Crystal structure and Hirshfeld surface analysis of 2-phenyl-1H-phenanthro[9,10-d]imidazol-3-ium benzoate

The title compound exists in the crystal as a dimer of ion pairs. Hydrogen bonding and weak π–π inter­actions along with N—H...π inter­actions are involved in consolidating this cluster. The three-dimensional crystal structure consists of stepped stacks of dimers of ion pairs associated by C—H...π(ring) and slipped π-stacking inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.104
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .          1 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT333_ALERT_2_G Large Aver C6-Ring C-C Dist C8       -C21      .       1.42 Ang.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          3 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         12 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 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
   5 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018/3 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2020).

2-Phenyl-1H-phenanthro[9,10-d]imidazol-3-ium benzoate

Crystal data

C21H15N2^+·C7H5O2^−	F(000) = 872
Mr = 416.46	Dx = 1.365 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4693 (4) Å	Cell parameters from 9121 reflections
b = 8.7384 (3) Å	θ = 3.2–28.1°
c = 24.5049 (9) Å	µ = 0.09 mm^−1
β = 91.792 (1)°	T = 100 K
V = 2026.70 (13) Å^3	Block, pink
Z = 4	0.39 × 0.28 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer	3269 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.0°, θmin = 2.3°
Tmin = 0.708, Tmax = 0.746	h = −11→11
25446 measured reflections	k = −10→10
3979 independent reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 1.042P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3979 reflections	Δρmax = 0.23 e Å^−3
289 parameters	Δρmin = −0.33 e Å^−3
0 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
O1	0.23573 (12)	0.35667 (14)	0.39271 (5)	0.0272 (3)
O2	0.43116 (12)	0.21182 (14)	0.39047 (5)	0.0277 (3)
N1	0.27589 (13)	0.51384 (15)	0.48272 (5)	0.0174 (3)
H1	0.259534	0.474240	0.451017	0.021*
N2	0.36868 (13)	0.65362 (15)	0.54849 (5)	0.0177 (3)
H2	0.421794	0.718335	0.565817	0.021*
C1	0.30537 (16)	0.24344 (19)	0.37667 (6)	0.0190 (3)
C2	0.23159 (16)	0.13699 (18)	0.33666 (6)	0.0174 (3)
C3	0.30647 (17)	0.0201 (2)	0.31269 (7)	0.0260 (4)
