Crystal structure of 4′-bromo-2′,5′-dimeth­oxy-2,5-dioxo-[1,1′-biphen­yl]-3,4-dicarbo­nitrile [BrHBQ(CN)₂] benzene hemisolvate

The geometry of the title hemibi­quinone is different from previous examples and may be correlated with the weak inter­actions in the crystal.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.028
• wR factor = 0.068
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check

Alert level G
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT335_ALERT_2_G Check Large C6 Ring    C-C Range C7     -C12           0.16 Ang.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         23 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density          16 Note

   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
   6 ALERT level G = General information/check it is not something unexpected

   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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b) SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

4'-Bromo-2',5'-dimethoxy-2,5-dioxo-[1,1'-biphenyl]-3,4-dicarbonitrile benzene hemisolvate

Crystal data

C16H9BrN2O4·0.5C6H6	Z = 2
Mr = 412.22	F(000) = 414
Triclinic, P1	Dx = 1.603 Mg m^−3
a = 8.0427 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.343 (2) Å	Cell parameters from 5182 reflections
c = 11.007 (2) Å	θ = 2.9–27.4°
α = 104.469 (2)°	µ = 2.43 mm^−1
β = 95.120 (2)°	T = 173 K
γ = 102.851 (2)°	Block, black
V = 854.1 (3) Å^3	0.21 × 0.11 × 0.06 mm

Data collection

Bruker AXS SMART APEXII CCD diffractometer	3382 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.022
phi and ω scans	θmax = 27.6°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.600, Tmax = 0.746	k = −13→13
11856 measured reflections	l = −14→14
3957 independent 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0307P)^2 + 0.3076P] where P = (Fo^2 + 2Fc^2)/3
3957 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

