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Details of the complex bonding environment present in the molecular centre of an alkyne-bridged dicobalt complex have been examined using a combination of experimental and theoretical charge-density modelling for two compounds which share a central Co2C2 tetrahedral moiety as their common motif. Topological analysis of the experimental electron density illustrates the problem of separating the Co-C bond-critical points (b.c.p.s) from the intervening ring-critical point (r.c.p.), due largely to the flat nature of the electron density in the CoC2 triangles. Such a separation of critical points is immediately obtained from a topological analysis of the theoretical electron density as well as from the multipole-projected theoretical density; however, the addition of random noise to the theoretical structure factors prior to multipole modelling leads to a failure in consistently distinguishing two b.c.p.s and one r.c.p. in such close proximity within the particular environment of this Co2C2 centre.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768109045091/pi5003sup1.cif
Contains datablock codim

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Portable Document Format (PDF) file https://doi.org/10.1107/S0108768109045091/pi5003sup2.pdf
Electron-density maps, histogram and table of geometrical and topological properties

txt

Text file https://doi.org/10.1107/S0108768109045091/pi5003sup3.txt
Multipole parameters

CCDC reference: 760239

Computing details top

Data collection: Apex2 (Bruker-Nonius,2007); cell refinement: Saint+(Bruker-Nonius,2007); data reduction: Saint+(Bruker-Nonius,2007); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).

(codim) top
Crystal data top
C28H10Co4O12F(000) = 1528
Mr = 774.08Dx = 1.819 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.8195 (3) ŵ = 2.37 mm1
b = 17.5085 (5) ÅT = 90 K
c = 18.3080 (5) ÅPrism, colourless
β = 90.444 (1)°0.55 × 0.24 × 0.15 mm
V = 2826.97 (15) Å3
Data collection top
Bruker X8 APEX-II
diffractometer
33537 independent reflections
Radiation source: fine-focus sealed tube27825 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 12.00 pixels mm-1θmax = 56.9°, θmin = 2.2°
Narrow slices collected using φ– and ω–scansh = 2020
Absorption correction: gaussiank = 040
Tmin = 0.288, Tmax = 0.737l = 040
252043 measured reflections
Refinement top
Refinement on F2677 parameters
Least-squares matrix: full0 restraints
R[F2 > 2σ(F2)] = 0.016 w2 = 1/[s2(Fo2)]
wR(F2) = 0.021(Δ/σ)max < 0.001
S = 1.53Δρmax = 0.52 e Å3
27825 reflectionsΔρmin = 0.58 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
