A new polymorph of 1,4-bis­(imida­zol-1-ylmeth­yl)benzene dihydrate and its hydrogen-bonded fivefold inter­penetrated CdSO₄ network

Single crystals of a new polymorph of 1,4-bis­(imidazol-1-yl­meth­yl)benzene dihydrate (bix·2H₂O), C₁₄H₁₄N₄·2H₂O, have been obtained by the hydro­thermal method. The asymmetric unit is composed of two independent half-bix mol­ecules, one on an inversion center and one on a twofold axial site, and two water mol­ecules. The disordered water mol­ecules link into discrete tetra­meric water units via two O-H...O hydrogen bonds, forming planar R₄⁴(8) rings. These tetra­meric water units and bix mol­ecules are further linked by two O-H...N hydrogen bonds into a three-dimensional network in which an (106) hydrogen-bonded ring is observed. These large rings lead to the formation of a fivefold inter­penetrated network. If both the tetra­meric water units and the bix mol­ecules can be regarded as connected nodes, one single three-dimensional net can then be rationalized as a CdSO₄ network. This study indicates that topological methodology can be applied in some cases in order to understand the inherent characteristics of some hydrogen-bonded supra­molecular assemblies.

S1. Comment

The crystal structure of another polymorph of the title compound (bix.2H₂O) has been reported previously [Cambridge Strcutural Database (Allen, 2002) refcode PUVQIG (Hoskins et al., 1997b; Abrahams et al., 1998). Interestingly, crystallization of bix via the hydrothermal method leads to a structure in the monoclinic space group C2/c with Z = 8 [polymorph (II)], in contrast to the previously reported structure [polymorph (I)] in space group P2₁/n with Z = 2, which was obtained by recrystallization from water. In this communication, we report the differences between these two polymorphs and give an illustration of their topological classification.

As a flexible ligand, bix has been often used in the synthesis of metal–organic frameworks as a linker molecule (Hoskins et al., 1997a; Abrahams et al., 2002; Carculli et al., 2005; Wen et al., 2005, Zhang et al., 2005) and in the construction of hydrogen-bonded supramolecular assemblies as hydrogen-bonding acceptors (Ma & Coppens, 2004; Ma et al., 2004; Shen et al., 2004; Aakeröy et al., 2005, 2006; Zhang et al., 2007). Recently, as a result of our interest in exploring the self-assembling nature of carboxylic acids with Lewis bases (Meng et al., 2007; Meng, Lin & Li, 2008; Meng, Xiao, Wang & Liu, 2008; Meng, Xiao, Zhang & Zhou, 2008), we have re-synthesized the N-containing Lewis base bix by the standard procedure (Hoskins et al., 1997b).

Single-crystal X-ray diffraction reveals that there are two independent half-bix molecules and two water molecules in the selected asymmetric unit of polymorph (II) (Fig. 1). In the N1-containing bix molecule, its two halves are related by an inversion center at (1/2, 1/2, 0). However, the two halves in the N2-containing bix molecule are related by a twofold axis. By comparison, the asymmetric unit of polymorph (I) consists of only one water molecule and half a bix molecule whose two halves are related by an inversion center at (0, 1, 1/2). Besides this, the cell volume (2956.0 ų) in polymorph (II) expands to ca four times of that in polymorph (I) (733.4 ų). The water molecules in (II) are linked into a discrete tetrameric R₄⁴(8) water ring (Fig. 2) by O—H···O hydrogen bonds. Conversely, water molecules in (I) are linked into one-dimensional water chains [O···O = 2.728 (2) and 2.782 (2) Å; symmetry codes: -x, -y + 2, -z; -x - 1, -y + 2, -z] running parallel to the [100] direction (Fig. 2). These apparent differences may mainly be attributed to (i) the crystallized [cystallization?] conditions, i.e. temperature and pressure, and (ii) the flexibility stemming from the –CH₂– group (Zhang et al., 2007).

