Syntheses and structures of bis(2-amino­py­rimi­dine-κN1)di­chlorido­zinc(II) (ortho­rhom­bic polymorph) and bis(2-am­ino­py­rimi­dine-κN1)di­iodido­zinc(II)

Näther, C.; Bhosekar, G.

doi:10.1107/S2056989026001878

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Volume 82| Part 3| March 2026| Pages 300-304

https://doi.org/10.1107/S2056989026001878

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Syntheses and structures of bis(2-aminopyrimidine-κN¹)dichloridozinc(II) (orthorhombic polymorph) and bis(2-aminopyrimidine-κN¹)diiodidozinc(II)

Christian Näther ^a ^* and Gaurav Bhosekar ^b

^aInstitut für Anorganische Chemie, Universität Kiel, Max-Eyth.-Str. 2, 24118 Kiel, Germany, and ^bSuman Ramesh Tulsiani Technical Campus - Faculty of Engineering. Kamshet, Pune, India
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 5 February 2026; accepted 19 February 2026; online 24 February 2026)

The title compounds, [ZnCl₂(C₄H₅N₃)₂] (1) and [ZnI₂(C₄H₅N₃)₂] (2) (C₄H₅N₃ = 2-aminopyrimidine), were prepared from a solvent mixture of trichloromethane and methanol and structurally characterized. The asymmetric unit of 1 consists of one Zn^II cation that is situated on a twofold rotation axis and one chloride anion as well as one 2-aminopyrimidine ligand in general positions. The asymmetric unit of 2 is built up of one Zn^II cation, two iodide anions and two 2-aminopyrimidine ligands, all of them located in general positions. In both compounds, the metal cations are tetrahedrally coordinated by two halide anions and two 2-aminopyrimidine ligands. In compound 1, the discrete complexes are linked by N—H⋯Cl hydrogen bonds into layers that are further connected by weak C—H⋯Cl interactions. In compound 2, the complexes are connected via N—H⋯I hydrogen bonds into layers that are further linked by a number of N—H⋯I and C—H⋯I hydrogen bonds. Compound 1 represents a second polymorphic modification of ZnCl₂(C₄H₅N₃)₂ that crystallizes in the orthorhombic non-centrosymmetric space group Pba2, whereas the known form crystallizes in the monoclinic, centrosymmetric space group C2/c [Lin & Zeng (2007 ). Acta Cryst. E63, m1597].

Keywords: crystal structure; coordination compounds; discrete complexes; hydrogen bonding; synthesis; zinc halide; 2-aminopyrimidine.

CCDC references: 2531977; 2531976

1. Chemical context

Investigations on the synthesis and crystal structures of new coordination compounds is still a major field in inorganic chemistry. Our interest is focused on coordination compounds based on transition-metal halides and N-donor coligands. In the beginning, we concentrated on compounds based on univalent cations such as Cu^I because they show a versatile structural behavior that can be traced back to the fact that the metal cations are frequently linked by bridging halide anions (Kromp & Sheldrick, 1999 ; Peng et al., 2010 ; Näther et al., 2001 , 2002 ). Moreover, multiple compounds with a different ratio between the metal halide and the coligand are often observed (Näther & Jess, 2002 ; Näther et al., 2003 ). In further work, we investigated coordination compounds with twofold positively charged metal cations such as Zn^II or Cd^II, but compared to the copper(I) halides these show a limited structural variability (Bhosekar et al., 2006 ; Neumann et al., 2018a ,b ). Such compounds, however, are of interest because of their luminescence properties (Zeng et al., 2010 ; Neumann et al., 2018a,b; Jess et al., 2020 ; Kokina et al., 2020 ).

In the course of our systematic investigations, we became interested in 2-aminopyrimidine (C₄H₅N₃) as coligand. On the one hand, the coordination of a metal cation might be more difficult, because of steric interference from the neighbouring amino group, but on the other strong hydrogen bonding can be expected.

