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

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.

Computing details

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)

Crystal data

NaCl·13(H2O)	F(000) = 632
Mr = 292.65	Dx = 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) Å^3	Platelet, colorless
Z = 4	0.3 × 0.3 × 0.1 mm

Data collection

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

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters not defined
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 3.3523P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max < 0.001
S = 0.96	Δρmax = 0.12 e Å^−3
360 reflections	Δρmin = −0.15 e Å^−3
35 parameters

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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)

Na1—O1	2.313 (4)	Na2—O3^vi	2.362 (5)
Na1—O1^i	2.313 (4)	Na2—O3	2.362 (5)
Na1—O2^ii	2.386 (3)	Na2—O4^ii	2.398 (3)
Na1—O2^iii	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—O1^i	180.00 (12)	O3^vi—Na2—O3	180.0
O1—Na1—O2^ii	87.13 (10)	O3^vi—Na2—O4^ii	88.13 (10)
O1^i—Na1—O2^ii	92.87 (10)	O3—Na2—O4^ii	91.87 (10)
O1—Na1—O2^iii	92.87 (10)	O3^vi—Na2—O4^vii	91.87 (10)
O1^i—Na1—O2^iii	87.13 (10)	O3—Na2—O4^vii	88.13 (10)
O2^ii—Na1—O2^iii	180.00 (16)	O4^ii—Na2—O4^vii	180.0
O1—Na1—O2^iv	87.13 (10)	O3^vi—Na2—O4^iv	88.13 (10)
O1^i—Na1—O2^iv	92.87 (10)	O3—Na2—O4^iv	91.87 (10)
O2^ii—Na1—O2^iv	88.13 (13)	O4^ii—Na2—O4^iv	95.53 (13)
O2^iii—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)
O1^i—Na1—O2^v	87.13 (10)	O3—Na2—O4^viii	88.13 (10)
O2^ii—Na1—O2^v	91.87 (13)	O4^ii—Na2—O4^viii	84.47 (13)
O2^iii—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)

Crystal data

NaCl·13(D2O)	F(000) = 10824
Mr = 318.81	Dx = 1.667 Mg m^−3
Monoclinic, C2/m	Neutron radiation, λ = 1 Å
a = 11.3436 (1) Å	Cell parameters from 50 reflections
b = 11.8254 (10) Å	θ = 53.8–84.2°
c = 10.8625 (2) Å	µ = 0.07 mm^−1
β = 119.3454 (4)°	T = 298 K
V = 1270.15 (11) Å^3	Platelet, colorless
Z = 4	0.10 × 0.10 × 0.10 mm

Data collection

Time-of-flight Laue-type single crystal neutron diffractometer	1086 independent reflections
Radiation source: spallation neutron	1086 reflections with I > 10σ(I)
Detector resolution: 4 pixels mm^-1	Rint = 0.145
time–of–flight Laue method scans	θmax = 80.9°, θmin = 9.2°
Absorption correction: numerical self-made program for diamond anvil cell	h = −14→16
Tmin = 0.474, Tmax = 0.853	k = −10→7
1086 measured reflections	l = −14→14

