catena-Poly­[[[di­aqua­cadmium(II)]-di-μ-4,4′-tri­methyl­enedi­pyridine-κ²N:N′] dinitrate 4,4′-tri­methyl­enedi­pyridine monohydrate]

The title compound, {[Cd(TMD)₂(H₂O)₂](NO₃)₂·TMD·H₂O}_n, where TMD is 4,4′-tri­methyl­enedi­pyridine (C₁₃H₁₄N₂), obtained using hydro­thermal synthesis followed by slow crystallization, is formed by strong hydrogen bonds between a one-dimensional coordination polymer and uncoordinated TMD, water mol­ecules and nitrate ions.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.025
• wR factor = 0.066
• Data-to-parameter ratio = 12.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_161  Alert C Missing or Zero su (esd) on x-coordinate for .       CD1

PLAT_162  Alert C Missing or Zero su (esd) on y-coordinate for .       CD1

PLAT_163  Alert C Missing or Zero su (esd) on z-coordinate for .       CD1

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ....       3.00 su-Ratio
                     O11  -H11A    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
                     O11  -H11B    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ....       3.00 su-Ratio
                     O12  -H12A    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ....       3.00 su-Ratio
                     O12  -H12B    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.88(4), Rep   0.880(10) ....       4.00 su-Ratio
                     O7W  -H7A     1.555   1.555

PLAT_731  Alert C Bond    Calc     0.87(3), Rep   0.880(10) ....       3.00 su-Ratio
                     O7W  -H7B     1.555   1.555

PLAT_735  Alert C D-H     Calc     0.88(4), Rep   0.880(10) ....       4.00 su-Ratio
                     O7W  -H7A     1.555   1.555

PLAT_735  Alert C D-H     Calc     0.87(3), Rep   0.880(10) ....       3.00 su-Ratio
                     O7W  -H7B     1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(4), Rep   0.850(10) ....       4.00 su-Ratio
                     O11  -H11B    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ....       3.00 su-Ratio
                     O12  -H12A    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ....       3.00 su-Ratio
                     O12  -H12B    1.555   1.555

PLAT_736  Alert C H...A   Calc     2.02(4), Rep   2.020(10) ....       4.00 su-Ratio
                     H7A  -O63     1.555   1.555

PLAT_736  Alert C H...A   Calc     2.03(3), Rep   2.030(10) ....       3.00 su-Ratio
                     H7B  -O53     1.555   1.555

PLAT_736  Alert C H...A   Calc     1.88(4), Rep   1.880(10) ....       4.00 su-Ratio
                     H11B -N42     1.555   1.556

PLAT_736  Alert C H...A   Calc     1.88(3), Rep   1.880(10) ....       3.00 su-Ratio
                     H12A -N41     1.555   1.545

PLAT_736  Alert C H...A   Calc     1.99(3), Rep   1.990(10) ....       3.00 su-Ratio
                     H12B -O62     1.555   1.656

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.94
         From the CIF: _reflns_number_total               6863
         Count of symmetry unique reflns         4494
         Completeness (_total/calc)            152.71%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2369
         Fraction of Friedel pairs measured     0.527
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 19 Alert Level C = Please check

---

S1. Comment

We are interested in the hydrothermal synthesis of novel metal–organic frameworks which incorporate not only rigid and symmetrical spacers, but also ligands capable of inducing supramolecular isomerism into the final structure (Almeida Paz et al., 2002).

The title compound, (I), contains a one-dimensional cationic coordination polymer, [Cd(TMD)₂(H₂O)₂]_n²ⁿ⁺ (Figs. 1 and 2), where TMD is 4,4'-trimethylenedipyridine, similar to the Co and Ni analogues previously reported (Plater et al., 2001). Uncoordinated TMD ligands, nitrate ions and water molecules are involved in an extensive hydrogen-bonding network with the cationic one-dimensional polymers (Table 2 and Fig. 3).

S2. Experimental

All chemicals were obtained from commercial sources and used as received. To a solution of Cd(NO₃)₂·6H₂O (0.629 g, Aldrich) in distilled water (12.5 g), 4,4'-trimethylenedipyridine (TMD, 0.407 g, Aldrich) was added and the mixture was stirred thoroughly for 1 h at ambient temperature. The suspension, with the Cd²⁺:TMD:H₂O composition 1:1.01:339, was placed in a Parr stainless steel Teflon-lined vessel (21 ml, 50% filled). The reaction took place under autogeneous pressure and static conditions in a preheated oven at 418 K for 3 h. The vessel was then cooled slowly inside the oven to 298 K at a rate of 5 K h⁻¹ before opening. The microcrystalline product was then cooled to 277 K. The solvent was allowed to evaporate at this temperature over a period of two months. Crystals of (I) were collected by vacuum filtration. Bulk homogeneity was confirmed using powder X-Ray diffraction and CHN elemental analysis; calculated (using single-crystal data): C 52.91, H 5.47, N 12.66%; found: 52.1, H 5.23, N 12.39%.

