In the title compound, (NH
4)[ZnCl
3(C
6H
12N
4)]·1.5H
2O, the Zn
II atom is in a tetrahedral environment, coordinated by one N atom of the hexamethylenetetramine ligand and by three Cl atoms. The charge of the hexamethylenetetraminetrichlorozincate(II) anion is counter-balanced by an ammonium cation. Two water molecules, one of which shows disorder and is only partly occupied, are also present. The structure is stabilized by weak intermolecular O—H
N, N—H
O and N—H
N hydrogen bonds.
Supporting information
CCDC reference: 630498
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (N-C) = 0.004 Å
- H-atom completeness 95%
- Disorder in main residue
- R factor = 0.040
- wR factor = 0.093
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.97
PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc.
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O2
PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O2'
PLAT431_ALERT_2_C Short Inter HL..A Contact Cl3 .. O2 .. 3.26 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1A .. CL1 .. 2.87 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A .. CL2 .. 2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A .. CL2 .. 2.86 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
PLAT731_ALERT_1_C Bond Calc 0.83(4), Rep 0.823(18) ...... 2.22 su-Ra
O1 -H1WA 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.842(19) ...... 2.11 su-Ra
O1 -H1WB 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.83(4), Rep 0.823(18) ...... 2.22 su-Ra
O1 -H1# 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.842(19) ...... 2.11 su-Ra
O1 -H2# 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.842(19) ...... 2.11 su-Ra
O1 -H2# 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.842(19) ...... 2.11 su-Ra
O1 -H2# 1.555 1.555
PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.842(19) ...... 2.11 su-Ra
O1 -H2# 1.555 1.555
PLAT736_ALERT_1_C H...A Calc 2.01(4), Rep 2.012(19) ...... 2.11 su-Ra
H1# -N4 1.555 1.555
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C6 H19 Cl3 N5 O1.5 Zn1
Atom count from the _atom_site data: C6 H18 Cl3 N5 O1.5 Zn1
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C6 H19 Cl3 N5 O1.50 Zn
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 24.00 24.00 0.00
H 76.00 72.00 4.00
Cl 12.00 12.00 0.00
N 20.00 20.00 0.00
O 6.00 6.00 0.00
Zn 4.00 4.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
20 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
5 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Ammonium trichloro(hexamethylenetetramine)zincate 1.5-hydrate
