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The X-ray crystal structure of the title compound, [ZnCl(C6H14NO3)], was redetermined with a CCD area detector at 150 (2) K. The crystal appeared to be non-merohedrally twinned. Appropriate handling of the twinning, together with the low measurement temperature, allowed the localization and refinement of the H atoms, which was not possible with the film data from the literature [Follner (1972), Acta Cryst. B28, 157-160]. The precision of the other geometrical data has also significantly improved.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001533/bt6232sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001533/bt6232Isup2.hkl
Contains datablock I

CCDC reference: 204661

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.021
  • wR factor = 0.053
  • Data-to-parameter ratio = 17.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Triethanolamine is mostly encountered as a four-coordinating ligand with a few exceptions, in which the ligand is found to be three (Topcu et al., 2001) or even two coordinating (Kapteijn et al., 1997).

The crystal structure of the title compound, (I), was first described by Follner (1972), based on Weissenberg data. The author mentions a needle-shaped crystal form and a pseudo-monoclinic symmetry of the triclinic unit cell, but does not find an indication for twinning.

Compound (I) has a very low solubility in most solvents. We therefore prepared the crystals by gel crystallization from a tetramethoxysilane gel (Arend & Connelly, 1982). The crystals are needle-shaped and elongated along the b axis. All crystals appeared to be non-merohedrally twinned, with a twofold rotation around uvw = [010] as twin operation. A crystal with a small contribution of the second twin domain was chosen for the diffraction experiment. The refinement was performed with the HKLF5 option of the SHELXL97 program (Herbst-Irmer & Sheldrick, 1998). The proper handling of the twinned data led to a significant decrease in the discrepancy factors; peaks of residual electron density disappeared.

A molecular plot of (I) is depicted in Fig. 1. The Zn atom is five-coordinated by the three O atoms and the N atom of the triethanolamine ligand and by the Cl atom, and is situated 0.309 (1) Å below the O3 plane of the triethanolamine ligand. The coordination geometry is intermediate between a trigonal bipyramid and a square pyramid. The τ descriptor (Addison et al., 1984) has a value of 0.77, which is closer to a trigonal bipyramid (τ = 1) than to a square pyramid (τ = 0). This is consistent with the pseudorotation (Holmes, 1984), which is 0.23 on the pathway from trigonal bipyramid to square pyramid. It should be noted, that in the case of five coordinated zinc compounds, a basal angle of 158° has to be used in the calculation of the pseudorotation (Vahrenkamp, 1999).

One of the three hydroxyl groups of the triethanolamine ligand is deprotonated, resulting in a short O1—-Zn1 distance of 2.0014 (12) Å due to the negative charge on atom O1 (Table 1). The O2—Zn1 and O3—Zn1 distances of the neutral hydroxyl groups are correspondingly longer, with values of 2.1056 (13) and 2.0935 (13) Å, respectively. The hydroxyl H atoms point in opposite directions, thus increasing the O2—Zn1–O3 angle to 123.54 (5)°, while the other two O—Zn—O angles are significantly smaller than 120°. This distortion is also reflected in a tilt of Cl1 in the direction of O2 and O3, resulting in a Cl1—Zn1—N1 angle of 169.79 (4)°.

The deviation from a perfect threefold symmetry can also be seen in the ring conformations. A ring-puckering analysis (Evans & Boeyens, 1989) of the three five-membered chelate rings results in coefficients of 86 and 84% for the envelope conformations of rings Zn1—O1—C2—C1—N1 and Zn1—O2—C4—C3—N1, respectively. Ring Zn1—O3—C6—C5—N1, however, has a coefficient of 64% for the twist conformation.

The compound forms two intermolecular hydrogen bonds, in which the deprotonated atom O1 is the acceptor and the neutral hydroxyl groups at atoms O2 and O3 are the donors (Table 2). This hydrogen bonding is the main reason for the arrangement of the hydroxyl H atoms in opposite directions and the resulting distortions of the coordination polyhedron. The hydrogen bonds lead to the formation of one-dimensional chains running parallel to the crystallographic b axis. A mis-arrangement of the chains is the most probable reason for the non-merohedral twinning with a twofold rotation around the b axis as twin operation (Fig. 2).

Experimental top

Crystals of (I) were obtained by gel crystallization (Arend & Connelly, 1982). 4.5 ml of an aqueous ZnCl2 solution (1 molar) was stirred with 0.5 ml tetramethoxysilane until a clear solution was obtained. This solution was poured into test tubes and allowed to solidify for 12 h. Then an aqueous solution of triethanolamine (1 molar) was carefully put on top of the gel. After 24 h, crystals of suitable size were obtained.

