Constructor graph description of the hydrogen-bonding supra­molecular assembly in two ionic compounds: 2-(pyrazol-1-yl)ethylammonium chloride and diaquadichloridobis­(2-hydroxy­ethyl­ammonium)cobalt(II) dichloride

Covalent bond tables are used to generate hydrogen-bond pattern designator symbols for the crystallographically characterized title compounds. 2-(Pyrazol-1-yl)ethyl­ammon­ium chloride, C₅H₁₀N₃⁺·Cl⁻, (I), has three unique, strong, charge-assisted hydrogen bonds of the types N—H...Cl and N—H...N that form unary through ternary levels of graph-set inter­actions. Diaquadichloridobis(2-hydroxy­ethyl­ammonium)­cobalt(II) dichloride, [CoCl₂(C₂H₈NO)₂(H₂O)₂]Cl₂, (II), forms five unique charge-assisted hydrogen bonds of the types O—H...Cl and N—H...Cl. These form graph-set patterns up to the quinary level. The Co complex in (II) resides at a crystallographic inversion center; thus the number of hydrogen bonds to consider doubles due to their G-equivalence, and the handling of such a case is demonstrated.

S1. Comment

Metal ions are known to catalyze the hydrolysis of free imines (Nolan & Hay, 1974; Satchell & Satchell, 1979; Hay, 1987), although metal ions are also known to stabilize imines. Surprisingly, hydrolysis of imines is observed even when Schiff base ligands form metal complexes (Bähr & Thämlitz, 1955; Bähr & Döge, 1957). In fact, formation of imines followed by metal-assisted hydrolysis back to amines is now widely used as a way of protecting amines in organic synthesis (Deng et al., 2002; Kurita, 2001; Shelley et al., 1999) . So why do imines hydrolyze in the presence of metal ions in some instances but generally metal ions stabilize imines? It appears counter ions associated with the metal ion have a role to play in the hydrolysis. Recent reports by Gosh and co-workers (Chattopadhyay et al., 2007) have shown that counter ions associated with metals ions have a role in the hydrolysis of imines. Using nickel chloride and nickel thiocyanate they were able to show that in the presence of strongly coordinating SCN–, the Ni^II ion is unable to catalyze the hydrolysis of tetradentate Schiff base ligands; but with a weaker coordinating Cl– the Schiff base ligands hydrolyzed to the parent amine (Lee et al., 1948). In spite of the apparent role counter ions play in metal-assisted hydrolysis of imines, the Lewis acidity of the metal and the nature of the imine remain the crucial factors in determining if a metal ion will stabilize or hydrolyze an imine. We have recently found that 2-{[2-(3,5-dimethylpyrazol-1-yl)ethylimino]-methyl}-4,6-ditertiarybutyl-phenol is stabilized by CoCl₂ and PdCl₂ (Boltina et al., 2010), but the unsubstituted pyrazolyl analog was hydrolyzed by FeCl₂ (see Scheme), while CoCl₂ hydrolyzed 2-(hydroxyethylimino)phenol (see Scheme); in both cases to the ammonium chloride compounds, (C₅H₁₀N₃₎⁺Cl^-, (I), and [CoCl₂(C₂H₈NO)₂(H₂O)₂]Cl₂, (II), that self-assemble via hydrogen bonding.

Recently, we demonstrated the application of graph-set analysis to the description of complex hydrogen-bonding interaction in the structures of (3,5-dimethyl-1H-pyrazol-4-ylmethyl)isopropylammonium chloride monohydrate (Guzei, Keter et al., 2007) and N,N'-bis(2-hydroxy-1-methylethyl)phthalamide (Guzei, Spencer et al., 2007) .In this paper we illustrate the use of `covalent bond tables' for the generation of the proper graph-set pattern designators. Both (I) and (II) have extensive hydrogen-bonding frameworks and provide suitable systems for studying supramolecular motifs. The `covalent bond table' approach was originally introduced by Grell et al. (1999), but herein we (a) describe our method of generating the covalent bond table based on a diagram showing a convenient minimum number of necessary hydrogen bonds using (I) as an example, and (b) provide an example [compound (II)] where the symmetry-related hydrogen bonds (due to the main molecule residing on an inversion center) complicate the creation of the covalent bond table. The latter complexity arises from the crystallographic equivalence of hydrogen-bonding interactions and two possibilities of completing an entry in the table.

