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Acta Cryst. (2020). E76, 270-272
https://doi.org/10.1107/S205698902000081X
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B. L. Westcott, G. Crundwell and N. L. Alicea-Velázquez
The reaction of 1,3-dipyridyl-1,2-propane-1,3-dione (dppo) with nickel(II) bromide in HBr-acidified methanol produces a bromide salt containing the [(C13H11N2O2)(H2O)4Ni]+3 cation. The ligand is in its enol form— the O atoms bond to the nickel whereas the pyridyl N atoms are protonated as pyridinium rings. The nickel completes its octahedral coordinatin sphere by binding four waters. Three bromides balance the charge of the cation and there are two waters of hydration. The mean plane of the flat ligand makes an angle of 19.480 (17)° with respect to the plane defined by the nickel and its four equatorial O atoms. There is exstensive hydrogen bonding involving the anions, waters, and pyridinium N atoms.
Keywords: crystal structure; dipyridylpropanedione; pyridinium; nickel.
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Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S205698902000081X/zl2768sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S205698902000081X/zl2768Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S205698902000081X/zl2768sup3.pdf |
CCDC reference: 1979583
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.043
- wR factor = 0.125
- Data-to-parameter ratio = 28.5
checkCIF/PLATON results
No syntax errors foundAlert level BPLAT420_ALERT_2_B D-H Without Acceptor O8 --H8A . Please CheckPLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min). 21 Note
Alert level CPLAT222_ALERT_3_C NonSolvent Resd 1 H Uiso(max)/Uiso(min) Range 6.1 RatioPLAT230_ALERT_2_C Hirshfeld Test Diff for N2 --C9 . 6.5 s.u.PLAT260_ALERT_2_C Large Average Ueq of Residue Including O8 0.106 CheckPLAT420_ALERT_2_C D-H Without Acceptor N1 --H1 . Please CheckPLAT420_ALERT_2_C D-H Without Acceptor N2 --H2 . Please CheckPLAT480_ALERT_4_C Long H...A H-Bond Reported H1 ..BR1 . 2.94 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H2 ..BR1 . 3.02 Ang.PLAT480_ALERT_4_C Long H...A H-Bond Reported H8A ..BR3 . 3.06 Ang.PLAT481_ALERT_4_C Long D...A H-Bond Reported O8 ..BR3 3.88 Ang.PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ...... 3.299 CheckPLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 6 Report
Alert level GPLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 18 NotePLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 ReportPLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records 2 ReportPLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 CheckPLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 CheckPLAT432_ALERT_2_G Short Inter X...Y Contact Br2 ..C10 3.31 Ang. x,y,-1+z = 1_554 CheckPLAT432_ALERT_2_G Short Inter X...Y Contact Br3 ..C4 3.33 Ang. 1-x,1-y,1-z = 3_666 CheckPLAT794_ALERT_5_G Tentative Bond Valency for Ni1 (II) . 2.07 InfoPLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 12 NotePLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 744 NotePLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF .... 1 NotePLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 6 NotePLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 2 Info 0 ALERT level A = Most likely a serious problem - resolve or explain 2 ALERT level B = A potentially serious problem, consider carefully 11 ALERT level C = Check. Ensure it is not caused by an omission or oversight 13 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
Computing details top
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) andMercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Bourhis et al., 2015).
