Bis(3,5-di­nitro­benzoato-κO)bis­(ethane-1,2-di­amine-κ2N,N′)cadmium(II)

Ibragimov, A.

doi:10.1107/S2414314620008433

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 7| July 2020| x200843

https://doi.org/10.1107/S2414314620008433

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Bis(3,5-dinitrobenzoato-κO)bis(ethane-1,2-diamine-κ²N,N′)cadmium(II)

Avazbek Ibragimov ^a ^*

^aInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek Str 83, Tashkent 700125, Uzbekistan
^*Correspondence e-mail: alex.ibragimov@inbox.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 June 2020; accepted 23 June 2020; online 3 July 2020)

During systematic investigations of bioavailability and biological action enhancement of well known compounds with low bioactivity, a new mixed-ligand metal complex, [Cd(DNBA)₂(en)₂)] (DNBA = 3,5-dinitrobenzoate, C₇H₃N₂O₆; en = ethylendiamine, C₂H₈N₂), has been synthesized. The complex molecules are located on inversion centers. Two DNBA anions monodentately coordinate the Cd^II atom through an oxygen atom of the carboxylate group while two en molecules coordinate in a chelate fashion, resulting in a distorted O₂N₄ coordination set. There is a weak intramolecular hydrogen bond of 3.099 (4) Å between the non-coordinating oxygen atom of the carboxylate group and one of the en amine groups. Three relatively weak intermolecular N—H⋯O hydrogen bonds associate complex molecules into sheets extending parallel to (0 $[\overline{1}]$ 1), which are further stabilized by π–π interactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯O/O⋯H (50.2%) and H⋯H (21.1%) interactions.

Keywords: crystal structure; mixed-ligand complex; 3,5-dinitrobenzoic acid; ethylendiamine.

CCDC reference: 2011747

Structure description

DNBA (= 3,5-dinitrobenzoic acid) is an organic compound that is an important corrosion inhibitor applied in photography and is used by chemists to identify alcohol components in esters and in the fluorometric analysis of creatinine (Chandrasekaran et al., 2013 ). DNBA demonstrates low antimicrobial activity against bacteria and yeasts with values of the half maximal inhibitory concentration (IC50) and minimum inhibition concentration (MIC) of more than 3 mmol l⁻¹ but shows medium biological action against filamentous fungi M. gypseum with IC50 and MIC values of 2.1 and 3 mmol l⁻¹ (microbicide effect), respectively (Vaskova et al., 2009 ).

En (ethylendiamine) is used in large quantities for the production of many industrial chemicals. It is a well known bidentate chelating ligand for coordination complexes (Matsushita & Taira, 1999 ). En itself is not biologically active against different strains of microorganisms, but its Co^III complex demonstrates a strong antifungal action against a broad spectrum of Candida species (Turecka et al., 2018 ).

The water solubility of DNBA is low (1.35 g l⁻¹ at 25°C; Rogers & Stovall, 2000 ). In order to enhance its water solubility and antimicrobial activity, we tried to apply some of the presently available approaches (Jain et al., 2015 ). However, more encouraging is the combination of organic salts, DNBA and en as well as mixed-ligand complexes comprising respective ligands. Promising results have already been achieved in the case of 4-nitrobenzoic acid (Ibragimov et al., 2017 ), 4-aminobenzoic acid (Ibragimov et al., 2016 ) and 3-hydroxybenzoic acid (Ibragimov, 2016 ). A search of the Cambridge Structural Database (Groom et al., 2016 ) has revealed that organic salts on the basis of DNBA have already been obtained [refcodes VUJXIH (Nethaji et al., 1992 ) and FONCER (Jones et al., 2005 )] and therefore we made another attempt and synthesized a cadmium-based mixed-ligand complex. The choice of Cd is explained by the fact that compounds based on cadmium are toxic for living organisms including fungi.

