Efficient modulation of a barium metal–organic framework using amino acids

In recent years, significant advances have been made in the precise control of the physical properties of metal–organic frameworks (MOFs) via the linker-modulated method in which modulators compete with linkers and impose kinetic limitations through crystal growth. In this regard, the structure of a new barium–organic framework [Ba(H₂BTC)₂(H₂O)₄]_n, BaBTC (BTC = 1,3,5-benzene tri­carb­oxy­lic acid) is introduced, which allows the competitive coordination strategy and growth orientation of an alkaline-earth metal–organic framework (AEMOF) to be probed without sacrificing phase purity, porosity and crystallinity. The modulator effect of an assortment of amino acids on the particle size and morphology of BaBTC is investigated. Additionally, another new MOF [Ba(BTC)₂(H₂O)₃]_n.nH₂O, BaBTC-2, is synthesized through a change in the ligand concentration. This work gives a successful example of a modulation method for AEMOF synthesis by amino acids that may contribute towards targeting future avenues of nanomaterial synthesis.

Computing details

For both structures, data collection: CrysAlis CCD 1.171.38.43 (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO 1.171.38.43 (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO 1.171.38.43 (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT-2014/7 (Sheldrick, 2014). Program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014) for BaBTC; SHELXL2018/3 (Sheldrick, 2018) for BaBTC-2. For both structures, molecular graphics: Brandenburg & Putz (2006). Diamond 3.0. Crystal and Molecular Structure Visualisation, University of Bonn, Germany. Software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2014) for BaBTC; SHELXL2018/3 (Sheldrick, 2018) for BaBTC-2.

(BaBTC)

Crystal data

C18H16BaO15·H2O	F(000) = 1240
Mr = 627.66	Dx = 2.019 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.0784 (3) Å	Cell parameters from 3757 reflections
b = 13.3979 (5) Å	θ = 3.0–26.8°
c = 22.0090 (12) Å	µ = 2.01 mm^−1
β = 98.359 (5)°	T = 100 K
V = 2065.05 (17) Å^3	Neddle, colourless
Z = 4	0.22 × 0.07 × 0.05 mm

Data collection

KUMA KM-4 with CCD detector diffractometer	4705 independent reflections
Radiation source: fine-focus sealed X-ray tube	3300 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.096
ω–scan	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→9
Tmin = 0.943, Tmax = 1.000	k = −16→17
27941 measured reflections	l = −28→28

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)] = 0.046	Hydrogen site location: mixed
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0393P)^2] where P = (Fo^2 + 2Fc^2)/3
4705 reflections	(Δ/σ)max = 0.002
346 parameters	Δρmax = 1.84 e Å^−3
8 restraints	Δρmin = −0.92 e Å^−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.

