Crystal structure and fluorescence study of (μ-N-[(3,5-dimethyl-1H-pyrrol-2-yl)methyl­idene]-N-{4-[(3,5-dimethyl-1H-pyrrol-2-yl)methyl­idene­aza­nium­yl]phen­yl}aza­nium)bis­[di­fluorido­boron(IV)]

In the title compound, each boron atom is four-coordinated by two fluorine atoms, a pyrrole N atom and an imine N atom. Both imine CH=N groups adopt a trans conformation. In the crystal, the mol­ecules self-assemble into a pillar structure through C—H...F hydrogen bonds and π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.048
• wR factor = 0.126
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.539 Check

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT300_ALERT_4_G Atom Site Occupancy of H5A        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H5B        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H5C        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H6A        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H6B        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H6C        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H19A       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H19B       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H19C       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H20A       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H20B       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H20C       Constrained at        0.5 Check
PLAT367_ALERT_2_G Long?  C(sp?)-C(sp?) Bond  C4       - C6       .       1.50 Ang.
PLAT367_ALERT_2_G Long?  C(sp?)-C(sp?) Bond  C18      - C20      .       1.50 Ang.
PLAT789_ALERT_4_G Atoms with Negative _atom_site_disorder_group  #         12 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        69% Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  19 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
  13 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: ShelXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(µ-N-[(3,5-Dimethyl-1H-pyrrol-2-yl)methylidene]N-{{4-[(3,5-dimethyl-1H-pyrrol-2-yl)methylideneazaniumyl]phenyl}azanium)bis[difluoridoboron(IV)]

Crystal data

C20H20B2F4N4	Dx = 1.479 Mg m^−3
Mr = 414.02	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pnma	Cell parameters from 1337 reflections
a = 20.2495 (9) Å	θ = 3.9–73.0°
b = 6.8046 (5) Å	µ = 0.99 mm^−1
c = 13.4969 (5) Å	T = 110 K
V = 1859.74 (17) Å^3	Block, brown
Z = 4	0.25 × 0.14 × 0.13 mm
F(000) = 856