CO(1)0.834583 (4)0.356449 (2)0.202525 (2)0.009
CO(2)0.678305 (4)0.240432 (2)0.208812 (1)0.009
CO(3)0.807934 (4)0.388564 (2)0.432837 (2)0.009
CO(4)0.547264 (4)0.339192 (2)0.438139 (2)0.009
O(1)0.88621 (3)0.513994 (13)0.251917 (12)0.023
O(2)1.12736 (3)0.283736 (14)0.244438 (12)0.023
O(3)0.85532 (3)0.371195 (14)0.041843 (10)0.024
O(4)0.40213 (3)0.160665 (14)0.255912 (12)0.024
O(5)0.91304 (3)0.128305 (13)0.254849 (11)0.022
O(6)0.66649 (2)0.210154 (12)0.049991 (9)0.019
O(7)1.11988 (3)0.389558 (15)0.376976 (13)0.025
O(8)0.72760 (3)0.549725 (13)0.401884 (12)0.024
O(9)0.87872 (3)0.389794 (15)0.591427 (10)0.028
O(10)0.30197 (2)0.236567 (13)0.390197 (12)0.021
O(11)0.38967 (3)0.487830 (13)0.422938 (11)0.021
O(12)0.54217 (3)0.305419 (16)0.596587 (10)0.029
C(1)0.48182 (3)0.391441 (14)0.197253 (11)0.01
C(2)0.44314 (3)0.456458 (16)0.237842 (13)0.016
C(3)0.31826 (4)0.500665 (19)0.218176 (17)0.022
C(4)0.23068 (3)0.480398 (19)0.157216 (17)0.023
C(5)0.26858 (3)0.41587 (2)0.116500 (14)0.022
C(6)0.39351 (3)0.371593 (17)0.136323 (12)0.016
C(7)0.61352 (3)0.346353 (13)0.219023 (10)0.009
C(8)0.69231 (3)0.325890 (13)0.279900 (10)0.009
C(9)0.69510 (3)0.329717 (13)0.357794 (10)0.009
C(10)0.73512 (3)0.284097 (13)0.414922 (10)0.009
C(11)0.78885 (3)0.205602 (13)0.424020 (10)0.01
C(12)0.94328 (3)0.189532 (16)0.432963 (13)0.015
C(13)0.99487 (3)0.114248 (17)0.434724 (14)0.019
C(14)0.89298 (4)0.053719 (16)0.428440 (14)0.02
C(15)0.73859 (4)0.069212 (16)0.421058 (14)0.019
C(16)0.68636 (3)0.144390 (15)0.419007 (13)0.015
C(17)0.86743 (3)0.453403 (15)0.231468 (12)0.014
C(18)1.01720 (3)0.312821 (15)0.228349 (12)0.014
C(19)0.84827 (3)0.365950 (15)0.103749 (12)0.014
C(20)0.50910 (3)0.191681 (15)0.237918 (12)0.015
C(21)0.82186 (3)0.170984 (15)0.238995 (12)0.014
C(22)0.66860 (3)0.220977 (14)0.111427 (11)0.013
C(23)0.99871 (3)0.388018 (16)0.398207 (13)0.015
C(24)0.76117 (3)0.488148 (15)0.413708 (12)0.014
C(25)0.85199 (3)0.389056 (16)0.530567 (12)0.016
C(26)0.39756 (3)0.276355 (16)0.407520 (12)0.014
C(27)0.44799 (3)0.429880 (16)0.427678 (12)0.014
C(28)0.53996 (3)0.319181 (17)0.536034 (12)0.017
H(2)0.5109950.4724020.2849810.03
H(3)0.2887620.5506090.2499420.045
H(4)0.1336190.514790.1416370.054
H(5)0.2001640.4003860.0694070.047
H(6)0.4220960.3216370.104380.033
H(12)1.0235980.235980.4386530.032
H(13)1.1149040.1026930.4410030.04
H(14)0.9335570.0046580.4292760.042
H(15)0.6587560.02240.4167490.038
H(16)0.5660530.1556070.4135010.03
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
CO(1)0.009199 (13)0.008047 (13)0.008989 (9)0.000075 (10)0.001769 (9)0.000274 (8)
CO(2)0.011424 (13)0.007101 (12)0.008423 (9)0.000484 (10)0.000966 (9)0.000775 (8)