top
Crystal data top
(NH4)[ZnCl3(C6H12N4)]·1.5H2O | F(000) = 728 |
Mr = 357.96 | Dx = 1.650 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3136 reflections |
a = 8.7692 (19) Å | θ = 2.3–27.0° |
b = 9.621 (2) Å | µ = 2.26 mm−1 |
c = 17.137 (4) Å | T = 273 K |
β = 94.842 (4)° | Block, colourless |
V = 1440.6 (5) Å3 | 0.37 × 0.35 × 0.32 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3136 independent reflections |
Radiation source: fine-focus sealed tube | 2694 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
φ and ω scans | θmax = 27.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −11→9 |
Tmin = 0.444, Tmax = 0.499 | k = −8→12 |
8538 measured reflections | l = −18→21 |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.9695P] where P = (Fo2 + 2Fc2)/3 |
3136 reflections | (Δ/σ)max = 0.001 |
187 parameters | Δρmax = 0.33 e Å−3 |
3 restraints | Δρmin = −0.35 e Å−3 |
Special details top
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.64545 (3) | 0.04267 (3) | 0.83373 (2) | 0.03070 (12) | |
Cl1 | 0.69797 (10) | 0.04665 (9) | 0.70755 (5) | 0.0479 (2) | |
Cl2 | 0.72682 (9) | −0.15574 (8) | 0.89069 (5) | 0.0429 (2) | |
Cl3 | 0.73478 (10) | 0.23086 (10) | 0.90084 (6) | 0.0576 (3) | |
O1 | 0.1794 (3) | 0.4063 (3) | 0.97510 (14) | 0.0424 (5) | |
N5 | 0.0184 (3) | 0.6316 (3) | 0.89970 (17) | 0.0352 (6) | |
O2 | 0.4684 (18) | 0.511 (2) | 1.0414 (10) | 0.078 (4) | 0.25 |
O2' | 0.4768 (19) | 0.5626 (16) | 0.9878 (16) | 0.079 (4) | 0.25 |
N1 | 0.4053 (2) | 0.0394 (2) | 0.83495 (13) | 0.0243 (5) | |
N2 | 0.1795 (3) | −0.0946 (2) | 0.86587 (15) | 0.0317 (5) | |
N3 | 0.1616 (3) | 0.0665 (3) | 0.75544 (14) | 0.0341 (6) | |
N4 | 0.1887 (3) | 0.1553 (2) | 0.88907 (14) | 0.0321 (5) | |
C1 | 0.3468 (3) | −0.0951 (3) | 0.86481 (17) | 0.0311 (6) | |
H1A | 0.3767 | −0.1705 | 0.8318 | 0.037* | |
H1B | 0.3931 | −0.1115 | 0.9174 | 0.037* | |
C2 | 0.1113 (3) | −0.0675 (3) | 0.78613 (18) | 0.0358 (7) | |
H2A | 0.0007 | −0.0674 | 0.7862 | 0.043* | |
H2B | 0.1395 | −0.1417 | 0.7518 | 0.043* | |
C3 | 0.1198 (3) | 0.1767 (3) | 0.80870 (19) | 0.0376 (7) | |
H3A | 0.0093 | 0.1797 | 0.8091 | 0.045* | |
H3B | 0.1532 | 0.2656 | 0.7895 | 0.045* | |
C4 | 0.3553 (3) | 0.1522 (3) | 0.88707 (17) | 0.0297 (6) | |
H4A | 0.4025 | 0.1380 | 0.9397 | 0.036* | |
H4B | 0.3898 | 0.2412 | 0.8686 | 0.036* | |
C5 | 0.3289 (3) | 0.0635 (3) | 0.75469 (17) | 0.0331 (6) | |
H5A | 0.3638 | 0.1511 | 0.7345 | 0.040* | |
H5B | 0.3577 | −0.0100 | 0.7200 | 0.040* | |
C6 | 0.1358 (3) | 0.0197 (3) | 0.91692 (17) | 0.0330 (6) | |