In this context it is noted that two compounds with the composition ZnCl₂(C₄H₅N₃)₂ (CSD refcode YIDPAD; Lin & Zeng, 2007) and ZnBr₂(C₄H₅N₃)₂ (LOBPOI; Qu et al., 2008 ) are already reported in the CSD (Version 5.43, 2025; Groom et al., 2016 ), as found using a CONQUEST (Bruno et al., 2002 ) search. Both of them consist of discrete neutral complexes that are linked by intermolecular hydrogen bonds. In the course of our investigations, we obtained crystals of the missing compound with ZnI₂, and with ZnCl₂ we obtained crystals of a second polymorph of ZnCl₂(C₄H₅N₃)₂ (Lin & Zeng, 2007).

2. Structural commentary

ZnCl₂(C₄H₅N₃)₂ (1) represents a second polymorphic modification of the form that is already reported in the literature (Lin & Zeng, 2007). In contrast to the reported form that crystallizes in the centrosymmetric monoclinic space group C2/c, compound 1 crystallizes in the non-centrosymmetric orthorhombic space group Pba2. The asymmetric unit of 1 consists of one Zn^II cation located on a twofold rotation axis and one chloride anion and one 2-aminopyrimidine ligand in general positions (Fig. 1). In the crystal structure, the Zn^II cations are fourfold coordinated by two symmetry-related halide anions and two symmetry-related 2-aminopyrimidine ligands (Fig. 1). Bond lengths and angles show that the tetrahedra are only slightly distorted (Table 1). The overall geometry is very similar to the form reported in the literature (Lin & Zeng, 2007). Compound 1 was crystallized from the mixed solvents of methanol and trichloromethane (see Synthesis and crystallization) whereas the form reported by Lin & Zeng was crystallized from an ethanol solution.

Table 1
Selected geometric parameters (Å, °) for 1

Zn1—N1	2.028 (3)	Zn1—Cl1	2.2613 (10)

N1ⁱ—Zn1—N1	111.5 (2)	N1—Zn1—Cl1	111.64 (9)
N1—Zn1—Cl1ⁱ	105.22 (9)	Cl1ⁱ—Zn1—Cl1	111.79 (6)
Symmetry code: (i) .

Figure 1
The molecular structure of 1 with displacement ellipsoids drawn at the 50% probability level and intramolecular N—H⋯Cl hydrogen bonding shown as dashed lines. Symmetry code: (i) −x + 1, −y + 1, z.

The iodide compound ZnI₂(C₄H₅N₃)₂ (2) is not isotypic to any of the zinc(II) halide compounds known in the literature and also not to 1. Its asymmetric unit is built up of one Zn^II cation as well as two crystallographically independent iodide anions and 2-aminopyrimidine ligands that are located in general positions (Fig. 2). As in 1, the Zn^II cations are fourfold coordinated by two iodide anions and two 2-aminopyrimidine ligands within slightly distorted tetrahedra (Fig. 2 and Table 2).

Table 2
Selected geometric parameters (Å, °) for 2

Zn1—N11	2.040 (3)	Zn1—I2	2.5686 (6)
Zn1—N1	2.052 (4)	Zn1—I1	2.5948 (6)

N11—Zn1—N1	103.25 (14)	N11—Zn1—I1	109.47 (10)
N11—Zn1—I2	110.46 (10)	N1—Zn1—I1	114.82 (10)
N1—Zn1—I2	107.01 (10)	I2—Zn1—I1	111.50 (2)

Figure 2
The molecular structure of 2 with displacement ellipsoids drawn at the 50% probability level and the intramolecular N—H⋯I hydrogen bonding shown as a dashed line.

