Benzoic acid-2,9-dimethyl-phenanthroline (1/1).

The constituents of the title 1:1 co-crystal, C(7)H(6)O(2)·C(14)H(12)N(2), are connected into dimeric aggregates by a bifurcated O-H⋯N hydrogen bond; the hydroxyl-H atom is hydrogen bonded to the two N atoms of the 2,9-dimethyl-phenanthroline. The hydrogen-bonded residues are almost orthogonal to each other [dihedral angle = 78.56 (7) °]. In the crystal packing, the aggregates are assembled into layers in the bc plane by π⋯π inter-actions [ring centroid⋯ring centroid distance = 3.5577 (16) Å] involving the pyridyl rings, and C-H⋯π contacts involving the phenanthroline-H atom and the phenyl ring of the acid.

Related literature

For related studies on co-crystal formation, see: Broker & Tiekink (2007 ▶); Broker et al. (2008 ▶).

Experimental

Crystal data

C7H6O2·C14H12N2

M = 330.37

Monoclinic,

a = 13.575 (5) Å

b = 11.645 (4) Å

c = 11.148 (4) Å

β = 104.832 (6)°

V = 1703.6 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 98 K

0.46 × 0.31 × 0.20 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.864, T max = 1

13167 measured reflections

3907 independent reflections

3589 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.156

S = 1.09

3907 reflections

231 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.38 e Å−3

Δρmin = −0.55 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536810029065/bt5303sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029065/bt5303Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H6O2·C14H12N2	F(000) = 696
Mr = 330.37	Dx = 1.288 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6463 reflections
a = 13.575 (5) Å	θ = 2.1–40.6°
b = 11.645 (4) Å	µ = 0.08 mm−1
c = 11.148 (4) Å	T = 98 K
β = 104.832 (6)°	Block, colourless
V = 1703.6 (11) Å3	0.46 × 0.31 × 0.20 mm
Z = 4

Rigaku AFC12K/SATURN724 diffractometer	3907 independent reflections
Radiation source: fine-focus sealed tube	3589 reflections with I > 2σ(I)
graphite	Rint = 0.035
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −17→17
Tmin = 0.864, Tmax = 1	k = −15→15
13167 measured reflections	l = −12→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0717P)2 + 0.8352P] where P = (Fo2 + 2Fc2)/3
3907 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.38 e Å−3
1 restraint	Δρmin = −0.55 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.25983 (16)	0.62242 (12)	0.73806 (12)	0.0586 (5)
H1O	0.276 (2)	0.5534 (8)	0.733 (2)	0.088*
O2	0.22317 (11)	0.60724 (11)	0.53150 (11)	0.0383 (3)
N1	0.20135 (10)	0.37901 (11)	0.76126 (12)	0.0224 (3)
N2	0.39950 (10)	0.44243 (10)	0.79467 (11)	0.0203 (3)
C1	0.22858 (14)	0.66340 (14)	0.62456 (15)	0.0290 (4)
C2	0.20107 (11)	0.78707 (13)	0.62330 (14)	0.0223 (3)
C3	0.22051 (12)	0.85085 (14)	0.73285 (15)	0.0252 (3)
H3	0.2497	0.8147	0.8102	0.030*
C4	0.19729 (14)	0.96692 (15)	0.72878 (18)	0.0335 (4)
H4	0.2113	1.0104	0.8033	0.040*
C5	0.15377 (16)	1.01962 (16)	0.6164 (2)	0.0409 (5)
H5	0.1376	1.0991	0.6138	0.049*
C6	0.13392 (15)	0.95635 (17)	0.50764 (19)	0.0388 (4)
H6	0.1037	0.9926	0.4307	0.047*
C7	0.15784 (12)	0.84071 (15)	0.51025 (16)	0.0290 (4)
H7	0.1448	0.7980	0.4352	0.035*
C8	0.02727 (13)	0.41778 (19)	0.65105 (17)	0.0383 (4)
H8A	0.0627	0.4698	0.6070	0.058*
H8B	−0.0154	0.4626	0.6926	0.058*
H8C	−0.0156	0.3648	0.5916	0.058*
C9	0.10420 (12)	0.35052 (15)	0.74590 (15)	0.0270 (3)
C10	0.07329 (13)	0.26372 (16)	0.81689 (16)	0.0320 (4)
H10	0.0032	0.2450	0.8033	0.038*
C11	0.14511 (14)	0.20691 (15)	0.90530 (16)	0.0307 (4)
H11	0.1252	0.1483	0.9535	0.037*
C12	0.24909 (12)	0.23568 (13)	0.92478 (14)	0.0241 (3)
C13	0.27308 (11)	0.32317 (12)	0.84953 (13)	0.0202 (3)
C14	0.32829 (14)	0.18039 (14)	1.01699 (14)	0.0280 (4)
H14	0.3116	0.1210	1.0668	0.034*
C15	0.42676 (13)	0.21252 (14)	1.03328 (14)	0.0278 (4)
H15	0.4784	0.1751	1.0945	0.033*
C16	0.45439 (12)	0.30185 (13)	0.95988 (14)	0.0225 (3)
C17	0.37851 (11)	0.35697 (12)	0.86771 (13)	0.0192 (3)
C18	0.55556 (12)	0.33981 (14)	0.97563 (14)	0.0260 (3)
H18	0.6092	0.3058	1.0372	0.031*
C19	0.57615 (12)	0.42575 (14)	0.90205 (15)	0.0261 (3)
H19	0.6441	0.4520	0.9123	0.031*
C20	0.49563 (12)	0.47512 (13)	0.81070 (14)	0.0225 (3)
C21	0.51601 (14)	0.56796 (15)	0.72651 (16)	0.0315 (4)
H21A	0.4683	0.5603	0.6445	0.047*
H21B	0.5860	0.5609	0.7186	0.047*
H21C	0.5071	0.6433	0.7615	0.047*

