N,N′-Di­benzyl-4,7-phenanthrolinium dibromide methanol solvate

The structure of the phenanthroline-derived viologen, C₂₆H₂₂N₂²⁺·2Br⁻·CH₃OH, as the methanol solvate, was determined as part of a fluorescence-quenching study. There is intermolecular π–π stacking of the phenanthroline and benzyl arms as well as methanol hydrogen bonding to a bromide.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.071
• Data-to-parameter ratio = 22.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.76
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.84 Ratio

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C27 H26 Br2 N2 O1
            Atom count from _chemical_formula_moiety:C28 H30 Br2 N2 O2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

N,N'-Dibenzyl-4,7-phenanthrolinium dibromide methanol solvate

Crystal data

C26H22N2^2+·2Br^−CH4O	F(000) = 1120
Mr = 554.32	Dx = 1.604 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 778 reflections
a = 21.134 (4) Å	θ = 5.7–30°
b = 7.6390 (15) Å	µ = 3.55 mm^−1
c = 14.384 (3) Å	T = 90 K
β = 98.625 (7)°	Plate, yellow
V = 2296.0 (8) Å^3	0.43 × 0.31 × 0.06 mm
Z = 4

Data collection

Bruker SMART 1000 diffractometer	6700 independent reflections
Radiation source: normal-focus sealed tube	5903 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 8.3 pixels mm^-1	θmax = 30.0°, θmin = 2.0°
ω scans	h = −29→29
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −10→10
Tmin = 0.280, Tmax = 0.815	l = −20→20
29338 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: difference Fourier map
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0363P)^2 + 0.9274P] where P = (Fo^2 + 2Fc^2)/3
6700 reflections	(Δ/σ)max = 0.002
293 parameters	Δρmax = 0.99 e Å^−3
1 restraint	Δρmin = −0.36 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.053086 (7)	0.18874 (2)	0.090326 (11)	0.01265 (5)
Br2	0.318598 (8)	0.98179 (2)	0.128976 (12)	0.01553 (5)
O1	0.35044 (6)	0.57958 (17)	0.05525 (10)	0.0199 (3)
H1A	0.3468 (12)	0.682 (2)	0.0704 (17)	0.024*
N1	0.12182 (7)	0.68792 (16)	0.11132 (9)	0.0098 (2)
N2	0.27335 (6)	0.27579 (17)	0.37566 (9)	0.0108 (2)
C1	0.06057 (8)	0.7209 (2)	0.11723 (12)	0.0119 (3)
H1	0.0360	0.7909	0.0705	0.014*
