Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680100592X/na6068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680100592X/na6068Isup2.hkl |
CCDC reference: 165630
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.017
- wR factor = 0.053
- Data-to-parameter ratio = 9.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.812 0.993 Tmin and Tmax expected: 0.400 0.675 RR = 1.380 Please check that your absorption correction is appropriate. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.679 Tmax scaled 0.675 Tmin scaled 0.552 REFLT_03 From the CIF: _diffrn_reflns_theta_max 24.97 From the CIF: _reflns_number_total 933 Count of symmetry unique reflns 933 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Colourless single crystals of the title complex were grown as transparent needles from a saturated aqueous solution containing sarcosine and zinc chloride in a stoichiometric ratio.
H atoms were placed at calculated positions and were allowed to ride on their respective parent atoms using SHELXL97 (Sheldrick, 1997) defaults. The positions of the water H atoms were calculated using HYDROGEN (Nardelli, 1999), with O—H = 0.85 Å, H—O—H = 107° and U(H)eq= 1.2Ueq of the parent atoms, and were not included in the refinement.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
[ZnCl3(C3H8NO2)]·H2O | F(000) = 280 |
Mr = 279.84 | Dx = 1.894 Mg m−3 Dm = 1.90 (3) Mg m−3 Dm measured by floatation in a mixture of carbon tetrachloride and bromoform |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6181 (12) Å | Cell parameters from 1017 reflections |
b = 7.4989 (11) Å | θ = 6–15° |
c = 9.900 (4) Å | µ = 3.28 mm−1 |
β = 92.62 (2)° | T = 293 K |
V = 490.8 (2) Å3 | Plates, colourless |
Z = 2 | 0.38 × 0.24 × 0.12 mm |
Enraf-Nonius sealed tube diffractometer | 913 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.008 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω–2θ scans | h = 0→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→8 |
Tmin = 0.812, Tmax = 0.993 | l = −11→11 |
1017 measured reflections | 2 standard reflections every 200 reflections |
933 independent reflections | intensity decay: 0.1% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0239P)2 + 0.1562P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.053 | (Δ/σ)max < 0.001 |
S = 1.28 | Δρmax = 0.30 e Å−3 |
933 reflections | Δρmin = −0.24 e Å−3 |
101 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.051 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.010 (18) |
[ZnCl3(C3H8NO2)]·H2O | V = 490.8 (2) Å3 |
Mr = 279.84 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6181 (12) Å | µ = 3.28 mm−1 |
b = 7.4989 (11) Å | T = 293 K |
c = 9.900 (4) Å | 0.38 × 0.24 × 0.12 mm |
β = 92.62 (2)° |
Enraf-Nonius sealed tube diffractometer | 913 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.008 |
Tmin = 0.812, Tmax = 0.993 | 2 standard reflections every 200 reflections |
1017 measured reflections | intensity decay: 0.1% |
933 independent reflections |
R[F2 > 2σ(F2)] = 0.017 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.053 | Δρmax = 0.30 e Å−3 |
S = 1.28 | Δρmin = −0.24 e Å−3 |
933 reflections | Absolute structure: Flack (1983) |