Selected FT–IR data (cm⁻¹): ν(water, O—H) = 3545 (m); hydrogen-bonded pyridine rings ν(═C—H) = 3254 (m), 3070 (m) and 3026 (m); ν_antisym(C—H in —CH₂—) = 2925 (w); ν_sym(C—H in —CH₂—) = 2860 (w); weak overtone and combination bands observed in the range 2020–1800 cm⁻¹ characteristic of 4-monosubstituted pyridines (three bands); 4-monosubstituted pyridine aromatic ring ν(═C—H) = 1607 (s), 1558 (m), 1503 (m), 1424 (s) and 1010 (m); 4-monosubstituted pyridine aromatic ring δ(═C—H) = 1222 (m), 1068 (m) and 840 (m); characteristic vibration frequencies of the nitrate ion at 1385 (s), 816 (m) and 760 (m); δ(Cd—OH₂) = 800 (m); ν(Cd—OH₂) = 510 (m).

S3. Refinement

H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement with U_iso(H) = 1.2U_eq(C). Water H atoms were located in difference Fourier maps and refined with a single isotropic displacement parameter common to all H atoms. O—H distances were restrained to 0.85 (1) Å and H···H distances to 1.39 (1) Å; the restraints ensure a reasonable geometry for the water molecules.

Computing details

Data collection: COLLECT (Nonius 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), represented with ellipsoids drawn at the 50% probability level for non-H atoms. H atoms on atom O7W are not shown.
	Fig. 2. The one-dimensional cationic [Cd(TMD)2(H2O)2]n^2n+ coordination polymer in (I), running parallel to the c direction. H atoms have been omitted for clarity.
	Fig. 3. A perspective view of (I) along the a direction, showing the O—H···O^− and O—H···N hydrogen-bond network (black fragmented lines). H atoms have been omitted for clarity.

catena-Poly[[[diaquacadmium(II)]-di-µ-4,4'-trimethylenedipyridine-κ²N:N'] dinitrate 4,4'-trimethylenedipyridine monohydrate]