In the crystal of the title compound, the complex molecules are located on inversion centers. Two symmetry-related DNBA anions monodentately coordinate to Cd^II through one of the oxygen atoms of the carboxylate group. The two en ligands coordinate in a chelate fashion through the two N atoms (Fig. 1). The bond lengths Cd—O1, Cd—N3 and Cd—N4 are 2.344 (2), 2.337 (4) and 2.322 (3) Å, respectively, and the cis-bond angles vary from 77.34 (12) to 102.66 (12)°, indicating a rather strong distortion from the ideal octahedral shape. The conformation of the complex molecule is stabilized through a weak intramolecular hydrogen bond [3.099 (4) Å and 143 (3)°] between the N4—H4A donor and the O2 acceptor (Table 1) defining a six-membered ring with graph-set notation S(6). Most coplanar with the aromatic ring is the N1O₂ nitro group [dihedral angle of 3.873 (3)°] while the carboxylate group is considerably twisted from the aromatic ring [dihedral angle = 19.332 (9)°]. The arrangement of the N2O₂ nitro group is intermediate between the latter two, the corresponding dihedral angle being 13.529 (6)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2	0.92 (1)	2.32 (2)	3.099 (4)	143 (3)
N4—H4A⋯O4ⁱ	0.92 (1)	2.56 (3)	3.268 (4)	134 (3)
N4—H4B⋯O4ⁱⁱ	0.92 (1)	2.39 (2)	3.237 (4)	153 (4)
N3—H3B⋯O5ⁱⁱⁱ	0.92 (1)	2.52 (7)	3.312 (5)	145 (10)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y+1, z+1; (iii) -x+2, -y, -z+1.

Figure 1
The molecular structure of the coordination complex [Cd(DNBA)₂(en)₂)] with displacement ellipsoids shown at the 30% probability level. The crystallographically independent part of the molecule is labelled, the atoms of the remaining part are generated by inversion symmetry. [Symmetry code: (i) −x + 2, −y + 1, −z + 2].

There are three relatively weak intermolecular hydrogen bonds in the crystal structure (Table 1). N4—H4A⋯O4ⁱ and N4—H4B⋯O4ⁱⁱ hydrogen bonds define rings with graph-set notation R₄²(8). The rings are further connected via N3—H3B⋯O5ⁱⁱⁱ hydrogen bonds, forming sheets extending parallel to (0 $[\overline{1}]$ 1) (Fig. 2). The sheets are stabilized by π–π stacking interactions [Cg1⋯Cg1 = 3.715 (3) Å, slippage = 1.608 Å, symmetry operation: 1 − x, −y, 1 − z; Cg1 is the centroid of the phenyl (C1–C6) ring].

Figure 2
The crystal packing of the coordination complex [Cd(DNBA)₂(en)₂)] showing N—H⋯O hydrogen bonds as dashed lines. For clarity, H atoms not involved in hydrogen bonding are omitted.

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis was carried out using Crystal Explorer 17.5 (Turner et al., 2017 ). The Hirshfeld surface mapped over d_norm (Fig. 3) shows the expected bright-red spots near atoms O2, O4, O5, H3B, H4A and H4B involved in the N—H⋯O hydrogen-bonding interactions described above. Fingerprint plots, Fig. 4, reveal that while H⋯O/O⋯H interactions make the greatest contribution to the surface contacts, as would be expected for a molecule with such a predominance of O atoms, H⋯H and H⋯C/C⋯H contacts are also substantial. The C⋯O/O⋯C, O⋯O, N⋯O/O⋯N, C⋯C, C⋯N/N⋯C and H⋯N/N⋯H contacts are less significant.

Figure 3
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.2200 to 1.2846 a.u..

Figure 4
Full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯O/O⋯H, (c) H⋯H, (d) H⋯C/C⋯H, (e) C⋯O/O⋯C, (f) O⋯O, (g) N⋯O/O⋯N, (h) C⋯C and (i) C⋯N/N⋯C interactions. The d_i and d_e values are the closest internal and external distances (in Å) from a given point on the Hirshfeld surface. Relative contributions are indicated.