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 > 2sigma(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
Ba	0.10759 (4)	0.32229 (2)	0.51410 (2)	0.01239 (10)
C1	0.3514 (6)	0.2501 (4)	0.3198 (2)	0.0090 (10)
C2	0.3333 (6)	0.2494 (4)	0.2561 (2)	0.0108 (10)
H2	0.295732	0.308640	0.233863	0.013*
C3	0.3693 (6)	0.1634 (4)	0.2246 (2)	0.0117 (10)
C4	0.4304 (6)	0.0779 (4)	0.2586 (2)	0.0112 (10)
H4	0.455553	0.018147	0.237907	0.013*
C5	0.4548 (6)	0.0800 (4)	0.3232 (2)	0.0113 (10)
C6	0.4134 (6)	0.1664 (3)	0.3536 (2)	0.0107 (10)
H6	0.427539	0.167863	0.397176	0.013*
C7	0.3047 (6)	0.3432 (4)	0.3523 (2)	0.0128 (11)
O1	0.2442 (5)	0.3416 (2)	0.40168 (15)	0.0142 (8)
O2	0.3339 (5)	0.4242 (2)	0.32175 (15)	0.0166 (8)
H2A	0.306637	0.474491	0.341541	0.025*
C8	0.3452 (7)	0.1603 (4)	0.1555 (2)	0.0115 (11)
O3	0.2714 (5)	0.0819 (2)	0.12888 (15)	0.0164 (8)
O4	0.3952 (5)	0.2339 (2)	0.12606 (15)	0.0149 (8)
C9	0.5295 (7)	−0.0091 (4)	0.3591 (2)	0.0139 (11)
O5	0.6130 (5)	−0.0023 (2)	0.41186 (15)	0.0167 (8)
O6	0.4978 (5)	−0.0939 (2)	0.32857 (15)	0.0157 (8)
H6A	0.551985	−0.140889	0.349588	0.024*
C11	0.3620 (6)	0.3379 (3)	0.7248 (2)	0.0100 (10)
C12	0.3343 (6)	0.2521 (4)	0.7580 (2)	0.0099 (10)
H12	0.296025	0.191986	0.736813	0.012*
C13	0.3617 (6)	0.2530 (4)	0.8217 (2)	0.0109 (10)
C14	0.4231 (6)	0.3393 (4)	0.8532 (2)	0.0123 (11)
H14	0.443321	0.339794	0.896846	0.015*
C15	0.4551 (6)	0.4258 (3)	0.8207 (2)	0.0101 (10)
C16	0.4233 (6)	0.4244 (3)	0.7561 (2)	0.0083 (10)
H16	0.443912	0.483188	0.733861	0.010*
C17	0.3190 (7)	0.3357 (4)	0.6553 (2)	0.0120 (11)
O11	0.2653 (5)	0.4150 (2)	0.62669 (14)	0.0131 (7)
O12	0.3321 (5)	0.2539 (2)	0.62741 (14)	0.0154 (8)
C18	0.3308 (6)	0.1603 (3)	0.8575 (2)	0.0113 (11)
O13	0.3181 (5)	0.1630 (2)	0.91213 (14)	0.0130 (7)
O14	0.3180 (5)	0.0797 (2)	0.82362 (15)	0.0154 (8)
H14A	0.284600	0.031413	0.843958	0.023*
C19	0.5209 (7)	0.5183 (3)	0.8551 (2)	0.0111 (10)
O15	0.6072 (5)	0.5162 (2)	0.90750 (15)	0.0182 (8)
O16	0.4780 (5)	0.6003 (2)	0.82360 (15)	0.0129 (7)
H16A	0.523 (7)	0.656 (4)	0.842 (2)	0.019*
O1W	−0.1934 (5)	0.4777 (3)	0.51036 (16)	0.0172 (8)
H1WA	−0.289 (5)	0.446 (3)	0.493 (2)	0.026*
H1WB	−0.204 (8)	0.466 (4)	0.5473 (8)	0.026*
O2W	0.5117 (5)	0.3255 (3)	0.51917 (15)	0.0174 (8)
H2WA	0.562 (7)	0.2693 (18)	0.516 (3)	0.026*
H2WB	0.546 (8)	0.342 (4)	0.5560 (8)	0.026*
O3W	0.2349 (5)	0.1338 (3)	0.49455 (16)	0.0197 (8)
H3WA	0.197 (8)	0.093 (3)	0.4665 (17)	0.029*
H3WB	0.284 (7)	0.101 (4)	0.5253 (16)	0.029*
O4W	−0.2291 (6)	0.1657 (3)	0.50050 (16)	0.0201 (8)
H4WA	−0.212 (8)	0.122 (3)	0.5282 (18)	0.030*
H4WB	−0.273 (8)	0.122 (3)	0.475 (2)	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba	0.01500 (15)	0.00961 (16)	0.01210 (14)	0.00119 (15)	0.00045 (11)	−0.00052 (14)
C1	0.005 (2)	0.007 (3)	0.014 (2)	0.0019 (19)	0.001 (2)	−0.0017 (19)
C2	0.009 (2)	0.006 (2)	0.018 (3)	0.000 (2)	0.006 (2)	−0.001 (2)
C3	0.006 (2)	0.013 (3)	0.016 (2)	−0.001 (2)	0.0001 (19)	0.000 (2)
C4	0.014 (3)	0.006 (3)	0.014 (2)	−0.003 (2)	0.003 (2)	−0.0040 (19)
C5	0.006 (2)	0.010 (3)	0.017 (3)	0.000 (2)	0.000 (2)	0.002 (2)
C6	0.009 (2)	0.012 (3)	0.012 (2)	−0.001 (2)	0.0036 (19)	−0.001 (2)
C7	0.005 (2)	0.017 (3)	0.016 (3)	0.005 (2)	−0.001 (2)	−0.001 (2)
O1	0.0156 (18)	0.013 (2)	0.0136 (17)	0.0021 (15)	0.0006 (15)	−0.0039 (14)
O2	0.025 (2)	0.0078 (19)	0.0180 (19)	0.0004 (16)	0.0071 (16)	−0.0010 (15)
C8	0.009 (2)	0.012 (3)	0.014 (2)	0.001 (2)	0.004 (2)	0.002 (2)
O3	0.029 (2)	0.0056 (18)	0.0140 (18)	−0.0068 (16)	0.0012 (16)	−0.0017 (14)
O4	0.024 (2)	0.0062 (18)	0.0145 (18)	−0.0024 (15)	0.0020 (16)	−0.0003 (14)
C9	0.013 (3)	0.013 (3)	0.017 (3)	−0.003 (2)	0.005 (2)	0.002 (2)
O5	0.023 (2)	0.0101 (19)	0.0155 (18)	0.0010 (15)	−0.0032 (16)	0.0011 (14)
O6	0.020 (2)	0.0077 (19)	0.0177 (19)	0.0025 (15)	−0.0037 (16)	0.0006 (15)
C11	0.008 (2)	0.011 (3)	0.011 (2)	0.001 (2)	0.0010 (19)	−0.0019 (19)
C12	0.005 (2)	0.006 (2)	0.018 (3)	0.0025 (19)	0.001 (2)	−0.0024 (19)
C13	0.008 (2)	0.012 (3)	0.013 (2)	−0.003 (2)	0.003 (2)	−0.002 (2)
C14	0.008 (2)	0.018 (3)	0.011 (2)	0.001 (2)	0.0005 (19)	0.000 (2)
C15	0.006 (2)	0.009 (3)	0.016 (3)	0.003 (2)	0.002 (2)	0.000 (2)
C16	0.005 (2)	0.007 (2)	0.012 (2)	−0.0006 (19)	0.0010 (19)	0.0015 (19)
C17	0.010 (2)	0.015 (3)	0.011 (2)	−0.001 (2)	0.003 (2)	−0.002 (2)
O11	0.0214 (19)	0.0064 (18)	0.0107 (17)	0.0012 (15)	−0.0001 (15)	0.0018 (14)
O12	0.0215 (19)	0.0128 (19)	0.0113 (17)	0.0049 (16)	0.0005 (15)	−0.0010 (14)
C18	0.006 (2)	0.010 (3)	0.018 (3)	0.003 (2)	0.002 (2)	0.001 (2)
O13	0.0178 (18)	0.0094 (19)	0.0121 (17)	−0.0005 (14)	0.0035 (15)	−0.0013 (14)
O14	0.023 (2)	0.0080 (18)	0.0150 (18)	−0.0026 (16)	0.0029 (16)	0.0024 (14)
C19	0.015 (3)	0.006 (3)	0.013 (2)	−0.001 (2)	0.005 (2)	0.002 (2)
O15	0.024 (2)	0.012 (2)	0.0159 (19)	−0.0011 (16)	−0.0039 (16)	−0.0009 (15)
O16	0.0202 (19)	0.0052 (18)	0.0115 (17)	−0.0040 (15)	−0.0035 (15)	−0.0007 (14)
O1W	0.020 (2)	0.014 (2)	0.0175 (19)	−0.0038 (16)	0.0025 (17)	−0.0036 (16)
O2W	0.0167 (19)	0.021 (2)	0.0140 (17)	0.0013 (17)	−0.0010 (15)	−0.0016 (18)
O3W	0.029 (2)	0.014 (2)	0.013 (2)	0.0035 (17)	−0.0041 (17)	−0.0010 (15)
O4W	0.027 (2)	0.014 (2)	0.018 (2)	0.0015 (18)	0.0010 (17)	0.0033 (16)