A molecular drawing of (I) is shown in Fig. 1.The bond distances and angles within the cation are typical, as confirmed by the Mogul structural check (Bruno et al., 2004). There are three charge-assisted hydrogen-bonding interactions, denoted a–c (Table 2), of two types (N—H···Cl and N—H···N). These hydrogen bonds feature rather short D···A distances and D—H···A angles ranging between 155.0 (14) and 161.4 (15)°, and are comparable to other similar hydrogen bonds in the Cambridge Structural Database (CSD; Version 1.11, January 2009 release; Allen, 2002).

Our procedure for generating the appropriate pattern designators for all possible hydrogen-bonding R (ring) and C (chain) patterns is based on the methodology of Grell et al. and involves the following steps:

(1) Assignment of a letter code to each unique bond such as a, b, etc.;

(2) Creation of a molecular drawing showing all hydrogen bonds (with labels) formed by both cation and anion.

(3) Generation of the covalent bond table containing the number of covalent bonds between each pair of hydrogen bonds a→, b←, etc. The arrows denote the direction of the hydrogen bond: → designates a donor-to-acceptor D—H···A interaction, whereas ← represents an acceptor-to-donor A···H—D orientation.

(4) Generation of a packing diagram showing the hydrogen-bonding interactions with the letter labels a, b, etc.

(5) Identification of hydrogen-bonding motifs such as ring R(a→b←) or chain C(c→d→).

(6) Assignment of numerical values to the number of donors, acceptors and length of the pattern in the pattern designator symbol G^acceptors_donors(size) with the use of the covalent bond table.

The workflow for compound (I) was executed as follows. After each hydrogen bond is assigned a label (step 1, Table 2), a molecular drawing with the necessary hydrogen bonds is generated (step 2, Fig. 2). One can easily follow all possible primary and secondary hydrogen-bond sequences using this drawing.

Step 3. The covalent bond table is a symmetric matrix with the dimension of twice the number of the hydrogen bonds, since each bond will have two representations, for the `forward' bond (e.g. a→) and `backward' bonds (e.g. a←) (Table 3). Note that the columns list bonds in the order a→a←b\</i>→b←c→c\</b>← whereas the rows starts with a `backward' bond a←a→b\</i>←b→c←c\</b>→. The number of covalent bonds (or covalent edges) is now very easy to count with the help of Fig. 2. The first column is filled as follows. The number of covalent edges between bonds a→ (column 1) and a← (row 1) is zero, since the forward bond a goes from atom H3A to Cl1 and the backward a bond is from Cl1 to H3A (there are no covalent bonds in the chloride). In generating the covalent bond table, the order in which the bonds are considered is important. When counting the covalent bonds between two hydrogen bonds, the covalent bonds are counted starting at the hydrogen bond in the column going to the hydrogen bond in the row. The second entry for bonds a→ (column 1) and a→ (row 2) is non-existent, since the forward a bond ends at Cl1 and there is no a bond originating from the chloride. The entry for bond a→ (column 1) and b← (row 3) is absent, because there are no covalent bonds between bonds N3—H3A···Cl1 (a→) and N1···H3B—N3 (b←). The a→b→ entry is also absent, the entry for bond a→ (column 1) and c← (row 5) is again zero because the bonds meet at the chloride, and the a→c← entry is absent. The table is symmetric; thus the first row contains the same entries as the first column. The second column corresponding to a← contains more numerical entries. The first entry corresponding to a←a← is non-existent, the second cell corresponding to a←a→ is zero. The third cell shows the number of covalent bonds between bond a← (column 2) and bond b← (row 3) - there are five bonds, H3A—N3, N3—C5, C5—C4, C4—N2 and N2—N1. The fourth cell in column 2 corresponds to a←b→ and the number of covalent bonds between atoms H3A and H3B is two. The fifth cell (entry is non-existent) represents the covalent bond count in the sequence a←c←. The last entry a←c→ is the number of covalent bonds between H3A and H3C, which is two. The second row is identical to the second column. The rest of the table is filled out in a similar fashion.

Step 4. The packing diagram showing the color-coded hydrogen bonds is presented in Fig. 3. To facilitate the hydrogen-bonding pattern identification it may be easier to eliminate all the covalent edges from the drawing in order to depict all the interactions schematically (Fig. 4).

Step 5. An examination of projections along the a and b axes clearly reveals that the ions are linked into chains C(b→) in the crystallographic b direction (Fig. 5) and into zigzag chains C(a→c←) in the crystallographic a direction (Fig. 6). These zigzag rows of alternating a and c hydrogen bonds are connected by the b hydrogen bond to form two-dimensional sheets.