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
C1	0.1145 (2)	−0.15670 (19)	−0.05223 (15)	0.0248 (4)
C2	0.2309 (2)	−0.02953 (19)	−0.02559 (16)	0.0249 (4)
H2	0.2677	0.0071	−0.0925	0.030*
C3	0.2939 (2)	0.04468 (18)	0.10043 (16)	0.0240 (4)
C4	0.2382 (2)	−0.01088 (18)	0.19817 (15)	0.0216 (3)
C5	0.1153 (2)	−0.13776 (18)	0.16872 (15)	0.0219 (3)
H5	0.0746	−0.1731	0.2353	0.026*
C6	0.0521 (2)	−0.21285 (18)	0.04302 (16)	0.0235 (4)
C7	0.3088 (2)	0.06338 (17)	0.33278 (15)	0.0207 (3)
C8	0.5003 (2)	0.10333 (17)	0.36973 (15)	0.0207 (3)
C9	0.5736 (2)	0.19577 (17)	0.50147 (15)	0.0207 (3)
C10	0.4713 (2)	0.21563 (17)	0.59112 (15)	0.0212 (3)
C11	0.2798 (2)	0.15131 (17)	0.55889 (16)	0.0215 (3)
C12	0.2090 (2)	0.08304 (18)	0.42447 (16)	0.0224 (3)
H12	0.0872	0.0513	0.4011	0.027*
C13	0.4568 (3)	0.2362 (2)	0.04085 (19)	0.0327 (4)
H13A	0.5171	0.1797	−0.0155	0.049*
H13B	0.5338	0.3282	0.0801	0.049*
H13C	0.3540	0.2445	−0.0084	0.049*
C14	−0.1132 (3)	−0.4035 (2)	0.10228 (19)	0.0356 (4)
H14A	−0.1932	−0.4943	0.0630	0.053*
H14B	−0.1695	−0.3463	0.1616	0.053*
H14C	−0.0097	−0.4148	0.1483	0.053*
C15	0.5379 (2)	0.29235 (19)	0.72153 (16)	0.0260 (4)
C16	0.7587 (2)	0.24907 (19)	0.52856 (16)	0.0257 (4)
C17	0.3212 (2)	0.45790 (19)	0.48189 (19)	0.0298 (4)
H17	0.1988	0.4292	0.4699	0.036*
C18	0.4079 (3)	0.43078 (19)	0.37931 (18)	0.0301 (4)
H18	0.3454	0.3836	0.2969	0.036*
C19	0.5876 (3)	0.4731 (2)	0.39738 (18)	0.0306 (4)
H19	0.6478	0.4547	0.3271	0.037*
N1	0.9050 (2)	0.2909 (2)	0.55007 (17)	0.0393 (4)
N2	0.5915 (2)	0.35262 (19)	0.82435 (15)	0.0399 (4)
O1	−0.06536 (16)	−0.33788 (13)	0.00550 (12)	0.0311 (3)
O2	0.40645 (18)	0.17220 (13)	0.13801 (12)	0.0327 (3)
O3	0.59685 (17)	0.05565 (14)	0.30356 (12)	0.0308 (3)
O4	0.19158 (16)	0.15713 (14)	0.64297 (12)	0.0303 (3)
Br1	0.04198 (3)	−0.26003 (2)	−0.22428 (2)	0.03965 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0214 (8)	0.0332 (10)	0.0170 (8)	0.0076 (7)	0.0021 (6)	0.0015 (7)
C2	0.0256 (9)	0.0318 (10)	0.0200 (8)	0.0081 (8)	0.0074 (7)	0.0098 (7)
C3	0.0254 (9)	0.0231 (9)	0.0231 (8)	0.0045 (7)	0.0069 (7)	0.0062 (7)
C4	0.0235 (8)	0.0217 (9)	0.0190 (8)	0.0055 (7)	0.0057 (6)	0.0042 (6)
C5	0.0225 (8)	0.0242 (9)	0.0194 (8)	0.0058 (7)	0.0062 (6)	0.0059 (7)
C6	0.0180 (8)	0.0256 (9)	0.0248 (8)	0.0044 (7)	0.0040 (6)	0.0035 (7)
C7	0.0242 (8)	0.0165 (8)	0.0211 (8)	0.0021 (7)	0.0053 (6)	0.0065 (6)
C8	0.0230 (8)	0.0193 (8)	0.0212 (8)	0.0033 (7)	0.0081 (6)	0.0085 (6)
C9	0.0208 (8)	0.0199 (8)	0.0229 (8)	0.0041 (7)	0.0039 (6)	0.0093 (7)
C10	0.0239 (8)	0.0208 (9)	0.0195 (8)	0.0034 (7)	0.0048 (6)	0.0080 (6)
C11	0.0223 (8)	0.0208 (8)	0.0220 (8)	0.0048 (7)	0.0068 (6)	0.0065 (6)
C12	0.0205 (8)	0.0226 (9)	0.0218 (8)	0.0015 (7)	0.0047 (6)	0.0051 (7)
C13	0.0354 (10)	0.0330 (10)	0.0332 (10)	0.0033 (9)	0.0115 (8)	0.0182 (8)
C14	0.0371 (11)	0.0271 (10)	0.0350 (10)	−0.0038 (9)	0.0107 (8)	0.0037 (8)
C15	0.0250 (9)	0.0292 (10)	0.0240 (9)	0.0031 (8)	0.0054 (7)	0.0108 (7)
C16	0.0256 (9)	0.0307 (10)	0.0227 (8)	0.0059 (8)	0.0056 (7)	0.0114 (7)
C17	0.0237 (9)	0.0242 (9)	0.0399 (10)	0.0022 (8)	0.0026 (8)	0.0105 (8)
C18	0.0329 (10)	0.0237 (9)	0.0293 (9)	0.0030 (8)	−0.0015 (8)	0.0053 (7)
C19	0.0329 (10)	0.0282 (10)	0.0322 (10)	0.0088 (8)	0.0098 (8)	0.0083 (8)
N1	0.0243 (9)	0.0536 (12)	0.0407 (10)	0.0062 (8)	0.0046 (7)	0.0181 (9)
N2	0.0457 (10)	0.0428 (10)	0.0235 (8)	−0.0013 (8)	0.0018 (7)	0.0077 (7)
O1	0.0283 (7)	0.0286 (7)	0.0267 (6)	−0.0046 (6)	0.0027 (5)	0.0013 (5)
O2	0.0445 (8)	0.0254 (7)	0.0232 (6)	−0.0044 (6)	0.0095 (6)	0.0078 (5)
O3	0.0284 (7)	0.0338 (7)	0.0307 (7)	0.0086 (6)	0.0142 (5)	0.0058 (6)
O4	0.0271 (7)	0.0380 (8)	0.0241 (6)	0.0055 (6)	0.0113 (5)	0.0054 (5)
Br1	0.03537 (12)	0.05225 (15)	0.01873 (10)	−0.00172 (9)	0.00001 (7)	0.00002 (8)

Geometric parameters (Å, º)

