5-Bromo-1H-indole-3-carbaldehyde 2-nitro­phenyl­hydrazone hemihydrate

In the title compound, C₁₆H₁₁BrN₄O₃·0.5H₂O, the water mol­ecule lies on a twofold rotation axis. Symmetry-related mol­ecules are linked to form an N—H...O and O—H...O hydrogen-bonded layer structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.110
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.306     0.677
            Tmin(prime) and Tmax expected:      0.457     0.655
            RR(prime) =      0.649
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.63
PLAT731_ALERT_1_B Bond    Calc     0.86(6), Rep   0.850(10) ......       6.00 su-Rat
              O1W  -H1W     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.86(6), Rep   0.850(10) ......       6.00 su-Rat
              O1W  -H1W     1.555   1.555

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT128_ALERT_4_C Non-standard setting of Space group P2/c    ....    P2/a
PLAT736_ALERT_1_C H...A   Calc     2.21(6), Rep     2.22(2) ......       3.00 su-Rat
              H1W  -O2      1.555   4.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

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

   6 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

5-Bromo-1H-indole-3-carbaldehyde 2-nitrophenylhydrazone hemihydrate

Crystal data

C16H11BrN4O3·0.5H2O	F(000) = 796
Mr = 396.21	Dx = 1.674 Mg m^−3
Monoclinic, P2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ya	Cell parameters from 9035 reflections
a = 16.547 (4) Å	θ = 3.4–27.5°
b = 6.053 (2) Å	µ = 2.64 mm^−1
c = 16.924 (4) Å	T = 295 K
β = 111.93 (2)°	Block, orange
V = 1572.3 (8) Å^3	0.29 × 0.21 × 0.16 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	3491 independent reflections
Radiation source: fine-focus sealed tube	2481 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ω scans	h = −21→21
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→7
Tmin = 0.306, Tmax = 0.677	l = −21→21
14182 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0557P)^2 + 0.5445P] where P = (Fo^2 + 2Fc^2)/3
3491 reflections	(Δ/σ)max = 0.001
234 parameters	Δρmax = 0.41 e Å^−3
3 restraints	Δρmin = −0.63 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.60735 (3)	0.39133 (7)	0.478770 (19)	0.08539 (18)
O1	0.77660 (14)	0.3966 (3)	0.19932 (14)	0.0688 (6)
O2	0.69688 (12)	0.6026 (3)	0.09707 (11)	0.0518 (4)
O3	0.60965 (11)	1.0913 (3)	0.07535 (11)	0.0500 (4)
O1w	0.2500	−0.2399 (5)	0.0000	0.0643 (7)
H1w	0.229 (5)	−0.334 (7)	0.025 (4)	0.21 (3)*
N1	0.73165 (13)	0.5611 (3)	0.17262 (13)	0.0441 (5)
N2	0.53040 (12)	0.8034 (3)	0.08791 (12)	0.0422 (5)
H2n	0.4931 (14)	0.832 (4)	0.0383 (9)	0.050 (7)*
N3	0.51749 (12)	0.6348 (3)	0.13724 (12)	0.0395 (4)
N4	0.36706 (14)	0.0092 (4)	0.15065 (14)	0.0481 (5)
H4n	0.3365 (18)	−0.107 (3)	0.138 (2)	0.073 (10)*
C1	0.72150 (15)	0.7175 (4)	0.23365 (14)	0.0410 (5)
C2	0.77546 (18)	0.6908 (5)	0.31817 (16)	0.0578 (7)