Crystal data
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[Ni(C13H11N2O2)(H2O)4]3Br·2H2O | F(000) = 1248 |
Mr = 633.77 | Dx = 1.922 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8071 (6) Å | Cell parameters from 4741 reflections |
b = 23.8031 (16) Å | θ = 4.6–32.1° |
c = 13.6302 (10) Å | µ = 6.40 mm−1 |
β = 97.476 (9)° | T = 293 K |
V = 2189.7 (3) Å3 | Block, orange |
Z = 4 | 0.32 × 0.28 × 0.19 mm |
Data collection
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Agilent Xcalibur Sapphire3 diffractometer | 7970 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5803 reflections with I > 2σ(I) |
Detector resolution: 16.1790 pixels mm-1 | Rint = 0.034 |
ω scans | θmax = 33.7°, θmin = 4.3° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −10→10 |
Tmin = 0.503, Tmax = 1.000 | k = −36→36 |
26929 measured reflections | l = −20→21 |
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Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: mixed |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0561P)2 + 2.3402P] where P = (Fo2 + 2Fc2)/3 |
7970 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 1.10 e Å−3 |
12 restraints | Δρmin = −1.39 e Å−3 |
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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)
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x | y | z | Uiso*/Ueq | ||
Br1 | 0.28363 (5) | 0.60904 (2) | 0.46388 (3) | 0.04291 (10) | |
Br2 | 0.22784 (5) | 0.48206 (2) | 0.10507 (2) | 0.03503 (9) | |
Br3 | 0.80885 (8) | 0.76767 (2) | 0.39510 (3) | 0.05624 (13) | |
Ni1 | 0.15038 (6) | 0.37164 (2) | 0.81987 (3) | 0.02833 (10) | |
O1 | 0.2089 (4) | 0.37484 (8) | 0.67975 (15) | 0.0311 (4) | |
O2 | 0.2542 (4) | 0.45031 (9) | 0.83901 (15) | 0.0318 (5) | |
O3 | 0.0917 (5) | 0.37407 (10) | 0.96216 (18) | 0.0439 (6) | |
O4 | 0.0286 (4) | 0.29148 (10) | 0.79662 (19) | 0.0417 (6) | |
O5 | 0.4287 (5) | 0.33525 (12) | 0.8585 (2) | 0.0489 (6) | |
O6 | −0.1333 (4) | 0.40312 (11) | 0.77851 (19) | 0.0414 (5) | |
N1 | 0.2313 (5) | 0.45128 (15) | 0.4508 (2) | 0.0488 (8) | |
H1 | 0.2437 | 0.4862 | 0.4669 | 0.059* | |
N2 | 0.3028 (5) | 0.59168 (13) | 0.7459 (2) | 0.0473 (7) | |
H2 | 0.3017 | 0.5882 | 0.6831 | 0.057* | |
C1 | 0.2240 (6) | 0.43458 (18) | 0.3530 (2) | 0.0464 (9) | |
H1A | 0.2312 | 0.4615 | 0.3041 | 0.056* | |
C2 | 0.2062 (7) | 0.37877 (18) | 0.3273 (2) | 0.0480 (9) | |
H2A | 0.2029 | 0.3677 | 0.2617 | 0.058* | |
C3 | 0.1935 (6) | 0.33996 (17) | 0.3999 (2) | 0.0432 (8) | |
H3 | 0.1814 | 0.3020 | 0.3841 | 0.052* | |
C4 | 0.1984 (4) | 0.35680 (12) | 0.49387 (18) | 0.0241 (5) | |
H4 | 0.1874 | 0.3297 | 0.5420 | 0.029* | |