	U11	U22	U33	U12	U13	U23
O1	0.1251 (15)	0.0251 (7)	0.0210 (6)	0.0281 (8)	0.0100 (8)	0.0043 (5)
O2	0.0607 (9)	0.0301 (7)	0.0209 (6)	0.0070 (6)	0.0049 (6)	−0.0025 (5)
N1	0.0235 (6)	0.0242 (6)	0.0198 (6)	0.0004 (5)	0.0060 (5)	−0.0013 (5)
N2	0.0254 (6)	0.0179 (6)	0.0175 (6)	−0.0008 (5)	0.0054 (5)	−0.0013 (4)
C1	0.0404 (9)	0.0242 (8)	0.0206 (7)	0.0036 (7)	0.0046 (7)	0.0022 (6)
C2	0.0206 (7)	0.0234 (7)	0.0234 (7)	0.0014 (5)	0.0065 (6)	0.0042 (6)
C3	0.0262 (7)	0.0261 (8)	0.0251 (8)	0.0012 (6)	0.0096 (6)	0.0023 (6)
C4	0.0398 (9)	0.0256 (8)	0.0416 (10)	0.0008 (7)	0.0221 (8)	−0.0022 (7)
C5	0.0503 (11)	0.0248 (8)	0.0562 (12)	0.0117 (8)	0.0293 (10)	0.0124 (8)
C6	0.0396 (10)	0.0386 (10)	0.0408 (10)	0.0120 (8)	0.0150 (8)	0.0197 (8)
C7	0.0262 (8)	0.0337 (9)	0.0268 (8)	0.0031 (6)	0.0063 (6)	0.0078 (6)
C8	0.0252 (8)	0.0568 (12)	0.0318 (9)	0.0056 (8)	0.0050 (7)	0.0026 (8)
C9	0.0248 (8)	0.0330 (8)	0.0235 (8)	0.0002 (6)	0.0067 (6)	−0.0058 (6)
C10	0.0292 (8)	0.0389 (10)	0.0305 (9)	−0.0096 (7)	0.0124 (7)	−0.0077 (7)
C11	0.0391 (9)	0.0296 (8)	0.0273 (8)	−0.0099 (7)	0.0155 (7)	−0.0029 (6)
C12	0.0341 (8)	0.0205 (7)	0.0193 (7)	−0.0034 (6)	0.0098 (6)	−0.0022 (6)
C13	0.0264 (7)	0.0184 (7)	0.0164 (6)	−0.0008 (5)	0.0066 (6)	−0.0032 (5)
C14	0.0424 (9)	0.0213 (7)	0.0209 (7)	−0.0022 (6)	0.0089 (7)	0.0029 (6)
C15	0.0382 (9)	0.0234 (8)	0.0199 (7)	0.0055 (6)	0.0039 (7)	0.0036 (6)
C16	0.0285 (8)	0.0210 (7)	0.0173 (7)	0.0039 (6)	0.0046 (6)	−0.0019 (5)
C17	0.0254 (7)	0.0172 (6)	0.0152 (6)	0.0009 (5)	0.0055 (6)	−0.0026 (5)
C18	0.0252 (7)	0.0285 (8)	0.0220 (7)	0.0064 (6)	0.0016 (6)	−0.0020 (6)
C19	0.0221 (7)	0.0302 (8)	0.0267 (8)	0.0004 (6)	0.0073 (6)	−0.0054 (6)
C20	0.0274 (7)	0.0213 (7)	0.0201 (7)	−0.0012 (6)	0.0086 (6)	−0.0048 (5)
C21	0.0354 (9)	0.0294 (9)	0.0315 (9)	−0.0072 (7)	0.0121 (7)	0.0008 (7)