Crystal data

[Cd(C13H14N2)2(H2O)2](NO3)2·C13H14N2·H2O	Z = 1
Mr = 885.25	F(000) = 458
Triclinic, P1	Dx = 1.420 Mg m^−3
a = 9.8088 (3) Å	Mo Kα radiation, λ = 0.7107 Å
b = 10.6080 (3) Å	Cell parameters from 8531 reflections
c = 12.0502 (4) Å	θ = 1.0–27.5°
α = 93.500 (2)°	µ = 0.59 mm^−1
β = 110.936 (2)°	T = 180 K
γ = 114.273 (2)°	Block, colourless
V = 1035.21 (6) Å^3	0.25 × 0.21 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	6863 independent reflections
Radiation source: fine-focus sealed tube	6828 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Thin–slice ω and ϕ scans	θmax = 26.9°, θmin = 3.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −12→12
Tmin = 0.803, Tmax = 0.910	k = −13→13
11297 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.2087P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
6863 reflections	Δρmax = 0.45 e Å^−3
533 parameters	Δρmin = −0.60 e Å^−3
14 restraints	Absolute structure: (Flack, 1983), 2369 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.031 (11)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.4220	0.0047	0.4997	0.02355 (6)
O11	0.2618 (3)	0.1236 (3)	0.4693 (3)	0.0286 (6)
H11A	0.183 (4)	0.109 (5)	0.4015 (18)	0.067 (6)*
H11B	0.242 (5)	0.149 (5)	0.528 (2)	0.067 (6)*
O12	0.5781 (4)	−0.1135 (3)	0.5175 (3)	0.0297 (7)
H12A	0.547 (6)	−0.184 (3)	0.461 (2)	0.067 (6)*
H12B	0.616 (6)	−0.131 (4)	0.5867 (17)	0.067 (6)*
N21	0.2218 (4)	−0.1874 (4)	0.5343 (3)	0.0261 (8)
N22	0.2929 (4)	−0.0879 (4)	1.2850 (3)	0.0285 (7)
C21	0.0771 (5)	−0.1917 (5)	0.5223 (4)	0.0288 (9)
H21A	0.0402	−0.1343	0.4751	0.035*
C22	−0.0189 (5)	−0.2754 (5)	0.5754 (4)	0.0285 (9)
H22B	−0.1193	−0.2746	0.5646	0.034*
C23	0.0316 (5)	−0.3610 (4)	0.6448 (4)	0.0251 (9)
C24	0.1762 (5)	−0.3598 (4)	0.6540 (4)	0.0287 (9)
H24A	0.2140	−0.4182	0.6992	0.034*
C25	0.2664 (5)	−0.2746 (4)	0.5980 (4)	0.0289 (9)
H25A	0.3645	−0.2775	0.6046	0.035*
C26	−0.0624 (5)	−0.4450 (5)	0.7136 (4)	0.0315 (9)
H26A	−0.0813	−0.5447	0.6957	0.038*
H26B	−0.1712	−0.4467	0.6844	0.038*
C27	0.0305 (5)	−0.3813 (4)	0.8529 (3)	0.0273 (8)
H27A	−0.0346	−0.4414	0.8935	0.033*
H27B	0.1371	−0.3840	0.8822	0.033*
C28	0.0633 (4)	−0.2278 (3)	0.8909 (3)	0.0310 (6)
H28A	0.1367	−0.1653	0.8567	0.037*
H28B	−0.0419	−0.2229	0.8571	0.037*
C29	0.3805 (4)	−0.0776 (4)	1.2201 (3)	0.0338 (7)
H29A	0.4966	−0.0394	1.2630	0.041*
C210	0.3115 (4)	−0.1197 (4)	1.0936 (3)	0.0325 (7)
H21B	0.3795	−0.1102	1.0516	0.039*
C211	0.1424 (4)	−0.1759 (3)	1.0285 (3)	0.0272 (6)
C212	0.0505 (4)	−0.1880 (3)	1.0949 (3)	0.0326 (7)
H21C	−0.0660	−0.2279	1.0539	0.039*
C213	0.1288 (4)	−0.1417 (3)	1.2219 (3)	0.0315 (6)
H21D	0.0639	−0.1483	1.2660	0.038*
N31	0.5398 (4)	0.1171 (4)	0.7113 (3)	0.0260 (7)
N32	0.6233 (4)	0.1973 (4)	1.4660 (3)	0.0242 (8)
C31	0.5513 (4)	0.0513 (3)	0.8031 (3)	0.0307 (6)
H31A	0.5270	−0.0460	0.7855	0.037*
C32	0.5967 (4)	0.1173 (4)	0.9225 (3)	0.0310 (7)
H32B	0.6041	0.0657	0.9843	0.037*
C33	0.6313 (3)	0.2585 (3)	0.9516 (3)	0.0273 (6)
C34	0.6242 (3)	0.3290 (3)	0.8577 (3)	0.0294 (6)
H34A	0.6509	0.4271	0.8737	0.035*
C35	0.5782 (3)	0.2558 (3)	0.7409 (3)	0.0264 (6)
H35A	0.5734	0.3059	0.6781	0.032*
C36	0.6740 (4)	0.3332 (4)	1.0786 (3)	0.0355 (7)
H36A	0.6046	0.2663	1.1131	0.043*
H36B	0.6487	0.4144	1.0737	0.043*
C37	0.8573 (4)	0.3887 (5)	1.1654 (4)	0.0331 (9)
H37A	0.8812	0.3069	1.1745	0.040*
H37B	0.9269	0.4512	1.1287	0.040*