A search of the Cambridge Structural Database (Version 5.41, November 2019; Groom et al., 2016) attested that over 300 crystal structures based on DNBA are registered. Among these structures, eleven compounds are monoligand complexes while 120 ones belong to mixed-ligand coordination compounds. There are two mixed-ligand complexes closely related to the [Cd(DNBA)₂(en)₂)] complex. The silver complexes with refcodes EQOKEA (Zhu et al., 2003 ) and EQOKEA01 (Qiu et al., 2005 ) consist of discrete and polymeric components. In the discrete component, Ag^I is coordinated by two DNBA molecules in a monodentate mode whereas in the second component silver ions are associated by en ligands into polymeric chains. There are also DNBA, en and –NO₂ ligands in the Co^I complex with refcode KICCEF (Sharma et al., 2007 ). In this complex, the metal ion is chelated by two en ligands, and one DNBA and one NO₂ molecules each in a monodentate mode.

Synthesis and crystallization

To an aqueous solution (2.5 ml) of Cd(CH₃COO)₂ (0.115 g, 0.5 mmol) was slowly added an ethanol solution (4 ml) containing en (60 μl) and DNBA (0.212 g, 1 mmol) under constant stirring. A colourless crystalline product was obtained at room temperature by slow solvent evaporation after 6 d. Single crystals for X-ray structure determination were selected from this product. Yield: 65%. Elemental analysis for C₁₈H₂₂CdN₈O₁₂ (654.83): calculated C 33.02; H 3.39; N 17.11%; found: C 32.96; H 3.32; N 17.08%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cd(C₇H₃N₂O₆)₂(C₂H₈N₂)₂)]
M_r	654.83
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	291
a, b, c (Å)	7.191 (5), 8.698 (5), 10.987 (5)
α, β, γ (°)	112.289 (5), 92.827 (5), 101.656 (5)
V (Å³)	616.7 (6)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	7.81
Crystal size (mm)	0.22 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur, Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.397, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4512, 2482, 2406
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.06
No. of reflections	2482
No. of parameters	195
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.51
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2011747

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620008433/wm4132sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620008433/wm4132Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(3,5-dinitrobenzoato-κO)bis(ethane-1,2-diamine-κ²N,N')cadmium(II) top

Crystal data top

[Cd(C₇H₃N₂O₆)₂(C₂H₈N₂)₂)]	Z = 1
M_r = 654.83	F(000) = 330
Triclinic, P1	D_x = 1.763 Mg m⁻³
a = 7.191 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.698 (5) Å	Cell parameters from 3166 reflections
c = 10.987 (5) Å	θ = 4.4–75.1°
α = 112.289 (5)°	µ = 7.81 mm⁻¹
β = 92.827 (5)°	T = 291 K
γ = 101.656 (5)°	Block, colorless
V = 616.7 (6) Å³	0.22 × 0.18 × 0.16 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur, Ruby diffractometer	2482 independent reflections
Radiation source: fine-focus sealed X-ray tube	2406 reflections with I > 2σ(I)
Detector resolution: 10.2576 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 75.8°, θ_min = 4.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	h = −8→8
T_min = 0.397, T_max = 1.000	k = −10→10
4512 measured reflections	l = −11→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0513P)² + 0.2183P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2482 reflections	Δρ_max = 0.45 e Å⁻³
195 parameters	Δρ_min = −0.51 e Å⁻³
5 restraints	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: Intrinsic-phasing	Extinction coefficient: 0.0032 (5)