O1—C1	1.317 (2)	C9—C10	1.412 (2)
O1—H1O	0.839 (12)	C10—C11	1.367 (3)
O2—C1	1.213 (2)	C10—H10	0.9500
N1—C9	1.328 (2)	C11—C12	1.412 (2)
N1—C13	1.3597 (19)	C11—H11	0.9500
N2—C20	1.327 (2)	C12—C13	1.410 (2)
N2—C17	1.3614 (19)	C12—C14	1.436 (2)
C1—C2	1.487 (2)	C13—C17	1.448 (2)
C2—C7	1.394 (2)	C14—C15	1.355 (2)
C2—C3	1.396 (2)	C14—H14	0.9500
C3—C4	1.386 (2)	C15—C16	1.432 (2)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.385 (3)	C16—C17	1.410 (2)
C4—H4	0.9500	C16—C18	1.410 (2)
C5—C6	1.385 (3)	C18—C19	1.367 (2)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.384 (3)	C19—C20	1.411 (2)
C6—H6	0.9500	C19—H19	0.9500
C7—H7	0.9500	C20—C21	1.503 (2)
C8—C9	1.502 (2)	C21—H21A	0.9800
C8—H8A	0.9800	C21—H21B	0.9800
C8—H8B	0.9800	C21—H21C	0.9800
C8—H8C	0.9800
C1—O1—H1O	108 (2)	C10—C11—C12	119.76 (15)
C9—N1—C13	118.52 (14)	C10—C11—H11	120.1
C20—N2—C17	118.58 (13)	C12—C11—H11	120.1
O2—C1—O1	124.10 (16)	C13—C12—C11	117.00 (15)
O2—C1—C2	123.66 (15)	C13—C12—C14	120.36 (15)
O1—C1—C2	112.24 (14)	C11—C12—C14	122.64 (15)
C7—C2—C3	119.61 (15)	N1—C13—C12	122.99 (14)
C7—C2—C1	119.28 (15)	N1—C13—C17	118.06 (13)
C3—C2—C1	121.09 (14)	C12—C13—C17	118.94 (14)
C4—C3—C2	120.00 (15)	C15—C14—C12	120.29 (15)
C4—C3—H3	120.0	C15—C14—H14	119.9
C2—C3—H3	120.0	C12—C14—H14	119.9
C5—C4—C3	120.17 (17)	C14—C15—C16	121.19 (15)
C5—C4—H4	119.9	C14—C15—H15	119.4
C3—C4—H4	119.9	C16—C15—H15	119.4
C4—C5—C6	119.92 (17)	C17—C16—C18	117.04 (14)
C4—C5—H5	120.0	C17—C16—C15	119.87 (15)
C6—C5—H5	120.0	C18—C16—C15	123.08 (14)
C7—C6—C5	120.49 (17)	N2—C17—C16	122.89 (14)
C7—C6—H6	119.8	N2—C17—C13	117.76 (13)
C5—C6—H6	119.8	C16—C17—C13	119.34 (13)
C6—C7—C2	119.82 (17)	C19—C18—C16	119.79 (14)
C6—C7—H7	120.1	C19—C18—H18	120.1
C2—C7—H7	120.1	C16—C18—H18	120.1
C9—C8—H8A	109.5	C18—C19—C20	119.44 (15)
C9—C8—H8B	109.5	C18—C19—H19	120.3
H8A—C8—H8B	109.5	C20—C19—H19	120.3
C9—C8—H8C	109.5	N2—C20—C19	122.25 (14)
