Crystal structure and Hirshfeld surface analysis of aqua-bis-(nicotinamide-κN1)bis-(2,4,6-tri-methyl-benzoato-κ2O,O')cadmium(II).

The asymmetric unit of the title complex, [Cd(C10H11O2)2(C6H6N2O)2(H2O)], contains one half of the complex mol-ecule, with the CdII cation and the coordinated water O atom residing on a twofold rotation axis. The CdII cation is coordinated in a bidentate manner to the carboxyl-ate O atoms of the two symmetry-related 2,4,6-tri-methyl-benzoate (TMB) anions and to the water O atom at distances of 2.297 (2), 2.527 (2) and 2.306 (3) Å to form a distorted penta-gonal arrangement, while the distorted penta-gonal-bipyramidal coordin-ation sphere is completed by the two pyridine N atoms of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371 (3) Å in the axial positions. In the crystal, mol-ecules are linked via inter-molecular N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds with R22(12), R33(8), R33(14), R33(16), R33(20), R33(22), R44(22), R55(16), R66(16) and R66(18) ring motifs, forming a three-dimensional architecture. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are H⋯H (56.9%), H⋯C/C⋯H (21.3%) and H⋯O/O⋯H (19.0%) inter-actions.

Chemical context

Nicotinamide (NA) is one form of n class="Chemical">niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974 ▸). The crystal structure of NA was first determined by Wright & King (1954 ▸). The NA ring is the reactive part of nicotinamide adenine dinucleotide (NAD) and its phosphate (NADP), which are the major electron carriers in many biological oxidation–reduction reactions (You et al., 1978 ▸). The nicotinic acid derivative N,N-di­ethyl­nicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ▸).

Transition metal n class="Chemical">complexes with ligands of biochemical inter­est such as imidazole and some N-protected amino acids show inter­esting physical and/or chemical properties, through which they may find applications in biological systems (Antolini et al., 1982 ▸). Crystal structures of metal complexes with benzoic acid derivatives have been reported extensively because of the varieties of the coordination modes. For example, Co and Cd complexes with 4-amino­benzoic acid (Chen & Chen, 2002 ▸), Co complexes with benzoic acid (Catterick et al., 1974 ▸), 4-nitro­benzoic acid (Nadzhafov et al., 1981 ▸) and phthalic acid (Adiwidjaja et al., 1978 ▸), and Cu complexes with 4-hydro­chloric acid (Shnulin et al., 1981 ▸) have been described.

The structure–function–coordination relationships of the aryl­carboxyl­ate ion in n class="Chemical">CdII complexes of benzoic acid deriv­atives change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand mol­ecule or solvent, and the pH and temperature of synthesis (Shnulin et al., 1981 ▸). When pyridine and its derivatives are used instead of water mol­ecules, the structure is completely different (Catterick et al., 1974 ▸).

The structures of some mononuclear complexes obtained from the reactions of transition n class="Chemical">metal(II) ions with nicotinamide (NA) and some benzoic acid derivatives as ligands have been determined previously, e.g. [Zn(C7H5O3)2(C6H6N2O)2] [(II); Necefoğlu et al., 2002 ▸], [Mn(C7H4ClO2)2(C10H14N2O)2(H2O)2] [(III); Hökelek et al., 2008 ▸], [Zn(C8H8NO2)2(C6H6N2O)2]·H2O [(IV); Hökelek et al., 2009a ▸], [Mn(C9H10NO2)2(C6H6N2O)(H2O)2] [(V); Hökelek et al., 2009b ▸] and [Co(C9H10NO2)2(C6H6N2O)(H2O)2] [(VI); Hökelek et al., 2009c ▸]. The structure determination of the title compound, (I), a cadmium complex with two 2,4,6-tri­methyl­benzoate (TMB) and two nicotinamide (NA) ligands and one coordinated water mol­ecule, was undertaken in order to compare the results obtained with those reported previously. In this context, we synthesized the CdII-containing title compound and report herein its crystal and mol­ecular structures along with the Hirshfeld surface analysis.

Structural commentary

The asymmetric unit of the crystal structure of the mononuclear title complex n class="Chemical">contains half of a CdII cation (site symmetry 2), one 2,4,6-tri­methyl­benzoate (TMB) anion and one nicotin­amide (NA) mol­ecule together with half of a water mol­ecule (point group symmetry 2), the TMB and NA ligands coord­inating in bidentate and monodentate manners, respectively (Fig. 1 ▸).