101 parameters | Absolute structure parameter: 0.010 (18) |
1 restraint |
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 > σ(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 | 0.67915 (6) | 0.40483 (7) | 0.26537 (4) | 0.02369 (18) | |
Cl1 | 0.86420 (18) | 0.66062 (16) | 0.26939 (12) | 0.0336 (3) | |
Cl2 | 0.37724 (17) | 0.45863 (16) | 0.15902 (13) | 0.0368 (3) | |
Cl3 | 0.64383 (18) | 0.30575 (18) | 0.47779 (12) | 0.0374 (3) | |
O1 | 0.8288 (5) | 0.2418 (4) | 0.1452 (3) | 0.0281 (7) | |
O2 | 1.0144 (5) | 0.1081 (5) | 0.3096 (3) | 0.0294 (7) | |
H1 | 1.1007 | 0.1815 | 0.3336 | 0.044* | |
N1 | 1.2102 (5) | −0.1049 (7) | 0.1347 (4) | 0.0318 (8) | |
H1A | 1.2284 | −0.1872 | 0.0703 | 0.038* | |
H1B | 1.1574 | −0.1611 | 0.2053 | 0.038* | |
C1 | 0.9639 (6) | 0.1327 (6) | 0.1911 (4) | 0.0213 (9) | |
C2 | 1.0611 (7) | 0.0262 (7) | 0.0814 (5) | 0.0318 (11) | |
H2A | 0.9562 | −0.0360 | 0.0284 | 0.038* | |
H2B | 1.1275 | 0.1076 | 0.0216 | 0.038* | |
C3 | 1.4107 (7) | −0.0335 (7) | 0.1794 (6) | 0.0383 (12) | |
H3A | 1.4655 | 0.0341 | 0.1072 | 0.057* | |
H3B | 1.5001 | −0.1304 | 0.2032 | 0.057* | |
H3C | 1.3966 | 0.0423 | 0.2565 | 0.057* | |
O1W | 0.1661 (4) | 0.4117 (6) | 0.4685 (3) | 0.0297 (6) | |
H1W | 0.0981 | 0.3789 | 0.5349 | 0.036* | |
H2W | 0.2062 | 0.5186 | 0.4851 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0218 (3) | 0.0221 (3) | 0.0272 (3) | 0.0014 (2) | 0.00139 (16) | 0.0002 (2) |
Cl1 | 0.0324 (6) | 0.0266 (6) | 0.0423 (6) | −0.0071 (5) | 0.0061 (5) | −0.0030 (5) |
Cl2 | 0.0278 (6) | 0.0390 (8) | 0.0426 (6) | 0.0047 (4) | −0.0079 (5) | 0.0031 (5) |
Cl3 | 0.0374 (6) | 0.0450 (8) | 0.0305 (6) | 0.0116 (6) | 0.0085 (5) | 0.0086 (5) |
O1 | 0.0320 (17) | 0.0245 (16) | 0.0280 (16) | 0.0076 (14) | 0.0032 (13) | 0.0010 (14) |
O2 | 0.0337 (18) | 0.0299 (17) | 0.0250 (17) | 0.0040 (14) | 0.0031 (13) | −0.0014 (14) |
N1 | 0.0332 (19) | 0.0196 (18) | 0.043 (2) | 0.003 (2) | 0.0091 (15) | −0.002 (2) |
C1 | 0.022 (2) | 0.018 (2) | 0.025 (2) | −0.0030 (17) | 0.0043 (16) | −0.0023 (17) |
C2 | 0.035 (2) | 0.032 (3) | 0.028 (2) | 0.010 (2) | 0.0010 (19) | −0.007 (2) |
C3 | 0.028 (2) | 0.041 (3) | 0.046 (3) | 0.002 (2) | 0.005 (2) | −0.002 (2) |
O1W | 0.0319 (15) | 0.0305 (15) | 0.0268 (14) | −0.0015 (18) | 0.0032 (11) | −0.0016 (18) |
Zn1—O1 | 1.999 (3) | N1—H1B | 0.9000 |
Zn1—Cl2 | 2.2519 (13) | C1—C2 | 1.515 (6) |
Zn1—Cl3 | 2.2525 (14) | C2—H2A | 0.9700 |
Zn1—Cl1 | 2.2751 (13) | C2—H2B | 0.9700 |
O1—C1 | 1.280 (5) | C3—H3A | 0.9600 |
O2—C1 | 1.219 (5) | C3—H3B | 0.9600 |
O2—H1 | 0.8200 | C3—H3C | 0.9600 |
N1—C2 | 1.473 (6) | O1W—H1W | 0.850 (3) |
N1—C3 | 1.480 (6) | O1W—H2W | 0.857 (4) |
N1—H1A | 0.9000 | ||
O1—Zn1—Cl2 | 106.53 (10) | O2—C1—C2 | 120.2 (4) |
O1—Zn1—Cl3 | 115.41 (10) | O1—C1—C2 | 113.3 (4) |
Cl2—Zn1—Cl3 | 111.58 (5) | N1—C2—C1 | 113.2 (4) |
O1—Zn1—Cl1 | 104.18 (10) | N1—C2—H2A | 108.9 |
Cl2—Zn1—Cl1 | 108.82 (5) | C1—C2—H2A | 108.9 |
Cl3—Zn1—Cl1 | 109.91 (5) | N1—C2—H2B | 108.9 |
C1—O1—Zn1 | 122.5 (3) | C1—C2—H2B | 108.9 |
C1—O2—H1 | 109.5 | H2A—C2—H2B | 107.7 |
C2—N1—C3 | 116.3 (4) | N1—C3—H3A | 109.5 |
C2—N1—H1A | 108.2 | N1—C3—H3B | 109.5 |
C3—N1—H1A | 108.2 | H3A—C3—H3B | 109.5 |