H8A—C8—H8C	109.5	N2—C20—C21	117.01 (14)
H8B—C8—H8C	109.5	C19—C20—C21	120.74 (14)
N1—C9—C10	122.31 (16)	C20—C21—H21A	109.5
N1—C9—C8	116.68 (15)	C20—C21—H21B	109.5
C10—C9—C8	120.99 (15)	H21A—C21—H21B	109.5
C11—C10—C9	119.42 (15)	C20—C21—H21C	109.5
C11—C10—H10	120.3	H21A—C21—H21C	109.5
C9—C10—H10	120.3	H21B—C21—H21C	109.5
O2—C1—C2—C7	6.1 (3)	C14—C12—C13—C17	−0.6 (2)
O1—C1—C2—C7	−174.24 (17)	C13—C12—C14—C15	0.6 (2)
O2—C1—C2—C3	−172.06 (17)	C11—C12—C14—C15	−178.93 (15)
O1—C1—C2—C3	7.6 (2)	C12—C14—C15—C16	0.1 (2)
C7—C2—C3—C4	−0.3 (2)	C14—C15—C16—C17	−0.8 (2)
C1—C2—C3—C4	177.84 (15)	C14—C15—C16—C18	178.49 (15)
C2—C3—C4—C5	0.7 (3)	C20—N2—C17—C16	0.2 (2)
C3—C4—C5—C6	−0.4 (3)	C20—N2—C17—C13	179.49 (12)
C4—C5—C6—C7	−0.4 (3)	C18—C16—C17—N2	0.7 (2)
C5—C6—C7—C2	0.8 (3)	C15—C16—C17—N2	−179.97 (13)
C3—C2—C7—C6	−0.5 (2)	C18—C16—C17—C13	−178.60 (13)
C1—C2—C7—C6	−178.63 (16)	C15—C16—C17—C13	0.7 (2)
C13—N1—C9—C10	−0.7 (2)	N1—C13—C17—N2	−0.3 (2)
C13—N1—C9—C8	177.54 (14)	C12—C13—C17—N2	−179.36 (13)
N1—C9—C10—C11	0.4 (3)	N1—C13—C17—C16	179.01 (13)
C8—C9—C10—C11	−177.79 (16)	C12—C13—C17—C16	0.0 (2)
C9—C10—C11—C12	0.1 (2)	C17—C16—C18—C19	−0.6 (2)
C10—C11—C12—C13	−0.3 (2)	C15—C16—C18—C19	−179.93 (15)
C10—C11—C12—C14	179.27 (15)	C16—C18—C19—C20	−0.3 (2)
C9—N1—C13—C12	0.6 (2)	C17—N2—C20—C19	−1.1 (2)
C9—N1—C13—C17	−178.42 (13)	C17—N2—C20—C21	178.74 (13)
C11—C12—C13—N1	−0.1 (2)	C18—C19—C20—N2	1.2 (2)
C14—C12—C13—N1	−179.61 (14)	C18—C19—C20—C21	−178.67 (14)
C11—C12—C13—C17	178.91 (13)

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.839 (12)	2.327 (16)	2.973 (2)	134 (2)
O1—H1o···N2	0.839 (12)	2.09 (2)	2.788 (2)	141 (2)
C19—H19···Cgi	0.95	2.60	3.426 (2)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.84 (1)	2.33 (2)	2.973 (2)	134 (2)
O1—H1o⋯N2	0.84 (1)	2.09 (2)	2.788 (2)	141 (2)
C19—H19⋯Cgi	0.95	2.60	3.426 (2)	145

Symmetry code: (i) .