Geometric parameters (Å, º)

Ba—O3W	2.736 (4)	O6—H6A	0.8400
Ba—O1	2.796 (3)	C11—C16	1.386 (6)
Ba—O1W^i	2.817 (4)	C11—C12	1.393 (6)
Ba—O13^ii	2.817 (3)	C11—C17	1.515 (6)
Ba—O2W	2.846 (4)	C12—C13	1.387 (6)
Ba—O11	2.850 (3)	C12—H12	0.9500
Ba—O12	2.904 (3)	C13—C14	1.385 (6)
Ba—O1W	2.971 (4)	C13—C18	1.504 (7)
Ba—O4W	3.156 (4)	C14—C15	1.397 (6)
Ba—O4^iii	3.158 (3)	C14—H14	0.9500
Ba—C17	3.253 (5)	C15—C16	1.405 (6)
C1—C6	1.382 (6)	C15—C19	1.492 (6)
C1—C2	1.389 (6)	C16—H16	0.9500
C1—C7	1.498 (6)	C17—O11	1.265 (5)
C2—C3	1.388 (6)	C17—O12	1.266 (5)
C2—H2	0.9500	C18—O13	1.219 (6)
C3—C4	1.402 (6)	C18—O14	1.308 (5)
C3—C8	1.506 (6)	O14—H14A	0.8400
C4—C5	1.408 (6)	C19—O15	1.224 (5)
C4—H4	0.9500	C19—O16	1.312 (5)
C5—C6	1.389 (6)	O16—H16A	0.88 (5)
C5—C9	1.486 (6)	O1W—H1WA	0.841 (5)
C6—H6	0.9500	O1W—H1WB	0.840 (5)
C7—O1	1.225 (6)	O2W—H2WA	0.840 (5)
C7—O2	1.309 (6)	O2W—H2WB	0.840 (5)
O2—H2A	0.8400	O3W—H3WA	0.839 (5)
C8—O4	1.258 (5)	O3W—H3WB	0.839 (5)
C8—O3	1.276 (5)	O4W—H4WA	0.841 (5)
C9—O5	1.226 (6)	O4W—H4WB	0.840 (5)
C9—O6	1.323 (6)
O3W—Ba—O1	77.41 (10)	C6—C5—C9	119.8 (4)
O3W—Ba—O1W^i	139.71 (11)	C4—C5—C9	120.2 (4)
O1—Ba—O1W^i	68.35 (10)	C1—C6—C5	119.4 (4)
O3W—Ba—O13^ii	99.07 (10)	C1—C6—H6	120.3
O1—Ba—O13^ii	66.03 (9)	C5—C6—H6	120.3
O1W^i—Ba—O13^ii	86.16 (10)	O1—C7—O2	124.9 (4)
O3W—Ba—O2W	70.60 (11)	O1—C7—C1	122.6 (4)
O1—Ba—O2W	63.81 (9)	O2—C7—C1	112.5 (4)
O1W^i—Ba—O2W	75.52 (11)	C7—O1—Ba	175.7 (3)
O13^ii—Ba—O2W	129.83 (9)	C7—O2—H2A	109.5
O3W—Ba—O11	116.26 (10)	O4—C8—O3	122.3 (4)
O1—Ba—O11	125.94 (9)	O4—C8—C3	120.0 (4)
O1W^i—Ba—O11	71.56 (9)	O3—C8—C3	117.7 (4)
O13^ii—Ba—O11	144.05 (9)	C8—O4—Ba^iv	114.6 (3)
O2W—Ba—O11	72.25 (10)	O5—C9—O6	124.6 (4)
O3W—Ba—O12	72.08 (10)	O5—C9—C5	121.9 (4)
O1—Ba—O12	124.94 (9)	O6—C9—C5	113.5 (4)
O1W^i—Ba—O12	110.97 (10)	C9—O6—H6A	109.5
O13^ii—Ba—O12	161.83 (9)	C16—C11—C12	119.1 (4)
O2W—Ba—O12	63.24 (10)	C16—C11—C17	121.4 (4)
O11—Ba—O12	45.12 (9)	C12—C11—C17	119.4 (4)
O3W—Ba—O1W	153.33 (11)	C13—C12—C11	120.9 (5)
O1—Ba—O1W	104.44 (9)	C13—C12—H12	119.5
O1W^i—Ba—O1W	60.11 (12)	C11—C12—H12	119.5
O13^ii—Ba—O1W	59.56 (9)	C14—C13—C12	120.1 (5)
O2W—Ba—O1W	134.66 (10)	C14—C13—C18	119.1 (4)
O11—Ba—O1W	84.68 (9)	C12—C13—C18	120.8 (4)
O12—Ba—O1W	123.05 (9)	C13—C14—C15	119.8 (4)
O3W—Ba—O4W	68.48 (11)	C13—C14—H14	120.1
O1—Ba—O4W	109.33 (9)	C15—C14—H14	120.1
O1W^i—Ba—O4W	142.65 (10)	C14—C15—C16	119.6 (4)
O13^ii—Ba—O4W	61.28 (9)	C14—C15—C19	119.3 (4)
O2W—Ba—O4W	138.96 (10)	C16—C15—C19	121.1 (4)
O11—Ba—O4W	124.53 (9)	C11—C16—C15	120.4 (4)
O12—Ba—O4W	100.56 (9)	C11—C16—H16	119.8
O1W—Ba—O4W	86.25 (10)	C15—C16—H16	119.8
O3W—Ba—O4^iii	96.20 (10)	O11—C17—O12	121.5 (4)
O1—Ba—O4^iii	167.80 (9)	O11—C17—C11	119.2 (4)
O1W^i—Ba—O4^iii	121.06 (9)	O12—C17—C11	119.2 (4)
O13^ii—Ba—O4^iii	105.34 (9)	O11—C17—Ba	60.5 (2)
O2W—Ba—O4^iii	124.23 (9)	O12—C17—Ba	62.9 (2)
O11—Ba—O4^iii	66.18 (9)	C11—C17—Ba	164.2 (3)
O12—Ba—O4^iii	61.18 (9)	C17—O11—Ba	96.8 (3)
O1W—Ba—O4^iii	76.57 (9)	C17—O12—Ba	94.3 (3)
O4W—Ba—O4^iii	58.47 (9)	O13—C18—O14	125.3 (4)
O3W—Ba—C17	94.87 (11)	O13—C18—C13	121.9 (4)
O1—Ba—C17	132.08 (10)	O14—C18—C13	112.8 (4)
O1W^i—Ba—C17	92.75 (11)	C18—O13—Ba^v	129.7 (3)
O13^ii—Ba—C17	159.65 (10)	C18—O14—H14A	109.5
O2W—Ba—C17	69.00 (11)	O15—C19—O16	124.3 (4)
O11—Ba—C17	22.71 (10)	O15—C19—C15	122.5 (4)
O12—Ba—C17	22.83 (10)	O16—C19—C15	113.3 (4)
O1W—Ba—C17	102.48 (11)	C19—O16—H16A	115 (3)
O4W—Ba—C17	111.31 (11)	Ba^i—O1W—Ba	119.89 (12)
O4^iii—Ba—C17	58.18 (10)	Ba^i—O1W—H1WA	125 (4)
C6—C1—C2	120.9 (4)	Ba—O1W—H1WA	101 (4)
C6—C1—C7	119.6 (4)	Ba^i—O1W—H1WB	114 (4)
C2—C1—C7	119.6 (4)	Ba—O1W—H1WB	90 (4)
C3—C2—C1	120.9 (5)	H1WA—O1W—H1WB	99 (5)
C3—C2—H2	119.6	Ba—O2W—H2WA	115 (4)
C1—C2—H2	119.6	Ba—O2W—H2WB	101 (4)
C2—C3—C4	118.5 (4)	H2WA—O2W—H2WB	105 (5)
C2—C3—C8	121.7 (4)	Ba—O3W—H3WA	130 (4)
C4—C3—C8	119.8 (4)	Ba—O3W—H3WB	118 (4)
C3—C4—C5	120.3 (4)	H3WA—O3W—H3WB	108 (5)
C3—C4—H4	119.8	Ba—O4W—H4WA	112 (4)
C5—C4—H4	119.8	Ba—O4W—H4WB	137 (4)
C6—C5—C4	120.0 (4)	H4WA—O4W—H4WB	90 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3^vi	0.84	1.70	2.537 (5)	171
O6—H6A···O12^vii	0.84	1.76	2.578 (5)	164
O14—H14A···O11^viii	0.84	1.74	2.569 (5)	167
O16—H16A···O4^ix	0.88 (5)	1.70 (5)	2.585 (5)	177 (5)
O1W—H1WA···O2W^x	0.84 (1)	2.27 (4)	2.945 (5)	138 (5)
O1W—H1WB···O3^iii	0.84 (1)	1.94 (1)	2.774 (5)	171 (6)
O2W—H2WA···O4W^xi	0.84 (1)	2.09 (2)	2.887 (5)	158 (5)
O2W—H2WB···O3^v	0.84 (1)	2.33 (3)	3.075 (5)	148 (5)
O2W—H2WB···O12	0.84 (1)	2.62 (5)	3.015 (5)	111 (4)
O3W—H3WA···O15^ii	0.84 (1)	2.00 (1)	2.833 (5)	173 (5)
O3W—H3WB···O5^vii	0.84 (1)	1.98 (1)	2.804 (5)	169 (6)
O4W—H4WA···O15^viii	0.84 (1)	2.06 (2)	2.889 (5)	167 (5)
O4W—H4WB···O5^x	0.84 (1)	2.24 (1)	3.081 (5)	176 (6)

Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (v) x+1/2, −y+1/2, z+1/2; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+1, −y, −z+1; (viii) −x+1/2, y−1/2, −z+3/2; (ix) −x+1, −y+1, −z+1; (x) x−1, y, z; (xi) x+1, y, z.

