Butane-1,2,3,4-tetra­carb­oxy­lic acid–1,10-phenanthroline–water (1/2/2)

The asymmetric unit of the title compound, 2C₁₂H₈N₂·C₈H₁₀O₈·2H₂O, contains one 1,10-phenanthroline mol­ecule, one half-mol­ecule of butane-1,2,3,4-tetra­carb­oxy­lic acid (H₄BTC) and a water mol­ecule, with the complete tetra-acid generated by crystallographic inversion symmetry. Inter­molecular O—H...O hydrogen bonds and π–π stacking inter­actions [centroid–centroid distances = 3.672 (2) and 3.708 (2) Å form an extensive three-dimensional network, which consolidates the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.048
• wR factor = 0.188
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         28

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT793_ALERT_4_G The Model has Chirality at C3      (Verify) ....          S

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Systems with butane-1,2,3,4-tetracarboxylic acid (H₄BTC) as a ligand have been widely studied (Delgado et al., 2007; Liu et al., 2008; Xu et al., 2010; Zhu et al., 2011). A search of the Cambridge structural database (version 5.32, May 2011) (Allen, 2002) showed that most of the literature dealing with butane-1,2,3,4-tetracarboxylic acid concentrated on metal-organic coordination complexes. In contrast, utilization of the butane-1,2,3,4-tetracarboxylic acid seems relatively limited in the construction of co-crystals (Cheng et al., 2009; Najafpour et al., 2008). In this paper, we report the structure of the title cocrystal.

The asymmetric unit of the title cocrystal consists of one 1,10-phenanthroline, unit one half molecule of butane-1,2,3,4-tetracarboxylic acid and a water molecule as depicted in Figure 1. The present 1,10-phenanthroline molecule preserves a nearly perfect coplanarity with a maximum deviation from the best fit meanplane 0.123 (1) Å. The carboxylato group with C1 and C4 atoms is gauche with the C1–C2–C3–C4 torsion angle being 63.35 (2)°. These values agree well with reported structures (Cheng et al., 2009; Najafpour et al., 2008;). The butane-1,2,3,4-tetracarboxylic acid molecules and water molecules are interlinked via O–H···O hydrogen bonds to generate a 1-dimensional supramolecular chain (Figure 2), which is further interconnected by interchain O–H···N hydrogen bonds to construct a 2-dimensional layer parallel to the (001) plane (Figure 3). The resulting layers are arranged in such a way that the 1,10-phenanthroline ligands are each sandwiched between two antiparallel phen neighbors from different adjacent layers, and the mean interplanar distances between the neighboring phen ligands are 3.67 Å and 3.71 Å, suggesting significant intermolecular face-to-face π–π stacking interactions. Such interlayer interactions are regarded as the driving forces to assemble the layers into a three-dimensional supramolecular architecture as shown in Figure 4.

Related literature

For the use of H₄BTC as a ligand in metal–organic coordination complexes, see: Delgado et al.(2007); Liu et al. (2008); Xu et al. (2010); Zhu et al.(2011). For co-crystals involving H₄BTC, see: Cheng et al.(2009); Najafpour et al. (2008). For details of the Cambridge Structural Database, see: Allen (2002).

S2. Experimental

All chemicals were obtained from commerical sources and were used as obtained. 1,10-phenanthroline (0.1983 g, 1.00 mmol) was added to a stirred mixture solution of butane-1,2,3,4-tetracarboxylic acid (0.1173 g, 0.50 mmol) in 10 ml H₂O and 10 ml me thanol, and the resulting mixture was stirred for 30 min. Colorless crystals were obtained from the solution after standing at room temperature for two months.

S3. Refinement

H atoms bonded to C atoms were placed in geometrically calculated positions and were refined using a riding model, with U_iso(H) = 1.2 U_eq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O–H distances fixed as initially found and with U_iso(H) values set at 1.2 U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The content of asymmetric unit showing the atomic numbering and 45% probability displacement ellipsoids [Symmetry codes: (i) -x, -y + 1, -z + 1].
	Fig. 2. Supramolecular assembly of a one-dimensional chain via O–H···O hydrogen bonds.
	Fig. 3. Supramolecular assembly of a two-dimensional layer via O–H···N hydrogen bonds.
	Fig. 4. Supramolecular assembly of three-dimensional architecture through π–π stacking interactions.