C38	0.9014 (5)	0.4726 (5)	1.2926 (4)	0.0343 (10)
H38A	1.0213	0.5122	1.3430	0.041*
H38B	0.8760	0.5535	1.2831	0.041*
C39	0.7509 (5)	0.1884 (5)	1.4567 (4)	0.0307 (9)
H39A	0.7773	0.1169	1.4866	0.037*
C310	0.8463 (5)	0.2780 (5)	1.4057 (4)	0.0325 (10)
H31B	0.9375	0.2686	1.4034	0.039*
C311	0.8095 (5)	0.3819 (5)	1.3578 (4)	0.0272 (9)
C312	0.6814 (5)	0.3946 (4)	1.3731 (4)	0.0286 (9)
H31C	0.6554	0.4679	1.3473	0.034*
C313	0.5917 (5)	0.3013 (4)	1.4254 (4)	0.0272 (8)
H31D	0.5034	0.3115	1.4330	0.033*
N41	0.4421 (3)	0.6472 (3)	0.3384 (3)	0.0390 (6)
N42	0.1758 (3)	0.2016 (3)	−0.3557 (3)	0.0389 (6)
C41	0.4710 (4)	0.6321 (3)	0.2393 (3)	0.0397 (7)
H41B	0.5405	0.7151	0.2228	0.048*
C42	0.4045 (4)	0.5013 (3)	0.1594 (3)	0.0349 (7)
H42B	0.4288	0.4961	0.0902	0.042*
C43	0.3024 (4)	0.3780 (3)	0.1806 (3)	0.0305 (7)
C44	0.2694 (4)	0.3949 (4)	0.2810 (3)	0.0358 (8)
H44A	0.1967	0.3144	0.2977	0.043*
C45	0.3424 (4)	0.5293 (4)	0.3577 (3)	0.0376 (7)
H45A	0.3198	0.5374	0.4274	0.045*
C46	0.2260 (4)	0.2321 (3)	0.0980 (3)	0.0359 (7)
H46A	0.2371	0.1640	0.1488	0.043*
H46B	0.2862	0.2356	0.0466	0.043*
C47	0.0419 (4)	0.1787 (3)	0.0144 (3)	0.0332 (7)
H47A	−0.0064	0.0783	−0.0303	0.040*
H47B	−0.0167	0.1812	0.0658	0.040*
C48	0.0153 (3)	0.2677 (3)	−0.0779 (3)	0.0326 (7)
H48A	−0.1035	0.2411	−0.1177	0.039*
H48B	0.0757	0.3697	−0.0341	0.039*
C49	0.0457 (5)	0.0981 (4)	−0.3461 (4)	0.0381 (9)
H49A	−0.0114	0.0076	−0.4024	0.046*
C410	−0.0087 (4)	0.1174 (4)	−0.2581 (3)	0.0343 (8)
H41C	−0.1014	0.0414	−0.2551	0.041*
C411	0.0725 (3)	0.2477 (3)	−0.1749 (3)	0.0267 (6)
C412	0.2066 (4)	0.3542 (3)	−0.1844 (3)	0.0300 (6)
H41D	0.2657	0.4457	−0.1293	0.036*
C413	0.2539 (4)	0.3265 (4)	−0.2746 (3)	0.0342 (7)
H41E	0.3471	0.4006	−0.2788	0.041*
N5N	−0.1543 (3)	−0.0132 (3)	0.2509 (3)	0.0349 (6)
O51	−0.0179 (3)	0.0847 (3)	0.2691 (2)	0.0456 (6)
O52	−0.1587 (4)	−0.0958 (6)	0.3156 (5)	0.117 (2)
O53	−0.2834 (3)	−0.0250 (3)	0.1696 (2)	0.0508 (7)
N6N	−0.3649 (4)	−0.3129 (4)	−0.2645 (3)	0.0421 (7)
O61	−0.4231 (6)	−0.3966 (5)	−0.3604 (4)	0.1066 (17)
O62	−0.3194 (3)	−0.1835 (3)	−0.2541 (3)	0.0573 (8)
O63	−0.3566 (5)	−0.3593 (4)	−0.1706 (4)	0.0764 (10)
O7W	−0.4988 (5)	−0.2764 (5)	−0.0327 (4)	0.0947 (13)
H7A	−0.433 (4)	−0.302 (4)	−0.050 (2)	0.067 (6)*
H7B	−0.434 (3)	−0.202 (3)	0.029 (3)	0.067 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02512 (8)	0.02546 (9)	0.01762 (8)	0.00936 (6)	0.00936 (6)	0.00436 (6)
O11	0.0297 (14)	0.0347 (16)	0.0239 (14)	0.0157 (13)	0.0130 (12)	0.0069 (12)
O12	0.0305 (14)	0.0260 (14)	0.0319 (16)	0.0137 (13)	0.0123 (12)	0.0038 (12)
N21	0.0279 (17)	0.0288 (18)	0.0211 (19)	0.0103 (15)	0.0131 (15)	0.0074 (15)
N22	0.0295 (14)	0.0311 (15)	0.0217 (16)	0.0129 (12)	0.0095 (12)	0.0017 (12)
C21	0.0278 (17)	0.035 (2)	0.0260 (18)	0.0160 (16)	0.0120 (14)	0.0098 (15)
C22	0.0292 (18)	0.031 (2)	0.0283 (19)	0.0141 (17)	0.0147 (15)	0.0083 (15)
C23	0.026 (2)	0.0221 (19)	0.021 (2)	0.0058 (17)	0.0096 (17)	−0.0017 (16)
C24	0.0331 (18)	0.0250 (17)	0.0252 (19)	0.0102 (15)	0.0128 (14)	0.0087 (14)
C25	0.0265 (17)	0.0297 (18)	0.0294 (19)	0.0143 (15)	0.0096 (14)	0.0050 (15)
C26	0.031 (2)	0.0255 (18)	0.031 (2)	0.0058 (16)	0.0149 (17)	0.0049 (16)
C27	0.0323 (19)	0.0280 (16)	0.0225 (16)	0.0107 (15)	0.0158 (15)	0.0084 (13)
C28	0.0389 (15)	0.0327 (15)	0.0201 (14)	0.0184 (13)	0.0093 (12)	0.0049 (12)