Figure 1

The mol­ecular structure of the title complex with the atom-numbering scheme. Unlabelled atoms are related to labelled atoms by the symmetry operation (1 − x, y,  − z). Displacement ellipsoids are drawn at the 50% probability level.

The CdII cation is n class="Chemical">coordinated bidentately to the carboxyl­ate O atoms (O1, O2, O1i and O2i) of two symmetry-related 2,4,6-tri­methyl­benzoate (TMB) anions and to the water O atom (O4) at distances of 2.297 (2), 2.527 (2) and 2.306 (3) Å, respectively, to form a distorted penta­gonal arrangement. The sum of the bond angles O1—Cd1—O1i [87.57 (11)°], O1—Cd1—O2 [53.63 (7)°], O1i—Cd1—O2i [53.63 (7)°], O2—Cd1—O4 [84.47 (5)°] and O2i—Cd1—O4 [84.47 (5)°] in the basal plane around CdII cation is 363.77° [symmetry code: (i) 1 − x, y,  − z]. This confirms the presence of the CdII cation with a small deviation from the basal plane. The distorted penta­gonal–bipyramidal coordination sphere is completed by the two pyridine N atoms (N1 and N1i) of the two symmetry-related monodentate nicotinamide (NA) ligands at distances of 2.371 (3) Å in the axial positions (Fig. 1 ▸).

The near equalities of the C1—O1 [1.249 (4) Å] and C1—O2 [1.253 (3) Å] bonds in the carboxyl­ate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2—C1—O1 bond angle [121.7 (3)°] seems to be slightly decreased than that present in a free acid [122.2°]. The O2—C1—O1 bond angle may be n class="Chemical">compared with the corresponding values of 123.5 (2) and 120.4 (2)° in (II), 125.2 (5)° in (III), 119.2 (3) and 123.8 (2)° in (IV), 123.6 (3) and 119.4 (3)° in (V) and 123.86 (13) and 118.49 (14)° in (VI), where the benzoate ions are coordinated to the metal atoms only monodentately in (III), and both monodentately and bidentately in (II), (IV), (V) and (VI). The Cd1 atom lies 0.0192 (1) Å above of the planar (O1/O2/C1) carboxyl­ate group. The O1—Cd1—O2 angle is 53.63 (7)°. The corresponding O—M—O angles are 58.79 (6)° in (II), 59.02 (8)° in (IV), 58.45 (9)° in (V) and 60.70 (4)° in (VI). In the TMB anion, the carboxyl­ate group is twisted away from the attached benzene ring, A (C2–C7), ring by 60.94 (18)°, while the benzene and pyridine rings [pyridine = B (N1/C11–C15)], are oriented at a dihedral angle of 50.32 (11)°. The four-membered ring D (Cd1/O1/O2/C1) is nearly planar with a maximum deviation of 0.0029 (30) Å (for C1) from the mean plane, and it is oriented at dihedral angles of 60.98 (11) and 81.91 (7)°, with respect to the A and B rings.

Supra­molecular features

In the crystal, the mol­ecules are linked via inter­molen class="Chemical">cular N—HNA⋯ONA, N—HNA⋯OC, O—HW⋯ONA and C—HTMB⋯OC (NA = nicotinamide, C = carboxyl­ate, W = water and TMB = 2,4,6-tri­methyl­benzoate) hydrogen bonds (Table 1 ▸) with (12), (8), (14), (16), (20), (22), (22), (16), (16) and (18) ring motifs (Fig. 2 ▸), forming a three-dimensional architecture. Hydrogen-bonding and van der Waals contacts are the dominant inter­actions in the crystal packing. No significant π–π or C—H⋯π inter­actions are observed.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3vi	0.89 (3)	2.26 (4)	3.047 (4)	147 (3)
N2—H2B⋯O2vii	0.81 (3)	2.03 (3)	2.830 (4)	168 (4)
O4—H41⋯O3iii	0.80 (3)	1.92 (3)	2.714 (3)	170 (3)
C8—H8C⋯O1viii	0.96	2.55	3.468 (5)	161

Symmetry codes: (iii) ; (vi) ; (vii) ; (viii) .

