*3.2. Crystal Structures of Compounds 6 and 7*

Compounds **6** and **7** both crystallized in the monoclinic system, with a P21/c space group and Cc space group, respectively. The molecular structures of compounds **6** and **7** are described in Figure 2a,b, and selected molecular structure parameters, including bond lengths and bond angles for compound **6** and **7,** are listed in Tables 2 and 3, respectively. Packing diagrams of compounds **6** and **7** are shown in Figure 3a,b respectively.

The selected bond lengths and bond angles of the phenyl ring and pyrimidine ring in the crystal structure of compounds **6** and **7** are similar to those of compounds reported in the literature, which are in accordance with normal ranges [29–32]. According to the data in Figure 2a, compound **6** is composed of four molecular moieties (two phenyl rings, a chlorine-substituted pyrimidine ring, and a (*Z*)-methyl 2-iodo-3-methoxyacrylate group). The phenyl ring, formed by C(16)–C(17)–C(18)– C(19)–C(20)–C(21), and the pyrimidine ring, formed by C(15)–N(2)–C(14)–C(13)– C(12)–N(1), are linked by a C(15)–C(16) bridge. The bond length of C(15)–C(16), a single bond, is 1.556(5) Å, and the torsion angle of N(2)−C(15)−C(16) is 119.8(3) Å. The phenyl ring, defined as C(1)–C(2)–C(3)–C(4)– C(5)–C(6), and the pyrimidine ring, are linked by an oxygen atom. The bond angle of C(12)−O(1)−C(1) is 115.3(3) Å. The acrylate moiety assumes an *E* configuration double bond C(7)=C(10) (1.391(6) Å) of the vinyl group. The bond lengths of C(8)–O(3) in the acrylate group are 1.229(6) Å, which is similar to the general length reported for C=O, indicating that it is a double bond [33–35]. The dihedral angles between the mean planes of C(15), N(2), C(14), C(13), C(12), N(1) with C(16), C(17), C(18), C(19), C(20), C(21), C (19) and C(1), C(2), C(3), C(4), C(5), C(6) are 3.368(109)◦ and 66.294(120)◦ , respectively.

Compound **7** is composed of a chlorine-substituted pyrimidine ring and two phenyl rings (Figure 2b). The phenyl ring, formed by C(1)–C(2)–C(3)–C(4)–C(5)–C(6), is linked with the pyrimidine ring, formed by C(7)–N(1)–C(8)–C(9)–C(10)–N(2) via a C(1)–C(7) bridge. The bond length of C(1)–C(7) is 1.482(4) Å and the torsion angle of N(2)−C(7)−C(1) is 117.3(2) Å. The pyrimidine ring above and phenyl ring defined as C(11)–C(12)–C(13)–C(14)–C(15)–C(16) are linked by a nitrogen atom, with a torsion angle C(10)−N(3)−C(11) of 126.5(2) Å. The dihedral angles between the mean planes of C(7), N(1), C(8), C(9), C(10), N(2) with C(1), C(2), C(3), C(4), C(5), C(6)and C(11), C(12), C(13), C(14), C(15), C(16) are 8.447(74)◦ and 45.236(88)◦ , respectively.

Based on whole structural analysis, molecule **6,** forms C–H···N (symmetry code: 1 − x, 1 − y, 1 − z) and C–H···O hydrogen bonding interactions (symmetry code: 1 + x, y, z) with the phenyl C atom (Table 4), to from three-dimensional networks. The C···N distances between donor (D) and acceptor (A) molecules were 3.341(6) Å for C(5)–H(5)···N(2), and 2.8711(16) Å for C(11)–H(11B)···O(3), respectively. The distances between hydrogen atom and acceptor atom were 2.53 Å for H(5)···N(2), and 2.30 Å for H(11B)···O(3), respectively. Both of the bond lengths were shorter than sum of van der Waals radii (2.66 Å for H(5)···N(2) and 2.63 Å for H(11B)···O(3)) [36]. As shown in Table 5, N(3)–H(3)···N(1) hydrogen bonds (N···N 3.190(3) Å,N–H···N 146◦ ; symmetry code: <sup>1</sup> 2 + x, −1/2 − y, <sup>1</sup> 2 + z) link the neighboring molecules of compound **7** to form a three-dimensional framework. Weak hydrogen bonds C(2)–H(2)···N(1), C(6)–H(6)···N(2), and C(12)–H(12)···N(2) also stabilize the crystal structure. *Crystals* **2020**, *10*, x FOR PEER REVIEW 7 of 13

**Figure 2.** Crystal structure of compound **6 (2a**) and **7** (2**b**). **Figure 2.** Crystal structure of compound **6** (2**a**) and **7** (2**b**).

The selected bond lengths and bond angles of the phenyl ring and pyrimidine ring in the crystal structure of compounds **6** and **7** are similar to those of compounds reported in the literature, which are in accordance with normal ranges [29–32]. According to the data in Figure 2a, compound **6** is composed of four molecular moieties (two phenyl rings, a chlorine-substituted pyrimidine ring, and

torsion angle of N(2)−C(15)−C(16) is 119.8(3) Å. The phenyl ring, defined as C(1)–C(2)–C(3)–C(4)– C(5)–C(6), and the pyrimidine ring, are linked by an oxygen atom. The bond angle of C(12)−O(1)−C(1) is 115.3(3) Å . The acrylate moiety assumes an *E* configuration double bond C(7)=C(10) (1.391(6) Å ) of the vinyl group. The bond lengths of C(8)–O(3) in the acrylate group are 1.229(6) Å , which is similar to the general length reported for C=O, indicating that it is a double bond


**Table 2.** Selected bond lengths (Å) and bond angles (◦ ) for compound **6**.

**Table 3.** Selected bond lengths (Å) and bond angles (◦ ) for compound **7.**


C(16)−C(11)−C(12) 119.6(3) N(3)−C(10)−C(9) 119.5(2) C(12)−C(11)−N(3) 121.9(2) N(2)−C(10)−N(3) 119.4(2) C(15)−C(16)−C(11) 120.3(3) N(2)−C(10)−C(9) 121.1(2) C(2)−C(1)−C(7) 120.7(2) C(3)−C(2)−C(1) 120.7(3) C(2)−C(1)−C(6) 118.6(3) C(2)−C(3)−C(4) 120.2(3) C(6)−C(1)−C(7) 120.7(2) C(5)−C(6)−C1) 120.6(3)

**(a)**

**(b)**

**Figure 3.** Packing diagram of compound **6 (3a**) and **7 (3b**). Dashed lines represent hydrogen bonds. **Figure 3.** Packing diagram of compound **6 (3a**) and **7 (3b**). Dashed lines represent hydrogen bonds.

Based on whole structural analysis, molecule **6,** forms C–H···N (symmetry code: 1 − x, 1 − y, 1 − **Table 4.** Hydrogen bonding interactions in compound **7**.


and 2.30 Å for H(11B)···O(3), respectively. Both of the bond lengths were shorter than sum of van der Waals radii (2.66 Å for H(5)···N(2) and 2.63 Å for H(11B)···O(3)) [36]. As shown in Table 5, Symmetry transformations used to generate the equivalent atoms: #1: 1 − x, 1 − y, 1 − z; #2: 1 + x, y, z.

N(3)–H(3)···N(1) hydrogen bonds (N···N 3.190(3) Å ,N–H···N 146°; symmetry code: ½ + x, −1/2 − y, ½ **Table 5.** Hydrogen bonding interactions in compound **6**.


Symmetry transformations used to generate the equivalent atoms: <sup>1</sup> 2 + x, −1/2 − y, <sup>1</sup> 2 + z.