C2	0.03214 (8)	0.6540 (2)	0.19116 (12)	0.0131 (3)
H2	−0.0118	0.6757	0.1938	0.016*
C3	0.06786 (8)	0.5570 (2)	0.25987 (12)	0.0118 (3)
H3	0.0496	0.5185	0.3128	0.014*
C4	0.13152 (7)	0.51429 (19)	0.25205 (11)	0.0094 (3)
C5	0.17196 (7)	0.41283 (19)	0.32226 (11)	0.0092 (3)
C6	0.15097 (8)	0.3574 (2)	0.40607 (11)	0.0112 (3)
H6	0.1081	0.3789	0.4156	0.013*
C7	0.19255 (8)	0.2723 (2)	0.47398 (11)	0.0124 (3)
H7	0.1795	0.2415	0.5323	0.015*
C8	0.25384 (8)	0.2317 (2)	0.45652 (11)	0.0123 (3)
H8	0.2824	0.1714	0.5031	0.015*
C9	0.23477 (7)	0.37170 (19)	0.30785 (11)	0.0096 (3)
C10	0.25840 (8)	0.4303 (2)	0.22563 (11)	0.0111 (3)
H10	0.2999	0.3959	0.2148	0.013*
C11	0.22191 (8)	0.5353 (2)	0.16241 (11)	0.0105 (3)
H11	0.2391	0.5798	0.1098	0.013*
C12	0.15819 (7)	0.57863 (19)	0.17477 (11)	0.0095 (3)
C13	0.15216 (8)	0.7925 (2)	0.04230 (11)	0.0114 (3)
H13A	0.1938	0.8368	0.0743	0.014*
H13B	0.1247	0.8953	0.0235	0.014*
C14	0.16345 (8)	0.69694 (19)	−0.04570 (11)	0.0105 (3)
C15	0.22303 (8)	0.7166 (2)	−0.07512 (11)	0.0119 (3)
H15	0.2559	0.7797	−0.0370	0.014*
C16	0.23480 (8)	0.6444 (2)	−0.16015 (12)	0.0133 (3)
H16	0.2754	0.6587	−0.1800	0.016*
C17	0.18676 (8)	0.5517 (2)	−0.21520 (12)	0.0136 (3)
H17	0.1945	0.5015	−0.2729	0.016*
C18	0.12722 (8)	0.5320 (2)	−0.18634 (12)	0.0133 (3)
H18	0.0945	0.4684	−0.2246	0.016*
C19	0.11502 (8)	0.6045 (2)	−0.10191 (11)	0.0120 (3)
H19	0.0742	0.5912	−0.0828	0.014*
C20	0.33660 (8)	0.2078 (2)	0.35787 (12)	0.0133 (3)
H20A	0.3311	0.1546	0.2944	0.016*
H20B	0.3503	0.1138	0.4039	0.016*
C21	0.38919 (8)	0.3428 (2)	0.36402 (12)	0.0138 (3)
C22	0.44581 (9)	0.2916 (2)	0.33310 (13)	0.0193 (3)
H22	0.4492	0.1778	0.3077	0.023*
C23	0.49714 (9)	0.4057 (3)	0.33929 (15)	0.0244 (4)
H23	0.5358	0.3695	0.3190	0.029*
C24	0.49215 (10)	0.5729 (3)	0.37501 (15)	0.0264 (4)
H24	0.5274	0.6512	0.3790	0.032*
C25	0.43579 (10)	0.6258 (3)	0.40490 (14)	0.0246 (4)
H25	0.4322	0.7409	0.4286	0.029*
C26	0.38437 (9)	0.5102 (2)	0.40027 (13)	0.0182 (3)
H26	0.3460	0.5458	0.4219	0.022*
C27	0.40382 (10)	0.5052 (3)	0.11371 (17)	0.0279 (4)
H27A	0.4430	0.5317	0.0877	0.042*
H27B	0.3983	0.3781	0.1167	0.042*
H27C	0.4069	0.5546	0.1771	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01325 (8)	0.01301 (8)	0.01175 (8)	0.00146 (5)	0.00204 (6)	−0.00090 (5)