Data collection

Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, AtlasS2 diffractometer	1815 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1375 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 5.2740 pixels mm^-1	θmax = 67.1°, θmin = 3.9°
ω scans	h = −17→24
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	k = −7→8
Tmin = 0.478, Tmax = 1.000	l = −13→16
4486 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0648P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
1815 reflections	Δρmax = 0.27 e Å^−3
179 parameters	Δρmin = −0.32 e Å^−3
6 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.47574 (6)	0.5830 (2)	0.79642 (10)	0.0251 (3)
F2	0.27560 (6)	0.58327 (19)	0.39551 (9)	0.0214 (3)
N1	0.57949 (12)	0.750000	0.83332 (18)	0.0181 (6)
N2	0.54122 (11)	0.750000	0.66808 (19)	0.0152 (5)
N3	0.37529 (11)	0.750000	0.33323 (18)	0.0146 (5)
N4	0.27854 (11)	0.750000	0.2358 (2)	0.0167 (6)
C1	0.63149 (14)	0.750000	0.7670 (2)	0.0175 (6)
C2	0.60426 (15)	0.750000	0.9262 (2)	0.0196 (7)
C3	0.67356 (15)	0.750000	0.9190 (2)	0.0215 (7)
H3	0.702742	0.750000	0.972227	0.026*
C4	0.69141 (14)	0.750000	0.8194 (2)	0.0183 (6)
C5	0.56119 (16)	0.750000	1.0158 (2)	0.0256 (7)
H5A	0.550754	0.617060	1.033709	0.038*	0.5
H5B	0.521163	0.820249	1.001678	0.038*	0.5
H5C	0.583911	0.812692	1.069602	0.038*	0.5
C6	0.76010 (14)	0.750000	0.7777 (3)	0.0223 (7)
H6A	0.788406	0.827009	0.819538	0.034*	0.5
H6B	0.759521	0.805418	0.712325	0.034*	0.5
H6C	0.776318	0.617573	0.774672	0.034*	0.5
C7	0.60731 (14)	0.750000	0.6711 (2)	0.0174 (6)
H7	0.633991	0.750000	0.615007	0.021*
C8	0.50243 (14)	0.750000	0.5815 (2)	0.0153 (6)
C9	0.43380 (14)	0.750000	0.5922 (2)	0.0190 (7)
H9	0.415253	0.750000	0.655206	0.023*
C10	0.39326 (14)	0.750000	0.5099 (2)	0.0212 (7)
H10	0.347688	0.750000	0.518466	0.025*
C11	0.41924 (14)	0.750000	0.4141 (2)	0.0150 (6)
C12	0.48845 (14)	0.750000	0.4035 (2)	0.0169 (6)
H12	0.507081	0.750000	0.340566	0.020*
C13	0.52863 (13)	0.750000	0.4856 (2)	0.0183 (7)
H13	0.574212	0.750000	0.477137	0.022*
C14	0.39064 (13)	0.750000	0.2381 (2)	0.0172 (6)
H14	0.433769	0.750000	0.214397	0.021*
C15	0.33467 (13)	0.750000	0.1766 (2)	0.0169 (6)
C16	0.31589 (16)	0.750000	0.0770 (2)	0.0199 (7)
C17	0.24674 (15)	0.750000	0.0784 (2)	0.0208 (7)
H17	0.219502	0.750000	0.022896	0.025*
C18	0.22542 (14)	0.750000	0.1769 (2)	0.0192 (7)