3. Supramolecular features

In the extended structure of 1, the discrete complexes are linked via N—H⋯Cl hydrogen bonds between the amino H atom and the chloride anions (Fig. 3). One of these H atoms acts as donor for an intramolecular, the second for an intermolecular hydrogen bond. The H⋯Cl distances are relatively short and the N—H⋯Cl angles close to linear indicate strong hydrogen bonding (Table 3). In this way, layers are formed,that lie parallel to the ab plane with the hydrogen bonds pointed in the direction of the crystallographic b axis (Fig. 3). These layers are further linked by C—H⋯Cl hydrogen bonds between one of the H atoms of the six-membered rings and the chloride anions (Fig. 4 and Table 3). From Fig. 4 it may be seen that all the pyrimidine rings point in the crystallographic c-axis direction, clearly proving the non-centrosymmetry of this structure (Fig. 4).

Table 3
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1ⁱⁱ	0.91 (2)	2.52 (3)	3.431 (4)	177 (5)
N3—H3B⋯Cl1	0.92 (2)	2.43 (3)	3.311 (4)	162 (4)
C2—H2⋯Cl1ⁱⁱⁱ	0.94	2.92	3.772 (5)	152
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-1]$ .

Figure 3
Crystal structure of 1 with a view onto the layers formed by intermolecular N—H⋯Cl hydrogen bonds (shown as dashed lines).

Figure 4
Crystal structure of 1 with a view along the a-axis direction showing the non-centrosymmetry of this structure. Intermolecular hydrogen bonds are shown as dashed lines.

The structure of 1 is completely different from that of the other polymorph already reported in the literature. In this modification, each complex is linked to neighbouring complexes by centrosymmetric pairs of N—H⋯N hydrogen bonds (Fig. 5). The second N—H H atom is only involved in intramolecular N—H⋯Cl hydrogen bonding but in contrast to the form presented here, the N—H⋯N and N—H⋯Cl angles are far from linear, surprisingly indicating weaker interactions. Finally, in contrast to the title polymorph, in the known form the complexes are linked into chains that propagate in the c-axis direction (Fig. 5).

Figure 5
Crystal structure of the second polymorph of 1 already reported in the literature (Lin & Zeng, 2007

) with intermolecular N—H⋯N and N—H⋯Cl hydrogen bonds shown as dashed lines.

In the iodide compound 2, the discrete complexes are linked by intermolecular N—H⋯I hydrogen bonds into layers that in this compound are parallel to the bc plane (Fig. 6). As in compound 1, one amine H atom is involved in an intramolecular hydrogen bond, whereas the second H atom shows intermolecular hydrogen bonding. Bond lengths and angles also indicate a significant interaction (Table 4). These layers are further linked by pairs of C—H⋯I interactions between the iodide anions and the H atoms of the pyrimidine rings (Fig. 7).

Table 4
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯I1	0.88 (2)	2.96 (3)	3.742 (4)	150 (4)
N3—H3B⋯I1ⁱ	0.89 (2)	3.03 (2)	3.922 (4)	173 (5)
C2—H2⋯I2ⁱⁱ	0.94	3.31	3.982 (5)	130
C4—H4⋯N11	0.94	2.67	3.275 (6)	123
N13—H13A⋯I1	0.90	2.84	3.738 (4)	173
N13—H13B⋯I2ⁱⁱⁱ	0.90	2.81	3.693 (4)	169
C13—H13⋯I2^iv	0.94	3.10	4.001 (5)	162
C14—H14⋯I2	0.94	3.14	3.815 (5)	130
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) .

Figure 6
Crystal structure of 2 along the b-axis direction with a view onto the layers and intermolecular N—H⋯I hydrogen bonds shown as dashed lines.

Figure 7
Crystal structure of 2 with a view along the a-axis direction and intermolecular hydrogen bonds shown as dashed lines.

4. Database survey

A search in the CSD (Version 5.43, 2025; Groom et al., 2016) using CONQUEST (Bruno et al., 2002) revealed that two Zn halide coordination compounds with the composition ZnCl₂(C₄H₅N₃)₂ (Lin & Zeng, 2007) and ZnBr₂(C₄H₅N₃)₂ (Qu et al., 2008) are already reported (see above). There are additional Zn compounds with different anions that are related to the title compounds, including (Zn(NCS)₂(C₄H₅N₃)₂ (Jin et al., 2010 ), (Zn(NO₃)₂(C₄H₅N₃)₂(H₂O) (Gao & Ng, 2010 ) and (Zn(C₁₁H₅O₂F₃)₂(C₄H₅N₃)₂ (Perdih, 2016 ) that also consists of discrete complexes. There is also a compound with mixed hydroxide nitrate anions that forms a polymeric structure (Kang et al., 2011 ).