Figure 2

Part of the crystal structure. O—HW⋯ONA, N—HNA⋯OC and N—HNA⋯ONA (W = water, C = carboxyl­ate and NA = nicotinamide) hydrogen bonds, enclosing (12), (8), (14), (16), (20), (22), (22), (16), (16) and (18) ring motifs are shown as dashed lines. C-bound H atoms have been omitted for clarity.

Hirshfeld surface analysis

Visulization and exploration of inter­molecular close n class="Chemical">contacts of a structure is invaluable, and this can be achieved using Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ▸; Spackman & Jayatilaka, 2009 ▸). An HS analysis was carried out by using CrystalExplorer17.5 (Turner et al., 2017 ▸) to investigate the locations of atom⋯atom short contacts with the potential to form hydrogen bonds and the qu­anti­tative ratios of these inter­actions and the π-stacking inter­actions in the crystal structure of the title complex.

In the HS plotted over d norm (Fig. 3 ▸), the white surface indicates n class="Chemical">contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ▸). The bright-red spots appearing near NA-O3, TMB-O1 and O2, and hydrogen atoms H2A, H2B, H41 and H8C indicate their role as the respective donors and acceptors in the dominant O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ▸; Jayatilaka et al., 2005 ▸) as shown in Fig. 4 ▸. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π inter­actions. Fig. 5 ▸ clearly suggests that there are no π–π inter­actions in (I).

Figure 3

View of the three-dimensional Hirshfeld surface of the title complex plotted over d norm in the range −0.6741 to 1.6440 a.u.

Figure 4

View of the three-dimensional Hirshfeld surface of the title complex plotted over electrostatic potential energy in the range −0.1379 to 0.1988 a.u. using the STO-3G basis set at the Hartree–Fock level of theory. The N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bond donors and acceptors are viewed as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 5

Hirshfeld surface of the title complex plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 6 ▸ a, and those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, H⋯N/N⋯H, C⋯C and O⋯C/C⋯O contacts (McKinnon et al., 2007 ▸) are illustrated in Fig. 6 ▸ b–g, respectively, together with their relative n class="Chemical">contributions to the Hirshfeld surface. The most important inter­action is H⋯H, contributing 56.9% to the overall crystal packing, which is reflected in Fig. 6 ▸ b as widely scattered points of high density due to the large hydrogen content of the mol­ecule. The single spike in the centre at d e = d i = 1.2 Å in Fig. 6 ▸ b is due to a short inter­atomic H⋯H contact (Table 2 ▸). In the absence of C—H⋯π inter­actions in the crystal, the pair of characteristic wings resulting in the fingerprint plot delineated into H⋯C/C⋯H contacts, with 21.3% contribution to the HS, Fig. 6 ▸ c; the pair of thin edges at d e + d i ∼ 1.67 Å result from short inter­atomic H⋯C/C⋯H contacts (Table 2 ▸). In the fingerprint plot delineated into H⋯O/O⋯H contacts, Fig. 6 ▸ d, the 19.0% contribution to the HS arises from inter­molecular O—H⋯O hydrogen bonding and is viewed as a pair of spikes with the tip at d e + d i ∼ 1.74 Å. The short H⋯O/O⋯H contacts are masked by strong O—H⋯O hydrogen bonding in this plot. The H⋯N/N⋯H contacts in the structure, with a 1.9% contribution to the HS, has a symmetrical distribution of points, Fig. 6 ▸ e, with the tips at d e + d i ∼ 2.96 Å arising from the short inter­atomic H⋯N/N⋯H contact listed in Table 2 ▸. The Hirshfeld surface representations with the function d norm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯N/N⋯H inter­actions in Fig. 7 ▸ a–d, respectively.

Figure 6

The full two-dimensional fingerprint plots for the title complex, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/O⋯H, (e) H⋯N/N⋯H, (f) C⋯C and (g) O⋯C/C⋯O inter­actions. The d i and d e values are the closest inter­nal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Table 2

Selected interatomic distances (Å)

O1⋯H8C i	2.55	N2⋯H13	2.75
O2⋯H2B ii	2.03 (3)	C6⋯H14ii	2.80
O3⋯H41iii	1.92 (3)	C16⋯H41iii	2.85 (3)
O3⋯H2A iv	2.26 (4)	H8A⋯H8A v	2.54

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

Figure 7

The Hirshfeld surface representations with the function d norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯O/O⋯H and (d) H⋯N/N⋯H inter­actions.

