Low-temperature modification of Ba(BF₄)₂(H₂O)₃

The crystal structure of the low-temperature modification of Ba(BF₄)₂(H₂O)₃, barium bis(tetra­fluorido­borate) trihydrate, was determined at 150 K. In contrast to the room-temperature modification, which crystallizes in the space group C222₁ [a = 7.1763 (6), b = 18.052 (2), c = 7.1631 (6) Å, V = 927.93 (15) ų at 300 K, Z = 4; Charkin et al. (2023). J. Struct. Chem. 64, 253–261], the low-temperature phase is monoclinic, space group P2₁ [a = 7.0550 (4), b = 7.1706 (3), c = 9.4182 (6) Å, β = 109.295 (7)^o, V = 449.68 (5) ų, Z = 2]. The structure of the low-temperature modification of Ba(BF₄)₂(H₂O)₃ features O—H...F and O—H...O hydrogen bonding between water mol­ecules and BF₄⁻ anions. One of the coordinating water mol­ecules in the low-temperature modification is disordered over two sets of sites.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](F-B) = 0.018 Å
• Disorder in solvent or counterion
• R factor = 0.036
• wR factor = 0.089
• Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom F3              has ADP max/min Ratio .....        3.6 prolat
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         B1 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         B2 Check
PLAT755_ALERT_4_C D-H     Calc     0.83000, Rep   0.829(10) ......  Senseless s.u.
              O1       -H1A             1_555   1_555 ........     #    1 Check
PLAT755_ALERT_4_C D-H     Calc     0.84000, Rep   0.842(10) ......  Senseless s.u.
              O1       -H1B             1_555   1_555 ........     #    2 Check
PLAT755_ALERT_4_C D-H     Calc     0.97000, Rep    0.974(9) ......  Senseless s.u.
              O2       -H2A             1_555   1_555 ........     #    3 Check
PLAT755_ALERT_4_C D-H     Calc     0.98000, Rep    0.977(9) ......  Senseless s.u.
              O2       -H2B             1_555   1_555 ........     #    4 Check
PLAT756_ALERT_4_C H...A   Calc     2.07000, Rep    2.075(8) ......  Senseless s.u.
              H1A      -F5              1_555   1_455 ........     #    1 Check
PLAT756_ALERT_4_C H...A   Calc     2.02000, Rep    2.016(7) ......  Senseless s.u.
              H1B      -F7              1_555   2_746 ........     #    2 Check
PLAT756_ALERT_4_C H...A   Calc     2.33000, Rep    2.331(9) ......  Senseless s.u.
              H2A      -F4              1_555   1_555 ........     #    3 Check
PLAT756_ALERT_4_C H...A   Calc     2.05000, Rep   2.053(11) ......  Senseless s.u.
              H2B      -F8              1_555   2_755 ........     #    4 Check
PLAT758_ALERT_4_C D-H..A  Calc      137.00, Rep    137.4(5) ......  Senseless s.u.
              O2      -H2A     -F4         1_555  1_555  1_555     #    3 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          8 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          3 Report
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  5  )       100% Note
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  6  )       100% Note
PLAT304_ALERT_4_G Non-Integer Number of Atoms in ..... (Resd  5  )       1.68 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms in ..... (Resd  6  )       1.32 Check
PLAT417_ALERT_2_G Short Inter D-H..H-D       H3AA     ..H2B      .       2.07 Ang.
                                               2-x,1/2+y,-z  =      2_755 Check
PLAT434_ALERT_2_G Short Inter HL..HL Contact F1       ..F8       .       2.84 Ang.
                                               1-x,1/2+y,-z  =      2_655 Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2 Note
              B F4
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4 Note
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          5 Note
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          6 Note
              H2 O
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         80 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter Values Differ by .       0.14 Check
PLAT931_ALERT_5_G CIFcalcFCF  Twin Law ( 0 0 1)         Est.d BASF       0.22 Check
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          5 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        2.1 Low

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  12 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  20 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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
  21 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2023); cell refinement: CrysAlis PRO (Rigaku OD, 2023); data reduction: CrysAlis PRO (Rigaku OD, 2023); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: DIAMOND (Putz et al., 2023); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Barium bis(tetrafluoridoborate) trihydrate

Crystal data

Ba(BF4)2(H2O)32(BF4)·3(H2O)·Ba	F(000) = 336
Mr = 365.01	Dx = 2.696 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.0550 (4) Å	Cell parameters from 5692 reflections
b = 7.1706 (3) Å	θ = 3.0–28.2°
c = 9.4182 (6) Å	µ = 4.53 mm^−1
β = 109.295 (7)°	T = 150 K
V = 449.68 (5) Å^3	Plate, colourless
Z = 2	0.36 × 0.27 × 0.07 mm

