6-Chloro-2′-(2-hydroxy­benzyl­idene)­nicotinohydrazide monohydrate

The asymmetric unit of the title compound, C₁₃H₁₀ClN₃O₂·H₂O, consists of a Schiff base mol­ecule and a solvent water mol­ecule. The Schiff base mol­ecule displays a trans configuration with respect to the C=N double bond. The dihedral angle between the benzene and pyridine rings is 22.3 (3)°. In the crystal structure, mol­ecules are linked through inter­molecular O—H...O and N—H...O hydrogen bonds, forming layers parallel to the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.091
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.899(10) ......       3.00 su-Ra
              N2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.899(10) ......       3.00 su-Ra
              N2   -H2      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.98(3), Rep   1.982(14) ......       2.14 su-Ra
              H2   -O3      1.555   2.564

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               2141
           Count of symmetry unique reflns         1498
           Completeness (_total/calc)            142.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       643
           Fraction of Friedel pairs measured     0.429
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

Schiff base compounds have been of great interest for a long time. These compounds play an important role in the development of coordination chemistry (Musie et al., 2001; Bernardo et al., 1996; Paul et al., 2002). Recently, we have reported a few Schiff base compounds (Yang, 2006a,b,c,d,e, 2007; Yang & Guo, 2006). As a further investigation of this work, the crystal structure of the title compound is reported here.

The asymmetric unit of the title compound, C₁₃H₁₀ClN₃O₂·H₂O, consists of a Schiff base molecule and a water molecule (Fig. 1). The Schiff base molecule displays a trans configuration with respect to the C═ N double bond. All the bond lengths are within normal ranges (Allen et al., 1987). The C7═N1 bond length of 1.279 (3) Å conforms to the value for a double bond. The bond length of 1.343 (4) Å between atoms C8 and N2 is intermediate between an C—N single bond and an C═N double bond, because of conjugation effects in the molecule. The dihedral angle between the benzene ring and the pyridine ring is 22.3 (3)°. In the crystal structure, molecules are linked through intermolecular O—H···O and N—H···O hydrogen bonds, forming layers parallel to the bc plane (Fig. 2).

Related literature

For related structures, see Yang (2006a,b,c,d,e, 2007); Yang & Guo (2006). For related literature, see: Allen et al. (1987); Bernardo et al. (1996); Musie et al. (2001); Paul et al. (2002).

S2. Experimental

Salicylaldehyde (0.1 mmol, 12.0 mg) and 6-chloronicotinic acid hydrazide (0.1 mmol, 17.0 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Crystals of the title compound were formed by gradual evaporation of the solvent over a period of 5 days at room temperature.

S3. Refinement

Atoms H2, H3A and H3B were located in a difference Fourier map and refined isotropically, with O—H distances restrained to 0.85 (1) Å, N—H distance restrained to 0.90 (1) Å, H···H distance restrained to 1.37 (2) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with O—H distance of 0.82 Å, C—H distances of 0.93 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. Molecular packing as viewed along the b axis. Hydrogen bonds are shown as dashed lines.

6-Chloro-2'-(2-hydroxybenzylidene)nicotinohydrazide monohydrate

Crystal data

C13H10ClN3O2·H2O	F(000) = 608
Mr = 293.71	Dx = 1.480 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 28.125 (11) Å	Cell parameters from 1313 reflections
b = 3.8193 (15) Å	θ = 2.5–26.7°
c = 12.281 (5) Å	µ = 0.30 mm^−1
β = 92.764 (5)°	T = 298 K
V = 1317.7 (9) Å^3	Block, colourless
Z = 4	0.32 × 0.28 × 0.27 mm

Data collection

Bruker SMART CCD diffractometer	2141 independent reflections
Radiation source: fine-focus sealed tube	1826 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −33→36
Tmin = 0.910, Tmax = 0.923	k = −4→4
3648 measured reflections	l = −15→13

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.2959P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2141 reflections	Δρmax = 0.27 e Å^−3
192 parameters	Δρmin = −0.17 e Å^−3
6 restraints	Absolute structure: Flack (1983), 643 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.15 (9)