The crystal packings of polymorphs (I) and (II) are also very different from each other. In (II), bix and water molecules are linked by O—H···O and N—H···O hydrogen bonds (Table 1) into a continuous three-dimensional network. Two types of hydrogen-bonded rings are formed; one is the R₄⁴(8) ring as mentioned above and the other is a very large R₁₄²⁰(106) hydrogen-bond ring (Bernstein et al., 1995), which is constructed via N—H···O hydrogen bonds. Topological analysis indicates that if one considers the tetrameric water units to be four-connected nodes and the bix molecules to be bridges (Fig. 3a), one single net can then be rationalized as a three-dimensional net with CdSO₄ (cds) topology. Fig. 3(b) reveals the topology displayed by this structure with short and long Schläfli symbols 6⁵.8 and 6.6.6.6.6₂.*, respectively (* means there are no rings for this angle; Batten, 2001; Batten & Robson, 1998). Further analysis indicates that five independent three-dimensional networks of this type related by a translation vector of ca 2.1436 Å along the [100] direction make up the final fivefold interpenetrated network (Fig. 3b). These interpenetrated networks are strengthened by π–π and C—H···π interactions [Cg1···Cg2ⁱⁱ = 3.934 (2) Å, Cg3···Cg3ⁱⁱⁱ = 3.593 (2) Å, and H3···Cg3^iv = 2.95 Å, C3···Cg3^iv = 3.829 (2) Å and C3—H3···Cg3^iv = 158°; Cg1, Cg2 and Cg3 are the centroids of the rings involving C1, C8 and N4, respectively; symmetry codes: (ii) x - 1, y, z - 1, (iii) -x + 2, y, -z + 3/2; (iv) -x + 2, y, -z + 1/2]. By contrast, bix molecules in polymorph (I) are joined together by the only O_water···N_imidazole [2.821 (2) Å] hydrogen bond, which originates from two sides of the one-dimensional water chain, resulting in a simple two-dimensional sheet running parallel to the (010) plane (Fig. 4a). We can regard the two-dimensional sheet as a Shubnikov hexagonal plane (hcb) net with a total Schläfli symbol of 6³ (Fig. 4b). The neighbouring sheets are linked by C1—H1···O1(-x - 1/2, y - 1/2, -z + 1/2) interactions into a simple three-dimensional network. No other interactions are observed in polymorph (I).

Related literature

For related literature, see: Aakeröy et al. (2005, 2006); Abrahams et al. (1998, 2002); Batten (2001); Batten & Robson (1998); Bernstein et al. (1995); Carculli et al. (2005); Hoskins et al. (1997a, 1997b); Ma & Coppens (2004a); Ma et al. (2004b); Meng et al. (2007, 2008a, 2008b, 2008c); Shen et al. (2004); Wen et al. (2005); Zhang et al. (2005, 2007).

S2. Experimental

The title compound was prepared according to the literature method (Hoskins et al., 1997b). A 30.0 mg sample was sealed in a 23 ml Teflon-lined stainless steel autoclave, heated at 400 K for 2 d under autogenous pressure and cooled slowly to room temperature. Plate-shaped single crystals suitable for X-ray diffraction were obtained at the bottom of the autoclave.