H3	0.400888	0.004987	0.322848	0.031*
C4	0.24293 (19)	−0.0746 (2)	0.27379 (7)	0.0327 (4)
H4	0.294737	−0.151762	0.257587	0.039*
C5	0.10194 (18)	−0.0537 (2)	0.25920 (7)	0.0261 (4)
H5	0.059013	−0.115598	0.232633	0.031*
C6	0.02506 (17)	0.05930 (19)	0.28422 (7)	0.0225 (4)
H6	−0.070461	0.071109	0.275216	0.027*
C7	0.08921 (16)	0.15524 (18)	0.32262 (6)	0.0194 (3)
H7	0.037017	0.231785	0.338992	0.023*
C8	0.20749 (15)	0.47649 (18)	0.52979 (6)	0.0172 (3)
C9	0.09665 (15)	0.36873 (18)	0.53830 (6)	0.0185 (3)
C10	0.03891 (16)	0.27684 (18)	0.49600 (7)	0.0214 (4)
H10	0.070829	0.286745	0.460668	0.026*
C11	−0.06499 (16)	0.17229 (19)	0.50718 (7)	0.0241 (4)
H11	−0.102982	0.111124	0.479346	0.029*
C12	−0.11351 (17)	0.1577 (2)	0.56009 (7)	0.0267 (4)
H12	−0.183127	0.086184	0.567421	0.032*
C13	−0.05897 (17)	0.2486 (2)	0.60154 (7)	0.0243 (4)
H13	−0.093418	0.238283	0.636479	0.029*
C14	0.04783 (15)	0.35686 (18)	0.59221 (7)	0.0201 (3)
C15	0.10846 (15)	0.45281 (18)	0.63613 (6)	0.0197 (3)
C16	0.06231 (17)	0.4443 (2)	0.69008 (7)	0.0244 (4)
H16	−0.010480	0.377451	0.698225	0.029*
C17	0.12253 (17)	0.5328 (2)	0.73112 (7)	0.0263 (4)
H17	0.090928	0.523517	0.766521	0.032*
C18	0.23025 (17)	0.6361 (2)	0.72023 (7)	0.0243 (4)
H18	0.269913	0.695635	0.748191	0.029*
C19	0.27759 (16)	0.64963 (19)	0.66800 (6)	0.0213 (4)
H19	0.348675	0.719290	0.660521	0.026*
C20	0.21874 (15)	0.55833 (18)	0.62580 (6)	0.0187 (3)
C21	0.26552 (15)	0.56429 (18)	0.57097 (6)	0.0173 (3)
C22	0.37202 (15)	0.62210 (18)	0.49467 (6)	0.0174 (3)
C23	0.46252 (15)	0.69837 (18)	0.45586 (6)	0.0180 (3)
C24	0.55209 (16)	0.81660 (19)	0.47343 (7)	0.0224 (4)
H24	0.554159	0.846890	0.509828	0.027*
C25	0.63769 (17)	0.8886 (2)	0.43664 (7)	0.0264 (4)
H25	0.697088	0.967356	0.448523	0.032*
C26	0.63607 (17)	0.8448 (2)	0.38243 (7)	0.0264 (4)
H26	0.695022	0.892778	0.358048	0.032*
C27	0.54566 (18)	0.7287 (2)	0.36468 (7)	0.0260 (4)
H27	0.543584	0.699591	0.328159	0.031*
C28	0.45880 (17)	0.65616 (19)	0.40079 (7)	0.0224 (4)
H28	0.397852	0.579232	0.388489	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0306 (6)	0.0247 (6)	0.0259 (6)	−0.0004 (5)	−0.0033 (5)	−0.0090 (5)
O2	0.0214 (6)	0.0332 (7)	0.0279 (6)	−0.0035 (5)	−0.0069 (5)	−0.0051 (5)
N1	0.0161 (6)	0.0172 (7)	0.0185 (7)	0.0026 (5)	−0.0037 (5)	−0.0023 (5)
N2	0.0151 (6)	0.0177 (7)	0.0200 (7)	−0.0006 (5)	−0.0035 (5)	−0.0032 (5)