Butane-1,2,3,4-tetracarboxylic acid–1,10-phenanthroline–water (1/2/2)

Crystal data

2C12H8N2·C8H10O8·2H2O	Z = 1
Mr = 630.60	F(000) = 330
Triclinic, P1	Dx = 1.397 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9472 (16) Å	Cell parameters from 4546 reflections
b = 9.884 (2) Å	θ = 3.1–27.5°
c = 10.628 (2) Å	µ = 0.11 mm^−1
α = 84.37 (3)°	T = 293 K
β = 70.12 (3)°	Block, colorless
γ = 72.72 (3)°	0.58 × 0.34 × 0.10 mm
V = 749.7 (3) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3396 independent reflections
Radiation source: fine-focus sealed tube	1960 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
Tmin = 0.950, Tmax = 0.990	k = −12→12
7400 measured reflections	l = −13→13

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.188	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0607P)^2 + 0.4694P] where P = (Fo^2 + 2Fc^2)/3
3396 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.34 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
O1	−0.5184 (3)	0.7050 (2)	0.4404 (3)	0.0745 (7)
H1A	−0.5899	0.7919	0.4447	0.089*
O2	−0.3498 (3)	0.8187 (2)	0.4902 (3)	0.0734 (7)
C1	−0.3757 (4)	0.7102 (3)	0.4718 (3)	0.0434 (6)
C2	−0.2475 (4)	0.5669 (3)	0.4825 (3)	0.0484 (6)
H2A	−0.2240	0.5103	0.4055	0.058*
H2B	−0.3086	0.5200	0.5619	0.058*
C3	−0.0619 (3)	0.5737 (2)	0.4898 (2)	0.0389 (5)
H3A	−0.0862	0.6351	0.5647	0.047*
C4	0.0425 (4)	0.6356 (2)	0.3614 (2)	0.0408 (5)
O3	0.0605 (3)	0.5952 (2)	0.25216 (19)	0.0652 (6)
O4	0.1121 (3)	0.73303 (19)	0.37990 (18)	0.0532 (5)
H4A	0.1639	0.7706	0.3054	0.064*
N1	0.0963 (3)	1.0528 (2)	0.2323 (2)	0.0514 (6)
C5	−0.0353 (5)	1.1744 (3)	0.2717 (3)	0.0613 (8)
H5A	−0.0890	1.1934	0.3629	0.074*
C6	−0.0969 (5)	1.2746 (3)	0.1844 (4)	0.0705 (9)
H6A	−0.1915	1.3571	0.2170	0.085*
C7	−0.0175 (5)	1.2505 (3)	0.0505 (3)	0.0677 (9)
H7A	−0.0565	1.3168	−0.0096	0.081*
C8	0.1230 (4)	1.1255 (3)	0.0040 (3)	0.0546 (7)
C9	0.2172 (5)	1.0959 (4)	−0.1356 (3)	0.0696 (9)
H9A	0.1810	1.1599	−0.1982	0.084*
C10	0.3561 (6)	0.9781 (4)	−0.1774 (3)	0.0734 (10)
H10A	0.4185	0.9633	−0.2687	0.088*
C11	0.4106 (4)	0.8744 (3)	−0.0853 (3)	0.0571 (7)
C12	0.5552 (5)	0.7492 (4)	−0.1252 (4)	0.0746 (10)
H12A	0.6236	0.7328	−0.2154	0.089*
C13	0.5961 (5)	0.6515 (4)	−0.0328 (4)	0.0777 (10)