C29	0.0252 (13)	0.0467 (18)	0.0231 (15)	0.0132 (14)	0.0087 (12)	0.0011 (13)
C210	0.0301 (17)	0.0473 (19)	0.0223 (16)	0.0168 (15)	0.0149 (14)	0.0071 (14)
C211	0.0324 (15)	0.0286 (15)	0.0189 (14)	0.0145 (13)	0.0091 (12)	0.0037 (12)
C212	0.0280 (13)	0.0379 (16)	0.0257 (15)	0.0131 (13)	0.0086 (12)	−0.0003 (13)
C213	0.0278 (13)	0.0396 (17)	0.0248 (14)	0.0134 (13)	0.0121 (12)	0.0029 (13)
N31	0.0247 (14)	0.0267 (14)	0.0194 (15)	0.0057 (12)	0.0092 (12)	0.0042 (11)
N32	0.0252 (16)	0.0231 (17)	0.0208 (19)	0.0091 (14)	0.0090 (15)	0.0019 (14)
C31	0.0353 (15)	0.0247 (14)	0.0269 (15)	0.0112 (12)	0.0106 (12)	0.0076 (12)
C32	0.0338 (19)	0.0350 (17)	0.0230 (16)	0.0139 (16)	0.0124 (15)	0.0106 (14)
C33	0.0234 (12)	0.0372 (16)	0.0213 (14)	0.0136 (12)	0.0106 (11)	0.0037 (12)
C34	0.0300 (13)	0.0257 (14)	0.0279 (15)	0.0124 (12)	0.0088 (12)	0.0030 (12)
C35	0.0298 (13)	0.0249 (14)	0.0218 (14)	0.0112 (11)	0.0094 (11)	0.0086 (11)
C36	0.0310 (15)	0.051 (2)	0.0222 (15)	0.0184 (15)	0.0115 (13)	0.0005 (14)
C37	0.0242 (17)	0.0391 (19)	0.0271 (18)	0.0063 (14)	0.0126 (14)	0.0004 (15)
C38	0.030 (2)	0.033 (2)	0.0197 (19)	−0.0035 (16)	0.0126 (16)	−0.0035 (16)
C39	0.0314 (18)	0.0267 (19)	0.034 (2)	0.0127 (16)	0.0140 (16)	0.0078 (15)
C310	0.0273 (18)	0.033 (2)	0.038 (2)	0.0107 (17)	0.0195 (17)	0.0011 (17)
C311	0.029 (2)	0.025 (2)	0.0124 (19)	0.0015 (17)	0.0068 (16)	−0.0032 (15)
C312	0.0295 (16)	0.0298 (18)	0.0229 (18)	0.0131 (15)	0.0082 (14)	0.0060 (14)
C313	0.0265 (17)	0.0307 (18)	0.0233 (17)	0.0109 (15)	0.0117 (14)	0.0093 (14)
N41	0.0409 (14)	0.0307 (14)	0.0352 (15)	0.0123 (12)	0.0116 (12)	0.0006 (11)
N42	0.0412 (15)	0.0503 (17)	0.0360 (15)	0.0274 (14)	0.0207 (13)	0.0076 (13)
C41	0.0350 (16)	0.0278 (16)	0.0422 (19)	0.0059 (14)	0.0120 (15)	0.0070 (14)
C42	0.0371 (15)	0.0345 (16)	0.0314 (16)	0.0150 (14)	0.0146 (13)	0.0075 (13)
C43	0.0237 (13)	0.0276 (15)	0.0339 (16)	0.0132 (12)	0.0042 (12)	0.0057 (13)
C44	0.0289 (16)	0.0278 (18)	0.036 (2)	0.0033 (14)	0.0102 (15)	0.0018 (15)
C45	0.0430 (17)	0.0344 (18)	0.0342 (17)	0.0167 (15)	0.0174 (14)	0.0022 (14)
C46	0.0417 (16)	0.0295 (15)	0.0327 (17)	0.0198 (14)	0.0082 (14)	0.0043 (13)
C47	0.0360 (15)	0.0260 (15)	0.0283 (15)	0.0064 (12)	0.0141 (13)	0.0009 (12)
C48	0.0255 (13)	0.0383 (16)	0.0331 (16)	0.0161 (13)	0.0110 (12)	0.0021 (13)
C49	0.0397 (19)	0.0325 (17)	0.0339 (18)	0.0123 (16)	0.0149 (15)	−0.0083 (14)
C410	0.0313 (16)	0.0346 (18)	0.0331 (18)	0.0104 (14)	0.0165 (14)	0.0002 (15)
C411	0.0251 (13)	0.0314 (14)	0.0260 (14)	0.0163 (12)	0.0096 (11)	0.0059 (12)
C412	0.0329 (14)	0.0266 (14)	0.0303 (15)	0.0134 (12)	0.0139 (12)	0.0045 (12)
C413	0.0374 (17)	0.0363 (17)	0.0374 (17)	0.0202 (15)	0.0203 (14)	0.0129 (14)
N5N	0.0266 (12)	0.0377 (15)	0.0350 (15)	0.0135 (11)	0.0087 (11)	0.0122 (12)
O51	0.0304 (11)	0.0460 (14)	0.0510 (15)	0.0112 (11)	0.0139 (11)	0.0184 (12)
O52	0.0358 (17)	0.137 (4)	0.156 (5)	0.020 (2)	0.025 (3)	0.123 (4)
O53	0.0330 (11)	0.0611 (16)	0.0444 (15)	0.0220 (12)	0.0011 (11)	0.0146 (12)
N6N	0.0285 (14)	0.0427 (19)	0.0510 (19)	0.0197 (14)	0.0089 (14)	0.0100 (16)
O61	0.117 (3)	0.090 (3)	0.077 (3)	0.068 (3)	−0.014 (3)	−0.021 (2)
O62	0.0497 (14)	0.0353 (13)	0.0680 (19)	0.0155 (12)	0.0085 (13)	0.0205 (13)
O63	0.097 (3)	0.068 (2)	0.099 (3)	0.051 (2)	0.057 (2)	0.059 (2)
O7W	0.072 (2)	0.098 (3)	0.073 (3)	0.002 (2)	0.038 (2)	−0.017 (2)