(BaBTC-2)

Crystal data

C18H16BaO15·H2O	Dx = 1.899 Mg m^−3
Mr = 627.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6737 reflections
a = 7.2781 (3) Å	θ = 3.0–25.7°
b = 13.4581 (4) Å	µ = 1.89 mm^−1
c = 22.4129 (6) Å	T = 100 K
V = 2195.31 (14) Å^3	Neddle, colourless
Z = 4	0.28 × 0.08 × 0.06 mm
F(000) = 1240

Data collection

KUMA KM-4 with CCD detector diffractometer	4311 independent reflections
Radiation source: fine-focus sealed X-ray tube	3802 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.056
ω–scan	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.899, Tmax = 1.000	k = −16→16
29814 measured reflections	l = −27→27

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0312P)^2 + 22.2577P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
4311 reflections	Δρmax = 1.83 e Å^−3
321 parameters	Δρmin = −2.44 e Å^−3
0 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.43 (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 inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ba	0.62643 (14)	0.60662 (6)	0.50811 (3)	0.0415 (3)
C1	0.6223 (14)	0.6137 (7)	0.7217 (4)	0.0132 (18)
C2	0.6709 (13)	0.5277 (7)	0.7523 (4)	0.014 (2)
H2	0.719487	0.472068	0.731551	0.017*
C3	0.6467 (14)	0.5244 (7)	0.8148 (4)	0.0110 (19)
C4	0.5897 (13)	0.6085 (8)	0.8457 (4)	0.015 (2)
H4	0.577787	0.606649	0.887877	0.018*
C5	0.5507 (14)	0.6940 (8)	0.8151 (5)	0.015 (2)
C6	0.5676 (13)	0.6975 (7)	0.7525 (4)	0.011 (2)
H6	0.541518	0.757218	0.731534	0.013*
C7	0.6332 (15)	0.6114 (8)	0.6538 (4)	0.0151 (19)
O1	0.6634 (12)	0.6898 (5)	0.6248 (3)	0.0208 (17)
O2	0.6091 (13)	0.5291 (5)	0.6279 (3)	0.0222 (18)
C8	0.6935 (14)	0.4325 (7)	0.8483 (5)	0.016 (2)
O3	0.6849 (12)	0.4257 (5)	0.9020 (3)	0.0261 (19)
O4	0.7437 (11)	0.3576 (5)	0.8128 (3)	0.0190 (16)
H4O	0.765020	0.307390	0.833860	0.028*
C9	0.4904 (14)	0.7844 (8)	0.8489 (5)	0.014 (2)
O5	0.4175 (11)	0.7787 (6)	0.8981 (3)	0.0203 (17)
O6	0.5250 (10)	0.8687 (5)	0.8219 (3)	0.0173 (16)
H6O	0.447260	0.911170	0.831610	0.026*
C11	0.3604 (15)	0.4835 (7)	0.3262 (4)	0.015 (2)
C12	0.3344 (14)	0.4816 (7)	0.2640 (5)	0.016 (2)
H12	0.290061	0.538844	0.243746	0.019*
C13	0.3739 (15)	0.3959 (8)	0.2324 (4)	0.0152 (18)
C14	0.4324 (13)	0.3115 (7)	0.2619 (5)	0.014 (2)
H14	0.456263	0.252335	0.240116	0.017*
C15	0.4563 (14)	0.3129 (8)	0.3235 (5)	0.014 (2)
C16	0.4248 (14)	0.4002 (9)	0.3561 (4)	0.019 (2)
H16	0.447152	0.402280	0.397868	0.022*
C17	0.3299 (14)	0.5757 (7)	0.3607 (5)	0.017 (2)
O11	0.3819 (12)	0.5898 (5)	0.4112 (3)	0.0253 (17)
O12	0.2400 (12)	0.6434 (6)	0.3289 (4)	0.0275 (19)
H12O	0.225820	0.694350	0.349940	0.041*
C18	0.3529 (13)	0.3931 (8)	0.1649 (4)	0.0146 (19)
O13	0.3219 (11)	0.3118 (5)	0.1399 (3)	0.0218 (18)
O14	0.3708 (13)	0.4736 (5)	0.1369 (3)	0.0222 (17)
C19	0.5196 (14)	0.2219 (8)	0.3554 (5)	0.015 (2)
O15	0.5882 (12)	0.2236 (6)	0.4049 (4)	0.030 (2)
O16	0.4926 (10)	0.1399 (5)	0.3243 (3)	0.0193 (17)
H16O	0.543640	0.091580	0.342110	0.029*