C5 | 0.2182 (4) | 0.41042 (12) | 0.52228 (19) | 0.0267 (5) | |
C6 | 0.2239 (5) | 0.41925 (12) | 0.6312 (2) | 0.0267 (5) | |
C7 | 0.2441 (5) | 0.47393 (12) | 0.6692 (2) | 0.0300 (6) | |
H7 | 0.2477 | 0.5037 | 0.6254 | 0.036* | |
C8 | 0.2593 (4) | 0.48545 (11) | 0.7704 (2) | 0.0264 (5) | |
C9 | 0.2832 (4) | 0.54534 (11) | 0.8042 (2) | 0.0246 (5) | |
C10 | 0.2865 (4) | 0.55252 (11) | 0.90202 (18) | 0.0216 (5) | |
H10 | 0.2701 | 0.5211 | 0.9408 | 0.026* | |
C11 | 0.3121 (6) | 0.60228 (14) | 0.9464 (3) | 0.0387 (7) | |
H11 | 0.3170 | 0.6051 | 1.0148 | 0.046* | |
C12 | 0.3313 (6) | 0.64942 (15) | 0.8900 (3) | 0.0469 (9) | |
H12 | 0.3490 | 0.6845 | 0.9198 | 0.056* | |
C13 | 0.3243 (6) | 0.64421 (14) | 0.7904 (3) | 0.0450 (8) | |
H13 | 0.3339 | 0.6760 | 0.7517 | 0.054* | |
O7 | 0.6193 (5) | 0.29510 (15) | 0.7017 (3) | 0.0586 (8) | |
O8 | 0.6929 (11) | 0.2404 (2) | 0.9388 (4) | 0.1057 (17) | |
H3A | 0.120 (13) | 0.4061 (18) | 0.986 (6) | 0.159* | |
H3B | 0.140 (12) | 0.349 (3) | 1.000 (5) | 0.159* | |
H4A | −0.095 (3) | 0.289 (4) | 0.791 (7) | 0.159* | |
H4B | 0.061 (14) | 0.272 (3) | 0.752 (5) | 0.159* | |
H5A | 0.489 (13) | 0.317 (4) | 0.818 (6) | 0.159* | |
H5B | 0.448 (15) | 0.304 (2) | 0.886 (7) | 0.159* | |
H6A | −0.169 (13) | 0.402 (4) | 0.7173 (18) | 0.159* | |
H6B | −0.178 (13) | 0.432 (2) | 0.802 (7) | 0.159* | |
H7A | 0.592 (15) | 0.319 (3) | 0.656 (5) | 0.159* | |
H7B | 0.513 (8) | 0.281 (4) | 0.673 (7) | 0.159* | |
H8A | 0.789 (10) | 0.252 (4) | 0.980 (6) | 0.159* | |
H8B | 0.658 (15) | 0.2068 (16) | 0.945 (8) | 0.159* |
Atomic displacement parameters (Å2)
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U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.03826 (18) | 0.0478 (2) | 0.04137 (18) | −0.00130 (14) | 0.00006 (14) | 0.00498 (15) |
Br2 | 0.04109 (18) | 0.04094 (18) | 0.02300 (13) | 0.00484 (13) | 0.00390 (12) | −0.00060 (11) |
Br3 | 0.0857 (3) | 0.02834 (17) | 0.0548 (2) | −0.00371 (17) | 0.0097 (2) | −0.01026 (15) |
Ni1 | 0.0437 (2) | 0.02121 (17) | 0.02022 (16) | −0.00070 (14) | 0.00474 (15) | 0.00139 (12) |
O1 | 0.0497 (13) | 0.0228 (9) | 0.0210 (9) | 0.0008 (9) | 0.0051 (9) | 0.0011 (7) |
O2 | 0.0510 (13) | 0.0230 (9) | 0.0213 (9) | −0.0049 (9) | 0.0038 (9) | 0.0000 (7) |
O3 | 0.0761 (19) | 0.0318 (12) | 0.0258 (10) | −0.0031 (12) | 0.0139 (12) | 0.0026 (9) |
O4 | 0.0597 (16) | 0.0247 (10) | 0.0418 (13) | −0.0045 (11) | 0.0105 (12) | −0.0001 (9) |
O5 | 0.0583 (17) | 0.0447 (15) | 0.0407 (13) | 0.0133 (13) | −0.0053 (12) | 0.0019 (11) |
O6 | 0.0482 (14) | 0.0358 (12) | 0.0392 (12) | 0.0026 (11) | 0.0021 (11) | −0.0038 (10) |
N1 | 0.064 (2) | 0.0480 (18) | 0.0351 (15) | 0.0050 (16) | 0.0085 (15) | 0.0064 (13) |