Geometric parameters (Å, º)

Cd1—O12	2.311 (3)	C36—C37	1.544 (4)
Cd1—O11	2.339 (3)	C36—H36A	0.990
Cd1—N21	2.362 (4)	C36—H36B	0.990
Cd1—N22^i	2.363 (3)	C37—C38	1.540 (6)
Cd1—N32^i	2.366 (4)	C37—H37A	0.990
Cd1—N31	2.377 (3)	C37—H37B	0.990
O11—H11A	0.85 (1)	C38—C311	1.497 (7)
O11—H11B	0.85 (1)	C38—H38A	0.990
O12—H12A	0.85 (1)	C38—H38B	0.990
O12—H12B	0.85 (1)	C39—C310	1.381 (7)
N21—C25	1.348 (5)	C39—H39A	0.950
N21—C21	1.356 (5)	C310—C311	1.390 (6)
N22—C29	1.333 (5)	C310—H31B	0.950
N22—C213	1.346 (4)	C311—C312	1.390 (6)
N22—Cd1^ii	2.363 (3)	C312—C313	1.382 (6)
C21—C22	1.376 (6)	C312—H31C	0.950
C21—H21A	0.950	C313—H31D	0.950
C22—C23	1.391 (6)	N41—C45	1.329 (5)
C22—H22B	0.950	N41—C41	1.338 (5)
C23—C24	1.378 (6)	N42—C413	1.330 (4)
C23—C26	1.514 (7)	N42—C49	1.348 (5)
C24—C25	1.377 (6)	C41—C42	1.386 (5)
C24—H24A	0.950	C41—H41B	0.950
C25—H25A	0.950	C42—C43	1.388 (5)
C26—C27	1.538 (6)	C42—H42B	0.950
C26—H26A	0.990	C43—C44	1.379 (5)
C26—H26B	0.990	C43—C46	1.508 (4)
C27—C28	1.529 (5)	C44—C45	1.388 (5)
C27—H27A	0.990	C44—H44A	0.950
C27—H27B	0.990	C45—H45A	0.950
C28—C211	1.507 (4)	C46—C47	1.545 (4)
C28—H28A	0.990	C46—H46A	0.990
C28—H28B	0.990	C46—H46B	0.990
C29—C210	1.383 (5)	C47—C48	1.524 (4)
C29—H29A	0.950	C47—H47A	0.990
C210—C211	1.387 (4)	C47—H47B	0.990
C210—H21B	0.950	C48—C411	1.504 (4)
C211—C212	1.380 (4)	C48—H48A	0.990
C212—C213	1.391 (4)	C48—H48B	0.990
C212—H21C	0.950	C49—C410	1.386 (5)
C213—H21D	0.950	C49—H49A	0.950
N31—C31	1.340 (4)	C410—C411	1.380 (4)
N31—C35	1.348 (4)	C410—H41C	0.950
N32—C39	1.335 (5)	C411—C412	1.386 (4)
N32—C313	1.339 (5)	C412—C413	1.385 (4)
N32—Cd1^ii	2.366 (4)	C412—H41D	0.950
C31—C32	1.386 (5)	C413—H41E	0.950
C31—H31A	0.950	N5N—O52	1.206 (5)
C32—C33	1.383 (5)	N5N—O51	1.240 (3)
C32—H32B	0.950	N5N—O53	1.244 (3)
C33—C34	1.392 (4)	N6N—O61	1.198 (5)
C33—C36	1.506 (4)	N6N—O62	1.239 (4)
C34—C35	1.382 (4)	N6N—O63	1.251 (5)
C34—H34A	0.950	O7W—H7A	0.88 (1)
C35—H35A	0.950	O7W—H7B	0.88 (1)
O12—Cd1—O11	176.52 (14)	N31—C35—C34	123.6 (3)
O12—Cd1—N21	91.17 (11)	N31—C35—H35A	118.2
O11—Cd1—N21	90.38 (11)	C34—C35—H35A	118.2
O12—Cd1—N22^i	89.69 (11)	C33—C36—C37	112.4 (3)
O11—Cd1—N22^i	87.10 (11)	C33—C36—H36A	109.1
N21—Cd1—N22^i	93.77 (12)	C37—C36—H36A	109.1
O12—Cd1—N32^i	88.73 (11)	C33—C36—H36B	109.1
O11—Cd1—N32^i	89.74 (11)	C37—C36—H36B	109.1
N21—Cd1—N32^i	179.74 (15)	H36A—C36—H36B	107.8
N22^i—Cd1—N32^i	86.47 (12)	C38—C37—C36	111.8 (3)
O12—Cd1—N31	96.68 (11)	C38—C37—H37A	109.2
O11—Cd1—N31	86.50 (11)	C36—C37—H37A	109.2
N21—Cd1—N31	87.98 (12)	C38—C37—H37B	109.2
N22^i—Cd1—N31	173.37 (13)	C36—C37—H37B	109.2
N32^i—Cd1—N31	91.80 (11)	H37A—C37—H37B	107.9
Cd1—O11—H11A	124 (3)	C311—C38—C37	112.4 (4)
Cd1—O11—H11B	120 (3)	C311—C38—H38A	109.1
H11A—O11—H11B	109 (2)	C37—C38—H38A	109.1
Cd1—O12—H12A	121 (3)	C311—C38—H38B	109.1
Cd1—O12—H12B	117 (3)	C37—C38—H38B	109.1
H12A—O12—H12B	109 (2)	H38A—C38—H38B	107.9
C25—N21—C21	116.5 (4)	N32—C39—C310	123.3 (4)