Refinement top

X-ray intensities were obtained using two different orientation matrices. The HKLF5 reflection file contains the non-overlapping reflections of the first twin domain and the overlapping reflections. The non-overlapping reflections of the second twin domain were disregarded. The twin fraction of the second domain refined to 0.0878 (19).

The direction cosines of all reflections were calculated with respect to the orientation matrix of the first twin domain. An analytical absorption correction was performed using the ABST routine of the program PLATON (Spek, 2002). Afterwards, equivalent reflections were merged using a locally written program.

Hydroxyl H atoms were refined freely with isotropic displacement parameters. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.99–1.00 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVAL14 (Duisenberg, 1998); program(s) used to solve structure: coordinates taken from the literature (Follner, 1972); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: manual editing of SHELXL97 cif output.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. C—H H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The packing of compound (I) in the crystal, viewed along the crystallographic b axis. The hydrogen-bonded chains are running parallel to this direction. A twofold rotation around this direction is the twin operation.
chloro(triethanolaminato)zinc(II) top
Crystal data top
[ZnCl(C6H14NO3)]Z = 2
Mr = 249.00F(000) = 256
Triclinic, P1Dx = 1.788 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4014 (9) ÅCell parameters from 31 reflections
b = 8.0163 (6) Åθ = 3.4–19.5°
c = 8.2906 (12) ŵ = 2.91 mm1
α = 89.413 (9)°T = 150 K
β = 77.541 (9)°Needle, colourless
γ = 74.655 (8)°0.54 × 0.12 × 0.06 mm
V = 462.62 (10) Å3
Data collection top
Nonius KappaCCD
diffractometer
2106 independent reflections
Radiation source: rotating anode1961 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
ϕ and ω scansθmax = 27.6°, θmin = 2.5°
Absorption correction: analytical
(PLATON; Spek, 2002)
h = 99
Tmin = 0.41, Tmax = 0.85k = 1010
10000 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: difference Fourier map
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0234P)2 + 0.291P]
where P = (Fo2 + 2Fc2)/3
2106 reflections(Δ/σ)max = 0.001
118 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
[ZnCl(C6H14NO3)]γ = 74.655 (8)°
Mr = 249.00V = 462.62 (10) Å3
Triclinic, P1Z = 2
a = 7.4014 (9) ÅMo Kα radiation
b = 8.0163 (6) ŵ = 2.91 mm1
c = 8.2906 (12) ÅT = 150 K
α = 89.413 (9)°0.54 × 0.12 × 0.06 mm
β = 77.541 (9)°
Data collection top
Nonius KappaCCD
diffractometer
2106 independent reflections
Absorption correction: analytical
(PLATON; Spek, 2002)
1961 reflections with I > 2σ(I)
Tmin = 0.41, Tmax = 0.85Rint = 0.050
10000 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.50 e Å3
2106 reflectionsΔρmin = 0.38 e Å3
118 parameters
Special details top

