Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021575/fj2016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021575/fj2016Isup2.hkl |
CCDC reference: 650542
Key indicators
- Single-crystal X-ray study
- T = 302 K
- Mean (C-C) = 0.008 Å
- R factor = 0.065
- wR factor = 0.174
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.05 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn1 - Cl1 .. 7.75 su PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT731_ALERT_1_C Bond Calc 0.87(6), Rep 0.87(2) ...... 3.00 su-Ra N1 -H1A 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.85(5), Rep 0.85(2) ...... 2.50 su-Ra N1 -H1B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.87(6), Rep 0.87(2) ...... 3.00 su-Ra N1 -H1A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.85(5), Rep 0.85(2) ...... 2.50 su-Ra N1 -H1B 1.555 1.555
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.85 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A solution of ZnCl2 (0.5 mmol) in ethanol (10 ml) and 2-aminopyrimidine (1.0 mmol) was stirred at room temperature for 12 h and then filtered. The filtrate was kept at room temperature in the dark for two weeks, affording white crystals of (I). The crystals were isolated, washed three times with ethanol and dried in a vacuum desiccator using anhydrous CaCl2. Analysis calculated for C8N6H10 Zn Cl2: C 29.43, N 25.74, H 3.09%; found: C 29.11, N 25.34,H 3.22%.
The H atoms bonded to the C atoms were placed in calculated positions, and were allowed to ride on their parent atoms, with a C—H distance of 0.93 Å for aromatic H atoms and Uiso(H) = 1.2 times of its parent atom. The H atom positions of the NH2 group were obtained from a Fourier difference map and were refined with a restrained N—H distance of 0.86 (0.02) Å. The isotropic displacement parameters were set equal to 1.2Ueq(parent atom). The highest and lowest residual density peaks are 0.94 Å and 0.77 Å respectively from the Zn atom.
Aminopyrimidine is an active component of antibiotics, antimicrobials, anticonvulsants, antispasmatics, antineoplastics and antidiabetogenics, and many derivatives have been used in seed dressings, crop-disease control and veterinary drugs etc (Cookson et al., 1993, Katritzky et al., 1984, Santra et al., 1999). In coordination chemistry, the meta-related nitrogen in pyrimidine has played an important role in connecting different metal atoms, transmitting antiferromagnetic interactions and for obtaining magnetic systems of high nuclearity (Munno et la, 1998; Groen et al., 1998). Because of the peripheral N heteroatom, the excited state of the pyrimidine moiety undergoes protonation in aqueous solution and the complexes exhibit proton-dependent photophysics and photochemistry. Recently, the design of molecular architecture with aminopyrimidine and bipyrimidine has aroused interest in the fields of coordination, bioinorganic and magnetochemistry (Arwaroli,1997). We report here a new bichlorobis(2-aminopyrimidine) zinc(II) complex(I), (C4H5N3)2ZnCl2.
In the crystal structure of the title complex(I), the ZnII atom lies on a twofold rotation axis, the asymmetric unit is composed of a ZnII ion, two 2-aminopyrimidine ligands and two Cl anions. The molecular structure of (I) is shown in Fig. 1. The ZnII ion is four-coordinated in an approximately tetrahedral environment by two N atoms[N2 and N2i; symmetry code: (i) x- 1, y- 1, z] of two 2-aminopyrimidine ligands and two Cl anions [Cl1 and Cl1i]. The bond distances and angles around the zinc atoms are quite normal. [Zn—N 2.056 (2)Å and Zn—Cl 2.249 (3) Å].
The 2-aminopyrimidine molecules are planar within experimental error (pyrimidine ring the greatest deviation C3 within 0.0119 (3) Å)) and the amino N atoms lie approximately in the corresponding molecular planes (N1 off of the pyrimidine ring plane within 0.0183 (3) Å). The bond distances and angles of the 2-aminopyrimidine ligand are similar to those found in other complexes (Kennard et al., 1985; Etter et al., 1990; Zanchini et al., 1990;Lumme et al., 1996).