H13A	0.6935	0.5690	−0.0586	0.093*
C14	0.4888 (5)	0.6777 (3)	0.1014 (4)	0.0709 (9)
H14A	0.5149	0.6093	0.1639	0.085*
C15	0.3153 (4)	0.8952 (3)	0.0537 (3)	0.0466 (6)
C16	0.1741 (4)	1.0267 (3)	0.0985 (2)	0.0449 (6)
N2	0.3519 (3)	0.7946 (2)	0.1444 (2)	0.0552 (6)
O5	0.2570 (3)	0.9523 (2)	0.4390 (2)	0.0597 (6)
H5B	0.2932	1.0275	0.4404	0.072*
H5C	0.1736	0.9754	0.4011	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0631 (13)	0.0483 (11)	0.131 (2)	−0.0092 (10)	−0.0622 (14)	0.0059 (12)
O2	0.0697 (14)	0.0409 (11)	0.124 (2)	−0.0077 (10)	−0.0544 (14)	−0.0078 (11)
C1	0.0420 (13)	0.0434 (13)	0.0460 (14)	−0.0107 (11)	−0.0188 (11)	0.0070 (11)
C2	0.0450 (14)	0.0369 (12)	0.0677 (17)	−0.0104 (11)	−0.0269 (13)	0.0080 (12)
C3	0.0394 (12)	0.0340 (11)	0.0442 (13)	−0.0094 (10)	−0.0166 (10)	0.0046 (10)
C4	0.0475 (14)	0.0363 (12)	0.0392 (13)	−0.0102 (10)	−0.0178 (11)	0.0053 (10)
O3	0.0941 (17)	0.0659 (13)	0.0441 (11)	−0.0352 (12)	−0.0239 (11)	0.0055 (9)
O4	0.0683 (13)	0.0509 (11)	0.0502 (11)	−0.0332 (10)	−0.0205 (9)	0.0110 (8)
N1	0.0597 (14)	0.0524 (13)	0.0431 (12)	−0.0176 (11)	−0.0171 (11)	0.0022 (10)
C5	0.068 (2)	0.0575 (17)	0.0536 (17)	−0.0092 (15)	−0.0186 (15)	−0.0078 (14)
C6	0.077 (2)	0.0546 (17)	0.080 (2)	−0.0035 (16)	−0.0384 (19)	−0.0002 (16)
C7	0.082 (2)	0.0611 (19)	0.070 (2)	−0.0191 (17)	−0.0424 (19)	0.0141 (16)
C8	0.0687 (18)	0.0576 (16)	0.0503 (16)	−0.0299 (15)	−0.0282 (14)	0.0125 (13)
C9	0.093 (3)	0.083 (2)	0.0443 (16)	−0.041 (2)	−0.0266 (17)	0.0164 (16)
C10	0.091 (3)	0.096 (3)	0.0380 (15)	−0.048 (2)	−0.0102 (16)	0.0071 (17)
C11	0.0575 (17)	0.0677 (18)	0.0488 (16)	−0.0326 (15)	−0.0060 (13)	−0.0067 (14)
C12	0.066 (2)	0.086 (2)	0.066 (2)	−0.0365 (19)	0.0029 (17)	−0.0179 (19)
C13	0.058 (2)	0.064 (2)	0.098 (3)	−0.0149 (16)	−0.0048 (19)	−0.025 (2)
C14	0.068 (2)	0.0519 (17)	0.082 (2)	−0.0128 (15)	−0.0131 (18)	−0.0047 (16)
C15	0.0533 (15)	0.0488 (14)	0.0434 (14)	−0.0281 (12)	−0.0121 (12)	0.0034 (11)
C16	0.0548 (15)	0.0496 (14)	0.0382 (13)	−0.0246 (12)	−0.0179 (11)	0.0054 (11)
N2	0.0594 (15)	0.0461 (12)	0.0576 (14)	−0.0170 (11)	−0.0144 (12)	0.0017 (11)
O5	0.0634 (13)	0.0495 (11)	0.0780 (14)	−0.0128 (9)	−0.0418 (11)	0.0047 (10)

Geometric parameters (Å, º)