C2—N1—H1B | 108.2 | N1—C3—H3C | 109.5 |
C3—N1—H1B | 108.2 | H3A—C3—H3C | 109.5 |
H1A—N1—H1B | 107.4 | H3B—C3—H3C | 109.5 |
O2—C1—O1 | 126.5 (4) | H1W—O1W—H2W | 107.0 (3) |
Cl2—Zn1—O1—C1 | −152.6 (3) | Zn1—O1—C1—C2 | −178.5 (3) |
Cl3—Zn1—O1—C1 | −28.2 (3) | C3—N1—C2—C1 | −77.7 (5) |
Cl1—Zn1—O1—C1 | 92.4 (3) | O2—C1—C2—N1 | 1.4 (6) |
Zn1—O1—C1—O2 | 2.7 (6) | O1—C1—C2—N1 | −177.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1Wi | 0.82 | 2.21 | 2.919 (5) | 144 |
N1—H1A···O1ii | 0.90 | 2.21 | 3.001 (5) | 146 |
N1—H1B···O2 | 0.90 | 2.48 | 2.726 (5) | 96 |
N1—H1B···Cl1iii | 0.90 | 2.46 | 3.224 (4) | 142 |
O1W—H1W···O2iv | 0.85 | 2.45 | 2.943 (5) | 118 |
O1W—H1W···Cl1v | 0.85 | 2.54 | 3.220 (4) | 138 |
O1W—H2W···Cl3iv | 0.86 | 2.39 | 3.246 (4) | 173 |
C2—H2A···Cl2vi | 0.97 | 2.82 | 3.702 (5) | 152 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+1; (v) −x+1, y−1/2, −z+1; (vi) −x+1, y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl3(C3H8NO2)]·H2O |
Mr | 279.84 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6181 (12), 7.4989 (11), 9.900 (4) |
β (°) | 92.62 (2) |
V (Å3) | 490.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.28 |
Crystal size (mm) | 0.38 × 0.24 × 0.12 |
Data collection | |
Diffractometer | Enraf-Nonius sealed tube diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.812, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1017, 933, 913 |
Rint | 0.008 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.053, 1.28 |
No. of reflections | 933 |
No. of parameters | 101 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.24 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.010 (18) |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
O1—Zn1—Cl2 | 106.53 (10) | C2—N1—C3 | 116.3 (4) |
O1—Zn1—Cl3 | 115.41 (10) | O2—C1—O1 | 126.5 (4) |
Cl2—Zn1—Cl3 | 111.58 (5) | O2—C1—C2 | 120.2 (4) |
O1—Zn1—Cl1 | 104.18 (10) | O1—C1—C2 | 113.3 (4) |
Cl2—Zn1—Cl1 | 108.82 (5) | N1—C2—C1 | 113.2 (4) |
Cl3—Zn1—Cl1 | 109.91 (5) | ||
C3—N1—C2—C1 | −77.7 (5) | O1—C1—C2—N1 | −177.5 (4) |
O2—C1—C2—N1 | 1.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1Wi | 0.82 | 2.21 | 2.919 (5) | 144 |
N1—H1A···O1ii | 0.90 | 2.21 | 3.001 (5) | 146 |
N1—H1B···O2 | 0.90 | 2.48 | 2.726 (5) | 96 |
N1—H1B···Cl1iii | 0.90 | 2.46 | 3.224 (4) | 142 |
O1W—H1W···O2iv | 0.85 | 2.45 | 2.943 (5) | 118 |
O1W—H1W···Cl1v | 0.85 | 2.54 | 3.220 (4) | 138 |
O1W—H2W···Cl3iv | 0.86 | 2.39 | 3.246 (4) | 173 |
C2—H2A···Cl2vi | 0.97 | 2.82 | 3.702 (5) | 152 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, y−1/2, −z; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+1; (v) −x+1, y−1/2, −z+1; (vi) −x+1, y−1/2, −z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Sarcosine (N-methylglycine, CH3NH2+CH2COO-), an α-amino acid present in several biologically important compounds, forms a number of addition compounds with inorganic acids and salts besides forming metallic complexes. The crystal structure of sarcosine itself was determined earlier in our laboratory (Mostad & Natarajan, 1989). The present study reports the crystal structure of a complex of sarcosine with ZnCl2, namely trichloro(sarcosinio)zinc(II) monohydrate, (I).