H6A | 0.1802 | 0.0036 | 0.9699 | 0.040* | |
H6B | 0.0254 | 0.0214 | 0.9179 | 0.040* | |
H5F | −0.047 (4) | 0.638 (4) | 0.935 (2) | 0.052 (11)* | |
H5E | 0.078 (4) | 0.567 (4) | 0.912 (2) | 0.042 (10)* | |
H5C | −0.034 (5) | 0.611 (4) | 0.849 (3) | 0.075 (13)* | |
H1WA | 0.178 (5) | 0.333 (3) | 0.950 (3) | 0.11 (2)* | |
H1WB | 0.267 (4) | 0.426 (5) | 0.997 (3) | 0.15 (3)* | |
H5D | 0.064 (5) | 0.715 (5) | 0.891 (3) | 0.088 (15)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.02226 (18) | 0.0319 (2) | 0.0383 (2) | 0.00374 (13) | 0.00418 (13) | 0.00107 (14) |
Cl1 | 0.0440 (5) | 0.0569 (5) | 0.0454 (5) | 0.0089 (4) | 0.0193 (4) | 0.0106 (4) |
Cl2 | 0.0416 (4) | 0.0394 (4) | 0.0460 (4) | 0.0145 (3) | −0.0051 (3) | 0.0039 (3) |
Cl3 | 0.0395 (5) | 0.0479 (5) | 0.0851 (7) | −0.0072 (4) | 0.0043 (4) | −0.0217 (5) |
O1 | 0.0507 (15) | 0.0371 (13) | 0.0405 (13) | 0.0130 (11) | 0.0104 (11) | 0.0021 (10) |
N5 | 0.0349 (15) | 0.0373 (16) | 0.0339 (15) | 0.0104 (13) | 0.0057 (12) | 0.0075 (12) |
O2 | 0.085 (10) | 0.072 (10) | 0.073 (11) | 0.013 (9) | −0.019 (8) | −0.023 (11) |
O2' | 0.071 (9) | 0.082 (11) | 0.079 (12) | 0.001 (8) | −0.013 (8) | −0.027 (11) |
N1 | 0.0208 (11) | 0.0245 (12) | 0.0277 (11) | 0.0008 (9) | 0.0026 (9) | −0.0002 (9) |
N2 | 0.0244 (12) | 0.0294 (12) | 0.0414 (14) | −0.0029 (10) | 0.0038 (10) | 0.0020 (11) |
N3 | 0.0230 (12) | 0.0462 (15) | 0.0325 (13) | −0.0001 (10) | −0.0014 (10) | 0.0042 (11) |
N4 | 0.0214 (11) | 0.0328 (13) | 0.0426 (14) | 0.0015 (10) | 0.0048 (10) | −0.0070 (11) |
C1 | 0.0294 (14) | 0.0244 (14) | 0.0395 (16) | 0.0012 (11) | 0.0026 (12) | 0.0040 (12) |
C2 | 0.0266 (14) | 0.0386 (17) | 0.0417 (17) | −0.0054 (12) | −0.0007 (12) | −0.0085 (13) |
C3 | 0.0237 (14) | 0.0339 (16) | 0.0549 (19) | 0.0052 (12) | 0.0019 (13) | 0.0081 (14) |
C4 | 0.0219 (13) | 0.0297 (15) | 0.0375 (15) | 0.0013 (11) | 0.0016 (11) | −0.0064 (12) |
C5 | 0.0250 (14) | 0.0459 (18) | 0.0281 (14) | −0.0007 (12) | 0.0016 (11) | 0.0034 (12) |
C6 | 0.0259 (14) | 0.0408 (17) | 0.0328 (15) | −0.0013 (12) | 0.0052 (11) | 0.0010 (13) |
Geometric parameters (Å, º) top
Zn1—N1 | 2.108 (2) | N3—C3 | 1.466 (4) |
Zn1—Cl2 | 2.2335 (9) | N3—C5 | 1.469 (3) |
Zn1—Cl1 | 2.2487 (10) | N3—C2 | 1.474 (4) |
Zn1—Cl3 | 2.2500 (10) | N4—C4 | 1.464 (3) |
O1—H1WA | 0.823 (18) | N4—C3 | 1.471 (4) |
O1—H1WB | 0.842 (19) | N4—C6 | 1.477 (4) |
N5—H5F | 0.87 (4) | C1—H1A | 0.9700 |
N5—H5E | 0.82 (4) | C1—H1B | 0.9700 |
N5—H5C | 0.97 (4) | C2—H2A | 0.9700 |
N5—H5D | 0.92 (5) | C2—H2B | 0.9700 |
O2—O2i | 1.58 (3) | C3—H3A | 0.9700 |
O2'—O2'i | 1.33 (3) | C3—H3B | 0.9700 |