CO(3)0.008751 (13)0.008459 (13)0.009414 (9)0.000146 (10)0.000454 (9)0.001418 (8)
CO(4)0.008348 (13)0.009896 (13)0.008582 (9)0.000760 (10)0.001502 (8)0.000598 (8)
O(1)0.03107 (12)0.01133 (9)0.02546 (8)0.00453 (9)0.00508 (8)0.00448 (7)
O(2)0.01614 (10)0.02639 (12)0.02602 (9)0.00792 (8)0.00264 (7)0.00118 (8)
O(3)0.03595 (13)0.02469 (11)0.01071 (6)0.00229 (10)0.00393 (7)0.00189 (6)
O(4)0.02198 (12)0.02139 (11)0.02863 (9)0.01008 (9)0.00985 (8)0.00469 (8)
O(5)0.02598 (12)0.01799 (10)0.02318 (8)0.00971 (9)0.00137 (8)0.00247 (7)
O(6)0.02499 (10)0.02074 (10)0.00991 (5)0.00060 (8)0.00036 (6)0.00229 (6)
O(7)0.01100 (9)0.03253 (14)0.03100 (10)0.00265 (9)0.00399 (8)0.00528 (9)
O(8)0.03028 (13)0.01035 (10)0.03115 (10)0.00293 (9)0.00469 (9)0.00317 (7)
O(9)0.02950 (12)0.04315 (15)0.01221 (7)0.01084 (10)0.00626 (7)0.00328 (8)
O(10)0.01366 (9)0.02370 (11)0.02682 (9)0.00517 (8)0.00060 (7)0.00734 (8)
O(11)0.02059 (10)0.01531 (10)0.02684 (9)0.00766 (8)0.00130 (8)0.00313 (7)
O(12)0.03157 (13)0.04343 (15)0.01176 (7)0.00639 (11)0.00231 (7)0.00693 (8)
C(1)0.00959 (9)0.01146 (9)0.01015 (6)0.00080 (7)0.00015 (6)0.00129 (6)
C(2)0.01490 (11)0.01315 (11)0.01856 (8)0.00473 (9)0.00096 (8)0.00145 (7)
C(3)0.01693 (13)0.01799 (14)0.03079 (12)0.00823 (10)0.00105 (10)0.00267 (10)
C(4)0.01168 (11)0.02718 (16)0.02926 (12)0.00496 (10)0.00024 (9)0.01273 (11)
C(5)0.01245 (11)0.03333 (17)0.01882 (9)0.00068 (11)0.00421 (8)0.00794 (10)
C(6)0.01270 (10)0.02283 (13)0.01233 (7)0.00016 (9)0.00266 (7)0.00050 (7)
C(7)0.01006 (9)0.00902 (9)0.00892 (6)0.00090 (7)0.00015 (6)0.00014 (5)
C(8)0.01008 (9)0.00855 (9)0.00778 (6)0.00037 (7)0.00048 (6)0.00016 (5)
C(9)0.00923 (8)0.00851 (9)0.00783 (6)0.00046 (6)0.00045 (6)0.00018 (5)
C(10)0.01031 (9)0.00787 (9)0.00927 (6)0.00116 (7)0.00004 (6)0.00009 (5)
C(11)0.01227 (9)0.00880 (9)0.01001 (6)0.00183 (7)0.00053 (6)0.00003 (6)
C(12)0.01320 (11)0.01327 (11)0.01848 (8)0.00437 (8)0.00249 (8)0.00168 (7)
C(13)0.02061 (13)0.01571 (12)0.02197 (10)0.00926 (10)0.00363 (9)0.00207 (8)
C(14)0.03014 (15)0.01126 (11)0.01840 (9)0.00817 (10)0.00309 (9)0.00095 (7)
C(15)0.02685 (15)0.00895 (11)0.02206 (9)0.00117 (10)0.00230 (10)0.00020 (8)
C(16)0.01684 (12)0.00925 (10)0.01983 (9)0.00033 (8)0.00150 (8)0.00084 (7)
C(17)0.01613 (11)0.00977 (10)0.01520 (7)0.00184 (8)0.00318 (7)0.00102 (6)
C(18)0.01185 (10)0.01513 (11)0.01529 (7)0.00242 (8)0.00062 (7)0.00055 (7)
C(19)0.01795 (11)0.01389 (11)0.01027 (7)0.00088 (8)0.00293 (7)0.00086 (6)
C(20)0.01699 (12)0.01176 (11)0.01577 (8)0.00399 (9)0.00417 (8)0.00227 (7)
C(21)0.01802 (12)0.01013 (10)0.01403 (7)0.00274 (8)0.00017 (7)0.00003 (6)
C(22)0.01614 (10)0.01238 (10)0.00961 (7)0.00054 (8)0.00049 (7)0.00155 (6)