Br2	0.01506 (8)	0.01796 (8)	0.01363 (9)	−0.00064 (6)	0.00232 (6)	−0.00264 (6)
O1	0.0177 (6)	0.0159 (6)	0.0242 (7)	0.0023 (5)	−0.0035 (5)	−0.0028 (5)
N1	0.0127 (6)	0.0075 (6)	0.0093 (6)	−0.0004 (5)	0.0017 (5)	−0.0004 (4)
N2	0.0119 (6)	0.0093 (5)	0.0109 (6)	0.0003 (5)	0.0007 (5)	−0.0004 (5)
C1	0.0121 (7)	0.0101 (6)	0.0129 (7)	0.0010 (5)	−0.0002 (6)	−0.0019 (6)
C2	0.0104 (7)	0.0123 (7)	0.0168 (8)	−0.0005 (6)	0.0027 (6)	−0.0011 (6)
C3	0.0115 (7)	0.0098 (6)	0.0146 (7)	−0.0015 (5)	0.0033 (6)	−0.0010 (5)
C4	0.0107 (7)	0.0072 (6)	0.0103 (7)	−0.0017 (5)	0.0019 (5)	−0.0027 (5)
C5	0.0121 (7)	0.0066 (6)	0.0089 (7)	−0.0011 (5)	0.0010 (5)	−0.0008 (5)
C6	0.0135 (7)	0.0083 (6)	0.0123 (7)	−0.0020 (5)	0.0037 (6)	−0.0015 (5)
C7	0.0155 (7)	0.0110 (6)	0.0108 (7)	−0.0022 (6)	0.0027 (6)	−0.0001 (5)
C8	0.0168 (8)	0.0092 (6)	0.0102 (7)	−0.0008 (6)	0.0002 (6)	0.0008 (5)
C9	0.0118 (7)	0.0074 (6)	0.0094 (7)	−0.0009 (5)	0.0005 (5)	−0.0007 (5)
C10	0.0114 (7)	0.0117 (6)	0.0105 (7)	−0.0003 (5)	0.0022 (6)	−0.0009 (5)
C11	0.0119 (7)	0.0105 (6)	0.0097 (7)	−0.0009 (5)	0.0031 (6)	−0.0010 (5)
C12	0.0112 (7)	0.0079 (6)	0.0092 (7)	−0.0004 (5)	0.0008 (5)	−0.0018 (5)
C13	0.0158 (7)	0.0091 (6)	0.0099 (7)	−0.0009 (5)	0.0034 (6)	0.0013 (5)
C14	0.0137 (7)	0.0086 (6)	0.0090 (7)	0.0023 (5)	0.0014 (5)	0.0019 (5)
C15	0.0133 (7)	0.0103 (6)	0.0116 (7)	0.0016 (5)	0.0004 (6)	0.0017 (5)
C16	0.0143 (7)	0.0120 (7)	0.0140 (7)	0.0037 (6)	0.0042 (6)	0.0038 (6)
C17	0.0211 (8)	0.0087 (6)	0.0110 (7)	0.0041 (6)	0.0027 (6)	0.0018 (5)
C18	0.0179 (8)	0.0101 (6)	0.0112 (7)	−0.0006 (6)	−0.0005 (6)	0.0005 (5)
C19	0.0135 (7)	0.0110 (7)	0.0115 (7)	0.0007 (6)	0.0018 (6)	0.0017 (5)
C20	0.0138 (7)	0.0110 (7)	0.0150 (7)	0.0023 (6)	0.0016 (6)	−0.0001 (6)
C21	0.0123 (7)	0.0163 (7)	0.0121 (7)	−0.0006 (6)	−0.0001 (6)	0.0032 (6)
C22	0.0152 (8)	0.0204 (8)	0.0227 (9)	0.0037 (6)	0.0037 (7)	0.0030 (7)
C23	0.0134 (8)	0.0319 (10)	0.0285 (10)	0.0008 (7)	0.0047 (7)	0.0069 (8)
C24	0.0198 (9)	0.0328 (10)	0.0259 (10)	−0.0121 (8)	0.0009 (8)	0.0030 (8)
C25	0.0272 (10)	0.0221 (9)	0.0244 (10)	−0.0096 (8)	0.0037 (8)	−0.0041 (7)
C26	0.0175 (8)	0.0198 (8)	0.0177 (8)	−0.0030 (6)	0.0042 (7)	−0.0031 (6)
C27	0.0193 (9)	0.0235 (9)	0.0381 (12)	0.0010 (7)	−0.0054 (8)	0.0045 (8)