Step 6. The designators pattern symbol G^acceptors_donors(size) is generated. The covalent bond table was created specifically for this step. Chains C(b→) are formed by b bonds only (Fig. 5); therefore the number of donors and acceptors is one apiece. The full symbol would thus be C¹₁ (size), but one donor and one acceptor are the default values not explicitly written in the designator. The size of the pattern corresponds to the b→b→ entry in the covalent bond table (5) plus the number of hydrogen bonds the pattern involves (1). Thus, the correct pattern designator for the primary level chain C(b→) is C¹₁(6), or simply C(6).

For the pattern C(a→c←) (Fig. 6) two entries from the covalent bond table are necessary, corresponding to a→c← (0), and to c←a→ (2) because the pattern repeats. There are two hydrogen bonds involved; therefore the size is 0 + 2 + 2 = 4. There are two hydrogen bonds, and therefore two donors (for exceptions see Grell et al., 1999). The number of acceptors is the number of bonds minus the number of arrows in the pattern pointing toward each other (meaning there is only one acceptor involved).In the pattern a→c← in question the two arrows point toward each other, hence the number of acceptors is 2 -1 = 1. Consequently, the pattern designator for a secondary-level chain C(a→c←) is C₂¹ (7). These results could also be obtained by visual inspection, but our approach is substantially less error prone.

Since this system features three types of hydrogen bonds it is possible to construct tertiary systems, such as chain C(c→a←b\</i>←) and ring R(a→c←b\</i>←b←c→a\</b>←b←b← ). The covalent bond table makes generation of the designator pattern symbol G_donors^acceptors(size) a trivial exercise. For C(c→a←b\</i>←) we have three donors, two acceptors (two arrows point toward each other), and the size is 0 (c→a← table entry) + 5 (a←b← table entry) + 2 (b←c→ table entry) + 3 (number of hydrogen bonds) = 10. Thus, the symbol for the C(c→a←b\</i>←) chain is C₃²(10). Similarly, for ring R(a→c←b\</i>←b←c→a\</b>←b←b←) one obtains R₈⁶(32). In this case the size is determined as the sum of 0 + 5 + 5 + 2 + 0 + 5 + 5 + 2 + 8 (number of hydrogen bonds) = 32. The program Mercury (Bruno et al., 2002) now has an option for conveniently calculating graph sets, but it may not generate a symbol for a particular pattern one is interested in.

Compound (II) crystallizes in a centrosymmetric triclinic space group P1 .The cation occupies a crystallographic inversion center (Fig. 7). The bond distances and angles within the cation are unexceptional, as confirmed by the Mogul structural check. There are five strong, charge-assisted hydrogen-bonding interactions, denoted a–e (Table 4), of two types (O—H···Cl and N—H···Cl). These hydrogen bonds feature rather short D···A distances and D—H···A angles spanning the range 152.2 (17)–171.3 (18)°, and are comparable to other similar hydrogen bonds in the CSD. Thus each cation acts as a donor in ten hydrogen bonds and an acceptor in two, while each chloride anion acts as an acceptor in four hydrogen bonds.

The structure of the ionic compound presented us with an interesting dilemma. As a result of the large number of acidic H atoms (six in the asymmetric unit) and hydrogen-bond acceptors, one of which is formally negatively charged (Cl2), we had to evaluate the significance of each possible hydrogen-bonding interaction (Table 4). The bonds can be classified as `classic' bifurcated and trifurcated. There are six classic hydrogen bonds, but only five satisfy the usual criterion of direction (D—H···A angle between 150 and 180°). The other bond is clearly outside the range of D—H···A angles considered acceptable for strong, classic hydrogen bonds.

Our graph-set analysis will follow the previously outlined six steps. The results of step 1, assignment of a letter code to each type of bond, are presented in Table 4.

Step 2, preparation of a molecular drawing showing all hydrogen bonds, is accomplished with Fig. 8. The cation occupies a crystallographic inversion center; therefore each hydrogen bond has a symmetry-related counterpart. Hydrogen bonds related by inversion are G-equivalent, in the sense that a symmetry transformation g in the space group G will map one bond onto the other. This will present ambiguities when graph-set notations are generated because it would be possible to select paths with the same bond-label sequences but with a different number of bonds. To avoid these ambiguities all G-equivalent bonds are also assigned a number; thus bond a1 is related by inversion to a2, b1 is related by inversion to b2, etc. Hydrogen bonds related by translation are T-equivalent and have the same letter codes in Fig. 8.