O1W	1.131 (2)	0.3603 (7)	0.4863 (4)	0.058 (3)
H1W1	1.096513	0.319724	0.513142	0.087*
H2W1	1.155620	0.328615	0.454333	0.087*
O2W	0.9718 (19)	0.5433 (9)	0.5246 (5)	0.070 (4)
H1W2	0.982970	0.487960	0.509600	0.105*
H2W2	0.991100	0.538570	0.560970	0.105*
O3W	0.271 (2)	0.7050 (11)	0.5245 (5)	0.090 (5)
H1W3	0.197339	0.665511	0.510192	0.135*
H2W3	0.254439	0.702544	0.560650	0.135*
O4W	0.509 (3)	0.4292 (13)	0.5100 (9)	0.042 (4)*	0.5
H1W4	0.579709	0.388429	0.534186	0.063*	0.5
H2W4	0.394138	0.424329	0.528008	0.063*	0.5
O5W	0.658 (3)	0.3937 (17)	0.4990 (11)	0.067 (6)*	0.5
H1W5	0.678292	0.351166	0.540494	0.101*	0.5
H2W5	0.535603	0.351446	0.484105	0.101*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba	0.0727 (6)	0.0363 (4)	0.0156 (3)	−0.0247 (4)	0.0137 (4)	−0.0058 (3)
C1	0.014 (5)	0.008 (4)	0.018 (4)	−0.005 (4)	0.001 (4)	0.004 (4)
C2	0.011 (5)	0.014 (5)	0.016 (5)	−0.002 (4)	0.000 (4)	−0.001 (4)
C3	0.007 (5)	0.011 (5)	0.015 (5)	−0.007 (4)	−0.002 (4)	0.001 (4)
C4	0.018 (5)	0.016 (5)	0.011 (4)	0.003 (5)	−0.006 (4)	−0.003 (4)
C5	0.014 (5)	0.010 (5)	0.019 (5)	0.000 (4)	0.004 (4)	−0.001 (4)
C6	0.010 (5)	0.009 (5)	0.015 (5)	−0.003 (4)	−0.001 (4)	−0.001 (4)
C7	0.019 (5)	0.010 (4)	0.016 (4)	−0.011 (5)	−0.003 (4)	0.002 (4)
O1	0.034 (5)	0.015 (4)	0.013 (4)	−0.002 (3)	0.004 (3)	−0.001 (3)
O2	0.039 (5)	0.012 (4)	0.016 (4)	−0.002 (4)	0.005 (4)	0.000 (3)
C8	0.016 (5)	0.009 (5)	0.023 (6)	−0.004 (4)	−0.005 (4)	−0.002 (4)
O3	0.042 (5)	0.013 (4)	0.023 (4)	0.003 (3)	−0.007 (4)	0.001 (3)
O4	0.030 (4)	0.006 (3)	0.021 (4)	0.003 (3)	−0.001 (3)	0.000 (3)
C9	0.017 (5)	0.009 (5)	0.017 (5)	−0.007 (4)	−0.004 (4)	0.000 (4)
O5	0.031 (5)	0.016 (4)	0.014 (4)	0.001 (4)	0.005 (3)	0.000 (3)
O6	0.024 (4)	0.011 (4)	0.016 (4)	0.000 (3)	0.003 (3)	0.004 (3)
C11	0.015 (5)	0.009 (5)	0.022 (5)	−0.001 (4)	0.003 (5)	−0.002 (4)
C12	0.015 (5)	0.007 (5)	0.025 (6)	0.001 (4)	0.010 (5)	0.002 (4)
C13	0.018 (5)	0.009 (4)	0.018 (4)	−0.002 (5)	−0.001 (5)	0.001 (4)
C14	0.006 (5)	0.011 (5)	0.025 (6)	−0.001 (4)	0.003 (4)	0.001 (4)
C15	0.010 (5)	0.005 (5)	0.027 (6)	0.002 (4)	0.000 (4)	0.001 (4)
C16	0.019 (5)	0.019 (5)	0.018 (5)	−0.001 (4)	0.006 (4)	0.004 (5)
C17	0.013 (5)	0.015 (5)	0.025 (6)	0.006 (4)	0.006 (4)	0.005 (4)
O11	0.041 (5)	0.020 (4)	0.015 (3)	0.007 (4)	0.000 (4)	0.002 (3)
O12	0.040 (5)	0.014 (4)	0.028 (4)	0.011 (4)	−0.010 (4)	−0.002 (3)
C18	0.012 (5)	0.011 (4)	0.022 (5)	−0.008 (4)	−0.003 (4)	0.007 (4)
O13	0.035 (5)	0.011 (4)	0.019 (4)	−0.005 (3)	0.003 (3)	−0.001 (3)
O14	0.032 (4)	0.011 (4)	0.024 (4)	−0.002 (4)	0.001 (4)	0.002 (3)
C19	0.011 (5)	0.006 (5)	0.028 (6)	0.005 (4)	0.002 (5)	0.002 (4)
O15	0.040 (6)	0.015 (4)	0.035 (5)	0.005 (4)	−0.016 (4)	0.004 (3)
O16	0.020 (4)	0.010 (4)	0.028 (4)	0.004 (3)	−0.008 (3)	0.003 (3)
O1W	0.095 (8)	0.052 (6)	0.028 (5)	−0.011 (7)	0.005 (7)	−0.011 (5)
O2W	0.106 (10)	0.058 (7)	0.045 (7)	−0.013 (7)	0.023 (7)	−0.021 (5)
O3W	0.133 (13)	0.098 (10)	0.039 (7)	0.060 (10)	0.008 (7)	0.006 (7)