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.075	(Δ/σ)max = 0.019
wR(F^2) = 0.182	Δρmax = 1.26 e Å^−3
S = 1.78	Δρmin = −1.39 e Å^−3
1086 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
139 parameters	Extinction coefficient: 0.0020 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl	0.4053 (8)	0.000000	0.3063 (9)	0.017 (3)*
Na1	0.000000	0.000000	0.000000	0.018 (9)*
Na2	0.000000	0.000000	0.500000	0.007 (7)*
O1	0.1057 (18)	0.000000	0.2433 (19)	0.019 (5)*
O2	0.8542 (14)	0.141 (2)	0.0073 (18)	0.026 (4)*
O3	0.2391 (16)	0.000000	0.6277 (18)	0.021 (5)*
O4	0.9954 (17)	0.148 (2)	0.3485 (16)	0.029 (4)*
O5	0.3464 (16)	0.170 (2)	0.5176 (19)	0.031 (3)*
O6	0.7411 (15)	0.245 (2)	0.2486 (16)	0.029 (3)*
O7	0.4810 (18)	0.156 (2)	0.1264 (19)	0.029 (4)*
O8	0.305 (2)	0.000000	0.916 (3)	0.039 (5)*
D1A	0.1984 (17)	0.000000	0.2768 (17)	0.035 (5)*
D1B	0.079 (2)	0.059 (3)	0.281 (2)	0.030 (6)*	0.5
D2A	0.7969 (12)	0.101 (2)	0.0362 (15)	0.056 (4)*
D2B	0.8940 (17)	0.206 (3)	0.0622 (19)	0.042 (5)*	0.88 (2)
D2C	0.803 (7)	0.144 (9)	−0.091 (10)	0.00 (2)*	0.12 (2)
D3	0.2679 (10)	0.0640 (17)	0.5944 (13)	0.042 (4)*
D4A	1.048 (2)	0.212 (3)	0.392 (2)	0.039 (5)*	0.86 (3)
D4B	1.036 (3)	0.107 (4)	0.299 (3)	0.045 (8)*	0.5
D4C	0.907 (2)	0.183 (3)	0.309 (2)	0.048 (7)*	0.64 (3)
D5A	0.3002 (15)	0.183 (2)	0.423 (2)	0.042 (5)*	0.86 (3)
D5B	0.4097 (14)	0.107 (2)	0.5225 (16)	0.062 (5)*
D5C	0.412 (8)	0.224 (13)	0.573 (8)	0.008 (19)*	0.14 (3)
D6A	0.7233 (14)	0.299 (2)	0.1728 (19)	0.046 (5)*	0.88 (2)
D6B	0.819 (4)	0.207 (5)	0.269 (3)	0.035 (11)*	0.36 (3)
D6C	0.656 (3)	0.208 (3)	0.215 (2)	0.038 (6)*	0.62 (2)
D6D	0.776 (12)	0.27 (2)	0.35 (2)	0.08 (4)*	0.14 (3)
D7A	0.4615 (10)	0.1146 (18)	0.1913 (14)	0.037 (4)*
D7B	0.571 (4)	0.180 (6)	0.175 (4)	0.042 (11)*	0.38 (2)
D7C	0.436 (3)	0.113 (5)	0.040 (4)	0.054 (8)*	0.5
D7D	0.441 (10)	0.218 (15)	0.105 (9)	0.01 (2)*	0.12 (2)
D8A	0.2894 (16)	0.000000	0.817 (2)	0.047 (5)*
D8B	0.374 (3)	0.056 (4)	0.960 (4)	0.063 (9)*	0.5

Geometric parameters (Å, º)

