055	0.188*
H4W	0.2579	0.1496	0.5595	0.188*
O3	0.6053 (4)	0.8065 (2)	0.2856 (2)	0.0739 (8)
O4	0.6980 (4)	0.87012 (19)	0.12727 (19)	0.0619 (6)
N1	0.2917 (3)	0.6858 (2)	0.56161 (17)	0.0364 (4)
N2	0.6293 (3)	0.41008 (18)	0.17134 (17)	0.0353 (4)
N3	0.2678 (3)	0.0997 (2)	0.11238 (19)	0.0429 (4)
H3A	0.1697	0.1239	0.1265	0.051*	0.780 (10)
H3B	0.3071	0.1225	0.0476	0.051*	0.780 (10)
H3C	0.2002	0.1532	0.1062	0.051*	0.220 (10)
H3D	0.3192	0.0863	0.0479	0.051*	0.220 (10)
N4	0.3717 (3)	−0.0048 (2)	0.30277 (19)	0.0445 (5)
H4A	0.4522	−0.0522	0.2930	0.053*	0.780 (10)
H4B	0.3529	0.0051	0.3776	0.053*	0.780 (10)
H4C	0.4641	−0.0346	0.3276	0.053*	0.220 (10)
H4D	0.3025	0.0006	0.3600	0.053*	0.220 (10)
C1	0.2052 (3)	0.3777 (2)	0.3123 (2)	0.0347 (4)
C2	0.1904 (3)	0.5085 (2)	0.38534 (19)	0.0315 (4)
C3	0.2937 (3)	0.5680 (2)	0.4933 (2)	0.0357 (4)
H3	0.3691	0.5233	0.5199	0.043*
C4	0.1810 (4)	0.7494 (2)	0.5236 (2)	0.0412 (5)
H4	0.1777	0.8311	0.5702	0.049*
C5	0.0722 (4)	0.6972 (3)	0.4178 (2)	0.0468 (6)
H5	−0.0040	0.7429	0.3940	0.056*
C6	0.0771 (3)	0.5761 (3)	0.3470 (2)	0.0407 (5)
H6	0.0058	0.5405	0.2749	0.049*
C7	0.6597 (4)	0.7856 (2)	0.1908 (2)	0.0428 (5)
C8	0.6792 (3)	0.6441 (2)	0.1471 (2)	0.0326 (4)
C9	0.6207 (3)	0.5384 (2)	0.20765 (19)	0.0333 (4)
H9	0.5737	0.5576	0.2761	0.040*
C10	0.6977 (3)	0.3842 (2)	0.0733 (2)	0.0386 (5)
H10	0.7041	0.2955	0.0478	0.046*
C11	0.7595 (4)	0.4825 (3)	0.0076 (2)	0.0399 (5)
H11	0.8065	0.4605	−0.0603	0.048*
C12	0.7494 (3)	0.6147 (2)	0.0455 (2)	0.0358 (4)
H12	0.7895	0.6829	0.0030	0.043*
C13A	0.2200 (8)	−0.0529 (4)	0.1059 (4)	0.0548 (13)	0.780 (10)
H13A	0.3186	−0.0828	0.0767	0.066*	0.780 (10)
H13B	0.1052	−0.1059	0.0539	0.066*	0.780 (10)
C14A	0.1963 (8)	−0.0807 (5)	0.2237 (4)	0.0604 (14)	0.780 (10)
H14A	0.0978	−0.0504	0.2527	0.072*	0.780 (10)
H14B	0.1602	−0.1808	0.2193	0.072*	0.780 (10)
C13B	0.1473 (18)	−0.0289 (13)	0.1436 (17)	0.056 (4)	0.220 (10)
H13C	0.0625	−0.0923	0.0769	0.067*	0.220 (10)
H13D	0.0740	−0.0052	0.2019	0.067*	0.220 (10)
C14B	0.270 (2)	−0.0967 (12)	0.1881 (13)	0.052 (4)	0.220 (10)
H14C	0.3580	−0.1059	0.1354	0.062*	0.220 (10)
H14D	0.1959	−0.1898	0.1967	0.062*	0.220 (10)