The Hirshfeld surface analysis confirms the importance of H-atom n class="Chemical">contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H inter­actions suggest that van der Waals inter­actions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ▸).

Synthesis and crystallization

The title compound was prepared by the reaction of 3n class="Chemical">CdSO4·8H2O (0.64 g, 2.5 mmol) in water (50 ml) and nicotinamide (0.61 g, 5 mmol) in water (25 ml) with sodium 2,4,6-tri­methyl­benzoate (0.93 g, 5 mmol) in water (150 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for six weeks, giving colourless single crystals (yield: 1.42 g, 85%). Combustion analysis: found; C, 57.07, H, 5.67, N, 7.92%. Calculated: C32H36CdN4O7 C, 57.42; H, 5.43, N, 8.34%. FT–IR: 3390, 3122, 2921, 1669, 1619, 1539, 1445, 1399, 1113, 1038, 847, 731, 641 cm−1.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The n class="Disease">H atoms of the NH2 group and of the water mol­ecule were located in difference-Fourier maps and refined freely. The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with U iso(H) = k × U eq(C), where k = 1.5 for methyl H-atoms and k = 1.2 for aromatic H-atoms.

Table 3

Experimental details

Crystal data
Chemical formula	[Cd(C10H11O2)2(C6H6N2O)2(H2O)]
M r	701.05
Crystal system, space group	Orthorhombic, P b c n
Temperature (K)	296
a, b, c (Å)	23.6876 (5), 15.6711 (4), 9.0682 (2)
V (Å3)	3366.21 (13)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.70
Crystal size (mm)	0.45 × 0.28 × 0.21
Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.784, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	68263, 4213, 3681
R int	0.028
(sin θ/λ)max (Å−1)	0.669
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.047, 0.099, 1.32
No. of reflections	4213
No. of parameters	215
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.32, −0.47

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018001494/xu5916sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018001494/xu5916Isup2.hkl

CCDC reference: 1818756

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cd(C10H11O2)2(C6H6N2O)2(H2O)]	F(000) = 1440
Mr = 701.05	Dx = 1.383 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 9766 reflections
a = 23.6876 (5) Å	θ = 2.6–28.4°
b = 15.6711 (4) Å	µ = 0.70 mm−1
c = 9.0682 (2) Å	T = 296 K
V = 3366.21 (13) Å3	Block, colorless
Z = 4	0.45 × 0.28 × 0.21 mm

Bruker SMART BREEZE CCD diffractometer	4213 independent reflections
Radiation source: fine-focus sealed tube	3681 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −31→31
Tmin = 0.784, Tmax = 0.867	k = −20→20
68263 measured reflections	l = −11→12

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.32	w = 1/[σ2(Fo2) + (0.0171P)2 + 5.5549P] where P = (Fo2 + 2Fc2)/3
4213 reflections	(Δ/σ)max = 0.001
215 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