Special details top

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. N-bound H atoms were located in a difference Fourier map and were refined with bond-length restraints of 0.92 (1) Å.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	1.000000	0.500000	1.000000	0.04436 (14)
O2	0.6549 (4)	0.5433 (4)	0.7930 (3)	0.0651 (7)
O1	0.8216 (4)	0.3493 (3)	0.7881 (2)	0.0620 (7)
O3	0.1233 (4)	0.3373 (4)	0.4291 (3)	0.0715 (8)
O4	0.1282 (4)	0.1278 (4)	0.2450 (3)	0.0767 (9)
O6	0.8565 (4)	−0.0927 (4)	0.3594 (3)	0.0730 (8)
N1	0.1978 (4)	0.2284 (4)	0.3583 (3)	0.0517 (6)
N4	1.0222 (4)	0.7651 (3)	0.9904 (3)	0.0487 (6)
O5	0.6643 (5)	−0.1370 (4)	0.1882 (3)	0.0757 (8)
N2	0.7258 (4)	−0.0609 (4)	0.3057 (3)	0.0516 (6)
C2	0.6271 (4)	0.3000 (4)	0.5940 (3)	0.0381 (6)
C3	0.4603 (4)	0.3208 (4)	0.5398 (3)	0.0396 (6)
H3	0.402141	0.406126	0.589595	0.047*
C7	0.7155 (4)	0.1743 (4)	0.5164 (3)	0.0395 (6)
H7	0.827318	0.158989	0.551588	0.047*
C6	0.6340 (4)	0.0733 (4)	0.3869 (3)	0.0397 (6)
C4	0.3822 (4)	0.2132 (4)	0.4114 (3)	0.0401 (6)
C5	0.4662 (4)	0.0883 (4)	0.3320 (3)	0.0426 (6)
H5	0.411582	0.017367	0.245051	0.051*
N3	1.2449 (5)	0.5152 (5)	0.8698 (4)	0.0714 (10)
C1	0.7084 (4)	0.4101 (4)	0.7390 (3)	0.0443 (7)
C8	1.2033 (6)	0.8097 (5)	0.9427 (4)	0.0622 (9)
H8A	1.307671	0.851575	1.015179	0.075*
H8B	1.200122	0.900523	0.912486	0.075*
C9	1.2380 (7)	0.6594 (6)	0.8321 (5)	0.0725 (11)
H9A	1.136935	0.622053	0.758114	0.087*
H9B	1.358522	0.693491	0.802584	0.087*
H4A	0.922 (4)	0.747 (5)	0.928 (3)	0.050 (10)*
H4B	1.024 (6)	0.846 (4)	1.074 (2)	0.072 (13)*
H3A	1.336 (4)	0.586 (4)	0.940 (3)	0.053 (11)*
H3B	1.285 (10)	0.419 (8)	0.821 (8)	0.27 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0539 (2)	0.0461 (2)	0.03613 (18)	0.01547 (13)	0.00951 (12)	0.01752 (13)
O2	0.0524 (14)	0.0699 (16)	0.0509 (13)	0.0237 (12)	−0.0022 (10)	−0.0035 (12)
O1	0.0744 (17)	0.0650 (15)	0.0418 (12)	0.0244 (13)	−0.0096 (11)	0.0144 (11)
O3	0.0556 (15)	0.086 (2)	0.0744 (18)	0.0318 (14)	−0.0012 (13)	0.0279 (16)
O4	0.0756 (19)	0.0665 (17)	0.0712 (18)	0.0104 (14)	−0.0354 (15)	0.0181 (15)
O6	0.0684 (17)	0.0780 (19)	0.0744 (18)	0.0403 (15)	0.0103 (14)	0.0209 (15)
N1	0.0464 (14)	0.0535 (16)	0.0554 (16)	0.0080 (12)	−0.0075 (12)	0.0257 (13)
N4	0.0558 (16)	0.0437 (14)	0.0428 (14)	0.0192 (12)	0.0014 (11)	0.0099 (11)
O5	0.096 (2)	0.0711 (18)	0.0481 (15)	0.0316 (16)	0.0140 (13)	0.0040 (13)
N2	0.0561 (16)	0.0472 (15)	0.0494 (15)	0.0136 (12)	0.0162 (12)	0.0154 (12)
C2	0.0365 (13)	0.0420 (15)	0.0356 (13)	0.0062 (11)	0.0038 (10)	0.0169 (12)
C3	0.0384 (14)	0.0408 (15)	0.0400 (14)	0.0085 (11)	0.0056 (11)	0.0172 (12)
C7	0.0385 (14)	0.0437 (15)	0.0388 (14)	0.0109 (11)	0.0052 (11)	0.0185 (12)
C6	0.0446 (15)	0.0374 (14)	0.0381 (14)	0.0090 (11)	0.0086 (11)	0.0161 (12)
C4	0.0394 (14)	0.0412 (15)	0.0415 (14)	0.0063 (11)	−0.0018 (11)	0.0208 (12)
C5	0.0483 (16)	0.0400 (15)	0.0350 (13)	0.0043 (12)	0.0011 (11)	0.0139 (12)
N3	0.068 (2)	0.073 (2)	0.098 (3)	0.0355 (19)	0.038 (2)	0.047 (2)
C1	0.0386 (14)	0.0523 (17)	0.0350 (14)	0.0083 (12)	0.0034 (11)	0.0112 (13)
C8	0.064 (2)	0.052 (2)	0.074 (2)	0.0088 (16)	0.0048 (18)	0.0329 (19)
C9	0.074 (3)	0.086 (3)	0.082 (3)	0.029 (2)	0.035 (2)	0.052 (2)

