Literature DB >> 24860303

Piperazine-1,4-diium bis-(hexa-hydroxido-hepta-oxidohexa-borato-κ(3) O,O',O'')cobaltate(II) hexa-hydrate.

Nabil Jamai1, Mohamed Rzaigui1, Samah Akriche Toumi1.   

Abstract

In the title hydrate, (C4H12N2)[Co{B6O7(OH)6}2]·6H2O, both the dication and dianion are generated by crystallographic inversion symmetry. The Co(2+) ion in the dianion adopts a fairly regular CoO6 octa-hedral coordination geometry arising from the two O,O',O''-tridentate ligands. In the crystal, the dianions and water mol-ecules are linked by O-H⋯O hydrogen bonds, generating a framework with large [100] channels, which are occupied by the organic dications. N-H⋯O and C-H⋯O hydrogen bonds consolidate the structure.

Entities:  

Year:  2014        PMID： 24860303      PMCID： PMC4011254          DOI： 10.1107/S1600536814007090

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For related structures, see: Natarajan et al. (2003 ▶); Negro et al. (1971 ▶); Zhihong et al. (2005 ▶); Yue et al. (2003 ▶).

Experimental

Crystal data

(C4H12N2)[Co(H6B6O13)2]·6H2O M = 813.00 Triclinic, a = 8.226 (3) Å b = 10.157 (2) Å c = 11.298 (4) Å α = 65.98 (2)° β = 74.20 (3)° γ = 69.03 (5)° V = 796.2 (4) Å3 Z = 1 Ag Kα radiation λ = 0.56087 Å μ = 0.35 mm−1 T = 298 K 0.23 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer 9895 measured reflections 7785 independent reflections 6118 reflections with I > 2σ(I) R int = 0.014 2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.049 wR(F 2) = 0.153 S = 1.06 7785 reflections 259 parameters 12 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 2.42 e Å−3 Δρmin = −0.99 e Å−3 Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814007090/hb7207sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007090/hb7207Isup2.hkl CCDC reference: 994558 Additional supporting information: crystallographic information; 3D view; checkCIF report
(C4H12N2)[Co(H6B6O13)2]·6H2OZ = 1
Mr = 813.00F(000) = 417
Triclinic, P1Dx = 1.696 Mg m−3
Hall symbol: -P 1Ag Kα radiation, λ = 0.56087 Å
a = 8.226 (3) ÅCell parameters from 25 reflections
b = 10.157 (2) Åθ = 9–11°
c = 11.298 (4) ŵ = 0.35 mm−1
α = 65.98 (2)°T = 298 K
β = 74.20 (3)°Prism, pink
γ = 69.03 (5)°0.23 × 0.15 × 0.11 mm
V = 796.2 (4) Å3
Enraf–Nonius CAD-4 diffractometerRint = 0.014
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.1°
Graphite monochromatorh = −13→13
non–profiled ω scansk = −16→16
9895 measured reflectionsl = −3→18
7785 independent reflections2 standard reflections every 120 min
6118 reflections with I > 2σ(I) intensity decay: 2%
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0924P)2 + 0.2147P] where P = (Fo2 + 2Fc2)/3
7785 reflections(Δ/σ)max < 0.001
259 parametersΔρmax = 2.42 e Å−3
12 restraintsΔρmin = −0.99 e Å−3
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.
xyzUiso*/Ueq