Step 3 involves the creation of the covalent bond table. This procedure is moderately labor intensive due to the presence of five hydrogen bonds and their G-equivalents, and we generate entries both for `forward' and `backward' bonds. The table dimensions are 20 x 20, but all diagonal elements are zeros and the symmetry of the table reduces the number of entries we must generate by half, which means that instead of 400 values only 190 have to be tabulated. Table 5 is the outcome of our visual inspection of Fig. 8.

Step 4. The strong hydrogen-bonding interactions link the ions in two-dimensional sheets in the ac plane (Fig. 9). The sheets are then stacked along the b axis (Fig. 10). The sheets are linked by a hydrogen-bonding interaction, N1—H1E···Cl2, with a donor-to-acceptor distance of 3.3815 (18) Å, which is considered to be weak because of the suboptimal N1—H1-···Cl2 angle of 140.5 (15)°. This weak interaction was not included in the constructor graph and graph-set analysis that follows.

Steps 5 and 6. The hydrogen-bonding interaction network in (II) can be readily visualized with the help of the constructor graph (Fig. 11). Primary-level patterns (those formed with one type of hydrogen bond) include the chain C(e→) equivalent to chains C(e1→) and C(e2→). The size of this C(e→) pattern is 3 (the e1→e1→entry in Table 5) +1 (number of hydrogen bonds) = 4. Thus, the pattern designator symbol is C(4). Another primary pattern, ring R(e1→e2→), has a size of 3 + 3 + 2 = 8 and the full symbol of R²₂(8).

Secondary-level patterns include the chain C(b1→c1←) and the ring R(a1→d1←). The number of hydrogen donors in each pattern is 2, but the number of acceptors is 1 (the arrows in the patterns point head to head, and involve a Cl^- anion that is the acceptor of both bonds). The covalent bond table is used for facile pattern size determination. For the C(b1→c1←) it is the sum of 0(b1→c1← entry in the table) + 5(c1←b1→ entry in the table) + 2(number of hydrogen bonds) =7, resulting in the C¹₂(7) designator. Similarly, rings R(a1→d1←) are described with R¹₂(9).

Tertiary patterns are exemplified by the chain C(a1→b1←\<b>d1→b1←) and the ring R(b2→c2←\<b>e1→). The chain pattern has four donors but two (4 - 2 = 2) acceptors with the size of 0 + 10 + 0 + 7 + 4 = 21. This patterns is described with C²₄(21). The ring pattern is created with three donors but two acceptors, its size computed by summation of four terms 0 + 4 + 6 + 3 = 12. Thus, the pattern designator is R²₃(13).

A quaternary zigzag chain pattern is identified with the sequence a1→b1←d2\</i>→c2← . There are four donors, two acceptors (4 - 2 = 2), the size is 10 (0 + 2 + 0 + 4 + 4), for the pattern designator C²₄(10).

An obvious pentary-level pattern is ring a1→c1←e2\</i>→d2→b2←.\</i>It involves two chloride anions (and there are two occurrences of arrows pointing head-to-head); thus there are three acceptors for the five donors, and the size is 0 + 4 + 6 + 0 + 7 + 5 = 22. The pattern designator is R³₅(22).

The currently used pattern designators do not allow for the inclusion of the pattern level value in its symbol.

Compounds (I) and (II) have unexceptional molecular geometries but form interesting two- and three-dimensional supramolecular structures as a result of hydrogen-bonding interactions. We have explained and demonstrated the use of covalent bond tables and constructor graph diagrams for identification and classification of hydrogen-bonding pattern designators. These compounds provide examples of the usefulness of such tools and the need for their mainstream use in crystallography.

Related literature

For related literature, see: Allen (2002); Bähr & Döge (1957); Bähr & Thämlitz (1955); Bruno et al. (2002, 2004); Chattopadhyay et al. (2007); Deng et al. (2002); Guzei et al. (2007a, 2007b); Hay (1987); Kurita (2001); Lee et al. (1948); Nolan & Hay (1974); Satchell & Satchell (1979); Shelley et al. (1999).

S2. Experimental

For the synthesis of (I). To a solution of L1 {[2-(pyrazol-1-yl)ethylimino]-4,6-ditertiarybutyl-phenol} (0.26 g, 0.80 mmol) in CH₂Cl₂ (20 ml) was added FeCl₂ (0.051 g, 0.40 mmol). The solution was stirred for 18 h under nitrogen, after which the reaction mixture was filtered and the filtrate concentrated to about 10 ml. Subsequent addition of an equal volume of hexane precipitated a dark green powdery paramagnetic material. A CH₂Cl₂ solution of this material slowly formed white crystals of (I) over several days, while the bulk of the solution remained green.