Finally, it is noted that some compounds are reported in which the 2-aminopyrimidine ligands are protonated, but none of them contain zinc(II) as cation. These include, for example, 2-amino-1,3-dihydropyrimidiniumtetrabromocopper(II) (Pon et al., 1997 ), 2-aminopyrimidiniumtetrabromocobalt(II) monohydrate (Masaki et al., 2002 ), 2-amino-1,3-dihydropyrimidiniumtetraaquadibromomanganese(II) dibromide (Lee et al., 2003 ) and 2-amino-1,3-dihydropyrimidiniumtetraaquadibromonickel(II) dibromide (Masaki et al., 2002). In three additional compounds, the 2-aminopyridine ligand is also protonated and act as counter-cation for Mo and W cluster compounds (Chen et al., 2015 ; Xiao et al., 2018 ).

5. Synthesis and crystallization

Zinc chloride and zinc iodide as well as 2-aminopyrimidine were purchased from Sigma-Aldrich.

To prepare 1, 0.500 mmol (68.1 mg) of zinc chloride and 1.00 mmol (95.1 mg) of 2-aminopyrimidine were reacted in a solvent mixture of 1 ml of trichloromethane and 1 ml of methanol. Within 3 d, crystals suitable for single crystal X-ray diffraction were obtained in the form of colorless blocks.

Compound 2 was prepared by reacting 0.500 mmol (159.6 mg) of zinc iodide and 1.00 mmol (95.1 mg) of 2-aminopyrimidine in a solvent mixture of 3 ml of trichloromethane and 3 ml of methanol. Within 3 d, colorless blocks suitable for single crystal X-ray diffraction were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The C—H hydrogen atoms were positioned with idealized geometry and were refined as riding atoms with U_iso(H) = 1.2U_eq(C). The N—H H atoms were located in difference maps and were refined isotropically with restraints (DFIX).

Table 5
Experimental details

	1	2
Crystal data
Chemical formula	[ZnCl₂(C₄H₅N₃)₂]	[ZnI₂(C₄H₅N₃)₂]
M_r	326.49	509.39
Crystal system, space group	Orthorhombic, Pba2	Monoclinic, P2₁/n
Temperature (K)	220	220
a, b, c (Å)	7.6628 (7), 12.0590 (8), 6.8735 (4)	9.5469 (6), 15.3764 (13), 10.1518 (6)
α, β, γ (°)	90, 90, 90	90, 95.884 (7), 90
V (Å³)	635.15 (8)	1482.40 (18)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	2.34	5.81
Crystal size (mm)	0.18 × 0.16 × 0.14	0.16 × 0.10 × 0.06

Data collection
Diffractometer	Stoe IPDS1	Stoe IPDS1
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008 )	Numerical (X-RED and X-SHAPE; Stoe, 2008)
T_min, T_max	0.636, 0.842	0.296, 0.471
No. of measured, independent and observed [I > 2σ(I)] reflections	5690, 1490, 1251	14800, 3491, 2946
R_int	0.045	0.091
(sin θ/λ)_max (Å⁻¹)	0.660	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.080, 1.00	0.036, 0.094, 1.03
No. of reflections	1490	3491
No. of parameters	87	163
No. of restraints	3	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.43	1.17, −1.28
Absolute structure	Flack x determined using 505 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	–
Absolute structure parameter	0.007 (13)	–
Computer programs: X-AREA (Stoe, 2008), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and XP in SHELXTL-PC (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2531977; 2531976