Data collection

New Gemini, Dual, Cu at home/near, Atlas diffractometer	2386 measured reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2386 independent reflections
Graphite monochromator	2212 reflections with I > 2σ(I)
Detector resolution: 10.6426 pixels mm^-1	θmax = 28.6°, θmin = 2.3°
ω scans	h = −9→9
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2023)	k = −9→9
Tmin = 0.075, Tmax = 0.472	l = −12→12

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0656P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max = 0.009
S = 1.07	Δρmax = 0.93 e Å^−3
2386 reflections	Δρmin = −1.05 e Å^−3
120 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
1 restraint	Absolute structure parameter: −0.03 (4)

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.

Refinement. Refined as a 2-component twin.

1. Twinned data refinement Scales: 0.738 (3) 0.262 (3) 2. Fixed Uiso At 1.5 times of: All O(H,H,H,H,H,H,H,H) groups 3. Uiso/Uaniso restraints and constraints Uanis(O3B) = Uanis(O3A) Uanis(B2) = Uanis(B1) Uanis(F4) = Uanis(F2) 4. Others Sof(O3B)=Sof(H3BA)=Sof(H3BB)=1-FVAR(1) Sof(O3A)=Sof(H3AA)=Sof(H3AB)=FVAR(1) Fixed X: H1A(1.393391) H1B(1.25841) H3AA(0.82474) H3AB(0.919749) H3BA(0.70805) H3BB(0.82046) H2A(1.436299) H2B(1.27384) Fixed Y: H1A(0.843861) H1B(0.70964) H3AA(1.34448) H3AB(1.39917) H3BA(1.19412) H3BB(1.354321) H2A(0.999499) H2B(1.11445) Fixed Z: H1A(0.62203) H1B(0.62415) H3AA(0.77378) H3AB(0.663441) H3BA(0.651361) H3BB(0.66705) H2A(1.1758) H2B(1.21389)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ba1	0.84596 (6)	0.54566 (15)	0.18707 (5)	0.01069 (17)
F1	0.1744 (12)	0.6957 (9)	−0.0772 (9)	0.0392 (19)
F2	0.4423 (11)	0.5754 (14)	0.0977 (9)	0.0449 (16)
F3	0.1320 (13)	0.4559 (13)	0.0610 (12)	0.050 (3)
F4	0.2873 (13)	0.4098 (13)	−0.1086 (11)	0.0449 (16)
F5	1.4219 (11)	0.4296 (12)	0.4972 (9)	0.0361 (18)
F6	1.2726 (11)	0.2125 (11)	0.5958 (8)	0.0299 (16)
F7	1.1150 (11)	0.4849 (9)	0.5097 (9)	0.0311 (18)
F8	1.1510 (13)	0.2707 (18)	0.3442 (11)	0.035 (3)
O1	0.6644 (13)	0.2926 (16)	0.3248 (12)	0.031 (2)
O2	0.6901 (12)	0.565 (2)	−0.1296 (9)	0.033 (2)
B1	0.2610 (14)	0.537 (4)	−0.0048 (10)	0.0136 (15)
B2	1.2421 (17)	0.3491 (17)	0.4874 (13)	0.0136 (15)
O3A	1.128 (3)	0.813 (4)	0.298 (2)	0.025 (4)	0.56 (2)
O3B	1.197 (4)	0.756 (4)	0.284 (3)	0.025 (4)	0.44 (2)
H1A	0.606609	0.343861	0.377970	0.038*
H1B	0.741590	0.209640	0.375850	0.038*
H3AA	1.175261	0.844480	0.226220	0.038*	0.56 (2)
H3AB	1.080250	0.899170	0.336559	0.038*	0.56 (2)
H3BA	1.291950	0.694120	0.348640	0.038*	0.44 (2)
H3BB	1.179539	0.854321	0.332950	0.038*	0.44 (2)
H2A	0.563701	0.499499	−0.175799	0.038*
H2B	0.726160	0.614450	−0.213891	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.0098 (2)	0.0107 (2)	0.0114 (3)	−0.0003 (4)	0.00317 (18)	−0.0011 (4)
F1	0.044 (5)	0.021 (3)	0.049 (5)	0.011 (3)	0.010 (4)	0.022 (3)
F2	0.029 (3)	0.052 (4)	0.052 (4)	0.000 (3)	0.011 (3)	−0.013 (3)
F3	0.043 (5)	0.048 (5)	0.082 (7)	0.010 (4)	0.051 (5)	0.030 (5)
F4	0.029 (3)	0.052 (4)	0.052 (4)	0.000 (3)	0.011 (3)	−0.013 (3)
F5	0.014 (4)	0.056 (5)	0.038 (5)	−0.005 (3)	0.008 (3)	0.003 (4)
F6	0.037 (4)	0.031 (4)	0.022 (4)	0.005 (3)	0.010 (3)	0.016 (3)
F7	0.028 (4)	0.024 (4)	0.040 (5)	0.008 (3)	0.009 (3)	0.001 (3)
F8	0.040 (6)	0.048 (6)	0.011 (4)	0.006 (4)	0.000 (3)	−0.002 (5)
O1	0.029 (5)	0.022 (5)	0.045 (7)	0.002 (3)	0.017 (5)	0.008 (4)
O2	0.026 (4)	0.055 (7)	0.013 (3)	0.006 (6)	0.000 (3)	−0.001 (6)
B1	0.010 (3)	0.021 (4)	0.010 (3)	−0.003 (4)	0.003 (3)	0.002 (4)
B2	0.010 (3)	0.021 (4)	0.010 (3)	−0.003 (4)	0.003 (3)	0.002 (4)
O3A	0.020 (10)	0.028 (11)	0.034 (8)	−0.007 (6)	0.017 (7)	−0.017 (7)
O3B	0.020 (10)	0.028 (11)	0.034 (8)	−0.007 (6)	0.017 (7)	−0.017 (7)