C1	0.0211 (8)	0.0216 (8)	0.0144 (7)	−0.0032 (7)	0.0002 (6)	0.0011 (6)
C2	0.0184 (7)	0.0192 (8)	0.0146 (7)	−0.0039 (6)	0.0010 (6)	0.0011 (6)
C3	0.0166 (7)	0.0336 (10)	0.0277 (9)	0.0000 (7)	−0.0019 (7)	−0.0089 (8)
C4	0.0264 (9)	0.0371 (11)	0.0343 (10)	0.0034 (8)	−0.0006 (8)	−0.0185 (9)
C5	0.0269 (9)	0.0285 (9)	0.0226 (8)	−0.0054 (7)	−0.0046 (7)	−0.0076 (7)
C6	0.0180 (7)	0.0245 (9)	0.0245 (8)	−0.0022 (7)	−0.0051 (7)	0.0006 (7)
C7	0.0192 (8)	0.0187 (8)	0.0203 (8)	0.0010 (6)	−0.0007 (6)	−0.0003 (6)
C8	0.0145 (7)	0.0173 (8)	0.0197 (8)	0.0042 (6)	−0.0019 (6)	−0.0001 (6)
C9	0.0143 (7)	0.0156 (8)	0.0254 (8)	0.0045 (6)	−0.0036 (6)	0.0004 (6)
C10	0.0177 (8)	0.0183 (8)	0.0281 (9)	0.0042 (6)	−0.0035 (7)	−0.0017 (7)
C11	0.0182 (8)	0.0171 (8)	0.0364 (10)	0.0028 (7)	−0.0075 (7)	−0.0035 (7)
C12	0.0178 (8)	0.0200 (9)	0.0420 (11)	0.0001 (7)	−0.0019 (7)	0.0058 (8)
C13	0.0185 (8)	0.0255 (9)	0.0288 (9)	0.0015 (7)	−0.0009 (7)	0.0054 (7)
C14	0.0141 (7)	0.0181 (8)	0.0278 (9)	0.0046 (6)	−0.0025 (6)	0.0019 (7)
C15	0.0147 (7)	0.0207 (8)	0.0234 (8)	0.0060 (6)	−0.0007 (6)	0.0013 (7)
C16	0.0192 (8)	0.0275 (9)	0.0264 (9)	0.0037 (7)	0.0013 (7)	0.0027 (7)
C17	0.0241 (8)	0.0347 (10)	0.0201 (8)	0.0076 (8)	0.0022 (7)	0.0002 (7)
C18	0.0217 (8)	0.0299 (9)	0.0212 (8)	0.0068 (7)	−0.0044 (7)	−0.0032 (7)
C19	0.0162 (7)	0.0227 (9)	0.0247 (9)	0.0040 (6)	−0.0035 (6)	−0.0023 (7)
C20	0.0152 (7)	0.0190 (8)	0.0217 (8)	0.0064 (6)	−0.0033 (6)	−0.0002 (6)
C21	0.0137 (7)	0.0166 (8)	0.0214 (8)	0.0026 (6)	−0.0032 (6)	0.0000 (6)
C22	0.0150 (7)	0.0157 (8)	0.0214 (8)	0.0051 (6)	−0.0032 (6)	−0.0016 (6)
C23	0.0144 (7)	0.0171 (8)	0.0224 (8)	0.0051 (6)	−0.0021 (6)	0.0009 (6)
C24	0.0190 (8)	0.0243 (9)	0.0236 (8)	0.0014 (7)	−0.0024 (7)	−0.0011 (7)
C25	0.0194 (8)	0.0265 (9)	0.0330 (10)	−0.0021 (7)	−0.0045 (7)	0.0038 (8)
C26	0.0203 (8)	0.0286 (10)	0.0304 (9)	0.0034 (7)	0.0014 (7)	0.0097 (8)
C27	0.0301 (9)	0.0264 (9)	0.0215 (8)	0.0057 (7)	0.0000 (7)	0.0018 (7)
C28	0.0234 (8)	0.0191 (8)	0.0243 (8)	0.0021 (7)	−0.0029 (7)	−0.0011 (7)

Geometric parameters (Å, º)

O1—C1	1.2588 (19)	C12—C13	1.377 (2)
O2—C1	1.2587 (19)	C12—H12	0.9300
N1—C22	1.339 (2)	C13—C14	1.409 (2)
N1—C8	1.380 (2)	C13—H13	0.9300
N1—H1	0.8600	C14—C15	1.467 (2)
N2—C22	1.349 (2)	C15—C16	1.407 (2)
N2—C21	1.379 (2)	C15—C20	1.422 (2)
N2—H2	0.8600	C16—C17	1.378 (2)