Crystal structure: contains datablocks 1, 2. DOI: https://doi.org/10.1107/S2056989026001878/hb8195sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989026001878/hb81951sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989026001878/hb81952sup3.hkl

checkCIF report

Computing details top

Bis(2-aminopyrimidine-κN¹)dichloridozinc(II) (1) top

Crystal data top

[ZnCl₂(C₄H₅N₃)₂]	D_x = 1.707 Mg m⁻³
M_r = 326.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pba2	Cell parameters from 6615 reflections
a = 7.6628 (7) Å	θ = 3.0–28.0°
b = 12.0590 (8) Å	µ = 2.34 mm⁻¹
c = 6.8735 (4) Å	T = 220 K
V = 635.15 (8) Å³	Block, colorless
Z = 2	0.18 × 0.16 × 0.14 mm
F(000) = 328

Data collection top

Stoe IPDS-1 diffractometer	1251 reflections with I > 2σ(I)
Phi scans	R_int = 0.045
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	θ_max = 28.0°, θ_min = 3.2°
T_min = 0.636, T_max = 0.842	h = −10→10
5690 measured reflections	k = −15→15
1490 independent reflections	l = −8→9

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0537P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.032	(Δ/σ)_max < 0.001
wR(F²) = 0.080	Δρ_max = 0.49 e Å⁻³
S = 1.00	Δρ_min = −0.43 e Å⁻³
1490 reflections	Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
87 parameters	Extinction coefficient: 0.038 (7)
3 restraints	Absolute structure: Flack x determined using 505 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.007 (13)
Hydrogen site location: mixed

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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.500000	0.500000	0.88265 (9)	0.0219 (2)
Cl1	0.74418 (15)	0.50555 (6)	1.06713 (13)	0.0302 (3)
N1	0.4752 (4)	0.6381 (3)	0.7166 (5)	0.0222 (7)
N2	0.4748 (6)	0.8362 (4)	0.6738 (8)	0.0446 (12)
N3	0.5753 (6)	0.7516 (3)	0.9660 (7)	0.0349 (9)
H3A	0.623 (6)	0.819 (3)	0.998 (8)	0.035 (12)*
H3B	0.634 (5)	0.692 (3)	1.018 (7)	0.029 (12)*
C1	0.5104 (5)	0.7413 (4)	0.7842 (6)	0.0232 (8)
C2	0.4046 (7)	0.8250 (4)	0.4924 (8)	0.0388 (11)
H2	0.378192	0.888020	0.417373	0.047*
C3	0.3723 (6)	0.7190 (4)	0.4194 (6)	0.0372 (11)
H3	0.328392	0.709206	0.292874	0.045*
C4	0.4057 (6)	0.6306 (3)	0.5345 (7)	0.0304 (9)
H4	0.379338	0.559649	0.486091	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0307 (3)	0.0128 (3)	0.0223 (3)	−0.0020 (2)	0.000	0.000
Cl1	0.0370 (6)	0.0213 (5)	0.0322 (6)	0.0024 (4)	−0.0098 (4)	−0.0014 (5)
N1	0.0293 (18)	0.0158 (14)	0.0215 (17)	−0.0022 (11)	−0.0010 (13)	0.0017 (13)
N2	0.058 (3)	0.029 (2)	0.047 (3)	0.0026 (17)	0.004 (2)	0.008 (2)
N3	0.058 (2)	0.0152 (14)	0.032 (2)	−0.0020 (19)	−0.011 (2)	−0.0034 (14)
C1	0.0279 (19)	0.0170 (18)	0.025 (2)	−0.0020 (15)	0.0059 (17)	0.0000 (16)
C2	0.055 (3)	0.030 (2)	0.031 (2)	0.008 (2)	−0.002 (2)	0.0150 (19)
C3	0.046 (2)	0.042 (2)	0.024 (3)	0.005 (2)	−0.0037 (18)	0.0048 (18)
C4	0.035 (2)	0.030 (2)	0.026 (2)	−0.0036 (16)	−0.0062 (18)	−0.0002 (16)