C25—N21—Cd1	119.3 (3)	N32—C39—H39A	118.3
C21—N21—Cd1	121.8 (3)	C310—C39—H39A	118.3
C29—N22—C213	117.0 (3)	C39—C310—C311	120.3 (4)
C29—N22—Cd1^ii	121.4 (2)	C39—C310—H31B	119.9
C213—N22—Cd1^ii	121.3 (3)	C311—C310—H31B	119.9
N21—C21—C22	123.1 (4)	C310—C311—C312	115.9 (5)
N21—C21—H21A	118.4	C310—C311—C38	121.7 (4)
C22—C21—H21A	118.4	C312—C311—C38	122.4 (4)
C21—C22—C23	119.8 (4)	C313—C312—C311	120.4 (4)
C21—C22—H22B	120.1	C313—C312—H31C	119.8
C23—C22—H22B	120.1	C311—C312—H31C	119.8
C24—C23—C22	117.1 (4)	N32—C313—C312	123.1 (4)
C24—C23—C26	121.2 (4)	N32—C313—H31D	118.5
C22—C23—C26	121.7 (4)	C312—C313—H31D	118.5
C25—C24—C23	120.4 (4)	C45—N41—C41	116.9 (3)
C25—C24—H24A	119.8	C413—N42—C49	116.8 (3)
C23—C24—H24A	119.8	N41—C41—C42	123.1 (3)
N21—C25—C24	123.0 (4)	N41—C41—H41B	118.4
N21—C25—H25A	118.5	C42—C41—H41B	118.4
C24—C25—H25A	118.5	C41—C42—C43	119.9 (3)
C23—C26—C27	112.2 (3)	C41—C42—H42B	120.0
C23—C26—H26A	109.2	C43—C42—H42B	120.0
C27—C26—H26A	109.2	C44—C43—C42	116.6 (3)
C23—C26—H26B	109.2	C44—C43—C46	120.5 (3)
C27—C26—H26B	109.2	C42—C43—C46	122.9 (3)
H26A—C26—H26B	107.9	C43—C44—C45	120.1 (3)
C28—C27—C26	113.4 (3)	C43—C44—H44A	119.9
C28—C27—H27A	108.9	C45—C44—H44A	119.9
C26—C27—H27A	108.9	N41—C45—C44	123.3 (3)
C28—C27—H27B	108.9	N41—C45—H45A	118.3
C26—C27—H27B	108.9	C44—C45—H45A	118.3
H27A—C27—H27B	107.7	C43—C46—C47	111.9 (2)
C211—C28—C27	110.7 (3)	C43—C46—H46A	109.2
C211—C28—H28A	109.5	C47—C46—H46A	109.2
C27—C28—H28A	109.5	C43—C46—H46B	109.2
C211—C28—H28B	109.5	C47—C46—H46B	109.2
C27—C28—H28B	109.5	H46A—C46—H46B	107.9
H28A—C28—H28B	108.1	C48—C47—C46	112.6 (3)
N22—C29—C210	123.6 (3)	C48—C47—H47A	109.1
N22—C29—H29A	118.2	C46—C47—H47A	109.1
C210—C29—H29A	118.2	C48—C47—H47B	109.1
C29—C210—C211	119.5 (3)	C46—C47—H47B	109.1
C29—C210—H21B	120.3	H47A—C47—H47B	107.8
C211—C210—H21B	120.3	C411—C48—C47	112.5 (2)
C212—C211—C210	117.4 (3)	C411—C48—H48A	109.1
C212—C211—C28	121.9 (3)	C47—C48—H48A	109.1
C210—C211—C28	120.6 (3)	C411—C48—H48B	109.1
C211—C212—C213	119.8 (3)	C47—C48—H48B	109.1
C211—C212—H21C	120.1	H48A—C48—H48B	107.8
C213—C212—H21C	120.1	N42—C49—C410	123.1 (3)
N22—C213—C212	122.7 (3)	N42—C49—H49A	118.4
N22—C213—H21D	118.7	C410—C49—H49A	118.4
C212—C213—H21D	118.7	C411—C410—C49	119.6 (3)
C31—N31—C35	116.2 (3)	C411—C410—H41C	120.2
C31—N31—Cd1	125.8 (2)	C49—C410—H41C	120.2
C35—N31—Cd1	117.3 (2)	C410—C411—C412	117.4 (3)
C39—N32—C313	116.8 (4)	C410—C411—C48	119.6 (3)
C39—N32—Cd1^ii	120.9 (3)	C412—C411—C48	123.0 (3)
C313—N32—Cd1^ii	120.2 (3)	C413—C412—C411	119.6 (3)
N31—C31—C32	123.6 (3)	C413—C412—H41D	120.2
N31—C31—H31A	118.2	C411—C412—H41D	120.2
C32—C31—H31A	118.2	N42—C413—C412	123.4 (3)
C33—C32—C31	119.9 (3)	N42—C413—H41E	118.3
C33—C32—H32B	120.0	C412—C413—H41E	118.3
C31—C32—H32B	120.0	O52—N5N—O51	118.1 (3)
C32—C33—C34	116.9 (3)	O52—N5N—O53	120.7 (3)
C32—C33—C36	122.0 (3)	O51—N5N—O53	121.2 (3)
C34—C33—C36	121.1 (3)	O61—N6N—O62	123.5 (4)