C19	0.35899 (15)	0.750000	−0.0125 (2)	0.0260 (7)
H19A	0.358113	0.622295	−0.042734	0.039*	0.5
H19B	0.403441	0.781639	0.006382	0.039*	0.5
H19C	0.343184	0.846066	−0.058910	0.039*	0.5
C20	0.15647 (15)	0.750000	0.2183 (3)	0.0276 (8)
H20A	0.138964	0.881066	0.216494	0.041*	0.5
H20B	0.157389	0.704099	0.285535	0.041*	0.5
H20C	0.129033	0.664835	0.179283	0.041*	0.5
B1	0.51243 (16)	0.750000	0.7788 (2)	0.0164 (7)
B2	0.29629 (15)	0.750000	0.3467 (3)	0.0163 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0203 (6)	0.0351 (8)	0.0197 (6)	−0.0089 (6)	−0.0011 (5)	0.0052 (6)
F2	0.0177 (6)	0.0275 (7)	0.0190 (6)	−0.0052 (5)	0.0007 (5)	0.0037 (6)
N1	0.0159 (12)	0.0255 (14)	0.0128 (12)	0.000	−0.0019 (10)	0.000
N2	0.0108 (10)	0.0211 (13)	0.0137 (12)	0.000	−0.0022 (10)	0.000
N3	0.0109 (11)	0.0196 (12)	0.0133 (12)	0.000	0.0000 (10)	0.000
N4	0.0114 (11)	0.0199 (13)	0.0187 (13)	0.000	−0.0012 (10)	0.000
C1	0.0144 (13)	0.0195 (15)	0.0186 (15)	0.000	−0.0019 (12)	0.000
C2	0.0233 (15)	0.0194 (15)	0.0163 (15)	0.000	−0.0034 (13)	0.000
C3	0.0203 (15)	0.0230 (16)	0.0213 (15)	0.000	−0.0064 (13)	0.000
C4	0.0147 (13)	0.0166 (14)	0.0235 (15)	0.000	−0.0078 (12)	0.000
C5	0.0239 (14)	0.0358 (19)	0.0169 (15)	0.000	−0.0045 (13)	0.000
C6	0.0140 (13)	0.0262 (17)	0.0267 (17)	0.000	−0.0062 (13)	0.000
C7	0.0115 (13)	0.0221 (15)	0.0185 (15)	0.000	−0.0007 (12)	0.000
C8	0.0136 (13)	0.0182 (14)	0.0142 (15)	0.000	−0.0024 (11)	0.000
C9	0.0136 (13)	0.0309 (17)	0.0126 (14)	0.000	0.0015 (12)	0.000
C10	0.0099 (12)	0.0345 (17)	0.0193 (16)	0.000	0.0000 (12)	0.000
C11	0.0128 (13)	0.0179 (14)	0.0144 (14)	0.000	−0.0024 (11)	0.000
C12	0.0123 (13)	0.0259 (15)	0.0124 (14)	0.000	0.0029 (11)	0.000
C13	0.0085 (12)	0.0255 (16)	0.0209 (16)	0.000	−0.0008 (12)	0.000
C14	0.0118 (13)	0.0200 (15)	0.0198 (15)	0.000	−0.0010 (12)	0.000
C15	0.0119 (12)	0.0179 (14)	0.0209 (16)	0.000	0.0006 (12)	0.000
C16	0.0213 (14)	0.0212 (15)	0.0173 (14)	0.000	−0.0064 (13)	0.000
C17	0.0196 (14)	0.0264 (17)	0.0166 (15)	0.000	−0.0093 (13)	0.000
C18	0.0158 (14)	0.0235 (16)	0.0183 (15)	0.000	−0.0044 (12)	0.000
C19	0.0229 (15)	0.0370 (18)	0.0182 (16)	0.000	−0.0004 (13)	0.000
C20	0.0148 (14)	0.045 (2)	0.0234 (17)	0.000	−0.0037 (13)	0.000
B1	0.0160 (15)	0.0232 (18)	0.0100 (16)	0.000	−0.0018 (13)	0.000
B2	0.0092 (14)	0.0238 (18)	0.0158 (15)	0.000	−0.0036 (13)	0.000