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
Cd1	0.5000	0.746100 (17)	0.2500	0.03358 (9)
O1	0.43935 (10)	0.64030 (14)	0.1751 (3)	0.0472 (6)
O2	0.42005 (10)	0.76163 (14)	0.0676 (3)	0.0468 (6)
O3	0.42068 (10)	0.98712 (14)	0.6880 (3)	0.0471 (5)
O4	0.5000	0.8932 (2)	0.2500	0.0481 (8)
H41	0.5257 (14)	0.924 (2)	0.272 (4)	0.041 (10)*
N1	0.44028 (11)	0.75971 (16)	0.4585 (3)	0.0392 (6)
N2	0.41074 (13)	0.91347 (19)	0.9004 (3)	0.0434 (7)
H2A	0.4139 (15)	0.960 (2)	0.957 (4)	0.053 (11)*
H2B	0.4105 (15)	0.867 (2)	0.939 (4)	0.050 (11)*
C1	0.41017 (13)	0.68404 (18)	0.0888 (3)	0.0344 (6)
C2	0.36190 (13)	0.64076 (19)	0.0124 (3)	0.0387 (7)
C3	0.30699 (16)	0.6685 (3)	0.0358 (5)	0.0587 (10)
C4	0.26341 (18)	0.6243 (4)	−0.0346 (6)	0.0812 (15)
H4	0.2264	0.6419	−0.0194	0.097*
C5	0.2733 (2)	0.5561 (4)	−0.1254 (6)	0.0801 (15)
C6	0.32799 (19)	0.5306 (3)	−0.1478 (5)	0.0662 (12)
H6	0.3351	0.4847	−0.2100	0.079*
C7	0.37317 (16)	0.5717 (2)	−0.0798 (4)	0.0475 (8)
C8	0.43251 (18)	0.5435 (3)	−0.1127 (5)	0.0715 (13)
H8A	0.4488	0.5186	−0.0259	0.107*
H8B	0.4546	0.5919	−0.1425	0.107*
H8C	0.4320	0.5021	−0.1907	0.107*
C9	0.2941 (2)	0.7424 (4)	0.1375 (7)	0.099 (2)
H9A	0.3084	0.7301	0.2343	0.149*
H9B	0.2540	0.7509	0.1424	0.149*
H9C	0.3118	0.7932	0.1004	0.149*
C10	0.2234 (3)	0.5105 (5)	−0.1995 (8)	0.143 (3)
H10A	0.2204	0.4535	−0.1614	0.214*
H10B	0.2295	0.5083	−0.3041	0.214*
H10C	0.1892	0.5411	−0.1792	0.214*
C11	0.44160 (12)	0.82871 (18)	0.5440 (3)	0.0361 (6)
H11	0.4655	0.8732	0.5176	0.043*
C12	0.40932 (12)	0.83775 (17)	0.6698 (3)	0.0314 (6)
C13	0.37296 (15)	0.7725 (2)	0.7083 (4)	0.0445 (8)
H13	0.3509	0.7761	0.7929	0.053*
C14	0.37015 (16)	0.7016 (2)	0.6178 (4)	0.0529 (9)
H14	0.3455	0.6572	0.6398	0.064*
C15	0.40397 (16)	0.6973 (2)	0.4953 (4)	0.0470 (8)
H15	0.4017	0.6493	0.4353	0.056*
C16	0.41406 (12)	0.91928 (18)	0.7553 (3)	0.0357 (6)

	U11	U22	U33	U12	U13	U23
Cd1	0.03990 (16)	0.02586 (14)	0.03497 (16)	0.000	−0.00070 (14)	0.000
O1	0.0606 (14)	0.0357 (11)	0.0452 (13)	−0.0048 (10)	−0.0166 (11)	0.0054 (10)
O2	0.0552 (14)	0.0349 (11)	0.0504 (14)	−0.0075 (10)	−0.0097 (12)	0.0037 (10)
O3	0.0675 (15)	0.0323 (11)	0.0413 (12)	−0.0071 (10)	−0.0008 (12)	0.0041 (10)
O4	0.0467 (19)	0.0269 (14)	0.071 (2)	0.000	−0.0015 (19)	0.000
N1	0.0449 (14)	0.0373 (13)	0.0356 (14)	−0.0081 (11)	0.0017 (11)	−0.0062 (11)
N2	0.0645 (19)	0.0310 (13)	0.0346 (14)	0.0058 (13)	−0.0028 (13)	−0.0019 (12)
C1	0.0408 (15)	0.0326 (14)	0.0299 (14)	−0.0032 (12)	0.0014 (12)	−0.0019 (12)
C2	0.0418 (16)	0.0375 (15)	0.0369 (16)	−0.0074 (13)	−0.0042 (13)	0.0058 (13)
C3	0.0457 (19)	0.073 (3)	0.057 (2)	−0.0045 (18)	0.0016 (17)	−0.003 (2)
C4	0.042 (2)	0.121 (4)	0.081 (3)	−0.018 (2)	−0.003 (2)	0.005 (3)
C5	0.072 (3)	0.101 (4)	0.067 (3)	−0.043 (3)	−0.016 (2)	0.001 (3)
C6	0.085 (3)	0.056 (2)	0.058 (2)	−0.030 (2)	−0.011 (2)	−0.0060 (19)
C7	0.061 (2)	0.0349 (16)	0.0465 (19)	−0.0115 (15)	−0.0078 (16)	0.0007 (14)
C8	0.074 (3)	0.057 (2)	0.083 (3)	0.010 (2)	−0.005 (2)	−0.032 (2)
C9	0.055 (3)	0.130 (5)	0.113 (5)	0.017 (3)	0.009 (3)	−0.042 (4)
C10	0.103 (4)	0.189 (7)	0.137 (6)	−0.085 (5)	−0.034 (4)	−0.022 (5)
C11	0.0391 (15)	0.0323 (14)	0.0368 (15)	−0.0100 (12)	0.0041 (13)	0.0004 (12)
C12	0.0359 (14)	0.0310 (13)	0.0274 (13)	−0.0027 (11)	−0.0015 (11)	0.0032 (11)
C13	0.0507 (19)	0.0490 (18)	0.0340 (16)	−0.0122 (15)	0.0065 (14)	0.0034 (14)
C14	0.068 (2)	0.0449 (18)	0.0457 (19)	−0.0277 (17)	0.0084 (17)	0.0038 (15)
C15	0.067 (2)	0.0339 (15)	0.0403 (17)	−0.0140 (15)	0.0006 (16)	−0.0033 (14)
C16	0.0361 (14)	0.0356 (14)	0.0353 (14)	0.0009 (11)	−0.0012 (13)	0.0013 (13)