For the synthesis of (II). A solution of L2 [2-(hydroxyethylimino)phenol] (0.50 g, 3.00 mmol) and CoCl₂ (0.39 g, 3.00 mmol) in THF [tetrahydrofuran] (15 ml) was stirred at room temperature for 24 h, resulting in a dark green solution. After the concentrating the solution to half its volume and adding about 10 ml of hexane, a dark green solid precipitated. This material was re-dissolved in CH₂Cl₂, layered with hexane and left for about a week during which time purple crystals of compound (II) formed while the bulk of the solution remained green.

S3. Refinement

All H atoms were placed in idealized locations and refined as riding with appropriate displacement parameters U_iso(H) = 1.2 or 1.5U_eq(parent atom). The outlier reflections were omitted based on the statistics test described in Prince & Nicholson (1983) and Rollett (1988), and implemented in program FCF_filter (Guzei, 2007). The number of omitted outliers is 2 for (I) and 4 for (II).

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), modiCIFer (Guzei, 2007), publCIF (Westrip, 2010).

Figures

	Fig. 1. A molecular diagram of (I) shown with 50% probability ellipsoids. The dashed line represents a hydrogen-bonding interaction.
	Fig. 2. A diagram of (I) shown with 50% probability ellipsoids and with the convenient minimum number of hydrogen bonds to generate the covalent bond table.
	Fig. 3. A packing diagram of (I) viewed along the a axis. Hydrogen bonds are colored as follows: a, blue; b, red; and c, green.
	Fig. 4. A constructor graph representation of (I) viewed along the a axis. Circles denote the cations and triangles denote the chloride anions. Arrows point from the donor to the acceptor.
	Fig. 5. A constructor graph projection of the hydrogen-bonding interaction b of (I) along the a axis. Circles denote the cations. Arrows point from the donor to the acceptor.
	Fig. 6. A constructor graph projection of the hydrogen-bonding interactions a and c of (I) onto the ac plane. Circles denote the cations and triangles denote the chloride anions. Arrows point from the donor to the acceptor.
	Fig. 7. A molecular diagram of (II) shown with 50% probability ellipsoids. The atoms designated `i' are the symmetry-equivalent atoms generated through inversion. All H atoms residing on C atoms were omitted for clarity.
	Fig. 8. A diagram of (II) shown with 50% probability ellipsoids and with a convenient minimum number of hydrogen bonds to generate the covalent bond table. All H atoms connected to C atoms were omitted for clarity.
	Fig. 9. A packing diagram of (II) viewed in the ac plane. Two- dimensional sheets are formed by the strong hydrogen bonds, a–e. The hydrogen bonds are colored as followed: a, orange; b, red; c, green; d , purple; and e, blue.
	Fig. 10. A packing diagram of (II) viewed along the c axis. Two- dimensional sheets are stacked along the b axis. The hydrogen bonds are colored as followed: a, orange; b, red; c, green; d, purple; and e, blue.
	Fig. 11. A constructor graph representation of (II) viewed along the b axis .Circles denote the cations and triangles denote the chloride anions. Arrows point from the donor to the acceptor. The bonds with index 2 are G-equivalents of bonds with index 1.

(I) 2-pyrazol-1-ylethylammonium chloride

Crystal data

C5H10N3^+·Cl^−	F(000) = 312
Mr = 147.61	Dx = 1.373 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7682 reflections
a = 6.9634 (11) Å	θ = 2.9–30.0°
b = 9.3732 (14) Å	µ = 0.45 mm^−1
c = 10.9416 (17) Å	T = 100 K
V = 714.15 (19) Å^3	Block, colourless
Z = 4	0.45 × 0.27 × 0.11 mm

Data collection

Bruker CCD 1000 area detector diffractometer	2035 independent reflections
Radiation source: fine-focus sealed tube	1991 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
0.30° ω and 0.4 ° ϕ scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
Tmin = 0.824, Tmax = 0.952	k = −12→12
10559 measured reflections	l = −14→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.022	All H-atom parameters refined
wR(F^2) = 0.060	w = 1/[s^2(Fo^2) + (0.0388P)^2 + 0.0937P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2035 reflections	Δρmax = 0.36 e Å^−3
123 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)

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.