Experimental. 363 ϕ-scans and 520 ω-scans were measured at a constant detector distance of 40.0 mm with a rotation angle of 1° per frame. The exposure time was 30 s per frame with a generator setting of 60 kV, 50 mA.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.63638 (3)0.71692 (2)0.00582 (2)0.01096 (7)
Cl10.67525 (6)0.70219 (6)0.27158 (5)0.01732 (10)
O10.35226 (16)0.78095 (15)0.09658 (14)0.0126 (2)
O20.77712 (18)0.45419 (16)0.02228 (16)0.0142 (3)
H2O0.738 (4)0.387 (4)0.019 (3)0.035 (8)*
O30.76654 (18)0.91815 (17)0.01298 (16)0.0146 (3)
H3O0.726 (4)1.012 (4)0.015 (3)0.035 (7)*
N10.6540 (2)0.71347 (18)0.26123 (18)0.0107 (3)
C10.4630 (2)0.6993 (2)0.3500 (2)0.0135 (3)
H1A0.43980.73830.46740.016*
H1B0.45990.57670.34630.016*
C20.3054 (2)0.8093 (2)0.2719 (2)0.0145 (3)
H2A0.18300.78040.31790.017*
H2B0.28710.93330.30000.017*
C30.8110 (2)0.5608 (2)0.2796 (2)0.0130 (3)
H3A0.79930.53610.39810.016*
H3B0.93640.58610.23840.016*
C40.8035 (2)0.4031 (2)0.1838 (2)0.0139 (3)
H4A0.92450.31030.17460.017*
H4B0.69570.35820.24190.017*
C50.6922 (3)0.8776 (2)0.3056 (2)0.0134 (3)
H5A0.74790.86310.40490.016*
H5B0.57030.97060.33170.016*
C60.8310 (2)0.9276 (2)0.1624 (2)0.0147 (3)
H6A0.83801.04680.18350.018*
H6B0.96110.84810.15160.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01265 (11)0.01166 (11)0.00974 (11)0.00424 (8)0.00383 (7)0.00195 (7)
Cl10.0239 (2)0.0194 (2)0.0103 (2)0.00769 (18)0.00509 (16)0.00208 (16)
O10.0131 (6)0.0161 (6)0.0096 (6)0.0040 (5)0.0048 (4)0.0013 (5)
O20.0197 (6)0.0125 (6)0.0127 (6)0.0061 (5)0.0061 (5)0.0006 (5)
O30.0210 (6)0.0125 (6)0.0137 (6)0.0070 (5)0.0082 (5)0.0047 (5)
N10.0129 (6)0.0095 (6)0.0110 (7)0.0036 (5)0.0044 (5)0.0019 (5)
C10.0136 (8)0.0168 (8)0.0117 (8)0.0064 (7)0.0030 (6)0.0035 (6)
C20.0130 (8)0.0179 (8)0.0116 (8)0.0029 (7)0.0024 (6)0.0009 (7)
C30.0150 (8)0.0115 (8)0.0134 (8)0.0021 (6)0.0070 (7)0.0026 (6)
C40.0165 (8)0.0129 (8)0.0131 (8)0.0044 (7)0.0047 (6)0.0021 (7)
C50.0180 (8)0.0117 (8)0.0124 (8)0.0052 (6)0.0058 (7)0.0001 (6)
C60.0171 (8)0.0126 (8)0.0181 (9)0.0071 (7)0.0081 (7)0.0034 (7)
Geometric parameters (Å, º) top
Zn1—O12.0014 (12)C1—H1A0.9900
Zn1—O22.1056 (13)C1—H1B0.9900
Zn1—O32.0935 (13)C2—H2A0.9900
Zn1—N12.1489 (14)C2—H2B0.9900
Zn1—Cl12.2557 (6)C3—C41.520 (2)
O1—C21.425 (2)C3—H3A0.9900
O2—C41.435 (2)C3—H3B0.9900
O2—H2O0.78 (3)C4—H4A0.9900
O3—C61.430 (2)C4—H4B0.9900
O3—H3O0.79 (3)C5—C61.519 (2)
N1—C11.479 (2)C5—H5A0.9900
N1—C31.480 (2)C5—H5B0.9900
N1—C51.482 (2)C6—H6A0.9900
C1—C21.526 (2)C6—H6B0.9900
O1—Zn1—O3115.10 (5)O1—C2—H2A109.4
O1—Zn1—O2114.74 (5)C1—C2—H2A109.4
O3—Zn1—O2123.54 (5)O1—C2—H2B109.4
O1—Zn1—N184.55 (5)C1—C2—H2B109.4
O3—Zn1—N180.63 (5)H2A—C2—H2B108.0
O2—Zn1—N179.34 (5)N1—C3—C4110.76 (14)
O1—Zn1—Cl1105.60 (4)N1—C3—H3A109.5
O3—Zn1—Cl195.70 (4)C4—C3—H3A109.5
O2—Zn1—Cl195.04 (4)N1—C3—H3B109.5
N1—Zn1—Cl1169.79 (4)C4—C3—H3B109.5
C2—O1—Zn1111.81 (9)H3A—C3—H3B108.1
C4—O2—Zn1115.59 (10)O2—C4—C3108.15 (13)
C4—O2—H2O110 (2)O2—C4—H4A110.1
Zn1—O2—H2O116 (2)C3—C4—H4A110.1
C6—O3—Zn1112.85 (10)O2—C4—H4B110.1
C6—O3—H3O110 (2)C3—C4—H4B110.1
Zn1—O3—H3O123.7 (19)H4A—C4—H4B108.4
C1—N1—C3112.55 (13)N1—C5—C6109.82 (14)
C1—N1—C5112.44 (13)N1—C5—H5A109.7
C3—N1—C5111.76 (13)C6—C5—H5A109.7
C1—N1—Zn1103.75 (10)N1—C5—H5B109.7
C3—N1—Zn1107.69 (10)C6—C5—H5B109.7
C5—N1—Zn1108.12 (10)H5A—C5—H5B108.2
N1—C1—C2110.68 (13)O3—C6—C5109.43 (13)
N1—C1—H1A109.5O3—C6—H6A109.8
C2—C1—H1A109.5C5—C6—H6A109.8
N1—C1—H1B109.5O3—C6—H6B109.8
C2—C1—H1B109.5C5—C6—H6B109.8
H1A—C1—H1B108.1H6A—C6—H6B108.2
O1—C2—C1111.38 (13)
O3—Zn1—O1—C270.90 (11)O1—Zn1—N1—C5100.94 (11)
O2—Zn1—O1—C281.69 (11)O3—Zn1—N1—C515.66 (10)
N1—Zn1—O1—C26.08 (11)O2—Zn1—N1—C5142.59 (11)
Cl1—Zn1—O1—C2175.07 (10)Cl1—Zn1—N1—C585.3 (2)
O1—Zn1—O2—C475.52 (12)C3—N1—C1—C2155.10 (14)
O3—Zn1—O2—C474.47 (12)C5—N1—C1—C277.61 (17)
N1—Zn1—O2—C43.34 (11)Zn1—N1—C1—C238.97 (15)
Cl1—Zn1—O2—C4174.73 (10)Zn1—O1—C2—C129.81 (16)
O1—Zn1—O3—C690.38 (11)N1—C1—C2—O147.84 (19)
O2—Zn1—O3—C659.51 (12)C1—N1—C3—C470.66 (18)
N1—Zn1—O3—C610.97 (11)C5—N1—C3—C4161.70 (14)
Cl1—Zn1—O3—C6159.42 (10)Zn1—N1—C3—C443.08 (15)
O1—Zn1—N1—C118.64 (10)Zn1—O2—C4—C326.95 (16)
O3—Zn1—N1—C1135.23 (11)N1—C3—C4—O246.33 (18)
O2—Zn1—N1—C197.84 (10)C1—N1—C5—C6152.46 (14)
Cl1—Zn1—N1—C1155.12 (17)C3—N1—C5—C679.84 (17)
O1—Zn1—N1—C3138.14 (11)Zn1—N1—C5—C638.52 (15)
O3—Zn1—N1—C3105.26 (11)Zn1—O3—C6—C534.98 (16)
O2—Zn1—N1—C321.67 (10)N1—C5—C6—O349.10 (18)
Cl1—Zn1—N1—C335.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O1i0.78 (3)1.83 (3)2.6156 (18)174 (3)
O3—H3O···O1ii0.79 (3)1.78 (3)2.5678 (17)175 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+2, z.