Geometric parameters (Å, º) top

Cd1—N4ⁱ	2.322 (3)	C2—C7	1.397 (4)
Cd1—N4	2.322 (3)	C2—C1	1.524 (4)
Cd1—N3	2.337 (4)	C3—C4	1.374 (4)
Cd1—N3ⁱ	2.337 (4)	C3—H3	0.9300
Cd1—O1	2.344 (2)	C7—C6	1.379 (4)
Cd1—O1ⁱ	2.344 (2)	C7—H7	0.9300
O2—C1	1.235 (4)	C6—C5	1.375 (4)
O1—C1	1.257 (4)	C4—C5	1.380 (4)
O3—N1	1.216 (4)	C5—H5	0.9300
O4—N1	1.226 (4)	N3—C9	1.471 (6)
O6—N2	1.218 (4)	N3—H3A	0.914 (10)
N1—C4	1.473 (4)	N3—H3B	0.916 (10)
N4—C8	1.462 (5)	C8—C9	1.485 (6)
N4—H4A	0.916 (10)	C8—H8A	0.9700
N4—H4B	0.917 (10)	C8—H8B	0.9700
O5—N2	1.216 (4)	C9—H9A	0.9700
N2—C6	1.474 (4)	C9—H9B	0.9700
C2—C3	1.388 (4)