O1—C1	1.302 (3)	C7—H7A	0.9300
O1—H1A	0.8734	C8—C16	1.406 (4)
O2—C1	1.196 (3)	C8—C9	1.431 (4)
C1—C2	1.499 (3)	C9—C10	1.333 (5)
C2—C3	1.525 (3)	C9—H9A	0.9300
C2—H2A	0.9700	C10—C11	1.423 (5)
C2—H2B	0.9700	C10—H10A	0.9300
C3—C4	1.514 (3)	C11—C12	1.399 (5)
C3—C3^i	1.540 (4)	C11—C15	1.416 (4)
C3—H3A	0.9800	C12—C13	1.359 (5)
C4—O3	1.214 (3)	C12—H12A	0.9300
C4—O4	1.303 (3)	C13—C14	1.393 (5)
O4—H4A	0.8635	C13—H13A	0.9300
N1—C5	1.330 (4)	C14—N2	1.321 (4)
N1—C16	1.361 (3)	C14—H14A	0.9300
C5—C6	1.387 (4)	C15—N2	1.354 (4)
C5—H5A	0.9300	C15—C16	1.438 (4)
C6—C7	1.359 (5)	O5—H5B	0.8756
C6—H6A	0.9300	O5—H5C	0.8533
C7—C8	1.393 (4)
Cg1···Cg3^ii	3.672 (2)	Cg2···Cg3^iii	3.708 (2)
C1—O1—H1A	106.5	C7—C8—C16	118.4 (3)
O2—C1—O1	123.2 (2)	C7—C8—C9	122.2 (3)
O2—C1—C2	123.5 (2)	C16—C8—C9	119.4 (3)
O1—C1—C2	113.4 (2)	C10—C9—C8	121.1 (3)
C1—C2—C3	112.9 (2)	C10—C9—H9A	119.5
C1—C2—H2A	109.0	C8—C9—H9A	119.5
C3—C2—H2A	109.0	C9—C10—C11	121.3 (3)
C1—C2—H2B	109.0	C9—C10—H10A	119.4
C3—C2—H2B	109.0	C11—C10—H10A	119.4
H2A—C2—H2B	107.8	C12—C11—C15	117.1 (3)
C4—C3—C2	109.7 (2)	C12—C11—C10	123.0 (3)
C4—C3—C3^i	108.5 (2)	C15—C11—C10	119.8 (3)
C2—C3—C3^i	112.0 (2)	C13—C12—C11	120.3 (3)
C4—C3—H3A	108.9	C13—C12—H12A	119.8
C2—C3—H3A	108.9	C11—C12—H12A	119.8
C3^i—C3—H3A	108.9	C12—C13—C14	118.6 (3)
O3—C4—O4	124.0 (2)	C12—C13—H13A	120.7
O3—C4—C3	122.1 (2)	C14—C13—H13A	120.7
O4—C4—C3	113.9 (2)	N2—C14—C13	123.5 (4)
C4—O4—H4A	111.9	N2—C14—H14A	118.2
C5—N1—C16	117.5 (2)	C13—C14—H14A	118.2
N1—C5—C6	123.7 (3)	N2—C15—C11	122.0 (3)
N1—C5—H5A	118.1	N2—C15—C16	119.6 (2)
C6—C5—H5A	118.1	C11—C15—C16	118.5 (3)
C7—C6—C5	119.1 (3)	N1—C16—C8	121.9 (3)
C7—C6—H6A	120.4	N1—C16—C15	118.4 (2)
C5—C6—H6A	120.4	C8—C16—C15	119.7 (2)
C6—C7—C8	119.4 (3)	C14—N2—C15	118.3 (3)
C6—C7—H7A	120.3	H5B—O5—H5C	107.6
C8—C7—H7A	120.3

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z; (iii) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

Cg1, Cg2 and Cg3 are the centroids of the N1/C5-C8/C16/, N2/C14-C11/C15, and C8-C11/C15/C16, rings respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5^iv	0.87	1.70	2.565 (3)	172
O4—H4A···N2	0.86	1.90	2.723 (3)	159
O5—H5B···O2^v	0.88	1.98	2.817 (3)	160
O5—H5C···N1	0.85	2.09	2.858 (3)	149

Symmetry codes: (iv) x−1, y, z; (v) −x, −y+2, −z+1.