Geometric parameters (Å, º)

Ba—O4W	2.538 (17)	C11—C16	1.388 (14)
Ba—O2W	2.680 (14)	C11—C12	1.408 (14)
Ba—O3^i	2.781 (8)	C11—C17	1.478 (13)
Ba—O11	2.818 (8)	C12—C13	1.383 (14)
Ba—O3W^ii	2.841 (13)	C12—H12	0.9500
Ba—O1	2.858 (7)	C13—C14	1.382 (14)
Ba—O5W	2.88 (2)	C13—C18	1.522 (12)
Ba—O2	2.882 (7)	C14—C15	1.390 (15)
Ba—O3W	2.929 (14)	C14—H14	0.9500
Ba—C7	3.266 (9)	C15—C16	1.404 (15)
C1—C6	1.380 (14)	C15—C19	1.492 (14)
C1—C2	1.391 (14)	C16—H16	0.9500
C1—C7	1.525 (12)	C17—O11	1.207 (13)
C2—C3	1.412 (13)	C17—O12	1.330 (12)
C2—H2	0.9500	O12—H12O	0.8386
C3—C4	1.390 (14)	C18—O13	1.250 (12)
C3—C8	1.486 (13)	C18—O14	1.258 (12)
C4—C5	1.368 (15)	C19—O15	1.215 (13)
C4—H4	0.9500	C19—O16	1.320 (13)
C5—C6	1.411 (14)	O16—H16O	0.8494
C5—C9	1.499 (14)	O1W—H1W1	0.8512
C6—H6	0.9500	O1W—H2W1	0.8522
C7—O1	1.257 (12)	O2W—H1W2	0.8207
C7—O2	1.263 (12)	O2W—H2W2	0.8295
C8—O3	1.208 (13)	O3W—H1W3	0.8200
C8—O4	1.335 (12)	O3W—H2W3	0.8200
O4—H4O	0.8385	O4W—H1W4	0.9278
C9—O5	1.226 (13)	O4W—H2W4	0.9279
C9—O6	1.310 (12)	O5W—H1W5	1.1016
O6—H6O	0.8330	O5W—H2W5	1.1103
O4W—Ba—O2W	90.9 (5)	O1—C7—C1	120.5 (9)
O4W—Ba—O3^i	92.0 (5)	O2—C7—C1	118.0 (8)
O2W—Ba—O3^i	66.7 (3)	O1—C7—Ba	60.2 (5)
O4W—Ba—O11	74.0 (5)	O2—C7—Ba	61.4 (5)
O2W—Ba—O11	132.3 (3)	C1—C7—Ba	176.2 (7)
O3^i—Ba—O11	68.9 (2)	C7—O1—Ba	97.3 (5)
O4W—Ba—O3W^ii	165.8 (5)	C7—O2—Ba	96.0 (5)
O2W—Ba—O3W^ii	88.4 (4)	O3—C8—O4	123.4 (9)
O3^i—Ba—O3W^ii	74.7 (3)	O3—C8—C3	123.6 (9)
O11—Ba—O3W^ii	96.2 (3)	O4—C8—C3	113.0 (9)
O4W—Ba—O1	112.6 (5)	C8—O3—Ba^iii	146.9 (8)
O2W—Ba—O1	84.8 (3)	C8—O4—H4O	108.9
O3^i—Ba—O1	142.9 (2)	O5—C9—O6	123.5 (10)
O11—Ba—O1	142.8 (2)	O5—C9—C5	122.0 (10)
O3W^ii—Ba—O1	81.4 (3)	O6—C9—C5	114.5 (9)
O2W—Ba—O5W	67.5 (5)	C9—O6—H6O	110.1
O3^i—Ba—O5W	75.2 (5)	C16—C11—C12	120.6 (9)
O11—Ba—O5W	85.2 (5)	C16—C11—C17	118.4 (9)
O3W^ii—Ba—O5W	147.1 (6)	C12—C11—C17	120.9 (9)
O1—Ba—O5W	116.5 (5)	C13—C12—C11	119.6 (9)
O4W—Ba—O2	68.2 (5)	C13—C12—H12	120.2
O2W—Ba—O2	78.3 (3)	C11—C12—H12	120.2
O3^i—Ba—O2	139.6 (2)	C14—C13—C12	120.3 (9)
O11—Ba—O2	131.4 (2)	C14—C13—C18	119.1 (9)
O3W^ii—Ba—O2	125.4 (3)	C12—C13—C18	120.5 (9)
O1—Ba—O2	45.05 (19)	C13—C14—C15	120.2 (9)
O5W—Ba—O2	73.1 (5)	C13—C14—H14	119.9
O4W—Ba—O3W	97.2 (5)	C15—C14—H14	119.9
O2W—Ba—O3W	162.7 (3)	C14—C15—C16	120.5 (10)
O3^i—Ba—O3W	127.9 (3)	C14—C15—C19	120.3 (9)
O11—Ba—O3W	64.9 (3)	C16—C15—C19	119.2 (10)
O3W^ii—Ba—O3W	87.48 (19)	C11—C16—C15	118.7 (9)
O1—Ba—O3W	78.0 (3)	C11—C16—H16	120.7
O5W—Ba—O3W	122.0 (6)	C15—C16—H16	120.7