Geometric parameters (Å, º) top

Zn1—N1ⁱ	2.028 (3)	N3—C1	1.351 (6)
Zn1—N1	2.028 (3)	N3—H3A	0.91 (2)
Zn1—Cl1ⁱ	2.2612 (10)	N3—H3B	0.92 (2)
Zn1—Cl1	2.2613 (10)	C2—C3	1.396 (7)
N1—C1	1.355 (6)	C2—H2	0.9400
N1—C4	1.363 (6)	C3—C4	1.352 (6)
N2—C2	1.365 (7)	C3—H3	0.9400
N2—C1	1.401 (6)	C4—H4	0.9400

N1ⁱ—Zn1—N1	111.5 (2)	N3—C1—N1	118.4 (4)
N1ⁱ—Zn1—Cl1ⁱ	111.64 (9)	N3—C1—N2	119.8 (4)
N1—Zn1—Cl1ⁱ	105.22 (9)	N1—C1—N2	121.7 (4)
N1ⁱ—Zn1—Cl1	105.22 (9)	N2—C2—C3	119.3 (4)
N1—Zn1—Cl1	111.64 (9)	N2—C2—H2	120.4
Cl1ⁱ—Zn1—Cl1	111.79 (6)	C3—C2—H2	120.4
C1—N1—C4	117.0 (3)	C4—C3—C2	118.6 (4)
C1—N1—Zn1	122.8 (3)	C4—C3—H3	120.7
C4—N1—Zn1	119.9 (3)	C2—C3—H3	120.7
C2—N2—C1	119.4 (4)	C3—C4—N1	124.0 (4)
C1—N3—H3A	117 (3)	C3—C4—H4	118.0
C1—N3—H3B	118 (3)	N1—C4—H4	118.0
H3A—N3—H3B	114 (4)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1ⁱⁱ	0.91 (2)	2.52 (3)	3.431 (4)	177 (5)
N3—H3B···Cl1	0.92 (2)	2.43 (3)	3.311 (4)	162 (4)
C2—H2···Cl1ⁱⁱⁱ	0.94	2.92	3.772 (5)	152

Symmetry codes: (ii) −x+3/2, y+1/2, z; (iii) x−1/2, −y+3/2, z−1.

Bis(2-aminopyrimidine-κN¹)diiodidozinc(II) (2) top

Crystal data top

[ZnI₂(C₄H₅N₃)₂]	F(000) = 944
M_r = 509.39	D_x = 2.282 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5469 (6) Å	Cell parameters from 8000 reflections
b = 15.3764 (13) Å	θ = 10.4–25.7°
c = 10.1518 (6) Å	µ = 5.81 mm⁻¹
β = 95.884 (7)°	T = 220 K
V = 1482.40 (18) Å³	Block, colorless
Z = 4	0.16 × 0.10 × 0.06 mm

Data collection top

Stoe IPDS-1 diffractometer	2946 reflections with I > 2σ(I)
Phi scans	R_int = 0.091
Absorption correction: numerical (X-Red and X-Shape; Stoe, 2008)	θ_max = 28.0°, θ_min = 2.4°
T_min = 0.296, T_max = 0.471	h = −12→12
14800 measured reflections	k = −20→20
3491 independent reflections	l = −13→13

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0549P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 1.17 e Å⁻³
3491 reflections	Δρ_min = −1.28 e Å⁻³
163 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0054 (4)
Primary atom site location: dual