Cd1—O1	2.297 (2)	C4—H4	0.9300
Cd1—O1i	2.297 (2)	C5—C10	1.536 (6)
Cd1—O2	2.527 (2)	C6—C5	1.371 (7)
Cd1—O2i	2.527 (2)	C6—H6	0.9300
Cd1—O4	2.306 (3)	C7—C6	1.392 (5)
Cd1—N1	2.371 (3)	C7—C8	1.503 (5)
Cd1—N1i	2.371 (3)	C8—H8A	0.9600
Cd1—C1	2.759 (3)	C8—H8B	0.9600
Cd1—C1i	2.759 (3)	C8—H8C	0.9600
O1—C1	1.249 (4)	C11—H11	0.9300
O2—C1	1.253 (3)	C12—C11	1.380 (4)
O3—C16	1.236 (4)	C12—C13	1.382 (4)
O4—H41	0.80 (3)	C12—C16	1.499 (4)
N1—C11	1.331 (4)	C13—C14	1.382 (5)
N1—C15	1.344 (4)	C13—H13	0.9300
N2—C16	1.321 (4)	C14—H14	0.9300
N2—H2A	0.90 (4)	C15—C14	1.371 (5)
N2—H2B	0.81 (4)	C15—H15	0.9300
C1—C2	1.499 (4)	C9—H9A	0.9600
C2—C3	1.388 (5)	C9—H9B	0.9600
C2—C7	1.394 (5)	C9—H9C	0.9600
C3—C4	1.397 (6)	C10—H10A	0.9600
C3—C9	1.512 (6)	C10—H10B	0.9600
C4—C5	1.370 (7)	C10—H10C	0.9600
O1···H8Cii	2.55	N2···H13	2.75
O2···H2Biii	2.03 (3)	C6···H14iii	2.80
O3···H41iv	1.92 (3)	C16···H41iv	2.85 (3)
O3···H2Av	2.26 (4)	H8A···H8Avi	2.54
O1—Cd1—O1i	87.57 (11)	C7—C2—C1	118.9 (3)
O1—Cd1—O2	53.63 (7)	C2—C3—C4	117.9 (4)
O1i—Cd1—O2	137.06 (8)	C2—C3—C9	121.5 (4)
O1—Cd1—O2i	137.06 (8)	C4—C3—C9	120.6 (4)
O1i—Cd1—O2i	53.63 (7)	C3—C4—H4	118.8
O1—Cd1—O4	136.22 (6)	C5—C4—C3	122.3 (4)
O1i—Cd1—O4	136.22 (6)	C5—C4—H4	118.8
O1—Cd1—N1	85.85 (9)	C4—C5—C6	118.6 (4)
O1i—Cd1—N1	101.67 (9)	C4—C5—C10	119.7 (5)
O1—Cd1—N1i	101.67 (9)	C6—C5—C10	121.8 (5)
O1i—Cd1—N1i	85.85 (9)	C5—C6—C7	121.8 (4)
O1—Cd1—C1	26.66 (8)	C5—C6—H6	119.1
O1i—Cd1—C1	112.62 (9)	C7—C6—H6	119.1
O1—Cd1—C1i	112.62 (9)	C2—C7—C8	121.7 (3)
O1i—Cd1—C1i	26.66 (8)	C6—C7—C2	118.5 (4)
O2—Cd1—O2i	168.94 (10)	C6—C7—C8	119.7 (4)
O2—Cd1—C1	26.97 (7)	C7—C8—H8A	109.5
O2i—Cd1—C1	163.57 (8)	C7—C8—H8B	109.5
O2—Cd1—C1i	163.57 (8)	C7—C8—H8C	109.5
O2i—Cd1—C1i	26.97 (7)	H8A—C8—H8B	109.5