O2—Ba—O3W	90.5 (3)	O11—C17—O12	123.3 (9)
O4W—Ba—C7	90.4 (5)	O11—C17—C11	125.1 (9)
O2W—Ba—C7	81.6 (3)	O12—C17—C11	111.6 (9)
O3^i—Ba—C7	148.3 (3)	C17—O11—Ba	158.9 (8)
O11—Ba—C7	141.4 (2)	C17—O12—H12O	108.6
O3W^ii—Ba—C7	103.5 (3)	O13—C18—O14	123.3 (9)
O1—Ba—C7	22.4 (2)	O13—C18—C13	119.0 (9)
O5W—Ba—C7	95.1 (5)	O14—C18—C13	117.6 (9)
O2—Ba—C7	22.6 (2)	O15—C19—O16	124.0 (10)
O3W—Ba—C7	83.0 (3)	O15—C19—C15	123.3 (10)
C6—C1—C2	120.4 (8)	O16—C19—C15	112.7 (9)
C6—C1—C7	122.0 (9)	C19—O16—H16O	109.0
C2—C1—C7	117.6 (9)	H1W1—O1W—H2W1	109.6
C1—C2—C3	118.9 (9)	Ba—O2W—H1W2	109.0
C1—C2—H2	120.5	Ba—O2W—H2W2	108.6
C3—C2—H2	120.5	H1W2—O2W—H2W2	108.5
C4—C3—C2	120.3 (9)	Ba^iv—O3W—Ba	134.3 (6)
C4—C3—C8	119.7 (9)	Ba^iv—O3W—H1W3	103.6
C2—C3—C8	119.9 (9)	Ba—O3W—H1W3	103.6
C5—C4—C3	119.8 (8)	Ba^iv—O3W—H2W3	103.6
C5—C4—H4	120.1	Ba—O3W—H2W3	103.6
C3—C4—H4	120.1	H1W3—O3W—H2W3	105.3
C4—C5—C6	120.5 (9)	Ba—O4W—H1W4	112.2
C4—C5—C9	119.4 (9)	Ba—O4W—H2W4	112.1
C6—C5—C9	120.1 (9)	H1W4—O4W—H2W4	101.9
C1—C6—C5	119.7 (9)	Ba—O5W—H1W5	117.9
C1—C6—H6	120.2	Ba—O5W—H2W5	117.8
C5—C6—H6	120.2	H1W5—O5W—H2W5	95.4
O1—C7—O2	121.5 (8)
C6—C1—C2—C3	6.0 (15)	C4—C5—C9—O6	154.5 (10)
C7—C1—C2—C3	−174.4 (9)	C6—C5—C9—O6	−25.2 (14)
C1—C2—C3—C4	−5.2 (15)	C16—C11—C12—C13	−0.1 (16)
C1—C2—C3—C8	178.6 (9)	C17—C11—C12—C13	176.4 (10)
C2—C3—C4—C5	2.2 (15)	C11—C12—C13—C14	2.3 (16)
C8—C3—C4—C5	178.5 (9)	C11—C12—C13—C18	−178.0 (10)
C3—C4—C5—C6	0.1 (16)	C12—C13—C14—C15	−1.6 (16)
C3—C4—C5—C9	−179.6 (9)	C18—C13—C14—C15	178.7 (9)
C2—C1—C6—C5	−3.7 (15)	C13—C14—C15—C16	−1.2 (15)
C7—C1—C6—C5	176.7 (9)	C13—C14—C15—C19	−179.9 (10)
C4—C5—C6—C1	0.6 (15)	C12—C11—C16—C15	−2.6 (16)
C9—C5—C6—C1	−179.7 (9)	C17—C11—C16—C15	−179.2 (9)
C6—C1—C7—O1	27.9 (16)	C14—C15—C16—C11	3.3 (15)
C2—C1—C7—O1	−151.7 (10)	C19—C15—C16—C11	−178.0 (9)
C6—C1—C7—O2	−151.4 (11)	C16—C11—C17—O11	11.8 (17)
C2—C1—C7—O2	29.0 (15)	C12—C11—C17—O11	−164.8 (11)
O2—C7—O1—Ba	3.6 (12)	C16—C11—C17—O12	−169.4 (9)
C1—C7—O1—Ba	−175.7 (9)	C12—C11—C17—O12	14.0 (14)
O1—C7—O2—Ba	−3.6 (11)	O12—C17—O11—Ba	−121.5 (16)
C1—C7—O2—Ba	175.7 (8)	C11—C17—O11—Ba	57 (2)
C4—C3—C8—O3	0.1 (16)	C14—C13—C18—O13	26.1 (15)
C2—C3—C8—O3	176.3 (10)	C12—C13—C18—O13	−153.7 (10)
C4—C3—C8—O4	179.2 (9)	C14—C13—C18—O14	−152.9 (10)
C2—C3—C8—O4	−4.5 (14)	C12—C13—C18—O14	27.4 (15)
O4—C8—O3—Ba^iii	63.3 (17)	C14—C15—C19—O15	160.2 (11)
C3—C8—O3—Ba^iii	−117.6 (12)	C16—C15—C19—O15	−18.5 (16)
C4—C5—C9—O5	−24.4 (16)	C14—C15—C19—O16	−20.0 (14)
C6—C5—C9—O5	155.9 (10)	C16—C15—C19—O16	161.3 (9)