N4ⁱ—Cd1—N4	179.999 (11)	C6—C7—C2	118.8 (3)
N4ⁱ—Cd1—N3	102.66 (12)	C6—C7—H7	120.6
N4—Cd1—N3	77.34 (12)	C2—C7—H7	120.6
N4ⁱ—Cd1—N3ⁱ	77.34 (12)	C5—C6—C7	122.6 (3)
N4—Cd1—N3ⁱ	102.66 (12)	C5—C6—N2	118.6 (3)
N3—Cd1—N3ⁱ	180.0	C7—C6—N2	118.8 (3)
N4ⁱ—Cd1—O1	86.36 (10)	C3—C4—C5	122.8 (3)
N4—Cd1—O1	93.64 (10)	C3—C4—N1	118.4 (3)
N3—Cd1—O1	80.38 (15)	C5—C4—N1	118.8 (3)
N3ⁱ—Cd1—O1	99.63 (15)	C6—C5—C4	117.1 (3)
N4ⁱ—Cd1—O1ⁱ	93.64 (10)	C6—C5—H5	121.5
N4—Cd1—O1ⁱ	86.36 (10)	C4—C5—H5	121.5
N3—Cd1—O1ⁱ	99.62 (15)	C9—N3—Cd1	106.2 (2)
N3ⁱ—Cd1—O1ⁱ	80.37 (15)	C9—N3—H3A	90 (3)
O1—Cd1—O1ⁱ	180.00 (8)	Cd1—N3—H3A	95 (3)
C1—O1—Cd1	122.9 (2)	C9—N3—H3B	126 (8)
O3—N1—O4	124.1 (3)	Cd1—N3—H3B	121 (7)
O3—N1—C4	118.6 (3)	H3A—N3—H3B	110 (2)
O4—N1—C4	117.3 (3)	O2—C1—O1	128.6 (3)
C8—N4—Cd1	107.5 (2)	O2—C1—C2	117.4 (3)
C8—N4—H4A	109 (2)	O1—C1—C2	114.0 (3)
Cd1—N4—H4A	105 (2)	N4—C8—C9	111.1 (3)
C8—N4—H4B	109 (3)	N4—C8—H8A	109.4
Cd1—N4—H4B	110 (3)	C9—C8—H8A	109.4
H4A—N4—H4B	117 (4)	N4—C8—H8B	109.4
O5—N2—O6	123.1 (3)	C9—C8—H8B	109.4
O5—N2—C6	118.1 (3)	H8A—C8—H8B	108.0
O6—N2—C6	118.8 (3)	N3—C9—C8	112.9 (4)
C3—C2—C7	119.7 (3)	N3—C9—H9A	109.0
C3—C2—C1	119.7 (3)	C8—C9—H9A	109.0
C7—C2—C1	120.5 (3)	N3—C9—H9B	109.0
C4—C3—C2	118.9 (3)	C8—C9—H9B	109.0
C4—C3—H3	120.5	H9A—C9—H9B	107.8
C2—C3—H3	120.5

C7—C2—C3—C4	1.8 (4)	O4—N1—C4—C5	0.0 (4)
C1—C2—C3—C4	−175.9 (3)	C7—C6—C5—C4	1.5 (4)
C3—C2—C7—C6	0.0 (4)	N2—C6—C5—C4	178.9 (3)
C1—C2—C7—C6	177.8 (3)	C3—C4—C5—C6	0.5 (4)
C2—C7—C6—C5	−1.8 (4)	N1—C4—C5—C6	−177.3 (3)
C2—C7—C6—N2	−179.2 (3)	Cd1—O1—C1—O2	−8.4 (5)
O5—N2—C6—C5	9.9 (4)	Cd1—O1—C1—C2	172.57 (19)
O6—N2—C6—C5	−168.6 (3)	C3—C2—C1—O2	−19.2 (4)
O5—N2—C6—C7	−172.6 (3)	C7—C2—C1—O2	163.0 (3)
O6—N2—C6—C7	8.9 (4)	C3—C2—C1—O1	159.9 (3)
C2—C3—C4—C5	−2.2 (4)	C7—C2—C1—O1	−17.8 (4)
C2—C3—C4—N1	175.6 (3)	Cd1—N4—C8—C9	42.2 (4)
O3—N1—C4—C3	1.3 (5)	Cd1—N3—C9—C8	41.0 (5)
O4—N1—C4—C3	−177.9 (3)	N4—C8—C9—N3	−59.1 (5)
O3—N1—C4—C5	179.2 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2	0.92 (1)	2.32 (2)	3.099 (4)	143 (3)
N4—H4A···O4ⁱⁱ	0.92 (1)	2.56 (3)	3.268 (4)	134 (3)
N4—H4B···O4ⁱⁱⁱ	0.92 (1)	2.39 (2)	3.237 (4)	153 (4)
N3—H3B···O5^iv	0.92 (1)	2.52 (7)	3.312 (5)	145 (10)

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

Percentage contributions to the Hirshfeld surface for (I). top

Contacts	Included surface area %
H···O/O···H	50.2
H···H	21.1
H···C/C···H	8.4
C···O/O···C	6.4
O···O	5.1
N···O/O···N	3.8
C···C	2.7
C···N/N···C	1.4
H···N/N···H	1.0

Funding information

This work was supported by a Grant for Fundamental Research from the Center of Science and Technology, Uzbekistan (No. BA–FA–F7–004).

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