A large number of N—H···N hydrogen bonds and N—H···Cl hydrogen bonds (Table 2) help to establish the crystal packing. The N—H···N hydrogen bonds bind the complex molecules to form a one-dimensional supramolecular structure along the c axis. The supramolecular chains are parallel to each other and the N—H···Cl hydrogen bonds link them into a two-dimensional network into the ac plane. There are only weaker van der Waals interactions in the b axis (Fig.2).
For related literature, see: Arwaroli et al. (1997); Cookson & Tiekink (1993); Etter et al. (1990); Groen et al. (1998); Katritzky et al. (1984); Kennard et al. (1985); Lumme et al. (1996); Munno et al. (1998); Santra et al. (1999); Zanchini & Willett (1990).
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 19907a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
[ZnCl2(C4H5N3)2] | F(000) = 656 |
Mr = 326.49 | Dx = 1.716 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2860 reflections |
a = 10.744 (4) Å | θ = 2.0–28.3° |
b = 13.454 (5) Å | µ = 2.35 mm−1 |
c = 8.806 (3) Å | T = 302 K |
β = 97.012 (6)° | Block, white |
V = 1263.4 (8) Å3 | 0.28 × 0.18 × 0.16 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 1378 independent reflections |
Radiation source: fine-focus sealed tube | 1140 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
φ and ω scans | θmax = 27.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.512, Tmax = 0.685 | k = −17→17 |
4933 measured reflections | l = −11→11 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0993P)2 + 1.9733P] where P = (Fo2 + 2Fc2)/3 |
1378 reflections | (Δ/σ)max = 0.002 |
84 parameters | Δρmax = 1.35 e Å−3 |
2 restraints | Δρmin = −0.66 e Å−3 |
[ZnCl2(C4H5N3)2] | V = 1263.4 (8) Å3 |
Mr = 326.49 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.744 (4) Å | µ = 2.35 mm−1 |
b = 13.454 (5) Å | T = 302 K |
c = 8.806 (3) Å | 0.28 × 0.18 × 0.16 mm |
β = 97.012 (6)° |
Siemens SMART CCD area-detector diffractometer | 1378 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1140 reflections with I > 2σ(I) |
Tmin = 0.512, Tmax = 0.685 | Rint = 0.045 |
4933 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 2 restraints |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 1.35 e Å−3 |
1378 reflections | Δρmin = −0.66 e Å−3 |
84 parameters |
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 > 2σ(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 | ||
Zn1 | 0.0000 | 0.24505 (6) | 0.2500 | 0.0411 (3) | |
C1 | 0.0696 (5) | 0.3725 (4) | −0.0120 (5) | 0.0419 (11) | |
C2 | 0.2323 (5) | 0.3378 (4) | 0.1742 (6) | 0.0494 (13) | |
H2 | 0.2627 | 0.3089 | 0.2673 | 0.059* | |
C3 | 0.3158 (6) | 0.3857 (5) | 0.0918 (7) | 0.0586 (15) | |
H3 | 0.4001 | 0.3929 | 0.1291 | 0.070* | |
C4 | 0.2666 (5) | 0.4222 (4) | −0.0492 (6) | 0.0521 (13) | |
H4 | 0.3210 | 0.4522 | −0.1099 | 0.063* | |
Cl1 | −0.12680 (12) | 0.15173 (10) | 0.08506 (13) | 0.0479 (4) | |
N1 | −0.0526 (4) | 0.3712 (4) | −0.0641 (5) | 0.0553 (12) | |