C(23)0.00974 (10)0.01704 (12)0.01814 (8)0.00116 (8)0.00072 (8)0.00342 (7)
C(24)0.01632 (11)0.00924 (10)0.01696 (8)0.00003 (8)0.00112 (8)0.00035 (7)
C(25)0.01611 (11)0.01974 (12)0.01154 (7)0.00339 (9)0.00303 (7)0.00204 (7)
C(26)0.01013 (10)0.01578 (11)0.01584 (8)0.00127 (8)0.00130 (7)0.00237 (7)
C(27)0.01231 (10)0.01297 (11)0.01614 (8)0.00331 (8)0.00111 (7)0.00221 (7)
C(28)0.01721 (11)0.02211 (13)0.01046 (7)0.00214 (9)0.00296 (7)0.00182 (7)
H(2)0.0290520.0342890.0278960.0005480.0044590.007822
H(3)0.0375370.0306520.0666250.0137250.0056040.010703
H(4)0.0338950.0547260.0722310.023530.013970.014871
H(5)0.0358890.0726970.0311810.002980.0184380.004179
H(6)0.0308150.0391910.0282380.0006620.0000350.011385
H(12)0.0281170.0279090.0390990.0046060.0024390.005852
H(13)0.028860.0427880.0476420.0169770.0130890.00678
H(14)0.0593350.0180.0498310.0167540.0093580.004067
H(15)0.0465440.0211450.0450920.0101990.0028460.003046
H(16)0.0213310.0331160.0364770.0026590.0010370.000823
Geometric parameters (Å, º) top
CO(1)—C(7)1.9832 (2)O(11)—C(27)1.1405 (3)
CO(1)—C(8)1.9735 (2)O(12)—C(28)1.1345 (3)
CO(1)—C(17)1.8011 (3)C(1)—C(2)1.4030 (4)
CO(1)—C(18)1.8409 (3)C(1)—C(6)1.3994 (3)
CO(1)—C(19)1.8210 (2)C(1)—C(7)1.4574 (3)
CO(2)—C(7)1.9500 (2)C(2)—C(3)1.3913 (4)
CO(2)—C(8)1.9863 (2)C(2)—H(2)1.0830 (2)
CO(2)—C(20)1.8033 (3)C(3)—C(4)1.3981 (4)
CO(2)—C(21)1.8374 (3)C(3)—H(3)1.0830 (3)
CO(2)—C(22)1.8165 (2)C(4)—C(5)1.3955 (5)
CO(3)—C(9)1.9795 (2)C(4)—H(4)1.0830 (3)
CO(3)—C(10)1.9652 (2)C(5)—C(6)1.3930 (4)
CO(3)—C(23)1.8027 (3)C(5)—H(5)1.0830 (2)
CO(3)—C(24)1.8250 (3)C(6)—H(6)1.0830 (3)
CO(3)—C(25)1.8280 (2)C(7)—C(8)1.3570 (2)
CO(4)—C(9)1.9801 (2)C(8)—C(9)1.4277 (3)
CO(4)—C(10)1.9665 (2)C(9)—C(10)1.3604 (3)
CO(4)—C(26)1.8045 (3)C(10)—C(11)1.4628 (3)
CO(4)—C(27)1.8226 (3)C(11)—C(12)1.3991 (3)
CO(4)—C(28)1.8278 (2)C(11)—C(16)1.4046 (4)
O(1)—C(17)1.1367 (3)C(12)—C(13)1.3947 (4)
O(2)—C(18)1.1338 (3)C(12)—H(12)1.0830 (3)
O(3)—C(19)1.1393 (3)C(13)—C(14)1.3937 (5)
O(4)—C(20)1.1394 (4)C(13)—H(13)1.0830 (3)
O(5)—C(21)1.1339 (3)C(14)—C(15)1.3940 (4)
O(6)—C(22)1.1406 (3)C(14)—H(14)1.0830 (3)
O(7)—C(23)1.1403 (4)C(15)—C(16)1.3949 (4)
O(8)—C(24)1.1383 (3)C(15)—H(15)1.0830 (3)
O(9)—C(25)1.1372 (3)C(16)—H(16)1.0830 (3)
O(10)—C(26)1.1369 (3)
C(7)—CO(1)—C(8)40.115 (8)C(1)—C(6)—H(6)120.04 (2)
C(7)—CO(1)—C(17)101.261 (11)C(5)—C(6)—H(6)119.72 (2)
C(7)—CO(1)—C(18)141.542 (10)CO(1)—C(7)—CO(2)77.350 (9)
C(7)—CO(1)—C(19)103.428 (10)CO(1)—C(7)—C(1)133.825 (17)
C(8)—CO(1)—C(17)98.398 (10)CO(1)—C(7)—C(8)69.561 (14)
C(8)—CO(1)—C(18)105.247 (10)CO(2)—C(7)—C(1)136.257 (16)
C(8)—CO(1)—C(19)141.721 (10)CO(2)—C(7)—C(8)71.280 (13)
C(17)—CO(1)—C(18)100.201 (12)C(1)—C(7)—C(8)140.32 (2)