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+3/2, −y+1, z+1/2; (iv) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O13^v	0.84	1.76	2.578 (10)	165.3
O6—H6O···O2^vi	0.83	1.87	2.622 (10)	148.8
O12—H12O···O1^iv	0.84	1.72	2.535 (10)	163.5
O16—H16O···O14^vii	0.85	1.77	2.600 (10)	165.2
O2W—H1W2···O1W	0.82	2.09	2.854 (16)	153.8
O2W—H2W2···O14^iii	0.83	1.98	2.775 (14)	159.3
O3W—H1W3···O2W^viii	0.82	2.35	3.08 (2)	149
O3W—H2W3···O13^ix	0.82	1.87	2.682 (14)	170
O4W^a—H1^W^4a···O5^x	0.93	2.12	2.94 (2)	147
O4W^a—H2^W^4a···O1W^viii	0.93	2.30	2.95 (2)	127
O5W^b—H1^W^5b···O5^x	1.10	1.82	2.83 (3)	150
O5W^b—H2^W^5b···O15	1.11	2.50	3.16 (2)	116

Symmetry codes: (iii) −x+3/2, −y+1, z+1/2; (iv) x−1/2, −y+3/2, −z+1; (v) x+1/2, −y+1/2, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+1, y−1/2, −z+1/2; (viii) x−1, y, z; (ix) −x+1/2, −y+1, z+1/2; (x) −x+1, y−1/2, −z+3/2.