N2 | 0.064 (2) | 0.0373 (15) | 0.0405 (15) | −0.0065 (15) | 0.0061 (15) | −0.0003 (13) |
C1 | 0.061 (2) | 0.055 (2) | 0.0230 (13) | 0.0033 (18) | 0.0076 (15) | 0.0093 (14) |
C2 | 0.058 (2) | 0.066 (3) | 0.0200 (13) | 0.0027 (19) | 0.0057 (15) | −0.0077 (14) |
C3 | 0.054 (2) | 0.0456 (19) | 0.0301 (15) | −0.0022 (16) | 0.0045 (15) | −0.0164 (14) |
C4 | 0.0314 (13) | 0.0240 (11) | 0.0170 (10) | −0.0010 (10) | 0.0033 (10) | −0.0048 (9) |
C5 | 0.0314 (14) | 0.0292 (13) | 0.0193 (10) | 0.0021 (11) | 0.0029 (10) | −0.0013 (10) |
C6 | 0.0349 (14) | 0.0250 (12) | 0.0201 (10) | 0.0019 (11) | 0.0038 (10) | 0.0000 (9) |
C7 | 0.0476 (17) | 0.0219 (12) | 0.0204 (11) | −0.0025 (11) | 0.0040 (12) | 0.0018 (9) |
C8 | 0.0341 (14) | 0.0219 (11) | 0.0227 (11) | −0.0020 (10) | 0.0021 (11) | −0.0011 (9) |
C9 | 0.0275 (12) | 0.0226 (12) | 0.0232 (11) | −0.0021 (10) | 0.0022 (10) | −0.0023 (9) |
C10 | 0.0260 (12) | 0.0190 (11) | 0.0202 (10) | −0.0032 (9) | 0.0052 (9) | −0.0035 (8) |
C11 | 0.0496 (19) | 0.0339 (16) | 0.0346 (15) | −0.0085 (14) | 0.0135 (15) | −0.0141 (13) |
C12 | 0.062 (2) | 0.0276 (16) | 0.053 (2) | −0.0092 (15) | 0.0142 (18) | −0.0108 (14) |
C13 | 0.065 (2) | 0.0242 (14) | 0.0465 (19) | −0.0097 (15) | 0.0092 (18) | 0.0011 (14) |
O7 | 0.0591 (18) | 0.0536 (18) | 0.0612 (19) | 0.0006 (14) | 0.0002 (15) | 0.0041 (14) |
O8 | 0.161 (5) | 0.071 (3) | 0.086 (3) | 0.024 (3) | 0.020 (3) | 0.020 (3) |
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Ni1—O1 | 2.003 (2) | C2—C3 | 1.365 (6) |
Ni1—O2 | 2.006 (2) | C2—H2A | 0.9300 |
Ni1—O3 | 2.031 (2) | C3—C4 | 1.339 (4) |
Ni1—O6 | 2.080 (3) | C3—H3 | 0.9300 |
Ni1—O5 | 2.088 (3) | C4—C5 | 1.336 (4) |
Ni1—O4 | 2.088 (2) | C4—H4 | 0.9300 |
O1—C6 | 1.258 (3) | C5—C6 | 1.495 (4) |
O2—C8 | 1.259 (3) | C6—C7 | 1.401 (4) |
O3—H3A | 0.84 (2) | C7—C8 | 1.396 (4) |
O3—H3B | 0.83 (2) | C7—H7 | 0.9300 |
O4—H4A | 0.84 (2) | C8—C9 | 1.501 (4) |
O4—H4B | 0.82 (2) | C9—C10 | 1.341 (3) |
O5—H5A | 0.84 (2) | C10—C11 | 1.331 (4) |
O5—H5B | 0.84 (2) | C10—H10 | 0.9300 |
O6—H6A | 0.84 (2) | C11—C12 | 1.376 (5) |
O6—H6B | 0.83 (2) | C11—H11 | 0.9300 |
N1—C1 | 1.386 (5) | C12—C13 | 1.358 (5) |
N1—C5 | 1.387 (4) | C12—H12 | 0.9300 |
N1—H1 | 0.8600 | C13—H13 | 0.9300 |
N2—C9 | 1.376 (4) | O7—H7A | 0.84 (2) |
N2—C13 | 1.389 (5) | O7—H7B | 0.85 (2) |
N2—H2 | 0.8600 | O8—H8A | 0.85 (2) |
C1—C2 | 1.375 (6) | O8—H8B | 0.84 (2) |
C1—H1A | 0.9300 | ||
O1—Ni1—O2 | 88.75 (9) | C3—C2—C1 | 118.7 (3) |
O1—Ni1—O3 | 176.19 (9) | C3—C2—H2A | 120.6 |
O2—Ni1—O3 | 87.65 (9) | C1—C2—H2A | 120.6 |
O1—Ni1—O6 | 91.18 (10) | C4—C3—C2 | 119.7 (3) |
O2—Ni1—O6 | 89.88 (10) | C4—C3—H3 | 120.2 |
O3—Ni1—O6 | 87.57 (12) | C2—C3—H3 | 120.2 |