Co10.50000.50000.50000.01614 (7)
B10.7384 (2)0.59885 (17)0.23924 (15)0.0163 (2)
B20.8734 (2)0.33738 (17)0.39832 (16)0.0167 (2)
B30.8346 (2)0.12594 (18)0.36263 (17)0.0200 (3)
B40.6375 (2)0.37212 (16)0.26842 (15)0.0161 (2)
B50.6174 (2)0.59847 (19)0.06603 (16)0.0210 (3)
B61.0368 (2)0.5217 (2)0.29973 (17)0.0203 (3)
O1240.77220 (13)0.43050 (11)0.28482 (10)0.01562 (17)
O450.58438 (15)0.46319 (12)0.14086 (11)0.02026 (19)
O340.71305 (15)0.21657 (12)0.28139 (12)0.02037 (19)
O160.89561 (14)0.62883 (13)0.24323 (12)0.0225 (2)
O150.69605 (17)0.66434 (13)0.10864 (11)0.0232 (2)
O230.91602 (16)0.17965 (12)0.41590 (12)0.0229 (2)
O10.58976 (15)0.65398 (12)0.33104 (12)0.02076 (19)
H10.595 (4)0.7336 (18)0.330 (3)0.031*
O20.75590 (15)0.36962 (14)0.51227 (11)0.0222 (2)
H20.793 (4)0.361 (3)0.5750 (18)0.033*
O30.8757 (2)−0.02567 (13)0.38981 (16)0.0321 (3)
H30.9463−0.07010.44210.048*
O40.51422 (14)0.61177 (12)0.62547 (11)0.01811 (18)
H40.528 (4)0.6931 (17)0.578 (2)0.027*
O50.5670 (2)0.67326 (16)−0.05561 (13)0.0352 (3)
H50.52050.6238−0.07080.053*
O61.17955 (16)0.57172 (15)0.27863 (15)0.0286 (3)
H61.26280.50030.30700.043*
O261.03454 (14)0.37793 (13)0.37106 (12)0.0223 (2)
O1W0.6861 (3)0.8794 (2)−0.2835 (2)0.0489 (4)
H1W10.622 (4)0.833 (4)−0.216 (3)0.073*
H2W10.773 (3)0.818 (3)−0.314 (3)0.073*
O2W0.5784 (2)0.87545 (16)0.41668 (16)0.0349 (3)
H1W20.676 (2)0.882 (3)0.423 (3)0.052*
H2W20.511 (3)0.959 (2)0.375 (3)0.052*
O3W1.2705 (3)0.9010 (3)0.2089 (3)0.0675 (7)
H2W31.253 (5)0.981 (2)0.223 (5)0.101*
H1W31.35780.83340.24300.101*
N10.9898 (3)0.8815 (2)0.1223 (2)0.0443 (4)
H1A0.95380.80010.17630.053*
H1B1.05450.89820.16460.053*
C10.8360 (3)1.0119 (2)0.0893 (2)0.0355 (4)
H1C0.76531.02900.16860.043*
H1D0.76380.99350.04580.043*
C21.1021 (4)0.8520 (2)−0.0001 (3)0.0441 (5)
H2A1.20280.76510.02350.053*
H2B1.03390.8314−0.04500.053*
U11U22U33U12U13U23
Co10.01484 (11)0.01703 (12)0.01733 (12)−0.00406 (8)−0.00425 (8)−0.00587 (9)
B10.0158 (5)0.0161 (5)0.0180 (6)−0.0053 (4)−0.0062 (5)−0.0038 (5)
B20.0157 (5)0.0159 (5)0.0194 (6)−0.0025 (4)−0.0083 (5)−0.0050 (5)
B30.0214 (6)0.0157 (6)0.0240 (7)−0.0030 (5)−0.0078 (5)−0.0070 (5)
B40.0168 (5)0.0154 (5)0.0179 (6)−0.0039 (4)−0.0071 (5)−0.0053 (5)
B50.0255 (7)0.0211 (6)0.0173 (6)−0.0073 (5)−0.0086 (5)−0.0034 (5)
B60.0160 (6)0.0245 (7)0.0241 (7)−0.0074 (5)−0.0055 (5)−0.0090 (6)
O1240.0151 (4)0.0150 (4)0.0180 (4)−0.0037 (3)−0.0070 (3)−0.0046 (3)
O450.0244 (5)0.0208 (4)0.0182 (4)−0.0091 (4)−0.0102 (4)−0.0025 (4)
O340.0233 (5)0.0158 (4)0.0252 (5)−0.0029 (3)−0.0108 (4)−0.0078 (4)
O160.0176 (4)0.0203 (4)0.0316 (6)−0.0072 (4)−0.0091 (4)−0.0058 (4)
O150.0321 (6)0.0206 (5)0.0194 (5)−0.0107 (4)−0.0116 (4)−0.0014 (4)
O230.0262 (5)0.0148 (4)0.0294 (5)−0.0011 (4)−0.0159 (4)−0.0058 (4)
O10.0199 (4)0.0178 (4)0.0254 (5)−0.0055 (3)−0.0020 (4)−0.0088 (4)