The sarcosine molecule exists in the cationic form with a positively charged amino group and a protonated carboxylic acid group. In the cases of complexes with metallic salts, the amino acid normally remains as a zwitterion. The formation of the zinc complex observed in the crystals may be justified by a complex series of hydrolytic equilibria involving the solvent water molecules, the Cl- ions and the sarcosine zwitterion. In the three other crystal structures of amino acid complexes with ZnCl2 known so far, amino acid molecules exist as zwitterions in glycine with ZnCl2 (Hariharan et al., 1989) and L-proline with ZnCl2 (Yukawa et al., 1985) and adopts a cationic form in L-histidine with ZnCl2 (Foster et al., 1993).
In Fig. 1, the molecular structure and the atom-numbering scheme adopted is shown. The molecular main chain deviates from planarity, the C3—N1—C2—C1 torsion angle (Table 1) indicating that the C3—N1 bond is synclinal to C2—C1. Similar observations have been made in the structures of sarcosine cadmium chloride (Krishnakumar & Natarajan, 1996), sarcosine telluric acid adduct (Averbuch-pouchot, 1988) and sarcosinium tartrate (Krishnakumar et al., 2001). C3—N1 is antiperiplanar to C2—C1 in the crystal structure of sarcosine (Mostad & Natarajan, 1989), sarcosine barium chloride (Krishnakumar et al., 1995), sarcosine sucrose (Krishnakumar & Natarajan et al., 1995), sarcosine oxalic acid monohydrate (Krishnakumar et al., 1999) and diaquabis(sarcosinato)copper(II) (Krishnakumar et al., 1994). The value of the O1—C1—O2—H1 torsion angle is -85.6°. This unusual value observed may be justified by the fact that the position of the hydrogen (H1) is determined by the two hydrogen bonds O2—H1···O1Wi (intermolecular) and N1—H1B···O2 (intramolecular), in which O2 is involved [symmetry code: (i) x + 1, y, z]. It is important to notice that both these hydrogen bonds justify the cationic status of the coordinating amino-acid ligand (see Table 2). It is interesting to notice also that the C1—O1 bond distance is remarkably longer than C1—O2 (Δ/σ = 10.25) (see Table 1), when usually in carboxylic acids, the contrary is observed [sp2═O = 1.214 (19) Å and Csp2—OH = 1.308 (19) Å; Allen et al., 1987] and is justified by the coordination of O1 to metal and the hydrogen bond O2 forms with the water molecule.
Zinc is known to have both tetrahedral and octahedral coordination in crystal structures (Cingi et al., 1972). Zinc in the present structure has a tetrahedral coordination with three chlorines and a carboxyl O atom of the amino acid taking part. The angles around the Zn atom range from 104.2 (1) to 115.4 (1)°. Fig. 2 shows the packing of the molecules viewed down the b axis. A head-to-tail N—H···O hydrogen bond between the screw-related molecules is present. One of the three chlorines participates in a C—H···Cl hydrogen bond (see Table 2). The N1—H1A···O1ii and N1—H1B···Cliii hydrogen bonds form a ring of R44(12) graph-set motif (Etter et al., 1990), while the O2—H1···O1Wi and O1W—H2W···Cl3 interactions form a C22(8) chain running along [100] [symmetry codes: (ii) 2 - x, y - 1/2, -z; (iii) x, y - 1, z].