H2	0.8136	0.5716	0.3351	0.069*
C3	0.7717 (2)	0.8436 (6)	0.37656 (18)	0.0704 (9)
H3	0.8069	0.8271	0.4337	0.084*
C4	0.7165 (2)	1.0198 (7)	0.35112 (19)	0.0725 (9)
H4	0.7144	1.1230	0.3911	0.087*
C5	0.66361 (18)	1.0458 (5)	0.26639 (18)	0.0590 (7)
H5	0.6274	1.1686	0.2496	0.071*
C6	0.66381 (15)	0.8916 (4)	0.20639 (14)	0.0397 (5)
C7	0.60033 (14)	0.9336 (4)	0.11715 (15)	0.0388 (5)
C8	0.45421 (14)	0.5073 (4)	0.09694 (14)	0.0404 (5)
H8	0.4232	0.5325	0.0393	0.049*
C9	0.42911 (14)	0.3263 (4)	0.13752 (14)	0.0383 (5)
C10	0.37329 (15)	0.1621 (4)	0.09513 (15)	0.0442 (5)
H10	0.3438	0.1562	0.0364	0.053*
C11	0.45910 (14)	0.2716 (4)	0.22621 (14)	0.0381 (5)
C12	0.51457 (16)	0.3730 (4)	0.30105 (15)	0.0442 (5)
H12	0.5400	0.5093	0.3000	0.053*
C13	0.52987 (18)	0.2632 (5)	0.37606 (15)	0.0544 (7)
C14	0.4940 (2)	0.0577 (5)	0.38068 (18)	0.0611 (7)
H14	0.5082	−0.0124	0.4330	0.073*
C15	0.4381 (2)	−0.0412 (5)	0.30834 (18)	0.0575 (7)
H15	0.4130	−0.1776	0.3104	0.069*
C16	0.41983 (16)	0.0688 (4)	0.23177 (16)	0.0444 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0893 (3)	0.1081 (3)	0.03974 (18)	0.0001 (2)	0.00225 (16)	−0.01727 (16)
O1	0.0749 (14)	0.0508 (11)	0.0621 (13)	0.0208 (10)	0.0043 (11)	0.0021 (9)
O2	0.0521 (10)	0.0590 (11)	0.0361 (9)	0.0088 (8)	0.0070 (8)	−0.0019 (8)
O3	0.0448 (10)	0.0533 (10)	0.0436 (9)	−0.0068 (8)	0.0070 (8)	0.0117 (8)
O1w	0.0598 (18)	0.0640 (18)	0.0598 (17)	0.000	0.0116 (14)	0.000
N1	0.0375 (11)	0.0440 (11)	0.0429 (11)	0.0016 (9)	0.0059 (9)	0.0012 (9)
N2	0.0330 (10)	0.0465 (11)	0.0368 (10)	−0.0006 (8)	0.0011 (8)	0.0108 (9)
N3	0.0352 (10)	0.0414 (10)	0.0362 (10)	−0.0003 (8)	0.0070 (8)	0.0077 (8)
N4	0.0479 (12)	0.0440 (12)	0.0498 (12)	−0.0108 (10)	0.0154 (10)	−0.0050 (11)
C1	0.0374 (12)	0.0464 (13)	0.0336 (11)	−0.0023 (10)	0.0067 (9)	0.0008 (10)
C2	0.0519 (16)	0.0702 (17)	0.0374 (13)	0.0077 (13)	0.0005 (11)	0.0076 (13)
C3	0.0621 (19)	0.102 (2)	0.0326 (13)	0.0061 (17)	0.0008 (12)	−0.0035 (15)
C4	0.0592 (18)	0.107 (3)	0.0454 (15)	0.0052 (18)	0.0126 (14)	−0.0265 (17)
C5	0.0432 (14)	0.0777 (18)	0.0497 (15)	0.0099 (13)	0.0100 (12)	−0.0140 (14)
C6	0.0315 (11)	0.0508 (13)	0.0341 (11)	−0.0018 (10)	0.0093 (9)	0.0002 (10)
C7	0.0339 (12)	0.0433 (12)	0.0359 (11)	0.0031 (9)	0.0093 (9)	0.0032 (10)
C8	0.0337 (12)	0.0461 (12)	0.0343 (11)	0.0032 (10)	0.0045 (9)	0.0023 (10)
C9	0.0336 (11)	0.0408 (11)	0.0370 (11)	0.0005 (9)	0.0093 (9)	−0.0002 (10)
C10	0.0377 (12)	0.0506 (13)	0.0384 (12)	−0.0022 (10)	0.0073 (10)	−0.0033 (11)
C11	0.0336 (11)	0.0396 (12)	0.0391 (11)	0.0024 (9)	0.0111 (9)	0.0004 (10)
C12	0.0415 (13)	0.0459 (13)	0.0399 (12)	0.0009 (10)	0.0092 (10)	−0.0056 (10)
C13	0.0521 (15)	0.0701 (18)	0.0346 (12)	0.0057 (13)	0.0088 (11)	−0.0080 (12)
C14	0.0686 (19)	0.0705 (19)	0.0447 (14)	0.0048 (15)	0.0216 (14)	0.0114 (14)
C15	0.0658 (18)	0.0544 (15)	0.0553 (16)	−0.0028 (13)	0.0261 (14)	0.0072 (13)
C16	0.0430 (13)	0.0459 (13)	0.0439 (13)	−0.0026 (10)	0.0159 (11)	−0.0016 (11)

