The hydrogen-bond network in sodium chloride tridecahydrate: analogy with ice VI

Yamashita, K.; Nakayama, K.; Komatsu, K.; Ohhara, T.; Munakata, K.; Hattori, T.; Sano-Furukawa, A.; Kagi, H.

doi:10.1107/S2052520623007199

The hydrogen-bond network in sodium chloride tridecahydrate: analogy with ice VI

K. Yamashita, K. Nakayama, K. Komatsu, T. Ohhara, K. Munakata, T. Hattori, A. Sano-Furukawa and H. Kagi

The structure of a recently found hyperhydrated form of sodium chloride (NaCl·13H₂O and NaCl·13D₂O) has been determined by in situ single-crystal neutron diffraction at 1.7 GPa and 298 K. It has large hydrogen-bond networks and some water molecules have distorted bonding features such as bifurcated hydrogen bonds and five-coordinated water molecules. The hydrogen-bond network has similarities to ice VI in terms of network topology and disordered hydrogen bonds. Assuming the equivalence of network components connected by pseudo-symmetries, the overall network structure of this hydrate can be expressed by breaking it down into smaller structural units which correspond to the ice VI network structure. This hydrogen-bond network contains orientational disorder of water molecules in contrast to the known salt hydrates. An example is presented here for further insights into a hydrogen-bond network containing ionic species.

Keywords: salt hydrate; hydrogen bonds; high pressure; single-crystal neutron diffraction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520623007199/ne5013sup1.cif Contains datablocks global, NaCl_13H2O, NaCl_13D2O
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520623007199/ne5013NaCl_13H2Osup2.hkl Contains datablock NaCl_13H2O
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520623007199/ne5013NaCl_13D2Osup3.hkl Contains datablock NaCl_13D2O
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520623007199/ne5013sup4.pdf Supporting information

CCDC references: 2288971; 2288972

Computing details top

Data collection: STARGazer (Ohhara, 2009) for NaCl_13D2O. Cell refinement: STARGazer (Ohhara, 2009) for NaCl_13D2O. Data reduction: STARGazer (Ohhara, 2009) for NaCl_13D2O. Program(s) used to solve structure: SHELXL2018/3 (Sheldrick, 2018) for NaCl_13D2O. For both structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).

Sodium chloride tridecahydrate (NaCl_13H2O) top

Crystal data top

NaCl·13(H₂O)	F(000) = 632
M_r = 292.65	D_x = 1.511 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71075 Å
a = 11.403 (4) Å	Cell parameters from 1289 reflections
b = 11.882 (2) Å	θ = 4.1–33.9°
c = 10.905 (3) Å	µ = 0.38 mm⁻¹
β = 119.475 (13)°	T = 299 K
V = 1286.3 (6) Å³	Platelet, colorless
Z = 4	0.3 × 0.3 × 0.1 mm

Data collection top

RAXIS conversion diffractometer	360 independent reflections
Radiation source: Sealed Tube	360 reflections with I > 2σ(I)
Cmf monochromator	R_int = 0.024
Detector resolution: 10 pixels mm^-1	θ_max = 26.3°, θ_min = 4.3°
dtprofit.ref scans	h = −11→12
Absorption correction: numerical self-made program for diamond anvil cell	k = −11→12
T_min = 0.484, T_max = 0.569	l = −13→13
646 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters not defined
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0543P)² + 3.3523P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.099	(Δ/σ)_max < 0.001
S = 0.96	Δρ_max = 0.12 e Å⁻³
360 reflections	Δρ_min = −0.15 e Å⁻³
35 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl	0.40651 (15)	0.000000	0.30805 (14)	0.0279 (5)*
Na1	0.000000	0.000000	0.000000	0.0262 (7)*
Na2	0.000000	0.000000	0.500000	0.0256 (7)*
O2	0.8523 (3)	0.1397 (2)	0.0056 (3)	0.0321 (7)*
O1	0.1066 (5)	0.000000	0.2434 (5)	0.0328 (9)*
O4	0.9949 (3)	0.1494 (2)	0.3497 (3)	0.0314 (7)*
O6	0.7407 (3)	0.2464 (2)	0.2477 (3)	0.0338 (8)*
O3	0.2379 (5)	0.000000	0.6261 (5)	0.0310 (9)*
O8	0.3064 (5)	0.000000	0.9121 (5)	0.0339 (9)*
O5	0.3445 (3)	0.1626 (2)	0.5159 (3)	0.0309 (7)*
O7	0.4808 (3)	0.1576 (2)	0.1272 (3)	0.0356 (8)*

Geometric parameters (Å, º) top

Na1—O1	2.313 (4)	Na2—O3^vi	2.362 (5)
Na1—O1ⁱ	2.313 (4)	Na2—O3	2.362 (5)
Na1—O2ⁱⁱ	2.386 (3)	Na2—O4ⁱⁱ	2.398 (3)
Na1—O2ⁱⁱⁱ	2.386 (3)	Na2—O4^vii	2.398 (3)
Na1—O2^iv	2.386 (3)	Na2—O4^iv	2.398 (3)
Na1—O2^v	2.386 (3)	Na2—O4^viii	2.398 (3)

O1—Na1—O1ⁱ	180.00 (12)	O3^vi—Na2—O3	180.0
O1—Na1—O2ⁱⁱ	87.13 (10)	O3^vi—Na2—O4ⁱⁱ	88.13 (10)
O1ⁱ—Na1—O2ⁱⁱ	92.87 (10)	O3—Na2—O4ⁱⁱ	91.87 (10)
O1—Na1—O2ⁱⁱⁱ	92.87 (10)	O3^vi—Na2—O4^vii	91.87 (10)
O1ⁱ—Na1—O2ⁱⁱⁱ	87.13 (10)	O3—Na2—O4^vii	88.13 (10)
O2ⁱⁱ—Na1—O2ⁱⁱⁱ	180.00 (16)	O4ⁱⁱ—Na2—O4^vii	180.0
O1—Na1—O2^iv	87.13 (10)	O3^vi—Na2—O4^iv	88.13 (10)
O1ⁱ—Na1—O2^iv	92.87 (10)	O3—Na2—O4^iv	91.87 (10)
O2ⁱⁱ—Na1—O2^iv	88.13 (13)	O4ⁱⁱ—Na2—O4^iv	95.53 (13)
O2ⁱⁱⁱ—Na1—O2^iv	91.87 (13)	O4^vii—Na2—O4^iv	84.47 (13)
O1—Na1—O2^v	92.87 (10)	O3^vi—Na2—O4^viii	91.87 (10)
O1ⁱ—Na1—O2^v	87.13 (10)	O3—Na2—O4^viii	88.13 (10)
O2ⁱⁱ—Na1—O2^v	91.87 (13)	O4ⁱⁱ—Na2—O4^viii	84.47 (13)
O2ⁱⁱⁱ—Na1—O2^v	88.13 (13)	O4^vii—Na2—O4^viii	95.53 (13)
O2^iv—Na1—O2^v	180.00 (12)	O4^iv—Na2—O4^viii	180.0

Symmetry codes: (i) −x, −y, −z; (ii) x−1, −y, z; (iii) −x+1, y, −z; (iv) x−1, y, z; (v) −x+1, −y, −z; (vi) −x, −y, −z+1; (vii) −x+1, y, −z+1; (viii) −x+1, −y, −z+1.

Deuterated sodium chloride tridecahydrate (NaCl_13D2O) top