C1—C2	1.507 (2)	C16—H16	0.9300
C2—C3	1.384 (2)	C17—C18	1.394 (2)
C2—C7	1.390 (2)	C17—H17	0.9300
C3—C4	1.386 (2)	C18—C19	1.374 (2)
C3—H3	0.9300	C18—H18	0.9300
C4—C5	1.383 (2)	C19—C20	1.407 (2)
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.382 (2)	C20—C21	1.429 (2)
C5—H5	0.9300	C22—C23	1.461 (2)
C6—C7	1.386 (2)	C23—C24	1.396 (2)
C6—H6	0.9300	C23—C28	1.398 (2)
C7—H7	0.9300	C24—C25	1.382 (2)
C8—C21	1.369 (2)	C24—H24	0.9300
C8—C9	1.430 (2)	C25—C26	1.382 (2)
C9—C10	1.408 (2)	C25—H25	0.9300
C9—C14	1.417 (2)	C26—C27	1.389 (2)
C10—C11	1.376 (2)	C26—H26	0.9300
C10—H10	0.9300	C27—C28	1.381 (2)
C11—C12	1.395 (2)	C27—H27	0.9300
C11—H11	0.9300	C28—H28	0.9300
C22—N1—C8	108.53 (13)	C13—C14—C9	117.21 (15)
C22—N1—H1	125.7	C13—C14—C15	122.08 (15)
C8—N1—H1	125.7	C9—C14—C15	120.70 (14)
C22—N2—C21	108.28 (13)	C16—C15—C20	116.92 (15)
C22—N2—H2	125.9	C16—C15—C14	122.22 (15)
C21—N2—H2	125.9	C20—C15—C14	120.86 (14)
O2—C1—O1	126.11 (15)	C17—C16—C15	121.50 (16)
O2—C1—C2	117.05 (14)	C17—C16—H16	119.3
O1—C1—C2	116.84 (14)	C15—C16—H16	119.3
C3—C2—C7	119.04 (14)	C16—C17—C18	120.82 (16)
C3—C2—C1	119.87 (14)	C16—C17—H17	119.6
C7—C2—C1	121.09 (14)	C18—C17—H17	119.6
C2—C3—C4	121.02 (15)	C19—C18—C17	119.72 (16)
C2—C3—H3	119.5	C19—C18—H18	120.1
C4—C3—H3	119.5	C17—C18—H18	120.1
C5—C4—C3	119.58 (16)	C18—C19—C20	120.15 (16)
C5—C4—H4	120.2	C18—C19—H19	119.9
C3—C4—H4	120.2	C20—C19—H19	119.9
C6—C5—C4	119.83 (15)	C19—C20—C15	120.88 (15)
C6—C5—H5	120.1	C19—C20—C21	122.89 (15)
C4—C5—H5	120.1	C15—C20—C21	116.23 (14)
C5—C6—C7	120.51 (15)	C8—C21—N2	107.21 (14)
C5—C6—H6	119.7	C8—C21—C20	122.93 (14)
C7—C6—H6	119.7	N2—C21—C20	129.85 (14)
C6—C7—C2	119.97 (15)	N1—C22—N2	108.77 (14)
C6—C7—H7	120.0	N1—C22—C23	126.05 (14)
C2—C7—H7	120.0	N2—C22—C23	125.15 (14)
C21—C8—N1	107.20 (13)	C24—C23—C28	119.31 (15)
C21—C8—C9	122.75 (15)	C24—C23—C22	119.99 (14)
N1—C8—C9	130.06 (14)	C28—C23—C22	120.69 (14)
C10—C9—C14	120.94 (15)	C25—C24—C23	119.90 (16)
C10—C9—C8	122.55 (15)	C25—C24—H24	120.0
C14—C9—C8	116.51 (14)	C23—C24—H24	120.0
C11—C10—C9	119.71 (16)	C26—C25—C24	120.80 (16)
C11—C10—H10	120.1	C26—C25—H25	119.6
C9—C10—H10	120.1	C24—C25—H25	119.6
C10—C11—C12	120.25 (16)	C25—C26—C27	119.43 (16)
C10—C11—H11	119.9	C25—C26—H26	120.3
C12—C11—H11	119.9	C27—C26—H26	120.3
C13—C12—C11	120.41 (16)	C28—C27—C26	120.56 (16)
C13—C12—H12	119.8	C28—C27—H27	119.7