Geometric parameters (Å, º)

O1—C27	1.421 (2)	C13—H13B	0.9900
O1—H1A	0.816 (16)	C14—C15	1.395 (2)
N1—C1	1.334 (2)	C14—C19	1.397 (2)
N1—C12	1.382 (2)	C15—C16	1.398 (2)
N1—C13	1.4919 (19)	C15—H15	0.9500
N2—C8	1.334 (2)	C16—C17	1.385 (2)
N2—C9	1.384 (2)	C16—H16	0.9500
N2—C20	1.492 (2)	C17—C18	1.391 (2)
C1—C2	1.395 (2)	C17—H17	0.9500
C1—H1	0.9500	C18—C19	1.394 (2)
C2—C3	1.368 (2)	C18—H18	0.9500
C2—H2	0.9500	C19—H19	0.9500
C3—C4	1.405 (2)	C20—C21	1.509 (2)
C3—H3	0.9500	C20—H20A	0.9900
C4—C12	1.408 (2)	C20—H20B	0.9900
C4—C5	1.446 (2)	C21—C26	1.390 (2)
C5—C9	1.409 (2)	C21—C22	1.394 (2)
C5—C6	1.411 (2)	C22—C23	1.384 (3)
C6—C7	1.376 (2)	C22—H22	0.9500
C6—H6	0.9500	C23—C24	1.386 (3)
C7—C8	1.391 (2)	C23—H23	0.9500
C7—H7	0.9500	C24—C25	1.386 (3)
C8—H8	0.9500	C24—H24	0.9500
C9—C10	1.423 (2)	C25—C26	1.394 (3)
C10—C11	1.362 (2)	C25—H25	0.9500
C10—H10	0.9500	C26—H26	0.9500
C11—C12	1.423 (2)	C27—H27A	0.9800
C11—H11	0.9500	C27—H27B	0.9800
C13—C14	1.511 (2)	C27—H27C	0.9800
C13—H13A	0.9900
C27—O1—H1A	108.8 (18)	C15—C14—C19	119.67 (15)
C1—N1—C12	121.40 (14)	C15—C14—C13	117.72 (14)
C1—N1—C13	117.33 (13)	C19—C14—C13	122.35 (14)
C12—N1—C13	120.73 (13)	C14—C15—C16	120.66 (15)
C8—N2—C9	121.45 (14)	C14—C15—H15	119.7
C8—N2—C20	117.62 (13)	C16—C15—H15	119.7
C9—N2—C20	120.80 (13)	C17—C16—C15	119.40 (15)
N1—C1—C2	120.82 (15)	C17—C16—H16	120.3
N1—C1—H1	119.6	C15—C16—H16	120.3
C2—C1—H1	119.6	C16—C17—C18	120.20 (15)
C3—C2—C1	119.69 (15)	C16—C17—H17	119.9
C3—C2—H2	120.2	C18—C17—H17	119.9
C1—C2—H2	120.2	C17—C18—C19	120.72 (15)
C2—C3—C4	119.93 (15)	C17—C18—H18	119.6
C2—C3—H3	120.0	C19—C18—H18	119.6
C4—C3—H3	120.0	C18—C19—C14	119.35 (15)
C3—C4—C12	118.93 (14)	C18—C19—H19	120.3
C3—C4—C5	122.75 (14)	C14—C19—H19	120.3
C12—C4—C5	118.26 (14)	N2—C20—C21	115.02 (13)
C9—C5—C6	118.86 (14)	N2—C20—H20A	108.5
C9—C5—C4	119.19 (13)	C21—C20—H20A	108.5
C6—C5—C4	121.93 (14)	N2—C20—H20B	108.5
C7—C6—C5	119.97 (14)	C21—C20—H20B	108.5
C7—C6—H6	120.0	H20A—C20—H20B	107.5
C5—C6—H6	120.0	C26—C21—C22	119.50 (16)
C6—C7—C8	119.36 (15)	C26—C21—C20	123.78 (15)
C6—C7—H7	120.3	C22—C21—C20	116.70 (15)
C8—C7—H7	120.3	C23—C22—C21	120.31 (17)
N2—C8—C7	121.26 (15)	C23—C22—H22	119.8
N2—C8—H8	119.4	C21—C22—H22	119.8
C7—C8—H8	119.4	C22—C23—C24	120.11 (18)
N2—C9—C5	118.87 (14)	C22—C23—H23	119.9
N2—C9—C10	120.60 (14)	C24—C23—H23	119.9