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
Cl1	0.53442 (3)	0.6124 (2)	0.35665 (6)	0.0658 (3)
O1	0.22659 (8)	−0.2060 (6)	−0.05359 (16)	0.0570 (6)
H1	0.2498	−0.1108	−0.0233	0.086*
O2	0.36101 (7)	0.0985 (6)	0.00747 (15)	0.0554 (6)
O3	0.30098 (9)	0.3904 (7)	0.84650 (17)	0.0631 (6)
N1	0.27769 (8)	0.0670 (6)	0.10791 (18)	0.0420 (5)
N2	0.31879 (8)	0.2013 (7)	0.15714 (18)	0.0435 (5)
C1	0.19752 (9)	−0.1146 (7)	0.1247 (2)	0.0355 (6)
C2	0.19157 (10)	−0.2361 (7)	0.0176 (2)	0.0396 (6)
C3	0.14878 (11)	−0.3907 (8)	−0.0177 (2)	0.0504 (8)
H3	0.1446	−0.4695	−0.0892	0.060*
C4	0.11279 (11)	−0.4269 (8)	0.0528 (3)	0.0527 (8)
H4	0.0844	−0.5320	0.0287	0.063*
C5	0.11802 (11)	−0.3107 (8)	0.1582 (3)	0.0524 (7)
H5	0.0933	−0.3369	0.2053	0.063*
C6	0.16008 (11)	−0.1548 (7)	0.1940 (2)	0.0446 (6)
H6	0.1636	−0.0752	0.2655	0.054*
C7	0.24163 (9)	0.0418 (7)	0.1670 (2)	0.0399 (6)
H7	0.2437	0.1251	0.2383	0.048*
C8	0.35906 (10)	0.1958 (7)	0.1026 (2)	0.0410 (6)
C9	0.40330 (9)	0.3079 (7)	0.16605 (19)	0.0388 (6)
C10	0.44136 (11)	0.4366 (8)	0.1104 (2)	0.0480 (7)
H10	0.4391	0.4588	0.0349	0.058*
C11	0.48227 (11)	0.5306 (9)	0.1682 (2)	0.0525 (8)
H11	0.5083	0.6190	0.1333	0.063*
C12	0.48349 (10)	0.4898 (8)	0.2797 (2)	0.0449 (7)
N3	0.44856 (9)	0.3663 (7)	0.33543 (19)	0.0485 (6)
C13	0.40865 (10)	0.2742 (8)	0.2784 (2)	0.0459 (7)
H13	0.3834	0.1838	0.3159	0.055*
H2	0.3168 (13)	0.308 (10)	0.2220 (17)	0.080*
H3B	0.2754 (7)	0.427 (11)	0.880 (2)	0.080*
H3A	0.3231 (8)	0.362 (10)	0.895 (2)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0493 (4)	0.0758 (6)	0.0706 (5)	−0.0109 (4)	−0.0159 (4)	−0.0117 (4)
O1	0.0617 (13)	0.0726 (16)	0.0371 (10)	−0.0075 (12)	0.0061 (10)	−0.0067 (10)
O2	0.0486 (12)	0.0836 (16)	0.0335 (10)	0.0052 (11)	−0.0034 (8)	−0.0114 (9)
O3	0.0608 (14)	0.0869 (18)	0.0417 (12)	0.0111 (14)	0.0046 (10)	0.0117 (11)
N1	0.0385 (12)	0.0491 (13)	0.0377 (12)	0.0004 (11)	−0.0044 (10)	−0.0004 (10)
N2	0.0392 (12)	0.0571 (15)	0.0337 (11)	−0.0034 (11)	−0.0037 (10)	−0.0062 (10)
C1	0.0364 (13)	0.0331 (14)	0.0364 (13)	0.0042 (11)	−0.0043 (10)	0.0022 (10)
C2	0.0466 (15)	0.0392 (15)	0.0327 (13)	0.0031 (13)	−0.0022 (12)	−0.0008 (10)
C3	0.0596 (19)	0.0456 (18)	0.0441 (16)	0.0002 (14)	−0.0161 (14)	−0.0011 (12)
C4	0.0434 (16)	0.0455 (17)	0.068 (2)	−0.0047 (14)	−0.0133 (15)	0.0086 (14)
C5	0.0452 (16)	0.0514 (18)	0.061 (2)	0.0013 (14)	0.0037 (15)	0.0076 (14)
C6	0.0485 (16)	0.0469 (16)	0.0386 (14)	0.0027 (13)	0.0027 (12)	0.0020 (11)
C7	0.0434 (15)	0.0432 (15)	0.0323 (12)	0.0027 (12)	−0.0059 (11)	0.0001 (11)
C8	0.0432 (15)	0.0454 (16)	0.0335 (13)	0.0039 (12)	−0.0067 (11)	−0.0003 (11)
C9	0.0382 (14)	0.0438 (16)	0.0343 (13)	0.0021 (11)	−0.0006 (11)	−0.0002 (10)
C10	0.0458 (15)	0.065 (2)	0.0337 (13)	−0.0018 (15)	0.0035 (11)	0.0057 (13)
C11	0.0427 (16)	0.065 (2)	0.0495 (17)	−0.0066 (14)	0.0028 (13)	0.0060 (14)
C12	0.0374 (15)	0.0464 (16)	0.0502 (15)	−0.0016 (12)	−0.0067 (12)	−0.0063 (12)
N3	0.0422 (13)	0.0643 (17)	0.0384 (12)	−0.0036 (12)	−0.0038 (10)	−0.0032 (11)
C13	0.0413 (15)	0.0594 (19)	0.0366 (15)	−0.0067 (13)	−0.0016 (11)	0.0025 (12)