Geometric parameters (Å, º)

F1—B1	1.378 (2)	C6—H6C	0.9600
F2—B2	1.377 (2)	C7—H7	0.9300
N1—C1	1.382 (4)	C8—C9	1.397 (4)
N1—C2	1.350 (4)	C8—C13	1.399 (4)
N1—B1	1.544 (4)	C9—H9	0.9300
N2—C7	1.339 (4)	C9—C10	1.381 (4)
N2—C8	1.408 (4)	C10—H10	0.9300
N2—B1	1.604 (4)	C10—C11	1.396 (4)
N3—C11	1.408 (4)	C11—C12	1.409 (4)
N3—C14	1.321 (4)	C12—H12	0.9300
N3—B2	1.610 (4)	C12—C13	1.374 (4)
N4—C15	1.389 (4)	C13—H13	0.9300
N4—C18	1.338 (4)	C14—H14	0.9300
N4—B2	1.538 (4)	C14—C15	1.404 (4)
C1—C4	1.404 (4)	C15—C16	1.398 (4)
C1—C7	1.384 (4)	C16—C17	1.400 (4)
C2—C3	1.407 (4)	C16—C19	1.491 (5)
C2—C5	1.491 (5)	C17—H17	0.9300
C3—H3	0.9300	C17—C18	1.398 (5)
C3—C4	1.393 (5)	C18—C20	1.504 (4)
C4—C6	1.500 (4)	C19—H19A	0.9600
C5—H5A	0.9600	C19—H19B	0.9600
C5—H5B	0.9600	C19—H19C	0.9600
C5—H5C	0.9600	C20—H20A	0.9600
C6—H6A	0.9600	C20—H20B	0.9600
C6—H6B	0.9600	C20—H20C	0.9600
C1—N1—B1	111.2 (2)	N3—C11—C12	123.4 (3)
C2—N1—C1	108.6 (2)	C10—C11—N3	118.7 (2)
C2—N1—B1	140.2 (3)	C10—C11—C12	117.9 (3)
C7—N2—C8	125.6 (3)	C11—C12—H12	119.7
C7—N2—B1	109.6 (2)	C13—C12—C11	120.5 (3)
C8—N2—B1	124.8 (2)	C13—C12—H12	119.7
C11—N3—B2	122.7 (2)	C8—C13—H13	119.3
C14—N3—C11	127.2 (2)	C12—C13—C8	121.4 (3)
C14—N3—B2	110.1 (2)	C12—C13—H13	119.3
C15—N4—B2	111.6 (2)	N3—C14—H14	123.7
C18—N4—C15	108.4 (3)	N3—C14—C15	112.6 (3)
C18—N4—B2	140.0 (3)	C15—C14—H14	123.7
N1—C1—C4	109.4 (3)	N4—C15—C14	108.7 (3)
N1—C1—C7	109.6 (2)	N4—C15—C16	109.3 (2)
C7—C1—C4	140.9 (3)	C16—C15—C14	142.0 (3)
N1—C2—C3	107.9 (3)	C15—C16—C17	105.0 (3)
N1—C2—C5	122.4 (3)	C15—C16—C19	128.4 (3)
C3—C2—C5	129.8 (3)	C17—C16—C19	126.6 (3)
C2—C3—H3	125.5	C16—C17—H17	125.6
C4—C3—C2	109.0 (3)	C18—C17—C16	108.7 (3)
C4—C3—H3	125.5	C18—C17—H17	125.6
C1—C4—C6	127.8 (3)	N4—C18—C17	108.5 (3)
C3—C4—C1	105.2 (3)	N4—C18—C20	121.7 (3)
C3—C4—C6	127.1 (3)	C17—C18—C20	129.8 (3)
C2—C5—H5A	109.5	C16—C19—H19A	109.5
C2—C5—H5B	109.5	C16—C19—H19B	109.5
C2—C5—H5C	109.5	C16—C19—H19C	109.5
H5A—C5—H5B	109.5	H19A—C19—H19B	109.5
H5A—C5—H5C	109.5	H19A—C19—H19C	109.5
H5B—C5—H5C	109.5	H19B—C19—H19C	109.5
C4—C6—H6A	109.5	C18—C20—H20A	109.5
C4—C6—H6B	109.5	C18—C20—H20B	109.5
C4—C6—H6C	109.5	C18—C20—H20C	109.5
H6A—C6—H6B	109.5	H20A—C20—H20B	109.5
H6A—C6—H6C	109.5	H20A—C20—H20C	109.5
H6B—C6—H6C	109.5	H20B—C20—H20C	109.5
N2—C7—C1	112.5 (3)	F1—B1—F1^i	111.1 (3)
N2—C7—H7	123.8	F1—B1—N1	113.08 (16)
C1—C7—H7	123.8	F1^i—B1—N1	113.08 (16)
C9—C8—N2	118.0 (3)	F1—B1—N2	110.87 (17)
C9—C8—C13	118.2 (3)	F1^i—B1—N2	110.87 (17)