C5—C9—C10	120.52 (14)	C25—C24—C23	120.00 (18)
C11—C10—C9	120.38 (14)	C25—C24—H24	120.0
C11—C10—H10	119.8	C23—C24—H24	120.0
C9—C10—H10	119.8	C24—C25—C26	120.06 (18)
C10—C11—C12	120.35 (14)	C24—C25—H25	120.0
C10—C11—H11	119.8	C26—C25—H25	120.0
C12—C11—H11	119.8	C21—C26—C25	120.00 (17)
N1—C12—C4	118.90 (14)	C21—C26—H26	120.0
N1—C12—C11	120.06 (14)	C25—C26—H26	120.0
C4—C12—C11	121.04 (14)	O1—C27—H27A	109.5
N1—C13—C14	115.88 (13)	O1—C27—H27B	109.5
N1—C13—H13A	108.3	H27A—C27—H27B	109.5
C14—C13—H13A	108.3	O1—C27—H27C	109.5
N1—C13—H13B	108.3	H27A—C27—H27C	109.5
C14—C13—H13B	108.3	H27B—C27—H27C	109.5
H13A—C13—H13B	107.4
C12—N1—C1—C2	3.7 (2)	C3—C4—C12—N1	2.8 (2)
C13—N1—C1—C2	−167.85 (14)	C5—C4—C12—N1	−174.63 (13)
N1—C1—C2—C3	1.7 (2)	C3—C4—C12—C11	−178.34 (14)
C1—C2—C3—C4	−4.7 (2)	C5—C4—C12—C11	4.2 (2)
C2—C3—C4—C12	2.5 (2)	C10—C11—C12—N1	178.78 (14)
C2—C3—C4—C5	179.75 (15)	C10—C11—C12—C4	−0.1 (2)
C3—C4—C5—C9	178.31 (14)	C1—N1—C13—C14	−106.06 (16)
C12—C4—C5—C9	−4.4 (2)	C12—N1—C13—C14	82.29 (18)
C3—C4—C5—C6	−3.3 (2)	N1—C13—C14—C15	−134.06 (15)
C12—C4—C5—C6	173.97 (14)	N1—C13—C14—C19	51.8 (2)
C9—C5—C6—C7	3.1 (2)	C19—C14—C15—C16	−0.2 (2)
C4—C5—C6—C7	−175.23 (14)	C13—C14—C15—C16	−174.43 (14)
C5—C6—C7—C8	−4.2 (2)	C14—C15—C16—C17	−0.3 (2)
C9—N2—C8—C7	3.5 (2)	C15—C16—C17—C18	0.5 (2)
C20—N2—C8—C7	−172.48 (14)	C16—C17—C18—C19	−0.1 (2)
C6—C7—C8—N2	0.9 (2)	C17—C18—C19—C14	−0.4 (2)
C8—N2—C9—C5	−4.4 (2)	C15—C14—C19—C18	0.5 (2)
C20—N2—C9—C5	171.40 (14)	C13—C14—C19—C18	174.53 (14)
C8—N2—C9—C10	174.60 (14)	C8—N2—C20—C21	−107.88 (17)
C20—N2—C9—C10	−9.6 (2)	C9—N2—C20—C21	76.16 (19)
C6—C5—C9—N2	1.1 (2)	N2—C20—C21—C26	11.7 (2)
C4—C5—C9—N2	179.49 (13)	N2—C20—C21—C22	−169.87 (15)
C6—C5—C9—C10	−177.91 (14)	C26—C21—C22—C23	0.7 (3)
C4—C5—C9—C10	0.5 (2)	C20—C21—C22—C23	−177.85 (17)
N2—C9—C10—C11	−175.21 (14)	C21—C22—C23—C24	−1.0 (3)
C5—C9—C10—C11	3.8 (2)	C22—C23—C24—C25	0.2 (3)
C9—C10—C11—C12	−4.0 (2)	C23—C24—C25—C26	0.9 (3)
C1—N1—C12—C4	−5.9 (2)	C22—C21—C26—C25	0.4 (3)
C13—N1—C12—C4	165.37 (13)	C20—C21—C26—C25	178.82 (17)
C1—N1—C12—C11	175.18 (14)	C24—C25—C26—C21	−1.2 (3)
C13—N1—C12—C11	−13.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br2	0.82 (2)	2.54 (2)	3.3514 (14)	170 (2)
C1—H1···Br1^i	0.95	2.76	3.6067 (18)	149
C20—H20A···Br2^ii	0.99	2.70	3.6865 (18)	175

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