	U11	U22	U33	U12	U13	U23
Cd1	0.04196 (9)	0.02134 (7)	0.03364 (8)	0.01255 (6)	0.00412 (6)	0.00197 (5)
O1	0.0542 (11)	0.0569 (11)	0.0438 (9)	0.0363 (9)	−0.0027 (8)	−0.0076 (8)
O1W	0.0458 (9)	0.0247 (7)	0.0671 (12)	0.0154 (7)	0.0149 (8)	0.0040 (7)
O2	0.0444 (9)	0.0463 (9)	0.0415 (9)	0.0158 (8)	−0.0034 (7)	−0.0076 (7)
O2W	0.162 (4)	0.189 (4)	0.075 (2)	0.125 (3)	0.040 (2)	0.022 (2)
O3	0.135 (2)	0.0523 (12)	0.0625 (14)	0.0592 (14)	0.0451 (15)	0.0202 (11)
O4	0.1147 (19)	0.0276 (8)	0.0537 (12)	0.0330 (10)	0.0270 (12)	0.0143 (8)
N1	0.0429 (10)	0.0330 (9)	0.0338 (9)	0.0176 (8)	0.0026 (7)	0.0023 (7)
N2	0.0440 (10)	0.0227 (7)	0.0409 (10)	0.0147 (7)	0.0038 (8)	0.0067 (7)
N3	0.0484 (11)	0.0411 (10)	0.0368 (10)	0.0151 (9)	0.0021 (8)	0.0062 (8)
N4	0.0578 (13)	0.0339 (9)	0.0417 (11)	0.0138 (9)	0.0093 (9)	0.0124 (8)
C1	0.0322 (10)	0.0333 (10)	0.0352 (10)	0.0108 (8)	0.0063 (8)	0.0012 (8)
C2	0.0308 (9)	0.0300 (9)	0.0341 (10)	0.0113 (8)	0.0082 (8)	0.0059 (8)
C3	0.0391 (11)	0.0335 (10)	0.0361 (10)	0.0182 (9)	0.0038 (8)	0.0026 (8)
C4	0.0532 (14)	0.0342 (11)	0.0413 (12)	0.0234 (10)	0.0066 (10)	0.0060 (9)
C5	0.0578 (15)	0.0456 (13)	0.0460 (13)	0.0309 (12)	0.0013 (11)	0.0102 (11)
C6	0.0422 (12)	0.0442 (12)	0.0375 (11)	0.0198 (10)	0.0008 (9)	0.0068 (9)
C7	0.0629 (15)	0.0264 (9)	0.0439 (12)	0.0223 (10)	0.0083 (11)	0.0071 (9)
C8	0.0362 (10)	0.0228 (8)	0.0394 (10)	0.0122 (7)	0.0018 (8)	0.0064 (7)
C9	0.0402 (11)	0.0248 (9)	0.0367 (10)	0.0141 (8)	0.0050 (8)	0.0066 (8)
C10	0.0504 (13)	0.0262 (9)	0.0410 (11)	0.0191 (9)	0.0041 (9)	0.0028 (8)
C11	0.0485 (13)	0.0355 (11)	0.0404 (11)	0.0207 (10)	0.0128 (9)	0.0065 (9)
C12	0.0399 (11)	0.0279 (9)	0.0406 (11)	0.0112 (8)	0.0087 (9)	0.0102 (8)
C13A	0.069 (3)	0.0353 (17)	0.0425 (19)	0.0009 (17)	−0.0001 (18)	0.0024 (14)
C14A	0.062 (3)	0.048 (2)	0.052 (2)	−0.007 (2)	0.006 (2)	0.0158 (19)
C13B	0.043 (7)	0.043 (7)	0.063 (10)	0.004 (5)	−0.002 (6)	−0.004 (6)
C14B	0.055 (8)	0.024 (5)	0.064 (9)	0.001 (5)	0.011 (6)	0.003 (5)

Cd1—N3	2.321 (2)	N4—H4D	0.8980
Cd1—O1	2.325 (2)	C1—C2	1.509 (3)
Cd1—N4	2.344 (2)	C2—C3	1.385 (3)
Cd1—O1W	2.348 (2)	C2—C6	1.394 (3)
Cd1—N1i	2.349 (2)	C3—H3	0.9300