S3. Refinement

In polymorph (II), the water molecules were both disordered over two positions. Because of the existence of the discrete hydrogen-bonding networks, the disorder parameters of O1 and O2 were coupled and their final occupancies were refined to be 0.59 (1):0.41 (1) for the major and minor components, respectively. All H atoms bonded to C atoms were positioned geometrically, with C—H distances of 0.93 (aromatic) and 0.97 Å (methylene), and treated as riding, with U_iso(H) set at 1.2U_eq(C). H atoms bonded to water O atoms were found in difference maps and refined with the constraints O—H = 0.82 (1) Å, H—H = 1.35 (1) Å and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003), Mercury (Version 1.4; Bruno et al., 2002) and DIAMOND (Brandenburg, 2004); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structures of bix.2H2O in polymorphs (I) and (II), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 10% probability level and H atoms are shown as small spheres of arbitrary radii. Hydorgen bonds are shown as dashed lines. In polymorph (II), atoms labeled with the suffixes A and B are at the symmetry positions (-x + 1, -y + 1, -z) and (-x +3, y, -z + 3/2), respectively. The minor components of the disorder water molecules have been omitted for clarity. In polymorph (I), atoms labeled with the suffix C are at the symmetry position (-x, -y + 2, -z + 1).
	Fig. 2. Parts of the crystal structures of bix.2H2O in polymorphs (I) (a) and (II) (b), respectively, showing the formation of the R4^4(8) and R12^20(106) hydrogen-bond rings in (II) and the one-dimensional water chain running parallel to the [100] direction in (I). Hydrogen bonds are shown as dashed lines. The minor components of the disordered water moleculesin (II) have been omitted for clarity.
	Fig. 3. Simplification of the crystal structure of bix.2H2O in polymorph (II): (a) a schematic view of the formation of a single three-dimensional network and (b) a schematic view of the formation of the fivefold interpenetrated network. [In (a) in the electronic version of the paper, blue and aqua balls represent R4^4(8) water units and bix molecules, respectively.]
	Fig. 4. Simplification of the crystal structure of bix.2H2O in polymorph (I): (a) a schematic view of the formation of the two-dimensional network running parallel to the (010) plane and (b) a schematic view of the Shubnikov hexagonal plane (hcb) net. [In (a) in the electronic version of the paper, blue and aqua balls represent bix and water molecules, respectively.]

1,4-bis(imidazol-1-ylmethyl)benzene dihydrate

Crystal data

C14H14N4·2H2O	F(000) = 1168
Mr = 274.32	Dx = 1.233 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2032 reflections
a = 10.7178 (8) Å	θ = 2.3–23.8°
b = 17.9925 (14) Å	µ = 0.09 mm^−1
c = 15.3662 (12) Å	T = 299 K
β = 94.006 (2)°	Prism, colorless
V = 2956.0 (4) Å^3	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3369 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2237 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
0.3° wide ω exposures scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −13→13
Tmin = 0.965, Tmax = 0.983	k = −18→23
9245 measured reflections	l = −19→19