O20.0187 (4)0.0287 (5)0.0192 (5)−0.0025 (4)−0.0074 (4)−0.0091 (4)
O30.0400 (7)0.0156 (5)0.0460 (8)−0.0014 (4)−0.0265 (6)−0.0085 (5)
O40.0174 (4)0.0182 (4)0.0203 (4)−0.0065 (3)−0.0039 (3)−0.0061 (3)
O50.0583 (9)0.0321 (6)0.0227 (6)−0.0253 (6)−0.0218 (6)0.0042 (5)
O60.0177 (5)0.0287 (6)0.0403 (7)−0.0093 (4)−0.0100 (5)−0.0069 (5)
O260.0156 (4)0.0235 (5)0.0282 (5)−0.0055 (4)−0.0087 (4)−0.0059 (4)
O1W0.0409 (9)0.0369 (8)0.0484 (10)−0.0071 (7)0.0027 (7)−0.0038 (7)
O2W0.0407 (7)0.0262 (6)0.0426 (8)−0.0149 (5)−0.0062 (6)−0.0116 (6)
O3W0.0612 (14)0.0639 (14)0.0861 (17)−0.0129 (11)−0.0395 (13)−0.0203 (13)
N10.0550 (12)0.0363 (9)0.0406 (10)−0.0197 (8)−0.0131 (9)−0.0026 (8)
C10.0392 (10)0.0318 (8)0.0291 (8)−0.0099 (7)0.0008 (7)−0.0081 (7)
C20.0509 (13)0.0232 (8)0.0485 (12)−0.0079 (8)0.0024 (10)−0.0111 (8)
Co1—O22.0539 (17)B6—O61.368 (2)
Co1—O2i2.0539 (17)B6—O161.369 (2)
Co1—O12.0648 (14)O1—H10.820 (10)
Co1—O1i2.0648 (14)O2—H20.811 (10)
Co1—O4i2.1926 (12)O3—H30.8200
Co1—O42.1926 (12)O4—B4i1.490 (2)
B1—O151.434 (2)O4—H40.810 (10)
B1—O161.4462 (19)O5—H50.8200
B1—O11.475 (2)O6—H60.8200
B1—O1241.5123 (18)O1W—H1W10.861 (10)
B2—O261.4447 (19)O1W—H2W10.856 (10)
B2—O231.4510 (19)O2W—H1W20.852 (10)
B2—O21.462 (2)O2W—H2W20.854 (10)
B2—O1241.5041 (19)O3W—H2W30.846 (10)
B3—O341.357 (2)O3W—H1W30.847 (2)
B3—O231.363 (2)N1—C11.466 (3)
B3—O31.371 (2)N1—C21.517 (4)
B4—O341.4360 (19)N1—H1A0.9000
B4—O451.4463 (19)N1—H1B0.9000
B4—O4i1.490 (2)C1—C2ii1.508 (3)
B4—O1241.5117 (18)C1—H1C0.9700
B5—O151.356 (2)C1—H1D0.9700
B5—O51.368 (2)C2—C1ii1.508 (3)
B5—O451.368 (2)C2—H2A0.9700
B6—O261.355 (2)C2—H2B0.9700
O2—Co1—O2i180.0B2—O124—B4118.01 (11)
O2—Co1—O188.68 (6)B2—O124—B1116.87 (11)
O2i—Co1—O191.32 (6)B4—O124—B1117.76 (11)
O2—Co1—O1i91.32 (6)B5—O45—B4124.30 (12)
O2i—Co1—O1i88.68 (6)B3—O34—B4120.52 (12)
O1—Co1—O1i180.0B6—O16—B1124.47 (12)
O2—Co1—O4i88.17 (5)B5—O15—B1120.85 (12)
O2i—Co1—O4i91.83 (5)B3—O23—B2123.44 (12)
O1—Co1—O4i87.03 (5)B1—O1—Co1118.94 (9)
O1i—Co1—O4i92.97 (5)B1—O1—H1109.3 (19)
O2—Co1—O491.83 (5)Co1—O1—H1121.9 (19)
O2i—Co1—O488.17 (5)B2—O2—Co1121.28 (9)
O1—Co1—O492.97 (5)B2—O2—H2122 (2)
O1i—Co1—O487.03 (5)Co1—O2—H2114 (2)
O4i—Co1—O4180.0B3—O3—H3109.5
O15—B1—O16110.89 (12)B4i—O4—Co1116.22 (9)
O15—B1—O1110.91 (13)B4i—O4—H4110.6 (19)
O16—B1—O1110.56 (12)Co1—O4—H4107.3 (19)
O15—B1—O124109.07 (12)B5—O5—H5109.5
O16—B1—O124108.17 (12)B6—O6—H6109.5
O1—B1—O124107.12 (12)B6—O26—B2119.33 (13)
O26—B2—O23109.16 (13)H1W1—O1W—H2W1112 (2)
O26—B2—O2112.53 (12)H1W2—O2W—H2W2113 (2)
O23—B2—O2110.85 (13)H2W3—O3W—H1W3111 (2)
O26—B2—O124109.35 (12)C1—N1—C2110.90 (19)
O23—B2—O124109.28 (12)C1—N1—H1A109.5
O2—B2—O124105.58 (12)C2—N1—H1A109.5
O34—B3—O23122.88 (14)C1—N1—H1B109.5
O34—B3—O3117.27 (14)C2—N1—H1B109.5
O23—B3—O3119.85 (14)H1A—N1—H1B108.0
O34—B4—O45111.78 (12)N1—C1—C2ii109.0 (2)
O34—B4—O4i109.79 (12)N1—C1—H1C109.9
O45—B4—O4i110.85 (12)C2ii—C1—H1C109.9