Cd1—N2	2.406 (2)	C4—C5	1.378 (4)
O1—C1	1.264 (3)	C4—H4	0.9300
O1W—H1W	0.8187	C5—C6	1.387 (3)
O1W—H2W	0.8450	C5—H5	0.9300
O2—C1	1.247 (3)	C6—H6	0.9300
O2W—H3W	0.8365	C7—C8	1.519 (3)
O2W—H4W	0.8232	C8—C12	1.385 (3)
O3—C7	1.240 (3)	C8—C9	1.395 (3)
O4—C7	1.243 (3)	C9—H9	0.9300
N1—C3	1.339 (3)	C10—C11	1.384 (3)
N1—C4	1.344 (3)	C10—H10	0.9300
N1—Cd1i	2.349 (2)	C11—C12	1.388 (3)
N2—C10	1.334 (3)	C11—H11	0.9300
N2—C9	1.343 (3)	C12—H12	0.9300
N3—C13B	1.477 (12)	C13A—C14A	1.504 (6)
N3—C13A	1.484 (4)	C13A—H13A	0.9700
N3—H3A	0.8860	C13A—H13B	0.9700
N3—H3B	0.8955	C14A—H14A	0.9700
N3—H3C	0.8870	C14A—H14B	0.9700
N3—H3D	0.8982	C13B—C14B	1.479 (15)
N4—C14A	1.474 (5)	C13B—H13C	0.9700
N4—C14B	1.507 (12)	C13B—H13D	0.9700
N4—H4A	0.9105	C14B—H14C	0.9700
N4—H4B	0.9088	C14B—H14D	0.9700
N4—H4C	0.9180
N3—Cd1—O1	90.64 (7)	O2—C1—C2	118.9 (2)
N3—Cd1—N4	76.38 (8)	O1—C1—C2	115.1 (2)
O1—Cd1—N4	100.83 (9)	C3—C2—C6	117.3 (2)
N3—Cd1—O1W	97.31 (8)	C3—C2—C1	120.63 (19)
O1—Cd1—O1W	169.36 (7)	C6—C2—C1	122.1 (2)
N4—Cd1—O1W	87.95 (7)	N1—C3—C2	124.0 (2)
N3—Cd1—N1i	168.76 (7)	N1—C3—H3	118.0
O1—Cd1—N1i	84.28 (7)	C2—C3—H3	118.0
N4—Cd1—N1i	94.70 (7)	N1—C4—C5	122.1 (2)
O1W—Cd1—N1i	89.07 (7)	N1—C4—H4	119.0
N3—Cd1—N2	91.32 (7)	C5—C4—H4	119.0
O1—Cd1—N2	88.34 (7)	C4—C5—C6	119.5 (2)
N4—Cd1—N2	164.61 (7)	C4—C5—H5	120.2
O1W—Cd1—N2	84.44 (7)	C6—C5—H5	120.2
N1i—Cd1—N2	98.52 (7)	C5—C6—C2	119.1 (2)
C1—O1—Cd1	130.80 (16)	C5—C6—H6	120.4
Cd1—O1W—H1W	120.5	C2—C6—H6	120.4
Cd1—O1W—H2W	121.2	O3—C7—O4	125.6 (2)
H1W—O1W—H2W	113.0	O3—C7—C8	117.7 (2)
H3W—O2W—H4W	113.8	O4—C7—C8	116.7 (2)
C3—N1—C4	118.0 (2)	C12—C8—C9	118.18 (19)
C3—N1—Cd1i	119.65 (15)	C12—C8—C7	121.6 (2)
C4—N1—Cd1i	122.28 (16)	C9—C8—C7	120.2 (2)
C10—N2—C9	117.98 (19)	N2—C9—C8	122.8 (2)
C10—N2—Cd1	117.60 (14)	N2—C9—H9	118.6
C9—N2—Cd1	124.23 (16)	C8—C9—H9	118.6
C13B—N3—Cd1	107.2 (6)	N2—C10—C11	123.4 (2)
C13A—N3—Cd1	107.0 (2)	N2—C10—H10	118.3
C13B—N3—H3A	80.3	C11—C10—H10	118.3
C13A—N3—H3A	109.8	C10—C11—C12	118.3 (2)
Cd1—N3—H3A	109.2	C10—C11—H11	120.8
C13B—N3—H3B	135.6	C12—C11—H11	120.8
C13A—N3—H3B	111.4	C8—C12—C11	119.4 (2)
Cd1—N3—H3B	109.0	C8—C12—H12	120.3
H3A—N3—H3B	110.3	C11—C12—H12	120.3
C13B—N3—H3C	107.7	N3—C13A—C14A	109.3 (4)