C13—C8—N2	123.8 (3)	N1—B1—N2	97.1 (2)
C8—C9—H9	119.7	F2—B2—F2^i	110.9 (2)
C10—C9—C8	120.6 (3)	F2—B2—N3	110.86 (15)
C10—C9—H9	119.7	F2^i—B2—N3	110.86 (15)
C9—C10—H10	119.3	F2—B2—N4	113.23 (15)
C9—C10—C11	121.4 (3)	F2^i—B2—N4	113.23 (15)
C11—C10—H10	119.3	N4—B2—N3	97.0 (2)
N1—C1—C4—C3	0.000 (1)	C11—N3—C14—C15	180.000 (1)
N1—C1—C4—C6	180.000 (1)	C11—N3—B2—F2^i	61.82 (18)
N1—C1—C7—N2	0.000 (1)	C11—N3—B2—F2	−61.81 (18)
N1—C2—C3—C4	0.000 (1)	C11—N3—B2—N4	180.000 (1)
N2—C8—C9—C10	180.000 (1)	C11—C12—C13—C8	0.000 (1)
N2—C8—C13—C12	180.000 (1)	C13—C8—C9—C10	0.000 (1)
N3—C11—C12—C13	180.000 (1)	C14—N3—C11—C10	180.000 (1)
N3—C14—C15—N4	0.000 (1)	C14—N3—C11—C12	0.000 (1)
N3—C14—C15—C16	180.000 (1)	C14—N3—B2—F2	118.19 (18)
N4—C15—C16—C17	0.000 (1)	C14—N3—B2—F2^i	−118.18 (18)
N4—C15—C16—C19	180.000 (1)	C14—N3—B2—N4	0.000 (1)
C1—N1—C2—C3	0.000 (1)	C14—C15—C16—C17	180.000 (1)
C1—N1—C2—C5	180.000 (1)	C14—C15—C16—C19	0.000 (1)
C1—N1—B1—F1^i	−116.3 (2)	C15—N4—C18—C17	0.000 (1)
C1—N1—B1—F1	116.3 (2)	C15—N4—C18—C20	180.000 (1)
C1—N1—B1—N2	0.000 (1)	C15—N4—B2—F2^i	116.33 (18)
C2—N1—C1—C4	0.000 (1)	C15—N4—B2—F2	−116.32 (18)
C2—N1—C1—C7	180.000 (1)	C15—N4—B2—N3	0.000 (1)
C2—N1—B1—F1	−63.7 (2)	C15—C16—C17—C18	0.000 (1)
C2—N1—B1—F1^i	63.7 (2)	C16—C17—C18—N4	0.000 (1)
C2—N1—B1—N2	180.000 (1)	C16—C17—C18—C20	180.000 (1)
C2—C3—C4—C1	0.000 (1)	C18—N4—C15—C14	180.000 (1)
C2—C3—C4—C6	180.000 (1)	C18—N4—C15—C16	0.000 (1)
C4—C1—C7—N2	180.000 (1)	C18—N4—B2—F2^i	−63.67 (18)
C5—C2—C3—C4	180.000 (1)	C18—N4—B2—F2	63.68 (18)
C7—N2—C8—C9	180.000 (1)	C18—N4—B2—N3	180.000 (1)
C7—N2—C8—C13	0.000 (1)	C19—C16—C17—C18	180.0
C7—N2—B1—F1^i	118.07 (18)	B1—N1—C1—C4	180.000 (1)
C7—N2—B1—F1	−118.07 (18)	B1—N1—C1—C7	0.000 (1)
C7—N2—B1—N1	0.000 (1)	B1—N1—C2—C3	180.000 (1)
C7—C1—C4—C3	180.000 (1)	B1—N1—C2—C5	0.000 (1)
C7—C1—C4—C6	0.000 (1)	B1—N2—C7—C1	0.000 (1)
C8—N2—C7—C1	180.000 (1)	B1—N2—C8—C9	0.000 (1)
C8—N2—B1—F1^i	−61.93 (18)	B1—N2—C8—C13	180.000 (1)
C8—N2—B1—F1	61.93 (18)	B2—N3—C11—C10	0.000 (1)
C8—N2—B1—N1	180.000 (1)	B2—N3—C11—C12	180.000 (1)
C8—C9—C10—C11	0.000 (1)	B2—N3—C14—C15	0.000 (1)
C9—C8—C13—C12	0.000 (1)	B2—N4—C15—C14	0.000 (1)
C9—C10—C11—N3	180.000 (1)	B2—N4—C15—C16	180.000 (1)
C9—C10—C11—C12	0.000 (1)	B2—N4—C18—C17	180.000 (1)
C10—C11—C12—C13	0.000 (1)	B2—N4—C18—C20	0.000 (1)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···F2^ii	0.96	2.49	3.336 (3)	147

Symmetry code: (ii) −x+1, y+1/2, −z+1.