C11—C12—H12	119.8	C26—C27—H27	119.7
C12—C13—C14	121.48 (16)	C27—C28—C23	119.98 (16)
C12—C13—H13	119.3	C27—C28—H28	120.0
C14—C13—H13	119.3	C23—C28—H28	120.0
O2—C1—C2—C3	−6.4 (2)	C15—C16—C17—C18	1.1 (2)
O1—C1—C2—C3	172.81 (15)	C16—C17—C18—C19	−0.3 (2)
O2—C1—C2—C7	174.49 (15)	C17—C18—C19—C20	−0.7 (2)
O1—C1—C2—C7	−6.2 (2)	C18—C19—C20—C15	1.0 (2)
C7—C2—C3—C4	2.3 (3)	C18—C19—C20—C21	−178.48 (15)
C1—C2—C3—C4	−176.81 (16)	C16—C15—C20—C19	−0.2 (2)
C2—C3—C4—C5	−1.0 (3)	C14—C15—C20—C19	−179.56 (14)
C3—C4—C5—C6	−1.2 (3)	C16—C15—C20—C21	179.29 (13)
C4—C5—C6—C7	2.0 (3)	C14—C15—C20—C21	−0.1 (2)
C5—C6—C7—C2	−0.7 (2)	N1—C8—C21—N2	−0.15 (16)
C3—C2—C7—C6	−1.4 (2)	C9—C8—C21—N2	179.75 (13)
C1—C2—C7—C6	177.64 (14)	N1—C8—C21—C20	178.83 (13)
C22—N1—C8—C21	−0.49 (16)	C9—C8—C21—C20	−1.3 (2)
C22—N1—C8—C9	179.62 (15)	C22—N2—C21—C8	0.74 (16)
C21—C8—C9—C10	−178.91 (14)	C22—N2—C21—C20	−178.15 (15)
N1—C8—C9—C10	1.0 (2)	C19—C20—C21—C8	−179.40 (15)
C21—C8—C9—C14	0.3 (2)	C15—C20—C21—C8	1.1 (2)
N1—C8—C9—C14	−179.82 (14)	C19—C20—C21—N2	−0.7 (2)
C14—C9—C10—C11	−1.0 (2)	C15—C20—C21—N2	179.84 (14)
C8—C9—C10—C11	178.22 (14)	C8—N1—C22—N2	0.96 (16)
C9—C10—C11—C12	0.3 (2)	C8—N1—C22—C23	−176.97 (14)
C10—C11—C12—C13	0.6 (2)	C21—N2—C22—N1	−1.05 (16)
C11—C12—C13—C14	−0.8 (2)	C21—N2—C22—C23	176.90 (14)
C12—C13—C14—C9	0.2 (2)	N1—C22—C23—C24	175.89 (14)
C12—C13—C14—C15	−179.05 (15)	N2—C22—C23—C24	−1.7 (2)
C10—C9—C14—C13	0.7 (2)	N1—C22—C23—C28	−3.0 (2)
C8—C9—C14—C13	−178.51 (13)	N2—C22—C23—C28	179.44 (14)
C10—C9—C14—C15	179.95 (14)	C28—C23—C24—C25	−1.2 (2)
C8—C9—C14—C15	0.7 (2)	C22—C23—C24—C25	179.97 (14)
C13—C14—C15—C16	−1.0 (2)	C23—C24—C25—C26	−0.1 (2)
C9—C14—C15—C16	179.84 (14)	C24—C25—C26—C27	1.0 (2)
C13—C14—C15—C20	178.35 (14)	C25—C26—C27—C28	−0.6 (2)
C9—C14—C15—C20	−0.8 (2)	C26—C27—C28—C23	−0.7 (2)
C20—C15—C16—C17	−0.8 (2)	C24—C23—C28—C27	1.5 (2)
C14—C15—C16—C17	178.53 (15)	C22—C23—C28—C27	−179.60 (14)

Hydrogen-bond geometry (Å, º)

Cg4 is the centroid of the C15–C20 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.77	2.6159 (17)	168
N2—H2···O2^i	0.86	1.83	2.6523 (16)	158
C7—H7···Cg4^ii	0.93	2.79	3.585 (2)	145
C10—H10···O1	0.93	2.40	3.265 (2)	155
C19—H19···O2^i	0.93	2.54	3.372 (2)	150
C24—H24···O2^i	0.93	2.50	3.343 (2)	152
C28—H28···O1	0.93	2.48	3.365 (2)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.