Experimental details

Crystal data
Chemical formula[ZnCl(C6H14NO3)]
Mr249.00
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)7.4014 (9), 8.0163 (6), 8.2906 (12)
α, β, γ (°)89.413 (9), 77.541 (9), 74.655 (8)
V3)462.62 (10)
Z2
Radiation typeMo Kα
µ (mm1)2.91
Crystal size (mm)0.54 × 0.12 × 0.06
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionAnalytical
(PLATON; Spek, 2002)
Tmin, Tmax0.41, 0.85
No. of measured, independent and
observed [I > 2σ(I)] reflections
10000, 2106, 1961
Rint0.050
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.053, 1.08
No. of reflections2106
No. of parameters118
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.50, 0.38

Computer programs: COLLECT (Nonius, 1999), DIRAX (Duisenberg, 1992), EVAL14 (Duisenberg, 1998), coordinates taken from the literature (Follner, 1972), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), manual editing of SHELXL97 cif output.

Selected geometric parameters (Å, º) top
Zn1—O12.0014 (12)Zn1—N12.1489 (14)
Zn1—O22.1056 (13)Zn1—Cl12.2557 (6)
Zn1—O32.0935 (13)
O1—Zn1—O3115.10 (5)O2—Zn1—N179.34 (5)
O1—Zn1—O2114.74 (5)O1—Zn1—Cl1105.60 (4)
O3—Zn1—O2123.54 (5)O3—Zn1—Cl195.70 (4)
O1—Zn1—N184.55 (5)O2—Zn1—Cl195.04 (4)
O3—Zn1—N180.63 (5)N1—Zn1—Cl1169.79 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O1i0.78 (3)1.83 (3)2.6156 (18)174 (3)
O3—H3O···O1ii0.79 (3)1.78 (3)2.5678 (17)175 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+2, z.
 

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