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
Cl1	0.15432 (3)	1.26216 (2)	0.34917 (2)	0.01617 (7)
N1	0.33063 (12)	0.88210 (9)	0.34936 (8)	0.01526 (16)
N2	0.44073 (12)	0.93306 (9)	0.44199 (8)	0.01315 (16)
N3	0.59370 (13)	1.21254 (10)	0.36615 (8)	0.01509 (17)
H3A	0.478 (3)	1.2049 (16)	0.3681 (14)	0.026 (4)*
H3B	0.622 (2)	1.2794 (17)	0.3128 (16)	0.027 (4)*
H3C	0.628 (2)	1.2444 (17)	0.4370 (17)	0.031 (4)*
C1	0.15571 (16)	0.86651 (11)	0.39779 (9)	0.01705 (19)
H1	0.053 (2)	0.8308 (15)	0.3487 (13)	0.025 (4)*
C2	0.15402 (17)	0.90628 (11)	0.52127 (9)	0.0182 (2)
H2	0.054 (3)	0.9062 (17)	0.5779 (15)	0.031 (4)*
C3	0.33888 (16)	0.94834 (10)	0.54662 (9)	0.01606 (18)
H3	0.395 (2)	0.9783 (17)	0.6194 (15)	0.028 (4)*
C4	0.64532 (16)	0.95855 (10)	0.42396 (9)	0.01516 (18)
H4B	0.706 (2)	0.8746 (16)	0.3929 (13)	0.019 (4)*
H4A	0.693 (2)	0.9792 (15)	0.4993 (14)	0.016 (3)*
C5	0.68471 (14)	1.07498 (11)	0.33072 (9)	0.01545 (19)
H5B	0.638 (2)	1.0512 (15)	0.2534 (13)	0.017 (3)*
H5A	0.813 (2)	1.0916 (14)	0.3249 (12)	0.014 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.01601 (11)	0.01895 (11)	0.01355 (11)	0.00191 (8)	−0.00060 (8)	0.00019 (8)
N1	0.0144 (4)	0.0161 (3)	0.0152 (3)	−0.0004 (3)	−0.0020 (4)	−0.0030 (3)
N2	0.0133 (4)	0.0133 (3)	0.0129 (4)	0.0001 (3)	−0.0004 (3)	−0.0004 (3)
N3	0.0145 (4)	0.0164 (4)	0.0143 (4)	0.0003 (3)	0.0002 (3)	0.0018 (3)
C1	0.0143 (4)	0.0170 (4)	0.0198 (4)	−0.0013 (4)	−0.0005 (4)	−0.0004 (3)
C2	0.0165 (5)	0.0200 (4)	0.0180 (5)	−0.0009 (4)	0.0043 (4)	0.0012 (3)
C3	0.0181 (4)	0.0167 (4)	0.0134 (4)	0.0002 (4)	0.0011 (4)	−0.0001 (3)
C4	0.0118 (4)	0.0152 (4)	0.0184 (4)	0.0005 (4)	−0.0010 (4)	0.0008 (3)
C5	0.0132 (4)	0.0167 (4)	0.0164 (4)	0.0002 (3)	0.0015 (4)	0.0003 (3)

Geometric parameters (Å, º)

N1—C1	1.3363 (14)	C1—H1	0.955 (15)
N1—N2	1.3576 (12)	C2—C3	1.3745 (17)
N2—C3	1.3543 (14)	C2—H2	0.934 (17)
N2—C4	1.4579 (13)	C3—H3	0.932 (16)
N3—C5	1.4881 (13)	C4—C5	1.5189 (14)
N3—H3A	0.812 (17)	C4—H4B	0.954 (15)
N3—H3B	0.879 (17)	C4—H4A	0.909 (15)
N3—H3C	0.864 (19)	C5—H5B	0.934 (14)
C1—C2	1.4015 (14)	C5—H5A	0.912 (14)
C1—N1—N2	104.90 (8)	N2—C3—C2	106.83 (9)
C3—N2—N1	111.87 (9)	N2—C3—H3	122.2 (10)
C3—N2—C4	127.50 (9)	C2—C3—H3	130.9 (10)
N1—N2—C4	120.56 (8)	N2—C4—C5	112.65 (8)
C5—N3—H3A	110.8 (11)	N2—C4—H4B	110.0 (9)
C5—N3—H3B	110.4 (10)	C5—C4—H4B	105.9 (9)
H3A—N3—H3B	107.8 (15)	N2—C4—H4A	105.5 (9)
C5—N3—H3C	114.5 (11)	C5—C4—H4A	113.0 (9)
H3A—N3—H3C	106.5 (16)	H4B—C4—H4A	109.8 (13)
H3B—N3—H3C	106.6 (15)	N3—C5—C4	111.76 (8)
N1—C1—C2	111.15 (10)	N3—C5—H5B	107.0 (9)
N1—C1—H1	119.9 (9)	C4—C5—H5B	111.9 (9)
C2—C1—H1	129.0 (9)	N3—C5—H5A	106.8 (9)
C3—C2—C1	105.25 (10)	C4—C5—H5A	110.3 (9)
C3—C2—H2	124.6 (11)	H5B—C5—H5A	108.8 (13)
C1—C2—H2	130.2 (11)
C1—N1—N2—C3	0.48 (10)	C4—N2—C3—C2	−177.33 (9)
C1—N1—N2—C4	177.74 (8)	C1—C2—C3—N2	0.02 (11)
N2—N1—C1—C2	−0.46 (11)	C3—N2—C4—C5	−118.73 (10)
N1—C1—C2—C3	0.29 (12)	N1—N2—C4—C5	64.48 (11)
N1—N2—C3—C2	−0.31 (11)	N2—C4—C5—N3	58.16 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N1^i	0.879 (17)	2.046 (18)	2.8920 (13)	161.4 (15)
N3—H3A···Cl1	0.812 (17)	2.323 (17)	3.1003 (11)	160.4 (15)
N3—H3C···Cl1^ii	0.864 (19)	2.348 (19)	3.1522 (11)	155.0 (14)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1/2, −y+5/2, −z+1.