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.7501P] where P = (Fo^2 + 2Fc^2)/3
3369 reflections	(Δ/σ)max < 0.001
224 parameters	Δρmax = 0.17 e Å^−3
12 restraints	Δρmin = −0.13 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	Occ. (<1)
C1	0.53974 (17)	0.42695 (9)	−0.00846 (10)	0.0546 (4)
C2	0.42190 (18)	0.44231 (10)	0.01619 (12)	0.0630 (5)
H2	0.3681	0.4034	0.0273	0.076*
C3	0.61776 (17)	0.48557 (11)	−0.02467 (12)	0.0616 (5)
H3	0.6979	0.4762	−0.0415	0.074*
C4	0.5846 (2)	0.34798 (10)	−0.01634 (12)	0.0721 (6)
H4A	0.5131	0.3149	−0.0213	0.087*
H4B	0.6289	0.3431	−0.0690	0.087*
C5	0.6319 (2)	0.30087 (11)	0.13498 (14)	0.0743 (6)
H5	0.5491	0.2917	0.1461	0.089*
C6	0.8285 (2)	0.31079 (12)	0.14960 (16)	0.0814 (6)
H6	0.9106	0.3097	0.1735	0.098*
C7	0.7936 (2)	0.33287 (11)	0.06809 (14)	0.0727 (5)
H7	0.8456	0.3495	0.0261	0.087*
C8	1.37872 (15)	0.45287 (11)	0.77603 (10)	0.0551 (4)
C9	1.43993 (17)	0.51832 (11)	0.76292 (14)	0.0716 (6)
H9	1.3997	0.5632	0.7716	0.086*
C10	1.43998 (16)	0.38752 (11)	0.76313 (12)	0.0624 (5)
H10	1.4000	0.3426	0.7722	0.075*
C11	1.24523 (17)	0.45326 (14)	0.80100 (12)	0.0757 (6)
H11A	1.2279	0.4075	0.8313	0.091*
H11B	1.2330	0.4944	0.8403	0.091*
C12	1.12161 (18)	0.52399 (12)	0.68190 (13)	0.0668 (5)
H12	1.1415	0.5722	0.6997	0.080*
C13	1.05094 (18)	0.50388 (12)	0.61061 (13)	0.0685 (5)
H13	1.0128	0.5368	0.5703	0.082*
C14	1.10934 (17)	0.40531 (11)	0.67441 (13)	0.0645 (5)
H14	1.1211	0.3553	0.6880	0.077*
N1	0.66770 (15)	0.32609 (8)	0.05926 (9)	0.0606 (4)
N2	0.7272 (2)	0.29034 (10)	0.19224 (12)	0.0840 (6)
N3	1.15841 (12)	0.46048 (9)	0.72304 (9)	0.0569 (4)
N4	1.04272 (14)	0.42884 (10)	0.60531 (10)	0.0693 (5)
O1	0.716 (2)	0.2775 (11)	0.3763 (4)	0.115 (4)	0.59 (1)
H1A	0.717 (7)	0.277 (5)	0.3227 (8)	0.172*	0.59 (1)
H1B	0.786 (4)	0.276 (6)	0.402 (4)	0.172*	0.59 (1)
O2	0.8981 (14)	0.3183 (8)	0.5088 (10)	0.102 (2)	0.59 (1)
H2A	0.923 (8)	0.358 (3)	0.530 (4)	0.152*	0.59 (1)
H2B	0.847 (8)	0.296 (4)	0.537 (5)	0.152*	0.59 (1)