H1A | −0.108 (5) | 0.340 (4) | −0.018 (7) | 0.066* | |
H1B | −0.088 (5) | 0.404 (4) | −0.140 (5) | 0.066* | |
N2 | 0.1090 (4) | 0.3313 (3) | 0.1258 (4) | 0.0403 (9) | |
N3 | 0.1469 (4) | 0.4169 (3) | −0.1027 (5) | 0.0491 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0449 (5) | 0.0541 (6) | 0.0248 (4) | 0.000 | 0.0067 (3) | 0.000 |
C1 | 0.056 (3) | 0.047 (3) | 0.025 (2) | 0.001 (2) | 0.0112 (19) | −0.0044 (17) |
C2 | 0.052 (3) | 0.065 (3) | 0.030 (2) | −0.005 (2) | 0.002 (2) | −0.003 (2) |
C3 | 0.052 (3) | 0.077 (4) | 0.047 (3) | −0.020 (3) | 0.003 (2) | −0.003 (3) |
C4 | 0.058 (3) | 0.057 (3) | 0.044 (3) | −0.013 (2) | 0.020 (2) | −0.006 (2) |
Cl1 | 0.0497 (8) | 0.0568 (8) | 0.0362 (6) | −0.0088 (5) | 0.0012 (5) | −0.0068 (5) |
N1 | 0.047 (3) | 0.083 (4) | 0.037 (2) | 0.005 (2) | 0.0075 (19) | 0.013 (2) |
N2 | 0.046 (2) | 0.052 (2) | 0.0238 (18) | −0.0043 (18) | 0.0078 (15) | −0.0017 (15) |
N3 | 0.062 (3) | 0.057 (3) | 0.030 (2) | −0.007 (2) | 0.0117 (19) | −0.0010 (17) |
Zn1—N2 | 2.056 (4) | C2—C3 | 1.380 (8) |
Zn1—N2i | 2.056 (4) | C2—H2 | 0.9300 |
Zn1—Cl1 | 2.2492 (13) | C3—C4 | 1.380 (8) |
Zn1—Cl1i | 2.2492 (13) | C3—H3 | 0.9300 |
C1—N1 | 1.337 (7) | C4—N3 | 1.316 (7) |
C1—N2 | 1.355 (6) | C4—H4 | 0.9300 |
C1—N3 | 1.358 (6) | N1—H1A | 0.87 (2) |
C2—N2 | 1.344 (6) | N1—H1B | 0.85 (2) |
N2—Zn1—N2i | 111.3 (2) | C4—C3—H3 | 122.0 |
N2—Zn1—Cl1 | 108.13 (11) | C2—C3—H3 | 122.0 |
N2i—Zn1—Cl1 | 108.59 (12) | N3—C4—C3 | 123.5 (5) |
N2—Zn1—Cl1i | 108.59 (12) | N3—C4—H4 | 118.2 |
N2i—Zn1—Cl1i | 108.13 (11) | C3—C4—H4 | 118.2 |
Cl1—Zn1—Cl1i | 112.13 (8) | C1—N1—H1A | 123 (4) |
N1—C1—N2 | 119.2 (4) | C1—N1—H1B | 126 (4) |
N1—C1—N3 | 116.7 (4) | H1A—N1—H1B | 111 (6) |
N2—C1—N3 | 124.0 (5) | C2—N2—C1 | 116.5 (4) |
N2—C2—C3 | 122.9 (5) | C2—N2—Zn1 | 118.2 (3) |
N2—C2—H2 | 118.6 | C1—N2—Zn1 | 124.8 (3) |
C3—C2—H2 | 118.6 | C4—N3—C1 | 117.1 (4) |
C4—C3—C2 | 115.9 (5) | ||
N2—C2—C3—C4 | −3.6 (8) | Cl1—Zn1—N2—C2 | −134.8 (3) |
C2—C3—C4—N3 | 2.9 (9) | Cl1i—Zn1—N2—C2 | −12.9 (4) |
C3—C2—N2—C1 | 1.5 (8) | N2i—Zn1—N2—C1 | −82.6 (4) |
C3—C2—N2—Zn1 | 173.6 (4) | Cl1—Zn1—N2—C1 | 36.6 (4) |
N1—C1—N2—C2 | −177.9 (5) | Cl1i—Zn1—N2—C1 | 158.5 (4) |
N3—C1—N2—C2 | 1.6 (7) | C3—C4—N3—C1 | −0.1 (8) |
N1—C1—N2—Zn1 | 10.6 (7) | N1—C1—N3—C4 | 177.2 (5) |
N3—C1—N2—Zn1 | −169.9 (4) | N2—C1—N3—C4 | −2.3 (7) |
N2i—Zn1—N2—C2 | 106.0 (4) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.87 (2) | 2.70 (5) | 3.367 (5) | 134 (5) |
N1—H1B···N3ii | 0.85 (2) | 2.28 (4) | 3.048 (6) | 149 (6) |
Symmetry code: (ii) −x, y, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C4H5N3)2] |
Mr | 326.49 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 302 |
a, b, c (Å) | 10.744 (4), 13.454 (5), 8.806 (3) |
β (°) | 97.012 (6) |
V (Å3) | 1263.4 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.35 |
Crystal size (mm) | 0.28 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.512, 0.685 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4933, 1378, 1140 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.174, 1.14 |