C35—C34—C33	119.7 (3)	O61—N6N—O63	118.4 (4)
C35—C34—H34A	120.2	O62—N6N—O63	118.0 (4)
C33—C34—H34A	120.2	H7A—O7W—H7B	105 (2)
O12—Cd1—N21—C25	25.5 (3)	C31—C32—C33—C34	−2.4 (5)
O11—Cd1—N21—C25	−157.6 (3)	C31—C32—C33—C36	177.3 (3)
N22^i—Cd1—N21—C25	115.3 (3)	C32—C33—C34—C35	2.3 (4)
N31—Cd1—N21—C25	−71.1 (3)	C36—C33—C34—C35	−177.4 (3)
O12—Cd1—N21—C21	−172.7 (3)	C31—N31—C35—C34	−1.3 (5)
O11—Cd1—N21—C21	4.2 (3)	Cd1—N31—C35—C34	170.1 (2)
N22^i—Cd1—N21—C21	−82.9 (3)	C33—C34—C35—N31	−0.5 (5)
N31—Cd1—N21—C21	90.7 (3)	C32—C33—C36—C37	82.4 (4)
C25—N21—C21—C22	2.5 (6)	C34—C33—C36—C37	−97.9 (4)
Cd1—N21—C21—C22	−159.8 (3)	C33—C36—C37—C38	176.6 (3)
N21—C21—C22—C23	−0.2 (7)	C36—C37—C38—C311	63.0 (5)
C21—C22—C23—C24	−1.7 (6)	C313—N32—C39—C310	−1.5 (6)
C21—C22—C23—C26	174.8 (4)	Cd1^ii—N32—C39—C310	162.2 (4)
C22—C23—C24—C25	1.2 (6)	N32—C39—C310—C311	−1.7 (7)
C26—C23—C24—C25	−175.2 (4)	C39—C310—C311—C312	4.4 (7)
C21—N21—C25—C24	−3.0 (6)	C39—C310—C311—C38	−174.8 (4)
Cd1—N21—C25—C24	159.8 (3)	C37—C38—C311—C310	72.0 (5)
C23—C24—C25—N21	1.2 (6)	C37—C38—C311—C312	−107.1 (5)
C24—C23—C26—C27	68.7 (5)	C310—C311—C312—C313	−4.3 (6)
C22—C23—C26—C27	−107.6 (5)	C38—C311—C312—C313	175.0 (4)
C23—C26—C27—C28	60.0 (5)	C39—N32—C313—C312	1.7 (6)
C26—C27—C28—C211	175.6 (3)	Cd1^ii—N32—C313—C312	−162.1 (3)
C213—N22—C29—C210	−0.4 (6)	C311—C312—C313—N32	1.3 (6)
Cd1^ii—N22—C29—C210	−174.6 (3)	C45—N41—C41—C42	−1.0 (5)
N22—C29—C210—C211	0.0 (6)	N41—C41—C42—C43	0.1 (5)
C29—C210—C211—C212	−0.5 (5)	C41—C42—C43—C44	1.7 (4)
C29—C210—C211—C28	−177.6 (3)	C41—C42—C43—C46	−179.8 (3)
C27—C28—C211—C212	−92.5 (4)	C42—C43—C44—C45	−2.5 (5)
C27—C28—C211—C210	84.5 (4)	C46—C43—C44—C45	179.0 (3)
C210—C211—C212—C213	1.4 (5)	C41—N41—C45—C44	0.1 (5)
C28—C211—C212—C213	178.4 (3)	C43—C44—C45—N41	1.7 (5)
C29—N22—C213—C212	1.2 (5)	C44—C43—C46—C47	75.0 (4)
Cd1^ii—N22—C213—C212	175.5 (2)	C42—C43—C46—C47	−103.4 (3)
C211—C212—C213—N22	−1.8 (5)	C43—C46—C47—C48	65.9 (4)
O12—Cd1—N31—C31	−53.8 (3)	C46—C47—C48—C411	69.6 (3)
O11—Cd1—N31—C31	127.7 (3)	C413—N42—C49—C410	0.6 (5)
N21—Cd1—N31—C31	37.2 (3)	N42—C49—C410—C411	−0.3 (6)
N32^i—Cd1—N31—C31	−142.7 (3)	C49—C410—C411—C412	0.1 (5)
O12—Cd1—N31—C35	135.8 (3)	C49—C410—C411—C48	−178.9 (3)
O11—Cd1—N31—C35	−42.7 (2)	C47—C48—C411—C410	66.8 (4)
N21—Cd1—N31—C35	−133.2 (3)	C47—C48—C411—C412	−112.1 (3)
N32^i—Cd1—N31—C35	46.9 (3)	C410—C411—C412—C413	−0.4 (4)
C35—N31—C31—C32	1.2 (5)	C48—C411—C412—C413	178.6 (3)
Cd1—N31—C31—C32	−169.3 (3)	C49—N42—C413—C412	−0.9 (5)
N31—C31—C32—C33	0.7 (5)	C411—C412—C413—N42	0.8 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7W—H7A···O63	0.88 (1)	2.02 (1)	2.821 (5)	152 (3)
O7W—H7B···O53	0.88 (1)	2.03 (1)	2.901 (4)	178 (5)
O11—H11B···N42^ii	0.85 (1)	1.88 (1)	2.734 (4)	174 (4)
O12—H12A···N41^iii	0.85 (1)	1.88 (1)	2.715 (4)	169 (5)
O12—H12B···O62^iv	0.85 (1)	1.99 (1)	2.834 (4)	174 (5)

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