O1—Ni1—O5 | 88.26 (11) | C5—C4—C3 | 123.5 (3) |
O2—Ni1—O5 | 93.54 (11) | C5—C4—H4 | 118.2 |
O3—Ni1—O5 | 93.21 (12) | C3—C4—H4 | 118.2 |
O6—Ni1—O5 | 176.52 (11) | C4—C5—N1 | 118.7 (3) |
O1—Ni1—O4 | 90.82 (9) | C4—C5—C6 | 114.3 (2) |
O2—Ni1—O4 | 177.08 (11) | N1—C5—C6 | 127.1 (3) |
O3—Ni1—O4 | 92.72 (10) | O1—C6—C7 | 126.6 (3) |
O6—Ni1—O4 | 87.24 (11) | O1—C6—C5 | 114.3 (2) |
O5—Ni1—O4 | 89.34 (12) | C7—C6—C5 | 119.1 (2) |
C6—O1—Ni1 | 124.99 (19) | C8—C7—C6 | 122.6 (3) |
C8—O2—Ni1 | 124.54 (18) | C8—C7—H7 | 118.7 |
Ni1—O3—H3A | 109 (6) | C6—C7—H7 | 118.7 |
Ni1—O3—H3B | 117 (6) | O2—C8—C7 | 126.7 (3) |
H3A—O3—H3B | 112 (9) | O2—C8—C9 | 114.5 (2) |
Ni1—O4—H4A | 118 (7) | C7—C8—C9 | 118.8 (2) |
Ni1—O4—H4B | 120 (7) | C10—C9—N2 | 118.8 (3) |
H4A—O4—H4B | 104 (8) | C10—C9—C8 | 114.5 (2) |
Ni1—O5—H5A | 123 (7) | N2—C9—C8 | 126.8 (3) |
Ni1—O5—H5B | 124 (7) | C11—C10—C9 | 123.3 (3) |
H5A—O5—H5B | 77 (8) | C11—C10—H10 | 118.3 |
Ni1—O6—H6A | 114 (6) | C9—C10—H10 | 118.3 |
Ni1—O6—H6B | 125 (7) | C10—C11—C12 | 119.2 (3) |
H6A—O6—H6B | 109 (8) | C10—C11—H11 | 120.4 |
C1—N1—C5 | 118.5 (3) | C12—C11—H11 | 120.4 |
C1—N1—H1 | 120.8 | C13—C12—C11 | 119.4 (3) |
C5—N1—H1 | 120.8 | C13—C12—H12 | 120.3 |
C9—N2—C13 | 118.8 (3) | C11—C12—H12 | 120.3 |
C9—N2—H2 | 120.6 | C12—C13—N2 | 120.4 (3) |
C13—N2—H2 | 120.6 | C12—C13—H13 | 119.8 |
C2—C1—N1 | 120.9 (3) | N2—C13—H13 | 119.8 |
C2—C1—H1A | 119.5 | H7A—O7—H7B | 80 (8) |
N1—C1—H1A | 119.5 | H8A—O8—H8B | 116 (10) |
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D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.86 | 2.94 | 3.774 (4) | 165 |
N2—H2···Br1 | 0.86 | 3.02 | 3.852 (3) | 165 |
C1—H1A···Br2 | 0.93 | 2.75 | 3.567 (3) | 147 |
C4—H4···Br3i | 0.93 | 2.47 | 3.330 (3) | 154 |
C10—H10···Br2ii | 0.93 | 2.48 | 3.305 (3) | 149 |
O3—H3A···Br2ii | 0.84 (2) | 2.48 (4) | 3.285 (3) | 161 (9) |
O3—H3B···Br3iii | 0.83 (2) | 2.40 (3) | 3.212 (2) | 165 (8) |
O4—H4A···O7iv | 0.84 (2) | 2.16 (5) | 2.917 (4) | 150 (9) |
O4—H4B···Br3i | 0.82 (2) | 2.48 (3) | 3.284 (3) | 167 (9) |
O5—H5A···O7 | 0.84 (2) | 1.99 (3) | 2.808 (5) | 163 (10) |
O5—H5B···O8 | 0.84 (2) | 2.29 (6) | 3.002 (6) | 142 (9) |
O6—H6A···Br1v | 0.84 (2) | 2.51 (2) | 3.342 (3) | 175 (9) |
O6—H6B···Br2v | 0.83 (2) | 2.45 (3) | 3.266 (3) | 165 (9) |
O7—H7A···Br1i | 0.84 (2) | 2.59 (6) | 3.335 (4) | 149 (9) |
O7—H7B···Br3i | 0.85 (2) | 2.54 (2) | 3.386 (3) | 173 (9) |
O8—H8A···Br3vi | 0.85 (2) | 3.06 (3) | 3.880 (7) | 165 (9) |
O8—H8B···Br1iii | 0.84 (2) | 2.65 (6) | 3.393 (5) | 149 (9) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z+1; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1, y, z; (v) −x, −y+1, −z+1; (vi) −x+2, y−1/2, −z+3/2.