No. of reflections | 1378 |
No. of parameters | 84 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.35, −0.66 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 19907a), SHELXL97 (Sheldrick, 1997a), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.87 (2) | 2.70 (5) | 3.367 (5) | 134 (5) |
N1—H1B···N3i | 0.85 (2) | 2.28 (4) | 3.048 (6) | 149 (6) |
Symmetry code: (i) −x, y, −z−1/2. |
Aminopyrimidine is an active component of antibiotics, antimicrobials, anticonvulsants, antispasmatics, antineoplastics and antidiabetogenics, and many derivatives have been used in seed dressings, crop-disease control and veterinary drugs etc (Cookson et al., 1993, Katritzky et al., 1984, Santra et al., 1999). In coordination chemistry, the meta-related nitrogen in pyrimidine has played an important role in connecting different metal atoms, transmitting antiferromagnetic interactions and for obtaining magnetic systems of high nuclearity (Munno et la, 1998; Groen et al., 1998). Because of the peripheral N heteroatom, the excited state of the pyrimidine moiety undergoes protonation in aqueous solution and the complexes exhibit proton-dependent photophysics and photochemistry. Recently, the design of molecular architecture with aminopyrimidine and bipyrimidine has aroused interest in the fields of coordination, bioinorganic and magnetochemistry (Arwaroli,1997). We report here a new bichlorobis(2-aminopyrimidine) zinc(II) complex(I), (C4H5N3)2ZnCl2.
In the crystal structure of the title complex(I), the ZnII atom lies on a twofold rotation axis, the asymmetric unit is composed of a ZnII ion, two 2-aminopyrimidine ligands and two Cl anions. The molecular structure of (I) is shown in Fig. 1. The ZnII ion is four-coordinated in an approximately tetrahedral environment by two N atoms[N2 and N2i; symmetry code: (i) x- 1, y- 1, z] of two 2-aminopyrimidine ligands and two Cl anions [Cl1 and Cl1i]. The bond distances and angles around the zinc atoms are quite normal. [Zn—N 2.056 (2)Å and Zn—Cl 2.249 (3) Å].
The 2-aminopyrimidine molecules are planar within experimental error (pyrimidine ring the greatest deviation C3 within 0.0119 (3) Å)) and the amino N atoms lie approximately in the corresponding molecular planes (N1 off of the pyrimidine ring plane within 0.0183 (3) Å). The bond distances and angles of the 2-aminopyrimidine ligand are similar to those found in other complexes (Kennard et al., 1985; Etter et al., 1990; Zanchini et al., 1990;Lumme et al., 1996).
A large number of N—H···N hydrogen bonds and N—H···Cl hydrogen bonds (Table 2) help to establish the crystal packing. The N—H···N hydrogen bonds bind the complex molecules to form a one-dimensional supramolecular structure along the c axis. The supramolecular chains are parallel to each other and the N—H···Cl hydrogen bonds link them into a two-dimensional network into the ac plane. There are only weaker van der Waals interactions in the b axis (Fig.2).