O1'	0.779 (3)	0.2557 (8)	0.3734 (5)	0.108 (5)	0.41 (1)
H1C	0.756 (10)	0.262 (6)	0.3217 (17)	0.162*	0.41 (1)
H1D	0.776 (13)	0.293 (4)	0.404 (5)	0.162*	0.41 (1)
O2'	0.869 (2)	0.3192 (12)	0.5294 (16)	0.113 (4)	0.41 (1)
H2C	0.921 (10)	0.350 (6)	0.546 (6)	0.169*	0.41 (1)
H2D	0.831 (10)	0.299 (6)	0.567 (5)	0.169*	0.41 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0723 (12)	0.0509 (10)	0.0390 (9)	0.0055 (9)	−0.0087 (8)	0.0010 (7)
C2	0.0679 (12)	0.0560 (11)	0.0642 (11)	−0.0079 (9)	−0.0020 (9)	0.0129 (9)
C3	0.0609 (11)	0.0673 (12)	0.0568 (11)	0.0079 (9)	0.0061 (8)	0.0083 (9)
C4	0.0997 (15)	0.0580 (12)	0.0554 (11)	0.0141 (10)	−0.0174 (10)	−0.0065 (9)
C5	0.0941 (15)	0.0609 (12)	0.0672 (13)	0.0047 (11)	0.0011 (11)	0.0089 (10)
C6	0.0914 (16)	0.0671 (14)	0.0817 (16)	0.0108 (12)	−0.0214 (13)	−0.0054 (11)
C7	0.0808 (14)	0.0658 (13)	0.0709 (13)	0.0088 (10)	0.0017 (11)	0.0025 (10)
C8	0.0477 (9)	0.0769 (12)	0.0392 (9)	0.0028 (9)	−0.0074 (7)	−0.0025 (8)
C9	0.0575 (10)	0.0633 (12)	0.0910 (15)	0.0105 (9)	−0.0159 (10)	−0.0108 (11)
C10	0.0575 (10)	0.0627 (12)	0.0659 (12)	−0.0080 (9)	−0.0042 (9)	0.0073 (9)
C11	0.0524 (11)	0.1278 (19)	0.0459 (10)	0.0071 (11)	−0.0029 (8)	−0.0009 (11)
C12	0.0650 (12)	0.0681 (12)	0.0664 (12)	0.0042 (10)	−0.0025 (9)	−0.0081 (10)
C13	0.0630 (12)	0.0832 (15)	0.0580 (12)	0.0108 (10)	−0.0046 (9)	0.0029 (10)
C14	0.0600 (11)	0.0670 (12)	0.0664 (12)	−0.0036 (9)	0.0035 (9)	0.0015 (10)
N1	0.0847 (11)	0.0452 (8)	0.0503 (9)	0.0111 (7)	−0.0064 (8)	−0.0004 (7)
N2	0.1220 (16)	0.0694 (11)	0.0581 (10)	0.0145 (11)	−0.0109 (11)	0.0079 (8)
N3	0.0441 (8)	0.0784 (11)	0.0476 (8)	0.0012 (7)	−0.0013 (6)	−0.0043 (7)
N4	0.0614 (10)	0.0872 (13)	0.0579 (10)	−0.0058 (8)	−0.0058 (8)	−0.0086 (9)
O1	0.123 (7)	0.153 (7)	0.068 (3)	−0.010 (6)	0.004 (3)	0.004 (3)
O2	0.095 (5)	0.119 (4)	0.092 (5)	−0.035 (3)	0.017 (3)	−0.009 (3)
O1'	0.137 (12)	0.134 (6)	0.052 (3)	0.012 (6)	0.001 (4)	−0.002 (3)
O2'	0.103 (8)	0.140 (7)	0.097 (8)	−0.071 (6)	0.017 (5)	−0.029 (6)