C13A—N3—H3C	133.5	N3—C13A—H13A	109.8
Cd1—N3—H3C	108.4	C14A—C13A—H13A	109.8
C13B—N3—H3D	115.9	N3—C13A—H13B	109.8
C13A—N3—H3D	86.8	C14A—C13A—H13B	109.8
Cd1—N3—H3D	108.1	H13A—C13A—H13B	108.3
H3C—N3—H3D	109.4	N4—C14A—C13A	110.5 (4)
C14A—N4—Cd1	108.3 (2)	N4—C14A—H14A	109.6
C14B—N4—Cd1	103.7 (6)	C13A—C14A—H14A	109.6
C14A—N4—H4A	110.7	N4—C14A—H14B	109.6
C14B—N4—H4A	85.4	C13A—C14A—H14B	109.6
Cd1—N4—H4A	109.4	H14A—C14A—H14B	108.1
C14A—N4—H4B	112.2	N3—C13B—C14B	107.7 (12)
C14B—N4—H4B	137.7	N3—C13B—H13C	110.2
Cd1—N4—H4B	109.4	C14B—C13B—H13C	110.2
H4A—N4—H4B	106.8	N3—C13B—H13D	110.2
C14A—N4—H4C	131.2	C14B—C13B—H13D	110.2
C14B—N4—H4C	110.1	H13C—C13B—H13D	108.5
Cd1—N4—H4C	109.3	C13B—C14B—N4	107.3 (12)
C14A—N4—H4D	88.0	C13B—C14B—H14C	110.3
C14B—N4—H4D	116.6	N4—C14B—H14C	110.3
Cd1—N4—H4D	109.8	C13B—C14B—H14D	110.3
H4C—N4—H4D	107.1	N4—C14B—H14D	110.3
O2—C1—O1	126.0 (2)	H14C—C14B—H14D	108.5
N3—Cd1—O1—C1	−33.5 (2)	O1—C1—C2—C3	−4.8 (3)
N4—Cd1—O1—C1	−109.7 (2)	O2—C1—C2—C6	−5.8 (3)
O1W—Cd1—O1—C1	105.0 (4)	O1—C1—C2—C6	173.7 (2)
N1i—Cd1—O1—C1	156.5 (2)	C4—N1—C3—C2	0.8 (4)
N2—Cd1—O1—C1	57.8 (2)	Cd1i—N1—C3—C2	−175.37 (17)
N3—Cd1—N2—C10	−65.68 (18)	C6—C2—C3—N1	−0.4 (4)
O1—Cd1—N2—C10	−156.28 (18)	C1—C2—C3—N1	178.1 (2)
N4—Cd1—N2—C10	−29.2 (4)	C3—N1—C4—C5	−0.2 (4)
O1W—Cd1—N2—C10	31.54 (18)	Cd1i—N1—C4—C5	175.8 (2)
N1i—Cd1—N2—C10	119.76 (17)	N1—C4—C5—C6	−0.6 (4)
N3—Cd1—N2—C9	109.32 (19)	C4—C5—C6—C2	0.9 (4)
O1—Cd1—N2—C9	18.72 (18)	C3—C2—C6—C5	−0.4 (4)
N4—Cd1—N2—C9	145.8 (3)	C1—C2—C6—C5	−179.0 (2)
O1W—Cd1—N2—C9	−153.46 (19)	O3—C7—C8—C12	−176.1 (3)
N1i—Cd1—N2—C9	−65.24 (19)	O4—C7—C8—C12	4.7 (4)
O1—Cd1—N3—C13B	−87.9 (8)	O3—C7—C8—C9	5.8 (4)
N4—Cd1—N3—C13B	13.1 (8)	O4—C7—C8—C9	−173.4 (3)
O1W—Cd1—N3—C13B	99.2 (8)	C10—N2—C9—C8	0.3 (3)
N1i—Cd1—N3—C13B	−25.0 (9)	Cd1—N2—C9—C8	−174.71 (16)
N2—Cd1—N3—C13B	−176.2 (8)	C12—C8—C9—N2	−0.2 (3)
O1—Cd1—N3—C13A	−121.2 (3)	C7—C8—C9—N2	178.0 (2)
N4—Cd1—N3—C13A	−20.2 (3)	C9—N2—C10—C11	−0.1 (4)
O1W—Cd1—N3—C13A	65.9 (3)	Cd1—N2—C10—C11	175.22 (19)
N1i—Cd1—N3—C13A	−58.3 (5)	N2—C10—C11—C12	−0.1 (4)
N2—Cd1—N3—C13A	150.4 (3)	C9—C8—C12—C11	−0.1 (3)
N3—Cd1—N4—C14A	−10.2 (3)	C7—C8—C12—C11	−178.2 (2)