(II) Diaqua-dichlorido-bis(hydroxyethylammonium)cobalt(II) dichloride

Crystal data

[CoCl2(C2H8NO)2(H2O)2]Cl2	Z = 1
Mr = 360.95	F(000) = 185
Triclinic, P1	Dx = 1.738 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.258 (2) Å	Cell parameters from 4185 reflections
b = 6.653 (3) Å	θ = 2.5–27.5°
c = 8.369 (3) Å	µ = 2.02 mm^−1
α = 83.57 (3)°	T = 100 K
β = 86.37 (5)°	Block, pink
γ = 86.19 (2)°	0.43 × 0.29 × 0.14 mm
V = 344.9 (2) Å^3

Data collection

Bruker CCD 1000 area detector diffractometer	1560 independent reflections
Radiation source: fine-focus sealed tube	1555 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
0.30° ω and 0.4 ° ϕ scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
Tmin = 0.478, Tmax = 0.766	k = −8→8
4432 measured reflections	l = −10→10

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 0.0978P] where P = (Fo^2 + 2Fc^2)/3
1560 reflections	(Δ/σ)max = 0.001
110 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.46 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.

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
Co1	1.0000	1.0000	1.0000	0.00824 (7)
Cl1	1.27823 (4)	1.16070 (4)	0.82207 (3)	0.01190 (8)
Cl2	0.21103 (4)	0.75252 (4)	0.49085 (3)	0.01212 (8)
O1	0.76421 (13)	1.18219 (12)	0.88347 (10)	0.01181 (16)
H1A	0.784 (3)	1.197 (3)	0.791 (2)	0.027 (4)*
H1B	0.641 (3)	1.153 (3)	0.899 (2)	0.029 (4)*
O2	0.98975 (13)	0.80000 (11)	0.82614 (9)	0.01244 (16)
H2	1.072 (3)	0.809 (3)	0.748 (2)	0.023 (4)*
N1	0.69566 (16)	0.74081 (16)	0.56857 (12)	0.01391 (19)
H1E	0.773 (3)	0.645 (3)	0.522 (2)	0.029 (4)*
H1D	0.761 (3)	0.856 (3)	0.550 (2)	0.025 (4)*
H1F	0.574 (3)	0.759 (3)	0.525 (2)	0.025 (4)*
C1	0.86676 (17)	0.62552 (16)	0.82628 (13)	0.0114 (2)
H1C	0.954 (2)	0.525 (2)	0.7784 (17)	0.010 (3)*
H1G	0.836 (2)	0.573 (2)	0.9373 (18)	0.012 (3)*
C2	0.65838 (17)	0.67923 (16)	0.74477 (13)	0.0120 (2)
H2B	0.578 (3)	0.788 (2)	0.7895 (19)	0.017 (4)*
H2A	0.571 (2)	0.564 (2)	0.7549 (18)	0.015 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00803 (11)	0.00918 (11)	0.00782 (11)	−0.00128 (7)	−0.00134 (7)	−0.00140 (7)
Cl1	0.00988 (13)	0.01495 (14)	0.01076 (13)	−0.00276 (9)	0.00006 (9)	−0.00006 (9)
Cl2	0.00994 (13)	0.01639 (14)	0.01031 (13)	−0.00114 (9)	−0.00046 (9)	−0.00243 (9)
O1	0.0098 (4)	0.0144 (4)	0.0109 (4)	−0.0015 (3)	−0.0011 (3)	0.0006 (3)
O2	0.0137 (4)	0.0141 (4)	0.0105 (4)	−0.0057 (3)	0.0016 (3)	−0.0041 (3)
N1	0.0103 (4)	0.0189 (5)	0.0125 (4)	−0.0014 (4)	−0.0027 (3)	0.0000 (4)
C1	0.0122 (5)	0.0104 (5)	0.0121 (5)	−0.0025 (4)	−0.0018 (4)	−0.0020 (4)
C2	0.0118 (5)	0.0129 (5)	0.0114 (5)	−0.0015 (4)	0.0000 (4)	−0.0021 (4)