Geometric parameters (Å, º)

C1—C2	1.372 (3)	C11—N3	1.470 (2)
C1—C3	1.379 (2)	C11—H11A	0.9700
C1—C4	1.508 (2)	C11—H11B	0.9700
C2—C3^i	1.375 (3)	C12—C13	1.337 (3)
C2—H2	0.9300	C12—N3	1.351 (2)
C3—C2^i	1.374 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—N4	1.355 (3)
C4—N1	1.467 (2)	C13—H13	0.9300
C4—H4A	0.9700	C14—N4	1.308 (2)
C4—H4B	0.9700	C14—N3	1.329 (2)
C5—N2	1.314 (3)	C14—H14	0.9300
C5—N1	1.330 (2)	O1—H1A	0.824 (10)
C5—H5	0.9300	O1—H1B	0.822 (10)
C6—C7	1.342 (3)	O1—H1C	1.01 (7)
C6—N2	1.358 (3)	O1—H1D	0.80 (11)
C6—H6	0.9300	O2—H2A	0.823 (10)
C7—N1	1.353 (2)	O2—H2B	0.822 (10)
C7—H7	0.9300	O2—H2C	0.84 (7)
C8—C10	1.368 (2)	O2—H2D	1.24 (4)
C8—C9	1.370 (3)	O1'—H1B	0.58 (8)
C8—C11	1.507 (2)	O1'—H1C	0.822 (10)
C9—C9^ii	1.374 (4)	O1'—H1D	0.820 (10)
C9—H9	0.9300	O2'—H2A	0.91 (5)
C10—C10^ii	1.375 (3)	O2'—H2C	0.818 (10)
C10—H10	0.9300	O2'—H2D	0.820 (10)
C2—C1—C3	118.51 (16)	N3—C11—H11A	109.5
C2—C1—C4	121.14 (17)	C8—C11—H11A	109.5
C3—C1—C4	120.35 (18)	N3—C11—H11B	109.5
C1—C2—C3^i	120.87 (17)	C8—C11—H11B	109.5
C1—C2—H2	119.6	H11A—C11—H11B	108.1
C3^i—C2—H2	119.6	C13—C12—N3	106.53 (18)
C2^i—C3—C1	120.62 (17)	C13—C12—H12	126.7
C2^i—C3—H3	119.7	N3—C12—H12	126.7
C1—C3—H3	119.7	C12—C13—N4	110.46 (18)
N1—C4—C1	111.64 (14)	C12—C13—H13	124.8
N1—C4—H4A	109.3	N4—C13—H13	124.8
C1—C4—H4A	109.3	N4—C14—N3	112.77 (18)
N1—C4—H4B	109.3	N4—C14—H14	123.6
C1—C4—H4B	109.3	N3—C14—H14	123.6
H4A—C4—H4B	108.0	C5—N1—C7	106.85 (17)
N2—C5—N1	112.1 (2)	C5—N1—C4	126.02 (19)
N2—C5—H5	123.9	C7—N1—C4	126.96 (18)
N1—C5—H5	123.9	C5—N2—C6	104.38 (18)
C7—C6—N2	110.5 (2)	C14—N3—C12	106.11 (16)
C7—C6—H6	124.7	C14—N3—C11	126.53 (17)
N2—C6—H6	124.7	C12—N3—C11	127.10 (17)
C6—C7—N1	106.1 (2)	C14—N4—C13	104.13 (16)
C6—C7—H7	126.9	H1A—O1—H1B	114 (2)
N1—C7—H7	126.9	H1A—O1—H1D	119 (10)
C10—C8—C9	118.55 (17)	H1C—O1—H1D	100 (9)
C10—C8—C11	120.99 (18)	H2A—O2—H2B	115 (2)
C9—C8—C11	120.42 (18)	H1A—O1'—H1B	112 (9)
C8—C9—C9^ii	120.72 (11)	H1B—O1'—H1C	132 (10)
C8—C9—H9	119.6	H1C—O1'—H1D	115 (2)
C9^ii—C9—H9	119.6	H2A—O2'—H2B	162 (10)
C8—C10—C10^ii	120.73 (11)	H2B—O2'—H2C	144 (10)
C8—C10—H10	119.6	H2A—O2'—H2D	133 (10)
C10^ii—C10—H10	119.6	H2C—O2'—H2D	116 (2)
N3—C11—C8	110.55 (14)
C3—C1—C2—C3^i	−0.1 (3)	N2—C5—N1—C4	−175.90 (16)
C4—C1—C2—C3^i	178.90 (16)	C6—C7—N1—C5	0.3 (2)
C2—C1—C3—C2^i	0.1 (3)	C6—C7—N1—C4	175.69 (16)
C4—C1—C3—C2^i	−178.90 (16)	C1—C4—N1—C5	84.0 (2)
C2—C1—C4—N1	−101.9 (2)	C1—C4—N1—C7	−90.5 (2)
C3—C1—C4—N1	77.0 (2)	N1—C5—N2—C6	0.4 (2)
N2—C6—C7—N1	−0.1 (2)	C7—C6—N2—C5	−0.2 (2)
C10—C8—C9—C9^ii	0.2 (3)	N4—C14—N3—C12	−0.6 (2)
C11—C8—C9—C9^ii	−177.6 (2)	N4—C14—N3—C11	−175.09 (16)
C9—C8—C10—C10^ii	−0.5 (3)	C13—C12—N3—C14	0.6 (2)
C11—C8—C10—C10^ii	177.3 (2)	C13—C12—N3—C11	175.05 (16)
C10—C8—C11—N3	−94.3 (2)	C8—C11—N3—C14	89.2 (2)
C9—C8—C11—N3	83.5 (2)	C8—C11—N3—C12	−84.2 (2)
N3—C12—C13—N4	−0.4 (2)	N3—C14—N4—C13	0.3 (2)
N2—C5—N1—C7	−0.5 (2)	C12—C13—N4—C14	0.1 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N2	0.82 (1)	2.03 (2)	2.848 (7)	172 (9)
O1—H1B···O2	0.82 (1)	2.10 (5)	2.815 (16)	145 (8)
O2—H2A···N4	0.82 (1)	2.10 (4)	2.869 (13)	157 (9)
O2—H2B···O1^iii	0.82 (1)	2.03 (5)	2.811 (17)	158 (11)
O1′—H1C···N2	0.82 (1)	2.06 (3)	2.868 (10)	170 (13)
O1′—H1D···O2′	0.82 (1)	2.15 (7)	2.77 (2)	132 (8)
O2′—H2C···N4	0.82 (1)	2.09 (2)	2.902 (17)	172 (11)
O2′—H2D···O1′^iii	0.82 (1)	1.82 (3)	2.625 (17)	165 (11)

Symmetry code: (iii) −x+3/2, −y+1/2, −z+1.