O34—B4—O124109.48 (12)N1—C1—H1D109.9
O45—B4—O124107.67 (11)C2ii—C1—H1D109.9
O4i—B4—O124107.13 (11)H1C—C1—H1D108.3
O15—B5—O5117.83 (14)C1ii—C2—N1109.18 (18)
O15—B5—O45122.48 (14)C1ii—C2—H2A109.8
O5—B5—O45119.68 (14)N1—C2—H2A109.8
O26—B6—O6122.85 (15)C1ii—C2—H2B109.8
O26—B6—O16122.54 (14)N1—C2—H2B109.8
O6—B6—O16114.61 (14)H2A—C2—H2B108.3
O26—B2—O124—B4158.42 (12)O1—B1—O15—B5−88.84 (17)
O23—B2—O124—B438.99 (17)O124—B1—O15—B528.90 (19)
O2—B2—O124—B4−80.28 (14)O34—B3—O23—B24.1 (3)
O26—B2—O124—B1−52.13 (16)O3—B3—O23—B2−176.41 (15)
O23—B2—O124—B1−171.56 (11)O26—B2—O23—B3−136.34 (15)
O2—B2—O124—B169.17 (15)O2—B2—O23—B399.17 (17)
O34—B4—O124—B2−47.01 (16)O124—B2—O23—B3−16.8 (2)
O45—B4—O124—B2−168.73 (11)O15—B1—O1—Co1128.21 (10)
O4i—B4—O124—B271.99 (15)O16—B1—O1—Co1−108.36 (12)
O34—B4—O124—B1163.82 (12)O124—B1—O1—Co19.28 (14)
O45—B4—O124—B142.10 (16)O2—Co1—O1—B137.04 (10)
O4i—B4—O124—B1−77.18 (14)O2i—Co1—O1—B1−142.96 (10)
O15—B1—O124—B2160.84 (12)O1i—Co1—O1—B13 (100)
O16—B1—O124—B240.14 (16)O4i—Co1—O1—B1−51.19 (10)
O1—B1—O124—B2−79.05 (14)O4—Co1—O1—B1128.81 (10)
O15—B1—O124—B4−49.63 (16)O26—B2—O2—Co1125.40 (11)
O16—B1—O124—B4−170.33 (12)O23—B2—O2—Co1−112.03 (12)
O1—B1—O124—B470.47 (15)O124—B2—O2—Co16.19 (15)
O15—B5—O45—B4−3.7 (3)O2i—Co1—O2—B2−124 (100)
O5—B5—O45—B4177.61 (16)O1—Co1—O2—B2−47.25 (11)
O34—B4—O45—B5−135.19 (15)O1i—Co1—O2—B2132.75 (11)
O4i—B4—O45—B5101.96 (17)O4i—Co1—O2—B239.82 (11)
O124—B4—O45—B5−14.9 (2)O4—Co1—O2—B2−140.18 (11)
O23—B3—O34—B4−12.8 (2)O2—Co1—O4—B4i−134.31 (9)
O3—B3—O34—B4167.68 (15)O2i—Co1—O4—B4i45.69 (9)
O45—B4—O34—B3151.66 (14)O1—Co1—O4—B4i136.92 (10)
O4i—B4—O34—B3−84.90 (16)O1i—Co1—O4—B4i−43.08 (10)
O124—B4—O34—B332.44 (19)O4i—Co1—O4—B4i10 (100)
O26—B6—O16—B1−7.6 (3)O6—B6—O26—B2174.61 (15)
O6—B6—O16—B1172.53 (15)O16—B6—O26—B2−5.2 (2)
O15—B1—O16—B6−129.57 (16)O23—B2—O26—B6152.56 (14)
O1—B1—O16—B6106.99 (17)O2—B2—O26—B6−83.94 (17)
O124—B1—O16—B6−10.0 (2)O124—B2—O26—B633.05 (19)
O5—B5—O15—B1174.55 (16)C2—N1—C1—C2ii−59.8 (3)
O45—B5—O15—B1−4.2 (3)C1—N1—C2—C1ii59.9 (3)
O16—B1—O15—B5147.91 (15)
D—H···AD—HH···AD···AD—H···A
O1—H1···O2W0.82 (1)2.00 (2)2.7525 (19)153 (3)
O2—H2···O6iii0.81 (1)2.11 (1)2.876 (2)157 (3)
O3—H3···O23iv0.821.932.745 (2)172
O4—H4···O2W0.81 (1)2.08 (1)2.864 (2)164 (3)
O5—H5···O45v0.821.912.7159 (18)169
O6—H6···O4iii0.821.952.734 (2)160
O1W—H1W1···O50.86 (1)1.96 (2)2.771 (2)158 (4)
O1W—H2W1···O26vi0.86 (1)2.27 (1)3.108 (3)167 (3)
O1W—H2W1···O23vi0.86 (1)2.51 (3)3.158 (3)133 (3)
O2W—H1W2···O3vii0.85 (1)2.05 (2)2.861 (2)159 (3)
O2W—H2W2···O1Wviii0.85 (1)2.01 (1)2.838 (3)164 (3)
O3W—H2W3···O1Wii0.85 (1)2.05 (2)2.842 (3)155 (3)
O3W—H1W3···O1ix0.85 (1)2.24 (1)3.088 (3)179 (1)
N1—H1A···O160.901.782.654 (2)165
N1—H1A···O60.902.462.986 (3)117
N1—H1B···O3W0.901.982.836 (3)157
C1—H1C···O34vii0.972.563.321 (3)136
Table 1