Geometric parameters (Å, º)

Ba1—F1^i	2.700 (6)	F4—B1	1.39 (2)
Ba1—F2	2.698 (7)	F5—B2	1.369 (13)
Ba1—F3^ii	2.735 (7)	F6—B2	1.379 (14)
Ba1—F4^iii	2.791 (9)	F7—B2	1.385 (14)
Ba1—F6^iv	2.728 (7)	F8—B2	1.406 (16)
Ba1—F7	3.035 (8)	O1—H1A	0.83
Ba1—F8	2.933 (10)	O1—H1B	0.84
Ba1—O1	2.777 (9)	O2—H2A	0.97
Ba1—O2	2.821 (8)	O2—H2B	0.98
Ba1—O3A	2.71 (2)	O3A—H3AA	0.88
Ba1—O3B	2.78 (2)	O3A—H3AB	0.84
F1—B1	1.36 (2)	O3B—H3BA	0.86
F2—B1	1.352 (12)	O3B—H3BB	0.88
F3—B1	1.387 (15)
F1^i—Ba1—F3^ii	64.4 (3)	O2—Ba1—F7	164.1 (2)
F1^i—Ba1—F4^iii	142.9 (3)	O2—Ba1—F8	122.1 (3)
F1^i—Ba1—F6^iv	134.8 (2)	O3A—Ba1—F3^ii	77.3 (5)
F1^i—Ba1—F7	100.8 (2)	O3A—Ba1—F4^iii	65.1 (6)
F1^i—Ba1—F8	60.4 (3)	O3A—Ba1—F6^iv	76.6 (4)
F1^i—Ba1—O1	66.3 (3)	O3A—Ba1—F7	65.2 (6)
F1^i—Ba1—O2	71.8 (3)	O3A—Ba1—F8	87.7 (5)
F1^i—Ba1—O3A	138.1 (5)	O3A—Ba1—O1	132.5 (5)
F1^i—Ba1—O3B	123.8 (6)	O3A—Ba1—O2	110.6 (6)
F2—Ba1—F1^i	92.1 (3)	O3B—Ba1—F7	63.6 (6)
F2—Ba1—F3^ii	137.5 (3)	O3B—Ba1—F8	76.9 (6)
F2—Ba1—F4^iii	67.4 (3)	O3B—Ba1—O2	108.2 (6)
F2—Ba1—F6^iv	69.2 (2)	B1—F1—Ba1^iii	157.8 (7)
F2—Ba1—F7	124.8 (2)	B1—F2—Ba1	149.2 (8)
F2—Ba1—F8	137.2 (3)	B1—F3—Ba1^v	141.5 (12)
F2—Ba1—O1	66.1 (3)	B1—F4—Ba1^i	133.4 (10)
F2—Ba1—O2	70.4 (2)	B2—F6—Ba1^vi	148.7 (7)
F2—Ba1—O3A	128.9 (6)	B2—F7—Ba1	99.9 (6)
F2—Ba1—O3B	142.5 (6)	B2—F8—Ba1	104.0 (8)
F3^ii—Ba1—F4^iii	109.7 (3)	Ba1—O1—H1A	113.0
F3^ii—Ba1—F7	95.4 (3)	Ba1—O1—H1B	115.0
F3^ii—Ba1—F8	62.4 (3)	H1A—O1—H1B	109.0
F3^ii—Ba1—O1	124.7 (3)	Ba1—O2—H2A	115.0
F3^ii—Ba1—O2	68.8 (3)	F1—B1—F3	108.8 (10)
F3^ii—Ba1—O3B	64.1 (6)	F1—B1—F4	109.7 (8)
F4^iii—Ba1—F7	116.4 (2)	F2—B1—F1	110.5 (17)
F4^iii—Ba1—F8	152.8 (3)	F2—B1—F3	111.8 (9)
F4^iii—Ba1—O2	72.2 (4)	F2—B1—F4	108.7 (10)
F6^iv—Ba1—F3^ii	151.8 (3)	F3—B1—F4	107.3 (17)
F6^iv—Ba1—F4^iii	68.2 (3)	F5—B2—F6	109.6 (9)