O4—Cd1—O2	84.47 (5)	H8A—C8—H8C	109.5
O4—Cd1—O2i	84.47 (5)	H8B—C8—H8C	109.5
O4—Cd1—N1	84.84 (6)	C3—C9—H9A	109.5
O4—Cd1—N1i	84.84 (6)	C3—C9—H9B	109.5
O4—Cd1—C1	110.64 (6)	C3—C9—H9C	109.5
O4—Cd1—C1i	110.64 (6)	H9A—C9—H9B	109.5
N1—Cd1—O2	93.81 (9)	H9A—C9—H9C	109.5
N1i—Cd1—O2	85.20 (9)	H9B—C9—H9C	109.5
N1—Cd1—O2i	85.20 (9)	C5—C10—H10A	109.5
N1i—Cd1—O2i	93.81 (9)	C5—C10—H10B	109.5
N1—Cd1—N1i	169.68 (12)	C5—C10—H10C	109.5
N1—Cd1—C1	89.67 (9)	H10A—C10—H10B	109.5
N1i—Cd1—C1	93.97 (9)	H10A—C10—H10C	109.5
N1—Cd1—C1i	93.97 (9)	H10B—C10—H10C	109.5
N1i—Cd1—C1i	89.67 (9)	N1—C11—C12	123.5 (3)
C1—Cd1—C1i	138.71 (12)	N1—C11—H11	118.3
C1—O1—Cd1	97.78 (18)	C12—C11—H11	118.3
C1—O2—Cd1	86.90 (18)	C11—C12—C13	118.6 (3)
Cd1—O4—H41	127 (2)	C11—C12—C16	118.3 (3)
C11—N1—Cd1	121.6 (2)	C13—C12—C16	123.1 (3)
C11—N1—C15	117.5 (3)	C12—C13—C14	118.3 (3)
C15—N1—Cd1	120.9 (2)	C12—C13—H13	120.8
C16—N2—H2A	121 (2)	C14—C13—H13	120.8
C16—N2—H2B	120 (3)	C13—C14—H14	120.3
H2A—N2—H2B	119 (4)	C15—C14—C13	119.5 (3)
O1—C1—Cd1	55.57 (15)	C15—C14—H14	120.3
O1—C1—O2	121.7 (3)	N1—C15—C14	122.6 (3)
O1—C1—C2	117.6 (3)	N1—C15—H15	118.7
O2—C1—Cd1	66.13 (17)	C14—C15—H15	118.7
O2—C1—C2	120.7 (3)	O3—C16—N2	124.0 (3)
C2—C1—Cd1	173.1 (2)	O3—C16—C12	119.1 (3)
C3—C2—C1	120.2 (3)	N2—C16—C12	116.9 (3)
C3—C2—C7	121.0 (3)
O1i—Cd1—O1—C1	−160.5 (2)	N1i—Cd1—C1—O2	−71.26 (19)
O2—Cd1—O1—C1	−0.25 (18)	C1i—Cd1—C1—O1	14.27 (18)
O2i—Cd1—O1—C1	175.96 (17)	C1i—Cd1—C1—O2	−165.28 (19)
O4—Cd1—O1—C1	19.5 (2)	Cd1—O1—C1—O2	0.5 (3)
N1—Cd1—O1—C1	97.6 (2)	Cd1—O1—C1—C2	−178.5 (2)
N1i—Cd1—O1—C1	−75.3 (2)	Cd1—O2—C1—O1	−0.4 (3)
C1i—Cd1—O1—C1	−169.85 (13)	Cd1—O2—C1—C2	178.6 (3)
O1—Cd1—O2—C1	0.25 (17)	Cd1—N1—C11—C12	−177.2 (2)
O1i—Cd1—O2—C1	29.9 (2)	C15—N1—C11—C12	2.4 (5)