Geometric parameters (Å, º)

Cl1—C12	1.742 (3)	C4—C5	1.370 (5)
O1—C2	1.353 (3)	C4—H4	0.9300
O1—H1	0.8200	C5—C6	1.377 (4)
O2—C8	1.230 (3)	C5—H5	0.9300
O3—H3B	0.856 (10)	C6—H6	0.9300
O3—H3A	0.849 (10)	C7—H7	0.9300
N1—C7	1.279 (3)	C8—C9	1.498 (3)
N1—N2	1.377 (3)	C9—C13	1.387 (4)
N2—C8	1.343 (4)	C9—C10	1.387 (4)
N2—H2	0.899 (10)	C10—C11	1.370 (4)
C1—C6	1.394 (4)	C10—H10	0.9300
C1—C2	1.398 (3)	C11—C12	1.377 (4)
C1—C7	1.451 (3)	C11—H11	0.9300
C2—C3	1.391 (4)	C12—N3	1.312 (4)
C3—C4	1.370 (4)	N3—C13	1.341 (3)
C3—H3	0.9300	C13—H13	0.9300
C2—O1—H1	109.5	C1—C6—H6	119.5
H3B—O3—H3A	107 (2)	N1—C7—C1	121.0 (2)
C7—N1—N2	116.8 (2)	N1—C7—H7	119.5
C8—N2—N1	119.0 (2)	C1—C7—H7	119.5
C8—N2—H2	123 (2)	O2—C8—N2	123.8 (2)
N1—N2—H2	118 (2)	O2—C8—C9	120.4 (3)
C6—C1—C2	118.6 (2)	N2—C8—C9	115.8 (2)
C6—C1—C7	119.0 (2)	C13—C9—C10	118.3 (2)
C2—C1—C7	122.4 (2)	C13—C9—C8	122.6 (2)
O1—C2—C3	118.7 (2)	C10—C9—C8	119.1 (2)
O1—C2—C1	121.5 (2)	C11—C10—C9	119.1 (3)
C3—C2—C1	119.8 (3)	C11—C10—H10	120.4
C4—C3—C2	120.0 (3)	C9—C10—H10	120.4
C4—C3—H3	120.0	C10—C11—C12	117.7 (3)
C2—C3—H3	120.0	C10—C11—H11	121.1
C3—C4—C5	121.0 (3)	C12—C11—H11	121.1
C3—C4—H4	119.5	N3—C12—C11	125.2 (3)
C5—C4—H4	119.5	N3—C12—Cl1	115.5 (2)
C4—C5—C6	119.5 (3)	C11—C12—Cl1	119.3 (2)
C4—C5—H5	120.2	C12—N3—C13	116.8 (2)
C6—C5—H5	120.2	N3—C13—C9	122.9 (3)
C5—C6—C1	121.0 (3)	N3—C13—H13	118.5
C5—C6—H6	119.5	C9—C13—H13	118.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^i	0.85 (1)	1.98 (2)	2.771 (3)	155 (4)
O3—H3B···O1^ii	0.86 (1)	2.15 (2)	2.917 (4)	149 (4)
N2—H2···O3^iii	0.90 (1)	1.98 (1)	2.864 (3)	167 (4)
O1—H1···N1	0.82	1.89	2.610 (3)	147

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