Ammonium trichloro­(hexa­methyl­enetetra­mine)zincate(II) sesquihydrate

In the title compound, (NH₄)[ZnCl₃(C₆H₁₂N₄)]·1.5H₂O, 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.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](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

---

Computing details

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

Crystal data

(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) Å^3	0.37 × 0.35 × 0.32 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 0.9695P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—O2^i	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)

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···O2^i	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···O1^ii	0.87 (4)	2.05 (4)	2.894 (4)	163
N5—H5C···N3^iii	0.97 (4)	2.08 (4)	3.040 (4)	176 (3)
N5—H5D···N2^iv	0.92 (5)	2.15 (5)	3.067 (4)	177 (4)
C1—H1A···Cl1^v	0.97	2.87	3.673 (3)	141
C5—H5A···Cl2^vi	0.97	2.90	3.679 (3)	138
C6—H6A···Cl2^vii	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.