N1—C4 | 1.494 (3) | C4—H4A | 0.9700 |
N1—C5 | 1.496 (3) | C4—H4B | 0.9700 |
N1—C1 | 1.498 (3) | C5—H5A | 0.9700 |
N2—C2 | 1.468 (4) | C5—H5B | 0.9700 |
N2—C1 | 1.469 (3) | C6—H6A | 0.9700 |
N2—C6 | 1.476 (4) | C6—H6B | 0.9700 |
| | | |
N1—Zn1—Cl2 | 105.41 (6) | N1—C1—H1B | 109.2 |
N1—Zn1—Cl1 | 107.20 (6) | H1A—C1—H1B | 107.9 |
Cl2—Zn1—Cl1 | 110.54 (3) | N2—C2—N3 | 112.2 (2) |
N1—Zn1—Cl3 | 108.17 (6) | N2—C2—H2A | 109.2 |
Cl2—Zn1—Cl3 | 112.32 (4) | N3—C2—H2A | 109.2 |
Cl1—Zn1—Cl3 | 112.77 (4) | N2—C2—H2B | 109.2 |
H1WA—O1—H1WB | 113 (3) | N3—C2—H2B | 109.2 |
H5F—N5—H5E | 109 (3) | H2A—C2—H2B | 107.9 |
H5F—N5—H5C | 110 (3) | N3—C3—N4 | 112.1 (2) |
H5E—N5—H5C | 108 (3) | N3—C3—H3A | 109.2 |
H5F—N5—H5D | 112 (4) | N4—C3—H3A | 109.2 |
H5E—N5—H5D | 115 (3) | N3—C3—H3B | 109.2 |
H5C—N5—H5D | 103 (4) | N4—C3—H3B | 109.2 |
C4—N1—C5 | 107.8 (2) | H3A—C3—H3B | 107.9 |
C4—N1—C1 | 107.3 (2) | N4—C4—N1 | 111.8 (2) |
C5—N1—C1 | 107.9 (2) | N4—C4—H4A | 109.2 |
C4—N1—Zn1 | 109.81 (15) | N1—C4—H4A | 109.2 |
C5—N1—Zn1 | 111.01 (16) | N4—C4—H4B | 109.2 |
C1—N1—Zn1 | 112.80 (15) | N1—C4—H4B | 109.2 |
C2—N2—C1 | 108.5 (2) | H4A—C4—H4B | 107.9 |
C2—N2—C6 | 108.3 (2) | N3—C5—N1 | 111.4 (2) |
C1—N2—C6 | 108.6 (2) | N3—C5—H5A | 109.3 |
C3—N3—C5 | 108.8 (2) | N1—C5—H5A | 109.3 |
C3—N3—C2 | 108.2 (2) | N3—C5—H5B | 109.3 |
C5—N3—C2 | 108.4 (2) | N1—C5—H5B | 109.3 |
C4—N4—C3 | 108.2 (2) | H5A—C5—H5B | 108.0 |
C4—N4—C6 | 109.4 (2) | N2—C6—N4 | 111.2 (2) |
C3—N4—C6 | 108.1 (2) | N2—C6—H6A | 109.4 |
N2—C1—N1 | 111.9 (2) | N4—C6—H6A | 109.4 |
N2—C1—H1A | 109.2 | N2—C6—H6B | 109.4 |
N1—C1—H1A | 109.2 | N4—C6—H6B | 109.4 |
N2—C1—H1B | 109.2 | H6A—C6—H6B | 108.0 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1WA···N4 | 0.82 (2) | 2.01 (2) | 2.834 (3) | 176 (3) |
O1—H1WB···O2 | 0.84 (2) | 2.04 (2) | 2.871 (17) | 169 (3) |
O1—H1WB···O2′ | 0.84 (2) | 2.28 (2) | 3.002 (16) | 144 (3) |
O1—H1WB···O2i | 0.84 (2) | 2.54 (2) | 3.225 (17) | 139 (3) |
O1—H1WB···O2′i | 0.84 (2) | 2.25 (2) | 3.043 (17) | 158 (3) |
N5—H5E···O1 | 0.82 (4) | 2.05 (4) | 2.838 (4) | 160 (3) |
N5—H5F···O1ii | 0.87 (4) | 2.05 (4) | 2.894 (4) | 163 |
N5—H5C···N3iii | 0.97 (4) | 2.08 (4) | 3.040 (4) | 176 (3) |
N5—H5D···N2iv | 0.92 (5) | 2.15 (5) | 3.067 (4) | 177 (4) |
C1—H1A···Cl1v | 0.97 | 2.87 | 3.673 (3) | 141 |
C5—H5A···Cl2vi | 0.97 | 2.90 | 3.679 (3) | 138 |
C6—H6A···Cl2vii | 0.97 | 2.86 | 3.655 (3) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+2; (iii) −x, y+1/2, −z+3/2; (iv) x, y+1, z; (v) −x+1, y−1/2, −z+3/2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+1, −y, −z+2. |