O1—Cd1—N4—C14A	77.8 (3)	C10—C11—C12—C8	0.2 (4)
O1W—Cd1—N4—C14A	−108.2 (3)	C13B—N3—C13A—C14A	−46.9 (11)
N1i—Cd1—N4—C14A	162.9 (3)	Cd1—N3—C13A—C14A	48.5 (6)
N2—Cd1—N4—C14A	−47.9 (5)	C14B—N4—C14A—C13A	−46.1 (10)
N3—Cd1—N4—C14B	20.6 (7)	Cd1—N4—C14A—C13A	39.8 (6)
O1—Cd1—N4—C14B	108.7 (7)	N3—C13A—C14A—N4	−61.5 (8)
O1W—Cd1—N4—C14B	−77.4 (7)	C13A—N3—C13B—C14B	47.9 (10)
N1i—Cd1—N4—C14B	−166.3 (7)	Cd1—N3—C13B—C14B	−46.7 (16)
N2—Cd1—N4—C14B	−17.1 (8)	N3—C13B—C14B—N4	70 (2)
Cd1—O1—C1—O2	30.5 (4)	C14A—N4—C14B—C13B	49.7 (10)
Cd1—O1—C1—C2	−148.90 (17)	Cd1—N4—C14B—C13B	−53.2 (15)
O2—C1—C2—C3	175.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O4ii	0.82	1.84	2.659 (2)	174
O1W—H2W···O2iii	0.84	1.93	2.762 (3)	169
O2W—H3W···O2Wiv	0.84	2.25	3.041 (10)	158
O2W—H4W···O3i	0.82	1.97	2.742 (5)	157
N3—H3A···O2	0.89	2.37	3.099 (3)	139
N3—H3B···O4v	0.90	2.11	2.966 (3)	160
N3—H3C···O2	0.89	2.36	3.099 (3)	141
N3—H3D···O4v	0.90	2.24	2.966 (3)	138
N4—H4A···O3ii	0.91	2.16	3.054 (3)	169
N4—H4B···O2W	0.91	2.22	2.975 (4)	140
N4—H4C···O3ii	0.92	2.26	3.054 (3)	145
N4—H4D···O2W	0.90	2.13	2.975 (4)	157

Compound	Bonding mode	M···M	Chromophore
Ia	µ2-nic-κ2N:O	7.355 (1)	CdN4O2
IIb	µ2-nic-κ2N:O	6.904 (2)	CuN4O
IIIc	µ2-nic-κ2N:O	6.972 (2)	CuN4O
IVd	µ3-nic-κ3N:O:O'	7.208 (1)	MnN2O4
Ve	µ3-nic-κ3N:O:O'	7.304 (3)	CdN2O4
VIf	µ3-nic-κ3N:O:O'	6.736 (1)	CuN3O2
VIIg	µ3-nic-κ3N:O:O'	6.680 (1)	CuN3O2
VIIIh	µ3-nic-κ3N:O:O'	6.646 (2)	NiN2O4
IXi	µ3-nic-κ3N:O:O'	6.90 (1)	NiN2O4
Xj	µ3-nic-κ3N:O:O'	6.622 (2)	NiN2O4
XIk	µ3-nic-κ3N:O:O'	7.324 (1)	MnN2O4
XIIl	µ3-nic-κ3N:O:O'	6.890 (2)	NiN2O4
	µ2-nic-κ2N:O	7.027 (2)	NiN3O3

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O4i	0.82	1.84	2.659 (2)	174
O1W—H2W⋯O2ii	0.84	1.93	2.762 (3)	169
O2W—H3W⋯O2Wiii	0.84	2.25	3.041 (10)	158
O2W—H4W⋯O3iv	0.82	1.97	2.742 (5)	157
N3—H3A⋯O2	0.89	2.37	3.099 (3)	139
N3—H3B⋯O4v	0.90	2.11	2.966 (3)	160
N3—H3C⋯O2	0.89	2.36	3.099 (3)	141
N3—H3D⋯O4v	0.90	2.24	2.966 (3)	138
N4—H4A⋯O3i	0.91	2.16	3.054 (3)	169
N4—H4B⋯O2W	0.91	2.22	2.975 (4)	140
N4—H4C⋯O3i	0.92	2.26	3.054 (3)	145
N4—H4D⋯O2W	0.90	2.13	2.975 (4)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .