The X-ray constrained wavefunction of the [Mn(CO)₄{(C₆H₅)₂P-S-C(Br₂)-P(C₆H₅)₂}]Br complex: a theoretical and experimental study of dihalogen bonds and other noncovalent interactions

The synthesis and X-ray structure determination of the [Mn(CO)₄{(C₆H₅)₂P-S-C(Br₂)-P(C₆H₅)₂}]Br complex (1) are described. The C—Br...Br dihalogen bond present in 1 has been characterized by means of topological studies of the electron density. Both the quantum theory of atoms in molecules and the electron localization function approaches have been applied to several theoretically calculated wavefunctions as well as to an X-ray constrained wavefunction. In addition, a number of theoretical techniques, such as the source function, the reduced density gradient method and the interacting quantum atoms approach, among others, have been used to analyse the dihalogen bond as well as several intramolecular interactions of the type C—H...Br—C which have also been detected in 1. The results show clearly that while bonding in the latter interactions are dominated by electrostatic components, the former has a high degree of covalency.

Computing details

Data collection: Bruker APEX2 software; cell refinement: SAINT V8.34A integration software; data reduction: SORTAV (Blessing, 1989); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

(I)

Crystal data

C29H20Br3MnO4P2S	F(000) = 1608
Mr = 821.12	Dx = 1.545 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 25 reflections
a = 15.366 (2) Å	θ = 14.2–15.7°
b = 16.035 (2) Å	µ = 3.95 mm^−1
c = 14.327 (1) Å	T = 293 K
β = 91.21 (1)°	Fragment, yellow
V = 3529.3 (7) Å^3	0.26 × 0.23 × 0.10 mm
Z = 4

Data collection

Bruker APEX-II diffractometer	2399 reflections with I > 2σ(I)
φ or ω oscillation scans	Rint = 0.057
Absorption correction: multi-scan SADABS-2014/5 - Bruker AXS area detector scaling and absorption correction	θmax = 26.0°, θmin = 1.4°
Tmin = 0.528, Tmax = 0.996	h = −18→18
3749 measured reflections	k = 0→19
3603 independent reflections	l = −17→0

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0824P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
3603 reflections	Δρmax = 0.68 e Å^−3
361 parameters	Δρmin = −0.49 e Å^−3
1 restraint	Absolute structure: No quotients, so Flack parameter determined by classical intensity fit
0 constraints	Absolute structure parameter: 0.040 (14)
Primary atom site location: dual

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. A rather disordered solvent area could not be modeled by means of any combination of constraints and restraints and it was treated by the SQUEEZE routine included in the PLATON program package (Spek, 2009).

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

	x	y	z	Uiso*/Ueq
Mn1	1.25719 (9)	0.95207 (10)	0.73293 (9)	0.0419 (4)
C1	1.3001 (6)	0.8493 (9)	0.6891 (7)	0.052 (3)
O1	1.3276 (6)	0.7898 (6)	0.6633 (6)	0.074 (3)
C2	1.2121 (7)	1.0541 (7)	0.7705 (7)	0.050 (3)
O2	1.1836 (6)	1.1166 (6)	0.7889 (7)	0.077 (3)
C3	1.2482 (6)	0.9902 (8)	0.6119 (7)	0.056 (3)
O3	1.2474 (6)	1.0137 (7)	0.5391 (5)	0.088 (3)
C4	1.3705 (7)	0.9881 (7)	0.7362 (7)	0.050 (2)
O4	1.4398 (5)	1.0056 (6)	0.7319 (6)	0.071 (2)
S1	1.08960 (16)	0.82918 (18)	0.84977 (16)	0.0473 (6)
C5	1.1591 (6)	0.8836 (6)	0.9304 (6)	0.040 (2)
Br1	1.11187 (7)	0.99513 (7)	0.95985 (9)	0.0600 (3)
Br2	1.15083 (7)	0.81779 (7)	1.04760 (6)	0.0495 (3)
Br3	1.11204 (9)	0.71159 (8)	1.22123 (8)	0.0695 (4)
P1	1.11926 (16)	0.89320 (18)	0.72509 (16)	0.0435 (6)
C6	1.1088 (6)	0.8109 (7)	0.6386 (7)	0.047 (2)
C7	1.1062 (7)	0.8324 (8)	0.5444 (7)	0.059 (3)
H7	1.10287	0.888541	0.528349	0.071*
C8	1.1082 (8)	0.7746 (12)	0.4750 (9)	0.084 (5)
H8	1.10447	0.791355	0.412851	0.101*
C9	1.1156 (9)	0.6935 (11)	0.4962 (10)	0.084 (4)
H9	1.118773	0.654182	0.448673	0.1*
C10	1.1184 (9)	0.6682 (10)	0.5878 (12)	0.093 (5)
H10	1.121197	0.61153	0.601505	0.112*
C11	1.1172 (8)	0.7270 (8)	0.6618 (8)	0.063 (3)
H11	1.121898	0.709983	0.723785	0.076*
C12	1.0237 (6)	0.9579 (7)	0.7016 (7)	0.046 (2)
C13	0.9427 (8)	0.9338 (8)	0.7307 (9)	0.067 (3)
H13	0.935797	0.884975	0.764811	0.08*
C14	0.8717 (8)	0.9836 (9)	0.7080 (11)	0.083 (4)
H14	0.817836	0.968767	0.731412	0.1*
C15	0.8759 (9)	1.0508 (10)	0.6553 (10)	0.079 (4)
H15	0.825631	1.080232	0.639044	0.094*
C16	0.9554 (9)	1.0766 (10)	0.6249 (10)	0.088 (5)
H16	0.959862	1.125054	0.589669	0.106*
C17	1.0296 (8)	1.0301 (9)	0.6470 (9)	0.077 (4)
H17	1.083449	1.047126	0.625392	0.093*
P2	1.27082 (15)	0.90355 (16)	0.88659 (17)	0.0387 (5)
C18	1.3301 (6)	0.8058 (7)	0.8915 (6)	0.041 (2)
C19	1.4212 (8)	0.8114 (10)	0.8920 (8)	0.069 (3)
H19	1.448835	0.862737	0.899002	0.083*
C20	1.4694 (8)	0.7387 (9)	0.8820 (8)	0.068 (3)
H20	1.529854	0.741715	0.88198	0.082*
C21	1.4294 (10)	0.6624 (10)	0.8720 (9)	0.074 (4)
H21	1.462193	0.614394	0.863561	0.089*
C22	1.3414 (10)	0.6583 (9)	0.8746 (8)	0.072 (4)
H22	1.314601	0.606394	0.869981	0.087*
C23	1.2901 (7)	0.7288 (6)	0.8839 (8)	0.050 (3)
H23	1.229751	0.724428	0.884965	0.061*
C24	1.3255 (6)	0.9662 (6)	0.9770 (6)	0.041 (2)
C25	1.3469 (6)	1.0501 (7)	0.9571 (7)	0.050 (3)
H25	1.332171	1.0743	0.899939	0.06*
C26	1.3903 (7)	1.0942 (8)	1.0254 (8)	0.056 (3)
H26	1.407795	1.148408	1.012494	0.067*
C27	1.4084 (8)	1.0626 (7)	1.1097 (8)	0.059 (3)
H27	1.434541	1.095533	1.155836	0.071*
C28	1.3876 (8)	0.9801 (8)	1.1277 (8)	0.068 (3)
H28	1.402153	0.956794	1.185331	0.082*
C29	1.3455 (7)	0.9323 (7)	1.0603 (7)	0.052 (3)
H29	1.331129	0.877098	1.07261	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0353 (8)	0.0478 (9)	0.0425 (7)	−0.0031 (7)	−0.0042 (6)	0.0071 (7)
C1	0.027 (5)	0.092 (9)	0.038 (5)	−0.009 (6)	−0.001 (4)	−0.010 (5)
O1	0.064 (6)	0.074 (6)	0.083 (6)	0.013 (5)	0.020 (5)	−0.019 (5)
C2	0.051 (6)	0.040 (6)	0.058 (6)	−0.008 (5)	−0.004 (5)	−0.007 (5)
O2	0.074 (6)	0.058 (6)	0.099 (7)	0.010 (5)	−0.009 (5)	0.001 (5)
C3	0.048 (6)	0.067 (7)	0.052 (6)	−0.002 (6)	−0.001 (5)	0.007 (6)
O3	0.085 (6)	0.122 (9)	0.057 (5)	−0.013 (6)	−0.003 (4)	0.042 (6)
C4	0.050 (6)	0.042 (6)	0.055 (6)	0.001 (5)	−0.014 (5)	0.010 (5)
O4	0.051 (5)	0.072 (6)	0.090 (6)	−0.014 (5)	0.002 (4)	−0.005 (5)
S1	0.0483 (14)	0.0502 (16)	0.0433 (12)	−0.0130 (13)	−0.0037 (10)	0.0039 (12)
C5	0.037 (5)	0.038 (5)	0.045 (5)	−0.010 (4)	−0.004 (4)	0.012 (4)
Br1	0.0485 (6)	0.0542 (7)	0.0777 (8)	0.0082 (5)	0.0080 (5)	−0.0057 (6)
Br2	0.0535 (6)	0.0541 (6)	0.0411 (5)	−0.0051 (5)	0.0029 (4)	0.0005 (5)
Br3	0.0986 (10)	0.0580 (7)	0.0521 (6)	0.0135 (7)	0.0052 (6)	0.0008 (6)
P1	0.0406 (13)	0.0498 (16)	0.0399 (12)	−0.0035 (12)	−0.0047 (10)	0.0027 (12)
C6	0.038 (5)	0.046 (6)	0.055 (5)	0.011 (5)	−0.003 (4)	−0.010 (5)
C7	0.068 (7)	0.054 (7)	0.054 (6)	0.000 (6)	−0.015 (5)	−0.007 (6)
C8	0.058 (8)	0.134 (15)	0.060 (7)	0.021 (9)	−0.006 (6)	−0.019 (9)
C9	0.071 (9)	0.110 (14)	0.069 (9)	0.011 (9)	−0.005 (7)	−0.023 (9)
C10	0.087 (10)	0.068 (10)	0.123 (14)	−0.008 (8)	−0.014 (9)	−0.046 (10)
C11	0.080 (8)	0.052 (7)	0.056 (6)	0.006 (6)	−0.005 (6)	−0.006 (6)
C12	0.038 (5)	0.046 (6)	0.054 (6)	0.005 (5)	−0.013 (4)	−0.001 (5)
C13	0.061 (7)	0.059 (8)	0.080 (8)	−0.010 (6)	0.001 (6)	0.011 (6)
C14	0.045 (7)	0.077 (11)	0.128 (12)	0.024 (7)	−0.018 (7)	−0.014 (9)
C15	0.069 (9)	0.081 (10)	0.085 (9)	0.021 (8)	−0.030 (7)	−0.006 (8)
C16	0.072 (9)	0.102 (12)	0.089 (10)	0.027 (9)	−0.020 (8)	0.025 (9)
C17	0.061 (7)	0.082 (9)	0.089 (9)	0.006 (7)	−0.014 (6)	0.044 (8)
P2	0.0330 (12)	0.0429 (14)	0.0400 (12)	−0.0010 (11)	−0.0015 (10)	0.0024 (11)
C18	0.036 (5)	0.057 (7)	0.029 (4)	0.012 (5)	0.002 (4)	0.011 (4)
C19	0.060 (7)	0.084 (9)	0.063 (7)	0.000 (7)	−0.004 (5)	−0.006 (7)
C20	0.055 (7)	0.077 (10)	0.073 (8)	0.019 (7)	−0.005 (6)	0.006 (7)
C21	0.081 (10)	0.075 (10)	0.067 (8)	0.037 (8)	−0.002 (7)	0.008 (7)
C22	0.098 (11)	0.066 (9)	0.054 (7)	0.004 (8)	0.006 (7)	0.003 (6)
C23	0.050 (6)	0.034 (6)	0.068 (7)	−0.005 (5)	0.010 (5)	−0.007 (5)
C24	0.038 (5)	0.037 (5)	0.047 (5)	−0.003 (4)	−0.009 (4)	−0.002 (4)
C25	0.036 (5)	0.058 (7)	0.057 (6)	0.004 (5)	−0.005 (5)	−0.005 (5)
C26	0.051 (6)	0.047 (6)	0.068 (7)	0.012 (5)	−0.005 (6)	−0.010 (6)
C27	0.058 (7)	0.054 (7)	0.064 (7)	0.002 (6)	−0.019 (6)	−0.002 (6)
C28	0.067 (7)	0.081 (10)	0.055 (6)	−0.004 (7)	−0.019 (6)	0.010 (6)
C29	0.059 (7)	0.041 (6)	0.054 (6)	−0.014 (5)	−0.017 (5)	0.004 (5)

Geometric parameters (Å, º)

Mn1—C4	1.835 (11)	C14—C15	1.32 (2)
Mn1—C3	1.841 (11)	C14—H14	0.93
Mn1—C2	1.861 (12)	C15—C16	1.37 (2)
Mn1—C1	1.888 (14)	C15—H15	0.93
Mn1—P1	2.321 (3)	C16—C17	1.393 (17)
Mn1—P2	2.340 (3)	C16—H16	0.93
C1—O1	1.109 (14)	C17—H17	0.93
C2—O2	1.127 (13)	P2—C18	1.813 (10)
C3—O3	1.108 (12)	P2—C24	1.829 (9)
C4—O4	1.104 (12)	C18—C23	1.383 (15)
S1—C5	1.785 (10)	C18—C19	1.402 (15)
S1—P1	2.118 (3)	C19—C20	1.390 (19)
C5—P2	1.868 (9)	C19—H19	0.93
C5—Br1	1.978 (10)	C20—C21	1.38 (2)
C5—Br2	1.989 (9)	C20—H20	0.93
P1—C6	1.816 (10)	C21—C22	1.35 (2)
P1—C12	1.823 (10)	C21—H21	0.93
C6—C11	1.391 (16)	C22—C23	1.388 (17)
C6—C7	1.392 (15)	C22—H22	0.93
C7—C8	1.361 (18)	C23—H23	0.93
C7—H7	0.93	C24—C29	1.341 (14)
C8—C9	1.34 (2)	C24—C25	1.416 (16)
C8—H8	0.93	C25—C26	1.369 (15)
C9—C10	1.37 (2)	C25—H25	0.93
C9—H9	0.93	C26—C27	1.333 (16)
C10—C11	1.420 (18)	C26—H26	0.93
C10—H10	0.93	C27—C28	1.386 (18)
C11—H11	0.93	C27—H27	0.93
C12—C13	1.377 (15)	C28—C29	1.384 (16)
C12—C17	1.401 (16)	C28—H28	0.93
C13—C14	1.386 (17)	C29—H29	0.93
C13—H13	0.93
C4—Mn1—C3	88.4 (5)	C14—C13—H13	120.7
C4—Mn1—C2	94.3 (5)	C15—C14—C13	123.9 (14)
C3—Mn1—C2	87.7 (5)	C15—C14—H14	118
C4—Mn1—C1	86.8 (5)	C13—C14—H14	118
C3—Mn1—C1	89.8 (5)	C14—C15—C16	118.9 (13)
C2—Mn1—C1	177.2 (5)	C14—C15—H15	120.5
C4—Mn1—P1	174.2 (4)	C16—C15—H15	120.5
C3—Mn1—P1	92.3 (3)	C15—C16—C17	119.9 (14)
C2—Mn1—P1	91.5 (3)	C15—C16—H16	120.1
C1—Mn1—P1	87.4 (3)	C17—C16—H16	120.1
C4—Mn1—P2	90.8 (3)	C16—C17—C12	120.4 (13)
C3—Mn1—P2	179.2 (3)	C16—C17—H17	119.8
C2—Mn1—P2	92.7 (3)	C12—C17—H17	119.8
C1—Mn1—P2	89.9 (3)	C18—P2—C24	103.0 (4)
P1—Mn1—P2	88.49 (10)	C18—P2—C5	107.7 (4)
O1—C1—Mn1	178.1 (9)	C24—P2—C5	105.5 (4)
O2—C2—Mn1	176.6 (10)	C18—P2—Mn1	111.0 (3)
O3—C3—Mn1	176.3 (10)	C24—P2—Mn1	120.9 (3)
O4—C4—Mn1	174.1 (10)	C5—P2—Mn1	108.0 (3)
C5—S1—P1	99.9 (3)	C23—C18—C19	120.0 (11)
S1—C5—P2	114.0 (5)	C23—C18—P2	123.1 (7)
S1—C5—Br1	111.3 (5)	C19—C18—P2	116.5 (9)
P2—C5—Br1	105.1 (4)	C20—C19—C18	118.6 (13)
S1—C5—Br2	103.8 (4)	C20—C19—H19	120.7
P2—C5—Br2	116.7 (5)	C18—C19—H19	120.7
Br1—C5—Br2	105.6 (4)	C21—C20—C19	121.2 (12)
C6—P1—C12	103.2 (5)	C21—C20—H20	119.4
C6—P1—S1	101.9 (4)	C19—C20—H20	119.4
C12—P1—S1	104.2 (3)	C22—C21—C20	119.1 (12)
C6—P1—Mn1	113.3 (3)	C22—C21—H21	120.5
C12—P1—Mn1	120.6 (4)	C20—C21—H21	120.5
S1—P1—Mn1	111.65 (13)	C21—C22—C23	122.2 (13)
C11—C6—C7	118.2 (10)	C21—C22—H22	118.9
C11—C6—P1	122.2 (8)	C23—C22—H22	118.9
C7—C6—P1	118.8 (9)	C18—C23—C22	118.8 (10)
C8—C7—C6	122.6 (13)	C18—C23—H23	120.6
C8—C7—H7	118.7	C22—C23—H23	120.6
C6—C7—H7	118.7	C29—C24—C25	120.9 (9)
C9—C8—C7	119.9 (14)	C29—C24—P2	120.0 (8)
C9—C8—H8	120.1	C25—C24—P2	119.0 (8)
C7—C8—H8	120.1	C26—C25—C24	117.3 (10)
C8—C9—C10	120.3 (14)	C26—C25—H25	121.3
C8—C9—H9	119.8	C24—C25—H25	121.3
C10—C9—H9	119.8	C27—C26—C25	122.7 (12)
C9—C10—C11	121.1 (15)	C27—C26—H26	118.6
C9—C10—H10	119.4	C25—C26—H26	118.6
C11—C10—H10	119.4	C26—C27—C28	119.0 (11)
C6—C11—C10	117.8 (12)	C26—C27—H27	120.5
C6—C11—H11	121.1	C28—C27—H27	120.5
C10—C11—H11	121.1	C29—C28—C27	120.4 (11)
C13—C12—C17	118.1 (10)	C29—C28—H28	119.8
C13—C12—P1	120.9 (9)	C27—C28—H28	119.8
C17—C12—P1	120.8 (8)	C24—C29—C28	119.4 (10)
C12—C13—C14	118.7 (12)	C24—C29—H29	120.3
C12—C13—H13	120.7	C28—C29—H29	120.3
P1—S1—C5—P2	−43.5 (5)	S1—C5—P2—C24	175.8 (5)
P1—S1—C5—Br1	75.2 (4)	Br1—C5—P2—C24	53.6 (5)
P1—S1—C5—Br2	−171.6 (3)	Br2—C5—P2—C24	−63.1 (6)
C12—P1—C6—C11	−131.2 (10)	S1—C5—P2—Mn1	45.1 (6)
S1—P1—C6—C11	−23.4 (10)	Br1—C5—P2—Mn1	−77.0 (4)
Mn1—P1—C6—C11	96.7 (10)	Br2—C5—P2—Mn1	166.3 (4)
C12—P1—C6—C7	59.2 (9)	C24—P2—C18—C23	139.5 (8)
S1—P1—C6—C7	167.0 (8)	C5—P2—C18—C23	28.3 (9)
Mn1—P1—C6—C7	−72.9 (8)	Mn1—P2—C18—C23	−89.7 (8)
C11—C6—C7—C8	2.5 (18)	C24—P2—C18—C19	−48.1 (8)
P1—C6—C7—C8	172.5 (10)	C5—P2—C18—C19	−159.3 (7)
C6—C7—C8—C9	−2 (2)	Mn1—P2—C18—C19	82.7 (8)
C7—C8—C9—C10	2 (2)	C23—C18—C19—C20	1.9 (16)
C8—C9—C10—C11	−3 (2)	P2—C18—C19—C20	−170.7 (9)
C7—C6—C11—C10	−2.9 (17)	C18—C19—C20—C21	−0.3 (18)
P1—C6—C11—C10	−172.6 (9)	C19—C20—C21—C22	−1.8 (19)
C9—C10—C11—C6	3 (2)	C20—C21—C22—C23	2.2 (19)
C6—P1—C12—C13	77.4 (10)	C19—C18—C23—C22	−1.6 (15)
S1—P1—C12—C13	−28.7 (10)	P2—C18—C23—C22	170.6 (8)
Mn1—P1—C12—C13	−155.0 (8)	C21—C22—C23—C18	−0.5 (18)
C6—P1—C12—C17	−97.5 (10)	C18—P2—C24—C29	−44.4 (10)
S1—P1—C12—C17	156.4 (9)	C5—P2—C24—C29	68.4 (10)
Mn1—P1—C12—C17	30.2 (11)	Mn1—P2—C24—C29	−169.0 (8)
C17—C12—C13—C14	−2.6 (18)	C18—P2—C24—C25	134.9 (8)
P1—C12—C13—C14	−177.6 (10)	C5—P2—C24—C25	−112.3 (8)
C12—C13—C14—C15	4 (2)	Mn1—P2—C24—C25	10.3 (9)
C13—C14—C15—C16	−4 (2)	C29—C24—C25—C26	1.3 (15)
C14—C15—C16—C17	2 (2)	P2—C24—C25—C26	−178.0 (8)
C15—C16—C17—C12	−1 (2)	C24—C25—C26—C27	−3.5 (16)
C13—C12—C17—C16	1.3 (19)	C25—C26—C27—C28	4.2 (18)
P1—C12—C17—C16	176.3 (11)	C26—C27—C28—C29	−2.7 (19)
S1—C5—P2—C18	−74.8 (6)	C25—C24—C29—C28	0.0 (17)
Br1—C5—P2—C18	163.1 (4)	P2—C24—C29—C28	179.3 (9)
Br2—C5—P2—C18	46.4 (6)	C27—C28—C29—C24	0.6 (19)