F6^iv—Ba1—F7	63.8 (2)	F5—B2—F7	109.0 (10)
F6^iv—Ba1—F8	105.8 (3)	F5—B2—F8	110.6 (10)
F6^iv—Ba1—O1	68.5 (3)	F6—B2—F7	109.8 (9)
F6^iv—Ba1—O2	131.5 (3)	F6—B2—F8	109.7 (10)
F6^iv—Ba1—O3B	88.8 (5)	F7—B2—F8	108.2 (10)
F8—Ba1—F7	44.5 (2)	Ba1—O3A—H3AA	108.0
O1—Ba1—F4^iii	124.6 (3)	Ba1—O3A—H3AB	110.0
O1—Ba1—F7	70.8 (3)	H3AA—O3A—H3AB	117.0
O1—Ba1—F8	72.5 (3)	Ba1—O3B—H3BA	111.0
O1—Ba1—O2	116.6 (3)	Ba1—O3B—H3BB	110.0
O1—Ba1—O3B	134.4 (6)	H3BA—O3B—H3BB	104.0
Ba1^iii—F1—B1—F2	25 (2)	Ba1^i—F4—B1—F3	−3.8 (15)
Ba1^iii—F1—B1—F3	148.0 (14)	Ba1^vi—F6—B2—F5	136.5 (11)
Ba1^iii—F1—B1—F4	−95 (2)	Ba1^vi—F6—B2—F7	16.9 (19)
Ba1—F2—B1—F1	−111 (2)	Ba1^vi—F6—B2—F8	−101.9 (14)
Ba1—F2—B1—F3	127.5 (12)	Ba1—F7—B2—F5	103.0 (8)
Ba1—F2—B1—F4	9 (3)	Ba1—F7—B2—F6	−137.0 (8)
Ba1^v—F3—B1—F1	−31.2 (17)	Ba1—F7—B2—F8	−17.3 (9)
Ba1^v—F3—B1—F2	91.1 (18)	Ba1—F8—B2—F5	−101.1 (9)
Ba1^v—F3—B1—F4	−149.9 (11)	Ba1—F8—B2—F6	138.0 (7)
Ba1^i—F4—B1—F1	−121.8 (12)	Ba1—F8—B2—F7	18.2 (10)
Ba1^i—F4—B1—F2	117.3 (11)

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z; (iv) −x+2, y+1/2, −z+1; (v) x−1, y, z; (vi) −x+2, y−1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···F5^v	0.829 (10)	2.075 (8)	2.892 (12)	168.8 (7)
O1—H1B···F7^vi	0.842 (10)	2.016 (7)	2.849 (13)	170.5 (7)
O2—H2A···F4	0.974 (9)	2.331 (9)	3.119 (13)	137.4 (5)
O2—H2B···F8^vii	0.977 (9)	2.053 (11)	3.002 (15)	163.5 (7)
O3A—H3AA···O2^vii	0.88 (2)	2.191 (11)	2.96 (3)	146.5 (18)
O3A—H3AB···F7^iv	0.84 (2)	2.386 (8)	3.13 (2)	147.7 (17)
O3B—H3BA···F5	0.86 (3)	2.355 (9)	3.15 (3)	153.0 (16)

Symmetry codes: (iv) −x+2, y+1/2, −z+1; (v) x−1, y, z; (vi) −x+2, y−1/2, −z+1; (vii) −x+2, y+1/2, −z.

Transformation matrix oC–mP (HT–LT phase transition of Ba(BF₄)₂(H₃O)₃

-1	0	0
0	0	-1
1/2	-1/2	0