Geometric parameters (Å, º)

Co1—O1^i	2.0683 (12)	N1—C2	1.4934 (15)
Co1—O1	2.0683 (12)	N1—H1E	0.89 (2)
Co1—O2	2.0852 (11)	N1—H1D	0.883 (19)
Co1—O2^i	2.0853 (11)	N1—H1F	0.860 (19)
Co1—Cl1	2.4400 (12)	C1—C2	1.5132 (16)
Co1—Cl1^i	2.4400 (11)	C1—H1C	0.941 (15)
O1—H1A	0.77 (2)	C1—H1G	0.967 (15)
O1—H1B	0.81 (2)	C2—H2B	0.953 (16)
O2—C1	1.4345 (14)	C2—H2A	0.963 (15)
O2—H2	0.805 (19)
O1^i—Co1—O1	180.0	Co1—O2—H2	120.1 (13)
O1^i—Co1—O2	91.51 (5)	C2—N1—H1E	110.5 (12)
O1—Co1—O2	88.49 (5)	C2—N1—H1D	111.7 (12)
O1^i—Co1—O2^i	88.49 (5)	H1E—N1—H1D	109.5 (17)
O1—Co1—O2^i	91.51 (5)	C2—N1—H1F	109.4 (12)
O2—Co1—O2^i	180.0	H1E—N1—H1F	108.1 (16)
O1^i—Co1—Cl1	89.17 (4)	H1D—N1—H1F	107.6 (16)
O1—Co1—Cl1	90.83 (4)	O2—C1—C2	111.40 (9)
O2—Co1—Cl1	85.86 (4)	O2—C1—H1C	108.2 (9)
O2^i—Co1—Cl1	94.14 (4)	C2—C1—H1C	113.1 (9)
O1^i—Co1—Cl1^i	90.83 (4)	O2—C1—H1G	107.7 (9)
O1—Co1—Cl1^i	89.17 (4)	C2—C1—H1G	109.5 (9)
O2—Co1—Cl1^i	94.14 (4)	H1C—C1—H1G	106.8 (12)
O2^i—Co1—Cl1^i	85.86 (4)	N1—C2—C1	111.81 (10)
Cl1—Co1—Cl1^i	180.0	N1—C2—H2B	107.4 (9)
Co1—O1—H1A	113.4 (14)	C1—C2—H2B	111.9 (9)
Co1—O1—H1B	118.8 (13)	N1—C2—H2A	106.6 (9)
H1A—O1—H1B	105.5 (18)	C1—C2—H2A	110.5 (9)
C1—O2—Co1	130.05 (7)	H2B—C2—H2A	108.4 (13)
C1—O2—H2	109.6 (13)
O1^i—Co1—O2—C1	87.56 (9)	Cl1^i—Co1—O2—C1	−3.38 (8)
O1—Co1—O2—C1	−92.44 (9)	Co1—O2—C1—C2	93.56 (10)
O2^i—Co1—O2—C1	77 (28)	O2—C1—C2—N1	67.04 (12)
Cl1—Co1—O2—C1	176.62 (8)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2^ii	0.77 (2)	2.34 (2)	3.1094 (14)	171.3 (18)
O1—H1B···Cl1^iii	0.81 (2)	2.39 (2)	3.1315 (14)	152.2 (17)
O2—H2···Cl2^iv	0.805 (19)	2.329 (19)	3.0884 (16)	157.6 (17)
N1—H1F···Cl2	0.860 (19)	2.313 (19)	3.1360 (16)	160.3 (16)
N1—H1D···Cl2^ii	0.883 (19)	2.608 (19)	3.4349 (19)	156.4 (15)
N1—H1E···Cl2^v	0.89 (2)	2.651 (19)	3.3815 (19)	140.4 (15)

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