Butane-1,2,3,4-tetra-carb-oxy-lic acid-1,10-phenanthroline-water (1/2/2).

The asymmetric unit of the title compound, 2C(12)H(8)N(2)·C(8)H(10)O(8)·2H(2)O, contains one 1,10-phenanthroline mol-ecule, one half-mol-ecule of butane-1,2,3,4-tetra-carb-oxy-lic acid (H(4)BTC) and a water mol-ecule, with the complete tetra-acid generated by crystallographic inversion symmetry. Inter-molecular O-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distances = 3.672 (2) and 3.708 (2) Å form an extensive three-dimensional network, which consolidates the crystal packing.

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 ▶).

Experimental

Crystal data

2C12H8N2·C8H10O8·2H2O

M = 630.60

Triclinic,

a = 7.9472 (16) Å

b = 9.884 (2) Å

c = 10.628 (2) Å

α = 84.37 (3)°

β = 70.12 (3)°

γ = 72.72 (3)°

V = 749.7 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.58 × 0.34 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.950, T max = 0.990

7400 measured reflections

3396 independent reflections

1960 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.188

S = 1.17

3396 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.34 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021398/sj5157sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021398/sj5157Isup2.hkl

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

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) Å3

Rigaku R-AXIS RAPID diffractometer	3396 independent reflections
Radiation source: fine-focus sealed tube	1960 reflections with I > 2σ(I)
graphite	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 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.188	H-atom parameters constrained
S = 1.17	w = 1/[σ2(Fo2) + (0.0607P)2 + 0.4694P] where P = (Fo2 + 2Fc2)/3
3396 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.34 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	−0.5184 (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*

	U11	U22	U33	U12	U13	U23
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)

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—C3i	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···Cg3ii	3.672 (2)	Cg2···Cg3iii	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—C3i	108.5 (2)	C15—C11—C10	119.8 (3)
C2—C3—C3i	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
C3i—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

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···O5iv	0.87	1.70	2.565 (3)	172
O4—H4A···N2	0.86	1.90	2.723 (3)	159
O5—H5B···O2v	0.88	1.98	2.817 (3)	160
O5—H5C···N1	0.85	2.09	2.858 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5iii	0.87	1.70	2.565 (3)	172
O4—H4A⋯N2	0.86	1.90	2.723 (3)	159
O5—H5B⋯O2iv	0.88	1.98	2.817 (3)	160
O5—H5C⋯N1	0.85	2.09	2.858 (3)	149

Symmetry codes: (iii) ; (iv) .