Special details top

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

	x	y	z	U_iso*/U_eq
Zn1	0.75540 (4)	0.82087 (3)	0.75052 (5)	0.02767 (14)
I1	0.86634 (3)	0.67008 (2)	0.71225 (3)	0.03788 (12)
I2	0.83722 (3)	0.93595 (2)	0.59175 (3)	0.03509 (12)
N1	0.7972 (4)	0.8692 (2)	0.9389 (3)	0.0299 (7)
N2	0.9550 (5)	0.9284 (3)	1.1144 (5)	0.0474 (10)
N3	1.0345 (4)	0.8344 (3)	0.9503 (5)	0.0391 (9)
H3A	1.031 (5)	0.792 (2)	0.892 (4)	0.033 (13)*
H3B	1.113 (4)	0.837 (4)	1.006 (5)	0.049 (16)*
C1	0.9279 (4)	0.8763 (3)	1.0011 (4)	0.0293 (8)
C2	0.8455 (5)	0.9696 (3)	1.1649 (5)	0.0407 (10)
H2	0.861854	1.004769	1.240675	0.049*
C3	0.7096 (5)	0.9592 (4)	1.1032 (6)	0.0460 (11)
H3	0.632564	0.985892	1.137634	0.055*
C4	0.6905 (5)	0.9095 (3)	0.9917 (5)	0.0403 (10)
H4	0.598736	0.902899	0.949621	0.048*
N11	0.5413 (3)	0.8105 (2)	0.7281 (4)	0.0286 (7)
N12	0.3223 (4)	0.7503 (3)	0.7851 (5)	0.0480 (10)
N13	0.5463 (4)	0.7037 (3)	0.8897 (4)	0.0405 (9)
H13A	0.627117	0.693806	0.853657	0.061*
H13B	0.493126	0.664756	0.928267	0.061*
C11	0.4698 (4)	0.7547 (3)	0.8001 (4)	0.0296 (8)
C12	0.2495 (4)	0.8033 (3)	0.6940 (5)	0.0370 (10)
H12	0.150638	0.801076	0.681757	0.044*
C13	0.3224 (5)	0.8608 (3)	0.6193 (5)	0.0397 (10)
H13	0.273687	0.898093	0.557058	0.048*
C14	0.4642 (5)	0.8618 (3)	0.6384 (5)	0.0371 (9)
H14	0.512675	0.899989	0.586882	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0211 (2)	0.0315 (2)	0.0306 (3)	−0.00168 (16)	0.00331 (19)	0.00062 (17)
I1	0.02970 (17)	0.03171 (17)	0.0529 (2)	0.00108 (10)	0.00748 (13)	−0.00385 (11)
I2	0.03910 (19)	0.02980 (17)	0.03796 (19)	−0.00264 (10)	0.01170 (13)	0.00272 (10)
N1	0.0257 (16)	0.0353 (18)	0.0290 (18)	−0.0031 (13)	0.0035 (14)	−0.0019 (13)
N2	0.048 (2)	0.045 (2)	0.049 (3)	−0.0071 (18)	0.003 (2)	−0.0010 (18)
N3	0.0285 (19)	0.046 (2)	0.042 (2)	0.0032 (15)	−0.0006 (17)	−0.0062 (17)
C1	0.0274 (19)	0.0267 (19)	0.033 (2)	−0.0041 (14)	0.0008 (16)	0.0029 (15)
C2	0.049 (3)	0.036 (2)	0.037 (2)	−0.0031 (19)	0.006 (2)	−0.0065 (19)
C3	0.042 (3)	0.049 (3)	0.048 (3)	0.003 (2)	0.009 (2)	−0.013 (2)
C4	0.027 (2)	0.049 (3)	0.045 (3)	0.0028 (18)	0.0058 (19)	−0.012 (2)
N11	0.0200 (15)	0.0340 (17)	0.0314 (19)	−0.0005 (12)	0.0000 (14)	0.0044 (13)
N12	0.034 (2)	0.055 (3)	0.055 (3)	−0.0010 (17)	0.0069 (19)	0.000 (2)
N13	0.0268 (18)	0.050 (2)	0.044 (2)	−0.0027 (15)	0.0034 (16)	0.0186 (18)
C11	0.0246 (19)	0.034 (2)	0.031 (2)	−0.0015 (14)	0.0058 (16)	0.0016 (15)
C12	0.0203 (19)	0.052 (3)	0.038 (3)	0.0063 (17)	0.0002 (17)	−0.004 (2)
C13	0.034 (2)	0.043 (3)	0.040 (3)	0.0090 (18)	−0.0064 (19)	0.0030 (19)
C14	0.034 (2)	0.034 (2)	0.043 (3)	−0.0013 (17)	−0.0001 (19)	0.0050 (18)