Geometric parameters (Å, º)

Br1—C13	1.898 (3)	C4—C5	1.382 (4)
O1—N1	1.224 (3)	C4—H4	0.93
O2—N1	1.216 (3)	C5—C6	1.380 (4)
O3—C7	1.231 (3)	C5—H5	0.93
O1w—H1w	0.85 (1)	C6—C7	1.505 (3)
N1—C1	1.456 (3)	C8—C9	1.435 (3)
N2—C7	1.333 (3)	C8—H8	0.93
N2—N3	1.385 (3)	C9—C10	1.364 (3)
N2—H2n	0.85 (1)	C9—C11	1.433 (3)
N3—C8	1.274 (3)	C10—H10	0.93
N4—C10	1.349 (3)	C11—C12	1.398 (3)
N4—C16	1.372 (3)	C11—C16	1.408 (3)
N4—H4n	0.85 (1)	C12—C13	1.370 (4)
C1—C6	1.381 (3)	C12—H12	0.93
C1—C2	1.384 (3)	C13—C14	1.393 (4)
C2—C3	1.372 (4)	C14—C15	1.366 (4)
C2—H2	0.93	C14—H14	0.93
C3—C4	1.365 (5)	C15—C16	1.386 (4)
C3—H3	0.93	C15—H15	0.93
O2—N1—O1	122.6 (2)	O3—C7—C6	121.2 (2)
O2—N1—C1	118.49 (19)	N2—C7—C6	117.2 (2)
O1—N1—C1	118.8 (2)	N3—C8—C9	122.2 (2)
C7—N2—N3	121.33 (19)	N3—C8—H8	118.9
C7—N2—H2n	117 (2)	C9—C8—H8	118.9
N3—N2—H2n	121 (2)	C10—C9—C11	106.5 (2)
C8—N3—N2	113.86 (19)	C10—C9—C8	124.4 (2)
C10—N4—C16	109.3 (2)	C11—C9—C8	129.0 (2)
C10—N4—H4n	126 (2)	N4—C10—C9	110.3 (2)
C16—N4—H4n	125 (2)	N4—C10—H10	124.9
C6—C1—C2	122.2 (2)	C9—C10—H10	124.9
C6—C1—N1	120.5 (2)	C12—C11—C16	119.0 (2)
C2—C1—N1	117.2 (2)	C12—C11—C9	134.5 (2)
C3—C2—C1	118.7 (3)	C16—C11—C9	106.5 (2)
C3—C2—H2	120.6	C13—C12—C11	117.3 (2)
C1—C2—H2	120.6	C13—C12—H12	121.4
C4—C3—C2	120.3 (3)	C11—C12—H12	121.4
C4—C3—H3	119.8	C12—C13—C14	123.4 (2)
C2—C3—H3	119.8	C12—C13—Br1	118.6 (2)
C3—C4—C5	120.4 (3)	C14—C13—Br1	118.0 (2)
C3—C4—H4	119.8	C15—C14—C13	120.1 (3)
C5—C4—H4	119.8	C15—C14—H14	120.0
C4—C5—C6	120.8 (3)	C13—C14—H14	120.0
C4—C5—H5	119.6	C14—C15—C16	117.7 (3)
C6—C5—H5	119.6	C14—C15—H15	121.1
C1—C6—C5	117.5 (2)	C16—C15—H15	121.1
C1—C6—C7	126.9 (2)	N4—C16—C15	130.1 (2)
C5—C6—C7	115.6 (2)	N4—C16—C11	107.4 (2)
O3—C7—N2	121.5 (2)	C15—C16—C11	122.4 (2)
C7—N2—N3—C8	−171.3 (2)	N3—C8—C9—C11	8.5 (4)
O2—N1—C1—C6	9.2 (3)	C16—N4—C10—C9	−0.5 (3)
O1—N1—C1—C6	−172.7 (2)	C11—C9—C10—N4	−0.5 (3)
O2—N1—C1—C2	−167.1 (2)	C8—C9—C10—N4	176.2 (2)
O1—N1—C1—C2	11.0 (3)	C10—C9—C11—C12	−178.4 (3)
C6—C1—C2—C3	−0.4 (4)	C8—C9—C11—C12	5.1 (4)
N1—C1—C2—C3	175.8 (3)	C10—C9—C11—C16	1.4 (3)
C1—C2—C3—C4	−0.9 (5)	C8—C9—C11—C16	−175.1 (2)
C2—C3—C4—C5	0.2 (5)	C16—C11—C12—C13	2.3 (3)
C3—C4—C5—C6	1.8 (5)	C9—C11—C12—C13	−178.0 (3)
C2—C1—C6—C5	2.3 (4)	C11—C12—C13—C14	0.8 (4)
N1—C1—C6—C5	−173.7 (2)	C11—C12—C13—Br1	178.27 (18)
C2—C1—C6—C7	−178.0 (2)	C12—C13—C14—C15	−2.3 (4)
N1—C1—C6—C7	6.0 (4)	Br1—C13—C14—C15	−179.8 (2)
C4—C5—C6—C1	−3.0 (4)	C13—C14—C15—C16	0.7 (4)
C4—C5—C6—C7	177.3 (3)	C10—N4—C16—C15	−176.4 (3)
N3—N2—C7—O3	−175.9 (2)	C10—N4—C16—C11	1.4 (3)
N3—N2—C7—C6	−0.9 (3)	C14—C15—C16—N4	179.9 (3)
C1—C6—C7—O3	−111.8 (3)	C14—C15—C16—C11	2.4 (4)
C5—C6—C7—O3	68.0 (3)	C12—C11—C16—N4	178.1 (2)
C1—C6—C7—N2	73.2 (3)	C9—C11—C16—N4	−1.7 (3)
C5—C6—C7—N2	−107.1 (3)	C12—C11—C16—C15	−3.9 (4)
N2—N3—C8—C9	−178.4 (2)	C9—C11—C16—C15	176.3 (2)
N3—C8—C9—C10	−167.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O3^i	0.85 (1)	2.09 (1)	2.937 (3)	173 (3)
N4—H4n···O1w	0.85 (1)	2.37 (3)	2.973 (3)	128 (3)
N4—H4n···O1^ii	0.85 (1)	2.43 (2)	3.142 (3)	142 (3)
O1w—H1w···O2^ii	0.85 (1)	2.22 (2)	3.061 (3)	171 (7)

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