Na1—O1^i	2.305 (18)	O3—D3	0.962 (16)
Na1—O1	2.305 (18)	O4—D4A	0.93 (3)
Na1—O2^ii	2.381 (19)	O4—D4C	0.97 (3)
Na1—O2^iii	2.381 (19)	O4—D4B	0.99 (4)
Na1—O2^iv	2.381 (19)	O5—D5A	0.913 (19)
Na1—O2^v	2.381 (19)	O5—D5C	0.94 (13)
Na1—D2C^ii	2.59 (9)	O5—D5B	1.02 (3)
Na1—D2C^iii	2.59 (9)	O6—D6B	0.91 (4)
Na1—D2C^iv	2.59 (9)	O6—D6C	0.95 (3)
Na1—D2C^v	2.59 (9)	O6—D6D	1.0 (2)
Na2—O3^vi	2.365 (16)	O6—D6A	0.98 (3)
Na2—O3	2.365 (16)	O7—D7D	0.83 (17)
Na2—O4^ii	2.388 (19)	O7—D7B	0.94 (4)
Na2—O4^vii	2.388 (19)	O7—D7C	0.96 (5)
Na2—O4^iv	2.388 (19)	O7—D7A	0.97 (2)
Na2—O4^viii	2.388 (19)	O8—D8B	0.96 (4)
O1—D1A	0.929 (16)	O8—D8B^ix	0.96 (4)
O1—D1B^ix	0.93 (3)	O8—D8A	1.00 (2)
O1—D1B	0.93 (3)	D4C—D6B	0.92 (4)
O2—D2C	0.93 (8)	D6B—D4C	0.92 (4)
O2—D2B	0.93 (3)	D6C—D7B	0.90 (4)
O2—D2A	0.974 (18)	D7B—D6C	0.90 (4)
O3—D3^ix	0.962 (16)
O1^i—Na1—O1	180.0	O3—Na2—O4^iv	92.0 (5)
O1^i—Na1—O2^ii	93.4 (5)	O4^ii—Na2—O4^iv	94.5 (10)
O1—Na1—O2^ii	86.6 (5)	O4^vii—Na2—O4^iv	85.5 (10)
O1^i—Na1—O2^iii	86.6 (5)	O3^vi—Na2—O4^viii	92.0 (5)
O1—Na1—O2^iii	93.4 (5)	O3—Na2—O4^viii	88.0 (5)
O2^ii—Na1—O2^iii	180.0 (9)	O4^ii—Na2—O4^viii	85.5 (10)
O1^i—Na1—O2^iv	93.4 (5)	O4^vii—Na2—O4^viii	94.5 (10)
O1—Na1—O2^iv	86.6 (5)	O4^iv—Na2—O4^viii	180.0
O2^ii—Na1—O2^iv	89.3 (10)	D1A—O1—D1B^ix	112 (2)
O2^iii—Na1—O2^iv	90.7 (10)	D1A—O1—D1B	112 (2)
O1^i—Na1—O2^v	86.6 (5)	D1B^ix—O1—D1B	98 (4)
O1—Na1—O2^v	93.4 (5)	D1A—O1—Na1	107.6 (17)
O2^ii—Na1—O2^v	90.7 (10)	D1B^ix—O1—Na1	113.9 (19)
O2^iii—Na1—O2^v	89.3 (10)	D1B—O1—Na1	113.9 (19)
O2^iv—Na1—O2^v	180.0 (7)	D2C—O2—D2B	122 (7)
O1^i—Na1—D2C^ii	72 (2)	D2C—O2—D2A	104 (5)
O1—Na1—D2C^ii	108 (2)	D2B—O2—D2A	113 (2)
O2^ii—Na1—D2C^ii	21.0 (18)	D2C—O2—Na1^x	92 (6)
O2^iii—Na1—D2C^ii	159.0 (18)	D2B—O2—Na1^x	117.8 (15)
O2^iv—Na1—D2C^ii	90 (2)	D2A—O2—Na1^x	104 (2)
O2^v—Na1—D2C^ii	90 (2)	D3^ix—O3—D3	104 (3)
O1^i—Na1—D2C^iii	108 (2)	D3^ix—O3—Na2	106.4 (14)
O1—Na1—D2C^iii	72 (2)	D3—O3—Na2	106.4 (14)
O2^ii—Na1—D2C^iii	159.0 (18)	D4A—O4—D4C	98 (3)
O2^iii—Na1—D2C^iii	21.0 (18)	D4A—O4—D4B	109 (3)
O2^iv—Na1—D2C^iii	90 (2)	D4C—O4—D4B	129 (3)
O2^v—Na1—D2C^iii	90 (2)	D4A—O4—Na2^x	116.6 (16)
D2C^ii—Na1—D2C^iii	180 (5)	D4C—O4—Na2^x	107 (2)
O1^i—Na1—D2C^iv	72 (2)	D4B—O4—Na2^x	99 (3)
O1—Na1—D2C^iv	108 (2)	D5A—O5—D5C	116 (6)
O2^ii—Na1—D2C^iv	90 (2)	D5A—O5—D5B	100 (2)
O2^iii—Na1—D2C^iv	90 (2)	D5C—O5—D5B	99 (6)
O2^iv—Na1—D2C^iv	21.0 (18)	D6B—O6—D6C	123 (5)
O2^v—Na1—D2C^iv	159.0 (18)	D6B—O6—D6D	93 (9)
D2C^ii—Na1—D2C^iv	82 (4)	D6C—O6—D6D	108 (8)
D2C^iii—Na1—D2C^iv	98 (4)	D6B—O6—D6A	107 (3)
O1^i—Na1—D2C^v	108 (2)	D6C—O6—D6A	103 (2)
O1—Na1—D2C^v	72 (2)	D6D—O6—D6A	124 (10)
O2^ii—Na1—D2C^v	90 (2)	D7D—O7—D7B	101 (8)
O2^iii—Na1—D2C^v	90 (2)	D7D—O7—D7C	103 (7)
O2^iv—Na1—D2C^v	159.0 (18)	D7B—O7—D7C	128 (4)
O2^v—Na1—D2C^v	21.0 (18)	D7D—O7—D7A	111 (5)
D2C^ii—Na1—D2C^v	98 (4)	D7B—O7—D7A	109 (3)
D2C^iii—Na1—D2C^v	82 (4)	D7C—O7—D7A	104 (4)
D2C^iv—Na1—D2C^v	180 (5)	D8B—O8—D8B^ix	88 (5)
O3^vi—Na2—O3	180.0	D8B—O8—D8A	101 (3)
O3^vi—Na2—O4^ii	88.0 (5)	D8B^ix—O8—D8A	101 (3)
O3—Na2—O4^ii	92.0 (5)	O2—D2C—Na1^x	67 (5)
O3^vi—Na2—O4^vii	92.0 (5)	D6B—D4C—O4	173 (5)
O3—Na2—O4^vii	88.0 (5)	O6—D6B—D4C	165 (6)
O4^ii—Na2—O4^vii	180.0	D7B—D6C—O6	173 (4)
O3^vi—Na2—O4^iv	88.0 (5)	D6C—D7B—O7	174 (7)
D2B—O2—D2C—Na1^x	125 (3)	D6D—O6—D6B—D4C	−28 (24)
D2A—O2—D2C—Na1^x	−106 (3)	D6A—O6—D6B—D4C	99 (20)
D6C—O6—D6B—D4C	−142 (19)

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; (ix) x, −y, z; (x) x+1, y, z.