Geometric parameters (Å, º) top

Zn1—N11	2.040 (3)	C3—H3	0.9400
Zn1—N1	2.052 (4)	C4—H4	0.9400
Zn1—I2	2.5686 (6)	N11—C11	1.356 (5)
Zn1—I1	2.5948 (6)	N11—C14	1.361 (6)
N1—C1	1.344 (5)	N12—C12	1.368 (6)
N1—C4	1.349 (6)	N12—C11	1.403 (6)
N2—C2	1.367 (7)	N13—C11	1.356 (6)
N2—C1	1.403 (6)	N13—H13A	0.9000
N3—C1	1.351 (6)	N13—H13B	0.9001
N3—H3A	0.876 (19)	C12—C13	1.396 (7)
N3—H3B	0.89 (2)	C12—H12	0.9400
C2—C3	1.391 (7)	C13—C14	1.348 (6)
C2—H2	0.9400	C13—H13	0.9400
C3—C4	1.363 (7)	C14—H14	0.9400

N11—Zn1—N1	103.25 (14)	N1—C4—C3	123.1 (4)
N11—Zn1—I2	110.46 (10)	N1—C4—H4	118.5
N1—Zn1—I2	107.01 (10)	C3—C4—H4	118.5
N11—Zn1—I1	109.47 (10)	C11—N11—C14	117.3 (4)
N1—Zn1—I1	114.82 (10)	C11—N11—Zn1	122.9 (3)
I2—Zn1—I1	111.50 (2)	C14—N11—Zn1	119.8 (3)
C1—N1—C4	118.6 (4)	C12—N12—C11	118.6 (4)
C1—N1—Zn1	123.4 (3)	C11—N13—H13A	104.5
C4—N1—Zn1	117.0 (3)	C11—N13—H13B	112.8
C2—N2—C1	119.2 (4)	H13A—N13—H13B	127.6
C1—N3—H3A	129 (4)	N11—C11—N13	117.5 (4)
C1—N3—H3B	111 (4)	N11—C11—N12	121.8 (4)
H3A—N3—H3B	115 (5)	N13—C11—N12	120.7 (4)
N1—C1—N3	118.8 (4)	N12—C12—C13	119.9 (4)
N1—C1—N2	121.0 (4)	N12—C12—H12	120.1
N3—C1—N2	120.2 (4)	C13—C12—H12	120.1
N2—C2—C3	119.5 (4)	C14—C13—C12	118.5 (4)
N2—C2—H2	120.3	C14—C13—H13	120.7
C3—C2—H2	120.3	C12—C13—H13	120.7
C4—C3—C2	118.5 (5)	C13—C14—N11	123.8 (4)
C4—C3—H3	120.7	C13—C14—H14	118.1
C2—C3—H3	120.7	N11—C14—H14	118.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···I1	0.88 (2)	2.96 (3)	3.742 (4)	150 (4)
N3—H3B···I1ⁱ	0.89 (2)	3.03 (2)	3.922 (4)	173 (5)
C2—H2···I2ⁱⁱ	0.94	3.31	3.982 (5)	130
C4—H4···N11	0.94	2.67	3.275 (6)	123
N13—H13A···I1	0.90	2.84	3.738 (4)	173
N13—H13B···I2ⁱⁱⁱ	0.90	2.81	3.693 (4)	169
C13—H13···I2^iv	0.94	3.10	4.001 (5)	162
C14—H14···I2	0.94	3.14	3.815 (5)	130

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+2, −z+2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x+1, −y+2, −z+1.

Acknowledgements

Financial support by the State of Schleswig-Holstein is gratefully acknowledged.

References

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Volume 82| Part 3| March 2026| Pages 300-304

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