O2i—Cd1—O2—C1	−166.18 (18)	Cd1—N1—C15—C14	177.8 (3)
O4—Cd1—O2—C1	−166.18 (18)	C11—N1—C15—C14	−1.8 (5)
N1—Cd1—O2—C1	−81.75 (19)	O1—C1—C2—C3	118.2 (4)
N1i—Cd1—O2—C1	108.55 (19)	O1—C1—C2—C7	−60.7 (4)
C1i—Cd1—O2—C1	36.3 (5)	O2—C1—C2—C3	−60.9 (4)
O1—Cd1—N1—C11	−162.7 (3)	O2—C1—C2—C7	120.2 (3)
O1i—Cd1—N1—C11	110.6 (2)	C1—C2—C3—C4	−178.2 (4)
O1—Cd1—N1—C15	17.7 (3)	C1—C2—C3—C9	0.1 (6)
O1i—Cd1—N1—C15	−68.9 (3)	C7—C2—C3—C4	0.7 (6)
O2—Cd1—N1—C11	−109.6 (2)	C7—C2—C3—C9	179.0 (4)
O2i—Cd1—N1—C11	59.3 (2)	C3—C2—C7—C6	−0.3 (5)
O2—Cd1—N1—C15	70.8 (3)	C1—C2—C7—C6	178.6 (3)
O2i—Cd1—N1—C15	−120.2 (3)	C3—C2—C7—C8	176.8 (4)
O4—Cd1—N1—C11	−25.6 (2)	C1—C2—C7—C8	−4.3 (5)
O4—Cd1—N1—C15	154.9 (3)	C2—C3—C4—C5	−0.5 (7)
N1i—Cd1—N1—C11	−25.6 (2)	C9—C3—C4—C5	−178.8 (5)
N1i—Cd1—N1—C15	154.9 (3)	C3—C4—C5—C6	−0.2 (8)
C1—Cd1—N1—C11	−136.3 (2)	C3—C4—C5—C10	−180.0 (5)
C1i—Cd1—N1—C11	84.8 (3)	C7—C6—C5—C4	0.6 (7)
C1—Cd1—N1—C15	44.1 (3)	C7—C6—C5—C10	−179.6 (5)
C1i—Cd1—N1—C15	−94.7 (3)	C2—C7—C6—C5	−0.4 (6)
O1i—Cd1—C1—O1	21.1 (3)	C8—C7—C6—C5	−177.6 (4)
O1—Cd1—C1—O2	−179.6 (3)	C13—C12—C11—N1	−1.1 (5)
O1i—Cd1—C1—O2	−158.40 (18)	C16—C12—C11—N1	−179.1 (3)
O2—Cd1—C1—O1	179.6 (3)	C11—C12—C13—C14	−0.8 (5)
O2i—Cd1—C1—O1	−9.8 (4)	C16—C12—C13—C14	177.1 (3)
O2i—Cd1—C1—O2	170.68 (14)	C11—C12—C16—O3	36.2 (4)
O4—Cd1—C1—O1	−165.73 (18)	C11—C12—C16—N2	−143.9 (3)
O4—Cd1—C1—O2	14.72 (19)	C13—C12—C16—O3	−141.7 (3)
N1—Cd1—C1—O1	−81.4 (2)	C13—C12—C16—N2	38.2 (4)
N1i—Cd1—C1—O1	108.3 (2)	C12—C13—C14—C15	1.3 (6)
N1—Cd1—C1—O2	99.07 (19)	N1—C15—C14—C13	0.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3vii	0.89 (3)	2.26 (4)	3.047 (4)	147 (3)
N2—H2B···O2viii	0.81 (3)	2.03 (3)	2.830 (4)	168 (4)
O4—H41···O3iv	0.80 (3)	1.92 (3)	2.714 (3)	170 (3)
C8—H8C···O1ix	0.96	2.55	3.468 (5)	161