Selected bond lengths (Å)

Co1—O22.0539 (17)
Co1—O12.0648 (14)
Co1—O42.1926 (12)
Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
O1—H1⋯O2W 0.82 (1)2.00 (2)2.7525 (19)153 (3)
O2—H2⋯O6i 0.81 (1)2.11 (1)2.876 (2)157 (3)
O3—H3⋯O23ii 0.821.932.745 (2)172
O4—H4⋯O2W 0.81 (1)2.08 (1)2.864 (2)164 (3)
O5—H5⋯O45iii 0.821.912.7159 (18)169
O6—H6⋯O4i 0.821.952.734 (2)160
O1W—H1W1⋯O50.86 (1)1.96 (2)2.771 (2)158 (4)
O1W—H2W1⋯O26iv 0.86 (1)2.27 (1)3.108 (3)167 (3)
O1W—H2W1⋯O23iv 0.86 (1)2.51 (3)3.158 (3)133 (3)
O2W—H1W2⋯O3v 0.85 (1)2.05 (2)2.861 (2)159 (3)
O2W—H2W2⋯O1W vi 0.85 (1)2.01 (1)2.838 (3)164 (3)
O3W—H2W3⋯O1W vii 0.85 (1)2.05 (2)2.842 (3)155 (3)
O3W—H1W3⋯O1viii 0.85 (1)2.24 (1)3.088 (3)179 (1)
N1—H1A⋯O160.901.782.654 (2)165
N1—H1A⋯O60.902.462.986 (3)117
N1—H1B⋯O3W 0.901.982.836 (3)157
C1—H1C⋯O34v 0.972.563.321 (3)136

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

  1 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290
  1 in total
  1 in total

1.  Crystal structure of MgK0.5[B6O10](OH)0.5·0.5H2O, poly[dimagnesium potassium bis(hexa-borate) hy-droxide monohydrate].

Authors:  Qi-Ming Qiu; Jian-Biao Song
Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2022-09-08
  1 in total

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