C(17)—CO(1)—C(19)101.205 (11)CO(1)—C(8)—CO(2)76.737 (8)
C(18)—CO(1)—C(19)103.200 (11)CO(1)—C(8)—C(7)70.324 (14)
C(7)—CO(2)—C(8)40.320 (8)CO(1)—C(8)—C(9)134.279 (16)
C(7)—CO(2)—C(20)100.256 (11)CO(2)—C(8)—C(7)68.400 (13)
C(7)—CO(2)—C(21)143.350 (9)CO(2)—C(8)—C(9)133.658 (17)
C(7)—CO(2)—C(22)105.119 (10)C(7)—C(8)—C(9)144.36 (2)
C(8)—CO(2)—C(20)102.143 (10)CO(3)—C(9)—CO(4)76.772 (7)
C(8)—CO(2)—C(21)105.202 (9)CO(3)—C(9)—C(8)136.252 (17)
C(8)—CO(2)—C(22)141.867 (10)CO(3)—C(9)—C(10)69.265 (12)
C(20)—CO(2)—C(21)99.660 (12)CO(4)—C(9)—C(8)137.700 (16)
C(20)—CO(2)—C(22)99.699 (11)CO(4)—C(9)—C(10)69.298 (13)
C(21)—CO(2)—C(22)101.432 (11)C(8)—C(9)—C(10)137.97 (2)
C(9)—CO(3)—C(10)40.346 (8)CO(3)—C(10)—CO(4)77.417 (8)
C(9)—CO(3)—C(23)102.634 (10)CO(3)—C(10)—C(9)70.389 (13)
C(9)—CO(3)—C(24)104.621 (9)CO(3)—C(10)—C(11)138.612 (16)
C(9)—CO(3)—C(25)141.601 (11)CO(4)—C(10)—C(9)70.376 (14)
C(10)—CO(3)—C(23)103.948 (11)CO(4)—C(10)—C(11)135.151 (18)
C(10)—CO(3)—C(24)141.636 (9)C(9)—C(10)—C(11)136.140 (19)
C(10)—CO(3)—C(25)103.559 (11)C(10)—C(11)—C(12)121.09 (2)
C(23)—CO(3)—C(24)98.497 (12)C(10)—C(11)—C(16)120.11 (2)
C(23)—CO(3)—C(25)98.764 (11)C(12)—C(11)—C(16)118.66 (2)
C(24)—CO(3)—C(25)103.258 (11)C(11)—C(12)—C(13)120.66 (3)
C(9)—CO(4)—C(10)40.326 (8)C(11)—C(12)—H(12)119.71 (2)
C(9)—CO(4)—C(26)101.686 (10)C(13)—C(12)—H(12)119.63 (2)
C(9)—CO(4)—C(27)108.269 (10)C(12)—C(13)—C(14)120.44 (3)
C(9)—CO(4)—C(28)137.796 (11)C(12)—C(13)—H(13)119.83 (3)
C(10)—CO(4)—C(26)104.443 (11)C(14)—C(13)—H(13)119.72 (3)
C(10)—CO(4)—C(27)144.046 (11)C(13)—C(14)—C(15)119.26 (3)
C(10)—CO(4)—C(28)98.863 (11)C(13)—C(14)—H(14)120.25 (3)
C(26)—CO(4)—C(27)98.555 (11)C(15)—C(14)—H(14)120.49 (3)
C(26)—CO(4)—C(28)99.003 (12)C(14)—C(15)—C(16)120.56 (3)
C(27)—CO(4)—C(28)104.447 (12)C(14)—C(15)—H(15)119.59 (3)
C(2)—C(1)—C(6)119.18 (2)C(16)—C(15)—H(15)119.85 (3)
C(2)—C(1)—C(7)119.418 (18)C(11)—C(16)—C(15)120.40 (3)
C(6)—C(1)—C(7)121.40 (2)C(11)—C(16)—H(16)119.82 (2)
C(1)—C(2)—C(3)120.64 (2)C(15)—C(16)—H(16)119.78 (3)
C(1)—C(2)—H(2)119.74 (2)CO(1)—C(17)—O(1)177.74 (2)
C(3)—C(2)—H(2)119.62 (3)CO(1)—C(18)—O(2)177.78 (3)
C(2)—C(3)—C(4)119.78 (3)CO(1)—C(19)—O(3)179.08 (2)
C(2)—C(3)—H(3)120.21 (3)CO(2)—C(20)—O(4)179.59 (2)
C(4)—C(3)—H(3)120.00 (3)CO(2)—C(21)—O(5)177.17 (2)
C(3)—C(4)—C(5)119.91 (2)CO(2)—C(22)—O(6)177.83 (2)
C(3)—C(4)—H(4)119.98 (3)CO(3)—C(23)—O(7)178.22 (3)
C(5)—C(4)—H(4)120.10 (3)CO(3)—C(24)—O(8)177.99 (3)
C(4)—C(5)—C(6)120.24 (2)CO(3)—C(25)—O(9)179.51 (3)
C(4)—C(5)—H(5)119.58 (3)CO(4)—C(26)—O(10)178.09 (2)
C(6)—C(5)—H(5)120.18 (3)CO(4)—C(27)—O(11)177.42 (2)
C(1)—C(6)—C(5)120.24 (3)CO(4)—C(28)—O(12)176.77 (3)
 

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