C1—C2	1.379 (3)	C11—O4	1.213 (2)
C1—C6	1.399 (2)	C11—C12	1.470 (2)
C1—Br1	1.8928 (17)	C12—H12	0.9500
C2—C3	1.393 (2)	C13—O2	1.434 (2)
C2—H2	0.9500	C13—H13A	0.9800
C3—O2	1.364 (2)	C13—H13B	0.9800
C3—C4	1.403 (2)	C13—H13C	0.9800
C4—C5	1.399 (2)	C14—O1	1.436 (2)
C4—C7	1.482 (2)	C14—H14A	0.9800
C5—C6	1.392 (2)	C14—H14B	0.9800
C5—H5	0.9500	C14—H14C	0.9800
C6—O1	1.362 (2)	C15—N2	1.138 (2)
C7—C12	1.349 (2)	C16—N1	1.141 (2)
C7—C8	1.493 (2)	C17—C18	1.382 (3)
C8—O3	1.212 (2)	C17—C19^i	1.390 (3)
C8—C9	1.506 (2)	C17—H17	0.9500
C9—C10	1.346 (2)	C18—C19	1.394 (3)
C9—C16	1.443 (2)	C18—H18	0.9500
C10—C15	1.443 (2)	C19—C17^i	1.390 (3)
C10—C11	1.506 (2)	C19—H19	0.9500
C2—C1—C6	122.44 (15)	O4—C11—C10	119.64 (15)
C2—C1—Br1	118.35 (13)	C12—C11—C10	117.32 (14)
C6—C1—Br1	119.19 (13)	C7—C12—C11	123.04 (15)
C1—C2—C3	119.35 (15)	C7—C12—H12	118.5
C1—C2—H2	120.3	C11—C12—H12	118.5
C3—C2—H2	120.3	O2—C13—H13A	109.5
O2—C3—C2	124.46 (15)	O2—C13—H13B	109.5
O2—C3—C4	115.94 (15)	H13A—C13—H13B	109.5
C2—C3—C4	119.59 (16)	O2—C13—H13C	109.5
C5—C4—C3	119.93 (15)	H13A—C13—H13C	109.5
C5—C4—C7	119.47 (14)	H13B—C13—H13C	109.5
C3—C4—C7	120.60 (15)	O1—C14—H14A	109.5
C6—C5—C4	120.83 (15)	O1—C14—H14B	109.5
C6—C5—H5	119.6	H14A—C14—H14B	109.5
C4—C5—H5	119.6	O1—C14—H14C	109.5
O1—C6—C5	124.89 (15)	H14A—C14—H14C	109.5
O1—C6—C1	117.32 (15)	H14B—C14—H14C	109.5
C5—C6—C1	117.79 (16)	N2—C15—C10	179.5 (2)
C12—C7—C4	123.16 (15)	N1—C16—C9	179.8 (2)
C12—C7—C8	118.87 (15)	C18—C17—C19^i	120.29 (17)
C4—C7—C8	117.58 (14)	C18—C17—H17	119.9
O3—C8—C7	123.21 (15)	C19^i—C17—H17	119.9
O3—C8—C9	118.80 (15)	C17—C18—C19	119.66 (17)
C7—C8—C9	117.66 (14)	C17—C18—H18	120.2
C10—C9—C16	122.54 (15)	C19—C18—H18	120.2
C10—C9—C8	120.68 (15)	C17^i—C19—C18	120.05 (18)
C16—C9—C8	116.49 (14)	C17^i—C19—H19	120.0
C9—C10—C15	122.68 (15)	C18—C19—H19	120.0
C9—C10—C11	120.23 (15)	C6—O1—C14	117.33 (14)
C15—C10—C11	117.03 (14)	C3—O2—C13	117.42 (14)
O4—C11—C12	123.04 (16)
C6—C1—C2—C3	2.2 (3)	C4—C7—C8—C9	171.61 (14)
Br1—C1—C2—C3	−176.22 (13)	O3—C8—C9—C10	−158.87 (16)
C1—C2—C3—O2	−178.67 (17)	C7—C8—C9—C10	14.8 (2)
C1—C2—C3—C4	0.0 (3)	O3—C8—C9—C16	15.1 (2)
O2—C3—C4—C5	176.45 (16)	C7—C8—C9—C16	−171.25 (14)
C2—C3—C4—C5	−2.3 (3)	C16—C9—C10—C15	0.3 (3)
O2—C3—C4—C7	−3.8 (2)	C8—C9—C10—C15	173.92 (15)
C2—C3—C4—C7	177.44 (16)	C16—C9—C10—C11	−176.80 (15)
C3—C4—C5—C6	2.5 (3)	C8—C9—C10—C11	−3.2 (2)
C7—C4—C5—C6	−177.20 (15)	C9—C10—C11—O4	171.98 (16)
C4—C5—C6—O1	178.97 (16)	C15—C10—C11—O4	−5.3 (2)
C4—C5—C6—C1	−0.4 (3)	C9—C10—C11—C12	−7.8 (2)
C2—C1—C6—O1	178.57 (16)	C15—C10—C11—C12	174.96 (15)
Br1—C1—C6—O1	−3.0 (2)	C4—C7—C12—C11	177.18 (15)
C2—C1—C6—C5	−2.0 (3)	C8—C7—C12—C11	4.5 (2)
Br1—C1—C6—C5	176.44 (12)	O4—C11—C12—C7	−172.59 (17)
C5—C4—C7—C12	−47.4 (2)	C10—C11—C12—C7	7.1 (2)
C3—C4—C7—C12	132.83 (18)	C19^i—C17—C18—C19	0.0 (3)
C5—C4—C7—C8	125.34 (17)	C17—C18—C19—C17^i	0.0 (3)
C3—C4—C7—C8	−54.4 (2)	C5—C6—O1—C14	−7.0 (3)
C12—C7—C8—O3	158.02 (17)	C1—C6—O1—C14	172.39 (16)
C4—C7—C8—O3	−15.1 (2)	C2—C3—O2—C13	2.9 (3)
C12—C7—C8—C9	−15.3 (2)	C4—C3—O2—C13	−175.80 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.